WO2019180797A1 - チタン系多孔体及びその製造方法 - Google Patents
チタン系多孔体及びその製造方法 Download PDFInfo
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- WO2019180797A1 WO2019180797A1 PCT/JP2018/010907 JP2018010907W WO2019180797A1 WO 2019180797 A1 WO2019180797 A1 WO 2019180797A1 JP 2018010907 W JP2018010907 W JP 2018010907W WO 2019180797 A1 WO2019180797 A1 WO 2019180797A1
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- porous body
- powder
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- porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1103—Making porous workpieces or articles with particular physical characteristics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2027—Metallic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2027—Metallic material
- B01D39/2031—Metallic material the material being particulate
- B01D39/2037—Metallic material the material being particulate otherwise bonded
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/004—Filling molds with powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/801—Sintered carriers
- H01M4/803—Sintered carriers of only powdered material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0471—Surface coating material
- B01D2239/0485—Surface coating material on particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1208—Porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1241—Particle diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1291—Other parameters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F2003/1042—Sintering only with support for articles to be sintered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/20—Refractory metals
- B22F2301/205—Titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
Definitions
- the present invention relates to a titanium-based porous body made of a titanium-based powder used as an electrode or a filter of a secondary battery or a fuel cell, or a manufacturing method thereof.
- titanium-based porous bodies As a performance required as an electrode of a battery, a method for producing a titanium-based porous body having high porosity and electrical conductivity is desired.
- a method for producing a titanium-based porous body by sintering titanium fibers and having a high porosity is known (for example, see Patent Document 1).
- the titanium-based porous body obtained by sintering the fiber has a high porosity of 70 to 90%, the specific surface area is small and the sintered area between the fibers is small, so the conductivity of the titanium-based porous body is low. There is a problem.
- a small specific surface area means that when a catalyst is supported on a titanium-based porous body and used as a carrier for reacting a gas or liquid near the surface of the titanium-based porous body, the titanium-based porous body and the reaction solution or reaction gas This leads to a problem that the reaction efficiency is lowered because the reaction field is reduced.
- a method for obtaining a titanium-based porous body having a through-hole and capable of flowing a liquid substance from one side to the other side by kneading and sintering a paste-like binder in titanium powder Is also known (see, for example, Patent Document 2).
- the method of kneading and sintering the binder involves a complicated manufacturing process and may increase the carbon content of the sintered body. Further, there are problems that the porosity is as low as 10 to 50% and the air permeability and water permeability are poor. Furthermore, a titanium-based porous body manufactured by sintering gas atomized titanium powder without using a paste is known (see, for example, Patent Document 3). However, since titanium powder having a high bulk density is used, a titanium-based porous body having a porosity of 55% or more cannot be produced, and there is a problem that air permeability and water permeability are poor.
- the present invention has been made in view of the above circumstances, and the problem to be solved by the present invention is to have a high specific surface area in order to exhibit excellent reaction efficiency, and to ensure air permeability and water permeability.
- An object of the present invention is to provide a titanium-based porous body having a high porosity for the purpose.
- Specific surface area is 4.5 ⁇ 10 ⁇ 2 to 1.5 ⁇ 10 ⁇ 1 m 2 / g, porosity is 50 to 70%, thickness is 4.0 ⁇ 10 ⁇ 1 to 1.6 mm, at least A sheet-like titanium-based porous body having a surface roughness on one side of 8.0 ⁇ m or less.
- a deformed titanium powder having an average particle size of 10 to 50 ⁇ m, D90 of less than 75 ⁇ m, and an average circularity of 0.50 to 0.90 on a setter in a dry and non-pressurized state, 800 to 1100 ° C.
- a method for producing a sheet-like titanium-based porous body characterized in that sintering is carried out. [3] The method for producing a sheet-like titanium porous body according to [2], wherein the setter is made of quartz. [4] An electrode using the sheet-like titanium-based porous material according to [1].
- the present invention controls a specific surface area and porosity of a titanium-based porous body, thereby maintaining good electrical conductivity, air permeability, and water permeability while maintaining practically required bending strength. Can be provided.
- the titanium-based porous body of the present invention has a specific surface area of 4.5 ⁇ 10 ⁇ 2 to 1.5 ⁇ 10 ⁇ 1 m 2 / g, a porosity of 50 to 70%, and a surface roughness of not more than 8.0 ⁇ m on one side.
- the specific surface area of the titanium-based porous body is preferably 5.0 ⁇ 10 ⁇ 2 to 1.3 ⁇ 10 ⁇ 1 m 2 / g and a porosity of 55 to 68%, more preferably 7.
- the specific surface area of the present invention is measured by the BET method based on JIS Z 8831: 2013. Krypton was used as the measurement gas.
- the surface roughness of at least one surface is 8.0 ⁇ m or less, and there is no limitation on the lower limit of the surface roughness, but it is preferably 0.1 ⁇ m or more.
- the surface roughness of the present invention is a value measured according to JIS B 0601-2001, and is an arithmetic average roughness Ra.
- the porosity of the present invention is the percentage of voids per unit volume of the titanium-based porous body, expressed as a percentage.
- the volume V (cm 3 ) of the titanium-based porous body and the mass M of the titanium-based porous body. and (g), (in the case of for example pure titanium true density 4.51 g / cm 3) true density D (g / cm 3) of the titanium-based material is that the calculated value from that calculated by the following formula Can do.
- Porosity (%) ((M / V) / D) ⁇ 100 (A)
- the carbon concentration of the titanium-based porous material of the present invention is 0.05% by weight or less, more preferably 0.03% by weight or less.
- the titanium-based porous body of the present invention has an advantage that the strength is not lowered and the electric resistance is not increased due to the influence of contamination by impurities because the carbon concentration in the porous body is low.
