This invention teaches rechargeable manganese dioxide cells having alkaline electrolytes, zinc negative electrodes and manganese dioxide positive electrodes. In keeping with the present invention, the positive electrode is essentially unconstrained--that is, no cage is used in the cell to confine the positive electrode. During discharge of a rechargeable alkaline cell, the positive electrode may be inclined to swell, and during the charge cycle it may be inclined to contract or reduce its dimensions. However, the positive electrode is dimensioned so as to substantially fill the entire space allotted for it within the cell, while allowing for a slight accommodation for height-wise or longitudinal expansion or growth in bobbin cells. The positive electrode may include additives such as carbon or graphite to increase its electrical conductivity; hydrophobic agents such as PTFE, polyethylene or polypropylene to enhance the hydrogen permeability of the positive electrode and thereby lead to increased hydrogen recombination rates; and similar hydrophobic agents as well as hydrophillic additives to serve as lubricants and to reduce tool wear during manufacturing processes. Also, the discharge capacity of the negative electrode may be established so as to be in the range of from about 60% to about 120% of the theoretical one electron discharge capacity of the positive MnO.sub.2 electrode.

It must always be recognized and kept in mind that when cells have an alkaline electrolyte, negative electrodes as discussed above, and rechargeable manganese dioxide positive electrodes, they are assembled in their fully charged state. Accordingly, the first cycle to which any such cell is subjected in use is a discharge cycle, after which the cell is required to be recharged for subsequent use. This is, of course, in contradistinction to nickel cadmium (Ni/Cd) or nickel metal hydride (NiMeH) cells, which must first be charged before they are capable of being used. The present invention may extend to button cells, although the discussion is particularly directed to bobbin cells. In any event, any cell in keeping with the present invention is subjected to discharge when it is first put into use; and then to charge and discharge cycles. However, because of the tendency of manganese dioxide positive electrodes to swell on discharge, especially in the presence of an alkaline electrolyte, care must be taken to ensure that the positive electrode maintains its integrity and does not disintegrate or substantially swell in such a manner as to disturb the internal structure of the cell. Otherwise, the cell could be rendered ineffective for further use.
Generally, cells in keeping with the present invention have a manganese dioxide positive electrode--as discussed in greater detail hereafter--together with a negative electrode, a separator, and an alkaline electrolyte, all in a suitable container. The container is sealed by a suitable closure. In general, cells in keeping with the present invention will have a potassium hydroxide electrolyte which is 1N to 15N, and which may further have zinc oxide dissolved in it.
The separator which is used between the positive electrode and the negative electrode generally consists of an absorbent layer, which serves as an electrolyte "wick", and a barrier layer whose purposes is to prevent short circuits in the cell due to the growth of zinc dendrites which may otherwise extend between the positive electrode and the negative electrode. These properties are best obtained using a two-layer separator system, or a laminated separator.
When the negative electrode is zinc, it is generally a zinc powder mixed with a gelling agent. The gelling agent may be such as potassium polymethacrylate or polymethacrylic acid, carboxymethyl cellulose, starches, and derivatives thereof. Metallic corrosion inhibitors such as lead, cadmium, indium, gallium, bismuth, and even mercury in very small quantities, may also be included in the formulation of the negative electrode, as well as organic corrosion inhibitors, so as to reduce hydrogen gassing within the cell. Optionally, zinc oxide powder may also be included in the negative electrode formulation.
The discharge reaction of manganese dioxide is quite complex, and may proceed in various steps. A description of the manganese dioxide discharge mechanism in the presence of an alkaline solution that has been proposed by Kozawa is generally accepted, and is described in Chapter 3 of "Batteries", Volume 1, Manganese Dioxide--edited by K. Kordesch. The MnO.sub.2 discharge curve has a sloping characteristic, indicating an homogenous phase reaction. The potential of the MnO.sub.2 changes continuously while protons originating from the water of the electrolyte are introduced into the lattice of the manganese dioxide, according to the equation: EQU MnO.sub.2 +H.sub.2 O+e.sup.- =MnOOH+OH.sup.- (Equation 1).
However, the MnO.sub.2 lattice expands as an increasing number of protons are inserted into the lattice, and at a certain point during the discharge the discharge mechanism changes. After that time, the discharge may occur in a heterogenous phase reaction, according to the equation: EQU MnOOH+H.sub.2 O+e.sup.- =Mn(OH).sub.2 +OH.sup.- (Equation 2).
This second reaction step involves the dissolution of MnOOH in the form of {Mn(OH).sub.4 }.sup.-, with electrochemical reduction on the graphite additive found in the manganese dioxide positive electrode Mn(OH).sub.4.sup.=, and the precipitation of Mn(OH).sub.2 from it.
Manganese dioxide electrodes, when used as rechargeable positive electrodes in electrochemical cells, are known to be rechargeable only if the manganese dioxide is charged and discharged no more than between its nominal status of MnO.sub.2 and its fully discharged one electron status of MnOOH. For purposes of the present discussion, the theoretical discharge capacity of the MnO.sub.2 electrode between the MnO.sub.2 status and the MnOOH status is termed or designated as the theoretical one electron discharge capacity of the MnO.sub.2 electrode. If the discharge process of the MnO.sub.2 positive electrode continues beyond the MnOOH level, an irreversible phase change has been reported to occur, so that the manganese dioxide electrode is no longer fully rechargeable.
Specifically, Equation 1, above, is descriptive of the discharge reaction which takes place as the MnO.sub.2 discharges towards its MnOOH one electron discharge level in the presence of an aqueous electrolyte. Generally, the theoretical one electron discharge capacity of MnO.sub.2, as it follows the discharge reaction of equation 1, is considered to be 308 mAh/g of MnO.sub.2. It must not be overlooked that during such discharge, the structure or lattice of the MnO.sub.2 electrode expands or at least tends to expand.
Moreover, at a certain point of further discharge, the discharge mechanism may change; and after that point the discharge, which is in the second electron discharge level of the MnO.sub.2 electrode, occurs following a heterogeneous phase reaction which is set forth in Equation 2, above. Particularly with reference to alkaline manganese dioxide/zinc cells, the second step described in Equation 2, above, occurs at a voltage which is too low to contribute significantly if at all to the service life of the cell, since it occurs below 0.9 volts. Generally, it is found that with practical cells formulations, the second discharge step described above is irreversible, thereby rendering the MnO.sub.2 electrode to be non-rechargeable. Therefore, this second discharge step must be prevented from happening.
In other words, MnO.sub.2 is, in principle, capable of giving up twice its one electron recharge capacity. However, the second electron discharge capacity of MnO.sub.2, past its first electron discharge capacity, is not rechargeable in practical cells in any meaningful way, and occurs in any event at too low voltage to be useful.
With respect to prior art MnO.sub.2 /Zn cells, there have been a number of steps taken to ensure rechargeability; and specifically, steps have been taken to severely limit the discharge capacity of the negative electrode, or to provide electronic means to preclude overdischarge of the MnO.sub.2 positive electrode, so as to provide rechargeable MnO.sub.2 /Zn cells. This has been particularly of concern when it was intended to provide MnO.sub.2 /Zn cells in sufficient quantities as to make them commercially viable, meaning especially that ordinary commercially available battery grade manganese dioxide had to be relied upon.
Of course, it is generally to be noted, as well, that it is the MnO.sub.2 electrode that provides the difficulty as to rechargeability; it being generally known that it is the material of the negative electrode that is rechargeable over most if not all of the cycle life of the cell.
Historically, rechargeable alkaline MnO.sub.2 /Zn cells that have been brought to the market in the late 1960's and early 1970's were not successful because of the constraints placed upon them. Those constraints were, as noted above, the use of electronic controls to determine the end of the discharge--that is, to cut off the discharge at a certain point--or even placing the onus on the user of the cell to keep records of the amount of use that the cells were put to, and then to place the cells in the charger for recharging at an appropriate time--which must be neither too early nor too late. In general, such cells were merely modified primary alkaline MnO.sub.2 /Zn cells, and generally they had the same ratio between the active materials in the negative electrode and positive electrode as primary cells but merely employed binders such as cement to preclude structural failure of the MnO.sub.2 electrodes, as well as additives to suppress gas formation, and of course improved separators to preclude the chance of shorting between the negative electrode and positive electrode. Such cells were also quite low in respect of their energy densities: for example, a D cell may have been rated at only 2 Ah as a rechargeable cell, and it could deliver a total of only 6 Ah before the cell was completely exhausted and not further rechargeable. In such cells, the theoretical capacity of the zinc negative electrode was generally set higher than that of the theoretical one electron discharge capacity of the MnO.sub.2, at about 125% to 135% of the theoretical one electron discharge capacity. A more full discussion of the above is found in FALK and SALKIND Alkaline Storage Batteries, published by John Wiley & Sons, New York, 1969, at pages 180 to 185, and also pages 367 to 370.
Kordesch, in U.S. Pat. No. 2,962,540 describes cement bonded anodes for use in single use dry cells. The positive electrodes may have bobbin configuration, or plate configuration, and the structure of the positive electrodes is such that they are integrally united with 5% to 20% of cement additives. Optionally, a further 2% to 20% of steel wool may be employed as further cathode reinforcement. The purpose of the patent is to overcome the electrical resistance that is noted in unbonded positive electrodes, which electrical resistance is caused by the expansion of the positive electrode during discharge.
