A manufacturing apparatus and a manufacturing method of pet food are provided. The manufacturing apparatus comprises a material inlet through which a kneaded material is fed, the kneaded material being obtained through kneading a raw pet food material; an extrusion molding section configured to extrude the kneaded material through an extruding outlet; a cutter configured to cut the kneaded material extruded through the extruding outlet at desired intervals to form material grains; a reservoir disposed in a location to receive the material grains falling due to the cutting; an agitating section provided in the reservoir and configured to agitate the material grains; a heating section configured to heat the material grains while the material grains are agitated by the agitating section; and a drying section configured to dry the material grains within the reservoir after the heating.

Currently 30-40 million dogs and cats are fed in Japan. 70% or more of them eat commercially available pet food. On the one hand commercially available pet food is widely used for a reason that it has an advantage that long term storage is possible and an advantage that nutrients necessary to a pet are contained in a balanced manner, or other reasons, but on the other hand problems are pointed out that a great amount of additives such as preservative, antiseptic, antioxidant or the like are contained so that there is a risk that pet's health is impaired, and that the nutrients contained are from chemical substances.
In view of such problems, guardians are increasing who do not use commercial pet food but prepare handmade food at home. However, preparing food for a pet everyday requires great care and is not easy. Especially, though a guardian sometimes entrusts a pet to a pet hotel or an acquaintance during a travel or a business trip, it is not easy, in such a case, to prepare food for a few days or to instruct the pet hotel or the acquaintance to give properly the prepared food to the pet. As a result of such problems, many guardians tend to use commercial pet food for convenience, though they believe that handmade food is preferable for maintaining pet's health.
Incidentally, a manufacturing method of additive-free pet food is disclosed in Patent Document 1. According to this document, it is possible to manufacture pet food that can be stored as long as one year or more by combining a plurality of heating processes and cooling processes. Although the pet food manufactured by such a method is much more preferable for pet's health than pet food containing additives, it is accompanied by problems that the cost is necessarily high owing to complicated processes, and that it is difficult to vary the nutrient components, texture, taste and the like of the pet food in accordance with the health condition, constitution, and preference of individual pets, because mass production of pet food of the same kind is assumed.
Further, a manufacturing method of pet food which allows manufacturing pet food in accordance with the guardian's request is disclosed in Patent Document 2. According to the method disclosed in this document, since pet food is manufactured of materials in accordance with the guardian's request, it is possible to satisfy the health condition, constitution, or preference of individual pets to a certain degree. However, the method is implemented by a large scale apparatus disposed in a pet-related shop, so that it is necessary to go to the pet-related shop every time the pet food is required, and since no additives are included, a long-term storage is limited so that it is not practical to buy a large amount at once, which makes it necessary to go frequently to the pet-related shop and is troublesome.

Apparatus and method for manufacturing pet food

National University Corporation Tottori University


A process for reducing odor emission in aqueous polymer dispersions and in polymer powders comprises admixing an aqueous dispersion of a polymer obtained by free-radical polymerization of one or more ethylenically unsaturated monomers, after conclusion of the polymerization, with an odor-reducing composition containing a) one or more water-soluble compounds selected from metal salts of copper(II), silver, aluminum, zinc and iron(III), potassium permanganate, imidazoline, and imidazoline derivatives, optionally in combination with b) one or more water-soluble reducing agents selected from ascorbic acid, isoascorbic acid, iron(II) salts, zinc formaldehydesulfoxylate and alkali metal formaldehydesulfoxylate, and optionally drying the thus treated aqueous polymer dispersion to form a polymer powder.

1. Field of the Invention
This invention relates to a process for reducing odor emission in aqueous polymer dispersions and in polymer powders.
2. Background Art
Polymer dispersions and polymer powders are used as binders in the building, coating and textile sectors. One problem of such dispersions and polymer powders is that they generally still contain volatile odor-intensive constituents such as mercaptans, which are used as chain transfer agents in polymerization; ammonia, which is used for neutralization; residual monomers; nonpolymerizable impurities of the monomers; volatile reaction products of the monomers that are formed under reaction conditions; and volatile degradation products of the polymers. The resulting odor is perceived as unpleasant not only by manufacturers but also by users/consumers, which is why there is a need for deodorized aqueous polymer dispersions and polymer powders.
In addition to the intrinsic odor of polymer dispersions, there are often odor sources which arise during processing. One example is in the production of fibers. Fibers are subjected to a high mechanical load in the course of processing. In order that they may be able to withstand this high mechanical stress, they are treated with pretreatment agents such as sizes, textile auxiliaries for dyeing and printing, and fiber finishes. Typical textile auxiliaries include dispersants (e.g. naphthalenesulfonates, fatty alcohol ethoxylates, polyacrylates), dyeing wetters, dyeing accelerants, dyes (e.g. indigo, sulfur dyes). Finishes include optical brighteners, agents for improving the wrinkling and creasing characteristics, antistats, hydrophobicizers, and flame retardants. All these additives are subjected to a high thermal load together with the polymers in the course of pressing operations. Decomposition reactions which take place lead to a multiplicity of chemical compounds which are responsible for an unpleasant odor.
It is known to deodorize polymer dispersions by physical or chemical aftertreatment. Physical processes, for example, include distillative processes, especially steam distillation, and also stripping with inert gases, as disclosed in EP-A 327006. The disadvantage of this process is that many dispersions are insufficiently stable for this kind of deodorization, so that coagulum formation occurs, which necessitates costly and inconvenient filtration before further use. The process has a further disadvantage, in that although it is able to reduce the fraction of volatile materials in the aqueous polymer dispersion, it does not resolve the issue of disposing of these materials.
It is also known to free polymer dispersions of odor-intensive monomers by chemical aftertreatment. For instance, DE-A 4419518 describes a free-radical postpolymerization using redox initiator systems to lower the level of residual monomers by chemical means. U.S. Pat. No. 4,529,753 describes a process whereby the level of residual monomers in aqueous polymer dispersions can be reduced by the action of particular free-radical redox initiator systems in a free-radical postpolymerization subsequent to the end of the main polymerization reaction. Such redox initiator systems comprise at least one oxidizing agent, at least one reducing agent and also one or more transition metal ions occurring in various valency states.
However, the above-recommended processes are disadvantageous in that, although they are in some instances able to lower the residual monomer content when used in odor-intensive polymer dispersions, they are not effectively able to control the unpleasant odor due to odor-intensive by-products, nonpolymerizable impurities of the monomers, volatile reaction products of the monomers, or volatile degradation products of the polymers. Nor are these measures able to effectively prevent the odor emission which is due to auxiliaries which are-used in the course of the processing of the polymer dispersions or polymer powders.
U.S. Pat. No. 4,906,462 discloses an odor-inhibiting composition which contains a phosphoric acid component, a copper compound and optionally a reducing agent. JP-A 62-204755 utilizes a combination of copper sulfate and ascorbic acid for deodorization in air-conditioning systems. GB-A 2340505 describes the use of imidazole compounds for odor minimization in natural gas and crude oil.
It is an object of the present invention to provide a process for effectively reducing the odor emission of polymer dispersions and polymer powders, in particular during their processing. These and other objects are achieved by admixing an aqueous polymer dispersion, post-polymerization, with a selected group of water soluble deodorizing compounds.

Process for reducing odor emission in aqueous polymer dispersions and in polymer powders


A flexible actuator assembly (20) including a flexible bladder device (22) having an expandable sealed chamber (23) adapted to substantially directionally displace between a deflated condition and an inflated condition, displacing a proximal portion (25) of the bladder device (22) away from a distal portion (26) thereof. An elongated tendon member (27) includes a distal portion (28) oriented outside the chamber (23), while an anchor portion (30) extends into the chamber (23) through a distal opening (31) in the bladder device (22). The tendon anchor portion (30) is further coupled proximate to the bladder proximal portion (25) in a manner adapted to: selectively invert displaceable portions (32) of the bladder device (22) when urged toward the deflated condition to position the anchor portion (30) and the bladder proximal portion (25) relatively closer to the bladder distal portion (26); and selectively evert the inverted displaceable portions (32) of the bladder device (22) when displaced toward the inflated condition which positions the anchor portion (30) and the bladder proximal portion (25) relatively farther away from the bladder distal portion (26) for selective movement of the tendon distal portion (28) between an extended condition and a retracted condition, respectively.

