WO2013103043A1 - 多孔質アルミニウムの製造方法 - Google Patents
多孔質アルミニウムの製造方法 Download PDFInfo
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- WO2013103043A1 WO2013103043A1 PCT/JP2012/078351 JP2012078351W WO2013103043A1 WO 2013103043 A1 WO2013103043 A1 WO 2013103043A1 JP 2012078351 W JP2012078351 W JP 2012078351W WO 2013103043 A1 WO2013103043 A1 WO 2013103043A1
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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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- 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
- B22F3/02—Compacting only
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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
- C22C1/0408—Light metal alloys
- C22C1/0416—Aluminium-based alloys
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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
- C22C1/08—Alloys with open or closed pores
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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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
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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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
- H01M4/665—Composites
- H01M4/666—Composites in the form of mixed materials
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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
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. 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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- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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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
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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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
- B22F3/12—Both compacting and sintering
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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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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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
Definitions
- the present invention relates to a method for producing porous aluminum having a high porosity and a uniform pore size, which is suitable for a current collector of a lithium ion secondary battery, various filters, a catalyst carrier, a heat exchanger, a sound absorbing material, and the like.
- Patent Document 1 As a method for producing a porous metal, a molten metal foaming method (Patent Document 1) in which a foaming agent such as titanium hydride is mixed in a molten metal and the generated gas is solidified, or metal powder and sodium chloride is used.
- Patent Document 2 A spacer method (Patent Document 2) is known in which a spacer material such as the above is mixed and compression-molded and then the metal powder is energized and heated to remove the spacer material.
- the resulting porous body is a closed cell type, which is not suitable for a current collector that must be filled with an active material or a filter that requires fluid permeability.
- the conventional spacer method that uses electric heating to sinter requires a large current, so that the size is limited and it is difficult to produce a practical porous metal.
- the present inventors appropriately select the particle size and volume ratio of the aluminum powder and support powder used in the spacer method, and further control the pressure molding conditions and heat treatment conditions.
- a method for easily producing a porous metal having a high porosity has been found, and the present invention has been completed.
- the present invention is the mixed powder of the aluminum powder and the supporting powder according to claim 1, wherein the mixed powder having a volume ratio of 5-30% of the aluminum powder with respect to the whole of the mixed powder is pressure-molded at a pressure of 200 MPa or more.
- a step of sintering the pressure molded body by heat treatment in an inert atmosphere at a temperature higher than the melting point of the aluminum powder and less than 700 ° C., and a step of removing the supporting powder from the sintered body A method for producing porous aluminum containing
- the present invention according to claim 2 is the method according to claim 1, wherein the mixed powder and the metal plate are combined with a metal plate under pressure molding at a pressure of 200 MPa or more, and the pressure molded body is melted in an inert atmosphere.
- the above includes a step of sintering by heat treatment in a temperature range of less than 700 ° C. and a step of removing the supporting powder from the sintered body.
- the aluminum powder according to the first or second aspect is covered with the aluminum powder defined by the particle diameter and volume of the aluminum powder as dal and Val, respectively, and the particle size and volume of the support powder as ds and Vs, respectively.
- the coverage area ratio C ⁇ (Val ⁇ ds) / (4Vs ⁇ dal) ⁇ ⁇ 100 on the surface of the support powder is 70% or more.
- the supporting powder is sodium chloride, potassium chloride, or a mixture thereof.
- the aluminum powder contains at least one of pure aluminum powder and aluminum alloy powder.
- the aluminum powder according to the fifth aspect includes an additive element powder.
- the aluminum powder and the supporting powder are adjusted to have a particle size, and the volume ratio thereof is adjusted so that the aluminum powders are brought into contact with each other, and the oxide film on the surface of the aluminum powder is destroyed by applying sufficient pressure. To expose the new surface. Then, the aluminum powder and the supporting powder can be firmly bonded to each other by heat-treating the mixed powder of the aluminum powder and the supporting powder in an inert atmosphere at a temperature higher than the melting point of the aluminum powder and less than 700 ° C. it can. As a result, it is possible to obtain an open cell porous aluminum having a high porosity. Moreover, the intensity
- porous aluminum can be improved by adding aluminum alloy powder or additive element powder as aluminum powder to alloy aluminum and further contain an intermetallic compound of aluminum and another metal. And by such a manufacturing method, the porous aluminum which does not have a restriction
- Porous aluminum The porous aluminum produced according to the present invention is obtained by pressure-molding a mixed powder of an aluminum powder and a support powder mixed at a predetermined volume ratio, and then pressing the pressure-molded body in an inert atmosphere. It is obtained by sintering by heat treatment and finally removing the supporting powder. Further, the mixed powder may be combined with a metal plate. Porous aluminum is composed of voids from which the support powder has been removed and bonded metal powder walls of sintered aluminum powder that form the periphery of the voids. Many fine holes are formed in the bonded metal powder wall. Porous aluminum has an open cell structure in which voids are connected by these micropores.