In U.S. Pat. No. 3,113,050, Kordesch describes positive electrodes that may be used in both primary and rechargeable cells. Those positive electrodes are cement and latex bonded so as to reduce expansion and contraction during discharge and charge cycles. The cement and latex binder additives are each present in the range of from 2.5% to 20%. An additional 2% to 20% of cement and/or latex binder additives can additionally be incorporated.
Alternatively, so as to overcome the limitations noted above, cells were developed by which the discharge capacity of the cell was limited by imposing negative electrode limitation on the capacity of the cell--by which it was made impossible to discharge the MnO.sub.2 to more than a predetermined amount because of the available capacity of the negative electrode. Generally, that meant that the discharge capacity of the zinc negative electrode was allowed to become no more than about 30% of the theoretical one electron discharge capacity of the MnO.sub.2 positive electrode. This, at least, preserved the rechargeable characteristics of the cell, but resulted in a cell having quite low deliverable energy capacity and density. Those limitations, understandably, mitigated against the commercial acceptability of such cells.
Reference is made to Amano et al U.S. Pat. No. 3,530,496, issued Sep. 22, 1970. Amano et al make a very strong statement of their intent to limit the depth of discharge of the MnO.sub.2 electrode by providing a negative electrode that has its capacity limited to between 20% to 30% of the theoretical one electron MnO.sub.2 discharge capacity. Amano et al prevent the mechanical failure of the positive electrode through the addition of nickel powder, which also increases the electrical conductivity of the positive electrode, and as well significantly enhances its mechanical strength. By adding nickel powder to the positive electrode, Amano et al observed a diminished tendency of the positive electrode to swell and to peel or delaminate. However, according to Amano et al, without the addition of a reinforcing agent such as the nickel powder, which acts as a binder for the positive electrode, the electrode can only be discharged to about 20% of its theoretical one electron capacity without experiencing mechanical failure of the positive electrode. As the positive electrode is only discharged to such a shallow depth, the expansion and contraction of the electrode during cycling are not extensive enough so as to cause mechanical failure. Amano et al have reported that the addition of nickel binder and graphite in a weight ratio of MnO.sub.2 :graphite:nickel of 8:1:1 increases the cycle life of the positive electrode having negatie electrodes that have capacities up to about 30% of the theoretical one electron discharge capacity of the MnO.sub.2 positive electrode. Amano et al also report that the nickel additive reduces "spring back" action of the pre-molded cathode pellets as they are released from the molding die.
How Amano et al achieve their zinc negative electrode limitations is that they provide positive electrodes having dimensions that are essentially equal to those of primary alkaline cells, and then reduce the zinc capacity of the negative electrodes by placing an annular or hollow cylindrical gelled zinc negative electrode adjacent to the MnO.sub.2 positive electrode and separated from it by a suitable two component separator. Then, the center of the negative electrode is filled with gelled electrolyte that does not have any active negative electrode material added to it. Amano et al also prefer that amalgamated copper particles be included in the negative electrode so as to enhance its conductivity. Moreover, in the negative electrode Amano et al also provide a zinc oxide reserve mass, they employ PTFE as a binder, and they must use a perforated coated screen current collector rather than a single nail which would otherwise be used in a primary MnO.sub.2 /Zn alkaline cell.
Ogawa et al, in U.S. Pat. No. 3,716,411, issued Feb. 13, 1973, teach a rechargeable alkaline manganese cell, the discharge capacity of the negative electrode of which is controlled within such a range that the positive electrode can be recharged; and wherein the negative electrode and positive electrode face each other through a gas permeable and dendrite impermeable separator. However, the Ogawa et al cell is strictly negative electrode limited in that the capacity of the negative electrode is held to be not more than about 40% of the theoretical one electron discharge capacity of the manganese dioxide. Ogawa et al discuss the fact that if a zinc-manganese dioxide cell is discharged so that its terminal voltage reaches a voltage below 0.9 volts and down to about 0.75 volts, and where the capacity of the zinc negative electrode is about the same or slightly smaller than that of the manganese dioxide positive electrode, then the effect of the discharge on the manganese dioxide is such that it is non-reversible at least in part. Ogawa et al insist that under no conditions should the depth of discharge of the negative electrode be permitted to exceed 60% of the theoretical one electron discharge capacity of the manganese dioxide positive electrode. Ogawa et al provide an alternative structure which comprises two positive electrodes, one on either side of the negative electrode, and wherein the inner positive electrode is contained within a perforated nickel plate steel pocket or canister.
It should be noted that Ogawa et al also describe an MnO.sub.2 positive electrode for secondary cells using a carbonyl nickel binder in an approach that is similar to the one described by Amano et al. Moreover, Ogawa et al utilize an unusually thick separator, having a thickness of between 0.5 and 4 mm, with the anticipation that the thick separator will provide a confinement to preclude swelling of the positive electrode in a manner similar to the metal cages used by Kordesch et al in U.S. Pat. No. 4,384,029, described below. The negative electrode employed by Ogawa et al is formed by applying a paste which contains zinc particles to a copper net or screen, which serves as the current collector. However, the negative electrode is so viscous and stiff that it must be kneaded before it is inserted into the cell. Still further, the metal screen also provides confinement for the positive electrode so as to constrain its tendency to swell during charge and discharge cycling.
Tomantschger et al, in a commonly owned U.S. patent application Ser. No. 07/893,793 filed Jun. 4, 1992, provide rechargeable alkaline manganese zinc cells that utilize an MnO.sub.2 positive electrode and a zinc negative electrode, wherein the negative electrode capacity of the zinc is limited to greater than 60% and up to 100% of the theoretical one electron discharge capacity of the MnO.sub.2. That provides a rechargeable alkaline manganese cell having higher capacity and higher energy density than has been available from the prior art cells.
What the present invention provides is cells with a manganese dioxide electrode, and which have a high capacity and a high drain capability relative to prior art cells. A negative electrode is provided, with a separator between the negative electrode and the MnO.sub.2 electrode, together with appropriate terminal means contacting the negative electrode and MnO.sub.2 electrode so as to provide respective negative and positive terminals for the cell. The manganese dioxide of the unconstrained MnO.sub.2 electrode is capable of being charged and discharged at or below the theoretical one electron discharge capacity of the MnO.sub.2 electrode, which is between the MnO.sub.2 status and the MnOOH status.
In its broadest terms, the present invention contemplates negative electrodes where the principal active component may be chosen from the group consisting of zinc, hydrogen, and metal hydrides. Other elements such as iron, lead, or cadmium might also be considered under certain conditions for special use purposes. The principal component of the aqueous electrolyte is chosen to accommodate the specific couple between the negative electrode and the positive MnO.sub.2 electrode, and particularly may be chosen from the group consisting of alkali metal hydroxides--e.g., KOH--or an acid such as H.sub.2 SO.sub.4, H.sub.3 BO.sub.3, or H.sub.3 PO.sub.4, or mixtures thereof; or a solution of salt which may be ZnCl.sub.2, NH.sub.4 Cl, or KCl, or mixtures thereof. The negative electrode is, of course, rechargeable.
In keeping with the provisions of the present invention, the theoretical discharge capacity of the negative electrode is in the range of from 60% to 120% of the theoretical one electron discharge capacity of the MnO.sub.2 electrode. In other words, the electrode balance of cells in keeping with the present invention is in the order of from 60% to 120%.
In a typical embodiment of cells according to the present invention, where the cells are intended for commercial exploitation, the active material of the negative electrode is zinc, and the electrolyte is 1N to 15N potassium hydroxide.
Cells according to the present invention may have a number of additives for purposes of enhancing the performance of the MnO.sub.2 positive electrode, or for catalyzing oxygen evolution or hydrogen recombination, or for ease of MnO.sub.2 electrode manufacturing processes, and so on. The MnO.sub.2 electrode may include at least one electrically conductive additive which is chosen from the group consisting of 5% to 15% by weight of graphite, and 0.1% to 15% by weight of carbon black. The carbon black may be present as a porous additive in the MnO.sub.2 electrode.
The addition of various barium compounds such as barium oxide, barium hydroxide, and barium sulphate in the range of from 3% to 25% may also be desired. The use of the barium compounds results in an increased cycle life and in an improved cumulative capacity of the cell.
To promote hydrogen gas recombination within the positive electrode, the electrode composition may include hydrogen recombination catalysts such as those taught in commonly owned U.S. Pat. No. 5,162,169 issued Nov. 10, 1992. The MnO.sub.2 electrode may comprise from 0.01% to 5% of a hydrogen recombination catalyst such as one chosen from the group consisting of silver, oxides of silver, silver salts, platinum, and compounds of silver and platinum.
Alternatively, the addition of a wet proofing agent such as from about 0.1% to about 3% and up to 5% of PTFE, polyethylene, or polypropylene, will enhance the gas transport within a single use or a rechargeable MnO.sub.2 positive electrode to such an extent that, as noted above, significant hydrogen recombination rates can be obtained even with uncatalyzed MnO.sub.2 electrodes. Moreover, the addition of porous additives such as acetylene black in the range of from about 0.1% to about 15%, especially if those additives have been rendered hydrophobic, also greatly enhances the gas transport capabilities of the positive electrode. It follows that the combination of a partially hydrophobic positive electrode which further employs wet proofed porous additives and which may also include a hydrogen recombination catalyst, will provide for the maximum hydrogen gas recombination rates.