In the recent past, industrial robotic devices have played an increasing and more pivotal role in the manufacture of commercial products. These robotic actuator devices can typically be classified into either linear-type actuators or rotary-type actuators, both of which are generally constructed as rigid mechanical structures generating substantial forces and/or torque. These industrial devices, however, are often not suitable for use in biorobotics due to their non-natural compliance of robotic movement, as compared to natural human movement.
Biorobotic actuator devices which have been found suitable for use with, or as a replacement of, biological musculo-skeletal anatomies often include rigid skeletal structures moved by flexible artificial muscle actuators constructed to mimic the form and function of the biological components of real animals or humans. The artificial muscle, therefore, must be designed to function even when laterally deformed, and to include exceptional volumetric efficiency for the amount of linear displacement produced.
Rotary-type actuators, which transmits energy by applying a torque to a shaft rotating about a longitudinal axis thereof, are typically difficult to incorporate as artificial muscle replacements. The electric motors employed necessitate the application of additional conversion mechanisms to convert rotary motion into useable linear motion. These conversion mechanisms, such as linkages, cams, gears, pulleys, etc., become very cumbersome to arrange when attempting to apply these actuators to prosthetic devices which often require that many actuators fit into a small deformable volume while maintaining the high volumetric functional efficiencies of biological musculo-skeletal systems. One such patented system, however, is disclosed in U.S. Pat. No. 4,843,921 to Kremer.
Hydraulic cylinder actuators, by comparison, may be better adapted to mimic biological muscle since both generate a linear force and thus a linear motion. Generally, the outward pressure urged outwardly upon on the cylinder walls is converted into an axial force urging the piston into or out of the chamber. One substantial problem associated with hydraulic cylinders is that they must be substantially rigid since a fluid tight seal must be formed between the cylinder walls and the opposed surface of the inner piston. These small clearances, however, are difficult to maintain for flexible materials. Therefore, conventional hydraulic cylinders are usually substantially rigid structures which oppose substantial deformation and thus lack pliability of biological muscles. Compared to real muscle tissue which can and does operate when laterally deformed, the rigid physical property of hydraulic cylinder actuators limit their application in duplicating biological anatomy.
To address these deficiencies, several artificial muscle assemblies have been developed in the recent past which produce linear displacement and are flexible in nature. The most well renown is the McKibben Artificial Muscle, developed by Dr. Joseph McKibben, in the 1950's for use in an arm prosthesis. Briefly, this design employs an elongated, expandable inner bladder positioned inside a larger diameter braided or woven tube having strategically oriented fiber filaments. This woven tube arrangement enables a controlled radial expansion of the expandable bladder, when pressurized, which causes the opposed ends to axially contract. Thus, the overall longitudinal dimension of the artificial muscle contracts to produce the linear displacement relative the opposed ends of the inner bladder and woven tube.
The primary problem associated with this design is that the bladder and tube combination is only capable of contracting about thirty (30) percent of its rest length. This relatively small linear displacement substantially limits its use in biomechanical systems since the joint dimensions, as well as the tendon attachment and routing, become very critical. In addition to substandard joint geometry and/or tendon routing, other factors may substantially affect the range of motion of the joint such as tendon stretching and mechanical wear. Typical of the basic McKibben artificial muscle design is disclosed in U.S. Pat. No. 5,474,485 to Srnrt; U.S. Pat. No. 5,351,602 to Monroe; U.S. Pat. No. 5,185,932 and U.S. Pat. No. 5,021,064 to Caines; and U.S. Pat. No. 4,739,692 to Wassam et al.
Finally, hydrogels (pH muscles) are also presently being developed as a means for artificial muscle. These hydrogel muscles have several characteristics similar to human muscle, and may change in volume by as much as 1000% when the pH is altered. The present designs, however, are relatively slow to operate and currently produce much smaller linear forces than would be operationally feasible. Moreover, hydrogel muscles are acid based which increases the difficulty in handling, transport and operation.


A heat-pipe type heat sink (100) includes a plurality of fins (10), at least a heat pipe (20) extending through the fins, and soldering material (40) disposed between the heat pipe and the fins. Each of the fins defines therein a through hole (12) and a cutout (13) adjacent to the through hole. A sidewall of the through hole forms a collar (122) contacting with the heat pipe, whilst a sidewall of the cutout forms at least a fringe (132) connecting with the collar. The fringe guides the soldering material in molten state to flow from the cutout towards the collar to fill in a gap formed between the heat pipe and the fins to bond the heat pipe and the fins together after the molten soldering material is cooled.

1. Field of the Invention
The present invention relates generally to a heat sink, and more particularly to a heat-pipe type heat sink for dissipating heat generated by electronic components.
2. Description of related art
A conventional heat-pipe type heat sink includes a plurality of fins and a heat pipe extending through the fins. Each of the fins defines a larger hole, and a smaller hole above the larger hole. The smaller hole partially connects with the larger hole at a bottom end thereof.
In assembly of the heat sink, the heat pipe extends through the larger holes of the fins, while a solder stick extends through the smaller holes of the fins. The solder stick is heated to melting point so that the molten solder flows into the larger holes and fills gaps formed between the heat pipe and the fins. The molten solder is cooled so as to firmly bond the heat pipe to the fins to complete the assembly of the heat sink.
When the molten solder flows towards the larger holes, a part of the molten solder can not be timely guided towards the gaps and therefore bleeds towards spaces formed between two adjacent fins. When that part of the molten solder is cooled, a plurality of solder beads are formed between the fins. Therefore, the solder cannot fully fill the gaps, which results in an incomplete connection between the heat pipe and the fins, and further decreases the thermal connection between the heat pipe and the fins. Furthermore, the solder bleeds adversely affect the aesthetic appearance of the heat sink and cause a waste of the solder. Thus, an improvement is required to overcome the defects of the prior art.

Fu Zhun Precision Industry (Shen Zhen) Co., Ltd.


A cathode in a state prior to a first charging process is provided having an active cathode material and lithium peroxide. A lithium ion battery or an electrochemical cell includes the same cathode. A method is also provided for forming a lithium ion battery, and a lithium ion battery is provided which includes a cathode having an active cathode material, a separator, an anode having an active anode material, and an electrolyte, wherein after a formed cell is fully discharged, the active cathode material holds the same lithium content as before the formation process.