- the titanium-based porous body of the present invention has a thickness of 4.0 ⁇ 10 ⁇ 1 to 1.6 mm. More preferably, it is 4.0 ⁇ 10 ⁇ 1 to 1.0 mm, and still more preferably 4.0 ⁇ 10 ⁇ 1 to 6.0 ⁇ 10 ⁇ 1 mm. By making it in this range, the final product can be miniaturized while maintaining the bending strength necessary for practical use.
- the thickness of the titanium-based porous body is less than 4.0 ⁇ 10 ⁇ 1 mm, the uniformity of the voids in the titanium-based porous body is lowered, and the bending strength of the titanium-based porous body is lowered.
- the thickness of the titanium-based porous body is thicker than 1.6 mm, it becomes difficult to use it for a secondary battery whose size has been reduced.
- the titanium-based porous body of the present invention is composed of pure titanium, a titanium alloy, pure titanium or a titanium alloy coated with titanium nitride or titanium silicide, or a composite material combining these.
- Pure titanium is titanium composed of metallic titanium and other inevitable impurities.
- the titanium alloy is an alloy of titanium and a metal such as Fe, Sn, Cr, Al, V, Mn, Zr, and Mo.
- Ti-6-4 Ti-6Al-4V
- Ti— 5Al-2.5Sn Ti-8-1-1 (Ti-8Al-1Mo-1V)
- Ti-6-2-4-2 Ti-6Al-2Sn-4Zr-2Mo-0.1Si
- Ti- 6-6-2 Ti-6Al-6V-2Sn-0.7Fe-0.7Cu
- Ti-6-2-4-6 Ti-6Al-2Sn-4Zr-6Mo
- SP700 Ti-4.
- a titanium-based porous body composed of pure titanium, pure titanium coated with titanium nitride or titanium silicide, or a composite material in combination of these is preferable because it can reduce the electrical resistance when used for an electrode,
- a titanium-based porous body composed of pure titanium is more preferable.
- the titanium-based powder used for producing the titanium-based porous body of the present invention has (1) average particle size (D50 volume basis) of 10 to 50 ⁇ m, (2) D90 of less than 75 ⁇ m, and (3) average circularity of 0. .50-0.90 deformed titanium-based powder.
- D50 average particle size
- the specific surface area of the sintered body becomes less than 4.5 ⁇ 10 ⁇ 2 m 2 / g.
- it is less than 10 ⁇ m it is difficult to handle the titanium-based powder.
- the average particle diameter here refers to the value of the particle diameter D50 (median diameter) of the particle size distribution (volume basis) obtained by the laser diffraction scattering method.
- Second About D90 Deformed titanium powder having a particle size distribution (volume basis) particle size D90 of less than 75 ⁇ m is preferred. By setting D90 to less than 75 ⁇ m, a sintered body having high strength can be manufactured.
- the surface roughness of the titanium-based porous body depends on the particle diameter D90, and the smaller the D90, the smaller the surface roughness value and the better the strength of the titanium-based porous body.
- D90 refers to the particle diameter corresponding to 90% of the integrated volume distribution in the particle size distribution measurement by the laser diffraction scattering method.
- the deformed titanium-based powder includes primary particles that do not have a true spherical shape or a true spherical shape, and the average circularity of the primary particles is This means a titanium-based powder of 0.50 to 0.90.
- Examples of the deformed titanium-based powder include titanium-based powder manufactured by the HDH method, titanium-based powder manufactured by the pulverization method, and titanium-based powder obtained by mixing these. The shape of the titanium-based powder obtained by these production methods is irregular and non-spherical.
- the specific surface area of the sheet-like titanium-based porous body is less than 4.5 ⁇ 10 ⁇ 2 m 2 / g, and the porosity is less than 50%. It becomes.
- the circularity is B / A when the circumference (A) of the projected area of the particle is measured from an electron microscope or an atomic microscope and the circumference of a circle having the same area as the projected area is (B). Defined.
- the average circularity can be calculated by, for example, flowing particles together with a carrier liquid into a cell, taking a large amount of particle images with a CCD camera, and calculating the perimeter of the projected area of each particle from 1000 to 1500 individual particle images.
- the circularity can be calculated by measuring the circumference (B) of a circle having the same area as (A) and the projected area, and can be obtained as an average value of the circularity of each particle.
- the numerical value of the circularity increases as the particle shape approaches a true sphere, and the circularity of a particle having a complete true sphere shape becomes 1. Conversely, the numerical value of circularity decreases as the particle shape moves away from the true sphere.
- the titanium-based powder of the present invention is pure titanium powder, titanium alloy powder, hydrogenated pure titanium powder or titanium alloy powder, or pure titanium powder or titanium alloy powder coated with titanium nitride or titanium silicide.
- the pure titanium powder is a titanium powder composed of metallic titanium and other inevitable impurities.
- An example of the titanium alloy powder titanium alloy is the same as that described above.
- pure titanium powder, hydrogenated pure titanium powder, pure titanium powder coated with titanium nitride or titanium silicide, or a composite material combining these is preferable, and pure titanium powder is particularly preferable.
- a deformed titanium-based powder having an average particle size of 10 to 50 ⁇ m, D90 of less than 75 ⁇ m, and an average circularity of 0.50 to 0.90 is dry-type and applied without pressure. Placed on. Since the powder is packed more densely than only its own weight, it becomes difficult to produce a titanium-based porous body having a porosity of more than 70%.
- the setter should just be a material which does not react easily with titanium-type porous bodies, such as quartz and BN.
- a flat plate-like shape or a flat plate-like shape provided with a counterbore portion can be used, and a flat plate-like shape provided with a counterbore portion is particularly preferable.
