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BACKGROUND OF THE INVENTION
[0001] This application is a continuation of U.S. patent application Ser. No. 09/351,895, filed Jul. 13, 1999, and now pending, which is a continuation-in-part of application Ser. No. 08/428,960, filed Apr. 24, 1995 and now U.S. Pat. No. 5,622,166, and incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The field of the invention is inhalers. More specifically, the invention relates to inhalers for delivering drugs in a solid finely divided dry powder or fluid form.
[0003] Inhalers are used to deliver drugs into a patient's lungs. Typically, an inhaler contains or provides a mixture of drugs and air or propellants. The mixture is delivered via the patient inhaling from a mouthpiece on the inhaler, for treatment of various conditions, for example, bronchial asthma. However, delivery of drugs via inhalation can be used for many other treatments, including those unrelated to lung condition.
[0004] One well known inhaler, the Diskhaler, described in U.S. with each successive dose. However, while the device described in U.S. Pat. No. 4,627,432 has met with varying degrees of success, disadvantages remain in indexing or advancing a blister disk within an inhaler, with opening the blisters to access the drug contents, with reliably providing intended dosages, and in other areas.
[0005] Accordingly, it is an object of the invention to provide an improved inhaler.
SUMMARY OF THE INVENTION
[0006] To these ends, the present inhaler preferably includes a cover plate pivotably attached to a lid on an inhaler housing. A blister pack disk is rotatably mounted on the housing under the cover plate, and is movable in a single forward direction. An actuator in the housing is most desirably aligned with a lever on the cover plate. The patient pushes the actuator which shears open a blister on the disk and then causes the lever to crush the blister, to deliver the drug powder contents of the blister into a duct within the housing, for subsequent inhalation by the patient.
[0007] Other and further objects will appear hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] In the drawings, wherein similar reference characters denote similar elements throughout the several views:
[0009] [0009]FIG. 1 is perspective view of the present inhaler with the mouthpiece covered by the cover assembly;
[0010] [0010]FIG. 2 is a perspective view thereof with the mouthpiece uncovered;
[0011] [0011]FIG. 3 is a plan view of the inhaler as shown in FIG. 1;
[0012] [0012]FIG. 4 is a plan view of the inhaler as shown in FIG. 2;
[0013] [0013]FIG. 5 is an exploded perspective view of the inhaler of FIGS. 1 and 2;
[0014] [0014]FIG. 6 is an plan view of the inhaler of FIGS. 1 and 2 with the lid open;
[0015] [0015]FIG. 7 is a partial section view taken along line 7 - 7 of FIG. 6;
[0016] [0016]FIG. 8 is an enlarged top and front perspective view of the cover assembly on the inhalers of FIGS. 1 and 2;
[0017] [0017]FIG. 9 is a bottom and rear perspective view of the cover assembly of FIG. 8;
[0018] [0018]FIG. 10 is an enlarged view of features shown in FIG. 9;
[0019] [0019]FIG. 11 is a partial section view taken along line 11 - 11 of FIG. 5;
[0020] [0020]FIG. 12 is similar view showing positions of various components during use of the device;
[0021] [0021]FIG. 13 is a partial section view taken along line 13 - 13 of FIG. 3;
[0022] [0022]FIG. 14 is a partial section view taken along line 14 - 14 of FIG. 4;
[0023] [0023]FIGS. 15, 16 and 17 are partial section view fragments illustrating movement of components within the device;
[0024] [0024]FIG. 18 is a section view taken along line 18 - 18 of FIG. 5;
[0025] [0025]FIG. 19 is a similar view thereof with various components omitted for drawing clarity, and showing positions of components during use;
[0026] [0026]FIG. 20 is an exploded perspective view of a blister disk for use with the inhaler shown in FIGS. 1 and 2;
[0027] [0027]FIG. 21 is a partial plan view thereof; and
[0028] [0028]FIG. 22 is a section view taken along line 22 - 22 of FIG. 21.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] Turning now in detail to the drawings, as shown in FIGS. 1 - 4 , a dry powder inhaler includes a housing 32 having a lid 38 attached to the housing with a hinge 36 . The lid 38 is preferably a transparent material, e.g., clear plastic. A removable mouthpiece 34 is provided on one side of the housing 32 . A sliding cover assembly 40 may be pivoted on the lid 38 from a closed position covering the mouthpiece 34 , as shown in FIGS. 1 and 3, to an opened position exposing the mouthpiece 34 , as shown in FIGS. 2 and 4. As best shown in FIGS. 3 and 4 (looking down through the transparent lid 38 ), a disk 42 having a plurality of radially spaced apart blisters 44 is generally centered on top of the housing 32 on a center post 140 extending upwardly from the housing 32 . A lid stop 46 on the housing 32 limits sliding movement of the cover assembly 40 in the opened position.
[0030] Turning momentarily to FIGS. 8 and 9, the sliding cover assembly 40 includes an enclosure 48 having a front curved wall 54 , a side wall 56 , a top wall 58 and a bottom wall 60 . A rim 62 extends upwardly and radially inwardly on the top wall 58 .
[0031] Referring now to FIG. 9, a glide block 64 and an outside retainer 66 extend downwardly and inwardly on the underside of the top wall 58 . A generally flat cover plate 50 is preferably integrally formed with the enclosure 48 , with the cover plate 50 and enclosure comprising the cover assembly 40 . An inside retainer 68 on the cover plate 50 extends radially outwardly. A lever 74 is pivotably supported on a lever pin 76 held in place by lever blocks 72 on the underside of the cover plate 50 . The lever 74 can pivot through a lever opening 78 in the cover plate 50 , as best shown in FIG. 8. A ramp 80 and a guide wall 82 project downwardly from the cover plate 50 , adjacent to the lever 74 , as shown in FIG. 9. The entire cover assembly 40 , which includes the enclosure 48 and cover plate 50 is pivotably attached to the lid 38 , with the lid post 52 extending through a center hub 84 on the cover plate 50 . Clearance holes 70 through the cover plate 50 on either side of the lever opening 78 allow the cover plate to sit on top of the blister disk, as shown in FIG. 18, without excessive vertical interference.
[0032] Referring to FIGS. 8, 9 and 10 , a spring arm 86 having a downwardly projecting end tab 88 is attached to or integral with the cover plate 50 . As shown in FIG. 13, the spring arm 86 includes an arm wedge 96 at its free end, alongside the tab 88 . As shown in FIG. 10, an arm lifter 102 extends downwardly from the lid 38 . An outer slot 94 through the cover plate 50 overlies the spring arm 86 . An inner slot 92 adjoining the outer slot 94 through the cover plate 50 provides clearance for the arm lifter 102 , and allows the cover assembly 40 to rotate (preferably about 90°). The arm lifter 102 includes an internal ramp, and is dimensioned to engage the arm wedge 96 , and lift the arm 86 up towards the lid 38 , as the arm wedge 96 moves into full engagement with the lifter 102 .
[0033] Turning now to FIG. 5, the housing 32 includes a mixing chamber 120 , and a staging chamber 124 connected to the mixing chamber 120 via a duct 122 . Referring now also to FIGS. 6 and 7, an inlet duct 126 extends from one side of the housing 32 to the staging chamber 124 via a duct recess 130 . A crescent barrier 128 around the top of the staging chamber 124 creates an indirect air flow path from outside of the housing, through the inlet duct 126 and into the staging chamber 124 .
[0034] In a first embodiment of the present invention, referring once again to FIG. 5, a pressure port or opening 132 in the housing 32 alongside the mixing chamber 120 connects to a pressure switch 170 via a tube 172 . The pressure port aligns with a mouthpiece port 135 leading into the central opening of the mouthpiece. This provides a continuous duct from the mouthpiece opening to the pressure switch. The mouthpiece 34 or an alternative embodiment mouthpiece 136 is secured to the housing 32 with a hook 134 . The mouthpiece is removable by twisting or rotating the mouthpiece, to disengage the hook 134 , and then by pulling it off. Rachet posts 142 having angled top surfaces project slightly above the flat top surface 138 of the housing 32 . An actuation button 146 has a post 148 extending entirely through a post opening 144 in the housing 32 .
[0035] Referring momentarily to FIG. 18, a detent 145 on the housing engages and holds the post 148 in the up position (driving the lever to crush a blister), until the disk is advanced to the next blister. At the front of the housing, behind the mixing chamber 120 , is an inwardly projecting housing inner rim 150 , and an outwardly projecting housing outer rim 152 . The outer rim 152 is engaged by the outside retainer 66 , and the inner rim is engaged by the inside retainer 68 , as the cover assembly 40 is moved between opened and closed positions. The interaction of the inner rim 150 and inside retainer 68 and outer rim 152 and outside retainer 66 , holds the cover assembly and lid down on top of the housing 32 .
[0036] Referring still to FIG. 5, a bottom cover 158 attached to the housing 32 has a button recess 164 around the actuation button 146 , so that the actuation button 146 does not project beyond the bottom surface of the cover 158 . An impeller 162 within the mixing chamber 120 is supported on the shaft of an electric motor 160 behind the mixing chamber 120 in the housing 32 . The motor 160 is wired to batteries 168 and the pressure switch 170 . A battery indicator LED 174 and a status indicator LED 176 are positioned in the housing 32 , above the pressure switch 170 .
[0037] Turning now to FIGS. 20 - 22 , the disk 42 includes a blister foil ring 190 , preferably a metal or aluminum foil having generally conical blisters formed in it. The blister foil ring 190 and a foil seal ring 192 are adhered or bonded onto a carrier disk 194 . As shown in FIG. 21, the carrier disk 194 has tabs 196 suspended within tab slots 198 by bridges 200 . Each blister 44 on the blister foil ring 190 is aligned over a tab 196 . The bridges 200 hold the tabs 196 in position, but allow the tab to pivot about the bridges, with nominal torque. As shown in FIG. 22 , powdered drug 202 is sealed within the blisters 44 . The carrier disk 194 is preferably plastic. The tab supports 200 are small enough to support the tabs 196 , but also to allow the tab to pivot under force of the post of the actuation button.
[0038] In use, a disk 42 is first loaded into the inhaler 30 by sliding the cover assembly 40 from the closed position shown in FIG. 1 to the open position shown in FIG. 2. In this position, the lid 38 and cover assembly 40 are still held down on top of the housing 32 by the interaction of the outside retainer 66 and inside retainer 68 on the housing outer rim 152 and inner rim 150 . The side wall 56 of the enclosure 48 is lifted slightly away from the housing 32 , to a allow it to pass over the lid stop 46 . As this occurs, the retainers 66 and 68 move off of and release from the inner and outer rims 150 and 152 . The cover assembly 40 and lid 38 are then pivoted upwardly about the hinge 36 , to open up the inhaler 30 , as shown in FIG. 6, for placement or replacement of a disk 42 .
[0039] A disk 42 is placed over the center post 140 over the housing top surface 138 with the blisters 44 on top. The lid 38 and cover assembly 40 are pivoted back about the hinge 36 , from the position shown in FIG. 6, to the position shown in FIG. 2. The inhaler 30 is then ready for use.
[0040] The rachet posts 142 on the housing top surface 138 project slightly into the open ends 203 of the tab slots 198 . The disk 42 is accordingly oriented so that a blister 44 will be aligned over the staging chamber 124 . The rachet posts 142 also prevent the disk 42 from moving in reverse (i.e., clockwise in FIG. 6).
[0041] With the lid 38 closed, but with the cover assembly 40 opened (as shown in FIG. 2), the inner end of the lever 74 is aligned over the top of the post 148 . The outer end of the lever 74 is aligned over the top of a blister 44 , and over the staging chamber 124 .
[0042] With the inhaler 30 preferably held upright, the actuation button 146 is pushed up. As shown in FIGS. 11, 12 and 19 , the upward movement of the post 148 on the actuation button 146 first pivots the tab 196 on the blister 44 over the staging chamber 124 . The tab pivots on the bridges 200 . As this occurs, the foil seal ring 192 sealing the blister 44 on the bottom shears away opening the blister and allowing the powdered drug 202 to fall into the staging chamber 124 .
[0043] As upward movement of the post 148 continues, the post pivots the lever 74 causing the outer end of the lever to crush the blister 44 down, to release any residual powder into the staging chamber 124 .
[0044] With one dose of the powdered drug now delivered from a sealed blister 44 into the staging chamber 124 , the patient places the mouthpiece 34 into the mouth and inhales. The inhalation draws air from outside of the housing through the inlet duct 126 , around and under the crescent barrier 128 and into the staging chamber 124 . Air and powdered drug 202 move through the duct 122 and into the mixing chamber 120 . At the same time, upon inhalation, the reduced air pressure at the mouthpiece 136 is detected by the pressure switch 170 via the tube 172 extending to the pressure port 132 . The switch 170 turns on the motor 160 , spinning the impeller 162 within the mixing chamber 120 . The air and drug is mixed in the mixing chamber 120 , as further described in U.S. Pat. Nos. 5,327,883, and 5,577,497, incorporated herein by reference. As the impeller is already spinning at high speed when the drug enters the mixing chamber, the air/drug mixing and deagglomeration are enhanced.
[0045] The patient inhales on the mouthpiece drawing in the air/drug mixture from the mixing chamber 120 via holes 125 in the rear wall of the mouthpiece 34 (which rear wall also forms the front wall of the mixing chamber 120 ).
[0046] To prepare for delivery of the next dose, the cover assembly 40 is moved from the position shown in FIG. 2, to the position shown in FIG. 1, to cover the mouthpiece 34 . As this closing movement of the cover assembly 40 occurs, the arm wedge 96 on the spring arm 86 is released from the lifter 102 . This allows the spring arm 86 to flex downwardly with the tab 88 engaging into the opened end 202 of a tab slot 198 , approximately at position A as shown in FIGS. 3 and 6. With the continued closing motion of the cover assembly 40 to the position shown in FIG. 3, the tab 88 on the spring arm 86 advances the disk 42 to the next blister 44 (moving the disk 42 counter-clockwise in FIG. 3). For a disk having 16 blisters, the advancing movement, from engagement of the tab 88 to the disk 42 , until the end of movement, is about 22°. As the disk 42 is advanced by the spring arm 86 on the closing cover assembly 40 , the disk 42 rides up and over the angled top surfaces of the rachet posts 142 and then settles back down onto the housing surface 138 with the rachet posts 142 engaged into the next set of opened ends 203 of the tab slots 198 . In this manner, the next blister 44 on the disk 42 is positioned for delivery and inhalation, as described above. When the cover assembly 40 is reopened, to the position shown in FIG. 4, the disk 42 does not move, as the spring arm 86 is lifted up and out from engagement with the disk by the interaction of the lifter 102 on the lid 38 and the arm wedge 96 on the spring arm 86 . Through this repeated motion of opening and closing the cover assembly 40 , each blister 44 on the disk 42 can be sequentially accessed, until all of the blisters are used.
[0047] As the cover assembly 40 is closed, the ramp 80 on the cover plate 50 rides over the top of the post 148 , the push it down, resetting the actuation button 146 for the next dose, as shown in FIGS. 15 - 17 . Simultaneously, the guide wall 82 , which ramps upwardly from the lever 74 , pushes down on the pivoted tab 196 from the blister delivered. The tab 196 is accordingly pushed back down into the plane of the disk 42 , so that the disk can be advanced without interference. The rachet posts 142 prevent the disk 42 from moving in reverse (clockwise in FIG. 3) at anytime.
[0048] Accordingly, a novel inhaler is described and shown with various advantages over the prior art design. The above-described inhaler may contain various changes and modifications, including various substitutions and equivalents, without departing from the spirit and scope of the present invention. | A drug powder inhaler has a cover plate pivotably attached to a lid on an inhaler housing. A lever is pivotably attached to the cover plate. A blister pack disk is rotatably mounted on the housing under the cover plate. A powder duct in the housing extends from a staging chamber underneath one end of the lever to an aerosolizing chamber. An actuator in the housing is pressed to shear open a blister on the blister pack disk and thereby deliver the drug dose contents of the blister into the staging chamber. A switch senses pressure in the mouthpiece and switches on a motor spinning an impeller within the aerosolizing chamber, when inhalation is detected. | 0 |
RELATED APPLICATIONS
This nonprovisional application claims the benefit of provisional patent application U.S. Ser. No. 60/753,900, filed on Dec. 22, 2005 which is hereby incorporated by reference in its entirety.
TECHNICAL FIELD
The present invention relates generally to methods and systems for reservoir simulation predicting the flow of fluids in an underground reservoir, and more particularly, to enhancing reservoir performance forecasting by accounting for fluid flow effects due to heavy oil solution gas drive.
BACKGROUND OF THE INVENTION
Reservoir simulation is used to predict the flow of fluids in an underground reservoir. The fluid flow may include oil, gas and water. Such reservoir forecasting is important in reservoir management and estimating the potential recovery from a reservoir.
Reservoir simulation is well known throughout the oil industry and in the scientific literature. A good primer on the principles behind reservoir simulation is K. Aziz and A. Settari, Petroleum Reservoir Simulation , Elsevier Applied Science Publishers, London (1979). Another description of how reservoir simulation is generally performed is described in U.S. Pat. No. 6,052,520 to Watts III et al. These references, are hereby incorporated by reference in their entireties.
The following are general steps taken in a conventional reservoir simulation. First, a reservoir is selected for which the rock and fluid properties are to be modeled and simulated. The reservoir is modeled and discretized into a plurality of cells. Nonlinear governing equations are constructed for each cell, generally in the form of finite difference equations, which are representative of properties of rocks and fluids in the reservoir. Examples of rock properties include porosity, capillary pressure, and relative permeability for each phase of fluid (oil, water, gas.) Examples of fluid properties include oil viscosity, oil formation factor (B o ), and pressure, temperature, and saturation in each of the cells. Nonlinear terms in these equations are linearized to arrive at a set of linear-equations for each timestep of the simulation. These linear equations can then be solved to estimate solutions for unknowns such as pressure and saturation in the cells. From these values of pressure and saturation other properties can be estimated including the overall production of oil, gas and water from the reservoir in a timestep. The aforementioned steps are repeated over many such timesteps to simulate fluid flow over time in the reservoir.
One of the key properties needed in reservoir simulation is the permeability of a rock to flow. Absolute permeability K is a measure of a rock's ability to transmit flow and can vary greatly throughout a reservoir and surrounding formations. When gas, oil and water move through porous rock, they do not move at equal velocities. Rather, the fluids compete with one another. Relative permeability, k r , is the ratio of the effective permeability, k e , when more than one fluid is present, to the absolute permeability K. Effective permeability k e is the measured permeability of a porous medium to one fluid when another is present. The relationship between relative permeability k r and saturation S depends on the reservoir rock and fluid and may vary between formations. Also, the relative permeability k r depends on the relative proportion of the fluids present, i.e. fluid saturations.
FIG. 1 illustrates a typical relative permeability k rg versus saturation S g curve for gas. Gas cannot flow at any appreciable rate until gas saturation reaches a minimum threshold value. Looking to FIG. 1 , this threshold value is referred to as critical gas saturation S gc 0 and begins at a value of approximately 0.03 or about 3% saturation. At the other end of the curve is an endpoint relative permeability k rgro 0 which is the gas relative permeability value k rg at which movement of residual oil remaining in the rock is minimal. As reservoir rock will always contain a minimal amount of residual oil, gas saturation cannot reach 100%. The total percentage of saturation must add up to 100%. In this case, there is a maximum 76% gas saturation S g and 24% residual oil saturation S org . As seen in FIG. 1 , the maximum relative permeability, k rgro 0 , occurs at a saturation of approximately 0.76 with k r =0.40. These values of S gc 0 and k rgro 0 shall be referred to as endpoint baseline values for gas saturation S g and relative permeability k rg .
Ideally, relative permeability curves are developed through laboratory experiments on core samples taken from reservoirs for which reservoir simulation is to be performed. For example, displacement tests may be used to develop the relative permeability k rg vs. saturation S g curves. Such tests are well known. Particularly well known displacement test procedures are described in E. F. Johnson, D. P. Bossler, and V. O. Naumann, Calculations of Relative Permeability from Displacement Experiments , Trans. Am. Inst. Mining Engineers, Volume 216, 1959, pp. 370-378 and S. C. Jones and W. O. Roszelle, Graphical Techniques for Determining Relative Permeability from Displacement Experiments , Journal of Petroleum Engineering, Volume 30, pp. 807-817 (1978). These displacements experiments are usually conducted at slow depletion rates as it is commonly accepted that permeability curves are generally independent, of how fast gas flows through reservoir rock.
Alternatively, if core samples are not available, the relative permeability k rg versus saturation S k curves can be theoretically created. For example, the curves may be developed from comparable analogue reservoirs.
Once relative permeability k rg versus saturation S g curves have been obtained, then the relative permeabilities k rg to be used in a reservoir simulation can simply be obtained from these curves assuming saturations S g in the cells of the reservoir model are known. The saturations S g are generally known either from initial conditions established at the beginning of a simulation, from the last timestep in the simulation or else from calculations within an iteration in a timestep.
The production of heavy oil is initially driven primarily by oil pressure. Heavy oil may be considered to include oil having an API gravity 20° or less. Significant quantities of gas are often entrained within the heavy oil while under high reservoir pressures. After sufficient production of heavy oil from a reservoir, the pressure in portions of the reservoir may drop below the bubble point pressure. At this pressure, gas readily comes out of solution from the heavy oil. Once sufficient gas has been released from the oil, the gas is believed to form a continuous phase and gas can flow through the reservoir and the rate of production of gas is significantly enhanced. As indicated above, the saturation S g at which there is an initiation of gas flow is referred to as the critical gas saturation or S gc . FIG. 11 shows a graph of cumulative gas produced from a core sample versus time in minutes. The breakpoint in the curve shown there represents S gc .
Tests have shown that the amount of oil recovery from a heavy oil reservoir is dependent upon the rate of depletion of the reservoir. Often higher rates of depletion will lead to an overall enhanced oil recovery. As the mechanisms of heavy oil solution gas drive are not well understood, reservoir simulators typically utilize static gas relative permeability k rg versus saturation S g curves, such as the one seen in FIG. 1 , which are independent of fluid flow or depletion rates. Once these curves are developed for respective types of rock which are to be modeled, the curves will remain the same (i.e., endpoints of S gc 0 and k rgro 0 remain fixed) throughout the reservoir simulation regardless of the rate of flow through the reservoir cells. Such assumptions that permeability curves are static for general reservoir simulation of hydrocarbon bearing subterranean formations containing non-heavy oil are generally satisfactory.
However, in the case of heavy oil, non-equilibrium solution gas drive (“Foamy Oil”) is a significant production mechanism affecting critical gas saturation S gc and oil recovery. Currently, understanding of heavy oil solution gas drive at all scales (pore, core and field) is limited. Conventional reservoir simulators fail to accurately account for this solution gas drive in forecasting fluid flow in a reservoir. This is a significant shortcoming often resulting in forecasts which underestimate heavy oil production. The present invention overcomes this shortcoming by accounting for the effects of heavy oil solution gas drive.
SUMMARY OF THE INVENTION
A method of predicting a property of at least one fluid in a subterranean reservoir containing heavy oil entrained with gas is disclosed. For example, the property might include the overall production of fluids from the reservoir, i.e., oil, gas and water. The prediction is made using a reservoir simulator which uses a reservoir model having a plurality of cells representative of the reservoir. For at least some of the cells and for at least some of the iterations of the reservoir simulation, gas relative permeability k rg is dependent upon the local fluid velocities v a in the cells.
In a preferred embodiment of this method, a baseline correlation is developed for gas relative permeability k rg versus gas saturation S g , typically based on displacements tests performed at slow depletion rates. Next, a capillary number N ca dependent correlation is developed between at least one of, and most preferably, both of critical gas saturation S gc and capillary number N ca and endpoint of gas relative permeability K rgro and capillary number N ca . Non-limiting examples of how this correlation may be expressed include, by way of example and not limitation, using a mathematical equation which describes a curve or by creating a corresponding look-up table.
These experimentally derived capillary number N ca dependent correlations can then be used, in conjunction with reservoir simulation, to capture the effects that heavy oil solution gas drive and depletion rates have on the production of heavy oil and gas entrained therein. Capillary numbers N c are calculated for a plurality of cells in the reservoir model representative of the subterranean reservoir for which fluid properties are to be simulated. S gc and/or k rgro values are selected from the capillary number dependent correlations based upon the capillary numbers N c calculated for the cells. Adjusted baseline correlations are then developed. For example, the original endpoints of the baseline curve, i.e. S gc 0 and k rgro 0 , are replaced with the new capillary number dependent S gc and k rgro values and the curve therebetween adjusted, such as by linear scaling. FIG. 2 suggests that an adjusted baseline curve can be developed by changing the original endpoint values S gc 0 and k rgro 0 to other values of S gc and k rgro which are based, in part, upon the velocity of oil v a flow through the cells.
Gas relative permeabilities k rg for the plurality of cells are selected from corresponding adjusted baseline correlations. These relative permeabilities k rg are then used in a reservoir simulation to predict a property of at least one fluid in a subterranean reservoir containing heavy oil entrained with gas. This predicted property may be the production of oil, water or gas. Preferably, once saturation S g in a cell is equal to or greater than the critical gas saturation S gc level, the current adjusted baseline correlation for that cell is fixed for the remaining simulation time-steps. This fixing of the adjusted baseline correlation once gas begins to flow assists in maintaining stability during the solution of the system of equations modeling the reservoir.
One or both of the capillary dependent correlations of S gc or k rgro can be used in adjusting the baseline correlation to come up with an adjusted baseline correlation. These adjusted baseline correlations, through the use of the capillary numbers N c , capture tire effects that the depletion rate/fluid velocity flow and viscosity have on relative permeability during heavy oil production under heavy oil solution gas drive. Preferably, depletion experiments are performed at various depletion rates to develop the capillary number dependent correlations for the S gc and k rgro . However, if necessary, it is possible to theoretically predict what such capillary number dependent correlations should be.
Relative permeabilities k rg can fee selected which are dependent upon capillary numbers N c calculated at the beginning of a time step in a reservoir simulation. Alternatively, the capillary numbers N c can be repeatedly calculated throughout iterations in a timestep to provide constant updating of relative permeability curves during the simulation. Again, this updating of a capillary number N c for relative permeability curves of a cell is preferably stopped once the saturation S g in a cell remains at or above the critical gas saturation S g , during simulation.
It is an object of the present invention to enhance reservoir performance forecasting by better accounting for fluid flow effects due to heavy oil solution gas drive than in conventional reservoir simulators thereby improving the predictive capability of reservoir simulations involving heavy oil flow in subterranean formations which can lead to improved reservoir management strategies.
It is another object to experimentally determine values for critical gas saturations S gc and/or for endpoint of gas relative permeability k rgro for a core sample at a number of different depletion rates and correlate these values against capillary numbers N ca to create capillary number dependent correlations. These capillary number N ca dependent correlations can be used in conjunction with a reservoir model, and calculated capillary numbers N c calculated during a reservoir simulation, to more accurately estimate relative permeabilities k rg to be used in the reservoir simulation of heavy oil.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects, features and advantages of the present invention will become better understood with regard to the following description, pending claims and accompanying drawings where:
FIG. 1 shows a conventional gas relative permeability k rg versus saturation S g curve;
FIG. 2 depicts adjusting the conventional curve of FIG. 1 by modifying, the endpoints of S gc 0 and k rgro 0 to coincide with values of S gc and k rgro selected from capillary number dependent correlations of S gc versus N ca and k rgro versus N ca ;
FIG. 3 shows a flowchart of steps taken in a preferred embodiment of the present invention for carrying out reservoir simulation which utilizes gas relative permeabilities k rg which are dependent upon local velocities v a of fluid flow in cells;
FIG. 4 shows a schematic drawing of an experimental setup used to determine gas saturation S g from core and sandpack samples;
FIG. 5 depicts a graph of average sandpack pressure and pressure differential versus time across a sandpack sample in a last depletion experiment;
FIG. 6 illustrates a graph of cumulative oil and gas produced in the fast depletion experiment of FIG. 5 ;
FIG. 7 shows a graph of average sandpack sample pressure and effluent density for a slow depletion experiment;
FIG. 8 depicts a graph of average sandpack sample pressure and cumulative oil produced for a slow depletion experiment;
FIG. 9 shows a graph of oil recovery as a function of average pore pressure for sandpack experiments at depletion rates of 0.3 and 0.03 cc/min.;
FIG. 10 is a graph of oil recovery as a function of average pore pressure for core experiments at depletion rates of 0.082, 0.08, and 0.002 cc/min, respectively; and
FIG. 11 is a graph of cumulative gas produced (measured) and cumulative solution gas produced (calculated) vs. time.
DETAILED DESCRIPTION OF THE INVENTION
1. Introduction
The present invention accounts for the effects of heavy oil solution gas drive, and more particularly, for the effects that the rates of fluid depletion have on heavy oil production. Velocity or depletion rate dependent relative permeability values k rg are utilized in a heavy oil reservoir simulation to provide for more accurate reservoir simulation forecasts than are achieved with conventional reservoir simulation.
In a preferred embodiment, capillary numbers N r , which are dependent on oil velocities v a , are calculated for reservoir cells. These capillary numbers N c are used to adjust baseline relative permeability correlations to account for the velocity or depletion rate effects on relative permeability k rg . In this preferred embodiment, capillary number N ca dependent critical gas saturations S gc and/or endpoint relative permeabilities k rgro correlations are first developed, preferably based on laboratory experiments. Then values of S g , and/or k rgro , corresponding to the capillary number N c calculated for a cell, are used to adjust the baseline relative permeability correlation for that cell. Relative permeability k rg values are then selected from these capillary number adjusted baseline relative permeability correlations based upon the saturations S g in the cells.
FIG. 3 provides an exemplary flowchart of steps which may be used to implement the heavy oil solution gas drive reservoir simulation of the present invention. In step 100 , a baseline correlation is created between k rg and S g . Correlations are then developed between S gc and N ca and/or k rgro and N ca in step 110 . For a number of cells in a reservoir model, capillary numbers N c are calculated in step 120 . For each of these cells, adjusted baseline correlations between k rg and S g are established in step 130 which are dependent upon N c and the correlations developed in step 110 . Gas relative permeabilities k rg are then selected in step 140 for each of the cells from the adjusted baseline correlations between k rg and S g using saturation S g values from the cells. These capillary number dependent permeabilities k rg are then used in step 150 in a reservoir simulation to predict properties of fluid flow in the reservoir model.
A description of an exemplary test method for establishing correlations between S gc and N ca and between k rgro and N ca will be described. Then, modifications will be described which are made to a conventional reservoir simulator to incorporate the depletion rate/capillary number dependent S gc and/or k rgro correlations for selecting relative permeabilities k rg when conducting a reservoir simulation.
II. Establishing Correlations
A. Baseline Gas Relative Permeability k rg vs. Saturation S g Correlations
Correlations between gas relative permeability k rg and saturation S g are established so that relative permeability values k rg can be utilized by a reservoir simulator based upon known saturations values S g in cells of a reservoir model. Ideally, these correlations are experimentally developed from core samples from the reservoir for which the reservoir simulation is to be performed. Alternatively, representative sand packs and/or synthetic oil may also be used to develop the correlations. The preferred methods to establish these baseline correlations are the methods of Johnson, Bossler, and Naumann or else the method Jones and Roszell, which were cited above in the background section and are well known to those skilled in establishing permeability curves. Alternatively, there are many other well known schemes for establishing gas relative permeability k rg versus saturation S g curves for reservoir rocks and fluids. Typically, k rg is going to be a function of S g . For practical reasons, one often normalizes the gas saturation used in the k rg correlation. One such normalization is described in Eqn. 12. Such normalization allows the simulator to readily evaluate k rg for changing end-points, (e.g., S gc and S org )
If core samples are not available, then the correlations between relative permeability k rg and S g saturation S g can be theoretically estimated. As a non-limiting example, an analogous formation maybe used to initially establish baseline curves. Non-limiting examples of correlations may take several forms such as curves, mathematical expressions, look-up tables, etc.
FIG. 1 is an exemplary baseline curve or correlation of gas relative permeability k rg versus saturation S g . A baseline value for S gc 0 is shown at about 0.03 or 3%. Above this value, it is expected that gas will begin to flow freely rather than being primarily trapped within the the porous medium. The maximum gas saturation S g is about 76% with there being a 24% saturation of residual oil saturation S org . It is assumed there is very little presence of water for this example. At the maximum gas saturation S g =76%, the maximum gas relative permeability k rgro 0 , is approximately 0.4%.
B. Correlations Between S gc vs. N ca and k rgro vs. N ca
Laboratory experiments were conducted at various depletion rates to establish S gc vs. N ca and k rgro vs. N ca correlations. S gc is obtained in a method to be described below. N ca is calculated using Eqn. (8) below. From the experiments and history matching using reservoir simulations on core or sandpack samples, values of S gc , k rgro and N ca for each depletion rate were obtained. Then correlations between S gc and N ca and between k rgro and N ca were obtained by curve fitting the S gc , k rgro and N ca data. History matching of production data on the core samples may be used to enhance the accuracy of the correlations.
1. Live Oil Preparation
Live oil was prepared by combining unfiltered dead oil and methane. The water content of the oil was negligible. PVT (Pressure, Volume, and Temperature) data: Gas-Oil-Ratio (R s ), Oil Formation Volume Factor (B c ) and Gas Formation Volume Factors (B g ), were determined through a combination of experiments (constant composition expansion, flash, density measurement) and tuning of equation of states. Live oil viscosity was measured in a capillary viscometer (ID=0.05 in) at reservoir temperature. Table 1 lists relevant properties of the live oil at 178° F.
TABLE 1 Properties Of Crude Oil Bubble Point Pressure (Psia) 1350 Solution GOR (cc/cc) 20 B o at Bubble Point Pressure 1.0918 Live Oil Viscosity (cp) 240 Dead Oil Viscosity (cp) 1300
2. Depletion Experiments
Depletion experiments were conducted at constant depletion rates in either a horizontal 80-cm long sandpack or in a 29-cm horizontal composite core (4 plugs). The sand used in the sandpack experiments was clean Ottawa sand ranging in size from 75 to 125 μm. The sand was packed in a specially made Viton sleeve equipped with pressure ports. The sandpack and composite core porosities were measured with a helium porosimeter. Sandpack and composite core properties are listed in Table 2:
TABLE 2
Sandpack And Composite Core Properties
Composite
Sandpack
core
Temperature, ° F.
178
178
Length, cm
80
29
Diameter, cm
5.04
5.04
Overburden Pressure, psia
2050
2050
Porosity
0.33
0.27
Pore Volume, cm 3
560
162
Live Oil Permeability, md
2000
1850
Range of Depletion Rates, cm 3 /min
0.002 to 0.3
0.0003 to 0.03
The depletion rate was controlled using one or two ISCO pumps operating in a refill mode. FIG. 4 shows a schematic of the experimental set-up. During the depletion, the pressure (inlet, outlet, and at several points along the core), the production of oil and gas, and the density of the effluent was monitored. The coreholder was placed in a Siemens Somatom HiQ CT scanner to monitor spatial and temporal gas saturation.
3. Procedure
The dry sandpack was initially CT (Computer Tomography) scanned at reservoir conditions (i.e., under overburden stress and at temperature). The core was then flushed with CO 2 , evacuated and saturated with kerosene at a back pressure of ˜1600 psia. The sandpack (or composite core) permeability was measured with kerosene at several flow rates. The kerosene-saturated sandpack was also CT-scanned. The sandpack porosity was calculated using the wet and dry CT-scans and CT number of air and kerosene. Live oil was then slowly injected into the core to displace the kerosene. Permeability of the sandpack was also measured with live oil at several flow rates. The live-oil injection rate was then reduced so that the differential pressure across the core was less than 2 psi.
The live-oil saturated sandpack was CT-scanned to record initial conditions. Depletion was started at a pressure of ˜1500-1700 psia (about 150-350 psi above the bubble point pressure). The inlet valve was closed and the downstream Isco pump A was operated at a constant withdrawal rate. After a given depletion time, the pumps were switched and Isco pump B withdrew fluids while Isco pump A delivered oil and gas into the collection system. The pump cycle was repeated until the outlet pressure decreased to about 200 psia. Pressures, temperatures and fluid accumulation in the collection system were continuously recorded using conventional delta acquisition software. The density of the produced fluid was continuously measured using an in-line density meter. The sandpack was also periodically scanned to determine directly gas saturation, S g , as a function of time and position.
4. CT-Scanning
A Siemens Somatom HiQ CT scanner was used to monitor spatial and temporal gas saturation. This third generation CT-scanner has 768 stationary detectors and a rotating X-ray source. Scans were conducted at 133 kV and the scan time was 2.7 seconds. The voxel size was approximately 0.625 mm 3 for a scan thickness of 10 mm and the uncertainty in saturation measurement was +/−1.5 saturation units. Scan thicknesses of 10 mm and/or 5 mm were acquired.
5. Results
During the course of experiments pressure information along the core and at the closed core inlet and open core outlet, the amount of oil and gas produced, the effluent density and gas saturation (via the CT-scanner) were acquired. The typical responses observed during an experiment are shown in FIGS. 5 and 6 . FIG. 5 shows the average sandpack pressure and pressure differential across the sandpack during a fast depletion experiment. FIG. 6 illustrates the cumulative oil and gas produced during a fast depletion experiment.
While not wishing to be held to a particular theory, it is believed that at an early time, production is through oil and formation expansion only (there is no free gas in the system) and the pressure falls rapidly. At the (apparent) bubble point pressure, gas bubbles start to nucleate. As the pressure decreases below the bubble point pressure, gas bubbles slowly grow in size and oil production is dominated by gas expansion. As can be seen from FIG. 5 , the rate of pressure decrease was significantly reduced. Oil was the only moving phase and the gas collected was by liberation of dissolved gas in the collection system. At the critical gas saturation S gc , gas bubbles are connected throughout the sandpack and gas starts to flow freely. Note that there is a significant increase in gas production while the oil production tapered off (see the sharp break in the cumulative gas production plot at ˜270 minutes).
For the slower depletion rate experiments in the sandpacks and for the core experiments, the effluent density was also measured. FIGS. 7 and 8 show typical responses which were observed with this instrument. FIG. 7 illustrates the average sandpack pressure and effluent density for a slow depletion experiment. FIG. 8 depicts the average sandpack pressure, cumulative oil produced (collected in the separator and inferred based on the effluent density) for a slow depletion experiment.
6. Rate Effect
The main effect observed during the depletion experiments was that oil recovery is highly sensitive to the depletion rate. This phenomenon was observed with both large sandpack experiments ( FIG. 9 ) and small core experiments ( FIG. 10 ). FIG. 9 illustrates oil recovery as a function of average pore pressure (sandpack experiments−rates=0.3 and 0.03 cc/min). FIG. 10 shows oil recovery as a function of average pore pressure. (Core experiments−rates=0.082, 0.08, and 0.002 cc/min.)
In addition to the rate effect, note that the overall oil recovery observed in these experiments is quite large (up to ˜30% OOIP). Such high recovery and this dependency on depletion rates can not be readily explained by traditional physics. Moreover, this phenomenon is not modeled properly with current commercial simulators.
7. Data Analysis—S g and S gc Determination
The critical gas saturation S gc is the saturation at which the cumulative gas produced starts to increase significantly. FIG. 11 shows the cumulative gas produced (measured) and cumulative solution gas produced (calculated) vs. time. The critical gas saturation S gc can also be determined based on the effluent density.
With the set-up described in FIG. 4 , there are several ways to determine the gas saturation:
(1) direct in situ measurement with the CT-scanner; (2) material balance using the amount of fluids collected in the collection system; and (3) material balance using the density of the effluent stream.
Methods 2 and 3 require the use of PVT data (namely formation volume factor and density as a function of pressure).
Material Balance:
S g = 1 - S o ( 1 ) S O = ( N - N p ) × B O N × B Oi × ( 1 - c f ( P i - P ) ) ( 2 )
where N is the oil in place (stb) at the beginning of the experiment and at pressure P 1 , N p is the cumulative oil produced (stb) at pressure P (N p is measured with the collection system), B o and B oi are the oil formation volume factors at P and P 1 , respectively and c f is the rock or sandpack compressibility (1/psi).
Above the bubble point, oil is produced through oil and formation expansion only. That is
N p = ( c o + c f ) × ( P i - P ) B oi B o × N ( 3 )
where the oil compressibility is given by
c
O
=
B
O
-
B
Oi
B
Oi
×
(
P
i
-
P
)
(
4
)
With c o known, the sandpack and composite core compressibility are calculated using Eqn. (3).
As noted above, N p is measured through the collection system. Alternatively, the amount of oil produced can be based on the effluent density, ρ eff :
N
p
=
depletion_rate
×
ρ
off
-
ρ
g
ρ
o
-
ρ
g
×
Δ
t
×
1
B
o
+
N
ρ
-
1
(
5
)
Both porosity and gas saturation can be calculated using the CT-scanner. Porosity is given by
Φ = CT saturated_core - CT dry_core CT dry - CT gas ( 6 )
where CT saturated — core is the CT number for the sandpack saturated with kerosene (at initial pressure), and CT dry — core is, the CT number of the sandpack saturated, with gas. CT liq and CT gas are the CT numbers for kerosene and air, respectively.
Similarly, the gas saturation is obtained with the following equation:
S g = CT p - CT saturated_core CT dry_core - CT satrurated_core ( 7 )
where CT p is the CT number measured during the depletion (at pressure P), CT saturated — core is the CT number for the sandpack saturated with live oil (at initial pressure), and CT dry — core is the CT number of the sandpack saturated with air and at initial pressure.
8. Data Analysis—Capillary Number Calculation
For each experiment, the average capillary number (N ca ) was calculated using the pressure differential recorded during the depletion. The capillary number can be calculated in several ways. In this preferred embodiment, the following formula was used:
N ca = K × Δ P σ × L ( 8 )
where K is the permeability of the core or sandpack, σ is the gas-oil surface tension (estimated to be 80 dyn/cm for the oil used in the experiment), L is the sandpack length, and ΔP is the pressure differential observed before the gas is becomes mobile.
9. Data Analysis—S gc and k rgro as a Function of N ca
Based on the above analysis, S gc is plotted as a function of N ca for all the available experiments. The data is then curve fit, preferably, using an exponential function (Eqn. (9)) to interpolate/extrapolate the missing data. The coefficient “a” and exponent “b” values are specific to each oil/rock system.
By way example, and not-limitation, the preferred mathematical correlations between S gc and k rgro as functions of N ca are as follows:
S
→
gc
-
S
gc
o
=
a
·
log
(
N
→
ca
)
+
b
(
9
)
and
K
~
rgro
K
rgro
o
=
c
·
(
N
→
ca
)
d
(
10
)
S gc 0 and k rgro 0 are “conventional” critical gas saturation and end-point of gas relative permeability values, respectively, as described above in the background and as shown in FIG. 1 .
Reservoir simulations conducted on core samples at various depletion rates are used to determine the values for k rgro . For each simulation run, the critical gas saturation S gc is known, so this endpoint on a gas relative permeability k rg versus saturation S g is known. Various estimates are made for the other endpoint of the curve k rgro . A trial and error method is then used to determine which estimated value of k rgro matches the experimental production output from the core sample at a particular depletion rate. This history matching of experimental production results with simulated runs is used to determine k rgro at a number of depletion rates, which correspond to N ca values. These values of k rgro versus N ca are then curve fit to arrive at a capillary number dependent correlation. Most preferably, this correlation is in the form of Eqn. (10) with values of “c” and “d” being determined.
III. Reservoir Simulation Utilizing Heavy Oil Solution Gas Drive
Functional forms of S gc and k rgro vs. N ca , obtained from experimental data, are implemented in this exemplary embodiment, preferably, using a modified implicit algorithm in a reservoir simulator. By way example, and not limitation, the preferred forms for S gc and k rgro are input as functions of N ca using Eqns. (9) and (10) from above. The parameters a, b, c and d are user's input to the reservoir simulator. Note in FIG. 2 , that S gc is a function of a, b, and capillary number N ca . Similarly, k rgro is a function of c, d, and N ca . In the preferred embodiment of this invention, the following are default values: a=10 4 ; b=1.0; c=10 4 and d−1. Ideally, the calculated S gc and k rgro values are limited to user's specified maximums and minimums, respectively. For example, maximum S gc =0.1 and minimum value of k rgro =10 −4 may be used. Since N c is directional, S gc and k rgro are calculated for each cell face and thus are directional too.
To reduce oscillation and convergence problems, a modified implicit algorithm of the preferred embodiment is implemented to calculate S gc and k rgro . When the gas-phase is not mobile, i.e., saturation S g ≦S gc , S gc and k rgro are calculated, for example, using Eqns. (9) and (10), respectively. When the gas-phase is flowing, S gc and k rgro become invariant—neither increase nor decrease. Their values are calculated using the capillary number N c at the beginning of the time-step when the gas-phase becomes, mobile and fixed for all remaining time-steps.
A. Calculation of Cell Capillary Numbers N c
In this preferred exemplary embodiment, a modified expression for capillary number N c is preferably incorporated into the reservoir simulator using the following expression:
N → c = K → · ∇ Φ o σ og = K → · ∇ ( P o - ρ o g D ) σ og ( 11 )
where σ og is oil-gas inter-facial tension, K is rock permeability, Φ o is oil-phase potential, P o is the change in pressure across a face of a cell, ρ o =density of oil, g=gravitational constant, and D=change in depth from a datum.
This modified definition of N c leaves out oil relative permeability in the equation. Since N c is ideally computed implicitly, this greatly simplifies the calculation of derivatives for gas relative permeability (k rg ) as a function of primary variables during Jacobian generation. Also, the potential gradient in the N c calculation is directional and is based on the gradient across the face of the two adjacent grid blocks. For each Newton iteration, a capillary number N c is calculated for each grid-block face. In a 3-D model, there will be six directional N c for each grid block. Each N c corresponds to one of the six values at the cell faces. The use of directional N c results in a Jacobian that can be easily solved by conventional linear equation solvers. For wells, in this preferred embodiment, an averaged N c from all grid-block faces is calculated.
B. Adjusting Baseline Relative Permeability Correlations
Each cell is assigned a particular rock type or facies. Each of these rock types or facies corresponds to particular baseline gas relative permeability k rg vs. saturation S g curve, such as the one shown in FIG. 1 . These respective baseline curves are adjusted for each respective cell. This is accomplished for each cell by replacing the original values of S gc 0 and k rgro 0 with capillary number dependent values of S gc and k rgro calculated using Eqns. (9) and (10) and the particular capillary number N c calculated for each respective cell. The baseline curve connecting these endpoints is preferably adjusted by scaling. Scaling of the relative permeability could be done using several methods. Equation (12) shows such a method:
K
rg
=
F
(
S
g
-
S
gc
1
-
S
gc
-
S
org
)
(
12
)
Eqn. (12) simply states that k rg is a function of S g , S gc and S org . (For gas saturation greater than S org the oil phase is immobile—i.e., K ro =0). The function F could be (but is not limited to) a simple power law:
K
rg
=
K
rgro
0
(
S
g
-
S
gc
1
-
S
gc
-
S
org
)
2
(
13
)
In the conventional treatment of gas relative permeabilities, S gc in Eqn. 12 or 13 is equal to S gc 0 . However, with this formulation, S gc in Eqns. 12 and 13 is now a function of the capillary number.
Additionally, if the endpoint of gas relative permeability k rgro is decreased by 10% relative to the original k rgro 0 of the baseline curve, then all gas relative permeability values on the correlation or curve will be decreased by 10%. Those skilled in the art will appreciate that many other ways of adjusting the baseline curve to reflect changes in the updated values of endpoints S g , and/or k rgro can be used and are within the scope of this invention as well.
C. Selecting Gas Relative Permeabilities k rg for Incorporation into the Reservoir Simulator
Saturation values S g may come from initial conditions when the reservoir simulation is first started, from the previous time step, or else from values calculated during Iterations within a time step. The saturation S g of each reservoir cell is then examined and the corresponding relative permeability k rg is selected from the adjusted baseline correlation. As described above, if S g ≧S gc , then the correlation from the previously calculated curve is used to determine k rg .
D. Running Reservoir Simulation Using Selected Gas Relative Permeabilities k rg
Finite difference equations are solved to determine unknowns, such as pressure P or saturation S g . These finite difference equations rely upon the latest updated relative permeabilities k r , including the capillary number dependent gas permeabilities k rg for the reservoir cells. Such finite difference equations are well known those skilled in the art of reservoir simulation. Examples of well known solution methods for such equations include: (1) Fully Explicit; (2) Implicit Pressure, Explicit Saturation (IMPES); (3) fully Implicit; (4) Sequential Implicit (SEQ), Adaptive Implicit (AIM); and Cascade. In the preferred embodiment, a fully implicit method is used to solve these equations.
If the solutions to a state variable, i.e. pressure or saturation, are within a satisfactory tolerance range during an iteration, then final fluid properties will be established for a timestep. Volumes of production of gas, water and oil during the timestep can be established from these fluid properties, as is conventionally done with reservoir simulators. The reservoir simulator may then run over many more timesteps until a predetermined length of time is met. The cumulative production over these timesteps provides an estimation of the production from the subterranean formation.
The present invention also include a system for carrying out the above reservoir simulation using relative permeabilities k rg that are dependent upon depletion rate/fluid velocity and viscosities of crude oil. Further, the present invention also includes a program storage device which carries instructions for carrying out this reservoir simulation using fluid velocity dependent relative permeabilities.
While in the foregoing specification this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to alteration and that certain other details described herein can vary considerably without departing from the basic principles of the invention.
NOMENCLATURE
a=coefficient for calculating S gc ;
b=exponent for calculating S gc ;
B oi =oil formation volume factor at P 1 ;
B o =oil formation volume factor at P;
Bg=gas formation volume factor at P;
c=coefficient for calculating k rgro ;
c f =rock or core sample compressibility (1/psi);
c o =oil sample compressibility (1/psi):
CT dry — core =CT number of a sample saturated with gas;
CT saturated — core =CT number of a sample saturated with kerosene (at initial pressure);
CT p =CT number measured during depletion at pressure P;
CT liq =CT number for kerosene;
CT gas =CT number for air;
d=exponent for calculating k rgro ;
D=change in depth from a datum;
g=gravitational constant;
k e =effective permeability;
k r =relative permeability, dimensionless;
k rg =gas relative permeability, dimensionless;
k rgro =gas relative permeability with minimum residual oil; dimensionless;
k rgro 0 =endpoint gas relative permeability with minimum residual oil, dimensionless;
k ro =oil relative permeability, dimensionless;
K=rock permeability;
K=slope of the solution-gas curve, psi −1
N c =capillary number calculated for a particular cell of a reservoir model;
N ca =capillary number;
ΔP=change in pressure (psi);
L=length of test chamber (inches);
N=oil in place (stb) at initial conditions;
N p =cumulative oil produced (stb) at pressure P (cm 3 );
Φ o =oil-phase potential,
P 1 =pressure at time i, psi;
ΔP o =the change in pressure across a face,
ρ eff =effective density;
ρ g =density of gas;
ρ o =density of oil;
R s =Gas-to-oil ratio;
S=saturation, dimensionless;
S g =gas salutation, dimensionless;
S gc =critical gas saturation, dimensionless;
S o =oil saturation, dimensionless;
S gc o =endpoint critical gas saturation, dimensionless;
S org =residual oil saturation to gas for a particular rock region, dimensionless;
stb=stock tank barrel;
σ=interfacial tension;
σ og =oil-gas interfacial tension; and
v o =velocity of oil. | A method, a system and a program storage device for predicting a property of a fluid, such as fluid production from a subterranean reservoir containing heavy oil entrained with gas is described. The method includes developing a baseline correlation of gas relative permeability k rg versus gas saturation S g . A capillary number dependent correlation is determined capturing the relationship between at least one of critical gas saturation S gc and capillary number N ca and gas relative permeability k rgro and capillary number N ca phased upon a plurality of depletion rates. Capillary numbers N c are calculated for a plurality of cells in a reservoir model representative of the subterranean reservoir. The baseline correlation is then adjusted to comport with at least one of S gc and k rgro selected from the capillary number dependent correlation to produce a plurality of corresponding adjusted baseline, correlations. Gas relative permeabilities k rg for the plurality of cells are selected from the corresponding adjusted baseline correlations. A reservoir simulation is then run utilizing the selected relative permeabilities k rg to predict a property of at least one fluid in a subterranean reservoir containing heavy oil entrained with gas. | 4 |
FIELD OF THE INVENTION
[0001] This invention relates to the management of replaceable components in a system, and more particularly to determining the correct set of replaceable components to be used in the replaceable component life tracking system of an apparatus with variable configurations.
BACKGROUND OF THE INVENTION
[0002] Many systems have multiple components that wear at different rates and are replaced as they wear out in order to keep the whole system operating. In such systems the replacement of some or all worn out components may require specially trained service professionals such as field service engineers. Some systems may be provided with replaceable components that are replaceable by the system operator, thereby eliminating or, at least reducing the frequency of, the need to place a service call. This not only may reduce overall maintenance costs, but also reduces system down time by eliminating response time. In either case, replacement by a service call or by the operator, it is desirable to track the usage of replaceable components so as to accurately anticipate when they will fail. U.S. Pat. No. 6,718,285 issued to Schwartz, et al., issued Apr. 6, 2004, henceforth referred to as the Schwartz patent, discloses a replaceable component life tracking system and is hereby incorporated in this application by reference.
[0003] The Schwartz patent discloses a replaceable component life tracking system in which the usage of each replaceable component is tracked using a predetermined parameter. In a preferred embodiment, the system is a printing device and the usage of each replaceable component is tracked using the number of pages printed. The life expectancy of each replaceable component is predetermined, and as the usage of each replaceable component is tracked. It is compared to the predetermined life expectancy, and the result periodically reported to the system operator via an operator interface. If any replaceable component usage reaches the life expectancy of that replaceable component, the operator is notified immediately, and instructed that the replaceable component be replaced.
[0004] Some systems with replaceable components may have more than one possible configuration and each configuration may have a different set of replaceable components. This can occur with large systems that are, from time to time, updated at the customer site, with newly developed features, with modifications to correct problems not foreseen at product launch, with customer requested custom modifications, or various other reasons. If the set of replaceable components changes for the different configurations, the replaceable component life tracking system must obviously be made aware of the changes and loaded with the correct set of replaceable components. As the number of possible system configurations increases the task of identifying the correct set of replaceable components for the replaceable component life tracking system becomes more difficult and the possibility of an erroneous set becomes more likely, especially if the burden of maintaining the correct set of replaceable components is on the field service technician or the operator. The need exists for a more automated tool for maintaining the correct set of replaceable components.
SUMMARY OF THE INVENTION
[0005] In light of the above, the object of the present invention is to provide a tool for automatically maintaining, for life tracking purposes, the correct set of replaceable components in systems with variable configurations and replaceable components. The method and system of the invention use replaceable component data from four sources to determine the correct set of replaceable components for life tracking purposes. The four sources are: 1) hardware driven sensor data provided by the low level system control computer, 2) machine modification data from the list of upgrades that have been performed on the system, 3) configuration specific replaceable component data based on the replaceable component information that is known about each possible system configuration, and 4) replaceable component information obtained by prompting the field service engineer for any supplemental information that cannot be determined automatically from the first three sources.
[0006] The invention, and its objects and advantages, will become more apparent in the detailed description of the preferred embodiment presented below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is an illustration of a system having a digital printer, a digital front end, and a user interface that is a preferred embodiment of the invention;
[0008] FIG. 2 is an illustration of the digital printer of FIG. 1 with the cabinetry removed showing a number of operator replaceable components;
[0009] FIG. 3A is a basic high-level block diagram illustrating the pertinent software components of the digital printer, digital front end, and graphical user interface that is a preferred embodiment of the invention;
[0010] FIG. 3B is the block diagram of FIG. 3A with arrows illustrating the data retrieval steps in the preferred embodiment of the invention;
[0011] FIG. 3C is the block diagram of FIG. 3A with arrows illustrating the data filtering steps in the preferred embodiment of the invention; and
[0012] FIG. 3D is the block diagram of FIG. 3A with arrows illustrating the steps of communicating with the operator and/or field service engineer in the preferred embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0013] FIG. 1 is an illustration of a system 100 according to the preferred embodiment of the present invention, and includes a digital printer 103 , a Digital Front End (DFE) controller 104 , and a Graphical User Interface (GUI) 106 . Digital printer 103 is provided with Operator Replaceable Component (ORC) devices that enable a typical operator to perform the majority of maintenance on the system without requiring the services of a field engineer. The ORC devices of the present invention are those components within systems that become worn after periods of use and must be replaced. Specifically, the ORC devices of the preferred embodiment herein, are those components used within digital printing systems that wear with use and must be replaced. Digital printer 103 , in the preferred embodiment, is for example, a NexPress 2100 Color On Demand Printer, available from NexPress Solutions, Inc., of Rochester, N.Y. However, the present invention pertains to systems in general and digital printing systems in particular, and to such systems with replaceable components, whether the replaceable components are replaceable by the operator or require field service engineer intervention.
[0014] DFE controller 104 in the preferred embodiment is a control system located adjacent to the printer 103 , and includes a computational element 105 . Computational element 105 contains a substantial number of software processing components that perform a number of functions including raster image processing, database management, workflow management, job processing, and ORC service management including tracking of ORC usage. Graphical User Interface (GUI) 106 communicates with computational element 105 and with the operator. Tracking of ORC usage in this preferred embodiment is disclosed in the referenced Schwartz patent, U.S. Pat. No. 6,718,285. In the preferred embodiment, GUI 106 provides the operator with the ability to view the current status of ORC devices in the digital printer 103 and to thus perform maintenance in response to maintenance information provided on the graphical display on GUI 106 as well as to alerts that are provided from the DFE controller 104 . It should be understood that while the preferred embodiment details a system 100 with a digital printer 103 having at least one computational element and another computational element associated with DFE controller 106 , similar systems can be provided with more computational elements or fewer computational elements, and that these variations will be well known to those skilled in the art. In general, virtually any interactive device can function as DFE controller 104 , and specifically any Graphics User Interface (GUI) 106 can function in association with DFE controller 104 as employed by the present invention.
[0015] Referring now to FIG. 2 of the accompanying drawings, the area inside digital printer 103 is schematically illustrated, showing the image forming reproduction apparatus according to the preferred embodiment of the present invention, designated generally by the numeral 200 . The reproduction apparatus 200 is in the form of an electrophotographic reproduction apparatus, and more particularly, a color reproduction apparatus wherein color separation images are formed in each of four color modules and transferred in register to a receiver member as a receiver member is moved through the apparatus while supported on a paper transport web (PTW) 216 . The apparatus 200 illustrates the image forming areas for a digital printer 103 having four color modules, although the present invention is applicable to printers of all types, including printers that print with more or less than four color modules.
[0016] The elements in FIG. 2 that are similar from module to module have similar reference numerals with a suffix of B, C, M and Y referring to the color module for which it is associated; black, cyan, magenta and yellow, respectively. Each module ( 291 B, 291 C, 291 M, 291 Y) is of similar construction. PTW 216 , which may be in the form of an endless belt, operates with all the modules 291 B, 291 C, 291 M, 291 Y and the receiver member is transported by PTW 216 from module to module. Four receiver members, or sheets, 212 a, b, c and d are shown simultaneously receiving images from the different modules, it being understood that each receiver member may receive one color image from each module and that in this example up to four color images can be received by each receiver member. The movement of the receiver member with the PTW 216 is such that each color image transferred to the receiver member at the transfer nip of each module is a transfer that is registered with the previous color transfer so that a four-color image formed on the receiver member has the colors in registered superposed relationship on the receiver member. The receiver members are then serially detacked from the PTW 216 and sent to a fusing station (not shown) to fuse or fix the toner images to the receiver member under heat and/or pressure. The PTW 216 is reconditioned for reuse by providing charge to both surfaces using, for example, opposed corona chargers 222 , 223 which neutralize the charge on the two surfaces of the PTW 216 . These chargers 222 , 223 are operator replaceable components within the preferred embodiment and have an expected life span after which chargers 222 , 223 will require replacement.
[0017] Each color module includes a primary image-forming member (PIFM), for example a rotating drum 203 B, C, M and Y, respectively. The drums rotate in the directions shown by the arrows and about their respective axes. Each PIFM 203 B, C, M and Y has a photoconductive surface, upon which a pigmented marking particle image is formed. The PIFM 203 B, C, M and Y have predictable lifetimes and constitute operator replaceable components. The photoconductive surface for each PIFM 203 B, C, M and Y within the preferred embodiment is actually formed on outer sleeves 265 B, C, M and Y, upon which the pigmented marking particle image is formed. These outer sleeves 265 B, C, M and Y, have lifetimes that are predictable and therefore, are operator replaceable components. In order to form images, the outer surface of the PIFM is uniformly charged by a primary charger such as corona charging devices 205 B, C, M and Y, respectively or other suitable charger such as roller chargers, brush chargers, etc. The corona charging devices 205 B, C, M and Y each have a predictable lifetime and are operator replaceable components.
[0018] The uniformly charged surface is exposed by suitable exposure device, such as, for example, a laser 206 B, C, M and Y, or more preferably an LED or other electro-optical exposure device, or even an optical exposure device, to selectively alter the charge on the surface of the outer sleeves 265 B, C, M and Y, of the PIFM 203 B, C, M and Y to create an electrostatic latent image corresponding to an image to be reproduced.
[0019] The electrostatic latent image is developed by application of charged pigmented marking particles to the latent image bearing photoconductive drum by a development station 281 B, C, M and Y, respectively. The development station has a particular color of pigmented marking particles associated respectively therewith. Thus, each module creates a series of different color marking particle images on the respective photoconductive drum. The development stations 281 B, C, M and Y, have predictable lifetimes before they require replacement and are operator replaceable components. In lieu of a photoconductive drum, which is preferred, a photoconductive belt can be used.
[0020] Each marking particle image formed on a respective PIFM is transferred electrostatically to an intermediate transfer module (ITM) 208 B, C, M and Y, respectively. The ITM 208 B, C, M and Y have an expected lifetime and are, therefore, considered to be operator replaceable components. In the preferred embodiment, each ITM 208 B, C, M and Y, has an outer sleeve 243 B, C, M and Y that contains the surface to which the image is transferred from PIFM 203 B, C, M and Y. These outer sleeves 243 B, C, M and Y are considered operator replaceable components with predictable lifetimes. The PIFMs 203 B, C, M and Y are each caused to rotate about their respective axes by frictional engagement with their respective ITM 208 B, C, M and Y. The arrows in the ITMs 208 B, C, M and Y indicate the direction of their rotation. After transfer, the marking particle image is cleaned from the surface of the photoconductive drum by a suitable cleaning device 204 B, C, M and Y, respectively to prepare the surface for reuse for forming subsequent toner images. Cleaning devices 204 B, C, M and Y are considered operator replaceable components by the present invention.
[0021] Marking particle images are respectively formed on the surfaces 242 B, C, M and Y for each of the outer sleeve 243 B, C, M and Y for ITMs 208 B, C, M and Y, and transferred to a receiving surface of a receiver member, which is fed into a nip between the intermediate image transfer member drum and a transfer backing roller (TBR) 221 B, C, M and Y, respectively. The TBRs 221 B, C, M and Y have predictable lifetimes and are considered to be operator replaceable components by the invention. Each TBR 221 B, C, M and Y, is suitably electrically biased by a constant current power supply 252 to induce the charged toner particle image to electrostatically transfer to a receiver member. Although a resistive blanket is preferred for TBR 221 B, C, M and Y, the TBR 221 B, C, M and Y can also be formed from a conductive roller made of aluminum or other metal. The receiver member is fed from a suitable receiver member supply (not shown) and is suitably “tacked” to the PTW 216 and moves serially into each of the nips 210 B, C, M and Y where it receives the respective marking particle image in a suitable registered relationship to form a composite multicolor image. As is well known, the colored pigments can overlie one another to form areas of colors different from that of the pigments.
[0022] The receiver member exits the last nip and is transported by a suitable transport mechanism (not shown) to a fuser where the marking particle image is fixed to the receiver member by application of heat and/or pressure. A detack charger 224 may be provided to deposit a neutralizing charge on the receiver member to facilitate separation of the receiver member from the PTW 216 . The detack charger 224 is another component that is considered to be operator replaceable within the invention. The receiver member with the fixed marking particle image is then transported to a remote location for operator retrieval. The respective ITMs 208 B, C, M and Y are each cleaned by a respective cleaning device 211 B, C, M and Y to prepare it for reuse. Cleaning devices 211 B, C, M and Y are considered by the invention to be operator replaceable components having lifetimes that can be predicted.
[0023] In feeding a receiver member onto PTW 216 , charge may be provided on the receiver member by charger 226 to electrostatically attract the receiver member and “tack” it to the PTW 216 . A blade 227 associated with the charger 226 may be provided to press the receiver member onto the belt and remove any air entrained between the receiver member and the PTW. The PTW 216 , the charger 226 and the blade 227 are considered operator replaceable components.
[0024] The endless transport web (PTW) 216 is entrained about a plurality of support members. For example, as shown in FIG. 2 , the plurality of support members are rollers 213 , 214 with preferably roller 213 being driven as shown by motor M to drive the PTW. Support structures 275 a, b, c, d and e are provided before entrance and after exit locations of each transfer nip to engage the belt on the backside and alter the straight line path of the belt to provide for wrap of the belt about each respective ITM. This wrap allows for a reduced pre-nip ionization and for a post-nip ionization that is controlled by the post-nip wrap. The nip is where the pressure roller contacts the backside of the PTW or where no pressure roller is used, where the electrical field is substantially applied. However, the image transfer region of the nip is a smaller region than the total wrap. Pressure applied by the transfer backing rollers (TBRs) 221 B, C, M and Y is upon the backside of the belt 216 and forces the surface of the compliant ITM to conform to the contour of the receiver member during transfer. The TBRs 221 B, C, M and Y may be replaced by corona chargers, biased blades or biased brushes, each of which would be considered by the invention to be operator replaceable components. Substantial pressure is provided in the transfer nip to realize the benefits of the compliant intermediate transfer member, which are a conformation of the toned image to the receiver member and image content on both a microscopic and macroscopic scale. The pressure may be supplied solely by the transfer biasing mechanism or additional pressure applied by another member such as a roller, shoe, blade or brush, all of which are operator replaceable components as envisioned by the present invention.
[0025] The receiver members utilized with the reproduction apparatus 200 can vary substantially. For example, they can be thin or thick paper stock (coated or uncoated) or transparency stock. As the thickness and/or resistivity of the receiver member stock varies, the resulting change in impedance affects the electric field used in the nips 210 B, C, M, Y to urge transfer of the marking particles to the receiver members. Moreover, a variation in relative humidity will vary the conductivity of a paper receiver member, which also affects the impedance and hence changes the transfer field. Such humidity variations can affect the expected lifetime of operator replaceable components.
[0026] Appropriate sensors (not shown) of any well known type, such as mechanical, electrical, or optical sensors for example, are utilized in the reproduction apparatus 200 to provide control signals for the apparatus. Such sensors are located along the receiver member travel path between the receiver member supply, through the various nips, to the fuser. Further sensors are associated with the primary image forming member photoconductive drums 203 , the intermediate image transfer member drums 208 , the transfer backing members 221 , and the various image processing stations. As such, the sensors detect the location of a receiver member in its travel path, the position of the primary image forming member photoconductive drums 203 in relation to the image forming processing stations, and respectively produce appropriate signals indicative thereof.
[0027] All sensor signals are fed as input information to Main Machine Control (MMC) unit 290 , which contains a computational element, and communicates with DFE controller 104 . Based on such signals the MMC unit 290 produces signals to control the timing of the various electrostatographic process stations for carrying out the reproduction process and to control drive by motor 292 of the various drums and belts. The production of a program for a number of commercially available microprocessors, which are suitable for use with the MMC, is a conventional skill well understood in the art.
[0028] Referring now to FIGS. 3 A-D, there is shown a block diagram and a series of steps illustrating the preferred embodiment of the ORC management tool of the present invention. Items common to FIGS. 1, 2 , and 3 A-D are identified with the same numeral in all figures. The MMC 290 , DFE 104 , and GUI 106 are each composed of a substantial number of software processing components, but only those pertinent to the preferred embodiment of the present invention are illustrated. In the MMC 290 , the EP Component 42 represents the collection of sensors in the electrophotographic reproduction apparatus 200 described above, and the ORC Manager 40 is the component responsible for maintaining ORC data and tracking ORC life. ORC Manager 40 stores ORC life tracking data in the database ORC Data Tracking 48 . In the DFE 104 the Engine Component 36 is responsible for communicating with the EP Component 42 and routing the communications to the ORC Service Component 34 , which is responsible for all ORC service functions. Client Communications Layer 32 is responsible for communications with GUI 106 . In the GUI 106 , the Client ORC 16 component is responsible for displaying ORC database tables, and the Client Message Reporting 18 component reports messages to the operator.
[0029] Stored in separate databases are the ORC Configuration Specific Data 22 and ORC Full Set 24 . The ORC Configuration Specific Data 22 represents the ORC configuration specific data for the various configurations that can result from various updates that have become available to printing system 100 . These updates become available from time to time as the result of newly developed features, modifications to correct problems not foreseen at product launch, customer requested custom modifications, or for various other reasons. A specific printing system 100 embodiment as described above may receive none, some, or all of the available updates. Each configuration will have an ORC configuration specific set of ORCs associated with it, and this data is stored and identified as numeral 22 in FIGS. 3 A-D. For various reasons, all possible ORCs are not necessarily included in the ORC Configuration Specific Data 22 . For example, individual ORCs may have variations, such as development station 281 with different custom color marking particles, but only one variation can be used at a time. Also, some machine modifications may result in ORC changes but not configuration changes. Any time this type of machine modification is performed, pertinent modification data is stored in database Machine Mods 46 . Also, some ORCs may be sourced from more that one vendor, and the same ORCs from different vendors may not be interchangeable. ORC Full Set 24 represents the stored list of all possible ORCs that results from all of the possible configurations, modifications, or from any other reason.
[0030] ORC Configuration Tool Applet 20 receives input from four different sources to determine the correct ORC set to be used by ORC Manager 40 for ORC life tracking and by ORC Service Component 34 for any other ORC service functions. The four sources of ORC information used by ORC Configuration Tool Applet 20 are: 1) ORC Configuration Specific Data 22 , 2) machine mods 46 , 3) the sensors of the MMC EP Component 42 , collectively denoted by numeral 44 in FIGS. 3 A-D, and 4) any ORC data manually input to ORC Configuration Tool Applet 20 by a field engineer or operator. Based on the data from these four sources ORC Configuration Tool Applet 20 filters from ORC Full Set 24 the correct ORC set to be used by ORC Manager 40 for ORC life tracking and by ORC Service Component 34 for any other ORC service functions. ORC Configuration Tool Applet 20 stores the correct ORC set in database ORC Properties 38 .
[0031] FIGS. 3 B-D illustrate schematically the steps in the method embodied in the invention. FIG. 3B illustrates retrieval of data, by the ORC Configuration Tool Applet 20 , from the four sources described above. ORC Configuration Tool Applet 20 retrieves the stored ORC Configuration Specific Data 22 , represented by arrow 60 , Machine Mods 46 data, arrow 63 , and data from Sensors 44 of MMC 290 , arrow 64 . ORC Configuration Tool Applet 20 also interrogates the operator and/or field engineer 26 , arrows 61 and 62 , for any ORC information that cannot be determined from the other three automatic sources. In the next steps, illustrated in FIG. 3C , using the information gathered from the above sources, the ORC Configuration Tool Applet 20 then creates a filter 21 that identifies and extracts, from the ORC Full Set 24 , the correct ORC set to be used by ORC Manager 40 for ORC life tracking and by ORC Service Component 34 for any other ORC service functions. This step is illustrated by arrow 66 . ORC Configuration Tool Applet 20 then stores the correct ORC set in the database ORC Properties 38 , arrow 68 , and also disables in database ORC Data Tracking 48 any of the ORC Full Set 24 that may have been active in a previous configuration but are not now included in the correct ORC set, arrow 70 . FIG. 3D illustrates the step of communicating, to the operator and/or field engineer via GUI 106 , the correct ORC set from database ORC Properties 46 , arrows 72 and 74 , and the correct ORC set life tracking data from database ORC Data Tracking 48 , arrows 76 and 78 .
[0032] The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. | Automatically maintaining, for life tracking purposes, the correct set of replaceable components in systems with variable configurations and replaceable components using replaceable component data from four sources to determine the correct set of replaceable components for life tracking purposes. The four sources are: 1) hardware driven sensor data provided by the low level system control computer, 2) machine modification data from the list of upgrades that have been performed on the system, 3) configuration specific replaceable component data based on the replaceable component information that is known about each possible system configuration, and 4) replaceable component information obtained by prompting the field service engineer for any supplemental information that cannot be determined automatically from the first three sources. | 6 |
BACKGROUND OF THE INVENTION
The present invention relates to specialized machinery for laying traffic safety and control lines on roads, highways and parking lots.
Road surface marking with various combinations of lines, straight and curved, continuous and dashed, has become a universal medium of traffic control and essential information. Like the road surface substrate for these lines, they are subjected to considerable wear, abuse and destructive force. Consequently, road surface line marking must be frequently revised, renewed or reconditioned.
While interstate and autobahn type highways are striped by specialized, single purpose truck machines, more detailed and densely marked roads, parking lots and industrial material aisles require smaller, more agile striping machines. Moreover, due to the great variety of surfaces, striping patterns and striping objectives, it is desirable to include in the striping equipment inventory, a machine that will apply all sorts of striping materials to a roadway.
It is an object of the present invention therefore, to provide a selfpropelled, walk-behind vehicle for applying road striping.
Another object of the invention is a selfpropelled, walk-behind controlled vehicle for heating and applying thermoplastic road striping materials.
A further object of the present invention is a walk-behind line striping machine capable of applying paints or thermoplastics.
Also an object of the present invention is a walk-behind line striping vehicle that is mobilized by hydraulic wheel motors driven by an internal combustion engine powered pump and hydraulic circulation system.
Another object of the invention is an agile, walk-behind, self-driven vehicle for applying either paint or thermoplastics and energized by a single fuel source for both heat and power systems.
SUMMARY OF THE INVENTION
These and other objects of the invention to become apparent from the following detailed description of the preferred embodiment and drawings are accomplished by a combination of compactly unitized paint striping equipment assembled on a wheel supported platform. The combination includes a material melting tank heated by a coaxially contiguous tank of heat transfer oil. A petroleum gas or oil burner beneath the heat transfer oil tank bottom heats the heat transfer oil. A dedicated pump driven by a prime mover circulates the heated oil around the melting tank and along the outer jacket of a coaxial flow tube spray head support wand. A chimney annulus surrounding the heat transfer oil tank drafts combustion products and cooling air from a burner enclosure beneath the heat transfer oil tank. The prime mover also drives a hydraulic power fluid pump and an air compressor. The pressurized hydraulic power fluid energizes independent drive motors for the platform support wheels and a melting tank agitator motor. Air pressure energizes the melted thermoplastic material flow from the melt tank and the flow of glass beads into the melted plastic or paint flow stream.
BRIEF DESCRIPTION OF THE DRAWINGS
Relative to the drawings wherein like reference characters designate like or similar elements throughout the several figures of the drawings:
FIG. 1 is a plan view of the present invention mechanical layout.
FIG. 2 is a melt oil circulation schematic for the present invention.
FIG. 2A is a plan detail of the spray gun mounting plate that carries a hot oil circulation loop.
FIG. 3 is a fluid flow schematic for the pneumatic control circuit and the paint and bead delivery system.
FIG. 4 is a hydraulic power and control schematic.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Relative to the mechanical layout plan of FIG. 1, a traditional ladder type platform frame 10 is supported by unsprung drive wheels 12 and a single castering rear support wheel 14. Each drive wheel 12 is powered by a respective hydraulic motor 16 rigidly mounted in respective frame brackets. At the rear of the platform frame 10 is a subframe 18 having handle bars 19.
Mounted on the frame platform is a thermoplastic melt tank 20. Referring additionally to FIG. 2, melt tank 20 comprises an interior pressure tank 22 having an interior agitator 23 and an exterior agitator motor 24. The agitator drive motor 24 is hydraulically energized. In one embodiment of the pressure tank 22, the motor 24 and agitator 23 assembly are mounted on the tank lid 25 which is completely detachable from the lower, vessel portion of the tank 22. The detachable lid 25 is secured in operative position against internal pressure forces by threaded ring clamps 27. A trash screen 21 is secured to the tank 22 wall internally of the vessel to provide a final, material loading filter of contaminants that may be combined with the plastic or paint poured into the tank 22.
Surrounding the interior pressure tank 22 on the bottom and along a significant portion of the cylindrical length is an oil tank defined by a jacket wall 26 concentrically surrounding the pressure tank 22 wall at a spaced distance to an annular oil jacket volume 28. This annular volume 28 is closed at the top between the pressure tank 22 wall and the oil jacket wall 26 to provide a low pressure oil circulation zone around and below the pressure tank 22.
A third concentric cylindrical wall 29 with an integral bottom structurally encloses both, the hot oil tank 26 and the pressure tank 22 with an annular separation space 30 between the outer wall 29 and the hot oil wall 26. A lower extension of the outer wall 29 below the bottom portion of the hot oil jacket 28 volume provides a combustion chamber space 32. Within the chamber space 32 is a burner 34 for combustion of a fluid fuel such as prepare or liquified petroleum gas (LPG). Vents 36 in the combustion chamber 32 wall admit air to support the gas combustion and the chimney draft along annular space 30.
The outer wall 29 of the melt tank 20 is structurally secured to the frame 10 and also to the apex of an V truss 38. The base of the V truss is secured to the upper level of the steering subframe 18 proximate of the handle bars 19.
The frame 10 platform also supports a receiver structure for a portable propane or LPG tank to facilitate convenient removal of the tank 40 for filling and inspection but secures the tank stability and location. Gas flow from the LPG tank 40 in support of the oil jacket heating flame from burner 34 is controlled by a well known system not illustrated which includes a pressure reduction valve and a thermostatically operated flow control valve. The thermostatic valve responds to a sensor of the heat transfer oil temperature in the oil jacket 28 to maintain an oil temperature of about 350° F. to 400° F. which is about 75° F. to 125° F. above the 275° F. melting temperature of the thermoplastic striping material.
A hot oil pump 42, driven by a belt and sheave transmission from a small, 13 HP internal combustion engine 50, for example, keeps the hot oil within the jacket 28 circulating about a loop 44 that includes fluid supply conduits 46 to the spray head 48. A section of coaxial flow conduit 47 combines the oil flow loop 44 with the thermoplastic material supply conduit 46 in a heat transfer relationship to keep the plastic hot and the viscosity low as it flows from the melt tank 20 to the spray head 48. A valve 52 in the pressurized melt tank discharge pipe 45 isolates the tank interior from the delivery conduit 46 to facilitate cleaning and system repairs. Similarly, drain valve 54 below the conduit 46 junction with the tank valve 52 facilitates cleaning of the equipment.
For simplified logistics, the engine 50 is also fueled by propane or LPG from the same tank source 40 as supplies the melt tank burner 34.
Also driven by the engine 50 is a two-stage compressor 56 which supplies a pressure regulated, 26 ft 3 air receiver tank 58 and a pressure balancing manifold 60 with pressurized air. A receiver tank 58 reduces pressure variations and system pulsations. This facilitates control of the liquid striping material discharge spray. Regulators 62, 64 and 66 reduce the air pressure from the receiver tank and manifold pressure to a level appropriate for respective appliances. In the case of the thermoplastic material melt tank 20, regulator 62 is set to maintain a pressure of about 10 psi to about 12 psi in the tank pressure delivery line 70. Spray dispersal and control air to the spray guns 74 and 76 requires 40 psi to 50 psi from regulator 64. The pressure supply line 72 to the glass bead tank 68 is maintained at about 10 psi to 12 psi by regulator 66. Additionally, air to the bead tank 68 is passed through a dryer 67 for entrained moisture removal.
Air from the regulator 64 is divided between the spray dispersion conduit 78 and an operation control line 79 serving electrically operated solenoid valves 80 and 82. Solenoid 80 selectively supplies regulated air to the operating conduit 84 that serves the cylinder 86 for operating the caster wheel 14 pivot angle locking pin 88. Solenoid 82 selectively pressurizes conduit 90 to charge the spray gun trigger chamber and open the spray gun nozzle.
Although the frame 10 is provided with appendages 19 characterized as handlebars, direction and speed control is predominately exercised by the volume regulator 126 of pump 102 and the 3-way valve 112. The machine is turned by directing a volumetric flow difference to the wheel drive motors 16. The handlebars serve as a mounting location for the control devices convenient to a pedestrian operator.
In a closely confined operational environment requiring many reversals and short line lengths, pedestrian operation will be preferred. However, due to the capacity and versatility of the invention, long line lengths are practical tasks. In facilitation of such long and continuous applications, a surrey type of wheeled platform 130 is connected by a drawbar 132 to the frame 10 by a ball hitch 134 to support a standing operator.
Referring to the hydraulic schematic of FIG. 4, the system is shown to include a traditional sliding vane pump 100 and a radial ball piston pump 102 such as the Eaton Model 11 driven by the engine 50; preferably from a common drive shaft 104. The sliding vane pump 100 supplies the agitator motor 24 circulation loop 110 through a 3-way valve 112, an oil cooler 114 and a filter 116. The 3-way valve controls the flow orientation within the drive direction subloop 118 which thereby controls the direction of motor shaft rotation. At a third position, the motor 24 may be by-passed and idled.
From the filter 116, the circulation loop enters the supply port 120 of the radial ball piston pump 102. A 3-way valve 122 in the wheel motor loop 124 allows the wheel drive to be reversed and neutraled. Discharge flow from the radial ball piston pump is delivered to an oil reservoir 106. Pump volume regulator shaft 126 controls the rotational speed of wheel motors 16.
It should be understood that melt tank 20 may be used for either thermoplastic material such as vinyl or traditional paint, whether solvent or water based. Normally, the hot oil system would not be energized for paint striping except, perhaps in extremely cold climates and then at a reduced oil temperature. Omission of the melt tank heating function has no adverse consequence on the paint delivery system from the cold melt tanks.
Having fully described my invention, those of ordinary skill will perceive those alternatives and equivalents as may be used and practiced therewith. For example, it will be noted that the melt tank 20 air pressure drive may be omitted by connecting the tank with a gravity drain into a pump suction whereby paint or hot thermoplastic striping material is drawn from the melt tank only by a gravity feed and the pump suction and delivered by the pump with a positive pressure into spray gun 76. However, it is nevertheless preferred that the striping material, whether paint or thermoplastic, is dispersed from the gun 76 by air flow.
Another alternative of the present invention may include other fuels for the melt tank burner 34 and the engine 50. For example, diesel fuel corresponds directly to No. 1 heating oil and usually may be used interchangeably. Accordingly an oil fueled burner 34 may be combined with a diesel engine 50 with both engine and heating appliance supplied from the same, unpressurized, liquid fuel tank 40.
As my invention, therefore, | A self propelled, walk-behind or surrey drawn striping machine includes a single fluid tank for confining and, delivering under a pressure, fluid drive, heated thermoplastic, paint and the new, environmentally preferred, thin line thermoplastic. The machine is propelled by hydraulic wheel motors. A primary material tank comprises a pressurized interior vessel that is substantially surrounded by a heating fluid circulation jacket. A third wall around the fluid circulation jacket provides a heat riser insulating space. Combustion products from a burner head below the circulation jacket rise through the insulating space. A coaxial flow channel around the conduits that deliver the striping material to a spray head carries heat transfer medium such as hot oil drawn from the heating fluid circulation jacket. | 4 |
[0001] This application claims Convention priority from U.S. Patent Application No. 61/137,522, filed Jul. 30, 2008, and U.S. Patent Application No. 61/084,999, filed Jul. 31, 2008, said applications being wholly incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to novel analogs of molecules belonging to the cyclosporine family and in particular of Cyclosporine A (CsA), that have reduced or no immunosuppressive activity and bind cyclophilin (CyP).
BACKGROUND OF THE INVENTION
[0003] Cyclosporines are members of a class of cyclic polypeptides having potent immunosuppressant activity. At least some of these compounds, such as Cyclosporine A (CsA), are produced by the species Tolypocladium inflatum as secondary metabolites. CsA is a potent immunosuppressive agent that has been demonstrated to suppress humoral immunity and cell-mediated immune reactions, such as allograft rejection, delayed hypersensitivity, experimental allergic encephalomyelitis, Freund's adjuvant arthritis and graft versus host disease. It is used for the prophylaxis of organ rejection in organ transplants; for the treatment of rheumatoid arthritis; and for the treatment of psoriasis.
[0004] Although a number of compounds in the cyclosporine family are known, CsA is perhaps the most widely used medically. The immunosuppressive effects of CsA are related to the inhibition of T-cell mediated activation events. Immunosuppression is accomplished by the binding of cyclosporine to a ubiquitous intracellular protein called cyclophilin (CyP). This complex, in turn, inhibits the calcium and calmodulin-dependent serine-threonine phosphatase activity of the enzyme calcineurin. Inhibition of calcineurin prevents the activation of transcription factors, such as NFAT p/c and NF-κB, which are necessary for the induction of cytokine genes (IL-2, IFN-γ, IL-4, and GM-CSF) during T-cell activation.
[0005] Since the original discovery of cyclosporine, a wide variety of naturally occurring cyclosporines have been isolated and identified. Additionally, many cyclosporines that do not occur naturally have been prepared by partial or total synthetic means, and by the application of modified cell culture techniques. Thus, the class comprising cyclosporines is substantial and includes, for example, the naturally occurring cyclosporines A through Z; various non-naturally occurring cyclosporine derivatives; artificial or synthetic cyclosporines including the dihydro- and iso-cyclosporines; derivatized cyclosporines (for example, either the 3′-O-atom of the MeBmt residue may be acylated, or a further substituent may be introduced at the sarcosyl residue at the 3-position); cyclosporines in which the MeBmt residue is present in isomeric form (e.g., in which the configuration across positions 6′ and 7′ of the MeBmt residue is cis rather than trans); and cyclosporines wherein variant amino acids are incorporated at specific positions within the peptide sequence.
[0006] Cyclosporine analogues containing modified amino acids in the 1-position are disclosed in WO 99/18120 and WO 03/033527, which are incorporated herein by reference in their entirety. These applications describe a cyclosporine derivative known as “ISA TX 247” or “ISA247” or “ISA.” This analog is structurally identical to CsA, except for modification at the amino acid-1 residue. Applicants have previously discovered that certain mixtures of cis and trans isomers of ISA247, including mixtures that are predominantly comprised of trans ISA247, exhibited a combination of enhanced immunosuppressive potency and reduced toxicity over the naturally occurring and presently known cyclosporines.
[0007] Cyclosporine has three well established cellular targets; calcineurin, the CyP isoforms (which includes but is not limited to CyP-A, CyP-B and CyP-D), and P-glycoprotein (PgP). The binding of cyclosporine to calcineurin results in significant immunosuppression and is responsible for its traditional association with transplantation and autoimmune indications.
The Cyclophilin Family
[0008] CyPs (Enzyme Commission (EC) number 5.1.2.8) belong to a group of proteins that have peptidyl-prolyl cis-trans isomerase activity; such proteins are collectively known as immunophilins and also include the FK-506-binding proteins and the parvulins. CyPs are found in all cells of all organisms studied, in both prokaryotes and eukaryotes and are structurally conserved throughout evolution. There are 7 major CyPs in humans, namely CyP-A, CyP-B, CyP-C, CyP-D, CyP-E, CyP-40, and CyP-NK (first identified from human natural killer cells), and a total of 16 unique proteins (Galat A. Peptidylprolyl cis/trans isomerases (immunophilins): biological diversity-targets-functions. Curr Top Med Chem 2003, 3:1315-1347; Waldmeier P C et al. Cyclophilin D as a drug target. Curr Med Chem 2003, 10:1485-1506).
[0009] The first member of the CyPs to be identified in mammals was CyP-A. CyP-A is an 18-kDa cytosolic protein and is the most abundant protein for CsA binding. It is estimated that CyP-A makes up 0.6% of the total cytosolic protein (Mikol V et al. X-ray structure of monmeric cyclophilin A-cycloporin A crystal complex at 2.1 A resolution. J. Mol. Biol. 1993, 234:1119-1130; Galat A et al. Metcalfe S M. Peptidylproline cis/trans isomerases. Prog. Biophys. Mol. Biol. 1995, 63:67-118).
Cellular Location of Cyclophilins
[0010] CyPs can be found in most cellular compartments of most tissues and encode unique functions. In mammals, CyP-A and CyP-40 are cytosolic whereas CyP-B and CyP-C have amino-terminal signal sequences that target them to the endoplasmic reticulum protein secretory pathway (reviewed in Galat, 2003; Dornan J et al. Structures of immunophilins and their ligand complexes. Curr Top Med Chem 2003, 3:1392-1409). CyP-D has a signal sequence that directs it to the mitochondria (Andreeva, 1999; Hamilton G S et al. Immunophilins: beyond immunosuppression. J Med Chem 1998, 41:5119-5143); CyP-E has an amino-terminal RNA-binding domain and is localized in the nucleus (Mi H et al. A nuclear RNA-binding cyclophilin in human T cells. FEBS Lett 1996, 398:201-205) and CyP-40 has TPRs and is located in the cytosol (Kieffer L J et al. Cyclophilin-40, a protein with homology to the P59 component of the steroid receptor complex. Cloning of the cDNA and further characterization. J Biol Chem 1993, 268:12303-12310). Human CyP-NK is the largest CyP, with a large, hydrophilic and positively charged carboxyl terminus, and is located in the cytosol (Anderson S K et al. A cyclophilin-related protein involved in the function of natural killer cells. Proc Natl Acad Sci USA 1993, 90:542-546; Rinfret A et al. The N-terminal cyclophilin-homologous domain of a 150-kilodalton tumor recognition molecule exhibits both peptidylprolyl cis-transisomerase and chaperone activities. Biochemistry 1994, 33:1668-1673)
Function and Activity of the Cyclophilins
[0011] CyPs are multifunctional proteins that are involved in many cellular processes.
[0012] Because CyPs were highly conserved throughout evolution, this suggests an essential role for CyPs. Initially, it was found that CyPs have the specific enzymatic property of catalyzing cis-trans isomerization of peptidyl-prolyl bonds (Galat, 1995; Fisher G A, Halsey J, Hausforff J, et al. A phase I study of paclitaxel (taxol) (T) in combination with SDZ valspodar, a potent modulator of multidrug resistance (MDR). Anticancer Drugs. 1994; 5(Suppl 1): 43). Thus, CyPs are called peptidyl-prolyl-cis-trans isomerase (PPlase), which can act as an acceleration factor in the proper folding of newly synthesized proteins, PPlases are also involved in repairing damaged proteins due to environmental stresses including thermal stress, ultraviolet irradiation, changes in the pH of the cell environment, and treatment with oxidants. This function is known as molecular chaperoning activity. LYao Q et al. Roles of Cyclophilins in Cancers and Other Organs Systems. World J. Surg. 2005, 29: 276-280)
[0013] In addition, the PPlase activity of CyPs has recently been shown to be involved in diverse cellular processes, including intracellular protein trafficking (Andreeva L et al. Cyclophilins and their possible role in the stress response. Int J Exp Pathol 1999, 80:305-315, Caroni P et al. New member of the cyclophilin family associated with the secretory pathway. J Biol Chem 1991, 266:10739-42), mitochondrial function (Halestrap A P et al. CsA binding to mitochondrial cyclophilin inhibits the permeability transition pore and protects hearts from ischaemia/reperfusion injury. Mol Cell Biochem 1997, 174:167-72; Connern C P, Halestrap A P. Recruitment of mitochondrial cyclophilin to the mitochondrial inner membrane under conditions of oxidative stress that enhance the opening of a calcium-sensitive non-specific channel. Biochem J 1994, 302:321-4), pre-mRNA processing (Bourquin J P et al. A serine/argininerich nuclear matrix cyclophilin interacts with the Cterminal domain of RNA polymerase II. Nucleic Acids Res 1997, 25:2055-61), and maintenance of multiprotein complex stability (Andreeva, 1999).
[0014] Cyclosporine binds with nanomolar affinity to CyP-A via contacts within the hydrophobic pocket (Colgan J et al. Cyclophilin A-Deficient Mice Are Resistant to Immunosuppression by Cyclosporine. The Journal of Immunology 2005, 174: 6030-6038, Mikol, 1993) and inhibits PPlase activity. However, this effect is thought to be irrelevant for the immunosuppression. Rather, the complex between CsA and CyP-A creates a composite surface that binds to and prevents calcineurin from regulating cytokine gene transcription (Friedman J et al. Two cytoplasmic candidates for immunophilin action are revealed by affinity for a new cyclophilin: one in the presence and one in the absence of CsA. Cell 1991, 66: 799-806; Liu J et al. Calcineurin is a common target of cyclophilin-CsA and FKBP-FK506 complexes. Cell 1991, 66: 807-815).
Homology of the Cyclophilins
[0015] CyP-A, the prototypical member of the family, is a highly conserved protein in mammalian cells (Handschumacher R E et al. Cyclophilin: a specific cytosolic binding protein for CsA. Science 1984, 226: 544-7). Sequence homology analysis of human CyP-A shows that it is highly homologous to human CyP-B, CyP-C, and CyP-D (Harding M W, Handschumacher R E, Speicher D W. Isolation and amino acid sequence of cyclophilin. J Biol Chem 1986, 261:8547-55). The cyclosporine binding pocket of all CyPs is formed by a highly conserved region of approximately 109 amino acids. Of the known CyPs, CyP-D has the highest homology to CyP-A. In fact, in this region the sequence identity is 100% between CyP-A and CyP-D (Waldmeier 2003; Kristal B S et al. The Mitochondrial Permeability Transition as a Target for Neuroprotection. Journal of Bioenergetics and Biomembranes 2004, 36(4); 309-312). Therefore, CyP-A affinity is a very good predictor of CyP-D affinity, and visa versa (Hansson M J et al. The Nonimmunosuppressive Cyclosporine analogues NIM811 and UNIL025 Display Nanomolar Potencies on Permeability Transition in Brain-Derived Mitochondria. Journal of Bioenergetics and Biomembranes, 2004, 36(4): 407-413). This relationship has been repeatedly demonstrated empirically with Cyclosporine analogues (Hansson, 2004; Ptak Rg et al. Inhibition of Human Immunodeficiency Virus Type 1 Replication in Human Cells by Debio-025, a Novel Cyclophilin Binding Agent Antimicrobial Agents and Chemotherapy 2008: 1302-1317; Millay D P et al. Genetic and pharmacologic inhibition of mitochondrial dependent necrosis attenuates muscular dystrophy. Nature Medicine 2008, 14(4): 442-447; Harris R et al. The Discovery of Novel Non-Immunosuppressive Cyclosporine Ethers and Thioethers With Potent HCV Activity. Poster #1915, 59th Annual Meeting of the American Association for the Study of Liver Diseases ( AASLD ), 2008). The sequence homology across the CyPs suggests that all CyPs are potential targets for Cyclosporine analogues. Because of the multitude of cellular processes in which the CyPs are involved, this further suggests that CsA analogues which retain significant binding to CyP can be useful in the treatment of many disease indications.
Cyclophilin Mediated Diseases
Human Immunodeficiency Virus (HIV):
[0016] HIV is lentivirus of the retrovirus family and serves as an example fo the involvement of CyP in the process of infection and replication of certain viruses. CyP-A was established more than a decade ago to be a valid target in anti-HIV chemotherapy (Rosenwirth B A et al. Cyclophilin A as a novel target in anti-HIV-1 chemotherapy. Int Antivir. News 1995, 3:62-63). CyP-A fulfills an essential function early in the HIV-1 replication cycle. It was found to bind specifically to the HIV-1 Gag polyprotein (Luban J K L et al. Human immunodeficiency virus type 1 Gag protein binds to cyclophilins A and B. Cell 1993, 73: 1067-1078). A defined amino acid sequence around G89 and P90 of capsid protein p24 (CA) was identified as the binding site for CyP-A (Bukovsky A A A et al. Transfer of the HIV-1 cyclophilin-binding site to simian immunodeficiency virus from Macaca mulatta can confer both cyclosporine sensitivity and cyclosporine dependence. Proc. Natl. Acad. Sci. USA 1997, 94: 10943-10948; Gamble T R F et al. Crystal structure of human cyclophilin A bound to the amino-terminal domain of HIV-1 capsid. Cell 1996, 87: 1285-1294). The affinity of CyP-A for CA promotes the incorporation of CyP-A into the virion particles during assembly (Thali M A et al. Functional association of cyclophilin A with HIV-1 virions. Nature 1994, 372: 363-365). Experimental evidence indicates that the CyP-A-CA interaction is essential for HIV-1 replication; inhibition of this interaction impairs HIV-1 replication in human cells (Hatziioannou T D et al. Cyclophilin interactions with incoming human immunodeficiency virus type 1 capsids with opposing effects on infectivity in human cells. J. Virol. 2005, 79: 176-183; Steinkasserer A R et al. Mode of action of SDZ NIM 811, a nonimmunosuppressive CsA analog with activity against human immunodeficiency virus type 1 (HIV-1): interference with early and late events in HIV-1 replication. J. Virol 1995, 69: 814-824). The step in the viral replication cycle where CyP-A is involved was demonstrated to be an event after penetration of the virus particle and before integration of the double-stranded viral DNA into the cellular genome (Braaten D E K et al. Cyclophilin A is required for an early step in the life cycle of human immunodeficiency virus type 1 before the initiation of reverse transcription. J. Virol 1996 70: 3551-3560, Mlynar E D et al. The non-immunosuppressive CsA analogue SDZ NIM 811 inhibits cyclophilin A incorporation into virions and virus replication in human immunodeficiency virus type 1-infected primary and growth-arrested T cells. J. Gen. Virol 1996, 78: 825-835; Steinkasserer, 1995). The anti-HIV-1 activity of CsA was first reported in 1988 (Weinberg M A et al. The effect of CsA on infection of susceptible cells by human immunodeficiency virus type 1. Blood 1998, 72: 1904-1910). Evaluation of CsA and many derivatives for inhibition of HIV-1 replication revealed that nonimmunosuppressive CsA analogs had anti-HIV-1 activities equal to or even superior to those of immunosuppressive analogs (Bartz S R E et al. Inhibition of human immunodeficiency virus replication by nonimmunosuppressive analogs of CsA. Proc. Natl. Acad. Sci. USA 1995, 92: 5381-5385, Billich A F et al. Mode of action of SDZ NIM 811, a nonimmunosuppressive CsA analog with activity against human immunodeficiency virus (HIV) type 1: interference with HIV protein-cyclophilin A interactions. J. Virol 1995, 69: 2451-2461; Ptak, 2008).
Inflammation
[0017] Inflammation in disease involves the influx of Leukocytes (white blood cells) to the area of affection. The leukocytes are drawn to the area by chemokines, a family of chemoattracting agents. In vitro studies have shown that extracellular CyP-A is a potent chemoattractant for human leukocytes and T cells (Kamalpreet A et al. Extracellular Cyclophilins Contribute to the Regulation of Inflammatory Responses Journal of Immunology 2005; 175: 517-522; Yurchenko V G et al. Active-site residues of cyclophilin A are crucial for its signaling activity via CD147. J. Biol. Chem. 2002; 277: 22959-22965; Xu Q M C et al. Leukocyte chemotactic activity of cyclophilin. J. Biol. Chem. 1992; 267: 11968-11971; Allain F C et al. Interaction with glycosaminoglycans is required for cyclophilin B to trigger integrin-mediated adhesion of peripheral blood T lymphocytes to extracellular matrix. Proc. Natl. Acad. Sci. USA 2002; 99: 2714-2719). Furthermore, CyP-A can induce a rapid inflammatory response, characterized by leukocyte influx, when injected in vivo (Sherry B N et al. Identification of cyclophilin as a proinflammatory secretory product of lipopolysaccharide-activated macrophages. Proc. Natl. Acad. Sci. USA 1992; 89: 3511-3515). CyP-A is ubiquitously distributed intracellularily, however, during the course of inflammatory responses, CyP-A is released into extracellular tissue spaces by both live and dying cells (Sherry, 1992). Indeed, elevated levels of CyP-A have been reported in several different inflammatory diseases, including sepsis, rheumatoid arthritis, and vascular smooth muscle cell disease (Jin Z G et al. Cyclophilin A is a secreted growth factor induced by oxidative stress. Circ. Res. 2000; 87: 789-796; Teger, 1997; Billich, 1997). In the case of rheumatoid arthritis, a direct correlation between levels of CyP-A and the number of neutrophils in the synovial fluid of rheumatoid arthritis patients was reported (Billich, 1997).
Cancer
[0018] CyP-A has recently been shown to be over-expressed in many cancer tissues and cell lines, including but not limited to small and non-small cell lung, bladder, hepatocellular, pancreatic and breast cancer (Li, 2006; Yang H et al. Cyclophilin A is upregulated in small cell lung cancer and activates ERK1/2 signal. Biochemical and Biophysical Research Communications 2007; 361: 763-767; Campa, 2003). In cases where exogenous CyP-A was supplied this was shown to stimulate the cancer cell growth (Li, 2006; Yang, 2007) while CsA arrested the growth (Campa, 2003). Most recently it has been demonstrated the CyP (A and B) is intricately involved in the biochemical pathway allowing growth of human breast cancer cells and that CyP knockdown experiments decreased the cancer cell growth, proliferation and motility (Fang F et al. The expression of Cyclophilin B is Associated with Malignant Progression and Regulation of Genes Implicated in the Pathogenesis of Breast Cancer. The American Journal of Pathology 2009; 174(1): 297-308; Zheng J et al. Prolyl Isomerase Cyclophilin A Regulation of Janus-Activated Kinase 2 and the Progression of Human Breast Cancer. Cancer Research 2008; 68 (19): 7769-7778). Most interestingly, CsA treatment of mice xenografted with breast cancer cells induced tumor necrosis and completely inhibited metastasis (Zheng, 2008). The researchers conclude that “Cyclophilin B action may significantly contribute to the pathogenesis of human breast cancer” and that “cyclophilin inhibition may be a novel therapeutic strategy in the treatment of human breast cancer” (Fang, 2009; Zheng, 2008).
Hepatitis C
[0019] Hepatitis C Virus (HCV) is the most prevalent liver disease in the world and is considered by the World Health Organization as an epidemic. Because HCV can infect a patient for decades before being discovered, it is often called the “silent” epidemic. Studies suggest that over 200 million people worldwide are infected with HCV, an overall incidence of around 3.3% of the world's population. In the US alone, nearly 4 million people are or have been infected with HCV and of these; 2.7 million have an ongoing chronic infection. All HCV infected individuals are at risk of developing serious life-threatening liver diseases. Current standard therapy for chronic hepatitis C consists of the combination of pegylated interferon in combination with ribavirin, both generalized anti-viral agents (Craxi A et al. Clinical trial results of peginterferons in combination with ribavirin. Semin Liver Dis 2003; 23(Suppl 1): 35-46). Failure rate for the treatment is approximately 50% (Molino B F. Strategic Research Institute: 3 rd annual viral hepatitis in drug discovery and development world summit 2007. AMRI Technical Reports; 12(1)).
[0020] It has recently been demonstrated that CyP-B is critical for the efficient replication of the hepatitis C virus (HCV) genome (Watashi K et al. Cyclophilin B Is a Functional Regulator of Hepatitis C Virus RNA Polymerase. Molecular Cell 2005, 19: 111-122). Viruses depend on host-derived factors such as CyP-B for their efficient genome replication. CyP-B interacts with the HCV RNA polymerase NS5B to directly stimulate its RNA binding activity. Both the RNA interference (RNAi)-mediated reduction of endogenous CyP-B expression and the induces loss of NS5B binding to CyP-B decreases the levels of HCV replication. Thus, CyP-B functions as a stimulatory regulator of NS5B in HCV replication machinery. This regulation mechanism for viral replication identifies CyP-B as a target for antiviral therapeutic strategies. Unlike other HCV treatments, cyclophilin inhibition does not directly target the HCV virus. It is therefore thought that resistance to CyP binding drugs will occur more slowly than current HCV treatment drugs (Manns M P, et al. The way forward in HCV treatment-finding the right path. Nature Reviews Drug Discovery 2007; 6: 991-1000). In addition, by interfering at the level of host-viral interaction, CyP inhibition may open the way for a novel approach to anti-HCV treatment that could be complementary, not only to interferon-based treatment, but also to future treatments that directly target HCV replication enzymes such as protease and polymerase inhibitors (Flisiak R, Dumont J M, Crabbé R. Cyclophilin inhibitors in hepatitis C viral infection. Expert Opinion on Investigational Drugs 2007, 16(9): 1345-1354). Development of new anti-HCV drugs effecting HCV viral replication has been significantly impeded by the lack of a suitable laboratory HCV model. This obstacle has only recently been overcome by the development of several suitable cell culture models (Subgenomic HCV Replicon Systems) and a mouse model containing human liver cells (Goto K, et al. Evaluation of the anti-hepatitis C virus effects of cyclophilin inhibitors, CsA, and NIM811. Biochem Biophys Res Comm 2006; 343: 879-884; Mercer D F, et al. Hepatitis C virus replication in mice with chimeric human livers. Nat Med 2001; 7: 927-933). Cyclosporine has recently demonstrated anti-HCV activity in screening models and in small clinical trials (Watashi K, et al. CsA suppresses replication of hepatitis C virus genome in cultured hepatocytes. Hepatology 2003; 38:1282-1288; Inoue K, Yoshiba M. Interferon combined with cyclosporine treatment as an effective countermeasure against hepatitis C virus recurrence in liver transplant patients with end-stage hepatitis C virus related disease. Transplant Proc 2005; 37:1233-1234).
Muscular Degenerative Disorders
[0021] CyP-D is an integral part of the mitochondrial permeability transition pore (MTP) in all cells. The function of the MTP pore is to provide calcium homeostasis within the cell. Under normal conditions the opening and closing of the MTP pore is reversible. Under pathological conditions which involve an excessive calcium influx into the cell, this overloads the mitochondria and induces an irreversible opening of the MPT pore, leading to cell death or apoptosis. CsA has been reported to correct mitochondrial dysfunction and muscle apoptosis in patients with Ullrich congenital muscular dystrophy and Bethlam myopathy [(Merlini L et al. CsA corrects mitochondrial dysfunction and muscle apoptosis in patients with collagen VI myopathies. PNAS 2008; 105(13): 5225-5229]. CsA has been demonstrated in vitro to dose dependently inhibit mPTP opening in isolated cardiac mitochondria, thereby preventing apoptosis and allowing the cell precious time for repair (Gomez L et al. Inhibition of mitochondrial permeability transition improves functional recovery and reduces mortality following acute myocardial infarction in mice Am J Physiol Heart Circ Physiol 2007, 293: H1654-H1661). A clinical study in 58 patients who presented with acute myocardial infarction demonstrated that administration of CsA at the time of reperfusion was associated with a smaller infarct than that seen with placebo (Piot C et al. Effect of Cyclosporine on Reperfusion Injury in Acute Myocardial Infarction. New England Journal of Medicine 2008; 395(5): 474-481)).
Chronic Neurodegenerative Diseases
[0022] CsA can act as a neuroprotective agent in cases of acute cerebral ischemia and damage, as a result of head trauma (Keep M, et al. Intrathecal cyclosporine prolongs survival of late-stage ALS mice. Brain Research 2001; 894: 327-331). Animals treated with CsA showed a dramatic 80% survival rate relative to only a 10% survival rate in the absence of treatment. It was later established that this was largely the result of the binding of CsA to mitochondrial CyP-D. It has been subsequently established that the utility of CsA extends to chronic neurodegeneration, as was subsequently demonstrated in a rat model of Lou Gerhig's Disease (ALS) (U.S. Pat. No. 5,972,924) where CsA treatment more than doubled the remaining life-span. It has also recently been shown that CyP-D inactivation in CyP-D knockout mice protects axons in experimental autoimmune encephalomyelitis, an animal model of multiple sclerosis (Forte M et al. Cyclophilin D inactivation protects axons in experimental autoimmune encephalomyelitis, an animal model of multiple sclerosis. PNAS 2007; 104(18): 7558-7563). In an Alzheimer's disease mouse model CyP-D deficiency substantially improves learning and memory and synaptic function (Du H et al. Cyclophilin D deficiency attenuates mitochondrial and neuronal perturbation and ameliorates learning and memory in Alzheimer's disease Nature Medicine 2008, 14(10): 1097-1105). In addition, CsA has been shown to be effective in a rat model of Huntington's (Leventhal L et al. CsA protects striatal neurons in vitro and in vivo from 3-nitropropionic acid toxicity. Journal of Comparative Neurology 2000, 425(4): 471-478), and partially effective in a mouse model of Parkinson's (Matsuura K et al. CsA attenuates degeneration of dopaminergic neurons induced by 6-hydroxydopamine in the mouse brain. Brain Research 1996, 733(1): 101-104). Thus, mitochondrial-dependent necrosis represents a prominent disease mechanism suggesting that inhibition of CyP-D could provide a new pharmacologic treatment strategy for these diseases (Du, 2008). Cellular, Tissue and Organ Injury due to a Loss of Cellular Calcium Ion ( Ca 2÷ ) Homeostasis.
[0023] Ca 2+ is involved in a number of physiological processes at a cellular level, including the healthy mitochondrial function. Under certain pathological conditions, such as myocardial infarct, stroke, acute hepatotoxicity, cholestasis, and storage/reperfusion injury of transplant organs, mitochondria lose the ability to regulate calcium levels, and excessive calcium accumulation in the mitochondrial matrix results in the opening of large pores in the inner mitochondrial membrane. (Rasola A. et al. The mitochondrial permeability transition pore and its involvement in cell death and in disease pathogenesis. Apoptosis 2007, 12: 815-833.) Nonselective conductance of ions and molecules up to 1.5 kilodaltons through the pore, a process called mitochondrial permeability transition, leads to swelling of mitochondria and other events which culminate in cell death, including the induction of apoptosis. One of the components of the mitochondrial permeability transition pore (MPTP) is CyP-D. CyP-D is an immunophilin molecule whose isomerase activity regulates opening of the MPTP, and inhibition of the isomerase activity by CsA or CsA analogs inhibits creation of the MPTP, and thus prevents cell death.
Non-immunosuppressive Cyclosporine Analogue Cyclophilin Inhibitors
[0024] Despite the advantageous effects of CsA in the above mentioned indications the concomitant effects of immunosuppression limit the utility of CsA as a CyP inhibitor in clinical practice. At present, there are only a few CsA analogs that have been proven to have little or reduced immunosuppressive activity (i.e. <10% of the immunosppressive potency of CsA) and still retain their ability to bind CyP (i.e. >10% CyP binding capacity as compared to CsA).
[0000] NIM 811 (Melle 4 -cyclosporine)
[0025] NIM 811 is a fermentation product of the fungus Tolypocladium niveum , modified at amino acid 4 displays no immunosuppressive activity (due to lack of calcineurin binding) yet retains binding affinity for CyP-A (Rosenwirth B A et al. Inhibition of human immunodeficiency virus type 1 replication by SDZ NIM 811, a nonimmunosuppressive Cyclosporine Analogue. Antimicrob Agents Chemother 1994, 38: 1763-1772).
DEBIO 025 (MeAla 3 EtVal 4 -Cyclosporin)
[0026] DEBIO 025 is a dual chemical modification of CsA at amino acids 3 and 4, also displays no immunosuppressive activity yet retains binding affinity for CyP-A PPlase activity (Kristal, 2004).
[0000] SCY-635 (DimethylaminoethylthioSar 3 -hydroxyLeu 4 -Cyclosporin)
[0027] SCY-635 is a dual chemical modification of CsA at amino acids 3 and 4, also displays no immunosuppressive activity yet retains binding affinity for CyP-A PPlase activity (PCT Publication No. WO2006/039668).
[0028] Generally, these compounds have modification on the face of CsA that is responsible for binding calcineurin, and generally require the modification of amino acids 3 and 4. The modification of amino acids 3 and 4 is a laborious and complex, as this approach typically involves opening up the cyclosporine ring, replacing and/or modifying those amino acids and then closing up the ring to produce the modified cyclosporine.
[0029] In contrast, modification of the side chain of amino acid 1 does not require opening of the cyclosporine ring. However, amino acid 1 is associated with CyP binding (as opposed to calcineurin binding) and has been modified to increase the immunosuppressive efficacy of CsA. For example U.S. Pat. No. 6,605,593, discloses a single modification of amino acid 1 that results in a CsA analog with increased immunosuppressive potency.
[0030] Therefore, it would be desirable to have a non-immunosuppressive Cyclosporine analogue molecule (a “NICAM”) that are readily synthesized and are efficacious in the treatment of CyP mediated diseases.
SUMMARY OF THE INVENTION
[0031] One aspect of the invention relates to compounds represented by the chemical structure of Formula I:
[0000]
wherein
a. R′ is H or Acetyl; b. R1 is a saturated or unsaturated straight chain or branched aliphatic carbon chain from 2 to 15 carbon atoms in length; and c. R2 is selected from the group consisting of:
(i) a H; (ii) an unsubstituted, N-substituted, or N,N-disubstituted amide; (iii) a N-substituted or unsubstituted acyl protected amine; (iv) a carboxylic acid; (v) a N-substituted or unsubstituted amine; (vi) a nitrile; (vii) an ester; (viii) a ketone; (ix) a hydroxy, dihydroxy, trihydroxy, or polyhydroxy alkyl; and (x) a substituted or unsubstituted aryl;
or a pharmaceutically acceptable salt thereof.
[0046] A second aspect of the invention relates to compounds of Formula II:
[0000]
wherein
a. R′ is H or Acetyl;
b. R1 is a saturated or unsaturated straight chain or branched aliphatic carbon chain from 2 to 15 carbon atoms in length; and
c. R3 is selected from the group consisting of
(i) a saturated or unsaturated straight or branched aliphatic carbon chain containing one or more substituents selected from the group consisting of a hydrogen, a ketone, a hydroxyl, a nitrile, a carboxylic acid, an ester and a 1,3-dioxolane; (ii) an aromatic group containing one or more substituents selected from the group consisting of a halide, an ester and nitro; and (iii) a combination of said saturated or unsaturated, straight or branched aliphatic chain and said aromatic group.
or a pharmaceutically acceptable salt thereof.
[0054] A third aspect of the invention relates to compounds of Formula III:
[0000]
[0000] wherein
a. R′ is H or Acetyl; b. R1 is a saturated or unsaturated straight chain or branched aliphatic carbon chain from 2 to 15 carbon atoms in length; and c. R4 is selected from the group consisting of
[0000]
wherein
1. R5 is a saturated or unsaturated straight chain or branched aliphatic carbon chain between 1 and 10 carbons in length 2. R6 is a monohydroxylated, dihydroxylated, trihydroxylated or polyhydroxylated saturated or unsaturated straight chain or branched aliphatic carbon chain between 1 and 10 carbons in length;
or a pharmaceutically acceptable salt thereof.
[0061] A fourth aspect of the invention relates to compounds Formula IV:
[0000]
wherein
I. R′ is H or Acetyl; and II. R7 is selected from the group consisting of:
[0000]
[0000] or a pharmaceutically acceptable salt thereof.
[0065] According to another aspect of the invention, there is provided a process to produce a compound of said Formula I, comprising the steps of
a. reacting acetyl CsA aldehyde modified at amino acid 1 of Formula IX:
[0000]
with a phosphonium salt of Formula VIII:
[0000]
wherein
I. R13 is a saturated or unsaturated straight chain or branched aliphatic carbon chain from 1 to 14 carbon atoms in length; and II. R2 is as defined above for Formula I;
in the presence of a base to produce an acetylated compound of Formula X:
[0000]
b. deacetylating the compound of Formula X using a base; and
c. where R1 is saturated, hydrogenating the double bond of the compound of Formula X by reacting the compound with a hydrogenating agent to produce a saturated analogue of Formula I.
[0074] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XIV:
[0000]
comprising the steps of
a. reacting the compound of Formula XV:
[0000]
in the presence of a reducing agent and an acylating agent to produce acetylated compounds of Formula XVI:
[0000]
and
b. deacetylating the compound of Formula XVI using a base;
wherein R1 of Formulae XIV, XV and XVI is a saturated or unsaturated straight chain or branched aliphatic carbon chain between 2 and 15 carbons in length.
[0081] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XXI:
[0000]
comprising the steps of
a. by dissolving the compound of Formula XX:
[0000]
in an anhydrous solvent; and
b. reacting the solution with trifluoroacetic acid (TFA);
wherein R1 of Formulae XX and XXI is a saturated or unsaturated, straight chain or branched aliphatic carbon chain between 2 and 15 carbons in length.
[0087] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XIV:
[0000]
comprising the steps of
a. dissolving the compound of Formula XXI:
[0000]
in anhydrous pyridine;
b. reacting the solution with acylating agent; and
c. removing the solvent to yield the compound of Formula XIV;
wherein R1 of Formulae XIV and XXI is a saturated or unsaturated straight chain or branched aliphatic carbon chain between 2 and 15 carbons in length.
[0094] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XXIV:
[0000]
wherein
I. R1 is a saturated or unsaturated, straight or branched aliphatic carbon chain between 2 and 15 carbons in length; and II. R15 and R16 are independently hydrogen or a saturated or unsaturated straight chain or branched aliphatic group; or where NR15R16 together forms a morpholinyl moiety;
comprising the steps of
a. by combining the compound of Formula XXV:
[0000]
with thionylchloride to yield a residue of the Formula XXVI;
[0000]
b. dissolving the residue in anhydrous solvent and reacting with a compound of the Formula XXVII:
[0000] R15R16NH Formula XXVII
to yield the compound of Formula XXVIII
[0000]
and
c. deacetylating the compound of Formula XXIV with a base.
[0105] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XXIV:
[0000]
wherein
I. R1 is a saturated or unsaturated straight chain or branched aliphatic carbon chain between 2 and 15 carbons in length; II. R15 and R16 are independently hydrogen or a saturated or unsaturated straight chain or branched aliphatic group; or where NR15R16 together forms a morpholinyl moiety;
comprising the steps of
a. dissolving the compound of Formula XXV:
[0000]
in anhydrous solvent under nitrogen;
b. reacting with dicyclohexylcarvodiimide, 1-hydroxybenzotriazole hydrate and the compound of the Formula XVIII;
[0000] R15R16NH Formula XXVII
and c. deacetylating the compound of Formula XVIII with a base.
[0115] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XXXII:
[0000]
wherein
I. R1 is a saturated or unsaturated straight chain or branched aliphatic carbon chain between 2 and 15 carbons in length; and II. R17 is a saturated or unsaturated straight chain or branched aliphatic group, optionally containing a halogen or hydroxyl substituent;
by reacting the compound of Formula XXX:
[0000]
with a compound of Formula XXXI:
[0000] R17OH Formula XXXI
in the presence of an acid.
[0122] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XXVI:
[0000]
wherein
I. R1 is a saturated or unsaturated straight chain or branched aliphatic carbon chain between 2 and 15 carbons in length; and II. R20 is a saturated or unsaturated straight chain or branched aliphatic group;
by reacting the compound of Formula XXXV:
[0000]
wherein R′ is optionally H or acetyl
with sodium borohydride; and
where R′ is acetyl, deacetylating the compound of Formula XXXV with a base.
[0130] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XXIX:
[0000]
wherein R1 is a saturated or unsaturated straight chain or branched aliphatic carbon chain between 2 and 15 carbons in length;
by reacting the compound of Formula XXVIII:
[0000]
with borane-tetrahydrofuran and sodium peroxide.
[0134] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XLIII:
[0000]
wherein
I. R′ is H or Acetyl; and II. R1 is a saturated or unsaturated, straight or branched aliphatic chain from 2 to 15 carbons in length;
by reacting the compound of Formula XLI:
[0000]
with the compound of Formula XLII;
[0000]
in an anhydrous solvent; and
deacetylating the compound of Formula XVIII with a base.
[0142] According to another aspect of the invention, there is provided a process to produce a non-immunosuppressive compound of Formula XLVI:
[0000]
wherein
I. R1 is a saturated or unsaturated straight chain or branched aliphatic carbon chain from 2 to 15 carbon atoms in length; and II. R23 is a saturated or unsaturated straight chain or branched aliphatic group;
comprising the steps of:
a. reacting the compound of Formula XLV
[0000]
with hydrogen peroxide and formic acid;
b. reacting the product with a base to yield the compound of Formula XLVI; and
c. deacetylating the compound of Formula XLV with a base.
[0151] The present invention discloses non-immunosuppressive cyclosporine analogues. Such compounds bind CyP and are potentially useful in treating CyP mediated diseases.
[0152] In general, for Formulae I through XLVI:
[0153] “Carboxylic acid” includes a group in which the carboxylic acid moiety is connected to one of the following substituents:
1. alkyl which may be substituted (for example, alkyl of 2 to 15 carbons); 2. alkenyl which may be substituted (for example, alkenyl of 2 to 15 carbons); and 3. alkynyl which may be substituted (for example, alkynyl of 2 to 15 carbons);
[0157] The substituents of the above-described above may include halogen (for example, fluorine, chlorine, bromine, iodine, etc.), nitro, cyano, hydroxy, thiol which may be substituted (for example, thiol, C1-4 alkylthio, etc.), amino which may be substituted (for example, amino, mono-C1-4 alkylamino, di-C1-4 alkylamino, 5- to 6-membered cyclic amino such as tetrahydropyrrole, piperazine, piperidine, morpholine, thiomorpholine, pyrrole, imidazole, etc.), C1-4 alkoxy which may be halogenated (for example, methoxy, ethoxy, propoxy, butoxy, trifluoromethoxy, trifluoroethoxy, etc.), C1-4 alkoxy-C1-4 alkoxy which may be halogenated (for example, methoxymethoxy, methoxyethoxy, ethoxyethoxy, trifluoromethoxyethoxy, trifluoroethoxyethoxy, etc.), formyl, C2-4 alkanoyl (for example, acetyl, propionyl, etc.), C1-4 alkylsulfonyl (for example, methanesulfonyl, ethanesulfonyl, etc.), and the like, and the number of the substituents is preferably 1 to 3.
[0158] Further, the substituents of the above “amino which may be substituted” may bind each other to form a cyclic amino group (for example, a group which is formed by subtracting a hydrogen atom from the ring constituting nitrogen atom of a 5- to 6-membered ring such as tetrahydropyrrole, piperazine, piperidine, morpholine, thiomorpholine, pyrrole, imidazole, etc. so that a substituent can be attached to the nitrogen atom, or the like). The cyclic amino group may be substituted and examples of the substituent include halogen (for example, fluorine, chlorine, bromine, iodine, etc.), nitro, cyano, hydroxy, thiol which may be substituted (for example, thiol, C1-4 alkylthio, etc.), amino which may be substituted (for example, amino, mono-C.sub.1-4 alkylamino, di-C1-4 alkylamino, 5- to 6-membered cyclic amino such as tetrahydropyrrole, piperazine, piperidine, morpholine, thiomorpholine, pyrrole, imidazole, etc.), carboxyl which may be esterified or amidated (for example, carboxyl, C1-4 alkoxy-carbonyl, carbamoyl, mono-C1-4 alkyl-carbamoyl, di-C1-4 alkyl-carbamoyl, etc.), C1-4 alkoxy which may be halogenated (for example, methoxy, ethoxy, propoxy, butoxy, trifluoromethoxy, trifluoroethoxy, etc.), C1-4 alkoxy-C.sub.1-4 alkoxy which may halogenated (for example, methoxymethoxy, methoxyethoxy, ethoxyethoxy, trifluoromethoxyethoxy, trifluoroethoxyethoxy, etc.), formyl, C2-4 alkanoyl (for example, acetyl, propionyl, etc.), C1-4 alkylsulfonyl (for example, methanesulfonyl, ethanesulfonyl), and the like, and the number of the substituents is preferably 1 to 3. “Amine” includes a group which may be unsubstituted or in which the amine moiety is an N-substituted or N,N disubstituted having one or two substituents which may be independently selected from:
1. alkyl which may be substituted (for example, alkyl of 2 to 15 carbons); 2. alkenyl which may be substituted (for example, alkenyl of 2 to 15 carbons); 3. alkynyl which may be substituted (for example, alkynyl of 2 to 15 carbons); 4. formyl or acyl which may be substituted (for example, alkanoyl of 2 to 4 carbons (for example, acetyl, propionyl, butyryl, isobutyryl, etc.), alkylsulfonyl of 1 to 4 carbons (for example, methanesulfonyl, ethanesulfonyl, etc.) and the like); 5. aryl which may be substituted (for example, phenyl, naphthyl, etc.); and the like;
and connected to a substituent independently selected from the substituents as defined for “carboxylic acid” above.
[0164] “Amide” includes a compound in which the carboxylic group of the amide moiety is connected to a substituent independently selected from the substituents as defined for “carboxylic acid” above, connect to the amino group of the amide moiety is an N-substituted or N,N disubstituted having one or two substituents, respectively, which may be independently selected from:
1. alkyl which may be substituted (for example, alkyl of 2 to 15 carbons); 2. alkenyl which may be substituted (for example, alkenyl of 2 to 15 carbons); 3. alkynyl which may be substituted (for example, alkynyl of 2 to 15 carbons); 4. formyl or acyl which may be substituted (for example, alkanoyl of 2 to 4 carbons (for example, acetyl, propionyl, butyryl, isobutyryl, etc.), alkylsulfonyl of 1 to 4 carbons (for example, methanesulfonyl, ethanesulfonyl, etc.) and the like); 5. aryl which may be substituted (for example, phenyl, naphthyl, etc.); and the like
[0170] “Aryl” may be exemplified by a monocyclic or fused polycyclic aromatic hydrocarbon group, and for example, a C6-14 aryl group such as phenyl, naphthyl, anthryl, phenanthryl or acenaphthylenyl, and the like are preferred, with phenyl being preferred. Said aryl may be substituted with one or more substitutuents, such as lower alkoxy (e.g., C1-6 alkoxy such as methoxy, ethoxy or propoxy, etc.), a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), lower alkyl (e.g., C1-6 alkyl such as methyl, ethyl or propyl, etc.), lower alkenyl (e.g., C2-6 alkenyl such as vinyl or allyl, etc.), lower alkynyl (e.g., C.2-6 alkynyl such as ethynyl or propargyl, etc.), amino which may be substituted, hydroxyl which may be substituted, cyano, amidino which may be substituted, carboxyl, lower alkoxycarbonyl (e.g., C1-6 alkoxycarbonyl such as methoxycarbonyl or ethoxycarbonyl, etc.), carbamoyl which may be substituted (e.g., carbamoyl which may be substituted with C1-6 alkyl or acyl (e.g., formyl, C2-6 alkanoyl, benzoyl, C1-6 alkoxycarbonyl which may be halogenated, C1-6 alkylsulfonyl which may be halogenated, benzenesulfonyl, etc.) which may be substituted with a 5- to 6-membered aromatic monocyclic heterocyclic group (e.g., pyridinyl, etc.), 1-azetidinylcarbonyl, 1-pyrrolidinylcarbonyl, piperidinocarbonyl, morpholinocarbonyl, thiomorpholinocarbonyl (the sulfur atom may be oxidized), 1-piperazinylcarbonyl, etc.), or the like. Any of these substituents may be independently substituted at 1 to 3 substitutable positions.
[0171] “Ketone” includes a compound in which the carbonyl group of the ketone moiety is connected to one or two substituents independently selected from the substituents as defined above for said “carboxylic acid”.
[0172] “Ester” includes either a carboxylic or an alcohol ester wherein of the ester group is composed of one or two substituents independently selected from the substituents as defined for “carboxylic acid” or “aryl”.
[0173] “Alkyl” unless otherwise defined is preferably an alkyl of 1 to 15 carbon units in length.
[0174] “Aromatic group” may be exemplified by aryl as defined above, or a 5- to 6-membered aromatic monocyclic heterocyclic group such as furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, furazanyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl or the like; and a 8- to 16-membered (preferably, 10- to 12-membered) aromatic fused heterocyclic group.
[0175] “Non-immunosuppresive” refers to the ability of a compound to exhibit a substantially reduced level of suppression of the immune system as compared with CsA, as measured by the compounds ability to inhibit the proliferation of human lymphocytes in cell culture and preferably as measured by the method set out in Example 19 below.
[0176] “Analogue” means a structural analogue of CsA which differs from CsA in one or more functional groups. Preferably, such analogues preserve at least a substantial portion of the ability of CsA to bind CyP.
[0177] Preferred species of Formula I are those in which R′ is H, R1 is a saturated or unsaturated alkyl between 2 and 15 carbons in length and R2 is selected from:
1. carboxylic acid comprising a carboxyl group; 2. N-substituted of N,N-disubstituted amide wherein the substituents are independently selected from an H, an alkyl of between 1 and 7 carbons in length, or said substituents form a heterocylic ring of which the heterocyle is selected from O, N or S; 3. an ester of between 1 and 7 carbons in length; 4. an monohydroxylated, or dihydroxylated alkyl of between 1 and 7 carbons in length; 5. a N-substituted or unsubstituted acyl protected amine of between 1 and 7 carbons in length; 6. a nitrile; 7. a ketone wherein the carboxylic group of the ketone is connected to R1 and saturated or unsaturated alkyl chain of between 1 and 7 carbons in length; 8. phenyl, optionally substituted with one or more substituents independently selected from nitrogen dioxide, a fluorine, an amine, an ester or a carboxyl group.
[0186] The compounds of the present invention may exist in the form of optically active compounds. The present invention contemplates all enantiomers of optically active compounds within the scope of the above formulae, both individually and in mixtures of racemates. As well, the present invention includes prodrugs of the compounds defined herein.
[0187] According to another aspect, compounds of the present invention may be useful for treating or preventing or studying a cyclophilin mediated disease in a mammal, preferably a human. Such disease is usually mediated by the over expression of cyclophilin, such as a congenital over expression of cyclophillin.
[0188] Cyclophilin mediated diseases which may be treated by compounds of the present invention include:
a. a viral infection; b. inflammatory disease; c. cancer; d. muscular degenerative disorder; e. neurodegenerative disorder; and f. injury associated with loss of cellular calcium homeostasis.
[0195] Said viral infection may be caused by a virus selected from the group consisting of Human Immunodeficiency virus, Hepatitis A, Hepatitis B, Hepatitis C, Hepatitis D, and Hepatitis E. Said inflammatory disease is selected from the group consisting of asthma, autoimmune disease, chronic inflammation, chronic prostatitis, glomerulonephritis, hypersensitivity disease, inflammatory bowel disease, sepsis, vascular smooth muscle cell disease, aneurysms, pelvic inflammatory disease, reperfusion injury, rheumatoid arthritis, transplant rejection, and vasculitis. Said cancer may be selected from the group consisting of small and non-small cell lung, bladder, hepatocellular, pancreatic and breast cancer. Said muscular degenerative disorder may selected from the group consisting of myocardial reperfusion injury, muscular dystrophy, and collagen VI myopathies. Said neurodegenerative disorder may be selected from the group consisting of Alzheimer's disease, Parkinson's disease, Huntington's disease, Multiple Systems Atrophy, Multiple Sclerosis, cerebral palsy, stroke, diabetic neuropathy, amyotrophic lateral sclerosis (Lou Gehrig's Disease), spinal cord injury, and cerebral injury. Said injury associated with loss of cellular calcium homeostasis may be selected from the group consisting of myocardial infarct, stroke, acute hepatotoxicity, cholestasis, and storage/reperfusion injury of transplant organs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0196] These and other advantages of the invention will become apparent upon reading the following detailed description and upon referring to the drawings in which:
[0197] FIG. 1 is a line graph depicting the inhibition of CyP-D as measured by mitochondrial absorbance following addition of calcium chloride in the absence or presence of a CsA.
DETAILED DESCRIPTION
[0198] The compounds of this invention may be administered neat or with a pharmaceutical carrier to a warm-blooded animal in need thereof. The pharmaceutical carrier may be solid or liquid. The inventive mixture may be administered orally, topically, parenterally, by inhalation spray or rectally in dosage unit formulations containing conventional non-toxic pharmaceutically acceptable carriers, adjuvants and vehicles. The term parenteral, as used herein, includes subcutaneous injections, intravenous, intramuscular, intrasternal injection or infusion techniques.
[0199] The pharmaceutical compositions containing the inventive mixture may preferably be in a form suitable for oral use, for example, as tablets, troches, lozenges, aqueous or oily suspensions, dispersible powders or granules, emulsions, hard or soft capsules, or syrups or elixirs. Compositions intended for oral use may be prepared according to methods known to the art for the manufacture of pharmaceutical compositions and such compositions may contain one or more agents selected from the group consisting of sweetening agents, flavoring agents, coloring agents and preserving agents in order to provide pharmaceutically elegant and palatable preparation. Tablets containing the active ingredient in admixture with non-toxic pharmaceutically acceptable excipients may also be manufactured by known methods. The excipients used may be for example, (1) inert diluents such as calcium carbonate, lactose, calcium phosphate or sodium phosphate; (2) granulating and disintegrating agents such as corn starch, or alginic acid; (3) binding agents such as starch, gelatin or acacia, and (4) lubricating agents such as magnesium stearate, stearic acid or talc. The tablets may be uncoated or they may be coated by known techniques to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period. For example, a time delay material such as glyceryl monostearate or glyceryl distearate may be employed. They may also be coated by the techniques described in the U.S. Pat. Nos. 4,256,108; 4,160,452; and 4,265,874 to form osmotic therapeutic tablets for controlled release.
[0200] In some cases, formulations for oral use may be in the form of hard gelatin capsules wherein the active ingredient is mixed with an inert solid diluent, for example, calcium carbonate, calcium phosphate or kaolin. They may also be in the form of soft gelatin capsules wherein the active ingredient is mixed with water or an oil medium, for example peanut oil, liquid paraffin, or olive oil.
[0201] Aqueous suspensions normally contain the active materials in admixture with excipients suitable for the manufacture of aqueous suspensions. Such excipients may include: (1) suspending agents such as sodium carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, sodium alginate, polyvinylpyrrolidone, gum tragacanth and gum acacia; or (2) dispersing or wetting agents which may be a naturally-occurring phosphatide such as lecithin, a condensation product of an alkylene oxide with a fatty acid, for example, polyoxyethylene stearate, a condensation product of ethylene oxide with a long chain aliphatic alcohol, for example, heptadecaethyleneoxycetanol, a condensation product of ethylene oxide with a partial ester derived from a fatty acid and a hexitol such as polyoxyethylene sorbitol monooleate, or a condensation product of ethylene oxide with a partial ester derived from a fatty acid and a hexitol anhydride, for example polyoxyethylene sorbitan monooleate.
[0202] The aqueous suspensions may also contain one or more preservatives, for example, ethyl or n-propyl p-hydroxybenzoate; one or more coloring agents; one or more flavoring agents; and one or more sweetening agents such as sucrose, aspartame or saccharin.
[0203] Oily suspension may be formulated by suspending the active ingredient in a vegetable oil, for example arachis oil, olive oil, sesame oil or coconut oil, a fish oil which contains omega 3 fatty acid, or in a mineral oil such as liquid paraffin. The oily suspensions may contain a thickening agent, for example beeswax, hard paraffin or cetyl alcohol. Sweetening agents and flavoring agents may be added to provide a palatable oral preparation. These compositions may be preserved by the addition of an antioxidant such as ascorbic acid.
[0204] Dispersible powders and granules are suitable for the preparation of an aqueous suspension. They provide the active ingredient in a mixture with a dispersing or wetting agent, a suspending agent and one or more preservatives. Suitable dispersing or wetting agents and suspending agents are exemplified by those already mentioned above. Additional excipients, for example, those sweetening, flavoring and coloring agents described above may also be present.
[0205] The pharmaceutical compositions containing the inventive mixture may also be in the form of oil-in-water emulsions. The oily phase may be a vegetable oil such as olive oil or arachis oils, or a mineral oil such as liquid paraffin or a mixture thereof. Suitable emulsifying agents may be (1) naturally-occurring gums such as gum acacia and gum tragacanth, (2) naturally-occurring phosphatides such as soy bean and lecithin, (3) esters or partial ester 30 derived from fatty acids and hexitol anhydrides, for example, sorbitan monooleate, (4) condensation products of said partial esters with ethylene oxide, for example, polyoxyethylene sorbitan monooleate. The emulsions may also contain sweetening and flavoring agents.
[0206] Syrups and elixirs may be formulated with sweetening agents, for example, glycerol, propylene glycol, sorbitol, aspartame or sucrose. Such formulations may also contain a demulcent, a preservative, and flavoring and coloring agents.
[0207] The pharmaceutical compositions may be in the form of a sterile injectable aqueous or oleagenous suspension. This suspension may be formulated according to known methods using those suitable dispersing or wetting agents and suspending agents which have been mentioned above. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that may be employed are water, Ringer's solution and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose any bland fixed oil may be employed including synthetic mono- or di-glycerides. In addition, fatty acids such as oleic acid find use in the preparation of injectables.
[0208] The inventive mixture may also be administered in the form of suppositories for rectal administration of the drug. These compositions can be prepared by mixing the drug with a suitable non-irritating excipient which is solid at ordinary temperatures but liquid at the rectal temperature and will therefore melt in the rectum to release the drug. Such materials are cocoa butter and polyethylene glycols.
[0209] For topical use, suitable creams, ointments, jellies, solutions or suspensions, etc., containing that normally are used with cyclosporine may be employed.
[0210] In a particularly preferred embodiment, a liquid solution containing a surfactant, ethanol, a lipophilic and/or an amphiphilic solvent as non-active ingredients is used. Specifically, an oral multiple emulsion formula containing the isomeric analogue mixture and the following non-medicinal ingredients: d-alpha Tocopheryl polyethylene glycol 1000 succinate (vitamin E TPGS), medium chain triglyceride (MCT) oil, Tween 40, and ethanol is used. A soft gelatin capsule (comprising gelatin, glycerin, water, and sorbitol) containing the compound and the same non-medicinal ingredients as the oral solution may also preferably be used.
[0211] It will be understood, however, that the specific dose level for any particular patient will depend upon a variety of factors including the activity of the specific compound employed, the age, body weight, general health, sex, diet, time of administration, route of administration, rate of excretion, drug combination and the nature and severity of the particular disease or condition undergoing therapy.
Methodology
[0212] Reactions 1 to 18, set out below, are general examples of the chemical reactions able to synthesize the desired compounds modified at amino acid 1 of CsA; hereinafter depicted as
[0000]
[0000] using reagents that have the requisite chemical properties, and it would be understood by a person skilled in the art that substitutions of certain reactants may be made.
[0213] The identity and purity of the prepared compounds were generally established by methodologies including mass spectrometry, HPLC and NMR spectroscopy. Mass spectra (ESI-MS) were measured on a Hewlett Packard 1100 MSD system. NMR spectra were measured on a Varian MercuryPlus 400 MHz spectrometer in deuterated solvents (DMSO for phosphonium salts, benzene for all other compounds). Analytical and preparative reversed phase HPLC was carried out on an Agilent 1100 Series system.
Synthesis of Phosphonium Salt Compounds
[0214] Phosphonium salts are prepared through reaction of triphenylphosphine or any other suitable phosphines with alkyl halides (R—X; X═Cl, Br, or I). Suitable alkyl halides are any primary or any secondary aliphatic halide of any chain length or molecular weight. These alkyl halides may be branched or unbranched, saturated or unsaturated.
[0215] If the reaction is carried out in toluene (Reaction 1), the product precipitates directly from the reaction solution. Unreactive substrates, however, require a more polar solvent such as dimethylformamide (DMF) (Reaction 2) to shorten reaction times and to achieve satisfactory yields.
Reaction 1
[0216]
[0217] Where X is a halide (including but not limited to Cl, Br, and I), and R10 is a saturated or unsaturated. straight or branched aliphatic chain, optionally containing a substituent selected from the group of ketones, hydroxyls, nitriles, carboxylic acids, esters and 1,3-dioxolanes; an aromatic group, optionally containing a substituent selected from the group of halides, esters and nitro; or a combination of the aforementioned saturated or unsaturated, straight or branched aliphatic chain and the aformentioned aromatic groups.
Example 1
Synthesis of 404-15
[0218]
[0219] As an illustrative example, triphenylphosphine (13 mmol) is dissolved in 50 mL toluene and chloroacetone (10 mmol) is added to give a clear solution. The reaction is stirred under reflux over night. A colorless solid is filtered off, washed with toluene and hexane and dried in vacuum.
[0220] Using Reaction 1, the following compounds are further examples of the compounds that may be synthesized.
[0000]
Compound
Reactant (R10-X)
Conditions
404-08
benzyl bromide
4 hours at reflux
404-09
methyl iodide
RT over night
404-12
4-nitrobenzyl bromide
6 hours at reflux
404-15
chloracetone
reflux over night
404-64
4-fluorobenzyl bromide
reflux over night
404-77
methyl 3- bromomethylbenzoate
6 hours at reflux
404-87
3-nitrobenzyl bromide
6 hours at reflux
404-161
1-bromo-2-butanone
RT over night
404-170
4-bromobutyronitrile
reflux over night
[0221] Alternatively, suitable phosphonium salts may be synthesized through Reaction 2 as illustrated below:
Reaction 2
[0222]
[0223] Where X is a halide (including but not limited to Cl, Br, and I), and R10 is a saturated or unsaturated. straight or branched aliphatic chain, optionally containing a substituent selected from the group of ketones, hydroxyls, nitriles, carboxylic acids, esters and 1,3-dioxolanes; an aromatic group, optionally containing a substituent selected from the group of halides, esters and nitro; or a combination of the aforementioned saturated or unsaturated, straight or branched aliphatic chain and the aformentioned aromatic groups.
Example 2
Synthesis of 404-51
[0224]
[0225] As an illustrative example, triphenylphosphine (11 mmol) is dissolved in 10 mL DMF and 4-bromobutyric acid (10 mmol) is added. The reaction is stirred for 7 hours at 110° C. and is then allowed to cool over night. Fifty mL toluene is added and a crystalline, colorless solid is collected by filtration. The product is washed with toluene and hexane and dried in vacuum over night.
[0226] If crystallization does not set in after treatment with toluene, the product is extracted with 20 mL MeOH/H 2 O (1:1 mixture). The aqueous phase is washed with toluene and hexane and brought to dryness. The residue is stirred with 50 mL ethyl acetate (EtOAc) at reflux temperature for 20-30 min. If a crystalline solid is obtained, the product is collected by filtration, washed with EtOAc and hexane and dried. In case the product is obtained as an oil or gum, the EtOAc is decanted and the remaining product is dried in vacuum.
[0227] Using Reaction 2, the following compounds are further examples of the compounds that may be synthesized.
[0000]
Compound
Reactant (R11-X)
Conditions
404-14
1-bromobutane
6.5 hours at 120° C.
404-29
2-bromomethyl-1,3- dioxolane
120° C. over night
404-34
1-bromooctane
110° C. over night
404-51
5-bromovaleric acid
8 hours at 120° C.
404-78
6-bromohexanol
110° C. over night
404-116
4-bromobutyric acid
7 hours at 110° C.
416-01
1-bromohexane
110° C. over night
416-02
6-bromohexanoic acid
110° C. over night
419-132
7-bromoheptanenitrile
110° C. over night
419-134
6-chloro-2-hexanone
110° C. over night
419-136
9-bromo-1-nonanol
110° C. over night
420-32
methyl 7-bromohexanoate
110° C. over night
420-78
11-bromoundecanoic acid
110° C. over night
420-80
3-bromopropionitrile
110° C. over night
420-82
8-bromooctanoic acid
110° C. over night
420-90
6-bromohexanenitrile
110° C. over night
420-94
5-chloro-2-pentanone
110° C. over night
Wittig Reaction
[0228] The Wittig reaction is broadly applicable to a wide range of substrates and reactants. The side chain, which is introduced to the substrate in the reaction, can represent any number of branched and unbranched, saturated and unsaturated aliphatic compounds of variable length (R′) and may contain a broad range of functional groups.
[0229] In the Wittig reaction, a base, such as potassium tert-butoxide (KOtBu) is used to generate an ylide from a phosphonium salt. The ylide reacts with the carbonyl group of the substrate, CsA-aldehyde, to form an alkene. Phosphonium salts containing a carboxylic acid side chain require at least two equivalents of base to generate the ylide.
Reaction 3
Synthesis of an Acetylated Cyclosporine Analogue Intermediate Using a Phosphonium Salt Compound Through a Wittig Reaction
[0230]
[0231] Where X is a halide (including but not limited to Cl, Br, and I), and R12 is a saturated or unsaturated. straight or branched aliphatic chain, optionally containing a substituent selected from the group of ketones, hydroxyls, nitriles, carboxylic acids, esters and 1,3-dioxolanes; an aromatic group, optionally containing a substituent selected from the group of halides, esters and nitro; or a combination of the aforementioned saturated or unsaturated, straight or branched aliphatic chain and the aformentioned aromatic groups.
Example 3
Synthesis of Compound 404-20 Using a Phosphonium Salt Compound Through a Wittig Reaction
[0232]
[0233] As an illustrative example, an oven dried 250 mL flask is charged under argon atmosphere with triphenylbutylphosphonium bromide (6.0 mmol) and 40 mL anhydrous tetrahydrofuran (THF). The suspension is cooled to 0° C. and potassium tert-butoxide (6.0 mmol) is added to obtain an orange color. The reaction is stirred at ambient temperature for 1-2 hours, followed by addition of CsA-aldehyde (2.0 mmol, dissolved in 20 mL anhydrous THF). Stirring is continued for 3 hours at room temperature. The reaction is quenched with 10 mL sat. NH 4 Cl and 20 mL ice-water. The layers are separated and the aqueous phase is extracted with EtOAc. The organic layers are combined, washed with brine and dried over Na 2 SO 4 . The solvent is removed and the crude product is purified over silica gel (hexane/acetone 3:1).
[0234] Using Reaction 3, the following compounds are further examples of the compounds that may be synthesized.
[0000]
MS
Compound
Starting Material
(Na + )
Remarks
404-16
404-09
1252.9
404-19
404-08
1328.9
404-20
404-14
1294.9
404-30
404-12
1373.9
stirred at 60° C. over night
404-31
1324.9
stirred at 60° C. for 2 days
404-33
404-29
1325.0
404-40
404-34
1351.2
404-43
404-15
1295.1
stirred at reflux for 10 days
404-59
404-51
1338.9
2 eq of KOtBu
404-65
404-64
1347.1
404-79
404-77
1386.9
stirred at RT over night
404-89
404-87
1374.1
stirred at RT for 2 days
404-134
404-116
1325.0
2 eq of KOtBu; stirred at RT for 2 days
404-163
404-161
1308.8
stirred at reflux for 15 days
404-187
404-170
1305.9
stirred at RT over night
416-04
416-02
1353.0
2 eq of KOtBu
416-09
416-01
1323.1
420-40
420-32
1381.0
stirred at RT over night
420-85
420-78
1423.1
2 eq of KOtBu
420-89
420-80
1291.9
420-92
420-82
1381.1
2 eq of KOtBu
420-96
404-78
1338.9
420-101
419-132
1347.9
Deacetylation
Reaction 4
Deacetylation of Acetylated Cyclosporine Analogues
[0235]
[0236] Where R12 is a saturated or unsaturated. straight or branched aliphatic chain, optionally containing a substituent selected from the group of ketones, hydroxyls, nitriles, carboxylic acids, esters, amides, acyl-protected amines and 1,3-dioxolanes; an aromatic group, optionally containing a substituent selected from the group of halides, esters, amines and nitro; or a combination of the aforementioned saturated or unsaturated, straight or branched aliphatic chain and the aforementioned aromatic groups.
Example 4
Synthesis of Compound 404-90 Though Deacetylation
[0237]
[0238] As an illustrative example, a solution of 404-20 (0.16 mmol) in 10 mL MeOH is combined with a solution of tetramethylammoniumhydroxide pentahydrate (0.47 mmol) in 2 mL H 2 O. The mixture is stirred at room temperature for 2 days. The reaction is concentrated in vacuum and 5 mL H 2 O are added. The reaction is extracted with EtOAc, the extract is washed with brine, dried over Na 2 SO 4 and concentrated to dryness. The crude product is purified by reversed phase preparative HPLC.
[0239] Purification of deacetylated compounds is generally carried out over silica gel (hexane/acetone 2:1) or by Preparative HPLC. In the case of compounds 404-60, 404-137, 416-08, 420-98 and 420-100 (carboxylic acids), the reaction is acidified to pH 2-3 with 1 M HCl prior to extraction.
[0240] Using Reaction 4, the following compounds are further examples of the compounds that may be synthesized.
[0000]
MS
Compound
Starting Material
(Na + )
404-22
404-16
1210.9
404-25
404-19
1287.0
404-36
404-33
1283.0
404-44
404-40
1309.1
404-58
404-57
1257.1
404-60
404-59
1297.1
404-61
404-56
1255.1
404-66
404-65
1305.1
404-81-1
404-79-1
1331.1
404-81-2
404-79-1
1345.1
404-85
404-83
1326.2
404-90
404-20
1253.0
404-96-1
404-94
1333.0
404-96-2
404-94
1347.0
404-97
404-89
1331.9
404-125
404-120
1304.0
404-130
404-128
1270.1
404-132
404-129
1298.0
404-137
404-134
1283.0
404-154
404-150
1338.1
404-157
404-155
1310.0
404-173
404-172
1268.9
404-194
404-187
1263.9
416-08
416-04
1311.0
416-13
416-09
1281.1
420-17
420-08-1
1368.0
420-30-1
420-27
1312.0
420-43
420-40
1324.9
420-47
420-46
1327.0
420-98
420-85
1381.1
420-100
420-92
1339.1
420-102
420-96
1297.0
420-108
420-101
1305.9
420-117
420-109-1
1352.1
420-120
420-110-1
1410.0
420-122
420-107-2
1340.0
420-124
420-109-2
1354.0
420-125
420-110-2
1412.0
420-126
420-107-1
1337.9
420-131
420-130
1297.9
420-132
420-128-1
1380.0
Hydrogenation of the Double Bond
[0241] The double bond can be hydrogenated under atmospheric pressure to obtain the saturated side chain. Functional groups such as hydroxyl, carbonyl and carboxyl are stable under these conditions and do not require protection. R′ represents either an acetyl group or hydrogen. In the case of α,β-unsaturated carbonyl compounds the double bond has to be reduced prior to deacetylation to avoid cyclization through a nucleophilic addition of the free hydroxy group on the activated double bond.
Reaction 5
[0242]
[0243] Where R12 is a saturated or unsaturated. straight or branched aliphatic chain, optionally containing a substituent selected from the group of ketones, hydroxyls, nitriles, carboxylic acids, esters, amides, acyl-protected amines and 1,3-dioxolanes; an aromatic group, optionally containing a substituent selected from the group of halides, esters, amines and nitro; or a combination of the aforementioned saturated or unsaturated, straight or branched aliphatic chain and the aforementioned aromatic groups, and R′ is either a H or an acetyl group.
Example 5
Synthesis of 404-56
[0244]
[0245] As an illustrative example, 404-43 (0.34 mmol) is dissolved in 40 mL anhydrous EtOH and 43 mg Pd/C (10%) and 0.2 mL acetic acid are added. The mixture is stirred under hydrogen at atmospheric pressure for 2 days. The reaction is filtered through Celite and is concentrated in vacuum. The crude product is purified by Preparative HPLC.
[0246] Using Reaction 5, the following compounds are further examples of the compounds that may be synthesized.
[0000]
Compound
Starting Material
MS (Na + )
404-50
404-25
1289.1
404-56
404-43
1297.0
404-57
404-31
1327.1
404-63
404-60
1299.1
404-74
404-66
1307.1
404-92
404-90
1255.1
404-94
404-79
1388.9
404-168
404-134
1326.8
404-172
404-163
1310.9
420-19
416-08
1313.0
420-46
420-40
1383.1
420-68
420-134
1326.9
420-106
420-98
1383.1
420-111
420-100
1341.0
420-112
420-102
1298.9
420-130
420-123
1340.0
Reduction of the Nitrile Group
[0247] Reduction of the nitrile group to the corresponding primary amine can be achieved with nickel boride generated in situ from sodium borohydride (NaBH 4 ) and nickel(II)chloride (NiCl 2 ). Addition of a suitable trapping reagent leads to acyl-protected primary amines (carbamates or amides, respectively) and prevents the formation of secondary amines as an undesired side reaction. The double bond is partially reduced under the given conditions and a product mixture is obtained. Both, saturated and unsaturated protected amine compounds were isolated and purified. For reaction 420-123 the mixture was not separated. Instead, the mixture underwent catalytic hydrogenation to produce the fully saturated compound.
Reaction 6
[0248]
[0249] Where Acyl is any one of BOC, acetyl, or butyryl, acylating agent is any one of di-tert-butyldicarbonate, acetic anhydride, and butyric anhydride and R1 is a saturated or unsaturated straight chain or branched aliphatic group. It would be understood by one skilled in the art that the acylating agents described above may be replaced with a broad range of acylating agents to produce a similarly broad range of acyl-protected amines.
Example 6
Synthesis of 420-08
[0250]
[0251] As an illustrative example, 404-187 (0.257 mmol) is dissolved in 15 mL methanol and cooled to 0° C. Di-tert-butyldicarbonate (0.514 mmol) and nickel(II)chloride (0.025 mmol) are added to give a clear solution. Sodiumborohydride (3.85 mmol) is added in portions over 1 hour. The resulting mixture is stirred at ambient temperature over night. Additional sodiumborohydride (1.95 mmol) is added at 0° C. and stirring is continued for 3 hours at room temperature. HPLC shows a mixture of 420-08-1 (carbamate compound) and 420-08-2 (carbamate compound with double bond reduced). The reaction is stirred for 30 minutes with diethylenetriamine (0.257 mmol) and is then concentrated in vacuum. The residue is taken up in 75 mL EtOAc, washed with 20 mL sat. NaHCO 3 solution and dried over Na 2 SO 4 . The solvent is removed in vacuum. The crude product is purified by Preparative HPLC. Using Reaction 6, the following compounds are further examples of the compounds that may be synthesized.
[0000]
Pro-
tecting
MS
Compound
Starting Material
Reagent
(Na + )
420-08-1
404-197
di-tert- butyldi- carbon- ate
1410.0
420-08-2
404-197
di-tert- butyldi- carbon- ate
1412.1
420-107-1
404-197
butyric anhy- dride
1379.9
420-107-2
404-197
butyric anhy- dride
1382.1
420-109-1
420-101
acetic anhy- dride
1394.1
420-109-2
420-101
acetic anhy- dride
1396.1
420-110-1
420-101
di-tert- butyldi- carbon- ate
1452.1
420-110-2
420-101
di-tert- butyldi- carbon- ate
1454.1
420-123 1
420-89
acetic anhy- dride
1337.9/ 1339.9
420-128-1
420-101
butyric anhy- dride
1422.1
420-128-2
420-101
butyric anhy- dride
1424.1
1 mixture not separated
Amine Deprotection
[0252] The BOC protected amine (carbamate) can be converted into the free amine by acidic hydrolysis using trifluoroacetic acid (TFA).
Reaction 7
[0253]
[0254] Where R1 is a saturated or unsaturated, straight or branched aliphatic chain, and R′ is either a H or an acetyl group.
Example 7
Synthesis of 420-23
[0255]
[0256] As an illustrative example, 420-17 (0.026 mmol) is dissolved in 4 mL anhydrous DCM and 2 mL trifluoroacetic acid is added at 0° C. The reaction is stirred at room temperature for 3 hours. Twenty 20 mL dichloromethane is added. The reaction mixture is washed with H 2 O and sat. NaHCO 3 solution and is dried over Na 2 SO 4 . The solvent is removed and the crude product is purified by Preparative HPLC.
[0257] Using Reaction 7, the following compounds are further examples of the compounds that may be synthesized.
[0000]
Compound
Starting Material
MS (M + 1)
420-23
420-17
1246.0
420-25
420-13
1290.0
420-129
420-120
1288.0
Protection of the Amino Group
[0258] The free amino function can be protected using a wide range of protecting groups using established methods. A broader range of protecting agents is available compared to the reductive introduction starting from the nitrile. Together, reactions 7 and 8 offer an alternate route to reaction 6 for the preparation of acyl-protected amino compounds.
Reaction 8
[0259]
[0260] Where Acyl is any one of BOC, acetyl or butyryl, acylating agent is any one of di-tert-butyldicarbonate, acetic anhydride, butyric anhydride, It would be understood by one skilled in the art that a broad range of acylating agents including, dicarbonates, anhydrides and acyl halides can be employed to produce a broad range of acyl-protected amines, and R1 is a saturated or unsaturated straight chain or branched aliphatic group.
Example 8
Synthesis of 420-27
[0261]
[0262] As an illustrative example, 420-25 (0.039 mmol) is dissolved in 3 mL anhydrous pyridine under nitrogen. The reaction is cooled to 0° C. and acetic anhydride (0.59 mmol) is added. The mixture is stirred at ambient temperature overnight. The solvent is removed in vacuum and the residue is taken up in 25 mL EtOAc. The reaction is washed with 2×10 mL 1 M HCl, 2×10 mL sat. NaHCO 3 solution and 10 mL brine and is dried over Na 2 SO 4 . The solvent is removed in vacuum to give the product as a colorless solid.
Deprotection of Aldehyde
[0263] The 1,3-dioxolane moiety is converted into an aldehyde function through acidic hydrolysis.
Reaction 9 and Example 9
Synthesis of 404-47
[0264]
[0265] As an illustrative example, a solution of 404-33 (0.246 mmol) in 20 mL formic acid is stirred at room temperature for 45 minutes. One hundred mL ice-water and 200 mL sat. NaHCO 3 solution are added slowly to the reaction (strong foaming). The reaction is extracted with 2×150 mL EtOAc. The combined extracts are washed with sat. NaHCO 3 solution, water and brine and are dried over Na 2 SO 4 . The solvent is removed and the product is dried in vacuum.
Reduction of the Nitro Group
[0266] The aromatic nitro compound is reduced to the aniline through catalytic hydrogenation. The reaction leads to the reduction of the double bond.
Reaction 10 and Example 10
Synthesis of 404-120
[0267]
[0268] As an illustrative example, 404-89 (0.13 mmol) is dissolved in 2 mL ethanol and Raney-Nickel (0.18 g, 50% in H 2 O, washed 3 times with ethanol, then suspended in 2 mL ethanol) and 0.1 mL acetic acid are added. The reaction is stirred at room temperature for 2 days. The reaction is filtered through Celite and the filter cake is washed with methanol. The filtrate is brought to dryness. The residue is taken up in EtOAc, washed with NaHCO 3 solution and brine and is dried over Na 2 SO 4 . The solvent is removed in vacuum. The crude product is purified over silica gel (hexane/acetone 2:1).
Amide Synthesis
[0269] Amides are prepared from carboxylic acids by reaction of an amine with the corresponding acid chloride (Reaction 11). The synthesis can also proceed directly from the acid by use of appropriate coupling reagents, such as DCC and HOBt (Reaction 12).
Reaction 11
[0270]
[0271] Where R1 is a saturated or unsaturated, straight or branched aliphatic chain, R15 and R16 are independently hydrogen or a saturated or unsaturated, straight or branched aliphatic chain, or where NR15R16 together forms a morpholinyl moiety.
Example 11
Synthesis of 404-85
[0272]
[0273] As an illustrative example, 365-73 (0.04 mmol) and thionylchloride (68 mmol) are combined under nitrogen atmosphere and are heated to reflux for 2 hours. The reaction is allowed to cool and is concentrated to dryness. Twenty mL toluene is added and the reaction is concentrated to dryness again (2 times). The residue is taken up in 5 mL anhydrous toluene and diethylamine (0.48 mmol) is added. The reaction is stirred at room temperature over night. Five mL H 2 O are added and the mixture is extracted with 20 mL EtOAc. The extract is washed with brine and dried over Na 2 SO 4 . The solvent is removed in vacuum and the crude product is purified over silica gel (hexane/acetone 3:1).
[0274] Using Reaction 11, the following compounds are further examples of the compounds that may be synthesized.
[0000]
Compound
Starting Material
MS (Na + )
Amine
404-83
365-73
1368.2
diethylamine
404-128
404-124
1311.9
anhydrous ammonia 1
404-129
404-124
1340.1
Dimethyl- amine 2
1 passed through reaction for 10 min at 0° C.;
2 2M solution in THF
Reaction 12
[0275]
[0276] Where R1 is a saturated or unsaturated, straight or branched aliphatic chain, R15 and R16 are independently hydrogen or a saturated or unsaturated, straight or branched aliphatic chain, or where NR15R16 together forms a morpholinyl moiety.
Example 12
Synthesis of 420-104
[0277]
[0278] As an illustrative example, 420-98 (0.078 mmol) is dissolved in 10 mL anhydrous DCM under nitrogen atmosphere. Dicyclohexylcarbodiimide (DCC, 0.117 mmol) and 1-hydroxybenzotriazole hydrate (HOBt, 0.078 mmol) are added at 0° C. and the mixture is stirred for 15 minutes. Dimethylamine (0.78 mmol) is added to give a clear, colorless solution. The cooling bath is removed after 15 minutes and stirring is continued at ambient temperature for 5 days. The reaction is transferred to a separatory funnel and 20 mL DCM and 10 mL 0.5 M HCl are added. The organic layer is taken off, dried over Na 2 SO 4 and concentrated to dryness. The residue is taken up in 10 mL acetonitrile. Undissolved solid is filtered off and the filtrate is concentrated in vacuum. The crude product is purified by Preparative HPLC.
[0279] Using Reaction 12, the following compounds are further examples of the compounds that may be synthesized.
[0000]
MS
Compound
Starting Material
(Na + )
Amine
404-150
416-04
1380.1
Dimethyl- amine 2
404-155
404-134
1352.1
Dimethyl- amine 2
404-156
404-60
1324.1
Dimethyl- amine 2
404-162
416-08
1379.9
Morpholine
404-164
416-08
1309.8
anhydrous ammonia 1
404-178
404-137
1323.9
Propyl- amine
420-104
420-98
1408.1
Dimethyl- amine 2
420-114
420-100
1366.0
Dimethyl- amine 2
420-121
420-100
1338.0
anhydrous ammonia 1
1 passed through reaction for 10 min at 0° C.;
2 2M solution in THF
Esterification
[0280] Carboxylic acid esters are prepared from the corresponding carboxylic acids and an alcohol either using acidic catalysis (Reaction 13) or coupling reagents (DCC and DMAP, Reaction 14).
Reaction 13
[0281]
[0282] Where R1 is a saturated or unsaturated, straight or branched aliphatic chain, and R17 is a saturated or unsaturated, straight or branched aliphatic chain, optionally containing a halogen or hydroxyl substituent.
Example 13
Synthesis of 404-171
[0283]
[0284] As an illustrative example, a mixture of 404-60 (0.059 mmol), 4 mL EtOH and 2 μL conc. H 2 SO 4 is heated to reflux for 4 hours. The solvent is evaporated and the residue is taken up in acetonitrile. The crude product is purified by Preparative HPLC.
[0285] Using Reaction 13, the following compounds are further examples of the compounds that may be synthesized.
[0000]
Compound
Starting Material
MS (Na + )
Reagent
404-171
404-60
1368.2
ethanol
404-182
404-60
1311.9
ethylene glycol 1
420-103
420-98
1409.1
Ethanol
420-113
420-100
1366.9
ethanol
1 3 hours at 90° C.;
product extracted with EtOAc
Reaction 14
[0286]
[0287] Where R1 is a saturated or unsaturated, straight or branched aliphatic chain, and R17 is a saturated or unsaturated, straight or branched aliphatic chain, optionally containing a halogen or hydroxyl substituent.
Example 14
420-24
[0288]
[0289] As an illustrative example, 404-60 (0.053 mmol) is dissolved in 4 mL anhydrous DCM and cooled to 0° C. under nitrogen atmosphere. Dimethylaminopyridine (DMAP, 0.005 mmol), 2-fluoropropanol (0.27 mmol) and dicyclohexylcarbodiimide (DCC, 0.058 mmol) are added and the reaction is stirred for 15 min at 0° C. The cooling bath is removed and stirring is continued over night at ambient temperature. 20 mL DCM are added, the reaction is then washed with H 2 O and evaporated to dryness. The residue is taken up in 10 mL acetonitrile and filtered. The filtrate is concentrated in vacuum. The crude product is purified by Preparative HPLC.
Alcohols
[0290] Besides direct synthesis in the Wittig reaction, alcohols are obtained through a number of reactions. Reduction of a carbonyl group with sodium borohydride leads to primary (starting from aldehyde) or secondary (starting from ketone) alcohols, respectively.
[0291] Oxidation of a double bond through the hydroboration method can lead to a mixture of isomers. The reaction proceeds predominantly in anti-Markovnikov orientation. In the case of a terminal olefin the primary alcohol is the main product. An olefin can be converted into a diol through oxidation with hydrogen peroxide. Reaction of a carbonyl compound with a Grignard reagent leads to secondary (starting from aldehyde) and tertiary (starting from ketone) alcohols. This method allows for an extension of the carbon chain.
Reaction 15
[0292]
[0293] Where R′ is a H or acetyl, R1 is a saturated or unsaturated, straight or branched aliphatic chain, and R20 is a saturated or unsaturated, straight or branched aliphatic chain.
Example 15
Synthesis of 404-98
[0294]
[0295] As an illustrative example, 404-61 (0.0365 mmol) is dissolved in 4.5 mL anhydrous EtOH under nitrogen atmosphere. Sodium borohydride (0.15 mmol, suspended in 0.5 mL anhydrous EtOH) is added at 0° C. and the resulting mixture is stirred at ambient temperature over night. Additional sodium borohydride (0.08 mmol) is added and stirring is continued over night. The reaction is quenched with 5 mL 1 M HCl under ice-bath cooling and is extracted with EtOAc. The extract is washed with brine, dried over Na 2 SO 4 and concentrated to dryness. The crude product is purified by Preparative HPLC.
[0296] Using Reaction 15, the following compounds are further examples of the compounds that may be synthesized.
[0000]
Compound
Starting Material
MS (Na + )
404-98
404-61
1256.9
404-195
404-173
1271.0
404-198
404-172
1313.0
420-09
404-56
1298.9
Reaction 16
[0297]
[0298] Where R1 is a saturated or unsaturated, straight or branched aliphatic chain.
Example 16
Synthesis of 420-28-1
[0299]
[0300] As an illustrative example, 404-16 (0.081 mmol) is dissolved under nitrogen atmosphere in 4 mL anhydrous THF. The reaction is cooled to 0° C. and BH 3 ·THF (1 M sol. In THF, 0.06 mmol) is added. The reaction is stirred at room temperature over night. HPLC shows the reaction is incomplete. Additional BH 3 ·THF (0.5 mmol) is added and stirring is continued for 4 hours at room temperature. The reaction is cooled to 0° C. and 1.0 mL 1 M NaOH and 0.30 mL 30% hydrogen peroxide solution are added. The mixture is stirred at room temperature over night. The reaction is extracted with 25 mL EtOAc. The extract is washed with brine, dried over Na 2 SO 4 and concentrated to dryness. The product is purified by Preparative HPLC.
Reaction 17
[0301]
[0302] Where R1 is a saturated or unsaturated, straight or branched aliphatic chain, R′ is either a H or an acetyl group.
Example 17
Synthesis of 420-49
[0303]
[0304] As an illustrative example, 420-49 (0.037 mmol) is dissolved under argon atmosphere in 5 mL anhydrous THF. The reaction is cooled to −70° C. and allylmagnesium chloride (1 M sol. In THF, 0.22 mmol) is added. The reaction is stirred for 15 minutes at −70° C. and is then allowed to come to room temperature. After 90 minutes the reaction is quenched with sat. NH 4 Cl solution. The reaction is extracted with 25 mL EtOAc. The extract is washed with brine, dried over Na 2 SO 4 and concentrated to dryness. The product is purified by Preparative HPLC. A mixture of acetylated and deacetylated compound is obtained.
Reaction 18
[0305]
[0306] Where R1 is a saturated or unsaturated, straight or branched aliphatic chain, and R23 is a saturated or unsaturated, straight or branched aliphatic chain.
Example 18
Synthesis of 404-126
[0307]
[0308] As an illustrative example, 404-16 (0.054 mmol) is dissolved in 1 mL formic acid and hydrogen peroxide (30% aqueous solution, 0.52 mmol) is added. The reaction is stirred at room temperature over night and is then concentrated to dryness. The residue is dissolved in 25 mL EtOAc, washed with sat. NaHCO 3 solution and dried over Na 2 SO 4 . The solvent is removed in vacuum. The reaction is taken up in 9 mL THF and 3 mL 1 M NaOH, and is stirred for 4 hours at room temperature. The solvent is removed and the residue is partitioned between 25 mL EtOAc and 5 mL H 2 O. The organic layer is washed with brine and dried over Na 2 SO 4 . The solvent is evaporated and the crude product is purified by Preparative HPLC.
Example 19
Immunosuppression and Cyclophilin Isomerase Inhibition
Immunosuppressive Potency
[0309] The immunosuppressive potency of test compounds was assessed by measuring their ability to inhibit the proliferation of human lymphocytes in cell culture. Lymphocytes were isolated from blood of normal human volunteers by Ficoll-gradient centrifugation and stained with 2 μg/ml carboxyfluoroscein diacetate succinimydyl ester (CFSE), a fluorescent cell division tracer molecule. Cells were stimulated through the CD3/T-cell receptor by seeding cells at 300,000/well into 96-well flat-bottom, high-binding plates coated with 1 μg/ml UCHT-1 anti-human CD3 antibody. Test compounds were prepared first as 10 mg/ml stock solutions in dimethylsulfoxide (DMSO). Test solutions were prepared by 500-fold dilution of the DMSO stock solutions, then 3-fold serial dilutions in cell culture medium (RPMI+5% FBS+penicillin-steptomycin) for a total of 7 concentrations per compound. Test solutions were added in equal volume to the culture wells containing cells to achieve final concentrations after dilution of 13.7 ng/ml-10,000 ng/ml. The reference compound, CsA, was prepared similarly but at concentrations ranging from 1.37-1,000 ng/ml. CsA was assayed in every experiment as a quality control for each experiment and as a reference comparison to the test compounds. Following 3 days incubation cells were stained with CD95-APC (lymphocyte activation marker) and analyzed by flow cytometry with a Becton Dickinson FACSCalibur. Percentage cell division was assessed in forward/side-scatter-gated lymphocytes by measuring the proportion of cells that underwent one or more cell divisions as determined by serial halving of CFSE intensity. The nondivided parent population was determined from samples maintained in culture without anti-CD3 stimulation. IC50 values for inhibition of cell division were determined by nonlinear regression analysis. Relative potency was calculated by normalizing IC50 values of test compounds to CsA.
[0310] Immunosuppressive potency was additionally analyzed by measuring the reduction in cell surface CD95 expression compared to vehicle controls.
Cyclophilin D Inhibition Assay
[0311] A mitochondria swelling assay was used to measure the efficacy of NICAMs in blocking CyP-D and mitochondrial permeability transition. Under certain pathological conditions, mitochondria lose the ability to regulate calcium levels, and excessive calcium accumulation in the mitochondrial matrix results in the opening of large pores in the inner mitochondrial membrane. Nonselective conductance of ions and molecules up to 1.5 kilodaltons through the pore, a process called mitochondrial permeability transition, leads to swelling of mitochondria and other events which culminate in cell death. One of the components of the mitochondrial permeability transition pore (MPTP) is CyP-D. CyP-D is an immunophilin molecule whose isomerase activity regulates opening of the MPTP, and inhibition of the isomerase activity by CsA or CsA analogs inhibits creation of the MPTP. In general, mitochondria isolated from rat liver were exposed to calcium to induce MPTP opening in the absence or presence of test compounds, and calcium-induced swelling was measured as a reduction in light absorbance at 540 nm.
[0312] Mitochondria were isolated from fresh rat liver. Ice-cold or 4° C. conditions were used throughout all steps of the isolation. The liver was rinsed thoroughly and chopped in a small volume of isolation buffer (IB; 10 mM Hepes, 70 mM sucrose, 210 mM mannitol, 0.5 mM EDTA). Aliquots of the minced liver were homogenized in IB using a Teflon-glass Potter-Elvehjem tissue grinder and passed through a cell screen filter. The filtered homogenate was centrifuged at 600 g for 10 min, then the resulting supernatant centrifuged at 7000 g for 10 min. The supernatant was discarded, and the pellet resuspended in wash buffer (10 mM Hepes, 70 mM sucrose, 210 mM mannitol) and centrifuged a final time at 7000 g for 10 min. The supernatant was discarded, and the mitochondria-containing pellet suspended and stored on ice in 2 mL of respiration buffer (RB; 5 mM Hepes, 70 mM sucrose, 210 mM mannitol, 10 mM sodium succinate, 1 mM sodium phosphate dibasic).
[0313] Test compound solutions were prepared from 10 mg/ml stocks (dimethyl sulfoxide vehicle) first by diluting the test compound 1000× into respiration buffer #2 (RB2; 5 mM Hepes, 70 mM sucrose, 210 mM mannitol, 10 mM sodium succinate, 1 mM sodium phosphate dibasic, 1% fetal bovine serum, 2 μM rotenone), then by 3×-serial dilutions in RB2 to achieve test compound concentrations of 10000, 3333, 1111, 370, 123, 41, and 14 ng/mL. Polystyrene tubes and plates were used for all preparations.
[0314] Swelling assays were completed in a 96-well flat-bottom polystyrene plates. In each well a 10-μL aliquot of mitochondria suspension, equivalent to 100-200 μg total protein, was combined with 90 μL of test compound, incubated for 10 min, then the baseline absorbance measured on a plate reader (540 nm wavelength; A540). Swelling was induced by adding 5 μL of 4 mM calcium chloride to achieve a final calcium concentration of 190 μM. Mitochondria swelling was indicated by a decline in A540. A540 was measured immediately after calcium addition and at intervals up to 20 min, by which time no further reduction in A540 was observed. Duplicate samples were assayed for each test compound concentration.
[0315] FIG. 1 shows the time course of mitochondrial absorbance following addition of calcium chloride in the absence or presence of CsA. CsA inhibited mitochondria swelling in a concentration-dependent manner, as indicated by blocking the calcium-induced decline in A540. Means and ranges of duplicate samples are shown.
[0000]
TABLE 1
NICAM Compounds as Determined by Immunosuppressive Potency and
Cyp Binding Relative to CsA.
Immuno-
CYP-D
suppression
Inhibition
(% Relative to
(% Potency Vs
Compound #
Compound structure
CsA)
CsA)
404-26
25
58.4
404-44
1
1.2
404-126
<1
24.6
420-28
<1
78.0
420-102
9
77.9
420-112
2
106.7
404-98
3
162.7
404-195
2
143.1
420-49-1
3
143.6
404-194
2
123.2
420-108
1
88.6
420-23
<1
43.8
420-129
<1
58
420-17
2
66.2
420-120
3
9.4
420-125
6
42.4
404-130
<1
114.7
404-164
6
98.9
420-121
6
70.9
404-132
<1
122.0
404-157
<1
142.3
420-114
<1
63.4
420-104
11
55.8
404-156
1
82.2
404-154
2
119.4
404-85
2
128.7
404-178
<1
71.3
404-162
<1
91.1
404-172
3
75.5
420-113
<1
33.2
420-103
10
15.5
404-61
3
118.8
404-173
4
150.6
420-24
<1
71.9
404-182
1
134.8
420-30-1
2
131.5
420-122
1
91.2
420-126
1
101.9
420-132
4
89.9
420-131
<1
111.8
420-117
5
79.2
420-124
8
97.4
394-136
<1
9.2
404-60
<1
116.7
420-19
<1
193.6
420-43
1
123.6
420-47
3
118.0
404-81-2
4
104.4
404-95
4
93.4
404-97
6
112.2
404-125
6
135.4
404-93-1
<1
150.8
404-81-1
7
178.7
[0316] Table 1 sets out a number of identified NICAMS that are representative compounds that may be synthesized using Reactions 1-18 above. The NICAMS display<10% of the immunosuppressive potency of CsA while retaining >5% of the CyP binding of CsA. In many cases, the CyP binding of the NICAM has >50% of CsA, while reducing the immunosuppressive potency of the NICAM to <5% of that compared to CsA.
[0317] Although the present invention has been described by way of a detailed description in which various embodiments and aspects of the invention have been described, it will be seen by one skilled in the art that the full scope of this invention is not limited to the examples presented herein. The invention has a scope which is commensurate with the claims of this patent specification including any elements or aspects which would be seen to be equivalent to those set out in the accompanying claims. | The compounds of the present invention are non-immunosupressive cyclosporine analogue molecules that are able to bind cyclophilin. Said compounds include a modified side chain of amino acid I of cyclosporin A, consisting of an oxyalkyl having substituents R′, R1 and R2, where R′ is H or Acetyl; R1 is a saturated or unsaturated straight chain or branched aliphatic carbon chain; and R2 may be a hydrogen; a unsubstituted, N substituted or NN disubstituted amide; a N substituted or unsubstituted acyl protected amine; a carboxylic acid; a N substituted or unsubstituted amine; a nitrile; a ester; a ketone; a hydroxy, dihydroxy, trihydroxy or polyhydroxy alkyl; or a substituted or unsubstituted aryl. | 2 |
BACKGROUND OF THE INVENTION
The invention herein described was made in the course of or under a contract or subcontract with the Department of the Navy.
1. Field of the Invention
This invention relates to the field of nickel base superalloy articles used where high mechanical stresses are encountered at high temperatures. This invention is also related to the field of directionally solidified eutectics wherein an alloy of approximately eutectic composition may be directionally solidified so as to produce an aligned multiphase microstructure having anisotropic mechanical properties. The article of the present invention is comprised of a directionally solidified nickel base superalloy of approximately gamma prime-alpha (Mo) eutectic composition having exceptional mechanical properties combined with adequate oxidation and sulfidation resistance at elevated temperatures.
2. Description of the Prior Art
U.S. Pat. No. 2,542,962 to Kinsey describes a broad range of compositions in the aluminum, molybdenum, nickel system without mentioning eutectic compositions or directional solidification. It is now known that certain eutectic alloys respond to proper directional solidification conditions to produce useful second phase aligned microstructures as described in the patent to Kraft, U.S. Pat. No. 3,124,452. In a patent to Thompson, U.S. Pat. No. 3,554,817, there is described a promising pseudo binary eutectic alloy occurring between the inter-metallic compounds Ni 3 Al and Ni 3 Cb which responds to plane front solidification to produce a casting characterized by an aligned lamellar microstructure. As so solidified, this combination provides one of the strongest nickel base alloys known although its ductility is limited.
In a prior patent to Thompson and Lemkey, U.S. Pat. No. 3,564,940, there is described a class of compositions which solidify according to the monovariant eutectic reaction providing aligned polyphase structures including such systems as the ternary alloys identified as cobalt-chromium-carbon and nickel-aluminum-chromium. The advantage of compositions of this nature is that the desired microstructure can be achieved over a range of compositions in a given system. This provides a substantial increase in the freedom of selection of compositions permitting increased optimization of properties. In U.S. Pat. No. 3,671,223, the concept has been further developed to include those systems which solidify according to the multivariant eutectic reaction where two or more solid phases (N) crystallize simultaneously from the liquid consisting of (N+2) or more components.
U.S. Pat. No. 3,617,397 to Maxwell, assigned to the present assignee discloses a nickel base superalloy which contains 8 percent aluminum and 18 percent molybdenum. This alloy is far from the eutectic point, and the patent does not disclose the benefits available in the directionally solidified eutectic.
U.S. Pat. No. 3,793,010 to Lemkey and Thompson discloses a eutectic article which consists of a gamma-gamma prime matrix with an aligned delta second phase.
U.S. Pat. No. 4,012,241 to Lemeky discloses a monovariant eutectic which is related to the present invention. The nominal composition of this eutectic is 8% aluminum, 27% molybdenum, balance essentially nickel. This composition is preferably directionally solidified to produce a microstructure consisting of a gamma prime matrix containing aligned fibers of alpha molybdenum and preferably small precipitate particles of the gamma phase in the matrix.
U.S. Pat. No. 4,111,723 to Lemkey, assigned to the present assignee, discloses another extended monovariant eutectic based on the nickel-aluminum-molybdenum system. The nominal composition of this alloy is 4.6% aluminum, 35.8% molybdenum, balance essentially nickel. Upon directional solidification, microstructure will consist of a gamma matrix containing aligned alpha molybdenum fibers and preferably also containing precipitate particles of the gamma prime phase in the matrix.
U.S. Pat. No. 3,904,403 discloses a composition in the nickel-aluminum-molybdenum system and suggests the possibility of directional solidification. Additions of up to 3 atomic percent tantalum are suggested.
The most accurate previous work on the nickel-aluminum-molybdenum alloys is described in "The Form of the Equilibrium Diagrams of Ni-NiAl-Mo Alloys," Academy of Sciences USSR, 132, May-June 1960, pp. 491-495, however, this reference does not discuss the eutectic reaction relied upon in the present invention.
The technical article entitled "Nickel-Aluminum-Molybdenum Alloys for Service at Elevated Temperatures," found in ASM Transactions, Vol. 43, pp. 193-225 (1951) by Kinsey and Stewart, describes work connected with the previously mentioned U.S. Pat. No. 2,542,962.
SUMMARY OF THE INVENTION
The present invention includes a nickel base superalloy of gamma prime-alpha eutectic composition with a nominal composition of 6.9 weight percent aluminum, 15.2 weight percent tantalum, 18.5 weight percent molybdenum, balance essentially nickel which is directionally solidified to produce useful articles. This alloy may be cast and directionally solidified to produce a microstructure having a gamma prime [Ni 3 (Al,Ta)] matrix and an alpha body centered cubic (Mo) second phase in fibrous form. A directionally solidified article of the nominal composition will contain approximately 17 volume percent of the reinforcing second phase. Other elements chosen from the group consisting of columbium, titanium, vanadium, tungsten, yttrium, hafnium, carbon and boron may be incorporated into the alloy.
The directionally solidified article is characterized by room temperature high ductility. Since both the matrix and reinforcing second phase have a significant amount of ductility, thermal fatigue damage which has been a problem in prior eutectic alloy systems is minimized in the invention articles by internal stress relief by plastic deformation. The reduced volume fraction of fibers present, compared with similar prior art eutectic alloys, also contributes to reduced susceptibility to thermal fatigue. Most directionally solidified eutectics heretofore known in the art have been characterized by low ductilities, and particularly low transverse ductilities. The directionally solidified alloy and article of the present invention have longitudinal ductilities comparable to conventional nickel superalloys.
The foregoing, and other objects, features and advantages of the present invention will become more apparent in light of the following detailed description of the preferred embodiment thereof as shown in the accompanying drawings.
In the following description of the preferred embodiments, the term "fibrous" will be used to mean both rodlike and platelike morphologies. All percent figures are weight percent unless otherwise specified.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the relationship between the aluminum-molybdenum-tantalum contents of the present invention.
FIG. 2 shows the rupture life of the alloys of the invention as a function of tantalum content.
FIG. 3 shows the stress rupture of behavior of the alloys of the invention.
FIG. 4 shows the sulfidation behavior of the invention alloys.
FIG. 5 shows the tensile properties of the invention alloys as a function of temperature.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The eutectic alloy of the present invention has restricted composition limits. The most precise definition of the composition limits is given by the following equation which is presented in terms of atomic percent.
12.5±0.5% Mo+[(22.0±0.5)-X]% Al+X% Ta, balance nickel.
In this equation, X (the Ta content) varies between 3.4 and 7.5 and preferably between 4.1 and 7.5 As previously noted, the solidified microstructure of the present invention consists of Mo fibers in a gamma prime matrix. The pure gamma prime phase is an intermetallic compound of the composition Ni 3 Al. The Ta additions in the present alloy substitute for the Al on an atomic basis. The nominal Al+Ta content is 22 atom percent. Ta additions of 3.4, 4.1 and 7.5 atomic percent, therefore, represent substitutions (on an atomic basis) of Ta for 15.5%, 18.6% and 34% respectively for aluminum which would normally be found in the gamma prime phase. Thus, the microstructure of the present invention comprises Mo fibers in a gamma prime matrix wherein from at least 15.5% and preferably 18.6% to 34% of the nominal aluminum content has been replaced by Ta on an equiatomic basis.
If the molybdenum content is increased beyond the limits set forth in the equation, primary alpha molybdenum-dendrites form during solidification. If the molybdenum content is much less than that set forth in the equation, primary gamma prime dendrites will form. Both of these primary phases adversely affect the mechanical properties.
The nominal composition given by the preceding equation is 12.5 weight percent Mo, 5.45 weight percent Ta, 16.55 weight percent Al, balance nickel, the nominal composition of the preferred range is 12.5 weight percent Mo, 5.8 weight percent Ta, 16.2 weight percent Al, balance nickel. In weight percent, then two nominal compositions are 6.9 weight percent Al, 18.5 weight percent Mo, 15.2 weight percent Ta, balance essentially nickel and 18.4 weight percent Mo, 6.7 weight percent Al, 16.1 weight percent Ta, balance nickel respectively.
Alloys within the ranges previously described can be directionally solidified to produce aligned structures consisting of a gamma prime matrix containing alpha molybdenum fibers. In distinction to the structure described in U.S. Pat. No. 4,012,241, the matrix will be pure gamma prime with no gamma particles and the volume fraction of the molybdenum fibers will be about 17% eg. 15%-18% in contrast to the volume fraction of fibers in the prior art of at least 20%.
It is now well-known that certain eutectic compositions may be directionally solidified to produce an aligned microstructure. The solidification conditions employed are critical to achieving the desired aligned microstructure. These conditions may be summarized in terms of G, the thermal gradient at the liquid-solid interface and R, the solidification rate or the rate of motion of the liquid-solid interface. In particular, for every eutectic alloy, there is a minimum value of G/R which must be exceeded to obtain an aligned microstructure. For the alloys in question, satisfactory microstructures have been obtained for values of G/R as low as 550° F./hr/in 2 . It is believed that G/R values in excess of about 400° F./hr/in 2 will be satisfactory for the production of aligned microstructures by coupled growth. The experimental results described in this application were obtained on material processed under conditions of G/R of about 2000° F./hr/in 2 . It is also known that the size of the second phase varies with R. For the alloys of the present invention, solidification rates of 2 centimeters per hour produce fibers whose diameter is about 0.6 microns and which are spaced about 1.6 microns from each other.
Upon solidification of the alloy, the liquid material will transform directly to the gamma prime plus alpha molybdenum structure. It was previously thought that this reaction occurred in the alloy described in U.S. Pat. No. 4,012,241. However, it has now been determined that in the compositions described in this prior patent the beta phase is formed on a temporary basis at elevated temperatures and this beta phase subsequently transforms with gamma to form gamma prime plus alpha phases when the temperature is reduced. Elimination of the beta phase improves the high temperature mechanical properties of the present alloy. The beta phase elimination is accomplished by the addition of controlled amounts of tantalum to the alloy as a substitution on an atomic basis for aluminum. Favorable mechanical properties are obtained with tantalum contents in excess of about 10 weight percent (about 3.4 atomic percent) and preferably in excess of 12 weight percent (about 4.1 atomic percent). An upper Ta level of about 20 weight percent is set primarily on basis that higher tantalum levels result in alloys with unacceptably high densities.
FIG. 1 is a graphical presentation of the equation previously described. FIG. 1 shows how the aluminum-molybdenum-tantalum contents are interrelated. The lower horizontal axis has a scale corresponding to the weight percent of tantalum in the alloy. The upper horizontal scale shows the atomic percent of tantalum present. The lefthand horizontal scale shows the molybdenum content in weight percent and the righthand horizontal scale shows the weight percent of aluminum present.
Thus, for example, an alloy containing 16 weight percent tantalum could contain from about 6.25 to about 7 weight percent aluminum and from about 18.1 to about 18.65 weight percent molybdenum. Used in a different fashion, the chart indicates that an alloy containing about 7 weight percent aluminum should contain between about 12.7 and about 16 weight percent tantalum and from about 18.1 to about 18.95 weight percent molybdenum.
A particularly preferred composition having very good rupture properties contains 18.2 weight percent molybdenum, 6.8 weight percent aluminum, 16.6 weight percent tantalum, balance nickel. This alloy upon directional solidification contains about 17 volume percent of molybdenum fibers and has a density of about 8.95 g/cc. This density is somewhat in excess of the density of the commonly used nickel base superalloys. A widely used commercial alloy is known as MAR-M-200+Hf which has a nominal composition of 9% Cr, 10% Co, 5% Al, 2% Ti, 12.5% W, 1% Cb, 2% Hf, 11% C, 0.015% B, balance nickel has a density of about 8.6 g/cc. It is anticipated that the density of the invention alloy could be decreased by substituting a material selected from the group consisting of titanium, columbium and vanadium from up to about half the tantalum content on an atomic basis. The composition of this preferred alloy, with a substitution of titanium for half the tantalum, is 62.1 Ni, 19.5 Mo, 7.2 Al, 8.8 Ta, 2.3 Ti and the composition of an alloy having a substitution of columbium for half of the tantalum would be about 60.8 Ni, 19.1 Mo, 7 Al, 8.6 Ta, 4.4 Cb. The approximate density of these alloys would be about 8.4 g/cc and 8.5 g/cc respectively. In like manner, up to about 10% of the Mo may be replaced on an equiatomic basis by W although this will adversely affect the density. Up to about 25% of the nickel may be replaced by an equiatomic amount of Co with virtually no effect on density.
The longitudinal properties of polycrystalline articles fabricated from the invention alloy is extremely high. However, the transverse properties of the alloy are low as a consequence of grain boundaries. There are two solutions to this problem.
The first is a compositional modification involving the addition of one or more materials selected from the group consisting of up to 2 percent halfnium, up to 0.5 percent zirconium, up to 0.1 percent carbon and up to 0.1 percent boron. These elements are chemically active and tend to tie up the impurities which would normally segregate the high angle grain boundaries.
The second solution is to prepare the articles in the form of single crystals which are free from internal high angle grain boundaries. The term "high angle grain boundaries" refers to those boundaries which separate grains which are misoriented by more than about 2° F.
The effect of tantalum content on the stress rupture life of the alloy tested at 1900° F. and 30 ksi load are shown in FIG. 2. An alloy having a composition of 21 percent molybdenum, 9 percent aluminum and 6 percent tantalum (this alloy obeys the composition equation but contains only 2 atomic percent tantalum) had an average rupture life of about five hours. An alloy having a composition of 18.3 percent molybdenum, 6.8 percent aluminum, 16.6 percent tantalum, balance nickel, had an average rupture life in excess of 500 hours an improvement by a factor of almost 100 over the low tantalum alloy.
FIG. 3 shows the stress rupture life invention in the form of a Larson Miller parameter curve for the invention alloy, alloys described in U.S. Pat. Nos. 4,012,241 and 4,111,723 compared with MAR-M-200+Hf (previously described).
All of these curves show longitudinal properties for directionally solidified material. It can be seen that the present invention alloy article represents an improvement over the prior art eutectics and the improvement over the prior art eutectics is approximately the same as the improvement of the prior art eutectic over the conventional superalloys.
A further benefit provided by tantalum additions is reduced hot corrosion. FIG. 4 shows the weight gain of various alloys in hot corrosion tests in which specimens were coated with 0.5 mg/cm 2 Na 2 So 4 and tested in air 900° C. The chart shows the weight change as a function of time. Increasing weight indicates that corrosion is occurring accompanied by the formation of corrosion products. FIG. 4 also contains a curve showing the sulfidation resistance of alloy B1900, a commercially used superalloy which is moderately susceptible to sulfidation attack. The nominal composition of B1900 is 8% Cr, 10% Co, 6% Mo, 1% Ti, 6% Al, 4.3% Ta, 0.1% C, 0.015% B, 0.08% Zr. This chart shows that increasing the tantalum content decreases the sulfidation attack and that a tantalum content of about 11.6% reduced the sulfidation attack to a rate about twice that of a commercially superalloy. It is anticipated that alloys containing 16% tantalum would display even better resistance to sulfidation attack.
FIG. 5 shows tensile properties of the articles of the present invention as a function of temperature. The curve shows both yield strength and ultimate tensile strength of the present alloy, the eutectic articles described in prior U.S. Pat. No. 4,012,241 and MAR-M-200 a conventionally nickel base superally (directionally solidified) whose composition has been given previously. The superiority of the alloy of the present invention can readily be seen.
Thus what has been described is a modified alloy article having gamma prime matrix/molybdenum fiber microstructure. The tantalum modifications provided for improved mechanical properties in combination with improved resistance to environmental degradation.
Although this invention has been shown and described with respect to a preferred embodiment thereof, it should be understood by those skilled in the art that various changes and omissions in the form and detail thereof may be made therein without departing from the spirit and scope of the invention. | This disclosure relates to directionally solidified articles produced from a eutectic alloy in the nickel-aluminum-molybdenum system with tantalum added. The articles have a microstructure consisting of a ductile matrix phase of gamma prime containing a fibrous reinforcing second phase of alpha Mo. The nominal composition of the base alloy is 6.9 weight percent aluminum, 15.2 weight percent tantalum, 18.5 weight percent molybdenum, balance nickel. The directionally solidified alloy articles of the invention are characterized by exceptional mechanical properties combined with good oxidation resistance and reasonable sulfidation resistance at elevated temperatures. | 2 |
CROSS REFERENCE TO RELATED PATENTS
The present invention is related to the following patents which are specifically incorporated herein by reference:
Pending patent application Ser. No. 09/409,345 filed Sep. 30, 1999 by Cessna et al. entitled “Framework for Dynamic Hierarchical Grouping and Calculation based on Multidimensional Characteristics” and assigned to the assignee of the present invention. This patent is sometimes referred to herein as the Framework Patent.
Pending patent application Ser. No. 09/491,834 filed Jan. 26, 2000 by C. Bialik et al. entitled “Method and System for Database Management for Supply Chain Management” and assigned to the assignee of the present invention. This patent is sometimes referred to herein as the Database Patent.
Patent application Ser. No. 09/781,615 filed concurrently by the inventor of the present document, Iwao Hatanaka, and entitled “Method and System for Incorporating Legacy Applications into a Distributed Data Processing System” and assigned to the assignee of the present invention. This patent is sometimes called the Legacy Application Patent.
Issued U.S. Pat. No. 6,021,493 of Daryl C. Cromer et al. entitled “System and Method for Detecting When a Computer System is Removed from a Network” issued on Feb. 1, 2000 and assigned to the assignee of the present invention. This patent is sometimes referred to herein as the Heartbeat Patent and is useful in detecting whether a client is attached to a server.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is an improved system and method for automatically managing session resources in a distributed network of processors, such as a client-server environment, where the invention has the particular advantage of automatically releasing those resources allocated to a session when the session ends, whether through a normal ending or through an abnormal ending. More particularly, the present invention includes a session management framework which can be applied to release session resources when the session ends abnormally, e.g., through the halting of an application or the loss of a connection between the server and the client.
2. Background Art
In a client-server environment, a local terminal (sometimes referred to as a client) is connected to a server for the purpose of processing information in a distributed environment. Frequently, the client is itself a data processing system which communicates with a server which is generally a data processing system with increased resources, including applications and data which are not available at the client application. Such a system is described in some detail in the Framework Patent referenced above. In a client-server environment, resources may be centrally managed at the server as opposed to being disparately managed at each individual client. In some cases, the client does not have the capability of managing or maintaining large resources.
The client is frequently located at a distance from the server and communicates with the server using telecommunication facilities, including hardware and software operating over phone service such as might be provided using telephone lines, either alone or in combination with other communication systems such as satellite or microwave communications. A series of communications occur between a client and its server (for example, to execute an application on the server using data supplied by the client and report the results of the application back to the client) is sometimes referred to as a session, with a session including a plurality of communications between the server and the client. In any event, there are frequently several different links in the communications chain, and when one of the links fails to operate, the communications channel is disrupted and the session is terminated.
While the session was in existence, various resources at the server are dedicated or reserved for the use of the particular client which requests use of those resources. So, in a supply chain application, a variety of storage units associated with the server may be used by a client during a session and various applications and databases may be dedicated to the client and its session, often to the preclusion of using those same resources for other clients while a session with the one client is in progress. Such a preclusion is understandable, particularly when an application may be changing the application or the database, so access during a change by another application may provide the wrong execution or the wrong data.
A session with a client “ties up” resources generally (memory used for one application cannot be used at the same time for another application) and for some specific reasons (a client which is using a database typically marks the database so that another client cannot simultaneously use the database and change the information stored in the database while the other client is using the database, for example).
Since the resources are limited and other clients may want to use the same resources, it is advantageous to release the resources as soon as the resources are not needed, and the normal termination of a session (e.g., the completion of execution of a program) typically provides a release of the resources which have been used for the session as a part of the normal ending of the session.
But, when a session is abnormally terminated, it does not go through the normal ending or winding down process which releases the resources. In fact, many of the events which contribute to the abnormal termination of a session result from a total lack of communications with a client, perhaps because the connection between the client and the server is no longer functional. This is becoming more of a problem when the communication is over the public Internet or a virtual private networks, where a large number of users are connected through paths which are constantly changing as the network evolves, and the session depends on the continuing availability of a path between the client and the server.
The Legacy Application Patent describes an approach to allow use of legacy applications in a distributed processing environment, allowing legacy applications which were not designed to be utilized in a distributed processing system to be used in such a system. Such a system inherently requires that resources which are being used in a distributed data processing system be committed to the use and be released once the processing has ended.
Several approaches have been suggested for determining when a session is no longer active. One of these involves polling, or making sure that the client and the server remain active by periodically issuing an inquiry from the one to the other with an answer back if the connection is still in place. This involves setting up some kind of periodic inquiry system and keeping track of when an inquiry is due for each of the clients, an exercise which requires resources and does not necessarily provide a prompt notice that a client has been dropped by the network—that is, without a lot of repeated polling of each client every short interval, the server does not know which clients remain attached and which clients are no longer attached. But, polling requires continuing use of resource and suggests that polling ought to be done at lengthy intervals to reduce the use of network resources, but the longer the interval, the longer resources may be dedicated to serve a session which no longer exists.
A prior art system for determine whether a resource is attached sometimes uses a “heart beat” technique for determining whether the resource remains attached. But, in such a system a ping is sent out addressed to the remote user and the absence of a response is taken to mean that the resource is not attached, when, in fact, the ping or its response may have been misdirected or lost in the system without the resource actually being disconnected. Another disadvantage of polling is that message traffic is increased for each client which is added to the system. Also, there is the lack of an unequivocal indication that a resource is no longer needed or that a client is no longer connected.
Accordingly, the prior art systems have undesirable disadvantages and limitations.
SUMMARY OF THE INVENTION
The present invention overcomes the limitations and disadvantages of the prior art systems by providing a system and method for releasing resources dedicated to a session promptly, even when the session ends abnormally and without a termination message.
The present invention has the advantage that it is simple and easy to implement to allow for the release of resources held for a client when the client is no longer connected to the server.
The present invention allows for the prompt reallocation of resources from a client to an other client when the first client is no longer using the resource without polling or a periodic inquiry of the connected status of each of the clients using resources of a given server.
The present invention involves setting up a resource manager for each session and logging the use of resources associated with that session. Then, when the session is no longer active—for whatever reason, including normal disconnection or a lost connection, the resource manager consults the listing of resources associated with that session and releases the resources for use, allowing use with other sessions.
Using the resource manager for normal and abnormal session terminations means that it is not necessary to have two different types of session terminations, one for normal terminations and a different one for an abnormal termination.
The present system also allows for a table which identifies which resource is associated with which user.
The present application is suited for use in a system such as are described in the Legacy Application Patent. The use of a distributed data processing solution means that different processors may have reserved resources such as applications which need to be resolved when a session ends.
A system such as the Heartbeat Patent may be used to determine whether a client is attached to the server at any given time. By periodically querying the clients, it is possible to determine whether the client is still coupled to the server or if the connection has been lost for some reason. The Heartbeat Patent is one way (but certainly not the only way) to determine whether the client is still coupled to the server and capable of communicating. If the Heartbeat Patent detects that a given client is no longer attached, it can signal the server to allow release of the resources associated with the client.
Other objects and advantages of the present invention will be apparent to those skilled in the relevant art in view of the following description of the preferred embodiment, taken together with the accompanying drawings and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is an improved system and method for resource cleanup, an embodiment of which is illustrated with reference to the accompanying drawings in which:
FIG. 1 depicts a communications system representative of the preferred embodiment of the present invention;
FIG. 2 , consisting of FIG. 2A and FIG. 2B , are flow diagrams of the preferred embodiment of the present invention; and
FIG. 3 , consisting of FIG. 3A and FIG. 3B , are diagrams illustrating resource tables useful in practicing the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the following description of the preferred embodiment, the best implementation of practicing the invention presently known to the inventors will be described with some particularity. However, this description is intended as a broad, general teaching of the concepts of the present invention in a specific embodiment but is not intended to be limiting the present invention to that as shown in this embodiment, especially since those skilled in the relevant art will recognize many variations and changes to the specific structure and operation shown and described with respect to these figures.
FIG. 1 illustrates a communications system of the type used in the present invention. In this FIG. 1 , a first client (CLIENT 1 ) 100 is connected to a first server (SERVER 1 ) 110 through a network 120 . Additional clients (CLIENT 2 , CLIENT 3 , CLIENT 4 ) 131 , 132 , 133 , respectively are shown also connected to the first server 110 through the network 120 and additional servers (SERVER 2 , SERVER 3 and SERVER 4 ) 141 , 142 , 143 , respectively are also shown connected to the network 120 . While this is a simplistic view of a network in which a plurality of servers are connected to serve a plurality of clients, it will allow discussion of the problems with such an arrangement and an understanding of the present invention and its advantages. The first client 100 may involve an application which uses a resource at the first server 110 (for example, an application APPLN 1 referred to by the reference numeral 111 ) and a resource at the second server 141 (for example, a database DB referred to by the reference numeral 151 ) and store the result in a file 152 maintained on the third server 142 (the file 152 might be a file with pro forma income and profit projections), all of which data processing is accomplished through the communications network 120 which connects the client 110 with the servers 110 , 141 and 142 . Meanwhile, the second client 131 may wish to use resources at the first server 110 , the second server 141 and a fourth server 143 . If the second client 131 is using different resources at the servers from the other clients at any given time, then there is no problem. If, however, the first client 100 is using the particular application APPLN 1 111 at the first server 110 , then the second client may not be permitted to use the application APPLN 1 111 at that same time, but would be permitted to use an application APPLN 2 112 which is also at the first server.
The present invention leverages the fact that each client session with a server is associated with a single file descriptor in the server during a client connection to the server. All communications from and to that client takes place through that file descriptor. Through a callback program associated with that file descriptor, client termination events can be captured to trigger desired system processing at precisely the time that the client disconnects from the server. This functionality allows for automatic session clean-up by detecting client termination and then freeing up corresponding resources being held on the server for the terminated client session.
FIG. 2 illustrates in flow diagram form the logic of the present invention showing aspects of the present invention. FIG. 2 consists of FIG. 2A and FIG. 2B . FIG. 2A shows logic for the determination of whether a resource is available and assigning the resource to a particular requesting client while FIG. 2B shows logic for determining whether to release a resource and the steps taken to release that resource and allow for further use of the resource by other clients.
FIG. 2A illustrates the process of a client using resources at a server as was described in connection with FIG. 1 . The process starts at block 202 and at block 204 a request is received by the server for resources associated with that server, resources which may be use of an application, access to a database stored on the server or simply to a block of memory, for example, as a temporary storage for an application. While the server may have a large number of resources and many of these resources are not unique (one block of empty memory may be similar to the next), others of the resources are unique (the server may have a single copy of an application or a database) and the resources are limited (the server might well run out of memory if the memory were not released and reused by a second client after the first has completed its processing). Based on the request received at the block 204 for resources, at block 206 the server determines whether the resource is available to the requesting client. Such availability is determined in connection with resource listings such as FIG. 3 , particularly FIG. 3B which identifies each resource as being available or being used by a named client. If the client is requesting use of a database already in use by another client or if the memory requested is not available, then the request is denied at block 208 with an appropriate message (“resource in use; try again later” or “inadequate memory presently available; try elsewhere or try again later”). If, on the other hand, the resource is available for the client, then at block 210 , access is granted and the resource is logged (see FIG. 3 and the associated text for a discussion of the logging process to include identification of which resources are available and which are used by which clients) as assigned to the requesting client. In any event, following the disposition of a request for resources, either by granting it at block 210 or denying it at block 208 , control returns to the starting area where the next request can be processed by the block 204 .
FIG. 2B illustrates the process for releasing a resource which has been assigned to a client and for which the client no longer has a need for the resource. Such a release may be because the program using the resource has run its course and terminated successfully or because something unnatural has occurred, like the client has become disconnected from the server—i.e., either the server 110 or the client 100 is no longer connected to the network 120 or the client 100 is no longer operational. While a normal termination of an application program may issue the explicit command to release the resources that the application has been using, the program may abort or otherwise not issue such a command.
The process of FIG. 2B is as follows: starting from block 220 , at block 222 the question is asked whether a client has specifically released a resource. If not, then at block 224 , it is determined whether the client remains attached to the network. This determination can be made through any of a number of conventional approaches, such as “pinging” the client or by determining a heartbeat of the client using the Heartbeat Patent referenced above. If the client is present, then control passes to an optional set of time determinations which serve to limit the time that a resource can be held/used—either with activity or without activity. Associated with the resource (e.g., an application, database or memory) and/or the client are allowable time intervals. For example, a client may use a first application for 30 minutes but will be considered inactive if no activity occurs within a 15 minute time period. Thus, at block 226 the amount of time a resource has been used will be compared with an allowable time for such use (if any has been set) by comparing the present time with the beginning time which was stored in column 308 of FIG. 3A to determine the amount of time the resource has been in use. If the time that the resource has been used does not exceed the limit, then the amount of inactive time is compared at block 228 . That is, the period since the last use (in column 310 of FIG. 3 ) to the present is compared with a threshold (if set) to determine whether the resource has been held without activity longer than a preset period of time. If the client released the resource (at block 222 ), the client is not attached (at block 224 ), the time of use (block 226 ) or the time of inactivity (block 228 ) exceed the set limits, then the resource is released at block 230 with the entry in the table of resources being used ( FIG. 3A ) erased at block 232 and the resource marked as available in the listing of FIG. 3B at block 234 . Control then returns to the start for the next resource action.
FIG. 3 shows resource tables useful in practicing the present invention. In FIG. 3A , a first table 300 depicts in list form the resources currently being used and the client using each of the resources. Although only a portion of this table 300 is shown to illustrate the principles of the present invention, the table could be as large as necessary to contain data about all the clients using the server and the resources that each of the clients is currently using. The table includes a first column 302 which lists the resource being used, a second column 304 listing the client using the resource, a third column 306 indicating the type of access (whether it is read only or read/write), a fourth column 308 indicating the time which the resource was first accessed and a fifth column 310 indicating the time that the resource was last used. Use of the fourth column 308 with the beginning time allows for a time limit to be set for release of the resource after a fixed amount of time and the fifth column 310 (last use) allows for a time limit to be set that releases a resource if it has not been used within a fixed period of time. That is, the resource could be released after x minutes of use (based on a comparison of the current time with the start time stored in column 308 ) or after y minutes of nonuse (based on a comparison of the current time with the time in column 310 ). The times allowed (x minutes of use, y minutes of nonuse) are subject to system constraints and may be adjusted based on the type of use and whether concurrent uses are permitted. In some situations, a read-only access of a resource may not preclude others' use of the same resource and one client might be permitted to continue to use such a resource on a non-exclusive basis than would be permitted if the resource were being used on an exclusive basis. An optional sixth column 312 provides the time of the last indication that the client is connected, a time which may be provided by receiving a request from the client or from a return “ping” of the client as discussed elsewhere.
In FIG. 3B , a listing of the resources is provided and an associated status for each resource—whether the resource is “free” for use by a client or if it is currently committed to a client and not available. This FIG. 3B lists each of the resources along with its status, by resource. So, FIG. 3B includes a left column 330 which lists the resource and a right column 332 which either lists he resource as being used by a named client or being available. This, for the simple example of FIG. 1 , APPLN 1 is shown in block 334 as a resource and in block 344 , it is being used by client 110 . APPLN 2 is listed in block 336 as a resource and in block 346 , it is being used by client 131 . APPLN 3 is listed in block 338 as being available in block 348 . Similarly blocks of memory and other resources such as the database DB can be assigned to a particular client, and at the end of the use by that client, release by removing the entry in the columns of FIG. 3 .
The present invention can be realized in hardware, software, or a combination of hardware and software. A data processing tool according to the present invention can be realized in a centralized fashion in one computer system, or in a distributed fashion where different elements are spread across several interconnected computer systems. Any kind of computer system—or other apparatus adapted for carrying out the methods described herein—is suited. A typical combination of hardware and software could be a general purpose computer system with a computer program that, when being loaded and executed, controls the computer system such that it carries out the methods described herein. The present invention can also be embedded in a computer program product, which comprises all the features enabling the implementation of the methods described herein, and which—when loaded in a computer system—is able to carry out these methods.
“Computer program means” or “computer program” in the present context mean any expression, in any language, code or notation, of a set of instructions intended to cause a system having an information processing capability to perform a particular function either directly or after either or both of the following a) conversion to another language, code or notation; b) reproduction in a different material form.
While the present invention is described in the context of an apparatus and a method of providing resource management, the present invention may be implemented in the form of a service where collecting, maintaining and processing of information is located apart from the server and information is communicated as needed to the server.
Of course, many modifications of the present invention will be apparent to those skilled in the relevant art in view of the foregoing description of the preferred embodiment, taken together with the accompanying drawings. For example, the system for recognizing that the session between the client and the server no longer exists may be determined in any manner and is not limited to that disclosed in the foregoing material. Additionally, the location and type of information maintained about a session may be modified to suit the application and need not be the listing of resources associated with each client as disclosed. Such information may be stored in connection with each resource being used rather than in a central location, although there are advantages to having the information located centrally in that a central location makes it easier and quicker to release and reuse the resource again. Additionally, certain features of the present invention may be useful without the corresponding use of other features without departing from the spirit of the present invention. For example, a client may be using several resources associated with different applications and one application may end (so the resources associated with that application should be released) or the entire connection may terminate (so all applications terminate). Further, the system of FIG. 3B arranges data on resource use including the same data as FIG. 3A , and the two could be combined, if desired, using a single database to show what resources are in use and what clients are using the resource. Accordingly, the foregoing description of the preferred embodiment should be considered as merely illustrative of the principles of the present invention and not in limitation thereof. | A system and method of automatic session resource clean-up resulting from a client-server session wherein the client has requested use of server resources during the session. During each session, a list of the resources allocated to that session and associated with the client is maintained and, when the session terminates, either naturally or unnaturally, the allocated resources are released or freed up, allowing later use of the same resources by a different session, either with the same client or with a different client. Because unnatural terminations do not normally provide a farewell message from the client to the server there is no way for the server to release the resource and no naturally occurring message to the server that the client is not present. The present invention overcomes these disadvantages by determining when a session has ended and releasing the resources associated with the client. | 7 |
This is a continuation of application Ser. No. 11/291,249, filed Dec. 1, 2005, now U.S. Pat. No. 7,536,568, the entire content is incorporated herein by reference.
FIELD OF THE INVENTION
The present invention generally relates to electronic devices having a sleep mode. In particular, the invention relates to a method and apparatus for placing an electronic device in a power conserving sleep mode and waking it upon an input from a user.
BACKGROUND OF THE INVENTION
For many years, battery-operated devices have been popular. In early devices, the user was required to power down the device or manually disconnect the battery from the device via a switch so that the device did not drain the battery when not in use.
There are now a number of electronic devices that have been developed to operate with low power so that completely isolating the batteries via a user-operated switch is not necessary. More recent electronic devices have also been designed with a sleep state wherein the microprocessor of the device will use a switch to cut power to nonessential elements of the device thereby saving additional energy by eliminating the leakage currents in those elements. When a user presses a button or otherwise attempts to use the device, the device wakes up and the processor causes power to be restored to the deactivated elements. Even in their sleep state, these low power devices still have leakage currents.
Even small leakage currents can significantly impact battery life. The following Table 1 illustrates one model of shelf life of a 9 volt battery and a comparable set of AA batteries.
TABLE 1
Total Capacity
Self Discharge
(mAH)
(2% per yr)
9 V
580 mAH
11.6 mAH/yr
AA
2700 mAH
54 mAH/yr
Table 1 assumes a self discharge rate of 2% per year of the capacity of a battery. Assuming now that a battery will last a year in a device and that the device is idle for 16 hours every day, then this self discharge rate is equivalent to an idle current drain of 9.2 microamps in the case of the AA batteries and 1.99 microamps in the case of the 9V battery.
Modern electronic devices are generally designed to use very little power while idle. This is generally accomplished by use of a sleep state in which most components are designed not to conduct any current. However, a CMOS device inherently allows some current flow called leakage current. Leakage currents present a significant impediment to battery life and energy conservation. The following Table 2 illustrates the amount of power dissipated by a device with different leakage currents assuming that the battery lasts at least a year in a device and that the device is in its sleep state for 16 hours every day.
TABLE 2
40 uA leakage
5 uA leakage
1 uA leakage
Power Loss
% of total
Power Loss
% of total
Power Loss
% of total
(mAH/yr)
capacity
(mAH/yr)
capacity
(mAH/yr)
capacity
9 V
233.6
40.28%
29.2
5.03%
5.84
1.01%
AA
233.6
8.65%
29.2
1.08%
5.84
0.22%
As shown in Table 2, leakage currents can present a significant energy drain during a sleep state and impact battery life. For the above-described usage scenario, almost half of the capacity (40.28%) of a 9V battery is dissipated by a device with only 40 microamps of leakage current in its sleep state. Reducing the leakage current to 1 microamp means that at the end of the year, the battery has retained over 39% of its capacity that it would have otherwise lost to leakage currents. Additionally, since only 1% of the battery's capacity is lost to leakage currents during the device's sleep state, the battery's own self discharge rate (approximately 2% per year) becomes a relatively important factor in the life of the battery. Thus, it is highly desirable to decrease the sleep state current draw of these devices to improve battery life and/or generally conserve energy. More specifically, it is desirable to substantially eliminate leakage currents within the device while it is in its sleep state, and still be able to easily and quickly wake the device from its sleep state.
SUMMARY OF THE INVENTION
In accordance with one aspect of the invention, an apparatus is provided for selectively enabling power. The apparatus includes a power supply and a device having a controller and an input activated by a user. The controller is selectively powered by the power supply. A sensing circuit senses activation of the input activated by the user and enables the power supply to provide power to the device's controller in response to the sensed activation of the input by the user. The controller is responsive to the sensed activation of the input by the user for enabling a latch circuit and for subsequently disabling the latch circuit. The latch circuit causes the power supply to continue to provide power to the controller while it is enabled.
In accordance with another aspect of the invention, a method is provided for selectively enabling a power supply of a device having a controller selectively powered by the power supply. The activation of an input by a user of the device is sensed. The power supply is enabled to provide power to the controller in response to the sensed activation of the input by the user. The enabled power supply is latched to provide power to the controller during operation of the device. The power supply is disabled to discontinue providing power to the controller.
In accordance with another aspect of the invention, an apparatus is provided for selectively enabling power. The apparatus includes a power supply and a device having a controller and an input activated by a user. The controller is selectively powered by the power supply. The apparatus also includes a sensing circuit for sensing activation of the input by the user and for enabling the power supply to provide power to the controller in response to the sensed activation of the input by the user. The controller is responsive to the sensed activation of the input by the user for causing the sensing circuit to continue enabling the power supply to provide power to the controller during operation of the device and for causing the sensing circuit to disable the power supply from providing power to the controller.
Alternatively, the invention may comprise various other methods and apparatuses.
Other objects and features will be in part apparent and in part pointed out hereinafter.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram illustrating a wakeup circuit using a passive switch sensing circuit and a latch circuit according to one embodiment of the invention.
FIG. 2 is a block diagram illustrating a wakeup circuit using an active switch sensing circuit that eliminates the separate latch circuit according to one embodiment of the invention.
FIG. 3 is a schematic diagram illustrating a momentary switch and passive switch sensing circuit according to one embodiment of the invention.
FIG. 4 is a schematic diagram illustrating a single pole switch and passive switch sensing circuit according to one embodiment of the invention.
FIG. 5 is a schematic diagram illustrating a latch circuit according to one embodiment of the invention.
Corresponding reference characters indicate corresponding parts throughout the drawings.
DETAILED DESCRIPTION OF THE INVENTION
In one embodiment, the present invention is an ultra low power wake-up circuit which draws essentially no power while waiting for a user input. Power is supplied to components of the wake-up circuit directly from a power supply and power is selectively supplied to device components through a load switch. The wake-up circuit is adapted to wake up the device in response to any number of events, such as a user pushing any of the input keys on the device's user interface, removing or replacing a component from its docking position on the device, receiving a signal from another device, or opening or closing the cover of the device. For example, in the case of a clinical thermometer such as a predictive or infrared thermometer, the device should have the capability to wake up whenever the temperature probe is removed or replaced, whenever the probe cover is removed or replaced, whenever a button on the device is pressed, or whenever a device cover is opened or closed. The thermometer has a microprocessor responsive to the inputs from the buttons and the probe and performs functions in response to these inputs. In some embodiments, after the thermometer has performed its function, the microprocessor waits for a preset time and instructs the wake-up circuit to place the device in its sleep state. In general, the function of the device, the events that wake it up, and the events that return it to its sleep state are based on system-defined requirements and such activities can be hardwired or manual. One skilled in the art will recognize that the invention is also applicable to pulse meters, blood pressure monitors, predictive thermometers, blood sugar monitors, and other electrical devices.
The following discussion is focused on reducing power consumption of battery-powered devices so that their batteries have a longer life. One skilled in the art will notice that the invention is equally applicable to devices with other types of power supplies such as AC to DC converters, AC sources, and other power sources to reduce power consumption.
Referring now to FIG. 1 , an embodiment of the invention using a passive switch-sensing circuit and separate latch circuit is illustrated. A power supply 102 continuously supplies power to a latch circuit 104 , a switch 106 , a passive switch sensing circuit 110 , and a load switch 108 , all of which, optionally, may be configured to have substantially no leakage currents while waiting for a user input.
In one embodiment, this can be accomplished by designing the circuits and switches such that they are substantially free of CMOS components and rely instead on only NMOS devices. The power supply 102 may be batteries or any other power device such as an AC/DC power converter. Additionally, the switch 106 may be an array of user input switches (see FIG. 3 ).
The passive switch-sensing circuit 110 detects when a user actuates switch 106 of the device and provides a SENSE ENABLE signal of a preset duration to enable the load switch 108 to connect the power supply 102 and a microprocessor 112 via the load switch 108 and to connect any other device components such as memory and/or a communications component (not shown) to the power supply 102 . In response to receiving power, the microprocessor 112 activates the latch circuit 104 by a LATCH signal and performs functions based on user input IN from the actuated switch 106 . The activated latch circuit 104 provides a LATCH ENABLE signal to the load switch 108 to continue supplying power to the device's components including the microprocessor 112 . When the device has finished its operations, the microprocessor 112 waits for more user input for a preset time period (e.g. a timeout period set by the user) and then signals the latch circuit 104 via the LATCH signal to place the device back into its sleep state. For example, the microprocessor 112 may discontinue providing the LATCH signal to the latch circuit 104 . The latch circuit 104 signals the load switch 108 (e.g., discontinues providing the LATCH ENABLE signal) to stop supplying power to the device. The load switch 108 then changes state to discontinue supplying power VSW to the microprocessor 112 . The device thus returns to its sleep state wherein power VPS is only supplied to the user input switch 106 , passive switch sensing circuit 110 , latch circuit 104 , and the load switch 108 . It remains in this sleep state waiting for user input via switch 106 .
In operation, a user presses a switch 106 on the device to begin use of the device. The passive switch sensing circuit 110 senses the change of state of switch 106 and temporarily produces the SENSE ENABLE signal causing the load switch to provide power VSW to the microprocessor 112 . In response to the power, the microprocessor 112 starts up and provides the LATCH signal to the latch circuit. In response to the LATCH signal, the latch circuit provides the LATCH ENABLE signal to the load switch which continues to maintain load switch in its enabled state, causing it to continue supplying power from the power supply 102 to the microprocessor 112 . The user can then use the device for its intended purpose. When the device has finished its operations, the microprocessor 112 waits for further user input for a preset time. If no such input is received within a time-out period, the microprocessor 112 terminates the LATCH signal which causes the latch circuit to terminate the LATCH ENABLE signal, and the load switch stops supplying power VSW to the microprocessor 112 .
Referring now to FIG. 2 , an embodiment of the invention using an active switch sensing circuit is shown. In this embodiment, a power supply 202 continuously supplies power VPS to a user input switch 206 , an active switch sensing circuit 210 , and a load switch 208 , all of which, optionally, may be configured to have substantially no leakage currents while waiting for a user input.
In one embodiment, the active switch sensing circuit 210 is substantially a microprocessor from Microchip Corporation, PIC 10F202, which operates on less than 1 microamp of current while waiting for a switch 206 input. Some common ancillary circuitry may be required with this particular component to buffer the switch 206 input. The microprocessor used in the active switch sensing circuit 210 has limited capabilities which allow it to be designed to have low leakage currents. The active switch sensing circuit 210 is different from the passive switch sensing circuit 110 of FIG. 1 , in that most of the sensing circuit's functions are located in one device instead of a number of discrete components. This allows for a smaller overall product and possibly reduces manufacturing costs.
When a user actuates the input switch 206 , the active switch-sensing circuit 210 temporarily enables the load switch 208 to supply power VSW to the device's microprocessor 212 . The microprocessor 212 starts up and instructs the active switch-sensing circuit 210 to continue causing the load switch 208 to supply power (e.g., provides a LATCH signal). The device then performs operations based on the user input of the switch 206 . When the device has finished performing its operations, the microprocessor 212 waits for further user input for a preset period and then instructs the active switch-sensing circuit 210 to place the device into its sleep state. In response, the active switch-sensing circuit 210 signals the load switch 208 via the ENABLE signal to discontinue power VSW to the microprocessor 212 . The device is thus returned to its sleep state wherein power VPS is only being supplied to the user input switch 206 , active switch-sensing circuit 210 , and the load switch 208 . In this embodiment, the need for the separate latch circuit 104 has been eliminated by using an active switch-sensing circuit 210 which incorporates the function of the latch circuit 104 .
It is contemplated that the timeout function (e.g. a period of time during which the microprocessor waits for further user input for a preset period and then instructs the wake-up circuit to place the device into its sleep state) may be implemented in the microprocessor of the device, in a separate circuit of the device, by the wake-up circuit itself or by a combination thereof.
A device can, and usually will, have multiple user input switches. It should be apparent to one skilled in the art that the invention will work with all, a select few, or even just one user input switch of the device. For example, additional switches are shown in phantom in FIG. 3 .
The load switch also has multiple embodiments. In one preferred embodiment, it is a single p-channel FET. It may also be an array of p-channel FETs which may be required for devices that draw higher amounts of current when in use. In another embodiment, it may be an active load switch. One such active load switch is an FDC6323 manufactured by Fairchild Semiconductor. Active load switches may also be arrayed for additional current capacity.
It should be apparent to one skilled in the art that numerous combinations of sensing circuits, load switches, and user input switches can be made without deviating from the invention.
Referring now to FIG. 3 , one embodiment of a user input switch 106 is shown, along with a passive switch sensing circuit 110 . The input VPS is a supply of continuous power from the power supply 102 (e.g., nominally 4.5 volts in the case of 3 AAA batteries in series). When a user activates a momentary switch 302 , the SENSE ENABLE signal is pulled electrically low. When the switch 302 is released, the SENSE ENABLE signal remains temporarily low for a period of time determined by the values of resistor R 1 and capacitor C 1 . The SENSE ENABLE signal activates the load switch 108 and thus causes power to be supplied to the device's microprocessor 112 while the signal is present. The resistor R 1 and capacitor C 1 of the passive switch sensing circuit 110 are selected so that the microprocessor 112 has adequate time to startup and provide the LATCH signal. Example values of resistor R 1 and capacitor C 1 for providing a sufficiently long SENSE ENABLE signal while keeping power usage low, are 1 megaohm and 0.1 microfarad, respectively. The microprocessor 112 then reads the input signal IN and performs operations according to that and any other inputs. As shown in phantom, additional sensing circuits may be used to monitor additional inputs.
Referring now to FIG. 4 , an alternative embodiment of a user input switch 106 is shown, along with a passive switch-sensing circuit 110 ( FIG. 1 ). Whereas the switch in FIG. 3 is a momentary switch, a switch 402 in this embodiment is a single throw, single pole switch. The input VSW is a supply of switched power directly from the load switch 108 or a regulator powered or enabled by the switched power from the load switch 108 , and the input VPS is a supply of continuous power from the power supply 102 or an associated regulator. The switch 402 is suitable for connection as an indicator of a component or cover status of a device; e.g., whether the component is in a holder or not, whether there is a cover on a probe or not, and whether a cover is open or closed. An output pulse PR instructs the device's microprocessor 112 that the circuit was awakened by actuation of the associated component. An output signal PROBE tells the microprocessor 112 whether the switch 402 is open or closed, thus indicating the status of the component or cover. Changing the state of the switch 402 from open to closed wakes the device from its sleep state. The resistor R 2 and capacitor C 2 should be chosen so that the SENSE ENABLE signal is provided for a sufficient amount of time to start up the device's microprocessor 112 . Example values of resistor R 2 and capacitor C 2 for providing a sufficiently long SENSE ENABLE signal while keeping power usage low, are 1 megaohm and 0.1 microfarad, respectively. The microprocessor 112 then supplies the LATCH signal to the latch circuit 104 which, in turn, causes the load switch 108 to continue supplying power to the microprocessor 112 . The device is thus awakened from its sleep state and the microprocessor 112 can analyze to determine status, for example, if a cover has been placed on a probe through the use of the switch 402 and passive switch-sensing circuit 110 .
Referring now to FIG. 5 , one embodiment of a latch circuit 104 is shown. While the latch circuit 104 is in its sleep state, both FET 502 and 504 are open circuits. The latch circuit 104 thus conducts substantially no current while the device is awaiting a user input, and the LATCH ENABLE signal is electrically high (e.g., the same voltage as VPS).
When the wake-up circuit has sensed a user input, the microprocessor 112 provides an input signal LATCH to the latch circuit 104 . The LATCH signal causes the FET 502 to conduct current. This, in turn, raises the voltage at the gate of FET 504 causing it to conduct current and the LATCH ENABLE signal is pulled electrically low causing the load switch 108 to continue supplying power to the microprocessor 112 . After the device has finished its operations, the microprocessor 112 waits for a timeout period then discontinues the LATCH signal. The latch circuit 104 discontinues the LATCH ENABLE signal which causes the load switch 108 to discontinue power to the microprocessor 112 , placing the device in its sleep state.
It is contemplated that the embodiments in FIGS. 3-5 may be built into the circuitry of a device, or implemented as an add-on to existing device circuitry, such as in a daughterboard configuration.
Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.
The order of execution or performance of the methods illustrated and described herein is not essential, unless otherwise specified. That is, it is contemplated by the inventors that elements of the methods may be performed in any order, unless otherwise specified, and that the methods may include more or less elements than those disclosed herein. For example, it is contemplated that executing or performing a particular element before, contemporaneously with, or after another element is within the scope of the various embodiments of the invention.
When introducing elements of the present invention or the preferred embodiments(s) thereof, the articles “a”, “an”, “the” and “said” are intended to mean that there are one or more of the elements. The terms “comprising”, “including” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.
In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.
As various changes could be made in the above products and methods without departing from the scope of the invention, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. | An apparatus for selectively enabling power including a power supply, and a device having a controller and an input activated by a user. The controller is selectively powered by the power supply. While the device is in a sleep state, a sensing circuit senses activation of the input by the user and enables the power supply to provide power to the controller in response to the sensed activation of the input by the user. A latch circuit causes the power supply to continue to provide power to the controller. The controller is responsive to the sensed activation of the input by the user for enabling the latch circuit and for disabling the latch circuit, thereby reentering the device into a sleep state. | 6 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a communication system, and more particularly to an integrated smart local wireless spread spectrum communication system.
[0003] 2. Description of Prior Art
[0004] Currently, the use of local wireless communication system is restricted by its limited channel numbers, and thus the number of customer is difficult to increase. Moreover, if it is desired to track the movement of a user within the communication system, the transmitting power of the base station must be increased greatly for tracing the local position of the user. Accordingly, the system becomes more complex. Alternatively, a GPS system (global positioning system) can be used for positioning a user. However, it is required to launch several lower orbit satellites, and this will result in a high cost and further requiring purchasing some related software and database. Therefore, the current local wireless communication system still has many defects to be eliminated.
SUMMARY OF THE INVENTION
[0005] Accordingly, the primary object of the present invention is to provide an integrated smart local wireless spread spectrum communication system, which employs smart antennas to detect the movement of a user and increase the available channel number so as to increase the number of customers.
[0006] Another object of the present invention is to provide an integrated smart local wireless spread spectrum communication system, which is capable of providing a local positioning function, saving the power consumption of the base station, and reducing the system complexity.
[0007] A further object of the present invention is to provide an integrated smart local wireless spread spectrum communication system, wherein the unlicensed 2.4 GHz band is used so that the cost of communication is low.
[0008] To achieve above object, the integrated smart local wireless spread spectrum communication system in accordance with the present invention includes: at least one mobile wireless communication unit; at least one first base station and one second base station, each providing a cell and having at least one smart antenna array, so that the mobile wireless communication unit in a cell can communicates with a communication device via the base station; and a central control unit for controlling data exchange between the first base station and second base station, and storing user data of the mobile wireless communication unit. In the cell, communication band is divided into a plurality of channels. The first base station and the second base station trace the mobile wireless communication unit by their antennas, respectively, and signal strength of the mobile wireless communication unit received by the antennas are used to determine a moving direction of the mobile wireless communication units. When the mobile wireless communication unit moves from the first base station towards the second base station, the central control unit notifies the second base station, so that the second base station can prepare to perform a handoff process in advance.
[0009] The various objects and advantages of the present invention will be more readily understood from the following detailed description when read in conjunction with the appended drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] [0010]FIG. 1 is a systematic structure of the present invention.
[0011] [0011]FIG. 2 is a flowchart showing the user's wireless communication cells of the present invention.
[0012] [0012]FIG. 3 is a flowchart of the disconnection process of the present invention.
[0013] [0013]FIG. 4 is a flowchart of the handoff process of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] In one preferred embodiment of the present invention, a 2.4 GHz system is given as an example in which a mobile phone moves in various base stations. With reference to FIG. 1, there is shown a systematic construction of the present invention, which includes wireless communication units 11 and 12 , base stations 21 , 22 and 23 and a central control unit 3 .
[0015] In this embodiment, the wireless communication units 11 and 12 are mobile phones. Alternatively, the personal digital assistant (PDA), notebook computer and other personal portable devices may be employed. Each of the base stations 21 , 22 and 23 provides a wireless coverage, known as a cell. Therefore, a wireless communication unit 11 or 12 can be communicated with the other wireless communication unit 11 or 12 in its cell for transferring voice or data signal. Each of the base stations 21 , 22 and 23 has a smart antenna array for tracking the movement of the wireless communication unit 11 or 12 in a cell. Furthermore, the communication bandwidth of a cell is divided into a plurality of channels by the spread spectrum technology. Different cells are distinguished by employing different direct sequence spread spectrums (DSSS), so that adjacent cells can use the same channels to perform wireless communications for different wireless communication units 11 and 12 . Between two base stations, for example, base stations 21 and 22 , there is provided an overlap area 4 . The central control unit 3 serves for data exchange among different base stations 21 , 22 and 23 , and storage of user data. Therefore, a wide area wireless communication environment is constructed.
[0016] [0016]FIG. 2 is a flow diagram illustrating that a user moves in cells. When a user powers on the wireless communication unit 11 , the wireless communication unit 11 registers to the central control unit 3 through the base station 21 (step S 201 ). If the registration is successful, the base station 21 uses its smart antenna to detect the signal strength of the wireless communication unit 11 . If the registration is failed, the central control unit 3 interrupts the communication of the wireless communication unit 11 through the base station 21 (step S 202 ). When the base station 21 detects the signal strength of the wireless communication unit 11 , the signal strength is compared with a predetermined signal strength δ 1 . If the detected signal strength is larger than δ 1 , the detected signal strength is further compared with a predetermined signal strength δ 3 . If the detected signal strength is smaller than δ 1 , the communication of the wireless communication unit 11 is interrupted (step S 202 ). If the detected signal strength of the wireless communication unit 11 is still larger than δ 3 , a connection mode is entered to start a communication (step S 204 ); otherwise, an handoff process is performed for the wireless communication unit 11 (step S 203 ).
[0017] [0017]FIG. 3 shows the flowchart of the interruption process. If a verification is failed (step S 300 ), the base station 21 sends an error message of no system service to the wireless communication unit 11 (step 301 ) and disconnects the connection to the wireless communication unit 11 (step S 303 ′). When the base station 21 detects that the signal strength of the wireless communication unit 11 is smaller than δ 1 (for example, when the user turns off the mobile phone or the user is out of the cell), the base station 21 cancels the registration (step S 302 ), and the connection to the wireless communication unit 11 is disconnected (step S 303 ).
[0018] [0018]FIG. 4 shows the flowchart of the handoff process in accordance with the present invention. When a user having the wireless communication unit 11 moves from a position nearest to the base station 21 towards the base station 22 , and if the smart antenna of the base station 21 detects that the signal strength of the wireless communication unit 11 is smaller than δ 3 , the base station 21 performs a handoff process to the wireless communication unit 11 (step S 401 ). The base station 21 uses the smart antenna to trace the wireless communication unit 11 . Since the smart antenna traces only in one direction and power is transmitted from the base station 21 , the power is greatly reduced, in comparison with that of the conventional multi-direction antenna.
[0019] As the base station 21 keeps tracing the wireless communication unit 11 , the moving direction of the wireless communication unit 11 can be predicted, and thus an adjacent destination base station 22 can be notified of the moving direction (step S 402 ). Therefore, the base station 22 starts to detect the signal strength of the wireless communication unit 11 . At this moment, if the user holding the wireless communication unit 11 moves back to the base station 21 , the base station 21 detects that the signal strength of the wireless communication unit 11 is larger than δ 3 , and thus cancels the handoff process (step S 403 ).
[0020] If the user keeps moving towards the base station 22 and arrives at the overlap area 4 between the base stations 21 and 22 , the base station 21 detects that the signal strength of the wireless communication unit 11 is smaller than δ 2 . Then, the control is switched from the base station 21 to the destination base station 22 , and the corresponding services for the wireless communication unit 11 are then provided by the base station 22 . Moreover, the position of the wireless communication unit 11 is reported to the central control unit 3 (step S 404 ). The base station 22 is responsible for detecting the wireless communication unit 11 . After detecting such, the received signal strength of the wireless communication unit 11 in switching is used as a priority for arranging channels. If the received signal strength is strong, the wireless communication unit 11 has a higher priority. If the base station 21 detects that the signal strength of the wireless communication unit 11 is larger than δ 2 , it represents that the user still moves around in the overlap area 4 . Then, the wireless communication unit 11 is kept in detecting and the detected signal strength is compared with the predetermined signal strengths δ 2 and δ 3 .
[0021] In view of the foregoing, it is appreciated that in the present invention, the movement of the user is detected through smart antennas and the moving direction of the user can be predicted. The smart antenna transmits power toward the detected direction for reducing the loss of power. The base station in the direction is notified of performing a handoff process. Furthermore, a priority process is used for designating a channel to the detected wireless communication unit, thereby improving the quality of service and decreasing the possibility of interruption. Moreover, the spread spectrum technology is used for increasing the number of available communication channels.
[0022] Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed. | An integrated smart local wireless spread spectrum communication system is disclosed. Smart antennas of the base stations are used to detect the movement of the users. Furthermore, spread spectrum communication technology is used to increase the number of available channels. The signal strength received from the wireless communication unit is used to predict the movement of the communication units, and thus a handoff process can be prepared in advance as the wireless communication unit is in an overlap area between two cells. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to rotary drill bits for drilling boreholes into subterranean formations. More particularly, the invention relates to method of forming diamond elements for use in a novel rotary bit design utilizing diamond cutting elements.
Drill bits utilizing diamonds or similar hard cutting elements are commonly employed in drilling and coring operations, particularly in hard subterranean formations such as chert, quartzitic sandstones or the like. The construction of such diamond drill bits usually includes a body portion having means for interconnection of the bit onto a drill string, and a matrix portion for mounting the diamonds or other cutting elements. Drilling fluid is directed down to the bottom of the borehole through the drill string and from a port generally disposed in the central portion of the bit. Fluid passageways or water courses that cross the drilling surfaces of the bit are also provided to transport this drilling fluid across the bit face to cool and lubricate the drilling surface of the bit and to facilitate movement of drill cuttings from the drilling area.
The general theory of diamond bit operation is not simply to crush the formation and thereby make drilling progress, but rather to create tiny fractures as the cutting elements pass over the formation so that drilling fluid which is maintained at a higher pressure than the formation pressure, can enter these fractures and remove the fractured portions of the formation. While most diamond bits use this crushing or fracturing action to create the hole, some bits have been developed which utilize a shearing action to cut through the formation.
Many different types of "diamond" cutting elements have been developed and used. These include natural diamonds, synthetic diamonds, and composites which include combinations of diamonds with other compounds such as tungsten carbide. Additionally, many different types of diamond shapes have been used. These include natural round stones, mechanically and chemically rounded and polished stones, natural cubic stones and natural octahedral stones. These stones have been inserted in many different configurations in diamond drill bits and in bits of many different shapes.
Although diamond drill bits are the best type of bit for hard formations, their penetration rate is lower than other types of bits since they generally have to rely on crushing and fracturing action to cut through the formation. Accordingly, it would be a significant advancement in the art to provide a diamond drill bit which retains the advantages of having the hard diamonds as the cutting elements while providing a means for increasing the penetration rate of the bit. Such a bit is disclosed and claimed herein.
SUMMARY OF THE INVENTION
The present invention provides a novel drill bit which utilizes hemispherically shaped diamond inserts having a cleaved face to cut through rock formations. The diamond inserts can be formed by cleaving round diamonds in half. Alternatively, the diamond inserts can be formed by polishing and cleaving diamonds having other shapes.
In a preferred embodiment, the diamond inserts are formed from various shapes of natural diamonds. A diamond is selected and studied to determine the cleaving plane and its perpendicular axis. The diamond is then cut along two planes parallel to the central cleaving plane. The diamond is then polished to form a cylinder having as its axis, the axis perpendicular to the cleaving plane.
One end of the cylinder is then further polished to form a series of conical sections havign different angles to approximate a hemisphere. The diamond can then be cleaved to form a hemisphere. Depending on the shape and size of the diamond, the cleaved plane of the hemisphere may be the same as or parallel to the central cleaving plane.
The drill bit comprises a body portion having a matrix for holding the diamonds in place. Passageways are created across the face of the matrix to allow drilling fluid to cool and lubricate the bit and carry cuttings away. These passageways divide the face of the drill bit into a plurality of fins. A plurality of hemispherically shaped diamond cutting elements are mounted in each of the fins.
The hemispherically shaped diamond cutting elements are embedded in the matrix of the bit such that a portion of the cleaved, planar face of each element is exposed. The elements are positioned such that they have a leading edge in the direction of rotation of the bit and an outer edge which is distal from the matrix. The leading edge is inclined downward at a first angle α from a plane normal to the face of the bit and parallel to the direction of rotation to create a pitch. The outer edge is inclined downward at a second angle β from a plane normal to the face of the bit and parallel to the intersection of the planar face of the diamond element with the face of the bit.
The diamond edge penetrates and fractures the formation progressively and at the same time removes the fractured cuttings by grooving with the rotation of the bit. The pressure on the diamond is directed on the cleaved face which provides the maximum resistance without damaging the diamond.
The angle of inclination to create the pitch can be varied within suitable ranges depending upon the type of formation in which the bit will be used. For example, in extremely hard formations, the angles are smaller such that less material is removed with each rotation of the bit. For bits which are used in softer formations, the angles can be increased to provide for greater penetration rates.
When the diamond inserts are formed from a series of conical sections approximating a sphere, the points between adjacent sections help anchor the inserts in the matrix. Since the forces exerted on the diamond elements are only applied to one edge of the face, a torque is created which tries to turn the elements in the matrix. The sharp points between conical sections help resist the forces that are trying to turn the elements.
In the preferred embodiment, a plurality of fins are provided and only a single row of diamond cutting elements is arranged in each fin. However, it is also possible to provide arrangements with diamond cutting elements side-by-side, provided that the cutting surfaces of the diamonds are properly aligned.
The grooving action of the cleaved diamonds can complete the fracturing of the debris and remove the fractured pieces which are held in place by the hydraulic pressure of the drilling mud in addition to simply fracturing the rock formation.
One advantage of the drill bit of the present invention is that it provides faster penetration rates than conventional diamond drill bits. The cutting action of the hemispherically shaped diamond inserts which slice and groove into the formation creates a borehole faster than the crushing and fracturing action of the prior art drill bits. A further advantage of the present invention is that the diamond cutting elements can be recycled by removing them from the matrix and rotating them such that a new edge of the hemisphere is exposed. Another advantage is that the major cutting forces are applied to the cleaved face of the diamond. These and other advantages of the present invention will be more fully apparent from the following description and attached drawings taken in conjunction with the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a drill bit embodying the present invention;
FIG. 2 is a plan view of the crown end of the drill bit of FIG. 1;
FIGS. 3 and 3A are perspective views of a slice of the bit illustrated in FIGS. 1 and 2;
FIGS. 4 and 4A-4C are schematic views illustrating the orientation of the diamond inserts in the matrix of the bit;
FIG. 5 is a partial cross-sectional view of the bit of FIGS. 1 and 2;
FIG. 6 is a plan view of the crown end of a second preferred embodiment of the present invention;
FIG. 7 is a partial cross-sectional view of the bit of FIG. 6.
FIG. 8 is a perspective view of the center cutting element of the bit of FIGS. 6 and 7.
FIG. 9 is a bottom plan view of the element of FIG. 8.
FIG. 10 is a cross-sectional view taken along line 10--10 of FIG. 4A showing the grooving action of the diamond inserts of the present invention.
FIG. 11 is a plan view of a tool used to form a mold for casting the bit of the present invention.
FIGS. 12A-12E are schematic illustrations showing the steps involved in forming diamond inserts according to a preferred embodiment of the invention.
FIG. 13 is a cross-sectional view of a portion of a drill bit showing the insert of FIG. 12E embedded within a matrix.
FIG. 14 is a plan view of the cleaved face of a diamond insert according to a preferred embodiment of the invention.
FIG. 15 is a perspective view of a portion of a mold showing the formation of holes to receive a diamond insert.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides a novel design for a drill bit which utilizes cleaved, hemispherically shaped diamond cutting elements to provide a bit having increased penetration rates.
Referrence is now made to the drawings in which like parts are designated with like numerals throughout. Illustrated in FIGS. 1 and 2 is a drill bit 10 of the type which may be constructed in accordance with the instant invention. Drill bit 10 comprises a body 12 formed of suitable material to withstand stress during operation. The upper portion of the body is provided with an exteriorly threaded neck 14 so that the bit 10 may be interconnected at the bottom of a drill string. The lower body section or crown 16 of the bit 10 is surfaced with a metal matrix 18 in which the diamond cutting elements 20 may be embedded. The matrix is a relatively hard, tough material such as bronze, or a similar metal alloy such as copper nickel alloy containing powdered tungsten carbide in quantities sufficient to convey the required strength and erosion resistance. Alternatively, the matrix may be composed of a suitably hard plastic material capable of being cast upon the bit and having the properties of resisting wear and retaining the cutting elements. The material is of a suitable thickness to provide the required strength, resistance to erosion and abrasion, and to embed the diamond cutting elements firmly therein.
In casting the matrix material upon the bit body 12, it is common to provide recesses or a roughened surface on the bit body so that the matrix material will rigidly and firmly anchor to the bit body and form a permanent and fixed part of the drill bit.
In the embodiment illustrated in FIG. 1, the matrix of the drill bit is shaped to have a generally semitoroidal end face defining an outer cylindrical gauge face 22, a lower, generally curved drilling face 24, and an interior coring face 26. The interior face 26 opens into a central passageway 28 extending through the bit body, and through which drilling fluid is directed down the drill string to the formation and across the face of the bit. Matrix 18 is formed such that it has a plurality of fins 30 into which the diamond cutting elements 20 are embedded.
Fins 30 define a plurality of channels or water courses 32 which extend outwardly from the central passageway in the interior face, across the drilling face and up the gauge face of the bit. Accordingly, drilling fluid delivered through the drill pipe through passageway 28 is distributed through these flow passageways or water courses 32 to wash cuttings from the drilling area and upwardly to the top of the well as is well-known in the art. Additionally, in the embodiment illustrated, the matrix of the bit is provided with a series of junk slots 34 which are designed to discharge cuttings from the drilling area. It should be noted that a number of other configurations suitable for use in a diamond drilling bit would be obvious to those skilled in the art.
As can be best be seen in FIG. 5, a pair of hemispherically shaped diamond cutting elements 33 are placed in a projection 35 in central passageway 28. Cutting elements 33 remove the core that is formed as drilling face 24 progresses through the formation.
Reference is next made to FIGS. 3, 3A, 4 and 4A-4C which illustrate the manner in which diamond cutting elements 20 are embedded in the matrix 18 in accordance with the teachings of the present invention. Cutting elements 20 have a hemispherical shape and a planar surface 38 formed by cleaving a diamond. In one embodiment, cutting elements 20 are obtained by cleaving a round diamond in half.
As can best be seen in FIG. 4A and 4C, diamond cutting elements 20 are embedded in matrix 18 such that the center 21 of each element 20 is behind face 19 of matrix 18. Accordinglty, slightly over half of each cutting element 20 is embedded within the matrix to ensure that the elements are securely fixed in place.
Diamond cutting elements 20 are oriented within matrix 18 of fins 30 to provide the optimum cutting surface. Generally, the rounded surface of cutting element 20 is oriented toward the lowermost tip 31 of fin 30. The orientation of elements 20 can best be seen with reference to FIGS. 4 and 4A.
Illustrated in FIG. 4 are lines X--X', Y--Y' and Z--Z' which are oriented at 90 degrees to each other to define a three dimensional space and which intersect each other at center 21 of diamond element 20. The plane defined by Lines Y--Y' and Z--Z' is parallel to face 19 of fin 30 with line Y--Y' passing through the center 21 of diamond element 20. It should be appreciated that while line Y--Y' has been shown as a straight line for purposes of illustration in FIG. 4A, it is parallel to face 19 of fin 30 and will be a curved line where face 19 is curved. Line X--X' is perpendicular to face 19 of fin 30.
The flat or planar surface 38 which is defined by the cleaved face of element 20 is rotated in two directions with respect to the plane defined by lines X--X' and Z--Z'. First, as shown in FIG. 4B, leading edge 40 of element 20 is inclined downward around the X--X' axis at a first angle α as illustrated by line P--P' to create a pitch. This permits cutting element 20 to groove down into the rock formations. Angle α can be increased or decreased depending upon the type of formation in which the bit will be used. Generally, angle α is within the range of 30-60 degrees. Preferably, angle α is about 45 degrees.
The outer edge 44 of diamond cutting element 20 is also inclined downward around the P--P' axis from a plane defined by lines X--X' and P--P' at a second angle β as illustrated by line W--W' in FIG. 4. This downward inclination exposes the sharp cutting edge 44 and planar surface 38 of cutting element 20 to the formation being drilled. If angle β is formed before angle α, the rotation occurs around the Z--Z' axis as illustrated in FIG. 4C. Angle β can also be adjusted within a suitable range depending upon the size of the cutting element and the hardness of the formation in which bit 10 will be used. Generally, angle β is within the range of 15-30 degrees. Preferably, angle β is about 30 degrees.
As can be seen from the foregoing, lines P--P' and W--W' define the planar surface 38 of element 20. This plane is rotated in two directions from the plane defined by lines X--X' and Z--Z' if angle β is created first. Otherwise, angle β is measured from the plane defined by lines X--X' and P--P'.
As can be seen in FIGS. 3 and 3A, the orientation of diamond cutting elements changes as they progress from the outer face to the interior face of bit 10. The greatest change occurs adjacent lowermost tip 31 of fin 30.
Reference is next made to FIGS. 6-9 which illustrate another preferred embodiment of the present invention. In this embodiment, fins 30 are substantially identical to the embodiment illustrated in FIGS. 1 and 2. A core cutting insert 46 is provided at the center of central passageway 28 to remove the core which is left as the formation disk shaped with crossbars 48 and openings 49 formed in the center thereof. Insert 46 is positioned in central passageway 28 and is secured in place by threaded ring 51. Openings 49 permit drilling fluid to pass through insert 46 to clean and lubricate the face of bit 10. The upper edges of crossbars 48 are tapered to create as little turbulence as possible as the fluid passes through openings 49.
A pair of notches 50 are formed in the bottom of insert 46 to permit east alignment of insert 46 within central passageway 28. The notches 50 also help prevent rotation of insert 46 within bit 10.
A pair of diamond cutting elements 52 and 54 are positioned in crossbars 48 for removing the core. Diamond cutting elements 52 and 54 are generally hemispherical in shape and are formed by cleaving generally round diamonds in half. The flat faces 56 and 58 of elements 52 and 54 are positioned such that they face each other. However, elements 52 and 54 are offset such that they only slightly overlap each other. When diamond cutting elements 52 and 54 become worn or break, insert 46 can easily be removed and replaced. Because the core is not supported, it is easily destructed in small fragments without retartding the penetration of the bit.
Reference is next made to FIG. 10 which illustrates the cutting and grooving action of diamond cutting elements 20. As planar surface 38 of cutting element 20 engages rock formation 60, it fractures and grooves the rock thus forming pieces 62 which are carried away by the drilling fluid. A groove 64 is formed in rock formation 60 by the cutting action of element 20. As can further be seen in FIG. 10, only an outer portion 39 of element 20 engages rock formation 60. Accordingly, a space 61 remains between matrix 18 of the bit and rock formation 60. This provides a passageway for removal of chipped rock.
The diamond inserts of the present invention have an advantage over PDC cutters since the inserts are formed from a single crystal. Heat generated while cutting a rock formation is more readily dissipated throughout the diamond and into the bit matrix. This prolongs the life of the cutter.
FIG. 11 illustrates a tool 66 which can be used in the formation of a mold for casting bit 10. Generally, diamond bits are formed by mounting the diamonds in a graphite mold which is then filled with a metal powder that is sintered to form the matrix which holds the diamonds. Tool 66 includes a hemispherically shaped body 68 which is covered with a plurality of cutting blades 70. A ring 72, also covered with cutting blades is formed adjacent planar face 74 of body 68.
Body 68 is mounted on a shaft 76 for attachment to a suitable mill. Tool 66 is rotated by the mill and cuts a portion of a hemispherically shaped hole in the graphite mold into which diamond cutting elements 20 can be mounted. Since the edge of body 68 adjacent planar face 74 tends to wear first, ring 72 is provided to create a slightly larger opening adjacent the planar face. This ensures that the hole created by tool 66 is properly sized to receive the diamond cutting element 20, especially the sharp edge adjacent the cleaved face.
FIG. 15 illustrates the cutting of holes 120 in a mold 122 using tool 66. Mold 122 corresponds to the face of a fin 30. Shaft 76 of tool 66 is attached to a suitable mill which can be programmed to cut holes 120 having a planar surface 123 corresponding to the cleaved face of the diamond inserts and a concave surface 124 corresponding to the curved portion of the hemispherically diamond inserts. The axes of the hole 120 are shown by lines X--X', Y--Y', Z--Z', P--P' and W--W' which correspond to the axes illustrated in FIG. 4.
As tool 66 cuts holes 120, it moves along a plane defined by lines P--P' and W--W'. Methods of clamping mold 122 and programming a suitable mill are well known to those skilled in the art.
FIGS. 12A-12E illustrate a method whereby hemispherical inserts whithin the scope of the present invention can be formed from diamonds which are not round. In this process, a generally round diamond 80 is studied to determine a central cleaving plane 82 and the perpendicular axis 84 as shown in FIG. 12A. The diamond is then cut along two planes 86, 88 which are parallel to cleaving plane 82 as shown in FIG. 12B. Diamond 80 is then rotated about axis 84 and polished as shown in FIG. 12C to form a cylinder 90.
Cylinder 90 is then polished on one end is a series of steps to form a series of conical sections 92, 94, 96 as shown in FIG. 12D to approximate a hemisphere. While the illustrated embodiment shows three conical sections, it will be appreciated by those skilled in the art that different numbers of sections could be used and the angle of each section with respect to the axis 84 could be varied. The determination of the proper angles is within the level of skill in the art.
Diamond 80 is then notched at 97 and 99 so that it can be cleaved along plane 98 to form a hemisphere 101 as illustrated in FIG. 12E. Depending upon the shape of diamond 80 and the length of cylinder 90 additional hemispheres can be formed from the same diamond by repeating the polishing and cleaving steps illustrated in FIGS. 12D and 12E.
Any remaining portions of cylinder 90 can be cleaved to form diamond discs 100 as shown in FIG. 12D. These discs can be used in conventional diamond drill bits in place of synthetic diamond discs. The portion of diamond 80 that can be formed into discs 100 is used as a base to grasp the diamond as the conical sections are being polished.
An advantage of this method of forming hemispherical diamond inserts can be seen in FIG. 13. A series of sharp ridges 102, 104, 106 encircling hemisphere 101 are formed between the various conical sections. When hemisphere 101 is cast into matrix 18, ridges 102, 104 and 106 help anchor the diamond and prevent it from rotating as forces are applied to the face of the diamond during use.
A portion of mold 122 with hole 120 formed therein is also illustrated in FIG. 13. Cleaved plane 98 of hemisphere 101 is positioned along planar surface 123 of hole 120. Ridges 102 and 104 are positioned adjacent concave surface 124. Hemisphere 101 is glued into hole 120 to secure it in place while matrix 18 is being formed.
Reference is next made to FIG. 14 which illustrates a plan view of plane 98 of the diamond illustrated in FIG. 12E. The face of hemisphere 101 can be divided into six sections 110-115. Opposing sections 110 and 113 include notches 97 and 99. The remaining four sections 111, 112, 114 and 115 include a clean outer edge that can be used as the cutting edge for the diamond insert. When the edges of the diamond cutting elements become dull, the diamonds can be removed, rotated and used in a new bit.
As can be seen from the foregoing, the present invention provides a novel drill bit design which uses hemispherically shaped diamond inserts having a cleaved face as cutting elements. The inserts are positioned in the matrix of the bit to expose a sharp cutting surface which knives through the formation being drilled to provide faster penetration rates than other types of diamond drilling bits. The inserts can be formed by cleaving round diamonds in half or by polishing and cleaving diamonds to approximate a hemisphere.
While the invention has been described with respect to the presently preferred embodiments, it will be appreciated that changes and modifications can be made without departing from the scope or essential characteristics of the invention. Accordingly, the scope of the invention is defined by the appended claims rather than by the foregoing description. All changes or modifications which come within the meaning and range of equivalency of the claims are to be embraced within their scope. | A method of forming hemispherically shaped diamond cutting elements for use in a rotary drill bit is provided. The method includes identifying a cleaving plane in a diamond and a perpendicular axis, polishing the diamond to form a series of truncated cones approximating a hemisphere around said axis, and cleaving the diamond to form a cutting face. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims domestic priority to commonly owned, copending U.S. Provisional Patent Application Ser. No. 61/492,907, filed Jun. 3, 2011, the disclosure of which is hereby incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a process for the manufacture of haloalkane compounds, and more particularly, to an improved process for the manufacture of the compound 1,1,1,3,3-pentachloropropane (HCC-240fa). The present invention is also useful in the manufacturing processes for other haloalkane compounds such as HCC-250 and HCC-360.
BACKGROUND OF THE INVENTION
[0003] The compound 1,1,1,3,3-pentachloropropane (HCC-240fa) is a raw material for producing 1,1,1,3,3-pentafluoropropane (HFC-245fa), which is a non-ozone depleting chemical and can be used as blowing agent, energy transfer medium, and so on. Addition reactions for preparing useful haloalkanes, such as HCC-240fa, are known in the art. For example, U.S. Pat. No. 6,313,360 teaches a process for producing HCC-240fa by reacting carbon tetrachloride (CCl 4 ) and vinyl chloride (VCM) in the presence of a catalyst mixture comprising organophosphate, e.g., tributyl phosphate (TBP), metallic iron and ferric chloride under conditions sufficient to produce a product mixture containing HCC-240fa. The 240fa product is then recovered by separating it from reactants, catalyst and by-products. See also, U.S. Pat. Nos. 5,902,914, 6,187,978, 6,198,010, 6,235,951, 6,500,993, 6,720,466, 7,102,041, 7,112,709 and 7,265,082 and U.S. Patent Publication Nos. 2004/0225166 and 2008/0091053. The disclosures of all of these references are hereby incorporated herein by reference.
[0004] Iron powder is used as the primary catalyst during the synthesis of HCC-240fa via the coupling reaction between CCl 4 and VCM. The liquid medium, consisting of CCl 4 , TBP, and 240fa, forms a slurry with the iron powder. As such, the reactor effluent will contain a substantial quantity of suspended solids which could potentially upset the mechanical and chemical operations of downstream units. Furthermore, as catalyst is removed from the effluent, the reactivity will suffer, increasing the required make-up of lost iron powder. Hence, there is a need for means by which iron catalyst can be captured and recycled back to reactor. The present invention provides a solution to this problem.
SUMMARY OF THE INVENTION
[0005] The present invention employs an electromagnetic separation unit (EMSU), configured to allow for the continuous removal of iron particles from reactor effluent and for the recycle of captured iron particles during the catalytic formation of haloalkane compounds from CCl 4 .
[0006] In one embodiment, the present invention can be generally described as a method for capturing and recycling iron catalyst used in the production of 1,1,1,3,3-pentachloropropane, in which an electromagnetic separation unit (EMSU) is used to facilitate the reaction. When energized, the EMSU functions to remove all iron particles from the reactor effluent; when de-energized, the iron particles captured by the EMSU can be flushed back into the reactor for re-use.
[0007] Thus, one embodiment of the present invention is a method for capturing and recycling iron catalyst during in the production of 1,1,1,3,3-pentachloropropane, comprising the steps of:
[0008] (a) feeding CCl 4 and VCM into a reactor with a catalyst comprising iron powder and TBP to form HCC-240fa;
[0009] (b) removing the iron particles from the HCC-240fa reactor effluent by employing an energized electromagnetic separation unit (EMSU); and
[0010] (c) denenergizing the EMSU and recycling the iron particles and returning the iron particles to the reactor for re-use in step (a).
[0011] The present invention is also useful in the iron catalyzed manufacturing processes for other haloalkane compounds such as HCC-250 and HCC-360:
[0012] (1) HCC-250 may be made from CCl 4 and ethylene as per the following reaction:
[0000] CCl 4 +CH 2 =CH->CCl 3 CH 2 CH 2 Cl.
[0013] (2) HCC-360 may be made from CCl 4 and 2-chloropropene as per the following reaction:
[0000] CCl 4 +CH 2 =CClCH 3 ->CCl 3 CH 2 CCl 2 CH 3 .
BRIEF DESCRIPTION OF THE DRAWING
[0014] The FIGURE shows the process setup for the continual removal and recycle of catalytic solids in the production of HCC-240fa and other haloalkane compounds, in a continuous stirred tank reactor (CSTR).
DETAILED DESCRIPTION OF THE INVENTION
[0015] Iron is widely used in many catalyst applications wherein its powder form is suspended in a liquid mixture which would be composed of chemical reactants. Often these slurries are processed continuously and may require careful management of the solids present. Sometimes downstream equipment (i.e., pumps, valves, piping) is unable to handle streams large amounts solid material. Furthermore, undesirable chemistries (separations, side reactions) may exist in the presence of iron. While iron powder is preferred, any iron object can be used, such as iron balls, iron wire, iron shavings, and the like.
[0016] Filters are often used and strategically placed to prevent downstream carry-over of solids. However, these filters generally need to be removed from service when they are saturated with iron. As a result, valuable catalyst may be lost and/or process downtime may exist as a result of clean and maintenance of these filters.
[0017] The present invention is designed to minimize iron carry-over and process downtime, during the iron catalyzed formation of haloalkane compounds from CCl 4 , as well as to maximize catalyst retention in a process that employs suspensions of iron solids through the use of one or more electromagnetic separation units (EMSUs). Such devices are commercially available. One commercial manufacturer is Eriez of Erie, Pa.
[0018] More particularly, the present invention is designed to capture and recycle iron catalyst used in the production of 1,1,1,3,3-pentachloropropane, in which CCl 4 and VCM are continuously fed into the reactor at desired ratio and iron powder and the co-catalyst TBP can be added into reactor periodically or continuously. Additional co-catalysts useful herein are the following; tributylphosphate, triethylphosphate, trimethylphosphate, tripropylphosphate or any other trialkylphosphate compound, and mixtures of two or more of these.
[0019] The reaction of CCl 4 and VCM is preferably carried out at a residence time of from about 0.01 hours to about 24 hours, preferably from about 1 hour to about 12 hours. The reaction conditions are judicially selected for high VCM efficiency, high HCC-240fa yield, and low by-products production. While batch processing can be used for the reactions of the present invention, it is preferred that continuous manufacturing processing is used herein.
[0020] In a continuous operation, reactor contents are continually drawn through a tube immersed into the liquid slurry. As the slurry is removed from the reactor, the stream would be prepared by removing iron using an EMSU prior to downstream processing. Although this stream can be processed with a single EMSU, in a preferred embodiment, two (or more) tandem EMSUs are installed and operated in parallel, as shown in FIG. 1 .
[0021] At start-up, valves 1 are opened allowing feed material to prime the 240fa reactor though the bypass and effluent to be directed through EMSU “A”. Upon continuous operation, EMSU “A” will be energized. This energized EMSU accepts reactor effluent and operates to capture suspended iron particles. The liquid portion can then continue downstream free of iron. Once EMSU “A” becomes saturated with iron, valves 1 are closed and 3 are opened such that EMSU “B” can accept reactor effluent and begin removing iron.
[0022] While the EMSU “B” is operating, the saturated EMSU “A” is de-energized. Reactor supply can then be re-directed through the saturated EMSU “A” such that the iron catalyst is flushed back into the reactor. As such, a continuous process can be maintained by trading the tasks of each EMSU, either by opening valves 3 when EMSU “A” is saturated or valves 2 when EMSU “B” saturated, to prevent loss of iron to the downstream, maximize catalyst use, and mitigate process downtime.
[0023] After going through an EMSU where iron particles are trapped, the reactor effluent stream is flash-distilled to remove a “top” stream including unreacted CCl 4 and VCM (if any) feed materials and the HCC-240 reaction product, while the catalyst/co-catalyst mixture remains. The distillation may be performed in one or more distillation columns, which are well known in the art.
[0024] Preferably, the flash-distillation is conducted in two steps: first, flash-distillation is conducted at a temperature less than the reaction temperature under a pressure, preferably under vacuum, to remove any unreacted CCl 4 and/or VCM, followed by another vacuum flash-distillation at a lower pressure to remove the HCC-240fa reaction product. The “bottoms” stream is recycled back to the reactor. The distilled, unreacted CCl 4 and VCM may be recycled back to the reactor. Periodic purges may be applied to avoid accumulation of heavy by-products such as HCC-470 isomers in catalyst recycle stream.
[0025] In a later step of the process, the present invention provides for the purification of the crude product by distillation. Fractional vacuum distillation is carried out at about 5 to about 200 mm Hg and a temperature of about 50° C. to about 150° C. to recover the product. It has been discovered that when this purification step is carried out in the presence of a trialkyl phosphate such as tributyl phosphate or other metal chelating compound, the distillation yield of purified product is significantly improved.
[0026] While not wishing to be bound by any particular theory, it is believed that the tributylphosphate acts to prevent the decomposition of the HCC-240fa product. Thus, in a preferred embodiment, the purification step includes the addition of an amount of a metal chelating compound sufficient to improve the HCC-240fa product yield. Preferably, 5 weight percent of tributyl phosphate is used.
[0027] As used herein, the singular forms “a”, “an” and “the” include plural unless the context clearly dictates otherwise. Moreover, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.
[0028] It should be understood that the foregoing description is only illustrative of the present invention. Various alternatives and modifications can be devised by those skilled in the art without departing from the invention. Accordingly, the present invention is intended to embrace all such alternatives, modifications and variances that fall within the scope of the appended claims. | Disclosed is a method for capturing and recycling iron catalyst used in the production of haloalkane compounds and more particularly, to an improved process for the manufacture of the compound 1,1,1,3,3-pentachloropropane (HCC-240fa), in which an electromagnetic separation unit (EMSU) is used to facilitate the reaction. When energized, the EMSU functions to remove all iron particles from the reactor effluent; when de-energized, the iron particles captured by the EMSU can be flushed back into the reactor for re-use in the continued production of HCC-240fa. The present invention is also useful in the manufacturing processes for other haloalkane compounds such as HCC-250 and HCC-360. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to thermosetting photosensitive material, and specifically to a thermosetting photosensitive material for via-filling process in manufacturing printed circuit boards.
[0003] 2. The Prior Arts
[0004] In recent years, owing to the surging demands of mobile phones, personal electronic organizers and laptops, consumers are increasingly demanding electronic products lighter, thinner, and smaller. The printed-circuit-board (PCB) industry, which has to support the electronic industries in their development, are also pushed towards manufacturing processes that are capable of handling this trend. To make lighter, thinner, and smaller electronic products, people pack more circuit density onto the ever-decreasing board area, or so-called high-density-integration. The technology of multi-layered boards manufacturing also plays an essential role in the revolution towards high-density-integration.
[0005] Particular to the multi-layered board manufacturing technology, sets of via have to be drilled to leave room for the formation of electronic connection between different layers. As it might sound perplexing to those who know nothing about it, these sets of via then have to be filled generally by some polymeric materials after the connections made and then proceed to a thermal curing process at a temperature of 150° C. for about 30-60 minutes. The purpose of via-filling is to protect the electronic connection within the via. Without the via-filling material, the connector within via is subjected to oxidation by air trapped therein, which in turn leads to breaking of signal transmission and renders the product useless. Therefore, the via-filling process is really a critical step in the multi-layered board manufacturing processes.
[0006] Though it seems simple, via-filling process is complicated. Sometimes, it is really a challenging step. Generally speaking, problems encountered are such as bubbles inside the filling, volcanoes on the surface and recessed or bulged filling surface profiles along the plane of circuit patterns. Until now, the industry-wise yield-rate of this step is still far from satisfactory. A key factor for resolving this issue lies in the filling material itself. If the composition of the filling material can be improved so that it does not expand or contract much during the subsequent curing step, then there should not be much of surface bulge or recess. Also, if the solvent can be removed from the filling composition, there would not be problems of volcanoes and bubbles, which generally form as solvent evaporates.
[0007] FIG. 1 illustrates a via structure formed by a through hole in a conventional printed circuit board (PCB) manufacturing process. The via structure comprises a substrate ( 10 ), a via ( 20 ) formed by a through hole on the substrate ( 10 ), a circuit pattern layer ( 30 ) formed on the substrate ( 10 ) by forming a copper ring ( 21 ) on the via wall of the substrate ( 10 ).
[0008] As indicated in FIG. 2 , idealistically, the filling is solid and void-free after cross-linking of the via-filling material ( 40 ). Furthermore, the surface on both ends of the cylinder formed within the surrounding copper ring ( 21 ) must be a smooth surface ( 41 ) so as to avoid problems in the subsequent manufacturing process. However, smooth surface is difficult to acquire in practice. One common problem is the recess on the filling surface, which is illustrated in FIG. 3 , where a recess ( 42 ) is found on the via-filling material ( 40 ) after cross-linking.
[0009] Commercially available via-filling materials include both solvent and solvent-less types. In some printed circuit board manufacturing processes with less stringent requirements, people use solder resistant material for via filling. Since the solvent content for most commercial solder resistant products is relatively high, i.e. up to 25%, which results in voids or recessed surfaces. Such problems are due to evaporation of solvent in the subsequent baking process. The via-filling material shrinks as the loss of the volume of solvent, thus results in recessed surfaces or voids. Therefore, the existence of solvent is detrimental to the via-filling process.
[0010] To completely resolve problems occurring in the curing step, a solvent-less product is selected undoubtedly. Unfortunately, current commercial via-filling products still contain certain problems, so that the yield rate is largely limited. Sagging is a common problem, which is the flowing of the filling material out of via during the curing process. Sagging is caused by viscosity changes. The viscosity of the uncured filling material ( 40 ) is low at the curing temperature, such as 150° C. The filling material thus tends to flow out of via along the vertically mounted PCB ( 10 ) under the influence of the gravity, as shown in FIG. 4 . As a result, the lack of coverage of the filling material along the top edge of via and excessive coverage along the bottom edge of via forms.
SUMMARY OF THE INVENTION
[0011] Accordingly, the present invention is directed to a solventless thermosetting photosensitive material that substantially obviates the above-mentioned problems in the via-filling process of manufacturing printed circuit board.
[0012] To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, a solventless thermosetting photosensitive via-filling material according to the present invention comprises:
one or more liquid epoxy resins; one or more monomers; one or more photo-initiators; and one or more epoxy resin curing agents.
[0017] Furthermore, the solventless thermosetting photosensitive via-filling material comprises one or more optional inorganic fillers for adjusting physical properties thereof such as electrical insulation, acid resistance, Theological properties, etc.; and one or more optional organic adjuvants for achieving desired processing characteristics for the via-filling step.
[0018] For more detailed information regarding advantages and features of the present invention, examples of preferred embodiments will be described below with reference to the annexed drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The related drawings in connection with the detailed description of the present invention to be made later are described briefly as follows, in which:
[0020] FIG. 1 illustrates a via structure formed by a through hole in a conventional printed circuit board (PCB) manufacturing process;
[0021] FIG. 2 illustrates a via-filling material after curing;
[0022] FIG. 3 illustrates a recess on the via-filling material surface; ( 00171 FIG. 4 illustrates the problem of sagging caused by the lowering of viscosity of the filling material at curing temperature. It shows that the top edge lacks in coverage of filling material, while the lower edge is excessively covered with filling material; and
[0023] FIGS. 5 (A)- 5 (C) are schematic views of examples for filling up a via with a solventless thermosetting photosensitive material in the process of manufacturing printed circuit board.
DETAILED DESCRIPTION OF THE INVENTION
[0024] Preferred embodiments of the present invention will now be described in further detail. It should be understood that these examples are intended to be illustrative only and that the present invention is not limited to the conditions, materials or devices recited therein.
[0025] A solvent-less thermosetting photosensitive via-filling material according to the present invention, based on 100 parts of the epoxy resin, comprises:
one or more liquid epoxy resins; one or more monomers; one or more photo initiators; and one or more epoxy resin curing agents.
[0030] Furthermore, one or more optional inorganic fillers and organic adjuvants are added to achieve the desired properties.
[0031] Liquid epoxy resins as used herein comprise bisphenol-A epoxy resins, bisphenol-F epoxy resins, blends of bisphenol-A and bisphenol-F epoxy resins, phenol Novolac epoxy resins, rubber-modified epoxy resins, cycloaliphatic epoxy resins, hydrogenated bisphenol-A epoxy resins, dimmer-modified epoxy resins, flexible EPU modified epoxy resins and other hetero epoxy resins. The amount of liquid epoxy resins is determined by the actual need and referred as 100 parts for calculating the ratio of other compositions.
[0032] Bisphenol-A epoxy resins as used herein include DEN-330 from Dow, Epikote-828 from Shell, LER-840 from LG and NPEL-127 from Nan-ya. Bisphenol-F epoxy resins include DER-354 from Dow, Epikote-862 from Shell, LER-830 from LG and NPEF-170 from Nan-ya. Blends of bisphenol-A and bisphenol-F epoxy resins include DER-351 and DER-352 from Dow and NPEF-157 from Nan-ya. Phenol Novolac epoxy resins include LER-N730 from LG. Rubber-modified epoxy resins include TSR-960 from LG and NPEL-450 from Nan-ya. Cycloaliphatic epoxy resins include Cyracure-6610 from Dow. Hydrogenated bisphenol-A epoxy resins include EP-4080 from Adeka. Dimmer-modified epoxy resins include LER-1500 from LG and NPER-172 from Nan-ya. Flexible EPU modified epoxy resins include NPER-133 and NPER-133L from Nan-ya.
[0033] Monomers as used herein comprise mono-functional monomers, difunctional monomers, trifunctional monomers and tetra and penta-functional monomers. The amount of monomers used is from 2 to 50 parts based on 100 parts of epoxy resin by weight, and preferably in the range of 5 to 50 parts based on 100 parts of epoxy resin by weight, based on 100 parts by weight of the liquid epoxy resins. As the amount of monomers increases, the photosensitivity of the system increases but the solder-resistance decreases.
[0034] As used herein, typical examples of mono-functional monomers include allyl methacrylate, tetrahydrofurfuryl methacrylate, 2(2-thoxyethoxy)ethyl acrylate, 2-phenoxyethyl acrylate, and isodecyl acrylate. Typical examples of difunctional monomers include tetraethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate and tripropylene glycol diacrylate. Typical examples of trifunctional monomers include trinmethylolpropane trimethacrylate, trimethylolpropane triacrylate and tris(2-hydroxyethyl) isocyanurate triacrylate. Typical examples of tetra and penta-functional monomers include dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate.
[0035] Photo-initiators as used herein comprise free-radical photo-initiators. Typical examples of free-radical photo-initiators are selected from a group consisting of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 2-isopropyl thioxanthone, 2-hydroxy-2-methylphenylpropanone, 1-hydroxycyclohexyl phenylketone. They can be used separately or in the form of mixture. The amount of photo-initiators used is from 0.5 to 10 parts by weight based on 100 parts of epoxy resin by weight, and preferably in the range of 1 to 5 parts by weight, based on 100 parts by weight of the liquid epoxy resins.
[0036] Epoxy resin curing agents as used herein comprise epoxy resin thermal curing agents. Typical examples of epoxy resin thermal curing agent comprise dicyandiamine, amidoamines, polysulfides, amines, polyamides, aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, imidazoles, such as 2-methylimidazole 2,4-diamino-6-(2′-methylimidazolyl-(1′))-ethyl-S-triazine, 2,4-diamino-6-[2′-methylimidazoly-(1′)] ethyl-S-triazine isocyanuric acid addition compound; modified polyamine, such as EH-4070S from Adeka and Ancamine-2014FG from Air Products; and others, such as EH-4337S from Adeka. The amount of epoxy resin curing agent used is 2 to 70 parts by weight based on 100 parts of epoxy resin by weight, preferably 4 to 10 parts by weight, based on 100 parts by weight of said liquid epoxy resin.
[0037] For adjusting physical properties, other ingredients such as inorganic fillers are added optionally. Typical examples of inorganic fillers as used herein include silicon dioxide, barium sulfate, mica and talcum powder. The amount of inorganic filler added is 0-200 parts by weight, based on 100 parts by weight of said liquid epoxy resin.
[0038] For desired processing characteristics of the via-filling step, one or more optional organic adjuvants can be used, including de-forming agents, thixotropic agents, Theological additives, leveling agents and dyes. The amount of organic adjuvants added is 0 to 50 parts by weight, based on 100 parts by weight of said liquid epoxy resin.
[0039] FIGS. 5 (A)- 5 (C) are schematic views of examples for filling up via with a solvent-less thermosetting photosensitive material in the process of manufacturing printed circuit board. According to the present invention, the solventless thermosetting photosensitive material ( 40 ) is fill up the via ( 20 ) by screen printing on PCB ( 10 ), as shown in FIG. 5 (A). Then, the PCB ( 10 ) is mounted in a 7 kW ultraviolet exposure machine for a short-time exposure. As a result, solid barrier films ( 43 ) with a thickness of greater than 50 μm (about ⅕ the thickness of the PCB) form at both ends of the via-filling material, as shown in FIG. 5 (B). The solid barrier films prevent the internal solventless thernosetting photosensitive material from flowing out of via. The exposure energy must be high enough so that the integrity of the solid barrier film will not be destroyed during the thermal post-curing process; on the other hand, the energy should not be so high as to scorch the solid barrier films. To form optimal solid barrier films to keep the internal solventless thermosetting photosensitive material from flowing out of via, the exposure energy set is preferably from 0.5 to 5 mJ/cm 2 for the ultraviolet exposure machine.
[0040] After ultraviolet exposure, a thermal curing process is subsequently carried out. Preferably, the thermal curing process is carried out at a temperature of 100-260° C. for at least 3 minutes. The via-filling material ( 40 ), after thermal curing, is cylindrical in shape with flat surface profiles and solid interior containing no voids or holes, as shown in FIG. 5 (C).
EXAMPLE 1
[0041] A solventless thermosetting photosensitive via-filling material consists of 100 parts by weight bisphenol-A epoxy resins (LG N-730), 6 parts by weight 2,4-diamino-6[2′-methylimidazoly-(1′)] ethyl-S-triazine isocyanuric acid addition compound, 20 parts by weight tris(2-hydroxyethyl) isocyanurate triacrylate, 2 parts by weight 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 0.2 parts by weight 2-isopropyl thioxanthone, 2.5 parts by weight Aerosil R974 and 3 parts by weight Defoamer KS-66.
[0042] The solventless thermosetting photosensitive via-filling material is used to fill up the via by screen printing on PCB. Then, the PCB is mounted in a 7 kW ultraviolet exposure machine for a short-time exposure with exposure energy of 1 mJ/cm 2 . As a result, solid barrier films with a thickness of greater than 50 μm form at both ends of the via-filling material. The solid barrier films will prevent the internal solventless thermosetting photosensitive material from flowing out of via.
[0043] After ultraviolet exposure, a thermal curing process is subsequently carried out at a temperature of 150° C. for 20 minutes. The solventless thermosetting photosensitive material in via, after thermal curing, is cylindrical in shape with flat surface profiles and solid interior containing no voids or holes.
EXAMPLE 2
[0044] A solventless thermosetting photosensitive via-filling material consists of 100 parts by weight bisphenol-F epoxy resins (Epon-862), 6 parts by weight 2,4-diamino-6[2′-methylimidazoly-(1′)] ethyl-S-triazine isocyanuric acid addition compound, 15 parts by weight trimethylolpropane triacrylate, 2 parts by weight 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 0.2 parts by weight 2-isopropyl thioxanthone, 2.5 parts by weight Aerosil R974 and 3 parts by weight Defoamer KS-66.
[0045] The solventless thermosetting photosensitive via-filling material is used to fill up the via by screen printing on PCB. Then, the PCB is mounted in a 7 kW ultraviolet exposure machine for a short-time exposure with exposure energy of 1 mJ/cm 2 . As a result, solid barrier films with a thickness of greater than 50 μm form at both ends of the via-filling material. The solid barrier films prevent the internal solventless thermosetting photosensitive material from flowing out of via.
[0046] After ultraviolet exposure, a thermal curing process is subsequently carried out at a temperature of 150° C. for 20 minutes. The solventless thermosetting photosensitive material in via, after thermal curing, is cylindrical in shape with flat surface profiles and solid interior containing no voids or holes.
[0047] While the invention has been described in its preferred embodiments, this should not be construed as limitation on the scope of the present invention. Accordingly, the scope of the present invention should be determined not by the embodiment illustrated, but by the appended claims and their legal equivalents. | A via-filling material improves a via-filling process in manufacturing multi-layered printed circuit boards. The via-filling material is capable of undergoing UV pre-cure and thermal post-cure step. Exposed to ultraviolet light, the via-filling material filled up the two ends of the via form solid barrier films so that the inside via-filling material will not flow out during a thermal post curing process due to an lower viscosity of said material. The dual-cure treatment resolves the problems of polishing, sagging and bubbling in the via-filling process and ensures the integrity of the filling material. As a result, the via-filling material with smooth surface and a solid inside without void or hole therein formed. | 2 |
[0001] The present invention starts from known methods for the production of structures of electrically conducting material using printing methods. The invention relates to a method by means of which it is possible to deposit nanofibres in a targeted manner with a high spatial precision onto any desired surface. This is made possible by a specially adapted process of so-called electrospinning in conjunction with a material suitable for this purpose, from which the electrically conducting structures are formed, wherein the structures consist of electrically conducting particles or are subjected to a post-treatment in order to impart conductivity.
BACKGROUND OF THE INVENTION
[0002] Many structural parts (e.g. many internal fittings of automobiles; discs) and objects of daily use (e.g. beverage bottles) consist substantially of electrically insulating materials. This includes known polymers, such as polyvinyl chloride, polypropylene etc., but also ceramics, glass and other mineral materials. In many cases the insulating effect of the structural part is desired (e.g. in the case of housings of portable computers). However, there is often also a need to apply an electrically conducting surface or structure to such structural parts or objects, in order for example to integrate electronic functions directly into the structural part or the object.
[0003] Further requirements placed on the surface of articles of daily use and their material include as great an artistic freedom as possible in the design and configuration, positive mechanical properties (e.g. high impact strength), as well as specific optical properties (e.g. transparency, gloss, etc.), which are achieved in different degrees particularly by the materials listed above by way of example.
[0004] There is therefore the need to obtain the positive properties of the material and, specifically, to produce an electrically conducting surface. In particular the optical transparency and gloss are in this connection technically demanding. These can be achieved only in three ways. Either the substrate material itself is specifically made electrically conducting, without thereby adversely affecting its mechanical and optical properties, or a material is used that is conducting but is not visually recognisable by the human eye and can easily be applied in a targeted manner to the surface of the substrate, or a conducting material is used, which although itself is not transparent, can however be applied by means of a suitable process to the surface in such a way that the resulting structure is in general not perceivable by the human eye without the assistance of optical aids. In this way the properties of gloss and transparency of the substrate are not affected.
[0005] In general any structure which, when applied to a two-dimensional surface does not exceed a characteristic length of 20 μm in one of its two dimensions on the substrate plane, is regarded as visually non-recognisable. In order reliably to exclude any influencing of the surface recognition, structures in the submicron range (i.e. with a line width of ≦1 μm) are particularly desirable.
[0006] A large number of methods exist for applying in particular conducting material to surfaces. In particular conventional printing methods, such as screen printing or ink jet printing, are suitable for this purpose. Corresponding formulations for conducting materials—also termed inks—already exist particularly for these printing techniques, which in conjunction with the methods enable conducting structures to be formed on the surface.
[0007] Whereas screen printing methods on account of the very small available mesh width of the printing screen are in principle not able to produce structures with an optical resolution of less than 1 μm, ink jet printing methods for example would theoretically be suitable for this purpose, since the dimensions of the resulting structure on the substrate in the case of ink jet printing methods directly correlate to the nozzle diameter of the printing head that is used. However, in this connection the characteristic length of the minimal dimension of the resulting structure is as a rule larger than the diameter of the employed nozzle head [J. Mater. Sci 2006, 41, 4153; Adv. Mater 2006, 18, 2101]. Nevertheless, in principle structures with a line width of less than 1 μm could be produced if printers with nozzle openings of significantly less than 1 μm can be used. However, this is not feasible in practice since with increasing reduction of the nozzle diameter the requirements on the inks that can be used become much more stringent. Should the employed ink contain particles, then their mean diameter would have to match the reduction in the nozzle diameter, which in principle already excludes all inks with particles of size ≧1 μm. Furthermore, the requirements placed on the rheological properties of the ink (e.g. viscosity, surface tension, etc.) so that it can still be used for the printing head increase. In many cases these parameters cannot however be adjusted separately from the behaviour (e.g. spreading and adherence) of the ink on the respective substrate, which means that the ink and printing method combination cannot be used to produce conducting structures in this size range.
[0008] One method with which alternatively structures of size less than 1 μm can be produced on polymer surfaces is the so-called hot stamping method. By means of this method circular surface structures with a diameter of ca. 25 nm have already been produced [Appl Phys Lett 1995, 67, 3114; Adv Mater 2000, 12, 189]. The disadvantage of hot stamping however is that the structural shape is restricted to the shape of the stamping punch or stamping roller that is used in each case. A free choice in the configuration of the structure is not possible with this method. Particularly thin fibres, which potentially could also be applied to the surface of a suitable substrate, can be produced by means of a method that has become established under the name “electrospinning”. In this way it is possible by using a spinnable material to produce fibres of a few nanometres in diameter [Angew Chem 2007, 119, 5770-5805].
[0009] Electrospun fibres are however obtained only in the form of large, disordered fibre mats. Up to now ordered fibres can however be obtained only by spinning on a rotating roller [Biomacromolecules, 2002, 3, 232]. It is also known that in principle electrically conducting fibres can be spun by means of “electrospinning”. A corresponding conducting material for such an application utilising the conductivity of carbon nanotubes is also known [Langmuir, 2004, 20(22), 9852 ].
[0010] In US2001-0045547 methods and materials are disclosed, with which conducting fibre mats can be obtained.
[0011] A targeted deposition of non-conducting fibres on planar surfaces has also been achieved by reducing the distance between the spinning head and the substrate [Nano Letters, 2006, 6, 839].
[0012] Up to now no electrically conducting structures with a specific arrangement on a substrate surface have been produced by means of electrospinning.
[0013] In US2005-0287366 a method and a material are disclosed, by means of which conducting fibres can be produced. The method includes electrospinning at an interspacing of about 200 mm, with the result that disordered fibre mats are likewise obtained. The material is a polymer that is made electrically conducting by further post-treatment steps, including a thermal treatment. A targeted orientation and application of the resultant fibres to a substrate is not disclosed.
[0014] The object of the present invention is accordingly to develop a process with which, by using the electrospinning technique, conducting structures that are visually not directly recognisable by the human eye can be specifically produced on a surface.
SUMMARY OF THE INVENTION
[0015] This object is achieved by the use of an arrangement for the production of electrically conducting linear structures with a line width of at most 5 μm on an, in particular, non-electrically conducting substrate, which is the subject-matter of the invention, comprising at least one substrate holder, a spinning capillary, which is connected to a reservoir for a spinning liquid and to an electrical voltage supply, an adjustable movement unit for moving the spinning capillary and/or the substrate holder relative to one another, an optical measuring instrument, in particular a camera, for following the spinning process at the outlet of the spinning capillary, and a computing unit for regulating the distance of the spinning capillary relative to the substrate holder depending on the spinning process.
BRIEF DESCRIPTION OF THE DRAWING
[0016] FIG. 1 is a diagrammatic illustration of the spinning arrangement according to the invention.
DETAILED DESCRIPTION
[0017] Preferably the spinning capillary has an opening width of at most 1 mm. Particularly preferred is an arrangement in which the spinning capillary has a circular opening with an internal diameter of 0.01 to 1 mm, preferably 0.01 to 0.5 mm and particularly preferably 0.01 to 0.1 mm.
[0018] In a preferred implementation of the new arrangement the voltage supply source delivers an output voltage of up to 10 kV, preferably 0.1 to 10 kV, particularly preferably 1 to 10 kV and most particularly preferably 2 to 6 kV.
[0019] In a further preferred implementation the adjustable movement unit serves to move the substrate holder.
[0020] Also preferred is an arrangement which is characterised in that the spinning capillary can be adjusted to a distance of 0.1 to 10 mm, preferably 1 to 5 mm and particularly preferably 2 to 4 mm from the substrate surface.
[0021] In a particularly preferred variant of the arrangement, the reservoir for the spinning liquid is provided with a conveying device that conveys the spinning liquid to the spinning capillary. A plunger-type syringe which is provided with a motor spindle as the plunger drive is for example suitable for this purpose.
[0022] The invention also provides a method for producing electrically conducting linear structures with a line width of at most 5 μm on an, in particular, non-electrically conducting substrate by electrospinning and post treatment, characterised in that a spinning liquid containing an electrically conducting material or a precursor compound for an electrically conducting material is spun onto the substrate surface from a spinning capillary with an opening width of at most 1 mm under the application of an electrical voltage between the substrate or substrate holder and spinning capillary or spinning capillary holder of at least 100 V at an interspacing of at most 10 mm between the outlet of the spinning capillary and the surface of the substrate, and the substrate surface is moved relative to the outlet of the spinning capillary, wherein the relative movement is controlled depending on the spinning flow, followed by removal of the solvent of the spinning liquid and optionally post-treatment of the precursor compound to form an electrically conducting material.
[0023] Suitable substrates are electrically non-conducting or poorly conducting materials such as plastics, glass or ceramics, or semi-conducting substances such as silicon, germanium, gallium arsenide and zinc sulfide. In a preferred method the distance between the outlet of the spinning capillary and the substrate surface is adjusted to 0.1 to 10 mm, preferably 1 to 5 mm and particularly preferably 2 to 4 mm.
[0024] The viscosity of the spinning liquid is preferably at most 15 Pa·s, particularly preferably 0.5 to 15 Pa·s, more particularly preferably 1 to 10 Pa·s and most particularly preferably 1 to 5 Pa·s.
[0025] The spinning liquid consists preferably of at least one solvent, in particular at least one solvent selected from the group consisting of: water, C 1 -C 6 alcohols, acetone, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide and meta-cresol, a polymeric additive, preferably polyethylene oxide, polyacrylonitrile, polyvinylpyrrolidone, carboxymethylcellulose or polyamide, and a conducting material.
[0026] Particularly preferred is a method in which the spinning liquid contains as conducting material at least one member of the group consisting of: conducting polymer, a metal powder, a metal oxide powder, carbon nanotubes, graphite and carbon black.
[0027] Particularly preferably the conducting polymer is selected from the group consisting of: polypyrrole, polyaniline, polythiophene, polyphenylenevinylene, polyparaphenylene, polyethylenedioxythiophene, polyfluorene, polyacetylene, and mixtures thereof, particularly preferably polyethylenedioxythiophene/polystyrenesulfonic acid.
[0028] In the case where the spinning liquid preferably comprises a conducting material at least one metal powder of the metals silver, gold and copper, preferably silver, then water containing a dispersant and optionally in addition C 1 -C 6 alcohol is used as solvent, in which connection the metal powder is present in dispersed form and has a particle diameter of at most 150 nm.
[0029] Preferably the dispersant includes at least one agent selected from the following list: alkoxylates, alkylolamides, esters, amine oxides, alkylpolyglucosides, alkylphenols, arylalkylphenols, water-soluble homopolymers, water-soluble random copolymers, water-soluble block copolymers, water-soluble graft polymers, in particular polyvinyl alcohols, copolymers of polyvinyl alcohols and polyvinyl acetates, polyvinyl pyrrolidones, cellulose, starch, gelatins, gelatin derivatives, amino acid polymers, polylysine, polyaspartic acid, polyacrylates, polyethylene sulfonates, polystyrene sulfonates, polymethacrylates, condensation products of aromatic sulfonic acids with formaldehyde, naphthalene sulfonates, lignin sulfonates, copolymers of acrylic monomers, polyethyleneimines, polyvinylamines, polyallylamines, poly(2-vinylpyridines), block copolyethers, block copolyethers with polystyrene blocks and/or polydiallyldimethyl ammonium chloride.
[0030] A particularly preferred spinning liquid is characterised in that the silver particles a) have an effective particle diameter of 10 to 150 nm, preferably 40 to 80 nm, measured by laser correlation spectroscopy.
[0031] The silver particles a) are preferably contained in the formulation in an amount of 1 to 35 wt. %, particularly preferably 15 to 25 wt. %.
[0032] The content of dispersant in the spinning liquid is preferably 0.02 to 5 wt. %, particularly preferably 0.04 to 2 wt. %.
[0033] The size determination by means of laser correlation spectroscopy is known in the literature and is described for example in: T. Allen, Particle Size Masurements, Vol. 1, Kluver Academic Publishers, 1999.
[0034] In another variant of the new method a spinning liquid is used which comprises a precursor compound for an electrically conducting material that is selected from the group consisting of: polyacrylonitrile, polypyrrole, polyaniline, poly-ethylenedioxythiophene and which additionally contains a metal salt, in particular an iron(III) salt, particularly preferably iron(III) nitrate. Suitable solvents are for example acetone, dimethyl acetemide, dimethylformamide, dimethyl sulfoxide, meta-cresol and water.
[0035] The method is most particularly preferably carried out in such a way that the new arrangement described above or a preferred variant thereof is used to spin the spinning liquid.
[0036] The desired fine electrically conducting structures are produced by electrospinning by means of the above arrangement. Depending on the spinning solution that is used the structures have to be post-treated in order to achieve or increase the desired conductivity.
[0037] When a voltage is applied between the capillary or capillary holder and the substrate holder, a droplet from which the spinning thread emerges is formed at the opening of the capillary.
[0038] In addition receptacles for the capillary and substrate are configured so that a relative positioning of the capillary opening with respect to the substrate surface is possible. In a preferred embodiment the capillary can be positioned above the substrate by means of adjustment motors, while in another embodiment it is possible with adjustment motors to position the substrate underneath the capillary during the spinning. Preferably the substrate is moved underneath the capillary.
[0039] In order to produce the desired conducting structures from the spinning liquid, it should be ensured that the spinning process is stabilised in such a way that the resulting structure does not exhibit any breaks/discontinuities on the surface. Preferably this is achieved by regulating the capillary distance relative to the substrate surface, in which the forward movement of the line is interrupted by means of a regulating loop depending on a camera image, if the spinning thread obviously breaks. Particularly preferably the procedure is stabilised by arranging for a computer to analyse the camera image and interrupt the relative feed movement of the capillary with respect to the substrate if the analysis shows a break in the continuous fibre.
[0040] The minimum voltage to be applied in the method varies linearly with the adjusted interspacing and also depends on the nature of the spinning liquid. Preferably an operating voltage of 0.1 to 10 kV should be employed for the spinning process so as to obtain a structured deposition of the fibres, as described above.
[0041] Particularly good results are achieved with distances between the head of the capillary and substrate surface in the range of from about 0.1 to about 10 mm. It was also found that for the implementation of the method, the material to be spun should have a viscosity of in particular at most 15 Pa·s, in order reliably to produce conducting structures with the spinning material.
[0042] After the steps described above have been carried out the specified material is present in the desired form on the substrate, and can if necessary be post-treated in order to increase the conductivity.
[0043] This post-treatment includes for example supplying energy to the produced structures. In the case of conducting polymers (in particular polyethylene dioxythiophene) the polymer particles present in suspension in the solvent are fused with one another on the substrate by for example heating the suspension, the solvent being at least partially evaporated. Preferably the post-treatment step is carried out at least at the melting point of the electrically conducting polymer, and particularly preferably above its melting point. In this way continuous conducting paths are formed. Also preferred is a post-treatment of the structures/fibres on the substrate by means of microwave radiation.
[0044] In the case of a spinning material containing carbon nanotubes, the solvent between the particles present in dispersed form is evaporated by the post-treatment of the lines that are formed, so as to obtain continuous strips of carbon nanotubes capable of percolation. The treatment step is in this connection carried out in the region of the evaporation temperature or thereabove of the solvent contained in the material, and preferably above the evaporation temperature of the solvent. When the percolation boundary is reached, the desired conducting paths are formed.
[0045] Alternatively conducting structures can also be produced by depositing a precursor material for an electrically conducting material, for example polyacrylonitrile (PAN), on the substrate and then heat treating the substrate under alternating gaseous media so as to produce carbon in the form of a conducting substance, as described hereinafter.
[0046] In this case a solution of a polymer (e.g. PAN or carboxymethylcellulose) and a metal salt (e.g. an iron(III) salt such as iron nitrate) is prepared in a solvent (e.g. dimethylformamide (DMF)) that is suitable for both components. The polymer should be able to be converted into a material which is stable and conducting at such temperatures. Particularly preferred polymers are those that can be converted to carbon by high temperature treatment. Particularly preferred are graphitisable polymers (such as for example polyacrylonitrile at 700′-1000° C.). In the case of the metal salts those are preferred whose disintegration temperature or decomposition temperature under a reductive atmosphere lie below the decomposition temperature of the respective polymer (e.g. iron(III) nitrate nonahydrate at 150° C. to 350° C.). After the conversion of the metal salts into metal particles, preferably by purely thermal disintegration or using gaseous reducing agents, particularly preferably by hydrogen, the polymer is converted into carbon in the presence of the metal particles. Finally, carbon is optionally in addition deposited from the gaseous phase onto the structures, preferably by chemical gaseous phase deposition from hydrocarbons. For this purpose volatile carbon precursors are led at high temperatures over the structures. It is preferred to use short-chain aliphatic compounds in this case, particularly preferably for example methane, ethane, propane, butane, pentane or hexane, especially preferably the aliphatic hydrocarbons n-pentane and x-hexane that are liquid at room temperature. In this case the temperatures should be chosen so that the metal particles promote the growth of tubular carbon filaments and an additional graphite layer along the fibres. In the case of iron particles this temperature range is for example between 700° and 1000° C., preferably between 800° and 850°. The duration of the gaseous phase deposition in the above case is between 5 minutes and 60 minutes, preferably between 10 minutes and 30 minutes.
[0047] If according to the preferred procedure the aforedescribed suspensions of noble metal nanoparticles in solvents are used as spinning liquid to produce conducting structures, then the post-treatment can be carried out by heating the whole structural part or specifically the conducting paths to a temperature at which the metal particles sinter together and the solvent at least partially evaporates. In this connection particle diameters as small as possible are advantageous, since in the case of nanoscale particles the sintering temperature is proportional to the particle size, with the result that with small particles a lower sintering temperature is necessary. In this connection the boiling point of the solvent is as close as possible to the sintering temperature of the particles and is as low as possible, in order thermally to protect the substrate. Preferably the solvent of the spinning liquid boils at a temperature <250° C., particularly preferably at a temperature <200° C. and most preferably at a temperature <100° C. All the temperatures specified here refer to boiling points at a pressure of 1013 hPa. The sintering step is carried out at the specified temperatures until a continuous conducting path has been formed. The duration of the sintering step is preferably 1 minute to 24 hours, particularly preferably 5 minutes to 8 hours and most particularly preferably 2 to 8 hours.
[0048] The new method can be used in particular for the production of substrates that comprise conducting structures on their surface, that in one dimension have a length of not more than 1 μm, preferably 1 μm to 50 nm, and particularly preferably 500 nm to 50 nm, in which the conducting material is preferably a suspension of conducting particles, as described above, and the substrate is preferably transparent, for example of glass, ceramics, semiconductor material or a transparent polymer as described above.
[0049] The invention is described in more detail hereinafter by way of example and with reference to FIG. 1 , which shows diagrammatically the spinning arrangement according to the invention.
EXAMPLES
Example 1
Conducting Nanostructures with Carbon Nanotubes
[0050] The following apparatus (see FIG. 1 ) was used for spinning the spinning solution:
[0051] The holder 1 for the substrate 9 , which is a silicon disc, and the metallic holder 13 for the spinning capillary 2 , which is provided with a liquid reservoir 3 for the spinning solution 4 and is connected to an electrical voltage supply 5 . The voltage source 5 supplies D.C. voltage up to 10 kV. The spinning capillary 2 is a glass capillary with an internal diameter of 100 Mm. The controllable adjustment motor 6 serves to move the spinning capillary 2 and the adjustment motor 6 ′ serves to move the substrate holder 1 relative to one another so as to adjust the distance between them. The camera 7 is trained on the outlet of the spinning capillary 2 so as to follow the spinning procedure and is connected to a computer 8 with image processing software for evaluating the image data provided by the camera. The drive of the motor 6 ′ of the substrate holder 1 is adjusted by the computer 8 depending on the outflow of the spinning solution 4 from the spinning capillary 2 . A spinning solution 4 was prepared from 10 wt. % of polyacrylonitrile (PAN: mean molecular weight 210 000 g/mol) and 5 wt. % of iron(III) nitrate nonahydrate in dimethylformamide. The viscosity of the resultant solution was about 4.1 Pa·s. The spinning process was initiated at an interspacing of 0.6 mm between the capillary opening and surface of the substrate 9 at a voltage of 1.9 kV between the spinning capillary 2 and substrate 9 . After the establishment of a stable fibre flow the voltage was set to 0.47 kV and the interspacing was increased to 2.2 mm. At this setting the spinning solution 4 was spun onto the surface of the substrate 9 and the substrate was moved sideways so as to form lines.
[0052] The substrate 9 together with the contained PAN fibres was next heated from 20° to 200° C. within 90 minutes, and then treated for 60 minutes at 200° C. Following this the air of the drying oven in which the sample 9 was contained was replaced by argon and the temperature was raised to 250° C. within 30 minutes. Argon was then replaced by hydrogen. The temperature was again held for 60 minutes at 250° C. under this hydrogen atmosphere. This atmosphere was then replaced once again by argon as gas for the drying oven, and the sample 9 was heated to a temperature of 800° C. within 2 hours. Finally, hexane was metered into the argon for 7 minutes and following this the sample 9 was cooled once more under argon again to room temperature. The cooling process was not regulated in this case, but was monitored until the interior of the oven had again fallen to a temperature of 20° C.
[0053] A conducting line based substantially on carbon was formed. On contacting two points on the line spaced apart by 190 μm, a resistance of 1.3 kOhm was measured. The line had a line width of ca. 130 nm. | Apparatus and method for producing electrically conducting nanostructures by means of electrospinning, the apparatus having at least a substrate holder ( 1 ), a spinning capillary ( 2 ), connected to a reservoir ( 3 ) for a spinning liquid ( 4 ) and to an electrical voltage supply ( 5 ), an adjustable movement unit ( 6, 6′ ) for moving the spinning capillary ( 2 ) and/or the substrate holder ( 1 ) relative to one another, an optical measuring device ( 7 ) for monitoring the spinning procedure at the outlet of the spinning capillary ( 2 ), and a computer unit ( 8 ) for controlling the drive of the spinning capillary ( 2 ) relative to the substrate holder ( 1 ) in accordance with the spinning procedure. | 3 |
FIELD OF THE INVENTION
[0001] The present invention generally relates to apparatus and methods for extruding thermoplastic filaments and, more particularly, apparatus for spunbonding multi-component or single component filaments.
BACKGROUND OF THE INVENTION
[0002] Melt spinning techniques, such as spunbonding or meltblowing techniques, for extruding fine diameter filaments find many different applications in various industries including, for example, in nonwoven material manufacturing. This technology generally involves extruding a thermoplastic material from multiple rows of discharge outlets extending along the lower surface of an elongate spinneret. Spunbonded and/or meltblown materials are used in such products as diapers, surgical gowns, carpet backings, filters and many other consumer and industrial products. The machines for meltspinning such materials can be very large and include numerous filament discharge outlets.
[0003] For certain applications, it is desirable to utilize two or more types of thermoplastic liquid materials to form individual cross-sectional portions of each filament. Often, these multi-component filaments comprise two components and, therefore, are referred to as bicomponent filaments. For example, when manufacturing nonwoven materials for use in the garment industry, it may be desirable to produce bicomponent filaments having a sheath-core construction. The outer sheath may be formed from a softer material which is comfortable to the skin of an individual and the inner core may be formed from a stronger, but perhaps less comfortable material having greater tensile strength to provide durability to the garment. Another important consideration involves cost of the material. For example, a core of inexpensive material may be combined with a sheath of more expensive material. For example, the core may be formed from polypropylene or nylon and the sheath may be formed from a polyester or co-polyester. Many other multi-component fiber configurations exist, including side-by-side, tipped, and microdenier configurations, each having its own special applications. Various material properties can be controlled using one or more of the component liquids. These include, as examples, thermal, chemical, electrical, optical, fragrance, and anti-microbial properties. Likewise, many types of die tips exist for combining the multiple liquid components just prior to discharge or extrusion to produce filaments of the desired cross-sectional configuration.