Alternatively, carbon black may itself be wet proofed by treating it with PTFE. Such a product is available under the trade mark TAB-1 from IBA Shipping Center, of Torrance, Calif. The TAB-1 material is an acetylene black which has been rendered hydrophobic by the application of PTFE, and it has been developed for use in gas diffusion electrodes. Indeed, this product has been found to be well suited for maintaining gas permeability within a MnO.sub.2 primary or secondary electrode, thereby significantly enhancing the hydrogen gas permeation characteristics of the positive electrode.
Still further, so as to provide for overchange capability, an oxygen evolution catalyst as taught in commonly owned U.S. Pat. No. 4,957,827, issued Sep. 18, 1990, to Kordesch et al, may be utilized. Whatever catalyst is selected, it is chosen so as to be stable over a wide voltage range--typically from 0.75 volts versus Zn to 2.0 volts versus Zn--and also over a wide temperature range--typically from -40.degree. C. to +70.degree. C.--without any significant deterioration in performance of the cell. Such catalysts may be oxides, spinels, or perovskites of nickel, cobalt, iron, manganese, chromium, vanadium, titanium, and silver. As taught in U.S. Pat. No. 4,957,827, an oxygen evolution catalyst may be placed on the outer surface of the positive electrode, or it may be dispersed throughout the MnO.sub.2 electrode.
By adding lubricants to the positive electrode, a number of desirable effects can be achieved. In particular, the moldability of the positive electrode may be increased, and as well the amount of wear on the tools used for processing and manufacturing the positive electrode may be decreased. Moreover, it is well known that there is a "spring back" phenomenon which accompanies manufactured positive electrodes, where the positive electrode pellet will increase its size somewhat after it has been removed from the pellet press but prior to it being inserted into the cell. "Spring back" phenomenon can be significantly suppressed by using lubricants added to the positive electrode. The lubricants that have been tried are metal salts of stearic acid, or polyethylene, polypropylene, PTFE, or other polymeric materials which are otherwise benign when added to the positive electrode formulation. Such lubricant additives may be typically employed in concentrations of between 0.1% to about 3% and up to 5%, based on the weight of the positive electrode. It should be noted that such lubricant additives are becoming increasingly important in the case of low mercury or mercury free zinc MnO.sub.2 cell; and this is because any impurity which is introduced into the cell as a consequence of tool wear will generally increase the hydrogen gassing that may be experienced with the negative electrode of the cell. For example, it has been found that iron introduced into the positive electrode as a consequence of tool wear are may be fairly mobile within the cell electrolyte, so that it may eventually find its way to the zinc negative electrode of the cell. There, the presence of iron will suppress the hydrogen over-potential on zinc, and consequently it will enhance hydrogen generation within the cell.
Depending on the nature of the cell, the positive electrode may be molded into pellets and inserted into the can, followed optionally by recompaction. Otherwise, the positive electrode may be extruded directly into the can, or it may be rolled or cast as a flat electrode for use in spirally wound cells or even in respect of button or coin cells.
In any event, regardless of the specific nature of the positive electrode that are inserted into the can, it has been found that the application of a conductive carbon based coating to the inside surface of the can will provide a significant benefit in at least two respects. First, the effort required for pellet insertion or extrusion of a positive electrode into the can may be significantly reduced, and moreover, the electrical contact which is made between the can and the positive electrode is improved so that there will be a reduced internal resistance noted in the cell throughout its cycle life. Still further, an increased short circuit current for the cell will be achieved, and there will be better performance of the cell after extended periods of storage. A suitable can coating dispersion is available from Lonza Ltd. of Sins, Switzerland, under the product designation LGV 1188; and it provides a 43% aqueous dispersion of graphite and a polyvinylacetate co-polymer.
It has been well shown that a manganese dioxide positive electrode expands during discharge and contracts during charge. Kordesch et al in Electrochemica Acta 25 (1981) at 1495 to 1504, have shown that cycling an unconfined binderless manganese dioxide positive electrode resulted in electrode failure in just four discharge/charge cycles, due to its bulging and mechanical disintegration. For totally confined electrodes, 30 to 40 cycles were reported when various commercially available electrochemical manganese dioxide (EMD) were employed, and where the positive electrode was discharged only up to no more than 35% depth of discharge based on the theoretical one electron capacity of the positive electrode. Kordesch et al concluded that the failure mode was not a consequence of the build up of an insulating layer on the manganese dioxide electrode, but due to a mechanical disintegration of the electrode accompanied by a resistance increase of the electrode.
Kordesch et al also demonstrated in half cell experiments that if a similar electrode was confined by a perforated disk under pressure, the confined electrode continued its cycling life well beyond the fourth cycle; and moreover, that the change in dimension between the charged and the discharged electrode was only about half of that which occurred in the unconfined electrode. It was demonstrated that a mounting pressure of about 250 to about 750 N/cm.sup.2 was required to increase the cycle life from less than about 5 cycles--noted, above, to be because of poor conductivity and mechanical disintegration--to at least 75 cycles. A peak of 92 cycles was found at 500 N/cm.sup.2. However, it was also found that at higher mounting pressures, the cycle life would drop because of the loss of pore volume within the manganese dioxide electrode, thereby creating problems with respect to electrolyte penetration within the electrode.
When a manganese electrode is in the form of a sleeve or a disk, additional difficulties may arise. The internal resistance of the electrode may increase, and the mechanical disintegration of the electrode may be particularly severe. Kordesch, in "Batteries", Volume 1 at pages 201 to 219 discusses these problems. Several prior art references show attempts to preclude the expansion of a manganese dioxide electrode during discharge and, indeed, to try to prevent its contraction during charge. Such prior art attempts have included the addition of a binder such as cement (U.S. Pat. No. 2,962,540); the addition of graphitized textile fibres (U.S. Pat. No. 2,977,401); the addition of latex binders (U.S. Pat. No. 3,113,050); the use of combination binders such as cement and steel wool (U.S. Pat. No. 3,335,031); and the use of supplementing binders (U.S. Pat. No. 3,945,847), all as discussed above. None of those patents, however, could preclude the mechanical disintegration of the manganese dioxide electrode over many cycles, apparently due to the limited binding strength of the materials being used.
Kordesch and Gsellman in U.S. Pat. No. 4,384,029 issued May 17, 1983, teach cylindrical bobbin cells which may use mechanical enclosures such as tubes, springs, mechanical wedges, and perforated cylinders, to preclude expansion of the cathode during discharge of those bobbin cells. What that patent attempts to do is to create a constant volume manganese dioxide positive electrode, which means that the electrode must always be under a certain mounting pressure at all times. The patent suggests that by increasing the mounting pressure, the number of useable cycles for the cell will increase. By providing the metal cage, which is essentially rigid, the tendency of the manganese dioxide electrode to swell creates internal pressure within itself, which acts against the metal cage and between the cage and the can, thereby counteracting the tendency to swell; and by maintaining the manganese dioxide electrode under pressure, the electrode retains a substantially constant volume during discharge as well as charge.
A different approach, using combinations of binders with a mechanical retainer of multiple mechanical retainers is disclosed in a further patent which is commonly owned herewith, being U.S. Pat. No. 4,957,827 issued Sep. 18, 1990 in the names of Kordesch, Gsellman and Tomantschger.
While the two Kordesch et al patents noted immediately above show the use of means such as cages to accomplish rechargeable cells having cycle lives of up to several hundred cycles, there are also several disadvantages from the approaches taken in the two Kordesch et al patents that must be considered. In particular, where cement or other non-conductive binders are used, they are present in the range of typically 5% to 10%, or even up to about 20%, by volume of the manganese dioxide electrode, and therefore the quantity of active ingredient that can be placed in the electrode is reduced. This results, of course, in a decrease in the useable discharge capacity of the cell, and it may also result in a decrease in the conductivity of the manganese dioxide electrode. On the other hand, if an insufficient amount of binder is used, then typically the manganese dioxide electrode may tend to crumble and/or crack, so that a coherent electrode structure is not achieved and its integrity is seriously affected.
If mechanical structures such as cages or screens are employed, then there is a significant increase in the material cost of the cell, as well as a significant increase in the cost of assembly of the cell. Indeed, there may be a significant effect and complication with respect to the use of high speed production equipment. Moreover, the use of a mechanical component such as a perforated iron or copper cage or plate may significantly increase the probability of cell gassing within the cell.
Still further, the use of a mechanical cage of screen adjacent to the separator of the cell may significantly affect the capability of the cell to operate in high drain conditions. Any mechanical means which restricts the electrode interface between the positive electrode and the negative electrode will act to limit the current density achievable from within the cell.
In contradistinction to the prior art, which relied upon the use of mechanical structures such as cages or screens, or the use of binders such as cement and steel wool, commonly owned U.S. Pat. No. 5,108,852 issued Apr. 28, 1992 to Tomantschger and Michalowski describes the use of an unconstrained manganese dioxide electrode for use in rechargeable galvanic cells. There is no cage or screen, and the patent is directed to the manner in which the positive electrode is constrained from significantly changing its dimensions by essentially filling the entire space allotted for it within the cell, while permitting perhaps a slight accommodation for height-wise or longitudinal expansion or growth in bobbin cells, or crosswise expansion or growth in button cells. Certain additives are contemplated for use in the manganese dioxide electrode mix, including conductive fibres or graphite and optionally including metal-based additives.