- the counterbore part here refers to one having an edge around it and having a hole until it does not penetrate the plate, or one surrounded by a partition.
- the bottom of the counterbore may be flat, and the shape of the counterbore is more preferably the same as the shape of the final product.
- the method for placing titanium-based deformed powder is (1) A method of naturally dropping a deformed titanium-based powder from above the setter and placing it on the setter (2) After placing a frame-shaped powder filling jig of product dimensions on the setter, from above the setter, There is a method in which the irregular titanium-based powder is naturally dropped, and the powder-filling jig is filled up to the full without pressing the irregular titanium-based powder.
- the methods (2) and (3) are preferable because the powder remaining in the jig or the counterbore part is used as the product dimensions as it is.
- the surface roughness of the place (the surface of the setter or the bottom surface of the counterbore) where the titanium-based irregular shaped powder is placed is preferably 1.5 ⁇ m or less. By setting it as this range, the surface roughness of at least one surface of the sheet-like titanium-based porous body can be set to 8.0 ⁇ m or less.
- the titanium powder By placing the titanium-based powder without applying pressure (without applying pressure), the titanium powder can naturally bridge between the titanium powders to obtain a sintered titanium-based porous body having a porosity of 50 to 70%. it can.
- the term "no pressure" refers to a state in which no stress is applied toward the intentionally filled titanium powder surface. The stress applied to the titanium powder surface during filling accompanies when the powder is scraped in a direction parallel to the setter. It will be only what you do. Further, the bridge here means that the powder forms an arched cavity. Furthermore, it is preferable to fill the titanium-based powder by a dry method.
- the powders By filling the powder with a dry method, the powders can be naturally bridged to obtain a sintered body having a high porosity.
- the dry type here refers to a state in which powder and moisture or an organic solvent are not intentionally mixed.
- the titanium-based powder When the titanium-based powder is filled in a wet process, the titanium-based powder is deposited with anisotropy due to fluid resistance, and it becomes difficult to obtain a high porosity.
- an organic solvent when an organic solvent is used, the carbon concentration becomes as high as 0.1% by weight or more, and the strength of the sintered product of the titanium-based porous body may be reduced or the electrical resistance may be increased due to impurity contamination.
- the obtained titanium-based powder deposit is sintered at 800 to 1100 ° C.
- sintering is preferably performed at 800 to 1000 ° C.
- the sintering time is preferably 1 to 3 hours. Note that when hydrogenated pure titanium powder or titanium alloy powder is used as the raw material irregular titanium-based powder, dehydration is performed by removing the hydrogen contained in the powder by holding it at 400 to 600 ° C. once before the sintering step.
- a method of producing a porous body equivalent to that using HDH powder with higher bending strength as a raw material by sandwiching the elementary process is also included.
- the sheet-like titanium-based porous body of the present invention can be obtained by using a titanium-based powder having a specific average particle size and shape and molding and firing under specific conditions. For example, when the average particle diameter of the titanium-based powder is increased, the specific surface area of the sheet-like titanium-based porous body is decreased, and the porosity is increased. Moreover, when the circularity of the titanium-based powder increases, the porosity of the sheet-like titanium-based porous body decreases. The tendency of the circularity of the titanium-based powder to the specific surface area of the sheet-like titanium-based porous body shows a change having a maximum at a certain value.
- the specific surface area and porosity of the sheet-like titanium porous body are reduced.
- the specific surface area and porosity of the sheet-like titanium porous body can be adjusted.
- the thickness of the sheet-like titanium-based porous body can be adjusted by the thickness of the titanium-based irregular shaped powder, the height of the jig, or the depth of the sagging portion.
- surface of a sheet-like titanium-type porous body can be adjusted with the surface roughness of the bottom surface of the setter or counterbore part which mounts titanium type powder.
- the particles are flowed together with the carrier liquid in the cell, and a large number of particle images are taken with a CCD camera. From the individual particle images, the perimeter of the projected area of the particles (A) and the area equal to the projected area are taken. The circumference of the circle was measured as (B), and B / A was calculated as the circularity when the circumference of the projected area (A) and the circumference of the circle having the same area as the projected area were (B). . With respect to each of 1000 to 1500 particles, the circularity was measured, and the number average value was defined as the average circularity.
- Porosity calculated using the above formula (A) 2) Specific surface area: Measured by BET method based on JIS Z 8831: 2013 using ASAP2460 (manufactured by Micromeritics). Adsorbed gas is krypton. Pretreatment conditions are N 2 flow method (120 ° C. ⁇ 1 Hr). The measurement temperature is -196 ° C. 3) Conductivity: Measured according to JIS K 7194 using MCP-T610 (Mitsubishi Chemical Corporation). 4) Surface roughness: Measured according to JIS B 0601-2001 using a surf test SJ-310 (manufactured by Mitutoyo Corporation).
- Bending strength Measured according to JIS Z 248 using a 5582 type universal testing machine (Instron). The test conditions were evaluated by the maximum load (N) when the pusher diameter was 5 mm, the receiving 3R edge, the distance between external fulcrums was 40 mm, and the test speed was 4 mm / min. 6) Carbon concentration measurement method: Measured by combustion-infrared absorption method using EMIA-920V2 manufactured by Horiba, Ltd. 0.5 g of a sample, metal tin and metal tungsten were placed in an alumina crucible, heated and burned with a high-frequency current in an oxygen stream, and the generated CO 2 was detected and quantified by infrared rays to obtain the carbon concentration in the sample.
- a deformed titanium powder having a specific particle size distribution and circularity is used as the raw material powder. And the circularity was changed and the influence was investigated.