The present invention relates to a cathode in a state prior to a first charging (or formation) having an active cathode material and lithium peroxide, and a lithium ion battery including such cathode. The present invention also relates to a process for producing a lithium ion battery, and a lithium ion battery after formation.
The present invention further relates to a cathode having lithium peroxide (Li2O2), and a lithium ion battery including such cathode in a state prior to a first charging (or formation).
As used herein, the terms "lithium ion battery", "rechargeable lithium ion battery" and "secondary lithium ion battery" are used synonymously. These terms also encompass the terms "lithium battery", "lithium ion accumulator" and "lithium ion cell," and also all lithium or alloy batteries, in particular also Li sulfur and alloy systems. Thus, the term "lithium ion battery" is used herein as a collective term for the abovementioned terms customary known in the art. It refers to both rechargeable batteries (secondary batteries) and non-rechargeable batteries (primary batteries). In particular, as used herein, a "battery" within the meaning of the present invention also encompasses an individual or single "electrochemical cell".
Generally, as known in the art, the mode of action of a lithium ion battery can be described as follows: the electric energy is stored in lithium ions (at the negative electrode) and transition metal oxides (at the positive electrode) in a chemical process with a change of material. Here, lithium in ionized form (Li+) can migrate back and forth through the electrolyte between the two electrodes. In contrast to the lithium ions, the transition metal ions present at the cathode are fixed in place.
This flow of lithium ions is necessary to compensate the external flow of electric current during charging and discharging, so that the electrodes themselves remain electrically neutral. During discharging, the effective lithium atoms (or the negative active material containing the lithium ions) each release an electron at the negative electrode and this electron flows via the external current circuit (load) to the positive electrode. At the same time, the same number of lithium ions migrates through the electrolyte from the negative electrode to the positive electrode. However, the lithium ions do not take up the electron again at the positive electrode but instead the transition metal ions present there take up the electrons. Depending on the type of battery, these can be cobalt, nickel, manganese, iron ions, etc. The lithium thus continues to be in ionic form (Li+) at the positive electrode in the discharged state of the cell.
In general, lithium ion batteries are assembled or manufactured in the discharged state. That is to say, the cathode, e.g., LiCoO2, is completely intercalated with lithium ions, while the anode, e.g., carbon, is completely empty (i.e., it is not loaded with lithium).
During first charging, also referred to as a formation process, the anode is polarized in the negative direction (i.e., electrons flow into the active anode material, e.g., carbon or graphite) and lithium cations leave the active cathode material of the cathode, enter the electrolyte and are intercalated into the active anode material with formal reduction.
The first charging process is particularly complex since many reduction reactions and decomposition reactions occur here. As a result, not only actual charging but also the formation of a solid electrolyte interphase ("SEI"), to which mainly reductive decompositions of a small amount of organic electrolyte are ascribed, occurs. The formation of the SEI layer is quite desirable since it counters further decomposition of the electrolyte and thus effectively acts as a protective layer around the particles of the active material in the negative electrode, by means of which important electrical properties such as life and cycling stability of the lithium ion battery can be optimized.
During formation, however, lithium is required and consumed for creating the SEI layer and this is later no longer available for cycling. The ratio of the first charge/discharge is referred to as formation loss and is about 10% when LiCoO2 is used as the active cathode material and graphite is used as the anode material. Accordingly, the active cathode material as the sole source of lithium in a cell has to be over dimensioned by about 10% in this example. In the case of the active anode materials (e.g., silicon-based) being developed at present, the formation losses can even be more than 40%.
U.S. Pat. No. 5,531,920 provides a process for preparing LiMnO2, in which the starting compound Mn(OH)2 is oxidized by means of lithium peroxide (Li2O2). Since the lithium peroxide is completely reacted in this process, the end product no longer contains any lithium peroxide.
The document Electrochemistry Communications 12 (2010) 1344-1347 by D. Shanmukaraj et al. discloses a process in which nitrogen-based Li salts which are decomposed during formation are added to the cathode. However, such nitrogen-based salts can at least partly decompose in an uncontrolled manner as early as in the mixing process.
It is an object of the present invention to provide a lithium ion battery having an increased specific energy or energy density combined with lower production costs.
It is an object of the present invention to provide a cathode in a state prior to a first charging (or formation). The present invention also provides a lithium ion battery in a state prior to formation, and a process for forming a lithium ion battery. The present invention further provides a lithium ion battery in a state after formation.
The following definitions apply, where applicable, to all aspects according to the invention.
Lithium Ion Battery
As used herein, the term "lithium ion battery" is as defined above. In particular, the term also includes, according to the invention, an individual or single "electrochemical cell". In a "battery", two or more such electrochemical cells are preferably connected, either in series (i.e., after one another) or in parallel.
Electrodes
The electrochemical cell of the invention has at least two electrodes, i.e., a positive electrode (cathode) and a negative electrode (anode).
The two electrodes each have at least one active material. This is able to take up or release lithium ions and at the same time take up or release electrons.
As used herein, the term "positive electrode" means the electrode which is, when the battery is connected to a load, for example an electric motor, able to take up electrons. In this nomenclature, it represents the cathode.
As used herein, the term "negative electrode" means the electrode which is able to release electrons during operation. In this nomenclature, it represents the anode.
The electrodes include inorganic material or inorganic compounds or substances which can be used for or in or on an electrode or as electrode. These compounds or substances can take up (intercalate) lithium ions or metallic lithium and release them again under the operating conditions of the lithium ion battery due to their chemical nature. In the present description, such a material is referred to as "active cathode material" or "active anode material" or generally "active material". For use in an electrochemical cell or battery, this active material is preferably applied to a support, preferably to a metallic support, preferably aluminum for the cathode and copper for the anode. This support is also referred to as "power outlet lead" or as "collector" or "collector foil."
Cathode (the Positive Electrode)
As for the active material for the positive electrode or the cathode, it is possible to use active materials which are known in the art. These include but not limited to, for example, LiCoO2 (LCO), lithium nickel cobalt manganese oxide (NCM), lithium nickel cobalt aluminum oxide (NCA), high-energy NCM (HE-NCM), lithium iron phosphate or Li-manganese spinel (LiMn2O4). According to one aspect of the present invention, any suitable active material known in the art can be used for the positive electrode (or the cathode).
In a preferred embodiment, active materials for the cathode can be selected from the group consisting of lithium-transition metal oxide ("lithium-metal oxide"), layered oxides, spinels, olivine compounds, silicate compounds and mixtures thereof. These active cathode materials are described, for example, in Bo Xu et al. "Recent Progress in Cathode Materials Research for Advanced Lithium Ion Batteries", Materials Science and Engineering, R 73 (2012) 51-65. Preferably, the cathode material is HE-NCM. Layered oxides and HE-NCM are described in the patent documents U.S. Pat. Nos. 6,677,082 B2, 6,680,143 B2, and 7,205,072 B2 of the Argonne National Laboratory.
Examples of olivine compounds are lithium phosphates of the empirical formula LiXPO4 where X=Mn, Fe, Co or Ni, or combinations thereof.
Examples of lithium-metal oxide, spinel compounds and layered oxides are lithium manganite, preferably LiMn2O4, lithium cobaltate, preferably LiCoO2, lithium nickelate, preferably LiNiO2, or mixtures of two or more of these oxides, or mixed oxides thereof.
The active material can also contain mixtures of two or more of the substances mentioned.
To increase the electrical conductivity, further compounds, preferably carbon-containing compounds, or carbon, preferably in the form of conductive carbon black or graphite, can be present in the active material. The carbon can also be introduced in the form of carbon nanotubes. Such additions are preferably in an amount of from 0.1 to 6% by weight, more preferably from 1 to 3% by weight, based on the mass of the positive electrode applied to the support.
Anode (the Negative Electrode)
As for the active material for the negative electrode or the active anode material, it is possible to use active materials which are known in the art. According to one aspect of the present invention, any suitable active material known in the art can be used for the negative electrode (or the anode). Preferably, the active materials are partially lithiated, particularly preferable active materials are non-prelithiated.
The active material for the anode can be selected from the group consisting of lithium-metal oxides, such as lithium-titanium oxides, metal oxides (e.g., Fe2O3, ZnO, ZnFe2O4), carbon-containing materials such as graphite (e.g., synthetic graphite, natural graphite), graphene, mesocarbon, doped carbon, hard carbon, soft carbon, fullerenes, mixtures of silicon and carbon, silicon, lithium alloys and mixtures thereof. It is also possible to use niobium pentoxide, tin alloys, titanium dioxide, tin dioxide, and silicon as the active material for the anode (or the negative electrode).
In a preferred embodiment, the active anode material is a material which can be alloyed with lithium. This can be a lithium alloy or an unlithiated or partially lithiated precursor from which a lithium alloy is formed during formation. Preferred materials which are able to be alloyed with lithium are lithium alloys selected from the group consisting of silicon-based, tin-based and antimony-based alloys. These alloys are described, for example, in the article by W. J. Zhang, Journal of Power Sources, 196 (2011) 13-24.
Electrode Binder
The materials used for the positive electrode or for the negative electrode, for example the active materials, are held together by one or more binders which hold these materials on the electrode or on the power outlet lead.
The binders can be selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyethylene oxide (PEO), polytetrafluoroethylene, polyacrylate, styrene-butadiene rubber and carboxymethylcellulose (CMC) and mixtures and copolymers thereof. The styrene-butadiene rubber and optionally carboxymethylcellulose and/or further binders such as PVDF are preferably present in an amount of 0.5-8% by weight based on the total amount of the active material used in the positive or the negative electrode.
Separator
The electrochemical cell of the invention has a material which separates the positive electrode and the negative electrode from one another. This material is permeable to lithium ions, i.e., conducts lithium ions, but is a nonconductor for electrons. Such materials used in lithium ion batteries are also referred to as separators.
In a preferred embodiment of the present invention, polymers are used as separators. In one embodiment, the polymers are selected from the group consisting of: polyester, preferably polyethylene terephthalate; polyolefin, preferably polyethylene, polypropylene; polyacrylonitrile; polyvinylidene fluoride; polyvinylidene-hexafluoropropylene; polyether imide; polyimide, polyether; polyether ketone and mixtures thereof. The separator has porosity, so that it is permeable to lithium ions. In a preferred embodiment of the present invention, the separator consists of at least one polymer.
