WO2005077825A1 - アモルファスカーボン粒子およびこれを用いた複合材料 - Google Patents
アモルファスカーボン粒子およびこれを用いた複合材料 Download PDFInfo
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- WO2005077825A1 WO2005077825A1 PCT/JP2004/015073 JP2004015073W WO2005077825A1 WO 2005077825 A1 WO2005077825 A1 WO 2005077825A1 JP 2004015073 W JP2004015073 W JP 2004015073W WO 2005077825 A1 WO2005077825 A1 WO 2005077825A1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/022—Carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to amorphous carbon particles and a composite material using the same. More specifically, the present invention relates to amorphous carbon particles excellent in properties such as material strength, corrosion resistance, conductivity, heat resistance, dimensional stability, etc., and also excellent in economic efficiency, and use thereof.
- V it relates to a composite material.
- Amorphous carbon is a heterogeneous carbon material having a homogeneous vitreous structure, and has been applied to various fields in recent years because of its excellent mechanical strength, alkali resistance, acid resistance, conductivity and other properties. Is expected.
- a method for producing such amorphous carbon for example, as disclosed in Patent Document 1-13, a molded article of a thermosetting resin such as phenol resin or full furyl alcohol resin is calcined and carbonized.
- Amorphous carbon obtained by this method of calcining and carbonizing a thermosetting resin is not only expensive but also has a sufficient residual carbon ratio at the time of baking. In addition, the material strength etc. was inferior to the expected value.
- petroleum coaster is an inexpensive carbon-based fuel that generates a higher calorific value than coal, and is currently widely used as a fuel in industrial boilers and the like.
- combustion ash discharged from a combustion furnace using such petroleum coats generally contains unburned carbon in a proportion of 70% by mass or more, and the heat of drying is equal to that of coal, so It is used as a fuel in cement calcining kilns, or as a reducing carbon material for melting furnaces in refineries.
- the unburned carbon content in petroleum coatas combustion ash is extremely low in activity and reactivity, and the combustion ash contains a large amount of impurities other than carbon. In the near future, there is a high possibility that it will be treated as landfills etc. as fuel and carbon materials.
- Patent Document 1 Japanese Patent Publication No. 39-20061
- Patent Document 2 Japanese Patent Publication No. 63-59963
- Patent Document 3 Japanese Patent Application Laid-Open No. 3-164416
- Patent Document 4 Japanese Patent Application Laid-Open No. 7-213949
- Patent Document 5 Japanese Patent Application Laid-Open No. 10-281438
- the present invention for solving the above problems is an amorphous carbon particle extracted from combustion ash of petroleum coats, the particle has a non-circular cross section, and has a holding temperature of 500 ° C. for 60 minutes in the presence of air.
- Amorphous carbon particles characterized by having a mass loss ratio of less than 30% and an average particle diameter of 50-: L m.
- the present invention is also directed to the above amorphous, wherein the specific surface area measured by the BET method is 20-lm 2 Zg, and the pore volume measured by the nitrogen adsorption method is 0.200-0. OOl ml / g. It shows carbon particles.
- the present invention further relates to the above amorphous carbon particles having an interplanar spacing of 3.43 A or more measured by X-ray diffraction.
- the present invention for solving the above problems is also an amorphous carbon particle extracted from combustion ash of petroleum coatas in a matrix composed of organic or inorganic material, the particle having a non-circular cross section, Amorphous carbon particles characterized by having a weight loss ratio of less than 30% at a holding temperature of 500 ° C. for 60 minutes and an average particle diameter of 50 to 1 ⁇ m in the presence thereof are characterized. It is a composite material.
- the present invention also shows the above-mentioned composite material, which contains 10 to 70% by mass of the amorphous carbon particle force composite material.
- the present invention for solving the above problems is also an amorphous carbon particle extracted from the combustion ash of petroleum coatas described above, wherein the particle has a non-circular cross section and is maintained in the presence of air at a holding temperature of 500 ° C.
- Carbon-carbon characterized in that amorphous carbon particles characterized by having a weight loss ratio of 60 minutes less than 30% and having an average particle diameter of 50 to 1 ⁇ m are combined with other carbon particles. It is a composite material.
- the present invention is also a carbon-carbon composite material comprising amorphous carbon particles in an amount of 10 to 70% by mass of the composite material.
- the present invention for solving the above-mentioned problems is a cement composition characterized in that at least an inorganic binder and the above-mentioned amorphous carbon particles are blended.
- the present invention is also a cement yarn composition which is blended with 10 to 70% by mass of an amorphous carbon particle total solid component. Effect of the invention
- the amorphous carbon particles are incorporated into an organic substance such as resin! /, A rubber, an inorganic substance such as a metal, a glass or a ceramic, a cement composition, or another carbon material to obtain electric resistance. Since it is possible to provide composite materials with improved properties such as chargeability, chargeability, heat resistance, mechanical strength, etc., it is expected to be useful in the fields of various molded products and structures, semiconductor fields, heat transfer fields, etc. Be done.