- HDH titanium powder with an average particle size (D50) of 30 ⁇ m (D90: 47 ⁇ m) and an average circularity of 0.78 is packed on a countersunk quartz setter with a counterbore depth of 0.50 mm and a bottom surface roughness of the counterbore of 0.76 ⁇ m. And it sintered on the said sintering conditions, and obtained the titanium-type porous body.
- the thickness of the obtained titanium-based porous body was 0.47 mm, the porosity was 64%, the specific surface area was 8.4 ⁇ 10 ⁇ 2 m 2 / g, and the surface in contact with the counterbore quartz setter
- the surface roughness (same in the following examples) was 3.7 ⁇ m, the conductivity was 2.96 ⁇ 10 3 S / cm, and the maximum load in the bending test was 5.9 N.
- the carbon concentration in the titanium-based porous body was 0.02%.
- a titanium-based porous material was obtained under the same conditions as in Example 1 except that HDH titanium powder having an average particle size (D50) of 12 ⁇ m (D90: 19 ⁇ m) and an average circularity of 0.88 was used as a raw material.
- the obtained titanium-based porous body has a thickness of 0.45 mm, a porosity of 58%, a specific surface area of 1.1 ⁇ 10 ⁇ 1 m 2 / g, and a surface roughness of 2.4 ⁇ m.
- the conductivity was 3.15 ⁇ 10 3 S / cm, and the maximum load in the bending test was 14.7 N.
- the carbon concentration in the titanium-based porous body was 0.01%.
- a titanium-based porous body was obtained under the same conditions as in Example 1 except that HDH titanium powder having an average particle size (D50) of 50 ⁇ m (D90: 74 ⁇ m) and an average circularity of 0.82 was used as a raw material.
- the obtained titanium-based porous body has a thickness of 0.52 mm, a porosity of 59%, a specific surface area of 4.9 ⁇ 10 ⁇ 2 m 2 / g, and a surface roughness of 6.0 ⁇ m. Yes, the conductivity was 2.02 ⁇ 10 3 S / cm, and the maximum load in the bending test was 4.6 N. The carbon concentration in the titanium-based porous body was 0.03%.
- a titanium-based porous body was obtained under the same conditions as in Example 1 except that spherical titanium powder having an average particle diameter (D50) of 32 ⁇ m (D90: 48 ⁇ m) and an average circularity of 0.94 was used as a raw material.
- the obtained titanium-based porous body has a thickness of 0.49 mm, a porosity of 44%, a specific surface area of 4.3 ⁇ 10 ⁇ 2 m 2 / g, and a surface roughness of 3.3 ⁇ m. Yes, the conductivity was 5.28 ⁇ 10 3 S / cm, and the maximum load in the bending test was 22.2N.
- a titanium-based porous material was obtained under the same conditions as in Example 1 except that HDH titanium powder having an average particle size (D50) of 90 ⁇ m (D90: 107 ⁇ m) and an average circularity of 0.80 was used as a raw material.
- the obtained titanium-based porous body has a thickness of 0.47 mm, a porosity of 63%, a specific surface area of 3.3 ⁇ 10 ⁇ 2 m 2 / g, and a surface roughness of 8.4 ⁇ m. Yes, the conductivity was 1.31 ⁇ 10 3 S / cm, and the maximum load in the bending test was 1.6 N.
- a titanium-based porous body was obtained under the same conditions as in Example 1 except that titanium fibers having a size of ⁇ 20 ⁇ m ⁇ 2.5 mm (average circularity cannot be measured) were used as raw materials.
- the obtained titanium-based porous body has a thickness of 0.51 mm, a porosity of 80%, a specific surface area of 5.4 ⁇ 10 ⁇ 2 m 2 / g, and a surface roughness of 18 ⁇ m.
- the conductivity was 1.27 ⁇ 10 3 S / cm, and the maximum load in the bending test was 3.4N.
- the deformed titanium-based powder used as a raw material has D50 as specified in claim 2.
- a titanium-like porous body was obtained, which was excellent in conductivity and strength characteristics.
- Example 4 A titanium-based porous body was obtained under the same conditions as in Example 1 except that the temperature increase rate was 12 ° C./min and the ultimate temperature was 700 ° C.
- the obtained titanium-based porous body has a thickness of 0.49 mm, a porosity of 73%, a specific surface area of 1.1 ⁇ 10 ⁇ 1 m 2 / g, and a surface roughness of 4.5 ⁇ m.
- Example 4 Using a frame-shaped powder filling jig having a height of about 0.50 mm from the setter surface (surface roughness 1.1 ⁇ m), the HDH titanium powder of Example 1 is filled on the BN setter, and the degree of vacuum is 3. The temperature was raised at a rate of 10 ° C./min in an atmosphere of 0 ⁇ 10 ⁇ 3 Pa, kept at an ultimate temperature of 1100 ° C. for 1 Hr, and then cooled in the furnace to obtain a titanium-based porous body.
- the obtained titanium-based porous body has a thickness of 0.46 mm, a porosity of 57%, a specific surface area of 6.7 ⁇ 10 ⁇ 2 m 2 / g, and a surface roughness of 4.3 ⁇ m.
- the conductivity was 3.55 ⁇ 10 3 S / cm, and the maximum load in the bending test was 9.8 N.
- the carbon concentration in the titanium-based porous body was 0.03%.
- Example 5 A titanium-based porous body was obtained under the same conditions as in Example 1 except that the counterbore depth of the counterbore quartz setter was 1.50 mm. The obtained titanium-based porous body has a thickness of 1.5 mm, a porosity of 62%, a specific surface area of 7.3 ⁇ 10 ⁇ 2 m 2 / g, and a surface roughness of 4.2 ⁇ m.