- (B) Aluminum powder Pure aluminum powder, aluminum alloy powder, or a mixture thereof is used for the aluminum powder used in the present invention.
- the alloy components cause corrosion resistance deterioration under the usage environment, it is preferable to use pure aluminum powder.
- Pure aluminum is aluminum having a purity of 99.0 mass% or more.
- aluminum alloy powder or a mixture of this and pure aluminum powder.
- the aluminum alloy 1000 series, 2000 series, 3000 series, 4000 series, 5000 series, 6000 series, and 7000 series aluminum alloys are used.
- the particle size of the aluminum powder is preferably 1 to 50 ⁇ m. In order to uniformly cover the surface of the support powder with the aluminum powder in the production of porous aluminum, the particle size of the aluminum powder is preferably smaller, and more preferably 1 to 10 ⁇ m.
- the particle diameter of the aluminum powder is defined by the median diameter measured by the laser diffraction scattering method (microtrack method).
- the aluminum powder may be a mixture obtained by adding an additive element powder to pure aluminum powder.
- an additive element a plurality of elements composed of a single element selected from magnesium, silicon, titanium, iron, nickel, copper, zinc and the like or any combination of two or more are preferably used.
- Such a mixture forms an alloy of aluminum and an additive element by heat treatment.
- an intermetallic compound of aluminum and the additive element is further formed.
- porous aluminum contains such an alloy or intermetallic compound of aluminum, various effects can be obtained in porous aluminum. For example, in an aluminum alloy of aluminum and an additive element such as silicon or copper, the melting point of the aluminum powder is lowered, and the temperature required for the heat treatment can be lowered.
- porous aluminum As a result, energy required for production can be reduced, and the strength of porous aluminum can be improved by alloying.
- an intermetallic compound of aluminum and an additive element such as nickel when an intermetallic compound of aluminum and an additive element such as nickel is formed, heat is generated during the formation to promote sintering, and a structure in which the intermetallic compound is dispersed is formed. The strength of the porous aluminum can be increased.
- the aluminum powder may be an aluminum alloy powder added with additive element powder, or a mixture of aluminum alloy powder and pure aluminum powder with additive element powder added. In these cases, new alloy systems and intermetallic compounds are formed. Furthermore, an additive element alloy powder obtained by alloying a plurality of additive element powders may be used as the additive element powder.
- the addition amount of the additive element powder or additive element alloy powder to the aluminum alloy powder or pure aluminum powder is appropriately determined based on the chemical formula amount of the alloy or intermetallic compound to be formed.
- the particle diameter of the additive element powder is preferably 1 to 50 ⁇ m.
- the additive element powder preferably has a finer particle size.
- the additive element powder one having a particle size smaller than at least the particle size of the supporting powder is used.
- the particle size of the additive element powder is defined by the median diameter measured by the laser diffraction scattering method (microtrack method) in the same manner as the aluminum powder.
- Support powder In the present invention, the support powder does not react with the aluminum powder in the process from mixing to removal of the support powder, and is dissolved or decomposed from the object to be processed after becoming a pressure molded body. Those that can be easily removed are used.
- Such support powders include sodium chloride, ammonium chloride, calcium chloride, magnesium chloride, aluminum chloride, potassium chloride, nickel chloride, zinc chloride, ammonium bicarbonate, sodium hydrogen phosphate, sodium dihydrogen phosphate, diphosphate phosphate.