[0004] One problem associated with multi-component extrusion apparatus involves the cost and complexity of the manifolds used to transmit liquid(s) to the spinneret or extrusion die. Typical manifolds are machined with many different passages to ensure that the proper flow of each component liquid reaches the die under the proper pressure and temperature conditions. These manifolds are therefore relatively complex and expensive components of the melt spinning apparatus.
[0005] For these reasons, it would be desirable to provide a an extruding apparatus having a manifold system which may be easily manufactured while still achieving the goal of effectively transmitting the heated liquid or liquids to the die tip.
SUMMARY OF THE INVENTION
[0006] The invention generally provides a lamellar die apparatus for extruding a heated liquid into filaments preferably by spunbonding techniques. The apparatus is constructed with a plurality of plates each having opposite side faces. At least two of the side faces confront each other and have a liquid passage positioned therebetween for transferring the heated liquid. At least two of the side faces confront each other and have a heating element passage therebetween. A heating element is positioned within the heating element passage for heating the liquid in the liquid passage. An extrusion die is coupled with the plurality of plates and communicates with the liquid passage for discharging the heated liquid as multiple filaments.
[0007] The liquid passage is preferably formed by respective first and second recesses on adjacent plates that abut one another. Likewise, the heating element passage is formed by respective third and fourth recesses on adjacent plates that abut one another. Recesses from different ones of these pairs of recesses may, for example, be located on opposite sides of the same plate. In the preferred embodiment, multiple heating element passages are positioned between two of the plates and multiple heating elements are respectively contained in the heating element passages.
[0008] The liquid passage includes an inlet portion and an outlet portion with the outlet portion being wider than the inlet portion. The outlet portion of the liquid passage forms an elongate liquid outlet slot. The extrusion die includes an elongate liquid inlet slot aligned in communication with the elongate liquid outlet slot to facilitate liquid flow to the extrusion outlets.
[0009] The invention further contemplates methods of extruding liquid filaments, such as single or multiple component thermoplastic polymeric filaments, in general accordance with the use of the apparatus described above.
[0010] Various advantages, objectives, and features of the invention will become more readily apparent to those of ordinary skill in the art upon review of the following detailed description of the preferred embodiments, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is an exploded perspective view of a multi-component spunbonding apparatus constructed in accordance with a preferred embodiment of the invention.
[0012] FIG. 2 is a cross sectional view taken along line 2 - 2 of FIG. 3 .
[0013] FIG. 3 is a fragmented top view of the assembled apparatus of FIG. 1 taken generally along line 3 - 3 of FIG. 2 .
[0014] FIG. 4 is a cross sectional view similar to FIG. 2 , but illustrating an alternative embodiment of the apparatus and taken along line 4 - 4 of FIG. 5 .
[0015] FIG. 5 is a cross sectional view taken along line 5 - 5 of FIG. 4 .
[0016] FIG. 6 is a cross sectional view similar to FIG. 2 , but illustrating another alternative embodiment of the apparatus.
[0017] FIG. 7 is a cross sectional view similar to FIG. 4 , but illustrating another alternative embodiment of the apparatus.
DETAILED DESCRIPTION
[0018] FIGS. 1-3 illustrate a die apparatus 10 constructed in accordance with a first embodiment. Apparatus 10 is comprised of a manifold structure 12 coupled for fluid communication with an extrusion die 14 . Manifold structure 12 is a lamellar construction or plate assembly comprised of multiple plates 16 a - c , 18 a - c and 20 . These plates are securely fastened together in side-by-side relation using appropriate fasteners 22 (only one shown in FIGS. 2 and 3 ) extending through holes 24 in each of the plates. As best shown in FIG. 2 , respective outside pairs of plates 16 a , 16 b and 18 a , 18 b form optional air manifold sections and include respective quench air input ports 26 , 28 . Positive pressure quench air assists in quickly cooling the discharged filaments. Optionally, vacuum may be drawn through ports 26 , 28 for purposes of removing monomer gases at the filament discharge area. In each case, it will be understood that the appropriate openings (not shown) will be provided in or adjacent die 14 to allow the discharge of quench air or intake of monomer gases. Plates 16 a , 16 b and 18 a , 18 b respectively abut each other and contain air passages 27 , 29 therebetween. Air passages 27 , 29 are respectively formed by pairs of recesses 30 , 32 and 34 , 36 that align with each other in abutting faces of the plates 16 a , 16 b and 18 a , 18 b.
[0019] As shown best in FIG. 1 , these recesses 30 , 32 and 34 , 36 take the form of so-called coat hangar recesses which become wider in dimension from the inlet portion 40 located proximate input ports 26 , 28 to an outlet portion 42 located proximate respective distribution passages 44 . Distribution passages 44 extend respectively through plates 16 b and 18 b and lead to extrusion die 14 . Plates 16 c and 18 c respectively abut central plate 20 as shown.
[0020] Respective liquid passages 54 , 56 are formed between plates 16 c , 20 and 18 c , 20 and, again, are formed by respective pairs of coat hangar recesses 58 , 60 and 62 , 64 that align with each other in abutting surfaces of these plates 16 c , 20 and 18 c , 20 . As shown in FIG. 1A , these recesses 58 , 60 and 62 , 64 are also formed with a coat hangar configuration between inlet portions adjacent respective liquid input ports 66 , 68 and outlet portions which form elongate liquid outlet slots 70 , 72 for abutting the top surface of the extrusion die 14 and aligning with coextensive liquid inlet slots 73 , 75 . In this embodiment, the two liquid input ports 66 , 68 and coat hangar passages 54 , 56 are provided for producing bicomponent filaments from extrusion die 14 . Extrusion die 14 may be any suitable extrusion die having, for example, a laminated plate construction with appropriate porting and passages to combine and extrude filaments from the outlet orifices extending along the underside of the extrusion die 14 and to attenuate or otherwise affect those filaments with process air. Representative dies are, for example, disclosed in U.S. Pat. Nos. 5,562,930; 5,551,588; and 5,344,297, however, such dies would require modification with suitable passages to transfer and discharge quench air received from distribution passages 44 .
[0021] Also in accordance with the invention, heating elements 74 , 76 are respectively contained in passages 80 , 82 between plates 16 b , 16 c and 18 b , 18 c . Each passage is again preferably formed by respective pairs of aligned and abutting recesses 84 , 86 and 88 , 90 in plates 16 b , 16 c and 18 b , 18 c . These heating elements 74 , 76 , which are preferably electrically operated heating elements, may be advantageously situated between the respective air and liquid passages 27 , 54 and 29 , 56 so as to heat both the liquid and the air traveling to extrusion die 14 . Sufficient heat may also be supplied to heat the extrusion die 14 itself to the appropriate operating temperature.
[0022] FIGS. 4 and 5 illustrate another apparatus 10 ′ constructed in accordance with the invention. In this embodiment, apparatus 10 ′ again comprises a multiple plate assembly or manifold structure 12 ′ coupled with an extrusion die 14 ′. Manifold structure 12 ′ and die 14 ′ are similar to the first embodiment except that a five plate construction is used instead of a seven plate construction thereby eliminating the quench air. In this embodiment, plates 16 a , 18 a have been eliminated from the outside of the manifold structure 12 ′ to eliminate the quenching air to the extrusion die 14 ′. This quenching air can instead be discharged at the filaments by other means such as conventional components located below die 14 ′. Other elements indicated with like reference numerals to the first embodiment but have prime mark (′) designations are only slightly modified as shown. Elements having like numerals to the first embodiment are identical elements. In both cases, no further description is necessary to an understanding of the invention.
[0023] FIG. 6 illustrates another alternative die apparatus 200 having a laminated plate construction. This apparatus 200 is similar to that described above with respect to the first embodiment ( FIGS. 1-3 ), but is configured to discharge single component filaments or monofilaments rather than a bicomponent filament. Thus, the central plate 20 used in the first embodiment has been eliminated thereby resulting in a six plate construction rather than a seven plate construction for manifold structure 202 . As with the previous embodiments, an extrusion die 204 is coupled to manifold structure 202 for discharging one or more filaments and, optionally, discharging quenching air. A single liquid input port 206 and coat hanger passage 208 receive the liquid, such as a thermoplastic polymer. Coat hanger passage 208 is formed by aligned recesses 210 , 212 in abutting faces of plates 16 c ′ and 18 c ′. Plates 16 c ′ and 18 c ′ are designated with prime marks (′) to denote that they are slightly modified, as illustrated, from plates 16 c , 18 c . All other aspects of apparatus 200 are as described above with respect to the first embodiment and, therefore, identical reference numerals have been used and no further description is necessary.
[0024] FIG. 7 illustrates another alternative apparatus 220 similar to that described above with respect to FIGS. 4 and 5 but, like the embodiment of FIG. 6 , apparatus 220 is configured to discharge single component filaments or monofilaments rather than bicomponent filaments. Again, the central plate 20 of the embodiment illustrated in FIGS. 4 and 5 has been eliminated and a four plate manifold structure 222 results. Manifold structure 222 is configured to deliver a single type of liquid, such as a thermoplastic polymer, to an extrusion die 224 . A single liquid input port 206 and a coat hanger passage 208 is formed between abutting plates 16 c ′, 18 c ′ to communicate with an appropriate elongate inlet slot (not shown) in the top of the extrusion die 224 . Plates 16 c ′ and 18 c ′ are identical to those shown in FIG. 6 . All other aspects of the embodiment shown in FIG. 7 are described with respect to the first two embodiments described above and, therefore, identical reference numerals have been used and no further description is necessary.
[0025] While the present invention has been illustrated by a description of various preferred embodiments and while these embodiments has been described in some detail, it is not the intention of the Applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The various features of the invention may be used alone or in numerous combinations depending on the needs and preferences of the user. This has been a description of the present invention, along with the preferred methods of practicing the present invention as currently known. However, the invention itself should only be defined by the appended claims, wherein we claim: | A lamellar die apparatus for extruding a heated liquid into single or multiple component filaments. The apparatus includes a plurality of plates each having opposite side faces. At least two of the side faces confront each other and have a liquid passage positioned therebetween for transferring the heated liquid. At least two of the side faces confront each other and have a heating element passage therebetween. A heating element is positioned within the heating element passage for heating at least two of the plates. An extrusion die is coupled with the plurality of plates and communicates with the liquid passage for discharging the heated liquid as multiple filaments. | 3 |
The present application is a divisional of, and claims priority to, U.S. Patent application Ser. No. 08/799,007 filed on Feb. 7, 1997, the contents of which are expressly incorporated herein by reference.
FIELD OF THE INVENTION
This invention relates to surgical bone cement compositions and more particularly to bone cement compositions having anaesthetic properties, and to methods for producing local analgesia.
BACKGROUND OF INVENTION
Polymer based surgical bone cements have been used for many years to fill voids in bones and to improve fixation of implanted orthopaedic prosthetic devices. Typically such cements contain polymers or copolymers of alkyl methacrylate and/or copolymers of methyl methacrylate with methyl acrylate or styrene. The liquid compound consisting of esters of acrylic or methacrylic acid (typically methyl methacrylate) is packaged in an ampoule, possibly with additives such as premature polymerization preventers such as hydroquinone, and curing promoters such as N,N-dimethyl-p-toluidine. A polymerization initiator, typically an organic peroxy compound such as powdered benzoyl peroxide, is combined with the polymeric component and radiopacifier (such as barium sulphate or zirconium dioxide). The polymeric materials are generally sterilized by either irradiation or gas sterilization. In use, typically a bone is cut and prepared to receive a surgical implant and then the liquid and dry components of the cement, contained in the ampoule and a powder bag are mixed together to form a paste which can then be applied by the surgeon to the cut bone. The implant can then be set in the paste which, when fully polymerized, forms a continuous solid interface between the implant and the bone.
It is also known to incorporate therapeutic or diagnostic substances into the bone cement for various purposes. For example, U.S. Pat. No. 4,900,546, issued Feb. 13, 1990 to Poseyn Dowty et al, teaches the incorporation of antibiotics such as gentamycin, penicillin and tetracycline; anti-cancer drugs; anti-inflammatory drugs; immuno-stimulants; immuno-suppressants; osteogenic promoters and diagnostic substances such as radioactive tracers. While anti-inflammatory drugs may be defined as analgesics, such compounds are not anaesthetic agents.
Although local anaesthetics, such as lidocaine and prilocaine are known to have potent anti-microbial activity (anti-bacterial and anti-fungal), when used in relatively high dosages (0.5-2% solution) ( J. Infect. Diseases , Vol 121, No. 6,597-607, June 1970), heretofore such anaesthetic compounds have not been incorporated into bone cements for the promotion of anaesthesia. It has now been found that substantial pain relief can be achieved by incorporating into a known bone cement composition a local anaesthetic agent at a dosage level several orders of magnitude lower than would be required to achieve an anti-microbial effect with such agent.
OBJECT OF INVENTION
An object of the present invention is to provide novel bone cement compositions, having anaesthetic properties, which incorporate an analgesic. Another object of this invention is to provide a method for producing analgesia adjacent to a bone end.
BRIEF STATEMENT OF INVENTION
By a broad aspect of this invention, there is provided an anaesthetic bone cement comprising a bone cement composition including an effective amount up to about 5% by weight of a local anaesthetic agent.
By a preferred aspect of this invention, there is provided an anaesthetic bone cement composition comprising: (a) a liquid monomeric (meth)acrylate composition; (b) a powder comprising at least one of a homopolymer and a copolymer of methyl methacrylate containing an effective amount of a polymerization initiator and a radiopacifier; and (c) an effective amount up to about 5% by weight of said bone cement composition of a local anaesthetic agent.
By another aspect of this invention, there is provided a process for the production of an anaesthetic bone cement comprising combining: (a) a liquid monomeric (meth)acrylate; (b) a powdered component comprising at least one of a homopolymer and a copolymer of methyl methacrylate, an effective amount of a polymerization initiator and a radiopacifier; and (c) an effective amount up to about 5% by weight of a local anaesthetic agent.
By yet another aspect of this invention there is provided a method for producing analgesia at an orthopaedic implant site in a patient, comprising cutting and preparing bones at said site to receive said implant and applying to said prepared bones a bone cement composition comprising: (a) a liquid monomeric (meth)acrylate composition; (b) a powder comprising at least one of a homopolymer and a copolymer of methyl methacrylate containing an effective amount of a polymerization initiator and a radiopacifier; and (c) an effective amount up to about 5% by weight of said bone cement composition of a local anaesthetic agent.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a graph showing accumulation of lidocaine from Howmedica Cement.
FIG. 2 is a graph showing accumulation of lidocaine from Zimmer Cement; and
FIG. 3 is a graph showing accumulation of lidocaine from DePuy CMW Cement.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Local anaesthetic agents are generally amides or ester compounds which act to block neural receptors and thus deaden or block pain. NSAID analgesic compounds such as aspirin or acetaminophen act in an entirely different manner to provide analgesia but not anaesthesia. As used herein, the term “analgesia” means an absence of normal sensibility to pain without affecting consciousness, and the term “anaesthesia” means total or partial loss of sensation induced by administration of a drug. The present invention is concerned with the use of local anaesthetic agents, such as lidocaine, bupivacaine, prilocaine (amide family), and tetracaine (ester family) to provide an analgesic effect in body tissues surrounding a surgical site in which a bone cement has been employed. A preferred anaesthetic agent is Xylocaine® (Astra Pharmaceuticals) brand of lidocaine.
In order to determine whether local anaesthetics, such as lidocaine, elute from a bone cement containing from about 2.0% to about 5.0% by weight anaesthetic, a series of elution studies were performed.
Method
40 g ampoules of bone cement from each of three manufacturers: Howmedica (Simplex® bone cement), Zimmer (Osteobond) and DePuy (CMW3 bone cement), were mixed with 0.5, 1.0 and 2.0 g of gas sterilized lidocaine (Xylocaine®, Astra Pharmaceutical). The polymerization initiated mixtures were formed into discs 50 mm×1 mm and allowed to harden. The hardened discs were then placed in a stirred solution (100 ml) containing 0.2% saline at 37° C. 100 μl aliquots were taken at 1, 2, 3, 4, 6, 24, 48 and 72 hours and HPLC with electrochemical detection analysis was performed to determine the lidocaine level in each sample.
Results
Typical elution profiles are shown in FIGS. 1 (Howmedica), 2 (Zimmer) and 3 (DePuy). From these profiles it may be concluded that lidocaine elutes from the bone cement mixture in an amount proportional to the amount of lidocaine in the mixture. The rate of elution is at a maximum during the first 24 hours and then tapers off. The curves also indicate that there is a peak dose at about the 6 hour point. The peak dose then provides sustained release over a 72-hour test period. It may also be concluded that elution occurs mainly from the surface of the disc and related to the porosity and other surface properties of the disc.
EXAMPLE 1
A female patient, 68 years old, having a previous total knee replacement and a below-the-knee amputation, presented with latent infection in the knee. A revision to remove the knee prosthesis was performed and the cut ends of the bone were treated with an anti-bacterial bone cement to keep the bones spaced. Three weeks later, the bone cement was removed and tissue samples were taken for laboratory analysis for signs of infection. Bone cement was temporarily applied to keep the bones spaced and aligned, but this time the cement was Howmedica bone cement containing 2 g of lidocaine (Xylocaine®) per 40 g package of cement. The lidocaine laden-cement was gas sterilized but not irradiated. After recovery from anaesthesia the patient reported severe pain in the knee for a period of approximately 6 hours and thereafter no pain at all. 24 hours post surgery, the patient was sleeping without the aid of pain killers and was also able to receive physiotherapy without feeling undue discomfort.
From this example, it appears that lidocaine is eluted from bone cement and within 6 hours of placement, sufficient lidocaine has eluted to provide an analgesic effect which persists for at least 24 hours and probably at least several days before it metabolizes in the body.
The effects of lidocaine on the mechanical properties of CMW3 bone cement have also been evaluated and are summarized in table 1 below.
TABLE 1
CMW3 +
Cement Property
CMW3
Lidocaine
Dough time (min:sec)
2:50
7:05
Setting time (min:sec)
10.06
14.20
Exotherm (° C.)
70.8
69.1
Compressive strength (Mpa)
112.0
113.3
Flexural strength (Mpa)
65.0
66.3
Flexural modulus (Mpa)
2785
2753
Impact strength (J/m)
3.03
3.61
From the table it can be seen that addition of lidocaine to CMW3 improves impact strength by about 10%, but has little effect on compressive strength, flexural strength or flexural modulus. It is particularly noted that lidocaine additions increase the cement setting time by about 40% and the “doughing time,” i.e., the time needed to reach a working mix that can be readily handled by a factor of 3.
It will, of course, be appreciated that other proprietary bone cements can equally well be employed including CMW® Endurance™ by DePuy or Palacos®R which is distributed by Schering Plough in Europe and by Richards in North America. The local anaesthetics of the present invention may also be incorporated into proprietary bone wax compositions, such as Ethricon® Bone Wax, which is a sterile mixture of beeswax and isopropyl palmitate, a wax softening agent used to control bleeding from bone surfaces. The local anaesthetics may also be incorporated into injectable bone substitutes, or bone paste, such as Norican Skeletal Repair System (Norican SRS) developed by Norican Corp. of Cupertino, Calif. which is a calcium phosphate based cement which, when injected, forms carbonated apatite. | A polymethacrylate or other bone cement composition having analgesic properties is described. Bone cements containing up to 5% by weight of a local anaesthetic agent, such as lidocaine, have been demonstrated to elute sufficient lidocaine to provide an analgesic effect in vivo. | 0 |
BACKGROUND OF THE INVENTION
The present invention is directed to knob locking devices and, more particularly, is directed to a knob locking device which not only provides for the complete locking of the know without affecting the position of the knob setting, but also establishes variable amounts of drag on the knob to enhance the operator's fine tuning control of the knob to adjust the electrical component.
Several prior art arrangements are known to provide a locking device to securely hold a control knob setting on a variable electronic device or component. Two pertinent prior devices are shown in the Damon U.S. Pat. No. 2,833,158 patent and the Shalek U.S. Pat. No. 3,053,110. The Damon device is only a two position arrangement wherein the locking device is either in the locked position or the unlocked position. There is no ability in the device to provide variable drag on the control knob which is desirable in many cases when an operator is precision setting the component using the control knob. If the control knob is too loose or free moving, precise positioning of the control knob is very difficult. Therefore, placing a slight amount of drag on the control knob allows an individual to enhance his precise positioning of the control knob to accurately adjust the electrical component. Further, the Damon device is unnecessarily complicated in its construction, since it utilizes at least five separate parts which must be made and assembled to constitute the locking device.
The Shalek device is also somewhat complicated in its construction, since it requires at least four components to constitute the locking device. Further, the Shalek device does not provide for a locking directly on the knob, but rather acts as a biasing means on the control shaft itself. Further, because of the unnecessary complicated use of several parts to construct not only the Shalek device, but also the Damon device, the assembly of such locking devices is more costly and time consuming. This is a considerable disadvantage with respect to the efficient and economical production of control arrangements for variable controlled electrical components or devices.
SUMMARY OF THE INVENTION
The present invention comprises a knob locking device having only three assembled pieces which provide not only for the complete locking or unlocking of the movement of the control knob without affecting the set position of the knob, but also for drag as desired on the control knob to allow a more precise and controlled movement of the knob. The present invention incorporates the use of a mounting bushing on which are positioned a holding member and a locking washer. The holding member is threadably engaged to the bushing and moves the locking washer in a longitudinal direction with respect to the control knob shaft toward and away from the knob. The holding member and locking washer are positioned between the knob and the component to be controlled. Because the holding member is threadably engaged with the bushing for movement toward and away from the control knob, the holding member can force the locking washer in direct contact with the knob with sufficient force, so that the knob is completely locked and prevented from any rotational movement. Further, the threaded engagement of the holding member with the bushing permits the holding member to vary the amount of force which may be exerted by the locking washer on the control knob.
The utilization of only three elements, the bushing, the lock washer, and the holding member, provides for a greatly simplified locking device which provides much easier assembly and greater economy in the construction of control assemblies for use with various electrical components and devices. The present invention provides for a secure and reliable locking system. There is no free play of the knob after the locking washer has been biased into tight contact against the control knob by the holding member. The present invention provides a more positive type of locking as compared to prior art devices. Continued turning of the holding member on the threads in the direction toward the control knob provides a tighter locking of the control knob to ensure that it is locked and prevented from any possible movement which may affect a critical setting of the electrical component.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded perspective view of the present invention;
FIG. 2 is a top planar view of the present invention;
FIG. 3 is a partial sectional view of the present invention showing the locking device in the unlocked position; and
FIG. 4 is a partial sectional view of the present invention similar to FIG. 3 showing the locking device in the locked position.
DETAILED DESCRIPTION OF THE INVENTION
The locking device 10 of the present invention is shown in FIG. 1 having a bushing 12, a holding member 14, and a locking washer 16. The bushing has a base flange 18 which is designed to mate with the control panel 20, having an aperture 22 designed to receive the shaft 24 of a variable control electrical component 26, such as a potentiometer. The bushing has internal threads 28 which are designed to receive the external threads 30 on the electrical component 26. The bushing and the electrical component are, when threaded together through the aperture 22, secured to the control panel 20. It should be noted that the bushing also has external threads 32 which are designed to receive internal threads 34 of the holding member 14. The holding member is designed to be threadably engaged with the bushing 12 to provide rotatable movement of the holding member 14 on the bushing 12, so that the holding member will also move in an axial direction along the control shaft 24 of the electrical component 26.
The holding member 14 has an outer knurled grasping surface 36 which an operator uses to rotate the holding member 14 in either a clockwise or counterclockwise direction. Located in the holding member 14 is a central recessed area 38 with a shoulder 40. Projecting from the shoulder 40 is a support ring 39 having a bearing surface 41. Positioned within the recess 38 on the bearing surface 41 is the locking washer 16 which is a circular ring having two internally directed projections 42 and 44. These projections are designed to be engaged with the slots 46 and 48 in the bushing 12. Therefore, when the bushing receives the lock washer 16 with the projections 42 and 44 in the slots 46 and 48, the locking washer cannot be rotatable with respect to either the bushing or the holding member.
As the holding member 14 moves in a longitudinal direction with respect to the control shaft 24, the locking washer is similarly moved in a longitudinal direction. Although the width of the circular bearing surface 41 is made a sufficient enough size to adequately support the locking washer 16, the width of the bearing surface 41 is kept narrow enough to provide greater pressure by the locking washer 16 against the control knob 50 as will be explained below in the operation of the present invention.
The locking washer can be made of any appropriate size to accommodate the size of the control shaft and control knob of the particular electrical component on which it is used. Where the locking washer is for use with a potentiometer 26 of the type generally shown in FIG. 1, a preferred size is approximately 0.03 to 0.06 inch thick with the inside two lugs or projections 42 and 44 being about 0.10 inch long and wide opposite each other. The locking washer can be made of aluminum, brass, copper, stainless steel or plastic.
Securely mounted to the outer end 25 of the control shaft 24 which projects through the aperture 22, the bushing 12, the holding member 14 and the locking washer 16 is a control knob 50. The control knob is securely fastened by set screw 52 to the control shaft 24 of the electrical component 26. Therefore, any rotative motion of the control knob 50 causes a similar rotative motion of the shaft 24, causing an adjustment in the electrical component 26. The outer diameter of the control knob 50 is slightly smaller than the diameter of the recess 38 in the holding member 14, so that the control knob is positioned partially within the recess 38 when the device is completely assembled.
The holding member 14 could be a molded or machined part from a plastic material. The bushing may be constructed of brass or stainless steel with the bottom flange 18 preferably having a hexagonal shape.
Located on the top surface 54 of the holding knob 14, as shown more clearly in FIG. 2, are indicia 56 showing the direction in which to rotate or turn the holding member 14 to lock the control knob 50 to prevent it from moving from a preset position.
Turning to the operation of the present invention, attention is directed to FIGS. 3 and 4. In FIG. 3, the locking device is shown in the unlocked position allowing for the free rotational movement of the control knob 50. In this orientation, showing no physical contact between the locking washer 16 and the inside face 58 of the control knob 50, the control knob is free to rotate the control shaft 24 and adjust the electrical component 26 positioned on the inside face 60 of the control panel 20.
By rotating the holding member 14 in a counterclockwise direction with respect to FIG. 2, the holding member 14 will move toward the control knob 50 in FIG. 3. The locking washer 16 which is resting on the bearing surface 41 in the recess 38 of the holding member will move longitudinally with respect to the control shaft 24 in the slots 46 and 48 of the bushing 12. The locking washer 16 will move toward the bottom surface 58 of the control knob 50. By moving the holding member 14 in a counterclockwise direction until it is turned as tight as possible, the locking washer 16 in FIG. 4 will be in tight contact with the bottom surface 58 of the control knob 50. The width of the bearing surface 41 is relatively narrow and creates a more concentrated tight force on the control knob 50 by the locking washer 16 than if the locking washer 16 were located on the shoulder 40.
Any attempt to rotate the control knob 50 will be prevented, since it is locked and will hold the precise setting desired in the electrical component. It should be noted that, since the locking washer 16 moves only in a longitudinal direction with respect to the control shaft 24 and does not rotate, its contact with the bottom surface 58 is in a nonrotative motion. Therefore, no rotative motion can be imparted to the control knob 50 which could otherwise cause undesirable movement in the control shaft and affect the desired setting. To reset the control knob the holding member 14 is turned in a clockwise direction to disengage the locking washer 16 from the control knob as shown in FIG. 3.
In some instances it is desirable to provide a slight drag force on the rotative motion of the control knob 50 rather than to completely lock the control knob 50, so that the operator's fine tuning control of the knob can be more precise. When the knob has no drag placed on it, the operator may not have the manipulative control in his fingers to provide a very precise and critical setting in the knob. Therefore, since the holding member 14 is threadably engaged with the bushing 12, it is possible to move the holding member to a plurality of positions between the completely locked position in FIG. 4 and the unlocked position in FIG. 3. Depending on the amount of drag desired, the locking washer 16 will be in either tighter or looser contact with the bottom surface 58 of the control knob 50. Of course it should be noted that when the locking washer 16 is completely out of contact with the bottom surface 58 of the control knob, there is no drag imparted upon the movement of the knob 50. | A device for use with variable electrical components such as potentiometers to provide not only an independent means adjacent the control knob to lock the knob in a fixed position, but also to provide variable amounts of drag on the knob to enhance more precise and accurate control of the knob. The locking device is positioned between the controlled component and the control knob. The locking device can be moved to a plurality of positions adjacent the control knob to vary the amount of drag on the control knob. | 8 |
FIELD OF THE INVENTION
The present invention pertains generally to the field of computer networking. More particularly, the present invention pertains to software applications used for configuring networking hardware installed on a computer system.
BACKGROUND OF THE INVENTION
Computer networks can be arranged in numerous configurations and in a variety of network types. Some of the most popular types of networks are Ethernet (coaxial cable or twisted-pair cable), token ring, Fiber Distributed Data Interface (FDDI), Frame Relay, Integrated Services Digital Network (ISDN), X.25, and Synchronous Data Link Control (SDLC). Typically, these networks are arranged in local area networks (LANs) and wide area networks (WANs). Usually, LANs are distinguished from WANs based upon the geographical area they cover and sometimes the number of users connected to the network. For example, a group of personal computers (PC) in a home or single business site (location) usually communicate with each over a LAN. Groups of PCs that are at remote locations from one another, such as those in different homes, different companies, or different branch offices of the same company, typically communicate with each other over a WAN. Most WANs typically require significant resources to provide service to a large number of users spread over a vast geographical area causing a WAN to be relatively expensive to build and maintain.
Some users utilize the Internet for virtual private networking to avoid the costs of a true private WAN network and\or paying for long distance communication bills. In essence, virtual private networking entails encrypting and decrypting IP packets for transport across the Internet. In some virtual private networks (VPNs), the payload portion of an IP packet is encrypted for transport across the Internet. The header information is left intact so that routers can forward the packet as it traverses the Internet. In other VPNs, an entire IP packet is encrypted and then encapsulated into new IP packets for transport across the Internet.
One use of the VPN is that it allows a mobile computer system (e.g., a Laptop) to be connected to a remote LAN. Typically, a user of the mobile computer system initiates a local call to an Internet Service Provider (ISP) and establishes an Internet session. Then, the mobile computer system sends an Internet message via the Internet to the remote LAN. The mobile system and the remote LAN then engage in a security protocol or handshaking to verify the user is an authorized user permitted to have access to the LAN. Once it is established the user is authorized to have access to the second LAN, a VPN is established, allowing the user and the remote computer system to access data stored within the LAN.
Windows 95® and Windows 98® operating systems, however, do not provide native support for several types of VPNs. Therefore, a VPN software package is typically required to be installed in a system to provide for such specialized networking needs. “Virtual” network interface cards (NICs) are often installed as part of a VPN software package. By way of background, “real” NICs are those associated with one or more pieces of hardware installed on the computer. They include PCI NIC cards, ISA NIC cards, PCMCIA NIC cards, USB NIC cards, etc. A “virtual” NIC is one that is not associated with any hardware. Some examples of “virtual” NICs include “Dial-Up Networking,” “Internet Connection Sharing,” and “VPN.” Virtual NICs are well known in the art and are a common way of providing specialized networking support.
Windows 95® and Windows 98® operating systems store information about each NIC installed on the system in the system registry regardless of whether the NIC is “real” or “virtual.” Thus, problems may arise when network configuration software or network monitoring software are interested in dealing with information specific to each NIC card. For instance, using conventional techniques, network configuration software or network monitoring software would be able to identify the NICs that are installed in the computer system by examining each sub-key under the “Net” class registry key for the system's current services, and getting its “DeviceDesc” string value. However, conventional network configuration software or network monitoring software would not be able to distinguish whether a NIC is “real” or “virtual.”
One solution is to maintain a list of known “virtual” NICs that the network configuration software can check against. In the past, when there were only a small number of “virtual” NICs that were likely to be found on a computer, it was feasible for network configuration software to keep track of such a list. However, that approach is undesirable because, as VPNs gain popularity, more and more new “virtual” NICs are entering the marketplace. Consequently, network configuration software and network monitoring software having the latest list of known “virtual” NICs need to be constantly updated.
Therefore, what is needed is a method that allows a system administrator or end-user to more easily monitor or modify the settings for “real” NICs installed on a client computer. What is also needed is a method that allows users to differentiate between “real” NICs and “virtual” NICs installed on a computer system.
SUMMARY OF THE DISCLOSURE
Accordingly, the present invention provides a method of determining whether a network interface card entry within the system registry of a Windows™-based operating system pertains to “real” physical hardware or to a “virtual” device. In one particular embodiment, the present invention is implemented as part of a network configuration software or network monitoring software and allows users or system administrators to more easily monitor and modify the settings for network interface cards installed on a computer system running on Windows 95® or Windows 98® operating systems.
In accordance with one embodiment of the present invention, the method includes the steps of: (1) opening the “HKEY_LOCAL_MACHINE\System\CurrentControlSet\Services\Class\Net” key entry of the system registry; (2) examining each of the sub-keys for the “Net” key, and find one with a “DriverDesc” string value matching a NIC; (3) opening the “Ndi” key under the matching sub-key; (4) getting the “DeviceID” string value under the “Ndi” key; and, (5) searching the “DeviceID” string for a backslash “\” character. If the backslash character is found, then it can be concluded that the network interface card entry is associated with “real” physical hardware. Otherwise, it can be concluded that the network interface card entry is associated with a “virtual” device.
Embodiments of the present invention include the above and further include a computer readable medium having contained therein computer readable codes for causing a computer system running on a Windows™-based operating system to perform a method of determining whether a network interface card entry of a system registry of the computer system is associated with physical hardware device, the method comprising the steps of: (1) opening a Net key entry of the system registry wherein the Net key entry includes a plurality of sub-key entries and wherein the Net key entry stores registry entries pertinent to network interface cards; (2) opening a respective one of the plurality of sub-key entries; (3) examining a driver description string stored within the respective sub-key entry; (4) provided that a value stored as part of the driver description string matches the network interface card entry, opening an “Ndi” key under the respective sub-key entry and searching for a backslash character within a device identification string under the “Ndi” key, wherein presence of the backslash character indicates that the network interface card entry is associated with physical hardware device.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments of the present invention and, together with the description, serve to explain the principles of the invention.
FIG. 1 illustrates an exemplary computer system platform upon which embodiments of the present invention may be practiced.
FIG. 2 is a graphical representation of an exemplary system registry.
FIG. 3 is a flow chart diagram illustrating the method of determining whether a network interface card entry of the system registry is associated with a “real” network interface card or a “virtual” network interface card according to one embodiment of the present invention.
FIG. 4 is a flow chart diagram illustrating the method of determining whether a network interface card entry of the system registry is associated with a “real” network interface card or a “virtual” network interface card according to another embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced without these specific details. In other instances, well-known structures and devices are not described in detail in order to avoid obscuring aspects of the present invention.
Some portions of the detailed descriptions which follow are presented in terms of procedures, steps, logic blocks, processing, and other symbolic representations of operations on data bits within a computer memory. These descriptions and representations are the means used by those skilled in the data processing arts to most effectively convey the substance of their work to others skilled in the art. A procedure, computer executed step, logic block, process, etc., is here and generally conceived to be a self-consistent sequence of steps of instructions leading to a desired result. The steps are those requiring physical manipulations of data representing physical quantities to achieve tangible and useful results. It has proven convenient at times, principally for reasons of common usage, to refer to these signals as bits, values, elements, symbols, characters, terms, numbers or the like.
It should be borne in mind, however, that all of these and similar terms are to be associated with the appropriate physical quantities and are merely convenient labels applied to these quantities. Unless specifically stated otherwise as apparent from the following discussions, it is appreciated that throughout the present invention, discussions utilizing terms such as “accessing”, “determining”, “generating”, “associating”, “assigning” or the like, refer to the actions and processes of a computer system, or similar electronic computing device. The computer system or similar electronic device manipulates and transforms data represented as electronic quantities within the computer system's registers and memories into other data similarly represented as physical quantities within the computer system memories into other data similarly represented as physical quantities within the computer system memories or registers or other such information storage, transmission, or display devices.
COMPUTER SYSTEM PLATFORM
With reference to FIG. 1, portions of the present invention are comprised of computer-readable and computer executable instructions which reside, for example, in computer-usable media of a computer system. FIG. 1 illustrates an exemplary computer system 112 on which embodiments (e.g., process 300 and process 400 ) of the present invention may be practiced. It is appreciated that system 112 of FIG. 1 is exemplary only and that the present invention can operate within a number of different computer systems including general purpose computer systems, embedded computer systems, and stand alone computer systems specially adapted for controlling automatic test equipment.
Computer system 112 includes an address\data bus 100 for communicating information, a central processor 101 coupled with bus 100 for processing information and instructions, a volatile memory 102 (e.g., random access memory RAM) coupled with the bus 100 for storing information and instructions for the central processor 101 and a non-volatile memory 103 (e.g., read only memory ROM) coupled with the bus 100 for storing static information and instructions for the processor 101 . Computer system 112 also includes a data storage device 104 (“disk subsystem”) such as a magnetic or optical disk and disk drive coupled with the bus 100 for storing information and instructions. Data storage device 104 can include one or more removable magnetic or optical storage media (e.g., diskettes, tapes) which are computer readable memories. Memory units of system 112 include volatile memory 102 , non-volatile memory 103 and data storage device 104 .
Computer system 112 can further include an optional signal generating device 108 (e.g., a modem, or a network interface card “NIC”) coupled to the bus 100 for interfacing with other computer systems. Also included in computer system 112 of FIG. 1 is an optional alphanumeric input device 106 including alphanumeric and function keys coupled to the bus 100 for communicating information and command selections to the central processor 101 . Computer system 112 also includes an optional cursor control or directing device 107 coupled to the bus 100 for communicating user input information and command selections to the central processor 101 . An optional display device 105 can also be coupled to the bus 100 for displaying information to the computer user. Display device 105 may be a liquid crystal device, other flat panel display, cathode ray tube, or other display device suitable for creating graphic images and alphanumeric characters recognizable to the user. Cursor control device 107 allows the computer user to dynamically signal the two dimensional movement of a visible symbol (cursor) on a display screen of display device 100 . Many implementations of cursor control device 107 are known in the art including a trackball, mouse, touch pad, joystick or special keys on alphanumeric input device 106 capable of signaling movement of a given direction or manner of displacement. Alternatively, it will be appreciated that a cursor can be directed and\or activated via input from alphanumeric input device 106 using special keys and key sequence commands. The present invention is also well suited to directing a cursor by other means such as, for example, voice commands.
SYSTEM REGISTRY OF WINDOWS OPERATING SYSTEMS
The system registry is a database used for storing settings and options for the 32 bit versions of Microsoft® Windows™ operating systems including Windows 95® and Windows 98®. The registry contains information and settings for many of the hardware, software, users, and preferences of a computer system. Whenever a user makes changes to a “Control Panel” settings, file associations, system policies, or installs new software and\or hardware, the changes are usually reflected and stored in the system registry. In most Windows 95® and Windows 98® computer systems, the physical files that make up the registry are stored in two hidden files under the “C:\WINDOWS” directory, called “USER.DAT” and “SYSTEM.DAT,” and can be edited with a Registry Editor (regedit.exe) that is included in most versions of Windows™ operating systems.
The system registry has a hierarchical structure. Although the registry looks complicated, its structure is similar to the directory structure of a file system. An exemplary hierarchical structure of the system registry for Windows 95® and Windows 98®, as graphically illustrated by registry editor “regedit.exe” is shown in FIG. 2 . As illustrated, each main branch 210 a - 210 f (denoted by a folder icon) is called a hive, and hives contains keys. Each key can contain other keys (sometimes referred to as sub-keys), as well as values. The values contain the actual information stored in the system registry. In Windows 95® and Windows 98®, there are three types of values: string, binary, and DWORD. There are six main branches 210 a - 210 f , each containing a specific portion of the information stored in the system registry. The branch name and descriptions of their corresponding content are illustrated below in Table 1.
TABLE 1
Branch Names
Content Description
HKEY_CLASSES_ROOT
This branch contains file association
types, OLE information and
shortcut data.
HKEY_CURRENT_USER
This branch links to the section of
HKEY_USERS corresponding to the
user currently logged onto the PC.
HKEY_LOCAL_MACHINE
This branch contains computer
specific information about the type of
hardware, software, and other
preferences on a given PC. This
information is used by all users who
use the given computer.
HKEY_USERS
This branch contains individual
preferences for each user of the
computer. Each user is represented
by a SID sub-key located under
the main branch.
HKEY_CURRENT_CONFIG
This branch links to the section of
HKEY_LOCAL_MACHINE
appropriate for the current
hardware configuration.
HKEY_DYN_DATA
This branch points to the part of
HKEY_LOCAL_MACHINE,
for use with the Plug-&-Play features
of Windows ™, this section is
dynamic and will change as devices are
added and removed from the system.
METHODS OF DETERMINING WHETHER A NETWORK INTERFACE CARD ENTRY WITHIN THE SYSTEM REGISTRY IS “REAL” OR “VIRTUAL”
FIG. 3 is a flow chart diagram illustrating the process 300 of determining whether a network interface card entry of the system registry (e.g., a sub-key) is associated with a “real” NIC or a “virtual” NIC according to one embodiment of the present invention. It should be appreciated that, in furtherance of the present embodiment, process 300 may be carried out manually by using a system registry editor such as “regedit.exe” which is shipped with most Windows 95® and Windows 98® operating systems. Process 300 may also be carried out automatically when implemented as process steps of a network configuration software.
As illustrated, at step 310 , process 300 of the present embodiment opens the “HKEY_LOCAL_MACHINE\System\CurrentControlSet\Services\Class\N et” key (“Net” key) of the system registry. As discussed above, the system registry is a database for storing hardware and software configuration information of a computer system. Further, as discussed above, the “HKEY_LOCAL_MACHINE” branch of the system registry contains computer specific information about the hardware and software installed on the computer system. In particular, information regarding NICs is customarily stored under the “Net” key.
At step 320 , process 300 of the present embodiment examines the sub-keys under the “Net” key, and finds a sub-key that has a “DriverDesc” String value that matches the String value for the NIC entry under investigation.
At step 330 , it is determined whether a match is found. If it is determined that a match is not found, then, at step 340 , it can be concluded that there is no corresponding “real” or “virtual” NIC for the NIC entry. Then, the process 300 ends.
However, if it is determined that a match is found, process 300 opens the “Ndi” key under the matching sub-key at step 350 . In accordance with the present embodiment, if the “Ndi” key cannot be found, then it can be concluded that the NIC (whether “real” or “virtual”) is not installed correctly.
At step 360 , after the “Ndi” key is opened, process 300 gets the “DeviceID” String value under the “Ndi” key. In accordance with the present embodiment, if the “DeviceID” String value cannot be found, then it can be concluded that the NIC (whether “real” or “virtual”) is not installed correctly.
At step 370 , process 300 searches the “DeviceID” String value for a backslash ‘\’ character. In the present embodiment, the presence of the backslash ‘\’ character within the “DeviceID” String indicates that the NIC entry under investigation is associated with a physical hardware device. On the other hand, if the “DeviceID” String does not contain a backslash ‘\’ character, then it can be concluded that the NIC entry is not associated with any physical hardware device and is therefore “virtual.” Thereafter, process 300 ends.
FIG. 4 is a flow chart diagram illustrating the process 400 of determining whether a network interface card entry of the system registry is associated with a “real” network interface card or a “virtual” network interface card according to another embodiment of the present invention. In furtherance of the present embodiment, process 400 is implemented as process steps of a network configuration software and is performed automatically when the network configuration software is run. It should be appreciated that steps of process 400 may be implemented with well known Windows™ APIs (Application Programming Interfaces) that are not described herein in detail to avoid obscuring aspects of the present invention.
As illustrated, at step 410 , process 400 of the present embodiment opens the “HKEY_LOCAL_MACHINE\System\CurrentControlSet\Services\Class\N et” key (“Net” key) of the system registry. As discussed above, the system registry is a database for storing hardware and software configuration information of a computer system. Further, as discussed above, the “HKEY_LOCAL_MACHINE” branch of the system registry contains computer specific information about the hardware and software installed on the computer system. Further, information regarding NICs is customarily stored under the “Net” key.
At step 420 , process 400 of the present embodiment examines the sub-keys under the “Net” key, finds all the sub-keys and records all the “DriverDesc” String values of the sub-keys. Under normal Windows 95® or Windows 98® operations, each sub-key under the “Net” key should have at least one “DriverDesc” string.
At step 430 , it is determined whether any sub-keys are found. If it is determined that no sub-keys are found, then, at step 440 , it can be concluded that there are no “real” or “virtual” NICs present in the computer system. Then, at step 490 , process 400 reports that no “real” or “virtual” NIC is present. Thereafter, the process 400 ends.
However, if it is determined that at least one sub-key is found, process 400 opens the “Ndi” key under one of the sub-key(s) at step 450 . In accordance with the present embodiment, if the “Ndi” key cannot be found, then it can be concluded that the NIC described by the sub-key (whether “real” or “virtual”) is not installed correctly.
At step 460 , after the “Ndi” key is opened, process 400 gets the “DeviceID” String value under the “Ndi” key. In accordance with the present embodiment, if the “DeviceID” String value cannot be found, then it can be concluded that the NIC (whether “real” or “virtual”) is not installed correctly.
At step 470 , process 400 searches the “DeviceID” String value for a backslash ‘\’ character. In the present embodiment, the presence of the backslash ‘\’ character within the “DeviceID” String indicates that the NIC entry under investigation is associated with a physical hardware device. On the other hand, if the “DeviceID” String does not contain a backslash ‘\’ character, then it can be concluded that the NIC entry is not associated with any physical hardware device and is therefore “virtual.”
With reference still to FIG. 4, at step 480 , if more than one sub-keys is found at step 420 , steps 450 , 460 and 470 are repeated for each of the non-processed sub-keys.
At step 490 , after all the information contained within the sub-key(s) are processed, process 400 reports the identity of the NICs present and whether each NIC is “real” or “virtual”. Thereafter, process 400 ends.
In furtherance of one embodiment of the present invention, other network configuration steps are carried out based upon the results of process 300 or process 400 . For instance, when a “real” NIC is identified, network configuration software would then be able to alter the settings of the NIC.
The present invention, a method of determining whether a NIC entry within the system registry is associated with “real” hardware or is associated with a “virtual” device, has thus been disclosed. The present invention allows such determination to be made easily through the examination of the system registry. While the present invention has been described in particular embodiments, it should be appreciated that the present invention should not be construed as limited by such embodiments, but should be construed according to the claims below. | Methods of determining whether a network interface card entry within the system registry of a Windows™-based operating system pertains to “real” physical hardware or to a “virtual” device. In one embodiment of the present invention, the method includes the steps of: (1) opening the HKEY_LOCAL_MACHINE\System\CurrentControlSet\Services\Class\Net key entry of the system registry; (2) examining each of the sub-keys for the “Net” key, and find one with a “DriverDesc” string value matching a NIC; (3) opening the “Ndi” key under the matching sub-key; (4) getting the “DeviceID” string value under the “Ndi” key; and, (5) searching the “DeviceID” string for a backslash “\” character. If the backslash character is found, then it can be concluded that the network interface card entry is associated with “real” physical hardware. Otherwise, it can be concluded that the network interface card entry is associated with a “virtual” device. In one particular embodiment, the present invention is implemented as part of a network configuration software or network monitoring software and allows users or system administrators to more easily monitor and modify the settings for network interface cards installed on a computer system running on Windows 95® or Windows 98® operating systems. | 7 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a Continuation of U.S. patent application Ser. No. 11/380,884 filed Apr. 28, 2006, now U.S. Pat. No. 7,913,939, which claims priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application Ser. No. 60/676,621 filed Apr. 29, 2005, all applications being incorporated herein in their entirety by this reference.
FIELD OF THE INVENTION
[0002] This invention provides low-cost, non-thermal methods to transform and beneficiate bulk materials, including low rank coals, to provide premium feedstock for industrial or commercial uses.
BACKGROUND OF THE INVENTION
[0003] Low Rank Coals (LRC) comprise almost 50% of total coal production in the United States, and about one-third of the coal produced worldwide. LRCs are characterized by their high levels of porosity and their water content which is retained in three basic forms: interstitial, capillary and bonded. Removal of the voids in which air, gas, and water reside in these coals requires primary comminution followed by compaction and higher energy inputs as transformation becomes more rigorous. The excess constituents, including air, gas, and water that would otherwise dilute the combustible material, are progressively expelled as interstitial voids between particles, and pores contained in the particles are eliminated.
[0004] The utility and gasification industries have long recognized the benefits of reducing these constituents in coal. Numerous beneficiation systems of varied technical complexity have been designed, but almost all use some form of thermal energy such as flue gas, steam, hot oil, hot water or the like, to remove water and some organic material (see, Davy-McKee, Inc. Comparison of Technologies for Brown Coal Drying , Coal Corporation of Victoria, Melbourne Australia (1984)). The technical, economic and environmental benefits realized by the use of these thermal drying procedures have been well documented and include increased power plant efficiency, increased generating efficiency, reduced greenhouse gas emissions, reduced dependence on carbon dioxide disposal systems, increased value of the LRC resources and reduced parasitic power consumption. But while these thermal beneficiation systems are technically effective, they are also expensive to build, costly to operate, site restricted, and must compete with other market opportunities for the energy they consume.
[0005] Additionally, thermal drying can produce coal dust that leads to unacceptably dangerous fuel products. High temperature thermal drying of coal, especially LRCs, largely alters the chemical characteristics of the fuel. The dried product is more reactive to air and may rapidly rehydrate, thus providing greater opportunity for spontaneous combustion and catastrophic fires. High volumes of coal fines and dust associated with thermally dried LRC create handling problems and product losses during rail transportation and handling, and some thermal drying systems are unable to process LRC fines of less than one-quarter inch and require alternative processing or result in substantial waste.
[0006] Thus, new coal benefication techniques are needed that can realize the substantial benefits of drying LRCs without the economic disincentives and production hazards associated with thermal drying techniques.
SUMMARY OF THE INVENTION
[0007] This invention provides new beneficiation methods that can be applied to transform a wide range of bulk materials and that does not use thermal energy or adversely alter the chemical nature of these materials. This methodology takes advantage of the fact that most of the gas and water is held in microscopic voids in the structure of the bulk materials and especially in low rank coals (LRCs). Comminution and high compaction forces are applied to transform the structure of these bulk materials by destroying most of the internal voids to release the air, gas, and liquids and preventing their recapture by sorption. By reducing or destroying these voids, this methodology produces a dense, compact, solid material. In the case of coal transformation this methodology produces a fuel with higher energy and fewer deleterious components. The end products of these techniques may be customized for the mining, transportation and consumer industries.
[0008] The methods and apparatus disclosed herein exert extreme compaction forces on prepared LRC feedstocks in order to destroy the interstitial, capillary, pores and other voids, thus transforming the physical characteristics of LRC and other similar bulk materials. Air and gas are expelled and water is transferred to the surfaces of the LRC particles where it is removed by mechanical means or during pneumatic transfer to produce clean and compact final products.
[0009] Unlike many expensive batch processes that use thermal energy and low compaction forces to heat and squeeze the coal, the present invention uses no thermal energy and operates in a continuous mode. These continuous processes result in higher throughputs than batch processing, significantly lower operating costs as no thermal energy is required, and greater safety as no external heat is applied. Additionally, the products formed are more stable as minimal rehydration of the dried products takes place and therefore less dust and fines are generated compared to thermal drying techniques. The environmental impact of high temperature drying techniques are substantially reduced by the processes disclosed herein because the organic rich effluents that are produced by thermal drying are minimized or eliminated by the techniques of the present invention.
[0010] These inventive processes include compaction and comminution of the bulk coal feed material, and multiple stages of compaction and comminution can be used to achieve the desired heat content for either existing or new coal-fired projects. The products can then be agglomerated to a suitable top size for transportation or alternate uses.
[0011] In one preferred configuration, the bulk starting material is comminuted then compacted between counter-rotating rolls. In this process gases may be dissipated as internal voids within the material are destroyed, and expelled liquids are separated from the solids by mechanical removal in liquid phase from the rolls, and in gas phase during transport to a subsequent processing that may include additional cycles of comminution and compaction.
[0012] One embodiment is a method of transforming a bulk starting material including compacting a bulk material and then comminuting the compacted bulk material to form a comminuted material. The comminuted material may have fewer void spaces than the bulk starting material. The bulk material useful in these methods is composed of particles that hold gases or liquids within void spaces within the solid particles. Typically, the bulk material is a carbonaceous material such as bituminous coal, peat, low-rank coals, brown coal, lignite and subbituminous coal or carbonaceous materials that have been pre-processed using beneficiation procedures such as thermal drying, washing, biological and chemical beneficiation, dry screening or wet screening. The bulk material may also be gypsum, coke, expandable shales, oil shale, clays, montmorillonite, and other naturally-occurring salts including trona, nacolite, borite, and phosphates. When undergoing compaction at high pressures, gases and/or liquids are forced from void spaces in the bulk material.
[0013] In one embodiment, the bulk material is first crushed or broken to an average particle top size between about 0.006 inch and about 1 inch prior to moving the bulk material to the compacting machinery. If needed, the bulk material is stored in a collection vessel, such as a surge bin, after crushing and prior to compacting, and this allows the bulk material to be fed at a controlled rate to compacting machinery. The bulk material may be frozen, chilled or heated if desired. However, the bulk material is preferably processed and stored at ambient temperature to minimize energy expenditure and processing costs and to maintain liquids and gasses in the bulk materials in a liquid or gaseous state to facilitate their removal from the bulk materials during processing.
[0014] The bulk material is subjected to a compaction pressure of at least about 3000 psi, and typically at a pressure as high as about 80,000 psi. Preferably, the bulk material is subjected to a pressure between about 20,000 psi and about 60,000 psi during compaction, and more preferably, the bulk material is subjected to a pressure of about 40,000 psi during compaction. The compaction pressure is applied for short time periods of between about 0.001 seconds and about 10 seconds.
[0015] In one embodiment, the compacting is performed by feeding the bulk material between two counter-rotating rolls aligned in proximity to one another. The compaction pressure is applied to the bulk material as the material is fed between the rolls. In this embodiment, the void spaces within the bulk materials may be crushed and eliminated from the materials as the material passes between the counter-rotating rolls forcing liquids and gases from the bulk material. These counter-rotating rolls may be cleaned with companion rollers, squeegees or blades. The counter-rotating rolls may be driven by a reducer and an electric motor at a speed that provides a bulk material residence time within the compression zone of the rollers of between about 0.001 seconds and about 10 seconds. The bulk materials of this embodiment are compressed into a ribbon that exits the rollers and breaks or fractures into large compacts.
[0016] Compressed materials are comminuted to reduce the particle size of compacts that have been produced by the high compaction pressures described above. The comminuting may include cutting, chopping, grinding, crushing, milling, micronizing and triturating the compressed materials. Preferably, the comminuting methods used can accept and process compressed materials at a rate equal to the rate at which the compacts exit the compacting machinery. If this is not convenient, the compressed materials can be collected and stored or held briefly until they are introduced to the comminuting machinery at a controlled rate. The compressed material is comminuted to an average particle top size between about 0.006 inch and about 1 inch. The comminuted material may then be dried, packaged, stored, pneumatically transferred to another facility for additional processing such as separation of solids and gases, and the like.
[0017] These processes of compacting and comminuting the bulk material may then be repeated as many times as desired to continue the transformation of the material, further eliminating void spaces and the liquids or gases therein with each successive round of compaction and comminution.
[0018] In another embodiment, the comminuted bulk material is subjected to another compression step. This second compression may be designed to specifically remove liquids from the surfaces of the materials. In this embodiment, comminuted material is compressed using compaction machinery that absorbs liquids present on the transformed materials. This compaction is preformed at a compaction pressure between about 3,000 psi and about 15,000 psi. This compaction to remove additional liquids present is conducted by contacting the comminuted material with a porous compaction surface. This porous compaction surface may absorb liquids from the comminuted materials. The separated liquids may be carried away from the materials. Preferably, this compacting is performed using counter-rotating rolls composed of porous materials. These porous counter-rotating rolls may absorb liquid into the porous material to be pulled away from the comminuted materials and collected or discharged to the environment. Liquids may be removed from the surface of the porous counter-rotating rolls with a scraper blade. Bulk material exiting the porous counter-rotating rolls may have a lower liquid content than the comminuted feed material.
[0019] Another embodiment described herein is an absorptive roll assembly that can be used in the compaction between two counter-rotating rolls to remove liquids from a bulk material. These rolls are composed of a central shaft supported by bearings at each end of the central shaft and end pieces affixed around the central shaft between the bearings. Liquid receptors are affixed around the central shaft between the end pieces. The liquid receptors contain an absorptive porous material that can wick liquid from a bulk material compressed against the porous material. The end pieces preferably contain weep holes that direct liquids absorbed in the porous rolls towards the ends of the central shaft and away from the bulk materials. Preferably, liquid receptors can be independently detached and replaced on the central shaft.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 shows a schematic drawing of a plan view of a single absorber roll useful in an absorptive counter-rotating roll assembly.
[0021] FIG. 2 shows an elevation at section A-A of the roll of FIG. 2 .
[0022] FIG. 3 shows an elevation at section B-B of the roll of FIG. 2 .
[0023] FIG. 4 shows a schematic diagram of processing procedures of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The present invention is drawn to a process that efficiently transforms bulk materials such as low rank coal (LRC) into economically useful feedstocks with lower environmental impact and hazards production than has previously been possible. Additionally, apparatuses useful for carrying out these transformative processes on bulk materials are described herein.
[0025] Bulk materials contain interstitial spaces between the particles of bulk material as well as capillary or pore spaces that exist within each individual bulk particle. For the purposes of this disclosure, these interstitial, capillary and pore spaces are referred to collectively as “void” space within the bulk material. The transformation processes of the present invention are performed by applying compaction and comminution forces to a bulk material sufficient to collapse and destroy these void spaces that exist within the bulk materials. These processes expel substances, including gases and liquids that reside in the void spaces from the bulk material. In these transformation processes, the substances are separated from the bulk material.
[0026] These processes include compaction and comminution of the bulk materials followed by sorption of liquids from the comminuted products. The comminuted products may then be subjected to further evaporative drying steps to complete the initial transformation of the bulk products. The transformed products may optionally be subjected to subsequent rounds of these transformation steps.
[0027] Bulk materials suitable for transformation in the processing procedures of the present invention may include any solid feed materials that hold gases or liquids within void space or on the surface of the solids. These materials may be naturally occurring carbonaceous materials including bituminous coal, peat and low-rank coals (LRCs), which include brown coal, lignite and subbituminous coal. The bulk feed material may similarly contain carbonaceous materials that have undergone prior processing such as bituminous coal, peat, and LRCs that have undergone pre-processing using thermal drying methods, washing processes, biological beneficiation methods, or other pre-treatment processes, or dry or wet screening operations. Additionally, the bulk material may be gypsum, coke, expandable shales, oil shale, clays, montmorillonite, and other naturally-occurring salts including trona, nacolite, borite and phosphates.
[0028] Liquids or gasses commonly reside in the void spaces of these bulk materials or are adsorbed on the surfaces of the materials or absorbed within the pores or capillary spaces of these bulk materials. Any liquids present are typically water or organic chemicals associated with the bulk materials. The transformative processing disclosed herein forces these gas and liquid materials from the bulk materials as the interstitial or porous spaces in the materials are destroyed.
[0029] The bulk materials may optionally be prepared for the initial compaction stage by processes designed to size the bulk particles to a size acceptable as a feed to the compaction machinery. Typically, the bulk materials are reduced in size by processes such as pulverization, crushing, comminution or the like to a suitable feed size and passed to a collection device or vessel where they can be stored or fed at a controlled rate to the compaction machinery. A similar rate control apparatus may be used to house the bulk materials before they are fed to an initial comminution device to produce the desired average feed particle top size. This bulk material may then be subjected to the first compaction step of the transformation processes of the invention. In a preferred embodiment, the bulk materials are comminuted to a particle size distribution of a top size of at least about 0.006 inch, but less than about 1 inch. Preferably, the average particle top size of the bulk material is reduced to about 0.04 inch prior to passing the bulk material to a holding or rate control apparatus and before passing the bulk material to the first stage compaction step.
[0030] The initial process in the transformation of the bulk materials is compaction of the materials at high pressure. The compaction preferably removes void spaces within the particles of the bulk material. The compaction pressure applied must be sufficient to reduce or destroy at least a portion of any void spaces present in the bulk materials. Typically, the bulk material is compacted under a pressure of at least about 3000 psi. The bulk materials may be compacted at much higher pressures including as high as 80,000 psi or higher. Preferably, the compaction pressures are between about 20,000 psi and about 60,000 psi. More preferably, the compaction pressures are between about 30,000 psi and about 50,000 psi. Even more preferably, the compaction pressure applied to the bulk materials is about 40,000 psi.
[0031] The bulk materials are preferably compacted at ambient temperature although cold or even partially frozen materials may be successfully processed. If there is a liquid absorbed within or adsorbed to the bulk materials, the materials should be warm enough to drive the liquid from void spaces in the material and this is most efficient if the temperature of the compacted materials is sufficiently high to keep the liquids from freezing. Similarly, the products may be warmed or hot at the time of compaction although little transformative effect is gained by providing heated materials to the compaction step. Most preferably, the bulk materials are compacted at an ambient temperature at which any liquids present in the void spaces remain in a liquid or gaseous state thereby facilitating their removal from the bulk materials.
[0032] The compaction pressure is applied to the bulk materials for the time necessary to transform the feed. Typically, the compaction pressure is applied for a period of at least 0.001 seconds. The compaction pressure may be applied to the bulk material for as long as about 10 seconds or longer. Preferably the compaction pressure is applied for a time period between about 0.1 seconds and about 1 second.
[0033] In one embodiment, the compaction is carried out by feeding the bulk material through two counter-rotating rolls in proximity to one another so as to provide the appropriate compaction pressure to the bulk material. The two counter-rotating rolls apply mechanical compaction forces to the bulk feed material by compacting the material between a specified gap between the rolls with a force that is sufficient to transform the feed material, while allowing liquids and/or gases within the feed material to be separated from the compacted product as void spaces occurring in the material are eliminated. The counter rotating rolls used preferably provide a compaction pressure to the bulk material of at least 3000 psi and more preferably the rolls are adjustable within the range of about 3000 psi and about 80,000 psi as described above. As the bulk materials are compacted between the counter-rotating rolls, the rolls may be cleaned with companion rollers, squeegees, blades or the like to draw away liquids or debris such as roll scrapings separated from the bulk materials by the application of the compacting pressure. The two counter-rotating rolls providing the compaction pressure to the bulk materials may be driven by a suitable reducer and electric motor at a circumferential speed that provides the desired process capacity and material residence time within the compression zone. In one embodiment, the relative rotation rate of the compaction rolls may be unity. Alternatively, the compaction rolls may be rotated asynchronously to provide a shearing force as well as compaction force to the bulk material. In this instance, the additional shearing force combined with the high pressure compaction forces may further reduce the void spaces in the bulk material.
[0034] The compacted materials, or compacts, exit the first compaction step in a compressed form that has fewer or lower void space compared to the bulk material applied to the compaction step. In the instance in which the compaction processes is performed using two counter-rotating rolls, the compacts exit the compacting rolls as a ribbon that will subsequently break into compacted pieces of bulk material that typically have a top size between about 0.5 inch and about 10 inches.
[0035] The compacted products exiting the compaction process are then comminuted. Preferably, the comminution is sufficient to reduce the particle size of the material. Any suitable means of breaking up or crushing the compacted products to reduce the particle size is useful at this stage of the transformation process. Comminution in its broadest sense is the mechanical process of reducing the size of particles or aggregates and embraces a wide variety of operations including cutting, chopping, grinding, crushing, milling, micronizing and trituration. For the purposes of the present disclosure, comminution may be either a single or multistage process by which material particles are reduced through mechanical means from random sizes to a desired size required for the intended purpose. Materials are often comminuted to improve flow properties and compressibility as the flow properties and compressibility of materials are influenced significantly by particle size or surface area of the particle.
[0036] Preferably, a comminution technique is used that is capable of processing the compacted products at a feed capacity equal to, or greater than, the rate at which compacted materials are being continuously produced from the compactor. If comminuting machinery incapable of this processing speed is used, a suitable means of collecting the compacted products and regulating their feed rate into the comminuting machinery may be used. It should be noted that if counter-rotating rolls are used to compact the bulk materials as described above, the rate of compaction can be modified by adjusting the rotation rate of the rolls. Preferably, the type of comminution process used is chosen to produce a product of a particle size distribution best suited for compaction and transformation.
[0037] The compacted bulk materials are comminuted to an average particle top size of at least about 0.006 inch. The average particle top size is preferably less than about 1 inch. The average particle top size of the bulk material is more preferably reduced to about 0.04 inch in this comminution step prior to passing the bulk material onto further processing. The bulk materials that have been compacted and comminuted in the processes of the present invention have more desirable physical characteristics than the starting materials including, greater particle density, lower equilibrium moisture content, lower water permeability, lower gas permeability, lower porosity, lower friability index and lower gas content than the bulk starting materials. In the instance in which low rank coals are subjected to the transformation processes of the present invention, in addition to the desirable physical characteristics listed above, the compacted and comminuted coal products may also have a higher heating value, lower carbon dioxide content, lower soluble ash content and lower sulfur content than the LRC feed material. Additionally, the compacted and comminuted coal products may be added to water to form a slurry that has a greater heating value than a similar slurry formed from the LRC feed material.
[0038] Following comminution the comminuted products may be stored, subject to air or evaporative drying, pneumatically transferred to a cyclone, bag house, or similar gas/solids separator for further separation of gasses and vapors, subjected to additional compaction designed to remove liquids that may remain in the comminuted products or further processed for specialized commercial uses. The comminuted products may also be subject to additional cycles of compaction and comminution. Each succeeding round of compaction and comminution further transforms the bulk materials by removing more void space from the transformed materials.
[0039] In one embodiment, the comminuted products are subjected to further compaction configured to reduce the presence of liquids remaining in the comminuted products. Considerable liquid may reside on or near the surface of the comminuted material following a cycle of compaction and comminution. The use of additional absorptive machinery further separates this liquid from the solids using high pressures. This optional absorptive step may be performed using a second, absorptive compaction step in which the transformed bulk materials are compacted again using machinery designed to absorb liquids present in the transformed materials. This is preformed by applying a compaction pressure of at least about 3,000 psi. Preferably, the comminuted products undergoing this absorptive compaction are subjected to compaction pressures between about 5,000 psi and about 15,000 psi. Preferably, some or all of the liquids residing in the comminuted products are removed through the use of porous compaction machinery that will absorb liquids from the compacted materials and carry the liquids away from the materials. For example, another set of counter-rotating rolls composed of porous materials that allow liquids residing on the surface of the feed material to be separated from the solids may be used in this optional absorptive compaction step. The porous material of these rolls may contain a sintered metal that has low permeability and a mean pore size of less than about 2 microns. Alternatively, the porous material of these pores may be porous ceramic having a low permeability and a mean pore size of less than about 2 microns. Liquids present in the transformed materials are forced from the materials and driven into the pores of the rolls at a rate sufficient to produce a satisfactory product.
[0040] FIG. 1 shows a schematic drawing of a plan view of a single preferred absorber roll used in the absorptive counter-rotating roll assembly that may optionally be applied to the transformed products to pull liquids away from these materials. FIGS. 2 and 3 show two sectional elevations taken at sections A-A and B-B of the roll of FIG. 1 , respectively. Referring to FIG. 1 , the absorber roll unit consists of a central shaft ( 2 ) that is supported by bearings ( 3 ), end pieces ( 4 ) and liquid receptors ( 5 ). The receptors ( 5 ) are thin, ring-shaped pieces of material such as porous sintered metal or ceramic of a small pore opening and low permeability to provide a durable item that can withstand great mechanical stress, yet allow liquid/solid separation to take place under high pressure. These rings can be readily placed on the central shaft ( 2 ) to provide a unique roll configuration that suits the absorptive application of these compaction rolls. Damaged rings may therefore be removed and replaced without overhauling the entire roll assembly.
[0041] Referring to FIGS. 2 and 3 , the comminuted feed material ( 6 ) is diagrammatically shown entering under mechanical pressure from the left and exiting the right side of the horizontal roll assembly. Other orientations of feed entry are possible without consequence to the liquid/solid separation phenomena.
[0042] Companion rolls ( 7 ) identical in configuration to the roll assembly ( 1 ) described above are held in proximity to these rolls along a plane parallel to the axis of rotation. The rolls are propelled by a mechanical drive system of standard design to provide counter rotating motion. Mechanical means exert a specified force on the bearings ( 3 ) to maintain the gap between the rolls, thus providing the pressure to force liquid held on the comminuted feed material into the receptors. Liquid contained on the surface of the comminuted feed material ( 6 ) is compacted between the roll assembly ( 1 ) and companion roll ( 7 ). A portion of the liquid is absorbed under pressure by the receptors ( 5 ) as the comminuted feed is engaged by the rolls. Liquid absorbed by the receptors ( 5 ) migrates from the surface ( 8 ) of the receptors ( 5 ) and, after the receptors become saturated, flows ( 9 ) through numerous weep holes ( 10 ) in either of the end pieces ( 4 ). Liquid remaining on the surface ( 8 ) of the receptors ( 5 ) is collected and removed ( 11 ) from the roll assembly ( 1 ) by scraper blade ( 12 ). The collected and removed liquid ( 11 ) may be collected in a container ( 13 ) for disposal or further processing. In the instance in which LRCs are processed through the transformation methods of the present invention, the liquid recovered from this absorptive compaction processing will be primarily water and the water collected and recovered will be sufficiently clean for use in further industrial processes without additional purification. Unlike low-pressure roll devices, re-absorption of liquid into the product material is not of significance because the interstitial, capillary, pores, and other voids are largely absent due to the previous compaction. Compressed material ( 14 ) having a reduced liquid content exits this absorptive roll assembly for further processing.
[0043] Similar to the compacted products exiting the first, high-pressure compaction step, the compacts exiting this absorptive compaction step have a pressed form that has lower void space compared to the bulk material applied to this absorptive compaction step. Particularly, these compacts have a lower liquid and/or gas content than the bulk materials applied to the absorptive rollers. These compacts also exit the absorptive rollers in a compacted ribbon that subsequently breaks into compacts.
[0044] Similar to the post-compaction and comminution processing procedures described above, transformed materials processed through this optional absorptive compaction step may undergo additional processing including storage, air or evaporative drying, transfer to a bag house for further separation of gasses or further processed in preparation for specialized commercial uses. These bulk materials may also be fed to additional cycles of compaction and comminution to more extensively remove void space from the materials.
[0045] FIG. 4 shows a schematic representation of a preferred embodiment of these transformation processes applied to bulk materials, as well as machinery used in these processes. Referring to FIG. 4 , the feed preparation unit ( 21 ) accepts a bulk feed material ( 24 ) in a surge bin and feeder ( 25 ). A measured rate of material is reclaimed from the surge bin and crushed in comminution machinery ( 26 ) to the desired top size. Comminuted material ( 27 ) passes from the feed preparation unit to the first-stage compaction/crushing unit ( 22 ).
[0046] In the first-stage compaction/crushing unit ( 22 ), comminuted feed ( 27 ) is stored in a surge bin ( 28 ) and fed by a gravimetric feeder ( 29 ) at a controlled rate to the primary double-roll compaction machine ( 30 ). The machine produces primary compacted feed ( 31 ) and roll scrapings ( 32 ). The primary compacted product is crushed in comminution machinery ( 33 ). Comminuted product ( 34 ) is fed to an optional secondary double-roll absorption machine ( 35 ). The machine produces first-stage compacted product ( 36 ) and liquids ( 37 ) absorbed from the comminuted product ( 34 ). The first-stage compacted product ( 36 ) is collected in surge bin ( 38 ) where it is prepared for pneumatic transport. Atmospheric air ( 40 ) is pressurized by fan ( 39 ) to engage the prepared first-stage product to form a mixture ( 41 ) suitable for transport to a baghouse ( 42 ).
[0047] Fabric filters included in the baghouse ( 42 ) separate solids from vapor. An induced-draft fan ( 43 ) draws vapors ( 44 ) from the baghouse and discharges the gas to the atmosphere. Solids reclaimed by the baghouse ( 45 ) may optionally be directed to bypass further processing ( 46 ), or to additional processing ( 47 ) in a second compaction/crushing stage unit ( 23 ).
[0048] The second-stage compaction/crushing unit ( 23 ) is essentially identical to the first-stage compaction/crushing unit ( 22 ). Similar equipment includes the primary double-roll compaction machine, comminution machinery, optional secondary double-roll absorption machine, surge bin, and fan. Finished product ( 48 ) can pass to a final product collection device or to additional compaction/crushing stages. Additional rounds of compaction and comminution may be applied to the products ( 48 ) depending on the desired characteristics of final product. Deployment of the equipment needed to effect the transformative changes disclosed herein may be carried out rapidly and efficiently through the assembly and modification of commercially available equipment. Further processing may also include agglomeration and preparation for specific commercial uses.
[0049] Post-processing procedures may be applied to the transformed materials. These post-processing procedures are for the benefit of the mining, transportation or consumer industries. Any of these industries may benefit from the transformation of the bulk materials by realizing lower costs as estimated capital and operating costs may be less than 20% of bulk materials subjected to alternative thermal drying systems. Similarly, electricity inputs are estimated to be less than 20% of flue gas, steam, hot oil, and the like, used in some thermal processing options. With respect to the processing of LRCs using the processing technologies of the present disclosure, the heat value of the transformed products may exceed 10,000 Btu/lb, while the removal of some of the sulfur, sodium, oxygen, carbon dioxide and nitrogen emissions from the burning of the transformed coal may mitigate the production of greenhouse gas emissions. Additionally, with respect to dust control measures, the compaction procedures disclosed herein will mitigate most windage losses during handling and transportation of the transformed materials. Also, the potential for spontaneous combustion resulting from rehydration is minimized when internal voids are destroyed by compaction.
[0050] Another embodiment is the compacted product resulting from the application of the methods disclosed herein to bulk materials. These compacted materials can have many desirable physical characteristics for industrial use including a low equilibrium moisture content (EMQ). Thus, these compacted materials can have a very low level of rehydration. Typically, the EMQ of these compacted materials is less than about 26%. Preferably, the EMQ of these compacted materials is less than about 20% and more preferably less than about 15% and more preferably, less than about 10%. Typically, the EMQ of the compacted materials is between about 10% and about 25%. For some compacted materials, an EMQ of less than about 25% represents a significant and advantageous decrease in the EMQ of the starting bulk material, prior to processing according to the methodology of the present invention. Thus, using the techniques described herein, it is possible to reduce the EMQ of the starting material by at least about 5%. Typically, the EMQ of the starting bulk material is reduced by between about 5% to about 70% with successive rounds of compaction and comminution as disclosed herein. Preferably, the EMQ of the compacted material is reduced by about 10% compared to the EMQ of the non-compacted, starting materials. More preferably, the EMQ of the compacted material is reduced by about 20% compared to the EMQ of the starting (non-compacted) materials, and more preferably, the EMQ of the compacted material is reduced by about 30% compared to the EMQ of the starting materials, and more preferably, the EMQ of the compacted material is reduced by about 40% compared to the EMQ of the starting materials, and more preferably, the EMQ of the compacted material is reduced by about 50% compared to the EMQ of the starting materials and more preferably, the EMQ of the compacted material is reduced by about 60% compared to the EMQ of the starting materials.
[0051] Additional objects, advantages, and novel features of this invention will become apparent to those skilled in the art upon examination of the following examples thereof, which are not intended to be limiting.
EXAMPLES
Example 1
[0052] A detailed study of two bulk materials (high-moisture lignite from South Australia and brown coal from Victoria, Australia) was undertaken to assess the effects of particle size, washing and leaching, additives, agglomeration, briquetting, slurrying, rehydration, autoclaving, and the application of thermal energy and pressure, as effective methods of transforming or beneficiating low rank coal (LRC) to provide a more useful, cost effective, clean fuel. The test program revealed comminution to a specific particle size range and compaction, configured in the continuous mode of the present invention to be the most beneficial factors in the mechanical transformation of LRC into a high quality fuel.
[0053] Published reports (Anagnostolpoulos, A., Compressibility Behaviour of Soft Lignite , J. Geotechnical Engineering 108(12): (1982); and Durie, R. Science of Victorian Brown Coal: Structure, Properties and Consequences of Utilisation , CSIRO, Sydney, Australia (1991)) dealing with similar LRCs showed that some moisture can be removed when low pressures in the range of 1400 psi to 2300 psi are applied to the material over several days at ambient temperatures. Similarly, low pressures of about 500 psi have been used in combination with thermal processing in several prototype beneficiation systems (McIntosh, M. Pre - drying of High Moisture Content Australian Brown Coal for Power Generation, 22 nd Annual International Coal Preparation Conference, Lexington, Ky. (2005); and Van Zyl, R. History and Description of the KFx Pre - Combustion Coal Process, 22 nd Annual International Coal Preparation Conference, Lexington, Ky. (2005)).
[0054] The present inventors' research shows that low-pressure compaction does not permanently transform the physical characteristics of these bulk materials.
Example 2
[0055] Various LRC samples were processed using the procedures and equipment diagramed in FIG. 1 and described above. The effects of these mechanical transformation processes and the quality of the finished compacted products were evaluated.
[0056] To evaluate the transformative effects and the quality of the finished products, the equilibrium moisture content (EQM) of LRC feeds and products was measured. The EQM is defined by the American Society of Testing and Materials (ASTM) procedure ASTM D-1412. The EQM is the moisture content held by coal stored at a prescribed temperature of 30° C. under an atmosphere maintained at between 96% and 97% relative humidity. Under these conditions, moisture is not visible on the surface of the coal, but is held in the capillary, pores, or other voids. Coals with low EQM contain less capillary, pores, or other void volume to hold water. These coals have typically more useful thermal energy than coals with higher EQM, and are subsequently more valuable as feedstock for energy generation processes. Table 1 shows the results of EQM testing conducted on samples of subbituminous coal supplied from the Power River Basin, Wyo., USA and lignite from North Dakota, USA, prior to, and after five successive stages of compaction/comminution. In each cycle of compaction/comminution, a compaction pressure of about 30,000 psi was applied at ambient temperature for less than 1 second.
[0000]
TABLE 1
Equilibrium Moisture Contents of
Raw Feed and Compacted Products
Subbituminous Coal
Lignite
Material
(Powder River Basin)
(North Dakota)
Unprocessed Feed
27.0%
32.4%
1 st Stage Compaction/
16.4%
26.2%
Comminution Product
2 nd -Stage Compaction/
15.7%
23.6%
Comminution Product
3 rd -Stage Compaction/
14.3%
21.9%
Comminution Product
4 th -Stage Compaction/
12.9%
20.0%
Comminution Product
5 th -Stage Compaction/
11.9%
18.6%
Comminution Product
[0057] These data show that compaction and comminution of LRC bulk materials using the processes of the present invention can significantly reduce the EQM of the bulk materials and that, with each successive round of compaction and comminution, the EQM is reduced. Additionally, these data demonstrate the ability to reduce the EQM of bulk materials by 20-40% after only one round of compaction and comminution, while the EQM can be lowered by 40-60%, or more, with subsequent rounds of compaction and comminution.
[0058] The foregoing description of the present invention has been presented for purposes of illustration and description. Furthermore, the description is not intended to limit the invention to the form disclosed herein. Consequently, variations and modifications commensurate with the above teachings, and the skill or knowledge of the relevant art, are within the scope of the present invention. The embodiment described hereinabove is further intended to explain the best mode known for practicing the invention and to enable others skilled in the art to utilize the invention in such, or other, embodiments and with various modifications required by the particular applications or uses of the present invention. It is intended that the appended claims be construed to include alternative embodiments to the extent permitted by the prior art. | The invention provides low-cost, non-thermal methods to transform and beneficiate bulk materials, including low rank coals such as peat, lignite, brown coal, subbituminous coal, other carbonaceous solids or derived feedstock. High pressure compaction and comminution processes are linked to transform the solid materials by eliminating interstitial, capillary, pores, or other voids that are present in the materials and that may contain liquid, air or gases that are detrimental to the quality and performance of the bulk materials, thereby beneficiating the bulk products to provide premium feedstock for industrial or commercial uses, such as electric power generation, gasification, liquefaction, and carbon activation. The handling characteristics, dust mitigation aspects and combustion emissions of the products may also be improved. | 2 |
TECHNICAL FIELD
This invention relates generally to the provision of cooling or refrigeration and, more particularly, to the provision of cooling or refrigeration to superconducting cable.
BACKGROUND ART
Superconductivity is the phenomenon wherein certain metals, alloys and compounds at very low temperatures lose electrical resistance so that they have infinite electrical conductivity.
It is important in the use of superconducting cable to transmit electricity, that the cooling, i.e. refrigeration, provided to the superconducting cable not undergo interruption lest the cable lose its ability to superconduct and the electrical transmission be compromised. While systems which can provide the requisite refrigeration to superconducting cable are known, such systems, such as closed loop turbo mechanical refrigeration systems, are costly, complicated and subject to breakdown, necessitating the use of back up systems to ensure uninterrupted cooling of the superconducting cable.
Accordingly, it is an object of this invention to provide a reliable method for providing cooling to superconducting cable which can be used as the primary or a back up means for providing cooling to superconducting cable.
SUMMARY OF THE INVENTION
The above and other objects, which will become apparent to those skilled in the art upon a reading of this disclosure, are attained by the present invention, one aspect of which is:
A method for providing cooling to superconducting cable comprising:
(A) passing liquid cryogen from a storage vessel to a vacuum vessel, and flashing a portion of the liquid cryogen into the vacuum vessel to produce vapor and cooled liquid cryogen within the vacuum vessel;
(B) pumping vapor out from the vacuum vessel; and
(C) passing cooled liquid cryogen from the vacuum vessel to superconducting cable and providing cooling from the cooled liquid cryogen to the superconducting cable.
Another aspect of the invention is:
A method for providing cooling to superconducting cable comprising:
(A) passing liquid cryogen from a storage vessel to a vacuum vessel, and flashing a portion of the liquid cryogen into the vacuum vessel to produce vapor and cooled liquid cryogen within the vacuum vessel;
(B) pumping vapor out from the vacuum vessel; and
(C) cooling refrigerant fluid by indirect heat exchange with the cooled liquid cryogen to produce cooled refrigerant fluid, passing the cooled refrigerant fluid to superconducting cable, and providing cooling from the cooled refrigerant fluid to the superconducting cable.
As used herein the term “cryogenic temperature” means a temperature at or below 120K.
As used herein the term “superconducting cable” means cable made of material that loses all of its resistance to the conduction of an electrical current once the material attains some cryogenic temperature.
As used herein the term “refrigeration” means the capability to reject heat from a subambient temperature entity.
As used herein the term “indirect heat exchange” means the bringing of entities into heat exchange relation without any physical contact or intermixing of the entities with each other.
As used herein the term “direct heat exchange” means the transfer of refrigeration through contact of cooling and heating entities.
As used herein the term “vacuum vessel” means a vessel which has an internal pressure less than the pressure of liquid cryogen passed into the vacuum vessel from a storage vessel.
As used herein the term “vacuum pump” means a compressor used to move gas from subatmospheric pressure to atmospheric pressure.
As used herein the term “flashing” means the vaporization of a portion of liquid wherein the portion of liquid vaporized absorbs latent heat of vaporization from its surroundings and therefore cools its surroundings. In this case, the remaining liquid not vaporized is cooled. Lowering the vapor pressure of the liquid induces flashing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of one preferred embodiment of the invention wherein cooled liquid from the vacuum vessel is used to provide cooling to the superconducting cable.
FIG. 2 is a schematic representation of another preferred embodiment of the invention wherein cooled liquid provides cooling to recirculating refrigerant fluid which then provides cooling to the superconducting cable.
DETAILED DESCRIPTION
In general, the invention comprises the use of a lower pressure vessel into which liquid cryogen is flashed to produce cooled liquid cryogen which is then used to provide cooling to superconducting cable. The invention provides high reliability cooling to the superconducting cable and is especially useful as back up to a main refrigeration system for the superconducting cable.
The invention will be described in greater detail with reference to the Drawings. Referring now to FIG. 1, liquid cryogen is stored in liquid cryogen storage vessel 1 at a pressure generally within the range of from 15 to 80 pounds per square inch absolute (psia). The preferred liquid cryogen for use in the practice of this invention is liquid nitrogen.
The liquid cryogen is withdrawn from storage vessel 1 in line 2 , passed through valve 3 and in line 4 passed to valve 5 which serves to control the rate at which the cryogen is passed into the vacuum vessel. From valve 5 the liquid cryogen is passed in line 6 to vacuum vessel 7 . Vacuum vessel 7 is operating at a pressure, i.e. has an internal pressure, which is less than the pressure of storage vessel 1 . Generally the operating pressure of vacuum vessel 7 at least 1 psi less than that of storage vessel 1 and typically will be from 1 to 80 psi less than that of storage vessel 1 . Generally the operating pressure of vacuum vessel 7 will be within the range of from 1 to 3 psia.
Because of the low pressure within vacuum vessel 7 , as the liquid cryogen is passed in line 6 into vacuum vessel 7 , a portion of the incoming liquid cryogen is flashed to vapor leaving the remaining liquid cryogen in a cooled condition. The cooled liquid cryogen settles in a lower portion of vacuum vessel 7 while the vapor occupies an upper portion of vacuum vessel 7 . Saturated liquid from the bulk storage tank is introduced into the vacuum vessel initially at the saturation properties of the bulk tank. The normal saturation temperature of the bulk tank is higher than the saturation temperature in the vacuum vessel due to the lowered vapor pressure. This imbalance causes a portion of the liquid to vaporize immediately upon introduction into the vacuum vessel such that a saturated condition can be reestablished. The vaporized liquid provides cooling to the remaining liquid. This occurs because the portion of liquid vaporized absorbs latent heat of vaporization from its surroundings. The cooled remaining liquid is then able to attain its lowered saturation temperature that corresponds to the vapor pressure in the vacuum vessel. Liquid will continue to vaporize until the remaining liquid attains its lowered saturation temperature.
In order to maintain the internal or operating pressure of vacuum vessel 7 at the requisite lower pressure, the vapor is pumped out of the vacuum vessel. In the embodiment of the invention illustrated in FIG. 1, the vapor is pumped out of vacuum vessel 7 by operation of vacuum pump 8 . Vapor is withdrawn from vacuum vessel 7 in line or stream 9 , passed through valve 10 and in line 11 passed to electric heater 12 . A heater is used here to raise the temperature of the vaporized cryogen to a suitable level for the inlet of the vacuum pump. An electric heater is preferred because it provides a lower pressure drop over other types of heaters such as an atmospheric superheater. The vented vaporized cryogen still has refrigeration value and it may be used for other required cooling duty, in which case a smaller heater or no heater will be required. From electric heater 12 the vapor passes in line 13 to vacuum pump 8 and from there in line 14 is passed to vent 15 and released to the atmosphere.
Cooled liquid cryogen is withdrawn from the lower portion, preferably the bottom, of vacuum vessel 7 in line or stream 16 , passed to cryogenic pump 17 , and from there in line 18 is passed to superconducting cable 19 . The cooled liquid is warmed by either direct or indirect heat exchange with the superconducting cable thereby providing cooling, i.e. refrigeration, to the superconducting cable so as to maintain the superconducting cable at the requisite cryogenic temperature.
The liquid cryogen is withdrawn from superconducting cable segment 19 in line 20 . The liquid cryogen in line or stream 20 is generally and preferably still in a liquid state. The cooled liquid cryogen is then passed through valve 21 and then in line 22 is combined with the cooled liquid cryogen in line 6 for passage into vacuum vessel 7 for flashing and the further generation of cooled liquid cryogen.
FIG. 2 illustrates another embodiment of the invention wherein the cooled liquid cryogen is used to cool recirculating refrigerant fluid which is then employed to provide the cooling to the superconducting cable. The numerals of FIG. 2 are the same as those of FIG. 1 for the common elements, and these common elements will not be described again in detail.
Referring now to FIG. 2, refrigerant fluid in line or stream 23 is passed through heat exchanger 24 wherein it is cooled by indirect heat exchange with cooled liquid cryogen which has been produced as a result of the flashing of the liquid cryogen into vacuum vessel 7 . Preferably, as illustrated in FIG. 2, heat exchanger 24 , and the heat exchange between the refrigerant fluid and the cooled liquid cryogen, is located within vacuum vessel 7 . The preferred refrigerant fluid for use in the practice of this invention is nitrogen, which will always be in a liquid state.
The cooled refrigerant fluid is withdrawn from heat exchanger 24 and passed in line 25 to superconducting cable 19 wherein it provides cooling or refrigeration to the superconducting cable in a manner similar to that previously described with reference to FIG. 1 . The warmed refrigerant fluid is withdrawn from the superconducting cable segment in line 26 and passed through cryogenic pump 27 , emerging therefrom in line 23 for recirculation back to heat exchanger 24 .
Although the invention has been described in detail with reference to certain preferred embodiments, those skilled in the art will recognize that there are other embodiments of the invention within the spirit and the scope of the claims. | A method for providing cooling to superconducting cable wherein pressurized liquid cryogen is passed into a vacuum vessel, which is maintained at a lower pressure by a vacuum pump, and a portion of the liquid cryogen is flashed to produce cooled liquid cryogen. The evacuating energy combined with the pressurized liquid produces a pressure gradient which serves to provide a continuous supply of cooled liquid cryogen for providing cooling to the superconducting cable. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a Continuation Application of U.S. patent application Ser. No. 10/359,734, filed on Feb. 7, 2003, incorporated herein by reference, which is a Continuation Application of U.S. patent application Ser. No. 08/671,873, filed on Jun. 28, 1996, now U.S. Pat. No. 6,542,150, also incorporated herein by reference. The present invention is related to application Ser. No. 08/673,793, entitled “METHOD AND APPARATUS FOR EXPANDING GRAPHICS IMAGES FOR LCD PANELS” filed Jun. 27, 1996, now U.S. Pat. No. 6,067,071, also incorporated herein by reference.
FIELD OF THE INVENTION
The present invention is in the field of portable computers, namely laptop, notebook, or similar portable computers with flat panel displays with or without SIMULSCAN™ capability. In particular, the present invention relates to displaying graphics data on fixed resolution LCD panel displays.
BACKGROUND OF THE INVENTION
Popularity of portable computer systems has driven computer designers to integrate more processing power, more memory capacity, and more peripherals into a single portable unit. Advances in core logic, a term known in the art to comprise support logic, and other common circuitry integrated into a chip or chipset, allows more functionality to be placed in smaller, lighter packages.
A primary element of a portable computer system is a display. Since Cathode Ray Tube (CRT) displays are relatively large and heavy, with high power requirements, other alternatives have actively been sought. Flat panel display technology represents a significant alternative to CRT display technology. Flat panel displays may have several advantages over CRT displays. Flat panel displays include a number of different display types, Liquid Crystal Display (LCD) being most commonly used. LCD displays may have advantages of being compact and relatively flat, consuming little power, and in many cases displaying color.
Typical disadvantages of LCD displays may be poor contrast in bright light—especially bright natural light, inconsistent performance in cold temperatures, and display resolutions which may be constrained by a fixed number of row elements and column elements. Among these limitations, fixed resolution may cause significant problems for LCD operation in a multimedia environment. Multimedia users may demand a monitor which can be configured for different display resolutions. Analog CRT displays may be easily configured for different resolutions.
Flat panel displays may typically comprise two glass plates pressed together with active elements sandwiched between. High resolution flat panel displays use matrix addressing to activate pixels. Conductive strips for rows may be embedded on one side of a panel and similar strips for columns are located on the other side. Panels may be activated on a row by row basis in sequence. This process may be described in more detail in a text entitled: “High Resolution Graphics Display Systems”, Peddie 1.994 (pp. 191-225), incorporated herein by reference, however the general nature of LCD addressing is known in the art.
LCD flat panel display resolution may be dictated by physical construction of an LCD. CRT displays have a continuous phosphor coating and may be illuminated by an analog signal driving an electron beam. Because of the analog nature of CRT, scaling display resolution is relatively simple. LCD displays have a fixed array of physical pixels which may be turned on or off by applying or removing a charge.
While resolution of a CRT may be changed by changing scanning frequency parameters, LCDs are limited by a fixed number of row and column elements. Fixed resolution LCD displays are particularly troublesome in multimedia systems. Such systems may require changes in display resolution to take full advantage of applications displaying high resolution graphics. In addition, for a manufacturer of display controllers to claim full VGA, SVGA, and XGA compatibility limitations of fixed panel resolution must be overcome.
TABLE 1
Vertical scanning frequencies for different graphics
display modes
Typical
Vertical Scan
Panel Type
Resolution
Frequency
VGA Panel
640 × 480
25 Mhz
SVGA Panel
800 × 600
40 Mhz
XGA Panel
1024 × 768
65 Mhz
Like an analog CRT, an LCD panel may be controlled by a horizontal and vertical scanning signal. Data may be displayed in its respective screen position during an interval in time corresponding to when vertical and horizontal scan signals for a particular location coincide. Horizontal and vertical scan signals are set at a frequency proportional to display resolution. Table 1 contains vertical scanning frequencies for popular graphics display modes.
Typical vertical scanning frequencies may be 25 MHz for 640 pixels by 480 pixels display, 40 MHz for 800 pixels by 600 pixels, and 65 MHz for 1024 pixels by 768 pixels. New panels comprising 1280 pixels by 960 pixels may have an even higher vertical scanning frequency. A high resolution display therefore may have a higher scanning frequency than a relatively lower resolution display.
Most multimedia computers have the ability to select from one of several display resolutions. Common display resolutions may be 640 pixels by 480 pixels, 600 pixels by 800 pixels, and 1024 pixels by 768 pixels. A standard fixed resolution LCD display may be 600 pixels by 800 pixels. A standard universal VGA resolution may be 640 pixels by 480 pixels with 256 colors. When a low graphic resolution must be displayed on a fixed resolution LCD display certain problems may arise. To properly display all VGA modes in a portable computer environment with a fixed resolution LCD panel display, desired graphics resolution must be scaled to the panel resolution. Fewer problems are inherent in downscaling, when desired display resolution is larger than the panel. Upscaling however may present special problems.
Using the general principal stating high frequency is proportional to high resolution, some downscaling may be achieved by attempting to replicate lower scanning frequencies of low resolution display while maintaining native scanning resolution. On a fixed resolution display of 600 pixels by 800 pixels for example, a 640 pixel by 480 pixel resolution output may be scaled by lowering the frequency at which data is clocked to the display. This type of approach to expansion related problems may be considered synchronous. Synchronous approaches may have disadvantages for expanding certain resolutions.
Because of the relationship between scan frequencies for certain resolutions that need to be expanded, synchronous approaches to expansion may not be desirable. Visual anomalies such as flicker, and related line dropping may cause noticeable and annoying visual artifacts. Also, horizontal flicker may be noticed and is even more annoying as portions of the display shift from side to side. This is due to the inability of the expansion scheme to account for every line generated at one resolution to a corresponding line on a second resolution. Resolutions which divide evenly into each other may be best suited for synchronous approaches.
Asynchronous approaches may be necessary when the ratio of CRT display lines and LCD display lines, based on different desired display resolution and fixed resolution display capability, is non-integral and when it is generally considered desirable to decouple the time base upon which display data is generated from the time base upon which output display resolution is generated. Consider an example when 3 LCD display lines must be displayed for every 2 CRT lines.
Prior art methods use relatively expensive dual path approaches which may replicate hardware for each display sought to be driven. In addition to hardware costs, bandwidth requirements may be approximately doubled and available bandwidth cut by approximately half for a dual path approach. Other disadvantages of a dual path approach may be non-transparency of software. With a dual path approach, display related software may require separate modification to standard register contents, standard addresses or the like in order to operate at each resolution.
For transforming graphics resolutions, fewer problems are inherent in downscaling, when desired display resolution is larger than the panel. Upscaling however may present special problems. When attempting to display lower resolution graphics on a higher resolution, fixed resolution panel display a variety of compensation methods may be used. Compensation features may be made available through use of shadow registers and extension registers. Both compensation method and desired parameters, such as output resolution may be set through use of registers.
Some systems employ a compensation technique known as centering. With centering, a smaller resolution graphic image may be placed within a larger resolution display in the center of the display. One problem associated with centering a 640 pixel by 480 pixel display at full color within, for example, a 1024 pixel by 768 pixel display is limited bandwidth. On a display which supports 640 pixels by 480 pixels in native mode (e.g at native 640 pixel by 480 pixel timing of 25 Mhz), there may be sufficient bandwidth to support 24 or 32 bits per pixel of color.
As frequency increases such as on a fixed panel 1024 pixel by 768 pixel display which does not support the native timing for 640 pixels by 480 pixels resolution, bandwidth requirements increase in proportion to increase in frequency between resolutions. Most 32 or 64 bit controller may only support 24 or 32 bit full color at a native resolution of 640 pixels by 480 pixels. Another problem with centering and prior art expansion techniques is the scope of programming required to support it. Many shadow registers must be programmed, and protection mechanisms must be in place to configure and then preserve the expanded display settings.
FIG. 1 is a diagram illustrating a prior art technique of centering. During centering, Graphics Window 200 with a resolution of 640 pixels by 480 pixels may be displayed on Fixed Resolution Panel 201 which is capable of displaying at a fixed resolution of 1024 pixels by 768 pixels. Graphics Window 200 may be generated by a software application such as a computer game with high resolution graphics. For consistency and compatibility purposes, such a computer game may generate a display with a resolution of 640 pixels by 480 pixels regardless of the resolution capability of the display.
Differences in size must be accommodated to physically center a smaller display within a larger resolution panel. Additionally, differences in normal VGA timing which may be around 25 Mhz, and native timing of an LCD panel which, for a 1024 pixel by 768 pixel display, may be around 65 Mhz must be accommodated. In other words, during centering, a panel must actively accommodate the difference between lower resolution graphics mode and higher resolution panel by generating blank pixels. The resulting display is often too small to be viewed acceptably. For a 1024 by 768 pixel panel there may be 9 or 10 inches of display surface of which one third may go unused during centering. Not only does this waste panel capability, but refresh rates are poor because of timing translation and often the displayed information is too small to read either in Windows™ or in DOS text mode. From an economic standpoint, a user pays a premium for the increased resolution of the panel display only to receive inferior performance.
Another compensation technique for vertical scaling is known as line replication. In line replication or stretching, every Nth line may be duplicated on a subsequent line. In text mode, blank line insertion may be used to evenly fill an entire panel.
Yet another problem arises when attempting to drive two display devices with different display resolutions either through a SIMULSCAN™ output or an auxiliary output. For example, if Microsoft™ Windows™ is running, a dual display mode may be activated by way of an icon as is done for SIMULSCAN™ displays. Requests may then be passed by Windows™ Graphic Driver Interface (GDI) to an appropriate display driver and hardware. Only one graphics resolution, however, may be selected for one or both displays at one time. In other words, separate display resolutions may not be desirable for each display in a particular SIMULSCAN™ environment. Thus, on a notebook system with an 800 pixel by 600 pixel LCD display, if a 640 pixel by 480 pixel resolution is chosen, for example, to drive an external LCD projection panel as a SIMULSCAN™ output, then the LCD output must either be “centered” as described earlier or otherwise accommodated.
Typically, fixed resolution panels present the most difficulties in graphics scaling since other elements may more often be flexible. Every resolution capable of being generated by a system must be capable of being displayed on a fixed panel for true compatibility. Some CRT based projection systems, however, may be inflexible as to timing and resolution parameters and thus must be used in their native resolutions only. This native resolution may present special difficulties as it may use non-standard timing or resolution.
A typical native resolution for projection CRT displays is 640 pixels by 480 pixels. Use of fixed resolution projection systems leads to problems with fixed resolution panels in cases where projection system resolution does not match panel resolution. In such a case, shutting off LCD panel display may be an undesirable alternative. Another undesirable alternative may be the dual path method previously described which allows independent display of any two resolutions.
When such multimedia display equipment is used with conventional portable computers, because of fixed resolution related problems, a single display resolution only may be displayed on both displays (internal or projected) at the same time. In many instances, it may be desirable to project presentation material on an external monitor while displaying other information (e.g., speaker's notes) on an internal display.
It may also be desirable to switch between internal and external displays, such that a speaker may preview an image prior to projection display. Furthermore, a need for two video displays containing different images may arise in other situations where computers are used, such as CAD systems, spreadsheets, and word processors. In particular, use of Windows™ may make it desirable to allow a user to open one window (or application) on a first video display (e.g., laptop flat panel display) and open another application on another display (e.g., external monitor). Thus, for example, a user may be able to display a scheduler (daily organizer) program on one display while operating a word processing program on another.
Popular prior art approaches to providing multiple displays with different images driven by one computer such as in the dual path method previously described have disadvantages beyond mere hardware cost. In lap-top or notebook computers, dual path methods may increase power drain, weight and size in addition to cost. Minimizing power, cost, size, and weight is especially critical in highly competitive notebook computer markets.
Other methods to drive two displays involves two display signals sharing refresh rates. To faithfully provide two distinct display resolutions, it may be desirable to generate two separate signals for two video displays having different resolutions, pixel depths, and/or refresh rates. For example, it may be desirable to generate two displays in different graphics modes, or one display in a graphics mode and another in text mode.
Moreover, two different displays (e.g., flat panel display and CRT) may use refresh rates different from one another. Alternately, one display may provide improved performance operating at a particular refresh rate unavailable for the other display. In the context of upscaling an image to a fixed resolution display however, traditional methods such as interpolation may not be available or may be inefficient.
Interpolation is a well-known prior art technique used for upscaling video images. In an interpolation scheme, several adjacent pixels in a source video image are typically used to generate additional new pixels. During vertical interpolation of source image data, throughput performance problems may be encountered in a scan-line-dominant-order-of-storing scheme because vertical interpolation usually requires pixels from different scan lines. Accessing different scan lines may require retrieving data from different pages of display memory forcing a non-aligned or non-page mode read access. A non-page mode read access may require more clock cycles than a page mode access for memory locations within a pre-charged row. Thus average memory access time during vertical interpolation may be much higher than consecutive memory accesses within the same row. High average memory access time during vertical interpolation may result in a decrease in the overall throughput performance of a graphics controller chip.
To minimize number of accesses across different rows, a graphics controller chip may retrieve and store a previous scan line in a local memory element. For example, with respect to FIG. 2 , a graphics controller chip may retrieve and store all pixels corresponding to scan line A-B and store retrieved pixels in a local memory located in a graphics controller chip. The graphics controller chip may then retrieve pixels corresponding to scan line C-D, and interpolate using pixels stored in local memory.
SUMMARY OF THE INVENTION
In a computer system with at least one fixed resolution panel display and a fixed resolution CRT display such as a projection display, a display controller may be used for outputting at least one asynchronous display resolution to a fixed resolution panel display. Display data may be received by the controller in one resolution, for example 640 pixels by 480 pixels. The display data may be output to a CRT display and a time base converter for asynchronously converting display data to a resolution which matches a fixed higher resolution panel which may be at a fixed resolution of 600 pixels by 800 pixels, 1024 pixels by 768 pixels or the like.
A time base converter for comparing different timing signals and controlling asynchronous output of display lines according to a predetermined relationship may receive timing input from vertical clock VCLK, dot clock DCLK, CRT horizontal refresh CRT HDSIP, and LCD horizontal refresh LCD HDISP signals. A Horizontal Discrete Time Oscillator may receive input from H SIZE CRT size of CRT horizontal line, H TOTAL LCD total horizontal lines for LCD, and may output a Horizontal Phase signal to a Polyphase Interpolator which may control interpolation of pixels received from a line buffer, from a first and second D-type flip-flop, and directly from a time base converter. A line buffer as described may also function as a vertical line filter. In addition, a signal representing LCD HDISP may be output from a Horizontal Discrete Time Oscillator and input to a time base converter such as described above. A Vertical Discrete Time Oscillator may receive inputs from N and D signals representing Numerator and Denominator respectively. Also, a Vertical Phase signal may be output to a Polyphase Interpolator such as described above. An End of Scan (EOS) signal may be input to a time base converter such as described above to control the end of a vertical scanning sequence. Output from a Polyphase Interpolator may be input to an LCD panel interface which may be used to drive an LCD panel.
A line buffer such as described may receive and store a scan line of display data and two flip-flop elements may be used to delay input of display data to a polyphase interpolator by one clock cycle for the flip-flop elements and one scan line cycle for the line buffer respectively. Thus, four adjacent pixels may be input simultaneously into a polyphase interpolator for upscaling in the following manner. Display data generated within core VGA logic may be output a time base converter.
A time base converter outputs display data to a CRT display, a line buffer, an input terminal of a polyphase interpolator, and a flip-flop element. Flip-flop element output may be input to another input terminal of a polyphase interpolator, line buffer output may be input to yet another input terminal of a polyphase interpolator and another flip-flop element. Finally flip-flop output associated with line buffer output may be input to a fourth input terminal of a polyphase interpolator.
Thus, four inputs with associated delays, create four pixels horizontally and vertically adjacent being input to a polyphase interpolator which may then upscale graphics data to desired output display resolution. Interpolation may be accomplished using a Discrete Cosine Transform upon input pixels. Interpolation may be used to upscale lower resolution display data to a fixed resolution panel of higher resolution.
In a computer system with a fixed resolution panel display, a display controller may be used for outputting at least one of a plurality of different graphics display resolutions to a fixed resolution panel display. Display data may be received by the controller in one resolution, for example 640 pixels by 480 pixels. The display data may be output to a fixed resolution panel which may be at a fixed resolution of 600 by 800 pixels, 1024 by 768 pixels or similar.
A line store buffer may receive and store a scan line of display data and two flip flop elements may be used top delay input of display data to a polyphase interpolator by one clock cycle for the flip flop elements and one scan line cycle for the line buffer respectively. Thus, four adjacent pixels may be input simultaneously into a polyphase interpolator for upscaling in the following manner. Display data generated within core VGA logic may be output to a line store buffer, an input terminal of a polyphase interpolator, and a flip flop element.
Flip flop element output may be input to another input terminal of a polyphase interpolator, line store output may be input to yet another input terminal of a polyphase interpolator and another flip flop element. Finally flip flop output associated with line store output may be input to a fourth input terminal of a polyphase interpolator. Thus, four inputs with associated delays, create four pixels horizontally and vertically adjacent being input to a polyphase interpolator which may then upscale graphics data to desired output display resolution. Interpolation may be accomplished using a Discrete Cosine Transform upon input pixels. Interpolation may be used to upscale lower resolution display data to a fixed resolution panel of higher resolution.
The display controller of the present invention may receive vertical scan clock VCLK signal from a digital PLL circuit. Variations in timing between native VCLK timing for a fixed resolution panel and timing for desired resolution may be synchronized in a PLL block. A clock divider circuit may generate new VCLK signals proportional to a ratio between the fixed resolution display panel and a desired display resolution. Control registers may contain values associated with fixed panel resolution and desired resolution leading to simplified interfacing. Rather than developing device drivers, programmers may set registers with values corresponding to desired operating parameters.
Display data may then be output to an analog CRT driver or an LCD panel driver. Control registers within the display controller may be used to store output resolution, input resolution, SIMULSCAN™ mode, and other parameters.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram illustrating a prior art technique of centering.
FIG. 2 is a diagram illustrating adjacent source pixels and pixels generated through interpolation.
FIG. 3 is a block diagram illustrating components associated with the asynchronous expansion circuit of the present invention.
FIG. 4 is a diagram illustrating a Discrete Time Oscillator of the present invention.
FIG. 5 is a timing diagram illustrating the timing relationship between lines generated for a CRT and lines generated for an LCD panel.
FIG. 6 is a diagram illustrating an embodiment of a Discrete Time Oscillator of the present invention.
FIG. 7 is a block diagram illustrating components associated with the expansion circuit of the present invention.
FIG. 8 is a diagram illustrating an embodiment of a Discrete Time Oscillator of the present invention.
FIG. 9 is a block diagram illustrating a VCO and clock dividers.
DETAILED DESCRIPTION OF THE INVENTION
The descriptions herein are by way of example only illustrating the preferred embodiment of the present invention. However, the method and apparatus of the present invention may be applied in a similar manner in other embodiments without departing from the spirit of the invention.
FIG. 2 is a diagram illustrating adjacent source pixels and pixels generated through interpolation. FIG. 2 shows pixels (A, B, C, and D) of the original source video image and pixels (E-P) which are generated by interpolation resulting in upscaling the original source video image. Pixel E may be generated, for example, by formula (⅔ A+⅓ B). If each pixel is represented in RGB format, RGB components of pixel E may be generated by using corresponding components of pixels A, B. Pixel K may similarly be generated using the formula (⅓ A+⅔ C). Generation of pixels such as E, F may be termed horizontal interpolation as pixels E, F are generated using pixels A, B located horizontally. Generation of pixels such as G, K may be termed vertical interpolation.
FIG. 3 is a block diagram illustrating components associated with the asynchronous expansion circuit of the present invention. Expansion parameters used in the asynchronous expansion circuit of the present invention may be calculated as follows. Given the following parameters, H SIZE LCD —horizontal size of an LCD panel in pixels, H SIZE CRT —horizontal size of a CRT in pixels, V SIZE LCD —vertical size of the LCD in pixels, V SIZE CRT —vertical size of the CRT in pixels, H TOTAL CRT —horizontal total pixels for the CRT, V TOTAL CRT —vertical total pixels for the CRT, and F V =1/T V vertical frame rate or frequency, calculate frame clock rate F VCLK and T VCLK , vertical upscaling ratio, H TOTAL LCD and F DCLK and T DCLK , and reference parameters using equations 1-6.
For a given frame rate F V , F VCLK and T VCLK may be calculated as follows:
F VCLK =V TOTAL CRT ·H TOTAL CRT ·F V (1)
T VCLK =1 /F VCLK =T V /( V TOTAL CRT ·H TOTAL CRT ) (2)
To achieve proper upscaling, a ratio must be chosen which minimizes the size of the numerator and denominator such that:
N/D=V SIZE LCD /V SIZE CRT (3)
Next, H TOTAL LCD may be selected based on horizontal retrace requirements, and T DCLK may be selected and minimized using the following relationship:
H TOTAL CRT =D/N·T VCLK/T DCLK ·H TOTAL LCD (4)
Calculate other timing parameters for reference purposes using the relationships:
V TOTAL LCD =N/D·V TOTAL CRT (5)
T H LCD =H TOTAL LCD ·T DCLK (6)
To determine Vertical DTO 316 and Horizontal DTO 315 parameters, the following equation may be used:
PARAM/MODULO=( V SIZE CRT ·H TOTAL CRT )/(V SIZE LCD ·H TOTAL LCD ) (7)
PARAM may represent the P input to, for example, Horizontal DTO 315 . MODULO may represent the MOD Q input to Horizontal DTO 315 . When PARAM value reaches MODULO value, an output is generated which, in the case of Horizontal DTO 315 represents when sufficient HSIZE CRT 322 input has been received to fill the CRT, or a count equal to HTOTAL CRT 323 has been reached.
VGA core 300 represents a standard VGA controller known in the art for generating display data. VGA Core 300 may generate and output display data lines at a pixel frequency which corresponds to the display resolution for, in the preferred embodiment, a CRT projection panel. Lines 312 generated in RGB format at 24 bits per pixel in the preferred embodiment are output at a frequency 311 to CRT Driver 327 and Time Base Converter 313 . Lines 312 may also be generated at 32 bits per pixel. In the preferred embodiment, VGA Core 300 may generate display information at a frequency corresponding to 640 pixels by 480 pixels. CRT Driver 327 outputs lines to a CRT display 398 such as a projection screen which may employ standard CRT (RGB) display technology known in the art.
Time Base Converter 313 may receive inputs from VGA Core 300 , VCLK 311 , CRT HDISP 325 which is the horizontal retrace signal for the CRT, DCLK 326 or “Dot Clock” which is the rate at which pixels are output from VGA Core 300 , and Carry Out signal 321 and may use equations 1-6 to perform time base conversion between CRT lines and LCD lines in the following manner. Lines may be received at DCLK 326 proportional to CRT 398 resolution. Inside Time Base Converter 313 which also acts as a line store or line buffer, lines received at frequency 311 are compared against the lines required LCD panel display 399 frequency.
FIG. 5 illustrates the timing relationship between CRT lines and LCD lines. Since, for LCD panels of a higher resolution than CRT resolution, lines are required by LCD panel display 399 at a faster rate than lines are generated for CRT 398 , duplicate lines must be output to LCD panel display 399 . FIG. 5 illustrates how lines are asynchronously generated for LCD panel display 399 and CRT 398 . Since LCD panel display 399 is of a higher resolution than CRT 398 another line is required before the end of a line timing interval for CRT 398 . Line 312 in progress for CRT 398 will be repeated for LCD panel display 399 .
Display Data output from Time Base Converter 313 may be input to Vertical Filter/Line Buffer 314 , D-type Flip-flop 307 and Polyphase Interpolator 305 . Vertical Filter/Line Buffer 314 may receive display data from Time Base Converter 313 and filter display data using, for example, in the preferred embodiment, a Discrete Cosine Transform filter. Display data may be stored in Vertical Filter/Line Buffer 314 under control of Vertical Discrete Time Oscillator (DTO) 316 which may issue signal EOS 320 for signalling the end of a vertical scan. Display data output from Vertical Filter/Line Buffer 314 may be input to Polyphase Interpolator 305 and D-type Flip-flop 306 .
Horizontal DTO 315 and Vertical DTO 316 may be used to provide and control horizonal and vertical frequency related parameters such as H SIZE LCD , H SIZE CRT , V SIZE LCD , V SIZE CRT , H TOTAL CRT , and V TOTAL CRT . Horizonal DTO 315 receives HSIZE CRT signal 322 indicating size of a horizontal scan and HTOTAL CRT signal 323 indicating total number of horizontal scans. HPHASE 324 represents Horizontal Phase and may be input to Polyphase Interpolator 305 . Carry Out 321 from the comparison of HSIZE CRT 322 and HTOTAL CRT 323 of Horizontal DTO 315 may be input to Time Base Converter 313 and used to control the output of lines from Time Base Converter 313 .
Vertical DTO 316 receives D signal 317 and N signal 318 representing Denominator value D and Numerator value N in Equation 4. D signal 317 and N signal 318 may be programmed in registers or otherwise supplied by software depending on the relationships desired between parameters in Equation 4. Vertical Phase (VPH) signal 319 representing carry out is output to Polyphase Interpolator 305 .
Each D-type Flip-flop 306 and 307 may add an additional cycle of delay in the vertical direction such that Polyphase Interpolator 305 receives pixels X( 0 , 1 ), X( 0 , 0 ), X( 1 , 0 ), X( 1 , 1 ). These four pixels represent two adjacent pixels in each horizontal and vertical direction. Pixels generated in Polyphase Interpolator 305 , are output to Panel Interface 309 which may be used to generate display information on corresponding LCD panel display 399 .
FIG. 4 is a diagram illustrating a circuit for generating VCLK 406 . VCO PLL 400 generates and maintains frequency stability of DCLK 405 . DCLK 405 may be input to VCLK DTO 401 and gate 402 . Input P 403 and input Q 404 may also be input to VCLK DTO 401 and are proportional to desired output frequency and input frequency respectively. DCLK 405 and carry out from DTO 401 may be input to gate 402 and may be used to generate VCLK 406 .
FIG. 5 is a timing diagram illustrating the timing relationship between lines generated for a CRT projection display and lines generated for a fixed resolution LCD panel. CRT HS signal 501 represents a horizontal scan signal for a CRT and is synchronized with the end of CRT horizontal retrace interval as shown by time 505 , 506 , and 507 . Times 505 , 506 , and 507 are illustrated as corresponding to CRT line generation. L 0 and L 1 are arbitrary designators use to compare timing for corresponding lines generated for both CRT display and LCD display.
L 0 represents line 0 and L 1 represents line one; L 0 and L 1 are reused as reference numbers for subsequent lines. By designating L 0 and L 1 accordingly, the relationship between L 0 generated for the CRT and L 0 generated for the LCD may be seen. Data for L 0 is replicated for a second LCD line during, for example, time 506 . Since the present invention discloses an asynchronous relationship between CRT and LCD displays, any number of lines displayed for the LCD during the time interval between time 505 and 506 would be replicated as LO.
CRT HDISP signal 502 is shown as active during the time when a horizontal line is being displayed and not active during the retrace interval when returning to begin the next line scan. LCD HS 503 represents a horizontal scan signal for an LCD panel and coincides with the end of the retrace interval of LCD HDISP signal 504 . LCD HDISP signal 504 is shown as active during the time when a horizontal line is being displayed and not active during the retrace interval when returning to begin the next scan. As shown in FIG. 5 , three LCD lines may be displayed during an interval corresponding to display of two CRT lines. A scaling factor of 1.5 would result from a requirement to display 3 LCD lines for every 2 CRT lines.
Any number of LCD lines may be generated asynchronously as a function of CRT lines based on a ratio of CRT resolution and LCD panel fixed resolution in accordance with Equation (3). As display data for L 0 is being output as a CRT line, L 0 is being output as an LCD line. L 0 for the LCD is finished and a retrace interval begins before L 0 for the CRT is complete. Since L 0 for the CRT is still being output, then next line for the LCD begins to write L 0 again. Since display data for CRT lines and LCD lines are derived from a common data stream output from VGA Core 300 , only timing differences affect number of lines output to the LCD for each CRT line. Thus, within practical limitations, any number of LCD lines may be output asynchronously using display data originally generated as CRT output.
FIG. 6 is a diagram illustrating an embodiment of a Discrete Time Oscillator of the present invention. In order to implement Horizontal and Vertical DTO block of the present invention, a circuit of the kind illustrated in FIG. 6 may be used to perform a PLL function as well as a divide function. As background to FIG. 6 , equation (8) describes the relationship between values P 603 , Q, F in 602 and F out 604 of FIG. 6 :
f out =f in ( P/Q ) (8)
Value P 603 is input to accumulator 600 . Value P 603 represents the numerator of the rational expression on the right side of equation 1. Value P 603 may be proportional to the desired output frequency F out 604 . Denominator Q may be proportional to the input frequency F in 602 . In the preferred embodiment of the present invention, P 603 and Q may be proportional to vertical clock frequencies of desired display resolution and native display resolution respectively. Native display resolution means fixed panel display resolution.
F in 602 may be input to the clock terminal of gate 601 which, in the preferred embodiment, may be a flip-flop. The count output of accumulator 600 may be input to gate 601 . By indirectly coupling F in 602 through gate 601 , anomalies associated with dividing are minimized. As the count increments to value P 603 on each clock transition of F in 602 , carry out value representing mod Q is output as F out 604 .
FIG. 7 is a block diagram illustrating components associated with the expansion circuit of the present invention. VGA core 300 may generate display data one horizontal line at a time. Horizontal lines are output a pixel at a time at a frequency of VLCK 311 to Line Buffer 303 and D type Flip Flop 307 . Line Buffer 303 may store a line of display data and may represent one cycle of delay in the horizontal direction such that Line Buffer 303 may contain the previous line of data. Each D Flip Flop 306 and 307 may add an additional cycle of delay in the vertical direction such that Polyphase Interpolator 305 receives pixels X( 0 , 1 ), X( 0 , 0 ), X( 1 , 0 ), X( 1 , 1 ). These four pixels represent two adjacent pixels in each horizontal and vertical directions. Pixels generated in Polyphase Interpolator 305 , are output to CRT driver 308 and Panel interface 309 which may be used to generated display information on the corresponding display. Polyphase Interpolator 305 and Clock Divider 302 receive DCLK signal 310 from VCLK VCO & PLL block 301 . DCLK signal 310 represents the frequency at which data may be generated.
Clock Divider 302 may generate VCLK 311 at a value which represents a ratio between H sizeVGA and H sizeLCD . Thus, the ratio between H sizeVGA and H sizeLCD may be proportional to the ratio between DCLK 310 and VCLK 311 . The ratio of VCLK 311 and DCLK 310 may automatically set output scaling for the display. Control Logic 304 may store values corresponding to fixed display resolution and desired display resolution. By making values for fixed resolution and desired resolution settable in registers, output resolution is decoupled from a hardware implementation in core logic. Rather than write complex drivers on an individual basis for each display likely to be encountered, developers may simply set values in registers to drive displays of many types including fixed resolution displays. Polyphase Interpolator 305 may generate display lines automatically scaled to fit output size. Control Logic 304 may distribute control signals associated with register settings to VCLK VCO & PLL block 301 .
FIG. 8 is a diagram illustrating an embodiment of a Discrete Time Oscillator of the present invention. In order to implement VCLK VCO & PLL block 301 and Clock Divider 302 of the present invention, a circuit of the kind illustrated in FIG. 8 may be used to perform a PLL function as well as a divide function. As background to FIG. 8 , equation (1) describes the relationship between values P 403 , Q, F in 402 and F out 404 of FIG. 8 :
f out =f in ( P/Q ) (1)
Value P 403 is input to accumulator 400 . Value P 403 represents the numerator of the rational expression on the right side of equation 1. Value P 403 may be proportional to the desired output frequency F out 404 . Denominator Q may be proportional to the input frequency F in 402 . In the preferred embodiment of the present invention, P 403 and Q may be proportional to vertical clock frequencies of desired display resolution and native display resolution respectively. Native display resolution means fixed panel display resolution. F in 402 may be input to the clock terminal of gate 401 which in the preferred embodiment may be a flip flop. The count output of accumulator 400 may be input to gate 401 . By indirectly coupling F in 402 through gate 401 , anomalies associated with dividing are minimized. As the count increments to value P 403 on each clock transition of F in 402 , carry out value representing mod Q is output as F out 404 .
FIG. 9 is a block diagram illustrating a VCO and clock dividers. VCO 500 may generate DCLK 505 at a native frequency proportional to the scanning frequency for a fixed panel LCD which may be in use. DCLK 505 may be input to DTO divider 501 for generation of VCLK 503 according to a ratio P/Q as in equation (1). Ratio P/Q may represent the relationship between desired output frequency, which may be proportional to output resolution, and input frequency represented in this embodiment by DCLK 505 , which may be proportional to a fixed resolution. VCLK may be output from DTO divider 501 at a frequency proportional to ratio P/Q as in equation (1) and input to DTO divider 502 and other circuits within the controller of the present invention. DTO divider 502 may be used to generate MVA™ clock MCLK 504 . MCLK 504 may be used to further scale an MVA™ window within the main scaled graphics display. Since MVA™ window size may be changed during use and since color depth of an MVA™ window may be greater than background color depth, separate “scaling within scaling” must be performed for MVA™ display.
While the preferred embodiment and alternative embodiments have been disclosed and described in detail herein, it may be apparent to those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention. For example, while interpolation in the preferred embodiment may comprise a polyphase interpolator, the present invention could be practiced with virtually any interpolation means.
Similarly, while output is drawn to a fixed resolution CRT projection panel and a fixed resolution LCD panel, the present invention could be practiced on any system which requires asynchronous display timing for multiple displays operating from the same display data stream. Moreover, although the preferred embodiment is drawn to an integrated circuit, the present invention may be applied to a series of integrated circuits, a chipset, or in other circuitry within a computer system without departing from the spirit and scope of the present invention. | A display controller in a computer system controls the asynchronous output of graphics display data in a computer system having at least one fixed resolution flat panel display. Fixed panel displays may have problems displaying non-native resolutions particularly at lower resolutions. The controller of the present invention uses a time base converter, horizontal and vertical Discrete Time Oscillators (DTO), and polyphase interpolator, which may be Discrete Cosine Transform (DCT)-based to expand graphics display data asynchronously from native resolution to at least one resolution suitable for display on a fixed resolution panel. Graphics data may also be output asynchronously to a CRT. Time base converter receives frequency related input parameters and generates at least one asynchronous output at the desired output resolution. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 09/991,378, filed Nov. 11, 2001, which is a continuation of U.S. patent application Ser. No. 08/769,947, filed Dec. 19, 1996 and now abandoned, which is a continuation-in-part of U.S. patent application Ser. No. 08/238,750, filed May 5, 1994 and issued as U.S. Pat. No. 5,835,255, and is also a continuation-in-part of U.S. patent application Ser. No. 08/554,630, filed Nov. 6, 1995 and now abandoned. The above-referenced applications are herein incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] This invention relates to visible spectrum (which we define to include portions of the ultra-violet and infrared spectra) modulator arrays and interferometric modulation.
[0003] The first patent application cited above describes two kinds of structures whose impedance, the reciprocal of admittance, can be actively modified so that they can modulate light. One scheme is a deformable cavity whose optical properties can be altered by deformation, electrostatically or otherwise, of one or both of the cavity walls. The composition and thickness of these walls, which comprise layers of dielectric, semiconductor, or metallic films, allows for a variety of modulator designs exhibiting different optical responses to applied voltages.
[0004] The second patent application cited above describes designs which rely on an induced absorber. These designs operate in reflective mode and can be fabricated simply and on a variety of substrates.
[0005] The devices disclosed in both of these patent applications are part of a broad class of devices which we will refer to as IMods (short for “interferometric modulators”). An IMod is a microfabricated device that modulates incident light by the manipulation of admittance via the modification of its interferometric characteristics.
[0006] Any object or image supporter which uses modulated light to convey information through vision is a form of visual media. The information being conveyed lies on a continuum. At one end of the continuum, the information is codified as in text or drawings, and at the other end of the continuum, it is abstract and in the form of symbolic patterns as in art or representations of reality (a picture).
[0007] Information conveyed by visual media may encompass knowledge, stimulate thought, or inspire feelings. But regardless of its function, it has historically been portrayed in a static form. That is, the information content represented is unchanging over time. Static techniques encompass an extremely wide range, but in general include some kind of mechanism for producing variations in color and/or brightness comprising the image, and a way to physically support the mechanism. Examples of the former include dyes, inks, paints, pigments, chalk, and photographic emulsion, while examples of the latter include paper, canvas, plastic, wood, and metal.
[0008] In recent history, static display techniques are being displaced by active schemes. A prime example is the cathode ray tube (CRT), but flat panel displays (FPD) offer promise of becoming dominant because of the need to display information in ever smaller and more portable formats.
[0009] An advanced form of the FPD is the active matrix liquid crystal display (AMLCD). AMLCDs tend to be expensive and large, and are heavy users of power. They also have a limited ability to convey visual information with the range of color, brightness, and contrast that the human eye is capable of perceiving, using reflected light, which is how real objects usually present themselves to a viewer. (Few naturally occurring things emit their own light.)
[0010] Butterflies, on the other hand, achieve a broad range of color, brightness, and contrast, using incident light, processed interferometrically, before delivery to the viewer.
SUMMARY
[0011] In general, in one aspect, the invention features a modulator of light having an interference cavity for causing interference modulation of the light, the cavity having a mirror, the mirror having a corrugated surface.
[0012] In general, in another aspect of the invention, the interference modulation of the light produces a quiescent color visible to an observer, the quiescent color being determined by the spatial configuration of the modulator.
[0013] In implementations of the invention, the interference cavity may include a mirror and a supporting structure holding the mirror, and the spatial configuration may include a configuration of the supporting structure, or patterning of the mirror. The supporting structure may be coupled to a rear surface of the mirror. The invention eliminates the need for separately defined spacers and improves the fill-factor.
[0014] In general, in another aspect of the invention, the structure for modulating light includes modulators of light each including an interference cavity for causing interference modulation of the light, each of the modulators having a viewing cone. The viewing cones of the modulators are aligned in different directions.
[0015] In implementations of the invention, the viewing cones of the different modulators may be aligned in random directions and may be narrower than the viewing cone of the overall structure. Viewing a randomly oriented array of interference modulators effectively reduces the color shift.
[0016] In general, in another aspect of the invention, the modulators may be suspended in a solid or liquid medium.
[0017] In general, in another aspect of the invention, an optical compensation mechanism is coupled to the modulators to enhance the optical performance of the structure. In implementations of the invention, the mechanism may be a combination of one or more of a holographically patterned material, a photonic crystal array, a multilayer array of dielectric mirrors, or an array of microlenses. The brightness and/or color may be controlled by error diffusion. An array of modulators may be viewed through a film of material which, because of its tailored optical properties, enhances the view from a limited range of angles, or takes incident light of random orientation and orders it. The film may also enhance the fill factor of the pixel. The film may also comprise a patterned light emitting material to provide supplemental lighting.
[0018] In general, in another aspect of the invention, an optical fiber is coupled to the interference cavity. The invention may be used in the analysis of chemical, organic, or biological components.
[0019] In general, in another aspect of the invention, there is an array of interference modulators of light, a lens system, a media transport mechanism and control electronics.
[0020] In general, in another aspect, the invention features an information projection system having an array of interference modulators of light, a lens system, mechanical scanners, and control electronics. In implementations of the invention, the control electronics may be configured to generate projected images for virtual environments; and the array may include liquid crystals or micromechanical modulators.
[0021] In general, in another aspect, the invention features an electronics product having an operational element, a housing enclosing the operational element and including a display having a surface viewed by a user, and an array of interference modulators of light on the surface.
[0022] Implementations of the invention may include one or more of the following features. The operational element may include a personal communications device, or a personal information tool, or a vehicular control panel, or an instrument control panel, or a time keeping device. The array may substantially alter the aesthetic or decorative features of the surface. The aesthetic component may respond to a state of use of the consumer product. The array may also provide information. The modulation array of the housing may comprise liquid crystals, field emission, plasma, or organic emitter based technologies and associated electronics.
[0023] In general, in another aspect, the invention features devices in which aggregate arrays of interference modulators are assembled as a display, e.g., as a sign or a billboard.
[0024] In general, in another aspect, the invention features a vehicle having a body panel, an array of interference modulators of light on a surface of the body panel, and electronic circuitry for determining the aesthetic appearance of the body panel by controlling the array of interference modulators.
[0025] In general, in another aspect, the invention features a building comprising external surface elements, an array of interference modulators of light on a surface of the body panel, and electronic circuitry for determining the aesthetic appearance of the surface elements by controlling the array of interference modulators.
[0026] In general, in another aspect, the invention features a full color active display comprising a liquid crystal medium, and interferometric elements embedded in the medium.
[0027] In general, in another aspect, the invention features a structure including a substrate, micromechanical elements formed on the substrate, and electronics connected to control the elements, the electronics being formed also on the substrate.
[0028] Individual pixels of the array may consist of arrays of subpixels, allowing brightness and color control via the activation of some fraction of these subpixels in a process known as spatial dithering. Individual pixels or subpixel arrays may be turned on for a fraction of an arbitrary time interval to control brightness in a process known as pulse width modulation (PWM). Individual pixels or subpixel arrays may be turned on for a fraction of the time required to scan the entire array to control brightness in a process known as frame width modulation (FWM). These two schemes are facilitated by the inherent hysteresis of the IMod which allows for the use of digital driver circuits. Neighboring pixels yield a brightness value which is the average of the desired value when error diffusion is used. Brightness control may be achieved via a combination of spatial dithering, PWM/FWM, or error diffusion. Color control may be achieved by tuning individual colors to a particular color, or by combining pixels of different colors and different brightness. The terms pixels and IMods are interchangeable, but in general, pixel refers to a controllable element which may consist of one or more IMods or subpixels, and which is “seen” directly or indirectly by an individual.
[0029] The arrays may fabricated on a solid substrate of some kind which may be of any material as long as it provides a surface, portions of which are optically smooth. The material may be transparent or opaque. The material may be flat or have a contoured surface, or be the surface of a three dimensional object. The arrays may be fabricated on the surface, or on the opposite or both sides if the substrate is transparent. In a further aspect the invention can be viewed in a variety of ways.
[0030] Implementations of the invention may include one or more of the following features. The array may be directly viewed in that an individual can look at the array and see the represented information from any angle. The array may be directly viewed from a fixed angle. The array may be indirectly viewed in that the information is projected on to a secondary surface, or projected through an optical system, or both.
[0031] In yet another aspect the invention can be electrically controlled and driven in several ways.
[0032] Implementations of the invention may include one or more of the following features. The array may be fabricated on a substrate and the driver and controller electronics are fabricated on a separate substrate. The two substrates may be connected electrically or optically via cables, or optically, magnetically, or via radio frequencies via a free space connection. The array may be fabricated with driver, controller, or memory electronics, or some combination thereof, mounted on the same substrate and connected via conducting lines. The array may be fabricated on a substrate along with the driver, controller or memory electronics, or some combination thereof. The substrate may include active electronics which constitute driver, controller, or memory electronics, or some combination thereof, and the array may be fabricated on the substrate. The electronics may be implemented using microelectromechanical (MEM) devices.
[0033] In an additional aspect the invention modulates light actively, using an array of modulators or sections of arrays which are addressed in several ways.
[0034] Implementations of the invention may include one or more of the following features. Individual pixels or arrays of pixels may be connected to a single driver and may be activated independently of any other pixel or pixel array in a technique known as direct addressing. Individual pixels or arrays of pixels may be addressed using a two-dimensional matrix of conductors and addressed in a sequential fashion in a technique known as matrix addressing. Some combination of matrix or direct addressing may be used.
[0035] Among the advantages of the invention are one or more of the following.
[0036] Because interference modulators are fabricated on a single substrate, instead of a sandwich as in LCDs, many more possible roles are made available. The materials used in their construction are insensitive to degradation by UV exposure, and can withstand much greater variations in temperature. Extremely saturated colors may be produced. Extremely high resolutions make possible detail imperceptible to the human eye. Either transmitted or reflected light may be used as an illumination source, the latter more accurately representing how objects and images are perceived. The ability to fabricate these devices on virtually any substrate makes possible the surface modulation of essentially any man-made or naturally occurring object. It is possible to realize images which are much closer to what exists in nature and more realistic than what is possible using current printing methods.
[0037] Interferometric modulation uses incident light to give excellent performance in terms of color saturation, dynamic range (brightness), contrast, and efficient use of incident light, performance which may approach the perceptual range of the human visual system. The fabrication technology allows interference modulators to be manufactured in a great variety of forms. This variety will enable active visual media (and superior static visual media) to become as ubiquitous as the traditional static media which surround us.
[0038] In general, the invention provides the tools for creating an array of products and environments which are as visually rich and stimulating as anything found in nature.
[0039] Other advantages and features will become apparent from the following description and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] FIGS. 1A and 1B are top and perspective views of an IMod with spatially defined color.
[0041] FIG. 2 is a side view of an IMod with spatially defined color.
[0042] FIGS. 3A and 3B are top and side views of a spatially defined mirror. FIG. 3A shows a mirror with a 50% etch while FIG. 3B shows a mirror with a 75% etch.
[0043] FIG. 4 is a perspective view of a back-supported IMod with a good fill factor.
[0044] FIGS. 5A , 5 B, and 5 C are schematic views of an IMod and IMod array with a limited viewing cone. FIG. 5A shows the behavior of light within the viewing cone while FIG. 5B shows the behavior of light outside the cone. FIG. 5C shows the performance of an overall array.
[0045] FIGS. 6A , 6 B, 6 C, 6 D, and 6 E, 6 F are side views of optical compensation mechanisms used for minimizing color shift and enhancing fill factor. FIG. 6A shows a holographically patterned material, FIG. 6B shows a photonic crystal array, FIG. 6C shows a multilayer dielectric array, FIG. 6D shows an array of microlenses, while FIGS. 6E and 6F show side and top views of a supplemental lighting film.
[0046] FIGS. 7A and 7B are schematic views of an array which is addressed using spatial dithering. FIG. 7A shows a full-color pixel while FIG. 7B shows detail of a sub-pixel.
[0047] FIG. 8 is a timing diagram for driving a binary IMod.
[0048] FIG. 9 is a diagram of the hysteresis curve for an IMod device.
[0049] FIGS. 10A and 10B are a top view of an IMod array which is connected for matrix addressing and a digital driver. FIG. 10A shows the matrix array while FIG. 10B shows a digital driving circuit.
[0050] FIG. 11 is a side view of an IMod array configured for direct viewing.
[0051] FIG. 12 is a side view of an IMod array configured for direct viewing through an optical system.
[0052] FIG. 13 is a diagram of an IMod array configured for indirect viewing.
[0053] FIG. 14 is a perspective view of an IMod array and a separate driver/controller.
[0054] FIGS. 15 and 16 are perspective views of IMod arrays and driver/controllers on the same substrates.
[0055] FIGS. 17A and 17B are front views of a direct driven IMod subarray display. FIG. 17A shows a seven segment display while FIG. 17B shows detail of one of the segments.
[0056] FIGS. 18A and 18B are top views of a matrix driven subarray display. FIG. 18A shows a matrix display while FIG. 18B shows detail of one of the elements.
[0057] FIG. 19 is a side view of an IMod based fiber optic endcap modulator.
[0058] FIG. 20 is a perspective view of a linear tunable IMod array.
[0059] FIGS. 21A and 21B are a representational side view of a linear IMod array used in an imaging application and a components diagram. FIG. 21A shows the view while FIG. 21B shows the components diagram.
[0060] FIG. 22 is a perspective view of a two-dimensional tunable IMod array.
[0061] FIG. 23 is a perspective view of a two-dimensional IMod array used in an imaging application.
[0062] FIGS. 24A , 24 B, 24 C, 24 D, and 24 E are views of an IMod display used in a watch application. FIG. 24A shows a perspective view of a watch display, FIGS. 24B , 24 C, 24 D, and 24 E show examples of watch faces.
[0063] FIGS. 25A and 25B are views of an IMod display used in a head mounted display application. FIG. 25A shows a head mounted display while FIG. 25B shows detail of the image projector.
[0064] FIGS. 26A , 26 B, 26 C, and 26 D are perspective views of an IMod display used in several portable information interface applications and a components diagram. FIG. 26A shows a portable information tool, FIG. 26B shows the components diagram, FIG. 26C shows a cellular phone, while FIG. 26D shows a pager.
[0065] FIGS. 27A , 27 B, 27 C, 27 D, 27 E, 27 F and 27 G are views of an IMod display used in applications for information and decorative display, a remote control, and components diagrams. FIGS. 27A , 27 B, and 27 D show several examples, FIG. 27C shows a components diagram, FIG. 27E shows a remote control, and FIG. 27F shows another components diagram.
[0066] FIGS. 28A and 28B are side views of an IMod display used in an application for automotive decoration and a components diagram. FIG. 28A shows a decorated automobile, while FIG. 28B shows the components diagram.
[0067] FIGS. 29A , 29 B, and 29 C are views of an IMod array used as a billboard display and a components diagram. FIG. 29A shows a full billboard, FIG. 29B shows a display segment, and FIG. 29C shows a segment pixel.
[0068] FIGS. 30A and 30B are views of an IMod array used as an architectural exterior and a components diagram. FIG. 30A shows the skyscraper, while FIG. 30B shows the components diagram.
[0069] FIGS. 31A and 31B are drawings of a liquid crystal impregnated with an interferometric pigment. FIG. 31A shows the liquid crystal cell in the undriven state while FIG. 31B shows it in the driven state.
[0070] FIGS. 32A and 32B are drawings of an IMod array used in a projection display and a components diagram. FIG. 32A shows the projection system, while FIG. 32B shows the components diagram.
[0071] FIGS. 33A and 33B are drawings of an IMod array used in a chemical detection device and a components diagram. FIG. 33A shows the detection device, while FIG. 33B shows the components diagram.
[0072] FIGS. 34A , 34 B, and 34 C are front and side views of an IMod based automotive heads up display and a components diagram. FIG. 34A shows the front view, FIG. 34B shows the side view, and FIG. 34C shows the components diagram.
[0073] FIGS. 35A and 35B are drawings of an IMod display used in an instrument panel and a components diagram. FIG. 35A shows the panel while FIG. 35B shows the components diagram.
DETAILED DESCRIPTION
IMod Structures
[0074] Referring to FIGS. 1A and 1B , two IMod structures 114 and 116 each include a secondary mirror 102 with a corrugated pattern 104 etched into its upper (outer) surface 103 , using any of a variety of known techniques. The corrugation does not extend through the membrane 106 on which the mirror is formed so that the inner surface 108 of the mirror remains smooth. FIG. 1B reveals the pattern of etched corrugation 104 on the secondary mirror and the smooth inner surface 112 which remains after etch. The corrugated pattern, which can be formed in a variety of geometries (e.g., rectangular, pyramidal, conical), provides structural stiffening of the mirror, making it more immune to variations in material stresses, reducing total mass, and preventing deformation when the mirror is actuated.
[0075] In general, an IMod which has either no voltage applied or some relatively steady state voltage, or bias voltage, applied is considered to be in a quiescent state and will reflect a particular color, a quiescent color. In the previously referenced patent applications, the quiescent color is determined by the thickness of the sacrificial spacer upon which the secondary mirror is fabricated.
[0076] Each IMod 114 , 116 is rectangular and connected at its four corners to four posts 118 via support arms such as 120 and 122 . In some cases (see discussion below), the IMod array will be operated at a stated constant bias voltage. In those cases, the secondary mirror 102 will always maintain a quiescent position which is closer to corresponding primary mirror 128 than without any bias voltage applied. The fabrication of IMods with differently sized support arms allows for the mechanical restoration force of each IMod to be determined by its geometry. Thus, with the same bias voltage applied to multiple IMods, each IMod may maintain a different biased position (distance from the primary mirror) via control of the dimensions of the support arm and its resulting spring constant. The thicker the support arm is, the greater its spring constant. Thus different colors (e.g., red, green, and blue) can be displayed by different IMods without requiring deposition of different thickness spacers. Instead, a single spacer, deposited and subsequently removed during fabrication, may be used while color is determined by modifying the support arm dimensions during the single photolithographic step used to define the arms. For example, in FIG. 2 , IMods 114 , 116 are both shown in quiescent states with the same bias voltage applied. However, the gap spacing 126 for IMod 114 is larger than gap spacing 128 for IMod 116 by virtue of the larger dimensions of its respective support arms.
[0077] As shown in FIGS. 3A and 3B , in another technique for achieving spatially defined color, instead of affecting the quiescent position of the movable membrane, one or both of the mirrors (walls) comprising the IMod is patterned to determine its qualities spatially instead of by material thickness.
[0078] Thus, in FIG. 3A , mirror 300 has two layers 302 and 304 . By etching layer 302 the effective index of refraction of layer 302 , and thus the performance of mirror 300 , may be altered by controlling the percentage of the layer which remains after the etch. For example, a material with index of 2 maintains that value if there is no etch at all. However if 75% of the material is etched away, the average index falls to 1.75. Etching enough of the material results in an index which is essentially that of air or of the material which may fill in the etched area.
[0079] The mirror layer 308 in FIG. 3B , by contrast has an effective refractive index which is less than that of mirror layer 302 . Because the overall behavior of both mirrors is determined by their materials properties, and the behavior of the IMod by the mirror properties, then the color of an IMod incorporating mirror 300 is different from an IMod comprising mirror 306 by virtue of spatially varying, e.g., etching or patterning, one or more of the layers comprising the mirrors. This, again, can be done in a single photolithographic step.
[0080] Referring to FIG. 4 , in another type of IMod a back supporting mechanism is used instead of an array of posts and support arms (which consume useful surface area on the display). Here, the secondary mirror 402 is mechanically held by support arm 400 at location 406 . Arm 400 contacts the substrate 403 at locations 408 where it occupies a minimal footprint, thereby maximizing the amount of area devoted to the mirrors 402 , 404 . This effect is enhanced by notches 408 , 410 which allow mirrors 402 and 404 to conform to the support. Rear support could also be achieved in other ways, perhaps using multiple arms to maintain parallelism. The rear supports can also provide a basis for multilevel conductor lines. For example, an elevated conductor line 412 may be tied to support arm 400 . This configuration minimizes the area on the substrate required for such purposes.
Reducing Color Shift and Supplying Supplemental Illumination
[0081] As shown in FIGS. 5A through 5C , to minimize color shift as the angle of incidence changes (a characteristic of interferometric structures) IMod structures 502 , 506 are fabricated to have a very high aspect ratio, i.e., they are much taller than they are wide. Consequently, they only exhibit interferometric behavior within a narrow cone 501 of incidence angles. Incident light 500 which is within cone 501 , as in FIG. 5A , interacts with the multiple layers (shown by striped sections in the figure) the composition and configuration of which are dictated by the design of the IMod. In general, as indicated in the previous patent applications, these can consist of combinations of thin films of metals, metallic oxides, or other compounds. The important fact being that the geometry of the stack dictates that interference occurs only within a narrow cone of incidence angles. On the other hand, as seen in FIG. 5B , incident light 504 (outside of the cone) is relatively unaffected by the IMod because it interacts with only a very few layers. Such an IMod would appear, say blue, to a viewer who looks at it from a narrow range of angles.
[0082] As seen in FIG. 5C , if an array 507 of these structures 508 is fabricated such that they are oriented to cover many different viewing angles then the entire array can appear blue from a much larger range of angles. This random orientation may be achieved, for example, by fabrication on a randomly oriented surface or by random suspension in a liquid medium.
[0083] As seen in FIGS. 6A-6F , other techniques for minimizing color shift and for supplying supplemental illumination are possible. In these examples, a specially designed optical film is fabricated on the opposite surface of the substrate from the surface on which the IMod array resides. Such films can be designed and fabricated in a number of ways, and may be used in conjunction with each other.
[0084] In FIG. 6A , film 600 is a volume or surface relief holographic film. A volume holographic film may be produced by exposing a photosensitive polymer to the interference pattern produced by the intersection of two or more coherent light sources (i.e. lasers). Using the appropriate frequencies and beam orientations arbitrary periodic patterns of refractive indices within the film may be produced. A surface relief holographic film may be produced by creating a metal master using any number of microfabrication techniques known by those skilled in the art. The master is subsequently used to the pattern into the film. Such films can be used to enhance the transmission and reflection of light within a definable cone of angles, thus minimizing off-axis light. The colors and brightness of a display viewed with on axis light are enhanced and color shift is diminished because brightness goes down significantly outside of the cone.
[0085] In FIG. 6B , another approach is shown as device 604 in which an array of structures 606 is fabricated on the substrate. These structures, which can be fabricated using the techniques described in the previously referenced patent applications, can be considered photonic crystals, as described in the book “Photonic Crystals”, by John D. Joannopoulos, et al., and incorporated by reference. They are essentially three-dimensional interferometric arrays which demonstrate interference from all angles. This provides the ability to design waveguides which can perform a number of functions including channeling incident light of certain frequencies to the appropriately colored pixels, or by changing light of a certain incidence angle to a new incidence angle, or some combination of both.
[0086] In another example, seen in FIG. 6C , a three-layer polymeric film 610 contains suspended particles 611 . The particles are actually single or multi-layer dielectric mirrors which have been fabricated in the form of microscopic plates. These plates, for example, may be fabricated by deposition of multilayer dielectric films onto a polymer sheet which, when dissolved, leaves a film which can “ground up” in a way which produces the plates. The plates are subsequently mixed into a liquid plastic precursor. By the application of electric fields during the curing process, the orientation of these plates may be fixed during manufacture. The mirrors can be designed so that they only reflect at a range of grazing angles. Consequently, light is either reflected or transmitted depending on the incidence angle with respect to the mirror. In this case, layer 612 is oriented to reflect light 609 of high incidence that enters the film 610 closer to the perpendicular. Layer 614 reflects light 613 of lower incidence into a more perpendicular path. Layer 616 modifies the even lower angle incident light 615 . Because the layers minimally affect light which approaches perpendicularly, they each act as a separate “angle selective incidence filter” with the result that randomly oriented incident light couples into the substrate with a higher degree of perpendicularly. This minimizes the color shift of a display viewed through this film.
[0087] In another example, FIG. 6D , micro lenses 622 are used in an array in device 620 . Each lens 622 may be used to enhance the fill factor of the display by effectively magnifying the active area of each pixel. This approach could be used by itself or in conjunction with the previous color shift compensation films.
[0088] In another example, FIG. 6E , device 624 uses supplemental lighting in the form of a frontlighting array. In this case an organic light emitting material 626 , for example, Alq/diamine structures and poly(phenylene vinylene), can be deposited and patterned on the substrate. The top view, FIG. 6F , reveals a pattern 627 which corresponds with the IMod array underneath. That is, the light emitting areas 626 are designed to obscure the inactive areas between the IMods, and allow a clear aperture in the remaining regions. Light is emitted into the substrate onto the IMod and is subsequently reflected back to the viewer. Conversely, a patterned emitting film may be applied to the backplate of the display and light transmitted forward through the gaps between the sub-pixels. By patterning a mirror on the front of the display, this light can be reflected back upon the IMod array. Peripherally mounted light sources in conjunction with films relying on total internal reflection are yet another approach.
Brightness Control
[0089] Referring to FIG. 7A , a full color spatially dithered pixel 701 includes side-by-side sub-pixels 700 , 702 , and 704 . Sub-pixel 700 , for example, includes sub-arrays of IMods whose numbers differ in a binary fashion. For example, sub-array 706 is one IMod, sub-array 708 is 2 IMods, sub-array 710 is 4 IMods, while sub-array 718 is 128 IMods. Sub-array 712 is shown in greater detail in FIG. 7B . In the arrays, each IMod is the same size so that the amount of area covered by each sub-array is proportional to the total number of IMods in the array. Row electrodes 724 and column electrodes 722 are patterned to allow for the selective and independent actuation of individual sub-arrays. Consequently, the overall brightness of the pixel may be controlled by actuating combinations of the sub-arrays using a binary weighting scheme. With a total of 8 sub-arrays, each sub-pixel is capable of 256 brightness levels. A brightness value of 136 may be achieved, for example, by the actuation of sub-arrays 718 and 712 . Color is obtained by combining different values of brightness of the three sub-pixels.
[0090] The apparent dynamic range of the display may also be enhanced using a process known as error diffusion. In some applications, the number of bits available for representing the full range of brightness values (dynamic range) may be limited by the capabilities of the drivers, for example. In such a situation, the dynamic range may be enhanced by causing neighboring pixels to have a brightness value, the average of which is closer to an absolute value that cannot be obtained given the set number of bits. This process is accomplished electronically within the controller logic, and can be accomplished without significantly affecting the display resolution.
Digital Driving
[0091] In a digital driving scheme, as shown in FIGS. 8 , 9 , and 10 , FIG. 8 is a timing diagram showing one set of voltages required to actuate a matrix addressed array of IMods. Column select pulses 800 and 802 are representative of what would be applied to a particular column. Further detail is revealed in pulse 800 which is shown to switch from voltage level Cbias to voltage Cselect. Row select pulses 804 and 806 are also shown, with 804 revealing that the required voltage levels are Rselect, Rbias, and Roff (O volts). When a column select pulse is present, and a row select pulse is applied, the pixel which resides at the intersection of the two is actuated as shown in the case of pixel 808 which resides on the row driven by select pulse 804 , and subsequently in pixel 810 , which resides on the row driven by pulse 806 . When select pulse 804 is driven to the Roff level, pixel 808 is turned off. Pixel 812 illustrates the behavior of a pixel in an arbitrary state when a Roff value is placed on the row line, i.e., if it is on it turns off, or if it is off it remains off.
[0092] In FIG. 9 , the voltages are shown in the context of a hysteresis curve which is typical of an IMod. As the applied voltage is increased, the membrane does not move significantly until the value rises beyond a certain point, which is known as the collapse threshold. After this point, the membrane undergoes full displacement. This state is maintained until the voltage is dropped below a point where actuation began. Several conditions must be met in order for this scheme to be successful. The combination of Csel and Rsel must be higher than the collapse threshold voltage, the combination of Cbias and Rsel must not fully actuate the membrane, the combination of Cbias and Rbias must maintain a displaced state, and the combination of Roff and Cbias must free the membrane.
[0093] FIG. 10A is representative of a typical matrix addressed array illustrating column lines 1000 and row lines 1002 . FIG. 10B illustrates a typical shift register based driver circuit. The size of the display array and the number of bits in the register would determine how many of these components would be required for both rows and columns. Bits corresponding to the appropriate row and column values are shifted into the register and loaded on the outputs when they are required during the course of the scanning the display.
Viewing Modes
[0094] Referring to FIG. 11 , among the different generic ways to view an IMod display 1104 (the best one being selected based on the particular product application) are a direct viewing mode with the viewer 1100 perceiving the display without the aid of an image forming optical system. Direct viewing can occur in reflection mode, using reflected light 1102 , or transmitted mode, using transmitted light 1106 , or some combination of the two.
[0095] In another example, FIG. 12 , direct viewing configurations may rely on intervening optics to form an image from an image source generated by IMod display 1204 . Reflected light 1202 or transmitted light 1212 , or a combination of the two, may be manipulated by macro lens system 1206 . A more complicated or space critical application might require more elaborate optics. In such a case, a lens system might be implemented using a micro-lens array 1208 with or without the aid of redirection mirrors 1214 .
[0096] In FIG. 13 , indirect viewing may be achieved with respect to an image generated by display 1304 using either transmitted light 1310 or reflected light 1301 from light source 1300 . Lens system 1302 is then used to form an image on viewing surface, 1306 , which is where the viewer perceives the image.
Packaging and Driving Electronics
[0097] Referring to FIGS. 14 through 16 , different techniques for packaging and providing driver electronics are illustrated in order of degree of integration. FIG. 14 shows a configuration requiring two separate substrates. The IMod display array resides on substrate 1400 which could be any one of a variety of materials described in the referenced patent applications. The IMod array is not shown because it is obscured by backplate 1404 , which is bonded to substrate 1400 via seal 1402 . Backplate 1404 can also be of a number of different materials with the primary requirement being that it be impermeable to water, and that its thermal coefficient of expansion be close to that of the substrate. Seal 1402 can be achieved in a number of ways. One approach involves the application of an epoxy but this results in the generation of gases during the curing process which may interfere with the operation of the devices. Another approach involves fusion or eutectic bonding which utilizes heat to create a chemical or diffusion bond between two materials, in this case the substrate and the backplate. This process may be enhanced by forming a bead, in the form of seal 1402 , of additional materials such as silicon, aluminum, or other alloys which tend to bond well. This process may be further enhanced using a technique known as anodic bonding. This is similar to fusion bonding except that a voltage potential is applied across the backplate and substrate. This allows the bond to occur at a lower temperature. Other techniques are also possible.
[0098] The electronics 1410 comprise all of the row and column drivers, memory, and controller logic required to actuate the IMods in a controlled fashion. Exactly where each of these functions reside would depend on the application and degree of integration required for an application. Specific examples will be discussed in subsequent portions of this patent application. In FIG. 14 , the drive electronics 1410 are shown mounted on substrate 1412 . A connection is made between this substrate 1412 and the display substrate 1400 , by ribbon cable 1408 and subsequently to the display array via conductors 1406 . Many techniques exist for patterning the fine array of conductors for ribbon cable, as well as for connecting them to disparate substrates.
[0099] FIG. 15 shows a display where the electronics have been mounted on the display substrate. Display substrate 1500 serves as a support not only for the IMod array but also for the integrated circuits 1508 . Conductors 1506 are patterned to create appropriate paths between the ICs and the array. ICs 1508 may be mounted on the substrate using a number of techniques including TAB mounting and chip-on-glass techniques which rely on anisotropically conducting films.
[0100] FIG. 16 shows a display which includes fully integrated electronics and can be achieved in two fundamental ways.
[0101] In one case, substrate 1600 is an electronically inactive medium upon which the IMod array and electronics 1608 are fabricated separately or in a fabrication process with some overlap. Electronics may be fabricated using a number of techniques for building thin film transistors using materials such as amorphous silicon, polysilicon, or cadmium selenide. Electronics may also be fabricated using microelectromechanical (MEM) switches instead of, or in conjunction with thin film transistors. All of these materials are deposited on the surface of the substrate, and provide the electronically or electromechanically active medium for circuits. This implementation demonstrates a powerful approach to surface micromachining, which could be described as epi-fab. Essentially, in epi-fab all components of any microelectromechanical structure, both the mechanical and the electronic, are fabricated entirely on the surface of an inert substrate.
[0102] In the second case, the substrate is active silicon or gallium arsenide and the electronics are fabricated as a part of it. The IMod array is then fabricated on its surface. The electronics may also include more complex electronic circuits associated with the particular applications. Application specific circuits, e.g., microprocessors and memory for a laptop computer can be fabricated as well, further increasing the degree of integration.
[0103] FIGS. 17A and 17B show two drive/connection schemes. Direct drive is illustrated by a seven segment display 1700 . A common conductor 1702 connects all of the segments 1703 in parallel. In addition, separate segment conductors 1704 go to each segment individually. As shown in FIG. 17B , in a detailed corner 1712 of one segment, an array of IMods 1708 are connected in parallel and would be connected as a group to a segment conductor 1704 and the common conductor 1702 . The general microscopic nature of this type of IMod structure makes it necessary to group the IMods together to form larger elements to allow for direct viewing of the display. Application of a voltage between a selected one of the segment conductors and the common conductor actuates all of the IMods within that segment. The direct drive approach is limited by the fact that the number of conductors becomes prohibitive if the number of graphical elements gets large enough.
[0104] Referring to FIGS. 18A and 18B , an active matrix drive approach is shown. Row lines 1800 and column lines 1804 result in a two-dimensional array the intersections of which provide pixel locations such as 1802 . As seen in FIG. 18B , each of the pixel locations 1802 may be filled with an array of parallel connected IMods 1803 . In this scheme a common conductor 1808 may be connected to the row line, and the IMod array conductor, 1810 , may be connected to the column line, though this could be reversed.
Product and Device Applications
[0105] The remaining figures illustrate product and device applications which use the fabrication, drive, and assembly techniques described thus far.
[0106] The IMod as an easily fabricated, inexpensive, and capable modulator can be placed in an exceptional number of roles which require the manipulation of light. These areas fall into at least two categories: IMods which are used to modulate or otherwise affect light for purposes which do not result in direct visually perceived information (embedded applications); and IMods which are used to convey codified, abstract or other forms of information via light to be visually perceived by an individual (perceived applications). All of these applications, both embedded and perceived, can be roughly divided according to array size and geometry, however these boundaries are for descriptive purposes only and functional overlap can exist across these categories. They do not represent an exhaustive list of possibilities.
[0107] One category of applications utilizes single or individual modulators which are generally for embedded applications. These may be coupled to optical fibers or active electronics to provide, among other things, a mechanism for selecting specific frequencies on a wavelength division multiplexed fiber-optic communication system, as well as a low data rate passive fiber optic modulator. Single modulators may be coupled to semiconductor lasers to provide, among other things, a mechanism for selecting specific frequencies transmitted by the laser, as well as a low data rate laser modulator. Single modulators may be coupled to optical fibers, lasers, or active electronics to alter the phase of light reflected.
[0108] Linear arrays, though generally for embedded applications, also begin to have potential in perceived roles. Devices for printing imagery may utilize a linear array as the mechanism for impressing information on to reflected or transmitted light which is subsequently recorded in a light sensitive medium. Devices for scanning images may utilize a linear array to select different colors of a printed or real image for subsequent detection by a light sensitive device.
[0109] Yet another category of applications includes microscopic two-dimensional arrays of IMods which may be used to provide reconfigurable optical interconnects or switches between components. Such arrays may also be used to provide optical beam steering of incident light. Using a lens system, to be discussed later, may allow such an array to be readable.
[0110] Small arrays, on the order of 2″ square or smaller, may find a variety of uses for which this size is appropriate. Applications include direct view and projection displays. Projection displays can be used individually or in arrays to create virtual environments (VEs). A theater is an example of a single channel VE, while an omnimax theater, with many screens, represents a multi-channel virtual environment. Direct view displays can be used for alphanumeric and graphic displays for all kinds of consumer/commercial electronic products such as calculators, cellular phones, watches and sunglasses (active or static), jewelry, decorative/informative product labels or small format printing (business card logos, greeting card inserts, product labels logos, etc.); decorative clothing patches or inserts (sneakers, badges, belt buckles, etc.); decorative detailing or active/static graphic printing on products (tennis rackets, roller blades, bike helmets, etc.); and decorative detailing or active/static graphic printing on ceramic, glass, or metal items (plates, sculpture, forks and knives, etc.). Very large (billboard sized) displays may be produced by combining arrays of small arrays which are themselves directly driven. Embedded applications may include spatial light modulators for optical computing and optical storage. Modulator arrays fabricated on two dimensional light sensitive arrays, such as CCDs, may be used as frequency selective filter arrays for the selection of color separations during image acquisition.
[0111] Another size category of devices, medium arrays, may be defined by arrays of roughly 2″ to 6″ square. These include direct view displays for consumer electronic products including organizers, personal digital assistants, and other medium sized display-centric devices; control panels for electronic products, pocket TVs, clock faces (active and static); products such as credit cards, greeting cards, wine and other product labels; small product exteriors (walkmen, CD cases, other consumer electronic products, etc.); and larger active/static graphical patches or inserts (furniture, clothing, skis, etc.)
[0112] For arrays on the order of 6″ to 12″ square, large arrays, there exist other compelling applications. These include direct view displays for large format display-centric products (TVs, electronic readers for digital books, magazines and other traditionally printed media, special function tools); signs (window signs, highway signs, public information and advertising signs, etc.); large consumer product exteriors/active surfaces and body panels (microwave oven, telephone, bicycle, etc.); and furniture exteriors and lighting fixtures, high end products. Direct view 3-D displays and adaptive optics are also possible.
[0113] Arrays approximately 12″ square or larger, and aggregate arrays (which are combinations of smaller arrays to achieve a larger one), further define a unique set of devices, and provide the potential to affect our overall environment. These include direct view displays for very large formats (billboards, public spaces, highway, industrial/military situation displays, etc.); Body panels and active exteriors for very large products (cars, motorcycles, air and water craft, sails, refrigerators); and active/static exteriors/interiors for very large objects (buildings, walls, windows).
[0114] In FIG. 19 , a fiber optic detector/modulator 1901 includes a single IMod 1904 . An optical fiber 1900 is bonded to substrate 1902 . IMod 1904 resides on the substrate which is bonded to backplate 1910 by a seal 1908 using anodic bonding for example. The backplate also serves as a substrate for detector 1906 . Electronics 1912 are mounted on substrate 1902 via chip-on-glass or some other previously described technique. Device 1901 could provide a number of functions depending on the nature of the IMod. For example, a reflective mode IMod could act as a modulator of light which is incident through the optical fiber. Using a design which switches between absorbing or reflecting, the intensity of the reflected light may be modulated. Using a transmissive IMod, the device could act as a transceiver. Switching the IMod between fully transmissive or fully reflective would also modulate the reflected light and thus perform as a data transmitter. Holding it in the fully transmissive state would allow the detector 1906 to respond to light incident through the fiber, thus acting like a receiver. Use of a tunable IMod would allow the device to act as a frequency sensitive detector, while not precluding modulation as well.
[0115] Referring to FIGS. 20 and 21A , a linear array 2104 of IMods 2001 , 2003 , 2005 is supported on a substrate 2004 . Each of the IMods includes a primary mirror 2006 , a secondary mirror 2002 , electrodes 2008 , support arms 2000 , and support plate 2010 . Each IMod would be driven separately in a binary or analog fashion depending on the application. In the representative application shown in FIG. 21A , a transport mechanism 2106 moves a medium 2108 past a linear IMod array 2104 (the axis of the array is into the page). Two potential applications for such a configuration could include image acquisition or digital printing. In acquisition mode, component 2100 is a detector array which is coupled to IMod array 2104 via lens system 2102 . Component 2110 acts as a light source, illuminating pre-printed images which reside on media 2108 . By using the IMod as a tunable filter array, specific colors of the image on the media may be selected and detected, allowing for high resolution capture of graphical information residing on the media.
[0116] Alternatively, component 2100 could be a light source which uses lens system 2102 to couple and collimate light through IMod array 2104 onto media 2108 . In this case, the media would be a photosensitive material which would undergo exposure as it passed beneath the array. This would provide a mechanism for the printing of high resolution color images. No electronic components reside on the array substrate in this example. FIG. 21B shows a components diagram illustrating one way in which this product could be implemented using off-the-shelf components. In this case, they comprise a central controller 2112 , (including processor 2114 , memory 2116 , and low level I/O 2118 ), high level I/O components (user interface 2120 and logic 2122 , detector array 2130 ), control components (light source 2132 , media transport 2128 and logic 2126 ), display 2140 (logic 2138 , drivers 2136 , IMod array 2134 ) and power supply 2124 . The central controller handles general purpose operational functions, the high level I/O components and display dictate how information gets in and out of the product, and the controller components manipulate peripheral devices.
[0117] Referring to FIG. 22 , a two-dimensional IMod device 2201 is fabricated directly on a photosensitive detector array 2206 such as a charge coupled device (CCD) or other light sensitive array. Array 2206 has photosensitive areas 2202 and charge transport and IMod drive electronics 2204 . Planarization layer 2208 , deposited on the CCD, provides a flat surface for the fabrication of the IMod array 2200 . Such a layer could be in the form of a curable polymer or spun-on oxide. Alternatively, some form of chemical mechanical polishing might be used to prepare an optically smooth surface on the integrated circuit. Device 2201 provides a fully integrated 2-D, tunable light detection system which can be used for image capture or image printing (if the detector is replaced with a light source).
[0118] FIG. 23 illustrates a digital camera 2301 based on this device. Camera body 2300 provides mechanical support and housing for lens system 2304 and electronics and IMod detector array 2302 . Scene 2306 is imaged on the surface of the array using the lens system. By tuning the IMod array to the frequencies of light corresponding to red, green, and blue, a full color image may be acquired by combining successive digital exposures. Hyperspectral imagery (in other wavelength regions such as ultraviolet or infrared) may be obtained by tuning to frequencies between these points. Because of the high switching speed of the IMods, all three images may be acquired in the time it takes a conventional camera to capture one.
[0119] Referring to FIG. 24A , an application for small-sized displays is a digital watch 2400 (the back side of the watch is shown in FIG. 24A ) which includes a reflective IMod display at its core. The IMod display comprises an IMod array 2402 and drive electronics, 2404 . The display (see examples in FIGS. 24B-24E ) could vary in complexity from separate graphic elements driven in a direct drive manner, to a dense array using active matrix addressing, or some combination. The electronics could be fabricated on glass using polysilicon or amorphous silicon transistors, or MEM switches. While the direct drive approach would still exploit the saturated appearance of the IMod, a dense array would allow for the selection of arbitrary or pre-programmed graphical patterns such as FIG. 24B . This would add an exciting new fashion component to watches not unlike the art oriented Swatch® only in electronic form. Owners could select from a series of preprogrammed displays 2408 ( FIG. 24D ), say by pushing the stem, or download limited edition displays digitally from their favorite artists.
[0120] Referring to FIG. 25A , a small transmissive IMod array is shown in a head mounted display 2511 . Support 2508 provides a frame for mounting the display components and the viewer screen 2512 . Referring also to FIG. 25B , the display includes a light source 2500 , an IMod array 2502 , a lens system 2504 , and a reflector 2506 . The display is used in indirect mode with the image formed on screens 2512 for the benefit of viewer 2510 . Alternatively, the IMod array could be formed directly on the screen itself and thus be used in direct view mode. In both cases, the display could function to provide aesthetic imagery which could be seen by other individuals and provide an appealing dynamic external look.
[0121] Referring to FIGS. 26A through 26D , an IMod display 2604 is shown in a product with a very wide range of applications. In this case, the display is used in direct view mode, and could come in a variety of sizes depending on the specific product, but ranging in size from several inches across to about one foot diagonal. The primary goal is for a device that has a very small footprint and/or is portable, and the scheme is to facilitate mobility. The device 2600 could be described as a personal information tool, a portable digital assistant, a web browser, or by various other titles which are only now being coined to describe this class of products. In general its purpose would be to serve as a media interface for a variety of information gathering, processing, and dissemination functions, or as a mobile or stationary peripheral for a centralized processing station to which it is connected, perhaps via the internet or some wireless communications medium. A specialized peripheral in a home-based application might be a kitchen cooking assistant which would be portable and present easily readable recipes by virtue of the display and the fact that most of its processing is located in some other unit. Many other variations on this theme are possible. This tool comprises a display 2604 and some basic controls 2602 . Internal components would include some combination of processing electronics, information storage, and communications hardware. Representative products range from personal organizers and digital books and magazines, to application specific tools (construction, medical, scientific) or tools for browsing the internet. Techniques for operating such a tool are varied and could range from voice recognition, to touch sensitive screens. However, all of the products would have the ability to digitally display graphical information using reflected (preferred) or transmitted light with highly saturated colors. Because it is digital, the complexity and cost of the driving electronics would be significantly reduced, and because it can use reflected light, the power consumption is extremely low while the performance remains high. These two characteristics make such a high performance display oriented product viable from an economic and portability perspective. FIG. 26C is an example of one kind of personal communications device, a cellular phone in this case though the pager of FIG. 26D is an example of another. Display 2608 is capable of displaying both graphical and text information. FIG. 26B shows a components diagram illustrating one way in which these products could be implemented using available off-the-shelf components. In this case, they comprise a central controller 2610 (including processor 2612 , memory 2614 , and low level I/O 2616 ), high level I/O components (user interface 2618 and logic 2620 , audio I/O 2624 , digital camera 2628 , and wireless transceiver 2630 ), display 2638 (logic 2636 , drivers 2634 , IMod array 2632 ) and power supply 2622 . The central controller handles general purpose operational functions, while high level I/O components dictate how information gets in and out of the product.
[0122] Referring to FIG. 27A through 27G , several applications are shown which emphasize the aesthetic nature of an IMod display as well as its information conveying aspect. An IMod display could be included in a portable compact disc player 2700 of the kind that serves as a commodity status device made by many manufacturers. By virtue of an IMod display, a larger fraction of the exterior of the player may be devoted to information display functions, indicating status of the device as well as tracks playing. Because it consumes such a large fraction of the exterior, it would be possible to have the display play a more significant role in the appearance of the CD player. Static as well as dynamic patterns and images could be displayed which may or may not have any connection with the status of the player. However, because of the rich saturated colors, the appearance becomes a significant and distinct selling point for the manufacturer. This concept holds true for any number of consumer electronic devices whose form and function could be enhanced by an active exterior. A microwave oven which pulsed red when the food was done, or a bread baking machine whose exterior changed colors as the baking process progressed are just two examples. FIG. 27C shows a components diagram illustrating one way the CD player could be implemented using off-the-shelf components. In general, they comprise a central controller 2706 (including processor 2707 , memory 2710 , and low level I/O 2712 ), high level I/O components (user interface 2702 and logic 2704 ), display 2722 (logic 2720 , drivers 2718 , IMod array 2716 ) disc player mechanism 2714 , and power supply 2724 . The central controller handles general purpose operational functions, high level I/O components dictate how information gets in and out of the product, and the disc play mechanism manipulates mechanical servos.
[0123] The skis of FIG. 27D and the sneaker of FIG. 27F are examples of consumer goods which could benefit purely from the aesthetic potential for an active exterior. In both cases, an IMod array has been fabricated on a substrate, for example flexible plastic, along with electronics and integrated into the product using any number of techniques currently used for incorporating or laminating composite pieces into fabric or solid composites. Power could be supplied by piezoelectric like devices which convert the mechanical power of movement (e.g., ski flexing or walking) into electricity. Remote control, FIG. 27E , could be used to effect control over the images displayed. Further control could be exhibited to reflect the mode of use of the product. In the case of the skis, the pattern might become more dynamic as the skier gained speed, or in the case of the shoes the strength of the runner's stride. These are only a few of the possibilities for the aesthetic enhancement of consumer goods by the use of a dynamic exteriors. FIG. 27G illustrates how a display could respond to the state of the consumer product. The control mechanism would consist of a sensor 2732 , which could detect vibration (in a shoe or ski) or temperature (in a turkey), program logic 2734 , which would interpret the sensor output and provide preprogrammed (or reprogrammable) images or image data to display, communications input/output 2738 , and display control electronics 2736 .
[0124] Referring to FIGS. 28A and 28B , even larger IMod arrays are shown incorporated into the exterior of an automobile. In this case body panels 2800 , 2802 as well as windows 2804 , could use reflective and transmissive IMod designs respectively. Dynamic control of the exterior appearance of a car would be a very appealing option for the owner, providing the ability for the owner to customize the appearance himself, or to “download” exteriors in a digital fashion. Such a control 2806 could take the form of a small panel integrated into the dashboard which displayed various exteriors under button control. The same techniques could be applied to other highly style oriented goods in the class and functional category, including motorcycles, sailboats; airplanes and more. FIG. 28B shows a components diagram illustrating one way in which this product could be implemented using off-the-shelf components. In general, they comprise a central controller 2808 (including processor 2810 , memory 2812 , and low level I/O 2814 ), high level I/O components (user interface 2816 , and logic 2818 ), display 2828 (logic 2826 , drivers 2824 , IMod array 2822 ) and power supply 2820 . The central controller handles general purpose operational functions, while high level I/O components dictate how information gets in and out of the product.
[0125] Referring to FIGS. 29A through 29D , billboard-sized arrays 2900 of IMod display segments could be assembled and replace current static displays used for advertising and public service announcements. Display 2900 would include reflective devices to be illuminated by ambient light or a supplemental light source 2902 . A large display could be assembled from individual segments 2904 ( FIG. 29B ) which would support segment pixels 2906 . Each segment pixel would include three sets of sub-pixel arrays 2910 , 2912 , and 2914 , which would reside on pixel substrate 2908 ( FIG. 29C ). The resulting large displays could range from placards on the sides of buses and inside of subways, to billboards, to entire architectural structures such as homes or skyscrapers. In FIG. 30A , skyscraper 3000 is an example of a large building which exploits the aesthetic and cheap manufacture of the IMod array. All of the glass used in the manufacture of such structures is coated with thin films up to 4 or more layers thick to provide energy efficient coatings. Similar coating techniques could be applied to the manufacture of the IMod arrays. FIG. 30B shows a components diagram illustrating one way in which both of these products could be implemented using off-the-shelf components. In this case, they comprise a central controller 3002 (including processor 3004 , memory 3006 , and low level I/O 3006 ), high level I/O components (PC based user interface 3008 ), display 3020 (logic 3018 , drivers 3016 , IMod array 3014 ), lighting control 3012 , and power supply 3010 . The central controller handles general purpose operational functions, high level I/O components dictate how information gets in and out of the product, and the controller components manipulate supplementary lighting and peripheral components.
[0126] It should be noted that several alternative display technologies may also be applicable to some of the less rigorous aesthetic applications, in particular, small AMLCDs, LCDs fabricated on active crystalline silicon, field emission displays (FEDs), and possibly plasma based displays. These technologies are deficient due to their price, manufacturing complexity, and non-reflective (emissive) operation. However, certain high-end fashion oriented products (luxury watches, jewelry and clothing) may command a price and provide an environment which could make these viable approaches. Organic emitters could be particularly suited for exterior applications which are not necessarily exposed to environmental extremes and which might be seen in dimly lit situations. They are the only emissive technology which offers the potential for very low-cost and ease of manufacture. The Alq/diamine structures and poly(phenylene vinylene) materials, which were described before, could be patterned and directly addressed on a variety of substrates (plastic clothing inserts for example) to provide dynamic exteriors.
[0127] FIG. 31A shows interferometric particles suspended in a liquid crystal medium, 3100 , making possible full color liquid crystal displays based on the controlled orientation of the particles within the medium. As shown in FIG. 31B , application of a voltage between electrodes 3102 from source 3104 causes the particles to be driven from their random quiescent orientation 3106 defined by the liquid crystal and the surfaces of the substrate into an orderly orientation 3108 . When the particles are randomly oriented, light of a specific color 3110 is reflected. When the particles are ordered, light 3112 passes through.
[0128] Referring to FIG. 32A , two kinds of projection display units, 3200 and 3202 , are shown. Each unit comprises components consisting of light source/optics 3206 , electronics 3204 , projection optics 3210 , and IMod array 3208 . While the IMod array in projector 3200 is designed for use in transmission mode, the IMod array in projector 3202 is designed for use in reflection mode. The other components are essentially the same with the exception of the need to modify the optics to accommodate the difference in the nature of the optical path. Screen 3212 shows a representative projected image. FIG. 32B shows a components diagram illustrating one way in which this product could be implemented using off-the-shelf components. In this case, they comprise a central controller 3212 (including processor 3214 , memory 3216 , and low level I/O 3218 ), high level I/O components (user interface 3220 and logic 3222 ), display 3236 (logic 3234 , drivers 3232 , IMod array 3230 ) focus/light source control 3226 , and power supply 3224 . The central controller handles general purpose operational functions, high level I/O components dictate how information gets in and out of the product, and the controller components manipulate peripheral devices.
[0129] An application in chemical analysis is illustrated in FIG. 33A . Transparent cavity 3300 is fabricated such that gas or liquid medium 3302 may pass through its length. Light source 3304 is positioned to project broad spectrum light through the medium into tunable IMod array 3306 . This array could be coupled to a fiber 3308 , or reside on a detector array with 3308 acting as data link to electronics 3310 . By spectrally analyzing the light which passes through the medium, much can be determined about its composition in a compact space. Such a device could be used to measure the pollutants in an air stream, the components in a liquid, separations in an chromatographic medium, fluorescing compounds in a medium, or other analytes which can be measured using light, depending on the frequency of the light source. FIG. 33B shows a components diagram illustrating one way in which this product could be implemented using off-the-shelf components. In this case, they comprise a central controller 3312 (including processor 3314 , memory 3316 , and low level I/O 3318 ), high level I/O components (user interface 3320 , and logic 3322 ), IMod drivers 3330 and IMod 3328 , light source 3326 , and power supply 3324 . The central controller handles general purpose operational functions, high level I/O components dictate how information gets in and out of the product, and the controller components manipulate peripheral devices.
[0130] FIG. 34A illustrates an automotive application from a driver's viewpoint. FIG. 34B represents a side view of the windshield and dashboard. A direct view graphical display 3404 portrays a variety of information, for example, an enhanced view of the roadway. An image generated in the windshield via a heads-up display. Such a display is a variation on the previously discussed projection system. In this case, the inside of the windshield acts as a translucent projection screen, and the projector 3406 is mounted in the dashboard. Automotive applications have very stringent requirements for heat, and UV stability, as well as high brightness ambient conditions which would be ideal for an IMod application. FIG. 34C shows a components diagram illustrating one way in which these products could be implemented using off-the-shelf components. In this case, they comprise a central controller 3410 (including processor 3412 , memory 3414 , and low level I/O 3416 ), high level I/O components (user interface 3418 , digital camera 3428 , auto sensors 3424 ), display 3436 (logic 3434 , drivers 3432 , IMod array 3430 ) and power supply 3422 . The central controller handles general purpose operational functions, high level I/O components dictate how information gets in and out of the product, and the controller components manipulate peripheral devices.
[0131] FIG. 35A portrays an application involving an instrument panel, in this case an oscilloscope 3500 , though many kinds of special purpose tools could benefit from a graphical display. In this situation, display 3502 , is used to show a waveform plot but could also, as described previously, display text, or combinations of graphics and text. Portable low-power tools for field use would benefit greatly from a full-color fast response FPD. FIG. 35B shows a components diagram illustrating one way in which these products could be implemented. All of the components are available off-the-shelf and could be configured by one who is skilled in the art. In this case, they comprise a central controller 3508 (including processor 3510 , memory 3514 , and low level I/O 3516 ), high level I/O components (user interface 3518 and logic 3520 ), display 3534 (logic 3532 , drivers 3530 , IMod array 3528 ) and power supply 3522 . The central controller handles general purpose operational functions, while high level I/O components dictate how information gets in and out of the product.
[0132] Other embodiments are within the scope of the following claims. | A system and method for displaying an image using projection optics is disclosed. In one embodiment, a projector comprises an array of display elements, each display element comprising a first layer which is at least partially reflective and a second layer which is at least partially reflective and spaced a variable distance from the first layer, a controller configured to change the variable distances of the display elements based on image data representing an image, a light source configured to illuminate the array of display elements, and at least one lens configured to refract light reflected by or transmitted through the array so as project the image. | 6 |
FIELD OF THE INVENTION
[0001] This invention relates to a process of entrapping genetic materials in nanoparticles of inorganic compounds of size below 100 nm diameter to form non-viral carriers suitable for delivery of genes including those of therapeutic interest in appropriate cells.
BACKGROUND OF THE INVENTION
[0002] As it is known, the ability to safely and efficiently transfer foreign DNA into cells is a fundamental goal in biotechnology. In recent years, with the advent of recombinant DNA technology, a surge in research activity has occurred in the field of DNA transfer across cell lines. This activity, which has taken the shape of what is popularly known as gene therapy, is a medical/surgical intervention technique which is being developed as a ‘molecular medicine’ and requires genes to be introduced into cells in order to treat a wide variety of till now incurable human diseases. Potential applications are numerous, given the diversity of the genes to be used as well as the possible target cells.
[0003] Today's gene therapy research may be seen as pursuing intelligent drug design through a logical extension of results of fundamental biomedical research on the molecular basis of disease. The term gene therapy applies to approaches to disease treatment based on the insertion of genetic material (DNA and RNA) into a cell's genetic pool either to correct an underlying defect or to modify the characteristics of a cell via expression of the newly inserted gene. In order to successfully implement this technique, effective means of delivering the therapeutic gene to the target cell is required, in such a way that the gene can be expressed at the appropriate level and for a sufficient duration. Two broad approaches have been used to deliver DNA and RNA to cells, namely viral and non-viral vectors, which have different advantages as regards efficiency, ease of production and safety.
[0004] One of the most powerful methods for gene-transfer is the use of viral vectors. A viral vector is genetically engineered from ‘wild-type’ virus, and consists of a modified viral genome and virion structure. By retaining the protein coat of the original virus, the vector is able to bind and penetrate the cell more effectively while protecting the genome from endogenous enzymes. As for the original viral genome (wild-type), only the essential viral sequence necessary for transcription is retained. There are a number of viral vectors that are currently being used for transfecting cells. Of interest are retroviruses (enveloped single strand RNA), adenoviruses (non-enveloped double stranded DNA) and adeno-associated viruses (linear single stranded DNA). Due to their inherent nature of penetrating and inserting their genetic material (genome) into the target cell, viral vectors result in very high transfection rates. In addition to escaping the target cell's endonucleases, viral genes also possess promoters and enhancers that increase the probability of genetic expression.
[0005] Although viral vectors are attractive in terms of the scientific strategy of exploiting natural mechanism, there are some major drawbacks associated with them. They suffer from inherent difficulties of effective pharmaceutical processing, immunogenicity, difficulty in targeting to specific cell types, scale up and the possibility of reversion of an engineered virus to the wild type. The safety risks include ‘Insertional Mutagenesis’ and toxicity problems. Ever since the death of Jesse Gelsinger in September 2000, scientists have began to severely question the safety aspects related to viral vector mediated gene delivery. Consequently, a major focus is now being given at the development and use of alternative vectors based on synthetic, non-viral systems for safe and efficient gene delivery.
[0006] The problems associated with viral vectors have led to a growing interest in non-viral gene delivery systems. Non-viral vectors are techniques of introducing a coding DNA sequence without the means of a virus. The self-assembly of artificial plasmid (pDNA) containing vectors is required for the development of such vectors. These methods of gene transfer require only a small number of gene, have a virtually infinite capacity, have no infectious or mutagenic capability and large scale production is possible using pharmaceutical techniques. DNA itself is negatively charged, as is the cell membrane and therefore the entry of naked DNA is restricted due to electrical repulsion forces. To reduce this repulsion, many researchers have encased the polynucleotide with a cationic membrane so as to alter the electrical distribution and charge of the complex. These include lipid-based carriers, polycationic lipids, polylysine, polyomithine, histones and other chromosomal proteins, hydrogel polymers and precipitated calcium phosphate (CaPi). One of the major drawbacks of the use of these non-viral vectors is their low transfection efficiency which is caused due to exposure of DNA in the hostile DNAse environment due to simple electrostatic compaction of DNA with the polymeric materials. Among these, the technique of calcium phosphate co-precipitation for in vitro transfection is used as a routine laboratory procedure. This procedure involves a reaction of calcium chloride with sodium phosphate to form a water insoluble calcium phosphate precipitate, which can bind to pDNA. This method heavily relies on the fact that divalent metal cations, such as Ca 2+ , Mg 2+ , Mn 2+ and Ba 2+ can form ionic complexes with the helical phosphates of DNA. Calcium phosphate, therefore, forms complexes with the nucleic acid backbone and thus may impart a stabilizing function to certain DNA structures. When added to a cell monolayer, the cells take up the water insoluble calcium phosphate-pDNA complex (Ca Pi—pDNA) by transportation across the membrane through Ca 2+ ion mediated channel formation. This process is an example of ion channel mediated endocytosis. Once inside the cell, the CaPi-pDNA complex is broken down inside the endosome, thereby releasing the pDNA into the cytosol, which, under suitable circumstances, can be incorporated into the host cell genome. In addition, being inorganic particles, calcium phosphate is highly stable, non-toxic, non-antigenic and non-carcinogenic.
[0007] Although extremely safe, the major shortcoming of this process is the poor transfection efficiency as compared to that of viral vectors. The general belief is that the transfection with CaPi-DNA is a low efficiency procedure partly because most of the endocytosed DNA is quickly degraded and excreted to the cytosol. A small fraction of the remaining DNA macromolecules important for gene transfer may be delivered from the endosomal compartment through membrane bound organelles to the nucleus without traversing the cytosol. Moreover, although calcium phosphate precipitation method is simple, effective and still widely used in laboratory for in vitro transfection, the method is hampered by the difficulty of applying to in vivo studies, especially delivery of DNA to any particular cell types. Due to bulk precipitation of calcium phosphate, the method also suffers from variation in calcium phosphate-DNA particle size, which causes variation among experiments.
[0008] Process for production of inorganic nanoparticles has been described in U.S. Pat. Nos. 5,460,831 and 5,879,715. Although the process has described the method of preparation of particles of size as small as 10 nm diameter the preparative method does not describe anything about the encapsulation of biologically active materials inside the matrices of these nanoparticles. Calcium Phosphate nanoparticles of size 300 nm and above have been reported in U.S. Pat. No. 6,355,271, which have been, used as carriers and as controlled release matrices for biologically active materials. Virus-like-size particles i.e. particles of size below 100 nm diameter encapsulating genetic materials, which are biologically safe and cost effective, are the main criteria of a non-viral vector for effective delivery of genes. We have described in this invention of the preparation of below 100 nm diameter inorganic nanoparticles doped with genetic material such as DNA or RNA as a non-viral carrier for the delivery of genes or their modified compounds.
OBJECTS AND SUMMARY OF THE INVENTION
[0009] The object of this invention is to propose a novel process for the preparation of nearly monodispersed non-toxic and biocompatible inorganic materials such as calcium, magnesium, manganous phosphates and the like, encapsulating genetic materials such as DNA and RNA and having a size maximum upto 100 nm diameter with near monodispersity.
[0010] Another object of this invention is to propose a process for the preparation of nearly monodispersed inorganic nanoparticles of subcolloidal size with targeted DNA and RNA materials.
[0011] Yet another object of this invention is to propose a process for the preparation of nearly monodispersed inorganic nanoparticles dispersed in aqueous buffer and free from any toxic materials.
[0012] Further object of this invention is to propose a process for the complete encapsulation of the therapeutic genetic material into the matrix of the inorganic nanoparticles to secure them from outer intervention in vivo or cell culture in vitro till they are exposed to the target site within the cell.
[0013] A still further object of this invention is to propose a process for the preparation of nearly monodispersed DNA or RNA loaded inorganic nanoparticles covered with strongly adhesive and non-toxic biocompatible polymeric material chemically conjugated with targetable ligand so that the particles can be targeted to specific cell types in vivo, which obviates the disadvantages associated with these of the prior art.
[0014] To achieve these objectives, this invention provides a process of entrapping genetic materials in nanoparticles of inorganic compounds of size below 100 nm diameter to form non-viral carriers suitable for delivery of genes including those of therapeutic interest comprising the steps of:
[0015] (a) dissolving 0.01M to 1.0M of a surfactant or a mixture of surfactant and a cosurfactant in oil to obtain reverse micelles,
[0016] (b) adding an aqueous solution of genetic material to the reverse micelles,
[0017] (c) dividing the reverse micelles obtained in step (b) into two equal parts,
[0018] (d) dissolving aqueous solution of 0.1 to 1.0M inorganic metal salts in one part of reverse micelles (step c) to obtain optically clear and transparent reverse micelles after dissolution,
[0019] (e) adding aqueous solution of 0.1 to 1.0M precipitating agent in the second part of reverse micelles (step c) to obtain optically clear and transparent reverse micelles after dissolution,
[0020] (f) maintaining the same molar ratio of water to surfactant in steps d and
[0021] (g) mixing the reverse micelles of both steps (d) and (e) and stirring to form inorganic nanoparticles encapsulating added genetic material,
[0022] (h) separating the nanoparticles from reverse micelles, and
[0023] (i) dispersing the inorganic nanoparticles in water and dialyzing to remove free metal salts, surfactant and oil.
[0024] The above process further comprises coating the nanoparticles surface by adhesive polymeric compound and chemically conjugating ligand molecules for targeting the nanoparticels to specific cell type.
[0025] The surfactant is selected from the group containing anionic, cationic and non-ionic type.
[0026] The oil used for the preparation of reverse micelles is hydrocarbon oil.
[0027] The hydrocarbon oil is a saturated long chain or branched chain hydrocarbon of C 6 to C 10 chain length.
[0028] The hydrocarbon oil is n-Hexane.
[0029] The reverse micelles contain a long chain alcohol from butanol to octanol in the form of cosurfactant when it is required to stabilize the reverse micelles.
[0030] The genetic materials are selected from DNA and RNA and genetic modifications thereof.
[0031] The inorganic metal salts are selected from the group containing calcium chloride, magnesium sulphate and manganous sulphate and the precipitating agent is disodium hydrogen phosphate.
[0032] The inorganic metal salt is ferric chloride and the precipitating agent is ammonium hydroxide.
[0033] The separation of nanoparticle is carried out by precipitating with ethanol and ishing the precipitate with ethanol.
[0034] The inorganic nanoparticles are calcium phosphate, magnesium phosphate, manganous phosphate and ferric oxide.
[0035] The nanoparticles after separating from micelles be dispersed in water either by mild agitating, prolonged stirring or by sonication.
[0036] The molar ratio of water to surfactant (W 0 ) is in the range of W 0 =10 to W 0 =40.
[0037] The nanaoparticles encapsulating genetic material have diameter in the range of 10 nm to 100 nm.
[0038] The adhesive polymeric materials used for coating the nanoparticles is polyacrylic acid.
[0039] The ligand is a molecule having at least one amino group selected from the group containing sugar, an antibody, folic acid, transferrin and biotine or derivatives thereof
[0040] The carboxylic group of polyacrylic acid is conjugated with the amino group of the ligand molecule.
[0041] In accordance with this invention the aqueous core of a reverse micellar droplet is used as a nanoreactor for the preparation of nanoparticles. Near monodispersity of the inorganic particles is possible because reverse micellar droplets in which the precipitation reactions are carried out are highly monodispersed. The size of the nanoparticles is governed by the size of the aqueous core of reverse micellar droplets, which is dependent on the molar ratio of water to surfactant (wo) of the reverse micelles. The wo of reverse micelles is kept in the range of 10 to 40 and the nanoparticles formed in such reverse micelles have average size below 100 nm diameter.
[0042] The composition of aqueous phase of reverse micellar droplets is regulated in such a manner so as to keep the entire mixture in an optically transparent reverse micellar phase. The range of aqueous phase can not be defined apriori as this would depend on factors such as nature and solubility of the metal salt used the nature and solubility of the precipitating agent and their interaction with the polar head group of the surfactant. The only factor that is important is that the system should be in an optically transparent reverse micellar phase.
[0043] In accordance with the present invention the nanoparticles have size range of upto 100 nm diameter. In accordance with this invention the aqueous core of a reverse micellar droplet having a predetermined wo value is effectively used as nanoreactor to prepare ultrafine nanoparticles and to encapsulate the plasmid DNA, RNA or their derivatives. The process of the present invention has achieved extremely small size nanoparticles (diameter in the range of 10 nm to 100 nm) of greater uniformity.
[0044] The strategy involves precipitation of insoluble inorganic metal salts in the form of nanoparticles encapsulating DNA and RNA in the aqueous core of the reverse micellar droplets. As the aqueous core of reverse micelles are of nanosized dimensions, the particles prepared inside them are also nanometer sized. In addition, the aqueous core of reverse micelles has long been known as a medium for solubilizing biomolecules like enzymes, antibodies, other proteins, nucleic acids etc., without damaging their biological activities. In this work, we have achieved inorganic materials to undergo precipitation reaction inside the aqueous core of reverse micelles and have obtained nearly monodispersed nanoparticles completely encapsulating (more than 99%) genetic materials. We have also demonstrated that these nanoparticles doped with genetic material can be used as efficient non-viral vectors for delivery of genes in vitro and in vivo. Because of the extremely low size of the particles, their aqueous dispersion will have easy circulation in the blood. Additionally, these nanoparticles could also be targeted using ligands to receptors of specific cell types in vivo. For this we could cover the surface of these inorganic nanoparticles by some adhesive polymer having a suitable functional group, which can be chemically conjugated with appropriate ligand molecules. Through our invention we have overcome the two major impediments for using inorganic materials as non-viral vectors: (i) use of ultrafine nanoparticles so that the aqueous dispersion of these inorganic salts can become easily injectable systems and (ii) targeting these nanoparticles to specific cell types by coating the nanoparticle surface with adhesive polymer and conjugating them with appropriate ligand. By this way, inorganic nanoparticles mediated gene delivery can become more advantageous compared to other viral and non-viral carriers in the sense that the method is absolutely safe as well as cost effective. With the prospect of reviving this methodology of using calcium phosphate as carriers by improving on the preparative conditions, we have tried to devise a strategy that would make the process more efficient and useful, as well as suitable for in vivo applications.
BRIEF DESCRIPTION OF THE DRAWINGS
[0045] The invention will now be described with reference to the accompanying drawings and forgoing examples.
[0046] [0046]FIG. 1 shows a flow diagram for the preparation of inorganic nanoparticles in reverse micelles.
[0047] [0047]FIG. 2 a shows a QELS diagrams of the size of the particle.
[0048] [0048]FIG. 2 b shows TEM picture of the nanoparticles.
[0049] [0049]FIG. 3 shows gel electrophoresis of DNA free and encapsulated.
[0050] [0050]FIG. 4 shows in vitro transfection of pSVβgal in Jurkat cell lines.
[0051] [0051]FIG. 5 a shows in vivo biodistribution of pSVβgal loaded calcium phosphate nanoparticles administered through intramuscular route.
[0052] [0052]FIG. 5 b shows in vivo bio distribution of pSVβgal loaded calcium phosphate nanoparticles administered through interaperitoneal route.
[0053] [0053]FIG. 6 a shows β-galactosidase expression in vivo after administration of a galactopyranoside taged Calcium phosphate nanoparticles encapsulating pSVβgal through ip injections.
[0054] [0054]FIG. 6 b shows β-galactosidase expression in vivo after administration of galactopyranoside taged Calcium Phosphat nanoparticles encapsulating pSVβgal through im injections.
DETAILED DESCRIPTION
[0055] Reference is now made to FIG. 1 of the accompanying drawings, which illustrates the flow diagram for the preparation of inorganic nanoparticles using reverse micelles. Inorganic nanoparticles are prepared in the aqueous core of reverse micellar droplets as follows: When using AOT/water/n-Hexane reverse micelles, 0.1M sodium bis(ethylhexyl)sulphosuccinate (AOT) in hexane solution is prepared. In 0.1M AOT in hexane, aqueous solution of metal salt, double distilled water and the genetic material to be encapsulated are dissolved by continuous stirring to form reverse micelles A. In another AOT in hexane, aqueous solution of precipitating agent e.g. Na 2 HPO 4 , to precipitate metal phosphates or ammonium hydroxide to precipitate metal oxides, double distilled water, 0.2 M Tris-HCl buffer of required pH in which the precipitation of metal salt would have taken place and the genetic material to be encapsulated, is dissolved by continuous stirring to form reverse micelles B. Both the reverse micelles have same molar ratio of water to surfactant i.e. wo and are optically clear solutions. Then, reverse micelles B is slowly added to reverse micelles A at the rate of 5 mL per hour with continuous stirring at 8-10° C. The solution is then, further stirred in cold for some time. The resulting solution is translucent due to solid inorganic nanoparticles dispersed in the reverse micelles. Next, to separate the nanoparticles, the solution is centrifuged at 8000 rpm. Alternatively, after evaporation of the solvent, it can be treated with dry ethanol to precipitate nanoparticles. The nanoparticles (containing the entrapped genetic material) are settled at the bottom of the tube, and the supernatant solution is drained off. The pelleted nanoparticles are washed with hexane or ethanol three times to remove any residual surfactant. Finally, the nanoparticles are redispersed in 10 mL of double distilled water by mild agitation, stirring or sonication. The aqueous dispersed nanoparticles are dialysed in a 12 kD cutoff cellulose membrane whereby residual small molecules like surfactant, hexane, unentrapped DNA or RNA are separated leaving behind highly purified nanoparticles doped with added genes dispersed in water. This aqueous dispersion of nanoparticles is lyophilized to fine powder for further use.
[0056] The potential use of these inorganic nanoparticles have been explored as vectors for hepatic gene transfer. Nanoparticles are incubated with a highly adhesive polymer like polyacrylic acid (PAA), followed by dialysis to remove excess polymer. The PAA molecules adhered on the surface of the calcium phosphate nanoparticles are further modified by conjugating the carboxylic groups with p-aminophenyl-1-thio-β-D-galactopyranoside (PAG) using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDCI). The galactopyranoside moiety serves as a surface ligand for recognizing asialoglycoprotein receptor on liver cells. The tagged nanoparticles shows preferential expression in liver tissue relative to lung, spleen and muscle. These observations suggest redistribution of genetic material in relation to the particle surface characteristics.
EXAMPLES
[0057] The following examples are given by way of illustration of the present invention and should not be construed to limit the scope of present invention.
Example—1
[0058] Preparation of Calcium Phosphate Nanoparticles Encapsulating pSVβgal:
[0059] Calcium phosphate nanoparticles are prepared in the aqueous core of AOT/Hexane reverse micellar droplets as follows: 0.1M sodium bis(ethylhexyl)sulphosuccinate (AOT) in hexane solution is prepared. In 25 mL of 0.1M AOT in hexane, 50 μL of aqueous solution of CaCl 2 (1.3M), 390 μL double distilled water and 10 μL of pDNA (400 ug/1L) are dissolved by continuous stirring for 72 hours to form reverse micelles A. In another 25 ml of AOT in hexane, 50 μL of aqueous solution of Na 2 HPO 4 (5% w/v), 340 μL of double distilled water, 50 μL of 0.2 M Tris-HCI buffer (pH 6) and 10 μL of pDNA (400 μg/mL) are dissolved by continuous stirring for 48 hours to form reverse micelles B. Both the reverse micelles A and B have wo=10 and are optically clear solutions. Then, reverse micelle B is slowly added to reverse micelles A at the rate of 5 mL per hour with continuous stirring at 8-10° C. The solution is, then, further stirred in cold for another 6 hours. The resulting solution is translucent due to calcium phosphate nanoparticles dispersed in the reverse micelles.
Example—2
[0060] Calcium phosphate nanoparticles are prepared in the aqueous core of CTAB/nButanol/n-Octane reverse micellar droplets as follows: 0.1M of CTAB mixed with nButanol in the molar ratio 1:0.73 in n-Octane solution is prepared. In 25 mL of 0.1M reverse micelles, 50 μL of aqueous solution of CaCl 2 (1.3M), 390 μL double distilled water and 10 μL of pDNA (400 μg/mL) are dissolved by continuous stirring for 72 hours to form reverse micelles A. In another 25 ml of CTAB/n-Butanol/n-Octane reverse micelles of same composition as reverse micelles A, 50 μL of aqueous solution of Na 2 HPO 4 (5% w/v), 340 μL of double distilled water, 50 μL of 0.2 M Tris-HCl buffer (pH 6) and 10 μL of pDNA (400 μg/mL) are dissolved by continuous stirring for 48 hours to form reverse micelles B. Both the reverse micelles A and B have wo=10 and are optically clear solutions. Then, reverse micelle B is slowly added to reverse micelles A at the rate of 5 mL per hour with continuous stirring at 8-10° C. Then, reverse micelle B is slowly added to reverse micelles A at the rate of 5 mL per hour with continuous stirring at 8-10° C. The solution is, then, further stirred in cold for another 6 hours. The resulting solution is translucent due to calcium phosphate nanoparticles dispersed in the reverse micelles.
Example—3
[0061] Separation of Nanoparticles from Reverse Micelles and Redispersion in water.
[0062] Next, to separate the nanoparticles, the reverse micelle solution is centrifuged at 8×10 3 rpm for half an hour. The nanoparticles (containing the entrapped DNA) settle at the bottom of the centrifuge tube, and the supernatant solution is drained off. The pelleted nanoparticles are washed with hexane three times to remove any residual surfactant. Finally, the nanoparticles are redispersed in 10 mL of double distilled water by sonication in cold for two hours. The aqueous dispersed nanoparticles are dialysed for 10 hours in a 12 kD cut-off cellulose membrane whereby residual small molecules like surfactant, hexane, unentrapped DNA etc. are separated leaving behind highly purified calcium phosphate nanoparticles doped with pDNA dispersed in water.
Example—4
[0063] Separation of Nanoparticles from Reverse Micelles and Redispersion in water.
[0064] Alternatively, the nanoparticles doped with genetic materials can also be separated by the following method. The hydrocarbon solvent of the reverse micelles is removed using rotary vacuum evaporator. The mass left in the flask is treated with 10 ml of dry ethanol and it is vortexed for 30 minutes. The ethanolic solution is kept at 4° C. for 12 hours when the nanoparticles are settled at the bottom of the flask and the supernatant alcoholic solution is pipetted out. The nanoparticles are then washed thrice each time with 10 ml dry ethanol and is separated by centrifugation at 300 rpm for 10 minutes. The residue left after centrifugation is then dispersed in 10 ml sterile water and dialyzed for 2 hours to get a transluscent dispersed system of loaded nanoparticles in water.
Example—5
[0065] Preparation of pUC19 Entrapped Manganous Phosphate Nanoparticles:
[0066] The method of preparation is same as above (in Example 1). In 25 ml of 0.1M AOT in hexane, 70 ul of 1M Manganous sulphate, 360 μl of double distilled water and 20 μl of pUC19 DNA (150 ug/ml) are dissolved. In another set of 25 ml of reverse micelles, 70 μl of 5% w/v disodium hydrogen phosphate, 310 μl of double distilled water, 20 ul of pUC19 (150 ug/ml) and 50 μl of ammonium hydroxide+ammonium chloride buffer (pH=10) are added. The two reverse micelles are mixed together and stirred as mentioned in example 1. The nanoparticles are separated by using dry ethanol and washed and dried for further use following the procedure as shown in example 4.
Example—6
[0067] Size and Shape of These Nanoparticles Using QELS and TEM:
[0068] The size of the particles obtained is determined using quasi elastic light scattering (QELS) measurements. 10 mg of lyophilized powder is redispersed in 10 ml water and the aqueous solution is filtered through 0.2 um Millipore filter. 3 ml of such solution is used for size determination. B18000 Brookhaven light scattering instrument is used and the intensity of scattered light at 90° is analyzed through Brookhaven autocorrelator. The size and size distribution of the nanoparticles are calculated from Stoke Einstein equation. The particles are reasonably monodisperse with size around 80 nm in diameter (FIG. 2 a ). The sizes of the nanoparticles are influenced by wo as well as reaction temperature, concentration of calcium ions and speed of mixing of the two reverse micellar systems.
[0069] Transmission Electron Micrograph (TEM) shows that the particles are more or less spherical in shape having solid core with rough surface texture (FIG. 2 b ).
Example—7
[0070] Agarose Gel Electrophoresis Studies
[0071] We have subjected the DNA doped inorganic nanoparticles to extensive DNaseI treatment followed by electrophoresis on 1% agarose gel (FIG. 3). We have found that while free plasmid DNA (pUC19) moves at its usual position in the gel, pUC19 encapsulated in the matrix of the nanoparticle is right at the top of the gel and hardly moved. This is a positive indication that the DNA has been encapsulated by the nanoparticle matrix. Moreover, while free pUC19 is completely digested by DNAseI (5 mg/ml) treatment for half an hour, encapsulated pUC19 is totally protected against similar DNAseI digestion. As expected, this is quite contrary to the plasmid DNA adsorbed on the surface of the nanoparticles. In this case, we find that the level of protection offered to the DNA is extremely low and the DNA is highly prone to nearly total degradation by DnaseI.
[0072] [0072]FIG. 3 shows Agarose Gel electrophoresis of free, entrapped and adsorbed pUC19 DNA in different lanes.
[0073] Lane #1: Molecular Weight marker
[0074] Lane #2: Free pUC19 DNA
[0075] Lane #3: Free pUC19 DNA treated with DNaseI
[0076] Lane #4: pUC19 DNA entrapped in Calcium phosphate nanoparticles
[0077] Lane#5: pUC19 DNA entrapped in Calcium phosphate nanoparticles and treated with DNaseI
[0078] Lane #6: pUC19 DNA adsorbed on Calcium phosphate nanoparticles
[0079] Lane#7: pUC19 DNA adsorbed on Calcium phosphate nanoparticles and treated with DNaseI
Example—8
[0080] Invitro Transfection Studies in Mammalian Cell Lines Using DNA Doped Nanoparticles
[0081] Use of calcium phosphate nanoparticles encapsulating DNA has been observed to achieve the benefit of nanoparticle mediated gene transfer by co-delivery of calcium ions when these DNA doped nanoparticles are added to Jurkat cell line in vitro. The data is furnished in FIG. 4. The plasmid DNA used in this case is pSVβgal, which carries the reporter gene coding for the enzyme β-galactosidase. Therefore, the transfection efficiency can be determined by measuring the activity of β-galactosidase in the individual in vitro systems. As observed from the data given in the figure, the transfection efficiency, measured as the activity of the enzyme β-galactosidase, obtained using these nanoparticles is nearly comparable to that obtained using a commercially available transfecting reagent (Superfect, obtained from Promega, USA) and is significantly higher than that obtained using calcium phosphate DNA coprecipitate.
[0082] [0082]FIG. 4 shows In vitro transfection efficiency of DNA doped calcium phosphate nanoparticles in Jurkat cell line. The positive control is the commercially available transfecting agent (Superfect).
Example—9
[0083] Invivo Transfection Experiment: Biodistribution Studies
[0084] To assess the potential utility of calcium phosphate nanoparticle mediated gene delivery in the animal, in general, and to a specific organ of the animal, in particular, we have used the murine model. Experiments have been conducted on young Swiss albino mice, and we have studied the local gene expression, as well as expression in different body tissues. Interestingly, both intramuscular (i.m.) and intraperitoneal (i.p.) administration of encapsulated pSVβgal have resulted in expression of the β-galactosidase enzyme in major organs of the body (FIGS. 5 a & b ). Local expression is observed in the tibialis muscle bundle. The enzyme activity detected is over and above that of the background endogenous activity. Free DNA expression is negligible compared to that of the nanoparticles.
[0085] [0085]FIG. 6 a shows transfection efficiency as measured byO-galactosidase expression in different body tissues after in vivo administration of pSVβGal plasmid DNA encapsulated in calcium phosphate nanoparticles in young in swiss albino mice ( 15 g ) are injected intraperitoneally. FIG. 6 b shows the transfection efficiency as measured by β-galactosidase expression in different body tissues after in vivo administration of pSVβGal plasmid DNA encapsulated in calcium phosphate nanoparticles. Free plasmid DNA is injected into the tibialis muscle bundle of mice
Example—10
[0086] In vivo Transfection Studies using Surface Modified Calcium Phosphate Nanoparticles for Targeted Delivery of DNA to Liver Specific Cells.
[0087] The liver is an important target for gene therapy, because of its large size and protein synthetic capacity. Moreover, there is a need to target genes transfer to the liver for treatment of diseases involving defects in members of segmental enzymatic pathways that are unique to the organ. Models for hepatic gene delivery have been developed using viral vectors, virosomes and other non-viral vectors, but all of these methods have important limitations. In our studies we have explored the potential use of calcium phosphate nanoparticles as vectors for hepatic gene transfer. Nanoparticles are incubated with a highly adhesive polymer like polyacrylic acid (PAA), followed by dialysis to remove excess polymer. The PAA molecules which adhered on the surface of the calcium phosphate nanoparticles are further modified by conjugating the carboxylic groups with p-aminophenyl-1-thio-D-galactopyranoside (PAG) using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDCI). The galactopyranoside moiety serves as a surface ligand for recognizing asialoglycoprotein receptor on liver cells. The tagged nanoparticles show preferential expression in liver tissue relative to lung, spleen and muscle. These observations suggest redistribution of genetic material in relation to the particle surface characteristics. | The present invention relates to a process of entrapping genetic materials in nanoparticles of inorganic metal salts of size below 100 nm diameter to form non-viral carriers for delivery of genes. The process comprises the steps of dissolving surfactants and a cosurfactant in oil to obtain reverse micelles. An aqueous solution of genetic material is added to the reverse micelles. Thereafter the reverse micelles are divided into two equal parts. To one part, aqueous solution of inorganic metal salts is dissolved to obtain optically clear and transparent reverse micelles. To the second part aqueous solution of precipitating agent is added to obtain optically clear and transparent reverse micelles. The two equally divided parts of reverse micelles are mixed to form inorganic nanoparticles encapsulating added genetic material. Thereafter, the nanoparticles are separated from reverse micelles, the inorganic nanoparticles are dispersed in water and dialyzed to remove free metal salts, surfactant and oil. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a character display apparatus. More particularly, it relates to a Chinese language display apparatus.
2. Description of the Prior Art
When Chinese words that make up a sentence are spoken, they are intonated in accordance with the meaning of the sentence. A sentence acquires a different meaning depending upon the manner of intonation of the Chinese characters in that sentence. In the tone system of Chinese, tones are classified into the so-called four-tone and neutral-tone, and each character consisting a sentence is provided with one of the tones. The four-tone and neutral-tone are indicated by symbols as described below.
Each of the four-tones are represented by. The first-tone is to intonate flatly and is represented by the symbol "--". The second-tone corresponds to the rising tone and is represented by the symbol "/". The third-tone corresponds to the rising and falling tone and is represented by the symbol " ". The fourth-tone corresponds to the falling tone and is represented by the symbol " ". The neutral-tone is to pronounce lightly the corresponding word and is represented by the symbol "◯". The relations between the tones and the symbols are summarized in FIG. 3.
When a Chinese sentence corresponding to an English sentence, e.g., "Please say it once more." is to be displayed on a display of an electronic translator, it would be very preferable for a learner if a tone symbol is also displayed in the vicinity of each of the characters consisting the sentence, as shown in FIG. 7.
In such a translator, in order to display a tone symbol in the vicinity of a corresponding character, it is necessary to know the positional relation between the character and the tone symbol in advance of displaying them. The measure described below can with this requirement. Namely, a memory region is allocated to character data, and another memory region is allocated to tone symbol data and positional information for correlating tone symbols with characters. Since the positional information for correlating tone symbols with characters must be memorized, this measure has various drawbacks that the amount of data to be stored is increased, that a memory means of a larger capacity is required, and that the control of the display is difficult.
SUMMARY OF THE INVENTION
The character display apparatus of this invention, which overcomes the above-discussed and numerous other disadvantages and deficiencies of the prior art, comprises a font memory means for storing character fonts and tone symbol fonts. The improvement includes a first memory means for storing one or more strings of pairs of a character code and a tone code, said character code corresponding to a Chinese character in a sentence to be displayed and corresponding to one of said character fonts, said tone code indicating a tone symbol corresponding to the tone of the accompanying character which is to be produced in the sentence. The pairs are arranged in order of the character arrangement in the sentence; a code selection means reads out said character codes and tone codes from said first memory means in order of the character arrangement and distinguishes said character codes from said tone codes. There also is a second memory means having a first memory area for storing the character fonts respectively indicated by said character codes, in order of the character arrangement, and a second memory area for storing the tone symbol fonts respectively indicated by said tone codes.
In a preferred embodiment, the apparatus is a translator.
In a first preferred embodiment, the apparatus is a translator from a language other than Chinese into Chinese. In another preferred embodiment, the character codes are of two-byte codes and said tone codes are of one-byte codes. In further preferred embodiment, the tone codes are selected so as not to be identical with any of the upper digits of said character codes.
Thus, the invention described herein makes possible the objectives of:
(1) Providing a character display apparatus which can display characters and tone symbols without memorizing positional information for correlating the tone symbols with the characters;
(2) Providing a character display apparatus in which the capacity of a memory means can be reduced; and
(3) Providing a character display apparatus in which the control of displaying characters and tone symbols can be easily performed.
BRIEF DESCRIPTION OF THE DRAWINGS
This invention may be better understood and its numerous objects and advantages will become apparent to those skilled in the art by reference to the accompanying drawings as follows:
FIG. 1 is a view diagrammatically illustrating the arrangement of the character font and tone symbol font of one Chinese character in a displayed sentence.
FIG. 2 is a block diagram of a character display apparatus of the invention.
FIG. 3 shows a table illustrating the relation between the tones and the tone symbols.
FIG. 4A illustrates diagrammatically the contents of the first memory region of the ROM.
FIG. 4B illustrates diagrammatically the contents of the second memory region of the ROM.
FIG. 5 is a plan view of the character display apparatus of FIG. 2.
FIG. 6 is a flow chart illustrating the operation of the character display apparatus of FIG. 2.
FIG. 7 shows a Chinese sentence corresponding to "Please say it once more." in which a tone symbol is indicated in the vicinity of each character.
FIG. 8 is a diagram illustrating the arrangement of character fonts and tone symbol fonts in the RAM.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 2 shows a block diagram of a character display apparatus according to the invention. The character display apparatus 1 of FIG. 2 is used as a display means of a portable translator for translating a sentence from English into Chinese or vice versa. The apparatus 1 comprises a ROM 2, a RAM 4, a key board 6, a liquid crystal display device 8, a driving circuit 10 for the display device 8, and a CPU 12 for controlling the operation of the apparatus. FIG. 5 shows a plan view of the apparatus 1. In the key board 1, an on/off switch 7, a forward search key 6a and a backward search key 6b are disposed as shown in FIG. 5. The driving circuit 10 incorporates a display RAM (not shown) which temporarily stores character fonts and tone symbol fonts.
In this embodiment, a two-byte code is assigned to each Chinese character in the same manner as in JIS X 0208-83. Hereinafter, such a two-byte code representing a Chinese character is referred to as "a character code". As shown in FIG. 3, a one-byte code is assigned to each tone symbol. Hereinafter, such a one-byte code representing a tone symbol is referred to as "a tone code". In the first two bytes of all of the character codes, codes (e.g., 10 H -14 H ) which are assigned to the tone codes are not used.
The ROM 2 comprises first to third memory regions 2a to 2c. FIGS. 4A and 4B illustrate diagrammatically the contents of the first and second memory regions 2a and 2b, respectively. In the second memory region 2b, code groups D 1 , D 2 , . . . , D n , . . . are stored. Each of the code groups D 1 , . . . , D n , . . . represents a Chinese sentence corresponding to a English sentence such as "Please say it once more.", "Good morning." or the like. If the code group D n represents the sentence of FIG. 7 which means "Please say it once more.", pairs of one character code (e.g., 476B H ) and one tone code (e.g., 12 H ) are arranged in series to represent Chinese characters and tone symbols shown in FIG. 7. An end code (FF H ) representing the end of the sentence is disposed at the end of each code group. In a code group, character codes are arranged in order of the character arrangement in the sentence which the code group represents, and each tone code is positioned behind the corresponding character code.
In the first memory region 2a, stored are addresses A 1 , A 2 , . . . , A n , . . . each of which is an index of the corresponding one of the code groups D 1 , . . . , D n , . . . The third memory region 2c stores Chinese character fonts corresponding to the character codes, and tone symbol fonts corresponding to the tone codes. By operating the forward search key 6a or the backward search key 6b, one of the addresses A 1 , . . . , A n , . . . stored in the first memory region 2a of the ROM 2 is sequentially selected.
The RAM 4 comprises first to third memory regions 4a to 4c. The selected address is temporarily stored in the first memory region 4a. The CPU 12 reads out from the second memory region 2b of the ROM 2 a code group the address of which has been stored in the first memory region 4a, and send the read out code group to the second memory region 4b of the RAM 4. Character fonts and tone symbol fonts represented by the character codes and tone codes consisting the code group which has been stored in the second memory region 4b are read out from the third memory region 2c of the ROM 2 to be stored in the third memory region 4c. In the third memory region 4c, as shown in FIG. 8, the character fonts and tone symbol fonts are arranged in order of the character arrangement of the sentence to be displayed. More specifically, as illustrated in FIG. 8, tone symbol fonts are stored in address Nos. 0-111, and character fonts are stored in address Nos. 112-447.
The operation of the character display apparatus of this embodiment will be be described in more detail with reference to a flow chart shown in FIG. 6. First, the forward search key 6a is pressed n times (step 1). According to the number of operation of the key 6a or 6b, the CPU 12 searches one of the read-out initiating addresses (in this case, the address A n ) stored in the first memory region 2a of the ROM 2 (step 2) which is then stored in the first memory region 4a of the RAM 4. Thereafter, the CPU 12 searches the code group D n corresponding to the address A n , and reads the first one byte (in this case, 47 H ) of the code group D n (step 3).
The CPU 12 judges whether or not the data in the first byte is the end code (FF H ) (step 4). If the data is not judged as the end code, the CPU 12 then judges whether the data is a tone code or not (step 5). As described above, a tone code is selected so as not to be identical with the code in the first byte of any character codes.
In response to the detection of the end code (FF H ) in step 4, the CPU 12 controls the driving circuit 10 so that the character fonts and tone symbol fonts stored in the display RAM are sent to the liquid crystal display device 8 (step 10). The display device 8 displays the characters and tone symbols corresponding to the character codes and tone codes in the code group D n . Namely, a Chinese sentence which means "Please say it once more." is displayed in which each tone symbol is positioned above the corresponding Chinese character. FIG. 1 illustrates in more detail the arrangement of the character font and tone symbol font of the first Chinese character in the displayed sentence.
When the code of the first byte is not judged as a tone code, the process proceeds to step 6 wherein the CPU 12 reads the code (in this case, 6B H ) of the second byte succeeding the first byte, and stores the codes of the first and second bytes as a two-byte character code (in this case, 476B H ) in the second memory region 4b of the RAM 4. The character font corresponding to the two-byte character code (476B H ) stored in the memory region 4b is fetched from the third memory region 2c of the ROM 2 (step 7), and is stored in the address Nos. 112-127, 224-239 and 336-351 of the third memory region 4c of the RAM 4 as shown in FIG. 8. The first address (i.e., 112) is temporarily stored in a working area of the RAM. The character font of the character code (476B H ) is transferred to the display RAM in the driving circuit 10 to be stored therein in the same manner as in the memory region 4c (step 8). Then, the process returns to step 3.
When the code of the first byte is judged as a tone code in step 5, the code (in this case, 12 H ) is stored in the second memory region 4b of the RAM 4. The tone symbol font corresponding to the tone code (12 H ) stored in the memory region 4b is fetched from the third memory region 2c of the ROM 2, and is stored in the third memory region 4c (step 9). The first address number (0) of the addresses numbers (0-15) wherein the tone symbol font is stored has been obtained by subtracting 112 which has been stored from the first address (112) for the character font. The tone symbol font of the tone code (12 H ) in the memory region 4c is transferred to the display RAM in the driving circuit 10 to be stored therein in the same manner as in the memory region 4c (step 8). Then, the process returns to step 3. The steps 3 to 9 are repeated until when the end code (FF H ) is detected, so that the character fonts and tone symbol fonts of all of character codes and tone codes in the code group D n are stored in the memory region 4c and also in the display RAM. In this way, the apparatus of the invention can display characters and their associating tone symbols without positional information correlating therebetween.
It is understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the scope and spirit of this invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the description as set forth herein, but rather that the claims be construed as encompassing all the features of patentable novelty that reside in the present invention, including all features that would be treated as equivalents thereof by those skilled in the art to which this invention pertains. | A Chinese character display apparatus includes a font memory for storing character fonts and tone symbol fonts. There is a first memory for storing strings of pairs of a character code and a tone code arranged in order of the character arrangement in a sentence that is to be displayed. A code selection device reads out the character codes and tone codes from the first memory in order of the character arrangement and distinguishes the character codes from the tone codes. There is a second memory having a first memory area for storing the character fonts respectively indicated by the character codes, in order of the character arrangement, and a second memory area for storing the tone symbol fonts respectively indicated by the tone codes. | 6 |
FIELD OF THE INVENTION
The present invention relates to road milling, mining and excavating tools, and more particularly relates to cutting bits with wear rings that reduce wear of such tools.
BACKGROUND INFORMATION
Cutting bits are used in various road milling, mining and excavating operations. The bits are mounted on a support structure such as a rotary drum. Each bit typically has a hard wear resistant tip made of a material such as tungsten carbide attached to a generally conical steel head of the bit. A problem with such designs is that the softer steel backing material erodes during cutting operations.
Wear resistant cutting bits have been developed in order to increase erosion resistance. For example, U.S. Pat. No. 4,725,098 to Beach discloses the deposition of a hard facing material on the steel nose of a tool body. U.S. Pat. No. 5,417,475 to Graham et al. discloses the installation of a ring of hard material on the front surface of a steel nose surrounding the hard cutting tip of a cutting tool. U.S. Pat. No. 6,709,065 to Peay et al. discloses the use of an annular ledge of hard material mounted near the steel nose of a cutting tool. Published U.S. Application No. 2005/0035649 to Mercier et al. discloses the installation of hard wear rings on a stepped shoulder of a cutting bit body. Despite these known designs, a need still exists for cutting bits which exhibit improved wear resistance.
SUMMARY OF THE INVENTION
The present invention provides a rotary cutting bit for use in road milling, mining and/or excavating applications that includes a split wear ring which is harder than the steel cutting bit body. The cutting bit has a cutting tip made of hard material such as tungsten carbide brazed into a nose portion of the steel tool body. The split wear ring is positioned in an annular channel in the tool body near the steel nose of the tool body. In one embodiment, the split wear ring is positioned so that the inner diameter of the split wear ring is smaller than the outer diameter of the cutting tip. Such a configuration allows the split wear ring to be tucked under the outer diameter of the cutting tip, decreasing tool body wear that could otherwise occur, thus providing longer tool life and reduced operating costs. The split wear ring pieces may be retained in place by a retainer such as banding rings, epoxies, tape or wire. Such retainers hold the ring sections in place during the assembly operation, so the ring sections do not move and remain attached to the tool body.
An aspect of the present invention is to provide a cutting bit comprising a body having a nose and a shank, a cutting tip mounted on the nose of the body comprising a harder material than the body, and a split wear ring mounted in an annular channel in the body adjacent the nose comprising a harder material than the body, wherein the split wear ring has an inner diameter less than an outer diameter of the cutting tip.
Another aspect of the present invention is to provide a cutting bit comprising a body having a nose and a shank, a cutting tip mounted on the nose of the body comprising a harder material than the body, a split wear ring mounted on the body adjacent the nose comprising a harder material than the body, and a retainer ring surrounding at least a portion of the split wear ring.
A further aspect of the present invention is to provide a cutting bit assembly comprising a body having a nose and a shank, a cutting tip mounted on the nose of the body comprising a harder material than the body, a split wear ring mounted in an annular channel in the body adjacent the nose comprising a harder material than the body, and a retainer ring surrounding at least a portion of the split wear ring for maintaining the split wear ring in the annular channel.
Another aspect of the present invention is to provide a method of assembling a cutting bit. The method comprises providing a body having a nose and a shank, mounting a cutting tip on the nose of the body comprising a harder material than the body, positioning a split wear ring in an annular channel in the body adjacent the nose comprising a harder material than the body, and securing the split wear ring in the annular channel.
These and other aspects of the present invention will be more apparent from the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of a cutting bit with a split wear ring and retaining ring in accordance with an embodiment of the present invention.
FIG. 2 is a side view of a cutting bit with a split wear ring in accordance with an embodiment of the present invention.
FIG. 3 is a side view of the body portion of the cutting bit of FIG. 2 with the cutting tip, split wear ring and retaining ring removed.
FIG. 4 is a longitudinal sectional view of a cutting bit assembly including a split wear ring, retainer ring and braze ring in accordance with an embodiment of the present invention.
FIG. 5 is an isometric view of a split wear ring segment in accordance with an embodiment of the present invention.
FIG. 6 is a front view of the split wear ring segment of FIG. 5 .
FIG. 7 is a side view of the split wear ring segment of FIG. 5 .
FIG. 8 is an isometric view of a retainer ring for securing a split wear ring on a cutting bit in accordance with an embodiment of the present invention.
FIG. 9 is a front view of a retainer ring in accordance with an embodiment of the present invention.
FIG. 10 is a sectional view taken through section 10 - 10 of FIG. 9 .
FIG. 11 is an isometric view of a braze ring which may be used during assembly of a cutting bit in accordance with an embodiment of the present invention.
FIG. 12 is a front view of the braze ring of FIG. 11 .
FIG. 13 is a sectional view taken through section 13 - 13 of FIG. 12 .
FIGS. 14 and 15 are photographs of different cutting bits before and after they were subjected to wear testing. In each of the photographs, a cutting bit in accordance with an embodiment of the present invention is shown on the left, a cutting bit with a deposited hard facing material is shown in the middle, and a cutting bit with a relatively large unitary wear ring is shown on the right. As shown in FIG. 15 , the cutting bit of the present invention exhibits significantly improved erosion resistance in comparison with the other designs.
FIG. 16 is a photograph of a cutting bit in accordance with an embodiment of the present invention after it was subjected to wear testing.
FIG. 17 is a photograph of a conventional single ring body wear protection cutting bit after it was subjected to wear testing.
DETAILED DESCRIPTION
As shown in FIGS. 1 , 2 and 4 , a cutting bit 10 comprises a body 12 having a front nose 14 and rear shank 16 . The body 12 is typically made of steel. As shown most clearly in FIGS. 1 and 2 , a spring sleeve 17 may be installed around the shank 16 of the cutting bit 10 , and a washer 18 may surround the spring sleeve 17 . A cutting tip 20 is mounted in a pocket 21 in the nose 14 of the cutting bit body 12 by known methods such as brazing or epoxy. The pocket 21 extends longitudinally from the front surface of the nose 14 into the body 12 a distance P, shown in FIGS. 3 and 4 . The cutting tip is made of a relatively hard material, such as tungsten carbide, polycarbonite diamonds, ceramics, or any other material that is harder than the steel body.
As shown most clearly in FIGS. 2-4 , an annular channel 19 is provided in the body 12 of the cutting bit near the nose 14 . The annular channel 19 has a front wall 19 a and a rear wall 19 b, defining a width W of the annular channel 19 . In the embodiment shown in FIGS. 2-4 , the front and rear walls 19 a and 19 b are generally flat and extend in planes perpendicular to the axial direction of the cutting bit body 12 . However, other wall surfaces, shapes and orientations may be used. For example, curved or faceted wall surfaces may be used instead of the flat wall surfaces shown in the figures. Furthermore, the walls may be oriented at angles other than perpendicular to the axial direction as shown in the figures. The annular channel 19 also has a diameter C D that is less than a diameter N D of the nose 14 .
In accordance with the present invention, a split wear ring 30 is provided in the annular channel 19 . The hardness, size and location of the split wear ring 30 are selected in order to significantly reduce erosion and wear of the relatively soft body 12 of the cutting bit 10 . The split wear ring 30 has an outer diameter R OD , inner diameter R ID , and thickness T, as shown in FIGS. 2 , 4 and 7 . The split wear ring 30 may be made of any suitable hard material such as carbides, aluminum oxide, hard ceramic materials, hardened tool steels and the like. For example, the split wear ring 30 may be made of tungsten carbide. In one embodiment, the split wear ring 30 and cutting tip 20 are made of the same hard material. Furthermore, portions of the split wear ring 30 may be made of different materials, e.g., materials having different hardness and/or toughness properties, graded materials, and the like.
The distance N between the front surface of the nose 14 and the front wall 19 a of the annular channel 19 in which the split wear ring 30 is installed is minimized in order to provide improved wear resistance. For example, the distance N may be less than or equal to the width W of the annular channel 19 , and may be less than or equal to the thickness T of the split wear ring 30 . The distance N, width W of the annular channel 19 and thickness T of the split wear ring 30 are selected in order to provide the desired wear resistance for the body 12 . In one embodiment, the distance N may be from about 0.05 to about 0.5 inch, the width W of the annular channel 19 may be from about 0.1 to about 0.3 inch, and the thickness T of the split wear ring 30 maybe from about 0.1 to about 0.3 inch.
As shown most clearly in FIGS. 3 and 4 , the annular channel 19 and pocket 21 are arranged such that the distance P which the pocket 21 extends axially into the body 12 from the front surface of the nose 14 is greater than the distance N between the front surface of the nose 14 and the front wall 19 a of the annular channel 19 . In the embodiment shown in the figures, the distance P is such that the rear surface of the pocket 21 is located between the front wall 19 a and the back wall 19 b of the annular channel 19 in the axial direction of the body 12 . Thus, the annular channel 19 , and the split ring 30 mounted therein, surround the rear surface of the pocket 21 and the rear face of the cutting tip 20 mounted in the pocket.
As shown in the embodiment of FIGS. 1 and 4 , a retainer ring 32 is used to secure the split wear ring 30 within the annular channel 19 of the body 12 . The retainer ring 32 may be made of any suitable material such as spring steel, stainless steel, or any other material capable of withstanding the assembly attachment process for the split wear ring and cutting tip. As more fully described below, the retainer ring 32 is used to hold the split wear ring 30 in place during assembly of the cutting bit 10 , and may be retained on the cutting bit 10 after it has been fabricated.
As shown in the embodiment of FIG. 4 , a braze ring 34 may be positioned adjacent to the split wear ring 30 and the nose 14 of the cutting bit body 12 during fabrication of the cutting bit 10 . The assembly shown in FIG. 4 may be heated by any suitable means such as induction heating to melt the braze ring 34 to form a braze joint between the split wear ring 30 and the annular channel 19 of the body 12 . A braze alloy 22 may also be provided between a recess in the nose 14 of the body 12 and the rear portion of the cutting tip 20 . In one embodiment, the braze joint 22 is formed during the same heating step which melts the braze ring 34 to form the joint between the split wear ring 30 and the body 12 . The braze ring 34 and the braze joint 22 may be made of any suitable braze alloys such as high or low temperature copper based alloys. In one embodiment, the same braze alloy is used for the braze ring 34 and braze joint 22 . In an alternative embodiment, epoxy may be used to secure the split wear ring 30 in the annular channel 19 .
As shown in FIG. 4 , the inner diameter R ID of the split wear ring 30 is smaller than an outer diameter T OD of the cutting tip 20 . This arrangement provides significantly improved wear resistance by preventing steel wash more effectively. The inner diameter R ID of the split wear ring 30 is also smaller than the diameter N D of the nose 19 . The location of the split wear ring 30 in the annular channel 19 a relatively close distance N to the nose 14 of the tool body 12 provides significantly better wash protection. If the split wear ring 30 was not tucked under the nose 14 of the tool body 12 , it would rub in the cut due to its close proximity to the cutting tip 20 , causing decreased wear protection and tool performance. The outer diameter R OD of the split wear ring 30 is also smaller than a diameter S D of a shoulder of the body 12 . The shoulder diameter S D is measured at the edge where the rear wall 19 b of the channel 19 meets the generally frustoconical portion of the cutting bit body 12 . The smaller outer diameter R OD of the split wear ring 30 in comparison with the larger diameter S D of the tool body shoulder prevents the outside edge of the split wear ring 30 from rubbing in the cut.
With the split wear ring 30 located relatively close to the tool body nose 14 , the steel body 12 is better protected and it holds its original conical shape, creating less drag and reducing operating costs. If the wear ring was moved further down the body 12 , it would tend to blunt or become club-like during operation, slowing the machine down and increasing operating costs. The position of the split wear ring 30 in the upper portion of the body 12 can help aid in rotation by acting as a “steering wheel” in the cut. Thus, in addition to decreasing the body wear under the cutting tip 20 , the split wear ring 30 attached to the cutting tool body 12 can also aid in tool rotation, lessen cutting bit frictional forces in the cut of the material, and reduce operating costs. The split wear ring may optionally include features such as ribs, flutes, veins and/or dimples for aiding in tool rotation.
Details of a split wear ring section 30 a are shown in FIGS. 5-7 . In this embodiment, two of the split wear ring sections 30 a are used to form the split wear ring 30 . However, any other suitable member of split wear ring sections may be used, such as three sections, four sections, etc. When the split wear ring sections are assembled in the annular channel 19 , they may have flat faces which abut each other as shown in the embodiment of FIGS. 5-7 . Alternatively, the abutting faces may have other shapes such as tabs or other features which provide a contoured or interlocking connection between adjacent sections.
In the embodiment shown in FIG. 7 , the split wear ring 30 has a cross section with beveled corners forming angles A, B, C and D. In accordance with one embodiment, angles A and B are the same, and angles C and D are the same, such that the ring forms a mirror image and is symmetrical in a plane of the ring. Such a configuration facilitates assembly of the cutting bit 10 because when the split wear ring segments are mounted in the annular channel 19 , they are automatically aligned with the opposing split wear ring segment(s). In one embodiment, all of the angles A, B, C and D are the same. Each of the angles A, B, C and D typically range from about 30 to 60 degrees, with an angle of about 45 degrees being particularly suitable. The symmetrical shape allows universal fit in assembly operations, such that no particular orientation is required when fitting the parts.
FIGS. 8-10 illustrate details of the retainer ring 32 , and FIGS. 11-13 illustrate details of the braze ring 34 . As shown in FIGS. 4 and 8 - 13 , the retainer ring 32 has an inner diameter less than or equal to the outer diameter R OD of the split wear ring 30 . The braze ring 34 has an inner diameter equal to or slightly smaller than the outer diameter of the nose 14 of the body 12 . The inner diameter of the braze ring 34 is typically smaller than the inner diameter of the retainer ring 32 and the outer diameter R OD of the split wear ring 30 . As shown most clearly in FIG. 4 , the retainer ring 32 is seated against the rearward portion of the split wear ring 30 at the rear edge of the annular channel 19 . The braze ring 34 is seated against the forward portion of the split wear ring 30 and the forward edge of the annular channel 19 . The beveled cross sectional shape of the split wear ring 30 helps maintain the retainer ring 32 and braze ring 34 in their respective positions shown in FIG. 4 .
In addition to the split wear rings 30 of the present invention, additional ribs, flutes, veins and/or dimples may be attached to the tool body 12 either independently or in conjunction with the split wear ring 30 . The ribs, flutes, veins and/or dimples may be harder than the steel body 12 , and may be made from similar materials as the split wear ring 30 . Such ribs, flutes, veins and/or dimples may be used to protect the steel body 12 from erosion, e.g., caused by cutting of asphalt material, and to aid in rotation of the tool.
The retainer ring 32 holds the split wear ring segments 30 a in place when going through the braze coil or other brazing operations. The wear ring segments 30 a will tend to move apart by the magnetic action of the braze coil and the floating effect of the braze material if not held in place by the retainer ring. This aids in assembly. Operators do not need to hold the wear ring segments 30 a together while the braze ring 34 melts, which avoids safety issues associated with operators placing their hands in the braze coil. During the cutting operations, the retainer ring 32 may be removed in the milling cut after a few minutes, and will not interfere with tool cutting performance.
The braze ring 34 snaps over the nose 14 of steel body 12 allowing easier assembly operation with the split wear ring segments 30 a. The braze ring 34 helps lock down the split wear ring segments 30 a to the body shoulder to prevent the rings from moving in the braze coil. Thus, both the braze ring 34 and retainer ring 32 may help secure the split wear ring segments during assembly. The braze material flows down behind the split wear ring segments 30 a into the annular channel 19 to ensure better braze coverage and a more secure braze joint.
Comparative wear tests were performed on a cutting bit in accordance with an embodiment of the present invention in comparison with a conventional cutting bit having hard facing material deposited thereon and another cutting bit having a relatively large unitary wear ring. The comparative wear testing was performed by installing tools equally across an entire cutting drum so all tools are subject to similar wear and cutting conditions. The cutting drum was engaged in the material, e.g., asphalt, under normal job site cutting conditions across the full length of the cutting drum to ensure all tools are subject to the same wear pattern and conditions across the entire drum cutting surface. All parts were run in the asphalt material for the same amount of time or square footage. The parts were then removed from the cutting drum and examined and photographed to determine differences in wear.
FIG. 14 is a photograph showing the cutting bits before they were tested, and FIG. 15 is a photograph showing the cutting bits after they were subjected to wear testing. FIG. 16 is a photograph of a cutting bit of the present invention after it was subjected to wear testing. FIG. 17 is a photograph of a conventional single ring body wear protection cutting bit after it was subjected to wear testing.
Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims. | The present invention provides a rotary cutting bit for use in road milling, mining and/or excavating applications that includes a split wear ring which is harder than the steel cutting bit body. The cutting bit has a cutting tip made of hard material such as tungsten carbide brazed into a nose portion of the steel tool body. The split wear ring is positioned in an annular channel in the tool body near the steel nose of the tool body. In one embodiment, the split wear ring is positioned so that the inner diameter of the split wear ring is smaller than the outer diameter of the cutting tip. Such a configuration allows the split wear ring to be tucked under the outer diameter of the cutting tip, decreasing tool body wear that could otherwise occur, thus providing longer tool life and reduced operating costs. The split wear ring pieces may be retained in place by a retainer such as banding rings, epoxies, tape or wire. Such retainers hold the ring sections in place during the assembly operation, so the ring sections do not move and remain attached to the tool body. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 10/770,448, filed Feb. 4, 2004 and titled “Dynamic Rendering of Ink Strokes with Transparency,” now U.S. Pat. No. 7,091,963, which application is a continuation of U.S. patent application Ser. No. 09/918,484, filed Aug. 1, 2001, and titled “Dynamic Rendering of Ink Strokes with Transparency”, now U.S. Pat. No. 6,707,473. This application is related to U.S. patent application Ser. No. 10/972,390 , entitled “Dynamic Rendering of Ink Strokes with Transparency,” filed Oct. 26, 2004, U.S. patent application Ser. No. 09/918,721, entitled “Rendering Ink Strokes of Variable Width and Angle,” filed Aug. 1, 2001, and U.S. patent application Ser. No. 09/852,799, entitled “Serial Storage of Ink and its Properties,” filed May 11, 2001. All of said applications are hereby incorporated by reference as to their entireties.
FIELD OF THE INVENTION
The present invention is directed generally to rendering transparent digital ink, and more particularly to improved ways of rendering transparent digital ink dynamically.
BACKGROUND OF THE INVENTION
The term “digital ink” refers to one or more strokes that are recorded from a pointing device, such as a mouse, a stylus/pen on a digitizer tablet, or a stylus/pen on a display screen integrated with a digitizer tablet (e.g., a touch-sensitive display screen). As used herein, the term “ink” is shorthand for digital ink. Also, the term “pen” and “stylus” are used generically and interchangeably. Each stroke may be stored as one or more ink packets, in which each ink packet may contain coordinates (x, y) corresponding to the position of the pointing device. For example, a user may move a pen along a touch-sensitive display screen of a computer system so as to draw a line or curve, and the computer system may sample the coordinates (x, y) along the trajectory of the pen tip position over time (or on any other interval as known in the art) as the user moves the pen. These coordinates represent points along the curve or line and are stored as ink packets.
Ink may be either transparent or non-transparent, as used herein. Ink that is transparent means that the ink does not fully conceal the background behind it when displayed on a display or printed on a printer. Ink that is not transparent completely conceals or occludes the background behind it. Non-transparent ink may also be referred to as opaque ink. For instance, FIG. 1 shows ink strokes 101 , 102 , and 103 . Ink strokes 102 and 103 each overlay ink stroke 101 , but ink stroke 103 completely conceals its background, including the portion of ink stroke 101 that it overlays (i.e., the portion of ink stroke 101 that is a background behind ink stroke 103 ). Thus, ink stroke 103 is considered opaque. In contrast, ink stroke 102 allows some of ink stroke 101 , as well as some of the white background, to show through where ink stroke 102 overlays ink stroke 101 . Thus, ink stroke 102 is considered transparent. Ink can be of any transparency and still be considered transparent. Current graphics interfaces are capable of applying transparent paint with a prescribed degree of transparency. For example, ink may be 50% transparent, which means that 50% of the background is concealed, or ink may be 25% transparent, which means that 75% of the background is concealed. A transparent ink stroke can be analogized with a piece of glass, such as colored glass, in which objects behind the glass can be seen. A non-transparent ink stroke can be analogized with a brick wall that hides everything behind it.
It is often desirable to render a transparent ink stroke dynamically while the ink stroke is being drawn, in other words, to draw the ink stroke on the display screen while the pointing device moves and adds new points to the ink stroke or strokes. One way to accomplish this is to erase the entire screen and redraw everything on the screen each time a new point is added to the ink stroke. This is an imperfect solution, however, since in practice there is typically a short time interval between ink points, and repeatedly clearing and redrawing the screen uses massive amounts of processing power, not to mention causing the screen to flicker. A way to reduce the redrawing time would be draw each new segment of an ink stroke as it is drawn. The problem with this is that the transparencies of the overlapping portion of ink segments are reduced in an unexpected and unintended manner. The effect of redrawing transparent ink is shown in FIG. 2 , where the darker circles of an ink stroke 200 represent the overlapping start and end points of the segments. These overlapping areas are darker because they are each drawn twice—once when a segment ending with a particular point is drawn, and again when the next segment beginning with the same point is drawn—thereby reducing the transparency at the overlap. The result is an unintentionally non-uniform ink stroke. This is analogous to repeatedly making a glass window thicker, thereby making objects on the other side of the glass more difficult to see by making the window darker. The variable transparency of the rendered ink is unexpected to the user who would expect transparent ink to be rendered as transparent physical ink as applied to paper and/or over other ink.
There is also a need for providing various artistic features not provided by current systems, such as dynamically rendering ink responsive to variable width, pressure, speed, and angle of the pen.
SUMMARY OF THE INVENTION
Apparatus and methods are disclosed for dynamically rendering transparent ink strokes that solves at least one of the problems associated with rendering transparent ink. Using the present invention, the rendering of electronic ink (or ink as used herein) is improved. For example, the ink stroke may be dynamically rendered as a stroke having uniform transparency while it is being drawn. This may be performed without having to clear and redraw the entire screen.
To dynamically draw a transparent ink stroke, a computer system may draw only the segment that has most recently been added to the stroke. The system may further exclude areas of the new segment that overlap older portions of the stroke from being painted more than once, which would otherwise make the older segments less transparent. For instance, the color settings of pixels in the overlapping areas may be frozen before painting the new segment. Freezing the color settings may reduce or prevent unintended non-uniformities in the ink stroke.
These and other features of the invention will be apparent upon consideration of the following detailed description of preferred embodiments. It will be apparent to those skilled in the relevant technology, in light of the present specification, that alternate combinations of aspects of the invention, either alone or in combination with one or more elements or steps defined herein, may be used as modifications or alterations of the invention or as part of the invention. It is intended that the written description of the invention contained herein covers all such modifications and alterations.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing summary of the invention, as well as the following detailed description of preferred embodiments, is better understood when read in conjunction with the accompanying drawings, which are included by way of example, and not by way of limitation with regard to the claimed invention. In the accompanying drawings, elements are labeled with reference numbers, wherein the first digit of a three-digit reference number, and the first two digits of a four-digit reference number, indicates the drawing number in which the element is first illustrated. The same reference number in different drawings refers to the same or a similar element.
FIG. 1 is an exemplary embodiment of both transparent and non-transparent digital ink as they may be displayed, according to at least one aspect of the present invention.
FIG. 2 is an exemplary embodiment of transparent digital ink as it may be displayed, showing non-uniformities due to blending of multiple segments.
FIG. 3 is an exemplary embodiment of transparent digital ink as it may be displayed, without the non-uniformities of the ink shown in FIG. 2 , and according to at least one aspect of the present invention.
FIG. 4 is a functional block diagram of an exemplary embodiment of a computer system according to at least one aspect of the present invention.
FIG. 5 is a functional block diagram of an exemplary embodiment of an ink rendering system according to at least one aspect of the present invention.
FIG. 6 is an exemplary flowchart showing steps that may be performed in order to render transparent ink according to at least one aspect of the present invention.
FIG. 7 is an exemplary geometrical representation of stroke segments including circular pen tip instances and connecting quadrangles according to at least one aspect of the present invention.
FIG. 8 is an exemplary embodiment of digital ink corresponding to the stroke segments of FIG. 7 as it may be displayed, according to at least one aspect of the present invention.
FIG. 9 is an exemplary geometrical representation of a frozen region within a series of stroke segments, according to at least one aspect of the present invention.
FIG. 10 is a functional block diagram of an exemplary embodiment of another ink rendering system according to at least one aspect of the present invention.
FIG. 11 is an exemplary geometrical representation of a stroke including differently-sized circular pen tip instances and connecting quadrangles according to at least one aspect of the present invention.
FIG. 12 is an exemplary embodiment of digital ink corresponding to the stroke of FIG. 11 as it may be displayed, according to at least one aspect of the present invention.
FIG. 13 is an exemplary geometrical representation of a stroke including differently-sized and differently-angled oval pen tip instances and a connecting quadrangle according to at least one aspect of the present invention.
FIG. 14 is an exemplary embodiment of digital ink corresponding to the stroke of FIG. 13 as it may be displayed, according to at least one aspect of the present invention.
FIG. 15 is an exemplary geometrical representation of a stroke including differently-sized and differently-angled rectangular pen tip instances and a connecting quadrangle according to at least one aspect of the present invention.
FIG. 16 is an exemplary embodiment of digital ink corresponding to the stroke of FIG. 15 as it may be displayed, according to at least one aspect of the present invention.
FIGS. 17A and 17B are exemplary geometrical representations of a stroke including differently-sized and differently-angled rectangular pen tip instances and two different possible connecting quadrangles according to at least one aspect of the present invention.
FIG. 17C is an exemplary representation of the stroke of FIGS. 17A and 17B including all of the possible corner-connecting quadrangles according to at least one aspect of the present invention.
FIG. 18 is an exemplary embodiment of digital ink corresponding to the stroke of FIG. 17C as it may be displayed, including all possible connecting quadrangles, according to at least one aspect of the present invention.
FIG. 19 is a functional block diagram of an exemplary embodiment of yet another ink rendering system according to at least one aspect of the present invention.
FIG. 20 is a geometric representation of an exemplary ink stroke illustrating the sample points therein as well as a fitting curve for position, width, and rotation, in accordance with at least one aspect of the present invention.
FIG. 21 is a representation of a rendered exemplary ink stroke according to at least one aspect of the present invention.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
Improved transparent ink rendering systems and methods are disclosed. The various embodiments of the invention are described in the following sections: General Purpose Computing Environment, Ink Rendering System, and Ink Smoothing.
General Purpose Computing Environment
FIG. 4 illustrates a schematic diagram of an exemplary general-purpose digital computing environment that may be used to implement various aspects of the present invention. In FIG. 4 , a computer 400 such as a personal computer includes a processing unit 410 , a system memory 420 , and/or a system bus 430 that couples various system components including the system memory to processing unit 410 . System bus 430 may be any of several types of bus structures including a memory bus or memory controller, a peripheral bus, and a local bus using any of a variety of bus architectures. System memory 420 includes read only memory (ROM) 440 and random access memory (RAM) 450 .
A basic input/output system 460 (BIOS), containing the basic routines that help to transfer information between elements within computer 400 , such as during start-up, is stored in ROM 140 . The computer 400 also includes a hard disk drive 470 for reading from and writing to a hard disk (not shown), a magnetic disk drive 480 for reading from or writing to a removable magnetic disk 490 , and an optical disk drive 491 for reading from or writing to a removable optical disk 492 such as a CD ROM or other optical media. Hard disk drive 470 , magnetic disk drive 480 , and optical disk drive 491 are connected to the system bus 430 by a hard disk drive interface 492 , a magnetic disk drive interface 493 , and an optical disk drive interface 494 , respectively. The drives and their associated computer-readable media provide nonvolatile storage of computer readable instructions, data structures, program modules and other data for personal computer 400 . It will be appreciated by those skilled in the art that other types of computer readable media that can store data that is accessible by a computer, such as magnetic cassettes, flash memory cards, digital video disks, Bernoulli cartridges, random access memories (RAMs), read only memories (ROMs), and the like, may also be used in the example operating environment.
A number of program modules can be stored on hard disk drive 470 , magnetic disk 490 , optical disk 492 , ROM 440 , and/or RAM 450 , including an operating system 495 , one or more application programs 496 , other program modules 497 , and program data 498 . A user can enter commands and information into computer 400 through input devices such as a keyboard 401 and pointing device 402 . Other input devices (not shown) may include a microphone, joystick, game pad, satellite dish, scanner or the like. These and other input devices are often connected to processing unit 410 through a serial port interface 406 that is coupled to the system bus, but may be connected by other interfaces, such as a parallel port, game port or a universal serial bus (USB). Further still, these devices may be coupled directly to system bus 430 via an appropriate interface (not shown). A monitor 407 or other type of display device is also connected to system bus 430 via an interface, such as a video adapter 408 . In addition to the monitor, personal computers typically include other peripheral output devices (not shown), such as speakers and printers. In one embodiment, a pen digitizer 465 and accompanying pen or stylus 466 are provided in order to digitally capture freehand input. Although a direct connection between pen digitizer 465 and processing unit 410 is shown, in practice, pen digitizer 465 may be coupled to processing unit 410 via a serial port, parallel port, and/or other interface and system bus 430 as known in the art. Furthermore, although digitizer 465 is shown apart from monitor 407 , in some embodiments the usable input area of digitizer 465 be co-extensive with the display area of monitor 407 . Further still, digitizer 465 may be integrated in monitor 407 , or may exist as a separate device overlaying or otherwise appended to monitor 407 .
The computer 400 can operate in a networked environment using logical connections to one or more remote computers, such as a remote computer 409 . Remote computer 409 can be a server, a router, a network PC, a peer device or other common network node, and typically includes many or all of the elements described above relative to computer 400 , although only a memory storage device 411 has been illustrated in FIG. 4 . The logical connections depicted in FIG. 4 include a local area network (LAN) 412 and a wide area network (WAN) 413 . Such networking environments are commonplace in offices, enterprise-wide computer networks, intranets and the Internet.
When used in a LAN networking environment, the computer 400 is connected to local network 412 through a network interface or adapter 414 . When used in a WAN networking environment, the computer 400 typically includes a modem 415 or other device for establishing a communications over wide area network 413 , such as the Internet. Modem 415 , which may be internal or external, is connected to system bus 430 via the serial port interface 406 . In a networked environment, program modules depicted relative to the computer 400 , or portions thereof, may be stored in a remote memory storage device.
It will be appreciated that the network connections shown are exemplary and other techniques for establishing a communications link between the computers can be used. The existence of any of various well-known protocols such as TCP/IP, Ethernet, FTP, HTTP and the like is presumed, and the system can be operated in a client-server configuration to permit a user to retrieve web pages from a web-based server. Any of various conventional web browsers can be used to display and manipulate data on web pages.
Ink Rendering System
An exemplary ink rendering system 500 is illustrated in FIG. 5 . Some or all of the ink rendering system 500 may be software, hardware, and/or firmware, and may be a part of the computer system 400 or a separate unit. For instance, some or all of the ink rendering system 500 may be embodied as computer code stored in the RAM 450 as part of the operating system 495 , an application program 496 , and/or another program module 497 . The ink rendering system 500 may include an ink storage 501 coupled to a rendering environment 502 , which in turn may be coupled to a graphics toolbox 503 , which in turn may be coupled to an output device 504 such as a display screen (e.g., monitor 407 ) and/or printer. The ink storage 501 may include information relating to ink including a file structure having data points representing points of the ink. The file structure may also include alternatively (or in addition to the data points) other ways to represent the ink including vectors between points, data points, stroke width information, and/or any other ink storage scheme.
Stored ink may be rendered by calling the graphics toolbox 503 to perform various functions. The ink storage 501 may maintain a list of rendering environments, one for each view in which the application renders dynamically. Each rendering environment may maintain a list of the states, one for each stroke that is currently being dynamically rendered. Each state may represent the last pen tip position (e.g., point) recorded and/or a queue of geometric regions that are further described below. In at least one embodiment, the graphics toolbox 503 has transparent painting capabilities, such as does Microsoft WINDOWS GDI+.
FIG. 6 illustrates an example of the operation of the ink rendering system 500 . When a user draws a stroke, the ink rendering system 500 may receive a new pen tip position (step 601 ). More particularly, the ink storage 501 may receive the new pen tip position. Pen tip positions may be sampled and determined according to the position of the stylus 466 upon the digitizer 465 . Pen tip positions may further be determined according to the position of the stylus 466 within a known input window or area that defines a portion of the digitizer 466 surface. For instance, where the digitizer 465 and the monitor 407 are combined or co-extensive, there may be a predefined window displayed on the digitizer 465 within which input from the stylus 466 may be accepted, e.g., for drawing an object and/or for entering text.
Pen tip positions may be sampled at a particular rate. The sampling rate may be set at a rate at least high enough to capture sufficient pen tip positions based on the anticipated speed of a normal user. Once the new pen tip position is captured and received, the ink rendering system 500 (e.g., in particular, the ink storage 501 ) may determine the area (and/or the contour that outlines and defines the area) that is associated with the pen tip at the new position based on the size and/or shape of the virtual pen tip. This area is also known as a “pen tip instance.” For example, where the virtual pen tip is considered to be a 3-millimeter diameter circle, then the pen tip instance may be the 3-millimeter diameter circle centered at the new pen tip position. Or, where the virtual pen tip is considered to be a rectangle of 2 millimeters by 4 millimeters, then the pen tip instance may be the 2 by 4 millimeter rectangle centered at the new pen tip position. Examples of circular pen tip instances 701 , 702 , 703 , 704 are shown in FIG. 7 . The size and shape of the pen tip instance are considered properties of the pen tip position. Where the entire stroke has the same size and/or shape, then the size and/or shape may be a property of the entire stroke as opposed to each pen tip position. Of course, any shape may be used for a pen tip. Circular pen tip instances are used here for simplicity.
Each time a pen tip instance is determined, that pen tip instance (and/or the associated pen tip position) may be stored for later retrieval. Pen tip instances and/or positions may be stored as data in, e.g., RAM 450 . Data representing the position (e.g., (x, y) coordinate position), shape, and/or rotation of the pen tip instance may further be stored. Previous pen tip instances and/or positions may further be stored as part of digital ink storage such as in the serialized format described in U.S. patent application Ser. No. 09/852,799, entitled “Serial Storage of Ink and its Properties,” filed May 11, 2001.
Referring still to FIG. 6 , the ink rendering system 500 may render an ink segment that connects between the previous pen tip instance and a new pen tip instance in an ink stroke. To do so, the ink rendering system 500 may compute the new pen tip instance and/or one or more connecting quadrangles that connect between the new pen tip instance and a previous pen tip instance (step 602 ). Both the pen tip instances and the connecting quadrangles are referred to herein as “regions.”
The new pen tip instance is associated with the new pen tip position, and may be centered about the new pen tip position. The new connecting quadrangle may be determined in a variety of ways, and the method for determining the connecting quadrangle may depend upon the shapes of the new and previous pen tip instances. Various methods for determining connecting quadrangles will be discussed herein. Examples of connecting quadrangles 705 , 706 , 707 are shown in FIG. 7 . A new region may be defined as the new pen tip instance, the new connecting quadrangle, or the combination (e.g., union) of the new pen tip instance and the new connecting quadrangle. For example, the new region may be pen tip instance 704 , connecting quadrangle 707 , or the union of pen tip instance 704 and connecting quadrangle 707 . Conventional graphics toolboxes are capable of performing such a combination/union when provided with the shapes to be combined. In alternative embodiments, more than one new pen tip instance and/or new connecting quadrangle may be the new region. For instance, two consecutive new pen tip instances and their two corresponding new connecting quadrangles may be all unioned together as the new region. In this way, the method of FIG. 6 does not necessarily need to be performed between each and every pen tip instance.
The combination (e.g., union) of some or all of a plurality of previous regions may also be determined (step 603 ). These previous regions may be stored in a queue. A queue is an ordered list of items and is of a fixed, dynamic, maximum, or other controlled length. For example, a queue may have a maximum enforced length of 2, 3, or 4 items, although any length may be used. The queue may be configured as a first-in-first-out (FIFO) type queue, as in a pipeline. Where the maximum length of the FIFO queue is surpassed by adding another item to the queue, the oldest item is pushed out of the queue. The queue may separately store the actual items, or may have pointers that point to the items stored elsewhere. Where the items are stored elsewhere, they may be stored in a serialized or other format. In alternative embodiments, the items in the queue may be any items of data that represent some or all of the characteristics of pen tip positions and/or connecting quadrangles. In still further embodiments, each item in the queue may be a combined pen tip position and connecting quadrangle.
For example, referring to FIG. 9 , where the new pen tip instance is pen tip instance 905 , the new connecting quadrangle is connecting quadrangle 909 , and the queue has a maximum length of 4 regions, the queued regions to be combined may be pen tip instances 903 , 904 (two regions) and connecting quadrangles 907 , 908 (two more regions, for a total of four regions). The union of these queued regions is shown as the shaded area in FIG. 9 . The arrow 910 indicates the direction of movement of the pen tip, such that the pen tip instance 905 is the most recent and the pen tip instance 901 is the earliest in time. Note that although connecting quadrangle 906 and pen tip instance 901 may have been in the queue at an earlier time, these two regions were later pushed out of the queue due to the enforcement of its maximum length.
The ink rendering system 500 (in particular, e.g., the rendering environment 502 ) may freeze the color settings of the pixels (step 604 ) within the region defined by the combination (e.g., union) of the queued regions (e.g., the shaded area in FIG. 9 ). The combined queued regions thus become an excluding clip region that may be sent to the graphics toolbox 503 . Freezing the color settings means preventing the color and intensity of the pixels from changing. Thus, any further attempts at painting the frozen pixels will have no effect on the color and intensity of the frozen pixels. This is important where the colors are transparent, since the new connecting quadrangle (e.g., quadrangle 909 ) is likely to overlap with the union of the queued regions (e.g., the shaded area in FIG. 9 ). Without freezing the pixels in the queued regions, the overlapping portion will undergo a change in transparency when the new regions are painted. Conventional graphics toolboxes are capable of freezing the color settings of a group of pixels. An alternative to determining the union of the queued regions and then freezing the determined union region is to simply freeze each of the queued regions individually. This alternative provides the benefit of avoiding the step of determining the union. However, it increases the number of regions that need to be sent to the graphics toolbox for freezing.
The new region may be sent to the graphics toolbox 503 for painting (step 605 ). The new region may be painted in a transparent or nontransparent color as desired. After the new regions are painted, some or all of the pixels in the excluding clip region may be unfrozen (step 606 ). This step allows the color settings of the formerly frozen pixels to again be modified. More generally, the ink rendering system 500 may determine whether pixels within the new pen tip instance and/or new connecting quadrangle are also within the previous regions (such as those regions in the queue). For those pixels that are, the color settings of those pixels may not be changed. For those pixels that are in the new pen tip instance but not within any of the previous queued regions, the color settings may be changed.
The new region (e.g., connecting quadrangle 909 ) may then be pushed into the queue (step 607 ). Where the queue has rules that determine the queue length, one or more of the oldest regions may be pushed out of the queue as appropriate according to the queue rules. For example, referring to FIG. 9 , a queue having a maximum of 4 regions may currently contain the following regions in the following order: 907 , 903 , 908 , and 904 (wherein 904 is the oldest). When connecting quadrangle 909 (in this example, the new region) is pushed into the queue, then region 907 is pushed out the queue in order to maintain no more than 4 regions within the queue. Thus, the new queue would contain regions 903 , 908 , 904 , and 909 (in that order, with 903 being the oldest and 909 being the newest). The queue may have any maximum length, such as 1 region, between 2 and 4 regions inclusive, between 5 and 10 regions inclusive, or between 10 and 20 regions inclusive, 10 and 100 regions inclusive, or more. If the queue length is too short, then it is likely that a new pen tip instance from a slow-moving pen may overlap a region recently dropped from the queue, resulting in an unintended decrease in transparency in the overlapping area. This results in an unexpected rendering of ink. However, as processing time increases with queue length, using a long queue length may require the system to group numerous regions, objects, or shapes, thereby slowing the system during the rendering process and/or requiring higher processor speed to maintain adequate representation of ink in real-time.
Further, a queue length that is allowed to be too long may prevent certain desirable overlapping of transparent ink, such as when writing the script letter “e” as in FIG. 21 . For example, if the queue length were long enough to include all of points A through P of FIG. 21 , then the overlapping as shown would not occur since all of the pixels in the shown segments would be part of the excluding clip region. But if the maximum queue length were set to, e.g., 4 regions, then at point M, as the overlap begins to occur, the queue would contain only the regions of the connecting region between L and M, the region defined by the pen tip instance at point L, the connecting region between K and L, and the pen tip instance at point K. In such a case, the portion of the ink to be overlapped would not be part of the excluding clip region. It is thus desirable to use a queue length that balances the above considerations. For example, a queue with a length of 4 regions is a reasonable compromise between quality and speed for a digitizer having a resolution of about 12,000 by 9,000 pixels with a sampling rate of about 130 samples per second. The maximal queue length may depend upon the resolution of the input digitizer, the display resolution, the sampling rate, the pen speed, user settings, application settings, and/or other considerations. For instance, a larger maximal queue length may be desirable with a higher digitizer resolution and/or a higher sampling rate.
The exemplary method of FIG. 6 may be repeated for each new region. Following the example discussed above, after the new region 909 is pushed into the queue, the method of FIG. 6 may be practiced where the new region is pen tip instance 905 . Once pen tip instance 905 is painted in step 605 and the excluding clip region is unfrozen in step 606 , then the pen tip instance 905 may be pushed into the queue and pen tip instance 903 may be pushed out of the queue. This results in the queue containing regions 908 , 904 , 909 , and 905 .
As an alternative to determining the union of the queued regions and/or freezing the pixels in the union, the intersection (i.e., overlap) between the new region and one or more of the queued regions may be determined. Instead of freezing the entire union of the queued regions, it may be desirable to freeze only those pixels in the intersection. For instance, where connecting quadrangle 909 is the new region, the intersection between the new region and the union of regions 907 , 903 , 908 , and 904 may be determined (as an alternative to step 603 ), and only those pixels in the intersection would be frozen (as an alternative to step 604 ).
It is understood that one or more of the steps illustrated in FIG. 6 may be performed in a different order, combined with another step(s), and/or divided into further sub-steps as appropriate. For example, step 603 may be performed prior to step 602 or even prior to step 601 . Also, while embodiments of the present invention are described with the connections between pen tip instances being line segments, it is appreciated that the ink between the pen tip instances do not have to be actual line segments or quadrilaterals. The ink may include groupings of triangles, be bowed in shape, or assume a variety of shapes. One example of using curved lines is the advantage of being able to provide a degree of smoothing to an ink stroke.
The generation of connecting quadrangles is now discussed. Referring to FIG. 7 , a particular exemplary ink stroke may include four circular pen tip instances 701 , 702 , 703 , 704 , and three connecting quadrangles 705 , 706 , 707 . Connecting quadrangle 707 (for example) has four corners A, B, C, D, and four sides. The notation for an edge will refer to the end points of the edge. Thus, for example, the edge between corners A and B will be referred to as edge (or line or chord) AB.
The calculations for determining a connecting quadrangle may vary depending upon the relative shapes and sizes of the pen tip instances. Where the pen tip instances are both perfectly circular and of the same size, as in FIG. 7 , the connecting quadrangle 707 that connects pen tip instance 703 and 704 may be defined by lines AC, BD that are tangent to the outer edges of both pen tip instances, closed by the chords AB, CD that connect them. Note that in this example where the pen tip instances are of the same size and are circular, the chords AB, CD each defines the geometric diameter of its respective pen tip instance. Also note that in this example, the connecting quadrangles are each rectangles with orthogonal sides. However, as will be seen in further examples, the connecting quadrangles are not necessarily rectangles. They may be any type of quadrangle such as parallelograms and trapezoids.
Thus far the exemplary pen tip instances have all been identically sized circles. However, this is not always the case. Pen tip instances may be of any shape, such as circles, rectangles (including squares), triangles, ovals, blobs, stars, lines, arcs, points, or polygons. Pen tip instances may be symmetric or asymmetric. An example of an asymmetric pen tip instance is one configured to emulate the tip of a calligraphy pen. Pen tip instances may also be of varying size, such that two consecutive pen tip instances in the same set of ink may be of different sizes. Pen tip instances may further be of varying shape, such that two consecutive pen tip instances in the same set of ink may be of different shapes. Pen tip instances may further be of varying rotation, such that two consecutive pen tip instances in the same set of ink may be rotated at different angles. Of course, where the pen tip instance is an exact circle, the angle of rotation is meaningless. The rotation of a pen tip instance is also considered a property of each pen tip position and/or the entire stroke. To account for these potential variations in pen tip instance characteristics, another exemplary ink rendering system 1000 is shown in FIG. 10 . The ink rendering system 1000 includes, or is coupled to, a pen device 1000 that feeds the (x, y) coordinates of the pen tip to a contour generator 1002 . The pen device 1000 may also feed the pen tip instance size and/or rotation (e.g., angle) for each pen tip instance. The contour generator 1002 may be configured to generate a contour defining the outline of the pen tip instance based on the information provided by the pen device 1000 , as well as information about the particular pen tip instance shape selected. Alternatively, there may be a plurality of contour generators 1002 each specializing in a different shape or family of shapes. For example, there may be a first contour generator that is configured to generate contours for circular pen tip instances and a second contour generator that is configured to generate contours for rectangular (including square) pen tip instances.
The contour generator 1002 (or another specialized contour generator) may also generate contours that define the shape of the connecting quadrangles, based on the received and utilized pen tip instance characteristics and positions. The contour generator 1002 may then send the generated contours to a graphics toolbox 1004 . Where the ink is transparent, the contour generator 1002 may communicated with the graphics toolbox 1004 via a rendering environment 1003 , and the method of FIG. 6 may be implemented. The graphics toolbox 1004 may fill or freeze the provided contours as appropriate and then output pixel values to an output device 1005 such as the monitor 407 .
Referring to FIG. 11 , an exemplary ink stroke has four pen tip instances 1100 , 1101 , 1102 , 1103 of different sizes. Since the pen tip instances are circular, rotation is less important in this example and will be ignored in the present example. As this ink stroke was drawn, the size of the pen tip instances changed from medium (pen tip instance 1100 ), to larger (pen tip instances 1101 , 1102 ), and then smaller (pen tip instance 1103 ). The size, rotation, and/or pen tip shape may be adjusted automatically by a software application running on the computer 400 and/or by the user. For example, the user may have pressed then stylus/pen 466 down against the digitizer 466 with additional pressure, or may have moved the stylus/pen 466 more slowly, to select larger pen tip instances. Or the user may physically rotate the pen along its longitudinal axis in order to obtain different rotated pen tip instances. The connecting quadrangles for different-sized circular pen tip instances are, in some embodiments, generated by determining tangential lines (e.g., lines AC and BD in FIG. 11 ) between the pen tip instances and then connecting those lines at the tangents with connecting chords (e.g., chords AB, CD in FIG. 11 ).
Referring to FIG. 13 , the same method may be used as in FIG. 11 for determining connecting quadrangles (or other shapes). An exemplary ink stroke may include oval pen tip instances 1301 , 1302 . The connecting quadrangle may, in one example, be determined by calculating the lines that run tangent between the two ovals. In this case, those tangential lines would be lines AC and BD in FIG. 13 . The tangential lines would then be closed by connecting their endpoints at the tangents with lines AB, CD. Note that although these ovals are of different rotational angles, the rotation does not matter for ovals when determining the connecting quadrangles.
Next in FIG. 15 is shown an exemplary embodiment of a connecting quadrangle between two rectangular pen tip instances 1501 , 1502 , each having a different size and rotation. Although there are many possible connecting quadrangles, in this example, a connecting quadrangle 1503 connects corners A and E, corners A and C, corners C and G, and corners G and E. Another connecting quadrangle that could be used would connect corners A and H, corners D and F, corners B and G, and corners C and H. Another example is shown in FIGS. 17A and 17B , showing two different connecting quadrangles 1703 , 1704 that could be used to connect two pen tip instances 1701 , 1702 . Connecting quadrangle 1703 connects corners A and A′, corners C and C′, corners A and C, and corners A′ and C′. Connecting quadrangle 1704 connects corners B and B′, corners D and D′, corners B and D, and corners B′ and D′.
It may be desirable to utilize a connecting quadrangle that connects between the outermost portions of the two pen tip instances to be connected. For instance, where the two pen tip instances are both polygons (i.e., closed shapes having only straight edges connected at corners), it may be desirable to connect the outermost corners together to provide for the largest area possible covered by the connecting quadrangle. Such an embodiment may in many cases provide a very smooth transition between pen tip instances and a higher-quality ink that is pleasing to the eye. Also, some or all of the possible connecting quadrangles (or a subset thereof) may be determined, and the determined quadrangles may be combined together (e.g., by taking their collective union) into a single connecting region. For example, referring to FIG. 17C , all of the possible connecting quadrangles that connect the corners of the pen tip instances 1701 , 1702 are shown. A result of this is that every corner of pen tip instance 1701 is connected to every corner of pen tip instance 1702 via an edge of at least one of the connecting quadrangles. This method may be extended to any polygon having any number of sides and corners.
FIG. 18 illustrates the resulting ink when all of the connecting quadrangles of FIG. 17C are combined together.
FIGS. 8 , 12 , 14 , 16 , and 18 illustrate the rendered ink that corresponds to the pen tip instances and connecting quadrangles in FIGS. 7 , 11 , 13 , 15 , and 17 C respectively. The rendered ink in these figures is a result of using the rendering system 1000 as described.
Ink Smoothing
The ink-rendering process may also include smoothing the ink. Smoothing may be performed by the rendering system 500 , 1000 , such as by the graphics toolbox 503 , 1004 , using known smoothing functions. Another example of an ink rendering system 1900 is illustrated in FIG. 19 . The ink rendering system 1900 includes a pen device 1901 , a smoothing application or subroutine 1902 , a curve-sampling application or subroutine 1903 , a contour generator application or subroutine 1904 , and/or a recipient 1905 , which may be a graphics toolbox. In operation, the pen device 1901 (e.g., a digitizer and pen) may measure the pen's (x, y) location on the digitizer. The pen device 1901 may further determine the intended rotation angle and/or size of the pen tip. The smoothing application 1902 may receive a plurality of sampled pen tip positions, pen tip instance sizes, and/or angles of pen tip instance rotation and may smooth the position, size, and/or rotation amongst the plurality of pen samples. The curve-sampling algorithm 1902 may sample the smoothed (x, y) curve, the smoothed size function, and/or the smoothed rotation function and may output samples of these smoothed functions to the contour generator 1904 . The contour generator 1904 may then generate the desired contours such as the pen tip instances and/or the connecting quadrangles, and forward these contours on to the recipient 1905 .
Smoothing may be performed on the size and/or rotation parameters. The rendering system 1900 may use any smoothing technique such as least squares fitting. To smooth ink, samples of the ink may need to be taken. These samples may be taken anywhere along the ink stroke, but at least one sampling technique is to sample the locations that were originally sampled from the pen (i.e., the sampled pen tip locations).
An exemplary smoothing function may be implemented by the ink rendering system 1900 (more particularly, by, e.g., the smoothing application 1902 ) as follows for each sample along the ink stroke:
(smoothed width) i =A 1 *(original width) i−l +A 2 *(original width) i +A 3 *(original width) i+l , (1)
where A 1 , A 2 , and A 3 are constants that may be chosen as desired, i is the sample number along the sampled ink stroke, “smoothed width” is the width of the ink stroke at sample i after smoothing, and “original width” is the width of the ink stroke at sample i before smoothing. In some examples, the sum of these three constants should equal unity. A combination of A 1 =0.25, A 2 =0.5, and A 3 =0.25 works well. Angle of rotation can also be smoothed using any of the method for smoothing width, including substituting “smoothed width” and “original width” in equation 1 with “smoothed angle” and “original angle,” respectively. In another embodiment, both size and angle may be smoothed for the same ink stroke.
Referring to FIG. 20 , an exemplary ink stroke is shown having sampled points C l through C n (each denoted with an “x”). Each sampled point C also has an associated size and/or rotation. Size, or width, at sample point C i will be denoted as W i , and its associated rotation will be denoted as R i . It may be desirable to smooth the sampled ink as to the (x, y) positions of the sample points, the size or width of the sampled points, and/or the rotation of the sampled points.
For example, using a least-squares method for smoothing, the following algorithm may be used such that the fitting curve P minimizes the following:
minΣ{a(C i −P i ) 2 +b[W(C i )−W(P i )] 2 +c[R(C i )−R(P i )] 2 }, (2)
where a, b, and c are optional weighting constants; P i are the locations of the points on the fitting curve P; W(P i ) are the sizes/widths for each point P i ; and R(P i ) are rotations for each point P i . The fitting curve P may be any curve desired, such as one chosen from the family of parametric or Bezier curves. In effect, width/size and/or rotation are treated as additional dimensions other than position. Any subcombination of the dimensions in fitting a curve may also be used. For example, the third term c[R(C i )−R(P i )] 2 may be dropped from equation 2 so that rotation is not considered. Or, the second term b[W(C i )−W(P i )] 2 may be dropped from equation 2 so that width or size is not considered. Or, the first term a(C i −P i ) may be dropped from equation 2 so that sample position is not considered. Alternatively, both the first and second terms, or both the first and third terms, may be dropped from equation 2 so that only rotation or only width are considered in determining the fitting curve parameters.
While exemplary systems and methods embodying the present invention are shown by way of example, it will be understood, of course, that the invention is not limited to these embodiments. Modifications may be made by those skilled in the art, particularly in light of the foregoing teachings. For example, each of the elements of the aforementioned embodiments may be utilized alone or in combination with elements of the other embodiments. For example, while connecting quadrangles are discussed herein as a particularly advantageous shape, any shape of connecting regions other than quadrangular-shaped regions may be used. Also, while the above description discussed pen tip positions as being defined by (x, y) in a rectilinear coordinate system on the digitizer, any other coordinate system, such as polar, may be used. | Apparatus and methods for dynamically rendering transparent ink strokes, in some situations such that the rendered ink stroke has transparency similar to physical ink while it is being drawn. For example, the ink stroke may be dynamically rendered as a stroke having uniform transparency while it is being drawn. Only the new ink segment that has most recently been added to the stroke may be drawn, and areas of the new ink segment that overlap older segments of the ink stroke may be frozen, or excluded from being re-painted. | 6 |
REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application Ser. Nos. 60/696,658, filed Jul. 5, 2005, and 60/731,762, filed Oct. 31, 2005, the entire content of both of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention generally relates to food compositions and processes for their manufacture. In one specific embodiment, the present invention relates to food compositions including microorganisms isolated from the digestive system of an animal which is a traditional food source for a type of animal which is an intended recipient of an inventive composition.
BACKGROUND OF THE INVENTION
[0003] While modern science has elucidated many biological processes at the cellular and even molecular level, the interactions between microbial organisms and mammalian organisms have been largely uncharacterized, although there is considerable evidence of their importance.
[0004] In particular, it is well established that various types of microbes ordinarily live in the mammalian gut. Such microbes, termed intestinal flora, are known to have effects on the organism that they colonize. For example, some bacteria synthesize and make certain essential nutrients available to the host animal. In humans, for instance, vitamin K is an essential compound which may be provided by bacterial synthesis in the gut.
[0005] A role for microorganisms in digestion has been extensively studied in some animals, such as ruminants. In other species exact functions of digestive system microorganisms are less understood.
[0006] The gastrointestinal system varies between species but generally includes several different sections having specific functions in the digestive process of the animal. In particular, digestive systems are configured differently depending on the usual food source of the animal. For example, a typical carnivore digestive system is configured to digest protein efficiently along with fats and some carbohydrates. A carnivore system is characterized by anatomical structures functional to mechanically dissociate food, such as teeth, a single acid secreting stomach which includes acid activated enzymes functional to break down proteins, the small intestine for further digestion and absorption of the food, and the large intestine which also functions to absorb some nutrients. Microorganisms present in regions of the carnivore digestive system function to digest some substrates indigestible by the carnivore, as well as provide some essential nutrients.
[0007] In contrast, an herbivore gastrointestinal system is configured to utilize carbohydrates derived from plants. In this regard, herbivores include ruminants, a type of animal that has a specialized multigastric configuration of the digestive system, and non-ruminant herbivores. Ruminants are characterized by a multigastric system having 3 to 4 compartments, including the rumen, reticulum, omasum and abomasum. The multigastric configuration functions to allow repetitive mechanical breakdown of plant material and provides an environment conducive to fermentation of the plant material by resident microorganisms.
[0008] In addition to a role in digestive metabolism, microorganisms are believed to play a more general role in the health of host animals. A number of diseases and disorders are believed to be related to alterations of number and/or types of microorganisms represented in the intestinal flora. For example inflammatory bowel diseases, such as Crohn's disease and ulcerative colitis are associated with reduced diversity of intestinal flora. (Ott, S. J. et al., Reduction in diversity of the colonic mucosa associated bacterial microflora in patients with active inflammatory bowel disease. Gut, 53:685-693, 2004.) Further, modern “lifestyle” disorders such as cancer, heart disease, hypertension, diabetes, senile dementia, microbial or viral infection, auto-immune disorder, atopic dermatitis, as well as various allergies and food sensitivities, more prevalent in recent history, are thought to be associated with changes in intestinal flora.
[0009] Both human and cultivated animal diets have changed significantly in recent history. Modem humans and the animals they raise for food or as companions now consume highly processed foods and/or foods never or rarely consumed in the natural or primitive environment. Further, the advent of high volume food manufacturing and relatively inexpensive snack foods has contributed to changes in the overall composition of foods included in a modem diet compared to previous eras. For instance, populations of modem humans eat more simple carbohydrates than were available historically. A cultivated animal's diet is now constructed according to convenience and to promote fast growth, rarely providing the foods the animal would eat in the natural state or as cultivated in a primitive society. A companion animal's diet is sanitized and largely adapted to human concepts of a pet's food preferences. These relatively recent changes are believed to cause distortions of the intestinal flora in humans and animals exposed to modem habits since modem diets support different populations of microorganisms than a traditional or primitive diet based on natural foods.
[0010] In addition to changes in diet, both humans and cultivated animals are routinely exposed to antibiotics which affect not only pathogenic microorganisms but benign and beneficial microorganisms as well. The systemic treatment of an individual during a course of antibiotics may result in elimination of gut microorganisms, many varieties of which may not be replaced if exposure to microorganisms is limited.
[0011] The diversity of modem intestinal flora in humans and other animals is believed to be limited by the paucity of sources of potential exposure to microorganisms. Currently human and even animal hygiene standards are at their historical zenith, with both desirable and unanticipated less desirable results. There is evidence that limited exposure of humans to dirt, dust, animals, and the various antigens found therein, such as bacteria and viruses, can predispose an individual to immune disorders, such as allergies and asthma.
[0012] Current dietary preferences and/or habits based on available food products also have a role in limiting exposure of modern humans and other animals to microorganisms. In particular, modem humans who eat meat typically prefer the muscle meat of an animal rather than the organ meat. In contrast, earlier societies valued all parts of the body of a source animal, including internal organs such as the heart, liver, kidneys, and, importantly, the digestive system including the tongue, the stomach, intestines and intestinal contents. For example, an account of a traditional Native American diet describes the use of buffalo entrails as food including intestines “full of half-fermented, half-digested grass and herbs . . . ” (John Lame Deer & Richard Erdoes, Lame Deer, Seeker of Visions , p. 122, Simon & Schuster, 1972) Further, both cultivated and wild animals which are sources of nutrition for humans and pets historically had access to food likely to expose the animals to microorganisms, such as pasture grass and other wild growing plants which were not processed to remove or inhibit microorganisms.
[0013] In addition, the distorted diet of the modern human leads to disorders due to nutritional deficiencies and/or over-exposure to particular foods. For instance, certain conditions, such as cardiovascular disease, adult-onset diabetes and obesity are associated with a modern lifestyle, including fast food and highly processed foods. High volume food manufacturing creates such unnatural foods at relatively low prices, such that natural foods are available only at premium prices. This creates the situation in which low-income populations eat disproportionate amounts of manufactured unnatural foods and suffer disproportionately from associated disease.
[0014] Ironically, the natural environment is filled with nutrients unavailable to humans and many other animals due to an inability to digest many plant materials, such as cellulose. A traditional means of gaining the benefit of these nutrients has been through the cultivation of animals capable of utilizing such materials. As outlined above, ruminants in particular are able to gain nutritious benefit from plant materials through a cooperative arrangement with intestinal flora. The intestinal microorganisms have the ability to ferment plant materials to provide for their own growth and, in addition, produce materials which provide a nutritional benefit to the host organism.
[0015] However, the time and energy spent raising such animals makes their meat and milk products expensive. Further, efforts to decrease the cost of animal food products have led to animal feed which is non-natural, negatively affecting the meat and milk products.
[0016] Large amounts of plant material normally cannot be consumed by humans and certain pet animals due to the high level of cellulose. Plant materials, such as grass, are plentiful and could serve as a nutritious and health promoting food, if they could be adapted for human and animal digestion. By producing such products on a mass scale from such plentiful and widely available raw materials that have heretofore been considered unfit for consumption, nutritious foods can be cheaply and easily provided, for instance, to large masses of undernourished peoples around the globe, mitigating the loss of lives from starvation.
[0017] Thus, in view of the disorders associated with distortion of diversity of intestinal flora and there is a continuing need for compositions and methods designed to provide exposure to microorganisms in order to promote health of humans and other animals. In addition, current unavailability of nutritional content of many plants makes it highly desirable to produce compositions and methods for making these nutrients available.
SUMMARY OF THE INVENTION
[0018] A food composition is provided by the present invention which includes a digestion or fermentation product of a food component of the natural diet of a source animal. The source animal is a traditional food source of a second type of animal. The food component is preferably a food found in the native habitat of the source animal. In one embodiment, a food component includes a grass.
[0019] A food composition according to the present invention may further include microorganisms isolated from a source animal, a digestive enzyme typically found in the digestive system of the source animal and/or a non-enzymatic secretion of the digestive system of the source animal.
[0020] A food composition intended for consumption by humans is provided according to the present invention. In such an embodiment, the source animal is a traditional food source for a human. An example of such a source animal is a weaned ruminant.
[0021] Further provided is a food composition intended for consumption by an animal commonly kept as a household pet. Source animals which are traditional foods for cats or dogs include ruminants, pigs, poultry, birds, fish, rodents, rabbits, hares, reptiles and amphibians.
[0022] A process for producing a food composition is provided which includes contacting one or more foods typically consumed as a part of a natural diet of a source animal and a plurality of microorganisms isolated from the source animal to produce a mixture. The mixture is incubated under conditions suitable for reaction of the mixture to produce a product such as a fermentation product of the one or more foods, a digestion product of the one or more foods, or a combination of these.
[0023] Further included in an inventive process is a step of adding a component typically found in the digestive system of the source animal to the mixture. Such a component is illustratively an enzyme produced by a cell of the digestive system of the source animal, non-enzymatic digestive secretion produced by a cell of the digestive system of the source animal, or a combination of these.
[0024] Further provided by the present invention is a composition which includes a food component of the natural diet of a source animal having a native habitat, wherein the source animal is a traditional food source of a second type of animal; a plurality of microorganisms isolated from a source animal; and a digestion or fermentation product of the food component.
[0025] In a preferred example, the food component is a grass. Also preferred is an embodiment in which the source animal is a weaned ruminant
DETAILED DESCRIPTION OF THE INVENTION
[0026] Food compositions, as well as methods of generating them and using them, are provided according to the present invention.
[0000] Food Compositions
[0027] Compositions are provided which include microorganisms and/or which are generated using microorganisms.
[0028] Microorganisms for use in food compositions and related methods are isolated from the digestive system of an animal which is a traditional food source for a second type of animal. Such isolated microorganisms may be used directly in a food composition and/or related method, and may also be cultured and/or amplified for such use.
[0029] The animal from which microorganisms are obtained is called a “source animal” herein, to indicate both that this animal is a source of microorganisms included in an inventive composition and that the animal is a traditional food source for a second type of animal which is an intended recipient of an inventive composition as described in more detail below. The terms “second type of animal” and “individual of a second type of animal” as used herein refer to an intended recipient of an inventive composition.
[0030] The term “traditional food source” as used herein is intended to mean an animal eaten for nutritive purposes in a natural setting by a second type of animal. Thus, for example, any of various herbivores are a traditional food source for any of various carnivores or omnivores. In contrast however, a carnivore is not considered a traditional food source for an herbivore.
[0031] Illustratively, microorganisms are isolated from the digestive system of a ruminant. Ruminants are herbivores which are a traditional source of food for a number of other animals, especially humans, but also including other relatively large carnivores and/or omnivores. Ruminants include cattle, sheep, goats, bison, buffalo, deer, elk, antelope, moose, and llamas for instance.
[0032] In other examples, microorganisms are isolated from the digestive system of an animal such as a pig, a poultry animal such as a chicken or a turkey, a bird, including a game bird, a fish, a shellfish, a horse, a rodent, a rabbit, and a hare. Such animals are a traditional source of food for humans and other relatively large carnivores and/or omnivores.
[0033] In a further example, microorganisms are isolated from the digestive system of an animal such as pigs, poultry, birds, fish, rodents, rabbits, hares, small reptiles and amphibians which are traditional food sources for smaller carnivores and/or omnivores such as domesticated dogs and cats. In addition, some ruminants described above are a traditional source of food for dogs. For instance, dogs may kill and eat cattle, sheep, goats, bison, buffalo, deer, elk, antelope, moose, and/or llamas.
[0034] A source animal is preferably raised in an environment as similar as possible to the environment in which the species historically lived prior to domestication. Thus a preferred source animal has never been exposed to exogenously administered growth hormones, antibiotics, pesticides, or other drugs.
[0035] It is highly preferred that the source animal is an animal fed a “natural” diet” over the span of its life. Cultivated ruminants are currently fed a distorted diet in order to promote maximum growth. For example, a typical feed preparation for a growing cow may contain about 20% grain and 80% silage or other roughage such as hay. In the final stage of preparing the cow for market, it may be fed a “finishing” diet including about 80% grain or more. Such a feeding regimen includes a disproportionate amount of grain compared to the diet a foraging animal in an uncultivated pasture would consume. Further, it is believed that high grain content in a food source animal's diet results in changes in composition of the food products produced from the animal. For instance, it has been shown that grain fed beef can have a higher amount of saturated fatty acids and an unfavorable ratio of saturated fatty acids to unsaturated fatty acids. P. French et al., Fatty acid composition, including conjugated linoleic acid, of intramuscular fat from steers offered grazed grass, grass silage, or concentrate-based diets, J. Anim. Sci., 2000, 78:2849-2855. Thus, it is particularly preferred to isolate microorganisms from an animal fed on a “natural” diet.
[0036] The term “natural diet” as used herein is intended to mean that the source animal is fed food growing wild in the animal's native habitat, and which excludes foods not normally found in such a native habitat.
[0037] The term “native habitat” is intended to preferentially include the habitat of the breed of a source animal prior to human domestication. By way of example, but not limitation, cattle would not naturally be found in habitats that receive large amounts of snow, since they have no way to reach grass under the snow in winter.
[0038] Optionally, a source animal may be an animal whose native habitat is located on the continent of Africa. In particular, a source animal may be an animal whose native habitat is located in the tropical region of Africa, that is, the region on either side of the equator extending between two parallels of latitude on the earth, one 23°27′ north of the equator and the other 23°27′ south of the equator.
[0039] A source animal may be a carnivore, herbivore or omnivore.
[0040] In a particular example, a source animal having an African native habitat is an herbivore of the order Artiodactyla. Common names for African animals of this type include topi, hartebeest, wildebeest, waterbuck, gerenuk, gemsbok, impala, gnu, gazelle, giraffe, okapi, kudu and eland. A source animal of particular interest may be the African cape buffalo (Syncerus caffer). These and other African and non-African animals may be a source animal, including those animals described in standard references such as: Jones, C. 1984. Tubulidentates, Proboscideans, and Hyracoideans, in Orders and Families of Recent Mammals of the World. Edited by Anderson, S. and J. K. Jones, Jr. John Wiley and Sons, N.Y. pp. 523-535; Nowak, R. M. 1991. Walker's Mammals of the World. Fifth Edition. Johns Hopkins University Press, Baltimore; Thenius, E. 1990. Even-toed Ungulates. In Grzimek's Encyclopedia of Mammals. Volume 5. Edited by Parker, S. P. New York: McGraw-Hill. Pp. 1-15; and Webb, J. E., J. A. Wallwork, and J. H. Elgood. 1979, Guide to Living Mammals, Second Edition. Bell and Blain Ltd., Glasgow.
[0041] In this context it is to be understood that a source animal is preferably an animal that has been weaned. An unweaned animal typically has a different set of microorganisms in the gut since the animal has not yet been exposed to many of the typical sources of gut flora. Thus, milk, milk products, and milk components, such as whey, are not among foods considered “natural” for a weaned source animal.
[0042] The components of a natural diet will depend on the source animal. Animals in the wild will select a diet which they are adapted to digest and which corresponds to their usual food seeking behavior.
[0043] Common food seeking behavior of some animals includes “grazing” and “browsing”. For example, wild grazers will eat a diet composed primarily of grasses and other ground plants such as clover. Grazers include cattle and bison among others. Wild browsers will eat grasses and ground plants, and in addition, will eat leaves and small twigs from trees and bushes. Browsing animals include deer and goats among others.
[0044] Exemplary African source animals also display various food selection preferences. For instance browsers include such source animals as the giraffe and Guenther's dik-dik and grass or ground plant preferring animals include the hartebeest and wildebeest.
[0045] The diets of herbivores also contain other material ingested along with grasses and ground plants, such as small amounts of seeds and insects.
[0046] In addition to larger herbivores discussed above, smaller herbivores, such as rabbits and hares are considered source animals for humans and certain pets, including cats and dogs. The natural diet of such herbivores includes grasses and ground plants.
[0047] Rodents such as mice, rats and squirrels are typically natural omnivores, eating a natural diet they will consume such foods as insects, terrestrial non-insect arthropods, leaves, roots and tubers, wood, bark, stems, grains, nuts, fruit, seeds, fungi, young birds, eggs, amphibians and reptiles. Among rodents, rats are known to each nearly anything edible as part of a natural diet including birds, mammals, amphibians, reptiles, fish, eggs, carrion, insects, terrestrial non-insect arthropods, mollusks, terrestrial worms, aquatic crustaceans, echinoderms, other marine invertebrates, zooplankton, and fungus.
[0048] Small birds eating a natural diet consume such foods as insects, seeds, buds, berries, fruit, flower nectar, cereals, grain, and grass.
[0049] Poultry, including domestic or wild chickens, turkeys, guinea fowl, pheasants, quail, pigeons, doves and peacocks, are typically omnivores whose natural diet includes fruits, seeds, leaves, shoots, flowers, tubers, roots, arthropods, snails, worms, lizards, snakes, small rodents, avian nestlings and eggs, for example. Poultry also include aquatic birds such as ducks and geese, which are typically herbivores whose natural diet includes such foods as vegetation, including leaves, roots and tubers, seeds, grains, nuts and algae. These animals are also occasional omnivores whose natural diet may include worms, gastropods, arthropods, and small fish.
[0050] Pigs include members of the family Suidae. Pigs are typically omnivores whose natural diet includes bulbs, carrion, earthworms, eggs, fruit, fungi, leaves, roots, tubers, snails, and small vertebrates such as nesting birds and small rodents.
[0051] Small reptiles include skinks and lizards which are generally insectivorous, eating spiders, millipedes, crickets, termites, grasshoppers, caterpillars, non-insect arthropods, beetles, and beetle larvae; and snakes which eat small birds, small mammals, amphibians, fish, insects, terrestrial non-insect arthropods, mollusks, and terrestrial worms.
[0052] Amphibians, such as frogs and toads consume a natural diet including insects, annelids and gastropods.
[0053] The natural diet of fish includes fish, fish eggs, aquatic vegetation, and aquatic invertebrates such as plankton, brine shrimp, and krill.
[0054] A source animal may be bred and/or maintained as a cultivated animal by humans in order to obtain microorganisms and/or other contents of the gastrointestinal tract. Optionally, a source animal is caught in its native habitat, a sample of microorganisms and/or other contents of the gastrointestinal tract obtained for use in an inventive composition and/or amplification for use in an inventive composition. The animal may then be returned to the wild. In a further option, a source animal is caught in its native habitat and then maintained in captivity. Where a source animal is cultivated and/or maintained in captivity, it is fed a natural diet.
[0055] Grasses eaten as part of a natural diet include those of the family of “true grasses”, that is, those classified in the family Poaceae (also known as Graminae). There are about 700 genera and nearly 12,000 species of grasses. Such grasses generally have hollow stems with nodes at intervals in the stems where leaves may be located. The fruit of such grasses is known as a grain. The family Fabaceae also includes a number of plants found in the natural diet of herbivores including clover and alfalfa.
[0056] Some of the grasses in the family Poaceae are mass cultivated as food and are known as cereals, including maize (or corn), wheat, oats, rye, rice, and barley. It is these and similar cultivated cereal grains which are typically included in disproportionate amounts in the modern diet of a food source animal compared to a natural diet. It is particularly preferred that the animal is fed a diet of natural foods in the proportion that the animal would feed on in a natural diet. Thus, since cereal grain is relatively rare in the wild habitat, a grazing herbivore, such as a buffalo or cow, would have little cereal grain in its natural diet. An herbivore source animal from which microorganisms are isolated is therefore preferably an animal fed predominantly grass with little or no cereal grain. For instance, a preferred diet includes less than 5% cereal grain, and preferably less than 2% cereal grain. Highly preferred is a source animal fed substantially no cereal grain.
[0057] In addition to the composition of the source animal's diet, the quality of food consumed by a source animal is considered important as well since this can influence the number and identity of microorganisms present in the gut. A preferred source animal is one fed a diet of organically gown food throughout its life, that is, food which is minimally processed, not genetically modified, grown without pesticides and herbicides, and grown using only natural fertilizer if any is used.
[0058] Microorganisms and Isolation of Microorganisms
[0059] An isolated sample of microorganisms may be obtained from any of various regions of the digestive system of the source animal. For example, microorganisms may be isolated from the mouth, the esophagus, the pharynx, the stomach, the rumen, the omasum, the abomasum, the reticulum, the small intestine, the large intestine, the caecum, or combinations of these.
[0060] In one embodiment, the contents of a portion of the digestive system are obtained and a sample of microorganisms is isolated from the contents. For example, contents of the digestive system of an animal include ingested food particles, partially digested material and fecal material. In a further embodiment, microorganisms may be isolated from a digestive system tissue. Thus, for example, scrapings from the walls of the digestive system are one type of sample of microorganisms from a digestive system tissue. Optionally, an isolated sample of microorganisms obtained from the digestive system of a source animal may be combined with isolated samples from other animals.
[0061] In a further embodiment a sample of microorganisms is obtained from the digestive system of the source animal and amplified by growing the microorganisms on a culture medium to yield an amplified microorganism culture.
[0062] In a highly preferred embodiment the culture medium includes one or more foods traditionally consumed as a natural diet by the type of animal from which the microorganisms are obtained.
[0063] Thus, for example where the sample is obtained from the digestive system of an herbivore, a culture medium includes a grass and/or ground plant, such as clover, or an extract thereof. A grass included as a culture medium is preferably an organically grown and minimally processed natural grass of a type that would be found in the animal's native habitat. Grasses which may be included in a culture medium include those of the family of “true grasses”, that is, those classified in the family Poaceae (also known as Graminae). Another exemplary component is a plant from the family Fabaceae, such as a clover and/or alfalfa, which may also be included in a culture medium for microorganisms. However, a culture medium preferably includes little or no cereal grain from the grass family. For instance, a preferred culture medium contains less than 5% of a cereal grain and further preferably contains less than 2%. Highly preferred is a culture medium which contains substantially no cereal grain. Further, since microorganisms are obtained from weaned animals, a culture medium contains substantially no milk, milk products or milk components.
[0064] In an example where a source animal is a carnivore or omnivore, a culture medium includes typical contents of such an animal's digestive system and particularly, includes components of the animal's natural diet.
[0065] Techniques and other culture media and components thereof for amplification of microorganisms from a sample obtained from the digestive system of an animal are exemplified in J. P. Salanitro et al., Bacteria isolated from the duodenum, ileum, and cecum of young chicks, Appl. Environ. Microbiol. 35(4):782-790, 1978; W. E. C. Moore and L. V. Holdeman, Human Fecal Flora: The Normal Flora of 20 Japanese-Hawaiians, Appl. Microbiol. 27(5):961-979, 1974; M. Morotomi et al., Distribution of indigenous bacteria in the digestive tract of conventional and gnotobiotic rats, Infect. Immun. 11(5):962-968, 1975; P. Quinn, Clinical Veterinary Microbiology, Mosby, 1994; and R. M. Atlas, Handbook of Microbiological Media, CRC Press; 3rd ed., 2004.
[0066] In one embodiment a sample obtained from a source animal is tested prior to culture to determine the number and diversity of microorganisms present. For example, a portion of the sample may be subjected to cell or molecular analysis, such as polymerase chain reaction (PCR) analysis, to characterize the microorganisms present. Following obtention of an amplified microorganism culture, cell or molecular analysis, such as a PCR analysis, may be performed to determine the diversity of the amplified culture. Comparison of first and second PCR analyses may be performed to ascertain the number and diversity of microorganism species present in the sample and the amplified culture. This information may be used, for instance, to modify culture conditions to achieve a greater diversity in the amplified culture.
[0067] Cell analysis of a sample of microorganisms may include standard microbiological analysis, for instance growing a sample on a selective medium, microscopic examination, and/or staining. In addition other molecular techniques are applicable in analysis of microorganisms, such as isolation of nucleic acids and Southern or Northern blotting.
[0068] Cell and molecular analysis of microorganism samples and culture samples may be performed according to standard techniques. Exemplary protocols and conditions for PCR and other analyses of gut microorganisms are set forth in references such as J. Sambrook et al., Molecular Cloning: A Laboratory Manual, Cold Spring Harbor Laboratory Press; 3rd ed., 2001; Eckburg, P. B., et al., Diversity of the Human Intestinal Microbial Flora, Science. 308: 1635-1638, 2005; Nordgard, L. et al., Nucleic Acid isolation from ecological samples-vertebrate gut flora, Methods Enzymol., 395:38-48, 2005; Anderson, K L et al, Comparison of rapid methods for the extraction of bacterial DNA from colonic and caecal lumen contents of the pig, J. Appl. Microbiol., 94(6):988-93, 2003; McOrist, A L et al., A comparison of five methods for extraction of bacterial DNA from human faecal samples, J Microbiol Methods, 50(2):131-9, 2002; Yu, Z and Morrison, M, Improved extraction of PCR-quality community DNA from digesta and fecal samples, Biotechniques, 36(5):808-12, 2004; Hume ME et al., Poultry digestive microflora biodiversity as indicated by denaturing gradient gel electrophoresis, Poult Sci., 82(7):1100-7, 2003 and Sharma, R, et al., Extraction of PCR-quality plant and microbial DNA from total rumen contents, Biotechniques, 34(1):92-4, 96-7, 2003.
[0069] Optionally, particular microorganisms are selected for during an amplification step such that an amplified culture is enriched in a particular microorganism compared to the sample obtained from the source animal.
[0070] A sample of microorganisms obtained from the digestive system of a source animal is a complex mixture of microorganisms. Among the microorganisms in the sample may be a bacterium, a protozoan, a yeast, a fungus, a bacterial spore, a protozoal spore, a yeast spore, a fungal spore, or combinations of these. Further diverse species of these organisms are present in the digestive system of the animal from which the sample is taken. Thus, in one embodiment, diverse species of microorganisms are included in an inventive composition. In a preferred embodiment, more than one species of microorganism is included in an inventive composition. In a further preferred embodiment, 2-4 species of microorganism are included, and more preferably, 5 or more species of microorganism are included in an inventive composition.
[0071] In a highly preferred embodiment, at least 50% of the total number of species represented in a sample taken from the digestive system of the source animals are included in a composition according to the invention. Further preferred is an embodiment in which at least 75% of the total number of species represented in a sample taken from the digestive system of the source animals are included in a composition according to the invention. Additionally preferred is an embodiment in which at least 85% of the total number of species represented in a sample taken from the digestive system of the source animals are included in a composition according to the invention. Also preferred is an embodiment in which at least 85-100% of the total number of species represented in a sample taken from the digestive system of the source animals are included in a composition according to the invention.
[0072] Among the microorganisms included in an inventive composition may be a bacterium, a protozoan, a yeast, a fungus, a bacterial spore, a protozoal spore, a yeast spore, a fungal spore, or combinations of these.
[0073] Food Compositions
[0074] A food composition according to an embodiment of the present invention is intended to provide a nutritional benefit to a recipient animal. In particular, an embodiment of an inventive food composition is intended to provide a nutritional benefit to a recipient animal that would historically have been obtained by ingesting at least a portion of the contents of the digestive tract of a source animal. Thus, an embodiment of an inventive food composition includes a digestion and/or fermentation product of a food component of the natural diet of the source animal.
[0075] An inventive food composition includes a digestion and/or fermentation product of a food component of the natural diet of the source animal.
[0076] In a preferred embodiment, an inventive food composition includes microorganisms typically found in the digestive tract of the source animal and a digestion and/or fermentation product of a food component of the natural diet of the source animal.
[0077] Optionally, and preferably, a food composition according to the present invention contains little or substantially none of a food component of the natural diet of the source animal which is undigested or unfermented. Thus, for example, a food composition according to the present invention contains an amount a food component of the natural diet of the source animal which is undigested or unfermented in the range of about 0-5 percent of the total weight of the composition. In further embodiments, this amount is in the range of about 0-2 percent of the total weight of the composition. Preferred is a composition which is substantially free of an undigested or unfermented food component of the natural diet of the source animal.
[0078] In further preferred embodiments, an inventive food composition includes one or more digestive enzymes of the source animal, one or more non-enzymatic digestive components such as non-enzymatic digestive secretions of the source animal, as well as other components typically found in the intestinal contents of a source animal.
[0079] A food component of the natural diet of the herbivore source animal may be fermented by the action of microorganisms in the digestive system of the source animal and serves as a nutritive medium for such microorganisms. In addition, products of such fermentation, and digestion of the microorganisms themselves serve as a source of nutrition for the source animal.