- Example 6 A titanium-based porous body was obtained under the same conditions as in Example 1 except that a powder was filled on the BN setter using a frame-shaped powder filling jig having a height of about 0.30 mm from the setter surface. The obtained titanium-based porous body has a thickness of 0.30 mm, a porosity of 74%, a specific surface area of 7.4 ⁇ 10 ⁇ 2 m 2 / g, and a surface roughness of 9.0 ⁇ m. Yes, the conductivity was 1.22 ⁇ 10 3 S / cm, and the maximum load in the bending test was 0.8N.
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Abstract
Description
従来、チタン繊維を焼結し、高い空隙率を有するチタン系多孔体を製造する方法が知られている(例えば、特許文献1参照)。しかしながら、繊維を焼結したチタン系多孔体は70~90%の高い空隙率を有するものの、比表面積が小さく、また、繊維同士の焼結面積が小さいため、チタン系多孔体の導電率が低いという問題点がある。例えば、比表面積が小さいことは、チタン系多孔体上に触媒を担持し、チタン系多孔体表面近傍でガスや液を反応させる担体として用いた時、チタン系多孔体と反応溶液や反応ガスとの反応場が少なくなるため、反応効率が低下するという問題へ繋がる。
また、チタン粉末にペースト状のバインダーを混練し、焼結することで、貫通孔を有し、液状物質を一面側から他面側にむけて流通することが可能なチタン系多孔体を得る方法も知られている(例えば、特許文献2参照)。しかしながら、バインダーを混練し、焼結する方法は、製造工程が複雑な上に、焼結体のカーボン含有量が高くなるおそれがある。また、空隙率が10~50%と低く、通気性、通水性が悪いという問題点がある。
更に、ペーストを用いずに、ガスアトマイズチタン粉末を焼結することで、製造されるチタン系多孔体が知られている(例えば、特許文献3参照)。しかしながら、嵩密度が高いチタン粉を使用するため55%以上の空隙率のチタン系多孔体を製造することができず、通気性、通水性が悪いという問題点がある。
[1]比表面積が4.5×10-2~1.5×10-1m2/g、空隙率が50~70%、厚さが4.0×10-1~1.6mm、少なくとも片面の表面粗さが8.0μm以下であることを特徴とするシート状チタン系多孔体。
[2]平均粒径10~50μm、D90が75μm未満、平均円形度0.50~0.90の異形チタン系粉を、乾式かつ、無加圧でセッター上に載置後、800~1100℃で焼結させることを特徴とするシート状チタン系多孔体の製造方法。
[3]セッターの材質が、石英であることを特徴とする[2]に記載のシート状チタン系多孔体の製造方法。
[4][1]に記載のシート状チタン系多孔体を用いた電極。
≪比表面積・空隙率・表面粗さについて≫
本発明のチタン系多孔体は、4.5×10-2~1.5×10-1m2/gの比表面積、50~70%の空隙率、片面が8.0μm以下の表面粗さを有する。
まず、チタン系多孔体の比表面積は、5.0×10-2~1.3×10-1m2/g及び55~68%の空隙率であることが好ましく、さらに好ましくは、7.0×10-2~1.1×10-1m2/g及び60~66%の空隙率である。この範囲に設定することで、実用上必要な曲げ強度を維持しつつ、導電性及び通気性並びに通水性を良好に保つことができる。本発明の比表面積は、JIS Z 8831:2013に準拠したBET法で測定したものである。測定ガスにはクリプトンを使用した。
次に、少なくとも片面の表面粗さは8.0μm以下であり、表面粗さの下限の限定はないが、好ましくは、0.1μm以上である。本発明の表面粗さは、JIS B 0601-2001に準拠して測定した値であり、算術平均粗さRaのことである。
また、本発明の空隙率は、チタン系多孔体の単位体積あたりの空隙の割合を百分率で示したものであり、チタン系多孔体の体積V(cm3)と、チタン系多孔体の質量M(g)と、チタン系材料の真密度D(g/cm3)(例えば純チタンの場合は真密度4.51g/cm3)から算出した値のことであり、以下の式で算出することができる。
空隙率(%)=((M/V)/D)×100 ・・・(A)
本発明のチタン系多孔体の炭素濃度は、0.05重量%以下、より好ましくは0.03重量%以下である。本発明のチタン系多孔体は、多孔体中の炭素濃度が低いので、不純物による汚染の影響で強度が低下したり電気抵抗が大きくなる恐れがない、という利点を有する 。
本発明のチタン系多孔体は、4.0×10-1~1.6mmの厚さを有する。より好ましくは、4.0×10-1~1.0mmであり、さらに好ましくは4.0×10-1~6.0×10-1mmである。この範囲にすることで実用上必要な曲げ強度を維持しつつ、最終製品を小型化することができる。チタン系多孔体の厚さが、4.0×10-1mm未満だとチタン系多孔体の空隙の均一性が低くなり、チタン系多孔体の曲げ強度が低くなる。チタン系多孔体の厚さが1.6mmよりも厚くなると、小型化が進んでいる二次電池に使用することが難しくなる。