- Inorganic salts such as potassium hydrogen, potassium hydrogen phosphate, potassium hydrogen phosphite, potassium phosphate, magnesium sulfate, potassium sulfate and alkaline earth metal halides; sucrose classified as monosaccharide, disaccharide or trisaccharide, Crystalline carbohydrates such as lactose; organic polymer compounds such as polyvinyl alcohol, polyethylene oxide, polypropylene wax, sodium carboxymethyl cellulose; Of these, water-soluble inorganic salts are preferred. Sodium chloride and potassium chloride are particularly preferred from the standpoint of availability and handling. Since the space formed by removing the support powder becomes pores of porous aluminum, the particle size of the support powder is reflected in the pore diameter.
- the particle size of the support powder used in the present invention is preferably 10 to 1000 ⁇ m.
- the particle size of the support powder is defined by the opening of the sieve. Accordingly, porous aluminum having a uniform pore diameter can be obtained by making the particle diameter of the support powder uniform by classification.
- the metal plate is a non-porous plate or foil; and a net-like body such as a perforated wire mesh, expanded metal, or punching metal.
- the metal plate serves as a support, and the strength of the porous aluminum is improved and the conductivity is further improved.
- a material that does not evaporate or decompose during heat treatment specifically, a metal such as aluminum, titanium, iron, nickel, copper, SUS, or an alloy thereof can be suitably used.
- aluminum or SUS can be suitably used when used as an electrode for a lithium ion battery or the like.
- the composite of the mixed powder and the metal plate refers to an integrated state in which, for example, when a metal mesh is used for the metal plate, the entire net is covered with the mixed powder while filling the mixed powder in the mesh.
- a porous aluminum having a metal powder wall is provided on both sides of a metal plate and filled with, for example, a catalyst or an active material
- the metal plate is a perforated network, one of the porous plates separated by the metal plate If a catalyst and an active material are filled from aluminum, these can be filled to the other porous aluminum. Therefore, the metal plate is preferably a net-like body.
- the perforated means a mesh part of a metal mesh, a punch part of a punching metal, a mesh part of an expanded metal, and a gap part between fibers of metal fibers.
- the pore diameter of the pores of the network may be larger or smaller than the diameter of the holes obtained by removing the support powder from the joined mixed powder. It is preferable that the aperture ratio of the pores of the network is large so as not to impair the porosity of the porous aluminum.
- the mixing ratio of the aluminum powder and the support powder is such that Val / (Val + Vs), which is the volume ratio of the aluminum powder, is 5 to 30%, preferably 5 to 25%.
- the volumes Val and Vs are values obtained from the respective weights and specific gravity.
- the volume ratio of the aluminum powder exceeds 30%, the support powder content is too small, so the support powders exist independently without contacting each other, and the support powder cannot be removed sufficiently. . Support powder that cannot be removed causes corrosion of porous aluminum.
- the volume ratio of the aluminum powder is less than 5%, the wall constituting the porous aluminum becomes too thin, so that the strength of the porous aluminum becomes insufficient, and handling and shape maintenance become difficult.
- the aluminum powder has a sufficiently small particle size compared to the support powder (the dal / ds is 0.1 using dal and ds described later). It is preferable that the following is preferable.
- the coverage area ratio C (%) of the surface of the support powder covered with the aluminum powder represented by (Val ⁇ ds) / (4Vs ⁇ dal) ⁇ 100 70% or more, more preferably 100% or more and 4000% or less, and such dal, ds, Val, and Vs are selected.
- the additive powder is not included in the aluminum powder when calculating the covering area ratio C.
- the upper limit value of the particle size of the usable aluminum powder can be obtained. Is possible. That is, when ds, Vs, and Val are determined, aluminum is usable from dal ⁇ ⁇ (Val ⁇ ds) / (4Vs) ⁇ ⁇ ⁇ 100/70 ⁇ by obtaining dal so that C is 70% or more. The upper limit of the particle size of the powder can be determined.
- C (Va1 ⁇ ds) / (4Vs ⁇ da1) ⁇ 100 is less than 70%, the support powder is not sufficiently covered with the aluminum powder, and the connection between the aluminum powders is easily interrupted in the pressure-molded state. Become. As a result, at the time of heat treatment, the powder phase is not connected by the liquid phase of the aluminum powder, and it is difficult for the powder to be bonded. Thereby, there is a possibility that the bonding frequency between the aluminum powders is lowered, the strength of the porous aluminum is lowered, and the bonded metal powder wall is collapsed when the supporting powder is removed. Therefore, C is preferably 70% or more.