[0080] Many food components of the natural diet of a carnivore or omnivore source animal are digested by the action of enzymes and non-enzymatic components of the digestive system of the source animal. In addition, some of the food components may be fermented by the action of microorganisms in the digestive system of the source animal and serve as a nutritive medium for such microorganisms.
[0081] A product of microbial fermentation of a nutritive medium may be included in a food composition. Exemplary products of microbial fermentation of a cellulose-rich nutritive medium, such as grass, include short chain fatty acids such as acetic acid, propionic acid and butyric acid among others.
[0082] Digestion products of foods may also be included in an inventive food composition. Exemplary digestion products include peptides, amino acids, oligosaccharides, disaccharides, monosaccharides, glycerol and fatty acids.
[0083] Where a human is an intended recipient of an inventive food composition, an exemplary source animal is a weaned cow fed a natural diet over the span of its life. Thus, an inventive food composition includes digestion and/or fermentation products of a food component of the natural diet of such a cow. Preferably also included is an isolated sample of microorganisms, and/or an isolated amplified sample of such microorganisms, from the digestive tract of such a cow. Optionally further included are digestive enzymes and/or non-enzymatic digestive components, as well as other components typically found in the intestinal contents of such a cow.
[0084] Where a pet cat is an intended recipient of an inventive food composition, an exemplary source animal is a weaned rodent fed a natural diet over the span of its life. Thus, an inventive food composition includes digestion and/or fermentation products of a food component of the natural diet of such a rodent. Preferably also included is an isolated sample of microorganisms, and/or an isolated amplified sample of such microorganisms, from the digestive tract of such a rodent. Optionally further included are digestive enzymes and/or non-enzymatic digestive components, as well as other components typically found in the intestinal contents of such a rodent.
[0085] Where a pet dog is an intended recipient of an inventive food composition, an exemplary source animal is a weaned rabbit fed a natural diet over the span of its life. Thus, an inventive food composition includes digestion and/or fermentation products of a food component of the natural diet of such a rabbit. Preferably also included is an isolated sample of microorganisms, and/or an isolated amplified sample of such microorganisms, from the digestive tract of such a rabbit. Optionally further included are digestive enzymes and/or non-enzymatic digestive components, as well as other components typically found in the intestinal contents of such a rabbit.
[0086] Optionally, a substantial portion of the microorganisms are separated from the product of microbial fermentation in an inventive food composition. Where present, a substantial portion of microorganisms are preferably living when included in a food composition according to the invention. However, optionally, a substantial portion of the microorganisms are killed prior to consumption by a recipient animal.
[0087] The source animal is preferably weaned and an animal which has been fed a natural diet over a period of time extending from weaning to a time at which microorganisms are isolated from the digestive system of the source animal.
[0088] A composition formulated as a food may further include foods, flavorings, vitamins or other additives which provide nutritive value or other benefit to the consuming animal. Such other benefits include, for example, making the composition palatable.
[0089] A composition is provided which is an intermediate in a process for producing a food composition according to the present invention. Such a composition includes, in one embodiment, a plurality of microorganisms isolated from the digestive system of a source animal, a nutritive medium for the plurality of microorganisms and a product of fermentation of the nutritive medium by the microorganisms.
[0090] The nutritive medium for the microorganisms included in an embodiment of an inventive food composition is a food consumed by a source animal as part of a natural diet. Optionally, the nutritive medium is substantially indigestible by the second type of animal which is intended to consume the food composition.
[0091] In a highly preferred embodiment, the nutritive medium contains a grass and/or ground plant and substantially excludes a cereal grain. A nutritive medium is further preferably organically grown and minimally processed.
[0092] Methods Relating to Food Compositions
[0093] In one embodiment, a method of preparing an inventive food composition includes securing an animal that has been a traditional source of food for humans and that has been feeding from naturally occurring food in its native habitat and obtaining a fresh raw sample of at least partially digested contents from the animal intestine. Microorganisms from the partially digested contents are used to ferment the naturally occurring animal food, whereby the fermented naturally occurring animal food may be used as a food for use by humans. By way of example, microbacteria from the intestine of a cow can be used to ferment batches of grasses naturally eaten by that breed of cow.
[0094] In another embodiment, a method is provided for creating a food for use by humans which includes the steps of securing an animal that has been a traditional source of food for humans and that has been feeding from naturally occurring food in its native habitat and obtaining a fresh raw sample of at least partially digested contents from the animal intestine. Additional steps include extracting microorganisms from the partially digested contents and using the microorganisms to ferment batches of the naturally occurring animal food, whereby the fermented naturally occurring animal food may be used as a food for use by humans.
[0095] A method of preparing an inventive food composition according to one embodiment includes contacting a nutritive medium for microorganisms and a plurality of microorganisms to produce a mixture including the nutritive medium and the plurality of microorganisms. The mixture is incubated under conditions suitable for fermentation of the nutritive medium by at least a portion of the microorganisms to produce a fermentation product. Conditions suitable for fermentation of a nutritive medium are achieved by controlling factors such as temperature, oxygen level, volume, osmolality, nutritive medium concentration, product concentration, and pH. In one embodiment, conditions suitable for fermentation are designed to approximate the environment found in the portion of the source animal digestive system from which the microorganisms are extracted.
[0096] A process for producing a food composition in one embodiment includes contacting one or more foods typically consumed as a part of a natural diet of a source animal, a plurality of microorganisms isolated from a source animal and, optionally, a component typically found in the digestive system of the source animal, such as an enzyme produced by a cell of the digestive system of a source animal, a non-enzymatic digestive secretion produced by a cell of the digestive system of a source animal, or a combination thereof; to produce a mixture. The mixture is incubated under conditions suitable for reaction of the mixture to produce a fermentation product of the one or more foods and/or a digestion product of the one or more foods. Highly preferred are incubation conditions designed to approximate the environment found in the portion of the source animal digestive system from which the microorganisms are extracted.
[0097] Conditions suitable for fermentation and/or digestion which approximate the environment in a particular portion of the digestive system of a source animal are known, for instance, as described in Barnett, A. J. G. and Reid, R. L., Reactions in the Rumen, Edward Arnold Publishers, Ltd., 1961; Stevens, C. E. and Hume, I. D., Comparative Physiology of the Vertebrate Digestive System, 2 nd Ed., Cambridge University Press, 1995; and Dougherty, B. S. et al., Physiology of Digestion in the Ruminant, Butterworth, Inc., Washington, 1965. For example, such conditions include a temperature close to the body temperature of the source animal, in the range of about 35-43 degrees Centigrade. Such conditions further include a pH in the range of about pH 1-pH 8, depending on the portion of the digestive system concerned. Fermentation and/or digestion may be performed in volumes approximating the volume of a portion of the digestive system of a source animal or may be scaled up or down where desired.
[0098] In one embodiment, atmospheric conditions suitable for fermentation are generally low oxygen or anaerobic conditions, typically in an atmosphere containing less than 10% oxygen.
[0099] A mixture incubated under conditions suitable for fermentation and/or digestion to produce a fermentation and/or digestion product optionally includes further components promoting production of a fermentation and/or digestion product. For example, one or more salts may be added to adjust the ionic composition of the mixture.
[0100] In one embodiment, such further components are included so as to closely approximate the conditions present in the digestive system of the source animal in composition and concentration of the incubated mixture. For example, enzymes produced by cells of the digestive system of the source animal may be included. Such enzymes include lipases, poly- and oligo-saccharidases, proteases, peptidases and polynucleotide nucleases and oligonucleotide nucleases. Further, non-enzymatic digestive secretions such as bile, or components of bile, such as bile salts, may be included.
[0101] Digestive enzymes and non-enzymatic digestive secretions may be isolated from a source animal. Alternatively, digestive enzymes and/or non-enzymatic digestive secretions may be produced recombinantly or by chemical synthesis.
[0102] A mixture incubated under conditions suitable for fermentation and/or digestion to produce a fermentation and/or digestion product may further be subjected to movement to approximate the mixing and movement of intestinal contents in situ. Such movement may include gentle stirring or rocking of a container holding a mixture.
[0103] Fermentation and/or digestion reactions may be performed in batches or continuously. For instance, an incubation container having an inlet and an outlet is provided so that a food component of the natural diet of a source animal, microorganisms, gases and other components may be added through the inlet, incubated therein, and fermentation and/or digestion products, microorganisms, gases and other components may be removed via the outlet.
[0104] Fermentation and/or digestion reactions of a mixture may be performed for a time sufficient to ferment and/or digest the mixture such that substantially all of the food component is fermented and/or digested to produce a resulting food composition. Alternatively, an unfermented and/or undigested food component may be removed such that to produce a food composition substantially free of an unfermented and/or undigested food component. For example, unfermented and/or undigested food may be separated out by centrifugation.
[0105] Optionally, a substantial portion of the microorganisms is removed from the mixture following fermentation and/or digestion. Removal may be effected by physical separation, such as by centrifugation, and/or by killing the microorganisms, such as by lysis for example.
[0106] Any patents or publications mentioned in this specification are incorporated herein by reference to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference.
[0107] Methods and compositions described herein are presently representative of preferred embodiments. Thus, they are exemplary and are not intended as limitations on the scope of the invention or inventions. Changes therein and other uses will occur to those skilled in the art. Such changes and other uses are encompassed within the spirit of the invention as defined by the scope of the claims. | Compositions are provided according to the present invention which include microorganisms and/or products of microorganismal metabolism. Humans and other animals have difficulty gaining nutritional benefit from many highly abundant plant materials, such as cellulose. A traditional means of gaining the benefit of these nutrients has been through the cultivation of animals capable of utilizing such materials, subsequently consuming their meat and milk products. However, raising such animals is time consuming and expensive. Compositions and methods according to the present invention allow circumvention of the use of these cultivated animals for meat and milk. Microorganisms are isolated from an animal which is a traditional source of food for a second type of animal, such as humans or pets, in order to produce compositions of the invention. Such compositions provide nutritional benefit to the consumer. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the construction of glass blocks and the like and more particularly to a modular frame assembly that comprises a plurality of modular frame members that are assembled in an interconnecting arrangement to define a support structure for the construction of a glass block wall that does not require conventional cement grout material.
2. Description of the Prior Art
As is well known in the art, various problems and difficulties are encountered in providing suitable and efficient means for the installation and construction of glass-block wall structures. Many types of glass blocks have been tried over years and have been found lacking a simple solution whereby one can readily construct a sound wall quickly, without cracking or chipping the blocks, and further wherein the wall is assured of being assembled in a square and plumb manner. All of the known methods of assembling such glass block walls require the use of cement grout. When using cement grout, there is a problem in providing true horizontal and vertical course arrangement between each row of blocks. Spacing between each contiguous positioned block is still another problem. As is often the case, many glass block walls are installed after the structural wall has been erected having a specific opening left therein for later installation of the glass block assembly. Again, much time and effort are required for proper installation thereof. As examples of some known glass block assemblies, one may refer to any of the following U.S. patents.
There is disclosed in U.S. Pat. No. 2,227,842 to Milos Polivka a glass wall comprises individual glass blocks, each of which is recessed in its circumferential surface, and multiarmed anchoring elements located in planes angularly disposed relative to one another. The elements are adapted to be mounted near the intersections of each group of adjacent blocks, with their arms extending through the interstices between the adjacent blocks. There are means on the arms to engage the recesses of the blocks and bond them together to form a monolithic structure.
In U.S. Pat. No. 2,326,245 to Raymond Nichols et al, there is a wall structure comprising a series of panels, each panel being composed of a plurality of glass blocks, the panels being provided with a frame of perimeter bars, and the bars between adjacent edges of the panels being provided with stirrups comprising straps of metal and link-like key elements interconnecting the stirrups.
In U.S. Pat. No. 2,303,844 to Percy E. Knudsen, there is disclosed a mullion construction which comprises a pair of panels of glass blocks and a mullion between the two panels. The mullion comprises a core of an approximate I-beam section, with the flanges of the beam being approximately parallel the planes of the panels, providing a sheathing for the core. The sheathing comprises channel elements receiving packings against which the edges of the panels bear, the bottom portions of the channels being bent to provide groove portions and anchor elements embedded in the joints between the blocks in the panels and having projecting ends extending into the groove portions.
Other U.S. patents of interest are as follows;
U.S. Pat. No. 2,239,537 to William Owen.
U.S. Pat. No. 2,156,678 to Samuel Frank Cox.
U.S. Pat. No. 2,106,177 to Victor J. Hultquist.
U.S. Pat. No. 2,546,356 to John B. Boyd.
OBJECTS AND SUMMARY OF THE INVENTION
The present invention is defined as a modular frame assembly designed to provide an encasement for the erection of glass-block wall structures that overcomes the problems that now exist in the art of building glass block walls. The modular frame assembly comprises a plurality of perpendicular or upright frame members and a plurality of horizontal frame members that are assembled together with the perpendicular frame members. The horizontal frame members are of two types. One type is employed as an interposed spacer that is positioned between a pair of upright frame members on which a glass block is placed, and the other type horizontal frame member is arranged to establish the top and bottom frame members which extend the length of the finished frame assembly. Each upright frame member has a length that is approximately equal to the height of the wall formed by the glass blocks, with the horizontal spacer frame members having a length that is approximately equal to the length of the particular glass block that is to be assembled within the encasement defined by the frame assembly. All of the frame members are formed with a pair of back-to-back locking tracks that are arranged to receive respective locking tabs formed on the opposite ends of the horizontal spacer frame members.
Thus, the present invention has for an important object a provision wherein the frame assembly has only three basic frame members that are readily assembled without the use of tools. This is, each frame member is provided with respective interconnecting locking arrangements.
Another object of the present invention is to provide a novel modular frame assembly for mounting glass blocks that makes it simple, quick and easy to assemble the complete framework which has not been possible in the past.
Still another object of the invention is to provide a glass block encasement of the type that assures a square and plumb structure when completed.
It is still another object of the invention to provide a framework assembly that allows a glass block wall to be built without the use or need of cement grout material.
A further object of the invention is to provide a framework of this character that not only establishes an encasement structure but further provides a sealing system throughout the glass wall structure wherein the joints between the blocks are even throughout the vertical and horizontal seams thereof.
The characteristics and advantages of the invention are further sufficiently referred to in connection with the accompanying drawings, which represent two embodiments. Other variations may be made without departing from the principles disclosed and I contemplate the employment of any structures, arrangements or modes of operation that are properly within the scope of the appended claims.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
With the above and related objects in view, the invention consists in the details of construction and combination of parts, as will be more fully understood from the following description, when read in conjunction with the accompanying drawings and numbered parts, in which:
FIG. 1 is a pictorial view of a bottom corner view of a glass block wall structure showing the outer upright frame member broken away for illustrative purposes;
FIG. 2 is an enlarged exploded view showing the locking member of the upright and horizontal spacer frame members;
FIG. 3 is an enlarged cross-sectional view taken substantially along line 3--3 of FIG. 1, but without the glass block positioned therein;
FIG. 4 is an enlarged cross-sectional view taken substantially along line 4--4 of FIG. 1, wherein an upper and lower glass block are positioned on the respective sides of the horizontal spacer frame member;
FIG. 5 is an enlarged exploded view of the connecting ends of the horizontal and vertical peripheral frame members to illustrate their respective interlocking ends; and
FIG. 6 is an enlarged end view of the two peripheral frame members in an interlocked position.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring more particularly to FIG. 1, there is shown a pictorial view of a lower corner portion of a glass wall structure, generally indicated at 10, wherein the invention is depicted in its assembled form. This is, a plurality of glass blocks 12 are positioned vertically and horizontally to each other and are stacked in a juxtaposed fixed relation to each other by means of a modular frame assembly, designate at 14, that provides a peripheral encasement framework 15 which defines generally a quadrangle configuration of a glass wall structure 10.
The modular frame assembly 14 comprises a first set of elongated frame members that are positioned in an upright or perpendicular arrangement and a second set of frame members that are positioned in a horizontal arrangement. The upright frame members, generally designed at 16, are used to establish outer side frame members 16a which are part of the peripheral encasement framework 15, and inner frame members 16b which define fixed partitions that are positioned vertically between glass blocks 12. Both upright frame members 16a and 16b are identical in length and configuration, the length thereof being sufficient enough to cover the full length or height of the glass wall structure 10. The second set of frame members, generally indicated at 20, includes two types of horizontal frame members. One type of the horizontal frame members is used as part of the outer peripheral encasement framework 15 and comprises an elongated frame members 20a that is arranged to be positioned to cover the top and bottom rows of glass blocks 12, as shown in FIGS. 1 and 5. The top and bottom horizontal frame members 20a are formed having a length substantially sufficient enough to be connected to the corresponding ends of upright frame members 16a and 16b, the details of which will hereinafter be described.
The other horizontal frame member is designated generally at 20b and is designed to be used as a spacer between the upright members 16a and 16b, and will hereinafter be referred to as spacer frame member 20b. The spacer frame members 20b is formed such that each spacer frame member has the particular length of the glass blocks that are being used in the construction of the wall, and includes means on the outer ends thereof for attaching to the respective adjacent upright frame members 16. Accordingly, when modular framework is formed about the glass blocks, as illustrated in FIG. 1, a box-like receptacle or compartment 18 is defined in which each block 12 is mounted and secured therein.
The following is a description of how the wall is constructed together with a detailed description of each of the frame members. Starting with the top and bottom horizontal frame members 20a, there is provided a web portion 22 that extends the full length of the frame member, wherein a securing means is formed which is defined by a pair of securing tracks 24 that are spaced apart and extend throughout the length thereof. Each track 24, however, is in itself formed as a pair of securing tracks. That is, each track is provided with back-to-back, retaining flanged channels 25, also referred to as dual channels, whereby each web portion is formed having a securing means on both surfaces thereof. Web 22 extends outwardly from tracks 24 with each opposite longitudinal edge thereof being formed having a flange member 26 that helps to define outer longitudinal grooves 28, as illustrated in FIG. 5. Each groove 28 is formed having a plurality of aligned, equally spaced holes 30, which define part of the interconnecting means between horizontal frame members 20a and the connecting ends of the upright frame members 16a and 16b.
Referring now to FIG. 2, there is illustrated a partial perspective view of the intermediate spacer members 20b, wherein all space frame members 20b are also formed having securing means 24 which are identical to those formed in frame members 20a. Thus, for simplicity, the same reference characters will be employed for all of the identical parts or elements of the different frame members. In fact, all of the frame members 16 and 20 are formed as described above as having identical web portions 22, securing means 24, grooves 28 and flanges 26. However, horizontal frame members 20b are shorter in length with respect to the other types of frame members, whereby spacer frame members 20b are secured between the upright members 16.
Accordingly, the oppositely disposed ends of spacer frame members 20b are provided with hook-like tab members 32 that extend outwardly from the securing tracks 24 and are adapted to be slidably received in any one of the securing tracks of the various frame members. In FIG. 2 hook tabs 32 are shown spaced above the inner positioned tracks 24 of upright frame member 16a and ready for insertion therein.
In FIG. 3, which is a section view taken as 3--3 of FIG. 1, but without the glass block shown therein, hook tabs 32 are illustrated as being positioned in tracks 24. Note that end 33 of the central portion of web 22 abuts the central web of upright frame 16a. Thus, at this time frames 20b and 16a are secured together at right angles to each other which permits a glass block to be inserted therein, as seen in FIG. 1.
All of the upright frame members 16, and top and bottom frame members 20a, are adapted to be connected by means of holes 30 which are located in grooves 28 of frames 20a and by pins 34 that extend from the oppositely disposed ends 35 of frame members 16. This is, both arrangements of upright frame members 16a and 16b are provided with pins 34, whereby frame members 16, when connected to horizontal frame members 20a, will be positioned in a perpendicular and parallel arrangement to receive the glass blocks 12 therebetween. (See FIGS. 5 and 6.) Further, when all of the frame members are in place and the wall structure completed, the frame members 16 and 20 together provide a sealing means.
In constructing glass block walls using the present invention, it is suggested as an example that when the size of the glass wall is determined, a frame member 20a be positioned in place as a bottom encasement member followed by connecting the upright frame members 16 which are defined by both the upright outer encasement members 16a and the inner upright members 16b. Then, glass blocks 12 are inserted between the upright members 16, so as to define the first row of positioned blocks. Prior to the second row of blocks being positioned therein, a row of spacer members 20b is interposed between the upright members and locked at their opposite ends by inserting locking tabs 32 into the respective adjacent tracks 24 of the upright members 16, as illustrated in FIG. 1. Glass blocks are commonly formed having enlarged outer rims 40 which help to define a recessed body portion 42 (FIG. 4). As can be seen therein, the enlarged rims 40 suitably rest firmly within grooves 28, and the dual securing tracks 24 are readily positioned in the cavity provided by the oppositely disposed recessed bodies of the glass blocks 12. Accordingly, the same steps are made for inserting spacer frame members 20a and the glass blocks 12 until all of the necessary rows are completed. Thus, the last step is connecting the last horizontal frame member to complete the glass block wall. First, it should be understood that various methods may be employed in the construction of the frame members and blocks, and the above described method is only by way of one example. Further, it is important to note that because of the unique arrangement and design of the frame members there is no need for any cement grout material which is commonly used in such wall structures.
It may thus be seen that the objects of the present invention set forth herein, as well as those made apparent from the foregoing description, are efficiently attained. While preferred embodiments of the invention have been set forth for purpose of disclosure, modifications of the disclosed embodiments of the invention as well as other embodiments thereof may occur to those skilled in the art. Accordingly, the appended claims are intended to cover all embodiments which do not depart from the spirit and scope of the invention. | A framework assembly that consists of a multiplicity of vertical and horizontal frame members that are interconnected in a locking arrangement to provide a plurality of sealed compartments that are formed within a peripheral framework wherein glass blocks are readily mounted to define a glass-block wall structure held together by the frame members without the need for cement grout. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. application Ser. No. 11/276,216, filed Feb. 17, 2006, which is a continuation of U.S. application Ser. No. 10/820,366, filed Apr. 8, 2004, which application claims the benefit of Provisional Application No. 60/461,562, filed Apr. 9, 2003, each of which is incorporated herein by reference for all purposes. This application claims the benefit of Provisional Application No. 60/706,586, filed Aug. 8, 2005, which is incorporated herein by reference for all purposes.
Related application Ser. No. 11/162,902, filed Sep. 28, 2005, is incorporated herein by reference for all purposes.
FIELD OF THE INVENTION
This invention relates to a system and method for detecting and tracking packages, freight, animals, people, and other animate and inanimate objects. The invention also relates to novel radio frequency detection tags which are capable of communicating data, such as identification and positional data. In a preferred application, the novel tags can give active pre-emptive status warning about damage (e.g. due to shock) or a deteriorating condition (e.g. overheating) of the objects to which they are attached.
BACKGROUND OF THE INVENTION
Hundreds of detection devices that make use of radio frequency, have been developed for use in various detection applications, such as tracking animals, for identification of humans within secure areas, and for remote data logging and data collection, tracking of freight, payment of tolls on toll roads. Some of these devices are called RFID Tags, or RF Tags and are often designed to replace fixed barcodes or ID's in many processes. RFID and RF Tags can be categorized into two separate types:
RFID Tags are passive, and can be typified as low cost (as low as 10 cents), fixed ID, disposable and usually short range. Some are long range but can have only a single tag in the reading field. However, anti-collision methods can be used to read with groups of up to 500 tags within a reading field and it is possible to extend the detection range to miles. RFID detection tags work in frequency ranges of 100 Khz to 3 Ghz. (see U.S. Pat. No. 5,517,188, incorporated herein by reference).
RF Tags are active. They typically add a battery to the typical RFID design discussed hereinabove to enable longer reading ranges without powerful readers, and to enable digital clocks, memory, optional programmable ID. Cost can be as high as $1,000 and as low as $5, typically priced in range of $40. They typically work in a frequency range of 15 Mhz to 3 Ghz.
RFID tags and RF tags both operate as transponders—like an electronic mirror. The basic operating principle is that energy from the antenna of the reader generates an electromagnetic field, which induces a voltage in the coil of the tag and supplies the tag with energy. Data transmission from the reader to the tag is done by changing one parameter of the transmitting field (amplitude, frequency or phase) and reflected back. The tag digitally communicates back to the reader by reflecting the electro-magnetic filed back to the transmitter.
In most cases RFID and RF tags have a fixed ID which cannot be altered. The electronic reader is placed in critical area where it can read this ID when the tag is activated by the reader, in much the same way as a barcode is scanned by a barcode scanner at a supermarket. In some cases the RF tag can be programmed providing it is removed to an isolated area so that the programmer sees only a single tag, or the providing programmer has prior knowledge of the fixed ID contained in the tag, or a special encoded signal is used for programming (see U.S. Pat. No. 5,517,188, incorporated herein by reference).
These “transponder tags” all have many advantages. The RFID passive versions can cost as low as 10 cents and can, in effect, replace paper barcodes (see U.S. Pat. No. 6,280,544, incorporated herein by reference). The range and distance to read a tag is determined by the tag size and the power and frequency of the signal from the reader. It is possible to develop specialized high frequency transponder tags that can be read from miles away with a powerful high frequency signal or even from a radar scan. A stand-alone transmitting tag with its own transmitter, instead of modulation of a reflective high frequency signal would consume far too much power, for these long range applications. Low frequency (50 Khz to 500 Khz) transponder tags have short ranges, but may have cost advantages and may be readable even when attached to metal shipping containers or steel railroad cars. In most tracking applications a standalone two way transmitter and receiver as opposed to a transponder based system used in RF Tags and RFID tags would have too many disadvantages: too expensive, limited range, and require complex transmission RF circuitry, including crystals, and have high power consumption since all transmission power must come from the tag as opposed to the reader's interrogation signal.
A major disadvantage of all transponder based tag designs is that special anti-collision methods (see U.S. Pat. Nos. 6,377,203; 6,512,478; 6,354,493; 5,519,381, all incorporated herein by reference) must be used to read more than one tag within a reader's transmitted field, or alternatively a short range reader must be used to individually address each tag within the larger field (see U.S. Pat. No. 6,195,006, incorporated herein by reference). Also, to program a RF tag requires either a special signal and the tag must be isolated from other tags (only one in the field) or special hardware must be used. This makes difficult any “networks” of tags and real time inventory or automated real-time detection and tracking of many items all contained within a truck or warehouse for example difficult. It also makes impossible a network of interactive tags able to freely transmit, be programmed and receive as is the case in any conventional network, and the possibility of real-time freight tracking using the internet is difficult. A second major disadvantage is that to obtain long ranges (100 to 1,000 feet), higher frequencies are required, and these lead to high power consumption. This power may come from higher activation power of the transmitter signal to the RFID transponder, or from a battery contained within the RF transponder. The batteries are high capacity large (e.g. AA or C alkaline) and life is limited in these applications. Either special measures must be used to either conserve battery life (see U.S. Pat. No. 6,329,944, incorporated herein by reference) or special methods must be used that minimize power for even simple things like clocks or timers (see U.S. Pat. No. 6,294,997, incorporated herein by reference) in RFID or RF Tags.
Finally, active RF tags are typically larger (½ inch thick by 4″ by 5″) and expensive (over $50/unit) because of the battery size. Thin versions typically have limited battery life (two years). Active tags may be use to locate the pallet or shipment within a warehouse, as well as for tracking its progress through a supply chain. Several tags have been developed to include limited data tracking as well as the ability to remotely transmit the data. These tags however do not contain LED's or Displays buttons of any kind, and again represent, in effect, electronic smart barcodes.
SUMMARY OF THE INVENTION
The present invention broadly provides a system for detection and tracking of inanimate and animate objects, the aforesaid system comprising:
a) a low radio frequency tag carried by each of the objects, said tag comprising a tag antenna operable at a low radio frequency not exceeding 1 megahertz, a transceiver operatively connected to said antenna, said transceiver being operable to transmit and receive data signals at said low radio frequency, a data storage device operable to store data comprising identification data for identifying said detection tag, a programmed data processor operable to process data received from said transceiver and said data storage device and to send data to cause said transceiver to emit an identification signal based upon said identification data stored in said data storage device, and an energy source for activating said transceiver and said data processor; b) at least one field antenna disposed at an orientation and within a distance from each object that permits effective communication therewith at said low radio frequency; c) a reader in operative communication with said field antenna, said reader being operable to receive data signals from said low frequency tags; d) a transmitter in operative communication with said field antenna, said transmitter being operable to send data signals to said low frequency tags; and e) a central data processor (e.g. server) in operative communication with said reader and transmitter.
Preferably, the aforesaid low radio frequency does not exceed 300 kilohertz.
According to a preferred embodiment, the aforesaid field antenna, reader, and transmitter are combined into a unitary handheld device (as shown in FIGS. 7 and 8 ).
The aforesaid field antenna preferably comprises a large loop, and the distance from the field antenna to each object preferably does not exceed a major dimension of said loop. Where the large loop is substantially circular, the major dimension represents a diameter thereof.
According to a preferred embodiment, the aforesaid identification data comprises an internet protocol (IP) address, and the central data processor is operable for communication with an internet router.
Preferably, the tag further comprises a sensor operable to generate a status signal upon sensing a condition (e.g. temperature change, shock, dampness) experienced by an object that carries the detection tag, the transceiver being operable to automatically transmit a warning signal at said low radio frequency upon generation of the status signal. Preferably, the sensor comprises a GPS detector to help locate the tag and its associated object.
According to a preferred embodiment, the tag further comprises at least one indicator device (e.g. colored LED, audible tone generator) which is automatically operable upon receipt by said transceiver of a data signal that corresponds to said identification data stored at said data storage device. Where the tag is provided with the aforesaid sensor, the indicator device may also be automatically operable upon generation of its status signal.
Preferably, the tag may further comprise both
(i) a sensor operable to generate a status signal upon sensing a condition (e.g. temperature change, shock, dampness) experienced by an object that carries the detection tag, and (ii) a clock to generate a time signal corresponding to the status signal, the data storage device being operable to store corresponding pairs of status and time signals as a temporal history of conditions experienced by the object.
Advantageously, the tag's transceiver can then be operable to automatically transmit that temporal history at the aforesaid low radio frequency upon receipt by the transceiver of a data signal that corresponds to said identification data stored at the data storage device.
According to a preferred embodiment, the detection tag can further comprises a display (e.g. LCD) operable to display data relating to said tag and to an object carrying said tag.
Moreover, the tag can further comprise key buttons operable for manual entry of data.
Preferably, the novel tag can be formed with two major surfaces at opposite sides thereof, a first major surface on a first side of the tag is substantially flat to facilitate attachment to a surface of an object, while a second major surface of the tag can be substantially convex. Moreover, the second major surface can be tapered to a thin edge along a perimeter of said tag, thereby reducing the likelihood that the tag could catch against an obstruction and be ripped away from its object. Moreover, the tag can be provided with a transparent film overlying the second major surface, the film being removably adherent to the object while permitting visual inspection of the aforesaid second major surface.
Preferably, the tag can be provided with key buttons for manual entry of data, the second major surface can be provided with an LCD display and at least one LED indicator device.
Preferably, the tag's first major surface can be provided with the aforesaid key buttons, which can have frictional (e.g. rubberized) surfaces for reducing slippage with respect to said object. Also, at least one of the key buttons can be operable to automatically electronically detect whether or not the tag is in contact with a package or other object.
According to a preferred embodiment, the transceiver can be normally ON to receive data signals. Moreover, the programmed data processor of the tag is preferably operable to compare a transmitted ID code with one or more ID codes programmably stored in the data storage device and, in the event of a match, to respond to said transmitted ID code.
The invention further provides a method for detection and tracking of inanimate and animate objects, such as luggage and baggage, the aforesaid method comprising the steps of:
a) attaching a low radio frequency detection tag to each of the objects, each tag comprising a tag antenna operable at a low radio frequency not exceeding 1 megahertz, a transceiver operatively connected to said antenna, said transceiver being operable to transmit and receive data signals at said low radio frequency, a data storage device operable to store data comprising identification data for identifying said detection tag, a programmed data processor operable to process data received from said transceiver and said data storage device and to send data to cause said transceiver to emit an identification signal based upon said identification data stored in said data storage device, and an energy source for activating said transceiver and said data processor; b) storing, in the data storage device of each tag, shipping data selected from object description data, address-of-origin data, destination address data, object vulnerability data, and object status data; commingling the objects in a repository selected from an airplane, an air freight container, a warehouse and a truck, said repository being provided with at least one field antenna operable at said low radio frequency; said field antenna being disposed at a distance from each object that permits effective communication therewith at said low radio frequency; d) reading the identification data and shipping data from the transceiver of each tag by interrogating all tags in said repository with data signals via said field antenna; e) transmitting the identification data and shipping data from each tag to a central data processor to provide a tally of the objects in said repository.
The tag further preferably comprises a sensor, as discussed hereinabove, operable to generate a status signal upon sensing a condition (e.g. temperature change, shock, dampness, GPS position) experienced by an object that carries the detection tag, the method further comprising the step of:
(f) automatically transmitting a warning signal from the tag's transceiver at the aforesaid low radio frequency (e.g. 300 kilohertz) to the server or other central data processor upon generation of the sensor's status signal.
Preferably, the tag comprises both
(i) a sensor operable to generate a status signal upon sensing a condition (e.g. temperature change, shock, dampness, position) experienced by an object that carries said detection tag and (ii) at least one indicator device (e.g. colored LED, audible tone generator),
the method further comprising the step of:
(g) automatically activating said at least one indicator device upon generation of the sensor's status signal.
Preferably, the tag further comprises
(i) a sensor operable to generate a status signal upon sensing a condition (e.g. temperature change, shock, dampness, position) experienced by an object that carries the detection tag and (ii) a clock to generate a time signal corresponding to the status signal,
the method further comprising the steps of:
(h) storing corresponding pairs of status and time signals as a temporal history of conditions experienced by the object; and (j) transmitting, to the central data processor, the temporal history at said low radio frequency upon receipt by said transceiver of a data signal that corresponds to the identification data stored at the data storage device.
Moreover, the invention provides a novel detection tag for detection and tracking of animate and inanimate objects, the aforesaid detection tag comprising:
a) an antenna operable at a low radio frequency not exceeding 1 megahertz; b) a transceiver operatively connected to said antenna, said transceiver being operable to transmit and receive data signals at said low radio frequency; c) a data storage device operable to store data comprising identification data for identifying said detection tag; d) a data processor operable to process data received from said transceiver and said data storage device and to send data to cause said transceiver to emit an identification signal based upon said identification data stored in said data storage device; and e) an energy source for activating said transceiver and said data processor.
As will be readily understood, the novel inventive tag may preferably comprise the various characteristics disclosed hereinabove.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the invention, various features of preferred embodiments of the novel system, method, and tag, are illustrated in the drawings, as will be described hereinbelow:
FIG. 1 a is a schematic plan view of an RF tag in accordance with a first embodiment of the invention;
FIG. 1 b is a cross-sectional view of the RF tag of FIG. 1 a;
FIG. 2 a is a schematic plan view of the back of an RF tag in accordance with a second embodiment of the invention;
FIG. 2 b is a cross-sectional view of the RF tag of FIG. 2 a;
FIG. 3 a is a schematic plan view of an RF tag in accordance with the invention, showing its attachment to a surface of a freight box;
FIG. 3 b is a cross-sectional view of the RF tag of FIG. 3 a;
FIG. 4 is a schematic block diagram depicting the functional components of an RF tag in accordance with the invention;
FIG. 5 is a schematic view of a number of low frequency RF tags attached to freight packages in a warehouse repository, together with a large loop antenna and other components for reading the tags and communicating the information;
FIG. 6 is a schematic view of a number of low frequency RF tags attached to freight packages in a truck repository, together with a large loop antenna and other components for reading the tags and communicating the information to the internet or elsewhere;
FIG. 7 is a schematic view showing the use of a handheld reader to interrogate a selected individual RF tag;
FIG. 8 is a schematic view showing the use of a handheld reader to interrogate RF tags with reader; antennas of different sizes for different communication ranges;
FIG. 9 is a flowchart using block diagrams to describe the use of the invention and its use with the novel RF tags and other components; and
FIG. 10 is a table listing of advantages and features of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
We have discovered that by using lower frequencies (not exceeding 1 megahertz, and typically under 300 Khz) and a base station design that uses large loop antennas (such as 10.times.10 feet to 500.times.500 feet) and by transmitting a digital ID to selectively activate a selected client tag, rather than a non-selective signal which would activate many tags simultaneously, we have the ability to read and write to a full network of client tags (which are within the effective range of the loop) using both a simple polled protocol as well as on-demand communications from the client tags. Each such detection tag uses a full duplex transmitter and receive (transceiver), as opposed to transponder design used in RFID tags and RF Tags. In addition, these Networked RF Tags (NRF Tags) have significantly reduced power consumption, and long range (1000 sq feet to 10,000 sq feet per antenna), have the power capacity to add displays (e.g. LCD) and light emitting diodes (LED's) and detectors, and buttons so they may become fully interactive “tag clients” (this is not possible with transponder). These low frequencies are generally understood to have very short range (inches), have the disadvantage of limited transmission speed, but have the distinct advantage of operating in harsh environments with reduced interference (see Mar. 19, 2003 RFID Journal “Goodyear Opts for 125 KHz Tire Tag”). However, the range problem is solved by using full duplex communications and a base station with large loop antennas; moreover, the communication speed is not a serious issues in any of the expected applications.
Low frequencies make it possible to use low speed low-power integrated circuits. These integrated circuits may be fabricated using 4 micron CMOS for only 10 to 20 cents and use a standard flat (quarter size) alkaline battery or a lithium battery. The low frequencies provide extremely low power consumption and make it possible to leave the receiver on at all times, drive an LCD display at all times, transmit back to the base station as many as 100,000 times, yet the tag enjoys a lifetime of a minimum five years to maximum 20 years (lithium battery). The loop antennas have the advantage of communication to modules only contained within the loop, or depending upon the communications mode (AM of FM, or PM) up to one diameter away from the loop. This also makes it possible to estimate the location of an item down to the size of the loop approximately. These non-transponder NRF Tags are novel detection tags which have the ability to transmit and receive in the manner of any radio device and do not depend upon reflection of reader signals.
The NRF Tags have a range of hundreds of feet, and NRF Tags have long battery life (e.g. 10 years) with miniature button batteries, and only one or two active components. They can do this because they use very low frequencies (below 1 megahertz and preferably under 300 kilohertz) for both transmission and reception.
The novel NRF Tag, is low-cost (dollars) with full two duplex way transmission and reception, can be fully programmable within the network, and as many as 10,000 or more can all function within a network as clients, with a ten to fifteen year battery life This tag may be equipped with a LCD display, used for data tracking, and damage control applications. These tags have been specifically designed to easily attach to a package, using tape or other adhesive means. This provides the added advantage of programmability at one site, using a simple hand-held device, attachment to the package at the shipping site, followed by the ability to track the package as well as to log data about the status of the package throughout the entire supply chain. Thus the tag may be used as shipping data to store other shipping information such as addresses, freight contents, weight size, and shipping ID's with full programmable features. The tag has additional unique features including a LCD display that can optionally provide shipping data information about the shipment such as shipping ID or tracking number or other ID number, as well as to light emitting diodes (LED), that can be used for active sorting, and optimal placement either within a warehouse or truck. The tag may also have several buttons placed on its face, that can be used to confirm any action associated with the freight (e.g. it has been sorted or moved), or to scroll information contained in the tag on the LCD display. In addition the tag may be read as it passes through a “reading tunnel”, on a conveyor and/or automatically sorted, similar to systems now based on barcodes. Finally, many such tags may be attached to freight stored in a warehouse, and a single large loop antenna, or multiple overlapping loop antennas placed either in the floor or ceiling or on shelves can be used to interrogate the tags, read data, status and find the approximate location of the freight in the warehouse. This ability to Network many NRF Tags as clients within a region makes many other functions possible.
When the freight reaches its destination, the delivery person may optionally remove the tag from the freight, so that it can be reused again by the shipper. Alternatively the tag can stay with the freight and the recipient can take the tag, reprogram it for a return or for another shipment. The design of the tag includes optional rubber buttons placed on the tag back (a flat surface), that may be optionally used to enter a PIN identification numbers either by the shipper and whether recipient prior to attachment to the freight, or after its removal by recipient. This may be used to confirm identities of both shipper and recipient. This same rubber button pattern may also provide for a skid resistant attachment surface to the package, especially if the buttons or made of soft rubber. These buttons also may serve as an electronic detection means that the tag device is actually attached to a package, or has just been removed from the package. For example, the tag's memory could be automatically reset, after the tag is removed from the package by detecting that at least two or three of the rear buttons are then simultaneously depressed and released. Alternatively the same detection system could be used simply to display a message on the LCD that it is now available to be re-programmed and yet not erase memory.
Another unique feature of this system is its ability to be programmed within the network, providing the server knows the ID of the NRF detection tag client, or by a very low-cost hand-held device, in the warehouse, or in the truck, or at the shipper's site; also, an NRF tag can be programmed at the receiver's site with no knowledge of the clients tag's ID. The hand-held and tag communication range may be easily controlled to a few inches or even a few feet depending upon the size of the loop antenna is used for communication contained in the handheld, as well as power supplied to the antennas. This provides the ability for an individual to walk up to a piece of freight with the hand-held, within a warehouse, and interrogate the NRF Tag ID status, or reprogram tag, or carryout any other maintenance function without any prior knowledge of the shipping ID number or any other shipping data or other information that maybe contained in a separate database—it is done based simply by locating the physical freight These features will undoubtedly be limited to specific individuals with the authority to make such changes, however this ability makes maintenance in support of the tags low-cost and on the warehouse floor.
In addition, low cost detectors for humidity, angle, temperature, acceleration and jog's (Mercury switches) and GPS may be easily added to the NRF Tag as required. With the addition of internal memory such as a data storage device, data associated with these detectors may be logged over time and stored in the tag for reading and documenting the history the package. This may be particularly important for sensitive high-value electronic items, pharmaceuticals which must be maintained within a narrow temperature range, food items, and other hazardous items or high-valued shipments. In most cases disposable “onetime use” tags used to measure these parameters for freight often the cost more than the cost of this electronic damage detection tag. More importantly these electronic tags provide detailed times and dates when any data parameter changed or an action took place. For example is possible to identify the location and the precise time when a high-value package was dropped.
A final advantage of this system is its ability to transmit to the Base Station, independent of the base station interrogating the NRF Tag—on-demand tag transmission. This makes it possible if a fault occurs or damage occurs, or say the temp is out of range for the tag client to send to the base station an alarm condition.
Communications Protocol
Each NRF tag may have many ID's programmed into its memory. When manufactured all tags have the same-master ID, typically 00000000. The handheld or a special programming device (a base station) connected to a computer with limited range, sends out this unique master ID. The tag has an always on receiver and reads the transmitted ID, it compares this with the ID's contained in its memory and if it finds a match, transmits a signal containing the transmitted ID back to the transmitter, indicating that it is now full open to handle communication. The base station, may than provide the detection tag with one or more unique ID numbers which may simply be a unique tracking number, or other unique ID, as well as any information it may require to function (e.g. instructions to log temperature or physical impacts such as jogs). The tag is also provided with several random numbers stored in its memory that can be used to delay un-solicited transmissions to the base station to minimize likelihood of collisions.
Once programmed the tag may be attached to a piece of freight and placed in a warehouse. In most cases communication is via a simple lolled network system. The Base Station in the warehouse communicates to many thousands of tags located on the floor of the warehouse via a tuned loop antenna. The server attached to the base station sends as part of its transmission the tracking number or unique ID to the entire network of tags, and that number is compared by each tag to the numbers contained in the each tag's memory. If the tag does finds a match for the transmitted number, than the tag replies to the interrogation with that serial number or with the same ID or tracking number. Providing the numbers are unique only a single tag will reply, and full hand-shake communication can be carried out between the tag and the base station. At the end of the transmission, the base station sends a code to indicate it has completed all communication. The server can do a check-up on all tags by simply, polling each tag one after the other with its ID in the same manner as outlined above. The base station may also read and/or harvest the temperature history (logs) or other environmental information history contained in he individual tag's memory.
The novel NRF tags may also initiate communication, by transmitting their ID's to the base station. This could be in response to a button push or in response to an environmental condition (e.g. temperature too high or too low). In the rare case when two tags simultaneously transmit, the ID's will be non-readable and the base station will send out a single indicating an error has occurred. Two possible protocols may be initiated. The tags may be instructed to re-transmit, using a random delay stored in each tag's memory register, to eliminate the overlap. Alternatively, that server may simply poll all NRF tags in the field, one-by-one, until it locates the two tags that transmitted the signals.
APPLICATION EXAMPLES
The simplest application in use of the tag may be simply as a recording of shipping information. Many shipper's have far too low volume of packages to be shipped (three to four week inventory) to justify placing a full shipping system. The average cost for such a system, particularly if it includes a printer, may be thousands of dollars. The same customers however often refuse to fill out a paper waybill. This NRF tag system simplifies shipping for low volume shippers. In its simplest form, this can provide a very low-cost shipping system to low volume shippers, and reduce cost for the courier, and provide enhanced ability to sort, track and bill the customer.
In this example the low volume shipper would be provided a hand-held with a low-cost modem built into the cradle. The hand-held can dial out a phone line to a centrally located server, provide the server with information about shipments and also receive updates as well as a customer list. The shipper would simply remove the hand-held from the cradle scroll down through his personalized address list, and select a correct address. A tag could be placed on the package to be shipped, and the hand-held will program the tag with that address. The NRF tag may record a log of the time it was programmed as well as the identity the person programming. This identity may be confirmed with a PIN number, entered on the hand-held simply by the serial number of the hand-held itself. Other information may also be contained in the tag such as weight size of the package and service desired (next day, three-day, etc.). When the driver picks the package up he may also scan with his hand-held, confirming that it's been picked up. When the package is placed in the truck, it may also be tracked and identified with an antenna in the back in the truck. If the truck is equipped with GPS, the GPS coordinates of the package and the fact that it's been picked up may be transmitted again back to the server confirming time and location of the pickup. Thus the packages in the truck may be confirmed periodically by the computer contained in the truck and transmitted back to the central server; this optionally provides the real-time manifest and real-time tracking for the customer as well as for the courier.
When the package arrives at the distribution center, again the novel NRF tag may be read and identified for tracking purposes using either warehouse antenna or a special reader on a conveyor. This information may be used to automatically sort the package on a conveyor, or it may also be used to manually sort packages. In the manual sort cases all the packages can be placed on a circular conveyor, identified and read by a loop antenna around the conveyor. Once all tags have been identified a sorting program can determine which shipments are to be placed in Truck One for delivery, and the red LED's provided on their attached NRF tags can be flashed. The pickers therefore, simply remove packages on the circular conveyor that have a tag with a flashing red LED and put them in the Truck One. Similarly, the packages for Truck Two may next be identified with the flashing green LED. Again those packages remove the circular conveyor and placed in Truck Two. This procedure can be continued until all packages have been removed and paced into the correct trucks.
Once packages are placed in the correct trucks, they may also be correctly sorted for sequential delivery and then delivered using the same system. For this purpose, the trucks may be equipped with a small server and GPS, and a base station with loop antenna in the back. The packages can be identified by the server as it reads the GPS location of the truck and as the driver approaches a correct GPS-identified delivery address by simply flashing the LED on the corresponding attached NRF tag. It will be understood that each NRF tag and each server may be provided with an internet protocol (IP) address to enable communication and tracking from other internet addresses of the shipper and of the customers. These new NRF tags therefore provide real-time tracking as well as real-time picking and sorting throughout the entire supply chain with virtually no paperwork.
This same sequence can be used for heavier freight on pallets, or even large high-value items placed on long haul trucks. In many cases particularly for high-value pharmaceuticals or confectionery items temperature ranges must be monitored at all times to provide a warning alert for preventing damage (e.g. spoilage). Again this may be done in real-time providing the truck is equipped with GPS and a loop antenna system, or alternatively the tag may simply actively volunteer data important for the shipment. Of course, this data may be harvested to a central computing system via an IP-address-equipped server once the shipment reaches its destination
These NRF tags may also be used to identify and monitor individuals who are allowed entry into high security areas of using the same basic systems described above, and track individuals within buildings as they move from place to place. On the face of the tag in this case could be flat and contain picture ID, and the back could retain the button array. At critical entry points the user may, for example, be required to enter in a PIN number using buttons on the NRF tag as his positive identification.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
An embodiment of a freight damage alert RF tag 1 , in accordance with the invention, is shown in FIG. 1 a , which illustrates the front of RF tag 1 , and FIG. 1 b , which shows a cross-section A-A thereof. This front view includes an optional LCD display 2 , an optional set of buttons 3 , and an optional set light emitting diodes (LED) 4 . The LED's may be different colors. The display 2 can be used to show the waybill number, or other shipping information, while the buttons 3 can be used to confirm actions in the warehouse or truck or alternatively may be used to scroll information up-and-down on the display 2 . The LED's 4 are useful for picking and putting freight both in the warehouse as well as in the truck.
Tag 1 may be provided with a hole 7 to help attach the tag to freight packages.
One unique feature of the design is that the face 5 of the tag 1 is convexly curved to a thin peripheral edge so that conventional tape or specialized transparent adhesive film (TAF) 6 can be used to hold the tag in place on the package with no exposed edges. The curved face 5 offers a strong surface for the adhesive on the tape or TAF 6 and does not provide any edges so the tag 1 can be knocked off the package. However the tag 1 may be easily removed when necessary by simply grabbing the corner of the tape 6 and peeling off. This makes it easy to retrieve the tag 1 upon delivery if necessary. It also makes it easy to recycle tags for use on many packages and many repeated uses. Moreover, a suitable device or means 8 may conveniently be provided for attaching the back of tag 1 to a freight package.
Tags 1 may also introduced that have no LCD display 2 , no buttons and no LEDs 4 at a reduced cost. These inexpensive NRF tags may be used simply to data log the status of the package throughout its shipment lifecycle.
FIG. 2 a shows the back view of freight damage alert tag 1 , while FIG. 1 b shows a cross-section along A-A thereof. Buttons 9 may be optionally placed on the flat back surface 10 of the tag. These buttons 9 may be of soft rubber and, as a result, may offer a cushioned back making it more difficult for the tag 1 to move laterally on the package surface after attachment. Additionally these buttons 9 may also be used to detect the fact that the tag is actually attached to the package. It more than one button 9 is depressed or it becomes clear to the microprocessor provided on tag 1 (see FIG. 4 ) that the tag 1 is in direct contact with a surface of some kind, such as a freight package, and the pressure has been applied that is necessary to depress all buttons 9 .
The same buttons may also be used to confirm identity of the shipper or recipient via PIN numbers. For example the truck driver may deliver the freight to a recipient, remove the tag 1 and ask the recipient to enter a PIN number on the keypad of buttons 9 . Alternatively, the keypad 9 on the back 10 may be used to actually program the tag 1 for a specific destination. The shipper may have a list of destinations printed on a piece of paper each with a unique two digit ID. He may enter the two digit number on buttons 9 followed by the “#” sign to program the shipper's address in the tag 1 That number then appears on the LCD 2 to confirm that it has been programmed for that destination and the shipper may attach tag 1 to the package. This eliminates the need for a shipping system as well as even a low cost hand-held reader. This can significantly reduce cost and save time for both the shipper the courier in the recipient.
FIG. 3 shows the shape of tag 1 in the preferred attachment means for the tag. As can be seen, the front face of tag 1 a gentle curved from the top bottom and left edge to form an ellipse. This provides a continuous surface with the package for transparent adhesive film (TAF) 6 to make contact and hold the tag 1 in place (on freight package/box 11 ) without any exposed tag edges. Sharp edges can lead might be caught during shipment and accidentally knock the tag from the face of the package. This system makes it easy to stick tag 1 on the surface of the package at a very low-cost, and also to remove the tag 1 when necessary.
It is also optionally possible to emboss an area 6 a in the TAF attachment means 6 to the actual shape of the tag 1 so that the thickness of the tape 6 may be increased and conform to the shape of the tag 1 . These adhesive attachment films 6 may be attached to waxed heavy backing paper and provided to the customers so that attachment becomes quick and easy. It may also be possible in some cases to add an additional piece of transparent film in front of the adhesive film to form an envelope 6 b . This envelope 6 b can be used for waybill's and other paper, particularly useful if the tag does not have a LCD 2 or other optional features.
FIG. 4 is a block diagram showing functional components of a typical freight damage alert tag 1 . The heart of the freight damage alert tag is a custom radiofrequency modem 12 , created on a custom integrated circuit using 4 micron CMOS technology. This custom modem 12 is designed to communicate (transmit and receive), through a loop antenna 13 , made of thin wire wrapped many times around the outside edge of the tag 1 . All communications take place at very low frequencies (e.g. under 300 kHz). By using very low frequencies the range of the tag 1 is limited; however power consumption is also greatly reduced. The receiver of modem 12 may be on at all times and hundreds of thousands of communication transactions can take place, while maintaining a life of many years (e.g. up to 15 years) for battery 13 . The typical freight NRF tag 1 may also include a memory 16 and a four bit microprocessor 14 , using durable, inexpensive 4 micron CMOS technology and requiring very low power, with onboard LCD drivers, to control and drive the LCD display 2 , as well as drivers for the LED's 4 and the ability to detect and read analog voltages from various optional detectors 15 and read inputs from buttons 3 . For example, the tag 1 may contain a humidity detector and angle detector temperature detector a jog detector.
FIG. 5 shows how these novel NRF tags 1 may be placed as clients within a network served by larger loop antenna 17 in a warehouse setting. The larger antenna 17 may be placed in the floor ceiling or around shelves containing the freight 11 . One additional advantage of using low-frequency communication for the system, is the fact these low (e.g. 300 kHz) frequencies do not reflect from steel or metal. In fact, they are often enhanced and refocused effectively by steel shelves or other large iron frames. In many cases the antenna 17 may simply be wrapped around large steel shelves and the tags 1 will all be contained in the inductive low-frequency field. The loop antennas 17 can be up to several hundred feet square. However, as they get larger, the ability to detect an individual tag 1 decreases, and the power required to transmit to the tags 1 increases. Low-frequency communication has relatively low noise with antennas 17 in the range of 100 feet by hundred feet, however at 500 feet by 500 feet they began to detect thunderstorms occurring at a distance—often within 4 or 500 miles away from the antenna 17 . Thus, the optimal size for these antennas 17 is on the order of about 100 by 100 feet. However many such antennas 17 can be placed within a warehouse to create a checkerboard array for communication to any point. This also makes it possible to localize a specific tag 1 within a large warehouse at least within the distance of an antenna square. A single base station 18 can be used to connect to all such antennas 17 by time division multiplexing, or the like.
The antenna 17 is connected to a base station 18 which in turn is connected to a server 19 or computer controlling mechanism. The base station 18 is able to transmit and receive at much higher power than the tags 1 , but as long as the tags 1 are contained within a loop 17 , base station 18 can identify and talk to each tag 1 individually. The optimal protocol for this network is for the base station 18 to address the tag 1 based on a known ID. In other words the optimal protocol requires that the server 19 have a database of IDs found in the loop antenna 17 when using networks of tags 1 . As will be understood, for addressing of an individual tag 1 from the internet, the tag 1 may be provided with an IP address.
However, it is possible to actively talk to each tag 1 individually and program it to not respond to a given, signal transmitted by the base station 18 —a chirp command. In other words this chirp command tells all tags 1 that unless they have been programmed to not respond with their ID, to respond with their ID. If a tag 1 exists in the loop 17 that is not in the database it will transmit its ID with the chirp command. If multiple tags 1 exist in the database with unknown IDs they will talk together, and the base station 18 /server 19 combination can detect an ID collision. It is then possible to retransmit the chirp signal, but have the tags 1 transmit back with a random delay, so that ID's do not overlap this process may be repeated until all IDs are the found within the loop 17 . Other standard methods used in networks may be used to carry out by “binary” searches, to illuminate certain addresses until all tags 1 again are identified. In most routine cases however the servers 19 will have prior knowledge from the hand-held reader or other sources of tags and all IDs contained in the loop.
The server 19 may, on a periodic basis, interrogate each tag 1 to obtain a current temperature, status button pushes, etc. The same server may also selectively flash LEDs to indicate that the package or piece of freight 11 should be moved to another area, or can selectively flash LEDs to indicate which packages are placed first in a truck, or can selectively flash LEDs and change the display to provide other information or workers on the warehouse floor.
Moreover, it should be understood that once a package is removed from the loop, the server can detect that it has been removed and indicate that it is no longer in the database.
FIG. 6 shows a similar system as is depicted in FIG. 5 , except that it is contained in the trailer of a truck 20 as the repository for the freight boxes 11 . Again the system comprises a truck server 19 and an optional in-truck data communications means 21 , which comprise a digital cell phone or satellite link. An optional in truck GPS system 22 may also be included as an input to the server 19 . The server 19 then sends commands to a base station 18 (similar to the one depicted in FIG. 5 ) which may in turn connect to an array of antennas 17 that may be placed either in the ceiling of the truck 20 or in its floor to provide for full two way communication (reception/transmission, or “Rx/Tx) between server 19 and tags 1 .
The server 19 may, on a regular basis, interrogate all tags 1 contained in the truck 20 , locate tags 1 that are not contained in the database of server 19 and provide real-time confirmation of manifest or status of the freight 11 . By using the GPS input 22 about the changing location of truck 20 during its travels, this GPS information may be added to the information in the database of server 19 to thereby provide real-time tracking of individual freight items 11 as the truck 20 travels. In addition the server 19 may confirm the status or condition of the freight 11 (e.g. temperature, angle etc. in real-time) by reading the sensors 15 and transmitting them via the in-truck data communications system 21 . When the truck 20 reaches its destination the time and date of arrival can be placed in the log of the NRF tag 1 as an additional method of tracking the freight 11 to which tag 1 is attached. Moreover, such real-time tracking can be carried out via the internet if IP addresses are provided for the server 19 or for individual NRF tags 1 .
FIG. 7 shows the handheld reader 23 with a limited transmission and reception range 24 . By limiting the loop size of the antenna 17 (not shown) that is contained in the handheld reader 23 , as well as in the tag 1 itself, the handheld reader 23 may be used selectively communicate with an individual tag 1 by disposing reader 23 to within a distance of a few loop diameters of the handheld's antenna 17 . This limited range ability can only be achieved easily when using low-frequency (not exceeding 1 megahertz) loop communications. This ability makes it possible to selectively read, and write information to a selected tag 1 without prior knowledge of the tag's ID. Moreover, a worker may walk up to a piece of freight 11 with the handheld reader 23 properly programmed and read destination, current temperature and any other information from tag 1 by simply placing the handheld reader within 4 5 inches of the selected tag 1 and moving reader 23 back-and-forth along the direction of the 2-headed arrow, in much the same way as a bar-code might be scanned.
FIG. 8 shows that the distance between the hand-held and the tag for effective communications may be altered by simply changing the size of the small loop antennas. If a large antenna 17 a is used in the handheld reader 23 , the transmission reception range (Rx/Tx) 24 a can be several feet, while the Rx/Tx range 24 b of a smaller antenna 17 b may be limited to several inches. This ability to alter the range by designing optimal size of antenna 17 makes programmability and reading simple and low-cost.
FIG. 9 shows a typical flowchart for use of these freight NRF detection tags 1 . In Step 1, the handheld reader (“handheld”) 23 may read a bar-code or simply be manually programmed to write to the tag 1 at the shipment location. The waybill number or ID number may thus be programmed into the tag 1 .
In Step 2 the tag 1 may be placed on the freight box 11 , with tape, TAF, or other attachment means. The tag 1 may also be programmed with its ID and other information after tag 1 is attached to the freight 11 . Again, this can be done with the handheld reader 23 .
At Step 3, the handheld 23 transfers, to the server 19 (not shown), the data and information that handheld 23 has programmed into the tag 1 . This information may include the waybill number, shipment ID or other specific information that allows the large array antenna 17 of the base station 18 (see FIGS. 5 and 6 ) to identify and read tags 1 throughout the shipment life cycle for a freight package 11 . This data transfer may take place through the loop antenna 17 in the same way that the tag 1 and large loop antenna 17 communicate, or it may take place with a modem and phone line, or it may take place with a plug connected directly to the server 19 and the handheld 23 .
At Step 4, the base station large antenna array 17 can now freely interrogate tags 1 to track, sort and identify the freight 11 as it moves through the warehouse/truck delivery supply chain.
FIG. 10 lists a number of functions and advantageous features unique to the low frequency RF tags, method, and system of the invention, as follows:
1. Internal Transaction Data Log (Reads Writes+GPS) 2. Internal Temp Data Log (one month @1/hr) 3. Internal Humidity Data Log (one month @1/hr) 4. Internal Tilt Data Log (Events Log as needed) 5. Internal Jog Data Log (Events Log as needed) 6. Paperless Electronic Waybill 7. Automatic Freight Sort Based on Electronic Waybill 8. Real Time Freight Tracking (Trucks+Warehouse) 9. Real Time Truck Manifest 10. Real Time Data Logs 11. Real Time Web Enabled Reports (“8″11”). 12. Pick/Put Sorts of Freight (LED based) 13. Low Cost Tags (4 micron CMOS IC's) 14. Low Power Extended Battery Life (15 years)—due to Low Frequency RF (<1 MHz), for example 300 KHz 15. Low Cost Handhelds 16. Network of Tags within Large Loop Antenna 17. Individual Tag Reads and Writes (e.g. Conveyor) 18. Fully Programmable ID 19. No Fixed ID Required 20. Tags Secure On Package Using TAF 21. Tags “Retrievable” upon Delivery 22. Tags “Reusable” 100,000 or more transactions.
While the present invention has been described with reference to preferred embodiments thereof, numerous obvious changes and variations may readily be made by persons skilled in the fields of radio frequency tags and logistics. Accordingly, the invention should be understood to include all such variations to the full extent embraced by the claims. | The invention disclosed provides a method, system, and associated tag for detection and tracking of inanimate and animate objects. The novel method broadly comprises the steps of: a) attaching a low radio frequency detection tag to each of the objects, each tag comprising a tag antenna operable at a low radio frequency not exceeding 1 megahertz (preferably not exceeding 300 kilohertz), a transceiver operatively connected to the tag's antenna, the transceiver being operable to transmit and receive data signals at the low radio frequency, a data storage device operable to store data comprising identification data for identifying said detection tag, a programmed data processor operable to process data received from the transceiver and the data storage device and to send data to cause the transceiver to emit an identification signal based upon the identification data stored in said data storage device, and an energy source for activating the tag's transceiver and data processor; b) storing, in the data storage device of each tag, shipping data selected from object description data, address-of-origin data, destination address data, object vulnerability data, and object status data; c) commingling the objects in a repository selected from a warehouse and a truck, the repository being provided with at least one large loop field antenna operable at said low radio frequency; the field antenna being disposed at a distance from each object that permits effective communication therewith at the low radio frequency, d) reading the identification data and shipping data from the transceiver of each tag by interrogating all tags commingled in said repository with data signals, such as specific IP addresses or other identification codes, via said field antenna; and e) transmitting the identification data and shipping data from each tag to a central data processor to provide a tally of the objects in said repository. | 0 |
TECHNICAL FIELD
The present invention relates to 9-azanoradamantane N-oxyl compounds, organic oxidation catalysts containing 9-azanoradamantane N-oxyl compounds, methods for producing 9-azanoradamantane N-oxyl compounds, and alcohol oxidation methods for selectively oxidizing primary alcohol with the 9-azanoradamantane N-oxyl compounds.
BACKGROUND ART
Oxidation reactions of alcohols to carbonyl compounds represent one of the most fundamental reactions used for the organic syntheses of high value-added compounds such as medicaments, agricultural chemicals, flavoring ingredients, and chemical products. For this reason, many techniques have been developed in the past years. However, many of these methods involve use of toxic and explosive oxidizing agents, or require extremely low temperatures of −40 degrees or less. Over these backgrounds, a technique that uses 2,2,6,6-tetramethylpiperidine 1-oxyl (hereinafter also referred to as “TEMPO”) has attracted interest as a method that permits large-scale oxidation by taking advantage of the ability of this catalyst to oxidize alcohol even under very mild conditions of from 0 degree to room temperature using various co-oxidizing agents without using high toxicity reagents. It has been reported that many oxidizing agents have potential use as co-oxidizing agents (Non Patent Literature 3), including, for example, a low-cost and environmentally friendly sodium hypochlorite aqueous solution used in industrial and other processes (Non Patent Literature 1), iodobenzenediacetate (PhI(OAc) 2 ) that can coexist with a wide range of functional groups even in applications that use alcohols having double bonds and electron-rich aromatic rings (Non Patent Literature 2), and a molecular oxygen having high safety and high atom efficiency. The present inventors have reported that a nitroxyl radical having an azaadamantane skeleton (2-azaadamantane N-oxyl (hereinafter, also referred to as “AZADO”), and 1-methyl-2-azaadamantane N-oxyl (hereinafter, also referred to as “1-Me-AZADO”)), a nitroxyl radical having an azabicyclo[3.3.1]nonane skeleton (9-azabicyclo[3.3.1]nonane N-oxyl), and 9-azanoradamantane N-oxyl having an azanoradamantane skeleton (hereinafter, also referred to as “Nor-AZADO”) have higher catalytic activity than TEMPO, and promote a fast oxidation of bulky secondary alcohols that cannot be oxidized with TEMPO (Non Patent Literatures 4, 5, 6, 7, 8, and Patent Literatures 1, 2, 3, 4, and 5).
In oxidation reactions catalyzed by TEMPO, reaction that selectively oxidizes primary alcohols proceeds with a substrate that includes both primary alcohol and secondary alcohol (Non Patent Literature 9). Such selective oxidation of a specific alcohol is important as an alternative method of distinguishing a functional group in the synthesis of polyfunctional compounds commonly distinguished and synthesized with a protecting group. Such a reaction is also important because it can contribute to simplifying the synthesis process with the single step of alcohol oxidation reaction, as opposed to using a protecting group that requires protecting and deprotecting steps. In fact, there are many reports of synthesizing natural products using such reactions.
CITATION LIST
Patent Literature
Patent Document 1: WO2006/001387
Patent Document 2: JP-A-2009-114143
Patent Document 3: JP-A-2008-212853
Patent Document 4: WO2009/145323
Patent Document 5: WO2012/008228
Non Patent Literature
Non Patent Document 1: The Journal of Organic Chemistry, Vol. 52, Issue 12, pp. 2559-2562, 1987
Non Patent Document 2: The Journal of Organic Chemistry, Vol. 62, Issue 20, pp. 6974-6977, 1997
Non Patent Document 3: Journal of the American Chemical Society, Vol. 126, Issue 13, pp. 4112-4113, 2004
Non Patent Document 4: Journal of the American Chemical Society, Vol. 128, Issue 26, pp. 8412-8413, 2006
Non Patent Document 5: Chemical Communications, Issue 13, pp 1739-1741, 2009
Non Patent Document 6: The Journal of Organic Chemistry, Vol. 74, Issue 12, pp. 4619-4622, 2009
Non Patent Document 7: Syntheses, Issue 21, pp 3418-3425, 2011
Non Patent Document 8: Chemical and Pharmaceutical Bulletin, Vol. 59, Issue 12, pp 1570-1573, 2011
Non Patent Document 9: Tetrahedron Letters, Vol. 31, Issue 15, pp. 2177-2180, 1990
SUMMARY OF INVENTION
Technical Problem
However, the reactivity of TEMPO oxidation is not sufficient, and the reaction often requires large catalytic amounts of 20 mol % or higher, and a long reaction time. This may lead to poor yield. Further, TEMPO oxidation is not always applicable, and may necessitate changing the synthesis route.
The present inventors conducted intensive studies of catalysts that have higher activity than TEMPO yet maintain selectivity for primary alcohols, and found that 9-azanoradamantane N-oxyl compounds having an azanoradamantane skeleton with at least one alkyl group substituted at positions 1 and 5, and an oxygenated nitrogen atom show high catalytic activity for alcohol oxidation. The present invention was completed on the basis of this finding.
Solution to Problem
Specifically, the present invention is concerned with 9-azanoradamantane N-oxyl compounds, methods for producing same, and organic oxidation catalysts and alcohol oxidation methods that use the 9-azanoradamantane N-oxyl compounds.
(1) A 9-azanoradamantane N-oxyl compound represented by the following formula (1).
(In the formula (1), R 1 and R 2 represent hydrogen atoms or alkyl groups. When one of R 1 and R 2 is hydrogen, the other is an alkyl group.)
(2) An organic oxidation catalyst that comprises the 9-azanoradamantane N-oxyl compound of (1).
(3) The catalyst of (2), wherein the catalyst has primary alcohol selectivity.
(4) A method for producing the 9-azanoradamantane N-oxyl compound represented by the formula (1),
the method producing the 9-azanoradamantane N-oxyl compound through at least a step of oxidizing an azanoradamantane compound represented by the following formula (2).
(In the formula (2), R 1 and R 2 have the same definitions as described above.)
(5) A method for producing the 9-azanoradamantane N-oxyl compound represented by the formula (1),
the method producing the 9-azanoradamantane N-oxyl compound through at least a step of closing the ring of a hydrazonoazabicyclo[3.3.1]nonane compound of the formula (3) below and forming an azanoradamantane ring, and oxidizing the resulting azanoradamantane compound represented by the formula (2).
(In the formula (3), R 1 and R 2 have the same definitions as described above; R 3 represents at least one substituent selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an amino group, a formyl group, a carboxyl group, a sulfo group, a linear or branched C 1-12 alkyl group, a C 3-12 cycloalkyl group, a (C 1-12 alkyl)oxy group, a (C 3-12 cycloalkyl)oxy group, a (C 1-12 alkyl)thio group, a (C 3-12 cycloalkyl)thio group, a (C 1-12 alkyl)amino group, a (C 3-12 cycloalkyl)amino group, a di(C 1-6 alkyl)amino group, a di(C 3-6 cycloalkyl)amino group, a C 1-12 alkylcarbonyl group, a C 3-12 cycloalkylcarbonyl group, a (C 1-12 alkyl)oxycarbonyl group, a (C 3-12 cycloalkyl)oxycarbonyl group, a (C 1-12 alkyl)thiocarbonyl group, a (C 3-12 cycloalkyl)thiocarbonyl group, a (C 1-12 alkyl)aminocarbonyl group, a (C 3-12 cycloalkyl)aminocarbonyl group, a di(C 1-6 alkyl)aminocarbonyl group, a di(C 3-6 cycloalkyl)aminocarbonyl group, a (C 1-22 alkyl)carbonyloxy group, a (C 3-12 cycloalkyl)carbonyloxy group, a (C 1-12 alkyl)carbonylthio group, a (C 3-12 cycloalkyl)carbonylthio group, a (C 1-12 alkyl)carbonylamino group, a (C 3-12 cycloalkyl)carbonylamino group, a di(C 1-12 alkylcarbonyl)amino group, a di(C 3-12 cycloalkylcarbonyl)amino group, a C 1-6 haloalkyl group, a C 3-6 halocycloalkyl group, a C 2-6 alkenyl group, a C 3-6 cycloalkenyl group, a C 2-6 haloalkenyl group, a C 3-6 halocycloalkenyl group, a C 2-6 alkynyl group, a C 2-6 haloalkynyl group, a benzyl group which may be optionally substituted with Ra, a benzyloxy group which may be optionally substituted with Ra, a benzylthio group which may be optionally substituted with Ra, a benzylamino group which may be optionally substituted with Ra, a dibenzylamino group which may be optionally substituted with Ra, a benzylcarbonyl group which may be optionally substituted with Ra, a benzyloxycarbonyl group which may be optionally substituted with Ra, a benzylthiocarbonyl group which may be optionally substituted with Ra, a benzylaminocarbonyl group which may be optionally substituted with Ra, a dibenzylaminocarbonyl group which may be optionally substituted with Ra, a benzylcarbonyloxy group which may be optionally substituted with Ra, a benzylcarbonylthio group which may be optionally substituted with Ra, a benzylcarbonylamino group which may be optionally substituted with Ra, a di(benzylcarbonyl)amino group which may be optionally substituted with Ra, an aryl group which may be optionally substituted with Ra, an aryloxy group which may be optionally substituted with Ra, an arylthio group which may be optionally substituted with Ra, an arylamino group which may be optionally substituted with Ra, a diarylamino group which may be optionally substituted with Ra, an arylcarbonyl group which may be optionally substituted with Ra, an aryloxycarbonyl group which may be optionally substituted with Ra, an arylthiocarbonyl group which may be optionally substituted with Ra, an arylaminocarbonyl group which may be optionally substituted with Ra, a diarylaminocarbonyl group which may be optionally substituted with Ra, an arylcarbonyloxy group which may be optionally substituted with Ra, an arylcarbonylthio group which may be optionally substituted with Ra, an arylcarbonylamino group which may be optionally substituted with Ra, and a di(arylcarbonyl)amino group which may be optionally substituted with Ra, wherein the substituents may be the same or different when two or more substituents exist; Ra represents halogen, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 3-6 cycloalkyl group, a C 1-6 alkoxy group, a C 1-6 alkoxy C 1-6 alkyl group, a C 1-6 alkyl sulfenyl C 1-6 alkyl group, a C 1-6 haloalkoxy group, C 1-6 alkyl sulfenyl group, a C 1-6 alkylsulfinyl group, a C 1-6 alkylsulfonyl group, a C 1-6 haloalkylsulfenyl group, a C 1-6 haloalkylsulfinyl group, a C 1-6 haloalkylsulfonyl group, a C 2-6 alkenyl group, a C 2-6 haloalkenyl group, a C 2-6 alkenyloxy group, a C 2-6 haloalkenyloxy group, a C 2-6 alkenylsulfenyl group, a C 2-6 alkenylsulfinyl group, a C 2-6 alkenylsulfonyl group, a C 2-6 haloalkenylsulfenyl group, a C 2-6 haloalkenylsulfinyl group, a C 2-6 haloalkenylsulfonyl group, a C 2-6 alkynyl group, a C 2-6 haloalkynyl group, a C 2-6 alkynyloxy group, a C 2-6 haloalkynyloxy group, a C 2-6 alkynyl sulfenyl group, a C 2-6 alkynylsulfinyl group, a C 2-6 alkynylsulfonyl group, a C 2-6 haloalkynyl sulfenyl group, a C 2-6 haloalkynylsulfinyl group, a C 2-6 haloalkynylsulfonyl group, —NO 2 , —CN, a formyl group, —OH, —SH, —NH 2 , —SCN, a C 1-6 alkoxycarbonyl group, a C 1-6 alkylcarbonyl group, a C 1-6 haloalkylcarbonyl group, a C 1-6 alkylcarbonyloxy group, a phenyl group, a C 1-6 alkylamino group, or a di C 1-6 alkylamino group, wherein Ra is substituted in numbers of 1 to 5, and may be the same or different when two or more Ra exist; and X represents a hydrogen atom, or a group selected from an acyl group, a carbamoyl group, a sulfoneamide group, an alkyl group, an allyl group, a benzyl group, an aryl group, a silyl group, a hydroxyl group, an alkoxy group, and an oxygen atom.)
(6) A method for producing the 9-azanoradamantane N-oxyl compound represented by the formula (1),
the method producing the 9-azanoradamantane N-oxyl compound through at least a step of condensing a keto-azabicyclo[3.3.1]nonane compound of the formula (4) below with phenylhydrazine, closing the ring of the resulting hydrazonoazabicyclo[3.3.1]nonane of the formula (3) and forming an azanoradamantane ring, and oxidizing the resulting azanoradamantane compound represented by the formula (2).
(In the formula (4), R 1 , R 2 , and X have the same definitions as described above.)
(7) A method for producing the azanoradamantane N-oxyl compound represented by the formula (1),
the method comprising:
synthesizing a ketobicycloamine product through condensation of 2,6-heptanedione, ammonium chloride, and acetonedicarboxylic acid, the 2,6-heptanedione being obtained by methylating a Weinreb diamide produced from glutaryl chloride;
producing a hydrazone through condensation of the ketobicycloamine product with hydrazine;
forming an azanoradamantane skeleton under basic condition; and
oxidizing the amino group.
(8) A method for oxidizing alcohols,
the method comprising oxidizing an alcohol in the presence of the 9-azanoradamantane N-oxyl compound of (1) to synthesize a corresponding oxo product.
(9) The method according to (8), wherein the oxidation is performed in the presence of a co-oxidizing agent.
(10) The method according to (8), wherein the alcohol is a compound that includes a primary alcohol and/or a secondary alcohol.
(11) The method according to (8), wherein the alcohol is a compound that includes a primary alcohol and a secondary alcohol, and wherein the method selectively oxidizes the primary alcohol.
(12) The method according to any one of (8) to (11), wherein the 9-azanoradamantane N-oxyl compound is added in 0.001 mol % to 1000 mol % with respect to the alcohol.
(13) The method according to any one of (9) to (12), wherein the co-oxidizing agent is an oxidizing agent selected from the group consisting of peroxy acid, hydrogen peroxide, hypohalous acid and salts thereof, perhalic acid and salts thereof, persulfates, halides, halogenating agents, trihaloisocyanuric acids, (diacetoxyiodo)arenes, oxygen, and air.
Advantageous Effects of Invention
A nitroxyl radical having an azanoradamantane skeleton with at least one alkyl group substituted at positions 1 and 5 is used as an oxidation catalyst to enable a more efficient primary alcohol selective oxidation reaction that requires less catalytic amounts and a shorter reaction time than a reaction catalyzed by the conventional TEMPO with a substrate that includes both primary alcohol and secondary alcohol. Primary alcohols can be oxidized with higher selectivity than that of AZADO and 1-Me-AZADO.
DESCRIPTION OF EMBODIMENTS
The following specifically describes the 9-azanoradamantane N-oxyl compounds of the present invention, methods for producing same, and organic oxidation catalysts and alcohol oxidation methods that use the 9-azanoradamantane N-oxyl compounds.
As used herein, “primary alcohol selective oxidation”, “primary alcohol selective oxidation reaction”, “primary alcohol selective oxidation catalyst”, “primary alcohol selectivity”, and other such language used in the same meaning mean reactions, functions, and catalysts with which 50% or more, preferably 70% or more, further preferably 90% or more of the reaction product of an oxidation reaction of a substrate that includes both primary alcohol and secondary alcohol are the oxidation product of solely the primary alcohol.
The present invention uses the 9-azanoradamantane N-oxyl compound of the following formula (1) as an organic oxidation catalyst.
(In the formula (1), R 1 and R 2 represent hydrogen atoms or alkyl groups. When one of R 1 and R 2 is hydrogen, the other is an alkyl group.)
The alkyl groups represented by R 1 and R 2 of the formula (1) are not particularly limited, as long as these are known in the art, and can achieve the intended object. Examples include lower alkyl groups. Examples of the lower alkyl groups include C 1-5 alkyl groups, specifically, methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, sec-butyl, t-butyl, and pentyl. Particularly preferred is methyl.
The compound represented by the foregoing formula (1) may be synthesized through at least a step of oxidizing an azanoradamantane compound represented by the following formula (2).
(In the formula (2), R 1 and R 2 have the same definitions as described above.)
The azanoradamantane compound represented by the foregoing formula (2) may be synthesized by closing the ring of a hydrazonoazabicyclo[3.3.1]nonane compound of the following formula (3) and forming an azanoradamantane ring.
(In the formula (3), R 1 and R 2 have the same definitions as described above; R 3 represents at least one substituent selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an amino group, a formyl group, a carboxyl group, a sulfo group, a linear or branched C 1-12 alkyl group, a C 3-12 cycloalkyl group, a (C 1-12 alkyl)oxy group, a (C 3-12 cycloalkyl)oxy group, a (C 1-12 alkyl)thio group, a (C 3-12 cycloalkyl)thio group, a (C 1-12 alkyl)amino group, a (C 3-12 cycloalkyl)amino group, a di(C 1-6 alkyl)amino group, a di(C 3-6 cycloalkyl)amino group, a C 1-12 alkylcarbonyl group, a C 3-12 cycloalkylcarbonyl group, a (C 1-12 alkyl)oxycarbonyl group, a (C 3-12 cycloalkyl)oxycarbonyl group, a (C 1-12 alkyl)thiocarbonyl group, a (C 3-12 cycloalkyl)thiocarbonyl group, a (C 1-12 alkyl)aminocarbonyl group, a (C 3-12 cycloalkyl)aminocarbonyl group, a di(C 1-6 alkyl)aminocarbonyl group, a di(C 3-6 cycloalkyl)aminocarbonyl group, a (C 1-12 alkyl)carbonyloxy group, a (C 3-12 cycloalkyl)carbonyloxy group, a (C 1-12 alkyl)carbonylthio group, a (C 3-12 cycloalkyl)carbonylthio group, a (C 1-12 alkyl)carbonylamino group, a (C 3-12 cycloalkyl)carbonylamino group, a di(C 1-12 alkylcarbonyl)amino group, a di(C 3-12 cycloalkylcarbonyl)amino group, a C 1-6 haloalkyl group, a C 3-6 halocycloalkyl group, a C 2-6 alkenyl group, a C 3-6 cycloalkenyl group, a C 2-6 haloalkenyl group, a C 3-6 halocycloalkenyl group, a C 2-6 alkynyl group, a C 2-6 haloalkynyl group, a benzyl group which may be optionally substituted with Ra, a benzyloxy group which may be optionally substituted with Ra, a benzylthio group which may be optionally substituted with Ra, a benzylamino group which may be optionally substituted with Ra, a dibenzylamino group which may be optionally substituted with Ra, a benzylcarbonyl group which may be optionally substituted with Ra, a benzyloxycarbonyl group which may be optionally substituted with Ra, a benzylthiocarbonyl group which may be optionally substituted with Ra, a benzylaminocarbonyl group which may be optionally substituted with Ra, a dibenzylaminocarbonyl group which may be optionally substituted with Ra, a benzylcarbonyloxy group which may be optionally substituted with Ra, a benzylcarbonylthio group which may be optionally substituted with Ra, a benzylcarbonylamino group which may be optionally substituted with Ra, a di(benzylcarbonyl)amino group which may be optionally substituted with Ra, an aryl group which may be optionally substituted with Ra, an aryloxy group which may be optionally substituted with Ra, an arylthio group which may be optionally substituted with Ra, an arylamino group which may be optionally substituted with Ra, a diarylamino group which may be optionally substituted with Ra, an arylcarbonyl group which may be optionally substituted with Ra, an aryloxycarbonyl group which may be optionally substituted with Ra, an arylthiocarbonyl group which may be optionally substituted with Ra, an arylaminocarbonyl group which may be optionally substituted with Ra, a diarylaminocarbonyl group which may be optionally substituted with Ra, an arylcarbonyloxy group which may be optionally substituted with Ra, an arylcarbonylthio group which may be optionally substituted with Ra, an arylcarbonylamino group which may be optionally substituted with Ra, and a di(arylcarbonyl)amino group which may be optionally substituted with Ra, wherein the substituents may be the same or different when two or more substituents exist; Ra represents halogen, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 3-6 cycloalkyl group, a C 1-6 alkoxy group, a C 1-6 alkoxy C 1-6 alkyl group, a C 1-6 alkyl sulfenyl C 1-6 alkyl group, a C 1-6 haloalkoxy group, a C 1-6 alkyl sulfenyl group, a C 1-6 alkylsulfinyl group, a C 1-6 alkylsulfonyl group, a C 1-6 haloalkylsulfenyl group, a C 1-6 haloalkylsulfinyl group, a C 1-6 haloalkylsulfonyl group, a C 2-6 alkenyl group, a C 2-6 haloalkenyl group, a C 2-6 alkenyloxy group, a C 2-6 haloalkenyloxy group, a C 2-6 alkenylsulfenyl group, a C 2-6 alkenylsulfinyl group, a C 2-6 alkenylsulfonyl group, a C 2-6 haloalkenylsulfenyl group, a C 2-6 haloalkenylsulfinyl group, a C 2-6 haloalkenylsulfonyl group, a C 2-6 alkynyl group, a C 2-6 haloalkynyl group, a C 2-6 alkynyloxy group, a C 2-6 haloalkynyloxy group, a C 2-6 alkynyl sulfenyl group, a C 2-6 alkynylsulfinyl group, a C 2-6 alkynylsulfonyl group, a C 2-6 haloalkynyl sulfenyl group, a C 2-6 haloalkynylsulfinyl group, a C 2-6 haloalkynylsulfonyl group, —NO 2 , —CN, a formyl group, —OH, —SH, —NH 2 , —SCN, a C 1-6 alkoxycarbonyl group, a C 1-6 alkylcarbonyl group, a C 1-6 haloalkylcarbonyl group, a C 1-6 alkylcarbonyloxy group, a phenyl group, a C 1-6 alkylamino group, or a di C 1-6 alkylamino group, wherein Ra is substituted in numbers of 1 to 5, and may be the same or different when two or more Ra exist; and X represents a hydrogen atom, or a group selected from an acyl group, a carbamoyl group, a sulfoneamide group, an alkyl group, an allyl group, a benzyl group, an aryl group, a silyl group, a hydroxyl group, an alkoxy group, and an oxygen atom.)
X may be groups other than those exemplified above, provided that such groups do not have an adverse effect on the reaction that closes the ring of the hydrazono[3.3.1]nonane compound and forms the azanoradamantane ring.
Examples of the acyl group representing X include C 1-10 acyl groups such as formyl, acetyl, propanoyl, pivaloyl, and benzoyl. Examples of the carbamoyl group include C 1-10 carbamoyl groups such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, and benzyloxycarbonyl. Examples of the sulfoneamide group include sulfoneamide groups such as methanesulfoneamide, trifluoromethanesulfoneamide, ethanesulfoneamide, toluenesulfoneamide, and nitrotoluenesulfoneamide. Examples of the aryl group include C 6-18 aryl groups such as phenyl, tolyl, and xylyl. Examples of the silyl group include silyl groups with substituted three alkyl groups, such as trimethylsilyl, triethylsilyl, triisopropylsilyl, and tert-butyldimethylsilyl. Examples of the alkoxy group include C 1-10 alkoxy groups such as methoxy, ethoxy, and propoxy. The alkyl groups are as described for R 1 .
The compound represented by the foregoing formula (3) may be synthesized by condensation of a keto-azabicyclo[3.3.1]nonane compound represented by the following formula (4) with phenylhydrazine.
(In the formula (4), R 1 , R 2 , and X have the same definitions as described above.)
The compound represented by the foregoing formula (4) may be synthesized by condensing 2,6-heptanedione, ammonium chloride, and acetonedicarboxylic acid, the 2,6-heptanedione being obtained by methylating a Weinreb diamide produced from glutaryl chloride.
Evidently, the synthesis methods above are merely examples of methods used to synthesize the compound represented by the formula (1), and different methods may be used. The compounds represented by the formulae (1) to (4) include derivatives in which the azanoradamantane core is substituted with substituents such as an alkyl group, a halogen atom, and an alkoxy group at positions other than positions 1 and 5.
The alcohols to be oxidized in the present invention may be primary alcohols represented by the following general formula (5), or secondary alcohols represented by the following general formula (6).
The substituents X and Y in the general formulae (5) and (6) are not particularly limited, as long as these are substituents that do not have an adverse effect on the oxidation reaction. For example, X and Y may be optionally substituted linear or branched alkyl groups, optionally substituted cyclic alkyl groups, optionally substituted aromatic hydrocarbon groups, or optionally substituted aromatic heterocyclic groups. Other examples include compounds that have more than one of the structure units of the general formulae (5) and (6) within the molecule.
Examples of the linear or branched alkyl group of the optionally substituted linear or branched alkyl groups represented by X and Y include alkyl groups of about 1 to 16 carbon atoms, preferably alkyl groups of about 1 to 8 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, isohexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl, heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-propylbutyl, 4,4-dimethylpentyl, octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-propylpentyl, 2-ethylhexyl, and 5,5-dimethylhexyl.
The cyclic alkyl group may be, for example, cycloalkyl of about 3 to 7 carbon atoms, for example, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
The aromatic ring forming the aromatic cyclic hydrocarbon group may be a monocyclic aromatic hydrocarbon ring or a fused polycyclic aromatic hydrocarbon ring. Examples of the aromatic hydrocarbon group include aryl groups of about 6 to 14 carbon atoms, such as phenyl, naphthyl, anthryl, azulenyl, phenanthryl, and acenaphthylenyl.
Non-limiting examples of the heterocyclic ring forming the aromatic heterocyclic group include a five-membered or six-membered monocyclic heterocyclic ring, and a six-membered+five-membered, or six-membered+six-membered fused heterocyclic ring. The ring-forming heteroatom of the heterocyclic ring may be, but is not limited to, for example, 1 to 3 atoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom. The heterocyclic ring is preferably an aromatic ring, and may be saturated or partially saturated. When the heterocyclic ring is saturated or partially saturated, the heteroatom moiety is preferably protected by a suitable protecting group, or may not be protected at all.
Examples of the aromatic heterocyclic group include monocyclic aromatic heterocyclic groups such as furyl, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, furazanyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, and triazinyl; and 8- to 12-membered fused polycyclic aromatic heterocyclic groups such as benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzindazolyl, benzooxazolyl, 1,2-benzoisooxazolyl, benzothiazolyl, benzopyranyl, 1,2-benzoisothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, α-carbolinyl, β-carbolinyl, γ-carbolinyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, phenanthridinyl, phenanthrolinyl, indolizinyl, pyrrolo[1,2-b]pyridazinyl, pyrazolo[1,5-a]pyridyl, imidazo[1,2-a]pyridyl, imidazo[1,5-a]pyridyl, imidazo[1,2-b]pyridazinyl, imidazo[1,2-a]pyrimidinyl, 1,2,4-triazolo[4,3-a]pyridyl, and 1,2,4-triazolo[4,3-b]pyridazinyl. These aromatic heterocyclic groups may be saturated or partially saturated.
As used herein, “a group being optionally substituted” means that one or more of any substituents may exist at any position of the group, and the substituents may be the same or different when two or more substituents exist. The substituent is not particularly limited, as long as it is not detrimental to the reaction.
Examples of the substituents that may be present on the linear or branched alkyl group, the cyclic alkyl group, the aromatic hydrocarbon group, or the aromatic heterocyclic group include, but are not limited to, alkyl groups of about 1 to 6 carbon atoms (such as methyl, ethyl, and propyl), alkoxy groups of about 1 to 6 carbon atoms (such as methoxy, ethoxy, and propoxy), halogen atoms (such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), alkenyl groups of about 2 to 6 carbon atoms (such as vinyl, and allyl), alkynyl groups of about 2 to 6 carbon atoms (such as ethynyl, and propargyl), hydroxyl groups, optionally substituted amino groups, optionally substituted sulfonyl groups, optionally substituted sulfoneamide groups, cyano groups, nitro groups, nitroso groups, optionally substituted amidino groups, carboxy groups, alkoxycarbonyl groups of about 2 to 7 carbon atoms, optionally substituted carbamoyl groups, aromatic groups, aromatic heterocyclic groups, and acyl groups (for example, optionally substituted alkylcarbonyl groups, and optionally substituted arylcarbonyl groups). These substituents may be appropriately protected. The protecting group is not particularly limited. Protecting groups suited for hydroxyl groups and amino groups may be appropriately selected from those described in publications, for example, such as Greene et al., Protective Groups in Organic Synthesis, 3rd Edition, 1999, John Wiley & Sons, Inc. The protecting groups may be removed from the product aldehyde or ketone compound after the alcohol oxidation, using appropriate means.
The “co-oxidizing agent” (also referred to as “re-oxidizing agent” or “bulk oxidizing agent”) used in the present invention is not particularly limited, as long as it makes the catalyst oxidatively potent, and can oxidize a hydroxylamine to a nitroxyl radical or an oxoammonium salt, or a nitroxyl radical to an oxoammonium salt. Generally, the co-oxidizing agent may be appropriately selected from those used in oxidation reactions that use TEMPO. Examples of such co-oxidizing agents include peroxy acid, hydrogen peroxide, hypohalous acid and salts thereof, perhalic acid and salts thereof, persulfates, halides, halogenating agents (such as N-bromosuccinimide), trihaloisocyanuric acids, (diacetoxyiodo)arenes, oxygen, air, and a mixture of these. Preferred are peracetic acid, m-chloroperbenzoic acid, hydrogen peroxide, sodium hypochlorite, lithium hypochlorite, potassium hypochlorite, calcium hypochlorite, sodium hypobromite, lithium hypobromite, potassium hypobromite, calcium hypobromite, sodium hydrogen persulfate, sodium periodate, periodic acid, trichloroisocyanuric acid, tribromoisocyanuric acid, N-bromosuccinimide, N-chlorosuccinimide, chlorine, bromine, iodine, diacetoxyiodobenzene, oxygen, and air. The method of the present invention can achieve high oxidation efficiency also when air is used as the bulk oxidizing agent, and using air as the bulk oxidizing agent represents a preferred aspect of the present invention.
The oxidation reaction in the present invention may be performed in a solvent or without a solvent. When using a solvent, the solvent is not particularly limited, as long as it does not inhibit the reaction. Examples of such solvents include aliphatic hydrocarbons (such as hexane, heptane, and petroleum ether), aromatic hydrocarbons (such as benzene, toluene, and xylene), nitriles (such as acetonitrile, and propionitrile), halogenated hydrocarbons (such as dichloromethane, chloroform, 1,2-dichloroethane, and carbon tetrachloride), ethers (such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and diethylene glycol dimethyl ether), amides (such as formamide, dimethylformamide, dimethylacetoamide, and hexamethylphosphoric triamide), sulfoxides (such as dimethylsulfoxide), esters (such as ethyl formate, ethyl acetate, propyl acetate, butyl acetate, and diethyl carbonate), carboxylic acids (such as acetic acid, formic acid, and propionic acid), fluoroalcohols (such as trifluoroethanol, and hexafluoroisopropanol), tertiary alcohols (such as tert-butyl alcohol), sulfolane, and water. These may be used as a mixture. Preferred are aliphatic hydrocarbons, aromatic hydrocarbons, nitriles, halogenated hydrocarbons, esters, carboxylic acids, water, and mixtures of these. Further preferred are dichloromethane, acetonitrile, acetic acid, toluene, ethyl acetate, isopropyl acetate, water, and mixtures of these. Particularly preferred are dichloromethane, acetonitrile, acetic acid, a dichloromethane-water mixed solution, an acetonitrile-water mixed solution, a toluene-water mixed solution, and an ethyl acetate-water mixed solution.
Buffers such as mineral salts and organic salts may be appropriately added to the reaction mixture. Examples of the buffer include alkali metal or alkali earth metal carbonates, alkali metal or alkali earth metal bicarbonates, alkali metal or alkali earth metal hydroxides, alkali metal or alkali earth metal phosphates, and alkali metal or alkali earth metal acetates. Preferred examples include sodium bicarbonate, sodium carbonate, sodium acetate, and phosphates.
Additives that promote reaction may be appropriately added to the reaction mixture. When sodium hypochlorite is used as the co-oxidizing agent for example, the additive may be, for example, a quaternary ammonium salt, or an alkali metal halide, preferably tetrabutylammonium chloride, tetrabutylammonium bromide, sodium bromide, potassium bromide, or a mixture of these. When using oxygen as the co-oxidizing agent, the additive may be typically selected from those used in air oxidation reactions that use TEMPO. Examples of such additives include nitrites, alkyl nitrites, inorganic acids, organic acids, bromine, and transition metals such as copper, iron, and ruthenium. Preferred examples include a mixture of sodium nitrite and acetic acid, a mixture of sodium nitrite and bromine, a mixture of sodium nitrite and iron chloride, copper chloride, and tert-butyl nitrite.
The amount of compound (I) used with respect to the alcohol is not particularly limited, and is typically 0.0001 mol % to 1,000 mol % (0.0001% to 1,000% in terms of the number of moles with respect to the number of moles of the raw material alcohols), preferably 0.0001 mol % to 150 mol %, more preferably 0.001 mol % to 50 mol %, particularly preferably 0.1 mol % to 20 mol % with respect to the alcohols.
The reaction temperature varies with the amounts of the raw material compound, the bulk oxidizing agent, and the reagent used, and is typically −80° C. to 120° C., preferably 0 to 40° C.
The target oxidation product of the reaction may be isolated by isolation procedures such as extraction, recrystallization, and column chromatography after the usual post-processes performed after the reaction.
The oxidation reaction catalyzed by the nitroxyl radical represented by (1) in the present invention is believed to proceed with the same reaction mechanism generally thought to be involved in oxidation reactions catalyzed by TEMPO or AZADO. It follows from this that hydroxylamine products corresponding to the nitroxyl radical represented by (1), and oxoammonium salts are also believed to show the same or similar catalytic activity to that of the nitroxyl radical compounds.
The present invention is described below in greater detail using Examples or the like. It should be noted that the scope of the present invention is not limited by the following.
EXAMPLE 1
Synthesis Method of Compound Represented by Formula (1) with R 1 =R 2 =Me (1,5-dimethyl-9-azanoradamantane N-oxyl, hereinafter, “DMN-AZADO”)
EXAMPLE 1-1
Synthesis of Heptane-2,6-dione
N,O-Dimethylhydroxylamine hydrochloride (42 g, 431 mmol) was added to a dichloromethane (500 ml) solution of glutaryl chloride (25 ml, 196 mmol) at room temperature, and pyridine (95 ml, 1.18 mol) was dropped under ice-cooled condition. After being stirred at room temperature for 2 hours, the reaction mixture was celite filtered. The filtrate was concentrated under reduced pressure, and diethyl ether (300 ml) was added. The mixture was celite filtered again, and concentrated under reduced pressure to give a Weinreb diamide product. The Weinreb diamide product was dissolved in tetrahydrofuran (500 ml), and a 3 M diethyl ether solution (160 ml, 0.470 mol) methylmagnesium bromide was slowly dropped under ice-cooled condition. After being stirred at room temperature for 4 hours, the mixture was brought back to ice-cooled condition, and water was slowly added. After extraction with ethyl acetate, the reaction liquid was washed with saturated brine. The organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was then purified by silica gel column chromatography to give heptane-2,6-dione (20.3 g, 81%).
Heptane-2,6-dione: 1 H-NMR (400 MHz, CDCl 3 ) δ 2.47 (t, J=7.2 Hz, 4H), 2.13 (s, 6H), (quint, J=7.2 Hz, 2H); 13 C-NMR (100 MHz, CDCl 3 ) δ 208.3, 42.4, 29.9, 17.6; IR (neat, cm −1 ): 2983, 1714, 1357, 1156; MS m/z 128 (M + ), 43 (100%); HRMS (EI): calcd for C 7 H 12 O 2 128.0837 (M + ), found 128.0835.
EXAMPLE 1-2
Synthesis of 1,5-Dimethyl-9-azabicyclo[3.3.1]nonan-3-one
An aqueous solution (32 ml) of heptane-2,6-dione (4.96 g, 38.7 mmol) and acetonedicarboxylic acid (10.74 g, 73.5 mmol) was injected into a sealed tube, and 27 M KOH (6 ml), an ammonium chloride (6.20 g, 116 mmol) aqueous solution (60 ml), and sodium acetate (3.81 g, 46.4 mmol) were added in order under ice-cooled condition. The mixture was then brought to pH 9 with a 1 g/ml KOH aqueous solution. The reaction liquid was stirred inside the sealed tube in the dark at room temperature for 3 days. A 10% hydrochloric acid aqueous solution was slowly dropped until the carbon dioxide gas generation went to completion, and the mixture was washed with dichloromethane. After a separation procedure, the aqueous layer was brought to basic pH with a 10% sodium hydroxide aqueous solution, and extracted with dichloromethane. The organic layer was dried over potassium carbonate, concentrated under reduced pressure, and purified by silica gel column chromatography to give 1,5-dimethyl-9-azabicyclo[3.3.1]nonan-3-one (1.84 g, 28%).
1,5-Dimethyl-9-azabicyclo[3.3.1]nonan-3-one: 1 H-NMR (400 MHz, CDCl 3 ) δ 2.35 (d, J=16.2 Hz, 2H), 2.11 (d, J=16.2 Hz, 2H), 1.70-1.62 (m, 3H), 1.58-1.41 (m, 1H), 1.41-1.28 (m, 3H), 1.21 (s, 6H); 13 C-NMR (100 MHz, CDCl 3 ) δ 211.3, 52.9, 52.4, 37.9, 31.5, 19.4; IR (neat, cm −1 ): 3285, 3217, 2923, 1704, 1291, 850; MS m/z 167 (M + ), 124 (100%); HRMS (EI): calcd for C 10 H 17 NO 167.1310 (M + ), found 167.1292.
EXAMPLE 1-3
Synthesis of N-tert-Butoxycarbonyl-1,5-dimethyl-9-azabicyclo[3.3.1]nonan-3-one
Triphosgene (1.33 g, 4.48 mmol) was added in several portions to a dichloromethane solution (50 ml) of 1,5-dimethyl-9-azabicyclo[3.3.1]nonan-3-one (1.87 g, 11.2 mmol) and pyridine (2.3 ml, 28 mmol) under ice-cooled condition. After stirring the mixture for 30 min under ice-cooled condition, tert-butanol (2.2 ml, 22.4 mmol) was dropped, and the mixture was stirred for 8 h. The reaction was stopped by adding water to the reaction liquid. The reaction liquid was then extracted with diethyl ether, washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography, and N-tert-butoxycarbonyl-1,5-dimethyl-9-azabicyclo[3.3.1]nonan-3-one (0.37 g, 13%), and 1,5-dimethyl-9-azabicyclo[3.3.1]nonan-3-one (1.1 g, 59%) were collected. The collected 1,5-dimethyl-9-azabicyclo[3.3.1]nonan-3-one was subjected to the same procedure twice to give N-tert-butoxycarbonyl-1,5-dimethyl-9-azabicyclo[3.3.1]nonan-3-one (1.36 g, 44%).
N-tert-Butoxycarbonyl-1,5-dimethyl-9-azabicyclo[3.3.1]nonan-3-one: 1 H-NMR (400 MHz, CDCl 3 ) δ 2.65 (d, J=15.5 Hz, 2H), 2.26 (d, J=16.9 Hz, 2H), 1.78-1.70 (m, 2H), 1.59-1.51 (m, 13H), 1.39 (s, 6H); 13 C-NMR (100 MHz, CDCl 3 ) δ 210.5, 158.9, 81.2, 57.1, 50.5, 38.8, 29.8, 28.0, 19.1; IR (neat, cm −1 ): 1704, 1366, 1306, 1272; MS m/z 267 (M + ), 57 (100%); HRMS (EI): calcd for C 15 H 25 NO 3 267.1834 (M + ), found 267.1818.
EXAMPLE 1-4
Synthesis of N-tert-Butoxycarbonyl-1,5-dimethyl-3-(tosylhydrazono)-9-azabicyclo[3.3.1]nonane
p-Toluenesulfonyl hydrazine (6.37 g, 34.2 mmol) was added to a benzene solution (115 ml) of N-tert-butoxycarbonyl-1,5-dimethyl-9-azabicyclo[3.3.1]nonan-3-one (3.04 g, 11.4 mmol), and the mixture was heated under reflux for 6 h with a Dean-Stark device. After adding saturated sodium bicarbonate water under ice-cooled condition, the ice-cooled reaction liquid was extracted with ethyl acetate, washed with saturated brine, and dried over magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography to give N-tert-butoxycarbonyl-1,5-dimethyl-3-(tosylhydrazono)-9-azabicyclo[3.3.1]nonane (3.07 g, 62%).
N-tert-Butoxycarbonyl-1,5-dimethyl-3-(tosylhydrazono)-9-azabicyclo[3.3.1]nonane: 1 H-NMR (400 MHz, CDCl 3 ) δ 7.85 (d, J=7.7 Hz, 2H), 7.42 (br s, 1H), 7.30 (d, J=7.7 Hz, 2H), 2.53-2.22 (m, 4H), 2.42 (s, 3H), 1.74-1.60 (m, 2H), 1.60-1.35 (m, 4H), 1.44 (s, 9H), 1.32 (s, 3H), 1.30 (s, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 161.1, 158.6, 143.8, 135.6, 129.4, 127.8, 80.9, 56.2, 55.4, 43.5, 39.2, 38.1, 36.2, 30.3, 29.9, 27.9, 21.5, 18.8; IR (neat, cm −1 ): 2930, 1697, 1166, 1137; MS m/z 435 (M + ), 180 (100%); HRMS (EI): calcd for C 22 H 33 N 3 O 4 S 435.2192 (M + ), found 435.2206.
EXAMPLE 1-5
Synthesis of N-tert-Butoxycarbonyl-1,5-dimethyl-9-azanoradamantane
Sodium hydride (18.9 mg, 0.466 mmol) was added to a dimethylformamide solution (1 ml) of N-tert-butoxycarbonyl-1,5-dimethyl-3-(tosylhydrazono)-9-azabicyclo[3.3.1]nonane (40.6 mg, 93.2 μmol) at room temperature. The mixture was stirred for 15 min at room temperature, and heated under reflux for 15 min. After adding water under ice-cooled condition, the ice-cooled reaction liquid was extracted with diethyl ether, washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was then purified by silica gel column chromatography to give N-tert-butoxycarbonyl-1,5-dimethyl-9-azanoradamantane (13.6 mg, 58%).
N-tert-Butoxycarbonyl-1,5-dimethyl-9-azanoradamantane: 1 H-NMR (400 MHz, CDCl 3 ) δ 2.61 (quint m, J=5.4 Hz, 2H), 1.76 (d, J=10.1 Hz, 4H), 1.57-1.48 (m, 4H), 1.48 (s, 9H), 1.38 (s, 6H); 13 C-NMR (100 MHz, CDCl 3 ) δ 159.8, 80.2, 65.8, 48.3, 38.8, 28.1, 24.2; IR (neat, cm −1 ): 2926, 2857, 1698, 1351, 1149; MS m/z 251 (M + ), 195 (100%); HRMS (EI): calcd for C 15 H 25 NO 2 251.1885 (M + ), found 251.1895.
EXAMPLE 1-5-2
Synthesis of 1,5-Dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO)
Trifluoroacetic acid (0.56 ml, 6.0 mmol) was dropped onto a dichloromethane solution (7.5 ml) of N-tert-butoxycarbonyl-1,5-dimethyl-9-azanoradamantane (376 mg, 1.50 mmol) under ice-cooled condition. The mixture was stirred at room temperature for 1 h, and water was added. After extraction with dichloromethane, the organic layer was dried over potassium carbonate, and concentrated under reduced pressure. To a methanol solution (3.0 ml) of the resulting 1,5-dimethyl-9-azanoradamantane was then added sodium tungstate dihydrate (247 mg, 0.75 mmol), and the mixture was stirred at room temperature for 30 min. The mixture was further stirred at room temperature for 40 min after adding urea.hydrogen peroxide (urea peroxide or UHP (urea hydrogen peroxide); 564 mg, 6.0 mmol). This was followed by addition of saturated sodium bicarbonate water, and extraction with diethyl ether. The organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was then purified by silica gel column chromatography to give 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO; 69 mg, 28%).
DMN-AZADO: IR (neat, cm −1 ): 2955, 2869, 1732, 1456, 1374, 1337; MS m/z 166 (M + ), 93 (100%); HRMS (EI): calcd for C 10 H 16 NO 166.1232 (M + ), found 166.1232; Anal: calcd for C 10 H 16 NO: C, 72.25; H, 9.70; N, 8.43. found: C, 71.91; H, 9.61; N, 8.07.
EXAMPLE 2
The DMN-AZADO synthesized above, and the existing nitroxyl radical oxidation catalysts TEMPO and 1-Me-AZADO were compared and examined for their catalytic activity in selective oxidation reactions of primary alcohol. The reactions were performed by using sodium hypochlorite as the co-oxidizing agent.
TABLE 1
yield
entry
catalyst
hydroxyaldehyde
ketoaldehyde
SM
1
TEMPO
69%
17%
0%
2
1-Me-AZADO
70%
0%
24%
3
DMN-AZADO
94%
trace
0%
With 1.5 equivalents of sodium hypochlorite, 17% of the product was collected as an unreacted raw material in the reaction using TEMPO, whereas 24% of the product of the reaction using 1-Me-AZADO was a diketone product resulting from the oxidation of both the primary alcohol and the secondary alcohol. In contrast to these moderate yields in the reactions catalyzed by TEMPO and 1-Me-AZADO, the reaction using the DMN-AZADO produced the target hydroxyketone product in high yield at 94%. These results demonstrated that the DMN-AZADO functions as an alcohol oxidation reaction catalyst capable of oxidizing primary alcohol with high selectivity and reactivity.
The reactivity of DMN-AZADO for various diols was examined by comparison to TEMPO.
TABLE 2
yield
substrate
catalyst
time
hydroxyaldehyde
ketoaldehyde
SM
TEMPO DMN-AZADO
20 min 4 min
70% 93%
0% trace
7% trace
TEMPO DMN-AZADO
20 min 3 min
78% 91%
0% trace
8% trace
TEMPO DMN-AZADO
20 min 10 min
67% 90%
0% 0%
17% 0%
The yield of the target hydroxyketone product was only about 67 to 78% in 20 minutes of reactions with TEMPO, though the yield varied for different substrates. On the other hand, the reactions using DMN-AZADO produced the target hydroxyketone product in 90% or higher yield with different substrates, and the non-target compounds, including ketoaldehyde, were within limits of error. These results demonstrated that the DMN-AZADO functions as an alcohol oxidation reaction catalyst capable of more efficiently oxidizing primary alcohol with higher selectivity and reactivity than TEMPO, irrespective of the substrate.
EXAMPLE 2-1
Oxidation of (E)-Methyl 6-ethyl-5-hydroxy-6-(hydroxymethyl)-2-octenate
A saturated sodium bicarbonate aqueous solution (350 μl) of DMN-AZADO (0.367 mg, 2.2 μmol), potassium bromide (2.63 mg, 22 μmol), and tetrabutylammonium bromide (3.56 mg, 11 μmol) was added to a dichloromethane solution (0.59 ml) of (E)-methyl 6-ethyl-5-hydroxy-6-(hydroxymethyl)-2-octenate (51.0 mg, 0.221 mmol), and the mixture was ice cooled to 0° C. Thereafter, a mixed solution of a sodium hypochlorite aqueous solution (1.262 M, 210 μl) and a saturated sodium bicarbonate aqueous solution (240 μl) was dropped, and the mixture was stirred at 0° C. for 10 min. This was followed by addition of a 20% sodium thiosulfate aqueous solution (1 ml), and extraction with diethyl ether. The organic layer was washed with saturated brine, and dried over sodium sulfate. The solvent was evaporated under reduced pressure. The resulting residue was then purified by silica gel column chromatography to obtain the desired compound (45.6 mg, 90%).
(E)-Methyl 6-Ethyl-6-formyl-5-hydroxy-2-octenate: 1 H-NMR (400 MHz, CDCl 3 ) δ 9.63 (s, 1H), 7.03 (ddd, J=14.4 Hz, 7.2 Hz, 7.2 Hz, 1H), 5.94 (d, J=14.4 Hz, 1H), 3.98 (ddd, J=10.4 Hz, 4.8 Hz, 2.4 Hz, 1H), 3.74 (s, 3H), 2.44-2.21 (m, 2H), 2.29 (d, J=4.8 Hz, 1H), 1.80 (dq, J=14.8 Hz, 7.4 Hz, 1H), 1.78 (dq, J=14.8 Hz, 7.4 Hz, 1H), 1.70 (dq, J=14.8 Hz, 7.4 Hz, 1H), 1.58 (dq, J=14.8 Hz, 7.4 Hz, 1H), 0.94 (t, J=7.4 Hz, 3H), 0.87 (t, J=7.4 Hz, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 208.2, 166.7, 146.2, 123.3, 72.0, 55.4, 51.5, 34.6, 23.0, 22.0, 8.27, 7.97; IR (neat, cm −1 ): 3500, 2969, 2883, 1722, 1658, 1438, 1328, 1275, 1219, 1170, 1043, 978; MS m/z 229 (M + +H), 100 (100%); HRMS (EI) calcd for C 12 H 21 O 4 229.1434 (M + +H), found 229.1426.
EXAMPLE 2-2
Oxidation of 2,2-Dimethyl-5-phenylpentane-1,3-diol
2,2-Dimethyl-5-phenylpentane-1,3-diol (42.5 mg, 0.204 mmol) was oxidized in the same manner as in Example 2-1 to give 3-hydroxy-2,2-dimethyl-5-phenylpentanal (39.3 mg, 93%).
3-Hydroxy-2,2-dimethyl-5-phenylpentanal: 1 H-NMR (400 MHz, CDCl 3 ) δ 9.51 (s, 1H), 7.36-7.17 (m, 5H), 3.77 (d, J=9.7 Hz, 1H), 2.96 (ddd, J=14.0 Hz, 9.7 Hz, 5.4 Hz, 1H), 2.67 (ddd, J=14.0 Hz, 9.2 Hz, 7.3 Hz, 1H), 2.29 (br s, 1H), 1.83-1.64 (m, 2H), 1.11 (s, 3H), 1.04 (s, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 206.6, 141.6, 128.3, 125.8, 74.0, 50.3, 33.0, 32.5, 18.8, 16.3; IR (neat, cm −1 ): 3466, 2959, 2871, 1721, 1455, 1075, 1046, 700; MS m/z 188 (M + -H 2 O), 72 (100%); HRMS (EI) calcd for C 13 H 16 O 188.1201 (M + -H 2 O), found 188.1189.
EXAMPLE 2-3
Oxidation of Olean-12-ene-11-oxo-3β,30-diol
Olean-12-ene-11-oxo-3β,30-diol (41.2 mg, 0.090 mmol) was oxidized in the same manner as in Example 2-1 to give the desired compound (37.3 mg, 91%).
Olean-12-ene-3β-hydroxy-11-oxo-30-al: 1 H-NMR (400 MHz, CDCl 3 ) δ 9.42 (s, 1H), 5.66 (s, 1H), 3.23 (dd, J=10.6 Hz, 5.3 Hz, 1H), 2.79 (dt, J=13.6 Hz, 3.4 Hz, 1H), 2.34 (s, 1H), 2.14-1.96 (m, 2H), 1.96-1.77 (m, 3H), 1.77-1.52 (m, 6H), 1.52-1.34 (m, 7H), 1.34-1.09 (m, 8H), 1.09-0.90 (m, 8H), 0.81 (s, 3H), 0.80 (s, 3H), 0.70 (d, J=10.6 Hz, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 205.6, 200.0, 168.5, 128.6, 78.7, 61.8, 54.9, 47.6, 46.8, 45.4, 43.2, 39.13, 39.11, 38.4, 37.1, 32.7, 31.9, 28.5, 28.3, 28.1, 27.3, 26.4, 26.1, 24.0, 23.7, 18.7, 17.5, 16.3, 15.5; IR (neat, cm −1 ): 3461, 2927, 2864, 1728, 1655, 1456, 1387, 1209, 1075, 755; MS m/z 454 (M + ), 287 (100%); HRMS (EI) calcd for C 30 H 46 O 3 454.3447 (M + ), found 454.3436.
EXAMPLE 3
DMN-AZADO, TEMPO, 1-Me-AZADO, and AZADO were compared for catalytic activity under the conditions in which natural product betulin and diacetoxyiodobenzene were used as a substrate and a co-oxidizing agent, respectively. The existing oxidizing agent DMP (Dess-Martin periodinane) was also examined for comparison.
TABLE 3
yield
hydroxy-
keto-
entry
catalyst
time
aldehyde
aldehyde
SM
1
TEMPO
2
h
56%
0%
26%
2
1-Me-AZADO
15
min
49%
51%
0%
3
AZADO
15
min
48%
46%
0%
4
DMN-AZADO
45
min
97%
3%
0%
5
DMP (1.5 eq.) a
3
h
8%
13%
61%
a no use of PhI(OAc) 2 , CH 2 Cl 2 (0.1M)
The reactions using AZADO and 1-Me-AZADO yielded the diketone product in about 50%, whereas 26% of the raw material was collected after 2 hours of reaction with TEMPO. Over an extended reaction time, a decomposition reaction of the target product hydroxyaldehyde proceeded with TEMPO. On the other hand, the reaction with DMN-AZADO produced the target hydroxyaldehyde in high yield, though only a slight generation (3%) of diketone product was observed. Selectivity was not observed for DMP.
It was found from these results that the DMN-AZADO had higher reactivity than TEMPO, and higher primary alcohol selectivity than AZADO and 1-Me-AZADO even when used with the co-oxidizing agent diacetoxyiodobenzene.
EXAMPLE 4
The catalytic activity of TEMPO and DMN-AZADO was examined in greater detail with various catalytic amounts under the conditions in which betulin and diacetoxyiodobenzene were used as a substrate and a co-oxidizing agent, respectively.
TABLE 4
loading
yield
amount
hydroxy-
keto-
entry
catayst
(mol %)
time
aldehyde
aldehyde
SM
1
TEMPO
10
2
h
56%
0%
26%
2
20
3.5
h
98%
0%
0%
3
15
5.5
h
93%
0%
6%
4
DMN-
10
0.75
h
97%
3%
0%
5
AZADO
5
1
h
92%
2%
0%
6
3
1.3
h
94%
0%
5%
The primary alcohol selective reactions efficiently proceeded with TEMPO when the catalytic amount was increased to 15 mol %, whereas the reactions using DMN-AZADO efficiently proceeded with a catalytic amount as low as 3 mol %. DMN-AZADO advantageously afforded a shorter reaction time than TEMPO. DMN-AZADO was clearly more advantageous than TEMPO in terms of catalytic amount and reaction time.
EXAMPLE 5
The reactivity of DMN-AZADO for various diols was examined by comparison to TEMPO.
The primary alcohol selective oxidation reactions of various diols were faster, and more efficient with DMN-AZADO than with TEMPO. The primary alcohol oxidation at the neopentyl position also proceeded faster with DMN-AZADO, demonstrating that DMN-AZADO is a high-activity primary alcohol selective oxidation catalyst.
TABLE 5
loading
amount
yield/time
entry
substrate
(mol %)
TEMPO
DMN-AZADO
1
5
26%/1.5 h
92%/15 min
2
5
21%/2 h
80%/1 h
3 a
2
58%/4 h
85%/3 h
4 a
2
78%/2.5 h
79%/2 h
5
5
32%/4 h
92%/1 h
6
5
62%/2 h
99%/1 h
7
5
41%/2.5 h
95%/30 min
a 1.2 eq. PhI(OAc) 2 was used.
EXAMPLE 6
Primary Alcohol Selective Oxidation Reaction Using Diacetoxyiodobenzene as Co-Oxidizing Agent
EXAMPLE 6-1
DMN-AZADO (2.00 mg, 0.012 mmol) and diacetoxyiodobenzene (117 mg, 0.362 mmol) were added to a dichloromethane solution (0.24 ml) of 2,2-dimethyl-5-phenylpentane-1,3-diol (50.2 mg, 0.241 mmol), and the mixture was stirred at room temperature for 15 min. This was followed by addition of saturated sodium bicarbonate water (1 ml) and a sodium thiosulfate solution (1 ml), and extraction with diethyl ether. The organic layer was washed with saturated brine, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure. The resulting residue was then purified by silica gel column chromatography to give 3-hydroxy-2,2-dimethyl-5-phenylpentanal (49.2 mg, 92%).
3-Hydroxy-2,2-dimethyl-5-phenylpentanal: 1 H-NMR (400 MHz, CDCl 3 ) δ 9.51 (s, 1H), 7.36-7.17 (m, 5H), 3.77 (d, J=9.7 Hz, 1H), 2.96 (ddd, J=14.0 Hz, 9.7 Hz, 5.4 Hz, 1H), 2.67 (ddd, J=14.0 Hz, 9.2 Hz, 7.3 Hz, 1H), 2.29 (br s, 1H), 1.83-1.64 (m, 2H), 1.11 (s, 3H), 1.04 (s, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 206.6, 141.6, 128.3, 125.8, 74.0, 50.3, 33.0, 32.5, 18.8, 16.3; IR (neat, cm −1 ): 3466, 2959, 2871, 1721, 1455, 1075, 1046, 700; MS m/z 188 (M + -H 2 O), 72 (100%); HRMS (EI) calcd for C 13 H 16 O 188.1201 (M + -H 2 O), found 188.1189.
EXAMPLE 6-2
Oxidation of 2,2,4-Trimethylpentane-1,3-diol
2,2,4-Trimethylpentane-1,3-diol (41.7 mg, 0.285 mmol) was oxidized in the same manner as in Example 6-1 to give 3-hydroxy-2,2,4-trimethylpentanal (32.8 mg, 80%).
3-Hydroxy-2,2,4-trimethylpentanal: 1 H-NMR (400 MHz, CDCl 3 ) δ 9.63 (s, 1H), 3.55 (dd, J=5.8 Hz, 3.9 Hz, 1H), 1.96 (d, J=5.8 Hz, 1H), 1.88 (sept d, J=6.8 Hz, 3.9 Hz, 1H), 1.13 (s, 3H), 1.12 (s, 3H), 0.97 (d, J=6.8 Hz, 3H), 0.91 (d, J=6.8 Hz, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 206.5, 80.3, 30.0, 21.8, 19.9, 18.7, 17.3; IR (neat, cm −1 ): 3483, 1713; MS m/z 145 (M + +H), 127 (100%); HRMS (FAB) calcd for C 8 H 17 O 2 145.1229 (M + +H), found 145.1218.
EXAMPLE 6-3
Oxidation of 2-Ethylhexane-1,3-diol
2-Ethylhexane-1,3-diol (51.7 mg, 0.354 mmol) was oxidized in the same manner as in Example 6-1 using diacetoxyiodobenzene (137 mg, 0.425 mmol) to give the desired compound (43.2 mg, 85%).
2-Ethyl-3-hydroxyhexanal: 1 H-NMR (400 MHz, CDCl 3 ) δ9.78 (d, J=2.4 Hz, 0.4H), 9.76 (d, J=2.9 Hz, 0.6H), 3.98 (dt, J=8.7 Hz, 4.4 Hz, 0.4H), 3.88 (dt, J=5.8 Hz, 5.8 Hz, 0.6H), 2.37-2.23 (m, 1H), 2.06 (br s, 0.6H), 1.86 (br s, 0.4H), 1.84-1.73 (m, 1H), 1.73-1.61 (m, 1H), 1.58-1.42 (m, 3H), 1.42-1.29 (m, 1H), 1.05-0.89 (m, 6H); 13 C-NMR (100 MHz, CDCl 3 ) δ major 205.9, 70.8, 58.7, 37.1, 19.3, 18.6, 13.8, 11.4, minor 205.7, 70.5, 58.8, 36.5, 19.1, 17.4, 13.8, 12.1; IR (neat, cm −1 ): 3428, 2961, 2874, 1719, 1463, 1142, 978; MS m/z 145 (M + +H), 72 (100%); HRMS (EI) calcd for C 8 H 17 O 2 145.1229 (M + +H), found 145.1215.
EXAMPLE 6-4
Oxidation of Octadecane-1,12-diol
Octadecane-1,12-diol (51.7 mg, 0.180 mmol) was oxidized in the same manner as in Example 6-1 to give the desired compound (40.2 mg, 79%).
12-Hydroxyoctadecanal: mp 53-54° C. (Et 2 O-hexane); 1 H-NMR (400 MHz, CDCl 3 ) δ 9.76 (t, J=1.8 Hz, 1H), 3.58 (brs, 1H), 2.42 (td, J=7.2 Hz, 1.8 Hz, 2H), 1.63 (quint, J=7.2 Hz, 2H), 1.49-1.30 (m, 6H), 1.42-1.20 (m, 21H), 0.88 (t, J=6.5 Hz, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 202.9, 71.8, 43.8, 37.41, 37.38, 31.8, 29.6, 29.5, 29.4, 29.31, 29.25, 29.1, 25.6, 25.5, 22.5, 22.0, 14.0; IR (neat, cm −1 ): 3300, 3211, 2913, 2848, 1712, 1469, 1130, 1079, 719; MS m/z 283 (M + -H), 199 (100%); HRMS (EI) calcd for C 18 H 35 O 2 283.2637 (M + -H), found 283.2622.
EXAMPLE 6-5
Oxidation of Betulin
Betulin (50.4 mg, 0.114 mmol) was oxidized in the same manner as in Example 6-1 to give the desired compound (46.0 mg, 92%).
Betulinal: mp 168-169° C. (CHCl 3 -hexane); 1 H-NMR (400 MHz, CDCl 3 ) δ 9.68 (s, 1H), 4.76 (s, 1H), 4.63 (s, 1H), 3.18 (dd, J=10.6 Hz, 4.4 Hz, 1H), 2.86 (td, J=11.1 Hz, 5.8 Hz, 1H), 2.12-2.04 (m, 1H), 2.02 (td, J=12.1 Hz, 3.4 Hz, 1H), 1.96-1.82 (m, 1H), 1.82-0.84 (m, 35H), 0.82 (s, 3H), 0.75 (s, 3H), 0.67 (d, J=9.1 Hz, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 206.7, 149.7, 110.1, 78.9, 59.3, 55.3, 50.4, 48.0, 47.5, 42.5, 40.8, 38.8, 38.71, 38.67, 37.2, 34.3, 33.2, 29.8, 29.2, 28.8, 28.0, 27.4, 25.5, 20.7, 19.0, 18.2, 16.1, 15.9, 15.3, 14.2; IR (neat, cm −1 ): 3419, 2942, 2868, 1724, 1452, 1377, 910, 733; MS m/z 440 (M + ), 440 (100%); HRMS (EI) calcd for C 30 H 48 O 2 440.3654 (M + ), found 440.3656.
EXAMPLE 6-6
Oxidation of Olean-12-ene-11-oxo-3β,30-diol
Olean-12-ene-11-oxo-3β,30-diol (43.4 mg, 0.095 mmol) was oxidized in the same manner as in Example 6-1 to give the desired compound (42.8 mg, 99%).
Olean-12-ene-3β-hydroxy-11-oxo-30-al: 1 H-NMR (400 MHz, CDCl 3 ) δ 9.42 (s, 1H), 5.66 (s, 1H), 3.23 (dd, J=10.6 Hz, 5.3 Hz, 1H), 2.79 (dt, J=13.6 Hz, 3.4 Hz, 1H), 2.34 (s, 1H), 2.14-1.96 (m, 2H), 1.96-1.77 (m, 3H), 1.77-1.52 (m, 6H), 1.52-1.34 (m, 7H), 1.34-1.09 (m, 8H), 1.09-0.90 (m, 8H), 0.81 (s, 3H), 0.80 (s, 3H), 0.70 (d, J=10.6 Hz, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 205.6, 200.0, 168.5, 128.6, 78.7, 61.8, 54.9, 47.6, 46.8, 45.4, 43.2, 39.13, 39.11, 38.4, 37.1, 32.7, 31.9, 28.5, 28.3, 28.1, 27.3, 26.4, 26.1, 24.0, 23.7, 18.7, 17.5, 16.3, 15.5; IR (neat, cm −1 ): 3461, 2927, 2864, 1728, 1655, 1456, 1387, 1209, 1075, 755; MS m/z 454 (M + ), 287 (100%); HRMS (EI) calcd for C 30 H 46 O 3 454.3447 (M + ), found 454.3436.
EXAMPLE 6-7
Oxidation of Erythrodiol
Erythrodiol (44.0 mg, 0.099 mmol) was oxidized in the same manner as in Example 6-1 to give the desired compound (41.7 mg, 95%).
Oleanoaldehyde: [a ] D 22 +68.7 (c 0.41, CHCl 3 ); mp 184-185° C. (CHCl 3 -hexane); 1 H-NMR (400 MHz, CDCl 3 ) δ 9.40 (s, 1H), 5.34 (t, J=3.5 Hz, 1H), 3.21 (dd, J=11.2 Hz, 4.4 Hz, 1H), 2.63 (dd, J=13.7 Hz, 4.4 Hz, 1H), 1.98 (td, J=13.6 Hz, 3.9 Hz, 1H), 1.89 (t, J=3.9 Hz, 1H), 1.87 (m, 1H), 1.80-0.60 (m, 41H); 13 C-NMR (100 MHz, CDCl 3 ) δ 207.5, 142.9, 123.2, 78.9, 55.2, 49.1, 47.5, 45.6, 41.7, 40.4, 39.5, 38.7, 38.4, 37.0, 33.1, 33.0, 32.7, 30.6, 28.1, 27.7, 27.1, 26.7, 25.5, 23.40, 23.38, 22.1, 18.3, 17.0, 15.6, 15.3; IR (neat, cm −1 ): 3509, 2928, 2859, 1712, 1462, 1049, 1029, 997, 753; MS m/z 440 (M + ), 203 (100%); HRMS (EI) calcd for C 30 H 48 O 2 440.3654 (M + ), found 440.3649.
EXAMPLE 7
TEMPO and DMN-AZADO were compared and examined for catalyst efficiency and primary alcohol selectivity in the one-pot oxidation reaction of primary alcohol into carboxylic acid performed in the presence of a catalytic amount of sodium hypochlorite, and sodium chlorite used as a co-oxidizing agent.
TABLE 6
yield/time
entry
substrate
TEMPO
DMN-AZADO
1
50%/24 h
91%/3 h
2
49%/24 h
92%/7 h
3
81%/24 h
95%/12 h
4
85%/24 h
94%/14 h
5
77%/24 h
83%/9 h
DMN-AZADO was clearly more advantageous in terms of the yield of the target product and the reaction time also in the one-pot oxidation reaction of primary alcohol into carboxylic acid.
EXAMPLE 7-1
Oxidation of 2,2-Dimethyl-5-phenylpentane-1,3-diol
A sodium chlorite aqueous solution (81.0 mg, 0.717 mmol in H 2 O (0.4 ml)), and a sodium hypochlorite aqueous solution (0.0146 M, 0.16 ml) were separately and slowly dropped onto an acetonitrile (1.2 ml)-pH 6.8 phosphate buffer (1 M, 0.8 ml) of 2,2-dimethyl-5-phenylpentane-1,3-diol (49.7 mg, 0.239 mmol) and DMN-AZADO (3.97 mg, 0.024 mmol) at room temperature. The mixture was stirred at 25° C. for 1 h, and a pH 2.3 phosphate buffer was added until the mixture was brought to pH 4 or less. The aqueous layer was then saturated with a common salt, and extracted with dichloromethane. The organic layer was dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The resulting residue was dissolved in a diethyl ether solution, and treated with an excess amount of a diazomethane diethyl ether solution to produce a methyl ester product. After evaporating the solvent under reduced pressure, the product was purified by silica gel column chromatography to give a hydroxy ester compound (51.0 mg, 90%).
Methyl 3-Hydroxy-2,2-dimethyl-5-phenylpentanate: 1 H-NMR (400 MHz, CDCl 3 ) δ 7.38-7.15 (m, 5H), 3.69 (s, 3H), 3.62 (ddd, J=10.4 Hz, 7.0 Hz, 1.7 Hz, 1H), 2.95 (ddd, J=14.7 Hz, 9.8 Hz, 4.9 Hz, 1H), 2.65 (ddd, J=13.6 Hz, 9.2 Hz, 6.8 Hz, 1H), 2.57 (d, J=7.0 Hz, 1H), 1.87-1.70 (m, 1H), 1.70-1.50 (m, 1H), 1.19 (s, 3H), 1.16 (s, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 178.1, 142.0, 128.4, 128.3, 125.8, 76.0, 51.8, 47.1, 33.6, 32.8, 22.3, 20.3; IR (neat, cm −1 ): 3501, 2951, 1723, 1455, 1275, 1134, 1075, 701; MS m/z 236 (M + ), 117 (100%); HRMS (EI) calcd for C 14 H 20 O 3 236.1413 (M + ), found 236.1401.
EXAMPLE 7-2
Oxidation of Isopropyl 2,3-Deoxy-α-D-glucopyranoside
Isopropyl 2,3-deoxy-α-D-glucopyranoside (50.0 mg, 0.263 mmol) was oxidized in the same manner as in Example 7-1 to give the desired methyl ester compound (55.6 mg, 97%).
Methyl(isopropyl-2,3-deoxy-α-D-glucopyranoside)uronate: 1 H-NMR (400 MHz, CDCl 3 ) δ 5.01 (t, J=2.4 Hz, 1H), 4.19 (d, J=9.2 Hz, 1H), 3.95 (sept, J=6.3H, 1H), 3.83 (s, 3H), 3.84-3.74 (d m, J=2.4 Hz, 1H), 3.15 (s, 1H), 1.98-1.81 (m, 2H), 1.81-1.72 (m, 2H), 1.23 (d, J=6.3 Hz, 3H), 1.15 (d, J=6.3 Hz, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 172.3, 94.3, 72.2, 68.7, 67.4, 52.4, 28.9, 25.8, 23.2, 21.3; IR (neat, cm −1 ): MS m/z 175 (M + -C 3 H 7 ), 129 (100%); HRMS (EI) calcd for C 7 H 11 O 5 175.0607 (M + -C 3 H 7 ), found 175.0607.
EXAMPLE 7-3
Oxidation of 2,2,4-Trimethylpentane-1,3-diol
2,2,4-Trimethylpentane-1,3-diol (44.4 mg, 0.304 mmol) was oxidized in the same manner as in Example 7-1 to give the desired methyl ester compound (48.7 mg, 92%).
Methyl 3-Hydroxy-2,2,4-trimethylpentanate: 1 H-NMR (400 MHz, CDCl 3 ) δ 3.69 (s, 3H), 3.39 (dd, J=8.7 Hz, 3.6 Hz, 1H), 2.81 (d, J=8.7 Hz, 1H), 1.86 (sept d, J=6.9 Hz, 3.6 Hz, 1H), 1.28 (s, 3H), 1.19 (s, 3H), 0.97 (d, J=6.9 Hz, 3H), 0.81 (d, J=6.9 Hz, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 178.3, 81.2, 51.6, 45.8, 29.8, 23.0, 22.3, 21.3, 16.2; IR (neat, cm −1 ): 3506, 2961, 2878, 1729, 1472, 1264, 1143, 1030, 994; MS m/z 143 (M + -CH 3 O), 102 (100%); HRMS (EI) calcd for C 8 H 15 O 2 143.1072 (M + -CH 3 O), found 143.1063.
EXAMPLE 7-4
Oxidation of Methyl 2,3-bis-O-(Phenylmethyl)-β-D-glucopyranoside
Methyl 2,3-bis-O-(phenylmethyl)-β-D-glucopyranoside (41.8 mg, 0.112 mmol) was oxidized in the same manner as in Example 7-1 to give the desired methyl ester compound (42.3 mg, 94%).
Methyl (methyl-2,3-bis-O-(phenylmethyl)-β-D-glucopyranoside)uronate: 1 H-NMR (400 MHz, CDCl 3 ) δ 7.38-7.25 (m, 10H), 4.90 (d, J=11.2 Hz, 1H), 4.89 (d, J=11.2 Hz, 1H), 4.80 (d, J=11.2 Hz, 1H), 4.71 (d, J=11.2 Hz, 1H), 4.37 (d, J=8.3 Hz, 1H), 3.87-3.81 (m, 2H), 3.83 (s, 3H), 3.59 (s, 3H), 3.52 (dd, J=8.3 Hz, 8.3 Hz, 1H), 3.44 (dd, J=8.3 Hz, 8.3 Hz, 1H), 2.80 (s, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 169.7, 138.4, 138.3, 128.4, 128.3, 128.0, 127.9, 127.8, 127.7, 105.0, 83.0, 81.1, 75.3, 74.8, 74.2, 71.7, 57.4, 52.7; IR (neat, cm −1 ): 3490, 2909, 1749, 1454, 1210, 1069, 738, 698; MS m/z 402 (M + ), 311 (100%); HRMS (EI) calcd for C 22 H 26 O 7 402.1679 (M + ), found 402.1642.
EXAMPLE 7-5
Oxidation of Methyl 2-O-n-Butyl-α-D-ribofuranoside
Methyl 2-O-n-butyl-α-D-ribofuranoside (41.5 mg, 0.188 mmol) was oxidized in the same manner as in Example 7-1 to give the desired methyl ester compound (38.8 mg, 83%).
Methyl(methyl-2-O-n-butyl-α-D-ribofuranoside)uronate: 1 H-NMR (400 MHz, CDCl 3 ) δ 5.11 (d, J=4.4 Hz, 1H), 4.65 (d, J=2.0 Hz, 1H), 4.29 (ddd, J=8.8 Hz, 5.9 Hz, 2.0 Hz, 1H), 3.86 (dd, J=5.9 Hz, 4.4 Hz, 1H), 3.79 (s, 3H), 3.63 (dt, J=9.3 Hz, 6.8 Hz, 1H), 3.56 (dt, J=9.3 Hz, 6.8 Hz, 1H), 3.48 (s, 3H), 3.21 (d, J=8.8 Hz, 1H), 1.65 (dt, J=6.8 Hz, 6.8 Hz, 1H), 1.63 (dt, J=6.8 Hz, 6.8 Hz, 1H), 1.39 (dq, J=14.6 Hz, 7.3 Hz, 2H), 0.93 (t, J=7.3 Hz, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 170.7, 102.6, 83.7, 78.2, 71.8, 70.6, 55.5, 52.4, 31.6, 19.0, 13.7; IR (neat, cm −2 ): 3528, 2957, 1753, 1439, 1208, 1090, 1055; MS m/z 247 (M + -H), 159 (100%); HRMS (EI) calcd for C 11 H 19 O 6 247.1182 (M + -H), found 247.1179.
EXAMPLE 8
TEMPO and DMN-AZADO were compared for catalytic activity in the oxidation reaction of a diol into a medium-membered lactone using diacetoxyiodobenzene.
TABLE 7
loading amount
entry
catalyst
(mol %)
time
yield
1
TEMPO
10
8.5
h
82%
2
5
9
h
75%
3
DMN-AZADO
10
2
h
83%
4
5
3
h
78%
DMN-AZADO was shown to advantageously afford a shorter reaction time than TEMPO.
EXAMPLE 8-1
Oxidation of Dodecane-1,6-diol
DMN-AZADO (3.69 mg, 0.0222 mmol) and diacetoxyiodobenzene (179 mg, 0.555 mmol) were added to a dichloromethane solution (2.2 ml) of dodecane-1,6-diol (44.9 mg, 0.222 mmol), and the mixture was stirred at room temperature for 2 h. This was followed by addition of saturated sodium bicarbonate water and a saturated sodium thiosulfate solution, and extraction with dichloromethane. The organic layer was washed with saturated brine, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure. The residue was then purified by silica gel column chromatography to give a lactone product (36.5 mg, 83%).
6-Hexyl-ε-caprolactone: 1 H-NMR (400 MHz, CDCl 3 ) δ 4.23 (ddt, J=7.8 Hz, 3.9 Hz, 3.9 Hz, 1H), 2.78-2.48 (m, 2H), 2.06-1.81 (m, 3H), 1.81-1.40 (m, 6H), 1.40-1.18 (m, 7H), 0.88 (t, J=6.4 Hz, 3H); 1 C-NMR (100 MHz, CDCl 3 ) δ 175.8, 80.5, 36.3, 34.9, 34.5, 31.6, 29.0, 28.2, 25.3, 23.0, 22.5, 14.0; IR (neat, cm −1 ): 2931, 2859, 1730, 1448, 1175, 1013; MS m/z 199 (M + +H), 85 (100%); HRMS (EI) calcd for C 12 H 23 O 2 199.1698 (M + +H), found 199.1688.
TABLE 8
catalyst
yield/time
TEMPO
77%/18 h
DMN-AZADO
75%/2 h
DMN-AZADO was shown to advantageously afford a shorter reaction time than TEMPO even with a different substrate.
EXAMPLE 8-2
Oxidation of (1R,3S)-2,2-Dimethyl-3-(2-hydroxypropyl)-1-(2-hydroxyethyl)cyclopropane
(1R,3S)-2,2-Dimethyl-3-(2-hydroxypropyl)-1-(2-hydroxyethyl)cyclopropane (44.5 mg, 0.258 mmol) was oxidized in the same manner as in Example 8-1 to give the desired compound (32.7 mg, 75%).
(1R,7S)-5,8,8-Trimethyl-4-oxabicyclo[5.1.0]octan-3-one: 1 H-NMR (400 MHz, CDCl 3 ) δ 4.68-4.58 (m, 0.5H), 4.14 (dqd, J=12.0 Hz, 6.0 Hz, 3.0 Hz, 0.5H), 3.17 (dd, J=15.5 Hz, 4.8 Hz, 0.5H), 2.97 (dd, J=15.5 Hz, 4.1 Hz, 0.5H), 2.77 (dd, J=14.5 Hz, 8.0 Hz, 0.5H), 2.42 (dd, J=14.5 Hz, 10.1 Hz, 0.5H), 2.20-2.02 (m, 1H), 1.87 (dd, J=15.5 Hz, 1.9 Hz, 0.5H), 1.80 (ddd, J=15.9 Hz, 10.6 Hz, 5.3 Hz, 0.5H), 1.32 (d, J=6.0 Hz, 1.5H), 1.31 (d, J=6.0 Hz, 1.5H), 1.074 (s, 1.5H), 1.067 (s, 1H), 1.05 (s, 1.5H), 1.04 (s, 1.5H), 1.03-0.85 (m, 1H), 0.78-0.65 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 173.8, 173.1, 76.9, 73.9, 33.0, 30.7, 30.6, 29.1, 29.0, 28.5, 22.1, 22.0, 21.7, 20.7, 19.9, 19.8, 18.7, 18.0, 14.8, 14.7; IR (neat, cm −1 ): 2980, 2938, 2868, 1734, 1277, 1193, 1069, 1057; MS m/z 168 (M + ), 81 (100%); HRMS (EI) calcd for C 10 H 16 O 2 168.1150 (M + ), found 168.1143.
EXAMPLE 9
TEMPO and DMN-AZADO were compared for catalytic activity in an oxidation reaction from a diol, using 2,2-dimethyl-5-phenylpentane-1,3-diol.
TABLE 9
entry
catalyst
time
yield
1
TEMPO
24 h
72%
2
DMN-AZADO
18 h
90%
DMN-AZADO was shown to advantageously afford a shorter reaction time than TEMPO.
EXAMPLE 9-1
Oxidation of 2,2-Dimethyl-5-phenylpentane-1,3-diol
DMN-AZADO (3.16 mg, 19 μmol) and sodium nitrite (2.62 mg, 38 μmol) were added to an acetic acid solution (380 μl) of 2,2-dimethyl-5-phenylpentane-1,3-diol (39.6 mg, 0.190 mmol), and the mixture was stirred at room temperature (25° C.) under atmospheric pressure for 18 h. The mixture was diluted with diethyl ether, and rapidly cooled with saturated sodium bicarbonate and 20% sodium thiosulfate. The solution was then extracted with diethyl ether. The organic layer was dried over sodium sulfate, and concentrated under reduced pressure. The residue was then purified by silica gel column chromatography to give hydroxyaldehyde (35.4 mg, 90%).
3-Hydroxy-2,2-dimethyl-5-phenylpentanal: 1 H-NMR (400 MHz, CDCl 3 ) δ 9.51 (s, 1H), 7.36-7.17 (m, 5H), 3.77 (d, J=9.7 Hz, 1H), 2.96 (ddd, J=14.0 Hz, 9.7 Hz, 5.4 Hz, 1H), 2.67 (ddd, J=14.0 Hz, 9.2 Hz, 7.3 Hz, 1H), 2.29 (br s, 1H), 1.83-1.64 (m, 2H), 1.11 (s, 3H), 1.04 (s, 3H); 13 C-NMR (100 MHz, CDCl 3 ) δ 206.6, 141.6, 128.3, 125.8, 74.0, 50.3, 33.0, 32.5, 18.8, 16.3; IR (neat, cm −1 ): 3466, 2959, 2871, 1721, 1455, 1075, 1046, 700; MS m/z 188 (M + -H 2 O), 72 (100%); HRMS (EI) calcd for C 13 H 16 O 188.1201 (M + -H 2 O), found 188.1189.
INDUSTRIAL APPLICABILITY
The present invention provides an oxidation catalyst that is more active than the existing oxidation catalyst TEMPO, and is more selective than AZADO and 1-Me-AZADO in the selective oxidation reaction of primary alcohol.
The DMN-AZADO according to the present invention is applicable to primary alcohol selective oxidation reactions, contributing to simplifying the syntheses of high value-added organic compounds such as pharmaceuticals, pharmaceutical raw materials, agricultural chemicals, cosmetics, and organic materials. | An organocatalyst for oxidizing alcohols in which a primary alcohol is selectively oxidized in a polyol substrate having a plurality of alcohols under environmentally-friendly conditions. The organic oxidation catalyst has an oxygen atom bonded to a nitrogen atom of an azanoradamantane skeleton and at least one alkyl group at positions 1 and 5. The oxidation catalyst has higher activity than TEMPO, which is an existing oxidation catalyst, in the selective oxidation reaction of primary alcohols, and better selectivity than AZADO and 1-Me-AZADO. This DMN-AZADO can be applied to the selective oxidation reaction of primary alcohols that contributes to shortening the synthesizing process for pharmaceuticals, pharmaceutical raw materials, agricultural chemicals, cosmetics, organic materials, and other such high value-added organic compounds. | 2 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. patent application Ser. No. 10/165,851 filed Jun. 7, 2002 (now U.S. Pat. No. 6,781,120) which claims the benefit of U.S. Provisional Patent Application Ser. No. 60/296,850 filed Jun. 8, 2001 entitled “Method For Enhancement Of Electron Spectrometer Operation Using Maximum Likelihood Spectral Estimation Techniques,” the entire teachings of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates generally to a method for manufacturing a grid for gating a stream of charged particles.
[0003] Certain types of particle measurement instruments, such as ion mobility spectrometers, can require a gating device for turning on and off of a flowing stream of ions or other charged particles. This is accomplished by disposing a wire grid within the path of the ions; alternately energizing or de-energizing the grid then respectively traps the ions or allows them to flow.
[0004] Certain types of time of flight spectrometers, such as those described in the paper by Vlasak, P. R., et al., entitled “An interleaved comb ion deflection gate for m/z selection in time-of-flight mass spectrometery,” in Review of Scientific Instruments, Vol. 67, No. 1, January 1996, pp. 68-72, also utilize a gating device.
[0005] The most common methods for accomplishing this use an interleaved comb of wires also referred to as a Bradbury-Nielson Gate. Such a gate consists of two electrically isolated sets of equally spaced wires that lie in the same plane and alternate in potential. When a zero potential is applied to the wires relative to the energy of the charged particles, the trajectory of the charged particle beam is not deflected by the gate. To deflect the beam, bias potentials of equal magnitude and opposite polarity are applied to the two sets of wires. This deflection produces two separate beams, each of whose intensity maximum makes an angle alpha with respect to the path of the un-deflected beam.
[0006] One approach to manufacturing a gating grid is disclosed in U.S. Pat. No. 4,150,319 issued to Nowak, et al. In this technique, a ring-shaped frame is fabricated from a ceramic or other suitable high temperature material. The two sets of wires are wound or laced on the frame. Each set of wires is actually a single, continuous wire strand that is laced back and forth between two concentric series of through-holes that are accurately drilled around the periphery of the frame.
[0007] Another technique for manufacturing such a gate is described in U.S. Pat. No. 5,465,480 issued to Karl, et al. In this approach, the gating grid elements are produced from a thin metal foil by cutting or etching the foil to produce the grid structure. The gird elements are connected to side electrodes in a desired pattern to produce the two sets of wires. The foil grid structure is made mechanically stable by attaching it to an insulating support member. After the then-rigid grid structure is affixed to the insulating support member, the grid elements are selectively severed from the side electrodes to form the interdigitated grid.
[0008] Yet another approach for manufacturing such a grid is described in the paper by Kimmel, J. R., et al., entitled “Novel Method for the Production of Finely Spaced Bradbury-Nielson Gates,” in Review of Scientific Instruments, Vol. 72, No. 12, December 2001, pp. 4354-4357. In this method, a guide is first manufactured out of a polymer block. The guide has a series of evenly spaced parallel grooves. A hole is drilled through the center of the polymer block; this hole eventually carries the ion beam. The machined polymer block is mounted on an insulated face of an H-shaped portion of a single sided, copper clad circuit board, with the grooves running from top to bottom of the H. The polymer-to-copper clad contacts are then fixed using an epoxy. Two small portions of the single sided copper clad board are fixed on the bottom side of the polymer in the region where the block extends over the center bar of the H-shaped copper frame.
[0009] A hand cranked, rotating screw is then used as a weaving instrument. In particular, a gold-plated tungsten wire runs from a spool over a directing screw and is coupled to the hand cranked screw by a belt. The loose end of the wire is then fixed such as by using an epoxy. A weight is hung from the wire between the directing screw and the spool in order to provide a constant tension on the wire.
[0010] Beginning at one side of the center hole, the hand crank is turned, which rotates the frame, drawing the thread from the spool. While watching through a microscope, an assembler feeds a first wire set through alternating grooves in the surface of the polymer and around the frame, making sure to touch both contacts on each pass. After winding the wire across the entire width of the opening, the wire is bound to both copper contacts on either side of the hole using an epoxy. A razor blade is then used to remove the segment of the wire between the two contacts on the side of the frame opposite the polymer.
[0011] Using the same procedure as for the first wire set, a second wire set is then wound through the grooves located between the wires of the first set. The ends of the wires are then cut, leaving wire only on the polymer side of the frame.
SUMMARY OF THE INVENTION
[0012] There are deficiencies with each of the prior art approaches to fabricating such grid elements. For example, the technique described in the Nowak patent relies upon the precise placement of two sets of aligned holes on either side of a ring. Since it uses a single strand of wire which is hand woven through the holes, it does not take into consideration the need to assure a constant mechanical tension among wires in the assembled grid. Unless the mechanical tension is relatively uniform across all wires of the grid, undesirable artifacts are introduced by irregular tension. For example, at elevated operating temperatures, the larger coefficient of expansion of the metal as compared to the ceramic support could also cause the wires to sag, potentially shorting them out if they are not properly pre-tensioned. Likewise, the imprecise nature of tensioning the wire by hand often leads to wires that are not uniformly parallel. Therefore, the field normal to the grid does not decay as rapidly as theoretically possible.
[0013] Additionally, for high speed applications, the phase delays resulting from propagation of the bias current along the single continuous strands from the contact point may cause the ions to experience a deflection at different times, depending upon where they happen to be in the beam path.
[0014] Furthermore, because the frame in Nowak is circular, the individual wires are of different lengths. This means that each wire then presents a different characteristic impedance to current flowing through it. This likewise introduces different effects to different ions, depending upon where they happen to be in the beam path. Thus, ions traveling the center of the beam are subjected to a different electrical force than ions traveling in the outer portion of the beam where the grid wires are shorter.
[0015] Finally, the required thickness of the support structure in Nowak limits how closely two grids can be placed with respect to each other.
[0016] Kimmel's approach, similar to Nowak's, weaves a single thread around a frame. It also requires the assembler to carefully feed the wire through one of the alternately spaced grooves. The individual wires in the set are then bound to the copper contacts using epoxy. The method of machining a polymer block to small tolerances of 0.005 mm for each grid wire can require relatively expensive machine tools.
[0017] Furthermore, if the single wire breaks during winding or any part of the process one must start over again, from the beginning, to restring the wire. The assembly procedure envisioned is apparently so tedious that Kimmel himself estimates that it takes approximately three hours to manufacture a single gate.
[0018] The presence of large amounts of insulating polymer surfaces near the beam path may cause substantial charging effects which could be detrimental to the operation of the gate, particularly for gating low energy electrons. Furthermore, a device formed from a polymer with epoxy bindings may not survive the high expected operating temperatures of some applications such as ion mobility spectroscopy.
[0019] The process described in the Karl patent does provide a grid having wires with uniform tension. A separate support structure for the foil-like grid element is be fabricated from tubes and the thin metal foil must then be attached to the grid structure. This geometry is apparently convenient for ion mobility spectroscopy, but does not allow slit or apertures to be spaced closely on both sides. While the rapid charging and discharging of the gate is facilitated by the bus-like structure, the “ears” extending beyond the gate are likely to produce strong reflections which would be detrimental for ultra high speed operation such as in electron TOF spectroscopy. Finally, the rotational symmetry of the Karl device is not convenient for accurate alignment of the grid wires with respect to apertures placed before or after the gate.
[0020] The present invention seeks to overcome these deficiencies with a design for a gating electrode and method for fabricating it as follows.
[0021] The grid is fabricated using a substrate formed of a ceramic, such as alumina. The substrate serves as a rectangular frame for a grid of uniformly spaced wires stretched across a center rectangular hole. On either side of the frame, nearest the hole, a line of contact pads are formed.
[0022] Adjacent the line of contact pads, on the outboard side thereof, are formed a pair of bus bars. The contact pads and bus bars provide a way to connect the wires into the desired two separate wire sets of alternating potential. Specifically, the pads formed on each side of the opening serve as contact points for one end of each wire. The pads are alternately and evenly spaced along each side of the opening, inboard of the bus bars. In a preferred embodiment, the pads may be spaced, for example, down each side of the center opening. The pads serve as electrically open termination points for the ends of the grid wires that are not connected to the bus bars.
[0023] The bus bars serve to interconnect wires that belong to a given wire set.
[0024] Steps are also performed for fabrication of the grid according to the invention. First, the support frame is made from an insulating substrate such as alumina. A rectangular shaped center hole is formed in the alumina or other ceramic. The support frame, which may be laser cut, for example, may be one inch by one inch with a one-half inch by one-half inch hole placed in its center.
[0025] Metal film is then deposited on the surface of both sides of the ceramic through vacuum evaporation of gold, using chrome as an adhesion layer, for example. The metal film is then patterned on the front side to form the conducting elements on either side of the hole. These conducting elements include the ground plane, left and right bus bars, and pad elements. The desired metalization pattern can be defined by a photo-resist and chemical-etch process, a lift-off process, or by using a physical mask during an evaporation. The metal on the back side remains, as deposited, to serve as a ground plane.
[0026] In the next sequence of steps, the grid wires are attached to the fabricated frame. In this process, a spool of wire is provided that will serve as the grid wires. In one preferred embodiment, the wire is a 0.002-inch diameter gold wire and the spacing of adjacent wires is 0.020-inch, to achieve a transmission of approximately 90%. A tensioner is provided to place constant tension on the wire. The spool, for example, may be arranged on a mandrel, and a hanging weight attached to the end of a string wrapped around the mandrel. The weight is adjusted to tension the wire at a specific chosen value less than the yield strength of the wire.
[0027] The free end of the wire is then fixed to a wire clamp so that it may be precisely located with respect to the tip of a parallel gap welder. The frame is then moved so that the first pad on the left hand side of the frame is located under the tip. At this point, the wire is bonded to the center of the pad. The parallel gap welder provides a relatively immediate bond of the wire to the pad. The assembler can then pull the free end of the wire to break it free from the bond, or wait until later to cut off the free ends of all of the wires.
[0028] The wire is then bonded to the bus bar on the right hand side of the frame. The free end of the wire is then pulled to break it free from this bond pad, or it is cut.
[0029] In a next step, the frame is moved so that the bus bar on the left is located under the tip and the wire is centered between the first and second pad. The wire is then bonded to the left bus bar.
[0030] The free end of the wire is then pulled to break it free from the bond and the wire is then bonded to the center of the next available pad on the right hand side of the frame. The free end of the wire is then pulled to break the wire free from the bond, or the wire is cut at this point.
[0031] The process is then repeated to produce a parallel grid of uniformly spaced and tensioned wires at a uniform distance apart from each other. By individually fixing the free end of the wire, such as by parallel gap welding it to either the pad or the bus bar on one side of the frame while keeping the wire at a constant tension and then bonding it to the opposite side of the frame, absolute consistency in the tension applied to each wire of the entire grid is assured.
[0032] This wiring process can proceed by hand, by using a mechanical stage to accurately and easily position the assembly with respect to the tip of the welder. It can also be a computer controlled process similar to that used in the wire bonding of semiconductor devices into packages.
[0033] Fabricating the bus bar and termination pads as a patterned metal film on a ceramic substrate also produces an advantage that prior art techniques do not. In particular, the bus bars and wires form a characteristic impedance that is presented to the electronic circuitry that drives the grid voltage. By keeping the bus bars at a controlled tolerance in terms of their thickness and width on the ceramic substrate, as well as the size of the pads, the characteristic impedance of the wire grid assembly and, in particular, the bus bar itself, can be assured to match that of the driver circuitry. This, in turn, further eliminates another inconsistency with prior art approaches.
[0034] The method also allows fabrication of gates with wires several times smaller in diameter than that utilized by other methods.
[0035] The square shape of the center hole allows precise alignment of the orientation of the grid wires.
[0036] The metalized surfaces of the ceramic reduce the possibility of surface charge build-up during operation, since both the “front” as well as the “back” are metalized.
[0037] The wire can be selected to decrease the thermal coefficient of expansion of the wire relative to the ceramic, for example, using Alloy 46 .
[0038] A grid constructed according to the invention also lends itself to implementation in quadrupole and higher order multipole structures. For example, two grids may be placed face to face—in this case the spacing between the grids needs to be similar to the spacing between the wires. Nowak and similar prior art approaches that use relatively thick frames do not lend themselves to implementation in such multipole structures.
[0039] For example, the bus bars and the wires can be placed symmetrically with respect to a centerline of the support frame, such that by placing a second grid over the first, the bars of the same polarity are opposing each other (to avoid arcing between +V and −V) while wires of opposite polarity were opposing each other so as to produce a quadrupole field. The quadrupole field has a higher deflecting power for the same applied voltage, which reduces energy corruption effects.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] 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.
[0041] FIG. 1 is a plan view of the results of a first step of fabricating the frame in which the center hole has been cut.
[0042] FIG. 2 is a view of the frame after a second step showing metalization patterns for ground plane bus bar and pads.
[0043] FIG. 3 is a plan view of the complete grid.
[0044] FIG. 4 illustrates a portion of process for maintaining constant tension on the wire.
[0045] FIGS. 5-8 show how the frame is moved with respect to the bonder tip during assembly.
DETAILED DESCRIPTION OF THE INVENTION
[0046] A description of preferred embodiments of the invention follows.
[0047] The present invention can be used to manufacture an interleaved comb of wires known as a Bradbury-Nielson Gate. Such a gate consists of two electrically isolated sets of equally spaced wires that lie in the same plane and alternate in applied voltage potential.
[0048] These gates are generally recognized as having a much smaller effective field size than the more commonly used deflection plates. They can, for example, be used to modulate ion beams in time-of-flight mass spectrometers (TOF-MS), to achieve mass-to-charge selection. Such gates are also commonly used in ion mobility mass spectrometers to regulate the injection of ion packets into a drift tube.
[0049] They have also been applied to Hadmard time-of-flight mass spectrometers to modulate the source of ion beam with a pseudorandom sequence of on and off pulses. Because the detected signal is then a convolution of the TOF mass spectra, the signal can be deconvoluted by again applying the pseudorandom sequence to yield the single mass spectrum. The resulting resolution of the instrument depends on the modulation switching time, that is, how fast the necessary voltage can be applied to the wires.
[0050] FIG. 1 is an illustration of a frame 10 utilized for providing a substrate for a wire grid manufactured according to the present invention. The frame 10 consists of an insulating rigid material, typically a ceramic such as alumina. The frame 10 may have an exterior dimension of, for example, one inch by one inch, with a thickness of 0.015 inch. A hole 12 is cut in the center of the substrate material; here, the hole is approximately 0.5 inch by 0.5 inch. The hole may be cut by using a laser.
[0051] The next step is to deposit a metal film of a desired pattern. One such pattern is shown in FIG. 2 . The pattern includes, for example, ground plane areas 14 - 1 , 14 - 2 , 14 - 3 , 14 - 4 (collectively, the ground plane areas 14 ), bus bars 16 -L, 16 -R, and pads 18 -L- 1 , 18 -L- 2 , . . . 18 -L-n, and 18 -R- 1 , 18 -R- 2 , . . . 18 -R-m.
[0052] The metalization pattern can be manufactured by depositing a metal film on the surface of the ceramic substrate. Numerous techniques are known for accomplishing this. In a preferred embodiment, this can be by vacuum evaporation of gold with a chrome adhesion layer. The metalization patterns can then be defined, for example, by a photo resist and chemical etch process.
[0053] The ground plane areas 14 generally surround the periphery of the frame 10 . They serve to electrically define the region surrounding the grid of wires that are eventually strung across the hole 12 .
[0054] As will be understood shortly, the bus bars 16 provide a way to electrically connect each of the two sets of grid wires. Bus bar 16 -L, located on the left side of the frame, will be used to interconnect wires that terminate on the right side of the frame. Likewise, bus bar 16 -R, located on the right side of the frame, is used to interconnect wires that terminate on the left side of the frame.
[0055] The pads 18 provide a place to terminate one end of the respective wires. A first set of pads 18 -L- 1 , 18 -L- 2 , . . . 18 -L-n run along the left side of the frame adjacent the center hole 12 . A second set of pads 18 -R- 1 , 18 -R- 2 , . . . 18 -R-n run along the right side of the frame, also adjacent the hole 12 . Note that the pads 18 are defined such that metal is etched around the periphery on all four sides thereof. This isolates the pad 18 -L- 1 from the pad 18 -L- 2 , for example, providing an electrically open termination point.
[0056] The spacing of the pads 19 in a vertical direction is chosen to be approximately twice the desired ultimate spacing of the wires. For example, if it is desired to produce a parallel grid of two sets of uniformly spaced and tensioned wires at a grid spacing of 0.020 inches apart, the spacing between the pads 18 -L on the left side of the frame should be 0.040 inches. A similar set of pads 18 -R run along the right hand side of the hole 12 and serve to terminate the second set of wires; whereas the first set of pads 18 -L terminate the first set of wires.
[0057] Please note that the pads 18 -L on the left side of the frame are offset in vertical orientation with respect to the pads 18 -R on the right side of the frame. This offset is equal to the desired spacing between the grid wires; that is, 0.020 inches in the preferred embodiment. This provides a series of spaces 20 -L- 1 . . . 20 -L-n on the left side of the frame, and, similarly, 20 -R- 1 . . . 20 -R-m on the right hand side of the frame. As will be understood shortly, these spaces are important in that they provide a way for the wire to pass by a pad and connect to a bus bar without shorting to an adjacent one of the pads 18 on the side opposite in which it originated.
[0058] After fabricating the metalization pattern on the frame 10 , a next sequence of steps is used to attach grid wires across the hole 12 . Specifically, each grid wire is stretched from one side of the frame across to the other. One end of each grid wire ends up being attached to a section of a bus bar 16 ; the other end of each grid wire is attached to one of the pads 18 .
[0059] Turning more specifically now to FIG. 3 , there is shown a drawing of the completed grid. Note that the grid wires 22 have been strung across the hole. Each wire connects to a bus bar on one end and a pad on the other end. Specifically, the first set of the grid wires 24 - 1 have one end which is connected to a respective one of the termination pads 18 -L on the left side of the frame. Each of the wires in this first set 24 - 1 then connects to the common bus bar 16 - 2 on the right hand side of the frame. A second set of the grid wires 24 - 2 have a first end that connect to the common bus bar 16 -L and terminate at one of the termination pads 18 -R located on the right side of the frame.
[0060] A diagram illustrating a configuration for attaching the wires in this desired form is shown in FIG. 4 . Provided are a wire spool 50 and tensioner, including mandrel 52 , pulley 54 , string 64 , and weight 56 . A welding tip 62 such as from a parallel gap welder is also provided.
[0061] The wire 58 , in a preferred embodiment, is a gold wire of a diameter of 0.002 inches.
[0062] The tensioner is provided by mounting a spool on the mandrel 52 . A respective first end of the string 64 is wrapped around the mandrel 52 and is then fed across one or more pulleys 54 to a weight 56 . The weight 56 is allowed to hang freely. The amount of the weight is chosen to adjust the tension on a section of the wire 58 that is then stretched across the top portion of the frame 40 .
[0063] A x-y positioning stage 68 is provided which can precisely locate the frame in two orthogonal directions.
[0064] An assembly process can now be described with reference to FIG. 4 , which is a side view of one initial step, while also referring to FIGS. 5-8 , which are views taken from above during assembly. A center line 70 reference in FIGS. 5-8 illustrate how the frame can be positioned by an x-y positioning stage 68 —that is movable with respect to the welding tip 62 , to permit attachment of the wires to the bus bars 16 and pads 18 .
[0065] In a first assembly step, the free end of the wire is taken from the spool 50 and lead through a guide 66 , terminating in a wire clamp 60 . The wire clamp 60 provides a way to locate the wire 58 with respect to the tip 62 .
[0066] In a next step to produce a grid, the frame 40 is moved so that the tip 62 is centered on the first pad 18 -L- 1 on the left side of the frame, as shown in FIG. 5 . Welding tip 62 is then placed in close contact with the pad 18 -L- 1 to bond the wire to the center of pad 18 -L- 1 . A portion of the wire to the left of the pad is then pulled or bent to break it free from the bond. However, it should be understood that these free ends of wire, after having been released from the clamp, may be left in place and cut off later, such as with a cutting tool.
[0067] A next step is used to attach this new wire to the right side of the grid is then performed, as shown in FIG. 6 . In this step, the stage 68 is moved so that the bonding tip 62 is on the right side of the frame 40 . The wire, having now been attached to the pad 18 -L- 1 on the left side of the frame, is to be attached to the bus bar 16 -R on the right side of the frame. The frame 40 is moved to the left until the tip 62 is centered on the bus bar 16 -R. The frame 40 is not moved in the orthogonal direction, taking care to ensure that the wire passes through the space 20 -R- 1 , without shorting to any adjacent pads 18 -R on the right side of the frame. See FIG. 7 . The wire 58 is then attached to the bus bar 16 -R on the right side of the frame. This attachment is secured by parallel gap welding.
[0068] The frame 40 is then moved farther to the left as also shown in FIG. 7 , the clamp 60 engaged on the wire 58 , and the wire 58 is then pulled to break it free from the bond, or it is cut.
[0069] The next step is to fabricate a second wire section 23 , that is a wire that terminates at a bus bar 1 6 -L on its left side and a pad 18 -R- 1 on its right side. The frame is moved, as shown in FIG. 8 , precisely in the orthogonal direction by, for example, a screw mechanism on the stage 68 with an attached caliber mechanism to precisely measure the location in the orthogonal direction. The frame is moved in the orthogonal direction a distance equal to the grid wire spacing which is one half the distance between adjacent pads. The frame 40 is then moved until the tip 62 is centered on the bus bar 16 -L on the left, similar to FIG. 5 . Again, the frame 40 is not moved in the orthogonal direction ensuring that the wire passes through the space 20 -L- 1 between the first pad 18 -L- 1 and second pad 18 -L- 2 on the left side of the frame so that it does not short to either of those pads. The wire is then bonded to the bus bar 16 -L on the left side of the frame. The free end of the wire is then pulled to break it free from the bond, or left to be cut off later on.
[0070] The frame 40 is then moved until the tip 62 is centered on the pad 18 -R- 1 on the right side of the frame. After being bonded with the parallel gap welder, it is cut from the bond or otherwise broken.
[0071] This procedure is then repeated a number of times, to produce a parallel grid of two sets of wires that are uniformly spaced and tensioned.
[0072] It can be seen now how the bus bars 16 -L and 16 -R provide a convenient way to interconnect the wires associated with the respective one of the two sets. The inventors have also recognized that the bus bars 16 should be carefully chosen in their specific width 60 and film depth. Specifically, the bus bars 16 represent (as any electrical circuit) an impedance to the circuitry that drives the respective wire grid with the modulation voltage. The width of gold wires represent an electrical impedance and thus act in a way that is quite similar to a microstrip transmission line. A respective characteristic impedance of the bus bar and wire grid structure can thus be determined to optimize transmission of the electrical signal from the modulation circuitry to the grid. The width of the bus bars 16 is then chosen to match the characteristic impedance. In a preferred embodiment with a characteristic design characteristic impedance of 50 ohms and dimensions of the wire grid stated above, the width of the bus bar 16 is approximately 0.017 inches when the bus bar length is approximately 1 inch. The metalization pattern may be controlled such that the depth is about 0.010 mm.
[0073] It would also be convenient to pattern the gold such that surface mount resistors can be placed between the bus bars and the ground plane region, so as to provide on-board termination of the transmission line signals, especially for low voltage applications where total power dissipation is not a problem.
[0074] While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims. | A technique for providing a grid for a gate such as utilized in gating a stream of ions or other particles in a spectrometer instrument. The grid of wires may, for example, be a so-called Bradbury-Nielson Gate that consists of a set of two electrically isolated sets of equally spaced wires that lie substantially in the same plane and alternate in potential. The method utilized to provide is to first fabricate a frame of an insulating substrate having a hole and depositing metal film patterns such that conductive portions are formed on either side of the hole. Conductive portions on either side form a series of terminating pads on the portion of the substrate closest to the hole and a bus bar. Grid wires are then formed by stretching a section of wire with desired constant tension across the hole and bonding the ends of the wire to a respective one of the pads on one side and bus bar on the other side. The method provides a rapid, inexpensive way to fabricate such modulating devices. | 8 |
BACKGROUND OF THE INVENTION
In rotary regenerative heat exchange apparatus a mass of heat absorbent element commonly comprised of packed element plates is first positioned in a hot gas passageway to absorb heat from hot gases passing therethrough. After the plates become heated by the hot gases they are moved to a passageway for a cooler fluid where the then hot plates transmit their heat to cooler air or other gas passing therethrough.
The heat absorbent material is carried in a rotor that rotates between the hot and cool fluids, while a fixed housing including sector plates at opposite ends of the rotor is adapted to surround the rotor. To prevent mingling of the hot and cold fluids, the end edges of the rotor are provided with flexible sealing members that rub against the adjacent surface of the rotor housing and resiliently accommodate a limited degree of "turndown" or other distortion caused by mechanical loading and thermal deformation of the rotor.
To permit turning the rotor freely about its axis, certain minimum clearance space between the rotor and adjacent rotor housing is required, however, excessive clearance is to be avoided because it will dictate excessive leakage. However, under conditions marked by a rapid increase of temperature that is accompanied by excessive expansion of the rotor and of the rotor housing, excessive leakage may develop and a lowered effectiveness may result.
The expansion of the rotor and adjacent rotor housing assumes the greatest proportions directly adjacent the inlet for the hot fluid where an increase of temperature is maximum. An arrangement that compensates for a loss of sealing effectiveness at this, the "hot" end of a rotor, is shown by U.S. Pat. No. 3,786,868 where a plane sector plate is pivoted about a fulcrum carried by the housing. Although such an arrangement is partially effective, excessive fluid leakage between the sector plate and the rotor still continues because the sector plate distorts as a plane while the rotor distorts in a dished configuration.
SUMMARY OF THE INVENTION
In accordance with my invention, I therefore propose to provide a unique actuating device that forces the sector plate to assume a dished configuration that corresponds closely to the dished configuration of the adjacent face of the rotor whereby there will be a minimum clearance space that permits a minimum of leakage therebetween.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete understanding of my invention may be realized by referring to the following description in conjunction with the accompanying drawings in which:
FIG. 1 is a cross section of a rotary regenerative heat exchanger involving the present invention,
FIG. 2 is a side elevation of the invention,
FIG. 3 is a modified form of the invention that may be used with any given actuator,
FIG. 4 shows a modified form that utilizes an electric sensing device and actuator for carrying out the invention,
FIG. 5 is a plan view of the device shown in FIG. 2,
FIG. 6 is a plan view of the device shown in FIG. 3,
FIG. 7 is a cross section of the sector plate arrangement as seen from line 7--7 of FIG. 5,
FIG. 8 is a cross section of a modified sector plate as viewed from line 8--8 of FIG. 6, and
FIG. 9 is a diagrammatic representation of a rotary regenerative heat exchanger having rotor "turndown".
DESCRIPTION OF THE PREFERRED EMBODIMENT
The heat exchanger includes a vertical rotor post 6 and a concentric rotor shell 8 with a space therebetween that is filled with a mass of permeable heat absorbent element 12 in order that the heat absorbent material that is carried by a rotor and rotated slowly about its axis by a motor 23 may absorb heat from a heating fluid and transfer it to a fluid to be heated.
The hot gas or other heating fluid enters the heat exchanger through an inlet duct 14 and is discharged after traversing the heat absorbent material carried by the rotor 15 through an outlet duct 16. Cool air or other fluid to be heated enters the heat exchanger through an inlet duct 18 and is discharged after flowing over the heated material 12 through an outlet duct 20 to which an induced draft fan is usually connected. After passing over the heated material the cool air absorbs the heat therefrom and is then directed to its place of ultimate use.
A cylindrical housing 22 encloses the rotor in spaced relation thereto to provide an annular space 25 therebetween. Sector plates 28 intermediate ends of the rotor and the adjacent housing structure lie intermediate spaced apertures that admit and discharge the streams of gas and air. In order that streams of gas and air do not bypass the rotor, it is customary to affix flexible sealing means to an end edge of the rotor to confront the adjacent surface of the rotor housing and preclude the flow of fluid therebetween.
In a standard heat exchanger of the type defined herein, the hot gas enters the top of the heat exchanger and transfers its sensible heat to the heat absorbent material of the rotor before it is discharged as a cooled gas through outlet duct 16. Inasmuch as the inlet for the cool air lies at the bottom of the heat exchanger adjacent the cooled gas, the bottom end of the heat exchanger is called the "cold" end while that lying adjacent the hot gas inlet is termed the "hot" end of the rotor. It will be apparent that the "hot" end of the rotor will be subject to maximum temperature variation, while the "cold" end of the rotor will be subjected to a lesser amount.
Thus maximum thermal expansion of the rotor housing and the adjacent end of the rotor occurs at the top or "hot" end of the rotor, and in response to a resulting thermal gradient assumes a shape similar to that of an inverted dish shown by FIG. 9 and commonly termed rotor "turndown". The result of this relative thermal expansion of the rotor and the surrounding rotor housing is to increase the clearance space therebetween and substantially increase fluid leakage between the relatively movable parts.
A lower support bearing 32 is mounted rigidly on independent structure and is adapted to support the central rotor shaft 6 for rotation abouts its vertical axis. As the rotor and rotor shaft are heated, they expand axially through a guide bearing 36 that precludes radial displacement of the rotor shaft. Thus the upper portion of the rotor shaft moves upward, while excessive radial expansion of the rotor at the "hot" end of the rotor causes rotor "turndown" and an increase of clearance space between the rotor and rotor housing.
The present invention provides a sealing arrangement at the "hot" end of the rotor wherein the sector plate 28 that lies adjacent thereto is forced to assume a dished configuration that conforms essentially to the adjacent face of the rotor wherein the radial inboard end of the sector plate remains essentially flat, while the radial outboard end of the sector plate is forced to assume a radius of relatively small configuration.
To carry out this forced bending of the sector plate I provide an axially disposed hanger 42 that is subject to axial movement of the rotor post as effected by thermal expansion thereof whereby the hanger 42 will move up or down in accordance with its change of temperature. The lower end of hanger 42 supports the inboard end of frame 44 that surrounds sector plate 28 and extends radially outward to the periphery of the rotor. The radial inboard end of the frame 44 is carried by the hanger 42, while the inboard end of the surrounding sector plate is attached as by welding to the adjacent portion of the sector shaped frame. The radial outboard end of frame 44 is supported in fixed relation to the adjacent housing structure by a hanger 46, whereby the inboard end of the sector plate is integral with the frame, while the outboard end of the sector plate is axially movable with respect thereto. Sealing means 47 comprising an arrangement of overlapping leaves could be arranged along the radial edges of the sector plate and/or the adjacent surface of the frame 44 to preclude fluid flow through the space therebetween in the manner shown by FIG. 7.
Inasmuch as a rise of temperature causes the rotor to "turndown" in accordance with predetermined principles, the same increase of temperature is utilized to provide an actuating force that moves the outboard end of the upper sector plate into a similar configuration so there may be a minimum of fluid leakage therebetween.
An actuating lever 52 that extends radially outward over sector plate 28 is supported by a fulcrum 54 that is in turn carried by the fixed housing structure. The radial inboard end of the lever 52 is pivotally attached to the hanger 42, while the outboard end thereof is attached by means of a pivotal linkage 56 to the adjacent end of the sector plate 28 whereby axial movement of hanger 42 will produce an opposite movement of the sector plate at linkage 56.
Inasmuch as the sector plate 28 is rigidly attached to the surrounding frame member 44 and stiffeners 47 are provided at the inboard end thereof, the radial outer end of the sector plate is free to move up or down, and actuation by linkage 56 produces a dished configuration of the sector plate that may be made to substantially conform to thermal distortion of the rotor.
The degree of bend at the unsupported end of each sector plate may be varied to conform to the degree of bend on the adjacent face of the rotor by providing stiffeners 44 to the upper surface of the sector plate 28 and moving the fulcrum 54 radially in or out on the fixed housing structure.
A modified arrangement shown in FIG. 3 discloses a sector plate 28 welded to the inner end of a radial support beam 62. The radial beam 62 is carried at its inboard end by the hanger 42 while the outboard end thereof is connected to a "T" shaped member 45 that is in turn carried by housing 22 independent from the sector plate whereby the radial outer end of the sector plate 28 is always free to conform to the actuation of linkage 56. Radial ribs 64 are affixed to the sector plate 28 and adapted to bear against the outer surface of beam 62 sufficient to preclude relative movement in any but an axial direction. Similarly a radial diaphragm or wall is carried by fixed housing structure at the end of the rotor to laterally bear against the relatively movable ribs 68 on the surface of sector plate 28 in a rubbing relationship and thus permit axial movement therebetween. Inasmuch as there is normally a difference in static pressure between the air and the gas streams, contact between the diaphragm 66 and ribs 68 is continuously assured.
Although the invention has been disclosed with reference to a mechanical (lever) actuator, there would be no invention in providing a motor and drive mechanism 72 to drive the actuator 56 at the end of the sector plate. Limit switches 74 responsive to movement of the actuator 56 control movement of the motor-actuator 72 that determines movement of the actuator up or down, while limit switch 74 at the radial opposite end of the sector plate simply controls an "off-on" switch that actuates the drive motor.
It is therefore intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and limited only by the terms of the accompanying claims. | Rotary regenerative heat exchange apparatus having a rotor of heat absorbent element that is alternately exposed to a hot and a cold fluid in order that heat absorbed from the hot fluid may be transferred to the cold fluid. The rotor is surrounded by a housing including a sector plate at opposite ends of the rotor that separates the hot and cold fluids. The sector plate is forcefully deflected to conform to normal "turndown" experienced by the rotor in order that there will be minimum leakage of fluid through the space therebetween. | 5 |
TECHNICAL FIELD
The present invention relates to Session Initiation Protocol message handling in an IP Multimedia Subsystem (IMS), and in particular to a method and apparatus for allowing a SIP Application Server to identify the role of a SIP user associated with a SIP message.
BACKGROUND
IP Multimedia services provide a dynamic combination of voice, video, messaging, data, etc. within the same session. By growing the number of basic applications and the media which it is possible to combine, the number of services offered to the end users will grow, and the inter-personal communication experience will be enriched. This will lead to a new generation of personalised, rich multimedia communication services, including so-called “combinational IP Multimedia” services which are considered in more detail below.
IP Multimedia Subsystem (IMS) is the technology defined by the Third Generation Partnership Project (3GPP) to provide IP Multimedia services over mobile communication networks. The main IMS specification is TS24.229. IMS provides key features to enrich the end-user person-to-person communication experience through the use of standardised IMS Service Enablers, which facilitate new rich person-to-person (client-to-client) communication services as well as person-to-content (client-to-server) services over IP-based networks. The IMS makes use of the Session Initiation Protocol (SIP) to set up and control calls or sessions between user terminals (or user terminals and application servers). The Session Description Protocol (SDP), carried by SIP signalling, is used to describe and negotiate the media components of the session. Whilst SIP was created as a user-to-user protocol, IMS allows operators and service providers to control user access to services and to charge users accordingly.
FIG. 1 illustrates schematically how the IMS fits into the mobile network architecture in the case of a GPRS/PS access network. Call/Session Control Functions (CSCFs) operate as SIP proxies within the IMS. The 3GPP architecture defines three types of CSCFs: the Proxy CSCF (P-CSCF) which is the first point of contact within the IMS for a SIP terminal; the Serving CSCF (S-CSCF) which provides services to the user that the user is subscribed to; and the Interrogating CSCF (I-CSCF) whose role is to identify the correct S-CSCF and to forward to that S-CSCF a request received from a SIP terminal via a P-CSCF.
A user registers with the IMS using the specified SIP REGISTER method. This is a mechanism for attaching to the IMS and announcing to the IMS the address at which a SIP user identity can be reached. The user receives a unique URI from the S-CSCF that it shall use when it initiates a dialog. In 3GPP, when a SIP terminal performs a registration, the IMS authenticates the user, and allocates an S-CSCF to that user from the set of available S-CSCFs. Whilst the criteria for allocating S-CSCFs is not specified by 3GPP, these may include load sharing and service requirements. It is noted that the allocation of an S-CSCF is key to controlling (and charging for) user access to IMS-based services. Operators may provide a mechanism for preventing direct user-to-user SIP sessions which would otherwise bypass the S-CSCF.
During the registration process, it is the responsibility of the I-CSCF to select an S-CSCF if one is not already selected. The I-CSCF receives the required S-CSCF capabilities from the home network's Home Subscriber Server (HSS), and selects an appropriate S-CSCF based on the received capabilities. [It is noted that S-CSCF allocation is also carried out for a user by the I-CSCF in the case where the user is called by another party, and the user is not currently allocated an S-CSCF.] When a registered user subsequently sends a session request (e.g. SIP INVITE) to the IMS, the request will include the P-CSCF and S-CSCF URIs so that the P-CSCF is able to forward the request to the selected S-CSCF. This applies both on the originating and terminating sides (of the IMS). [For the terminating call the request will include the P-CSCF address and the UE address.]
Within the IMS service network, Application Servers (ASs) are provided for implementing IMS service functionality. Application Servers provide services to end-users in an IMS system, and may be connected either as end-points over the 3GPP defined Mr interface, or “linked in” by an S-CSCF over the 3GPP defined ISC interface. In the latter case, Initial Filter Criteria (IFC) are used by an S-CSCF to determine which Applications Servers should be “linked in” during a SIP Session establishment. Different IFCs may be applied to different call cases. The IFCs are received by the S-CSCF from an HSS during the IMS registration procedure as part of a user's User Profile. Certain Application Servers will perform actions dependent upon subscriber identities (either the called or calling subscriber, whichever is “owned” by the network controlling the Application Server). For example, in the case of call forwarding, the appropriate (terminating) application server will determine the new terminating party to which a call to a given subscriber will be forwarded.
The working group known as ETSI TISPAN initially developed the use of IMS for fixed broadband accesses, although this task has now been passed to 3GPP. One of their tasks is to develop supplementary services based upon the IMS defined by 3GPP. These supplementary services will be defined in separate specifications although they will impact upon core specifications such as TS24.229. FIG. 2 illustrates schematically the message flow within the IMS for a SIP INVITE, on the call originating side, according to TS24.229 (chapter 5.4.3.2). At step 1), the INVITE is sent from the originating User Equipment (UE) to the P-CSCF. This INVITE includes in its header a so-called P-Preferred identity, as well as including the URI of the P-CSCF at the topmost level of the SIP route header and the URI of the S-CSCF as the second entry. The UE also includes the identity of the communicating partner in the Request-URI. Upon receipt of the INVITE, the P-CSCF checks that the originating UE is allowed to use the identity included as the P-Preferred identity, and if so includes it as the P-Asserted Identity in the outgoing INVITE. The P-Asserted Identity is an identity that is used among trusted SIP entities, typically intermediaries, to carry the identity of the user sending a SIP message as it was verified by authentication. The P-CSCF identifies the S-CSCF allocated to the originating UE by looking in the Route Header, and at step 2) forwards the amended INVITE to that S-CSCF.
The S-CSCF handles the call according to an originating call case procedure. The S-CSCF uses the P-Asserted Identity to check whether any relevant restrictions have been placed on the originating UE, e.g. is the UE barred from using the requested service. The S-CSCF also uses the P-Asserted Identity and call case to determine the IFCs for the UE. In the example of FIG. 2 , it is assumed that the IFCs require that the S-CSCF forward (step 3)) the INVITE to a particular AS. The S-CSCF includes at the topmost level of the SIP route header the URI of the AS. It also includes in the subsequent level its own URI, together with an Original Dialog Identifier (ODI). The ODI is generated by the S-CSCF and uniquely identifies the call to the S-CSCF. The AS will itself perform authentication, for example based upon the P-Asserted Identity contained in the message (the originating case). The appropriate case is identified to the AS by the S-CSCF (e.g. by sending the message to an appropriate port of the AS). When the AS returns the INVITE (step 4)) to the S-CSCF, the AS strips the URI of the AS from the route header, leaving the URI of the S-CSCF together with the ODI tag. The ODI tag allows the S-CSCF to determine that the INVITE relates to an earlier dialogue.
It is possible for the AS logic to require the setting up of a new session, in which case it would be necessary to provide a mechanism which allows the AS to replace the original R-URI with the URI of the new terminating User (the existing TSs do not as yet provide for this re-routing scenario). In this case, the identity of the origin, i.e. the P-Asserted Identity of the INVITE at step 4), can be either the identity of the originating UE, the identity of the AS, or an identity of a third party on whose behalf the AS is setting up the new session. In this case, the S-CSCF will repeat the call restriction check and determine the IFCs based upon the P-Asserted Identity contained in the “new” INVITE, assuming that the originating case is used. However, it is possible that the AS may signal to the S-CSCF that the terminating case is to be used, in which case the checks are carried out using the R-URI of the INVITE. Assuming that no further ASs are to be linked-in based upon the IFCs, the S-CSCF forwards the INVITE to the Request URI (R-URI) contained in the INVITE. This may be the R-URI contained in the original INVITE, or a new R-URI contained in the new INVITE if that is different.
FIG. 3 illustrates schematically the message flow within the IMS for a SIP INVITE on the call terminating side (TS24.229: chapter 5.4.3.3). At step 1), the INVITE arrives from the I-CSCF (not shown) including the R-URI indicating the called party. The S-CSCF uses this R-URI to check for restrictions placed on the called party, and to obtain the IFCs. In this case, the IFCs do not indicate that an AS needs to be contacted. The S-CSCF will acquire the preloaded Route Headers for the called party, based on the R-URI, and send the INVITE forward to be UE based on these Route Header entries. The INVITE is received by the P-CSCF in accordance with the preloaded route in the S-CSCF, and the P-CSCF sends the INVITE to the UE in accordance with the contact header.
FIG. 4 illustrates an alternative INVITE message flow scenario, where a call from an originating terminal (UE-O) to a peer terminal (UE-F) is forwarded to a terminating terminal (UE-T). The call forwarding action is performed by an Application Server (AS-F). The call flow is as follows:
1) The INVITE is sent from UE-O addressed to UE-F (R-URI). The S-CSCF O performs the originating side call procedure as described with reference to FIG. 2 .
2) After interaction with the AS-O (no change is made to the R-URI at this stage) the S-CSCF O sends the INVITE to the I-CSCF (not shown) of UE-F's home network. The I-CSCF will acquire the address of the S-CSCF where the UE-F is registered from the HSS. The INVITE is sent to that S-CSCF, i.e. to S-CSCF F. The S-CSCF F will check the restriction requirement and obtain the IFCs as described above (for the terminating side case) with reference to FIG. 3 , i.e. based on the R-URI contained in the INVITE. In the scenario illustrated in FIG. 4 , the INVITE will be sent to the AS-F where the call forwarding is activated.
3) The AS-F will then change the R-URI in the INVITE header from that of UE-F to that of UE-T. The modified INVITE will be returned to the S-CSCF F.
4) The S-CSCF F will send the INVITE to the I-CSCF of the UE-T network, and the I-CSCF (not shown) will interrogate the HSS to get the address of the S-CSCF T of UE-T, and forward the INVITE to the S-CSCF T.
5) The S-CSCF T will perform the terminating procedure as described with reference to FIG. 3 , on the basis of the R-URI contained in the INVITE (that is the R-URI of UE-T)
As mentioned above, an Application Server may be required to perform an authorisation on one of the parties associated with the call, before returning a SIP message to the S-CSCF. Whilst this may be straightforward in the case of the originating and terminating cases of FIGS. 2 and 3 , the situation is more complex in the call forwarding case of FIG. 4 as the Application Server does not implicitly know which case to apply for which user. WO2007060074 describes a solution to this problem, proposing that, upon receipt of a SIP message at an S-CSCF and following a decision to forward the message to an AS, the S-CSCF introduce a new header into the message referred to as a “P-Served-User”. The proposal is also detailed in the IETF draft: http://tools.ietf.org/wg/sipping/draft-vanelburg-sipping-served-user-05.txt. The role of the new header is to explicitly identify the user that is being served by the S-CSCF and the session case associated with the call for the served user. Whilst in the simple call originating case ( FIG. 2 ) and call terminating case ( FIG. 3 ) the new header will contain the SIP URI of the originating and terminating users respectively, in the case of the call forwarding scenario ( FIG. 4 ), considering S-CSCF F, the header will contain the URL of the forwarding terminal, i.e. UE F. The header will also likely indicate either the originating or terminating call case, and whether or not UE-F is registered with the S-CSCF. An example header might be:
P-Served-User: <sip:bob@home2.net>;sesscase=orig;regstate=reg
Use of the P-Served-User allows the Application Server to apply a more appropriate authorisation procedure to the message.
Considering further the call forwarding scenario, FIG. 5 illustrates the case where a SIP INVITE originating at a user A (not shown in the Figure) is received for user B at an S-CSCF, message 1 . The Filter Criteria are evaluated by the S-CSCF and AS- 1 is invoked by the sending of message 2 . The S-CSCF includes the P-Served-User header to ensure that the correct served user is identified to the Application Server. AS- 1 determines that the INVITE should be diverted to a user C. The Request URI is modified to include C as the target of the request (R-URI), message 3 . Changing the Request URI in this way causes the S-CSCF to break the Filter Criteria chain with the result that any additional terminating services for user B are not performed upon receipt of message 3 at the S-CSCF. The S-CSCF is instructed to carry out originating services for user B by including the ‘orig’ parameter in the PSU header in message 3 . Alternatively, this could be indicated in the top route header. Evaluation of the originating filter criteria for user B at the S-CSCF invokes AS- 2 , message 4 , which performs the Originating Identity Restriction (OIR) service on behalf of user B (OIR and the related OIP service are considered in 3GPP TS24.607).
A result of the OIR service is the inclusion within the message header of user B's privacy settings, namely the “header” and “id” parameters to indicate to downstream nodes performing the OIP service that user identities within the P-Asserted Identity and other header fields should be hidden. These settings are included in the INVITE sent to the S-CSCF, message 5 . The S-CSCF forwards the INVITE to C, message 6 , maintaining the privacy settings of user B. This will result in a downstream OIP service deleting user A's identity from the message header, despite the fact that user A is happy to reveal its identity to the end receiver, as exhibited by the presence of the parameter “none” in the privacy header of the original request.
SUMMARY
It is an object of the present invention to provide a means whereby an IMS Application Server can determine the role of a user that is being served by an S-CSCF from which a SIP message has been forwarded. This object is achieved by allowing ASs to include role values into messages in dependence upon actions determined by the ASs.
According to a first aspect of the present invention there is provided a Session Initiation Protocol Application Server for use within an IP Multimedia Subsystem. The Application Server comprises a receiving unit for receiving a Session Initiation Protocol message from a Serving Call Session Control Function, the Serving Call Session Control Function serving an IP Multimedia Subsystem user and the message containing within a message header an explicit identification of said user. A processing unit determines an action to be applied to said message and includes within a header of the message a role value defining a role of said user in respect of the action. A transmitter unit returns the message including the role value to said Serving Call Session Control Function.
The processing unit may be configured to include said role value within a header field that contains said explicit identification of said user, e.g. within a P-Served-User header.
Considering further actions that may be determined by said processing unit, these may include transferring and diverting a call to which said message relates. In this case, the role value defines that the served user is the transferor or divertor of the call. Additionally, a further role value may be included within a header defining that the served user is to be treated as the originator or terminator of the call for the purpose of call case handling by the Serving Call Session Control Function.
In the case that the S-CSCF has already included a role value into the message header, e.g. indicating that it is presently applying an originating or terminating call case to the message, the processing unit may be arranged to include the new role value in the message header by replacing the pre-existing role value.
According to a second aspect of the present invention there is provided a Session Initiation Protocol Application Server for use within an IP Multimedia Subsystem. The Application Server comprises a receiving unit for receiving a Session Initiation Protocol message from a Serving Call Session Control Function, the Serving Call Session Control Function serving an IP Multimedia Subsystem user and the message containing within a message header an explicit identification of said user and one or more role values specifying the role of the served user in respect of the message. A processing unit is provided for determining an action to be applied to said message and for applying the action to the message in dependence upon the specified role(s). A transmitter unit then returns the message to said Serving Call Session Control Function.
According to an embodiment of the above second aspect of the invention, the Application Server may be configured to implement a privacy service, e.g. the Originating Identity Privacy service. In this case, said action is one of applying privacy settings to the message. For example, the processing unit may be being arranged to determine from a role value contained within the message whether or not the served user is responsible for a call diversion and, if so, to apply privacy to only a history header of the message. Alternatively, said processing unit may be arranged to determine from a role value contained within the message whether or not the served user is responsible for a call transfer and, if so, to apply privacy to only a Referred-By header of the message.
According to a third aspect of the present invention there is provided a method of handling a Session Initiation Protocol message within an IP Multimedia Subsystem. The method comprises receiving the message at a Serving Call Session Control Function, where the message includes a message header containing an identity of the user served by the Serving Call Session Control Function and to which the message relates. The message is forwarded to a first Application Server. Upon receipt of the message, the first Application Server determines an action to be applied to the message, e.g. call forwarding or call diversion, and includes in a message header a role value defining the role of the served user in respect of the action. The message is then returned to the Serving Call Session Control Function which in turn forwards it to a second Application Server. Upon receipt of the message at the second Application Server, this server determines an action to be applied to the message, e.g. a privacy setting, and applies that action in dependence upon the role value it contains.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates schematically the integration of an IP Multimedia Subsystem into a 3G mobile communications system;
FIG. 2 illustrates the flow of a SIP INVITE on the originating call side of the IMS;
FIG. 3 illustrates the flow of a SIP INVITE on the terminating call side of the IMS; and
FIG. 4 illustrates the flow of a SIP INVITE in a call forwarding scenario within the IMS;
FIG. 5 illustrates privacy handling of a SIP INVITE during a call forwarding scenario according to the prior art;
FIG. 6 shows an example SIP message header structure for conveying a served user role value;
FIG. 7 illustrates privacy handling of a SIP INVITE during a call forwarding scenario and making use of a served user role value included with the SIP message;
FIG. 8 illustrates schematically an Application Server configured to include a role value into a SIP message header in dependence upon an action performed by the Application Server; and
FIG. 9 illustrates schematically an Application Server configured to determine a role performed by a user associated with a SIP message, based upon a role value contained within the message.
DETAILED DESCRIPTION
As has already been considered, Session Initiation Protocol (SIP) messages including but not limited to SIP INVITES may not be handled correctly or appropriately by a SIP Application Server (AS) where the AS is unaware of the role being performed by a user that is being served by a Serving Call Session Control Function (S-CSCF) and that is associated with the message. That is to say that, whilst advantages are achieved by including a P-Served-User header (or alternative field for identifying the served user) in a SIP message forwarded from the S-CSCF to the AS, this in itself is not sufficient in certain cases.
An example that has been considered above is the inappropriate application of privacy settings in the case of a SIP INVITE forwarded to an AS which decides to implement call forwarding on behalf of the user served by the S-CSCF. By way of further background, privacy headers are defined in RFC3323 and further extended by RFC4244 (History-Info). Privacy headers allow the user to specify which of his identities can be revealed to other parties in the communication session. Privacy headers provide multiple values which relate to different identities included in the SIP messaging. For example, a privacy value of ‘id’ will prevent the user's authorised identity from being disclosed in the P-Asserted Identity header. A value of ‘headers’ will prevent the user's identity being included in any headers sent to a peer user. When the History-Info RFC (RFC4244) was written, the privacy header was extended to allow for the privacy of user identities included in History-Info headers. More specifically, this privacy feature is referenced by using the ‘history’ tag in the Privacy header or by including a parameter of ‘Privacy=history’ with a specific URI included in the History-Info header.
With reference to FIG. 5 , in order to apply privacy settings appropriately, AS- 2 , which performs the Originating Identity Restriction (OIR) based upon user B's identity, should be aware that user B is a diverting user, and not an originating user. This information allows AS- 2 to determine, for example, that the privacy settings should be applied only to user B's identity, and not to user A's identity, for example to cause a downstream OIP service to delete user B's identity from a History-Info header included by AS- 1 , whilst retaining user A's identity.
It is proposed here to include a new header or an additional parameter within an existing or other header, e.g. the proposed P-Served-User header, containing a served user “role” so that the AS, for example an MMTel AS, can ensure that the correct functionality is applied when service interaction occurs. An example of a new SIP message header might be:
P-Served-User-Role=“P-Served-User-Role” HCOLON Serveduserrole Serveduserrole=“userrole” EQUAL “orig”/“term”/“div”/“trans”/ . . .
The precise nature of a new parameter to be added to an existing or other header will depend upon the header. It could however be in the form of a generic parameter or a URI parameter. In the case that the parameter is to be included in the proposed P-Served-User header [as defined in the IEFT draft, http://tools.ietforg/wg/sipping/draft-vanelburg-sipping-served-user-05.txt], the header structure set out in FIG. 6 is possible, where EQUAL, HCOLON, SEMI, name-addr, addr-spec and generic-param are defined in RFC3261. The following is an example of a P-Served-User header field with the proposed new parameter:
P-Served-User: <sip:captain@buzz.com>; sescase=orig; regstate=reg; userrole=div
The actual “values” allowed for the user role can take any appropriate form. However, a number of likely roles are; originating user (orig), terminating user (term), diversion (div) and transferring (trans) as these are known roles which are useful to the AS, i.e. these values allow the services (AS) to identify if the served user is the originating or terminating party to the call or if they are a diverting or transferring user. The logic deployed by the services will then depend upon the user role in the session. Of course, the range of allowed values should remain extensible so that new roles can be defined when specific cases are identified.
FIG. 7 shows the updated sequence (vis-à-vis FIG. 5 ) where the user role parameter has been included in the P-Served-User header. The presence of the user role parameter (for user B) with value ‘div’ allows AS- 2 to determine the correct actions to take. It will be noted in particular that AS- 2 no longer chooses to include the fields “header” and “id” in the privacy header as these would cause user A's identity to be hidden. Rather, the OIR service adds the ‘history’ tag to the Privacy header, causing a downstream OIP service to hide only the history header which includes user B's identity. User B's identity is not contained in any other header fields and so remains anonymous to user C.
The role value may also be useful where a session has been transferred (nb. transfer of an ongoing call as opposed to diversion of a call during call establishment) and the transferor is identified in the “Referred-By” header introduced by the AS causing the transfer. The session case for the transferor (e.g. user B) in the session may be either originating or terminating, but the rules applying to a user role of originating or terminating user are not appropriate as this may cause a downstream modification of the privacy of the headers for either the true originating or terminating user. Thus, transferring AS introduces a role value “trans” into the P-Served User header. An OIR service at a subsequent AS identifies the presence of the trans role value and applies appropriate privacy settings for user B. This might involve adding a new parameter to the privacy header to specify that a downstream OIP service should delete the Referred-By header.
Another service that may use the role value is a charging service, where details of the role of the user in the session may be important to ensure that the correct identities are presented in the charging records produced.
FIG. 8 illustrates schematically an Application Server 1 configured to introduce action dependent role values into SIP messages received from an S-CSCF. The AS comprises a receiving unit or means 2 for receiving SIP messages sent across the ISC interface. The messages are passed to a processing unit or means 3 which comprises a header adaptation unit or means 4 . The processing unit is arranged to determine an action to be applied to the message, whilst the adaptation unit is configured to introduce into the message header an appropriate role value (or values). The modified message is passed to a sending unit 5 which returns the message to the S-CSCF.
FIG. 9 illustrates schematically an Application Server 6 configured to implement a role dependent service on behalf of users. For example, the AS may implement the OIR service. A receiving unit or means 7 receives SIP messages from an S-CSCF over the ISC interface. These messages are passed to a processing unit or means 8 . The processing unit is configured to apply an action to the message. A role determination unit or means 9 determines the role of the user served by the S-CSCF from a role value contained within the message header. The action applied is modified according to the user's role. The message is then passed to a sending unit 10 and returned to the S-CSCF. It is noted here that, if the S-CSCF determines that the SIP message should now be forwarded towards the called party, and not directly to another AS, the S-CSCF will strip out the P-Served User filed including the role value(s).
The mechanism proposed here enables a service deployed on a given application server to determine the correct functionality to apply to a session based upon actions taken by a previous application server in the routing path. By making use of multiple user role headers or parameters it would be possible to use a combination of different user roles applied by different application servers to resolve complex service interaction issues.
It will be appreciated by the person of skill in the art that various modifications may be made to the embodiments described above without departing from the scope of the present invention. | A Session Initiation Protocol Application Server for use within an IP Multimedia Subsystem. The Application Server comprises a receiving unit for receiving a Session Initiation Protocol message from a Serving Call Session Control Function, the Serving Call Session Control Function serving an IP Multimedia Subsystem user and the message containing within a message header an explicit identification of said user. A processing unit determines an action to be applied to said message and includes within a header of the message a role value defining a role of said user in respect of the action. A transmitter unit returns the message including the role value to said Serving Call Session Control Function. | 6 |
[0001] The application is a continuation application of and claims priority to U.S. application Ser. No. 09/762,152, filed on Feb. 1, 2001, which claims priority to International Patent Application No. PCT/CA99/01123, filed on Nov. 22, 1999, which claims priority to Canadian Application No. 2,254,645, filed on Nov. 23, 1998. Each of said applications are herein incorporated by reference in their entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to a method for suppressing pathogenic cells, as well as a method for the treatment of an animal, including a human, having pathogenic cells within its respiratory tract. These methods preferably comprise the exposure of the pathogenic cells to an effective amount of a source of nitric oxide, the nitric oxide source comprising nitric oxide or a compound or substance capable of producing nitric oxide and wherein the nitric oxide may have either an inhibitory or a cidal effect on such pathogenic cells.
[0003] Further, the present invention relates to the use of nitric oxide for suppressing pathogenic cells, the therapeutic use of nitric oxide for the treatment of an animal having pathogenic cells in its respiratory tract and a pharmaceutical composition for such treatment.
[0004] As well, in a preferred embodiment, the present invention relates to the use of nitric oxide in a gaseous form (NO) in the treatment of fungal, parasitic and bacterial infections, particularly pulmonary infection by mycobacterium tuberculosis . The invention also relates to an improved apparatus or device for the delivery, particularly pulsed-dose delivery, of an effective amount of nitric oxide for the treatment of microbial based diseases which are susceptible to nitric oxide gas. The device preferably provides nitric oxide replacement therapy at a desired dose for infected respiratory tract infections, or provides nitric oxide as a sterilizing agent for medical and other equipment, instruments and devices requiring sterilization.
BACKGROUND OF THE INVENTION
[0005] In healthy humans, endogenously synthesized nitric oxide (NO) is thought to exert an important mycobacteriocidal or inhibitory action in addition to a vasodilatory action. There have been a number of ongoing, controlled studies to ascertain the benefits, safety and efficacy of inhaled nitric oxide as a pulmonary vasodilator. Inhaled nitric oxide has been successfully utilized in the treatment of various pulmonary diseases such as persistent pulmonary hypertension in newborns and adult respiratory distress syndrome. There has been no attempt, however, to reproduce the mycobacteriocidal or inhibitory action of NO with exogenous NO.
[0006] Further background information relating to the present invention may be found in the following references:
1. Lowenstein, C. J., J. L. Dinerman, and S. H. Snyder. 1994. Nitric oxide: a physiologic messenger” Ann. Intern. Med. 120:227-237. 2. The neonatal inhaled nitric oxide study group. 1997. Inhaled nitric oxide in full-term and nearly full-term infants with hypoxic respiratory failure. N. Engl. J. Med. 336:597-604. 3. Roberts, J. D. Jr., J. R Fineman, F. C. Morin III, et al. for the inhaled nitric oxide study group. 1997. Inhaled nitric oxide and persistent pulmonary hypertension of the newborn. N. Engl. J. Med. 336:605-610. 4. Rossaint, R., K. J. Falke, F. Lopez, K. Slama, U. Pison, and W. M. Zapol. 1993. Inhaled nitric oxide for the adult respiratory distress syndrome. N. Engl. J. Med. 328:399-405. 5. Rook, G. A. W. 1997. Intractable mycobacterial infections associated with genetic defects in the receptor for interferon gamma: what does this tell us about immunity to mycobacteria? Thorax. 52 (Suppl 3):S41-S46. 6. Denis, M. 1991. Interferon-gamma-treated murine macrophages inhibit growth of tubercle bacilli via the generation of reactive nitrogen intermediates. Cell. Immunol. 132:150-157. 7. Chan, J., R. Xing, R. S. Magliozzo, and B. R. Bloom. 1992. Killing of virulent Mycobacterium tuberculosis by reactive nitrogen intermediates produced by activated murine macrophages. J. Exp. Med. 175:1111-1122. 8. Chan, J., K. Tanaka, D. Carroll, J. Flynn, and B. R. Bloom. 1995. Effects of nitric oxide synthase inhibitors on murine infection with Mycobacterium tuberculosis . Infect. Immun. 63:736-740. 9. Nozaki, Y., Y. Hasegawa, S. Ichiyama, I. Nakashima, and K. Shimokata. 1997. Mechanism of nitric oxide—dependent killing of Mycobacterium bovis BCG in human alveolar macrophages. Infect. Immun. 65:3644-3647. 10. Canetti, G. 1965. Present aspects of bacterial resistance in tuberculosis. Am. Rev. Respir. Dis. 92:687-703. 11. Hendrickson, D. A., and M. M. Krenz. 1991. Regents and stains, P. 1289-1314. In Balows, A, W. J. Hausler Jr., K. L. Herrmann, H. D. Isenberg, and 1-1i. Shadomy (eds.), Manual of Clinical Microbiology, 5th ed., 1991. American Society for Microbiology, Washington, D.C. 12. Szabo, C. 1996. The pathophysiological role of peroxynitrite in shock, inflammation and ischemia—reperfusion injury. Shock. 6:79-88. 13. Stavert, D. M., and B. E. Lehnert. 1990. Nitrogen oxide and nitrogen dioxide as inducers of acute pulmonary injury when inhaled at relatively high concentrations for brief periods. Inhal. Toxicol. 2:53-67. 14. Hugod, C. 1979. Effect of exposure to 43 PPM nitric oxide and 3.6 PPM nitrogen dioxide on rabbit lung. mt. Arch. Occup. Environ. Health. 42:159-167 15. Frostell, C., M. D. Fratacci, J. C. Wain, R. Jones and W. M. Zapol. 1991. Inhaled nitric oxide, a selective pulmonary vasodilator reversing hypoxic pulmonary vasoconstriction. Circulation. 83:2038-2047. 16. BuIt, H., G. R. Y. Dc Meyer, F. H. Jordaens, and A. G. Herman. 1991. Chronic exposure to exogenous nitric oxide may suppress its endogenous release and efficacy. J. Cardiovasc. Pharmacol. 17:S79-S82. 17. Buga, G. M., J. M. Griscavage, N. E. Rogers, and L. J. Ignarro. 1993. Negative feedback regulation of endothelial cell function by nitric oxide. Circ. Res. 73:808-812 18. Assreuy, J., F. Q. Cunha, F. Y. Liew, and S. Moncada. 1993. Feedback inhibition of nitric oxide synthase activity by nitric oxide. Br. J. Pharmacol. 108:833-837. 19. O'Brien, L., J. Carmichael, D. B. Lowrie and P. W. Andrew. 1994. Strains of Mycobacterium tuberculosis differ in susceptibility to reactive nitrogen intermediates in vitro. Infect. Immun. 62:5187-5190. 20. Long, R., B. Maycher, A. Dhar, J. Manfreda, E. Hershfield, and N. R. Anthonisen. 1998. Pulmonary tuberculosis treated with directly observed therapy: serial changes in lung structure and function. Chest. 113:933-943. 21. Bass, H., J. A. M. Henderson, T. Heckscher, A. Oriol, and N. R. Anthonisen. 1968. Regional structure and function in bronchiectasis. Am. Rev. Respir. Dis. 97:598-609.
SUMMARY OF THE INVENTION
[0028] In a first aspect of the invention, the invention relates to a method for suppressing pathogenic cells, and a method for treating an animal having pathogenic cells in its respiratory tract, utilizing a source of nitric oxide. More particularly, in the first aspect of this invention, the invention relates to a method for suppressing pathogenic cells comprising the step of exposing the pathogenic cells to an effective amount of a nitric oxide source. Further, the invention relates to a method for treating an animal having pathogenic cells in the respiratory tract of the animal comprising the step of delivering by the inhalation route to the respiratory tract of the animal an effective amount of a nitric oxide source.
[0029] In a second aspect of the invention, the invention relates to a use and a therapeutic use of a source of nitric oxide for suppressing or treating pathogenic cells. More particularly, in the second aspect of the invention, the invention relates to the use of an effective amount of a nitric oxide source for suppressing pathogenic cells exposed thereto. Further, the invention relates to the therapeutic use of an effective amount of a nitric oxide source for the treatment by the inhalation route of an animal having pathogenic cells in the respiratory tract of the animal. Preferably, as discussed further below, the present invention relates to the novel use of inhaled nitric oxide gas as an agent for killing bacterial cells, parasites and fungi in the treatment of respiratory infections.
[0030] In a third aspect of the invention, the invention relates to a pharmaceutical composition for use in treating an animal having pathogenic cells in its respiratory tract, which composition comprises a nitric oxide source. More particularly, in the third aspect of the invention, the invention relates to a pharmaceutical composition for use in the treatment by the inhalation route of an animal having pathogenic cells in the respiratory tract of the animal, the pharmaceutical composition comprising an effective amount of a nitric oxide source.
[0031] Finally, in a fourth aspect of the invention, the invention relates to an apparatus or device for supplying, delivering or otherwise providing a nitric oxide source. Preferably, the apparatus or device provides the nitric oxide source for the particular applications, methods and uses described herein. However, the apparatus or device may also be used for any application, method or use requiring the supply, delivery or provision of a nitric oxide source.
[0032] In all aspects of the invention, the nitric oxide source is preferably nitric oxide per se, and more particularly, nitric oxide gas. However, alternately, the nitric oxide source may be any nitric oxide producing compound, composition or substance. In other words, the nitric oxide source may be any compound, composition or substance capable of producing or providing nitric oxide, and particularly, nitric oxide gas. For instance, the compound, composition or substance may undergo a thermal, chemical, ultrasonic, electrochemical or other reaction, or a combination of such reactions, to produce or provide nitric oxide to which the pathogenic cells are exposed. As well, the compound, composition or substance may be metabolized within the animal being treated to produce or provide nitric oxide within the respiratory tract of the animal.
[0033] Further, in all aspects of the invention, the invention is for use in suppressing or treating any pathogenic cells. For instance, the pathogenic cells may be tumor or cancer cells. However, the pathogenic cells are preferably pathogenic microorganisms, including but not limited to pathogenic bacteria, pathogenic parasites and pathogenic fungi. More preferably, the pathogenic microorganisms are pathogenic mycobacteria. In the preferred embodiment, the pathogenic mycobacteria is M. tuberculosis.
[0034] Referring to the use of the nitric oxide source and method for suppressing pathogenic cells using the nitric oxide source, as indicated, the nitric oxide source is preferably nitric oxide per se. However, the nitric oxide source may be a compound, composition or substance producing nitric oxide. In either event, the pathogenic cells are suppressed by the nitric oxide. Suppression of the pathogenic cells by nitric oxide may result in either or both of an inhibitory effect on the cells and a cidal effect on the cells. However, preferably, the nitric oxide has a cidal effect on the pathogenic cells exposed thereto. Thus, it has been found that these aspects of the invention have particular application for the sterilization of medical and other equipment, instruments and devices requiring sterilization.
[0035] As well, the pathogenic cells may be exposed to the nitric oxide and the exposing step of the method may be performed in any manner and by any mechanism, device or process for exposing the pathogenic cells to the nitric oxide source, and thus nitric oxide, either directly or indirectly. However, in the preferred embodiment, the pathogenic cells are directly exposed to the nitric oxide. As a result, where desired, the effect of the nitric oxide may be localized to those pathogenic cells which are directly exposed thereto.
[0036] Similarly, the therapeutic use, method for treating and pharmaceutical composition for treatment all deliver the nitric oxide source to the pathogenic cells in the respiratory tract of the animal. The therapeutic use, method and composition may be used or applied for the treatment of any animal, preferably a mammal, including a human. Further, as indicated, the nitric oxide source in these instances is also preferably nitric oxide per se, however, the nitric oxide source may be a compound, composition or substance producing nitric oxide within the respiratory tract. In either event, the nitric oxide similarly suppresses the pathogenic cells in the respiratory tract of the animal. This suppression of the pathogenic cells may result in either or both of an inhibitory effect on the cells and a cidal effect on the cells. However, preferably, the nitric oxide has a cidal effect on the pathogenic cells in the respiratory tract exposed thereto.
[0037] As well, the pathogenic cells in the respiratory tract of the animal may be treated by nitric oxide and the delivering step of the therapeutic method may be performed in any manner and by any mechanism, device or process for delivering the nitric oxide source, and thus nitric oxide, either directly or indirectly to the respiratory tract of the animal. In the preferred embodiments of these aspects of the invention, the nitric oxide source is delivered directly by the inhalation route to the respiratory tract of the animal, preferably by either the spontaneous breathing of the animal or by ventilated or assisted breathing.
[0038] Further, in the preferred embodiments of these aspects of the invention, the pathogenic cells in the respiratory tract of the animal are treated by, and the delivering step of the therapeutic method is comprised of, exposing the pathogenic cells to the nitric oxide source, and thus nitric oxide, either directly or indirectly. More preferably, the pathogenic cells are directly exposed to the nitric oxide. As a result, where desired, the effect of the nitric oxide may be localized to those pathogenic cells which are directly exposed thereto within the respiratory tract of the animal.
[0039] In addition, in all aspects of the invention, an effective amount of the nitric oxide source is defined by the amount of the nitric oxide source required to produce the desired effect of the nitric oxide, either inhibitory or cidal, on the pathogenic cells. Thus, the effective amount of the nitric source will be dependent upon a number of factors including whether the nitric oxide source is nitric oxide per se or a nitric oxide producing compound, the desired effect of the nitric oxide on the pathogenic cells and the manner in which the pathogenic cells are exposed to or contacted with the nitric oxide. In the preferred embodiments of the various aspects of the invention, the effective amount of the nitric oxide source is the amount of nitric oxide required to have a cidal effect on the pathogenic cells exposed directly thereto. Thus, the effective amount for any particular pathogenic cells will depend upon the nature of the pathogenic cells and can be determined by standard clinical techniques. Further, the effective amount will also be dependent upon the concentration of the nitric oxide to which the pathogenic cells are exposed and the time period or duration of the exposure.
[0040] Preferably, the pathogenic cells are exposed to a gas or a gas is delivered to the respiratory tract of the animal being treated, wherein the gas is comprised of the nitric oxide source. More preferably, the pathogenic cells are exposed to a gas comprised of nitric oxide. For instance, the gas may be comprised of oxygen and nitric oxide for delivery by the inhalation route to the respiratory tract of the animal being treated.
[0041] Although in the preferred embodiments of the various aspects of the invention, any effective amount of nitric oxide may be used, the concentration of the nitric oxide in the gas is preferably at least about 25 parts per million. Further, the concentration of the nitric oxide in the gas is preferably less than about 100 parts per million. Most preferably, the concentration of the nitric oxide in the gas is between about 25 and 90 parts per million.
[0042] Although the pathogenic cells may be exposed to the gas for any time period or duration necessary to achieve the desired effect, the pathogenic cells are preferably exposed to the gas, or the gas is delivered to the respiratory tract of the animal, for a time period of at least about 3 hours. In the preferred embodiments of the various aspects of the invention, the pathogenic cells are exposed to the gas, or the gas is delivered to the respiratory tract of the animal, for a time period of between about 3 and 48 hours.
[0043] Finally, in the fourth embodiment of the invention, the apparatus or device is preferably comprised of a portable battery-operated, self-contained medical device that generates its own nitric oxide source, preferably nitric oxide gas, as a primary supply of nitric oxide. Further, the device may also include a conventional compressed gas supply of the nitric oxide source, preferably nitric oxide gas, as a secondary back-up system or secondary supply of nitric oxide.
[0044] Further, the device preferably operates to deliver nitric oxide in the gaseous phase to spontaneously breathing or to ventilated individual patients having microbial infections, by way of a specially designed nasal-cannula or a mask having a modified Fruman valve. In the preferred embodiment, nitric oxide gas is produced in cartridges through thermal-chemical, ultrasonic and/or electrochemical reaction and is released upon user inspiratory demand in pulsed-dose or continuous flow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0045] The nature and scope of the invention will be elaborated in the detailed description which follows, in connection with the enclosed drawing figures, in which:
[0046] FIG. 1 illustrates an airtight chamber for exposure of mycobacteria to varying concentrations of nitric oxide (NO) in tests of in vitro measurements of the cidal effects of exogenous NO;
[0047] FIG. 2 is a graphical representation of experimental data showing the relationship of percent kill of microbes to exposure time for fixed doses of NO;
[0048] FIG. 3 a shows the external features of a pulse-dose delivery device for nitric oxide according to the present invention;
[0049] FIG. 3 b illustrates schematically the internal working components of the device of FIG. 3 a;
[0050] FIG. 4 is a schematic illustration of the specialized valve used to control the delivery of nitric oxide in a preset dosage through the disposable nasal cannula of a device according to the present invention; and
[0051] FIG. 5 is a schematic drawing of the mask-valve arrangement of a pulsed-dose nitric oxide delivery device according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0052] Studies of the Applicant on the exposure of extra cellular M. tuberculosis to low concentrations of NO for short periods have led to the conclusion that exogenous NO exerts a powerful dose-dependent and time-dependent mycobacteriocidal action. Further, it may be inferred that the large population of extracellular bacilli in patients with cavitary pulmonary tuberculosis are also vulnerable to exogenous (inhaled) NO.
[0000] Measurements of Cidal Activity of Exogenous NO
[0053] Referring to FIG. 1 , to re-create a normal incubation environment that allowed for the exposure of mycobacteria to varying concentrations of NO, an airtight “exposure chamber” (20) was built that could be seated in a heated biological safetv cabinet ( 22 ). This chamber ( 20 ) measured 31×31×21 cm and is made of plexiglass. It has a lid ( 24 ) which can be firmly sealed, a single entry port ( 26 ) and a single exit port ( 28 ) through which continuous, low-flow, 5-10% CO 2 in air can pass, and a thermometer ( 30 ). A “Y” connector ( 32 ) in the inflow tubing allows delivery of NO, at predetermined concentrations, to the exposure chamber ( 20 ). Between the “Y” connector ( 32 ) and the exposure chamber ( 20 ) is a baffle box ( 34 ) which mixes the gases. Finally between the baffle box ( 34 ) and the exposure chamber ( 20 ) is placed an in-line NO analyzer ( 36 ), preferably a Pulmonox Sensor manufactured by Pulmonox Medical Corporation, Tofield, Alberta, Canada. This analyzer ( 36 ) continuously measures NO concentration in the gas mixture entering the exposure chamber ( 20 ).
[0054] The day before conducting the experiments, a precise quantity of actively growing virulent M. tuberculosis was plated on solid media ( 38 ) (Middlebrook 7H-10 with OADC enrichment) after careful dilution using McFarland nephelometry (1 in 10 dilution, diluted further to an estimated 103 bacteria/ml and using a 0.1 ml inoculate of this suspension) (see Reference No. 11 above under the Background of the Invention). Control and test plates were prepared for each experiment. Control plates were placed in a CO 2 incubator (Form a Scientific, Marietta, Ohio) and incubated in standard fashion at 37° C. in 5-10% CO 2 in air.
[0055] Test plates were placed in the exposure chamber ( 20 ) for a pre-determined period of time after which they were removed and placed in the incubator along with the control plates. The temperature of the exposure chamber ( 20 ) was maintained at 32-34° C. Colony counts were measured on control and test plates at 2, 3 and 6 weeks from the day of plating. Reported counts are those measured at three weeks expressed as a percentage of control.
[0056] Experiments were of two varieties: (1) those that involved exposure of the drug susceptible laboratory strain H37RV to fixed concentrations of NO, i.e. 0 (sham), 25, 50, 70 and 90 PPM for periods of 3, 6, 12, and 24 hours; and (2) those that involved exposure of a multidrug-resistant (isoniazid and rifampin) wild strain of M. tuberculosis to fixed concentrations of NO, i.e. 70 and 90 PPM for periods of 3, 6, 12 and 24 hours. One experiment at 90 PPM NO, that used both strains of M. tuberculosis , was extended to allow for a total exposure time of 48 hours. The NO analyzer ( 36 ) was calibrated at least every third experiment with oxygen (0 PPM of NO) and NO at 83 PPM.
[0000] Statistical Analysis
[0057] For each NO exposure time and NO concentration studied at least two, and in most cases three or four, separate experiments were performed with 3-6 exposure plates ( 38 ) per set. Colony counts performed on each exposure plate ( 38 ) were expressed as a percentage of the mean colony count of the matched non-exposed control plates. The values from all experiments at each NO concentration and exposure time were then averaged. These data were analyzed using two-way analysis of variance using the F statistic to test for independent effects of NO exposure time and NO concentration and of any interaction between them on the colony counts.
[0000] Experimental Results
[0058] A diagram of the incubation environment is shown in FIG. 1 . This environment exactly simulated the usual incubation environment of M. tuberculosis in the laboratory, with the following exceptions: (1) the temperature of our exposure chamber ( 20 ) was maintained at 32-34° C. rather than the usual 37° C. to avoid desiccation of the nutrient media upon which the bacteria were plated; and (2) the test plates were openly exposed. That a stable and comparable incubation environment was reproduced was verified in four sham experiments using the H37RV laboratory strain of M. tuberculosis . Colony counts on plates ( 38 ) exposed to 5-10% CO 2 in air (0 PPM NO) at 32-34° C. in the exposure chamber (20) were not significantly different from those on control plates placed in the laboratory CO 2 incubator at 37° C., as shown in Table 1, below:
TABLE 1 COLONY COUNTS AFTER EXPOSURE OF THE LABORATORY STRAIN (H37RV) OF M. TUBERCULOSIS TO VARYING CONCENTRATIONS OF NITRIC OXIDE FOR PERIODS OF 3, 6, 12 AND 24 HOURS Colony Counts (Mean ± SE) (expressed as percentage of control) Exposure Time (Hours) NO (PPM) 3 6 12 24 0 107 ± 5(6)* 100 ± 5(6) 97 ± 9(6) 105 ± 5(18) 25 09 ± 6(12) 109 ± 4(12) 102 ± 3(12) 66 ± 4(18) 50 97 ± 5(12) 96 ± 2(12) 69 ± 3(12) 41 ± 5(18) 70 80 ± 10(7) 63 ± 12(7) 58 ± 12(11) 21 ± 6(11) 90 101 ± 15(11) 67 ± 7(11) 64 ± 7(14) 15 ± 3(15) *Numbers in brackets refer to the number of plates prepared for each NO concentration at each time interval.
[0059] Seventeen experiments of the first variety, where plates (38) inoculated with a 0.1 ml suspension of 10 3 bacteria/ml of the H37RV strain of M. tuberculosis were exposed to a fixed concentration (either 0, 25, 50, 70 or 90 PPM) of NO for increasing periods of time (3, 6, 12, and 24 hours) were performed. The results have been pooled and are outlined in Table 1. There were both dose and time dependent cidal effects of NO that were very significant by two-way ANOVA (F ratio 13.4, P<0.001; F ratio 98.1, P<0.0001 respectively) and there was also a statistically significant interactive effect on microbial killing efficacy (F ratio 2.03, P<0.048). Although there was some variability in the percentage killed from experiment to experiment, increasing the standard error of the pooled data, the dose and time effect were highly reproducible. Only one control and one test (12 hour) plate at 90 PPM were contaminated. That the effect of NO was cidal and not inhibitory was confirmed by the absence of new colony formation beyond three weeks.
[0060] As described in FIG. 2 , the response to a fixed dose of NO was relatively linear with the slope of the line relating exposure time to percent kill increasing proportionally with the dose. Dose-related microbial killing did not appear to increase above 70 PPM NO, since colony counts at 70 and 90 PPM were indistinguishable. At 24 hours of NO exposure at both the 70 and 90 PPM NO levels, more than one third of the exposed plates were sterile. One experiment at 90 PPM NO was extended to allow for a total exposure time of 48 hours; all of these plates were sterile (see FIG. 2 and Table 2 below)
TABLE 2 COLONY COUNTS AFTER EXPOSURE OF A MULTIDRUG-RESISTANT WILD STRAIN OF M. TUBERCULOSIS TO NITRIC OXIDE FOR PERIODS OF 3, 6, 12, 24 AND 48 HOURS Colony Counts (Mean ± SE) (expressed as percentage of control) Exposure Time (Hours) NO (PPM) 3 6 12 24 48 70 113 ± 2(4) 75 ± 4(4) 85 ± 10(4) 66 ± 4(4) 50 ± 25(4) 10 ± 5(4) 90 97 ± 11(2) 91 ± 11(2) 71 ± 8(2) 36 ± 10(2) 59 ± 4(4) 32 ± 3(4) 0 ± 0(4) 79 ± 5(4) # 20 ± 3(4) # 0 ± 0(4) # *Each series represents an individual experiment; numbers in brackets refer to the number of plates prepared for each experiment at each time interval. # These results refer to the H37RV laboratory strain.
[0061] Four experiments of the second variety, where plates inoculated with a 0.1 ml suspension of 10 3 bacteria/ml of a multidrug-resistant wild strain of M. tuberculosis , were exposed to a fixed concentration (either 70 or 90 PPM) of NO for increasing periods of time (3, 6, 12 and 24 hours) were performed, two at each of 70 and 90 PPM NO. Again there was a significant dose and time dependent cidal effect (see Table 2 above). Although the percent kill at 24 hours was less than that observed with the H37RV strain, when an inoculum of this strain was exposed to 90 PPM NO for a period of 48 hours there was also 100% kill.
CONCLUSION
[0062] Using an in vitro model in which the nitric oxide concentration of the incubation environment was varied, we have demonstrated that exogenous NO delivered at concentrations of less than 100 PPM exerts a powerful dose and time dependent mycobacteriocidal action. When an inoculate of M. tuberculosis that yielded countable colonies (0.1 ml of a suspension of 10 3 bacteria/ml) was plated on nutrient rich media and exposed to exogenous NO at 25, 50, 70 and 90 PPM for 24 hours there was approximately 30, 60, 80 and 85% kill, respectively. Similarly when plates of the same inocula were exposed to a fixed concentration of exogenous NO, for example 70 PPM, for increasing durations of time, the percentage of kill was directly proportional to exposure time; approximately 20, 35, 40 and 80% kill at 3, 6, 12 and 24 hours, respectively.
[0063] Of added interest, the dose and time dependent mycobacteriocidal effect of NO was similar for both the H37RV laboratory strain and a multidrug-resistant (isoniazid and rifampin) wild strain of M. tuberculosis , (after 24 and 48 hours exposure to 90 PPM NO, there was 85 and 100% kill and 66 and 100% kill of the two strains, respectively) expanding the potential therapeutic role of exogenous NO and suggesting that the mechanism of action of NO is independent of the pharmacologic action of these cidal drugs.
[0064] The dominant mechanism(s) whereby intracellular NO, known to be produced in response to stimulation of the calcium-independent inducible nitric oxide synthase, results in intracellular killing of mycobacteria is still unknown (see Reference No. 5 above under the Background of the Invention). Multiple molecular targets exist, including intracellular targets of peroxynitrite, the product of the reaction between NO and superoxide (see Reference No. 12 above under the Background of the Invention). Whatever the mechanism(s), there is evidence that NO may be active not just in murine but also in human alveolar macrophages (see References No. 6-9 above under the Background of the Invention), and furthermore that this activity may be critical to the mycobacteriocidal action of activated macrophages. Whether macrophase inducible NOS produces NO that has extracellular activity is not known but it is reasonable to expect that a measure of positive (mycobacteriocidal) and negative (tissue necrosis) activity might follow the death of the macrophase itself.
[0065] The relative ease with which NO may be delivered exogenously, and its theoretical ability to rapidly destroy the extracellular population of bacilli in the patient with sputum smear positive pulmonary tuberculosis, especially drug-resistant disease, have great clinical appeal.
[0000] Primary Unit of the NO Post-Delivery Device
[0066] Referring to FIGS. 3 a and 3 b , the main unit ( 40 ) provides a small enclosure designed to hang on a belt. An A/C inlet ( 42 ) provides an electrical port to provide power to an internal rechargeable battery which powers the unit ( 40 ) if required. The user interface provides a multi-character display screen ( 44 ) for easy input and readability. A front overlay ( 46 ) with tactile electronic switches allow easy input from user to respond to software driven menu commands. LED and audible alarms ( 48 ) provide notification to user of battery life and usage. A Leur-type lock connector ( 50 ) or delivery outlet establishes communication with the delivery line to either the nasal cannula device ( 52 ) shown in FIG. 4 or the inlet conduit on the modified Fruman valve ( 54 ) shown in FIG. 5 .
[0067] More particularly, referring to FIG. 3 b , the main unit ( 40 ) houses several main components. A first component or subassembly is comprised of an electronic/control portion of the device. It includes a microprocessor driven proportional valve or valve system ( 56 ), an alarm system, an electronic surveillance system and data input/output display system and electronic/software watch dog unit ( 44 ).
[0068] A second component or subassembly includes one or more disposable nitric oxide substrate cartridges ( 58 ) and an interface mechanism. A substrate converter system or segment ( 60 ) processes the primary compounds and converts it into pure nitric oxide gas. The gas then flows into an accumulator stable ( 62 ) and is regulated by the proportional valve assembly ( 56 ) into a NO outlet nipple ( 64 ).
[0069] A third component or subassembly is comprised of a secondary or backup nitric oxide system ( 66 ). It consists of mini-cylinders of high nitric oxide concentration under low-pressure. This system ( 66 ) is activated if and when the primary nitric oxide source ( 58 ) is found faulty, depleted or not available.
[0000] Nasal Cannula Adjunct
[0070] Referring to FIG. 4 , there is shown a detailed drawing of a preferred embodiment of a valve ( 68 ) used to control the delivery of nitric oxide in a preset dosage through a disposable nasal cannula device ( 52 ) as shown. The valve ( 68 ) is controlled by the natural action of spontaneous respiration by the patient and the dosage is preset by the physical configuration of the device ( 52 ).
[0071] The device ( 52 ) including the valve ( 68 ) is constructed of dual lumen tubing ( 70 ). The internal diameter of the tubing ( 70 ) depends on the required dosage. The tubing ( 70 ) is constructed of material compatible with dry nitric oxide gas for the duration of the prescribed therapy. This tubing ( 70 ) is glued into the nasal cannula port ( 72 ).
[0072] The valve ( 68 ) is preferably comprised of a flexible flapper ( 74 ) that is attached by any mechanism, preferably a spot of adhesive ( 76 ), so as to be positioned over the supply tube ( 70 ). The flapper ( 74 ) must be sufficiently flexible to permit the valve action to be effected by the natural respiration of the patient. When the patient breathes in, the lower pressure in the nasal cannula device ( 52 ) causes the flapper ( 74 ) of the valve ( 68 ) to open and the dry gas is delivered from a reservoir ( 78 ) past the flapper ( 74 ) and into the patient's respiratory tract. When the patient exhales, positive pressure in the nasal cannula device ( 52 ) forces the flapper ( 74 ) of the valve ( 68 ) closed preventing any delivered gas entering the respiratory tract.
[0073] The supplied gas is delivered at a constant rate through the supply tube ( 70 ). The rate must be above that required to deliver the necessary concentration to the patient by filling the supply reservoir ( 78 ) up to an exhaust port ( 80 ) in the supply tube ( 70 ) during expiration. When the patient is exhaling the flapper ( 74 ) is closed and the supply gas feeds from a supply line ( 82 ) through a cross port ( 84 ) into the reservoir or storage chamber ( 78 ). The length of the reservoir chamber ( 78 ) given as dimension ( 86 ) determines the volume of gas delivered when the patient inhales. Inhaling opens the flapper ( 74 ) of the valve ( 68 ) and causes the reservoir chamber ( 78 ) to be emptied.
[0074] During exhalation when the flapper ( 74 ) is closed and the reservoir chamber ( 78 ) is filling, any excess gas exhausts through the exhaust port ( 80 ). During inhalation when the reservoir chamber ( 78 ) is emptied, the reservoir chamber ( 78 ) is displaced with atmospheric air through the exhaust port ( 80 ). There will continue to be supply gas from the supply line ( 82 ) through the cross port ( 84 ) during inhalation and this amount must be figured into the total delivered gas to determine the actual dosage. The tubing lumens ( 70 ) include various plugs ( 88 ) to direct the flow.
[0000] Mask/Valve Adjunct
[0075] Referring to FIG. 5 , there is shown a further embodiment of a nitric oxide valve ( 54 ) which is a modification and improvement of a Non-rebreathing valve for gas administration, referred to as a “Modified Fruman Valve,” as shown and particularly described in U.S. Pat. No. 3,036,584 issued May 29, 1962 to Lee.
[0076] More particularly, the within invention specifically redesigns the Modified Fruman Valve for use in inhaled nitric oxide therapy. Specifically, in the preferred embodiment shown in FIG. 5 , one end of a valve body ( 90 ) or valve body chamber is comprised of or includes a mask or mouth-piece (not shown) attached thereto. The connection is preferably standardized to a 22 mm O.D. to facilitate the attachment of the mask or mouth-piece. The other end of the valve body ( 90 ) is comprised of or provides an exhaust port ( 92 ). The exhaust port ( 92 ) entrains ambient air during the latter portion of inspiration and dilutes the nitric oxide coming from an inlet conduit ( 94 ).
[0077] The resultant nitric oxide concentration in the valve body ( 90 ) is determined by the dilutional factors regulated by the valve ( 54 ), tidal volume and the nitric oxide concentration in an attached flexed bag ( 96 ), being a fixed reservoir bag. The inlet conduit ( 94 ) is preferably spliced for the attachment of the small flexed bag ( 96 ). The purpose of the bag ( 96 ) is to act as a reservoir for nitric oxide gas. Further, an opening of the inlet conduit ( 94 ) is preferably modified to facilitate the attachment or connection of the inlet conduit ( 94 ) to a supply hose emanating from a nitric oxide supply chamber. Specifically, the opening of the inlet conduit ( 94 ) is preferably comprised of a knurled hose barb connector ( 98 ).
[0078] While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims. | Methods for suppressing, killing, and inhibiting pathogenic cells, such as microorganisms associated with a respiratory infection within the respiratory tract of an animal are described. Methods include the step of exposing the pathogenic cells to an effective amount of nitric oxide, such as through inhalation of nitric oxide gas. | 0 |
BACKGROUND OF THE INVENTION
The process of making a bed, including lifting a bed mattress and/or tucking in bed covers between the bed mattress and box spring mattress, or other support structure, can be physically taxing. Most often, beds are made manually without the aide of bed-making apparatus. Many of the known bed-making apparatus and methods of use experience one or more problems. Some representative problems with these bed-making apparatus and methods may include: requiring strenuous bed-making activity potentially resulting in fatigue and injury, requiring excessive time to make the bed, leading to poor quality made-beds, and/or other types of problems.
Bed-making apparatus and methods for their use are needed which may solve one or more problems in one or more of the existing bed-making methods and apparatus.
SUMMARY OF THE INVENTION
In one aspect of the invention, a kit is provided for tucking at least a portion of one bed cover under a mattress of a bed. The kit includes a wedge apparatus which comprises a wedge member for lifting a portion of the mattress of the bed. The wedge member includes a bottom surface and a sloped surface which form an acute angle. A first handle member is connected to the wedge member. The kit further includes a tuck apparatus. The tuck apparatus comprises a tuck member for tucking the portion of the bed cover under the mattress of the bed. At least one tucking surface is at one end of the tuck member. A second handle member is connected to the tuck member. At least one of the first and second handle members is oriented in non-parallel relationship with respect to the bottom surface of the wedge member and the tuck member respectively.
In another aspect of the invention, a method is provided of tucking a portion of a bed cover under a mattress of a bed. In one step, a sloped surface of a wedge apparatus is slid under the mattress of the bed in order to lift at least a portion of the mattress. In another step, a tucking surface of a tuck apparatus is pressed against a surface of the bed cover. In yet another step, the tucking surface is slid under the mattress in order to tuck the portion of the bed cover under the mattress.
These and other features, aspects and advantages of the invention will become better understood with reference to the following drawings, description and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of one embodiment of a bed-making kit under the invention;
FIG. 2 is a partial, perspective view showing the step of positioning the wedge apparatus of FIG. 1 with respect to a bed mattress under one method embodiment for making a bed under the invention;
FIG. 3 is a partial, perspective view showing the step of sliding the wedge apparatus of FIG. 2 under the bed mattress under one method embodiment for making a bed under the invention;
FIG. 4 is a partial, perspective view showing the step of positioning a tuck apparatus with respect to the bed mattress of FIG. 3 under one method embodiment for making a bed under the invention;
FIG. 5 is a partial, perspective view showing the step of sliding the tuck apparatus of FIG. 4 under the bed mattress under one method embodiment for making a bed under the invention; and
FIG. 6 is a partial, perspective view showing the step of sliding the tuck apparatus of FIG. 5 under and along one side of the bed mattress under one method embodiment for making a bed under the invention.
DETAILED DESCRIPTION OF THE INVENTION
The following detailed description is of the best currently contemplated modes of carrying out the invention. The description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the invention, since the scope of the invention is best defined by the appended claims.
In one embodiment of the invention, as shown in FIG. 1 , a kit 10 is provided for tucking at least a portion of a bed cover under a bed mattress. For purposes of this application, the word “tucking” or “tuck” is defined as locating and/or positioning a portion of a bed cover under a bed mattress. The kit 10 may include a wedge apparatus 12 and a tuck apparatus 14 . The wedge apparatus 12 may be adapted to aide in lifting a portion of a bed mattress in an upwardly direction off a box spring mattress in order to make it easier for a person making the bed to tuck in one or more bed covers between the bed mattress and box spring mattress. In other embodiments, the wedge apparatus 12 may be adapted to lift a portion of a bed mattress off other types of supporting structures. The tuck apparatus 14 may be adapted to tuck one or more portions of one or more bed covers under a bed mattress.
The wedge apparatus 12 of the kit 10 may comprise a wedge member 16 having a bottom surface 17 , a sloped surface 18 , and a first handle member 20 connected to the wedge member 16 . The bottom surface 17 and the sloped surface 18 may be adjoining, and may form an acute angle 19 which facilitates the sloped surface 18 engaging a surface of a bed mattress, and facilitates lifting of the bed mattress. The wedge member 16 may be adapted for lifting a portion of a bed mattress. Two holes 22 and 24 may define the wedge member 16 , and may extend horizontally through a cross-section of the wedge member 16 . The holes 22 and 24 may be used to reduce the weight of the wedge apparatus 12 , and may be circular or in other configurations, shapes, or quantities. A first connecting member 26 may connect the first handle member 20 to the wedge member 16 . In other embodiments, the first handle member 20 may be connected to the wedge member 16 directly, or through other means. The first connecting member 26 may be substantially rectangular, round, oval, or in other configurations or shapes. For ergonomic reasons, the first handle member 20 may be in non-parallel relation with respect to the first connecting member 26 , bottom surface 17 , wedge member 16 , and/or other portion of wedge apparatus 12 . The first handle member 20 may be at an angle 28 with respect to the first connecting member 26 in substantially the range of 30 degrees to 120 degrees. In other embodiments, angle 28 may be substantially in the range of 60 to 90 degrees. A grip member 30 may cover one or more portions of the first handle member 20 . The grip member 30 may be made of foam, rubber, or other materials.
Sloped surface 18 may be substantially linear, may begin at an end 32 of the wedge member 16 , and may end at a mattress receiving surface 34 . The mattress receiving surface 34 may be oriented in non-parallel relation with respect to sloped surface 18 . The wedge member 16 may include a substantially planar stabilizing surface 36 having a width 38 wider than a width 40 of the sloped surface 18 , and/or other portion of the wedge member 16 . One or more portions 41 of the substantially planar stabilizing surface 36 may be curved. Both the mattress receiving surface 34 and the substantially planar stabilizing surface 36 may be adapted to be oriented in substantially horizontal planes when the sloped surface 16 is slid under a bed mattress and/or above a box spring mattress. The substantially planar stabilizing surface 36 may be oriented in parallel alignment with the mattress receiving surface 34 . The first handle member 20 may be oriented in non-parallel alignment with both the substantially planar stabilizing surface 36 and the mattress receiving surface 34 . In other embodiments, the wedge apparatus 12 and/or wedge member 16 may include one or more stop members (not shown) which may prevent the wedge member 16 from slipping out of a position in between a bed mattress and/or a box spring mattress.
When the wedge member 16 is upright, as shown in FIG. 1 , so that it is oriented in a substantially vertical plane, the sloped surface 18 of the wedge member 16 may be adapted to be slid in between a bed mattress and a box spring mattress, locating one or more portions of the sloped surface 18 under the bed mattress and above the box spring mattress. In such manner, the bed mattress may be lifted upwardly off the box spring mattress due to the bed mattress being forced to slide up the sloped surface 18 of the wedge member 16 . The described movement of the wedge member 16 may be achieved by a person grasping the first handle member 20 to apply a force to the wedge member 16 in order to slide the sloped surface 18 under a bottom surface of the bed mattress and above a top surface of the box spring mattress. The substantially planar stabilizing surface 36 may be slid on top of the box spring mattress forcing the bed mattress to be slid up the sloped surface 18 until the bed mattress comes to rest on top of the mattress receiving surface 34 . In such manner, the bed mattress may be stabilized in a raised position on top of the mattress receiving surface 34 due to the use of the wedge apparatus 12 .
The use of the wedge apparatus 12 may reduce the force required to lift the bed mattress off the box spring mattress. In some embodiments, the force required to lift the bed mattress off the box spring mattress may be reduced substantially in the range of 10 to 90 percent. In other embodiments, the force may be reduced by varying percentages.
The wedge apparatus 12 may be made of plastic or other types of materials. In other embodiments, the wedge apparatus 12 may be of varying shapes, sizes, configurations, and orientations, with differing numbers and types of sloped surfaces 18 .
The tuck apparatus 14 of the kit 10 may comprise a tuck member 42 having a tucking surface 44 , and a second handle member 46 connected to the tuck member 42 by a second connecting member 52 . The tuck member 42 may be adapted for tucking a portion of a bed cover under a bed mattress. In other embodiments, the second handle member 46 may be directly connected to the tuck member 42 , or connected by other means. The second handle member 46 may be in non-parallel relation with respect to tuck member 42 , or other portion of tuck apparatus 14 . The tuck member 42 may comprise a substantially planar, triangular surface 48 . The tucking surface 44 of the tuck member 42 may lie at one end 50 of the tuck member 42 , may be substantially linear, and may be substantially perpendicular to the second connecting member 52 . A width 54 of the tucking surface 44 may be wider than a width 56 of the second connecting member 52 in order to allow contact with a greater portion of the bed cover being tucked in. The second connecting member 52 may be substantially rectangular, round, oval, or in other configurations or shapes. For ergonomic reasons, the second handle member 46 may be at an angle 58 with respect to the second connecting member 52 and/or tuck member 42 in substantially the range of 30 degrees to 120 degrees. In other embodiments, angle 58 may be substantially in the range of 60 to 90 degrees. A grip member 60 may cover one or more portions of the second handle member 46 . The grip member 60 may be made of foam, rubber, or other materials.
When the sloped surface 18 of the wedge member 16 of the wedge apparatus 12 is located under a bed mattress and the tuck member 42 is oriented in a substantially horizontal plane, the tucking surface 44 of the tuck apparatus 14 is adapted to be pressed against one or more surfaces of one or more bed covers overhanging the bed mattress. While in this position, the tucking surface 44 may be adapted to be slid under a surface of the bed mattress and above a surface of the box spring mattress, in order to force a portion of the bed cover in between the box spring mattress and mattress, thereby tucking in that portion of the bed cover. Movement of the tucking surface 44 in such manner may be achieved by a person grasping the second handle member 46 .
The use of the tuck apparatus 14 and/or wedge apparatus 12 may reduce the force required to tuck a portion of the bed cover under the bed mattress into a position in between the mattress and box spring mattress. In some embodiments, the force required to tuck the portion of the bed cover under the mattress may be reduced substantially in the range of 10 to 90 percent. In other embodiments, the force may be reduced by varying percentages.
The tuck apparatus 14 may be made of plastic or other types of materials. In other embodiments, the tuck apparatus 14 may be of varying shapes, sizes, configurations, and orientations, with differing numbers, types, and configurations of tucking members 42 and tucking surfaces 44 .
In another embodiment, a method is disclosed for tucking at least a portion of at least one bed cover under a mattress of a bed. The method may be used to tuck the bed cover in between a bed mattress and a box spring mattress, or other support structure. In one step of the method, as shown in FIG. 2 , the wedge apparatus 12 of FIG. 1 may be positioned adjacent to one or more bed covers 62 overhanging a bed mattress 64 and a box spring mattress 66 , or other support structure. In this position, a wedge member 16 of the wedge apparatus 12 may be aligned for engagement with a bottom surface of the bed mattress 64 and a top surface of the box spring mattress 66 . In other embodiments, the wedge apparatus 12 may be positioned adjacent bed and box spring mattresses 64 and 66 without the presence of bed covers 62 . The wedge apparatus 12 may be positioned adjacent a substantially center area 65 of a side portion 67 of the bed mattress 64 . In other embodiments, the wedge apparatus 12 may be positioned at different areas of the bed mattress 64 , such as the corners or other areas of the bed mattress 64 . The wedge apparatus 12 may comprise any of the wedge apparatus embodiments disclosed within this specification.
In another step of the method, as shown in FIG. 3 , a sloped surface 18 of the wedge apparatus 12 may be slid under the bed mattress 64 , and above the box spring mattress 66 or other support structure, in order to lift at least a portion of the bed mattress 64 upwardly. The sloped surface 18 of the wedge apparatus 12 may be slid under the substantially center area 65 of the side portion 67 of the bed mattress 64 . In other embodiments, the sloped surface 18 of the wedge apparatus 12 may be slid under different areas of the bed mattress 64 in order to lift different portions of the mattress 64 upwardly. For instance, the sloped surface 18 of the wedge apparatus 12 may be slid, at separate times, into substantially center areas of three different sides of the bed mattress 64 in order to aide in tucking in bed covers 62 on three sides of the bed mattress 64 . In other embodiments, the sloped surface 18 of the wedge apparatus 12 may be slid into varying areas of any side of the bed mattress 64 . The wedge apparatus 12 may be slid by a person grasping and applying a force to a first handle member 20 of the wedge apparatus 12 and sliding the sloped surface 18 under a bottom surface of the mattress 64 and above a top surface of the box spring mattress 66 or other support structure.
During this step, as shown in FIG. 3 , the wedge member 16 of the wedge apparatus 12 may be oriented upright in a substantially vertical plane, and both a mattress receiving surface 34 and a substantially planar stabilizing surface 36 of the wedge apparatus 12 may be oriented in substantially horizontal planes. As the sloped surface 18 of the wedge apparatus 12 is slid under the bed mattress 64 , the insertion of the sloped surface 18 may force a portion of one or more bed covers 62 overhanging the bed mattress 64 to be tucked between the bed mattress 64 and box spring mattress 66 in the area where the sloped surface 18 is inserted. After the sloped surface 18 of the wedge apparatus 12 is slid under the bed mattress 64 , the bed mattress 64 may abut against the mattress receiving surface 34 of the wedge apparatus 12 , which may be oriented in a substantially horizontal plane 36 to stabilize the mattress 64 in its position against the wedge apparatus 12 . Similarly, after the sloped surface 18 of the wedge apparatus 12 is slid under the bed mattress 64 , the box spring mattress 66 may be abutted against the substantially planar stabilizing surface 36 of the wedge apparatus 12 , which may be oriented in a substantially horizontal plane to stabilize the wedge apparatus 12 in its position against the box spring mattress 66 .
In yet another step of the method, as shown in FIG. 4 , after the wedge apparatus 12 is slid under the bed mattress 64 , a tuck member 42 of a tuck apparatus 14 may be oriented in a substantially horizontal plane, and a tucking surface 44 of the tuck apparatus 14 may be positioned adjacent and pressed against a surface of one or more of the bed covers 62 overhanging the bed mattress 64 and box spring mattress 66 , or other support structure. The tucking surface 44 of the tuck apparatus 14 may be positioned adjacent and pressed against a substantially center area 65 of the side portion 67 of the bed mattress 64 , just to the side of the location of the inserted wedge apparatus 12 . In other embodiments, the tucking surface 44 of the tuck apparatus 14 may be positioned in a variety of positions with respect to the bed mattress 64 , bed cover 62 , and/or wedge apparatus 12 . In still other embodiments, the tucking surface 44 of the tuck apparatus 14 may be positioned adjacent and pressed against different surfaces of the bed covers 62 along different areas of the bed mattress 64 in order to place the tucking surface 44 in position to tuck different portions of the bed covers 62 under different areas of the mattress 64 . For instance, the tucking surface 44 of the tuck apparatus 14 may be positioned adjacent and pressed against, at separate times, substantially center areas on three different sides of the bed mattress.
Movement of the tucking surface 44 of the tuck apparatus 14 may be accomplished by a person grasping a second handle member 46 of the tuck apparatus 14 . When the tucking surface 44 of the tuck apparatus 14 is positioned adjacent and pressed against a surface of one or more of the bed covers 62 , the tuck member 42 may be oriented in a substantially horizontal plane. In other embodiments, the tuck member 42 may be oriented in various configurations or orientations. For instance, the tuck member 42 may be oriented in a substantially vertical plane and/or horizontal plane and the tucking surface 44 may be positioned adjacent and pressed against a portion of bed cover 62 lying in between a bed headboard (not shown) and the bed mattress 64 . It should be noted that the tuck apparatus 14 may comprise any of the tuck apparatus embodiments disclosed within this specification.
In another step of the method, as shown in FIG. 5 , after the wedge apparatus 12 is slid under the bed mattress 64 , the tucking surface 44 of the tuck apparatus 14 may be slid, while the tuck member 42 is oriented in a substantially horizontal plane, under the bed mattress 64 and above the box spring mattress 66 or other support structure, in order to tuck a portion of the bed covers 62 in between the bed mattress 64 and box spring mattress 66 in the area where the tucking surface 44 is inserted. The tucking surface 44 of the tuck apparatus 14 may be slid under a substantially center area 65 of the side portion 67 of the bed mattress 64 , just to either side of the location of the inserted wedge apparatus 12 . In other embodiments, the tucking surface 44 of the tuck apparatus 14 may be slid under varying portions of the bed mattress 64 in varying positions relative to the placement of the wedge apparatus 12 . For instance, the tucking surface 44 of the tuck apparatus 14 may be slid under, at separate times, substantially center areas on three different sides of the bed mattress in order to tuck in different portions of the bed covers 62 at different areas of the bed mattress 64 . In another embodiment, the tucking surface 44 may be slid in between a bed headboard (not shown) and the bed mattress 64 in order to tuck a portion of bed cover 62 in between the bed headboard and bed mattress 64 . Movement of the tucking surface 44 may be accomplished by a person grasping the second handle member 46 of the tuck apparatus 14 in order to move the tucking surface 44 as described.
In still another step of the method, the tucking surface 44 of the tuck apparatus 14 may be slid, while the tuck member 42 is oriented in a substantially horizontal plane, under and along one side of the bed mattress 64 from its position shown in FIG. 5 to its end position 69 under the bed mattress 64 shown in FIG. 6 . In such manner the bed covers 62 may be tucked in between the bed mattress 64 and box spring mattress 66 , or other support structure, along the entire length of the bed mattress 64 that the tucking surface 44 is slid. In order to tuck in bed covers 62 along varying sides of the bed mattress 66 , the tucking surface 44 of the tuck apparatus 14 may be slid along various sides of the bed mattress 66 . For instance, the tucking surface 44 of the tuck apparatus 14 may be slid, at different times, from substantially center areas of three side portions of the mattress to three respective end portions of the mattress 64 in order to tuck in the bed covers 62 along three different sides of the mattress 64 . In other embodiments, the tucking surface 44 may be slid into and along different areas of varying sides of the bed mattress 66 . For instance, the tucking surface 44 may be slid in between, and along, a bed headboard (not shown) and the bed mattress 64 in order to tuck bed cover 62 in between the bed headboard and bed mattress 64 .
The wedge apparatus 12 and tuck apparatus 14 may be used in conjunction with each other to tuck in bed covers 62 around the entire mattress 64 . For instance, a portion of the wedge apparatus 12 may be slid under a portion of the mattress 64 on one side of the mattress 64 . The tuck apparatus 14 may be pressed against a portion of the bed covers 62 on that side of the mattress 64 . The tuck apparatus 14 may then be slid under and along that side of the mattress 64 in order to tuck in the bed covers 62 along that side of the mattress 64 . Subsequently, the wedge apparatus 12 may be removed from that side of the mattress 64 and slid under a portion of the mattress 64 on a second side of the mattress 64 . The tuck apparatus 14 may be pressed against a portion of the bed covers 62 on the second side of the mattress 64 . The tuck apparatus 14 may then be slid under and along the second side of the mattress 64 in order to tuck in the bed covers 62 along the second side of the mattress 64 . This process may be repeated to tuck in bed covers 62 along as many sides of the bed mattress 64 as desired in order to fully make the bed.
In another embodiment, the invention may comprise the wedge apparatus 12 shown in FIG. 1 without the tuck apparatus 14 . The wedge apparatus 12 may allow a portion of a bed mattress 64 to be lifted off a box spring mattress 66 , or other support structure. The structure of the wedge apparatus 12 may comprise any of the wedge apparatus 12 embodiments disclosed within this specification.
In still another embodiment, the invention may comprise the tuck apparatus 14 shown in FIG. 1 without the wedge apparatus 12 . The tuck apparatus 14 may allow one or more portions of one or more bed covers 62 to be tucked in between a bed mattress 64 and box spring mattress 66 , or other support structure. The structure of the tuck apparatus 14 may comprise any of the tuck apparatus embodiments disclosed within this specification.
In yet another embodiment, the invention may comprise a method of sliding the wedge apparatus 12 of FIG. 1 under a bed mattress 64 in order to lift one or more portions of the mattress in an upwardly direction off a box spring mattress 66 or other support structure. The method may not include use of tuck apparatus 14 . The structure of the wedge apparatus 12 may comprise any of the wedge apparatus embodiments disclosed within this specification. Similarly, the method of use of the wedge apparatus 12 may comprise any of the methods of use of the wedge apparatus as described in this specification.
In an additional embodiment, the invention may comprise a method of tucking a portion of at least one bed cover 62 under a bed mattress 64 utilizing the tuck apparatus 14 of FIG. 1 , without the use of wedge apparatus 12 . The structure of the tuck apparatus 14 may comprise any of the tuck apparatus embodiments disclosed within this specification. Similarly, the method of use of the tuck apparatus 14 may comprise any of the methods of use of the tuck apparatus as described in this specification.
One or more embodiments of the disclosed wedge and tuck apparatus and/or methods of the invention may solve one or more problems in lifting bed mattresses and/or tucking in bed covers. The invention may make it less difficult to make a bed, may decrease the force required to make a bed, may decrease the fatigue a person experiences in making a bed, may decrease the likelihood of injury a person may experience in making a bed, may improve efficiency in making a bed, may improve the quality of the made bed, may improve the accuracy, repeatability, and consistency of making a bed, and/or may address other types of problems known in the art.
It should be understood, of course, that the foregoing relates to exemplary embodiments of the invention and that modifications may be made without departing from the spirit and scope of the invention as set forth in the following claims. | The invention discloses differing embodiments of apparatus, and methods for their use, which are designed to aide in lifting bed mattresses and tucking in bed covers. In some embodiments, kits are disclosed which include wedge apparatus for lifting bed mattresses, and tuck apparatus for tucking in bed covers. In other embodiments, wedge apparatus for lifting portions of bed mattresses are disclosed. In still other embodiments, tuck apparatus for tucking in bed covers are provided. Additional embodiments disclose methods for using the kits, wedge apparatus, and tuck apparatus. | 0 |
This application is a division of Ser. No. 09/472,850 filed Dec. 28, 1999 U.S. Pat. No. 6,129,454, which is a division of Ser. No. 09/136,960 filed Aug. 20, 1998, U.S. Pat. No. 6,012,226, which is a division of Ser. No. 08,675,495 filed Jul. 3, 1996, U.S. Pat. No. 5,800,069.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a compound bearing assembly and a method of manufacturing the same, the compound bearing assembly being used in rotating portions of a computer and its peripheral devices.
2. Description of the Prior Art
As for a conventional compound bearing assembly constructed of a pair of ball bearing units A, B mounted on a rotary shaft D of rotating portions of a computer or its peripheral devices, as is clear from FIG. 4 ( a ), it is necessary to produce its components separately. Consequently, a sleeve-like spacer C and such pair of the ball bearing units A, B are produced separately from each other. These components A, B, C of the conventional compound bearing assembly are then delivered to a user. After receipt of the components, the user mounts the components A, B, C on the rotary shaft D to complete the conventional compound bearing assembly, as shown in FIG. 4 ( b ).
As described above, in the conventional compound bearing assembly, it is necessary for the user to mount the pair of the ball bearing units A, B and the spacer C on the rotary shaft D in a condition in which the ball bearing units A, B are spaced apart from each other through the spacer C. Consequently, the conventional compound bearing assembly suffers from the following problems:
(a) While keeping a sufficient rigidity, the rotary shaft D is required to be sized in outer diameter so as to engage with the inner race rings of the ball bearing units A, B;
(b) Since the spacer C is a separate component independent of the pair of the ball bearing units A and B, it is necessary for the spacer C to have its opposite end surfaces improved in parallelism therebetween and also in flatness thereof, taken in connection with the dimensions of the ball bearing units A, B being assembled together with the spacer C; and
(c) Since the spacer C is merely sandwiched between a pair of outer race rings of the ball bearing units A and B, it is necessary for the user to have the spacer C coaxially mounted on the rotary shaft D with high accuracy, which requires the spacer C to have its opposite axial end surfaces brought into uniform contact with axially inner end surfaces of the outer race rings of the ball bearing units A, B, and, therefore takes much time and labor.
SUMMARY OF THE INVENTION
It is an object of the present invention to solve the above problems by providing a compound bearing assembly and a method of manufacturing the same, the compound bearing assembly being easily mounted in rotating portions of a computer and its peripheral devices at the user's end.
According to a first aspect of the present invention, the above object of the present invention is accomplished by providing:
A compound bearing assembly characterized in that:
(a) a stepped-diameter shaft is provided with a large-diameter portion, a small-diameter portion and an inner raceway groove directly formed in an outer peripheral surface of the large-diameter portion of the shaft;
(b) the stepped-diameter shaft is encircled by a sleeve-like outer race ring which is provided with a single-piece outer race ring in one of its axially opposite ends and an outer raceway groove in an inner peripheral surface of the other of the axially opposite ends; and
(c) a plurality of first balls rotatably mounted in the inner raceway groove of the large-diameter portion of the shaft are held by the outer raceway groove of the single-piece outer race ring, and a plurality of second balls rotatably mounted in the inner raceway groove of the inner race ring are held by the outer raceway groove of the sleeve-like outer race ring or by that of the single-piece outer race ring.
According to a second aspect of the present invention, the above object of the present invention is accomplished by providing:
The compound bearing assembly as set forth in the first aspect of the present invention, wherein:
the first balls around the inner raceway groove of the large-diameter portion are held by the outer raceway groove of the single-piece outer race ring; and
the second balls around the inner raceway groove of the inner race ring mounted on the small-diameter portion are held by the outer raceway groove of the sleeve-like outer race ring.
According to a third aspect of the present invention, the above object of the present invention is accomplished by providing:
The compound bearing assembly as set forth in the first aspect of the present invention, wherein:
the first balls around the inner raceway groove of the large-diameter portion of the shaft are held by the outer raceway groove of the sleeve-like outer race ring; and
the second balls around the inner raceway groove of the inner race ring mounted on the small-diameter portion are held by the outer raceway groove formed in an inner peripheral surface of the outer race ring.
According to a fourth aspect of the present invention, the above object of the present invention is accomplished by providing:
A method of manufacturing a compound bearing assembly characterized in that:
a stepped-diameter shaft is provided with a large-diameter portion, a small-diameter portion and an inner raceway groove directly formed in an outer peripheral surface of the large-diameter portion of the stepped-diameter shaft;
the stepped-diameter shaft is encircled by a sleeve-like outer race ring which is provided with a single-piece outer race ring in one of its axially opposite ends and an outer raceway groove in an inner peripheral surface of the other of the axially opposite ends;
a plurality of first balls rotatably mounted in the inner raceway groove of the large-diameter portion of the shaft are held by the outer raceway groove of the single-piece outer race ring, and a plurality of second balls rotatably mounted in the inner raceway groove of the inner race ring are held by the outer raceway groove of the sleeve-like outer race ring or by that of the outer race ring;
in a condition in which a predetermined pre-load is applied to an outer end portion of the inner race ring or of the sleeve-like outer race ring, the inner race ring is firmly bonded to the small-diameter portion of the stepped-diameter shaft by means of an adhesive;
whereby the components such as the sleeve-like outer race ring, single-piece outer race ring, inner race ring and the like are assembled together with the stepped-diameter shaft into a compound bearing assembly.
According to a fifth aspect of the present invention, the above object of the present invention is accomplished by providing:
The method of manufacturing the compound bearing assembly, as set forth in the fourth aspect of the present invention, wherein:
the first balls around the inner raceway groove of the large-diameter portion of the shaft are held by the outer raceway groove of the single-piece outer race ring; and
the second balls around the inner raceway groove of the single-piece outer race ring are held by an outer raceway groove of the sleeve-like outer race ring, the outer raceway groove being formed in an inner peripheral surface of the sleeve-like outer race ring.
According to a sixth aspect of the present invention, the above object of the present invention is accomplished by providing:
The method of manufacturing the compound bearing assembly, as set forth in the fourth aspect of the present invention, wherein:
the first balls around the inner raceway groove of the large-diameter portion of the shaft are held by the outer raceway groove of the sleeve-like outer race ring; and
the second balls around the inner raceway groove of the inner race ring mounted on the small-diameter portion of the shaft are held by an outer raceway groove of the outer race ring, the outer raceway groove being formed in an inner peripheral surface of the outer race ring.
According to a seventh aspect of the present invention, the above object of the present invention is accomplished by providing:
A compound bearing assembly characterized in that:
an inner raceway groove is directly formed in an outer peripheral surface of a large-diameter portion of a stepped-diameter shaft which is provided with a small-diameter portion together with the large-diameter portion;
first balls disposed between the inner raceway groove and an outer raceway groove which is formed in an inner peripheral surface of a single-piece outer ring mounted around the large-diameter portion;
a ball bearing unit has its inner race ring mounted on the small-diameter portion of the stepped-diameter shaft and its balls disposed between its inner and its outer race ring; and
a sleeve-like spacer is axially sandwiched between the outer race ring of the ball bearing unit and the single-piece outer ring.
According to a eighth aspect of the present invention, the above object of the present invention is accomplished by providing:
A method of manufacturing a compound bearing assembly is characterized in that:
an inner raceway groove is directly formed in an outer peripheral surface of a large-diameter portion of a stepped-diameter shaft which is provided with a small-diameter portion together with the large-diameter portion;
first balls disposed between the inner raceway groove and an outer raceway groove which is formed in an inner peripheral surface of a single-piece outer ring mounted around the large-diameter portion;
a ball bearing unit has its inner race ring slidably mounted on the small-diameter portion of the stepped-diameter shaft and its balls disposed between its inner and its outer race ring;
a sleeve-like spacer is axially sandwiched between the outer race ring of the ball bearing unit and the single-piece outer ring; and
the inner race ring of the ball bearing unit is fixed to the small-diameter portion of the stepped-diameter shaft in a condition in which a predetermined pre-load is applied to an outer end surface of one of the inner and the outer race ring of the ball bearing unit.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a longitudinal sectional view of a first embodiment of the compound bearing assembly of the present invention;
FIG. 2 is a longitudinal sectional view of a second embodiment of the compound bearing assembly of the present invention;
FIG. 3 is a longitudinal sectional view of a third embodiment of the compound bearing assembly of the present invention;
FIG. 4 ( a ) is a longitudinal sectional view of a conventional compound bearing assembly, illustrating each of its components, i.e., a pair of ball bearing units and a spacer, from which the compound bearing assembly is assembled; and
FIG. 4 ( b ) is a longitudinal sectional view of the conventional compound bearing assembly after completion of assembling work thereof, illustrating both the ball bearing units and the spacer having been properly mounted on a shaft.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinbelow, the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 shows a first embodiment of a compound bearing assembly of the present invention.
As shown in FIG. 1, a a stepped-diameter shaft 1 is provided with a large-diameter portion 1 a and a small-diameter portion 1 b . Directly formed in an outer peripheral surface of the large-diameter portion 1 a of the shaft 1 is an annular inner raceway groove 2 a.
A single-piece outer race ring 3 is oppositely disposed from the inner raceway groove 2 a of the large-diameter portion 1 a of the shaft 1 , and provided with an annular outer raceway groove 2 b in its inner peripheral surface, so that a plurality of first balls 4 are rotatably mounted between the inner raceway groove 2 a of the shaft 1 and the outer raceway groove 2 b of the outer race ring 3 .
As is clear from FIG. 1, a sleeve-like outer race ring 5 is provided with an annular outer raceway groove 6 b in an inner peripheral surface of its outer-end portion (i.e., its right-hand portion as viewed in FIG. 1 ). This outer raceway groove 6 b of the outer race ring 5 is oppositely disposed from an inner race ring 7 a . This inner race ring 7 a is mounted on the small-diameter portion 1 b of the stepped-diameter shaft 1 in an insertion manner, and provided with an annular inner raceway groove 6 a in its outer peripheral surface. A plurality of second balls 8 a are rotatably mounted between the the outer raceway groove 6 b of the sleeve-like outer race ring 5 and the inner raceway groove 6 a of the inner race ring 7 a.
Further, an outer diameter of the inner race ring 7 a mounted on the small-diameter portion 1 b of the stepped-diameter shaft 1 is equal to an outer diameter of the large-diameter portion 1 a of the shaft 1 . Consequently, the first balls 4 and the second balls 8 a are the same in diameter.
In this first embodiment of the compound bearing assembly of the present invention, in its assembling work, for example, the inner race ring 7 a is first slidably mounted on the small-diameter portion 1 b of the shaft 1 in an insertion manner. Then, a predetermined pre-load is axially inwardly applied to an outer-end surface (i.e., a right-hand end surface as viewed in FIG. 1) of the inner race ring 7 a . Under such circumstances, the inner race ring 7 a is bonded to the small-diameter portion 1 b of the shaft 1 by means of a suitable adhesive or similar connecting means. Thus the outer race ring 3 , sleeve-like outer race ring 5 , inner race ring 7 a and the remaining components are assembled on the stepped-diameter shaft 1 to form the first embodiment of the compound bearing assembly of the present invention.
Incidentally, in FIG. 1 : the reference numeral 10 denotes a ball retainer coaxially arranged with the stepped-diameter shaft 1 so as to be mounted around the shaft 1 .
FIG. 2 shows a second embodiment of the compound bearing assembly of the present invention.
In this second embodiment, the inner raceway groove 2 a is directly formed in an outer peripheral surface of the large-diameter portion 1 a of the stepped-diameter shaft 1 .
As is clear from FIG. 2, in the second embodiment of the present invention, the sleeve-like outer race ring 5 is provided with an annular outer raceway groove 2 b ′ in an inner peripheral surface of its outer-end portion (i.e., its left-hand portion as viewed in FIG. 2 ). This outer raceway groove 2 b ′ of the outer race ring 5 is oppositely disposed from an inner raceway groove 2 a directly formed in an outer peripheral surface of the large-diameter portion 1 a of the stepped-diameter shaft 1 . A plurality of the first balls 4 are rotatably mounted between the outer raceway groove 2 b ′ of the sleeve-like outer race ring 5 and the inner raceway groove 2 a of the large-diameter portion 1 a of the shaft 1 .
A ball bearing unit 7 is a conventional one comprising an outer race ring 7 b , the inner race ring 7 a , a plurality of third balls 8 b rotatably mounted between these race rings 7 b , 7 a , a ball retainer 10 and the inner race ring 7 a , and has its inner race ring 7 a fixedly mounted on the small-diameter portion 1 b of the stepped-diameter shaft 1 in an insertion manner.
Further, as is clear from FIG. 2, an outer diameter of the inner race ring 7 a of the ball bearing unit 7 is the same as that of the large-diameter portion 1 a of the shaft 1 , while an outer and an inner diameter of the outer race ring 7 b of the ball bearing unit 7 are the same as those of the sleeve-like outer race ring 5 . Consequently, the balls 4 , 8 b are the same in diameter.
In this second embodiment of the present invention shown in FIG. 2, in its assembling work, for example, the inner race ring 7 a is first slidably mounted on the small-diameter portion 1 b of the shaft 1 in an insertion manner. Then, a predetermined pre-load is axially inwardly applied to an outer-end surface (i.e., a right-hand end surface as viewed in FIG. 2) of the inner race ring 7 a . Under such circumstances, the inner race ring 7 a is bonded to the small-diameter portion 1 b of the shaft 1 by means of a suitable adhesive or similar connecting means. Thus the sleeve-like outer race ring 5 , outer race ring 7 b , inner race ring 7 a and the remaining components are assembled on the stepped-diameter shaft 1 to form the second embodiment of the compound bearing assembly of the present invention.
FIG. 3 shows a third embodiment of the compound bearing assembly of the present invention.
This third embodiment of the compound bearing assembly is assembled on the stepped-diameter shaft 1 which is provided with the annular inner raceway groove 2 a in its outer peripheral surface. In the third embodiment, the single-piece outer race ring 3 is provided with the annular outer raceway groove 2 b in its inner peripheral surface, and coaxially mounted around the large-diameter portion 1 a of the stepped-diameter shaft 1 while spaced apart from the large-diameter portion 1 a to define an annular space therebetween. Rotatably mounted in this annular space are a plurality of the first balls 4 .
On the other hand, the conventional ball bearing unit 7 , which comprises the outer race ring 7 b , inner race ring 7 a , a plurality of third balls 8 b rotatably mounted between these race rings 7 b and 7 a and the ball retainer 10 , has its inner race ring 7 a mounted on the small-diameter portion 1 b of the shaft 1 . A sleeve-like spacer 11 is fixedly sandwiched between the single-piece outer race ring 3 and the outer race ring 7 b of the ball bearing unit 7 so as to be coaxially arranged with the shaft 1 .
An outer diameter of the inner race ring 7 a of the ball bearing unit 7 is equal to that of the large-diameter portion 1 a of the stepped-diameter shaft 1 . Further, an outer and an inner diameter of the outer race ring 7 b of the ball bearing unit 7 are equal to those of the single-piece outer race ring 3 , respectively. Consequently, the first balls 4 and the second balls 6 are the same in diameter.
Also in this third embodiment of the present invention as is in the second embodiment of the present invention, the inner race ring 7 a of the ball bearing unit 7 is axially slidably mounted on the small-diameter portion 1 b of the stepped-diameter shaft 1 in an insertion manner. Then, a predetermined pre-load is axially inwardly applied to the outer-end surface (i.e., the right-hand end surface as viewed in FIG. 3) of the inner race ring 7 a of the ball bearing unit 7 . Under such circumstances, the inner race ring 7 a is firmly bonded to the small-diameter portion 1 b of the shaft 1 . Thus the components of the compound bearing assembly of the present invention such as the outer race ring 3 , sleeve-like spacer 11 , inner race ring 7 a and the like are assembled on the stepped-diameter shaft 1 to complete the third embodiment of the compound bearing assembly of the present invention.
Incidentally, in the drawings: the reference numerals 9 a and 9 b denote an inner raceway groove and an outer raceway groove, respectively.
Although the balls 4 , 8 a , 8 b are the same in diameter in any one of the above embodiments of the compound bearing assembly of the present invention, it is also possible to use first balls 4 , which are different in diameter from the other balls 8 a and 8 b , in the large-diameter portion 1 a of the stepped-diameter shaft 1 .
The compound bearing assembly of the present invention having the above construction has the following actions and effects:
(1) Since the components such as the single-piece outer race ring 3 , balls 4 , sleeve-like spacer 5 , ball bearing unit 7 and the like are already assembled on the stepped-diameter shaft 1 by a bearing maker to form the compound bearing assembly of the present invention, the user is released from a cumbersome assembling work of the compound bearing assembly, so that the compound bearing assembly of the present invention is easily mounted inside a sleeve-like rotating element of a desired instrument by inserting the assembly into the rotating element and fixing the assembly therein;
(2) Since the compound bearing assembly of the present invention uses the stepped-diameter shaft 1 provided with the large-diameter portion 1 a having its outer peripheral surface formed into the annular inner raceway groove 2 a , it is possible for the compound bearing assembly of the present invention to eliminate the conventional type inner race ring in the large-diameter portion 1 a of the stepped-diameter shaft 1 , which permits the shaft 1 to be partially improved in rigidity;
(3) Since the stepped-diameter shaft 1 is provided with the large-diameter portion 1 a , and, therefore improved in rigidity, it is possible to increase the resonance point of a spindle motor which is provided with the compound bearing assembly of the present invention and used in office automation instruments and similar systems, so that the spindle motor provided with the compound bearing assembly of the present invention may be prevented from resonating to the remaining components of the instruments, whereby these instruments are improved in reliability;
(4) The number of the conventional ball bearing units used in the compound bearing assembly of present invention is only one particularly which is the ball bearing unit 7 . Consequently, the compound bearing assembly of the present invention uses only one inner race ring 7 a , and therefore has a small number of components in comparison with the conventional compound bearing assemblies; and
(5) The sleeve-like outer race ring 5 and the spacer 11 may be fabricated by the bearing maker so as to align with the ball bearing unit 7 and the single-piece outer race ring 3 with high accuracy.
In each of the first and the second embodiments of the compound bearing assembly of the present invention, a sleeve-like outer race ring 5 serves as both a conventional outer race ring and a sleeve-like spacer. Consequently, the following actions and effects are further obtained:
(6-1) Since the sleeve-like outer race ring 5 also serves as a spacer, it is possible to eliminate a conventional independent spacer, which makes it possible for the compound bearing assembly of the present invention to reduce the number of its components;
(6-2) In comparison with the conventional compound bearing assembly in which a pair of the ball bearing units A, B are disposed in axially opposite sides of the spacer C, it is possible for the compound bearing assembly of the present invention to reduce its entire axial length, which makes it possible to downsize the instruments provided with the compound bearing assembly of the present invention; and
(6-3) In the sleeve-like outer race ring 5 , one of its axially opposite end surfaces must be machine-finished so as to be brought into uniform contact with the axially inward end surface of the outer race ring 3 or 7 b . However, the other of the axially opposite end surfaces of the sleeve-like outer race ring 5 may remain unmachined, which permits a reduction of the number of process steps in manufacturing of the compound bearing assembly the present invention. | A single-piece outer race ring 3 , a sleeve-like spacer 11 , a plurality of first balls 4 , a conventional ball bearing unit 7 , a stepped-diameter shaft 1 and the like are assembled into a compound bearing assembly by a bearing maker with high accuracy to enable a user to be free from a cumbersome assembling work of rotating portions or cylindrical rotary shaft and its bearing means of a computer and its peripheral devices. In use, the compound bearing assembly is coaxially mounted in the cylindrical rotary shaft and the like at the user's end to rotatably support the cylindrical rotary shaft and the like in the computer and its peripheral devices. | 5 |
This is a continuation of application Ser. No. 947,787, filed Dec. 30, 1986, now abandoned.
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to but in no way dependent upon copending applications Ser. Nos. 832,559; 832,493; and 832,556; filed Feb. 21, 1986 and of common ownership herewith.
BACKGROUND OF THE INVENTION
This invention relates generally to cathode ray tubes (CRTs) and is particularly directed to a low cost flat faceplate and front assembly, and method of production therefor, for use in a color CRT having a flat tensioned shadow mask.
Most glass produced in the past has been in the form of sheet, window or drawn glass which is characterized as having two smooth or fire polished surfaces which typically require no further processing once produced. Over the years, this has been the most important type of flat glass for the construction industry and is used primarily for windows. This type of glass is initially formed as plate glass by drawing the glass vertically from a tank by means of a metal "bait", whereupon the glass is immediately contacted by cooled side-rollers to prevent it from flowing together and is then directed horizontally before entering an annealing lehr. The degree of flatness and parallelism achieved by thus rolling the malleable glass is of a relatively high standard, which is typically improved by optical methods such as grinding, polishing and acid etching.
Since the 1960s, however, sheet glass has increasingly been replaced by float glass which is manufactured by a process wherein the glass floats like an endless ribbon on a bath of molten tin to produce high quality glass having flat surface planes. Float glass has been used for glazing whenever transparency is required in buildings and is also used as a raw material for making safety glass, mirrors and otherwise finished or processed flat glass for furniture as well as for liquid crystal diode (LCD) displays.
Video displays such as CRTs have a glass construction which to date has not been amenable to either of the aforementioned glass production techniques. A CRT generally consists of an evacuated envelope having a neck portion, a faceplate, and a funnel portion therebetween. An electron gun disposed in the neck portion of the envelope emits energetic electrons which are directed onto the inner surface of the faceplate. Disposed on the inner surface of the faceplate are a large number of phosphor elements which glow momentarily when struck from the rear by electrons from the electron gun to produce a video image which is visible through the faceplate.
Prior art CRTs have generally been of the curved faceplate type wherein the faceplate is generally convex as seen by a viewer. The faceplate is initially formed in a pressing mold which typically includes a hollow mold into which a glass gob is deposited. The glass gob is then hydraulically or pneumatically pressed by a sealing ring-guided plunger until the glass is pressed into all areas of the mold and assumes the desired curvature. After solidification, the plunger is withdrawn and the solid glass faceplate is removed from the hollow mold. One example of a method of press shaping glass faceplates using a rotary press-molding machine is disclosed in U.S. Pat. No. 3,615,328 to Coleman. This method as well as other prior art approaches involves the step-wise, sequential fabrication of individual faceplates and requires long periods of pressing time and is thus lengthy and expensive.
Recent developments in video displays have led to a color CRT having a substantially flat faceplate and incorporating a shadow mask of the tensioned foil type which offers various advantages over the aforementioned prior art curved faceplate CRTs including improved brightness and/or contrast of the video image. Although not subjected to the curvature inducing sagging operation, flat faceplates for use in CRTs having flat tensioned shadow masks are also generally formed by the aforementioned pressing process. As a result, flat faceplates as in the case of the aforementioned curved CRT faceplates have not yet been amenable to low cost, simplified production techniques.
The commercial success of CRTs employing a substantially flat faceplate depends, in large part, upon the cost to manufacture this type of CRT. Much effort has thus been expended to reduce the cost of CRTs having a substantially flat faceplate and incorporating a shadow mask of the flat tensioned foil type. The present invention is the result of such efforts in that it contemplates a method of producing, as well as the composition of, a flat glass faceplate for a color CRT which substantially simplifies and reduces the cost of the faceplate, while providing a high degree of video image acuity.
OBJECTS OF THE INVENTION
Accordingly, it is an object of the present invention to provide a low cost flat faceplate for use in a color CRT.
It is another object of the present invention to reduce the cost of color CRTs having a flat tensioned shadow mask which offer high video image acuity.
A further object of the present invention is to provide a method of producing a flat faceplate for use in a color CRT which involves neither the grinding, polishing or acid etching of the faceplate.
A still further object of the present invention is to provide a low cost front assembly for a color CRT having a flat faceplate and a flat tensioned shadow mask mounted thereto.
BRIEF DESCRIPTION OF THE DRAWINGS
The appended claims set forth those novel features which characterize the invention. However, the invention itself, as well as further objects and advantages thereof, will best be understood by reference to the following detailed description of a preferred embodiment taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a simplified schematic diagram illustrating a float glass system for producing flat faceplates for color CRTs in accordance with the present invention; and
FIG. 2 is a partially cutaway perspective view of flat tensioned shadow mask CRT incorporating a flat faceplate in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, there is shown a simplified schematic diagram of a system 10 for fabricating flat glass faceplates for use in color CRTs in accordance with the present invention.
The flat faceplate manufacturing system 10 includes first, second, third and fourth supply reservoirs 12, 14, 16 and 18 which provide the raw materials from which flat faceplates in accordance with the present invention are made. Thus, the first supply reservoir 12 contains a quantity of sand 12a, the second supply reservoir 14 contains a supply of lime 14a, the third supply reservoir 16 holds a supply of soda 16a, and the fourth supply reservoir 18 contains an X-ray absorbing material 18a, such as barium oxide, lead oxide, or strontium oxide. The flat glass faceplate must contain a minimum amount of any of these heavy oxides to prevent the escape of X-rays produced in the CRT. Each of the supply reservoirs deposits its contents in the proper proportion into a feed hopper 20 in forming a glass frit mixture 20a therein. The proportions of the various components of the glass frit mixture 20a may vary depending upon the particular type of flat glass faceplate it is desired to produce. The specific proportions used for the various applications are well known to those skilled in the art and do not form a part of the present invention.
From the feed hopper 20, the glass frit mixture 20a is deposited into a glass melting tank 22 which is typically an oil-fired continuous tank furnace. The glass frit mixture 20a is reduced to a glassmelt 24 within the glassmelting tank 22 and emerges therefrom as a continuous glass band 24a. The continuous glass band 24a is directed onto and between a plurality of transport rollers 25, 26, 27 and 28. The transport rollers, in turn, direct the continuous glass band 24a through an inlet slot 30a in a float bath 30 which contains a pool of molten tin 40. The glass band 24a is positioned on the upper surface of the molten tin 40 and is heated from above in a heated zone 32 by appropriate combustible gases introduced into the float bath 30 via a hot gas inlet 38. The continuous glass band 24a is thus heated to a temperature which renders it fluid, so that it assumes the form of the plane-parallel film of the required thickness on the bath of molten tin 40. The tin is maintained in a molten state by heating it within the float bath 30 from below. The continuous glass band 24a floats like an endless ribbon on the molten tin 40 from the inlet slot 30a to an outlet slot 30b in the float bath 30.
Adjacent to the inlet slot 30a, where the glass first makes contact with the tin surface, the temperature of the molten metal is typically about 1000° C. At the outlet slot 30b of the float bath 30, the temperature is maintained at approximately 600° C. Because tin is a liquid at 600° C. and does not develop appreciable vaporization pressure at 1000° C., the molten tin 40 is able to support the glass band 24a and to allow it to flow through the float bath 30 in a continuous manner. The float bath 30 contains a fire polishing zone 34 wherein the surfaces of the glass band 24a assume a polished smoothness. To guard against oxidation of the molten tin 40 by atmospheric oxygen, which would degrade the transparency of the produced glass, the tin bath is maintained in a weakly reducing, carefully controlled protective gas by means of a controlled atmosphere zone 36 within the float bath 30. Once past the heated zone 32, the gas flows through the controlled atmosphere zone 36 and is discharged from the float bath 30 via the outlet slot 30b in the form of a solidified continuous glass band 24a which is transported to an annealing lehr 46 via a transport roller 44. The transport roller 44 is typically of the cooling type, with the continuous glass band 24a being displaced within the annealing lehr via internal rollers 48 and exiting from the annealing lehr at a temperature of approximately 200° C. After cooling to room temperature on an open roller track depicted as transport roller 50, the continuous glass band is transported through a glass cutting station 52. The cutting station 52 includes at least one cutting element 54 for cutting the continuous glass band 24a into a plurality of sections 24b, each of which forms a flat glass faceplate for use in a color CRT having a flat tensioned shadow mask. The glass faceplates thus produced retain the fire polish of crown glass and vertically drawn sheet glass and possess a degree of flatness and parallelism which closely approaches that of glass produced by the more costly grinding and polishing processes.
The individual sections 24b of the cut-up glass band are then subjected to various operations to put them in condition for use as a faceplate in a CRT. For example, each rectangular glass section may have its four corners rounded such as by grinding. In addition, the edges of each glass section would typically be ground smooth to remove irregularities for facilitating handling of the faceplate and attaching it to the front, open end of a CRT funnel. In another embodiment, the individual faceplates may be formed by rough cutting of the glass band into rectangular sections which are not subjected to further processing before incorporation in a video display.
Referring to FIG. 2, there is shown a color CRT 120 having a front assembly 122 including a tensioned metal foil shadow mask 150 and a flat glass faceplate 124 in accordance with the present invention. The color CRT 120 also includes a funnel 132, to the forward edge portion of which is securely mounted the front assembly 122. As in the case of the flat faceplate 124, the funnel 132 is also comprised of glass, with the enclosed structure thus formed evacuated by conventional means (not shown) after various electronic components are positioned therein and the structure is then sealed. Positioned within the neck portion 166 of the funnel 132 is an in-line electron gun 168 which is aligned with the anterior-posterior axis of the CRT designated by the numeral 156. The in-line electron gun 168 emits a plurality of electron beams 170, 172 and 174 which are directed through apertures 152 in the tensioned metal foil shadow mask 150 which is closely spaced relative to the inner surface 126 of the flat faceplate 124. A magnetic deflection yoke 176 is positioned about the funnel's neck 166. Horizontal and vertical deflection currents are provided to the magnetic deflection yoke 176 for deflecting the three electron beams in a timed manner across the CRT's flat faceplate 124.
A high voltage electron accelerating potential is applied from a power supply (not shown) via a conductor 164 to an anode button 162 on the CRT's funnel 132. The anode button 162 extends through the CRT's funnel 132 and is in electronic contact with an internal conductive coating 160 on the inner surface of the funnel 132. A contact spring 178 is electrically coupled to the internal conductive coating 160 and is further coupled to the metal foil shadow mask 150 such as by means of weldments. Electrical contact is also established between the metal foil shadow mask 150 and a metal cap (not shown) on each of four rails 148 which are used for mounting and positioning the metal foil shadow mask within the CRT 120. Disposed on the inner surface of the CRT's glass faceplate 124 is a film of reflective and electrically conductive aluminum 130. Mounted to the faceplate and positioned between the reflective and conductive aluminum film 130 and the flat tension shadow mask 150 is a phosphor screen 128 responsive to electrons incident thereon for emitting light in forming a video image.
As described above, the flat tension shadow mask 150 includes a plurality of apertures which are illustrated in greatly enlarged size in FIG. 2. The shadow mask support structure is generally rectangular in shape and is comprised of four elongated, linear members 148, each of which is coupled at one end thereof to another elongated, linear support structure element. The shadow mask structure 148 is typically comprised of steel, such as stainless or a rolled steel, but may also be comprised of a ceramic material, and is affixed to the inner surface of the CRT's faceplate 124 by means of a glass sealing frit cement which is heated to its annealing temperature during manufacture of the CRT's front assembly 122. The flat tension shadow mask 150 is securely attached to the aft surfaces of the four shadow mask support structures 148 by tack welding the flat tension shadow mask around its periphery. Where the shadow mask support structure 148 is comprised of a ceramic material, the flat tension shadow mask 150 may be affixed to the support structure by means of a glass sealing frit cement as previously described with respect to the mounting of the shadow mask support structure 148 to the CRT's faceplate 124. FIG. 2 is shown for illustrative purposes only and does not represent a limitation of the present invention as the flat glass faceplate of the present invention may be incorporated in a color CRT in various ways and may have a shadow mask support structure affixed to it in various mounting arrangements. Moreover, the flat glass faceplate of the present invention is not limited to use in a color CRT, but may equally as well be used in a black-and-white CRT.
As shown in FIG. 2, in a typical color CRT having a flat faceplate 124, the forward edge portion of the funnel 132 is affixed to the rear edge portion of the flat faceplate 124 in a sealed manner. The dimensions of the flat faceplate 124 are typically such that its periphery extends beyond the front edge portion of the CRT's funnel 132 so as to provide a lip which extends beyond the funnel's periphery. This outer lip of the flat faceplate 124 comprised of its peripheral edge portion facilitates secure mounting of the CRT's funnel 132 to the inner surface of the faceplate by means of a frit sealing cement to allow the interior of the CRT to be evacuated. Thus, a flat glass faceplate 124 made in accordance with the principles of the present invention would not have to be precisely sized with respect to the CRT's funnel dimensions in order to permit secure coupling of the faceplate and funnel in a sealed manner. As used in a CRT, the thickness of the flat faceplate would typically range from 0.25 inch to 1 inch, with the faceplate's thickness determined primarily by structural strength requirements for a given tube size and X-ray absorption criteria. Its length and width would, of course, be determined by the size of the video display in which it is incorporated.
There has thus been shown a self-polished color CRT flat glass faceplate, and method of fabrication therefor, which represents a low cost approach to the manufacture of color CRTs having a flat faceplate and a metal foil shadow mask maintained in a stretched condition under high tension. The self-polished surfaces of a CRT flat faceplate formed in accordance with the present invention eliminate the conventional steps of polishing and acid etching of the faceplate. The flat faceplate may be cut from a larger float glass section without requiring special shaping or edging procedures because of the manner in which the flat faceplate interfaces with and is mounted to the CRT's funnel.
While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects. Therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention. The matter set forth in the foregoing description and accompanying drawings is offered by way of illustration only and not as a limitation. The actual scope of the invention is intended to be defined in the following claims when viewed in their proper perspective based on the prior art. | The use of a flat faceplate comprised of self-polished float glass substantially reduces the cost of a cathode ray tube incorporating a flat tensioned shadow mask while affording a high degree of video image acuity. The float glass flat faceplate does not require polishing and acid etching to provide a high degree of smoothness in its inner and outer surfaces and, in combination with a flat tensioned shadow mask mounted to the flat faceplate, offers a low cost, easily manufactured and assembled color CRT front assembly. | 2 |
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates to an improvement in a specific heat based moisture sensor, and more specifically to a specific heat based moisture sensor for measuring moisture content included in moisture bearing substances such as soil, sand, rock wool used for gardening facility, caltivation apparatus, etc.
2. Description of the Prior Art
In cultivation apparatus provided with a culture medium carrier such as rock wool, for instance, it is very important to measure and control the moisture content thereof, because the moisture content of the culture medium carrier exerts a serious influence upon the growth of cultured plants.
The same applicant has already proposed a specific heat based moisture sensor which can measure moisture content more easily and quickly than the conventional tension meter- or infrared ray-based moisture measurement instruments, in Japanese Published Unexamined (Kokai) Patent Appli. No. 63-47644.
In the specific heat based moisture sensor disclosed in the above Japanese patent document, a cylindrical metallic vessel is closed at one end and opened at the other end; wires are taken out of the open end thereof; a heater is provided within the vessel; a first high temperature sensor is arranged within the vessel a predetermined distance apart from the heater; a second low temperature sensor is arranged within the vessel without being subjected to the influence of heat of the heater; the vessel is filled with a plastic as a heat loss substance; and the wires are connected to a moisture meter.
In use of the above-mentioned specific heat based moisture sensor, the cylindrical vessel is inserted into the substance to be measured (e.g. culture medium carrier) and the heater is activated. In this case, although the heat is transmitted from the heater to the first high temperature sensor, since part of heat quantity of the substance to be measured is absorbed into the substance according to the moisture content of the substance, it is possible to measure the moisture content of the substance by measuring a change in temperature between the two temperature sensors, while keeping the heating power of the heater at a constant value.
In the above-mentioned proposed moisture sensor, since the cylindrical vessel is made of metal, there exists a serious problem in that the vessel is corroded and therefore metallic ions are produced and enter the culture medium, so that the cultured plant is subjected to a harmful influence of these ions.
SUMMARY OF THE INVENTION
With these problems in mind, therefore, it is the primary object of the present invention to provide a specific heat based moisture sensor which can prevent the cylindrical vessel from being corroded and therefore prevent metallic ions from entering the culture medium, and additionally can measure moisture content of the substance to be measured quickly and precisely without increasing the cost and the size thereof.
To achieve the above-mentioned object, the specific heat based moisture sensor according to the present invention comprises: (a) a cylindrical member (20) formed with two parallel axially-extending hollow portions (21, 22); (b) a heater (30) provided on an outer circumferential surface of said cylindrical member; (c) a temperature sensor (40, 41, 42) formed by leads passed through the two hollow portions of said cylindrical member; and (d) a waterproof synthetic resin (60) formed so as to cover said cylindrical member and said heater.
The cylindrical member is made of ceramic to improve the temperature sensitivity from the outer heater to the inner temperature sensor. The waterproof synthetic resin vessel is formed with a sharp tip to facilitate insertion of the sensor into substance to be measured. The temperature sensor is a thermocouple including a first wire and a second wire connected in such a way that a first high temperature sense point between the two wires is located within one of the cylindrical hollow portion of the cylindrical member and a second low temperature sense point between the two wires is located outside the cylindrical hollow portion thereof. The heater is a nichrome wire wound around the outer circumferential surface of the cylindrical member at regular pitches.
In the specific heat based moisture sensor according to the present invention, the cylindrical member is formed with two axially extending hollow portions through which wire is passed; a heater is wound around the outer circumference of the cylindrical portion; and further the cylindrical member and the heater are molded integral with each other by a waterproof synthetic resin. Therefore, it is possible to reduce the difference in the distance between the heater and the temperature sensor among manufactured products, simplify the manufacturing process, minimize the shape and the cost thereof, and further eliminating the harmful influence upon the cultured plant due to metallic corrosion.
Further, since the end of the specific heat based moisture sensor according to the present invention is formed into a sharp tip, it is possible to easily insert the sensor into the substance to be measured such as a culture medium carrier, thus facilitating the measurement process.
Further, in the moisture sensor according to the present invention, since a ceramic cylindrical member (whose thermal conductivity is higher than that of resin) is used for the cylindrical member for supporting the heater and the sensor, it is possible to improve the sensor sensitivity with respect to heat, thus permitting higher sensitivity and higher precision measurement of moisture content.
In summary, the specific heat based moisture sensor according to the present invention can improve the detection sensitivity and precision of moisture content, simplify the measurement, and reduce the shape and cost thereof, thus realizing a specific heat based moisture sensor of higher performance as compared with the conventional specific heat moisture sensor.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration for assistance in explaining the specific heat based moisture sensor according to the present invention;
FIG. 2 is a perspective view showing the ceramic cylindrical member shown in FIG. 1;
FIG. 3 is a basic circuit diagram of the specific heat based moisture sensor according to the present invention;
FIG. 4 is a graphical representation showing the relationship between the volumetric moisture content rate (abscissa) and the sensor electromotive force (ordinate) obtained when moisture content in a rock wool was measured by the moisture sensor according to the present invention in comparison with the prior-art moisture sensor;
FIG. 5 is a graphical representation showing the relationship between the weight moisture content rate (abscissa) and the sensor electromotive force (ordinate) obtained when moisture content in a black soil was measured by the moisture sensor according to the present invention in comparison with the prior-art moisture sensor; and
FIG. 6 is a graphical representation showing the relationship between the measurement time (abscissa) and the heater power (ordinate) consumed when moisture content was measured.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
An embodiment of the specific heat based moisture sensor according to the present invention will be described in further detail with reference to the attached drawings.
FIG. 1 is a side view showing a specific heat based moisture sensor according to the present invention, and FIG. 2 is a perspective view showing a ceramic cylindrical member shown in FIG. 1.
In FIGS. 1 and 2, the specific heat based moisture sensor 10 according to the present invention comprises a ceramic cylindrical member 20 formed with two axially extending cylindrical hollow portions 21 and 22, a nichrome heating wire 30 wound around an outer circumferential surface of the cylindrical member 20 at regular pitch intervals, a thermocouple composed of a first lead 41, second lead 42 both passed through these two cylindrical hollow portions 21 and 22 and a third lead 43, a first high temperature sense point 51 connected between the first lead 41 and a second lead 42 within the cylindrical member 20 so as to be heated by the heater 30, a second low temperature sense point 52 connected between the second lead 42 and the third lead 43 outside the cylindrical member 20 so as not to be subjected to the influence of heat of the heater 30, and a waterproof synthetic resin tubular vessel 60. The first and third leads 41 and 43, respectively, are led out of the tubular vessel 60 and connected to a moisture meter (not shown). Further, the heater 30 is led out of the tubular vessel 60 via two heater leads 45 and 46 and connected to a power source E via a switch SW (both shown in FIG. 3).
The thermocouple is a temperature sensor in which two different metallic wires are connected in a ring shape and an electromotive force (V) generated between the free ends of the one wire is measured by a voltammeter when two junction points are placed at two different temperatures. In practice, a first junction point is kept at a constant temperature, and the temperature at a second junction point is detected on the basis of the measured electromotive force (V). The two different metals are platinum and platinum rhodium (300° to 1400° C.), alumel and chromel (0° to 750° C.), iron and constantan, etc.
Without being limited to the thermocouple, it is also possible to use a platinum thin film resistor or other temperature sensors for the moisture sensor according to the present invention.
The ceramics used for forming the cylindrical member 20 include sintered bodies of metallic oxide, boride, carbide and nitride of silane, aluminium, magnesium, zinc, etc. or these mixtures and compounds, which are excellent in strength and heat resistance.
The synthetic resin tubular vessel 60 is formed of a waterproof synthetic resin such as glass fiber reinforcing polybutyleneterephtarate, and preferably formed with a pencil-shaped sharp end (tip) portion 61 to facilitate insertion of the sensor 10 into a substance to be inspected.
FIG. 3 shows a basic circuit of the thermocouple moisture sensor according to the present invention, in which E denotes a power source such as a battery; H (30) denotes a nichrome heating wire; V out denotes a sensor output voltage; SH (51) denotes a high temperature sense point; and SL (52) denotes a low temperature sense point.
When the moisture content of a substance to be checked is required to be measured by use of the moisture sensor according to the present invention, the sharp end portion 61 of the sensor 10 is inserted into the substance and a constant voltage is supplied from the battery E to the heater H (30) to generate heat from the heater H (30). In this case, where the substance includes moisture, since part of heat from the heater H (30) is absorbed into the substance according to the degree of the moisture content, a change in temperature at the high temperature sense point SH (51) is measured to detect the moisture content, on condition that the heat quantity generated by the heater H (30) is kept constant, in comparison with the temperature at the low temperature sense position SL (52).
In the moisture sensor according to the present invention, since the cylindrical member 20 is formed of ceramics, the thermoconductivity is high and therefore the heat loss is small, thus improving the sensor sensitivity.
Further, since the measurement time can be reduced as short as about 60 sec, it is possible to economize the battery power, thus allowing the moisture sensor to be most suitable for use together with a portable moisture meter.
In addition, since the moisture sensor according to the present invention is molded integral in the form of a synthetic resin tubular vessel 60, the manufacturing process can be simplified and the manufacturing cost can be reduced. Further, since the end 61 of the synthetic resin tubular vessel 60 is formed into a sharp shape, the sensor 10 can be easily inserted into a substance to be checked. Further, since the sensor 10 is covered by a synthetic resin entirely, it is possible to eliminate the harmful influence upon the cultured plant due to corrosion or rust or metallic ion generation from the corroded metal. Furthermore, since the distance between the thermocouple temperature sensor element 40 within the two hollow portions and the heater 30 wound outside the cylindrical member 20 can be kept constant at any time, it is possible to reduce the difference in performance between the manufactured sensors.
The effect of the specific heat moisture sensor according to the present invention will be explained on the basis of test examples.
TEST EXAMPLE 1
Rock wool measurement
A well dried rock wool was cut into a 30×30×7.5 cm size, and the weight and volume was measured. The sharp end of the moisture sensor according to the present invention was inserted into a middle position of a height (7.5 cm) of the 30×30 cm rock wool for measurement preparation.
Thereafter, water is supplied from under the rock wool for about 30 min to allow the rock wool to contain water all over it. The water content rate of the entire rock wool was measured as 90 volume %. Under these conditions, a voltage of 6.0 V was applied to the nichrome heating wire for about 1 min to measure the thermocouple electromotive force. Further, the water content rate of the rock wool was adjusted to 70, 50 and 30 volume %, and the thermocouple electromotive forces were measured under the same conditions. These measured results are plotted by white circles in FIG. 4.
On the other hand, a prior-art moisture sensor in which a Teflon (Trademark) cylindrical member was insertion molded within the synthetic resin vessel instead of the ceramic cylindrical member was prepared, and the thermocouple electromotive forces were measured under the same conditions for comparison. These measured results are plotted by black circles in FIG. 4.
Further, the electromotive forces of the prior-art moisture sensor provided with the Teflon cylindrical member were measured on condition that the measurement time was 3 min. These measured results are plotted by black triangles in FIG. 4.
FIG. 4 indicates that a difference in the electromotive force of the invention moisture sensor at the measurement time of 1 min is roughly equal to that of the prior-art moisture sensor at the measurement time of 3 min. However, since FIG. 4 indicates that the gradient of electromotive force in the invention moisture sensor is larger than that in the prior-art moisture sensor in the higher water content range (at about 90 volume %), the invention moisture sensor is high in measurement sensitivity all over the water content range and in the higher water content range, in particular. Further, the difference in the electromotive force between 30 and 90 volume % of the invention sensor is twice larger than that of the prior-art sensor. This indicates the higher sensitivity all over the water content range.
TEST EXAMPLE 1
Black soil measurement
Water was added little by little to well dried black soil and mixed therewith to obtain samples of 10, 20, 30 and 36% by weight in water content rate. Each of these samples was put into a plastic container. The moisture sensor according to the present invention was inserted vertically into each of these samples at four different positions. A voltage of 6 V was applied to the nichrome wire for 60 sec for each measurement to measure the thermocouple electromotive force. The measured results are plotted by white circles in FIG. 5.
FIG. 5 indicates that the maximum measurement dispersion at each different measurement point is about ±2 to 3% (shown by a short vertical line) and it is possible to practically use the moisture sensor according to the present invention even in such a short measurement time as 60 sec. Further, the gradient of the thermocouple electromotive force is sharp in a higher water content range and therefore the sensor sensitivity is high in the high water content range.
On the other hand, a prior-art moisture sensor in which a Teflon cylindrical member was insertion molded within the synthetic resin vessel instead of the ceramic cylindrical member was prepared, and the thermocouple electromotive forces were measured under the same conditions for comparison. These measured results are plotted by black circles in FIG. 5.
FIG. 5 indicates that the maximum measurement dispersion at each different measurement point is almost the same as that (2 to 3%) of the present invention. However, since the difference in measurement value between 10 and 36 weight % of the prior-art sensor is small, the measurement error increases as high as 8 to 10% at the maximum all over the water content range, and therefore the measurement time of 60 sec is not sufficient for the prior-art sensor. This is because the sensor sensitivity of the prior-art sensor is not sufficient as compared with that of the invention sensor.
Further, FIG. 6 shows the relationship between the consumed heater power (W) and the measurement time in each of the invention moisture sensor and the prior-art moisture sensor, when moisture content was measured.