- FIG. 1 is an electron micrograph showing a particle shape of amorphous carbon particles according to the present invention at a magnification of 1000 times.
- FIG. 2 is an electron micrograph showing a particle shape of amorphous carbon particles according to the present invention at a magnification of 20000.
- FIG. 3 is an electron micrograph (magnification: 2000) showing the state when the amorphous carbon particles according to the present invention are blended in a resin.
- the amorphous carbon particles according to the present invention are extracted from the combustion ash of petroleum coats.
- the present inventors acid-wash ash (metal oxide) from combustion ash, separate solid from the carbon content, and dry, grind, and adjust the carbon content.
- the carbon obtained by granulation is amorphous, that is, it is amorphous and has excellent rigidity, strength and heat resistance, and particles having extremely small specific surface area and pore volume are not flaky or spherical but acute angles. It is a non-circular cross section with an edge and shows a complex shape having sharp projections and a smooth curved surface on the particle surface, either alone or as a matrix such as resin or rubber. It has been found that the compound of the present invention exhibits excellent performance by being incorporated thereinto, resulting in the present invention.
- a raw material of the amorphous carbon powder of the present invention petroleum cotas, as is well known, is a heavy residual oil (asphalt fraction) which is mainly produced by a vacuum distillation apparatus in the process of crude oil purification at 500 ° C-600. It is a carbon product which is by-produced as a solid after separation of gasoline, kerosene, gas oil fraction and the like which causes coking reaction by heating to ° C, and which is pyrolyzed and volatilized.
- the amorphous carbon of the present invention is extracted from a combustion furnace using such petroleum cotas as a fuel, for example, a combustion ash that also generates power such as a pulverized coal boiler and a gasification furnace.
- a combustion furnace using such petroleum cotas as a fuel, for example, a combustion ash that also generates power such as a pulverized coal boiler and a gasification furnace.
- a condition such as 124 hours at 800-1300 ° C. in an oxidizing atmosphere can be exemplified.
- composition of the combustion ash as the raw material is not particularly limited.
- composition can be exemplified as a composition such as 02-0. 80%, Ni 3500-6500 mg / Kg, Mo50-1OOmg ZKg. In addition, if one typical composition is shown for reference, HO 0.5 mass%, C 78.9 mass%, H 0.8
- such petroleum oil particles may be used as a method of producing the amorphous carbon particles according to the present invention.
- the combustion ash collected by the dust collector is recovered in a boiler that uses TAS as fuel, and acid water and, if necessary, a reducing agent are added, and the metal oxides and insolubles that are dissolved in the acid by heating and stirring.
- the carbon content is separated from solid and liquid, washed and then dried and crushed.
- humidification treatment is performed on combustion ash to improve the handling of combustion ash and facilitate the elution of metal components in metal extraction. It can be
- sulfuric acid, hydrochloric acid, nitric acid or a mixture thereof can be used as the acid of the acidic water to be used, but preferably the solubility of the metal is preferred.
- sulfuric acid or hydrochloric acid, most preferably sulfuric acid are preferred.
- acid water is not added! And this is not preferable because the extraction rate of the metal component in the metal extraction process decreases.
- the pH of the acidic water is not particularly limited, but is preferably, for example, pHO.110, more preferably pHO.5-1.0. If it is less than pHO.1, a large amount of acidic water may be used for the treatment, while if the pH is more than 3.0, the extraction efficiency for vanadium may be reduced. is there.
- the addition amount of the acidic water is not particularly limited, and is, for example, an amount that is 2 to 10 times the amount of combustion ash (dry mass) to be treated. If the amount of acidic water added is less than twice, there is a possibility that sufficient dissolution processing of the soluble matter can not be performed. On the other hand, if the amount added is more than 10 times, it is not only uneconomical, but also the labor required for waste liquid treatment after solid-liquid separation as described later may be large.
- the reducing agent to be added is not particularly limited, and, for example, sulfurous acid, hydrazine, hydroxylamine and the like can be used, and preferably, It is a sulfurous acid or hydrazine which is excellent in the reducing action, more preferably a sulfurous acid.
- Such a reducing agent is added to the combustion ash at approximately the same time as the above-mentioned acidic water and before heating.
- the amount of the reducing agent to be added is not particularly limited, but the reducing agent is, for example, 0.10 parts by mass, preferably 0. 1 part by mass with respect to 100 parts by mass of combustion ash (dry mass). It is desirable to add 1 to 0.6 parts by mass.
- the amount of reducing agent added is less than 0.02 parts by mass If it is more than 1.0 parts by mass, it may be necessary to treat the remaining reducing agent, which may complicate the process operation. This is because there is
- Acidic water and, if necessary, a reducing agent are added to the combustion ash, and heated to a temperature of, for example, 40 ° C. or more, more preferably 50-80 ° C. Stir by the number to dissolve the metal soluble in acid in the combustion ash sufficiently.