- C is 70% or more and less than 100%, C is not less than 70%, but the bonding frequency between aluminum powders tends to be low. Furthermore, when C exceeds 4000%, the supporting powder tends to remain in the porous aluminum. For example, when sodium chloride is used as the support powder, there is a possibility that the remaining sodium chloride causes corrosion of porous aluminum. Therefore, C is more preferably 100 to 4000%.
- a vibration agitator for mixing aluminum with the supporting powder
- a container rotating mixer for mixing aluminum with the supporting powder
- a vibration agitator for mixing aluminum with the supporting powder
- a container rotating mixer for mixing aluminum with the supporting powder
- (G) Compounding method As a compounding method, a method of compounding the mixed powder and the metal plate when the mixed powder is filled in a molding die is used. As a composite form, a metal plate may be sandwiched between mixed powders, or a mixed powder may be sandwiched between metal plates. Further, the composite of the mixed powder and the metal plate can be repeated to make multiple stages. In the case of compounding, mixed powders having different particle sizes and mixing ratios of aluminum powder and support powder, and a plurality of different types of metal plates can be combined.
- the pressure at the time of pressure molding needs to be 200 MPa or more.
- the aluminum powders rub against each other, and the strong oxide film on the surface of the aluminum powder that inhibits the sintering of the aluminum powders is destroyed.
- This oxide film traps molten aluminum and prevents molten aluminum from contacting each other.
- this oxide film is inferior in wettability with molten aluminum and has the action of rejecting liquid aluminum. Therefore, when the pressure of pressure molding is less than 200 MPa, the destruction of the oxide film on the surface of the aluminum powder becomes insufficient, and the aluminum melted during heating oozes out of the molded body to form a ball-shaped aluminum lump. .
- the porosity of the porous aluminum is considerably higher than the desired value due to the formation of the aluminum lump, and the molten aluminum flows out, leading to a decrease in strength. Therefore, the formation of such an aluminum lump is detrimental in that the porosity of the porous aluminum cannot be controlled. In addition, there is a problem in that the shape collapses due to the formation of an aluminum lump and must be removed. Since the porous aluminum wall formed by a larger molding pressure becomes stronger, it is preferable to increase the molding pressure as long as the apparatus and mold used allow it. However, when the molding pressure exceeds 400 MPa, the effect tends to be saturated.
- a lubricant such as a fatty acid such as stearic acid, a metal soap such as zinc stearate, various waxes, synthetic resins, and olefinic synthetic hydrocarbons.
- the heat treatment is performed at a temperature not lower than the melting point of the aluminum powder to be used and lower than 700 ° C.
- the melting point of the aluminum powder is a temperature at which a liquid phase of pure aluminum or an aluminum alloy is generated.
- the melting point of the aluminum alloy having the lowest melting point is set.
- the melting point of the aluminum powder when the additive element powder is further added to the pure aluminum powder, the aluminum alloy powder or a mixture thereof, in the system in which the melting point is lowered by alloying during the heat treatment due to the presence of the additive element powder The temperature at which the liquid phase occurs in the system is taken as the melting point.
- the eutectic temperature at which the liquid phase is generated in this system is 577 ° C .
- the eutectic temperature at which the liquid phase is generated in this system is 548 ° C. as the melting point.
- the heat treatment temperature is lower than the above melting point, the aluminum does not melt, so the aluminum powder does not melt, and in the case of compounding, the bond between the aluminum powder and the metal plate becomes insufficient. Moreover, when heated above the melting point, the aluminum covering the surface of the support powder located on the outermost surface of the sintered body is removed, and a sintered body having a surface with a large aperture ratio can be formed reliably.
- the aperture ratio of the sintered body is large, for example, it is advantageous to fill the active material when porous aluminum is applied to the current collector.
- the heat treatment temperature is lower than the melting point of aluminum, it is difficult to obtain a sintered body having a surface with a large aperture ratio.
- the heat treatment is performed at a temperature of less than 700 ° C, preferably less than 680 ° C.
- the heat treatment temperature is 700 ° C. or higher, the viscosity of the molten aluminum decreases, the molten aluminum oozes out to the outside of the pressure-formed body, and a convex aluminum lump is formed.
- the porosity of the porous aluminum is considerably higher than a desired value due to the formation of the aluminum lump, and the molten aluminum flows out, leading to a decrease in strength.
- the formation of such an aluminum lump is detrimental in that the porosity of porous aluminum cannot be controlled.
- the heat holding time in the heat treatment is preferably about 1 to 60 minutes.