Manganese dioxide positive electrode for rechargeable cells, and cells containing the same


A method for fabricating a light emitting apparatus in which at least a portion of a light emitting element is covered with a light transmissive resin containing phosphor which emits light when excited by light emitted by the light emitting element, the method including directly processing the phosphor by irradiating the phosphor with a laser beam which passes through the light transmissive resin, to adjust the chromaticity of light to be emitted by the light emitting apparatus.

As a light emitting apparatus (a light emitting device) which emits white light, a light emitting apparatus which includes blue LED chips sealed with a light transmissive resin containing phosphor is known.
In such a light emitting apparatus, a portion of blue light emitted by the blue LED chip excites the phosphor, which causes the phosphor to emit yellow phosphor light. Then, the blue light emitted by the blue LED chip and the yellow phosphor light emitted by the excited phosphor are mixed and white light is obtained. The chromaticity of the white light provided by the light emitting apparatus depends on a ratio between an amount of blue light emitted by the blue LED chip and an amount of yellow phosphor light emitted by the phosphor.
Such a light emitting apparatus causes variations in performance of the blue LED chips, and variation in chromaticity of the white light depending on an amount of the phosphor.
To solve such problems, Patent Literature (PTL) 1 discloses a technique of removing a phosphor layer comprising phosphor by irradiating the phosphor layer with a laser beam, for adjusting the chromaticity of an emission color of the light emitting apparatus.

Method and apparatus for fabricating light emitting apparatus

PANASONIC INTELLECTUAL PROPERTY MANAGEMENT CO., LTD.


A method for compressing digital breast tomosynthesis data, a system and a control unit for image reconstruction of three-dimensional digital breast tomosynthesis volumes (DBT). The volume to be reconstructed is analyzed in order to identify clusters of regions in the volume with a low and high degree of diagnostically relevant information. Depending on the affiliation or belonging to a certain cluster, a specific reconstruction algorithm and a specific slab thickness are determined in order to be used for reconstruction of the cluster. Thus, different clusters are reconstructed differently.

Digital breast tomosynthesis volumes provide more information than regular full field digital mammography (FFDM—Full Field Digital Mammography) images for early detection of abnormalities and cancer. Unfortunately, the reading time and therefore the cost of examination increases more than two-fold with digital breast tomosynthesis imaging compared to FFDM methods.
In conventional projection mammography it is possible that certain anatomical structures (for example calcium deposits or certain opacities) are not spotted or represented on the respective image, because superimposed structures disturb the visibility of underlying structures of the breast and in the end may lead to a falsely positive interpretation of the image.
In order to overcome the limitations of conventional mammography, digital breast tomosynthesis methods have been developed, which acquire several projections of an object (the breast) at different angles and thereafter reconstruct the three-dimensional distribution of the detected grey values in a detector by means of a tomography reconstruction algorithm. With digital breast tomosynthesis it is possible to detect any lesion that might have been masked during the superimposition of the tissues that takes place during a classic mammography projection acquisition. In digital breast tomosynthesis the breast is imaged under compression. A sequence of projection views is acquired by the digital detector as the X-ray source is rotated to different angular positions about a fulcrum over a finite angular range. Anatomical structures or objects at different heights (or depths in the breast) are projected differently at different angles. The subsequent image reconstruction algorithm leads to a stack or a slab of slice images of the different depth layers parallel to the detector surface. This technique enables the physician during diagnosis to "browse through" the interior of the female breast without obstruction by surrounding superimposed tissue.
Further details and principles of digital breast tomosynthesis and respective apparatuses are disclosed in "Digital breast tomosynthesis using an amorphous selenium flat panel detector", M. Bissonnette et al., SPIE Vol. 5745, page 529 ff. For further information relating to reconstruction algorithms, particularly to filtered backprojection reconstruction algorithms it is referred to: "Optimizing filtered backprojection reconstruction for a breast tomosynthesis prototype device", T. Mertelmeier et al. in: SPIE 6142 (2006). The full content of these papers is incorporated here by reference.
A major drawback of tomosynthesis systems, however, is to be seen in that, typically, the digital volume contains 50 to 80 slices. Thus, the volume to be loaded, processed and stored is high.
One of the usual ways of reducing the amount of data for read and for storage in regular computer tomography is the reconstruction of the volume in thick slices. While the modern computertomographs are capable of producing images of less than 0.5 mm slice thickness (for example in thoracic or in abdominal images), radiologists often read and analyze three-dimensional images reconstructed as thick slices or thick slabs (for example 2 to 5 mm).
However, a major drawback of state of the art reconstruction methods is that the diagnostically relevant information may be easily overlooked during diagnosis, because the diagnostic relevant regions are not uniformly distributed throughout the volume. Some slices could be combined into 5 mm slabs without any loss of diagnostically relevant image features, while in other areas, where the probability of finding a lesion or an anatomical abnormality is high, a corresponding higher resolution is required for an accurate diagnosis. Thus, known conventional methods, which are based on reconstructing the volume in slabs with fixed thickness and with one single reconstruction algorithm for the whole volume, are not best suited. On the one hand, imaging the entire organ with very high resolution is not always possible, because of the storage space and reading time limitations. On the other hand, reconstructing only the relevant sub-volume with high resolution and not visualizing the surrounding areas of tissue at all does not provide enough diagnostic context.
Therefore, there is a need to provide a reconstruction method and system which considers non-uniformly distribution of lesions in the volume and reconstruction methods, considering these distribution differences and taking into account that different reconstruction algorithms may be applied to different anatomical structures (lesions) in the same volume to be examined. Moreover, there is a need for a reconstruction algorithm which processes slabs with variable slice thickness and with variable resolution within each of the slices.

Method, control system, and computer program for compression of digital breast tomosynthesis data


A method and system are provided for authenticating a user of a computer over a computer network. In one embodiment of the invention, the method includes transmitting an applet having a challenge string and a first encryption key, receiving a login packet having the challenge string and a password that is encrypted using the first encryption key, decrypting the password, receiving information from an authentication provider, and authenticating the password by using the information provided by the authentication provider. The challenge string can be either a sequence number or a session identifier. The authentication provider can be a software program or an authentication server. An advantage of embodiments of the present invention is that a computer can provide secure Internet communications using a web browser that does not support SSL and can provide secure integration with third party security systems.

The Secure Socket Layer (SSL) is a well known security protocol developed by Netscape® for transmitting private documents securely over the Internet. The SSL protocol works by using a private key to encrypt data that's transferred over an SSL connection. Many web sites use the SSL protocol to obtain confidential user information, such as a credit card number. The use of this protocol may not be desirable for all uses, however, because the use of SSL can require the purchase of a certificate.
A device that can authenticate users over the Internet is the Web/SNMP management card that has part number AP9606 and is manufactured by the American Power Conversion, Corp. of West Kingston, R.I. When the AP9606 card is first installed, the user programs it with an authentication phrase. This authentication phrase becomes a shared secret between the AP9606 card and the user. The AP9696 card provides security by transmitting an applet from the AP9606 card to a web browser, and the applet uses the shared secret to authenticate the user. Additionally, the AP9606 card also secures form data using this applet by hashing form fields with the shared secret. The AP9606 card can also provide management of uninterruptible power supplies (UPS's) via multiple open standards like Telnet, HTTP, and SNMP. Through the AP9606 card, a user can monitor and configure UPS's to complete tasks, such as shutting down and rebooting a user's computer system, receiving email alerts and providing an event log. However, due to the frequent necessity of conducting secure communications over the Internet and other networks, a system having even more secure access to web pages is desired.


Allelic variations in the genes PLEKHA1 and LOC387715 are identified herein as risk factor for Age Related Maculopathy (ARM). A method is therefore provided for identifying a risk of development of ARM in an individual that comprises identification of allelic variations in PLEKHA1 and/or LOC387715. Related apparatus, such as an array, are identified as being useful in implementing those methods.