なお、本発明のチタン系多孔体は、純チタン、チタン合金、窒化チタンやチタンシリサイドでコーティングされた純チタンまたはチタン合金、あるいはこれらを組み合わせた複合材料等から構成される。純チタンは、金属チタンとその他不可避不純物からなるチタンである。チタン合金は、チタンとFe,Sn,Cr,Al,V,Mn,Zr,Mo等の金属との合金であり、具体例としては、Ti-6-4(Ti-6Al-4V)、Ti-5Al-2.5Sn、Ti-8-1-1(Ti-8Al-1Mo-1V)、Ti-6-2-4-2(Ti-6Al-2Sn-4Zr-2Mo-0.1Si)、Ti-6-6-2(Ti-6Al-6V-2Sn-0.7Fe-0.7Cu)、Ti-6-2-4-6(Ti-6Al-2Sn-4Zr-6Mo)、SP700(Ti-4.5Al-3V-2Fe-2Mo)、Ti-17(Ti-5Al-2Sn-2Zr-4Mo-4Cr)、β-CEZ(Ti-5Al-2Sn-4Zr-4Mo-2Cr-1Fe)、TIMETAL555、Ti-5553(Ti-5Al-5Mo-5V-3Cr-0.5Fe)、TIMETAL21S(Ti-15Mo-2.7Nb-3Al-0.2Si)、TIMETAL LCB(Ti-4.5Fe-6.8Mo-1.5Al)、10-2-3(Ti-10V-2Fe-3Al)、Beta C(Ti-3Al-8V-6Cr-4Mo-4Cr)、Ti-8823(Ti-8Mo-8V-2Fe-3Al)、15-3(Ti-15V-3Cr-3Al-3Sn)、BetaIII(Ti-11.5Mo-6Zr-4.5Sn)、Ti-13V-11Cr-3Al等が挙げられる。
特に、純チタン、窒化チタンやチタンシリサイドでコーティングされた純チタン、あるいはこれらを組み合わせた複合材料から構成されたチタン系多孔体が、電極に用いた際の電気抵抗を下げることができるため好ましく、より好ましくは純チタンで構成されるチタン系多孔体である。
≪チタン粉の性質について≫
本発明のチタン系多孔体を製造する際に使用するチタン系粉は、(1)平均粒径(D50体積基準)10~50μm、(2)D90が75μm未満、(3)平均円形度が0.50~0.90の異形チタン系粉である。以下、それぞれの特性について説明する。
(1)平均粒径(D50)について
平均粒径が50μmより大きいと、焼結体の比表面積が4.5×10-2m2/g未満となる。一方、10μm未満の場合には、チタン系粉のハンドリングが困難である。なお、ここでいう平均粒径は、レーザー回折散乱法によって得られた粒度分布(体積基準)の粒子径D50(メジアン径)の値を指す。
(2)D90について
粒度分布(体積基準)の粒子径D90が75μm未満の異形チタン系粉が好ましい。D90を75μm未満にすることで、強度が高い焼結体を製造することができる。
また、チタン系多孔体の表面粗さは、粒子径D90に依存し、D90が小さくなるほど表面粗さの値も小さくなり、チタン系多孔体の強度が良好となる。D90とはレーザー回析散乱法による粒度分布測定における体積分布の積算値が90%に相当する粒子径を指す。
(3)平均円形度が0.50~0.90の異形チタン系粉について
異形チタン系粉とは、真球あるいは真球形の形状を有しない一次粒子を含み、一次粒子の平均円形度が、0.50~0.90のチタン系粉を意味する。異形チタン系粉の例としては、HDH法で製造されたチタン系粉及び粉砕法で製造されたチタン系粉、並びにこれらを混合してなるチタン系粉が挙げられる。これらの製法で得られるチタン系粉の形状は、不定形であり非球形である。一次粒子の平均円形度が、0.90より大きいチタン系粉を用いた場合、シート状チタン系多孔体の比表面積は4.5×10-2m2/g未満、空隙率は50%未満となる。
ここで、円形度は、電子顕微鏡や原子顕微鏡から粒子の投影面積の周囲長(A)を測定し、前記投影面積と等しい面積の円の周囲長を(B)とした場合のB/Aとして定義される。また、平均円形度は、例えば、セル内にキャリア液とともに粒子を流し、CCDカメラで多量の粒子の画像を撮り込み、1000~1500個の個々の粒子画像から、各粒子の投影面積の周囲長(A)と投影面積と等しい面積の円の周囲長(B)を測定して円形度を算出し、各粒子の円形度の平均値として求めることができる。上記円形度の数値は粒子の形状が真球に近くなるほど大きくなり、完全な真球の形状を有する粒子の円形度は1となる。逆に、粒子の形状が真球から離れるにつれて円形度の数値は小さくなる。
セッターは、石英やBNなどチタン系多孔体と反応しにくい材質であれば良い。形状は、平面の板状のもの、ザグリ部を設けた平面の板状のものを使用することができ、特にザグリ部を設けた平面の板状のものが好ましい。ここでいうザグリ部とは、まわりに縁があり、板に貫通しないまでの穴が開いているものや、仕切りで周りを囲っているものを指す。ザグリの底が平らになっていても良く、また、ザグリの形状は、最終製品の形状と同様であるとより好ましい。
(1)セッター上方から、異形チタン系粉を自然落下させ、セッター上に載置する方法
(2)セッター上に製品寸法の枠状の粉末充填用治具を載置したのち、セッター上方から、異形チタン系粉を自然落下させ、異形チタン系粉を加圧することなく、粉末充填用治具のすりきり一杯まで充填する方法、などがある。
ザグリ部を設けたセッターを用いる場合には、
(3)ザグリ部にチタン系異形粉を自然落下により投入した後、チタン系異形粉を加圧することなく、板状の治具でザグリ部から溢れた粉末を擦切る方法、などがある。
特に(2)、(3)の方法は、治具内またはザグリ部に残存する粉末がそのまま製品寸法とする方法となり好ましい。
チタン系異形粉を載置される場所(セッターの表面またはザグリ部の底面)の表面粗さは1.5μm以下が好ましい。この範囲とすることで、シート状チタン系多孔体の少なくとも片面の表面粗さを8.0μm以下とすることができる。
チタン系粉末を加圧することなく(無加圧で)載置することによって、チタン粉末同士が自然な状態でブリッジし、空隙率50~70%のチタン系多孔体の焼結体を得ることができる。ここでいう無加圧とは、意図的に充填したチタン粉末面に向かって応力を加えない状態を指し、充填時にチタン粉末面に加わる応力は、セッターと平行方向に粉末を擦切る際に付随するもののみになる。また、ここでいうブリッジとは粉末がアーチ状の空洞を形成することを指す。