- a load may be applied to the pressure formed body during the heat treatment to compress the pressure formed body, and heating and cooling may be repeated a plurality of times.
- the heat treatment is performed in an inert atmosphere.
- an atmosphere of vacuum nitrogen, argon, hydrogen, decomposed ammonia and a mixed gas thereof is preferably used, and a vacuum atmosphere is preferable.
- the vacuum atmosphere is preferably an atmosphere reduced in pressure to 2 ⁇ 10 ⁇ 2 Pa or less, more preferably 1 ⁇ 10 ⁇ 2 Pa or less. When it exceeds 2 ⁇ 10 ⁇ 2 Pa, the moisture adsorbed on the surface of the aluminum powder is not sufficiently removed, and the oxidation of the aluminum surface proceeds during the heat treatment.
- the oxide film formed on the aluminum surface by the progress of such oxidation is inferior in wettability with the liquid aluminum, so that the molten aluminum oozes out to form a ball-like lump, causing a harmful effect.
- an inert gas atmosphere such as nitrogen, it is preferable that the oxygen concentration is 1000 ppm or less and the dew point is ⁇ 30 ° C. or less.
- the support powder in the sintered body is preferably removed by eluting the support powder into water.
- the supporting powder can be easily eluted by a method such as immersing the sintered body in a sufficient amount of water bath or flowing water bath.
- the water that elutes it is preferably water with few impurities, such as ion exchange water or distilled water, but there is no particular problem with tap water.
- the immersion time is usually appropriately selected within the range of several hours to 24 hours.
- Elution of the supporting powder can be promoted by applying vibration to the sintered body being immersed by ultrasonic waves or the like.
- Example 1 Invention Examples 1 to 18 and Comparative Examples 1 to 5>
- the aluminum powder the following pure aluminum powders (A1, A2, A6), alloy powders (A4), and powders (A5) in which A1 and A4 were mixed at a weight ratio of 4: 1 were used.
- As support powders sodium chloride powders (B1 to B3) having different particle diameters and potassium chloride powder (C1) having a particle diameter of 605 ⁇ m were used. The support powder was classified to obtain the median particle size of sieve openings shown below, and the particle size was made uniform.
- pure aluminum powder and support powder were mixed at a predetermined volume ratio to prepare a mixed powder.
- This mixed powder was filled in a mold having a 12 mm ⁇ 30 mm hole, and pressure-molded at the pressure shown in Tables 1 and 2.
- the filling amount of the mixture was set to a weight at which the thickness of the pressure-molded body was 1 mm.
- a sintered body was produced by heat-treating the pressure-molded body at a temperature and time shown in Tables 1 and 2 in an atmosphere having a maximum ultimate pressure of 1 ⁇ 10 ⁇ 2 Pa or less.
- the obtained sintered body was immersed in flowing water (tap water) at 20 ° C. for 6 hours to elute the supporting powder, thereby preparing a porous aluminum sample (width 12 mm ⁇ length 30 mm ⁇ thickness 1 mm).
- the total of the sodium content and the potassium content is less than 0.1% by mass as pass ( ⁇ ), and the sum of 0.1% and less than 0.5% is also acceptable ( ⁇ ) And 0.5% or more were rejected (x).
- the load roller 1 when the load roller 1 was further lowered by 2 mm from the point where the maximum load was reached, the load was 60% or more of the maximum load ( ⁇ ), and the load was 50% or more and less than 60% ( (Triangle
- the descending speed of the load roller 1 was 1 mm / min.
- Example 2 (Example 2 ⁇ Invention Examples 19 to 22 and Comparative Examples 6 to 10>) A1 to A3 were used as the aluminum powder, and B2 was used as the support powder. Further, precision expanded metal (4AL8-4 / 0) manufactured by Taiyo Wire Mesh Co., Ltd. was used as the metal plate. As shown in Tables 3 and 4, pure aluminum powder and support powder were mixed at a predetermined volume ratio to prepare a mixed powder. In Invention Examples 19 and 21, this mixed powder is filled in a mold having a 12 mm ⁇ 30 mm hole, and is placed so that the metal plate is positioned in the center in the thickness direction of the mixed powder, and the mixed powder and the metal plate are combined. Turned into.
- Invention Examples 19 to 22 passed all evaluations. Inventive Examples 19 and 21 were improved in strength compared to Inventive Examples 20 and 22 in which no expanded metal was combined.