- the heating temperature is set to 40 ° C. or higher is that the extraction rate is lowered at a temperature lower than that.
- the stirring method is not particularly limited, and it is possible to use a general method such as stirring using an impeller with four inclined blades, for example.
- the stirring conditions are appropriately changed depending on the concentration of acidic water in the extract, the solution temperature and the like.
- a sulfuric acid aqueous solution of p HO. 6 is added in a mass ratio of 2 times the combustion ash, and in the case of a solution temperature of 60 ° C., stirring for about 90 minutes is appropriate.
- metal components such as V, Al, Fe, Mg, Mo, and Ni, which are contained in combustion ash, are dissolved in water.
- carbon remains insoluble as a solid.
- the solid-liquid separation step is not particularly limited.
- a press filter for example, a centrifuge, a decanter, a belt filter, a tray filter, a precoat filter, a ceramic filter, a cricket filter, a press roll filter, etc. It can be implemented by processing using.
- the wet carbon content obtained by solid-liquid separation is thoroughly washed with warm water of, for example, about 20-80 ° C., preferably about 60 ° C., as necessary.
- warm water for example, about 20-80 ° C., preferably about 60 ° C., as necessary.
- various apparatuses can be used which are not particularly limited as long as the adhering acidic water can be sufficiently removed.
- the drying step is not particularly limited, and may be treatment such as air drying at a temperature of 100 to 200 ° C., oven drying, or natural drying.
- Amorphous power according to the present invention It is also conceivable to use a method of drying by energization by utilizing the fact that single carbon particles have conductivity. Even in the case of misalignment, the amorphous carbon particles according to the present invention are excellent in heat conductivity such that the specific surface area and pore volume are extremely small, and therefore, they can be dried very efficiently. is there.
- the pulverizing step is not particularly limited, and is carried out by pulverizing treatment using a physical pulverizer such as a turbo mill, a ball mill, a jet mill, a roller mill and the like.
- a physical pulverizer such as a turbo mill, a ball mill, a jet mill, a roller mill and the like.
- a jet mill as the pulverizing apparatus because the carbon content to be pulverized is high in hardness and already in the form of fine powder. After the grinding process, classification can be carried out as required.
- the particles have a non-circular shape having a flake-like shape like graphite or a spherical non-spherical edge such as carbon black. It is a cross section and has a complicated shape having sharp protrusions and a smooth curved surface on the particle surface. Also, its average particle size is 1 50/50 ⁇ ⁇ , more preferably 1 1 1 O / z m.
- the shape of the non-circular cross section having such a sharp edge is, for example, the anchoring effect with the matrix material at the time of compounding to the matrix material such as resin, rubber, cement, metal, etc. A spike effect can be expected.
- the weight loss rate of 60 minutes at a holding temperature of 500 ° C is less than 30%, more preferably less than 20%, and it is a highly reactive, highly stable carbon. .
- the amorphous carbon particles according to the present invention have an amorphous structure, for example, because the interplanar spacing measured by X-ray diffraction is 3.43 A or more.
- the amorphous carbon particles according to the present invention have a specific surface area of 120 m 2 / g as measured by BET method and a pore volume of about 0.200-0. OOl ml / g as measured by nitrogen adsorption method. And have relatively compact surface properties.
- the bulk specific gravity measured by the manual filling method is measured according to 0.5-0.7 g / mU JISK21515.
- the true specific gravity is 1. 9-2.
- the amorphous carbon particles according to the present invention can be used as it is, for example, as various catalyst carriers, fluid bed media, and the like.
- the amorphous carbon particles according to the present invention have an affinity for both the oil-based substrate and the aqueous substrate, so that the conductivity is improved, the rigidity and mechanical strength are improved, and the dimensional stability is achieved.
- Organic substances such as various resins and rubbers for the purpose of improving Can be blended into a matrix material made of an inorganic substance such as cement, metal and the like.
- resins or rubber molding materials resins or rubber molding materials, colorants such as light-shielding fibers, modifiers or fillers for resins or rubbers, conductivity imparting agents for resins or rubbers, for example, antistatic materials, It can be preferably used in various applications such as resistance resistance materials in copying machines, electrical resistance adjustment materials in planar heating elements using PTC characteristics, artificial marble, and the like.
- coloring compositions such as lubricants, traction drive fluids, electroviscous fluids, non-linear optical materials, various inks, paints, etc. may be considered. .
- a coloring agent e.g., a filler, an aggregate and the like, and a matrix material consisting of a cement composition, an inorganic material such as a metal, glass, etc., for various uses.
- carbon / carbon composites having new properties can be prepared.