Age-related maculopathy (also know as age-related macular degeneration) is a leading cause of central blindness in the elderly population and numerous studies support a strong underlying genetic component to this complex disorder. Genome-wide linkage scans using large pedigrees, affected sib pairs, and more recently, discordant sib pairs, have identified a number of potential susceptibility loci (Klein et al. 1998 Age-related macular degeneration. Clinical features in a large family and linkage to chromosome 1q. Archives of Ophthalmology 116:1082-1088.; Weeks et al. 2000 A full genome scan for age-related maculopathy. Human Molecular Genetics 9:1329-1349; Majewski et al. 2003 Age-related macular degeneration—a genome scan in extended families. Am J Hum Genet 73:540-550; Schick et al. 2003 A whole-genome screen of a quantitative trait of age-related maculopathy in sibships from the Beaver Dam Eye Study. Am J Hum Genet 72:1412-1424; Seddon et al. 2003 A genomewide scan for age-related macular degeneration provides evidence for linkage to several chromosomal regions. Am J Hum Genet 73:780-790; Abecasis et al. 2004—Age-related macular degeneration: a high-resolution genome scan for susceptibility Loci in a population enriched for late-stage disease. Am J Hum Genet 74:482-494; Iyengar et al. 2004 Dissection of genomewide-scan data in extended families reveals a major locus and oligogenic susceptibility for age-related macular degeneration. Am J Hum Genet 74:20-39; Kenealy et al. 2004 Linkage analysis for age-related macular degeneration supports a gene on chromosome 10q26. Mol Vis 10:57-61; Schmidt et al. 2004 Ordered subset linkage analysis supports a susceptibility locus for age-related macular degeneration on chromosome 16p12. BMC Genet 5:18 Weeks et al. 2004 Age-related maculopathy: a genomewide scan with continued evidence of susceptibility loci within the 1q31, 10q26, and 17q25 regions. Am J Hum Genet 75:174-189; Santangelo et al. 2005 A Discordant Sib-Pair Linkage Analysis of Age-Related Macular Degeneration. Ophthalmic Genetics 26:61-68). Genome-wide linkage screen strongly implicated the 10q26 region as likely to contain an age-related macular degeneration (AMD) gene (Weeks et al. 2004); this region has also been supported by many other studies and is the top-ranked region in a recent meta analysis (Fisher et al. 2005 Meta-analysis of genome scans of age-related macular degeneration. Hum Mol Genet. 2005 Aug. 1; 14(15):2257-64). Recently, three papers appeared in Science (Edwards et al. 2005 Complement Factor H Polymorphism and Age-Related Macular Degeneration. Science 308, 421-424; Haines et al. 2005 Complement Factor H Variant Increases the Risk of Age-Related Macular Degeneration. Science 308, 419-421. Klein et al. 2005 Complement Factor H Polymorphism in Age-Related Macular Degeneration. Science 308, 385-389) identifying an allelic variant in complement factor H (CFH) as responsible for the linkage signal seen on Chromosome 1 and accounting for a significant attributable risk for ARM in both familial and sporadic cases. These findings have been confirmed (Conley et al. 2005 Candidate gene analysis suggests a role for fatty acid biosynthesis and regulation of the complement system in the etiology of age-related maculopathy. Hum Mol Genet 14: 1991-2002; Hageman et al. (2005a) From The Cover: A common haplotype in the complement regulatory gene factor H (HF1/CFH) predisposes individuals to age-related macular degeneration. Proc Natl Acad Sci USA 102:7227-7232; and Zareparsi et al. 2005a Strong Association of the Y402H Variant in Complement Factor H at 1 q32 with Susceptibility to Age-Related Macular Degeneration. Am J Hum Genet 77:149-53). CFH has been previously suspected of playing a role in ARM due to the work of Hageman and Anderson (Hageman and Mullins 1999 Molecular composition of drusen as related to substructural phenotype. Molecular Vision 5:28; Johnson et al. 2000 A potential role for immune complex pathogenesis in drusen formation. Experimental Eye Research 70:441-449 Complement activation and inflammatory processes in Drusen formation and age related macular degeneration. Experimental Eye Research 73:887-896; Mullins et al. 2000 Drusen associated with aging and age-related macular degeneration contain proteins common to extracellular deposits associated with atherosclerosis, elastosis, amyloidosis, and dense deposit disease. FASEB Journal 14:835-846; Hageman et al. 2001 An integrated hypothesis that considers drusen as biomarkers of immune-mediated processes at the RPE-Bruch's membrane interface in aging and age-related macular degeneration. Progress in Retinal & Eye Research 20:705-732.; Johnson et al. 2001), who have shown that the subretinal deposits (drusen) that are observed in many ARM patients contain complement factors. However until other genes that contribute to ARM are identified, CFH remains an isolated piece of the puzzle, implicating the alternative pathway and inflammation as part of the ARM pathogenesis, but failing to account for the unique pathology that is observed in the eye.

Susceptibility genes for age-related maculopathy (ARM) on chromosome 10q26

University of Pittsburgh-Of the Commonwealth System of Higher Education


The embodiments of the present application disclose a method and apparatus for acquiring wireless access points information. One specific embodiment of the method comprises: in response to detecting a user operation of initiating a target application, acquiring a Wifi privilege; in response to detecting that the user opening a system interface for displaying a wireless access points information list, acquiring the wireless access points information list; in response to detecting a switch from the system interface for displaying the wireless access points information list to an interface of the target application, presenting the wireless access points information list in the interface of the target application. The embodiment implements displaying the wireless access points information list in the interface of the target application of a terminal device.

With the development of wireless communication technologies, Wi-Fi (Wireless-Fidelity) networks have become an important way of accessing networks by users in daily life and have brought great convenience to the users. As an example, in some public areas configured with free and open wireless access points (AP), users are able to connect to these free and open wireless access points without having to input passwords. In households, however, private wireless access points are usually configured. These private wireless access points are usually provided with passwords. Users have to input passwords for connecting to these private wireless access points and may only be connected to these private wireless access points after successful authentication.
However, for terminal devices equipped with iOS (a mobile operating system of Apple Inc.), except for particular WiFi connections by installation of description documents, users have to select from a system wireless access points list for wireless access points connection. The system wireless access points list is unable to provide personalized ranking and filtering.

Methods and apparatus for acquiring wireless access points information

SHANGHAI SHANGWANG NETWORK TECHNOLOGY CO., LTD.


The invention discloses a method for forming an interfacial passivation layer on the Ge semiconductor. The supercritical CO2 fluids is used to form an interfacial passivation layer between Ge channel and gate insulator layer, and improve the dielectric characteristics of gate insulator after high-temperature thermal annealing process.

1. Field of the Invention
The invention relates to a method for forming a protection layer on the semiconductor, particularly to a method for forming an interfacial passivation layer on the germanium semiconductor.
2. Description of the Prior Art
At present, the development trend for the manufacturing technology of the integrated circuit (IC) is still kept to the trend of miniaturizing transistor size, in order to reach the goal of high efficacy and high density. Due to the efficacy of conventional polycrystalline silicon/silicon dioxide/silicon channel metal-oxide-semiconductor field effect transistor is unable to be increased by the miniaturizing technology, thus, how to increase the mobility of carrier and the dielectric capacitance of gate has become the key technology and goal for the development of field effect transistor in the next generation. Wherein, the mobility for the electron and hole of Ge semiconductor is 2 times and 4 times higher than those of silicon, respectively. The basic process is similar to the silicon semiconductor technology. Thus, the germanium metal-oxide-semiconductor field-effect transistor (Ge-MOSFET) has been considered as the most promising candidate for the next generation of semiconductor industry.
In the past development process of Ge-MOSFET, various different gate insulators had been tried, such as the germanium dioxide (GeO2), silicon dioxide (SiO2), or the material with high dielectric constant (high-k), such as hafnium dioxide (HfO2), aluminum dioxide (Al2O3), in order to improve the capacitor coupling ability of gate insulator layer. However, large density of state contained between the high-k dielectric and germanium channel, and diffusion of germanium in high-k dielectric during inevitable thermal process, result in threshold voltage shift and gate leakage current increasing.
According to prior art, introduce a thin high-quality protection layer between high-k dielectric film and germanium semiconductor is able to prevent the generation of defect on germanium interface, wherein the germanium dioxide has the best efficacy.
In the US Patent No. 2006/0099872 of "Method for forming an interface between germanium and other materials", the sulfide, such as H2S or SF6 is used to form an interface on semiconductor surface. The process is still a conventional method, and the interface has to be formed before gate insulator layer deposition. Thus, the interface is unable to be formed after the gate insulator deposition, and the defect generation in gate insulator could occur again during sequent thermal process.
In the US Patent No. 2006/0292872A1 of "Atomic layer deposition of thin films on Germanium", before the method of atomic layer deposition is used to grow gate insulator layer with high dielectric constant, the germanium oxynitride is formed at the interface. The process temperature could be too high, and the interface is unable to be formed after the gate insulator deposition, and the defects could generate in gate insulator during sequent thermal process
In the US Patent No. 2007/0099398A1 of "Method and system for forming A nitride Germanium-containing layer using plasma processing", the plasma method is used to form the germanium nitride, the germanium dioxide or the nitride germanium oxide as the interface. Although it is a low-temperature process, it requires the vacuum system, only the interface is able to be formed. The interface is unable to be formed after the gate insulator deposition, and the defects could generate in gate insulator during sequent thermal process.
In current Ge-MOSFET manufacture process, it is inevitable to use the high-temperature process (such as dopant activation after the ion implantation or the annealing process after the metal sputtering). It will always cause the significant thermal diffusion of germanium and the surface damage of germanium. The poor thermal stability of germanium oxide cause chemical reaction of germanium oxide and germanium substrate. Sequent thermal decomposition of germanium oxide results poor interface between gate dielectric and germanium substrate, and thermal diffusion of germanium in gate dielectric. Thus, how to develop a low-temperature process to form a high-quality protection layer between germanium substrate and gate dielectric layer to prevent the generation of defect has become an important gate engineering technology.
Therefore, in order to produce more efficient germanium semiconductor surface protection layer technology, provide the industry to grasp better production process, and apply it on the manufacturing of Ge-MOSFET, it is necessary to research and develop the innovative method for forming an interfacial passivation layer on the germanium semiconductor, to improve the production efficiency for the interfacial passivation layer on the germanium semiconductor and reduce the manufacturing cost of the semiconductor.

Method for forming an interfacial passivation layer on the Ge semiconductor


A package for optical module includes a flat-plate-shaped metal base, and a ceramic circuit board in which a plurality of terminals are arranged in a longitudinal direction, and which is joined to an upper surface of the metal base by soldering. The ceramic circuit board has a shape change portion in which the ceramic circuit board is changed in shape along the longitudinal direction, and a region of the ceramic circuit board not including the shape change portion is joined to the metal base by soldering. The shape change portion of the ceramic circuit board is a portion where a width is changed along the longitudinal direction, or a portion where a thickness is changed along the longitudinal direction.