- Comparative Example 6 since the volume ratio of the aluminum powder was small, there were many portions where the contact between the aluminum powders was interrupted, and the shape was not acceptable. In Comparative Example 7, some sodium chloride (support powder) existed independently because the volume ratio of the aluminum powder was too large, and the support powder persistence was not possible because this independent support powder could not come into contact with water. It was a failure. In Comparative Example 8, since the pressure forming pressure was too low, the exposure of the new surface of the aluminum powder was insufficient, and the molten aluminum oozed out during the heat treatment and the appearance was unacceptable. In Comparative Example 9, since the heat treatment temperature was too high, the molten aluminum oozed out and the appearance was unacceptable. In Comparative Example 10, since the heat treatment temperature was lower than the melting points of the aluminum powder and the expanded metal, the sintering did not proceed, and separation occurred at the portion where the expanded metal was sandwiched during the maximum load measurement, and the load measurement could not be performed.
- Example 3 (Example 3 ⁇ Invention Examples 23 to 26 and Comparative Examples 11 to 15>) A1, A2, A4 and A5 were used as the aluminum powder, and B1 and B2 were used as the supporting powder. Further, the following D1 and D2 were used as additive element powders. Each powder was mixed as shown in Tables 5 and 6 to prepare a mixed powder. This mixture was filled in a mold having 12 mm ⁇ 30 mm holes, and pressure-molded with the pressures shown in Tables 5 and 6. The filling amount of the mixture was set to a weight at which the thickness of the pressure-molded body was 1 mm.
- a sintered body was produced by heat-treating the pressure-molded body at a temperature and time shown in Tables 5 and 6 in an atmosphere having a maximum ultimate pressure of 1 ⁇ 10 ⁇ 2 Pa or less.
- the obtained sintered body was immersed in flowing water (tap water) at 20 ° C. for 6 hours to elute the supporting powder, thereby preparing a porous aluminum sample (width 12 mm ⁇ length 30 mm ⁇ thickness 1 mm).
- Example 2 The same evaluation as in Example 1 was performed using the porous aluminum sample produced as described above. The evaluation results are shown in Tables 5 and 6.
- Comparative Example 11 since the volume ratio of the aluminum powder was small, there were many portions where contact between the aluminum powders was interrupted, and the shape was not acceptable. In Comparative Example 12, some sodium chloride (supporting powder) existed independently because the volume ratio of the aluminum powder was too large, and the support powder persistence was not possible because this independent supporting powder could not contact with water. It was a failure. In Comparative Example 13, since the pressure forming pressure was too low, the exposure of the new surface of the aluminum powder was insufficient, and the molten aluminum oozed out during heat treatment, resulting in an unacceptable appearance. In Comparative Example 14, since the heat treatment temperature was too high, the molten aluminum oozed out and the appearance was unacceptable. In Comparative Example 15, since the heat treatment temperature was lower than the eutectic temperature of aluminum and silicon, the sintering did not proceed, and the load maintainability was unacceptable.
- the present invention it is possible to provide a porous aluminum having a high porosity and a uniform pore size, which is suitable for a current collector of a lithium ion secondary battery, various filters, a single catalyst, a heat exchanger, sound absorption, and the like. Furthermore, the present invention makes it possible to produce porous aluminum that is basically unlimited in size.