- the composite material according to the present invention is formed by blending the amorphous carbon particles according to the present invention as described above in a matrix comprising an organic substance such as resin or rubber or a cement composition, an inorganic substance such as metal or glass. It is a thing.
- the compounding amount also depends on the purpose of addition and organic substances such as resin, which is a matrix, or an organic material such as rubber, cement composition, and inorganic substances such as metal and glass. It is possible to blend about 70% by mass, and even if the blending amount is as high as 70% by mass, it can be blended in a uniformly dispersed state in the matrix. This is because the amorphous carbon particles according to the present invention have an affinity for both the oily substrate and the aqueous substrate, and because they have the cross-sectional non-circular particle shape as described above, It is believed that the anchor effect is high, and high dispersion can be maintained.
- the composite material according to the present invention does not have a desired compounding amount as a product, and is used to improve uniform dispersibility in producing a product with a relatively low compounding amount, so-called masterno ⁇
- masterno ⁇ The form in the form of vines is also included.
- the amorphous carbon particles are mixed with a resin or rubber composition in a fluid state, as is known. It can be prepared by mixing or kneading. In the case of a cement composition, it can be blended in the powder state or in the paste state to which water is added, and in the case of metal, glass, etc., it is in the powder state. can do
- the resin or rubber to be a matrix to which the amorphous carbon particles according to the present invention are mixed is not particularly limited.
- a thermoplastic resin polyethylene, chlorinated polyethylene, ethylene may be used.
- Olefin-based resins such as vinyl acetate copolymer, ethylene acrylic acid ethyl copolymer, polypropylene, ethylene propylene copolymer, polybutylene, poly 4-methylpentene 1, etc., and copolymers thereof;
- Polyvinyl chloride polyvinyl chloride, polyvinyl chloride, vinyl acetate copolymer, poly vinyl acetate copolymer, poly vinyl (meth) acrylate copolymer, polyvinyl chloride copolymer -Chloride-based systems such as tolyl copolymer, ethylene-monochloride-vinyl copolymer, propylene-monochloride-vinyl copolymer, polychloride-vinyldalarite-ethylene, ethylene-butyl-copolymer, etc.
- Acrylic acid such as methyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, methacryl
- Acrylic acid such as methyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate
- acrylic acid based resins such as homopolymers and copolymers of methacrylic acid based monomers, and copolymers thereof;
- Polyamide-based resins such as nylon 6, nylon 66, nylon 610, nylon 11, nylon
- Cellulose-based oils such as cenorelose acetate, cenollose acetate butyrate, cenolerose estenole, cenoreose ethylate;
- Thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate;
- thermosetting resin is not particularly limited.
- phenol resin urea resin, melamine resin, xylene resin, furan resin, diaryl phthalate
- resin unsaturated polyester resin, alkyd resin, epoxy resin, urethane resin, alkylbenzene resin, benzoguanamine resin, and various modified resins thereof.
- the rubber is not particularly limited.
- natural rubber such as natural rubber, chlorinated rubber, hydrochloric acid rubber, cyclized rubber, etc., and derivatives thereof; styrene butadiene rubber (SBR) Butadiene based synthetic rubbers such as nitrile rubber (butadiene / acrylonitrile copolymer, NBR), croup rubber rubber, etc .; Olefin based synthetic rubbers such as polyisoprene and butyl rubber; epichlorohydrin rubber; brominated butyl rubber silicone A, silicone B Acrylic rubber; Chlorosulfone polyethylene; and, also as a thermoplastic resin as described above, for example, vinyl chloride resin elastomer 1, ethylene glycol, etc.
- SBR styrene butadiene rubber
- NBR nitrile rubber
- croup rubber rubber etc.
- Olefin based synthetic rubbers such as polyisoprene and butyl rubber
- thermoplastic elastomers examples include: propylene elastomers 1, ethylene acetates bule elastomers 1, chlorinated polyethylene elastomers 1, styrene butadiene elastomers 1, thermoplastic polyurethane elastomers 1 and other thermoplastic elastomers; silicone rubber, fluorinated rubber, urethane rubber, etc. .
- the composite material of the present invention may be any of various additives known in the prior art, in addition to the amorphous carbon powder as described above, in the matrix also having the above-mentioned resin or rubber power. Ingredients can be added as needed.
- heat stabilizers examples include heat stabilizers, antioxidants, ultraviolet absorbers, plasticizers, colorants, flame retardants, foaming agents, and fillers other than the above-mentioned amorphous carbon.
- Agents, mold release agents, surface treatment agents, lubricants, antiblocking agents, antistatic agents, etc. are not limited to these.
- heat stabilizer for example, lead stearate, dibutyltin laurate, tribenzyltin laurate, stearic acid domium, sulfur stearate, barium stearate, barium stearate, strontium stearate, magnesium stearate, magnesium stearate, to name just a few.