In recent years, development of optical front-end modules for digital coherent receivers has been advancing. As optical front-end modules for receivers, there have been known modules described in Patent Literature 1, for example. A package used for such a module has been standardized in terms of a shape, pin layout and the like. A package is provided with DC leads in two opposed side faces thereof, i.e., 20 DC leads arranged at a pitch of 1.27 mm in each side face. In the package, one of side faces orthogonal to the two opposed side faces is provided with an optical input terminal and the other side face is provided with 20 RF leads arranged at a pitch of 1 mm.
As packages used for aforementioned modules, a metal package is often used in which ceramic circuit boards each having SMT leads are joined by being embedded in side wall faces of the package. For example, as illustrated in FIGS. 1A and 1B, a conventional package is often hermetically sealed in such a way that a lid being a flat plate lid (not illustrated) is seam-welded to a bathtub-shaped package base 10. As illustrated in FIG. 1A, the optical front-end module for receiver includes a waveguide optical element 20, an optical component 30, an optical semiconductor and electronic circuit 40, and the like, which are mounted inside the package 10. Moreover, two opposed side faces of the package 10 are provided with ceramic circuit boards 50 having multiple DC leads 60 connected thereto, and the side surfaces orthogonal to the two opposed side surfaces are provided with a fiber F and output terminals 70.

Nippon Telegraph and Telephone Corporation


An optical element is provided which comprises a plurality of fluorophores disposed in a medium. The fluorophores have a quantum yield greater than 50% and an absorption spectrum with a maximum intensity at wavelengths less than 400 nm, and emit a spectrum of light having a maximum intensity at wavelengths within the range of 400 nm to 1200 nm. The optical element is at least partially transparent over the visible region of the spectrum. The optical element is especially useful as a window or other optical component of a greenhouse structure.

Luminescent solar concentrators (LSCs) are devices which utilize luminescent materials to concentrate solar radiation, typically for the purpose of generating electricity. A common set-up 101 of such a device for this purpose is depicted in FIG. 1. As seen therein, the solar concentrator 103 is utilized to collect solar radiation 109 over a relatively large area, and to concentrate it onto a relatively small area (here, the active surface of a photovoltaic cell 105). The photovoltaic cell 105 then converts the radiation into electricity to provide power for end user devices. One of the first reports of an LSC can be found in U.S. Ser. No. 06/001,585 (Zewail et al), entitled "Luminescent Solar Energy Concentrator Devices," filed in 1979, which notes that "Snell's law dictates that a large fraction, typically 75%, of this reemission strikes the surface of the substrate with an angle of incidence greater than the critical angle, so that this fraction of the light is then trapped in the substrate by internal reflection until successive reflection carries it to the edge of the plate where it enters an absorber placed at the edge of the plate."
Since electricity is one of the biggest expenses for a greenhouse operator or indoor plant grower, there are opportunities for LSCs to be used in agriculture. This type of approach was applied in U.S. Ser. No. 14/372,389 (Carter et al), entitled "Luminescent Electricity-Generating Window for Plant Growth" and filed in 2012, which notes that "there is a need in the art for luminescent solar collectors which are can produce power with no harm to plant growth." Another approach to generating electricity for a greenhouse can be found in U.S. Ser. No. 12/505,523 (Chuang et al), entitled "Photovoltaic Greenhouse Structure," filed in 2009, which notes that "light which is not absorbed by the thin-film solar cell module freely passes through the thin-film solar cell module and enters the greenhouse inner space."
Referring again to FIG. 1, the solar concentrator 103 is essentially an optical waveguide comprising a luminescent material which is embedded in a substrate. The substrate is typically glass or a polymeric material of optical quality. When solar radiation impinges on the luminescent material, the luminescent material undergoes luminescence (and most commonly, fluorescence), and emits light into the waveguide. From there, the entrapped light is directed to the photovoltaic cell 105. Since the radiation emitted by the luminescent material through fluorescence is typically emitted at different wavelengths than the radiation initially absorbed by the luminescent material, the solar concentrator 103 has the effect of both concentrating and modifying the spectral footprint of the radiation which is impingent on it.
There have been attempts to utilize fluorescent materials to enhance plant growth. For example, U.S. Pat. No. 3,352,058 (Brant), entitled "Organic Fluorescent Colorants For Stimulating The Growth Of Plants", and filed in 1966, notes that "if the colorant is properly selected so that the transmitted light is predominantly composed of red and blue wave lengths with a minimum of green wave lengths, optimum results are frequently achieved." This approach is lacking because a purely down conversion film will lose roughly 50% of the light by fluorescence back out of the top of the film (directed away from the plants). Additionally, approaches such as those employed by Zewail, Brant and Carter rely on dyes wherein blue light is mostly transmitted, whereas there are many situations where blue light should be a small fraction of the spectrum incident on the plants. For example, in the paper titled "Sensitivity of Seven Diverse Species to Blue and Green Light: Interactions with Photon Flux" by Snowden et al., published in PLOS ONE in 2016, it is stated that "at the higher photosynthetic photon flux (500 micromoles m−2 s−1), increasing blue light in increments from 11 to 28% reduced growth in tomato, cucumber, and pepper by 22, 26, and 14% respectively, . . . " Additionally, dyes suffer strongly from instability under sunlight.
There have been attempts to modify the directionality of sunlight to enhance plant growth without waveguides, relying instead on scattering. For example, U.S. Ser. No. 13/064,600 (Krasnov), entitled "Light Scattering Coating For Greenhouse Applications, And/Or Coated Article Including The Same", filed in 2011, states that "(a) light having a wavelength of greater than or equal to about 800 nm incident thereon to primarily scatter to angles less than 30 degrees relative to a major surface of the substrate and (b) light having a wavelength of less than or equal to about 700 nm incident thereon to primarily scatter to angles greater than 20 degrees relative to the major surface of the substrate." The approach suffers from attenuation through the film due to scattering which lowers the amount of useful light impinging on plants, and also from lack of wavelength conversion capability which would shift photons from one range of the spectrum to another more useful range.

Luminescent optical elements for agricultural applications


A method of detecting rpoB sequences of Mycobacterium tuberculosis present in a biological sample that includes steps of amplifying the M. tuberculosis rpoB sequence in vitro in a nucleic acid amplification mixture that includes specific disclosed primer sequences, and detecting the amplified sequences using multiple probes that provide sequence information by their specific hybridization to portions of the amplified nucleic acid. Compositions for amplifying and detecting in vitro the rpoB sequences of M. tuberculosis in a sample are disclosed.

Rifampin (RIF), an antibiotic synthesized from rifamycin B, is a key component of drug therapy against Mycobacterium tuberculosis. Rifampin has a unique site of action on the beta subunit of prokaryotic RNA polymerase. In Escherichia coli, missense mutations and short deletions in the central region of the RNA polymerase subunit gene (rpoB) result in strains resistant to rifampin (Lisityn et al., 1984, Mol. Gen. Genet. 196 :173–174). Similarly, in M. tuberculosis a wide variety of mutations in the rpoB gene have been identified that confer rifampin resistance (Telenti et al., 1993, Lancet 341: 647–650). More than 90% of rifampin-resistant M. tuberculosis isolates are also resistant to isoniazid, and, therefore, rifampin resistance is a valuable surrogate marker for multiple drug resistance. Thus, there is a need for tests that can detect rapidly the genetic basis for rifampin resistance for diagnosis that leads to appropriate treatment of infected individuals.
Early detection of drug resistance in clinical M. tuberculosis isolates is crucial for appropriate treatment and to prevent the spread of resistant strains. Conventional methods of detecting drug-resistance by growth of M. tuberculosis on solid media, and more recent methods that rely on growth in liquid media have provided susceptibility results in 3 days to over 4 weeks (Rusch-Gerdes et al., 1999, J. Clin. Microbiol. 37: 45–48).
Genetic techniques that rely on the polymerase chain reaction (PCR) have been devised to detect rifampin resistance. Such techniques include direct sequencing of PCR products, single strand conformation polymorphism analysis, heteroduplexing and dideoxy fingerprinting (Telenti et al., 1993, Lancet 342: 841–844; Williams et al., 1994, Antimicrobial Agents Chemotherapy 38: 2380–2386; De Beenhouwer, 1995, Tubercle and lung disease 76: 425–430). Other assays and reagents for detecting resistance to rifampin in M. tuberculosis isolates or identifying Mycobacteria species using rpoB gene have been previously disclosed, for example, in U.S. Pat. No. 5,643,723 (Persing et al.), U.S. Pat. No. 5,851,763 (Heym et al.), U.S. Pat. No. 6,228,575 (Gingeras et al.), and 6,242,584 (Kook et al.).
The present invention provides compositions and simple diagnostic methods to detect rifampin resistance in M. tuberculosis that may be present in a clinical sample.

Detection of rpoB sequences of Mycobacterium tuberculosis


A method for interactive transmission garage shifts includes receiving a request for a transmission garage shift; controlling the transmission to bring the vehicle to a stop state based on determining that the vehicle is rolling backwards on a grade above a predetermined grade threshold and at a speed below a predetermined speed threshold; controlling an electric park brake (EPB) to hold the vehicle at the stop state; controlling the transmission to engage a dog clutch so as to place the transmission in a forward drive gear; and controlling the EPB to i) deactivate if the dog clutch is determined to be engaged, or ii) maintain activation to maintain the vehicle at the stop state if the dog clutch is determined to be disengaged.