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Abstract
Description
本発明によって製造される多孔質アルミニウムは、所定の体積割合で混合したアルミニウム粉末と支持粉末の混合粉末を加圧成形した後に、その加圧成形体を不活性雰囲気中で熱処理して焼結し、最終的に支持粉末を除去することで得られる。また、混合粉末を金属板と複合化してもよい。多孔質アルミニウムは、支持粉末が除去された空隙と、その空隙の周囲を形成する焼結したアルミニウム粉末の結合金属粉末壁とによって構成される。結合金属粉末壁には、多くの微細な孔が形成されている。多孔質アルミニウムは、空隙同士がこれら微細孔によって連結されたオープンセル型の構造を有する。
本発明で用いるアルミニウム粉末には、純アルミニウム粉末、アルミニウム合金粉末又はこれらの混合物が用いられる。使用環境下において合金成分が耐食性劣化の原因となるような場合には、純アルミニウム粉末を用いるのが好ましい。純アルミニウムとは、純度99.0mass%以上のアルミニウムである。
アルミニウム粉末は、純アルミニウム粉末に添加元素粉末を加えた混合物でもよい。このような添加元素には、マグネシウム、珪素、チタン、鉄、ニッケル、銅及び亜鉛等から選択される単独又は二以上の任意の組み合わせからなる複数の元素が好適に用いられる。このような混合物は、熱処理によりアルミニウムと添加元素との合金を形成する。また、添加元素の種類によっては、アルミニウムと添加元素との金属間化合物が更に形成される。多孔質アルミニウムが、このようなアルミニウムの合金や金属間化合物を含有することにより、多孔質アルミニウムにおいて様々な効果が得られる。例えば、珪素や銅などの添加元素とアルミニウムとのアルミニウム合金では、アルミニウム粉末の融点が低下し、熱処理に必要な温度を下げることができる。その結果、製造に必要なエネルギーを削減できると共に、合金化によって多孔質アルミニウムの強度を向上させることができる。また、アルミニウムとニッケルなどの添加元素との金属間化合物が形成される場合は、形成の際に発熱が起こって焼結が促進されると共に、金属間化合物が分散した組織が形成されることで多孔質アルミニウムの高強度化が図られる。
また、添加元素粉末の粒径は、1~50μmが好ましい。純アルミニウム粉末、アルミニウム合金粉末、支持粉末との十分な混合を図るために、添加元素粉末の粒径は、より微細であるのが好ましい。添加元素粉末は、その粒径が少なくとも支持粉末の粒径よりも小さいものが用いられる。添加元素粉末の粒径は、アルミニウム粉末と同様にレーザー回折散乱法(マイクロトラック法)で測定したメジアン径で規定される。
本発明では支持粉末としては、混合から支持粉末の除去に至る工程でアルミニウム粉末と反応することが無く、かつ、加圧成形体となる以後の被処理体から溶解や分解によって容易に除去可能なものが用いられる。このような支持粉末としては、塩化ナトリウム、塩化アンモニウム、塩化カルシウム、塩化マグネシウム、塩化アルミニウム、塩化カリウム、塩化ニッケル、塩化亜鉛、重炭酸アンモニウム、リン酸水素ナトリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、リン酸水素カリウム、亜リン酸水素カリウム、リン酸カリウム、硫酸マグネシウム、硫酸カリウム及びアルカリ土類金属のハロゲン化物などの無機塩;単糖類、二糖類または三糖類として分類されるスクロース、ラクトースなどの結晶性炭水化物;ポリビニルアルコール、ポリエチレンオキシド、ポリプロピレンワックス、カルボキシメチルセルロースナトリウムなどの有機高分子化合物;が用いられる。これらのうち、水溶性の無機塩が好ましい。入手や取り扱いの容易性から、塩化ナトリウムと塩化カリウムが特に好ましい。支持粉末が除去されることにより形成される空間が多孔質アルミニウムの孔になることから、支持粉末の粒径が孔径に反映される。そこで、本発明で用いる支持粉末の粒径は、10~1000μmとするのが好ましい。支持粉末の粒径は、ふるいの目開きで規定される。従って、分級によって支持粉末の粒径を揃えることで、孔径の揃った多孔質アルミニウムが得られる。
本発明においては、混合粉末を金属板と複合化した状態で用いてもよい。金属板とは無孔の板や箔;及び、有孔の金網、エキスパンドメタル、パンチングメタル等の網状体;である。金属板が支持体となり多孔質アルミニウムの強度が向上し、更に導電性が向上する。金属板としては熱処理時に蒸発又は分解しない素材、具体的にはアルミニウム、チタン、鉄、ニッケル、銅、SUS等の金属やその合金製のものが好適に利用できる。特にリチウムイオン電池等の電極用途として用いる場合には、アルミニウム、SUSを好適に用いることができる。