- fatty acid metal salts or esters such as calcium phosphate, cadmium laurate, zinc laurate, barium laurate, strontium laurate, magnesium laurate, calcium laurate and the like.
- examples of the antioxidant include, for example, alkylphenols, amines, quinones and the like, to mention just one example.
- Ultraviolet absorbers include, for example, salicylic acid esters and benzene acid esters, to mention just one example.
- the plasticizer may vary depending on the type of resin added.
- phthalic acid ester for example, phthalic acid ester, sebacic acid ester, adipic acid ester, phosphoric acid ester, aliphatic dibasic acid ester, polyester compound Epoxy compounds, chlorine-containing compounds, ricinoleic acid esters, diethylene glycol, butadiene acrylic nitrile, sulfonamides and the like.
- Coloring agents include various pigments (including extender pigments) and dyes.
- the flame retardant for example, parachloride chloride, tricresyl phosphate, chlorinated oil, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, tetrabromobisphenol A, antimony oxide, aluminum hydroxide, for example.
- blowing agents by way of example, propane for physical foaming, low boiling point solvents such as butane, and azo-to-triyl compound for psychic foaming, benzene These include sulfophorhydrazine compounds and diazoamide compounds.
- the filler other than the above amorphous carbon for example, glass fiber, glass bead, calcium carbonate, calcium carbonate, titanium white, lignin, asbestos, silica, acid aluminum, There are magnesium oxide, boron nitride, silica, natural and synthetic fibers, carbon black and white carbon.
- a mold release agent or surface treatment agent for example, natural and synthetic waxes such as carbauba wax and paraffin wax, polyethylene wax, silicone oil and the like can be mentioned, for example.
- lubricant for example, metal stearates, isobutyl stearate and the like can be mentioned to a single example.
- antiblocking agent for example, talc powder, rosin powder, coroidal silica, hydrophobic silica, hydrophobic titanium, inorganic particles such as hydrophobic zirconia, and others, polystyrene beads, There are organic fine particles such as meta) acrylic resin beads.
- examples of the antistatic agent include, for example, various surfactants such as aliphatic sulfonates and higher alcohol sulfates, and silane coating agents.
- the composite material of the present invention for the purpose of improving the dispersibility of the amorphous carbon powder in the above-mentioned matrix that also has a resin or rubber power, it has an affinity for these matrices.
- a substance having an affinity for amorphous carbon powder such as a block having a block or graft chain exhibiting an affinity for the matrix and a block or graft chain having an affinity for amorphous carbon powder, It is also possible to add graft polymers, various surface-active substances, amphiphilic mixtures and the like.
- the block or graft polymer also includes, for example, so-called oligomers having a relatively low molecular weight and an average molecular weight of 3000 or less.
- crosslinking agent examples include aromatic divinyl compounds such as dibutyl benzene, divinyl naphthalene, derivatives thereof, ethylene glycol dimetatalylate, diethylene glycol dimetatalylate, triethylene glycol dimetatalylate, trimethylolpropane triarylate.
- Aryl methacrylate, t-butylaminoethyl methacrylate All, diethylenically unsaturated carboxylic acid esters such as tetraethylene glycol dimetatalylate, 1,3 butanediol dimetatalylate, etc., N, N-divinyl alcohol, divinyl ether, dibutyl sulfide, divinyl sulfonic acid And compounds having 3 or more vinyl groups. Further, polybutadiene, polyisoprene, unsaturated polyester, chlorosulfonated polyolefin and the like are also effective. In addition, since the crosslinking agent or curing agent in the case of the matrix force thermosetting resin and rubber is conventionally used for these, it is possible to use a well-known one or a different one, so the description will be omitted. .
- the method for preparing the composite material according to the present invention which comprises amorphous carbon particles mixed in a matrix made of rubber, is not particularly limited depending on the kind of the resin or rubber, for example, It can be carried out by melt-kneading, compounding and dispersing in an uncrosslinked prepolymer composition, kneading before vulcanization, etc. Further, these treatments may be carried out by using a ball mill, mixer, kneader, etc. It can be carried out using a stirring tank used for stirring, and also, in primary molding by extrusion molding, injection molding, etc., of a product made of such a composite material, molding can be substantially performed in these molding devices. It is also possible to do it simultaneously.
- the composite material according to the present invention that can be prepared in this manner has a high content such as 70% by weight of alpha carbon composite particles, for example. Also, since the dispersibility in various resins or rubber matrices is good, the properties of the composite material such as electric resistance, charging characteristics, heat resistance, mechanical strength and the like are also excellent. On the other hand, since the amorphous carbon particles of the present invention have various excellent physical properties as described above, the electrical resistance and charging characteristics of the resulting composite material can be obtained without extremely increasing the amount thereof. The improvement effect in characteristics such as heat resistance and mechanical strength can be expected sufficiently.