Electrolyte
As used herein, the term "electrolyte" refers to a liquid in which a lithium electrolyte salt has been dissolved. The liquid is preferably a solvent for the electrolyte salt. The Li electrolyte salt is then preferably present as electrolyte solution.
Suitable solvents are preferably inert solvents. Examples of suitable solvents include preferably organic solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, sulfolanes, 2-methyltetrahydrofuran and 1,3-dioxolane. Preference is given to using organic carbonates.
In one aspect of the present invention, the ionic liquids can also be used as solvents. The ionic liquids contain exclusively ions. Examples of cations include those which can, in particular, be alkylated, are imidazolium, pyridinium, pyrrolidinium, guanidinium, uronium, thiouronium, piperidinium, morpholinium, sulfonium, ammonium and phosphonium cations. Examples of anions which can be used are halide, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, phosphinate and tosylate anions.
Examples of ionic liquids include but not limited to: N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide, N-butyl-N-trimethylammonium bis(trifluoromethylsulfonyl)imide, triethyl sulfonium bis(trifluoromethylsulfonyl)imide and N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide.
Preference is given to using two or more of the abovementioned liquids. Preferred electrolyte salts are lithium salts which have inert anions and are preferably nontoxic. Suitable lithium salts are preferably lithium hexafluorophosphate (LiPF6), or lithium tetrafluoroborate (LiBF4) and mixtures of one or more of these salts. In one embodiment, the separator is impregnated or wetted with the lithium salt electrolyte.
Various objects, advantages and novel features of the present invention will become apparent from the following detailed description of one or more preferred embodiments.
In one aspect of the present invention, the invention is directed to a cathode in a state prior to a first charging process (or formation process) having an active cathode material and lithium peroxide.
According to one aspect of the present invention, the cathode contains lithium peroxide (Li2O2).
The lithium peroxide serves to compensate formation losses and is therefore preferably added in an amount that matches to the anode on installation in an electrochemical cell. In contrast to the invention, the lithium peroxide used in conventional art oversizes the cathode material to compensate for the formation losses. In the case of the lithium ion batteries used in the conventional art, a solid phase which does not contribute to the capacity remains in the cathode after formation. Since, according to the invention, active cathode material is replaced, in comparison with the conventional art, by less expensive and lighter lithium peroxide (Li2O2) in the cathode, the cathode according to the invention is less costly and has a higher specific capacity compared to those used in the conventional art. In addition, lithium peroxide has a lower molar mass compared to known active cathode materials, based on the equivalent molar amount of lithium. Thus, the cathode has, even in the state prior to first charging, a lower weight per unit area compared to those cathodes used in the conventional art. This effect is reinforced further by the formation of the lithium cell, since the lithium peroxide decomposes according to the following reaction equation during formation:Li2O2→2Li++2e−+O2 (gas)
The lithium formed in this way can then, e.g., in a layer formed on the anode during formation, react according to the following reaction equation (as described by Tasaki et al., J. Electrochem. Soc., 2009, 156, 12, A1019-A1027):ROCO2R+2Li++2e−→2LiOR+CO  (gas); or2(CH2)2CO+2Li++2e−→(CH2OCO2Li)2+C2H4  (gas)
The oxygen gas from the decomposition of the lithium peroxide can be removed together with the other gases involved during formation from the lithium ion battery. Methods of removing gases which are formed during formation are well known in the art.
The cathode according to the present invention is particularly suitable for use together with active anode materials which display high formation losses. Such materials are shown in Table 1 below:
TABLE 1Typical formation losses for various anode active materials:Formation losses;Materialapproximate figuresSynthetic graphite6-8%Natural graphite 8-12%Soft carbon12-20%Hard carbon15-25%Si—C blend comprising 10% of Si15-20%Si—C blend comprising 20% of Si20-25%Si—C blend comprising 50% of Si30-40%Pure silicon50%
The cathode according to the present invention is also particularly suitable for use with the abovementioned lithium alloys which are described in the article W. J. Zhang, Journal of Power Sources, 196 (2011) 13-24. The commercial use of these alloys has hitherto been limited by, in particular, the high irreversible capacity loss (formation loss).
The cathode according to the present invention can include the lithium peroxide as a mixture with the active cathode material or in separate regions of the cathode. For example, it is also possible to apply the lithium peroxide as a covering layer to the active cathode material.
The cathode of the present invention preferably includes the lithium peroxide as a mixture with the active cathode material. In this way, the porosity of the cathode can be increased by the oxygen gas evolved in the decomposition of the lithium peroxide during formation. The increased porosity of the cathode has a favorable effect on the wetting by electrolyte, life and loading capability of the cathode.
The proportion of lithium peroxide based on the lithium content of the active cathode material is preferably from 1 to 60 mol %, more preferably from 1 to 50 mol %, particularly preferable, from 2 to 35 mol %.
The mixture preferably further includes a binder and electrical conductivity additive.
In another aspect, the present invention provides a lithium ion battery in a state prior to a first charging (or formation) which includes a cathode in a state prior to a first charging (or formation) having an active cathode material and lithium peroxide, a separator, an anode and an electrolyte.
The anode preferably includes an active anode material selected from the group consisting of carbon, graphite, mixtures of silicon and carbon, mixtures of silicon and graphite, mixtures of silicon, carbon and graphite, silicon, lithium-metal oxide, materials which are able to be alloyed with lithium, and mixtures thereof.
The amount of lithium peroxide is preferably selected such that the expected formation loss is compensated at least partly on a cell level, preferably substantially completely on a cell level.
The electrolyte preferably includes at least one constituent which decomposes during formation and contributes to a buildup of the solid electrolyte interphase (SEI). Examples of constituent include organic carbonates.
The lithium ion battery according to the present invention can be produced by processes known in the art using a cathode according to the present invention.
The electrodes and the separator are preferably manufactured together so as to give an electrode-separator assembly.
In another aspect, the present invention provides a process for forming a lithium ion battery, which includes providing a lithium ion battery in a state prior to formation that includes a cathode in a state prior to a first charging (or formation) having an active cathode material and lithium peroxide, a separator, an anode, and an electrolyte; and carrying out at least one charging operation to the maximum permitted upper voltage or operating voltage of the lithium ion battery.
In yet another aspect, the invention provides a lithium ion battery which includes a cathode having an active cathode material, a separator, an anode having an active anode material and an electrolyte, wherein the active cathode material still holds the same lithium content after complete discharge of the cell, preferably to 0 V, as compared to a state prior to formation. The lithium content can be determined by, for example, detachment of the active material from the power output lead and elemental analysis by means of ICP-OES.
Since the cathode material used in the lithium ion battery can typically be determined by a person skilled in the art, the person skilled in the art can calculate back the above reference point "state prior to formation" without having to examine the battery prior to formation. The transition metal:Li ratio depends on the material actually used. The determination of the actual active material can be carried out by a person skilled in the art using a combination of various known analytical methods.
The active cathode material is preferably selected from the group consisting of lithium-metal oxide, coated oxides, spinels, olivine compounds, silicate compounds and mixtures thereof.
The active anode material is preferably selected from the group consisting of graphite, carbon, mixtures of silicon and carbon, mixtures of silicon and graphite, mixtures of silicon, carbon and graphite, silicon, lithium-metal oxide, materials which are able to be alloyed with lithium, and mixtures thereof.
In the present invention, particular preference is given to using a cathode in which the lithium peroxide is present as a mixture with the active cathode material.
The following example according to the present invention is compared to an example using a conventional cell (comparative example). In each case, the following values are used:
Molar mass of LiCoO2=97.87 g/mol, molar mass of Li2O2=45.88 g/mol.
Comparative example (e.g., using a commercially available cell):
The electrochemical cell according to the comparative example has a formation loss of 12% and a nominal capacity of 60 mAh (1 C, 2.8-4.2 V).
LiCoO2 (KD10, Umicore) vs. natural graphite (B.T.R.).
Weights per unit area: cathode=15 mg/cm2, anode=7 mg/cm2
That is to say, 12% of the usable lithium (since charging (taking out of Li) is only possible to Li0.5CoO2, which then corresponds to only 6% of the total Li present) of the cathode (LiCoO2) are consumed irreversibly.
Formation (first charging) was carried out at a rate of C/5=12 mA.
The electrochemical cell was produced as follows:
A mixture of 90 g, 5 g, 5 g of LiCoO2, conductivity additive (Super P®) and polyvinyl difluoride (PVDF) is suspended in 100 g of N-methyl-2-pyrrolidone (NMP) at 20° C. using a mixing device providing high shear. This gives a homogeneous coating composition which is applied by doctor blade to a 20 μm aluminum support. After taking off the NMP, a cathode film having a weight per unit area of 15 mg/cm2 is obtained. This is built into a cell using an anode with 7 mg/cm2 (1% by weight of conductivity additive (Super P®)), 1% by weight of carboxymethylcellulose (CMC), 2% by weight of styrene-butadiene rubber (SBR), 96% by weight of natural graphite (from BTR), Celgard® 2500 separator, (25 μm) and an electrolyte composed of a 1 M solution of LiPF6 in ethylene carbonate (EC)/diethylene carbonate (DEC) (3:7) (packaging aluminum composite film). The cell is charged for the first time up to 4.2 V (C/5) and subsequently discharged at C/2 to 2.8 V. First charging 68 mAh; first discharging 60 mAh; a formation loss of about 12% results.
An example according to the present invention:
Replacement of 12% LiCoO2 by a Li equivalent amount of Li2O2.
Correspondingly adapted weight per unit area.
A mixture of 79.2 g of LiCoO2, 2.53 g of Li2O2 (Rockwood Lithium), 5 g of Super P® and 5 g of PVDF is suspended in 100 g of NMP at 20° C. using a mixing device providing high shear. This gives a homogeneous coating composition which is applied by doctor blade to a 20 μm aluminum support. After taking off the NMP, a cathode film having a weight per unit area of 13.8 mg/cm2 was obtained (here, it was taken into account that part of the LiCoO2 has been replaced by Li2O2). This is built into a cell using an anode with 7 mg/cm2 (1% of Super P®, 1% of CMC, 2% of SBR, 96% of BTR natural graphite), Celgard® 2500 separator, (25 μm) and an electrolyte composed of a 1 M solution of LiPF6 in EC/DEC (3:7) (packaging aluminum composite film). The cell is charged for the first time to 4.2 V (C/5) and subsequently discharged at C/2 to 2.8 V. First charging 69 mAh; first discharging 60 mAh; a formation loss of about 13% results.
Similar behavior is thus observed in both cases. This shows that it is possible to compensate formation losses by means of comparatively less expensive and light lithium peroxide (Li2O2).
The above description of the present invention serves only for illustrative purposes and not for the purpose of restricting the invention. Various alterations and modifications are possible within the framework of the invention, without going outside the scope of the invention and its equivalents.