さらにチタン系粉末の充填は乾式で行うことが好ましい。乾式で粉末を充填することによって、粉末同士が自然な状態でブリッジし、高い空隙率を持つ焼結体を得ることができる。ここでいう乾式とは、意図的に粉末と水分や有機溶剤を混合しない状態を指す。湿式でチタン系粉末を充填すると、流体の抵抗によりチタン系粉末が異方性を持って堆積し、高い空隙率を得ることが困難になる。また、有機溶媒を用いた場合は炭素濃度が0.1重量%以上と高くなり、不純物のコンタミによりチタン系多孔体の焼結品の強度が低下したり電気抵抗が大きくなるおそれがある。
得られたチタン系粉末の堆積体は、800~1100℃で焼結する。石英セッターを使用する場合は800~1000℃で焼結することが好ましい。この範囲の温度で焼結を行うことで、実用上必要な強度を持ち、表面の平滑な焼結体を製造することができる。焼結時間は1~3時間が好ましい。
なお、原料の異形チタン系粉として、水素化した純チタン粉またはチタン合金粉を用いる場合は、焼結工程の前に一旦400~600℃で保持することにより粉末に含まれる水素を抜きとる脱水素工程をはさむことで、より曲げ強度の高いHDH粉を原料としたものと同等の多孔体を製造する方法なども挙げられる。
上述したように、平均粒径、形状が特定のチタン系粉を用い、特定の条件で成型、焼成することにより、本発明のシート状チタン系多孔体を得ることができる。
例えば、チタン系粉の平均粒径が大きくなると、シート状チタン系多孔体の比表面積、は小さくなり、空隙率は大きくなる。また、チタン系粉の円形度は大きくなると、シート状チタン系多孔体の空隙率は小さくなる。チタン系粉の円形度のシート状チタン系多孔体の比表面積に対する傾向は、ある値で極大を有する変化を示す。焼成温度は高温になると、シート状チタン系多孔体の比表面積、空隙率は小さくなる。これらのパラメータを制御することで、シート状チタン系多孔体の比表面積、空隙率を調整することができる。
シート状チタン系多孔体の厚さは、チタン系異形粉の載置した厚さ、治具の高さまたはサグリ部の深さにより調整することができる。また、シート状チタン系多孔体の片面の表面粗さは、チタン系粉を載置するセッターまたはザグリ部の底面の表面粗さにより調整できる。
実施例で使用した設備および条件を以下に示す。
1.原料チタン系粉末
1)製造方法:水素化脱水素法
2)平均粒径・粒度分布の測定方法:LMS-350(セイシン企業社製)を用いて、JIS Z 8825:2013に準拠し測定した。得られた粒度分布(体積基準)より体積分布の積算値が50%及び90%に相当する粒子径D50、D90を求めた。
3)平均円形度の測定方法:セイシン企業社製のPITA3を用いて測定を行った。具体的には、セル内にキャリア液とともに粒子を流し、CCDカメラで多量の粒子の画像を撮り込み、個々の粒子画像から、粒子の投影面積の周囲長(A)と投影面積と等しい面積の円の周囲長を(B)を測定し、投影面積の周囲長(A)と、前記投影面積と等しい面積の円の周囲長を(B)とした場合のB/Aを円形度として求めた。1000~1500個の各粒子を対象とし、円形度を測定し、その個数平均値を平均円形度とした。
1)セッター:ザグリ付石英セッター(ザグリ寸法:60×60×0.5tmm,サグリ部底面の表面粗さ:0.76μm)
2)真空度:3.0×10-3Pa
3)昇温速度:15℃/min
4)到達温度:900℃(保持時間1Hr)
5)冷却方法:900℃から100℃まで炉冷
1)空隙率:上記(A)式を用いて算出
2)比表面積:ASAP2460(マイクロメリティックス社製)を用い、JIS Z 8831:2013に準拠したBET法にて測定。
吸着ガスはクリプトン。前処理条件はN2流通法(120℃×1Hr)。測定温度は―196℃。
3)導電率:MCP―T610(三菱化学社製)を用い、JIS K 7194に準拠して測定。
4)表面粗さ:サーフテストSJ-310(株式会社ミツトヨ製)を用い、JIS B 0601-2001に準拠して測定。
5)曲げ強さ:5582型万能試験機(インストロン社製)を用い、JIS Z 248に準拠し、測定。試験条件は、押し子直径5mm、受け3Rエッジ、外部支点間距離40mm、試験速度4mm/minで行ったときの最大荷重(N)で評価した。
6)炭素濃度の測定方法:株式会社堀場製作所製EMIA-920V2を使用して、燃焼-赤外線吸収法により測定した。試料0.5gと金属錫および金属タングステンをアルミナるつぼに入れ、酸素気流中で高周波電流によって加熱、燃焼させ、発生したCO2を赤外線により検出、定量し、試料中の炭素濃度とした。
本件発明に係るシート状チタン系多孔体の製造方法では、原料粉末として特定の粒度分布と円形度を有する異形チタン系粉末を使用するが、粒度分布と円形度を変化させて、その影響を調べた。
[実施例1]
平均粒径(D50)30μm(D90:47μm)、平均円形度0.78のHDHチタン粉末をザグリ深さ0.50mm、ザグリ部の底面の表面粗さ0.76μmのザグリ付石英セッター上に充填し、上記焼結条件で焼結し、チタン系多孔体を得た。
得られたチタン系多孔体の厚さは0.47mmであり、空隙率は64%であり、比表面積は8.4×10-2m2/gであり、ザグリ付石英セッターに接した面の表面粗さ(以下の実施例で同じ)は3.7μmであり、導電率は2.96×103S/cmであり、曲げ試験での最大荷重は5.9Nであった。また、チタン系多孔体中の炭素濃度は0.02%であった。
[実施例2]
平均粒径(D50)12μm(D90:19μm)、平均円形度0.88のHDHチタン粉末を原料とした以外、実施例1と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは0.45mmであり、空隙率は58%であり、比表面積は1.1×10-1m2/gであり、表面粗さは2.4μmであり、導電率は3.15×103S/cmであり、曲げ試験での最大荷重は14.7Nであった。
また、チタン系多孔体中の炭素濃度は0.01%であった。
[実施例3]