- various inorganic compounds to be used as a matrix such as various metal! / Shrinkage metal alloys, various glasses, hydraulic compositions represented by cement, hydraulic compositions, or ceramics, etc. Can be used.
- the carbon material is not particularly limited, but natural or artificial graphite (graphite), carbon black, amorphous carbon other than the amorphous carbon particles according to the present invention carbon, fullerene, nanotube, nano cone, nanofiber
- graphite graphite
- amorphous carbon other than the amorphous carbon particles according to the present invention carbon
- fullerene carbon
- nanotube nano cone
- nanofiber Various forms such as powder, fiber, milled fiber, mat, felt, paper and film-like carbon material mesocarbon microbeads are also included. It includes those of various shapes such as spherical carbon material.
- aggregate particles of milled carbon fibers in addition to black lead (that is, aggregate particles of milled graphite fibers), those having a low degree of graphite, or carbonization level Can also be used.
- a carbon fiber precursor, a carbon source and the like can also be used.
- the carbon fiber precursor may make any fiber force that can be made to carbon or graphite by heating.
- the fibers include PAN (polyacrylonitrile) fibers, preacidified acrylonitrile resin fibers, pitch fibers, CVD carbon fibers, pyrolyzed natural fibers such as pyrolyzed cotton fibers, and mixtures thereof.
- a carbon source to be generally used as a matrix material any carbon source which can be converted to black lead by heating can be used.
- CVI Hydrometric vapor phase permeation
- pyrolytic carbon source such as phenol resin , Pitch, and hydrocarbons such as methane, ethane, propane and the like and mixtures thereof.
- the method for producing the carbon-carbon composite according to the present invention is not particularly limited.
- a method for mixing or contacting the amorphous carbon particles according to the present invention with other carbon materials and compression molding It is possible to use various known methods such as a method of forming, heating and carbonizing with a self-sintering carbon source or carbon precursor and a method of using a binder.
- the blending amount of the amorphous carbon particles according to the present invention is not particularly limited, but for example, blending of 10 to 70% by mass of the composite is Thermal stability of the resulting carbon-carbon composite, thermal shock resistance and low thermal expansion due to high thermal conductivity, toughness, strength and rigidity in high temperature applications Desirable from the point of improving the
- the cement composition according to the present invention is characterized in that an inorganic binder and at least the above amorphous particles according to the present invention are blended.
- the binder includes various cements which are not particularly limited, and, if necessary, other fine powders, expandable admixtures and the like.
- cement various kinds of mixed cement such as ordinary 'early strong' moderate heat 'low heat portland cement such as Portland cement, blast furnace cement' fly ash cement, etc., waste of incineration ash in urban area ⁇ waste such as sewage sludge incineration Cement (Ecocement), etc. used as Other fine powders include silica powder, silica dust, silica stone powder, limestone powder and the like.
- Examples of expandable admixtures include calcium sulfoaluminate-based expansive agents and lime-based expansive agents.
- fine aggregate such as river sand, land sand, sea sand, crushed sand or a mixture thereof, river gravel, mountain gravel, sea gravel, crushed stone or a mixture thereof, as necessary.
- Coarse aggregates such as lignin, naphthalenesulfonic acid, melamine and polycarboxylic acid water reducing agents, and water reducing agents such as AE water reducing agents can be added.
- the compounding amount of the amorphous carbon particles is not particularly limited, but for example, it is possible to mix 10 to 70% by mass of the total solid component, the strength after cement hardening Also desirable to improve the characteristics of the etc.
- the preparation method (kneading method) of the cement composition is not particularly limited, and the cement, the fine powder and the expansive admixture are mixed beforehand, and the mixture, Carbon, fine aggregate, coarse aggregate, water reducing agent, and water may be introduced into a mixer and kneaded to prepare, cement, ultra fine powder, expansive admixture, amorphous carbon, fine aggregate, coarse aggregate
- the water-reducing agent and water may be introduced into the mixer at almost the same time, and they may be mixed and prepared.
- the mixer may be a conventional mixer.
- the curing method is not particularly limited. Underwater curing, steam curing, etc. may be performed.
- Example 1 Preparation of amorphous carbon particles
- combustion ash collected by a dust collector was recovered.
- the particle diameter of the carbon particles thus obtained was determined by laser diffraction method, and the average particle diameter was 4.2 m, the standard deviation was 0.183, and 0.75 ⁇ m. Particles of less than and greater than 20.0 m were not detected.
- the specific surface area was 10.8 m 2 Zg measured by the BET method, and the pore volume was 0.103 ml Zg measured by the nitrogen adsorption method.
- the bulk density measured by the filling method was 5.05 g / mU, and the true specific gravity measured according to JIS K 21515.3 was 2.05.
- FIGS. 1 and 2 The electron micrographs of the obtained carbon particles are shown in FIGS. 1 and 2.