FIG. 6 indicates that the invention moisture sensor consumes about 1.9 W in each sufficient measurement time of 1 min but the prior-art moisture sensor consumes about 2.55 W in each sufficient measurement time of 3 min, thus economizing the power consumption rate as much as about 30% in the case of the moisture sensor according to the present invention.
As described above, in the specific heat based moisture sensor according to the present invention, it is possible to improve the detection sensitivity and precision, reduce the size and the cost, simplify the measurement process, etc. thus realizing a specific heat based moisture sensor of higher performance as compared with the prior-art specific heat based moisture sensor. | A specific heat based moisture sensor comprises: a cylindrical member formed with two parallel axially-extending hollow portions; a heater provided on an outer circumferential surface of the cylindrical member; a temperature sensor formed by leads passed through the two hollow portions of the cylindrical member; and a waterproof synthetic resin formed so as to cover said cylindrical member and the heater. Since the difference in distance between the heater and the temperature sensor lead is determined precisely, the sensing reliability can be improved. Since the ceramic cylindrical member is used, temperature sensitivity can be improved. Since the sensor is covered with a waterproof resin, it is possible to prevent metallic ions from entering the substance to be sensed, without increasing the size and cost of the moisture sensor. | 6 |
This is a division of application Ser. No. 155,277, filed June 2, 1980, now U.S. Pat. No. 4,345,986.
Solid polymer electrolyte chlor-alkali cells, i.e., for the electrolysis of potassium chloride or sodium chloride brines are characterized by an electrode bearing cation selective permionic membrane separating the anolyte liquor from the catholyte liquor. For example, either the anodic electrocatalyst or the cathodic electrocatalyst, or both may compressively and removably bear upon the permionic membrane, that is, be in contact with, but not physically or chemically bonded to the surfaces of the permionic membrane. Alternatively, either the anodic electrocatalyst or the cathodic electrocatalyst or both may be embedded in or physically or chemically bonded to the permionic membrane.
The commonly assigned co-pending U.S. application Ser. No. 76,898 filed Sept. 19,1979 for SOLID POLYMER ELECTROLYTE CHLOR-ALKALI PROCESS AND ELECTROLYTIC CELL by William B. Darlington and Donald W. DuBois describes a solid polymer electrolyte chlor-alkali cell where either the anode or the cathode or both compressively bear upon, but are neither embedded in nor bonded to the permionic membrane.
The commonly assigned co-pending U.S. application Ser. No. 120,217, filed Feb. 11, 1980, for SOLID POLYMER ELECTROLYTE CHLOR-ALKALI PROCESS AND ELECTROLYTIC CELL of William B. Darlington and Donald W. DuBois, a continuation-in-part of U.S. application Ser. No. 76,898, describes a solid polymer electrolyte electrolytic cell where there is no electrolyte gap, that is, no liquid gap between the anodic electrocatalyst which compressively bears upon the anodic surface of the permionic membrane and the membrane, while the cathodic electrocatalyst is bonded to and embedded in the cathodic surface of the permionic membrane.
It is there disclosed that the high current density and low voltage of the solid polymer electrolyte cell are obtained while simple mechanical current collectors and electrode supports are retained on the anolyte side of the cell. However, a solid polymer electrolyte electrolytic cell where the cathodic electrocatalyst is bonded to and embedded in the permionic membrane is subject to high anolyte hydrogen and chlorate, and low current efficiency.
The commonly assigned, co-pending U.S. application Ser. No. 135,960, filed Mar. 31, 1980, of William B. Darlington, Donald W. DuBois and Preston S. White for SOLID POLYMER ELECTROLYTE-CATHODE UNIT attributes the high anolyte hydrogen and chlorate, and the low current efficiency to the formation of hydroxyl ion within the permionic membrane, and describes the importance of avoiding the formation of hydroxyl ion within the permionic membrane.
As there described, a compressive cathode solid polymer electrolyte, i.e., a solid polymer electrolyte where the cathode bears compressively upon the permionic membrane but is neither bonded to nor embedded in the membrane, is characterized by a higher cathodic current efficiency and a lower anolyte H 2 content than a conventional solid polymer electrolyte. Conversely, a conventional solid polymer electrolyte, i.e., a solid polymer electrolyte where the cathodic electrocatalyst is bonded to and embedded in the permionic membrane, is characterized by a lower voltage than a compressive cathode solid polymer electrolyte. Accordingly, a particularly desirable solid polymer electrolyte would be one combining the high cathode current efficiency and low anolyte H 2 attributes of a compressive cathode solid polymer electrolyte with the low voltage characteristics of a bonded electrode solid polymer electrolyte.
Darlington et al. disclose that cathode current efficiency, anolyte H 2 content, and to a lesser extent, the anolyte oxygen and chlorate contents are inter-related with the diminished cathode current efficiency and increased anolyte H 2 and chlorate of the conventional solid polymer electrolyte relative to the compressive cathode solid polymer electrolyte, both being the result of the electrolytic reaction,
H.sub.2 O+e.sup.- →OH.sup.- +H.sub.1.sup.O,
occurring within the permionic membrane. The inefficiencies are disclosed to be the result of the migration of the hydroxyl ion, formed within the membrane and not being subject to exclusion by the permionic membrane, toward the anode.
Moreover, Darlington et al. disclose that the higher voltage of the compressive solid polymer electrolyte over the conventional solid polymer electrolyte is caused by electrolytic conduction of sodium ion within the catholyte liquor, even a thin film of catholyte liquor.
My commonly assigned, co-pending U.S. application Ser. No. 155,278, now U.S. Pat. No. 4,299,674, issued Nov. 10, 1981 for SOLID POLYMER ELECTROLYTE, filed of even date herewith, describes how the advantages of a conventional, bonded solid polymer electrolyte, e.g., low voltage, as well as the advantages of a compressive solid polymer electrolyte, e.g., high cathode current efficiency and low anolyte H 2 content, may be obtained when th cathodic reaction is carried out in a portion of the membrane of reduced cation selectivity on the cathodic side of the membrane separated from the anolyte by a region of increased cation selectivity. As described therein, one particularly desirable solid polymer electrolyte unit may be provided having cathode catalyst particles bonded to and embedded in the permionic membrane, where the cathode electrocatalyst carrying region of the permionic membrane is of lower cation permselectivity than the anodic side of the permionic membrane. As there described, while the evolution of hydroxyl ion within the permionic membrane may not be eliminated, the transport of hydroxyl ion to the anolyte liquor is substantially eliminated. As also described therein, the cathode current efficiency of a solid polymer electrolyte wherein the cathode electrocatalyst removably and compressively bears upon the permionic membrane may be enhanced where the catholyte facing surface or portion of the permionic membrane is of lower cationic selectivity than the anolyte facing surface or portion of the permionic membrane. In both exemplifications, an ion selective means, zone or region of high cation selectivity is interposed between the portion of the membrane in contact with the cathode, and the anolyte. The ion selective means, i.e., the barrier or zone, has a higher cation selectivity than the cathodic portion of the permionic membrane, and is interposed between the cathodic portion of the permionic membrane and the anode means.
It has now been found that high current efficiency of the removable, compressed cathode structure may be retained while avoiding some of the cell voltage penalty associated therewith if the cathode is a microporous metal sheet, compressively bearing upon the permionic membrane. The geometry of the microporous metal sheet should be such as to conform to the permionic membrane, whereby the bulk of the reaction
H.sub.2 O+e.sup.- →OH.sup.- +H
occurs at the membrane-cathode-catholyte interface, thereby avoiding electrolytic conduction of anions through the catholyte and evolution of either hydrogen or hydroxyl ion within the permionic membrane. Moreover, the geometry of the microporous sheet should be such as to avoid blocking off, blanking off, or blinding off portions of the permionic membrane, as evidenced by trapping or entraining product between the permionic membrane and the cathode.
THE FIGURES
FIG. 1 is an isometric view from the cathodic side of an element of a solid polymer electrolyte having a microporous cathode bearing upon the permionic membrane.
FIG. 2 is an isometric view from the anodic side of an element of the solid polymer electrolyte of FIG. 1 having a microporous cathode sheet bearing upon the permionic membrane.
FIG. 3 is a cutaway view of the solid polymer electrolyte of FIGS. 1 and 2 having a microporous cathode bearing upon the permionic membrane.
DETAILED DESCRIPTION
The chlor-alkali solid polymer electrolyte shown in the Figures has a solid polymer electrolyte unit 1 separating the anolyte liquor from the catholyte liquor. The solid polymer electrolyte unit 1 has a permionic membrane 11 with an anodic unit 21 on the anolyte surface thereof, and a cathodic unit 41 on the catholyte surface thereof. The anodic unit includes anode mesh 23, which bears upon the permionic membrane 11, deforming the anode surface of the permionic membrane 11, as shown for example, in FIG. 3 by anode element deformate 13.
The cathode unit has a microporous cathode element 45 bearing upon the permionic membrane 11. Bearing upon the cathode element 45 are a fine mesh cathode conductor 41 and a coarse mesh cathode conductor 43.
It has now been found that the cathodic energy efficiency, i.e., the product of the cell voltage, the current density, and the cathode current efficiency, is enhanced, at constant anode configuration, anode chemistry and membrane chemistry, the anolyte chlorate content is reduced and the voltage is reduced when the cathode element 45 bearing upon the permionic membrane 11 is a flexible, thin, microporous, metal sheet.
As herein contemplated, the flexible, thin, microporous, metallic sheet cathode element 45 conforms to the permionic membrane 11. In this way the major portion, and preferably substantially all of the reaction
H.sub.2 O+e.sup.- →OH.sup.- +H
occurs at the membrane-catholyte-cathode interface, and substantially no hydroxyl ion or hydrogen is evolved either within the catholyte liquor 30 or within the permionic membrane 11. Moreover, the cathode element 45 does not interfere with the free transport of either the hydroxyl ion or the hydrogen evolved at the membrane-catholyte-cathode interface.
This is because the cathode element 45 is thin and porous. The cathode element 45 is less than 2.5 millimeters thick, and preferably less than 1.3 millimeters thick, and preferably from about 0.01 to about 1 millimeter thick but thin enough that it is capable of conforming to the permionic membrane 11.
The porosity of the cathode element 45 is from about 20 percent to about 80 percent. The porosity is defined by the relationship
Porosity=1-(Measured Density/Theoretical Density)
The pores are less than about 0.25 millimeters in diameter, preferably less than about 0.05 millimeters in diameter, and preferably larger than about 0.001 millimeters in diameter.
The cathode element 45 compressively bears upon the permionic membrane 11, so as to conform to the permionic membrane 11 while partially deforming the permionic membrane 11. The imposed pressure on the permionic membrane, as will be described more fully hereinafter, is from about 1 pound per square inch to about 20 pounds per square inch.
The material used in preparing the cathode element is a corrosion resistant metal. In one preferred exemplification it is ductile and malleable, whereby to allow being drawn into a thin sheet, as a foil, and perforated, e.g., by gas jets, liquid jets, electron beam, selective dissolution, photolithography, or the like, or by laser. As herein contemplated, the foil or sheet is fabricated of iron, steel, cobalt, nickel, copper, or a ductile precious metal as silver or gold. The foil or sheet may have an electrocatalytic material on the surface thereof. That is, the surface may contain nickel, porous nickel, graphite, or a catalytic precious metal as a platinum group metal, platinum black, or platinum oxide.
According to an alternative exemplification, the cathode element 45 may be prepared by power metallurgy techniques. That is, the cathode element 45 may be prepared by shaping metal powder to form the cathode element 45. As herein contemplated, metal powder, e.g., mixed powders of nickel and a sacrificial metal, or iron powder, are compacted in the form of the cathode element 45. The resulting green form of the element 45 is then sintered, whereby to form the cathode element 45. Thereafter the sacrificial metal is leached out, whereby to form the porous cathode element 45.
Alternatively, the powder, e.g., iron powder, nickel powder, or nickel powders with powders of a sacrificial metal, may be sintered without compaction, whereby to provide a sintered product of high porosity.
According to a still further exemplification, the cathode element 45 may be a porous coating, film, or layer on the fine mesh 41. For example, a fine screen could be coated with metal powder, metal particles, or the like, e.g., by sintering, chemical deposition, electrodeposition, painting, or the like, and the surface bearing upon the membrane thereafter coated with a suitable catalyst. The resulting composite structure is characterized by having a surface 45, adapted to bear upon the permionic membrane 11, of about 20 percent to 80 percent porosity, with pores of about 0.001 to about 0.025 millimeters in size.
The anode 21, i.e., mesh 23, bears upon the permionic membrane 11, and partially deforms the permionic membrane 11, as shown by deformate 13. The cathode element 45 bears upon and partially deforms the opposite surface of the permionic membrane. The anodic voltage, anode current efficiency, cathode voltage, and cathode current efficiency are believed to be functions of the pressure of the anodic element 21 and cathode element 45 bearing upon the permionic membrane 11. Thus, it has been found that the voltage initially decreases with increasing pressure, that is, with increasing compression of the permionic membrane 11 between the anodic mesh 23 and the cathode element 45. Thereafter, the rate of voltage decrease with increasing pressure diminishes and, ultimately, a constant voltage is attained, which voltage is substantially independent of increasing pressure. The pressure at which substantially constant voltage versus pressure is attained is also a function of the geometry of the mesh 23, i.e., orientation of the openings, solid material thickness, size of openings, percent open area, electrode materials of construction, electrode material resiliency, and openings per unit area.
The pressure-voltage relationship is a function of the resiliency and elasticity of the cathode current conductors 41 and 43, the cathode catalyst element 45, and of the anode substrate 23, as well as the resiliency and elasticity of the permionic membrane 11, the geometry of the anode substrate 23 and the cathode current collectors 41 and 43, and cathode element 45, the size of the individual substrate and current collector elements, the internal reinforcement of the permionic membrane 11, the thickness of the permionic membrane 11, and the materials of construction of the electrode elements.
For any electrode-permionic membrane combination, the determination of a satisfactory pressure, that is, a pressure at which increasing imposed pressures give no significant decrease in voltage, is a matter of routine experimentation.
For unreinforced Asahi Glass Flemion (TM) carboxylic acid membranes, where the anode substrate 23 is of eight to ten strands per inch of 1 millimeter diameter titanium and the fine cathode current collector 41 has forty to sixty percent open area and about 200 to 300 openings per square centimeter, and is steel or nickel, compressive pressures between the cathode current collector 41 and the anode substrate 23 of from at least one pound per square inch, up to about 20 pounds per square inch yield voltage reductions.
The anode substrate 23, and the cathode current collectors 41 and 43, are preferably fine mesh having a high percentage of open area, e.g., above about 40 percent open area to about 80 percent open area, and a narrow pitch, e.g., about 0.1 to 2 millimeters between individual elements thereof. Suitable anode substrates 23, and cathode current collectors 41 and 43, have about 10 to 60 strands per inch, where the individual strands are from about 0.5 to about 2.5 millimeters apart, center line to center line, and a diameter such as to provide at least 40 percent open area, preferably 60 to 80 percent open area, and from about 15 to about 600 openings per square centimeter.
The permionic membrane 11 should be chemically resistant, cation selective, with anodic chlorine evolution catalyst 23 bearing upon, or bonded to, or bonded to and embedded in the anodic surface and cathodic catalyst element 45 compressively bearing thereon.
The fluorocarbon resin permionic membrane 11 used in providing the solid polymer electrolyte 1 is characterized by the presence of cation selective ion exchange groups, the ion exchange capacity of the membrane, and the glass transition temperature of the membrane material.
The fluorocarbon resins herein contemplated have the moieties: ##STR1## where X is --F, --Cl, --H, or --CF 3 ; X' is --F, --Cl, --H, --CF 3 or CF 3 (CF 2 ) m --; m is an integer of 1 to 5; and Y is --A, --3--A, --P--A, or --O--(CF 2 ) n (P, Q, R)--A.
In the unit (P, Q, R), P is --(CF 2 ) a (CXX') b (CF 2 ) c , Q is (--CF 2 --O--CXX') d , R is (--CXX'O--CF 2 ) e and (P, Q, R) contains one or more of P, Q, R, and is a discretionary grouping thereof.
φ is the phenylene group; n is 0 or 1; a, b, c, d and e are integers from 0 to 6.
The typical groups of Y have the structure with the acid group A, connected to a carbon atom which is connected to a fluorine atom. These include (CF 2 ) A, and side chains having ether linkages such as: ##STR2## where x, y and z are respectively 1 to 10; Z and R are respectively --F or a C 1-10 perfluoroalkyl group, and A is the acid group as defined below.
In the case of copolymers having the olefinic and olefin-acid moieties above described, it is preferable to have 1 to 40 mole percent, and preferably especially 3 to 20 mole percent of the olefin-acid moiety units in order to produce a membrane having an ion-exchange capacity within the desired range.
A is an acid group chosen from the group consisting of:
--SO 3 H
--COOH
--PO 3 H 2 , and
--PO 2 H 2 ,
or a group which may be converted to one of the aforesaid groups by hydrolysis or by neutralization. Whenever a completed, assembled solid polymer electrolyte installed in an electrolytic cell is referred to as being in the acid form it is to be understood that the alkali salt form is also contemplated.
In one exemplification, A may be either --SO 3 H or a functional group which can be converted to --SO 3 H by hydrolysis or neutralization, or formed from --SO 3 H such as --SO 3 M', (SO 2 --NH) M", --SO 2 NH--R 1 --NH 2 , or --SO 2 NR 4 R 5 NR 4 R 6 ; M' is an alkali metal; M" is H, NH 4 , an alkali metal, or an alkaline earth metal; R 4 is H, Na or K; R 3 is a C 3 to C 6 alkyl group, (R 1 ) 2 NR 6 , or R 1 NR 6 (R 2 ) 2 NR 6 ; R 6 is H, Na, K or --SO 2 ; and R 1 is a C 2 -C 6 alkyl group.
In a particularly preferred exemplification of this invention, A may be either --COOH, or a functional group which can be converted to --COOH by hydrolysis or neutralization such as --CN, --COF, --COCl, --COOR, --COOM, --CONR 2 R 3 ; R 1 is a C 1-10 alkyl group and R 2 and R 3 are either hydrogen or C 1 to C 10 alkyl groups, including perfluoralkyl groups, or both. M is hydrogen or an alkali metal; when M is an alkali metal it is most preferably sodium or potassium.
Cation selective permionic membranes where A is either --COOH, or a functional group derivable from or convertible to --COOH, e.g., --CN, --COF, COCl, --COOR 1 , --COOM, or --CONR 2 R 3 , as described above, are especially preferred because of their voltage advantage over sulfonyl membranes. This voltage advantage is on the order of about 0.1 to 0.4 volt at a current density of 150 to 250 amperes per square foot, a brine content of 150 to 300 grams per liter of sodium chloride, and a caustic soda content of 15 to 50 weight percent sodium hydroxide. Additionally, the carboxylic acid type membranes have a current efficiency advantage over sulfonyl type membranes.
The membrane materials useful in the solid polymer electrolyte herein contemplated have an ion exchange capacity of from about 0.5 to about 2.0 milligram equivalents per gram of dry polymer, and preferably from about 0.9 to about 1.8 milligram equivalents per gram of dry polymer, and in a particularly preferred exemplification, from about 1.1 to about 1.7 milligram equivalents per gram of dry polymer. When the ion exchange capacity is less than about 0.5 milligram equivalents per gram of dry polymer, the voltage is high at the high concentrations of alkali metal hydroxide herein contemplated, while when the ion exchange capacity is greater than about 2.0 milligram equivalents per gram of dry polymer, the current efficiency of the membrane is too low.
The content of ion exchange groups per gram of absorbed water is from about 8 milligram equivalents per gram of absorbed water to about 30 milligram equivalents per gram of absorbed water, and preferably from about 10 milligram equivalents per gram of absorbed water to about 28 milligram equivalents per gram of absorbed water, and in a preferred exemplification, from about 14 milligram equivalents per gram of absorbed water to about 26 milligram equivalents per gram of absorbed water. When the content of ion exchange groups per unit weight of absorbed water is less than about 8 milligram equivalents per gram the voltage is too high, and when it is above about 30 milligram equivalents per gram, the current efficiency is too low.
The glass transition temperature is preferably at least about 20° C. below the temperature of the electrolyte. When the electrolyte temperature is between about 95° C. and 110° C., the glass transition temperature of the fluorocarbon resin permionic membrane material is below about 90° C., and in a particularly preferred exemplification, below about 70° C. However, the glass transition temperature should be above about -80° C. in order to provide satisfactory tensile strength of the membrane material. Preferably the glass transition temperature is from about -80° C. to about 70° C., and in a particularly preferred exemplification, from about -80° C. to about 50° C.
When the glass transition temperature of the membrane is within about 20° C. of the electrolyte or higher than the temperature of the electrolyte, the resistance of the membrane increases and the permselectivity of the membrane decreases. By glass transition temperature is meant the temperature below which the polymer segments are not energetic enough to either move past one another or with respect to one another by segmental Brownian motion. That is, below the glass transition temperature, the only reversible response of the polymer to stresses is strain, while above the glass transition temperature the response of the polymer to stress is segmental rearrangement to relieve the externally applied stress.
The fluorocarbon resin permionic membrane materials contemplated herein have a water permeability of less than about 100 milliliters per hour per square meter at 60° C. in four normal sodium chloride at a pH of 10 and preferably lower than 10 milliliters per hour per square meter at 60° C. in four normal sodium chloride of the pH of 1. Water permeabilities higher than about 100 milliliters per hour per square meter, measured as described above, may result in an impure alkali metal hydroxide product.
The electrical resistance of the dry membrane should be from about 0.5 to about 10 ohms per square centimeter and preferably from about 0.5 to about 7 ohms per square centimeter.
The thickness of the permionic membrane 11 should be such as to provide a membrane 11 that is strong enough to withstand pressure transients and manufacturing processes, but thin enough to avoid high electrical resistivity. The membrane is from 10 to 1000 microns thick and, in a preferred exemplification, from about 50 to about 400 microns thick. Additionally, internal reinforcement, or increased thickness, or crosslinking, or even lamination may be utilized whereby to provide a strong membrane.
According to a particularly desirable alternative exemplification, the cathodic side of the permionic membrane 11 may be separated from the anolyte by a region within the permionic membrane 11 of higher cation selectivity. That is, the region of the permionic membrane 11 in contact with the cathodic element 45 may be of low cation selectivity, and a region of higher cation selectivity may be interposed between said low selectivity region and the anolyte. In this way, as described in my commonly assigned, co-pending U.S. application Ser. No. 155,278, now U.S. Pat. NO. 4,299,674 issued Nov. 10, 1981 for SOLID POLYMER ELECTROLYTE, filed of even date herewith, and the disclosure of which is incorporated herein by reference, the transport through the permionic membrane 11 of hydroxyl ions inadvertantly formed within the membrane 11 is reduced, or even eliminated.
According to one preferred exemplification of this invention, the solid polymer electrolyte unit 1 consists of a permionic membrane 11 from about 10 to about 1000 microns thick, having an anode element 21 of anode mesh 23 of from 6 to 20 strands of about one millimeter diameter ruthenium dioxide-titanium dioxide coated titanium mesh per inch, and the cathode element 45 is a 0.05 millimeter thick porous foil having pores of 0.001 to 0.025 millimeter diameter, and a porosity of 20 to 80 percent. Preferably the cathode element 45 is nickel. The cathode current carriers 41 and 43, and the anode substrate 21 provide compressive pressures of about 1 pound per square inch up to about 20 pounds per square inch.
The solid polymer electrolyte prepared as described above may be used at high current densities, for example, in excess of 200 amperes per square foot. Thus, according to a particularly preferred exemplification, electrolysis may be carried out at a current density of 800 or even 1200 amperes per square foot, where the current density is defined as the total current passing through the cell divided by the surface area of one side of the permionic membrane 11.
While this invention has been described in terms of specific details and embodiments, the description is not intended to limit the invention, the scope of which is as defined in the claims appended hereto. | Disclosed is a solid polymer electrolyte unit, an electrolytic cell containing the unit, and an electrolytic process utilizing the unit. The solid polymer electrolyte unit has anodic and cathodic means contacting opposite surfaces thereof, and is characterized by the structure of the cathode. The cathode removably and compressively bears upon the permionic membrane, and is a microporous, metallic cathode. | 2 |
[0001] This application claims the benefit of Taiwan application Serial No. 105113925, filed May 5, 2015, the subject matter of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The invention relates in general to a multimedia device, and more particularly to a multimedia device with a timeshift function.
Description of the Related Art
[0003] A multimedia device (e.g., a player, a television or a set-top box) with a timeshift function provides a pause function, and allows a user to temporarily leave without missing brilliant program details. FIG. 1 shows a flowchart of a conventional multimedia playing multimedia data and performing a timeshift function. When the multimedia device receives a multimedia signal, it parses the multimedia signal to obtain multimedia data carried in the multimedia signal (step S 110 ). For example, if the multimedia signal is transmitted in a format of a transport stream, this step removes various kinds of headers in the transport stream to leave multimedia data carrying video and audio information. Before a pause signal is received (the determination result of step S 115 is negative), the multimedia data is directly parsed (step S 120 ), and pre-playback processes are performed on the multimedia data (step S 130 ) by the multimedia device, e.g., de-interlacing, scaling. The multimedia data is then played (step S 140 ).
[0004] When the multimedia device receives the pause signal (the determination result of step S 115 is affirmative), a control circuit of the multimedia device first pauses playing the multimedia data (step S 150 ), starts writing the multimedia data to a multimedia buffer unit (step S 160 ), and writes the multimedia data into a storage unit (step S 170 ). In general, an access speed of a multimedia buffer unit is faster than that of a storage unit, with however the storage unit having a greater storage space. For example, the multimedia buffer unit is a volatile memory (e.g., a DRAM or SRAM), and the storage unit is a non-volatile memory (e.g., a flash, solid-state drive (SSD) or magnetic disk).
[0005] When playback is resumed (decoding, performing pre-playback processes and playing a multimedia file stored in a storage unit) after the conventional timeshift function, a black screen of a display device is often resulted. The reason is that, the multimedia device only starts storing current undecoded multimedia data after it receives the pause signal, while the image currently being played on the display device is an earlier image (previously decoded and having undergone pre-playback processes). Thus, there may be a difference of several frames in between (depending on the format of the multimedia data and the processing speed of the multimedia device). These “lost frames” are the main cause of the black screen observed during the timeshift function.
SUMMARY OF THE INVENTION
[0006] The invention is directed to a control method of a multimedia device and a data processing method thereof to improve user experiences in using the timeshift function.
[0007] The present invention discloses a data processing method for multimedia device. The multimedia device pauses playback of multimedia data in response to a pause signal. The method includes: buffering the multimedia data before the pause signal is received to obtain prerecorded multimedia data; writing the prerecorded multimedia data into a storage unit in response to the pause signal; reading the prerecorded multimedia data from the storage unit in response to a playback signal; and playing the prerecorded multimedia data.
[0008] The present invention further discloses a control circuit of a multimedia device. The multimedia device includes a multimedia buffer unit and a storage unit, and pauses playback of multimedia data in response to a pause signal. The control circuit includes: a transport stream processing unit, parsing a multimedia signal to generate the multimedia data; and a control unit, performing operations of: buffering the multimedia data to the multimedia buffer unit before the pause signal is received to obtain prerecorded multimedia data; writing the prerecorded multimedia data into the storage unit in response to the pause signal; reading the prerecorded multimedia data from the storage unit in response to a playback signal; and playing the prerecorded multimedia data.
[0009] The control method and the data processing method of the present invention are capable of prerecording the multimedia data before playback is paused, in a way that the subsequent resume operation may be seamlessly performed to enhance user experiences. Compared to a conventional technology, the control circuit and the data processing method of the present invention are capable of preventing the black screen.
[0010] The above and other aspects of the invention will become better understood with regard to the following detailed description of the preferred but non-limiting embodiments. The following description is made with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a flowchart of a conventional multimedia device playing multimedia data and performing a timeshift function;
[0012] FIG. 2 is a function block diagram of a multimedia device according to an embodiment of the present invention;
[0013] FIG. 3 is a flowchart of a data processing method according to an embodiment of the present invention; and
[0014] FIG. 4 is a process of a multimedia device performing playback of prerecorded multimedia data according an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0015] This application discloses a control circuit of a multimedia device and a data processing method thereof capable of preventing a black screen to enhance user experiences. In possible implementation, one person skilled in the art can choose equivalent elements or steps to realize the present invention based on the disclosure of the application. That is, the implementation of the present invention is not limited to the non-limiting embodiments below.
[0016] FIG. 2 shows a function block diagram of a multimedia device according to an embodiment of the present invention. The multimedia device 200 includes a control signal receiving unit 210 , a control circuit 220 , a multimedia buffer unit 230 , a storage unit 240 , and a frame buffer unit 250 . The control signal receiving unit 210 receives a control signal, e.g., a pause signal or a playback signal. The control circuit 220 processes a data signal to generate image data to be played. The image data to be played is buffered in the frame buffer unit 250 (e.g., implemented by a DRAM) before transmitted to and played by a display device (not shown). The multimedia buffer unit 230 and the storage unit 240 store rerecorded multimedia that the timeshift function generates. For example but not limited to, the multimedia buffer unit 230 may be implemented by a storage medium having a faster access speed (e.g., a volatile memory such as a DRAM or SRAM), and the storage unit 240 may be implemented by a storage medium having a greater storage capacity (e.g., a non-volatile memory such as a flash, SSD and magnetic disk). The control circuit 220 includes a demodulating unit 221 , a transport stream processing unit 223 , a video decoding unit 225 , an audio decoding unit 227 and a control unit 229 .
[0017] Referring to FIG. 3 showing a flowchart of a data processing method of a multimedia device of the present invention, operation details of the multimedia device of the present invention are given as below. After the multimedia device 200 receives a data signal, the demodulating unit 221 demodulates the data signal to generate a multimedia signal (step S 310 ). The transport stream processing unit 223 performs parsing processes such as removing the header on the multimedia signal in a transport stream format to generate multimedia data (step S 320 ). The control unit 229 then writes the multimedia data into the multimedia buffer unit 230 , and prerecorded multimedia data is obtained from the multimedia buffer unit 230 (step S 330 ). Next, the control unit 229 receives a pause signal sent from the control signal receiving unit 210 (step S 340 ), controls the video decoding unit 225 and the audio decoding unit 227 to suspend respective operations to cause the multimedia device 200 pause playback of the multimedia data (step S 350 ), and writes the prerecorded multimedia data into the storage unit 240 (step S 360 ). In step S 350 , while the control unit 229 controls the video decoding unit 225 to suspend operations of the video decoding unit 225 , it further records a decoding state of the video decoding unit 225 at that time. This decoding state is a presentation timestamp (PTS) and group of pictures (POC) of the frame that the video decoding unit 225 is currently decoding. The decoding state of the video decoding unit 225 may be used as a basis for later determining whether seamless playback can be performed when the playback is subsequently resumed. By recording the frame that is currently being decoded, the decoding operation of the video decoding unit 225 in the subsequent playback process can be prevented from interference (with associated details to be given in the playback process). When the user later resumes watching, the control unit 229 receives the playback signal sent from the control signal receiving unit 210 (step S 370 ), reads the prerecorded multimedia data from the storage unit 240 , and transmits the multimedia data to the video decoding unit 225 and the audio decoding unit 227 to play the prerecorded multimedia data.
[0018] In the multimedia device and the data processing method according to embodiments of the present invention, since the multimedia data has already been stored before the pause signal is received, the multimedia data corresponding to the frame (to be referred to as a target frame) that the video decoding unit 225 is currently decoding at the time when the pause signal is received is in fact stored in advance (i.e., included in the abovementioned prerecorded multimedia data). Thus, when the prerecorded multimedia data is played in step S 380 , the playback may be resumed from the target frame, hence eliminating the issue of lost frames or black screen as in the conventional technology.
[0019] In step S 330 , if the multimedia buffer unit 230 is fully written, the newly generated multimedia data overwrites the oldest multimedia data. It should be noted that, in different embodiments, given the storage capacity of the multimedia buffer unit 230 is large enough, the storage unit 240 may be omitted from the multimedia device 200 , and the prerecorded multimedia data may be entirely stored in the multimedia buffer unit 230 . When the playback is later resumed, the control unit 229 reads the prerecorded multimedia data from the multimedia buffer unit 230 . In the above scenario, step S 360 may be correspondingly omitted.
[0020] FIG. 4 shows an operation process of a multimedia device performing playback of prerecorded multimedia data according to an embodiment of the present invention, i.e., the detailed process of step S 380 in FIG. 3 . After receiving the playback signal, the control unit 229 reads the prerecorded multimedia data from the storage unit 240 , transmits the prerecorded multimedia data to the video decoding unit 225 and the audio decoding unit 227 (step S 405 ), and controls the video decoding unit 225 to suspend receiving the multimedia data that the transport stream processing unit 223 outputs. The control unit 229 then determines whether seamless playback can be performed according to the decoding state of the video decoding unit 225 recorded in step S 350 (step S 410 ). More specifically, in step S 410 , the control unit 229 determines whether there are records of PTS and POC of the target frame. The PTS and POC are the basis for the video decoding unit 225 to later search for the target frame. Thus, if the PTS and POC are not successfully recorded in step S 350 , it means that the target frame cannot be identified from the prerecorded multimedia data, nor can seamless playback be performed. If seamless playback cannot be performed, the video decoding unit 225 is reactivated, and the video decoding unit 225 and the audio decoding unit 227 are caused to decode the prerecorded multimedia data in order to play the prerecorded multimedia data (step S 415 ). Conversely, if the control unit 229 determines in step S 415 that seamless playback can be performed, the control unit 229 controls the audio decoding unit 227 to suspend the decoding process (step S 420 ), and the video decoding unit 225 decodes the prerecorded multimedia data. To prevent the decoding operation of the video decoding unit 225 from interference, the control unit 229 writes a previous frame (still stored in the buffer unit of the video decoding unit 225 or may be obtained from the prerecorded multimedia data) of the frame that the video decoding unit 225 is currently decoding, as previously recorded in step S 350 , to fill up the entire frame buffer unit 250 (step S 425 ), and determines a predetermined time according to the data amount and format of the prerecorded multimedia data (step S 430 ). This predetermined time is for the video decoding unit 225 to search for the target frame from the prerecorded multimedia data. Because the video decoding unit 225 needs to decode the prerecorded multimedia data, if the amount of the multimedia data is large or each frame includes a larger amount of pixel data, the time need for the video decoding unit 225 to search for the target frame is inevitably longer. In general, when the multimedia device 200 receive the pause signal, the data amount between the multimedia data that the video decoding unit 225 is currently decoding and the target frame is approximately a playback period of 1 second. Therefore, based on the data format of a highest resolution (i.e., the longest time period that the video decoding unit 225 needs to decode one frame) and the decoding capability of the decoding unit 225 , the control unit 229 may estimate the maximum value of the search time. If the video decoding unit 225 searches beyond this search time, the control unit 229 determines that the target frame cannot be found from the prerecorded multimedia data.
[0021] Next, the control unit 229 controls the video decoding unit 225 to search the prerecorded multimedia for the target frame (step S 435 ). The video decoding unit 225 searches for the target frame according to a decoding order of the frames, and the decoding order may be learned from the PTS or POC of the frames. In steps S 440 , S 445 and S 450 , the control unit 229 continues monitoring whether the video decoding unit 225 finds the target frame within the predetermined time. More specifically, the video decoding unit 225 decodes the prerecorded multimedia data, and the target frame is found if the PTS and POC or the decoded frame are identical to the PTS and POC recorded in step S 350 . When the video decoding unit 225 finds the target frame within the predetermined time (when the determination result of step S 440 is affirmative), the video decoding unit 225 sends a signal to notify the control unit 229 , which then controls the audio decoding unit 227 to reactivate (step S 455 ), and controls the video decoding unit 225 and the audio decoding unit 227 to discard the multimedia data earlier than the target frame and start decoding the multimedia data from the target frame as the starting point (step S 460 ). When the multimedia data that has been decoded achieves video and audio synchronization (step S 465 ), the multimedia data can then be played (step S 470 ).
[0022] On the other hand, if the video decoding unit 225 fails to find the target frame within the predetermined time (the determination result of step S 445 is negative), the control unit 229 controls the video decoding unit to stop searching for the target frame (step S 450 ), followed by similarly performing steps S 455 to S 470 . However, playback cannot be resumed in continuation from the target frame. Even though seamless playback cannot be achieved, having already stored in advance the multimedia data before the pause signal is received, the present invention still provides preferred user experiences as opposed to conventional technologies.
[0023] For example, the data signal may be various types of live stream signals, e.g., live digital television signals, live analog television signals and Internet live signals.
[0024] One person skilled in the art can understand implementation details and variations of the method of the present invention in FIG. 3 and FIG. 4 based on the disclosure of the device of the present invention in FIG. 2 . While the invention has been described by way of example and in terms of the preferred embodiments, it is to be understood that the invention is not limited thereto. On the contrary, it is intended to cover various modifications and similar arrangements and procedures, and the scope of the appended claims therefore should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements and procedures. | A data processing method of a multimedia device is disclosed. The multimedia device pauses playback of multimedia data in response to a pause signal. The method includes: buffering the multimedia data before the pause signal is received to obtain prerecorded multimedia data; writing the prerecorded multimedia data into a storage unit in response to the pause signal; reading the prerecorded multimedia data from the storage unit in response to a playback signal; and playing the prerecorded multimedia data. | 7 |
BACKGROUND OF THE INVENTION
The invention relates to improvements in containers for stacked items and more particularly to an improved dispensing container which holds and protects the items and is readily separated to provide ready access to the items for removing individual items from the container.
More particularly, the invention relates to a container and dispenser especially well suited for reclosable plastic bags. While the features of the invention are particularly useful in the packaging and dispensing of small individual plastic bags made of a slippery plastic material, and the disclosure contained herein will be primarily directed to a description of packaging and dispensing this type of item, it will be appreciated by those versed in the art upon reviewing the disclosure that certain features of the invention may be used for packaging and dispensing other items.
In the development of inexpensive reclosable plastic bags, such bags are used for a multitude of purposes and improved manufacturing techniques and structures have reduced the cost of the bags so that they are used for many purposes and in many circumstances. For example, such bags may be used individually by a householder having the bags available in the kitchen or workroom. Also, the bags may be used in merchandising such as in a retail store where individual bags are used for packaging hardware items such as nuts and bolts or are used for packaging foodstuffs.
For these uses, the bags are conveniently contained and shipped in cartons and a number of problems in handling are present. The bags usually being formed of a plastic such as polyethylene are slippery and must be contained so as to be easily handled prior to usage. Generally, banding or handling which distorts the bags is not the best solution and it is useful to package the bags so that they retain their original flat undistorted shape.
Further, it is desirable that when the bags are received by the user, they can be utilized one by one and a means of dispensing individual bags is desirable. If the user can remove the bags one at a time from a holder without disturbing the shape or containment of the other bags, such packaging is desirable.
It is accordingly an object of the present invention to provide an improved method and structure for packaging stackable items such as plastic bags wherein the package holds and protects the bags in their lay-flat undistorted shape and can be easily opened for removal of the bags.
A further object of the invention is to provide a structure and a method for containing stackable items such as plastic bags which provides a protective enclosure and a means of handling the bags until use and additionally provides a means for dispensing the bags whereby they can be readily accessible and individually withdrawable from the container.
A feature of the invention is the provision of a rectangular container for bags which has a tear strip extending around the center and wherein the container holds two opposed stacks of bags with their tops adjacent each other. In a preferred form the tops are interconnected and the container is arranged such that a separating thread is contained in the container which can be simultaneously drawn through the center of the stacks of bags to separate them as the container is opened. A further feature is the provision of such container which continues to keep the bags arrayed in their stacked fashion after it is opened and additionally provides free access to individual bags by exposing their edges so that they can be independently and individually drawn from the halves of the opened container. The container is arranged so that it readily sets on a counter or flat space and provides a dispenser as well as a retainer for the stacks of bags permitting withdrawal individually or in plural numbers for the user.
Other objects, advantages and features will become more apparent with the teaching of the principles of the invention in connection with the disclosure of the preferred embodiments thereof in the specification, claims and drawings, in which:
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a container holding plastic bags or like items in accordance with the principles of the invention;
FIG. 2 is a perspective view in slightly modified form of the invention;
FIG. 3 is a perspective view of the container shown in FIG. 2 opened for dispensing bags;
FIG. 4 is a perspective view of the container of FIG. 1 opened for dispensing bags;
FIG. 5 is an enlarged fragmentary perspective view of the connection between the tops of the bags which are held within the container;
FIG. 6 is a perspective view of still another form of the invention;
FIG. 7 is a perspective view of a further form of the invention;
FIG. 8 is a sectional view taken substantially along line VIII--VIII of FIG. 6 showing the interior of the container;
FIG. 9 is a vertical sectional view of the container before it is opened taken substantially along line X--X of FIG. 7; and
FIG. 10 is a sectional view similar to FIG. 9, taken along line X--X of FIG. 7 and illustrating the process of separating the bags and opening the carton.
DESCRIPTION
As illustrated in FIG. 1, a container or carton 11 is provided for housing bags shown in broken line at 12 and 13. The bags are arranged in parallel stacks with their top ends meeting at 16. The bags are of the type which are openable and reclosable and have a rib and groove zipper element adjacent the top as shown at 14 for the stack of bags 12 and at 15 for the stack of bags 13.
The carton 11 is of board or other semi-rigid material and is of a size to tightly enclose the bags 12 and 13. The bags being of polyethylene or similar plastic material are slippery so that the carton has an interior dimension substantially equal or only slightly larger than the outer dimension of the bags to hold them in their oriented stacks. The carton can thus be handled for packing in larger cartons for shipping and for usage without losing the orientation of the stacked bags within. Even if the carton is tossed or dropped, the bags will remain in their position within the carton and heavy handling or usage with a denting of the carton will not adversely affect the carton which is to be opened at the time the bags are to be used.
Extending along three walls of the carton is a frangible line or strip 20. In a preferred form, the frangible strip is a tear strip which can be grasped by a tab at one end 20a and torn from the carton to separate it into two equal sections 20b and 20c which can be seen better in FIG. 4. The container has a first wall 11a, a second wall 11b and a third wall 11c across which the tear strip 20 extends. The fourth wall, shown on the underside of FIG. 1 at 11d has a fold line 18 which is aligned with the ends of the tear strip so that the sections 20b and 20c of the carton can be folded back after the removal of the tear strip.
After the tear strip is torn from the three sides of the container 11, the two equal sections are folded back along the fold line 18 to assume the position shown in FIG. 4. The stacks 12 and 13 of bags are then exposed with their tops projecting a short distance from the two sections 20b and 20c of the carton. The removal of the tear strip 20 provides the exposure of the ends of the bags which are at the location shown at 16 in FIG. 1.
In the arrangement of FIG. 1, and in the arrangement of FIG. 2, the bags are in two separate stacks with their tops merely touching each other or lightly connected so that when the sections of the cartons are folded back, the tops of the bags separate.
Since the bags are of very slippery material, the tops can be individually gripped as they appear in FIG. 4, and individually pulled from the container 11. The bags can then be pulled either individually or in any number that the user wishes to use and the carton will provide a servicing dispensing container for the remaining bags. The bags can be pulled from either side of the carton and it provides a stable erect container and dispenser for the bags.
If desired, the two sections of the carbon can be secured to each other along the confronting faces of the wall 11d. Attaching means are provided such as strips of adhesive tape 22 and 23 for securing the contronting faces 11d.
In the arrangement of FIG. 2, a carton 21 is arranged similar to that of FIG. 1 but with a fold line 19 on a different surface so that when the carton is opened, the stacks of bags 26 and 27 therein are situated lengthwise relative to each other. For this purpose, a fold line 19, FIG. 2, is provided along a narrow face 21d of the carton. A tear strip 17 extends along three faces of the carton, namely faces 21a, 21b and 21c. When the tear strip 17 is torn from the carton, it separates it into two sections and the sections are folded back along the fold line 19 to provide a dispensing container arrangement as shown in FIG. 3. Attaching means shown in the form of adhesive tapes 24 and 25 may be provided for securing the confronting faces 21d to each other, FIG. 3.
While the tops of the bags 26 and 27 may be lightly attached or not attached in the arrangement of FIG. 3, the bag arrangements can be arranged so that the tops of the bags are attached such as by perforations 16a shown in FIG. 5. The breaking open of the carton, after removing the tear strip 17, will normally tear the bags along their top separation line 16, FIG. 5, or a cutting means may be provided to complete the separation of the bags from their parallel stacks. In FIG. 5 the stacks are shown at 12 and 13 with their top edges shown at 16.
FIGS. 6 and 7 show a means for separating or cutting the tops of the bags, and in the arrangement shown the carton is separated into its sections and the bags are cut in the same operation.
In the arrangement of FIG. 6, a carton 31 is shown with stacks 43 and 44 of bags therein. The carton is of a size so that the bags are snuggly located therein as with the arrangement of FIGS. 1 and 2.
A tear strip 32 extends along three faces 31a, 31b and 31c of the carton. A fold line will exist on the fourth face 31d at the location of the tear strip.
The tear strip is uniquely constructed in that it is provided with a severing or cutting thread 33 extending within the carton along beneath the stacks of bags. A lead end 33a of the thread is connected to the tear strip 32. The other end 33b of the thread is anchored within the carton to the interior lower edge of the wall 31c.
When the user is ready to use the bags, he pulls upwardly on the tear strip 32 thus pulling the thread 33 upwardly and drawing it through between the tops of the bag stacks 43 and 44 thus cutting the tops of the bags and separating them. A full removal of the tear strip 32 will pull the severing thread 33 completely between the stacks of bags thoroughly separating them. Then when the carton is bent back in its two sections about the fold line, the tops of the bags will project upwardly so they generally will have the appearance illustrated in FIG. 4. The thread will be discarded along with the tear strip 32, out of the way. The operation of the cutting thread in being drawn upwardly is illustrated in FIG. 8 as a cutting tension is applied to the thread 33 simultaneously with the tear strip 32 being pulled upwardly by being grasped at its lead end 33a. The removal of the tear strip and the upward pulling of the cutting thread can be done quickly with a mere flick of the wrist and the remaining carton sections bent back of each other to provide the dispensing container with the bags held oriented therein ready for individual withdrawal.
In the arrangement of FIG. 7, the broad tear strip is omitted and a cutting thread 36 not only separates the bags but also separates the sections of a container 41. The container and the bags therein have the same construction as with the arrangement of FIGS. 1, 2 and 6 and the bags will be lightly joined at their tops such as by a perforate line as shown at 16a in FIG. 5. The cutting thread 36 is anchored within the carton at 34. The other end of the cutting thread has a tab 35 which projects exteriorly of the carton in a location to be easily gripped as illustrated in FIG. 9. As the user grips the tab 35 and pulls it upwardly, the cutting thread severs the carton along the line 37, FIG. 7. When this is completed, the thread 36 can be completely pulled from the carton and discarded and the carton bent open about a fold line on the back surface 41d which is in alignment with the line of severance 37 and the carton will then essentially have the appearance of FIG. 4. Inasmuch as the severance line 37 is at a single location so that material is not removed as is the case with the tear strip, the bags normally will not project beyond the top edge of the two sections of the carton. However, in some cases stacks of bags may be used which slightly overlap at their top edges and in that case, the bag tops will project. It will be understood that the tear thread 36 can be used with interconnected bags or with bags with stacks that merely touch and are not interconnected in which case the thread 36 will serve only to cut the container 41 into sections.
In operation a user receives the carton such as shown in the form in which it appears when shipped as illustrated in FIGS. 1, 2, 6 or 7. The user pulls the tear strip from the container, and in the arrangement of FIG. 6 also pulls the cutting thread 33, and in the arrangement of FIG. 7, only pulls the cutting thread 36. This separates the stacks of bags within the container and also separates the container into sections so that it can be folded open to expose the stacks of bags and provide a handy dispensing container for ready removal of the bags. | A container dispenser assembly containing stacks of flat bags with their tops adjacent and releasably interconnected and held in a rectangular cardboard container having a central tear strip extending over three walls with the tear strip removable and the separated sections of the container foldable about a fourth wall. In one form a thread is anchored within the container to be drawn between the tops of the bags and separate them. When the container is folded open, the bags may be withdrawn one by one from the two halves of the container. | 8 |
RELATED APPLICATIONS
Pursuant to 35 U.S.C. § 119, this application claims priority to German Patent Application No. 10 2004 046 432.4, filed Sep. 24, 2004, and to German Utility Application No. 20 2005 005 880.7, filed Apr. 13, 2005, the contents of both applications being incorporated by reference herein.
FIELD OF THE INVENTION
The invention relates to a flanging device for roll-flanging a rim of a component or other work piece along a flanging edge, and to a flanging method.
BACKGROUND OF THE INVENTION
The situation presented, in which an outer part of the body has to be connected to an inner part by hemming, arises for example in the case of wheel arches of vehicle bodies. The outer shell of the body has a circular arced, preferably semi-circular section, on the rim of which the so-called wheel arch is fastened on the inner side of the body. The problem here is that the outer side of the outer shell should not be deformed or at least deformed as little as possible, i.e. must not for example receive any dents or scratches, since these would be immediately visible when the outer shell is subsequently painted, and would spoil the aesthetic effect which the vehicle body is intended to impart.
In principle, this therefore prohibits using hemming device comprising pressing and counter pressure rollers, since the counter pressure roller would then run along the outer side of the outer shell and could deform it. The solutions known hitherto get by using sliders which are moved radially outwards behind the rim of the outer shell, with respect to the wheel section, and thus turn it inwards. Since a counter pressure is omitted here, the quality of the hem is not always satisfactory. Moreover, this is relatively involved equipment which only caters specifically for the body of one type of vehicle in each case, which makes using it in production facilities in which different types of body are built problematic.
SUMMARY OF THE INVENTION
The invention relates to a flanging device for roll-flanging a rim of a component or other work piece along a flanging edge, and to a flanging method. The flanging device preferably forms a hemming device for producing a hem connection. The component is preferably a body part, as such or already assembled. The invention is then particularly advantageous if the body part forms a viewed area, for example an outer part of the body, in the subsequent finished product, preferably a vehicle.
The invention preferably relates to a device for hemming the rim of a first body part which preferably forms an outer side of a body, wherein the rim of a second body part which for example forms an inner part of the body lies in the hem slot of the first body part. The device comprises a flanging head with at least one counter pressure roller supported on the outer side of the first body part and preferably at least two pressing rollers which oppose the counter pressure roller or each oppose one counter pressure roller, for successively turning over the rim of the first body part.
It is an object of the invention to turn over the rim of a component, preferably vehicle a body part and in particular an outer metal sheet, using simple means, such that the component is not deformed. The device should also be configured such that it can be quickly adapted to different component shapes.
The invention relates to a flanging device comprising a flanging head, at least one first flanging roller and at least one second flanging roller which are each pivoted by the flanging head. In the case of roll-flanging, the first flanging roller forms a pressing roller which rolls off on a rim to be beaded, preferably a narrow rim strip of the component. The second flanging roller acts as a counter pressure roller for the first flanging roller, i.e. it takes up the force to be applied by the first flanging roller in order to bead the rim strip by for example 30° or 45°. In accordance with their respective function, the first flanging roller is referred to below as the pressing roller and the second flanging roller is referred to below as the counter pressure roller. The flanging head can in particular be fastened to one end of a robot arm which preferably exhibits all six degrees of freedom of movement, but at least exhibits the degrees of freedom required for the flanging process itself.
In accordance with the invention, the flanging device further includes a stable protective structure which can be fastened to the component or is fastened during roll-flanging. For the counter pressure roller, the protective structure either forms a rolling surface itself, on which the counter pressure roller rolls off during roll-flanging, or it only forms the rolling surface indirectly, by supporting a rolling surface on which the counter pressure roller directly rolls off. In the first case, an inner side of the protective structure abuts the component and is preferably shaped so as to be adapted to its surface. An outer side of the protective structure forms the rolling surface for the counter pressure roller. In the second case, the protective structure is arranged in the inner region of the flanging edge to be formed and abuts the inner side of the component, wherein the protective structure is preferably shaped so as to be adapted to the surface of the inner side. Because it is supported on the inner side, the component can itself form the rolling surface for the counter pressure roller in the second case and is nonetheless not deformed by the pressing counter pressure roller, or far less than without the support on the inner side.
If the protective structure forms the rolling surface itself, the counter pressure roller does not roll off directly on the component, but on the protective structure which preferably forms a sort of matrix which is adapted to the inner side of the outer contour of the component, such that even the smallest spatial configurations of the component can be exactly copied and deformations need not be feared. The flanging head itself can be a standard type which can also be used for other flanging processes. Above all, this has the advantage that a number of different bodies can be processed for example on a production line for vehicle bodies, preferably automobile bodies. It is merely necessary to retain respectively adapted protective structures which can be initially placed onto the body or inserted in the inner region of the flanging edge, before the flanging process is started.
In preferred embodiments, the area of the protective structure with which the protective structure abuts the area to be protected is shaped so as to conform to said abutting area of the component, such that the protective structure and the component abut full-face.
The bodies and the protective structure preferably each have at least one marker which allows the protective strip to be placed in an exact fit on the rim to be flanged over. The at least one marker on the body can be a contour or edge which is inherently predefined, such as sections for doors, beams or the like. At least one hole can also be specifically introduced. In preferred embodiments, the protective structure possesses a centring element, preferably a positioning pin, and at least one stopper element which is used as a contour abutment. Alternatively, the protective structure can also be provided with just two centring elements, preferably positioning pins, or with just two stopper elements. Using such pairs of positioning means which co-operate with corresponding positioning means of the component or—in the assumed example—with the body, the protective structure is exactly positioned relative to the flanging edge when it abuts the abutting area of the component. In the alternative embodiment, in which the protective structure is arranged in the inner region of the flanging edge, a single positioning element—preferably a stopper element—can be sufficient for positioning.
In one development, the flanging head mounts a third flanging roller which forms another counter pressure roller for at least one of the first flanging roller and the second flanging roller in a flanging process. A closed flow of force may be obtained by means of such a third flanging roller. Such an embodiment is particularly advantageous for a protective structure arranged in the inner region of the flanging edge. The third flanging roller, acting as a suppressor, can also serve to fasten the protective structure. Thus, in particular in a protective structure arranged in the inner region of the flanging edge, an additional fastening can even be completely omitted. In principle, this also applies to a protective structure abutting on the outside.
In another development, a sensing element is fastened to or formed on the flanging head, preferably pivoted as a sensing roller, in addition to the at least two flanging rollers, and the protective structure forms a guiding path for the sensing element, preferably another rolling surface, which follows the course of the flanging edge. The sensing element, which is guided on the guiding path along the flanging edge in a flanging process, in turn guides the flanging head, enabling the expenditure which has to be made for controlling the movements of the flanging head, in particular the measuring expenditure, to be reduced. For roll-flanging along the flanging edge, it is in principle even possible to completely omit controlling or regulating on the basis of positional signals obtained by measurement. If the flanging head is guided along the flanging edge by means of a sensing element, by guiding the guiding element on a guiding cam which is preferably formed by the protective strip but could in principle for example also be formed by the flanging edge itself, the flanging head is preferably mounted such that it can move back and forth in a direction pointing at least substantially normally with respect to the guiding path, preferably against an elastic restoring force. The elastic restoring force can expediently be a pneumatic force.
Advantageously, a sensor, preferably a distance sensor, is provided. The sensor is preferably mounted on the flanging head or a platform to which the flanging head is fastened. By means of the sensor the distance between the flanging head and the component or the protective structure can be ascertained. The sensing element can be replaced by a distance sensor which operates without contact, by moving the distance sensor along the guiding path described with respect to the sensing element during roll-flanging, constantly measuring the distance without contact, and using the readings to regulate the movement of the flanging head. A 1D sensor is sufficient as the distance sensor.
In developments, a two-dimensional sensor is provided which operates without contact, i.e. a 2D sensor using which the position of the flanging head relative to the component, in particular its flanging edge, can be ascertained in a plane of view onto the component. The 2D sensor is preferably mounted on the flanging head or a platform to which the flanging head is fastened. In the preferred application—roll-flanging on a body part—the plane of view extends in the XZ plane of the usual co-ordinate system of vehicle bodies. This sensor system is only required, and in advantageous method embodiments also only used, to place the flanging head for roll-flanging on the flanging edge. If a mechanical sensing element or the distance sensor cited is not provided, the 2D sensor or another substitute sensor system, for example two 1D sensors, can also be used to regulate the movements of the flanging head during roll-flanging. Preferably, however, the 2D sensor system is provided in addition to the sensing element or distance sensor cited. Sensing and regulating in the XZ plane is particularly advantageous for hemming a so-called drop flange. If, however, it may be assumed that the components to be flanged always assume the position provided for roll-flanging with sufficient accuracy, and are themselves always shaped with sufficient accuracy, then a 2D sensor system can be omitted, since in this case, it is possible to rely on the fact that it is sufficient if the flanging head moves to a predefined position, for example a pre-programmed position. In the circumstances cited, the sensing element and the distance sensor can also be omitted.
The protective structure, or at least the part of it which forms the rolling surface or rolling surface support, is advantageously shaped in a moulding method and is in this sense preferably a moulded structure. The protective structure can be sufficiently pre-formed by moulding that, if the protective structure forms the rolling surface, the moulded piece ideally only needs the surface forming the rolling surface to be reworked. In general, however, other surface processing will also be necessary. Preferably, assembly points are thus provided on the protective structure after moulding, for example for the positioning elements of the positioning apparatus or as applicable for fastening elements of a fastening apparatus. Although, if strong enough, the protective structure can be made of plastic, it is preferably as cast metal structure made of a metal or metal alloy. In particular, it can be a grey cast iron structure. Alternatively, however, it would also be conceivable for the protective structure to be made of steel. Furthermore, it would also be conceivable to form the protective structure as a composite structure, for example with a rolling surface consisting of steel or a ceramic material and a bearer structure made of grey cast iron or plastic. A protective structure consisting entirely of a ceramic material is also not to be ruled out.
The flanging head preferably consists of a bearer which can be shifted relative to a holder and on which at least one counter pressure roller is mounted, and of a carriage held such that it can shift on the bearer and on which the at least one pressing roller, preferably at least two pressing rollers, is/are mounted at different approach angles, wherein an actuating apparatus is preferably provided between the bearer and the carriage and can be arrested or set such that it exerts a predetermined actuating force. In order to turn the rim over by a particular angle, a corresponding pressing roller is selected on the head and encloses the desired angle with a counter pressure roller. This pair of rollers is moved along the rim of the component, preferably a vehicle body, which is to be hemmed over, such that the rim is turned over by the desired angle. This process is repeated two or three times, wherein the turning-over angle becomes tighter and tighter, until the hem is finally closed or, if a hem connection is not being produced, the desired bending angle has been obtained.
When the rim is only partially turned over, the actuating apparatus is arrested such that the rim is set to the predefined angle, irrespective of the forces necessary for this. When completely closing a hem, by contrast, it is crucial that a particular force is exerted in order to pinch the rim of a second body part, lying in the hem slot. To this end, the actuating apparatus is preferably controlled such that it exerts a predetermined actuating force.
The bearer and the carriage guided on it are in turn mounted on a holder such that they can shift, the holder generally being connected to a robot arm which moves the holder in pre-calculated trajectories. In order to hem over a rim, the robot guides the flanging head along the rim, wherein the shifting bracket of the bearer on the holder enables an automatic equalisation perpendicular to the component. This also equalises tolerances with regard to the orientation of the component relative to a target pre-set which is known to the robot. It is therefore not necessary to separately and exactly detect the actual position of the component, preferably a metal body sheet.
The actuating apparatus is preferably a pneumatic cylinder, wherein the latter, when arrested, is charged with highly pressurised air, which all but amounts to being arrested. When performing a final hemming process, the pressure in the cylinder determines the forces exerted on the hem.
The flanging head is particularly simple to handle if a counter pressure roller is provided on the bearer for each of the pressing rollers on the carriage, since the head then merely needs to be re-orientated as a whole from flanging step to flanging step.
As mentioned above, it is possible for the bearer to be able to be freely shifted on the holder, within limits. However, in order that movements of the robot arm do not lead to jolting oscillations between the limits, a damper can be arranged between the bearer and the holder.
The invention further relates to a method such as has already been outlined above. Crucially, a protective structure is initially placed onto the component rim to be hemmed over or inserted into the inner region of the flanging edge and forms or supports a rolling surface for the counter pressure roller. Using a device in accordance with the invention, different component shapes can therefore be processed. It is merely necessary to retain a respectively compatible protective structure. The flanging head can remain unchanged; merely its control is advantageously adapted to the respective body, wherein the thickness of the protective structure should also be taken into account.
Furthermore, when partially turning over, the actuating apparatus of the flanging head is preferably arrested such that the bending angle predefined by the actuating angle is maintained during roll-flanging. When finally hemming, by contrast, a defined force is advantageously exerted which leads to the hem slot being optimally closed and generates sufficiently large clamping forces on the rim of the second component, lying in the hem slot.
Wherever the invention has been explained above with respect to a hemming device, these embodiments also apply analogously to a flanging device, i.e. to a device by means of which a hem connection can be formed but which can also serve to merely bead the component rim by a predetermined angle. During flanging or hemming, the rim can be completely, i.e. parallel to the opposing component region, or only partially beaded.
In addition to the device itself, the subject of the invention also includes a method which can in particular be performed using the flanging device. This is a method for roll-flanging a component along a flanging edge, on one side of which the component forms a viewed area or in any event an area which is to be treated gently, and on the other side of which the component forms a rim, preferably a rim strip, which is to be flanged around the flanging edge. In accordance with the method, the rim is flanged around the flanging edge by means of a pressing roller which rolls off on the rim and a counter pressure roller, wherein the counter pressure roller does not roll off directly on the component but rather on a protective structure protecting the component, in order to take up the bending force exerted by the pressing roller on the rim. In the alternative embodiment, the counter pressure roller can roll off directly on the component, as applicable also on another structure placed onto the component, but the component is supported by the protective structure on its inner side facing away from the counter pressure roller. In the case of the protective structure being arranged in the inner region of the flanging edge, said protective structure can in principle support the rim of the component and in this way, while not taking up the force exerted by the pressing roller for beading, can nonetheless support the rim acting as a rolling surface for the pressing roller. The protective structure is preferably fastened to the component or to a structure, the fixed constituent of which is formed by the component, either using an additional fastening apparatus or by an additional roller acting as a suppressor, or both in combination. As applicable, the pressing roller and counter pressure roller can already form the fastening apparatus together with the component. The protective structure is preferably shaped to follow the course of the flanging edge, at least on a rim facing the flanging edge. In principle, however, the protective structure could also be shaped differently, which however could require a larger flanging head, since the latter encompasses the flanging edge and the protective structure in the region of the pressing roller and the counter pressure roller co-operating with it. Advantageously, the protective structure is at least substantially as narrow as the counter pressure roller which rolls off directly on the protective strip or the rolling surface supported by it.
The subject of the invention also includes a method in which the work piece is beaded by a first angle by means of a first pair of rollers consisting of a pressing roller and a counter roller and is further beaded by a second angle by means of a second pair of rollers consisting of a pressing roller and a counter roller, wherein the rollers of the first pair of rollers in the first flanging step form a more rigid arrangement than the second pair of rollers in the second flanging step. In the first flanging step, the rollers of the first pair of rollers are preferably arrested with respect to each other, such that their rotational axes can be regarded as axes which are fixed with respect to each other. In the second flanging step, the rollers of the second pair of rollers are preferably resiliently mounted with respect to each other, such that the rotational axes of these rollers can move resiliently with respect to each other. As applicable, they are also mounted such that they are only damped with respect to each other or such that they are resilient and damped with respect to each other. In the second flanging step, the rim is preferably completely beaded, such that it comes to rest at least substantially parallel to an area of the work piece opposing across the flanging edge, as is for example usual in hem connections. Other flanging steps can be provided between the first flanging step and the second flanging step, preferably by means of yet another or a number of other pairs of rollers. One or more other flanging steps can also precede the first flanging step. The two flanging steps can also be performed in the same run, if the first pair of rollers and the second pair of rollers form a tandem, i.e. if the second pair of rollers follows the first pair of rollers.
In preferred embodiments, the protective strip is shaped and fastened to the work piece or to a structure including the work piece, such that no “air” remains between the surface to be protected and the protective strip. This prevents the work piece from giving way relative to the protective structure during roll-flanging. The protective structure can abut the surface in a line along the length of the flanging edge. More preferably, however, it abuts full-face along the width of the counter roller or along the width of the rolling surface formed by the protective structure, i.e. the protective structure is shaped so as to conform to the area to be protected or supported.
Advantageous features are also described in the sub-claims and combinations of the same. The features disclosed by the sub-claims and the embodiments described above also complement each other reciprocally. The flanging devices described in accordance with the present invention, of claims 20 and 25 and methods which may be performed using them, are preferably used in combination with the protective structure, but are also advantageous without the protective structure.
BRIEF DESCRIPTION OF THE DRAWINGS
An example embodiment of the invention is explained below on the basis of figures. Features disclosed by the example embodiment, each individually and in any combination, advantageously develop the subjects of the claims and the embodiments described above. Therefore, the foregoing summary and the following description will be better understood in conjunction with the drawing figures, in which:
FIG. 1 is a perspective view of a protective strip comprising a holding structure in accordance with the present invention;
FIG. 2 is a perspective view of a flanging head;
FIGS. 3 a - 3 c are partially truncated schematic views illustrating different stages of a flanging process in accordance with the present invention;
FIG. 4 is a perspective view of a protective strip comprising an integrated positioning and fastening apparatus in accordance with the present invention;
FIG. 5 is a partially truncated schematic view illustrating the use of an interior protective structure during a flanging step in accordance with the present invention; and
FIG. 6 is a partially truncated schematic view illustrating a flanging step using a modified flanging head and an exterior protective structure in accordance with the present invention.
DETAILED DESCRIPTION
FIG. 1 shows a protective strip 1 in a framework 2 in accordance with the present invention. As will be recognised, the protective strip 1 follows the course of a wheel section. Its inner side 1 i , visible in the figure, exhibits a contour which copies the desired outer contour of the body on the wheel arch, as a negative. The outer contour is generally in no way smooth, but is often provided with different facets and vertical structures, in order to obtain a particular aesthetic effect and/or a smooth transition to the adjacent body portions. On no account should this contouring be breached.
The framework 2 comprises a number of markers in the form of positioning pins 4 which engage with corresponding holes in the body, whereby the protective strip 1 is definitively fixed with respect to the body. Mechanical clamps 5 hold the framework 2 and therefore the protective strip 1 clamped on the body.
The outer side of the protective strip 1 is smooth and forms a rolling surface 1 a ( FIG. 3 ) for a counter pressure roller of a flanging head.
Such a flanging head 10 is shown in FIG. 2 . It consists of a holder 11 , a bearer 12 , a carriage 13 , as well as three pressing rollers 14 a , 14 b , 14 c and three counter pressure rollers 15 a , 15 b , 15 c.
The bearer 12 is held such that it can move in a carriage guide 11 a relative to the holder 11 , wherein a damping apparatus 16 limits and simultaneously damps this movement. In any event, this ability to move the bearer 12 means that the holder 11 does not have to be moved along the rolling surface 1 a exactly with regard to its transverse orientation; rather, an automatic equalisation perpendicular to the body, i.e. in the Y direction, results.
The pressing rollers 14 a, b, c on the carriage 13 oppose the counter pressure rollers 15 a, b, c on the bearer 12 , wherein each pair a, b, c encloses a different angle. The hem is set to 90° using the pair a recognisable in the background, a hemming angle of 45° is obtained using the pair b recognisable in the foreground, and the hem is closed to form a hem slot using the pair c recognisable in the top of the figure. At this point, it may be noted that it is also possible to provide only one counter pressure roller, but that a revolver or other roller changer should then be provided on the carriage 13 , in order to place the respectively compatible pressing roller opposite the one counter pressure roller. Yet other pairs of rollers can also be provided, in order to complete the beading in smaller angular increments.
The actuating apparatus 17 between the carriage 13 and the bearer 12 comprises a pneumatic cylinder which with can be charged with a high pressure, such that the carriage 13 is ultimately arrested on the bearer 12 . This setting is selected if the pairs of rollers a and b are active.
When finally closing the hem using the pair of rollers c, a predefined pressure is exerted on the pneumatic cylinder, such that a particular actuating force or closing force is exerted when closing the hem.
The successive hemming steps are shown in FIGS. 3 a , 3 b and 3 c . Before roll-hemming, the body part 20 already exhibits a pre-formed hemming edge. On the one side of the hemming edge, the body part 20 forms a viewed area 21 , and on the other side a rim strip 22 which is already beaded by an angle of for example 45° or 60°. The rim of a second body part 24 is inserted into the inner region of the flanging edge delineated by the viewed area 21 and the rim strip 22 , said second body part 24 being fixedly connected to the body part 20 by the roll-hemming. The protective strip 1 and in particular its rolling surface 1 a are just as wide as the counter pressure roller 15 a . The inner side 1 i of the protective strip 1 lies full-face against the viewed area 21 in the immediate vicinity of the hemming edge. In three flanging steps a, b and c, the rim strip 22 is further beaded successively by an angle predefined by the angular position of the pressing roller 14 a , 14 b or 14 c being respectively used. In Step a ( FIG. 3 a ), a hemming angle of 90° is set, and in Step b, an angle of about 45°. In these steps, a fixed spatial assignment of the counter pressure roller and the pressing roller is set.
In the subsequent Step c, the rim is closed, wherein the actuating force exerted is determined by the pressure in the actuating apparatus. This pinches the rim of the body part 24 in the hem slot formed.
FIG. 4 shows an advantageously reduced protective strip 1 , for which the framework 2 has been omitted. The suction apparatus 6 consists of two suckers arranged in the region of the two ends of the protective strip 1 . Another sucker, or as applicable also a number of other suckers, can be arranged between the two suckers, following the course of the rolling surface 1 a . The positioning pin 4 is furthermore arranged near the rolling surface 1 a and likewise at one of the two ends of the protective strip 1 . A stopper element 7 is arranged at the other end of the protective strip 1 , either formed on it in one piece or preferably fastened to it, and in conjunction with the positioning pin 4 ensures that the protective strip 1 is positioned on the body part 20 in an exact fit. The stopper element 7 serves as a contour abutment. Thus, its area facing the protective strip 1 can for example form a stopper area for a lower edge of the body part 20 . At least the part of the protective strip 1 which forms the rolling surface 1 a is formed in one piece by moulding and can in particular consist of grey cast iron. The positioning pin 4 can be formed integrally with the protective strip 1 in the mould or can also be fastened to the moulded protective strip 1 only after moulding. The same applies to the stopper element 7 which, however, is preferably made of plastic and fastened to the moulded piece. For positioning and fastening, the positioning pin 4 is inserted into a hole provided on the body part 20 or on another part of the body. The protective strip 1 is then rotated about the pivot formed by the positioning pin 4 until the stopper element 7 abuts the counter contour of the body part 20 or another part of the body. The inner side 1 i of the protective strip 1 is placed against the viewed area 21 , either slightly pressed or already suctioned by the suction apparatus 6 , and is then positioned relative to the flanging edge and fastened to the component 20 . The suction apparatus 6 can be embodied to be active or passive, which moreover also applies to the suction apparatus 6 of FIG. 1 . In its active embodiment, it can be charged with a partial vacuum via a conduit system. In its passive embodiment, it merely acts as an elastic suction cup which, however, can be ventilated in order to release the protective structure. In addition to the suction apparatus 6 , one or more mechanical clamps can be attached to the protective structure 1 . One or more mechanical clamps can also be provided instead of the suction apparatus 6 .
FIG. 5 shows a flanging step in a flanging method, in which an interior protective structure 3 is used. The protective structure 3 is inserted into the inner region of the flanging edge and supports the viewed area 26 of a body part 25 which then serves directly as a rolling surface. The flanging head 10 is used. The counter pressure roller 15 b rolls off directly on the viewed area 26 , along the flanging edge. The viewed area 26 thus forms the rolling surface. This rolling surface, however, is supported from within, i.e. on the inner side of the viewed area 26 , by the protective structure 3 . The protective structure 3 takes up the force exerted by the counter pressure roller 15 b during roll-flanging, such that the viewed area 26 cannot be deformed. The protective structure 3 comprises an abutting area which faces the counter pressure roller 15 b and is shaped so as to conform to the inner side of the viewed area 26 , such that it abuts full-face, i.e. faying. Furthermore, the protective structure 3 forms an abutting area for the pressing roller 15 b , wherein this support is not received until directly after the rim strip 27 has been beaded. In this sense, the rim strip 27 also forms a rolling surface supported by the protective structure 3 .
During roll-flanging as shown in FIG. 5 , the rim of the component 25 is only beaded. A hem connection is not produced. The pair of rollers 14 b and 15 b performs the final flanging step, wherein the pressing roller 14 b can be set resilient relative to the counter pressure roller 15 b by means of the actuating apparatus 17 .
In order to obtain a closed flow of force during roll-flanging, another counter pressure roller 18 which serves as a suppressor during roll-flanging can advantageously be pivoted on the flanging head 10 in addition to the pressing and counter pressure rollers already described, as in the example embodiment of FIG. 5 . The protective structure 3 forms a rolling surface 3 f for the counter pressure roller 18 on a side facing away from the pressing roller 14 b and the counter pressure roller 15 b , said rolling surface 3 f being orientated with respect to the rollers 14 b and 15 b such that the forces F 14 , F 15 and F 18 exerted by the three rollers 14 b , 15 b and 18 form a closed triangle of forces, as likewise indicated in FIG. 5 .
If, using the interior protective strip 3 , the rim strip 27 is not only to be beaded, but a hem connection to an interior body part is also to be produced, then the rim of the interior body part is arranged between the inner side of the viewed area 26 and the protective strip 3 , such that two layers of material are situated between the protective strip 3 and the counter pressure roller 15 b . For a strong hem connection, it is not absolutely necessary for the rim strip 27 to be completely beaded, i.e. placed onto the interior body part. The two body parts are preferably pre-jointed before roll-hemming, for example by means of spot welding or adhesion, wherein a full-face connection in the inner region is preferable to just a spot connection.
FIG. 6 shows the hemming step of FIG. 3 a in a modification. In said modification, a sensing roller 19 is pivoted on the flanging head 10 in addition to the pressing and counter pressure rollers 14 a - 15 c . During hemming, the sensing roller 19 rolls off on a guiding path 1 f of the protective structure 1 . The flanging head 10 follows the movement of the rotational axis of the sensing roller 19 along the flanging edge and is thus guided by the sensing roller 19 . In roll-flanging with an interior protective strip 3 , the counter pressure roller 18 can analogously be used as a sensing roller guiding the flanging head 10 . Using a sensing roller 19 or 18 reduces the measuring and regulating expenditure which has to be made for guiding the flanging head 10 . The sensing roller 19 , which could in principle be replaced by a sliding piece, is arranged between the rollers 14 b and 15 b and within the range of angles at which the rollers 14 b and 15 b encompass the flanging edge.
If the flanging head 10 possesses such a sensing roller 19 or 18 , it is preferable if the flanging head 10 is pressed against the guiding path 1 f or 3 f by an elasticity force. The elasticity force is advantageously generated pneumatically. In one further development, the flanging head 10 can then be arranged such that it can move back and forth, preferably along the Z axis ( FIG. 2 ), by means of another linear guide, for example by guiding the holder on a platform such that it can move in the Z direction or by additionally forming such a linear guide between the holder 11 and the rest of the flanging head 10 . Another damping apparatus, comparable to the damping apparatus 16 , would be provided for this optional other linear guide. Instead of a linear guide, a pivoting apparatus could for example also be provided. Only an ability to move normally with respect to the guiding cam 1 f or 3 f is necessary for pressing the sensing roller 19 or 18 .
The sensing roller 19 —and also the counter pressure roller 18 ( FIG. 5 ), if the latter is only or also used to act as a sensing roller—can be replaced by a distance sensor which operates without contact and which can be arranged instead of the sensing roller 19 and/or roller 18 , in order to scan the guiding path 1 f or 3 f without contact.
In the foregoing description, a preferred embodiment of the invention has been presented for the purpose of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiment was chosen and described to provide the best illustration of the principals of the invention and its practical application, and to enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth they are fairly, legally, and equitably entitled. | A flanging device for roll-flanging a rim of a component includes a flanging head, a first flanging roller which is mounted by the flanging head and can be rolled off on the rim during roll-flanging, and a second flanging roller which is mounted by the flanging head and forms a counter pressure roller for the first flanging roller, the flanging device including a stable protective structure which is or can be fastened to the component and forms a rolling surface for one of the flanging rollers or supports a rolling surface. | 1 |
REFERENCE TO RELATED APPLICATIONS
[0001] This application claims one or more inventions which were disclosed in Provisional Application No. 61/756211, filed Jan. 24, 2013, entitled “CLOSED CYCLE 1 K REFRIGERATION SYSTEM”. The benefit under 35 USC §119(e) of the United States provisional application is hereby claimed, and the aforementioned application is hereby incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention pertains to the field of cryorefrigeration. More particularly, the invention pertains to closed cycle cryorefrigerators for temperatures below about 4.2 Kelvin.
[0004] 2. Description of Related Art
[0005] Liquid helium has a boiling point at 1 atm (atmosphere of pressure) of 4.2 K, and is by-product of natural gas production. Helium is found in two isotopes, helium-3 ( 3 He) and helium-4 ( 4 He). Helium-4 is by far the most abundant isotope, and constitutes over 99.9% of the helium on Earth. As such, liquid helium makes an ideal cooling medium for a wide range of low temperature devices and low temperature applications, such as particle detectors, Superfluid Helium Droplet Spectroscopy (SHeDS), Superconducting Quantum Interference Devices (SQUIDs), and construction of high accuracy gyroscopes, for example.
[0006] Unfortunately, sources of natural gas that also contain helium are limited, and atmospheric helium migrates into space and is lost. The primary sources for helium production have been the United States, Russia, and a variety of other smaller producers across the globe. As helium is a limited resource, and world-wide demand has increased dramatically over several decades, the cost of this irreplaceable natural resource has also increased dramatically. According to a report by the United States Government Accounting Office (Urgent Issues Facing BLM's Storage and Sale of Helium Reserves, Feb. 14, 2013, incorporated herein by reference), the price of helium has tripled during the period from 2000 to 2012.
[0007] In addition to cost considerations, helium is a critical natural resource that is a fundamental requirement for many technologies. According to the same GAO report, approximately 26% of helium consumption is directed at cryogenic applications such as superconducting magnets, basic science research, and industrial processing. Other major applications include: controlled atmospheres in manufacturing processes (22%), aerospace pressurization and purging operations (17%), and welding (17%), among others.
[0008] Therefore it is clear that a shortage, or worse depletion, of world helium reserves could potentially have a dramatic negative effect on the production and use of critical technologies such as magnetic resonance imaging, fiber optics and semi-conductor manufacturing, space exploration, and military rockets, for example.
[0009] In order to reduce the reliance of low temperature devices on a ready supply of helium, and reduce the boil-off rate of the helium contained in a device cryostat, cryocoolers, known in the art as “cold heads”, have been developed to remove heat directly from the helium in a cryostat, thereby reducing the rate at which it boils off to the ambient atmosphere, and extending the time required between refills.
[0010] Cryocooler cold heads in common use operate on one of two principles: Gifford-McMahon cryocooler cold heads; and pulse-tube cryocooler cold heads. Both types of cryocooler are regenerative cryocollers, and generally operate on compression-expansion cycle and have a hot section outside the cryostat, and a cold section inside the cryostat. Further details of the operating principles of Gifford-McMahon cryocooler cold heads and pulse-tube cryocooler cold heads generally need not be elaborated for the purpose of this description.
[0011] It is relevant to note however, that a single cryocooler cold head can only achieve temperatures down to approximately 10 K. However, in both Gifford-McMahon and pulse-tube cryocooler cold heads, the expansion systems can be ganged together in serial stages, such that the cooled gas of one stage may be used as a pre-cooler for a second stage, thus achieving a lower temperature. Two stage cold heads currently in use can achieve temperatures in the range of 2.5 K to 4.2 K.
[0012] In many cases, the devices to which cryocooler cold heads are to be connected for cooling purposes are extremely sensitive to vibration. However, both Gifford-McMahon and pulse-tube type cryocooler cold heads produce vibrations which complicate their direct use in such applications.
[0013] While in some applications a cryocooler cold head cools a helium bath which acts as a primary conductive heat transfer medium in which a coil, circuit or detector is immersed, in other applications they may be in thermal contact with substrates that are in direct thermal contact with magnet coil windings, detector systems, or electronics components.
[0014] Cooling helium below its Lambda point (2.17 K for 4 He) results in a state change from a classical liquid state to a “superfluid” state. Superfluids are notable, and useful, for the fact that they exhibit zero viscosity and have infinite thermal conductivity. These properties can be utilized in a wide variety of commercial, experimental, and research applications. One interesting property of superfluid helium is that it forms what is known in the art as a “Rollin film”. A Rollin film is a result of the superfluid helium having zero viscosity, which in turn allows superfluid helium to migrate, or “creep”, along surfaces and coat a vessel it is contained in, for example, and other objects it comes in contact with to form a thin film. In one application, an electronics package in bath of superfluid 4 He will be surrounded by a Rollin film. Hence, rather than immersing an object in helium to cool it, cooling the object and the helium to 2.17 K or less will coat the entire object with helium and provide uniform and immediate heat transfer (due to infinite thermal conductivity in superfluid helium) from the object through the helium Rollin film.
[0015] In some applications, temperatures below 2 K are obtained by pumping liquid helium through a Joule-Thomson valve. During the pumping process, the exhausted helium vapor is vented from a cryostat into the environment. This mode of operation requires costly periodic refills of the system's liquid helium. While regenerative refrigerators, such as GM and pulse tube cryocoolers, have been developed to reach low temperatures, in the range of 4 K or less, with helium-4, they are not able to produce temperatures below the helium-4 Lambda line near approximately 2.1 K.
SUMMARY OF THE INVENTION
[0016] A closed-cycle refrigeration provides cooling to extremely low temperatures, particularly in the range of 0.5 K to 2.0 K. Furthermore, being a closed system, the closed-cycle refrigerator also addresses both the economic and resource conservation challenges previously existing in the prior art. Further, in some embodiments, the closed-cycle refrigerator decouples vibrations produced by cryocooler cold heads from low temperature devices.
[0017] A 4 K pulse tube cryocooler cold head or Gifford-McMahon (G-M) cryocooler cold head liquefies helium in a first cooling chamber at a pressure of approximately 1 atm. Liquid helium flows from the first cooling chamber through a Joule-Thomson valve and into a second cooling chamber that is evacuated by a pump. The discharged gas from the pump is routed back to the first cooling chamber to be re-condensed. This design creates a closed-cycle refrigerator that provides continuous cooling below 2 K.
[0018] The closed-cycle refrigerator also has an extra low vibration design. Cryocooler cold head cold sections of the closed-cycle refrigerator have no physical contact with subsequent cooling elements of the closed-cycle refrigerator, such as the first and second cooling chambers. In some embodiments the entire cryocooler cold head is connected to a vacuum chamber via a vibration damping coupler to further reduce the transfer of vibrations to other closed-cycle refrigerator elements. In other embodiments, the closed-cycle refrigerator cold sections are contained in a vacuum chamber as a cryostat, where a first radiation shield is thermally coupled to the first cooling chamber and a second radiation shield is thermally coupled to the first cooling chamber.
BRIEF DESCRIPTION OF THE DRAWING
[0019] FIG. 1 shows a schematic of the closed-cycle refrigerator.
[0020] FIG. 2 shows a schematic of the closed-cycle refrigerator system with a vibration damping coupling between the cryocooler cold head and a vacuum chamber flange.
[0021] FIG. 3 shows a schematic of the closed-cycle refrigerator system with a counter-flow heat exchanger between the first cooling chamber and the second cooling chamber.
[0022] FIG. 4 shows a schematic of the closed-cycle refrigerator with a counter-flow heat exchanger and an adjustable Joule-Thompson valve located outside the second cooling chamber.
[0023] FIG. 5 shows a schematic of the closed-cycle refrigerator with a counter-flow heat exchanger directly above the second cooling chamber.
[0024] FIG. 6 shows a schematic of one embodiment of the closed-cycle refrigerator in conjunction with a cryostat including a vacuum chamber and two radiation shields.
DETAILED DESCRIPTION OF THE INVENTION
[0025] A closed-cycle refrigerator capable of producing temperatures down to 1 K or less, and doing so in an economic and reliable manner, has a number of practical applications. Integration of a 1 K closed-cycle refrigerator in a superconducting magnet allows for substantially 100% recovery and recycling of gaseous helium from the magnet cryostat. In other applications, the 1 K closed-cycle refrigerator can be used to cool a variety of detectors and low noise electronic circuitry. Further, when the working fluid is 4 He (Helium-4, an abundant isotope of helium), temperatures below 2.17 K (at approximately 1 atm) cause the 4 He to act as a superfluid. Superfluid 4 H has a number of applications in basic quantum mechanical research (superfluid 4 He is a Bose-Einstein condensate), and practical application in Superfluid Helium Droplet Spectroscopy (SHeDS) and construction of high accuracy gyroscopes, for example.
[0026] Referring now to FIG. 1 and FIG. 2 , a schematic of a closed-cycle refrigerator capable of achieving temperatures of 1 K or less is shown. A cryocooler cold head 110 of the pulse-tube type is specifically shown. However, either the Gifford-McMahon or pulse-tube type cryocooler cold head can be equally employed, and this schematic representation is not meant to be limiting on the type of cryocooler cold head used. Henceforth, this cryocooler cold head 110 representation is intended to include both Gifford-McMahon and pulse-tube type cryocooler cold heads.
[0027] The cryocooler cold head 110 has a hot section 116 and a cold section 115 . The hot section 116 , containing, for example, rotary valves, chambers, orifices, and other cryocooler cold head 110 elements, is outside the vacuum chamber 30 , in ambient atmosphere. The vacuum chamber 30 is only shown in relation to a flange 20 . One skilled in the art of cryocooler cold heads 110 will appreciate that vacuum chambers 30 may be constructed in a variety of configurations, and the operation of the closed-cycle refrigerator is not directly dependent on the specific configuration of vacuum chamber 30 employed. The hot section 116 of the cryocooler cold head 110 is connected to a helium compressor through high pressure 5 and low pressure 6 lines.
[0028] The cold section 115 includes, in this example, a first stage having a first stage heat exchanger 112 and first stage tubes 12 , and a second stage having second stage tubes 11 and a second stage heat exchanger 111 having a helium condenser 113 . It will be understood that cryocooler cold heads with more stages can be used within the teachings of the invention. The cold section 115 is mounted in a first cooling chamber 40 that is also connected to a 4 K cooling station 41 , which is within a vacuum chamber 30 . The 4 K cooling station 41 is generally a plate of material with a high thermal conductivity, such as copper, aluminum, or similar material. Typical operating temperatures for the cryocooler cold head 110 are below 5 K, and preferably in the range 2.5 K to 4.5 K.
[0029] Preferably, as shown in FIG. 2 , the cryocooler cold head 110 is mounted on a flange 10 , which is in turn mounted to a vibration damper 15 , which in turn mates to the vacuum chamber flange 20 . Transfer of vibration from the cryocooler cold head 110 to the liquid helium in first cooling chamber 40 and the 4 K cooling station 41 is preferably minimized by this arrangement.
[0030] A condenser 113 is attached to the lowest stage heat exchanger (here, second stage exchanger 111 ). Operation of the cryocooler cold head 110 produces a nominal operating temperature near 4 K at the condenser 113 . After precooling at the cryocooler cold head 110 first stage tubes 12 , first stage heat exchanger 112 , and second stage tubes 11 , gas condenses upon the condenser 113 and drips into the bottom 118 of the first cooling chamber 40 .
[0031] An outlet 117 in the bottom of the first cooling chamber 40 allows withdrawal of condensed liquid, which is led to a second cooling chamber 60 and 1 K cooling station 61 . The 1 K cooling station is generally constructed as a plate of a material having a high thermal conductivity, including but not limited to, copper, aluminum, and other similar materials.
[0032] As helium flows from the first cooling chamber 40 to the second cooling chamber 60 , the liquid helium flows through a J-T (Joule-Thomson) expansion valve 50 (J-T valves are also called “isenthalpic expansion valves”). As the helium passes through the J-T valve 50 , it experiences a negative pressure change, as the working pressure (−1 atm) of the first cooling chamber 40 is greater than the working pressure of the second cooling chamber 60 . Henceforth, the term “Joule-Thompson” (“J-T”) valve refers to any number of expansion valves that can effectively be used to expand a fluid for the purposes of cooling the fluid, including, but not limited to, needle valves, capillary tube arrays, and porous ceramic constructions, for example.
[0033] The helium flowing from the first cooling chamber 40 is well below the helium Joule-Thomson inversion temperature (approximately 55 K) and therefore cools as it transitions to the second cooling chamber 60 . Depending on the pressure differential between the first cooling chamber 40 and the second cooling chamber 60 , the helium will be preferably cooled below the Lambda point of helium to a temperature in the range of 2.17 K (He-4 Lambda point) to 1 K or less. At this point, the helium ( 4 He) is a superfluid.
[0034] Helium vapor is then pumped from the second cooling chamber 60 through passage 70 by the pump 80 , and is returned to the first cooling chamber through lines 100 for re-condensing, completing the closed cycle of the refrigerator. In some preferred embodiments, the pump 80 is of the oil-free dry type.
[0035] At the start of operation, the closed cycle refrigerator is charged by opening a charging valve 91 to allow helium gas from a supply 90 of helium stored in a tank or dewar into the first cooling chamber 40 , where it is condensed to liquid helium. Once the first cooling chamber 40 accumulates enough liquid helium, the charging valve 91 is closed, and the supply 90 of helium is no longer needed. Then, the pump 80 is turned on to generate a vacuum in the second cooling chamber 60 and circulate helium from the second cooling chamber 60 through passages 70 and 100 back to the first cooling chamber 40 and cryocooler cold head 110 for re-condensing.
[0036] As the liquefaction process of the cryocooler cold head 110 within the first cooling chamber 40 takes place at a working pressure of approximately 1 atm, flow between the first cooling chamber 40 and the second cooling chamber 60 is driven by a pressure differential created by the pump 80 . In other words, in the process of transferring helium from the second cooling chamber back to the cryocooler cold head 110 and first cooling chamber 40 , a pressure below 1 atm is created in the second cooling chamber 60 , and liquid helium flows from the first cooling chamber 40 , through the J-T valve 50 , to the second cooling chamber 60 .
[0037] Thus, the closed-cycle refrigerator creates a closed loop for refrigeration below the helium Lambda point. In addition to achieving very low temperatures, mechanical isolation of the cryocooler cold head 110 from the first cooling chamber 40 and second cooling chamber 60 via the vibration damper coupling 15 ( FIG. 2 ) minimizes mechanical vibrations created by the cryocooler cold head compression/expansion mechanisms from being transferred to the first cooling chamber 40 and second cooling chamber 60 . Elimination of vibration can be important in some applications such as high resolution detectors and precision gyroscopes, as external vibration can negatively impact their performance.
[0038] The superfluid helium present in the second cooling chamber 60 can be applied to cool devices in thermal contact 120 a with the 1 K cooling station 61 , and/or, devices located inside 120 b the second cooling chamber 60 .
[0039] Referring now to FIGS. 3-5 , additional elements may be added to the embodiments previously described in FIGS. 1-2 to improve overall cooling efficiency of the closed-cycle refrigerator. The operation of the closed-cycle refrigerator remains substantially unchanged from that described herein in relation to FIGS. 1-2 , and identical reference numbers refer to the same components. However, a counter-flow heat exchanger 320 is added at the top of the second cooling chamber 60 .
[0040] In these embodiments, liquid helium is drawn from the first cooling chamber 40 through a port 117 in the bottom 118 of the first cooling chamber 40 , and passes through a first channel of the counter-flow heat exchanger 320 before passing through the J-T valve 50 . Colder helium vapor inside the second cooling chamber 60 is simultaneously drawn past a second channel of the counter-flow heat exchanger 320 for return to the cryocooler cold head 110 cold section 115 and second cooling chamber 40 . Thus, the liquid helium flowing inside the counter-flow heat exchanger 320 from the first cooling chamber 40 is pre-cooled before reaching the J-T valve 50 .
[0041] As shown in FIGS. 3-4 , the counter-flow heat exchanger 320 can be an independent element located in the flow path between the first cooling chamber 40 and the J-T valve 50 . In some embodiments, shown in FIGS. 3-4 , the J-T valve 50 is located outside the second cooling chamber 60 . In alternate embodiments, shown in FIGS. 5-6 , the first channel of the counter-flow heat exchanger 320 is located in a volume of the second cooling chamber 60 . In these embodiments, the second cooling chamber 60 defines the second channel of the counter-flow heat exchanger 320 , and the J-T valve 50 may be located outside the second cooling chamber 60 ( FIG. 5 ), or inside the second cooling chamber 60 ( FIG. 6 ).
[0042] In some embodiments, shown in FIG. 4 , an adjustable J-T valve 50 is used, and a low thermal conductive tube 330 is provided to allow variation of flow through the J-T valve from the room temperature side of the closed-cycle refrigerator for the purpose of temperature optimization in the second cooling chamber 60 .
[0043] Referring to FIG. 6 , the closed-cycle refrigerator is shown in relation to a vacuum chamber 30 and radiation shields 300 , 310 that would preferably be included in a practical implementation of the closed-cycle refrigerator described herein. Cold components are contained within a vacuum vessel 30 to minimize convective heat transfer from the ambient environment to the low temperature components of the closed-cycle refrigerator.
[0044] Radiation shields 300 , 310 are preferably incorporated to minimize radiant heat transfer from the environment to the closed-cycle refrigerator. A 4 K radiation shield 310 surrounds the second cooling chamber 60 , J-T valve 50 , and associated helium transfer lines, and is in thermal contact with the first cooling chamber 40 , being coupled to the 4 K cooling station 41 in some embodiments. A 50 K radiation shield 300 surrounds the 4 K radiation shield and part of the first cooling chamber 40 , and is in thermal contact with the first cooling chamber 40 . The point of thermal contact between the 50 K radiation shield 300 and the first cooling chamber 40 is preferably near the cryocooler cold head first stage heat exchanger 112 .
[0045] As with other embodiments described herein, the embodiments shown in FIGS. 3-6 produce superfluid helium in the second cooling chamber 60 that can be applied to cool devices in thermal contact 120 a with the 1 K cooling station 61 , and/or, devices located inside 120 b the second cooling chamber 60 .
[0046] FIGS. 3-6 also show a cryocooler cold head 110 configuration in which moving parts, such as a motor and rotary valve assembly 7 , are separated from the cryocooler cold head 110 by a bi-directional flow line 8 . This physical separation provides an added level of vibration damping within critical areas of the closed-cycle refrigerator, for example, the second cooling chamber 60 .
[0047] The closed-cycle refrigerator described herein can provide cooling temperatures down to 1 K or below and an almost vibration free environment. Further, compared to multi-stage cryocooler cold heads, the closed-cycle refrigerator is more reliable and less costly as it has almost no additional moving parts. Furthermore, in contrast to prior art devices, the closed-cycle refrigerator can achieve temperatures below approximately 2 K with no loss of helium to the ambient environment, thus providing a solution that is more cost effective and conservative of a limited natural resource.
[0048] Accordingly, it is to be understood that the embodiments of the invention herein described are merely illustrative of the application of the principles of the invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features regarded as essential to the invention. | A closed-cycle refrigerator provides cooling to extremely low temperatures, particularly in the range of 0.5 K to 2.0 K. A 4 K pulse-tube cryocooler cold head or G-M cryocooler cold head liquefies helium in a first cooling chamber at a pressure at approximately 1 atmosphere. Liquid helium flows from the first cooling chamber, through a Joule-Thomson valve, and into a second cooling chamber under a pressure differential created by a pump. Helium vapor extracted from the second cooling chamber by the pump is routed back to the first cooling chamber to be re-condensed. This closed-cycle design provides continuous cooling below 2 K. Cryocooler cold head cold sections have no physical contact with subsequent cooling elements, such as the first and second cooling chambers to reduce vibration transfer. In some embodiments the cryocooler cold head is connected to a vacuum chamber via a vibration damping coupler to further reduce vibration transfer. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a digital scan converter for a pulse radar apparatus provided with: a random-access memory, each cell of which containing brightness data; a circuit connected to the memory for reading out the brightness data and for presenting corresponding video signals on a raster scan display at positions unit for supplying persistence data and address information to process the persistence data; switching means for passing either radar video signals or the persistence data; and a logical unit for supplying, in response to the radar video signals and the persistence data, respectively, and to the brightness data stored in memory, new brightness data overwriting that stored in memory, whereby the memory positions are determined by an address conversion circuit which converts the radar video addresses and the persistence data addresses established in polar coordinates by the pulse radar apparatus and the control unit, respectively, into addresses expressed in Cartesian coordinates.
2. Description of the Prior Art
Such a digital scan converter is known from the U.S. Pat. No. 4,165,506. This converter contains a timing unit, which delivers brightness-reducing command signals at such fixed instants of time, that a persistence is obtained resembling that of a long-persistence phosphor on the display. The addresses pertaining to these command signals are generated in a pseudo-random sequence to effect a uniform reduction in brightness on the display. The present invention however has for its object to provide a digital scan converter, as set forth in the opening paragraph, attaining a persistence that resembles that of a PPI display, where the displayed radar scan shows a tangential persistence, i.e. a persistence proceeding in its direction of motion.
SUMMARY OF THE INVENTION
According to the invention the digital scan converter is characterised in that, to renew the stored brightness data, either simultaneously with a radar scan or between the generation of two successive radar scans, synchronously with a radar scan in obtaining a desired persistence on the raster scan display, the digital scan converter is provided with: a control code circuit for supplying, in response to signals from the control unit determining the conditions for and the frequency of the persistence data processing, a signal to indicate that only a radar scan must be presented on the display, a signal to indicate that simultaneously and in the same sequence therewith persistence data must be processed, or a signal to indicate that only persistence data must be processed in the same sequence as a radar scan; and a control code register in which the signals supplied via the switching means are supplemented with the output signals of the control code circuit.
The processing of persistence data is therefore oriented to the radar scan, i.e. the memory cells are subjected to a brightness-reducing process in the same sequence as that in which they were stored with radar data. This sequence thus describes, like the radar scan, a radius referred to as persistence scan hereinafter. By processing persistence data is here meant that a persistence scan is generated. The duration of the persistence is determined by the frequency at which such persistence scans are generated.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be explained with reference to the accompanying figures, of which
FIG. 1 is a block diagram of an embodiment of the digital scan converter according to the invention; and
FIGS. 2 and 3A, 3B are diagrams useful in explaining certain properties of the digital scan converter.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In FIG. 1 the random-access memory is denoted by 1. Each cell of this memory corresponds with a point of the raster of a raster scan display 2 and contains the information required for displaying a video signal at a corresponding position on the raster scan display. The memory-stored data is read out at such a frequency that a steady flicker-free picture is generated. A circuit 3 is thereto connected to memory 1 to read out the memory data, to process this data for the generation of video signals, and to present these video signals on display 2. Each memory cell comprises a given number of bit positions. The contents of such a memory cell determines the intensity at which radar video signals are presented on the raster scan display 2 at a position corresponding with the respective memory cell; the contents of a memory cell is hereinafter termed "brightness data". To read the brightness data out of memory, circuit 3 supplies the required memory addresses via line 4 and switch 5. Switch 5 will then be in the R(read) position, not shown in the figure. Memory 1 is fed alternately, via switch 5, with the address information of the video data processed in the scan converter and with the address information required for reading out memory 1. With switch 5 in the RMW(read/modify/write) position, as shown in the figure, the memory cell addressed is that of which the contents must be re-established. The video data processed in the scan converter is therefore fed to a logical unit 7 via line 6. This unit also receives the contents of the memory cell allocated by the associated address information. From the information applied to logical unit 7, the contents of the relevant memory cell is re-established via line 9. It should be noted that this does not imply that the contents of this memory cell differs per se from the foregoing contents of this cell.
As already stated, the contents of the memory cell consist of brightness data. The data to be processed in the scan converter, i.e. the data applied via line 6, need not contain any brightness data itself. This will however be so when this data consists of a quantised and digitised radar video signal. On the other hand, the data supplied via line 6 may consist of command signals, in consequence of which the brightness data in memory 1 has to be altered.
The memory cells of which the contents must be re-established are addressed from the address conversion circuit 10. This circuit converts the addresses established in polar coordinates in accordance with the radar scan pattern into addresses expressed in Cartesian coordinates. The address conversion circuit 10 thereto contains an azimuth counter 11, an adder 12, a sine/cosine generator 13 and an address register 14. The azimuth pulses B indicative of the radar antenna orientation and a pulse N indicative of an angular reference are supplied to azimuth counter 11. This counter supplies a signal representing the angular value φ between the direction in which the radar transmits the pulses and a selected reference direction. If desired, φ can be increased by a signal supplied to the azimuth counter, which signal represents the angular value .0. for rotating the picture presented on the raster scan display. The angular value .0. is supplied by a control unit 15. In adder 12 the angular value φ+.0. from the azimuth counter can be increased by k.Δφ, where k=0, 1, 2, . . . . The meaning of this will be discussed later. Control unit 15 also supplies the angular value Δφ. The angular value φ+.0.+k.Δφ is supplied to the sine/cosine generator which then produces the values sin (φ+.0.+k.Δφ) and cos (φ+.0.+k.Δφ) and sends these values to address register 14. After receiving the range increment count pulses ΔR and the radar coordinate values x o , y o from control unit 15, this register supplies the memory addresses
x=x.sub.o +n.ΔR. cos (φ+.0.+k.Δφ) and y=y.sub.o +n.ΔR. sin (φ+.0.+k.Δφ),
where n=0, 1, 2, . . . , N and N.ΔR is the set radar range.
The video data, to which the brightness data in an addressed memory cell must be adapted, is quantised in the video processing unit 16 and supplied to control code register 19 via switching means 17 and delay element 18. The video data stored in control code register 19 is fed to logical unit 7 via buffer register 20. At the same time the corresponding memory address is stored in memory 1 via register 20.
The brightness data in memory 1 should not only be adapted to the results of the radar scans but should also be subjected at certain intervals to a brightness-reducing process. To effect this reduction, the video data is replaced by "persistence" data at a certain frequency. The processing of this persistence data is oriented to the radar scans; the memory cells are subjected to the brightness-reducing process in the same sequence as that in which they are stored with the radar data. This sequence generates a "persistence" scan. In principle, it should be possible to generate persistence scans between two successive radar scans. With this process the following situations occur:
1. the brightness-reducing process is executed several times each antenna revolution; several persistence scans should therefore be generated between two successive radar scans;
2. the brightness-reducing process is executed once each antenna revolution; this is preferably done simultaneously with the the processing of the radar data, in which case the generation of addresses for displaying radar scans and generating a persistence scan occur simultaneously;
3. the brightness-reducing is executed once each N antenna revolutions; this is preferably done on the N th revolution simultaneously with the radar scan.
Control unit 15 supplies signals which determine the frequency of generation of the persistence scans, viz. N 1 : the number of persistence scans each antenna revolution, or N 2 : the number of antenna revolutions in which a persistence scan must be generated. It will be clear that signals N 1 and N 2 determine the persistence period and hence the tail length of moving targets on the display. Control unit 15 also supplies the signal A, indicative of the persistence data. The persistence data takes the position of the radar video data on starting the brightness-reducing process. Finally, control unit 15 produces the "validity" signals, viz. V 1 ,V 2 =0,0, indicating that no persistence scans may be generated, and V 1 ,V 2 =1,1, indicating that the persistence scans may be generated in accordance with N 1 or N 2 . The signals .0., Δφ, (x o , y o ), N 1 , N 2 ), A and (V 1 , V 2 ) from control unit 15 can be determined indirectly by a computer in communication with the control unit.
The control code register 19 receives the persistence data A via switching means 17 and delay element 18. Signal B v thereto sets switching means 17 in the position not shown in the figure; signal B v is the azimuth pulse delayed with respect to pulse B such that a radar scan can be performed during the delay period. In the embodiment in question, the video data or the persistence data taking the position thereof in the control code register 19, is indicated by bits CD 0-2 . The bits CD 3-5 to be written in control code register 19 are from the control code circuit 21; this circuit comprises two control circuits 22 and 23. Control circuit 22 determines the bits CD 3 ,4 after receiving signals (N 1 ,N 2 ) and (V 1 ,V 2 ). In this embodiment these bits are 1,1 if the data in control code register 19 are only to refer to a radar scan to be processed; CD 3 ,4 =0,1 if the latter data concern a combined processing of a radar scan and the generation of a persistence radian; CD 3 ,4 =1,0 if these data only concern the generation of persistence scans. Control circuit 23 determines bit CD 5 after receiving signals (N 1 ,N 2 ) and a signal L ref ; bit CD 5 is to prevent that, in case the same x,y cell is addressed by two successive radar scans and hence by two successive persistence scans, the brightness level of this cell is reduced twice. This issue will be further discussed below.
FIG. 2 illustrates a number of radar scans where, for the part of the scans situated near the origin, addresses of points of successive scans expressed in Cartesian coordinates may be equal; for instance:
x=(n-1)ΔR cos φ.sub.1 =(n-1)ΔR cos φ.sub.2 =(n-1)ΔR cos φ.sub.3 and
y=(n-1)ΔR sin φ.sub.1 =(n-1)ΔR sin φ.sub.2 =(n-1)ΔR sin φ.sub.3.
The error made by this equalisation would imply that, without taking countermeasures, the brightness data of the memory cells corresponding with parts of the scans situated near the origin and hence those of the persistence scans would be changed at or after successive scans, whereas the brightness data of the cells corresponding with parts of the scans situated at a distance from the origin would be changed at the frequency determined by N 1 or N 2 . To prevent such an error an "administration" bit is added to each cell of memory 1. The administration bit indicates that a memory cell is describing a persistence scan, which may or may not be combined with a radar scan, has already been addressed. The administration bit is compared with bit CD 5 from control circuit 23; the latter bit assumes the values 0, 1, 0, 1, . . . alternately for the persistence scans generated in the pulse repetition time. In case of unequivalence of the administration bit and bit CD 5 the brightness data of the cell is changed and the administration bit is made equal to bit CD 5 . At or after a following scan the same persistence scans are again generated with the same bits CD 5 . If now the same memory cells are covered as at or after the previous scan, the administration bit and bit CD 5 will already be equal for each of these cells, and the brightness data in the memory will not be subject to another change unless the brightness level of the video signal supplied in the last scan is greater than that of the video signal at the previous scan, the brightness data of the latter video signal already being stored in the memory.
FIG. 3A illustrates a radar scan SW and persistence scans A 1 , A 2 and A 3 . If a persistence scan is generated simultaneously with the processing of the radar scan, N 1 =4. The persistence scans are described at angles k.Δφ=1/2π, where k=0, 1, 2 and 3. If for scan SW the bit CD 5 =1 and the administration bit of a cell covered by scan SW equals 0, the brightness data will be changed and the administration bit becomes 1. After a period, corresponding with a quarter of an antenna revolution, the particular cell is covered by persistence scan A 1 ; for this scan CD 5 =0. There is again unequivalence between CD 5 and the administration bit; the brightness data is again changed and the administration bit turns 0 again. Thus after half an antenna revolution with the generation of persistence scan A 2 , for which CD 5 =1, the administration bit returns to 1; after three quarters of an antenna revolution with the generation of persistence scan A 3 , for which CD 5 =0, the administration bit turns 0 again; after a complete antenna revolution with the generation of the next radar scan, for which CD 5 =1, the administration bit turns 1 again, etc. This process will however come to a deadlock in the case of the situation shown in FIG. 3B. If a persistence scan is generated simultaneously with the processing of radar scan SW and thereafter the persistence scans A 1 and A 2 , then N 1 =3. The persistence scans are generated at angles k.Δφ=2/3kπ, where k=0, 1 and 2. If again for scan SW the bit CD 5 =1 and the administration bit of a cell covered by this scan is 0, the brightness data will be changed and the administration bit becomes 1. After one third of an antenna revolution with the generation of persistence scan A 1 , for which CD 5 =0, the administration bit is 0; after two thirds of an antenna revolution with the generation of persistence scan A 2 , for which CD 5 =1, the administration bit is 1. However, after a complete antenna revolution with the generation on the next scan SW, the bit CD 5 is again 1. Bit CD 5 is already equal to the administration bit and hence the brightness data is not changed. This undesired situation is prevented by changing bit CD 5 each antenna revolution in the cases when an odd number of persistence scans must be generated in the pulse repetition time. To achieve this, a reference signal L ref is derived from the angular value of the adding circuit 12, using an angle reference circuit 24. Signal L ref changes bit CD 5 in the control circuit 23 each antenna revolution.
FIG. 2 also shows that two successive points of radar scans can cover the same memory cell; for instance:
x=nΔR cos φ.sub.2 =(n+1)ΔR cos φ.sub.2 and y=nΔR sin φ.sub.2 =(n+1)ΔR sin φ.sub.2.
The error made with this equalisation would imply that, without taking countermeasures, the brightness data of the same cell would be changed twice in successive range increments. To prevent this error, a comparator 25 is incorporated and the delay time of element 18 is made equal to the time in which a radar signal passes through a range increment ΔR twice. Comparator 25 determines whether the stronger of the video signals is in range increment n or in range increment n+1. Bits CD 0-5 and the x, y address information of the range increment that contains the weaker video signal are blocked, while bits CD 0-5 and the (same) x, y address information of the range increment that contains the greatest video signal are passed to logical unit 7 and memory 1 respectively. Buffer register 20 can be blocked to this effect by a control signal from blocking circuit 26. In the address conditional circuit 27, connected to address register 14, the x, y addresses of each two successive range increments are compared; in case of equivalence a signal indicative of such a situation is supplied to blocking circuit 26 that, depending on the signal from comparator 25, produces said control signal. | A digital scan converter is provided with a memory, each cell of which contains brightness data for presenting a corresponding video signals on a raster scan display at positions corresponding with the respective cells; a logical unit for supplying, in response to the applied video signals and the brightness data stored in memory, new brightness data overwriting that stored in memory; an address conversion circuit for converting the addresses established in polar coordinates into addresses expressed in Cartesian coordinates to store the new brightness data in memory; and with a circuit connected to the memory for reading out the brightness data and for presenting corresponding video signals on the raster scan display. To renew the stored brightness data synchronously with the radar scans such that a prefixed persistence appears on the raster scan display, the digital scan converter comprises a control unit for supplying persistence data and azimuth values to process the persistence data and a control code register for storing the persistence data in intervals between successive radar scans. Furthermore, in said interval the latter azimuth values are supplied to the address conversion circuit for generating the addresses of the memory cells and the contents of said memory cells are adapted to the persistence data in the control code register by means of the logical unit communicating with said control code register. | 6 |
[0001] The present invention relates to methods for demonstrating stain removal. In particular, the present invention relates to in vitro methods for demonstrating stain removal by oral care compositions. The present invention also relates to staining solutions and their use in methods for demonstrating stain removal.
BACKGROUND
[0002] White teeth are seen as desirable by consumers and a variety of oral care compositions with the ability to remove stains from teeth are available. Oral care compositions with whitening efficacy can remove extrinsic stains and thereby whiten teeth. However, the stain removal process is gradual and it may take time for a consumer to notice the benefit. In certain circumstances it may take a week of brushing twice a day for a detectable shade difference to develop.
[0003] It would be desirable to be able to demonstrate the stain removal benefit of an oral care composition instantly to consumers.
BRIEF SUMMARY
[0004] According to one aspect of the present invention there is provide an in vitro method for demonstrating the stain removal efficacy of an oral care composition comprising
a. providing a substrate, b. providing a staining solution, c. providing a treatment solution comprising the oral care composition, d. immersing the substrate in the staining solution, e. removing the substrate from the staining solution, f. evaluating the color of the stained substrate, g. applying the treatment solution to the substrate and h. evaluating the color of the treated substrate,
wherein the staining solution comprises coffee.
[0013] Optionally the staining solution comprises instant coffee powder. Optionally the staining solution comprises instant coffee powder and an acid. Optionally the staining solution comprises instant coffee powder at a concentration of from about 0.10 g/ml to about 0.60 g/ml. Optionally the staining solution comprises instant coffee powder at a concentration of from about 0.20 g/ml to about 0.40 g/ml. Optionally the staining solution comprises instant coffee powder at a concentration of about 0.25 g/ml.
[0014] Optionally the staining solution comprises acetic acid. Optionally the staining solution comprises from about 0.5% to about 2.0% by volume glacial acetic acid. Optionally the staining solution comprises about 1.25% by volume glacial acetic acid. Optionally the staining solution comprises instant coffee powder at a concentration of about 0.25 g/ml and glacial acetic acid at a concentration of about 1.25% by volume.
[0015] Optionally the substrate comprises calcium carbonate. Optionally the substrate comprises the exoskeleton of a marine bivalve mollusk. Optionally the substrate comprises the exoskeleton of a marine bivalve mollusk in the family Arcidae.
[0016] Optionally the oral care composition is a dentifrice. Optionally the oral care composition comprises silica and pyrophosphate. Optionally the treatment solution comprises a slurry of an oral care composition and water. Optionally the treatment solution comprises a slurry of a dentifrice and water in a ratio of from about 1:2 to about 1:4 by weight. Optionally the treatment solution comprises a slurry of a dentifrice and water in a ratio of about 1:3 by weight.
[0017] Optionally step d comprises immersing the substrate in the staining solution for from about 20 to about 60 minutes. Optionally step d comprises immersing the substrate in the staining solution for about 45 minutes. Optionally the method additionally comprises step e (ii) wherein the substrate is air-dried.
[0018] Optionally step d comprises immersing the substrate in the treatment solution for a period of from about 20 seconds to about 2 minutes. Optionally step g comprises immersing the substrate in the treatment solution for a period of about 1 minute. Optionally step g further comprises agitating the substrate in the treatment solution.
[0019] Optionally the treatment solution is applied to the substrate using a brush.
[0020] Optionally the color of the stained substrate and the treated substrate is evaluated by measuring the L*a*b* values of the stained substrate and the treated substrate.
[0021] According to a further aspect of the invention there is provided a staining solution comprising instant coffee powder at a concentration of from about 0.10 g/ml to about 0.60 g/ml and from about 0.5% to about 2.0% by volume glacial acetic acid. Optionally the staining solution comprises instant coffee powder at a concentration of from about 0.20 g/ml to about 0.40 g/ml and from about 0.5% to about 2.0% by volume glacial acetic acid. Optionally the staining solution comprises instant coffee powder at a concentration of about 0.25 g/ml and about 1.25% by volume glacial acetic acid.
[0022] According to a further aspect of the invention there is also provided use of a staining solution as disclosed herein in the methods disclosed herein.
[0023] 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.
DETAILED DESCRIPTION
[0024] 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.
[0025] As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. In addition, all references cited herein are hereby incorporated by referenced in their entireties. In the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls.
[0026] Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight. The amounts given are based on the active weight of the material.
[0027] The methods of the present invention provide a way of demonstrating instantly the whitening and/or stain removal efficacy of an oral care composition. These in vitro methods can therefore be used to demonstrate the benefits of an oral care composition to consumers in a compelling and engaging way.
[0028] The methods of the present invention utilize a staining solution to stain a substrate before the application of an oral care composition. The substrate is selected to represent the tooth enamel surface of a mammal. The staining solution comprises coffee. It has surprisingly been found that coffee solution can be used in the methods of the present invention to demonstrate stain removal by an oral care composition. For example, in the methods of the present invention, a staining solution comprising coffee can be used to demonstrate the stain removal and/or whitening efficacy of an oral care composition such as a dentifrice. In certain embodiments, the staining solution comprises instant coffee powder, for example freeze-dried or spray-dried coffee powder or granules. In certain embodiments the staining solution comprises an instant coffee-chicory mixture. In certain embodiments the staining solution comprises an instant coffee-chicory mixture comprising from about 50 to about 80% by weight coffee. In certain embodiments the staining solution comprises an instant coffee-chicory mixture comprising from about 60 to about 70% by weight coffee. In certain embodiments the staining solution comprises an instant coffee-chicory mixture comprising about 60% by weight coffee. In certain embodiments the staining solution comprises an instant coffee-chicory mixture comprising about 70% by weight coffee. In certain embodiments the staining solution comprises NESTLE NESCAFÉ SUNRISE instant coffee, NESTLE NESCAFÉ SUNRISE Premium instant coffee, NESTLE NESCAFÉ SUNRISE STRONG instant coffee and mixtures of one or more thereof. In the methods of the present invention, the staining solution comprising coffee is used to stain a substrate which represents a tooth surface. Thus the coffee stained substrate can be used to demonstrate the stain removal and/or whitening efficacy of an oral care composition. This stain removal and/or whitening can be demonstrated much more quickly using the methods of the invention than if the oral care composition was applied by a consumer to his or her own teeth.
[0029] In certain embodiments, the staining solution comprises instant coffee powder at a concentration of from about 0.10 g/ml to about 0.60 g/ml, for example from about 0.10 g/ml to about 0.50 g/ml, from about 0.10 g/ml to about 0.40 g/ml, from about 0.10 g/ml to about 0.30 g/ml, from about 0.20 g/ml to about 0.60 g/ml or from about 0.25 g/ml to about 0.60 g/ml. In certain embodiments the staining solution comprises about 50 g coffee powder in about 150 ml water.
[0030] In certain embodiments, the staining solution comprises both coffee powder and an acid. In certain embodiments, the staining solution comprises acetic acid. In certain embodiments, the staining solution comprises from about 0.5% to about 2.0% by volume glacial acetic acid. For example the staining solution may comprise from about 0.5% to about 1.5% or from about 1.0% to about 1.5% by volume glacial acetic acid. In certain embodiments the staining solution comprises about 1.25% by volume glacial acetic acid.
[0031] In certain embodiments, the staining solution comprises both instant coffee powder and glacial acetic acid. For example, in certain embodiments the staining solution comprises from about 0.10 g/ml to about 0.60 g/ml, from about 0.10 g/ml to about 0.50 g/ml, from about 0.10 g/ml to about 0.40 g/ml, from about 0.10 g/ml to about 0.30 g/ml, from about 0.20 g/ml to about 0.60 g/ml or from about 0.25 g/ml to about 0.60 g/ml instant coffee powder and from about 0.5% to about 2.0% by volume glacial acetic acid, from about 0.5% to about 1.5% or from about 1.0% to about 1.5% by volume glacial acetic acid. In certain embodiments the staining solution comprises about 50 g coffee powder in about 150 ml water together with about 50 ml 5% glacial acetic acid. The staining solutions of the present invention evenly stain the substrate and do not fade rapidly. For example, the staining solutions of the present invention stain the substrate for at least about 1 hour, at least about 2 hours, at least about 4 hours, at least about 8 hours, at least about 12 hours, at least about 24 hours or at least about 48 hours. Once dried on the substrate, the staining solutions of the present invention cannot be removed by merely rinsing the stained with water.
[0032] In certain embodiments, the substrate comprises solid calcium carbonate. In certain embodiments, the substrate comprises the exoskeleton of a marine bivalve mollusk, for example of the family Arcidae. In certain embodiments, the substrate is a shell, for example a white ark shell. In certain embodiments the substrate is a medium size white ark shell approximately 1-3 inches (2.54 to 7.62 cm) in width. In certain embodiments the substrate is of uniform white appearance with substantially no uneven spots or discoloration and substantially no damage to the surface. In the methods of the invention, the substrate acts as an in vitro model for the tooth enamel of a mammalian tooth surface, allowing the effect of oral care compositions in cleaning oral surfaces (such a tooth surfaces) to be demonstrated. In certain embodiments, white ark shells are washed in tap water prior to use in the methods of the invention in order to remove any trapped dirt.
[0033] In certain embodiments, the methods of the present invention are used to demonstrate the stain removal efficacy of a dentifrice. For example, the methods may be used to demonstrate, in vitro, the stain removal and/or whitening effects of a dentifrice. By comparing the substrate before and after application of a treatment solution comprising an oral care composition, the stain removal and/or whitening effects of an oral care composition can be demonstrated to a consumer. In the methods of the present invention, the stain removal and/or whitening effects of an oral care composition can be demonstrated in a few minutes or hours, rather than in the days or weeks required if a consumer were to use the oral care composition on their own teeth and then observe the effects.
[0034] In certain embodiments the oral care composition is a dentifrice comprising pyrophosphates, peroxide, SLS and/or high cleaning silica. In certain embodiments the oral care composition is a dentifrice comprising hydrogen peroxide. In certain embodiments the oral care composition is a dentifrice comprising sodium tripolyphosphate, tetra potassium pyrophosphate and high cleaning silica. In certain embodiments the oral care composition is a dentifrice comprising about 2-4 weight % sodium tripolyphosphate, about 2-4 weight % tetra potassium pyrophosphate and about 18 to about 26 weight % high cleaning silica. In certain embodiments the oral care composition is COLGATE VISIBLE WHITE, COLGATE OPTIC WHITE or COLGATE LUMINOUS WHITE toothpaste.
[0035] In the methods of the present invention, a treatment solution comprising the oral care composition is applied to the substrate to demonstrate the cleaning effectiveness of the oral care composition by the removal of the coffee staining from the substrate. In certain embodiments the treatment solution comprises a slurry of the oral care composition and water, for example a slurry of dentifrice and water. In certain embodiments, the treatment solution comprises a slurry of dentifrice and water in a ratio of from about 1:2 to about 1:4 by weight. For example, the treatment solution may comprise dentifrice:slurry in a ratio of from about 1:2.5 to about 1:3.5, or for example a ratio of about 1:3 by weight. The treatment solution may be prepared by thoroughly mixing a dentifrice and water in an appropriate ratio with a magnetic stirrer immediately prior to application to the substrate.
[0036] In certain embodiments, the substrate is washed and air-dried and is then immersed in the staining solution. By “air-dried” it is meant that the substrate is allowed to dry at room temperature without aid from any heating apparatus. Once “air dry”, the substrate is substantially dry to the touch and any surface water has substantially evaporated. In certain embodiments the substrate is immersed in the staining solution for from about 20 to about 60 minutes. For example, the substrate may be immersed in the staining solution for from about 20 to about 50 minutes, from about 25 to about 50 minutes, from about 30 to about 50 minutes or from about 40 to about 50 minutes. In certain embodiments the substrate is immersed in the staining solution for about 45 minutes. The substrate can then be removed from the staining solution and allowed to air dry at room temperature such that the substrate is substantially dry to the touch and such that substantially all surface water has evaporated.
[0037] In certain embodiments the stained substrate is mounted on a slide or flat stick to facilitate application of the treatment solution comprising the oral care composition.
[0038] The stained substrate is assessed for staining by the staining solution by evaluating the color of the stained substrate. The color of the stained substrate is then compared to the color of the substrate after application of the treatment solution for visual comparison. In certain embodiments, this assessment is done by the naked eye. For example, a consumer may be shown the stained substrate both before and after application of the treatment solution.
[0039] In certain embodiments the evaluation of the color of the stained substrate is quantified using measurement of the L*a*b* color space. (L*a*b* refers to stain score in accordance with the Commission International de L'Eclairage Laboratory (CIELAB) color scale. L* (lightness-darkness scale), a* (red-green chroma) and b* (yellow-blue chroma)).
[0040] From measurement of the L*a*b* values, a whitening index can be calculated: ΔW*=W*final−W*initial, where W*=(a* 2 +b* 2 +(L*−100) 2 ) 1/2 . L*a*b* values can be measure using an optic shade-taking system to analyse and identify the color of a substrate. For example, the color of the stained substrate can be measured using a Spectroshade machine.
[0041] Following evaluation of the color of the stained substrate, the treatment solution is applied to the substrate. In certain embodiments the treatment solution is applied to the substrate by immersing the substrate in the treatment solution. In certain embodiments the substrate may be immersed in the treatment solution and agitated gently. In certain embodiments the substrate may be immersed in the treatment solution by immersing the substrate in a beaker comprising the treatment solution. In certain embodiments the treatment solution is applied to the substrate using a brush, for example using a toothbrush. In certain embodiments, the treatment solution is applied to the substrate by hand using a manual or electric toothbrush.
[0042] In certain embodiments the substrate is immersed in the treatment solution for a period of from about 20 s to about 2 minutes. In certain embodiments the substrate is immersed in the treatment solution for a period of from about 30 s to about 100 s, from about 45 s to about 90 s, from about 45 s to about 90 s or from about 50 s to about 80 s. In certain embodiments the substrate is immersed in the treatment solution for a period of about 1 minute.
[0043] In certain embodiments the treatment solution is applied to the substrate by manually brushing the substrate with the treatment solution for a period of from about 30 s to about 100 s, from about 45 s to about 90 s, from about 45 s to about 90 s or from about 50 s to about 80 s. In certain embodiments the substrate is brushed with the treatment solution for a period of about 60 s.
[0044] Following application of the treatment solution to the substrate, the color of the treated substrate is evaluated. In certain embodiments, this assessment is done by the naked eye. In certain embodiments the evaluation of the color of the treated substrate is quantified using measurement of the L*a*b* color space. From measurement of the L*a*b* values, a whitening index can be calculated. Comparison of the color of the treated substrate with the color of the stained substrate allows the efficacy of the oral care composition to be demonstrated.
EXAMPLE
Example 1
[0045] A staining solution is prepared using 50 g of Nestle Classic Sunrise instant coffee dissolved in 150 ml tap water and 50 ml 5% glacial acetic acid. This is mixed well at 60° C. for about 5 minutes with continuous stirring. A dentifrice slurry treatment solution is prepared by mixing 1 part Colgate Visible White toothpaste (comprising 3.00% sodium tripolyphosphate, 2.44% tetra potassium pyrophosphate and 22.0% high cleaning silica) with 3 parts tap water and mixing thoroughly with a magnetic stirrer. 50 white Ark shells of size 1-3 inches (2.54-7.62 cm) are washed in tap water and placed in a container comprising the staining solution in a sufficient quantity for the shells to be submerged. The shells are soaked at room temperature for 45 minutes and are then removed and air-dried. Stained shells are stuck to one end of a flat stick and placed in a beaker containing 50-100 ml slurry or 50-100 ml tap water as a control. 25 shells are submerged in a treatment solution and 25 shells are submerged in water as a control. The shells are immersed in the treatment solution (or water) for 1 minute with mild agitation. The shells are then removed from the treatment solution or water, rinsed in tap water and air-dried.
[0046] Both the treated and control shells are evaluated for staining using a Spectroshade machine. The results for the treated sea shells are shown in Table 1:
[0000]
TABLE 1
Treated
W* = (a* 2 + b* 2 +
Sea Shells
L*
a*
b*
(L* − 100) 2 ) 1/2
1
82.2
−1.4
7
19.18
2
86.8
−0.9
7.6
15.26
3
89.4
−0.9
4.5
11.55
4
87
−0.9
7.1
14.84
5
83
0.4
6.9
18.35
6
79
−0.7
7.8
22.41
7
79.9
−1.7
7.7
21.59
8
79
1
9.6
23.11
9
81.5
−0.2
5.6
19.33
10
85.1
−1.2
6.3
16.22
11
78.5
−0.2
8.9
23.27
12
85.5
−0.9
6.1
15.76
13
81.7
0.4
8.7
20.27
14
79.4
−0.6
6.8
21.70
15
75.6
0.9
0.8
24.43
16
79.8
0.9
7.2
21.46
17
84.7
−1.3
6.6
16.71
18
84.1
−0.1
6.5
17.18
19
81.1
0.8
7.6
20.39
20
85.8
−1
6.5
15.65
21
84.4
0.3
7.8
17.44
22
82.1
−1.9
7.9
19.66
23
88.3
−1.4
6.7
13.56
24
78.6
−0.3
7.1
22.55
25
86.5
−0.9
5.1
14.46
Avg.
82.76
−0.472
6.816
18.65
StdDev.
3.55
0.86
1.68
3.46
[0047] The results for the untreated (stained) shells are shown in Table 2:
[0000]
TABLE 2
Stained Sea
W* = (a* 2 + b* 2 +
Shells
L*
a*
b*
(L* − 100) 2 ) 1/2
1
67.4
2.1
33.5
46.79
2
57.9
3.1
26.6
49.90
3
64.7
3.1
23.2
42.35
4
73.1
3.1
29.3
39.90
5
70.8
3.4
28.9
41.22
6
64.7
3.1
23.2
42.35
7
61.6
2.5
22
44.33
8
64.7
3.1
23.2
42.35
9
65
4.5
26.3
44.01
10
74.6
3.5
29.5
39.09
11
61.2
4
20.4
44.02
12
69.9
4.1
26
39.99
13
70.8
4.1
28.8
41.22
14
62.1
4.6
23.9
45.04
15
72.2
4.2
28.6
40.11
16
69.6
3.9
27.9
41.45
17
71.8
3.2
27.6
39.59
18
67.6
3.1
23.2
39.97
19
56.5
5.7
22.6
49.35
20
76
3.8
29.8
38.45
21
64.8
5.8
27.2
44.86
22
65.3
4.8
27.1
44.29
23
69.8
4.3
27.1
40.80
24
71.1
4.5
28.6
40.91
25
64
4.8
24.8
43.98
Avg.
67.088
3.856
26.372
42.65
StdDev.
5.047881
0.91108
3.073749
3.0
[0048] The whitening index for both the treated and untreated (stained) shells was then calculated. The results are shown in Table 3:
[0000]
TABLE 3
Whitening
L*
a*
b*
Index
Stained
Avg.
67.088
3.856
26.372
42.652339
Shells
Treated
Avg.
82.76
−0.472
6.816
18.653035
Shells
[0049] A clear difference in the whitening index of the treated and untreated (stained) shells is seen, demonstrating that the efficacy of the oral care composition Colgate Visible White can be demonstrated quickly and easily to consumers. The effects are also visible to the naked eye.
[0050] As those skilled in the art will appreciate, numerous changes and modifications may be made to the embodiments described herein without departing from the spirit of the invention. It is intended that all such variations fall within the scope of the appended claims. | An in vitro method for demonstrating the stain removal efficacy of an oral care composition comprising (a) providing a substrate, (b) providing a staining solution, (c) providing a treatment solution comprising the oral care composition, (d) immersing the substrate in the staining solution, (e) removing the substrate from the staining solution, (f) evaluating the color of the stained substrate, (g) applying the treatment solution to the substrate and (h) evaluating the color of the treated substrate, wherein the staining solution comprises coffee is provided. | 0 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a fuel injector for an internal-combustion engine. In particular, the invention relates to an injector comprising a casing, fixed on which is a nebulizer having a nozzle for the fuel under pressure, an axially mobile needle for opening and closing the nozzle by means of a first end thereof, and a rod for controlling the needle, which is controlled by the fuel under pressure, aided by a compression spring.
[0003] 2. Description of the Related Art
[0004] As is known, the control rod is substantially coaxial with the needle, which is normally pushed into a closing position of the nozzle by the fuel under pressure in a control chamber, associated to a metering solenoid valve. The compression spring is set in a cavity of the casing and acts on the needle in general through a washer or other element for adjustment of the lift of the needle and/or of the pre-loading of the spring. Furthermore, in general, set between the rod and the needle is an intermediate element, which is provided in classes, such as to enable adjustment of the total axial dimensions of the ensemble formed by the needle, the intermediate element and the rod. The intermediate element presents the drawback of generally causing a certain transverse component of the action of the rod on the needle, which leads to an irregular wear and hence a faster deterioration of the injector. In order to limit this drawback, generally the intermediate element must be made with very high precision, which consequently renders it relatively costly and complex to provide.
[0005] In a known injector, the needle has a second end having a conical depression, on which the rod acts. In order to guarantee a perfectly axial resultant of the mutual action of the second end of the needle by the rod, the conical depression of the needle is engaged through an intermediate ball. In a variant of this injector, the conical depression of the needle is engaged directly by one end of the rod, which is shaped so as to guarantee a perfectly axial resultant of the mutual action. This known injector is relatively costly to produce, also on account of the conformation of the two engagement ends and of the shims for the spring.
BRIEF SUMMARY OF THE INVENTION
[0006] The aim of the invention is to provide a fuel injector that will present high reliability and a limited cost, and provide better performance of fuel injectors according to the known art.
[0007] According to the invention, the above aim is achieved by a fuel injector for an internal-combustion engine, as claimed herein.
[0008] In particular, the spring acts on the needle through a perforated intermediate member axially engaging with a portion adjacent to the end of the rod and are formed by a bushing having an area or surface of engagement with the needle with an external diameter that is smaller than or equal to that of the needle.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0009] For a better understanding of the invention a preferred embodiment is described herein by way of example with the aid of the annexed drawings, wherein:
[0010] FIG. 1 is an axial section of a fuel injector according to the invention;
[0011] FIG. 2 is a part of FIG. 1 at an enlarged scale; and
[0012] FIGS. 3 and 4 are two sections of two variants of a detail of FIG. 2 .
DETAILED DESCRIPTION OF THE INVENTION
[0013] With reference to FIG. 1 , number 1 designates as a whole a fuel injector for an internal-combustion engine, in particular for a diesel engine (not illustrated). The injector 1 comprises an external hollow casing 2 , which extends along an axis 3 and has a side inlet 5 , designed to be supplied with fuel at a high pressure. The injector 1 further comprises a terminal nebulizer 7 , for injecting the fuel into a corresponding cylinder of the engine. Normally, the nebulizer 7 is kept closed by a conical end 8 of a shutter needle 9 .
[0014] In particular, the nebulizer 7 is carried by a body, referred to hereinafter as nozzle 10 , which is coaxial with respect to the casing 2 and is fixed in a known way to a portion 11 of the casing 2 itself. Another portion 12 of the casing 2 is set on the opposite side with respect to the nozzle 10 and houses an electromagnetically controlled metering valve 13 , of a known type and not described in detail. The valve 13 has an outlet 14 for sending, towards the usual fuel tank (not illustrated), the fuel discharged by the valve 13 itself and the part of fuel that leaks through the internal components of the injector 1 .
[0015] The nozzle 10 carries a cylindrical axial compartment 16 , which comprises a cylindrical hole 17 , axially guided in which is, in a fluid-tight way, a portion 18 of the needle 9 , which hence shares the axis 3 . The compartment 16 is engaged by a second portion 19 of the needle 9 , which terminates with the end 8 and has a diameter slightly smaller than that of the portion 18 . Defined between the portion 19 and the wall of the axial compartment 16 is a channel 20 , which, on one side, gives out into the nebulizer 7 and on the other is in communication with the inlet 5 , through a pipe 21 and an annular injection chamber 22 .
[0016] The injector 1 further comprises an axial control rod 23 , which, under the control of the valve 13 , is designed to slide in a compartment 24 of the portion 11 of the casing 2 , which also shares the axis 3 . In particular, the valve 13 comprises a valve body 25 fixed to the body 2 of the injector 1 , which is provided with an axial hole 26 , guided in which is, in a fluid-tight way, a portion 27 of the rod 23 . The portion 27 terminates at the top with a surface 28 that defines a control chamber 29 . The chamber 29 is in communication with the inlet 5 for the fuel via a calibrated inlet hole 30 and with the outlet 14 via a calibrated discharge hole 31 . The latter is normally kept closed by a shutter 32 controlled in a known way by an electromagnet 33 .
[0017] The rod 23 is provided with one end 34 opposite to the surface 28 , which is designed to act on a second end 35 of the needle 9 opposite to the conical end 8 . The rod 23 is thus subjected to the opposite axial thrusts of the pressure of the fuel present in the injection chamber 22 on the needle 9 and of the pressure of the fuel present in the control chamber 29 . Normally, with the valve 13 closed, the pressure of the fuel on the rod 23 prevails over the pressure on the needle 9 so that the nebulizer 7 is kept closed.
[0018] Furthermore, the compartment 24 of the portion 11 of the casing 2 comprises a bottom portion 36 having a larger diameter, which forms an annular shoulder 37 . The rod 23 is provided with a portion 38 adjacent to the end 34 , set around which is a compression spring 39 housed in the portion 36 of the compartment 24 and designed to contribute to carrying the needle 9 into a closing position, as will be seen in greater detail in what follows.
[0019] According to the invention, the spring 39 acts on the needle 9 through perforated intermediate means, designated as a whole by 40 , which are in axial engagement with the portion 38 of the rod 23 , the end 34 of which is designed to engage directly and at the front the second end 35 (see also FIG. 2 ) of the needle 9 , adjacent to the portion 18 . In particular, the end 34 of the rod 23 and the end 35 of the needle 9 are represented by two corresponding front surfaces, which are in contact with one another. Preferably, the end 34 of the rod 23 has an arched shaped or is shaped like a spherical cap, whilst the end 35 of the needle 9 is preferably plane.
[0020] The perforated intermediate means 40 comprise an area 43 , which is able to slide axially, with a certain amount of play, in the portion 36 of the compartment 16 . Furthermore, the intermediate means 40 comprise an area 44 having an external diameter smaller than that of the area 43 and smaller than the diameter of the portion 18 of the needle 9 . In this way, any possible displacement of the area 43 in the portion 17 of the compartment 16 of the nozzle 10 is allowed, in the case where the end 35 of the needle 9 were to be inside the portion 17 itself, ensuring that the load of the spring 39 will be transmitted only to the needle 9 excluding the nozzle 10 from said load.
[0021] The two areas 43 and 44 each have an axial hole 45 of a diameter corresponding to the diameter of the portion 38 of the rod 23 so that the means 40 are guided axially by the portion 38 of the rod 23 through said hole 45 . The portion 38 has a diameter smaller than that of the portion 18 of the needle 9 so that also the end 34 of the rod 23 has a diameter smaller than that of the end 35 of the needle 9 . According to the variant of FIGS. 1 and 2 , the two areas 43 and 44 are made of a single piece and form a single bushing 40 . The two areas 43 and 44 are cylindrical and have two external annular, plane, surfaces 47 and 48 , which are opposite and perfectly parallel to one another. The two areas 43 and 44 form between them an annular shoulder 49 , which is also external. The compression spring 39 can act directly on the plane surface 47 of the bushing 40 , whilst the plane surface 48 is designed to act directly against an annular portion of the end or surface 35 of the needle 9 .
[0022] In use, when the electromagnet 33 causes opening of the metering valve 13 , the pressure in the control chamber 29 drops rapidly so that the pressure in the injection chamber 22 acting on the needle 9 prevails over the resultant of the reduced pressure acting on the rod 23 and of the spring 39 acting on the bushing 40 . The needle 9 is hence displaced upwards thus opening the nebulizer 7 and compressing the spring 39 against the shoulder 37 of the compartment 16 . When then the electromagnet 33 is no longer energized and the shutter 32 closes under the action of elastic contrast means, in themselves known, the pressure of the fuel in the control chamber 29 is restored so that, on the one hand, the end 34 of the rod 23 pushes the needle 9 towards the nebulizer 7 and, on the other hand, the spring 39 acts on the bushing 40 , which, by means of its surface 48 , contributes to the thrust of the needle 9 in the direction of the nebulizer 7 .
[0023] According to the variant of FIG. 3 , the two areas 43 a and 44 a also form a single bushing 40 a , but the area 44 a has the shape of a truncated cone instead of being cylindrical. The surface 48 of the area 44 a acts also against the end 35 of the needle 9 (see also FIG. 2 ), but its external diameter and the angle of opening of the conical area 44 a are such that, when the needle 9 is in the position for closing the nebulizer 7 , the external surface shaped like a truncated cone of the area 44 a will not touch the edge of the cylindrical hole 17 of the nozzle 10 .
[0024] According to the variant of FIG. 4 , the intermediate means 40 b comprise two areas formed by two separate bushings 43 b and 44 b , which both have cylindrical external lateral surfaces. In this case, the two plane surfaces in contact with the two bushings 43 b and 44 b must be machined with a precision sufficient to guarantee the parallelism of the two external plane surfaces 47 and 48 .
[0025] From the above description, it is evident that, in all the variants described of the intermediate means 40 , 40 a , 40 b , the surfaces 47 and 48 are external to the hole 45 and are hence in sight. In particular, they are without any projection in the bottom area so that machining thereof is simpler and more precise. Furthermore, there is no need to have any adjustable element between the spring 39 and the intermediate means 40 , 40 a and 40 b nor a resting element between the spring 39 itself and the shoulder 37 . However, such an adjustment or resting element does not modify operation of the injector 1 .
[0026] It is understood that various modifications and improvements can be made to the injector described herein without departing from the scope of the claims. For example, the surfaces of contact of the ends 34 , 35 of the rod 23 and of the needle 9 can both be plane or curved in a complementary way. In turn, the bushing 40 of FIG. 2 can be provided with a groove made between the shoulder 49 and the external lateral surface of the area 44 , for example, for machining requirements. It is moreover possible to provide between the cylindrical areas 43 and 44 a linked area of transition different from the conical one. The external surface of the area 44 a of the bushing 40 a can also be shaped differently, or the areas 43 a and 44 a can be englobed in a single conical surface between the plane surfaces 47 and 48 . Also the external surface of the bushing 44 b can be conical or with a shaped profile. Finally, the bushing 40 can have a constant diameter, whereas the portion 18 of the nozzle 9 can be provided with an undercut for enabling its displacement, or else said portion 18 can have a length such that its end 35 will remain always outside the hole 17 .
[0027] All of the above 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.
[0028] From the foregoing it will be appreciated that, although specific embodiments of the invention have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the invention. Accordingly, the invention is not limited except as by the appended claims. | The fuel injector comprises a hollow casing, fixed on which is a nozzle having a nebulizer for the fuel under pressure, a needle axially mobile for opening and closing the nebulizer by means of a first end thereof, and a control rod, substantially coaxial with the needle and in direct engagement therewith. The needle is normally pushed into a closing position of the nozzle by the fuel under pressure acting on the rod, aided by a compression spring, which acts on the needle through a sleeve that is in axial engagement with a portion of the rod. The sleeve further comprises a surface designed to engage at the front and directly one end of the needle. The spring engages another surface of the sleeve so as to transmit its action directly onto the needle. | 5 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. provisional patent application No. 60/316.120, filed Aug. 30, 2001, and entitled “Method of Reducing Air-Rush Noise Created by Throttle Plate”.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention is directed to reducing noise in a motor vehicle, and in particular, a new throttle plate and method of design to reduce air rush noise generated as air moves past a partially opened throttle plate into the vehicle intake manifold.
[0004] 2. Background and Description of the Prior Art
[0005] Electronic fuel injection systems in vehicles have replaced carburetor systems in an effort to reduce engine emissions and increase fuel efficiency. When the driver depresses the gas pedal on a fuel injected vehicle, the throttle valve opens inside the throttle body, letting in more air. The air travels through the engine intake manifold, where it mixes with fuel from the fuel injectors and enters the engine cylinders to increase power to the vehicle. When the air rushes through the throttle body into the manifold, increased turbulent air flow is created, which can make significant noise.
[0006] Noise reduction has been a major goal of automakers in motor vehicles for the past several years. With global competition in vehicle sales, automakers often try to differentiate their vehicles from the competition by their “sound characteristics.” As major vehicle noises are reduced, other long-standing background noises must be addressed. Air rush noise through the intake system when the throttle plate is opened is one of those noises.
[0007] High frequency flow noise can be created when a butterfly valve (the throttle plate) is opened from the fully closed position to some partially open position. Due to its inherent lower material density, this can be especially troublesome in composite-based air intake systems. The convergence of turbulent air streams through the openings created on either side of the throttle plate creates what is described as a ‘whoosh’ noise by customers. The condition can exist at ‘tip-in’ (the rapid opening of the fully closed throttle plate) or at a steady state, part-throttle condition.
[0008] Several designs currently exist to reduce the air rush noise in a vehicle. One method is seen in U.S. Pat. No. 5,722,357 issued to Choi. This patent describes a gasket-like piece that is added between the throttle body and the manifold to diffuse the air flow downstream from the throttle plate. Vanes project from the interior of the circular opening to diffuse the air flow and reduce the noise. Since the vanes are not located at the source of noise, this method is less effective at reducing the noise. The addition of these protrusions can also act to partially impede the flow resulting in an increased pressure drop leading to a minor loss of power when the throttle plate is fully open. This method, however, requires an extra component to be installed on every vehicle. This is not cost-effective for mass production.
[0009] The use of protrusions downstream of the throttle plate is also discussed in U.S. Pat. No. 5,970,963 issued to Nakase et al. Several different types of protrusions from the downstream side of the throttle valve are discussed. These protrusions severely complicate the die cast tooling necessary to make the throttle body. Slides will need to be added to the die cast tool and extra machining of the casting will be necessary. This adds cost to the component and reduces production volume. The addition of these protrusions can also act to partially impede the flow resulting in an increased pressure drop further leading to a minor loss of power when the throttle plate is fully open.
[0010] Adding protrusions to the throttle plate to reduce the air rush noise has been addressed in U.S. Pat. No. 5,881,995 issued to Tse et al. and U.S. Pat. No. 5,465,756 issued to Royalty et al. Both patents describe noise reduction components added to the throttle plate to attenuate the noise. The fins on the designs, however, are of a fixed geometry to the throttle plate. While these will reduce some of the air rush noise, they may not eliminate it in all vehicle models. Manifolds and throttle bodies vary in shape, which changes the fluid dynamics and noise in the vehicles necessitating an adaptable throttle plate design. The subject matter of the above referenced patents may also have reduced power when the throttle plate is fully open due to the pressure drop caused by protrusions of these types. There still exists a need to optimize these protrusions. No optimization techniques are discussed.
[0011] The need thus still exists for a flexible throttle plate design that reduces the air rush noise across vehicle models. There needs to be a method to accomplish the noise reduction while not causing a power loss when the throttle plate is fully open. There also needs to be a method of optimizing and customizing the design to reduce the air rush noise in each individual vehicle to accommodate the different manifold and throttle body designs.
SUMMARY OF THE INVENTION
[0012] In accordance with the present invention, these and other objects are accomplished by providing an apparatus and a method for reducing the air rush noise in a variety of motor vehicles when the throttle plate is open. This reduction is for throttle plates that are gradually opened, held in a partially-open position or are rapidly opened.
[0013] On a vehicle, the throttle plate opens when the engine needs to deliver more power. The air flow over the throttle plate inside the throttle bore can cause increased turbulence and vorticies. Fins added to the throttle plate can prevent the vorticies from being generated and act to straighten the flow, thus mitigating the turbulence in the flow downstream of the plate. The fins delay convergence of the turbulent air to a point further downstream when the energy has been dissipated. This, in turn, mitigates the source of the noise. With the fins attached to one or both sides of the throttle plate, the designer has the ability to tune the acoustical response as well as the restriction imposed by the fins minimizing the effect on the engine's power output. The fins may be of constant width and spaced consistently across the throttle plate, or the spacing and width may vary.
[0014] The present invention uses fins in one or more orientations on the throttle plate to manage the flow of the air through the throttle bore to the manifold to mitigate the source of the noise. The throttle bore may be cylindrical, oval, elliptical, or a similar shape. A variety of computational fluid dynamics and other computer aided engineering methods, along with bench testing, can be used to simulate the flow of the air through the specific throttle body/manifold design to simulate the air flow and optimize the design of the fins of the throttle plate. This optimization depends upon many factors including the duct section geometry of the induction system, the airflow rate, and customer design specifications for pressure drop and radiated sound levels. The fins can be fabricated of various materials such as composite plastics or die cast aluminum. The fins can be attached to the throttle plate by various methods such as a mechanical joint, adhesive or welding. The fins could also be integrated into the plate as a one-piece design.
[0015] Additional benefits and advantages of the present invention will become apparent to those skilled in the art to which the present invention relates from the subsequent description of the preferred embodiments and the appended claims, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] [0016]FIG. 1 is a perspective view of the throttle body and manifold system showing the present invention;
[0017] [0017]FIG. 2 is a sectional view cut through the throttle bore of FIG. 1
[0018] [0018]FIG. 3 is an end view of the throttle plate of the present invention within the throttle body in the closed position;
[0019] [0019]FIG. 4 is an end view of the throttle plate of the present invention within the throttle body in the open position;
[0020] [0020]FIG. 4A is a cross-sectional view of the throttle plate of the present invention within the throttle body in the open position;
[0021] [0021]FIG. 5 is a perspective view of the throttle plate according to another embodiment of the present invention;
[0022] [0022]FIG. 6 is a side view of the embodiment shown in FIG. 5; and
[0023] [0023]FIG. 7 is a perspective view of an embodiment of the throttle plate of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0024] Referring now in detail to the drawings, shown in FIG. 1, the throttle body 4 and intake manifold 11 portion of the air intake system of an electronically fuel injected vehicle is shown. The manifold 11 is the portion of the air intake system that interacts with the fuel components. Air enters the plenum portion 6 of the manifold 11 from the throttle body 4 . The plenum portion 6 of the manifold 11 evens out the pulses in the air to help fuel economy and emissions before the air enters the inlet tracks 7 . The air from the inlet tracks 7 mixes with the fuel spray from the fuel injectors mounted on a fuel rail at the exit of the inlet tracks 7 (not shown). Thereafter, the fuel-air mixture is combusted in the combustion chamber of the engine.
[0025] The manifold 11 is attached to the throttle body 4 on the plenum 6 side of the manifold 11 at the manifold inlet 13 . The throttle body 4 mounts via a mounting flange 15 to a mounting surface 14 of the manifold inlet 13 . Fasteners, such as bolts, screws or other means, fastened through manifold attachment holes 17 and 19 , respectively formed in the mounting surface 14 and mounting flange 15 , secure the throttle body 4 to the manifold inlet 13 of the manifold 11 .
[0026] The throttle body 4 determines how much air will flow into the plenum 6 and therefore the engine. A throttle plate 2 fits snugly inside a throttle bore 28 defined within a cylindrical ring 21 of the throttle body 4 . The throttle plate 2 is attached to a throttle shaft 12 by fasteners 18 , such as bolts, screws and other means. Rotation of the shaft 12 causes the throttle plate 2 to open and close to regulate the air stream. When the driver depresses the accelerator pedal of the automobile, the throttle shaft 12 is rotated, thus opening the throttle plate 2 and allowing air to flow into the manifold 11 . The air flows through the throttle bore 28 into the manifold inlet 13 in flow direction 20 .
[0027] As seen in FIG. 2, attachment of the throttle plate 2 inside of the cylindrical ring 21 , to the throttle body 4 is shown in a sectional view as seen from the manifold 11 attachment side thereof. The throttle bore 28 has two rod holes 30 extending through its sides. The rod holes 30 extend along a common axis 31 and the throttle rod 12 fits through rod holes 30 in the throttle bore 28 . Attached to the throttle rod 12 , the throttle plate 2 fit snugly inside throttle bore 28 to substantially block air flow when the throttle plate 2 is in the closed position. As shown in FIG. 2, the throttle plate 2 is partially open.
[0028] The throttle plate 2 may be attached to the throttle rod 12 by screws or bolts 18 extending through mounting rings 25 formed within the throttle rod 12 and into the throttle plate 2 . Formed on or mounted to the throttle plate 2 are fins 8 . Preferably, the fins 8 are on the trailing edge of the throttle plate 2 . As such, when the throttle rod 12 is turned and the throttle plate 2 is opened, the fins 8 operate to mitigate the noise by straightening the air flow in direction 20 .
[0029] Referring now to FIG. 3, an end view from the mounting flange 15 of the throttle body 4 is shown. The throttle plate 2 in this view is in the closed position inside the throttle bore 28 and air flow is blocked by the snug fit between the throttle plate 2 and the throttle bore 28 . The fins 8 can be seen facing the mounting flange 15 of the throttle body 4 . When the throttle plate 2 is in this closed position, the fins 8 have no effect on the air intake system.
[0030] [0030]FIG. 4 is a view from the mounting flange 15 of the throttle body 4 , similar to that seen in FIG. 3. In this view, the throttle rod 12 has been rotated almost to the open position inside the throttle bore 28 . Rotated as such, the fins 8 move away from an orientation facing the mounting flange 15 towards an angle perpendicular or 90° relative to the closed position (wide open throttle).
[0031] Referring now to FIG. 4A, the partially open throttle plate 2 from FIG. 4 is shown in a cross-sectional view. The throttle rod 12 is rotated to open the throttle plate 2 . Air flows in air direction 20 through the throttle bore 28 . The fins 8 manage the air flow through the throttle bore 28 to reduce the air rush noise generated by the air flow over the throttle plate 2 which may be heard in the vehicle.
[0032] When the throttle plate 2 is opened, as the air travels in air flow direction 20 , it travels through the fins 8 , which are aligned in the air flow direction 20 path. With the throttle plate 2 open, the fins 8 overhang the throttle plate 2 by overhang distance 26 or height. The intrusion of fins 8 by fin overhang distance 26 modifies the air flow by preventing the vortices from being produced from turbulent flow to laminar flow, quieting the air rush noise of the air flow through the throttle bore 28 into manifold 6 .
[0033] Referring now to FIG. 5, a perspective view of one embodiment of the fins 8 of the throttle plate 2 is shown. The fins 8 themselves are formed on a separate fin attachment plate 50 . The fin attachment plate 50 is fastened, using an adhesive or a mechanical fastener, onto the rear side of the throttle plate 2 and on the lower side which forms the leading edge side 51 .
[0034] After attachment, the fins 8 progress from approximately the center of the throttle plate 2 and rise from there until reaching the end of the throttle plate 2 , a fin tip height 22 at a fin angle 24 , calculated by using the fin start location 32 and measuring angle between a ray along the fin length 36 and a ray toward the fin tip height 22 . Because of the generally round shape of the throttle plate 2 , the fin length 36 will generally be different for each fin 8 . FIG. 6 is an opposing view of the fin attachment plate 50 to that of FIG. 5. The fins 8 are seen as being equally spaced 10 between each fin 8 . The fin width 24 is shown to be consistent throughout the fin attachment 50 .
[0035] Seen in FIG. 7 is a perspective view of a further embodiment of the present invention. In this embodiment, the fins 8 are manufactured as a unitary part of the throttle plate 2 . The throttle plate 2 with the unitary fins 8 can be a one-piece die casting or made by another manufacturing method. There is no separate fin attachment piece with this embodiment.
[0036] In this latter embodiment, the fins 8 start at fin start height 34 , generally along the diameter of the throttle plate 2 . The fins 8 then rise diagonally towards the outer edge of the throttle plate 2 to fin edge height 22 . The fins 8 are again equally spaced with fin spacing 10 . The throttle plate attachment holes 25 are shown near the center of the throttle plate 2 . Formed in this manner, the fins 8 extend completely across the opening created during rotation of the throttle plate 2 , regardless of the open angle of the throttle plate 2 .
[0037] While the above description constitutes the preferred embodiments of the present invention, it will be appreciated that the invention is susceptible to modification, variation and change without departing from the proper scope and fair meaning of the accompanying claims. | A throttle body for use in the air intake system of a motor vehicle comprising a throttle body defining a throttle bore. The throttle plate is rotatably mounted within the throttle bore, having an outside diameter smaller than an inside diameter of the throttle bore. A plurality of fins, located on the throttle plate, extend from the throttle plate in a direction generally perpendicular to a plane defined by said throttle plate. The fins are optimized in number, thickness, spacing, length, shape, and angle to reduce air-rush noise without impacting engine performance. | 5 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2000-269223 filed on Sep. 5, 2000, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
This invention relates to a semiconductor memory device and, more particularly, to a nonvolatile ferroelectric memory device.
Semiconductor memory is currently used in all electric products including main memory devices of large-scale computers, personal computers, household electric appliances, cellular phones and others.
Various kinds of semiconductor memory such as volatile DRAM (dynamic RAM), SRAM (static RAM), nonvolatile MROM (mask ROM), flash EEPROM (electrically erasable programmable memory), and so on, are commercially available. Among those, DRAM is volatile but currently occupies almost all of the market because of its advantages in the sense of its cell area being ¼ as compared with SRAM and its speediness equivalent to flash EEPROM.
On the other hand, since electrically erasable programmable flash EEPROM is nonvolatile, it permits cut of power. However, it involves such drawbacks that, for example, the rewritable frequency (W/E frequency) is in the order of only 10 6 , and therefore it takes the order of micro seconds for writing and a high voltage (12V through 22V) is required for writing, its market is not yet so wide as that of DRAM.
In contrast, nonvolatile memory using a ferroelectric capacitor (ferroelectric memory) has been under development by various manufacturers since it was proposed in 1980 because it has advantages, namely, nonvolatility, rewritable frequency as high as 10 12 , read and write time equivalent to that of DRAM, operability under 3V through 5V, and so on, and it might possibly replace the entire memory market.
FIG. 18 shows a conventional ferroelectric memory cell MC 1 having one-transistor and one-capacitor, its cell array, sense amplifier and dummy cell circuit. FIG. 19 is a timing chart showing their behaviors.
As apparent from FIG. 18, each memory cell of the conventional ferroelectric memory is made up of a transistor and a capacitor connected in series. A cell array is a matrix arrangement of such memory cells, and includes bit lines/BL, BL for reading data, word lines WL 0 , WL 1 for selecting a memory cell transistor, and plate lines PL 0 , PL 1 each for driving one end of a ferroelectric capacitor. The sense amplifier is connected to the bit lines, and the dummy cell circuit is disposed symmetrically to the memory cell.
Behaviors of the ferroelectric memory are explained with reference to FIG. 19 .
In an active mode where the memory cell MC 1 , for example, has been selected, the word line WL 0 connected to MC 1 is HIGH and the plate line PL 0 is HIGH. As a result, memory cell data is read out to one of a pair of bit lines pre-charged to VSS. In case of this example, cell data is read out to the bit line /BL (/BLSA), and the potential of the bit line rises. If the memory cell data is “1”, then polarization of the ferroelectric capacitor is reversed, and the bit line is raised to a high potential. If the memory cell data is “0”, then polarization reversal does not occur, but potential of the bit line rises as much as the paraelectric component of the ferroelectric capacitor and the capacitance ratio of the bit line capacitance.
In this manner, although the bit line potential rises from Vss for both data “1” and “0”, there is a difference between the potentials. Therefore, if the reference bit line BL (BLSA) can be adjusted to an intermediate potential between those potentials, it is possible to determine whether the cell data is “1” or “0” by amplifying the difference between the bit line and the reference bit line with the sense amplifier.
Conventionally, potential of the reference bit line was generated using a dummy cell circuit as shown in FIG. 18 . In a standby mode, the transistors Q 1 and Q 2 , in which dummy word lines SWL 0 , DWL 1 are connected to gates, are turned OFF, and one end N 1 of the paraelectric capacitor C 1 is pre-charged to the source potential of Q 3 , i.e. Vss, by turning the transistor Q 3 ON. In an active mode, a transistor of a dummy word line connected to the reference bit line, which is the transistor Q 1 in this example, is turned ON to connect BL and N 1 , and then the potential of the dummy plate line, which is the other end of C 1 , is raised from Vss to VDC potential. Through these operations, potential Vref of reference BL can be raised from Vss to the intermediate potential between those corresponding to “1” and “0” data by coupling of the paraelectric capacitor C 1 .
However, the dummy cell circuit system of FIG. 18, reviewed above, involved the following problems. For example, in the 0.5 μm rule class, the bit line capacitance CB is about 1000 fF. In case a memory cell capacitor having the area of 3 μm 2 is used, if the potential at the HIGH side of the bit line amplitude is 3V (=Vaa), then the read-out potential to the bit line of “1” data is about 1.2 V in average of all cells whereas the read-out potential to the bit line of “0” data is about 0.4 V in average of all cells. Therefore, 0.8 V is required as the reference bit line potential, and taking account of fluctuation of ferroelectric capacitors, a reference potential to the level of 1.5 V (=½ Vaa) including estimation for distribution is required.
In order to generate the reference bit line potential of ½ Vaa by using the conventional dummy cell circuit shown in FIG. 18, a very large paraelectric capacitor is required. Its reason will be explained below.
FIG. 20 shows value of reference bit line potential Vref under the condition in which the capacitance of the paraelectric capacitor C 1 of the dummy cell circuit is CD, bit line capacitance is CB, and source potential for the dummy cell is VDC ((0<VDC≦Vaa): here let the maximum value be Vaa). The reference bit line potential is a value obtained by dividing VDC×CD, which is the charge of the surplus for raising the paraelectric capacitor CD from Vss to VDC, by the total capacitance (CB+CD). Therefore, to obtain ½ Vaa potential, a large paraelectric capacitor capacitance CD (=1000 fF) equal to the bit line capacitance CB is required. Then, if MOS capacitors of 8 nm are used, a dummy cell capacitor as large as 225 μm 2 is required, and the chip size will increase significantly. More specifically, to generate Vref of 1 V, capacitance as large as CD=½CB is required, and to generate of Vref of ½ Vaa or more, CB<CD. Thus, CD itself becomes a load capacitance, and there is a large difficulty.
These problems were conventionally avoided by using two other methods.
On of these methods uses a ferroelectric capacitor used in a memory cell to make up such a dummy capacitor without using a paraelectric capacitor such as MOS capacitor having a small dielectric constant. With this method, since the ferroelectric material has a very large dielectric constant, a small dummy cell circuit can be realized.
This method, however, involves the following drawbacks, among others,
1) capacitance value of the ferroelectric capacitor itself largely fluctuates;
2) the ferroelectric capacitor changes in value due to fatigue if it is subjected to polarization reversal;
3) capacitance value of the ferroelectric material decreases when polarization takes place; and
4) characteristic of the ferroelectric capacitor changes due to generation of imprint. So, it is preferable that the paraelectric capacitor is usable.
The second of those methods raises the plate potential in the read-out mode to bring about polarization reversal of the memory cell and read out a signal, and uses the bit line potential after being lowered to Vss as the read-out potential.
In this case, since the plate line potential returns to the original value beforehand, there is the effect that no paraelectric component of the memory cell capacitor is recognized. Therefore, both the “1” data potential and “0” data potential become low potentials, and a dummy cell even of a small paraelectric capacitor can generate a sufficient reference bit line potential.
This method, however, involved the following drawbacks.
1) since sense-amplifying operation takes place after the plate line is raised and lowered, random access time becomes very long, and
2) since it needs operations of again raising and lowering the plate line upon re-writing data, it results in raising and lowering the plate line twice, and cycle time becomes very long.
The Inventor has already proposed, in U. S. Pat. No. 5,903,492, as nonvolatile ferroelectric memory, a new type of ferroelectric memory simultaneously satisfying three requirements, namely,
(1) memory cell of a small size,
(2) planar transistor easy to manufacture, and
(3) versatile random access function.
FIG. 21 shows configuration of that earlier ferroelectric memory, and FIG. 22 shows an example of its operations. Since that earlier invention also uses the same read-out principle as the conventional ferroelectric memory, it similarly uses the dummy cell circuit shown in FIG. 21, which is similar to FIG. 18, for generating the reference bit line potential.
In its standby mode, the transistors Q 1 , Q 2 of the dummy word lines are turned OFF and the transistor Q 3 is held ON, one end N 1 of the paraelectric capacitor C 1 is pre-charged to the source potential of Q 3 , i.e. vss potential.
In an active mode, a transistor of a dummy word line connected to the reference bit line, which is the transistor Q 1 in this example, is turned ON to connect BL and N 1 , and then the potential of the dummy plate line, which is the other end of C 1 , is raised from Vss to VDC potential. Through these operations, potential Vref of reference BL can be raised from Vss to the intermediate potential between those corresponding to “1” and “0” data by coupling of the paraelectric capacitor C 1 .
Therefore, also in the earlier application, problems shown in FIGS. 19 and 20 occur. As compared with the conventional ferroelectric memory, the bit line capacitance in the earlier application is about ¼ per cell, and the number of cells for each sense amplifier (bit line) can be increased to 4 times. In this case, the number of dummy cell circuits themselves can be reduced to ¼, and influences of the area of the dummy cells are not so large as the conventional ferroelectric memory. Nevertheless, it still occupies several % of the chip area, and reduction of the dummy cell area is desirable. For example, in case the number of cells per bit line is ½ and a reduced amount of CB is used for enhancing signals, CB is about 500 fF in the 0.5 μm rule class, and in case a memory cell capacitor with the are of 3 μm 2 is used and the HIGH side potential of the bit line amplitude is 3V (=Vaa), the read-out potential to the bit line of “1” data is about 1.5 V in average of all cells and the read-out potential to the bit line of “0” data is about 0.5 V in average of all cells. Therefore, 1 V is required as the reference bit line potential, and taking account of fluctuation of ferroelectric capacitors, a reference potential to the level of 1.5 V (=½ Vaa) is required. In order to generate the reference bit line potential of ½ Vaa by using the conventional dummy cell circuit as shown in FIG. 21, a very large paraelectric capacitor as shown in FIG. 20 is required similarly to the conventional ferroelectric memory. To obtain ½ Vaa potential, a large paraelectric capacitor capacitance CD (=500 fF) of the same value as the bit line capacitance CB has to be used . Then, if MOS capacitors of 8 nm are used, a dummy cell capacitor as large as 112 μm 2 is required, and the chip size will increase significantly. Also for generating Vref of 1 V, capacitance as large as CD=½CB is required, and for generating of Vref of ½ Vaa or more, CB<CD. Thus, CD itself becomes a load capacitance, and there is a large difficulty.
As reviewed above, the conventional ferroelectric memory and the ferroelectric memory of the earlier application involved the problem of an increase of the chip size because of the need for a large capacitor area when using a paraelectric capacitor to generate a high reference bit line potential. The method of generating the reference bit line potential by using a ferroelectric capacitor to remove that problem involved problems of variance, deterioration, decrease and fluctuations, and involved the problems of undesirable change in reference bit line potential and a decrease of the signal read-out margin. Additionally, although there is a method for avoiding the problems by raising and lowering the plate line twice and thereby lowering the reference bit line potential, the method had the problem of a slow operation.
SUMMARY OF THE INVENTION
According to an embodiment of the invention, there is provided a semiconductor memory device comprising:
a plurality of memory cell blocks each including a serial connection of at least a plurality of memory cells each including a cell transistor and a ferroelectric capacitor connected in parallel between source and drain terminals of said cell transistor;
a plurality of word lines connected to said cell transistors;
a plurality of bit line pairs connected to said memory cell blocks;
a plurality of amplifier circuits connected to said bit line pairs to amplify a signal difference between bit lines in each of said bit line pair; and
a dummy cell circuit to generate a potential for one of said bit line pair, which is a reference bit line to which data is not read out from said memory cells, said dummy cell circuit including at least one paraelectric capacitor;
wherein in a standby mode, a first terminal of said paraelectric capacitor is pre-charged to first potential higher than ground potential, and a second terminal of said paraelectric capacitor is pre-charged to ground potential; and
in an active mode, said first terminal is connected to said reference bit line, and said second terminal is raised from ground potential to a second potential higher than ground potential.
According to another embodiment of the present invention, there is provided A semiconductor memory device comprising:
a plurality of memory cell blocks each including a serial connection of at least a plurality of memory cells each including a cell transistor and a ferroelectric capacitor connected in parallel between source and drain terminals of said cell transistor;
a plurality of word lines connected to said cell transistors;
a plurality of bit line pairs connected to said memory cell blocks;
a plurality of amplifier circuits connected to said bit line pairs to amplify a signal difference between bit lines in each of said bit line pair; and
a dummy cell circuit including a first dummy cell portion having a first paraelectric capacitor to generate a first potential of a first bit line of said bit line pair and a second dummy cell portion having a second paraelectric capacitor to generate a second potential of a second bit line of said bit line pair,
wherein a first terminal of the first paraelectric capacitor is connected to the first bit line via a first transistor and to a first dummy cell power supply potential via a second transistor, and a second terminal of the first paraelectric capacitor is connected to a first dummy plate line, and a first terminal of the second paraelectric capacitor is connected to the second bit line via a third transistor and to a second dummy cell power supply potential via a fourth transistor, and a second terminal of the second paraelectric capacitor is connected to a second dummy plate line.
According to further embodiment of the present invention, there is provided a semiconductor memory device comprising:
a plurality of memory cells made up of a serial connection of cell transistors and ferroelectric capacitors;
a plurality of word lines connected to said cell transistors;
a plurality of bit line pairs connected to said memory cells;
a plurality of amplifier circuits connected to said bit line pairs to amplify a signal difference between bit lines in each said bit line pair; and
a dummy cell circuit for generating a potential in one of bit lines in each said bit line pair, which is a reference bit line to which data is not read out from memory cells, said dummy cell circuit having at least one paraelectric capacitor;
wherein in a standby mode, a first terminal of said paraelectric capacitor being pre-charged to a first potential higher than ground potential, and a second terminal of said paraelectric capacitor being pre-charged to ground potential; and
in an active mode, said first terminal being connected to said reference bit line, and said second terminal being raised from ground potential to a second potential higher than ground potential.
According to still further embodiment of the present invention, there is provided a semiconductor memory device comprising:
a plurality of memory cells each including a serial connection of a cell transistor and a ferroelectric capacitor;
a plurality of word lines connected to said cell transistors;
a plurality of bit line pairs connected to said cell transistors;
a plurality of amplifier circuits connected to said bit line pairs to amplify a signal difference between bit lines in each of said bit line pair; and
a dummy cell circuit to generate a potential for one of said bit line pair, which is a reference bit line to which data is not read out from said memory cells, said dummy cell circuit including at least one paraelectric capacitor;
wherein in a standby mode, a first terminal of said paraelectric capacitor is pre-charged to first potential higher than ground potential, and a second terminal of said paraelectric capacitor is pre-charged to ground potential; and
in an active mode, said first terminal is connected to said reference bit line, and said second terminal is raised from ground potential to a second potential higher than ground potential.
According to yet further embodiment of the present invention, there is provided a semiconductor memory device comprising:
a plurality of memory cells each including a serial connection of a cell transistor and a ferroelectric capacitor;
a plurality of word lines connected to said cell transistors;
a plurality of bit line pairs connected to said memory cell blocks;
a plurality of amplifier circuits connected to said bit line pairs to amplify a signal difference between bit lines in each of said bit line pair; and
a dummy cell circuit including a first dummy cell portion having a first paraelectric capacitor to generate a first potential of a first bit line of said bit line pair and a second dummy cell portion having a second paraelectric capacitor to generate a second potential of a second bit line of said bit line pair,
wherein a first terminal of the first paraelectric capacitor is connected to the first bit line via a first transistor and to a first dummy cell power supply potential via a second transistor, and a second terminal of the first paraelectric capacitor is connected to a first dummy plate line, and
a first terminal of the second paraelectric capacitor is connected to the second bit line via a third transistor and to a second dummy cell power supply potential via a fourth transistor, and a second terminal of the second paraelectric capacitor is connected to a second dummy plate line.
BRIEF DESCRIPTION OF THE DRAWINGS
In the attached drawings:
FIG. 1 is a circuit diagram that shows configuration of an array, sense amplifier and dummy cell circuit of ferroelectric memory according to the first embodiment of the invention;
FIG. 2 is a timing chart that shows an example of operation timing of the configuration of FIG. 1;
FIG. 3 is a graph that shows an effect of the first embodiment of the invention;
FIG. 4 is a circuit diagram that shows a control circuit of the dummy cell of FIG. 1;
FIG. 5 is a circuit diagram that shows a generating circuit of DWL 0 ;
FIG. 6 is a circuit diagram that shows a drive circuit of a DRST signal;
FIG. 7 is a timing chart that shows a relation among signals output in FIGS. 4 through 6;
FIG. 8 is a circuit diagram that shows configuration of an array, sense amplifier and dummy cell circuit of ferroelectric memory taken as the second embodiment of the invention;
FIG. 9 is a timing chart that shows an example of operation timing of the circuit of FIG. 8;
FIG. 10 is a circuit diagram that shows configuration of an array, sense amplifier and dummy cell circuit of ferroelectric memory taken as the third embodiment of the invention;
FIG. 11 is a timing chart that shows an example of operation timing of the circuit of FIG. 10;
FIG. 12 is a circuit diagram that shows configuration of an array, sense amplifier and dummy cell circuit of ferroelectric memory taken as the fourth embodiment of the invention;
FIG. 13 is a timing chart that shows an example of operation timing of the circuit of FIG. 12;
FIG. 14 is a circuit diagram that shows configuration of an array, sense amplifier and dummy cell circuit of ferroelectric memory taken as the fifth embodiment of the invention;
FIG. 15 is a timing chart that shows an example of operation timing of the circuit of FIG. 14;
FIG. 16 is a circuit diagram that shows configuration of an array, sense amplifier and dummy cell circuit of ferroelectric memory taken as the sixth embodiment of the invention;
FIG. 17 is a timing chart that shows an example of operation timing of the circuit of FIG. 16;
FIG. 18 is a circuit diagram that shows configuration of an array, sense amplifier and dummy cell circuit of ferroelectric memory by a conventional technique;
FIG. 19 is a timing chart that shows an example of operation timing of the circuit of FIG. 18;
FIG. 20 is a graph that shows values of a reference bit line potential Vref in a conventional dummy cell circuit;
FIG. 21 is a circuit diagram that shows configuration of ferroelectric memory of an earlier application; and
FIG. 22 is a timing chart that shows an example of operations in FIG. 21 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to the drawings, embodiments of the invention will be described below.
FIGS. 1 and 2 illustrate configuration of the first embodiment of the invention, in which FIG. 1 shows configuration of an array, sense amplifier and dummy cell circuit of the invention, and FIG. 2 is its operation timing chart. FIG. 3 is a diagram that shows its effect.
A single memory cell is made up of a cell transistor and a ferroelectric capacitor connected in parallel. A single memory cell block is made of serially connecting a plurality of such parallel-connected memory cells, with one end thereof being connected to a bit line via a block selecting transistor and the other end being connected to a plate. With this configuration, 4F2-size memory cells can be realized by using planar transistors.
As shown in FIG. 1, by providing two kinds of block selecting transistors and block selecting signals BS 0 , BS 1 for /BL and BL, respectively, and rendering one of the block selecting transistors (BS 0 , B 1 ) HIGH, folded bit lines can be realized, in which only one of data of the two cell blocks is read out to the bit line and the other of the pair of bit liens is used as a reference bit line, and a 1T/1C cell, which uses one cell transistor and one ferroelectric capacitor to store one-bit data can be made. Further, by preparing two kinds of plate lines and driving only one of the plate lines on the part of the selected bit line, application of a voltage to a non-selected cell on the reference side can be prevented.
Behaviors of the circuit are briefly explained. In a standby mode, all (sub)word lines WL 0 through WL 3 are held HIGH, memory cell transistors are held ON, the block selecting signals BS 0 , BS 1 are set LOW, and the block selecting transistor is held OFF. In this manner, since opposite sides of the ferroelectric capacitor is electrically short-circuited by the cell transistors held ON, no potential difference is produced between opposite ends, and the memory polarization is maintained stably.
In an active mode, the pair of bit lines pre-charged to Vss are changed to the floating state. Then by turning off only the memory cell transistor connected in parallel to the ferroelectric capacitor to be read out, the block selection transistor is turned ON. For example, in case of selecting the ferroelectric memory cell capacitor MC 1 in FIG. 1, WL 2 is set LOW. After that, by setting the plate line PL 0 on the part of MC 1 HIGH and setting the block selecting signal BS 0 on the part of MC 1 HIGH, a potential difference between PL 0 and /BL is applied only to opposite ends of the ferroelectric capacitor MC 1 connected in parallel to the memory cell transistor having turned OFF, and polarization information of the ferroelectric capacitor is read out to the bitline /BL (/BLSA) having floated to Vss. Therefore, even with cells connected in series, by selecting a desired sub-word line, cell information of a desired ferroelectric capacitor can be read out, and fully random access is realized.
When data is “1”, polarization reversal occurs in the ferroelectric capacitor, and the bit line is raised to a high potential (BLh). When data is “0”, polarization reversal does not occur, but the bit line rises (BL 1 ) as much as the paraelectric component of the ferroelectric capacitor and the capacitance ratio of the bit line capacitance. In this manner, although the bit line potential rises from Vss for both data “1” and “0”, there is a difference between the potentials. Therefore, if the reference bit line BL (BLSA) can be adjusted to an intermediate potential between those potentials, it is possible to determine whether the cell data is “1” or “0” by amplifying the difference between the bit line and the reference bit line with the sense amplifier.
The dummy cell circuit that generates the reference bit line potential is configured by using the circuit as shown in FIG. 1 .
In a standby mode, the transistors Q 1 , Q 2 of the dummy word lines are turned OFF, and one end N 1 of the paraelectric capacitor C 1 is pre-charged to the source potential of Q 3 , i.e. VDC (>Vss) potential by holding the transistor Q 3 ON. The dummy plate line DPL at the other end of the paraelectric capacitor is held at Vss potential. That is, the voltage VDC is applied to opposite ends of the paraelectric capacitor to have it hold the charge of CD×VDC.
In an active mode, a transistor of a dummy word line connected to the reference bit line, which is the transistor Q 1 in this example, is turned ON to connect BL and N 1 . As a result, the charge stored in the paraelectric capacitor is discharged to the reference bit line. After that, potential of the dummy plate line DPL, which is the other end of C 1 , is raised from Vss to VDC′ potential. Through these operations, a value corresponding to the charge of CD×VDC′ is generated by coupling of the paraelectric capacitor C 1 , and the charge is shared by the reference bit line and the paraelectric capacitor.
Through the series of operations, the reference BL potential: Vref′ can be raised from Vss to the intermediate potential between those corresponding to “1” and “0” data. As a result, the reference bit line potential becomes a value obtained by dividing the total charge =(CD×VDC′+CD×VDC) by the load capacitance (CD+CB).
In case of VDC=VDC′, as shown in FIG. 2, it results in Vref′=(2CD×VDC)/(CD+CB)=2Vref=×2×(CD×VDC)/(CD+CB), and it is possible to generate a reference bit line potential double that of the conventional dummy cell system, i.e. Vref=(CD×VDC)/(CD+CB), with the same paraelectric capacitor capacitance.
From the opposite viewpoint, while the conventional system required a large CD value because Vref=½VDC when CD=CB, the first embodiment of the invention can use a dummy capacitor having an area only ⅓ of that of the conventional system because Vref′=½VDC when CD=⅓CB, and can reduce the chip size significantly.
For example, when CB=500 fF is employed, the conventional system requires the dummy capacitor capacitance of 500 fF, and a MOS capacitor having an 8 nm thick oxide film needs the capacitor area as large as 112 μm 2 per each dummy cell. In contrast, the first embodiment of the invention can significantly reduce the capacitor area per each dummy cell to 37 μm 2 with the capacitance of 500 fF/3=167fF.
Additionally, to generate a potential larger than ½VDC, CB<CD in the conventional system. Therefore, CD itself affects as a load capacitance, and it is possible to generate a potential. The first embodiment of the invention, however, can generate the potential as large as Vref′=VDC=Vaa when CD=CB. Therefore, the embodiment can realize ferroelectric memory without using a ferroelectric capacitor that decreases in operation margin due to fluctuations, deformations, and so on. At the same time, it can realize ferroelectric memory with a small dummy capacitor area without raising and lowering the plate twice. Therefore, high-speed operation is possible.
The first embodiment of the invention explained above is configured to share the paraelectric capacitor by the pair of bit lines and thereby reduce the dummy cell capacitor area. The paraelectric capacitor may be a gate capacitor of a MOS transistor. In this case, it is preferably a depletion-type transistor.
The dummy word lines DWL 0 , DWL 1 may be changed to LOW prior to sensing operation to disconnect the dummy cell and the reference bit line as shown by (2) in the timing chart. It is also acceptable to do it after sensing operation (1). After that, the node reset signal DRST is changed to HIGH, and DPL is decreased to LOW after pre-charging the node N 1 to VDC to return to the same status as the standby mode. It is preferable to raise DPL after changing DWL 0 to HIGH and discharging a certain amount of the charge stored to the VDC voltage to the reference bit line. For simplicity of the circuit, VDC=VDC′ is also desirable. Other methods are also usable, such as a method of fixing VDC=Vaa and changing only VDC′ in potential to generate the reference bit line potential, a method of fixing VDC=Vaa and changing only VDC in potential to generate the reference bit line potential, and so forth. It is also preferable that the amplitude potential of the DRST signal is not lower than VDC+Vt for writing VDC at N 1 , i.e. the raised potential Vpp. Potential of DWL 0 and DWL 1 may be Vpp, or may be the Vaa amplitude if the reference bit line potential +Vt<Vaa.
FIGS. 4 through 7 are circuit diagrams that show configurations of driving circuits of respective control signals used in the circuit of FIG. 1 .
The circuit shown in FIG. 4 is a circuit for driving the dummy cell source voltage VDC for pre-charging the node N 1 and the dummy plate line DPL. A stable capacitance C 3 is connected to Vss between a VDC generator 10 and the node N 1 . A PMOS transistor Q 11 and an NMOS transistor Q 12 are connected in series between the node Nx and Vss at the common connection point of these gates, an inverter 11 controlled by the HIGH-side potential Vss of the line amplitude is connected, and the connection point of both transistors gives the dummy plate line DPL a driving potential.
This is a circuit for the case of VDC=VDC′ discussed above, and if Vaa≧VDC, output of the Vaa amplitude can be directly input to the driver of the VDC source.
FIG. 5 is a circuit diagram that shows configuration of a circuit for generating potential of the dummy word line DWL 0 .
This circuit is an example of generating circuit of a driving potential of the dummy word line DWL 0 , connecting a PMOS transistor Q 13 and an NMOS transistor Q 14 in series between the HIGH-side potential Vaa of the bit line amplitude and Vss, and connecting to the common junction of their gates an inverter 12 controlled by the HIGH-side potential Vaa of the bit line amplitude such that the junction of both transistors give the dummy word line DWL 0 a driving potential. In this circuit, amplitude of the DWL 0 driving potential is Vss.
FIG. 6 is a circuit diagram that shows an example of driving circuit of the node reset signal DRST.
In this circuit, a PMOS transistor Q 15 and an NMOS transistor Q 16 are serially connected between the raised potential Vpp and Vss, and an inverted output of the signal level converter is connected to the common junction of their gates such that the junction of both transistors supplies the DRST signal. The signal amplitude converter circuit is used to extend the amplitude of the DRST signal to VPP.
FIG. 7 is a timing chart that shows a relation among signals output in FIGS. 4 through 6. Apparently, the relation is just the same as that shown in FIG. 2 .
FIG. 8 is a circuit diagram that shows configuration of an array, sense amplifier and dummy cell circuit of ferroelectric memory according to the second embodiment of the invention, and FIG. 9 is a timing chart showing their operations.
The circuit shown in FIG. 8 has substantially the same circuit configuration as FIG. 1, but it is different in that while the transistor Q 3 of FIG. 1 for pre-charging the N 1 node to VDC is NMOS, here is used PMOS and the opposite-phase signal/DRST is used in FIG. 8 .
As shown in FIG. 9, this circuit has substantially the same operations as the circuit of FIG. 1 . However, while the circuit of FIG. 1 has to raise or boost the DRST signal to Vaa in case of VDC+Vt>Vaa when pre-charging the N 1 node to VDC, the circuit shown here, using PMOS, can pre-charge it to VDC by adjusting /DRST to Vss if VDC<Vaa, and it is possible to limit the amplitude of /DRST to Vaa and can remove the booster circuit.
FIGS. 10 and 11 show the third embodiment of the invention, in which FIG. 10 is its circuit diagram and FIG. 11 is a timing chart of its operations.
With reference to FIG. 10, the circuit arrangement is substantially the same as FIG. 1, but it is different in that the dummy cell circuit is provided for each of the pair or bit lines.
The first dummy cell circuit has a first paraelectric capacitor C 1 , and its first terminal is connected to the bit line BL via a transistor Q 21 which is controlled by DWL 0 and is connected to VDC via a transistor Q 22 which is controlled by DRST 0 . The second terminal of the first paraelectric capacitor C 1 is connected to DPL 0 . Similarly, the second dummy cell circuit has a second paraelectric capacitor C 2 , and its first terminal is connected to the bit line /BL via a transistor Q 23 which is controlled by DWL 1 and is connected to VDC via a transistor Q 24 which is controlled by DRST 1 . The second terminal of the second paraelectric capacitor C 2 is connected to DPL 1 .
In case that /BL is the reference bit line, DWL 1 , DRST 1 and DPL 1 may be activated. In case that BL is the reference bit line, DWL 0 , DRST 0 and DPL 0 may be activated.
FIGS. 12 and 13 show the fourth embodiment of the invention, in which FIG. 12 is its circuit diagram showing configuration of the array, sense amplifier and dummy cell circuit of the fourth embodiment of the invention and FIG. 13 is a timing chart of its operations.
With reference to FIG. 12, the instant embodiment relates to a dummy cell in a conventional type of ferroelectric memory. A single memory cell is of a 1T1C type made up of a cell transistor and a ferroelectric capacitor.
Behaviors of this circuit are briefly explained below. In a standby mode, all (sub)word lines WL 0 through WL 1 are set LOW, plate lines PL 0 and PL 1 are also set LOW, and the bit lines are pre-charged to Vss as well.
In an active mode, the pair of bit lines pre-charged to Vss are changed to the floating state. Then only the memory cell transistor connected in parallel to the ferroelectric capacitor to be read out is turned ON. For example, in case the ferroelectric memory cell capacitor MC 1 in FIG. 12 is selected, WL 0 is set HIGH. After that, when the plate line PL 0 on the part of MC 1 is set HIGH, a potential difference between PL 0 and /BL is applied across opposite ends of the ferroelectric capacitor MC 1 , and polarization information of the ferroelectric capacitor is read out to the bit line /BL (/BLSA) held floating. Therefore, even with cells connected in series, cell information of any desired ferroelectric capacitor can be read out by selecting a desired (sub)word line, and absolutely random access is realized.
When data is “1”, polarization reversal occurs in the ferroelectric capacitor, and the bit line is raised to a high potential (BLh). When data is “0”, polarization reversal does not occur, but the bit line rises (BL 1 ) as much as the paraelectric component of the ferroelectric capacitor and the capacitance ratio of the bit line capacitance. In this manner, although the bit line potential rises from Vss for both data “1” and “0” there is a difference between the potentials. Therefore, if the reference bit line BL (BLSA) can be adjusted to an intermediate potential between those potentials, it is possible to determine whether the cell data is “1” or “0” by amplifying the difference between the bit line and the reference bit line with the sense amplifier.
The dummy cell circuit that generates the reference bit line potential has the circuit arrangement as shown in FIG. 12 .
In a standby mode, the transistors Q 1 , Q 2 of the dummy word lines are turned OFF, and one end N 1 of the paraelectric capacitor C 1 is pre-charged to the source potential of Q 3 , i.e. VDC (>Vss) potential by holding the transistor Q 3 ON. The dummy plate line DPL at the other end of the paraelectric capacitor is held at Vss potential. That is, the voltage VDC is applied to opposite ends of the paraelectric capacitor to have it hold the charge of CD×DVC.
In an active mode, a transistor of a dummy word line connected to the reference bit line, which is the transistor Q 1 in this example, is turned ON to connect BL and N 1 . As a result, the charge stored in the paraelectric capacitor is discharged to the reference bit line. After that, potential of the dummy plate line DPL, which is the other end of C 1 , is raised from Vss to VDC′ potential. Through these operations, a value corresponding to the charge of CD×VDC′ is generated by coupling of the paraelectric capacitor C 1 , and the charge is shared by the reference bit line and the paraelectric capacitor. Through the series of operations, the reference BL potential: Vref′ can be raised from Vss to the intermediate potential between those corresponding to “1” and “0” data. As a result, the reference bit line potential becomes a value obtained by dividing the total charge =(CD×VDC′+CD×VDC) by the load capacitance (CD+CB).
In case of VDC=VDC′, as shown in FIG. 3, it results in Vref′=(2CD×VDC)/(CD+CB)=2Vref=2×(CD×VDC)/(CD+CB), and it is possible to generate a reference bit line potential double that of the conventional dummy cell system, i.e. Vref=(CD×VDC)/(CD+CB), with the same paraelectric capacitor capacitance.
From the opposite viewpoint, while the conventional system required a large CD value because Vref=½VDC when CD=CB, according to the fourth embodiment of the present invention can use a dummy capacitor having an area only ⅓ of that of the conventional system because Vref′=½VDC when CD=⅓CB, and can reduce the chip size significantly. For example, when CB=1000 fF, the conventional system requires the dummy capacitor capacitance of 1000 fF, and a MOS capacitor having an 8 nm thick oxide film needs the capacitor area as large as 225 μm 2 per each dummy cell. In contrast, the first embodiment of the invention can significantly reduce the capacitor area per each dummy cell to 75 μm 2 with the capacitance of 1000 fF/3=333 fF.
Additionally, to generate a potential larger than ½VDC, CB<CD in the conventional system. Therefore, CD itself affects as a load capacitance, and it is possible to generate a potential. According to the fourth embodiment of the present invention, however, the potential as large as Vref′=VDC=Vaa when CD=CB can be generated. This system enables realization of ferroelectric memory without using a ferroelectric capacitor that decreases in operation margin due to fluctuations, deformations, and so on. It can also realize ferroelectric with a small dummy capacitor area without raising and lowering the plate twice. Therefore, high-speed operation is possible.
The fourth embodiment of the present invention is configured to share the paraelectric capacitor by the pair of bit lines using the transistors Q 1 and Q 2 and thereby reduce the dummy cell capacitor area. The paraelectric capacitor may be a gate capacitor of a MOS transistor. A depletion-type transistor is preferable. The dummy word lines DWL 0 , DWL 1 may be changed to LOW prior to sensing operation to disconnect the dummy cell and the reference bit line as shown by (2) in the timing chart shown in FIG. 13 . It is also acceptable to do it after sensing operation (1). After that, DRST is changed to HIGH, and DPL is decreased to LOW after pre-charging the node N 1 to VDC to return to the same status as the standby mode. It is preferable to raise DPL after changing DWL 0 to HIGH and discharging a certain amount of the charge stored to the VDC voltage to the reference bit line. For simplicity of the circuit, VDC=VDC′ is also desirable. Other methods are also usable, such as a method of fixing VDC=Vaa and changing only VDC′ in potential to generate the reference bit line potential, a method of fixing VDC′=Vaa and changing only VDC in potential to generate the reference bit line potential, and so forth. It is also preferable that the amplitude potential of the DRST signal is not lower than VDC+Vt for writing VDC at N 1 , i.e. the raised potential Vpp. Potential of DWL 0 and DWL 1 may be Vpp, or may be the Vaa amplitude if the reference bit line potential +Vt<Vaa.
Needless to say, the driving circuits shown in FIGS. 4 through 6 are also applicable to the system of FIG. 12 .
FIG. 14 is a circuit diagram that shows the fifth embodiment of the invention, and FIG. 15 is a timing chart of its behaviors. This circuit has substantially the same circuit configuration as FIG. 12, but it is different in that while the transistor Q 3 of FIG. 12 for pre-charging the N 1 node to VDC is NMOS, the circuit of FIG. 16 uses PMOS and the opposite-phase signal /DRST.
For pre-charging the N 1 node to VDC, the circuit of FIG. 12 has to raise or boost the DRST signal to above Vaa in case of VDC+Vt>Vaa. The circuit shown here, however, which uses PMOS, can pre-charge it to VDC by adjusting /DRST to Vss if VDC<Vaa, and it is possible to limit the amplitude of /DRST to Vaa and can remove the booster circuit.
FIG. 16 is a circuit diagram that shows the sixth embodiment of the invention, and FIG. 17 is a timing chart of its behaviors.
The circuit shown in FIG. 16 has substantially the same circuit configuration as FIG. 12, but it is different in that the dummy cell circuit is provided for each of the pair of two bit lines. If /BL is the reference bit line, DWL, DRST 1 and DPL 1 may be activated. If BL is the reference bit line, DWL 0 , DRST 0 and DPL 0 may be activated.
As described above, since the invention controls the potential applied to the terminal of the paraelectric capacitor of the dummy cell to an optimum value in either a standby mode or an active mode, it can realize ferroelectric memory not requiring a ferroelectric capacitor subjected to large fluctuations and liable to decrease in operation margin due to deformation, for example, and can realize ferroelectric memory with a small dummy capacitor area without the need of raising and lowering the plate potential in an complicated manner. Therefore, it enables high-speed operation. | A dummy cell circuit, used in semiconductor memory capable of high-speed operation without inviting enlargement of the chip size even when using a paraelectric capacitor, includes at least one paraelectric capacitor and have a specific relation between potentials applied to its terminals. For example, in a standby mode, a first terminal of the paraelectric capacitor is precharged to a first potential higher than ground potential whereas a second terminal of the paraelectric capacitor is pre-charged to ground potential. In an active mode, the first terminal is connected to one of paired bit lines, which is a reference bit line to which data is not read-out from memory cell, and the second terminal is raised from ground potential to a second potential higher than ground potential. | 6 |
This application claims the benefit of U.S. Ser. No. 60/409,694, filed Sep. 10, 2002, the contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to diazabicyclic compounds useful in treating central nervous system (CNS) diseases, disorders and conditions, such as, but not limited to, nicotine addiction, schizophrenia, depression, Alzheimer's disease, Parkinson's disease and ADHD. The present invention further comprises pharmaceutical compositions containing such compounds and methods of treatment comprising the use of such compounds. The compounds of the invention bind to neuronal nicotinic acetylcholine specific receptor sites and are useful in modulating cholinergic function.
By the use of a CNS-penetrant nicotinic receptor modulating compounds of the present invention, it is possible to treat a number of central nervous system diseases, disorders and conditions, including addictions, in patients for whom conventional therapy is not wholly successful or where dependence upon the therapeutic drug is prevalent.
Copending applications U.S. Ser. No. 10/068,692 and U.S. Ser. No. 10/047,850 are drawn to 1,4-diazabicyclo[3.2.2]nonane-4-carboxyl or 4-thiocarboxyl compounds; and benzoxazole- and azabenzoxazole-diazabicyclic derivative compounds; respectively, and both are useful in the treatment of CNS disorders.
Other published references recite diazabicycloalkane compounds as having activity towards nicotinic receptors. Such compounds recited in the field are 1,4-diazabicyclo[3.2.2]nonane derivatives (WO 00/34279); 2,5-diazabicyclo[2.2.1]heptane derivatives (WO 00/34284); 1,4-diaza-bicyclo[3.2.2]nonane-4-carboxylate and carboxamide derivatives (WO 00/58311); 1,4-diazabicyclo[3.2.2]nonane-phenylisoxazoles (WO 01/92259);4-(2-phenylthiazol-5-yl)-1,4-diazabicyclo[3.2.2]nonanes (WO 01/92260); 1,4-diazabicyclo[3.2.2]nonabenzoxazole, -benzthiazole and benzimidazole derivatives (WO 01/92261); and 4-heteroaryl-1,4-diazabicyclo[3.2.2]nonane compounds (WO 01/55150). In addition, another reference, WO 00/45846, recites compositions containing nicotine or a nicotinic receptor ligand and an inhibitor of a monoamine oxidase for use in smoking cessation treatment.
SUMMARY OF THE INVENTION
The present invention relates to compounds of the formula I
wherein:
A=CR 1 or N,
B=CR 2 or N,
D=CR 3 or N,
E=CR 4 or N and
F=CR 5 or N;
and the maximum number of nitrogen atoms amongst A, B, D, E, and F is two;
where m=1-3 and n=1-3
and excluding all compounds where m=n=2;
where each R 1 , R 2 , R 3 , R 4 and R 5 is independently selected from F, Cl, Br, I, nitro, cyano, CF 3 , —NR 6 R 7 , —NR 6 C(═O)R 7 , —NR 6 C(═O)NR 7 R 8 , —NR 6 C(═O)OR 7 , —NR 6 S(═O) 2 R 7 , —NR 6 S(═O) 2 NR 7 R 8 , —OR 6 , —OC(═O)R 6 , —OC(═O)OR 6 , —OC(═O)NR 6 R 7 , —OC(═O)SR 6 , —C(═O)OR 6 , —C(═O)R 6 , —C(═O)NR 6 R 7 , —SR 6 , —S(═O)R 6 , —S(═O) 2 R 6 , —S(═O) 2 NR 6 R 7 , and a substituent from the definition of R 6 ;
each R 6 , R 7 , and R 8 is independently selected from H, straight chain or branched (C 1 -C 8 )alkyl, straight chain or branched (C 2 -C 8 )alkenyl, straight chain or branched (C 2 -C 8 )alkynyl, (C 3 -C 8 )cycloalkyl, (C 4 -C 8 )cycloalkenyl, 3-8 membered heterocycloalkyl, (C 5 -C 11 )bicycloalkyl, (C 7 -C 11 )bicycloalkenyl, 5-11 membered heterobicycloalkyl, 5-11 membered heterobicycloalkenyl, (C 6 -C 11 )aryl, and 5-12 membered heteroaryl; wherein each R 6 , R 7 , and R 8 is optionally substituted with from one to six substituents, independently selected from F, Cl, Br, I, nitro, cyano, CF 3 , —NR 9 R 10 , —NR 9 C(═O)R 10 , —NR 9 C(═O)NR 10 OR 11 , —NR 9 C(═O)OR 10 , —NR 9 S(═O) 2 R 10 , —NR 9 S(═O) 2 NR 10 R 11 , —OR 9 , —OC(═O)R 9 , —OC(═O)OR 9 , —OC(═O)NR 9 R 10 , —OC(═O)SR 9 , —C(═O)OR 9 , —C(═O)R 9 , —C(═O)NR 9 R 10 , —SR 9 , —S(═O)R 9 , —S(═O) 2 R 9 , —S(═O) 2 NR 9 R 10 and R 9 ;
or R 1 and R 2 , or R 2 and R 3 , or R 3 and R 4 , or R 4 and R 5 , may form another 6-membered aromatic or heteroaromatic ring sharing A and B, or B and D, or D and E, or E and F, respectively, and may be optionally substituted with from one to four substituents independently selected from the group of radicals set forth in the definition of R 6 , R 7 and R 8 above;
each R 9 , R 10 and R 11 is independently selected from H, straight chain or branched (C 1 -C 8 )alkyl, straight chain or branched (C 2 -C 8 )alkenyl, straight chain or branched (C 2 -C 8 )alkynyl, (C 3 -C 8 )cycloalkyl, (C 4 -C 8 )cycloalkenyl, 3-8 membered heterocycloalkyl, (C 5 -C 11 )bicycloalkyl, (C 7 -C 11 )bicycloalkenyl, 5-11 membered heterobicycloalkyl, (5-11 membered) heterobicycloalkenyl, (C 6 -C 11 )aryl or 5-12 membered heteroaryl; wherein each R 9 , R 10 and R 11 is optionally substituted with from one to six substituents independently selected from F, Cl, Br, I, nitro, cyano, CF 3 , —NR 12 R 13 , —NR 12 C(═O)R 13 , —NR 12 C(═O)NR 13 R 14 , —NR 12 C(═O)OR 13 , —NR 12 S(═O) 2 R 13 , —NR 12 S(═O) 2 NR 13 R 14 , —OR 12 , —OC(═O)R 12 , —OC(═O)OR 12 , —OC(═O)NR 12 R 13 , —OC(═O)SR 12 , —C(═O)OR 12 , —C(═O)R 12 , —C(═O)NR 12 R 13 , —SR 12 , —S(═O)R 12 , —S(═O) 2 R 12 , —S(═O) 2 NR 12 R 13 and R 12 ;
each R 12 , R 13 , and R 14 is independently selected from H, straight chain or branched (C 1 -C 8 )alkyl, straight chain or branched (C 2 -C 8 )alkenyl, straight chain or branched (C 2 -C 8 )alkynyl, (C 3 -C 8 )cycloalkyl, (C 4 -C 8 )cycloalkenyl, 3-8 membered heterocycloalkyl, (C 5 -C 11 )bicycloalkyl, (C 7 -C 11 )bicycloalkenyl, 5-11 membered heterobicycloalkyl, 5-11 membered heterobicycloalkenyl, (C 6 -C 11 )aryl and (5-12 membered) heteroaryl;
and all enantiomeric, diastereomeric, and tautomeric isomers and pharmaceutically acceptable salts thereof.
Preferred compounds of the invention are those compounds of formula I wherein one or two of A, B, D or E is N.
Further, preferred compounds of the invention are those compounds of formula I wherein A and B are both N.
Further, preferred compounds of the invention are those compounds of formula I wherein A and E are both N.
Further, preferred compounds of the invention are those compounds of formula I wherein B and E are both N.
Further, preferred compounds of the invention are those compounds of formula I wherein one of A, B or E is N.
Further, preferred compounds of the invention are those compounds of formula I wherein one of A or B is N.
Preferred compounds of the invention are those compounds of formula I wherein each R 1 , R 2 , R 3 , R 4 and R 5 is independently selected from H, halo, (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, (C 1 -C 6 )fluoroalkyl, cyano, (C 1 -C 6 )alkoxycarbonyl; phenyl substituted or unsubstituted with halo, (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, (C 1 -C 6 )fluoroalkyl; and heteroaryl. Further preferred is where any one of the R 1 and R 2 , or R 2 and R 3 , or R 3 and R 4 , or R 4 and R 5 pairs located on adjacent carbon atoms join to form an unsaturated (C 4 )alkylene bridge.
Preferred compounds of the invention are those compounds of formula I wherein m=1 and n=1.
Preferred compounds of the invention are those compounds of formula I wherein m=1 and n=2.
Preferred compounds of the invention are those compounds of formula I wherein m=1 and n=3.
Preferred compounds of the invention are those compounds of formula I wherein m=2 and n=3.
Preferred compounds of the invention are those compounds of formula I wherein m=3 and n=3.
Examples of specific compounds of this invention are the following compounds of the formula I and their pharmaceutically acceptable salts, hydrates, solvates and optical and other stereoisomers. Particular preferred compounds of the invention are those where n=2 and m=1 and are selected from the group consisting of:
4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-Pyridin-2-yl-1,4-diaza-bicyclo[3.2.1]octane; 4-Pyridin-3-yl-1,4-diaza-bicyclo[3.2.1]octane: 4-Pyridin-4-yl-1,4-diaza-bicyclo[3.2.1]octane: 4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.2.1]octane; 4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.2.1]octane; 4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.2.1]octane; 5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-nicotinonitrile; 4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 3-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-quinoline; 4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-nicotinic acid ethyl ester; 4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; 4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; 5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-[3,4′]bipyridinyl; and 4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane.
Further preferred compounds of the invention are:
(+)-4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-Pyridin-2-yl-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-Pyridin-3-yl-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-Pyridin-4-yl-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-nicotinonitrile; (+)-4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-3-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-quinoline; (+)-4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(3-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-nicotinic acid ethyl ester; (+)-4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (+)-4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (+)-5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-[3,4′]bipyridinyl; and (+)-4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane.
Further preferred compounds of the invention are:
(−)-4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-Pyridin-2-yl-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-Pyridin-3-yl-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-Pyridin-4-yl-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-nicotinonitrile; (−)-4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-3-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-quinoline; (−)-4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-nicotinic acid ethyl ester; (−)-4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane; (−)-4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane; (−)-5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-[3,4′]bipyridinyl; and (−)-4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane.
Further preferred compounds of the invention are those where n=1 and m=1 and are selected from the group consisting of:
4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-Pyridin-2-yl-1,4-diaza-bicyclo[3.1.1]heptane; 4-Pyridin-3-yl-1,4-diaza-bicyclo[3.1.1]heptane; 4-Pyridin-4-yl-1,4-diaza-bicyclo[3.1.1]heptane; 4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.1.1]heptane; 4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.1.1]heptane; 4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.1.1]heptane; 5-(1,4-Diaza-bicyclo[3.1.1]hept-4-yl)-nicotinonitrile; 4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3. 1.1]heptane; 4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 3-(1,4-Diaza-bicyclo[3.1.1]hept-4-yl)-quinoline; 4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 5-(1,4-Diaza-bicyclo[3.1.1]hept-4-yl)-nicotinic acid ethyl ester; 4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.1.1]heptane; 4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane; 5-(1,4-Diaza-bicyclo[3.1.1]hept-4-yl)-[3,4′]bipyridinyl; and 4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.1.1]heptane.
Further preferred compounds of the invention are those where n=3 and m=selected from the group consisting of:
4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-Pyridin-2-yl-1,4-diaza-bicyclo[3.3.1]nonane; 4-Pyridin-3-yl-1,4-diaza-bicyclo[3.3.1]nonane; 4-Pyridin-4-yl-1,4-diaza-bicyclo[3.3.1]nonane; 4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.3.1]nonane; 4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.3.1]nonane; 4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.3.1]nonane; 5-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-nicotinonitrile; 4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 3-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-quinoline; 4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 5-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-nicotinic acid ethyl ester; 4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; 4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; 5-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-[3,4′]bipyridinyl; and 4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane.
Further preferred compounds of the invention are selected from:
(+)-4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-Pyridin-2-yl-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-Pyridin-3-yl-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-Pyridin-4-yl-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-5-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-nicotinonitrile; (+)-4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-3-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-quinoline; (+)-4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-5-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-nicotinic acid ethyl ester; (+)-4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (+)-4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (+)-5-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-[3,4′]bipyridinyl; and (+)-4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane.
Further preferred compounds of the invention are selected from the group consisting of:
(−)-4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-Pyridin-2-yl-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-Pyridin-3-yl-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-Pyridin-4-yl-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-5-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-nicotinonitrile; (−)-4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-3-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-quinoline; (−)-4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-5-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-nicotinic acid ethyl ester; (−)-4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[(5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.1]nonane; (−)-4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane; (−)-5-(1,4-Diaza-bicyclo[3.3.1]non-4-yl)-[3,4′]bipyridinyl; and (−)-4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.1]nonane.
Further preferred compounds of the invention are those where n=3 and m=2 selected from the group consisting of:
4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-Pyridin-2-yl-1,4-diaza-bicyclo[3.3.2]decane; 4-Pyridin-3-yl-1,4-diaza-bicyclo[3.3.2]decane; 4-Pyridin-4-yl-1,4-diaza-bicyclo[3.3.2]decane; 4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.3.2]decane; 4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.3.2]decane; 4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.3.2]decane; 5-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-nicotinonitrile; 4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 3-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-quinoline; 4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 5-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-nicotinic acid ethyl ester; 4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; 4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; 5-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-[3,4′]bipyridinyl; and 4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane.
Further preferred compounds of the invention are selected from the group consisting of:
(+)-4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-Pyridin-2-yl-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-Pyridin-3-yl-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-Pyridin-4-yl-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-5-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-nicotinonitrile; (+)-4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-3-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-quinoline; (+)-4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-5-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-nicotinic acid ethyl ester; (+)-4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (+)-4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (+)-5-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-[3,4′]bipyridinyl; and (+)-4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane.
Further preferred compounds of the invention are selected from the group consisting of:
(−)-4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-Pyridin-2-yl-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-Pyridin-3-yl-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-Pyridin-4-yl-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-5-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-nicotinonitrile; (−)-4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-3-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-quinoline; (−)-4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-5-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-nicotinic acid ethyl ester; (−)-4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.2]decane; (−)-4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane; (−)-5-(1,4-Diaza-bicyclo[3.3.2]dec-4-yl)-[3,4′]bipyridinyl; and (−)-4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.2]decane.
Further preferred compounds of the invention are those where n=3 and m=3 selected from the group consisting of:
4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-Pyridin-2-yl-1,4-diaza-bicyclo[3.3.3]undecane; 4-Pyridin-3-yl-1,4-diaza-bicyclo[3.3.3]undecane; 4-Pyridin-4-yl-1,4-diaza-bicyclo[3.3.3]undecane; 4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.3.3]undecane; 4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.3.3]undecane; 4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.3.3]undecane; 5-(1,4-Diaza-bicyclo[3.3.3]undec-4-yl)-nicotinonitrile; 4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 3-(1,4-Diaza-bicyclo[3.3.3]undec-4-yl)-quinoline; 4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 5-(1,4-Diaza-bicyclo[3.3.3]undec-4-yl)-nicotinic acid ethyl ester; 4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(2,4-Dichloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-(5-p-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.3.3]undecane; 4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane; 5-(1,4-Diaza-bicyclo[3.3.3]undec-4-yl)-[3,4′]bipyridinyl; and 4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.3.3]undecane.
The term “alkyl”, as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight or branched moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, and t-butyl.
The term “alkenyl”, as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon-carbon double bond wherein alkyl is as defined above. Examples of alkenyl include, but are not limited to, ethenyl and propenyl.
The term “alkynyl”, as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon-carbon triple bond wherein alkyl is as defined above. Examples of alkynyl groups include, but are not limited to, ethynyl and 2-propynyl.
The term “cycloalkyl”, as used herein, unless otherwise indicated, includes non-aromatic saturated cyclic alkyl moieties wherein alkyl is as defined above. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. “Bicycloalkyl” groups are non-aromatic saturated carbocyclic groups consisting of two rings. Examples of bicycloalkyl groups include, but are not limited to, bicyclo-[2.2.2]-octyl and norbornyl. The term “cycloalkenyl” and “bicycloalkenyl” refer to non-aromatic carbocyclic cycloalkyl and bicycloalkyl moieties as defined above, except comprising of one or more carbon-carbon double bonds connecting carbon ring members (an “endocyclic” double bond) and/or one or more carbon-carbon double bonds connecting a carbon ring member and an adjacent non-ring carbon (an “exocyclic” double bond). Examples of cycloalkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl. A non-limiting example of a bicycloalkenyl group is norborenyl. Cycloalkyl, cycloalkenyl, bicycloalkyl, and bicycloalkenyl groups also include groups similar to those described above for each of these respective categories, but which are substituted with one or more oxo moieties. Examples of such groups with oxo moieties include, but are not limited to oxocyclopentyl, oxocyclobutyl, oxocyclopentenyl, and norcamphoryl.
The term “aryl”, as used herein, unless otherwise indicated, includes an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen atom. Examples of aryl groups include, but are not limited to phenyl and naphthyl.
The terms “heterocyclic” and “heterocycloalkyl”, as used herein, refer to non-aromatic cyclic groups containing one or more heteroatoms, preferably from one to four heteroatoms, each selected from O, S and N. “Heterobicycloalkyl” groups are non-aromatic two-ringed cyclic groups, wherein at least one of the rings contains a heteroatom (O, S, or N). The heterocyclic groups of this invention can also include ring systems substituted with one or more oxo moieties. Examples of non-aromatic heterocyclic groups include, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepinyl, piperazinyl, 1,2,3,6-tetrahydropyridinyl, oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidino, morpholino, thiomorpholino, thioxanyl, pyrrolinyl, indolinyl, 2H-pyranyl, 4H-pyranyl, dioxanyl, 1,3-dioxolanyl, pyrazolinyl, dihydropyranyl, dihydrothienyl, dihydrofuranyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, 3-azabicyclo[3.1.0]hexanyl, 3-azabicyclo[4.1.0]heptanyl, 3H-indolyl, quinuclidinyl and quinolizinyl.
The term “heteroaryl”, as used herein, refers to aromatic groups containing one or more heteroatoms (O, S, or N). A multicyclic group containing one or more heteroatoms wherein at least one ring of the group is aromatic is a “heteroaryl” group. The heteroaryl groups of this invention can also include ring systems substituted with one or more oxo moieties. Examples of heteroaryl groups include, but are not limited to, pyridinyl, pyridazinyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, quinolyl, isoquinolyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxazolyl, isothiazolyl, pyrrolyl, quinolinyl, isoquinolinyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, indolizinyl, phthalazinyl, pyridazinyl, triazinyl, isoindolyl, purinyl, oxadiazolyl, thiazolyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, dihydroquinolyl, tetrahydroquinolyl, dihydroisoquinolyl, tetrahydroisoquinolyl, benzofuryl, furopyridinyl, pyrolopyrimidinyl, and azaindolyl.
The foregoing heteroaryl, heterocyclic and heterocycloalkyl groups may be C-attached or N-attached (where such is possible). For instance, a group derived from pyrrole may be pyrrol-1-yl (N-attached) or pyrrol-3-yl (C-attached).
Unless otherwise indicated, the term “one or more substituents”, as used herein, refers to from one to the maximum number of substituents possible based on the number of available bonding sites.
The term “treatment”, as used herein, refers to reversing, alleviating, inhibiting the progress of, or preventing the disorder or condition to which such term applies, or one or more symptoms of such condition or disorder. The term “treatment”, as used herein, refers to the act of treating, as “treating” is defined immediately above.
Compounds of formula I may contain chiral centers and therefore may exist in different enantiomeric and diastereomeric forms. Individual isomers can be obtained by known methods, such as optical resolution, optically selective reaction, or chromatographic separation in the preparation of the final product or its intermediate. This invention relates to all optical isomers and all stereoisomers of compounds of the formula I, both as racemic mixtures and as individual enantiomers and diastereomers of such compounds, and mixtures thereof, and to all pharmaceutical compositions and methods of treatment defined above that contain or employ them, respectively.
In so far as the compounds of formula I of this invention are basic compounds, they are all capable of forming a wide variety of different salts with various inorganic and organic acids. Although such salts must be pharmaceutically acceptable for administration to animals, it is often desirable in practice to initially isolate the base compound from the reaction mixture as a pharmaceutically unacceptable salt and then simply convert to the free base compound by treatment with an alkaline reagent and thereafter convert the free base to a pharmaceutically acceptable acid addition salt. The acid addition salts of the base compounds of this invention are readily prepared by treating the base compound with a substantially equivalent amount of the chosen mineral or organic acid in an aqueous solvent or in a suitable organic solvent, such as methanol or ethanol. Upon careful evaporation of the solvent, the desired solid salt is readily obtained. The acids which are used to prepare the pharmaceutically acceptable acid addition salts of the aforementioned base compounds of this invention are those which form non-toxic acid addition salts, i.e., salts containing pharmaceutically acceptable anions, such as the hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate or bisulfate, phosphate or acid phosphate, acetate, lactate, citrate or acid citrate, tartrate or bi-tartrate, succinate, maleate, fumarate, gluconate, saccharate, benzoate, methanesulfonate, ethanesulfonate, benzenesulfonate, p-toluenesulfonate and pamoate (i.e., 1,1′-methylene-bis-(2-hydroxy-3-naphthoate))salts.
The present invention also includes isotopically labeled compounds, which are identical to those recited in formula I, but for the fact that one or more atoms are replaced by an atom having an atomic mass or mass number different from the atomic mass or mass number usually found in nature. Examples of isotopes that can be incorporated into compounds of the present invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorous, sulfur, fluorine and chlorine, such as 2 H, 3 H, 13 C, 11 C, 14 C, 15 N, 18 O, 17 O, 31 P, 32 P, 35 S, 18 F, and 36 Cl, respectively. Compounds of the present invention, prodrugs thereof, and pharmaceutically acceptable salts of said compounds or of said prodrugs which contain the aforementioned isotopes and/or other isotopes of other atoms are within the scope of this invention. Certain isotopically labeled compounds of the present invention, for example those into which radioactive isotopes such as 3 H and 14 C are incorporated, are useful in drug and/or substrate tissue distribution assays. Tritiated, i.e., 3 H, and carbon-14, i.e., 14 C, isotopes are particularly preferred for their ease of preparation and detectability. Further, substitution with heavier isotopes such as deuterium, i.e., 2 H, can afford certain therapeutic advantages resulting from greater metabolic stability, for example increased in vivo half-life or reduced dosage requirements and, hence, may be preferred in some circumstances. Isotopically labeled compounds of formula I of this invention and prodrugs thereof can generally be prepared by carrying out the procedures disclosed in the Schemes and/or in the Examples below, by substituting a readily available isotopically labeled reagent for a non-isotopically labeled reagent.
The present invention also relates to a pharmaceutical composition for treating a disorder or condition selected from inflammatory bowel disease (including but not limited to ulcerative colitis, pyoderma gangrenosum and Crohn's disease), irritable bowel syndrome, spastic dystonia, chronic pain, acute pain, celiac sprue, pouchitis, vasoconstriction, anxiety, panic disorder, depression, bipolar disorder, autism, sleep disorders, jet lag, amyotrophic lateral sclerosis (ALS), cognitive dysfunction, drug/toxin-induced cognitive impairment (e.g., from alcohol, barbiturates, vitamin deficiencies, recreational drugs, lead, arsenic, mercury), disease-induced cognitive impairment (e.g., arising from Alzheimer's disease (senile dementia), vascular dementia, Parkinson's disease, multiple sclerosis, AIDS, encephalitis, trauma, renal and hepatic encephalopathy, hypothyroidism, Pick's disease, Korsakoff's syndrome and frontal and subcortical dementia), hypertension, bulimia, anorexia, obesity, cardiac arrhythmias, gastric acid hypersecretion, ulcers, pheochromocytoma, progressive supramuscular palsy, chemical dependencies and addictions (e.g., dependencies on, or addictions to nicotine (and/or tobacco products), alcohol, benzodiazepines, barbiturates, opioids or cocaine), headache, migraine, stroke, traumatic brain injury (TBI), obsessive-compulsive disorder (OCD), psychosis, Huntington's chorea, tardive dyskinesia, hyperkinesia, dyslexia, schizophrenia, multi-infarct dementia, age-related cognitive decline, epilepsy, including petit mal absence epilepsy, attention deficit hyperactivity disorder (ADHD), Tourette's Syndrome, particularly, nicotine dependency, addiction and withdrawal; including use in smoking cessation therapy in a mammal, comprising an amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof, that is effective in treating such disorder or condition and a pharmaceutically acceptable carrier.
The present invention also relates to a method of treating a disorder or condition selected from inflammatory bowel disease (including but not limited to ulcerative colitis, pyoderma gangrenosum and Crohn's disease), irritable bowel syndrome, spastic dystonia, chronic pain, acute pain, celiac sprue, pouchitis, vasoconstriction, anxiety, panic disorder, depression, bipolar disorder, autism, sleep disorders, jet lag, amyotrophic lateral sclerosis (ALS), cognitive dysfunction, drug/toxin-induced cognitive impairment (e.g., from alcohol, barbiturates, vitamin deficiencies, recreational drugs, lead, arsenic, mercury), disease-induced cognitive impairment (e.g., arising from Alzheimer's disease (senile dementia), vascular dementia, Parkinson's disease, multiple sclerosis, AIDS, encephalitis, trauma, renal and hepatic encephalopathy, hypothyroidism, Pick's disease, Korsakoff's syndrome and frontal and subcortical dementia), hypertension, bulimia, anorexia, obesity, cardiac arrhythmias, gastric acid hypersecretion, ulcers, pheochromocytoma, progressive supramuscular palsy, chemical dependencies and addictions (e.g., dependencies on, or addictions to nicotine (and/or tobacco products), alcohol, benzodiazepines, barbiturates, opioids or cocaine), headache, migraine, stroke, traumatic brain injury (TBI), obsessive-compulsive disorder (OCD), psychosis, Huntington's chorea, tardive dyskinesia, hyperkinesia, dyslexia, schizophrenia, multi-infarct dementia, age-related cognitive decline, epilepsy, including petit mal absence epilepsy, attention deficit hyperactivity disorder (ADHD), Tourette's Syndrome, particularly, nicotine dependency, addiction and withdrawal; including use in smoking cessation therapy in a mammal, comprising administering to a mammal in need of such treatment an amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof, that is effective in treating such disorder or condition.
The present invention also relates to a pharmaceutical composition for treating a disorder or condition selected from inflammatory bowel disease (including but not limited to ulcerative colitis, pyoderma gangrenosum and Crohn's disease), irritable bowel syndrome, spastic dystonia, chronic pain, acute pain, celiac sprue, pouchitis, vasoconstriction, anxiety, panic disorder, depression, bipolar disorder, autism, sleep disorders, jet lag, amyotrophic lateral sclerosis (ALS), cognitive dysfunction, drug/toxin-induced cognitive impairment (e.g., from alcohol, barbiturates, vitamin deficiencies, recreational drugs, lead, arsenic, mercury), disease-induced cognitive impairment (e.g., arising from Alzheimer's disease (senile dementia), vascular dementia, Parkinson's disease, multiple sclerosis, AIDS, encephalitis, trauma, renal and hepatic encephalopathy, hypothyroidism, Pick's disease, Korsakoff's syndrome and frontal and subcortical dementia), hypertension, bulimia, anorexia, obesity, cardiac arrhythmias, gastric acid hypersecretion, ulcers, pheochromocytoma, progressive supramuscular palsy, chemical dependencies and addictions (e.g., dependencies on, or addictions to nicotine (and/or tobacco products), alcohol, benzodiazepines, barbiturates, opioids or cocaine), headache, migraine, stroke, traumatic brain injury (TBI), obsessive-compulsive disorder (OCD), psychosis, Huntington's chorea, tardive dyskinesia, hyperkinesia, dyslexia, schizophrenia, multi-infarct dementia, age-related cognitive decline, epilepsy, including petit mal absence epilepsy, attention deficit hyperactivity disorder (ADHD), Tourette's Syndrome, particularly, nicotine dependency, addiction and withdrawal; including use in smoking cessation therapy in a mammal, comprising an nicotinic receptor modulating amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier.
The present invention also relates to a method of treating a disorder or condition selected from inflammatory bowel disease (including but not limited to ulcerative colitis, pyoderma gangrenosum and Crohn's disease), irritable bowel syndrome, spastic dystonia, chronic pain, acute pain, celiac sprue, pouchitis, vasoconstriction, anxiety, panic disorder, depression, bipolar disorder, autism, sleep disorders, jet lag, amyotrophic lateral sclerosis (ALS), cognitive dysfunction, drug/toxin-induced cognitive impairment (e.g., from alcohol, barbiturates, vitamin deficiencies, recreational drugs, lead, arsenic, mercury), disease-induced cognitive impairment (e.g., arising from Alzheimer's disease (senile dementia), vascular dementia, Parkinson's disease, multiple sclerosis, AIDS, encephalitis, trauma, renal and hepatic encephalopathy, hypothyroidism, Pick's disease, Korsakoff's syndrome and frontal and subcortical dementia), hypertension, bulimia, anorexia, obesity, cardiac arrhythmias, gastric acid hypersecretion, ulcers, pheochromocytoma, progressive supramuscular palsy, chemical dependencies and addictions (e.g., dependencies on, or addictions to nicotine (and/or tobacco products), alcohol, benzodiazepines, barbiturates, opioids or cocaine), headache, migraine, stroke, traumatic brain injury (TBI), obsessive-compulsive disorder (OCD), psychosis, Huntington's chorea, tardive dyskinesia, hyperkinesia, dyslexia, schizophrenia, multi-infarct dementia, age-related cognitive decline, epilepsy, including petit mal absence epilepsy, attention deficit hyperactivity disorder (ADHD), Tourette's Syndrome, particularly, nicotine dependency, addiction and withdrawal; including use in smoking cessation therapy in a mammal, comprising administering to a mammal in need of such treatment a nicotinic receptor modulating amount of a compound of the formula I, or a pharmaceutically acceptable salt thereof.
DETAILED DESCRIPTION OF THE INVENTION
Compounds of the formula I can be readily prepared according to the methods described below. In the reaction schemes and discussion that follow, A, B, D, E, and F, unless otherwise indicated, are defined as they are above in the definition of compounds of the formula I.
As used herein, the expression “inert reaction solvent” refers to a solvent system in which the components do not interact with starting materials, reagents, or intermediates or products in a manner which adversely affects the yield of the desired product.
During any of the following synthetic sequences it may be necessary and/or desirable to protect sensitive or reactive groups on any of the molecules concerned. This may be achieved by means of conventional protecting groups, such as those described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999.
Referring to Scheme I, a compound of formula I can be prepared by the coupling of a compound of formula II to a compound of formula II, wherein X is a leaving group or a group that has the ability to undergo oxidative addition (e.g., fluoride, chloride, bromide, iodide, triflate, methyl sulfide, alkyl sulfide, aryl sulfide, alkyl sulfoxide, or aryl sulfoxide) in the presence or absence of base. This coupling can be facilitated by the use of an organometallic reagent such as palladium, nickel or copper and the preferred method is that of Buchwald as described in: Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 2000, 65, 1144-1157; Wolfe et al J. Org. Chem. 2000, 65, 1158-1174; Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 1997, 62, 6066-6068.
In this coupling process, the palladium catalyst may be formed from the combination of a palladium compound selected from, but not limited to, the group consisting of palladium(II) acetate, palladium(II) chloride, bis-acetonitrile palladium(II) chloride, bis-benzonitrile palladium(II) chloride, palladium(II) bromide, tris(dibenzylideneacetone)dipalladium(0), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct, palladium (0) tetrakis(triphenylphosphine), allyl palladium chloride dimer, dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct; more preferably tris(dibenzylideneacetone)dipalladium(0); and a phosphine ligand selected from, but not limited to, 1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, dicyclohexylphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, tri-isopropylphosphine, tri-n-propylphosphine, tri-isobutylphosphine, tri-n-butylphosphine, tri-o-tolylphosphine, triphenylphosphine, 2-(dicyclohexylphosphino)-biphenyl, 2-(di-tert-butylphosphino)-biphenyl, 2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl, or 2-di-tert-butylphosphino-2′-(N,N-dimethylamino)biphenyl; more preferably 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl.
This step is conducted in the presence or absence of a base selected from, but not limited to, triethylamine, diisopropylamine, pyridine, 2,6-lutidine, sodium or potassium hydroxide, lithium or sodium or potassium or cesium carbonate, cesium fluoride, sodium or potassium tert-butoxide, sodium or potassium or cesium acetate, diisopropylethylamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene; more preferably sodium tert-butoxide.
The reaction may be carried out in the presence or absence of an inert reaction solvent such as water, methanol, ethanol, isopropanol, acetonitrile, methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, diethylether, dioxane, 1,2-dimethoxyethane, benzene, toluene, dimethylformamide, or dimethylsulfoxide, more preferably toluene. The aforesaid process of Scheme I can normally be carried out at a temperature between from about −10° C. to about 150° C., preferably near 110° C.
A compound of formula II can be prepared by methods known in the literature or through other means by those skilled in the art. In the compound of formula III, X is defined as a functional group that has leaving group ability and/or the ability to undergo oxidative addition such as, but not limited to, F, Cl, Br, I, triflate, methyl sulfide, alkyl sulfide, aryl sulfide, alkyl sulfoxide, or aryl sulfoxide.
A compound of formula II where m=1 and n=1 can be prepare by two different procedures which are shown in Scheme II and III. Referring to Scheme II, (4-benzyl-piperazin-2-yl)-methanol, IV, was made by the procedure of Naylor, et al. J. Med. Chem. 1993, 36, 2075, and the secondary amine functional group was protected as the trifluoroacetamide giving a compound of formula V according to the procedures described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999. The procedure using trifluoroacetic anhydride and pyridine with dichloromethane as a solvent from 0° C. to ambient temperature is preferred. The benzyl group in V is removed according to the procedures described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999, to provide a compound of formula VI. The procedure using hydrogen gas at 50 psi and 10% palladium on carbon as a catalyst and ethanol/concentrated HCl as the solvent at ambient temperature is preferred. Treatment of a compound of formula VI with diethyl azodicarboxylate or diisopropyl azodicarboxylate, where diethyl azodicarboxylate is preferred and a phosphine reagent such as, but not limited to, dicyclohexylphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, tri-isopropylphosphine, tri-n-propylphosphine, tri-isobutylphosphine, tri-n-butylphosphine, tri-o-tolylphosphine, triphenylphosphine, 2-(dicyclohexylphosphino)-biphenyl, 2-(di-tert-butylphosphino)-biphenyl, 2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl, 2-di-tert-butylphosphino-2′-(N,N-dimethylamino)biphenyl or polymer supported triphenylphosphine; more preferably triphenylphosphine in an inert reaction solvent such as water, methanol, ethanol, isopropanol, acetonitrile, methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, diethylether, 1,4-dioxane, 1,2-dimethoxyethane, benzene, toluene, dimethylformamide, or dimethylsulfoxide, more preferably tetrahydrofuran at 0° C. to 100° C., where 20° C. is preferred results in a diazabicycle compound of formula VII. Alternative methods for this conversion would include converting the primary alcohol functional group of VI in to a good leaving group such as, but not limited to, Cl, Br, I, tosylate, mesylate followed by cyclization to the desired bicycle VII under thermal conditions with or without the addition of a base. The trifluoroacetamide group in VII is removed according to the procedures described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999, where the procedure using sodium carbonate in a methanol/water reaction solvent at 60° C. is preferred to form a compound of formula II, where m=1 and n=1.
The second method for preparing a compound of formula II where m=1 and n=1 is described in Scheme III. Referring to Scheme III, commercially available N-benzhydrylazetidine-3-ol was converted to a compound of formula VIII using the procedure of Sum, F. W. and Hu, B. in WO 02/06221. The amine of compound VIII is acylated with bromoacetyl bromide or bromoacetyl chloride in a suitable inert solvent or mixture of solvents such as, but not limited to, toluene, benzene, methylene chloride, 1,2-dichloroethane, 1,4-dioxane or water in the presence of a suitable base such as, but not limited to, triethylamine, diisopropyethylamine, pyridine, 2,6-lutidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, sodium or potassium carbonate, sodium or potassium bicarbonate, sodium or potassium hydroxide. The most preferred conditions use bromoacetyl bromide in a mixture of toluene and saturated aqueous sodium bicarbonate solution to give a compound of formula IX. The compound of formula IX is heated under reflux in an inert solvent such as, but not limited to toluene, tetrahydrofuran, methylene chloride, 1,2-dichloroethane, dimethylformamide, dimethylsulfoxide, 1,2-dimethoxyethane or 1,4-dioxane, with the more preferred solvent being toluene, to form a compound of formula X. The benzhydryl protecting group of compound X is removed according to the procedures described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999, to provide a compound of formula XI. The procedure using hydrogen gas at 50 psi and 10% palladium on carbon as a catalyst and ethanol is preferred. Lactam XI is reduced with a suitable reducing agent such as, but not limited to, lithium aluminum hydride, borane, alane, or di-isobutyl aluminum hydride, where lithium aluminum hydride is preferred in an inert solvent such as ether, THF, 1,2-dimethoxyethane, or 1,4-dioxane, where THF is preferred at 0° C. to 150° C., where 50° C. is preferred to form the compound of formula XII. The benzyl group in XII is removed according to the procedures described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999. The procedure using hydrogen gas at 50 psi and 10% palladium on carbon as a catalyst and ethanol/concentrated HCl as the solvent at ambient temperature is preferred providing a compound of formula II where m=1 and n=1.
A compound of formula II where m=1 and n=2 can be prepared by three different procedures. The first method is according to the procedures described by Strum; et al. J. Med. Chem., 1977, 20, 1333-7. The second and third methods are shown in the following Schemes IV and V. Referring to Scheme IV, azabicyclo[2.2.1]alkan-3-one of formula XIII was prepared according to the procedures described by Saunders; et al., J. Chem. Soc., Chem. Commun., 1988, 1618-9. The compound of formula XIII is converted to the corresponding oxime compound of formula XIV upon treatment with hydroxylamine hydrochloride in the presence of a base such as, but not limited to, lithium or sodium or potassium or cesium carbonate, lithium or sodium or potassium hydroxide, sodium or potassium acetate, sodium or potassium t-butoxide, where sodium carbonate is preferred. This reaction is carried out in an inert reaction solvent such as methanol, ethanol, n- or i-propanol, dimethylsulfoxide, dimethylformamide, dimethoxyethane, where methanol is preferred from 0° C. to 150° C., where 70° C. is preferred. The oxime compound XIV undergoes ring expansion via the Beckmann Rearrangment upon treatment with a suitable acid such as, but not limited to, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid, or polyphosphoric acid at 0° C. to 150° C. Alternatively, the oxime XIV can be treated with phosphorus tri-chloride or phosphorus tri-bromide in an inert reaction solvent such as dichloromethane, 1,2-dichloroethane or chloroform. Preferably, the oxime XIV was dissolved in concentrated sulfuric acid and heated to 100° C. to form the lactam compound of formula XV. Lactam XV is reduced with a suitable reducing agent such as, but not limited to, lithium aluminum hydride, borane, alane, or di-isobutyl aluminum hydride, where lithium aluminum hydride is preferred in an inert solvent such as ether, THF, 1,2-dimethoxyethane, or 1,4-dioxane, where THF is preferred at 0° C. to 150° C., where 50° C. is preferred to form the compound of formula II where m=1 and n=2.
The third method for preparing a compound of formula II where m=1 and n=2 is described in Scheme V. Referring to Scheme V, the commercially available piperazine compound of formula XVI is protected as the benzyl amine compound XVII according to the procedures described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999, where the procedure using benzyl bromide in ethanol at 60° C. is preferred. A compound of formula XVII is reduced using a suitable reducing agent such as, but not limited to, lithium aluminum hydride, borane, alane, or di-isobutyl aluminum hydride, where lithium aluminum hydride is preferred in an inert solvent such as ether, THF, 1,2-dimethoxyethane, hexanes or 1,4-dioxane where THF is preferred at 0° C. to 100° C., where 0° C. to ambient temperature is preferred to form 2-(piperazinyl)-ethanol compound of formula XVIII. Reaction of a compound of formula XVIII with diethyl azodicarboxylate or diisopropyl azodicarboxylate, where diethyl azodicarboxylate is preferred and a phosphine reagent such as but not limited to dicyclohexylphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, tri-isopropylphosphine, tri-n-propylphosphine, tri-isobutylphosphine, tri-n-butylphosphine, tri-o-tolylphosphine, triphenylphosphine, 2-(dicyclohexylphosphino)-biphenyl, 2-(di-tert-butylphosphino)-biphenyl, 2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl, 2-di-tert-butylphosphino-2′-(N,N-dimethylamino)biphenyl or polymer supported triphenylphosphine; more preferably triphenylphosphine in an inert reaction solvent such as water, methanol, ethanol, isopropanol, acetonitrile, methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, diethylether, dioxane, 1,2-dimethoxyethane, benzene, toluene, dimethylformamide, or dimethylsulfoxide, more preferably tetrahydrofuran at 0° C. to 100° C., where 20° C. is preferred produces a diazabicycle compound of formula XIX. Alternative methods for this conversion would include converting the primary alcohol functional group of XVII in to a good leaving group such as, but not limited to, Cl, Br, I, tosylate, mesylate followed by cyclization to the desired bicycle XIX under thermal conditions with or without the addition of a base. Removal of the benzyl protecting group in XIX to afford 1,4-diazabicyclo[3.2.1]octane (a compound of formula II, where m=1 and n=2) is accomplished by a variety of conditions as detailed in in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999, with the preferred conditions being hydrogenation at 50 psi H 2 , using palladium on carbon as a catalyst and EtOH and HCl as solvent at room temperature.
A compound of formula II where m=1 and n=3 is prepared according to two methods. The first method is according to the procedures described by Rubstov, M. V.; et al. Zh. Obshch. Khim. 1964, 61, 9481. The second method is according to the procedures described in Scheme VI. Referring to Scheme VI, 3-(4-benzyl-piperazin-2-yl)-propionic acid methyl ester (XX) was made according to the procedure of Van den Branden, S.; et al. J. Chem. Soc. Perkin Trans. 1 1992, 1035. A compound of formula XX was reduced by reaction with lithium aluminum hydride, RED-AL, or alane, in an inert reaction solvent such as ether, THF, 1,4-dioxane, 1,2-dimethoxyethane, hexane, benzene or toluene at 0° C. to the solvent reflux temperature with lithium aluminum hydride in THF at 0° C. to ambient temperature being preferred to give a compound of formula XXI. The compound of formula XXI was protected as the trifluoroacetamide giving a compound of formula XXII according to the procedures described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999, where the procedure using trifluoroacetic anhydride and pyridine with dichloromethane as a solvent from 0° C. to ambient temperature is preferred. The benzyl group in XXII is removed according to the procedures described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999, where the procedure using hydrogen gas at 50 psi and 10% palladium on carbon as a catalyst and ethanol/concentrated HCl as the solvent at ambient temperature is preferred to give a compound of formula XXIII. Treatment of a compound of formula XXIII with diethyl azodicarboxylate or diisopropyl azodicarboxylate, where diethyl azodicarboxylate is preferred and a phosphine reagent such as but not limited to dicyclohexylphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, tri-isopropylphosphine, tri-n-propylphosphine, tri-isobutylphosphine, tri-n-butylphosphine, tri-o-tolylphosphine, triphenylphosphine, 2-(dicyclohexylphosphino)-biphenyl, 2-(di-tert-butylphosphino)-biphenyl, 2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl, 2-di-tert-butylphosphino-2′-(N,N-dimethylamino)biphenyl or polymer supported triphenylphosphine; more preferably triphenylphosphine in an inert reaction solvent such as water, methanol, ethanol, isopropanol, acetonitrile, methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, diethylether, 1,4-dioxane, 1,2-dimethoxyethane, benzene, toluene, dimethylformamide, or dimethylsulfoxide, more preferably tetrahydrofuran at 0° C. to 100° C., where 20° C. is preferred produces a diazabicycle compound of formula XXIV. Alternative methods for this conversion would include converting the primary alcohol functional group of XXIII in to a good leaving group such as, but not limited to, Cl, Br, I, tosylate, mesylate followed by cyclization to the desired bicycle XXIV under thermal conditions with or without the addition of a base. The trifluoroacetamide group in XXIV is removed according to the procedures described in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1999, where the procedure using sodium carbonate in a methanol/water reaction solvent at 60° C. is preferred to form a compound of formula II, where m 1 and n=3.
A compound of formula II where m=2 and n=3 is prepared according to the procedures outlined in Scheme VII. Referring to Scheme VII, 1-aza-bicyclo[3.2.2]nonan-6-one (XXV), made by the procedure of Lowe; et al. Bioorg . & Med. Chem. Lett. 1993, 3(5), 921-924, was converted to the oxime compound of formula XXVI upon treatment with hydroxylamine hydrochloride in the presence of a base such as, but not limited to, lithium or sodium or potassium or cesium carbonate, lithium or sodium or potassium hydroxide, sodium or potassium acetate, sodium or potassium t-butoxide, where sodium carbonate is preferred. This reaction is carried out in an inert reaction solvent such as methanol, ethanol, n- or i-propanol, dimethylsulfoxide, dimethylformamide, 1,2-dimethoxyethane, where methanol is preferred from 0° C. to 150° C., where 70° C. is preferred. The oxime compound XXVI undergoes ring expansion via the Beckmann Rearrangment upon treatment with a suitable acid such as, but not limited to, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid, or polyphosphoric acid at 0° C. to 150° C. Alternatively, the oxime XXVI can be treated with phosphorus tri-chloride or phosphorus tri-bromide in an inert reaction solvent such as dichloromethane, 1,2-dichloroethane or chloroform. Preferably, the oxime XXVI was dissolved in concentrated sulfuric acid and heated to 100° C. to form the lactam compound of formula XXVII. Lactam XXVII is reduced with a suitable reducing agent such as, but not limited to, lithium aluminum hydride, borane, alane, or di-isobutyl aluminum hydride, where lithium aluminum hydride is preferred in an inert solvent such as ether, THF, 1,2-dimethoxyethane, or 1,4-dioxane, where THF is preferred at 0° C. to 150° C., where 50° C. is preferred to form the compound of formula II where m=2 and n=3.
A compound of formula II where m=3 and n=3 is prepared according to the procedures outlined in Scheme VIII. 5-Oxo-azocane-1-carboxylic acid methyl ester (XXVIII) was made by the procedure of Miyano; et al. Heterocycles 1986, 24(8), 2121-2125, and was reacted with tosylmethylisocyanide (tosmic) in the presence of a base such as, but not limited to, lithium or sodium or potassium or cesium carbonate, lithium or sodium or potassium hydroxide, sodium or potassium methoxide, sodium or potassium ethoxide, sodium or potassium acetate, sodium or potassium t-butoxide, where potassium t-butoxide is preferred, in an inert reaction solvent such as, but not limited to, ether, tetrhydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane, more preferable 1,2-dimethoxyethane at ambient temperature to the solvent reflux temperature where 60° C. is preferred to give a compound of formula XXIX. The compound of formula XXIX was refluxed with aqueous acid such as, but not limited to, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, phosphoric acid, or formic acid, more preferably hydrochloric acid and then with methanol or ethanol, preferably methanol, saturated with gaseous HCl to give a compound of formula XXX. The resulting amine compound of formula XXX was refluxed with methyl bromoacetate and a base such as, but not limited to, triethylamine, diisopropylethylamine, pyridine, 2,6-lutidine, and 1,8-diazabicyclo[5.4.0]undec-7-ene; more preferable triethylamine, in an inert reaction solvent such as dichlormethane, 1,2-dichloroethane, 1,4-dioxane, toluene or tetrahydrofuran, more preferable dichloromethane at ambient temperature to the reflux temperature of the solvent, more preferable ambient temperature, to give a compound of formula XXXI. The diester compound of formula XXXI was reacted with a strong base such as, but not limited to, sodium or potassium methoxide, sodium or potassium ethoxide, or sodium or potassium t-butoxide; more preferable potassium ethoxide in a mixture of alcohol and hydrocarbon solvent; more preferable ethanol/toluene at ambient temperature up to the reflux point of the solvent; more preferably the reflux temperature followed by treatment with refluxing aqueous hydrochloric or sulfuric acid to give a compound of formula XXXII. The compound of formula XXXII was converted to the oxime compound of formula XXXIII upon treatment with hydroxylamine hydrochloride in the presence of a base such as, but not limited to, lithium or sodium or potassium or cesium carbonate, lithium or sodium or potassium hydroxide, sodium or potassium acetate, sodium or potassium t-butoxide, where sodium carbonate is preferred. This reaction is carried out in an inert reaction solvent such as methanol, ethanol, n- or i-propanol, dimethylsulfoxide, dimethylformamide, 1,2-dimethoxyethane, where methanol is preferred from 0° C. to 150° C., where 70° C. is preferred. The oxime compound XXXIII undergoes ring expansion via the Beckmann Rearrangment upon treatment with a suitable acid such as, but not limited to, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid, or polyphosphoric acid at 0° C. to 150° C. Alternatively, the oxime XXXIII can be treated with phosphorus tri-chloride or phosphorus tri-bromide in an inert reaction solvent such as dichloromethane, 1,2-dichloroethane or chloroform. Preferably, the oxime XXXIII was dissolved in concentrated sulfuric acid and heated to 100° C. to form the lactam compound of formula XXXIV. Lactam XXXIV is reduced with a suitable reducing agent such as, but not limited to, lithium aluminum hydride, borane, alane, or di-isobutyl aluminum hydride, where lithium aluminum hydride is preferred in an inert solvent such as ether, THF, 1,2-dimethoxyethane, or 1,4-dioxane, where THF is preferred at 0° C. to 150° C., where 50° C. is preferred to form the compound of formula II where m=3 and n=3.
Compounds of formula III, namely substituted phenyl, pyridine, pyrazine, pyrimidine and pyridazine compounds, can be purchased or prepared by methods well known to those of skill in the art.
Compounds of formula IIIA wherein one of the groups defined by A, B, D, E, or F is substituted with a (C 6 -C 11 )aryl or 5-12 membered hetero aryl group, R 6 as defined above, are prepared according to the methods detailed in Scheme IX. Referring to Scheme IX, the synthesis is initiated from a compound of formula III wherein one of the groups defined by A, B, D, E, or F above contains a C-Z group. The functional group Z is defined as a group with the ability to undergo oxidative addition, such as but not limited to Cl, Br, I, OTf, by an organometallic reagent. These compounds of formula III are commercially available or are prepared according to procedures described in the literature and can be prepared easily by one skilled in the art of organic synthesis. Preferred organometallic reagents contain metal such as palladium, nickel or copper with palladium being the most preferred. Referring to Scheme IX, treatment of a compound of the formula III wherein Z is chloro, bromo, iodo or triflate (OTf) with bis(pinacolato)diboron and a palladium catalyst such as palladium (0) tetrakis(triphenylphosphine), palladium (II) acetate, allyl palladium chloride dimer, tris(dibenzylideneacetone)dipalladium (0), tris(dibenzylidene-acetone)dipalladium (0) chloroform adduct, palladium (II) chloride or dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct, preferably dichloro[1,1′-bis(diphenylphosphino)-ferrocene]palladium (II) dichloromethane adduct, in the presence or absence of a phosphine ligand such as 1,1′-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-o-tolylphosphine, tri-tert-butylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane, BINAP, 2-biphenyl dicyclohexylphosphine, 2-biphenyl-di-tert-butylphosphine, 2-(N,N-dimethylamino)-2′-di-tert-butylphosphino-biphenyl or 2-(N,N-dimethylamino)-2′-dicyclohexylphosphinobiphenyl, preferably 1,1′-bis(diphenylphosphino)ferrocene, and in the presence or absence of a base such as potassium acetate, sodium acetate, cesium acetate, sodium carbonate, lithium carbonate, potassium carbonate, cesium carbonate or cesium fluoride, preferably potassium acetate, yields a compound of the formula XXXV wherein the Z group has been replaced with M, wherein M=borane pinacol ester. Generally, this reaction is carried out in a reaction inert solvent such as 1,4-dioxane, acetonitrile, methyl sulfoxide, tetrahydrofuran, ethanol, methanol, 2-propanol, toluene, preferably methyl sulfoxide, at a temperature from about from 0° C. to about 200° C., preferably from about 80° C. to about 120° C.
Other methods of converting a compound of the formula III with the Z group mentioned above into a compound of the formula XXXV wherein the Z group is replaced with M, wherein M is boronic acid, boronic acid ester or trialkylstannane, are known in the art. For instance, treatment of a compound of the formula III, wherein Z is Br or I, with an alkyl lithium reagent such as, but not limited to n-butyl lithium, sec butyl lithium or tert-butyl lithium, in a solvent such as diethyl ether, tetrahydrofuran, dimethoxyethane, hexane, toluene, dioxane or a similar reaction inert solvent, at a temperature from about −100° C. to about 25° C. affords the corresponding compound of the formula XXXV wherein Z is Li. Treatment of a solution of this material with a suitable boronic ester such as trimethoxyborane, triethoxyborane or triisopropylborane, followed by a standard aqueous work-up with acid will afford the corresponding compound of the formula XXXV wherein M is boronic acid.
Alternatively, treating a mixture of a compound of the formula III wherein Z is Br or I and a boronic ester with an alkyl lithium reagent, as described above, followed by a standard aqueous work-up with acid will afford the corresponding compound of formula XXXV wherein M is boronic acid. Alternatively, treating a compound of the formula III wherein Z is Br or I with an alkyl lithium reagent such as, but not limited to n-butyl lithium, sec butyl lithium or tert-butyl lithium, in a solvent such as diethyl ether, tetrahydrofuran, dimethoxyethane, hexane, toluene, dioxane or a similar reaction inert solvent, at a temperature from about −100° C. to about 25° C. will afford the corresponding compound of the formula XXXV wherein M is Li. Treatment of a solution of this material with a suitable trialkylstannyl halide such as, but not limited to trimethylstannyl chloride or bromide or tributylstannyl chloride or bromide, followed by a standard aqueous work-up will afford the corresponding compound of the formula XXXV wherein M is trimethyl or tributylstannane.
Treatment of a compound of the formula XXXV wherein M is a boronic acid, boronic ester, or trialkylstannane group, with an aryl or heteroaryl chloride, aryl or heteroaryl bromide, aryl or heteroaryl iodide, or aryl or heteroaryl triflate of the formula XXXVI, preferably an aryl or heteroaryl bromide, with a palladium catalyst such as palladium (0) tetrakis(triphenylphosphine), palladium (II) acetate, allyl palladium chloride dimer, tris(dibenzylideneacetone)dipalladium (0), tris(dibenzylideneacetone)dipalladium (0) chloroform adduct, palladium (II) chloride or dichloro[1,1′-bis (diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct, preferably palladium (0) tetrakis(triphenylphosphine), in the presence or absence of a phosphine ligand such as 1,1′-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-o-tolylphosphine, tri-tert-butylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane, BINAP, 2-biphenyl dicyclohexylphosphine, 2-biphenyl-di-tert-butylphosphine, 2-(N,N-dimethylamino)-2′-di-tert-butylphosphino-biphenyl or 2-(N,N-dimethylamino)-2′-dicyclohexylphosphinobiphenyl, preferably triphenylphosphine, and in the presence or absence of a base such as potassium phosphate, potassium acetate, sodium acetate, cesium acetate, sodium carbonate, lithium carbonate, potassium carbonate, cesium fluoride or cesium carbonate, preferably potassium phosphate, affords a compound of formula IIIA. This reaction is typically carried out in a reaction inert solvent such as 1,4-dioxane, acetonitrile, methyl sulfoxide, tetrahydrofuran, ethanol, methanol, 2-propanol, or toluene, preferably 1,4-dioxane, in the presence or absence of from about 1%-about 10% water, preferably about 5% water, at a temperature from about 0° C. to about 200° C., preferably from about 60° C. to about 100° C.
Alternatively, referring to Scheme IX, a compound of the formula III can be reacted with a compound of the formula XXXVII, wherein M is a boronic acid, boronic acid ester, borane pinacol ester or trialkylstannane group, preferably an aryl or heteroaryl boronic acid or boronic acid ester, with a palladium catalyst such as palladium (0) tetrakis(triphenylphosphine), palladium (II) acetate, allyl palladium chloride dimer, tris(dibenzylideneacetone)dipalladium (0), tris(dibenzylideneacetone)dipalladium (0) chloroform adduct, palladium (II) chloride or dichloro[1,1′-bis (diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct, preferably palladium (0) tetrakis(triphenylphosphine), in the presence or absence of a phosphine ligand such as 1,1′-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-o-tolylphosphine, tri-tert-butylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane, BINAP, 2-biphenyl dicyclohexylphosphine, 2-biphenyl-di-tert-butylphosphine, 2-(N,N-dimethylamino)-2′-di-tert-butylphosphino-biphenyl or 2-(N,N-dimethylamino)-2′-dicyclohexylphosphinobiphenyl, preferably triphenylphosphine, and in the presence or absence of a base such as potassium phosphate, potassium acetate, sodium acetate, cesium acetate, sodium carbonate, lithium carbonate, potassium carbonate, cesium fluoride or cesium carbonate, preferably sodium carbonate, affording a compound of formula IIIA. This reaction is typically carried out in a reaction inert solvent such as 1,4-dioxane, acetonitrile, methyl sulfoxide, tetrahydrofuran, ethanol, methanol, 2-propanol, or toluene, preferably ethanol, in the presence or absence of from 0%-10% water, preferably about 0% water, at a temperature from about 0° C. to about 200° C., preferably from about 60° C. to about 100° C.
Compounds of formula IA wherein one of the groups defined by A, B, D, E, or F is substituted with a (C 6 -C 11 )aryl or 5-12 membered hetero aryl group, R 6 as defined above, are prepared according to the methods detailed in Scheme I using a compound of formula IIIA as described above. Alternatively, compounds of formula IA can be prepared according to the methods detailed in Scheme X. Referring to Scheme X, the synthesis is initiated from a compound of formula I wherein one of the groups defined by A, B, D, E, or F above contains a C-Z group. The functional group Z is defined as a group with the ability to undergo oxidative addition, such as but not limited, to Cl, Br, I, OTf, by an organometallic reagent. These compounds of formula I are prepared according to procedures described in Scheme I. Preferred organometallic reagents contain metal such as palladium, nickel or copper with palladium being the most preferred. Referring to Scheme X, treatment of a compound of the formula I wherein Z is chloro, bromo, iodo or triflate (OTf) with bis(pinacolato)diboron and a palladium catalyst such as palladium (0) tetrakis(triphenylphosphine), palladium (II) acetate, allyl palladium chloride dimer, tris(dibenzylideneacetone)dipalladium (0), tris(dibenzylidene-acetone)dipalladium (0) chloroform adduct, palladium (II) chloride or dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct, preferably dichloro[1,1′-bis(diphenylphosphino)-ferrocene]palladium (II) dichloromethane adduct, in the presence or absence of a phosphine ligand such as 1,1′-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-o-tolylphosphine, tri-tert-butylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane, BINAP, 2-biphenyl dicyclohexylphosphine, 2-biphenyl-di-tert-butylphosphine, 2-(N,N-dimethylamino)-2′-di-tert-butylphosphino-biphenyl or 2-(N,N-dimethylamino)-2′-dicyclohexylphosphinobiphenyl, preferably 1,1′-bis(diphenylphosphino)ferrocene, and in the presence or absence of a base such as potassium acetate, sodium acetate, cesium acetate, sodium carbonate, lithium carbonate, potassium carbonate, cesium carbonate or cesium fluoride, preferably potassium acetate, yields a compound of the formula XXXVIII wherein the Z group has been replaced with M, wherein M=borane pinacol ester. Generally, this reaction is carried out in a reaction inert solvent such as 1,4-dioxane, acetonitrile, methyl sulfoxide, tetrahydrofuran, ethanol, methanol, 2-propanol, toluene, preferably methyl sulfoxide, at a temperature from about from 0° C. to about 200° C., preferably from about 80° C. to about 120° C.
Other methods of converting a compound of the formula I with the Z group mentioned above into a compound of the formula XXXVIII wherein the Z group is replaced with M, wherein M is boronic acid, boronic acid ester or trialkylstannane, are known in the art. For instance, treatment of a compound of the formula I, wherein Z is Br or I, with an alkyl lithium reagent such as, but not limited to n-butyl lithium, sec butyl lithium or tert-butyl lithium, in a solvent such as diethyl ether, tetrahydrofuran, dimethoxyethane, hexane, toluene, dioxane or a similar reaction inert solvent, at a temperature from about −100° C. to about 25° C. affords the corresponding compound of the formula XXXVIII wherein Z is Li. Treatment of a solution of this material with a suitable boronic ester such as trimethoxyborane, triethoxyborane or triisopropylborane, followed by a standard aqueous work-up with acid will afford the corresponding compound of the formula XXXVIII wherein M is boronic acid.
Alternatively, treating a mixture of a compound of the formula I wherein Z is Br or I and a boronic ester with an alkyl lithium reagent, as described above, followed by a standard aqueous work-up with acid will afford the corresponding compound of formula XXXVIII wherein M is boronic acid. Alternatively, treating a compound of the formula I wherein Z is Br or I with an alkyl lithium reagent such as, but not limited to n-butyl lithium, sec butyl lithium or tert-butyl lithium, in a solvent such as diethyl ether, tetrahydrofuran, dimethoxyethane, hexane, toluene, dioxane or a similar reaction inert solvent, at a temperature from about −100° C. to about 25° C. will afford the corresponding compound of the formula XXXVIII wherein M is Li. Treatment of a solution of this material with a suitable trialkylstannyl halide such as, but not limited to trimethylstannyl chloride or bromide or tributylstannyl chloride or bromide, followed by a standard aqueous work-up will afford the corresponding compound of the formula XXXVIII wherein M is trimethyl or tributylstannane.
Treatment of a compound of the formula XXXVIII wherein M is a boronic acid, boronic ester, or trialkylstannane group, with an aryl or heteroaryl chloride, aryl or heteroaryl bromide, aryl or heteroaryl iodide, or aryl or heteroaryl triflate of the formula XXXIX, preferably an aryl or heteroaryl bromide, with a palladium catalyst such as palladium (0) tetrakis(triphenylphosphine), palladium (II) acetate, allyl palladium chloride dimer, tris(dibenzylideneacetone)dipalladium (0), tris(dibenzylideneacetone)dipalladium (0) chloroform adduct, palladium (II) chloride or dichloro(1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct, preferably palladium (0) tetrakis(triphenylphosphine), in the presence or absence of a phosphine ligand such as 1,1′-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-o-tolylphosphine, tri-tert-butylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane, BINAP, 2-biphenyl dicyclohexylphosphine, 2-biphenyl-di-tert-butylphosphine, 2-(N,N-dimethylamino)-2′-di-tert-butylphosphino-biphenyl or 2-(N,N-dimethylamino)-2′-dicyclohexylphosphinobiphenyl, preferably triphenylphosphine, and in the presence or absence of a base such as potassium phosphate, potassium acetate, sodium acetate, cesium acetate, sodium carbonate, lithium carbonate, potassium carbonate, cesium fluoride or cesium carbonate, preferably sodium carbonate, affords a compound of formula IA. This reaction is typically carried out in a reaction inert solvent such as 1,4-dioxane, acetonitrile, methyl sulfoxide, tetrahydrofuran, ethanol, methanol, 2-propanol, or toluene, preferably ethanol, in the presence or absence of from about 0%-about 10% water, preferably about 0% water, at a temperature from about 0° C. to about 200° C., preferably from about 60° C. to about 100° C.
Alternatively, referring to Scheme X, a compound of the formula I can be reacted with a compound of the formula XL, wherein M is a boronic acid, boronic acid ester, borane pinacol ester or trialkylstannane group, preferably an aryl or heteroaryl boronic acid or boronic acid ester, with a palladium catalyst such as palladium (0) tetrakis(triphenylphosphine), palladium (II) acetate, allyl palladium chloride dimer, tris(dibenzylideneacetone)dipalladium (0), tris(dibenzylideneacetone)dipalladium (0) chloroform adduct, palladium (II) chloride or dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct, preferably palladium (0) tetrakis(triphenylphosphine), in the presence or absence of a phosphine ligand such as 1,1′-bis(diphenylphosphino)ferrocene, triphenylphosphine, tri-o-tolylphosphine, tri-tert-butylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)-propane, BINAP, 2-biphenyl dicyclohexylphosphine, 2-biphenyl-di-tert-butylphosphine, 2-(N,N-dimethylamino)-2′-di-tert-butylphosphino-biphenyl or 2-(N,N-dimethylamino)-2′-dicyclohexylphosphinobiphenyl, preferably triphenylphosphine, and in the presence or absence of a base such as potassium phosphate, potassium acetate, sodium acetate, cesium acetate, sodium carbonate, lithium carbonate, potassium carbonate, cesium fluoride or cesium carbonate, preferably sodium carbonate, affording a compound of formula IA. This reaction is typically carried out in a reaction inert solvent such as 1,4-dioxane, acetonitrile, methyl sulfoxide, tetrahydrofuran, ethanol, methanol, 2-propanol, or toluene, preferably ethanol, in the presence or absence of from 0%-10% water, preferably about 0% water, at a temperature from about 0° C. to about 200° C., preferably from about 60° C. to about 100° C.
Isolation and purification of the products can be accomplished by standard procedures that are known to a chemist of ordinary skill. In each of the reactions discussed above, or illustrated in Schemes above, pressure is not critical unless otherwise indicated. Pressures from about 0.5 atmospheres to about 5 atmospheres are generally acceptable, with ambient pressure, i.e., about 1 atmosphere, being preferred as a matter of convenience.
The compounds of the formula I and their pharmaceutically acceptable salts (hereafter “the active compounds”) can be administered via either the oral, transdermal (e.g., through the use of a patch), intranasal, sublingual, rectal, parenteral or topical routes. Transdermal and oral administration are preferred. These compounds are, most desirably, administered in dosages ranging from about 0.25 mg up to about 1500 mg per day, preferably from about 0.25 to about 300 mg per day in single or divided doses, although variations will necessarily occur depending upon the weight and condition of the subject being treated and the particular route of administration chosen. However, a dosage level that is in the range of about 0.01 mg to about 10 mg per kg of body weight per day is most desirably employed. Variations may nevertheless occur depending upon the weight and condition of the persons being treated and their individual responses to said medicament, as well as on the type of pharmaceutical formulation chosen and the time period and interval during which such administration is carried out. In some instances, dosage levels below the lower limit of the aforesaid range may be more than adequate, while in other cases still larger doses may be employed without causing any harmful side effects, provided that such larger doses are first divided into several small doses for administration throughout the day.
The active compounds can be administered alone or in combination with pharmaceutically acceptable carriers or diluents by any of the several routes previously indicated. More particularly, the active compounds can be administered in a wide variety of different dosage forms, e.g., they may be combined with various pharmaceutically acceptable inert carriers in the form of tablets, capsules, transdermal patches, lozenges, troches, hard candies, powders, sprays, creams, salves, suppositories, jellies, gels, pastes, lotions, ointments, aqueous suspensions, injectable solutions, elixirs, syrups, and the like. Such carriers include solid diluents or fillers, sterile aqueous media and various non-toxic organic solvents. In addition, oral pharmaceutical compositions can be suitably sweetened and/or flavored. In general, the active compounds are present in such dosage forms at concentration levels ranging from about 5.0% to about 70% by weight.
For oral administration, tablets containing various excipients such as microcrystalline cellulose, sodium citrate, calcium carbonate, dicalcium phosphate and glycine may be employed along with various disintegrants such as starch (preferably corn, potato or tapioca starch), alginic acid and certain complex silicates, together with granulation binders like polyvinylpyrrolidone, sucrose, gelatin and acacia. Additionally, lubricating agents such as magnesium stearate, sodium lauryl sulfate and talc can be used for tabletting purposes. Solid compositions of a similar type may also be employed as fillers in gelatin capsules; preferred materials in this connection also include lactose or milk sugar, as well as high molecular weight polyethylene glycols. When aqueous suspensions and/or elixirs are desired for oral administration the active ingredient may be combined with various sweetening or flavoring agents, coloring matter and, if so desired, emulsifying and/or suspending agents, together with such diluents as water, ethanol, propylene glycol, glycerin and various combinations thereof.
For parenteral administration, a solution of an active compound in either sesame or peanut oil or in aqueous propylene glycol can be employed. The aqueous solutions should be suitably buffered (preferably pH greater than 8), if necessary, and the liquid diluent first rendered isotonic. These aqueous solutions are suitable for intravenous injection purposes. The oily solutions are suitable for intraarticular, intramuscular and subcutaneous injection purposes. The preparation of all these solutions under sterile conditions is readily accomplished by standard pharmaceutical techniques well known to those skilled in the art.
It is also possible to administer the active compounds topically and this can be done by way of creams, a patch, jellies, gels, pastes, ointments and the like, in accordance with standard pharmaceutical practice.
The effectiveness of the active compounds in suppressing nicotine binding to specific receptor sites can be determined by the following procedure, which is a modification of the methods of Lippiello, P. M. and Fernandes, K. G. (in “The Binding of L-[ 3 H]Nicotine To A Single Class of High-Affinity Sites in Rat Brain Membranes”, Molecular Pharm., 29, 448-54, (1986)) and Anderson, D. J. and Arneric, S. P. (in “Nicotinic Receptor Binding of 3 H-Cytisine, 3 H-Nicotine and 3 H-Methylcarmbamylcholine In Rat Brain”, European J. Pharm., 253, 261-67 (1994)). Male Sprague-Dawley rats (200-300 g) from Charles River were housed in groups in hanging stainless steel wire cages and were maintained on a 12 hour light/dark cycle (7 a.m.-7 p.m. light period). They received standard Purina Rat Chow and water ad libitum. The rats were killed by decapitation. Brains were removed immediately following decapitation. Membranes were prepared from brain tissue according to the methods of Lippiello and Fernandez ( Molec. Pharmacol., 29, 448-454, (1986)) with some modifications. Whole brains were removed, rinsed with ice-cold buffer, and homogenized at 0° in 10 volumes of buffer (w/v) using a Brinkmann Polytron™ (Brinkmann Instruments Inc., Westbury, N.Y.), setting 6, for 30 seconds. The buffer consisted of 50 mM Tris HCl at a pH of 7.5 at room temperature. The homogenate was sedimented by centrifugation (10 minutes; 50,000×g; 0° to 4° C.). The supernatant was poured off and the membranes were gently resuspended with the Polytron and centrifuged again (10 minutes; 50,000×g; 0° C. to 4° C.). After the second centrifugation, the membranes were resuspended in assay buffer at a concentration of 1.0 g/100 mL. The composition of the standard assay buffer was 50 mM Tris HCl, 120 mM NaCl, 5 mM KCl, 2 mM MgCl 2 , 2 mM CaCl 2 and had a pH of 7.4 at room temperature.
Routine assays were performed in borosilicate glass test tubes. The assay mixture typically consisted of 0.9 mg of membrane protein in a final incubation volume of 1.0 mL. Three sets of tubes were prepared wherein the tubes in each set contained 50 μL of vehicle, blank, or test compound solution, respectively. To each tube was added 200 μL of [ 3 H]-nicotine in assay buffer followed by 750 μL of the membrane suspension. The final concentration of nicotine in each tube was 0.9 nM. The final concentration of cytisine in the blank was 1 μM. The vehicle consisted of deionized water containing 30 μL of 1 N acetic acid per 50 mL of water. The test compounds and cytisine were dissolved in vehicle. Assays were initiated by vortexing after addition of the membrane suspension to the tube. The samples were incubated at 0° to 4° C. in an iced shaking water bath. Incubations were terminated by rapid filtration under vacuum through Whatman GF/B™ glass fiber filters (Brandel Biomedical Research & Development Laboratories, Inc., Gaithersburg, Md.) using a Brandel™ multi-manifold tissue harvester (Brandel Biomedical Research & Development Laboratories, Inc., Gaithersburg, Md.). Following the initial filtration of the assay mixture, filters were washed two times with ice-cold assay buffer (5 ml each). The filters were then placed in counting vials and mixed vigorously with 20 ml of Ready Safe™ (Beckman, Fullerton, Calif.) before quantification of radioactivity. Samples were counted in a LKB Wallac Rackbeta™ liquid scintillation counter (Wallac Inc., Gaithersburg, Md.) at 40-50% efficiency. All determinations were in triplicate.
Calculations: Specific binding (C) to the membrane is the difference between total binding in the samples containing vehicle only and membrane (A) and non-specific binding in the samples containing the membrane and cytisine (B), i.e.,
Specific binding=( C )=( A )−( B ).
Specific binding in the presence of the test compound (E) is the difference between the total binding in the presence of the test compound (D) and non-specific binding (B), i.e.,
( E )=( D )−( B ).
% Inhibition=(1−(( E )/( C ))times 100.
The compounds of the invention that were tested in the above assay exhibited IC 50 values of less than 100 μM.
[ 125 I]-Bungarotoxin binding to nicotinic receptors in GH 4 Cl cells: Membrane preparations were made for nicotinic receptors expressed in GH 4 Cl cell line. Briefly, one gram of cells by wet weight were homogenized with a polytron in 25 mls of buffer containing 20 mM Hepes, 118 mM NaCl, 4.5 mM KCl, 2.5 mM CaCl 2 , 1.2 mM MgSO 4 , pH 7.5. The homogenate was centrifuged at 40,000×g for 10 min at 4° C., the resulting pellet was homogenized and centrifuged again as described above. The final pellet was resuspended in 20 mls of the same buffer. Radioligand binding was carried out with [ 125 I] alpha-bungarotoxin from New England Nuclear, specific activity about 16 uCi/ug, used at 0.4 nM final concentration in a 96 well microtiter plate. The plates were incubated at 37° C. for 2 hours with 25 μl drugs or vehicle for total binding, 100 μl [ 125 I] Bungarotoxin and 125 μl tissue preparation. Nonspecific binding was determined in the presence of methyllycaconitine at 1 μM final concentration. The reaction was terminated by filtration using 0.5% Polyethylene imine treated Whatman GF/B™ glass fiberfilters (Brandel Biomedical Research & Development Laboratories, Inc., Gaithersburg, Md.) on a Skatron cell harvester (Molecular Devices Corporation, Sunnyvale, Calif.) with ice-cold buffer, filters were dried overnight, and counted on a Beta plate counter using Betaplate Scint. (Wallac Inc., Gaithersburg, Md.). Data are expressed as IC50's (concentration that inhibits 50% of the specific binding) or as an apparent Ki, IC50/1((+))[L]/KD. [L]=ligand concentration, KD=affinity constant for [ 125 I] ligand determined in separate experiment.
The compounds of the invention that were tested in the above assay exhibited IC 50 values of less than 10 μM.
[ 125 I]-Bungarotoxin binding to alpha1 nicotinic receptors in Torpedo electroplax membranes: Frozen Torpedo electroplax membranes (100 μl) were resuspended in 213 mls of buffer containing 20 mM Hepes, 118 mM NaCl, 4.5 mM KCl, 2.5 mM CaCl 2 , 1.2 mM MgSO 4 , pH 7.5 with 2 mg/ml BSA. Radioligand binding was carried out with [ 125 I] alpha-bungarotoxin from New England Nuclear, specific activity about 16 uCi/ug, used at 0.4 nM final concentration in a 96 well microtiter plate. The plates were incubated at 37° C. for 3 hours with 25 μl drugs or vehicle for total binding, 100 μl [ 125 I] Bungarotoxin and 125 μl tissue preparation. Nonspecific binding was determined in the presence of alpha-bungarotoxin at 1 μM final concentration. The reaction was terminated by filtration using 0.5% Polyethylene imine treated GF/B filters on a Brandel cell harvester with ice-cold buffer, filters were dried overnight, and counted on a Beta plate counter using Betaplate Scint. Data are expressed as IC50's (concentration that inhibits 50% of the specific binding) or as an apparent Ki, IC50/1+[L]/KD. [L]=ligand concentration, KD=affinity constant for [125] ligand determined in separate experiment.
The compounds of the invention that were tested in the above assay exhibited IC 50 values of less than 100 μM.
EXAMPLES
The following examples illustrate the methods and compounds of the present invention. It will be understood, however, that the invention is not limited to the specific Examples. In the examples, commercial reagents were used without further purification. Purification by chromatography was done on prepacked silica columns from Biotage (Dyax Corp, Biotage Division, Charlottesville, Va.). Melting points (mp) were obtained using a Mettler Toledo FP62 melting point apparatus (Mettler-Toledo, Inc., Worthington, Ohio) with a temperature ramp rate of 10° C./min and are uncorrected. Proton nuclear magnetic resonance ( 1 H NMR) spectra were recorded in deuterated solvents on a Varian INOVA400 (400 MHz) spectrometer (Varian NMR Systems, Palo Alto, Calif.). Chemical shifts are reported in parts per million (ppm, δ) relative to Me 4 Si (δ 0.00). Proton NMR splitting patterns are designated as singlet(s), doublet (d), triplet (t), quartet (q), quintet (quin), sextet (sex), septet (sep), multiplet (m) apparent (ap) and broad (br). Coupling constants are reported in hertz (Hz). Carbon-13 nuclear magnetic resonance ( 13 C NMR) spectra were recorded on a Varian INOVA400 (100 MHz). Chemical shifts are reported in ppm (δ) relative to the central line of the 1:1:1 triplet of deuterochloroform (δ 77.00), the center line of deuteromethanol (δ 49.0) or deuterodimethylsulfoxide (δ 39.7). The number of carbon resonance's reported may not match the actual number of carbons in some molecules due to magnetically and chemically equivalent carbons and may exceed the number of actual carbons due to conformational isomers. Mass spectra (MS) were obtained using a Waters ZMD mass spectrometer using flow injection atmospheric pressure chemical ionization (APCI) (Waters Corporation, Milford, Mass). Gas chromatography with mass detection (GCMS) were obtained using a Hewlett Packard HP 6890 series GC system with a HP 5973 mass selective detector and a HP-1 (crosslinked methyl siloxane) column (Agilent Technologies, Wilmington, Del.). HPLC spectra were recorded on a Hewlett Packard 1100 series HPLC system with a Zorbax SB-C8, 5 μm, 4.6×150 mm column (Agilent Technologies, Wilmington, Del.) at 25° C. using gradient elution. Solvent A is water, Solvent B is acetonitrile, Solvent C is 1% trifluoroacetic acid in water. A linear gradient over four minutes was used starting at 80% A, 10% B, 10% C and ending at 0% A, 90% B, 10% C. The eluent remained at 0% A, 90% B, 10% C for three minutes. A linear gradient over one minute was used to return the eluent to 80% A, 10% B, 10% C and it was held at this until the run time equaled ten minutes. Room temperature (RT) refers to 20-25° C.
Example 1
4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) (1-Benzyl-3-oxo-piperazin-2-yl)-acetic acid ethyl ester
Benzyl bromide (7.7 mL, 77 mmol) was added to a solution of ethyl-2-piperazine-3-one acetate (13 g, 70 mmol, Maybridge) in ethanol (100 mL). The mixture was heated at 60° C. for 6 hrs. Additional benzyl bromide (0.7 mL, 7 mmol) was added and the mixture was heated at 60° C. for 8 hrs. The solvent was removed in vacuo and the residue was dissolved in a mixture of water (100 mL) and ethyl acetate (100 mL) (note, pH=1.5). Partition and extract with ethyl acetate (3×100 mL). Wash the combined extracts with saturated NaHCO 3 , dry over Na 2 SO 4 , filter and concentrate to a solid. The solid was triturated with hexanes and the remaining solid was collected to yield 11 g (58%) of the title compound: 1 H NMR (CDCl 3 , 400 MHz) δ 7.33-7.24 (m, 5H), 6.60 (br s, 1H), 4.23-4.10 (m, 2H), 3.69 (2H, AB, J AB =13.3 Hz), 3.50 (br s, 1H), 3.33-3.22 (m, 2H), 3.09-3.04 (m, 1H), 2.98-2.88 (m, 2H), 2.51-2.44 (m, 1H), 1.25 (t, 3H, J=7.3 Hz); APCI MS m/z 277.1 (M+1).
B) 2-(1-Benzyl-piperazin-2-yl)-ethanol
Lithium aluminum hydride (4.6 grams, 120 mmol) was slowly added to a solution of (1-benzyl-3-oxo-piperazin-2-yl)-acetic acid ethyl ester (11 g, 40 mmol) in THF (150 mL) at 0° C. The mixture was allowed to stir for 18 h while warming to RT. The mixture was placed in and ice/water bath and additional lithium aluminum hydride (3.0 g, 80 mmol) was added. The mixture was allowed to stir for 20 h while warming to RT. 1 N NaOH was added until all of the LAH was consumed resulting in a white solid. The mixture was filtered through a pad of celite, washing with additional THF (50 mL). The filtrate was concentrated in vacuo to give 8 g (90%) of the title compound as an oil: APCI MS m/z 221.2 (M+1).
C) 4-Benzyl-1,4-diaza-bicyclo[3.2.1]octane
Diethyl azodicarboxylate (15.8 mL, 100 mmol) was slowly added to a solution of triphenylphosphine (26.2 g, 100 mmol) in THF (200 mL) while maintaining the reaction temperature below 20° C. After stirring this mixture for 30 min at RT, a solution of 2-(1-benzyl-piperazine-2-yl)-ethanol (11 g, 50 mmol) in THF (100 mL) was added while maintaining the reaction temperature below 20° C. The reaction mixture became turbid and the solvent was removed in vacuo after a period of 1 h. The residue was partitioned between water (20 mL) and ethyl acetate (50 mL) and the pH was adjusted to 2 with 6 N HCl. The phases were separated and the aqueous phase was extracted with EtOAc (50 mL) at pH 3.0, 4.5 and 10 (4×). The pH 10 extracts were combined, dried (Na 2 SO 4 ), filtered and concentrated to an oil. The oil was triturated three times with hot hexanes (100 mL) to remove any remaining triphenylphosphine and triphenylphosphine oxide and the hexanes were decanted. The remaining oil was dried resulting in 7.5 g (74%) of the title compound: APCI MS m/z 203.2 (M+1).
D) 1,4-Diaza-bicyclo[3.2.1]octane dihydrochloride
A mixture of 4-benzyl-1,4-diaza-bicyclo[3.2.1]octane (7.5 g, 37 mmol), 5% palladium on carbon (0.75 g, wet), concentrated HCl (7.5 mL) in EtOH (150 mL) was shaken under hydrogen (50 psi) for a period of 20 h at RT. The product precipitated out of the mixture and water was added in order to dissolve the product. The mixture was filtered through a pad of celite and washed with EtOH. The filtrate was concentrated in vacuo to a solid that was azeotroped with EtOH (3×50 mL). The resulting solid was triturated with hot isopropanol and stirred 18 h at RT. The resulting solid was collected by filtration giving 5.6 g (80%) of the title compound: 1 H NMR (d6-DMSO, 400 MHz) δ 4.26 (br s, 1H), 3.72 (d, 1H, J=12 Hz), 3.60-3.53 (m, 1H), 3.48-3.35 (m, 7H), 2.33-2.27 (m, 2H); GCMS m/z 112
E) 4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochoride
A solution of NaOMe (0.48 mL, 2.2 mmol, 4.6 M in MeOH) was added to a solution of 1,4-diaza-bicyclo[3.2.1]octane dihydrochloride (0.2 g, 1.1 mmol) in MeOH (15 mL) at 50° C. The solvent was removed in vacuo and the resulting residue was triturated with toluene (5 mL). The toluene solution was added to a flask containing 3,5-dibromopyridine (0.26 g, 1.1 mmol), 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.2 g, 0.33 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.1 g, 0.11 mmol), and NaOtBu (0.15 g, 1.5 mmol) under and atmosphere of nitrogen. The resulting mixture was heated at 80° C. for 20 h. The mixture was cooled to RT, diluted with CHCl 3 (10 mL) and washed with water (10 mL). The organic layer was concentrated and purified by chromatography using a gradient elution (20/1 CHCl 3 /MeOH to 10/1 CHCl 3 /MeOH) to give 90 mg (30%) of the title compound as its free base. This material was dissolved in EtOH and treated with concentrated HCl (0.2 mL). The solvent was removed in vacuo and the EtOH was added and the solvent was once again removed in vacuo. This procedure was repeated until concentration resulted in a solid (3× total). The resulting solid was triturated with iPrOH and the resulting solid was collected to give 82 mg (22%) of the title compound: (data for free base) 1 H NMR (CDCl 3 , 400 MHz) δ 8.13 (d, 1H, J=2.9 Hz), 8.06 (d, 1H, J=2.1 Hz), 7.21-7.19 (m, 1H), 4.20-4.17 (m, 1H), 3.15-3.08 (m, 3H), 3.04-2.80 (m, 4H), 2.66-2.62 (m, 1H), 1.87-1.72 (m, 2H); 13 C NMR (CDCl 3 , 100 MHz) δ 147.0, 140.5, 136.4, 124.2, 121.1, 59.9, 57.0, 52.9, 50.7, 41.7, 29.9; APCI MS m/z 270.1, 268.1 (M+1).
Example 2
4-(5-Phenyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
4-(5-Bromo-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochoride (50 mg, 0.15 mmol) was added to a mixture of phenylboronic acid (25 mg, 0.20 mmol), tetrakis(triphenylphosphine)palladium(0) (7 mg, 0.006 mmol), sodium carbonate (63 mg, 0.60 mmol) in EtOH (5 mL) and water (5 mL). The reaction mixture was placed in an oil bath at 80° C. for 3 h, and then 60° C. for 18 h. The mixture was cooled to RT, diluted with water (10 mL) and extracted with EtOAc (3×15 mL). The combined organic extracts were dried (Na 2 SO 4 ), filtered and concentrated. The residue was dissolved in EtOH (10 mL) and conc. HCl (0.2 mL) was added. The mixture was concentrated and EtOH (10 mL) was added and the solution was concentrated. This procedure was repeated three times and the resulting solid was triturated in EtOAc. The remaining solids were collected via filtration to give 40 mg (78%) of the title compound: (data for free base) 1 H NMR (CD 3 OD, 400 MHz) δ 8.55 (br s, 1H), 8.50 (br s, 1H), 8.33 (br s, 1H), 7.83-7.81 (m, 2H), 7.60-7.53 (m, 3H), 5.12 (br s, 1H), 4.06-4.04 (m, 1H), 3.70-3.59 (m, 5H), 3.54-3.51 (m, 2H), 2.51-2.47 (m, 1H), 2.26-2.23 (m, 1H); APCI MS m/z 266.2 (M+1).
Example 3
4-Pyridin-2-yl-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 2-bromopyridine: (data for free base) 1 H NMR (CDCl 3 , 400 MHz) δ 8.14 (dd, 1H, J=5.0, 1.7 Hz), 7.44-7.40 (m, 1H), 6.56 (dd, 1H, J=7.0, 5.0 Hz), 7.51 (d, 1H, J=8.7 Hz), 4.94 (dd, 1H, J=5.8, 3.3 Hz), 3.51-3.47 (m, 1H), 3.07-2.90 (m, 5H), 2.79-2.75 (m, 1H), 2.62-2.58 (m, 1H), 1.91-1.84 (m, 1H), 1.76-1.71 (m, 1H); 13 C (CDCl 3 , 100 MHz) δ 159.1, 148.2, 137.6, 113.3, 107.4, 60.0, 53.8, 53.2, 50.8, 40.0, 31.1; APCI MS m/z 190.2 (M+1).
Example 4
4-Pyridin-3-yl-1.4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromopyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 146.2, 140.3, 138.5, 123.7, 122.2, 60.0, 57.1, 53.0, 50.8, 41.9, 29.4; APCI MS m/z 190.2 (M+1).
Example 5
4-Pyridin-4-yl-1.4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 4-bromopyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 153.2, 150.3, 108.5, 59.7, 55.0, 53.0, 50.8, 40.6, 30.8; APCI MS m/z 190.2 (M+1).
Example 6
4-(5-Bromo-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 2,5-dibromopyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 157.3, 148.7, 139.9, 108.7, 107.6, 59.8, 53.8, 53.1, 50.8, 40.0, 31.2; APCI MS m/z 270.1, 268.1 (M+1).
Example 7
4-(5-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-chloro-5-phenylpyridazine (Rival, Y.; Hoffmann, R.; Didier, B.; Rybaltchenko, V.; Bourguignon, J.-J.; Wermuth, C. G. J. Med. Chem. 1998, 41, 311): (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 160.0, 142.5, 140.0, 136.2, 129.8, 129.5, 127.3, 109.6, 59.9, 54.0, 53.2, 50.8, 39.8, 31.5; APCI MS m/z 267.2 (M+1).
Example 8
4-(6-Phenyl-pyridazin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-chloro-6-phenylpyridazine: (data for free base) 1 H NMR (CDCl 3 , 400 MHz) δ 8.00 (d, 2H, J=7.1 Hz), 7.66 (d, 1H, J=9.5 Hz), 7.49-7.40 (m, 4H), 6.94 (d, 1H, J=9.5 Hz), 5.11 (dd, 1H, J=5.4,3.3 Hz), 3.80 (dd, 1H, J=12.9, 5.4 Hz), 3.28-3.04 (m, 5H), 2.94-2.91 (m, 1H), 2.77-2.74 (m, 1H), 2.09-2.01 (m, 1H), 1.94-1.89 (m, 1H); APCI MS m/z 267.1 (M+1).
Example 9
4-Pyrazin-2-yl-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 2-chloropyrazine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 142.0, 133.1, 131.4, 59.8, 53.2, 53.0, 50.7, 39.4, 31.4; APCI MS m/z 191.1 (M+1).
Example 10
4-Pyrimidin-5-yl-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 5-bromopyrimidine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 149.5, 143.7, 59.8, 56.3, 52.8, 50.7, 41.2, 29.8; APCI MS m/z 191.1 (M+1).
Example 11
4-(5-Chloro-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3,5-dichloropyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 146.8, 138.3, 136.0, 132.3, 121.4, 59.9, 57.0, 52.9, 50.8, 41.8, 29.9; APCI MS m/z224.1 (M+1).
Example 12
4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(3-trifluoromethyl-phenyl)-pyridine
A mixture of 3,5-dibromopyridine (1.2 g, 5 mmol), 3-trifluoromethylphenyl boronic acid (0.95 g, 5 mmol), tetrakis(triphenylphosphine)palladium (0) (0.23 g, 0.2 mmol), and sodium carbonate (1.1 g, 10 mmol) in EtOH (10 mL) and water (1 mL) were heated in an oil bath at 70° C. for 3 days. The mixture was cooled to RT and diluted with EtOAc (20 mL) and water (10 mL). The layers were partitioned and the organic layer was dried (Na 2 SO 4 ), filtered and concentrated. Purification by chromatography (eluting with 10:1 hexanes/EtOAc) resulted in 0.4 g (26%) of the title compound: 1 H NMR (CDCl 3 , 400 MHz) δ 8.76 (d, 1H, J=2.1 Hz), 8.71 (d, 1H, J=2.1 Hz), 8.06 (dd, 1H, J=2.1, 2.1 Hz), 7.80 (s, 1H), 7.74-7.61 (m, 3H); APCI MS m/z 304.0, 302.0 (M+1).
B) 4-[5-(3-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3,5-dichloropyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 146.2, 139.6, 138.7, 137.9, 135.6, 130.8, 129.7, 124.9, 124.8, 124.3, 124.2, 120.6, 60.1, 57.2, 53.1, 50.8, 42.0, 29.7; APCI MS m/z 344.1 (M+1).
Example 13
4-(3-Bromo-phenyl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 1,3-dibromobenzene: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 151.7, 130.6, 123.6, 121.9, 118.6, 114.3, 60.1, 57.5, 53.1, 50.9, 42.2, 29.6; APCI MS m/z 269.0, 267.0 (M+1).
Example 14
5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-nicotinonitrile dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-cyanopyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 145.4, 141.5, 141.4, 123.3, 117.4, 109.9, 59.8, 56.6, 52.8, 50.7, 41.5, 30.1; APCI MS m/z215.1 (M+1).
Example 15
4-(5-Trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-chloro-5-trifluoromethylpyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 145.6, 141.0, 136.0, 135.9, 117.84, 117.81, 59.9, 56.9, 52.9, 50.7, 41.6, 29.9; APCI MS m/z 258.1 (M+1).
Example 16
4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(2-trifluoromethyl-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 2-trifluoromethylphenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.70 (d, 1H, J=2.1 Hz), 8.49 (d, 1H, J=1.7 Hz), 7.82-7.77 (m, 2H), 7.63-7.53 (m, 2H), 7.30 (d, 1H, J=7.5 Hz); APCI MS m/z 304.0, 302.0 (M+1).
B) 4-[5-(2-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane Dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(2-trifluoromethyl-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 145.2, 139.9, 138.1, 137.7, 135.6, 132.2, 131.8, 129.0, 128.3, 126.5, 125.5, 122.9, 59.9, 57.1, 53.0, 50.8, 41.9, 29.4; APCI MS m/z 334.2 (M+1).
Example 17
4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(4-trifluoromethyl-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 4-trifluoromethylphenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.76 (d, 1H, J=1.7 Hz), 8.71 (d, 1H, J=2.1 Hz), 8.04 (t, 1H, J=2.1 Hz), 7.75 (d, 2H, J=8.3 Hz), 7.67 (d, 2H, J=7.9 Hz); APCI MS m/z 304.0, 302.0 (M+1).
B) 4-[5-(4-Trifluoromethyl-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(4-trifluoromethyl-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 146.2, 142.1, 138.7, 138.0, 135.6, 127.8, 126.13, 126.09, 120.7, 60.0, 57.2, 53.0, 50.8, 41.9, 29.6; APCI MS m/z 334.2 (M+1).
Example 18
4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(2-fluoro-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 2-fluorophenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.73 (d, 1H, J=1.7 Hz), 8.67 (d, 1H, J=2.1 Hz), 7.99 (t, 1H, J=2.1 Hz), 7.48-7.42 (m, 1H), 7.34-7.23 (m, 2H), 7.15-7.10 (m, 1H); APCI MS m/z 252.0, 254.0 (M+1).
B) 4-[5-(2-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(2-fluoro-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 164.8, 162.1, 146.2, 141.1, 138.7, 137.7, 135.8, 130.8, 130.7, 123.2, 120.6, 115.1, 114.9, 114.5, 114.3, 60.0, 57.2, 53.0, 50.8, 42.0, 29.6; APCI MS m/z284.3 (M+1).
Example 19
4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(4-fluoro-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 4-fluorophenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.70 (d, 1H, J=1.7 Hz), 8.64 (d, 1H, J=2.5 Hz), 7.97 (t, 1H, J=2.1 Hz), 7.54-7.46 (m, 2H), 7.20-7.14 (m, 2H); APCI MS m/z 252.0, 254.0 (M+1).
B) 4-[5-(4-Fluoro-phenyl)-pyridin-3-yl]-1.4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(4-fluoro-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 164.2, 161.9, 146.1, 138.8, 137.2, 136.1, 134.6, 129.2, 129.1, 120.6, 116.2, 116.0, 60.1, 57.3, 53.0, 50.8, 42.0, 29.6; APCI MS m/z 284.3 (M+1).
Example 20
3-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-quinoline dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromoquinoline: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 145.0, 143.9, 142.8, 129.1, 129.0, 127.2, 126.7, 126.4, 116.7, 60.2, 58.1, 53.0, 50.9, 42.3, 29.0; APCI MS m/z 240.2 (M+1).
Example 21
4-(3-Trifluoromethyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 2-bromo-3-trifluoromethyl-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 158.0, 150.8, 137.82, 137.77, 125.8, 123.0, 115.8, 60.3, 60.0, 53.5, 51.1, 42.9, 30.1; APCI MS m/z 258.2 (M+1).
Example 22
4-(6-Methoxy-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 2-bromo-6-methoxy-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 163.2, 157.8, 140.3, 98.6, 98.2, 59.9, 53.8, 53.3, 53.2, 50.7, 40.1, 31.0; APCI MS m/z 220.2 (M+1).
Example 23
4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(2-methoxy-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 2-methoxyphenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.68 (d, 1H, J=1.7 Hz), 8.60 (d, 1H, J=2.5 Hz), 8.02 (t, 1H, J=2.1 Hz), 7.41-7.37 (m, 1H), 7.31-7.28 (m, 1H), 7.07-6.99 (m, 2H), 3.83 (s, 3H); APCI MS m/z 266.1, 264.1 (M+1).
B) 4-[5-(2-Methoxy-phenyl)-pyridin-3-yl]-1.4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(2-methoxy-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 156.8, 145.6, 141.2, 136.8, 134.3, 130.9, 129.6, 127.8, 123.7, 121.2, 111.5, 60.1, 57.3, 55.8, 53.1, 50.9, 42.1, 29.4; APCI MS m/z 296.2 (M+1).
Example 24
4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(3-methoxy-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 3-methoxyphenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.74 (d, 1H, J=1.7 Hz), 8.68 (d, 1H, J=2.1 Hz), 8.01 (t, 1H, J=2.1 Hz), 7.39 (t, 1H, J=7.9 Hz), 7.14-7.13 (m, 1H), 7.12-7.11 (m, 1H), 7.06-6.95 (m, 1H), 3.86 (s, 3H); APCI MS m/z 266.1, 264.1 (M+1).
B) 4-[5-(3-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(2-methoxy-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 160.2, 146.1, 140.3, 139.1, 137.4, 137.0, 130.2, 120.9, 120.0, 113.4, 60.1, 57.3, 55.6, 53.0, 50.8, 42.0, 29.5; APCI MS m/z 296.2 (M+1).
Example 25
4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-o-tolyl-pyridine
The title compound was prepared by the methods described in Example 12A starting with o-tolyl-boronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.66 (d, 1H, J=2.1 Hz), 8.51 (d, 1H, J=1.7 Hz), 7.82 (t, 1H, J=2.1 Hz), 7.35-7.26 (m, 3H), 7.20-7.18 (m, 1H), 2.28 (s, 3H); APCI MS m/z 250.1, 248.1 (M+1).
B) 4-(5-o-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-o-tolyl-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 145.7, 140.5, 138.8, 137.6, 136.9, 135.9, 130.7, 130.0, 128.2, 126.2, 123.0, 60.1, 57.2, 53.1, 50.8, 42.1, 29.5, 20.6; APCI MS m/z280.3 (M+1).
Example 26
5-(1.4-Diaza-bicyclo[3.2.1]oct-4-yl)-nicotinic acid ethyl ester dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 5-bromo-nicotinic acid ethyl ester: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 166.2, 145.8, 141.8, 140.9, 126.4, 122.4, 61.6, 60.0, 57.1, 53.0, 50.8, 41.8, 29.7, 14.5; APCI MS m/z 262.2 (M+1).
Example 27
4-(5-Chloro-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 2,5-dichloropyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 146.5, 137.4, 108.1, 59.8, 54.0, 53.0, 50.7, 40.1, 31.0; APCI MS m/z 224.1 (M+1).
Example 28
4-(6-Methyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 2-methyl-5-bromopyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 137.9, 123.8, 123.3, 60.0, 57.7, 52.9, 50.8, 42.1, 28.8, 23.5; APCI MS m/z204.2 (M+1).
Example 29
4-[5-(3-Trifluoromethyl-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 2 starting with 3-trifluoromethylphenylboronic acid: (data for the free base) 13 C NMR (CDCl 3 , 100 MHz) δ 158.1, 146.6, 139.5, 136.3, 132.2, 129.6, 129.5, 125.2, 123.6, 123.0, 107.2, 59.8, 54.0, 53.0, 50.7, 39.9, 31.1; APCI MS m/z 334.2 (M+1).
Example 30
4-[5-(4-Chloro-phenyl)-pyridin-2-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 2 starting with 4-chlorophenylboronic acid: (data for the free base) 13 C NMR (CDCl 3 , 100 MHz) δ 146.3, 137.2, 136.2, 133.1, 132.2, 129.3, 129.0, 127.6, 125.2, 107.2, 59.8, 54.0, 53.0, 50.7, 40.0, 31.1; APCI MS m/z300.2 (M+1).
Example 31
4-(5-o-Tolyl-pyridin-2-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 2 starting with 2-methylphenylboronic acid: (data for the free base) 13 C NMR (CDCl 3 , 100 MHz) δ 157.7, 148.1, 138.8, 138.6, 136.0, 130.7, 130.1, 127.5, 127.1, 126.2, 106.6, 59.9, 53.9, 53.2, 50.8, 40.1, 31.1, 20.8; APCI MS m/z280.3 (M+1).
Example 32
4-[5-(3-Chloro-phenyl)-pyridin-2-yl]-1.4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 2 starting with 3-chlorophenylboronic acid: (data for the free base) 13 C NMR (CDCl 3 , 100 MHz) δ 158.2, 146.4, 140.4, 136.3, 135.0, 130.4, 126.9, 126.4, 125.0, 124.4, 107.2, 59.8, 53.8, 53.0, 50.7, 39.9, 31.1; APCI MS m/z 300.2 (M+1).
Example 33
4-[5-(3-Fluoro-phenyl)-pyridin-2-yl]-1.4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 2 starting with 3-fluorophenylboronic acid: (data for the free base) 13 C NMR (CDCl 3 , 100 MHz) δ 164.7, 158.3, 146.4, 140.84, 140.77, 136.2, 130.64, 130.56, 125.0, 121.9, 113.8, 113.6, 113.2, 113.0, 107.1, 59.8, 53.8, 53.1, 50.7, 40.0, 31.2; APCI MS m/z284.2 (M+1).
Example 34
4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1.4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(4-chloro-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 4-chlorophenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.72 (d, 1H, J=2.1 Hz), 8.66 (d, 1H, J=2.1 Hz), 8.00 (t, 1H, J=2.1 Hz), 7.51-7.44 (m, 4H); APCI MS m/z 270.0, 268.0 (M+1).
B) 4-[5-(4-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane Dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(4-chloro-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 146.0, 138.8, 137.5, 137.1, 135.8, 134.4, 129.4, 128.7, 120.6, 60.0, 57.3, 53.0, 50.8, 41.9, 29.5; APCI MS m/z 300.2 (M+1).
Example 35
4-[5-(2.4-Dichloro-phenyl)-pyridin-3-yl]-1.4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(2,4-dichloro-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 2,4-dichlorophenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.70, (d, 1H, J=2.5 Hz), 8.57 (d, 1H, J=1.7 Hz), 7.92 (t, 1H, J=2.1 Hz), 7.53 (d, 1H, J=2.1 Hz), 7.35 (dd, 1H, J=8.3, 2.1 Hz), 7.26 (d, 1H, J=8.3 Hz); APCI MS m/z 308.0, 306.0, 304.0, 302.0 (M+1).
B) 4-[5-(2.4-Dichloro-phenyl)-pyridin-3-yl]-1.4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(2,4-dichloro-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 145.3, 140.4, 137.8, 136.2, 135.0, 134.2, 133.8, 132.2, 130.2, 127.6, 123.2, 59.9, 57.2, 52.9, 50.7, 41.9, 29.4; APCI MS m/z 336.2, 334.1 (M+1).
Example 36
4-[5-(3-chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(3-chloro-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 3-chlorophenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.73, (d, 1H, J=2.1 Hz), 8.68 (d, 1H, J=2.5 Hz), 8.00 (t, 1H, J=2.1 Hz), 7.54 (t, 1H, J=1.7 Hz), 7.45-7.41 (m, 3H); APCI MS m/z 270.0, 268.0 (M+1).
B) 4-[5-(3-Chloro-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(3-chloro-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 146.1, 140.5, 138.8, 137.7, 135.7, 135.1, 130.4, 128.3, 127.6, 125.7, 120.7, 60.0, 57.3, 52.9, 50.8, 41.9, 29.5; APCI MS m/z 302.2, 300.2 (M+1).
Example 37
4-(5-D-Tolyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(D-tolyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with p-tolylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.72 (d, 1H, J=2.1 Hz), 8.60 (d, 1H, J=2.1 Hz), 7.96 (t, 1H, J=2.1 Hz), 7.42 (d, 2H, J=8.3 Hz), 7.26 (d, 2H, J=7.9 Hz), 2.39 (s, 3H); APCI MS m/z250.1, 248.1 (M+1).
B) 4-[5-(p-Tolyl-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane Dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(p-tolyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 146.1, 139.0, 138.1, 137.0, 136.9, 135.7, 129.9, 127.3, 120.7, 60.1, 57.3, 53.1, 50.8, 42.0, 29.5, 21.4; APCI MS m/z 280.3 (M+1).
Example 38
4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
A) 3-Bromo-5-(4-methoxy-phenyl)-pyridine
The title compound was prepared by the methods described in Example 12A starting with 4-methoxyphenylboronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.72 (d, 1H, J=2.1 Hz), 8.60 (d, 1H, J=2.1 Hz), 8.00 (t, 1H, J=2.1 Hz), 7.50 (d, 2H, J=8.7 Hz), 7.01 (d, 2H, J=8.7 Hz), 3.86 (s, 3H); APCI MS m/z 266.1, 264.1 (M+1).
B) 4-[5-(4-Methoxy-phenyl)-pyridin-3-yl]-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-(4-methoxy-phenyl)-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 159.9, 146.1, 138.9, 136.8, 136.6, 131.0, 128.5, 120.5, 114.6, 60.1, 57.3, 55.6, 53.0, 50.8, 42.0, 29.5; APCI MS m/z 296.3 (M+1).
Example 39
4-(5-Methoxy-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-bromo-5-methoxypyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 156.4, 147.0, 131.5, 127.1, 108.3, 59.9, 57.4, 55.8, 52.9, 50.7, 41.9, 29.4; APCI MS m/z 220.3 (M+1).
Example 40
5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-[3.4′]bipyridinyl dihydrochloride
A) 5-Bromo-[3,4′]bipyridinyl
The title compound was prepared by the methods described in Example 12A starting with pyridine-4-boronic acid: 1 H NMR (CDCl 3 , 400 MHz) δ 8.80 (d, 1H, J=2.1 Hz), 8.75-8.73 (m, 3H), 8.07 (t, 1H, J=2.1 Hz), 7.52-7.50 (m, 2H), 2.71 (br s, 1H); APCI MS m/z 237.1, 235.1 (M+1).
B) 5-(1,4-Diaza-bicyclo[3.2.1]oct-4-yl)-[3.4′]bipyridinyl dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 5-bromo-[3,4′]bipyridinyl: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 150.6, 146.2, 146.1, 138.7, 138.4, 134.1, 122.0, 120.2, 60.0, 57.2, 52.9, 50.8, 41.8, 29.6; APCI MS m/z267.3 (M+1).
Example 41
4-(2-Methyl-5-trifluoromethyl-pyridin-3-yl)-1,4-diaza-bicyclo[3.2.1]octane dihydrochloride
The title compound was prepared by the methods described in Example 1E starting with 3-chloro-2-methyl-5-trifluoromethyl-pyridine: (data for free base) 13 C NMR (CDCl 3 , 100 MHz) δ 158.0, 146.2, 139.0, 138.9, 125.3, 124.7, 124.4, 122.1, 122.0, 60.7, 59.8, 53.1, 51.1, 43.2, 28.0, 22.5; APCI MS m/z 272.3 (M+1). | The present invention relates to a compounds of formula I:
wherein A, B, D, E and F are defined herein; that are useful in treating central nervous system (CNS) diseases, disorders and conditions, such as but not limited to nicotine addiction, schizophrenia, depression, Alzheimer's disease, Parkinson's disease and ADHD. The present invention further comprises pharmaceutical compositions containing such compounds and methods of treatment comprising the use of such compounds. | 2 |
CROSS REFERENCE
[0001] This application is a continuation of U.S. Ser. No. 11/313,554, filed Dec. 20, 2005 entitled: “METHODS AND APPARATUS FOR CONDITIONING AND DEGASSING LIQUIDS AND GASES IN SUSPENSION”, incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to methods and apparatus for conditioning mixtures of gas and liquids by agglomerating gas bubbles existing with or in a liquid or for coalescing droplets of liquid dispersed in another liquid.
BACKGROUND OF THE INVENTION
[0003] Liquids produced in oilfield applications comprise a hydrocarbon component, (which may be a low density oil, termed condensate, or a medium density oil, termed medium oil, or a high density oil, termed heavy oil) and some accompanying water which may be naturally occurring with the oil or may have been pumped into the reservoir to help drive out the oil. In order to process the oil successfully, the water must be separated out allowing relatively dry oil to be exported. In turn the water itself must be treated to an acceptable content of oil suitable for disposal.
[0004] Separation of water from a predominantly oil stream or treatment of a water stream to remove oil is generally more difficult and expensive as the droplet size of the dispersed, minority phase decreases. In many cases, there is a need to increase droplet size to improve separation or reduce costs of separation.
[0005] In most oilfield applications there is a need to remove gas from the liquid phase. This may be in the form of foam which needs to be broken down, discrete gas bubbles in a liquid which are required to be removed as part of a separation process, or dissolved gas which needs to be evolved from solution as discrete bubbles and removed as part of the separation process. Foaming is deleterious to the separation function since it may, for example, fill process equipment. It is commonly suppressed by the continuous use of additive chemicals. Furthermore, foaming can lead to false readings on apparatus such as level detectors in vessels. Therefore it is desirable to break down foam as quickly and cheaply as possible without the use of chemicals.
[0006] US Statutory Invention Registration No. H1568 discloses a coalescer which proposes the application of a standing wave ultrasonic field with a frequency range between 20 kHz and 1 MHz, with 680 kHz disclosed as an optimum frequency, for wastewater. The standing wave is created using at least two radially opposed pairs of transducers to cause coalescence of oil droplets in a flowing wastewater stream, with subsequent separation in conventional separators. The wastewater flows through a circular section vessel and the preferred embodiment includes seven pairs of transducers in groups at particular positions axially along and external to the treatment vessel. Intensity of application of acoustic energy is below cavitation levels.
[0007] However, the applicant's research has shown that the configuration disclosed in this document is unlikely to succeed as the fluid velocities typically encountered in pipe-flow are too high and the flow is too turbulent for the ultrasonic forces to be effective. Also the residence in the field of the transducers is too short.
[0008] U.S. Pat. No. 5,527,460 described a multi-layered composite resonator system using a plane transducer and an opposing and parallel plane mirror for separating particles suspended in a fluid on a small scale. The technique uses an ultrasonic resonant wave.
[0009] Other prior art solutions include the use of electrostatic treatments which aim to use forces created by the interaction of electrically charged bodies to cause coalescence. For oil-from-water separation, filter-coalescers are commonly used to grow drop size by means of interference coalescence such as meshes or packing. Such techniques, in the case of electrostatic coalescers are not effective on water continuous-mixtures, or in the case of filter coalescers have limitations due to the likelihood of blockage.