Vehicle garage shifts include stationary or substantially stationary garage shifts, such as shifts from park (P) to drive (D) and neutral (N) to D. Vehicle garage shifts can also include stationary or rolling garage shifts, such as from reverse (R) to D and D to R. Vehicle transmissions typically include a plurality of clutches for transmitting rotational energy from the engine to the wheels of the vehicle. The plurality of clutches are selectively engaged and disengaged to shift the transmission into the desired ratio, such as when performing a stationary or rolling garage shift. When a vehicle is on a grade, the vehicle may move or roll due to the grade while a driver of the vehicle is requesting a garage shift. Such rolling may result in poor shift quality and/or, under certain conditions, prevent the transmission from shifting into the desired gear. Thus, while current vehicle transmission shift strategies work for their intended purpose, there remains a need for improvement in the relevant art.

Interactive transmission shift techniques


The present invention provides an air compressor having inflating and aerosol spraying functions for tires. The air compressor has an innovative actuator with an eccentric cam so that the present invention can not only perform singly inflating function for the flat tire but also perform fixing function for the rupture tire. The present invention comprises a case containing an air compressor and a tire fixing aerosol containing chemical sol therein with an actuator, which enables the present invention to shift the operation of the air compressor and tire fixing aerosol between the singly inflating and fixing functions for tire with easy manipulation.

1. Field of the Invention
The present invention provides an air compressor for inflating a tire and spraying aerosol spraying onto tires, including an actuator with an eccentric cam for switching between the two different functions of inflating and aerosol spraying.
2. Description of the Prior Art
The essential structure of a conventional tire fixing aerosol comprises a cover, a canister and an inner dip tube, wherein the canister is filled with chemical sol therein for urgently fixing a ruptured tire temporarily; the cover usually includes two manifolds such that one manifold is used to connect with a compressed air output from an air compressor while the other manifold is used to connect with a chemical sol muzzle from the canister; and the inner dip tube, which is linked to the cover, is disposed inside of the canister when the cover is engaged with the cover. Currently, most conventional apparatus for fixing a ruptured tire temporarily in an urgent situation include a separate tire fixing aerosol with two manifolds together with a case containing an air compressor therein, which is to supply compressed air to the tire fixing aerosol. In practical operation of fixing a ruptured tire, a user can connect the first manifold of the tire fixing aerosol to a compressed air output from the case while connect the other second manifold of the tire fixing aerosol to the nozzle of the ruptured tire. Then, the user starts the air compressor to initiate the propellant of the chemical sol forced out of the canister into the ruptured tire for accomplishing the tire sealing and fixing temporarily. However, the conventional design of tire fixing aerosol with a case, which is limited in used for fixing a ruptured tire, can-not be used in inflating a flat tire. Having realized and addressed forgoing drawbacks of the conventional tire fixing aerosol, the inventor of the present invention contrives an innovative actuator with an eccentric cam to switch between two manifolds of tire fixing aerosol so as to independently perform inflating function for flat tires and aerosol spraying function for ruptured tires.

Air compressor having inflating and aerosol spraying functions for tires


A method is provided for making aromatic carbonates, such as diphenyl carbonate by the carbonylation of an aromatic hydroxy compound, such as phenol in the presence of a palladium catalyst and an organic cocatalyst, such as a terpyridine compound.

The present invention relates to a method for making aromatic organic carbonates such as diphenyl carbonate by effecting reaction between an aromatic organic hydroxy compound, such as phenol, and carbon monoxide and oxygen in the presence of an effective amount of a palladium carbonylation catalyst. More particularly, the present invention relates to the carbonylation of an aromatic organic hydroxy compound utilizing an organic cocatalyst, such as a terpyridine in combination with the palladium carbonylation catalyst.
Procedures for making diorganic carbonates are shown by Hallgren, U.S. Pat. Nos. 4,361,519 and 4,410,464, utilizing a molecular sieve as a drying agent for the water formed during the reaction. A procedure for making aromatic organic carbonates by catalytic carbonylation is shown by Japanese patent 01,165,551. Aromatic organic carbonates are of particular interest to thermoplastic manufacturers, since they offer an alternative non-phosgene route to aromatic polycarbonates by melt transesterification. A procedure for making aromatic organic carbonates using an organic solvent, such as methylene chloride, is shown by Chalk, U.S. Pat. No. 4,187,242. Reference also is made to T. C. Chang in EPA 8911158.8, Jun. 26, 1989, and EP350-700-A, utilizing a divalent or trivalent manganese salt, or cobalt (II) salt in combination with hydroquinone and a palladium catalyst, to catalyze the conversion of an aromatic organic hydroxy compound, such as phenol, to an aromatic organic carbonate. U.S. Pat. No. 4,218,391, Romano et al employ a copper salt to prepare organic esters of carbonic acid. Attempts to use such catalyst with aromatic organic hydroxy compounds, such as phenol, under constant flow conditions have been found to provide unsatisfactory results with respect to % carbonate yields and % carbonate selectivity as compared to the use of aliphatic hydroxy compounds, such as methanol, in preparing aliphatic carbonates under substantially the same conditions.
In application EP350-700-A and copending application Ser. No. 07/906,681, carbonylation of aromatic organic hydroxy compound was achieved utilizing a divalent or trivalent manganese salt or cobalt (II) salts and organic cococatalyst such as hydroquinone or benzoquinone in combination with a palladium catalyst. Although the aforementioned cocatalyst system provides improved yields of aromatic organic carbonate as a result of the carbonylation of aromatic organic hydroxy compounds, organic cocatalyst, such as benzoquinone has to be utilized in the range of 10-40 equivalents per equivalent of palladium, to show a reasonable rate of aromatic organic carbonate production. In addition it has been found that benzoquinone organic cocatalyst based systems are often readily degraded resulting in the production of color bodies and reduced catalyst stability following exposure to ambient conditions. As a result it was not feasible to recycle palladium carbonylation catalyst used in the manufacture of aromatic organic carbonates at elevated conditions of temperature and pressure and there after allow the introduction of make-up aromatic organic hydroxy compound into the reactor under ambient conditions.


Disclosed is a method for removing aldehyde impurities from a methyl acetate supply. The method comprises reacting the methyl acetate supply with a polyol and converting the aldehyde impurities to cyclic acetals. The acetals are subsequently removed from the methyl acetate supply by, e.g., distillation. The purified methyl acetate supply is used for carbonylation to produce acetic acid.

Carbonylation of methanol produces acetic acid. Prior to 1970, acetic acid was made using cobalt catalysts. A rhodium carbonyl iodide catalyst was developed in 1970 by Monsanto. The rhodium catalyst is considerably more active than the cobalt catalyst. Most importantly, the rhodium catalyst gives high selectivity to acetic acid.
One problem associated with the original Monsanto process is that a large amount of water (about 14%) is needed to produce hydrogen in the reactor via the water-gas shift reaction. Water and hydrogen are needed to react with precipitated Rh(III) and inactive [RhI4(CO)2] to regenerate the active Rh(I) catalyst. The large amount of water increases the amount of hydrogen iodide, which is highly corrosive and leads to engineering problems.
Millennium Petrochemical Company developed a new rhodium carbonylation catalyst system. The catalyst system uses a pentavalent Group VA oxide such as triphenylphosphine oxide as a catalyst stabilizer. The catalyst system not only reduces the amount of water needed but also increases the carbonylation rate and acetic acid yield. See U.S. Pat. No. 5,817,869.
One challenge still facing the industry is that lowering water concentration in the methanol carbonylation results in increased aldehyde formation. Methods for reducing aldehyde concentration in acetic acid are known. For instance, U.S. Pat. No. 7,208,625 teaches reducing aldehyde and other permanganate-reducing impurities from acetic acid by contacting acetic acid with peracetic acid and air. Co-pending application Ser. Nos. 11/496,900 and 11/508,109 teaches removing aldehyde impurities from acetic acid by reacting the aldehydes with hydroxyl compounds to form acetals which are then removed from acetic acid by distillation. Co-pending application Ser. No. 11/810,167 teaches extracting the aldehyde impurities with a polyol from a methyl iodide solution in the acetic acid production process.
Methyl acetate is commonly used in methanol carbonylation. One source of methyl acetate is the byproducts of polyvinyl acetate hydrolysis or methanolysis. These byproducts are often supplied as mixtures of methyl acetate and methanol and they contain various amounts of aldehyde impurities. It is important to remove aldehyde impurities from the methyl acetate supply because these impurities complicate the methanol carbonylation and increase the impurity level in the acetic acid product. However, some aldehyde impurities, such as acetaldehyde, are not easy to separate from methyl acetate because of their close boiling points. Thus, new methods for removing aldehyde impurities from methyl acetate are needed.

Methyl acetate purification and carbonylation


An apparatus and a method for controlling a volume in a mobile terminal are provided. The apparatus includes a motion detector and a controller. The motion detector outputs motion information from a user's movement. The controller determines the user's activity from the motion information output from the motion detector, and determines an appropriate output volume level responsive to the activity.