Cathode, cathode-containing lithium ion battery in the state prior to the first charging process, method for forming a lithium ion battery, and lithium ion battery after formation

Bayerische Motoren Werke Aktiengesellschaft


A method of estimating a load on a vehicle (10), the method comprising: obtaining a first load estimate using a first load estimation technique; obtaining a second load estimate using a second load estimation technique; analysing characteristics of the first load estimate and the second load estimate; and, based on the analysis selecting either the first load estimate or the second load estimate as an output load estimate.

All vehicles are subject to a force that acts in opposition to acceleration of the vehicle, which is known as the 'road load' or 'vehicle load'. The vehicle load is a product of the total vehicle mass, the gradient of the road on which the vehicle travels, and other factors such as headwinds and road surface type and condition.
Passengers, luggage, trailers, etc., can all add to the total vehicle mass, which may therefore be different for each journey that the vehicle makes.
Vehicle load has an impact on various aspects of vehicle control. For example, it may be desirable to adjust the control of an automatic transmission to account for varying vehicle load, since an increase in load entails a corresponding rise in the engine output required to provide a given vehicle acceleration, and also a rise in the stall speed of a torque converter of the transmission. It is therefore desirable to delay gear upshifts when ascending a hill, for example, to account for the increased work that the vehicle engine must perform to propel the vehicle while climbing due to the increase in vehicle load entailed by a positive road gradient.
In view of this, increasing vehicle load, for example as a result of a rising road gradient, is typically compensated for by controlling the transmission to adopt a more aggressive profile, so that gear shifts are implemented at higher engine speeds relative to when travelling on a level surface.
For example, the transmission may be controlled based on gear shift maps, which define the points at which gear changes are triggered in accordance with inputs including the vehicle speed and the accelerator pedal position. So, for example, the gear shift map may indicate that, for a particular gear ratio, the gear shift point is at a higher vehicle speed when the pedal is fully depressed than when the pedal is depressed to a lesser extent. This acknowledges that fully depressing the pedal typically indicates a driver demand for high acceleration.
The gear shift map is therefore a two-dimensional function, in that the shift points that it defines vary with respect to both vehicle speed and pedal position.
A set of gear shift maps may be used, each map being compensated for a particular discrete road gradient. For example, the set of maps may include a shift map for 2% gradient, 6% gradient, and so on. To provide effective control at gradients not precisely matching these discrete values, the pair of maps relating to gradients immediately above and below the estimated gradient are identified, and the gearshift points to implement based on the actual estimated gradient are determined using linear interpolation. For example, if the estimated gradient is 4%, the vehicle interpolates between the map for 2% gradient and the map for 6% gradient to produce a set of shift points corresponding to a 4% gradient.
In order to account for varying vehicle load, an effective road gradient may be calculated based on an estimated value of the vehicle load. The effective gradient is a gradient which would impart the estimated value of vehicle load on an otherwise unloaded vehicle. A shift map corresponding to the effective gradient may then be selected and a set of shift points may then be produced, as described above, using this effective road gradient. In this respect, the effective road gradient takes into account the actual road gradient, the mass of the vehicle and each of the other factors contributing to the vehicle load. The effective road gradient may be calculated using a function based on a predetermined relationship between vehicle load and effective road gradient.
Various techniques are known for estimating vehicle load, each with their respective strengths and weaknesses.
In a common approach, measurements of a load on a transmission output shaft and an output acceleration of that transmission shaft are obtained and cross-referenced with a calibrated model of vehicle road loads over a range of speeds on a horizontal surface.
Any deviation of the measurements from the calibrated model can be used to derive an estimate of the vehicle load, noting that an increasing vehicle road load reduces the acceleration output for a given transmission load. This approach is commonly referred to as a 'road load model' estimate. As described above, this estimate of the vehicle load is then used to determine an effective road gradient which in turn is used to determine a set of shift points for the transmission.
As an alternative to taking measurements from the transmission shaft, wheel speed measurements could be obtained so that actual vehicle acceleration can be compared with a predicted vehicle acceleration. Other sources of acceleration data are also possible; in each case, the road load model applies the same principle of comparing predicted acceleration with actual acceleration to detect deviations in vehicle load relative to its base load.
It is noted that the road load model estimate cannot distinguish between the different factors that contribute towards vehicle load. For example, adding weight to the vehicle, a positive road gradient and a headwind will all elevate the transmission load required to deliver a given acceleration, but the estimation model is unable to distinguish between these causes of increased load.
Factors that may cause inaccuracy in the estimated vehicle load provided by the road load model include: pressing the vehicle brakes, which artificially increases the load; a loss of traction of one or more road wheels, which gives the appearance of decreased load; a gear shift being in progress, which temporarily releases the load from the transmission shaft; the vehicle transitioning from a state of acceleration to one of deceleration; and the vehicle speed being below a calibrated threshold that relates to physical limitations of sensors used to measure the transmission shaft speed or wheel speed.
In another approach, the vehicle load estimate may be based on the longitudinal acceleration of the vehicle as indicated by an on-board accelerometer. Such accelerometers are able to detect a gravitational component of acceleration when the vehicle is on a gradient, which can be used to estimate the actual road gradient. The estimated actual road gradient can in turn be combined with an estimated vehicle mass to produce an estimation of the vehicle load. As described above, this estimate of the vehicle load is then used to determine an effective road gradient which in turn is used to determine a set of shift points for the transmission.
The accelerometer-based approach is particularly accurate when the vehicle is stationary, as the signal noise is low; although the technique can be used at all times.
While the vehicle is stationary, the accelerometer will indicate a longitudinal acceleration of zero m/s2 if the vehicle is on a perfectly horizontal road. However, if the actual road gradient is non-zero, the indicated longitudinal acceleration will also be non-zero due to a gravitational component of acceleration acting on the accelerometer. Therefore, hypothetically, if the vehicle were on a 90° incline the accelerometer would indicate longitudinal acceleration of 1g, where 'g' represents acceleration due to gravity on earth, which is approximately equal to 9.8 m/s2.
If attempting to estimate the actual road gradient in this way while the vehicle is moving, the longitudinal acceleration indicated by the accelerometer can be compared with vehicle acceleration as indicated by wheel speed data to resolve the gravitational component of acceleration accurately from the overall detected acceleration.
As already noted, the actual gradient estimate can be combined with an estimate of the total vehicle mass to generate a vehicle load estimate. The mass estimate may need to be accurate to within 100 kg, for example, to provide an acceptably accurate vehicle load estimate.
In this respect, it is noted that the vehicle may include optional extras that add additional bulk on top of the vehicle base mass, knowledge of which is not necessarily held by the vehicle in advance. In addition, as already noted the total vehicle mass may be different for each journey that the vehicle makes due to additional mass in the form of luggage, trailers, etc.
The vehicle must therefore estimate its overall mass for each journey that it undertakes. This is typically achieved through analysing vehicle dynamics over time, noting that the total mass is equal to the resultant force acting on the vehicle divided by the vehicle acceleration. It can take a significant period to refine the estimate to a reasonable level of accuracy, until which point the accelerometer-based actual gradient estimate cannot be converted into an accurate vehicle load estimate.
Although the actual gradient estimate based on measurements produced by the accelerometer is relatively reliable, the mass estimate that is required to convert it into a vehicle load estimate is susceptible to error in a similar way to the road load model. Various factors including those mentioned above can distort a mass estimate. Additionally, a headwind, insofar as it resists movement of the vehicle in a similar way to additional mass, may cause the vehicle to overestimate the total mass.
It is also known, for example from US 2014/0067153, to use more than one technique in parallel to provide multiple road gradient estimates. The final road gradient estimate is then selected from the set of estimates available based on indications of the vehicle state, so that each technique is used during specific vehicle operating conditions. However, this approach is relatively inflexible and cannot dynamically respond to changes in estimate reliability caused by factors such as activation of the brakes or traction control system, or gear shift events, for example.
It is against this background that the present invention has been devised.