- Example 1 As a comparison, the weight loss ratio of coal coats at 500 ° C. for 60 minutes was examined under the same conditions as in Example 1 to be 60.0%, and it was found that the characteristics were apparently different.
- Example 2-4 Preparation of Polypropylene Composite Material
- Example 1 the mixture of the amorphous carbon particles obtained in a proportion of 30% by mass and 70% by mass of nylon 6 polyamide (Novamitsu 101 3C5 manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
- the composite material was prepared by melt-kneading with a TEX-30 twin-screw kneader (manufactured by Tokushu Co., Ltd.) under the conditions of a rotation speed of 300 rpm and a resin temperature of 270-280 ° C. Furthermore, the resulting composite material is injected into a mold (JIS mold) using a molding machine (120T injection molding machine manufactured by Japan Steel Works, Ltd.) to obtain a dumbbell-shaped test piece (JIS No.
- the 10 8 ⁇ cm was measured by the 50 ⁇ electrode method.
- FIG. 3 is a photomicrograph at 2000 ⁇ magnification showing the cross-sectional state of the composite material thus obtained. As shown in this photograph, it can be seen that amorphous carbon particles of non-circular cross section are uniformly dispersed in the resin matrix.
- a composite material is prepared in the same manner as in Example 5 except that the compounding amount of the amorphous carbon particles obtained in Example 1 is changed to 45% by mass, and a dumbbell shape is obtained.
- Test pieces JIS No. 1 dumbbell
- flat test pieces length 80 mm x width 120 mm x thickness 2 mm
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2555799 CA2555799A1 (en) | 2004-02-12 | 2004-10-13 | Amorphous carbon particle and composite material containing the same |
US10/588,958 US20070172408A1 (en) | 2004-02-12 | 2004-10-13 | Amorphous carbon particles and composite material used thereof |
DE200411002724 DE112004002724T5 (de) | 2004-02-12 | 2004-10-13 | Amorphe Kohlenstoffteilchen und sie enthaltendes Verbundmaterial |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2004-035668 | 2004-02-12 | ||
JP2004035668A JP2005225712A (ja) | 2004-02-12 | 2004-02-12 | アモルファスカーボン粒子およびこれを用いた複合材料 |
Publications (1)
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WO2005077825A1 true WO2005077825A1 (ja) | 2005-08-25 |
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PCT/JP2004/015073 WO2005077825A1 (ja) | 2004-02-12 | 2004-10-13 | アモルファスカーボン粒子およびこれを用いた複合材料 |
Country Status (7)
Country | Link |
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US (1) | US20070172408A1 (ja) |
JP (1) | JP2005225712A (ja) |
CN (1) | CN1938222A (ja) |
CA (1) | CA2555799A1 (ja) |
DE (1) | DE112004002724T5 (ja) |
TW (1) | TW200526517A (ja) |
WO (1) | WO2005077825A1 (ja) |
Families Citing this family (25)
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---|---|---|---|---|
RU2327733C1 (ru) * | 2007-02-06 | 2008-06-27 | Сергей Дмитриевич Кущ | Триботехническая смазка и смазочная композиция |
US8728328B2 (en) | 2007-10-23 | 2014-05-20 | General Electric Company | Methods for removing suspended solids from a gasification process stream |
US8956556B2 (en) | 2008-07-02 | 2015-02-17 | Eaton Corporation | Dielectric isolators |
US8003014B2 (en) * | 2008-07-02 | 2011-08-23 | Eaton Corporation | Dielectric isolators |
US9136036B2 (en) * | 2008-07-02 | 2015-09-15 | Miller Waster Mills | Injection moldable, thermoplastic composite materials |
US9085678B2 (en) | 2010-01-08 | 2015-07-21 | King Abdulaziz City For Science And Technology | Clean flame retardant compositions with carbon nano tube for enhancing mechanical properties for insulation of wire and cable |
DE102010010957A1 (de) * | 2010-03-10 | 2011-09-15 | H.C. Carbon Gmbh | Baumaterial mit wärmedämmender Eigenschaft |