[0010] U.S. Pat. No. 6,210,470 describes apparatus for degassing a moving liquid. The apparatus uses a transducer and reflector arrangement to produce ultrasonic standing waves which are inclined at an acute angle to a horizontal axis of liquid flow.
[0011] The techniques described below act to coalesce the dispersed droplets into larger droplets thereby improving the downstream separation efficiency and/or reducing the cost of downstream separation. In another embodiment the techniques described below are used to breakdown foam or promote the separation of suspended or dissolved gas, which also improves separation and/or reduces the costs of downstream separation.
SUMMARY OF THE INVENTION
[0012] The present invention generally relates to a method and apparatus for the controlled application of ultrasonic energy for conditioning of mixtures of gas and liquids by evolving and/or agglomerating gas bubbles existing with or in a liquid or for coalescing droplets of liquid dispersed in another liquid.
[0013] In a first aspect of the invention, there is provided coalescing apparatus for increasing the droplet size of a mixture formed as a liquid dispersed in another liquid comprising an ultrasonic transducer arranged to impart vibrational energy preferably in the frequency range 200 kHz to 1.5 MHz and more particularly in the range 400 kHz-1.5 MHz, to the mixture and a reflector located generally opposite the transducer, the apparatus further including at least one baffle extending in a direction generally between the transducer and the reflector and which divides the space between the transducer and reflector into separate volumes, the baffles being arranged in use to be sufficiently rigid to generally prevent substantial fluid flow between the volumes.
[0014] This provides the controlled application of ultrasonic energy in the form preferably of a resonant standing wave to generate coalescence in a dispersion (which may be static or flowing) of one liquid in another where separation of the liquid phases is a process objective. Differences in acoustic properties between the liquids allows the imposed acoustic radiation force to drive the droplets to the nodes or antinodes of the standing wave, thereby increasing local concentrations of the dispersion and the chances of droplet interaction. The coalescence this achieves provides a basis for improved performance of downstream separators, the efficiencies of which are generally strongly dependent on drop size.
[0015] Thus the ultrasonic energy is used for coalescing droplets of one liquid dispersed in another liquid where the liquids have differing acoustic properties. This is particularly, applicable when the liquids constitute an oil phase and a water phase.
[0016] In a second aspect of the invention there is provided de-gassing apparatus arranged to evolve and/or agglomerate gaseous bubbles in a gas/liquid mixture comprising a transducer arranged to impart vibrational energy to the mixture and a reflector located generally opposite the transducer, the transducer being arranged to impart vibrational energy in the frequency range 200 kHz to 3 MHz and more particularly in the range 20 kHz to 800 kHz. In this case, the ultrasonic energy is used for evolving and/or agglomerating gas bubbles (foam) developed in or with liquids. More particularly, when the gas is hydrocarbon gas and the liquids are hydrocarbon liquids and or water. Most particularly when the gas and liquids result from the activities of production, transport and storage of natural gas and crude oil.
[0017] In a further aspect, the invention provides a cell comprising a transducer couplable to drive electronics, a reflector and at least one baffle extending between the transducer and the reflector and dividing the space between the transducer and reflector into separate volumes, the baffles being arranged in use to be sufficiently rigid to generally prevent vibration passing between the volumes.
[0018] Preferably a plurality of such cells may be arranged to be generally co-planar in a matrix or honeycomb configuration in order to condition a larger volume of material over time than a single cell.
[0019] Optionally, a plurality of such cells may be arranged in series along a pipe, the pipe being arranged to carry a flow of material to be conditioned.
[0020] In a method aspect, the invention provides a method of increasing droplet size of a liquid dispersed in another liquid comprising passing vibrational energy through the liquid in a plurality of volumes defined by at least one baffle extending between a transducer and a reflector.
[0021] In a further method aspect, the invention provides evolving and/or agglomeration of bubbles of gaseous material dispersed in liquid by passing vibrational energy through the liquid in a plurality of volumes defined by at least one baffle extending between a transducer and a reflector.
[0022] Although techniques are described below in connection with separation of a dispersed oil phase in a continuous water phase, it will be understood that they have general application in the treatment of any liquid dispersed in another liquid, and/or any liquid containing dissolved or dispersed gas.
[0023] Preferred embodiments of the invention will now be described with reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is a schematic cross-section of a generally square section vessel with apparatus in accordance with the invention applied to the external surface thereof;
[0025] FIG. 2 is a schematic cross-section of a generally square section vessel with apparatus generally in accordance with the invention contained internally;
[0026] FIG. 3 is a schematic cross-section of a generally circular section vessel with apparatus in accordance with the invention contained therein;
[0027] FIG. 4 is a schematic cross-section of a generally circular section vessel with apparatus in accordance with the invention applied to the external surface;
[0028] FIG. 5 is a schematic cross-section of a generally circular section vessel showing apparatus in accordance with the invention contained therein; and
[0029] FIG. 6 is a schematic cross-section of a generally circular vessel with a matrix of cells in accordance with the invention contained therein.
DETAILED DESCRIPTION
[0030] With reference to FIG. 1 , a generally square section vessel 2 has a transducer 4 mounted along one side and a reflector 6 mounted on the opposite side of the vessel 2 . The transducer 4 is typically formed as a piezoelectric layer 5 which converts an oscillating electrical voltage applied across the layer into a corresponding mechanical vibration, with an optional carrier 8 . Typically, the layer 5 is made from a piezoceramic material.
[0031] The transducer 4 is optionally coupled to the vessel 2 by a carrier 8 which effectively provides impedance matching between the transducer and the vessel wall. The carrier 8 represents an electrically insulative layer which isolates the piezoceramic layer 5 from the liquid. Its thickness and acoustic impedance are important for achieving efficient transmission of acoustic energy into the vessel 2 . However, in some applications and including the other embodiments described below, the transducer 4 may be mounted directly to the wall of the vessel 2 and the carrier 8 may be omitted. Similarly, the reflector 6 may also be omitted in some applications.
[0032] In use, the transducer 4 is electrically coupled to a drive circuit (not shown) which is operable to cause the transducer to vibrate at ultrasonic frequencies (typically in the range 200 kHz to 1.5 MHz and optionally in the range 400 kHz to 1.5 MHz for coalescing operation or 20 kHz to 800 kHz for defoaming/degassing operation. The transducer 4 may, for example, be made from a piezoceramic material which changes dimension with the application of voltage across the material.
[0033] In the space generally marked 10 , fluid is contained. In a preferred embodiment, the fluid flows between the transducer 4 and the reflector 6 in a plane into or out of the drawing sheet. Also, the transducer and reflector are generally co-extensive into and/or out of the plane of the sheet. Thus fluid flowing through the apparatus spends a period of time flowing between the reflector and transducer (the period depending on the flow rate of the liquid and the length of extension of the transducer and reflector).
[0034] In coalescer operation, as ultrasonic energy is passed through the liquid, if standing waves are set up within the vessel 2 , material of different densities within the liquid tend to separate and material gathers at the nodes or antinodes of the standing wave which is created. In the case of oil dispersed in water, typically oil droplets begin to coalesce at the pressure antinodes of the standing waves. These coalesced droplets may then more readily be separated using conventional apparatus downstream of the ultrasonic coalescing portion of the vessel.
[0035] Thus the vessel may, for example, be a pipe and advantageously may be retro-fitted with the transducer 4 , carrier 8 and reflector 6 . Alternatively, a single transducer may be used in which case the pipe wall may act as both carrier and reflector. Also, a transducer may act as a reflector. Thus any combination of these components (carrier, transducer and reflector) may be used in appropriate circumstances; the minimum configuration being an unmounted transducer 5 . The components may be duplicated , for example, by placing a plurality of transducers, carrier and reflectors in a direction extending into the plane of the figure. This allows the units to have a cumulative effect as fluid flows along the pipe. Different units may also be tuned differently (by adjusting power, transducer/reflector characteristics and/or frequency) to take account of differing average droplet sizes along the length of the pipe.
[0036] Typically the distance between the transducer and reflector is of the order of 10 to 100 mm for droplet coalescence, and may be up to 250 mm or more for defoaming/degassing applications. This has been found to give good results in the frequency range mentioned above, with fine dispersions of water in oil or oil in water having dispersion droplets of the order of 1 to 100 μm and at flow rates of tens of m 3 /hr at velocities in the range 0.01 to 0.2 m/s.
[0037] Preferably, the frequency of the transducer operation is automatically controlled to keep the whole system at resonance (which will generally provide standing waves). Input power levels are preferably kept as high as possible; the limiting factor being cavitation within the liquid and/or acoustic streaming which causes turbulence and results in turbulent mixing of the fluid. Typically, following coalescence or defoaming, the fluid is passed through a separator. The output quality of the oil or water stream may be monitored downstream of the separator and the results may be used to produce a feedback signal to adjust the operating parameters of the transducer.
[0038] Generally, increased power levels are desirable since this produces a stronger coalescing or de-foaming/degassing effect. By providing baffles 12 which divide the area of the vessel 2 into a matrix of smaller channels, the point at which acoustic streaming occurs with increasing ultrasonic power put into the fluid, may be deferred. Thus higher power intensities may be applied to the fluid using baffles of the type shown in FIG. 1 .
[0039] Streaming typically is a function of non-linearities in power emission over the surface of the transducer. Without constraint this can lead to acoustically driven turbulence which may disrupt the coalescing effect. The constraint offered by baffles tends to delay the onset of streaming and ensures that if it occurs it does so only in localised areas.
[0040] The dimensions of the channels formed by the baffles has been found to be most effective when the distance L between the carrier 8 and reflector 6 is greater than the width W of the channel defined between the baffles 12 .
[0041] With reference to FIG. 2 , an alternative approach is to insert a cell 20 having baffles 12 ′, a transducer 4 ′,and reflector 6 ′ contained within a vessel 22 . Preferably, the area between the cell 20 and the inner surface of the vessel 22 is made substantially fluid tight (although some leaks may be permitted) to force flowing fluid through the cell 20 . An alternative is to carry out conditioning in a batch process whereby a body of liquid is let into the vessel, the vessel is closed, the apparatus is activated and subsequently the vessel is opened to release liquid having larger droplet sizes for the dispersed phase.
[0042] FIG. 3 shows an alternative embodiment in which a cell 20 is contained within a generally circular section vessel 24 . In other respects, the cell 20 may be similar to that of FIG. 2 .
[0043] FIG. 4 shows the application of the technique to a circular section vessel 30 . In this case, the vessel 30 is surrounded by carrier material 32 which acts both as carrier and reflector (as in the case of the earlier embodiments in which the same material may be used).
[0044] A curved or flat transducer 34 is mounted to the outside of the carrier 32 . Baffles 36 preferably form smaller channels as discussed above and extend generally away from the transducer 34 towards the opposite side of the vessel 30 . This embodiment may readily be retro-fitted to an existing pipe arrangement.
[0045] FIG. 5 shows an alternative embodiment for dealing with circular section vessels. In this case, a vessel 40 has a generally axial transducer 42 mounted centrally therein. An optional carrier 44 surrounds the transducer 42 and a reflector 46 surrounds the outer surface of the vessel 40 . Radial baffles 48 improve the power absorption characteristics of the fluid in the way described above.
[0046] FIG. 6 shows a technique for dealing with large section vessels or pipes. The drawing shows a circular section vessel 50 although it will be appreciated that the vessel may be any section. Presently, the size of the cell 20 ( FIG. 2 ) has been found to have a limited maximum size. This is due, for example, to losses in the liquid (and the above mentioned limitation on the amount of power which may be put into the liquid before cavitation/streaming occurs) and non-linearities in the transducers particularly at high driving levels. Nevertheless, for situations in which the vessel cross-section is very much larger than a maximum desired size of cell 20 , the cells may simply be placed into a generally co-planer matrix or honeycomb form as shown in FIG. 6 . In this way, no liquid bottleneck is caused and yet the performance of the individual cells is unaffected. It will be appreciated that the matrix may be formed in any shape and need not be a 9×9 matrix as shown here.
[0047] Similarly, it will be appreciated that several cells could be placed in series. Alternative embodiments may include apparatus mounted at the oil interfaces in an existing separator in order to increase the rate of resolution of and to promote separation at the interface and provide a more sharply defined interface between liquids such as oil and water or at a gas/liquid interface. Thus it will be appreciated that the use of the apparatus may conveniently be targeted at problem areas in existing process equipment.
[0048] Other adjustments include operating the apparatus for longer periods of time at lower powers (which achieves the same result although slower) and using alternative materials for the transducer such as magneto-restrictive materials (which typically have lower operating frequencies of the order of 100 KHz or less). In the case of the embodiments of FIGS. 2 and 3 , it will be noted that the space between the outside of the cell 20 and the internal surface of the vessels ( 22 and 24 respectively) typically would be pressurised to the same pressure as the liquid flowing through the cell 20 . In oil processes, the pressure within the cell may be of the order of 10 bar or higher. Using a fluid connection from the internal area of the cell via a suitable isolating diaphragm, clean generally non-compressible, material such as transformer oil, may be used to pressurize the reverse side of the cell 20 (i.e. the area between the cell outer surface and the cell inner surface). Alternatively, process liquid may be allowed into the area behind the cell. This not only helps to prevent damage to the cell from loads caused by excessive pressure differentials but may also provide an insulating medium to facilitate electrical connection to the transducer(s) and to ensure that all process liquid is treated. | A method and apparatus are provided for the controlled application of ultrasonic energy for conditioning of mixtures of gas and liquids by evolving and/or agglomerating gas bubbles existing with or in a liquid or for coalescing droplets of liquid dispersed in another liquid. The invention in preferred embodiments thereof comprises a coalescing apparatus for increasing the droplet size of a mixture formed as a liquid dispersed in another liquid, and a de-gassing apparatus arranged to evolve and/or agglomerate gaseous bubbles in a gas/liquid mixture. In the apparatuses, ultrasonic transducers are used to impart vibrational energy to the mixtures. | 2 |
This is a continuation in part of U.S. patent application Ser. No. 10/602,198 filed Jun. 24, 2003, now abandoned which in turn claims the benefit of U.S. Provisional Patent Application Ser. No. 60/391,333, filed Jun. 25, 2002, each of which is hereby incorporated by reference entirely.
BACKGROUND OF THE INVENTION
This invention relates to masonry veneer or cavity wall construction and, more particularly, to devices used in association with window and door installations in a veneer/cavity wall system for proper transition between the window or door installation and the masonry veneer.
Wall systems having a masonry exterior are typically constructed of at least one vertical layer of masonry and at least a second vertical layer of a material forming a back-up system. The back-up system may be constructed of lumber, light gauge steel studs or of a concrete masonry unit. The masonry and back-up system are typically bonded together by horizontal metallic ties spaced apart vertically. A space is often provided in such wall systems (e.g., cavity wall systems) between the masonry and back-up system for moisture drainage. Normally, a 1 to 2 inch air space between the masonry and back-up system is adequate to provide drainage. Insulation may also be placed in the space to improve the energy efficiency of masonry buildings.
Masonry veneer, and cavity wall construction in general, has many advantages and is commonly utilized in residential and commercial construction. Problems often arise during construction, however, in maintaining a proper transition between the wall structure and window, door and other openings or discontinuities in the wall. For example, the dimensioning of the window or door frame installed in the wall is frequently different and incompatible with the thickness, geometry and dimensions of the masonry veneer or cavity wall construction. Caulk is often used along the wall jamb and header in an effort to provide a water tight seal and aesthetic transition to the window or door frame.
One example of a window or door frame is called a J-channel frame which has an outwardly directed open channel along the jamb portions of the frame. The J-channel frame is specifically designed for use on siding clad exterior walls and not masonry exterior walls. The often rough cut ends of the siding are inserted into and concealed within the channel of the frame to present a neat and finished appearance at the transition from the wall to the frame. Nevertheless, the J-channel frame is often used with masonry walls for a variety of reasons. In such cases, the channel is vacant and must be flashed for a proper installation and must receive a backer material for the effective placement of caulking and sealant.
However, due to the incompatibility of the J-channel frame with the masonry veneer, effective and aesthetic caulk application is nearly impossible. As a result, the detailing and finishing work required for proper installation of a window or door into a masonry veneer or cavity wall construction is typically very labor intensive, non-uniform and highly dependent upon the skill and experience of the particular contractor or tradesman performing the installation particularly when a J-channel is used. Because of the importance and wide spread popularity of such masonry structures, a better method for proper and consistent installation of windows and doors in such construction is needed.
SUMMARY OF THE INVENTION
This invention provides a solution to these and other problems in the art and allows an efficient and reliable installation for a water tight and an aesthetically pleasing transition from surrounding the window or door to the masonry veneer. Generally, in one embodiment this invention includes a backer unit or finishing member installed adjacent the J-channel window frame or door frame to provide a proper transition from the frame to the masonry wall structure. In one embodiment, the finishing member has a generally L-shaped configuration with a first leg of the member being mounted in the cavity defined by the channel of the J-channel frame. The second leg of the finishing member projects generally perpendicularly from the first leg and between the forward edge of the window or door J-channel frame and the masonry outer wall. In one embodiment, the first leg is frangibly joined to the second leg by a perforated joint for selective separation of the second leg from the first leg.
After the finishing member is installed adjacent to the frame and the inner and outer wall construction is complete, the terminal end portion of the second leg is removed by being torn along the frangible joint. After the terminal end portion is removed, a recess is exposed at a juncture with the frame and the remainder of the finishing member. A bead of caulk or similar finishing material is applied in the recess to provide a smooth and aesthetically pleasing transition from the J-channel frame to the masonry wall. Additionally, the juncture between the frame and the wall is sealed by the caulk bead to inhibit and/or prevent the entry of moisture or other foreign material and the void in the J-channel is substantially filled.
Advantageously, the finishing member is readily adaptable for use with a wide variety of window and door J-channel or other frame designs and construction specifications without requiring highly skilled or specialized installation and construction techniques.
BRIEF DESCRIPTION OF THE DRAWINGS
The objectives and features of the invention will become more readily apparent from the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is an exemplary view of a window installation in a masonry wall;
FIG. 2 is a perspective cross sectional view taken along line 2 - 2 in FIG. 1 of a transition between the wall jamb and a J-channel window frame according to one embodiment of this invention;
FIG. 3 is a cross sectional plan view taken along line 2 - 2 of FIG. 1 showing the transition between the wall jamb and window frame shown in FIG. 2 ; and
FIG. 4 is a perspective view of a finishing member according to one embodiment of this invention adapted to be used in the frame of FIGS. 1-3 .
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1 , an exemplary window installation 10 in a masonry wall 12 is shown. The window installation 10 includes a perimeter window frame 14 , one or more window panes 16 , and a window opening 18 in the wall defined by a pair of jambs 20 and a header 22 above and a sill 24 below the window frame 14 . Although one example of a window installation is shown in FIG. 1 , this invention is readily applicable for a variety of closure elements in openings in the wall such as other types of window installations, frame designs, doors and the like.
As shown more clearly in FIGS. 2-3 , the masonry wall 12 for the exterior of a building, in one embodiment, is comprised of an outer wall of masonry or brick veneer 26 and an insulated interior wall 28 . The brick veneer outer wall 26 is constructed from a plurality of bricks or blocks 30 arranged in a vertical pattern. Each brick 30 is of a substantially rectangular shape having a uniform length, height and depth. The brick veneer 26 is built up by placing one layer of bricks 30 over another layer, with the upper layer vertically offset from the lower layer by a distance of approximately one-half the length of a brick 30 . Thus, as shown in FIG. 1 , a brick 30 on one layer is positioned directly over the space between two bricks 30 on the layer immediately beneath it. The spaces between adjacent bricks 30 and between adjacent layers of bricks are filled with mortar 32 . Alternatively, the veneer 26 may be stone or other masonry components.
The interior wall 28 includes wood framing studs 34 , dry wall 36 , and outer sheathing material 38 . Other materials may be used as is well known in the art. For example, a liner board (not shown) as disclosed in U.S. patent application Ser. No. 10/417,761 filed Apr. 17, 2003 and hereby incorporated by reference, may be used on the outer sheathing material 38 . In any event, the building wall 12 is constructed so that there is a small cavity or airspace A between the back side of the brick veneer 26 and the outer surface of the interior wall 28 . The airspace A between the back side of the brick veneer 26 and the surface of the interior wall 28 is usually at least about one to two inches deep, although the exact dimension may vary depending upon the nature of the construction.
Referring to FIGS. 2-4 , a first embodiment of a finishing member 40 is shown installed in the installation 10 to provide a proper transition from the window frame 14 to the wall 12 . The member 40 is installed along the jambs 20 of the window opening 18 in cooperation with the corresponding portions of the window frame 14 . As shown in FIGS. 2 and 3 , a nailing flange 46 is typically provided from the portion of the window frame 14 adjacent the jamb 20 and extending to the outer surface of the inner wall 28 . Nails or other mechanical fasteners (not shown) are inserted through the nailing flange 46 into the sheathing material 38 , thereby securing the window frame 14 in position.
The cross-sectional configuration of the J-channel frame 14 includes an outwardly directed open channel 48 joined to the proximal end of the nailing flange 46 along the jamb portion. As previously stated, the J-channel frame 14 and the outwardly open channel 48 are typically intended for use with siding clad walls in which the rough cut edges of the siding are inserted into the open channel 48 and concealed therein for a finished and aesthetically pleasing appearance to the installation. Nevertheless, commonly the J-channel frame design is utilized with masonry walls 12 and previously the channel 48 was improperly flashed or sealed or not filled at all.
The channel 48 is generally U-shaped in which a bight portion 50 of the channel 48 separates a pair of channel side walls 52 , 54 . A forwardmost surface 56 of the J-channel frame 14 is separated from the adjacent channel side wall 54 by a connecting leg 58 of the frame 14 as shown in FIGS. 2-3 .
In one embodiment, the finishing member 40 is generally L-shaped, in which a first leg 42 of the member 40 is inserted into the channel 48 of the frame 14 , and a second leg 44 of the member 40 projects generally perpendicular to the plane of the wall 12 and is juxtaposed to the outer wall or veneer 26 at the window opening 18 to provide a transition from the window frame 14 to the wall 12 . Commonly, a standard backer rod is used to fill a gap between a frame and the wall 12 and provide a surface on which caulk or other sealant can be applied to provide a sealed transition between the standard frame and the wall 12 . However, the gap and spacing between the J-channel frame 14 and the wall 12 is significantly larger, deeper (on the order of ⅛ to ¼ inch or greater) and of a geometry that is not compatible for standard backer rod materials. The standard backer rod materials would not be secure in the gap nor provide a stable backing for the application of the caulk or sealant. Therefore, a proper transition from the window frame 14 to the wall 12 that is effectively sealed against wind, rain, and other elements as well as aesthetically pleasing is often difficult if not impossible. The wide variety, sizes and configurations of window frames 14 available from various manufacturers increases the complexity and difficulty with providing a proper transition from the window frame 14 to the wall 12 . Nevertheless, the finishing member 40 of this invention provides a solution.
The finishing member 40 also allows for expansion and contraction of the window frame 14 relative to the wall 12 during a variety of climatic conditions. In one embodiment, the member 40 is made of closed cell foam and bends, contracts, expands or deflects to accommodate of the wall 12 relative to the frame 14 . In combination with the beads of caulk as appropriate, the finishing member 40 of this invention serves as a backer material and provides for a durable, reliable, easily installed and sealed transition from the window frame 14 to the wall 12 . In certain other embodiments, the member 40 is extruded from a variety of thermoplastic or other polymeric materials. Alternatively, the member 40 may be aluminum or other materials resistant to rust and weather.
In one embodiment of the invention, the leg 42 of the member 40 is approximately ⅞″ in length and ⅝″ thick; whereas the leg 44 is approximately ⅝″ in length and ¼″ thick, although other dimensions of the member 40 are possible within this invention as compatible with the frame 14 configurations and sizes.
Referring to FIG. 4 , a perspective view of the finishing member 40 , according to this invention, is shown. In this embodiment, the member 40 is generally L-shaped in which the first leg 42 is adapted to mount to the frame 14 and be inserted in the channel 48 , and the second leg 44 of the member 40 projects generally perpendicular to provide a transition from the frame 14 to the wall 12 . The second leg 44 is constructed of closed cell foam and includes a terminal end portion 60 joined to a remainder of the member 40 by a frangible connection 62 such as a series of perforations to provide for the convenient and easy removal of the terminal end portion 60 . The second leg 44 may include multiple spaced connections 62 for use with a variety of configurations.
During installation of the finishing member 40 and in construction of the cavity wall 12 , the inner wall 28 is constructed with an opening 18 for the window, door or other installation. The frame 14 , is inserted into the opening 18 and the member 40 is mounted to the channel of the frame 14 as previously described. The outer veneer wall 26 is constructed with courses of masonry units 30 and mortar 32 . After construction of the outer veneer wall 26 is completed, the terminal end portion 60 of the second leg 44 may be removed along the frangible connection 62 thereby exposing a recess at the juncture between the frame 14 , the remainder of the member 40 and the wall 12 . As shown in FIG. 3 , the recess may be filled with a bead of caulk 64 to provide an aesthetically pleasing transition from the frame 14 to the wall 12 , as well as sealing the juncture between the frame 14 and the wall 12 .
From the above disclosure of the general principles of the present invention and the preceding detailed description of at least one preferred embodiment, those skilled in the art will readily comprehend the various modifications to which this invention is susceptible. Therefore, I desire to be limited only by the scope of the following claims and equivalents thereof. | A finishing member for masonry walls allows for simple installation and accurate placement of caulking around windows and doors in cavity wall construction. This invention accommodates a wide variety of window or door frame profiles, particularly those having an outwardly directed channel such as so called J-channel frames, for the detailing and finishing work required for proper installation of a window or door into a masonry veneer or cavity wall construction without requiring a highly skilled and labor intensive installation. | 4 |
FIELD OF THE INVENTION
The present invention relates to plants for treating at least one fluid, of the type comprising at least one mass of particulate material through which the fluid flows in a main direction.
BACKGROUND OF THE INVENTION
Plants of this type find many applications in the technical field, using particulate materials such as catalysts and/or adsorbents. In most of these applications, achieving the optimum performance depends on good control of the flows of the fluid through the mass of adsorbent.
SUMMARY OF THE INVENTION
The object of the present invention is to propose an improved fluid treatment plant that simply, inexpensively and effectively channels the fluid flow lines in boundary regions of the mass of particulate material without disorganizing this mass or its arrangement in a container.
To do this, according to one characteristic of the invention, the plant includes, in the vicinity of at least one boundary region of the mass of particulate material, at least one deflecting surface extending so as to project into the mass from a wall bounding the mass, the deflecting surface making an angle with the main direction in order locally to divert the flow of the fluid in the mass and making with a horizontal plane an angle (a) greater than the angle of repose of the particulate material.
A further object of the present invention is the use of a plant as above for the separation of at least one constituent of a gas mixture, for example the drying or purification of a gas and/or the separation of at least one constituent of a gas mixture, for example the purification of a flow of air to be distilled or the production of oxygen and/or nitrogen from a flow of air.
BRIEF DESCRIPTION OF THE DRAWINGS
Further characteristics and advantages of the present invention will emerge from the following description of embodiments, given by way of illustration but in no way implying limitation, in conjunction with the appended drawings in which:
FIG. 1 is a diagrammatic sectional view of a first embodiment of a plant according to the invention in which the fluid flows vertically;
FIG. 2 is a partial diagrammatic sectional view of a second embodiment of a plant according to the invention, in which the fluid flows horizontally;
FIG. 3 is a partial sectional view similar to that in FIG. 2, showing an alternative embodiment; and
FIG. 4 is a vertical sectional view of a third embodiment of a plant according to the invention with an annular bed of particulate material.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows the outline of a vertical container 1, typically one which is axisymmetric, containing at least one mass 2 of particulate material, for example an adsorbent, for the purification or separation of a gas mixture, resting on a perforated bottom partition. According to the invention, in order to cause local lengthening of the path travelled by the fluid along the walls of the peripheral shell 3 of the container 1, and to force the fluid to encounter a larger number of particles of material at this point, deflecting surfaces 4 are attached to the shell 3 at regular intervals, these deflecting surfaces extending over a short distance upwards and inwards into the container and making an angle a with the horizontal greater than the angle of repose of the particulate material poured onto a receiving support, thus avoiding the formation of a cavity with a free slope in the particulate material under the said surface. The deflecting surface may be finished with a baffle in order to form, as shown at the top right and top left in FIG. 1, V-shaped deflecting elements which may or may not be symmetrical and may or may not be contiguous. In such an arrangement, it will be understood that the fluid will be obliged to follow an undulating path, as depicted in the left-hand part of FIG. 1, along the vertical edges of the mass 2, thereby lengthening its path in a region where particulate-material bypass channels are conventionally found, yet the deflecting surfaces 4 do not prevent uniform filling of the container 1 when the particulate material is poured via the upper charging orifice 5 of the container 1.
FIG. 2 shows a container 1 having a horizontal arrangement, the mass 2 of particulate material resting on a horizontal bottom arranged in the container 1, the particulate material being poured into the latter via charging orifices 5 distributed along the upper surface of the container 1. According to the invention, in addition to the deflectors 4 (not shown) on the side walls of the container 1, the latter comprises vertical transverse deflectors 40 which consist, for example, of single flat rings or bars arranged at regular intervals along the bottom wall of the container, and the upper charging orifices 5 are provided with distributing hoods 41 in the form of truncated pyramids with contiguous bases. As depicted by the arrows in FIG. 2, the arrangement according to the invention forces the fluid to follow a sinuous path along both the top and bottom, avoiding bypasses at the gravity-fed charging regions. It will be noted in FIGS. 1 and 2 that there is a transverse baffle 30 at the point where the flow enters/leaves the mass 2 in order to encourage the flow downstream to diverge locally here and therefore to slow down locally near the wall.
FIG. 3 shows an alternative embodiment of the horizontal arrangement in FIG. 2. Here, the upper deflectors consist of pairs of plates 42 which converge towards each other, towards the orifices 5, from suspension partitions 6, but which leave a charging slot or opening 7 opposite each orifice 5, thus allowing easy filling of the container, which is continued until the plates 42 are buried in a top reserve of particulate material, enabling in particular any compaction of the material that may occur in the active part of the container to be relieved. The plates 42 make, as previously, an angle α with respect to the horizontal greater than the angle of repose of the particulate material used, conventionally lying between 20 and 30 degrees.
FIG. 4 shows a vertical container 1 which contains at least one annular mass 2 of particulate material retained between two concentric perforated walls 8 and 9 which bound, inside the container 1, inner 10 and outer 11 chambers between which the fluid flows by passing through the mass 2 radially. According to the invention, in addition to the vertical deflectors 42, which in this case are annular, on the bottom, which in this case is domed, supporting the mass 2, the container includes, as shown in the left-hand part of FIG. 4, two annular deflecting surfaces 43 which extend towards each other from the junction regions between, respectively, the grills 8, 9 and the shells 80, 90 from which the latter are suspended and which have, as in the embodiment in FIG. 3, a vertical V-shaped cross-section leaving, at their apex, an annular passage 7 lying substantially vertically below the charging orifices 5 and enabling the space between the grills 8 and 9 to be charged with particulate material via these orifices, the charging being carried out, here too, until the deflecting plates 81 and 91 are well buried, as shown in the figure. As depicted in the latter by the upper arrow, the deflecting surfaces 43 force the fluid at the upper end of the grills 8 and 9 to flow almost directly from the space 10 to the space 11, or vice versa, without leaking away through the reserve of particular material between the shells 80 and 90.
In a variant, as shown in the right-hand part of FIG. 4, it is possible to use only one frustoconical annular deflecting plate 4, the annular passage 7 then being defined between the end of the plate and the now shortened suspension shell (80) opposite.
Although the present invention has been described in relation to particular embodiments, it is not limited thereby but is, on the contrary, susceptible of modifications and variants which will be apparent to one skilled in the art. | An apparatus for improving the flow of fluid to be treated in boundary regions of a mass (2) of particulate material. The apparatus has at least one deflecting surface (4), making an angle with the main direction of the flow of fluid passing through the mass, in the boundary region in order to divert the flow of the fluid locally. The apparatus may be used in plants for purifying or separating gas mixtures. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2006-157082 filed in Japan on Jun. 6, 2006, the entire contents of which are hereby incorporated by reference.
TECHNICAL FIELD
This invention relates to an additive for imparting flame retardancy with an organic resin, a flame retardant resin composition, and an article molded from such composition. More specifically, this invention relates to an additive for imparting flame retardancy with an organic resin capable of realizing excellent flame retardancy which does not contain environmentally harmful halogen flame retardant or phosphorus flame retardant, and this invention also relates to a flame retardant polycarbonate resin composition adapted for use in producing various components in electric, electronic, and OA appliance which are required to have excellent mechanical properties including impact strength as well as good moldability and outer appearance, and which are also required to meet extremely strict flame retardancy standards. This invention also relates to an article molded from such composition.
BACKGROUND ART
Polycarbonate resins (hereinafter sometimes abbreviated as “PC”) are widely used in various industrial fields including automobile, OA appliance, and electric and electronic products. However, there is a strong demand for improvement of the flame retardancy for the resin materials used in the applications including OA appliance, and electric and electronic products, and numerous flame retardants have been developed to fulfill such demands. The flame retardants used for the polycarbonate resin have mostly been bromine compounds which were optionally used with antimony trioxide. Such resin composition, however, generates bromine gas in the burning of the resin, and this invites environmental contamination. In view of such situation, use of a phosphorus flame retardant, for example, a phosphate ester simultaneously with or without the bromine compound has been recently reported as an attempt to reduce the amount of the bromine compound used. However, such phosphorus flame retardants has a drawback that it decomposes during its use inviting loss of the mechanical strength of the resin composition, and such phosphorus flame retardants could not completely solve the problem of environmental contamination.
With regard to such non-phosphorus flame retardant materials or non-phosphorus, non-bromine flame retardant materials, Patent Document 1 (JP-A 51-045159), for example, proposes a flame retardant polycarbonate resin composition comprising an organic acid salt such as sulfonate salt of an alkaline metal or alkaline earth metal, polytetrafluoroethylene, and an aromatic polycarbonate; Patent Document 2 (JP-A 06-073281) proposes a flame retardant polycarbonate resin composition comprising a polycarbonate, an alkali metal salt or an alkaline earth metal salt of a perfluoroalkanesulfonic acid, and epoxy resin; and Patent Document 3 (JP-A 2004-155938) proposes a flame retardant polycarbonate resin composition comprising a polycarbonate resin, a metal salt of an aromatic sulfur compound, a fiber-forming fluorine-containing polymer, and a polyorganosiloxane. These flame retardant polycarbonate resin compositions, however, did not exhibit the excellent transparency characteristic to the polycarbonate resin, and also suffered from the drawbacks including loss of melt thermal stability when the flame retardant is added at an amount sufficient for realizing the intended flame retardancy, yellowing and silvering of the molded article, and drastic decrease in the mechanical strength.
Patent Document 4 (JP-A 2003-064229) proposes a flame retardant resin composition comprising a metal sulfonate salt of styrene polymer in which an aromatic monomer unit having sulfonate group in the aromatic skeleton constitutes 15 to 45% by mole of the total monomer units, a styrene polymer having a content of the metal sulfate of up to 5% by weight, and a polycarbonate. This flame retardant resin composition suffered from insufficient thermal stability that invited yellowing of the composition as well as insufficient weatherability.
In the case of the polycarbonate resin compositions having incorporated therein a halogen-free, phosphorus-free flame retardant as described above, the compositions suffered from the drawback that the composition was insufficient in the flame retardancy, and when a flame retardant was incorporated at an amount sufficient for realizing the flame retardancy, the composition exhibited loss of the melt thermal stability and the molded article underwent yellowing and drastic loss of mechanical strength.
In the meanwhile, a number of polymer alloys with another thermoplastic resin have been developed to further improve and modify various properties of the polycarbonate resin. One such polycarbonate composition is the one prepared by blending a polycarbonate resin with a styrene/acrylonitrile graft copolymer such as ABS resin, and this material is widely used in the field of automobiles as well electric and electronic appliances because it is a thermoplastic resin material having excellent mechanical properties, flowability, and thermal properties. In the field where the flame retardancy is required, a flame retardant is blended in such composition. Exemplary halogen-free flame retardant materials having reduced environmental stress include a resin composition comprising a polycarbonate resin and an ABS resin having a phosphorus flame retardant incorporated therein (see for example, Patent Documents 5 and 6: JP-A 02-115262 and JP-A 02-032154). These materials, however, suffered from the problems such as decrease in the distortion temperature under load as well as generation of the mold deposit.
Patent Document 7 (JP-A 11-172063) proposes a resin composition comprising a polycarbonate resin and an ABS resin having a metal sulfonate salt of the polystyrene incorporated therein. However, when the metal sulfonate salt was incorporated at an amount sufficient for realizing the flame retardancy, impact strength and distortion temperature under load of the resin composition decreased, and the molded article exhibited insufficient outer appearance. Patent Document 8 (JP-A 2002-167499) proposes a flame retardant resin composition formed form a polymer comprising a polycarbonate resin, a styrene resin, silicon, boron, and oxygen which has skeleton substantially constituted from silicon-oxygen bond and boron-oxygen bond, and which has aromatic ring in its molecule. This resin composition, however, was insufficient in the flame retardancy and impact strength. Patent Document 9 (JP-A 2004-035587) proposes a flame retardant resin composition comprising an aromatic polycarbonate resin, a styrene resin, an organic alkali metal salt and/or organic alkaline earth metal salt, and a silicone compound having functional groups. This flame retardant resin composition was commercially unpractical due to the insufficient glossiness and insufficient tensile elongation at the welded portion.
As described above, the resin compositions comprising a polycarbonate resin, a styrene resin such as ABS, and a flame retardant have been insufficient in distortion temperature under load, impact strength, and weld strength, and exhibited mold deposit and unfavorable outer appearance, and, currently available flame retardant resin compositions have been unacceptable for use in commercial applications.
DISCLOSURE OF THE INVENTION
The present invention has been completed in view of the situation as described above, and an object of the present invention is to provide an additive for imparting flame retardancy with an organic resin which does not use the environmentally harmful halogen or phosphorus flame retardant which also adversely affects the performance of the product but which satisfies the severe flame retardancy requirements of the level equivalent to those employing such flame retardants. Another object of the present invention is to provide a flame retardant polycarbonate resin composition adapted for use in producing a product having excellent mechanical properties, moldability, and outer appearance as well as an article molded therefrom.
In order to realize the objects as described above, the inventors of the present invention made an intensive study and found that a resin composition produced by blending a polycarbonate resin or a polymer alloy of the polycarbonate resin and another thermoplastic resin with a small amount of a novel silicone compound having phenyl group, an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group, and siloxane bond generates a large amount of carbide in the burning of the polycarbonate resin, and the thus formed carbide covers the surface of the burning resin to cause delay in the supply of the decomposed gas generated in the interior of the resin to the site of burning to thereby realize a high level flame retardancy.
The inventors also found that such silicone compound exhibits good dispersibility in the polycarbonate resin, and when such silicone compound is incorporated in a polycarbonate resin composition, the article produced by the curing of such composition has excellent mechanical strength and outer appearance. The present invention has been completed on the bases of such findings.
Accordingly, the present invention provides an additive for imparting flame retardancy with an organic resin comprising a silicone compound having phenyl group bonded to silicon atom, an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group bonded to silicon atom via a hydrocarbon group (optionally containing a hetero atom), and siloxane bond.
The present invention also provides a flame retardant resin composition comprising 100 parts by weight of a resin comprising 50 to 100% by weight of a polycarbonate resin (A) and 0 to 50% by weight of a thermoplastic resin (B) other than the polycarbonate resin; and 0.01 to 5.0 parts by weight of an additive for imparting flame retardancy with an organic resin (C) comprising a silicone compound having phenyl group bonded to silicon atom, an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group bonded to silicon atom via a hydrocarbon group (optionally containing a hetero atom), and siloxane bond.
EFFECTS OF THE INVENTION
The additive for imparting flame retardancy with an organic resin comprising a silicone compound according to the present invention is useful as a flame retardant for a thermoplastic resin, such as polycarbonate resin, silicone modified polycarbonate resin, polystyrene resin, acrylonitrile/butadiene/styrene (ABS) resin, polyphenylene ether resin, polyester resin, polyamide resin, polyethylene, polypropylene, polybutene, polysulfone, polylactic acid, polyvinyl acetate, ethylene-vinyl acetate copolymer, polymethyl methacrylate, polyoxyethylene, cellulose acetate, and cellulose nitrate. In particular, a flame retardant resin composition prepared by incorporating this additive for imparting flame retardancy with an organic resin in a polycarbonate resin or a polymer alloy of a polycarbonate resin and another thermoplastic resin, and an article molded therefrom do not use the environmentally harmful halogen or phosphorus flame retardant which also adversely affects the performance of the product but satisfy the severe flame retardancy requirements at the level equivalent to those employing such flame retardants. Such flame retardant resin and article molded therefrom are also excellent in mechanical properties such as impact strength, moldability, outer appearance, and thermal stability, and therefore, they are well adapted for use in various applications, and in particular, in the application of electric, electronic, OA components as well as application of precision components.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Next, the present invention is described in detail.
The additive for imparting flame retardancy with an organic resin of the present invention comprises a silicone compound having phenyl group bonded to the silicon atom, an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group bonded to the silicon atom via a hydrocarbon group (optionally containing a hetero atom), and siloxane bond.
The silicone compound used is the one having phenyl group bonded to the silicon atom in the molecule in view of the dispersibility in the organic resin, and in particular, in a polycarbonate resin and capability of imparting the flame retardancy with such resin. Examples of the siloxane unit constituting the silicone compound include phenylsilsesquioxane unit and diphenylsiloxane. In view of imparting such properties, content of the phenyl group in relation to total organic groups bonded to the silicon atom in the molecule is preferably 20 to 90% by mole, and more preferably, 30 to 70% by mole.
The silicone compound used is also the one containing an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group (—SO 3 M group) bonded to the silicon atom via a hydrocarbon group (optionally containing a hetero atom) in the molecule in view of the capability of imparting flame retardancy with the organic resin, and in particular, with a polycarbonate resin. In view of imparting such properties, content of the hydrocarbon group containing the alkali metal sulfonate salt group or the alkaline earth metal sulfonate salt group in relation to the total organic groups bonded to the silicon atom in the molecule is preferably 3 to 50% by mole, and more preferably, 5 to 40% by mole.
The metal atom M in the alkali metal sulfonate salt group or the alkaline earth metal sulfonate salt group (—SO 3 M group) may be, for example, an alkali metal such as lithium, sodium, or potassium; or an alkaline earth metal such as magnesium, calcium, or barium. In view of providing the flame retardancy, the metal atom M is preferably sodium and/or potassium.
In this case, the alkali metal sulfonate salt group or the alkaline earth metal sulfonate salt group bonded to the silicon atom via the hydrocarbon group is, for example, an aryl group such as phenyl group, an alkenyl group such as vinyl group, allyl group, an alkyl group substituted with epoxy group, a halogenated alkyl group, or an alkyl group substituted with mercapto group bonded to an alkali metal or an alkaline earth metal sulfonate. The hydrocarbon group is preferably the one containing 1 to 18 carbon atoms, and in particular, the one containing 2 to 10 carbon atoms.
Exemplary organic groups other than the phenyl group or the hydrocarbon group having the alkali metal sulfonate salt group or the alkaline earth metal sulfonate salt group include unsubstituted monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups other than phenyl group, and aralkyl groups, and substituted monovalent hydrocarbon groups containing 1 to 18, and in particular, 1 to 10 carbon atoms. Also included are such monovalent hydrocarbon groups substituted with a halogen atom, epoxy group, mercapto group. Content of such groups is preferably 0 to 77% by mole, and in particular, 0 to 65% by mole in relation to the total organic groups bonded to the silicon atom in the molecule.
When the silicone compound of the present invention is used as the additive for imparting flame retardancy with an organic resin, the alkali metal sulfonate salt group or the alkaline earth metal sulfonate salt group in the molecule is assumed to promote formation of the carbide layer by accelerating thermal decomposition of the organic resin during the burning, and such action together with the synergetic actions such as coupling action by the phenyl group in the same molecule and formation of an inorganic flame retardant layer by the siloxane backbone promptly blocks supply of the oxygen to thereby extinguish fire and prevent dripping.
For an efficient realization of such effects, the silicone compound of the present invention should be a polymer having a siloxane bond and not a monomer compound, and in view of the capability of forming the flame retardant layer, the silicone compound is preferably a polymer having a branched structure.
In the silicone compound used in the present invention, the ratio of the tetrafunctional unit SiO 2 , trifunctional unit RSiO 3/2 , difunctional unit R 2 SiO, and monofunctional unit R 3 SiO 1/2 is preferably such that:
SiO 2 unit: 0 to 50% by mole, and in particular, 0 to 30% by mole,
RSiO 3/2 unit: 20 to 100% by mole, and in particular, 40 to 90% by mole,
R 2 SiO unit: 0 to 80% by mole, and in particular, 10 to 60% by mole, and
R 3 SiO 1/2 unit: 0 to 30% by mole, and in particular, 0 to 20% by mole.
In the formula, R represents the organic group as defined above.
Such silicone compound may be any silicone compound having a non-limited composition and structure, and use of a combination of two or more silicone compounds having different composition and structure is also acceptable. The production method used in producing such silicone composition is not particularly limited, and the silicone compound may be produced by a method known in the art.
For example, a silane having a structure corresponding to the target silicone compound or a precursor of such silane compound may be simultaneously hydrolyzed optionally in the presence of an appropriate organic solvent, and an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group may be incorporated in the hydrolysate to thereby obtain the target product. Alternatively, when an alkoxysilane, a silicone oil, or a cyclic siloxane having an organic residue such as phenyl group, methyl group, vinyl group, glycidoxypropyl group, chloropropyl group, or mercaptopropyl group in the molecule is used for the starting material, an acid catalyst such as hydrochloric acid, sulfuric acid, or methanesulfonic acid may be used optionally by adding water for hydrolysis to thereby promote the polymerization, and an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group may be thereafter introduced to obtain the intended product.
In such production method, the phenyl group which is a substituent critical in the silicone compound of the present invention can be introduced by using phenyltrichlorosilane, diphenyldichlorosilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and the like for the starting material. In order to produce a compound having a branched structure, use of a trifunctional phenyl silane such as phenyltrichlorosilane or phenyltrimethoxysilane is preferable.
Exemplary methods used in introducing the alkali metal sulfonate salt group or the alkaline earth metal sulfonate salt group include (1) a method in which the phenyl group is sulfonated by sulfuric acid or anhydrous sulfuric acid, and neutralized by sodium hydroxide, potassium hydroxide, or the like to produce an alkali metal sulfonate salt; (2) a method in which an alkenyl group is turned into an alkali metal sulfonate salt by sodium hydrogen sulfite or potassium hydrogen sulfite; (3) a method in which epoxy group is turned into an alkali metal sulfonate salt by sodium hydrogen sulfite or potassium hydrogen sulfite; (4) a method in which a halogenated alkyl group is turned into an alkali metal sulfonate salt by sodium hydrogen sulfite or potassium hydrogen sulfite; and (5) a method in which mercapto group is sulfonated by hydrogen peroxide, and then neutralized by sodium hydroxide or potassium hydroxide to thereby produce an alkali metal sulfonate salt. In view of the reactivity and handling convenience, the preferred are the methods of (3) and (5), and the more preferable is the method of (5).
In the most preferable production method, a method may be employed in which a silane mixture comprising
SiX 4 : 0 to 50% by mole, and in particular, 0 to 30% by mole,
R 1 SiX 3 : 20 to 100% by mole, and in particular, 40 to 90% by mole,
R 1 2 SiX 2 : 0 to 80% by mole, and in particular, 10 to 60% by mole, and
R 1 3 SiX: 0 to 30% by mole, and in particular, 0 to 20% by mole,
(wherein X is a halogen atom such as chlorine or a hydrolyzable group such as alkoxy group or acyloxy group; and R 1 independently represents phenyl group or an optionally substituted monovalent hydrocarbon group other than the phenyl group which constitutes the R as defined above after conversion of a part of the phenyl group and/or a part or all of the optionally substituted monovalent hydrocarbon group other than the phenyl group into the alkali metal or the alkaline earth metal sulfonate salt) is simultaneously hydrolyzed, condensed, and a part of the phenyl group and/or a part or all of the optionally substituted monovalent hydrocarbon group other than phenyl group is turned into an alkali metal or an alkaline earth metal sulfonate salt as described above.
In an exemplary embodiment, the production is conducted by dissolving a phenyl group-containing silane (for example, phenyltrimethoxysilane or diphenyldimethoxysilane), a mercapto group-containing silane (for example, mercaptopropyltrimethoxysilane or mercaptopropylmethyldimethoxysilane), and an optional silane other than such silanes (for example, methyltrimethoxysilane or dimethyldimethoxysilane) in a hydrophilic organic solvent such as methanol; adding a predetermined amount of aqueous solution of hydrogen peroxide dropwise for maturing to thereby oxidize mercapto group and produce sulfonate group; simultaneously conducting hydrolysis by water in the reaction system using the sulfonate group for the catalyst to produce a polymer having siloxane bond; neutralizing the sulfonate group by adding aqueous solution of sodium hydroxide or potassium hydroxide for substitution to thereby generate an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group such as sodium sulfonate salt group or potassium sulfonate salt group. After the reaction, the low boiling content or the impurities are removed by the operation such as heating for removal by distillation, washing with water, or drying to produce the silicone compound containing 100% of the effective component. When the resulting product is a solid, the solid is preferably pulverized to obtain a product in the form of a fine powder. When the silicone compound is produced by such production method, the product may contain residual mercapto group or sulfonate group which failed to undergo the reaction in addition to the target alkali metal sulfonate salt group or the alkaline earth metal sulfonate salt group. Such presence of the functional groups, however, is acceptable as long as such presence does not adversely affect various properties of the flame retardant resin composition produced by adding such silicone compound to the organic resin as a flame retardant additive.
The silicone compound having phenyl group bonded to the silicon atom, an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group bonded to the silicon atom via a hydrocarbon group (optionally containing a hetero atom), and siloxane bond of the present invention can be used as a flame retardant for various thermoplastic resins including polycarbonate resins, silicone modified polycarbonate resins, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, polyphenylene ether resins, polyester resins, polyamide resins, polyethylene, polypropylene, polybutene, polysulfone, polylactic acid, polyvinyl acetate, ethylene-vinyl acetate copolymer, polymethyl methacrylate, polyoxyethylene, cellulose acetate, and cellulose nitrate.
The flame retardant resin composition comprising a polycarbonate resin (A) or a polymer alloy of a polycarbonate resin (A) and a thermoplastic resin (B) other than the polycarbonate resin (A) blended with an additive for imparting flame retardancy with an organic resin (C) comprising a silicone compound having phenyl group bonded to the silicon atom, an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group bonded to the silicon atom via a hydrocarbon group (optionally containing a hetero atom), and siloxane bond is particularly useful as a material for producing a molded article having various excellent properties including the excellent flame retardancy.
Examples of the polycarbonate resin used for the component (A) of the flame retardant resin composition of the present invention include a straight chain or branched homopolymer or a copolymer of the thermoplastic aromatic polycarbonate produced by reacting an aromatic dihydroxy compound or a mixture of an aromatic dihydroxy compound and a small amount of polyhydroxy compound with phosgene or a carbonate diester. Exemplary polymerization methods used in producing the polycarbonate resin includes interfacial polycondensation (phosgeneation) and melt polymerization (transesterification).
The aromatic dihydroxy compound used for the starting material include at least one member selected from 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A), tetramethylbisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene, hydroquinone, resorcinol, 4,4′-dihydroxy diphenyl, and the like, and the preferred is bisphenol A. In producing a branched aromatic polycarbonate resin a polyhydroxy compound such as phloroglucin, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-3-heptene, 1,3,5-tris(4-hydroxyphenyl) benzene, or 1,1,1-tris(4-hydroxyphenyl)ethane; or 3,3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol), 5-chloroisatin bisphenol, 5,7-dichloroisatin bisphenol, 5-bromoisatin bisphenol or the like may be used with the aromatic dihydroxy compound as described above. Such compound is preferably used at 0.01 to 10% by mole, and more preferably at 0.1 to 2% by mole in relation to the total amount of the aromatic dihydroxy compound and the polyhydroxy compound.
Molecular weight of the polycarbonate resin can be adjusted in the course of the polycarbonate resin production, and more specifically, by supplying an alkaline aqueous solution of the aromatic dihydroxy compound and a monovalent aromatic hydroxy compound as a chain terminator, and the halogenated carbonyl compound at a predetermined constant molar ratio to the organic solvent in the presence of a polymerization catalyst. Exemplary monovalent aromatic hydroxy compounds used for the chain terminator include m- or p-methyl phenol, m- or p-propyl phenol, p-tert-butylphenol, and long chain alkyl-substituted phenol. Exemplary preferable polycarbonate resin used include a polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane and a polycarbonate copolymer derived from 2,2-bis(4-hydroxyphenyl)propane and another aromatic dihydroxy compound. Alternatively, the resin may be a polymer having siloxane structure, and for example, an oligomer having siloxane structure may be incorporated in order to improve the flame retardancy. The polycarbonate resin may preferably have a molecular weight in the range of 15,000 to 40,000, and more preferably, 16,000 to 30,000 as measured in terms of viscosity average molecular weight calculated from the viscosity of the solution using methylene chloride for the solvent at a temperature of 25° C.
The thermoplastic resin (B) other than the polycarbonate resin used in the flame retardant resin composition of the present invention is not particularly limited as long as it is the one commonly used for producing an article molded from a thermoplastic resin. Examples of typical such thermoplastic resins include silicone modified polycarbonate resin, polystyrene resin, acrylonitrile/butadiene/styrene (ABS) resin, polyphenylene ether resin, polyester resin, and polyamide resin, and also, polyethylene, polypropylene, polybutene, polysulfone, polylactic acid, polyvinyl acetate, ethylene-vinyl acetate copolymer, polymethyl methacrylate, polyoxyethylene, cellulose acetate, and cellulose nitrate. Among such thermoplastic resins, the particularly preferred is the rubber modified styrene/(meth)acrylonitrile graft copolymer produced by polymerizing styrene monomer and (meth)acrylonitrile in the presence of a rubber because such resin is widely used as a polymer alloy with the polycarbonate resin. In the present invention, such copolymer is sometimes referred to as the “rubber modified styrene/(meth)acrylonitrile copolymer”. If desired, the “rubber modified styrene/(meth)acrylonitrile copolymer” may be produced by simultaneously polymerizing other compolymerizable monomer with the main styrene monomer, acrylonitrile and/or methacrylonitrile.
Exemplary styrene monomers used for the starting material of the rubber modified styrene/(meth)acrylonitrile copolymer include styrene, α-methylstyrene, p-methylstyrene, and the preferred is styrene. Examples of the (meth)acrylonitrile include acrylonitrile and methacrylonitrile. Other copolymerizable monomers include alkyl (meth)acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, and ethyl methacrylate, maleimide, and N-phenylmaleimide, and the preferred is the alkyl (meth)acrylate. In the present invention, “(meth)acrylonitrile” means acrylonitrile and/or methacrylonitrile, and “(meth)acryl” means acryl and/or methacryl.
The rubber in the presence of which the polymerization is conducted is preferably a rubber having a glass transition temperature of up to 10° C. Exemplary such rubbers include diene rubbers, acryl rubbers, ethylene/propylene rubbers, and silicone rubbers, and the preferred are diene rubbers and acryl rubbers.
Exemplary diene rubbers include polybutadiene, butadiene/styrene copolymer, polyisoprene, a lower alkyl ester copolymer of butadiene/(meth)acrylic acid, and a lower alkyl ester copolymer of butadiene/styrene/(meth)acrylic acid. Examples of the lower alkyl ester of (meth)acrylic acid include include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Proportion of the lower alkyl ester of (meth)acrylic acid in the lower alkyl ester copolymer of butadiene/(meth)acrylic acid or the lower alkyl ester copolymer of butadiene/styrene/(meth)acrylic acid is preferably up to 30% by weight of the rubber weight.
Exemplary acrylic rubbers include synthetic rubbers produced from an alkyl ester of acrylic acid. The alkyl group constituting the ester is preferably in the range of 1 to 8. Examples of the alkyl acrylate rubber include ethyl acrylate, butyl acrylate, and ethylhexyl acrylate. The alkyl acrylate rubber may optionally contain a crosslinkable ethylenically unsaturated monomer, and the crosslinking agent may be, for example, an alkylenediol, di(meth)acrylate, polyester di(meth)acrylate, divinylbenzene, trivinyl benzene, triallyl cyanurate, allyl (meth)acrylate, butadiene, or isoprene. The acrylic rubber may also be a core-shell type polymer having a crosslinked diene rubber for the core.
In the rubber modified styrene/(meth)acrylonitrile copolymer, content of the styrene monomer is typically 10 to 90% by weight, and preferably 25 to 85% by weight; content of the (meth)acrylonitrile is typically 5 to 40% by weight, and preferably 5 to 25% by weight; and content of the rubber is typically 5 to 80% by weight, and preferably 10 to 50% by weight. Content of other copolymerizable monomers in the rubber modified styrene/(meth)acrylonitrile copolymer is typically up to 20% by weight, and preferably up to 10% by weight.
The method used in the graft polymerization of the styrene monomer and the (meth)acrylonitrile monomer in the presence of a rubber is not particularly limited. The graft polymerization, however, is typically accomplished by emulsion polymerization or mass polymerization. The rubber modified styrene/(meth)acrylonitrile copolymer used in the present invention may be the one produced by either method.
The rubber modified styrene/(meth)acrylonitrile copolymer is typically a graft copolymer in which the rubber has grafted thereto a copolymer of monomers at least including styrene and (meth)acrylonitrile, or a mixture containing a copolymer in which only the monomers are mutually copolymerized. Exemplary such graft copolymers produced by polymerizing the styrene monomer and the (meth)acrylonitrile in the presence of a rubber include ABS resin, AES resin, and AAS resin.
In the resin components of the flame retardant resin composition of the present invention, content of the component (B) is 0 to 50% by weight because inclusion of the component (B) at a content in excess of 50% by weight is likely to invite loss of heat resistance, and the content is preferably 0 to 35% by weight.
In the flame retardant resin composition of the present invention, the component (C), namely, the additive for imparting flame retardancy with an organic resin with an organic resin comprising a silicone compound having phenyl group bonded to the silicon atom, an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group bonded to the silicon atom via a hydrocarbon group (optionally containing a hetero atom), and siloxane bond is incorporated at a content of 0.01 to 5.0 parts by weight, preferably at 0.05 to 3.0 parts by weight, and more preferably at 0.1 to 2.0 parts by weight in relation to 100 parts by weight of the resin component comprising 50 to 100% by weight of a polycarbonate resin (A) and 0 to 50% by weight of a thermoplastic resin (B) other than the polycarbonate resin. When the additive for imparting flame retardancy with an organic resin (C) is incorporated at a content of less than 0.01 parts by weight, flame retardancy will be insufficient, and when the content is in excess of 5.0 parts by weight, the resulting composition is likely to experience thermal decomposition detracting from the mechanical strength and the outer appearance.
The flame retardant resin composition of the present invention may also have optionally incorporated therein an additive such as a polyfluoroethylene resin capable of forming fibrils, a silicone compound other than the component (C), a flame retardant known in the art (which is preferably not a halogen flame retardant or a phosphorus flame retardant), an elastomer, a UV absorbent, a phenol antioxidant, a phosphorus thermal stabilizer, a pigment, a dye, a lubricant, a mold releaser, a plasticizer, an antistatic agent, or a slidability improving agent; a reinforcing agent such as glass fiber, glass flake, carbon fiber, or metal fiber; a whisker such as potassium titanate, aluminum borate, or calcium silicate; or an inorganic filler such as mica, talc, or clay at an amount that does not adversely affect the benefits of the present invention. The addition may be accomplished by any method known in the art adequate for realizing the benefit of adding the respective additive component.
The method used in the mixing the components (A) to (C) and other optional components for producing the flame retardant resin composition of the present invention is not particularly limited. For example, the components may be kneaded in a kneading apparatus such as a single screw or multi screw kneader, a Banbury mixer, rolls, or a Brabender plastogram, and cooled for solidification. Alternatively, the components may be added to an appropriate solvent such as a hydrocarbon solvent, for example, hexane, heptane, benzene, toluene, or xylene or derivatives thereof to thereby mix the soluble components in the solvent or mix the soluble and insoluble components in the state of suspension. In the case of melt kneading, the kneading is preferably accomplished by using a single screw or multi screw kneader.
The method used in producing a molded article from the flame retardant resin composition of the present invention is not particularly limited, and any method commonly used with the thermoplastic resin can be employed. Exemplary such methods include moldings such as injection molding, blow molding, extrusion, sheet forming, thermal molding, rotational molding, and lamination.
EXAMPLES
Next, the present invention is described in further detail by referring to the Examples, which are presented to show various embodiments of the present invention, and which by no means limit the scope of the present invention unless the Examples exceed the scope defined in the claims. The Examples and the Comparative Examples were conducted by using the following starting materials.
[Starting Material]
(1) polycarbonate resin: poly-4,4-isopropylidene diphenyl carbonate; product name, Iupilon (Registered Trademark) S-3000 (viscosity average molecular weight, 21,500; manufactured by Mitsubishi Engineering-Plastics Corporation, hereinafter abbreviated as “PC resin”).
(2) ABS resin: CBT-698, manufactured by Techno Polymer Co., Ltd.
(3) Additive for imparting flame retardancy with an organic resin according to the present invention comprising a silicone compound having phenyl group bonded to the silicon atom, an alkali metal sulfonate salt group bonded to the silicon atom by an intervening hydrocarbon group, and siloxane bond; Silicone compounds 1 to 4 produced in the Synthesis Examples 1 to 4 as described below.
(4) Silicone compound outside the scope of the present invention not having phenyl group bonded to the silicon atom, and having an alkali metal sulfonate salt group bonded to the silicon atom by an intervening hydrocarbon group and siloxane bond; Silicone compound 5 manufactured in Comparative Synthesis Example 1 as described below; and a silicone compound not containing an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group bonded to the silicon atom by an intervening hydrocarbon group, and having phenyl group and siloxane bond bonded to the silicon atom; Silicone compound 6, polymethylphenyl siloxane, product name, KF50, manufactured by Shin-Etsu Chemical Co., Ltd.
(5) Phosphorus flame retardant: triphenyl phosphate manufactured by Daihachi Chemical Industry Co., Ltd. (hereinafter abbreviated as “TPP”).
(6) Phenol antioxidant: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], product name, IRGANOX 1010, manufactured by Ciba Specialty Chemicals (hereinafter abbreviated as “antioxidant”).
(7) Thermal stabilizer: tris(2,4-di-tert-butylphenyl)phoshite, product name, ADK STAB 2112, manufactured by ADEKA Corporation (hereinafter abbreviated as “thermal stabilizer”).
The silicone compounds obtained in the Synthesis Examples were evaluated for their content of S element and Na element or K element by decomposing the silicone compound with nitric acid and conducing ICP-AES.
Synthesis Example 1
Synthesis of Silicone Compound 1
To a 1.2 L flask equipped with a stirrer, a cooling condenser, a thermometer, and a drop funnel were added 59.5 g (0.3 moles) of phenyltrimethoxysilane, 48.9 g (0.2 moles) of diphenyldimethoxysilane, 58.9 g (0.3 moles) of γ-mercaptopropyltrimethoxysilane, 24.0 g (0.2 moles) of dimethyldimethoxysilane, and 450.0 g of methanol, and the mixture was stirred to prepare a homogeneous solution. To this solution, 30% by weight (119.0 g) of aqueous solution of hydrogen peroxide was added dropwise in 2 hours while maintaining the inner temperature at 20 to 30° C. in a water bath. The solution was stirred for 5 hours for maturing while heating the flask to an inner temperature of 67° C. in refluxing methanol. The reaction solution gradually started to get cloudy in the course of this maturing under reflux, and upon completion of the maturing, the solution was a cloudy homogeneous dispersion. pH of this reaction solution was confirmed to be in the range of 1 to 2 by a pH test paper, and the amount of the hydrogen peroxide remaining in the reaction solution was 0.5 mg/L or less when confirmed by a hydrogen peroxide checker (test paper).
To this reaction solution, 30% by weight (72.6 g) of aqueous solution of potassium hydroxide was added dropwise in 30 minutes while maintaining the inner temperature to the range of 20 to 50° C. in a water bath. The reaction mixture was then stirred for 3 hours while heating the flask to an inner temperature of 67° C. with stirring in refluxing methanol. The pH of the reaction solution was then confirmed to be 9. The reaction mixture was heated in an oil bath at 110° C. to substantially remove methanol and water by distillation, and the reaction mixture was cooled to room temperature. After adding 500 g of methanol again, the reaction mixture was stirred at room temperature for 1 hour, and the resulting homogeneous dispersion was filtered to remove the unreacted content which dissolves in methanol. The content in the form of cake which failed to dissolve in the methanol was added to a mixed solvent of 200 g of methanol and 300 g of ion exchanged water, and the mixture was stirred for 1 hour with cooling in an ice water. The resulting homogeneous dispersion was filtered to remove the remaining ionic impurities. The resulting product in the form of a cake was washed with acetone, and then dried at 100° C. for 5 hours at a reduced pressure of 10 Torr to remove the remaining acetone and water. The resulting product was pulverized in a mortar to obtain 128 g of a fine white powder.
The thus obtained silicone compound 1 has a theoretical structure such that content of the phenyl group in relation to all organic groups bonded to the silicon atom in the molecule is 50% by mole; content of the potassium sulfonate salt group bonded to the silicon atom by the intervening propyl group in relation to all organic groups bonded to the silicon atom in the molecule is 21.4% by mole; it has siloxane bond; content of the branched structure containing trifunctional siloxane unit in all siloxane unit is 60% by mole. When this product was analyzed by nitric acid decomposition and ICP-AES procedure, and content of the S element was 6.1% by weight (theoretical value, 6.1% by weight), content of the K element was 6.9% by weight (theoretical value, 7.5% by weight).
Synthesis Example 2
Synthesis of Silicone Compound 2
The procedure of Synthesis Example 1 was repeated except that the 30% by weight (72.6 g) of aqueous solution of potassium hydroxide was replaced with 30% by weight (45.4 g) of aqueous solution of sodium hydroxide to produce 119 g of fine white powder.
The thus obtained silicone compound 2 has a theoretical structure such that content of the phenyl group in relation to all organic groups bonded to the silicon atom in the molecule is 50% by mole; content of the sodium sulfonate salt group bonded to the silicon atom by the intervening propyl group in relation to all organic groups bonded to the silicon atom in the molecule is 21.4% by mole; it has siloxane bond; content of the branched structure containing trifunctional siloxane unit in all siloxane unit is 60% by mole. When this product was analyzed by nitric acid decomposition and ICP-AES procedure, and content of the S element was 6.5% by weight (theoretical value, 6.3% by weight), content of the Na element was 4.1% by weight (theoretical value, 4.5% by weight).
Synthesis Example 3
Synthesis of Silicone Compound 3
To a 1.2 L flask equipped with a stirrer, a cooling condenser, a thermometer, and a drop funnel were added 99.1 g (0.5 moles) of phenyltrimethoxysilane, 58.6 g (0.24 moles) of diphenyldimethoxysilane, 19.6 g (0.1 moles) of γ-mercaptopropyltrimethoxysilane, 19.2 g (0.16 moles) of dimethyldimethoxysilane, and 580.0 g of methanol, and the mixture was stirred to prepare a homogeneous solution. To this solution, 30% by weight (39.7 g) of aqueous solution of hydrogen peroxide was added dropwise in 2 hours while maintaining the inner temperature at 20 to 30° C. in a water bath. The solution was stirred for 5 hours for maturing while heating the flask to an inner temperature of 67° C. in refluxing methanol. The reaction solution gradually started to get cloudy in the course of this maturing under reflux, and upon completion of the maturing, the solution was a cloudy homogeneous dispersion. pH of this reaction solution was confirmed to be in the range of 2 to 3 by a pH test paper, and the amount of the hydrogen peroxide remaining in the reaction solution was 1 mg/L or less when confirmed by a hydrogen peroxide checker (test paper).
To this reaction solution, 30% by weight (24.2 g) of aqueous solution of potassium hydroxide was added dropwise in 30 minutes while maintaining the inner temperature to the range of 20 to 50° C. in a water bath. The reaction mixture was then stirred for 3 hours while heating the flask to an inner temperature of 67° C. with stirring in refluxing methanol. The pH of the reaction solution was then confirmed to be 8 to 9. The reaction mixture was heated in an oil bath at 110° C. to substantially remove methanol and water by distillation, and the reaction mixture was cooled to room temperature. After adding 500 g of methanol again, the reaction mixture was stirred at room temperature for 1 hour, and the resulting homogeneous dispersion was filtered to remove the unreacted content which dissolves in methanol. The content in the form of cake which failed to dissolve in the methanol was added to a mixed solvent of 200 g of methanol and 300 g of ion exchanged water, and the mixture was stirred for 1 hour with cooling in an ice water. The resulting homogeneous dispersion was filtered to remove the remaining ionic impurities. The resulting product in the form of a cake was washed with acetone, and then dried at 100° C. for 5 hours at a reduced pressure of 10 Torr to remove the remaining acetone and water. The resulting product was pulverized in a mortar to obtain 134 g of a fine white powder.
The thus obtained silicone compound 3 has a theoretical structure such that content of the phenyl group in relation to all organic groups bonded to the silicon atom in the molecule is 70% by mole; content of the potassium sulfonate salt group bonded to the silicon atom by the intervening propyl group in relation to all organic groups bonded to the silicon atom in the molecule is 7.1% by mole; it has siloxane bond; content of the branched structure containing trifunctional siloxane unit in all siloxane unit is 60% by mole. When this product was analyzed by nitric acid decomposition and ICP-AES procedure, and content of the S element was 2.1% by weight (theoretical value, 2.2% by weight), content of the K element was 2.0% by weight (theoretical value, 2.7% by weight).
Synthesis Example 4
Synthesis of Silicone Compound 4
To a 1.2 L flask equipped with a stirrer, a cooling condenser, a thermometer, and a drop funnel were added 69.4 g (0.35 moles) of phenyltrimethoxysilane, 9.8 g (0.04 moles) of diphenyldimethoxysilane, 88.4 g (0.45 moles) of γ-mercaptopropyltrimethoxysilane, 19.2 g (0.16 moles) of dimethyldimethoxysilane, and 600.0 g of methanol, and the mixture was stirred to prepare a homogeneous solution. To this solution, 30% by weight (178.6 g) of aqueous solution of hydrogen peroxide was added dropwise in 2 hours while maintaining the inner temperature at 20 to 30° C. in a water bath. The solution was stirred for 5 hours for maturing while heating the flask to an inner temperature of 67° C. in refluxing methanol. In the course of this maturing under reflux, the reaction solution gradually started to get cloudy from the start of the maturing, and upon completion of the maturing, the solution was a cloudy homogeneous dispersion. pH of this reaction solution was confirmed to be in the range of 1 to 2 by a pH test paper, and the amount of the hydrogen peroxide remaining in the reaction solution was 0.5 mg/L or less when confirmed by a hydrogen peroxide checker (test paper).
To this reaction solution, 30% by weight (108.9 g) of aqueous solution of potassium hydroxide was added dropwise in 30 minutes while maintaining the inner temperature to the range of 20 to 50° C. in a water bath. The reaction mixture was then stirred for 3 hours while heating the flask to an inner temperature of 67° C. with stirring in refluxing methanol. The pH of the reaction solution was then confirmed to be 9 to 10. The reaction mixture was heated in an oil bath at 110° C. to substantially remove methanol and water by distillation, and the reaction mixture was cooled to room temperature. After adding 600 g of methanol again, the reaction mixture was stirred at room temperature for 1 hour, and the resulting homogeneous dispersion was filtered to remove the unreacted content which dissolves in methanol. The content in the form of cake which failed to dissolve in the methanol was added to a mixed solvent of 400 g of methanol and 300 g of ion exchanged water, and the mixture was stirred for 1 hour with cooling in an ice water. The resulting homogeneous dispersion was filtered to remove the remaining ionic impurities. The resulting product in the form of a cake was washed with acetone, and then dried at 100° C. for 5 hours at a reduced pressure of 10 Torr to remove the remaining acetone and water. The resulting product was pulverized in a mortar to obtain 111 g of a fine white powder.
The thus obtained silicone compound 4 has a theoretical structure such that content of the phenyl group in relation to all organic groups bonded to the silicon atom in the molecule is 35.8% by mole; content of the potassium sulfonate salt group bonded to the silicon atom by the intervening propyl group in relation to all organic groups bonded to the silicon atom in the molecule is 37.5% by mole; it has siloxane bond; content of the branched structure containing trifunctional siloxane unit in all siloxane unit is 80% by mole. When this product was analyzed by nitric acid decomposition and ICP-AES procedure, and content of the S element was 9.1% by weight (theoretical value, 9.0% by weight), content of the K element was 9.7% by weight (theoretical value, 11.0% by weight).
Comparative Synthesis Example 1
Synthesis of Silicone Compound 5 (for Comparison Purpose)
To a 1.2 L flask equipped with a stirrer, a cooling condenser, a thermometer, and a drop funnel were added 40.9 g (0.3 moles) of methyltrimethoxysilane, 58.9 g (0.3 moles) of γ-mercaptopropyltrimethoxysilane, 48.1 g (0.4 moles) of dimethyldimethoxysilane, and 400.0 g of methanol, and the mixture was stirred to prepare a homogeneous solution. To this solution, 30% by weight (119.0 g) of aqueous solution of hydrogen peroxide was added dropwise in 2 hours while maintaining the inner temperature at 20 to 30° C. in a water bath. The solution was stirred for 5 hours for maturing while heating the flask to an inner temperature of 67° C. in refluxing methanol. The reaction solution gradually started to get cloudy in the course of this maturing under reflux, and upon completion of the maturing, the solution was a cloudy homogeneous dispersion. pH of this reaction solution was confirmed to be in the range of 1 to 2 by a pH test paper, and the amount of the hydrogen peroxide remaining in the reaction solution was 0.5 mg/L or less when confirmed by a hydrogen peroxide checker (test paper).
To this reaction solution, 30% by weight (72.6 g) of aqueous solution of potassium hydroxide was added dropwise in 30 minutes while maintaining the inner temperature to the range of 20 to 50° C. in a water bath. The reaction mixture was then stirred for 3 hours while heating the flask to an inner temperature of 67° C. with stirring in refluxing methanol. The pH of the reaction solution was then confirmed to be 9. The reaction mixture was heated in an oil bath at 110° C. to substantially remove methanol and water by distillation, and the reaction mixture was cooled to room temperature. After adding 500 g of methanol again, the reaction mixture was stirred at room temperature for 1 hour, and the resulting homogeneous dispersion was filtered to remove the unreacted content which dissolves in methanol. The content in the form of cake which failed to dissolve in the methanol was added to a mixed solvent of 200 g of methanol and 300 g of ion exchanged water, and the mixture was stirred for 1 hour with cooling in an ice water. The resulting homogeneous dispersion was filtered to remove the remaining ionic impurities. The resulting product in the form of a cake was washed with acetone, and then dried at 100° C. for 5 hours at a reduced pressure of 10 Torr to remove the remaining acetone and water. The resulting product was pulverized in a mortar to obtain 83 g of a fine white powder.
The thus obtained silicone compound 5 has a theoretical structure such that content of the phenyl group in relation to all organic groups bonded to the silicon atom in the molecule is 0% by mole; content of the potassium sulfonate salt group bonded to the silicon atom by the intervening propyl group in relation to all organic groups bonded to the silicon atom in the molecule is 21.4% by mole; it has siloxane bond; content of the branched structure containing trifunctional siloxane unit in all siloxane unit is 60% by mole. When this product was analyzed by nitric acid decomposition and ICP-AES procedure, content of the S element was 8.8% by weight (theoretical value, 8.5% by weight), and content of the K element was 6.5% by weight (theoretical value, 10.3% by weight).
Examples 1 to 7 and Comparative Examples 1 to 7
The components were blended by the formulation as shown in Tables 1 and 2, and the mixture was kneaded and pelletized in a single shaft extruder VS-40 (manufactured by Tanabe Plastic) at a barrel temperature of 260° C. The resulting pellets were dried at 120° C. (110° C. in the case of ABS resin) for 5 hours, and injection molded by using Sicap M-2 manufactured by Sumitomo Heavy Industries, Ltd. under the conditions including a clamping force of 75T, a cylinder temperature of 270° C. (260° C. in the case of ABS resin), and a mold temperature of 100° C. to produce test pieces at a cycle of 60 seconds. The resulting test pieces were evaluated by the procedure as described below. The results are shown in Tables 1 and 2. As evident from the comparison of the results shown in Tables 1 and 2, the flame retardant resin compositions of the present invention were superior in flame retardancy, Izod impact strength, total light transmittance (transparency/resin system containing PC resin), outer appearance of the molded article (resin system containing ABS resin), and resistance to mold deposit (resin system containing ABS resin).
[Evaluation of Test Piece]
(1) Flammability: Burn test was conducted according to UL94 vertical burn test for a test piece having a thickness of 2.0 mm.
(2) Izod impact strength: Measurement was conducted according to ASTM D256.
(3) Light transmission: Total light transmission was measured according to ASTM D1003 by molding a plate of 80 mm×40 mm×3.2 mm (evaluation was conducted only for the resin system containing PC resin).
(4) Outer appearance of molded article: The area near the gate of a test piece for tensile strength with no weld portion was visually inspected. A test piece with no flow mark was evaluated A, a test piece with few flow marks was evaluated B, and a test piece with flow marks was evaluated C (evaluation was conducted only for the resin system containing ABS resin).
(5) Mold deposit: Continuous molding was conducted for 500 shots under the conditions described in the Examples, and after the completion of the molding, the molded article was evaluated for the presence of the mold deposit (evaluation was conducted only for the resin system containing ABS resin).
TABLE 1
Example
1
2
3
4
5
6
7
Composition (parts by weight)
PC resin
100
100
100
100
100
90
80
ABS resin
10
20
Silicone compound 1
0.5
1
1
2
Silicone compound 2
1
Silicone compound 3
2
Silicone compound 4
1
Silicone compound 5
Silicone compound 6
TPP
Antioxidant
0.02
0.02
0.02
0.05
0.02
0.02
0.05
Thermal stabilizer
0.02
0.02
0.02
0.05
0.02
0.02
0.05
Performance
Flammability: UL94
V-1
V-0
V-1
V-0
V-0
V-0
V-1
Impact strength: J/m
720
690
700
700
660
560
510
Total light transmittance: %
91
88
87
90
85
—
—
Outer appearance of molded article
—
—
—
—
—
A
A
Mold deposit
—
—
—
—
—
No
No
TABLE 2
Comparative Example
1
2
3
4
5
6
7
Composition (parts by weight)
PC resin
100
100
100
100
100
90
90
ABS resin
10
10
Silicone compound 1
6
6
Silicone compound 2
Silicone compound 3
Silicone compound 4
Silicone compound 5
1
Silicone compound 6
1
TPP
5
5
Antioxidant
0.02
0.02
0.02
0.02
0.05
0.02
0.05
Thermal stabilizer
0.02
0.02
0.02
0.02
0.05
0.02
0.05
Performance
Flammability: UL94
HB
V-2
V-2
V-2
V-2
NG
V-2
Impact strength: J/m
720
250
570
680
120
520
350
Total light transmittance: %
92
90
63
84
54
—
—
Outer appearance of molded article
—
—
—
—
—
C
B
Mold deposit
—
—
—
—
—
Yes
No
Japanese Patent Application No. 2006-157082 is incorporated herein by reference.
Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims. | An additive for imparting flame retardancy with an organic resin is provided. This additive does not use environmentally harmful halogen or phosphorus flame retardant which also adversely affects the performance of the product, and this additive satisfies severe flame retardancy requirements at the level equivalent to those employing such flame retardants. Also provided are a flame retardant polycarbonate resin composition adapted for use in producing a product having excellent mechanical properties, moldability, and outer appearance as well as an article molded therefrom.
The additive for imparting flame retardancy with an organic resin comprises a silicone compound having phenyl group bonded to silicon atom, an alkali metal sulfonate salt group or an alkaline earth metal sulfonate salt group bonded to silicon atom via a hydrocarbon group (optionally containing a hetero atom), and siloxane bond. | 2 |
This invention relates to the treatment of polluted water, and especially to the treatment of effluent water from septic-tank systems, being effluent water which has too high a phosphorus content.
BACKGROUND TO THE INVENTION
The quantity of phosphorus in effluent water from residences is often the factor which limits the concentration of residences that can be accommodated around the banks of a lake. Too much phosphorus in the lake water leads to a nutrient imbalance, a depletion of the oxygen content of the water, a damaging effect on the fish population, and other effects.
In order to permit more residences around the lake, or to enable the water of the lake to be kept clean, a system for removing the phosphorus from the effluent water is desirable. The invention is aimed at providing a more practical and cost-effective system for removing phosphorus from effluent water than has been available hitherto.
GENERAL FEATURES OF THE INVENTION
The invention makes use of the fact that inorganic phosphate dissolved in water can be adsorbed and precipitated out of solution as an insoluble phosphate, by passing the phosphate-laden water over and through grains of a treatment material, such as iron oxide.
The iron oxide, Fe 2 O 3 , containing a ferric ion, gives rise to an ion exchange reaction, whereby ferric phosphate, Fe 2 (PO 4 ) 3 is formed, which precipitates.
Under conditions of oxygen depletion, the iron oxide is more likely to have a ferrous form, whereby the ion exchange leads to ferrous phosphate Fe 3 (PO 4 ) 2 , or the hydrated vivianite form, Fe 3 (PO 4 ) 2 .8H 2 O. Additives such as limestone may be added to accelerate precipitation, or to buffer pH.
The phosphorus in the effluent emerging from a septic tank usually is mainly of the inorganic form; the organic form prevails in the water entering the septic tank, but the organic component is split away by bacterial action in the septic tank.
The ion exchange treatment reaction will not proceed in respect of the organic phosphate molecules, and so there would be little point in adding the iron oxide before the water enters the septic tank, nor until the water has had a good residence time within the tank. One possible location for the iron oxide would be to place the iron oxide at the very bottom of the septic tank, whereby the water does not interact with the iron oxide until the organic components have had time to have been-stripped away. However, there are obvious difficulties, not least in terms of accessibility for replenishment, associated with placing the iron oxide at the bottom of the septic tank.
It might be considered that the iron oxide could be mixed with an inert matrix material such as sand, and the water passed through that. However, it is difficult to get the permeability of a sand-oxide mixture just right, and to maintain that permeability over a long service period. Also, a sand bed cannot cope with a sudden overload of organic phosphate, as can occur occasionally even with well-managed systems. Besides, sand is heavy; and often there is no sand available of the right consistency at the site, and suitable sand has to be trucked in.
Preferably, in the invention, it is the effluent water from the septic tank that undergoes treatment. Preferably the water is treated before it passes to the tile-bed.
Incidentally, the phosphate could still be treated, from the chemical treatment standpoint, after the aerobic nitrification reaction which takes place in the tile bed, but, from the physical standpoint, it would be difficult to address treatment to the post-tile-bed water because that water is infiltrated into the ground below the tile-bed. Upon emerging from the septic tank, i.e before entering the tile-bed, the water is still contained in a pipe or conduit, and can easily be routed through a phosphate treatment station.
In the invention, the grains of the treatment material are contained within the cells or pores of a block of foam. The foam is resilient, i.e the foam quickly recovers its nominal shape after being squeezed and released. The foam is open-celled, i.e the cells or pores are connected, whereby when the foam is squeezed and released under water, water enters the cells throughout the whole inside of the block.
The material of the foam preferably is polyurethane, or related plastic material.
The grains of treatment material may be placed in the cells of the foam in a number of ways. Preferably, the squeezed foam block is placed in a wet slurry of the material, and released. The grains are carried into the cells by the water that then flows into and fills the cells--provided the cells and grains are of a compatible size. Details of this system are described below. It has been found that the squeeze-in-a-slurry system produces a surprising degree of uniformity in the spread of the material right through the whole foam block.
Alternatively, in some cases the treatment material can be electro-plated or electro-deposited into the cells.
Alternatively again, in some cases, the material may be in solution in the water that is drawn into the cells of the foam, and then the material is adsorbed onto the walls of the cells, and is thereby constrained against subsequent movement.
It is also possible in some cases to mix the grains of treatment material in with the polyurethane material from which the foam is made, prior to foaming. After foaming, often the grains tend to reside at the surface of the material, i.e protruding from the walls of the cell into the open centre of the cell.
The invention lies in providing a body of foam material, being foam material of the interconnected-cell, or open-cell, type, and in providing a quantity of grains of treatment material, for example grains of iron oxide. The grains of treatment material are placed in close adjacency to the foam.
The contaminated water is conducted into and through the foam material, whereby the water--that is to say, the contaminants in the water--are held, by the foam, in close adjacency to the grains of treatment material.
For the treatment to be effective, the contaminant should be of the type that is remediated by prolonged contact with the treatment material. For example, where the water is sewage water, and the contaminant is phosphorus, the contaminant may be adsorbed, and precipitated, as a result of prolonged contact with grains of, for example, iron oxide.
One of the benefits of passing the water through the open-cell foam is that foam tends to keeps the water static, or almost static, thereby preventing the water draining away, as it might otherwise tend to do, especially during periods between dosings. Thus, water might tend to drain out of a body of the grains of treatment material, in the absence of the foam. The foam increases the residence time, and promotes equality of residence time of the contaminated water. Also, when water passes through a body of, for example, iron oxide, after a period of time the water tends to create channels, whereby much of the water passes quickly through the channels, while some of the water is snagged and moves very slowly. The foam tends to prevent the water developing and flowing in such preferred channels.
Because the foam retains the water, the invention is most efficacious when the dosings are intermittent. If the flow rate of water were continuous, water retention, and the prevention of draining away between dosings, would not be so important.
On the other hand, in general, it may be regarded that the foam serves to retain water to an extent that may be compared with a fine-grained silt, and yet foam has a porosity that permits water to travel there through, over a long service period, without clogging up, in a manner that may be compared with gravel or sand.
In a domestic septic tank system, for example, dosing occupies less than 1 hour per day, whereby the water remains more or less static in the foam, and held near to the treatment material, for at least 23 hours per day. Then, the water is gradually progressed through the foam and treatment materials as further dosings are added.
The invention may be realised in two formats. In the first format, the treatment material, for example iron oxide, is dispersed through the foam, i.e the grains of iron oxide occupy the cells or pores of the foam, including those cells deep inside the block of foam, as will be described. In the second format, the iron oxide etc is provided in bags of the iron oxide, the bags preferably being configured into a stack of bags intercalated with blocks of foam.
The first format may be described in more detail as follows.
The grains of treatment material may be placed in the cells in the foam by the operation of squeezing and releasing the foam, repeatedly, under water in a container containing the grains of treatment material. If the grains are of the right size, in relation to the cell size, and if the squeezing and releasing is done with some vigour, the blocks of foam can be expected to be filled, more or less evenly throughout the blocks, with dispersed grains of iron oxide. When the water passes through the foam, the water cannot fail to be in close proximity to the treatment material throughout its (prolonged) passage. As the contaminants are adsorbed and precipitated by the action of the treatment material, the precipitates are retained in the foam. The longer the residence time of phosphorus in close proximity to iron oxide, the more precipitation has a chance to take place.
Preferably, the body of foam material is configured as a horizontal layer, and the contaminated water is passed through the layer in a vertical direction. The water may be passed either upwards or downwards. If the water passes upwards, the foam blocks generally remain saturated, i.e under water, all the time. In this case, the foam serves to even out, and slow down, the movement of the water. The problem of channelling is minimised, since foam generally is very resistant to the establishment of channels of flow. For upwards flow, it is generally necessary to place the foam and the treatment material in a container. The foam should be a tight fit in the container, to make sure there is no pathway for the water to by-pass the foam.
If the water passes downwards, gradual channelling of the treatment material would be a serious problem, if there were no foam. Generally, there is no need for a container if the water passes downwards. The foam blocks retain the water, and hold the water within the blocks, even though the foam is not contained, and any excess water in the foam can drain freely away.
Preferably, the foam is in separate layers of foam, which may be removed individually, for replenishment. Each layer may be a one-piece block, or may be a collection of smaller pieces of foam, preferably bagged.
In the first format, the grains are dispersed within the foam itself, and they are placed there by vigorously squeezing the foam in the presence of the grains, so the grains are drawn into the pores. The foam must therefore be of the type which can accomplish this activity. The foam must be soft, so it can be squeezed, and elastically resilient, so it will return to shape after being squeezed.
For original manufacture, the operation of dispersing the grains through the foam can be carried out in-factory, whereby the blocks of foam are shipped from the factory with the grains already in the cells. For replenishment, the user may squeeze the foam blocks himself.
When replenishing, preferably the old grains should be washed out of the foam first. The action of cleansing the foam, prior to replenishment, is accomplished by squeezing the foam out in clean water.
It may be noted that the foam can serve to retain the contaminants within itself. The foam can serve as a transport medium for conveying the contaminant away, if that should be necessary.
As mentioned, in the second format, the grains of treatment material are provided in a configuration that is physically separate from the body of foam material. Preferably, the iron oxide etc is contained in a bag (made of permeable material); that is to say, in several bags, which are arranged as a stack of intercalated bags of iron oxide and blocks of foam.
Preferably, the stack is dosed from above, whereby no container is needed: the foam blocks serve to prevent the water draining away between dosings. Preferably, the horizontal extent of the layers of foam is smaller than the horizontal extent of the treatment material, whereby water passing down from the foam cannot by-pass the treatment material, but must pass through the bag of treatment material.
Preferably, the bags of treatment material are replaceable, as bags, for replenishment and replacement by bags of fresh treatment material.
Typically, in the stack, each foam layer is no more than 15 cm thick, and each bag is no more than 3 cm thick.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
By way of further explanation of the invention, exemplary embodiments of the invention will now be described with reference to the accompanying drawings, in which:
FIG. 1 is a diagram of a septic tank treatment system, having a treatment station which embodies the invention;
FIG. 2 is cross-sectional side view of a component of the treatment station;
FIG. 3 is a diagram showing a stage in preparing the treatment station for use;
FIG. 4 is a magnified view of a portion of a block of foam;
FIG. 4A is a view corresponding to FIG. 4 of another block of foam;
FIG. 5 is a cross-sectional side view of a component of another treatment station.
The apparatuses shown in the accompanying drawings and described below are examples which embody the invention. It should be noted that the scope of the invention is defined by the accompanying claims, and not necessarily by specific features of exemplary embodiments.
FIG. 1 is a diagram of a septic tank sewage treatment system, of the kind used for residences in a region where there is no mains drainage and sewage treatment system laid on. Such systems are used, for example, for vacation cottages situated on the shores of lakes, and for rural residences of all kinds.
The conventional septic tank system comprises the septic tank itself 20, and an aerobic tile-bed or soakaway 23. The septic tank receives effluent water from the residence 25 via a pipe 27, and water is transferred from the septic tank 20 to the tile-bed 23 via a conduit 29. From the tile bed 23, the effluent water soaks into the ground.
In accordance with the invention, a further treatment station 30 is interposed between the septic tank 20 and the tile bed 23, i.e in the conduit 29. In the treatment station 30, the water is passed through sponge or foam containing iron oxide, in which the by-now-inorganic phosphate undergoes the ion-exchange reaction, and precipitates as insoluble iron phosphate.
The structure of the treatment station 30 is shown in FIG. 2. A receptacle 34 is formed as a moulding in plastic. The receptacle includes an inlet port 36 leading to a passageway 38 for conveying the incoming water from the septic tank to the bottom of the receptacle. The water then passes upwards through a compartment or chamber 40, and emerges through an outlet port 43, and passes thence, via conduit 29A, to the tile-bed 23.
The compartment 40 contains a number of blocks 43 of foam or sponge. The blocks are so sized and shaped as to fill the horizontal cross-sectional profile of the chamber 40. The foam is resilient, and the blocks are slightly oversized, whereby the blocks of foam are compressed (slightly) against the walls of the chamber 40. By over-filling the profile, it is ensured that water in passing upwards through the chamber 40 cannot by-pass the foam.
The foam may be provided in one deep block or, as shown, in a series of conveniently shallow blocks 43 placed one on top of another, which in aggregate make up the vertical depth of the chamber 40. It is preferred that the horizontal profile be filled by just one block, but it can be arranged that plural blocks are required to fill the profile: in that case, care must be taken, with the design of the blocks, that leak-channels are not allowed to become established between the blocks, or between the blocks and the walls of the chamber, whereby water could flow upwards through the chamber without passing through the foam.
In order to treat the (inorganic) phosphate dissolved in the water, particles of iron oxide are placed in the pores of the sponge or foam. As shown in FIG. 3, one of the blocks 43 is placed in a container 45, which contains a slurry of water 47 and a quantity 49 of iron oxide powder.
To charge the block with iron oxide, the foam block is placed into the water, and squeezed. (This may be done by hand, or mechanically, as desired.) Upon release, the water soaks into the pores of the foam, and the grains of iron oxide in the water are also carried into the pores. The squeezing and releasing is done several times, whilst agitating the water and stirring up the iron oxide powder.
It has been found that the iron oxide powder can easily be distributed substantially evenly throughout all the pores of the whole block of foam, in just a few squeezings: thus, it is not difficult for a person, with only a little skill and care, to charge the block of foam with an evenly-distributed quantity of iron oxide powder. Naturally, the foam must be of a sufficiently resilient consistency to be amenable to the operation of squeezing and releasing.
FIG. 4 shows the condition of the pores 50 of the foam after the block has received a charge of iron oxide powder. The foam is of the connected-cell type, whereby water, and the grains of iron oxide, can pass freely into and through the cells or pores.
The size of the grains of iron oxide powder is important, in relation to the size of the pores in the foam. FIG. 4 shows grains 52 of about the maximum size, in relation to pore size, whereby the grains will pass freely into and through the foam. Here the grains lodge in the pores more or less by mechanical constraint.
In FIG. 4A, the grains 54 are much smaller in relation to the pore size. Now, the grains are retained in the cells or pores more by adhesion to the material of the foam, i.e to the walls of the cells, than by mechanical constraint: that is to say, the grains become embedded in the walls of the cells. The shape of the grains can be important in how well the grains are retained in the cells: grains with angular corners will be more readily retained than rounded grains. Either way, however, the key is that the grains be small enough to enter and pass freely through the cells, and that the grains be retained in the cells, by some means.
When the pore size of the foam is 0.5 mm average, the grain size of the iron oxide particles should be between 0.05 mm and 0.3 mm.
It is important that the grains of iron oxide do not become dislodged due to the flow of water through the blocks, during operation. The retention of the grains within the cells is a key aspect of the treatment performance of the system; the fact that the water passes through the very cells in which the grains are retained, over and over from cell to cell, while the grains stay put, is what makes the system so efficacious.
Once the blocks have been loaded with iron oxide particles, the blocks are placed in the chamber 40, as shown in FIG. 2. Water passes through the conduits 29,29A, and percolates up through the blocks.
The inorganic phosphate in the water undergoes the ion exchange reaction, forming (insoluble) iron phosphate, as described above. The iron phosphate precipitates onto the grains, i.e into the cells of the foam.
Eventually, the cells become clogged with the precipitates (not just with phosphorus but with calcium carbonate and other salts), and the permeability of the block starts to become less, whereby the flow of water through the chamber 40 becomes restricted. Also eventually, the particles of iron oxide become enveloped in a coating of precipitated iron phosphate, whereby the particles become insulated from the ion exchange reaction. Generally, the potential of the reactive medium to adsorb P becomes diminished.
After a period of use, therefore, the used blocks of foam should be taken out, and replaced with clean blocks, containing a fresh charge of iron oxide powder.
The used blocks, containing precipitated iron phosphate, unused iron oxide, and, inevitably, particles of other solid material that has been carried through from the septic tank, may be cleaned (e.g by back-flushing). However, usually the used blocks will simply be discarded (in an environmentally-appropriate manner). Foam is an inexpensive material; and the foam can easily be transported, even by aircraft in very remote areas, especially if the foam is pre-compressed. The quantity of foam needed for an effective system can easily be brought in.
It may be noted that the used foam blocks can easily be stored, and will continue to retain the pollutant materials therein, pending transport away for disposal.
The designer may arrange that the water from the septic tank flows or trickles downwards through the foam blocks, rather than upwards. The foam does not have to be kept saturated in order for the ion exchange reaction to take place. However, flowing the water upwards leads to longer and more consistent residence times, and more efficient operation.
The size of the receptacle of course can be varied as to desired capacity, but a typical aggregate volume of the foam blocks would be 1 cu meter. The blocks in a system of that size, in a typical rural residence installation, would be subject to replenishment every several years, which is in keeping with the needs of the rest of the septic tank system.
Other substances, i.e other than iron oxide, can be utilised to provoke the ion exchange reaction that leads to an insoluble, precipitatable, phosphate. For example, under the conditions of pH, temperature, etc generally encountered in septic tank systems, iron hydroxides, or iron metal, will lead to insoluble (precipitatable) phosphates. Such substances are not so readily available as iron oxide in granular form, but may be preferred in some circumstances. Sometimes, iron itself can become dissolved in water in unacceptable quantities, which might indicate the use of another substance. Some other metals, such as aluminum, are liable to yield toxic concentrations in water, and are contra-indicated for that reason.
In FIG. 5, the treatment station comprises a stack 50 of blocks 52 of open-cell foam, intercalated with bags 54 containing iron oxide powder. The bags 54 are made of geofabric, which allows water to pass therethrough. The contaminated water is fed in, on top of the stack, at 56, and passes down through the stack, draining freely out from the bottom thereof, at 58. The water is collected in a tray 60, and conveyed away.
Dosing is intermittent. Between dosings, the open-cell foam acts to keep the water static, or almost static. After steady state conditions have been reached, the foam remains almost completely saturated between dosings, by sponge action. In fact, if the pore size of the foam is chosen accordingly, the water can be expected to remain static in the foam for a period of weeks, if no dosings should occur. It should be emphasised that the water remains static in the foam by sponge action: no container is required to contain the water, and prevent the water draining away. Insofar as some means is required to hold the stack together mechanically, a mesh basket 63 may be provided, which may be suspended from above, as shown.
Under equilibrium conditions, when a charge of water is dosed on top of the stack, that same volume of water drains out of the bottom of the stack. But the actual molecules of water that drain out the bottom are molecules of water that, by the time they drain out, have been present in the stack for a considerable period, having been gradually travelling down the stack as more dosings were added.
The foam keeps the water static, or nearly static, between dosings, whereby the treatment reactions and processes have ample time to take place, and to be completed. Without the foam to retain the water between dosings, the water, or some of the water, might pass through the stack too quickly for treatment to be completed. | Treatment of sewage water contaminated by phosphorus is accomplished by passing the water through iron oxide. The iron oxide is placed in close proximity to soft resilient open-cell foam, which serves to slow down, and even out, the rate of travel of the water while under treatment, thus increasing the residence time. | 8 |
FIELD OF INVENTION
This invention relates to improvements in lightweight collapsible support structures in the nature of easels, book rests, book ends or similar articles that upon unfolding and erection provide upstanding inclined or substantially vertical support or abutment surfaces for display purposes or for supporting or anchoring articles such as pads, books or similar items.
BACKGROUND TO THE INVENTION
Lightweight collapsible structures useful for a variety of purposes have been disclosed in a number of U.S. patents and Canadian patents exemplified by the following:
U.S. Pat. No. 433,635 issued August 1890;
U.S. Pat. No. 844,066 issued February 1907;
U.S. Pat. No. 1,875,460 issued September 1932;
U.S. Pat. No. Re. 21,371 issued February 1940;
U.S. Pat. No. 2,587,316 issued February 1952;
Canadian Pat. No. 312,291 issued June 1931;
Canadian Pat. No. 315,615 issued Sept. 29, 1931;
Canadian Pat. No. 641,733 issued May 1962.
This invention relates to improvements in such collapsible structures but particularly of the nature disclosed in my U.S. Pat. No. 3,990,669 which issued Nov. 9, 1976 and the Canadian counterpart, Canadian Pat. No. 1,010,008 issued May 10, 1977.
OBJECTS OF THE INVENTION
The principal object of this invention is to provide an improved, self-sustaining, lightweight collapsible support structure including several hingedly interconnected panels adapted upon being extended from a folded state to assume a substantially independent upright stable configuration presenting a principal surface of generally planar configuration from several panels either inclined or supported substantially vertically for display purposes or as a support abutment surface for pads or books or the like.
It is another very important object to provide an improved collapsible support structure of the type described which folds compactly for storing or for shipping or carrying but upon being unfolded and extended and deposited upon a suitable supporting surface assumes a stable configuration.
Still another object is to provide a support structure of minimal components readily unfolded and extended into its stable configuration and vice versa.
Still another important object is to provide a support structure which can be produced in several configurations for particular uses each having an overall appearance that is pleasing.
Still another object is to provide support structures capable of being fabricated from stiff lightweight sheet materials using fundamental manufacturing steps and apparatus which ensure efficiency in production.
FEATURES OF THE INVENTION
The principal feature of this invention resides in providing in a collapsible self-sustaining support structure having a substantial measure of rigidity derived from sheet-like panel portions hingedly interconnected along their common abutting edges to define fold axes for limited swinging movement towards and away from one another, a central panel portion flanked by hingedly interconnected side panel portions which are arranged to be supported in substantially fully extended upstanding side-by-side relation in which the central panel portion has a uniform generally quadrilateral perimetral configuration with its uppermost edge having an extent greater than the extent of its lowermost edge, the central and side panel portions flanking same each presenting hingedly interconnected ledge panel portions along their respective lowermost edges in side-by-side relation with the configuration of the lowermost edges being such that the hingedly inter-connected ledge panel portions are foldable in unison into a generally horizontal disposition only when the aforementioned central and side panel portions are in substantially fully extended side-by-side relation.
The aforementioned structure provides a relationship of panels whose relative positions can be fixed or secured against displacement through the manipulations outlined and when deposited upon a flat supporting surface is sufficiently rigid and stable so as to support or accommodate articles for display or books or in certain embodiments serve as book ends.
It is also a feature within the structure embodying the invention to provide through selected dimensioning of the principal central panels a range of self-sustaining configurations useful for a variety of purposes as earlier mentioned.
Still another feature resides in providing multiple or compound fold axes between the principal central panels and associated side or gusset panels whereby upon collapse and folding of the panel portions one upon the other one section can be received within the other whereby compactness may be readily achieved.
Still another feature resides in providing structures of the type indicated which can be cut or struck from a single sheet of suitable material with fold lines defining fold axes inscribed or impressed therein whereby jointing, bonding or interconnecting of only a minimum number of panel portions is required.
These and other objects and features are to be found in the following description to be read in conjunction with the accompanying sheets of drawings in which:
DRAWINGS
FIG. 1 is a perspective view of one preferred form of support structure embodying the invention in extended erect stable disposition illustrating one arrangement of three forwardly facing inclined panel portions with the lowermost locking ledge panel portions extending forwardly.
FIG. 2 is a perspective view of the support structure of FIG. 1 taken from a point to the rear and to the left below the support structure as viewed in FIG. 1.
FIG. 3 is a perspective view of the support structure of FIGS. 1 and 2 with the outermost side panel portions and associated ledge panel portions folded over upon each other and upon the central panels illustrating the fully collapsed position of same.
FIG. 4 is a plan view of a flattened sheet of suitable material having a perimetral configuration and impressed or inscribed with lines defining fold axes from which the support structure of FIGS. 1, 2 and 3 is derived.
FIG. 5 is an end elevational view of the support structure of FIG. 1 taken from the right side thereof.
FIG. 6 is a perspective view of the second preferred form of support structure embodying the invention in fully extended erect stable disposition.
FIG. 7 is a perspective view of the embodiment of FIG. 6 taken from a point to the rear and to the right below same.
FIG. 8 is a plan view of a flattened sheet of suitable material having a perimetral configuration and impressed or inscribed with fold axes from which the support structure of FIGS. 6 and 7 is derived.
FIG. 9 is a perspective view of the support structure of FIGS. 6 and 7 with the outermost side panel portions and associated ledge panel portions folded over upon each other and upon the central panels illustrating the fully collapsed position.
FIG. 10 is a perspective view of still another preferred form of support structure embodying the invention which is similar to the support structure illustrated in FIGS. 6 to 9 inclusive except that the arrangement of three forwardly facing panel portions extends substantially vertically in the fully erect stable dispostion and with the forwardly presented ledge formation at substantially right angles to the aforementioned panel portions.
FIG. 11 is a perspective view of the embodiment of FIG. 10 taken from a point to the rear and left below same.
FIG. 12 is a plan view of a flattened sheet of suitable material having a perimetral configuration and impressed or inscribed with fold axes from which the support structure of FIGS. 10 and 11 is derived.
FIG. 13 is a perspective view of the support structure of FIGS. 10 and 11 with the extended outermost side panels and associated ledge panel portions folded over upon each other in the manner indicated by the arrows and upon the central panels illustrating the fully collapsed disposition thereof.
DESCRIPTION OF THE INVENTION
The several embodiments of the support structures illustrated in FIGS. 1 to 13 inclusive, when unfolded and secured in the preferred configuration against collapse and deposited upon a suitable supporting surface are independently self-sustaining notwithstanding that they can be readily folded up compactly as illustrated in FIGS. 3, 9 and 13 respectively.
All embodiments illustrated and described are intended to be cut from a single stiff sheet of suitable material such as polyethylene or equivalent plastic sheeting or from suitable stiff cardboard sheeting.
Where desired the panel portions may take the form of stiff rigid perimetral inserts encased in suitable plastic sheeting or like material with the respective fold axes of such composite article being defined by several thicknesses of such sheeting formed together by sealing or by stitching or otherwise adhered.
The fold axes or hinged interconnections are coincident with the panel portion edges. According to the preferred approach which utilizes suitable stiff plastic sheeting the fold axes are defined by impressing or inscribing lines in such plastic sheeting in the die cutting operation. This leaves a minimal number of joints to be fabricated by heat sealing or by using appropriate adhesives.
The Embodiment of FIGS. 1 to 5 inclusive
The embodiment of FIGS. 1 to 5 inclusive is preferably derived from a one-piece layout or blank having the configuration illustrated in FIG. 4.
The blank of FIG. 4 includes a centrally located first panel portion 10 flanked by side panel portions 12 and 14 of opposite symmetry, along each of panel portions 10, 12 and 14 are presented integral ledge panel portions 16, 18 and 20 along lowermost edges 22, 24 and 26 respectively.
Central panel portion 10 has a uniform generally quadrilateral configuration with uppermost edge 28 thereof having a greater extent than lowermost edge 22 such that side edge formations separating the respective associated central and side panel portions and ledge panel portions generally indicated at 30, 32 are angled convergingly downwardly respectively and are constituted by pairs of impressed or inscribed fold lines indicated at 34a, 34b, 36a and 36b in FIG. 4.
Hingedly connected along uppermost edge 28 constituted by an impressed or inscribed fold line as indicated in FIG. 4 is a second central panel portion 42 adapted to support first mentioned central panel portion 10 in upstanding relation as may be better understood from FIG. 2 of the drawings. The hinged connection of the two central panel portions 10 and 42 allows for swinging movement of the central panel 10 with respect to the central panel 42 first forwardly from a next adjacent folded position to an inclined position, and then reversely when the structure is to be collapsed.
The preferred embodiment reveals a hinged connection along uppermost edge 28, whereas this connection may be omitted to provide a gap or slot therebetween for the reception of a flap or cover by means of which a pad can be anchored against dislodgement.
Central panel 42 is flanked by and hingedly connected to generally triangularly shaped side panel portions or gussets 44 and 46 which present along their respective hypotenuses as at 48 and 50 anchoring panel portions 52 and 54 which are adapted to be secured in abutting relation against the respective rear surfaces side panel portions 12 and 14 as best seen in FIG. 2 of the drawings.
The hinged connections extending along side edges of central panel portion 42 and flanking side panel portions 44 and 46 as indicated generally at 56 and 58 in FIG. 4 comprise separated pairs of fold lines in the case of hinge connections 56 as at 60a, 60b, 60c and 60d and in the case of hinge connection 58 as at 62a, 62b, 62c and 62d.
The hinged connections 56 and 58 so defined have an extent so as to embrace the enclosed central panel portions 10 and 42 and associated side panel and gussets when the support structure is collapsed as revealed by FIG. 3 of the drawings.
Also such hinged connections 56 and 58 add stability derived from the assumed column or shaping when the article is extended into the fully erect position revealed by FIG. 2.
It will be observed from the layout or blank of FIG. 4 from which the article of FIGS. 1, 2, 3 and 5is derived that by joining panel portions 52 and 54 to the rear surfaces of panel portions 12 and 14 along their abutting surface shown particularly in FIG. 2 that alignment of lower deges 22, 24 and 26 of panel portions 10, 12 and 14 respectively can be established only when they are arranged in substantially fully extended coplanar side-by-side relation emphasized in FIGS. 1, 2, and 5 of the drawings. In such fully extended side-by-side relation ledge panel portions 16, 18 and 20 can be folded in unison about their common respective edges or fold axes 22, 24 and 26 which secures panel portions 10, 12 and 14 respectively in substantially fully extended coplanar relation against collapse thereby inherently preserving the erect configuration, which structure so defined has a loading capability, and resists deformation when deposited upon a suitable supporting surface.
The support structure of FIGS. 1 to 5 inclusive is intended to carry an opened book supported lowermost on a suitable sponge pad 70 or the like mounted upon ledge panel portions 18 and 20 which sponge pad tends to prevent the cover of the book and pages from closing.
Ledge portions 18 and 20 are provided with notches 72 and 74 respectively which notches are adapted to cooperate with notches 76 and 78 respectively presented by side panel potions 12 and 14 in that elastics can be looped around the respective side panel 12 and ledge panel 18 and side panel 14 and ledge panel 20 and anchored in the aforementioned respective notches to hold the leaves or pages from flipping over.
The Embodiment of FIGS. 6 to 9 Inclusive
It will be understood, having regard to the embodiment of the invention illustrated in FIGS. 6 to 9 inclusive, that a modification to the pattern or layout of FIG. 4 may be undertaken without departing from the concept presented by FIGS. 1 to 5.
This may be understood first by considering the blank of FIG. 8 which includes the first central panel portion 80 flanked by and hingedly connected to side panel portions 82 and 84 each presenting hingedly inter-connected ledge panel portions 86, 88 and 90 lowermost respectively.
Fold axes formations indicated generally at 92 and 94 of FIG. 8 separate panel portions 80 from side panel portions 82 and 84 respectively with the uppermost edge 96 of central panel portion 80 constituting a fold axis of perimetral extent greater than the perimetral extent of lowermost edge 98a but provided with a slotted arrangement as at 98b.
Lowermost edge 98a defining the fold axis between central panel portion 80 and ledge panel portion 86 in the fully extended disposition is aligned with the fold axes 100 and 102 of ledge panel portions 88 and 90 respectively.
Central panel portion 80 is hingedly connected along the unslotted portion of uppermost edge 96 to a second central panel potion 104 flanked by gussets 106 and 108 along hinged connections 110 and 112 respectively in the same manner as described in relation to the embodiment of FIGS. 1 to 5 exclusive.
Gussets 106, 108 present securing panel portions 118 and 120 separated by fold lines 114, 116 respectively which are adapted to be secured to panel portions 82 and 84 respectively of central panel portion 80 as best seen in FIG. 7.
Upon erection of the embodiment of FIGS. 6 to 9 inclusive from the collapsed state of FIG. 9 to that of FIGS. 6 and 7 the panel portions are extended to the point where panels 80, 82 and 84 approach fully extended substantial coplanarity and fold axes 98a, 100 and 102 of ledge portions 86, 88 and 90 move into alignment for swinging in unison forwardly to secure all panel portions against collapse and so preserve the erect condition of the unit with panel portions 80, 82 and 84 inclined rearwardly from lowermost to uppermost edges and with the slot 98b uppermost serving as an aperture for anchoring a note book or pad by its cover to incline downwardly when resting upon same.
The Embodiment of FIGS. 10 to 13 Inclusive
FIGS. 10 to 13 inclusive disclose still another preferred embodiment of the invention.
FIG. 12 illustrates the layout blank used to fabricate the articles depicted in FIGS. 10, 11 and 13 and as with the embodiment of FIGS. 6 to 9 inclusive the layout blank includes a first central panel portion 120 flanked by and hingedly connected to side panel portions 122 and 124 each provided lowermost with ledge panel portions 126, 128 and 130 respectively. The uppermost perimetral edge 150 defines a fold axis along which a second central panel portion 132 is hingedly connected to first central panel portion 120. Central panel portion 132 is also flanked by side panel portions or gussets 134 and 136 carrying outermost connecting panel portions 138, 140 respectively, the fold axes defined by hinge formations 142 and 144 corresponding to those earlier described in connection with the first preferred embodiment of FIGS. 1 to 5 inclusive at 30 and 32 and the fold axes or hinges indicated at 146 and 148 reflecting a structure similar to those indicated at 56 and 58 of the embodiment of FIGS. 1 to 5 inclusive.
The erect support structure depicted in FIGS. 10 and 11 is achieved by securing connecting panels 138 and 140 to the rear surfaces of side panel portions 122 and 124 respectively, as best seen in FIG. 11. So erected, such structure presents front panel portions 120, 122 and 124 in substantially perpendicular relation to the composite forwardly extending ledge formation comprising ledge portions 126, 128 and 130.
This is achieved by selecting a dimension for front central panel portion 120 measured vertically that is less than as indicated at "a" in FIG. 12. The corresponding dimension of rear central panel portion "b" is distinguished from the measurements "a" and "b" of FIGS. 4 and 8 where "a" exceeds "b".
The collapsed configuration of the embodiment of FIGS. 10 to 12 and the direction of folding for that arrangement is as revealed in FIG. 13 by arrows 152 and 154.
In other respects the preferred embodiment of FIGS. 10 to 13 is fabricated and operates in a manner similar to that described in relation to the embodiments of FIGS. 1 to 5 inclusive and 6 to 9 inclusive.
It is emphasized that the substantially fully extended coplanarity achieved in accordance with the embodiments illustrated among the principal panel portions 10, 12 and 14 of FIG. 1 80, 82 and 84 of FIG. 6 and 120, 122 and 124 of FIG. 10 is a limit position and provides automatic alignment of the integral fold axes presented by the respective ledge panel portions which are adapted only in such limit position to move in unison to project forwardly and thereby secure the extended disposition of the respective principal panel portions and associated supporting panel portions to lock same against collapse and impart stability when the article support is deposited upon a suitable support surface.
While the preferred embodiments of the invention have been described and illustrated persons skilled in this field can make variations of alterations in the disclosed structures without departing from the spirit and scope of the invention as defined in the appended claims. | The invention relates to improvements in lightweight collapsible support structures in the nature of easels, book rests and the like which are self sustaining in a predetermined fully erected configuration, presenting in the fully erected configuration a multiplicity of forwardly facing panels upstanding in a rearwardly inclined or substantially vertical position to provide support surfaces for the displaying, supporting or anchoring of articles such as pads, books or the like and further presenting forwardly extending ledge portions from the bottom edges of such abutment surfaces, said ledges serving to rigidify and stabilize the erect configuration of these structures against collapse, but so adapted as to be foldable into a position allowing for such structures to be compactly folded up and collapsed for storage or for carrying when not in use. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to the prior patent application entitled, INFRARED DEFECT DETECTION SYSTEM AND METHOD FOR THE EVALUATION OF POWDERMETALLIC COMPONENTS, having a Ser. No. 60/814,451 and that was filed in the United States Patent and Trademark Office on Jun. 16, 2006,
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OF DEVELOPMENT
[0002] N/A
FIELD OF THE INVENTION
[0003] The present invention relates generally to the field of detecting defects in manufactured parts and in particular to detecting defects in parts manufactured using powder metallurgy techniques.
BACKGROUND OF THE INVENTION
[0004] To meet today's market requirements, metal parts manufacturers are turning to new technologies and processes as well as new implementations. Among these processes is the powdermetallic (P/M) production where low cost, high volume precision parts are efficiently manufactured. This process along with its benefits brings new challenges, including the need for a full quality assessment and control of each part, in other words one hundred percent testing. The ability to directly detect flaws as early as possible in the manufacturing cycle, in conjunction with the possibility to perform in-situ evaluations of components, will reduce overhead and improve yield. Today's process lacks this ability and relies only on indirect methods such as the measurement of weight along with statistical sampling to perform more comprehensive part evaluation through the measurement of density and using destructive methods to study the integrity.
[0005] For the above reasons, it would be beneficial to provide an apparatus and method for testing powder metallurgy parts directly and early in the manufacturing cycle.
SUMMARY OF THE INVENTION
[0006] A pulsed thermography defect detection is described that includes active and passive thermography for non-destructive testing (NDT) of powdermetallic (P/M) components for on-line and off-line inspection. The electric Joule heating effect in the sample under test, caused by either direct current (DC) or alternate current (AC), is used to generate a temperature profile throughout the P/M sample. Recording the surface temperature distribution with an infrared (IR) camera provides information that can be collected for the integrity and quality assessment of the samples. In addition, pulsed thermography is utilized whereby the sample is excited with a current pulse and the thermal response is recorded over time. Specifically, the IR imaging of sub-surface defects is based on a transient temperature recording approach that uses an electric control system to synchronize and monitor the thermal response due to an electrically generated heat source. This enhances the detection capabilities to include subsurface defects and relatively small surface and subsurface defects.
[0007] The P/M components may be in the pre-sinter (or green) state in an on-line manufacturing environment to ensure a substantially high percent quality assurance that may approach 100%. The inspection approach being developed may be used to test all green-state components as they exit the componention press at speeds of up to 1,000 parts per hour. Tests may be carried out for a statistical quality analysis on the components.
[0008] The pulsed thermography system described herein detects surface and subsurface defects in P/M components. In one embodiment, the pulsed thermography system includes a power source coupled to a powdermetallic component under test and provides an electric current to the powdermetallic component that is used to electrically heat it. A function generator, or a timing generator, is coupled to the power source and controls the shape and duration of the pulse or pluses of the electric current applied to the component. An infrared camera is optically coupled to the powdermetallic component and records an image of the heated component at infrared frequencies, and wherein the infrared camera further is controlled by the function generator. A signal processing system is coupled to the infrared camera and receives the recorded image and then processes the recorded image to detect flaws in the powdermetallic component. The power source may be a direct current (DC) current source or an alternating current (AC) current source of variable frequency. In addition, the present invention may include a switch for controlling the electric current under the control of the function generator that is coupled to the switch. The switch may be a solid state switching device and in particular, a so-called MOSFET or IGBT device. The present invention may include first and second electrode contacts that sandwich the component between them. The first and second electrode contacts are coupled to the power source and are sized and configured to provide substantially uniform current flow into the powdermetallic component. The present invention may also include a press drive system attached to the first and/or second contact and able to provide a biasing force against the contact(s) to maintain a consistent electrical connectivity between the contact(s) and the powdermetallic component.
[0009] In the event that AC current is used, the frequency of the AC current driving the induction coil is selected to provide a desired depth of penetration of the induced eddy currents in the powdermetallic component. The induction coil may be coupled to the AC power source, to induce electric currents in the powdermetallic component. An insulating platform may also be disposed between the induction coil and the powdermetallic component.
[0010] Alternatively, passive thermography may be used in which the heat remaining in a component after processing provides the heat that is sensed by the infrared camera.
[0011] The signal processing system receives an infrared image of the component and analyzes the image using threshold processing or profile processing. Threshold processing includes subtracting a threshold value from the value of each pixel in the image. Profile processing includes using two or more profiles on the surface of the powdermetallic component and separating thermal gradients generated by the defects from other effects by subtracting a first profile thermal gradient from a second profile thermal gradient. The analysis of the image may also include calculating the derivative of a thermal profile of a plurality of preselected areas on the surface of the powdermetallic component and/or calculating the so-called Laplacian of a thermal profile of a plurality of preselected areas on the surface of the powdermetallic component.
[0012] A method is also provided for using pulsed thermography to detect defects in a powdermetallic component comprising the steps of first injecting an electric current into the powdermetallic component and second inducing a temperature change in the powdermetallic component. One or more infrared images of the heated powdermetallic component are captured and analyzed to detect temperature differences that may be indicia of a defect in the powdermetallic component. The method may also include injecting a direct current (DC) into the component such that the powdermetallic component has substantially uniform current flow therethrough, or injecting an alternating current (AC) having a frequency selected to provide a desired penetration depth of the alternating current into the powdermetallic component. The AC current may be induced into the powdermetallic component via an induction coil or other induction apparatus. The captured infrared image may be analyzed by determining the thermal gradient on two or more profiles defined on the surface of the powdermetallic component and separating thermal gradients generated by the defects from other effects by subtracting a first profile thermal gradient from a second profile thermal gradient. Alternatively, the infrared image may be analyzed by determining the derivative of a thermal profile of one or more preselected areas on the surface of the powdermetallic component, determining the Laplacian of a thermal profile of a plurality of one or more preselected areas on the surface of the powdermetallic component, or a combination of these methods.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] For a better understanding of the present invention, together with other and further objects thereof, reference is made to the accompanying drawings and detailed description and its scope will be pointed out in the appended claims.
[0014] FIG. 1 shows a dynamic IR test system constructed in accordance with one embodiment of the present invention;
[0015] FIG. 2 is a photograph of the system of FIG. 1 showing the camera, the electric contacts and the switching circuit;
[0016] FIG. 3 shows a system constructed in accordance with another embodiment of the present disclosure to conduct dynamic recording with an induction heating source;
[0017] FIG. 4 is a photograph of the system of FIG. 3 ;
[0018] FIG. 5 shows an IR image recording from a cylindrical green-state component with four artificially created surface-breaking defects;
[0019] FIG. 6 shows a plot of pixel intensity along the two dotted lines in FIG. 5 , with a spatial pixel to pixel distance of 300 μm;
[0020] FIG. 7 shows a plot of the difference in intensity between adjacent pixels along Line 1 and Line 2 shown in FIG. 6 ;
[0021] FIG. 8( a ) shows an IR image of the cylindrical part of FIGS. 1 and 5 after thresholding;
[0022] FIG. 8( b ) shows a profile along the centerline with a spatial pixel-to-pixel distance of 300 μm;
[0023] FIG. 9 shows a P/M gear component with a surface crack situated on the tooth surface;
[0024] FIG. 10( a ) shows an IR image from a gear component similar to that shown in FIG. 9 , except without surface crack 42 , which component has been subjected to inductive AC heating in the system 30 of FIG. 3 ;
[0025] FIG. 10( b ) shows a thermal profile taken along the dotted line 54 in FIG. 10( a );
[0026] FIG. 11( a ) shows an IR image of the defective gear component 50 shown in FIG. 9 , which component has been subjected to inductive AC heating in the system 30 of FIG. 3 ;
[0027] FIG. 11( b ) shows a thermal profile taken through gear component 50 of FIG. 11( a ) in a manner similar to the profile of FIG. 10( b );
[0028] FIG. 12 is a picture of a green-state P/M part to be tested at a manufacturing facility;
[0029] FIG. 13( a ) shows an IR image from the gear 50 of FIG. 12 at a speed of 0.3 m/s;
[0030] FIG. 13( b ) shows a thermal profile along the dotted line;
[0031] FIG. 14 shows a thermal image indicating the temperature monitoring point;
[0032] FIG. 15 shows a temperature plot (in K) of a single IR image pixel recorded over time for a production line of component P/M gears 50 without defects;
[0033] FIG. 16 shows a close-up view of a portion of the temperature plot of FIG. 15 ;
[0034] FIG. 17( a ) shows a second image from the IR recording of the gear shown in FIG. 12 , at a speed of 0.13 ms, and (b) thermal profile along the dotted line;
[0035] FIG. 18 shows a temperature plot (in K) of a single IR image pixel recorded over time for a production line of component P/M gears 50 , wherein the componenting process is changed first to introduce defects into the gears and then changed again to produce gears without defects;
[0036] FIG. 19 is a close-up or zoomed-in view of the portion of the plot of FIG. 18 , wherein defective parts are shown; and
[0037] FIG. 20 depicts a flow chart illustrating a method of practicing the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0038] FIG. 1 depicts a pulsed thermography apparatus for detecting defects in a powdermetallic component according to an embodiment of the present invention. As used herein, powder metallic components includes powder metallic compacts as well as other powder metallic parts. In particular, the apparatus 10 includes a powdermetallic component 12 , which is the object under test, sandwiched between first and second electric contacts 14 . A direct current (DC) power source 16 is coupled to the first and second electric contacts 14 , via switch 20 , to provide current injection into the component 12 . The component 12 is heated by the injected current and emits infrared radiation that varies according to the temperature in known relationships. An infrared camera 22 is configured and oriented such that the component 12 is within the infrared camera's field of view. During the process of heating component 12 , the infrared camera 22 records one or more images of the component 12 , typically within the 8-12 um wavelength range. A function generator 18 controls the switch 20 and the operation of the infrared camera 20 using either a pulse or a step-function transient signal 24 , where the leading edge of the pulse or step-function is used as trigger od the infrared camera 20 to start recording and for the switch 20 to switch to a conductive state. The function generator may also be a timing signal generator. Typically, the switch 20 is a solid state device, such as a metal oxide semiconductor field effect transistor (MOSFET) or insulated gate bipolar transistor (IGBT) switch, which is used to shape the current waveform as needed and to maintain the fall and rise time of the electric current within certain parameters. The signal processing system 26 is coupled to both the power source 16 to control the electric current level and the infrared camera 20 to control the capturing of images during the testing process.
[0039] FIG. 2 depicts a physically realized system that includes large aluminum contacts that are selected in size to provide a substantially uniform electric current flowing into the component 12 . A substantially uniform electric current is needed to ensure that the component 12 is uniformly heated via Joule heating. In addition, FIG. 2 further includes a press system 28 that has been integrated to the aluminum contacts to maintain a constant and consistent electric connection between the component 12 and the electrical contacts 14 . The press system 28 may include a stepper motor coupled to one or both of the electrical contacts 14 .
[0040] FIG. 3 depicts an apparatus for detecting defects in a powdermetallic component according to another embodiment of the present invention. In particular, the apparatus 30 includes a powdermetallic component 12 , which is the object under test, disposed upon an insulating platform 38 . An alternating current (AC) power source 32 is coupled to an induction coil 36 , to provide induced electrical currents within the component 12 . The frequency of the AC current is selected as a function of the desired depth of penetration of the induced eddy currents within the component 12 and the material that the component 12 is comprised of. Typically, the frequency is selected to ensure that the electric current flows at or near the surface of component 12 . In this way, the thermal signature of a defect is raised to a detectable level. The component 12 is heated by the induced current and emits infrared radiation that varies according to the temperature in a known relationship. An infrared camera 22 is configured and oriented such that the component 12 is within the infrared camera's field of view. During the process of heating component 12 , the infrared camera 22 records one or more images of the component 12 , typically within the 8-12 um wavelength range. A timing generator 40 provides timing pulses to control the AC power source 32 and the operation of the infrared camera 22 , where the leading edge of the timing pulse is used a s trigger the infrared camera 20 to start recording and for the AC power source 32 to provide current to the induction heating system 34 . The signal processing system 26 is coupled to the AC power source 32 to control the electric current level, the infrared camera 20 to control the capturing of images during the testing process, and the timing unit for the necessary clocking signals. Additionally, the parts may be moved past the camera using a conveyer system, wherein the conveyer system is part of the insulating platform.
[0041] FIG. 4 depicts a photograph of the system of FIG. 3 and in particular, provides additional details for the induction heating system 34 , including insulating platform 38 .
[0042] FIG. 5 depicts a thermal image of a cylindrical shaped P/M component subject to DC current excitation by system 10 , as described above with reference to FIGS. 1 and 2 . In an effort to evaluate the effects of flaw size, shape, and orientation, a number of defects were artificially created in the P/M component 12 with the aid of a knife. The dimensions of those defects are listed in Table 1.
[0000]
TABLE 1
Flaw parameters in green-state cylindrical parts (the
location is defined as distance from the top).
Length
Width
Depth
Location
Flaw #
[mm]
[μm]
[μm]
Orientation
[mm]
1
10
<20
<20
Horizontal
10
2
1
20
20
Horizontal
20
3
2
20
20
Vertical
30
4
10
<20
<20
Vertical
50
[0043] These defects were created in a cylindrical P/M component 12 consisting of 1000 B iron powder without lubricant. The component 12 was then subjected to a DC current flow of 20 A. The infrared image, depicted in FIG. 5 , was acquired by camera 22 , stored in the signal processing computer 26 , and post-processed by the signal processing computer using one or more image analysis techniques such as profiling and thresholding. In one embodiment, the image is recorded in an index image format, which is transformed in camera 22 to a gray-scale where each pixel has a value ranging from 0 (no intensity) to 255 (full intensity). The image may be stored as an intensity matrix where the value of each pixel is stored in the matrix. This image may then paletted for viewing using a simple coloring scheme where the base temperature is encoded in green, cooler areas are represented in blue, and hot spots are displayed in red.
[0044] As depicted in FIG. 5 , the defects 46 are disposed on the surface of component 12 . To quantify the temperature gradient caused by the presence of one of the defects 46 , a path 42 on the surface of component 12 is selected and the temperature profile is generated along the path 42 . A path 44 is also selected, where the path 44 is a path clear of defects and parallel to the path 42 . A temperature profile is then generated for the path 44 . FIG. 6 depicts the temperature profiles along paths 42 and 44 . While it is apparent from FIG. 6 that path 42 has defects, as shown by the large deviations in temperature at particular locations, post processing is needed to ensure that the defects are detected
[0045] In the post-processing step, the thermal gradients generated by the defects are separated from the effects of material density variations, contact resistance and reflections. FIG. 7 shows a difference plot, where intensity values along Line 42 have been subtracted from values along Line 44 , resulting in the profile shown. As depicted in FIG. 7 , the defects 46 are clearly identifiable due to the intensity difference between the paths 42 and 44 .
[0046] In one embodiment, a simple thresholding concept can be applied to the raw intensity data depicted in FIG. 6 . In this embodiment, any areas with intensities below a preset value are set to zero. Areas with intensities above the preset value are assigned their intensity value. In one embodiment, the pixels having an intensity below the threshold value are set to black and the pixels having an intensity above the threshold value are set to a “bright” value. FIG. 8 a depicts an image of the component 12 during heating, where the intensity data has been filtered using a threshold filter, in which pixels below the preset value are set to 0, i.e., black, and the pixels having a value above the preset value are set to a “bright” value. As can be seen in FIG. 8 a , all four of the defects introduced to the component 12 , and described in Table 1 above, are visible.
[0047] Many algorithms may be used to automate this operation. A convenient scheme utilizes the histogram (a representation of the number of pixels at each level), while more elaborate algorithms use contextual and statistical information including information from adjacent pixels. The choice of a particular algorithm is based upon the particular physical characteristics of the component 12 , the materials used to form the component 12 , and other system requirements. In addition, any number of profile paths may be used to examine the parts for defects and two profile paths was shown for exemplary purposes only and is not meant to be limiting.
[0048] Although the system 10 described above employs basic image analysis techniques, a fault detection system according to the present disclosure could additionally employ a graphical display whereby the captured thermal image is visualized, and an image processing and evaluation algorithm is employed that can be used to assess the integrity of the sample from the captured image.
[0049] The component 12 used in FIGS. 5-8 above was a simple cylinder having no protrusions, crevices, or other complex shapes. FIG. 9 depicts a P/M gear component that presents a more complex geometric shape and is therefore it is more difficult to detect defects in this component. In particular, the gear teeth cause non-uniform density distributions in the part, which in turn causes reflections of heat, which depending on the orientation of the gear component and infrared camera may result in either areas being colder or warmer than the surrounding material. In addition, the multilevel nature of the part also makes it prone to corner cracks 52 which cannot easily be detected as a result of complicated heat transfer mechanisms at the corner. The steel powder gear component 50 used as an example in this embodiment is constructed with 1.0% Cu, 0.2% C and lubricated with 0.8% wax. The density ranges from 6.8 g/cm 3 to 7.1 g/cm 3 .
[0050] The geometry of the gear depicted in FIG. 9 , and in general any other complex geometric shaped part, makes it difficult to ensure that a DC current used to heat the component has substantially uniform current throughout the part. As discussed above, uniform current is desirable so that the entire component is heated substantially uniformly. To ensure a substantially uniform current density in a gear or other complex shaped component may require high current density and additional electrode contacts. Thus, in some instances, for example more complex parts like gear component 50 , it is advantageous to utilize an AC current excitation and induce electric currents within the component. In the case of an AC signal, it is well known that the frequency of the AC signal and the conductivity of the component determine the penetration depth of the induced AC currents. By selecting an appropriate frequency, the induced currents will flow on and near the surface of the component. Accordingly, the thermal signature of the defect will be increased to a detectable level.
[0051] FIG. 10 depicts infrared images for 2D surface and line profiles (along the dotted line). The data is collected with an IR camera positioned 50 cm away (viewed from the side) and operated at a frame rate of 30 Hz. The field of view of the 240 by 320 pixel picture is 15 cm by 15 cm. The total line length of 10 cm is subdivided into 180 points (i.e. with a point-to-point resolution of 0.5 mm) whereas the thermal pixel intensity is displayed in discrete increments up to a maximum discrete level of 260 (or 460K). FIG. 10 ( b ) depicts a thermal profile of an un-defective gear part taken along the dotted line in FIG. 10( a ). FIG. 11( a ) depicts a defective gear part being heated by induction heating, and FIG. 11( b ) depicts the thermal profile of the defective gear. A comparison of FIGS. 11( b ) and 10 ( b ) illustrates how the profile of a defective part differs from a un-defective part.
[0052] The present system and method is also appropriate for real time use on a manufacturing process as it maintains stable performance and is immune from temperature fluctuations in a plant arising from production equipment such as presses, motors, and sinter furnaces. In addition, the present system and method may be extended to detect defects regardless of material composition. For example, Aluminum powder presents a unique challenge as it is a highly reflective material with very low emissivity (0.1 to 0.2) when compared to steel parts with high graphite content where the emissivity is of the order of 0.6.
[0053] Because of the characteristics of the powdermetallic parts, it is also possible to passively test the parts without using an additional heating source or electric current. In this embodiment, the parts are imaged using the residual heat in the part as it exits from the manufacturing press system. In general this method uses the I/R camera, computer system and processing methods substantially similar in nature to the embodiments in which the parts have been heated using an electric current. This embodiment may also be used in conjunction with a conveyer system for automatic defect detection.
[0054] FIG. 12 shows the green-state steel P/M sample. The component is a two level gear with 13 mm in height by 60 mm in diameter and is typically manufactured at a rate of approximately 600 parts per hour, although parts per hour measured in the thousands are possible. FIGS. 13 and 14 depict 2-D surface and line profiles (recorded along the dotted line in FIG. 13( a )) of parts that are expected to be defect-free. The images are recorded with the IR camera positioned 50 cm away (viewed from the side) and operated at a frame rate of 30 Hz. The field of view of the 240 by 320 pixel viewing is 15 cm by 15 cm. The total line length of 10 cm is subdivided into 180 points (i.e. with a point-to-point resolution of 0.5 mm) whereas the thermal pixel intensity is displayed in discrete increments from a baseline of 0 (or 200K) to 260 (or 460K).
[0055] A long IR image sequence of 45 seconds recording duration generates 1350 recorded temperature sampling points with an intensity profile depicted in FIG. 15 (recorded along the tracking point depicted in FIG. 14 ). As expected, as soon as a component moves past the fixed spatial sensing location, the temperature increases.
[0056] FIG. 16 depicts a portion of FIG. 15 that has been zoomed-in on; it allows a more detailed analysis to be performed on the graphical data. Apart from small variations, the temperature profiles are reproducible. This is consistent with the fact that the parts are defect-free. Therefore, we attribute these thermal fluctuations to instabilities in the industrial manufacturing process.
[0057] FIG. 17( a ) depicts a second image of the gear depicted in FIG. 12 at a speed of 0.13 m/s and FIG. 17( b ) shows a thermal profile along the dotted line. FIG. 18 shows an entire 45 sec inspection duration, or 1350 frames. Defects were introduced into the gears by changing press settings during press operations during the manufacturing of the gears. FIG. 18 identifies the points were the process was modified and the defects introduced. During the first 20 seconds we see defective parts and later, after the process adjustment, the response of defect-free parts. As depicted in FIG. 19 , a magnified portion of FIG. 18 between 1 and 10 seconds, defects may be identified using, a simple subtraction technique as discussed above would be sufficient to flag defective components.
[0058] As can be seen by directly comparing FIG. 19 with FIG. 16 , several parts are defective. As a result, this methodology has the potential of being a very simple, yet reliable methodology that allows the identification of defective parts in an on-line setting.
[0059] FIG. 20 depicts a method for detecting defects in a powdermetallic component. In particular, the method includes the steps of: injecting an electric current into the powdermetallic component, step 2002 . The injected current causes the powdermetallic component to heat; it produces a temperature change in the powdermetallic component. Capturing one or more infrared images of the heated powdermetallic component, step 2004 , and analyzing the captured images to detect temperature differences, step 2006 , where the detected temperature differences may be indicia of a defect in the powdermetallic component.
[0060] In the embodiment in which the parts to be examined are passed by the I/R camera, additional processing is necessary to ensure that the part is entirely within the image. One method to do this is to detect the part boundaries. Once the part is within the image area, image frames are taken and saved and processed as would be known in the art.
[0061] The current that is injected into the powdermetallic component method may be direct current or an alternating current. The current is to be maintained substantially constant throughout the powdermetallic component. If the component is a simple design, direct current is typically used, but where the component is a more complex shape, such as a gear, alternative current is used, where the frequency of said alternating current is selected to provide a desired penetration depth of said alternating current into the powdermetallic component. In the embodiment in which alternating current is utilized, induction rather than direct physical contact may be used to inject the alternating current into the component. The analyzing of the captured infrared image may include determining the thermal gradient contained on two or more profiles defined on the surface of the component and separating the thermal gradients generated by a defect from other effects by subtracting the first profile thermal gradient from a second profile thermal gradient. In addition, the analysis of the data includes determining the derivative of a thermal profile of one or more preselected areas on the surface of the powdermetallic component. In another embodiment, the analysis of the thermal data may include determining the Laplacian of a the thermal profile of one or more preselected areas on the surface of said powdermetallic component
[0062] While the pulsed thermography defect detection system has been described in detail and with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. Thus, it is intended that the appended claims, and their equivalents, define the invention. | A pulsed thermography defect detection apparatus including active and passive infrared (IR) thermography for non-destructive testing (NDT) of powdermetallic (P/M) components for on-line and off-line inspection. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This Application claims priority from, and incorporates by reference the entire disclosure of, U.S. Provisional Application No. 61/233,199 filed on Aug. 12, 2009.
BACKGROUND
[0002] 1. Technical Field
[0003] This invention relates generally to electronic classification of data and more particularly, but not by way of limitation, to a system and method for classifying human-resource information into a master taxonomy.
[0004] 2. History of Related Art
[0005] Human-capital management (HCM) business entities have for decades unsuccessfully endeavored to establish an industry-standard job-classification taxonomy and data-management solution that adequately enables productizing of human-capital resources. Although a variety of widely-recognized taxonomic solutions (e.g., Standard Occupational Classification and Major Occupational Groups) have been developed and implemented, these solutions have proven to be significantly deficient in facilitating rudimentary HCM data-management requirements.
[0006] For example, existing taxonomic structures/solutions do not logically relate to how HCM business entities manage, deploy and analyze human-capital resources. The existing taxonomic structures/solutions were developed external to a HCM market segment and therefore are not sufficiently granular to support human-resource productizing. By way of further example, fine-grain attributes applicable to jobs, even when combined with traditional clustering methods, are not categorized, prioritized, contextualized or applied so as to drive accurate classification necessary to support the HCM market segment.
[0007] Because of these deficiencies, it has become standard practice within the HCM market segment for HCM business entities to develop custom job-classification constructs. Additionally, these deficiencies have in many cases forced customers (e.g., those that consume large numbers of personnel, temporary staffing) to also develop custom job-classification constructs. A result is an industry in which hundreds and perhaps thousands of disparate job-classification schemas are utilized.
SUMMARY OF THE INVENTION
[0008] In one embodiment, a method includes configuring a human-capital-management (HCM) master taxonomy and a HCM language library. The HCM master taxonomy includes a plurality of levels that range from more general to more specific, each level of the plurality of levels comprising a plurality of nodes. The plurality of levels include a job-species level and a job-family level, the job-species level including a level of greatest specificity in the plurality of levels, the job-family level including a level of specificity immediately above the job-species level. In addition, the method includes transforming human-capital information via the HCM language library. Further, the method includes classifying the transformed human-capital information into a job-family node selected from the plurality of nodes at the job-family level.
[0009] In another embodiment, a computer-program product includes a computer-usable medium having computer-readable program code embodied therein, the computer-readable program code adapted to be executed to implement a method. The method includes configuring a human-capital-management (HCM) master taxonomy and a HCM language library. The HCM master taxonomy includes a plurality of levels that range from more general to more specific, each level of the plurality of levels comprising a plurality of nodes. The plurality of levels include a job-species level and a job-family level, the job-species level including a level of greatest specificity in the plurality of levels, the job-family level including a level of specificity immediately above the job-species level. In addition, the method includes transforming human-capital information via the HCM language library. Further, the method includes classifying the transformed human-capital information into a job-family node selected from the plurality of nodes at the job-family level.
[0010] The above summary of the invention is not intended to represent each embodiment or every aspect of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] A more complete understanding of the method and apparatus of the present invention may be obtained by reference to the following Detailed Description when taken in conjunction with the accompanying Drawings wherein:
[0012] FIG. 1A illustrates a system that may be used to ingest, classify and leverage information for a subject-matter domain;
[0013] FIG. 1B illustrates various hardware or software components that may be resident and executed on a subject-matter-domain server;
[0014] FIG. 2 illustrates a flow that may be used to ingest, classify and leverage information for the subject-matter domain;
[0015] FIG. 3 illustrates an exemplary HCM language library;
[0016] FIG. 4 illustrates an exemplary HCM master taxonomy;
[0017] FIG. 5 illustrates exemplary database tables for a HCM master taxonomy;
[0018] FIG. 6 illustrates a raw-data data structure that may encapsulate raw data from an input record;
[0019] FIG. 7 illustrates an exemplary process for a parsing-and-mapping engine;
[0020] FIG. 8A illustrates an exemplary parsing flow that may be performed by a parsing-and-mapping engine;
[0021] FIG. 8B illustrates an exemplary parsed data record;
[0022] FIG. 9 illustrates a spell-check flow that may be performed by a parsing-and-mapping engine;
[0023] FIG. 10 illustrates an abbreviation flow that may be performed by a parsing-and-mapping engine;
[0024] FIG. 11A illustrates an inference flow that may be performed by a parsing-and-mapping engine;
[0025] FIG. 11B illustrates a graph that may utilized in various embodiments;
[0026] FIG. 12 illustrates an exemplary multidimensional vector;
[0027] FIG. 13 illustrates an exemplary process that may be performed by a similarity-and-relevancy engine; and
[0028] FIG. 14 illustrates an exemplary process that may be performed by an attribute-differential engine.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS OF THE INVENTION
[0029] Various embodiments of the present invention will now be described more fully with reference to the accompanying drawings. The invention may, however, be embodied in many different forms and should not be constructed as limited to the embodiments set forth herein; rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
[0030] FIG. 1A illustrates a system 100 that may be used to ingest, classify and leverage information for a subject-matter domain. The system 100 may include, for example, a subject-matter-domain server 10 , a data steward 102 , a web server 104 , a network switch 106 , a site administrator 108 , a web browser 110 , a web-service consumer 112 and a network 114 . In various embodiments, the web server 104 may provide web services over the network 114 , for example, to a user of the web browser 110 or the web-service consumer 112 . In a typical embodiment, the provided web services are enabled by the subject-matter-domain server 10 . The web server 104 and the subject-matter-domain server are typically communicably coupled via, for example, the network switch 106 . The data steward 102 may maintain and provide subject-matter-expertise resident on the subject-matter-domain server 10 . In a typical embodiment, the site administrator may, for example, define and implement security policies that control access to the subject-matter-domain server 10 . Exemplary functionality of the web server 104 and the subject-matter-domain server 10 will be described in more detail with respect to the ensuing FIGURES.
[0031] FIG. 1B illustrates various hardware or software components that may be resident and executed on a subject-matter-domain server 10 a . In various embodiments, the subject-matter-domain server 10 a may be similar to the subject-matter-domain server 10 of FIG. 1A . In a typical embodiment, the subject-matter-domain server 10 a may include a parsing-and-mapping engine 14 , a similarity-and-relevancy engine 16 , an attribute-differential engine 11 and a language library 18 . Exemplary embodiments of the parsing-and-mapping engine 14 , the similarity-and-relevancy engine 16 , the attribute-differential engine 11 and the language library 18 will be discussed with respect to FIG. 2 and the ensuing Figures.
[0032] FIG. 2 illustrates a flow 200 that may be used to ingest, classify and leverage information for the subject-matter domain. As will be described in more detail in the foregoing, in a typical embodiment, a language library 28 enables numerous aspects of the flow 200 . In a typical embodiment, the language library 28 is similar to the language library 18 of FIG. 1B . The language library 28 , in a typical embodiment, includes a collection of dictionaries selected and enriched via expertise in the subject-matter domain. In some embodiments, for example, the subject-matter domain may be human-capital management (HCM). In a typical embodiment, a set of subject dictionaries within the collection of dictionaries collectively define a vector space for the subject-matter domain. Other dictionaries may also be included within the collection of dictionaries in order to facilitate the flow 200 . For example, one or more contextual dictionaries may provide context across the set of subject dictionaries. In various embodiments, the language library 28 , via the collection of dictionaries, is operable to encapsulate and provide access to knowledge, skill and know-how concerning, for example, what words and phrases of the input record 22 may mean in the subject-matter domain.
[0033] The flow 200 typically begins with an input record 22 for ingestion and classification. In various embodiments, the input record 22 may be either a structured record or an unstructured record. As used herein, a structured record is a record with pre-defined data elements and known mappings to the vector space for the subject-matter domain. Conversely, as used herein, an unstructured record is a record that lacks pre-defined data elements and/or known mappings to the vector space. Thus, the input record 22 may be, for example, a database, a text document, a spreadsheet or any other means of conveying or storing information. Substantively, the input record 22 typically contains information that it is desirable to classify, in whole or in part, into a master taxonomy 218 . In one embodiment, for example, résumés, job descriptions and other human-capital information may be classified into a human-capital-management (HCM) master taxonomy.
[0034] A parsing-and-mapping engine 24 typically receives the input record 22 and operates to transform the input record 22 via the language library 28 . The parsing-and-mapping engine 24 is typically similar to the parsing-and-mapping engine 14 of FIG. 1B . In a typical embodiment, the parsing-and-mapping engine 24 may parse the input record 22 into linguistic units. Depending on, inter alia, whether the input record 22 is a structured record or an unstructured record, various methodologies may be utilized in order to obtain the linguistic units. The linguistic units may be, for example, words, phrases, sentences or any other meaningful subset of the input record 22 . In a typical embodiment, the parsing-and-mapping engine 24 projects each linguistic unit onto the vector space. The projection is typically informed by the language library 28 , which is accessed either directly or via a dictionary-stewardship tool 210 . Although illustrated separately in FIG. 2 , in various embodiments, the dictionary-stewardship tool 210 and the language quarantine 212 may be part of the language library 28 .
[0035] The dictionary-stewardship tool 210 generally operates to identify and flag “noise words” in the input record 22 so that the noise words may be ignored. Noise words may be considered words that have been predetermined to be relatively insignificant such as, for example, by inclusion in a noise-words dictionary. For example, in some embodiments, articles such as ‘a’ and ‘the’ may be considered noise words. In a typical embodiment, noise words are not removed from the input record 22 but instead are placed in a language quarantine 212 and ignored for the remainder of the flow 200 .
[0036] The dictionary-stewardship tool 210 also is typically operable to place into the language quarantine 212 linguistic units that are not able to be enriched by the language library 28 . In some embodiments, these linguistic units are not able to be enriched because no pertinent information concerning the linguistic units is able to be obtained from the language library 28 . In a typical embodiment, the dictionary-stewardship tool 210 may track the linguistic units that are not able to be enriched and a frequency with which the linguistic units appear. As the frequency becomes statistically significant, the dictionary-stewardship tool 210 may flag such linguistic units for possible future inclusion in the language library 28 .
[0037] The parsing-and-mapping engine 24 generally projects the linguistic unit onto the vector space to produce a multidimensional vector 206 . Each dimension of the multidimensional vector 206 generally corresponds to a subject dictionary from the set of subject dictionaries in the language library 28 . In that way, each dimension of the multidimensional vector 206 may reflect one or more possible meanings of the linguistic unit and a level of confidence in those possible meanings.
[0038] A similarity-and-relevancy engine 26 , in a typical embodiment, is operable to receive the multidimensional vector 206 , reduce the number of possible meanings for the linguistic units and begin classification of the linguistic units in the master taxonomy 218 . The similarity-and-relevancy engine is typically similar to the similarity-and-relevancy engine 16 of FIG. 1B . The master taxonomy 218 includes a plurality of nodes 216 that, in various embodiments, may number, for example, in the hundreds, thousands or millions. The master taxonomy 218 is typically a hierarchy that spans a plurality of levels that, from top to bottom, range from more general to more specific. The plurality of levels may include, for example, a domain level 220 , a category level 222 , a subcategory level 224 , a class level 226 , a family level 228 and a species level 238 . Each node in the plurality of nodes 216 is typically positioned at one of the plurality of levels of the master taxonomy 218 .
[0039] Additionally, each node in the plurality of nodes 216 may generally be measured as a vector in the vector space of the subject-matter domain. In various embodiments, the vector may have direction and magnitude in the vector space based on a set of master data. The set of master data, in various embodiments, may be data that has been reliably matched to ones of the plurality of nodes 216 in the master taxonomy 218 by experts in the subject-matter domain. One of ordinary skill in the art will appreciate that, optimally, the set of master data is large, diverse and statistically normalized. Furthermore, as indicated by a node construct 230 , each node in the plurality of nodes 216 may have a label 232 , a hierarchy placement 234 that represents a position of the node in the master taxonomy 218 and attributes 236 that are relevant to the subject-matter domain. The attributes 236 generally include linguistic units from data in the set of master data that have been reliably matched to a particular node in the plurality of nodes 216 .
[0040] The similarity-and-relevancy engine 26 typically uses a series of vector-based computations to identify a node in the plurality of nodes 216 that is a best-match node for the multidimensional vector 206 . In addition to being a best match based on the series of vector-based computations, in a typical embodiment, the best-match node must also meet certain pre-defined criteria. The pre-defined criteria may specify, for example, a quantitative threshold for accuracy or confidence in the best-match node.
[0041] In a typical embodiment, the similarity-and-relevancy engine 26 first attempts to identify the best-match node at the family level 228 . If none of the nodes in the plurality of nodes 216 positioned at the family level 228 meets the predetermined criteria, the similarity-and-relevancy engine 26 may move up to the class level 226 and again attempt to identify the best-match node. The similarity-and-relevancy engine 26 may continue to move up one level in the master taxonomy 218 until the best-match node is identified. As will be described in more detail below, when the master taxonomy is based on a large and diverse set of master data, it is generally a good assumption that the similarity- and relevancy engine 26 will be able to identify the best-match node at the family level 228 . In that way, the similarity-and-relevancy engine 26 typically produces, as the best-match node, a node in the plurality of nodes 216 that comprises a collection of similar species at the species level 238 of the master taxonomy 218 . In a typical embodiment, the collection of similar species may then be processed by an attribute-differential engine 21 .
[0042] In a typical embodiment, each node at the species level 238 may have a product key 248 that defines the node relative to a spotlight attribute. The product key 248 may include, for example, a set of core attributes 250 , a set of modifying attributes 252 and a set of key performance indicators (KPIs) 254 . The spotlight attribute, in a typical embodiment, is an attribute in the set of core attributes 250 that is of particular interest for purposes of distinguishing one species from another species. For example, in a human-capital-management master taxonomy for a human-capital-management subject-matter domain, the spotlight attribute may be a pay rate for a human resource. By way of further example, in a life-insurance master taxonomy for a life-insurance subject-matter domain, the spotlight attribute may be a person's life expectancy.
[0043] The core attributes 250 generally define a node at the species level 238 . The modifying attributes 252 are generally ones of the core attributes that differentiate one species from another. The KPIs 254 are generally ones of the modifying attributes that significantly affect the spotlight attribute and therefore may be considered to statistically drive the spotlight attribute. In a typical embodiment, the attribute-differential engine 21 is operable to leverage the KPIs 254 in order to compare an unclassified vector 242 with each species in the collection of similar species. The unclassified vector 242 , in a typical embodiment, is the multidimensional vector 206 as modified and optimized by the similarity-and-relevancy engine 26 .
[0044] In a typical embodiment, the attribute-differential engine 21 is operable to determine whether the unclassified vector 242 may be considered a new species 244 or an existing species 246 (i.e., a species from the collection of similar species). If the unclassified vector 242 is determined to be the existing species 244 , the unclassified vector 242 may be so classified and may be considered to have the spotlight attribute for the existing species 244 . If the unclassified vector 242 is determined to be the new species 246 , the new species 244 may be defined using the attributes of the unclassified vector 242 . A spotlight attribute for the new species 244 may be defined, for example, as a function of a degree of similarity, or distance, from a most-similar one of the collection of similar species, the distance being calculated via the KPIs 254 .
[0045] FIGS. 3-14 illustrate exemplary embodiments that utilize a human-capital management (HCM) vector space and leverage expertise in a HCM subject-matter domain. As one of ordinary skill in the art will appreciate, HCM may involve, for example, the employment of human capital, the development of human capital and the utilization and compensation of human capital. One of ordinary skill in the art will appreciate that these exemplary embodiments with respect to HCM are presented solely to provide examples as to how various principles of the invention may be applied and should not be construed as limiting.
[0046] As one of ordinary skill in the art will appreciate, HCM may involve, for example, the development of labor-related issues that impact a business's strategic and operational objectives. Human-capital management may include, for example, the employment of human resource and the development of human resources; and the utilization, maintenance, and compensation human resources.
[0047] FIG. 3 illustrates a HCM language library 38 . In various embodiments, the HCM language library 38 may be similar to the language library 28 of FIG. 2 and the language library 18 of FIG. 1B . The HCM language library 38 typically includes a HCM master dictionary 356 , an abbreviation dictionary 362 , an inference dictionary 360 and a plurality of subject dictionaries 358 that, in a typical embodiment, collectively define the HCM vector space. The plurality of subject dictionaries 358 may include a place dictionary 358 ( 1 ), an organization dictionary 358 ( 2 ), a product dictionary 358 ( 3 ), a job dictionary 358 ( 4 ), a calendar dictionary 358 ( 5 ) and a person dictionary 358 ( 6 ). For example, the plurality of subject dictionaries 358 may include, respectively, names of places (e.g., “California”), names of organizations or business that may employ human capital (e.g., “Johnson, Inc.”), names of products (e.g., “Microsoft Windows”), job positions (e.g., “database administrator”), terms relating to calendar dates (e.g., “November”) and human names (e.g., “Jane” or “Smith”). In a typical embodiment, the abbreviation dictionary 362 , the inference dictionary 360 and, for example, a noise words dictionary may be considered HCM-contextual dictionaries because each such dictionary provides additional context across the plurality of subject dictionaries.
[0048] In a typical embodiment, the HCM master dictionary 356 is a superset of the abbreviation dictionary 362 , the inference dictionary 360 and the plurality of subject dictionaries 358 . In that way, the HCM master dictionary 356 generally at least includes each entry present in the abbreviation dictionary 362 , the inference dictionary 360 and the plurality of subject dictionaries 358 . The HCM master dictionary 356 may, in a typical embodiment, include a plurality of Boolean attributes 356 a that indicate parts of speech for a linguistic unit. The plurality of Boolean attributes 356 a may indicate, for example, whether a linguistic unit is a noun, verb, adjective, pronoun, preposition, article, conjunction or abbreviation. As illustrated in FIG. 3 , each of the plurality of subject dictionaries 358 may also include relevant Boolean attributes.
[0049] In a typical embodiment, the HCM master dictionary 356 , the abbreviation dictionary 362 , the inference dictionary 360 and the plurality of subject dictionaries 358 may be created and populated, for example, via a set of HCM master data. The set of HCM master data, in various embodiments, may be data that has been input into the HCM language library 38 , for example, by experts in the HCM subject-matter domain. In some embodiments, standard dictionary words and terms from various external dictionaries may be integrated into, for example, the plurality of subject dictionaries 358 .
[0050] FIG. 4 illustrates a HCM master taxonomy 418 that may be used, for example, to classify human-capital information such as, for example, résumés, job descriptions and the like. In various embodiments, the HCM master taxonomy 418 may be similar to the master taxonomy 218 of FIG. 2 . The HCM master taxonomy 418 typically includes a job-domain level 420 , a job-category level 422 , a job-subcategory level 424 , a job-class level 426 , a job-family level 428 and a job-species level 438 .
[0051] In various embodiments, the HCM master taxonomy 418 and the HCM language library 38 are configured and pre-calibrated, via HCM subject-matter expertise, to a set of HCM master data in manner similar to that described with respect to the language library 28 and the master taxonomy 218 of FIG. 2 . More particularly, the set of HCM master data may include a series of records such as, for example, job descriptions, job titles, résumés segments, and the like. As described with respect to the master taxonomy 218 of FIG. 2 , each node in the HCM master taxonomy 418 may be measured as a vector in the HCM vector space of the HCM subject-matter domain. Therefore, each node in the HCM master taxonomy 418 may have direction and magnitude in the HCM vector space based on the set of HCM master data. The set of HCM master data, in various embodiments, may be data that has been reliably matched to nodes of the HCM master taxonomy 418 by experts in the HCM subject-matter domain. One of ordinary skill in the art will appreciate that, optimally, the set of HCM master data is large, diverse and statistically normalized.
[0052] FIG. 5 illustrates exemplary database tables for a HCM master taxonomy 518 . In a typical embodiment, a job hierarchy 502 may include one or more job nodes 508 . Each of the one or more job nodes 508 may typically have a job-node type 514 . The job-node type 514 may be, for example, one of the following described with respect to FIG. 4 : the job-domain level 420 , the job-category level 422 , the job-subcategory level 424 , the job-class level 426 , the job-family level 428 and the job-species level 438 . Each of the one or more job nodes 508 may have one or more job-node attributes 506 . In a typical embodiment, one or more of the job-node attributes 506 may be KPIs for a spotlight attribute of the one or more job nodes 508 . In a typical embodiment, each of the job-node attributes 506 may have a job-node-attribute type 512 . A job-node alternate 510 may, in a typical embodiment, provide an alternate means of identifying the job node 508 .
[0053] FIG. 6 illustrates a raw-data data structure 62 that may encapsulate raw data from an input record such as, for example, the input record 22 of FIG. 2 . The raw data may be converted and conformed to the raw-data data structure 62 so that the raw data is usable by a parsing-and-mapping engine such as, for example, the parsing-and-mapping engine 24 of FIG. 2 . In a typical embodiment, the raw-data data structure 62 may include, for example, a job-title attribute 604 , a skills-list attribute 606 , a product attribute 608 , an organization-information attribute 610 , a date-range attribute 612 , a job-place attribute 614 and a job-description attribute 616 . Various known technologies such as, for example, optical character recognition (OCR) and intelligent character recognition (ICR) may be utilized to convert the raw data into the raw-data data structure 62 . One of ordinary skill in the art will recognize that various known technologies and third-party solutions may be utilized to convert the raw data into the raw-data data structure 702 of FIG. 7 .
[0054] FIG. 7 illustrates an exemplary process 700 for a parsing-and-mapping engine 74 . In various embodiments, the parsing-and-mapping engine 74 may be similar to the parsing-and-mapping engine 24 of FIG. 2 and the parsing-and-mapping engine 14 of FIG. 1B . In a typical embodiment, the process 700 is operable to transform an input record such as, for example, the input record 22 of FIG. 2 via, for example the HCM language library 38 of FIG. 3 . At a parsing step 702 , the parsing-and-mapping engine 74 parses raw data such as, for example, an instance of the raw-data data structure 62 of FIG. 6 , into linguistic units. In a typical embodiment, steps 704 , 706 , 708 and 710 proceed individually with respect to each linguistic unit of the linguistic units parsed at the step 702 .
[0055] At spell-check step 704 , the parsing-and-mapping engine 74 may perform a spell check of a linguistic unit from the linguistic units that were parsed at the step 702 . At an abbreviation step 706 , if the linguistic unit is an abbreviation, the parsing-and-mapping engine 74 attempts to identify one or more meanings for the abbreviation. At an inference step 708 , the parsing-and-mapping engine 74 identifies any inferences that may be made either based on the linguistic unit or products of the steps 704 and 706 . At step 710 , as a cumulative result of steps 702 , 704 , 706 and 708 , the linguistic unit is categorized, for example, into one or more of a plurality of subject dictionaries such as, for example, the plurality of subject dictionaries 358 of FIG. 3 . Additionally, a confidence level, or weight, of the linguistic unit may be measured. In that way, the parsing-and-mapping engine 74 is operable to transform the raw data via, for example, the HCM language library 38 of FIG. 3 .
[0056] FIG. 8A illustrates a parsing flow 800 that may be performed during a parsing step such as, for example, the parsing step 702 of FIG. 7 . At step 802 , a parsing method is determined. As noted with respect to FIG. 2 , an input record such as, for example, the input record 22 of FIG. 2 may be a structured record or an unstructured record. A structured record is a record with pre-defined data elements and known mappings, in this case, to the HCM vector space. Therefore, if an input record such as, for example, the input record 22 of FIG. 2 , is a structured record, the known mappings may be followed for purposes of parsing.
[0057] However, if an input record such as, for example, the input record 22 of FIG. 2 , is an unstructured record, other parsing methods may be utilized such as, for example, template parsing and linguistic parsing. Template parsing may involve receiving data, for example, via a form that conforms to a template. In that way, template parsing may involve identifying linguistic units based on placement of the linguistic units on the form. One of ordinary skill in the art will appreciate that a variety of third-party intelligent data capture (IDC) solutions may be utilized to enable template parsing.
[0058] Linguistic parsing may be used to parse an unstructured record when, for example, template parsing is either not feasible or not preferred. In a typical embodiment, linguistic parsing may involve referencing a HCM language library such as, for example, the HCM language library 38 of FIG. 3 . Using a HCM language library such as, for example, the HCM language library 38 of FIG. 3 , the parsing-and-mapping engine 74 of FIG. 7 may identify each linguistic unit in the unstructured record and determine each linguistic unit's part of speech. One of ordinary skill in the art will recognize that a linguistic unit may be a single word (e.g., “database”) or a combination of words that form a logical unit (e.g., “database administrator”). In a typical embodiment, linguistic parsing is tantamount to creating a linguistic diagram of the unstructured record.
[0059] At step 804 of FIG. 8A , the parsing-and-mapping engine 74 may parse an input record such as, for example, the input record 22 of FIG. 2 , according to the parsing method determined at step 802 . In typical embodiment, the step 804 may result in a plurality of parsed linguistic units. At step 806 , the parsing-and-mapping engine 74 may flag noise words in the input record using, for example, the HCM language library 38 of FIG. 3 . In various embodiments, the flagging of noise words may occur in a manner similar to that described with respect to FIG. 2 . After step 806 , the parsing flow 800 is complete.
[0060] FIG. 8B illustrates an exemplary parsed data record 82 that, in various embodiments, may be produced by the parsing flow 800 . In a typical embodiment, the parsed data record 82 includes the plurality of parsed linguistic units produced by the parsing flow 800 . The plurality of parsed linguistic units may be, for example, words. As shown, in a typical embodiment, the parsed data record 82 may be traced to the raw-data data structure 702 of FIG. 7 .
[0061] FIG. 9 illustrates a spell-check flow 900 that may be performed by the parsing-and-mapping engine 74 during, for example, the spell-check step 704 of FIG. 7 . Typically, the spell-check flow 900 begins with a parsed linguistic unit, for example, from the plurality of parsed linguistic units produced by the parsing flow 800 of FIG. 8A . Table 1 includes an exemplary list of spell-check algorithms that may be performed during the step 902 , which algorithms will be described in more detail below.
[0000]
TABLE 1
SPELL-CHECK ALGORITHM
RESULT
Character Standardization
Translates a linguist unit into a
standard character set.
Exact Match
Returns either 0 or 1.
Edit-Distance Ratio
Returns a value between 0 and 1,
inclusive.
Double-Metaphone Ratio
Returns a value between 0 and 1,
inclusive.
[0062] At step 902 , the parsing-and-mapping engine 74 may perform a character-standardization algorithm on the parsed linguistic unit. For example, one of ordinary skill in the art will appreciate that an “em dash,” an “en dash,” a non-breaking hyphen and other symbols are frequently used interchangeably in real-world documents even though each is a distinct symbol. In various embodiments, performing the character-standardization algorithm operates to translate the parsed linguistic unit into a standard character set that removes such ambiguities. In that manner, the efficiency and effectiveness of the spell-check flow 900 may be improved.
[0063] At step 904 , the parsing-and-mapping engine may select a subject dictionary for searching. In a typical embodiment, the subject dictionary selected for searching may be one of a plurality of subject dictionaries such as, for example, the plurality of subject dictionaries 358 of FIG. 3 . In various embodiments, the parsing-and-mapping engine 74 may check the plurality of subject dictionaries 358 of FIG. 3 in a predetermined order as a performance optimization. The performance optimization is typically based on a premise that an exact match in a higher-ranked dictionary is much more significant than an exact match in a lower-ranked dictionary. Therefore, an exact match in a higher-ranked dictionary may eliminate any need to search other dictionaries in the plurality of subject dictionaries 358 .
[0064] Depending on a particular objective, various orders may be utilized. For example, in some embodiments, the parsing and mapping engine 74 may check the plurality of subject dictionaries 358 in the following order: the job dictionary 358 ( 4 ), the product dictionary 358 ( 3 ), the organization dictionary 358 ( 2 ), the place dictionary 358 ( 1 ), the calendar dictionary 358 ( 5 ) and the person dictionary 358 ( 6 ). In these embodiments, if an exact match for the parsed linguistic unit is found in the job dictionary 358 ( 4 ), that match is used and no further dictionaries are searched. In that way, computing resources may be preserved.
[0065] At step 906 , the parsing-and-mapping engine 74 may attempt to identify an exact match for the parsed linguistic unit in the subject dictionary selected for searching at the step 904 . In a typical embodiment, the parsing-and-mapping engine 74 of FIG. 7 may perform an exact-match algorithm for the parsed linguistic unit against the subject dictionary selected for searching. In a typical embodiment, the exact-match algorithm returns a one if an exact match for the parsed linguistic unit is found in the dictionary selected for searching and returns a zero otherwise.
[0066] If, at the step 906 , an exact match is found for the parsed linguistic unit in the subject dictionary selected for searching, in a typical embodiment, the spell-check flow 900 proceeds to step 908 . At the step 908 , the exact match is kept and no other spell-check algorithm need be performed with respect to that dictionary. Additionally, the exact match may be assigned a match coefficient of one. The match coefficient will be discussed in more detail below. From the step 908 , the spell-check flow 900 proceeds directly to step 914 .
[0067] If the exact-match algorithm returns a zero for the parsed linguistic unit at the step 906 , the spell-check flow 900 proceeds to step 910 . At the step 910 , the parsing-and-mapping engine 74 may identify top matches in the subject dictionary selected for searching via a match coefficient. As used herein, a match coefficient may be considered a metric that serves as a measure of a degree to which a first linguistic unit linguistically matches a second linguistic unit. As part of calculating the match coefficient, an edit-distance-ratio algorithm and a metaphone-ratio algorithm may be performed.
[0068] As one of ordinary skill in the art will appreciate, a formula for calculating an edit-distance ratio between a first linguistic unit (i.e., ‘A’) and a second linguistic unit (i.e., ‘B’) may be expressed as follows:
[0000] Max_Length=Max( A .Length, B .Length)
[0000] Edit-Distance Ratio( A,B )=(Max_Length−Edit Distance( A,B ))/Max_Length
[0069] An edit distance between two linguistic units may be defined as a minimum number of edits necessary to transform the first linguistic unit (i.e., ‘A’) into the second linguistic unit (i.e., ‘B’). A length of the first linguistic unit (i.e., ‘A’) may be defined as the number of characters contained in the first linguistic unit. Similarly, a length of the second linguistic unit (i.e., ‘B’) may be defined as the number of characters contained in the second linguistic unit. One of ordinary skill in the art will recognize that the only allowable “edits” for purposes of calculating an edit distance are insertions, deletions or substitutions of a single character. One of ordinary skill in the art will further recognize that the formula for edit-distance ratio expressed above is exemplary in nature and, in various embodiments, may be modified or optimized without departing from the principles of the present invention. In that way, an edit-distance ratio between the parsed linguistic unit and a target linguistic unit in the subject dictionary selected for searching may be similarly calculated.
[0070] As one of ordinary skill in the art will appreciate, a formula for calculating a double-metaphone ratio may be expressed as follows:
[0000] Double-Metaphone Ratio( A,B )=Edit-Distance Ratio( A .Phonetic_Form, B .Phonetic_Form)
[0000] As one of ordinary skill in the art will appreciate, the double-metaphone ratio algorithm compares a phonetic form for the first linguistic unit (i.e., ‘A’) and the second linguistic unit (i.e., ‘B’) and returns a floating number between 0 and 1 that is indicative of a degree to which the first linguistic unit and the second linguistic unit phonetically match. In various embodiments, the double-metaphone ratio algorithm may vary as, for example, as to how A.Phonetic_Form and B.Phonetic_Form are determined and as to how an edit-distance ratio between A.Phonetic_Form and B.Phonetic_Form are calculated. In that way, a double-metaphone ratio between the parsed linguistic unit and a target linguistic unit in the subject dictionary selected for searching may be similarly calculated.
[0071] For example, as one of ordinary skill in the art will recognize, the double-metaphone algorithm may determine a primary phonetic form for a linguistic unit and an alternate phonetic form for the linguistic unit. Therefore, in some embodiments, it is possible for both the parsed linguistic unit and a target linguistic unit in the subject dictionary selected for searching to each yield a primary phonetic form and an alternate phonetic form. If the primary phonetic form and the alternate phonetic form for both the parsed linguistic unit and the target linguistic unit in the subject dictionary selected for searching are considered, one of ordinary skill in the art will recognize that four edit-distance ratios may be calculated. In some embodiments, the double-metaphone ratio may be a maximum of the four edit-distance ratios. In other embodiments, the double-metaphone ratio may be an average of the four edit-distance ratios. In still other embodiments the double-metaphone ratio may be a weighted average of the four edit-distance ratios such as, for example, by giving greater weight to ratios between primary phonetic forms.
[0072] In some embodiments, greater accuracy for the double-metaphone algorithm may be achieved by further considering a double-metaphone ratio for a backwards form of the parsed linguistic unit. The backwards form of the parsed linguistic unit is, in a typical embodiment, the parsed linguistic unit with its characters reversed. As discussed above, the double-metaphone ratio for the backwards form of the parsed linguistic unit may be considered via, for example, an average or weighted average with the double-metaphone ratio for the parsed linguistic unit in its original form. One of ordinary skill in the art will recognize that any formulas and methodologies for calculating a double-metaphone ratio expressed above are exemplary in nature and, in various embodiments, may be modified or optimized without departing from the principles of the present invention.
[0073] Still referring to the step 910 of FIG. 9 , in a typical embodiment, an overall edit-distance ratio and an overall double-metaphone ratio may be calculated using, for example, one or more methodologies discussed above. Using the double-metaphone ratio and the edit-distance ratio, a match coefficient may be calculated, for example, as follows:
[0000] Match Coefficient( A,B )=(Exact-Match( A,B )+Edit-Distance Ratio( A,B )+Double-Metaphone Ratio( A,B ))/3
[0000] As one of ordinary skill in the art will recognize, by virtue of reaching the step 910 , no exact match for the raw linguistic typically exists in the dictionary selected for searching. Therefore, “Exact-Match (A, B)” will generally be zero.
[0074] In various embodiments, a result of the step 910 is that the parsing-and-mapping engine 74 identifies the top matches, by match coefficient, in the subject dictionary selected for searching. In a typical embodiment, any matches that have a match coefficient that is less than a dictionary coefficient for the subject dictionary selected for searching may be removed from the top matches. The dictionary coefficient, in a typical embodiment, is a metric representing an average edit distance between any two nearest neighbors in a dictionary. For example, a formula for the dictionary coefficient may be expressed as follows:
[0000] Dictionary Coefficient=(½)+(Average_Edit_Distance(Dictionary)/2)
[0000] In this manner, in terms of edit distance, it may be ensured that the top matches match the parsed linguistic unit at least as well as any two neighboring linguistic units in the subject dictionary selected for searching, on average, match each other.
[0075] In a typical embodiment, after the step 910 , the spell-check flow 900 proceeds to step 912 . At the step 912 , the parsing-and-mapping engine 74 may determine whether, for example, others of the plurality of subject dictionaries 358 of FIG. 3 should be searched according to the predetermined order discussed above. If so, the spell-check flow 900 returns to the step 904 for selection of another subject dictionary according to the predetermined order. Otherwise, the spell-check flow 900 proceeds to step 914 .
[0076] At the step 914 , the parsing-and-mapping engine 74 may perform statistical calculations on a set of all top matches identified across, for example, the plurality of subject dictionaries 358 of FIG. 3 . As will be apparent from discussions above, the set of all top matches may include, in a typical embodiment, exact matches and matches for which a match coefficient is greater-than-or-equal-to an applicable dictionary coefficient. Table 2 describes a plurality of frequency metrics that may be calculated according to a typical embodiment.
[0000]
TABLE 2
FREQUENCY METRIC
DESCRIPTION
Local Frequency
Number of occurrences of a
particular linguistic unit from a
particular subject dictionary in a
set of master data.
Max Frequency
Maximum of all local frequencies
Total Frequency
Sum of all local frequencies
[0077] In a typical embodiment, a local frequency may be calculated for each top match of the set of all top matches. As mentioned above with respect to FIG. 3 , in a typical embodiment, the HCM language library 38 of FIG. 3 may be configured and pre-calibrated, via HCM subject-matter expertise, to the set of HCM master data. Therefore, in various embodiments, the local frequency may represent a total number of occurrences of a particular top match from the set of all top matches in a corresponding subject dictionary from the plurality of subject dictionaries 358 of FIG. 3 . In a typical embodiment, the local frequency may already be stored in the corresponding subject dictionary. Therefore, a max frequency may be identified by determining which top match from the set of all top matches has the largest local frequency. A total frequency may be calculated by totaling local frequencies for each top match of the set of all top matches.
[0078] From the step 914 , the spell-check flow 900 proceeds to step 916 . At the step 916 , the parsing-and-mapping engine 74 may compute a weighted score for each top match in the set of all top matches. In various embodiments, the weighted score may be calculated as follows:
[0000] Weighted Score=Match Coefficient*Local_Frequency/Total Frequency
[0000] One of ordinary skill in the art will note that the weighted score yields a value between 0 and 1. In that way, the parsing-and-mapping engine may weight a particular top match's match coefficient based on a frequency of that top match relative to frequencies of other top matches.
[0079] From step 916 , the spell-check flow 900 proceeds to step 918 . At the step 918 , the parsing-and-mapping engine 74 may identify overall top matches in the set of all top matches. In a typical embodiment, the overall top matches in the set of all top matches are those matches that meet one or more predetermined statistical criteria. An exemplary pre-determined statistical criterion is as follows:
[0000] Local Frequency>=Max_Frequency−(3*Standard_Deviation(Local_Frequencies))
[0000] Thus, in some embodiments, the overall top matches may include each top match in the set of all top matches for which the local frequency meets the exemplary pre-determined statistical criterion. After the step 918 , the spell-check flow 900 ends. In a typical embodiment, the process 900 may be performed for each of the plurality of parsed linguistic units produced by the parsing flow 800 of FIG. 8A .
[0080] FIG. 10 illustrates an abbreviation flow 1000 that may be performed by the parsing-and-mapping engine 74 during, for example, the abbreviation step 706 of FIG. 7 . It should be noted that, in a typical embodiment, if it can be determined that none of the overall total matches from the spell-check flow 900 and the parsed linguistic unit are abbreviations, then the process 1000 need not be performed. This may be determined, for example, by referencing the HCM master dictionary of FIG. 3 and a part-of-speech identified, for example, during the parsing flow 800 of FIG. 8B . At step 1002 , the parsing-and-mapping engine 74 may check an abbreviation dictionary such as, for example, the abbreviation dictionary 362 of FIG. 3 . In a typical embodiment, the abbreviation dictionary may be checked with respect to each parsed linguistic unit in the plurality of parsed linguistic units produced by the parsing flow 800 of FIG. 8A and each of the overall top matches from the spell-check flow 900 .
[0081] At step 1004 , the parsed linguistic unit and each of the overall top matches are mapped to any possible abbreviations listed, for example, in the abbreviation dictionary 362 of FIG. 3 . One of ordinary skill in the art will recognize that the abbreviation dictionary 362 , in a typical embodiment, may yield possible abbreviations, for example, across the plurality of subject dictionaries 358 of FIG. 3 . In a typical embodiment, a weighted score for each of the possible abbreviations may be obtained, for example, from the abbreviation dictionary 362 . Following the step 1004 , the abbreviation flow 1000 ends.
[0082] FIG. 11A illustrates an inference flow 1100 that may be performed by the parsing-and-mapping engine 74 during, for example, the inference step 708 of FIG. 7 . At step 1102 , the parsing-and-mapping engine 74 may check an inference dictionary such as, for example, the inference dictionary 360 of FIG. 3 . In various embodiments, with respect to a parsed linguistic unit in the plurality of parsed linguistic units from the parsing flow 800 of FIG. 8A , the parsed linguistic unit, the overall top matches from the spell-check flow 900 of FIG. 9 and the possible abbreviations from the abbreviation flow 1000 of FIG. 10 are all checked in the inference dictionary 360 of FIG. 3 . To facilitate the discussion of the inference flow 1100 , the parsed linguistic unit, the overall top matches from the spell-check flow 900 of FIG. 9 and the possible abbreviations from the abbreviation flow 1000 of FIG. 10 will be collectively referenced as source linguistic units. Table 3 lists exemplary relationships that may be included in the inference dictionary 360 of FIG. 3 . Other types of relationships are also possible and will be apparent to one of ordinary skill in the art.
[0000]
TABLE 3
RELATIONSHIP
RANKING
“IS-A” Relationship
Rank = 1
Synonym
Rank = 1
Frequency-Based Relationship
Rank from 1 to n based on
frequency
[0083] As shown in Table 3, the inference dictionary 360 of FIG. 3 may yield, for example, “IS-A” relationships, synonyms and frequency-based relationships. In a typical embodiment, an “IS-A” relationship is a relationship that infers a more generic linguistic unit from a more specific linguistic unit. For example, a linguistic unit of “milk” may have an “IS-A” relationship with “dairy product” since milk is a dairy product. “IS-A” relationships may be applied in a similar manner in the HCM subject-matter domain. In a typical embodiment, a synonym relationship is a relationship based on one linguistic unit being synonymous, in at least one context, with another linguistic unit. A frequency-based relationship is a relationship based on two linguistic units being “frequently” related, typically in a situation where no other relationship can be clearly stated. With a frequency-based relationship, the inference dictionary 360 typically lists a frequency for the relationship, for example, from the set of master data for the HCM language library 38 of FIG. 3 . In a typical embodiment, the inference dictionary 360 of FIG. 3 may list one or more relationships for each of the source linguistic units.
[0084] At step 1104 , each of the source linguistic units are mapped to any possible inferences, or inferred linguistic units, from the inference dictionary 360 . In a typical embodiment, “IS-A” relationships and synonym relationships are each given a rank of one. Additionally, in a typical embodiment, frequency-based relationships are ranked from one to n based on, for example, a frequency number provided in the inference dictionary 360 . The inferred linguistic units are, in a typical embodiment, retained and stored with the source linguistic units, that is, the parsed linguistic unit, the overall top matches from the spell-check flow 900 of FIG. 9 and the possible abbreviations from the abbreviation flow 1000 of FIG. 10 . After the step 1104 , the inference flow 1100 ends.
[0085] FIG. 11B illustrates a graph 1150 that may utilized in various embodiments. One of ordinary skill in the art will recognize that the graph 1150 is a Cauchy distribution. In a typical embodiment, the graph 1150 may be utilized to convert, for example, a rank on the x-axis to a weighted score between zero and one on the y-axis. For example, the graph 1150 may be utilized to convert and store a rank associated with each of the inferred linguistic units produced in the process 1100 of FIG. 11A into a weighted score. One of ordinary skill in the art will appreciate that, in various embodiments, other distributions may be used in place of the Cauchy distribution.
[0086] FIG. 12 illustrates an exemplary multidimensional vector 1202 that may, in various embodiments, be produced as a result of the parsing flow 800 , the spell-check flow 900 , the abbreviation flow 1000 and the inference flow 1100 . In various embodiments, the multidimensional vector 1202 may be similar to the multidimensional vector 206 of FIG. 2 . As shown, in a typical embodiment, the multidimensional vector 1202 may be traced to the raw-data data structure 702 of FIG. 7 and the parsed data record 82 of FIG. 8B .
[0087] In various embodiments, the multidimensional vector 1202 represents a projection of the plurality of parsed linguistic units produced in the parsing flow 800 of FIG. 8A onto the HCM vector space. The multidimensional vector 1202 generally includes the plurality of parsed linguistic units produced in the parsing flow 800 of FIG. 8A . The multidimensional vector also generally includes, for each parsed linguistic unit in the plurality of parsed linguistic units: each of the overall top matches from the spell-check flow 900 of FIG. 9 , each of the possible abbreviations from the abbreviation flow 1000 of FIG. 10 and each of the inferred linguistic units from the inference flow 1100 as dimensions of the multidimensional vector 1202 . Each dimension of the multidimensional vector 1202 is thus a vector that has direction and magnitude (e.g., weight) relative to the HCM vector space. More particularly, each dimension of the multidimensional vector 1202 typically corresponds to a subject dictionary, for example, from the plurality of subject dictionaries 358 . In a typical embodiment, each dimension of the multidimensional vector 1202 thereby provides a probabilistic assessment as to one or more meanings of the plurality of parsed linguistic units in the HCM subject-matter domain. In that way, each dimension of the multidimensional vector 1202 may reflect one or more possible meanings of the plurality of parsed linguistic units and a level of confidence, or weight, in those possible meanings.
[0088] FIG. 13 illustrates an exemplary process 1300 that may be performed by a similarity-and-relevancy engine 1326 . In various embodiments, the similarity-and-relevancy engine 1326 may be similar to the similarity-and-relevancy engine 26 of FIG. 2 and the similarity-and-relevancy engine 16 of FIG. 1B . At step 1302 , subject to various performance optimizations that may be implemented, a node-category score may be calculated for each of a plurality of subject dictionaries, for each node of a HCM master taxonomy between a domain level and a family level and across the plurality of parsed linguistic units produced, for example, by the parsing flow 800 of FIG. 8A . In various embodiments, the plurality of subject dictionaries may be, for example, the plurality of subject dictionaries 358 of FIG. 3 and the HCM master taxonomy may be, for example, the HCM master taxonomy 418 of FIG. 4 . Further, in a typical embodiment, the node-category score may be calculated for each node of the HCM master taxonomy 418 beginning at the job-domain level 420 through the job-family level 428 .
[0089] In a typical embodiment, each of the overall top matches from the spell-check flow 900 of FIG. 9 , each of the possible abbreviations from the abbreviation flow 1000 of FIG. 10 and each of the inferred linguistic units from the inference flow 1100 may represent a possible meaning of a particular parsed linguistic unit. Further, as noted above, each such possible meaning typically has a weighted score indicating a degree of confidence in the possible meaning In a typical embodiment, calculating the node-category score at the step 1302 may involve, first, identifying a highest-weighted possible meaning at a dimension of the multidimensional vector for a particular one of the parsed linguistic units. The highest-weighted possible meaning is generally a possible meaning with the highest weighted score.
[0090] Typically, the highest-weighted possible meaning is identified for each parsed linguistic unit in the plurality of parsed linguistic units produced in the parsing flow 800 of FIG. 8A . In a typical embodiment, the node-category score involves summing the weighted scores for the highest-weighted possible meaning for each of the plurality of parsed linguistic units produced in the parsing flow 800 of FIG. 8A . In that way, a node-category score may be calculated, for example, for a particular dimension of the multidimensional vector 1202 of FIG. 12 . In a typical embodiment, the step 1302 may be repeated for each dimension of the multidimensional vector 1202 of FIG. 12 . In various embodiments, following the step 1302 , a node-category score is obtained for each node of the HCM master taxonomy 418 from the job-domain level 420 through the job-family level 428 .
[0091] Various performance optimizations may be possible with respect to the step 1302 . For example, one of ordinary skill in the art will recognize that a master taxonomy such as, for example, the HCM master taxonomy 418 may conceivably include thousands or millions of nodes. Therefore, in various embodiments, it is beneficial to reduce a number of nodes for which a node-category score must be calculated. In some embodiments, the number of nodes for which the node-category score must be calculated may be reduced by creating a stop condition when, for example, a node-category score is zero. In these embodiments, all nodes beneath a node having a node-category score of zero may be ignored under an assumption that the node-category score for these nodes is also zero.
[0092] For example, if a node-category score of zero is obtained for a node at the job-domain level 420 , all nodes beneath that node in the HCM master taxonomy 418 , in a typical embodiment, may be ignored and assumed to similarly have a node-category score of zero. In various embodiments, this optimization is particularly effective, for example, at domain, category and subcategory levels of a master taxonomy such as, for example, the master taxonomy 418 . Additionally, in various embodiments, utilization of this optimization may result in faster and more efficient operation of a similarity-and-relevancy engine such as, for example, the similarity- and relevancy engine 1326 . One of ordinary skill in the art will recognize that other stop conditions are also possible and are fully contemplated as falling within the scope of the present invention.
[0093] In various embodiments, performance of the step 1302 may also be optimized through utilization of bit flags. For example, in a typical embodiment, a node in the HCM master taxonomy 418 , hereinafter a flagged node, may have a bit flag associated with a node attribute for the flagged node. In a typical embodiment, the bit flag may provide certain information regarding whether the associated node attribute may also be a node attribute for the flagged node's siblings. As one of ordinary skill in the art will appreciate, all nodes that immediately depend from the same parent may be considered siblings. For example, with respect to the HCM master taxonomy 418 of FIG. 4 , all nodes at the job-family level 438 that immediately depend from a single node at the job-family level 428 may be considered siblings.
[0094] In a typical embodiment, the bit flag may specify: (1) an action that is taken if a particular condition is satisfied; and/or (2) an action that is taken if a particular condition is not satisfied. For example, in various embodiments, the bit flag may specify: (1) an action that is taken if the associated node attribute matches, for example, a dimension of the multidimensional vector 1202 of FIG. 12 ; and/or (2) an action that is taken if the associated node attribute does not match, for example, a dimension of the multidimensional vector 1202 of FIG. 12 . Table 4 provides a list of exemplary bit flags and various actions that may be taken based thereon. One of ordinary skill in the art will recognize that other types of bit flags and actions are also possible.
[0000]
TABLE 4
ACTION IF VECTOR
ACTION IF VECTOR
DOES NOT MATCH
BIT FLAG
MATCHES ATTRIBUTE
ATTRIBUTE
Attribute Only Exists
For flagged node, add
No action.
weighted score to the node-
category score; for all siblings,
node-category score = 0.
Attribute Must Exist
For flagged node, add
For flagged node, node-
weighted score to the node-
category score = 0; for all siblings,
category score; for siblings, no action.
node-category score = 0.
Attribute Can Exist
For flagged node, add
No action.
weighted score to the node-category
score; for siblings, no action.
Attribute Must Not Exist
For flagged node, node-
No action.
category score = 0; for all
siblings, node-category score = 0.
[0095] For example, as shown in Table 4, in a typical embodiment, the similarity-and-relevancy engine 1326 may utilize an attribute-only-exists bit flag, an attribute-must-exist bit flag, an attribute-can-exist bit flag and an attribute-must-not-exist bit flag. In some embodiments, every node in a master taxonomy such as, for example, the HCM master taxonomy 418 may have bit flag associated with each node attribute. In these embodiments, the bit flag may be one of the four bit flags specified in Table 4.
[0096] In a typical embodiment, the attribute-only-exist bit flag indicates that, among the flagged node and the flagged node's siblings, only the flagged node has the associated attribute. Therefore, according to the attribute-only-exist bit flag, if the associated node attribute matches, for example, a dimension of the multidimensional vector 1202 of FIG. 12 , the similarity-and-relevancy engine 1326 may skip the flagged node's siblings for purposes of calculating a node-category score as part of the step 1302 of FIG. 13 . Rather, the similarity-and-relevancy engine 1326 may take the action specified in Table 4 under “Action if Vector Matches Attribute.” Otherwise, no action is taken. In this manner, the similarity-and-relevancy engine 1326 may proceed more quickly and more efficiently.
[0097] In a typical embodiment, the attribute-must-exist flag indicates that, in order for the flagged node or any of the flagged node's siblings to be considered to match a dimension of a multidimensional vector such as, for example, the multidimensional vector 1202 of FIG. 12 , the associated attribute must independently match the dimension of the multidimensional vector. If the associated attribute does not independently match the dimension of the multidimensional vector, the similarity-and-relevancy engine 1326 may skip the flagged node's siblings for purposes of calculating a node-category score as part of the step 1302 of FIG. 13 . Rather, the similarity-and-relevancy engine 1326 may take the action specified in Table 4 under “Action if Vector Does Not Match Node Attribute.” Otherwise, the similarity-and-relevancy engine 1326 may take the action specified in Table 4 under “Action if Vector Matches Attribute.” In this manner, the similarity-and-relevancy engine 1326 may proceed more quickly and more efficiently.
[0098] In a typical embodiment, the attribute-can-exist bit flag indicates that the associated node attribute may exist but provides no definitive guidance as to the flagged node's siblings. According to the attribute-can-exist flag, if the associated node attribute matches, for example, a dimension of the multidimensional vector 1202 of FIG. 12 , the similarity-and-relevancy engine 1326 may take the action specified in Table 4 under “Action if Vector Matches Attribute.” Otherwise, no action is taken.
[0099] In a typical embodiment, the attribute-must-not-exist bit flag indicates that neither the flagged node nor the flagged node's siblings have the associated node attribute. Therefore, according to the attribute-must-not-exist bit flag, if the associated node attribute matches, for example, a dimension of the multidimensional vector 1202 of FIG. 12 , the similarity-and-relevancy engine 1326 may skip the flagged node's siblings for purposes of calculating a node-category score as part of the step 1302 of FIG. 13 . Rather, the similarity-and-relevancy engine 1326 may take the action specified in Table 4 under “Action if Vector Matches Attribute.” Otherwise, no action is taken. In this manner, the similarity-and-relevancy engine 1326 may proceed more quickly and more efficiently.
[0100] Following the step 1302 , the process 1300 proceeds to step 1304 . At the step 1304 , an overall node score may be calculated for each node of the HCM master taxonomy 418 of FIG. 4 from the job-domain level 420 through the job-family level 428 . In a typical embodiment, the overall node score may be calculated, for example, by performing the following calculation for a particular node:
[0000] Overall_Node_Score=Square-Root(( C*S 1 )̂2+( C*S 2 )̂2+ . . . +( C*S n )̂2)
[0000] In the formula above, C represents a category weight, S 1 and S 2 each represent a node-category score and ‘n’ represents a total number of node-category scores for the particular node. In a typical embodiment, a category weight is a constant factor that may be used to provide more weight to node-category weights for certain dimensions of the multidimensional vector 1202 of FIG. 12 than others. Table 5 provides a list of exemplary category weights that may be utilized in various embodiments.
[0000]
TABLE 5
SUBJECT
WEIGHT
Job
1
Product
0.86
Organization
0.66
Person
0.32
Place
0.20
Date
0.11
[0101] From the step 1304 , the process 1300 proceeds to step 1306 . At the step 1306 , the similarity-and-relevancy engine 1326 may calculate a node lineage score for each node at a particular level, for example, of the HCM master taxonomy 418 of FIG. 4 . In a typical embodiment, the node lineage score is initially calculated for each node at the job-family level 428 of the HCM master taxonomy 418 of FIG. 4 . In a typical embodiment, a maximum node lineage score may be identified and utilized in subsequent steps of the process 1300 . For example, a node lineage score may be expressed as follows:
[0000] Node_Lineage_Score Node =Square-Root((Node_Level_Weight Node *Overall_Node_Score Node )̂2+ . . . +(Node_Level_Weight Domain *Overall_Node_Score Domain )̂2)
[0102] As part of the formula above, calculating the node lineage score for a particular node (i.e., Node_Lineage_Score Node ) may involve calculating a product of a node-level weight for the particular node (i.e., Node_Level_Weight Node ) and an overall node score for the particular node (i.e., Overall_Node_Score Node ). Typically, as shown in the formula above, a product is similarly calculated for each parent of the particular node up to a domain level such as, for example, the job-domain level 420 . Therefore, a plurality of products will result. In a typical embodiment, as indicated in the formula above, each of the plurality of products may be squared and subsequently summed to yield a total. Finally, in the formula above, a square-root of the total may be taken in order to obtain the node lineage score for the node (i.e., Node_Lineage_Score Node ).
[0103] In various embodiments, as indicated in the exemplary formula above, the node lineage score may utilize a node-level weight. The node-level weight, in a typical embodiment, is a constant factor that may be used to express a preference for overall node scores of nodes that are deeper, for example, in, the HCM master taxonomy 418 . For example, Table 6 lists various exemplary node-level weights that may be used to express this preference. One of ordinary skill in the art will recognize that other node-level weights may also be utilized without departing from the principles of the present invention.
[0000]
TABLE 6
NODE
LEVEL
WEIGHT
Domain
1
Category
2
Sub-Category
3
Class
4
Family
5
[0104] From the step 1306 , the process 1300 proceeds to step 1308 . At the step 1308 , the similarity-and-relevancy engine 1326 may calculate a distance between the maximum node-lineage score identified at the step 1306 and each sibling of a node having the maximum node-lineage score. For simplicity of description, the node having the maximum node-lineage score will be referenced as a candidate node and a sibling of the candidate node will be referenced as a sibling node. In various embodiments, an objective of the step 1306 is to use the distance between the candidate node and each sibling node to help ensure that the candidate node more closely matches, for example, the multidimensional vector 1202 of FIG. 12 than it does any sibling node. In other words, the step 1306 may provide a way to ensure a certain level confidence in the candidate node.
[0105] In a typical embodiment, for a particular sibling node, the step 1308 generally involves processing node attributes of the particular sibling node as a first hypothetical input into the similarity-and-matching engine 1326 solely with respect to the candidate node. In other words, the step 1302 , the step 1304 and the 1306 may be performed with the hypothetical input in such a manner that ignores all nodes except for the candidate node. The first hypothetical input, in a typical embodiment, yields a first hypothetical node-lineage score that is based on a degree of match between the node attributes of the sibling node and the candidate node.
[0106] Similarly, in a typical embodiment, the step 1308 further involves processing node attributes of the candidate node as a second hypothetical input into the similarity-and-matching engine 1326 solely with respect to the candidate node. In other words, the step 1302 , the step 1304 and the 1306 may be performed with the second hypothetical input in such a manner that ignores all nodes except for the candidate node. The second hypothetical input, in a typical embodiment, yields a second hypothetical node-lineage score based on a degree of match between the node attributes of the candidate node and the candidate node.
[0107] Therefore, in various embodiments, a distance between the candidate node and the particular sibling node may be considered to be the first hypothetical node-lineage score divided by the second hypothetical node-lineage score. Similarly, in various embodiments, a distance between, for example, the multidimensional vector 1202 of FIG. 12 and the candidate node may be considered to be the maximum node-lineage score divided by the second hypothetical node-lineage score. In a typical embodiment, the calculations described above with respect to the particular sibling node may be performed for each sibling node of the candidate node.
[0108] From the step 1308 , the process 1300 proceeds to step 1310 . At the step 1310 , a best-match node, for example, for the multidimensional vector 1202 of FIG. 12 may be selected. In a typical embodiment, the candidate node must meet at least one pre-defined criterion in order to be deemed the best-match node. For example, in a typical embodiment, for each sibling node of the candidate node, the distance between the multidimensional vector 1202 of FIG. 12 and the candidate node must be less than the distance between the candidate node and the sibling node. In a typical embodiment, if the at least one pre-defined criterion is not met, the step 1306 , the step 1308 and the step 1310 may be repeated one level higher, for example, in the HCM master taxonomy 418 of FIG. 4 . For example, if the best-match node cannot be identified at the job-family level 428 , the step 1306 , the step 1308 and the step 1310 may proceed with respect to the job-class level 426 . In a typical embodiment, the HCM master taxonomy 418 is optimized so that, in almost all cases, the best-match node may be identified at the job-family level 428 . Therefore, in a typical embodiment, the step 1310 yields a collection of similar species at the job-species level 438 , species in the collection of similar species having the best-match node as a parent. Following the step 1310 , the process 1300 ends.
[0109] FIG. 14 illustrates an exemplary process 1400 that may be performed by an attribute-differential engine 1421 . In various embodiments, the attribute-differential engine 1421 may be similar to the attribute-differential engine 21 of FIG. 2 . At step 1402 , the attribute-differential engine 1421 may identify differences between node attributes for each species of the collection of similar species produced by the process 1300 of FIG. 13 . Identified differences may be similar, for example, to the modifying attributes 252 of FIG. 2 . From step 1402 , the process 1400 proceeds to step 1404 . At the step 1404 , an impact of the identified differences may be analyzed relative to a spotlight attribute such as, for example, a pay rate for a human resource. In a typical embodiment, the attribute-differential engine 1421 may statistically measure the impact in the HCM vector space based on, for example, the HCM language library 38 . From the step 1404 , the process 1400 proceeds to step 1406 .
[0110] At the step 1406 , a set of KPIs may be determined. In a typical embodiment, the set of KPIs may be similar to the set of KPIs 254 of FIG. 2 . In a typical embodiment, the set of KPIs may be represent ones of the identified differences that statistically drive, for example, the pay rate for a human resource. From step 1406 , the process 1400 proceeds to step 1408 .
[0111] At the step 1408 , the attribute-differential engine 1421 is operable to determine whether, for example, the multidimensional vector 1202 of FIG. 2 may be considered a new species or an existing species (i.e., a species from the collection of similar species). If the multidimensional vector 1202 is determined, based on the set of KPIs, to be an existing species for a particular species in the collection of similar species, the multidimensional vector 1202 may be so classified at step 1410 . In that case, the multidimensional vector 1202 may be considered to have, for example, a same pay rate as the particular species. Following the step 1410 , the process 1400 ends. However, if at the step 1408 the multidimensional vector 1202 is determined to be a new species, the new species may be created and configured at step 1412 . In a typical embodiment, the new species may be configured to have, for example, a pay rate that is calculated as a function of a distance from species in the collection of similar species. Following the step 1412 , the process 1400 ends.
[0112] Although various embodiments of the method and apparatus of the present invention have been illustrated in the accompanying Drawings and described in the foregoing Detailed Description, it will be understood that the invention is not limited to the embodiments disclosed, but is capable of numerous rearrangements, modifications and substitutions without departing from the spirit of the invention as set forth herein. | A method includes configuring a human-capital-management (HCM) master taxonomy and a HCM language library. The HCM master taxonomy includes a plurality of levels that range from more general to more specific, each level of the plurality of levels comprising a plurality of nodes. The plurality of levels include a job-species level and a job-family level, the job-species level including a level of greatest specificity in the plurality of levels, the job-family level including a level of specificity immediately above the job-species level. In addition, the method includes transforming human-capital information via the HCM language library. Further, the method includes classifying the transformed human-capital information into a job-family node selected from the plurality of nodes at the job-family level. | 6 |
FIELD OF THE INVENTION
The present invention relates to generating and distributing clock signals in digital systems. More specifically, the present invention relates to minimizing skew in such clock signals.
DESCRIPTION OF THE RELATED ART
It is common for digital systems to send and receive data by placing data on a bus in harmony with a clock signal such that the data is valid on the bus at a time defined by an edge of the clock signal. Of course, it is also often desirable to transmit data as fast as possible, and therefore it is desirable to operate the clock signal at the highest possible frequency.
In a digital system having a component that reads data from a bus, the maximum frequency at which a clock signal can operate is primarily limited by three factors; the set-up time of the data with respect to the clock signal, the hold time of the data with respect to the clock signal, and clock skew. Clock skew can include clock-to-clock skew wherein an edge of a clock signal is skewed with respect to the same edge of the clock signal in a different portion of a circuit, and clock-to-data skew wherein an edge of a clock is skewed with respect to data on a bus.
In digital systems it is common to have many components coupled to a single clock signal, and it is impractical to have a single driver circuit drive the clock inputs of all the components. Therefore, clock buffers are used to make copies of the clock signal for distribution to all components that need the clock signal. However, clock buffers introduce clock skew. To attempt to minimize clock skew, prior art configuration often have clock buffers arranged in a tree-like clock distribution network such that the clock signal supplied to each component traverses the same number of clock buffers. While such arrangements help, there can be significant deviations in skew between clock buffers.
In the field of computing, synchronous dynamic random access memories (SDRAMs) are often used to provide main memory storage in a computer system. Typically, the SDRAMs used in a computer system are mounted onto single in-line memory modules (SIMMs) or dual in-line memory modules (DIMMs), which are then inserted into DIMM or SIMM sockets on a board of the computer system. As is discussed below in the section entitled Detailed Description of the Preferred Embodiments, clock skew found in prior art SIMM and DIMM configurations effectively limits the clock frequency at which SDRAMs are accessed to approximately 100 MHz. In such configurations, the logic state associated with each clock pulse propagates completely through the clock distribution network before the logic state switches.
Since the clock frequency at which SDRAMs operate is limited to 100 MHz, computer designers have focused on increasing the data path width of memory systems to increase memory bandwidth. However, this approach is expensive. As data path widths increase from 64 bits to 128 bits, 256 bits, and beyond, the number of circuit board traces, along with the required circuit board space, becomes prohibitive.
U.S. Pat. No. 5,432,823 to Gasbarro et al. is entitled "Method and Circuitry for Minimizing Clock-Data Skew in a Bus System" and is assigned to Rambus, Inc (the term Rambus® is a registered trademark of Rambus, Inc.). By using the skew minimization techniques taught by Gasbarro et al., as well as several other techniques, Rambus has been able to commercially produce memory subsystems that operate at speeds up to 500 MHz using the same type of dynamic random access memory (DRAM) core used in SDRAMs. At such frequencies, the clock distribution network may simultaneously have more than one clock pulse "in-transit" to a component coupled to the network. The Rambus design provides a large increase in memory bandwidth without having to dramatically increase the width of the data bus.
FIG. 1 is a block diagram adapted from FIG. 3 of Gasbarro et al. and illustrates how clock skew is minimized in Rambus memory systems. In FIG. 1, digital system 10 comprises master receiver/transmitter 12 and slave receiver/transmitters 14, 16, 18, and 20. Master receiver/transmitter 12 and slave receiver/transmitters 14, 16, 18, and 20 are coupled to a data bus 22 and clock distribution system 24. Clock distribution system 24 comprises clock source 25 and clock line 27.
Because of the high frequencies at which clock distribution system 24 operates, clock line 27 may contain more than one clock pulse at any given time. Therefore, the clock pulse present at one receiver/transmitter may not correspond to the clock pulse present at another receiver/transmitter. To address this problem, Gasbarro et al. discloses using two separate segments of clock line 27. The first segment is ClockToMaster 28 and the second segment is ClockFromMaster 26. The two segments are coupled at end 29. Each segment has the same approximate length and electrical characteristics of the conductors of data bus 22.
Segment 26 is used when data is transmitted from master receiver/transmitter 12 to one of the slave receiver/transmitters. For example, consider a write operation from master receiver/transmitter 12 to slave receiver/transmitter 20. A clock pulse is generated at clock source 25 and traverses first segment 28 and end 29. As the pulse begins to traverse second segment 26, it enters the TCLK 0 input of master receiver/transmitter 12, which causes master receiver/transmitter 12 to drive data onto data bus 22. The data propagates on data bus 22 roughly in parallel with the clock pulse that entered the TCLK 0 input until the clock pulse reaches RCLK 3 input of slave receiver/transmitter 20, at which point slave receiver/transmitter 20 clocks in the data. Since the portion of segment 26 traversed by the clock pulse is matched to the portion of data bus 22 traversed by the data, minimal clock skew is introduced. Segment 28 is used in a similar manner when performing a read operation from one of the slaver receiver/transmitters to master receiver/transmitter 12.
Accordingly, each receiver/transmitter 12, 14, 16, 18, and 20 must be able to couple data onto data bus 22 at the instant that its active clock travels past. Gasbarro et al. describe this as being analogous to surfing, in which the surfer watches and anticipates the crest of the wave to catch it and travel with it.
Having two separate clocks coupled to each receiver/transmitter creates synchronization problems within each receiver/transmitter. For a device coupled close to end 29, the phase difference between the transmit clock and the receive clock is minimal. However, devices at the other end, such as slave receiver/transmitter 20, may see a substantial phase difference between the transmit clock and the receive clock. Accordingly, if receiver/transmitters are to be interchangeable and able to assume any position with respect to end 29, each receiver/transmitter must include synchronization circuitry that is able to account for different phase relationships between the transmit and receive clocks.
FIG. 2 is a block diagram of a Rambus 64 megabit DRAM 30 and is adapted from a Rambus 64-Megabit Rambus DRAM Product Summary published Nov. 29, 1995. DRAM 30 is configured as a slave receiver/transmitter, with a Rambus controller configured as a master receiver/transmitter. DRAM 30 is coupled to ClockFromMaster segment 26 and ClockToMaster segment 28, as well as various control and data signals. The purpose in showing FIG. 2 is to illustrate the relative complexity of DRAM 30. As disclosed by Gasbarro et al., each receiver/transmitter must have a phase locked loop to generate phase-shifted versions of the transmit clock. In addition, within each receiver/transmitter, each data line must have a delay element, a phase comparator, a mux, a latch, and several additional stages.
While Rambus memory systems have successfully achieved high transfer frequencies, the design is quite complex and very different from prior art memory subsystems. Phase locked loops can be difficult to implement in high density CMOS implementations, and are susceptible to switching noise frequently present in CMOS memory subsystems. More importantly, phase locked loops are not compatible with clock stopping techniques that are used for reducing power and latency because phase locked loops require a start-up period to lock onto a signal. What is needed in the field of computing is a memory design that is similar to prior art SIMM and DIMM configurations, yet achieves transfer frequencies similar to those achieved by Rambus memory systems.
SUMMARY OF THE INVENTION
The present invention is a method and apparatus for generating and distributing clock signals with minimal skew. In one embodiment, the present invention includes a memory controller and at least one memory module that exchange data at high transfer rates by minimizing clock skew. When writing data to the memory module, the memory controller generates a clock signal that travels along a first clock line segment. The data bus carries the write data and the electrical characteristics of the data bus and first clock line segment are matched such that incident wavefronts of the data bus and clock signal arrive at the memory module in fixed relation to one another. When reading data, the first clock line segment is looped back from the memory module to the memory controller along a second clock line segment, with a copy of the clock signal provided on the second clock line segment. The data bus carries the read data and the electrical characteristics of the data bus and the second clock line segment are matched such that incident wavefronts of the data bus and clock signal arrive at the memory controller in fixed relationship to one another.
In one configuration, the memory module is provided with dummy loads that are coupled to the second clock segment. The dummy load ensure that the electrical characteristics of the second clock segment track the electrical characteristics of the data bus as memory modules are inserted and removed.
The present invention provides a substantial increase in memory bandwidth with minimal design changes to prior art memory modules. In one embodiment, a prior art memory module may be configured to operate in accordance with the present invention simply by coupling an output from a clock buffer on the memory module to an unused pin of the memory module.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram adapted from FIG. 3 of U.S. Pat. No. 5,432,823 to Gasbarro et al. and illustrates how clock skew is minimized in Rambus memory systems.
FIG. 2 is a block diagram of a Rambus 64 megabit DRAM and is adapted from a Rambus 64-Megabit Rambus DRAM Product Summary published Nov. 29, 1995.
FIG. 3 is a block diagram of a prior art memory system using dual in-line memory modules (DIMM).
FIG. 4 is a block diagram of a memory system in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 3 is a block diagram of a prior art memory system 32. Memory system 32 includes memory controller application-specific integrated circuit (ASIC) 34, dual in-line memory modules (DIMMs) 36, 38, and 40, global system clock buffer 42, and memory subsystem clock buffer 44. Each DIMM module includes one or more synchronous dynamic random access memory (SDRAM) circuits and a low skew clock buffer. For example, DIMM 40 includes SDRAMs 46A, 46B, 46C, 46D, and 46E and low skew clock buffer 48.
Memory controller ASIC 34 includes an internal clock buffer 50, data bus drivers 52, data receivers 54, and data registers 56. Data bus 58 is coupled to memory controller ASIC 34 and each of the DIMM modules 36, 38, and 40. Clock signals are distributed to ASIC 34 by the clock distribution network comprised of clock buffers 42 and 44. Buffer 42 receives a master clock signal on line 60, and fans that signal to ASIC 34 via line 62 and buffer 44 via line 64. Buffer 44 fans out the clock signal to DIMMs 36, 38, and 40 via lines 66, 68, and 70, respectively.
As discussed above in the section entitled Description of the Related Art, the frequency at which a clock signal can operate is primarily limited by three factors; the set-up time of the data with respect to the clock signal, the hold time of the data with respect to the clock signal, and clock skew. Skew is a term that is well known in the art of computing. Briefly, skew is the difference between the minimum and maximum times it takes for an event to occur. Skew is additive, so if a signal traverses two gates, and each gate has a skew of 1.0 nS, the total skew is 2.0 nS. To calculate total skew of a circuit, one starts at a point where clock and data, for example, are gated by a common device or exist on at a common point of a net, such as a clock net or clock buffer that drives both an output driver and a clock buffer. From that point, one adds the skew for all devices traversed until the signals reconverge at a clocked device, such as a register, or an output pin. Setup and hold times must also be included when calculating minimum allowable cycle time. An example of such a calculation is set forth below.
One type of skew arises from the total propagation delay (TPD) time of a device as a signal propagates from the input of the device to the output of the device. This type of skew will be referred to herein as TPD skew. Another type of skew arises between potential time differences observed at separate outputs of a device. This type of skew will be referred to herein as output-to-output skew.
Output-to-output skew is easy to control because it is a function of a single semiconductor device whose transistors are fundamentally matched. The single device has a common temperature and common voltage, and any variations caused be fabrication anomalies affect all outputs, and therefore cancel out. On the other hand, TPD skew is much larger because it reflects potential differences in separate semiconductor devices. For example, a typical TPD skew of memory subsystem clock buffer 44 is 1.000 nS, while a typical output-to-output skew is 0.175 nS. Typically, the TPD skew of a device includes the output-to-output skew of a device, so the output-to-output skew of a device is only a factor when the TPD skew is not relevant.
Prior art SDRAM ICs have a setup time of approximately 2.5 nS, a hold time of approximately 1.0 nS, and a TPD skew from clock-to-data of approximately 3.0 nS. However, it is the belief of the inventors of the present invention that these times can and will be improved significantly by using various techniques, such as compensating the delay of the SDRAM output buffers to reduce skew. The inventors anticipates that future versions of SDRAMs will have a setup time of approximately 0.5 nS, a hold time of approximately 0.25 nS, and a TPD skew of approximately 0.75 nS.
As will be shown below, using prior art SDRAM ICs the present invention increases the maximum operating frequency of a memory system constructed from SDRAMs improves by a factor of nearly two. However, using SDRAM ICs having timing characteristics similar to those anticipated by the inventors, the present invention increases the maximum operating frequency by a factor of approximately three to four.
The following timing budgets are calculated using times from prior art SDRAMS. The budgets set forth the setup and hold times and skew times of memory system 32 when performing read and write operations, and define the minimum allowable cycle time for system 32. All budgets assume first incident wavefront switching on data bus 58, wherein data is placed on a data bus as soon as the first wavefront of a clock pulse reaches an output buffer. First wavefront incident switching is easily achieved with the high performance CMOS FET transistors utilized in SDRAM and ASIC devices. The times below are representative of the times of such devices.
______________________________________SDRAM Read Budget for Memory System 32Using Prior Art ComponentsDelayNo. Delay Description Delay Time______________________________________1 Clock Buffer 42 Output-To-Output Skew 0.175 nS2 Clock Buffer 44 TPD Skew 1.000 nS3 DIMM Clock Buffer TPD Skew (e.g., Buffer 48) 1.000 nS4 SDRAM TPD Skew (e.g., SDRAM 46A) 3.000 nS5 Backplane TPD Skew (0.250 nS/Slot * 4 Slots) 1.000 nS6 ASIC 34 Internal Clock Buffer 50 TPD Skew 2.000 nS7 ASIC 34 Setup Time 0.250 nS8 ASIC 34 Hold Time 0.250 nS Total: 8.675 nS Maximum Cycle Frequency 115.3 MHz______________________________________
______________________________________SDRAM Write Budget for Memory System 32Using Prior Art ComponentsDelayNo. Delay Description Delay Time______________________________________ 9 Clock Buffer 42 Output-To-Output Skew 0.175 nS10 ASIC 34 Internal Clock Buffer 50 TPD Skew 2.000 nS11 ASIC 34 Data Bus Driver 52 TPD Skew 0.750 nS12 Backplane TPD Skew (0.250 nS/Slot * 4 Slots) 1.000 nS14 SDRAM Setup Time (e.g., SDRAM 46A) 2.500 nS15 SDRAM Hold Time (e.g., SDRAM 46A) 1.000 nS16 Clock Buffer 44 TPD Skew 1.000 nS17 DIMM Clock Buffer TPD Skew (e.g., Buffer 48) 1.000 nS Total: 9.425 nS Maximum Cycle Frequency 106.1 MHz______________________________________
The calculation of the read budget of circuit 32 starts at buffer 42. Since the outputs of buffer 42 are derived from line 60, only the output-to-output skew of buffer 40 is included in delay 1. Delays 2 and 3 are caused by the TPD skews of clock buffer 44 and the DIMM buffer (e.g., buffer 48), respectively. Delay 4 is the skew introduced by the clock and bus drivers found in each SDRAM.
In many computer systems, memory is organized into N memory subsystems, with each memory subsystem driving M DIMMs for a total of N*M DIMMs. Accordingly, in FIG. 3, M equals three. It takes about 0.250 nS for a signal to traverse the data bus between DIMMs, so in a three DIMM subsystem, the DIMM closest to the memory controller ASIC will receive data about 0.7500 nS before the farthest DIMM. In addition, a bus such as that shown in FIG. 3 will have propagation variation of approximately 0.250 nS. Since data must flow in both direction, the length of the clock line cannot be used to compensate for this delay. Accordingly, a designer must attempt to equalize the clock length flowing to the DIMMs such that the clock can be used for both read and write operations. Delay 5 accounts for propagation variation of 0.250 nS and the skew introduced by the fact that data traveling to different DIMMs traverses different lengths of data bus 58, while the clock signal travels approximately equal lengths. Of course, delay 5 will vary based on the number of DIMMs in a memory subsystem.
Delay 6 is the TPD skew of clock buffer 50 in ASIC 34. Delay 6 also includes the clock-to-data skew of ASIC 34. Delay 7 is the setup time of ASIC 34, and delay 8 is the hold time of ASIC 34. As seen above, the read budget of circuit 32 produces a maximum read cycle frequency 115.3 MHz.
The calculation of the write budget of circuit 32 also starts at buffer 42. Delay 9 is the output-to-output skew of clock buffer 42 and corresponds to delay 1 in the read budget. Delay 10 represents TPD skew of clock buffer 50 of ASIC 34 and corresponds to delay 6 in the read budget. Delay 11 is the TPD skew of bus driver 52 of ASIC 34. Delay 12 is the delay associated with the DIMM backplane and corresponds to delay 5 of the write budget. Delays 14 and 15 are the setup time and the hold time, respectively, of the SDRAM ICs, such as SDRAM 46A. Delay 16 is the TPD skew of clock buffer 44, and delay 17 is the TPD skew of a DIMM clock buffer, such as buffer 48. As seen above, the write budget of circuit 32 produces a maximum write cycle frequency 106.1 MHz, which is the maximum frequency at which circuit 32 may operate.
FIG. 4 is a block diagram of a memory system 72 in accordance with the present invention. Memory system 72 includes memory controller ASIC 74, DIMMs 76, 78, and 80, global system clock buffer 82, data bus 84, clock lines 86, 92, 94, and 96 and delay lines 98, 104, 106, and 108. Each of the clock lines is provided with one of the delay lines. Each DIMM includes a clock buffer and at least one SDRAM IC. For example, DIMM 80 has SDRAMs 110A, 110B, 110C, 110D, and 110E, and buffer 120. Each DIMM clock buffer has outputs that are coupled to the clock inputs of the SDRAMs. In addition, one line of each clock buffer is sent back to ASIC 74 via a clock line. Each DIMM also has connections for dummy loads, which will be described in greater detail below.
Memory controller ASIC 74 includes a clock driver 122, data bus drivers 130, data bus receivers 132, and registers 134, 136, and 138. Registers 134, 136, and 138 are clocked by clock signals provided by the clock buffers on the DIMMs.
A fundamental difference between prior art memory system 32 of FIG. 3 and memory system 72 of the present invention is that the clock that is used by ASIC 74 to clock in read data from a DIMM is provided by the clock buffer on that DIMM. Therefore, clock pulses always travel in the same direction as data. By designing clock lines that have electrical characteristics that correspond to data bus 84, the present invention is able to provide a substantial improvement in the maximum allowable cycle frequency of a memory subsystem. A detailed discussion of these techniques will be presented in view of the SDRAM read and write budgets for circuit 72. The following timing budgets set forth the setup and hold times and skew times of memory circuit 72 when performing read and write operations and define the minimum allowable cycle time for circuit 72. All budgets assume first incident wavefront switching on data bus 84. To show the benefits of the present invention, the timing budgets are calculated using prior-art clock buffers, SDRAMs, and ASICs having timing characteristics identical to those shown in FIG. 3. However, the clock and data paths on the circuit board that connect the clock buffers, SDRAMs, and ASICs must be closely matched, as will be discussed below. To aid in comparing the present invention to prior art memory system 32 of FIG. 1, the delay reference numbers used below are unique from those used above.
______________________________________SDRAM Read Budget for Memory System 72Using Prior Art ComponentsDelay No. Delay Description Delay Time______________________________________18 DIMM Clock Buffer Output-To-Output Skew 0.175 nS (e.g., Buffer 120)19 SDRAM TPD Skew (e.g., SDRAM 110A) 3.000 nS20 Backplane TPD Skew 0.250 nS21 ASIC 74 Data-To-Clock Skew 0.250 nS22 ASIC 74 Data Setup Time 0.250 nS23 ASIC 74 Data Hold Time 0.250 nS Total: 4.175 nS Maximum Cycle Frequency 239.5 MHz______________________________________
______________________________________SDRAM Write Budget for Memory System 72Using Prior Art ComponentsDelayNo. Delay Description Delay Time______________________________________24 ASIC 74 Clock Driver-To-Data Driver Skew 0.500 nS25 Backplane TPD Skew 0.250 nS27 SDRAM Setup Time (e.g., SDRAM 110A) 2.500 nS28 SDRAM Hold Time (e.g., SDRAM 110A) 1.000 nS29 DIMM Clock Buffer TPD Skew (e.g., Buffer 120) 1.000 nSTotal: 5.250 nSMaximum Cycle Frequency 190.5 MHz______________________________________
In memory system 32 of FIG. 3, the calculation of the read budget started at global system clock buffer 42. In the present invention, the clock that is used by ASIC 74 to validate read data is provided by the DIMM clock buffer. One of the advantages provided by this is that the calculation of the read budget begins at a DIMM clock buffer. This eliminates the skew from the global system clock buffer and the memory subsystem clock buffer, and converts the skew of the DIMM clock buffer from a TPD skew to and output-to-output skew. As discussed above, output-to-output skews are much smaller than TPD skews. Accordingly, delay 18 is the output-to-output skew of a DIMM clock buffer, such as buffer 120.
Delay 19 is the SDRAM TPD skew. This delay corresponds with delay 4 of system 32.
As discussed above with respect to FIG. 3, prior art memory system 32 has significant backplane skew. However, in FIG. 4, the clock line running from each DIMM to ASIC 74 is precisely matched to the corresponding data lines of bus 84. In addition, data from each DIMM is clocked into corresponding and separate registers in ASIC 74. For example, data from DIMM 78 is clocked into register 136. The result is that the propagation delay due to the backplane connection between DIMMs is minimized and does not change with the number of DIMMs. Accordingly, delay 20 represents the propagation variation of 0.250 nS associated with bus 84, but does not include skew introduced by data traversing different lengths of data bus 58.
Delay 21 is data-to-clock skew of ASIC 74. In circuit 32, this time was included in the TPD skew of internal clock buffer 50 of ASIC 34 (delay 6). By supplying the clock and data from the DIMMs along matched lines, the present invention substitutes a TPD skew with a much smaller data-to-clock skew.
Delays 22 and 23 are the data setup time and data hold time, respectively, of ASIC 74. These times correspond with delays 7 and 8 of system 32. As seen above, the read budget of circuit 72 produce a maximum read cycle frequency 239.5 MHz. This is a vast improvement over the maximum read cycle frequency of 115.3 MHz provided by circuit 32. However, both circuits use components have similar timing characteristics.
In the present invention, when reading data from the DIMMs, the clock and data originate from the DIMMs and travel along matched lines. Likewise, when writing data to the DIMMs, the clock and data originate from ASIC 74 and travel along matched lines.
In memory system 32 of FIG. 3, the calculation of the write budget started at global system clock buffer 42. In memory system 72 of the present invention, the calculation of the write budget starts at the clock and data outputs of ASIC 74. By routing the clock into and out of ASIC 74, the skew generated by the global system clock buffer is eliminated and the internal clock buffer skew of the ASIC is substituted with a clock driver-to-data driver skew, which is much smaller because ASIC 74 is a single device. Delay 24 is the clock driver-to-data driver skew of ASIC 74.
As discussed above, the present invention minimizes backplane skew. Delay 25 is the back plane skew.
Delays 27 and 28 are the setup time and hold time of the SDRAMs, such as SDRAM 110A. Delays 27 and 28 correspond to delays 14 and 15, respectively, of memory system 32.
Delay 29 is the DIMM clock buffer TPD skew (such as buffer 120) and corresponds to delay 17 of system 32. As seen above, the write budget of circuit 72 produces a maximum read cycle frequency 190.5 MHz, a significant improvement over the maximum read cycle frequency of 106.1 MHz provided by system 32. Accordingly, the memory system of the present invention operates at 190.5 MHz while the memory system of the prior art operates at 106.1 MHz. The present invention therefore provides an 80% improvement in maximum operating frequency using prior art components.
The components used to calculate the read and write budgets of system 72 have timing characteristics identical to those of prior art system 32 of FIG. 3. However, with such components there is a significant discrepancy between the read cycle timing (239.5 MHz) and the write cycle timing (190.5 MHz) of memory system 72. With a minor component substitution, this discrepancy can be reduced substantially.
The value of the TPD skew of the clock buffers used on the DIMMS in systems 32 and 72 is 1.000 nS. This corresponds with low-voltage TTL clock buffers commonly used on DIMMS. However, if a higher cost ECL clock buffer is used on each DIMM, the TPD skew of the buffer drops to 0.200 nS. This drops the total minimum allowable write cycle time to 4.45 nS, and therefore raises the maximum allowable write frequency to 224.7 MHz, thereby moving the write frequency closer to the read frequency. This substitution also provides a small increase in the maximum allowable read frequency because the output-to-output skew of the DIMM clock buffer is also reduced, though to a lesser extent.
Now assume that the prior art memory system 32 and memory system 72 of the present invention are constructed using future versions of SDRAMs having a setup time of approximately 0.5 nS, a hold time of approximately 0.25 nS, and a TPD skew of approximately 0.75 nS, as anticipated by the inventors. The read and write budgets are as follows:
______________________________________SDRAM Read Budget for Memory System 32Using Future ComponentsDelayNo. Delay Description Delay Time______________________________________30 Clock Buffer 42 Output-To-Output Skew 0.175 nS31 Clock Buffer 44 TPD Skew 1.000 nS32 DIMM Clock Buffer TPD Skew (e.g., Buffer 48) 1.000 nS33 SDRAM TPD Skew (e.g., SDRAM 46A) 0.750 nS34 Backplane TPD Skew (0.250 nS/Slot * 4 Slots) 1.000 nS35 ASIC 34 Internal Clock Buffer 50 TPD Skew 2.000 nS36 ASIC 34 Setup Time 0.250 nS37 ASIC 34 Hold Time 0.250 nS Total: 6.425 nS Maximum Cycle Frequency 155.6 MHz______________________________________
______________________________________SDRAM Write Budget for Memory System 32Using Future ComponentsDelayNo. Delay Description Delay Time______________________________________38 Clock Buffer 42 Output-To-Output Skew 0.175 nS39 ASIC 34 Internal Clock Buffer 50 TPD Skew 2.000 nS40 ASIC 34 Data Bus Driver 52 TPD Skew 0.750 nS41 Backplane TPD Skew (0.250 nS/Slot * 4 Slots) 1.000 nS42 SDRAM Setup Time (e.g., SDRAM 46A) 0.500 nS43 SDRAM Hold Time (e.g., SDRAM 46A) 0.250 nS44 Clock Buffer 44 TPD Skew 1.000 nS45 DIMM Clock Buffer TPD Skew (e.g., Buffer 48) 1.000 nS Total: 6.675 nS Maximum Cycle Frequency 149.8 MHz______________________________________
Accordingly, prior art memory system 32 will operate 149.8 MHz when using future SDRAMs, as anticipated by the inventors.
______________________________________SDRAM Read Budget for Memory System 72Using Future ComponentsDelay No. Delay Description Delay Time______________________________________46 DIMM Clock Buffer Output-To-Output Skew 0.175 nS (e.g., Buffer 120)47 SDRAM TPD Skew (e.g., SDRAM 110A) 0.750 nS48 Backplane TPD Skew 0.250 nS49 ASIC 74 Data-To-Clock Skew 0.250 nS50 ASIC 74 Data Setup Time 0.250 nS51 ASIC 74 Data Hold Time 0.250 nS Total: 1.925 nS Maximum Cycle Frequency 519.5 MHz______________________________________
______________________________________SDRAM Write Budget for Memory System 72Using Future ComponentsDelayNo. Delay Description Delay Time______________________________________52 ASIC 74 Clock Driver-To-Data Driver Skew 0.500 nS53 Backplane TPD Skew 0.250 nS54 SDRAM Setup Time (e.g., SDRAM 110A) 0.500 nS55 SDRAM Hold Time (e.g., SDRAM 110A) 0.250 nS56 DIMM Clock Buffer TPD Skew (e.g., Buffer 120) 1.000 nS Total: 2.5 nS Maximum Cycle Frequency 400.0 MHz______________________________________
Accordingly, memory system 72 will operate at 400.0 MHz when using future SDRAMs, as anticipated by the inventors. This is an improvement of 167% over prior art circuit 32. If ECL DIMM clock buffers are used in both circuit 32 and 72, the frequencies jump to 170 MHz and 588 MHz. With ECL buffers and future SDRAMS, memory system 72 is 246% faster than prior art memory system 32.
One of the advantages of prior art SIMMs and DIMMs is that they provide for easy installation and removal of memory. The dummy load connections on each DIMM allow the present invention to continue this advantage, without sacrificing performance. Basically, the dummy loads seek to duplicate on the clock lines the effect that adding additional DIMMS has on the data bus. For example, assume that data is being read from DIMM 80 to ASIC 74, and DIMMs 76 and 78 are installed. DIMM 80 must drive the capacitances of the portions of data bus 84 that extend into DIMMs 76 and 78, and dummy loads 140 and 142 duplicate the electrical effect of these portions, thereby keeping the electrical characteristics of clock line 92 and data bus 84 matched between DIMM 80 and ASIC 74. Now assume that DIMM 78 is removed. Removing DIMM 78 also removes a portion of data bus 84. However, it also removes dummy load 142, so the electrical characteristics of clock line 92 remain matched to those of data bus 84. The number of dummy loads that must be provided on each DIMM is equal to the number of DIMMs that may be placed in a memory subsystem minus one.
Delay line 98 may be needed to create the setup time needed by the SDRAMs when writing to the SDRAMs. The delay lines may simply be an additional routing length, or some other type of delay line as is known in the art. Alternatively, delay line 98 may be moved into ASIC 74, where it could be easy to make the delay of delay line 98 variable.
Likewise, delay lines 104, 106, and 108 may be needed to compensate for the SDRAM propagation delay and to create the setup time needed by ASIC 74. Delay lines 104, 106, and 108 may also be moved into ASIC 74, where it could be easy to make the delay of the delay lines variable.
The delay required by delay line 98 is dependant on the propagation delay of the DIMM clock buffers and the setup time required by the SDRAMs. Delay lines 98, 104, 106, and 108 may also be adjusted to center the clock in the middle of a valid data window so that clock and data arrive at the DIMMS and ASIC 74 with the proper phase relationship.
The present invention provides a substantial improvement in performance over prior art memory systems based on DIMMs and SIMMs with minimal changes to prior art DIMM and SIMM designs. A prior art DIMM design may be modified by simply routing an output of a clock buffer on the DIMM to an unused pin on the DIMM, and providing dummy loads on other unused pins as described above. An additional substantial gain in performance may be achieved by simply replacing a low-voltage TTL clock buffer on the DIMM with an ECL clock buffer.
Although the present invention provides substantial benefits when applied to current memory configurations, the concepts disclosed herein can provide even more benefits when SDRAMs are designed to operated with the present invention. For example, in a small system where the number of SDRAM packages is reduced such that the DIMM clock buffers are eliminated and the clock is provided directly to the SDRAM, and the SDRAM provides a clock out pin that can be sent along with the data to the memory controller ASIC, memory system frequencies may be increased even further. In such a configuration, the SDRAM TPD skew (0.750 nS) would be removed from the read budget, and the DIMM clock buffer output-to-output skew would be substituted with output-to-output skew at the outputs of the SDRAM. This would reduce the read cycle time to 1.175 nS and increase the maximum read cycle frequency to 851.0 MHz. Likewise, such a configuration would remove the DIMM clock buffer TPD skew (1.000 nS) from the write budget, which would reduce the write cycle time to 1.5 nS and increase the maximum read cycle frequency to 666.7 MHz.
The present invention has been described herein with reference to a memory controller and memory modules. However, those skilled in the art will recognize that the present invention may be adapted for use in many other type of digital systems wherein data is sent between first and second data blocks and is validated with a clock signal. In addition, some of the advantages of the present invention can be achieved by simply placing a shadow clock buffer proximate a DIMM socket, and the shadow clock buffer to generate the return clock. In this configuration, many of the advantages of the present invention may be achieved using prior-art DIMMS.
While the present invention provides a substantial improvement in performance over prior art DIMM and SIMM memory configurations, it also has several advantages over high speed prior art memory systems, such as those manufactured by Rambus, Inc. While such high speed prior art memory systems operate at frequencies greater than 500 MHz, they require complex phase detectors, phase locked loops, delay lines, and the like in order to manage clock skew. The present invention achieves speeds that are at least as fast without using such techniques. All that is required are several additional interconnections and careful attention to clock and data lines to ensure that their electrical characteristics are properly matched, and (optionally) the use of a high-speed clock buffer on each DIMM. Finally, since the present invention does not depend on phase locked loops, it is easy to employ clock stopping techniques that are used for reducing power and latency. Phase locked loops require a start-up period to lock onto a signal.
In conclusion, the present invention provides a low-cost, high-performance memory system solution that will meet the challenges created by future generations of processors that will operate at speed of many hundreds of megahertz. Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. | A memory controller and at least one memory module exchange data at high transfer rates by minimizing clock skew. When writing data to the memory module, the memory controller generates a clock signal that travels along a first clock line segment. The data bus carries the write data, and the electrical characteristics of the data bus and first clock line segment are matched such that incident wavefronts of the data bus and clock signal arrive at the memory module in fixed relation to one another. When reading data, the first clock line segment is looped back from the memory module to the memory controller along a second clock line segment, with a copy of the clock signal provided on the second clock line segment. The data bus carries the read data, and the electrical characteristics of the data bus and the first clock line segment are matched such that incident wavefronts of the data bus and clock signal arrive at the memory controller in fixed relationship to one another. The present invention provides a substantial increase in memory bandwidth with minimal design changes to prior art memory systems. | 6 |
BACKGROUND
[0001] This disclosure is related to the field of detection of hypocenters (origin time and position in the subsurface) from passive seismic signals. Passive seismic signals are those detected resulting from microseismic events occurring in the Earth's subsurface, whether the microseismic events are naturally occurring or induced by other activities. More specifically, the disclosure relates to methods for using semblance of corrected amplitudes of passively detected and recorded seismic signals to determine what in the signals are caused by actual microseismic events and to determine the hypocenters of such events.
[0002] Passive seismic signal detection and signal processing methods are widely used for microseismic monitoring of hydraulic fracturing. In such uses, large arrays of seismic sensors deployed at the Earth's surface, buried in shallow boreholes or installed in monitoring wells are used to map induced seismicity. The goals of microseismic data processing include event detection, estimation of hypocenter locations, determination of source mechanisms and magnitudes characterizing induced events. These results may then be used for creation of geomechanical models or simple computation of stimulated rock volume representing a response of the reservoir to stimulation. See, Neuhaus, C. W., Blair, K. Telker, C. and Ellison, M. (2013), Hydrocarbon Production and Microseismic Monitoring—Treatment Optimization in the Marcellus Shale, 75th EAGE Conference & Exhibition incorporating SPE EUROPEC 2013, SPE-164807-MS, and Hummel, N. and Shapiro, S. (2013). Nonlinear diffusion - based interpretation of induced microseismicity: A Barnett Shale hydraulic fracturing case study, Geophysics, 78(5), B211-B226. doi: 10.1190/geo2012-0242.1.
[0003] Because the exact origin time of a microseismic event is not known a priori, in passive seismic surveying seismic signals are acquired continuously for a selected time duration and search routines are implemented to detect events in the acquired signals. To do so one may use multichannel processing of large data sets where events are represented by compressional (P) and/or shear (S) wave arrivals in each seismic sensor signal record trace (a time indexed recording of seismic signal amplitude). However, P and S wave arrivals may not be detectable (e.g., by visual observation or threshold amplitude detection) due to a low signal-to-noise ratio (SNR) which makes event detection in unstacked trace gathers difficult. While generally background noise is higher for surface deployed seismic sensor arrays than for arrays deployed in one or more wellbores, lower amplitude arrivals in both surface and borehole arrays can usually compensated by stacking of signals from a large number of seismic sensors covering a wide range of offsets and azimuths, typically then processed with migration techniques (See, Duncan, P. and Eisner, L. (2010), Reservoir characterization using surface microseismic monitoring, Geophysics, 75(5), 75A139-75A146. doi: 10.1190/1.3467760). An object of microseismic monitoring techniques is to detect microseismic events, including events that are not readily detectable in unstacked trace gathers.
[0004] Migration-based microseismic event detection techniques usually rely on obtaining a high value of a trace sum stack along a moveout curve (a seismic sensor offset dependent time shift for each trace related to the seismic energy velocity distribution in the subsurface) computed from a hypothetical source position, thereby improving the SNR of unstacked traces. See, Duncan and Eisner, 2010, Chambers, K., Kendall, J.-M., Brandsberg-Dahl, S. and Rueda, J. (2010), Testing the ability of surface arrays to monitor microseismic activity, Geophysical Prospecting, 58: 821-830. doi: 10.1111/j.1365-2478.2010.00893.x, Gharti, H., Oye, V., Roth, M., and Kühn, D. (2010), Automated microearthquake location using envelope stacking and robust global optimization, Geophysics, 75(4), MA27-MA46. doi: 10.1190/1.3432784, and Bradford, I., Probert, T., Raymer, D., Ozbek, A., Primiero, P., Kragh, E., Drew, J. and Woerpel, C. (2013), Application of Coalescence Microseismic Mapping to Hydraulic Fracture Monitoring Conducted Using a Surface Array, 75th EAGE Conference & Exhibition incorporating SPE EUROPEC 2013. doi: 10.3997/2214-4609.20131028). However, typical microseismic events do not radiate seismic energy symmetrically as do controlled seismic sources such as dynamite explosions, seismic vibrators and seismic air guns deployed in water. The radiated energy and amplitude polarity of the energy from microseismic events or microearthquakes are strongly directional and have specific signatures due to the specific energy radiation patters of various microseismic source mechanisms. Recorded seismic signal amplitudes from a particular microseismic event may have different polarities and amplitudes at different seismic sensors that differ markedly from what would be anticipated assuming simple symmetrical geometrical spreading of seismic energy from the origin of any microseismic event. Hence, if one simply stacked both positive and negative polarity seismic signals with respect to position or offset one would obtain very low stacked signal amplitude values. The foregoing result may be overcome by stacking the absolute values of signal amplitudes, but at the cost of reducing the SNR of the stacked signal amplitudes. Zhebel, O. and Eisner, L. (2012), Simultaneous microseismic event localization and source mechanism determination, SEG Technical Program Expanded Abstracts 2012: pp. 1-5. doi: 10.1190/s egam2012-1033.1 and Chambers, K., Clarke, J., Velasco, R. and Dando B. (2013), Surface Array Moment Tensor Microseismic Imaging, 75th EAGE Conference & Exhibition incorporating SPE EUROPEC 2013, doi: 10.3997/2214-4609.20130404 describe methods capable of simultaneously determining the origin location and source mechanism of microseismic events. The foregoing methods use a moment tensor inversion of P-wave (or S-wave) amplitudes taken along the moveout direction for every potential origin point in three dimensional (3D) subsurface space and then correct the polarity of detected signal amplitudes using the inverted moment tensor before stacking. Thus, the foregoing methods may obtain the highest stack value for the correct event origin location and source mechanism.
[0005] A challenge in using stacking is that only a few, or in extreme cases even one high amplitude noisy trace may result in high stack amplitudes indicating a spurious detection, the so called “false positive.” See, Thornton, M. and Eisner, L., “ Uncertainty in surface microseismic monitoring, SEG Technical Program Expanded Abstracts, 2011: pp. 1524-1528. doi: 10.1190/1.3627492
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 shows an example of acquisition of passive seismic signals that may be processed according to example embodiments according to the present disclosure.
[0007] FIG. 2 shows a flow chart of an example processing technique according to the present disclosure.
[0008] FIG. 3 shows an example programmable computer that may be used in some embodiments.
DETAILED DESCRIPTION
[0009] FIG. 1 shows an example arrangement of seismic sensors as they may be used in one application of a method according to the present disclosure The embodiment illustrated in FIG. 1 is associated with an application for passive seismic emission tomography known as “fracture monitoring.” It should be clearly understood that the application illustrated in FIG. 1 is only one possible application of a method according to the present disclosure and that use of methods according to the present disclosure are not limited to use with fracture monitoring.
[0010] In the example embodiment of FIG. 1 , each of a plurality of seismic sensors, shown generally at 12 , is deployed at a selected position proximate the Earth's surface 14 . In marine applications, the seismic sensors may be deployed on the water bottom in a device known as an “ocean bottom cable.” The seismic sensors 12 in the present embodiment may be geophones, but may also be accelerometers or any other sensing device known in the art that is responsive to velocity, acceleration or motion of the particles of the Earth proximate the seismic sensor. The seismic sensors 12 generate electrical or optical signals in response to the particle motion, velocity or acceleration, and such signals are ultimately coupled to a recording unit 10 for making a time-indexed recording of the signals from each seismic sensor 12 for later interpretation by a method according to the present disclosure. In other implementations, the seismic sensors 12 may be disposed at various positions within one or more wellbores drilled through subsurface formations. A particular advantage of a method according to the present disclosure is that it provides generally useful results when the seismic sensors are disposed at or near the Earth's surface. Surface deployment of seismic sensors is relatively cost and time effective as contrasted with subsurface seismic sensor emplacements needed in methods known in the art prior to the present disclosure.
[0011] In some embodiments, the seismic sensors 12 may be arranged in sub-groups having spacing therebetween less than about one-half the expected wavelength of seismic energy from the Earth's subsurface that is intended to be detected. Signals from all the seismic sensors 12 in one or more of the sub-groups may be added or summed to reduce the effects of noise in the detected signals.
[0012] In other embodiments, the seismic sensors 12 may be placed in a wellbore, either permanently for certain long-term monitoring applications, or temporarily, such as by wireline conveyance, tubing conveyance or any other sensor conveyance technique known in the art. Irrespective of the manner of deployment or placement of the seismic sensors 12 , they may be arranged proximate the expected positions of seismic events occurring within the subsurface. Proximate in the present context means distances of up to about 10 to 15 km from the position of the seismic event to the most distant seismic sensor.
[0013] A wellbore 22 is shown drilled through various subsurface Earth formations 16 , 18 , through a hydrocarbon producing formation 20 . A wellbore pipe or tubing 24 having perforations 26 formed therein corresponding to the depth of the hydrocarbon producing formation 20 is connected to a valve set known as a wellhead 30 disposed at the Earth's surface. The wellhead 30 may be hydraulic communication with a pump 34 in a fracture fluid pumping unit 32 . The fracture fluid pumping unit 32 is used in the process of pumping a fluid, which in some instances includes selected size solid particles, collectively called “proppant”, are disposed. Pumping such fluid, whether propped or otherwise, is known as hydraulic fracturing. The movement of the fluid is shown schematically at a fluid front 28 (the position of the laterally outward most extent of a body of the pumped fluid) in FIG. 1 . In hydraulic fracturing techniques known in the art, the fluid is pumped at a pressure which exceeds the fracture pressure of the particular producing formation 20 , causing it to rupture, and form fissures therein. The fracture pressure is generally related to the pressure exerted by the weight of all the formations 16 , 18 disposed above the hydrocarbon producing formation 20 , and such pressure is generally referred to as the “overburden pressure.” In propped hydraulic fracturing operations, the particles of the proppant move into such fissures and remain therein after the fluid pressure is reduced below the fracture pressure of the formation 20 . The proppant, by appropriate selection of particle size distribution and shape, forms a high permeability channel in the hydrocarbon producing formation 20 that may extend a substantial lateral distance away from the pipe or tubing 24 , and such channel remains permeable after the fluid pressure is relieved. The effect of the proppant filled channel is to increase the effective fluid drainage radius of the wellbore 24 that is in hydraulic communication with the producing formation 20 , thus substantially increasing productive capacity of the wellbore 24 to fluid, particularly hydrocarbons.
[0014] The hydraulic fracturing of the formation 20 by the fluid pressure creates seismic energy that is detected by the seismic sensors 12 . The time at which the seismic energy is detected by each of the seismic sensors 12 with respect to the time-dependent position in the subsurface of the formation fracture caused at the fluid front 28 is related to the acoustic velocity of each of the formations 16 , 18 , 20 , and the position of each of the seismic sensors 12 .
[0015] Having explained one type of passive seismic data that may be used with methods according to the present disclosure, an example method for processing such seismic data will now be explained. The seismic signals recorded from each of the seismic sensors 12 may be processed first by certain procedures well known in the art of seismic data processing, including the summing described above, and various forms of filtering. In some embodiments, the seismic sensors 12 may be arranged in directions substantially along a direction of propagation of acoustic energy that may be generated by the pumping unit 32 , in the embodiment of FIG. 1 radially outward away from the wellhead 30 . By such arrangement of the seismic sensors 12 , acoustic noise from the pumping unit 32 and similar sources near the wellhead 30 may be attenuated in the detected seismic signals by, e.g., frequency-wavenumber (f k) filtering. Other processing techniques for noise reduction and/or signal enhancement will occur to those of ordinary skill in the art.
[0016] Having acquired seismic signals in the manner explained above, an example processing technique according to the present disclosure will be explained with reference to FIG. 2 . The process actions performed as explained below may be performed on a computer, on a computer system or any similar electronic system. A non-limiting example of a computer will be explained with reference to FIG. 3 . If the computer or computer system is digital, it will be appreciated that the recorded seismic signals may be recorded in or digitized to convert their form to digital, wherein seismic signals are represented by number pairs corresponding to a measured signal amplitude at each of a plurality of signal times. The signal times may be generated as the product of a signal index number referenced to the start of recording and a time based digital sample rate. In implementing such process in a computer or computer system, signals detected and/or recorded from the seismic sensors as explained with reference to FIG. 1 may be communicate to the computer or computer system as input thereto. At 40 , a moveout time, t r , (i.e., a seismic energy travel time) from any considered (selected) position x in a subsurface volume or interest to the position of each seismic sensor r is calculated. The moveout time may be calculated using a seismic velocity model of the subsurface volume of interest, for example as may be obtained from surface reflection seismic surveys. Other sources for the subsurface velocity model may include wellbore seismic surveys either alone or in conjunction with surface reflection seismic surveys. At 42 , the moveout time determined for each seismic sensor position r is added to a considered (preselected) microseismic event origin time t 0 following which an event signal amplitude a r is retrieved from the time sample in each seismic signal recording corresponding to the recorded signal time defined by (t r +t 0 ). The foregoing may be repeated for any or all of the remaining seismic signal recordings. At 44 , the event signal amplitudes a r are used to obtain a vectorized moment tensor M, which may be determined using an expression such as one described in: Sipkin, S. A., 1982, Estimation of earthquake source parameters by the inversion of waveform data: synthetic waveforms, Physics of the Earth and Planetary Interiors, 30(23), 242-259, Special Issue Earthquake Algorithms, and Anikiev, D., Stanek, F., Valenta, J., and Eisner, L. (2013), Imaging microseismic events by diffraction stacking with moment tensor inversion, SEG Technical Program Expanded Abstracts 2013: pp. 2013-2018. doi: 10.1190/segam2013-0830.1. The moment tensors obtained at 44 are then used to determine, at 46 , a predicted seismic event amplitude b r at each seismic sensor position r. The predicted seismic event amplitude may be determined by a scalar product of G r (the vectorized derivative of Green's function, described in Sipkin, 1982 and Anikiev et al., 2014) with M as in following expression:
[0000] b r =G r ·M (1)
[0017] The predicted seismic event amplitudes and the event signal amplitudes a r determined at 42 may be used, at 48 to calculate a semblance for one or more selected seismic sensor traces. The semblance, at 50 , may be calculated using amplitudes corrected by the polarity of the predicted seismic event amplitudes b r or with the event signal amplitudes corrected by values of predicted seismic event amplitudes. The semblance may be calculated in the form of a ratio of a squared sum of amplitudes from signals from all the seismic sensors and a sum of squared amplitudes divided by a number of the seismic sensors. Such calculation may be performed according to the following expression:
[0000]
S
(
A
)
=
(
∑
i
=
1
N
A
i
)
2
N
·
∑
i
=
1
N
A
i
2
(
2
)
[0018] Semblance values range from 0 to 1. Semblance S of N event signal amplitudes A i reaches a maximum value of 1 when the set of event signal samples A i have a uniform distribution, i.e., all A i are equal. The minimum semblance value 0 is obtained for a set of amplitudes with zero average, for example, when A consists of random Gaussian noise. However this means that the semblance computed from amplitudes corresponding to sources with directionally dependent polarity and amplitude can never reach the maximum value of 1 because amplitudes of seismic energy radiating toward the seismic sensors are dependent on the actual seismic energy radiation pattern for each microseismic event, which as previously explained is related to the source mechanism. In the present example embodiment, a new application of semblance may be used where the samples A i are not raw amplitudes but amplitudes corrected for the seismic energy radiation pattern. To apply these criteria for detection of microseismic events from time-continuous seismic data one may use joint inversion of microseismic event location and its corresponding source mechanism, and correct both the amplitude polarity and magnitude before the semblance computation is performed. The latter may also be used during post-processing to verify whether the determined microseismic events correspond to true microseismic events.
[0019] One may then compare synthetically computed, uncorrected signal amplitudes and amplitudes with corrected polarities based on the source mechanism using the expression:
[0000] A i =a i ·sign( b i ) (3)
[0000] and amplitudes corrected in both polarity and size:
[0000]
A
i
=
a
i
·
1
b
i
(
4
)
[0000] where a i is an original amplitude and b i is a synthetic amplitude modeled for the i th seismic sensor resulting from the moment tensor M inverted from all amplitudes a i (i.e., set a).
[0020] At 52 , if the calculated semblance is above a selected threshold, then the considered spatial position x and origin time t 0 (collectively a “hypocenter”) are determined to correspond to an actual microseismic event, rather than a false positive indication of a microseismic event.
[0021] In other embodiments, signals from only those of the seismic sensors are selected by values of synthetic event amplitudes having a value above a selected threshold to determine origin time and spatial position of the microseismic event(s).
[0022] Referring to FIG. 3 , the foregoing process as explained with reference to FIGS. 1 and 2 may be embodied in computer-readable code. The computer-readable code can be stored on a computer readable medium, such as solid state memory card 164 , CD-ROM 162 or a magnetic (or other type) hard drive 166 forming part of a general purpose programmable computer. The computer, as known in the art, includes a central processing unit 150 , a user input device such as a keyboard 154 and a user display 152 such as a flat panel LCD display or cathode ray tube display. According to this aspect of the invention, the computer readable medium includes logic operable to cause the computer to execute acts as set forth above and explained with respect to the previous figures. The computer, as explained above, may be in the recording unit ( 10 in FIG. 1 ) or may be any other computer located at any desired location.
[0023] While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Accordingly, the scope of the invention should be limited only by the attached claims. | A method for determining hypocenters of microseismic events includes entering as input to a computer seismic signals recorded by a plurality of seismic sensors disposed proximate a volume of subsurface to be evaluated. For each point in space in the volume, and for a plurality of preselected origin times, a seismic energy arrival time at each seismic sensor is determined. Event amplitudes for each arrival time are determined. A synthetic event amplitude is calculated for each arrival time. A semblance between the determined event amplitudes and the synthetic event amplitudes is determined. Existence of an actual microseismic is determined event when the semblance exceeds a selected threshold. | 6 |
This application is a continuation-in-part of application Ser. No. 07/735,995, filed Jul. 25, 1991 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an assembly for mixing and dispensing preparations of two or more components.
2. Description of the Related Art
A number of devices have been developed which are intended to serve as a shipping, storage, mixing and dispensing container for small quantities of preparations made of two or more components. Some of these devices are particularly desirable for single-use applications such as one-patient applications in the medical and dental fields. Certain devices, for example, are used in dentistry for two-component glass ionomer cement systems that serve as adhesives, bases, liners, luting agents, sealants, and filling materials for restorative or endodontic use.
Ionomer cement systems typically are made by mixing a small quantity of glass powder with an aqueous solution of polycarboxylic acid. Representative ionomer cement systems are described in U.S. Pat. Nos. 4,872,936, 4,209,434 and 3,814,714 as well as European Patent Application Nos. 0 323 120 and 0 329 268. Dental ionomer cement systems are often characterized as having relatively short working times (e.g., on the order of one to two minutes) and as a consequence preferably are applied directly to the tooth cavity or other work site from a capsule or other small container that is used for both mixing and dispensing the cement.
Mixing and dispensing capsules for two-component dental preparations are described in U.S. Pat. Nos. 3,595,439 and 4,648,532 and U.K. Patent Application No. 2 220 914. In brief, such capsules include a hollow capsule body having an outlet on one end, a piston received in an opposite end, and a barrier within the body that initially separates the two components. When desired, the barrier is ruptured and the components are mixed by placing the capsule in an amalgamator. The capsule is then placed in a dispensing device to advance the piston and eject the mixed preparation through the outlet.
The barrier of the capsule described in U.S. Pat. No. 3,595,439 is ruptured by placing the capsule in a pressure-inducing device that together advances a cap and plunger toward a tubular body portion. After the components are mixed in an amalgamator, the capsule is placed in a receptacle of a hand extruder having a ram which is movable through a hole in the capsule cap for advancement of the plunger to dispense the preparation while the cap remains stationary.
Advantageously, the overall length of the capsule shown in U.S. Pat. No. 3,595,439 is too large to fit within the receptacle of the extruder unless the barrier has been ruptured by advancement of the cap and plunger toward the tubular body of the capsule. Such construction serves to remind the user that there are two components in the capsule that should be mixed by the amalgamator before beginning the dispensing operation.
However, the mixing and dispensing capsule described in U.S. Pat. No. 3,595,439 is used with two tools: the pressure-inducing device to rupture the barrier and "activate" the capsule, and the hand extruder for discharging the mixed preparation from the capsule. The purchase, handling and cleaning of two tools results in additional time and expense.
U.K. Patent Application No. 2 220 914 describes in one embodiment an assembly of a capsule and a single dispensing device, wherein the dispensing device is placed in a first position to rupture a barrier and then placed in a second position to eject the contents. However, there is a possibility that a ram of the dispensing device may be advanced too far when such a capsule is in its first position, resulting in unintentional discharge of the contents of the capsule before the contents have been properly mixed.
SUMMARY OF THE INVENTION
An assembly in accordance with the invention for mixing and dispensing a preparation comprises a capsule including a body having a chamber and a front end portion with outlet structure. The capsule includes a piston received in the chamber. The piston is movable in the chamber along a limited path of travel toward the front end portion. The capsule includes a barrier in the chamber. The assembly further includes a dispensing device including a housing having a receptacle with a reference axis. The receptacle includes structure for detachably receiving the capsule in either a first orientation or a second orientation spaced from the first orientation in a direction along the axis. The device includes a lever movably coupled to the housing and a ram connected to the lever. The ram is operable to move the piston in a direction along the axis when the capsule is received in the receptacle and the lever is moved relative to the housing.
When the capsule is received in the first orientation, the ram is operable to move the piston to a certain location wherein the barrier opens as the piston reaches the certain location. When the capsule is received in the second orientation, the ram is operable to move the piston to a certain position that is substantially the same as the forwardmost limit of the path of travel of the piston in the chamber. The first orientation is spaced from the second orientation a distance that is at least as great as the distance between the certain location and the certain position.
The barrier provides initial separation of a first component from a second component of the preparation. Preferably, the ram of the device reaches its limit of travel once the barrier is opened and the capsule is in the first orientation, in order to avoid undue reduction in the space available for mixing the components. Reaching the end of possible movement of the ram also provides tactile feedback to the user that the first stage of operation is essentially complete.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side cross-sectional view of a capsule and a dispensing device in accordance with one embodiment of the invention;
FIG. 2 is a view somewhat similar to FIG. 1 except that a lever of the dispensing device has been pivoted to advance a ram of the device to its limit of forward movement;
FIG. 3 is a fragmentary, enlarged top view of the capsule and dispensing device shown in FIG. 1;
FIG. 4 is a fragmentary, enlarged top view of the capsule and dispensing device depicted in FIG. 2, showing a piston of the capsule moved forward to expel a second component of a preparation into a chamber that contains a first component;
FIG. 5 is a view somewhat similar to FIG. 3 except that the capsule has been moved to a second orientation in a receptacle of the dispensing device;
FIG. 6 is a view somewhat similar to FIG. 5 except that the ram of the dispensing device has been advanced to move a piston of the capsule forward in the chamber and expel a preparation from the chamber;
FIG. 7 is a perspective view of the capsule shown in FIGS. 1-6;
FIG. 8 is a fragmentary, perspective view of a front end portion of the dispensing device shown in FIGS. 1-6;
FIG. 9 is a fragmentary, plan view of a capsule and a dispensing device in accordance with another embodiment of the invention;
FIG. 10 is a fragmentary, side cross-sectional view of the capsule and dispensing device illustrated in FIG. 9;
FIG. 11 is a view somewhat similar to FIG. 10 except that a ram of the dispensing device has been advanced to move a piston of the capsule to a certain location to open a barrier;
FIG. 12 is a view somewhat similar to FIG. 11 except that the capsule has been placed in a second orientation in the dispensing device and the ram has been retracted;
FIG. 13 is a view somewhat similar to FIG. 12 except that the ram has been advanced to move the piston forward and expel a preparation through outlet structure; and
FIG. 14 is an enlarged perspective view of an inner cup of the capsule.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A capsule 10 for mixing and dispensing a preparation made of two or more components is shown in FIGS. 1-7. Preferably, the capsule is used in combination with a dispensing device 12 that is illustrated in FIGS. 1 and 2. The capsule 10 and the device 12 constitute a two-stage mixing and dispensing assembly 13.
As can be observed in, for example, FIG. 3, the capsule 10 includes a generally cylindrical, tubular body 14 having an internal, cylindrical chamber 16 that contains a first component 18 of the preparation. Additionally, the body 14 has a front end portion 20 with outlet structure 22 that comprises a projecting nozzle. Although not shown, the outlet structure 22 is initially covered by a cap, and has partial Luer-type threads for twist-on connection with a nozzle extension useful for reaching areas of the oral cavity that might otherwise be difficult to access.
As shown for example in FIG. 7, the periphery of the body 14 is somewhat star-shaped, and presents a plurality of elongated, front-to-back ridges 24 for enhancing the user's grip on the capsule body 14 when turning the body 14 and/or the nozzle extension relative to the dispensing device 12.
The body 14 also includes a first peripheral, circumscribing flange 26 that extends radially outwardly from a longitudinal, central axis of the body 14. The first flange 26 has a first wall section 28 that faces the front end portion 20. The body has a second flange 30 that is similar to the first flange 26 and has a second wall section 32 that also faces the front end portion 20.
A cylindrical piston 34 is initially received in a rear end portion 36 of the body 14 as shown in FIG. 3, and has an outer diameter that is complemental and approximately equal to the inner diameter of the chamber 16. The piston 34 is movable in the chamber 16 along a path coincident with the central, longitudinal axis of the chamber 16 and the body 14.
A generally circular disc 38 is received in the chamber 16 and has a central opening 40 as well as four tabs 42 spaced equally around the periphery of the disc 38. When assembling the disc 38 and the body 14, the tabs 42 are guided along four mating slots 44 until reaching the front end of the latter. The disc 38 is similar to a disc of a two-component capsule of Ernst Muhlbauer KG (Hamburg, Germany).
As illustrated in FIG. 3, a barrier in the nature of a pouch or pillow 46 is made of a layered polyethylene and aluminum foil material. The pillow 46 is located between the disc 38 and the piston 34 and has an internal, initially closed compartment 48 that receives a second component 50 of the preparation.
The capsule 10 may be conveniently used to dispense dental ionomer cement systems such as the system described in the aforementioned European Patent Application No. 0 323 120. In such an instance, the first component 18 comprises a glass powder and the second component 50 comprises an aqueous solution of polycarboxylic acid. However, the capsule 10 is also useful for mixing and dispensing other preparations made of two or more components.
The dispensing device 12 is preferably used in combination with the capsule 10 and is similar to the device described in U.S. Pat. No. 4,198,756. The device 12 includes a housing 52 having a transverse grip 54 as shown in FIGS. 1 and 2. A rear lever 56 is connected to the grip 54 by a pivotal connection 58 for swinging movement between the positions shown in FIGS. 1 and 2.
The housing 52 includes a cylindrical channel that slidably receives a ram 60 having a necked-down, cylindrical front section with a flat front end. A rear end of the ram 60 has a somewhat semi-spherical, enlarged head 62, and a coiled compression spring 64 surrounding the ram 60 between the head 62 and the grip 54 urges the ram 60 in a rearward direction toward the lever 56.
A curved cam surface 66 is formed on the lever 56 and is in sliding engagement with the head 62. As the lever 56 is moved toward the grip 54 in arc about the pivotal connection from its orientation shown in FIG. 1 and to its orientation shown in FIG. 2 (as would occur when the hand of the user squeezes the lever 56 against the grip 54), the head 62 rides along the cam surface 66 and moves the ram 60 in a forward direction toward a front portion of the dispensing device 12. When the lever 56 is released, the spring 64 moves both the ram 60 and the lever 56 from the respective positions shown in FIG. 2 and to the positions shown in FIG. 1.
The front end portion of the dispensing device 12 includes a receptacle 68 having a longitudinal reference axis that is collinear with the central axis and the path of sliding movement of the ram 60 and its necked-down front portion. The receptacle 68 terminates at its front end by a generally U-shaped retention wall member 70 (see FIGS. 3-6 and 8) and at its rear end by a rear wall having a hole 71 (FIG. 8) for receiving the front necked-down section of the ram 60.
In use, the capsule 10 is initially placed in the receptacle 68 in a first orientation that is shown in FIGS. 1-4 wherein the first wall section 28 is in abutting contact with a rear-facing wall surface 72 of the retention member 70. Next, the lever 56 is moved in an arc about the pivotal connection 58 to advance the ram 60 and cause the front end of the ram 60 to engage the rear end of the piston 34. Continued movement of the lever 56 to its orientation shown in FIG. 2 shifts the ram 60 and the piston 34 therewith to the respective positions shown in FIG. 4.
As the piston 34 is moved from its initial position shown in FIG. 3 and to its intermediate position shown in FIG. 4, the pillow 46 is compressed against the disc 38, causing the pillow 46 to rupture and open. Continued movement of the piston 34 to its position shown in FIG. 4 compresses the pillow 46 against the disc 38, and causes the second component 50 to be expelled from the compartment 48 and discharged into the chamber 16 through the opening 40. As can be appreciated, the disc 38 serves as a means to open the barrier or pillow 46, discharge the second component 50 from the compartment 48, and bring the second component 50 into substantial contact with the first component 18 when the piston 34 is moved to the position shown in FIG. 4. As the piston 34 continues to advance toward the front end portion 20 and flatten the pillow 46 against the disc 38, the disc 38 breaks away from the tabs 42 and advances from its position shown in FIG. 3 to its position shown in FIG. 4. The severed tabs 42 remain in the slots 44.
The ram 60 has an overall, limited extent of forward movement that is determined by the position of the ram 60 when the spring 64 is fully compressed as shown in FIG. 2. When the ram 60 has reached its forward limit of travel, the rear face of the piston 34 is flush with the rear surface of the first flange 26 and the disc 38 is in the position shown in FIG. 4 with the tabs 42 severed and the second component 50 substantially fully expelled into the chamber 16. Such construction ensures that the user cannot continue to advance the ram 60 and prematurely dispense the first component 18 and the second component 50 from the chamber 16 through the outlet structure 22.
Next, the capsule 10 is removed from the receptacle 60 and placed in an amalgamator. The amalgamator is activated for a sufficient amount of time to thoroughly mix the first component 18 and the second component 50 in the chamber 16 to form a preparation.
The capsule 10 is then returned to the receptacle 68, but in this instance is placed in a second orientation that is illustrated in FIGS. 5 and 6 wherein the second wall section 32 of the second flange 30 is in abutting contact with the rear surface 72 of the retention member 70. It should be noted, however, that if the user accidentally returns the capsule 10 to the first orientation (as shown in FIGS. 1-4), the user will soon realize that the capsule is in the wrong orientation for dispensing since the ram 60 will be unable to advance the piston 34 past its position shown in FIG. 4 and discharge of the preparation will not occur. As can be appreciated, the wall sections 28, 32 together with the retention member 70 comprise structure for detachably receiving the capsule 10 in either a first orientation or a second orientation spaced from the first orientation in a direction along the longitudinal reference axis of the receptacle 68.
Once the capsule 10 is in its second orientation as depicted in FIGS. 5 and 6, the lever 56 is pivoted toward the grip 54 to advance the ram 60 and move the piston 34 from its position shown in FIG. 5 and toward its position shown in FIG. 6. During such movement, the disc 38 and the pillow 46 are moved with the piston 34 toward the front end portion 20, and as the chamber 16 is reduced in volume the mixed preparation is extruded through the outlet structure 22, preferably directly to an application site such as a tooth cavity.
As the ram 60 is moved by the lever 56 to its forwardmost allowable position, the piston 34 is advanced toward the front end portion 20 to a position wherein a front surface of the disc 38 is in firm, face-to-face contact with a flat, rear facing annular wall 74 of the chamber 16. As a result, substantially all of the preparation is expelled from the chamber 16 when the ram 60 and the piston 34 reach their forward limits of travel. Further, forward movement of the ram 60 is restricted by the fully compressed spring 64 so that the piston 34 and disc 38 do not burst through the front end portion 20 of the capsule 10.
When the ram 60 is in its forwardmost position and the capsule 10 is in its first orientation as shown in FIG. 4, the piston 34, and particularly the front end of the piston 34, is located a certain dimension that is marked A in FIG. 4 from the first wall section 28 of the first flange 26. When the capsule 10 is in its second orientation and the ram 60 is advanced to its forwardmost position (that is shown in FIG. 6), the front end of the piston 34 is located a dimension marked B in FIG. 6 from the second wall section 32 of the second flange 30. Advantageously, dimension A is equal to dimension B, so that in either instance the ram 60 travels along the same limited path of travel, and the entire extent of the mechanical advantage offered by the lever 56 is utilized. (Dimensions A and B could be taken from a portion of the piston other than its front end so long as the same portion was used for each measurement.)
Rearward movement of the ram 60 is normally limited by detents formed in the pivotal connection 58 such that, in normal use, the front end of the ram 60 retracts only to its position shown in FIGS. 1, 3 and 5. Consequently, the effective length of the receptacle 68 for reception of the capsule 10 is limited by the distance E (see FIG. 3) between the front end of the ram 60 and the rearwardly facing surface 72 of the retention member 70.
In addition, as can be observed in FIG. 3, the rear end of the piston 34 initially projects a certain distance marked C in FIG. 3 from the first wall section 28 of the first flange 26. Also, the first wall section 28 is spaced from the second wall section 32 by a dimension D (see FIG. 3). The sum of dimensions C and D is greater than the dimension E (measured between the surface 72 and the front end of the ram 60 when in its rearwardmost position) in order to prevent the capsule 10 from being placed in its second orientation until such time as the piston 34 has been advanced. Preferably, the dimension E is only slightly greater than the sum of dimension D and the thickness of the first flange 26 to ensure that the piston 34 has moved to its orientation shown in FIG. 4 with the contents of the compartment 48 fully expelled and the tabs 42 severed from remaining portions of the disc 38.
The overall limited movement of the ram 60 is not greater than dimension E regardless of whether the capsule 10 is in its first orientation or its second orientation in order to provide a relatively compact arrangement and still utilize in either instance the substantial mechanical advantage provided by the lever 56. As an alternative, the dimension A may be greater than the dimension B if desired.
The foregoing assembly 13 ensures that the user removes the capsule 10 from the receptacle 68 after the pillow 46 is ruptured. As a result, the user is reminded to place the capsule in an amalgamator to thoroughly mix the components 18, 50 and avoid discharging the components 18, 50 through the outlet structure 22 before thorough mixing in an amalgamator has occurred.
Fracture of the tabs 42 from the remaining portions of the disc 38 when the capsule 10 is in the first orientation provides tactile as well as audible feedback to the user that the proper position of the piston 34 has been reached and that the second component 50 is substantially discharged from the compartment 48.
Further, if desired, the tolerance between the piston 34 and the chamber 16 may be selected to allow the user to shift the piston 34 to its position shown in FIG. 4 by using the thumb rather than the dispensing device 12.
An assembly 113 according to a second, currently preferred embodiment of the invention is shown in FIGS. 9-13. The assembly 113 includes a capsule 110 and a dispensing device 112. The device 112 is substantially similar to the device 12 except for a front portion of the device 112 that is adjacent a receptacle 168 for receiving the capsule 110.
The capsule 110 includes a cylindrical, tubular polyethylene body 114 having an inner chamber 116. A first component 118 (FIG. 10) of a preparation is received in a front end portion 120 of the capsule 110 next to curved outlet structure 122 having a removable plug 123 with a tail that initially extends to the forward end of the chamber 116.
A rear portion of the capsule body 114 is circumscribed by two spaced apart flanges. The flanges present a pair of spaced apart wall sections that define a peripheral groove 127 having a U-shaped configuration in cross-section. A polyethylene cup 129 (illustrated alone in FIG. 14) is received in the rear portion of the chamber 116. The cup 129 includes a rear ring 131 that is initially connected in integral fashion at spaced apart locations by tabs 133 to a central cup section 135 that defines a compartment 148 (FIG. 10) for receiving a second component 150 of a dental preparation.
A frangible forward wall or barrier 137 of the cup 129 is provided with lines of weakness 139 (FIG. 14) having a pattern of a square with somewhat weaker (i.e., more pronounced) lines extending along both diagonals of the square. A cylindrical piston 134 is received in the compartment 148 and has a rear section that initially projects outwardly from the capsule 110 as illustrated in FIGS. 9-10.
In use, the capsule 110 is initially placed in a first orientation that is shown in FIGS. 9-11, wherein the groove 127 receives a first, forward, generally U-shaped retention member 170 of the device 112. A lever of the device 112 is then moved to advance a longitudinally movable ram 160 to a position as depicted in FIGS. 9-10 wherein the forward end of the ram 160 contacts the rear end of the piston 134.
Additional movement of the ram 160 shifts the piston 134 forwardly until the pressure within the compartment 148 causes the lines of weakness of the barrier 137 to rupture. The barrier opens in petal-like fashion and, once opened, enables passage of the second component 150 into the chamber 116.
Continued advancement of the ram 60 causes the front end of the piston 134 to bear against remaining outer, unruptured regions of the barrier 137 and causes the cup section 135 along with the barrier 137 to advance toward the outlet structure 122. As the cup section 135 advances, the tabs 133 break, detaching the ring 131 from the cup section 135.
The lines of weakness of the barrier 137 are constructed to open under the influence of pressure within the compartment 148 of a value that is less than the pressure needed to fracture the tabs 133. As a result, the second component 150 is discharged from the compartment 148 before the ring 131 detaches from the cup section 135. Breakage of the tabs 133 provides both visual and tactile feedback to the user that the capsule 110 has been "activated" by bringing the second component 150 into contact with the first component 118.
Further, the ram 160 reaches its forwardmost limit of travel (as depicted in FIG. 11) once the barrier 137 opens and the tabs 133 fracture. As a consequence, sufficient space is available in the chamber 116 for mixing the first component 118 with the second component 150 and undue reduction in the space is avoided. The forwardmost limit of movement of the ram 160 also essentially prevents dispensing of the components 118, 150 through the outlet structure 122 when the capsule 110 is in the first orientation, so that dispensing of an unmixed preparation is not likely to occur.
Next, the capsule 110 and the ring 131 are removed from the receptacle 168. The capsule 110 is placed in an amalgamator and the amalgamator is activated for a sufficient amount of time to thoroughly mix the components 118, 150 in the chamber 116 to form a preparation. Subsequently, the capsule 110 is returned to the receptacle 168 in a second orientation as shown in FIGS. 12 and 13 wherein the groove 127 engages a second generally U-shaped retention member 173 of the device 112.
Next, the plug 123 is removed from the outlet structure 122. The lever of the device 112 is then moved to advance the ram 160 and thereby shift the piston 134 from its position as shown in FIG. 12 and toward its position as shown in FIG. 13, causing the preparation to be dispensed through the outlet structure 122.
To ease use, the handles of the dispensing device are not fully closed (i.e., are not adjacent one another) when the ram 160 reaches the end of its necessary path of travel to advance the piston 134 to the position shown in FIG. 11 when the capsule 110 is in its first orientation, or to the position shown in FIG. 13 when the capsule 110 is in its second orientation. Preferably, one of the handles has a protrusion that contacts the other handle and precludes further closing of the handles if an attempt is made to advance the ram 160 past the position shown in FIG. 11.
The first orientation of the capsule 110 in the receptacle 168 is spaced from the second orientation of the capsule 110 by a distance represented by the letter F in FIG. 13 (for exemplary purposes, the location of each orientation is determined by the location of the groove 127 when the capsule 110 is placed in either orientation). The letter G in FIG. 13 represents the dimension of the distance between the certain location of the piston 134 as shown in FIG. 11 and the certain position of the piston 134 as shown in FIG. 13 (as determined for exemplary purposes from the forward end of the piston 134). The dimension F is equal, or at least as great as the dimension G so that (1) the space available in the chamber 116 for mixing the components 118, 150 after the barrier 137 is ruptured is not unintentionally reduced, and (2) dispensing of the components 118, 150 is essentially precluded when the capsule 110 is in the first orientation. | An assembly for mixing and dispensing preparations such as dental cements includes a capsule and a lever actuated dispensing device. The capsule is received in a first orientation of the dispensing device for initial movement of a piston of the capsule to combine two components in a mixing chamber of the capsule. The capsule is received in a second orientation when dispensing of the components is desired. The capsule includes flanges engageable with one or more retention members of the dispensing device, and the flanges are positioned to substantially utilize the mechanical advantage provided by the dispensing device regardless of whether the capsule is in the first orientation or in the second orientation. The flanges are also arranged to substantially prohibit bursting of the capsule when the components are discharged from the mixing chamber, and essentially preclude dispensing of the components when the capsule is in the first orientation. | 0 |
STATEMENT OF GOVERNMENT INTEREST
The invention described herein may be manufactured, used, and licensed by or for the Government for Governmental purposes without the payment to me of any royalties thereon.
BACKGROUND OF THE INVENTION
This invention relates to line sensors; and more particularly to a line integrated combination magnetic and strain line sensor.
There are many instances where one wishes to protect a given area against intrusion by a person or by an object such as a vehicle or the like. Many different types of alarm systems and detectors exist for protecting a given area. One such system is a line sensor. Line sensors are buried in the ground of the area to be protected and respond to any intrusion into the area. Both strain responsive and magnetic responsive line sensors are utilized.
The prior-art strain sensors commonly use a coaxial cable (strain cables) responsive to soil transmitted strain. The response between the center conductor and outer braid of the cable results in an analog signal, generated on the inner conductor, which can be processed electronically to actuate an alarm.
Prior art magnetic sensors commonly utilize a buried passive magnetic loop. Such loops are generally 300 meters long, coplanar with the earth's surface and are transposed at intervals. The transpositions are provided to nullify geomagnetic perturbations which can induce nuisance alarms. While such magnetic sensors have proved effective, they have inherent deficiencies which can limit their effectiveness. For example, if there is any unbalance in opposing loop areas, a net noise "Capture" area exists and this results in system vulnerability to nuisance alarming caused by lightning and other sources of geomagnetic noise. In order to minimize such false alarming, precise loop balance is required and such loop balancing can be accomplished only by trained personnel. Further, due to the required transpositions, these prior art loops are not readily buried in the ground since they require a multitude of cross trenches at five feet intervals.
This invention provides a combination magnetic and strain line sensor that is readily installed and operated by relatively unskilled personnel and is not as vulnerable to nuisance alarming caused by lightning or other geomagnetic noise as the prior transposed magnetic loop systems.
SUMMARY OF THE INVENTION
The combination magnetic and strain line sensor of this invention comprises two coaxial cable loops and processing electronic circuitry. Three parallel trenches are dug and the loops are placed in the trenches such that one leg of each loop occupies the middle trench. Magnetic sensing and processing circuitry is provided to actuate a magnetic pick-up alarm and strain sensing and processing circuitry is provided to actuate a pressure alarm. In addition, circuitry is provided to actuate a combined strain and magnetic alarm. The braid of the coaxial cable used to make up the loops provides magnetic sensing and the center conductor of the cables provides strain sensing.
BRIEF DESCRITION OF THE DRAWING
The exact nature and structural details of the invention will become apparent from the following detailed description when read in conjunction with the annexed drawing in which:
FIG. 1 shows a prior magnetic line sensor system;
FIG. 2 shows a preferred embodiment of this invention; and
FIG. 3 shows in block diagram form circuitry that may be utilized with the preferred embodiment of FIG. 2.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, this Figure shows a typical layout of a prior art magnetic line sensor. The magnetic line sensor 1 of FIG. 1 includes a passive magnetic loop 2 that has the three transpositions or cross-overs 3, 4 and 5, forming subloops 13, 14, 15 and 16. The trenches 6, 7 and 8 accomodate the outer perimeter of loop 2 and the trenches 9, 10 and 11 accomodate transpositions 3, 4 and 5 respectively. After the trenches are dug and loop 2 is placed in the trenches, these trenches are covered over to conceal loop 2. The open end of loop 2 is coupled to the processing electronic circuitry 12.
If any object containing magnetic material or any person carrying an object or objects containing magnetic material passes over any subloop of loop 2, loop 2 senses the magnetic disturbance caused by such objects and electronic circuitry 12 will produce a signal or alarm indicating that an intrusion has occurred in the area of loop 2.
Magnetic line sensors such as sensor 1 of FIG. 1 provide effective magnetic sensing; however such devices have inherent deficiencies. Subloop pairs 13 and 14 and 15 and 16 delineate opposing subloop areas which serve to nullify geomagnetic perturbances. However, if any unbalance exists in these opposing subloop areas, a net noise "capture" area exists, and this results in vulnerability to nuisance alarming caused by lightning or other geomagnetic noise. Thus, the opposing subloop must be perfectly balanced to prevent such nuisance alarming. Loop balance is a precise operation requiring trained and skilled personnel. However, even with trained personnel, precise subloop balance is difficult, if not impossible, to obtain in the field. Even under laboratory conditions, perfect subloop balance is difficult to obtain. Thus, even if carefully installed and balanced, the chances are great that some unbalance will be present in the opposing subloop formed by the transpositions 3, 4 and 5 and a net noise capture area will exist in loop 2, thereby rendering loop 2 susceptible to nuisance alarming.
FIG. 2 shows a preferred embodiment of this invention which overcomes the problems of transducer 2 of FIG. 1 and provides both magnetic and strain sensing. As shown in FIG. 2, transducer 20 includes the two loops 21 and 22. Loops 21 and 22 are formed from coaxial cable having a braid and an inner conductor.
The three parallel trenches 23, 24 and 25 and the short end trench 26 are provided to accomodate loop 21 and 22. After trenches 23, 24, 25, and 26 are dug, loops 21 and 22 are placed in these trenches such that leg 28 of loop 21 and leg 29 of loop 22 are placed parallel in trench 24 with leg 30 of loop 21 placed in trench 23, leg 31 of loop 22 placed in trench 25 and the short or closed ends of loops 21 and 22 placed in trench 26. These trenches are, of course, then filled with dirt to conceal loops 21 and 22. The open end of loop 21 and the open end of loop 22 are both coupled to the electronic circuitry 32. Electronic circuitry 32 is utilized to process any signals from loops 21 and 22 and provide an alarm or indication that an intrusion has occured.
Loops 21 and 22 are generally up to 300 meters long and are generally equal in area but need not be precisely equal in area. Only a casual attempt is made to balance loops 21 and 22 since any disparity can be compensated by automatic gain control circuitry in electronic circuitry 32. Referring back to sensor 1 of FIG. 1, it is also obvious that loops 21 and 22 do not contain the transpositions of loop 2 of sensor 1. Thus, the inherent balancing problems encountered with loop 2 of sensor 1 and the noise "capture" problems of loop 2 are not present in loops 21 and 22 of sensor 20 of FIG. 2.
As mentioned above, sensor 21 is both a magnetic and a strain sensor. The braid of the coaxial cables used to form loops 21 and 22 provide magnetic pick-up and the inner conductor provides the strain sensing. By providing for magnetic and strain sensing, sensor 21 can operate in any one of three modes, strain sensing only mode, magnetic sensing only mode and combined strain and magnetic sensing mode. The strain only mode of operation will occur if a magnetically clean intruder, who may be carrying plastic explosives for example, attempts to penetrate the area being monitored by sensor 20. As this person crosses loops 21 and 22, a force or strain transmitted by the ground will be applied to loops 21 and 22 and an analog signal will be generated. No magnetic sensing will take place since plastic explosives are magnetically clean and the intruder was assumed to be magnetically clean. The analog signal will be processed by electronic circuitry 32, and by providing appropriate circuitry, a strain only indication or alarm is generated by electronic circuitry 32.
The magnetic sensing only mode can occur if, for example, the ground covering and surrounding loops 21 and 22 are heavily frozen. If the ground is frozen, the ground may not transmit the pressure to loops 21 and 22. If this is the case, only the magnetic disturbance created by the intruder will be picked up by loops 21 and 22. The signal caused by this magnetic disturbance will be processed by electronic circuitry 32 and if appropriate circuitry is provided, a magnetic only indication or alarm, distinct from the strain only alarm, is generated. Of course, if magnetic sensing only can be obtained because of frozen ground, the intruder cannot be magnetically clean or no alarm will occur. This is not a serious problem since, magnetic sensing only will rarely occur.
The most common mode of operation of sensor 20 will be the combined magnetic and strain mode. In this mode both a strain signal and a magnetic signal are generated in response to an intrusion in the area protected by loops 21 and 22 and both these signals are processed by electronic circuitry 32 to produce a combination alarm or indication. The combination alarm may be distinct from the magnetic only alarm and the strain only alarm if appropriate processing circuitry is provided. Of course only a single alarm or indication need be provided for all three modes of operation. However, with only a single alarm or indication, one cannot determine the mode of operation of sensor 20.
FIG. 3 shows, in block diagram form, circuit blocks that may be utilized to fabricate electronic circuitry 32 of FIG. 2 to provide three distinct alarms that distinguish the three modes of operation. Referring to FIG. 3, the braid of the coaxial cable of loop 21 is coupled to the magnetic input transformer 33 and the braid of the coaxial cable of loop 22 is coupled to the magnetic input transformer 34. The center conductor of loop 21 and the center conductor of loop 22 are coupled to separate inputs of the strain channel differential amplifier 35. The output of strain channel differential amplifier 35 is coupled to the input of strain processing circuitry 37. Strain processing circuitry 37 is any suitable circuitry that processes the output of differential amplifier 35 to provide the desired output. For example, in FIG. 3, the output lead 39 is shown as going to a strain alarm. The strain alarm may be an audio alarm such as a bell, siren or the like or may be a visual indicator such as a light or meter. Thus, processing circuitry 37 need merely provide an output on lead 39 in response to an input from differential amplifier 35 that will actuate the alarm device utilized. Differential amplifier 35 and processing circuitry 37 provide an output on lead 39 to actuate an alarm that indicates that only a strain response has been obtained from loops 21 and 22, thus indicating that sensor 20 is operating in the strain only mode.
Magnetic input transformer 33 is coupled to one input of the magnetic processing circuitry 36 and the output of magnetic input transformer 34 is coupled to the other input of magnetic processing circuitry 36. In response to an input from magnetic input transformer 33 and magnetic input transformer 34, processing circuitry 36 provides an output signal on the lead 41 which is shown as going to a magnetic alarm. As is the case with the strain alarm, the magnetic alarm can be an audio alarm or a visual alarm and processing circuitry 36 need merely provide a signal on lead 41 that will actuate the alarm utilized. Input transformers 33 and 34 and processing circuitry 36 provide a signal on lead 41 to indicate that only a magnetic response has been received from loops 21 and 22 and that therefore sensor 20 is operating in the magnetic only mode.
Strain processing circuitry 37 has a second output lead, the lead 40, and magnetic processing circuitry 36 also has a second output lead, the lead 42. Output lead 40 of strain processing circuitry 37 is coupled to one input of the combination processing circuitry 38 and output lead 42 of magnetic processing circuitry 36 is coupled to the other input of combined processing circuitry 38. In response to a signal from both strain processing circuitry 37 and magnetic processing circuitry 36, combined processing circuitry 38 provides an output signal on lead 43 which is shown as going to a combined alarm. The combined alarm may, for example, be an audio or visual alarm and combined processing circuitry 38 need merely provide a signal on lead 43 that will actuate the alarm utilized. When such a signal appears on line 43, sensor 20 is operating in the combined magnetic and strain mode.
The circuitry of FIG. 3 is shown in block diagram form since all the circuits utilized are well known circuits and in fact various different known circuits could be utilized to achieve the desired results. As shown in FIG. 3, the circuitry does provide for distinct indications of the three modes of operation of sensors 20. That is, an output will appear only on lead 39 in the strain mode, only on lead 41 in the magnetic mode and no output appears on lead 43 unless sensor 20 is operating in the combined mode. In the combined mode of operation, a signal would also normally appear on lead 39 and on lead 41 and therefore all three alarms would be actuated unless the signals on leads 39 and 41 are inhibited. Whether all three alarms operate in the combined mode or only the combined alarm operates is really a matter of choice since all three alarms being actuated would provide a distinct combined alarm indication. If only the combined alarm is to be actuated, the signals that would appear on leads 39 and 41 could be inhibited or the associated alarms could be inhibited during combined operation in any well known manner. Further, only one alarm need be provided if one does not wish to distinguish between modes of operation or combined processing circuit 38 could be eliminated since actuation of both the strain alarm and magnetic alarm would provide an indication of the combined mode of operation. These variations of the circuitry of FIG. 3 are mentioned to illustrate that the circuitry of FIG. 3 is given by way of example and that various modifications can be made to this circuitry and that other well known circuitry can be utilized.
In addition to providing only an indication that an intrusion has taken place in areas protected by sensor 20 and in which of three modes sensor 20 is operating, more sophisticated but known circuitry could be provided in electronic circuitry 32 to obtain additional information. Tests of sensor 20 have shown that the loops 21 and 22 provide signals having well defined waveshapes. Further, these well defined waveshapes are different for different intruders. That is, a person walking in the protected area produces a given waveshape that is different from the waveshape produced by a vehicle and a wheeled vehicle may produce a waveshape that is different than the waveshape produced by a tracked vehicle such as a tank. The waveshape of an intruder is called the signature of that intruder. Thus, by utilizing known wave analyzing and logic circuitry, it is possible to distinguish between various different types of intrusion. Of course, the signatures of various intruders must be significantly different to be able to distinguish between different types of intrusion. For example, the difference between the signature of a person and the signature of a heavy truck will be significantly different but the difference between the signature of a truck, even a heavy truck, and the signature of an automobile may not be sufficiently different to provide, even with complex circuitry, an output that will distinguish between an automobile and a truck.
While the invention has been described with reference to a specific embodiment, it will be obvious to those skilled in the art that various changes and modifications, other than those specifically mentioned, can be made to the embodiment shown and described without departing from the spirit and scope of the invention as set forth in the claims. | The disclosed invention pertains to an intruder detection system incorporng paired sensors with minimum sensor balance restraints. The sensor requires as few as three generally parallel trenches and an end trench and thus is suitable for installation by unskilled personnel in a relatively short time period. The sensor of this invention may provide up to three intrusion alarms indicative of a magnetic disturbance alone, or of a combined magnetic and strain disturbance. | 6 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of Provisional applications 60/889,545 filed Feb. 13, 2007, 60/890,823 filed Feb. 20, 2007 and 60/809,856 filed Feb. 21, 2007 the entire contents of which is hereby expressly incorporated by reference herein.
DESCRIPTION
FIELD OF THE INVENTION
[0002] This invention relates to improvements in soap dispensing. More particularly, the present invention relates to a bar of soap that has wood or other cylindrical object placed through the bar of soap and extends out both sides of the bar. A soap dish and soap holder is also disclosed that suspends the bar of soap to aid in drying the soap.
BACKGROUND OF THE INVENTION
[0003] Most people when they bathe use soap of one form or another. Typically when multiple people use the same bathroom the bar of soap becomes softer as each person uses the bar of soap. After the person is done washing the soap sits on a surface and will continue to collect moisture. Some inventions have been patented that will allow the bar of soap to hang or drain. Exemplary examples are described herein.
[0004] U.S. Pat. No. 1,416,962 issue May 23, 1922 to Fred Meeks, U.S. Pat. No. 3,341,457 issued Sep. 12, 1967 and U.S. Pat. No. 3,693,923 issued Sep. 26, 1972 all disclose a bar of soap having a strap of tape, plastic or similar material that a user can grab and hold to reduce the possibility that the bar of soap will slip from their hand. While these patents disclose a bar of soap with material that extends through the ends of the bar of soap the strap is not a rigid member and after the bar of soap is used it is either placed in a dish where it can become soggy or must be suspended from a hook making it not conducive for use near a sink.
[0005] U.S. Pat. No. 606,024 issued Jun. 21, 1898 to M. Peraglie & F. Barro, U.S. Pat. No. 2,099,484 issue Nov. 16, 1937 to L. De F. Hokerk and U.S. Pat. No. 3,51 9,568 issued Jul. 7, 1970 to L. Needleman all disclose soap on a rope or tether. The rope or tether allows a person to hang the bar of soap from a shower head where it drips onto the floor of a shower. While these patents work well in the shower or where there is a deep sink, they do not work around a typical sink and further in a shower if multiple soaps on a rope are used they all will collect together and each person using the shower will make all the bars of soap wet in addition the first bather.
[0006] U.S. Pat. No. 5,642,871 issued Jul. 1, 1997 to Repert et al., discloses a bar of soap with a magnetic material imbedded or cast within the bar of soap. This patent allows a user to maintain the bar of soap in a fixed and elevated location. While this patent is intended for use near a sink, it requires the use of a ferric material that is susceptible to rust and requires the metal to be embedded into a side of the soap. As the soap is used the metal or magnet must be continually pressed into the soap or requires the user to use only one side of the bar of soap.
[0007] What is needed is a bar of soap with a member extending through the bar of soap such that a portion of the member extends out each side of the soap. This allows the bar of soap to be suspended for drying. The proposed application provides this solution with a bar of soap having a stick or similar object extending though the soap bar and further includes optional holding mechanisms for suspending the soap on the stick.
BRIEF SUMMARY OF THE INVENTION
[0008] It is an object of the soap on a stick to provide a bar of soap that has a bar of soap with a stick or similar object extending through the ends of the stick. This form of suspending the bar keeps the bar off of a counter or sink rim. The stick also makes the bar of soap easier to hold without touching the slippery soap surface. The stick allows a moist bar of soap to be transported without the user touching the bar of soap. The stick can be made from a variety of materials, shape and may be made from a rolled note.
[0009] It is an object of the soap on a stick to provide a bar of soap that is suspendable from a soap dish or soap holder that allows the soap to dry evenly without resting in a pool of water. The ability to suspend the soap prevents soggy soap and reduces wasting soap.
[0010] It is an object of the soap on a stick to provide a bar of soap with various scents, fragrances, sizes, colors or properties to suit the bathing needs of the user.
[0011] It is an object of the soap on a stick for use with multiple bathers. The first person bathing often gets the bar of soap with an outer surface that is dry. The second and subsequent bathers must use a bar of soap that is moist soggy and in some cases more liquid than solid. The soap on a stick reduces or prevents this by suspending the bar of soap and allows for multiple bars of soap to be placed in or around a shower or bath.
[0012] It is another object of the soap on a stick to also be provided with a soap rack. The soap rack is a soap dish with appendages to support the opposing stick portions of the soap on a stick. The rack suspends the bar of soap and prevents the problem of soggy and deteriorated soap by allowing the bar of soap to dry and make it ready for subsequent users.
[0013] It is still another object of the soap on a stick to also be provided with a wall mountable rack. The wall mount soap rack has appendages that extend from the wall mounting structure and have arms that are curved to prevent the stick from rolling off the end of each appendage. The wall mounting structure has adhesive backing for bonding the structure to the wall of a shower at a height that is suitable for the height of the bather. The rack suspends the bar of soap and prevents the problem of soggy and deteriorated soap by allowing the bar of soap to dry and make it ready for subsequent users.
[0014] Various objects, features, aspects, and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the invention, along with the accompanying drawings in which like numerals represent like components.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 shows an elliptical soap on a stick.
[0016] FIG. 2 shows a rectangular soap on a stick.
[0017] FIG. 3 shows soap on a stick supported on a soap rack.
[0018] FIG. 4 shows a soap on a stick supported on a wall mount soap rack.
DETAILED DESCRIPTION
[0019] FIG. 1 shows an elliptical soap on a stick in the preferred embodiment. The stick 30 - 33 is made from a rigid or semi rigid material such as wood plastic or treated paper and is called a stick or rigid member interchangeably. The stick material allows the soap bar 20 to be suspendable on the stick 30 - 33 . In the preferred embodiment the stick is made from wood with rounded opposing ends 33 . In the embodiment shown a single stick is shown extending from one side 30 through the center of the bar of soap 20 and exiting the bar of soap 20 on the opposite side. It is also contemplated that multiple sticks can be used and one example is shown and described in FIG. 2 .
[0020] The stick is molded, cast or pressed in or through the bar of soap so it is essentially concentric with the bar of soap. In stick has a length that allows it to extend out both sides of the bar of soap 20 approximately 1.5 inches but this dimension is variable based upon the overall length of the bar of soap 20 and the overall length of the stick. In the preferred embodiment the stick has an overall length of 6 to 7 inches with a diameter between ¼ to ⅜ inch, and the bar of soap 20 has an overall length of 3 to 5 inches with a preferred length of 4 inches. The bar of soap 20 is made in an ellipse shape with a diameter of 2 inches. Other shapes are contemplated including but not limited to round, triangular, square, pentagonal, octagonal and rectangular.
[0021] FIG. 2 shows a rectangular soap on a stick. In this embodiment the bar of soap 21 is rectangular in cross section. Multiple sticks 40 and 41 are used. The sticks are also rectangular in cross section. The rectangular cross section prevents the bar of soap from rolling on round sticks. It should also be noted that the sticks 40 and 41 are placed in bar of soap 21 at an angle to allow any drops of water to drip from the bottom edge 22 of the bar of soap to prevent the bottom of the bar of soap from becoming soggy. The two sticks 40 and 41 are molded, cast or pressed into the bar of soap.
[0022] FIG. 3 shows soap on a stick supported on a soap rack dish. This embodiment of a soap rack is intended for use on a counter and is similar to a standard soap dish except for the appendages that extend upward in a perpendicular arrangement with the base of the dish to support the stick ends 30 and 32 . The bottom 60 of the dish is essentially flat. A lip 65 extends around the base to prevent any drippings from spilling out of the interior dish 64 portion. The raised appendages 61 and 62 are supports for the rigid members or stick(s) 30 and 32 . When the bar of soap is placed on the raised appendages 61 and 62 the bar of soap is maintained out of any drippings or water that may rest in the inter dish portion 64 . The raised appendages have niches 63 on the top of the appendages in effect rack to hold a bar of soap on a stick. The soap rack dish can be fabricated from a number of materials including but not limited to plastic, metal, glass and ceramics.
[0023] The bar of soap shown in this figure has a wrapper 50 that extends around the bar of soap. The wrapper 50 is placed on the bar when it is made to minimize damage to the bar in transit and identifies any unique properties of the bar of soap including but not limited to color, scent, fragrance or additives such as aloe or moisturizer. The wrapper 50 is removed when the bar of soap 20 is going to be used.
[0024] FIG. 4 shows a soap on a stick supported on a wall mount soap rack. This wall mount soap rack has a back wall 70 mounting structure with one or more adhesive bonding strips 80 . The bonding strip(s) allows the wall mount soap rack to be bonded to the wall of a shower or bath wall. The back wall 70 is mounted to a vertical surface. The appendages or arms 71 and 74 extend outward from the back wall structure 70 . The ends of the arms are slightly raised and curved 72 . This curvature creates a depression 73 where the stick(s) 30 and 32 rest to prevent the bar of soap from rolling off the end of the arms 71 and 74 . Any drippings that fall from the bar of soap 20 will fall past the wall mounted structure and into the shower of tub. The wall mounted soap rack can be fabricated from a number of material including but not limited to plastic, metal, glass and ceramics.
[0025] It is contemplated that the rack shown in FIG. 3 is ideal for a family where multiple bathers use the same washing area. Each bather can place their own preferred soap on a stick within the tub or shower where it is available when needed without the undesirable problem of soggy or deteriorated soap.
[0026] In another contemplated embodiment the rigid member of stick is made from roller plastic or paper that is treated to prevent deterioration from water and soap. This rolled paper of plastic can include a note, or coupons. If the rolled paper is a note the note could be standard or uniquely customized by the person giving the soap on a stick as a gift.
[0027] Thus, specific embodiments of soap on a stick have been disclosed. It should be apparent, however, to those skilled in the art that many more modifications besides those described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the appended claims. | A bar of soap with a stick or other similar object placed through the bar of soap and extends out both sides of the bar is disclosed. The soap on a stick maintains the bar of soap off dish or other surface to promote drying the bar of soap and reduces how sogginess of the soap. The soap can be made from number of different materials and may contain colors, scents and conditioners. A soap dish is also disclosed with raised side members that the supports the ends of the stick to keep the bar of soap suspended above the dish. Drippings from the soap are collected in the base of the soap holder. An additional soap holder is disclosed that has elongated fingers to hold the ends of the stick. In this soap holder the drippings from the soap will fall into a shower or basin. | 0 |
BACKGROUND OF THE INVENTION
This invention relates to a leveling device for an asphalt finisher, a base paver or the like.
As is well known in the art, for an asphalt finisher as shown in FIG. 1, while a vehicle body 1 is moving, bituminous material supplied from a hopper 2 is delivered to a spreading screw 4 by means of a bar feeder 3 and the asphalt compound is uniformly spread to the right and left by the spreading screw 4 and is then leveled by a screed 5.
In case where a conventional asphalt finisher as described above paves a relatively wide road, auxiliary screeds 6 are provided on either side of the screed 5 as shown in FIG. 2 to cover the entire width of the road. However, this method is disadvantageous in that mounting the auxiliary screeds requires a great deal of time, labor and skill.
In order to eliminate this disadvantage, a technique has been proposed in the art in which, as shown in FIG. 3, wideners 7 are provided on both sides of the screed 5 in such a manner that they are extendably and retractably provided with respect to the screed 5 by hydraulic cylinders. However, this technique is disadvantageous in that, since the wideners 7, unlike the screed 5, have no tamping function, the material leveled by the wideners 7 is different in finish from the material leveled by the screed 5.
In view of the foregoing, an object of the invention is to provide a leveling device by which the leveling width can be readily changed, leveling can be achieved with a uniform finish, and a crown can be provided at a desired position.
SUMMARY OF THE INVENTION
This, as well as other objects of the invention, may be met by a leveling device for an asphalt finisher or the like including a pair of screeds for leveling a material such as bituminous material which is to be spread over a surface such as road surface, wherein the screeds are positioned at the front part of one side of the device and at the rear part of the opposite side of the device with the screeds being movable laterally and tiltable sidewards.
The device preferrably includes a main frame, a pair of supporting arms adapted at one end to be coupled to the body of a vehicle upon which the device is mounted, means for pivotably supporting the main frame on the supporting arms, and an auxiliary frame coupled to and movable vertically with respect to the main frame. The auxiliary frame has bearing means. At least one adjustment screw is provided for maintaining the position of the auxiliary frame at a selected fixed position relative to the main frame. The bearing means may include a pair of bushings which receive a corresponding pair of guided pipes supporting the screeds. The pivotable mounting means for the main frame is a supporting shaft extending through holes in both frames and at least one adjustment screw for maintaining the position of the main frame at a selected fixed tilt position relative to the supporting arms. Means may also be provided for vibrating the screeds. Also, the preferred embodiment includes at least one deflector means laterally slidably mounted to the main frame.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of an asphalt finisher equipped with a conventional leveling device;
FIGS. 2 and 3 are explanatory diagrams for a description of a conventional leveling width adjusting method;
FIG. 4A is a top view of a leveling device according to the present invention;
FIG. 4B is a diagram showing the mounting structure of a deflector;
FIG. 5 is a rear view of the leveling device according to the invention;
FIG. 6 is a sectional view taken along line VI--VI in FIG. 5;
FIG. 7 is a side view of the essential components of the leveling device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 4 through FIG. 7 show a preferred embodiment of the invention. In these figures, reference numeral 11 designates supporting arms. Two supporting arms 11 extend backwardly from a vehicle body (not shown), as in the prior art construction, and support a main frame 13 which has an auxiliary frame 12 at the central part thereof. The main frame 13 is pivotally supported by the supporting arms 11 through a supporting shaft 14 so that the main frame 13 can be inclined forwardly and backwardly with the supporting shaft 14 as a fulcrum by operating main frame vertical position adjusting screws 16 screwed in threaded holes 15 (FIG. 7) formed in the supporting arms 11. The auxiliary frame 12 is provided with bearing units 22 and 23 which permit sliding insertion of guide pipes 17 and 18 into bushings 19 and 20, so that it can be moved vertically with respect to the main frame 13 by operating crown adjustment screws 25 which are screwed into threaded holes 24 formed in the main frame 13. Bearing units 26 and 27 FIG. 4A are provided at both end portions of the main frame 13 which confront the bearing units 22 and 23. The bearing units 26 and 27 are adapted to support the guide pipes 17 and 18 in cooperation with the bearing units 22 and 23 so that the guide pipes can slide laterally. The bearing units 22, 23, 26 and 27 are identical in construction and can be moved vertically by means of screed height adjusting screws 33, 34, 35 and 36 which are engaged with threaded holes 28, 29, 31 and 32 formed in the auxiliary frame 12 and the main frame 13. The pairs of adjusting screws 33, 34, 25, 35 and 36 are turned simultaneously by means of sprocket wheels 37a, 37b, 37c, 37d and 37e and chains 38a, 38b, 38c 38d and 38e which interconnect them for moving the bearing units vertically. Operating handles 39 are detachably provided for the adjusting screws 16,25,33, 34, 35 and 36 to turn the latter, respectively.
FIG. 4A shows the state wherein the guide pipe 18 is retracted most leftwardly, while the guide pipe 17 is extended most leftwardly. The guide pipes 17 and 18 have frame members 41 and 42, respectively. The guide pipes 18 closer to the vehicle body are moved to the right in FIG. 4A by a cylinder 44 while the remaining guide pipes 17 are moved to the left in FIG. 4A by a cylinder 43. Each of the frame members 41 and 42 includes a tamper 45, a vertical moving means 46 for moving the tamper 45 vertically, a screed 47 and a vibrator device 48 for vibrating the screed 47. Each tamper 45 is mounted through a pin 52 on the end portion of a rotary arm 51 which is rotatably connected to a pivotal shaft 49 supported on the frame members 41 and 42. The upper end portion of the tamper 45 is pivotally mounted through an eccentric bushing 58 on a tamper shaft 57 which is rotated through a driving pulley 54, a belt 55 and a driven pulley 56 by a tapering hydraulic motor 53. Thus, the tamper 45 is moved up and down with the shaft 49 acting as a fulcrum by the vertical moving means 46 including the hydraulic motor 53 and the eccentric bushing 58.
The screed 47 is vibrated vertically when a vibrator shaft 63 to which a counterweight 62 is coupled is rotated by a screed hydraulic motor 64. The vibrator shaft 63, being supported by bearings 63a, is mounted to the screed 47 and is coupled to the hydraulic motor 64 through a driving pulley 65, a belt 66 and a driven pulley 67. The aforementioned vibrator device 48 includes the hydraulic motor 64, the vibrator shaft 63 and the counterweight 62.