1. Field of the Invention
The present invention relates to a mobile terminal that can detect a user's movement. More particularly, the present invention relates to an apparatus and a method for controlling a volume of a mobile terminal to variably control an output volume suitable for activity depending on a user's movement.
2. Description of the Related Art
Today, various types of portable terminals such as cellular phones provide various functions to meet well-being trends in addition to traditional multimedia functions, which include music reproduction, moving image reproduction, Digital Multimedia Broadcasting (DMB) viewing, etc. More particularly, as an interest in health of people grew, various mobile terminals having a health-related function are competitively brought to the market. For example, there is a terminal mounted on a human body for measuring a user's exercise amount and in turn displaying an exercise effect.
Therefore, occasionally, a user may exercise while listening to music output from a mobile terminal via an earphone connected to the mobile terminal. Of course, the user may talk with a counterpart using the earphone during an exercise. However, when the user transitions to more intense exercise, music that has been reproduced at a previously set volume may not be heard. For example, when a user walks slowly and then suddenly runs, the user cannot properly listen to the music at a previously set volume due to elevated noise level associated with the running. Therefore, the user has an inconvenience of having to stop the exercise for a momentarily and resume, or try adjust the volume during the run.

Apparatus and method for controlling volume in portable terminal

Samsung-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do


An integrated optical head has first and second channels forming an interferometer. A electro-optically phase-shiftable waveguide channel is associated with one of the first and second channels of the interferometer for electro-optical phase shifting of one channel with respect to the other channel. The interferometer is formed on a silicon substrate and the phase-shiftable waveguide channel is formed of Langmuir-Blodgett thin-film electro-optic polymers described on the silicon substrate.

Optical heads, whether of the bulk or integrated optic variety, must provide at least three separate functions. First of all, it must retrieve the data signal encoded on the light reflected off of the optical disk. Second, it must measure tracking errors that are displacement errors associated with motion of the disk in the plane of the disk. Finally, it must measure focus errors that are displacement errors associated with motion of the disk in a direction perpendicular to the plane of the disk. Integrated Guided Wave Optical Heads (IGWOH) represent compact, low mass alternatives to bulk optical head assemblies for reading and writing information on optical data storage disks.
U.S. Pat. No. 4,798,437 discloses a method and apparatus for processing analog optical wave signals. This patent describes the use of Mach-Zehnder (M-Z) interferometer arrays formed on inorganic electro-optic substrates, such as LiNbO.sub.3 for example, to analyze wavefront profiles. Among the devices mentioned is an integrated optical waveguide range finder wherein free space radiation from a point source is end-fire coupled into an array of channel waveguides. The distance of the point source from the analyzer determines the curvature of the wavefront incident on the analyzer. Portions of the wavefront falling on adjacent channel waveguides are shifted slightly in phase due to this curvature. Adjacent channels are joined together at a Y-junction and the relative phase shift results in interference between light from these two channels. The signal exiting the interferometer, when taken together with the signals from other interferometers in the array, provide a measure of the wavefront curvature and hence of the distance to the source. Other light signals provide intensity reference levels. Control electrodes permit electro-optical phase-shifting of one channel with respect to the other. This feature provides a means of compensating for slight differences in the optical path lengths of the two channels or of biasing one channel with respect to the other.
It is desirable to use newer technology and have waveguides formed from new thin-film electro-optic polymers deposited on silicon substrates and to integrate electronic functions such as photodetection, amplification, and switching with the optic functions. Current conventional bulk heads for readout of optical data are limited in performance by weight and physical size. Integrated optic heads offer the possibility of low weight, compact size, and higher performance. A co-filed application entitled Waveguide Optical Pick-Up Head Using a Mach-Zehnder Interferometer Wavefront Sensor, which is incorporated herein by reference, descries an integrated optic waveguide pick-up head which can be more easily fabricated than prior art integrated optic heads. It is necessary to impose a .+-.90.degree. phase retardation on one arm relative to the other of each channel waveguide Mach-Zehnder (M-Z) interferometer in order for the device to function properly. A non-linear optical material exhibiting the so-called linear electro-optic or Pockels effect is incorporated in or deposited on top of one arm of each M-Z interferometer and permits voltage controlled tuning of the phase retardation. Inorganics such as LiNbO.sub.3 and organics such as spin-coated azo-benzene sulfone dye co-polymer are examples of suitable non-linear optic materials.
The idea of using M-Z interferometers to sense focus error in a waveguide optical pick-up head was advanced in the co-filed application. The use of the Langmuir-Blodgett (L-B) technique as a means of forming optically transparent poled films of noncentrosymmetric molecules was advanced by Penner, et al., in co-pending application Ser. No. 07/735,550, filed Jul. 25, 1991 entitled Improved Conversion Efficiency Second Harmonic Generator. It is desirable to extend the use of L-B films to include use as the nonlinear optical medium in one arm of M-Z interferometers used in waveguide optical pick-up heads.

Langmuir-Blodgett films in a waveguide optical pick-up head using Mach-Zehnder interferometers


A method for using a candida antigen in the treatment of psoriasis. In an embodiment, the method comprises periodically administering, to a patient having psoriasis, a candida antigen until clearance of the psoriasis is achieved.

1. Field of the Invention
The embodiments described herein are generally directed to the treatment of psoriasis, and, more particularly, to a method or process of using a candida antigen as a treatment for psoriasis.
2. Description of the Related Art
Candida is a genus of yeast that can cause infections. For instance, candida albicans is a species of candida which is commonly known to cause oral and genital infections in humans. Candida yeast is frequently used as the basis of a recall antigen for detecting delayed-type hypersensitivity, through intradermal testing. Specifically, candida antigen has been useful in evaluating the cellular immune response in patients suspected of having a reduced cellular hypersensitivity. For example, when delivered to a patient as a shot, if the patient's immune system is working properly, the skin near the injection site should turn red within a few days. The CANDIN® skin test antigen—manufactured by Allermed Laboratories, Inc. in San Diego, Calif.—is one example of a candida ablicans antigen.
Currently, in the field of dermatology, candida albicans antigens (e.g., CANDIN®) are used to stimulate cellular immune response as a way of treating warts. Warts, which can exist in a number of varieties (e.g., plantar warts), are caused by infections of the human papilloma virus. When the candida antigen is injected into or otherwise delivered to a wart (e.g., plantar wart), a properly functioning human immune system will become very active in the area of the wart. Specifically, the body will attack the candida to remove it, and, in the process, attack the wart as well. In this manner, the wart may be removed through the cellular immune response caused by the delivery of candida antigen to the wart.
Psoriasis is an immune-mediated skin disease. Even today, the cause of psoriasis is not fully understood. Thus, while there are various treatments that can help control the symptoms of psoriasis, there is presently no cure. While candida antigens have been previously used to treat warts, such as plantar warts, it has not been previously contemplated or expected that candida antigens may be useful in the treatment of psoriasis.

Methods of treating psoriasis using candida antigen


A device for conducting protons at a temperature below 550° C. includes a LAMOX ceramic body characterized by an alpha crystalline structure.

Ion transport membranes composed of proton conducting materials are a critical component for: future fuel processing such as separations, for example; energy production systems such as fuel cells, for example; and ancillary technologies such as sensors and electrolyzers for example.
Ceramic oxide hydrogen ion transport membranes ("proton conductors") are presently limited in availability and performance. Presently known hydrogen ion conductors are characterized by low conductivities, lack of stability in reducing environments and/or susceptibility to chemical attack by contaminants such as sulfur (H2S) and CO2.
Incorporated herein by reference is the entire disclosure of U.S. Patent Application No. 20030160216 published Aug. 28, 2003, PCT filed Apr. 5, 2001 by Francois Goutenoire, at al.

Low temperature proton conducting oxide devices


Precipitated silica particulates having a BET specific surface ranging from 20 to 300 m.sup.2 /g, a CTAB specific surface ranging from 10 to 200 m.sup.2 /g, an oil uptake (DBP) ranging from 80 to 400 cm.sup.3 /100 g, a pore volume ranging from 1 to 10 cm.sup.3 /g and a mean pore diameter ranging from 10 to 50 nm, well adapted for such applications as the coating of paper and catalysis, are prepared by (a) simultaneously introducing a silicate and an acid into a dispersion of colloidal silica, thereby providing a silica suspension, (b) next decreasing the pH of such suspension to a value ranging from 3 to 7, and (c) then separating the silica particulates from the final suspension and drying them.

1. Field of the Invention
The present invention relates to novel silica particulates, and, more especially, to novel precipitated silica particulates having a controlled porosity, as well as to a process for the production thereof.
2. Description of the Prior Art
Silica is known to this art to be useful for certain applications because of its porosity characteristics, in particular for catalysis, inks and paper, in the food industry, etc.
In catalysis, the silica is used as a catalytic support, or as a porous layer coated or impregnated on monolithic supports.
Due to its optical whiteness and opacity, silica is used as an inorganic charge in papers, particularly those used for newspapers, as a coating material for coated papers and also specialty papers. When silica is used in paper, a greater porosity is required in order to facilitate ink absorption.
More particularly in the field of animal feeds, silica is used as a result of its absorption properties as a feed support, particularly as a support for methionine, vitamins, particularly vitamins A and E, for sucroglycerides, etc.
Thus, for these and numerous other applications, it is necessary for the silica to have certain morphological characteristics, including particular porosity.

Precipitated silica particulates having controlled porosity