The present disclosure is generally related to the field of printing, and other processes based on the continuous deposition of material, including industrial molding or extrusion processes, and more particularly to techniques for grouping object quality anomalies in a specified region of an object based on context-specific characterization and shared descriptive profile features.

The present disclosure is generally related to the field of printing, and other processes based on the continuous deposition of material, including industrial molding or extrusion processes, and more particularly to techniques for grouping object quality anomalies in a specified region of an object based on context-specific characterization and shared descriptive profile features.
In many industrial processes, for example in extrusion or molding processes, the product may contain defects that appear as streaking in the direction of the manufacturing process. For example, the defects might take the form of ridges in the finished material. In the printing industry, the same type or a similar defect may result in dark or light lines across or through the printed image. Different process faults can cause different patterns of streaking in the finished materials. Defects are generally characterized within the printing industry as "streaking" if the defect occurs along the process direction of the printed or manufactured product, or as "banding" or another periodic defect if it appears in the cross-process direction.
Previous work with regard to streaking has focused mainly on detecting the streak or process defect, and on characterizing the streaks or defects, including techniques related to model-based diagnosis. Diagnosis of streaking in industrial processes is largely a manual process that requires trained technicians with direct experience on the equipment in question.
In the printing industry, diagnosis has focused predominantly on streak detection and analysis, and on a clustering-related technique that provides a generic mechanism for the clustering of streaks based solely on visual features. Though these techniques are available for use with regard to identifying streaks, none focus specifically on interpreting the identified streaks. More specifically, no technique provides for focusing on the characterization and classification of streaks using a specific formulation of features for recognizing a cluster of similar streaks, and then for further identifying those streaks in the cluster that share more focused similarities based on a given set of descriptors.

Robust recognition of clusters of streaks at multiple scales


In a film forming unit (FU) for a sputtering apparatus according to this invention, a supporting plate is provided with: a target having bonded thereto a backing plate; a magnet unit; and driving device for reciprocating the target along the supporting plate relative to the magnet unit. The backing plate is provided, in a protruded manner, with a supply pipe and a discharge pipe in communication with a coolant passage for the backing plate. A slit hole, which is elongated in the reciprocating direction of the target and through which the supply pipe and the discharge pipe penetrate, is formed in the supporting plate. The supporting plate has on its lower surface a cap body which hermetically encloses those portions of the supply pipe and the discharge pipe, inclusive of the slit hole, which are protruded downward from the slit hole.

This kind of film forming unit for a sputtering apparatus is known, e.g., in Patent Document 1. The unit in question is provided with a box-shaped enclosure (displacement part) which is mounted on an inner wall surface of a vacuum chamber in which film forming is performed, and a displacement plate is disposed on that side surface of the enclosure which looks inward of the vacuum chamber. The displacement plate has fixed thereto, through a supporting body, a backing plate which has a target bonded to one surface as a cathode. Further, positioned on the inside of an opening which is provided in the displacement plate, a magnet unit for causing to function a leakage magnetic field on the surface of the target is fixed to the inside of the supporting body.
The inside of the enclosure is divided by a partition wall into two chambers. One of the chambers is in communication, through a penetrating hole opened in the enclosure, with a space on the side of the target, i.e., with the vacuum chamber which is evacuated for performing film forming processing therein. The other chamber is provided with a driving motor, and a driving shaft of the driving motor penetrates the partition wall to protrude into said one chamber. At a tip of this protruded driving shaft, there is provided a connection rod, and the connection rod is connected to a displacement plate. In this arrangement, when the driving motor is driven, the backing plate which is fixed to the displacement plate through a supporting plate and, consequently, the target makes a relative movement in relation to the magnet unit. According to this arrangement, when a rare gas or a reactive gas for electric discharging at the time of reactive sputtering is introduced into the vacuum chamber and, while the target is sputtered by applying predetermined electric power, e.g., with negative potential, the relative positions of the magnet unit do not change, even if the target is moved, and of a deposition-preventive plate (anode) to be provided in front of the target which looks inward of the vacuum chamber, do not change. Changes in the conditions of the plasma such as the position, density and the like of plasma on the surface of the target can thus be restrained.
In the above-mentioned prior art, however, since the enclosure of the film forming unit is directly mounted on the inner wall surface of the vacuum chamber, there are problems in that the mounting and dismounting of the film forming unit are troublesome, resulting in inconvenience in maintenance. Further, during sputtering, it is necessary to supply the backing plate with cooling medium such as cooling water. For that purpose, it is necessary to separately provide the wall surface of the vacuum chamber with water supply pipes and water distributing pipes separately, thereby resulting in complex apparatus arrangement.

Film forming unit for sputtering apparatus


An apparatus for drying moist or wet carbon particles in a series of tubular drying sections by electrical resistance heating where the current is introduced into the column of carbon particles through a graphite block positioned at the center of the top of the column and suspended above the top of the column by attachment to a steel plate that includes a flat or a V-shaped shelf and that is provided with openings to allow the moisture to escape in the form of steam, and wherein the section consisting of graphite block, carbon column, and steel plate may provide entry of the carbon into a second or into a sequential plurality of similar sections provided with similar graphite blocks similarly positioned.