JP2012179588A (ja) * | 2011-02-10 | 2012-09-20 | Sony Corp | 酸化ストレス物質除去方法、酸化還元電位低下方法、濾材及び水 |
US8317891B1 (en) * | 2011-06-06 | 2012-11-27 | Cool Planet Biofuels, Inc. | Method for enhancing soil growth using bio-char |
EP2746337B1 (en) * | 2011-08-19 | 2017-10-04 | Sekisui Chemical Co., Ltd. | Carbon fiber composite material |
US8871019B2 (en) * | 2011-11-01 | 2014-10-28 | King Abdulaziz City Science And Technology | Composition for construction materials manufacturing and the method of its production |
KR101230532B1 (ko) * | 2012-09-03 | 2013-02-06 | 국방과학연구소 | 탄소 복합재료 |
ITMI20121808A1 (it) * | 2012-10-24 | 2014-04-25 | Versalis Spa | Composizioni polimeriche concentrate di polimeri e/o copolimeri vinilaromatici |
JP6364692B2 (ja) * | 2014-02-28 | 2018-08-01 | 小松精練株式会社 | 融雪用ブロック |
DE102015102041A1 (de) * | 2015-02-12 | 2016-08-18 | Danfoss Silicon Power Gmbh | Leistungsmodul |
USD780339S1 (en) * | 2015-09-11 | 2017-02-28 | Cambria Company Llc | Slab |
USD780344S1 (en) * | 2015-09-21 | 2017-02-28 | Cambria Company Llc | Portion of a slab |
USD780343S1 (en) * | 2015-09-21 | 2017-02-28 | Cambria Company Llc | Slab |
WO2017063434A1 (zh) * | 2015-10-15 | 2017-04-20 | 济南圣泉集团股份有限公司 | 一种含碳纳米结构的复合物、使用其的高分子材料及制备方法 |
CN106782723B (zh) * | 2016-12-05 | 2018-06-01 | 益阳金宙建材科技有限公司 | 一种用于隔离核泄漏的防辐射砂浆 |
DE102017208905B3 (de) | 2017-05-26 | 2018-05-30 | kipan GmbH | Leichtbauformteil mit Graphitpartikeln, Sandwichbauteile und Verfahren zur Herstellung des Leichtbauformteils |
JP6603005B2 (ja) * | 2017-09-29 | 2019-11-06 | 積水化学工業株式会社 | 強化繊維束、強化繊維開繊織物、および繊維強化複合体、並びにそれらの製造方法 |
CN109835901B (zh) * | 2019-03-26 | 2020-12-29 | 厦门大学 | 一种高比表面积活性炭及其制备方法 |
DE102021117451A1 (de) | 2021-03-12 | 2022-09-15 | Harold Scholz & Co. Gmbh | Elektrisch leitfähiges Baumaterial, insbesondere Beton, mit einem elektrisch leitfähigen Additiv auf Basis von Graphit |
DE102021117442A1 (de) | 2021-03-12 | 2022-09-15 | Harold Scholz & Co. Gmbh | Elektrisch leitfähiges Baumaterial, insbesondere Beton, mit einem elektrisch leitfähigen Additiv auf Basis von Kohlenstofffasern und Graphit |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0543318A (ja) * | 1991-08-09 | 1993-02-23 | Ibiden Co Ltd | 炭素成形体用組成物 |
JPH05194006A (ja) * | 1992-01-16 | 1993-08-03 | Kawatetsu Steel Prod Corp | グレーコンクリートの製造法 |
JPH06128008A (ja) * | 1992-09-03 | 1994-05-10 | Hiroshima Gas Kk | 帯電防止用セメント組成物 |
JP2001179214A (ja) * | 1999-12-28 | 2001-07-03 | Taiheiyo Cement Corp | 石油系燃焼灰の処理方法 |
JP2001192749A (ja) * | 1999-12-28 | 2001-07-17 | Taiheiyo Cement Corp | 石油系燃焼灰の処理方法 |
-
2004
- 2004-02-12 JP JP2004035668A patent/JP2005225712A/ja active Pending
- 2004-10-13 US US10/588,958 patent/US20070172408A1/en not_active Abandoned
- 2004-10-13 CN CNA2004800427251A patent/CN1938222A/zh active Pending
- 2004-10-13 DE DE200411002724 patent/DE112004002724T5/de not_active Withdrawn
- 2004-10-13 CA CA 2555799 patent/CA2555799A1/en not_active Abandoned
- 2004-10-13 WO PCT/JP2004/015073 patent/WO2005077825A1/ja active Application Filing
- 2004-10-26 TW TW93132341A patent/TW200526517A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0543318A (ja) * | 1991-08-09 | 1993-02-23 | Ibiden Co Ltd | 炭素成形体用組成物 |
JPH05194006A (ja) * | 1992-01-16 | 1993-08-03 | Kawatetsu Steel Prod Corp | グレーコンクリートの製造法 |
JPH06128008A (ja) * | 1992-09-03 | 1994-05-10 | Hiroshima Gas Kk | 帯電防止用セメント組成物 |
JP2001179214A (ja) * | 1999-12-28 | 2001-07-03 | Taiheiyo Cement Corp | 石油系燃焼灰の処理方法 |
JP2001192749A (ja) * | 1999-12-28 | 2001-07-17 | Taiheiyo Cement Corp | 石油系燃焼灰の処理方法 |
Also Published As
Publication number | Publication date |
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US20070172408A1 (en) | 2007-07-26 |
JP2005225712A (ja) | 2005-08-25 |
CN1938222A (zh) | 2007-03-28 |
CA2555799A1 (en) | 2005-08-25 |
DE112004002724T5 (de) | 2008-03-06 |
TW200526517A (en) | 2005-08-16 |
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