平均粒径(D50)50μm(D90:74μm)、平均円形度0.82のHDHチタン粉末を原料とした以外、実施例1と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは0.52mmであり、空隙率は59%であり、比表面積は4.9×10-2m2/gであり、表面粗さは6.0μmであり、導電率は2.02×103S/cmであり、曲げ試験での最大荷重は4.6Nであった。
また、チタン系多孔体中の炭素濃度は0.03%であった。
[比較例1]
平均粒径(D50)32μm(D90:48μm)、平均円形度0.94の球状チタン粉末を原料とした以外、実施例1と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは0.49mmであり、空隙率は44%であり、比表面積は4.3×10-2m2/gであり、表面粗さは3.3μmであり、導電率は5.28×103S/cmであり、曲げ試験での最大荷重は22.2Nであった。
[比較例2]
平均粒径(D50)90μm(D90:107μm)、平均円形度0.80のHDHチタン粉末を原料とした以外、実施例1と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは0.47mmであり、空隙率は63%であり、比表面積は3.3×10-2m2/gであり、表面粗さは8.4μmであり、導電率は1.31×103S/cmであり、曲げ試験での最大荷重は1.6Nであった。
[比較例3]
寸法φ20μm×2.5mmのチタン繊維(平均円形度は、測定不能)を原料とした以外、実施例1と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは0.51mmであり、空隙率は80%であり、比表面積は5.4×10-2m2/gであり、表面粗さは18μmであり、導電率は1.27×103S/cmであり、曲げ試験での最大荷重は3.4Nであった。
平均円形度(比較例1)、D50及びD90が上記範囲を逸脱するもの(比較例2)、チタン繊維を原料としたもの(比較例3)は、良好なシート状チタン系多孔体を得ることができなかった。
本発明に係るシート状チタン系多孔体の製造方法では、焼結の際の到達温度を800~1100℃としているが、その影響を調べた。
[比較例4]
昇温速度12℃/min、到達温度700℃とした以外、実施例1と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは0.49mmであり、空隙率は73%であり、比表面積は1.1×10-1m2/gであり、表面粗さは4.5μmであり、導電率は4.76×102S/cmであり、曲げ試験での最大荷重は0.5Nであった。
[実施例4]
セッター表面(表面粗さ1.1μm)から約0.50mmの高さの枠状の粉末充填用治具を用いて、実施例1のHDHチタン粉末をBNセッター上に充填し、真空度3.0×10-3Paの雰囲気で10℃/minの速さで昇温し、到達温度1100℃で1Hr保持後炉冷することでチタン系多孔体を得た。
得られたチタン系多孔体の厚さは0.46mmであり、空隙率は57%であり、比表面積は6.7×10-2m2/gであり、表面粗さは4.3μmであり、導電率は3.55×103S/cmであり、曲げ試験での最大荷重は9.8Nであった。
また、チタン系多孔体中の炭素濃度は0.03%であった。
[比較例5]
実施例4の到達温度を1100℃から1200℃へ変更した以外、実施例4と同様にチタン系多孔体の製造を試みたが、粉末とセッターが反応し、セッターからチタン系多孔体の剥離不可となり、チタン系多孔体を得ることはできなかった。
本発明に係るシート状チタン系多孔体は、厚さを4.0×10-1~1.6mmと 特定するが、その値を変化させて、特性のシート厚のシート特性に対する影響を調べた。
[実施例5]
ザグリ付石英セッターのザグリ深さを1.50mmとした以外、実施例1と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは1.5mmであり、空隙率は62%であり、比表面積は7.3×10-2m2/gであり、表面粗さは4.2μmであり、導電率は3.09×103S/cmであり、曲げ試験での最大荷重は50.2Nであった。
また、チタン系多孔体中の炭素濃度は0.01%であった。
[比較例6]
セッター表面から約0.30mmの高さの枠状の粉末充填用治具を用いて、BNセッター上に粉末を充填した以外は実施例1と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは0.30mmであり、空隙率は74%であり、比表面積は7.4×10-2m2/gであり、表面粗さは9.0μmであり、導電率は1.22×103S/cmであり、曲げ試験での最大荷重は0.8Nであった。
Claims (4)
- 比表面積が4.5×10-2~1.5×10-1m2/g、空隙率が50~70%、厚さが4.0×10-1~1.6mm、少なくとも片面の表面粗さが8.0μm以下であることを特徴とするシート状チタン系多孔体。
- 平均粒径10~50μm、D90が75μm未満、平均円形度0.50~0.90の異形チタン系粉を、乾式かつ、無加圧でセッター上に載置後、800~1100℃で焼結させることを特徴とするシート状チタン系多孔体の製造方法。
- セッターの材質が、石英であることを特徴とする請求項2に記載のシート状チタン系多孔体の製造方法。
- 請求項1に記載のシート状チタン系多孔体を用いた電極。
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WO2022075038A1 (ja) * | 2020-10-05 | 2022-04-14 | 東邦チタニウム株式会社 | 多孔質金属体の製造方法及び、多孔質金属体 |
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