As shown in FIG. 4A, a deflector 71 is provided in front of the main frame 13 on the side of the vehicle body. The deflector 71 has one end connected to the frame member 41 through a connecting member 69, and has the other end provided with a guide rod 72 which is supported by the auxiliary frame 12. Thus, the deflector 72 is movable laterally in accordance with the lateral movement of the frame member 41. The guide rod 72 as shown in FIG. 4B is secured between frames which are provided at the central line and the right edge of the deflector 71, respectively. The guide rod 72 is supported through a spherical bushing 70 to a deflector adjusting screw 74 which is screwed into a threaded hole 73 formed in a supporting member 12a which extends towards the vehicle body from the auxiliary frame 12 thus being movable vertically. Furthermore, the left end portion of the deflector 71 is supported by the lower end of a vertical adjusting screw 75 which is screwed into the end supporting member 69a of the connecting member 69.
The bearing units 22, 23, 26 and 27 are of the automatic centering type utilizing a spherical bushing.
The operation of the leveling device thus constructed according to the invention will next be described.
Similar to the prior art construction, the leveling device according to the invention is installed on a vehicle body. In the case where the leveling device is installed on an asphalt finisher for instance, the leveling device operates to uniformly level the asphalt compound which is delivered to the spreading screw through the bar feeder from the hopper and which is spread thereby.
Before starting leveling work as described above, first the position of the main frame 13 is corrected by operating the main frame vertical position adjusting screw 16 after which two sets of guide pipes 17 and 18, the screeds 47 relating thereto, the deflector 71, etc. are moved vertically by operating the screed height adjusting screws 33, 34, 35 and 36, so that the height or thickness of the leveled material is set at a desired level. The cylinders 43 and 44 are operated to horizontally move the guide pipes 17 and 18 and the associated mechanisms thereby to determine the width of the leveled material. It goes without saying that the leveling width can be continuously changed from the width of one screed 47 when the cylinders 43 and 44 are contracted maximally to the width of two screeds 47 when the cylinders 43 and 44 are expanded maximally.
In the case where it is required that the leveled surface have a crown, the crown adjusting screws 25 are operated to lift the auxiliary frame 12 and accordingly the inner ends of the guide pipes 17 and 18 are moved upwardly. If in this case the two sets of screeds 47 are coincident in height, the crown contour will coincide with the central line of the auxiliary frame 12. However, if the front screed 47, that is the screed closer to the vehicle body, is lower than the rear screed 47, the crown contour is shifted to the left as viewed in FIG. 4 from the central line of the auxiliary frame 12 depending on the vertical difference between the screeds 47 and the degree of inclination thereof. If the front screed 47 is higher than the rear screed 47, the crown contour is shifted to the right from the central line. The deflector 71 is horizontally moved together with the guide pipe 17 and the frame member 41 through the connecting member 69 by the cylinder 43. The height of the deflector 71 is adjusted by operating the deflector adjusting screws 74 and 75.
Once the above-described preparation has been completed, the vehicle body is run while the vertically moving means 46 and the vibrating means 48 are operated so that the paving material such as bituminous material is supplied to the right side of the deflectors 68 and 71 in FIG. 6. The material spread in front of the deflector is first suitably leveled by the deflector after which its flatness and compaction are increased as the tamper 45 is moved up and down by the vertical moving means 46. Finally, the material thus treated is tamped by the vibration of the screeds 47.
As is apparent from the above description, in a leveling device according to the invention, two screeds 47 are positioned at the front part and the rear part thereof, respectively, and are movable laterally. Therefore, the leveling width can be quickly and correctly changed by moving the screeds 47 laterally. In addition, as the screeds 47 can be tilted sidewards, it is possible to provide the leveled surface with a crown. Furthermore, it is possible to provide a crown contour at a desired position by the lateral movement and inclination of the screeds. | A leveling device for an asphalt finisher or the like including a pair of screeds disposed at front and rear portions of the device on auxiliary frames which are slidably coupled to a main frame. The main frame is pivotably mounted to a pair of supporting arms extending from the vehicle body. The screeds are both movable laterally and tiltable sidewards so that a predetermined depth of asphalt coating can be attained and a crown portion provided if desired. | 4 |
BACKGROUND OF THE INVENTION
Fluorinated polymers with pendant side chains containing ion exchange groups in the form such as sulfonic acid are known in the prior art. These resins are particularly useful where it is necessary to have thermal and chemical stability, e.g., for use as a membrane or a diaphragm in an electrolytic chlor-alkali cell. Suitable disclosures of ion exchange polymers are set forth in U.S. Pat. Nos. 3,773,634 and 3,793,163 wherein films are employed in a chlor-alkali cell for formation of chlorine and caustic. A teaching of use of an ion exchange polymer in a porous diaphragm for formation of chlorine and caustic is disclosed in U.S. Pat. No. 3,775,272.
SUMMARY OF THE INVENTION
The present invention is directed to formation of knitted and woven ion exchange fabrics formed from filaments of a fluorinated polymer containing pendant side chains in the SO 2 X form wherein X represents fluorine or chlorine and preferably fluorine. Conversion of the sulfonyl groups of the polymer to ionic form takes place whereby the polymer has ion exchange properties.
It is highly desirable for many applications that a thick film or a thick filament not be employed. For example, with thick gauges in a film or filament the resulting material will be thicker, heavier, more costly and generally will possess higher electrical resistance. Additionally, in use such as in a chlor-alkali cell, a penalty in operation may be imposed due to a lower current efficiency. To overcome these disadvantages, the amount of polymer for a unit area is most desirably minimized.
It is set forth in my copending application Ser. No. 430,754 filed Jan. 4, 1974 that it is possible to form a tightly woven fabric with minimum passage of liquid through fiber interstices. The use of a fabric overcomes limitations in a film whereby the physical strength of the film is unduly low. Also, in a film, a tear or perforation may quickly progress in length which is characteristic of many low gauge films.
The present invention encompasses the tightly woven fabrics set forth in my copending application Ser. No. 430,754. Additionally, the formation and use of woven or knitted fabrics is included which allow passage of liquid through fiber interstices.
The present invention permits the use of knitted and woven fabrics and overcomes an inherent weakness of low strength filaments. In weaving and/or knitting operations, a higher strength supporting material is employed with the ion exchange polymer precursor or the ion exchange polymer in filament form. Most desirably, a supporting filament is twisted with the filament comprising the ion exchange polymer precursor or ion exchange polymer. However, alternate manners of support are possible. Illustratively, a coating which imparts strength may be applied to the filament.
The high strength supporting material permits the weaving or knitting operation as if the fluorinated polymer possessed high strength. Thereafter, the high strength filament may be destroyed either before or at the time the ion exchange polymer is utilized.
DETAILED DESCRIPTION OF THE INVENTION
A fluorinated polymer with terminal sulfonyl groups present in the --SO 2 X form with X representing fluorine or chlorine and preferably fluorine represents the starting polymer which is formed into filaments. Illustratively, starting or precursor ion exchange polymers are set forth in Connolly et al. U.S. Pat. No. 3,282,875 and Grot U.S. Pat. No. 3,718,627. While it is highly desirable that the filament be supported when the sulfonyl groups are in the --SO 2 X form, nevertheless it is within the scope of the invention to have the sulfonyl groups in ionic form at the time of the weaving or knitting operation.
With the fluorinated polymer in the --SO 2 X form at the time of supporting operation, less difficulty is generally introduced into the weaving or knitting operation. Illustratively, in many instances with the polymer in ionic form, the filaments are more brittle and are more difficult to weave or knit into a uniform product. The fluorinated polymer with terminal groups in --SO 2 X form with X representing fluorine or chlorine is melt processable, i.e., it can be extruded and worked by application of elevated temperature. In contrast, the fluorinated polymer with sulfonyl groups in ionic form generally cannot be melt processed. Additionally, if a tightly woven fabric is necessary, the supporting operation with the high strength reinforcing material should take place prior to the conversion of the fluorinated polymer to ionic form.
By ionic form is denoted that the sulfonyl group will carry a negative charge under the conditions of ion exchange as opposed to covalent bonding present in the sulfonyl halide (--SO 2 X) form. Included within this definition of ionic form are sulfonyl groups which will convert to ionic form by splitting off of a hydrogen ion (under suitable pH conditions). An example of an ionizable group which will split off a hydrogen ion is a sulfonamide group (e.g., see Resnick and Grot, U.S. patent application Ser. No. 406,361 filed Nov. 16, 1973).
The denier (dry basis) of the filaments of fluorinated polymer with sulfonyl groups in --SO 2 X form or in ionic form will be less than 400. With a high denier and use of a supporting material, less care is necessary in the weaving or knitting operation to prevent breaks. A preferred denier (dry basis) is below 200 (and preferably above 50) in order to minimize the amount of polymer. Generally, it is not possible to directly weave or knit these fluorinated polymer filaments without excessive filament breakage. Use of the high strength supporting material overcomes the breakage problem.
The techniques of supporting the fluorinated polymer filaments are varied. A preferred manner is by twisting a high strength, low denier filament with the fluorinated polymer filament. Illustratively, a polyester, a polyamide (e.g., nylon) or a metal filament may serve as the supporting filament. Another technique is to coat the high strength supporting material onto the fluorinated polymer filament. Illustratively, the fluorinated polymer may be drawn through a bath of molten polymer for the coating application.
As employed herein, fluorinated polymer denotes a polymer with a backbone fluorocarbon chain which has sulfonyl groups attached either directly to a main fluorocarbon chain of the polymer or to a fluorocarbon side chain attached to a main chain, and where either the main chain or a side chain (or both) may contain ether oxygen atoms.
The intermediate polymers are prepared from monomers which are fluorine substituted vinyl compounds. The polymers are made from at least two monomers with at least one of the monomers coming from each of the two groups described below. The first group comprises fluorinated vinyl compounds such as vinyl fluoride, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro(alkyl vinyl ether), tetrafluoroethylene and mixtures thereof.
The second group is the sulfonyl containing monomers containing the precursor --SO 2 F or --SO 2 Cl. One example of such a comonomer is CF 2 =CFSO 2 F. Additional examples can be represented by the generic formula CF 2 =CFR f SO 2 F wherein R f is a bifunctional perfluorinated radical comprising 2 to 8 carbon atoms. The particular chemical content or structure of the radical linking the sulfonyl group to the copolymer chain is not critical and may have fluorine, chlorine or hydrogen atoms attached to the carbon atom to which is attached the sulfonyl group. If the sulfonyl group is attached directly to the chain, the carbon in the chain to which it is attached must have a fluorine atom attached to it. The R f radical of the formula above can be either branched or unbranched, i.e., straight chained and can have one or more ether linkages. It is preferred that the vinyl radical in this group of sulfonyl fluoride containing comonomers be joined to the R f group through an ether linkage, i.e., that the comonomer be of the formula CF.sub. 2 =CFOR f SO 2 F. Illustrative of such sulfonyl fluoride containing comonomers are ##EQU1## The most preferred sulfonyl fluoride containing comonomer is perfluoro(3,5-dioxa-4-methyl-7-octenesulfonyl fluoride), ##EQU2## The sulfonyl containing monomers are disclosed in such references as U.S. Pat. No. 3,282,875 to Connolly et al. and U.S. Pat. No. 3,041,317 to Gibbs et al. and in U.S. Pat. No. 3,718,627 to Grot.
The preferred intermediate copolymers are perfluorocarbon although others can be utilized as long as there is a fluorine atom attached to the carbon atom which is attached to the sulfonyl group of the polymer. The most preferred copolymer is a copolymer of tetrafluoroethylene and perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) which comprises 10 to 60 percent, preferably, 25 to 50 percent by weight of the latter.
The intermediate copolymer is prepared by general polymerization techniques developed for homo- and copolymerizations of fluorinated ethylenes, particularly those employed for tetrafluoroethylene which are described in the literature. Nonaqueous techniques for preparing the copolymers of the present invention include that of U.S. Pat. No. 3,041,317, issued to H. H. Gibbs and R. N. Griffin on June 26, 1962; that is, by the polymerization of a mixture of the major monomer therein, such as tetrafluoroethylene, and a fluorinated ethylene containing sulfonyl fluoride in the presence of a free radical initiator, preferably a perfluorocarbon peroxide or azo compound, at a temperature in the range of 0°-200°C. and at pressures in the range 1-200, or more, atmospheres. The nonaqueous polymerization may, if desired, be carried out in the presence of a fluorinated solvent. Suitable fluorinated solvents are inert, liquid, perfluorinated hydrocarbons, such as perfluoromethylcyclohexane, perfluorodimethylcyclobutane, perfluorooctane, perfluorobenzene and the like.
Aqueous techniques for preparing the intermediate copolymer include contacting the monomers with an aqueous medium containing a free-radical initiator to obtain a slurry of polymer particles in non-water-wet or granular form, as disclosed in U.S. Pat. No. 2,393,967, issued to M. M. Brubaker on Feb. 5, 1946; contacting the monomers with an aqueous medium containing both a free-radical initiator and a telogenically inactive dispersing agent, to obtain an aqueous colloidal dispersion of polymer particles, and coagulating the dispersion, as disclosed, for example, in U.S. Pat. No. 2,559,752 issued to K. L. Berry on July 10, 1951, and U.S. Pat. No. 2,593,583 issued to J. F. Lontz on Apr. 22, 1952.
The intermediate polymer is formed into a filament by conventional techniques such as extrusion melt spinning. Such extrusion melt spinning is well known in the prior art and conventional techniques are suitable in the present case. In the melt spinning operations, an increase in length during the drawing operation conventionally occurs such as of the order of 50 to 400 percent wherein the diameter is reduced. By this fashion, an orientated fiber is obtained in the drawing operation.
The intermediate fluorinated polymer which is formed into a filament desirably is supported by a high strength material prior to a weaving or knitting operation. The filament comprising a fluorinated polymer generally will not be of high strength. Where a tight weave is required such as disclosed in my copending patent application Ser. No. 430,754, use of thick filament will result in a heavy fabric which results in added weight and higher electrical resistance. The present disclosure by employment of the high strength supporting material allows the desired weaving into the final fabric form.
The types of supporting materials are varied which are suitable in the present disclosure. Generally, the supporting material will have a high strength to volume ratio in comparison to the fluorinated polymer. Illustratively, in employment of a supporting filament, a strong low denier supporting filament is desirable. Suitable supporting materials include polyamides (such as nylons), polyesters and metals. Since the supporting materials will not have the ion exchange properties in the manner of the fluorinated polymer with groups in ionic form, it is most desirable that the supporting material be destroyed after weaving or knitting. The destruction of the supporting material eliminates interference with ion exchange properties of the fabric.
The manner of destruction of the reinforcing material is varied and will be dependent on the reinforcing material and the state of the fluorinated polymer, i.e., sulfonyl groups in --SO 2 X or ionic form. Illustratively, with sulfonyl groups in --SO 2 X form, acid conditions may be employed to destroy the filaments. Illustratively, a supporting material of metal may be destroyed.
If caustic conditions will cause destruction of the supporting material, destruction of this material and conversion of the sulfonyl groups (--SO 2 X) of the fluorinated polymer to ionic form may take place simultaneously.
In another manner of destruction of the supporting material, the intermediate fluorinated polymer may be first converted to ionic form. This conversion may be undertaken by conventional techniques. Thereafter, the supporting filament may be destroyed by either an acid or caustic.
It is also possible to cause destruction of the supporting filament at the time of use of the fabric for ion exchange purposes. Illustratively, in a chlor-alkali cell, caustic conditions may remove the supporting material. In this event, the supporting material will serve as reinforcement until the time of actual employment of the fabric for its intended use.
It is desirable in many instances that the final article fabricated from the fabric be essentially impermeable to physical passage of liquids between the fabric strands. Water will swell the polymer and will diffuse directly through the polymer in ionic form. However, the construction of a tightly woven fabric minimizes passage between the interstices of the fabric of undesired components, e.g., salt passage into caustic formation of caustic and chlorine from a brine solution.
As employed herein, essentially impermeable denotes the ability of the woven fabric to pass at most a limited quantity of water. More specifically, the term denotes the passage of less than 100 ml of water through a square inch of fabric exposed to a vertical head of 19 inches of water during a 60-hour time period. The fabric is preconditioned prior to the test procedure by soaking in boiling water for one-half hour.
Upon conversion to the final polymer, shrinkage of the fiber takes place in the longitudinal direction while swelling of the fiber occurs along its width which causes the impermeability of the final woven fabric.
For purposes of explanation only as set forth in my copending application Ser. No. 430,754, it is considered that the final polymer in ionic form has a memory compared to the individual film from the intermediate fabric. In other words, in the melt spinning in a drawing operation, an increase in the length of the fiber takes place with a decrease in the diameter of this intermediate polymer form. It is considered upon conversion of the polymer to ionic form that the polymer remembers its original dimensions before the drawing operation and attempts to return to this state. The polymer shrinks along its longitudinal direction but in contrast swells along the fiber diameter. For all practical purposes, the volume of the fiber does not change greatly, if at all, but the physical volume is redistributed and swelling along the width denotes that the fiber is thicker in the final woven fabric. Therefore, the physical property of the final fabric of essential impermeability to the flow of liquids is realized, and the important utility of the invention is obtained wherein high strength is obtained in comparison to films of the polymer per se.
In an alternate manner, the intermediate polymer may be converted to ionic form prior to removal of the reinforcing material.
The exact technique employed will be dependent upon utility of the final article. More specifically, if a tightly woven fabric is necessary, the removal of the reinforcing material will take place before the polymer in its precursor form (sulfonyl groups present as --SO 2 X) is converted to the ionic form. However, if a fabric either woven or knitted is desired which is to contain spaces between the fibers, conversion may be undertaken to ionic form prior or after removal of the supporting material.
Conversion of the intermediate polymer to the ionic form will be by chemical reaction of the sulfonyl groups of the intermediate polymer.
The sulfonyl groups of the intermediate polymer may be converted from the --SO 2 X form to the form of --(SO 2 NH) m Q, wherein Q is selected from the group consisting of H, cation of an alkali metal and cation of an alkaline earth metal and m is the valence of Q or to the form of --(SO 3 ) n Me, wherein Me is a metallic cation, H, or NH 4 and n is the valence of Me.
In the above definition, preferred members include cations of alkali metals such as sodium or potassium.
For conversion of the intermediate sulfonyl groups to the --(SO 2 NH) m Q form wherein Q is H, contact may be undertaken with anhydrous ammonia in liquid or gaseous form. Conversion to Q as a cation of an alkali metal or alkaline earth metal may involve contact with the hydroxide of the cation of the alkali metal or cation of the alkaline earth metal.
Illustratively, conversion of the --SO 2 F groups to --SO 2 NH 2 may take place by contact with anhydrous ammonia which can be in the gaseous form, the liquid form, as a mixture with air or other gases which will not react with the sulfonyl group or the remaining portion of the polymer or ammonia in a solvent which is nonaqueous and which is nonreactive with the polymer.
To convert the sulfonyl groups in --SO 2 X form to --(SO 3 ) n Me form, the intermediate polymer may be contacted with a hydroxide of the metallic cation such as sodium hydroxide. In specific instances of Me, it may be necessary to form --SO 3 Na by reaction with sodium hydroxide followed by ion exchange with a solution of the salt of the desired Me.
Suitable disclosures of conversion from the intermediate to the final polymer are set forth in U.S. Pat. No. 3,282,825 and U.S. Pat. No. 3,770,567.
To further illustrate the innovative aspects of the present invention, the following Examples are provided.
EXAMPLE 1
A copolymer of tetrafluoroethylene and ##EQU3## (mole ratio of 7.5:1) was extruded at a temperature of 280°C. downwards through a 13 hole spinneret with a take off speed of 250 yards per minute. The yarn was then drawn at a rate of 1000 yards per minute over a pipe heated to about 150°C. resulting in a 300 percent elongation. The yarn bundle thus obtained had a thickness of about 2.5 mils while the 13 individual fibers have a thickness of 0.7 mil. For the subsequent weaving, one strand of this yarn was plied together with a 15-denier nylon filament.
Thereafter, the yarn was woven into a plain weave with a thread count of 120. The nylon monofilament in the fabric was destroyed by a treatment with a 1:1 mixture of 37 percent hydrochloric acid and acetic acid. This treatment caused a decrease in both length and width of the fabric of about 7 percent and microscopic examination revealed the voids left by the removal of the nylon monofilament. The fabric was then converted with the sulfonyl group in --SO 3 K form by treating with a solution containing 10 percent KOH and 30 percent DMSO at 70°C. for 5 hours. After washing with water and air drying the fabric showed a total shrinkage of 32 percent in length and 25 percent in width.
Microscopic examination showed that the voids left the removal of the nylon have been closed.
EXAMPLE 2
The disclosure of Example 1 was directly followed except the chemical treatment conditions were reversed. In other words, the sulfonyl groups in the fabric were converted to --SO 3 K form prior to destruction of the nylon filament with hydrochloric acid and acetic acid.
The yarn had a wrinkled appearance which upon microscopic examination showed voids left by the removal of the nylon.
Although the invention has been described by way of specific embodiments, it is not intended to be limited thereto. As will be apparent to those skilled in the art, numerous embodiments can be made without departing from the spirit of the invention or the scope of the following claims. | A woven or knitted fabric to be employed for ion exchange purposes comprises filaments of a fluorinated polymer with sulfonyl containing pendant side chains either in ionic or nonionic form whereby the filaments are supported by higher strength material prior to a weaving or knitting operation. Thereafter the supporting material is desirably removed. The final fabric may be woven so that the fabric is essentially impermeable to passage of fluids through fiber interstices or in an alternate manner is woven or knitted to allow controlled passage of liquid through fiber interstices. The polymer employed in the fabric possesses permselectivity giving desirable performance in electrolytic as well as membrane ion exchange and reverse osmosis devices. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of bags which are used to retain sporting equipment and in particular equipment used to play the game of baseball and softball, including uniforms, balls, ball catching gloves, and bats. The present invention also relates to the field of sporting bags which can be hung from a chain link fence to facilitate ready access to the equipment retained inside of the bag, both before and during the playing of the baseball game or softball game.
2. Description of the Prior Art
In general, the concept of a bag used to retain sporting equipment for use in games such as baseball and softball is known in the prior art. The following Eighteen (18) patents and published patent applications are relevant to the field of the present invention:
1. U.S. Pat. No. 4,793,532 issued to Dennis R. Cash on Dec. 27, 1988 for “Carrier For Ball Game Items” (hereafter the “Cash patent”);
2. U.S. Pat. No. 4,801,010 issued to Miriam S. Levitas on Jan. 31, 1989 for “Garment Bag With Strap To Secure Closure Flap In Bundled Configuration” hereafter the “Levitas patent”);
3. U.S. Pat. No. 4,890,731 issued to Edward J. Mroz on Jan. 2, 1990 for “Personal Sports Equipment Carrier” (hereafter the “Mroz patent”);
4. U.S. Pat. No. 5,407,111 issued to Alan J. Lanouette et al. on Apr. 18, 1995 for “Sports Accessory Bag With Convertible Suspension Means” (hereafter the “Lanouette patent”);
5. U.S. Pat. No. 5,425,449 issued to Charles A. Boorady on Jun. 20, 1995 for “Convertible Bag And A Method For Converting The Bag Between Two Functional Carrying Modes” (hereafter the “Boorady patent”);
6. U.S. Pat. No. 5,460,363 issued to Rex F. Tomer on Oct. 24, 1995 for “Sports Utility Accessory” (hereafter the “Tomer patent”);
7. U.S. Design Pat. No. Des 370,560 issued to David R. Doerbaum on Jun. 11, 1996 for “Baseball Equipment Bag” (hereafter the “Doerbaum Design patent”);
8. U.S. Pat. No. 5,562,204 issued to Rachel T. Sapyta et al. and assigned to Rachel Theora Sapyta on Oct. 8, 1996 for “Foldable Carrying Case” (hereafter the “Sapyta patent”);
9. U.S. Pat. No. 6,039,474 issued to Daniel A. DeChant on Mar. 21, 2000 for “Miniature Golf Bag Travel Organizer” (hereafter the “474 DeChant patent”);
10. U.S. Pat. No. 6,193,034 B1 issued to Marc Fournier on Feb. 27, 2001 for “Sports Bag” (hereafter the “034 Fournier patent”);
11. U.S. Pat. No. 6,196,718 B1 issued to Daniel A. DeChant on Mar. 6, 2001 for “Miniature Golf Bag Travel Organizer” (hereafter the “718 B1 DeChant patent”);
12. U.S. Pat. No. 6,276,501 B1 issued to Joy Tong on Aug. 21, 2001 for “Composite Suitcase” (hereafter the “Tong patent”);
13. United States Patent Application Publication No. 2003/0062328 A1 issued to Dave Millard on Apr. 3, 2003 for “Sports Equipment Holder” (hereafter the “Millard Published patent application”);
14. U.S. Pat. No. 6,681,936 issued to Donald E. Godshaw et al. and assigned to Travel Caddy, Inc. Jan. 27, 2004 for “Cosmetic Utility Kit” (hereafter the “Godshaw patent”);
15. U.S. Design Pat. No. D489,898 issued to Ralph C. Oberhelman on May 18, 2004 for “Sports Equipment Bag” (hereafter the “Oberhelman Design patent”);
16. U.S. Pat. No. 6,948,599 issued to Kathleen Rodrigue et al. and: assigned to Sports P.A.L. Inc., on Sep. 27, 2005 for “Sports Bag Insert” (hereafter the “Rodrigue patent”);
17. PCT Application No. WO 98/52439 issued to Marc Fournier filed on Apr. 9, 1998 for “Sports Bag” (hereafter the “52439 Fournier PCT Application”).
18. U.S. Pat. No. 6,732,863 issued to Speck and assigned to Hillerich & Bradsby Co. On May 11, 2004 for “Baseball/Softball Equipment Bag (hereafter the Speck patent”).
The Cash patent discloses a carrier for ball game items such as baseball bats. The device is designed to hang from a fence and essentially can be unfolded so that it hangs by two suitable hooks, 70 and 72 , so that there is access to the bats. This device discloses the concept of a hanging a bag in the vertical orientation so that the baseball bats can be accessed from the top of the bag by lifting the baseball bats vertically up and over and out of the bag.
The Levitas patent discloses a garment bag with a strap so that it can be carried and permitted to be hung vertically so that access can be achieved to various pockets within the bag.
The Mroz patent is a sports equipment carrier which has openings to permit it to carry one or more baseball bats. Further, the device can be carried by the handle. There is also disclosed two eyelets 28 which permit the sports bag to hang on hooks or nails that may be provided to protrude from a wall so that the equipment carrier 10 and the equipment carried therein can be readily stored when the equipment is not in use. The islets are strictly for storage.
The Lanouette patent is a small sports accessory bag to carry small items but definitely not baseball bats. It discloses suspension loops 16 and 17 which can be used to hang the bag from a horizontal bar such as an exercise apparatus as disclosed in FIG. 3 .
The Boorady patent discloses a convertible bag. The bag contains a suspending device 34 which can be used to hang the bag from a hook on a door or wall enabling the loading and unloading of articles 24 from the interior 22 of the carrier 10 .
The Tomer patent discloses a sports utility accessory which in its unfolded position can be used as a target for pitching and when in its folded position, used as a light bag to carry a baseball glove and a baseball which is used for pitching. It is essentially a fold over bag configuration which cannot be used to securely carry a baseball bat. The bag can also be hung by hooks as shown in FIG. 4 .
The Doerbaum patent discloses a design patent for a baseball equipment bag. It has carrying straps but does not disclose any means by which the bag can be hung from a fence.
The Sapyta patent is a patent for a foldable carrying case which does disclose the concept of being able to hang the bag so that it hangs vertically so that horizontal pockets are exposed for access.
The '474 DeChant patent discloses a golf bag organizer. It can be hung vertically so that it can be accessed from a horizontal opening but the vertical hanging member is just simply hook 70 .
The Fournier patent discloses a sports bag but its design enables the entire bag to completely open so that it is a generally flat configuration and then the bag can be hung from hook 12 .
The '718 DeChant patent is just a continuation of the previous '474 DeChant patent and has the same disclosure. The organizer is a miniature golf bag. The sidewall of the organizer is re-closable with the slide fastener which has a track that defines a bent U-shape.
The Tong patent discloses a composite suitcase. It discloses drawbars 14 which permit a removable hanging hook 15 to be attached thereto so that the device•can be hung from the hanging hook 15 .
The Millard Published patent application discloses a sports equipment holder which as disclosed best in FIG. 19 can be used to hold bats by being attached by horizontal tie members. The hook members 60 permit the sports equipment holder to be hung from a chain link fence.
The Godshaw patent discloses a cosmetic case which has two means by which the case can be hung vertically and one can gain access to the pockets which themselves hang vertically.
The Oberhelman patent is a design patent. It discloses the design and shape of a sports equipment bag. It does show the concept of having clip members but the clip members are attached at the vertical location so that the bag hangs vertically.
The Rodrigue patent discloses a sports bag insert which can be hung vertically by loop member 20 with the compartments exposed.
The PCT Application is PCT application based upon the Fournier patent which was already discussed.
The Speck patent discloses an equipment bag which has pockets for retaining sports equipment and a compartment for retaining a baseball bat. It also discloses a hook by which the sports bag can be retained on a chain link fence by hanging in a vertical orientation. As a result, to remove the baseball bat, the bat must by lifted out of and over the bag.
While the general concept of a sports bag to retain sporting equipment has been disclosed, there is a significant need for an improved bag configuration which enables easier access to the equipment, especially baseball bats, retained within the bag when the bag is hung from a fence.
SUMMARY OF THE INVENTION
The present invention is a sports equipment carrying bag which contains internal compartments of conventional design to enable sporting equipment such as uniforms, a baseball or softball, a catcher's mask, ball catching gloves and baseball or softball bats to be retained and carried therein. The unique feature of the present invention is that the carrying bag incorporates two bag retaining members which enable the sports bag to be hung from a fence such as a chain link fence in a manner which enables the bag to be horizontally oriented so that it is much easier to remove items from the bag without the items falling out and much easier to remove the baseball bats from the bag so that bats are horizontally removed and it is not necessary to lift the bats out of and over the sports bag when the bag is hung from the chain link fence.
It has been discovered, according to the present invention, that if a sports bag contains compartments including an elongated compartment which permits baseball bats to be retained in a horizontal orientation therein when the bag is carried, and the bag further contains means to retain the bag in a horizontal orientation when the bag is hung from a fence such as a chain link fence, then the horizontal orientation enables objects to be more easily removed from the bag and the baseball bats can be horizontally slid out of the bag when the bag is hung in a horizontal orientation, thereby facilitating a much easier removal of the baseball bats than was conventionally known in the prior art.
It has further been discovered, according to the present invention, that if the bag retaining means is comprised of a pair of spaced apart straps which are opened and closed by hook and loop fasteners, then the straps can be fed through links in the chain link fence and securely retained on the fence to enable the bag to be hung in a horizontal orientation; from the chain link fence.
It has additionally been discovered, according to the present invention, that if the straps with hook and loop fasteners thereon are incorporated into the sides of one of the carrying straps of the bag, the attachment is more secure and enables to bag to be more stabile as it is hung in a horizontal orientation from a than link fence.
It has also been discovered, according to the present invention, that if the bag retaining means is comprised of a pair of spaced apart hook and clip members, then the hooks can be inserted onto and through links in the chain link fence and securely retained on the fence through their respective clip members to enable the bag to be hung in a horizontal orientation from the chain link fence.
It has further been discovered, according to the present invention, that if the hook and clip members are respectively incorporated into straps which are connected to the sides of one of the carrying straps of the bag, the attachment is more secure and enables to bag to be more stabile as it is hung in a horizontal orientation from a chain link fence.
It is thereafter an object of the present invention to provide a sports bag which contains compartments including an elongated compartment which permits baseball bats to be retained in a horizontal orientation therein when the bag is carried, and the bag further contains means to retain the bag in a horizontal orientation when the bag is hung from a fence such as a chain link fence, then the horizontal orientation thereby enables objects to be more easily removed from the bag and the baseball bats can be horizontally slid out of the bag when the bag is hung in a horizontal orientation, thereby facilitating a much easier removal of the baseball bats than was conventionally known in the prior art.
It is a further object of the present invention to provide a bag retaining means which is comprised of a pair of spaced apart straps which are opened and closed by hook and loop fasteners, so that the straps can be fed through links in the chain link fence and securely retained on the fence to enable the bag to be hung in a horizontal orientation from the chain link fence.
It is an additional object of the present invention the incorporate the straps with hook and loop fasteners thereon into the sides of one of the carrying straps of the bag, so that the attachment is more secure and enables to bag to be more stabile as it is hung in a horizontal orientation from a chan link fence.
It is also an object of the present invention provide a the bag retaining means which is comprised of a pair of spaced apart hook and clip members so that the hooks can be inserted onto and through links in the chain link fence and securely retained on the fence through their respective clip members to enable the bag to be hung in a horizontal orientation from the chain link fence.
It is a further object of the present invention to respectively incorporate the hook and clip members into straps which are connected to the sides of one of the carrying straps of the bag, so that the attachment is more secure and enables to bag to be more stabile as it is hung in a horizontal orientation from a chain link fence.
Further novel features and other objects of the present invention will become apparent from the following detailed description, discussion and the appended claims, taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring particularly to the drawings for the purpose of illustration only and not limitation, there is illustrated:
FIG. 1 is a perspective view of the present invention sports bag illustrating one attaching means which is a pair of spaced apart straps to which are attached mating hook and loop fasteners, and also illustrating the bag in the opened condition to disclose compartments for retaining sporting objects such as gloves, baseballs, etc. and illustrating baseball bats retained in a horizontal orientation and hanging out of the bag;
FIG. 2 is a perspective view of the present invention sports bag illustrating one attaching means which is pair of spaced apart straps to which are attached mating hook and loop fasteners, with one strap in the closed condition and one strap in the opened condition, the straps being incorporated into one of the carrying straps of the bag;
FIG. 3 is a perspective view of the present invention sports bag illustrating one attaching means which is pair of spaced apart straps to which are attached mating hook and loop fasteners, the straps being incorporated into one of the carrying straps of the bag, the straps being fed through links in a chain link fence and respectively closed by their mating hook and loop fasteners to thereby retain the bag in a horizontal orientation on the chain link fence;
FIG. 4 is a perspective view of another embodiment of the present invention sports bag illustrating an alternative attaching means which is a pair of spaced apart hook and clip members, and also illustrating the bag in the opened condition to disclose compartments for retaining sporting objects such as gloves, baseballs, etc. and illustrating baseball bats retained in a horizontal orientation and hanging out of the bag;
FIG. 5 is a perspective view of the present invention sports bag illustrating the alternative attaching means which is pair of spaced apart hook and clip members, the hook and clip members being incorporated into one of the carrying straps of the bag; and
FIG. 6 is a perspective view of the present invention sports bag illustrating one attaching means which is pair of straps to which are respectively attached mating hook and clip members, the straps being incorporated into one of the carrying straps of the bag, the hooks being fed through links in a chain link fence and respectively closed by their mating clip members to thereby retain the bag in a horizontal orientation on the chain link fence.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Although specific embodiments of the present invention will now be described with reference to the drawings, it should be understood that such embodiments are by way of example only and merely illustrative of but a small number of the many possible specific embodiments which can represent applications of the principles of the present invention. Various changes and modifications obvious to one skilled in the art to which the present invention pertains are deemed to be within the spirit, scope and contemplation of the present invention as further defined in the appended claims.
Referring to FIG. 1 , there is illustrated at 10 a bag for retaining sports equipment. The bag 10 has an exterior surface 12 which contains at least one opening and closing means 14 such as a zipper. In the embodiment illustrated in FIG. 1 , the exterior surface 12 supports two zippers 14 and 16 , each leading to an interior compartment within the bag 10 . Zipper 14 is in the opened conditioned as illustrated in FIG. 1 (Zipper 14 is in the closed condition in FIG. 2 ). When opened, zipper 14 leads to an interior chamber 19 which has at least one compartment 20 and preferably a multiplicity of compartments 18 , 20 and 22 as illustrated, which can house various sports equipment such as uniforms, a ball catching glove, baseballs, and a catcher's mask. Zipper 16 when in the opening condition as illustrated in FIG. 1 leads to a lower elongated chamber 24 which can house at least one and preferably a multiplicity of baseball bats 100 , as illustrated.
The bag 10 is carried by a pair of carrying straps 26 and 36 . Carrying strap 26 has a first strap side 28 and a second strap side 30 by which the carrying strap 26 is attached to the exterior surface 12 of the bag 10 by attaching means such as stitching. The first strap side 28 and second strap side 30 each extend to a central grip portion 32 . Similarly, carrying strap 36 has a first strap side 38 and a second strap side 40 by which the carrying strap 36 , is attached to the exterior surface 12 of the bag 10 by attaching mean such as stitching. The first strap side 38 and second strap side 40 each extend to a central grip portion 42 . The bag 10 is carried by pushing the two grip sections 32 and 42 together and carrying the bag with the fingers of one hand surrounding the two gripping sections 32 and 42 . It is also possible to have a closing wrap (not shown) which surrounds the two grip section 32 and 42 of handles or carrying straps 26 and 36 to make the bag easier to carry.
The first embodiment of the present invention fence attaching member 50 is illustrated in FIGS. 1 and 2 . The attaching member 50 is comprised of a pair of spaced apart straps 52 and 62 . Strap 52 is permanently affixed at one end 54 to first strap side 38 of carrying strap 26 by means such as stitching or removably affixed by means of mating fastening members. At its other end 56 , strap 52 has one of an attaching means 58 , which by way of example can be a hook and loop fastener known as Velcro®. A mating attaching means 60 , which by way of example can be a mating hook and loop fastener known as Velcro®, is positioned at a location on the first strap side 38 remote from where the strap 52 is affixed to the first strap side 38 . In place of hook and loop, the fastening means can be mating snap fasteners or any other connecting means well known in the art. Strap 62 is permanently affixed at one end 64 to second strap side 40 of carrying strap 36 by means such as stitching or removably affixed by means of mating fastening members. At its other end 66 , strap 62 has one of an attaching means 68 , which by way of example can be a hook and loop fastener known as Velcro®. A mating attaching means 70 , which by way of example can be a mating hook and loop fastener known as Velcro®, is positioned at a location on the second strap side 40 remote from where the strap 62 is affixed to the second strap side 40 . In place of hook and loop, the fastening means can be mating snap fasteners or any other connecting means well known in the art.
Referring to FIG. 3 , the bag 10 is shown attached to a chain link fence 200 . The chain line fence 200 has a multiplicity of links 210 extending in one direction and a multiplicity of cross-links 220 extending in the opposite direction to form a multiplicity of open spaces 230 between links 210 and cross-links 220 . Strap 52 is opened and fed through at least one crossed set of links 210 and cross-links 220 and thereafter closed by mating attaching means 58 and 60 . Similarly, strap 62 is opened and fed through at least one crossed set of links 210 and cross-links 220 and thereafter closed by mating attaching means 68 and 70 . As a result, bag 10 is held on the fence 200 in a horizontal orientation. This orientation makes the bag much easier to open and remove its contents than conventional sports bags known in the prior art which are vertically oriented. In particular, baseball bats are horizontally oriented and therefore, instead of having to lift the bat up vertically and raise it over the bag 10 , all that is necessary is to horizontally slide the bat out, a much easier and safer removal technique. It is possible to have the bag 10 attached to the fence 200 with only one attaching assembly 52 or 62 and its associated attaching means 58 and 60 or 68 and 70 but the bag will then not hang perfectly horizontally.
The straps 52 and 62 of the attaching means 58 and 68 have been illustrated as attached to a portion of a carrying straps 26 and 36 . It will be appreciated that it is also within the spirit and scope of the present invention to have the straps 52 and 62 directly attached to the exterior surface 12 of the bag 10 instead of to a portion of a carrying straps. In that case, the mating attaching means 60 and 70 would be on a carrying strap or on a separate strap which aligns two attaching means together, or on another portion of the sports bag 10 .
Referring to FIG. 4 , there is illustrated at 110 an alternative embodiment of a bag for retaining sports equipment. The bag 110 has an exterior surface 112 which contains at least one opening and closing means 114 such as a zipper. In the embodiment illustrated in FIG. 4 , the exterior surface 4 supports four zippers, a pair of oppositely disposed zippers 114 and 114 A and a third zipper 116 , and a fourth zipper 117 . Zippers 114 and 114 a lead to an interior compartment within bag 110 and zipper 117 leads to the same or another interior compartment within the bag 110 . Zippers 114 and 114 A are in the opened conditioned as illustrated in FIG. 4 and zipper 117 is in the closed condition. In FIG. 5 , zippers 114 and 114 a are in the closed condition. As illustrated in FIG. 4 , when opened, zippers 114 and 114 a lead to an interior chamber 119 which has at least one compartment 120 and preferably a multiplicity of compartments 118 , 120 and 122 as illustrated, which can house various sports equipment such as uniforms, a ball catching glove, baseballs, and a catcher's mask. Zipper 116 when in the opened condition as illustrated in FIG. 4 leads to a lower elongated chamber 124 which can house at least one and preferably a multiplicity of baseball bats 100 , as illustrated.
The bag 110 is carried by a pair of carrying straps 126 and 136 . Carrying strap 126 has a first strap side 128 and a second strap side 130 by which the carrying strap 126 is permanently attached to the exterior surface 112 of the bag 110 by attaching mean such as stitching or removably attached by mating fastening members. The first strap side 128 and second strap side 130 each extend to a central grip portion 132 . Similarly, carrying strap 136 has a first strap side 138 and a second strap side 140 by which the carrying strap 136 is permanently attached to the exterior surface 112 of the bag 110 by attaching means such as stitching or removably attached by mating fastening members. The first strap side 138 and second strap side 140 each extend to a central grip portion 142 . The bag 110 is carried by pushing the two grip sections 132 and 142 together and carrying the bag with the fingers of one hand surrounding the two gripping sections 132 and 142 . It is also possible to have a closing wrap 144 which surrounds the two grip section 132 and 142 of handles or carrying straps 126 and 136 to make the bag easier to carry.
The second alternative embodiment of the present invention fence attaching member 150 is illustrated in FIGS. 4 and 5 . The attaching member 150 is comprised of a pair of spaced apart straps 152 and 162 . Strap 152 is permanently affixed at one end 154 to first strap side 138 of carrying strap 126 by means such as stitching or removably affixed by mating fastening means. At its other end 156 , strap 152 has one of an attaching means 158 , which by way of example can be a hook 159 with a closing clip 160 . Strap 162 is permanently affixed at one end 164 to second strap side 140 of carrying strap- 136 by means such as stitching or removably affixed by mating fastening means. At its other end 166 , strap 162 has an attaching means 168 , which by way of example can be a hook 169 with a closing clip 170 .
Referring to FIG. 6 , the bag 110 is shown attached to a chain link fence 200 . The chain line fence 200 has a multiplicity of links 210 extending in one direction and a multiplicity of cross-links 220 extending in the opposite direction to form a multiplicity of open spaces 230 between links 210 and cross-links 220 . The hook assembly 158 is clipped onto the fence 200 at the intersection of at least one set of links 210 and cross-links 220 by snapping the hook 159 over the cross-links and closing it with the closing clip 160 . Similarly, the hook assembly 158 is clipped onto the fence 200 at the intersection of at least one set of links 210 and cross-links 220 by snapping the hook 169 over the cross-links and closing it with the closing clip 170 . This orientation makes the bag much easier to open and remove its contents than conventional sports bags known in the prior art which are vertically oriented. In particular, baseball bats are horizontally oriented and therefore, instead of having to lift the bat up vertically and raise it over the bag 110 , all that is necessary is to horizontally slide the bat out, a much easier and safer removal technique. It is possible to have the bag 110 attached to the fence 200 with only one hook assembly 158 or 168 but the bag will then not hang perfectly horizontally.
The straps 152 and 162 of the hook assemblies 158 and 168 and•their associated hook and closing clip 159 and 160 , and 169 and 170 have been illustrated as attached to a portion of a carrying strap 126 and 136 . It will be appreciated that it is also within the spirit and scope of the present invention to have the straps 152 and 162 directly attached to the exterior surface 112 of the bag 110 instead of to a portion of a carrying strap, or attached to another portion of the carrying bag 10 :
The bags 10 and 110 have been illustrated only to show representative examples of sports bags with which the present invention novel attaching means have been incorporated. It will be appreciated that the present invention novel attaching means which enables the sports equipment bag to be attached to a fence and hang in a horizontal orientation can be incorporated into any multiplicity of differently designed sports bags. In addition, the facts that the first attaching means 50 was illustrated with bag 10 should not be interpreted to limit this attaching means to bag 10 . Attaching means 50 can be used with alternative bag 110 or any other sports bag. Similarly, the fact that attaching means 150 was illustrated with alternative bag 110 should not be interpreted to limit this attached means to sports bag 110 . Attaching means 110 can be used with bag 10 or any other sports bag.
Defined in detail, the present invention is a sports equipment bag to be hung from a chain link fence having a given vertical height and having a multiplicity of links extending in one direction, a multiplicity of cross-links extending in the opposite direction, and open spaces between the intersections of adjacent links and cross-links, the invention comprising: (a) a sports equipment bag having an exterior surface surrounding at least one interior compartment with means to gain access to the at least one interior compartment, the at least one interior compartment having sufficient length to house at least one bat, the bag having at least a first carrying strap having a first strap side of a given length, a second strap side of a given length and a central gripping portion; (b) a first elongated strap having a first end and a second end, the first elongated strap attached to the first strap side at a location adjacent the first end of the first elongated strap and having an attaching means on the first elongated strap adjacent its second end, a mating attaching means located on the first strap side and aligned with the attaching means on the first elongated strap; and (c) a second elongated strap having a first end and a second end, the second elongated strap attached to the second strap side at a location adjacent the first end of the second elongated strap and having an attaching means on the second elongated strap adjacent its second end, a mating attaching means located on the second strap side and aligned with the attaching means on the second elongated strap; (d) whereby the sports bag is hung from the chain link fence by opening said first elongated strap at the location of the mating attaching means and feeding the first elongated strap through at least one opening in the chain link fence and closing the attaching means, and opening said second elongated strap at the location of the mating attaching means and feeding the second elongated strap through at least one opening in the chain link fence and closing the attaching means, with both elongated straps affixed at the same vertical height to the chain link fence so that the sports bag hangs horizontally on the chain link fence and after the at least one compartment is opened, the at least one bat can be removed from the sports bag through a horizontal motion.
Defined broadly, the present invention is a sports equipment bag to be hung from a chain link fence having a given vertical height and having a multiplicity of links extending in one direction, a multiplicity of cross-links extending in the opposite direction, and open spaces between the intersections of adjacent links and cross-links, the invention comprising: (a) a sports equipment bag having an exterior surface surrounding at least one interior compartment with means to gain access to the at least one interior compartment, the at least one interior compartment having sufficient length to house at least one bat, the sports bag having means to enable the sports bag to be carried; (b) a first elongated strap having a first end and a second end, the first elongated strap attached to the sports bag at a location adjacent the first end of the first elongated strap and having an attaching means on the first elongated strap adjacent its second end, a mating attaching means located on a portion of the sports bag; and (c) a second elongated strap having a first end and a second end, the second elongated strap attached to the sports bag at a location adjacent the first end of the second elongated strap and having an attaching means on the second elongated strap adjacent its second end, a mating attaching means located on a portion of the sports bag; (d) whereby the sports bag is hung from the chain link fence by opening said first elongated strap at the location of the mating attaching means and feeding the first elongated strap through at least one opening in the chain link fence and closing the attaching means, and opening said second elongated strap at the location of the mating attaching means and feeding the second elongated strap through at least one opening in the chain link fence and closing the attaching means, with both elongated straps affixed at the same vertical height to the chain link fence so that the sports bag hangs horizontally on the chain link fence and after the at least one compartment is opened, the at least one bat can be removed from the sports bag through a horizontal motion.
Defined more broadly, the present invention is a sports equipment bag to be hung from a chain link fence having a given vertical height and having a multiplicity of links extending in one direction, a multiplicity of cross-links extending in the opposite direction, and open spaces between the intersections of adjacent links and cross-links, the invention comprising: (a) a sports equipment bag having an exterior surface surrounding at least one interior compartment with means to gain access to the at least one interior compartment, the at least one interior compartment having sufficient length to house at least one bat, the bag having at least a first carrying strap having a first strap side of a given length, a second strap side of a given length and a central gripping portion; (b) a first elongated strap having a first end and a second end, the first elongated strap attached to the first strap side at a location adjacent the first end of the first elongated strap and having a first attaching means on the first elongated strap adjacent its second end; and (c) a second elongated strap having a first end and a second end, the second elongated strap attached to the second strap side at a location adjacent the first end of the second elongated strap and having a second attaching means on the second elongated strap adjacent its second end; (d) whereby the sports bag is hung from the chain link fence by attaching the first attaching means onto at least one link on the fence and attaching the second attaching means onto at least one link on the fence, with both attaching means affixed at the same vertical height to the chain link fence so that the sports bag hangs horizontally on the chain link fence and after the at least one compartment is opened, the at least one bat can be removed from the sports bag through a horizontal motion.
Defined even more broadly, the present invention is a sports equipment bag to be hung from a chain link fence having a given vertical height and having a multiplicity of links extending in one direction, a multiplicity of cross-links extending in the opposite direction, and open spaces between the intersections of adjacent links and cross-links, the invention comprising: (a) a sports equipment bag having an exterior surface surrounding at least one interior compartment with means to gain access to the at least one interior compartment, the at least one interior compartment having sufficient length to house at least one bat, the sports bag having means to enable the sports bag to be carried; (b) a first elongated strap having a first end and a second end, the first elongated strap attached to the sports bag at a location adjacent the first end of the first elongated strap and having an attaching means on the first elongated strap adjacent its second end; and (c) a second elongated strap having a first end and a second end, the second elongated strap attached to the sports bag at a location adjacent the first end of the second elongated strap and having an attaching means on the second elongated strap adjacent its second end; (d) whereby the sports bag is hung from the chain link fence by attaching the first attaching means onto at least one link on the fence and attaching the second attaching means onto at least one link on the fence, with both attaching means affixed at the same vertical height to the chain link fence so that the sports bag hangs horizontally on the chain link fence and after the at least one compartment is opened, the at least one bat can be removed from the sports bag through a horizontal motion.
Of course the present invention is not intended to be restricted to any particular form or arrangement, or any specific embodiment, or any specific use, disclosed herein, since the same may be modified in various particulars or relations without departing from the spirit or scope of the claimed invention hereinabove shown and described of which the apparatus or method shown is intended only for illustration and disclosure of an operative embodiment and not to show all of the various forms or modifications in which this invention might be embodied or operated. | The present invention is a sports equipment carrying bag which contains internal compartments of conventional design to enable sporting equipment to be retained and carried therein. The unique feature of the present invention is that the carrying bag incorporates two bag retaining members which enable the sports bag to be hung from a fence such as a chain link fence in a manner which enables the bag to be horizontally oriented so that it is much easier to remove items from the bag without the items falling out and much easier to remove baseball bats from the bag so that bats are horizontally removed and it is not necessary to lift the bats out of and over the sports bag when the bag is hung from the chain link fence. | 0 |
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 62/156,654, filed May 4, 2015, which is incorporated herein by reference in its entirety.
BACKGROUND
[0002] Architectural precast panels are widely used in the commercial construction industry. They provide a low cost and efficient exterior paneling system for multistory buildings. Architectural panels also have the s chedule advantage of being fabricated off-site and then transported to the building site when needed. Architectural precast panels are easy to install and are relatively easy to repair when compared to other forms of exterior panel construction.
[0003] Architectural precast construction relies on mechanical connectors at discrete locations that are subjected to very large forces in a blast event, posing specific design problems to the engineer. These problems can be overcome with proper detailing.
[0004] Architectural panels typically have a row of connections at the top of the panel and row of connections at the bottom of the panel. Some architectural panels also have a row of connections along the sides of the panels. These connections are then attached to the structure through mounting brackets that are welded to the structural steel frame or embedded in the structural concrete.
[0005] For aesthetic reasons it is usually desired to have the panels as close together as possible. The gaps between the panels are typically filled with an elastomeric sealant Large gaps between panels are visually unattractive and the sealant must be maintained more frequently than the architectural panels. Multistory buildings are flexible structures that are designed to accommodate external forces. Common forces include horizontal and vertical ground forces (e.g earthquakes) or horizontal forces (e.g. wind pressure and blast pressure).
[0006] Although the internal steel structure is flexible, the exterior architectural panels are relatively rigid in comparison. When an external force causes the building to flex the panel connections must accommodate relative movements between flexing structure and the rigid panels. The capacity of a panel to deform significantly and absorb energy is dependent on the ability of its connections to maintain integrity throughout the blast response. If connections become unstable at large displacements, failure can occur. The overall resistance of the panel assembly will reduce, thereby increasing deflections or otherwise impairing panel performance.
[0007] It is also important that connections for blast loaded members have sufficient rotational capacity. A connection may have sufficient strength to resist the applied load; however, when significant deformation of the member occurs this capacity may be reduced due to buckling of stiffeners, flanges, or changes in nominal connection geometry, etc.
[0008] Both bolted and welded connections can perform well in a blast environment, if they can develop strength at least equal to that of the connected elements (or at least the weakest of the connected elements).
[0009] For a panel to absorb blast energy (and provide ductility) while being structurally efficient, it must develop its full plastic flexural capacity which assumes the development of a collapse mechanism. The failure mode should be yielding of the steel and not splitting, spilling or pulling out of the concrete. This requires that connections are designed for at least 20% in excess of the member's bending capacity. Also, the shear capacity of the connections should be at least 20% greater than the member's shear capacity, steel-to-steel connections should be designed such that the weld is never the weak link in the connection. Coordination with interior finishes needs to be considered due to the larger connection hardware required to resist the increased forces generated from the blast energy.
[0010] Where possible, connection details should provide for redundant load paths, since connections designed for blast may be stressed to near their ultimate capacity, the possibility of single connection failures must be considered. Consideration should be given to the number of components in the load path and the consequences of a failure of any one of them. The key concept in the development of these details is to trace the load or reaction through the connection. This is much more critical in blast design than in conventionally loaded structures. Connections to the structure should have as direct a load transmission path as practical, using as few connecting pieces as
[0011] Rebound forces (load reversal) can be quite high. These forces are a function of the mass and stiffness of the member as well as the ratio of blast load to peak resistance. A connection that provides adequate support during a positive phase load could allow a member to become dislodged during rebound. Therefore, connections should be checked for rebound loads. It is conservative to use the same load in rebound as for the inward pressure. More accurate values may be obtained through dynamic analysis and military handbooks.
[0012] The protection of multistory buildings to damage from earthquakes is described in the prior art. U.S. Pat. No. 3,638,377 issued on Dec. 3, 1969 to Caspe, describes an earthquake resistant multi-story structure that isolates the structure from the relative ground motions. U.S. Pat. No. 3,730,463 issued on Apr. 20, 1971 to Richard, describes a shock mounting apparatus to isolate the building footings. U.S. Pat. No. 4,166,344 issued on Mar. 31, 1977 to Ikonomen describes a system that allows the relative motion of a building structure relative to the ground using frangible links.
[0013] Architectural precast concrete can also be designed to mitigate the air pressure effects of a bomb blast. Rigid façades, such as precast concrete, provide needed strength to the building through in-plane shear strength and arching action. However, these potential sources of strength are not usually taken into consideration in conventional design as design requirements do not need those strength measures. Panels are designed for dynamic blast loading rather than the static loading that is more typical. Precast walls, being relatively thin flexural elements, should be designed for a ductile response. There are design tradeoffs between panel stiffness and the load on panel connections. For a surface blast, the most directly affected building elements are the façade and structural members on the lower four stories. Although the walls can be designed to protect the occupants, a very large vehicle bomb at small standoffs will likely breach any reasonably sized wall at the lower levels. There is also a decrease in pressure with height due to the increase in distance and angle of incidence of the air blast. Chunks of concrete dislodged by blast forces move at high speeds and are capable of causing injuries.
[0014] Therefore, what is desired is an improved system for connecting pre-cast architectural panels to the structure of the building to accommodate structural movements during earthquakes or high forces due to air pressure events.
SUMMARY
[0015] Architectural precast construction relies on mechanical connectors at discrete locations that may be damaged in a blast event, or large seismic event posing specific design problems to the engineer. These problems can be overcome with proper detailing. Precast concrete cladding wall panel connection details may be strengthened compared to conventional connections by incorporating a significant increase in connection hardware, the present inventive subject matter describes the connection details that improve the performance of architectural precast concrete cladding systems subjected to seismic and blast events.
[0016] In its broadest form, the inventive subject matter provides an embodiment describing a system for protecting the interiors of a building from earth quakes and explosive blasts, mainly comprising of precast architectural panel connectors. The precast architectural panel connector is comprised of a (i) precast panel mounted on to a building structure; (ii) a structural element, which is connected to the precast panel via a threaded rod and a bracket. (iii) crushing tube being placed on the threaded rod, which is positioned against the bracket by using adjusting nuts (iv) a coil spring placed on the threaded rod between the nuts and the crushing tube.
[0017] An embodiment of the present inventive subject matter describes an impact absorbing apparatus for a precast architectural panel connector comprising a crushing tube, the crushing tube having a hollow tube like structure with a rectangular cross section. A first face of the rectangular tube like structure having a central aperture and the second face being flat and also having a central aperture; further the first face being parallel to the second face of the rectangular tube frame like structure. The central aperture is adapted to receive a threaded rod which can bring in an impact such that upon impact, the first face of the crushing tube is resiliently deformed thus absorbing the impact, and the second face still remaining intact.
[0018] A further embodiment of the present inventive subject matter describes an impact absorbing apparatus comprising of a coil spring that is positioned on the threaded rod between the adjusting nut and the crushing tube or the structural bracket. The spring absorbs impact energy by elastic compression and returns to its original shape after impact.
[0019] A further embodiment of the inventive subject matter describes a method for installing an architectural panel connector comprising the steps of: (i) mounting a precast panel on to a building structure; (ii); (ii) connecting the precast panels to the structural elements via a threaded rod and a bracket; (iii) placing crushing tubes on both sides of the bracket; (iv) adjusting the position of the crushing tubes against the brackets by using the adjusting nuts (v) placing a coil spring on the threaded rod between the nuts and the crushing tube.
[0020] These and other embodiments are described in more detail in the following detailed descriptions and the FIG.s. The foregoing is not intended to be an exhaustive list of embodiments and features of the present inventive subject matter. Persons skilled in the art are capable of appreciating other embodiments and features from the following detailed description in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 is a side view assembly drawing.
[0022] FIG. 2 is a close-up view of the components surrounding a crushing tube and a coil spring.
[0023] FIG. 3 is a close-up view of the effect on the crushing tube when relative force of an architectural panel exceeds a predetermined amount in an inward direction.
[0024] FIGS. 4A and 4B is a close-up view of the effect on the crushing tube when relative force of the architectural panel exceeds a predetermined amount in an outward direction.
[0025] FIGS. 5 and 5A is a close-up view of the crushing tube.
[0026] FIG. 6 is an installed view of the crushing member.
[0027] FIG. 7 is a graphical representation of variation of load with respect to displacement for a 8″ inch crushing tube.
[0028] FIG. 8 is a graphical representation of variation of load with respect to displacement for a 8.5″ inch crushing tube.
[0029] FIG. 9 is a graphical representation of variation of load with respect to displacement for a 9.0″ inch crushing tube.
[0030] FIG. 10 is a graphical representation of the cumulative results of experimental results and theoretical predictions.
OVERVIEW OF THE SELECTED REFERENCE CHARACTERS
[0031]
[0000]
Pre-cast panel
110
Pre-cast panel width
112
Pre-cast panel distance from
114
pre-cast panel to structure
Pre-cast panel to panel gap
116
Building floor
120
Perimeter Structural Beam
130
Bracket
140
Threaded Rod
150
Adjusting Nut
160
Bearing Connection
170
Crushing Tube
180
Coil Spring
200
DETAILED DESCRIPTION
[0032] The representative embodiments are shown in FIGS. 1-6 , where similar features share common reference numerals. The notation ′ ″ or characters A,B,C etc represent a repetition of the same element.
[0033] Now referring to FIG. 1 which illustrates a side view of a multistory building 100 with architectural pre-cast panel 110 mounted on the side of the building, typically mounted one per building floor 120 . The architectural pre-cast panel 110 is connected to the perimeter structural beam 130 using a bracket 140 via a threaded rod 150 . The threaded rod 150 is securely affixed to the architectural pre-cast panel 110 . At the base of the architectural pre-cast panel 110 is a bearing connection 170 that supports the weight of the architectural pre-cast panel 110 . The architectural pre-cast panel 110 is positioned relative to the building floor 120 by adjusting nuts 160 A/ 160 B that are threaded onto the threaded rod 150 . Placed on the threaded rod 150 are crushing tubes 180 A/ 180 B. The adjusting nut 160 A/ 160 B are tightened against the crushing tubes 180 A/ 180 B.
[0034] Now referring to FIG. 2 which shows a close-up view of the crushing tubes 180 A/ 180 B which are placed on the threaded rod 150 on either side of the bracket 140 . The crushing tubes 180 A/ 180 B are tightened against the bracket 140 via the adjusting nut 160 A/ 160 B on either side of the crushing tubes 180 A/ 180 B. The coil spring 200 is placed on the rod between the crushing tube and the adjusting nut.
[0035] Now referring to FIG. 3 which shows an inward lateral movement 148 of the bracket 140 that is attached to the structural beam 130 relative to the pre-cast panel 110 . The inward movement deforms 192 B the crushing tube 180 B and creates a deformed crushing tube 190 B.
[0036] Now referring to FIG. 1 , FIG. 2 and FIG. 4A , whereby FIG. 4A shows an outward lateral movement 144 of the bracket 140 that is attached to the structural beam 130 relative to the precast panel 110 . The outward movement compresses the coil spring 200 and creates a fully compressed spring 210 .
[0037] Now referring to FIG. 1 , FIG. 2 and FIG. 4B , whereby FIG. 4B shows an additional outward lateral movement 145 of the bracket 142 that is attached to the structural beam 130 relative to the pre-cast panel 110 . The additional outward movement deforms the crushing tube 180 A and creates a deformed crushing tube 190 A.
[0038] Now referring to FIG. 5 which shows a close up view of the crushing tube 180 A and a side view of the crushing tube 180 B is as shown in FIG. 5A .
[0039] Now referring to FIG. 6 which depicts a representative assembly having the threaded rod 150 that is approximately one inch in diameter with nuts that can thread on the rod. The crushing tube may have dimension of four or six or eight inches in height and two or three inches in width. It should appreciated by those of ordinary skill that the specific dimensional descriptions are exemplary only. Crushing tubes with other dimensions may be used that generally fall within the spirit and scope of the present inventive subject matter. The threaded rod 150 is typically connected to the architecture panel via an embedded u-shaped bar that has a welded plate to allow the passage of the threaded rod. Other means of securing the rod to the panel could be devised without changing the concept of the system.
[0040] FIGS. 7, 8 and 9 are the graphical representation of the variation of yield load with respect to displacement for an 8 inches, 8.5 inches and 9.0 inches crushing tube respectively.
[0041] Table-1 given below shows variation of yield with load for an 8 inch crushing tube. FIG. 7 describes the graphical representation 700 for the same. Thus for a 8 inches crushing tube the yield load increases with increasing displacement 710 and plateaus 720 at 10,750 pounds.
[0000]
TABLE 1
8 inches
S.N
Load
PSI
delta
1
500
100
0
2
1550
500
0
3
2850
1000
1/32
4
3550
1250
1/32
5
4175
1500
3/64
6
4850
1750
1/16
7
5500
2000
1/16
8
6800
2500
1/8
9
8175
3000
5/32
10
9450
3500
7/32
11
10750
4000
1/4
12
10750
4000
5/16
13
10750
4000
3/8
14
10750
4000
7/16
15
11400
4250
1/2
16
10750
4000
9/16
17
10750
4000
11/16
18
10750
4000
13/16
19
10750
4000
7/8
20
10750
4000
1
21
10750
4000
1 1/8
22
10750
4000
1 1/4
[0042] Table-2 given below shows variation of yield with load for an 8.5 inch crushing tube. FIG. 8 describes the graphical representation 800 for the same. Thus for a 8.5 inches crushing tube the yield load increases 810 with increasing displacement and plateaus 820 at 11,400 pounds.
[0000]
TABLE 2
8.5 inches
S.N
Load
PSI
delta
1
1550
500
0
2
2850
1000
0
3
4175
1500
1/32
4
4850
1750
1/16
5
5500
2000
1/16
6
6800
25000
3/32
7
8175
3000
1/8
8
9450
3500
3/16
9
10750
4000
1/4
10
11400
4250
5/16
11
11400
4250
3/8
12
11400
4250
1/2
13
11400
4250
5/8
14
11400
4100
3/4
15
11000
4000
15/16
16
10750
4000
1 1/16
17
10750
4000
1 3/16
[0043] Table-3 given below shows variation of yield with load for a 9.0 inch crushing tube. FIG. 9 describes the graphical representation 900 for the same. Thus for a 9.0 inch crushing tube the yield load increases with increasing displacement and plateaus 920 at 12,800 pounds.
[0000]
TABLE 3
9.0 inches
S.N
Load
PSI
delta
1
1550
500
0
2
2850
1000
0
3
4175
1500
1/32
4
4850
1750
1/16
5
4850
2000
1/16
6
6800
2500
3/32
7
8175
3000
1/8
8
9450
3500
3/16
9
10750
4000
1/4
10
12050
4500
5/16
11
12050
4500
3/8
12
13400
5000
1/2
13
14041
5250
5/8
14
13400
5000
3/4
15
13400
5000
15/16
16
12700
4750
1 1/16
17
12700
4750
1 3/16
[0044] The moment carrying capacity of a steel member M P also called as the plastic moment for the section of the tube wall can be calculated by the formula M P =Fy (Yield Stress)*z (Plastic section modulus); M P =57,290*b*0.188 2 /4; M P =506*b: Where b=Tube Length
[0045] Further the yield load “P” on the whole tube can be calculated by the formula
[0000] P* 0.62=4 M P (1/2.625),thus P= 2.46 M P
[0046] By assuming a 10% over strength factor, P=1245.3*1.1*b=1370*b
[0047] For b (Tube Length)=4 inches: P=5480 Pounds
[0048] For b (Tube Length)=12 inches: P=16440 Pounds
[0049] FIG. 10 represents the graphical representation 1000 of the cumulative results based on the experimental findings and the theoretical predictions. Length of the tube (in inches) is plotted on the horizontal axis and the yield load (in pounds) is plotted on the vertical axis. 1010 and 1030 represent the two end points determined by theoretical calculations described above. The three central points 1020 are determined by experimental results described in FIGS. 7, 8 and 9 . The linear equation for the line drawn through the experimental and theoretical results can be generally represented by y=1380.5x−83.796 with R 2 =0.9949. The conclusion drawn by these efforts is that the yield load is linearly proportional to tube length. This allows for designing the crushing tube to conform to the specific requirements of each application.
[0050] Referring to Table-4 which represents the mill certificate showing the results for manufactured product—ASTM A500 GR B—2010, wherein “T” represents the thickness of the crushing tube as manufactured. All the material products were tested for variation in size, mechanical and chemical properties under various thermal conditions. A 0.188″ thickness crushing tube was used as the base sample for comparison purposes. The mill certificate certifies the products to be of the desired good quality and indicates the yield strength of the specific material used for the crushing tube.
[0000]
TABLE 4
Tensile
Y.P
S.N
Heat No.
T
L
(psi)
(psi)
1.
472005537
0.188
40
65,702
46,977
2.
473005414
0.250
20
67,008
47,853
3.
473005419
0.250
40
65,267
46,290
4.
473002067
0.188
20
70,199
57,290
5.
473002067
0.188
40
70,199
57,290
6.
473005414
0.250
20
67,008
47,863
[0051] Persons skilled in the art will recognize that many modifications and variations are possible in the details, materials, and arrangements of the parts and actions which have been described and illustrated in order to explain the nature of this inventive concept and that such modifications and variations do not depart from the spirit and scope of the teachings and claims contained therein.
[0052] All patent and non-patent literature cited herein is hereby incorporated by references in its entirety for all purposes. | Architectural precast concrete construction relies on mechanical connectors at discrete locations that may be damaged in a blast or seismic event, posing specific design problems to the engineer. These problems can be overcome with proper detailing. The performance of precast concrete cladding wall panel connection details may be enhanced by incorporating a specific connection hardware, herein described, that deforms elastically or inelastically to accommodate relative displacements due to building motion and/or energy associated with blast pressures. | 4 |
STATEMENT CONCERNING FEDERALLY SPONSORED RESEARCH
[0001] This invention was made with government support under NSF CBET-0755054. The government has certain rights in the invention.
FIELD OF THE INVENTION
[0002] The present invention relates to photon-based radiosurgery and more specifically to dynamic photon painting. The present invention provides for using a dynamically changing radiation beam (such as speed, direction, and/or dose) to irradiate a target thereby significantly increasing a radiation dose falloff rate.
BACKGROUND OF THE INVENTION
[0003] Radiosurgery is a non-invasive medical procedure for various kinds of tumors and one of the most effective means for treating local and regional targets such as brain tumors. Instead of a surgical incision, radiosurgery delivers a high dose of high energy photons in radiated beams to destroy the tumor. Radiosurgery is a very efficient method for treating cancers and avoids loss in quality of life compared to other more invasive methods such as surgery or chemotherapy. Since radiated high energy photons can also damage normal cells that are irradiated as the beam passes through a patient to irradiate a tumor, the key of a good radiosurgery plan is to maintain a sharp radiation dose falloff from the high radiation dose regions (high dose regions) inside the tumor to the low radiation dose regions (low dose regions) of nearby healthy structures. The steep radiation falloff rate of dose distribution—known as the “dose falloff rate”—guarantees that normal, healthy tissue and other body parts or structures near the target receive a low dose of radiation while the center of the target or tumor receives a high dose of radiation. Sharper radiation dose falloff will results in better tumor control and less damage to the normal tissue and other body parts surrounding the tumor that are irradiated by the radiation beams.
Focused Beam Geometry:
[0004] Currently, most radiosurgeries are performed in a “step-and-shoot” manner and use a number of precisely focused external beams of radiation that are aimed at the target from different directions to increase the dose falloff rate (see FIG. 1 ). In this technique, as the number of radiation beams increases, the dose falloff rate improves. Therefore, a large number of radiation beams focus on a target to create a high dose region around the target at the point of intersection of the beams. Intuitively, if the number of beams is increased, the contribution of each beam inevitably decreases, resulting in a lower dose to the tissues and structures some distance away from the target. This is because more beams pass through different parts of the body at lower radiation doses but collectively provide the same radiation dose to the target.
[0005] However, in these conventional radiation treatments the number of radiation beams is constrained to several hundred beams due to various spatial and physical constraints. For example, in Gamma Knife® radiosurgery, the number of radiation beams is limited to about two hundred beams. Physically, it is not possible to drill a large number of apertures in a fixed size metal screen without eventually causing interference among the beams escaping from the apertures.
[0006] For intensity-modulated radiation therapy (IMRT), it is usually not practical to deliver more than a dozen beams due to prolonged treatment time. Even with rotational techniques, such as Tomotherapy, intensity-modulated arc therapy (IMAT), volumetric modulated arc therapy (VMAT), and arc-modulated radiation therapy (AMRT), the maximum number of radiation beams is still limited to a few hundred.
Fundamental Physics Underlying Photon Radiosurgery:
[0007] The fundamental physics underlying photon-based radiosurgeries includes high energy photon production and photon interactions with matter.
[0008] Generally, high energy photons used in current radiosurgeries are produced either by radioactive decay from Cobalt-60 sources or bremsstrahlung interactions in a linear accelerator. In the linear accelerator, electrons are accelerated in an electric field to a high energy and then collide with a metal target. This generates radiation particles or photons in a bremsstrahlung process. The photons produced from Cobalt-60 are called “γ-ray” or gamma rays whereas the photons produced from a linear accelerator are called “X-ray” or X-rays.
[0009] Typically photons produced by different sources are heterogeneous in energy. For example, the energies of γ-rays emitted by Cobalt-60 are 1.17 and 1.33 MeV. The energy spectrum of X-rays from a linear accelerator shows a continuous distribution of energies for the bremsstrahlung photons superimposed by characteristic radiation of discrete energies. The energies of photon beams created by a 6 MV accelerator are continuous from 0 to 6 MeV with a large number of photons having energy around 2 MeV. For examples, Gamma Knife®(see FIG. 3 ) uses γ-rays emitted from radioactive Cobalt-60 sources to irradiate tumors, while Cyberknife® (see FIG. 4 ), which is essentially a linear accelerator carried by a robotic arm, uses X-rays to irradiate tumors.
[0010] When photons pass through matter, they interact in one of three ways: Photoelectric effect, Compton effect and Pair production. For radiosurgery, the predominant interaction is the Compton effect, where the incident photons collide elastically with orbit electrons. During this elastic collision, energy is imparted from the incident photons to orbiting electrons and sets off a chain of reactions. These electrons know as secondary electrons, as they travel through matter, produce ionization and excitation along their path. On a cellular level, these ionizations damage DNA and cause cell death in the body.
Important Beam Characteristics for Treatment Planning:
[0011] A percent depth dose curve relates the absorbed dose deposited by a radiation beam into a medium. FIG. 2( a ) shows the percent depth dose curve of Cobalt-60 with an 80 cm Source Surface Distance (SSD). Two parameters of a radiation beam are its Tissue Maximum Ratio (TMR) and Off Center Ratio (OCR). TMR is defined as the ratio of the dose at a given point in phantom to the dose at the same point at the reference depth of maximum dose. OCR is the ratio of the absorbed dose at a given off-axis point relative to the dose at the central axis at the same depth. FIG. 2( b ) shows the TMR of Cobalt-60 and a 6 MV accelerator. FIG. 2( c ) shows the OCR of a 6 MV accelerator.
SUMMARY OF THE INVENTION
[0012] The present invention improves the quality of radiosurgery by increasing the dose fall-off rate. The dose fall-off rate is determined from high dose regions inside a target such as a tumor to low dose regions of nearby healthy tissues and body parts or structure.
[0013] In order to further improve the focusing power of radiosurgery, dynamic strategies are implemented in the present invention. A beam source is directed around a focused point in a three dimensional (3D) trajectory and may provide a constant change of dose rate, speed, and beam directions to create kernels. The dynamic motion is equivalent to focusing tens of thousands of beams at a focus point and therefore creates kernels with a much sharper dose falloff.
[0014] The present invention uses a new optimization paradigm called “kernelling and de-convolution”. The paradigm uses two key steps: (1) kernelling, in which a subset of beams is “grouped” together by convolution to form “dose kernels”, and then optimized based on the kernels. (2) de-convolution, in which, once kernel level optimization is done, the kernels are de-convolved into individual beams to form a final dynamic plan. Instead of relying on numerical optimization, the present invention uses a hybrid geometric technique that involves geometric routing in both steps, and thus avoids the daunting task of optimizing hundreds of thousands of beams numerically.
[0015] Specifically, a radiation beam is moved along a helical type trajectory to dynamically irradiate a target and thereby further improve the dose falloff rate. This approach according to the present invention is termed herein as “dynamic photon painting” (DPP). The dose distribution from this convergence of tens of thousands of beams on a small volume is used as the DPP kernel.
[0016] As mentioned previously, the key to radiosurgery is the dose falloff rate. According to the present invention, DPP moves a beam source around an isocenter in a 3D trajectory, which is equivalent to focusing thousands of beams on a single point, to increase the dose falloff rate. FIG. 5 illustrates the trajectories of the radiation beam in DPP. The beam source rotates around the center of the target from latitude angle φ 1 to φ 2 , and 360° around in longitude angle.
[0017] The present invention also overcomes computational problems using the DPP approach. The least square problem often occurs as a key sub-problem of some larger computational problem, such as radiosurgery treatment planning. The least square problem is defined as min ∥Ax−b∥ 2 . Intuitively in this model, each column of A represents a radiation beam, the column vector b represents the ideal dose distribution and the goal of the optimization is to find the optimal “beam on time” for each column (i.e. X) to create a distribution as close to b as possible. Since in reality, “beam on time” must be non-negative, it is required x≧0, which gives the Non-Negative Least Square (NNLS). The following is a brief discussion of the solution of a least square problem and NNLS problem. If the total treatment time must stay under a given threshold T, we end up with the constrained least square problem with the constraint
[0000]
∑
x
∈
X
x
≤
T
.
[0000] There are many algorithmic solutions to the least square problems as is known to those skilled in the art.
[0018] The present invention and its attributes and advantages further understood, are further appreciated with reference to the detailed description below of some presently contemplated embodiments, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The preferred embodiments of the invention are described in conjunction with the appended drawings provided to illustrate and not to the limit the invention, where like designations denoted like elements, and in which:
[0020] FIG. 1 illustrates the cross-firing technique used in radiosurgery;
[0021] FIGS. 2( a )-( c ) illustrate the Percent Depth Dose, Tissue Maximum Ratio and Off Center Ratio curves of Cobalt-60 and 6 MV accelerator sources of radiosurgery;
[0022] FIG. 3 illustrates a conventional Gamma Knife® machine used in radiosurgery;
[0023] FIG. 4 illustrates a conventional CyberKnife® machine used in radiosurgery;
[0024] FIG. 5 illustrates the trajectories of the radiation beam in dynamic photon painting according to the present invention;
[0025] FIGS. 6( a )-( b ) illustrate curve fitting results according to the present invention;
[0026] FIGS. 7( a )-( b ) illustrate radiation dose profile comparisons between dynamic photon painting (DPP) kernels and Gamma Knife® perfexion 4 mm kernels according to the present invention;
[0027] FIGS. 8( a )-( d ) illustrate isodose comparisons between DPP kernels and Gamma Knife® perfexion 4 mm kernels according to the present invention;
[0028] FIGS. 9( a )-( b ) illustrate dose profile comparisons between kernels created by Cobalt-60 source and CyberKnife® cone beam according to the present invention;
[0029] FIGS. 10( a )-( c ) illustrate comparisons between the DPP kernel and 116 MeV proton according to the present invention;
[0030] FIGS. 11( a )-( b ) illustrate the impact of lateral angular range on the dose gradient of DPP kernels according to the present invention;
[0031] FIGS. 12( a )-( d ) illustrate isodose distributions of DPP kernels of different latitude angular ranges according to the present invention;
[0032] FIGS. 13( a )-( b ) illustrate the impact of complementary error function (ERFC) parameter on the dose gradient of DPP kernels according to the present invention;
[0033] FIGS. 14( a )-( d ) illustrate the isodose distributions of DPP kernels of different ERFC parameters according to the present invention;
[0034] FIGS. 15( a )-( c ) illustrate treatment planning of painting a three-dimensional (3D) tumor volume with a spherical “paintbrush” according to the present invention;
[0035] FIG. 16 illustrates comparisons of dose-volume histograms (DVH) according to the present invention;
[0036] FIGS. 17( a )-( b ) illustrate dose profile comparisons between a DPP plan and a Gamma Knife® plan according to the present invention;
[0037] FIGS. 18( a )-( d ) illustrate isodose comparisons between a DPP plan and a Gamma Knife® plan according to the present invention;
[0038] FIGS. 19( a )-( b ) illustrate a plot of C-shaped tumor phantom according to the present invention;
[0039] FIG. 20 illustrates comparisons of DVH according to the present invention;
[0040] FIGS. 21( a )-( c ) illustrate dose profile comparisons between a DPP plan and a Gamma Knife® plan according to the present invention;
[0041] FIGS. 22( a )-( d ) illustrates isodose comparisons between a DPP plan and a Gamma Knife® plan according to the present invention;
[0042] FIG. 23 illustrates comparisons of DVH according to the present invention;
[0043] FIGS. 24( a )-( c ) illustrate dose profile comparisons between various DPP plans according to the present invention;
[0044] FIG. 25( a )-( d ) illustrate isodose comparisons between various DPP plans according to the present invention; and
[0045] FIG. 26 illustrates an exemplary computer system, or network architecture, that may be used to implement the methods according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0046] The present invention is now described in detail with reference to preferred embodiments as illustrated in the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It is apparent, however, to one skilled in the art, that the present invention may be practiced without some or all of these specific details. In other instances, well known process steps and/or structures are not described in detail in order to not unnecessarily obscure the present invention.
[0047] The present invention uses a new optimization paradigm, in which “kernelling and de-convolution” occurs in the following steps: Step 1—(Kernelling) Dose kernels approximating the radiation dose distributions of about 10,000 focused beams are created by convolving thousands of equivalent beams via preset 3D trajectories; Step 2—(Dose painting) The dose kernel is viewed as a 3D “paintbrush” and an optimal route of the paintbrush is calculated to dynamically “paint” the targeted tumor volume; and Step 3—(De-convolution) The kernel is de-convolved along the route from Step 2 into a single or a few merged trajectories extending into a 4π solid angle of varying source-to-focal distances, which are connected into a dynamic treatment plan using geometric routing algorithms.
[0048] One advantage of the present invention kernelling and de-convolution paradigm is routing convolved kernels rather than numerically optimizing individual beams. By doing this process, the daunting task of optimizing hundreds of thousands of beams simultaneously is avoided, which even if implemented may prove to be too computational intensive to be practical.
[0049] Kernels are created by convolving 2,000 to 10,000 individual beams along preset 3D trajectories. This step requires a determination of the kind of beam profiles, cross-section shapes, and 3D trajectories that are mostly suited for dynamic radiosurgery in terms of creating the most sharp dose fall-offs in the kernels.
[0050] As an integral part of the planning system, a library of kernels is created using different beam shapes, profiles, and trajectories. The characteristics of each kernel in the library can be investigated for producing useful dose focusing powers.
[0051] By convolving individual beams into kernels and optimizing kernels rather than individual beams, directly optimizing a large number of beams is avoided, and treatment planning is shifted to routing the kernels to dynamically cover the target. To solve this routing problem, techniques from computational geometry are utilized.
[0052] The route calculated in the dose painting step will create a high quality plan, however to deliver it using robotic radiosurgery, this route of the kernels must be converted to a feasible dynamic route of a single beam. To accomplish this process, the kernels to individual beams along the route are de-convolved, which results in a set of beams with different orientation and locations. These individual beams are then connected into a tour, which will be the final dynamic radiosurgery plan. Specifically, the following problem is solved: Given a planar region with the presence of polygonal obstacles (e.g., the robotic arm in a CyberKnife® unit is not allowed in certain region for fear of collision with patient or patient table) and a set of sites, find a tour to visit all the sites.
[0053] Turning now to FIG. 5 , the above process as dynamic photon painting (DPP) may be performed by using a CyberKnife® cone radiation beam that is revolved in a hemispherical trajectory around a target. As shown in FIG. 5 and described above, the beam source rotates around the center of a target from latitude angle φ 1 to φ 2 , and 360° around in a longitude angle. The CyberKnife® beam model is obtained from curve fitting of measured Tissue Phantom Ratio (TPR) and Off Center Ratio (OCR) tables.
[0054] FIG. 6( a ) illustrates the curve fitting results for TPR and FIG. 6( b ) illustrates the curve fitting results for OCR. The functions used for curve fitting are:
[0000]
TPR
(
d
)
=
{
∑
i
=
1
5
a
i
d
i
-
1
for
d
<
d
max
-
a
6
·
(
d
-
a
7
)
for
d
>
d
max
and
OCR
(
SAD
,
r
)
=
0.5
·
(
erfc
(
a
·
(
r
·
800
SAD
-
b
)
)
+
erfc
(
a
·
(
r
·
800
SAD
+
b
)
)
)
,
[0000] where d is the depth and r is the off-center radius of the calculation point, Source to Axis Distance (SAD)=Source Surface Distance (SSD)+d, and
[0000]
erfc
(
x
)
=
2
π
∫
x
∞
-
t
2
t
[0000] is the error function. For a 10 mm cone, the curve fitting parameters for TPR are a 1 =0.8185, a 2 =0.0203, a 3 =0.004, a 4 =−0.0006, a 5 =0.00002, a 6 =0.0061, a 7 =15, and for OCR a=0.4317 and b=4.9375. (Note that the parameter b here is essentially the radius of the field at 800 mm standard SAD).
[0055] The motion trajectory of the beam source (see FIG. 5 ) is described using the following parameters: (1) latitude angular range [φ 1 ,φ 2 ], (2) longitude angular range [θ 1 , θ 2 ], and (3) source to axis distance.
[0056] By rotating the radiation beam in a dynamic manner, DPP kernels are created. Comparisons were carried out with Gamma Knife® kernels and proton Bragg Peaks. The DPP kernels were compared with Gamma Knife® Perfexion 4 mm kernels. The Gamma Knife® kernel is a 41×41×41 matrix with 0.5 mm steps.
[0057] FIGS. 7( a )-( b ) show the dose profile comparisons between DPP kernels and Gamma Knife® kernels. As shown, the DPP kernels were created using a 10 mm cone of the CyberKnife® beam model, a SAD of 320 mm, and a latitude angular range of 1° to 50°. The SAD was chosen so that the diameter of the DPP kernel at the isocenter is 4 mm. FIG. 7( a ) illustrates the dose profiles in the XY plane (along lateral directions) and FIG. 7( b ) illustrates the dose profiles in the XZ plane (along longitudinal directions).
[0058] FIGS. 8( a )-( d ) show the isodose comparisons of the two kernels, specifically between the DPP kernel and Gamma Knife® Perfexion 4 mm kernels. In these plots, the planes are defined as in FIG. 5 . FIG. 8( a ) illustrates the DPP kernel in the XY plane. FIG. 8( b ) illustrates the Gamma Knife® kernel in the XY plane. FIG. 8( c ) illustrates the DPP kernel in the XZ plane. FIG. 8( d ) illustrates the Gamma Knife® kernel in the XZ plane. The plot shown contains isodose lines from 10% to 100% with 10% steps. The DPP kernel of the present invention has a sharper lateral fall off than the conventional Gamma Knife® kernel.
[0059] In order to understand whether the DPP strategy or a specific beam source makes the kernel better, the same DPP trajectory was evaluated using a Cobalt-60 Gamma Knife® beam source as the beam source to create kernels and compared to DPP kernels created with the CyberKnife® cone beam. FIGS. 9( a )-( b ) show the dose profile comparisons between kernels created by the Cobalt-60 source and the CyberKnife® cone beam. FIG. 9( a ) illustrates the dose profiles in the XY plane (along the lateral direction). FIG. 9( b ) illustrates the dose profiles in the XZ plane (along the longitudinal direction). The dose profiles are almost identical, which means the impact of beam source is not significant and the DPP strategy causes kernels to have better dose falloff rates.
[0060] The same DPP kernels were compared with a pristine 116 MeV proton beam. The proton beam was generated in a water phantom with 10 6 primary protons. The proton beam had a circular Gaussian profile with σ=2 mm. The kernel had a 40 mm radius and bins with 0.5 mm sides and was calculated using the Fluka simulation program. FIG. 9( a ) shows the dose profile comparison in the longitudinal direction. FIG. 10( b ) shows the dose profile comparison in the lateral direction. FIG. 10( c ) shows the VDH comparison. As can be seen, the DPP kernel deposits most of its energy in a small region.
[0061] The impact of latitude angular ranges [φ 1 ,φ 2 ] on the dose gradient of the DPP kernels is also considered. By varying φ 1 and φ 2 , a set of kernels is obtained and their dose profiles and isodose distributions are compared as discussed below.
[0062] FIGS. 11( a )-( b ) show the comparisons of dose profiles with latitude angular ranges of 1° to 40° 1° to 45°, 1° to 50°, 1° to 55°, 1° to 60°, and 1° to 65°. As Δφ=φ 1 −φ 2 increases, the dose gradient increases in the XY plane (i.e., along the latitude direction) and decreases in the XZ plane (i.e., along the longitudinal direction). The optimal angular range is a tradeoff between the sharpness of dose in the XY plane to that in the XZ plane. In addition to the above comparisons, the impact of φ 1 is considered, the starting latitude angle when Δφ is fixed. The comparisons of the XZ isodose distributions of DPP kernels of different latitude angular ranges are shown in FIGS. 12( a - d ).
[0063] FIG. 12( a ) illustrates a latitude angular range of 1° to 50°. FIG. 12( b ) illustrates a latitude angular range of 5° to 55°. FIG. 12( c ) illustrates a latitude angular range of 10° to 60°. FIG. 12( d ) illustrates the Gamma Knife® 4 mm kernel. The plots shown contain isodose lines from 5% to 100% with 5% steps. As φ 1 increases, the isodose distributions in the XZ plane become more and more irregular at low dose levels in comparison to that of the Gamma Knife® kernels. The impact of the error function (ERFC) sharpness parameter on DPP kernels is also considered as discussed below.
[0064] The Off Center Ratio (OCR) curve is fitted using function f=0.5*(erfc(a(x−b))+erfc(a(x+b))), where erfc(x) is defined as:
[0000]
erfc
(
x
)
=
2
π
∫
x
∞
-
t
2
t
.
[0000] Mathematically, the parameter “a” reflects the sharpness, while “b” represents the width or radius of the field. FIGS. 13( a )-( b ) show the comparison of dose profiles with a=1 and a=10. Specifically, FIG. 13( a ) illustrates the profile comparison in the XY plane. FIG. 13( b ) illustrates the profile comparisons in the XZ plane. FIGS. 14( a - d ) show the isodose comparison of DPP kernels with different ERFC parameters. Specifically, FIG. 14( a ) illustrates the isodose distributions of the DPP kernel with a=10 in the XY plane. FIG. 14( b ) illustrates the isodose distributions of the DPP kernel with a=1 in the XY plane. FIG. 14( c ) illustrates the isodose distributions of the DPP kernel with a=10 in the XZ plane. FIG. 14( d ) illustrates the isodose distributions of the DPP kernel with a=1 in the XZ plane. The plots shown contain isodose lines from 10% to 100% with 10% steps. As can be seen from these figures, the dose falloff rate increases as “a” increases.
[0065] To demonstrate the advantage of DPP approach, the DPP kernels are replaced with the Gamma Knife® kernels and the resulting radiation dose distributions are compared. Gamma Knife® has long been consider the “gold standard” of various radiosurgery modalities. Since the DPP approach can outperform Gamma Knife®, the DPP approach is advancing the state of the art.
[0066] Two examples comparing the treatment planning result when using DPP kernels versus Gamma Knife® kernels are now discussed. In the first embodiment, a 3D spherical phantom is used with a 80 mm radius and a spherical tumor with a 7.5 mm radius at the center. Both optimizations ran with identical parameters. To ensure that the best possible Gamma Knife® plan is obtained, only 4 mm shots were used in the planning phase. The current Gamma Knife® system can produce kernels ranging from 4 mm to 16 mm, with the 4 mm kernel being the sharpest kernel. FIG. 16 shows the DVH comparisons. FIGS. 17( a )-( b ) and FIGS. 18( a )-( d ) show the comparisons between dose profiles and isodose distributions.
[0067] FIG. 17( a ) illustrates the dose profiles in the XY plane with the DPP plan shown by line 10 and the Gamma Knife® plan shown by line 12 . FIG. 17( b ) illustrates the dose profiles in the XZ plane, again, with the DPP plan shown by line 10 and the Gamma Knife® plan shown by line 12 . FIG. 18( a ) illustrates the isodose distributions of the DPP plan in the XY plane. FIG. 18( b ) illustrates the isodose distributions of the Gamma Knife® plan in the XY plane. FIG. 18( c ) illustrates the isodose distributions of the DPP plan in the XZ plane. FIG. 18( d ) illustrates the isodose distributions of the Gamma Knife® plan in the XZ plane. The plot shown contains isodose lines from 10% to 100% with 10% steps. As can be seen from these plots, the DPP plan and the Gamma Knife® plan are very similar with the DPP plans being slightly better and more uniform.
[0068] However, the precision of these comparisons is limited by the resolution of the Gamma Knife® kernels obtained from Zlekta at 5 mm. With such a sharp dose gradient, the numerical limit is approached. If these comparisons could be conducted at a much higher resolution, the sharper dose gradient of DPP plans of the present invention would be more pronounced.
[0069] The DPP kernels and Gamma Knife® kernels are also considered for a more challenging phantom, which contains a C-shaped tumor surrounding a spherical critical structure as shown in FIGS. 19( a )-( b ) with the line 14 defining the outer perimeter of the tumor, surrounding a spherical critical structure having an outer perimeter defined by line 16 . Specifically, FIG. 19( a ) illustrates the phantom in the XY plane and FIG. 19( b ) illustrates the phantom in the XZ plane.
[0070] The goal is to have the tumor receive a 2100 cGy radiation dose. FIG. 20 shows the DVH comparison. FIGS. 21( a )-( c ) and FIGS. 22( a )-( d ) show the comparisons between dose profiles and between isodose distributions. FIGS. 21( a )-( c ) illustrate the dose profiles with the DPP plan shown by line 18 and the Gamma Knife® plan shown by line 20 . Specifically, FIG. 21( a ) illustrates the dose provides along the X direction; FIG. 21( b ) illustrates the dose profiles along the Y direction; and FIG. 21( c ) illustrates the does profiles along the Z direction. FIG. 22( a ) illustrates the isodose distribution of the DPP plan in the XY plane; FIG. 22( b ) illustrates the isodose distributions of the Gamma Knife® plan in the XY plane; FIG. 22( c ) illustrates the isodose distributions of the DPP plan in the XZ plane; FIG. 22( d ) illustrates the isodose distributions of the Gamma Knife® plan in the XZ plane. The plots shown contains isodose lines from 10% to 100% with 10% steps. The DPP plan is better than the Gamma Knife® plan. This is because, in the DPP plan, the target receives a higher dose and critical structures receive a lower dose than with the Gamma Knife® plan.
[0071] Since the DPP approach uses a single cone beam to dynamically treat a target, it is possible to modify the beam profiles of the cone beam (e.g., beam sharpness) to further improve the dose gradient. To demonstrate this, two sets of DPP kernels are created with two different ERFC sharpness parameters a=1 and a=10. These kernels are used in the Dynamic Gamma Knife® Radiosurgery Treatment Planning System. The goal is to let the tumor receive a 2100 cGy dose. FIG. 23 shows the DVH comparison. FIGS. 24( a )-( c ) illustrates the dose profiles with the DPP plan shown by line 22 and the Gamma Knife® plan shown by line 22 . FIGS. 25( a )-( d ) show the comparisons between dose profiles and isodose distributions. FIG. 24( a ) illustrates dose profiles along the X direction;
[0072] FIG. 24( b ) illustrates dose profiles along the Y direction; and FIG. 24( c ) illustrates dose profiles along the Z direction. FIG. 25( a ) illustrates the isodose distributions of the DPP plan with a=10 in the XY plane; FIG. 25( b ) illustrates the isodose distributions of the DPP plan with a=1 in the XY plane; FIG. 25( c ) illustrates the isodose distribution of the DPP plan with a=10 in the XZ plane; and FIG. 25( d ) illustrates the isodose distribution of the DPP plan with a=1 in the XZ plane. The plots shown contain isodose lines from 10% to 100% with 10% steps. As the ERFC sharpness parameter increases, the target receives a higher dose and critical structures receive a lower dose, which results in an improved treatment plan using the present invention as compared to conventional treatment plans. In reviewing the profile comparisons shown in FIGS. 24( a )-( c ), it can be seen that the DPP plan with a=10 has a lower dose at a low dose region than a DPP plan with a=1. This means the critical structure receives a lower dose as the ERFC parameter increases.
[0073] CyberKnife® robotic radiosurgery may be used to implement dynamic photon painting according to the present invention. In one embodiment, it is contemplated that the computational challenge of optimizing thousands of beams can be solved using one or more of cloud computing, GPU technologies, vector instructions, and multithreading.
[0074] Dynamic photon painting for radiation therapy and radiosurgery may be used in place of proton therapy and Gamma Knife® radiosurgeries.
[0075] In addition to CyberKnife® robotic radiosurgery, FIG. 26 illustrates an exemplary computer system 100 , or network architecture, that may be used to implement certain methods according to the present invention. One or more computer systems 100 may carry out the methods presented herein as computer code. One or more processors, such as processor 104 , which may be a special purpose or a general-purpose digital signal processor, is connected to a communications infrastructure 106 such as a bus or network. Computer system 100 may further include a display interface 102 , also connected to communications infrastructure 106 , which forwards information such as graphics, text, and data, from the communication infrastructure 106 or from a frame buffer (not shown) to display unit 130 . Computer system 100 also includes a main memory 105 , for example random access memory (RAM), read-only memory (ROM), mass storage device, or any combination thereof. Computer system 100 may also include a secondary memory 110 such as a hard disk drive 112 , a removable storage drive 114 , an interface 120 , or any combination thereof. Computer system 100 may also include a communications interface 124 , for example, a modem, a network interface (such as an Ethernet card), a communications port, a PCMCIA slot and card, wired or wireless systems, etc.
[0076] It is contemplated that the main memory 105 , secondary memory 110 , communications interface 124 , or a combination thereof function as a computer usable storage medium, otherwise referred to as a computer readable storage medium, to store and/or access computer software and/or instructions.
[0077] Removable storage drive 114 reads from and/or writes to a removable storage unit 115 . Removable storage drive 114 and removable storage unit 115 may indicate, respectively, a floppy disk drive, magnetic tape drive, optical disk drive, and a floppy disk, magnetic tape, optical disk, to name a few.
[0078] In alternative embodiments, secondary memory 110 may include other similar means for allowing computer programs or other instructions to be loaded into the computer system 100 , for example, an interface 120 and a removable storage unit 122 . Removable storage units 122 and interfaces 120 allow software and instructions to be transferred from the removable storage unit 122 to the computer system 100 such as a program cartridge and cartridge interface (such as that found in video game devices), a removable memory chip (such as an EPROM, or PROM) and associated socket, etc.
[0079] Communications interface 124 allows software and instructions to be transferred between the computer system 100 and external devices. Software and instructions transferred by the communications interface 124 are typically in the form of signals 125 which may be electronic, electromagnetic, optical or other signals capable of being received by the communications interface 124 . Signals 125 are provided to communications interface 124 via a communications path 126 . Communications path 126 carries signals 125 and may be implemented using wire or cable, fiber optics, a phone line, a cellular phone link, a Radio Frequency (“RF”) link or other communications channels.
[0080] Computer programs, also known as computer control logic, are stored in main memory 105 and/or secondary memory 110 . Computer programs may also be received via communications interface 124 . Computer programs, when executed, enable the computer system 100 , particularly the processor 104 , to implement the methods according to the present invention. The methods according to the present invention may be implemented using software stored in a computer program product and loaded into the computer system 100 using removable storage drive 114 , hard drive 112 or communications interface 124 . The software and/or computer system 100 described herein may perform any one of, or any combination of, the steps of any of the methods presented herein. It is also contemplated that the methods according to the present invention may be performed automatically, or may be invoked by some form of manual intervention.
[0081] The invention is also directed to computer products, otherwise referred to as computer program products, to provide software to the computer system 100 . Computer products store software on any computer useable medium. Such software, when executed, implements the methods according to the present invention. Embodiments of the invention employ any computer useable medium, known now or in the future. Examples of computer useable mediums include, but are not limited to, primary storage devices (e.g., any type of random access memory), secondary storage devices (e.g., hard drives, floppy disks, CD ROMS, ZIP disks, tapes, magnetic storage devices, optical storage devices, Micro-Electro-Mechanical Systems (“MEMS”), nanotechnological storage device, etc.), and communication mediums (e.g., wired and wireless communications networks, local area networks, wide area networks, intranets, etc.). It is to be appreciated that the embodiments described herein can be implemented using software, hardware, firmware, or combinations thereof.
[0082] The computer system 100 , or network architecture, of FIG. 26 is provided only for purposes of illustration, such that the present invention is not limited to this specific embodiment. It is appreciated that a person skilled in the relevant art knows how to program and implement the invention using any computer system or network architecture.
[0083] The invention is also directed to computer products (also called computer program products) comprising software stored on any computer useable medium. Such software, when executed, at least in part, in one or more data processing devices, causes the data processing device(s) to operate as described herein. Embodiments of the invention employ any computer useable or readable medium, known now or in the future. Examples of computer useable mediums include, but are not limited to, primary storage devices (e.g., any type of random access memory), secondary storage devices (e.g., hard drives, floppy disks, CD ROMS, ZIP disks, tapes, magnetic storage devices, optical storage devices, MEMS, nanotechnological storage device, etc.), and communication mediums (e.g., wired and wireless communications networks, local area networks, wide area networks, intranets, etc.). It is to be appreciated that the embodiments described herein can be implemented using software, hardware, firmware, or combinations thereof.
[0084] While the disclosure is susceptible to various modifications and alternative forms, specific exemplary embodiments thereof have been shown by way of example in the drawings and have herein been described in detail. It should be understood, however, that there is no intent to limit the disclosure to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure as defined by the appended claims. | Photon-based radiosurgery is widely used for treating local and regional tumors. The key to improving the quality of radiosurgery is to increase the dose falloff rate from high dose regions inside the tumor to low dose regions of nearby healthy tissues and structures. Dynamic photon painting (DPP) further increases dose falloff rate by treating a target by moving a beam source along a dynamic trajectory, where the speed, direction and even dose rate of the beam source change constantly during irradiation. DPP creates dose gradient that rivals proton Bragg. Peak and outperforms Gamma Knife® radiosurgery. | 0 |
TECHNICAL FIELD
The present invention relates to a method and control means for controlling a robot, in particular human-collaborating robot while resolving a robot- or task-specific redundancy.
BACKGROUND
Presently designated as a human-collaborating robot in particular is a robot that physically interacts with a human being, for example by providing for a stay of the human being in a workspace of the robot. In particular in the case of such robot applications it is desirable to reduce the consequences of a collision of a contact point of the robot with its surroundings, in particular the human being. Up to now, to this end, for example under ISO-10218, limits were predefined, for example a maximum TCP speed of 0.2 to 0.25 m/s. However, this worst-case approach impedes the performance of in particular human-collaborating robots.
SUMMARY
In general the pose or position of a robot can be unambiguously described with f degrees of freedom by its joint coordinates q∈ ′. At the same time, the position and orientation of a reference point or system of the robot, in particular of its TCP, can be predefined by its coordinates z T =(x T ∈ m≦3 α T ∈ n≦3 ), where x for example describes the Cartesian coordinates of the TCP, α describes its orientation, say in Euler or Cardan angles. The difference f−(m+n) defines the redundancy of the manipulator. A robot-specific redundancy always arises when the manipulator has more than 6 degrees of freedom or joints, while a task-specific redundancy arises when fewer reference point coordinates are predefined than the manipulator has degrees of freedom, for example only the position of the TCP of a six-axle robot f−(m+n)=6−(3+0)=3). For more compact representation, also a six-axle manipulator with one or more additional axles, for example a portal or a tool bench, as well as a system of several manipulators cooperating with one another are generally referred to as a robot in terms of the present invention.
Descriptively, a redundant robot can constitute a predefined reference point coordinate vector in at least two, in particular in an infinite number of different redundant poses. In order to determine control quantities for the joint drives of the robot from predefined reference point coordinates, the redundancy must thus be resolved by calculation or one of the redundant poses must be selected.
To this end, up to now different quality criteria were minimized: thus the redundancy can be used to minimize the reciprocal value of the distance to singular poses and/or obstacles, to plan energy-efficient paths or the like.
The problem addressed by the present invention is that of improving the operation of a robot, in particular of a human-collaborating robot.
This problem is solved by a method with the features of claim 1 or a control means with the features of claim 10 . Claim 11 protects a computer program product, in particular a storage medium or a permanent or volatile storage medium with a computer program for carrying out an inventive method stored on it, the subsidiary claims relate to advantageous improvements. A means in terms of the present invention can be designed likewise by software or by hardware; in particular it can comprise a program or program module and/or a processing and memory unit. A control means can hence likewise be a hardware control of a robot, in particular its control cabinet and/or a computer for programming the robot as well as also a program (subroutine) running in it.
The invention is based on the idea of using a redundancy of a robot to reduce the consequences of a collision of a contact point of the robot with its surroundings, in particular with the human being: a redundant robot has a different hazard potential in different redundant poses. By selecting a favorable pose, for example in the case of a path plan, thus the consequences of a collision can be reduced in the case of constant operating speed. Similarly, it is possible to increase the operating speed and thus increase the performance of the robot.
In accordance with the invention, it is therefore proposed to minimize a pose-dependent inertia variable of the robot to resolve the redundancy. A reduction of an inertia variable reduces the impulse or impact which the robot maps onto the obstacle in the event of a collision and thus its hazard potential.
In one preferred design this inertia variable, in particular on the basis of joint coordinates and/or a predefined direction, is determined in advance, i.e. offline, or during operation, i.e. online. The determination on the basis of joint coordinates projects the physical inertias, for example link masses, in the direction of the degrees of freedom of the robot and is therefore advantageous in order to resolve its redundancy. The determination on the basis of one or more predefined directions makes it possible to specifically minimize the hazard potential for this direction(s). In particular, the inertia variable can be determined on the basis of a predefined direction of movement and/or at least of a possible collision-direction of impact of the robot, which for example can arise from a path plan, a manual control for teaching or the like. If the robot moves in this predefined direction, it has a reduced hazard potential in the case of a collision.
In particular, the inertia variable can comprise, preferably be an effective mass, an effective moment of inertia and/or a pseudo matrix of the kinetic energyΛ v , Λ w . In square format
1 2 q . T · M ( q ) · q .
of the kinetic energy the mass matrix M(q) describes the inertia properties of the manipulator in the configuration space. Also for redundant manipulators the Jacobi matrices of the translation and rotation
J = ( J v J ω )
the translational or rotational pseudo matrix of the kinetic energy Λ v ,Λ w is defined by:
Λ
v
-
1
(
q
)
=
(
∂
x
∂
q
)
︸
J
v
(
q
)
·
M
-
1
(
q
)
·
J
v
T
(
q
)
Λ
ω
-
1
(
q
)
=
(
∂
α
.
∂
q
.
)
︸
J
ω
(
q
)
·
M
-
1
(
q
)
·
J
ω
T
(
q
)
(
1
)
where preferably one or more possible contact points of the robot, with which it could collide with its surroundings, in particular with a cooperating human being, or also an outstanding reference point such as in particular its TCP, a center of mass of a robot-guided useful load or an operating point of a robot-guided tool can be selected as a reference point with the coordinates z T =(x T α T ).
For a direction predefined by the unit vector u
1
m
u
(
Λ
v
)
=
u
T
·
Λ
v
-
1
(
q
)
·
u
1
I
u
(
Λ
ω
)
=
u
T
·
Λ
ω
-
1
(
q
)
·
u
(
2
)
describes the effective mass m u (Λ v ) or the effective moment of inertia I u (Λ ω ). along the direction or around the axis of rotation u, i.e. in each case on the basis of the direction u. They graphically describe the translational or rotational inertia of the (redundant) manipulator along the direction or around the axis of rotation.
In the following the invention will be further explained in particular using the example of the effective mass which arises for the TCP as a reference point and whose direction of movement is predefined by u. However, in addition or as an alternative, other directions, for example directions of movement, as result in the event of a malfunction of drives of the robot, and/or other points, for example vertices of the robot, which are especially collision-endangered, can be applied. In addition or as an alternative to one or more effective masses, for example eigenvalues of the pseudo matrices of the kinetic energy can be applied as inertia variables.
With the effective mass m u (Λ v (q)), a mathematical inertia variable can be determined for each pose of the robot clearly predefined by the joint angle q. This can be used in one design as a quality criterion of a path plan. In the process, the inventive minimized inertia variable can constitute the only quality criterion of a path plan. Similarly, it can be taken into consideration, in particular as a weighted quality, together with other quality criteria such as an energy optimality, a distance to obstacles, unique, target and/or previous poses, for example in a Pareto- or functional optimization. Thus, for example in the case of a path plan the achievement of target poses can be predefined as a quality criterion or second-order condition, the minimization of the inertia variable as (a further) quality criterion.
In particular in the case of an optimization within the scope of a path plan or in the case of online control of the robot, for example when approaching reference poses to be taught, in one advantageous improvement a gradient of the inertia variable, preferably numerical, in particular discretized, can be determined and a pose of the robot can be varied in one direction of this gradient. If the effective mass m u (Λ v (q)) is again applied as an example, a gradient has
∇
m
u
=
(
∂
m
u
∂
q
)
≈
(
m
u
(
q
2
)
-
m
u
(
q
1
)
q
2
-
q
1
)
(
3
)
in the direction of the greatest increase of the effective mass. By changing the pose in negative gradient direction corresponding poses can be determined with lower effective masses.
In addition or as an alternative to such a gradient-based minimization, an inertia variable can also be minimized in one preferred design by determining the associated inertia variable in each case for two or more redundant poses and selecting the pose with a lower, in particular with the lowest inertia variable. As becomes clear in particular from this, a minimization within the meaning of the present invention is defined in particular as the selection of a pose which has a smallest inertia variable at least locally. In the process however, the invention is not restricted to such an absolute minimization; on the contrary, for improvement of the operation of the robot, in particular for reduction of its hazard potential and/or improvement of its performance through a higher operating speed it can be sufficient to select the pose with the smaller inertia variable of two or more redundant poses. Therefore, for more compact representation, also a reduction of an inertia variable will be referred to generally as minimization of the inertia variable within the meaning of the present invention.
In particular, when a path of the robot is planned in advance, in one preferred improvement the inertia variable can be minimized for one or more, preferably discrete, in particular equidistant or signalized, for example taught path points. In the process, preferably the path tangent is applied as the predefined direction in the respective path point. If the robot leaves the path that has ben planned in such a way, it has a reduced hazard potential preferably in its movement and thus one possible collision direction or said robot will be able to travel the path more rapidly at equal hazard potential.
In addition or as an alternative, the pose with a minimized inertia variable can be determined in advance and, saved preferably in tabular form, also for one or more, preferably equidistantly distributed spatial points, in particular points of the configuration or workspace of the robot, in each case preferably for one or more directions, for example coordinate axle directions of a global coordinate system. During operation or in the event of planning a path, it is then possible to interpolate or extrapolate from the closest saved poses in order to resolve the redundancy. In this way in the event of low computer performance or CPU time a minimization of the inertia variable can be carried out by resolving the redundancy of the robot. In one preferred improvement the resolution of the redundancy can also take place in several stages, on the one hand for example by determining one or more redundant degrees of freedom in such a way that the inertia variable is minimized, and using other degrees of freedom for representation of predefined reference point coordinates and/or for optimization of other quality criteria. Similarly, optimum poses can also be determined with respect to the inertia variable and other criteria for redundancy resolution and from these poses, for example by averaging, interpolation or the like a pose can be selected.
In one preferred design a pose with minimal inertia variable is predefined as a reference pose, for example as the initial value of an optimization. In one preferred improvement a virtual force is imprinted in the null space of the redundant robot, said virtual force harnessing its kinematics to the reference pose, so that the robot approaches during operation or in the event of path planning of the reference pose. Such null space can for example be imprinted in the case of path planning considering other quality criteria and/or second-order conditions in order at the same time to reduce the hazard potential or achieve better performance.
In the case of the minimization of the inertia variable one or more selected or likewise all degrees of freedom of the robot can be varied. For example, six joints, which represent a complete mapping of the workspace, can be used to achieve a predefined reference point pose, further joints for minimization of the inertia variable. Similarly, it can be advantageous to vary one or more joint coordinates that are closest in basis, for example an angle of rotation for a link arm or carousel, which are ordinarily represented by heavier robot links, for minimization of the inertia variable.
As explained above, by means of an inventive resolution of the redundancy while minimizing a pose-dependent inertia variable of the robot its hazard potential, in particular in the case of constant speed of the robot, can be lowered. Likewise it is possible to increase the speed of the robot at constant or reduced hazard potential. To this end, in one preferred design of the present invention a speed of the robot is predefined such that a pose-dependent motion variable does not exceed a threshold.
The motion variable can in particular contain, or in particular be a product of the inertia variable and of a power of a speed of the robot or one of its derivatives. If in one preferred improvement the inertia variable is the effective mass, its product with the speed of the reference point in the predefined direction of movement or also its product with the square of this speed can be determined as the motion variable. The former corresponds to an impulse projected in the direction of movement; the latter corresponds to a kinetic energy projected in the direction of movement. If one correspondingly predefines the speed of the robot, at which for example it travels a geometrically predefined path, it can travel the path as quickly as possible, wherein its hazard potential, described by the projected impulse or the projected kinetic energy, remains below a predefined threshold.
BRIEF DESCRIPTION OF THE FIGURES
Additional advantages and features arise from the subsidiary claims and the exemplary embodiments. To this end, the figures, partially in schematic form, show the following:
FIG. 1 : shows a task-redundant robot in different poses, and
FIG. 2 : shows the course of an inventive method.
DETAILED DESCRIPTION
In an exemplary embodiment simplified for illustrative purposes, FIG. 1 shows a three-joint robot 1 with a heavy link arm 1 . 1 supported on a fixed base, a distinctly lighter arm 1 . 2 flexibly mounted to it and a light hand 1 . 3 flexibly supported on its end opposite the link armwith the TCP. All three rotary joints have parallel axes of rotation that are vertically upright on the drawing plane of FIG. 1 .
If the task of a robot 1 consists in traveling a path B on the drawing plane with its TCP without consideration of its orientation, the robot is redundant with its three degrees of freedom q(q 1 , q 2 , q 3 ) T with respect to the predefined position z=x=(x y) T : one recognizes that different, redundant poses exist to the same Cartesian TCP position (x, y) on path B on the drawing plane of FIG. 1 or the workspace of the robot, said different, redundant positions of which FIG. 1 shows three.
If one calculates the effective mass m u (Λ v (q)) for each of these poses according to Eq (2) with respect to the tangent unit vector u to path b in the point (, y), the lowest effective mass results for the pose represented in solid lines, since here the projection of the mass of the massive link arm 1 . 1 disappears. Accordingly, in the case of planning a path for traveling path B with the TCP the redundancy is resolved as a result of the fact that for each sampling point the pose with the lowest effective mass is selected and predefined as the target pose. This can, as explained above, take place by determining the inertia variables m u (Λ v (q i,j )) for different redundant joint angle sets q i , which each yield the same TCP sampling position (x, y) j , and the selection of the joint angle combination with the lowest effective mass. Similarly, it is possible to determine in advance and save the pose q* a,b,c, with the minimum effective mass for equidistant spatial points (x a , y b ) and directions u c . In the planning of path B or likewise also with a manual online control of the robot 1 a position can then be automatically varied in the direction of the closest of these saved, hazard optimal poses while retaining the TCP position and considering the predefined direction of movement. Instead of this, the effective mass, in analytical or numerical form equally, can also be considered as a quality criterion in the planning of the path.
FIG. 2 illustrates this method in schematic form: in a first step S 1 sampling points (x, y) 1 , (x, y) 2 , . . . are predefined for the TCP in order to travel path B with said TCP.
Then, in step S 2 a predefined direction of movement u 1 is first determined for each of these sampling points (x, y) as a unit tangent vector to the path.
Then, in an optimization the pose q* i is determined, which meets the second-order condition (“NB”): (x,y)(q* i )=(x, y) i , i.e. in which pose the TCP occupies the predefined sampling point, and in the event that the effective mass m u (Λ v (q* i )) according to Eq (2) is minimal, i.e. less than the effective mass m u (Λ v (q i )) or at least one other redundant pose, for which the following applies: (x, y)(q i )=(x, y) i .
Finally, in a step S 3 the driving speed {dot over (q)} i of the robot is defined such that a function, in particular the product of the effective mass and the Cartesian TCP speed ({dot over (x)},{dot over (y)}) i =ψ({dot over (q)} i ) remains below a threshold. As becomes clear from this, the speed which is predefined (here the joint angle speed {dot over (q)} i ) and the speed which is used for determining the inertia variable do not have to be identical, however this can be the case if for example the TCP speed is predefined.
REFERENCE LIST
1 Robot
1 . 1 Link arm (light)
1 . 2 Arm (light)
1 . 3 Hand
B Path
TCP Tool Center Point (reference point) | According to a method according to the invention for controlling a robot, in particular a human-collaborating robot, a robot- or task-specific redundancy of the robot is resolved, wherein, in order to resolve the redundancy, a pose-dependent inertia variable of the robot is minimized. | 1 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims priority from U.S. Provisional Patent Application Ser. No. 60/272,709 filed on Mar. 1, 2001, the contents of which are fully incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention is related generally to the field of interpretation of measurements made by well logging instruments for the purpose of determining the properties of earth formations. More specifically, the invention is related to a method for inversion of measurements made by multi-component induction or propagation sensors.
[0004] 2. Background of the Art
[0005] Electromagnetic induction and wave propagation logging tools are commonly used for determination of electrical properties of formations surrounding a borehole. These logging tools give measurements of apparent resistivity (or conductivity) of the formation that when properly interpreted are diagnostic of the petrophysical properties of the formation and the fluids therein.
[0006] The physical principles of electromagnetic induction resistivity well logging are described, for example, in, H. G. Doll, Introduction to Induction Logging and Application to Logging of Wells Drilled with Oil Based Mud, Journal of Petroleum Technology, vol. 1, p. 148, Society of Petroleum Engineers, Richardson Tex. (1949). Many improvements and modifications to electromagnetic induction resistivity instruments have been devised since publication of the Doll reference, supra. Examples of such modifications and improvements can be found, for example, in U.S. Pat. No. 4,837,517; U.S. Pat. No. 5,157,605 issued to Chandler et al, and U.S. Pat. No. 5,452,761 issued to Beard et al.
[0007] A limitation to the electromagnetic induction resistivity well logging instruments known in the art is that they typically include transmitter coils and receiver coils wound such that the magnetic moments of these coils are substantially parallel only to the axis of the instrument. Eddy currents are induced in the earth formations from the magnetic field generated by the transmitter coil, and in the induction instruments known in the art these eddy currents tend to flow in ground loops which are substantially perpendicular to the axis of the instrument. Voltages are then induced in the receiver coils related to the magnitude of the eddy currents. Certain earth formations, however, consist of thin layers of electrically conductive materials interleaved with thin layers of substantially non-conductive material. The response of the typical electromagnetic induction resistivity well logging instrument will be largely dependent on the conductivity of the conductive layers when the layers are substantially parallel to the flow path of the eddy currents. The substantially non-conductive layers will contribute only a small amount to the overall response of the instrument and therefore their presence will typically be masked by the presence of the conductive layers. The non-conductive layers, however, are the ones which are typically hydrocarbon-bearing and are of the most interest to the instrument user. Some earth formations which might be of commercial interest therefore may be overlooked by interpreting a well log made using the electromagnetic induction resistivity well logging instruments known in the art.
[0008] Baker Atlas and Shell International E&P jointly developed a new multicomponent induction logging tool, 3DEX to measure the electrical anisotropy of these sequences. This logging tool and its use is described in U.S. Pat. No. 6,147,496 to Strack et al. The instrument comprises three mutually orthogonal transmitter-receiver configurations that provide all necessary data to compute horizontal and vertical resistivities of the formation. These resistivities may then be used in an integrated petrophysical analysis to provide an improved estimate of the laminar sand resistivity and corresponding net oil-in-place.
[0009] U.S. Pat. No. 5,999,883 issued to Gupta et al, (the “Gupta patent”), the contents of which are fully incorporated here by reference, discloses a method for determination of the horizontal and vertical conductivity of anisotropic earth formations. Electromagnetic induction signals induced by induction transmitters oriented along three mutually orthogonal axes are measured. One of the mutually orthogonal axes is substantially parallel to a logging instrument axis. The electromagnetic induction signals are measured using first receivers each having a magnetic moment parallel to one of the orthogonal axes and using second receivers each having a magnetic moment perpendicular to a one of the orthogonal axes which is also perpendicular to the instrument axis. A relative angle of rotation of the perpendicular one of the orthogonal axes is calculated from the receiver signals measured perpendicular to the instrument axis. An intermediate Measurement tensor is calculated by rotating magnitudes of the receiver signals through a negative of the angle of rotation. A relative angle of inclination of one of the orthogonal axes, which is parallel to the axis of the instrument is calculated, from the rotated magnitudes, with respect to a direction of the vertical conductivity. The rotated magnitudes are rotated through a negative of the angle of inclination. Horizontal conductivity is calculated from the magnitudes of the receiver signals after the second step of rotation. An anisotropy parameter is calculated from the receiver signal magnitudes after the second step of rotation. Vertical conductivity is calculated from the horizontal conductivity and the anisotropy parameter.
[0010] However, the new horizontal magnetic field responses, H xx and H xx , that are sensitive to the vertical resistivity of the formation can suffer from strong borehole and near-zone effects. These effects increase with borehole size, borehole fluid conductivity, and invasion depth. Co-pending U.S. patent application Ser. No. 09/676,097 by Kriegshäuser et al. describes a method for applying shoulder bed corrections to this data. However, in large borehole sizes and conductive mud systems, these corrections cannot completely eliminate the near-zone effects.
[0011] However, a rigorous 2-D inversion is too time-intensive and prohibitive for typical logging applications, because the 2-D forward model response is time consuming and also because inversion schemes typically require the determination of a Jacobian matrix defining the sensitivity of each of the measurements to every one of the parameters in the model.
[0012] Tabarovsky and Rabinovich (U.S. Pat. No. 5,703,773) teach a computationally fast method for 2-D inversion of induction logging data. The method includes skin effect correcting the responses of the receivers by extrapolating the receiver responses to zero frequency. A model is generated of the media surrounding said instrument. Conductivities of elements in the model are then adjusted so that a measure of misfit between the skin-effect corrected receiver responses and simulated receiver responses based on the model is minimized. The geometry of the model is then adjusted so that the measure of misfit between the skin-effect corrected receiver responses and the simulated receiver responses based on the model is further minimized. In a preferred embodiment of the invention, the step of adjusting the geometry includes minimizing the measure of misfit between the simulated responses and the receiver responses from selected ones of the receivers closely spaced to the transmitter. Numbers of and positions of radial boundaries are then determined by minimizing the measure of misfit for all the receiver responses. However, Tabarovsky does not address the problem of inversion of multi-component data.
[0013] There is a need for a method of inversion of multicomponent induction logging data that gives reasonably accurate results without using an inordinate amount of computer time. The present invention satisfies this need.
SUMMARY OF THE INVENTION
[0014] An electromagnetic logging tool having a plurality of transmitters and receivers (3DEX) is used to obtain multicomponent measurements indicative of horizontal and vertical resistivities of subsurface formations. A model for the horizontal resistivity, length of the invasion zone and resistivity of the invasion zone may be obtained from High Definition Induction Logging (HDIL) tools. Such an induction logging tool comprises transmitter and receiver coils with axes parallel to the tool axis: measurements are made at multiple frequencies and/or with multiple transmitter-receiver spacings. An example of such a tool is given in U.S. Pat. No. 5,452,761 to Beard et al. An initial model is defined that includes the obtained model and vertical resistivities for the formations. In one embodiment of the invention, the vertical resistivities for the initial model are set equal to the horizontal resistivities. In alternate embodiment of the invention, the horizontal and vertical resistivities may be related by a predefined anisotropy factor. A 2-D forward response modeling is carried out and a difference between the model output and the actual measurements made with the 3DEX is determined. If the difference is small, the model is acceptable. Otherwise, the model is iteratively updated with only a subset of the model parameters being changed, so as to reduce the difference. The updating uses only the sensitivity of a subset of the measurements to the subset of the model parameters being changed.
[0015] In a preferred embodiment of the invention, the subset of the model parameters being changed includes the layer horizontal and vertical resistivities, while the layer thicknesses, length of the invasion zone and resistivity of the invasion zone are kept fixed.
[0016] In a preferred embodiment of the invention, the subset of measurements for which the sensitivity is used includes the H == component and at least one of (i) the H xx component, (ii) the H yy component, and, (iii) an average of the H xx and H yy components.
BRIEF DESCRIPTION OF THE FIGURES
[0017] The present invention is best understood with reference to the following figures in which like numbers refer to like components
[0018] [0018]FIG. 1 (Prior Art) shows an induction instrument disposed in a wellbore penetrating earth formations.
[0019] [0019]FIG. 2 (Prior Art) shows the arrangement of transmitter and receiver coils in a preferred embodiment of the present invention marketed under the name 3DExplorer™
[0020] [0020]FIG. 3 is a schematic illustration of the model used in the present invention
[0021] [0021]FIG. 4 shows a generic data flow of the inversion scheme employed in the present invention
[0022] [0022]FIG. 5 shows a comparison of back transformed singular values for a 1-D and 2-D formation model.
[0023] [0023]FIG. 6 shows a comparison of inversion results using a 1-D inversion and the P2D inversion method of the present invention with a model.
DETAILED DESCRIPTION OF THE INVENTION
[0024] Referring now to FIG. 1, an electromagnetic induction well logging instrument 10 is shown disposed in a wellbore 2 drilled through earth formations. The earth formations are shown generally at 4 . The instrument 10 can be lowered into and withdrawn from the wellbore 2 by means of an armored electrical cable 6 or similar conveyance known in the art. The instrument 10 can be assembled from three subsections: an auxiliary electronics unit 14 disposed at one end of the instrument 10 ; a coil mandrel unit 8 attached to the auxiliary electronics unit 14 ; and a receiver/signal processing/telemetry electronics unit 12 attached to the other end of the coil mandrel unit 8 , this unit 12 typically being attached to the cable 6 .
[0025] The coil mandrel unit 8 includes induction transmitter and receiver coils, as will be further explained, for inducing electromagnetic fields in the earth formations 4 and for receiving voltage signals induced by eddy currents flowing in the earth formations 4 as a result of the electromagnetic fields induced therein.
[0026] The auxiliary electronics unit 14 can include a signal generator and power amplifiers (not shown) to cause alternating currents of selected frequencies to flow through transmitter coils in the coil mandrel unit 8 .
[0027] The receiver/signal processing/telemetry electronics unit 12 can include receiver circuits (not shown) for detecting voltages induced in receiver coils in the coil mandrel unit 8 , and circuits for processing these received voltages (not shown) into signals representative of the conductivities of various layers, shown as 4 A through 4 F of the earth formations 4 . As a matter of convenience the receiver/signal processing/telemetry electronics unit 12 can include signal telemetry to transmit the conductivity-related signals to the earth's surface along the cable 6 for further processing, or alternatively can store the conductivity related signals in an appropriate recording device (not shown) for processing after the instrument 10 is withdrawn from the wellbore 2 .
[0028] Referring to FIG. 2, the configuration of transmitter and receiver coils in a preferred embodiment of the 3DExplorer™ induction logging instrument of Baker Hughes is shown. Three orthogonal transmitters 101 , 103 and 105 that are referred to as the T x , T z , and T y transmitters are shown (the z-axis is the longitudinal axis of the tool). Corresponding to the transmitters 101 , 103 and 105 are associated receivers 107 , 109 and 111 , referred to as the R x , R z , and R y receivers, for measuring the corresponding magnetic fields. In a preferred mode of operation of the tool, the H xx , H yy , H zz , H xy , and H xz components are measured, though other components may also be used.
[0029] [0029]FIG. 3 is a schematic illustration of the model used in the present invention. The subsurface of the earth is characterized by a plurality of layers 201 a , 201 b , . . . 201 i . The layers have thicknesses denoted by h 2 , h 3 . . . h i-j . The horizontal and vertical resistivities in the layers are denoted by R h1 , R h2 , . . . R h1 and R v1 , and R v2 , . . . R v1 respectively. Note that the top and bottom layers are semi-infinite in the model. The borehole is indicated by 202 and associated with each of the layers are invaded zones in the vicinity of the borehole wherein borehole fluid has invaded the formation and altered its properties so that the electrical properties are not the same as in the uninvaded portion of the formation. The invaded zones have lengths L x01 , L x02 , . . . L x01 extending away from the borehole. The resistivities in the invaded zones are altered to values R x01 , R x02 , . . . R x01 . In the embodiment of the invention discussed here, the invaded zones are assumed to be isotropic while an alternate embodiment of the invention includes invaded zones that are anisotropic, i.e., they have different horizontal and vertical resistivities. The assumption of an isotropic invasion zone is reasonable because in the case that the borehole fluid is conductive and invades a laminated sand/shale layer, then the pore fluid of the sand laminae is filled with conductive borehole mud fluid. Hence, the sand laminae become as conductive as the shale laminae, making this invaded zone isotropic. If the borehole fluid is resistive and invades the sand/shale layer, then the resistive pore fluid of the sand laminae is replaced by resistive borehole fluid. Hence, there is no significant resistivity contrast between the invasion zone and the anisotropic formation layer.
[0030] The observed data D may be defined as a function of the model parameters m as
[0031] D=f(m)
[0032] or, in matrix form,
[ d 1 d 2 ⋮ d l - 1 d l ] = [ f 1 ( m ) f 2 ( m ) ⋮ f l - 1 ( m ) f l ( m ) ]
[0033] is the vector of observations
[0034] where
[ m]=[m 1 m 2 m 3 m 4 m 5 . . . m 1-4 m 1-3 m 1-2 m 1-1 m 1 ] T =[R x01 L x01 R h1 R vl R x02 L x02 R h2 R v2 h 2 . . . h k-1 R x0k L x0k R hk R vk ] (1)
[0035] is a model vector comprising layer thicknesses, horizontal and vertical resistivities of the layers, length of the invasion zones in each of the layers and resistivity of the invasion zone in each of the layers. There are k layers in all, so that for the preferred embodiment of the invention where the invaded zone is characterized by a length of the invaded zone and a single resistivity, m is a vector of length 5 k-2 For a full 2-D inversion, the data vector could comprise all the components of measurements made with the 3DEX SM tool. In a preferred embodiment of the present invention, the H z,900 component and at least one of (i) the H xx component, (ii) the H yy component, and, (iii) an average of the H xx and H yy components are used. As would be known to those versed in the art, in a borehole drilled perpendicular to bedding, for example a vertical wellbore and horizontal formation layering, all cross-components are zero.
[0036] The pseudo 2-D inversion scheme uses a full forward solution of the 2-D formation model (Tamarchenko and Tabarovsky, 1994) to compare the synthetic responses with the measured data. The method disclosed therein is a fast hybrid numerical technique that combines integral equations and finite difference methods to simulate the electromagnetic field of an arbitrary source. FIG. 4 shows a generic data flow of the inversion scheme employed. An initial estimate of a 2-D model is defined 311 . This may be done using prior art methods: for example, the model of layer thicknesses and horizontal resistivity may be obtained by analysis of conventional High Definition Induction Logs (HDIL) obtained from prior art devices comprising a coaxial transmitter and a plurality of coaxial receivers at different spacings from the transmitter. The parameters of the invasion zone may similarly be obtained from HDIL data.
[0037] In the initial model, the vertical resistivity may be set equal to the horizontal resistivity in each layer. Alternatively, if the lithology of the individual layers is known (from other logs), an assumption may be made relating the anisotropy ratio of each layer (the ratio of vertical to horizontal resistivity) to the lithology. The inversion scheme then generates a 2-D forward solution to the model 313 using, for example, the Tamarchenko and Tabarovsky method. The output of the model 313 is compared with actual field measurements made by the 3DEX tool to determine if the model is acceptable 315 . If the model is acceptable, then the model may be further analyzed to provide petrophysical information 325 about the subsurface formations using known methods. If the model is not acceptable, a sensitivity matrix is determined that relates the model output to the model parameters 317 and the model is then updated 319 . The formation parameters are updated using a Marquardt-Levenberg method.
[0038] In conventional 2-D inversion, the sensitivity matrix would be determined for the entire set of observations using the entire 2-D model vector as defined above with reference to FIG. 3. This is would be done by iteratively updating m to minimize
O d =||D obs −f ( m )|| 2 (2)
[0039] where D obs are the observations and O d is a data objective function.
[0040] In FIG. 4, the full 2-D inversion would involve the minimization of eq. (2), using the full model vector m from 321 , and determining the full sensitivity matrix of O d to all the parameters in the model. This requires determination and inversion of a Jacobian matrix of sensitivities
[ ∂ d i ∂ m j ] ,
[0041] which is a matrix comprising l rows and 5 k-2 columns. In the present invention, a partial Jacobian matrix of sensitivities is used with respect to a subset m′ of model parameters.
[0042] The subset m′ of the model m comprises only the formation parameters, i.e., the layer thicknesses and resistivities, and the remaining components of the model m are assumed to be known. The invasion zone parameters, Rxo and Lxo, can for example, be derived from HDIL data or any other a priori information. However, the inversion process does not alter these parameters of the invasion zone. In other words, the iterative procedure only updates the model m′. Note, however, that the forward model solution 313 is still a full 2-D model including the invasion zone effects.
[0043] As a further approximation, the sensitivity matrix is determined for only a subset of the measurements 323 using only the H and at least one of (i) the H xx component, (ii) the H yy component, and, (iii) the average of the Hxx and Hyy components of the data. The sensitivity matrix, however, is determined for an objective function defined for a layered 1-D model of a horizontally layered formation.
O′=||{circumflex over (D)} obs −{circumflex over (f)} ( m ′)|| 2 (3)
[0044] By using this approximation of the sensitivity matrix, computations are greatly speeded up.
EXAMPLE
[0045] Next, an illustrative example of the use of the pseudo 2-D inversion scheme on a simple but yet realistic and typical 2-D model is shown. The formation parameters of the layered anisotropic background model are shown in Table 1. The borehole diameter is 12.25 inches, and the borehole mud resistivity is 0.1 Ohm-m. The synthetic example shown is typical for well logging applications, when seawater is used as drilling fluid.
TABLE 1 RESISTIVITY MODEL PARAMETERS Layer boundaries R h (Ω-m) R v (Ω-m) <0 0.8 1.2 36893 1.1 5 36955 1.5 7.9 37048 10 12 37080 1 1.3 37147 15 17 14-16 1 1.3 16-20 12 15 20-22 2.4 10.7 22-24 1 4.3 >24 0.9 0.9
[0046] The parameter resolution can be studied qualitatively with ‘back-transformed singular values’ (BTSV) (Jupp and Vozoff, 1977; Hördt, 1992). To define the BTSV, we begin with the singular value decomposition of the Jacobian matrix J, J=USV T , where U is the orthonormal matrix of data eigenvectors, V is the orthonormal parameter eigenvector matrix and S is the diagonal matrix containing the singular values of J T J (e.g., Jupp and Vozoff, 1974).
[0047] Now, we introduce the diagonal matrix K, composed of the normalized singular values (k j =s j /s(1)j=1,2 . . . m) as diagonal. S(1) is the largest singular value; m is the number of parameters. The norm of each column of the matrix VK is called the back-transformed singular value (BTSV), and is considered to be a measure of the importance of the contribution of parameter p 1 to reduce the data misfit in the inverse process. BTSV varies between zero and one, where the value is directly proportional to the importance of the parameter.
[0048] [0048]FIG. 5 shows the corresponding BTSV for both the 1-D and 2-D formation models. The bar chart clearly shows that the BTSV are almost identical for the 1-D and the 2-D models. This similarity indicates that a 1-D Jacobian can be used in the pseudo 2-D inversion process and that the formation parameter resolution should be almost identical compared to the full 2-D inversion.
[0049] These synthetic responses are then inverted using a 1-D inversion scheme and the results compared with the final iterate of the pseudo 2-D inversion scheme (FIG. 6). In the inverse process we only inverted for horizontal and vertical resistivities of the formation layers. The 1-D inversion scheme assumes no borehole and invasion zones in the synthetic formation model. Layer boundaries and borehole parameters are known and fixed during inversion. This assumption is usually valid in logging applications. FIG. 6 shows a comparison of the true formation resistivity parameters, the recovered model parameters using a 1-D inversion scheme, and the pseudo 2-D final iterates (P2D).
[0050] The horizontal resistivity values for the 1-D inversion and the P2D inversion are substantially the same as the true value 401 . The vertical resistivity obtained by the P2D is substantially identical to the true value 411 but the 1-D inversion 413 is clearly erroneous at certain depths, so that the determined resistivity ratio from the P2D is correct 421 while the determined resistivity ratio from the 1-D inversion 423 deviates from the correct value.
[0051] For this simple model, the computation time for convergence of the P2D method on a SUN Ultra 5 workstation is comparable to that of 1-D inversion for the horizontal resistivity while the 2-D inversion took approximately 5 times as long. For the vertical resistivity, the P2D method took about 12 times as long as the 1-D inversion while the 2-D inversion took about 7 times as long as the P2D inversion. There is thus a significant saving in computation as a result of using the method of the present invention over a full 2-D inversion with little loss in accuracy.
[0052] The present invention has been discussed above with respect to measurements made by a transverse induction logging tool conveyed on a wireline. This is not intended to be a limitation and the method is equally applicable to measurements made using a comparable tool conveyed on a measurement-while-drilling (MWD) assembly or on coiled tubing.
[0053] While the foregoing disclosure is directed to the preferred embodiments of the invention, various modifications will be apparent to those skilled in the art. It is intended that all variations within the scope and spirit of the appended claims be embraced by the foregoing disclosure. | A fast, efficient and accurate pseudo 2-D inversion scheme for resistivity determination of an anisotropic formation uses data from a tool (3DEX) comprising three transmitters and three corresponding receivers sampling the formation in a plurality of spatial directions. An initial model of the formation including invasion zones is obtained using a conventional multifrequency and/or multispacing logging tool. A pseudo 2-D inversion scheme combines an accurate full 2-D forward solution of the synthetic responses of the earth model with a 1-D approximation of the sensitivity matrix of the horizontally layered anisotropic background model. The timesaving compared to a regular 2-D inversion scheme can be tremendous. The applicability of this scheme is important in cases when borehole and near-zone effects do not allow an interpretation based on 1-D inversion. A comparison of the pseudo 2-D inversion scheme versus a full 2-D inversion using a realistic synthetic example shows that the pseudo 2-D inversion scheme performs as well as the full 2-D inversion, but in a much shorter time. | 6 |
TECHNICAL FIELD
[0001] The present invention relates to an apparatus and method for mounting a semiconductor light emitting element on a mounting board.
BACKGROUND ART
[0002] In recent years, semiconductor light emitting elements have been reduced in thickness and rigidity with increasing luminance and efficiency. Further, flip-chip mounting has been adopted as a technique for mounting bare chips of semiconductor light emitting elements on mounting boards. The flip-chip mounting is a technique for forming a metal electrode on the electrode portion of a semiconductor light emitting element to electrically join the metal electrode on the semiconductor light emitting element to a metal electrode on a mounting board.
[0003] The process of flip-chip mounting is complicated, so that the joining surface cannot be directly observed. Thus, Patent Literature 1 proposes a technique for bringing a probe needle into direct contact with a semiconductor light emitting element before flip-chip mounting to evaluate the optical properties and electrical properties of the semiconductor light emitting element.
[0004] Further, Patent Literature 2 proposes a technique for performing evaluations on a semiconductor element and a mounting board after flip-chip mounting using X-ray equipment or an infrared microscope. The inspection device is configured as shown in FIG. 10 .
[0005] In FIG. 10 , X-rays irradiated from an X-ray generator 100 pass through a flip chip 103 and a circuit board 102 , and an X-ray sensor 104 converts the rays to light with the sensor surface to obtain images. The flip chip 103 is flip-chip joined onto the circuit board 102 . For the flip-chip joining portion, a heavy metal material such as lead and gold having high X-ray absorption is used. Thus, the flip-chip joining portion is darker than the surrounding in an X-ray image, so that the position of the joining portion can be easily specified. A position level with the underside of the flip chip 103 corresponding to the upper part of the joining portion is measured by a laser focus displacement meter 105 . The laser focus displacement meter 105 can measure the position from the side via a mirror 106 allowing the passage of X-rays without affecting the X-ray photography.
[0006] Patent Literature 3 describes a die bonding method in which, in the assembly of an optical head, a light emitting element is electrified to correct a displacement of the light emitting element.
[0007] Patent Literature 4 describes a technique for retaining a light emitting element by suction before mounting and electrifying the retained light emitting element to measure the luminance and select the light emitting element.
[0008] Patent Literature 5 describes a technique for mounting a semiconductor element suctioned and retained by a bonding tool on a printed circuit board while detecting the pressing force with the bonding tool.
CITATION LIST
Patent Literatures
[0000]
Patent Literature 1: Japanese Patent Application Laid-Open Publication No. 2005-158932
Patent Literature 2: Japanese Patent Application Laid-Open Publication No. 11-183406
Patent Literature 3: Japanese Patent Application Laid-Open Publication No. 6-45652
Patent Literature 4: Japanese Patent Application Laid-Open Publication No. 9-92699
Patent Literature 5: Japanese Patent Application Laid-Open Publication No. 7-161770
SUMMARY OF INVENTION
Technical Problem
[0014] However, in the technique of Patent Literature 1, only the properties of the semiconductor light emitting element before mounting can be secured.
[0015] Further, in the technique of Patent Literature 2, only the final joining reliability of the semiconductor light emitting element after mounting can be secured. In other words, the technique of Patent Literature 2 is not designed for securing optical properties and requires the replacement of a semiconductor light emitting element having defective optical properties. Thus, large amounts of losses may be incurred.
[0016] Further, since a typical mounting technique is implemented by open-loop control, joining energy may be applied to a semiconductor light emitting element although joining has been already completed. Moreover, the mounting step of the semiconductor light emitting element may be completed in the state of insufficient joining. As a result, cracks in the semiconductor light emitting element or defects due to damage on a light emitting layer in the semiconductor light emitting element may occur.
[0017] An object of the present invention is to provide a technique for mounting a semiconductor light emitting element on a mounting board with higher reliability.
Solution to Problem
[0018] A method for mounting a semiconductor light emitting element according to the present invention includes: supplying power to the electrode portion of a mounting board to allow a semiconductor light emitting element to emit light while the electrode portion of the semiconductor light emitting element and the electrode portion of the mounting board are joined to each other; and detecting the optical properties of the semiconductor light emitting element while the element emits light and controlling the joining of the electrode portion of the semiconductor light emitting element and the electrode portion of the mounting board based on the detected optical properties.
[0019] Further, a method for mounting a semiconductor light emitting element according to the present invention includes: supplying power to the electrode portion of a mounting board to allow a semiconductor light emitting element to emit light while the electrode portion of the semiconductor light emitting element and the electrode portion of the mounting board are joined to each other; and detecting the optical properties of the semiconductor light emitting element while the element emits light and controlling the joining of the electrode portion of the semiconductor light emitting element and the electrode portion of the mounting board based on the detected optical properties, wherein the controlling of the joining comprises: controlling the joining with pressing; and then controlling the joining with ultrasonic waves.
[0020] A method for mounting a semiconductor light emitting element according to the present invention includes: supplying power to the electrode portion of a mounting board to allow a semiconductor light emitting element to emit light while the electrode portion of the semiconductor light emitting element and the electrode portion of the mounting board are joined to each other; and detecting the optical properties of the semiconductor light emitting element while the element emits light, and completing the joining when detecting that the chromaticity of the optical properties falls within a prescribed chromaticity range and the luminance of the optical properties reaches at least prescribed luminance.
[0021] An apparatus for mounting a semiconductor light emitting element according to the present invention includes: a pressing mechanism including a suction hole for suctioning a semiconductor light emitting element, for pressing the suctioned semiconductor light emitting element; a stage holding a mounting board; a power supply unit for supplying power to the electrode portion of the mounting board held by the stage; an optical property detector for detecting the optical properties of light from the suction hole; and a processing control unit for controlling the pressing of the pressing mechanism based on a value detected by the optical property detector.
[0022] Further, an apparatus for mounting a semiconductor light emitting element according to the present invention includes: a pressing mechanism including a suction hole for suctioning a semiconductor light emitting element, for pressing the suctioned semiconductor light emitting element; an ultrasonic wave applying mechanism for applying ultrasonic waves to the semiconductor light emitting element; a stage holding a mounting board; a power supply unit for supplying power to the electrode portion of the mounting board held by the stage; an optical property detector for detecting the optical properties of light from the suction hole; and a processing control unit for controlling the pressing of the pressing mechanism or the ultrasonic waves applied by the ultrasonic wave applying mechanism based on a value detected by the optical property detector.
[0023] Moreover, an apparatus for mounting a semiconductor light emitting element according to the present invention includes: a pressing mechanism including a suction hole for suctioning a semiconductor light emitting element and an optical waveguide disposed along the inner circumference of the suction hole, for pressing the suctioned semiconductor light emitting element; a stage holding a mounting board; a power supply unit for supplying power to the electrode portion of the mounting board held by the stage; a first optical property detector for detecting the optical properties of light from the suction hole; a second optical property detector for detecting the optical properties of light from the optical waveguide; and a processing control unit for controlling the pressing of the pressing mechanism based on values detected by the first optical property detector and the second optical property detector.
Advantageous Effects of Invention
[0024] According to the present invention, the electrode of a semiconductor light emitting element and the electrode portion of a mounting board can be joined to each other stably and satisfactorily, so that the semiconductor light emitting element can be mounted on the mounting board with higher reliability.
BRIEF DESCRIPTION OF DRAWINGS
[0025] FIG. 1 is a configuration diagram showing an apparatus for mounting a semiconductor light emitting element according to a first embodiment of the present invention.
[0026] FIG. 2 is a cross-sectional view showing the main part of a head and the periphery thereof according to the first embodiment.
[0027] FIG. 3( a ) shows a first step according to the first embodiment. FIG. 3( b ) shows a second step according to the first embodiment. FIG. 3( c ) shows a third step according to the first embodiment. FIG. 3( d ) shows a fourth embodiment according to the first embodiment. FIG. 3( e ) shows a fifth embodiment according to the first embodiment.
[0028] FIG. 4 is a flowchart of processing control according to the first embodiment.
[0029] FIG. 5 is a relationship diagram of a detected optical property value and a mounting condition.
[0030] FIG. 6 is a chart showing an example of controlling a pressing force according to the first embodiment.
[0031] FIG. 7 is a configuration diagram showing the main part of an apparatus for mounting a semiconductor light emitting element according to a second embodiment of the present invention.
[0032] FIG. 8 is a configuration diagram showing an apparatus for mounting a semiconductor light emitting element according to a third embodiment of the present invention.
[0033] FIG. 9 is a detected signal waveform diagram of the main part of the apparatus for mounting a semiconductor light emitting element according to the third embodiment.
[0034] FIG. 10 is a configuration diagram showing a mounting apparatus according to the related art.
DESCRIPTION OF EMBODIMENTS
[0035] Embodiments of the present invention will be described below in accordance with the accompanying drawings.
First Embodiment
[0036] FIG. 1 is a configuration diagram showing an apparatus for mounting a semiconductor light emitting element according to a first embodiment of the present invention. FIG. 2 is an enlarged cross-sectional view showing the main part of a head and the periphery thereof according to the first embodiment. FIGS. 3( a ) to 3 ( e ) show first to fifth steps according to the first embodiment. FIG. 2 shows the cross sections of a pressing mechanism 9 and a moving mechanism 10 only in a head 4 . FIG. 3( a ) shows a mounting board 3 , a semiconductor light emitting element 2 and the peripheral parts thereof holding the mounting board and semiconductor light emitting element from above and below. The mounting board, the semiconductor light emitting element, and the peripheral parts are vertically illustrated at intervals.
[0037] A mounting apparatus 1 of FIG. 1 includes the head 4 , a stage 5 , a power feeder 6 , an optical property measuring part 7 , and a processing control unit 8 . The head 4 retains the semiconductor light emitting element 2 with bump electrodes 26 as an electrode portion, as shown in FIG. 3( b ). On the stage 5 , the mounting board 3 is placed on which the semiconductor light emitting element 2 is to be mounted. The power feeder 6 supplies power to the semiconductor light emitting element 2 while mounting. The optical property measuring part 7 measures the optical property value of the semiconductor light emitting element 2 while mounting. The processing control unit 8 controls operations of the mounting apparatus 1 .
[0038] As shown in FIG. 2 , the head 4 includes the pressing mechanism 9 and the moving mechanism 10 . The pressing mechanism 9 presses the retained semiconductor light emitting element 2 down. The moving mechanism 10 moves the pressing mechanism 9 to a predetermined mounting position of the mounting board 3 . The pressing mechanism 9 is cylindrically-shaped with a suction hole 11 formed therein. The diameter of the pressing mechanism 9 is 1.0 times to 1.5 times as large as the diagonal diameter of the semiconductor light emitting element 2 . The diameter of the suction hole 11 is not smaller than 0.05 mm and not more than 0.2 times as large as the diagonal diameter of the semiconductor light emitting element 2 . The diagonal diameter of the semiconductor light emitting element 2 is typically about 0.3 mm to 1.0 mm.
[0039] A suction passage 13 communicating with a negative-pressure source 12 is connected to the suction hole 11 . The semiconductor light emitting element 2 is retained via the suction hole 11 and the suction passage 13 by the suctioning of the negative-pressure source 12 .
[0040] As shown in FIG. 2 , an optical property detector (first optical property detector) 14 is provided at the terminal end of the suction hole 11 opening at the distal end of the pressing mechanism 9 . The optical property detector 14 detects light having entered the suction hole 11 . Further, the optical property detector 14 sends intensity information according to the wavelength unit of the detected light to a processing part 15 of the processing control unit 8 via the optical property measuring part 7 . The inner circumferential surface (surface) of the suction hole 11 is coated with a coating material 16 with a low refractive index which reflects or propagates light with high efficiency. The coating material 16 guides light having entered the suction hole 11 to the optical property detector 14 at a low attenuation rate with high efficiency. The coating material 16 enables the optical property detector 14 to detect even weak light having entered the suction hole 11 . The coating material 16 is preferably SiO 2 and MgF 2 both having a refractive index of about 1.5. Further, the inner circumferential surface (surface) of the suction hole 11 may be mirror-finished. The inner circumferential surface of the suction hole 11 (surface of optical waveguide) having been mirror-finished can easily form a reflecting surface with slightly reduced reflectivity.
[0041] The stage 5 includes a mounting board holder 17 and a moving mechanism 18 . The mounting board holder 17 holds the placed mounting board 3 by suction. The moving mechanism 18 moves the mounting board holder 17 in a horizontal plane.
[0042] The power feeder 6 includes a DC power supply 19 for supplying electric power, a probe 22 , a voltage measuring device 20 for measuring a voltage, and a probe 23 . The probe 22 contacts an electrode portion 21 on the mounting board 3 to electrically connect the DC power supply 19 and the electrode portion 21 . The probe 23 contacts another electrode portion 21 on the mounting board 3 to electrically connect the voltage measuring device 20 and the electrode portion 21 .
[0043] The optical property measuring part 7 performs processing on an output from the optical property detector 14 and sends the output to the processing part 15 of the processing control unit 8 .
[0044] The processing control unit 8 has a circuit for performing calculations and drive circuits. The processing control unit 8 controls the head 4 , the stage 5 , the power feeder 6 , and the optical property measuring part 7 . FIG. 1 shows only the processing part 15 , a press control part 24 , and a memory 25 as the constituents of the main part of the processing control unit 8 . The processing part 15 performs processing on a measured value from the optical property measuring part 7 . The press control part 24 controls the force of the pressing mechanism 9 . The memory 25 stores data and so on for determining a threshold value Φ th .
[0045] The following will describe the specific configuration of the processing control unit 8 with reference to the flowchart of FIG. 4 .
[0046] In step S 1 , as shown in FIG. 3( b ), the semiconductor light emitting element 2 is suctioned and retained by the pressing mechanism 9 of the head 4 . Further, the mounting board 3 is suctioned and retained on the mounting board holder 17 . In other words, the semiconductor light emitting element and the mounting board are loaded.
[0047] In step S 2 , as shown in FIG. 3( c ), the moving mechanisms 10 and 18 move the semiconductor light emitting element 2 and the mounting board 3 to a predetermined mounting position, and the semiconductor light emitting element 2 and the mounting board 3 are aligned.
[0048] In step S 3 , as shown in FIG. 2 , the probes 22 and 23 contact the electrode portions 21 on the mounting board 3 , and the DC power supply 19 and the voltage measuring device 20 measure an electrical property value of the mounting board 3 . The electrical property value indicates a physical quantity such as an impedance value and capacitance.
[0049] In step S 4 , based on the measurement result in step S 3 , it is determined whether or not defects such as an electrode short are caused on the mounting board 3 . When defects are detected in step S 4 (in the case of “YES” in response to the question “defect?” in step S 4 ), the process advances to step S 11 which will be described later.
[0050] When it is confirmed that there are no defects in step S 4 (in the case of “NO” in response to the question “defect?” in step S 4 ), the routine of step S 5 to step S 8 is repeated until the completion of joining is determined in step S 7 .
[0051] In step S 5 , the press control part 24 controls the pressing mechanism 9 to press the semiconductor light emitting element 2 toward the mounting board 3 .
[0052] In step S 6 , while the semiconductor light emitting element 2 continues to be pressed (during the pressing of step S 5 ), the power feeder 6 supplies electric power to the semiconductor light emitting element 2 , so that the semiconductor light emitting element 2 emits light. Further, in step S 6 , concurrently with the light emitting of the semiconductor light emitting element 2 , the optical property detector 14 measures the optical property value of the mounting board 3 . The optical property value indicates a physical quantity such as luminance and chromaticity.
[0053] In step S 7 , based on the measurement result in step S 6 , the processing part 15 determines the completion of joining.
[0054] Specifically, the processing part 15 compares the optical property value measured by the optical property measuring part 7 with the threshold value Φ th stored in the memory 25 , and determines the completion of joining when the measurement result exceeds the threshold value Φ th. The threshold value Φ th will be specifically described in accordance with FIG. 5 .
[0055] FIG. 5 shows the transition of the optical property value when the bump electrodes 26 of the semiconductor light emitting element 2 continued to be pressed to the electrode portions 21 on the mounting board 3 at a constant pressure. The time when the bump electrodes 26 of the semiconductor light emitting element 2 come into contact with the electrode portions 21 on the mounting board 3 is indicated by T 1 . It is noted from FIG. 5 that the optical property value of the light emitting portion of the semiconductor light emitting element 2 had increased for a while after T 1 , and thereafter had been kept virtually constant. The optical property value of the light emitting portion of the semiconductor light emitting element 2 had increased and thereafter had been kept virtually constant, no matter whether the joining was defective or not.
[0056] Even when the joining was nondefective (in the case of 30 in FIG. 5 ), after the bump electrodes 26 continued to be pressed at the constant pressure, redundant energy caused damage on the light emitting portion of the semiconductor light emitting element 2 , the short or open of the bump electrodes 26 , or cracks on the light emitting portion in some cases. At a point of 30 a of FIG. 5 , the light emitting portion cracked. When the joining was defective (in the cases of 31 and 32 in FIG. 5 , even when the bump electrodes 26 of the semiconductor light emitting element 2 continued to be pressed to the electrode portions 21 of the mounting board 3 at the constant pressure, the optical property value of the mounted semiconductor light emitting element 2 did not reach the threshold value Φ th .
[0057] Since the optical property value reached at least the constant value (Φ th in FIG. 5 ) in the case of nondefective mounting, the optical property value of the mounted semiconductor light emitting element 2 can be determined with reference to the threshold value Φ th , so that the joining state during mounting can be determined without destruction.
[0058] In step S 7 , when it is determined that the joining is uncompleted (in the case of “NO” in response to the question “joining completed?” in step S 7 ), the process advances to step S 8 . In step S 8 , the processing part 15 determines whether or not defects occur on the joining, the process returns to step S 5 when it is determined that there are no defects (in the case of “NO” in response to the questions “defect?” in step S 8 ), and steps S 5 to S 7 are performed.
[0059] When the completion of joining is determined in step S 7 (in the case of “YES” in response to the question “joining completed?” in step S 7 ), step S 9 is performed.
[0060] In step S 9 , the processing part 15 sends a notification signal of completion of joining to the press control part 24 . The press control part 24 having received the signal stops the pressing mechanism 9 from pressing the semiconductor light emitting element 2 .
[0061] Subsequently in step S 10 , as shown in FIG. 3( d ), in a state where the suction and retention of the mounting board 3 by the mounting board holder 17 are released, the head 4 is elevated and the mounting board 3 with the semiconductor light emitting element 2 is unloaded. The mounting board 3 is unloaded and the suction and retention of the semiconductor light emitting element 2 by the pressing mechanism 9 is released, so that the mounting of the semiconductor light emitting element 2 is completed as shown in FIG. 3( e ).
[0062] In step S 8 , for example, in the case where the optical property value of the semiconductor light emitting element 2 does not exceed the threshold value Φ th despite the pressing for a certain period of time (in the case of “YES” in response to the question “defect?” in step S 8 ), the process advances to step S 11 . At this point, in response to “YES” to the question “defect?” in step S 8 , it is determined that defects occur which include cracks or damage on the light emitting portion of the semiconductor light emitting element 2 and the short or open of the bump electrodes 26 . In step S 11 , a notification signal of defects is sent to the press control part 24 . The press control part 24 having received the notification signal in step S 11 stops the pressing mechanism 9 from pressing the semiconductor light emitting element 2 in step S 9 .
[0063] As described above, in the mounting apparatus 1 of the first embodiment, during the pressing step of joining the semiconductor light emitting element 2 to the mounting board 3 , the optical property measuring part 7 measures the optical property value of the semiconductor light emitting element 2 . Then, based on the measured optical property value, it is determined whether or not the joining of the semiconductor light emitting element 2 and the mounting board 3 is completed. This prevents the joining operation from being completed despite an inadequate optical property value, so that stable joining strength and optical properties can be obtained.
[0064] Further, the joining operation can be prevented from being excessively performed despite an adequate optical property value. Thus, the occurrence of cracks or damage on the light emitting portion of the semiconductor light emitting element 2 and defects on the bump electrodes 26 (short, open and so on) can be suppressed.
[0065] In the first embodiment, the timing of completion of pressing is controlled according to the detected optical property value. The present invention is not limited to this point. In other words, in addition to the timing of completion of pressing, any parameter of the pressing may be controlled according to the detected optical property value in real time. An example of the parameter to be controlled is the pressing force in the pressing step.
[0066] FIG. 6 shows an example of controlling the pressing force according to the detected optical property value. FIG. 6 shows the example in which the pressing force is increased while the detected optical property value is low, and the pressing force is reduced with an increase in the detected optical property value. In this case, data showing the relationship between the optical property value and the pressing force as shown in FIG. 6 is beforehand stored in the memory 25 as data for determination. Based on the data for determination, the processing part 15 may send a control signal to the press control part 24 according to the pressing force. As a matter of course, the example of controlling the pressing force in FIG. 6 is one example among many, and appropriate control may be performed according to actual mounting conditions.
[0067] In the present embodiment, the optical property detector 14 is provided in the pressing mechanism 9 to reduce the size of the apparatus. The present invention, however, is not limited to this configuration. For example, the optical property detector 14 may be provided on the exterior of the pressing mechanism 9 to guide light incident through the suction hole 11 to the optical property detector 14 by an optical fiber and so on.
Second Embodiment
[0068] FIG. 7 is a configuration diagram showing the main part of an apparatus for mounting a semiconductor light emitting element according to a second embodiment of the present invention. In the first embodiment, the suction hole 11 is an air passage, the optical property detector 14 detects light propagated through the passage, and the processing control unit 8 controls the pressing force of joining via the optical property measuring part 7 .
[0069] However, the propagation frequency characteristics of the suction hole 11 are affected by the reflection characteristics of the coating material 16 . Thus, in order that the processing control unit 8 controls the pressing force of joining by measuring luminance in a wide range of chromaticity, it is desirable that the propagation frequency characteristics of the detected light be further flattened.
[0070] In the second embodiment, a plurality of optical fibers 33 are circularly arranged along the inner circumferential surface of a suction hole 11 . The optical fiber 33 is an optical waveguide having a core material which includes a distal end positioned on the suction hole 11 on the side of a semiconductor light emitting element 2 and another end positioned on the side of an optical property detector 14 . Further, in the second embodiment, in addition to the optical property detector 14 , another optical property detector 34 is provided. Light having propagated through the core materials of the optical fibers 33 is detected by the optical property detector 34 . In this case, the optical property detector 14 detects only light propagated through an air passage surrounded by the circularly-arranged optical fibers 33 . The outer peripheral surface of the optical fiber 33 may be coated by a coating material 16 .
[0071] An output detected by the optical property detector 14 (hereinafter, will be referred to as the first detected output) and an output detected by the other optical property detector 34 (hereinafter, will be referred to as the second detected output) are inputted to a processing control unit 8 through an optical property measuring part 7 . Specifically, the optical property measuring part 7 is a spectrometer for measuring and outputting light intensity for each frequency.
[0072] The first detected output and the second detected output inputted through the optical property measuring part 7 to the processing control unit 8 are weighted in a processing part 15 such that the weighted outputs have the same ratio per unit area even when the optical property detector 14 and the other optical property detector 34 are different in incidence area. After the outputs are thus weighted such that the weighted outputs have the same ratio per unit area, the first detected output and the second detected output are added and outputted to a press control part 24 .
[0073] The weighting in the processing part 15 will be specifically described. The first detected output is denoted by A 1 , the incidence area of the optical property detector 14 is denoted by N 1 , the second detected output is denoted by A 2 , and the incidence area of the other optical property detector 34 is denoted by N 2 . In this case, the output from the processing part 15 is represented, for example, as follows:
[0000] A1·N2+A2·N1
[0000] In the second embodiment, other numeral values and calculations are the same as those in the first embodiment, and an explanation thereof is omitted.
[0074] In the second embodiment, with this configuration, the frequency properties of a detected signal inputted through the optical property measuring part 7 to the processing control unit 8 can be more flattened than in the first embodiment. Thus, it is possible to achieve a mounting condition in which variations in luminance and chromaticity are reduced.
Third Embodiment
[0075] FIGS. 8 and 9 show an apparatus for mounting a semiconductor light emitting element according to a third embodiment of the present invention.
[0076] In the following explanation, an example of a semiconductor light emitting element is backlight for illuminating a liquid crystal display panel from behind. Backlighting requires a large number of light emitting elements emitting white light to be vertically and horizontally mounted at predetermined intervals. Backlighting also requires few variations in brightness and luminescent color between the adjacent light emitting elements.
[0077] The following will discuss why variations occur in brightness and luminescent color.
[0078] Bump electrodes formed on the electrode portion of the light emitting element are pressed to electrode portions 21 of a mounting board 3 to be mounted on the mounting board 3 . Even when there are no variations in the brightness and luminescent color of the light emitting elements before pressing the bump electrodes to be mounted, variations in pressing force lead to variations in the deformed conditions of the bump electrodes 26 , resulting in variations in the contact area of the bump electrodes 26 with the electrode portions 21 .
[0079] Specifically, when the contact area of the bump electrodes 26 with the electrode portions 21 is large, heat generated from the light emitting element by electric conduction is satisfactorily conducted to the electrode portions 21 via the bump electrodes 26 . On the other hand, when the contact area of the bump electrodes 26 with the electrode portions 21 is small, heat generated from the light emitting element by electric conduction is insufficiently conducted to the electrode portions 21 via the bump electrodes 26 . Thus, when the contact area is small, the temperature of the light emitting element increases and the brightness decreases with the passage of conduction time.
[0080] Further, even when the contact area of the bump electrodes 26 with the electrode portions 21 is constant, the chromaticity of the luminescent color slightly fluctuates depending on the condition of the interfaces between the bump electrodes 26 and the electrode portions 21 .
[0081] In response, in the third embodiment, the chromaticity is brought closer to the target chromaticity, in addition to bringing the luminance closer to the target luminance. Thus, in the third embodiment, below the mounting board 3 and between a mounting board holder 17 and a moving mechanism 18 , an ultrasonic wave applying mechanism 35 is interposed. Further, a processing control unit 8 performs control as shown in FIG. 9( a ). Other configurations are the same as in the second embodiment, and an explanation thereof is omitted.
[0082] In FIG. 9( a ), the abscissa indicates time, the left ordinate indicates a load applied when a semiconductor light emitting element 2 is pressed toward the mounting board 3 by a pressing mechanism 9 controlled by a press control part 24 , and the right ordinate indicates the intensities of ultrasonic waves vibrating the semiconductor light emitting element 2 in a lateral direction parallel to the board surface of the mounting board 3 . In FIG. 9( b ), the abscissa indicates time, and the ordinate indicates the detected luminance of the semiconductor light emitting element 2 while being mounted. In FIG. 9( c ), the abscissa indicates time, and the ordinate indicates the detected chromaticity of the semiconductor light emitting element 2 while being mounted. In FIGS. 9( a ) to 9 ( c ), the time is denoted by t 0 , t 1 , and t 2 to clearly show the correspondence of timings.
[0083] As shown in FIG. 9( a ), the processing control unit 8 of the third embodiment presses the semiconductor light emitting element 2 toward the mounting board 3 by the pressing mechanism 9 until the detected luminance reaches the target luminance value Ys of FIG. 9( b ).
[0084] After detecting that the detected luminance reaches the target luminance value Ys of FIG. 9( b ), the processing control unit 8 maintains the load of the pressing mechanism 9 at this point as shown in FIG. 9( a ). Further, after detecting that the detected luminance reaches the target luminance value Ys of FIG. 9( b ), the processing control unit 8 causes the ultrasonic wave applying mechanism 35 to generate ultrasonic vibrations as shown in FIG. 9( a ), thereby applying lateral vibrations to the semiconductor light emitting element 2 .
[0085] In joining under the lateral ultrasonic vibrations, there is no remarkable change in the contact area of the bump electrodes 26 with the electrodes 21 and little change in the heat dissipation properties of the semiconductor light emitting element 2 . Thus, as shown in FIG. 9( b ), the detected luminance exhibits extremely few fluctuations compared to the rate of change of load until the detected luminance reaches the target luminance value Ys. However, as shown in FIG. 9( c ), the detected chromaticity changes in one direction due to the ultrasonic lateral vibrations. The processing control unit 8 determines the completion of joining when the detected luminance reaches at least the target luminance value Ys and the detected chromaticity reaches the target chromaticity value Cs. Further, the processing control unit 8 instructs the ultrasonic wave applying mechanism 35 to turn off the ultrasonic output and the pressing mechanism 9 to take a load off.
[0086] The configuration of the third embodiment makes it possible to bring the detected luminance to at least the target luminance and bring the detected chromaticity closer to the target chromaticity. Thus, the configuration is particularly effective for the manufacturing of backlight for illuminating a liquid crystal display panel from behind.
INDUSTRIAL APPLICABILITY
[0087] The present invention is applicable to various apparatuses for manufacturing electronic equipment which require a semiconductor light emitting element to be mounted on a board. | When bump electrodes 26 of a semiconductor light emitting element 2 and electrode portions 21 of a mounting board 3 are joined to each other, power is supplied to the electrode portions 21 of the mounting board 3 to allow the semiconductor light emitting element 2 to emit light, the optical properties of the semiconductor light emitting element 2 having emitted light are detected, and the detected value of optical properties is processed to obtain the joining state of the bump electrodes 26 of the semiconductor light emitting element 2 and the electrode portions 21 of the mounting board 3 , so that the completion of joining is determined. Thus, the semiconductor light emitting element can be satisfactorily joined to the electrode portions on the mounting board via the metal electrodes formed on the semiconductor light emitting element. | 8 |
FIELD OF THE INVENTION
The present invention r elates to jewel ry, and more particularly to methods and apparatus for precisely adjusting the length of jewelry, such as necklaces, to easily accommodate the fashion desires, size, and clothing of the wearer.
BACKGROUND
For many years, people have worn necklaces at various different lengths depending upon the prevailing fashion at the time. During some years the common length has been a short choker length of approximately fifteen inches. During other years the common length has been eighteen inches or longer. The trends in length have come and gone repeatedly over the decades.
Necklaces commonly comprise a fixed length of flexible chain made from one or more precious metals, such as gold, silver and platinum, and these chains are available in a wide variety of designs. The flexible chains are also commonly adorned with a wide variety of pendants, which generally comprise one or more precious stones, such as diamonds, rubies and sapphires, mounted in settings of precious metal. Purchasers of fine jewelry currently select a pendant of a desirable style and size and have it mounted on a flexible chain having a fixed length, which is usually fifteen, eighteen, twenty-four, or thirty inches. If the popular fashion changes, for example, the pendant can in many cases later be mounted on a chain of a different length, but this generally requires the purchase of a new chain and also often requires the services of a professional jeweler to remove the pendant from the old chain and mount it on the new chain. Thus, mounting a pendant on a new chain can be inconvenient, time consuming and expensive.
In fine jewelry the most common commercially-available necklace length during the last twenty years has been approximately eighteen inches, which generally allows the looped end to hang about two to three inches below an average-sized person's collar bone. A twenty-four-inch necklace has also been fashionable from time to time, which length generally allows the looped end to hang about three inches lower than the eighteen-inch chain. A thirty-inch necklace has been another common length, but this has generally been the longest commercially-available necklace length.
People, of course, come in a wide variety of body shapes and sizes, and a necklace chain of a given length will therefore hang quite differently on different people. An eighteen-inch necklace chain, for example, which hangs at a fashionable length on an average-sized person, would not hang at the same fashionable length on a relatively larger or relatively smaller person. Particularly large people and particularly small people, including children, have therefore, in some cases, been unable to wear necklaces and other jewelry at appropriate fashionable lengths.
Moreover, the style and type of a person's clothing can interfere with the appearance of a necklace and affect the way the necklace hangs. For example, a pendant which hangs at approximately the same length as the neckline of the person's clothing can often be hidden from view by the clothing. A necklace chain that hangs at a fashionable length when worn over light clothing may not hang at the same fashionable length when worn over relatively bulky clothing.
It is therefore desirable to provide methods and apparatus which allow the length of jewelry, such as necklaces, to be precisely adjusted to quickly and conveniently accommodate the particular fashion desires, size and clothing of the wearer. Such methods and apparatus would permit the wearer to precisely adjust the length of the necklace chain so that the pendant or other ornament hangs at the most fashionable, appropriate and flattering position, regardless of the person's particular size and clothing. It is also desirable to provide methods and apparatus which allow the person to adapt a necklace to accommodate a variety of different fashionable lengths without requiring the person to purchase a new chain of a different length and have the pendent mounted on the new chain.
SUMMARY OF THE INVENTION
The present invention provides methods and apparatus for precisely adjusting the length of jewelry, such as necklaces, to easily and conveniently accommodate the particular fashion desires, size and clothing of the wearer. Since the present invention allows the necklace to be precisely adjusted to any desired length, the necklace can be custom fit to match the prevailing fashion at the time, regardless of the particular size and clothing of the wearer. Those skilled in the art will understand that the present invention is not limited to necklaces, but can also be readily applied to jewelry commonly worn elsewhere, such as around the waist, wrist and ankle.
The apparatus according to the present invention comprises a flexible member, such as a chain, which is looped upon itself to form a loop portion, a first leg terminating in a first free end and a second leg terminating in a second free end. Alternatively, the flexible member can be formed of a single, continuous length of material, which itself forms a loop and thus has no free ends. The flexible member can be a chain formed of a precious metal, such as gold, silver and platinum, or can be a length of some other flexible material, such as fabric, string, plastic or silicone.
A slidable clamping device is mounted on the flexible member so that the first leg and the second leg of the flexible member project through the slidable clamping device. The slidable clamping device, when positioned on the flexible member, securely prevents relative movement between the clamping device, the first leg and the second leg of the flexible member. The slidable clamping device, however, can be adapted to slide freely along the lengths of the first leg and the second leg of the flexible member, thereby increasing and decreasing the size of the loop portion of the flexible member. The slidable clamping device can be easily moved to any desired position along the lengths of the first and second legs of the flexible member, and, thus, the size of the loop portion of the flexible member can be precisely adjusted. Once positioned so that the desired size of the loop portion has been obtained, the slidable clamping device can be adapted to once again securely prevent relative movement between the slidable clamping device, the first leg and the second leg of the flexible member. When the necklace is worn, the slidable clamping device is generally positioned at the back of the person's neck with the loop portion of the flexible member extending around the person's neck and hanging down the chest, depending upon the size of the loop portion.
The invention also preferably comprises one or more ornaments, such as pendants, mounted on the flexible member, but this is not a necessary aspect of the invention. First and second end stops also can be attached to the first and second free ends, respectively, of the flexible member. The first and second end stops are preferably sized so that they are too large to pass through the slidable clamping device. Thus, the first and second end stops can provide added security to prevent the slidable clamping device from inadvertently sliding completely off either the first leg, the second leg or both. If one or more ornaments are mounted on the flexible member, the first and second end stops will also provide added security to prevent an ornament from inadvertently sliding completely off either the first leg or the second leg of the flexible member and becoming lost.
The method according to the present invention is a method for precisely adjusting the length of jewelry, such as a necklace, to easily and conveniently accommodate the particular fashion desires, size and clothing of the wearer. The method comprises the steps of providing a flexible member; looping the flexible member upon itself to form a loop portion, a first leg and a second leg; positioning a slidable clamping device on the flexible member so that the first leg and the second leg of the flexible member project through the slidable clamping device, adapting the slidable clamping device so that it slides freely along the lengths of the first leg and the second leg of the flexible member and thereby increases and decreases the size of the loop portion of the flexible member so that it hangs at the desired length. The method can also comprise the step of mounting a pendent of a desired style and design on the loop portion of the flexible member, but this is not a necessary aspect of the invention. The method can further comprise the step of positioning the slidable clamping device so that it hangs at the back of the neck of the wearer.
Those skilled in the art will further appreciate the features and advantages of the present invention, together with other aspects thereof, upon reading the detailed description of preferred embodiments, which follows, in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are front and rear views, respectively, showing an article of adjustable jewelry according to the present invention in place around the neck of a wearer, in which the article of adjustable jewelry is depicted as adjusted to a short length;
FIGS. 1C and 1D are front and rear views similar to FIGS. 1A and 1B, respectively, in which the article of jewelry is depicted as adjusted to a medium length;
FIGS. 1E and 1F are front and rear views similar to FIGS. 1A and 1B, respectively, in which the article of jewelry is depicted as adjusted to a long length;
FIG. 2A is a perspective view of an article of adjustable jewelry according to the present invention;
FIG. 2B is an exploded perspective view of a slidable clamping device according to the present invention;
FIG. 2C is a sectional perspective view of the assembled slidable clamping device of FIG. 2A;
FIG. 3 is a detailed view of a preferred embodiment of a slidable clamping device according to the present invention; and
FIG. 4 is a cross-sectional view through the lines 4 — 4 of FIG. 3 showing a detailed sectional view of a preferred embodiment of a slidable clamping device according to present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIGS. 1A through 1F show a combination of front and rear views of an article of adjustable jewelry 10 according to the present invention. The article of adjustable jewelry 10 comprises a flexible member 20 and a slidable clamping device 100 . Flexible member 20 can be formed of any suitable flexible material, such as metal, fabric, string, plastic or silicone. Flexible member 20 is preferably formed of a precious metal, such as gold, silver and platinum, using methods that are well known in the art. Loop portion 21 of flexible member 20 can extend around the neck of the wearer. First leg 22 and second leg 23 of flexible member 20 can extend down the back of the wearer's neck. First leg 21 terminates in a first free end to which first end stop 24 is attached by methods well known in the art, such as soldering. Second leg 23 terminates in a second free end to which second end stop 25 is attached by similar methods. First and second end stops 24 and 25 can be fashioned in a wide variety of decorative and ornamental shapes and can also comprise precious stones, such as diamonds, rubies and sapphires. Alternatively, flexible member 20 can be a single continuous length of material which itself forms a loop and which therefore would not have a first free end or a second free end. Thus, in this alternative embodiment, first end stop 24 and second end stop 25 also would not be present.
Ornament 30 , which can be a pendant comprising one or more precious stones, such as diamonds, rubies, sapphires and others, can be mounted on loop portion 21 of flexible member 20 . Ornament 30 is preferably mounted on flexible member 20 according to methods well known in the art so that ornament 30 can freely slide along the length of loop portion 21 of flexible member 20 .
As depicted in FIGS. 1A through 1F, slidable clamping device 100 can be adapted to slide freely along the length of first leg 22 and second leg 23 so that loop portion 21 of flexible member 20 can be precisely adjusted to any desired size. When slidable clamping device 100 is adjusted so that loop portion 21 is relatively small, ornament 30 , if utilized, hangs relatively higher on the front of wearer's neck, and first and second legs 22 and 23 extend relatively farther down the wearer's back. When slidable clamping device 100 is adjusted so that loop portion 21 is relatively large, ornament 30 , if utilized, hangs relatively lower on the wearer's neck or chest, and first and second legs 22 and 23 do not extend as far down the wearer's back. It will be appreciated that, since slidable clamping device 100 can be positioned at any desired location along first and second legs 22 and 23 , loop portion 21 of flexible member 20 can be adjusted to any desired size and thereby accommodate any desired fashionable length, regardless of the wearer's relative size and clothing.
FIG. 2A is a perspective view of the article of adjustable jewelry 10 according to the invention. First and second legs 22 and 23 of flexible member 20 extend through first passage 102 and second passage 103 , respectively, of slidable clamping device 100 . FIG. 3 is a more detailed view of slidable clamping device 100 .
The construction of slidable clamping device 100 is best shown in the exploded view of FIG. 2B, the sectional view of FIG. 2 C and the detailed cross-sectional view of FIG. 4 . Slidable clamping device 100 comprises an insert 110 having a first end 112 and a second end 113 , first cap 120 , second cap 130 , first biasing member 140 and second biasing member 150 . First cap 120 has aperture 102 a and a corresponding aperture 102 c (shown in FIG. 4 ). Apertures 102 a and 102 c of first cap 120 are sized to receive first leg 22 of flexible member 20 . Second cap 103 has aperture 103 a and corresponding aperture 103 c (shown in FIG. 4 ), which are sized to receive second leg 23 of flexible member 20 . Insert 110 preferably has a first bore 102 b and a second bore 103 b , which are sized to receive first leg 22 and second leg 24 , respectively, of flexible member 20 . The interior of first cap 120 is dimensioned to slidably receive a first end 112 of insert 110 , and the interior of second cap 130 is dimensioned to slidably receive second end 113 of insert 110 . First biasing member 140 is dimensioned to be received within the interior of first cap 120 , and second biasing member 150 is dimensioned to be received within the interior of second cap 130 .
To assemble clamping device 100 , first biasing member 140 is placed within the interior of first cap 120 , and first cap 120 is then, in turn, placed over the first end 112 of insert 110 , thereby compressing first biasing member 140 so that aperture 102 a and corresponding aperture 102 c of first cap 120 align with first bore 102 b of insert 110 . First leg 22 of flexible member 20 , without first end stop 24 attached, is then passed through passage 102 formed by the alignment of aperture 102 a , first bore 102 b and corresponding aperture 102 c . Ornament 30 , if desired, is then mounted to flexible member 20 . Second biasing member 150 is then placed within the interior of second cap 130 , and second cap 130 is, in turn, placed over the second end 113 of insert 110 , thereby compressing second biasing member 150 so that aperture 103 a and corresponding aperture 103 c of second cap 130 align with second bore 103 b of insert 110 . Second leg 23 of flexible member 20 , without second end stop 25 attached, is then passed through passage 103 formed by the alignment of aperture 103 a , second bore 103 b and corresponding aperture 103 c . First end stop 24 can then be attached to the first free end of first leg 22 and second end stop 25 can then be attached to the second free end of second leg 23 , respectively, using a conventional attachment method, such as soldering. First and second end stops 24 and 25 are sized so that they are larger than the diameter of passages 102 and 103 , and, therefor, first and second end stops 24 and 25 cannot pass through passages 102 and 103 .
In its normal, resting condition, slidable clamping device 100 securely prevents relative movement between slidable clamping device 110 , first leg 22 and second leg 23 . Relative movement is prevented by shear forces applied to first and second legs 22 and 23 by first and second biasing members 140 and 150 , respectively. First biasing member 140 tends to force first cap 120 away from the first end 112 of insert 110 , and thereby creates a misalignment between aperture 102 a and first bore 102 b as well as misalignment between first bore 102 b and corresponding aperture 102 c . This misalignment produces a shear force on first leg 22 at aperture 102 b and corresponding aperture 102 c . Second biasing member 150 applies another shear force to second leg 23 by creating a misalignment between aperture 103 a and second bore 103 b as well as a misalignment between second bore 103 b and corresponding aperture 103 c . The shear forces applied to first and second legs 22 and 23 keep them firmly secured within passages 102 and 103 and prevent relative movement. While coil springs are preferable for first and second biasing members 140 and 150 , a wide variety of other biasing members can be utilized, including compressible materials, such as rubber, as long as the biasing members exert sufficient force to prevent relative movement between sildable clamping device 100 , first leg 22 and second leg 23 .
Slidable clamping device 100 can easily be adapted to slide freely along the lengths of first and second legs 22 and 23 by depressing first and second caps 120 and 130 , as shown best in FIGS. 2A-2C, to compress first and second biasing members 140 and 150 . This external compressive force reduces the misalignment between aperture 102 a , corresponding aperture 102 c and first bore 102 b and reduces the misalignment between aperture 103 a , corresponding aperture 103 c and second bore 103 b , which, in turn, reduces the shear forces applied to first and second legs 22 and 23 . With the shear forces reduced, slidable clamping device 100 can be freely slid along the lengths of first and second legs 22 and 23 to adjust the size of loop portion 21 of flexible member 20 . Slidable clamping device 100 can then be adapted to once again prevent relative movement between slidable clamping device 100 and first and second legs 22 and 23 by simply removing the external compressive force applied to first cap 120 and second cap 130 .
It will be understood by those skilled in the art that, while an insert 110 having two passages 102 and 103 is preferable, insert 110 can, alternatively, have a single passage, with first leg 22 and second leg 23 both extending through the single passage. In this alternative embodiment of the invention, it would only be necessary to utilize a single cap, such as first cap 120 , and a single biasing member, such as first biasing member 140 . It will also be recognized that slidable clamping device 100 can be partially enclosed within a decorative housing, and that the housing can comprise precious stones and other ornamental features.
Thus, while certain preferred embodiments of the invention have been shown and described, it will be appreciated from this description that many changes and modifications can be made thereto without departing from the spirit and scope of the invention. | Methods and apparatus for precisely adjusting an article of jewelry to quickly and conveniently accommodate the particular fashions desires, size and clothing of the wearer. According to the invention, a flexible member, such as a necklace chain, is looped upon itself to form a loop portion, a first leg and a second leg. A slidable clamping device is mounted on the first and second legs of the flexible member. The slidable clamping device is adapted, in response to the application of an external compressive force, to slide freely along the lengths of the first and second legs of the flexible member, thereby precisely adjusting the size of the loop portion. When the external compressive force is released, the slidable clamping device securely prevents relative movement between the slidable clamping device, the first leg and the second leg of the flexible member. | 5 |
BACKGROUND
[0001] The present disclosure relates to vehicle exhaust systems for treating exhaust gas and more particularly, to systems and methods for improving the NOx reduction of exhaust gas.
[0002] In vehicles such as trucks, exhaust gas (which is a combination of gas and particulate matter) is processed in multiple stages prior to being released to the atmosphere as illustrated in FIG. 1 . Exhaust from an engine 110 may be processed by a diesel oxidation catalyst (DOC) 120 to remove hydrocarbons, by a diesel particulate filter (DPF) 130 to remove particulate matter, and by a selective catalytic reduction device (SCR) 140 to reduce NOx to Nitrogen gas and water vapor. For the SCR 140 stage, diesel exhaust fluid (DEF) is injected into and mixed with the exhaust upstream of the SCR device 140 .
[0003] Currently, trucks have an onboard tank that contains DEF. DEF is composed of approximately 32.5% Urea and 67.5% demineralized water. In most DEF injection systems, DEF is delivered through an injector. DEF delivering injectors can be of a plurality of designs which rely on a pressure gradient across an orifice (high pressure in the injector, low pressure on the outside) to atomize the fluid. DEF is injected by applying approximately nine bar pressure to the fluid. The pressure forces the fluid through the orifices into the exhaust where it is then atomized. In other systems, DEF is mixed with compressed air before it enters the injection nozzle to improve atomization.
[0004] It is desirable to have smaller droplet sizes (of the DEF) during atomization to increase the efficiency and effectiveness of the after treatment process of the exhaust gas or fluid.
SUMMARY
[0005] In accordance with an exemplary embodiment, a fluid injection system comprises: a mixing chamber locatable in an exhaust gas conduit upstream of a selective catalytic reduction device (SCR), the chamber providing a flow path for exhaust gas and a space for receiving an injected fluid; an injector having a plurality of bundled capillary tubes each having an inlet and an outlet wherein the inlet is configured to receive a fluid for injection into the chamber, the injector being mounted on the chamber with the tube outlets in fluid communication with the space in the chamber; a base plate disposed in the chamber spaced from and aligned with the bundled capillary tubes; a voltage supply connected to the tubes and to the base plate wherein the voltage supply provides a charge to the tubes and to the base plate to create an electric field to the fluid in the tubes; and a valve disposed on a wall of the chamber for at least one of priming and purging of the tubes.
[0006] In accordance with another exemplary embodiment, a fluid injection method is comprises the steps of: keying on a diesel engine; opening an exit valve and a prime/purge valve of an exhaust chamber associated with the engine; priming a plurality of capillary tubes that inject diesel exhaust fluid (DEF) into the chamber; closing the prime/purge valve; opening an entry valve of the exhaust chamber; cranking the engine on; applying a voltage to the tubes to electrically charge the fluid in the tubes; and drawing the electrically charged fluid into the chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The several features, objects, and advantages of exemplary embodiments will be understood by reading this description in conjunction with the drawings. The same reference numbers in different drawings identify the same or similar elements. In the drawings:
[0008] FIG. 1 illustrates schematically a typical exhaust treatment system of a vehicle;
[0009] FIGS. 2A and 2B illustrate schematically injection systems in accordance with exemplary embodiments;
[0010] FIG. 3 illustrates an atomization process in accordance with exemplary embodiments;
[0011] FIG. 4 illustrates exemplary states of a plurality of valves used in exemplary embodiments; and
[0012] FIG. 5 illustrates a method in accordance with exemplary embodiments.
DETAILED DESCRIPTION
[0013] In the following description, numerous specific details are given to provide a thorough understanding of embodiments. The embodiments can be practiced without one or more of the specific details, or with other methods, components, materials, etc. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the exemplary embodiments.
[0014] Reference throughout this specification to an “exemplary embodiment” or “exemplary embodiments” means that a particular feature, structure, or characteristic as described is included in at least one embodiment. Thus, the appearances of these terms and similar phrases in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. The headings provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0015] According to exemplary embodiments, an injector having a plurality of capillary tubes is disclosed. An exemplary arrangement of an injector 200 is illustrated in FIG. 2A . Injector 200 may include or consist of a plurality of capillary tubes 202 arranged as a bundle. A capillary tube is a thin walled conduit made partly or entirely of conductive material. The tubes are arranged parallel to each other. Each tube 202 may have an inlet 204 and an outlet 206 . The inner diameter of the capillary tube may be approximately 0.25 mm but not more than 2.5 mm to utilize capillary action. The term “injector” may be used interchangeably with the terms “bundle” or “capillary tube bundle” within this disclosure.
[0016] Diesel exhaust fluid (DEF) may be delivered to an inlet end 204 of each of the capillary tubes 202 from a DEF reservoir or tank 250 . An exhaust gas path chamber 280 is located downstream of a DPF 290 and upstream of an SCR 295 . The injector 200 is mounted on the chamber 280 with the outlet end 206 of each of the capillary tubes 202 in the chamber 280 . The outlets are in fluid communication with an inner portion or interior space of the chamber 280 . The diameter of the chamber 280 may vary according to the application under which the aftertreatment system is needed. For example, the inner diameter of the chamber for a large engine (such as that of a truck, for example) will be greater than the inner diameter of the chamber for a passenger vehicle (such as sedan, for example).
[0017] A base plate 248 is mounted in the exhaust gas path chamber 280 spaced from and aligned with the tube outlets 206 . The base plate 248 may be made of a conductive material and located on an interior surface of the chamber opposite to the outlets. A voltage source 240 may be connected between the base plate 248 and the capillary tube bundle 200 . Voltage may be applied to the capillary tube bundle and to the base plate such that the tube bundle forms anode 244 and the base plate becomes a cathode 248 . The voltage supply circuit is also grounded as illustrated.
[0018] As the liquid enters (and passes through) the tubes 202 , the fluid becomes electrically charged and is subjected to the electric field. Coulombic attraction between the anode 244 and cathode 248 draws the charged fluid from the anode through outlets 206 toward the cathode base plate 248 . The fluid from outlets 206 becomes atomized within chamber 280 as described below with reference to FIG. 3 .
[0019] The atomization of the fluid is illustrated in FIG. 3 . As described above, due to coulombic attraction between cathode 348 and anode 344 , the charged fluid in tube 302 flows through outlet 306 . Due to surface tension, electrostatic and hydrodynamic forces at outlet 306 of capillary tube 302 , above a threshold voltage the fluid may form a Taylor cone 380 from which an electrostatic jet of charged fluid 382 emanates.
[0020] As the jet 382 gets closer to the cathode, it becomes unstable and atomizes into a plume 386 of charged fluid. The atomized fluid mixes with the exhaust gas flowing through the exhaust gas path chamber (i.e. exhaust gas path chamber 280 of FIG. 2A ).
[0021] Referring to FIG. 2A , flow of exhaust gas through chamber 280 may be controlled by butterfly valves (BVs) 210 and 220 . A first butterfly valve 210 (BV 1 ) upstream of the injector 200 regulates exhaust gas flow from DPF 290 into chamber 280 . A second butterfly valve 220 (BV 2 ) downstream of the injector 200 regulates exhaust gas flow which contains exhaust gas mixed with atomized DEF out of mixing chamber 280 into SCR 295 . Upon exposure to the heat of the exhaust, the atomized DEF breaks down into CO 2 and NH 3 .
[0022] A third butterfly valve 230 (BV 3 ) disposed on a wall of the mixing chamber 280 can regulate flow of air into the mixing chamber. BV 3 230 may be connected to a pressure modifying device, which may be vacuum source or a pump 260 that is connected to an air tank or air compressor 265 .
[0023] BV 3 230 may selectively prime or purge injector 200 by altering the pressure in chamber 280 . BV 3 230 may prime injector 200 by lowering the air pressure in chamber 280 with respect to the atmosphere. Conversely, BV 3 230 may purge injector 200 by raising the air pressure in chamber 280 with respect to the atmosphere.
[0024] In other embodiments, the injector can also be primed by using air tank 265 to pressurize DEF tank 250 as illustrated in FIG. 2B . This would have the same effect as lowering the pressure in mixing chamber 280 . A fourth butterfly valve 235 (BV 4 ) may regulate flow between air tank 265 and DEF tank 250 in this exemplary embodiment.
[0025] Referring back to FIG. 2A , when the engine is keyed off and is not cranking (i.e. ignition off and engine off), BV 1 , BV 2 and BV 3 are all in a “close” position (i.e. not permitting gas or air flow). This may be referred to as Phase 1.
[0026] When the engine is keyed on but is not cranking (i.e. ignition on and engine off), BV 1 remains in a “close” position while BV 2 is changed to an “open” position. BV 3 is changed to an “open” position to prime the injector 200 . This may be referred to as Phase 2. The injector 200 may be primed by adjusting the pressure in chamber 280 to a level that is lower than the pressure in the DEF holding tank 250 . Priming results in the DEF being drawn from DEF tank 250 into each of the tubes 202 that form injector (or bundle) 200 .
[0027] As the engine starts cranking and is keyed on (i.e. ignition on and engine on), BV 1 is changed to an open position. BV 2 remains in the “open” position. BV 3 is changed to a “close” position as the injector 200 is primed. This may be referred to as Phase 3. Exhaust from DPF 290 enters chamber 280 and mixes with atomized DEF from injector 200 and exits chamber 280 to SCR 295 .
[0028] When the engine is not cranking and is still keyed on (i.e. ignition on and engine off), BV 1 and BV 2 are changed to a “close” position. BV 3 is changed to an “open” position to purge the injector 200 . This may be referred to as Phase 4. The injector may be purged by adjusting the pressure in chamber 280 to a level that is higher than the pressure in the DEF holding tank 250 . Purging results in evacuating the tube bundle 200 of DEF from each of the capillary tubes 202 and forcing it back into DEF tank 250 . The removal of DEF from the tubes eliminates the freezing or crystallization of the urea in the tubes.
[0029] When the engine is turned off and keyed off (i.e. ignition off and engine off), BV 1 and BV 2 remain in “close” position and BV 3 changes to “close” position. This may be referred to as Phase 5 which is identical to Phase 1.
[0030] The position of each of the butterfly valves BV 1 , BV 2 and BV 3 as well as the state of engine ignition and engine crank for each phase described above with reference to FIG. 2A is illustrated in table 400 of FIG. 4 .
[0031] The number of capillary tubes 202 included within a bundle that forms the injector 200 may depend on the amount of DEF needed to effectively treat the exhaust gas as well as packaging constraints. For example, the tube bundle as described herein may include one hundred and sixty (160) individual capillary tubes assuming an optimized circle packing constant of 0.9069 is achieved in order to meet a required DEF flow rate of 2 grams per second for example. A packing constant may be defined as the area used divided by the area available (packing constant=area used/area available).
[0032] Other factors that may affect the number of tubes include, but are not limited to, the temperature, pressure, electric field potential (i.e. voltage applied), fluid contaminants, and fluid viscosity. The voltage is applied after the injector has been primed and the injection of DEF is needed or desired.
[0033] A method in accordance with exemplary embodiments may be described with reference to FIG. 5 . For purposes of describing an exemplary method 500 , valve BV 1 may be referred to as entry valve, BV 2 may be referred to as exit valve and BV 3 may be referred to as prime/purge valve.
[0034] An engine may be keyed on at step 510 (Phase 2). Exit valve 220 (BV 2 ) and prime/purge valve 230 (BV 3 ) may open at step 512 . This allows tubes 200 to be primed at step 514 by reducing air pressure in exhaust chamber 280 . The tubes may be primed by drawing fluid from DEF tank 250 . The prime/purge valve 230 (BV 3 ) may be closed at step 516 . The entry valve 210 (BV 1 ) may be opened at step 518 (BV 2 220 remains open).
[0035] The engine may start cranking at step 520 (i.e. Phase 3). A voltage 240 may be applied to injector 200 to charge the fluid at step 524 . The charged fluid may be drawn to chamber 280 at step 528 .
[0036] The engine may be shut off or stop cranking at step 530 (Phase 4). Voltage supply to the tubes 200 may be switched off step 532 . Entry valve 210 (BV 1 ) and exit valve 220 (BV 2 ) may be closed at step 534 . Prime/purge valve 230 (BV 3 ) may be opened at step 535 . Tubes 200 may be purged at step 536 . After the injector (made up of the tubes) is purged, prime/purge valve 230 (BV 3 ) may be closed at step 538 . The engine may be keyed off at step 540 (Phase 5).
[0037] Exemplary embodiments as described herein facilitate the production of an advantageously small droplet size of the atomized diesel exhaust fluid that facilitates the DEF being mixed with the exhaust gas. Droplets having a size (i.e. diameter) of 1 to 100 micrometers may be formed. Existing systems are not believed capable of producing droplets having such a size. The voltage supply may range between 5 volts (V) to 200 kilovolts (kV). An airless urea dosing system may also be realized utilizing exemplary embodiments. An airless system refers to not using compressed air to facilitate the pressure drop across the injector orifice, i.e. atomization.
[0038] Although exemplary embodiments have been disclosed, it will be apparent to those skilled in the art that various changes and modifications can be made which will achieve some of the advantages of embodiments without departing from the spirit and scope of the disclosure. Such modifications are intended to be covered by the appended claims in which the reference signs shall not be construed as limiting the scope.
[0039] In the description and the appended claims the meaning of “comprising” is not to be understood as excluding other elements or steps. Further, “a” or “an” does not exclude a plurality, and a single unit may fulfill the functions of several means recited in the claims.
[0040] The above description of illustrated embodiments, including what is described in the Abstract, is not intended to be exhaustive or to limit the embodiments to the precise forms disclosed. Although specific embodiments of and examples are described herein for illustrative purposes, various equivalent modifications can be made without departing from the spirit and scope of the disclosure, as will be recognized by those skilled in relevant art.
[0041] The various embodiments described above can be combined to provide further embodiments. Aspects of the embodiments can be modified, if necessary to employ concepts of the various patents, applications and publications to provide yet further embodiments.
[0042] 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. | A fluid injection system includes a mixing chamber locatable in an exhaust gas conduit upstream of a selective catalytic reduction device for providing an exhaust gas flow path and space for receiving injected fluid, an injector with a plurality of bundled capillary tubes each having an inlet configured to receive a fluid for injection into the chamber and an outlet wherein the injector is mounted on the chamber with the tube outlets in fluid communication with the chamber space, a base plate disposed in the chamber spaced from and aligned with the bundled tubes, a voltage supply connected to the tubes and to the base plate for providing a charge to the tubes and to the base plate to create an electric field to the fluid in the tubes, and a valve disposed on a wall of the chamber for at least one of priming and purging of the tubes. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority benefit from U.S. Provisional Application No. 61/330,575, filed on May 3, 2010, and is related to the following commonly-owned, co-pending U.S. patent application Ser. No. 1) 12/782,973, filed May 19, 2010, entitled “Fresh Flush Recycling Toilet;”
BACKGROUND
[0002] This invention relates to the transport of portable structures, particularly portable toilets. Conventional portable or transportable structures such as portable toilet units are typically used at construction sites, outdoor public events and various other venues where a running water supply is unavailable. These structures generally comprise a housing within which a waste material storage tank is positioned. The housings of the portable toilet are usually made of large sheets of plastic materials which are formed into rear and side walls and a front wall having a doorway and a suitable door, a roof and a floor. The structures are typically light enough to be moved and/or loaded onto a trailer by one person who tips the structure down and slides it into place on the bed of a conventional flat bed trailer.
[0003] It is desirable to transport portable toilet structures in an upright position to minimize the likelihood that waste will leak from the collection tank into the interior portion of the housing. Towing one or more portable toilet structures on a trailer presents challenges, particularly in windy conditions due to the shape of the structures and the wind resistance exerted against the housing walls as they are towed at normal driving speeds behind a truck or a car. While wind diverters and other devices have been conceived to help reduce wind resistance while towing using trailers, these devices are clumsy and must be mounted to the towing vehicle or the trailer. Examples of wind diverters can be found in U.S. Pat. No. 3,596,974 to Adams, U.S. Pat. No. 3,695,673 to Meadows and U.S. Pat. No. 3,768,854 to Johnson et al.
[0004] Conventional flat bed and other trailer types are unsatisfactory or inconvenient to use for transporting portable toilet or other portable structures because there is no standardized element on a conventional trailer for quickly and easily securing the portable toilet structure to the conventional trailer. Also, the height or covered housing structure of a conventional trailer may make it difficult to load and unload the portable toilet structure. An example of a conventional flat bed trailer is disclosed in U.S. Pat. No. 3,731,831 to Huff. A standard trailer with a housing is disclosed in U.S. Pat. No. 4,807,894 to Walker.
[0005] Specialty trailers for towing portable structures are also known. Examples of such trailers are disclosed in U.S. Pat. No. 7,401,804 to Rupp, U.S. Pat. No. 4,653,125 to Porter and U.S. Pat. No. 5,548,856 to Julian.
[0006] It is desirable to provide a trailer for transporting one or more portable structures in which it is relatively quick and simple for a portable structure to be loaded onto, secured to and unloaded from a trailer. It is also desirable for the trailer to be designed such that the wind resistance incurred while towing the portable toilet structure at normal driving speeds, particularly on an interstate highway is reduced from the oncoming forward direction of the vehicle and for cross-winds from either side. The invention of the present application addresses these problems and provides an improved trailer for transporting portable structures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIGS. 1A-1D show various views of a portable structure;
[0008] FIG. 2A and FIG. 2B show perspective views of a trailer for transporting a portable structure;
[0009] FIG. 3 is a top down view of the trailer;
[0010] FIGS. 4A-4B are side views of the trailer;
[0011] FIG. 5 is a rear view of the trailer;
[0012] FIG. 6 is a top view of the trailer showing wind deflection direction as the trailer is being towed; and
[0013] FIG. 7 is a top view of the trailer with a configuration to accommodate four portable structures.
DETAILED DESCRIPTION
[0014] FIGS. 1A-1D show different views of a portable structure 10 where FIG. 1A is a perspective view, FIG. 1B is a front view, FIG. 1C is a side view, and FIG. 1D is a bottom view. Portable structure 10 has a hinged door 12 and a base 16 that is formed of horizontal skid plates 18 running from one side of structure 10 to the opposing side.
[0015] As shown in the FIGS. 2A-6 , a trailer 100 for transporting portable structure 10 includes a central axle 102 to which are affixed wheels 104 at either end, a tow bar 106 , a base frame 108 , a stabilizer bar 110 , a tow bar support 112 , a hitch 114 and fenders 116 . It should be understood that the function of tow bar support 112 can be alternatively achieved by integrating a support shape into tow bar 106 as shown in FIGS. 2B and 4B . The height of the dip in the support shape may be configured for different uses and the drawings are not drawn to scale. For example, in the case of the trailer of the present invention, the dip in the support shape may be a few inches, or just enough to keep the hitch off the ground when the bottom of the support shape is resting on the ground. This configuration will prevent dirt or other debris from collecting in the hitch, but will not interfere with road topology where it is undesirable for the bottom of the support shape to drag on the ground while being towed. In other cases, the dip may be much more pronounced to raise the level of the hitch higher off the ground. The general purpose of the support shape is to eliminate the need for a jack stand (not shown) that is common on trailers of all types.
[0016] A handle 113 may also be attached to the top of tow bar 106 to make it easier to lift tow bar 106 and place hitch 114 over the corresponding ball (not shown) extending from a vehicle. Base frame 108 holds the base of a portable structure by engaging one end of skid plates 18 formed at base 16 of portable structure 10 . Base frame 108 further includes a step bar 118 , bottom support members 120 that support the portable structure 10 underneath skid plates 18 , top skid plate engagement element 122 and securing rods 124 . Also attached to each of fenders 116 is a taillight cluster 126 housing taillights, brake lights and back-up lights that connect to the electrical system of the tow vehicle.
[0017] The T-shaped trailer components consisting of axle 102 and tow bar 106 as well as fenders 116 , taillight clusters 126 , wheels 104 , hitch 114 and tow bar support member 112 will not be described in greater detail herein. Base frame 108 is mounted to the top of axle 102 and tow bar 106 . Base frame 108 is a rectangular or square shape that has dimensions slightly exceeding the base portion of portable structure 10 , including skid plates 18 that form base 16 of portable structure 10 . Each component of base frame 108 making up the four sides of base frame 108 is formed of an L-shape angled component 120 such that portable structure 10 comes into contact and sits atop the lower horizontal portion 120 a of each L-shape angled component 120 with opposing ends of skid plates 18 contacting the vertical side portion 120 b of L-shape angled component 120 at the both ends of each skid plate 18 . By having the dimensions of base frame 108 slightly exceed the dimensions of portable structure base 16 , portable structure 10 fits snugly inside of base frame 108 without shifting during transport.
[0018] Base frame 108 is preferably mounted with a leading corner 128 affixed to tow bar 106 . Mounting can be accomplished by bolting base frame 108 to tow bar 106 , but is preferably accomplished by welding base frame 108 to tow bar 106 and axle 102 . Alternatively, it can be mounted through the use of permanent rivets or bolts and nuts. With lead corner 128 affixed to tow bar 106 , side corners 130 align with axle 102 inside of wheels 104 . Side corners 130 of base frame 108 are also preferably mounted to axle 102 by welding, rivets or bolts. Configuring base frame 108 with respect to axle 102 and tow bar 106 as described results in portable structure 10 sitting at a 45 degree angle to leading corner 128 bisected by an axis through tow bar 106 . This alignment results in natural wind flow deflection to the sides of portable structure 10 . The deflection occurs at a gentle 45 degree angle as the wind hits leading corner 128 and a corresponding corner of portable structure 10 . The wind then flows evenly and gently across the angled sidewalls of portable structure 10 affixed to trailer 100 as the portable structure 10 is towed on trailer 100 by a tow vehicle. The wind deflection is approximately equal on both sides and naturally stabilizes portable structure 10 during towing, particularly as compared to prior art designs where the wind hits the leading wall of portable structure 10 head-on resulting in a tendency to blow it over making trailers using such a design unstable and difficult to maneuver, particularly at highway speeds.
[0019] In addition, the angled placement design of the present invention dictates that axle 102 be wider than that of a trailer for transporting a portable structure at a position angled 90 degrees to tow bar 106 . This is because the angled configuration must accommodate the diagonal dimension of a portable toilet structure which is greater than the side dimension of a portable structure 10 . The use of a wider axle 102 further increases the stability of trailer 100 resulting in better handling on the road.
[0020] It should also be recognized that cross winds blowing from either side of trailer 100 will be broken at a 45 degree angle by side corners 130 in a manner similar to that described with respect to leading corner 128 . Wind resistance being directed from the front or side of the trailer during towing with the design of the present invention will be greatly reduced resulting in smoother operation for trailer 100 and a significant increase in the level of safety for the occupants of the vehicle towing trailer 100 , as well as others who may be occupants in vehicles on the road in the vicinity of trailer 100 during transport.
[0021] In operation, portable structure 10 is loaded onto trailer 100 by tilting it and sliding the skids of the portable toilet structure up onto and over step bar 118 into base frame 108 . As can be seen in FIGS. 1A-1D , Skid plates 18 on the bottom of portable structure 10 protrude beyond the walls of structure 10 . This protrusion of skid plates 18 provides a means for engaging portable structure 10 inside of base frame 108 . At one side of base frame 108 is a fixed skid plate engagement element 122 . The ends of skid plates 18 of portable structure 10 are positioned under plate 122 . Once base 16 of portable structure 10 is positioned in base frame 108 with skid plates 18 under plate 122 , the other end of skid plates 18 are secured at the opposing side of base frame 108 using securing rods 124 . These rods pass through anchor holes in skid plates 18 and through aligned holes in base frame 108 . The rods can be implemented in a number of ways including using screws, spring loaded rods or any other apparatus for holding skid plates 18 in place. Alternatively, a second fixed skid plate engagement element (not shown) can be locked down over the opposite ends of skid plates 18 . It is also possible to implement the second fixed skid plate engagement element using a spring loaded mechanism that can be easily and quickly opened during positioning of portable structure 10 and then locked over the ends of skid plates 18 . Once portable structure 10 is secured, it may be safely towed on trailer 100 .
[0022] It is to be understood that the above descriptions and drawings are only for illustrating variations of the present invention and are not intended to limit the scope thereof. Any variation or derivation from the above description and drawings are included in the scope of the present invention. For example, FIG. 7 shows a configuration of a trailer that can accommodate 4 portable structures. In such a configuration, the size of the underlying trailer frame could be made larger while maintaining the basic “diamond” shape. To accommodate the 3 additional portable structures, the opposing sides of the base frame could be lengthened to form an elongated rectangular base frame with the ability to hold two portable structures, while a second elongated base frame could be positioned adjacent to and behind the first base frame to accommodate two additional portable structures. In such a configuration, the trailer width and axle would need to be made at least as wide as the diagonal dimension of two portable structures. Additional elongated base frames could be added to a longer trailer to increase the number of portable structures to be carried. | A trailer for use primarily for transporting a portable structure in which a frame is mounted on an undercarriage with the wheels of the undercarriage near the longitudinal center and the portable structure is positioned at an angle to reduce wind resistance while the structure is being transported on the trailer. The portable structure is secured to the trailer by placing the skid plates of the portable structure under frame elements affixed to the trailer frame. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
Cross-Reference to Provisional Patent Application
[0001] The inventor claims domestic priority, pursuant to 35 U.S.C. §119(e), on the basis of U.S. Provisional Patent Application No. 60/510,398, filed Oct. 14, 2003, the entire disclosure of which shall be deemed to be incorporated by reference herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates, generally, to an oil-free viscoelastic elastomer gel, which may be shaped and molded for being beneficially applied to a person's skin.
[0004] More particularly, the present invention relates to a composite article comprising a thermoplastic, heat-formable, and heat reversible, gelatinous elastomer composition, which is formed into a composite by heating with at least one substrate material, which may be applied to human skin. The elastomer composition is formed from one or more hydrogenated styrene/isoprene/butadiene block polymers and specialty esters and/or conventionally known compositions used to provide esthetic properties and emolliency to cosmetic formulations.
[0005] The composite articles of the invention, which include an oil-free thermoplastic, gelatinous elastomer composition, can be used to form viscoelastic elastomer-based gels that are well-suited for topical application (e.g., being appropriately moldable and formable into a variety of shapes and conformations.)
[0006] 2. Description of the Prior Art
[0007] The prior art discloses a large number of compositions comprised of oil-extended thermoplastic block copolymers. Such teachings are to be found in U.S. Pat. Nos. 4,369,284; 4,618,213; 5,153,254; 5,633,286; 6,148,830; and 6,552,109, with the compositions disclosed therein generally including certain low viscosity triblock copolymers which have been plasticized with high levels of oil.
[0008] The inherent properties of the gelatinous elastomer compositions and articles made therefrom are many, with the gel compositions taught by the enumerated patents above exhibiting high dimensional stability, crack, tear, craze and creep resistance, excellent tensile strength and high elongation, long-service life under stress and capability of repeated handling, excellent processing ability for cast molding, are non-toxic, nearly tasteless and odorless, extremely soft and strong, highly flexible and possessing elastic memory, substantially with little or no plasticizer bleed out.
[0009] The oil plasticizers utilized by the prior art, which are generally present at levels significantly higher than the polymers themselves (typically about 3- to 15-times higher), serve a major role. The plasticized gels resist tearing under tensile loads or dynamic deformation, unlike unplasticized triblock copolymer gels, such as styrene-ethylene-butylene-styrene (“SEBS”) and styrene-ethylene-propylene-styrene (“SEPS”) gels, which possess high tensile strength, but will catastrophically snap apart into two reflective clean smooth surfaces when cut or notched under tensile or dynamic loads. A plasticized gel can be stretched by a first tensile load with uniform deformation to a measured length, and upon the application of higher tensile loads, the gel can be further extended without breaking. Upon release, the gel returns immediately to its original shape and any necking quickly disappears.
[0010] The nature of the oil plasticizers that are used in these products limits the application of these gels in a number of personal care, topical skin products. Examples of representative commercially available plasticizing oils include polybutenes, hydrogenated polybutenes, polybutenes with epoxide functionality at one end of the polybutene polymer, liquid poly(ethylene/butylene), liquid hetero-telechelic polymers of poly(ethylene/butylene/styrene) with epoxidized polyisoprene, and poly(ethylene/butylene) with epoxidized polyisoprene. Also cited as appropriate examples of various commercially oils are ARCO PRIME, DURA-PRIME and TUFFLO (trademarks) oils, and other white mineral oils, such as the BAYOL (trademark) series. The oily nature of these materials can often make them unsuitable for use of the gels for cosmetic application and topical medical delivery systems.
[0011] As used in this disclosure, the linear triblock co-polymers poly(styrene-ethylene-ethylene-propylene-styrene) is denoted by the abbreviation “SEEPS”; poly(styrene-ethylene-butylene-styrene) is denoted by the abbreviation “SEBS”; poly(styrene-ethylene-propylene-styrene) is denoted by the abbreviation “SEPS”; the branched copolymers poly(styrene-ethylene-propylene) is denoted by the abbreviation “SEP”; and poly(styrene-ethylene-butylene) is denoted by the abbreviation “SEB.”
[0012] The present invention is the result of efforts to develop a way for modifying the rigidity of these triblock copolymers, such as SEBS and SEPS gels, so as to provide a similar type of viscoelasticity in gels that are more readily applicable to personal care products in the cosmetic and medical delivery fields.
SUMMARY OF THE INVENTION
[0013] It is, therefore, an object of the present invention to provide a viscoelastic elastomer gel, which includes a thermoplastic, heat-formable, and heat reversible, gelatinous elastomer composition, for application to a person's skin, which avoids the use of oil plasticizers, but which is nevertheless highly flexible and possesses high resistance to tearing under tensile loads or dynamic deformation.
[0014] The foregoing and related objects are achieved by the oil-free viscoelastic elastomer gel of the present invention, which comprises a composite article having a thermoplastic, heat formable and heat reversible gelatinous elastomer composition, which is formed into a composite by heat with one or more substrate materials. The gelatinous elastomer includes at least one hydrogenated styrene/isoprene/butadiene block copolymers and at least one polymer or copolymer of the group poly(styrene-butadiene-styrene), poly(styrene-butadiene), polystyrene-isoprene-styrene), poly(styrene-isoprene), poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene-styrene) and poly(styrene-ethylene-butylene). Preferably, the polymers or copolymers are the KURARAY SEPTON 4000 Series Block Polymer Nos. 4033, 4045, 4055, made from hydrogenated styrene isoprene/butadiene styrene block copolymers. The hydrogenated styrene block polymer preferably includes 2-methyl-1,3-butadiene and 1,3-butadiene.
[0015] Optionally, the gelatinous elastomer should also include at least one specialty esters and/or other conventionally utilized materials for providing an esthetic property and emolliency to a cosmetic formulation. The specialty esters found to be useful are those composed of long-chain fatty acids esterfied with long-chain alcohols and gycols. Commercial brand names (trademarks) for these ester products include those in the HEST, CRODAMOL, ALZO and DUMOL series, and the like. Chemical names of these specialty esters generally include isodecyl- and octyl-based esters such as iso- and iso-octyl dodecyl myristate and isostearate, isodecyl- and isooctyl isocetyl stearate and isostearate, Glycereth-18 ethyl hexanoate, octyldodecyl myristate, etc. Generally, esterified combinations of both alcohols/gycols and acids, with C 8 -C 24 carbon chains, are appropriate to impart both beneficial cosmetic and medical delivery benefits to the elastomer. Preferred combinations are those which, because of chain length and steric structure, are liquid at ambient temperatures, or are readily liquefiable near ambient temperatures. The other conventionally utilized materials include various animal-derived non-oil materials, such as lanolin and its derivatives, squalene and cholesterol esters.
[0016] The elastomer gels of the present invention have also been found suitable as solvent bases for dissolution, and subsequent release of a variety of cosmetic and cosmeceutical materials of recognized benefit to human skin.
[0017] Other objects and features of the present invention will become apparent when considered in view of the following detailed description of the invention, which provides certain preferred embodiments and examples of the present invention. It should, however, be noted that the accompanying detailed description is intended to discuss and explain only certain embodiments of the claimed invention and is not intended as a means for defining the limits and scope of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] The gelatinous elastomer composition and oriented gel composition are generally prepared by blending together the components, including other additives, as desired, at ambient temperature to about 100° C. to form a paste-like mixture, and then heating (or further heating, as necessary) the mixture uniformly to about 150° C. to about 200° C. until a homogeneous molten blend is obtained. The temperatures selected depend upon such factors as the viscosity of the specialty esters or specialty components and the amounts and nature of the polymer mixtures used. These components blend easily in the melt and a heated vessel equipped with a stirrer is all that is required. Conventional vessel with pressure and/or vacuum application can be utilized in forming typical batches of the instant compositions from relatively small amounts (e.g., from about 40 lbs., or less, to about 10,000 lbs, or more.) For example, in a large vessel, inert gases can be employed for removing the composition from a closed vessel at the end of mixing and a partial vacuum can be applied to remove any entrapped bubbles. Stirring rates utilized for large batches can range from approximately (and somewhat less than) 10 rpm to about 40 rpm, or even higher.
[0019] For use in the present invention, the molecular chain lengths (molecular weights) of the triblock and branch co-polymers must be sufficient to meet the high solution Brookfield Viscosities requirements described herein that are necessary for making the extremely soft and strong gel compositions. The high viscosity triblock and branched copolymers: SEEPS, SEBS, SEPS, (SEB) n and (SEP) n can be measured under varying conditions of weight-percent solution concentrations in toluene. The most preferred and useful triblock and branched copolymers selected have Brookfield Viscosity values ranging from about 1,800 cps to about 8,000 cps and higher, when measured at 20 weight-percent solution in toluene at 25° C., about 4,000 cps to about 40,000 cps and higher, when measured at 25 weight-percent solids solution in toluene. Typical examples of Brookfield Viscosity values for branched copolymers (SEB) n and (SEP) n at 25 weight-percent solids solution in toluene at 25 ° C. can range from about 3,500 cps to about 30,000 cps and higher; more commonly, about 9,000 cps and higher. Other preferred and acceptable triblock and branched copolymers can exhibit viscosities (as measured with a Brookfield model RVT viscometer at 25° C. at 10 weight-percent solution in toluene) of about 400 cps and higher and at 15 weight-percent solution in toluene of about 5,600 cps and higher. Other acceptable triblock and branched copolymers can exhibit about 8,000 to about 20,000 cps at 20 weight percent solids solution in toluene at 25° C.
[0020] Examples of most preferred high viscosity triblock and branched copolymers can have Brookfield viscosities, at 5 weight-percent solution in toluene at 30° C., of from about 40 to about 50 cps and higher. While less preferred polymers can have a solution viscosity at 10 weight-percent solution in toluene at 30° C. of about 59 cps and higher. The high viscosity triblock, radial, star-shaped and multiarm copolymer of the present invention can have a broad range of styrene end block to ethylene and butylene center block ratio of about 20:80 or less to about 40:60 or higher. Examples of high viscosity triblock copolymers that can be utilized to achieve one or more of the novel properties of the present invention are styrene-ethylene-butylene-styrene block copolymers (SEBS) available from Shell Chemical Company and Pecten Chemical Company (divisions of Shell Oil Company) under trade designations Kraton G 1651, Kraton G 1654X, Kraton G 4600, Kraton G 4609, and the like. Shell Technical Bulletin SC:1393-92 gives solution viscosity as measured with a Brookfield model RVT viscometer at 25° C. for Kraton G 1654X at 10% weight in toluene of approximately 400 cps and at 15% weight in toluene of approximately 5,600 cps. Shell publication SC:68-79 gives solution viscosity at 25° C. for Kraton G 1651 at 20 weight-percent in toluene of approximately 2,000 cps. When measured at 5 weight-percent solution in toluene at 30° C., the solution viscosity of Kraton G 1651 is about 40. Examples of high viscosity SEBS triblock copolymers includes Kuraray's SEBS 8006, which exhibits a solution viscosity at 5 weight-percent at 30° C. of about 51 cps. Kuraray's Septon 8005 SEBS is similarly applicable.
[0021] Kuraray's 4055 SEEPS (styrene-ethylene/ethylene-propylene-styrene) block polymer, made from hydrogenated styrene isoprene/butadiene block copolymer or, more specifically, made from hydrogenated styrene block polymer with 2-methyl-1,3-butadiene and 1,3-butadiene, exhibits a viscosity at 5 weight-percent solution in toluene at 25° C. of about 90 mPa-S, and at 10 weight-percent about 5800 mPa-S. Kuraray's Septon 4044 and 4033 SEEPS are similarly useful. Kuraray's 2006 SEPS polymer exhibits a viscosity at 20 weight-percent solution in toluene at 25° C. of about 78,000 cps, at 5 weight-percent of about 27 mPa-S, at 10 weight percent of about 1220 mPa-S, and at 20 weight-percent 78,000 cps. Kuraray SEPS 2005 polymer exhibits a viscosity at 5 weight-percent solution in toluene at 30° C. of about 28 mPa-S, at 10 weight percent of about 1200 mPa-S, and at 20 weight percent 76,000 cps. Other grades of SEBS, SEPS, (SEB) n , (SEP) n polymers can also be utilized in the present invention, provided such polymers exhibit the required high viscosity. Such SEBS polymers include (high viscosity) Kraton G 1855X, which has a specific gravity of 0.92, Brookfield Viscosity of a 25 weight-percent solids solution in toluene at 25° C. of about 40,000 cps, or about 8,000 to about 20,000 cps at a 20 weight-percent solids solution in toluene at 25° C. The styrene to ethylene and butylene (S:EB) weight ratios for the Shell designated polymers can have a low range of 20:80 or less. Although the typical ratio values for Kraton G 1651, 4600, and 4609 are approximately about 33:67 and for Kraton G 1855X approximately about 27:73, Kraton G 1654X (a lower molecular weight version of Kraton G 1651 with somewhat lower physical properties, such as lower solution and melt viscosity) is approximately about 31:69; these ratios can vary broadly from the typical product specification values. In the case of Kuraray's SEBS polymer 8006 the S:EB weight ratio is about 35:65. In the case of Kuraray's 2005, 2006 and 4055, the S:EEP weight ratios are 20, 35 and 30, respectively. Much like S:EB ratios of SEBS and (SEB) n , the S:EP ratios of very high viscosity SEPS, (SEP) n copolymers are expected to be about the same and can vary broadly. The S:EB, S:EP weight ratios of high viscosity SEBS, SEPS, (SEB) n and (SEP) n useful in forming the gel compositions of the invention can range from lower than about 20:80 to above about 40:60, and higher. More specifically, the values can be 19:81, 20:80, 21:79, 22:78, 23:77, 24:76, 25:75, 26:74, 27:73, 28:72, 29:71, 30:70, 31:69, 32:68, 33:67, 34:66, 35:65, 36:64, 37:63, 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65, 45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:49, etc. Other ratio values of less than 19:81, or higher than 51:49, are also possible.
[0022] Broadly, the styrene block to elastomeric block ratio of the high viscosity triblock, radial, star-shaped, and multi-arm copolymers of the present invention is about 20:80 to about 40:60, or higher, less broadly about 31:69 to about 40:60; preferably about 32:68 to about 38:62; more preferably about 32:68 to about 36:64; particularly more preferably about 32:68 to about 34:66; even more preferably about 33:67 to about 36:64; and most preferably about 33:67. In accordance with the present invention, triblock copolymers, such as, for example, Kraton G 1654X having ratios of 31:69 or higher, and can be used, and do exhibit about the same physical properties in many respects to Kraton G 1651, while Kraton G 1654X, with ratios below 31:69, may also be use, but they are less preferred due to their decrease in the desirable properties of the final gel. Other polymers and copolymers (in major or minor amounts) can be selectively melt blended with one or more of the high viscosity polymers as mentioned above without substantially decreasing the desired properties; these polymers include (SBS) styrene-butadiene-styrene block copolymers, (SIS) styrene-isoprene-styrene block copolymers, (low styrene content SEBS) styrene-ethylene-butylene-styrene block copolymers, (SEP) styrene-ethylene-propylene block copolymers, (SEPS) styrene-ethylene-propylene-styrene block copolymers, (SB) n styrene-butadiene and (SEB) n , (SEBS) n , (SEP) n , (SI) n styrene-isoprene multi-arm, branched or star-shaped copolymers and the like. Still, other polymers include homopolymers which can be utilized in minor amounts; these include: polystyrene, polybutylene, polyethylene, polypropylene and the like.
[0023] The variations in formulations for creating the oil-free viscoelastic gels, which may be beneficially applied to a person's skin, can be best illustrated through reference to the following Examples. These Examples and data provide a basis for understanding the metes and bounds of the invention and are not to be taken as a limitation upon the overall scope of the present invention.
EXAMPLE 1
[0024] A SEPTON SEB triblock copolymer with an S/EB ratio of 29:71, is melt blended with HEST I-20-18B, an octyldodecyl isostearate, a double-branched ester, from the Global Seven Company. For every 100 parts of the SEB polymer an eight-fold amount (800 parts) of the ester was employed. The initial combination was prepared by addition of the HEST I-20-18B to granulated triblock polymer.
[0025] The resulting product has superior tensile strength and high elongation, excellent memory, is suitable for cast molding and is capable of repeated handling with no plasticizer bleed out. This particular composition can be molded into a substrate material, e.g., a cushion, such as a wheelchair cushion, with a fabric cover. The substrate material could also be, for example, a wrist band or a back support.
EXAMPLE 2
[0026] A melt blend is prepared from 100 parts of Kuraray's SEPTON 4055 SEEPS (a (styrene-ethylene/ethylene-propylene-styrene) block polymer made from hydrogenated styrene isoprene/butadiene block copolymer) mixed with 450 parts of Alzo's DERMOL DISD (Diisostearyl Dimer Dilinoleate) at room temperature to form a paste-like mixture; and then heated uniformly to about 165° C. until a homogeneous molten blend is obtained. The mixture is then cooled to ambient temperature.
[0027] The gel in this example resists tearing under tensile loads or during deformation, so that any surface breaks caused by stretching or deformation do not readily propagate further through the gel.
[0028] While only several embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that many modifications may be made to the present invention without departing from the spirit and scope thereof. | A composite article, which may be beneficially applied to the skin, includes a thermoplastic gelatinous elastomer composition, which is formed into a composite by heat with a substrate material. The gelatinous elastomer includes at least one hydrogenated styrene/isoprene/butadiene block copolymers and at least one polymer or copolymer of the group poly(styrene-butadiene-styrene), poly(styrene-butadiene), poly(styrene-isoprene-styrene), poly(styrene-isoprene), poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-butylene). The thermoplastic gelatinous elastomer composition further includes a non-oil plasticizer, which may be a specialty ester, an animal-derived non-oil material for imparting an esthetic property and emolliency to a cosmetic formulation, or a combination thereof. The specialty esters preferably include long-chain fatty acids estified with long-chain alcohols and gycols. The animal-derived non-oil material may include lanolin, a derivative of lanolin, squalene, a cholesterol ester or a combination thereof. The thermoplastic gelatinous elastomer composition avoids the use of plasticized oil. | 2 |
[0001] The present application is a continuation of U.S. patent application Ser. No. 13/615,475, filed on Sep. 13, 2012, which is a continuation of U.S. patent application Ser. No. 13/036,949, filed on Feb. 28, 2011 now issued as U.S. Pat. No. 8,429,543, which is a continuation of U.S. patent application Ser. No. 12/115,193, filed on May 5, 2008 now issued as U.S. Pat. No. 7,900,148, which is a continuation of U.S. patent application Ser. No. 10/326,548, filed on Dec. 23, 2002 now issued as U.S. Pat. No. 7,370,277, which is a continuation-in-part of U.S. patent application Ser. No. 10/259,844, filed on Sep. 30, 2002 now issued as U.S. Pat. No. 7,421,661, which claims priority to U.S. provisional application Ser. No. 60/376,181, filed Apr. 30, 2002. Each of the aforementioned patent(s), and application(s) are hereby incorporated by reference in their entirety.
TECHNICAL FIELD
[0002] The following description relates generally to providing a user interface and more particularly to providing an informational tool tip for an e-mail user interface.
BACKGROUND
[0003] Online service providers facilitate access to information and services by providing interactive L/Is (User Interfaces) that help users navigate to desired resources. Generally, a UI allows a user to execute particular commands or to link to certain locations by simply selecting screen objects such as icons, windows, and drop-down menus. The design of a UI has a significant impact on a user's online experience. In particular, the icons, the windows, and the menus of a UI may be arranged to enable a user to locate preferred information and services quickly and easily.
SUMMARY
[0004] In one general aspect, an interface enables perception of information regarding e-mail communications. The interface includes an e-mail application user interface that enables perception of e-mail message information for one or more e-mails received by an e-mail participant and that enables active display of one or more of the received e-mails selected by the e-mail participant. The interface also includes a mechanism that determines a request for e-mail message information for one of the e-mails from within a desired e-mail message that is not actively displayed. The interface further includes an informational tool tip that provides a temporary perceivable indication to the e-mail participant of at least a portion of the requested information for the desired e-mail message while maintaining active display of the selected e-mails.
[0005] Implementations may include one or more of the following features. For example, the tool tip may be activated in response to participant selection of the desired e-mail message. In one implementation, the participant selection is inferred based upon a position of an input device relative to a user interface. For instance, the selection may be inferred based upon maintaining the input device in a position relative to the user interface for a predetermined threshold period of time. In another implementation, the user selection may be an overt selection activity. For instance, the overt selection may be carried out by manipulating a user input device.
[0006] In one implementation, the informational tool tip may be rendered in a pop up window, and may be rendered as an overlay. The tool tip may provide a perceivable indication of less than all of the determined content of the desired e-mail message session. The tool tip is closed automatically based on a timeout or an inferred intent to close the tool tip, rather than based on an express or overt closing instruction by the user. For example, intent to close the tool tip may be inferred based upon the position of a user input device, the movement of a user input device, or a combination of the position of a user input device and the expiration of a predetermined length of time.
[0007] In one implementation, the user interface is a visual interface. For example, the desired e-mail message may include a text message and the temporary perceivable indication may include at least a portion of the text message. The desired e-mail message may also include an audio-video message (e.g., a video message) and the temporary perceivable indication may include at least a portion of the audio-video message. In another implementation, the user interface may be an audible interface. For example, the desired e-mail message may include an audio message and the temporary perceivable indication may include at least a portion of the audio message.
[0008] In another general aspect, e-mail information for at least one received e-mail is shown on a visual user interface. The user interface receives a request for e-mail information other than the e-mail information shown by the visual user interface, and a pop-up window is rendered with e-mail information other than the information displayed on the visual user interface while the display of information in the visual user interface is maintained.
[0009] Aspects of the informational tool tip may be implemented by an apparatus and/or by a computer program stored on a computer readable medium. The computer readable medium may comprise a disc, a client device, a host device, and/or a propagated signal. In addition, aspects of the informational tool tip may be implemented in a client/host context or in a standalone or offline client device. The informational tool tip may be rendered in a client/host context and may be accessed or updated through a remote device in a client/host environment. The informational tool tip also may be rendered by the standalone/offline device and may be accessed or updated through a remote device in a non-client/host environment such as, for example, a LAN server serving an end user or a mainframe serving a terminal device.
[0010] Other features will be apparent from the following description, including the drawings, and from the claims.
DESCRIPTION OF DRAWINGS
[0011] FIGS. 1 and 2 are block diagrams of a communications system.
[0012] FIGS. 3 and 7 are flow charts of processes that may be implemented by the systems of FIGS. 1 and 2 .
[0013] FIGS. 4A , 4 B, 5 A, 5 B, 6 A, 6 B, and 6 C are illustrations of different graphical user interfaces that may be implemented by the systems of FIGS. 1 and 2 when executing the processes of FIGS. 3 and 7 .
[0014] Like reference symbols in the various drawings indicate like elements. For brevity, several elements in the figures described below are represented as monolithic entities. However, as would be understood by one skilled in the art, these elements each may include numerous interconnected computers and components designed to perform a set of specified operations and/or may be dedicated to a particular geographical region.
DETAILED DESCRIPTION
[0015] In general, an informational tool tip may be provided for an e-mail user interface (UI). An informational tool tip for the e-mail UI is capable of presenting to the user a perceivable indication of at least a portion of an e-mail message that is not being actively displayed. As such, the informational tool tip is able to accommodate a user who seeks to perceive information about one of the e-mail messages that is not actively displayed to the user, while maintaining active display of the currently displayed e-mail message. Although such functionality may be applied to other communications environments, it may have particular utility when applied to an e-mail environment, where it may be used to quickly view content from within a received message without requiring the user to open a persistent window dedicated to that message, and without requiring the user to otherwise change a current view.
[0016] In order to activate the informational tool tip, the user may select a desired e-mail message that is not being actively displayed. For example, to activate and render the informational tool tip, the user may position a mouse or other viewer input device proximate to or over an interface tab or icon corresponding to the desired e-mail message. In response, the informational tool tip may be rendered as a pop-up window and may be rendered in any location on the display.
[0017] The informational tool tip may be used to present all or a portion of the desired e-mail message other than the selected or default message displayed in the preview pane 417 or other e-mail message UI, and to do so without affecting the display of the default or selected e-mail message. In one implementation, a predetermined number of lines or characters of content from within the desired e-mail message are presented. In another implementation, one or more predetermined fields of the message are presented. In another implementation, the content presented in the tool tip is variable and may depend, for example, upon the manner or context in which the tool tip was invoked. The contents of the desired e-mail message may be made available to the tool tip by, for example, a client system or a host system, or a combination thereof.
[0018] For illustrative purposes, FIGS. 1 . and 2 show an example of a communications system for implementing techniques for transferring electronic data such as e-mail messages.
[0019] Referring to FIG. 1 , a communications system 100 is capable of delivering and exchanging data between a client system 105 and a host system 110 through a communications link 115 . The client system 105 typically includes one or more client devices 120 and/or client controllers 125 , and the host system 110 typically includes one or more host devices 135 and/or host controllers 140 . For example, the client system 105 or the host system 110 may include one or more general-purpose computers (e.g., personal computers), one or more special-purpose computers (e.g., devices specifically programmed to communicate with each other and/or the client system 105 or the host system 110 ), or a combination of one or more general-purpose computers and one or more special-purpose computers. The client system 105 and the host system 110 may be arranged to operate within or in concert with one or more other systems, such as, for example, one or more LANs (“Local Area Networks”) and/or one or more WANs (“Wide Area Networks”).
[0020] The client device 120 and the host device 135 are generally capable of executing instructions under the command of, respectively, a client controller 125 and a host controller 140 . The client device 120 and the host device 135 are connected to, respectively, the client controller 125 and the host controller 140 by, respectively, wired or wireless data pathways 130 and 145 , which are capable of delivering data.
[0021] The client device 120 , the client controller 125 , the host device 135 , and the host controller 140 typically each include one or more hardware components and/or software components. An example of a client device 120 or a host device 135 is a general-purpose computer (e.g., a personal computer) or software on such a computer capable of responding to and executing instructions in a defined manner. Other examples include a special-purpose computer, a workstation, a server, a device, a component, other physical or virtual equipment, or some combination of these capable of responding to and executing instructions. The client device 120 and the host device 135 may include devices that are capable of establishing peer-to-peer communications.
[0022] An example of client controller 125 or host controller 140 is a software application loaded on the client device 120 or the host device 135 for commanding and directing communications enabled by the client device 120 or the host device 135 . Other examples include a program, a piece of code, an instruction, a device, a computer, a computer system, or a combination of these for independently or collectively instructing the client device 120 or the host device 135 to interact and operate as described. The client controller 125 and the host controller 140 may be embodied permanently or temporarily in any type of machine, component, physical or virtual equipment, storage medium, or propagated signal capable of providing instructions to the client device 120 and the host device 135 .
[0023] The communications link 115 typically includes a delivery network 160 making a direct or indirect communication between the client system 105 and the host system 110 , irrespective of physical separation. Examples of a delivery network 160 include the
[0024] Internet, the World Wide Web, WANs, LANs, analog or digital wired and wireless telephone networks (e.g. Public Switched Telephone Network (PSTN), Integrated Services Digital Network (ISDN), and Digital Subscriber Line (xDSL)), radio, television, cable, or satellite systems, and other delivery mechanisms for carrying data. The communications link 115 may include communication pathways 150 and 155 that enable communications through the one or more delivery networks 160 described above. Each of the communication pathways 150 and 155 may include, for example, a wired, wireless, cable or satellite communication pathway.
[0025] FIG. 2 illustrates a communications system 200 including a client system 105 communicating with a host system 110 through a communications link 115 .
[0026] The client device 120 typically includes a general-purpose computer 270 having an internal or external memory 272 for storing data and programs such as an operating system 274 (e.g., DOS, Windows™, Windows 95™, Windows 98™, Windows 2000™, Windows Me™, Windows XP™, Windows NT™, OS/2, or Linux) and one or more application programs. Examples of application programs include authoring applications 276 (e.g., word processing, database programs, spreadsheet programs, or graphics programs) capable of generating documents or other electronic content; client applications 278 (e.g., America Online (AOL) client, CompuServe client, AOL Instant Messenger (AIM) client, interactive television (ITV) client, Internet Service Provider (ISP) client, or instant messaging (IM) client) capable of communicating with other computer users, accessing various computer resources, and viewing, creating, or otherwise manipulating electronic content; and browser applications 280 (e.g., Netscape's Navigator or Microsoft's Internet Explorer) capable of rendering standard Internet content and other content formatted according to standard protocols such as the Hypertext Transfer Protocol (HTTP).
[0027] One or more of the application programs may be installed in the internal or external memory 272 of the general-purpose computer 270 . Alternatively, in another implementation, the client controller 125 may access application programs externally stored in and/or performed by one or more device(s) external to the general-purpose computer 270 .
[0028] The general-purpose computer 270 also includes a central processing unit 282 (CPU) for executing instructions in response to commands from the client controller 125 . The general-purpose computer 270 may include a communication device 284 for sending and receiving data. One example of the communication device 284 is a modem. Other examples include a transceiver, a set-top box, a communication card, a satellite dish, an antenna, a network adapter, or some other mechanism capable of transmitting and receiving data over the communications link 115 through a wired or wireless data pathway 150 . The general-purpose computer 270 also may include a television (“TV”) tuner 286 for receiving television programming in the form of broadcast, satellite, and/or cable TV signals. As a result, the client device 120 can selectively and/or simultaneously display network content received by communications device 284 and TV programming content received by the TV tuner 286 .
[0029] The general-purpose computer 270 may include an input/output interface 288 that enables wired or wireless connection to various peripheral devices 290 . Examples of peripheral devices 290 include, but are not limited to, a mouse 291 , a mobile phone 292 , a personal digital assistant 293 (PDA), an MP3 player (not shown), a keyboard 294 , a display monitor 295 with or without a touch screen input, a TV remote control 296 for receiving information from and rendering information to users, and an audiovisual input device 298 .
[0030] Although FIG. 2 illustrates devices such as a mobile telephone 292 , a PDA 293 , and a TV remote control 296 as being peripheral with respect to the general-purpose computer 270 , in another implementation, such devices may themselves include the functionality of the general-purpose computer 270 and operate as the client device 120 . For example, the mobile phone 292 or the PDA 293 may include computing and networking capabilities and function as a client device 120 by accessing the delivery network 160 and communicating with the host system 110 . Furthermore, the client system 105 may include one, some or all of the components and devices described above.
[0031] Referring to FIG. 3 , an exemplary procedure 300 generally involves rendering an informational tool tip for an e-mail UI. The procedure 300 may be implemented by any type of hardware, software, device, computer, computer system, equipment, component, program, application, code, storage medium, or propagated signal.
[0032] In procedure 300 , the client system 105 receives one or more e-mail messages from one or more e-mail senders (step 305 ). For instance, client system 105 may connect to the host system 110 across a network (e.g., network 160 ) by supplying a user identification and password to a server (e.g., a login server) in order to obtain access to the host system 110 . The host system 110 may deliver an e-mail message from an e-mail sender across a network 160 , and the e-mail message may include, for example, a text message portion, a time of delivery, and a screen name or other identifier for its source.
[0033] Next, the client system 105 renders a user interface (UI) illustrating aspects of at least one of the received messages, examples of which are described below with respect to FIGS. 4A , 4 B, 5 A, 5 B, 6 A, 6 B, and 6 C (step 310 ). In one implementation, the client system 105 renders the UI when an e-mail message from an e-mail sender is provided, and may render other portions of the UI separately at different times. In another implementation, the entire UI, including the e-mail message, may be rendered when the e-mail message is provided. In another implementation, the UI is rendered in response to a user action. For example, the UI may be rendered in response to user selection of an e-mail message. As shown, the UI may provide a preview of a default or selected message, or it may merely show the subjects of the e-mail messages. The UI may be presented using a Web page having text, images, audio, video, and/or other type of content.
[0034] While maintaining the default or the selected message, the user may desire to perceive information about a received e-mail message other than the selected or default message, and may do so by activating an informational tool tip (step 315 ). For example, as discussed below with respect to FIGS. 4B , 5 B, 6 B, and 6 C, the user may invoke an informational tool tip by positioning a mouse 425 or other user input device proximate to or directly over an interface item corresponding to the desired e-mail message. In one implementation, the informational tool tip 430 is activated as soon as the mouse 425 or other user input device is positioned proximate to or directly over the interface tab. In another implementation, the informational tool tip 430 is activated and rendered after the mouse 425 or other user input device remains proximate to or positioned over the interface tab for a predetermined threshold period of time, or after some overt selection activity using the mouse or input device. In yet another implementation, the tool tip may be activated by positioning a mouse or other input device over or proximate to other features of the UI. For example, as shown in FIG. 6B , a user may position the mouse over a new mail status indicator 615 to invoke a tool tip that displays at least a portion of a new message. Also, as shown in FIG. 6C , a user may position the mouse over an icon representing the desired e-mail message 620 to enable activation of the tool tip.
[0035] However, if the user is not configured to invoke the informational tool tip or the tool tip feature is not enabled, the current UI display is maintained (step 320 ).
[0036] If the user is able to invoke the informational tool tip, then the tool tip is invoked (step 325 ). Invoking the tool tip may include rendering the tool tip for a selected e-mail message. As discussed with respect to FIGS. 4B , 5 B, 6 B, and 6 C, the informational tool tip 430 may display all or a portion of the desired e-mail message. In one implementation, a pre-determined or limited number of lines or characters of the desired e-mail message are displayed. In another implementation, a pre-determined number of e-mail fields are displayed. For instance, as shown with respect to tool tip 430 of FIG. 4B , the tool tip may be limited to include two fields of the e-mail message (e.g., the “from” field 415 c and the “subject” field 415 d ) in their entirety and a portion a third field (e.g., the message text). As shown in FIGS. 5B , 6 B, and 6 C, the tool tip 430 may be limited to include only two fields of the e-mail message (e.g., the “from” field 415 c and the “subject” field 415 d ). The fields of the desired e-mail message may be made available to the tool tip by, for example, the client system 105 or the host system 110 , or a combination thereof. The informational tool tip may be rendered in various locations on the display, or it may be non-visual.
[0037] Display of the informational tool tip may be maintained until revoked (step 330 ). Display of the tool tip may be revoked upon expiration of a predetermined period of time, or if the user takes some action to implicitly command removal of the tool tip, e.g., moving the cursor away from a position used to trigger the tool tip (step 335 ). For example, the informational tool tip 430 may be automatically closed or deactivated if the user moves the mouse or input device 425 , or if the mouse or input device 425 is moved from a position over or proximate to the desired e-mail message.
[0038] If the user has revoked the informational tool tip and/or the user is no longer enabled to invoke the informational tool tip, then the display described with respect to step 320 is maintained. If the tool tip has not been revoked, then the display described with respect to step 330 is maintained.
[0039] While some functions of procedure 300 may be performed entirely by the client system 105 , as described, other functions may be performed by the collective operation of the client system 105 and the host system 110 . For example, the informational tool tip may be rendered entirely by the client. However, the informational tool tip may be rendered based upon the host system acting in cooperation with the client.
[0040] In one of various possible implementations, a client system 105 and a host system 110 may interact according to procedure 300 to provide an e-mail tool tip for an e-mail UI. Although not shown in FIG. 3 , the client system 105 and the host system 110 may be directly or indirectly interconnected through known or described delivery networks, examples of which are described with respect to network 160 of FIG. 1 . In such an environment, the e-mail UI may be accessed or updated through a remote device. In another implementation, the procedure 300 may be implemented in a standalone or offline client context. The e-mail UI may be rendered by the standalone/offline device and may be accessed or updated through a remote device in a non-client/host environment such as, for example, a LAN server serving an end user or a mainframe serving a terminal device. Thus, procedure 300 may be implemented for any e-mail UI of any OSP, ISP., or browser.
[0041] FIG. 4A illustrates one example of an e-mail user interface (UI) 400 A that may be presented to a user in response to user manipulation of a general interface actionable item, such as item 610 discussed with respect to FIGS. 6A and 6B . Although UI 400 A may be generated remotely and delivered to a user client system 105 , in general, the UI 400 A will be rendered on or at the client system 105 using software stored on the client system 105 . The UI 400 A includes a folder list 405 that lists the various folders in which e-mail may be placed. For example, new mail folder 405 a may contain new e-mail messages, old mail folder 405 b may contain old e-mail messages, sent mail folder 405 c may contain mail sent by the user, and deleted mail folder 405 d may contain e-mail messages deleted by the user.
[0042] UI 400 A also includes a display area 415 that displays e-mail messages within a designated folder 405 a contained in folder list 405 . For example, as shown in FIG. 4A , display area 415 contains a list of messages 410 contained in designated new mail folder 405 a. The messages 410 include messages 410 a, 410 b, 410 c, 410 d, and 410 e. Each message 410 contains one or more fields. For example, the messages 410 shown in display area 415 each contain a type field 415 a, a date field 415 b, a from field 415 c, and a subject field 415 d. A set of controls 420 is provided for the user to manipulate each of the e-mail messages 410 . Controls 420 include a control 422 that enables the user to read one of the e-mail messages 410 . Once control 422 is acted on by a user, the corresponding e-mail message is read and a separate UI is rendered in order for the user to read the designated e-mail message.
[0043] A preview pane 417 is provided to allow a user to preview a default or a selected message. In the example of FIG. 4A , the preview pane 417 shows information about a selected or default message 410 a, including the “From” field 415 c, the “To” field 417 a, the “Date” field 415 b, the “Subject” field 415 d, and a portion of the message text 417 b. The preview pane display remains visible unless manually deactivated by user manipulation of UI display control options.
[0044] FIG. 4B illustrates another example of an e-mail UI 400 B that is similar to the example discussed above with respect to FIG. 4A . In the example of FIG. 4B , an informational tool tip 430 is invoked on the e-mail UI to provide the user with a perceivable indication of least of a portion of an e-mail message that is not otherwise being actively displayed. For example, the informational tool tip 430 may show all or a portion of the desired e-mail message 410 b.
[0045] In the example of FIGS. 4A and 4B , the standard interface being displayed includes a subject line for the non-selected e-mail messages 410 b, 410 c, 410 d, 410 e, but it does not display the body of these non-selected e-mail messages. Yet, in the example of FIG. 4B , in response to a user action with respect to e-mail message 410 b (e.g., movement of a cursor 425 over e-mail 410 b ), the tool tip 430 is invoked to enable perception of at least a portion of the body of e-mail message 410 b. More specifically, to activate and render the informational tool tip 430 , the user may position a pointer 425 of a mouse or other user input device proximate to or over a field corresponding to e-mail message 410 b.
[0046] As shown in FIG. 4B , the pointer 425 is positioned over the type field 415 a for e-mail message 410 b. In another implementation, the informational tool tip 430 is activated and rendered after the pointer 425 remains proximate to or positioned over a field of the desired e-mail message 410 b for a predetermined threshold period of time, or after some overt activities taken using the mouse or input device with respect to e-mail 410 b.
[0047] The user may close or deactivate the informational tool tip 430 . In one implementation, the informational tool tip 430 may be automatically closed or deactivated if the user moves the pointer 425 . For example, if the pointer 425 is moved from a position over or proximate to the desired e-mail message 410 b. As shown in the implementation of FIG. 4B , the informational tool tip shows all or a portion of the body of the desired e-mail message 410 b.
[0048] FIG. 5A illustrates one example of an e-mail user interface (UI) 500 A displaying a particular received e-mail message 410 a. The UI 500 A shows information about the selected or default message 410 a, including the “From” field 415 c, the “To” field 417 a, the “Date” field 415 b, the “Subject” field 415 d, and the message text 417 b. UI 500 A may include interface controls 505 , including interface controls that display the previous 505 a and the next 505 b e-mail messages.
[0049] FIG. 5B illustrates an example of an UI 500 B similar to UI 500 A described above with respect to FIG. 5A . In the example of FIG. 5B , an informational tool tip 530 may be provided for UI 500 B to provide the user with a perceivable indication of at least a portion of an e-mail message that is not otherwise being actively displayed by UI 500 A. For example, in response to a mouse rollover of the Next button, the informational tool tip 530 may show all or a portion of the desired e-mail message 410 b with e-mail sender “GabbyGrace,” without the user needing to take action that would cause the desired e-mail message 410 b to replace e-mail message 410 a as the selected or default message. In the example of FIG. 5B , the tool tip 530 shows the from field and the subject field of message 410 b. The informational tool tip may be rendered in various locations on the display. For example, the tool tip may be rendered proximate or close to the interface control 405 b to which the tool tip corresponds, which, in this case, is near the Next button.
[0050] FIG. 6A illustrates an example of a user interface (UI) 600 A that may be presented to a user of an online service provider such as AOL. The UI 600 includes a toolbar 605 for quickly enabling activation of features such as, for example, reading or writing e-mail, exchanging IM messages with another user, entering chat areas with other users, shopping or accessing the Internet. The toolbar 605 may include one or more general interface actionable items 610 , 620 , 630 , 640 , and 650 , each of which is configured to enable activation of an associated UI. The actionable item may be, for example, a button or a tab.
[0051] FIG. 6B illustrates another example of an e-mail user interface (UI) 600 B that may be presented to a user. UI 600 B is similar to the examples discussed above with respect to FIG. 6A . In the example of FIG. 6B , an informational tool tip 630 may be provided for the UI 600 B to provide the user with perceivable indication that at least a portion of an e-mail message not otherwise actively displayed. For example, as shown in FIG. 6B , the display of all e-mail UIs have been minimized, and a new mail indicator 615 is provided for the user and indicates that a new e-mail message is present. As shown, a user has positioned a pointer 425 proximate to or directly over new mail indicator 615 in order to render the informational tool tip 630 . In response, the informational tool tip 630 is activated as described previously with respect to FIGS. 4B and 5B .
[0052] FIG. 6C illustrates another example of an e-mail user interface (UI) 600 C that may be presented to a user. UI 600 C is similar to the examples discussed above with respect to FIGS. 6A and 6B . In the example of FIG. 6C , icons 620 , 625 , 630 correspond to e-mail messages which have been minimized and are not presently being displayed. In the example of FIG. 6C , a user has positioned a pointer 425 proximate to or over icon 620 in order to render the informational tool tip 630 .
[0053] FIG. 7 illustrates an exemplary procedure 700 for opening and populating a tool tip window. The procedure 700 may be implemented by any type of hardware, software, device, computer, computer system, equipment, component, program, application, code, storage medium, or propagated signal.
[0054] In procedure 700 , the overt or inferred selection of an interface tab or other interface item corresponding to an e-mail is detected (step 705 ). For example, a selection may be inferred by the positioning of a pointer over or proximate to the interface tab or other interface item. In one implementation, if the position of the pointer is proximate to or positioned over the interface tab, or remains so positioned for a predetermined threshold period of time, a selection of the interface tab or other interface item is inferred. An overt selection of an interface tab or other interface item may also be made. For example, a button or other control on a mouse or other input device may be manipulated to make the overt selection.
[0055] The current window information is maintained (step 710 ). For example, referring to FIG. 5A , display of the selected or default e-mail message 410 a is maintained.
[0056] Next content from within the e-mail message corresponding to the interface tab or other interface item is retrieved (step 715 ). In one implementation, all of the content of the e-mail message is retrieved. In another implementation, only a portion of the content of the e-mail message is retrieved. The tool tip is then opened and populated (step 720 ) with the retrieved content. For example, the tool tip may be opened and may appear as a rectangular pop-up window proximate to the interface tab over which the mouse is positioned. In other implementations, the tool tip may be opened in other locations on the display. The window may be automatically closed based on a timeout or based on an inferred intent to close the window, rather than an express or overt closing instruction by the user.
[0057] The relative placement of steps of described processes with respect to other steps and with respect to each other, such as, for example, steps 305 - 335 in FIG. 3 and steps 705 - 720 in FIG. 7 , may vary, and one or more steps may be eliminated altogether.
[0058] Other implementations are within the scope of the following claims. For example, although the examples above are given in an e-mail context, other communications systems with similar attributes may be used. Also, the UI may be a viewable interface, an audible interface, a tactile interface, or any combination thereof. | An interface enables perception of information regarding e-mail communications. The interface includes an e-mail application user interface that enables perception of e-mail message information for one or more e-mails received by an e-mail participant and that enables active display of one or more of the received e-mails selected by the e-mail participant, The interface also includes a mechanism that determines a request for e-mail message information for one of the e-mails from within a desired e-mail message that is not actively displayed. The interface further includes an informational tool tip that provides a temporary perceivable indication to the e-mail participant of at least a portion of the requested information for the desired e-mail message while maintaining active display of the one or more selected e-mails. | 7 |
BACKGROUND OF THE INVENTION
[0001] This invention relates to piezoelectric ink jet modules.
[0002] A piezoelectric ink jet module includes a module body, a piezoelectric element, and an electrical connection element for driving the piezoelectric element. The module body, usually carbon or ceramic, is typically a thin, rectangular member into the surfaces of which are machined a series of ink reservoirs that serve as pumping chambers for ink. The piezoelectric element is disposed over the surface of the jet body to cover the pumping chambers and position the piezoelectric material in a manner to pressurize the ink in the pumping chambers to effect jetting.
[0003] In a typical shear mode piezoelectric ink jet module, a single, monolithic piezoelectric element covers the pumping chambers to provide not only the ink pressurizing function but also to seal the pumping chambers against ink leakage. The electrical connection is typically made by a flex print positioned over the exterior surface of the piezoelectric element and provided with electrical contacts at locations corresponding to the locations of the pumping chambers. An example of a piezoelectric shear mode ink jet head is described in U.S. Pat. No. 5,640,184, the entire contents of which is incorporated herein by reference.
[0004] In one known ink jet module, available from Brother, a resin diaphragm is provided next to each of the pumping chambers. The central region of each diaphragm is pumped by a piezoelectric feature. Electrodes are embedded in the piezoelectric material.
SUMMARY OF THE INVENTION
[0005] This invention relates to a piezoelectric ink jet head that includes a polymer, preferably a flex print, located between the piezoelectric element and the pumping chambers in the jet body. The polymer seals the pumping chambers and also positions the electrodes on the side of the piezoelectric element in which motion is effected, which can reduce the magnitude of the drive voltage required for operation. The compliant flex print material also can provide electrical, mechanical, and fluidic pressure isolation between pumping chambers, which improves jetting accuracy.
[0006] Thus, in one aspect, the invention features a piezoelectric element that is positioned to subject the ink within an ink reservoir to jetting pressure. A flexible material carries electrical contacts arranged for activation of said piezoelectric element and is positioned between the reservoir and the piezoelectric element in a manner to seal the reservoir.
[0007] Implementations of the invention may include one or more of the following features. The material may be a polymer. The ink reservoir may be defined by a multi-element module body. An ink fill flow path leading to the reservoir may be sealed by the polymer. The polymer may include an area that is not supported. The piezoelectric element may be sized to cover the reservoir without covering the ink fill flow path. The module may include a series of reservoirs all covered by a single piezoelectric element, or in other examples by separate respective piezoelectric elements. The module may be a shear mode piezoelectric module. The piezoelectric element may be a monolithic piezoelectric member.
[0008] In other general aspects of the invention, the flexible material over the flow path contains an area that is not supported; the piezoelectric element spans the ink reservoir and is positioned to subject the ink within the reservoir to jetting pressure; and electrical contacts are located only on a side of the piezoelectric element adjacent to the ink reservoir. In some implementations, the contacts may be thinner than 25 microns, preferably thinner than 10 microns.
[0009] Other features and advantages will become apparent from the following description and from the claims.
DESCRIPTION
[0010] We first briefly describe the drawings.
[0011] FIG. 1 is an exploded view of a shear mode piezoelectric ink jet print head;
[0012] FIG. 2 is a cross-sectional side view through an ink jet module;
[0013] FIG. 3 is a perspective view of an ink jet module illustrating the location of electrodes relative to the pumping chamber and piezoelectric element;
[0014] FIG. 4A is a graph of the field lines in a piezo electric element, while FIG. 4B illustrates element displacement when a driving voltage is applied;
[0015] FIG. 5 is an exploded view of another embodiment of an ink jet module;
[0016] FIG. 6 is a graph of jet velocity data for a 256 jet embodiment of the print head.
[0017] Referring to FIG. 1 , a piezoelectric ink jet head 2 includes multiple modules 4 , 6 which are assembled into a collar element 10 to which is attached a manifold plate 12 , and an orifice plate 14 . Ink is introduced through the collar 10 to the jet modules which are actuated to jet ink from the orifices 16 on the orifice plate 14 . An exemplary ink jet head is described in U.S. Pat. No. 5,640,184, incorporated supra, and is available as Model CCP-256 (Spectra, Inc., Hanover, N.H.).
[0018] Each of the ink jet modules 4 , 6 includes a body 20 , which is formed of a thin rectangular block of a material such as sintered carbon or ceramic. Into both sides of the body are machined a series of wells 22 which form ink pumping chambers. The ink is introduced through an ink fill passage 26 which is also machined into the body.
[0019] The opposing surfaces of the body are covered with flexible polymer films 30 , 30 ′ that include a series of electrical contacts arranged to be positioned over the pumping chambers in the body. The electrical contacts are connected to leads, which, in turn, can be connected to a flex print 32 , 32 ′ including driver integrated circuit 33 , 33 ′. The films 30 , 30 ′ may be flex prints (Kapton) available from Advanced Circuit Systems located in Franklin, N.H. Each flex print film is sealed to the body 20 by a thin layer of epoxy. The epoxy layer is thin enough to fill in the surface roughness of the jet body so as to provide a mechanical bond, but also thin enough so that only a small amount of epoxy is squeezed from the bond lines into the pumping chambers.
[0020] Each of the piezoelectric elements 34 , 34 ′, which may be a single monolithic PZT member, is positioned over the flex print 30 , 30 ′. Each of the piezoelectric elements 34 , 34 ′ have electrodes that are formed by chemically etching away conductive metal that has been vacuum vapor deposited onto the surface of the piezoelectric element. The electrodes on the piezoelectric element are at locations corresponding to the pumping chambers. The electrodes on the piezoelectric element electrically engage the corresponding contacts on the flex print 30 , 30 ′. As a result, electrical contact is made to each of the piezoelectric elements on the side of the element in which actuation is effected. The piezoelectric elements are fixed to the flex prints by thin layers of epoxy. The epoxy thickness is sufficient to fill in the surface roughness of the piezo electric element so as to provide a mechanical bond, but also thin enough so that it does not act as an insulator between the electrodes on the piezoelectric element and the electrodes on the flex print. To achieve good bonds, the electrode metallization on the flex print should be thin. It should be less than 25 microns, and less than 10 microns is preferred.
[0021] Referring to FIG. 2 , the piezoelectric elements 34 , 34 ′ are sized to cover only the portion of the body that includes the machined ink pumping chambers 22 . The portion of the body that includes the ink fill passage 26 is not covered by the piezoelectric element. Thus the overall size of the piezoelectric element is reduced. Reducing the size of the piezoelectric element reduces cost, and also reduces electrical capacitance of the jet, which reduces jet electrical drive power requirements.
[0022] The flex prints provide chemical isolation between the ink and the piezoelectric element and its electrodes, providing more flexibility in ink design. Inks that are corrosive to metal electrodes and inks that may be adversely affected by exposure to electrical voltages such as water based inks can be used.
[0023] The flex prints also provide electrical isolation between the jet body and the ink, on one hand, and the piezoelectric element and its electrodes on the other hand. This allows simpler designs for jet drive circuitry when the jet body or the ink in the pumping chamber is conductive. In normal use, an operator may come into contact with the orifice plate, which may be in electrical contact with the ink and the jet body. With the electrical isolation provided by the flex print, the drive circuit does not have to accommodate the instance where an operator comes in contact with an element of the drive circuit.
[0024] The ink fill passage 26 is sealed by a portion 31 , 31 ′ of the flex print, which is attached to the exterior portion of the module body. The flex print forms a non-rigid cover over (and seals) the ink fill passage and approximates a free surface of the fluid exposed to atmosphere. Covering the ink fill passage with a non-rigid flexible surface reduces the crosstalk between jets.
[0025] Crosstalk is unwanted interaction between jets. The firing of one or more jets may adversely affect the performance of other jets by altering jet velocities or the drop volumes jetted. This can occur when unwanted energy is transmitted between jets. The effect of providing an ink fill passage with the equivalent of a free surface is that more energy is reflected back into the pumping chamber at the fill end of a pumping chamber, and less energy enters the ink fill passage where it could affect the performance of neighboring jets.
[0026] In normal operation, the piezoelectric element is actuated first in a manner that increases the volume of the pumping chamber, and then, after a period of time, the piezoelectric element is deactuated so that it returns to its original position. Increasing the volume of the pumping chamber causes a negative pressure wave to be launched. This negative pressure starts in the pumping chamber and travels toward both ends of the pumping chamber (towards the orifice and towards the ink fill passage as suggested by arrows 33 , 33 ′). When the negative wave reaches the end of the pumping chamber and encounters the large area of the ink fill passage (which communicates with an approximated free surface), the negative wave is reflected back into the pumping chamber as a positive wave, travelling towards the orifice. The returning of the piezoelectric element to its original position also creates a positive wave. The timing of the deactuation of the piezoelectric element is such that its positive wave and the reflected positive wave are additive when they reach the orifice. This is discussed in U.S. Pat. No. 4,891,654, the entire content of which is incorporated herein by reference.
[0027] Reflecting energy back into the pumping chamber increases the pressure at the orifice for a given applied voltage, and reduces the amount of energy transmitted into the fill area which could adversely affect other jets as crosstalk.
[0028] The compliance of the flex print over the fill area also reduces crosstalk between jets by reducing the amplitude of pressure pulses that enter the ink fill area from firing jets. Compliance of a metal layer in another context is discussed in U.S. Pat. No. 4,891,654.
[0029] Referring to FIG. 3 , the electrode pattern 50 on the flex print 30 relative to the pumping chamber and piezoelectric element is illustrated. The piezoelectric element has electrodes 40 on the side of the piezoelectric element 34 that comes into contact with the flex print. Each electrode 40 is placed and sized to correspond to a pumping chamber 45 in the jet body. Each electrode 40 has an elongated region 42 , having a length and width generally corresponding to that of the pumping chamber, but shorter and narrower such that a gap 43 exists between the perimeter of electrode 40 and the sides and end of the pumping chamber. These electrode regions 42 , which are centered on the pumping chambers, are the drive electrodes. A comb-shaped second electrode 52 on the piezoelectric element generally corresponds to the area outside the pumping chamber. This electrode 52 is the common (ground) electrode.
[0030] The flex print has electrodes 50 on the side 51 of the flex print that comes into contact with the piezoelectric element. The flex print electrodes and the piezoelectric element electrodes overlap sufficiently for good electrical contact and easy alignment of the flex print and the piezoelectric element. The flex print electrodes extend beyond the piezoelectric element (in the vertical direction in FIG. 3 ) to allow for a soldered connection to the flex print 32 that contains the driving circuitry. It is not necessary to have two flex prints 30 , 32 . A single flex print can be used.
[0031] Referring to FIGS. 4A and 4B , a graphical representation of the field lines in a piezoelectric element and the resulting displacement of the piezoelectric element are shown for a single jet. FIG. 4A indicates theoretical electric field lines in the piezoelectric element, and FIG. 4B is an exaggeration of the displacement of the piezoelectric element during actuation for illustration purposes. The actual displacement of the piezoelectric element is approximately 1/10,000 the thickness of the piezoelectric element (1 millionth of an inch). In FIG. 4A , the piezoelectric element is shown with electrodes 70 , 71 on the lower surface next to the jet body 72 , and air 74 above the piezoelectric element 76 . For simplicity, the kapton flex print between the piezoelectric element and jet body is not shown in this view. The drive electrodes 70 are centered on the pumping chambers 78 , and the ground electrode is located just outside the pumping chambers. Application of a drive voltage to the drive electrode results in electric field lines 73 as shown in FIG. 4A . The piezoelectric element has a poling field 75 that is substantially uniform and perpendicular to the surface containing the electrodes. When the electric field is applied perpendicularly to the poling field, the piezoelectric element moves in shear mode.
[0032] When the electric field is applied parallel to the poling field, the piezoelectric element moves in extension mode. In this configuration with ground and drive electrodes on the side of the piezoelectric element that is next to the pumping chambers, for a given applied voltage, the displacement of the surface of the piezoelectric element adjacent to the pumping chamber can be substantially greater than if the electrodes were on the opposite surface of the piezoelectric element.
[0033] The bulk of the displacement is due to the shear mode effect, but in this configuration, parasitic extension mode works to increase the displacement. In the piezoelectric element, in the material between the common and the drive electrodes, the electric field lines are substantially perpendicular to the poling field, resulting in displacement due to shear mode. In the material close to the electrodes, the electric field lines have a larger component that is parallel to the poling field, resulting in parasitic extension mode displacement. In the area of the common electrodes, the piezoelectric material extends in a direction away from the pumping chamber. In the area of the drive electrode, the component of the electric field that is parallel to the poling field is in the opposite direction. This results in compression of the piezoelectric material in the area of the drive electrode. This area around the drive electrode is smaller than the area between the common electrodes. This increases the total displacement of the surface of the piezoelectric element that is next to the pumping chamber.
[0034] Overall, more displacement may be achieved from a given drive voltage if the electrodes are on the pumping chamber side of the piezoelectric element, rather than on the opposite side of the piezoelectric element. In embodiments, this improvement may be achieved without incurring the expense of placing electrodes on both sides of the piezoelectric element.
[0035] Referring to FIG. 5 , another embodiment of a jet module is shown. In this embodiment, the jet body is comprised of multiple parts. The frame of the jet body 80 is sintered carbon and contains an ink fill passage. Attached to the jet body on each side are stiffening plates 82 , 82 ′, which are thin metal plates designed to stiffen the assembly. Attached to the stiffening plates are cavity plates 84 , 84 ′, which are thin metal plates into which pumping chambers have been chemically milled. Attached to the cavity plates are the flex prints 30 , 30 ′, and to the flex prints are attached the piezoelectric elements 34 , 34 ′. All these elements are bonded together with epoxy. The flex prints that contain the drive circuitry 32 , 32 ′, are attached by a soldering process.
[0036] Describing the embodiment shown in FIG. 5 in more detail, the jet body is machined from sintered carbon approximately 0.12 inches thick. The stiffening plates are chemically milled from 0.007 inch thick kovar metal, with a fill opening 86 per jet that is 0.030 inches by 0.125 inches located over the ink fill passage. The cavity plates are chemically milled from 0.006 inch thick kovar metal. The pumping chamber openings 88 in the cavity plate are 0.033 inches wide and 0.490 inches long. The flex print attached to the piezoelectric element is made from 0.001 inch Kapton, available from The Dupont Company. The piezoelectric element is 0.010 inch thick and 0.3875 inches by 2.999 inches. The drive electrodes on the piezoelectric element are 0.016 inches wide and 0.352 inches long. The separation of the drive electrode from the common electrode is approximately 0.010 inches. The above elements are bonded together with epoxy. The epoxy bond lines between the flex print and the piezoelectric element have a thickness in the range of 0 to 15 microns. In areas were electrical connection must be made between the flex print and the piezoelectric element, the thickness of the epoxy must be zero at least in some places, and the thickness of the epoxy in other places will depend on surface variations of the flex print and the piezoelectric element. The drive circuitry flex print 32 is electrically connected to the flex print 30 attached to the piezoelectric element via a soldering process.
[0037] Referring to FIG. 6 , velocity data is shown for a 256 jet print head of the design in FIG. 5 . The velocity data is presented normalized to the average velocity of all the jets. Two sets of data are overlaid on the graph. One set is the velocity Of a given jet measured when no other jets are firing. The other set of data is the velocity of a given jet when all other jets are firing. The two sets of data almost completely overlaying one another is an indication of the low crosstalk between jets that this configuration provides.
Other Embodiments
[0038] In another embodiment, the piezoelectric, elements 34 , 34 ′ do not have electrodes on their surfaces. The flex prints 30 , 30 ′ have electrodes that are brought into sufficient contact with the piezoelectric element and are of a shape such that electrodes on the piezoelectric material are not required. This is discussed in U.S. Pat. No. 5,755,909, the entire content of which is incorporated herein by reference.
[0039] In another embodiment, the piezoelectric elements 34 , 34 ′ have electrodes only on the surface away from the pumping chambers.
[0040] In another embodiment, the piezoelectric elements shave drive and common electrodes on the surface away from the pumping chambers, and a common electrode on the side next to the pumping chambers. This electrode configuration is more efficient (more piezoelectric element deflection for a given applied voltage) than having electrodes only on the surface of the piezoelectric element away from the pumping chambers.
[0041] This configuration results in some electric field lines going from one surface of the piezoelectric element to the other surface, and hence having a component parallel to the poling field in the piezoelectric element. The component of the electric field parallel to the poling field results in extension mode deflection of the piezoelectric element. With this electrode configuration, the extension mode deflection of the piezoelectric element causes stress in the plane of the piezoelectric element. Stress in the plane of the piezoelectric element caused by one jet can adversely affect the output of other jets. This adverse effect varies with the number of jets active at a given time, and varies with the frequency that the jets are activated. This is a form of crosstalk. In this embodiment, efficiency is traded for crosstalk.
[0042] In the embodiment with electrodes on the surface of the piezoelectric element adjacent to the pumping chambers, no efficiency is gained from adding a ground electrode on the surface of the piezoelectric element away from the pumping chambers. Adding a ground electrode to the surface of the piezoelectric element away from the pumping chamber will increase the electrical capacitance of the jet and so will increase the electrical drive requirements.
[0043] In another embodiment, the piezoelectric elements 34 , 34 ′ have drive and common electrodes on both surfaces.
[0044] Still other embodiments are within the scope of the following claims. For example, the flex print may be made of a wide variety of flexible insulative materials, and the dimensions of the flex print may be any dimensions that will achieve the appropriate degrees of compliance adjacent the ink reservoirs and adjacent the fill passage. In regions where the flex print seals only the fill passage and is not required to provide electrical contact, the flex print could be replaced by a compliant metal layer. | A piezoelectric ink jet head that includes a polymer film, for example a flex print, located between the piezoelectric element and the reservoirs in the jet body. The film provides an efficient seal for the reservoirs and also positions the electrodes on the side of the piezoelectric element in which motion is effected, which can reduce the magnitude of the drive voltage. This location of the compliant flex print material also can enhance electrical and mechanical isolation between reservoirs, which improves jetting accuracy. The compliance of the polymer also reduces strain on the ink jet head. | 1 |
BACKGROUND OF THE INVENTION
This invention pertains generally to missile control systems and particularly to a system of such type used to interdict a guided missile in flight toward a target.
It has been known for some time that so-called "repeater" jammers carried on an expendable decoy may effectively be employed to protect a target against a radar-controlled guided missile. Briefly, such a jammer includes a responder which produces signals that are, substantially, replicates of the echo signals from a target to be protected except that the amplitude, or apparent origin, or some other significant characteristic of such replicates differ from the echo signals from the target to be protected. As a result, the guidance system on the attacking missile is caused to track the decoy rather than the target to be protected.
It is apparent that, if successful diversion of a radar-controlled guided missile from a target to be protected is to be effected, "tracking" on the decoy must be maintained until the guided missile cannot be maneuvered to impact on the target intended to be protected. The requisite deception is, however, difficult to achieve because guidance systems for attacking missiles are now designed to distinguish between echo signals from a target and signals from a decoy whenever the signals from the latter differ to an appreciable degree from a predetermined norm. That is to say, if any one of the many parameters (such as power level, pulse shape, angle, or range rate, to mention a few) of signals from a decoy differs substantially from what may be expected from a target, a modern guidance system will soon recognize the presence of the decoy. In all probability, then, sufficient time will still be available for the attacking missile to be guided to impact on the target desired to be protected.
SUMMARY OF THE INVENTION
With the foregoing background of the invention in mind, it is a primary object of this invention to provide an improved decoy which is also adapted to destroy an attacking radar-controlled guided missile.
The foregoing and other objects, not mentioned, of this invention are attained generally by providing, in an expendable decoy launchable from a target to be protected toward an attacking missile, (a) a repeater jammer for transmitting amplified replicas of echo signals from such target; (b) flight control means for the decoy for causing the amplified replicas from the decoy to appear to an attacking missile to have originated at substantially the same range as the target to be protected but from a different direction so that such missile is diverted from its intended course; and (c) a warhead with requisite fuzing for exploding such warhead when attacking missile arrives within lethal range of the decoy.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of this invention, reference is made to the following description of a preferred embodiment of this invention as shown in the accompanying drawings, wherein:
FIG. 1 is a sketch, greatly exaggerated for illustrating purposes, of a tactical situation in which the concepts of this invention are intended to be used; and
FIGS. 2A and 2B are sketches showing how a decoy according to this invention is effective to divert an attacking missile from its intended course.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, it will be realized that a target to be protected, here a ship 10, is equipped with any known fire control system 12 (as, for example, a system such as the one shown and described in the copending United States patent application entitled "Shipboard Point Defense System", Ser. No. 823,890 filed Jul. 28, 1977 and assigned to the same assignee as this application). Briefly, the just-mentioned system includes a radar for searching the air space around a ship to detect and track any objects, such as a missile 14 (here assumed to be a guided missile equipped with an active radar guidance system 16) on a collision course with the ship 10. The fire control system 12 preferably, but not necessarily, is adapted to determine the probable position of the missile 14 at any future moment. The guidance system 16 on the missile 14 here is assumed to include a pulse radar (not shown) with a beam having a main lobe of finite size initially illuminating the ship 10 to provide echo signals from which guidance commands for the missile 14 are provided in any known manner. For example, the guidance system 16 could be operating under well-known proportional navigation principles whereby the missile 14 is intended to be guided to an intercept with the ship 10 by minimizing the "line of sight" error rate. It will also be assumed that the guidance system 16 also includes signal processing equipment which is adapted to measure various parameters of chosen echo signals normally to allow echo signals from the ship 10 to be separated from unwanted echo signals. Specifically, well-known discriminants such as, for example, range gates, Doppler filters, range rate, angle rate and amplitude detectors are assumed to be incorporated in the guidance system 16. Such discriminants also must be satisfied by any decoy before the missile 14 may be diverted from its intended course. Obviously, then, rather stringent requirements are placed on the nature and time of occurrence of any signals from the decoy so that "capture" of the guidance system 16 may be effected in order to divert the missile 14 from its intended course.
The air frame and propulsion means of the decoy 18 here is contemplated to be similar to those of a SEA SPARROW missile, although other types of missiles or drone aircraft could be used so long as the chosen vehicle may be maneuvered in a way to be discussed to reach a position near the line of sight between the ship 10 and the missile 14 (such as indicated at "t L+1 " in FIG. 2A). That is to say, the chosen missile or drone aircraft here is of a type which may be launched and maneuvered into a position along the line of sight between the missile 14 and the ship 10.
A transponder 18T, here simply a rear antenna 18R, an amplifier 18A and a front antenna 18F is provided on the decoy 18 to retransmit echo signals from the ship 10 to the missile 14. It will be recognized that, when the decoy 18 and ship 10 are on the same line of sight from the missile 14, (absent any delay or distortion in the transponder 18T) the retransmitted echo signals (referred to hereinafter as the "decoy signals") at the missile 14 correspond substantially with the echo signals from the ship 10. To put it another way, under such conditions, the time of arrival and the frequency spectrum of the echo signals from the ship 10 are the same as the decoy signals; it is evident, however, that the amplitude of the decoy signals is greater (as a function of the overall gain of the transponder 18T and the geometry existing in any particular situation) than the amplitude of the echo signals. Because the only substantial difference between two signals received at the missile 14 is the difference between the amplitudes of the two, the guidance system 16 is constrained to track the decoy signals.
The decoy 18 is then caused to move away from the line of sight between the missile 14 and the ship 10 to a position such as is illustrated at "t L+2 " in FIG. 2A. The then existing exemplary relationships (shown in FIG. 2B) between the ship, the decoy and the missile (such elements being represented respectively by the numerals 10', 18', 14') obtain. Remembering that the decoy 18' is being tracked by the missile 14' and that the ship 10' and the decoy 18' are not on a common line of sight, it may be seen that the accumulated angle error, E, in the course of the missile 14' is a function of the angle A and, for a given range, R SM , between the missile 14' and the ship 10' a function of the ratio between the ranges between the ship 10' and the decoy 18' and between the decoy 18' and the missile 14'. It will also be recognized that the difference between the times of arrival at the missile 14' of the echo signals from the ship 10' and the decoy signals is directly related to the difference between the lengths (measured from the ship 10' to the missile 14') of the paths of the two signals. With the lengths of the paths of the two signals remaining substantially equal, it is still not possible to discriminate between the two on a "difference in range" basis.
It will be noted in FIG. 2B that, with the accumulated angle error, E, as shown the main lobe 21A of the radar beam originating at the missile 14' is pointed at the decoy 18' and that an area, designated the effective illuminated area 23A, centered on point 18' and containing the ship 10' is illuminated. It will be appreciated that sea echoes are returned from points (not indicated) within the effective illuminated area 23A, the size and distribution of such echoes being dependent upon sea conditions and the shape of the main lobe 21A. In contrast, if the ship 10' were being tracked, the main lobe of the radar beam (indicated in broken line and designated main lobe 27I) would be positioned to illuminate an area (designated intended illumination area 23I) centered on the ship 10'. Again, sea echoes, substantially the same as the sea echoes from the effective illuminated area 23A, would also be returned. The amplitude of the echo signals from the ship 10' would, however, be less in the former situation than in the latter by reason of the fact that the full "two-way" gain of the radar antenna is not there achieved. That is to say, the shape of the main lobe 21A and its orientation with respect to the ship 10' may be deemed to cause "two-way" attenuation of any target not on the centerline of the main lobe 21A. On the other hand, in the former situation when the decoy 18' is near the ship 10', the decoy signals are subjected only to "one-way" attenuation. This means, then, that the accumulated angle error, E, may exceed the beamwidth of the main lobe 21A (meaning that the ship 10' may be illuminated by a side lobe (not shown)) and still provide sufficiently high signals to the decoy 18' for adequate decoy signals to be transmitted.
If successful deception of the missile 14' is to be effected, the rate of change of the accumulated angle error, E, and the apparent range rate of the decoy signals must not exceed limits defined by the speed and maneuverability of the ship 10 (FIG. 1). To put it another way, if successful deception is to be effected, the dynamic characteristics of the decoy signals must match the possible characteristics of the ship 10. If matching does not occur the guidance system 16 (FIG. 1) may sense the fact that a true target, i.e. the ship 10, is not being tracked and the guidance system 16 may be caused to search for echo signals from the ship 10 (FIG. 1), disregarding the sensed decoy signals.
Fortunately, with a transponder such as the transponder 18T (FIG. 1) carried close to the line of sight between the ship 10' and the missile 14', the apparent propagation delay of the decoy signals always approximates the actual propagation delay of the echo signals from the ship 10', regardless of any maneuvering of the ship 10' or of the actual position of the decoy 18' in flight toward the missile 14'. Therefore, when the accumulated error, E, begins to approach the width of the antenna beam of the radar sensor 16, a "capture" of the missile 14 occurs resulting in missile 14 homing against a point (the decoy) which is outside the angle resolution cell of the ship.
With the missile 14' tracking the decoy 18' and the two approaching each other head-on (or almost head-on) as shown in FIG. 2A, it is apparent that (say at time t L+3 ), the missile 14' and decoy 18' pass closely to one another. If the missile 14' and decoy 18' were to pass one another, the decoy signals would disappear making it necessary for the guidance system 16 (FIG. 1) to reacquire and to track new target signals, such as echo signals from the ship 10'. The pointing error, D, when such a search is begun, may be equal to, or less than, the beam width of the active radar in the guidance system 16 (FIG. 1) and the range error is very small. Therefore, in the situation being discussed, the missile 14' probably could be maneuvered to follow its required recovery course (shown in dashed line) to impact on the ship 10'. Such a course would not be possible, however, if the range from the ship 10' to the point at which the missile 14' and decoy 18' pass each other were too short to allow the requisite maneuvering of the missile 14' to be effected. It would be extremely dangerous to depend entirely on such a possibility because it would entail allowing the missile 14' to close to a rather short range from the ship 10'.
It is contemplated here, in view of the foregoing, to provide a way to destroy the missile 14' before it closes to a short range to the ship 10'. Thus, for example, as shown in FIG. 1, the decoy 18 is provided with a proximity fuze 18PF and a warhead 18W (both of conventional construction) to interdict the missile 14 at a relatively long range, depending upon the range at t L and the relative speeds of the missile 14 and the decoy 18.
It will be observed that the course of the decoy 18 (FIG. 1) is constrained in any given tactical situation to cause the decoy signals to simulate actual target signals. Fortunately, however, with the positions and velocities of the ship 10 and the missile 14 measured and the flight characteristics of the decoy 18 known, a priori, the particular course to be taken by the decoy 18 in any particular tactical system may be calculated and a programmer 18P (here a conventional read-only memory) may be set up immediately prior to launch to provide the requisite command signals to a conventional flight control assembly 18FC in the decoy 18.
Having described a preferred embodiment of the invention, it will now be apparent to one of skill in the art that many changes may be made without departing from the inventive concepts. For example, as mentioned hereinbefore, it is not essential to the invention that the "Sea Sparrow" airframe be used. As a matter of fact, it may be advantageous to modify the "Sea Sparrow" airframe, or to provide a different airframe, to optimize the aerodynamic characteristics of the airframe actually used in a decoy according to the invention so that the "fly-by" range (meaning the range from the ship to be protected to the decoy when the latter is proximate to the attacking missile) is such that the attacking missile cannot be maneuvered to impact on the ship to be protected. A moment's thought will make it clear that such a "fly-by" range is relatively short compared to the range at which an attacking missile may be detected. It follows then that a short "fly-by" range may not readily be achieved with a high speed missile carrying a decoy .unless such a missile is allowed to close to an short range before the decoy is launched. Obviously, then, the ideal airframe would be one which may be accelerated quickly (as may that of the Sea Sparrow) and then, after capture by the decoy of the guidance system on the attacking missile, be decelerated to a speed comparable to that of the ship to be protected. Such an aerodynamic capability, for example, could be achieved by modifying the "Sea Sparrow" to deploy braking parachutes after launch so that, regardless of the range of the attacking missile when the decoy is launched, "fly-by" would not occur until such missile could not be maneuvered to impact on the ship being protected. It is felt, therefore, that this invention should not be restricted to its disclosed embodiment, but rather should be limited only by the spirit and scope of the appended claims. | A method of interdicting a guided missile equipped with an active radar-controlled guidance system is shown to include generating decoy signals in a transponder on an armed decoy launched from a ship being attacked toward such missile, such decoy signals initially obscuring echo signals from the ship to cause the apparent position of the ship (as measured by the active radar-controlled guidance system) to differ from the actual position of the ship, and, when the decoy and guided missile are in proximity with one another, exploding a warhead on the decoy to destroy the guided missile. | 5 |
FIELD OF THE INVENTION
The present invention relates to a method for the localization of heating in a tempering furnace for glass panels, wherein the glass panels are carried and supported by rollers and heated to a desired tempering temperature with hot convection air blasted to the opposite surfaces of the glass panels.
The invention relates also to an apparatus for the localization of heating in a tempering furnace for glass panels, which is provided with rollers for carrying the glass panels, nozzle boxes with nozzles for blasting hot convection air to the opposite surfaces of a glass panel, blowers in a flow communication with the nozzle boxes, intake ports within the furnace in a flow communication with the blowers, and heating resistances for heating the air circulated by the blowers.
BACKGROUND OF THE INVENTION
This type of method and apparatus is disclosed in the Patent publication EP-649821. The heating of glass panels with a convection air blast involves certain problems in terms of providing the glass panels with a uniform distribution of heat over the entire surface area. In particular, the border areas of sizable glass panels tend to heat more than the central areas.
SUMMARY OF THE INVENTION
An object of the invention is to provide a method and apparatus of the above type, capable of controlling more effectively than before the temperature distribution over various areas of a load or individual glass panels to be heated in a convection furnace.
BRIEF DESCRIPTION OF THE DRAWINGS
One exemplary embodiment of the invention will now be described in more detail with reference made to the accompanying drawings, in which
FIG. 1 shows in a schematic plan view an apparatus for implementing a method of the invention;
FIG. 2 shows in a vertical section a convection heating furnace included in an apparatus of the invention, provided with an arrangement of the invention for localized extra heating;
FIG. 2A shows a detail of FIG. 2 in a larger scale; and
FIG. 3 shows a top section of the furnace of FIG. 2 in a cross-section.
DETAILED DESCRIPTION OF THE INVENTION
The description deals first with an apparatus for implementing the method. The apparatus shown in FIG. 1 includes a loading table 1, a convection heating furnace 2, and a chilling station 3. As depicted in more detail in FIGS. 2 and 3, the furnace 2 is provided with nozzle boxes 4 above and nozzle boxes 14 below conveyor rollers 11. The blast of hot convection air for heating a glass panel is effected from nozzle heads 5, 15 associated with the nozzle boxes 4, 14, the nozzles present therein comprising e.g. slit nozzles, jet orifices or jet pipes. The convection air circulation is effected by means of blowers 6, which are in a flow communication with intake ports 16 opening into the furnace. Between the blowers 6 and the intake ports 16 are resistances 17 for heating the air to be circulated. FIG. 3 illustrates an overhead air circulation system, and a respective circulation system is constructed below the array of rollers 11.
The nozzle boxes 4, 14 are parallel to the rollers 11 and the nozzle heads 5, 15 concentrate a blast between the rollers 11.
For the purposes of localized extra heating, the furnace is provided, between the upper nozzle heads 5, with resistances 10 which are spaced in a lateral direction of the furnace as discrete resistances 10a, 10b, 10c, which are selectively switchable on and off, whereby the extra heating can be performed either by means of the middle resistances 10b or with either one of the side resistances 10a, 10c or with a combination of the middle resistance 10b and either one of the side resistances 10a, 10c. As for the resistances arranged successively lengthwise of the furnace, it is possible to switch on one or more resistances anywhere along the length of the furnace.
The resistances 10a have their own power cables 12a, the resistances 10b have their own power cables 12b, and the resistances 10c have their own power cables 12c. The cable system 12 is extended through a heat-insulated furnace roof 13 and connected to current distribution rails present within housings 18. These are in turn connected to a unit 9, fitted with controlled current switches which are operated by means of a computer-aided control system 8. On the other hand, the control system 8 receives the control-required information from scanning or detecting means 7, located in the loading station 1 or between the loading station 1 and the furnace 2. The scanning and detecting means 7 can be based e.g. on the back-reflection of electromagnetic radiation or sound waves from glass. The means 7 may also comprise CCD-cameras or video cameras. The scanning or detecting means 7 are used for reading the load picture of glass panels, i.e. the dimensions and positions of individual glass panels. It is also possible to use glass-contact scanning, e.g. by means of yielding rollers, or scanning carried out by means of small air jets, in which case the jets, when in line with the glass panels, do not transmit the plane of passage of the glass panels. The read load picture is stored in the memory of the control system 8 and compared with predetermined parameters. The comparison results in the identification of critical glass panels, and the resistances 10 are used for focusing radiation heating on the central areas of the critical glass panels for providing extra heating therefor.
The control system 8 may also include a load picture monitor, displaying at the same time a matrix for a multi-zonal radiation heating system and resistances activated for heating at any given time. By means of a display of this type, it is possible to teach the system to choose automatically a given resistance heating picture for a given load picture, such that the extra heating is always focused on the central areas of critical glass panels. The control system 8 includes a program which makes use of preset parameter data to determine the degree of extra heating required for a given glass panel in terms of its thickness, width and length. This requirement for extra heating may still vary according to whether the glass panel is positioned in the mid-section or side section of a furnace. Thus, a decision in terms of resistances to be selectively activated is made automatically on the basis of the program and parameter data used thereby. It is possible to vary such parameter data manually on the basis of operating experiences.
In addition to a resistance picture to be selected, it is of course necessary to make a decision about the starting moment and duration of extra heating in terms of each resistance or resistance zone. This decision is also made on the basis of a communication between the visualization system and the control computer. the selected resistances or resistance zones switch automatically on and off and this switching action can be visible on the monitor of the control system 8 along with a load picture.
The heating resistances 10 may comprise a wound single-wire electrical resistance or double-coated direct resistances (e.g. Thermociax from Philips). The radiation heating elements must be quick in terms of the action time thereof. In addition to overhead radiation heaters, it is possible to employ lower radiation heaters underneath the rollers 11. As an alternative, the resistance heaters 10 can be fitted in the nozzle boxes 4 for producing the locally focused and temporally controlled overheating of convection air to be blasted.
The heating resistances 10 have an outer diameter and positioning between the nozzle heads dimensioned in such a way that the pressure loss of circulation air will be increased as little as possible thereby. In order to achieve this, it is preferred that the distance between the heating elements 10 and the external side surfaces of the nozzle heads 5 be greater than or equal to a half of the minimum distance between the nozzle boxes 4.
Since extra or supplemental heating is not required near the sidelines of a furnace, the resistances 10a, 10b, 10c, set one after the other laterally of the furnace, are only adapted to extend beyond the mid-section of the furnace by about 2/3 of the width of the furnace, providing the edges of the furnace with zones not occupied by resistances. The resistances 10 may cover the entire length of a furnace between all nozzle boxes 4 or just part of the length of a furnace between just a few nozzle boxes.
The invention is not limited to the use of automated visualization system of the load pattern.
The operator may manually select (by push buttons) one of different radiation heat localization programs after having visually assessed the load pattern or dimensions of a glass panel. For instance, if large glass panels of predetermined width are loaded, the operator selects a push button, which is indicated to be used by large glass panels having their width within a predetermined range. | The invention relates to a method and apparatus for the localization or focusing of heating in a tempering furnace for glass panels. Glass panels are carried and supported in a furnace (2) by rollers (11). The furnace is provided with upper and lower nozzle boxes (4, 14), including nozzle heads (5, 15) for blasting hot convection air to heat the glass panels to a tempering temperature. The arrival of a load in the furnace is preceded by reading a load picture and by controlling radiation heat resistances (10) present in the furnace in such a way that radiation heating can be focused on the central areas of critical glass panels to provide extra heating therefor. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an electric blind of vertical type and, more particularly, to an actuator for driving rotating rods borne in the casing frame of the electric blind (which may be either a vertical blind or curtain of electric type) with respective electric motors.
2. Description of the Prior Art
Representatives of the vertical blind according to the prior art are disclosed in U.S. Pat. Nos. 4,306,608 4,262,728 and 4,261,408, for example.
In these vertical blinds, generally speaking, two traverse and tilt rods for traversing and tilting slats are rotatably borne in the casing frame in juxtaposition to each other such that the traverse rod is rotated by its drive motor to traverse a plurality of runners reciprocally in the casing frame and such that the tilt rod is rotated by its drive motor to tilt the slats reciprocally, each of which is suspended from the corresponding one of the runners.
Incidentally, in the vertical blind of electric type, the traverse rod and the tilt rod are borne in the casing frame in parallel with each other such that the traverse rod has its one end connected through a drive transmission to its drive motor and such that the tilt rod has its other end connected through a drive transmission to its drive motor. Thus, in some actuator for actuating the vertical blind of the prior art, each of the rotating rods, i.e., the traverse rod or the tilt rod is given the driving force of the corresponding one of the motors at its one end.
In the prior art described above, either in case the slats suspended from the hooks of the runners are heavy or in case the rotating rods are long, the rotating rods require accordingly increased forces so that large-sized motors have to be mounted in the casing frame. As a result, the casing frame per se has to be enlarged in size, thus raising a problem that it is large-sized to have a rather ugly appearance.
Since a driving force is applied to one end of each rotating rod, moreover, in case the heavy slats are suspended, there arise a problem that a torsion is generated to twist the rotating rods or that the driving force fails to be completely transmitted to the other end of each rotating rod.
In the vertical blind, still moreover, the traverse rod and the tilt rod carry such supports as will be reciprocated by the rotations of the traverse rod so that the gap between the two rods and the gap between the two rods and the casing frame may be held constant to prevent the traverse rod from running out. For this purpose, the plural supports are reciprocated by the rotations of the traverse rod to keep the rod steady. As the vertical blind becomes the larger, the load to be applied to the runners becomes the higher to raise another problem that the traverse rod cannot be kept steady, varying from support to support.
SUMMARY OF THE INVENTION
It is, therefore, a first object of the present invention to provide an actuator for a vertical blind of electric type, which can eliminate the deformations such as torsions of rotating rods to ensure their rotations.
A second object of the present invention is to provide an actuator of the above type, which can easily adjust the tension to be applied to a traverse rod to an appropriate value.
A third object of the present invention is to provide an actuator of the above type, which can prevent rotation transmitting means from being displaced even if the tension is applied to the traverse rod.
A fourth object of the present invention is to provide an actuator of the above type, which has such bearings for the traverse rod as are enabled to endure a high torque by dispersing it.
In an electric blind to be mounted on a mounting support face, comprising: a generally elongatetd casing frame having a pair of longitudinally extending guide rails; relatively long rotating rod means borne rotatably in the longitudinal direction of said casing frame; a plurality of runners made rotatable to run one after another on said guide rails when said rotating rod means is driven; and a plurality of slats each suspended from the corresponding one of said runners, according to a major feature of the present invention, there is provided an actuator for actuating said electric blind, comprising: at least one pair of drive means disposed at two end portions of said casing frame for driving the two ends of said rotating rod means in a manner to eliminate any deformation of said rotating rod means; drive transmission means for transmitting therethrough the driving forces of said drive means to said rotating rod means; and bearing means for bearing said rotating rod means.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects, features and advantages of the present invention will become apparent from the following description to be made with reference to the accompanying drawings
In FIGS. 1 to 7 showing a first embodiment of the present invention:
FIG. 1 is a top plan view showing the overall structure of a vertical blind of electric type incorporating an actuator according to the present invention;
FIG. 2 is a longitudinal vertical section showing the overall structure of FIG. 1;
FIG. 3 is an enlarged transverse section taken along line A--A of FIG. 1;
FIG. 4 is an enlarged transverse section taken along B--B of FIG. 1;
FIG. 5 is an enlarged transverse section taken along line C--C of FIG. 2;
FIG. 6 is an enlarged logitudinal verticla section taken along line D--D of FIG. 2; and
FIG. 7 is a graph presenting the characteristics of motors.
FIGS. 8, 9 and 10 are partially cut-away top plan views showing the overall structure of an actuator according to other embodiments of the present invention.
In FIGS. 11 to 17 showing traverse rod tensing mechanisms to be used with the actuator of the present invention:
FIG. 11 is a partially cut-away top plan view showing a traverse rod tensing mechanism;
FIG. 12 is an exploded perspective view showing the tensing mechanism of FIG. 11;
FIG. 13 is a transverse section taken along line E--E of FIG. 11;
FIG. 14 is a traverse section taken along line F-F of FIG. 11;
FIG. 15 is a longitudinal vertical section showing an essential portion of the traverse rod tensing mechanism of FIGS. 11 to 14;
FIG. 16 is a partially cut-away top plan view showing a modification of the traverse rod tensing mechanism; and
FIG. 17 is a schematic diagram for explaining the actions of the traverse rod tensing mechanisms of FIGS. 15 and 16.
In FIGS. 18 to 22 showing a fitting structure to be used with the actuator of the present invention:
FIG. 18 is a longitudinal section showing a fitting structure for fitting a rotation transmitting mechanism;
FIG. 19 is a perspective view showing the fitting structure of FIG. 18;
FIG. 20 is a longitudinal section showing the fitting structure of FIGS. 18 and 19;
FIG. 21 is a section taken along line G--G of FIG. 20 but shows a modification of the fitting structure; and
FIG. 22 is similar to FIG. 21 but shows another modification of the fitting structure.
In FIGS. 23 to 25 showing a bearing unit to be used with the actuator of the present invention:
FIG. 23 is an exploded perspective view showing the bearing unit;
FIG. 24 is a longitudinal vertical section showing an essential portion of the bearing unit; and
FIG. 25 is an exploded perspective view showing the essential portion of FIG. 24.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described in the following in connection with the embodiments thereof with reference to the accompanying drawings.
In FIGS. 1 to 7, reference numeral 1 generally denotes a casing frame which is made of an aluminum alloy or the like and has a generally square section opened upward. This casing frame 1 is suspended from a support such as the upper frame of a window or a ceiling by means of not-shown mounting brackets. Denoted at numeral 2 is a rod chamber which is defined to extend at one side in the lower portion and along the whole length of the casing frame 1. At the two side walls of the rod chamber 2, there are formed a pair of guide rails 3 which are opposed to each other. In each of the guide rails 3, there are fitted a plurality of pairs of rollers 5, the paired ones of which are pivotally borne at the two ends of each runner 4, such that they can run on the guide rails 3. As shown in FIGS. 4 and 5, the runner 4 is constructed of a casing 6 which is made of a synthetic resin or the like in a flattened shape. This casing 6 is divided into two compartments 7 and 8, and a worm shaft 9 is rotatably fitted upright in the center of the casing 6 between the two compartments 7 and 8. This worm shaft 9 is in meshing engagement with a worm gear 10 which is rotatably borne in the compartment 7. This worm gear 10 is formed on its axis with a square-shaped fitting bore 11 to which is keyed in a meshing and slidable engagement a tilt rod 12 having a cross section. Denoted at numeral 13 is a hook which is connected to the lower end of the worm shaft 9 and from which is suspended a slat 14. This slat 14 is offset from the center line of the casing frame 1 such that its edge portion 14a is positioned inside of the perpendicular E of the end portion of the casing frame 1.
On the other hand, the other compartment 8 of the casing 6 of the runner 4 does not accommodate anything therein but is formed on its center line with a circular bore 15 in which is slidably and loosely fitted a traverse rod 16 having the construction of a screw shaft. The compartment 8 is further formed in its side wall with an opening 18 in which is fitted a spacer 17. On the other hand, the not-shown leading one of the runners 4 has its compartment 8 formed in its side wall with a circular hole in which is slidably and loosely fitted the traverse rod 16. The other wall of the compartment 8 is formed with a cross-shaped fitting hole to which is keyed the traverse rod 16. Moreover, the leading runner is preceded by a not-shown steady support.
In the rod chamber 2 formed at one side of the lower portion of the casing frame 1, there are arranged in parallel the aforementioned traverse rod 16 and tilt rod 12 which are pivotally borne by means of bearings 22 and 23 in side plates 20 and 21 which in turn are fastened to the two ends of the casing frame 1 by screws 19.
At one end portion of the casing frame 1 and over the rod chamber 2, there are accommodated sequentially in the recited order a traverse controller 24 of the traverse rod 16, a first traverse drive motor 25, a tilt controller 26 of the tilt rod 12, a first tilt drive motor 27, and a control box 28 for accommodating a not-shown electric circuit or the like therein.
Within the traverse and tilt controllers 24 and 26, respectively, there are borne in limit boxes 32 and 33 threaded rods 30 and 31 which are connected to the respective output shafts of the drive motors 25 and 27. Transverse and tilt control members 34 and 35 are movably screwed on those threaded rods 30 and 31. 0n threaded rods 36 and 37 which are borne in parallel with the threaded rods 30 and 31, respectively, there are movably carried microswitches 38a and 38b, and 39a and 39b, the paired ones of which are positioned across the aforementioned traverse and tilt control members 34 and 35, respectively. As the threaded rods 30 and 31 are rotated by the driving forces of the first traverse drive motor 25 and a later-described second traverse drive motor 25a, and the first tilt drive motor 27 and a later-described second tilt drive motor 27a, the traverse and tilt control members 34 and 35 are moved to turn on the microswitches 38a, 38b, 39a and 39b to send forward, backward and stop commands to the drive motors 25, 25a, 27 and 27a.
On the other hand, the threaded rod 30 connected to the output shaft of the first traverse drive motor 25 of the traverse rod 16 has its one end borne pivotally through the bearing 22 in the inner plate 20a of the side plate 20. A gear 40a is fixed on the inserted end of the threaded rod 30. This gear 40a is connected through three intermediate gears 42a, 42b and 42c to a gear 41 which in turn is fixed on the end portion of the traverse rod 16, as shown in FIG. 3. On the other hand, the threaded rod 31 connected to the output shaft of the first tilt drive motor 27 has its one end borne pivotally by a bearing 43a of a bearing plate 43 which is interposed between the first traverse drive motor 25 and the tilt controller 26. A gear 44a is fixed on the inserted end of the threaded rod 31. Below the first traverse drive motor 25 and the traverse controller 24, there is arranged a transmission rod 45 which is positioned in a side portion of the rod chamber 2 to have its two ends borne in the bearing plate 43 and the inner plate 20a. On the transmission rod 45 at the side of the bearing plate 43, there is fixed a gear 46 which is connected through two intermediate gears 47a and 47b to the gear 44a fixed on the threaded rod 31. On an end portion of the transmission rod 45 at the side of the inner plate 20a, on the other hand, there is fixed a gear 48 which is connected through one intermediate gear 50 to a gear 49 fixed on one end portion 12a of the tilt rod 12.
These gears 44a, 47b, 47a, 46, 48, 50 and 49 and the transmission rod 45 constitutes a first tilt rod transmission 44 altogether.
Moreover, the gears 40a, 42c, 42b, 42a and 41 constitute altogether a first traverse rod transmission 40.
At the other end side of the casing frame 1, on the other hand, there are accommodated in series in an upper portion of the rod chamber 2 the second traverse drive motor 25a for driving the other end 16b of the traverse rod 16 and a second tilt drive motor 27a for driving the other end 12b of the tilt rod 12. The other end 16b of the traverse rod 16 is connected to the second traverse drive motor 25a through a second traverse transmission 40b similar to the first one 40, whereas the second tilt drive motor 27a is connected to the other end 12b of the tilt rod 12 through both a second tilt transmission 44b similar to the first one 44 and a transmission rod 45a.
At one side of the lower portion of the casing frame 1, there is defined the rod chamber 2 to which is juxtaposed side by side a cord chamber 53 opened upward. A cover 55 is removably fitted in the upper opening of the cord chamber 53 through fitting grooves 54. Reference numeral 56 denotes reduction gear mechanisms which are attached to the drive motors 25, 25a, 27 and 27a, respectively.
When the first traverse drive motor 25 of the traverse rod 16 of the electric blind thus constructed is excited, its rotating force is transmitted sequentially through the threaded rod 30 and the gears 40a, 42c, 42b, 42a and 41 to one end 16a of the traverse rod 16 to rotate this rod 16. Simultaneously with this, the rotating force of the second traverse drive motor 25a is transmitted to the other end 16b of the traverse rod 16 through the second traverse transmission 40b. As this traverse rod 16 is rotated, the not-shown leading runner is traversed forward along the guide rails 3 through the corresponding rollers 5. This leading runner proceeds to a target position while sequentially pulling the succeeding runners 4 through the corresponding spacers 17. At that target position, the rotations of the traverse rod 16 are stopped. If the first tilt drive motor 27 is excited, on the other hand, its driving force is transmitted sequentially through the threaded rod 31, the gears 44a, 47b, 47a and 46, the transmission rod 45 and the gears 48, 50 and 49 to the end 12a of the tilt rod 12 to rotate the tilt rod 12. Simultaneously with this, the second tilt drive motor 27a is driven to transmit its driving force through the second tilt transmission 44b to the other end 12b of the tilt rod 12. As this tilt rod 12 is rotated, the worm shaft 9 is rotated through the worm gear 10 so that the slats 14 are tilted and opened to an arbitrary angle. If, at the retraction, the traverse rod 16 is rotated backward, the leading runner retracts to return to its initial position while sequentially pushing the succeeding runners 4. If the tilt rod 12 is then rotated backward, the slats 14 restore their initial angle. Moreover, the forward and backward rotations and the stops of the aforementioned drive motors 25, 25a, 27 and 27a are controlled by the traverse and tilt controllers 24 and 26.
As described above, the driving force of the first traverse drive motor 25 is transmitted through the first traverse transmission 40 to the end 16a of the traverse rod 16 borne in the frame casing 1, and the driving force of the second traverse drive motor 25a is transmitted through the second traverse transmission 40b to the other end 16b of the traverse rod 16. As a result, the total of the torques of the motors 25 and 25a can be applied from the two ends 16a and 16b of the traverse rod 16, as shown in FIG. 7, to substantially eliminate any occurrence of torsion. Even if the slats 14 are heavy, moreover, the driving force can be increased to ensure the operations. Since the rotational driving force of the traverse rod 16 can be dispersed, furthermore, the first and second traverse drive motors 25 and 25a can be small-sized to reduce the overall size of their accommodating casing frame 1 thereby to present an excellently fine appearance when the electric blind is mounted.