1. Field of the Invention
This invention relates to an apparatus and process for drying of carbonaceous feedstocks by electrical resistance heating. It particularly relates to an improved apparatus for conducting an improved electrical resistance heating process in which the energy cost of drying is reduced, and the process is more efficient and faster and can accept carbonaceous feedstocks with higher moisture contents, larger ranges of particle size, and more variable particle size distributions as compared with previously described electrical resistance processes for the drying of carbon.
2. Description of the Related Art
The drying of wet powdered or granular solids requires the vaporization of the moisture followed by its physical removal, usually by a stream of air or other gas. The process is hastened by the application of heat either to the wet material or to the gas stream that is made to flow over or through the material. When the powdered or granular material is carbon, electrical resistance heating may be applied directly to the solid, as is well known in the prior art relating to the activation of various carbonaceous feedstocks or to the reactivation of spent activated carbons, as described, for example, in U.S. Pat. No. 5,089,457 and prior patents cited therein. Effective rapid drying of wet carbons requires temperatures only about or modestly above the boiling point of water, such as temperatures in the range from 100.degree. C. to about 150.degree. C., whereas the activation of carbon feedstocks or the reactivation of spent activated carbons commonly requires temperatures of about 750.degree. C. or higher.
When a moist or wet carbonaceous feedstock is activated or a wet spent activated carbon is reactivated by electrical resistance heating, the carbon is either dried prior to the activation or reactivation step, or else some or substantially all of the moisture is removed in the process of the activation or reactivation. In the latter case, as the vaporized moisture moves toward the furnace exit, through and past the section that preheats the carbon, it recondenses and offers increased resistance to the movement of other gases (such as CO and H.sub.2) that are produced in the activation process or that are desorbed in the reactivation of spent activated carbons and that must escape to the exit. Still another disadvantage is the uneven current distribution that results from the variation in electrical resistance in different portions of the wet carbon.
It is accordingly an object of this invention to provide an improved apparatus for the drying of wet granular or powdered carbon by electrical resistance heating.
It is another object of this invention to provide such improvement when the carbon contains any amount of moisture up to and including full saturation, so long as no free liquid water is present.
It is another object of this invention to provide such improvement when the carbon is a carbonaceous feedstock, such as wood char, coconut char, or petroleum coke, for the production of activated carbon, or is an exhausted activated carbon that is to be reactivated.
It is another object of this invention to provide that the electric current passing through the carbon being dried is distributed uniformly therethrough.
It is yet another object of this invention to insure that the moisture being removed from the carbon does not recondense on the carbon before it escapes.
The achievements of these and other objects will be apparent from the following description of the subject invention.

Apparatus for drying of granular or powdered carbon by electrical resistance heating


A vehicular rearview assembly with a heating element. The heating element is affixed behind and in thermal communication with the mirror element of the assembly. The heating element includes a plurality of heating zones that operate in alternation according to a pre-determined time-sequence. A peripheral area of the mirror element is heated up to at least as high a temperature as an inner area of the mirror element. Switching the heating zones on and off so as to have only one heating zone on at a time is determined by a controlling circuitry at least a portion of which may be separated from the assembly and disposed in a different part of the vehicle.

An automotive reflective mirror element such as that which is part of an automotive rearview assembly often has to be heated during a cold season in order to defrost the surface of the mirror element. With most such mirror elements, an electrical heating element is arranged adjacent to a back surface of the mirror. Existing automotive mirror heating technologies relying on resistive heaters (such as constant-wattage, or CW, heaters and positive temperature coefficient, PTC, heaters) typically make use of a single heating element and one continuous heating circuit. As will be appreciated, conventional heaters used in vehicular rearview assemblies are deficient in several respects. Specifically, either of the abovementioned conventional heater tends to generate an output having a substantially uniform spatial profile that, considering asymmetry of shape and/or volume of an automotive mirror, results in a non-uniform heating profile across the mirror element. The resulting temperature gradients across the mirror produces stress in the glass of the mirror that can ultimately lead to glass fracture and mirror failure as a result of activation of a conventional defrosting heater. In addition, output power and power consumption characteristics of the CW and PTC heater designs are known to be subject to significant variations from part to part and from car to car. Prior attempts to create self-regulating automotive CW heaters have made use of mechanical thermostats, which are rather unreliable and even raise safety concerns due to overheating.

Heaters for automotive mirrors and rearview assemblies using the same


A porphyrin array represented by the following general formula (1-1) or (1-2):

This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2002-25983, filed Feb. 1, 2002, the entire contents of which are incorporated herein by reference.
1. Field of the Invention
The present invention relates to a novel material exhibiting a third-order nonlinear optical property. More specifically, the present invention relates to a porphyrin array having bis(imidazolyl porphyrin metal complex) as structural unit thereof, which array exhibiting excellent third-order nonlinear optical properties.
2. Description of the Related Art
A third-order nonlinear optical material is essentially required for the development of optical fast optical switch and an optical modulation element. However, in order to employ such a third-order nonlinear optical material in actual applications, it is considered that the performance of the material, converted and expressed as the value of third-order susceptibility ("khgr"(3)), must be enhanced by the order of three digits or so, as compared with the organic materials which have been reported. When an organic compound exhibiting significant nonlinearity is designed, it is important that the polarizability of the molecule is increased by increasing the degree of overlap of the orbitals by expanding the xcfx80 electron conjugate system, and by combining an electron donor with an electron acceptor.
Porphyrin is a cyclic tetrapyrrole in which four pyrrole nucleuses are alternatively bridged by four methine groups and has a large conjugate system constituted of 18xcfx80 electrons. Due to this, porphyrin has been studied as a nonlinear optical material. In the conventional study, Anderson reported that the one-dimensional linear porphyrin array, in which free base or metalloporphyrins are connected to each other with butadiyne bonds, exhibits more large nonlinearity, as compared with the porphyrin complex monomer (Chem. Phys., 248, 181 (1999)). However, in this case, the length of the resulting polymer cannot be regulated due to the use of tile covalent bonds. Further, as neither introduction of a hetero metal thereto nor introduction of a donor or acceptor at the terminal substituent thereof is easy, the nonlinear property of the resulting polymer cannot be improved any further. On the other hand, Osuka et al. synthesized a one-dimensional linear porphyrin array in which free base or metalloporphyrins are directly connected to each other at the meso position thereof and a one-dimensional linear porphyrin array in which the porphyrin complexes are bridged to each other with phenylene groups, and measured the degree of nonlinearity of the synthesized porphyrin structures. However, as the donor or acceptor is not introduced thereto, the resulting polymer of Osuga et al. failed to exhibit a significantly large nonlinear property (J. Appl. Phys., 81, 2946 (1997)). In short, it is difficult, by using a covalent bond, to introduce a donor and an acceptor which should provide a high polarizability to a one-dimensional linear porphyrin array. Therefore, significantly large nonlinear property cannot be realized by the conventional method of synthesizing a porphyrin array.
An object of the present invention is to provide a material that exhibits a third-order nonlinear optical response of a significantly large magnitude.
Another object of the present invention is to provide a method of producing such a material.
In order to attain the objects described above, the inventors of the present invention synthesized a novel porphyrin dimer consisting of a metal complex of porphyrin having an imidazolyl group and porphyrin having an imidazolyl group but no metal (hereinafter this dimer is referred to as a mono-metal porphyrin complex dimer). The inventors found that the mono-metal porphyrin complex dimer can be a terminal molecule of the porphyrin array, and serves as an electron donor and acceptor. Specifically, the metal complex of porphyrin having an imidazolyl group serves as a donor and the porphyrin having an imidazolyl group but no metal serves as an acceptor.
The inventors had discovered, prior to the synthesis of the mono-metal porphyrin complex dimer described above, that by coordinating a nitrogen atom of an imidazolyl group of one imidazolyl porphyrin metal complex to the metal atom of another imidazolyl porphyrin metal complex, thereby forming bridges between the porphyrin complexes, a porphyrin array in which a plurality of imidazolyl porphyrin complex dimers are connected to each other by way of coordinate bonds, can be obtained (hereinafter, the diner consisting of two porphyrin complexes are also referred to as bis-porphyrin complex diner). The inventors also discovered that, in a reaction system, the coordinate bonds of the porphyrin array can be cleaved and reconstructed by adding and removing a solvent, such as methanol or pyridine, respectively (JP-A 2001-213883, which corresponds to the allowed U.S. application Ser. No. 09/767,900, and JP-A 2001-253883, which corresponds to a co-pending application Ser. No. 09/802,923).
The inventors found that a mixture of the newly synthesized mono-metal porphyrin complex dimers and a porphyrin array having, as its structural unit, bis-porphyrin complex dimers, may be re-organized in a polar solvent, such as methanol or pyridine, thereby a material exhibiting a significantly large nonlinear optical response can be formed, and accomplished the present invention.
Accordingly, the present invention provides a porphyrin array represented by the following general formula (1-1) or (1-2):
wherein R1 represents an alkyl group or a substituted or unsubstituted aryl group; M1 represents a metal ion;
R2 and R3 independently represent an electron acceptor or an electron donor, preferably selected from the group consisting of free base porphyrin, gold porphyrin, pyromellitic diimide, dialkylviologen, benzoquinone and ferrocene; Im represents IM1 or Im2 shown below:
xe2x80x83wherein R4 represents a hydrogen atom or a methyl group); and n represents an integer in the range of 1 to 100.
The present invention also provides a method of producing the porphyrin array represented by the general formula (1-1) or (1-2) of the present invention comprising:
reacting, in the presence of a polar solvent, either one or both of porphyrin metal complexes represented by the general formulae (2-1) and (2-2):
xe2x80x83wherein R1, R2, R3, M1 and Im have the same meanings as in the general formula (1-1) or (1-2) with bis-porphyrin complex dimer represented by the general formula (3):
xe2x80x83wherein R1, M1 and Im have the same meanings as in the general formula (1-1).
As an example of the porphyrin metal complex represented by the general formula (2-1) or (2-2), a nono-metal porphyrin complex dimer represented by the general formula (2xe2x80x2) may be used:
wherein R1, M1 and Im have the same meanings as in the general formulae (1-1).
The porphyrin array represented by the general formula (1-2) may be synthesized by reacting, in the presence of a polar solvent, either one of both of the porphyrin metal complexes represented by the general formulae (2-1) and (2-2). The present invention also provides this method of preparing the porphyrin array represented by the general formula (1-2).
The present invention also provide the porphyrin metal complex represented by the general formula (2-1) or (2-2).
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.