Likewise, the driving force of the first tilt motor 27 can be transmitted through the first tilt transmission 44 to the end 12a of the tilt rod 12, and the driving force of the second tilt drive motor 27a can be transmitted through the second tilt transmission 44b to the other end 12b of the tilt rod 12. This makes it possible to substantially reduce any occurrence of torsion and to ensure the operations. Since the rotational driving force of the tilt rod 12 can be dispersed, the first and second tilt drive motors 27 and 27a can be small-sized to reduce the size of their accommodating casing frame 1.
Furthermore, the rotating force is transmitted between the first and second traverse drive motors 25 and 25a and the traverse rod 16 through the first and second traverse transmissions 40 and 40b. As a result, the first and second traverse drive motors 25 and 25a can be arranged in the upper portion of the casing frame 1 so that the traverse rod 16 is enabled to have substantially the same total length as that of the casing frame 1. Likewise, the tilt rod 12 and the casing frame 1 are enabled to have a substantially equal length by interposing the first and second tilt transmissions 44 and 44b between the first and second tilt drive motors 27 and 27a and the tilt rod 12.
Since, moreover, the transmission rod 45 of the first tilt transmission 44 is arranged clear of the first traverse drive motor 25 and the traverse controller 24, the first traverse drive motor 27 and the first tilt drive motor 25 can be compactly arranged in alignment with each other. Since the transmission rod 45a of the second tilt transmission 44b is likewise arranged clear of the second traverse drive motor 25a and so on, the second traverse drive motor 25a and the second tilt drive motor 27a can be compactly arranged in alignment with each other.
FIGS. 8 to 10 show other embodiments of the present invention, in which the same portions as those of the foregoing first embodiment are denoted at common reference numerals so that their detailed descriptions will be omitted.
In the embodiment of FIG. 8, the first traverse drive motor 25 is disposed at one side of one end of the casing frame 1, i.e., at the outside of the guide rails 3 whereas the first tilt drive motor 27 is disposed at the other side of the one end of the casing frame 1. Moreover, the second traverse drive motor 25a is disposed at one side of the other end of the casing frame 1 whereas the second tilt drive motor 27a is disposed at the other side of the other end of the casing frame 1. In other words, the first traverse drive motor 25 and the first tilt drive motor 27 are juxtaposed to each other at one end of the frame casing 1 whereas the second traverse drive motor 25a and the second tilt drive motor 27a are juxtaposed to each other at the other end of the frame casing 1. The driving forces of the first and second traverse drive motors 25 and 25a are transmitted through the first and second traverse transmissions 40 and 40b to the two ends 16a and 16b of the traverse rod 16. On the other hand, the driving forces of the first and second tilt drive motors 27 and 27a are transmitted through the first and second tilt transmissions 44 and 44b to the two ends 12a and 12b of the tilt rod 12.
Turning to FIG. 9, the tilt rod 12 and the traverse rod 16 are borne in juxtaposition in the frame casing 1. The first and second tilt drive motors 27 and 27a are disposed at the two ends 12a and 12b of and in alignment with the tilt rod 12. On the other hand, the first and second traverse drive motors 25 and 25a are disposed at the two ends 16a and 16b of and alignment with the traverse rod 16. Moreover, the tilt rod 12 is directly connected to the first and second tilt drive motors 27 and 27a through the corresponding one of the reduction gear mechanisms 56, a controller and so on. On the other hand, the traverse rod 16 is connected directly to the first and second traverse drive motors 25 and 25a through the corresponding one of the reduction gear mechanisms 56, a controller and so on.
The embodiments described above with reference to FIGS. 8 and 9 can be applied to the case in which the drive motors 25, 25a, 27 and 27a are relatively small-sized.
In the embodiment shown in FIG. 10, only one of the traverse rod 16 and the tilt rod 12 is borne in the casing frame 1 so that only the traverse drive motors 25 and 25a are provided in the case of provision of the traverse rod 16 only whereas the tilt drive motors 27 and 27a are provided in the case of provision of the tilt rod 12 only. Thus, the actuator of the present invention may be exemplified by providing only one of the tilt rod 12 and the traverse rod 16.
Incidentally, the present invention should not be limited to the foregoing embodiments. In the first embodiment, for example, the tilt drive motors may be disposed at the outer side whereas the traverse drive motors may be disposed at the inner side. Alternatively, the traverse rod may be driven by two drive motors whereas the tilt rod may be driven by one drive motor, or vice versa. The drive motors used in the embodiments are of AC type but may be modified into DC type.
FIGS. 11 to 22 show tensing mechanisms for tensing the traverse rod. The amount of tension to be imparted to the traverse rod has to be 0.04 mm or more, for example, as given from the following equation in case a traverse rod having a length of l=5500.00 mm is subjected to a depression of l 1 =10 mm, as shown in FIG. 17, because the length after depression of l 2 =2750.02 mm:
2750.02×2=5500.04.
This implies that dispersions arise at a unit of 1/100 mm, thus raising a problem that fine adjustments of the tension are difficult. The description to be made in the following is directed to tensing mechanisms for the traverse rod of the electric blind or the like, which can easily adjust the tension to be applied to the traverse rod at an appropriate value.
FIGS. 11 to 15 show a tensing mechanism of one-side type, in which a traverse rod 66 and a tilt rod 67 have their respective one ends fitted in the fitting bores 73 of receiving heads 72 and 72 formed at the respective one ends of tensing threaded rods 71 and 71. Screws 74 are fastened to integrate together the traverse rod 66 and one tensing threaded rod 71, and the tilt rod 67 and the other tensing threaded rod 71. Incidentally, the receiving heads 72 and 72 may be biased toward the rods 66 and 67 by means of not-shown springs.
To one end of the casing frame 1, there is fastened by means of not-shown screws a gear accommodating side plate assembly 75 which is composed of an inner plate 75a and an outer plate 75b. The other ends of the tensing threaded rods 71 and 71 are inserted into the gear accommodating side plate assembly 75. These inside portions of the tensing threaded rods 71 and 71 inserted into the gear accommodating side plate assembly 75 are formed into a gear fitting square shanks 76 and 76 having square sections. Gears 77 and 77 have their square holes 78 and 78 fitted on those square shanks 76 of the tensing threaded rods 71 and 17 so that they can slide in the axial directions but engage in the circumferential directions with the tensing threaded rods 71 and 71. From the two ends of the gears 77 and 77, respectively, there are projected cylindrical flanges 79 and 79, one of which is pivotally fitted in a circular hole 80 formed in the inner plate 75a of the side plate assembly 75 and the other of which is pivotally fitted in a circular hole 80 formed in the outer plate 75b.
Tensing nuts 84 and 84 are fastened through bearing plates 82 and 82 and bearings 83 and 83 on threaded portions 81 and 81 of the tensing threaded rods 71 extending to the outside from the outer plate 75b. Denoted at numeral 85 is a cover for covering the bearings 83 and 83 and the nuts 84 and 84.
The other ends of the traverse rod 66 and the tilt rod 67 are inserted into a side plate 86 which is fastened to the other end of the casing frame 1 by means of not-shown screws. Stoppers 89 and 89 are fastened to the inserted ends of the rods 66 and 67 through a bearing plate 87 and bearings 88 and 88 by means of screws 90 and 90. Reference numeral 91 denotes a cover.
A traverse drive motor 92 is disposed in an upper portion of the casing frame 1. A threaded rod 93 is connected at its one end to the not-shown drive shaft of the traverse drive motor 92 and at its other end to the aforementioned gear 77 through a traverse controller 94, a gear 95 and intermediate gears 96 so that the driving force of the drive motor 92 is transmitted to the traverse rod 66 through the threaded rod 93 and the gears 95, 96 and 77. Incidentally, the driving force of the not-shown tilt drive motor is also transmitted to the tilt rod 67 by the structure similar to the aforementioned one.
If the tensing nuts 84 and 84 are fastened after the assembly of the electric blind thus constructed, their tensions are applied to the traverse rod 66 and the tilt rod 67 through the tensing threaded rods 71 and 71 because the traverse rods 66 and the tilt rod 67 have their other ends fixed by the rod stoppers 89 and 89. At this time, fine adjustments of the tensions are available depending upon the fastening extents of the nuts 84 and 84 so that appropriate tensions can be applied.
Thus, according to the present embodiment described above, the electric blind can be easily assembled including the tensing means without any requirement for the attachment and detachment of the tensing mechanism, and the tensions after the assembly can be adjusted. These adjustments can be finely performed merely by adjusting the fastening extents of the tensing nuts 84. Moreover, the traverse rod 66 and the tilt rod 67 can be pulled and straightened, even if they are slightly bent, so that they can be used as they are, because the tensions can be introduced by fastening the tensing nuts 84. Still moreover, even if the tensions of the tensing nuts 84 are applied to the tensing threaded rods 71, the gears can be prevented from coming out to cause troubles in the transmission of the driving forces, because the gears 77 are fitted on the square shanks 76 in a manner to freely slide in the axial directions. Furthermore, the traverse rod 66 can be prevented from any deflection by introducing the tension thereinto so that it can stand a slat load as high as about 70 Kg.
FIG. 16 shows a traverse rod tensing mechanism of two-side type, which has a similar structure to that of the aforementioned tensing mechanism of one-side type at one end of the traverse and tilt rods 66 and 67, and the description of the similar structure will be omitted. The other ends of the traverse rod 66 and the tilt rod 67 are fitted in the fitting bores 73 and 73 of the receiving heads 72 and 72 of tensing threaded rods 71a which have no gear fitting shank. Those other rod ends and the receiving heads 72 and 72 are fastened by means of the screws 74 and 74 to integrate the traverse rod 66 with one tensing threaded rod 71a, and the tilt rod 67 with the other tensing threaded rod 71a. Moreover, the threaded portions 81 and 81 of the tensing threaded rods 71a and 71a are inserted into the side plate 86, and tensing nuts 84a and 84a are fastened on the outside extensions of the threaded portions 81 and 81 through the bearing plate 87 and the bearings 88 and 88.
If the tensing nuts 84a and 84a are fastened on the two ends of the traverse rod 66 and the tilt rod 67 after the assembly of the electric blind thus constructed, tensions are applied from the two ends to the traverse rod 66 and the tilt rod 67 through the tensing threaded rods 71 and 71a. At this time, fine adjustment of the tensions can be achieved depending upon the fastening extents of the nuts 84 and 84a so that appropriate tensions can be applied.
Incidentally, the tensing mechanism according to the present invention should not be limited to the foregoing embodiments but can be modified in various fashions within the scope of the present invention. For example, the connecting structure for connecting the tensing threaded rod and the traverse rod and the fitting structure for fitting the gear on the tensing threaded rod may be appropriately selected within the scope of the present invention. The tensing means may be disposed at least at the side of the traverse rod. The associating structure for the gear and the tensing threaded rod may be disposed either at one of the two ends of the traverse rod or together with the support. On the other hand, the drive motors may be connected to the respective two ends of the traverse rod and the tilt rod.
FIGS. 18 to 22 show a rotation transmitting mechanism which is appropriate for the aforementioned tensing mechanisms, as will be described by denoting the common reference numerals at the portions identical to those of the foregoing embodiments.
From the two ends of the gear 77, as shown in FIGS. 18 and 19, there are integrally projected the cylindrical flanges 79 and 79 which are fitted in the circular holes 80 and 80 formed in opposed positions in the outer and inner plates 75b and 75a of the gear accommodating side plate assembly 75 or the frame of the rotation transmitting mechanism. Thus, the gear 77 is pivotally fitted in the outer plate 75b and the inner plate 75a. The gear 77 is further formed at its center with the fitting hole 78 having a square section. The tensing rod 71, which is connected to the traverse rod 66 to form part of the rod 66, is formed with the gear fitting shank 76 having a square section and with the receiving head 72 at its axial end. Thus, the square shank 76 is inserted into the square hole 78 of the gear 77 so that the tensing rod 71 and the gear 77 are so fitted one in the other as to slide in the axial direction relative to each other but to engage with each other in the circumferential direction, thus constructing the aforementioned rotation transmitting mechanism.
If the tensing nuts 84 and 84 are fastened after the assembly of the electric blind thus constructed, the tensions are applied to the traverse rod 66 and the tilt rod 67 through the tensing rods 71 and 71 because the other ends of the rods 66 and 67 are fixed by the rod stoppers 89 and 89. At this time, fine adjustment of the tensions can be achieved depending upon the fastening extents of the nuts 84 and 84 so that appropriate tensions can be applied.
Thus, according to the aforementioned embodiment, the gear 77 is held in a pivotal state by the fitting engagement of the circular hole 80 and the flange 79, even if the tension of the tensing nut 84 is applied to the tensing rod 71. This is because the gear 77 and the tensing rod 71 are allowed to freely slide in the axial direction relative to each other so that no deviating force is applied to the gear 77. As a result, the tension can be adjusted after the assembly so that it can be maintained at an appropriate value.
The description thus made in connection with the present embodiment is directed to the case in which the gear 77 is fitted on the tensing rod 71 forming part of the traverse rod 66. As shown in FIGS. 20 and 21, however, the traverse rod 66 may be formed at its end portion with a gear fitting shank 76a having a triangular section, which is inserted into a triangular hole 78a of the gear 77 of the rotation transmitting mechanism. In an alternative, as shown in FIG. 22, a gear fitting shank 76b may be formed with an axial key 98 whereas the gear 77 may be formed with a key way hole 78b shaped to correspond to the key shank 76b so that this key shank 76b may be inserted into the key way hole 78b.
FIGS. 23 to 25 show a bearing unit which is appropriate for the traverse rod of the electric blind shown in FIGS. 1 to 10.
A casing frame 101 has its right and left open ends closed with side plates 102. In each of these side plates 102, there are pivotally fitted two bearings 105 in which are fitted the end portions of a tilt rod 103 and a traverse rod 104. This traverse rod 104 is formed at its two end portions with axial ridge portions 106, and the bearings 105 have their fitting bores 107 each formed into a square shape having such corners 109 as to receive the axial ridge portion 106 and fit their axial straight ridges 108 therein. Denoted at numeral 110 are screws for fastening the tilt rod 103 and the traverse rod 104 to prevent them from coming out from the bearings 105.
Thus, the traverse rod 104 of the bearing unit according to the present invention is formed at its two end portions with the axial ridge portions 106 having no helical thread, and the fitting bores 107 formed in the bearings 105 fitted pivotally in the side plate 102 are formed to have the square shape capable of fitting the individual straight ridges 108 of the axial ridge portions 106. As a result, in case the traverse rod 104 is rotated to open or close the electric blind, its rotating torque is transmitted from the corners 109 engaging with the four ridges 108 to the bearings 105. Since, in this way, the rotating torque is transmitted through the inner faces of the four corners 109, it is dispersed without any play so that the bearing 105 and the traverse rod 104 can be firmly connected to prevent the latter 104 from being broken. Incidentally, the screws 110 are driven into the traverse rod 104, but the driving force is transmitted mainly through the corners 109 and the straight ridges 108 so that the screws 110 are used to prevent the traverse rod 104 from coming out.
The embodiment detailed above can be modified within the scope of the present invention.
As shown in FIG. 25, for example, the traverse rod 104 may be formed with three axial straight ridges 108 at each extension of its helical threaded portion 111. In this modification, the fitting bore 107 of the bearing 105 is formed into a triangular shape having three corners 109 to engage with the respective ridges 108. On the other hand, the number of these axial straight ridges 108 may be set at various ones so that the shape of the fitting bore 107 of the bearing 105 may correspond to that number. | Herein disclosed is an actuator for actuating an vertical blind or curtain of electric type to be mounted on a mounting support face. The actuator is enabled to eliminate the deformations such as torsions of rotating rods thereto to ensure their rotations by driving the two ends of each of the rotating rods with the torques of a pair of motors. The tension to be applied to a traverse rod can be easily adjusted to an appropriate value by fastening a nut on a tensing threaded rod connected to the traverse rod to tense the traverse rod. Rotation transmitting unit can be held in position in a pivotal state even if the tension is applied to the traverse rod. Since the traverse rod is fitted in a bearing by the face contact between ridges and corners, moreover, the rotating torque is dispersed to enhance the breaking stress at the fitted connection. | 8 |
REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Application No. 61/939,950 filed on Feb. 14, 2014.
BACKGROUND
A gas turbine engine typically includes a fan section, a compressor section, a combustor section and a turbine section. Air entering the compressor section is compressed and delivered into the combustion section where it is mixed with fuel and ignited to generate a high-speed exhaust gas flow. The high-speed exhaust gas flow expands through the turbine section to drive the compressor and the fan section. The compressor section typically includes low and high pressure compressors, and the turbine section includes low and high pressure turbines.
A mid-turbine frame is sometimes provided between the high pressure turbine and the low pressure turbine to aid in supporting bearing assemblies. The low pressure turbine case requires cooling air to maintain temperatures within a desired limit. Cooling air is extracted from the compressor section and routed to a cavity within the mid-turbine frame. Cooling air from the cavity within the mid-turbine frame is then routed to cool the low pressure turbine case. In some applications, the mid-turbine frame is at a temperature such that cooling air within the cavity is heated above a temperature capable of sufficiently cooling the low pressure turbine case.
Accordingly, it is desirable to design and develop cooling features and systems for maintaining desired temperatures within the turbine case.
SUMMARY
A turbine engine according to an exemplary embodiment of this disclosure, among other possible things includes a turbine section including a turbine case disposed about an axis. A frame assembly defines an outer cavity. The outer cavity includes radially outer wall, a radially inner wall and at least one opening configured and adapted to communicate cooling air to the turbine case. A baffle is configured to receive cooling air through the radially outer wall and direct cooling airflow within the outer cavity to prevent impingement on the inner wall.
In a further embodiment of any of the foregoing turbine engines, the baffle includes a plurality of openings for directing cooling air transverse to the radially inner wall of the outer cavity.
In a further embodiment of any of the foregoing turbine engines, the baffle is disposed within the outer cavity.
In a further embodiment of any of the foregoing turbine engines, the plurality of openings are disposed about an outer periphery of the baffle for directing cooling airflow forward, aft and circumferentially within the outer cavity.
In a further embodiment of any of the foregoing turbine engines, the plurality of openings includes holes.
In a further embodiment of any of the foregoing turbine engines, the plurality of openings includes slots.
In a further embodiment of any of the foregoing turbine engines, includes a compressor section in communication with a supply tube for supplying cooling air to the baffle.
In a further embodiment of any of the foregoing turbine engines, the compressor section includes a high pressure compressor.
In a further embodiment of any of the foregoing turbine engines, the turbine section includes a high pressure turbine and a low pressure turbine and the frame is a mid-turbine frame which defines a flow path between the high pressure turbine and the low pressure turbine.
A frame assembly for a turbine engine according to an exemplary embodiment of this disclosure, among other possible things includes a plurality of vane struts extending radially outward relative to an axis, an outer cavity which includes an opening for communicating cooling air to a turbine section of the turbine engine, and a baffle within the outer cavity configured and adapted to receive cooling air. The baffle includes a plurality of openings for directing cooling airflow into the outer cavity for preventing impingement on a radially inner wall of the outer cavity for maintaining a desired temperature of the cooling air within the outer cavity.
In a further embodiment of any of the foregoing frame assemblies, the plurality of openings direct cooling airflow forward, aft and circumferentially within the outer cavity.
In a further embodiment of any of the foregoing frame assemblies, the plurality of openings includes a plurality of holes.
In a further embodiment of any of the foregoing frame assemblies, the plurality of openings includes a plurality of slots.
In a further embodiment of any of the foregoing frame assemblies, the plurality of openings define an total opening area for metering cooling airflow into the outer cavity.
In a further embodiment of any of the foregoing frame assemblies, includes an inner cavity radially inward of the plurality of vane struts. The inner cavity is in communication with the outer cavity.
In a further embodiment of any of the foregoing frame assemblies, the opening for communicating cooling air to the turbine section include a plurality of openings disposed circumferentially within the outer cavity.
In a further embodiment of any of the foregoing frame assemblies, the baffle includes at least two baffles directing cooling air within the outer cavity.
Although the different examples have the specific components shown in the illustrations, embodiments of this disclosure are not limited to those particular combinations. It is possible to use some of the components or features from one of the examples in combination with features or components from another one of the examples.
These and other features disclosed herein can be best understood from the following specification and drawings, the following of which is a brief description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of an example gas turbine engine.
FIG. 2 is an axial section view of an example mid-turbine frame assembly.
FIG. 3 is a sectional view of a portion of the example mid-turbine frame assembly.
FIG. 4 is a perspective view of a portion of an outer cavity of the mid-turbine frame assembly.
FIG. 5 is a schematic view of the outer cavity and example baffle.
FIG. 6 is a top schematic view of the example baffle.
FIG. 7 is a sectional view of cooling airflow within the example mid-turbine frame assembly.
DETAILED DESCRIPTION
FIG. 1 schematically illustrates an example gas turbine engine 20 that includes a fan section 22 , a compressor section 24 , a combustor section 26 and a turbine section 28 . Alternative engines might include an augmenter section (not shown) among other systems or features. The fan section 22 drives air along a bypass flow path B while the compressor section 24 draws air in along a core flow path C where air is compressed and communicated to a combustor section 26 . In the combustor section 26 , air is mixed with fuel and ignited to generate a high pressure exhaust gas stream that expands through the turbine section 28 where energy is extracted and utilized to drive the fan section 22 and the compressor section 24 .
Although the disclosed non-limiting embodiment depicts a turbofan gas turbine engine, it should be understood that the concepts described herein are not limited to use with turbofans as the teachings may be applied to other types of turbine engines; for example a turbine engine including a three-spool architecture in which three spools concentrically rotate about a common axis and where a low spool enables a low pressure turbine to drive a fan via a gearbox, an intermediate spool that enables an intermediate pressure turbine to drive a first compressor of the compressor section, and a high spool that enables a high pressure turbine to drive a high pressure compressor of the compressor section.
The example engine 20 generally includes a low speed spool 30 and a high speed spool 32 mounted for rotation about an engine central longitudinal axis A relative to an engine static structure 36 via several bearing systems 38 . It should be understood that various bearing systems 38 at various locations may alternatively or additionally be provided.
The low speed spool 30 generally includes an inner shaft 40 that connects a fan 42 and a low pressure (or first) compressor section 44 to a low pressure (or first) turbine section 46 . The inner shaft 40 drives the fan 42 through a speed change device, such as a geared architecture 48 , to drive the fan 42 at a lower speed than the low speed spool 30 . The high-speed spool 32 includes an outer shaft 50 that interconnects a high pressure (or second) compressor section 52 and a high pressure (or second) turbine section 54 . The inner shaft 40 and the outer shaft 50 are concentric and rotate via the bearing systems 38 about the engine central longitudinal axis A.
A combustor 56 is arranged between the high pressure compressor 52 and the high pressure turbine 54 . In one example, the high pressure turbine 54 includes at least two stages to provide a double stage high pressure turbine 54 . In another example, the high pressure turbine 54 includes only a single stage. As used herein, a “high pressure” compressor or turbine experiences a higher pressure than a corresponding “low pressure” compressor or turbine.
The example low pressure turbine 46 has a pressure ratio that is greater than about 5. The pressure ratio of the example low pressure turbine 46 is measured prior to an inlet of the low pressure turbine 46 as related to the pressure measured at the outlet of the low pressure turbine 46 prior to an exhaust nozzle.
A mid-turbine frame assembly 58 of the engine static structure 36 is arranged generally between the high pressure turbine 54 and the low pressure turbine 46 . The mid-turbine frame assembly 58 further supports bearing systems 38 in the turbine section 28 as well as setting airflow entering the low pressure turbine 46 .
Airflow through the core airflow path C is compressed by the low pressure compressor 44 then by the high pressure compressor 52 mixed with fuel and ignited in the combustor 56 to produce high speed exhaust gases that are then expanded through the high pressure turbine 54 and low pressure turbine 46 .
The mid-turbine frame assembly 58 includes vanes 60 , which are in the core airflow path C and function as an inlet guide vane for the low pressure turbine 46 . Temperatures of the exhaust gases are such that cooling of the mid-turbine frame assembly 58 may be required. A low temperature cooling air flow (LTCA) supply tube 66 communicates relatively cool air from the compressor section 24 to the turbine section 28 . In this example, the supply tube 66 communicates relatively low temperature cooling air 18 from one of the initial stages of the high pressure compressor 52 to the mid-turbine frame assembly 58 .
Utilizing the vane 60 of the mid-turbine frame assembly 58 as the inlet guide vane for low pressure turbine 46 decreases the length of the low pressure turbine 46 without increasing the axial length of the mid-turbine frame assembly 58 . Reducing or eliminating the number of vanes in the low pressure turbine 46 shortens the axial length of the turbine section 28 . Thus, the compactness of the gas turbine engine 20 is increased and a higher power density may be achieved.
The disclosed gas turbine engine 20 in one example is a high-bypass geared aircraft engine. In a further example, the gas turbine engine 20 includes a bypass ratio greater than about six (6), with an example embodiment being greater than about ten (10). The example geared architecture 48 is an epicyclical gear train, such as a planetary gear system, star gear system or other known gear system, with a gear reduction ratio of greater than about 2.3.
In one disclosed embodiment, the gas turbine engine 20 includes a bypass ratio greater than about ten (10:1) and the fan diameter is significantly larger than an outer diameter of the low pressure compressor 44 . It should be understood, however, that the above parameters are only exemplary of one embodiment of a gas turbine engine including a geared architecture and that the present disclosure is applicable to other gas turbine engines.
A significant amount of thrust is provided by airflow through the bypass flow path B due to the high bypass ratio. The fan section 22 of the engine 20 is designed for a particular flight condition—typically cruise at about 0.8 Mach and about 35,000 feet (10.67 km). The flight condition of 0.8 Mach and 35,000 ft (10.67 km), with the engine at its best fuel consumption—also known as “bucket cruise Thrust Specific Fuel Consumption (‘TSFC’)”—is the industry standard parameter of pound-mass (lbm) of fuel per hour being burned divided by pound-force (lbf) of thrust the engine produces at that minimum point.
“Low fan pressure ratio” is the pressure ratio across the fan blade alone, without a Fan Exit Guide Vane (“FEGV”) system. The low fan pressure ratio as disclosed herein according to one non-limiting embodiment is less than about 1.50. In another non-limiting embodiment the low fan pressure ratio is less than about 1.45.
“Low corrected fan tip speed” is the actual fan tip speed in ft/sec divided by an industry standard temperature correction of [(Tram° R)/(518.7° R)] 0.5 . The “Low corrected fan tip speed”, as disclosed herein according to one non-limiting embodiment, is less than about 1150 ft/second (350 meters/second).
The example gas turbine engine includes the fan 42 that comprises in one non-limiting embodiment less than about 26 fan blades. In another non-limiting embodiment, the fan section 22 includes less than about twenty (20) fan blades. Moreover, in one disclosed embodiment the low pressure turbine 46 includes no more than about six (6) turbine rotors schematically indicated at 34 . In another non-limiting example embodiment the low pressure turbine 46 includes about three (3) turbine rotors. A ratio between the number of fan blades 42 and the number of low pressure turbine rotors is between about 3.3 and about 8.6. The example low pressure turbine 46 provides the driving power to rotate the fan section 22 and therefore the relationship between the number of turbine rotors 34 in the low pressure turbine 46 and the number of blades 42 in the fan section 22 disclose an example gas turbine engine 20 with increased power transfer efficiency.
Referring to FIGS. 2, 3 and 4 an example mid-turbine frame assembly 58 includes an outer cavity 62 and an inner cavity 64 . The outer cavity 62 is disposed radially outward of the airfoils 60 and the inner cavity 64 is disposed radially inward of the airfoils 60 . Several LTCA supply pipes 66 deliver cooling air from the compressor section 24 to the outer cavity 62 . In this example, four (4) supply tubes 66 are arranged ninety (90) degrees apart about the circumference of the mid-turbine vane assembly 58 . As appreciated, different numbers of supply tubes 66 could be utilized in different locations about the mid-turbine vane assembly 58 . In this example, cooling air 18 is extracted from an initial stage of the high pressure compressor 52 . As appreciated, cooling air may be obtained from other portions of the engine 20 that include air at appropriate pressures and temperatures.
The mid-turbine frame assembly 58 includes a plurality of airfoils 60 and vane struts 76 arranged circumferentially about the engine axis A. The airfoils 60 define passages between the high pressure turbine 54 and the low pressure turbine 46 . The vane struts 76 provide support for structures such as bearings supported radially inward of the airfoils 60 . The outer cavity 62 and inner cavity 64 are provided with cooling air 18 that is circulated from the outer cavity 62 to the inner cavity 64 through openings between the airfoils 60 and vane struts 76 .
The outer cavity 62 is defined between a radially outer wall 80 and a radially inner wall 78 . The radially inner wall 78 is exposed to high temperature gas flow 82 and it therefore operates at a substantially higher temperature than the radially outer wall 80 .
Cooling air 18 is communicated to the outer cavity 62 to cool the mid-turbine frame 58 . The cooling air 18 is also communicated through the outer cavity 62 to a low pressure turbine (LPT) cavity 86 defined within a turbine case 74 ( FIG. 3 ) through a plurality of supply holes 72 . Cooling air 18 may also be communicated to the LPT cavity 86 through a feather seal 72 defined at an aft portion of the outer cavity 62 .
The mid-turbine frame assembly 58 is very hot and therefore the temperature of the cooling air 18 provided to cool the low pressure turbine case 74 may require additional cooling features to provide a flow of a desired temperature determined to provide the desired cooling of the low pressure turbine 46 . Cooling air 18 that directly impinges on the radially inner wall 78 is heated and can reach temperatures above desired threshold values for fooling the turbine case 74 . Additionally, direct impingement of cooling air onto the inner wall 78 can result in non-uniform temperatures of the inner wall 78 that can increase thermal stresses.
Accordingly, the example mid-turbine frame assembly 58 includes features that prevent direct impingement and provide a more uniform temperature distribution within the inner wall 78 .
Referring to FIGS. 5, 6, and 7 , the supply pipe 66 , communicates cooling air flow 18 to a baffle 68 . The baffle 68 is disposed within the outer cavity 62 and includes a plurality of openings 86 . In the disclosed example, the baffle 68 directs incoming cooling air outward in a direction transverse to the inner radial wall 78 to prevent direct impingement of cooling air on the inner radial wall 78 .
The example baffle 68 receives cooling air flow 18 and distributes the cooling airflow as indicated by arrows 84 forward, aft, and circumferentially within the outer cavity 62 such that the cooling air flow 84 is directed transverse relative to the incoming airflow 18 . The transverse direction can include components in the forward and aft direction parallel with the axis A and also include a circumferential component within the outer cavity 62 .
In this example, the baffle 68 is cylindrical and includes openings disposed about an outer periphery to distribute cooling airflow 84 into the outer cavity 62 . It should be understood that although a cylindrical shape is disclosed, the baffle 68 may comprise any shapes desired to direct airflow within the outer cavity 62 . Moreover, the openings 86 are holes that provide a desired flow area for the cooling airflow 84 . The openings 86 may be holes, slots, or any other shape that provides a desired direction of cooling airflow into the outer cavity 62 .
The openings 86 combine to provide a desired flow area for the cooling airflow 84 . The flow area provided by the plurality of openings 86 can be tailored to provide a desired metering of cooling airflow as is desired for cooling of both the mid-turbine frame and the turbine case 74 .
The directed airflow 84 does not directly impinge on the inner radial wall 78 and therefore does not become heated above desired threshold limits. Moreover, the baffle directs cooling airflow 84 to provide a substantially uniform temperature of the radially inner wall 78 . The reduction in heating of the cooling airflow 84 within the outer cavity 64 provides a uniform flow of cooling air into through the openings 72 into the cavity 88 of the turbine case 74 .
Accordingly, the disclosed baffle 68 prevents impingement of cooling airflow on the radially inner wall 78 of the cavity 62 to generate a more uniform temperature. Additionally, the baffle 68 directs cooling air transverse to the radially inner wall 78 such that cooling air within the cavity 62 may be maintained at a lower temperature within a desired threshold temperature range for cooling of a turbine case 74 .
The example mid-turbine frame 58 includes baffles 68 at each inlet for cooling airflow 18 ( FIG. 7 ) such that airflow is directed circumferentially about the axis A. In this example, inlets 66 are spaced evenly apart about the axis A and provide cooling air to a corresponding baffle 68 . The baffle 68 distributes the cooling airflow 84 transverse to incoming airflow 18 and to the inner radial wall 78 to prevent absorption of excessive heat in any one location. The distribution provided by the baffles 68 generate a more uniform temperature distribution in both the radial wall 78 and the cooling air 84 circulating though the outer cavity 62 .
Although an example embodiment has been disclosed, a worker of ordinary skill in this art would recognize that certain modifications would come within the scope of this disclosure. For that reason, the following claims should be studied to determine the scope and content of this disclosure. | A turbine engine includes a frame assembly including an outer cavity and an inner cavity with the outer cavity including at least one opening configured and adapted to communicate cooling air to the turbine case. A baffle within the outer cavity includes a plurality of openings for directing cooling airflow into the outer cavity for preventing impingement on a radially inner wall of the outer cavity for maintaining a desired temperature of the cooling air within the outer cavity. | 5 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/308,934 filed Feb. 27, 2010, copending.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the invention
[0003] The invention generally relates to fishing and in particular to signal devices.
[0004] 2. Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 1.98
[0005] Fishing reels often have a built in drag system that can be adjusted or calibrated by the angler by means of a knob or lever. This allows the angler to apply more or less resistance pressure on the fishing line before the fishing line unspools from the fishing reel. The main reason for this drag system is to prevent the fishing line from breaking when more pressure is applied on the fishing line than the fishing line can withstand. When a fish is on the end of the fishing line and exerts more pressure than the fishing line can withstand, the fishing line would part and the fish would be lost if it were not for the drag system on the fishing reel allowing the fishing line to unspool, as necessary, off of the fishing reel with less pressure than the breaking point of the fishing line.
[0006] One problem for a fisherman is that common fishing reels have no mechanism to measure and report the fishing reel drag setting. Typically the drag setting will be adjusted with consideration for the test strength of the line. Currently it is adjusted by feel. Through the years many improvements have been made to fishing reels by fishing reel manufacturers including materials used to build fishing reels. No improvements have been made or added to fishing reels over many years with regards to setting the fishing reel drag. Most anglers set the fishing reel drag by feel, the same way it has been done for decades.
[0007] Because fishing equipment is used in a harsh marine environment, corrosion and deterioration to a fishing reel and fishing rod components from salt and outdoor elements have always been a problem. Mechanical equipment or equipment relying upon moving parts is prone to failure due to contact with salt water, dirt, and contaminants. The records of the United States Patent Office show several devices and methods of mechanically measuring drag. These devices have required moving parts and mechanical elements. They share a likelihood of failure or loss of calibration when used in a marine setting.
[0008] U.S. Pat. No. 7,318,295 to Pekin shows a fishing rod with integrated line tension measurement system and readout in selected units of force, such as pounds. The reel mount on the Pekin rod is arranged to slide linearly on a seat portion of the rod. The reel mount is located on a splined portion of the rod in front of the handle. The splines prevent the reel mount from twisting on the rod. The fishing line pulls both the reel and the reel mount forward, against a pressure sensor that measures the forward force. The pressure sensor communicates the measurement to an electronic system with readout display. The fisherman is allowed to preset a threshold tension limit. If the threshold is reached, the electronic system actuates an audible alarm.
[0009] It would be desirable for a tension measurement system to have no moving parts to maintain. The Pekin device is illustrated as being sandwiched on the fishing rod at the fishing rod butt. This positioning makes disassembly of the tubular spline impossible for cleaning, lubrication, inspection and maintenance. Without the ability to disassemble clean and lubricate moving parts, the Pekin device can be expected to fail after being exposed to a marine environment.
[0010] More generally, it would be desirable for a drag sensor to not require the presence of a reel seat. Not every rod has a predefined a reel seat. A fishing rod without a fishing reel seat allows the fisherman to mount the fishing reel in the location of choice on the fishing rod. The advantage of this option is a fishing reel can be mounted in a location most comfortable for the fisherman. A tall person with long arms sometimes is not comfortable with a fishing reel mounted in the same location on the fishing rod as a small person with short arms. It would be desirable to have a drag sensor that can be mounted to any fishing rod, with or without a reel seat.
[0011] A common problem for many fishermen is to achieve proper the fishing technique. Particularly in deep sea fishing, the battle with a large fish can extend for a long time. A novice fisherman frequently desires to hold the rod quite high, perhaps to protect his own back against fatigue during the lengthy battle to land the fish. Skilled fishermen believe that a high rod position is not desirable, on the basis that the fish is subjected to less than a desired amount of force or pressure from the rod. However, convincing the student fisherman to employ a more effective rod angle has proven to be difficult, because the novice is not convinced that another angle is better.
[0012] It would also be desirable to have the capability to show a novice fisherman how much force or pressure he is applying against a fish during a lengthy battle. A suitable device showing tension on a rod during the battle can guide the fisherman to hold the rod in an effective position to tire the fish.
[0013] A common fishing reel is equipped with two methods for mounting to a common fishing rod. One method is a mounting foot with two ears. The foot with ears on the fishing reel is in a location centered under the fishing reel with the two ears opposing each other with one ear facing toward the tip and the other ear toward the bottom of the butt of a fishing rod in linear alignment. A common fishing reel seat will accommodate the fishing reel foot with ears and by securing them by two rings on the fishing reel seat. The rings can slide over the ears to a snug position and firmly secure the fishing reel.
[0014] The other method common to fishing reels is by means of a clamp. There are two bolts centered under the fishing reel and extending downward, spaced to receive the fishing rod between them. A clamp is bridged between the two bolts to sandwich the fishing rod between the clamp and the reel. The clamp is firmly secured to the rod by placing and tightening nuts on the two bolts. This method does not require a fishing reel seat. The fishing reel can be secured to the fishing rod by clamping it at a desired location along the length of the rod.
[0015] Where a sensor relies upon movement along a spline or slide, it is important for the sliding motion to be free. Thus, the position of a sensor with respect to a fishing rod can influence its accuracy. A sliding sensor relying on forward fishing line tension, where the fishing line is at an angle from the center of the spline or slide as found in Pekin, can lead to binding and give inaccurate measurement. Where a sensor must be positioned to communicate with a fishing line applying forward angular tension, it is desirable for the sensor to have no moving parts to bind or cause inaccurate reading.
[0016] A sensor placed where the fisherman will touch it will produce false readings. With the Pekin device, the fisherman has a hand on the fishing reel handle. Touching any part of the reel will change the tension being exerted and cause a false reading. It would be desirable for a sensor to be placed where the fisherman need not touch it while battling a fish, so that the sensor will always read accurately while sufficient tension is applied by the fishing line to cause the fishing rod to flex.
[0017] U.S. Pat. No. 5,259,252 to Kruse shows a transducer that determines force on a rod by responding to the deflection of the rod. With increased deflection, the circuitry increases a time period for counting signals. The greater the number of signals that are counted, the greater the force is reported on a display. The transducer must be mounted either inside the fishing rod or in a groove that must be formed on the underside of the rod.
[0018] It would be desirable to mount a sensing device on a fishing rod without adversely affecting the integrity, strength and performance of the fishing rod. Having to place a transducer inside a rod or having to form a groove in the rod to receive a transducer limits the application of the transducer. A further limitation on use arises in a scheme as taught by Kruse because complicated circuitry with many moving parts can lead to loss of performance in a harsh marine environment. The complexity of the circuitry also requires a skilled technician to perform calibration. As it is likely that the calibration will change when the device is in actual use in a marine environment, a more reliable and user friendly sensor system would be desirable.
[0019] U.S. Pat. No. 7,322,353 to Owens discloses a handgrip that attaches to a fishing rod and contains various sensors for detecting tension of the fishing line. The device has multi-mode ability, in one mode responding to lateral pull on the rod tip and in the second mode responding to axial pull on the fishing line.
[0020] It would be desirable for any tension measuring device to be independent of a handgrip on the rod. Employing the tension measurement device as a hand grip introduces limitations in how the fishing rod is handled. For example, the angler may prefer to hold the rod elsewhere, whether to aid handling the reel or to obtain leverage, but such variation in handling alters the functionality of the Owens device.
[0021] The handgrip adds the further disadvantage of employing moving parts to sense tension. Moving parts require cleaning, lubrication, and maintenance, which is a disadvantage in a marine environment. Moving parts can easily fail after being exposed to a fishing environment. The use of a handgrip to take measurements is likely to be inaccurate because the fisherman has a hand wrapped tightly around the handgrip. The hand will exert added pressure to the tension of the fishing line. Line tension will change due to the hand tension being exerted and cause a false reading. The angler is likely to introduce additional inaccuracy and perhaps cause binding due to expected human variation in hand placement.
[0022] It would be desirable for a tension measurement device to take into account the specific characteristics of the associated fishing rod. The Owens handgrip derives tension information without regard to the physical parameters of the rod itself. It would be an improvement for the sensing device to use the fishing rod to obtain information.
[0023] To set fishing reel drag by feel, the angler typically pulls on the fishing line with one hand while holding the rod and reel with the other until the line unspools off the fishing reel. In this fashion the fisherman can feel how much pressure it took to make the fishing line unspool off of the fishing reel. If the angler is not satisfied with the amount of resistance pressure, the fishing reel drag lever is adjusted higher or lower until the drag pressure feels right. A huge question is “What feels right?” An experienced angler has an idea from past experience but it is still a guess and it changes based on the line strength (test). An inexperienced angler has no idea and may be caught in a dilemma.
[0024] If the fishing reel drag is set too tight, a large fish may break the fishing line. If the fishing reel drag is set too loose, a large fish may just unspool all the fishing line off of the fishing reel and keep going. In either event the fish will be lost.
[0025] Common fishing line has a manufacturer's pound test rating. This rating indicates the maximum pressure in pounds of force that it will take to part the line. It is agreed by most experienced anglers that a fishing reel drag should be set at 25% of the fishing line pound test rating. For example, if a fishing reel has 40-pound test fishing line, then fishing reel drag should be set at 10 pounds of drag. When the drag of this example is set properly and more than 10 pounds of pressure is put on the fishing line, it should unspool from the fishing reel.
[0026] Another problem the angler encounters is that fishing reel drag pressure changes constantly and inadvertently when a fish is fought. What was right a few moments before may have changed due to unforeseen circumstances. The angler has no way of knowing if this has happened except for feel. A few of the many things that contribute to change in fishing reel drag are heat from fishing reel drag friction, moisture from the marine environment, change in diameter of the fishing reel arbor when fishing line is paid out, or that the angler accidentally has bumping the drag adjustment lever on the fishing reel in the heat of battle with a fish.
[0027] It would be desirable to have a means for guiding and assisting the angler in setting the fishing reel drag to a more accurate setting than just empirical feel, prior to deploying the fishing equipment.
[0028] To achieve the foregoing and other objects and in accordance with the purpose of the present invention, as embodied and broadly described herein, the method and apparatus of this invention may comprise the following.
BRIEF SUMMARY OF THE INVENTION
[0029] Against the described background, it is therefore a general object of the invention to provide a means for guiding and assisting the angler in setting the fishing reel drag to a more accurate setting than just empirical feel, prior to deploying the fishing equipment.
[0030] A further object is to provide a sensing device and method of operation that will (1) measure fishing line tension in real time; (2) digitally display the line tension on deployed fishing line in real time while fishing, utilizing electronic technology; (3) allow current drag line adjustment during read out phase; (4) have the capability to be permanently mounted a fishing rod; (5) have the capability to be integrated into new fishing rod designs; or (6) be attached to existing fishing rods; (7) has no moving parts that require maintenance, and, (8) can be used on any fishing rod that has the ability to flex when tension is applied.
[0031] Another object is to provide a sensing device that operates in real time to advise the fisherman on the effectiveness of various rod positions during a battle to land a fish.
[0032] The invention satisfies these objects by providing a strain gauge to sense rod strain during a hook-up, electronically sends that data to a microprocessor. Typically the microprocessor is mounted on circuit board carrying such additional components as needed, which may include a memory chip containing imbedded software. This assembly of components and operating software is effective to convert the data into a digital report that allows the angler to continually monitor the amount of tension that is on the fishing line in real time during a battle with a fish. It will permit the angler to adjust the fishing reel drag if it has changed from the desired setting when the fishing line is unspooling off of the fishing reel.
[0033] All common fishing rods are built to flex when pressure is applied by fishing line tension. The amount of flex will change based on the amount of pounds pressure applied by the fishing line tension and read out in accordance with an algorithm within the operating software. An electronics package, which includes a microprocessor on a circuit board, connected to a strain gauge attached to the rod, measures the rod's deflection, calculates the line tension and converts the line tension into digitally recognizable numbers.
[0034] In another aspect, software provides for calibration of the strain gauge and electronic package to specific fishing rods. The software also controls an LCD read-out device to allow the user to preset a known drag resistance force in suitable units of measure on the fishing reel and to continually read out the amount of force pressure on the fishing line after hook-up so that a user can apply maximum pressure on a fish while fighting the fish without breaking the fishing line.
[0035] According to the invention, apparatus for sensing drag of a fishing line is applied to a longitudinally elongated fishing rod having a reel with fishing line mounted thereon. When pulling force is applied to the fishing line out of alignment with the longitudinal dimension of the rod, the rod flexes. A strain gauge is bonded to the fishing rod such that the strain gauge senses the degree of flex of the fishing rod. The strain gauge generates an output signal indicative of the sensed degree of flex. A microprocessor is in communication with the strain gauge to receive an input signal responsive to the output signal from the strain gauge. The microprocessor processes the input signal to derive tension on the fishing line and to produce a corresponding readout signal of line tension in a selected unit of measurement. An output device communicates with the microprocessor to receive the readout signal and express a human perceptible indication of fishing line tension in the selected unit of measurement.
[0036] According to a method of determining utility fishing line tension, a specific, preselected fishing rod can be calibrated according to its own characteristics. A sensor device employs a strain gauge measuring flex of the fishing rod. A microprocessor in the sensor device receives and converts inputs of measured flex from the strain gauge into line tension and outputs line tension that has been converted into units of force. An output device receives the line tension outputs and expresses this line tension in humanly perceptible form. The sensor device is operated in calibration mode by programming the microprocessor to request benchmark values of line tension based on a target value. The microprocessor is programmed to receive and record inputs of rod flex associated with benchmark values of line tension. The microprocessor is also programmed to operate in utility mode by receiving an input of rod flex and by automatically outputting an associated line tension by derivation from the recorded benchmark values. The user establishes calibration mode and then inputs a target line drag to the microprocessor. The user receives a programmed request from the microprocessor for the fishing rod to be flexed to a first degree, producing an associated first benchmark line tension readout that is lower than the target line drag. The user flexes the preselected fishing rod to the first degree and inputs the first benchmark line tension readout and associated strain gauge output signal to the microprocessor. The user receives a programmed request from the microprocessor for the fishing rod to be flexed to a second degree, producing an associated second benchmark line tension readout higher than the target line drag. The user flexes the preselected fishing rod to the second degree and inputs the second benchmark line tension readout and associated strain gauge output signal to the microprocessor. The sensor device is operated in utility mode by flexing the preselected fishing rod to an unknown degree and receiving an associated value of line tension from the output device.
[0037] The accompanying drawings, which are incorporated in and form a part of the specification, illustrate preferred embodiments of the present invention, and together with the description, serve to explain the principles of the invention. In the drawings:
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0038] FIG. 1 is a fragmentary view of a fishing rod, broken away at the center, showing the mounted sensing device.
[0039] FIG. 2 is a perspective view showing the sensing device on a fishing rod with line tension applied.
[0040] FIG. 3 is a schematic view of the sensing device in operation, showing human interface actions at the left column, showing sensor logic operations in the middle column, and showing display operations in the right column.
DETAILED DESCRIPTION OF THE INVENTION
[0041] The invention is an apparatus and method for sensing drag of a fishing line. The apparatus is a sensing device 10 composed of four elements: a strain gauge 12 , a signal conditioning circuit, a microprocessor, and an LCD Display, with the latter three elements referred to collectively as the electronics package 16 . The electronics package 16 may further include other elements that may be needed, such a memory serving the microprocessor, or such other elements may be included within the architecture of the microprocessor. Several components of the sensing device 10 may be obtained from commercial sources. These include the strain gauge, utilizing known technology in a new application. The microprocessor is a commercially produced element that is mounted on a common circuit board carrying all necessary supporting elements, including a commercially produced LCD display. The strain gauge 12 is bonded to a fishing rod 14 . The remaining elements, which together are shown as the electronics package 16 , are mounted in a water proof case and connected to the strain gauge by a suitable means for transmitting signals, which may be a wire conduit 18 .
[0042] Wireless communication may be employed between the electronics package 16 and the strain sensor 12 . A short-range system such as Bluetooth enables the electronics package to be mounted at any remote location near the fisherman but not necessarily on the rod 14 . The electronics package 16 can be modified by the addition of a global positioning system chip, providing the ability to collect information of where and when a fish was hooked and where the battle ended. A timer can provide information on how long the battle lasted.
[0043] The strain gauge 12 is bonded with epoxy or glued to the base material of a bending beam, which in this case is the fishing rod 14 . The attachment is by bonding in order to adapt the strain gauge to any fishing rod, while not requiring the structural integrity of the rod to be degraded. In addition, bonding to the rod has been found to produce reliable sensitivity in the performance of the strain gauge. The term, “bonding,” refers to the use of glue, epoxy, silicone, or other agents causing the strain gauge to be functionally attached to the rod. Either the angler or a fishing equipment outfitter may attach the strain gauge to the fishing rod. The electronics package 16 will be placed in a remote location on the fishing rod, such as beyond the location where an angler would hold the fishing rod while fighting a fish so as not to interfere with the fishing line 20 or the fisherman.
[0044] The strain gauge 12 has the ability to sense and measure the flex of the fishing rod 14 . When a fish or other means applies tension to the fishing line 20 , the fishing rod 14 will flex as illustrated by way of example in FIG. 2 . When greater tension is placed on the fishing line 20 , the fishing rod will flex even more. When less tension is applied to the fishing line 20 , the fishing rod will flex less.
[0045] The rod 14 can be substantially any longitudinally elongated fishing rod, as the strain gauge 12 requires no special groves, compartments, or intrusions on the rod structure. Because a major purpose of the sensing device 10 is to determine line tension, the rod 14 should carry a reel with fishing line. The fishing line is strung through the rod in conventional fashion, generally parallel to the longitudinal dimension of the rod, usually through eyelets. The reel and fishing line are mounted on the rod such that the rod flexes when pulling force is applied to the fishing line from an angle out of alignment with the longitudinal dimension of the rod, as suggested in FIG. 2 .
[0046] The strain gauge senses the degree of flex of the fishing rod and generates an output signal indicative of the sensed degree of flex, such as by a signal that is proportionate to the sensed degree of flex. In any event, the output signal consists of data reflecting the flex of the fishing rod. The data is transmitted to the microprocessor in electronics package 16 , where the microprocessor uses the data to determine line tension. The electronics package or microprocessor are in communication with the strain gauge to receive an input signal responsive to the output signal from the strain gauge. The input signal may be the same output signal sent by the strain gauge, but the input signal typically will be a modified or conditioned signal. The microprocessor is a commercially available component separate from the strain gauge 12 . A suitable microprocessor is a Microchip Technology brand PIC16F914.
[0047] Typically, the signal from the strain gauge 12 is sent to a signal conditioning circuit that is mounted on the printed circuit board (PCB) with the microprocessor. A suitable signal conditioning circuit may amplify the signal, using an amplifier such as a Linear brand LT1789-1 single chip instrumentation amplifier. The output of the signal conditioning circuit is sent to the microprocessor.
[0048] The microprocessor is programmed to receive the conditioned input signal, to processes the input signal by performing programmed steps to determine tension on the fishing line, and to produce a corresponding readout signal of tension on the fishing line in a selected unit of measurement. Suitable software steps are programmed into the microprocessor, or otherwise communicated to the microprocessor, to determine line tension. The microprocessor converts or processes the input signal into a readout signal that is expressed in selected units of force. Typically, the readout signal is expressed in pounds.
[0049] An output device such as LCD display 22 is in communication with the microprocessor to receive the readout signal. The output device expresses the tension on the fishing line in the selected unit of measurement. The output may be in any humanly perceptible form. Either audio or video devices are suitable. LCD display 22 can express the tension reading as a digital number. It is not necessary that the digital display express the unit of measurement, as this is likely to be constant and to be an assumed element of the readout.
[0050] The electronics package 16 of the sensing device has the means for calibration employing code suitable to cause it to digitally display the actual amount of fishing line tension expressed in suitable units, such as in pounds of force. The electronics package 16 electronically calculates the force based on the amount of flex that the sensing device 12 senses in the fishing rod 14 . As described, fishing line tension causes the flex, which the strain gauge 12 detects and electrically transmits to the electronics package 16 . There, the flex is converted into pounds of force and displayed in LCD format.
[0051] No two fishing rods flex exactly the same. After the electronic sensor 12 is installed on a preselected fishing rod 14 , the electronics package 16 and strain gauge are calibrated to indicate accurately the fishing line pressure for the particular fishing rod 14 being used. Software developed as a part of the invention accomplishes the calibration. The ability to calibrate the sensing device 12 for the individual characteristics of a particular fishing rod 14 significantly improves the performance of each application.
[0052] The angler should perform calibration based on how many pounds of tension is desired on the fishing line before the drag from the fishing reel 24 will allow the fishing line 20 to unspool. This is commonly known as “drag setting.” The calibration is performed by interface between the fisherman and the electronics package 16 , where software and settings may be recorded in the microprocessor or related memory. The interface consists of the digital display 22 and a keyboard 26 , which may include hard keys, soft keys, or a combination of both. Hard keys are buttons on a fixed or permanent keypad. Soft keys are buttons that are defined on a touch screen. The keypad illustrated in FIG. 1 is composed of an array of buttons, which may include a number keypad and such additional buttons as are desired. As examples, one additional key might be the “on” or “calibrate” key. Another might be the “enter” key. Still another might be the “off” key. These keys of these examples can be varied, combined, substituted, or eliminated according to specific needs of the software.
[0053] With reference to FIG. 3 , a preliminary portion of the calibration process takes place with substantially no line tension. For example, the fisherman may hold the rod in horizontal position with the fishing line hanging free. The line applies no substantial pressure on the preselected rod 14 . Thus, the strain gauge reads the flex of the preselected rod at approximately zero flex and zero line tension.
[0054] The sensor device 10 is operated in calibration mode by programming the microprocessor to request benchmark values of line tension based on a target value. The microprocessor is programmed to receive and record inputs of rod flex associated with benchmark values of line tension. The microprocessor is also programmed to operate in utility mode by receiving an input of rod flex and by automatically outputting an associated line tension by derivation from the recorded benchmark values.
[0055] In general operation of calibration mode, the user triggers calibration mode and then inputs a target value for line drag to the microprocessor. In response, the microprocessor sends to the user a programmed request for the fishing rod to be flexed to a first degree, to produce an associated first benchmark of line tension readout that is lower than the target value for line drag. The user flexes the preselected fishing rod to the first degree. The user then inputs the resulting first benchmark value for line tension readout to the microprocessor. The associated first strain gauge output signal is already available to the microprocessor and can be recorded in association with the first benchmark for line tension readout.
[0056] The microprocessor also sends to the user a programmed request for the fishing rod to be flexed to a second degree, to produce an associated second benchmark for line tension readout that is higher than the target value for line drag. The user flexes the preselected fishing rod to the second degree and inputs the second benchmark value for line tension readout to the microprocessor. The associated second strain gauge output signal is already available to the microprocessor and can be recorded in association with the second benchmark for line tension readout.
[0057] In general operation of utility mode, the sensor device 10 operates according to its operational programming by receiving an input of rod flex and by automatically outputting an associated line tension by derivation from the recorded benchmark values. The user merely fishes, with the result that when a fish is caught, the rod flexes to an unknown degree. The sensor device presents the derived values on the output device, allowing the user to compensate for unacceptable line tension readouts by controls on the reel.
[0058] More specifically, FIG. 3 shows human interface actions at the left column, sensor logic actions at the center column, and display actions at the right column. In this initial stage, it is desirable to record in memory the output from the strain gauge when the rod is substantially non-flexed. This setting zeros the strain gauge and electronics package, establishing a zero base for later readings and eliminating possible errors in the performance of the particular strain gauge and the particular electronics package.
[0059] To establish zero reading, the angler will first push a control button at 30 triggering the sensor device to enter into calibration mode, and thereby setting sensor logic at 32 to recognize a “Null Zero” point on the digital display of the electronics package. Once the sensor 10 is in calibration mode, the digital display of the electronics package will show a prompt at 34 for the angler to enter at 36 the selected, desired fishing reel drag setting. This desired drag setting may be selected according to the manufacturer's recommendation for the fishing line in use. The angler enters the desired fishing reel drag setting at 36 into the electronics package, which receives and stores the desired setting at 38 . The sensor logic employs this desired setting as the target setting when prompting for additional inputs.
[0060] Next, the display shows a prompt at 40 to apply a low-end “pounds of force” tension to the fishing line. The angler applies low tension at 42 by causing pulling on the line sufficiently for the fishing rod to flex slightly, to produce a prompted-for line drag reading. The strain gauge detects the low-tension flex at 44 and sends a signal that results in line tension readout at 46 . This low-end line tension readout will be lower than the desired fishing reel drag setting. The angler will enter the displayed low tension data into the sensor system 10 by pushing “enter” at 48 on the electronics package 16 , which stores the low flex output signal level and low line tension readout at 50 . This low tension setting in memory is a function of the reading taken by the strain gauge at the associated low degree of flex. Thus, the microprocessor has available a known signal level from the strain gauge at a known line drag readout that is below the desired drag limit.
[0061] Next, in response to having stored the low-tension reading, the digital display of the electronics package shows a prompt at 52 to apply a high foot-pound “pounds of force” tension to the fishing line. The angler at 54 applies higher tension to the fishing line, which causes the fishing rod to flex by a greater amount. This high line tension will be higher than the desired fishing reel drag setting. The strain gauge detects the greater flex associated with the higher tension at 56 and outputs a corresponding signal. The microprocessor calculates a corresponding higher readout of line tension at 58 . The angler will store the data associated with this high setting at 60 by pushing “enter” on the electronics package, which stores the high tension setting at 62 . This high tension setting in memory is a function of the output signal from the strain gauge at the associated high degree of flex. Thus, the microprocessor has available a known signal level from the strain gauge at a known line drag readout that is above the desired drag limit.
[0062] Calibration of the sensor is now complete, causing the calibrated sensor to enter operating mode. The sensor takes utility readings at 64 , where the readout is now accurate for line tension and associated flex in use at 66 . According to software control, and based on the amount of fishing rod flex at the remembered high fishing line tension and low fishing line tension settings, the electronics package can mathematically average, proportion, or interpolate at 68 the operational or utility fishing rod flex into a line tension readout for other amounts of pressure applied to the fishing line. At all times, the digital display at 70 will show how much tension is being placed on the fishing line based on the amount of associated flex measured in the preselected fishing rod.
[0063] Changing the reel or changing to a fishing line of different pound test value will have little or no effect on the electronics package, and it will continue to display accurate readings at 70 with respect to the preselected fishing rod. If an angler decides to change a desired fishing reel drag setting by more to than 25%, it is advisable to recalibrate the electronics package in order to maintain accuracy. Recalibration is accomplished by duplicating the steps 30 - 62 described above.
[0064] The calibration enables the sensing device to determine how much tension or pressure is on the fishing line and to display this result at 70 in appropriate units, such as in pounds of force. The sensing device digitally displays this result in pounds force as a result of calibration, which converts foot-pounds into pounds force. With this information available, the angler will be able to monitor and adjust the fishing reel drag to the desired foot pound tension as suggested by the fishing line manufacturer, by employing the drag adjustment means provided on common fishing reels. When the fisherman adjusts the fishing reel drag, the digital read out of the electronics package instantaneously indicates the new tension in foot-pounds. All common fishing lines have a manufacturer's pound test rating, which the fisherman can use at 36 to select a desired fishing reel drag according to operational readout at 70 .
[0065] As an example, a sensing device 10 may employ a strain gauge 12 of the type known as a foil strain gauge with ability to read in more than one axis. This choice enables the strain gauge to be mounted either on top or bottom of the fishing rod. Mounting with slightly less than perfect alignment does not adversely affect performance. The ability to perform with less than perfect alignment is enabled by employing a strain gauge that reads on more than one axis, coupled with the described calibration technique.
[0066] The calibration technique employs averaging or any other suitable proportioning technique for determining a reading between known upper and lower readings. A desired drag is selected, after which the sensing device displays a greater tension, which is entered, and a lesser tension, which is entered. The desired tension is centered between the high and low tension settings. As a further example, if ten pounds is the desired drag, the sensing device might ask for eight and twelve pounds for respective low and high. A tightly defined range between the low and high settings achieves the greatest accuracy. Testing various rods has shown a flex curve that is almost a straight line, which aids the accuracy of the calibration technique.
[0067] In addition, it is desirable to use balanced tackle. Fishing rods often have a manufacturer's recommended pound test line for use on the rod. Staying within the rod manufacturer's recommendations aids sensor accuracy. If overly heavy line is used and, resultantly, the fisherman applies more pressure than the rated amount for the rod, the rod can react by what is known as “bottoming out.” At this point, the rod may not flex any further and could break. If light line is used on a rod rated for heavy line, the rod will be too stiff for the light line and will not flex properly at correspondingly light pressures. Thus, the use of balanced tackle, wherein the rod, reel and line all have similar manufacturer's rating or recommendations, is beneficial to achieving accuracy.
[0068] A proposed mechanism of operation for the sensing device and method is that a force on the fishing line creates a bending torque on the rod. The downward bend of the rod is more or less proportional to the angle and force of the line. As the rod bends, the outside edge of the rod is in compression on the bottom surface and in tension on the top surface. The strain gauge 12 measures resistance that is proportional to the amount of compression/tension, which is proportional to force on the line. The signal conditioning circuit on the PCB converts the resistance of the strain gauge to a voltage that is presented to the microprocessor. This voltage is similarly proportional to the force on the fishing line. The microprocessor converts the voltage to a number and then uses several constants, which are determined during the calibration process, to calculate the force on the line in lbs. The calculated value is then displayed on the LCD.
[0069] It is the desire of most fishermen to put the maximum pressure or braking force, commonly known as drag on the fishing line 20 , as is possible while a fish 28 is on the fishing line without having it break or part the fishing line. Most common fishing line is pound test rated, such that the fishing line will most likely break if the pound test rating is exceeded with more tension. Maximum fishing line tension without breaking the fishing line enables the fisherman to land a fish in a minimum amount of time. The longer a fish is on the fishing line, the higher the odds that the fish will be lost.
[0070] Time works against a fisherman's chance of success in landing a fish. A few of the endless reasons that can contribute to losing a fish are: (a) the fish may inadvertently come unhooked from the fishing line; (b) with time the fishing line may fatigue and break because it can no longer withstand forces applied at it's pound test rating; (c) the fishing line may rub against a foreign underwater object and abrade to cause weakness to the point that it breaks; (d) the struggling fish may even be eaten by a shark; or (e) the point of attachment to the fish gets worn and the fish simply comes unhooked.
[0071] Measuring fishing line tension or “drag” has always been a subjective deduction by a fisherman. Most often a fisherman pulls on the line by hand and adjusts the drag or braking force on the fishing reel based on what the pull “feels” like. Many fish are lost because the fisherman adjusts fishing reel drag at a drag setting beyond the rated test of the fishing line. While a fish is pulling on the fishing line, it is difficult to determine or accurately gauge how much tension is on the line. The sensing device and method will enable anglers to determine how much line tension or reel braking pressure, commonly known as drag, is applied to the fishing line. This determination is accurate in real time. The angler will know the drag pressure by observing the electronic digital LCD 22 read out on the sensing device anytime tension is exerted on the deployed fishing line. Instead of relying on “feel” to determined tension, the angler will see the amount of tension displayed on the electronic digital LCD display. As a result, the fisherman can accurately adjust the fishing reel drag to a real time pressure equal to or less than the pound test rating of the fishing line. This adjustment is made by means of a lever or other control that commonly is present on a fishing reel to adjust drag.
[0072] The marine environment where a fishing rod and a fishing reel are used is very harsh due to salt, dirt, other foreign matter, corrosion, and the like. If a fishing rod and fishing reel are not cleaned and lubricated after use, they will deteriorate and cease to function properly. The sensing device of this invention has no moving parts that could be affected by such a harsh environment. Because the sensing device has no moving parts and requires no routine maintenance, the sensing device is reliable in long term operation.
[0073] The foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly all suitable modifications and equivalents may be regarded as falling within the scope of the invention. | An electronic sensor employs a strain gauge controlled by a microprocessor on a circuit board. The processor operates software to measure electric impulses from the strain gauge and to convert them into digitally recognizable numbers. Software provides for calibration of the electronic sensor specific fishing rods. The software also controls an LCD read-out device to allow the user to preset a known drag resistance force in suitable units of measure on the fishing reel and to continually read out the amount of force pressure on the fishing line after hook-up so that a user can apply maximum pressure on a fish while fighting the fish without breaking the fishing line. | 0 |
REFERENCE TO RELATED APPLICATIONS
[0001] This application is a 371 National Stage application based on PCT/KR2009/003769, filed Jul. 9, 2009, which is based on Korean Application KR 10-2009-0058215, filed Jun. 29, 2009.
FIELD
[0002] The present invention is related to a solar power generation apparatus. More specifically, the present invention is related to a solar power generation apparatus and its tracking method which tracks the sunlight by changing the angle of the solar panel.
BACKGROUND
[0003] Recently, the development of a variety of energy substitution such as, a clean energy source and environment friendly energy are emerging to replace fossil fuels due to the shortage of fossil fuels, environmental contamination issues and etc. One of the solutions is to use solar energy. This type of solar energy use can be categorized into three types; one of the types converts solar energy to heat energy and uses it for heating or boiling water. The converted heat energy can also be used to operate a generator to generate electric energy. The second type is used to condense sunlight and induce it into fiber optics which is then used for lighting. The third type is to directly convert light energy of the sun to electric energy using solar cells.
[0004] In any case, in order to use solar energy, it is necessary to have a device to collect the solar energy. For an energy collection device, a solar panel, which will directly face the direct sunlight, is generally used. This type of solar panel has a structure of multiple solar cells laying on a flat surface structure or has conduits to circulate operating fluids and its efficiency depends on the elevation of the sun.
[0005] Additionally, to face the sun correctly, a program or device to track the sun is necessary. This is called a sunlight tracking system or tracking system. The method to track the sunlight can generally be categorized as a method of using a sensor or a method of using a program. First of all, the method of using a sensor has an advantage of having a simple structure but the scope of sensing the location of the sun is limited and when a certain amount of time has passed while the sun is blocked by clouds and the sun has passed the sensing range of the sensor, it is impossible to track the sun.
[0006] Accordingly, a method of using a tracking program has been developed. Even though it has the disadvantage of needing a compensatory step due to an accumulation of errors, it has the advantage of being able to track the sun regardless of weather conditions. This type of method is used to track the location of the sun by programming the sun's location by observing the sun's changing location due to the earth's spin and rotation around the sun in a tilted state.
[0007] On the other hand, the said tracking system can be categorized as a one-axis system or two-axis system depending on the number of rotational axes and is designed to gain maximum efficiency by adjusting the angle of the solar panel automatically or manually depending on the elevation of the sun based on measured or previously gathered data.
[0008] On the other hand, in terms of a power generation system using solar energy, a large number of solar panels are generally installed on a vast area of flat land and as it is impossible to install more than two panels of solar panels to overlap, a vast space of land is required. Because of this, the power transmission structure that delivers power generated from a generator or an actuator to each solar panel is complex and the power loss during the transmission is greater as well.
[0009] But, when multiple solar panels are installed, a shade can occur due to interference between the solar panels, and sunlight cannot be fully absorbed when the sun does not arise above a certain angle or due to weather conditions.
[0010] In addition, even if the power generation apparatus and its tracking system according to traditional technology is tracking the location of the sun according to the pre-determined programming, there is a problem of errors due to the installation location of solar panels which include said solar cells and particularly with the direction of the installation. In other words, there is an issue of a lower rate of sunlight absorption due to environmental problems such as the land where the solar power generation apparatus is installed and the difference between true north and magnetic north.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a schematic block diagram of a solar power generation apparatus according to the present invention;
[0012] FIG. 2 is a schematic flow chart of the solar tracking system of a solar power generation apparatus according to the present invention;
[0013] FIG. 3 is a concept diagram to explain the sun tracking operation in FIG. 1 and FIG. 2 ;
[0014] FIG. 3 is a concept diagram to explain shade prevention operation in FIG. 1 and FIG. 2 ;
[0015] FIG. 5 shows display screen in FIG. 1 and FIG. 2 ;
[0016] FIG. 6 shows one example of a solar panel in FIG. 1 and FIG. 2 ;
[0017] FIG. 7 shows detailed structure of solar panels in FIG. 6 ;
[0018] FIG. 8 shows the elevation of the sun depending on the general season;
[0019] FIG. 9 is a concept diagram to explain the relationship between the elevation of the sun, its azimuth and control angle.
DETAILED DESCRIPTION
[0020] The current invention is to solve said problems and deliver a solar power generation apparatus and its tracking method where it improves its solar absorption rate by controlling the solar panel's rotational angle when multiple solar panels are installed.
[0021] In addition, another purpose is to deliver a solar power generation apparatus and its tracking method where it rotates its solar cells or solar panels correctly to a desired direction depending on the elevation and angle of the sun and its azimuth.
[0022] In addition, another purpose is to deliver a solar power generation apparatus and its tracking method where it improves the solar absorption rate by rotating the solar cells or solar panels in relation to sun's elevation and its azimuth thus compensating for the error due to its installation location and especially installation direction of the solar panel which houses the solar cells.
Technical Solutions
[0023] A Solar power generation apparatus and its tracking method, according to the present invention, in order to accomplish said purposes is characterized by having one or more solar panels which contains one or more solar cells to absorb sunlight, a rotational angle processing unit which processes a rotational angle to rotate said solar panel in order to maintain the solar cell to a constant angle to said sun based on the elevation of the sun and its azimuth, a differential angle processing unit which processes the differential angle between the installation direction of said solar panel and true north, a control angle processing unit which processes a control angle based on said rotational angle and differential angle, a drive unit which rotates said solar panel according to said control angle and the said control angle processing unit determines whether one of the solar panels is creating shade to another solar panel and when it is determined that shade is occurring, it performs a shade avoiding mode. In addition, said control angle processing unit compares said control angle to a tracking limit angle and outputs said control angle to said drive unit or starts shade avoiding mode depending on the comparison result. In addition, the said control angle processing unit outputs said control angle to said a drive unit when said control angle is greater than said tracking limit angle and is less than 180°—tracking limit angle, and performs shade avoiding mode when said control angle is less than said tracking limit angle or larger than 180°—tracking limit angle. In here, said shade avoiding mode is a mode which rotates said solar panel to a pre-determined control angle for pre-determined duration or can be a mode which rotates said panel to a lesser angle than said tracking limit angle to absorb sunlight and when said absorbed sunlight is above a certain sunlight amount it stops said solar panel. Said constant angle is controlled so the solar panel is perpendicular to sunlight. In addition, said constant angle can be determined by the combination of one or two conditions from time of sunrise, time of sunset, the distance between solar panels, the location of solar panels, the size of sunlight and its related weather data.
[0024] In addition, the present invention is comprised of a communication unit which can communicate with an external system wirelessly or wired. Said elevation of the sun and its azimuth can be determined by the information received from the external weather observation system.
[0025] In addition, the present invention can additionally be comprised of a memory unit which can store the date, time, location and its related weather data and said elevation of the sun and its azimuth can be processed based on the stored date, time, location and its related weather data. The elevation of the sun and its azimuth based on said date, time and location and its related weather data can be pre-programmed into the memory unit.
[0026] In addition, the present invention can additionally be comprised of an input-output unit which can receive commands externally and send current statuses externally and said input-output unit can particularly be a display unit which can receive commands from the screen and displays current status to the screen.
[0027] Solar power generation apparatus and its tracking method, according to the present invention, in order to accomplish said purposes, has one or more solar panels and is characterized by having a rotational angle processing step which processes the rotational angle to maintain said cell's constant angle to said sun based on the elevation of the sun and its azimuth, a differential angle processing step which processes a differential angle between the direction of said solar cell and true north, a control angle processing step which processes a control angle based on said rotational angle and differential angle, a driving step which changes the direction of said solar cell depending on the said control angle, a comparison step which compares said control angle and pre-determined tracking limit angle and a drive step to change the direction of said solar cell based on said comparison result. It is here, the said drive step is characterized by changing the direction of said solar cell according to said limiting angle when said control angle is greater than said tracking limit angle and is less than 180°—tracking limit angle, and performs a shade avoiding mode when said control angle is less than said tracking limit angle or larger than 180°—tracking limit angle.
[0028] It is here, that the said shade avoiding mode is a mode which rotates said solar panel to a pre-determined control angle for a pre-determined duration or can be a mode which rotates said panel to a lesser angle than said tracking limit angle to absorb sunlight and when said absorbed sunlight is above a certain sunlight amount it stops said solar panel.
[0029] Said elevation of the sun and its azimuth can be determined by the received information from the external weather observation system or can be determined by pre-stored date, time and location or can be processed based on weather data from these elements. In addition, said constant angle can be determined by the combination from one or two conditions from time of sunrise, time of sunset, the distance between solar panels, the location of solar panel, the size of sunlight and weather data.
[0030] When multiple solar panels according to the present invention are installed, the sunlight absorption rate can be improved by controlling the rotational angle of solar panels.
[0031] In addition, solar cells or solar panels can be correctly rotated to a desired angle according to the elevation of the sun and its azimuth.
[0032] In addition, according to the present invention, the error that can occur due to the installation location, especially due to installation direction of solar panel which contains said solar cell can be corrected and consequently, the sunlight absorption rate can be improved.
[0033] Solar power generation apparatus and its tracking method, according to the present invention where using one or more solar cells to absorb sunlight, is characterized by controlling the constant angle of said solar cell to sunlight based on the differential angle between installation direction of said solar cell and true north. In here, said constant angle is either the angle where the sun is perpendicular to said solar cell's plane or the angle which is determined by a combination of one or more conditions from time of sunrise, time of sunset, the distance between solar panels, location of solar panel, size of sunlight and weather data.
[0034] From here on, the solar power generation apparatus and its tracking method, according to the present invention, will be explained with the attached drawings.
[0035] As illustrated in FIG. 1 , the solar power generation apparatus and its tracking method according to the present invention is comprised of one or more solar panels ( 100 ) which contains one or more solar cells ( 110 ), a rotational angle processing unit ( 310 ) which rotates said solar panel to maintain a constant angle of solar cells to said sun depending on the elevation of the sun and its azimuth, a differential angle processing unit ( 320 ) which processes the differential angle between the installation direction of said solar panel and true north, a control angle processing unit ( 330 ) which processes the control angle based on said rotational angle and differential angle, a drive unit ( 200 ) which rotates said solar panel according to said control angle. The said control angle processing unit ( 330 ) is characterized by determining whether one of the solar panels is creating shade to the other solar panel and performing a shade avoiding mode when it is determined that shade occurs based on said determination process.
[0036] In addition, said control angle processing unit ( 330 ) compares said control angle and pre-determined tracking limit angle and outputs said control angle to said drive unit or performs shade avoiding process depending on the result. In addition, a said control angle processing unit ( 330 ) outputs said control angle to said drive unit ( 200 ) when said control angle is larger than said tracking limit angle and less than 180°—tracking limit angle, and performs shade avoiding mode when said control angle is less than said tracking limit angle or larger than 180°—tracking limit angle.
[0037] In here, said shade avoiding mode is a mode which rotates said solar panel to a pre-determined control angle for a pre-determined duration or can be a mode which rotates said panel to a lesser angle than said tracking limit angle to absorb sunlight and when said absorbed sunlight is above a certain sunlight amount it stops said solar panel.
[0038] Said constant angle is controlled to be perpendicular between the solar cell plate and sunlight. Or, said constant angle can be determined by the combination from one or two conditions from time of sunrise, time of sunset, the distance between solar panels, the location of solar panel, the size of sunlight and weather data.
[0039] The location of the sun, for example the elevation of the sun, can be changed depending on the season and time. If you refer to FIG. 8 , you can see the different elevation in spring, summer, fall and winter in Gwangju area (in Korea) which is located on latitude N. 35°, longitude E. 126°.
[0040] On the other hand, if you refer to FIG. 9 , the relationship of the control angle depending on the elevation of the sun and its azimuth, which will be processed according to the present invention, is illustrated.
[0041] Said constant angle is controlled to be perpendicular between the solar cell plate and the sun. When the weather condition is normal, the solar cell has to be perpendicular, that is 90°, in order for the cell to receive maximum sunlight. Said constant angle is 90°.
[0042] But when the current time is during sunrise or sunset, the location of the sun is relatively low and shade can occur between solar panels due to the location of said sun. In this case, in order to remove or reduce shade experimentally or intentionally, it can be set to a specific degree by the user. In this case, the constant angle may not be 90°.
[0043] In addition, said constant angle can change depending on the distance between solar panels, the location of solar panel, size of sunlight and weather data and it also can be set experimentally or intentionally by a combination of one or more variables. For example, when the distance between the solar panels is large or there is no obstacle around it, as the possibility of shade is decreased relatively, the constant angle can be set to 90°. But, if the situation is contrary, by assigning a limited angle, to be described later, the shade can be removed or reduced.
[0044] In addition, solar power generation apparatus according to the present invention can also include a communication unit ( 360 ) which can communicate wired or wirelessly with an external system. In here, said elevation of the sun and its azimuth can be determined by the received information from external weather observation system through said communication unit. Said external weather observation system can be NOAA (National Oceanic and Atmospheric Administration), astronomy researcher, other external weather related sites or server system. In addition, said communication unit ( 360 ) will send and receive data with external weather observation system using wired and wireless communication including internet.
[0045] In addition, solar power generation apparatus according to the present invention can also include a memory unit ( 340 ) to store information about the date, time, location and its related weather data. In here, said elevation of the sun and its azimuth can be processed based on the date, time, location and its related weather data. On the other hand, the date, time, location and its related weather data can be stored in said memory unit ( 340 ) beforehand. In this case, said elevation of the sun and its azimuth can be directly read.
[0046] In addition, solar power generation apparatus according to the present invention can also include an input-output unit which can receive instructions from the outside and can send the current status to the outside. In here, said input-output unit can be a display unit which receives instruction through a screen and displays current status to a screen. In other words, the input unit or output unit can generally not only be a keyboard, mouse, key pad, touch pad, monitor, LED (Light Emitting Diode), LCD (Liquid Crystal Display) but also a display unit such as touch screen and depending on the communication method, wireless device such as mobile phone, PDA (Personal Digital Assistant) or smart phone can be used to control instructions or monitoring.
[0047] FIG. 5 illustrates one example of the display unit of the solar power generation apparatus according to the present invention and the display can be generally organized to have an input portion and output portion. For example, the input portion will be categorized as a basic input area (A) which can be used to input data such as date, time, latitude and longitude, installation parameter (B) to East-West direction and installation parameter (C) to North-South direction. In addition, the output area can comprise of a basic display area (D) which shows the elevation of the sun and its azimuth, area (E) to display rotational angle to East-West direction and control angle, area (F) to display rotational angle to North-South direction and control angle.
[0048] If you refer to FIG. 3 , solar power generation apparatus according to the present invention is described. Rotational angle a in FIG. 3 can be calculated by following mathematical formula 1.
[0000]
tan
(
90
°
-
d
)
=
sin
a
cos
a
×
sin
b
Mathematical
Formula
1
[0049] In here, a is an elevation, b is 180°—azimuth, d is a rotational angle to east-west direction and f is a rotational angle to south-north direction.
[0050] On the other hand, d′ is a control angle to east-west direction and f′ is a control angle to south-north direction.
[0051] That is, when there is a differential angle between the direction of solar panel and true north, a difference arises between the calculated rotational angle and the control angle, which defines the angle in which the solar cell is to be rotated and accordingly, a low absorption of sunlight will occur.
[0052] In the solar power generation apparatus according to the present invention, said rotational angle processing unit ( 310 ) calculates the rotational angle (d) in relation to the elevation of the sun and its azimuth. Said mathematical formula 1 can be simply used.
[0053] After that, said differential angle processing unit ( 320 ) processes differential angle (g) between the installation direction of solar panel including solar cells and true north. This differential angle (g) can be processed in various ways. That is, if a solar panel is installed parallel to magnetic north, the difference between magnetic north and true north of the area where the solar panel is installed, that is magnetic declination can be used as differential angle (g). On the other hand, if a solar panel is installed at certain angles to magnetic north, the differential angle (g) can be calculated with consideration of the differential angle between magnetic north and true north and the angle which said panel is faced to magnetic north in the area where the solar panel is installed. For example, if a solar panel is installed parallel to magnetic north in Seoul, the magnetic declination 7° 16′ will be a differential angle (g). Differential angle (g) can be processed using grid convergence or GM angle that is the difference between grid north and true north or the difference between grid north and magnetic north.
[0054] Said control angle processing unit ( 330 ) will determine the control angle (d′) using the trigonometric functions with said rotational angle (d) and said differential angle (g).
[0055] On the other hand, the control angle (f′) in north-south direction can also be calculated using said method. This invention can be applied not only to a one-axis system but also to a two-axis system.
[0056] Avoiding shade during the solar tracking process and improving the sunlight absorption rate will be briefly explained using FIG. 4 . For example, if solar panels are installed according to FIG. 4 , the installation distance will be L 1 , the distance between the solar cells when the solar cell is tracking the sun is L 2 and the width of the solar panel where solar cells are installed is L 3 . In addition, the limiting angle where it stops tracking the sun is h, and the initial control angle to avoid shade is j. Then the control action to avoid shade will occur when angle j is greater than angle h and can be determined by mathematical formula 2 and 3. The said sun tracking method compares the control angle that is processed and said tracking limit angle (h), it is then determined whether to keep tracking the sun by facing the sun at a right angle or to perform a process to avoid shade. On the other hand, tracking limit angle (h) can be set to a constant angle such as 45°. That is when said control angle is between 45° and 135°, it will track the sun and when the control angle is below 45° or above 135°, it can perform an operation to avoid shade.
[0000]
L
2
2
=
L
1
2
+
L
3
2
-
2
×
L
1
×
L
3
×
cos
(
h
)
Mathematical
Formula
2
cos
(
90
°
-
j
)
=
L
1
2
+
L
2
2
-
L
3
2
2
×
L
1
×
L
2
Mathematical
Formula
3
[0057] As illustrated in FIG. 2 , in the solar power generation apparatus and its tracking method according to the present invention where one or more solar cells are used to absorb sunlight to track the sun for the solar power generation apparatus includes a rotational angle processing step (S 200 ) to maintain solar cell to keep constant angle to the sun in relation to the elevation of the sun and its azimuth, a differential angle processing step (S 300 ) to process the differential angle between the direction of solar cell and true north, a control angle processing step (S 400 ) to process control angle based on the rotational angle and differential angle, a comparison step (S 510 ) to compare said control angle and pre-determined tracking limit angle and drive step (S 520 , S 530 ) to change the direction of said solar cell based said comparison result. In here, the structure of the system can be referred to FIG. 1 .
[0058] In here, said drive step is characterized by changing the direction of solar cell according to said control angle when said control angle is larger than said tracking limit angle and less than 180°—tracking limit angle (S 520 ), performing shade avoiding mode when said control angle is less than said tracking limit angle or larger than 180°—tracking limit angle (S 530 ).
[0059] In here, said shade avoiding mode is a mode which rotates said solar panel to a pre-determined control angle for a pre-determined duration or can be a mode which rotates said panel to a lesser angle than said tracking limit angle to absorb sunlight and when said absorbed sunlight is above certain sunlight amount, it stops said solar panel.
[0060] In the solar tracking method according to the present invention, said elevation of the sun and its azimuth can be determined by the received information from an external weather observation system or can be determined based on pre-stored, date, time, location and its related weather data or can be determined based on date, time, location and its related weather data.
[0061] That is, the solar tracking system according to the present invention pre-stores date, time, location and its related weather data (S 111 ), the elevation of the sun and its azimuth will be processed based on the said stored date, time, location and its related weather data (S 112 ).
[0062] In addition, the solar tracking system according to the present invention pre-stores the elevation of the sun and its azimuth based on the date, time, location and its related weather data and derives its information (S 120 ).
[0063] In addition, the solar tracking system according to the present invention connects to an external weather observation system (S 131 ) and receives information about the elevation of the sun and its azimuth from the connected external weather observation system (S 132 ). Said external weather observation system can be NOAA (National Oceanic and Atmospheric Administration), astronomy researcher, other external weather related sites or server system. In addition, it will send and receive data with external weather observation system using wired and wireless communication including internet.
[0064] The location of the sun, for example the elevation of the sun, can be changed depending on the season and time. If you refer to FIG. 8 , you can see the different elevation in spring, summer, fall and winter in Gwangju area (in Korea) which is located in latitude N. 35°, longitude E. 126°.
[0065] On the other hand, if you refer to FIG. 9 , the relationship of the control angle depending on the elevation of the sun and its azimuth which will be processed according to the present invention is illustrated.
[0066] In addition, the solar tracking system's said constant angle, according to the present invention, is either the sun perpendicular to the solar cell plane or the angle which is determined by a combination of one or more conditions from time of sunrise, time of sunset, the distance between solar panels, location of solar panel, size of sunlight and weather data. Said constant angle is controlled to have said solar cell's plane to be perpendicular to said sunlight.
[0067] Said constant angle is controlled to be perpendicular between the solar cell plate and the sun. When the weather condition is normal, the solar cell has to be perpendicular, that is 90°, in order for the cell to absorb the maximum amount of sunlight. Said constant angle is 90°.
[0068] But when the current time is during sunrise or sunset, the location of the sun is relatively low and shade can occur between solar panels due to the location of said sun. In this case, in order to remove or reduce shade, it can be set to a specific angle by the user experimentally or intentionally. In this case, the constant angle may not be 90°.
[0069] In addition, said constant angle can change depending on the distance between solar panels, the location of, solar panel, size of sunlight and weather data and it also can be set experimentally or intentionally by a combination of one or more variables. For example, when the distance between solar panels is large or there is no obstacle around it, as the possibility of shade is decreased relatively, the constant angle can be set to 90°. But, if the situation is contrary, by assigning a limiting degree to be described later, it can remove or reduce the shade.
[0070] Solar tracking method will be explained by referring to FIG. 3 . The rotational angle a can be calculated by a mathematical formula 4.
[0000]
tan
(
90
°
-
d
)
=
sin
a
cos
a
×
sin
b
Mathematical
Formula
4
[0071] In here, a is an elevation, b is 180°—azimuth, d is a rotational angle to east-west direction and f is a rotational angle to south-north direction.
[0072] On the other hand, d′ is a control angle to east-west direction and f′ is a control angle to south-north direction.
[0073] That is, when there is a differential angle between the direction of solar panel and true north, a difference arises between the calculated rotational angle and the control angle, which defines the angle in which the solar cell is to be rotated and accordingly, a low absorption of sunlight will occur. In the present invention, said rotational angle processing unit ( 310 ) first calculates rotational angle (d) in relation to the elevation of the sun and its azimuth. Simply said mathematical formula 1 can be used (S 200 ).
[0074] After that, said differential angle processing unit ( 320 ) processes differential angle (g) (S 300 ) between the installation direction of the solar panel including solar cells and true north. This differential angle (g) can be processed in various ways. That is, if a solar panel is installed parallel to magnetic north, the difference between magnetic north and true north of the area where the solar panel is installed, that is magnetic declination can be used as a differential angle (g). On the other hand, if a solar panel is installed at a certain angle to magnetic north, the differential angle (g) can be calculated with consideration to the differential angle between magnetic north and true north and the angle which said panel is faced to magnetic north in the area where the solar panel is installed. For example, if a solar panel is installed parallel to magnetic north in Seoul, the magnetic declination 7° 16′ will be a differential angle (g). Differential angle (g) can be processed using grid convergence or GM angle that is the difference between grid north and true north or the difference between grid north and magnetic north.
[0075] Said control angle processing unit ( 330 ) will determine the control angle (d′) (S 400 ) using the trigonometric functions with said rotational angle (d) and said differential angle (g).
[0076] When solar panel with solar cells are controlled by said determined control angle (d′), more amount of sunlight can be absorbed (S 500 ).
[0077] On the other hand, the control angle (f′) in north-south direction can also be calculated using said method. This invention can be applied not only to a one-axis system but also to a two-axis system.
[0078] Avoiding shade during the solar tracking process and improving the sunlight absorption rate will be briefly explained using FIG. 4 . For example, if solar panels are installed according to FIG. 4 , the installation distance will be L 1 , the distance between the solar cells when the solar cell is tracking the sun is L 2 and the width of the solar panel where solar cells are installed is L 3 . In addition, the limiting angle where it stops the sun tracking is h, and the initial control angle to avoid shade is j. Then the control action to avoid shade will occur when angle j is greater than angle h and it can be determined by mathematical formula 5 and 6. The said sun tracking method compares the control angle that is processed and said tracking limit angle (h), it is then determined whether to keep tracking the sun by facing the sun at a right angle or to perform a process to avoid shade. On the other hand, tracking limit angle (h) can be set to constant angle such as 45°. That is when said control angle is between 45° and 135°, it will track the sun and when the control angle is below 45° or above 135°, it can perform an operation to avoid shade.
[0000]
L
2
2
=
L
1
2
+
L
3
2
-
2
×
L
1
×
L
3
×
cos
(
h
)
Mathematical
Formula
5
cos
(
90
°
-
j
)
=
L
1
2
+
L
2
2
-
L
3
2
2
×
L
1
×
L
2
Mathematical
Formula
6
[0079] FIG. 6 illustrates one example of solar panel of FIG. 1 and FIG. 2 and FIG. 7 illustrates a detailed diagram of solar panel in FIG. 6 . Solar panel will be explained by referring to FIG. 6 and FIG. 7 from now on. FIG. 6 is an expanded view of FIG. 1 and the solar panels with solar cells are placed in 14 rows and they are connected to be controlled by one control device ( 300 ). The structure in FIG. 6 and FIG. 7 can be modified appropriately as long as it does not deviate from the substance of the present invention.
[0080] If you refer to FIG. 6 , solar panels placed in multiple rows are attached to a torque tube. In FIG. 6 , solar panels are placed to have 14 rows and under each row of solar panels a torque tube is placed. On the other hand, a motor is located in the center of the rows of solar panels. Said motor generates power to rotate torque tube where solar panels are attached and transmits the power. A connection unit to transmit the power generated from said motor is placed to pierce each row of said solar panels. Specifically, said connection unit is extended to intersect the center of the solar panel from under said torque tube and it is connected to each torque tube by a lever arm. Said lever is not only performing a function of supporting said connecting unit but also converts the reciprocal movement of connecting unit to rotational movement of said torque tube.
[0081] If you refer to FIG. 6 and FIG. 7 , said connecting unit is placed in an east-west direction. Said control device ( 300 ) controls the control angle of said solar panel and accordingly it controls said drive unit ( 200 ) so that it controls solar panel ( 100 ) to be placed in a predetermined angle.
[0082] As described previously, the solar tracking system and its tracking method, according to the present invention, has an error due to installation location especially installation direction of solar panels with solar cells can be compensated and accordingly by processing and determining the control angle, solar cell or solar panels can be rotated to a desired direction and sunlight absorption rate. When multiple solar panels are placed according to the present invention, the sunlight absorption rate can be increased by controlling the solar panels in a specific rotational angle.
[0083] On the other hand, a solar tracking method can be used to use a program which does not deviate from a solar tracking system according to the present invention and the tracking method thereof, and it can increase the convenience of the user by storing this program in the storage media. | A solar power generating apparatus and a solar tracking method for the same. When a plurality of solar collector plates are arranged, the solar collector plates may be adjusted at certain rotation angles to maintain a high level of solar absorption efficiently with respect to shade, and errors caused by the installed positions (particularly, the installed directions) of the solar collector plates having solar cells can be compensated for, to accordingly calculate and determine adjustment angles in order to accurately rotate the solar cells or solar collector plates to a desired direction and to increase solar absorption efficiency. | 8 |
FIELD OF THE INVENTION
The present invention relates to an embroidery machine. More particularly, the present invention relates to an embroidery machine and method for transferring an embroidery frame contained in the embroidery machine backward when a thread is broken at an embroidery operation.
DESCRIPTION OF THE PRIOR ART
Generally, an embroidery machine embroiders an embroidery design on a fabric fixed on an embroidery frame during a needle holder contained in a sewing device moves up and down, and simultaneously, the embroidery frame moves to X-axis and Y-axis directions. Because the embroidery machine embroiders the embroidery design on the fabric while the embroidery frame moves to the X-axis and Y-axis directions, an accurate movement and a low vibration of the embroidery frame are closely involved with the quality of embroidery.
Conventionally, the embroidery machine includes an alternating current (AC) servomotor or an induction motor for moving the needle holder up and down. Further, the embroidery machine includes a stepping motor for moving the embroidery frame to the X-axis and Y-axis directions. Twelve to twenty-five sewing machines are serially connected in the form of one shaft so as to improve the productivity of the embroidery machine. Because the embroidery machine embroiders the embroidery design on the fabric with threads of different colors, each sewing device has six to twelve needle holders and needles contained in each needle holder are threaded with the threads of the different colors.
Recently, a convenient input, copy, save, and edition of an embroidery design data is needed in the embroidery machine. Also a user prefers an automatic embroidery machine. The automatic embroidery machine has an automatic thread changing function according to the embroidery design. After the embroidery operation has been completed, the automatic embroidery machine has a function capable of cutting a thread. When the thread is broken at the embroidery operation, the automatic embroidery machine has a function capable of stopping the automatic embroidery machine and displaying an alarm indication. When the automatic embroidery machine is stopped due to an abnormal power-off, the automatic embroidery machine has a function capable of recovering a power supply. Furthermore, a manufacturer or a merchandiser wants to use the embroidery machine including a computer or a microprocessor for implementing the embroidery machine having multiple functions.
Referring to FIG. 1, there is shown a block diagram illustrating a conventional embroidery machine. As shown, the conventional embroidery machine includes a function selection panel 10 , an embroidery frame driver 20 , a thread breakage detector 30 , and a control unit 40 . The function selection panel 10 has function selection keys for selecting a plurality of functions. The embroidery-frame driver 20 drives the embroidery frame in response to a control signal outputted from the control unit 40 . The thread breakage detector 30 detects a broken thread. The control unit 40 controls the embroidery machine with a memory storing a program necessary to control the embroidery machine. If the thread breakage detector 30 detects the broken thread, the control unit 40 stops the embroidery operation. In addition, the control unit 40 is coupled to a setting data storage 50 and an embroidery design storage 60 . The setting data storage 50 and the embroidery design storage 60 can be located in the inside or outside of the control unit 40 . The setting data storage 50 stores a plurality of setting data needed for the embroidery operation, wherein the setting data includes an embroidery operation speed, selected needle holder-related information, etc. The embroidery design storage 60 stores embroidery design information. The control unit 40 can be implemented as a microprocessor. When the user selects a desired embroidery design from embroidery designs stored in the embroidery design storage 60 , the control unit 40 controls the embroidery-frame driver 20 .
When the thread is broken at the embroidery operation, the thread breakage detector 30 detects the broken thread and transmits a detection signal to the control unit 40 . The control unit 40 can include a display, a lamp or a buzzer not shown in FIG. 1 . When the thread is broken, the control unit 40 alarms the user through the display unit, the lamp or the buzzer. At this time, the control unit 40 controls the embroidery-frame driver 20 to stop the operation of the embroidery frame. Further, the user recognizes the broken thread through the display, the lamp or the buzzer. Then, the user finds out a needle of the broken thread and re-threads the needle of the broken thread.
At a state that the embroidery frame contained in the conventional embroidery machine is moved forward, the user should re-thread the needle of the broken thread. When the user re-threads the needle of the broken thread, the embroidery frame moved forward can be obstruction. Accordingly, the user employs a footstool to reach the needle of the broken thread. However, in case that the length of the embroidery machine is more than 750 mm, the user cannot easily re-thread the needle of the broken thread.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide an embroidery machine and method capable of transferring an embroidery frame backward so that a user can easily re-thread a needle of a broken thread in case of thread breakage.
It is, therefore, another object of the present invention to provide an embroidery machine and method capable of transferring an embroidery frame backward when a thread, especially, an upper-positioned thread is broken.
It is, therefore, further another object of the present invention to provide an embroidery machine and method capable of selectively setting an embroidery-frame transfer distance.
It is, therefore, still further another object of the present invention to provide an embroidery machine including an embroidery frame, which can be transferred backward or forward in response to a user request.
In accordance with a first aspect of the present invention, there is provided an embroidery machine for transferring an embroidery frame backward in case of thread breakage, the embroidery machine including the embroidery frame and needle holders holding needles, comprising: detection means for detecting the thread breakage to generate a thread breakage signal if the thread breakage occurs at a needle contained in the needle holders; transfer means for transferring the embroidery frame backward in response to a control signal; and control means, coupled to said detection means and said transfer means, for generating the control signal to control said transfer means in response to the thread breakage signal.
In accordance with a second aspect of the present invention, there is provided an embroidery machine for transferring an embroidery frame backward in case of thread breakage, the embroidery machine including the embroidery frame and needle holders holding needles, comprising: generation means for generating an embroidery-frame transfer request signal in response to a user request if the thread breakage occurs at a needle contained in the needle holders; transfer means for transferring the embroidery frame backward in response to a control signal; and control means, coupled to said transfer means and said generation means, for generating the control signal to control said transfer means in response to the embroidery-frame transfer request signal.
In accordance with a third aspect of the present invention, there is provided a method for transferring an embroidery frame backward in case of thread breakage, comprising the steps of: a) detecting the thread breakage to generate a thread breakage signal if the thread breakage occurs at a needle contained in needle holders; b) generating the control signal to control an embroidery-frame driver in response to the thread breakage signal; and c) transferring the embroidery frame backward in response to the control signal.
In accordance with a fourth aspect of the present invention, there is provided a method for transferring an embroidery frame backward in case of thread breakage, comprising the steps of: a) generating an embroidery-frame transfer request signal in response to a user request if the thread breakage occurs at a needle contained in needle holders; b) generating a control signal to control an embroidery-frame driver in response to the embroidery-frame transfer request signal; and c) transferring the embroidery frame backward in response to the control signal.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects and features of the instant invention will become apparent from the following description of preferred embodiments taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a block diagram illustrating a conventional embroidery machine;
FIG. 2 is an exemplary block diagram illustrating an embroidery machine for transferring an embroidery frame backward in case of thread breakage in accordance with the present invention;
FIG. 3 is an exemplary flow chart illustrating a method for transferring an embroidery frame backward in case of thread breakage in accordance with the present invention; and
FIG. 4 is another exemplary block diagram illustrating an embroidery machine for transferring an embroidery frame backward in response to a user request in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 2 is, there is shown an exemplary block diagram illustrating an embroidery machine for transferring an embroidery frame backward in case of thread breakage. The embroidery machine embroiders an embroidery design on a fabric fixed on an embroidery frame. The embroidery machine has the embroidery frame, the fabric fixed on the embroidery frame, needle holders having a plurality of needles. To perform an embroidery operation, the embroidery frame moves to X-axis and Y-axis directions and the needle holder moves up and down. A thread is threaded with a needle at the embroidery operation, wherein the thread includes an upper-positioned thread and an under-positioned thread. The embroidery machine includes a function selection panel 110 , an embroidery-frame driver 120 , a thread breakage detector 130 , an embroidery-frame transfer data storage 140 , and a control unit 150 . The function selection panel 110 includes a plurality of keys for selecting a function. The embroidery-frame driver 120 drives the embroidery frame, contained in the embroidery machine, in response to a control signal outputted from the control unit 150 . The thread breakage detector 130 , located at a plurality of needle holders, detects the thread breakage. The embroidery-frame transfer data storage 140 stores an embroidery-frame transfer distance data even if the power of the embroidery machine is off. The control unit 150 generates the control signal so as to control the embroidery-frame driver 120 . After the thread breakage detector 130 detects the thread breakage, the embroidery frame driver 120 transfers the embroidery frame backward in response to the control signal outputted from the control unit 150 . At this time, the embroidery-frame driver 120 transfers the embroidery frame backward by an embroidery-frame transfer distance of the embroidery-frame transfer distance data.
Furthermore, the control unit 150 can be implemented as a microprocessor. A setting data storage 160 and an embroidery design storage 170 are coupled to the control unit 150 , respectively. The setting data storage 160 and the embroidery design storage 170 can be located in the inside or outside of the control unit 150 . The setting data storage 160 stores a plurality of setting data including an embroidery operation speed, a selected needle holder-related information, etc., wherein the plurality of setting data can be inputted by the user at the embroidery machine. The embroidery design storage 170 stores embroidery design information so that the user at the embroidery machine can select a desired embroidery design from the embroidery design information. Furthermore, the embroidery-frame transfer data storage 140 can be implemented as a flash memory, a nonvolatile random access memory (RAM) or a floppy disk. The embroidery-frame transfer distance data can be read from the embroidery-frame transfer data storage 140 . Further, the embroidery-frame transfer distance data can be written to the embroidery-frame transfer data storage 140 .
Referring to FIG. 3, there is shown an exemplary flow chart describing a method for transferring the embroidery frame backward in case of the thread breakage. First, at step S 111 , the user at the embroidery machine selects a desired embroidery design stored in the embroidery design storage 170 through the function selection panel 110 . At this time, the user sets the embroidery operation speed and the selected needle holder-related information. Then, at step S 112 , the control unit 150 determines whether the user presses a start key contained in the function selection panel 110 to start the embroidery operation. If the start key is pressed, at step S 113 , the embroidery-frame driver 120 drives the embroidery frame in response to a start key signal from the control unit 150 .
Hereinafter, at step S 114 , the control unit 150 reads an embroidery operation data with respect to the desired embroidery design stored in the embroidery design storage 170 . Then, at step S 115 , the control unit 150 determines whether the embroidery operation data represents an embroidery operation completion data. If the embroidery operation data represents the embroidery operation completion data, at step S 116 , the control unit 150 carries out an embroidery operation stop routine. Otherwise, if the embroidery operation data does not represent the embroidery operation completion data, at step S 117 , the control unit 150 determines whether there is a thread breakage signal from the thread breakage detector 130 . Then, if there is not the thread breakage signal from the thread breakage detector 130 , at step S 118 , the embroidery machine resumes the embroidery operation.
Otherwise, if there is the thread breakage signal from the thread breakage detector 130 , at step S 119 , the control unit 150 carries out the embroidery operation stop routine. Then, at step S 120 , the control unit 150 determines whether the upper-positioned thread or the under-positioned thread is broken. If the upper-positioned thread is broken, at step S 122 , the lamp is turned off or the display displays an upper-positioned thread breakage indication. Then, at step S 123 , the control unit 150 reads the embroidery-frame transfer distance data from the embroidery-frame transfer data storage 140 so as to generate the control signal for controlling the embroidery-frame driver 120 . Then, at step S 124 , the embroidery-frame driver 120 transfers the embroidery frame backward by an embroidery-frame transfer distance of the embroidery-frame transfer distance data in response to the control signal. Then, the user re-threads the needle of the upper-positioned thread. Then, at step S 125 , the control unit 150 determines whether the user presses the start key to re-start the embroidery operation. If the user presses the start key, at step S 126 , the embroidery-frame driver 120 returns the embroidery frame to a previous embroidery-frame position. In other words, the embroidery-frame driver 120 transfers the embroidery frame forward by the embroidery-frame transfer distance of the embroidery-frame transfer distance data.
Otherwise, if the under-positioned thread is broken, at step S 121 , the lamp is turned on or the display displays an under-positioned thread breakage indication. At this time, the user re-threads the needle of the under-positioned thread. Then, the embroidery operation is repeated from the steps S 112 .
Referring to FIG. 4, there is shown another exemplary block diagram illustrating an embroidery machine for transferring the embroidery frame backward according to a user request. As shown, the embroidery machine includes a function selection unit 210 , an embroidery design storage 220 , a thread breakage detector 230 , an embroidery-frame transfer limit sensor 240 , a control unit 250 , a setting data storage 260 and an embroidery-frame driver 270 . Further, the embroidery machine further includes a display or a lamp. The display or the lamp indicates the thread breakage in response to a thread breakage signal outputted from the thread breakage detector 230 . Accordingly, when the display or the lamp indicates the thread breakage, the user sends the user request through a plurality of keys so that the embroidery-frame driver 270 can transfer the embroidery frame forward or backward.
As compared to the embroidery machine shown in FIG. 2, the embroidery machine shown in FIG. 4 further includes the embroidery-frame transfer limit sensor 240 . The embroidery-frame transfer limit sensor 240 senses a movement of the embroidery frame, e.g., the embroidery-frame transfer distance. The embroidery-frame transfer limit sensor 240 generates an embroidery-frame transfer stop signal if the embroidery frame reaches a predetermined limit position. The control unit 250 generates the control signal in response to the embroidery-frame transfer stop signal. The embroidery-frame driver 270 stops the embroidery-frame transfer in response to the control signal. The embroidery-frame transfer limit sensor 240 can be positioned on top, bottom, left and right side of the embroidery machine.
Further, the function selection panel 210 includes an embroidery-frame transfer data setting key, an embroidery-frame transfer key and an embroidery-frame return key. In order to transfer the embroidery frame backward when the thread is broken at the embroidery operation, the user can employ the embroidery-frame transfer data setting key, the embroidery-frame transfer key and the embroidery-frame return key.
The user can set the embroidery-frame transfer distance through the embroidery-frame transfer data setting key. Further, the setting data storage 260 stores an embroidery-frame transfer distance data, which is set through the embroidery-frame transfer data setting key. The user can transfer the embroidery frame backward by an embroidery-frame transfer distance of the embroidery-frame transfer distance data through the embroidery-frame transfer key. At this time, the function selection panel 210 generates the embroidery-frame transfer request signal. Then, the control unit 250 controls the embroidery-frame driver 270 in response to the embroidery-frame transfer request signal so that the embroidery-frame driver 270 can transfer the embroidery frame by the embroidery-frame transfer distance of the embroidery-frame transfer distance data.
The embroidery frame can be returned to a previous embroidery-frame position according to the user request through the embroidery-frame return key. At this time, the function selection panel 210 generates an embroidery-frame return request signal. Then, the control unit 250 controls the embroidery-frame driver 270 in response to the embroidery-frame return request signal so that the embroidery-frame driver 270 can return the embroidery frame to the previous embroidery-frame position. At this time, the embroidery-frame driver 270 transfers the embroidery frame forward by the embroidery-frame transfer distance of the embroidery-frame transfer distance data. As described above, the embroidery machine and method in accordance with the present invention can transfer the embroidery frame backward so that the user can easily re-thread the needle of the broken thread.
Although the preferred embodiments of the invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. | A method for transferring an embroidery frame backward in case of thread breakage, includes the steps of: a) detecting the thread breakage to generate a thread breakage signal if the thread breakage occurs at a needle contained in needle holders; b) generating the control signal to control an embroidery-frame driver in response to the thread breakage signal; and c) transferring the embroidery frame backward in response to the control signal. | 3 |
FIELD OF THE INVENTION
The present invention relates to a ganglioside GM3 derivative containing fluorine atoms in a ceramide portion thereof, to intermediates thereof and to processes for preparing the same.
DESCRIPTION OF THE PRIOR ART
Glycolipids of mammals belong to a sphingoglycolipid which consists of a lipid portion so called ceramide in which a sphingosine of a long chain aminoalcohol is bonded to a long chain carboxylic acid via an amide linkage, a oligosaccharide chain in various types and sialic acid. Ganglioside is a collective name of sphingoglycolipids which particularly contain sialic acid.
Many of the gangliosides are generally localized on cell surfaces of animals, and a sialic saccharide chain portion thereof is directed to outside of the cell. Recent studies reveal that the gangliosides play an important role in fundamental life phenomena such as discrimination in cells, reception and response of information in cells, receptor function for hormone, virus, bacteria, cell toxin, etc., interceller distinction, differentiation and propagation of cells, malignant alteration, immunity, etc.
Among the gangliosides, attention is paid to ganglioside GM3 as a molecule which can develop various physiological activities relating to information communication in cells, differentiation and propagation of cells (S. Hakomori, J. Biol. Chem., 265 (1990), 18713-18716; M. Iwamori, Yukagaku, 40, 361-369 (1991)). In order to clarify the relationship between molecular structures of GM3 derivatives and physiological activities thereof, it is important to prepare various types of the GM3 derivatives which are constituents of biomembrane. Hasegawa synthesized a GM3 derivative in which a sialic acid portion thereof was modified in order to make the role of the sialic acid portion in ganglioside GM3 clear (A. Hasegawa, Carbohydr. Res., 230, 273 (1992)). However, modification of a ceramide portion in the ganglioside GM3 has scarcely been effected (A. Hasegawa et al., Carbohydr. Res., 9, 201 (1990)). If a GM3 derivative in which the ceramide portion thereof is modified is synthesized, physiological significance of the ceramide portion is expected to be made clear.
Hasegawa et al. also found out a process for introducing sialic acid to a specific position in a saccharide chain, which process is important for systematic and easy synthesis of gangliosides, and filed for patent application (Japanese Patent Kokai No. 101691/1991). However, according to the process, dimethyl(methylthio)sulfonium triflate (referred to as DMTST hereinafter) which is a reaction accelerator must be prepared immediately before the reaction. In addition, it is extremely difficult to reproduce a yield of 47%, which is described in the patent literature, in the synthesis of a sialyllactose portion which is a saccharide chain of ganglioside GM3 (see Comparative Example 1 of the present invention).
Kusumoto et al. report synthesis of a sialyllactose portion using similar compounds by a combination of N-bromosuccinimide and tetrabutylammonium triflate as reaction accelerators (K. Fukase et al., Tetrahedron Lett., 34, 2187, (1993)). The present inventor attempted to follow the process. However, the intended sialyllation did not proceed at all, and the lactose portion used as a starting substance was quantitatively recovered (see Comparative Example 2 of the present invention). Therefore, it is desired to provide a simpler process for synthesizing GM3 intermediates in higher yield.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a GM3 derivative having fluorine atoms in a ceramide portion thereof which is a lipid portion of ganglioside GM3, and intermediates thereof.
The present invention provides a fluorinated ganglioside GM3 derivative of the general formula (I): ##STR2## in which m is an integer of at least 2, n is an integer of 0 to 7 provided that m is larger than n, and R represents an alkyl group or a fluoroalkyl group.
The present invention also provides a fluorinated 2-azide sphingosine of the general formula (II): ##STR3## in which m is an integer of at least 2, n is an integer of 0 to 7 provided that m is larger than n, R 4 and R 5 independently represent a hydrogen atom or a protective group for a hydroxyl group, which is an intermediate of the compound represented by the general formula (I).
The present invention also provides a fluorinated α,β-unsaturated aldehyde of the general formula (III): ##STR4## in which m is an integer of at least 2, n is an integer of 0 to 7 provided that m is larger than n,
which is an intermediate of the compound represented by the general formula (II).
Furthermore, the present invention provides a process for preparing a ganglioside GM3 intermediate of the general formula (VI): ##STR5## in which R 1 represents a protective group for a hydroxyl group, R 2 represents a protective group for a carboxylic acid, R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently represent a hydrogen atom or a protective group for a hydroxyl group, and R 18 represents a trialkylsilylethyl group in which the alkyl group contains 1 to 4 carbon atoms, which comprises the step of reacting a compound of the general formula (IV): ##STR6## in which R 11 represents a hydrogen atom or a protective group for a hydroxyl group, and R 12 to R 18 are the same as defined above, with a compound of the general formula (V): ##STR7## in which R 1 and R 2 are the same as defined above, and R 3 represents an alkyl group containing 1 to 10 carbon atoms or a phenyl group optionally having substituents, in the presence of N-iodosuccineimide and trifluoromethanesulfonate
DETAILED DESCRIPTION OF THE INVENTION
The ganglioside GM3 derivative of the general formula (I) according to the present invention containing fluorine atoms in a ceramide portion thereof is, for example, synthesized in the following sequence:
(1) Synthesis of a fluorinated α,β-unsaturated aldehyde
(2) Synthesis of a fluorinated 2-azide sphingosine from the fluorinated α,β-unsaturated aldehyde
(3) Condensation of a GM3 saccharide chain portion with the fluorinated 2-azide sphingosine
(4) Reduction of an azide group in the condensed product to an amino group
(5) Condensation of the aminated condensed product with a carboxylic acid
(6) Elimination of protective groups
The reactions will be illustrated in order hereinafter.
(1) Synthesis of a fluorinated α,β-unsaturated aldehyde
At first, a fluorinated α,β-unsaturated aldehyde of the general formula (III) is synthesized for example in the following route:
(1-1) Scheme 1 ##STR8## Notes: Br(CH 2 ) 10 OTHP: 10-bromo-1-[(3,4,5,6-tetrahydro-2H-pyran-2-yl) oxy]tetradecane
p-TsOH: p-toluenesulfonic acid
PCC: pyridinium clorocromate
PhSCl: benzenesulfenyl chloride
LDA: lithium diethylamide
PhSSPh: diphenyl sulfide
Details of reaction conditions in every reaction are described in Examples 2 to 8.
(1-2) Scheme 2 ##STR9## Details of reaction conditions in every reaction are described in Examples 20 to 23
(1-3) Scheme 3 ##STR10##
Details of reaction conditions in every reaction are described in Examples 35 to 40.
It can be understood that appropriate selection of starting substances provides the fluorinated α,β-unsaturated aldehyde of the general formula (III).
(2) Synthesis of a fluorinated 2-azide sphingosine
A fluorinated 2-azide sphingosine of the general formula (II) is synthesized from the fluorinated α,β-unsaturated aldehyde obtained above. The synthesis is effected, for example, according to the process described in Carbohydrate Researches, 202 (1990), 177-191, in the following way: ##STR11## Notes: Bu 2 BOTf: di-(n-butyl)boron triflate
Et 3 N: triethylamine
Et 2 O: diethyl ether
TBDMSOTf: tert.-butyldimethylsilyl triflate
TBAF: tetrabutylammonium fluoride
TrCl: triphenylmethyl chloride
BzCl: benzoyl chloride
Triethylamine and Bu 2 BOTf are added to (4S)-3-bromoacetyl-4-isopropyl-2-oxazolidinone dissolved in anhydrous ether at a temperature of -78° C. The mixture is warmed to a room temperature and again cooled to -78° C. The α,β-unsaturated aldehyde obtained above which was dissolved in an anhydrous ether is dropwise added to the mixture, followed by purification procedure, to obtain (4S)-3-[(2'S, 3'R,4'E)-2'-bromo-fluorinated-3'-hydroxy-4-(isopropyl)-4'-octadecenoyl]-2-oxazolidinone. The compound obtained is reacted with sodium azide in the presence of dimethyl sulfoxide to form an azide. The azide is reacted with 2,6-lutidine and TBDMSOTf at 0° C. in the presence of anhydrous THF, followed by the reaction with lithium boron hydride at 0° C. for 1.5 hours, to obtain (2S,3R,4E)-2-azide-3-O-tert.-butyldimethylsilyl-fluorinated-4-octadecene-1,3-diol. TBAF is reacted with the compound to obtain (2S,3R,4E)-2-azide-fluorinated-4-octadecene-1,3-diol in which a tert.-butyldimethylsilyl group is eliminated. The azide sphingosine obtained is reacted with TrCl in a THF-chloroform-pyridine mixed solvent to form a tritylated compound. It is reacted with BzCl in a pyridine-toluene mixed solvent to form a benzoylated compound. Finally, the trityl group therein is removed in methanol using BF 3 -Et 2 O to obtain an intermediate, i.e., (2S,3R,4E)-2-azide-3-O-benzoyl-fluorinated-octadecene-1,3-diol.
Details of reaction conditions in every reaction are described in Examples 9 to 16, 24 to 31 and 41 to 48.
(3) Condensation of a GM3 saccharide chain portion with the fluorinated 2-azide sphingosine
The fluorinated 2-azide sphingosine of the general formula (II) obtained above in which R 4 represents a protective group for a hydroxyl group and R 5 represents a hydrogen atom, is condensed with a GM3 saccharide chain portion of the general formula (VII): ##STR12## in which R 1 represents a protective group for a hydroxyl group, and R 2 represents a protective group for a carboxylic acid group, to obtain a compound of the general formula (VIII): ##STR13## in which R 1 , R 2 , m and n are the same as defined above.
In the present invention, the protective groups for a hydroxy group include an acetyl group, a pivaloyl group, a benzoyl group and the like. The protective groups for a carboxylic acid group include an alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, etc., a benzyl group optionally containing substituents (for example, a methyl, an ethoxy, and an acetoamide group) in the phenyl group, etc.
The compound of the general formula (VII) can be synthesized according to the process described in Japanese Patent Kokai No. 101691/1991. It is synthesized in the present invention as follows: ##STR14## Notes: NIS: N-iodosuccinimide
Et 4 NOTf: tetraethylammonium triflate
MS4A: Molecular Sieve 4A
DBU: 1,8-diazabicyclo[5,4,0]undec-7-ene
Condensation of the GM3 saccharide chain portion with the fluorinated azide sphingosine was carried out, for example, as follows: The compound of the general formula (11) and the compound of the general formula (VII) are dissolved in dichloromethane. Activated Molecular Sieve 4A is added to the mixture, followed by stirring under an argon atmosphere for 30 minutes. Then boron trifuoride-diethyl ether is dropwise added thereto under ice-cooling to react at 0° C. Details are described in Examples 17, 32 and 49.
(4) Reduction of an azide group in the condensed product into an amino group
An azide group in the condensed product of the general formula (VIII) is reduced to an amino group, for example, using a triphenylphosphine-water system, or a hydrogen sulfide-pyridine system, as described in Examples 18, 33, 50, 52 and 54 to obtain a compound of the general formula (IX): ##STR15## in which R 1 , R 2 , m and n are the same as defined above. (5) Condensation with a carboxylic acid
The amino group of the compound of the general formula (IX) is condensed with a carboxyl group in a carboxylic acid of the general formula (X):
RCOOH (X)
in which R represents an alkyl group or a fluoroalkyl group, using a dehydrating agent such as dicyclohexylcarbodiimde (DCC), diisopropylcarbodiimide (DIPC), N-ethyl-N'-3-dimethylaminopropylcarbodiimide (WSCI) to form an amide group to obtain a compound of the general formula (XI): ##STR16## in which R 1 , R 2 , R, m and n are the same as defined above.
A molar ratio of the compound of the general formula (IX) to the compound of the general formula (X) is in the range of 1:0.5 to 1:2.0, preferably in the range of 1:1 to 1:1.1. The dehydrating agent is used in an amount of 1 to 2 moles, preferably 1 to 1.1 moles per mole of the compound of the general formula (IX). Examples of preferred solvents are dichloromethane, chloroform, dichloroethane, dimethylformamide, etc. The reaction is usually carried out at a temperature of 15° to 25° C. After completion of the reaction, posttreatments such as extraction, distillation-off of solvent, etc. are effected and, if necessary, the product is purified by means of column chromatography.
Examples of the condensation reaction are described in Example 18, 33, 50, 52 and 54.
(6) Release of protective groups
Protective groups of hydroxyl groups and a carboxyl group in the compound of the general formula (XI) are released to obtain a compound of the general formula (I): ##STR17## in which R, m and n are the same as defined above.
The release of the protective groups are, for example, effected as follows: The compound of the general formula (XI) is dissolved in anhydrous methanol, followed by addition of sodium methoxide in an amount of 2 to 4 equivalents per equivalent of the compound of the general formula (XI). The reaction mixture is reacted at a temperature of a room temperature to 50° C. for a period of 30 minutes to 10 hours to release the protective groups of a hydroxyl groups. Then the protective group of a carboxylic group is released by cooling the mixture to 0° C., adding water thereto and stirring the resulting mixture at 0° C. for 1 to 6 hours. After removing salts therein with a cation-exchange resin (H+ type), column purification is effected, for example, using Sephadex LH-20 to obtain an ganglioside GM3 derivative of the general formula (I) which contains fluorine atoms in a ceramide portion thereof. Examples of the release of the protective groups are described in Examples 19, 34, 51, 53 and 55.
The present invention also relates to a process for bonding sialic acid with a saccharide chain portrion to synthesize a GM3 saccharide chain portion of the general formula (VII) which is used as a raw substance for synthesizing the compound of the general formula (I). That is, the present invention relates to a process for preparing a ganglioside GM3 intermediate, comprising the step of reacting a compound the general formula (IV): ##STR18## in which R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 each represent a hydrogen atom or a protective group of a hydroxyl group and R 18 represents a trialkylsilylethyl group wherein the alkyl group contains 1 to 4 carbon atoms,
with a compound of the general formula (V): ##STR19## in which R 1 represents a protective group of a hydroxyl group, R 2 represents a protective group of a carboxyl group and R 3 represents an alkyl group containing 1 to 10 carbon atoms or a phenyl group optionally having substituents, in the presence of N-iodosuccinimide and trifluoromethanesulfonate to obtain a compound of the general formula (VI): ##STR20## in which R 1 to R 18 are the same as defined above.
In the reaction, a molar ratio of the compound of the general formula (IV) to the compound of the general formula (V) is in the range of 1:3 to 2:1. N-iodosuccinimide is used in an amount of 1 to 10 equivalents per equivalent of the compound of the general formula (V). Examples of trifluoromethanesulfonates are tetramethylammonium, tetraethylammonium, tetrabutyulammonium, and triethylbenzylammonium thereof. The trifuoromethanesulfonate is used in amount of 0.01 to 0.5 equivalent per equivalent of N-iodosuccinimide. Examples of preferred solvents are acetonitrile, propionitrile, and the like. The reaction is preferably carried out at temperatures of -45° to -40° C.
For example, the compound of the general formula (IV) and the compound of the general formula (V) are dissolved in acetonitrile. Powdery Molecular Sieve 4A is then added to the solution in twice the total weight of the compounds of the general formulae (IV) and (V). Thereafter, the resulting suspension is stirred and then cooled to -45° C. N-iodosuccinimide and then trifluoromethanesulfonate are added thereto. The mixture is stirred under an argon atmosphere at temperatures of -45° to -40° C. for about 2 hours. An example of the reaction is shown in Example 1. Conventional processes are also shown in Comparative Examples 1 and 2.
EXAMPLES
The present invention will be illustrated by Examples, but is not limited thereto.
In Examples and Comparative Examples, abbreviation s used in NMR column are as follows: Me: methyl group, Ac: acetyl group, Ph: phenyl group
Comparative Example 1
Synthesis of 2-(trimethylsilyl)ethyl-O-methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-2,6-di-O-benzoyl-β-D-glucopyranoside) (referred to as "Compound (1)" hereinafter)
140 mg (0.268 mmol) of methyl(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosylonate) (referred to as "Compound (B)" hereinafter) and 75 mg (0.1 mmol) of 2-(trimethylsilyl)ethyl-O-(6-O-benzoyl-β-D-galactopyranosyl)-(1.fwdarw.4)-2,6-di-O-benzoyl-β-D-glucopyranoside (referred to as "Compound (A)" hereinafter) were dissolved in 1 ml of acetonitrile under an argon atmosphere to form a solution. 150 mg of powdery Molecular Sieve 4A was then added thereto, followed by stirring for 16 hours. The resulting suspension was cooled to -30° C., followed by the addition of 200 mg of powdery Molecular Sieve 4A containing 245 mg of DMTST, and stirred under an argon atmosphere at around -20° C. for 24 hours. The reaction suspension was diluted with dichloromethane and then filtered. The filtrate was washed with an aqueous saturated sodium carbonate solution and then with water, dried over anhydrous sodium sulfate and then concentrated to obtain a syrup. It was subjected to column chromatography (a packing material: silica gel 60 (9385), an eluent: ethyl acetate/hexane=7/2) to obtain 5 mg of Compound (1). Yield: 4.1%. NMR(CDCl 3 , δ lactose unit; 0.86(m, 2H), 3.58(m,1H), 4.40(d, J=8 Hz, 1H), 4.57(dd, J=12 Hz,5 Hz, 1H), 4.63(d, J=8 Hz, 1H), 4.73(dd, 1H 5.24(dd, J=9 Hz, 1H), 7.27-8.08 (m, 15H), sialic acid unit; 2.65(dd, 1H, J=13 Hz, 5 Hz), 3.80(s, 3H), 5.03(m, 1H), 5.70(d, 1 H, J=9 Hz)
Comparative Example 2
Synthesis of Compound (1)
140 mg (0.268 mmol) of the Compound (B) and 75 mg (0.1 mmol) of the Compound (A) were dissolved in 1.5 ml of anhydrous propionitrile under an argon atmosphere to form a solution. 370 mg of powdery Molecular Sieve 4A was then added thereto, followed by stirring for 16 hours. The resulting suspension was cooled to -55° C., before 48 mg (0.270 mmol) of N-bromosuccinimide and then 20 mg (0.051 mmol) of tetrabutylammonium triflate were added. The suspension was stirred under an argon atmosphere at temperatures of -55° to -40° C. for 3.5 hours. The reaction suspension was diluted with dichloromethane and then filtered. The filtrate was washed with an aqueous saturated sodium bicarbonate solution and then with water, dried over anhydrous sodium sulfate and then concentrated to obtain a syrup. It was subjected to column chromatography (a packing material: silica gel 60 (9385), an eluent: ethyl acetate/hexane=7/2). The fractions containing the Compound (A) were collected and concentrated under a reduced pressure to obtain a residue, which was subjected to a column chromatography (a packing material: Wako gel C-200, an eluent: methanol/dichloromethane=1/5→1/20) to recover 70 mg of the Compound (A). Recovery ratio: 93.3%.
Example 1
Synthesis of Compound (1)
728 mg (1.40 mmol) of the Compound (B) and 460 mg (0.61 mmol) of the Compound (A) were dissolved in 6 ml of anhydrous acetonitrile under an argon atmosphere to form a solution. 2.4 g of powdery Molecular Sieve 4A was then added thereto, followed by stirring for 16 hours. The resulting suspension was cooled to -45° C., followed by the addition of 820 mg (3.65 mmol) of N-iodosuccinimide and then 140 mg (0.358 mmol) of tetrabutylammonium triflate, and stirred under an argon atmosphere at temperatures of -45° to -40° C. for 2 hours. The reaction suspension was diluted with dichloromethane and then filtered. The filtrate was washed with an aqueous saturated sodium carbonate solution and then with water, dried over anhydrous sodium sulfate and then concentrated to obtain a syrup. It was subjected to column chromatography (a packing material: silica gel 60 (9385), an eluent: ethyl acetate/hexane=7/2) to obtain 360 mg of the Compound (1). Yield: 48.0%. ##STR21##
Example 2
Synthesis of 14,14,14-trifluoro-1-[(3,4,5,6-tetrahydro-2H-pyrane-2-yl)oxy]tetradecane (referred to as "Compound (2)" hereinafter)
0.3 g (1.57 mmol) of 4,4,4-trifuorobromobutane was added under an argon atmosphere to 0.39 g (16.0 mmol) of magnesium in a form of flakes and a piece of iodine which had been suspended in 10 ml of tetrahydrofuran. After stirring for 3 minutes, the temperature of the reaction mixture was elevated and its color due to iodine disappeared. 2.9 g (16.4 mmol) of 4,4,4-trifluorobromobutane dissolved in 13 ml of anhydrous tetrahydrofuran was dropwise added under mild reflux. After the completion of dropwise addition, the reaction mixture was refluxed for 30 minutes to obtain a solution, which was cooled to a room temperature. The reaction solution was dropwise added to 3.2 g (10.0 mmol) of 10-bromo-1-[(3,4,5,6-tetrahydro-2H-pyrane-2-yl)oxy]tetradecane dissolved in 15 ml of anhydrous tetrahydrofuran which had been cooled to -78° C. After 6 ml (0.6 mmol) of 0.1 M dilithium tetrachlorocuplate in tetrahydrofuran was added at -78° C., the reaction mixture was warmed to a room temperature over 3 hours and further stirred for 20 hours. The reaction mixture was poured into an aqueous 1 M ammonium chloride solution and then extracted with ether. The ether layer was washed with an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue, which was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ether/hexane=1/19) to obtain 1.73 g of Compound (2). Yield: 49.1%. NMR(CDCl 3 ,TMS): δ 4.58(m, 1H, O-CH-O), 3.9-3.2(m, 4H, CH 2 O), 2.2-1.9(m, 2H, CF 3 CH 2 ), 1.85-1.1(m, 28H, 14×CH 2 ) 19 F-NMR(CDCl 3 , CFCl 3 ): δ -66.79(t, J=11 Hz, 3F, CF 3 )
Example 3
Synthesis of 14,14,14-trifluoro-1-tetradecanol (referred to as "Compound (3)" hereinafter)
5.25 g (14.89 mmol) of the Compound (2) was dissolved in 100 ml of methanol to form a solution. 0.28 g (1.47 mmol) of p-toluenesulfonic acid monohydrate was added thereto to obtain a reaction mixture, which was stirred at a room temperature for 2 hours. After the solvent was distilled off under a reduced pressure, the residue obtained was dissolved in ether to form a solution. It was washed with an aqueous saturated sodium bicarbonate solution and then with an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/5) to obtain 3.50 g of Compound (3). Yield: 87.6%. It was recrystallized from ethanol-water to obtain a needle crystal.
m.p. 46.5°˜47.0° C. NMR(CDCl 3 ,TMS): δ 3.65 (t, J=6 Hz, 2H, CH 2 --O), 2.2-1.9 (m, 2H, CF 3 CH 2 ) 1.7-1.1(m, 23H, 11×CH 2 +OH.)
Example 4
Synthesis of 14,14,14-trifluoro-1-tetradecanal (referred to as "Compound (4)" hereinafter)
153 mg (0.710 mmol) of the Compound (3) which had been dissolved in 2.5 ml of dichloromethane was added to 107 mg (0.399 mmol) of pyridinium chlorochromate dissolved in 1 ml of dichloromethane to obtain a reaction mixture. It was stirred at a room temperature for 8 hours, diluted with ether and filtered using Celite. The filtrate was subjected to distillation to obtain a residue. It was purified by flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/10) to obtain 70 mg of Compound (4). Yield: 66.0%.
NMR(CDCl 3 ,TMS): δ 9.77(t, J=2 Hz, 1H, CHO), 2.42(dt, J=7 Hz,2 Hz,2H,CH 2 CHO), 2.2-1.9(m, 2H, CF 3 CH 2 ), 1.8-1.1(m, 20H, 10×CH 2 ) 19 F-NMR(CDCl 3 , CFCl 3 ): δ -66.79(t, J=11 Hz, 3F, CF 3 )
Example 5
Synthesis of 16,16,16-trifluoro-3-hydroxy-1-hexadecene (referred to as "Compound (5)" hereinafter)
60 mg (0.225 mmol) of the Compound (4) was dissolved in 1 ml of anhydrous tetrahydrofuran under an argon atmosphere to form a solution. The solution was dropwise added to 0.4 ml (0.4 mmol) of 1 M vinyl bromide magnesium in tetrahydrofuran under ice water-cooling (about 5° C.). After the completion of the dropwise addition, the reaction mixture was warmed to a room temperature, stirred at a room temperature for 30 minutes, and again cooled with ice water. The reaction mixture was treated with an aqueous saturated ammonium chloride solution, followed by extraction with ether. An organic layer was washed with an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was then subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/10) to obtain 58 mg of Compound (5). Yield: 87.5%.
NMR(CDCl 3 ,TMS): δ 5.87(ddd, J=17 Hz,10 Hz,6 Hz, 1H, --CH═C), 5.16(m, 2H, C═CH 2 ), 4.10(q, J=7 Hz, 1H, CH--(OH)), 2.2-1.9(m, 2H, CF 3 CH 2 ), 1.8-1.1(m,23H, 11×CH 2 .+OH)
Example 6
Synthesis of 1-[(2E)-16,16,16-trifluoro-2-hexadecenyl]phenyl sulfoxide (referred to as "Compound (6)" hereinafter)
1.33 g (4.52 mmol) of the Compound (5) was dissolved in 20 ml of anhydrous tetrahydrofuran under an argon atmosphere to form a solution. 3.1 ml (4.53 mmol) of 1.46 M butyl lithium in hexane was dropwise added thereto at -20° C., followed by addition of 0.70 g (4.84 mmol) of benzenesulfenyl chloride dissolved in 1 ml of anhydrous tetrahydrofuran at -20° C. After the reaction mixture was warmed to a room temperature, it was stirred for 15 minutes and concentrated under a reduced pressure to obtain a residue. it was diluted with ether before it was washed with an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was then subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ether/hexane=2/3) to obtain 1.69 g of Compound (6). Yield: 92.9%.
m.p. 44.5°-46.0° C. NMR(CDCl 3 ,TMS): δ 7.65-7.40(m, 5H, aromatic), 5.56(dt, J=15 Hz, 6 Hz, 1H, C═CHCH 2 S), 5.27(dt, J=15 Hz, 7 Hz, 1H, C--CH 2 CH═CH--), 3.49(d, J=7 Hz, 2H, CH 2 --S(O)Ph), 2.2-1.9(m, 4H, CF 3 CH 2 +C--CH 2 --CH═CH), 1.7-1.1(m, 20H, 10×CH 2 )
Example 7
Synthesis of (16,16,16-trifluoro-3-hydroxy-1-hexadecenyl)phenyl sulfide (referred to as "Compound (7)" hereinafter)
0.67 ml (3.84 mmol) of diisobutylamine was added to 10 ml of anhydrous tetrahydrofuran under an argon atmosphere to form a mixture. 2.65 ml (3.87 mmol) of 1.46 M butyl lithium in hexane was dropwise added thereto at -78° C. After stirring of the resulting mixture at -78° C., 1.33 g (4.52 mmol) of the Compound (6) in 1.5 ml of anhydrous tetrahydrofuran was added at a stroke thereto. The resulting mixture was stirred at -78° C. for 1 hour and then at temperatures of -65° to -60° C. for 1 hour before it was again cooled to -78° C. The mixture was added through a cannula to 0.92 g (4.21 mmol) of diphenyl disulfide dissolved in 6 ml of anhydrous tetrahydrofuran which had been cooled to 0° C. After the mixture was stirred at 0° C. for 1 hour, it was poured into 70 ml of an aqueous 10% hydrochloride solution and then extracted with chloroform. An organic layer was washed with an aqueous saturated sodium bicarbonate solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure, to obtain a brown oily residue. It was immediately subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/9) to obtain 1.28 g of Compound (7). Yield:90.6%.
NMR(CDCl 3 ,TMS): δ 7.5-7.1(m, 5H, aromatic), 6.42(d, J=16 Hz, 1H, C═CHPh), 5.86(dd, J=16 Hz, 7 Hz, 1H, --CH═C--SPh), 4.17(q, J=7 Hz, 1H, CH(OH)), 2.2-1.9(m, 2H, CF 3 CH 2 ), 1.7-1.1(m, 23H, 11×CH 2 +OH)
Example 8
Synthesis of 16,16,16-trifluoro-trans-2-hexadecenal (referred to as "Compound (8)" hereinafter)
1.27 g (3.15 mmol) of the Compound (7) was dissolved in a mixed solvent of 25 ml of acetonitrile and 5 ml of water to form a solution, to which 0.901 g (3.32 mmol) of mercury chloride (II) was added. The resulting reaction mixture was stirred at temperatures of 40° to 50° C. for 15 hours, and spontaneously cooled to a room temperature before it was filtered using Celite. Undissolved portions were washed with chloroform and the filtrate and the washing liquid were combined. The combined liquid was washed with an aqueous 10% sodium bicarbonate solution. A water layer was extracted with chloroform. Organic layers which were combined were dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ether/hexane=1/10) to obtain 0.61 g of Compound (8). Yield: 74.8%.
NMR(CDCl 3 ,TMS): δ 9.51(d, J=8 Hz, 1H, --CHO), 6.86(dt, J=16 Hz,7 Hz, 1H, CH 2 CH═CH), 6.12(dd, J=16 Hz,8 Hz, 1H, C═CH--CHO), 2.34(dt, J=7 Hz, 7 Hz, 2H, CH 2 --CH═C), 2.2-1.9(m, 2H, CF 3 CH 2 ), 1.7-1.1(m, 20H, 10×CH 2 ) ##STR22##
Example 9
Synthesis of (4S)-3-[(2'S,3'R,4'E)-2'-bromo-18',18',18',-trifluoro-3'-hydroxy-4-(isopropyl)-4'-octadecenoyl-2-oxazolidinone (referred to as "Compound (9)" hereinafter)
0.65 ml (4.67 mmol) of triethylamine was added to 0.821 g (3.28 mmol) of (4S)-3-(bromoacetyl)-4-(isopropyl)-2-oxazolidinone dissolved in 11 ml of anhydrous ether at -78° C. under an argon atmosphere to form a mixture. After stirring for 5 minutes, 0.85 ml (3.38 mmol) of di-(n-butyl)boron triflate was slowly dropwise added thereto. After the reaction mixture was stirred at -78° C. for 15 minutes, refrigerants were removed and the mixture was stirred at a room temperature for 2 hours. The reaction mixture was again cooled to -78° C. gradually before 0.60 g (2.05 mmol) of the Compound (8) dissolved in 10 ml of anhydrous ether was dropwise added thereto. The resulting mixture was stirred at -78° C. for 45 minutes and then at 0° C. for 1.5 hours before it was diluted with 80 ml of ether. The resulting mixture was poured into 70 ml of an aqueous 1 M sodium hydrogensulfate solution. An organic layer was taken, washed with 30 ml of an aqueous 1 M sodium hydrogensufate solution and then with an aqueous saturated sodium chloride solution and concentrated under a reduced pressure to obtain a residue. It was again dissolved in 11 ml of ether and cooled to 0° C. A solution of 5.5 ml of methanol and 5.5 ml of an aqueous 30% hydrogen peroxide solution was gradually dropwise added thereto and the resulting reaction mixture was stirred at 0° C. for 1 hour. The reaction mixture was diluted with 30 ml of ether and washed with an aqueous saturated sodium bicarbonate solution before a water layer was twice extracted with 20 ml of ether. Organic layers were combined, washed with 30 ml of an aqueous saturated sodium bicarbonate solution and then with 20 ml of an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/4) to obtain 1.02 g of Compound (9). Yield:91.6%.
m.p. 42.5°-43.2° C. [α] D 22 +51.9° (c 0.268, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.85(dt, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.68(d, J=5 Hz, 1H, CHBr), 5.47(dd, J=16 Hz,7 Hz, 1H, CH═CH--CH 2 ), 4.6-4.2(m, 4H, CH 2 --O, CH--O, CH--NCO), 3.15(d, J=1 Hz, 1H, OH), 2.41 (m, 1H, CHMe 2 ), 2.2-1.9(m, 4H, CF 3 CH 2 , C═C--CH 2 ), 1.7-1.1(m, 20H, 10×CH 2 ), 0.95(d, J=7 Hz, 6H, 2×CH 3 )
Example 10
Synthesis of (4S)-3-[(2'R,3'R,4'E)-2'-azide-18',18',18'-trifluoro-3'-hydroxy-4-(isopropyl)-4'-octadecenoyl]-2-oxazolidinone (referred to as "Compound (10)" hereinafter)
1.02 g (1.88 mmol) of the Compound (9) was dissolved in 5 ml of dimethylsulfoxide to form a solution, to which 0.25 g (3.85 mmol) of sodium azide was added at a room temperture to obtain a reaction mixture. The mixture was stirred at the room temperature for 2 hours before it was diluted with 30 ml of ether, washed three times with 10 ml of water and then with 10 ml of an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/4) to obtain 0.65 g of Compound (10). Yield: 68.5%.
m.p. 29.0°˜31.5° C. [α] D 22 +21.4° (c 2.285, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.89(dt, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.61 (dd, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.10(d, J=8 Hz, 1H, CHN 3 ), 4.6-4.2(m, 4H CH 2 --O, CH--O, CH--NCO), 2.6-2.25(m, 2H, CHMe 2 , OH), 2.2-1.9(m, 4H, CF 3 CH 2 , C═C--H 2 ), 1.7-1.1(m, 20H, 10×CH 2 ), 0.90(d, J=7 Hz, 6H, 2×CH 3 )
Example 11
Synthesis of (4S)-3-[(2'R,3'R,4'E)-2'-azide-3'-O-tert.-butyldimethylsilyl-18',18',18'-trifluoro-3'-hydroxy-4-(isopropyl)-4'-octadecenoyl]-2-oxazolidinone (referred to as "Compound (11)" hereinafter)
0.65 g (1.29 mmol) of the Compound (10) dissolved in 7 ml of anhydrous terahydrofuran was cooled to 0° C. under an argon atmosphere. 0.3 ml (2.58 mmol) of 2,6-lutidine was then added, followed by addition of 0.45 ml (1.96 mmol) of tert.-butyldimethylsilyl triflate to obtain a reaction mixture. It was stirred at 0° C. for 30 minutes and then at a room temperature for 1 hour. It was then diluted with 25 ml of ethyl acetate, washed with 10 ml of water and then with 10 ml of an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/6) to obtain 0.648 g of Compound (11). Yield: 81.1%.
[α] D 22 -1.60° (c 4.03, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.74(dt, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.52(dd, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.22(d, J=7 Hz, 1H, CHN 3 ), 4.63(dd, J=7 Hz,7 Hz, 1H, CHOSi), 4.49(m, 1H, CH--NCO), 4.4-4.2(m, 2H, CH 2 --O), 2.3(m, 1H, CHMe 2 ), 2.2-1.9(m, 4H, CF 3 CH 2 , C═C--CH 2 ), 1.7-1.1(m, 20H, 10×CH 2 ), 0.95-0.8(m, 15H, 2×CH 3 , SiCMe 3 ), 0.08(s, 3H, SiCH 3 ), 0.06(s,3H, SiCH 3 )
Example 12
Synthesis of (2S,3R,4E)-2'-azide-3-O-tert.-butyldimethylsilyl-18,18,18-trifluoro-4-octadecene-1,3-diol (referred to as "Compound (12)" hereinafter)
648 mg (1.28 mmol) of the Compound (11) dissolved in 7 ml of anhydrous terahydrofuran was cooled to 0° C. under an argon atmosphere. 85 mg (3.90 mmol) of lithium boron hydride was then added in three portions. The resulting mixture was stirred at 0° C. for 1.5 hours and then at a room temperature for 30 minutes, and again cooled to 0° C. It was diluted with 10 ml of ethyl acetate before 10 ml of an aqueous saturated ammonium chloride solution was gradually added thereto in order to decompose excessive lithium boron hydride. An organic layer was taken and a water layer was extracted with ethyl acetate. The organic layers were combined, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/8) to obtain 320 mg of Compound (12). Yield: 50.5%. [α] D 22 -36.6° (c 4.51, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.70(dt, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.45(dd, J=15 Hz,7 Hz, 1H, CH═CH--CH 2 ), 4.22(dd, J=7 Hz,5 Hz, 1 H, CHOSi), 3.8-3.6(m, 2H, CH 2 --OH), 3.41(ddd, 1H, CHN 3 ), 2.2-1.9(m, 5H, CF 3 CH 2 , C═C--CH 2 , OH), 1.7-1.1(m, 20H, 10×CH 2 ), 0.90(s, 9H, SiCMe 3 ), 0.09(s, 3H, SiCH 3 ), 0.05(s, 3H, SiCH 3 ) 19 F-NMR(CDCl 3 ,CFCl 3 ): δ -66.79(t, J=11 Hz, 3F, CF 3 )
Example 13
Synthesis of (2S,3R,4E)-2-azide-18,18,18-trifluoro-4-octadecene-1,3-diol (referred to as "Compound (13)" hereinafter)
320 mg (0.648 mmol) of the Compound (12) dissolved in 6 ml of anhydrous terahydrofuran was cooled to 0° C. under an argon atmosphere. 1.0 ml (1.0 mmol) of 1.0 M tetrabutylammonium fluoride in tetrahydrofuran was then dropwise added. The resulting mixture was stirred at a room temperature for 1 hour. It was diluted with 200 ml of ethyl acetate, washed with water (50 ml×2) and then with 50 ml of an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/3) to obtain 255 mg of Compound (13). Yield: 100%.
[α] D 25 -28.9° (c 4.03, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.83(dt, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.54(dd, J=16 Hz,7 Hz, 1H, CH═CH--CH 2 ), 4.25(m, 1H, CHOH), 3.85-3.65(m, 2H, CH 2 --OH),3.51(dt, J=5 Hz, 5 Hz, 1H, CHN 3 ), 2.2-1.9(m, 5H, CF 3 CH 2 , C═C--CH 2 , OH), 1.7-1.1(m, 21H, 10×CH 2 , OH)
Example 14
Synthesis of (2S,3R,4E)-2-azide-18,18,18-trifluoro-1-triphenylmethoxy-4-octadecene-3-ol (referred to as "Compound (14)" hereinafter)
250 mg (0.629 mmol) of the Compound (13) was dissolved in a mixed solvent of anhydrous terahydrofuran-chloroform-pyridine (0.8 ml, 0.8 ml, 0.8 ml) under an argon atmosphere to form a solution. 240 mg (0.861 mmol) of triphenylmethyl chloride was added thereto at 0° C. The resulting mixture was stirred at a room temperature for 50 hours and concentrated under a reduced pressure to obtain a residue. It was dissolved in ether and was washed with an aqueous saturated sodium bicarbonate solution. A water layer was extracted twice with 20 ml of ether. Organic layers were combined, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/8) to obtain 420 mg of crude Compound (14). Yield: >100%.
NMR(CDCl 3 ,TMS): δ 7.6-7.15(m, 15H, 3×Ph), 5.66(dt, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.32(dd, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 4.20(m, 1H, CHOH), 3.50(dt, J=5 Hz, 5 Hz, 1H, CHN 3 ), 3.30(d, J=5 Hz, 2H, CH 2 --OTr), 2.2-1.9(m, 5H, CF 3 CH 2 , C═C--CH 2 , OH), 1.7-1.1(m, 20H, 10×CH 2 )
Example 15
Synthesis of (2S,3R,4E)-2-azide-3-benzoyloxy-18,18,18-trifluoro-1-triphenylmethoxy-4-octadecene (referred to as "Compound (15)" hereinafter)
420 mg (0.676 mmol) of the crude Compound (14) was dissolved in a mixed solvent of 2 ml of anhydrous toluene and 0.5 ml of pyridine to form a solution. 0.18 ml (1.55 mmol) of benzoyl chloride was added thereto at 0° C. The mixture was warmed to a room temperature, and stirred for 3 hours. It was poured into ice-cooled water and extracted with ether. An organic layer was dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/20) to obtain 360 mg of Compound (15). Yield: 75.3%.
[α] D 23 -15.2° (c 7.11, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 8.1-7.1(m, 20H, 4×Ph), 5.82(dt, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.63(dd, J=9 Hz, 5 Hz, 1H, CHOBz), 5.42(dd, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 3.86(dt, J=6 Hz, 5 Hz, 1H, CHN 3 ), 3.29 and 3.20(dd and dd, 2H, CH 2 --OTr), 2.2-1.9(m, 4H, CF 3 CH 2 , C═C--CH 2 ), 1.7-1.1(m, 20H, 10×CH 2 )
Example 16
Synthesis of (2S,3R,4E)-2-azide-3-benzoyloxy-18,18,18-trifluoro-4-octadecene-1-ol (referred to as "Compound (16)" hereinafter)
To 360 mg (0.496 mmol) of the Compound (15) dissolved in a mixed solvent of 1.8 ml of anhydrous toluene and 1.2 ml of anhydrous methanol, 83 ml (0.675 mmol) of boron trifluoride-diethyl ether complex was dropwise added at 0° C. under an argon atmosphere. The reaction mixture was stirred at a room temperature for 11 hours, poured into an aqueous saturated sodium bicarbonate solution which had been cooled with ice, and extracted with ether. An organic layer was dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/5) to obtain 229 mg of Compound (16). Yield: 95.5%.
[α] D 25 -42.0° (c 4.04, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 8.1-7.4(m, 5H, Ph), 6.1-5.8(m, 1H, CH═CH--CH 2 ), 5.7-5.5(m, 2H, CHOBz, CH═CH--CH 2 ), 3.8-3.5(2m, 3H, CHN 3 , CH 2 --OH), 2.2-1.7(m, 5H, CF 3 CH 2 , C═C--CH 2 , OH), 1.6-1.1(m, 20H, 10×CH 2 ) ##STR23##
Example 17
Synthesis of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-O-(3-O-acetyl-2,6-di-O-benzoyl-β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-2-azide-3-O-benzoyl-18,18,18-trifluoro-4-octadecene-1,3-diol (referred to as "Compound (17)" hereinafter)
289 mg (0.207 mmol) of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-3-O-acetyl-2,6-di-O-benzoyl-.alpha.-D-glucopyranosyl trichloroacetoimidate and 200 mg (0.414 mmol) of the Compound (16) were dissolved in 6 ml of anhydrous dichloromethane under an argon atmosphere to form a solution. 3.45 g of Molecular Sieve 4A was added thereto. The mixture was stirred at a room temperature for 30 minutes. It was cooled to 0° C. before 60 mg (0.423 mmol) of boron trifluoride-diethyl ether complex was added. The reaction mixture was stirred at 0° C. for 4 hours. It was filtered using Celite and undissolved portions were washed with dichloromethane. The filtrate and the washing liquid were combined, washed with an aqueous 1 M sodium bicarbonate solution and then with water, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=3/1) to obtain 300 mg of Compound (17). Yield: 84.4%.
[α] D 25 -2.49° (c 0.59, CHCl 3 ) IRmax(KBr)(cm -1 ): 3390(NH), 2110(N 3 ), 1740,1230 (ester), 1690,1540 (amide), 710 (phenyl) NMR(CDCl 3 ,TMS): lactose unit; δ 4.60 (dd, J=10 Hz, 3 Hz, 1H, H-3'), 4.68(d, J=8 Hz, 1H, H-1), 4.88(d, J=8 Hz, 1H, H-1'), 5.00(d, 1H, H-4'), 5.05(d, 1H, J=10 Hz, H-2') 5.25(dd, J=9 Hz, 1H, H-2), 7.3-8.1 (m, 20H, 4×Ph), sialic acid unit; δ 1.66 (dd, J=13 Hz, 13 Hz, 1H, H-3a), 1.84(s, 3H, N--COCH 3 ), 2.58(dd, J=13 Hz, 5 Hz, 1H, H-3e), 3.71(s, 3H, OCH3), 4.86(m, 1H, H-4), ceramide unit; δ 5.67(dt, J=13 Hz, 7 Hz, 1H, H-5), O-acetyl group; δ 1.98, 2.00, 2.01, 2.02, 2.03, 2.11, 2.20(7s, 21H, 7×Ac) 19 F-NMR(CDCl 3 ,CFCL 3 ): δ -66.79(t, J=11 Hz, 3F, CF 3 )
Example 18
Synthesis of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-O-(3-O-acetyl-2,6-di-O-benzoyl-β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-3-O-benzoyl-18,18,18-trifluoro-2-tetracosaneamide-4-octadecene-1,3-diol (referred to as "Compound (18)" hereinafter)
100 mg (0.058 mmol) of the Compound (17) was dissolved in a mixed solvent of 10 ml of pyridine and 2 ml of water to form a solution. Hydrogen sulfide gas was passed through the solution at a room temperature for 48 hours. After the starting substance was confirmed to disappear, hydrogen sulfide was removed from the reaction mixture and water and pyridine were then distilled off under a reduced pressure. The residue was dissolved in 5 ml of anhydrous dichloromethane to form a solution to which 44 mg (0.12 mmol) of tetracosanoic acid and 35 mg (0.18 mmol) of 1-ethyl-3-(3-dimethylaminoprpyl)carbodiimide hydrochloride (referred to as WSC hereinafter) were added under an argon atmosphere. The reaction mixture was stirred at a room temperature for 16 hours. It was then diluted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to silica gel column chromatography (a packing material: silica gel 60(7734), an eluent: methanol/chloroform=1/60→1/40) to obtain 85 mg of Compound (18). Yield: 71.5%.
[α] D 25 +9.3° (c 2.0, CHCl 3 ) IRmax(KBr)(cm -1 ): 3390(NH), 2930,2850(Me, methylene), 1740,1230(ester), 1690,1540(amide), 710(phenyl) NMR(CDCl 3 ,TMS): lactose unit; δ 4.61 (d, J=7.5 Hz, 1H, H-1), 4.83(d, J=8 Hz, 1H, H-1'), 5.00(d, 1H, H-4'), 5.01(d, J=10 Hz,8 Hz, 1H, H-2'), 5.25 (dd, J=9 Hz,7.5 Hz, 1H, H-2), 7.3-8.1 (m, 20H, 4×Ph), sialic acid unit; δ 1.66(dd, J=13 Hz, 13 Hz, 1H, H-3a), 1.84(s, 3H, N--COCH 3 ), 2.58(dd, J=13 Hz, 5 Hz, 1H, H-3e), 3.71(s, 3H, OCH 3 ), 4.86(m, 1H, H-4), ceramide unit; δ 5.63(d, J=9 Hz, 1H, NH), 5.67(dt, J=15 Hz, 7 Hz, 1H, H-5), O-acetyl group; δ 1.99(2), 2.01, 2.015, 2.02, 2.10, 2.18(7s, 21H, 7×Ac) 19 F-NMR(CDCl 3 ,CFCL 3 ): δ -66.79(t, J=11 Hz, 3F, CF 3 )
Example 19
Synthesis of O-(5-acetoamide-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonic acid)-(2→3)-O-(β-D-galactopyranosyl)-(1→4)-O-(β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-18,18,18-trifluoro-2-tetracosaneamide-4-octadecene-1,3-diol (referred to as "Compound (19)" hereinafter)
15 mg (0.28 mmol) of sodium methoxide was added under an argon atmosphere to 80 mg (0.039 mmol) of the Compound (18) dissolved in 3.6 ml of methanol. The resulting mixture was stirred at a room temperature for 9.5 hours. It was cooled to 0° C. and then 0.36 ml of water was added. The resulting mixture was stirred at 0° C. for 10 hours and then subjected to Amberlight IR120 (H+) column chromatography (an eluent: methanol). Eluted portions were concentrated to obtain a residue. It was washed with ether to obtain 39.3 mg of Compound (19). Yield: 76.2%.
[α] D 25 -0.27° (c 0.50, 1:1 CHCl 3 --CH 3 OH) IRmax(KBr)(cm -1 ): 3390(OH,NH), 2920,2850(Me, methylene), 1725(carbonyl), 1635,1560(amide), NMR(2: 1 CD 3 OD--CDCl 3 ,TMS): lactose unit; δ 4.30(d, J=8 Hz, 1H, H-1), 4.42(d, J=8 Hz, 1H, H-1'), sialic acid unit; δ 2.02(s, 3H, N--COCH 3 ), 2.79 (dd, J=12 Hz, 4 Hz, 1H, H-3e), ceramide unit; δ 0.88(t, J=7 Hz, 3H, CH 2 CH 3 ), 2.18(t, J=8 Hz, 2H, CH 2 CO), 4.21(dd, J=10 Hz,4 Hz, 1H, H-1), 5.46(dd, J=15 Hz,8 Hz, 1H, H-4), 5.70(dt, J=15 Hz, 7 Hz, 1H, H-5) 19 F-NMR(2: 1 CD 3 OD--CDCl 3 ,CFCL 3 ): d -66.79(t, J=11 Hz, 3F, CF 3 ) ##STR24##
Example 20
Synthesis of 12,12,13,13,13-pentafluorotridecanol (referred to as "Compound (20)" hereinafter)
3.0 ml (15.0 mmol) of 10-undecene-1-ol was dissolved in 110 ml of degassed hexane. 3.5 ml (25.5 mmol) of perfluoroethyl iodide was added 0° C. to the resulting solution. After stirring thereof for 5 minutes, 2.0 ml (2.0 mmol) of 1.0 M triethyl boran in hexane was added thereto to form a mixture which was stirred at 0° C. for 30 minutes and then at room temperature for 30 minutes to form a mixture. A residue which was obtained by condensation of the mixture under a reduced pressure was dissolved in a mixed solvent of 23 ml of ether and 23 ml of acetic acid. 1.35 g (20.7 mmol) of zinc powder was added to the solution at 0° C. and the resulting mixture was stirred at 0° C. for 30 minutes and then at a room temperature for 1 hour and 20 minutes. The reaction mixture was diluted with 200 ml of ether and filtered using Celite. The filtrate was washed with an aqueous 10% potassium hydroxide solution (100 ml×3) and then with an aqueous saturated sodium chloride solution (100 ml), dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/4) to obtain 3.04 g of Compound (20). Yield: 70.0%. Recrystallization thereof from hexane gave a white needle crystal.
m.p. 42.5°-43.5° C. NMR(CDCl 3 ,TMS): δ 3.64(t, J=7 Hz; 2H, CH 2 --OH), 2.2-1.8(m, 2H, CF 2 CH 2 ), 1.7-1.2(m, 19H, 9×CH 2 +OH)
Example 21
Synthesis of 13-bromo-1,1,1,2,2-pentafluorotridecane (referred to as "Compound (21)" hereinafter)
To 1.425 mg (4.91 mmol) of the Compound (21) which had been dissolved in 53 ml of anhydrous dichloromethane, 1.54 g (5.87 mmol) of triphenylphosphine and 2.47 g (7.45 mmol) carbon tetrabromide were added at a room temperature. The mixture was treated with 30 ml of an aqueous saturated sodium bicarbonate solution after 5 minutes. An organic layer was taken and a water layer was extracted with 20 ml of dichloromethane. The organic layers were combined, washed with an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was treated with 200 ml of hexane and an undissolved portion was filtered off. The filtrate was concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: hexane) to obtain 1.682 g of Compound (21). Yield: 97.0%.
NMR(CDCl 3 ,TMS): δ 3.41(t, J=7 Hz, 2H, CH 2 --Br), 2.2-1.75(m, 4H, CF 2 CH 2 , CH 2 CH 2 Br), 1.7-1.2(m, 16H, 8×CH 2 ) 19 F-NMR(CDCl 3 , CFCL 3 ): δ -85.74(s, 3F, CF 3 ), -118.47(t, J=18 Hz, 2F, CF 2 )
Example 22
Synthesis of 15,15,16,16,16-pentafluoro-1,3-bis(methylthio)-1-hexadecene (referred to as "Compound (22)" hereinafter)
To 1.36 ml (9.70 mmol) of diisopropylamine and 0.75 g (4.51 mmol) of 1,3-bis(methythio)-2-methoxypropane which had been dissolved in 14 ml of anhydrous terahydrofuran, 5.72 ml (9.15 mmol) of 1.6 M butyl lithium in hexane was added at -78° C. under an argon atmosphere. The mixture was warmed to a room temperature and stirred under an argon atmosphere for 100 minutes. It was again cooled to -78° C. before 1.62 g (4.59 mmol) of the Compound (21) dissolved in 14 ml of anhydrous tetrahydrofuran was dropwise added thereto to form a mixture. It was stirred at -78° C. for 2 hours. 0.4 ml of methanol was added at -78° C., diluted with ether and washed with an aqueous saturated ammonium chloride solution. An organic layer was washed with water and then with an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: dichloromethane/hexane=1/10) to obtain 1.26 g of Compound (22). Yield: 81.7%.
NMR(CDCl 3 ,TMS): δ 6.03(d,J=15 Hz, 1H,C═CHSMe), 5.17(dd, J=15 Hz,9 Hz,1H, CH═CHSMe), 3.12(m, 1H, CH(SMe)--CH═C), 2.27(s, 3H, C═CHSCH 3 ), 1.99(s, 3H, CH--SCH 3 ), 2.2-1.8(m, 2H, CF 2 CH 2 ), 1.7-1.1(m, 20H, 10×CH 2 )
Example 23
Synthesis of 15,15,16,16,16-pentafluoro-trans-2-hexadecenal (referred to as "Compound (23)" hereinafter)
To 1.256 mg (3.09 mmol) of the Compound (22) which had been dissolved in a mixed solvent of 8 ml of acetonitrile and 1 ml of water, 3.32 g (12.2 mmol) of mercury chloride (II) was added. The reaction mixture was stirred at 50° C. for 4 hours. After being spontaneously cooled to a room temperature, it was diluted with an aqueous saturated sodium chloride solution. It was extracted with ether. An organic layer was washed with water and then with an aqueous 10% sodium bicarbonate solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ether/hexane=1/10) to obtain 0.617 g of Compound (23). Yield: 60.8%.
NMR(CDCl 3 ,TMS): δ 9.51(d, J=8 Hz, 1H, --CHO), 6.86(dt, J=16 Hz,7 Hz, 1H, CH 2 CH═CH), 6.12(dd, J=16 Hz,8 Hz, 1H, C═CH--CHO), 2.34(dt, J=7 Hz, 7 Hz, 2H, CH 2 --CH═C), 2.2-1.8(m, 2H, CF 3 CH 2 ), 1.7-1.2(m, 18H, 9×CH 2 ) ##STR25##
Example 24
Synthesis of (4S)-3-[(2'S,3'R,4'E)-2'-bromo-17',17',18',18',18'-pentafluoro-3'-hydroxy-4-(isopropyl)-4'-octadecenoyl]-2-oxazolidinone (referred to as "Compound (24)" hereinafter)
To 0.570 g (2.28 mmol) of (4S)-3-(bromoacetyl)-4-(isopropyl)-2-oxazolidinone dissolved in 9 ml of anhydrous ether, 0.45 ml (3.23 mmol) of triethylamine was added at -78° C. under an argon atmosphere to form a solution. After stirring for 5 minutes, 0.58 ml (2.31 mmol) of di-(n-butyl)boron triflate was gradually dropwise added thereto. After the resulting mixture was stirred at -78° C. for 15 minutes, refrigerants were removed and the mixture was stirred at a room temperature for 2 hours. The mixture was again cooled to -78° C. gradually before 0.47 g (1.43 mmol) of the Compound (23) dissolved in 10 ml of anhydrous ether was dropwise added thereto. The resulting mixture was stirred at -78° C. for 45 minutes and then at 0° C. for 1.5 hours before it was diluted with 80 ml of ether. The resulting mixture was poured into 70 ml of an aqueous 1 M sodium hydrogensulfate solution. An organic layer was taken, washed with 30 ml of an aqueous 1 M sodium hydrogensulfate solution and then with an aqueous saturated sodium chloride solution and concentrated under a reduced pressure to obtain a residue. It was again dissolved in 8 ml of ether and cooled to 0° C. A solution of 4 ml of methanol and 4 ml of an aqueous 30% hydrogen peroxide solution was gradually dropwise added and the resulting reaction mixture was stirred at 0° C. for 1 hour. The reaction mixture was diluted with 30 ml of ether and washed with an aqueous saturated sodium bicarbonate solution. A water layer was twice extracted with 20 ml of ether. Organic layers were combined, washed with 30 ml of an aqueous saturated sodium bicarbonate solution and then with 20 ml of an aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/3) to obtain 0.822 g of Compound (24). Yield: 99.3%.
[α] D 22 +42.9° (c 0.225, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.85(dt, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.69(d, J=5 Hz, 1H, CHBr), 5.47(dd, J=16 Hz,7 Hz, 1H, CH═CH--CH 2 ), 4.6-4.2(m, 4H, CH 2 --O, CH--O, CH--NCO), 3.15(bs, 1H, OH), 2.40(m, 1H, CHMe 2 ), 2.2-1.8(m, 4H, CF 3 CH 2 , C═C--CH 2 ), 1.7-1.1(m, 18H, 9×CH 2 ), 0.95(d, J=7 Hz, 6H, 2×CH 3 )
Example 25
Synthesis of (4S)-3-[(2'R,3'R,4'E)-2'-azide-17',17',18',18',18'-pentafluoro-3'-hydroxy-4-(isopropyl)-4'-octadecenoyl]-2-oxazolidinone (referred to as "Compound (25)" hereinafter)
0.825 g (1.43 mmol) of the Compound (24) was dissolved in 4 ml of dimethyl sulfoxide to form a solution. 0.183 g (2.81 mmol) of sodium azide was added thereto at a room temperature. The resulting mixture was stirred at the room temperature for 2 hours. It was then diluted with 30 ml of ether, washed three times with 10 ml of water and then with 10 ml of an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/3) to obtain 0.529 g of Compound (25). Yield: 68.6%.
[α] D 22 +18.3° (c 2.25, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.90(dt, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.60(dd, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.10(d, J=8 Hz, 1H, CHN 3 ), 4.6-4.2(m, 4H CH 2 --O, CH--O, CH--NCO), 2.5-2.25(m, 2H, CHMe 2 , OH), 2.2-1.8(m, 4H, CF 3 CH 2 , C═C--CH 2 ), 1.7-1.1(m, 18H, 9×CH 2 ), 0.94 (d, J=7 Hz, 3H, CH 3 ), 0.90 (d, J=8 Hz, 3H, CH 3 )
Example 26
Synthesis of (4S)-3-[(2'R,3'R,4'E)-2'-azide-3'-O-tert.-butyldimethylsilyl-17',17',18',18',18'-pentafluoro-3'-hydroxy-4-(isopropyl)-4'-octadecenoyl]-2-oxazolidinone (referred to as "Compound (26)" hereinafter)
0.517 g (0.956 mmol) of the Compound (25) dissolved in 7 ml of anhydrous terahydrofuran was cooled to 0° C. under an argon atmosphere. 0.25 ml (2.15 mmol) of 2,6-lutidine was then added, followed by addition of 0.33 ml (1.44 mmol) of tert.-butyldimethylsilyl triflate to obtain a reaction mixture. The mixture was stirred at 0° C. for 30 minutes. After being stirred at a room temperature for 1 hour, it was diluted with 25 ml of ethyl acetate, washed with 10 ml of water and then with 10 ml of an aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/6) to obtain 0.554 g of Compound (26). Yield: 88.3%.
[α] D 22 -1.63° (c 4.085, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.74(dt, J=15 Hz, 6 Hz, 1H, CH═CH--CH 2 ), 5.52(dd, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.21 (d, J=6 Hz, 1H, CHN 3 ), 4.63(dd, J=7 Hz,7 Hz,1H, CHOSi), 4.49(m, 1H, CH--NCO), 4.4-4.2(m, 2H, CH 2 O),2.3(m, 1H, CHMe 2 ),2.2-1.8(m, 4H, CF 2 CH 2 , C═C--CH 2 ), 1.7-1.1(m, 18H, 9×CH 2 ), 0.95-0.8(m, 15H, 2×CH 3 , SiCMe 3 ), 0.08(s, 3H, SiCH 3 ), 0.06(s, 3H, SiCH 3 )
Example 27
Synthesis of (2S,3R,4E)-2-azide-3-O-tert.-butyldimethylsilyl-17,17,18,18,18-pentafluoro-4-octadecene-1,3-diol (referred to as "Compound (27)" hereinafter)
554 mg (0.845 mmol) of the Compound (26) dissolved in 5 ml of anhydrous terahydrofuran was cooled to 0° C. under an argon atmosphere. 55 mg (2.53 mmol) of lithium boron hydride was then added in three portions. The resulting mixture was stirred at 0° C. for 1.5 hours and then at a room temperature for 30 minutes, and again cooled to 0° C. It was diluted with 10 ml of ethyl acetate before 10 ml of an aqueous saturated ammonium chloride solution was gradually added thereto in order to decompose excessive lithium boron hydride. An organic layer was taken and a water layer was extracted with ethyl acetate. The organic layers were combined, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/9) to obtain 320 mg of Compound (27). Yield: 71.5%.
[α] D 25 -35.6° (c 4.535, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.70(dt, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.45(dd, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 4.22(dd, J=7 Hz,5 Hz, 1H, CHOSi), 3.8-3.6(m, 2H, CH 2 --OH), 3.41(ddd, 1H, CHN 3 ), 2.2-1.9(m, 5H, CF 2 CH 2 , C═C--CH 2 , OH), 1.7-1.1(m, 18H, 9×CH 2 ), 0.90(s, 9H, SiCMe 3 ), 0.09(s, 3H, SiCH 3 ), 0.05(s, 3H, SiCH 3 ) 19 F-NMR(CDCl 3 , CFCL 3 ): δ -85.74(s, 3F, CF 3 ), -118.47(t, J=18 Hz, 2F, CF 2 )
Example 28
Synthesis of (2S,3R,4E)-2-azide-17,17,18,18,18-pentafluoro-4-octadecene-1,3-diol (referred to as "Compound (28)" hereinafter)
302 mg (0.570 mmol) of the Compound (27) dissolved in 6 ml of anhydrous tetrahydrofuran was cooled to 0° C. under an argon atmosphere. 0.9 ml (0.9 mmol) of 1.0 M tetrabutylammonium fluoride in tetrahydrofuran was then dropwise added. The resulting mixture was stirred at a room temperature for 2 hours. It was diluted with 200 ml of ethyl acetate, washed with water (50 ml×2) and then with 50 ml of an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/2) to obtain 226 mg of Compound (28). Yield: 95.4%.
[α] D 25 -27.1° (C 4.02, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.83(dt, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.54(dd, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 4.25(m, 1H, CHOH), 3.85-3.65(m, 2H, CH 2 --OH), 3.51(dt, J=5 Hz, 5 Hz, 1H, CHN 3 ), 2.2-1.9(m, 5H, CF 3 CH 2 , C═C--CH 2 , OH), 1.7-1.1(m, 19H, 9×CH 2 , OH) 19 F-NMR(CDCl 3 ,CFCL 3 ): δ -85.7(s, 3F, CF 3 ), -118.4(t, J=18 Hz, 2F, CF 2 )
Example 29
Synthesis of (2S,3R,4E)-2-azide-17,17,18,18,18-pentafluoro-1-triphenylmethoxy-4-octadecene-3-ol (referred to as "Compound (29)" hereinafter)
224 mg (0.539 mmol) of the Compound (27) was dissolved in a mixed solvent of anhydrous tetrahydrofuran-chloroform-pyridine (0.7 ml, 0.7 ml, 0.7 ml) under an argon atmosphere to form a solution. 200 mg (0.717 mmol) of triphenylmethyl chloride was added thereto at 0° C. The mixture was stirred at a room temperature for 50 hours and concentrated under a reduced pressure to obtain a residue. It was dissolved in ether and washed with an aqueous saturated sodium bicarbonate solution. A water layer was extracted with 20 ml of ether twice. Organic layers were combined, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/7) to obtain 290 mg of Compound (29). Yield: 81.8%.
[α] D 25 -0.16° (C 1.49, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 7.6-7.15(m, 15H, 3×Ph), 5.66(dt, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.32(dd, J=15 Hz,7 Hz,1H,CH═CH--CH 2 ),4.20(m, 1H,CHOH), 3.51(dt, J=5 Hz,5 Hz,1H, CHN 3 ), 3.30(d, J=5 Hz, 2H, CH 2 -OTr), 2.2-1.9(m, 4H, CF 2 CH 2 , C═C--CH 2 ), 1.7-1.1(m, 19H, 9×CH 2 , OH)
Example 30
Synthesis of (2S,3R,4E)-2-azide-3-benzoyloxy-17,17,18,18,18-pentafluoro-1-triphenylmethoxy-4-octadecene (referred to as "Compound (30)" hereinafter)
290 mg (0.441 mmol) of the Compound (29) was dissolved in a mixed solvent of 2 ml of anhydrous toluene and 0.4 ml of pyridine to form a solution. 0.14 ml (1.21 mmol) of benzoyl chloride was added thereto at 0° C. The mixture was stirred at a room temperature for 13 hours, poured into ice-cooled water and extracted with ether. An organic layer was dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/20) to obtain 228 mg of Compound (30). Yield: 67.9%.
[α] D 23 -14.9° (c 3.20, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 8.1-7.1(m, 20H, 4×Ph), 5.82(dt, J=15 Hz, 7 Hz, 1H,CH═CH--CH 2 ), 5.63 (dd, J=9 Hz, 5 Hz, 1H, CHOBz), 5.42(dd, J=15 Hz, 7Hz, 1H, CH═CH--CH 2 ), 3.8(dt, J=6 Hz, 5 Hz, 1H, CHN 3 ), 3.29 and 3.20(dd and dd, 2H, CH 2 --OTr), 2.2-1.9(m, 4H, CF 2 CH 2 , C═C--CH 2 ), 1.7-1.1(m, 18H, 9×CH 2 )
Example 31
Synthesis of (2S,3R,4E)-2-azide-3-benzoyloxy-17,17,18,18,18-pentafluoro-4-octadecene-1-ol (referred to as "Compound (31)" hereinafter)
To 223 mg (0.293 mmol) of the Compound (30) dissolved in a mixed solvent of 1.1 ml of anhydrous toluene and 0.7 ml of anhydrous methanol, 50 ml (0.407 mmol) of boron trifluoride-diethyl ether complex was dropwise added at 0° C. under an argon atmosphere. The resulting mixture was stirred at a room temperature for 11 hours, poured into an aqueous saturated sodium bicarbonate solution which had been cooled with ice and extracted with ether. An organic layer was dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/5) to obtain 140 mg of Compound (31). Yield: 92.1%.
[α] D 25 -38.7° (c 3.16, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 8.1-7.4(m, 5H, Ph), 6.1-5.8(m, 1H, CHαCH--CH 2 ), 5.7-5.5(m, 2H, CHOBz, CH═CH--CH 2 ), 3.8-3.5(2m, 3H, CHN 3 , CH 2 --OH), 2.2-1.7(m, 5H, CF 2 CH 2 , C═C--CH 2 , OH), 1.6-1.2(m, 18H, 9×CH 2 ) ##STR26##
Example 32
Synthesis of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-O-(3-O-acetyl-2,6-di-O-benzoyl-β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-2-azide-3-O-benzoyl-17,17,18,18,18-pentafluoro-4-octadecene-1,3-diol (referred to as "Compound (32)" hereinafter)
188 mg (0.134 mmol) of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-3-O-acetyl-2,6-di-O-benzoyl-.alpha.-D-glucopyranosyl trichloroacetoimidate and 140 mg (0.269 mmol) of the Compound (31) were dissolved in 4 ml of anhydrous dichloromethane under an argon atmosphere to form a solution. 2.25 g of Molecular Sieve 4A was added thereto. The resulting mixture was stirred at a room temperature for 30 minutes. It was cooled to 0° C. before 34 ml (0.276 mmol) of boron trifluoride-diethyl ether complex was added. The reaction mixture was stirred at 0° C. for 2 hours. It was filtered using Celite and undissolved portion were washed with dichloromethane. The filtrate and the washing liquid were combined, washed with an aqueous 1 M sodium bicarbonate solution and then with water, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=3/1) to obtain 204 mg of Compound (32). Yield: 86.4%.
[α] D 25 -2.54° (c 0.57, CHCl 3 ) IRmax(KBr)(cm -1 ): 3390(NH), 2105(N3), 1740,1230(ester), 1690,1535(amide), 715(phenyl) NMR(CDCl 3 ,TMS): lactose unit; δ 4.60(dd, J=10 Hz,3 Hz, 1H, H-3'), 4.68(d, J=8 Hz, 1H, H-1), 4.87(d, J=8 Hz, 1H, H-1'), 5.01(d, J=3 Hz, 1H, H-4'), 5.02(dd, 1H, J=10 Hz,8 Hz, H-2'), 5.25(dd, J=9 Hz, 1H, H-2), 7.3-8.1 (m, 20H, 4×Ph), sialic acid unit; δ 1.66(dd, J=13 Hz,13 Hz, 1H, H-3a), 1.84(s, 3H, N--COCH 3 ), 2.57(dd, J=13 Hz, 5 Hz, 1H, H-3e), 3.71(s, 3H, OCH 3 ), 4.85(m, 1H, H-4), ceramide unit; δ 5.67(dt, J=13 Hz, 7 Hz, 1H, H-5), O-acetyl unit; δ 1.98, 1.99, 2.01, 2.02(×2), 2.11, 2.20(7s, 21H, 7×Ac) 19 F-NMR(CDCl 3 ,CFCL 3 ): δ -85.7(s, 3F, CF 3 ), -118.4(t, J=18 Hz, 2F, CF 2 )
Example 33
Synthesis of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-O-(3O-acetyl-2,6-di-O-benzoyl-β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-3-O-benzoyl-17,17,18,18,18-pentafluoro-2-tetracosaneamide-4-octadecene-1,3-diol (referred to as "Compound (33)" hereinafter)
130 mg (0.074 mmol) of the Compound (32) was dissolved in a mixed solvent of 12.5 ml of pyridine and 2.5 ml of water to form a solution. Hydrogen sulfide gas was passed through the solution at a room temperature for 48 hours. After the starting substance was confirmed to disappear, hydrogen sulfide was removed from the reaction mixture, and water and pyridine were then distilled off under a reduced pressure. The residue was dissolved in 6 ml of anhydrous dichloromethane to form a solution to which 35 mg (0.095 mmol) of tetracosanoic acid and 44 mg (0.23 mmol) of WSC were added under an argon atmosphere. The reaction mixture was stirred at a room temperature for 16 hours. It was then diluted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to silica gel column chromatography (a packing material: silica gel 60(7734), an eluent: methanol/chloroform=1/60→1/40)to obtain 96 mg of Compound (33). Yield: 62.4%.
[α] D 25 +8.5° (c 2.0, CHCl 3 ) IRmax(KBr)(cm -1 ): 3395(NH), 2930,2855(Me, methylene), 1750,1225(ester), 1685,1530(amide), 715(phenyl) NMR(CDCl 3 ,TMS): lactose unit; δ 4.61(d, J=8 Hz, 1H, H-1), 4.84(d, J=8 Hz, 1H, H-1'), 5.18(dd, J=10 Hz,8 Hz, 1H, H-2), 7.3-8.1 (m, 20H, 4×Ph), sialic acid unit; δ 1.66(dd, J=13 Hz,13 Hz, 1H, H-3a), 1.84(s, 3H, N--COCH 3 ), 2.58(dd, J=13 Hz, 5 Hz, 1H, H-3e), 3.71(s, 3H, OCH 3 ), 4.86(m, 1H, H-4), ceramid unit; δ 5.62(d, J=9 Hz, 1H, NH), 5.76(dt, J=15 Hz, 7 Hz, 1H, H-5), O-acetyl group; δ 1.99(2), 2.01, 2.015, 2.02, 2.10, 2.18(7s, 21H, 7×Ac)
Example 34
Synthesis of O-(5-acetoamide-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonic acid)-(2→3)-O-(β-D-galactopyranosyl)-(1→4)-O-(β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-17,17,18,18,18-pentafluoro-2-tetracosaneamide-4-octadecene-1,3-diol (referred to as "Compound (34)" hereinafter)
17 mg (0.31 mmol) of sodium methoxide was added under an argon atmosphere to 90 mg (0.043 mmol) of the Compound (33) dissolved in 4.0 ml of anhydrous methanol. The resulting mixture was stirred at a room temperature for 15 hours. It was cooled to 0° C. and 0.40 ml of water was then added thereto. The resulting mixture was stirred at 0° C. for 12 hours. It was subjected to Amberlite IR120 column (H+) chromatography (eluent: methanol). Eluted portions were concentrated under a reduced pressure to obtain a residue which was then subjected to column chromatography (packing agent: Sephadex LH-20, an eluent: methanol) to obtain 52.4 mg of Compound (34). Yield: 89.5%.
[α] D 25 -0.53° (c 0.50, 1:1 CH 3 OH--CHCl 3 ) IRmax(KBr)(cm -1 ): 3380(NH), 2920,2850(Me, methylene), 1730(carbonyl), 1640,1555(amide) NMR(2: 1 CD 3 OD--CDCl 3 ,TMS): lactose unit; δ 4.30(d, J=8 Hz, 1H, H-1), 4.42(d, J=8 Hz, 1H, H-1'), sialic acid unit; δ 2.02(s, 3H, N--COCH 3 ), 2.79(dd, J=12 Hz, 4 Hz, 1H, H-3e), ceramide unit; δ 0.89(t, J=7 Hz, 3H, CH 2 CH 3 ), 2.18(t, J=8 Hz, 2H, CH 2 CO), 4.21(dd, J=10 Hz,4 Hz, 1H, H-1), 5.46(dd, J=15 Hz,8 Hz, 1H, H-4), 5.70(dt, J=15 Hz, 7 Hz, 1H, H-5) 19 F-NMR(2: 1 CD 3 OD--CDCl 3 ): δ -118.0(t, J=18 Hz, 2F, CF 2 ), 85.7(s, 3F, CF 3 ) ##STR27##
Example 35
Synthesis of perfluorooctyl-1-hexanol (referred to as "Compound (35)" hereinafter)
1.0 ml (10.0 mmol) of 5-hexenol was dissolved in 110 ml of degassed hexane to form a solution. 5.46 g (10.0 mmol) of perfluorooctyl iodide was added at 0° C. thereto, followed by the addition of 1.0 ml (1.0 mmol) of 1.0 M triethyl boran in hexane to form a mixture. It was stirred at 0° C. for 30 minutes and then at a room temperature for 30 minutes. A residue which was obtained by concentration of the mixture under a reduced pressure was dissolved in a mixed solvent of 15 ml of ether and 15 ml of acetic acid. 0.90 g (13.8 mmol) of zinc powder was added to the solution at 0° C. and the resulting mixture was stirred at 0° C. for 30 minutes and then at a room temperature for 1 hour and 20 minutes. The reaction mixture was diluted with 200 ml of ether and filtered using Celite. The filtrate was washed with an aqueous 10% sodium hydroxide solution (100 ml×3) and then with an aqueous saturated sodium chloride solution (100 ml), dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/4) to obtain 3.70 mg of Compound (35). Yield: 71.2%. Recrystallization thereof from hexane-ether gave a white needle crystal.
m.p. 56.0°-57.0° C. NMR(CDCl 3 ,TMS): δ 3.66(t, J=6 Hz, 2H, CH 2 --OH), 2.25-1.85(m, 2H, CF 2 CH 2 ), 1.7-1.3(m, 9H, 4×CH 2 +OH)
Example 36
Synthesis of 6-perfluorooctylhexanal (referred to as "Compound (36)" hereinafter)
1.04 g (0.710 mmol) of the Compound (35) dissolved in 15 ml of dichloromethane was added to 770 mg (3.57 mmol) of pyridinium chlorochromate in 6 ml of dichloromethane. The resulting mixture was stirred at a room temperature for 8 hours, then diluted with ether and filtered using Celite. The filtrate was distilled to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/10) to obtain 750 mg of Compound (36). Yield: 72.4%.
m.p. 31.0°-35.0° C. NMR(CDCl 3 ,TMS): δ 9.79(t, J=1 Hz, 1H, CHO), 2.48(dt, J=7 Hz,1 Hz, 2H,CH 2 CHO), 2.2-1.85 (m, 2H, CF 2 CH 2 ), 1.8-1.3(m, 6H, 3×CH 2 )
Example 37
Synthesis of 8-perfluorooctyl-3-hydroxy-1-octene (referred to as "Compound (37)" hereinafter)
750 mg (1.45 mmol) of the Compound (36) which had been dissolved in 5 ml of anhydrous tetrahydrofuran under an argon atmosphere was dropwise added to 2.6 ml (2.6 mmol) of 1 M vinyl bromide magnesium in tetrahydrofuran under ice-water cooling (about 5° C.). After completion of the dropwise addition, the mixture was warmed to a room temperature, stirred at a room temperature for 30 minutes, and then again cooled with ice-water. The reaction mixture was treated with an aqueous saturated ammonium chloride solution, then extracted with ether. An organic layer was washed with an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/4) to obtain 560 mg of Compound (37). Yield: 70.8%. NMR(CDCl 3 ,TMS): δ 5.88(ddd, J=17 Hz,10 Hz,6 Hz, 1H, --CH═C), 5.18(m, 2H, C═CH 2 ), 4.11(q, J=6 Hz, 1H, CH--(OH)), 2.25-1.85(m, 2H, CF 2 CH 2 ), 1.8-1.25(m, 9H, 4×CH 2 +OH) 19 F-NMR(CDCl 3 ,CFCL 3 ): δ -126.3(s,2F,CH 2 CF 2 ),-121.5-124.0(m,10F, CH 2 CF 2 (CF 2 ) 5 CF 2 CF 3 ), -114.6(m, 2F, CF 2 CF 2 CF 3 ), -81.0(t, J=10 Hz, 3F, CF 3 ).
Example 38
Synthesis of [(2E)-8-perfluorooctyl-2-octenyl]phenyl sulfoxide (referred to as "Compound (38)" hereinafter)
To 5.00 g (9.15 mmol) of the Compound (37) which had been dissolved in 40 ml of anhydrous tetrahydrofuran under an argon atmosphere, 5.8 ml (9.28 mmol) of 1.46 M butyl lithium in hexane was dropwise added at -20° C. to obtain a mixture. 1.56 g (10.8 mmol) of benzenesulfenyl chloride in 2 ml of anhydrous terahydrofuran was added thereto at -20° C. The resulting mixture was heated to a room temperature, stirred for 15 minutes, concentrated under a reduced pressure to obtain a residue. It was diluted with ether, washed with an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ether/hexane=1/1) to obtain 4.69 g of Compound (38). Yield: 78.3%.
m.p. 44.5°-46.0° C. NMR(CDCl 3 ,TMS): δ 7.7-7.4(m, 5H, aromatic), 5.56(dt, J=15 Hz, 7 Hz, 1H, C═CHCH 2 S), 5.30(dt, J=15 Hz, 7 Hz, 1H, C--CH 2 CH═CH--), 3.49(m, 2H, CH 2 --S(O)Ph), 2.2-1.85(m, 4H, CF 2 CH 2 +C--CH 2 --CH═CH), 1.7-1.2(m, 6H, 3×CH 2 )
Example 39
Synthesis of (8-perfluorooctyl-3-hydroxy-1-octenyl)phenyl sulfide (referred to as "Compound (39)" hereinafter)
To 1.1 ml (7.85 mmol) of diisobutylamine which had been dissolved in 15 ml of anhydrous tetrahydrofuran at an argon atmosphere, 3.4 ml (6.12 mmol) of 1.46 M butyl lithium in hexane was dropwise added at -78° C. to obtain a mixture. It was stirred at -78° C. for 15 minutes, before 4.0 g (6.11 mmol) of the Compound (38) in 5 ml of anhydrous terahydrofuran was added at a stroke thereto. The resulting mixture was stirred at -78° C. for 1 hour and then at temperatures of -65° to -60° C. for 1 hour and again cooled to -78° C. The reaction mixture above was added through a cannula to 1.39 g (6.37 mmol) of diphenyl disulfide in 10 ml of anhydrous terahydrofuran. After being stirred at 0° C. for 1 hour, the solution was poured into 70 ml of an aqueous 10% hydrochloric acid solution and extracted with chloroform. An organic layer was washed with an aqueous saturated sodium bicarbonate solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a brown oily residue. It was immediately subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/5) to obtain 2.73 g of Compound (39). Yield: 68.3%. NMR(CDCl 3 ,TMS): δ 7.5-7.1(m, 5H, aromatic), 6.43(d, J=15 Hz, 1H, C═CHPh), 5.83(dd, J=15 Hz, 7 Hz, 1H, --CH═C-SPh), 4.17(q, J=7 Hz, 1H, CH(OH)), 2.25-1.85(m, 2H, CF 2 CH 2 ), 1.8-1.3(m, 9H, 4×CH 2 +OH)
Example 40
Synthesis of 8-perfluorooctyl-trans-1-octenal (referred to as "Compound (40)" hereinafter)
To 2.73 g (4.17 mmol) of the Compound (39) which had been dissolved in a mixed solvent of 42 ml of acetonitrile and 9 ml of water, 1.19 g (4.38 mmol) of mercury chloride (11) was added. The reaction mixture was stirred at temperatures of 40° to 50° C. for 15 hours, spontaneously cooled to a room temperature and filtered using Celite. Undissolved portions were washed with chloroform. The filtrate and the washing liquid were combined, washed with an aqueous 10% sodium bicarbonate solution. A water layer was extracted with chloroform. Organic layers were combined, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ether/hexane=1/10) to obtain 1.61 g of Compound (40). Yield: 70.9%. NMR(CDCl 3 ,TMS): δ 9.52(d, J=8 Hz, 1H, --CHO), 6.85(dt, J=16 Hz,7 Hz, 1H, CH 2 CH═CH) 6.13(dd, J=16 Hz,8 Hz, 1H, C═CH--CHO), 2.38(dt, J=7 Hz, 7 Hz, 2H, CH 2 --CH═C), 2.25-1.9(m, 2H, CF 3 CH 2 ), 1.8-1.3(m, 6H, 3×CH 2 ) ##STR28##
Example 41
Synthesis of (4S)-3-[(2'S,3'R,4'E)-2'-bromo-10-perfluorooctyl-3'-hydroxy-4-(isopropyl)-4'-decenoyl]-2-oxazolidinone (referred to as "Compound (41)" hereinafter)
To 0.55 g (2.20 mmol) of (4S)-3-(bromoacetyl)-4-(isopropyl)-2-oxazolidinone dissolved in 8 ml of anhydrous ether, 0.43 ml (3.09 mmol) of triethylamine was added at -78° C. under an argon atmosphere. After stirring for 5 minutes, 0.56 ml (2.22 mmol) of di-(n-butyl)boron triflate was gradually dropwise added. After the resulting mixture was stirred at -78C. for 15 minutes, refrigerants were removed and the mixture was stirred at a room temperature for 2 hours. The mixture was again cooled to -78° C. gradually before 0.75 g (1.38 mmol) of the Compound (40) dissolved in 8 ml of anhydrous ether was dropwise added thereto. The resulting mixture was stirred at -78° C. for 45 minutes and then at 0° C. for 1.5 hours before it was diluted with 80 ml of ether. The resulting mixture was poured into 70 ml of an aqueous 1 M sodium hydrogensulfate solution. An organic layer was taken, washed with 30 ml of an aqueous 1 M sodium hydrogensufate solution and then with 50 ml of an aqueous saturated sodium chloride solution, and concentrated under a reduced pressure to obtain a residue. It was again dissolved in 10 ml of ether and cooled to 0° C. A mixed solution of 5 ml of methanol and 5 ml of a aqueous 30% hydrogen peroxide solution was gradually dropwise added and the resulting reaction mixture was stirred at 0° C. for 1 hour. The reaction mixture was diluted with 30 ml of ether and washed with an aqueous saturated sodium bicarbonate solution before a water layer was twice extracted with 20 ml of ether. Organic layers were combined, washed with 20 ml of an aqueous saturated sodium bicarbonate solution and then with 20 ml of an aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane =1/2) to obtain 623 mg of Compound (41). Yield: 56.9%.
m.p. 71°-75° C. [α] D 22 +30.1° (c 0.256, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.85(dt, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.68(d, J=5 Hz, 1H, CHBr), 5.49(dd, J=15 Hz,6 Hz, 1H, CH═CH--CH 2 ), 4.6-4.2(m, 4H, CH 2 --O, CH--O, CH--NCO), 3.15(bs, 1H, OH), 2.40(m, 1H, CHMe 2 ), 2.2-1.9(m, 4H, CF 2 CH 2 , C═C--CH 2 ), 1.7-1.25(m, 6H, 3×CH 2 ), 0.95(d, J=7 Hz, 6H, 2×CH 3 )
Example 42
Synthesis of (4S)-3-[(2'R,3'R,4'E)-2'-azide-10-perfluorooctyl-3'-hydroxy-4-(isopropyl)-4'-decenoyl]-2-oxazolidinone (referred to as "Compound (42)" hereinafter)
0.58 g (0.73 mmol) of the Compound (41) was dissolved in 4 ml of dimethyl sulfoxide to form a solution. 0.10 g (1.54 mmol) of sodium azide was added thereto at a room temperature to obtain a reaction mixture. The mixture was stirred at a room temperature for 3 hours. It was then diluted with 30 ml of ether, washed three times with 10 ml of water and then with 10 ml of an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/3) to obtain 0.51 g of Compound (42). Yield: 92.3%.
m.p. 64°˜66° C. [α] D 22 +17.4° (c 2.40, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.89(dt,J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.62(dd, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.10(d, J=8 Hz, 1H, CHN 3 ), 4.6-4.2(m, 4H, CH 2 --O, CH--O, CH--NCO), 2.6-2.25(m, 6H, 3×CH 2 ), 0.94(d, J=8 Hz, 3H, CH 3 ), 0.90(d, J=7 Hz, 3H, CH 3 )
Example 43
Synthesis of (4S)-3-[(2'R,3'R,4'E)-2'-azide-3'-O-tert.-butyldimethylsilyl-10'-perfluorooctyl-3'-hydroxy-4-(isopropyl)-4'-decenoyl]-2-oxazolidinone (referred to as "Compound (43)" hereinafter)
445 mg (0.588 mmol) of the Compound (42) dissolved in 3 ml of anhydrous terahydrofuran was cooled to 0° C. under an argon atmosphere. 0.14 ml (1.20 mmol) of 2,6-lutidine was then added, followed by addition of 0.20 ml (0.871 mmol) of tert.-butyldimethylsilyl triflate to obtain a reaction mixture. The mixture was stirred at 0° C. for 30 minutes and then at a room temperature for 1 hour. It was then diluted with 25 ml of ethyl acetate, washed with 10 ml of water and then with 10 ml of an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/6) to obtain 475 mg of Compound (43). Yield: 92.7%.
m.p. 69.2°-70.2° C. [α] D 22 -0.672° (c 4.02, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.73(dt, J=16 Hz, 6 Hz, 1H, CH═CH--CH 2 ), 5.54(dd, J=16 Hz, 8 Hz, 1H, CH═CH--CH 2 ), 5.22(d, J=6 Hz, 1H, CHN 3 ), 4.64(dd, J=8 Hz,6 Hz, 1H, CHOSi), 4.48(m, 1H, CH--NCO), 4.4-4.2(m, 2H, CH 2 --O), 2.3(m, 1H, CHMe 2 ), 2.2-1.85(m, 4H, CF 2 CH 2 , C═C--CH 2 ), 1.7-1.3(m, 6H, 3×CH 2 ), 0.95-0.8(m, 15H, 2×CH 3 , SiCMe 3 ), 0.08(s, 3H, SiCH 3 ), 0.05(s, 3H, SiCH 3 )
Example 44
Synthesis of (2S,3R,4E)-2-azide-3-O-(tert.-butyldimethylsily)-10-perfluorooctyl-4-decene-1,3-diol (referred to as "Compound (44)" hereinafter)
475 mg (0.546 mmol) of the Compound (43) dissolved in 4 ml of anhydrous terahydrofuran was cooled to 0° C. under an argon atmosphere. 40 mg (1.84 mmol) of lithium boron hydride was then added in three portions. The resulting mixture was stirred at 0° C. for 1.5 hours and then at a room temperature for 30 minutes, and again cooled to 0° C. It was diluted with 10 ml of ethyl acetate before 10 ml of an aqueous saturated ammonium chloride solution was gradually added in order to decompose excessive lithium boron hydride. An organic layer was taken and a water layer was extracted with ethyl acetate.. The organic layers were combined, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/9) to obtain 263 mg of Compound (44). Yield: 64.8%.
[α] D 25 -25.57° (c 4.55, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.70(dt, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.48(dd, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 4.22(dd, J=7 Hz,5 Hz, 1H, CHOSi), 3.8-3.6(m, 2H, CH 2 --OH), 3.41(ddd, 1H, CHN 3 ), 2.2-1.9(m, 5H, CF 2 CH 2 , C═C--CH 2 , OH), 1.75-1.3(m, 6H, 3×CH 2 ), 0.90(s, 9H, SiCMe 3 ), 0.09(s, 3H, SiCH 3 ), 0.04(s, 3H, SiCH 3 ) 19 F-NMR(CDCl 3 , CFCL 3 ): δ -81.0(t, J=10H, 3F, CF 3 ), -114.6(m, 2F, CF 2 CF 3 ), -120.5-127.0 (m, 12F, 6×CF 2 )
Example 45
Synthesis of (2S,3R,4E)-2-azide-10-perfluorooctyl-4-decene-1,3-diol (referred to as "Compound (45)" hereinafter)
263 mg (0.353 mmol) of the Compound (44) dissolved in 4 ml of anhydrous terahydrofuran was cooled to 0° C. under an argon atmosphere. 0.6 ml (0.6 mmol) of 1.0 M tetrabutylammonium fluoride in tetrahydrofuran was then dropwise added. The resulting mixture was stirred at a room temperature for 1.5 hours. It was diluted with 200 ml of ethyl acetate, washed with water (50 ml×2) and then with 50 ml of an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/2) to obtain 186 mg of Compound (45). Yield: 83.5%.
m.p. 63°˜65° C. [α] D 25 -16.9° (C 4.01, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 5.83(dt, J=15 Hz,7Hz, 1H, CH═CH--CH 2 ), 5.55(dd, J=15 Hz,7Hz, 1H, CH═CH--CH 2 ), 4.25(m, 1H, CHOH), 3.85-3.65(m, 2H, CH 2 --OH), 3.51(dt, J=5 Hz, 5Hz, 1H, CHN 3 ), 2.2-1.85(m, 5H, CF 2 CH 2 , C═C--CH 2 , OH), 1.7-1.2(m, 7H, 3×CH 2 , OH)
Example 46
Synthesis of (2S,3R,4E)-2-azide-10-perfluorooctyl-1-triphenylmethoxy-4-decene-3-ol (referred to as "Compound (46)" hereinafter)
180 mg (0.285 mmol) of the Compound (45) was dissolved in a mixed solvent of anhydrous terahydrofuran-chloroform-pyridine (0.4 ml, 0.4 ml, 0.4 ml) under an argon atmosphere to form a solution. 130 mg (0.466 mmol) of triphenylmethyl chloride was added thereto at 0° C. The resulting mixture was stirred at a room temperature for 50 hours and concentrated under a reduced pressure to obtain a residue. It was dissolved in ether and washed with an aqueous saturated sodium bicarbonate solution. A water layer was extracted twice with 20 ml of ether. Organic layers were combined, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/7) to obtain 167 mg of Compound (46). Yield: 67.0%.
[α] D 25 +0.33° (c 2.14, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 7.5-7.15(m, 15H, 3×Ph), 5.66(dt, J=16 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.32(dd, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 4.21 (m, 1H, CHOH), 3.53(dt, J=5 Hz, 5 Hz, 1H, CHN 3 ), 3.30(d, J=5 Hz, 2H, CH 2 --OTr), 2.2-1.85(m, 4H, CF 2 CH 2 , C═C--CH 2 ), 1.7-1.2(m, 7H, 3×CH 2 , OH)
Example 47
Synthesis of (2S,3R,4E)-2-azide-3-benzoyloxy-10-perfluorooctyl-1-triphenylmethoxy-4-decene (referred to as "Compound (47)" hereinafter)
167 mg (0.191 mmol) of the Compound (46) was dissolved in a mixed solvent of 2 ml of anhydrous toluene and 0.2 ml of pyridine to form a solution. 60 ml (0.52 mmol) of benzoyl chloride was dropwise added thereto at 0° C. The resulting mixture was heated to a room temperature, stirred for 14 hours, poured into ice-cooled water and extracted with ether. An organic layer was dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/17) to obtain 171 mg of Compound (47). Yield: 91.5%
[α] D 23 -10.33° (c 3.03, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 8.1-7.1(m, 20H, 4×Ph), 5.81(dt, J=15 Hz, 7 Hz, 1H, CH═CH--CH 2 ), 5.64 (dd, J=8 Hz, 5 Hz, 1H, CHOBz), 5.44(dd, J=15 Hz, 8 Hz, 1H, CH═CH--CH 2 ), 3.83(dt, J=6 Hz, 5 Hz, 1H, CHN 3 ), 3.29 and 3.20(dd and dd, 2H, CH 2 --OTr), 2.2-1.9(m, 4H, CF 2 CH 2 , C═C--CH 2 ), 1.7-1.1(m, 6H, 3×CH 2 )
Example 48
Synthesis of (2S,3R,4E)-2-azide-3-benzoyloxy-10-perfluorooctyl-4-decene-1-ol (referred to as "Compound (48)" hereinafter)
To 170 mg (0.174 mmol) of the Compound (47) which had been dissolved in a mixed solvent of 1.0 ml of anhydrous toluene and 0.5 ml of anhydrous methanol, 30 ml (0.244 mmol) of boron trifluoridediethyl ether complex was dropwise added at 0° C. under an argon atmosphere. The mixture was stirred at a room temperature for 11 hours, poured into an aqueous saturated sodium bicarbonate solution which had been cooled with ice and extracted with ethyl acetate. An organic layer was dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=1/3) to obtain 117 mg of Compound (48). Yield: 91.5%.
[α] D 25 -25.7° (c 2.36, CHCl 3 ) NMR(CDCl 3 ,TMS): δ 8.1-7.4(m, 5H, Ph), 6.1-5.8(m, 1H, CH═CH--CH 2 ), 5.7-5.5(m, 2H, CHOBz, CH═CH--CH 2 ), 3.9-3.5(2m, 3H, CHN 3 , CH 2 --OH), 2.2-1.7(m, 4H, CF 2 CH 2 , C═C--CH 2 ), 1.7-1.2(m, 7H, 3×CH 2 , OH) 19 F-NMR(CDCl 3 , CFCL 3 ): δ -81.3(t, J=10H, 3F, CF 3 ), -114.8(m, 2F, CF 2 CF 3 ), -122-124 (m, 10F, 5×CF 2 ), -126.6(s, 2F, CH 2 CF 2 ) ##STR29##
Example 49
Synthesis of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-O-(3-O-acetyl-2,6-di-O-benzoyl-β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-2-azide-3-O-benzoyl-10-perfluorooctyl-4-decene-1,3-diol (referred to as "Compound (49)" hereinafter)
154 mg (0.110 mmol) of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-3-O-acetyl-2,6-di-O-benzoyl-.alpha.-D-glucopyranosyl trichloroacetoimidate and 116 mg (0.158 mmol) of the Compound (48) were dissolved in 3 ml of anhydrous dichloromethane under an argon atmosphere to form a solution. 1.9 g of Molecular Sieve 4A was added thereto. The resulting mixture was stirred at a room temperature for 30 minutes. It was cooled to 0° C. before 19 ml (0.154 mmol) of boron trifluoride-diethyl ether complex was added thereto. The resulting mixture was stirred at 0° C. for 4 hours. It was filtered using Celite, and undissolved portions were washed with dichloromethane. The filtrate and the washing liquid were combined, washed with an aqueous 1 M sodium bicarbonate solution and then with water, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to flash column chromatography (a packing material: silica gel 60K230, an eluent: ethyl acetate/hexane=3/1) to obtain 144 mg of Compound (49). Yield: 66,4%.
[α] D 25 -1.80° (c 0.58, CHCl 3 ) IRmax(KBr)(cm -1 ): 3390(NH), 2110(N 3 ), 1750,1230(ester), 1690,1540(amide), 715(phenyl) NMR(CDCl 3 ,TMS): lactose unit; δ 4.60(dd, J=10 Hz,3 Hz, 1H, H-3'), 4.68(d, J=8 Hz, 1H, H-1), 4.87(d, J=8 Hz, 1H, H-1'), 5.00(d, J=3 Hz, 1H, H-4'), 5.03(dd, J=10 Hz,8Hz, 1H, H-2'), 5.24(dd, J=10 Hz, J=8 Hz, 1H, H-2), 7.3-8.1 (m, 20H, 4×Ph), sialic acid unit; δ 1.66(dd, J=13 Hz, 13 Hz, 1H, H-3a), 1.84(s, 3H, N--COCH 3 ), 2.57(dd, J=13 Hz, 5 Hz, 1H, H-3e), 3.71(s, 3H, OCH 3 ), 4.85(m, 1H, H-4), ceramide unit; δ 5.67(dt, J=15 Hz, 7 Hz, 1H, H-5), O-acetyl group; δ 1.98, 1.99, 2.01, 2.02(×2), 2.11, 2.20(7s, 21H, 7×Ac) 19 F-NMR(CDCl 3 , CFCL 3 ): δ -81.0(t, J=10H, 3F, CF 3 ), -114.6(m, 2F, CF 2 CF 3 ), -121.5-124.0(m, 10F, 5×CF 2 ), -126.3(s, 2F, CH 2 CF 2 )
Example 50
Synthesis of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-O-(3-O-acetyl-2,6-di-O-benzoyl-β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-3-O-benzoyl-10-perfluorooctyl-2-teracosaneamide-4-decene-1,3-diol (referred to as "Compound (50)" hereinafter)
140 mg (0.071 mmol) of the Compound (49) was dissolved in a mixed solvent of 12 ml of pyridine and 2.4 ml of water to form a solution. Hydrogen sulfide gas was passed through the solution at a room temperature for 50.5 hours. After the starting substance was confirmed to disappear, hydrogen sulfide was removed from the reaction mixture, and water and pyridine was then distilled off under a reduced pressure. The residue was dissolved in 6 ml of anhydrous dichloromethane to form a solution to which 52 mg (0.14 mmol) of tetracosanoic acid and 42 mg (0.22 mmol) of WSC were added under an argon atmosphere. The resulting mixture was stirred at a room temperature for 16 hours. It was then diluted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to silica gel column chromatography (a packing material: silica gel 60(7734), an eluent: methanol/chloroform=1/60→1/40) to obtain 121 mg of Compound (50). Yield: 74.2%.
[α] D 25 +8.65° (c 1.85, CHCl 3 ) IRmax(KBr)(cm -1 ): 3390(NH), 2925,2855(Me, methylene), 1750,1230(ester), 1690,1535(amide), 715(phenyl) NMR(CDCl 3 ,TMS): lactose unit; δ 4.60(d, J=8 Hz, 1H, H-1), 4.83(d, J=8 Hz, 1H, H-1'), 5.18(dd, J=10 Hz, 8 Hz, 1H, H-2), 7.3-8.1 (m, 20H, 4×Ph), sialic acid unit; δ 1.66(dd, J=13 Hz, 13 Hz, 1H, H-3a), 1.84(s, 3H, N--COCH 3 ), 2.58(dd, J=13 Hz, 5 Hz, 1H, H-3e), 3.71(s, 3H, OCH 3 ), 4.86(m, 1H, H-4), ceramide unit; δ 5.62(d, J=9 Hz, 1H, NH), 5.76(dt, J=15 Hz, 7 Hz, 1H, H-5), O-acetyl group; δ 1.99, 2.00, 2.02(×2), 2.03, 2.11, 2.18(7s, 21H, 7×Ac)
Example 51
Synthesis of O-(5-acetoamide-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonic acid)-(2→3)-O-(β-D-galactopyranosyl)-(1→4)-O-(β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-10-perfluorooctyl-2-tetracosaneamide-4-decene-1,3-diol (referred to as "Compound (51)" hereinafter)
26 mg (0.48 mmol) of sodium methoxide was added under an argon atmosphere to 119 mg (0.052 mmol) of the Compound (50) dissolved in 4.0 ml of anhydrous methanol. The resulting mixture was stirred at a room temperature for 8 hours. It was cooled to 0° C. and then 0.60 ml of water was added. The resulting mixture was stirred at 0° C. for 4.5 hours. It was subjected to Amberlite IR120 (H+) column chromatography (eluent: methanol). Eluted portions were concentrated under a reduced pressure to obtain a residue which was then subjected to column chromatography (packing agent: Sephadex LH-20, an eluent: methanol) to obtain 77 mg of Compound (51). Yield: 94.6%
[α] D 25 +1.72° (c 0.51, 1:1 CH 3 OH--CHCl 3 ) IRmax(KBr)(cm -1 ): 3380(NH), 2925,2855(Me, methylene), 1730(carbonyl), 1630,1555(amide). NMR(2:1 CD 3 OD--CDCl 3 ,TMS): lactose unit; δ 4.30(d, J=8 Hz, 1H, H-1), 4.42(d, J=8 Hz, 1H, H-1'), sialic acid unit; δ 2.03(s, 3H, N--COCH 3 ), 2.86(dd, J=12 Hz, 4 Hz, 1H, H-3e), ceramide unit; δ 0.89(t, J=7 Hz, 3H, CH 2 CH 3 ), 2.18(t, J=8 Hz, 2H, CH 2 CO), 4.20(dd, J=10 Hz,4 Hz, 1H, H-1), 5.48(dd, J=15 Hz,7 Hz, 1H, H-4), 5.70(dt, J=15 Hz, 7 Hz, 1H, H-5) 19 F-NMR(2:1 CD 3 OD-CDCl 3 ): δ -81.8(t, J=10H, 3F, CF 3 ), -114.0(m, 2F, CF 2 CF 3 ), -121-123.5 (m, 10F, 5×CF 2 ), -125.8(s, 2F, CH 2 CF 2 ) ##STR30##
Example 52
Synthesis of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-)-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-O-(3-O-acetyl-2,6-di-O-benzoyl-β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-3-O-benzoyl-2-perfluorononaneamide-10-perfluorooctyl-4-decene-1,3-diol (referred to as "Compound (52)" hereinafter)
109 mg (0.055 mmol) of the Compound (49) was dissolved in a mixed solvent of 8.5 ml of pyridine and 1.7 ml of water to form a solution. Hydrogen sulfide gas was passed through the solution at a room temperature for 48.5 hours. After the starting substance was confirmed to disappear, hydrogen sulfide was removed from the reaction mixture, and water and pyridine was then distilled off under a reduced pressure. The residue was dissolved in 4.6 ml of anhydrous dichloromethane to form a solution, to which 52 mg (0.11 mmol) of perfluorononanoic acid and 35 mg (0.18 mmol) of WSC were added an argon atmosphere. The resulting mixture was stirred at a room temperature for 24 hours. It was then diluted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to silica gel column chromatography (a packing material: silica get 60 (7734), an eluent: diethyl ether/ethyl acetate=3/2) to obtain 99.5 mg of Compound (52). Yield: 75.3%. [α] D 25 +8.11° (c 1.03, 1: 1 CH 3 OH--CHCl 3 ) IRmax(KBr)(cm -1 ): 3390(NH), 2930(methylene), 1745,1235(ester); 1690,1535(amide ), 715(phenyl) NMR(CDCl 3 ,TMS): lactose unit; δ 4.60(d, J=8 Hz, 1H, H-1), 4.84(d, J=8 Hz, 1H, H-1'), 5.17(dd, J=10 Hz, 8 Hz, 1H, H-2), 7.3-8.1 (m, 20H, 4×Ph), sialic acid unit; δ 1.66(dd, J=13 Hz, 13 Hz, 1H, H-3a), 1.84(s, 3H, N--COCH 3 ), 2.57(dd, J=13 Hz, 5 Hz, 1H, H-3e), 3.71(s, 3H, OCH 3 ), 4.86(m, 1H, H-4), ceramide unit; δ 5.59(d, J=7 Hz, 1H, NH), 5.82(dt, J=15 Hz, 7 Hz, 1H, H-5), O-acetyl group; δ 1.99, 2.00(×2), 2.02(×2), 2.10, 2.18(7s, 21H, 7×Ac)
Example 53
Synthesis of O-(5-acetoamide-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonic acid)-(2→3)-O-(β-D-galactopyranosyl)-(1→4)-O-(β-D-gluocopyranosyl)-(1→1)-(2S,3R,4E)-2-perfluorononaneamid-10-perfluorooctyl-4-decene-1,3-diol (referred to as "Compound (53)" hereinafter)
15 mg (0.28 mmol) of sodium methoxide was added under an argon atmosphere to 95 mg (0.040 mmol) of the Compound (52) dissolved in 3.8 ml of anhydrous methanol. The resulting mixture was stirred at a room temperature for 15 hours. It was cooled to 0° C. and 0.74 ml of water was then added thereto. The resulting mixture was stirred at 0° C. for 3 hours. It was subjected to Amberlite IR120 (H+) column chromatography (eluent: methanol). Eluted portions were concentrated under a reduced pressure to obtain a residue which was then subjected to column chromatography (packing agent: Sephadex LH-20, an eluent: methanol) to obtain 51 mg of Compound (53). Yield: 76.4%
[α] D 25 +1.65° (c 0.20, 1: 1 CH 3 OH--CHCl 3 ) IRmax(KBr)(cm -1 ): 3410(NH), 2940(methylene), 1710(carbonyl), 1620,1560(amide) NMR(2: 1 CD 3 OD-CDCl 3 ,TMS): lactose unit; δ 4.31 (d, J=8 Hz, 1H, H-1), 4.41 (d, J=8 Hz, 1H, H-1'), sialic acid unit; δ 2.03(s, 3H, N--COCH 3 ), 2.83(dd, J=12 Hz, 4 Hz, 1H, H-3e), ceramide unit; δ 4.20(dd, J=8 Hz,4 Hz, 1H, H-1), 5.45(dd, J=15 Hz,8 Hz, 1H, H-4), 5.73(dt, J=15 Hz, 7 Hz, 1H, H-5) 19 F-NMR(2: 1 CD 3 OD--CDCl 3 ): δ -81.19(t, J=11H, 3F, CF 3 ), -81.17(t, J=11H, 3F, CF 3 ), -114.6(m, 2F, CF 2 CF 3 ), -119.6(m, 2F, CF 2 CF 3 ), -121-123.7 (m, 20F, 10×CF 2 ), -125.8(s, 4F, COCF 2 , CH 2 CF 2 ) ##STR31##
Example 54
Synthesis of O-(methyl-5-acetoamide-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-.alpha.-D-galacto-2-nonulopyranosylonate)-(2→3)-O-(2,4-di-O-acetyl-6-O-benzoyl-β-D-galactopyranosyl)-(1→4)-O-(3-O-acetyl-2,6-di-O-benzoyl-β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-3-O-benzoyl-10-perfluorooctyl-2-perfluorooctylhexadecaneamide-4-decene-1,3-diol (referred to as "Compound (54)" hereinafter)
141 mg (0.072 mmol) of the Compound (49) was dissolved in a mixed solvent of 11.9 ml of pyridine and 2.4 ml of water to form a solution. Hydrogen sulfide gas was passed through the solution at a room temperature for 52 hours. After the starting substance was confirmed to disappear, hydrogen sulfide was removed from the reaction mixture, and water and pyridine were then distilled off under a reduced pressure. The residue was dissolved in 6 ml of anhydrous dichloromethane to form a solution, to which 96.5 mg (0.143 mmol) of perfluorooctylhexadecanoic acid and 42 mg (0.22 mmol) of WSC were added under an argon atmosphere. The reaction mixture was stirred at a room temperature for 11.5 hours. It was then diluted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure to obtain a residue. It was subjected to silica gel column chromatography (a packing material: silica gel 60 (7734), an eluent: methanol/chloroform=1/60→1/40→1/30) to obtain 120 mg of Compound (54). Yield: 64.5%.
[α] D 25 +8.10° (c 2.06, CHCl 3 ) IRmax(KBr)(cm -1 ): 3390(NH), 2930,2855(Me, methylene), 1745,1240(ester), 1690,1525(amide), 715(phenyl) NMR(CDCl 3 ,TMS): lactose unit; δ 4.61(d, J=8 Hz, 1H, H-1), 4.84(d, J=8 Hz, 1H, H-1'), 5.18(dd, J=10 Hz, 8 Hz, 1H, H-2), 7.3-8.1 (m, 20H, 4×Ph), sialic acid unit; δ 1.66(dd, J=13 Hz, 13 Hz, 1H, H-3a), 1.84(s, 3H, N--COCH 3 ), 2.57(dd, J=13 Hz, 5 Hz, 1H, H-3e), 3.71(s, 3H, OCH 3 ), 4.87(m, 1H, H-4), ceramide unit; δ 5.65(d, J=9 Hz, 1H, NH), 5.75(dt, J=15 Hz, 7 Hz, 1H, H-5), O-acetyl group; δ7 1.99(×2), 2.01(×2), 2.02, 2.10, 2.18(7s, 21H, 7×Ac)
Example 55
Synthesis of O-(5-acetoamide-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonic acid)-(2→3)-O-(β-D-galactopyranosyl)-(1→4)-O-(β-D-glucopyranosyl)-(1→1)-(2S,3R,4E)-10-perfluorooctyl-2-perfluorooctylhexadecaneamide-4-decene-1,3-diol (referred to as "Compound (55)" hereinafter)
17 mg (0.31 mmol) of sodium methoxide was added under an argon atmosphere to 117 mg (0.045 mmol) of the Compound (54) dissolved in 14 ml of anhydrous methanol. The resulting mixture was stirred at a room temperature for 5 hours. It was cooled to 0° C., followed by addition of 0.42 ml of water, and diluted with 8 ml of methanol. The resulting mixture was stirred at a room temperature for 4 hours. It was subjected to Amberlite IR120 column chromatography (eluent: methanol). Eluted portions were concentrated under a reduced pressure to obtain a residue which was then subjected to column chromatography (packing agent: Sephadex LH-20, an eluent: methanol) to obtain 51 mg of Compound (55). Yield: 88.8%
[α] D 24 +1.90° (c 0.42, 2: 1 CH 3 OH--CHCl 3 ) IRmax(KBr)(cm -1 ): 3390(NH), 2930,2855(Me, methylene), 710(carbonyl), 1630,1555(amide) NMR(2: 1 CD 3 OD--CDCl 3 ,TMS): lactose unit; δ 4.30 (d, J=8 Hz, 1H, H-1), 4.42 (d, J=8 Hz, 1H, H-1'), sialic acid unit; δ 2.03(s, 3H, N--COCH 3 ), 2.85(dd, J=12 Hz, 4 Hz, 1H, H-3e), ceramide unit; δ 4.21(dd, J=10 Hz,4 Hz, 1H, H-1), 5.49(dd, J=15 Hz,8 Hz, H, H-4), 5.70(dt, J=15 Hz, 7 Hz, 1H, H-5). 19 F-NMR(2: 1 CD 3 OD--CDCl 3 ): δ -81.19(t, J=10H, 6F, 2×CF 3 ), -114.4(m, F, 2×CF 2 CF 3 ), -121-123.6 (m, 20F, 10×CF 2 ), -126.2(s, 4F, 2×CH 2 CF 2 )
The Compound (51) suppresses propagation of cell strain A 31 of normal mouse fibroblast phenotype; thus developing a new area of physiological activity of gangliosides. The fluorinated ganglioside according to the present invention can expected to be useful as a cancerocidal agent, a cancer metastasis suppressing agent, etc., based on a cell propagation suppressing mechanism. | A ganglioside GM3 derivative containing fluorine atoms in a ceramide portion thereof, represented by the formula: ##STR1## in which m is an integer of at least 2, n is an integer of 0 to 7 provided that m is larger than n, and R represents an alkyl group or a fluoroalkyl group is disclosed. | 2 |
FIELD OF THE INVENTION
This invention relates to elastomeric components such as rubber stoppers which are useful in pharmaceutical devices such as medicine-containing vials. Specifically, the elastomeric components are coated with a polyurethane film in order to improve the coefficient of friction of the component and thereby improve manufacturing efficiency using conventional manufacturing equipment.
BACKGROUND OF THE INVENTION
For many years, the most successful closure system for pharmaceutical products has been the use of rubber stoppers in glass or high-density plastic vials. The glass and rubber combination has been useful for a wide variety of pharmaceutical ingredients combining both safe storage of the medicines and easy access through the rubber stopper. Particularly when liquids are contained in the vial, a needle can easily penetrate the rubber stopper to withdraw the desired amount of ingredient without otherwise interfering with the completeness of the closure.
Because of the success of this type of pharmaceutical device, and as more and more systems started using rubber stoppers in glass containers, the rate at which these devices can be manufactured after filling the container contributes greatly to the economic efficiencies of the otherwise desirable design. Conventional pharmaceutical devices which are useful for filling vials rely upon a mechanical implantation of the rubber stopper into the neck of the vial or other shaped container. Just prior to the mechanical insertion, the rubber stoppers are transported from a hopper to the filling equipment, usually by centrifugal or gravity feed. It is essential that the rubber components not hang up on the transfer equipment but rather flow smoothly into the capping or closure forming device. The equipment especially for transferring components is normally made from stainless steel or other materials which can be kept extremely clean for pharmaceutical purposes.
In the prior art, the high coefficient of friction of rubber stoppers and other rubber materials which are being fed to closure devices and other pharmaceutical devices, has been the limiting factor in the speed of the machine. Use of gravity, centrifugal or vibration feeding devices require that the rubber stoppers or other elastomeric components move smoothly over the surface of the feeding unit. Typically, rubber devices of the type used in pharmaceutical closures have coefficients of friction of at least 1.2, which clearly acts as an impediment to rapid movement.
One solution which has been proposed to improve the general processibility of rubber closures and which has at least kept the individual rubber stoppers from bonding to one another during autoclaving and other treating steps is the use of silicone oil as a coating on the outside of the stoppers. Silicone oil has improved the lubricity of the rubber closures but has added additional problems by increasing the particle count found in inspection of various drug solutions. The Federal Drug Administration evaluates processes by counting the number of particles present, without concern for what the particles are made from. Silicone oil is normally not an undesirable particle in medicine but still adds to the count of particles and, therefore, detracts from the overall acceptance of its use in processing equipment. While the amount of silicone oil is minimal, only that amount necessary to prevent the individual stoppers from sticking to one another, it has not adequately affected the coefficient of friction of rubber stoppers for use in high-speed capping equipment so as to give uniform, faster movement, particularly with centrifugal feeding systems. Finally, the rubber stoppers which have been treated by the use of silicone oil are not as effective in surviving chemical tests concerning the compatibility and the contamination of the materials contained in the vials.
At the present time, there does not appear to be any suggestion in the prior art which would suggest the improvement of the coefficient of friction of rubber while maintaining other properties necessary for effective pharmaceutical closures. In U.S. Pat. No. 2,951,053, Reuter et al discusses an elastic polyurethane composition which has improved friction properties. The polyurethane is used to produce articles having moving surfaces, such as bearing designs and the like. Silicone oil and/or hydrocarbons are introduced into the polyurethane material. There is absolutely no suggestion that polyurethane may be used as a coating on the rubber products. U.S. Pat. No. 4,147,679 discloses a polyurethane which is suitable for forming a coating on substrates such as plastics, foam and the like. The use of polyurethane to solve the deficiencies outlined above in the use of elastomeric components in pharmaceutical devices has not been suggested by any of the prior art.
SUMMARY OF THE INVENTION
Accordingly, it has now been discovered that an improved stopper device for use on pharmaceutical closures may be made in the following manner. The elastomeric component used in pharmaceutical devices comprises an elastomeric part such as a stopper which is sized to function as a closure and a polyurethane coating on the stopper. The coating is such that it has a modulus sufficient to decrease the coefficient of friction of the stopper to less than 0.6 and preferably to between 0.35 and 0.45. The elastomeric stopper is coated with a polyurethane coating, and preferably a water soluble polyurethane coating applied by conventional coating techniques and crosslinked to promote adhesion and resistance to heat and other factors. The modulus is selected to improve the hardness of the polyurethane coating so as to reduce the coefficient of friction of the stopper. Typically the modulus may range from less than 1000 to greater than 5000, although higher modulus readings do not significantly improve the coefficient of friction. The coating thickness will vary, depending upon the specific polymer being employed and the degree of crosslinking which needs to be achieved in order to effectively adhere the coating to the substrate. Typically, the coating will range from about at least 0.2 mil to as much as 1.5 mil or larger.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The device of this invention may be manufactured from any conventional elastomeric material which has been used in pharmaceutical devices wherein elastomeric component is required. Rubber stoppers of conventional design must meet certain tests in order to be useable in the pharmaceutical industry. The present invention, which comprises the addition of a polyurethane coating on the elastomeric component, should be capable of improving the coefficient of friction so that it permits the use of high-speed capping equipment so as to give uniform, faster movement of the materials, particularly when fed with a centrifugal feed. Elimination of silicone oil in processing substantially reduces the particles which are found in the solution contained in the vial being capped or closed. Even though silicone oil is not necessarily harmful in minute quantities in pharmaceutical solutions, governmental requirements such as FDA requirements, sometimes count particles rather than distinguishing between what the various kinds of particles are. Thus, even completely harmless particles would be counted against the satisfactory purity of the solution. Elimination of silicone particles would be a great advantage in the art.
The elastomeric component of the pharmaceutical devices is manufactured from any of the elastomeric compounds which have conventionally been used in the pharmaceutical industry. Natural rubber, of course, was the original choice of materials for many elastomeric formulations and components in the pharmaceutical industry. Butyl rubber and many of the synthetic rubbers have been successfully used as stoppers, depending upon the stability during autoclaving or other high stress situations. A particular rubber which is admirably suited for the purposes of functioning as a rubber stopper in vials is butyl rubber.
The present invention is intended to be used on all of the conventional, presently existing stoppers and other elastomeric articles which are available in the pharmaceutical industry. Accordingly, any stopper which has been used or which would be useable if the coefficient of friction would permit its use in high-speed machines is, therefore, contemplated for use as the first component of the present invention.
Presently available rubber products are admirably suited for their purpose except for the delay caused in high-speed machines, and accordingly, the present invention seeks to improve the stoppers' functionality in two areas and maintain its functionality in all of the rest. Specifically, the present invention contemplates improving the coefficient of friction for use in high-speed capping equipment, particularly with centrifugal feeds, and it also contemplates the elimination of silicone oil and other processing aids. The effectiveness of rubber stopper as a barrier and as a stopper and as a product resistant to chemical attack is intended to be maintained when the second component is applied. Because rubber stoppers currently in use are admirably suited except for the two features mentioned above, there is no significant reason for improving any of the other properties. Nonetheless, it is necessary to maintain the resistance to chemical attack and the other properties when applying a coating as described hereinafter.
Polyurethanes form the second component of the device of this invention and are applied as a coating to the elastomeric stopper or other device used in pharmaceutical environments. The coating must be extensible so that it will stretch and move with the underlying rubber. In a preferred embodiment, it is highly desirable that the coating material be water based so as to reduce capital equipment requirements for handling solvents other than water. This is particularly important in pharmaceutical processing so as to prevent contamination by unremoved solvents. In addition, flammability and toxicity are always of concern when solvents other than water are used.
Polyurethanes have become known as extensible and non-toxic. For example, polyurethanes in some forms have been made into components of artificial hearts.
In considering polyurethanes as a coating for elastomers for use in the pharmaceutical industry so as to improve the coefficient of friction as described above, various difficulties were encountered. Most of the polyurethanes which are satisfactory for resisting the autoclave process, wherein the products are sterilized, are solvent based and, therefore, have limited use in the pharmaceutical industry. Water-based polyurethanes presented a significant dilemma in that if it is dispersible in water, it most oftentimes is not capable of resisting intense water exposure such as is found in the various autoclave cycles which pharmaceutical closure products which must survive. Attempts to crosslink water-based polyurethanes were not initially successful since those crosslinking agents which rendered the coating autoclave resistant also formed a yellowing to the coating which was objectionable.
One particular family of polyurethanes which are useful in the present invention are the aliphatic urethane polymers manufactured by Sanncor Industries, Inc. under the trade name Sancure®. Specifically, Sancure®867 is an aliphatic water formed urethane polymer which can be employed in making the coatings of the present invention. This aliphatic urethane polymer supplied as an aqueous solution of approximately 40% by weight solids and is in the form of a high molecular weight colloidal dispersion. Sancure®847 is another similar aliphatic urethane polymer manufactured by Sanncor Industries and is supplied as a clear to translucent colloidal dispersant at approximately 30% by weight total solids. This second aliphatic urethane polymer has increased strength over the other Sancure®867 and in parts an improved hardness to the coating. Both of these aliphatic water borne urethane polymers are curable using a variety of water-based curing agents which cause crosslinking and thereby enhance the autoclave resistance of the resulting film. It should be noted that crosslinking should not significantly affect the coefficient of friction which the coating imparts to the rubber product. It does, however, materially affect the ability to adhere to the rubber and survive the various tests which are necessary.
A preferred crosslinking agent is a commercial grade hexamethoxy methyl melamine such as the commercially available hexamethoxy methyl melamine marketed by American Cyanamid Company under the trade name Cymal®303. This crosslinking agent may be used with either of the Sanncor aliphatic water borne polymers described above to achieve crosslinked coatings according to the present invention.
Another aliphatic water borne urethane polymer which may be crosslinked with the hexamethoxy methyl melamine resins described above is the Polyvinyl Chemicals Industries aliphatic water borne urethane polymer sold under the name NeoRez®R-966 and R-967. Polyvinyls Chemical Industries is a division of ICI. This urethane polymer is supplied in water solution of approximately 33% by weight of the aliphatic urethane. Crosslinking of the resin with Cymal®303 made by American Cyanamid or other crosslinking agents yields an effective hard coating which adheres to the rubber product and which lowers the coefficient of friction of the resulting product in the manner described herein.
It is contemplated that occasionally the urethane polymers used in the present invention to coat the elastomeric components will not provide a coating which is adequately water resistant even after crosslinking as described above. In such cases, the addition of an additional synthetic resin to the coating may appropriately improve the water resistance. For example, Polyvinyl Chemicals Industries applies an aqueous acrylic propolymer under the trade name m-NeoCryl®A-622 which is an acrylic copolymer which is suitable for improving the water resistance in coatings. Normally, it is not necessary to modify the water resistance of the urethane resin.
For the purposes of this invention, the coefficient of friction of various elastomeric products is defined as follows. The coefficient of friction is the ratio of the frictional force resisting movement of the surface being tested to the force applied normal to the surface. In this case, the surface was a stainless steel plane. Four rubber stoppers were fixtured in a 256 gram weight such that they all lie on he stainless steel plane. The incline of the plane was then increased until the weight just started to slide, at which point the plane was locked and the angle was noted. The tangent of the angle is the static coefficient of friction.
It has been discovered that there is a correlation between the coefficient of friction as defined above for various products coated with polyurethane coatings and the 100% modulus of the coating. The 100% modulus is, of course, defined in the usual way. Specifically, modulus is defined as the ratio of nominal stress to corresponding strain. In this case, the modulus is considered at 100 percent strain and is expressed in pounds per square inch.
The modulus can range from less than 1000 psi to over 5000 psi or higher and will directly impact upon the coefficient of friction. It has been discovered that coatings having a 100% modulus ranging from 1000 psi to 5000 psi generally have coefficients of friction in the range which is desired for most centrifugal feed processing equipment.
In order to demonstrate the efficacy of the present invention, the following experiments were performed. In each example, the modulus of the coating was between 1000 psi and 5000 psi.
EXAMPLE 1
A mixture was made of 43.6 pounds of R-967 urethane polymer, 2.7 pounds of Cymel® curing agent, and 6.6 pounds of water. Pharmaceutical rubber stoppers were spray coated to a thickness of 1.2 mils. They were then cured for 6.5 minutes in an I.R. tunnel. Coefficient of friction was reduced from 1.7 on the uncoated stopper to 0.7 on the coated stopper.
EXAMPLE 2
A mixture of three products manufactured by Sanncor Industries, Inc. was made of 60.2 pounds of S-867 urethane polymer, 45 pounds of S-847 urethane polymer, 5 pounds of Sanncur 87 curing agent, and 4 pounds of water. Pharmaceutical rubber stoppers were spray coated to a thickness of 1.0 mils. They were then cured for 6.5 minutes in an I.R. tunnel. Coefficient of friction was reduced from 1.7 on the uncoated stopper to 0.2 on the coated stopper. Standard testing of the stoppers following United States Pharmacopeia methods showed no significant change in other stopper properties.
EXAMPLE 3
A mixture was made of 178.7 pounds of S-847 polyurethane, 8.7 pounds Sanncur 87 curing agent, and 4.2 pounds of water. Pharmaceutical rubber stoppers were spray coated to a thickness of 1.2 mils. They were cured in an I.R. tunnel for 6.5 minutes. Coefficient of friction was reduced from 1.7 on the uncoated stopper to 0.2 on the coated stopper standard testing of the stoppers following United States Pharmacopeia methods showed no significant change in other stopper properties.
EXAMPLE 4
A mixture of 43.6 pounds of Polyvinyl's R-967 urethane polymer, 2.7 pounds of Cymel®303 curing agent, and 6.6 pounds of water. Pharmaceutical rubber stoppers were spray coated to a thickness of 1.2 mils. They were cured in an I.R. tunnel for 6.5 minutes. Coefficient of friction was reduced from 1.7 on the uncoated stopper to 0.7 on the coated sample.
Presented below in Table I are the results of tests performed to demonstrate the suitability of the coated stoppers when compared to commercial stoppers. The values for each test are considered totally acceptable for use in pharmaceutical packaging.
TABLE I______________________________________Properties of Polyurethane-Coated Pharmaceutical Elastomers Uncoated Coated______________________________________COF 1.34 0.27Autoclave Stability1 hour at 250° F. No Effect No EffectToxicity Non-toxic Non-toxicParticle Generation 122 250(particles f 5 microns per stopper)USP-NF TestingpH shift (pH units) 0.3 0.3Nephelos (turbidity) 6.0 2.0Reducing Substances 0.02 0.13(mls I.sub.2)Total Solids (mg/100 mls) 3.6 5.4Extractable Zinc (ppm) 0.47 0.20Heavy Metals (Pb, ppm) 0.0 0.0______________________________________
EXAMPLES
Examples of Operation
One hundred pounds of S-867 urethane polymer were mixed with 10 pounds of Sanncor's S-847 urethane polymer, and 5.5 pounds of Cymel®303 curing agent. Pharmaceutical rubber stoppers were spray coated with 1.0 mils on the flange side and 0.8 mils on the cup side. The stoppers were trimmed and washed. They were then autoclave sterilized at 135° for 12 minutes. They were then loaded in a stoppering machine; the maximum speed of the stoppering machine was 330 vials per minute. The stoppering machine operated at maximum speed using the polyurethane coated stoppers, and demonstrated a significant improvement. The standard operating speed using uncoated stoppers lubricated with silicone oil was 220 vials per minute. | A stopper device for use on a pharmaceutical closure, comprising an elastomeric stopper sized to function as a closure; and a polyurethane coating on the stopper. The coating has a modulus sufficient to decrease the coefficient of friction of the stopper to less than 0.6. | 1 |
[0001] This invention is based on the results of a research project sponsored by the US DOE SBIR Program. The US government has certain rights on this invention.
FIELD OF THE INVENTION
[0002] The present invention relates generally to the field of nano materials, and more particularly to nano-graphene plate films and articles.
BACKGROUND OF THE INVENTION
[0003] Carbon is known to have four unique crystalline structures, including diamond, graphite, fullerene and carbon nano-tubes. The carbon nano-tube (CNT) refers to a tubular structure grown with a single wall or multi-wall, which can be conceptually obtained by rolling up a graphene sheet or several graphene sheets to form a concentric hollow structure. A graphene sheet is composed of carbon atoms occupying a two-dimensional hexagonal lattice. Carbon nano-tubes have a diameter on the order of a few nanometers to a few hundred nanometers. Carbon nano-tubes can function as either a conductor or a semiconductor, depending on the rolled shape and the diameter of the tubes. Its longitudinal, hollow structure imparts unique mechanical, electrical and chemical properties to the material. Carbon nano-tubes are believed to have great potential for use in field emission devices, hydrogen fuel storage, rechargeable battery electrodes, and composite reinforcements.
[0004] However, CNTs are extremely expensive due to the low yield and low production and purification rates commonly associated with all of the current CNT preparation processes. The high material costs have significantly hindered the widespread application of CNTs. Rather than trying to discover much lower-cost processes for nano-tubes, we have worked diligently to develop alternative nano-scaled carbon materials that exhibit comparable properties, but can be produced in larger quantities and at much lower costs. This development work has led to the discovery of processes for producing individual nano-scaled graphite planes (individual graphene sheets) and stacks of multiple nano-scaled graphene sheets, which are collectively called “nano-scaled graphene plates (NGPs).” Our invented processes include, as examples, (1) B. Z. Jang and W. C. Huang, “Nano-scaled Graphene Plates,” U.S. Pat. No. 7,071,258 (Jul. 4, 2004)]; (2) B. Z. Jang, et al. “Process for Producing Nano-scaled Graphene Plates,” U.S. patent pending, Ser. No. 10/858,814 (Jun. 3, 2004); and (3) Bor Z. Jang, Aruna Zhamu, and Jiusheng Guo, “Process for Producing Nano-scaled Platelets and Nanocomposites,” US Pat. Pending, Ser. No. 11/509,424 (Aug. 25, 2006). NGPs could provide unique opportunities for solid state scientists to study the structures and properties of nano carbon materials. The structures of these materials may be best visualized by making a longitudinal scission on the single-wall or multi-wall of a nano-tube along its tube axis direction and then flattening up the resulting sheet or plate ( FIG. 2 ). Studies on the structure-property relationship in isolated NGPs could provide insight into the properties of a fullerene structure or nano-tube. Furthermore, these nano materials could potentially become cost-effective substitutes for carbon nano-tubes or other types of nano-rods for various scientific and engineering applications.
[0005] For instance, the following researchers have pointed out the great potential of using NGPs as a new microelectronic device substrate material or a functional material:
1. K. S. Novoselov, et al., “Electric Field Effect in Atomically Thin Carbon Films,” Science 306 (2004) 666-669. 2. H. B. Heersche, et al., “Bipolar Supercurrent in Graphene,” Nature, 446 (March 2007) 56-59. 3. Y. Zhang, Y-W, Tan, H. L. Stormer and P. Kim, “Experimental Observation of the Quantum Hall Effect and Berry's Phase in Graphene,” Nature, 438 (2005) 201-204. 4. Y. Zhang, J. P. Small, M. E. Amori, and P. Kim, “Electric Field Modulation of Galvanomagnetic Properties of Mesoscopic Graphite,” Phys. Rev. Lett., 94 (2005) 176803. 5. C. Berger, et al., “Ultrathin Epitaxial Graphite: Two-dimensional Electron Gas Properties and a Route toward Graphene-based Nanoelectronics,” J. Phys. Chem. B 108 (2004) 19912-19916. 6. G. H. Chen, W. Weng, D. Wu, C. Wu, J. Lu, P. Wang, X. Chen, “Preparation and Characterization of Graphite Nanosheets from Ultrasonic Powdering Technique,” Carbon, 42 (2004) 753-759. 7. H. Fukushima and L. T. Drzal, “Graphite Nanoplatelets As Reinforcements for Polymers: Structural and Electrical Properties,” Proc. Of the 17 th Annual Conf. of the Am. Soc. For Composites, Purdue University, (2003). 8. H. Fukushima, S. H. Lee, and L. T. Drzal, “Graphite Platelet/Nylon Nanocomposites,” Proc. of SPE ANTEC (2004) 1441-1445. 9. W. Zheng, et al, “Transport Behavior of PMMA/Expanded Graphite Nanocomposites,” Polymer, 73 (2002) 6767-6773. 10. A. Yasmin and I. M. Daniel, “Mechanical and Thermal Properties of Graphite Platelet/Epoxy Composites,” Polymer, 45 (2004) 8211-8219.
[0016] The NGP material can be used as a nano-scaled reinforcement for a matrix material to obtain a nanocomposite. Advantages of nano-scaled reinforcements in a matrix material include: (1) when nano-scaled fillers are finely dispersed in a polymer matrix, the tremendously high surface area could contribute to polymer chain confinement effects, possibly leading to a higher glass transition temperature, stiffness and strength; (2) nano-scaled fillers provide an extraordinarily zigzagging, tortuous diffusion path that results in enhanced barrier or resistance against permeation of moisture, oxygen, other gases, and liquid chemical agents. Such a tortuous structure also serves as an effective strain energy dissipation mechanism associated with micro-crack propagation in a brittle matrix such as ceramic, glass, or carbon; (3) nano-scaled fillers can also enhance the electrical and thermal conductivities in a polymer, ceramic or glass matrix; and (4) carbon-based nano-scaled fillers have excellent thermal protection properties and, if incorporated in a matrix material, could potentially eliminate the need for a thermal protective layer, for instance, in rocket motor applications.
[0017] It may be noted that exfoliated graphite flakes (EGFs) are typically obtained by intercalating natural graphite flakes with strong acids to obtain a graphite intercalation compound (GIC). With a sudden exposure to a temperature in the range of 800-1050° C., the GIC expands by a factor of 30-300 to form a “worm,” which is a collection of exfoliated, but largely unseparated graphite flakes. These EGFs are often re-compressed to obtain flexible graphite sheets that typically have a thickness in the range of 0.125 mm (125 μm)-0.5 mm (500 μm).
[0018] It may be further noted that EGFs, if fully separated from one another and having a thickness smaller than 100 nm, are considered as nano-scaled graphene platelets (NGPs). It has been recently recognized by researchers in the field of composites that thin, presumably separated EGFs with an extremely high aspect ratio (length/thickness ratio>100˜1000), lead to a lower percolation threshold (typically 1-4% by weight EGF) for forming an electron-conducting path as compared to a threshold of typically 5-20% for other types of graphite particles. However, at these threshold EGF loadings, the electrical conductivity of the resulting composite, typically in the range of 10 −5 -10 −1 S/cm, is still too low to be used for many engineering applications. For instance, the US Department of Energy (DOE) has set forth a target bulk conductivity of 100 S/cm for composite-based fuel cell bipolar plates.
[0019] Conventional EGF composites typically contain many substantially unseparated graphite flakes, many of which are thicker than 100 nm. These composites with a high EGF loading either can not be formed into thin composite plate, can not be molded with mass production techniques, or are simply not processable into useful products. Although one would expect the electrical conductivity of an EGF composite to become higher if the EGF loading is greater (e.g., >20% by weight), no composite containing more than 20% by weight of well-dispersed, fully separated EG flakes has hitherto been reported. A need exists for a cost-effective method of preparing EGF/polymer composites with a high EGF loading.
[0020] Thus, it is an object of the present invention to provide a highly conductive, thin-film article comprising NGPs or fully separated EGFs wherein the article has a thickness thinner than 50 μm, but could be as thin as 0.1 μm. The thermal conductivity of the thin-film article is greater than 500 W/mK and, in many cases, greater than 1,000 W/mK.
[0021] It is another object of the present invention to provide a thin-film article, preferably in a non-woven mat form, comprising NGPs or fully separated EGFs wherein individual platelets or flakes have a thickness smaller than 10 nm.
[0022] It is yet another object of the present invention to provide a highly conductive thin-film article comprising NGPs or fully separated EGFs wherein the in-plane thermal conductivity is greater than 500 W/mK and in plane electrical conductivity is greater than 1,000 S/cm.
[0023] It is yet another object of the present invention to provide a composite comprising fully separated graphite platelets that are smaller than 100 nm in thickness (preferably smaller than 10 nm) and wherein the weight fraction of platelets is no less than 75%, preferably no less than 85%.
[0024] Still another object of the present invention is to provide a composite comprising at least 75% by weight of fully separated graphite platelets wherein the composite has an electrical conductivity greater than 200 S/cm, preferably greater than 500 S/cm.
[0025] A specific object of the present invention is to provide a composite comprising at least 75% by weight of fully separated graphite platelets wherein the composite has a thermal conductivity greater than 400 W/mK, preferably greater than 1,000 W/mK.
SUMMARY OF THE INVENTION
[0026] In summary, the present invention provides a nano-scaled graphene article comprising a non-woven aggregate of nano-scaled graphene platelets wherein each of the platelets comprises a graphene sheet or multiple graphene sheets and the platelets have a thickness no greater than 100 nm, and wherein platelets contact other platelets to define a plurality of conductive pathways along the article. Preferably, the article is a thin film with a thickness smaller than 50 μm and the platelets have an average thickness no greater than 10 nm. The platelets in the aggregate are preferably closely packed in such a manner that very little space exists between platelets. The article has a thermal conductivity greater than 500 Wm −1 K −1 , preferably and typically greater than 1,000 Wm −1 K −1 , and in many cases, greater than 1500 Wm −1 K −1 . Further, the article has an electrical conductivity greater than 1,000 S/cm, typically greater than 3,000 S/cm and, in many cases, greater than 4,000 S/cm.
[0027] The article may further comprise a desired amount of a nano-scaled filler selected from the group consisting of a carbon nanotube, carbon nano fiber, carbon black, metal nano-powder, and combinations thereof, wherein the amount is preferably no less than 0.1% by weight and no greater than 50% by weight based on the total weight of the nano-scaled filler and the nano-scaled graphene platelets.
[0028] The article, in the form of a thin non-woven mat or aggregate of NGPs, may comprise a matrix or binder material that impregnates or infiltrates the article to form a composite article. The composite article tends to have an improved thermal conductivity. Pyrolytic graphite-infiltrated mat has exceptionally high thermal conductivity that has not been achieved by other graphite materials.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIG. 1 A flow chart illustrating various prior art processes of producing exfoliated graphite products (flexible graphite and composites) and presently invented processes of producing a non-woven mat of aggregates of NGPs or fully separated EGFs.
[0030] FIG. 2 (a) Schematic of NGP structures in comparison with CNT structures; (b) Atomic force microscopic image of selected NGPs.
[0031] FIG. 3 (a) A SEM image of a graphite worm sample after exfoliation of graphite intercalation compounds (GICs); (b) Schematic of the exfoliated graphite flakes in a flexible graphite sheet, indicating that very many flakes are not aligned parallel to the two opposing surfaces of the flexible graphite sheet; (c) An SEM image of a cross-section of a flexible graphite sheet, confirming the non-parallel orientations of the constituent graphite flakes.
[0032] FIG. 4 Schematic of a non-woven, close-packed aggregate of separated EGFs or NGPs obtained by dispersing the EGFs or NGPs in a liquid medium to a relatively dilute state (e.g., <5% by weight of NGPs in water) and then re-assembling the platelets or flakes in a layer-wide manner to obtain a thin-film article.
[0033] FIG. 5 In-plane thermal conductivity values of a non-woven mat of expanded, separated graphite flakes or NGPs (data denoted by a solid diamond, ♦), a phenolic resin-impregnated mat (solid square, ▪), and a CVD pyrolitic graphite impregnated mat (solid triangle ), plotted as a function of the mat thickness on a 10-based log scale.
[0034] FIG. 6 In-plane electrical conductivity values of a non-woven mat of expanded, separated graphite flakes or NGPs (data denoted by a solid diamond, ♦), a phenolic resin-impregnated mat (solid square, ▪), and a CVD pyrolitic graphite impregnated mat (solid triangle ), plotted as a function of mat thickness on a 10-based log scale.
[0035] FIG. 7 (A) Schematic of a vacuum-assisted flake assembly apparatus for forming a non-woven, close-packed structure of NGP platelets; (B) Slurry spraying and filtration process for producing a non-woven article of NGPs.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0036] Graphite is made up of layer planes of hexagonal networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another. These layers of carbon atoms, commonly referred to as graphene layers or basal planes, are weakly bonded together in their thickness direction by weak van der Waals forces and groups of these graphene layers are arranged in crystallites. Highly ordered graphites consist of crystallites of considerable size: the crystallites being highly aligned or oriented with respect to each other and having well ordered carbon layers. These anisotropic structures give rise to many properties that are highly directional such as thermal and electrical conductivity.
[0037] The graphite structure is usually characterized in terms of two axes or directions: the “c” axis or direction and the “a” axes or directions. The “c” axis is the direction perpendicular to the basal planes. The “a” axes are the directions parallel to the basal planes (perpendicular to the “c” direction). The graphites suitable for manufacturing flexible graphite sheets are typically natural graphite flakes that possess a very high degree of orientation.
[0038] Due to the weak van der Waals forces holding the parallel graphene layers, natural graphite can be treated so that the spacing between the graphene layers can be appreciably opened up so as to provide a marked expansion in the “c” direction, and thus form an expanded graphite structure in which the laminar character of the carbon layers is substantially retained. The process for manufacturing flexible graphite is well-known and the typical practice is described in U.S. Pat. No. 3,404,061 to Shane et al., the disclosure of which is incorporated herein by reference. In general, flakes of natural graphite are intercalated in an acid solution to produce graphite intercalation compounds (GICs). The GICs are washed, dried, and then exfoliated by exposure to a high temperature for a short period of time. This causes the flakes to expand or exfoliate in the “c” direction of the graphite up to 80-300 times of their original dimensions. The exfoliated graphite flakes are vermiform in appearance and, hence, are commonly referred to as worms. These worms of graphite flakes which have been greatly expanded can be formed without the use of a binder into cohesive or integrated sheets of expanded graphite, e.g. webs, papers, strips, tapes, foils, mats or the like (typically referred to as “flexible graphite”) having a typical density of about 0.04-2.0 g/cm 3 for most applications.
[0039] FIG. 1 is a flow chart that illustrates the prior art processes used to fabricate flexible graphite, the resin-impregnated flexible graphite composite, and the conventional expanded graphite flake (EGF) composite that normally contains less than 15% by weight EGFs in a polymer matrix. The processes typically begin with intercalating graphite particles 20 (e.g., natural graphite or synthetic graphite flakes) with an intercalant (typically a strong acid or acid mixture) to obtain a graphite intercalant compound 22 (GIC). After rinsing in water to remove excess acid, the GIC becomes an expandable graphite. The GIC or expandable graphite is then exposed to a high temperature environment (e.g., in a tube furnace preset at a temperature in the range of 800-1,050° C.) for a short duration of time (typically for 15 seconds to 2 minutes). This thermal treatment allows the graphite to expand in its “c” direction by a factor of 30 to several hundreds to obtain a worm-like vermicular structure, which contains exfoliated, but largely unseparated graphite flakes 24 with large pores interposed between flakes.
[0040] In one prior art process, the exfoliated graphite is re-compressed by using a calendering or roll-pressing technique to obtain flexible graphite sheets or foils 26 , which are typically much thicker than 100 μm. It seems that no flexible graphite sheet thinner than 75 μm has ever been reported in the open literature. Commercially available flexible graphite sheets normally have an in-plane electrical conductivity of 1-3×10 3 S/cm, through-plane (thickness-direction) electrical conductivity of 15-30 S/cm, in-plane thermal conductivity of 140-190 W/(mK), and through-plane thermal conductivity of approximately 5 W/(mK).
[0041] In another prior art process, the exfoliated graphite worm 24 may be impregnated with a resin and then compressed and cured to form a flexible graphite composite 28 , which is normally of low strength. Alternatively, the exfoliated graphite worm may be impregnated with a monomer, which is then polymerized. This so-called “in situ polymerization” process also serves to partially separate the graphite flakes and the resulting graphite flake composite 32 tends to have relatively low thermal and electrical conductivities.
[0042] In a preferred embodiment of the present invention, the exfoliated graphite may be subjected to mechanical attrition/separation treatments using an air mill, ball mill, or ultrasonic device to produce separated graphite flakes 30 , which may have some flakes thicker than 100 nm. These separated flakes 30 preferably are subjected to further separation and size reduction treatments to obtain nano-scaled graphene plates 34 (NGPs) with all the graphite platelets thinner than 100 nm, preferably thinner than 10 nm. An NGP is composed of a graphite sheet or a plurality of graphite sheets with each sheet being a two-dimensional, hexagonal carbon structure ( FIG. 2(A) ). Several NGPs are shown in an atomic force microscopic image, FIG. 2(B) .
[0043] For the purpose of defining the geometry and orientation of an NGP, the NGP is described as having a length (the largest dimension), a width (the second largest dimension), and a thickness. The thickness is the smallest dimension, which is no greater than 100 nm, preferably smaller than 10 nm in the present context. When the platelet is approximately circular in shape, the length and width are referred to as diameter. In the presently defined NGPs, both the length and width can be smaller than 1 μm, but can be larger than 200 μm. Although expanded graphite flakes (EGFs) can have thickness greater than 100 nm, we prefer to use thin flakes or platelets that have a thickness smaller than 100 nm (most preferably thinner than 10 nm). The length and width of EGFs are normally greater than 1 μm, typically greater than 10 μm, and most typically between 10 μ and 200 μm.
[0044] The separated, expanded graphite flakes (EGFs) 30 , preferably thinner than 100 nm, or the NGPs 34 (preferably thinner than 10 nm) are dispersed in a fluid (e.g., water) to produce a low concentration of flakes or platelets suspended in the fluid. The flake or platelet concentration is preferably lower than 10% by weight in the suspension (most preferably smaller than 5%). The suspension (or slurry) is allowed to undergo controlled aggregation using techniques like vacuum-assisted filtration, spin coating, or paper-making. The resulting non-woven aggregates 36 of graphite flakes or platelets are such that flakes/platelets contact other flakes/platelets to form a network of conductivity pathways. This non-woven article is preferably a thin film with a thickness less than 50 μm, preferably less than 10 μm, further preferably less than 1 μm and can be thinner than 0.1 μm (100 nm). The non-woven article may be further compressed by using a calendering or roll-pressing technique. The resulting thin film may be schematically shown in FIG. 4 , wherein the thin-film structure is composed of close-packed flakes or platelets 46 , 48 .
[0045] The worms (e.g., FIG. 3(A) ) can be formed into integrated flexible graphite sheets by compression, without the use of any binding material, presumably due to the mechanical interlocking between the voluminously expanded graphite flakes. Although a significant proportion of these flakes are oriented in a direction largely parallel to the opposing surfaces of a flexible graphite sheet (as evidenced by the high degree of anisotropy with respect to thermal and electrical conductivity), many other flakes (e.g., as illustrated by 40 , 41 , 42 in FIG. 3(B) ) are distorted, kinked, bent over, or oriented in a direction non-parallel to these sheet surfaces. This observation has been well demonstrated in many scanning electron micrographs (SEM) published in open or patent literature (e.g., FIG. 3(C) ). As a consequence, the electrical or thermal conductivity of the resulting flexible graphite dramatically deviates from what would be expected of a perfect graphite single crystal or a graphene layer. For instance, the theoretical in-plane electrical conductivity and thermal conductivity of a graphene layer are predicted to be 1-5×10 4 S/cm and 2,000-3,000 W/(mK), respectively. However, the actual corresponding values for flexible graphite are 1-3×10 3 S/cm and 140-300 W/(mK), respectively; one order of magnitude lower than what could be achieved. By contrast, the corresponding values for the presently invented non-woven article of NGP aggregates are 3.4-5.5×10 3 S/cm and 580-2050 W/(mK), respectively (representative data given in FIG. 5 and FIG. 6 with data points denoted by a solid diamond, ♦).
[0046] The NGP aggregate-based non-woven article may be prepared using one of the following techniques:
A. Vacuum-Assisted Filtration and Subsequent Deposition, Impregnation, or Infiltration
[0047] As schematically shown in FIG. 7( a ), fully separated graphite flakes or NGP platelets may be dispersed in water to produce a dilute platelet suspension with the platelet concentration preferably lower than 5% by weight. This NGP-water suspension or slurry is then poured into a container 50 . At the bottom of this container is a nano-filter 52 (with pore sizes preferably of 100 nm-500 nm); e.g., GE TefSep™ filtering membrane. Water filters through this membrane filter 52 and collected at the bottom 56 of a container 54 . This container is connected to a vacuum line to promote the transport of water through the membrane.
[0048] It may be noted that the same apparatus may be used to impregnate the resulting non-woven mat with a resin or other type of matrix material (e.g., mesophase pitch or metal). Preferably, the nano-filter membrane is replaced by a regular filter paper after the non-woven mat is formed and dried. A resin (e.g., epoxy or phenolic resin), preferably diluted by a diluent first (e.g., acetone), is sprayed onto the top surface of the non-woven mat. The suction force created by the vacuum line will facilitate permeation of the resin through the mat. The diluent is dried and the resulting impregnated mat is then cured by heat to obtain a NGP mat-resin composite.
[0049] The non-woven mat of NGPs can be further modified with one or more of several surface treatment or volume infiltration techniques, e.g., chemical vapor deposition (or chemical vapor infiltration), electrodeposition, electro-less deposition, to tailor the structure and properties of the mat. An example is the chemical vapor deposition or infiltration of pyrolytic graphite on and in the mat. This can be done by introducing methane gas into a reactor that accommodates the NGP mat and allows chemical decomposition and carbon formation to occur at a temperature of 800-1500° C. first, then at a higher temperature up to 2,500-3,000° C. for a desired duration of time, typically from 1-10 hours.
[0050] Highly ordered pyrolytic graphites having densities near 2.2 g/cc and good thermal conductivity have been produced by vapor deposition of carbon. Highly oriented pyrolytic graphite (HOPG) may have a thermal conductivity on the order of 800 w/(mK). However, the HOPG materials by themselves are extremely fragile. In the present invention, only a small amount of pyrolytic graphite is needed in terms of infiltrating the non-woven NGP mat and NGPs provide high strength and stiffness.
[0051] Furthermore, the bulk graphite widely used commercially for fabricating articles such as crucibles and electrodes are largely amorphous, relatively low in density, and lacking the high thermal conductivity of crystal graphite. Some bulk graphites may be semi-crystalline with the crystalline component comprising large, randomly-oriented graphitic crystallites, generally greater in size than about 30 to 50 microns, embedded in a substantially amorphous carbon phase. These lower-density bulk graphite articles will generally exhibit only a fraction of the bulk thermal conductivity that characterizes highly organized crystalline graphite. By contrast, the pyrolytic graphite-modified NGP mat exhibits an exceptionally high thermal conductivity, typically higher than 1,500 W/(mK), which is 4-5 times higher than that of copper. This is an exceptional achievement!
[0052] The non-woven NGP mat may be infiltrated with mesophase or liquid crystal pitch, which may be readily transformed thermally into a more crystalline graphite. It is well-known that bulk mesophase pitch by itself, when processed in bulk into crystalline graphite, exhibits a bulk thermal conductivity considerably below that of crystal graphite. Surprisingly, the mesophase pitch, upon infiltration and pyrolization, imparts excellent conductivity to the non-woven mat. The resulting carbon-carbon composite (or, more accurately, graphite-graphite composite) have outstanding thermal and electrical conductivities ( FIG. 5 and FIG. 6 ; data denoted by ▴).
B. Spin Coating or Casting of NGP-Liquid Suspension
[0053] In one preferred embodiment, a thin mat comprising overlapping or closely-packed NGPs or EGFs can be prepared by dispersing NGPs or EGFs in a liquid medium to form a suspension, which is followed by spin-coating or spin-casting. Although spin-casting or spin-coating of a polymer-solvent solution is well-known in the art, it has never been adapted for forming an NGP mat without a resin. Surprisingly, the resulting mat comprises graphene flakes or platelets that are closely packed together to have a relatively high density.
C. Slurry Spraying and Filtration
[0054] In another preferred embodiment of the present invention, a porous mat can be made by using a continuous platelet-water suspension spraying technique. For instance, as shown in FIG. 7(B) , the process begins with pulling a web 86 (porous sheet) from a roller 84 . The moving web receives a stream of slurry 88 (flakes+water) from above the web. Water sieves through the web with all NGPs remaining on the surface of the web. These solid ingredients are moved forward to go through a compaction stage by a pair of compaction rollers 90 a, 90 b. The roll-pressed mat 91 may be collected by a winding roller 92 .
[0055] In addition to NGPs or EGFs, other conductive ingredient such as metal fibers, carbon nano-tubes, graphitic nano-fibers, carbon fibers, carbon blacks, or a combination thereof can be added to become part of a non-woven mat by using any of the aforementioned techniques. Preferably, these fillers occupy a weight fraction lower than 50%. The type and proportion of the conductive fillers are preferably chosen in such a way that they enhance other desired properties (e.g., mechanical integrity) without significantly compromising electrical and thermal conductivity of the resulting mat or its resin- or graphite-impregnated versions. All the NGP-based mats prepared by any of the aforementioned methods (B and C) can be subjected to resin/graphite impregnation or infiltration treatments as discussed in method A (vacuum-assisted filtration).
EXAMPLE 1
Preparation of Exfoliated Graphite and Separated Flakes
[0056] Natural flake graphite with an average diameter of 150 μm was used for preparing the exfoliated graphite. Concentrated sulfuric acid, nitric acid (chemically pure), glacial acetic acid, and potassium permanganate were used as the chemical intercalate and oxidizer to prepare graphite intercalation compounds (GICs). Chemically pure alcohol (95% by volume) and distilled water were used as a dispersing medium for the preparation of fully foliated and separated graphite flakes or NGPs.
[0057] Exfoliated graphite (EG) was prepared according to the following procedure: The natural flake graphite was first dried in a vacuum oven for 24 h at 80° C. Then, a mixture of concentrated sulfuric acid and fuming nitric acid (4:1, v/v) was slowly added, under appropriate cooling and stirring, to a three-neck flask containing graphite flakes. After 16 hurs of reaction, the acid-treated natural graphite was filtered and washed thoroughly with deionized water until the pH level of the solution reached 6. After being dried at 100° C. overnight, the resulting graphite intercalation compound (GIC) was subjected to a thermal shock at 1050° C. for 15 seconds in a muffle furnace to form exfoliated graphite (worms).
[0058] Five grams of the resulting EG were mixed with 2,000 ml alcohol solution consisting of alcohol and distilled water with a ratio of 65:35 for 12 hours to obtain a suspension. Then the mixture or suspension was subjected to ultrasonic irradiation with a power of 200 W for various times. After two hours of sonication, EG particles were effectively fragmented into thin expanded graphite flakes (EGFs). The suspension was then filtered and dried at 80° C. to remove residue solvents. The as-prepared EGFs are typically thinner than 30 nm and, hence, also referred to as nano-scaled graphene platelets (NGPs). These NGPs were then kept in a dry desiccator for testing and further use.
EXAMPLE 2
Preparation of Exfoliated Graphite and Separated Flakes
[0059] In this graphite intercalation route, the ratio among natural graphite, nitric acid, glacial acetic acid, and potassium permanganate was 1:1:0.8:0.06 by weight. The procedure began with mixing natural graphite particles with potassium permanganate in a glass beaker, which was cooled with an ice bath. Concentrated nitric acid was carefully poured into the beaker while the mixture was magnetically stirred. Then, glacial acetic acid was slowly added to the mixture using a pipette. After 21 hours of reaction, the acid-treated natural graphite was filtered and washed thoroughly with deionized water until the pH level of the solution reached 6. After being dried at 80° C. overnight, the resulting graphite intercalation compound was subjected to a thermal shock at 1050° C. for 15 seconds in a muffle furnace to form exfoliated graphite. Part of the exfoliated graphite worms was subjected to further size reduction and separation by using a high-intensity planetary ball mill for 24 hours.
EXAMPLE 3
Preparation of Exfoliated Graphite and Separated Flakes
[0060] The graphite intercalation procedure was similar to that used in Example 2, but nitric acid was replaced by sulfuric acid. The ratio among natural graphite, sulfuric acid, glacial acetic acid, and potassium permanganate was 1:0.5:2:0.07 by weight. After exfoliation at 1050° C. for 15 seconds, the expanded graphite worms were re-immersed in an intercalant solution for 21 hours, followed by washing, drying, and re-exfoliation again at 1050° C. for 15 seconds. The resulting graphite flakes are mostly thinner than 10 nm.
EXAMPLE 4
Preparation of Thin-Film Non-Woven Articles
[0061] The EGFs or NGPs prepared in Example 3 were used for the preparation of non-woven aggregates of EGFs wherein the flakes/platelets contact one another to form a network of multiple conductivity pathways. Fully separated graphite flakes or NGP platelets were dispersed in water to produce a dilute platelet suspension with the platelet concentration of approximately 4% by weight. Ultrasonic waves were employed to assist in the dispersion of NGPs in water. This NGP-water suspension or slurry was then poured into a container, as schematically shown in FIG. 7( a ). At the bottom of this container is a nano-filter 52 (GE TefSep™ filtering membrane with pore sizes of approximately 200 nm). Water filters through this membrane filter 52 and collected at the bottom 56 of a container 54 . A vacuum pump was utilized to assist in the transport of water through the membrane.
EXAMPLE 5
Preparation of Resin-Impregnated, Thin-Film Non-Woven Mat
[0062] The same apparatus was used to impregnate the resulting non-woven mat with a phenolic resin. The nano-filter membrane was replaced by a sheet of less expensive filter paper after the non-woven mat is formed and dried. Phenolic resin, diluted by acetone, was sprayed onto the top surface of the non-woven mat. Again, a vacuum pump was used to generate a suction force to facilitate the permeation of the resin through the mat. Acetone was allowed to vaporize at 60° C. under a chemical flume hood and the resulting impregnated mat was cured by heat to obtain a NGP mat-resin composite.
EXAMPLE 6
Preparation of Pyrolitic Graphite-Infiltrated Non-Woven Mat
[0063] The non-woven mat of NGPs can be modified with one or more of several surface treatment or volume infiltration techniques, e.g., chemical vapor deposition (or chemical vapor infiltration), electrodeposition, electro-less deposition, to tailor the structure and properties of the mat. Samples of non-woven mats obtained in Example 4 were subjected to chemical vapor deposition or infiltration of pyrolytic graphite. This was achieved by introducing methane gas into a reactor that accommodates the NGP mat and allows chemical decomposition and carbon formation to occur at a temperature of 1,000° C. first for 1 hour and then graphitized at a higher temperature of 3,000° C. for a 2 hours.
[0064] The in-plane and through-plane (thickness-direction) thermal and electrical conductivities of three series of NGP mats and their composites were investigated with the purposes of (a) comparing the properties of NGP mat, its resin-impregnated version, and its CVD graphite infiltrated version and (b) understanding how these properties vary with the mat or composite thickness. The through-plane thermal conductivity of all these samples are in the range of 14-15 W/(mK). As shown in FIG. 5 , the in-plane thermal conductivity values of the NGP mat and composites increase as the thickness decreases. Several significant observations can be made from this figure:
(1) At a thickness of approximately 105 μm, the thermal conductivity of an NGP non-woven mat is 580 W/(mK), much higher than 140-190 W/(mK), the values commonly associated with commercially available flexible graphite. (2) With fully separated, ultra-thin flakes or NGPs, we can obtain a non-woven mat of platelets much thinner than 100 μm (the practical lower limit of flexible graphite thickness). A sample as thinner than 100 nm can be readily obtained. Such a thin, well-packed NGP aggregate exhibits an exceptionally high thermal conductivity of approximately 2,000 W/(mK). (3) Resin impregnation of the non-woven mat slightly increases the thermal conductivity. Chemical vapor infiltration of the NGP mat with pyrolytic graphite increases the thermal conductivity to a much greater extent. Surprisingly high thermal conductivity values were observed with the NGP mat densified with pyrolytic graphite; values as high as 4-5 times the conductivity of pure copper.
[0068] The in-plane electrical conductivity values of the NGP mat and composites increase as the thickness decreases, as shown in FIG. 6 . Several significant observations can be made from this figure:
(1) At a thickness of approximately 105 μm, the electrical conductivity of an NGP non-woven mat is 3,450 S/cm, much higher than 1,100 S/cm, the values commonly associated with commercially available flexible graphite. (2) An NGP-based non-woven mat 90 nm thick exhibits an in-plane electrical conductivity of approximately 6,540 S/cm. (3) Resin impregnation of the non-woven mat appears to slightly decrease the thermal conductivity. Chemical vapor infiltration of the NGP mat with pyrolytic graphite significantly increases the electrical conductivity. Also quite surprisingly, very high electrical conductivity values (10,000-29,500 S/cm) were observed with the NGP mat densified with pyrolytic graphite.
[0072] In addition to carbon, graphite, and polymer, NGP mats may also be impregnated with or infiltrated by a metal, ceramic, or glass matrix. As indicated earlier, additional fillers (preferably nano-scaled) may be added to the NGP mats or composites to modify other properties such as friction, wear, strength, stiffness, and toughness. These nano-scaled fillers may be selected from the group consisting of carbon nanotubes, carbon nano fibers, carbon blacks, metal nano-powders, and combinations thereof.
[0073] In conclusion, we have successfully developed a new and novel class of highly conducting, non-woven materials and their nanocomposites that contain truly nano-scaled graphene platelets which have platelet thickness smaller than 100 nm. The thermal and electrical conductivities exhibited by the presently invented mat of NGPs are much higher than what prior art flexible graphite could achieve. The thermal and electrical conductivities exhibited by the presently invented mat of NGPs, infiltrated with CVD graphite, are among the highest that graphite-type materials could achieve. | Disclosed is a nano-scaled graphene article comprising a non-woven aggregate of nano-scaled graphene platelets wherein each of the platelets comprises a graphene sheet or multiple graphene sheets and the platelets have a thickness no greater than 100 nm (preferably smaller than 10 nm) and platelets contact other platelets to define a plurality of conductive pathways along the article. The article has an exceptional thermal conductivity (typically greater than 500 Wm −1 K −1 ) and excellent electrical conductivity (typically greater than 1,000 S/cm). Thin-film articles of the present invention can be used for thermal management in micro-electronic devices and for current-dissipating on an aircraft skin against lightning strikes. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of U.S. Ser. No. 12/831,849, filed Jul. 7, 2010 which is a continuation-in-part application of U.S. Ser. No. 10/516,297, filed Dec. 19, 2005, now U.S. Pat. No. 7,912,532 issued Mar. 22, 2011. U.S. Ser. No. 10/516,297 is a national stage application of PCT/EP03/06130, filed Jun. 11, 2003, and claims priority to DE 102 49 025.2, filed Oct. 21, 2002, and DE 102 26 361.2, filed Jun. 13, 2002. The entire content of each is incorporated herein by reference.
BACKGROUND
[0002] 1. Field of Invention
[0003] This disclosure relates to optimizing identification of a current position in surgical navigation, especially neuronavigation, in surgery with an operating microscope and at least one optoelectronic image receiver, which may also be integral or connectable to the microscope and a computer system.
[0004] 2. Discussion of the Related Art
[0005] Neuronavigation deals with the planning, but also with the performance of trajectories for surgical intervention at the human brain, the spine and the like. To this end, tomographies of the patient are made preoperatively, with markings provided on the patient's body which will likewise be detected by the tomography. Directly before the operation the three-dimensional location of said markers in space is determined by navigation, and a reference between the anatomy of the patient and the preoperatively recorded data records is thus produced. A corresponding process is called registration. Basically, a difference between optical navigation methods and magnetically working methods can be made. Both methods serve to determine the three-dimensional location and orientation of a special navigational pointer instrument in space, which serves to tap on relevant points. The location of the pointer tip in known optically working systems is not detected directly, but is determined with the aid of markers which, in most cases, are attached to the pointer in the form of balls. In the known systems reflectors for infrared light generated by special infrared light radiation sources are used as markers or marker substances. Two cameras located on a tie-bar then record the images and determine the location of the pointer in space.
[0006] According to methods based on magnetic fields, the pointers comprise sensors which serve to detect the spatial location either from a generated magnetic alternating field or from a pulsed magnetic continuous field.
[0007] Optical systems have the disadvantage that there is the danger of the camera being covered by the operating staff Magnetic systems fail to operate once objects made of soft iron are in the proximity thereof, which upset or distort the magnetic fields.
[0008] The basic object of the navigational systems available on the market resides in that—as was briefly outlined above—the position or the tip of an instrument, with which a detail in the field of operation is pointed to during the operation, is correlated with data from preoperative diagnostic methods, such as computerized tomography or magnetic resonance tomography. After such a correlation has taken place, for example, the position of a point in situs, to which the surgeon points with the aforementioned instrument during the operation, may be indicated to him in the images of the preoperative photographs in real-time. In this manner the surgeon obtains information with respect to the current position relative to a position of a structure recognizable in the CT- or MR-image, e.g. a tumor.
[0009] One possibility to represent this information to an operating surgeon is to register the position of the instrument tip in a previously selected CT- or MR-image as a point. For allowing the navigational system to fulfill this task, both the location and the orientation of the patient as well as those of the aforementioned surgical instrument must be known. As was explained, this information is, in current systems, detected for example by means of a pair of stereo cameras, which is located in the proximity of the operating table and detects the operating instrument.
[0010] Other known navigation systems moreover offer the possibility of overlapping images from preoperative diagnostic methods with the optical image of an operating microscope in the correct position, orientation and scale. In order to achieve this, the position and the orientation of the operating microscope as well as the currently selected magnification and plane of focus must additionally be detected. In the known navigational systems this detection of position and orientation of the operating microscope takes in most cases place by providing reflecting markings on the microscope which, just like the aforementioned markings on the pointer, are detected by said two cameras on the aforementioned tie-bar. Moreover, there is a known system according to which the relative position and orientation of the microscope is detected by means of angle of rotation transmitters in the microscope carrier system. The disadvantage in said last-mentioned systems resides in that the carrier systems used therefore required a reinforcement so as to ensure a sufficient exactness, which renders them disproportionately heavy and expensive. The overlapping itself may then, for example, be effected by reflecting the CT- or MR-image into the optical observation beam path of the microscope by means of a projector.
[0011] The navigational systems according to the prior art show some substantial disadvantages. This includes, inter alia, the fact that the markings on the surgical instrument or, respectively, on the pointer must at any time be visible to the pair of stereo cameras disposed on the camera arm. If the markings are covered, the functional capability is negatively influenced and errors in the data acquisition occur. According to experience the so-called position-identifying times of optical, but also of magnetic navigation systems are about ⅔. In addition, the large distance between the markings of the known optical instruments and the camera pair causes large measuring inaccuracies in the optical measurement, and relatively large-volume markings are required.
[0012] Another problem with current neurosurgical navigational systems resides in the motion of the brain tissue after the skullcap was opened and during the operation. This fact called brain shift results in that the geometry of the tissue during the operation no longer unlimitedly corresponds to the geometry of the tissue during the preoperative diagnostic method. This leads to errors, for example, in the aforementioned position indication of a pointer instrument relative to the tissue structures in a preoperative diagnostic MR- or CT-image. The error as described may be corrected, for example, by tracking the change of location of the tissue surface in the surroundings of the field of operation during the operation. To this end, the surgeon must, however, repeatedly tap on and mark several points on the aforementioned tissue surface with a marking instrument of the navigational system so as to make the data required for this correction available to the system. Given the stress, which in a neurosurgical operation is high enough anyhow, this constitutes a disadvantage, however.
[0013] By taking into account the aforementioned disadvantages of the prior art, the aim of navigational systems to be newly provided therefore resides in allowing a three-dimensional measurement of the field of operation and a tracking of the trajectories of the tip of the operating instrument, and in achieving an increased position identification, especially in the case of optical navigation. In addition, the large, expensive and occlusion-susceptible camera tie-bars are to be avoided. The handling of the systems is to be made simple and easy to survey so as to preclude error sources right from the beginning.
SUMMARY
[0014] According to the above it is, therefore, the object of the invention to provide an apparatus, system and method for optimizing the identification of the current position in navigation, especially neuronavigation, in surgery, which is based on an operating microscope known per se and at least one optoelectronic image receiver coupled to the observation beam path of the microscope.
[0015] Moreover, a partial object of the invention resides in creating a novel navigational instrument, especially for use in operations by means of an operational microscope.
[0016] The object of the invention is provided by an operating microscope and associated method for optimizing the identification of a current position. The operating microscope includes an optoelectronic image receiver, preferably a photonic mixer device (PMD), to detect a topography of a situs relative the microscope, and a modulated illumination device associated with the PMD to provide modulated illumination light.
[0017] In a preferred aspect, the PMD is arranged such that a sensor axis of the PMD is parallel to an optical axis of an observation beam path of the optoelectronic image receiver. Similarly, it is also preferred the observation beam path and the PMD are positioned at a common distance from the situs. Specifically, light from the situs travels a similar path, both in distance and angle, to the observation beam path and the PMD.
[0018] In additional aspects, optical filters are provided to protect the PMD from intensive illumination by unmodulated light, and the PMD detects markings on the situs, the markings including at least one of infrared reflectors or light emitting diodes. Further, a device is provided to generate a three-dimensional image of the situs from an image received from the optics of the microscope and the topography of the situs detected by the PMD.
[0019] In yet a further aspect, provided is an operating microscope including an optical unit for forming an image of an object plane in oculars of the microscope, an optoelectronic image receiver coupled to the microscope and optics to form images, of objects placed in a region between a front objective of the microscope and an object plane of the microscope, on the optoelectronic image receiver. The microscope has a magnification factor of the optics to form images, and a system to detect optical markings forming a markings pattern placed on a surgical instrument or an object placed in the region between the front objective of the microscope and the object plane of the microscope. The system calculates a geometrical position and orientation of the markings pattern in relation to the optoelectronic image receiver, relative the microscope.
[0020] Accordingly, the basic idea of the invention is to improve the position-identifying time of a navigational system by including the images from or parallel to the observation channels of the operating microscope in the actual image analysis of said system and to achieve additional advantageous effects, especially under the aspect of improving the exactness of the positional determination.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
[0022] FIG. 1 is a schematic illustration of a surgical suite according to aspects of this disclosure, including a navigation system;
[0023] FIG. 2 is a schematic diagram of a navigation system including a tracking camera positioned above a schematic drawn skull;
[0024] FIG. 3 is a generated three-dimensional image of the skull schematically shown in FIG. 2 ;
[0025] FIG. 4 is a schematic diagram of a computer system for processing the various algorithms and processes described in this disclosure; and
[0026] FIG. 5 is a flowchart depicting a process and algorithm in accordance with preferred aspects of this disclosure.
DETAILED DESCRIPTION
[0027] Data obtained from the at least one image receiver, each of which lie in the microscope field-of-view of the operator, contain information about the location of the operating instrument or pointer as used, especially of the tip thereof, wherein the actual position of the instrument in the x- and y-direction as well as in the z-direction of a three-dimensional coordinate system is continuously or intermittently determined from the relevant location data. For the positional determination in the z-direction either a distance determination is carried out by means of a depth of focus evaluation, or a stereoscopic image analysis is performed. Instead of two cameras with a stereoscopic image analysis also a novel optoelectronic image receiver designated as PMD array (PMD: Photonic Mixer Device) may be used. The measuring method of these sensors is related to the “time of flight” distance measuring method, but achieves, by novel principles with a smaller amount of apparatus and substantially smaller construction sizes, a better measuring exactness and may additionally be designed as a sensor array, with the result that it becomes feasible for the representation of an area to be topographed on a PMD array to obtain a complete topography with one measurement only. Since, due to the topography of a pointer, the pointer and the suitably formed markings thereof are easy to separate before the background of the field of operation, such a PMD array may also be used for tracking said pointer. If a PMD sensor is used, the object field of the sensor must be illuminated with an appropriately modulated and preferably narrow-banded light source, and the background light as well as the unmodulated white light of the operating microscope must be discriminated by suited filters prior to impinging the PMD array.
[0028] The optoelectronic image receiver(s) may directly be coupled to the observation beam path, especially by means of a beam splitter, wherein it also possible, however, to provide at least one separate image receiver beam path not being dependent on the observation beam path, which is likewise directed to the microscope field-of-view of the operator.
[0029] According to an embodiment the location of the operating microscope in space is detected, and said operating microscope positional data are supplied to a computer system known per se so as to transform the instrument positional data into a higher ranking space coordinate system by including existing data on the current position of the patient and preoperatively obtained three-dimensional data from the interior of the patient.
[0030] According to one embodiment of the invention it is possible, beside the data acquisition for the intraoperative location and position determination of a navigational instrument by means of known optical and/or magnetic methods, to carry out a supplementary three-dimensional position detection by means of the data provided by the image receiver of the operating microscope.
[0031] When using said two independent redundant systems, the hereinafter mentioned advantageous possibilities arise. If one of the systems does not supply any valid measured values, for example due to the covering of the markings, the measured values of the respective other system may be used, thereby allowing an increase of the position-identifying time. In case of redundant valid measured values the exactness of the measurement may be increased, for example, by averaging. In case of redundant valid measured values also the uncertainty of the measured values, e.g. due to the difference of the redundant measured values, may be quantified, whereby, for the first time, a navigational system is created which is more or less capable of performing a self-control. Even though the latter is standard for the major part of medical apparatus being critical for the safety of patients, it has so far not been realized in known navigational systems.
[0032] For detecting the location of the operating microscope in space a module is provided as an alternative to the known methods, which is integrated in the microscope or at least is connected with the microscope in a fixed and positionally invariant manner, which may do without the use of the space-filling tie-bars with cameras used in known systems and to be positioned next to the operating table. This module allows the microscope to detect its relative position in space or relative to the patient “by itself”. Therefore, numerous components and measuring methods may be individually or in a combination thereof. For minimizing the size of the aforementioned module, required infrastructure (power supply mechanisms, computers etc.) may be integrated, for example, in the base of the carrier system.
[0033] If the microscope “itself” is able to determine its position in space or, respectively, relative to the patient, and if also the tracking of the pointer is realized without the stereo camera pair of the conventional navigational system, the stereo camera pair of the conventional navigational system may be dropped. In this case, space in the operating theatre is considerably saved. Moreover, the initiation is facilitated since fewer devices with fewer cables have to moved and operated before the operation starts and, furthermore, the danger of occlusions during the operation is eliminated or at least considerably reduced.
[0034] With respect to the problems involved by the so-called brain shifting it is provided according to the invention to arrange marking points at or on the tissue surface of the patient, the change of location of which detected by the image receivers and determined by the computer system is used to carry out a correction of preoperatively obtained data in relation to the current state.
[0035] As is known, a stereoscopic light microscope may either consist of two convergent monocular mono-objective microscopes, or may comprise two optical channels brought out of center behind a common front lens. Due to construction-specific advantages operating microscopes are nearly exclusively structured as so-called common main objective (CMO) microscopes. The modeling of a CMO-microscope in an optical view is, however, extremely difficult as the treatment of so-called skew light beams becomes necessary. This is based on the lateral displacement of both optical channels behind the aforementioned common front lens.
[0036] If a stereoscopic analysis for neuronavigation becomes necessary, the person skilled in the art will at first preclude the use of CMO-microscopes by taking into account the aforementioned problems.
[0037] This prejudice is overcome herein by finding an exclusively analytic formulation of the microscope model, which eventually corresponds to two rectified pin diaphragm cameras where corresponding points in both views theoretically lie on the corresponding image parts. By this finding the additional image processing steps may strongly be facilitated and image processing techniques known per se may be used.
[0038] Therefore, in accordance herewith, the data obtained by the image receiver provided for each channel are corrected in view of the distortion errors in the x- and y-direction and in view of the disparity errors in the z-direction. This correction depends of the respective adjustments of the microscope, i.e. zoom and focus.
[0039] For the error correction a calibration is at first performed wherein, as was mentioned above, the operating microscope is described as a two-pin diaphragm camera on the image side. The calibration is carried out for all zoom and focus stages. The obtained calibration data are stored so as to allow an online or offline error correction at a later time. Of course, it is possible to store microscope-specific error correction data in a look-up table, so that the actual correction process can be facilitated under a calculation-technical aspect and thereby shortened.
[0040] All physical quantities required-for calculating the nominal pin diaphragm camera parameters for a CMO-microscope are easily accessible and can typically be inferred from the manufacturer's data sheet. Initial values for an iterative calibration may be measured on the microscope in an easy manner. The required data concerning the image receivers, e.g. CCD sensors, are likewise available as manufacturer's data. The knowledge of internal lens data is not necessary. The CMO-microscope-adapted stereoscopic image processing is accomplished by a method in which the representation from both two-dimensional cameral planes is formulated into the three-dimensional space by polynominal approximations of a smallest possible degree. A required control point quantity acts as supporting point quantity for the polynomials and is chosen in the entire volume.
[0041] For the practical application of microscopes with a continuously variable zoom and/or focus, it is proposed to calibrate the individual system parameters in several zoom and focus settings and, when setting intermediate values, to interpolate the corresponding system parameters from the calibrated supporting points. The current settings of zoom and focus are to be made available to the analyzing unit during the calibration procedure, but also during the measuring procedure, advantageously by the microscope via a data line.
[0042] In connection with the novel navigational instrument, especially for use in a method using image information from the beam path of a neuronavigational operating microscope, markings, especially micromarkings, are provided in the proximity of the instrument tip, namely basically when used lying in the field of view of the microscope. A certain minimum interspace to the instrument tip is due to the necessity that the markings are not to be contaminated by blood or other body liquids and, in case of convex markings, the use of the pointer instrument must not be obstructed.
[0043] The markings may, for example, be formed as at least three coplanar colored balls lying in one plane, which extends parallel to the longitudinal axis of the instrument, but does not include the same. Other embodiments are constituted by colored or reflecting annular markings. If the microscope is to be operated over a particularly large zoom and focus range, it may happen that the markings no longer completely lie in the field of view of the microscope if the magnifications are particularly strong and the lengths of focus too short, or that the markings are too small if the magnifications are particularly weak and the lengths of focus are large. In this case it is useful to attach several sets of markings having different sizes, wherein the smallest set of markings points or is attached closest to the instrument tip.
[0044] The navigational instrument according to the invention is sterilizable and can well be recognized through the microscope. Its one end is formed as a marked tip and may be employed as pointer. In the case where the tip is not directly visible for operative reasons, it can be detected via the aforementioned markings and the other information relating to the shape of the instrument.
[0045] The increased position identification in the case of optical systems is achieved by that the image recording is directly effected by the microscope, whereby it is ensured that the navigational instrument is not covered by the fingers or another operating set. The risk of covering by operating staff, as takes place with conventional optical navigational systems, is here precluded from the very beginning. Due to the ability to measure relative distances of points in the coordinate system of the microscope a further possibility consists in differential navigation, i.e. distances from points to a reference point can be measured.
[0046] In contrast to navigational instruments on the market so far the markings according to the invention are positioned close to the tip. Since a navigation is effected through the microscope, moreover, far smaller markings may be used. This, again, makes it possible to fabricate the navigational instrument itself smaller and more inexpensively and, above all, to use the same more flexibly and more ergonomically.
[0047] An exemplary navigational instrument is formed as a bayonet-type round steel of substantially 4 mm, tapered over a range of substantially 30 mm at the tip. The bayonet-like shape or cranking is useful under the aspect that it can be excluded that the instrument is covered by fingers or the like for the area detected by the camera.
[0048] According to one embodiment, the aforementioned coplanar balls are used as markers, which have, for example, a diameter of about 1.5 mm. For rendering the segmentation of the balls against the background as simple as possible, the same are lacquered in different colors. In view of the specific properties of the situs, blue, green and violet and/or brilliant yellow are preferably used. The use of infrared-reflecting balls is likewise possible, as is light emitting diodes (LED).
[0049] Since, the work may be performed with the light source provided on the microscope's side, the embodiment with colored markings can do without special ball coatings which reflect infrared radiation, for example, according to a distinct directional characteristic.
[0050] A further development resides in that the marker configuration is not placed upon and attached to the navigational instrument, but merely consists of overprints. In case of the required detection of the rotation of the navigational instrument about its own axis an angle coding extending in an azimuthal direction is, for example, conceivable.
[0051] The detection of the balls in the camera views is preferably accomplished by applying colored image processing methods. In dependence on the intensiveness of a possibly existing color cast, the same is directly compensated with the image recording by a white balance. To this end, a scaling of the intensities of the red and blue channel of each image receiver or each camera, respectively, takes place.
[0052] The feature extraction or pattern recognition, respectively, of the markings in the form of coplanar colored balls is effected by the fact that a ball-shaped object is imaged in a differentiated manner. If the central point of the ball does not lie on the vertical of the camera plane, the contour of the ball is projected as an ellipse. The form therefore allows conclusions to the position of the individual balls.
[0053] If the instrument tip is not directly visible in the camera images, the three-dimensional position of the pointer tip is determined from the three-dimensional positions of the ball centers.
[0054] Of course, the navigational instrument may also be formed of a common operation set in order to not unnecessarily interrupt the operation for navigational purposes.
[0055] For calculating the three-dimensional coordinates of the tip position from the three-dimensional ball centers, the underlying geometry is calibrated. To this end, a local instrument coordinate system originating from a ball in the middle is defined, from which two axes extend through the other two balls and the third axis is orthogonal to the so spanned plane. In this affine coordinate system the location of the pointer tip has three definite coordinates, so that it may be reconstructed indirectly via the reconstruction of the axes of the local instrument coordinate system. The affine coordinates are independent of the intrinsic or extrinsic parameters of the camera arrangement and can be calibrated for a number of predefined tip and ball coordinates.
[0056] Herein, the terms position and location are substantially used as synonyms. It lies within the range of knowledge of the person skilled in the art that, for detecting the location of a three-dimensional body in space, six coordinates, e.g. emission point/center of gravity or the like are to be indicated in x-, y- and z-orientation and with the three so-called Eulerian angles. One exception is only constituted by the instrument tip, which only requires three coordinates as spatial point for defining the location.
[0057] The disclosure will hereinafter be explained in more detail by means of embodiments.
First Embodiment
[0058] According to a first embodiment the field of operation lies inside the head of a patient, and an operating instrument is positioned with a corresponding marking in the field of view of the operating microscope.
[0059] The images of both observation channels are led via a beam splitter to two image receivers, e.g. CCD cameras. The camera images are then evaluated by a computer, and the position of the operating instrument is calculated in the coordinate system of the microscope from the stereoscopic image analysis and the device parameters, such as zoom and focus settings, which are additionally outputted by the microscope via a data connection.
[0060] At the same time, the location of the microscope and the patient is detected in the coordinate system of the stereo camera arm by a stereo camera pair with corresponding cameras, which is positioned in the proximity of the operating table, by means of stereoscopic image analysis and with the aid of the patient markings and the microscope markings. This allows the offsetting of the coordinate systems of the microscope and the patient and, for example, the position of the operating instrument may be indicated in coordinates of the patient.
[0061] Optionally, markings on the operating instrument may additionally be detected and evaluated by the camera pair, which results in a redundant measurement of the determination of the position of the operating instrument.
[0062] According to another embodiment, a generation of marking points, lines or a grating into the field of view of the microscope may be performed with visible light or with radiation in the near-infrared range. Said marking points, lines or gratings can then be recorded with a corresponding camera coupled to one of the observation channels. By evaluating the camera image, the location of the marking points can be detected in coordinates relative to the microscope.
[0063] Technically, the aforementioned teaching can be realized by that light is led via a diaphragm into the observation channel of the operating microscope and is imaged on one spot in the plane of focus of the microscope. This light spot is then detected by a camera, especially a CCD camera. With known coordinates in x- and y-direction of the diaphragm aperture in a Cartesian coordinate system perpendicular to the optical axis it then becomes possible, together with coordinates of the light spot on the camera chip, to work analogously to the common stereoscopic image analysis. Thus, the location of the spot, on which the light entering though the diaphragm is imaged, can be determined in coordinates of the microscope. As was mentioned above, light projection systems may be used instead of the illuminated diaphragm, each of which project a number of points, lines or gratings into the field of operation.
[0064] In case of a light grating, crossing points may be detected by the cameras. By means of the stereoscopic image analysis the coordinates of the crossing points of the light grating are then determinable on the surface of the field of operation in the coordinate system of the microscope. The information derived therefrom can then be represented as a three-dimensional perspective grating in the form of contour lines or the like on a display and may be used for the allocation of the location relative to preoperative recordings.
[0065] As part of quality assurance video recordings and photographs are, in most cases, made in today's operating theatres. Said video recordings and photographs do neither contain any quantitative three-dimensional information, nor can those generally be extracted from said video recordings and photographs.
[0066] If the recording of topographies of the field of operation during the operation is successful with an acceptable amount of work involved, the lack of the quantitative 3D-information of today's documentation would be inapplicable. Such topographies can be stored without problems and, within the framework of quality-assuring measures, for example, the actual resection profile can be compared with the findings from preoperative diagnostic data, such as the magnetic resonance tomography and the computerized tomography. Corresponding topographies may also be visualized to the doctor, for example, as relief diagrams, already during the operation. Thus, it becomes possible—in addition to postoperative quality assurance—to offer decision aids for optimizing the resection boundaries to the surgeon already during the operation.
[0067] In principle, a topography of the object field of the microscope can already be obtained with the above-described microscope comprising stereo cameras by means of common stereoscopic image analysis methods. Especially the correspondence analysis is, however, very time-consuming and susceptible to errors for natural, possibly weakly structured fields.
[0068] An improvement can be achieved by the following description of the methods and devices, inter alia, for the projection of light markings.
[0069] By means of light markings the corresponding points required for the stereoscopic image analysis can be determined fast, precisely and with an extremely low error rate.
[0070] One possible first embodiment makes use of stereo cameras permanently connected to the microscope and a projection system which need not necessarily be permanently connected to the microscope.
[0071] A second embodiment is based on the light projection device at the location of one of both stereo cameras, with the use of the optical channels/paths which were used in the first mentioned embodiment by exactly this camera. In this case the methods of stereoscopic image analysis can already be applied with one camera only, which is known by the term inverse camera.
[0072] According to another embodiment the topography is obtained directly from the data of a PMD array (PMD: Photonic Mixer Device) and an associated personal computer.
[0073] According to the first embodiment a generation of marking points, lines or gratings into the field of view of the microscope may be performed with visible light or with radiation in the near-infrared range.
[0074] The tissue in the field of view of the operating microscope can then be recorded together with the marking points, lines or gratings projected onto said tissue by two cameras which are, for example, coupled to the observation channels of the microscope. By evaluating the camera images with the stereoscopic image analysis the location of the marking points can be detected in coordinates relative to the microscope. The principal error source of the stereoscopic image analysis—the correspondence analysis—is thereby drastically facilitated and error-proof, since only the marked points of both camera images are included in the evaluation, in connection with which the uncertainty of the correspondence allocation is essentially smaller than with unmarked points.
[0075] For obtaining a topography of the marked points in coordinates of the patent—instead of in coordinates of the microscope—the relative location and orientation of the patient and the microscope must be detected, which may be accomplished in the explained manner.
Second Embodiment
[0076] The procedure according to the second embodiment is largely analogous to the first embodiment. Instead of the two cameras coupled to the observation channel of the microscope, however, one of the cameras is replaced by a diaphragm. The same lens system, which had previously imaged the object field onto said camera, is now used to image the diaphragm onto the object field. If a diaphragm structured with points, lines or gratings is used, and light is led through said diaphragm structures and the associated optical channel onto the object field, and if the correspondingly illuminated area is recorded with the remaining camera, the principle of the inverse camera is applicable, and the methods of stereoscopic image analysis are usable despite the use of one camera only. With respect to the error security here, too, the advantages of the first embodiments apply. If invisible light is used, visible light may additionally be admixed so as to make the supporting points of the topography visible already in the image of the ocular of the microscope.
Third Embodiment
[0077] In a third embodiment a PMD sensor array is used instead of the conventional cameras. For being able to use the same, modulated light must be used for illumination in addition to the visible light of the microscope. The PMD sensor is protected against a too intensive illumination by the white non-modulated light by suited optical filters. The topography of the field imaged on the PMD sensor array may be obtained with this new technology directly from the PMD chip with an associated computer having a suited interface.
[0078] The topographical data obtained in the above embodiments can then, for example, as three-dimensional perspective grating or in the form of contour lines or the like, be represented on a display. Moreover, said topographical data can be represented location-correlated with data from preoperative diagnostic data (nuclear resonance scanning data, computerized tomography data etc.).
Fourth Embodiment
[0079] In a fourth embodiment, which is an enhancement to the third embodiment, the PMD sensor array is provided as a component of the surgical microscope.
[0080] FIG. 1 illustrates a surgical suite, including a patient, a surgeon, an assistant, an operating microscope 100 and a computer system 200 . A portion of the operating microscope 100 is shown schematically in FIG. 2 . The operating microscope 100 in this embodiment includes an observation beam path portion 102 , preferably for stereoscopic inspection, and a tracking camera 104 positioned proximate the observation beam path portion 102 , the tracking camera 104 detecting a topography of a situs.
[0081] In preferred aspects, the tracking camera 104 is a PMD sensor array and is arranged such that a sensor axis of the PMD sensor array is parallel or substantially parallel/coaxial to an optical axis of the observation beam path portion 102 , where the optical axis is of the common main objective of the operating microscope 100 . In additional preferred aspects, a front objective of the observation beam path portion 102 and the tracking camera 104 are arranged at a common distance from the situs to have a common angle of receiving an image and detecting a topography, respectively, of the situs. The tracking camera 104 detects a topography and space positions of markings in a visual field thereof and, since it is a part of the operating microscope 100 , the detection is relative to the position of the observation beam path portion 102 .
[0082] As shown in FIG. 2 , the operating microscope 100 is positioned above a schematic diagram of a skull 106 . The skull 106 includes markings 108 . As discussed above, the markings 108 can include infrared reflectors, similar to an arrangement of reflective balls, or LEDs. Markings can also be provided on surgical instruments (not shown) which identify the surgical instruments. Specifically, markings patterns can be predefined and electronically stored in a storage unit to identify detected surgical instruments. Further, the surgical instruments can be correlated, in the storage unit, with predefined geometrical shapes for tracking and displaying with preoperative measurements of the situs or a currently obtained topography of the situs.
[0083] The field of view of the tracking camera 104 partly overlaps the object plane of the operating microscope 100 . The markings 108 are generally outside the field of view of the operating microscope 100 . Nonetheless, the markings 108 still need to be detected. By using the tracking camera, though, it is not necessary to use a stereo camera pair, as previously discussed.
[0084] As a result, by combining an image from the observation beam path portion 102 , which is preferably a stereoscopic image, with a topography image from the tracking camera 104 , a three-dimensional image can be generated. For example, a three-dimensional image (by use of the computer system 200 ) can be generated from the skull 106 and the markings 108 by the operating microscope 100 , as is shown by example in the image shown in FIG. 3 . As noted above, but not shown, the image may include a surgical instrument.
[0085] As a result, this fourth embodiment is operational with only one tracking camera (i.e., only one single measurement camera other than the functional components and optics of the operating microscope 100 ), and the following advantages are obtained:
[0086] Since the tracking camera receives the same alignment as the observation beam path/common main objective of the operating microscope, any problems caused by an obstructed view are largely removed. This leads to an improvement of the presence time and ergonomics of the navigation system, and thus, to a shorter operation time and minimization of complications.
[0087] The measurement volume of the tracking camera is reduced considerably (comparatively), which leads at the same time to a greater accuracy of the measuring system. Also, the navigation aids can be miniaturized correspondingly, so that the workspace in the operation room is not limited.
[0088] The required processing on the computer system 200 and/or a visual display (i.e. video processing) can be integrated into an existing video documentation system of the microscope. Therefore, double work steps (entering patient information, documentation, etc.) during/pre operation can be avoided. Space can also be reduced.
[0089] The combination of two cost-intensive apparatuses results in a considerable cost optimization.
[0090] An example of the aforementioned computer system 200 is shown in FIG. 4 , and includes various computer components, including a central processing unit, memory devices, a controller connected to a display, a network interface connected to a network, and an input/output interface connected to or connecting input peripherals and the aforementioned operating microscope and tracking camera.
[0091] As discussed above, with the use of a PMD sensor array as the tracking camera 104 , it is possible to highly integrate the PMD sensor array with the operating microscope 100 , including the processing aspects of the computer system 200 . Accordingly, it is not necessary that the computer system 200 , as shown in FIG. 1 , be a separate machine, but that it is possible for the functional components of the computer system 200 to be incorporated into the operating microscope 100 or as part of an existing video processing/recording component of the operating microscope 100 .
[0092] In a preferred aspect, operation of the fourth embodiment is consistent with the algorithm 300 shown in FIG. 5 . As such, the situs is illuminated with unmodulated light and modulated light at S 302 . An image of the situs is captured at S 304 by the optics of the microscope (from the non-modulated light), and at S 306 , non-modulated light directed to the PMD is filtered from the PMD to protect the PMD from intensive illumination by the non-modulated light. At S 308 , the topography of the situs is detected by the PMD of the microscope (from the modulated light illuminating the situs). Further, the markings on the situs are detected by PMD at S 310 , and finally, a three-dimensional image of the situs is generated from the image captured from the optoelectronic image receiver and the topography of the situs detected by the PMD.
[0093] As noted above, the generating can be performed by computer equipment similar to the computer system shown in FIG. 4 . However, as presented above, since the computational requirements in the fourth embodiment are reduced, the functional components of the computer equipment can be a component of the operating microscope. | An operating microscope including an optical unit for forming an image of an object plane in oculars of the microscope, an optoelectronic image receiver coupled to the microscope and optics to form images, of objects placed in a region between a front objective of the microscope and an object plane of the microscope, on the optoelectronic image receiver. The microscope has a magnification factor of the optics to form images, and a system to detect optical markings forming a markings pattern placed on a surgical instrument or an object placed in the region between the front objective of the microscope and the object plane of the microscope. The system calculates a geometrical position and orientation of the markings pattern in relation to the optoelectronic image receiver, relative to the microscope. | 0 |
RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 61/774,705, filed Mar. 8, 2013, which is incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to microwavable food packages and particularly, to peelable moisture and/or grease absorbent microwavable food packages.
BACKGROUND OF THE INVENTION
[0003] Foods such as bacon or sausage packaged in hermetically sealed containers that contain a large amount of water and solid grease can cause problems when cooked in a microwave oven. Water in such foods is vaporized by heating the food and condenses on contact with the packaging materials. Solid grease becomes liquefied upon heating. Water and melted grease may collect at the bottom of the package causing the food item to become soggy and appear unsightly. Controlling the undesired liquids that form within a food package during storage, display and/or heating of foods can play an important role by improving safety and shelf life of foods as well as enhancing aesthetics and controlling sogginess/over-dryness during heating. As convenience foods become more prevalent, microwaveable food packaging that enhances the flavor, texture and/or appearance of the food being heated is highly desirable. Also, maintaining freshness of packaged food is increasingly important since packaging, distribution and point of sale locations are increasingly more distant.
[0004] Absorbent food pads and films are described, for example, in US Patent Application Publication Nos. 2008/0199577 and US2012/0114808, and U.S. Pat. No. 7,771,812 and U.S. Pat. No. 7,141,770. Food pads are often utilized to absorb excess liquids from meat or seafood that is packaged for display and fresh sale and are also used to absorb moisture and fats from frozen or fresh foods that are packaged for in-package preparation such as bacon or breakfast sandwiches.
[0005] Traditional food pads and absorbent food packages can be costly to produce and even inconvenient for assembly of the packaging system. In addition, rising food costs and commoditization of the food packaging industry has applied pressure to food and food package manufacturers to achieve the desired packaging properties with increased flexibility in manufacturing and at a reduced cost.
[0006] Another area of concern is with respect to ease of use during cooking of the food items and subsequent dispensing of the food items once cooked. Minimal manipulations by the consumer are highly desired. Easy access to the food items is highly preferred. There is a need in the art for improved microwave food heating packages that address at least some of the above concerns, and other concerns related to manufacture and use of the packages. Therefore, there is still a need for microwavable packaging materials that can provide good liquid absorption yet are easily openable and inexpensive.
SUMMARY OF THE INVENTION
[0007] The present invention provides a peelable microwavable food package capable of absorbing undesired liquids released from packaged food products during storage, display, or heating, including microwave cooking. The present invention provides a peelably sealed microwavable food package in any packaging format including pouches, flow-wrap, horizontal form fill seal (HFFS), vertical form fill seal (VFFS), gas-flushed, vacuum-packaged, sealed rigid plastic containers and the like.
[0008] The present invention provides a peelable microwavable food package having a first film having an outer sealant layer which is capable of forming a peelable seal to a non-woven fabric of cellulosic and synthetic fibers such that the peelable seal has a peel strength of at least 100 gram/inch at a temperature of 149° C. (300° F.), preferably at least 200 gram/inch at a temperature of 149° C. (300° F.), and more preferably, at least 300 gram/inch at a temperature of 149° C. (300° F.).
[0009] The present invention relates to a peelable microwavable food package having a first film having an outer sealant layer comprising a heat-sealable material capable of sealing to an outer layer of a second film comprising a non-woven fabric of cellulosic and synthetic fibers having a basis weight greater than about 24 grams per square meters, and more preferably, at least about 54 grams per square meters, and a thickness of at least 200 microns, preferably, at least 300 microns, and most preferably, at least 330 microns. The first film is a thermoformable film which is configured to define a food item receiving space.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is one embodiment of a food package of the present invention. multilayer absorbent label of the present invention.
[0011] FIG. 2 is a cross sectional view of one embodiment of a multilayer first film of the present invention.
[0012] FIG. 3 is a cross sectional view of one embodiment of a multilayer second film of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0013] Referring to FIG. 1 , a peelable microwavable food package 100 is shown according to an exemplary embodiment. Food package 100 is suitable to contain any of a variety of food products, such as including a bread product and a meat product including, but not limited to breakfast items such as breakfast sandwiches, lunch items such as lunch sandwiches, etc., dinner items, snack items, and the like. As shown in FIG. 1 , package 100 includes a food item 110 provided within the interior of container 200 . Food item 110 may naturally contain moisture and/or solid grease that is released when food item 110 is heated as a result of undergoing a cooking process (e.g., microwave cooking, etc.).
[0014] According to one embodiment, peelable microwavable food package 100 includes a first film 101 and a second film 102 . First film 101 is configured to define a food item receiving space 200 (e.g., a pocket, receptacle, formed portion, etc.) It will be appreciated that food item receiving space 200 may be configured to provide a space or gap (e.g., “a steam dome”) about food item 110 when food item 110 is heated in a microwave oven. Second film 102 is affixed to first film 101 by the formation of a peelable heat-seal 104 which circumscribes food item receiving space 200 which includes joining first film 101 to second film 102 . As shown, second film 102 is configured to define a food item platform upon which food item 110 may be positioned and whereby moisture and/or grease released from food item 110 can be absorbed therein. It will be appreciated by those skilled in the art that peelable heat-seal 104 may also provide a barrier to microorganisms and/or prevents ingress of oxygen, moisture, humidity, and any outside contaminant into the sealed package which can degrade the food item container inside package 100 .
[0015] In one embodiment, the food package facilitates the cooking of food that exudes oil, grease, fat and the like during the cooking process such as bacon, sausage, or fried chicken. In another embodiment, the food package facilitates the cooking of food that releases moisture, including steam, during the cooking process such as a frozen breakfast sandwich, lunch or snack sandwich, or other food item. The food package of the present invention can further comprise features useful for microwaveable packaging systems such as venting systems, and reclosing means including re-seal strips or zippers.
[0016] Referring to FIG. 2 , one embodiment of a first film 101 is shown having seven layers. First film 101 may include any number of layers depending upon the desired functional requirements that are needed. According to the present invention, first film 101 with an outer sealant layer 11 capable of sealing to a non-woven fabric of cellulosic and synthetic fibers having a basis weight greater than about 24 grams per square meters, and more preferably, at least about 54 grams per square meters, and a thickness of at least 200 microns, preferably, at least 300 microns, and most preferably, at least 330 microns. In a preferred embodiment, the outer sealant layer 11 of the first film 101 comprises ethylene/vinyl acrylate copolymer (EVA) having at least 12% (wt.) vinyl acetate content. In another preferred embodiment, the outer sealant layer 11 of the first film 101 comprises ethylene/vinyl acrylate copolymer (EVA) having at least 18% (wt.) vinyl acetate content.
[0017] Preferably, the outer sealant layer 11 of the first film 101 comprises a heat-sealable material having a melt index of at least 5 V 0 min., at least 10 g/10 min., at least 15 g/10 min., or at least 20 g/10 min. as measured in accordance with ASTM D-1238 test method at 190° C./2.16 kg. In another embodiment, the outer sealant layer 11 of the first film 101 comprises a heat-sealable material having a melt index of at least 30 g/10 min. as measured in accordance with ASTM D-1238 test method at 190° C./2.16 kg.
[0018] In accordance with an important aspect of the present invention, the outer sealant layer 11 of the first film 101 comprises a heat-sealable material selected from the group consisting of acrylate-based resin, acrylic acid-based resin, ionomer, ethylene/α-olefin copolymer (EAO), polyethylene more preferably, a low-density polyethylene, preferably, an ultra-low density polyethylene copolymer, and blends thereof. Preferably, the acrylic acid-based resin may comprise a material selected from the group consisting of ethylene/acrylic acid copolymer (EAA), ethylene/methacrylic acid copolymer (EMAA), and blends thereof. Preferably, the acrylate-based resin may comprise a material selected from the group consisting of methyl/methacrylate copolymer (M/MA), ethylene/vinyl acrylate copolymer (EVA), ethylene/methacrylate copolymer (EMA), ethylene/n-butyl acrylate copolymer (EnBA), and blends thereof. Specific examples of suitable acrylate-based resins include ESCORENE™ LD 734 having a melt index of 30 g/10 min., vinyl acetate content of 19.3 (wt. %), a density of 0.940 g/cm 3 , and a melting point of 85° C., which is available from ExxonMobil Chemical Company of Houston, Tex., U.S.A.; ULTRATHENE® UE 662-249 having a melt index of 32 g/10 min., a vinyl acetate content of 18 (wt. %), a Vicat softening point of 54° C., which is available from Equistar Chemicals, LP of Houston, Tex. U.S.A.; and ELVAX® 3176 CW-3 having a melt index of 30 g/10 min., a vinyl acetate content of 18 (wt. %), a density of 0.940 g/cm 3 , and a melting point of 84° C., and a Vicat softening point of 54° C., which is available from E.I. de Pont de Nemours and Company, Wilmington, Del., U.S.A.
[0019] As depicted in FIG. 2 , first film 101 also includes second layer 12 , third layer 13 , fourth layer 14 , fifth layer 15 , sixth layer 16 , and seventh layer 17 .
[0020] Referring to FIG. 3 , the second film 102 includes an absorbent layer 21 , a polymeric bonding layer 22 , and a polymeric support film layer 23 .
[0021] In accordance with another important aspect of the present invention, the outer layer of the second film 102 is an absorbent layer. This absorbent layer 21 is a non-woven fabric of cellulosic and synthetic fibers having a basis weight greater than about 24 grams per square meters, and more preferably, at least about 54 grams per square meters, and a thickness of at least 200 microns, preferably, at least 300 microns, and most preferably, at least 330 microns. The absorbent layer 21 is capable of absorbing water, fats, or other undesired liquids that are released by packaged food products during storage, display or heating. Toward this end, it is preferred that the absorbent layer of the second film have a water absorption capacity of at least 100%, at least 200%, at least 300%, more preferably, at least 400%, and most preferably, at least 520%.
[0022] The absorbent layer 21 can comprise one or more absorbing elements such as cellulose, synthetic fibers, paper-based materials, non-woven fabrics and polymeric materials, or combinations thereof. In one embodiment, the absorbent layer comprises a non-woven fabric of cellulosic and synthetic fibers. In one embodiment, the absorbent layer may include two or more layers, such as, for example, an inner-facing paper-based layer and a polypropylene fiber layer.
[0023] In a preferred embodiment, the absorbent layer 21 of the second film 102 comprises a non-woven fabric of cellulosic and synthetic fibers having a wet tensile strength in the transverse direction (cross direction) of greater than about 400 grams per 25 millimeters, more preferably, greater than about 1000 grams per 25 millimeters, and most preferably, at least about 1450 grams per 25 millimeters. In another preferred embodiment, the absorbent layer 21 comprises a non-woven fabric of cellulosic and synthetic fibers having a wet tensile strength in the machine direction of greater about 1000 grams per 25 millimeters, more preferably, greater than about 2000 grams per 25 millimeters, and most preferably, at least about 2600 grams per 25 millimeters.
[0024] The absorbent layer 21 of the second film 102 faces food item and absorbs moisture and/or grease released from food item during heating (e.g., exposure to microwave energy) of food item. As such, the absorbent acts to control the moisture content of food item and prevent food item from becoming too soggy (due to excessive moisture) or too dry (due to lack of moisture).
[0025] In one embodiment, second film 102 further includes a bonding layer 22 and a support layer 23 where the bonding layer 22 joins the absorbent layer 21 to the support layer. In a preferred embodiment, the bonding layer 22 comprises a non-oriented polyolefin, more preferably non-oriented polyethylene and most preferable non-oriented low density polyethylene. In a preferred embodiment, the non-oriented low density polyethylene has a melt index of at least about 3.0 grams per 10 minutes, and more preferably, at least about 3.7 grams per 10 minutes. In a preferred embodiment, the non-oriented low density polyethylene has a density of less than about 1.0 grams per cubic centimeter, and more preferably, about 0.92 grams per cubic centimeter. Commercially available of such low density include LyondellBasell® PETROTHENE NA 216-000 produced by Equistar Chemical Company, Houston, Tex.
[0026] In one embodiment, support layer 23 of the second film 102 comprises an oriented film. In a preferred embodiment, support film layer 23 has a thickness of between about 44 gauge and about 48 gauge (about 11 micron and about 12 micron). In a preferred embodiment, support film layer 23 is an oriented film of polyethylene terephthalate. In another preferred embodiment, polymeric support film layer 23 is an oriented film of polypropylene. In another preferred embodiment, polymeric support film layer 23 is an oriented film of polyamide (nylon). In still another preferred embodiment, polymeric support film layer 23 is an oriented film of cast polyamide (nylon). Commercially available oriented polyethylene terephthalate include a 48 gauge Skyrol® SP65 produced by SKC Co., Ltd., Seoul, South Korea. In one preferred embodiment, polymeric support film layer is coated with an aqueous primer to assist with bonding to bonding polymeric layer. Commercially available primers include Aquaforte® 108-W produced by Aqua Based Technologies, Northvale, N.J.
[0027] In a preferred embodiment, second film 102 has the following structure: non-woven absorbent layer/bonding layer/support film layer as shown in FIG. 3 .
[0028] The following example illustrates certain particular embodiment of a first film structure suitable for use in the present invention and a comparative example. In all the following examples, resin composition percentages are based on the total weight of each film layer. In all the following examples, all film structures were produced using a single-bubble coextrusion apparatus and method which are well known to those skilled in the art. The single-bubble blown coextrusion film apparatus includes a multi-manifold circular die head for bubble blown film through which the film composition is forced and formed into a cylindrical bubble. The bubble is immediately quenched e.g., via cooled water bath, solid surface and/or air, and then ultimately collapsed and formed into a film.
EXAMPLES OF FIRST FILM
Example 1
[0029] Example 1 is one embodiment of a seven-layer blown coextruded film structure of the present invention having the following structure and layer composition as depicted in FIG.
Layer 1 (1 st out-sealant): a blend of about 55% ethylene vinyl acetate (EVA) having 18% (wt.) vinyl acetate content (ELVAX® 3176 CW-3 from E.I. de Pont de Nemours and Company, Wilmington, Del., U.S.A.), about 30% of polyethylene methylacrylate acid copolymer (EMAA) masterbatch containing antifog additive, about 10% of ethylene vinyl acetate masterbatch containing anti-block additive and about 5% ethylene vinyl acetate masterbatch containing slip additive Layer 2: (tie) a blend of about 90% ultra-low density polyethylene (ULDPE) (ATTANE® 4201G from The Dow Chemical Company, Midland, Mich., U.S.A.) and about 10% of maleic anhydride modified polyethylene (PLEXAR® PX 3308 from Equistar Chemicals, LP of Houston, Tex., U.S.A.) Layer 3: (barrier) a blend of about 85% nylon 6 (ULTRAMID® B36 from BASF Corporation, Mount Olive, N.J., U.S.A.) and about 15% nylon 6I/6T (DuPont SELAR® PA-3426R from E.I. du Pont de Nemours and Company, Wilmington, Del., U.S.A.) Layer 4: (barrier) 100% of ethylene vinyl alcohol copolymer (EVOH) (SOARNOL® DT2904R from Soarus L.L.C., Arlington Heights, Ill., U.S.A.) Layer 5: (barrier) a blend of about 85% nylon 6 (ULTRAMID® B36 from BASF Corporation, Mount Olive, N.J., U.S.A.) and about 15% nylon 6I/6T (DuPont SELAR® PA-3426R from E.I. du Pont de Nemours and Company, Wilmington, Del., U.S.A.) Layer 6: (tie) a blend of about 90% ultra-low density polyethylene (ULDPE) (ATTANE® 4201G from The Dow Chemical Company, Midland, Mich., U.S.A.) and about 10% of maleic anhydride modified polyethylene (PLEXAR® PX 3308 from Equistar Chemicals, LP of Houston, Tex., U.S.A.) Layer 7 (2 nd outer): a blend of about 77% nylon 6 (ULTRAMID® B36 from BASF Corporation, Mount Olive, N.J., U.S.A.), about 15% of nylon 6I/6T6 (ULTRAMID® B36 from BASF Corporation, Mount Olive, N.J., U.S.A.) and about 8% nylon masterbatch containing anti-block and slip additives.
Comparative Example 1
[0037] Comparative Example 1 (not of the invention) is a seven-layer blown coextruded film structure having the following structure and layer composition:
Layer 1 (1 st outer-sealant): a blend of about 88% ethylene vinyl acetate (EVA) having a 5% (wt.) vinyl acetate content (PETROTHENE® NA442-051 from Equistar Chemicals, LP of Houston, Tex., U.S.A.), about 10% polyethylene masterbatch containing antifog additive and about 2% polyethylene masterbatch containing slip additive Layer 2: a blend of about 88% ethylene vinyl acetate (EVA) having a 5% (wt.) vinyl acetate content (PETROTHENE® NA442-051 from Equistar Chemicals, LP of Houston, Tex., USA), about 10% polyethylene masterbatch containing antifog additive and about 2% polyethylene masterbatch containing slip additive Layer 3: (tie) 100% maleic anhydride modified polyethylene (ADMER® AT2118A from Mitsui Petrochemical Corporation of Tokyo, Japan) Layer 4: (barrier) 100% of ethylene vinyl alcohol copolymer (EVOH) (SOARNOL® ET3803 from Soarus L.L.C. Arlington Heights, Ill., U.S.A.) Layer 5: (tie) 100% maleic anhydride modified polyethylene (ADMER® AT2118A from Mitsui Petrochemical Corporation of Tokyo, Japan) Layer 6: a blend of about 64.1% of ultra-low density polyethylene (ULDPE) (ATTANE® NG 4701G from The Dow Chemical Company, Midland, Mich., U.S.A.), about 35% of linear low density polyethylene (LLDPE) (Exxon 1001.32 from ExxonMobil Chemical Company of Houston, Tex., U.S.A.) and about 0.9% polyethylene masterbatch containing processing additives Layer 7 (2 nd outer): a blend of about 64.1% of ultra-low density polyethylene (ULDPE) (ATTANE® NG 4701G from The Dow Chemical Company, Midland, Mich., U.S.A.), about 35% of linear low density polyethylene (LLDPE) (Exxon 1001.32 from ExxonMobil Chemical Company of Houston, Tex., U.S.A.) and about 0.9% polyethylene masterbatch containing processing additives
[0045] The total thickness of the films Example 1 and Comparative Example 1 were generally from about 12.7 μm (0.5 mil) to about 254 μm (10 mil), typically from about 50.8 μm (2 mil) to about 178 μm (7 mil), most typically from about 63.5 μm (2.5 mil) to about 127 μm (5 mil).
[0046] In accordance with the present invention, Example 1 had an oxygen transmission rate of less than about 1.0 cm 3 /100 in 2 /24 h at 73° F., 0% RH and 1 atm (or about 15.5 cm 3 /m 2 /24 h at 23° C., 0% RH and 1 atm), and preferably, about 0.5 cm 3 /100 in 2 /24 h at 73° F., 0% RH and 1 atm (or about 7.75 cm 3 /m 2 /24 h at 23° C., 0% RH and 1 atm). In accordance with the present invention, Example 1 had a water vapor transmission rate less than about 1.0 g/100 in 2 /24 h at 73° F., 90% RH and 1 atm (or about 15.5 g/m 2 /24 h at 23° C. 90% RH and 1 atm) and preferably, about 0.5 g/100 in 2 /24 h at 73° F. 90% RH and 1 atm for about 7.75 g/m 2 /24 h at 23° C., 90% RH and 1 atm).
[0047] In accordance with another important aspect of the present invention, the outer sealant layer of the first is capable of peelably sealing to the outer absorbent layer of the second film to form a heat seal having a peel strength of at least 100 gram/inch at a temperature of 132° C. (270° F.), preferably, at least 100 gram/inch at a temperature of 149° C. (300° F.), more preferably at least 200 gram/inch at a temperature of 149° C. (300° F.), and most preferably, at least 300 gram/inch at a temperature of 149° C. (300° F.).
[0048] Specimens of Example 1 and Comparative Example 1 were heat sealed to the surface of a non-woven absorbent first layer of a second film (as depicted in FIG. 3 ). The seal strengths of the outer sealant layer of the first film to the non-woven absorbent first layer of the second film were measure between a temperature of 132° C. and 210° C. (207° F. and 410° F.). The results are illustrated in TABLE 1 below.
[0000]
TABLE 1
SEAL STRENGTHS
(grams/inch)
Example 1
Comparative Example 1
132° C.
105
0
138° C.
342
0
143° C.
229
0
149° C.
367
0
154° C.
857
75
160° C.
834
172
166° C.
920
357
171° C.
1054
394
177° C.
1127
394
188° C.
Not measured
687
199° C.
Not measured
1165
210° C.
Not measured
1267
[0049] Specimens of Example 1 and Comparative Example 1 were heat sealed to the surface of a non-woven absorbent first layer of a second film. A cross-sectional sample of each specimen was prepared and examined under microscopic magnification. It was observed that for Example 1, the outer sealant layer of the first film penetrated through the non-woven absorbent first layer of the second film and was in contact with the adjacent bonding layer of the second film. Whereas for Comparative Example 1, the outer sealant layer of the first film did not penetrated through the non-woven absorbent first layer of the second film and was not in contact with the bonding layer of the second film. Without being bond to any particular theory, it is believed that the use of an outer sealant layer comprising ethylene/vinyl acrylate copolymer (EVA) having at least 12% (wt.) vinyl acetate content and/or a melt index of at least 20 g/10 min. enhances the flow characteristics of the sealant through the non-woven (first) layer to achieve fusion bonding between the sealant layer of the first film and the bonding (second) layer of the second film. It is believed that such fusion bonding of the sealant layer of the first film to the bonding (second) layer of the second film produces higher seal strengths within a sealing temperature range of between 132° C. and 177° C. as was observed in Example 1 compared to Comparative Example 1 above.
[0050] The above disclosure is for the purpose of illustrating the present invention and should not be interpreted as limiting the present invention to the particular embodiment s described but rather the scope of the present invention should only be limited by the claims which follow and should include those modifications of what is described which would be readily apparent to one skilled in the art. | The present invention provides a peelable microwavable food package capable of absorbing undesired liquids released from packaged food products during storage, display, or heating, including microwave cooking. The present invention provides a peelably sealed microwavable food package in any packaging format including pouches, flow-wrap, horizontal form fill seal (HFFS), vertical form fill seal (VFFS), gas-flushed, vacuum-packaged, sealed rigid plastic containers and the like. | 1 |
FIELD OF THE INVENTION
This invention relates to spring-loaded boat tethering devices. More particularly, it relates to an improved spring-loaded boat tethering device which provides reliable and repeatable extension and retraction of mooring lines, secure attachment to a vessel, and positive locking of the mooring line so as to provide fixed positioning of the vessel relative to another object such as a dock, a pier, or another vessel.
BACKGROUND OF THE INVENTION
The safe mooring of vessels to docks, piers or other vessels requires that the vessel or dock be equipped with sufficient lengths of tethering material, e.g. mooring rope or cable to enable the vessel to be secured and maintained out of harm's way under a variety of mooring conditions. The tethering material must be easily adjustable in length so as to satisfy a wide variety of mooring conditions. Furthermore, the tether must be easily stowed in a safe and orderly fashion so that it does not become a hazard to passengers or other equipment. A mechanism which can be affixed to a vessel or the adjacent mooring structure, and is capable of reliably and repeatably extending and retracting tethering lines while simultaneously providing positive locking of the tether would be highly desirable.
Various prior art devices have endeavored to provide such mechanisms. For example:
U.S. Pat. No. 4,846,090 discloses an automated boat mooring device. The device may be attached to the gunwale of a boat to dispense and retract mooring line. This device includes a length of rope coiled around a winding spool. The device includes a spring which becomes loaded as line is extended off the spool. In this way, the device automatically will retract line that has been extended for use. A locking-pin-and-pawl assembly selectively stops retracting motion of the spring-loaded spool.
U.S. Pat. No. 4,697,537 discloses a retractable line storage device designed for integral mounting within a boat. The device includes a hollow housing and a spring-loaded storage reel. A mooring line attached to the reel includes a specially shaped handle at a free end of the line. The handle is shaped to fit flush within a deck-mounted top plate.
U.S. Pat. No. 3,300,187 discloses a semi-automatic warping and mooring arrangement. This device teaches a motor-driven rotating spool and pulley assembly that eases docking of large ships.
U.S. Pat. No. 4,200,052 discloses a system for controlling the position of a moored floating vessel. The device is directed at maintaining a boat in a desired position. This device is not aimed at retracting line onto a boat.
U.S. Pat. No. 4,706,594 discloses a boat mooring line guide and holder designed to catch a thrown end of a mooring line during boat docking. This device, which includes a pair of Y-shaped arms mounted on a dock, is designed to engage the ball-shaped end of a modified mooring line. This device does not address the automatic winding features provided by the instant invention.
U.S. Pat. No. 5,634,421 discloses a watercraft mooring apparatus formed from a tubular element having fender elements at either end. Although this device includes a mooring line, no automatic winding features are discussed.
U.S. Pat. No. 4,036,476 discloses an automatic take-up winch used for taking up slack in chains or other flexible securing members. This device does not teach the spring-loaded take-up spool included in the instant invention.
Many of the prior art devices suffer from inherent design deficiencies which quickly render them wholly or partly inoperative when subjected to the constant rigors of a corrosive marine environment. For example, the spring mechanism of the Palmquist device (the '090 patent) suffers due to the fact that it turns upon itself while line is paid out. This causes friction and binding which results in erratic operation and premature failure of the spring motor. The Smith device (the '537 patent) does not provide for positive locking of the tether. Smith requires that an appropriate length of tether be first made fast to the boat's cleat and then to the appurtenant docking structure. This causes difficulty in accurately positioning the vessel because any adjustments would require that the tether be unfastened from the cleat when it is under tension from the vessel. This is an unsafe and dangerous practice at best.
It is therefore an object of the present invention to provide an improved spring-loaded boat tethering device which is able to provide reliable and repeatable extension and retraction of tethering lines and secure attachment of said lines to a vessel and/or structures appurtenant thereto.
It is a further object of the invention to provide positive spool locking means by which the spool to which the tethering lines are attached may be fixed so as to prevent unwanted slippage.
It is an additional object of the present invention to provide an improved preloaded spring motor which acts to provide uniform and relatively constant tension to the tethering line during the full extent of its travel while avoiding the friction related spring failure known to occur in the prior art devices.
It is also an important object of the present invention to provide a device wherein the tethering line may be in the form of a rope or cable, e.g. a vinyl-coated steel cable, which can be used for anchoring situations in addition to mooring of said vessel.
It is yet another object of the present invention to provide a device wherein the components are formed from materials which are corrosion resistant and designed to withstand the rigors of a marine environment.
Still another object of the present invention is to provide a device which can be mounted in place of a standard boat cleat and wherein the attachment means are rendered tamper resistant upon assembly.
Other objects and advantages of the present invention will become apparent to those skilled in the art from the following detailed description when read in conjunction with the accompanying drawings.
SUMMARY OF THE INVENTION
The present invention relates to a boat tethering device formed from corrosion resistant materials throughout and containing an extensible tethering means which is adapted to extend or retract from a housing. The housing is formed from two attachable pieces, a lower half and an upper half. The lower half is formed with integral mounting apertures suitable for facilitating the attachment of the housing to a boat or a dock while the upper half is formed so as to sealably engage the lower half. The assembled housing will contain a spool assembly which is characterized by a hollow and generally-cylindrical portion having a first end and a second end and being rotatably mounted within the housing. The generally-cylindrical portion has an outer region which provides an external tether supporting surface and an inner region which is delineated by an inner conical zone formed with spaced ribs along the circumference thereof. The diameter of the inner conical zone decreases in an axial direction from said first end to said second end. The spool assembly is further characterized by first and second opposed guidewalls which extend perpendicularly to the axis of said assembly and are positioned at each of said first and second ends respectively. The first guidewall is further adapted to receive a spool locking means; and the second guidewall is adapted to engage the spring biasing means. Lastly, the guidewalls are further characterized by bearing surfaces extending axially therefrom and are adapted to facilitate ease of rotation of the assembly within said housing. The device contains a spool locking means which has a cylindrical member adapted to frictionally engage the inner conical zone of said spool assembly and having corresponding ribs spaced along the outer circumference of said member. Upon insertion within said zone, the corresponding ribs interlock with the ribs of said zone thereby preventing rotation. Spring biasing means are preferably formed from an extended eye spring assembly adapted to provide relatively constant tension upon said tethering means. In operation, the tethering means can be simply extended and retracted from the housing and reliably locked in any position.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a pictorial view of the boat tethering device in accordance with the present invention showing the device attached to a personal watercraft.
FIG. 2 is a perspective view of the device with a cut-away to better illustrate the cooperation of the internal portions and the outer casing.
FIG. 3 is cross-sectional view of the device taken along line 3--3 of FIG. 2.
FIG. 4 is a cross-sectional view of the device detailing the spring-biasing apparatus taken along line 4--4 of FIG. 3.
FIG. 5 is a cross-sectional view of the device detailing the cooperation of the spool assembly and locking device taken along line 5--5 of FIG. 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, FIG. 1 shows an enlarged boat tethering device 1 in accordance with the present invention mounted to a personal watercraft 2. The device, as seen in FIGS. 2 and 3, broadly includes a tethering means 3, a housing 4, a spool assembly 5, a spring biasing means 6 and a locking means 7. The extensible tethering means 3 can be a rope or cable, and in a particularly preferred embodiment can be a vinyl-coated steel cable. In operation, the tethering means, which is anchored to the spool through aperture 28 in Fig.3, travels through a slot (36 in FIG. 5) in the lower half of the housing, and in a particularly preferred embodiment, a thermoplastic rubber wiper (37 in FIG. 5) may be included to add tension and aid the winding pattern. The housing 4 has a lower half 8 and an upper half 9. The lower half is formed with integral mounting apertures, generally described by numeral 10 suitable for facilitating attachment to a boat or a dock, with, for example, mounting bolts 11, as depicted in FIG. 3. The upper half sealably engages the lower half and is adapted to contain a spool assembly 5. The spool assembly is characterized by a hollow and generally-cylindrical portion 13 having a first end 14 and a second end 15 and being rotatably mounted within the housing. The generally-cylindrical portion has an outer region which provides an external tether supporting surface 16 and an inner region which is delineated by an inner conical zone 17 formed with spaced ribs or splines 18 along the circumference thereof. The diameter of said zone decreases in an axial direction from the first end to the second end. The spool assembly is further characterized by first and second opposed guidewalls which extending perpendicularly to the axis of the spool assembly and are positioned at each of said first and second ends respectively. The first guidewall 19 is adapted to receive a spool locking means 7; and said second guidewall 20 is adapted to engage spring biasing means 6. The guidewalls are further characterized by bearing surfaces 21 and 22 extending axially therefrom and are adapted to facilitate ease of rotation of said assembly within said housing. In the particularly preferred embodiment, as shown, thrust bearings 26 and 27 are included, which aid in maintaining the positioning of the spool assembly during the operation thereof. The spool locking means has a cylindrical member 23 adapted to frictionally engage the inner conical zone of said spool assembly and additionally has corresponding ribs or splines 24 spaced along the outer circumference of said member. Upon depressing the actuator knob 12 which causes insertion of the spool locking means into the housing and into frictional engagement with the inner conical zone of the spool assembly, the corresponding ribs or splines of the locking means interlock with both the integral grooves (35 in FIG. 5) in the housing and with the ribs or splines of said zone thereby preventing rotation. The spring biasing means 6, as best seen in FIG. 4 comprises an extended eye spring assembly. This spring assembly is a major advance over conventional backwound springs because it actually increases available torque with fewer initial turns or prewinds. In the extended eye design, prewinds are formed by alternating layers of the eye and spring element. In a particularly preferred embodiment, a 28 turn spring is utilized with 4 turns thereof devoted to the prewind. This results in a more economical spring design and improved performance due to the torque increase in the initial few turns producing a flatter torque curve over the entire working range of the spring. Thus, a relatively constant tension is applied to the tethering means while it is being extended and retracted from said housing which results in reliable and efficient operation. To allow for drainage of water, which is carried within the device by the tethering means, weep holes 25 are provided for drainage. Furthermore, it is contemplated to provide grease fittings (not shown) in the ends of the housing so as to enable grease or some equivalent lubricant to be inserted between the bearing surfaces of the spool assembly and the housing.
Those skilled in the art will appreciate that numerous variations of the specific embodiments set forth above may be practiced without departing from the spirit of the invention, as claimed below. | This instant invention is a spring-loaded boat tethering device. More particularly, it discloses an improved spring-loaded boat tethering device which provides reliable and repeatable extension and retraction of mooring lines, secure attachment to a vessel, and positive locking of the mooring line so as to provide fixed positioning of the vessel relative to another object such as a dock, a pier, or another vessel. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to methods and devices for organizing and capturing the responsibilities of a waiter in a restaurant. More specifically, the present invention relates to methods and devices for recording food orders placed by a restaurant patron, organizing and processing a receipt and/or monies associated with a restaurant check, and organizing the responsibilities of a restaurant waiter.
BACKGROUND
[0002] The following description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[0003] The responsibilities associated with a restaurant waiter or server involves numerous responsibilities and duties. Examples of various functions include memorizing the “specials of the day” and associated prices, memorizing various spices and additives in preparing a dish, as well as providing for chef suggestions to accompany certain dishes, and wine and drink pairings. In addition, a waiter must keep organized meal orders placed by different tables within the restaurant, and attend to the needs of restaurant patrons. Furthermore, a waiter must keep account of all receipts and monies exchanged throughout the night, accounting for such things as tips, bar tabs and making change for restaurant patrons.
[0004] As is customary in restaurants, a waiter may be responsible for upwards of eight tables, which could amount to servicing forty or so restaurant patrons at any given time. Restaurants are a service-related industry, and the degree of care and precision a waiter displays while servicing the restaurant patrons is part of the measure of a restaurant's performance. In fact, a well-known restaurant rating guide, ZAGAT, identifies service as the second most important factor in determining a restaurant's rating, second only to food quality. An organized waiter often can provide a better service experience for a restaurant patron.
[0005] In juggling their various duties and responsibilities, many waiters are faced with the time-consuming task of searching for the needed article or information throughout the service of their tables. This could reflect poorly on the service being provided to the restaurant patron, and result in a lower tip and a lower approval rating for the restaurant.
[0006] The present invention addresses these limitations by providing for a novel method and device for capturing and organizing information common to restaurant waiters. The present invention further provides a novel method and device for increasing efficiency and limiting errors associated with restaurant waiter duties and responsibilities.
SUMMARY OF THE INVENTION
[0007] The present invention provides methods and devices for capturing and organizing information common to restaurant waiters in performing their waiting duties and responsibilities.
[0008] In one embodiment, the organizer comprises a folding case with a leaf having an end affixed within an elongated compartment. The leaf may include a plurality of pockets. For example, the leaf may include a first and a second pocket, each pocket having an opening and configured to hold a card. The openings of the first and second pockets being accessible through the elongated opening of the elongated compartment. The first pocket is located adjacent the top interior side and the second pocket is located adjacent the bottom interior side, such that the pockets do not interfere with closing the folding case.
[0009] In another embodiment, the organizer comprises a folding case having a rear exterior side including a backing and a flexible shell covering at least a substantial portion of the rear exterior side of the folding case, and a v-shaped opening integrally formed in the flexible shell. The v-shaped opening creates a rear pocket between the flexible shell and the backing, and the rear pocket is configured to accept a card.
[0010] In another embodiment, the organizer comprises a folding case and an insert capable of being attached to one end of the folding case. The insert remains between the top interior panel and the bottom interior panel of the folding case when the folding case is in the closed position; the insert including a plurality of pages for holding cards such as credit cards or driver's licenses. Each of the plurality of pages is joined at one end, and the means for fastening is located adjacent the end opposite the one end where the plurality of pages are joined. A strap or clip may be used to attach the insert to one end of the folding case.
[0011] Other features and advantages of the present invention will become more apparent from the following detailed description of the invention, when taken in conjunction with the accompanying exemplary drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 depicts a top, front, perspective view of the foldable organizer in a closed position, in accordance with an embodiment of the present invention.
[0013] FIG. 2 is a left side elevation view of the foldable organizer in a closed position.
[0014] FIG. 3 is a right side elevation view of the foldable organizer in a closed position.
[0015] FIG. 4 is a bottom plan view of the foldable organizer in a closed position.
[0016] FIG. 5 is a rear elevation view of the foldable organizer in a closed position.
[0017] FIG. 6 is a top plan view of the foldable organizer in a closed position.
[0018] FIG. 7 is a front elevation view of the foldable organizer in a closed position.
[0019] FIG. 8 is a perspective view of the interior of the foldable organizer in an open position.
[0020] FIG. 9 is an elevational view of the exterior of the foldable organizer in an open position.
[0021] FIG. 10 is an elevational view of the interior of the foldable organizer in an open position with a writing pad shown in dashed lines.
[0022] FIG. 11 is a bottom plan view of the foldable organizer in an open position.
[0023] FIG. 12 is a top plan view of the foldable organizer in an open position.
[0024] FIG. 13 is a left side elevation view of the foldable organizer in an open position.
[0025] FIG. 14 is a right side elevation view of the foldable organizer in an open position.
[0026] FIG. 15 is a front, top, left exploded view of the interior section with the foldable organizer in an open position showing the insert removed.
[0027] FIG. 16 is a front, top, perspective view of the ORGANIZER in an open position showing the compartment slightly open and a separate pocketed leaf contained within the compartment.
[0028] FIG. 17 is a cross-sectional view taken along line 17 - 17 showing the front of the separate pocketed leaf attached to the bottom of the compartment of the ORGANIZER.
[0029] FIG. 18 is a rear, top, perspective view of the ORGANIZER in an open position showing the compartment slightly open and a separate pocketed leaf contained within the compartment.
[0030] FIG. 19 is a cross-sectional view taken along line 19 - 19 showing the rear of the separate pocketed leaf attached to the bottom of the compartment of the ORGANIZER.
[0031] FIG. 20 is a front elevational view of the insert for foldable organizer in an open position.
[0032] FIG. 21 is a side view of the insert for foldable organizer in an open position.
[0033] FIG. 22 is a front, side perspective view of the insert for the foldable organizer.
[0034] FIG. 23 is a rear, side perspective view of the insert for the foldable organizer
DETAILED DESCRIPTION OF EMBODIMENTS
[0035] In various embodiments, the foldable organizer comprises a folding case having a compartment for storing receipts. The foldable organizer also may be described as a stationary-type portfolio or as a padfolio, and may be suggestive of a wallet. In one embodiment, a foldable organizer designed to capture various information helpful to a waiter or server. Such a foldable organizer may include a folding case containing a notepad; at least one compartment for storing paper money and receipts; a clear pocket for inserting information; a writing utensil holder; a rear card pocket for holding a credit card; and a credit card swipe machine to processing credit cards. The folder organizer also may include an elongated leaf affixed within the compartment, dividing the compartment into two sections, and the leaf further having pockets for accepting and holding cards. The pockets are positioned on the leaf so as to avoid interfering with the closing of the folding case. Referring now to the drawings, like parts are designated by like reference characters throughout the several views.
[0036] FIGS. 1 and 7 depict a foldable organizer case 10 in a closed position, and showing the rear pocket 20 for storing cards such as a credit card or a point-of-sale (POS) computer swipe card. One suitable dimension for the rear pocket is 2.8 inches (7.2 cm) by 2.6 inches (6.7 cm). The rear pocket 20 is also illustrated in FIGS. 9 and 18 , depicting the foldable organizer case 10 in an open position.
[0037] The rear pocket 20 preferably is integrally formed on the rear exterior section 18 of the foldable organizer case 10 . The rear exterior section 18 includes a backing 22 and a flexible shell 24 covering substantially the entire rear exterior section of the folding case 10 . A v-shaped opening 26 is formed integrally in the flexible shell 24 . The v-shaped opening 26 creates the rear pocket between the flexible shell 24 and the backing 22 , and the rear pocket 20 is configured to accept a card such as a credit card or a POS card. The integrally formed rear pocket 20 streamlines the appearance and leaves a large surface on the rear exterior section 18 to deboss and/or print custom branding or logos.
[0038] Vinyl (or PVC) is a suitable material for the flexible shell 24 . Leather is another suitable material for the flexible shell. The backing 22 is preferably rigid. Cardboard may be a suitable material for the backing 22 . In one embodiment, a sheet 28 of vinyl is adhered to the backing 22 and behind the flexible shell on the rear exterior section 18 of the foldable organizer case 10 . In this manner, a card in the rear pocket 20 would be sandwiched between two layers of vinyl. The additional layer of material placed over the backing 22 and behind the flexible shell 24 of the rear exterior section 18 also helps avoid the seals or lines that a non-integrally formed rear pocket would create.
[0039] The rear pocket 20 is preferably sized and positioned on the rear exterior section to prevent the inserted card from getting lost in the void alongside the additional layer of material. The v-shape of the opening 26 for the rear pocket 20 facilitates removal of the card from the pocket. Preferably, the sides of the rear pocket 20 cover about two-thirds of the length of the card to be held by the pocket. The rear pocket 20 preferably also is located near the bottom left corner of the rear exterior section 18 of the foldable organizer case 10 . Otherwise, having the rear pocket positioned more toward the center of the rear exterior section of the foldable case, and cover most of the card, could increase the possibility that the inserted card may slip between the backing and the shell.
[0040] Where the rear exterior section 18 of the foldable organizer case has dimensions of about 6.6 inches (16.9 cm) by 4.6 inches (11.8 cm), a sheet 28 of vinyl having a preferable size of 4.75 inches (12.2 cm) by 6.5 inches (16.6 cm), is placed behind the backing 22 of the case 10 . The opening 26 in the shell 24 for the rear pocket 20 is preferably placed 2.9 inches (7.5 cm) right of center, and coincides with the placement of the vinyl sheet 28 on the backing 22 . The shell 24 preferably is constructed from vinyl, and so a card in the rear pocket would be sandwiched between two sheets of vinyl in this embodiment. A small sealed ridge may be placed around the pocket to make the rear opening stronger and less prone to tearing. A triangle or v-shaped opening 26 is preferred to reduce the likelihood of tearing at the top corner of the rear pocket 20 .
[0041] FIGS. 10 and 15 depict the foldable organizer case 10 in an open configuration. The foldable organizer case 10 comprises a folding case which may contain a notepad or waiter pad 30 for taking food orders placed by restaurant patrons, as well as special requests and other notes regarding the table. The foldable organizer case may include an upper interior pocket into which the back of the notepad may be inserted to hold the notepad in the case.
[0042] The bottom interior panel 34 and the top interior panel 36 are exposed when the foldable organizer case 10 is in the open configuration. In this embodiment, the waiter pad 30 is configured in the bottom interior panel 34 of the foldable organizer case 10 , however, the waiter pad 30 may be configured in any portion of the organizer case 10 . As illustrated in FIG. 15 , the top interior panel 36 of the organizer case 10 further comprises a clear interior pocket 38 for displaying various information related to the function of waiting tables, serving restaurant patrons, and/or other relevant information, when the organizer case 10 is in the open position. The foldable organizer case 10 also may include a lower interior pocket 32 for storing a card such as a credit card, preferably on the bottom interior panel 34 behind the pad 12 .
[0043] The organizer also may include a pen holder. The pen holder may be a channel in the fold of the case that will allow a pen to slide in and out. Another embodiment of the organizer may also include a light preferably located at the top of the top interior panel to illuminate the waiter pad 12 and or the clear pocket, or both, when the foldable organizer case is in the open position.
[0044] FIG. 16 further depicts at least one billfold compartment 40 for storing paper items, such as paper money, receipts, and bills. The compartment 40 preferably is elongated, with an opening that runs nearly the entire length of the open case 10 . The compartment may have only a single common storage space, or, in the alternative, the compartment may be divided into two separate areas, or sub-compartments. For example, one for cash, and one for credit card receipts. These sub-compartments 46 and 48 are separated or divided by a flexible leaf 50 . Preferably, the bottom of the leaf is affixed to the bottom 44 of the compartment 40 . In one preferred embodiment, the leaf 50 is positioned in the middle of the billfold compartment 40 , and does not to extend the entire length of the compartment 40 . The lateral ends of the leaf 50 are free or unaffixed to the compartment 40 . The leaf 50 may act as a divider without having its lateral ends affixed to the compartment 40 and still substantially isolate the sub-compartments created by the leaf 50 , while allowing for less constrictive access to the sub-compartments 46 and 48 . This also allows the billfold area to be closely positioned at the top and bottom, making the compartment tight in those areas, and allows for less bulk in the foldable organizer In one embodiment, the leaf 50 sits one centimeter below the height of the compartment, and only extends wide enough to hold two credit cards. The leaf 50 can be moved forward and back to provide the user with access to separate areas of the billfold compartment 40 , as well as to the pockets of the leaf 50 .
[0045] The leaf 50 preferably includes four pockets 52 , 54 , 56 , and 58 , each having an opening and configured to hold a card such as a credit card. The first pocket 52 preferably is located adjacent the top interior panel and the second pocket 54 is located adjacent the bottom interior panel such that the pockets do not interfere with closing the folding case 10 . Preferably, two pockets are placed symmetrically on each side of the leaf 50 . Thus, first pocket 52 and third pocket 56 are located adjacent the top interior panel and the second pocket 54 and fourth pocket 58 are located adjacent the bottom interior panel. Various guests' credit cards and/or driver's licenses can be stored in the leaf 50 within the billfold compartment 40 . Each pocket preferably includes a clear material to allow the user to identify each guest's credit card and/or driver's license. Preferably, each pocket opens toward the top of the billfold compartment.
[0046] The foldable organizer case 10 may be used with an insert 60 to store credit cards, driver's licenses, and similarly sized objects. The insert 60 preferably includes a plurality of sheets 62 with pockets 72 sized for holding credit cards. Preferably, each sheet includes three pockets on each side. The pocketed sheets 72 are sandwiched between a front sheet 64 and a back sheet 66 which are preferably clear to allow the user to identify the cards, as illustrated in FIGS. 8 , 15 , 22 and 23 . In one embodiment, the back sheet is a formed from a semi-rigid piece of solid colored PVC material having a thickness of about 0.75 mm to 1.0 mm. Preferably, the back sheet is made from the same material as the interior of the case. All of the sheets are attached at one end 72 , with the opposite end unattached to allow one to flip from one sheet to another in an accordion fashion, as illustrated in FIGS. 22 and 23 . The sheets of the insert 60 are accessible near the top of the case in the open position, as illustrated in FIG. 8 , as well as FIGS. 1 , 11 and 12 . The back sheet 66 includes an elastic fabric band 70 wraps around the front end of the case 10 to hold the insert 60 in place. Having the elastic fabric band 70 wrap around the top of the front end of the case 10 also allows access to the compartment 40 , and allows the sheets of the insert 60 to be accessible near the top of the case 10 in an accordion fashion. The elastic band may include branding or a logo. The elastic band 70 may be attached to the back sheet 66 by riveting, thermoplastic bonding, another suitable means of attachment. In an alternative embodiment, the insert may be held in place on the top of the case by a clip.
[0047] In FIG. 18 , an optional feature is illustrated on the front exterior side of the organizer 10 . A front exterior pocket 14 is formed on the front exterior side 16 of the organizer case 10 , which enables the user to insert and remove a logo, point of purchase advertisement, or other information chosen to be displayed to restaurant guests. Preferably, three sides of a clear plastic sheet are affixed to the front exterior section 16 of the foldable case 10 , with a thumb tab cutout formed on the open side of the exterior pocket 14 .
[0048] In one embodiment, the organizer may incorporate a credit card swipe machine for processing credit card transactions remotely from the organizer The credit card swipe machine may incorporate a wireless communications means for relaying information to an from a central processing system or network.
[0049] Although embodiments of the invention are described, it is understood that those skilled in the art may conceive modifications and/or variations to the specific embodiments shown and described herein. Any such modifications or variations that fall within the purview of this description are intended to be included therein as well. Unless specifically noted, the words and phrases in the specification and claims are intended to be given the ordinary and accustomed meanings to those of ordinary skill in the applicable art(s). It is, therefore, evident that the particular embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the invention. | A foldable organizer for restaurant waiters includes a folding case which may hold a notepad, an elongated compartment for storing paper money and receipts, a leaf having pockets for holding cards in the elongated compartment, and an exterior pocket for holding a card. The exterior pocket may be produced from a v-shaped opening integrally formed in a flexible shell that surrounds a backing A separate insert is capable of being attached to one end of the folding case, and remains between the two halves of the folding case when in the closed position. The insert including a plurality of pages for holding cards, wherein each of the plurality of pages is joined at one end to create an accordion structure. A strap or clip for fastening the insert to the folding case is located adjacent the end opposite the one end where the plurality of pages are joined. | 1 |
FIELD OF THE INVENTION
The present invention relates to valves and in particular, to electronic devices for indicating relative valve position and for adjusting the opening stop and lockout positions for a manual valve.
BACKGROUND OF THE INVENTION
Many valves, so-called point-of-use valves, used in pharmaceutical piping applications, are valves which are operated manually. Because systems in which these valves are used are periodically sterilized with steam, resulting in safety concerns for valve operators, and because many systems are now required to know the position of valves at all times, great emphasis is placed on indicating the valve position of manual valves, and on providing automatic means for correctly locating and locking out the relevant valves without manual intervention. A temperature-responsive locking mechanism for a manual valve is described in commonly assigned U.S. Pat. No. 5,462,226 issued Oct. 31, 1995, Temperature-Responsive, Locking Mechanism For, And In Combination With, A Fluid Valve, incorporated herein by reference. Until now, two methods have primarily been used to indicate valve position on a manual valve. In the first method, visual indication is used to identify whether a valve is open or closed. Here, bright colors are attached to a part of the valve which moves as the valve is opened or closed in order to identify what position the valve is in. This mechanical method, however, does not provide an operator precise knowledge of the valve position as the valve strokes, other than whether the valve is fully open or fully closed. Under the second method, electronic signals are sent to a programmable logic controller or digital control system by means of a mechanical or proximity switch located at either the open position, the closed position, or at each position to indicate the valve state. For mechanical switches, the switch sends a signal when it is tripped; proximity switches transmit a signal corresponding to an open or closed valve position when a conductor moves into the switch sensing area. This method also suffers the disadvantage of being unable to indicate continuous valve position as the valve strokes. Moreover, standard switches cannot limit the opening of a manual valve, but only provide an electrical output indicating that the valve is open or closed. In addition, because manual valves are often located in environments either open to the natural elements such as rain and snow, or requiring regular washdowns such as in a sanitary facility, a switch cannot simply be attached to the exterior of a manual valve, but must be located in a NEMA (National Electrical Manufactures Association) enclosure. A terminal connection must be used to provide electrical power to the switch, also in the NEMA enclosure, thus making the switch even larger and more difficult to attach to a valve.
Consequently, a compact means for providing an indication of valve position throughout the entire valve stroke, for providing an electronic manual override of a locked valve, and for preventing a valve from fully opening at any position throughout the valve stroke is greatly desired.
SUMMARY OF THE INVENTION
It is an object of this invention to provide an improved electronic valve position indicator apparatus for indicating the position of a manual valve throughout the valve stroke.
It is a further object of this invention to provide an improved electronic valve position indicator apparatus enclosed in a NEMA housing that can provide indication of valve open/closed anywhere throughout the valve stroke and is selectably adjustable.
Another object of this invention to provide an improved electronic valve position indicator apparatus providing adjustable indication of valve open/closed anywhere throughout the valve stroke and that can act as a stop to prevent the valve from fully opening.
Still another object of this invention to provide an improved electronic valve position indicator apparatus having selectable electrical output characteristics for meeting specific controller and output electronics requirements.
It is an object of this invention to disclose an apparatus for providing indication of valve position for a valve having a rotary, operating assembly journaled in a housing, the operating assembly comprising a handwheel, a bushing fastened to the handwheel, and a spindle threadedly engaged to the bushing to cause translation of the spindle in response to rotation of the handwheel and the bushing, the apparatus for enclosure in the housing comprising a hub coupled to the bushing for transmitting rotary motion in response to rotation of the bushing; translation means for translating the rotary motion into an electrical signal; and circuitry means responsive to the electrical signal for indicating position of the valve.
Further objects of this invention, as well as the novel features thereof, will become apparent by reference to the following description, taken in conjunction with the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
A complete understanding of the present invention may be gained by considering the following detailed description in conjunction with the accompanying drawing in which:
FIG. 1 shows a view of the handwheel valve which incorporates the embodiment of the invention therein;
FIG. 2 is an elevational view of FIG. 1, half of the illustration being axially cross-sectioned;
FIG. 3 is a perspective depiction of the housing;
FIG. 4 is a schematic diagram of the electrical circuitry of the thermal switch and solenoid;
FIG. 5 is a schematic diagram of a circuit formed on a circuit board.
FIG. 6 is a schematic diagram of another embodiment of a circuit formed on a circuit board;
FIG. 7 is a schematic diagram of a third embodiment of a circuit formed on a circuit board;
FIGS. 8A-8F illustrate pin connections of embodiments of circuits formed on a circuit board.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates a fluid control valve 10, operative by a handwheel 12, the valve 10 having a valve body 14, an outlet flange 16 and an inlet flange 18. A tee-shaped tube 20 is connected to the inlet flange 18. Between the body 14 and the handwheel 12 is a housing 22 in which are confined components of a temperature-responsive locking mechanism 24 and an electronic valve position indicator apparatus 87. A fluid-temperature-operated switch 26 is mounted onto tube 20 for actuation in response to a given temperature of fluid flow through the tube 20 and valve body 14. An electrical conduit 28 electrically connects switch 26 to an electronic circuit board 88 provided therefor in the housing. An end of a spindle 32 projects from the handwheel 12, and a portion of a spindle-enclosing bushing 34 is shown circumadjacent spindle 32.
The cross-sectional view in FIG. 2 shows the body 14 to have an opening 36 formed therein and, as shown, the opening is closed off by a flexible diaphragm 38. The diaphragm 38 is held against the opening by a compressor 40. A pin 42 fixes the compressor 40 to the spindle 32. An upper end of the spindle 32 is externally threaded and, thereat, threadedly engages internal threads formed on the bushing 34. A set screw 43, in penetration of the handwheel 12, fixes the handwheel to the bushing 34. Consequently, with rotation of the handwheel 12, the spindle 32 is caused to translate, and move the compressor 40 and the thereattached diaphragm 38 from or toward the opening 36. Within the opening 36 is a weir 44. The diaphragm 38, upon having closed against the weir 44, prevents fluid flow through the body 14. The diaphragm 38 must be removed from the weir 44 before flow can pass through the tube 20 and the body 14, and out the opposite end of the body, i.e., via outlet flange 16.
The housing 22 has a base 46 which serves as a platform for components of the locking mechanism 24 and the electronic valve position indicator apparatus 87, and a cover 48. The housing is joined to the bonnet by pins 52 and the bonnet 50 is fastened to the body 14 by hardware 54.
FIG. 3 better illustrates the housing-confined components of the electronic valve position indicator apparatus 87 and locking mechanism 24. Therein it can be seen that an annular hub 61 is set about the bushing 34 and secured thereto by a set screw 58 (shown in FIG. 2). The hub 61 has an upper portion 61a in toothed engagement with potentiometer gear 22, which is secured to multi-turn potentiometer 25 by a set screw 24a, and a lower ratchet portion 61b for potential engagement with locking mechanism 24. Mounted on the base 46 is a solenoid 60. The stroking rod 62 of the solenoid 60 is pivotably coupled to one end of a pawl 64. The pawl 64 is pivotably mounted to the base 46 by a shoulder bolt 66. An extension spring 68, fixed at one end to the base 46, and to the pawl 64 at the other end thereof urges the pawl into engagement with the ratchet portion 61b of hub 61.
As represented in FIG. 4, a source 70 of electric power is connected to the solenoid 60 and to the thermal switch 26. The circuits illustrated in FIGS. 5, 6, and 7 were found to provide satisfactory operation using the numeric values indicated for each labeled component and are given only by way of example. Source 70 is also connected to electronic circuit board 88 mounted to the base 46. Disposed on electronic circuit board 88 is an electronic circuit 88c as illustrated in FIGS. 5 and 8C having a terminal board 1 (tb1) with connector 1 coupled to source 70. Thermal switch 26 is coupled to electronic circuit board 88 at tb1 connector 3. As illustrated in FIG. 4, the temperature switch 26 is normally closed and, consequently, the solenoid is energized. As illustrated in FIG. 5, when temperature switch 26 is closed, power is supplied at tb1 connector 3. Voltage supplied at the positive terminal of coil element K1A of relay 59 induces element K1B to switch from normally closed position c1-c3 to energized position c1-c2, thereby energizing solenoid 60 over line 59a. Therefore, the pawl 64 is withdrawn from hub ratchet portion 61b and the valve 10 is unlocked. When valve 10 is unlocked, one can use the handwheel 12 to open or close the valve 10 at will. As the valve handwheel 12 is turned, the bushing 34 rotates. Hub 61, in lock step with bushing 34, also rotates, thereby transmitting rotary motion to potentiometer gear 22, resulting in either an increase or decrease in resistance of, and hence voltage across, wiper 25a of potentiometer 25, depending on the direction of rotation. For illustrative purposes, full counterclockwise rotation causes valve 10 to become full open, whereby the wiper voltage is minimized. Conversely, full clockwise rotation causes valve 10 to become full closed, thereby maximizing the voltage across wiper 25a. Wiper 25a of potentiometer 25 is coupled to electronic circuit board 88c over terminal strip 78 at terminal board 3 (tb3) connector 2, as illustrated in FIGS. 3, 5, and 8C. Power supply voltage Vcc1 supplied at tb1 connector 1 over line 1a energizes potentiometer 25 at tb3 connector 1. Potential ground is applied at tb1 connector 2 and tb3 connector 3 over line 2a. Therefore, as the valve 10 is turned in a clockwise fashion toward a closed position, bushing 34 rotates in the same direction, causing hub 61 to rotate. As hub 61 rotates, the upper portion 61a in toothed engagement with potgear 22 results in rotation of the potgear, causing a change (increase) in resistance and hence voltage increase across wiper 25a proportional to the degree of valve rotation. The voltage signal Vf is applied at tb3 connector 2 and fed over line 4a to tb1 connector 4 for transmission to a controller (not shown). Similarly, as valve 10 is rotated in a counterclockwise direction toward an open position, hub 61 rotates in the opposite direction, causing a change (decrease) in resistance and hence voltage decrease across wiper 25a proportional to the degree of valve rotation in the opposite direction. Since the voltage signal Vf at tb1 connector 4 fluctuates in magnitude proportional to the direction and degree of valve rotation, the apparatus thereby provides a continuous indicator of the position of the valve throughout the entire valve stroke.
As previously mentioned, the valve 10 is free to move when the temperature switch 26 is closed. However, when temperature sensing probe 80 exposed to the subject fluid reaches a set temperature, switch 26 opens, thereby opening the circuit illustrate in FIG. 4 and de-energizing solenoid 60. The solenoid rod 62 advances and, with the urging of the spring 68, the pawl pivots into ratchet portion 61b of hub 61. The valve 10 is then prevented from opening. As illustrated in FIG. 5, opening thermal switch 26 causes relay coil 59 to close to normally closed position c1-c3, thereby applying a voltage signal at tb3 connector 5 to light lamp 67, indicating a "hot condition" of the valve. Diodes D3 and D4 act as reverse polarity protectors, while diodes D1 and D2 are surge protectors to absorb any spike conditions. The valve can be closed, but it cannot be opened. A novel override feature of the present invention allows for manual override of the lock, thereby permitting further opening of the valve 10. Selection of normally open override switch 66 electrically coupled to tb3 connector 6 and to power source 70 at tb1 connector 1 generates power supply voltage at tb3 connector 4 as illustrated in FIG. 8c, thereby energizing solenoid 60. As solenoid 60 is energized, rod 62 displaces pawl from hub ratchet portion 61b, thereby disengaging locking mechanism 24.
In a second embodiment, referring to FIGS. 6 and 8F, an alternate control circuit 88f on circuit board 88 is illustrated. In this embodiment, the inventive apparatus provides a selectable position indicator for identifying when the rotation of valve 10 has reached a specified threshold value. A first potentiometer 50 coupled between voltage supply Vcc and ground potential serves as an open voltage reference signal Vo. Potentiometer 50 is adjustable such that counterclockwise rotation causes a voltage decrease of reference signal Vo while clockwise rotation increases reference signal Vo. A second potentiometer 51 coupled between supply voltage Vcc and ground potential serves as a close voltage reference signal Vc. Potentiometer 51 is adjustable such that counterclockwise rotation causes a voltage increase of reference signal Vc while clockwise rotation decreases reference signal Vc. When the valve 10 is in a particular position, a voltage Vf representative of the degree of valve rotation relative to a fully open valve position is applied across wiper 25a at tb3 connector 2. Valve rotation voltage Vf is applied across buffer amplifier U1d and resistors R6 and R8 for input at positive terminals 10c and 3o of comparator circuit amplifiers U1c and U1o respectively. Close reference voltage signal Vc is applied across resistor R7 and input to the negative terminal 9c of comparator U1c. Open reference voltage signal Vo is applied to the negative terminal 2o of comparator U1a. For amplifier U1c, when the voltage at positive terminal 10c exceeds the voltage at negative terminal 9c, a positive voltage is applied at terminal 8c. Light emitting diode D1 is therefore forward biased and will illuminate, thereby indicating a "valve closed" position has been reached. The positive voltage applied at node 8c will also bias transistor Q1, causing mechanical relay switch K1 to switch from normally closed position c1-c3 to open position c1-c2, resulting in an output voltage signal Vcr applied at tb2 connector 2 for notifying a controller that a threshold indicating a close valve position has been reached. When the voltage at the positive terminal 10c is less than the voltage at negative terminal 9c of comparator U1c, LED D1 is not forward biased and therefore does not conduct. Consequently, no current is induced in coil k1a and mechanical relay switch K1 remains in normally closed position c1-c3. Therefore, no output voltage signal Vcr is applied at tb2 connector 2.
In a similar manner, when the voltage at positive terminal 3o is less than the voltage at negative terminal 2o, a ground voltage is applied at terminal 1o. Light emitting diode D2 is therefore forward biased and will illuminate, thereby indicating a "valve open" position has been reached. The ground voltage applied at node 1o will bias transistor Q2, causing mechanical relay switch K2 to switch from normally closed position c1-c3 to open position c1-c2, resulting in an output voltage signal Vor applied at tb2 connector 4 for notifying a controller that a threshold indicating an open valve position has been reached. When the voltage at the positive terminal 3o exceeds the voltage at negative terminal 2o of comparator U1o, LED D2 is reverse biased and therefore does not conduct. Consequently, no current is induced in coil k2a and mechanical relay switch K2 remains in normally closed position c1-c3. Therefore, no output voltage signal Vor indicating "valve open" is applied at tb2 connector 4. For example, if first potentiometer 50 is adjusted to provide an open reference voltage signal Vo of 3V, and second potentiometer 51 is adjusted to provide a closed reference voltage signal Vc of 16V, then rotation of handwheel 12 in a direction whereby rotation voltage Vf applied cross amplifier U1d and resistor R8 is less than 3V results in illumination of "open" LED D2 and switching of mechanical relay K2 to indicate an "open valve" position. Rotating handwheel 12 in the opposite direction whereby rotation voltage Vf applied across amplifier U1d and resistor R8 exceeds 3V extinguishes LED D2 and causes switching of mechanical relay K2 to indicate valve is not in "open valve" position. While rotation voltage Vf is between Vc and Vo, neither LED1 or LED2 are illuminated and both mechanical relay switches K1 and K2 are in their normally closed positions. Continued rotation of handwheel 12 in the opposite direction whereby rotation voltage Vf exceeds 16V causes illumination of "close" LED D1 and switching of mechanical relay K1 to indicate a "close valve" position. Circuitry 68 provides current limiting and overvoltage protection to the rest of the circuit. Note that voltage Vo is less than voltage Vc, for proper detection of open and closed valve positions. Both the locking mechanism 24 and override switch 66 function in the identical manner as previously described. In this embodiment, the inventive apparatus therefor provides indication of valve open/closed at any two preselected positions through the valve stroke, with each of the preselected positions adjustable by means of a screwdriver.
In another embodiment of the invention, illustrated in FIGS. 7 and 8D and 8E, solid state proximity switches R1 and R2 are utilized in place of mechanical relay switches K1 and K2 to indicate "open valve" and "close valve" positions. As illustrated in FIG. 7, switches R1 and R2 are optically coupled field effect transistors. Circuit operation is identical to that described in FIG. 6, except for inclusion of selector circuitry 29 for providing the option of the electric output equivalent of a PNP, NPN or 2-wire DC proximity switch outputs. Center off switch SW1 is selectable to operate in: a) first state c1-c3, c4-c6 indicative of PNP operation; b) second state c1-c2, c4-c5 indicative of NPN operation; and c) third state c1-open, c4-open indicative of 2-wire operation. When configured for PNP operation, center-off switch SW1 is coupled between c1-c3 and c4-c6 for solid state relays R2 and R1 respectively. When the voltage output at terminal 1o of comparator U1o resulting from rotation voltage Vf is less than Vo, LED D2 is forward biased, thereby energizing Relay R2. Supply voltage Vcc1 from tb1 connector 1 is applied over line 21, across diode D4 and switch c1-c3 to Relay R2 terminal 6. Because Relay R2 is forward biased, current flows from terminal 4 through solid state fuse protector F2 to tb2 connector 4, indicating to a controller that the valve is open. When Center off switch SW1 is placed in NPN operation and "open valve" threshold is indicated, current flows from tb2 connector 4 through fuse F2 into terminal 4 and out terminal 6 through c1-c2 switch to ground. Similarly, when relay R2 is placed in 2-wire operation, c1 is open so current flows from tb3 connector 3 to terminal 6, across relay R2 at terminal 4, to tb2 connector 4.
Similarly, when LED D1 is forward biased indicating "valve closed" position and PNP switch position 1 is selected for SW1, supply voltage Vcc1 from tb1 connector 1 is applied over line 21, across diode D4 and switch c6-c4 to Relay R1 terminal 6. Because Relay R1 is forward biased, current flows from terminal 4 through solid state fuse protector F1 to tb2 connector 2, indicating to a controller that the valve 10 is closed. When Center off switch SW1 is placed in NPN operation and "close valve" threshold is indicated, current flows from tb2 connector 2 through fuse F1 over line 41 into terminal 4 and output at terminal 6 over line 61 through c4-c5 switch to ground. Similarly, when relay R2 is placed in 2-wire operation and "close valve" threshold is indicated, c4 is open, thereby allowing current flow from tb2 connector 1 to terminal 6 over line 61, across relay R1 at terminal 4, to tb2 connector 2 over line 41. By providing a 3 position center off switch SW1 for selecting the electric output equivalent of a PNP, NPN, or 2-wire DC proximity switch output, one can flexibly tailor the system configuration as needed by simply switching to the desired output.
In another embodiment of the invention, illustrated in FIGS. 6 and 8G, the inventive apparatus functions as an opening stop to limit the opening of the valve 10. In this embodiment, normally closed thermal switch 26 is electrically coupled to tb2 connector 3 and to power supply Vcc over line 19. As handwheel 12 is turned toward an open position, rotation voltage Vf decreases. Open voltage threshold Vo is adjusted to a predetermined level so that mechanical relay K2 is energized, thereby interrupting current flow through relay K2 contacts c1-c3 tb2 connector 3 and tb2 connector 5, thereby de-energizing solenoid 60 and causing valve 10 to lock. This prevents further opening of valve 10, unless a manual override is performed. The opening stop is adjustable via first potentiometer 50 to provide a flexible method of limiting valve flow.
As illustrated in FIG. 8F, the inventive apparatus is adaptable to receiving either DC voltage or both DC and AC voltage and operable to transmit DC voltage output. In a preferred embodiment, optional connector sockets 38 may be used to provide good electrical connections at each of the terminals. Preferably, 4 pin or 9 pin Brad Harrison connectors may be used, to provide electrical connections. In a preferred embodiment, thermal switch 26 is in a normally closed position, as a failure therefore results in fail safe condition. However, thermal switch 26 may also be configured as illustrated in FIG. 8H as normally open.
As will be appreciated from the foregoing description, the present invention provides a practical mechanism for indicating a variety of valve positions for a manual valve.
It will be understood that a person skilled in the art may make many variations and modifications to the described embodiments utilizing functionally equivalent elements to those described. Any variations or modifications to the invention described hereinabove are intended to be included within the scope of the invention as defined by the appended claims. | An apparatus for providing indication of valve position of a manual valve is disclosed for a valve having a rotary, operating assembly journaled in a housing, the operating assembly comprising a handwheel, a bushing fastened to the handwheel, and a spindle threadedly engaged to the bushing to cause translation of the spindle in response to rotation of the handwheel and the bushing, the apparatus for enclosure in the housing comprising a hub coupled to the bushing for transmitting rotary motion in response to rotation of the bushing; translation means for translating the rotary motion into an electrical signal; and circuitry means responsive to the electrical signal for indicating position of the valve. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to apparatus for the coiling of a moving a band web or strips which are cut from the band.
2. The Prior Art
Mechanical assemblies for the coiling of bands, or strips cut from the bands, are known, as shown for example in U.S. Pat. No. 817,025. In this patent, band-like material is first pulled off a roll in order to be fed to a longitudinal cutter. The original full width of the band on the uncoiling roll is cut in this longitudinal cutter by longitudinal cutting, that is, by cutting in the moving direction of the band, into individual, narrower strips. These strips run alternately to one of two coiling positions, whereby each coiling position is formed by two so-called idlers, that is, rollers on which at least one roll forming due to the coiling process can be supported by its own weight, for example. Since two coiling positions with two carrying rolls each are utilized, it is possible to feed one strip, to one coiling position with one pair of carrying rolls and the other, for example adjacent strip to the other pair of carrying rolls of the other coiling position. In this way, at least two relatively narrow rolls are coiled at the same time at the two coiling positions, whereby the sum of the widths of the rolls coiled in each case is identical to the width of the originally uncoiled band.
Another construction of idlers is shown for example in German Patent 25 06 235. Also in this case, an originally wide band is cut in a longitudinal cutter into narrower so-called strips, whereby each of the strips obtained is fed alternately to one of two coiling positions. In this case as well, the coiling positions are produced by two idlers, in particular by one pair of idlers in each case. The strips obtained from the wide band by longitudinal cutting are each coiled into a roll, whereby devices are provided to press each roll forming during the coiling process against the two idlers of each pair of idlers. In this way, the quality of the coiled rolls can be influenced.
Another type of mechanical device to coil strips obtained by longitudinal cutting from an originally wide band into rolls is shown in U.S. Pat. No. 3,883,085. In this case, a so-called supporting roller coiler is shown that has only one coiling position, however, whereby two groups of rolls forming can be supported on a common pressure roller during the coiling process. But other supporting roller coilers are also known that comprise several supporting rollers, preferably one supporting roller per group of rolls forming. For example, U.S. Pat. No. 4,374,575 shows such a device in which the originally wide band at least partially wraps around a central cylinder or roller in such a way that the individual narrow strips obtained by longitudinal cutting from the wide band can each run to one side to one group of rolls forming. In so doing, each group of rolls forming or each individual roll is assigned to a separate pressure roller, in such a way that at least two pressure rollers parallel to each other are present in the machine. However, this machine is basically nothing more than a machine with essentially one coiling position, that is, the originally wide band runs to this coiling position is divided only here into narrower strips in such a way that each strip can be individually rolled into a roll on its own.
A mixed form of supporting roller coiler and idler coiler is shown in European Patent Application 0 616965, wherein the individual rolls forming by coiling of strips are each supported by a pair of relatively small idlers against a common support cylinder. This mixed form of supporting roller coiler and idler coiler also only forms one coiling position however, because in this case as well, the originally wide band is cut only at this coiling position into individual strips in such a way that the strips obtained by the cutting process can be coiled alternately in the one idler bed or in the other idler bed.
Another mixed form of supporting roller coiler and idler coiler is shown in U.S. Pat. No. 4,508,283. Also in this case as the strips obtained by longitudinal cutting of a band are alternately fed to one or the other side of a common support cylinder, whereby the cutter is arranged immediately at or in the vicinity of the support cylinder, however. This known device also forms essentially only one coiling position. All of these known coiling machines have in common that rolls of different widths are to be coiled on them alternately. Based on customer wishes, wider or narrower strips are to be coiled into rolls in such a way that wider or narrower rolls are produced. Since the customer's wishes change frequently, however, it is typical to cut either relatively narrow or relatively wide strips and coil them into one roll, depending on what the customer wishes. But to design the respective machine so that it can be utilized for general purpose, however, the cutters and holders for the respective strips or rolls must be placed and attached differently within the machine, as the customer wishes. For this, conversion work is necessary, which means a corresponding loss of production for the machine. It is therefore necessary to keep this loss of production. as short as possible, which means avoiding it altogether as far as possible. For this reason, a device is needed that makes it possible to feed the band not yet cut into strips by longitudinal cutting to one or another coiling position at any given time, in such a way that the mechanical device of the one or the other coiling position is free for corresponding conversion works, and during conversion or adjusting of the one coiling position, the production of the mechanical device can continue at the other coiling position without interrupting production as far as possible, and to thereby further increase the mechanical device's availability as much as possible.
SUMMARY OF THE INVENTION
According to the present invention a coiling apparatus includes two coiling stations, at least one of the coiling stations including a supporting roller coiler, and guide rollers and guide plates providing guide channels for delivering a moving band or web to one or the other of the two coiling stations. Each coiling station can include cutting elements to divide the moving band or web into multiple strips which are also coiled.
Further features and advantages of the invention will become apparently by reference to the accompanying figure taken with the following discussion.
BRIEF DESCRIPTION OF THE FIGURE
The figure schematically depicts a coiling assembly in accordance with a preferred embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the accompanying figure, band 1 of paper, foil, tissue, metal, plastic or the like runs in the direction of the arrow 2 over guide rollers 3, 4, 5 and 6 to a deflection roller 7. The deflection roller 7 can work with at least one upper blade 8 in such a way that the deflection roller 7 and the at least one upper blade 8 represent a cutting device that is able to separate into individual narrower strips the band which is still in its full width or essentially full width and not yet divided, running in the moving direction of the band 1, i.e., in the direction of the arrow 2. Each strip obtained by the deflection roller 7 with the at least one upper blade 8 representing altogether a longitudinal cutter runs at least partially around the deflection roller 7, then wraps around either the supporting roller 9 or the supporting roller 10, to then be coiled in typical manner into a roll 11 or a roll 12. Several upper blades 8 can be arranged side-by-side. In addition, it is possible for several supporting rollers 9 and several supporting rollers 10 to be arranged side-by-side as is already known. Each roll 12 or the coiling shaft or the coiling tube assigned to it is rotatably supported with the aid of at least one support arm 13 during the coiling process. Each roll 11 is rotatably supported with the aid of at least one support arm 14 during the coiling process. Several support arms 13 and 14 may be arranged side-by-side, for example in such a way that two such support arms can support a forming roll and the coiling shaft or coiling tube assigned to it. In addition, the support arms 13 and 14 are equipped with devices that allow the respective forming roll to press against the related supporting rollers 9 and 10 in such a way that the rolls 11 and 12 and, should the occasion arise, further rolls, can be coiled flawlessly. For this purpose, the support arms 13 and 14 are swivel mounted by means of hinges 15 and 16 on slides 17 and 18. The slides 17 and 18 are supported on a guide 19, for example, in such a way that the support arms 13 and 14 can be shifted in the viewing direction of the figure depending on the width of the respective strips being coiled into the rolls 11 and 12 and can be fixed at the desired position. The positions of elements 6 through 19 represent in their entirety a first coiling station. In addition, the inventive assembly includes a second coiling station which includes a supporting roller 20, for example. Forming rolls 21 and 22 can be supported during the coiling process on this supporting roller, for example. For this purpose, the roll 22 is held and rotatably supported by means of at least one support lever 23 and the roll 21 by means of at least one support lever 24 during the coiling process. The pressing of the forming roll or the forming rolls 22 takes place by means of two supporting rollers 25 and 26 which are rotatably mounted in a frame 27. The frame 27 can be swung by means of a swivelling lever 28 around the fixed fulcrum 29 by means of a pressure roller 30 in the direction of the arrow 31. The roll 21 or rolls 21 are attached and supported in similar manner as the roll 22. The band 1 can be fed by means of guide rollers 32, 33 and 34 to the second coiling station. Here and only here can a cutting device with upper blade 35 divide the band 1 into individual narrower strips, in such a way that they can be coiled up into either the roll 21 or the roll 22. For example, the guide roller 34 can at the same time be the lower blade for the upper blade 35. In addition, it is possible to arrange several upper blades 35 side-by-side in such a way that more than two strips can be cut from the band 1. In addition, it is possible to arrange several rolls 21 and several rolls 22 side-by-side in such a way that rolls of different widths can be coiled from strips of different widths. The figure also shows a switch 36 which can be swivelled around the fulcrum 38 by means of a pressure roller 37. The switch 36, which operates as a deflection device for the band 1, may also be equipped with a blade that is able to cut through the entire band 1 crosswise to its moving direction if necessary. In addition, the switch 36 can be swivelled in such a way that the band 1 can run essentially in its full width either to a guide channel 39 or to a guide channel 40. The guide channel 39 guides the band 1 in its full width to the first coiling station, while the guide channel 40 guides the band 1 in its full width to the second coiling station. The guide channels 39 and 40 may consist of guide plates or guide rods, whereby it is ensured that the band is pushed through or dragged through the respective guide channel until reaching the given coiling station. This can take place, for example, in that air nozzles able to carry the band are arranged diagonally to the moving direction on the inside of the respective guide channels, to thereby guide or drive the band by airflow to the given coiling station. In addition, other types of band guiding are possible, for example traction belts or so-called draw-in devices. In simple cases, it may already be sufficient to use a simple carrying plate on one-side of the band or a carrying rod or the like to feed the band to the given coiling station. In this case, the so-called guide channel would become a simple path on which the band 1 is able to slide to the given coiling station. Because the first and the second coiling station for the band 1 or the strips cut from it are arranged behind the switch 36 in the moving direction indicated by the arrow 2 and, in addition, at least one cutting device consisting of the at least one upper blade 8 and the deflection roller 7 is assigned to the first coiling station and the cutting device with the at least one upper blade 35 and the guide roller 34 is assigned to the second coiling station, there is the possibility to guide the band 1 in its moving direction not only over the guide rollers 3 and 4 essentially in its full width up to the guide roller 5, but furthermore, depending on the station of the switch 36 essentially up to the deflection roller 7 or, in the other case, up to the guide roller 34. Only at the cutting devices with the upper blade 8 and the deflection roller 7 or, in the other case, with the upper blade 35 and the deflection roller 34, is the band 1 essentially present in its full width cut into individual strips in its moving direction in such a way that these individual strips can each be coiled into rolls. By switching the switch 36 into the one or the other direction, it is possible to use either the first coiling station or the second coiling station to coil up the band 1 or its parts. The respective unused coiling or the mechanical device there can be prepared for a new coiling process, i.e., the cutting device, the mountings for the forming rolls, etc. can be set to other widths, i.e., to other formats, while production continues uninterrupted at the other coiling station. In addition, it is possible to provide at any given time the same kind of coiling devices at both coiling station; but it is possible, as shown in the disclosed embodiment, to provide different types and designs of coiling devices at one or the other coiling station. In this way, it becomes possible to coil at any given time different bands 1 of different materials, for example either only at the one coiling station or only at the other coiling station. In this way, the proposed device can be used more generally than previous devices. It is also possible to drop all support levers 24, for example in such a way that coiling can only be done on one side of the support roller 20. It is also possible to adjust the one coiling station--the first one, for example in--such a way that the support arms 13 and 14 are stationary at specific station along the guide 19 or to dispense with a slide guide of the guide 19 altogether in such a way that a quasi-fixedformat operation can be adhered to for a specific sequence of coiling procedures. It is also possible, for example, to adjust the fixing of the slides 17 and 18 only for a respective longer duration of operation to another format, i.e., to another width of rolls to be coiled. It is also possible to adjust the support arms 13 and 14 and the support levers 23 and 24 in such a way that, for example, the support arms 13 and 14 keep a different distance or different distances from each other than is the case for the support levers 23 and 24. In the extreme case, in one coiling station, e.g., in the second coiling station, the full width of the band 1 can be coiled up, whereas the first coiling station is adjusted to coil certain narrower strips obtained from the band into relatively narrow rolls 11 and 12. The guide channel 39 includes the guide plate 41, for example, and the guide channel 40 includes the guide plates 42 and 43, for example. So that the support levers 23 and 24 can be guided appropriately, they are provided with hinges 44 and 45 around which they can be swivelled. In the moving direction of the band 1 indicated by the arrow 2, the second coiling station is situated seen in the moving direction clearly on the outside behind the first coiling station, although both coiling station can be operated alternately by means of the band deflection device produced by the switch 36. Unlike an idler coiler which comprises at least one but usually two idlers that receive the weight of at least one roll forming due to the coiling process and that carry at least one roll supporting it from below, so to speak, the so-called supporting roller coiler, as another kind of coiling device in the meaning of the present invention, has at least one roller or the like, against which the at least one roll forming during the coiling process can lean, i.e., essentially can be supported. Such a supporting roller coiler forms a coiling station in the meaning of the present invention; this coiling station may in turn comprise several groups of forming rolls. At least two such coiling station should be arranged essentially one behind the other in the moving direction of the band 1. The band 1 can also be cut straight, i.e., trimmed at its edges already before passing the deflection device, for example, something that essentially does not affect its width. It is also possible to operate the proposed device, with corresponding design of the deflection device (switch 36) and using a corresponding longitudinal cutter, in such a way that at any given time a part of the band 1 or at any given time at least a strip cut out of the band 1 is coiled at the same time at both coiling station. This increases the availability and the multiplicity of possibilities of use or utilization of the proposed mechanical device. To avoid unnecessary repetition and to describe the present invention as briefly as possible, the previous publications cited concerning the state of the art are referred to expressly to support and complete the present description. In addition, if necessary more than two coiling station can be provided in the moving direction of the band on the outside one behind the other, though increasing the expense accordingly. In the meaning of the present invention, an idler, for example, represents a certain kind of coiling machine and a supporting roller coiler, for example, represents another kind.
List of parts
1 band
2 arrow
3 guide roller
4 guide roller
5 guide roller
6 guide roller
7 deflection roller
8 upper blade
9 supporting roller
10 supporting roller
11 roll
12 roll
13 support arm
14 support arm
15 hinge
16 hinge
17 slide
18 slide
19 guide
20 supporting roller
21 rolls
22 rolls
23 support lever
24 support lever
25 supporting roller
26 supporting roller
27 frame
28 swivelling lever
29 fulcrum
30 pressure roller
31 arrow
32 guide roller
33 guide roller
34 guide roller
35 upper blade
36 switch
37 pressure roller
38 fulcrum
39 guide channel
40 guide channel
41 guide plate
42 guide plate
43 guide plate
44 hinge
45 hinge
SUMMARY
To be able to make good use of a device for coiling, at least one coiling station is occupied by a supporting roller coiler. | A coiling assembly for coiling webs of differing characteristics into a roll comprising first and second coiling station different from each other and a guide mechanism for guiding a moving web to one of the first and second coiling station. | 1 |
TECHNICAL FIELD
[0001] The present invention relates to a cyclopolyarylene metal complex and a method for producing the metal complex. The present invention also relates to a metal-substituted cyclopolyarylene compound and a functional-group-containing cyclopolyarylene compound, both obtained using the metal complex.
BACKGROUND ART
[0002] Previously known nanostructures containing carbon atoms include carbon nanotubes made of a cylindrically rolled two-dimensional graphene sheet, cyclic carbon nanotubes containing such carbon nanotubes, and the like.
[0003] Carbon nanotubes have extremely high mechanical strength and high temperature resistance, and efficiently discharge electrons when voltage is applied. With these advantageous properties, carbon nanotubes are expected to be applied in various fields, including chemistry, electronics, and life sciences.
[0004] Known methods of producing carbon nanotubes include arc discharge, laser furnaces, chemical vapor deposition, and the like. However, these methods have a disadvantage in that they can only produce mixtures of carbon nanotubes with various diameters and lengths.
[0005] As a replacement for tubular nanostructures such as carbon nanotubes with a certain length derived from a continuous linkage of carbon atoms, recent studies have focused attention on cyclic nanostructures. For example, cycloparaphenylene (CPP) is a simple and beautiful molecule in which benzenes are linked at the para-positions to form a circle. Recent studies have revealed that cycloparaphenylene has a significantly distinctive structure and nature. In particular, since CPP has various diameters depending on the number of benzene rings it contains, and thus has various natures, if CPP is selectively produced, it has the potential to produce carbon nanotubes with various diameters. Therefore, the thoroughly selective production of CPP having different numbers of benzene rings has been desired. However, although a method for obtaining CPP as a mixture is known, the selective synthesis of CPP has been successful in only a few cases.
[0006] The present inventors succeeded in the synthesis of various cycloparaphenylene compounds through a method using a cyclic cycloparaphenylene precursor that contains a cyclohexane ring as a flexural portion (for example, Patent Literature 1 and 2, and Non-patent Literature 1).
[0007] However, although cycloparaphenylene compounds have a significantly distinctive structure and nature as described above, the introduction of a new function by adding a functional group to these compounds has not been developed. Since cycloparaphenylene compounds are highly symmetrical molecules and have many equivalent reaction sites (for example, [12]CPP, which has 12 benzene rings, has 48 equivalent reaction sites), it is difficult to introduce a desired number of functional groups at desired positions.
[0008] Nevertheless, synthesis of functionalized cycloparaphenylene compounds has the potential to lead to synthesis of various unique compounds, such as dimers of cycloparaphenylene compounds. Thus, there is a need for a method to introduce a desired number of functional groups into desired portions of a cycloparaphenylene compound.
[0009] In such a situation, only a method for newly synthesizing cyclic compounds using functional-group-containing monomers (bottom-up method) is known (for example, Patent Literature 3 and Non-patent Literature 2).
CITATION LIST
Patent Literature
[0000]
PTL 1: WO2011/099588
PTL 2: WO2011/111719
PTL 3: WO2013/133386
Non-Patent Literature
[0000]
NPL 1: Takaba, H.; Omachi, H.; Yamamoto, Y.; Bouffard, J.; Itami, K. Angew. Chem. Int. Ed. 2009, 48, 6112
NPL 2: Ishii Y.; Matsuura S.; Segawa Y.; Itami K. Org. Lett. 2014, 16, 2174
SUMMARY OF INVENTION
Technical Problem
[0015] Since there are cycloparaphenylene compounds with various sizes, effective functionalization for each compound is required. The method of Patent Literature 3 and Non-patent Literature 2 (bottom-up method) is useful for obtaining such functionalized cycloparaphenylene compounds; however, it has been difficult to directly functionalize cycloparaphenylene compounds. If a method for directly functionalizing cycloparaphenylene compounds is developed, such a method is expected to be applied to any cycloparaphenylene compound, thus theoretically enabling introduction of a functional group into all cycloparaphenylene compounds. Therefore, a primary object of the present invention is to provide a method for easily functionalizing cycloparaphenylene compounds directly.
Solution to Problem
[0016] The inventors of the present invention conducted extensive research to solve the above problems and found that use of a metal complex obtained by complexation of a benzene ring of a cycloparaphenylene compound with a predetermined metal makes it possible to easily functionalize a cycloparaphenylene compound directly. In addition, since only the moiety coordinated to the metal is highly reactive in the metal complex, it is also possible to easily introduce a desired number of functional groups into a desired portion of a cycloparaphenylene compound through a deprotonation reaction, a reaction with an electrophile, or the like. The inventors conducted further research based on this finding and have accomplished the present invention. Specifically, the present invention encompasses the following features.
[0017] Item 1. A cyclopolyarylene metal complex in which a metal tricarbonyl is coordinated to one benzene ring of a cyclopolyarylene compound.
[0018] Item 2. The cyclopolyarylene metal complex according to Item 1, wherein the cyclopolyarylene compound is a cyclic compound in which at least one member selected from the group consisting of bivalent aromatic hydrocarbon groups and derivative groups thereof are continuously bonded.
[0019] Item 3. The cyclopolyarylene metal complex according to Item 1 or 2, wherein the metal constituting the metal tricarbonyl is chromium, molybdenum, tungsten, iron, ruthenium, osmium, manganese, or rhenium.
[0020] Item 4. A method for producing the cyclopolyarylene metal complex according to any one of Items 1 to 3, the method comprising the step of (I) reacting a cyclopolyarylene compound with a metal compound represented by Formula (2):
[0000] M(CO) 3 Y m ,
[0000] wherein M is a metal atom; Y is the same or different, and each represents a ligand; and m is an integer of 1 to 3.
[0021] Item 5. The method according to Item 4, wherein the step (I) is performed in the presence of an ether solvent or a hydrocarbon solvent.
[0022] Item 6. A metal-substituted cyclopolyarylene compound in which a metal atom is bonded to one carbon atom of one benzene ring of a cyclopolyarylene compound.
[0023] Item 7. The metal-substituted cyclopolyarylene compound according to Item 6, wherein the metal atom is an alkali metal atom.
[0024] Item 8. A method for producing a metal-substituted cyclopolyarylene compound, the method comprising the step of (II) reacting the cyclopolyarylene metal complex according to any one of Items 1 to 3 or a cyclopolyarylene metal complex obtained by the method according to Item 4 or 5 with a metal compound.
[0025] Item 9. The method according to Item 8, wherein the metal compound is an alkali metal compound.
[0026] Item 10. The method according to Item 8 or 9, wherein the metal compound is an alkyllithium.
[0027] Item 11. A functional-group-containing cyclopolyarylene compound in which a boronic acid group or an ester thereof, a silyl group, a carboxy group or an ester thereof, or a formyl group is bonded to one carbon atom of one benzene ring of a cyclopolyarylene compound.
[0028] Item 12. A method for producing a functional-group-containing cyclopolyarylene compound, the method comprising the step of (III) reacting the metal-substituted cyclopolyarylene compound according to Item 6 or 7 or a metal-substituted cyclopolyarylene compound obtained by the method according to any one of Items 8 to 10 with an electrophile.
Advantageous Effects of Invention
[0029] The metal complex of the present invention shows that various cycloparaphenylene compounds can be complexed by reacting them with a specific metal compound. In this complexation, only one benzene ring of the cycloparaphenylene compound can be complexed.
[0030] Use of the metal complex of the present invention makes it possible to easily perform, for example, direct metalation of cycloparaphenylene compounds (synthesis of metal-substituted cyclopolyarylene compounds) and direct functionalization of cycloparaphenylene compounds (synthesis of functional-group-containing cyclopolyarylene compounds), both of which were previously difficult.
[0031] In the metal complex of the present invention, only the moiety coordinated to the metal is highly reactive; therefore, into a desired portion of a cycloparaphenylene compound can be introduced a desired number of metals (synthesis of metal-substituted cyclopolyarylene compounds), functional groups (synthesis of functional-group-containing cyclopolyarylene compounds), or the like through a deprotonation reaction, a reaction with an electrophile, or the like. In other words, it is possible to achieve complexation with various metals, metalation, functionalization, or the like for various cycloparaphenylene compounds. Thus, the present invention is useful because it is highly versatile.
[0032] In particular, the present invention enables complexation, metalation, functionalization, and the like of cycloparaphenylene compounds and like cyclic compounds that are highly symmetrical and have many equivalent reaction sites (preferably introduction of a desired number of complexes, metals, functional groups, or the like into a desired portion).
[0033] It is expected that use of the metal complex of the present invention, the metal-substituted cyclopolyarylene compound of the present invention, or the functional-group-containing cyclopolyarylene compound of the present invention enables synthesis of cycloparaphenylene dimmers. Also expected is synthesis of carbon nanobelts in which all corresponding carbon atoms of two molecules of a cycloparaphenylene compound are bonded together. Unlike previously known methods, the method of the present invention allows complexation with various metals, metalation, functionalization, and the like for various cycloparaphenylene compounds; therefore, synthesis of various cycloparaphenylene dimmers, carbon nanobelts, carbon nanotubes, cyclic carbon nanotubes, and the like are also anticipated. The cyclopolyarylene compound of the present invention is thus expected to be applied in various fields, including chemistry, electronics, and life sciences.
DESCRIPTION OF EMBODIMENTS
[1] Cyclopolyarylene Metal Complex
[0034] The cyclopolyarylene metal complex of the present invention is a cyclopolyarylene metal complex in which a metal tricarbonyl is coordinated to one benzene ring of a cyclopolyarylene compound.
1-1. Cyclopolyarylene Compound
[0035] In the present invention, the cyclopolyarylene compound is a cyclic compound in which multiple arylene groups form a cyclic structure via single bonds and in which no complexes, metals, or substituents such as functional groups are introduced. More specifically, such a compound is a cyclic compound represented by Formula (A):
[0000]
[0000] wherein R is the same or different, and each represents an arylene group; and n is an integer of 5 to 30.
[0036] In Formula (A), R is an arylene group. Specifically, R is a bivalent group containing an aromatic ring, which is obtained by eliminating a hydrogen atom from each of two carbon atoms of the aromatic ring. Each R may be the same or different.
[0037] In addition to benzene rings, examples of aromatic rings include rings resulting from the condensation of multiple benzene rings (benzene-condensed rings), rings resulting from the condensation of benzene and other rings, and the like (hereafter, these rings resulting from the condensation of multiple benzene rings and rings resulting from the condensation of benzene and other rings may be collectively referred to as “condensed rings”). Examples of condensed rings include a pentalene ring, indene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, perylene ring, triphenylene ring, azulene ring, heptalene ring, biphenylene ring, indacene ring, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, and the like.
[0038] R is preferably a bivalent group that contains a 6-membered aromatic ring or a 6-membered heterocyclic aromatic ring among the above rings, and that has binding sites at the para-positions.
[0039] Further, the aromatic ring of R is preferably a monocyclic or condensed ring. A monocyclic ring is more preferable.
[0040] Among these, R is preferably a phenylene group (in particular, 1,4-phenylene group), a naphthylene group (in particular, 1,5-naphthylene group or 2,6-naphthylene group), or the like. A phenylene group (in particular, 1,4-phenylene group) is more preferable.
[0041] In the cyclic compound of the present invention, n, i.e., the number of arylene groups is an integer of 5 to 30, preferably an integer of 5 to 20, more preferably an integer of 5 to 18, even more preferably an integer of 5 to 16 or 18, and particularly preferably an integer of 6 to 15.
[0042] The cyclopolyarylene compound used in the present invention is preferably a cycloparaphenylene compound in which all of the organic ring groups are phenylene groups (in particular, 1,4-phenylene groups).
[0043] Among cyclopolyarylene compounds used in the present invention, a cycloparaphenylene compound consisting of 1,4-phenylene groups is, for example, a compound represented by Formula (A1):
[0000]
[0000] wherein a is an integer of 6 or more.
1-2. Method for Producing Cyclopolyarylene Compound
[0044] The cyclopolyarylene compound used in the present invention can be synthesized by using a known method or can be a commercially available product.
[0045] For example, the cyclopolyarylene compound used in the present invention can be produced according to the method described in Patent Literature 1, 2, or 3; Jasti, R. et al., J. Am. Chem. Soc., 2008, 130(52), 17646; Itami, K. et al., Angew. Chem. Int. Ed., 2009, 48, 6112 (Non-patent Literature 1); Itami, K. et al., Angew. Chem. Int. Ed., 2010, 49, 10202; Yamago, S. et al., Angew. Chem. Int. Ed., 2009, 49, 75; Jasti, R. et al., Nature Chemistry, 2014, 6, 404; Jasti, R. et al., J. Org. Chem., 2012, 77, 10473; Itami, K. et al., Chem. Sci. 2012, 3, 2340; or the like, or a method analogous to this method. If necessary, cyclopolyarylene compounds having various numbers of rings can be obtained by using various methods.
1-3. Metal Tricarbonyl
[0046] In the cyclopolyarylene metal complex of the present invention, there are no particular limitations on the metal constituting a metal tricarbonyl coordinated to the cyclopolyarylene compound described above. Examples of metals include chromium, molybdenum, tungsten, iron, ruthenium, osmium, manganese, rhenium, and the like. Among these, chromium, molybdenum, tungsten, and the like are preferable in terms of reactivity. The metal may be appropriately selected according to physical properties required for the cyclopolyarylene metal complex.
[0047] In the cyclopolyarylene metal complex of the present invention, only one metal tricarbonyl is coordinated to one benzene ring of the cyclopolyarylene compound. More specifically, the cyclopolyarylene metal complex of the present invention has a bivalent group represented by Formula (1):
[0000]
[0000] wherein M is a metal atom; and six dotted lines connecting M and the six carbon atoms of a benzene ring, and three dotted lines connecting M and three CO each represent a coordinate bond.
[0048] Examples of the metal atom represented by M in Formula (1) include chromium, molybdenum, tungsten, iron, ruthenium, osmium, manganese, rhenium, and the like. Among these, chromium, molybdenum, tungsten, and the like are preferable in terms of reactivity.
[0049] In the cyclopolyarylene metal complex of the present invention, groups other than the above bivalent group are preferably all 1,4-phenylene groups.
[0050] Specifically, the cyclopolyarylene metal complex of the present invention is preferably a compound represented by Formula (6):
[0000]
[0000] wherein R 2 is a bivalent group represented by Formula (1); and b is an integer of 0 to 25.
[0051] In Formula (6), b may be appropriately set according to required properties, and is preferably an integer of 0 to 25, more preferably an integer of 0 to 15, even more preferably an integer of 0 to 13, particularly preferably an integer of 0 to 11 or 13, and most preferably an integer of 1 to 10.
[0052] As stated above, the present invention makes it possible to coordinate a metal tricarbonyl to only one benzene ring; therefore, only one portion of the cyclopolyarylene compound can be functionalized.
[2] Method for Producing Cyclopolyarylene Metal Complex
[0053] Although there are no particular limitations, the cyclopolyarylene metal complex of the present invention can be obtained by using a production method comprising the step of (I) reacting a cyclopolyarylene compound with a metal compound represented by Formula (2):
[0000] M(CO) 3 Y m ,
[0000] wherein M is a metal atom; Y is the same or different, and each represents a ligand; and m is an integer of 1 to 3.
[0054] As the cyclopolyarylene compound, the cyclopolyarylene compound described above can be used.
[0055] Examples of the metal atom represented by M in Formula (2) include chromium, molybdenum, tungsten, iron, ruthenium, osmium, manganese, rhenium, and the like. Among these, chromium, molybdenum, tungsten, and the like are preferable in terms of reactivity.
[0056] In Formula (2), the ligand represented by Y is not particularly limited as long as it can be coordinated to the metal atom represented by M (such as chromium, molybdenum, tungsten, iron, ruthenium, osmium, manganese, or rhenium).
[0057] Examples of ligands include carbonyl (CO), isocyanide, arenes, olefins, pyridines, amines, phosphines, carbenes, nitriles, hydrogen (hydride; H − ), halogen, lower alkoxy, boron-containing ligands, phosphorus-containing ligands, antimony-containing ligands, arsenic-containing ligands, sulfonic-acid-based ligands, sulfate, perchlorate, nitrate, bis(triflyl)imide, tris(triflyl)methane, bis(triflyl)methane, carboxylates, and the like. The ligands are preferably all carbonyl groups.
[0058] Examples of nitriles as the ligand represented by Y in Formula (2) include benzonitrile, acetonitrile, propionitrile, and the like.
[0059] Examples of halogen atoms as the ligand represented by Y in Formula (2) include fluorine, chlorine, bromine, and iodine.
[0060] In Formula (2), m is an integer of 1 to 3, and preferably 3.
[0061] The metal compound represented by Formula (2) may be a known or commercially available metal compound. The ligands, i.e., carbon monoxide (CO) and Y, may be coordinated in advance or may be coordinated in the system. Specifically, in the coupling reaction of the present invention, a metal compound in which carbon monoxide (CO) and Y are coordinated may be used, or one or more predetermined ligand compounds and a predetermined metal compound may be used.
[0062] Such metal compounds may be used singly or in a combination of two or more. The metal compound is preferably selected according to physical properties required for the cyclopolyarylene metal complex of the present invention.
[0063] The amount of the metal compound varies depending on the type of metal it contains and, for example, is generally preferably about 0.5 to about 10 mol, and more preferably about 1 to about 3 mol, per mol of the cyclopolyarylene compound that is a substrate. When the metal compound is synthesized in the system, it is preferable that the amount of the metal compound in the system be adjusted within the above range.
[0064] It is preferable that step (I) be generally performed in the presence of a reaction solvent. Examples of reaction solvents include chain ethers such as dimethoxyethane, diisopropyl ether, di-n-butyl ether, and tert-butyl methyl ether; cyclic ethers such as dioxane and tetrahydrofuran; aliphatic hydrocarbons such as hexane, cyclohexane, and heptane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and the like. These may be used singly or in a combination of two or more. Among these, in the present invention, ether solvents (such as chain ethers and cyclic ethers) or hydrocarbon solvents (aliphatic hydrocarbons and aromatic hydrocarbons) are preferable. Ether solvents (such as chain ethers and cyclic ethers) are more preferable, and di-n-butyl ether, tetrahydrofuran, and the like are more preferable.
[0065] When the reaction solvent is used, the concentration of the cyclopolyarylene compound as a substrate in the reaction solvent is not particularly limited, and is preferably 1 to 10 mM.
[0066] The reaction temperature in the above reaction is generally selected from a temperature range of not less than 0° C. and not more than the boiling point of the reaction solvent. The reaction time may be a period of time sufficient for the reaction to proceed.
[0067] The reaction atmosphere is not particularly limited; an inert gas atmosphere, such as an argon gas atmosphere or a nitrogen gas atmosphere, is preferable. It is also possible to use air atmosphere.
[0068] After the reaction, a purification step may be performed as necessary. In the purification step, general post-treatment steps, such as solvent removal, washing, and chromatography separation, may be performed.
[3] Metal-Substituted Cyclopolyarylene Compound
[0069] In the metal-substituted cyclopolyarylene compound of the present invention, a metal atom is bonded to one carbon atom of one benzene ring of a cyclopolyarylene compound.
[0070] The metal atom bonded to one carbon atom of one benzene ring of a cyclopolyarylene compound is not particularly limited. Examples include alkali metal atoms, alkaline earth metal atoms, and the like. Alkali metals are preferable. Lithium atom, sodium atom, and the like are more preferable, and lithium atom is even more preferable.
[0071] Specifically, the metal-substituted cyclopolyarylene compound of the present invention is preferably, for example, a compound represented by Formula (7):
[0000]
[0000] wherein M 1 is a metal atom; and c is an integer of 0 or more.
[0072] The metal atom represented by M 1 in Formula (7) is not particularly limited. Examples include alkali metal atoms, alkaline earth metal atoms, and the like. Alkali metals are preferable. Lithium atom, sodium atom, and the like are more preferable, and lithium atom is even more preferable.
[0073] In Formula (7), c may be appropriately set according to required properties; c is preferably an integer of 0 to 25, more preferably an integer of 0 to 15, even more preferably an integer of 0 to 13, particularly preferably an integer of 0 to 11 or 13, and most preferably an integer of 1 to 10.
[0074] The metal-substituted cyclopolyarylene compound can also be obtained as a synthetic intermediate when a functional-group-containing cyclopolyarylene compound is obtained from the cyclopolyarylene metal complex described above.
[4] Method for Producing Metal-Substituted Cyclopolyarylene Compound
[0075] The metal-substituted cyclopolyarylene compound of the present invention can be produced, for example, by using a method comprising the step of (II) reacting the cyclopolyarylene metal complex of the present invention with a metal compound.
[0076] The metal compound is not particularly limited and is preferably an organic alkali metal compound. Examples include organic lithium compounds, organic sodium compounds, and the like. Organic lithium compounds are particularly preferable. Examples of organic lithium compounds include organic monolithium compounds, organic dilithium compounds, organic polylithium compounds, and the like.
[0077] Specific examples of organic lithium compounds include alkyllithiums, such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, and hexyllithium; cycloalkyllithiums, such as cyclohexyllithium; aryllithiums, such as phenyllithium; hexamethylene dilithium, cyclopentadienyl lithium, indenyl lithium, 1,1-diphenyl-n-hexyllithium, 1,1-diphenyl-3-methylpentyllithium, lithium naphthalene, butadienyl dilithium, isopropenyl dilithium, m-diisoprenyl dilithium, 1,3-phenylene-bis-(3-methyl-1-phenylpentylidene)bislithium, 1,3-phenylene-bis-(3-methyl-1,[4-methylphenyl]pentylidene)bislithium, 1,3-phenylene-bis-(3-methyl-1,[4-dodecylphenyl]pentylidene)bislithium, 1,1,4,4-tetraphenyl-1,4-dilithio butane, polybutadienyl lithium, polyisoprenyl lithium, polystyrene-butadienyl lithium, polystyrenyl lithium, polyethylenyl lithium, poly-1,3-cyclohexa dienyl lithium, polystyrene-1,3-cyclohexadienyl lithium, polybutadiene-1,3-cyclohexadienyl lithium, and the like. These may be used singly or in a combination of two or more. Among these, in terms of the yield, organic monolithium compounds are preferable, alkyllithiums, cycloalkyllithiums, aryllithiums, and the like are more preferable, and ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, hexyllithium, cyclohexyllithium, phenyllithium, and the like are even more preferable.
[0078] The amount of the metal compound is not particularly limited. In terms of the yield, the amount of the metal compound is generally preferably 2 to 50 mol, more preferably 3 to 30 mol, and even more preferably 5 to 20 mol, per mol of the cyclopolyarylene metal complex of the present invention.
[0079] The above reaction is generally performed in the presence of a reaction solvent. Examples of reaction solvents include ethers, such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and diisopropyl ether; hydrocarbon solvents, such as hexane and pentane; and the like. These may be used singly or in a combination of two or more. Among these, ethers (such as tetrahydrofuran and diethyl ether) are preferable in the present invention.
[0080] When the reaction solvent is used, the concentration of the cyclopolyarylene metal complex of the present invention in the reaction solvent is not particularly limited and is preferably 1 to 15 mM.
[0081] The reaction temperature is generally selected from a temperature range of not less than −100° C. and not more than the boiling point of the reaction solvent. The reaction time may be a period of time sufficient for the reaction to proceed.
[0082] The reaction atmosphere is not particularly limited; an inert gas atmosphere, such as an argon gas atmosphere or a nitrogen gas atmosphere, is preferable. It is also possible to use air atmosphere.
[0083] After the reaction step, a purification step may be performed as necessary. In the purification step, general post-treatment steps, such as solvent removal, washing, and chromatography separation, may be performed.
[5] Functional-Group-Containing Cyclopolyarylene Compound
[0084] In the functional-group-containing cyclopolyarylene compound of the present invention, a boronic acid group or an ester thereof, a silyl group, a carboxy group or an ester thereof, or a formyl group is bonded to one carbon atom of one benzene ring of a cyclopolyarylene compound.
[0085] The functional group bonded to one carbon atom of one benzene ring of a cyclopolyarylene compound is, for example, a boronic acid group or an ester thereof, a silyl group, a carboxy group or an ester thereof, a formyl group, or the like. The functional group is preferably a carboxy group or an ester thereof, or a formyl group.
[0086] The boronic acid group or an ester thereof is, for example, preferably a group represented by the formula below:
[0000]
[0000] wherein R′ is the same or different, and each represent a hydrogen atom or a lower alkyl group (in particular, C 1-10 alkyl group), and R′ may be bonded to each other to form a ring with the adjacent —O—B—O—.
[0087] R′ in the boronic acid group or an ester thereof is a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 10, more preferably 1 to 8, even more preferably 1 to 5 carbon atoms. Further, in the above formula, the two R′ may be the same or different. When R′ represents an alkyl group, the carbon atoms of the alkyl groups may be bonded to form a ring with the boron atom and the oxygen atoms.
[0088] Examples of such a boronic acid group or an ester thereof include groups represented by the formulae below:
[0000]
[0089] wherein R″ is the same or different, and each represents a hydrogen atom or a lower alkyl group (in particular, C 1-10 alkyl group). The boronic acid group or an ester thereof is particularly preferably a group represented by the formula below:
[0000]
[0090] Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and the like.
[0091] Examples of the carboxy group or an ester thereof include, in addition to a carboxy group, esters of a carboxy group, such as a carboxymethyl group and a carboxyethyl group.
[0092] The functional group may be appropriately selected according to required properties.
[0093] Specifically, the functional-group-containing cyclopolyarylene compound of the present invention is, for example, preferably a compound represented by Formula (8):
[0000]
[0000] wherein R 3 is a functional group (such as a boronic acid group or an ester thereof, a silyl group, a carboxy group or an ester thereof, or a formyl group); and d is an integer of 1 or more.
[0094] In Formula (8), d may be appropriately set according to required properties; d is preferably an integer of 1 or more, more preferably an integer of 1 to 50, even more preferably an integer of 2 to 30, and particularly preferably an integer of 3 to 20.
[6] Method for Producing Functional-Group-Containing Cyclopolyarylene Compound
[0095] The functional-group-containing cyclopolyarylene compound of the present invention can be produced, for example, by using a method comprising the step of (III) reacting the metal-substituted cyclopolyarylene compound of the present invention with an electrophile.
[0096] After the cyclopolyarylene metal complex of the present invention is reacted with a metal compound according to step (II) described above, an electrophile may be added as is.
[0097] The electrophile is not particularly limited. Examples of electrophiles include esterifying agents, borylating agents, substituted silylating agents, acylating or formylating agents, and the like.
[0098] Examples of esterifying agents include methyl iodoformate, ethyl iodoformate, methyl iodoacetate, ethyl iodoacetate, methyl bromoformate, ethyl bromoformate, methyl bromoacetate, ethyl bromoacetate, methyl chloroformate, ethyl chloroformate, methyl chloroacetate, ethyl chloroacetate, and the like. Among these, methyl chloroformate and the like are preferable.
[0099] Examples of borylating agents include methoxyboronic acid, ethoxyboronic acid, methoxyboronic acid pinacol ester, ethoxyboronic acid pinacol ester, and the like. Among these, methoxyboronic acid pinacol ester and the like are preferable.
[0100] Examples of substituted silylating agents include substituted silyl iodides, such as iodotrimethylsilane, iodotriethylsilane, iodotributylsilane, iodotricyclohexylsilane, and iodotriphenylsilane; substituted silyl bromides, such as bromotrimethylsilane, bromotriethylsilane, bromotributylsilane, bromotricyclohexylsilane, and bromotriphenylsilane; substituted silyl chlorides, such as chlorotrimethylsilane, chlorotriethylsilane, chlorotributylsilane, chlorotricyclohexylsilane, and chlorotriphenylsilane; substituted silyl mesylates, such as mesylate trimethylsilane, mesylate triethylsilane, mesylate tributylsilane, mesylate tricyclohexylsilane, and mesylate triphenylsilane; substituted silyl tosylates, such as tosylate trimethylsilane, tosylate triethylsilane, tosylate tributylsilane, tosylate tricyclohexylsilane, and tosylate triphenylsilane; substituted silyl triflates, such as triflate trimethylsilane, triflate triethylsilane, triflate tributylsilane, triflate tricyclohexylsilane, and triflate triphenylsilane; and the like. Among these, substituted silyl chlorides are preferable. Chlorotrimethylsilane and the like are more preferable.
[0101] The acylating or formylating agents may have a linear, branched, or cyclic structure, and may have one or more substituent. The acylating or formylating agents generally have about 1 to about 20 carbon atoms. Specific examples of acylating or formylating agents include N,N-dimethylformamide, N,N-diethylformamide, and the like. Among these, N,N-dimethylformamide and the like are preferable.
[0102] These may be used singly or in a combination of two or more.
[0103] The amount of the electrophile is not particularly limited. In terms of the yield, the amount of the electrophile is generally preferably 1 to 500 mol, more preferably 1 to 300 mol, and even more preferably 1 to 200 mol, per mol of the metal-substituted cyclopolyarylene compound of the present invention.
[0104] The reaction described above is generally performed in the presence of a reaction solvent. Examples of reaction solvents include ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and diisopropyl ether; hydrocarbon solvents, such as hexane and pentane; and the like. These may be used singly or in a combination of two or more. Among these, ethers (such as tetrahydrofuran and diethyl ether) are preferable in the present invention. When the reaction is performed continuously after the above-described step (II), the same solvent can be used. However, the reaction intermediate between the starting materials and the functional-group-containing cyclopolyarylene compound may have low solubility in the solvent used. In this case, another solvent may be added in advance or during the reaction.
[0105] When the reaction solvent is used, the concentration of the metal-substituted cyclopolyarylene compound of the present invention in the reaction solvent is not particularly limited and may be similar to the concentration of the cyclopolyarylene metal complex in the reaction solvent in step (II).
[0106] The reaction temperature is generally selected from a temperature range of not less than −100° C. and not more than the boiling point of the reaction solvent. The reaction time may be a period of time sufficient for the reaction to proceed.
[0107] The reaction atmosphere is not particularly limited; an inert gas atmosphere, such as an argon gas atmosphere or a nitrogen gas atmosphere, is preferable. It is also possible to use air atmosphere.
[0108] After the reaction step, a purification step may be performed as necessary. In the purification step, general post-treatment steps, such as solvent removal, washing, and chromatography separation, may be performed.
[0109] After the functional-group-containing cyclopolyarylene compound of the present invention is produced as described above, the functional group can be replaced by another functional group by a known method.
EXAMPLES
[0110] The present invention is described in detail below with reference to Examples, but is not limited to these.
[0111] Unless otherwise noted, all materials, including dry solvent were obtained from commercial suppliers and used without further purification. [9]CPP was synthesized according to an already published document (WO2011/111719). However, tetrahydrofuran (THF) and dibutyl ether were purified by passing through a solvent purification system (glass contour). All the reactions were performed using reagent-grade solvents under air. Ni(cod) 2 was synthesized according to an already published document.
[0112] Thin-layer chromatography (TLC) was performed using E. Merck silica gel 60 F254 precoated plates (0.25 mm). The chromatogram was analyzed with a UV lamp (254 nm and 365 nm). Flash column chromatography was performed using E. Merck silica gel 60 (230-400 mesh). Preparative thin-layer chromatography (PTLC) was performed using Wako-gel® B5-F silica coated plates (0.75 mm). High-resolution mass spectra (HRMS) were performed with a Thermo Fisher Scientific Exactive. Nuclear magnetic resonance (NMR) spectra were recorded with a JEOL JNM-ECA-600 ( 1 H 600 MHz, 13 C 150 MHz) spectrometer. Chemical shifts for 1 H NMR are expressed in parts per million (ppm) relative to CHCl 3 (δ7.26 ppm), CHDCl 2 (δ5.32 ppm), DMSO-d 5 (δ2.50 ppm), or THF-d 7 (δ1.72 ppm). Chemical shifts for 13 C NMR are expressed in parts per million (ppm) relative to CDCl 3 (δ77.0 ppm), CD 2 Cl 2 (δ53.8 ppm), DMSO-d 6 (δ39.5 ppm), or THF-d 8 (δ7.2 ppm). Data are reported in the following order: chemical shift, multiplicity (s=singlet, d=doublet, dd=doublet of doublets, t=triplet, m=multiplet), coupling constant (Hz), and integration.
Example 1
[0113]
[0114] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [9]CPP (5.0 mg, 7.30 μmol), Cr(CO) 6 (1.7 mg, 7.52 μmol), dibutyl ether (0.9 mL), and THF (0.1 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 10 hours in the dark and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (hexane/CHCl 3 ). As a result, the desired chromium-[9]CPP was obtained as an orange solid (2.1 mg, 35%).
[0115] 1H NMR (600 MHz, CDCl 3 ) δ 5.46 (s, 4H), 7.40 (d, J=9.0, 4H), 7.56-7.52 (m, 28H). HRMS (ESI) m/z calcd for C 57 H 36 O 3 CrCl [M.Cl] − : 855.1754. found 855.1782.
Example 2
[0116]
[0117] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [12]CPP (10.0 mg, 11.0 μmol), Cr(CO) (2.5 mg, 11.0 μmol), dibutyl ether (6.8 mL), and THF (0.8 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 2 hours in the dark and concentrated under reduced pressure to give a crude product.
[0118] 1 H NMR (600 MHz, CDCl 3 ) δ 5.61 (s, 4H). HRMS (ESI) m/z calcd for C 75 H 49 O 3 Cr [MH] + : 1049.3081. found 1049.3106.
Example 3
[0119]
[0120] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [9]CPP (5.0 mg, 7.30 μmol), Mo(CO) 6 (30.0 mg, 114 μmol), dibutyl ether (1.8 mL), and THF (0.2 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 1 hour in the dark and concentrated under reduced pressure to give a crude product.
[0121] 1 H NMR (600 MHz, CDCl 3 ) δ 5.72 (s, 4H), HRMS (ESI) m/z calcd for C 57 H 36 O 3 Mo [M.] + : 866.1728. found 866.1748.
Example 4
[0122]
[0123] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [12]CPP (2.5 mg, 2.74 μmol), Mo(CO) 6 (30.0 mg, 114 μmol), dibutyl ether (0.9 mL), and THF (0.1 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 1 hour in the dark and concentrated under reduced pressure to give a crude product.
[0124] 1 H NMR (600 MHz, CDCl 3 ) δ 5.86 (s, 4H). HRMS (ESI) m/z calcd for C 75 H 48 O 3 Mo [M.] + : 1094.2652. found 1094.2661.
Example 5
[0125]
[0126] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [9]CPP (5.0 mg, 7.30 mol), W(CO) 6 (4.0 mg, 11.4 μmol), dibutyl ether (1.8 mL), and THF (0.2 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 1 hour in the dark and concentrated under reduced pressure to give a crude product.
[0127] 1 H NMR (600 MHz, CDCl 3 ) δ 5.56 (s, 4H). HRMS (ESI) m/z calcd for C 57 H 36 O 3 W [M.] + : 952.2178. found 952.2155.
Example 6
[0128]
[0129] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [12]CPP (2.5 mg, 2.74 μmol), W(CO) 6 (70 mg, 199 μmol), dibutyl ether (2.7 mL), and THF (0.3 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 1 hour in the dark and concentrated under reduced pressure to give a crude dark and concentrated under reduced pressure to give a crude product.
[0130] 1 H NMR (600 MHz, CDCl 3 ) δ 5.69 (s, 4H). HRMS (ESI) m/z calcd for C 75 H 49 O 3 W [MH] + : 1181.3199. found 1181.3179.
Example 7
[0131]
[0132] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [9]CPP (20.0 mg, 29.2 μmol), Cr(CO) 6 (7.2 mg, 31.7 μmol), dibutyl ether (9.0 mL), and THF (1.0 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 1 hour in the dark and concentrated under reduced pressure. After the obtained product was dissolved in THF (5.0 mL), a hexane solution of 0.4 M n-butyllithium (150 μL, 60 μmol) was slowly added at −78° C. The reaction mixture was stirred for 30 minutes in the dark (at this point, lithiated [9]CPP was obtained). Thereafter, chlorotrimethylsilane (100 μL, 780 μmol) was added to the reaction mixture, and the resulting reaction mixture was warmed to room temperature and stirred for 1 hour in the dark. The reaction mixture was quenched with water and exposed to air and room light to perform decomplexation for 24 hours. The obtained reaction mixture was concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (hexane/CHCl 3 ). As a result, the desired trimethylsilyl-[9]CPP was obtained as a yellow solid (8.8 mg, 40%), and the starting material [9]CPP was recovered (9.1 mg, 46%).
[0133] 1 H NMR (600 MHz, CDCl 3 ) δ 0.36 (s, 9H), 6.85 (d, J=9 Hz, 1H), 7.08 (d, J=9 Hz, 2 Hz, 1H), 7.22 (d, J=9 Hz, 2H), 7.42 (d, J=9 Hz, 2H), 7.48-7.61 (m, 28H), 7.96 (d, J=2 Hz, 1H); 13 C NMR (150 MHz, CDCl 3 ) δ1.2 (CH 3 ), 127.08 (CH), 127.12 (CH), 127.2 (CH), 127.3 (CH), 127.4 (CH), 127.5 (CH), 127.7 (CH), 127.8 (CH), 129.6 (CH), 129.6 (CH), 129.9 (CH), 131.2 (CH), 132.8 (CH), 137.0 (4°), 137.5 (4°), 137.6 (4°), 137.75 (4°), 137.84 (4°), 137.9 (4°), 138.0 (4°), 138.1 (4°), 138.3 (4°), 138.75 (4°), 138.82 (4°), 142.3 (4°), 146.6 (4°); HRMS(ESI) m/z calcd for C 55 H 44 Si [M.] + : 756.3207. found 756.3182; not degraded or melted at 300° C. or more.
Example 8
[0134]
[0135] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [12]CPP (20.0 mg, 21.9 μmol), Cr(CO) 6 (9.9 mg, 43.8 μmol), dibutyl ether (15.3 mL), and THF (1.7 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 1.5 hours in the dark and concentrated under reduced pressure. After the obtained product was dissolved in THF (5.0 mL), a hexane solution of 0.4 M n-butyllithium (110 μL, 44 μmol) was slowly added at −78° C., and the reaction mixture was stirred for 30 minutes in the dark (at this point, lithiated [12]CPP was obtained). Thereafter, chlorotrimethylsilane (100 μL, 780 μmol) was added to the reaction mixture, and the resulting reaction mixture was warmed to room temperature and stirred for 1 hour in the dark. The reaction mixture was quenched with water and exposed to air and room light to perform decomplexation for 24 hours. The obtained reaction mixture was concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (hexane/CHCl 3 ). As a result, the desired trimethylsilyl-[12]CPP was obtained as a yellow solid (6.7 mg, 31%), and the starting material [12]CPP was recovered (11.9 mg, 60%).
[0136] 1 H NMR (600 MHz, CDCl 3 ) δ 0.32 (s, 9H), 6.96 (d, J=8 Hz, 1H), 7.23 (dd, J=8 Hz, 2 Hz, 1H), 7.30 (d, J=8 Hz, 2H), 7.52 (d, J=8 Hz, 2H), 7.58-7.66 (m, 40H), 7.98 (d, J=2 Hz, 1H); 13 C NMR (150 MHz, CDCl 3 ) δ1.2 (CH 3 ), 127.0 (CH), 127.10 (CH), 127.13 (CH), 127.17 (CH), 127.20 (CH), 127.27 (CH), 127.29 (CH), 127.32 (CH), 127.36 (CH), 127.41 (CH), 127.44 (CH), 127.5 (CH), 127.6 (CH), 127.7 (CH), 129.1 (CH), 129.6 (CH), 131.8 (CH), 132.3 (CH), 137.6 (4°), 138.1 (4°), 138.2 (4°), 138.3 (4°), 138.36 (4°), 138.46 (4°), 138.50 (4°), 138.57 (4°), 138.64 (4°), 138.68 (4°), 138.70 (4°), 138.2 (4°), 139.4 (4°), 142.9 (4°), 147.3 (4°); HRMS (ESI) m/z calcd for C 55 H 44 Si [M.] + : 984.4146. found 984.4133; a melting point of 300° C. or more.
Example 9
[0137]
[0138] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [9]CPP (20.0 mg, 29.2 μmol), Cr(CO) 6 (7.2 mg, 31.7 μmol), dibutyl ether (9.0 mL), and THF (1.0 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 1 hour in the dark and concentrated under reduced pressure. After the obtained product was dissolved in THF (5.0 mL), a hexane solution of 0.4 M n-butyllithium (150 μL, 60 μmol) was slowly added at −78° C., and the reaction mixture was stirred for 30 minutes in the dark (at this point, lithiated [9]CPP was obtained). Thereafter, methyl chloroformate (60 μL, 774 μmol) was added to the reaction mixture, and the resulting reaction mixture was warmed to room temperature and stirred for 1 hour in the dark. The reaction mixture was quenched with water and exposed to air and room light to perform decomplexation for 24 hours. The obtained reaction mixture was concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (hexane/CHCl 3 ). As a result, the desired carboxymethyl-[9]CPP was obtained as a yellow solid (8.2 mg, 38%), and the starting material [9]CPP was recovered (11.8 mg, 59%).
[0139] 1 H NMR (600 MHz, CD 2 Cl 2 ) δ3.85 (s, 3H), 7.04 (d, J=8 Hz, 1H), 7.25 (d, J=8 Hz, 2H), 7.33 (dd, J=8 Hz, 2 Hz, 1H), 7.47 (d, J=8 Hz, 2H), 7.51-7.62 (m, 28H), 8.38 (d, 2 Hz, 1H); 13 C NMR (150 MHz, CD 2 Cl 2 ) δ 52.5 (CH 3 ), 127.5 (CH), 127.60 (CH), 127.69 (CH), 127.77 (CH), 127.82 (CH), 127.86 (CH), 127.9 (CH), 128.1 (CH), 129.2 (CH), 129.3 (4°), 132.7 (CH), 134.3 (CH), 137.8 (4°), 137.9 (4°), 138.0 (4°), 138.26 (4°), 138.35 (4°), 138.47 (4°), 138.57 (4°), 138.64 (4°), 138.88 (4°), 140.5 (4°), 141.0 (4°), 168.6 (4°); HRMS (MALDI-TOF) m/z calcd for C 55 H 37 O [MH] + : 743.2945. found 743.2922. a melting point of 300° C. or more.
Example 10
[0140]
[0141] A magnetic stirring bar was placed in a J. Young® Schlenk flask, and [9]CPP (20.0 mg, 29.2 μmol), Cr(CO) 6 (7.2 mg, 31.7 μmol), dibutyl ether (9.0 mL), and THF (1.0 mL) were added to the flask. The reaction mixture was stirred at 160° C. for 1 hour in the dark and concentrated under reduced pressure. After the obtained product was dissolved in THF (5.0 mL), a hexane solution of 0.4 M n-butyllithium (150 μL, 60 μmol) was slowly added at −78° C., and the reaction mixture was stirred for 30 minutes in the dark (at this point, lithiated [9]CPP was obtained). Thereafter, methoxyboronic acid pinacol ester (50 μL, 305 μmol) was added to the reaction mixture, and the resulting reaction mixture was warmed to room temperature and stirred for 1 hour in the dark. The reaction mixture was quenched with water and exposed to air and room light to perform decomplexation for 24 hours. The obtained reaction mixture was concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (hexane/CHCl 3 ). As a result, the desired tetramethyldioxaboryl-[9]CPP was obtained as a yellow solid (4.7 mg, 20%), and the starting material [9]CPP was recovered (13.9 mg, 70%).
[0142] 1 H NMR (600 MHz, CDCl 3 ) δ 1.34 (s, 12H), 7.03 (d, J=8 Hz, 1H), 7.24 (dd, J=8 Hz, 2 Hz, 1H), 7.30 (d, J=9 Hz, 2H), 7.43 (d, J=9 Hz, 2H), 7.50-7.55 (m, 28H), 8.20 (d, J=2 Hz, 1H); 13 C NMR (150 MHz, CDCl 3 ) δ 24.6 (CH 3 ), 84.0 (4°), 127.08 (CH), 127.12 (CH), 127.18 (CH), 127.25 (CH), 127.36 (CH), 127.42 (CH), 127.44 (CH), 127.6 (CH), 127.7 (CH), 129.9 (CH), 131.3 (CH), 132.2 (CH), 132.5 (CH), 136.9 (CH), 137.66 (4°), 137.69 (4°), 137.73 (4°), 137.76 (4°), 137.82 (4°), 137.90 (4°), 137.92 (4°), 137.94 (4°), 137.99 (4°), 138.01 (4°), 138.4 (4°), 138.5 (4°), 140.9 (4°), 145.6 (4°); HRMS (ESI) m/z calcd for C 3 H 47 BO 2 [M.] + : 810.3664. found 810.3653. | If a method for directly functionalizing cycloparaphenylene compounds is developed, such a method is expected to be applied to any cycloparaphenylene compound, thus theoretically enabling introduction of a functional group into all cycloparaphenylene compounds. Therefore, a primary object of the present invention is to provide a method for easily functionalizing cycloparaphenylene compounds directly. A cyclopolyarylene metal complex in which a metal tricarbonyl is coordinated to one benzene ring of a cyclopolyarylene compound is provided. The cyclopolyarylene metal complex is obtained by using a production method comprising the step of reacting a cyclopolyarylene compound with a metal compound represented by the following formula:
M(CO) 3 Y m ,
wherein M is a metal atom; Y is the same or different, and each represents a ligand; and m is an integer of 1 to 3. | 2 |
BACKGROUND OF THE INVENTION
Systems for producing a yarn of staple glass filaments wherein streams of molten glass attenuated by the action of jets of steam or air are collected on a rotatable foraminous drum and subsequently shaped and drafted into a yarn to be ultimately wound as a package are well known in the art. For example, see U.S. Pat. No. 2,133,238 issued to G. Slayter et al on Oct. 11, 1938.
One of the limiting factors in the throughput in such a system is that commercially available winders are generally not adapted to tension the yarn sufficiently to draft the web of fibers into a yarn while maintaining proper package build.
SUMMARY OF THE INVENTION
Method and apparatus are provided for supplying a web of staple fibers to a first region, forming said web into a bundle at a zone intermediate said first region and an after-defined second region, tensioning said fibers at a second region to draft said bundle into a yarn advancing at a predetermined rate, and collecting said yarn at a third region spaced from said second region at a rate substantially equal to said predetermined rate of advancement of said yarn.
It is an object of this invention to provide an improved system for forming a yarn of staple fibers.
The foregoing, as well as other objects of the present invention, will become apparent to those skilled in the art from the following detailed description.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a semi-schematic front view of a staple yarn production system according to the principles of this invention.
FIG. 2 is a front view of the drafting means shown in FIG. 1.
DESCRIPTION OF THE INVENTION
As shown in FIG. 1, staple filaments 8 are produced by attenuating streams of molten material issuing from feeder 10 by means of blower assembly or attenuation means 12. The fibers can be of any suitable material such as glass or polymeric resin and can be produced by any other system capable of delivering a web of staple fibers.
Blower assembly 12 directs streams of gaseous blasts along the length of the streams or filaments at velocities sufficient to attenuate the streams into staple filaments 8, as is known in the art.
Preferably, blower 12 is of the type having a skirt 13 depending therefrom to enhance and control the attenuation forces. Also, blower 12 should be adjustable along the path of advancement of the filaments, and the orifice through which the filaments pass should be adjustable in size, preferably with respect to the width thereof, for improved control of the process.
As the filaments 8 emerge from blower 12, a liquid sizing and/or binder can be applied to the filaments by means of nozzles 14.
Downstream of the blower 12, a foraminous guide 16 which is comprised of a shell 17 having a plurality of apertures 18 therein, is adapted to dissipate the attenuating gases while retaining the staple filaments within guide 16. As such, the diameter of the apertures 18 should be substantially less than the length of the individual staple filaments 8, and guide 16 should be placed close enough to the vacuum section 22 of drum 20 to induce air inwardly through the apertures 18 at the exit region of guide 16.
As the staple filaments 8 emerge from the foraminous guide 16, the filaments 8 are collected upon a first collection means or drum 20 located in a first region. Drum 20 is comprised of a foraminous, circumferential surface 21 which is rotatably driven as is known in the art. Adjacent the exit of the foraminous guide 16 vacuum section 22 within drum 20 provides an inward flow of air through surface 21 to retain the individual filaments on surface 21, as is known in the art. As such, the individual filaments 8 form a web of inter-entangled filaments 24.
Web 24 then advances through a compacting or twisting means 26 at a zone spaced from the first region. Shaping or compacting means 26 is comprised of a hollow shaft through which the filaments 8 pass while the shaft is rotated at high speed. In forming systems wherein the drum rotates at a surface speed of approximately 400 feet per minute and the yarn is advancing at approximately 800 feet per minute, the compacting means is driven at approximately 3,700 rpm.
Web 24 emerges from the compacting means as a bundle of filaments 28 which is being advanced by means of drafting or tensioning means 30 at a second region. According to this invention, the web 24 is drafted into a yarn at a ratio of approximately 2.4:1. That is, the length of the yarn 60 is approximately 2.4 times that of the associated unit of web 24.
Drafting means 30 is comprised of a housing 32 and a plurality of driven, rotatable pull rolls which apply tension to bundle 28 sufficient to advance and draft web 24 and/or bundle 28 into yarn 60.
As shown in FIGS. 1 and 2, second pull roll 34 is rotatably journaled in housing 32 as is third pull roll 35. Pull rolls 34 and 35 each have a fixed axis of rotation and are spaced from each other. First, rotatable pull roll 36 is adapated for relative lateral movement with respect to pull rolls 34 and 35.
During start-up, moveable pull roll 36 is moved out of engagement with pull rolls 34 and 35 to facilitate the threading of bundle 28 through the drafting means 30. Once the operator is satisfied that the system is ready to begin production, the moveable pull roll 36 is moved to engage pull rolls 34 and 35 with bundle 28 therebetween. Pull rolls 34, 35, and 36 are synchronously driven at a predetermined rate or speed sufficient to draft the filaments into the yarn desired.
Pull rolls 34, 35, and 36 are driven by means of motor 38 which is connected to the first dual pulley 40 by a first drive belt 39. Second belt 42 engages first dual pulley 40 and pulleys 43 of pull rolls 34 and 35, as well as second dual pulley 46. Pulleys 43 are rotatably journaled on shafts 44 which can be suitably mounted on housing 32.
Third drive belt 48 engages second dual pulley 46 and third dual pulley 50. Third dual pulley 50 is rotatably journaled on shaft 51 which is mounted on housing 32.
Arm 52 is rotatably journaled on shaft 51, and third pull roll 36 is rotatably journaled at the opposite end of arm 52 on shaft 44 which is mounted on arm 52. Fourth drive belt 55 engages pulley 43 of pull roll 36 and third dual pulley 50 to drive pull rolls 34, 35, and 36 at substantially the same speed.
Arm 52 is adapted to pivot about shaft 51 to move third pull roll 36 along an arcuate path. However, it is to be understood that pull roll 36 need not be restricted to moving only along an arcuate path.
Extension 53 is suitably coupled with motive means, such as a dual acting air cylinder, 57 to pivot or move pull roll 36 at predetermined times. The body of cylinder 57 can be suitably attached to housing 32. Air cylinder 57 is connected to a suitable supply of pressurized air (not shown) which can be controlled by conventional valve means by the operator to raise and lower moveable pull roll 36 as desired.
Subsequent to drafting means 30, yarn 60 passes over guide roll 64 and under tension arm 67 of winder 66 to be wound as a package 70 upon collet 68 at a third region spaced from drafting means 30. Winder 66 can be of the commercially available type, such as a Leesona 959 winder.
According to the principles of this invention, staple yarns of glass fibers can be produced at rates of about 25 pounds per hour at velocities of about 200 to 1,000 feet per minute.
It is apparent within the scope of the invention, modifications and different arrangements can be made other than as herein disclosed. The present disclosures are merely illustrative, with the invention comprehending all variations thereof. | Method and apparatus are provided for producing a yarn comprising; supplying a web of staple fibers to a first region; forming said web into a bundle at a zone intermediate said first region and an after-defined second region; tensioning said fibers at a second region to draft said bundle into a yarn advancing at a predetermined rate; and collecting said yarn at a third region at a rate substantially equal to said predetermined rate of advancement. | 3 |
FIELD OF THE INVENTION
The invention relates to a cleaning machine for textile fibers transported in a current of delivery air, the machine including a horizontal opening roller fitted with beater elements and below the underside of the roller, adjustable grate bars are arranged which are adjustable in their setting angle.
BACKGROUND
A cleaning machine of the above type is known and obtainable on the market and it is also known that the grate bars, as a rule profile rods, with the object of altering their setting angle, are made capable of swiveling on their longitudinal parallel axes in order to make the adjustment to different fiber materials possible. This known adjustment possibility, however, only permits the same adjustment for all grate bars, that is, in a relatively limited range.
SUMMARY OF THE INVENTION
An object of the invention is to provide a cleaning machine of the above type but in which an improved adjustment is possible to suit different textile fiber materials in a wider range of characteristics.
The above object can be fulfilled according to the invention by providing at least some of the grate bars such that they are adjustable with respect to the roller, in order to alter the clearance between the grate bars and the roller.
Another object of the invention is to provide an arrangement wherein the grate bars can swivel to different amounts with respect to each other on an axis parallel to their own longitudinal axis.
A further object of the invention is to provide an arrangement wherein the two axial ends of the grate bars can be adjusted to different distances with reference to the opening roller.
According to the present invention, it is possible to provide a group of grate bars lying adjacent to each other in the circumferential direction of the roller, the grate bars at one end of the group (viewed in the circumferential direction) being adjustable to different distances with reference to the roller and if necessary, swivel differently compared to the grate bars at the other end of the group.
BRIEF DESCRIPTION OF THE DRAWINGS
An example of the cleaning machine according to the invention is explained in more detail with the aid of the accompanying drawings, in which:
FIG. 1 shows a schematic vertical section through a cleaning machine for textile fibers according to the invention;
FIG. 2 shows a vertical section through the machine shown in FIG. 1;
FIG. 3 shows a partial lateral view to a larger scale of the machine shown in FIG. 2, without the outer casing wall; and
FIG. 4 shows a detail of the machine shown in FIG. 1, but in an enlarged representation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The cleaning machine shown in FIGS. 1-4 has an opening roller 2 fitted with beater rods 1 and is supported to rotate on a horizontal axis in a casing 3. In operation, the opening roller 2 is rotated in the direction of the arrow according to FIG. 1 by a driving motor which is not shown. Above the upper side of the opening roller 2, the casing 3 has an inlet 4 and an outlet 5 for textile fibers in the form of flocks transported in a current of delivery air. The inlet 4 is arranged at one end of the roller 2, whilst the outlet 5 is arranged at the other end of the roller 2. On the upper side of the opening roller 2 and between the inlet 4 and the outlet 5, three deflectors 6, 7, 8 are arranged inclined to the axis of the roller so as to define two transfer chambers between the upper side of the roller 2 and the upper wall of the casing 3.
Bar grates are arranged below the underside of the opening roller 2 and include grate bars which are approximately parallel to the roller. Preferably, as shown in FIG. 1, there are two groups of grate bars 9 and 10 arranged one behind the other in the circumferential direction of the opening roller. The first and the last grate bar of the group 9 are also shown in FIG. 2, from which it can further be seen that, a third group of grate bars 11 is arranged in the direction of the axis of the roller 2, adjacent to the group of grate bars 9. In the same way, a fourth group Z of grate bars (not shown) lies in the direction of the axis of the roller 2, adjacent to the group of grate bars 10.
In operation, textile fibers to be cleaned and opened are conveyed through the inlet 4 in a current of delivery air. The delivery air with the fiber flocks next streams substantially around the underside of the rotating opening roller 2, then through the transfer chamber between the deflectors 6 and 7, which moves the air further in the axial direction of the opening roller 2, then again around the underside of the roller, then through the transfer chamber between the deflectors 7 and 8, and again around the underside of the roller, in order to leave the machine finally through the outlet 5. The fiber flocks are processed by the beater rods 1 with the circulation around the underside of the roller 2 and progressively opened during a stroking and beating process, so that impurities are separated through the four groups of grate bars 9, 10, 11, Z and sucked from the space under the grate bars by a suction device, not shown, which does not affect the current of delivery air.
The four groups of grate bars 9, 10, 11, Z (the group which is not shown), are preferably adjustable independently of each other with reference to the opening roller 2, respectively, with reference to the frame of the machine, in order to alter the clearance between the grate bars and the roller 2.
Preferably, in each of the four groups 9, 10, 11, Z, both axial ends of the grate bars are independently adjustable with reference to distances between the grate bars and the roller 2, and further, the two circumferential ends of each of the groups 9, 10, 11, Z extending in the circumferential direction of the roller 2 can both be likewise independently adjusted. For this purpose, a common, adjustable clearance controlling element is in contact with each axial end of each group of grate bars 9, 10, 11, Z, that is, both ends of the grate bars of each group are each in contact with a respective common, adjustable clearance controlling element.
As shown in FIG. 2, the right hand axial ends of the grate bars 9 are in contact with a clearance control template 12, whilst the left hand axial ends of the grate bars 9 are in contact with a clearance control template 13. The right hand axial ends of the grate bars 11 are in contact with a clearance control template 14, and the left hand axial ends of the grate bars 11 are in contact with a clearance control template 15. The clearance control template 12 and a further clearance control template 16, which is allocated to the group of grate bars 10 (FIG. 1), are also shown in FIG. 3.
The axial ends 9.1 of the grate bars 9 rest in holes in the template 12. Preferably, these holes, as indicated at the end 9.1 of the circumferentially outermost grate bar 9, are oblong holes, which are extended in the direction of the roller 2 and the ends 9.1 are further guided in radially extended oblong holes (not shown) and guided in a bearing plate 17 (FIG. 2) of the machine frame. The template 12 is variously adjustable with reference to the machine frame through two adjustment devices which can be activated independently of each other, which reach to the template in the area of the ends 9.1 of the circumferentially innermost and the outermost grate bars 9, respectively. These adjustable devices can be of any desired type.
For example, as shown in FIG. 3, each of the adjustment devices can include a doubled armed lever, which can be swivelled on a rigid (stationary) axis 18 or 19, respectively, on the machine frame. One arm 20 and 21, respectively, of each of these levers reaches in each case into a recess in the template 12, whilst the other arm, 22 and 23, respectively, of each of these levers is fitted to one end of a Bowden control cable 24 and 25, respectively, the other end of which is actuated by a linear motor 26 and 27, respectively, arranged rigidly on the frame. A conduit 28 and 29, respectively, of the Bowden control cable is anchored at both ends on a fastener 30 mounted rigidly on the frame.
A movable template, formed like the template 12, is allocated to each end of the groups of grate bars 9, 10, 11, Z.
The grate bars, which are as a rule, formed approximately as triangular profiles, for example, are in the cleaning machine according to the invention, preferably each arranged to swivel on an axis parallel to their own longitudinal axis, so that a setting angle beta (β), as shown in FIG. 4, of the grate bars can be altered with reference to the current of delivery air passing around the opening roller 2. A swivel device can be allocated to each of the four groups of grate bars 9, 10, 11, Z and this can preferably be so developed that it can swivel each of the grate bars 9, 10, 11, Z to a different extent at locations spaced apart in the circumferential direction of the roller 2.
The setting angle β of the grate bars can increase or decrease gradually within the group in the circumferential direction of the roller 2. In the example shown, the grate bars of every group 9, 10, 11, Z each have a crank arm 40 on one end which is swivelled on a common angle control element. In this way, the crank arms 40 of the group of grate bars 9 according to FIG. 2 are linked on an angle control template 41 and the crank arms 40 of the group of grate bars 11 are swivelled on an angle control template 42. The template 41 and a further angle control template 43, which is allocated to the group of grate bars 10 (FIG. 1) are also shown in FIG. 3, in which the crank arms associated with grate bars 10 are designated with 40.1. For the sake of simplicity, only one crank arm 40 and 40.1, respectively, on one end 9.1 or 10.1, respectively, of the circumferentially outermost grate bar of the group of grate bars 9 or 10, respectively, in FIG. 3 is represented by a dash dotted line.
The template 41 and 43, respectively, carries a row of pins 44, which supports the crank arms 40 and 40.1, respectively, of the group of grate bars 9 and 10, respectively. The template 41 is adjustable with reference to the clearance control template 12 through two adjustment devices which can be activated independently of each other, which reach to the template 41. These adjustable devices can also be of any desired type. For instance, in the example shown, each again has a doubled armed lever, which can be swivelled on a rigid (stationary) axis 45 and 46, respectively, carried on the template 12. One arm 47 and 48, respectively, of each of these levers reaches to an opening in the template 41, whilst on the other arm 49 and 50, respectively, of each of these levers, a Bowden control cable 51 and 52, respectively, is fitted, the other end of which is actuated by a linear motor 53 and 54, respectively, arranged rigidly on the frame. The conduits 55 and 56, respectively, of the Bowden control cables are anchored adjacent to the linear motor 53 and 54, respectively, on a fastener 57 or 58, respectively, and at the other end on a fastener 59 and 60, respectively, on the template 12.
FIG. 4 shows a single grate bar of the groups 9, 10, 11, Z to a larger scale, with a free area 70, a setting area 71, and a wedge angle gamma (γ) which is formed by the free area 70 and the setting area 71, the section line of which forms further a cutting edge 72. Further, the setting angle beta (β) previously mentioned is formed between the setting area 71 and an imaginary plane 73 which contains the cutting edge 72 and the axis of the roller 2 (not shown), whilst the free angle alpha (α) is formed between the free area 70 and an imaginary plane 74 containing the cutting edge 72. Thereby, the tangential plane 74 forms a right angle delta (δ) with the radial plane 73.
The free angle alpha (α) is adjustable between zero and 30°. The setting angle beta (β) is selected empirically according to the product at the time. The setting angle beta (β) can have a negative or positive value, as can be seen from FIG. 4, according to the selection of the wedge angle gamma (γ) in connection with the selection of the free angle alpha (α). However, a positive angle is preferable.
The adjustment possibilities previously mentioned regarding the clearances of the grate bars 69 to the roller 2 and the setting angles beta, bring the advantage that the clearances and setting angles can be differently selected per grate bar group 9, 10, 11, Z and within the group, so that a greater variation with reference to the technological effect, that is, cleaning effect, fiber protection, prevention of new formation etc, can be achieved according to the product processed.
When a machine is selected which does not operate as shown in FIG. 2 with four grate groups but simply with two, then it is possible, with continuous throughgoing grate bars and the use of the clearance control templates analogous to 12 and 15, to select the clearances to the roller 2 differently on both ends of the grate bars 2, seen in the axial direction of the roller, which likewise makes the technological effect variable in the direction of the axis.
Finally, it has still to be stated that a cover 80 covers the clearance control templates 13 and 14, in the mid-area of the machine, as shown in FIG. 2, as well as directly left, seen from FIG. 2, the control template 14 and, arranged on the right of the control template 13, the hearing plates 81 or 82, respectively, accepting the grate bars cover in such a way that no air-flocks mixture can fall between the bearing plates 81 and 82.
With the arrangement of the present invention, a number of adjustments with respect to the individual groups of bars are possible. For instance, a first distance between a first group of bars 9 and the roller 2 can be different than a second distance between a second group of bars 10 and the roller 2. Likewise, a third distance between a third group of bars 11 and the roller 2 can be different than the first and/or the second distances. Similarly, a fourth distance between a fourth group of bars Z and the roller 2 can be different from the first and/or second and/or third distances.
Another possibility with the arrangement according to the present invention is that the distances between the roller 2 and various bars of a particular group of bars 9, 10, 11 or Z can be equal to each other or be different from each other. For instance, with respect to the direction of travel of the delivery air around the roller 2, the upstream bars of an individual group of bars can be located closer to or further away from the roller 2 than downstream bars of the same group.
Another possibility with the arrangement according to the present invention is that the setting angle of the bars of one group of bars can be made different from the setting angle of a different group of bars. For instance, the group of bars 9 can have a setting angle which differs from the circumferentially adjacent group of bars 10 and/or the group of bars 9 can have a setting angle which differs from the axially adjacent group of bars 11. Likewise, the group of bars 9 can have a setting angle which differs from the group of bars Z circumferentially adjacent to the group of bars 11. In the same manner, the group of bars 10 can have a setting angle which differs from that of the group of bars 11 and/or the group of bars Z and the group of bars 11 can have a setting angle which differs from that of the group of bars Z.
In the case where the machine of the present invention includes two groups of grate bars, rather than four groups of grate bars, the provision of clearance control templates at each axial end of each group of bars allows the clearance between the bars and the roller 2 to be different at each axial end of the roller. For instance, if the group of bars 9 and the group of bars 11 are combined into a single group of bars and the axial ends of the bars are supported by the clearance control templates 12 and 15, respectively, the portions of the bars located closer to the template 12 can be located closer to or further from the roller 2 than the portions of the bars located closer to the template 15.
While the invention has been described with reference to the foregoing embodiments, changes and modifications may be made thereto which fall within the scope of the appended claims. | A machine for cleaning textile fibres including a casing, a horizontal opening roller rotatably mounted in the casing, the roller being fitted with beater elements and at least one group of grate bars arranged below the underside and approximately parallel to the opening roller. Textile fibres in the form of flocks are fed to the opening roller in a current of delivery air through an inlet located above and at one end of the opening roller. An outlet for removing the delivery air is arranged above and at the other end of the opening roller. A clearance between the grate bars and the opening roller is adjustable. Therewith, the machine can be optimally suited to the type of textile fibre material to be cleaned. The grate bars can also be further adjustable on a axis parallel to their own longitudinal axis, so that the setting angle of the grate bars, with reference to the current of delivery air, can also be adapted to the type of the textile fibre material. | 3 |
BACKGROUND OF THE INVENTION
1. Field of Invention
This invention relates to safety belt buckles for passengers in vehicles such as automobiles, and more particularly to improved means for housing and facilitating the operation of the components of the buckle.
2. Description of the Prior Art
Safety belt buckles have been developed in order to reduce the number of fatalities and serious injuries resulting from motor vehicle accidents. Most of these buckles include, as major components, a housing connected to a seat belt or strap anchored to the vehicle body and a latching mechanism adapted to coact with the tongue of another seat belt similarly secured to the vehicle. One of the problems encountered with such buckles is the difficulty of inserting the tongue into the housing and removing it therefrom. The magnitude of the biasing force exerted on the latching mechanism to prevent premature ejection of the tongue during collision conditions, provides for rough entry of the tongue upon insertion thereof into the housing and hinders the release effort, or force required to remove the tongue from the housing during normal operation of the vehicle. Another problem with such buckles is the relatively large size, weight and cost thereof. The present invention provides a means whereby the aforesaid problems are overcome.
SUMMARY OF THE INVENTION
In accordance with the present invention a safety belt buckle is provided that is compact, light-weight and strong, and which has plural features that virtually eliminate problems such as rough entry, premature ejection, high fastening and release effort and the like. The buckle has a housing having an opening therein and provided with a cavity extending from the opening to a wall of the housing opposite the opening. An inlet means of the housing communicates with the cavity for receiving the tongue of a seat belt. A connecting means is provided for connecting the housing to an anchorage point on the vehicle. The buckle has a latching means for engaging the seat belt tongue. A first biasing means connected to said housing biases the latching means into engagement with the tongue. The housing has a locking means slidably mounted thereon. A second biasing means connected to the housing biases the locking means into locking engagement with the latching means. A release means is slidably mounted on the housing for rotating the latching means to move the locking means out of locking engagement therewith.
The safety belt buckle of this invention has advantageous structural features. A unique coaction between the locking means and the latching means reduces the magnitude of forces applied against the latter during collision of the vehicle. The force provided by the first biasing means can be decreased, hard points within the housing cavity are removed and the release effort is reduced. Buckle holding strengths are increased and the size and weight of the buckle assembly is decreased. As a result, safety belt buckles incorporating the present invention are less expensive to produce, easier to fasten, more comfortable to wear and afford greater protection to vehicle occupants than previous safety belt buckles.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be more fully understood and further advantages will become apparent when reference is made to the following detailed description and the accompanying drawings in which:
FIG. 1 is an exploded view illustrating the safety belt buckle of this invention;
FIGS. 2 and 3 are sectional views of the buckle of FIG. 1, showing the relationship between the latching means, locking means and housing means; and
FIGS. 4 and 5 are sectional views of the buckle of FIG. 1, showing the relationship between the biasing means, latching means, locking means and housing means.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, there is illustrated one form of a safety belt buckle incorporating the present invention. Other forms of the safety belt buckle can also be used. The buckle, shown generally at 1 in the drawings, should therefore be interpreted as illustrative and not in a limiting sense. As illustrated, the buckle 1 includes a housing 10, shown generally at 10, having an opening 12 therein from which a cavity 14 extends to a wall 16 of the housing 10 opposite the opening 12. Housing 10 is provided with an inlet means 18 which communicates with the cavity 14 for receiving the tongue 20 of a seat belt. The housing 10 has a connecting means 22 for connecting the housing through a connector element 23, seat belt (not shown) or the like, to an anchorage point on the vehicle (not shown). A latching means, shown generally at 24, is provided for engaging the seat belt tongue 20. The buckle 1 has a first biasing means 26 connected to housing means 10 for biasing latching means 24 into engagement with tongue 20. Slidably mounted on housing 10 is a locking means, shown generally at 28. A second biasing means 30 connected to the housing 10 biases the locking means 28 into locking engagement with the latching means 24. A release means shown generally at 32 is slidably mounted on housing 10 for rotating the latching means 24 to move the locking means 28 out of locking engagement with the latching means 24.
Housing 10 is preferably formed of a plurality of laminated plates. As shown in FIG. 1, the top and bottom plates 34 and 36, respectively, have an opening 38 in the central portion thereof and the center plate 40 has an opening 42 extending from an edge 44 of the plate 40 into the central portion thereof, the opening 44 forming part of the inlet means 18. The center plate 40 has a guide means, generally indicated at 46, extending from the interior of the cavity to a point of termination 48 on the exterior surface of the housing 10 for guiding the tongue 20 into the cavity 14 of the housing 10.
The number of laminated plates employed can vary depending on the depth of the cavity and the type of material of the plates. Typically, the top and bottom plates 34 and 36 are die stamped from metal such as steel, aluminum or the like, and the center plate is injection molded or otherwise formed of a polymeric material. Suitable polymeric materials include thermoplastic resins such as acetal homopolymer or copolymer or polycarbonate, as well as thermosetting resins such as of the phenolic type. Preferably the housing 10 is composed of at least three plates, including top center and bottom plates. Each of the plates 34, 36 and 40 are formed using conventional equipment at very low cost.
The housing 10 is assembled by sandwiching first biasing means 26 and bottom and top plates 36, 34, respectively about center plate 40 and fastening the assembled plates together by mechanical fastening means, such as rivets 48. The plates can, alternatively, be spot-welded or adhesively secured together using suitable epoxy resins or the like. Upon assembly of the plates to form an integral laminated housing unit, guide means 46 is formed by spaced apart parallel walls 50 and bell-shaped extension 52 of which center plate 40 is comprised. The wall 50 and the extension 52 cooperate with the tip 54 of the tongue 20 to provide for smooth entry of the tongue 20 into cavity 14.
Referring to FIGS. 2-3 of the drawings, a latching means 24 and locking means 28 are shown in relation to the housing 10. The latching means 24 includes a biasing means 26, a latch bar 56 having a raised portion 58 adapted to mate with opening 60 of tongue 20. As best shown in FIGS. 4-5, mating end 68 of latch bar 56 has a beveled configuration. More specifically, the mating end 68 has a bottom edge 70 engaging the mating wall 72 of tongue 20 and the top edge 74 inclined away from said mating wall, the angle of inclination, φ, from said mating wall being about 3.0° to 30.0°. Latch bar 56 has a plurality of shoulders 62 adapted to move within passages 64 of center plate 40. End portion 66 of first biasing means 26 extends into passages 64 and provides smooth, continuous surface for co-action with latch bar 56. Each of shoulders 62 has a rear face 76 having a notch 78 therein and a forward face 80 having an angular or corner-like configuration, such as corner 79.
Locking means 28 comprises a lock bar 82 having a forward face 84 adapted to mate with the notch 78 of each shoulder 62 and a rear face 86 connected to the second biasing means 30. Release means 32 can comprise a release bar 88 having a first portion 90 for engaging the forward face 84 of said lock bar and a second portion 92 provided with a step 94 adapted to engage corner 79 on the forward face 84 of each shoulder 62. The first biasing means 26 latch bar 56 lock bar 82 and release bar 88 are disposed in the cavity 14 with at least portions thereof positioned in serial overlapping relationship in the direction in which the cavity extends into the housing. Preferably, a cover 110 is disposed around the housing 10. The cover 110 comprises a single piece of light weight plastic or the like. Cover 110 does not add appreciably to the strength or weight of the assembly but functions primarily to protect the components therein against contamination and accidental damage due to tampering. The cover 110 has sufficient strength and rigidity to withstand forces generated during movement of the release means 32, and may be used to support the first biasing means 26. Preferably, the first biasing means 26 is secured to housing 10 by the mechanical fastening means and does not contact the cover 110 when the latching means 24 is in the latched and unlatched positions. In the latter embodiment, the latching means 24 is functionally independent of the cover 110 and is not disabled by damage thereto. Latching means 24, locking means 28 and release means 32 can be arranged so that the distance, x, traveled by step 94 against the bias of second biasing means 30 is greater than the depth, y, of each notch 78. This arrangement of the latching means 24, locking means 28 and release means 32 minimizes the release effort, or force required to remove tongue 20 from housing 10 during normal operation of the vehicle.
In operation, the tongue 20 is inserted into inlet means 18 and cavity 14, bringing opening 60 above raised portion 58 of latch bar 56. The first biasing means 26 moves the raised portion 58 into engagement with opening 60 of tongue 20, while second biasing means 30 moves forward face 84 of lock bar 82 into engagement with notch 78 of latch bar 56, locking tongue 20 in housing 10. Due to the beveled configuration of mating end 68 relative to mating wall 72 of tongue 20, tensile forces applied against the tongue during collision conditions are transferred, in part, to lock bar 82. The latter cooperates with latch bar 56 to hold tongue 20 securely within housing 10. Movement of the release bar 88 toward lock bar 82 brings step 94 into contact with corner 79 on forward face 80 of shoulders 62. Latch bar 56 rotates downwardly in the direction of arrow 96. Simultaneously, lock bar 82 is displaced in the direction of arrow 98 against the bias of second biasing means 30 until forward face 84 is removed from notch 78. Depression of the latch bar 56 brings raised portion 58 below opening 60 of tongue 20, with the result that the tongue 20 can be freely removed from the housing 10. In order to further facilitate removal of tongue 20 from housing 10, the buckle 1 can be provided with an ejecting means 100, shown generally at 100, including an ejecting slide 102 having a forward edge 104 adapted to engage the tip 54 of tongue 20 and a rear edge 106 connected to a third biasing means 108. The third biasing means 108 exerts a biasing force on ejecting slide 102 which is applied against tip 54 of tongue 20 to station the tongue 20 in the housing 10 and urge it therefrom upon actuation of release means 32.
Having thus described the invention in rather full detail, it will be understood that these details need not be strictly adhered to but that various changes and modifications may suggest themselves to one skilled in the art, all falling within the scope of the invention as defined by the subjoined claims. | A safety belt buckle is provided with plural locking features that increase its holding strength and decrease fastening and release effort. The buckle has a housing containing means for receiving the tongue of a seat belt. A latching means engages the tongue and cooperates with a locking means to hold it within the housing. The buckle is small, light, strong, reliable, easy to fasten and unfasten, comfortable to wear and inexpensive to produce. | 8 |
RELATED APPLICATIONS
[0001] This application claims benefit of co-owned U.S. Provisional Patent Application 61/943,301 entitled “Apparatuses, Systems, and Methods for Lubrication of Positive Displacement Machines”, filed Feb. 21, 2014, which application is incorporated herein by reference in its entireties for all useful purposes. In the event of inconsistency between anything stated in this specification and anything incorporated by reference in this specification, this specification shall govern.
FIELD OF THE INVENTION
[0002] The present invention relates to apparatus, systems, and methods of lubricating fluid displacement machines, including positive displacement machines and, in particular, rotary screw expanders via the use of non-soluble, non-miscible, and/or undissolved lubricants mixed with the fluid upon which the machine acts or is acted upon by the machine.
BACKGROUND
[0003] Machines which incorporate the flow of a fluid as a characteristic of their operation have a myriad of applications. Devices that fall within this definition are those machines which provide compression, expansion, pumping functionality and therefore encompass all manner of compressors, expanders, and pumps. Positive displacement machines are a particularly useful subset of such fluid-based machines. Configurations include linear displacement machines, reciprocating displacement machines, and rotating displacement machines. In some positive displacement machine applications, a motive force is applied to the machine and a fluid, in liquid or gaseous state, is propelled from the inlet of the machine to the outlet via displacement of the fluid by one or more movable surfaces of the machine. In other applications, the mass flow of the fluid or a physical process experienced by the fluid within the machine, such as expansion, imposes a force on one or more movable surfaces within the machine thereby causing the fluid to be propelled from the inlet to the outlet of the machine while generating a corresponding force that may be applied to perform work on an interconnected device or system. Specific lubrication requirements are dictated by the specific machine, application, and operating conditions, but machines that operate at higher pressures, at higher temperatures, with greater internal forces and external load requirements, and with components operating at greater linear or angular velocities generally impose more stringent lubrication requirements than do other machines.
[0004] Due to the forces and pressures involved, positive displacement machines are usually fabricated from hardened metal alloys for strength. Such devices require considerable lubrication to minimize friction which would otherwise generate considerable heat and wear to the machine, resulting in poor performance and premature failure. A wide variety of lubrication methods and systems exist for each the many configurations of positive displacement machines in use.
[0005] One particular class of positive displacement machine for which proper lubrication is essential is a rotational positive displacement device known as a plural screw positive displacement machine as described in U.S. Pat. No. 6,296,461. Also referred to as a “twin screw expander”, the device comprises a pair of helical-style intermeshing rotors mounted on parallel axes. Such devices may be employed in combination with a working fluid, such as a refrigerant, in systems where the refrigerant is caused to expand within the machine, thereby providing a rotational torque at the shaft output of the machine that may be coupled to perform work on another device or system, such as driving an electric generator to produce electric power. One class of systems based on this general principle are referred to as “organic Rankine cycle”, or ORC, systems, named for their use of the thermal Rankine process. A closed-loop flow of liquid working fluid, often but not necessarily a refrigerant, is heated to a gaseous or semi-gaseous state by an available and sufficient source of heat, allowed to expand in a suitable device such as a twin screw expander, cooled back into its liquid state, and then pumped and re-heated for subsequent expansion in a continuous process. In this manner, heat energy is converted into mechanical energy which may be used for any other useful purpose such as generating electric power via a generator or when coupled to one or more alternative or additional systems or devices.
[0006] Heat energy recovery systems employing the organic Rankine cycle (ORC) have been developed and employed to recapture heat from sources such as large combustion engines, boilers, and the like. One typical prior art ORC system for electric power generation from waste heat is depicted in FIG. 1 . Heat exchanger 101 receives a flow of a heat exchange medium in a closed loop system heated by energy from a large internal combustion engine at port 106 .
[0007] For example, this heat energy may be directly supplied from the combustion engine via the jacket water heated when cooling the combustion engine, or it may be coupled to the ORC system via an intermediate heat exchanger system installed proximate to the source of hot exhaust gas of one or more combustion engines. In either event, matter heated by the combustion engine or heat exchanger is pumped to port 106 or its dedicated equivalent. The heated matter flows through heat exchanger 101 and exits at port 107 after transferring a portion of its latent heat energy to the separate but thermally coupled closed loop ORC system which typically employs an organic refrigerant as a working fluid. Under pressure from the system pump 105 , the heated working fluid, predominantly in a gaseous state, is applied to the input port of expander 102 , which may be a turbomachine, a positive displacement machine of various configurations, including but not limited to a twin screw expander, or the like. Here, the heated and pressurized working fluid is allowed to expand within the machine and such expansion produces rotational kinetic energy that is operatively coupled to drive electrical generator 103 and produce electric power which then may be delivered to a local isolated power grid or the commercial power grid. The expanded working fluid at the output port of the expander, which typically is a mixture of liquid and gaseous working fluid, is then delivered to condenser subsystem 104 where it is cooled until it has returned to its fully liquid state. Condenser subsystem 104 may optionally include or be operatively coupled to a receiver tank, reservoir, or equivalent vessel for storing a quantity of cooled working fluid to insure a sufficient supply for system pump 105 at all times.
[0008] ORC systems are not limited to use with combustion engines and electric generators. Any sufficient source of heat may be applied to port 106 to vaporize the ORC working fluid, including but not limited to boilers, geothermally-heated water, fluid used to cool large solar arrays, gas compressors, or other industrial processes, or the like. Likewise, the rotational kinetic energy presented by the expander in the form of mechanical power may be applied for any useful purpose in addition to, or in lieu of, driving an electric power generator. Such purposes may include, but are not limited to, driving at least one of any of a pump, a combustion engine, a fan, a turbine, a compressor, or returning power to the source of input heat.
[0009] The condenser subsystem sometimes includes an array of air-cooled or liquid-cooled radiators or another system of equivalent heat-removal performance through which the working fluid is circulated until it reaches the desired temperature and state, at which point it is applied to the input of system pump 105 . System pump 105 provides the motive force to pressurize the entire system and supply the liquid working fluid to heat exchanger 101 , where it is once again heated by the energy supplied by the input heat and experiences at least a partial phase change to its gaseous state as the organic Rankine cycle process continues. The presence of working fluid throughout the closed loop system ensures that the process is continuous as long as sufficient heat energy is present at input port 106 to provide the requisite energy to heat the working fluid to the necessary temperature. See, for example, Langson U.S. Pat. No. 7,637,108 (“Power Compounder”) which is hereby incorporated herein by reference in its entirety and for all useful purposes.
[0010] The lubrication of positive displacement machines in ORC system has been traditionally accomplished by one of several means. A separate lubrication subsystem, comprising a pump, sump, interconnected tubing or conduits, and/or other associated equipment provides the necessary recovery of lubrication oil from various points in the system and returns a continuous flow of oil to the bearings and surfaces of the machine requiring lubrication. In these prior art systems, lubrication is not intentionally combined with the working fluid, although they may flow simultaneously in certain regions of the system as separate fluids. Such lubrication subsystems increase the number of components required to support the machine's proper operation, thereby increasing its cost and decreasing reliability since failure of the lubrication subsystem will render the machine inoperable.
[0011] Another method of positive displacement machine lubrication described as particularly well-suited for twin screw expanders in ORC systems is taught by Smith in U.S. Pat. No. 8,215,114. Here, a lubricant that is soluble or miscible in the liquid phase of the working fluid is directly mixed with said working fluid and flows, as a homogenous, uniform, and stable mixture, throughout the ORC system. It is taught by Smith that when heated, the liquid working fluid vaporizes (evaporates), leaving a higher concentration of lubricant in liquid form which is ostensibly sufficient to provide the necessary lubrication for the machine's operation. In particular, this patent teaches that when the mixture of working fluid and lubricant is injected at a bearing location associated with a rotary element of the expander, the heat generated by said bearing evaporates the liquid phase of the working fluid to leave sufficient concentrated lubricant in the bearing for adequate lubrication. This system and method provides the distinct advantage of not requiring a separate lubrication subsystem, thereby providing increased reliability and a lower manufacturing cost. However, this method and does not address situations where the bearing heat may be insufficient to evaporate the working fluid.
[0012] As lubricants do not exhibit thermal energy transfer properties similar to those of refrigerants, a mixture of working fluid and lubricant will impose some degradation in ORC performance when compared to that of a lubricant-free system. For that reason, a relatively low concentration (not more than 5% by weight) of lubricant is prescribed within the working fluid mixture so as not to excessively degrade the operational performance of the ORC system, which is largely dependent on the unique pressure and temperature vaporization characteristics of each particular working fluid. It is important to note that as a homogenous, miscible solution, this concentration of lubricant is uniformly present throughout the entire system at all times. At that concentration of lubricant, experimental observations have disclosed that in certain applications, physical degradation of twin screw expander bearings leading to failure occurs at bearing operating temperatures well below those required for vaporization of the working fluid as taught by Smith. Put another way, the bearings are seen to approach failure from lack of proper lubrication having never reached a temperature sufficient to vaporize the working fluid and provide a sufficient concentration of lubricant as taught by Smith. With certain machines and under certain operating conditions, the technology taught by Smith does not provide adequate lubrication of the machine.
[0013] Further, the use of a relatively small proportion of a soluble or miscible lubricant mixed with a fluid flowing through a fluid displacement machine degrades the lubricity of said lubricant. At a minimum, dilution of the lubricant by the fluid decreases its effectiveness. Additionally, by combining or bonding in some manner with another substance at the molecular level, at least a portion, and perhaps most if not all, of the beneficial properties of lubricants are lost. Solving this problem by increasing the proportional component of lubricant in a system heavily reliant on the thermal properties of a working fluid, such as an ORC system, risks degrading the system's ability to efficiently convert heat energy into mechanical or electrical power. It is therefore desirable to use the minimum proportional component of lubricant necessary to ensure proper lubrication. The trade-off between lubrication and system performance degradation represents a compromise not resolvable in the known art.
[0014] Therefore, the problem of properly lubricating fluid displacement machines, and in particular certain types of rotational positive displacement machines requiring highly reliable and effective means of lubrication, cannot be solved by present technology. Systems and methods which solve this problem would advance the present knowledge and be immediately useful in the art. The apparatus, systems, and methods disclosed herein provide technology for lubrication in fluid displacement machines of all types that does not require a separate lubrication subsystem and provides for full lubrication in systems that generate insufficient bearing heat to vaporize working fluid mixed with lubricant(s) that are soluble or miscible in the liquid phase of that working fluid as taught in the prior art.
BRIEF SUMMARY OF SOME ASPECTS OF THE INVENTION
[0015] Apparatuses, systems, and methods are provided for the lubrication of fluid displacement machines, and in particular positive displacement machines such as twin screw expanders utilized in organic Rankine cycle (ORC) systems. Such lubrication systems and methods require neither a separate lubrication subsystem nor sufficient bearing heat for vaporization of working fluid mixed with a lubricant that is soluble or miscible in the liquid phase of the working fluid. In lieu of a soluble or miscible lubricant, this invention utilizes one or a combination of more than one wholly or substantially non-soluble or immiscible lubricant(s) mixed with the working fluid with special apparatus and methods to provide highly effective and reliable lubrication for a wide range of fluid displacement machines.
[0016] While the use of apparatuses, systems, and methods for non-soluble or immiscible lubrication of fluid displacement machines is particularly well-suited for use with positive displacement machines such as screw expanders, the disclosure herein is known to be useful with a wide variety of other machines as well. It should be understood that the use of the word “machine” herein is intended to apply to any and all machines, singularly or in combination with other machine(s), that may benefit from lubrication and through which a fluid passes, either as a driven media or as a media providing a driving force to the machine due to mass flow or any physical or state changes that may occur as the fluid passes through the machine. The addition of one or more non-soluble, immiscible lubricants to the fluid passing through any such machine to provide for its lubrication is within the scope of this invention and therefore envisioned by this disclosure.
[0017] In some embodiments, one or more lubricants that are not substantially soluble or miscible in the liquid phase of the working fluid are mixed in certain prescribed proportion with a working fluid for use in an ORC system. Such mixture of working fluid (“WF”) and one or more non-soluble, immiscible lubricant(s) (“NSIL”) comprises a non-homogenous colloidal WF/NSIL mixture of inherently unstable composition over time and that tends toward separation. During the normal operation of the system comprising the machine, the NSIL component of the colloidal WF/NSIL mixture is evenly dispersed at locations of interest in the system, At rest for a sufficient time, such colloidal mixture may achieve partial or nearly complete self-separation of the WF and NSIL components such that the NSIL component is no longer dispersed within the WF/NSIL mixture. Only traces of each component may by present in the separated strata of the other(s).
[0018] In some embodiments, the NSIL in the WF/NSIL mixture coats and lubricates the metallic surfaces of the machine and incidentally accumulates in the bearings and at other points requiring lubrication without the need for direct injection.
[0019] In some embodiments, the WF/NSIL mixture is directly supplied under positive pressure to one or more points in the system requiring lubrication with such lubrication provided by the NSIL component of the mixture. In particular, a lubrication line may be run from an extraction point in the system where a supply of the WF/NSIL mixture is available at a preferred temperature to communicate a portion of said mixture to the lubrication points. In some embodiments, cooled WF/NSIL mixture is extracted at the output of a system pump and operatively communicated to the housings of one or more bearings, the bearings directly, or other locations in the machine requiring lubrication. The NSIL present in the WF/NSIL mixture coats the bearings to provide exemplary lubrication as a result of the high affinity between the NSIL and metallic surfaces.
[0020] In some embodiments, WF/NSIL mixture is extracted from one or more other source points within the system and provided to the desired points of lubrication. If the pressure differential between the source of the WF/NSIL mixture and the lubrication input ports at the bearing housings and/or other points of lubrication is insufficient to provide the necessary flow, a supplemental lubrication pump may be employed to achieve reliable and controllable flow. In some ORC embodiments, expanded WF/NSIL mixture taken from the outlet of positive displacement machine 102 may be captured and immediately pumped back to the machine as necessary for lubrication. This WF/NSIL mixture may provide a source of lubrication closest to the operating temperature of the lubricated machine in circumstances when such temperature matching is optimal for the particular application. In a similar manner, WF/NSIL mixture may be obtained from any more desirable location within the system. However, it is generally preferred that the WF/NSIL mixture used for lubrication has a significant liquid component. Extracting wholly or substantially vaporized pre-expansion WF/NSIL mixture from the output of ORC heat exchanger 101 , for example, may not be well-suited for lubrication of a twin screw expander in some ORC embodiments due to its high temperature and potential extraction difficulties at the point of greatest system enthalpy. However, different types of machines used in applications other than ORCs may have a myriad of preferable sources from which the lubricating WF/NSIL mixture may be extracted and no single solution will necessarily be optimal for every conceivable application.
[0021] In some embodiments, WF/NSIL mixture may be extracted from one or more positions within a fluid reservoir or receiver tank and supplied, via a supplemental lubrication pump, to the desired points of lubrication. Due to the tendency of the colloidal WF/NSIL mixture to separate as described elsewhere herein, the position within the reservoir or receiver tank at which a portion of the mixture is extracted for lubrication purposes will largely determine the relative proportion of working fluid to NSIL. Also as described in greater detail elsewhere herein, the colloidal mixture will tend to separate into layers, or strata, with indefinite boundaries but with varied compositions of the mixture that vary from comprising predominantly working fluid to predominantly NSIL. When extracted via a supplemental lubrication pump supplying sufficient motive force to extract the desired mixture and communicate it to the desired points of lubrication, the mixture me be extracted from any desired point within the tank. This affords the system designer the ability to select the precise location of extraction, and therefore the precise composition of WF/NSIL mixture, to achieve the desired lubrication results. In some embodiments, the point of extraction of the WF/NSIL mixture for lubrication purposes may be variable, via a moveable inlet port or similar means, and controlled either manually or via a microprocessor-based control system further comprising sensors capable of determining the composition of the WF/NSIL mixture and adjusting the position accordingly. In some embodiments, multiple extraction locations may be used, with the WF/NSIL mixture extracted from the location most favorable at any particular time for lubrication purposes. Similarly, this embodiment may comprise either manual control or be operated via a microprocessor-based control system further comprising sensors responsive to the composition of the WF/NSIL mixture. A combination of multiple extraction locations and movable inlet ports may be utilized in other embodiments.
[0022] In some embodiments, WF/NSIL mixture may be extracted by use of one or more skimmer(s) disposed at fluid reservoirs or receiver tanks. As discussed elsewhere, when the NSIL has a lower specific gravity than the fluid comprising the balance of the WF/NSIL mixture, separation via gravitational force provides NSIL-enriched fluid in the upper strata of the tank. Use of a skimmer to extract a portion of the WF/NSIL mixture from that uppermost strata would advantageously yield the portion of the mixture richest in lubricant for injection at the desired lubrication points.
[0023] In some embodiments, no agents are present within the colloidal WF/NSIL mixture to increase its compositional stability. In some embodiments, one or more agent(s), such as emulsifying agent(s), are present in the WF/NSIL mixture to increase the stability of the WF/NSIL mixture over time and therefore reduce its tendency to separate due to gravity or other internal or external stimuli.
[0024] In some embodiments, the WF/NSIL mixture varies in the relative proportion of non-soluble immiscible lubricant and working fluid as a function of position in the system. In other words, samples of the WF/NSIL mixture extracted at various points throughout the closed loop within which the WF/NSIL mixture circulates may contain non-identical concentrations of NSIL. Within segments of the closed-loop path experiencing reduced fluid movement, such as in certain portions of the system where condensed WF/NSIL mixture is allowed to accumulate, observed separation of the WF/NSIL mixture will be the greatest and relative proportions of each component are likely to vary greatly with relatively minor variations in sampling position. Within other segments of the system where fluid movement is the greatest or that are proximate to points where mechanical agitation of the WF/NSIL mixture is occurring, the relative proportion of each component of the WF/NSIL mixture will be more uniform as a function of minor variations in the sampling position.
[0025] In some embodiments, the relative proportions of non-soluble immiscible lubricant and working fluid within the WF/NSIL mixture as measured at a fixed location in the closed-loop path within which the mixture is circulating may vary as a function of time. In this embodiment, repeated measurements of NSIL concentration taken at a single location over a period of time during operation of the ORC system will vary as a function of time until a state of equilibrium has been achieved. This is particularly true during the initial start-up of an ORC system previously at rest for any appreciable period. As the colloidal WF/NSIL mixture naturally tends toward separation when said mixture is at rest and is not being agitated by one or more internal or external force(s), a re-started system may begin operation with a highly non-uniform distribution of working fluid and non-soluble immiscible lubricant. In some embodiments, a disproportionately large concentration of NSIL may collect at certain strata within the reservoir or receiver tank used to store cooled working fluid or elsewhere within an idle system. Similar to the disclosure above, depending upon the position from which fluid is drawn from said receiver tank and the presence or lack of agitation applied to the WF/NSIL mixture, the initial draw of WF/NSIL mixture from said receiver tank may be highly enriched with or essentially depleted of non-soluble immiscible lubricant since the NSIL component of the WF/NSIL mixture is not evenly dispersed at points in the system where such dispersion is important to system operation. As the system continues to operate, the distribution of NSIL throughout the system will begin to approach the normally-expected distribution of NSIL mixture at each point in the system, eventually reaching the proper concentration of NSIL under essentially steady-state operating conditions, at which point such concentration may still vary with position as described with respect to a previous embodiment. The state of operation in which the optimal dispersion of NSIL within the WF/NSIL mixture is achieved for steady-state operation may be referred to as lubrication equilibrium.
[0026] In some embodiments, a fluid bypass circuit comprising a valve may be employed around the machine to prevent its operation during period when the WF/NSIL mixture has not yet reached the state of lubrication equilibrium. During such periods, insufficient lubrication for the rotating surfaces and bearings of the machine would likely cause damage to or failure of the machine were it operate, so the initial flow of WF/NSIL is routed around, rather than through, the machine to prevent the machine's operation under conditions of unfavorable lubricity. Once the WF/NSIL mixture has reached proper lubrication equilibrium, the bypass valve may be closed, blocking the bypass flow and allowing the properly reconstituted WF/NSIL mixture to flow through the machine as it begins to operate. Control of the bypass valve may be accomplished either by manual methods or by a microprocessor-based control system used to monitor and control other aspects of the ORC system's operation.
[0027] In some embodiments, the localized homogeneity of the WF/NSIL mixture is relatively uniform at all points in the closed-loop circulation path between the outlet of a system pump and the outlet of the machine once the WF/NSIL mixture has attained lubrication equilibrium. Within this segment of the closed-loop ORC system, the circulating WF/NSIL mixture driven by positive pressure from the system pump is subject to an increase in enthalpy from the transfer of heat energy from a external source via one or more heat exchangers and subsequent expansion in the positive displacement machine. All of the WF/NSIL mixture present at the pump output appears directly at the output of the machine without any change in overall composition. With an active flow and no appreciable reservoirs of WF/NSIL mixture in this segment of the WF/NSIL mixture closed-loop circuit, there is nothing to add to or subtract from the original WF/NSIL mixture flow and therefore the overall concentration of NSIL in the WF/NSIL mixture flow must be uniform on the whole. These embodiments are particularly applicable in systems with predominantly liquid, minimally vaporized working fluid.
[0028] In some embodiments, the localized homogeneity of the WF/NSIL mixture is not uniform at all points in the closed-loop circulation path between the outlet of a system pump and the outlet of the machine once the WF/NSIL mixture has attained lubrication equilibrium. Even though there are no inlets or outlets for the mixture between these two points, the fact that the working fluid is at least partially vaporized by the heat supplied to the ORC system in these embodiments while the lubricant is not vaporized will result in a mixture comprised of liquid NSIL, vaporized working fluid, and possibly liquid (non-vaporized) working fluid. Under such conditions, the relative proportion of NSIL in any remaining non-vaporized liquid mixture will understandably higher than if the entire working fluid at that point were still in its liquid state, as it exists at the outlet of the system pump prior to vaporization in the heat exchanger.
[0029] In some embodiments, the total non-homogenous WF/NSIL mixture within the entire closed-loop ORC system, including lubricant present on internal surfaces of the system and pooled in higher concentration in fluid reservoirs or receiver tanks, comprises between 3% and 8% NSIL by mass. Preferably, the NSIL component is between 5% and 6% of the total WF/NSIL mixture by mass.
[0030] In some embodiments, the portion of non-homogenous WF/NSIL mixture flowing within the segment of the closed-loop circuit between the system pump output and the outlet of the machine under conditions of lubrication equilibrium is between 1% and 3% NSIL by mass. Preferably, this concentration is approximately 2% NSIL by mass. In some embodiments where a portion of the WF/NSIL mixture is extracted at the output of the system pump, the concentration of NSIL in the extracted portion of the mixture is the same as the concentration of NSIL within the segment of the closed-loop circuit between the system pump output and the outlet of the machine because both mixture portions are obtained from a common source.
[0031] In some embodiments, the non-homogenous WF/NSIL mixture is subjected to intentional agitation for the purpose of temporarily increasing the homogeneity of said mixture. In some embodiments, no intentional attempt is made to increase the homogeneity of the colloidal WF/NSIL mixture and the only agitation provided is that which is incidental to the normal operation of the ORC system.
[0032] In some embodiments, the ORC system includes one or more receivers, reservoirs, or vessels in which a portion of the WF/NSIL mixture is allowed to accumulate. These locations introduce the greatest likelihood that the WF/NSIL mixture will separate as is collects there, temporarily not subjected to incidental kinetic forces experienced during fluid circulation and thermal transfer. As the colloidal WF/NSIL mixture separates, a substantial portion of the total NSIL present in the system begins to collect at the uppermost layer of the non-circulating WF/NSIL mixture where it provides no lubrication to the system. It has been found that reducing the concentration of NSIL within the system does not prevent this accumulation but instead reduces the concentration of NSIL available in the WF/NSIL mixture for lubrication purposes, to the detriment of system operation.
[0033] In some embodiments, the ORC system does not include any receiver(s), reservoirs, or other vessels that permit WF/NSIL mixture to accumulate. In this embodiment, there is no accumulation of NSIL in the system at locations where it provides no lubricating function and the total amount of NSIL added to the system may be reduced without adversely affecting the concentration of NSIL where necessary for lubrication.
[0034] By way of example and not limitation, implementations of these and other embodiments of the invention may include one or more of the features described in detail below and elsewhere herein.
[0035] The machine requiring lubrication may be any fluid displacement machine suitable for use in the preferred system, whether for expansion, compression, pumping, or other purposes. The machine may impose a force on the fluid passing there through or the fluid may impose a force on the machine due to physical phenomena such as, but not limited to, expansion of the fluid, fluid mass flow through the machine under pressure, or in any other manner. In some embodiments, the machine is a positive displacement machine such as a twin screw expander particularly suitable for use in ORC heat recovery systems. In some embodiments, the machine may be any manner of rotational, reciprocating, linear, or non-linear machine suitable for use in the desired application which requires lubrication and which is also suitable for use with a working fluid in liquid, gaseous, or mixed liquid/gaseous phases.
[0036] The working fluid may be an organic refrigerant of the hydrofluorocarbon (HFC) class such as R-245fa, commercially known as Genetron® and manufactured by Honeywell. However, any organic refrigerant including but not limited to R-123, R-134A, R-22, and the like, as well as any other suitable hydrocarbons or other fluids, may be employed in other embodiments. The working fluid may also be water or any other substance suitable for the intended purpose of the machine and the system.
[0037] In some embodiments, the NSIL may comprise mineral oil or one or more of any other suitable liquid lubricant(s) that are neither soluble nor miscible in the liquid phase of the working fluid. Mineral oil is not soluble or miscible in HFC refrigerants such as R-245fa and its use therewith is compatible with this disclosure. One such type of mineral oil demonstrated to be sufficiently non-soluble and immiscible with R-245fa is manufactured by Nu-Calgon of St. Louis, Mo. and available in several viscosities (C-3s, C-4s, and C-5s) for different applications. However, mineral oil is known to be miscible with other refrigerants, including those comprising chlorinated compounds such as CFCs or HCFCs, so a lubricant other than mineral oil would be required for use with such refrigerants to comport with the teaching in this disclosure. In some embodiments, the NSIL may comprise synthetic replacements for mineral oil or other lubricants that are similarly neither soluble nor miscible in the liquid phase of the chosen working fluid. One such synthetic alternative for mineral oil is the family of alkylbenzene oil compounds manufactured by Nu-Calgon under the product name Zerol®. As with mineral oil, this product is known to be miscible with CFC and HCFC refrigerants but neither soluble nor miscible with HFC refrigerants such as R-245fa, rendering it suitable for use as an NSIL according to this disclosure with HFC refrigerants but not with CFC or HFC refrigerants. Again, the particular formulation of NSIL used in accordance with this disclosure is critically dependent upon the type and characteristics of the working fluid as well as the operating temperatures and pressures of the system since the miscibility of lubricants is partially dependent upon its temperature. In some embodiments, the NSIL may comprise a solid lubricant additive compound held in colloidal suspension in the working fluid in combination with, or in lieu of, one or more non-soluble immiscible or other liquid lubricant(s). Such solid lubricant additives may be of the type manufactured under the Acheson brand name and available from Henkel Corporation in Rocky Hill, Conn.
[0038] In some embodiments, the system further comprises one or more filters through which the WF/NSIL mixture extracted for injection at desired lubrication points, such as bearings, is passed to remove impurities, including but not limited to moisture and particulate contaminants, that may accumulate over periods of extended use. Such impurities may degrade the lubricity of the NSIL and generally be harmful to bearing life, particularly when applied to bearings under a continuous and considerable load. Filters suitable for these embodiments may include, but are not limited to, the OF series of filters offered by the Sporlan Division of the Parker Hannifin Corporation of Washington, Mo., the HF2P series of filters offered by McMaster-Carr of Santa Fe Springs, Calif., and the HF4RL series of filters offered by HYDAC USA of Glendale Heights, Ill.
[0039] Agitation of the WF/NSIL mixture increases the homogeneity of the WF/NSIL mixture by dispersing the NSIL component within the WF/NSIL mixture, Such agitation may be provided incidental to the process of circulating said mixture through the ORC system. Kinetic energy imparted to the WF/NSIL mixture in the ORC-related acts of pumping, circulating, heating, expanding, and condensing the WF/NSIL mixture provides a “mixing” action that works to counteract the mixture's natural tendency to separate. In some embodiments, this incidental agitation is sufficient to meet system requirements for achieving and maintaining lubrication equilibrium. In some embodiments, this incidental agitation is insufficient to meet system requirements for achieving and maintaining lubrication equilibrium. In some embodiments, additional agitation is required for proper operation. Such agitation may be provided by passive techniques, including but not limited to the placement of flow inlets and outlets in receiver tanks that allow gravity to act on the WF/NSIL mixture flow in a manner that disperses the NSIL within the WF/NSIL mixture, the use of fixed vanes in conduits and/or vessels through which the WF/NSIL mixture flows, rotating devices propelled by the motive force of the system pump acting on the WF/NSIL mixture, and the like. Active means of agitation, including but not limited to stirrers, circulators and circulation pumps, mixers, injection jets, and other mechanical or electromechanical devices or methods may also be used to maintain a suitable dispersion of NSIL within the colloidal WF/NSIL mixture at system points of interest.
[0040] The use of a mixture of working fluid and non-soluble immiscible lubricant(s) solves the problems not adequately served by the known art. It provides exemplary lubrication to a wide variety of fluid displacement machines, including those designed for continuous operation, without the need for dedicated lubrication systems comprising additional components and their attendant operational and maintenance requirements.
[0041] All know prior art specifically teaches away from the use of non-soluble immiscible lubricants in fluid displacement machine which do not also comprise a separate oil recovery and circulation system. The system and methods disclosed herein impose no requirement for, and do not benefit from, separation of the NSIL from the WF/NSIL mixture at any point. Once combined, the lubricant and working fluid components of the mixture coexist at all times and are never intentionally separated in the manner taught for prior art oil recovery systems. While the mixture components do tend toward self-separation due to their physical compositions, the system is designed to operate normally with both components mixed and agitated to a state of satisfactory lubricant dispersion. The earlier technology was not able to overcome several notable problems with NSIL lubrication schemes, including the accumulation of lubricant at undesired points in the system resulting in unacceptable degradation in system performance. The apparatus, systems, and methods taught herein have been experimentally and operationally verified to achieve the problem of providing desired lubrication without an oil recovery system or the previously-experienced reduction in system efficiency.
BRIEF DESCRIPTION OF THE DRAWINGS
[0042] Without limiting the invention to the features and embodiments depicted, certain aspects this disclosure, including the preferred embodiment, are described in association with the appended figures in which;
[0043] FIG. 1 is a block diagram of a prior art ORC system used to convert heat energy into electric power;
[0044] FIG. 2 is a block diagram of an ORC system used with this invention depicting a lubrication feed system from the outlet of the system pump to the positive displacement machine;
[0045] FIG. 3 is a graph that depicts the concentration of non-soluble immiscible lubricant present at the outlet of a system pump as a function of time after startup; and
[0046] FIG. 4 is cross sectional side view of a receiver tank in an ORC system depicting the stratification of the mixture of working fluid and non-soluble immiscible lubricant.
DETAILED DESCRIPTION
[0047] FIG. 2 depicts an ORC system configuration suitable for use with the present invention. Here, lubrication line 108 is operatively connected between the output of system pump 105 and one or more points requiring lubrication in positive displacement machine 102 . In some embodiments, these points are bearing housings within which one or more ball, roller, sleeve, or other configuration of bearings are housed. The flow of WF/NSIL mixture under positive pressure from the system pump 105 , which may be controlled by a microprocessor-directed variable frequency drive (“VFD”) system, provides a stream of lubricating mixture to the bearings and/or other lubrication points. While the WF/NSIL mixture may be extracted from any convenient or desired point in the system, the output of system pump 105 is a particularly advantageous point of extraction for several reasons. It is the point of greatest positive pressure of any WF/NSIL mixture location in the ORC system, as system pump 105 is the sole source of such motive pressure for the WF/NSIL mixture in the particular system depicted. No additional pressure-inducing components are required if a small portion of the positive pressure generated by system pump 105 is used to supply a stream of WF/NSIL mixture for lubrication purposes.
[0048] Another significant advantage of obtaining WF/NSIL mixture for lubrication purposes at the output of system pump 105 is that this point also presents the lowest temperature WF/NSIL mixture anywhere in the ORC system. The WF/NSIL mixture at this point has been fully condensed and will provide the maximum heat dissipation when applied to the bearings or other lubrication points at the machine. While the use of warmer mixture may be acceptable or even desired in some embodiments, the cooler lubrication source is often preferred.
[0049] Regardless of the preferred source of WF/NSIL mixture used for lubrication, the flow rate may be controlled by one or more valves or other flow control devices so as to achieve the desired flow rate. This is particularly useful when the WF/NSIL mixture is obtained at the output of system pump 105 , as the speed of the VFD-controlled pump is dictated by the larger operational requirements of the ORC system and cannot be varied to accommodate lubrication concerns. In cases where a dedicated supplemental lubrication pump is employed for provide adequate pressure for the lubrication feed, the flow of WF/NSIL mixture to the bearings or other points of lubrication may be controlled in whole or in part by controlling the operation of said dedicated supplemental pump in place of, or in combination with, suitable valves or other flow control devices.
[0050] The choice of lubricant to be mixed with the chosen working fluid is critical. There are a wide variety of working fluids suitable for use in the many applications to which this disclosure applies. The essential characteristic of the WF/NSIL mixture of this invention is that the working fluid and the non-soluble immiscible lubricant form a colloidal mixture rather than a homogenous, uniform solution. By way of illustration and not limitation, examples will be provided using preferred ORC systems. The same principles apply to other applications when appropriately adjusted for their specific requirements. Some ORC systems utilize water, vaporized into steam by the input heat, as a working fluid. For those systems, a wide variety of oils and other lubricants not soluble in water may be appropriate for use, potentially including petroleum-based lubricants. Many ORC systems utilize refrigerants, including but not limited to organic refrigerants, in lieu of water as a working fluid. The complex chemical composition of refrigerants is an area of active development driven in large measure by concerns surrounding the potential effect of legacy refrigerants on the environment. As another non-limiting example, the refrigerant discussed above (R-245fa) is classified as a hydrofluorocarbon (HFC) compound and lacks the chlorine component of the earlier generation of chlorofluorocarbons (CFCs), such as R-12, as well as the later generation of hydrochlorofluorocarbon (HCFC) refrigerants, such as R-22, both now deprecated since being deemed environmentally undesirable. Due to their different compositions, certain lubricants soluble or miscible in chlorinated refrigerants are not similarly soluble or miscible in non-chlorinated refrigerants, including but not limited to HFCs such as R-245fa.
[0051] An essential element of this invention is the non-soluble immiscible character of the WF/NSIL mixture. It is not sufficient to identify a fluid and a lubricant independently of this requirement. Due to the differences in composition of both components, each must be carefully selected in full consideration of the characteristics of the other. In the embodiment described above, one such combination experimentally and operationally verified to produce the desired non-soluble immiscible WF/NSIL mixture consistent with this disclosure is the refrigerant R-245fa and mineral oil or its closely-related synthetic alternatives such as alkylbenzene oil. This example is illustrative of one preferred embodiment and is not limiting upon the scope of this invention in any way, as it is believed that numerous other combinations of fluids (refrigerants and non-refrigerants) and lubricants may be used to comprise an appropriate colloidal mixture for a wide variety of applications consistent with this disclosure.
[0052] Because the WF/NSIL mixture is colloidal in nature, it is by definition non-uniform at the microscopic level and for a certain sample range above that. Unlike soluble or miscible compositions where the components in a homogenous mixture may be difficult or even impossible to separate without elaborate processing, the colloidal WF/NSIL mixture is self-separating. Even with extreme agitation, visual inspection of the WF/NSIL mixture reveals the presence of NSIL droplets (as the discontinuous phase) distributed throughout the working fluid (as the continuous phase). The NSIL droplets constantly seek to combine with each other, forming larger droplets that collect on the upper layers of any accumulation of WF/NSIL mixture at rest as they are displaced in the mixture by the working fluid of greater specific gravity settling to the lower layers due to gravitational force.
[0053] With regard to any assessment of the composition of the colloidal WF/NSIL mixture, it must be understood that determination of the proportional composition of the colloidal WF/NSIL mixture requires a sample of appropriate size for the purpose at hand. By way of example and not limitation, a sample size of 5 mL or less may be optimal for the purpose of characterizing a WF/NSIL mixture at rest that has essentially separated into strata when the task at hand is to determine the boundaries of such strata as precisely as possible. When assessing the overall composition of a colloidal WF/NSIL mixture that is only slightly more agitated than in its fully separated state, a 5 mL sample taken at a particular location may be highly misleading due to the lack of uniformity in the WF/NSIL mixture. Instead, a sample between 100 and 500 mL, or greater, may be advisable. In circumstances involving a highly agitated and well-dispersed colloidal WF/NSIL mixture, a sample size of between 10 and 50 mL may suffice to accurately determine its proportional composition. All discussions herein regarding the proportional composition of a WF/NSIL mixture are predicated on the basis that such composition is based a suitable sample size for the state of dispersion of NSIL within the WF/NSIL mixture, as such state will vary greatly throughout the system as discussed below.
[0054] The time-dependent variation in the relative concentration of NSIL in the WF/NSIL mixture should understood to be a function of many characteristics of the materials and the system within which the WF/NSIL mixture circulates in a closed loop. Factors which affect the time-dependent concentration of NSIL in the WF/NSIL mixture include, but are not limited to, a) the time-dependent propensity for the WF/NSIL mixture to separate while at rest, b) the amount of time that has lapsed since the ORC system's last shutdown and/or the state of the WF/NSIL mixture at commencement of operation, c) the physical operating constants of the system, such as mass flow rate of the WF/NSIL mixture, the capacity of any WF/NSIL mixture receiver or storage tanks, temperature and pressure of the WF/NSIL mixture at any point, and the like, 4) the absence or presence of any mechanical or other agitation that would affect the time required for the WF/NSIL mixture to reach its optimum state of lubrication equilibrium, 5) sheer randomness in location and/or other factors under which the WF/NSIL mixture separates, and 6) any other factors that would enhance or retard the process of attaining an optimal WF/NSIL mixture. The tendency of the unstable colloidal WF/NSIL mixture to naturally separate on its own when the mixture is at rest and not subject to agitation (listed as factor (a) above) is a characteristic of the properties of the working fluid component(s) and non-soluble immiscible lubricant component(s) of the WF/NSIL mixture and is largely independent of the system in which the WF/NSIL mixture is utilized.
[0055] The degree of dispersion of NSIL in the WF/NSIL mixture is of interest only at certain points in the system. One such point is the location in the system where a portion of the mixture is extracted for application at desired points of lubrication. It important that the mixture obtained for direct injection lubrication contain the desired quantity of NSIL lubricant. Extracting lubricant-depleted mixture for lubrication purposes, particularly when done unintentionally, would jeopardize the operation of the machine. As described above, extracting a portion of the WF/NSIL mixture at the output of the system pump would be preferred in some embodiments. At this point in the system, having just been churned by the pump's impellers, the mixture would be relatively homogeneous and well-dispersed, and if the input flow to the system pump contained an appropriate concentration of lubricant, the portion extracted for lubrication purposes would likewise contain an appropriate concentration of NSIL evenly dispersed within the output flow of the system pump. In another embodiment, the mixture extracted for lubrication injection may be taken from a reservoir or receiver where the mixture has been allowed to rest relatively undisturbed for a period of time. Due to the self-separating nature of the colloidal mixture, the location of the extraction point within the reservoir or receiver tank will largely determine the concentration of lubricant in the extracted mixture. As described elsewhere herein, extracting fluid from the upper strata of separated mixture will yield a much higher concentration of lubricant than if the sample is extracted near the bottom of the tank. At certain points in the system, the relative concentration of lubricant in the WF/NSIL mixture is not critical to the operation of the system, although due to the closed-loop circulating nature of the system, the relative proportion of working fluid and lubricant(s) will generally be constant on the whole for a similar and appropriate sample size obtained between the source point and the exit point if a similar degree of agitation is maintained for the mixture.
[0056] In FIG. 3 , empirical test data related to the variation in NSIL concentration as a function of time after startup of an ORC system is depicted. In this series of measurements, the total WF/NSIL mixture contained in the closed-loop of an ORC system was 5.8% NSIL by mass (depicted by curve 301 ). For each trial, WF/NSIL mixture samples of sufficient quantity were collected at the output of system pump 105 in an ORC system configuration similar to that depicted in FIG. 2 . The machine was started and the proportional composition of the WF/NSIL mixture was measured at the start, at 10 minute increments for the first 30 minutes of operation, and again after 60 minutes of operation. Following collection of the data, the ORC system was stopped and the WF/NSIL mixture in the closed-loop system was allowed to rest without movement or agitation until it was believed to have reached its naturally quiescent state.
[0057] Curve 302 represents the data associated with the iteration with the maximum observed concentration of NSIL at the start, curve 304 represents the same data for the iteration with the lowest observed concentration at the start, and curve 303 represents the average (mean) data for all test iterations performed. It can be seen that the starting values varied widely over a range of almost 3:1. This variation is attributable to the fact that the WF/NSIL mixture readily separates when the ORC system is stopped and the data provides insight that the separation of the WF/NSIL mixture within the closed-loop circuit has at some degree of randomness and therefore is not a highly repeatable or predictable phenomenon.
[0058] A particularly valuable conclusion that may be drawn from the data is that regardless of the starting concentration of NSIL in the WF/NSIL mixture, the measured concentration of NSIL in the WF/NSIL mixture was seen to converge on a highly repeatable value of approximately 2%. It is also important to observe the difference between this value and the overall NSIL concentration of 5.8% based on known and carefully measured quantities installed at the test commissioning of this particular system. It is also important to note that this 2% concentration of lubricant flowing within the active portion of the system is substantially less than the 5% taught by Smith in that prior art system.
[0059] The difference between the overall concentration of NSIL and the observed concentration at the output of system pump 105 , which also represents the concentration at the output of positive displacement machine 102 due to the closed-loop circuit between those two points, is attributable to several factors. First, NSIL has extremely strong affinity to bond with metal surfaces in the ORC system, including but not limited to the surfaces and bearings of the positive displacement machine, the metallic inner surfaces of heat exchanger 101 , and metallic inner surfaces of condenser subsystem 104 , all of which are directly in contact with the WF/NSIL mixture flow. This affinity causes a thin film of NSIL to be deposited on these surfaces, providing lubrication on the case of the surfaces, bearings, and other lubrication points of the positive displacement machine. While no lubrication is specifically required for the inner metallic surfaces of the heat exchanger 101 and condenser subsystem 104 , the deposition of NSIL on these surfaces was observed to have a negligible effect on their thermal properties and performance. At the overall ORC system concentration of 5.8% NSIL by mass, the comprehensive performance of the ORC system was only de-rated by approximately 2%, which includes both the effect of the oil deposition within the thermal subsystems and the addition of non-refrigerant NSIL to the refrigerant working fluid required for proper operation of the ORC system. This 2% degradation in system performance is notable in that it is far less than reported in the prior art for similar systems utilizing a mixture of working fluid and soluble or miscible lubricants.
[0060] Additionally, the difference between the overall ORC system concentration of 5.8% NSIL by weight and the observed 2% concentration at the point of lubrication equilibrium is partially attributable to the accumulation of NSIL in the receiver tank associated with the condenser subsystem. FIG. 4 presents a representative depiction of the stratification of the components in the receiver tank 401 measured during ORC system operation at the point of lubrication equilibrium. While the boundaries between adjacent stratum are not clearly defined, the regions have distinct characteristics that provide valuable insight into the nature of this invention.
[0061] Stratum 402 is a faintly milky colloidal mixture comprising primarily organic refrigerant working fluid with a small quantity of suspended NSIL. This stratum extends upward approximately 9.5 inches from the bottom of the tank. Stratum 403 is a transition zone approximately 1 inch in depth and, although similarly milky in appearance, further comprises droplets of NSIL of increasing size and number toward its upper edge. Stratum 404 , approximately 1.5 inches thick, is largely comprised of NSIL with random droplets of working fluid refrigerant. Stratum 405 , approximately 0.5 inches high, is a region comprised of agitated working fluid and NSIL. Due to the agitation, the upper surface is irregular and subject to variation. Partially vaporized working fluid occupies the remaining volume between the upper surface of stratum 405 and the upper inside surface of receiver tank 401 .
[0062] The demonstrated and observed affinity of NSIL for the surfaces, bearings, and other lubrication points in the machine represent a noticeable and significant improvement over the present use of lubricants that are soluble or miscible in the working fluid. Experimental observations reveal a much higher concentration of NSIL at the critical points in the system despite the absence of sufficient bearing temperatures necessary for proper lubrication in the prior art. Further, experimental testing has revealed that the use of NSIL in lieu of soluble or miscible lubricants as taught in the prior art results in decreased bearing wear over significant periods of use. In the case of NSIL, bearing temperature under operating conditions is irrelevant as it is no longer necessary to vaporize working fluid to provide adequate lubrication as taught in the prior art. The use of lubricants that are inherently insoluble and immiscible in the working fluid represents a clear departure from prior teaching in this field. It is believed that the present art relied upon a presumption that a mixture of working fluid and lubricant was best achieved through the use of lubricants that were either soluble or miscible in the liquid phase of the working fluid that would yield a stable, homogenous mixture of lubricant and working fluid. However, the use of NSIL as taught herein provides superior performance despite the fact that the WF/NSIL mixture can, by definition, never be completely homogenous and its instantaneous composition inherently stable in colloidal form.
[0063] The description of this invention is intended to be enabling and not limiting. It will be evident to those skilled in the art that numerous combinations of the embodiments described above may be implemented together as well as separately, and all such combinations constitute embodiments effectively described herein. | Apparatuses, systems, and methods are provided for the lubrication of fluid displacement machines, in particular positive displacement machines such as twin screw expanders utilized in organic Rankine cycle systems, comprising a working fluid mixed with a lubricant that is neither soluble nor miscible in the liquid phase of the working fluid. | 5 |
BACKGROUND OF THE INVENTION
The invention relates to fluid-operated regulating apparatus, especially for use in motor vehicles, and more particularly to improvements in hydraulic or pneumatic apparatus wherein at least one valve, such as a magnetic valve, is adjustable by control means to vary the characteristics of a fluid in a path leading from a pump or another suitable fluid displacing and pressurizing machine to at least one consumer. The valve can be set up to act as a proportional valve, an on-off valve or a multi-way cock.
It is known to resort to pulse-width modulation as a method of controlling the manner in which a valve can influence a pressurized fluid in a path between a source of pressurized fluid and one or more consumers. Such mode of regulation was proposed for the purpose of achieving a reduction of hysteresis. It is also known to achieve a reduction of hysteresis by applying to a valve control signals which are subject to oscillation. Still further, it is known to employ a valve which is influenced by signals subject to frequency changes within the regulating range.
As a rule, hysteresis which develops when a valve is employed in a fluid-operated regulating apparatus exerts an adverse influence upon the operation of such apparatus. On the other hand, if the operation of the valve is controlled by resorting to a control value or parameter having a given frequency which has been found to be desirable because it exerts a positive influence upon the hysteresis, one is likely to adversely influence the mechanical characteristics of the valve. For example, if the valve is controlled by resorting to a low-frequency signal, the valving element is likely to impact upon the seat with a highly pronounced force (chatter). On the other hand, if the chosen frequency of a valve-controlling or regulating signal is too high, the inertia of the mass of the mobile valving element, such as a reciprocable piston or plunger, is likely to be too large to permit the valving element to follow the high-frequency changes of such signals.
OBJECTS OF THE INVENTION
An object of the invention is to provide a fluid-operated (hydraulic or pneumatic) regulating apparatus which is constructed and assembled in such a way that an optimal reduction of hysteresis can be achieved within the entire operating range.
Another object of the invention is to provide an apparatus wherein the chatter or impact(s) of the mobile valving element(s) upon the seat or seats of the valve or valves is or are still below an acceptable threshold value during each and every stage of operation of the apparatus.
A further object of the invention is to provide a simple, compact and inexpensive apparatus which exhibits the above outlined features and advantages.
An additional object of the invention is to provide a motor vehicle with a power train wherein the operation of at least one constituent of the power train is or can be regulated by an apparatus of the above outlined character.
Still another object of the invention is to provide a novel and improved fluid-operated regulating apparatus for a torque transmitting system and/or a transmission in the power train of a motor vehicle.
A further object of the invention is to provide novel and improved valve means for use in the above outlined apparatus.
Another object of the invention is to provide a novel and improved method of operating a hydraulic or pneumatic apparatus for the regulation of clutches, transmissions and/or other constituents of power trains in various types of motor vehicles.
SUMMARY OF THE INVENTION
One feature of the present invention resides in the provision of a fluid-operated (hydraulic or pneumatic) regulating apparatus for use in a motor vehicle. The improved regulating apparatus comprises at least one fluid displacing and pressurizing machine (such as a pump) which is arranged to supply at least one flow or stream of pressurized fluid along a predetermined path to at least one consumer (e.g., to a transmission and/or to a clutch in the power train of the motor vehicle), adjustable fluid pressure regulating valve means in the path, and control means for adjusting the valve means as a function of at least one variable parameter. The at least one parameter is generated by a plurality of components (e.g., by two components); one of the plurality of components is modulated at a first frequency, and another of such plurality of components is modulated at a second frequency.
In accordance with one embodiment of the invention, the at least one parameter is an electric current potential (voltage) and, in accordance with another embodiment, the at least one parameter is an electric current strength (amperage).
The first frequency can be higher than the second frequency; for example, the first frequency can be a whole multiple of the second frequency. Otherwise stated, the duration of a second frequency can be several times the duration of a first frequency.
The at least one parameter can have a modulatable amplitude.
It is also possible to operate the improved apparatus in such a way that the at least one parameter is the pressure of fluid in the predetermined path. For example, the at least one parameter can constitute a pilot control pressure of the valve means or a fluid pressure downstream of a mobile valving element of the valve means.
The control means can be set up to adjust the valve means so as to select a predetermined value of an amplitude of the pressure of fluid as adjusted by the valve means. Again, the at least one parameter can constitute a pilot control pressure of the valve means or a fluid pressure downstream of a mobile valving element of the valve means.
The apparatus can further comprise signal generating means (such as one or more sensors) for monitoring the pressure of fluid in the path and for transmitting the thus generated signals to the control means for the purpose of regulating the amplitude of fluid pressure. The valve means can comprise a preliminary or auxiliary valve arranged to establish a pilot control pressure in the path, and the monitoring means of such apparatus is preferably arranged to generate signals denoting the pilot control pressure. It is also possible to employ valve means comprising at least one adjustable main valving element (e.g., a reciprocable pusher or plunger) in the path, and the monitoring means of such apparatus can be arranged to monitor fluid pressure downstream of the at least one adjustable main valving element.
At least one component of the at least one variable parameter is or can be modulatable as a function of electric current. Furthermore, at least one of the components can have an amplitude which can be raised or lowered as a function of a parameter of the fluid. Still further, at least one of the components is or can be modulatable as a function of a temperature (such as the temperature of the fluid); for example, the amplitude of at least one of the components can be raised or lowered as a function of temperature.
At least one of the first and second frequencies is or can be modulatable. The frequencies can be selected as a function of the operating point of the regulating apparatus or of the motor vehicle. For example, the frequencies can be varied as a function of discrete parameters such as the temperature, the pressure and/or others. It is also possible (and often advisable) to change the pulse duty factor or keying ratio of the valve means as a function of the operating point of the regulating apparatus or the motor vehicle.
One of the components can have a frequency in the range of between about 100 and 1000 Hertz, preferably in the range of between about 200 and 600 Hertz.
As already mentioned above, one of the first and second frequencies can be lower than the other of these frequencies, for example, by a factor of between about 1/3 and 1/50.
Another feature of the invention resides in the provision of a method of adjusting a valve, such as a magnetic valve having at least one magnetic winding, as a function of at least one variable parameter. The improved method comprises the step of generating the at least one variable parameter by a plurality of components having different frequencies. For example, the at least one parameter can constitute or include an exciting current for the winding of a magnetic valve.
The method can further comprise the step of installing the valve in a path for the flow of a fluid from at least one fluid displacing and pressurizing machine (such as the aforementioned pump) to at least one consumer of pressurized fluid in a motor vehicle (e.g., to an automatically adjustable torque transmitting system between a prime mover and a transmission in the power train of a motor vehicle).
A further feature of the instant invention resides in the provision of a fluid-operated regulating apparatus which comprises an adjustable valve disposed in a path for a flow of a pressurizable fluid in a predetermined direction and including at least one mobile valving element arranged to vary the fluid pressure, at least one sensor (monitoring means) arranged to generate signals denoting the pressure of fluid in the path, and means for regulating the amplitude of the pressure of fluid in the path. For example, the at least one sensor can include or constitute means for monitoring an input control pressure of the fluid upstream of the at least one valving element; alternatively, or in addition thereto, the at least one sensor can include or constitute a means for monitoring the pressure of fluid downstream of the at least one valving element.
The novel features which are considered as characteristic of the invention are set forth in particular in the appended claims. The improved fluid-operated regulating apparatus itself, however, both as to its construction and the mode of installing, assembling and utilizing the same, together with numerous additional important and advantageous features thereof, will be best understood upon perusal of the following detailed description of certain presently preferred specific embodiments with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic partly sectional view of a fluid-operated regulating apparatus which embodies one form of the invention and is designed to vary the characteristics of a hydraulic fluid serving to regulate or control the operation of a consumer such as a torque transmitting system between the engine and the transmission in the power train of a motor vehicle; and
FIG. 2 is a diagram wherein the curves indicate variations of amperage and voltage serving to regulate the operation of a valve in the apparatus of FIG. 1.
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows a fluid-operated regulating apparatus 1 which can be utilized with advantage in the power train of a motor vehicle. For example, the apparatus 1 can operate a consumer 3, such as a torque transmitting system between a prime mover and a transmission of a motor vehicle. A torque transmitting system in the form of a friction clutch between the engine and the transmission of a power train in a motor vehicle is shown, for example, in commonly owned U.S. Pat. No. 5,450,934 (granted Sep. 19, 1995 to Paul Maucher for "FRICTION CLUTCH") the disclosure of which is incorporated herein by reference. In addition to constituting a friction clutch, the consumer 3 can constitute a lockup clutch or bypass clutch in a hydrokinetic torque converter, e.g., a lockup clutch of the type disclosed in U.S. Pat. No. 5,377,796 (granted Jan. 3, 1995 to Oswald Friedmann et al. for "APPARATUS FOR TRANSMITTING FORCE BETWEEN ROTARY DRIVING AND DRIVEN UNITS") the disclosure of which, too, is incorporated herein by reference. Still further, the consumer 3 can constitute a starter clutch or a direction reversing clutch. A direction reversing clutch is disclosed, for example, in U.S. Pat. No. 5,169,365 (granted Dec. 8, 1992 to Oswald Friedmann for "POWER TRAIN") the disclosure of which is also incorporated herein by reference.
The apparatus 1 is set up to vary the magnitude of torque which can be transmitted by a clutch (such as the consumer 3) in the power train of a motor vehicle. The illustrated apparatus 1 is assumed to be operated by a hydraulic fluid and comprises at least one pump 2 or an analogous fluid pressurizing and displacing machine. The path from the outlet of the pump 2 to a chamber 7 of the consumer 3 is defined by a conduit 4 leading directly from the outlet of the pump 2, a conduit 6 leading directly to the chamber 7 of the consumer 3, and a hole or bore 14 provided in the housing or body 20a of a valve 20, e.g., a proportional valve, to establish (when necessary) a more or less pronounced connection between the conduits 4 and 6. The purpose of a two-piece valving element 21, 5 of the valve 20 is to select the system pressure in the chamber 7 and hence the magnitude of the torque which can be transmitted by the consumer 3, it being assumed here that the consumer 3 is a clutch between a prime mover and a transmission in the power train of a motor vehicle.
The member 5 (e.g., a reciprocable piston) of the composite valving element 21, 5 of the valve 20 directly controls the flow of pressurized fluid (e.g., oil) from the conduit 4 into the conduit 6 and thence into the chamber 7. On the other hand, the axial position of the piston 5 is determined by the axial position of the second member 21 (e.g., a reciprocable plunger) of the composite valving element 5, 21 of the valve 20. The plunger 21 determines the pressure P S of fluid in a plenum chamber 8 at the left-hand axial end of the piston 5 in that it controls the rate of escape (if any) of fluid from the chamber 8 by way of a conduit 12 and a seat 22 which latter is engageable by the plunger 21.
A secondary or auxiliary valve 10 is installed in a bypass conduit 11, 13 which connects the conduit 4 with the conduit 12. The character 9 denotes an optional resilient energy storing element (e.g., at least one coil spring) which reacts against the valve body 20a and biases the piston 5 in a direction to the left, as viewed in FIG. 1, namely in a direction to reduce the rate of flow or to interrupt the rate of flow of pressurized fluid from the conduit 4 into the conduit 6.
As a rule, the pressure of fluid in the conduit 13 downstream of the auxiliary valve 10 matches or approximates the pressure P S in the conduit 12 and plenum chamber 8. The pressurized fluid in the chamber 8 can shift the piston 5 against the opposition of the energy storing element 9 and against the opposition of the fluid acting upon two confronting annular shoulders 5a, 5b in an annular compartment 17 defined by the valve body 20a and connected to the conduit 6 by a further conduit 18. The fluid in the compartment 17 assists the energy storing element 9 in opposing the action of fluid upon the left-hand end face of the piston 5 with a force which is proportional to the difference between the diameters A and B of those portions of the piston 5 which flank the smaller-diameter neck portion D of the piston 5 between the shoulders 5a and 5b.
If the proportional valve 20 is closed, i.e., if the conical tip of the plunger 21 engages the valve seat 22, the fluid medium in the plenum chamber 8 is maintained at a maximum pressure P S and the rate of possible fluid flow from the conduit 4 into the conduit 6 via bore or hole 14 is high. If the valving element or plunger 21 is caused to move away from actual engagement with the seat 22, e.g., merely for a short interval of time, a certain amount of fluid can escape in the direction of the arrow 23 (for example, into a sump 16 for the pump 2) and the pressure P S in the chamber 8 drops accordingly.
The piston 5 is provided with two additional shoulders 15a and 15b. The axial position of the shoulder 15a determines the extent of communication between the conduits 4, 6 via bore or hole 14, and the axial position of the shoulder 15b determines whether or not the conduit 6 can communicate with the sump 16. The pressure of fluid in the conduit 6 and chamber 7 drops (e.g., to zero) when the shoulder 15a seals the conduit 4 from the bore or hole 14 but the shoulder 15b establishes a passage for the flow of fluid from the chamber 7 via conduit 6 and bore or hole 14 into the sump 16. The exact axial force acting in the compartment 17 in a direction to assist the energy storing element 9 equals the fluid pressure in the compartment 17 multiplied by the difference between the diameters A and B.
The axial movements of the plunger 21 are initiated by an electronic control unit 30 having an output 32 connected with the winding 33 of the valve 20. The control unit 30 has several inputs (two are shown at 31a and 31b) which are connected to suitable monitoring means or sensors (two sensors 131a, 131b are shown in FIG. 1). As used herein, the term "sensor" or "monitoring means" is intended to encompass electronic and/or other circuits, e.g., those often associated with engines and/or transmissions in motor vehicles. Signals from the control unit 30 via output 32 to the winding 33 can be selected to ensure movements of the plunger 21 to predetermined axial positions relative to the seat 22 and/or to ensure movements of the plunger 21 through predetermined distances.
In order to minimize the hysteresis of the piston 5 when the apparatus 1 is in use, the plunger 21 is imparted an oscillatory movement which, in accordance with a feature of the invention, can be generated by resorting to a control signal which is the result of a superimposition of two components having different frequencies. One component of the control signal (such as a control current) has a relatively high frequency, for example, within the range of between about 100 and 1000 Hertz, preferably between about 200 and 600 Hertz. The other component of the control signal has a lower frequency, preferably smaller than the frequency of the first component by a factor of between 1/3 to 1/50, particularly between about 1/5 to 1/25.
Otherwise stated, the first component of the control signal is modulated with a first chopper frequency, and the second component of the control signal is regulated or controlled with a lower frequency. The current amplitude of the lower-frequency component of the control signal is regulated or controlled for the purpose of ensuring that the composite valving element 21, 5 does oscillate but the plunger 21 does not impact (chatter) against the seat 22 with a pronounced force. For example, the modulation of current amplitude can be effected in such a way that, when the fluid (such as oil) is cold and/or when the intput or pilot control pressures are low, the amplitude of the signals is high but the amplitude is low or nil when the fluid is hot and/or the input or pilot control pressures are high.
In accordance with an additional feature which brings about further improvements, the operation of the control unit 30 can be selected in such a way that the amplitude of oscillation of the valving element in the pilot or servo control circuit or in the valve 20 is regulated or controlled to rise exactly to a value such that the piston 5 barely carries out a certain oscillatory movement. By introducing the pressure amplitude of the main circuit as an input into a slow regulator of the control circuit 30, it is possible to compensate for fluctuations of the hysteresis of individual disturbances as well as variations during the entire useful life of the apparatus 1. Short-lasting variations, for example, as a function of pressure and temperature, are independent of such "slow regulator" of the control circuit 30.
The selection of the control value, such as the control current for the valve 20, for the purposes of reducing the hysteresis in a hydraulic control or regulating apparatus by varying the amplitude of the current, can be carried out by way of the valve 20 at a constant or at a variable basic chopper frequency.
The valve 20 of FIG. 1 is assumed to be a proportional valve. The piston 5 is the main valving element, and the valve 10 is a preliminary or auxiliary or pilot valve or servo valve which latter makes available a control pressure in the region of the conduit 12 and/or in the plenum chamber 8.
FIG. 2 illustrates two signals as a function of time. The curve 100 denotes changes of the voltage of the magnetic valve 20, and the curve 101 denotes changes of the current, both as a function of time. The periods of the high-frequency oscillation or of the high-frequency control signal share are shown at T 1 , and the duration of a period of the low-frequency component is shown at T 2 . The duration of the period of the low-frequency signal share or component, which is shown at T 2 , is a multiple of (e.g., exactly seven times) the duration of a period T 1 of the high-frequency oscillation of the high-frequency signal component.
Within a period T 1 , the voltage denoted by the curve 100 reaches a maximum value after the elapse of an interval ΔT 1 , and is essentially zero after the elapse of the immmediately following interval ΔT 2 of the same period T 1 . The ratio of ΔT 1 to ΔT 2 denotes the mark space ratio or pulse duty factor; a full signal is available during the interval ΔT 1 , and the signal is basically zero after the elapse of the immediately following interval ΔT 2 of each period T 1 . The voltage signal reaches a maximum value after elapse of the interval ΔT 1 , the value of the current (refer to the curve 101) rises from basically zero to a predeterminable value during the interval ΔT 1 but the current decreases again during the interval ΔT 2 . During the next period T 1 , the current increases at first to thereupon decrease again but the average current increases. The pulse duty factor ΔT 1 to ΔT 2 can be resorted to for the selection or regulation of the average current. During the first three periods T 1 , the duration of ΔT 1 basically exceeds ΔT 2 ; however, starting with the fourth period T 1 (at t), the pulse duty factor ΔT 1 to ΔT 2 is changed and the interval ΔT 1 is shorter than the interval ΔT 2 . This renders it possible to ensure that the average current decreases during the period T 1 . Thus, a modulation of the amplitude, namely a modulation of the pulse duty factor ΔT 1 to ΔT 2 , renders it possible to achieve a modulation of the average control current.
FIG. 2 shows clearly that the modulated increase and lowering of the current as a function of time, as well as that a long-wave oscillation, is superimposed upon the high-frequency rise and lowering of the current. When the pilot or input control pressure in the chamber 8 of the valve 20 shown in FIG. 1 is low, the amplitude of the oscillations can be high because a low pressure denotes that the plunger 21 is located at a relatively great distance from the seat 22, i.e., that the valve is open to a relatively large extent. Due to such pronounced opening of the valve 20, it is possible to achieve rather pronounced reciprocatory movements of the valving element 21 without risking strong (forcible) impacts (chatter) of the element 21 against the seat 22. If the pressure of fluid in the chamber 8 is higher, the amplitude of the displacement modulation of the plunger 21 should be less pronounced if a forcible impact (pronounced chatter) of the plunger 21 against the seat 22 is to be avoided. The impact against the seat 22 is more problematic at elevated fluid pressures because the valve 20 is open to a lesser extent and, therefore, the plunger 21 is apt to strike against the seat 22 even at low distance or movement modulations.
One of the sensors 131a, 131b can transmit to the control unit 30 signals denoting pilot control pressure of the valve 10 or 20, and the other of these sensors can transmit signals denoting the fluid pressure downstream of the piston 5 (as seen in the direction of fluid flow from the pump 2). Furthermore, at least one of the sensors 131a, 131b (or one or more additional sensors, not specifically shown) can include means for transmitting to the control unit 30 signals denoting the temperature of the fluid in a selected portion of the path for the flow of fluid from the pump 2 to the consumer 3 and/or to the seat 22 and/or to the sump 16 and/or to the valve 10.
Unless otherwise stated, the terms "control" and "regulate" are used interchangeably in the specification, claims and abstract.
The selection of a control signal or of a control value with a signal which consists of two oscillation components is shown in FIG. 2. In addition to the illustrated modulation of the pulse duty ratio, it is also possible to carry out a modulation of the amplitude of the high-frequency or low-frequency oscillation, for example, as a function of the current or control pressure or other operational parameters. It is also possible to carry out a frequency modulation of the low-frequency or high-frequency oscillation, for example, as a function of the current or the control pressure or another operational parameter.
If the proportional valve 20 is controlled or operated by a signal which includes a high-frequency component and a low-frequency component, the piston 5 normally responds to or follows only the low-frequency component because, as a rule, the inertia of the piston 5 prevents it from carrying out a high-frequency movement.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic and specific aspects of the above outlined contribution to the art of fluid-operated regulating apparatus and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the appended claims. | A fluid-operated regulating apparatus for use in a motor vehicle, particularly to control the operation of a consumer, such as a clutch which transmits torque between an engine and a transmission in the power train of a vehicle as a function of one or more parameters, comprises at least one pump which supplies a flow of pressurized hydraulic or pneumatic fluid to the consumer by way of a valve controlled by an electronic unit which receives signals from a plurality of sensors. The signals which the electronic unit transmits to the valve are dependent upon at least one variable parameter which is generated by a plurality of components. One of these components is modulated or modulatable at a first frequency, and another of these components is modulated or modulatable at a second frequency which can be higher or lower than the first frequency. This reduces the likelihood of pronounced knocking or chatter of a reciprocable valving element of the valve against its seat and ensures an optimal reduction of hysteresis within the entire operating range of the consumer. | 5 |
BACKGROUND OF THE INVENTION
[0001] Historically, living tissue has been most commonly surgically repaired by thread, such as a suture, introduced by a pointed metal needle and tied with just enough tension to establish hemostasis or control of bleeding by compressing the tissue. Correct tension is established by the surgeon based on observation and judgment derived from extensive training. Excess tension can cause necrosis (the localized death of living tissue) and eventual failure of the repair.
[0002] An alternate method of joining tissue using metal staples has evolved over the last 90 years to a point where specialized staples for both skin and internal tissue closure are in common use today. The staples, which have sharp points for penetrating tissue, are formed in place by delivery instruments which bend them to a permanent shape suitable for tissue retention. The delivery instruments include mechanisms, such as an anvil, which control to some extent the relationship between tissue and staple, including the compression necessary to control bleeding. To the extent that they do so, surgeon skill is less of a factor in successful wound closure.
[0003] For conventional surgery, the clinical results for suturing and stapling are essentially the same, but both have their disadvantages. Sutures are suitable for all types of wound closure, but require that the surgeon have adequate access to the wound site and possess the skill to choose and apply the suture correctly. Conventional staples can also be appropriate for internal use, but require that a strong, rigid anvil be placed behind the tissues to be joined. Furthermore, the application of staples requires that there be enough space for an instrument, which can produce the necessary force to form the staple against the anvil. Stapling, however, is generally faster and, as previously noted, requires a lower level of skill.
[0004] The recent development of a beneficial, less invasive technique for gall bladder removal has suggested the feasibility of other abdominal procedures, such as bowel and hernia repair, that require the remote application of an internal fastener. As a result, less invasive instruments have been developed for both suturing and stapling remotely from the wound site by the surgeon. At the same time, patient benefit considerations are driving the development of less invasive techniques for a full range of abdominal and thoracic procedures including coronary artery bypass and valve replacement.
[0005] To date, stapling has proven to be more suitable for less invasive surgery than suturing. Instruments developed for that purpose approximately replicate the functions of stapler developed for open surgery and are approximately as easy to use. Instruments developed for less invasive suturing, on the other hand, are slow and cumbersome and do not solve the essential problem of tensioning the suture and tying the knot remotely. Sutures will find limited use in less invasive surgery but it is most likely that related wound closure problems beyond the capability of conventional staples will be solved by innovative mechanical fasteners which can more easily be remotely applied.
[0006] For instance, a new fastener has been designed for a less invasive hernia repair in which a synthetic mesh is used to reinforce the repair by anchoring it to surrounding tissue. Suturing is feasible but difficult. Conventional stapling is not feasible because an anvil cannot access the distal side of the tissue. The new fastener has the shape of a coil spring with the wire sharpened at one end and has been used successfully to attach the mesh by screwing the coil through it into the tissue. This new fastener can access the wound site through a small port in the abdominal wall. This fastener, however, does not produce compression upon the synthetic and natural tissue layers and thus does not produce hemostasis because the fastener is screwed into the wound site in its natural shape. Because this fastener does not create hemostasis, it may not be suitable for a wide range of surgical applications.
[0007] Other surgical fasteners have been fabricated from shape memory alloy. U.S. Pat. No. 4,485,816 to Krumme discloses a shape-memory surgical staple that uses an electric current to heat the staple to make it close. U.S. Pat. No. 5,002,562 to Pyka et al. discloses a fastener made from shape memory alloy that has the shape of a suturing loop in its undeformed shape. As noted above, however, sutures and staples are not always desirable for all surgical applications.
[0008] It is believed that other applications exist or will be identified for fastening layers of tissue where anvil access is not practical and where compression must be applied to the tissue to achieve hemostasis. For example, these criteria apply to the attachment of a graft more or less at right angles to another, larger, blood vessel (“end to side” anastomosis) such as the aorta for vascular bypass purposes. The availability of a less invasive vascular bypass procedure implies a significant patient benefit. Another example is the use of the fastener in endovascular procedures to attach a graft within large vessels such as the aorta, iliac or femoral arteries to repair aneurysms and occlusions. Stents, which are currently used for this purpose, are often insufficiently compliant to prevent leakage and consequent failure of the repair. Direct fixation of the graft to the inner wall of the vessel by the fasteners described herein may overcome this inherent problem of current techniques for endovascular repair.
[0009] What is desired, therefore, is a mechanical fastener and deployment instrument that can access internal tissue through a small surgical access port or incision and that can be applied conveniently and remotely.
SUMMARY OF THE INVENTION
[0010] Accordingly, an object of the present invention is to provide a surgical fastener that can access internal tissue through a small surgical access port or incision.
[0011] It is a further object of the present invention to provide a surgical fastener that can be applied remotely.
[0012] It is yet another object of the present invention to provide a surgical fastener that uses the superelastic properties of a shape memory alloy without having to apply heat to the fastener.
[0013] It is still another object of the present invention to provide a deployment instrument that can be used to deploy the surgical fasteners of above.
[0014] These objects of the invention are achieved by a surgical fastener preferably made from a shape memory alloy that accesses internal tissue or other synthetic material through a small surgical access port or incision. After the fastener is deployed through layers of tissue, it assumes a shape that automatically applies to the layers of tissue an appropriate hemostatic compression which is relatively independent of tissue thickness. The fastener is a suitable replacement for conventional non bio-absorbable sutures and staples in certain clinical applications. Its shape, method of deployment and low force requirements make it suitable for standard surgical procedures and especially suitable for laparoscopic and other less invasive surgery where access to the wound site is limited including endovascular surgery. The invention is expected to be especially useful for attaching synthetic grafts to an aorta.
[0015] In one form of the invention, there is provided apparatus for inserting a surgical fastener through a plurality of portions of material from within an endovascular pathway, the apparatus comprising:
[0016] a surgical fastener having first and second ends and made from a material which enables the fastener to be transformed from a first stressed elongate shape to a second unstressed shape upon the release of the fastener from a stressed condition, the first stressed elongate shape of the fastener enabling the first end to be extended through a plurality of layers of material, and with the second shape of the fastener being in the form of a spring with a plurality of coils around a spring axis, with the coils being spring biased towards each other along the spring axis with sufficient axial force so as to enable coils on opposite sides of layers to clamp the layers of material together along the spring axis;
[0017] a delivery tube having third and fourth ends, first and second tube portions adjacent to the third and fourth ends, respectively, and forming a longitudinal axis between the third and fourth ends, the delivery tube including a material which enables transformation from a third stressed elongate shape to a fourth unstressed shape upon the release from a stressed condition to an unstressed condition, the third stressed elongate shape enabling the third end to be extended through an endovascular pathway, with the fourth unstressed shape being formed with the first and second tube portions being configured at an angle to one another;
[0018] delivery tube deployment means being configurable between a first position and a second position, the first position of the delivery tube deployment means restraining the delivery tube in the third stressed elongate shape, and the second position of the delivery tube deployment means releasing the delivery tube in the fourth unstressed shape;
[0019] penetration means adjacent the third end of the delivery tube, the penetration means being configured to pierce through a vascular structure in the endovascular pathway; and
[0020] insertion means adjacent to the first end of the delivery tube, the insertion means being configured to place the surgical fastener through the vascular structure pierced by the penetration means.
[0021] In another form of the invention, there is provided a method for inserting a surgical fastener through a plurality of portions of material from within an endovascular pathway, the method comprising:
[0022] providing apparatus for inserting a surgical fastener through a plurality of portions of material from within an endovascular pathway, the apparatus comprising:
[0023] a surgical fastener having first and second ends and made from a material which enables the fastener to be transformed from a first stressed elongate shape to a second unstressed shape upon the release of the fastener from a stressed condition, the first stressed elongate shape of the fastener enabling the first end to be extended through a plurality of layers of material, and with the second shape of the fastener being in the form of a spring with a plurality of coils around a spring axis, with the coils being spring biased towards each other along the spring axis with sufficient axial force so as to enable coils on opposite sides of layers to clamp the layers of material together along the spring axis;
[0024] a delivery tube having third and fourth ends, first and second tube portions adjacent to the third and forth ends, respectively, and forming a longitudinal axis between the third and fourth ends, the delivery tube including a material which enables transformation from a third stressed elongate shape to a fourth unstressed shape upon the release from a stressed condition to an unstressed condition, the third stressed elongate shape enabling the third end to be extended through an endovascular pathway, with the fourth unstressed shape being formed with the first and second tube portions being configured at an angle to one another;
[0025] delivery tube deployment means being configurable between a first position and a second position, the first position of the delivery tube deployment means restraining the delivery tube in the third stressed elongate shape, and the second position of the delivery tube deployment means releasing the delivery tube in the fourth unstressed shape;
[0026] penetration means adjacent the third end of the delivery tube, the penetration means being configured to pierce through a vascular structure in the endovascular pathway; and
[0027] insertion means adjacent to the first end of the delivery tube, the insertion means being configured to place the surgical fastener through the vascular structure pierced by the penetration means;
[0028] placing the delivery tube adjacent the vascular structure, with the delivery tube being configured in the third stressed elongate shape;
[0029] deploying the delivery tube from the third elongate shape to said fourth elongate shape with the delivery tube deployment means, the deployment of the delivery tube placing the third end adjacent to the vascular structure in the endovascular pathway;
[0030] penetrating the vascular structure in the endovascular pathway with the penetration means, the penetration of the vascular structure being performed at the third end of the delivery tube; and
[0031] inserting the surgical fastener through the plurality of portions of material using the insertion means, the insertion of the surgical fastener being performed from inside of the vascular structure.
[0032] The above and other features of the invention, including various novel details of construction and combinations of parts and method steps, will now be more particularly described with reference to the accompanying drawings and pointed out in the claims. It will be understood that the particular devices and method steps embodying the invention are shown by way of illustration only and not as limitations of the invention. The principles and features of this invention may be employed in various and numerous embodiments without departing from the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] These and other objects and features of the present invention will be more fully disclosed or rendered obvious by the following detailed description of the preferred embodiments of the invention, which are to be considered together with the accompanying drawings wherein like numbers refer to like parts, and further wherein:
[0034] [0034]FIGS. 1A, 1B and 1 C are an isometric view and two side views, respectively, of the first embodiment of the surgical fastener in accordance with the invention;
[0035] [0035]FIG. 2 is an isometric view of the second embodiment of the surgical fastener in accordance with the invention;
[0036] [0036]FIG. 3 is a side cutaway view of the second embodiment of the surgical fastener of FIG. 2 in accordance with the invention;
[0037] [0037]FIG. 4 a side cutaway view of the third embodiment of the surgical fastener in accordance with the invention;
[0038] FIGS. 5 A- 5 F are front cutaway views of a deployment instrument showing the insertion of the surgical fastener of FIG. 1;
[0039] FIGS. 6 A- 6 F are front isometric views of another embodiment of a deployment instrument showing the insertion of a surgical fastener;
[0040] [0040]FIG. 7 is a front isometric view of the deployment instrument of FIGS. 5 A- 5 F as it is shipped;
[0041] [0041]FIG. 8 is a front cutaway view of the deployment instruments of FIGS. 5 A- 5 F and 6 A- 6 F;
[0042] FIGS. 9 A- 9 D are side cutaway views showing the use of a deployment instrument with the surgical fastener of FIG. 2;
[0043] [0043]FIG. 10 is a diagrammatic view of apparatus for inserting a surgical fastener through a plurality of portions of material from within an endovascular pathway;
[0044] [0044]FIG. 11 is a diagrammatic view of the apparatus shown in FIG. 10 with a graft and a stent expanded in an aorta;
[0045] [0045]FIG. 12 is a diagrammatic view of the apparatus shown in FIGS. 10 and 11 with delivery tubes returning to an unstressed, preformed condition for penetration through the graft, stent and the aorta;
[0046] [0046]FIG. 13 is a diagrammatic view of the apparatus shown in FIGS. 10 - 12 with the delivery tubes in an unstressed, preformed configuration and positioned such that their ends penetrate through the wall of the aorta;
[0047] [0047]FIG. 14 is a diagrammatic view of the apparatus shown in FIGS. 10 - 13 , with first ends of the surgical fasteners emerging from the ends of delivery tubes penetrating through the wall of the aorta;
[0048] [0048]FIG. 15 is a diagrammatic view of the apparatus shown in FIGS. 10 - 14 , with delivery tubes withdrawn from second ends of the surgical fasteners such that the first and second ends of the surgical fasteners are biased closed toward one another;
[0049] [0049]FIG. 16 is a diagrammatic view of the distal end of the apparatus shown in FIG. 10 showing a closed configuration on a guide wire;
[0050] [0050]FIG. 17 is a diagrammatic view of the apparatus shown in FIG. 16 showing the outer endovascular graft delivery sheath partially withdrawn from the stent, with the stent surrounding the endovascular graft, which is partially withdrawn from the inner sheath, which is itself partially withdrawn from the delivery tubes;
[0051] [0051]FIG. 18 is a diagrammatic view of the apparatus shown in FIG. 17 with the graft and the stent extended and expanded over the ends of the delivery tubes (also shown in FIG. 11);
[0052] [0052]FIG. 19 is a diagrammatic view of the apparatus shown in FIG. 18, with delivery tubes returning to an unstressed, preformed configuration for penetration through the graft, stent and the aorta (also shown in FIG. 12);
[0053] [0053]FIG. 20 is a diagrammatic view of the apparatus shown in FIG. 19, with the delivery tubes in an unstressed, preformed configuration such that their ends penetrate through the wall of the aorta; and
[0054] [0054]FIG. 21 is another diagrammatic view of the apparatus shown in FIG. 20 with the delivery tubes penetrating through the wall of the aorta.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0055] Surgical fasteners, each in accordance with the invention, are shown in FIGS. 1 A- 4 . The surgical fastener is preferably a one piece metal or plastic element appropriately configured during manufacture to hold layers of tissue in compression. To apply the fastener, as shown in FIGS. 5 A- 5 F, 6 A- 6 F, and 9 A- 9 D, a straight tube or needle included in a delivery mechanism is preferably used to hold and deflect the fastener from its final shape into a straight configuration. In application, the tube is either inserted through the tissue or held against the tissue to be joined and the fastener is pushed from the tube until the fastener penetrates the tissue and gradually assumes its original shape, trapping and compressing the layers of tissue 18 between its various elements.
[0056] In order to straighten the various surgical wire fasteners described herein without permanent deformation, a superelastic alloy of nickel and titanium is preferably used to make the fasteners. The fastener is preferably made from a commercial material Nitinol, which is referred to as a “shape memory alloy.” Superelasticity can be conveniently likened to memory. Although forced into a straight line after forming, the superelastic fastener is able to “remember” its former shape and to return to it when no longer constrained within a straight tube. Nitinol in superelastic form has an extremely high elastic limit, which allows large amounts of bending without permanent deformation. In general, Nitinol is capable of strain ratios of up to 8% without experiencing permanent deformation. For round wire, the fastener is designed to function within the limits of d/2R equal to or less than 0.08, where d is the diameter of the wire and R is the radius to which the wire is formed. It should be noted that the fastener described herein can be made from any material so long as it is adequately elastic. Preferably, the material has superelastic characteristics.
[0057] The preferred embodiment of the fastener 10 , shown in FIGS. 1 A- 1 C, is essentially that of the body of an extension spring having coils 12 . At rest, the coils of this fastener 10 are spring biased towards each other so that a force is F A required to effect separation of said coils. The force at which the coils just begin to separate is the preload value for the fastener. Additional force causes separation of the coils 12 as a function of the gradient of the fastener. Shown in FIG. 1C, layers of tissue 18 that are trapped between adjacent coils 12 of the fastener will be clamped with a force F 1 being substantially normal to the surface of the tissue 18 and having a value somewhat higher than the preload value of the fastener. This force, which is a function of fastener material, dimensions and winding technique, is chosen to insure hemostasis when vascular tissue is to be clamped. It should be noted that a compression spring could be used in place of an extension spring so long as the tissue is thick enough that it is compressed between the coils of the fastener once it is in place. The theory and practice of winding preloaded coils of metallic wire is routinely practiced in the manufacture of extension springs and is well known to those skilled in the art.
[0058] When the fastener of FIGS. 1 A- 1 C is made of a superelastic material and the strain ratio limitation described above is observed, the fastener can be straightened to penetrate tissue 18 and then released to allow its coils to reform on both the proximate 14 and distal 16 sides of the tissue thereby clamping the tissue between two coils. The number of coils 12 is not especially critical. At least two full coils 12 are required and more, such as four coils, are preferable to make placement in the tissue less critical. The coils 12 preferably have a diameter of {fraction (3/16)} to ¼ of an inch. Preferably, the end of the fastener inside of the body rests flush next to the adjacent coil so that the body will not be injured from the fastener end.
[0059] [0059]FIGS. 2 and 3 show another embodiment of the fastener 20 before and after installation in two layers 14 , 16 of tissue 18 . The presence of the tissue layers prevents the fastener from returning completely to its original state. The force required to spread the spring biased fastener apart by this amount therefore also represents the substantially normal compressive force F 2 applied to the layers of tissue 18 . That force, which is a function of wire diameter and fastener geometry, is chosen by design to achieve homeostasis. Those parameters also determine the gradient or stiffness of the fastener as measured in terms of force F 2 versus deflection of the fastener. Since different tissue thicknesses produce different deflections, and therefore different compressive forces, the gradient must be sufficiently low to maintain reasonable hemostasis over the normal range of tissue thickness without inducing necrosis.
[0060] [0060]FIG. 2 is an isometric view of the fastener 20 shown schematically in FIG. 3. The lower coil 24 penetrates the tissue and curves in a half circle to re-enter the tissue layers. The upper coils 22 bear on the tissue and tend to trap it inside of the larger lower coil. The number of upper coils 22 can vary without altering the essential behavior of the fastener 20 . Preferably, two or more coils 22 are used to help distribute clamping forces more uniformly about the lower coil thereby preventing misorientation of the fastener 20 in the tissue 18 .
[0061] The fastener 40 in FIG. 4 has symmetrical coils to distribute stress uniformly on both sides of the tissues to be joined.
[0062] The fasteners in FIGS. 2 - 3 and 4 are similar to the fastener in FIGS. 1 A- 1 C in that they are spring biased and use coils to apply pressure. The coils in FIGS. 2 - 3 and 4 each have an axis that is oriented substantially transverse to the direction that the fastener takes when it is in a straightened form, whereas the coils in FIGS. 1 A- 1 C each have an have an axis that is substantially transverse to its straightened form.
[0063] The fasteners in FIGS. 1C, 3 and 4 all show a fastener clamping two layers of living tissue 18 which include a proximal layer 14 and a distal layer 16 of tissue. The fasteners described herein, however, can fasten any type of materials together, such as a graft or synthetic fibers which may be used as a substitute for tissue, or a combination thereof. The synthetic fibers, for example, may be a material such as Gore-Tex, Dacron or Teflon. Autogenous and nonautogenous human tissue, as well as animal tissue, may also be used.
[0064] For all fasteners described above, the leading end 21 of the fastener, shown in FIG. 2, can be sharpened for ease of penetration either by cutting the wire on a bias or by tapering the end to a sharp point during manufacture of the fastener. The bias cut is commonly used to make sharp points on conventional staples and taper pointing is used to make a certain class of suture needles. Both techniques are well known to those skilled in the art. Other sharpening techniques such as trocar points may also be effectively applied to the fastener. Alternatively or additionally, a tube 154 of a delivery instrument 150 that houses the fastener, as shown in FIGS. 5 A- 5 F and 6 A- 6 F, can have a sharpened tip which is used to penetrate the tissue 18 prior to pushing the fastener from said tube.
[0065] A wide variety of fasteners can be designed within the scope of this invention for an equally wide variety of fastening purposes. Some of these shapes are shown in FIGS. 1 A- 4 and it should be apparent that other variations are both possible and likely as the invention becomes more widely applied.
[0066] The surgical fasteners described herein can also be used in applications that require the insertion of a fastener from the interior. For example, the fasteners can be used in endovascular procedures to attach a graft within large vessels such as the aorta or iliac arteries to repair aneurysms or occlusions.
[0067] FIGS. 5 A- 5 F show a first embodiment of a deployment instrument 50 and the method for inserting the fastener. The deployment instrument 50 consists of a plunger 52 having a head portion 60 , a needle 54 having a head portion 55 , and a sleeve 51 having a head portion 57 and a stop 56 . The plunger 52 fits slidingly inside a lumen of the needle 54 , which fits slidingly inside of the sleeve 51 . FIGS. 5 A- 5 F show the fastener 10 being used to attach a graft 16 to a blood vessel having a first layer of tissue 14 and an opposite wall 17 . The fasteners described herein, however, can be used for any layers of material or tissue. Furthermore, the delivery instrument 50 can deliver any of the fasteners described herein.
[0068] Depending on the situation, support for the lower membrane 16 will be required in order to insert the fastener 10 . This normally will be the rigidity of the body tissue itself or a mechanical support which is provided separately, often as an integral part of the instrument that deploys the graft.
[0069] For the deployment instrument shown in FIGS. 5 A- 5 D, the head portion 60 of the plunger 52 has two stops 62 , 64 attached to it. One of the stops 62 pivotally engages of the head portion 55 of the needle 54 and also pivotally engages a stop 56 of the head portion 57 of the sleeve 51 . The other stop 64 can engage the head portion 55 of the needle 54 . These stops 62 , 64 are used to control the amount of depth that the needle and/or fastener may be inserted into the tissue 18 .
[0070] In FIG. 5A, the deployment instrument is shown ready to insert a fastener 10 into layers of tissue 18 with the tip of the instrument 50 placed against the tissue. First, the stop 62 is engaged against the head portion 55 of the needle 54 , such that the needle 54 and plunger 52 can be inserted into the tissue 18 in unison. The needle 54 and plunger 52 are inserted until the head portion 55 of the needle 54 rests upon the head portion 57 of the sleeve 51 , as shown in FIG. 5B. It should be apparent that if the needle is inserted into a blood vessel, as shown in FIGS. 5 A- 5 D, care should be taken not to insert the needle past the opposite wall 17 of the vessel.
[0071] In FIG. 5C, the stop 62 is swung to engage the stop 56 on the sleeve 51 . This will enable the needle 54 to be raised while the plunger 52 remains still. While the needle 54 is withdrawn, the restraining force of the needle 54 upon the fastener 10 is removed and the fastener begins to form in its unstressed and undeformed shape.
[0072] In FIG. 5D, the needle 54 is raised until its head portion 55 engages stop 64 . When the needle head portion 55 engages stop 64 , a doctor can be certain that the needle has exited the layers of tissue 18 . The lower portion of fastener 10 will now have formed itself in the shape of a coil.
[0073] In FIG. 5E, the stop 64 is swung away from the head portion 55 such that the needle 54 can be withdrawn fully. As shown, the fastener 10 begins to form in its unstressed shape as the needle 54 is removed.
[0074] [0074]FIG. 5F shows the full withdrawal of the deployment instrument 50 . The fastener 10 can now fully assume its unstressed shape. It should be noted that the unstressed coils of the fastener 10 shown in FIGS. 5D through 5F are shown having an exaggerated shape for the sake of clarity. The fastener 10 more accurately would appear as shown in FIG. 1C with the coils exerting a compressive pressure upon the layers of tissue 18 .
[0075] [0075]FIGS. 6A through 6F show a second embodiment of the delivery instrument 100 which can deliver any of the fasteners described herein. The plunger 102 has a head portion 110 having both a short stop 114 and a long stop 112 attached to it. The head portion 105 of the needle 104 has two slots 116 and 118 to accept the long 112 and short 114 stops, respectively, at different times of the process. The needle 104 is slidingly accepted by sleeve 101 having a head portion 107 . The tip of the delivery instrument 100 , fastener 10 and needle 104 for FIGS. 6 A- 6 F appear the same as in FIGS. 5 A- 5 F, respectively, and are not shown for the sake of clarity.
[0076] First, as shown in FIG. 6A, the long stop 112 is brought into contact with the head portion 105 of the needle 104 . The plunger 102 and needle 104 are then inserted into the tissue in unison by pushing down in the direction of arrow 120 until the needle's head portion 105 comes into contact with the sleeve's head portion 107 , as shown in FIG. 6B. The needle 104 and fastener have penetrated the layers of tissue.
[0077] The head portion 110 of the plunger 102 is then rotated as shown in FIG. 6C in the direction of arrow 122 until the long stop 112 can be inserted into slot 116 . The needle's head portion 105 is then raised in the direction of arrow 124 (FIG. 6D) until the needle's head portion 105 comes into contact with the short stop 114 , as shown in FIG. 6D. In FIG. 6D, the needle 104 will be fully withdrawn from the layers of tissue.
[0078] In FIG. 6E, the plunger's head portion 110 is rotated in the direction of arrow 126 until the short stop 114 can be inserted into slot 118 . The needle's head portion 105 is then fully raised in the direction of arrow 128 (FIG. 6F) until the head portion 105 comes into contact with the plunger's head portion 110 . The needle 104 is now fully retracted from the fastener which should be fastened in the tissue and formed in its unstressed state.
[0079] It should be apparent that many types of stops could be used to position the needle 54 , 104 and plunger 52 , 102 of the deployment instruments 50 , 100 , 105 . For example, the needle could function with only a single stop attached to the shaft of the plunger. Alternatively, visual indicators could be used, but would be inherently less reliable. It should be apparent that the delivery instruments as shown in FIGS. 5 A- 5 F and 6 A- 6 F could function properly without the short stops 64 , 114 , but not as reliably. Also, the delivery instruments, as shown in FIGS. 5 A- 5 F and 6 A- 6 F, could function without the sleeve 51 or 101 , respectively. It should be apparent that a plurality of any of these deployment instruments described herein could be integrated in a single deployment instrument for sequential or simultaneous deployment of the fastener.
[0080] [0080]FIG. 7 shows the deployment instrument 50 as it might be shipped from a manufacturer. The surgical fastener 10 preferably is already inserted and straightened inside of the needle 54 for ease of use. The deployment instrument 50 can be shipped with or without the sleeve 51 , which can be added later when the fastener is ready to be inserted.
[0081] [0081]FIG. 8 shows an enlarged view of the needle of either FIGS. 5 A- 5 F or 6 A- 6 F with a fastener inside of it. A typical aspect ratio of the length to diameter for this device can be in the order of 40 or 50 for less invasive use. The diameter of the fastener is preferably between 0.012 to 0.014 of an inch, more preferably its diameter is 0.013 of an inch, the inside diameter of the lumen 53 of the needle 54 is preferably 0.017 of an inch and the outside diameter of the needle is preferably 0.025 of an inch.
[0082] FIGS. 9 A- 9 D show a third embodiment of the deployment instrument 150 and the method for inserting the fastener. The third embodiment of the deployment instrument 150 is different from the first two embodiments in that a restraining tube 154 is not sharpened to penetrate tissue. Thus, the surgical fastener 20 used with the deployment instrument 150 should have a sharpened end to penetrate tissue. The deployment instrument 150 , consisting of slender tubes and rods, is inherently small in diameter compared to its length. Thus, FIGS. 9 A- 9 D are illustrated with a much less favorable aspect ratio for the sake of clarity. A typical aspect ratio of the length to diameter for this device can be in the order of 40 or 50 for less invasive use. It should be apparent that other ergonomically sophisticated designs for the deployment instrument 150 can be envisioned and realized. It should also be apparent that several of these deployment instruments could be integrated in a single deployment instrument 150 for sequential or simultaneous deployment of the fastener.
[0083] [0083]FIG. 9A shows a deployment instrument 150 resting on layers of tissue 18 to be joined. The deployment instrument 150 restrains a fastener by placing stress upon it. The fastener 20 , which in this example is the fastener of FIG. 1, resides in a substantially straightened form entirely within the restraining tube 154 . It should be apparent that any of the fasteners described herein if given a pointed end 21 can be used with the deployment instrument of FIGS. 9 A- 9 D. The pointed end 21 of the fastener 20 is facing toward the tissue. A plunger 152 rests on the fastener 20 and is configured to push the fastener partially out of the restraining tube 154 until the plunger 152 stops against a shield 156 as shown in FIG. 9B.
[0084] [0084]FIG. 9B shows the fastener 20 partially installed by the plunger 152 . As the fastener emerges from its restraining tube, the fastener 20 penetrates the proximal 14 and distal 16 layers of tissue and gradually assumes the remembered shape of its lower coil, piercing the distal tissue layer 16 again as it turns upward. The lower coil 24 of the fastener 20 , however, preferably remains substantially on the distal side of the tissue. At this point, plunger 152 bears on the shield 156 and can progress no further. Depending on the clinical application, it may be necessary to support the tissue 18 distally during penetration.
[0085] [0085]FIG. 9C shows restraining tube 154 moving upward, gradually freeing the fastener 20 to assume its remembered shape. It will obviously not be able to do so until the restraining tube 154 is completely clear, which happens when the restraining tube stops against plunger 152 . The restraining tube 154 tends to pull the fastener 20 out of the tissue due to friction producing forces exerted by the fastener on the restraining tube as the former tries to assume its remembered shape. This tendency is offset by the plunger 152 bearing on the upper end of the fastener as the restraining tube 154 moves upward.
[0086] [0086]FIG. 9D shows restraining tube 154 in its fully upward position as determined by the plunger 152 . The restraining tube 154 has cleared the fastener 20 and allowed it to assume its remembered, coiled shape 22 , bearing against the tissue 18 . The fastener 20 forms within a guide tube 151 , suggesting that the guide tube 151 , properly shaped, may serve to guide the fastener 20 as it forms above the tissue 18 . This may be a useful feature, especially for more complex fasteners which may re-form incorrectly when released from constraint.
[0087] The guide tube 151 can serve a dual function as described above, providing a reference stop for plunger 152 and a forming guide for the fastener 20 . In some cases the guide tube 151 will not be required.
[0088] The present invention also provides a system for improving fixation of endovascular grafts used to treat aortic aneurysms or occlusive disease of the aorta. In addition, present invention may be used to treat acute and chronic dissections of the aorta including those of the arch, thoracic and abdominal aorta.
[0089] More particularly, medicinal therapy for aortic aneurysms is totally ineffective. In the last 40 years, the incidence of aortic aneurysms has increased by as much as 300%, despite better control of hypertension and the risk factors of atherosclerosis.
[0090] Standard surgical repair of aortic aneurysms is by open repair. This requires a large incision for access, with a morbidity rate as high as 15-30% of patients and a mortality for elective repair of abdominal aortic aneurysms from 2-5%. With intensive care requirements and a long hospital stay of 7-14 days, surgical repair of abdominal aortic aneurysms can result in hospital charges of up to $40,000. In addition, the total recovery time is approximately 4-6 weeks.
[0091] Endovascular grafting was developed to provide a minimally invasive alternative to surgery. There are two FDA approved devices currently available for patient implantation in the United States. Many companies are developing new endovascular grafts and many of these are in clinical trials. Only one device uses hooks which imbed in the aortic wall to fix the proximal end of the graft to the aorta. The other device is reliant on stent technology, which provides fixation of the graft to the aorta by friction.
[0092] Fixation of the graft to the neck of the aneurysm is critical. Failure to achieve fixation prevents complete exclusion of the blood flow from the aneurysm sac. Thus the sac remains pressurized,with normal systematic blood pressure, which will result in enlargement and eventual rupture of the aneurysm. Because fixation of the graft is frequently dependent on friction, the length of normal aorta below the renal arteries (the neck) is the limiting factor in the successful deployment of these new graft devices. In general, the neck needs to be approximately 14-20 mm in length for successful deployment. Other factors limiting adequate apposition using stent technology include the size of the neck, whether it has a regular circumference or whether it bulges, and the angle between neck and the aneurysm.
[0093] With the above restrictions, and despite multiple technological innovations, only approximately 30-40% of patients with infrarenal abdominal aortic aneurysms are suitable candidates for endovascular techniques. The present invention provides an alternative method of fixation which is similar to the interrupted suture used by surgeons at open surgery and will significantly increase the potential patient pool able to undergo repair of the aneurysm by these minimally invasive devices.
[0094] Aortic dissection and dissecting aortic aneurysms are the most serious forms of aortic disease. In its acute stage, death may occur suddenly or within the first few hours or days after onset. Aortic dissection is characterized by a longitudinal separation within the layers of the aortic wall that extends parallel to its lumen. This separation usually arises from a tear that involves approximately 50% of the inner aortic circumference. The tear which marks the beginning of the dissection is located in the ascending arch in 68%, the transverse arch in 10%, the descending thoracic aorta in 20%, and the abdominal aorta in 2%, of patients. Surgical treatment is more difficult than other diseases of the aorta. The pathologic processes involved are more complex, more diffuse and frequently do not permit complete eradication of the disease. The aortic tissues in the acute stage are diffusely inflamed, more friable and less susceptible to secure suture. Total replacement, necessary to eradicate the process in the acute stage, is impractical and unsafe. Associated irreversible complications increase the risk and limit the incidence of a successful operation. Operation in the acute stage is limited to the aortic segment from which immediate complications arise and may be palliative rather than curative. More extensive curative replacement of the entire aorta is feasible in the more chronic stage but is still limited by the associated co-morbidity of the patient. New interventions using endovascular graft stenting have proven feasible and appear to reduce the patient morbitity in carefully selected cases. With the present invention, direct treatment of the tear and the dissection are possible.
[0095] The present invention provides a system for improving fixation of endovascular grafts used to treat aortic aneurysms or occlusive disease of the aorta. In addition, the present invention may be used to treat acute and chronic dissections of the aorta including those of the arch, thoracic and abdominal aorta. Unlike the most commonly used stent technology, which attaches the ends of the graft to the aorta or iliac vessels by friction, this system allows delivery of a special surgical fastener which penetrates through the graft and aorta to securely attach the graft to the aorta. By ensuring a direct and secure graft-aorta attachment, it is possible to sidestep the traditional requirement of a minimum length of normal artery (“neck of the aneurysm”) adjacent to the attachment site. This eliminates the anatomical limitations for endovascular grafting by the friction (stent) method. In those cases of aortic dissection, the delivery of the special surgical fastener through all layers of the aortic wall allows the re-approximation and adherence of these dissected and disrupted layers in a simple, safe and secure fashion without the need for graft placement either by open or endovascular means.
[0096] The present invention comprises a delivery catheter which is able to deploy the special fasteners from within the blood vessels to penetrate through the wall of the blood vessel, allowing attachment of an endovascular graft, including both a virgin endovascular graft and an endovascular graft previously deployed, as well as in the treatment of acute and chronic aortic dissection.
[0097] Looking now at FIGS. 10 - 21 , another preferred embodiment of the invention is shown including an endovascular grafting and repair system 200 and a method for delivery of fasteners using system 200 . In this preferred embodiment of the present invention, endovascular grafting and repair instrument 200 includes a guide wire 205 , a balloon catheter 210 , delivery tubes 215 (FIG. 12), a delivery tube deployment means 220 (shown as an inner sheath 220 ), an endovascular graft 225 , a stent 230 , an outer endovascular graft delivery sheath 235 , a plunger 245 , and fasteners 250 (FIG. 14). System 200 may be used to secure graft devices to the interior of a vascular structure, such as graft devices that rely on friction or hook technology to fix the proximal end of an endovascular graft to the interior of a vascular structure.
[0098] Still looking at FIGS. 10 - 21 , guide wire 205 is shown supporting balloon catheter 210 to allow placement of endovascular grafting and repair system 200 in a vessel 255 (FIG. 11). Generally, guide wire 205 is a stiff wire. In the preferred embodiment of the invention, vessel 255 is shown and discussed in the context of an aorta 255 , but is not limited to such a vessel. Balloon catheter 210 may provide intra-operative angiography to monitor deployment of fasteners 250 and balloon infiltration to ensure full expansion of endovascular graft 225 after attachment to the wall of aorta 255 . Such balloon infiltration also provides excellent apposition of graft 225 to aorta 255 .
[0099] Still looking at FIGS. 10 - 21 , delivery tubes 215 are shown in surrounding configuration to guide wire 205 . Delivery tubes 215 are preferably composed of a super-elastic material, such as Nitinol, and are restrained by inner sheath 220 in a stressed and deformed shape. This deformed shape is of a substantially linear configuration and parallel to guide wire 205 (see FIGS. 11, 16, 17 and 18 ). In a preferred embodiment of the invention, six to eight delivery tubes 215 are provided, and each one contains a preformed fastener 250 , as described herein. Delivery tubes 215 are preformed to return to a given angle relative to guide wire 205 after being deployed from inner sheath 220 (see FIGS. 12, 13 and 19 - 21 ). This angle is to some extent dependent on the diameter of the neck of aorta 255 proximal to an aneurysm (not shown) being repaired.
[0100] Referring now to FIGS. 12, 13, 14 and 16 - 21 , ends 260 of delivery tubes 215 are shown sharpened with a cutting edge for easier penetration through graft 225 and aorta 255 . In an alternative preferred embodiment of the present invention, fasteners 250 have a sharpened end (not shown) to penetrate graft 225 and aorta 255 . Delivery tubes 215 are advanced as a unit to penetrate graft 225 and aorta 255 at a predetermined distance once the site of fixation is determined and, if applicable, graft 225 is deployed. Inner sheath 220 confines delivery tubes 215 until deployment (see FIGS. 11, 16 and 18 ). The position of inner sheath 220 relative to the ends 260 of delivery tubes 215 helps control the angle assumed by the deployed portion of the delivery tubes 215 . This positioning is accomplished by withdrawing and advancing inner sheath 220 away from and toward ends 260 .
[0101] Still looking at FIGS. 10 - 21 , stent 230 is shown surrounding at least a portion of graft 225 , and outer endovascular graft delivery sheath 235 is shown as a slideable cover over the underlying system. Endovascular graft 225 may be made from various materials which include, but are not limited to, Dacron/PTFE. Graft 225 may also be surrounded by an attached stent “exoskeleton” such as is shown in the preferred embodiment. Stent 230 is part of graft 225 and may be a complete or partial stent “exoskeleton”. Outer endovascular graft delivery sheath 235 covers the underlying system for passage through blood vessels and accurate placement of the system.
[0102] Referring now to FIGS. 10 - 15 , plunger 245 is shown having a proximal end 265 and a distal end (not shown, located adjacent to a fastener 250 located at the distal end 260 of a delivery tube 215 ). Plunger 245 is configured for delivery of fasteners 250 once delivery tubes 215 have penetrated aorta 255 . The portion of fastener 215 placed on the distal side of aorta 255 is delivered by moving distal portion 265 of plunger 245 a predetermined distance toward ends 260 of delivery tubes 215 . The portion of fastener 250 placed on the proximal side of aorta 255 is subsequently deployed by withdrawing delivery tubes 215 away from aorta 255 and away from fastener 250 in the wall of aorta 255 . In addition, the withdrawal of delivery tubes 215 away from the wall of aorta 255 further decreases the length of delivery tube 215 surrounding fastener 250 while plunger 245 remains at a fixed location relative to the wall of aorta 255 .
[0103] Endovascular grafting and repair system 200 is preferably used in the following manner to deliver a graft (i.e., endovascular graft 225 and stent 230 ) to the interior of a vascular structure (e.g., aorta 255 ). First, guide wire 205 is positioned in the aorta. Then the remainder of the system, encased in outer sheath 235 , is moved down guide wire 205 until graft 225 is properly positioned in the aorta. Then outer sheath 235 is withdrawn, allowing graft 225 and stent 230 to deploy against the interior of aorta 255 . Then inner sheath 220 is withdrawn, allowing delivery tubes 215 to angulate outward. Next, inner sheath 220 and delivery tubes 215 are advanced distally, causing the sharp distal ends 260 of delivery tubes 215 to penetrate through graft 255 , stent 230 and the walls of aorta 255 . As this occurs, delivery tubes 215 carry fasteners 250 outward so that portions of fasteners 250 also extend through graft 225 , stent 230 and aorta 255 . Then plunger 245 is advanced so as to deploy the outer ends of fasteners 250 against the outside wall of aorta 255 . Next, delivery tubes 215 are retracted, thereby causing the inner ends of fasteners 250 to be deployed against the inside of graft 225 . As a result, graft 225 and stent 230 will be secured to aorta 255 by the coils 12 of fasteners 250 . Then balloon catheter 210 is inflated so as to ensure full expansion of graft 225 and stent 230 , whereby to ensure close apposition of the graft to the aortic wall.
[0104] It should also be appreciated that system 200 can be used to secure a previously-deployed endovascular graft to the wall of an aorta. More specifically, in some situations a previously-deployed endovascular graft may be in danger of migrating within the aorta. In this case system 200 (without graft 225 , stent 230 and inner sheath 220 ) may be used to set fasteners 250 through the previously-deployed graft, whereby to ensure proper fixation of the graft relative to the aorta.
[0105] It should be understood that the foregoing is illustrative and not limiting and that modifications may be made by those skilled in the art without departing from the scope of the invention. | A endovascular fastener and grafting apparatus preferably made from a shape memory alloy is provided which can access internal tissue or other synthetic material by catheter delivery through an endovascular pathway. After the fastener is deployed through layers of tissue or other material, it assumes a shape that automatically applies to the layers of tissue or other material an appropriate hemostatic compression which is relatively independent of tissue or material thickness. The fastener is a suitable replacement for conventional nonbio-absorbable sutures and staples in certain clinical applications. The shape, method of deployment and low force requirements make the disclosed apparatus suitable for standard endovascular surgical procedures where access to the deployment site is limited. A method for deploying the endovascular fastener and grafting apparatus is also provided. | 0 |
RELATED APPLICATION DATA
This application claims priority to U.S. Provisional Application No. 61/636,431 filed Apr. 20, 2012, the entire contents of which are incorporated herein by reference.
BACKGROUND
The present invention relates to system and method for predicting the condition of a cylinder. More specifically, the invention relates to a system and method that uses pressure or another parameter to determine the condition of a pneumatic or hydraulic cylinder.
Pneumatic and hydraulic cylinders are used throughout industry to operate equipment in manufacturing lines and to provide a motive force for various components. Over time, the operation of these cylinders can degrade. However, often, the degradation in performance is not detected until an ultimate failure of the cylinder occurs. If a user is unprepared for the failure, it can result in substantial down time or costs.
SUMMARY
In one embodiment, the invention provides a system that uses one or more pressure sensors to monitor the condition of a cylinder. The system includes a microprocessor/controller that compares measured pressure data to a known baseline for a particular cylinder performing a known function to determine if the operation is acceptable. The system can be standalone or part of a distributed control system. In some constructions, the system can include position sensors that detect the actual position of a piston within the cylinder.
In another construction, the invention provides an actuator system that includes a piston-cylinder arrangement including a piston that is movable with respect to a cylinder. A first flow path is in fluid communication with the piston-cylinder arrangement and a second flow path is in fluid communication with the piston-cylinder arrangement. A control system is operable to fluidly connect the first flow path to a source of high-pressure fluid and to connect the second flow path to a drain to move the piston in a first direction. A pressure sensor is fluidly connected to the first flow path and is operable to measure sufficient pressure data during the movement of the piston to generate a pressure versus time curve. The control system is operable to compare the generated pressure versus time curve to a known standard pressure versus time curve stored in the control system to determine the condition of the piston-cylinder arrangement.
In another construction, the invention provides an actuator system that includes a cylinder defining an internal space and including a first fluid port disposed adjacent a first end of the space and a second fluid port adjacent the second end of the space. A piston is disposed within the internal space and is operable to divide the space into a first side and a second side, the first side in fluid communication with the first fluid port and the second side in fluid communication with the second fluid port. A working member is coupled to the piston and is operable to perform work in response to movement of the piston and a control system is operable to selectively fluidly connect the first fluid port to one of a pressure source and a drain and to connect the second fluid port to the other of the drain and the pressure source to selectively move the piston away from the first port and toward the first port. A pressure sensor is in fluid communication with the first side and is operable to measure pressure data during movement of the piston. The control system is operable to compare the measured pressure data to a known standard to determine the condition of the system.
In yet another construction, the invention provides a method of predicting a failure in an actuator system. The method includes porting a high-pressure fluid to a first side of a piston-cylinder arrangement, draining a low-pressure fluid from a second side of the piston-cylinder arrangement to allow the piston to move with respect to the cylinder toward the second side, and taking a plurality of pressure measurements of the fluid adjacent the first side during the movement of the piston. The method also includes comparing the plurality of pressure measurements to a known set of pressure values and determining if a failure is likely based on the comparison of the plurality of pressure measurements to the known set of pressure values.
Other aspects of the invention will become apparent by consideration of the detailed description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of one possible arrangement of a system embodying the invention;
FIG. 2 is a plot illustrating measured pressure values versus time for a new actuator in the horizontal position with no load and no damping;
FIG. 3 is a plot illustrating measured pressure values versus time for a actuator in the same arrangement as that of FIG. 2 , wherein the actuator is known to be damaged;
FIG. 4 is a plot illustrating measured pressure values versus time for a new actuator in the horizontal position with no load but with damping;
FIG. 5 is a plot illustrating measured pressure values versus time for a actuator in the same arrangement as that of FIG. 4 , wherein the actuator is known to be damaged;
FIG. 6 is a plot illustrating measured pressure values versus time for a new actuator that has a larger diameter than the actuator of FIGS. 2-5 arranged in the horizontal position with no load but with damping;
FIG. 7 is a plot illustrating measured pressure values versus time for a actuator in the same arrangement as that of FIG. 6 , wherein the actuator is known to be damaged;
FIG. 8 is a plot illustrating measured pressure values versus time for a new actuator in the vertical position with a load and with damping;
FIG. 9 is a plot illustrating measured pressure values versus time for a actuator in the same arrangement as that of FIG. 8 , wherein the actuator is known to be damaged;
FIG. 10 is a schematic illustration of the arrangement of FIG. 1 and further including a position measurement system;
FIG. 11 is a schematic illustration of a multi-actuator system including a distributed control system;
FIG. 12 is a screen image of a monitoring system for use in monitoring the performance and condition of one or more actuators;
FIG. 13 is another screen image of the monitoring system of FIG. 12 for use in monitoring the performance and condition of one or more actuators;
FIG. 14 is an image of baseline test results for a known actuator;
FIG. 15 is an image of test results for the known actuator of FIG. 14 with a defective shaft or rod seal;
FIG. 16 is an image of test results for the known actuator of FIG. 14 with a defective rod-side piston seal; and
FIG. 17 is an image of test results for the known actuator of FIG. 14 with a defective rear head (opposite the rod) piston seal.
DETAILED DESCRIPTION
Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways.
FIG. 1 illustrates a system 10 that is suitable for use in predicting or evaluating the condition of an actuator 15 (e.g., pneumatic, hydraulic, etc.) or valve. The system 10 includes a cylinder 17 , a first pressure sensor 20 , a second pressure sensor 25 , and a microprocessor 30 . The illustrated actuator 15 is a typical double acting actuator 15 having a port 35 at either end of a cylinder 17 , a piston 40 disposed between the ports 35 and a rod 45 extending from the piston 40 and out one end of the cylinder 17 . The piston 40 divides the cylinder 17 into a first chamber 50 and a second chamber 55 . Each of the chambers 50 , 55 provides a variable volume that allows for movement of the piston 40 . As one of ordinary skill in the art will realize, the system 10 described herein can be applied to different types of actuators (e.g., rodless) and can be used with actuators powered with different working fluids (e.g., hydraulic fluid, oils, water, fuel, air, other gases, other liquids, etc.). In addition, while the illustrated actuator is not biased in any direction, this system could be applied to spring return actuators as well. In fact, the actual design of the actuator or valve is largely irrelevant as the invention can be adapted to many designs.
The working fluid is admitted into one port 35 and allowed to drain or escape from the other port 35 to move the piston 40 and rod 45 away from the port 35 in which fluid is being admitted. Because a large pressure differential exists during movement of the piston 40 , a seal 60 is provided between the piston 40 and the cylinder 17 . After some amount of use, this seal 60 can wear or otherwise degrade creating one point where failure may occur. A second seal 65 is provided at the end of the cylinder 17 through which the rod 45 extends. This second seal 65 reduces the amount of working fluid that escapes at the rod opening. Through use, this seal 65 can wear or otherwise degrade creating a second point of possible failure.
Typically, one or more valves 70 are used to direct the working fluid to and from the ports 35 as required to produce the desired movement. In a preferred arrangement, a three-way valve 70 allows the first port 35 to be open to a pressure supply 75 and the second port 35 to be opened to a drain 80 in a first position. In a second position, the ports 35 are reversed so that the first port 35 is open to the drain 80 and the second port 35 is open to the pressure supply 75 . The first position and the second position produce movement of the piston 40 and rod 45 in opposite directions. The valve 70 also provides a third operating position in which both ports 35 are closed, thereby trapping the working fluid on both sides of the piston 40 . The third position allows the piston 40 and rod 45 to be positioned and held at some point intermediate of the two extremes. In addition, variable flow rate valves or other flow control devices can be employed to control the rate of fluid flow into or out of the ports 35 to control the speed, acceleration, and exact position of the piston 40 and rod 45 as it moves.
With continued reference to FIG. 1 , the first pressure sensor 20 is positioned to measure a pressure within the first chamber 50 and the second sensor 25 is positioned to measure a pressure within the second chamber 55 . In the illustrated construction, the first sensor 20 is positioned within a first sensor port 85 that is spaced apart from the fluid port 35 already provided in the first chamber 50 of the cylinder 17 . Similarly, the second sensor 25 is positioned within a second sensor port 90 that is spaced apart from the fluid port 35 already provided in the second chamber 55 of the cylinder 17 . In other constructions, the pressure sensor 25 might be connected in line with the fluid lines that connect to the cylinder 17 and the valve 70 or may be connected to a tap line that extends from the feed line or the cylinder chambers 50 , 55 as may be desired.
The pressure sensors 20 , 25 preferably have a range of sensed pressures that exceeds 150 psi with an accuracy of about 0.01 psi with more or less accurate sensors also being possible. Of course, sensors operating at 250 psi or higher are also possible. Additionally, the sensor 20 , 25 is preferably sized to provide a response time that allows for data acquisition at a rate of about 1000 data points per second. Of course other pressure sensors could be employed if desired. For example, in one construction, sound pressure sensors, audio sensors, or other vibration sensors are employed to measure the desired operating characteristics of the actuator 15 .
In preferred constructions, the pressure sensors 20 , 25 are removably connected to the actuator 15 so that they may be reused with subsequent actuators 15 . Alternatively, the pressure sensors 20 , 25 can be manufactured as part of the actuator 15 and replaced with the actuator 15 .
The pressure sensors 20 , 25 convert the measured pressures within their respective chambers into a pressure signal that is transmitted to the microprocessor/controller 30 . In preferred constructions, the microprocessor/controller 30 is dedicated to capture data, stream data and/or analyze for faults or control values. Also, a data logger function can be provided to capture the number of operating cycles, minimum and maximum temperatures, maximum pressures, etc. Each microprocessor/controller 30 can include a unique ID. In the construction illustrated in FIG. 1 , a wired connection is illustrated. However, wireless connections such as infra-red, radio frequency and the like are also possible. The microprocessor/control 30 receives the pressure signals and compares the signals to known signals for actuators 15 to make decisions regarding the performance and condition of the actuator 15 to which it is connected. The microprocessor/controller 30 may include indicators such as lights or audio devices that can be actuated when a particular condition is detected. For example, a red light could be provided and illuminated when excessive wear or damage to the actuator 15 is detected. The microprocessor/controller 30 may have additional inputs (e.g., ambient temperature, pressure, control signals, etc.) and is provided with multiple output options (e.g., Ethernet, RS-485/422, RS-232, USB, RF, IR, LED blink code, etc.). As noted the microprocessor/controller 30 can perform the necessary comparisons and make decisions regarding the operation, maintenance, or condition of the actuator 15 or can transfer the raw data or decision information to a central computer that then displays the information for one or more actuators 15 to a user. Additionally, the microprocessor/controller can perform data logging functions and store data relating to virtually any measured parameter such as but not limited to the number of cycles, maximum and minimum pressures or temperatures, number of faults, etc.
In operation, the present system 10 can be applied to virtually any actuator 15 performing any operation. However, as one of ordinary skill in the art will realize, the performance of any given actuator 15 will vary with the load applied, the positioning of the actuator 15 and the load, the size of the actuator 15 , the distance from the pressure source 75 , and any number of other variables. As such, the preferred approach is to measure the performance of a known actuator 15 in the particular application and use that measured data as a baseline. The baseline represents an acceptable motion profile and is compared to the measured profiles by the microprocessor/controller 30 . This comparison is then used to determine fault condition and reporting.
FIG. 2 illustrates an example of one such baseline measurement that is exemplary and includes pressure measured and plotted versus time. As can be seen, the pressure varied between about 10 psi and 95 psi with other pressure ranges being possible. In addition, the entire stroke of the piston 40 in a first direction takes about 100 ms with faster or slower strokes being possible. In addition, the stroke in one direction can be faster than the stroke in the opposite direction due to the reduced piston area caused by the rod 45 .
With continued reference to FIG. 2 , there are two curves 95 , 100 where each curve 95 , 100 represents data from one of the pressure sensors 20 , 25 . The first pressure sensor 20 is measuring a pressure of slightly more than 10 psi and is therefore connected to the drain 80 . The second pressure sensor 25 is measuring slightly above 90 psi and is connected to the high pressure source 75 . Thus, the piston 40 is displaced to an extreme end nearest the first pressure sensor 20 . At a first time, the control valve 70 is moved to the second position such that the first chamber 50 and therefore the first pressure sensor 20 are exposed to the high pressure fluid 75 and the second chamber 55 and therefore the second pressure sensor 25 are opened to the drain 80 . The pressure within the second chamber 55 immediately begins to drop, following a substantially exponential curve. Simultaneously, the pressure within the first chamber 50 rises substantially linearly to a first pressure level. Upon reaching the first pressure level, the force produced by the high pressure fluid on the piston 40 overcomes the piston's mechanical inertia and any sticking friction and the piston 40 begins to move toward the second pressure sensor 25 . The movement of the piston 40 increases the volume in the first chamber 50 , thereby causing a drop in pressure to a level below the first pressure. Simultaneously, the volume within the second chamber 55 is reduced and the pressure drops toward a lower level at an accelerated rate. Once the piston 40 reaches its end of travel, the pressure within the first chamber 50 increases to a level about equal to the pressure of the high pressure source 75 and the pressure within the second chamber 55 drops to a level about equal to the drain pressure 80 .
As illustrated in FIG. 2 , movement in the opposite direction produces similar curves with slightly different pressure values and durations. The variations in the pressures and the durations are mainly due to the non-symmetric configuration of the chambers 50 , 55 . For example, the first pressure required to overcome inertia and sticking friction is lower in the one direction of FIG. 2 because the piston area is slightly larger due to the omission of the rod 45 on the second chamber side of the piston 40 . The total force on the piston 40 is about the same in both directions. Of course, if a load is applied, this relationship and the values will change based at least in part on that load.
FIG. 3 illustrates the same type of actuator 15 performing the same operation as the actuator 15 of FIG. 2 . However, the actuator 15 of FIG. 3 is known to be defective. A comparison of the curves 110 , 115 of FIG. 3 that correspond with the curves 95 , 100 of FIG. 2 illustrates several differences. For example, the magnitude 120 of the first pressure required to initiate movement of the piston 40 is noticeably higher in FIG. 3 than it is in FIG. 2 . In addition, once piston movement begins, the pressure within the first chamber 50 drops more significantly than it does with the actuator 15 of FIG. 2 . Thus, the pressure variation within the first chamber 50 during piston motion is larger with the damaged actuator 15 of FIG. 3 when compared to the good actuator 15 of FIG. 2 .
The curve representing the data measured by the opposite pressure sensor is also different between FIG. 2 and FIG. 3 . For example, the high pressure value 125 that is maintained prior to moving the valve 70 is lower in FIG. 3 than it is in FIG. 2 . In addition, when opened to the drain, the pressure within the second chamber 55 drops faster in the cylinder of FIG. 3 when compared to the cylinder of FIG. 2 .
The differences between the two curves 110 , 115 can also be illustrative of possible problems with the cylinder. For example, the difference between the maximum pressure within the second chamber 55 prior to switching the valve 70 and the first pressure required to initiate movement 120 of the piston 40 is significantly different between FIG. 2 and FIG. 3 . Additionally, the pressure difference between the two chambers 50 , 55 during motion of the piston 40 and at the end of the piston's stroke is much smaller for the actuator 15 of FIG. 3 when compared to the actuator 15 of FIG. 2 .
As noted, the loading and positioning of the actuator 15 , along with many other factors, greatly affect the pressure data collected by the pressure sensors 20 , 25 . FIGS. 4 and 5 illustrate actuators 15 similar to the actuators 15 of FIGS. 2 and 3 respectively but with the addition of damping to slow the movement of the piston 40 . Again, there are differences in the curves that are identifiable and that could be used to assess the condition of the actuators 15 ; however the curves are very different from those of FIGS. 2 and 3 .
FIGS. 6 and 7 illustrate the same actuator 15 during horizontal operation with no load and no damping. The actuator 15 is a larger diameter than the actuator 15 used to produce FIGS. 2-5 . FIG. 6 is data from a new actuator 15 with FIG. 7 illustrating data from an actuator 15 that is known to be damaged
FIGS. 8 and 9 illustrate a vertically mounted actuator 15 with a load and with damping. FIG. 8 is data from a new actuator 15 with FIG. 9 illustrating data from an actuator that is known to be damaged.
In addition to measuring the pressure in the first chamber 50 and the second chamber 55 , the system 10 is also capable of measuring the total time duration of the stroke and counting the total cycles or strokes of the piston 40 . Both of these values can be used for maintenance cycle purposes or to evaluate the condition of the actuator 15 . For example, the microprocessor/controller 30 could actuate a colored light to indicate that a predetermined number of cycles has occurred and routine maintenance should be performed or the actuator 15 should be replaced. The system 10 can also measure and monitor the maximum operating pressures and signal an alarm if one or more of the operating pressures are exceeded.
Other parameters could be monitored using the first sensor 20 and the second sensor 25 or additional sensors could be provided to monitor other parameters. For example, a temperature sensor could be coupled to the actuator 15 to monitor working fluid temperature, cylinder metal temperature, or any other temperature desired. The temperature data could be used to compensate for the effects of temperature on the operating pressure.
In addition to the monitoring functions described above, the system 10 can also be used to more directly control the operation of the actuator 15 . For example, the microprocessor/controller 30 could provide control signals to the valve 70 or valves controlling the flow of fluid to the actuator 15 to control the speed at which the piston 40 moves or the total force generate by the piston 40 . In addition, the present system 10 is capable of detecting the end of travel and stopping the piston 40 at that point or prior to that point if desired.
Another construction of a system 150 includes a position measurement system 155 that is capable of determining the actual position of the piston 40 within the cylinder 17 . The cylinder 17 illustrated schematically in FIG. 10 is identical to that of FIG. 1 but includes the position measurement system 155 . The position measurement system 155 includes a plurality of magnetic sensors 160 spaced along the length of the cylinder 17 . Each sensor 160 is capable of accurately measuring the angle 165 between it and another magnet 170 such as a magnet 170 placed within or coupled to the piston 40 . A signal indicative of the angle 165 is sent from each sensor 160 to the microprocessor/controller 30 . The microprocessor/controller 30 uses the various angles to triangulate and calculate the precise position of the piston 40 . This positional data can then be used to control the valves 70 to accurately control the position of the piston 40 at any time. This position information can also be used independently or in addition to other sensors for control and/or monitoring purposes.
The systems 10 , 150 described herein can be used alone to monitor and control the operation of a single actuator 15 . The system can signal when the condition of the actuator 15 changes significantly, can signal when maintenance is required and could signal when a replacement actuator 15 or seal is required. In addition, the system could be used to control the operation of the individual actuator 15 .
In another arrangement, the various microprocessor/controllers 30 communicate with a central computer 170 as illustrated in FIG. 11 . The central computer 170 is part of a distributed control system (DCS) that can monitor and control the individual actuators 15 from one location as may be required.
FIGS. 14-17 illustrate actual test results for a known actuators in good condition and the same actuator with three different known defects. FIGS. 14-17 illustrate one possible way in which the present system can be employed. Other types of actuators may have different failure modes and may therefore require slightly different analysis. In addition, the absolute pressures, times, and cycles discloses herein are exemplary and could vary depending on many factors including the application or actuator being used. However, FIGS. 14-17 are exemplary of one possible use for the system.
FIG. 14 illustrates a baseline measurement of a known actuator that is known to be in a good or acceptable condition. The actuator includes a shaft or rod seal a rod-side piston seal and a head piston seal positioned on the opposite side of the piston as the rod side seal. Any one of these seals can fail during use of the actuator and the present system is able to detect that failure before the actuator becomes unusable. As can be seen, the system generates waveforms (or curves) based on pressure measurements taken from both sides of the piston. As illustrated, three specific data points 301 , 302 , and 303 are identified. These three data points will be discussed with regard to the FIGS. 15-17 as these points move in response to particular failures. In addition, it should be noted that the maximum pressure of each side of the cylinder are substantially equal. This is typical of a good cylinder but is a function of any pressure or flow regulator that may be positioned upstream of the fluid ports. Additionally, the low pressure of each wave form is about equal to atmospheric pressure as is typical in a good actuator.
FIG. 15 illustrates similar waveforms for an identical actuator of that of FIG. 14 but with a known defect. Specifically, the rod seal is known to be damaged. As can be seen, the two waveforms no longer intersect at the first data point 301 . Rather, there is now a 2 psi difference between the two points 301 a and 301 b and they have shifted upward from the original 57 psi value. In addition, the second point 302 has shifted downward from 62 psi to 53 psi and the third point 303 has shifted downward from 55 psi to 48 psi. In addition, the maximum pressures of the two waveforms are different as a result of the defect. Any or all of these differences can be used to determine, not only that the actuator is operating abnormally but that the cause of the abnormal operation is likely a defective rod seal.
FIG. 16 illustrates similar waveforms for an identical actuator of that of FIG. 14 but with a known defect. Specifically, the rod side piston seal is known to be damaged. As can be seen, the two waveforms now include many differences. For example, the first point 301 has shifted upward about 3 psi. In addition, the second point 302 has shifted downward from 62 psi to 55 psi and the third point 303 has shifted downward from 55 psi to 49 psi. These changes are similar to those discussed with regard to the waveforms of FIG. 15 . However, the maximum pressure of the two waveforms now has a difference of about 3.5 psi. This is a larger difference than that seen as a result of the damaged rod seal. Furthermore, unlike with the damaged rod seal, the waveforms of FIG. 16 also show a pressure difference between the minimum pressures. Specifically, a difference of 1.5 psi is clearly visible. This difference was not present as a result of the defective rod seal. Thus, these differences can be used to determine, not only that the actuator is operating abnormally but that the cause of the abnormal operation is likely a defective rod side piston seal.
FIG. 17 illustrates similar waveforms for an identical actuator of that of FIG. 14 but with a known defect. Specifically, the head side piston seal is known to be damaged. As can be seen, the two waveforms now include many differences when compared to the waveforms of FIG. 14 as well as the waveforms of FIGS. 15 and 16 . For example, the first point 301 has not shifted when compared to the waveforms of FIG. 14 . This is different than what is seen in FIGS. 15 and 16 . Similarly, the second point 302 and the third point 303 have remained largely unchanged when compared to the waveforms of FIG. 14 . Thus, looking only at these three points, one would conclude that the actuator of FIG. 17 is in a good condition. However, the maximum pressure of the two waveforms now has a difference of greater than 3 psi. This difference is similar in magnitude to that of FIG. 16 but the direction is reversed (i.e., the opposite sensor is higher).
Furthermore, like the waveforms of FIG. 16 , the waveforms of FIG. 17 show a pressure difference between the minimum pressures. Specifically, a difference of about 2 psi is clearly visible. Like the maximum pressure difference, this difference was present in the waveforms of FIG. 16 , but again the direction is reversed (i.e., the opposite sensor is low). Thus, these differences can be used to determine, not only that the actuator is operating abnormally but that the cause of the abnormal operation is likely a defective head side piston seal.
It should be noted that the actuators used to generate the waveforms of FIGS. 14-17 were unloaded. As such, there was very little variation in the cycle times (the X-axis) as a result of the defects. However, in loaded cylinders, the defects discussed above also cause measurable variations in the cycle times. These variations can be measured and reported and can also be used to assess the status of the actuator. In addition to using time variations to determine if potential problems have occurred, some constructions utilize the area under the curve to assess if problems are occurring. More specifically, the area between the curves can be used in situations where the actuator is operated at varying pressures or at varying rates. In these situations, it has been found that the total area under the curve remains substantially uniform. Thus, an increase in this area is indicative of unwanted leakage or other performance failures. In other applications, variations in the area between the curves may be indicative of a particular failure mode alone or in combination with other measured parameters.
Furthermore, the start and the end of a cycle can be easily detected and reported for use in both controlling a process as well as accessing the condition of the actuator. In addition, if a cycle time is determined to be faster than necessary, or slower than necessary, the pressure can be adjusted to achieve the desired cycle time, thereby enhancing the quality of the process and possibly reducing the amount of air or compressed fluid used by the actuator.
FIGS. 12 and 13 illustrate images of one possible monitoring system for use with the systems discussed herein. FIG. 12 illustrates status page for the monitoring system. While the status page includes the status of one actuator, multiple actuators could be grouped together and illustrated as desired. The illustrated image includes three performance indicators with the first indicator providing a red, yellow or green status based on the waveform analysis discussed above. The second indicator provides an indication that the end of the stroke has been reached. The third indicator counts actuator cycles and provides an indication of actuator life based on the number of cycles. The life could be the actual useful life of the actuator or could be set to mirror recommended maintenance intervals for a particular sensor.
The second area of the status page provides numerical data for various operating parameters of the actuator. Other parameters could be measured and displayed as desired. The third area of the status page provides an efficiency analysis. In this example, the efficiency is based on cycle time. The data displayed is a comparison of the actual cycle time versus the desired cycle time with a space provided to provide recommended corrective action based on the result. In this example, the actuator is moving faster than desired. Thus, the pressure of the fluid could be lowered to slow the actuator and potentially reduce the cost of operation.
FIG. 13 illustrated one possible configuration page that provides data specific to the actuator being reviewed. In this example, the bore size, the stroke length, and the total cycle count can be added, stored, and displayed. In addition, the steps required to generate the baseline waveforms ( FIG. 14 ) can be initiated from this page. Finally, alarm set points for any measured parameters can be set with each having a high alarm, a low alarm, and a selector to activate or deactivate the alarm. Finally, a Firmware update status is provided to alert the user when a firmware update is required.
It should be noted that the invention is described as being used with an actuator (sometimes referred to as a cylinder, a pneumatic cylinder, or a hydraulic cylinder). However, in other applications, the invention is applied to a valve or any other flow device. A flow device would be any device that controls the flow of a fluid or operates in response to a flow of fluid being directed thereto. As such, the invention should not be limited to actuators alone.
Thus, the invention provides a system 10 , 150 for measuring and controlling the operation of an actuator 15 . The system 10 , 150 includes pressure sensors 20 , 25 that are capable of collecting data and a microprocessor/controller 30 capable of analyzing the data to determine the condition of the actuator 15 . | An actuator system includes a piston-cylinder arrangement including a piston that is movable with respect to a cylinder. A first flow path is in fluid communication with the piston-cylinder arrangement and a second flow path is in fluid communication with the piston-cylinder arrangement. A control system is operable to fluidly connect the first flow path to a source of high-pressure fluid and to connect the second flow path to a drain to move the piston in a first direction. A pressure sensor is fluidly connected to the first flow path and is operable to measure sufficient pressure data during the movement of the piston to generate a pressure versus time curve. The control system is operable to compare the generated pressure versus time curve to a known standard pressure versus time curve stored in the control system to determine the condition of the piston-cylinder arrangement. | 5 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Application No. 60/564,300 filed Apr. 21, 2004.
FIELD OF THE INVENTION
[0002] The present invention relates to a railroad tie and more particularly to a polymeric extruded railroad tie shaped to receive a steel tie.
BACKGROUND OF THE INVENTION
[0003] Railroad ties are used to support the rails of a railroad. Ties are of a given length and placed at regular intervals for the entire length of the rail system. Switch ties are longer to provide a wider base where switches are installed to switch rail transportation to a different line.
[0004] Railroad ties are traditionally constructed of wood. Wooden ties, however, eventually decompose. Decomposition is more rapid in wooden ties in contact with moisture in a hot wet climate. Insects and bacteria consume the wood and weaken the structure. Ties also crack due to absorbed water freezing and thawing and are subject to damage by equipment. When a tie deteriorates to the point it no longer sufficiently supports the rail, transportation along the rail may be disrupted until the tie is replaced. Replacement of ties consumes resources including time and profits.
[0005] Ties used in railways in underground operations, such as in tunnels and mines, are exposed to harsh conditions, including standing water, increased humidity, heavy loads and acidic conditions. Such ties deteriorate at a rapid pace due to these conditions.
[0006] Alternatives to plain wooden ties have been proposed. Treated wood, such as pressure treating and the addition of chemicals, including chromated copper arsenate or creosote, increases the wood's resistance to insects and decay. The most common treated wood currently used in the railroad market is wood treated with creosote. While treating wooden ties increases the tie's resistant to insects and decay, handling and cutting of pressure treated lumber carries health risks, and the use of creosote-soaked wood products is now banned in several states.
[0007] The cost of wood used to make railroad ties has also increasing due to decreasing supplies. Other types of materials have been developed as substitutes for wooden ties. Cast concrete ties are in use, but expensive to buy and very labor intensive to make and install. Concrete also breaks down over time when subject to freezing temperatures and acidic conditions, and cannot be inserted into track with existing wood ties.
[0008] Steel ties have been developed and are commonly used in mine and tunnel railways. A steel tie connects to and secures the rails with tie plates. Steel ties, however, typically lack good support, which shortens their lifespan compared to that of wooden ties. To add support, steel ties can be bolted to a base, creating an “iron clad tie.” Iron clad ties are useful for increased weight and wear and tear on a line and currently include many shapes, typically called flat, trough, grooved, roof, and box ties.
[0009] Currently, the only bases available are wood and concrete ties, in that the top of the base must conform to the shape of the steel tie. The shaping of the wood is expensive, shaping of rested wood exposes workers to harmful chemicals, and treated wood decomposes and must eventually be replaced. Concrete also is expensive and eventually breaks down in the elements. As relevant to mine use, convention height wooden or concrete rails are impractical as iron clad ties in that the total height of a tunnel may not allow clearance of equipment transported on rails supported with conventional ties.
[0010] Composite railroad ties are a new and growing segment of the railway market. Composite ties are formed from polymeric blends that may include cellulose, chemicals, other resins and fillers that are heated and molded or extruded. Polymeric railroad ties will not rot, crack, warp, or splinter.
[0011] A typical polymer in composites is polyolefin. Polyolefin monomers are the lower olefins: ethylene, propylene, butylene and isoprene. Polyolefins are made by joining these monomers to form long-chain polymers, such as polypropylene and polyethylene. Polyolefins are thermoplastic polymers, in that they become elastic upon heating and firm when cool, and, upon reheating and re-cooling, do not becoming brittle.
[0012] Composite ties are denser than wood and maintenance free in that they are waterproof and unaffected by insects, bacteria and molds. Composite ties, however, are sometimes heavy and difficult to install.
[0013] A need exists for an easy to install, lightweight, weather resistant tie able to serve as a base for a steel tie, which is insect, bacteria, mold and chemical resistant, eliminates environmental concerns and reduces the exposure of workers to hazardous materials. A need exists for a tie capable of supporting a steel tie for use in railways in mines, tunnels and the like.
SUMMARY OF THE INVENTION
[0014] The present invention relates to a tie for use in railways supported with steel ties, particularly for support of rails in mines and tunnels. The tie is made of a polymer blend having a top portion substantially conforming to the bottom shape of a steel tie. The tie is a thermoplastic blend formed by extrusion. The die used to extrude the tie varies to produce a final shape of the tie conforming to a steel tie. The tie is cut into any length after forming. The tie may be predrilled or drilled at the installation site for insertion of one or more than one bolt to secure the tie to the steel tie.
[0015] The present invention is an extruded railroad tie body. The body comprising a bottom, a first side and a second side essentially opposite each other and extending from opposite ends of the bottom and a top surface shaped to receive the bottom of a steel tie.
[0016] The invention further includes a shaping apparatus to extrude a tie for use in supporting a railway for use with a steel tie. The shaping apparatus may be a die with a cavity shaped to produce a tie having a bottom, a first side and a second side essentially opposite each other and extending from opposite ends of the bottom, and a top surface shaped to receive the bottom of a steel tie.
[0017] The invention is a method of making an extruded tie by heating a predetermined polymeric blend to produce a melt, extruding the melt through a die comprising a cavity that conforms to a shape of a bottom surface of a steel tie, and cooling and cutting the formed tie to a desired length.
[0018] The tie is inert in moist and acidic conditions and can be used in place of conventional natural wood ties, particularly those used in mines and tunnels. The tie is compatible with steel ties and can withstand heavy loads, impacts, standing water, insects, bacteria, molds and the like. The tie is such that the steel tie associated with it is easily replaceable.
[0019] Features, aspects, advantages and objects presented and accomplished by the present invention will become apparent and or be more fully understood with reference to the following description and detailed drawings of preferred and exemplary embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 is a perspective view of several embodiments of the extruded tie.
[0021] FIG. 2 shows several embodiments of basic dies used to extrude the tie.
[0022] FIG. 3 depicts several embodiments of shapes of the bottom of the tie.
[0023] FIG. 4 depicts several embodiments of top shapes, which may include side extensions, of the tie.
DETAILED DESCRIPTION OF THE INVENTION
[0024] In one aspect of the invention, there is provided an extruded tie for use in connection with steel ties connected to a railway, and more particularly rails in mines and tunnels, as a superior replacement for wood ties. Accordingly, the invention features a tie comprising a body having a top portion shaped to support the bottom of a steel tie, to be disposed between the steel tie and the ground, ballast, cement, or other bed of a railway. The railway may be located in a mine, tunnel or other like environment.
[0025] FIG. 1 illustrates several embodiments of the present invention. The tie is comprised of a polymer, polymer blend, composite polymer, or any suitable polymer or polymer mixed with additives. The polymer blend comprising the tie may be selected from the thermoplastic polymers, such as the polyolefins, or any other similarly suitable combination of polymers that provides sufficient flexibility, strength, lightness, stability, impermeability and easy processability for extruding the tie. Contemplated polyolefins include, but are not limited to, the C 2 -C 8 polyolefins and their copolymers, included but not limited to polypropylene, polyethylene, and ethylene vinyl acetate. The polymer blend may comprise recycled, off grade, reprocessed, regrind, and or virgin formulation of components blended optionally with resins, chemicals, additives and/or fillers. Fillers include cellulose, such as wood and/or other vegetative fibers, recycled materials, such as tires, door mats, and the like.
[0026] In an embodiment comprising a polyolefin, the materials are combined and thermally fluidized, homogenized and extruded by forcing the heated polymer through a die orifice, which produces the final shape of the finished product. Shapes include those that conform to the most common steel ties. The polymer blend is extruded with the use of conventional extrusion processing with the shaping apparatus of the present invention producing a tie having a top portion shaped to receive a variety of steel ties. The shaping apparatus comprises one or more die used to produce the desired shape of the tie. FIG. 2 depicts basic shapes used for dies. The dies are modified to produce shapes contemplated herein.
[0027] In the extrusion process used to create the tie of the present invention, a predetermined polymeric blend is heated and extruded through a die selected to form a shape that conforms to a particular steel tie. The die is further shaped to eliminate areas of the tie not required for support on order to reduce costs and overall weight of the tie. The die has a cavity shaped in the desired shape of a tie. The melt is forced through the die, cooled and collected.
[0028] When the formed tie passes though the die, it is a continuous length solid extruded shape, with or without projections and having angular and or curved portions forming the final shape of the tie. The extrusion is performed continuously, then cooled and the tie cut to predetermined lengths for given gauges of rails or other uses. The tie may be optionally predrilled upon manufacture or at the installation site to accept one or more bolt for fastening to the steel tie.
[0029] As shown in FIG. 1 , the tie functions similarly to a wooden tie to support a steel tie to form what is commonly known as an “iron clad” tie. In an embodiment of the invention, the tie is approximately 3 inches in height and approximately 7 inches in breadth to function as an iron clad tie for use in a tunnel. Alternatively, the tie may be smaller or of similar height and breadth as that of a conventional wooden tie. The tie may be cut to any desired length.
[0030] The tie comprises a first side 10 and second side 10 a . In an embodiment, the sides extend substantially at right angles from a bottom 11 . The sides may be planar or curved and may optionally include grooves or other modifications to the shape. In an embodiment, the sides extend equal distance from the bottom; however, unequal height sides are contemplated in the invention. In an embodiment of the invention, the sides extend approximately 3 inches from the bottom to accommodate a steel tie and provide a low profile support for rails in a tunnel, mine, or the like. Alternate embodiments of the tie include lower or higher profile sides. In an embodiment, the sides may be equal in height to that of a conventional wooden tie.
[0031] In an embodiment, the height of the sides 10 b , 10 c of the tie may be less than the overall height of the tie. In an embodiment, the steel tie may extend over one or more side of the tie, or alternatively abut to the end of one or more side of the tie at the end distal to the bottom.
[0032] The bottom 11 may be substantially flat, or may be angular or curvilinear to adapt to the ground, cement, ballast or other surface. In an embodiment, the bottom 11 comprises a chamfer 12 . Alternatively, the bottom may comprise other recesses, angles and shapes to reduce the weight of the tie and or to add resistance to movement against, and maintain the tie's position in or on the ballast, ground, cement, etc., upon which the tie is placed. The chamfer 12 and or other recesses, angles and shapes extend the length of the bottom of the tie. FIG. 3 depicts several embodiments of bottom shapes and chamfers contemplated by the invention.
[0033] The chamfer 12 may be of any shape, depth and width, provided structural support for the steel tie and railway is maintained. In an embodiment, the chamfer is relatively centered an equal distance from each of the sides. The chamfer is adapted to receive at least one nut and washer to secure at least one bolt extending through the tie into the chamfer. The washer, nut and extending portion of the bolt are thus distanced from the ground, ballast, or other surface upon which the tie is placed. The chamfer 12 preferably extends no more than approximately one-third of the total height at least one side from an end of the side distal to the bottom end.
[0034] Referring again to FIG. 1 , the tie further comprises a top surface 15 . The top surface is alternatively shaped to accept the bottom surface of a variety of steel tie. In one embodiment 100 the top surface 15 is approximately 8 inches in linear width. In another embodiment 110 , the top surface is approximately 6 inches in width. One skilled in the art should readily realize that the linear width of the top surface is contemplated to conform to a steel tie to be attached and thus is not restricted to the examples provided. In an embodiment, the width of the top surface 15 is substantially equal to the width of the bottom 11 . Alternatively, as shown in several embodiments of dies used to shape a tie depicted in FIG. 2 , the bottom is wider that the top surface (Column 220 ). In such embodiments the sides of the tie form acute angles with the bottom.
[0035] The top surface 15 of the tie is alternatively shaped to receive a variety of steel ties. The invention is adaptable to receive current steel ties as well as those contemplated in the future. In an embodiment, the top surface 15 extends at a substantially right angle from each of the sides. In an embodiment, the top surface 15 indents at a given distance from each side to provide an abutment for and accept the side ends of current steel ties. Each indent 20 , 20 a extends the length of the tie. Several embodiments of dies shaped to form a top surface with indents are embodiments depicting in Column 200 of FIG. 2 .
[0036] The top surface 15 extends center ward from each indent 20 , 20 a in a shape to conform to a steel tie. Contemplated shapes include but are not limited to flat, trough, grooved, roof, and box steel ties. Several embodiments of top surfaces of the tie are depicted in FIG. 4 .
[0037] Alternatively, the top surface 15 does not comprise indents. Column 210 of FIG. 2 depicts several embodiments of dies used to shape such ties. In these embodiments, the steel tie may enclose the top surface of the tie.
[0038] The top surface may be shaped to support any steel tie. FIG. 4 depicts several embodiments of top surfaces. As shown in FIG. 4 , the top surface may comprise additional chamfers, grooves and or channels to eliminate portions not required for support.
[0039] In an embodiment 100 depicted in FIG. 1 and shaped to support a trough steel tie, the top surface 15 comprises a modified convex curve extending from the indent 20 , 20 a to a first high point 21 and a second high point 21 a . Such curves support the bottom surface of the steel tie. Alternatively, the curves may comprise channels or grooves to reduce the weight of the tie in areas not essential to support the steel tie and the railway.
[0040] As shown in several embodiments of dies used to shape the top surface 15 depicted in FIG. 4 , the top surface may alternately be planar, rounded, and or angled. The top surface may or may not be essentially parallel to the bottom.
[0041] In an embodiment, the tie is channeled in an area corresponding to a center piece of a trough or grooved steel tie. The channel 22 runs the length of the tie and is adapted to receive at least one bolt to secure the steel tie to the tie of the invention. The tie may be optionally drilled at one or more predetermined section of the channel to receive one or more bolt. The channel enables a head of the bolt to be located below the outer most surface of the top surface. The predrilled holes and bolts extend from the top surface to the chamfer or bottom for attachment of one or more washer and or nut.
[0042] One skilled in the art will understand that the description of the present invention herein is presented for purposes of illustration and that the design of the present invention should not be restricted to only one configuration or purpose, but rather may be of any configuration or purpose which essentially accomplishes the same effect.
[0043] The foregoing descriptions of specific embodiments and examples of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teachings. It will be understood that the invention is intended to cover alternatives, modifications and equivalents. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated.
[0044] It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. | The present invention relates to an extruded railroad tie shaped to receive and support a steel tie. The extruded tie is useful for support of railways in mines, tunnels and the like. | 4 |
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