Porphyrin array having imidazolyl porphyrin metal complex as structural unit thereof and method of producing the same

Abstract: wherein R1 represents an alkyl group or a substituted or unsubstituted aryl group; M1 represents a metal ion; R2 and R3 independently represent an electron acceptor or an electron donor; Im represents Im1 or Im2 set forth below:

Abstract: wherein R4 represents a hydrogen atom or a methyl group; and n represents an integer in the range of 1 to 100.

Nara Institute of Science and Technology


A method and apparatus for parameterizing an input signal as a sum of N unrelated sine waves of various amplitudes, frequencies and phases using a 2N-order difference equation to describe the sine wave sum and converting the problem to a solution of the roots of an N-order polynomial.

In digital transmission systems, for a variety of reasons, the spectrum of the received wave form may differ from the spectrum of the transmitted signal. Such differences may be caused by the violation of bandwidth constraints, atmospheric transmission complications, adjacent channel interference and the like. In such cases, it is necessary, at the receiver, to perform a spectrum analysis to find the constituent frequencies which produce the composite spectrum.
The dominant mechanism currently in use to parameterize an ordinary real-world signal as an amplitude versus frequency distribution is a fourier transform in which a signal is assumed to be describeable by the formula ##EQU1##
Hardware (and computer program) methods for determining the set of amplitude and phase coefficients A.sub.k, B.sub.k, incorporating a technique known as the Fast Fourier Transform (FFT) are widely used. Another widely used mechanism to parameterize the received signal as an amplitude versus frequency distribution is to construct a parallel array of filters for an analog signal, each filter responding only to a very narrow band of frequencies, and digitize the amplitudes of the outputs of the filters to yield average values for each frequency band according to the formula ##EQU2## In such cases, however, the actual dominant frequencies must be inferred by peak detection and interpolation.
In the Fast Fourier Transform method, a large number of samples must be processed to yield the distribution. As a consequence, it can yield results only at a much lower rate than the sampling rate. In the filter array method, a very large number of filters are required and the narrowness of the individual filter passbands causes them to be slow in responding to changes in amplitude of the frequency components that they accept.
The present invention parameterizes the received signal to yield estimates of the three parameters frequency, amplitude and phase for each frequency component assumed to be present. These estimates are yielded at the same rate as the sampling rate with a constant time delay determined only by the assumed number of frequency components (N). The amount of hardware required depends only upon N and does not depend upon the bandwidth of the input signal as the filter array method does. The precision of the required output is determined only by the precision required of the components, rather than (as is the case for the Fast Fourier Transform methods) determining the number of components required and the time delay before results are available.
The apparatus includes a storage device such as a shift register for receiving and sampling the input digital signal at a time, t, with a time interval, h, between samples. Thus, the storage device stores samples from the most recent to the oldest sample. A weighted adder receives the parallel outputs from the shift register and calculates a matrix of row and column component signals, C.sub.nK, by adding selected ones of the stored samples using a weighting function. A matrix inverter is coupled to the weighted adder for receiving the C.sub.nK row and column signals and generating a set of symmetrical polynomials with each polynomial having coefficients, Z, representing the cosines of the N frequency components of the input signal. A polynomial solver is coupled to the matrix inverter for receiving the set of symmetrical polynomials and calculating the roots of each polynomial to obtain the cosine frequency components, Z.sub.m, where Z.sub.m =COS.omega..sub.m h where m= the input frequency component between 1 and N. A function inverter is coupled to the polynomial solver for calculating the frequency, .omega..sub.m, of each of the N unknown input sine waves for each of the digital samples according to the equation .omega..sub.m =1/hacosZ.sub.m.
Once the frequency is obtained, sine/cosine functions can be generated and, using the stored digital input samples, the respective signal amplitude coefficients and signal phase coefficients can be calculated. From these coefficients, the signal amplitude and signal phase can be determined.


A shade product is described that is made at least in part with a sheer material. Sheer materials are highly porous materials that allow significant amounts of light to pass through the material. When placed in an architectural opening, such as a window, sheer materials can provide a soft and elegant appearance while still providing privacy. When using sheer materials to construct shade products, one layer of the sheer material typically needs to be bonded to an adjacent material, such as another layer of the sheer material. In accordance with the present disclosure, an adhesive receptive coating is applied to the sheer material at the bond sites in order to prevent against adhesive migration. In one embodiment, the adhesive receptive coating is substantially transparent and therefore does not interfere with the overall look and aesthetic appeal of the product.

Various different coverings exist for architectural openings such as doors, windows and the like. The coverings, for instance, can provide privacy, can provide thermal insulation, and/or can be aesthetically pleasing. One type of covering is referred to as a shade. Although shades can take many different forms, shades typically include a fabric that is designed to be suspended adjacent to the top of an architectural opening by hardware that may be capable of raising and lowering the fabric.
The fabric can be configured to be raised and lowered in numerous ways. For instance, roller shades typically include a shade material that winds and unwinds on a rotating mandrel for retracting and extending the shade. Other shades include Roman shades that hang flat when lowered and pleated shades that include horizontal fold lines that allow the shade to collapse into a uniform stack when retracted. Another type of shade is typically referred to as a cellular shade. Cellular shades are made from a series of connected foldable cells.
One of the advantages to installing a shade within an architectural opening is the ability to select a shade material or fabric that lets a desired amount of light to pass through the shade. For instance, in one embodiment, a shade material may be selected that completely blocks light from entering through the architectural opening. In an alternative embodiment, a shade material may be selected that allows a small amount of light to pass through the material for allowing some light to enter through the architectural opening while also providing visual appeal. In still another embodiment, a shade material may be selected that allows a substantial amount of light to pass through the architectural opening. Such materials are typically referred to as "sheer" materials. Sheer materials, for instance, can be made with a relatively open weave and can be constructed from woven or knit monofilament yarns.
Although sheer materials are highly desirable in some applications, the use of sheer materials has created various problems for shade manufacturers. For example, many types of shades are made from multiple pieces of material. The multiple pieces of material are typically connected together to form the shade through the use of an adhesive, such as a liquid adhesive. Beads of adhesive, for instance, are typically used not only to construct individual cells in a cellular shape, but also typically used to interconnect the cells together. Unfortunately, however, such adhesives have a tendency to penetrate through highly porous materials, such as sheer materials. Not only can the adhesive be unsightly with respect to such materials, but adhesive migration can also cause unintended parts of the shade material to bond together creating an unusable product.
In view of the above problems, those skilled in the art have proposed various different methods and techniques for bonding together sheer materials when constructing shade products. For instance, U.S. Pat. No. 4,673,600 discloses cellular shades made from sheer materials wherein the sheer materials are bonded by allowing the adhesive to cure while the cells are in an expanded state.
U.S. Pat. No. 5,043,039 also discloses a method for forming cellular shades using a sheer material. In the '039 patent, strips of a non-bonding material are placed at selected locations within a cellular shade during application of an adhesive in order to prevent the adhesive from bonding unintended parts of the shade together. When the adhesive has set, the non-bonding strips are then removed from the product.
The present disclosure is directed to further improvements in shade products containing sheer materials. More particularly, the present disclosure is directed to further improvements in controlling adhesive migration through porous materials, such as sheer materials during the production of shade products.

Collapsible shade containing a sheer fabric