網状体の有孔の孔径は、接合した混合粉末から支持粉末を除去して得られる孔の径より大きくても、小さくてもよい。
網状体の有孔の開口率は、多孔質アルミニウムの気孔率を損なわないためにも大きい方が好ましい。
アルミニウム粉末と支持粉末の混合割合は、それぞれの体積をVal、Vsとしてアルミニウム粉末の体積率であるVal/(Val+Vs)が5~30%、好ましくは5~25%である。ここで体積Val、Vsはそれぞれの重量と比重から求めた値である。アルミニウム粉末の体積率が30%を超える場合には、支持粉末の含有率が少な過ぎるために支持粉末同士が接触することなく独立して存在することになり、支持粉末を十分に除去しきれない。除去しきれない支持粉末は、多孔質アルミニウムの腐食の原因となる。一方、アルミニウム粉末の体積率が5%未満の場合には、多孔質アルミニウムを構成する壁が薄くなり過ぎることで、多孔質アルミニウムの強度が不十分となり、取り扱いや形状維持が困難となる。
また、支持粉末をアルミニウム粉末で十分に覆われた状態を達成するために、アルミニウム粉末が支持粉末に比べて十分に小さな粒径(後述のdal、dsを用いて、dal/dsが0.1以下であることが好ましい)を有している必要がある。
また、Cが70%以上100%未満の場合には、Cが70%未満程ではないが、アルミニウム粉末間の結合頻度が低くなる傾向がある。更に、Cが4000%を超える場合には、多孔質アルミニウムに支持粉末が残留し易くなる。例えば、支持粉末として塩化ナトリウムを用いた場合には、残留した塩化ナトリウムが多孔質アルミニウムの腐食の原因になるといった不具合が生じる可能性がある。従って、Cを100~4000%とするのが更に好ましい。
複合化方法としては、混合粉末を成形用金型に充填する際に、混合粉末と金属板とを複合化する方法が用いられる。複合化の形態としては、混合粉末の間に金属板を挟んでもよく、混合粉末を金属板で挟んでもよい。また、混合粉末と金属板の複合化を繰り返して多段にすることもできる。複合化の際にはアルミニウム粉末や支持粉末の粒径、混合割合の異なる混合粉末や、種類の異なる複数の金属板を組み合わせることもできる。
加圧成形時の圧力は、200MPa以上とする必要がある。十分な圧力を加えて成形することでアルミニウム粉末同士が擦れ合い、アルミニウム粉末同士の焼結を阻害するアルミニウム粉末表面の強固な酸化皮膜が破壊される。この酸化皮膜は融解したアルミニウムを閉じ込め、融解アルミニウム同士が互いに接触することを妨げる。更に、この酸化皮膜は融解アルミニウムとの濡れ性に劣り、液体状のアルミニウムを排斥する作用を有する。そのため、加圧成形の圧力が200MPa未満の場合にはアルミニウム粉末表面の酸化皮膜の破壊が不十分となり、加熱時に融解したアルミニウムが成形体の外に滲み出して玉状のアルミニウム塊が形成される。アルミニウム塊が形成されたことで多孔質アルミニウムの気孔率は所望の値よりもかなり高くなると共に、融解したアルミニウムが流れ出すことで強度の低下に繋がる。従って、このようなアルミニウムの塊の形成は、多孔質アルミニウムの気孔率が制御できなくなってしまう点で弊害となる。また、アルミニウム塊の形成によって形状が崩れ、これを除去しなければならなくなる点でも問題となる。より大きな成形圧力によって形成される多孔質アルミニウム壁はより強固になるので、使用する装置や金型が許容する限り成形圧力を大きくするのが好ましい。しかしながら、成形圧力が400MPaを超えると効果が飽和する傾向がある。なお、加圧成形体の離型性を高める目的で、ステアリン酸等の脂肪酸、ステアリン酸亜鉛等の金属石鹸、各種ワックス、合成樹脂、オレフィン系合成炭化水素等の潤滑剤を使用することが好ましい。
熱処理は、使用するアルミニウム粉末の融点以上で、かつ、700℃未満の温度で行われる。アルミニウム粉末の融点とは、純アルミニウム又はアルミニウム合金の液相が生じる温度である。複数種のアルミニウム合金粉末を混合して使用する場合には、最も融点の低いアルミニウム合金の融点とする。また、純アルミニウム粉末、アルミニウム合金粉末又はこれらの混合物に、添加元素粉末を更に添加する場合におけるアルミニウム粉末の融点については、添加元素粉末の存在により熱処理時に合金化して融点が低下する系では、その系において液相が生じる温度を融点とする。例えば、純アルミニウム粉末に添加元素粉末として珪素粉末を添加した系では、この系で液相が生じる共晶温度577℃を融点とする。また、純アルミニウム粉末に添加元素粉末として銅粉末を添加した系では、この系で液相が生じる共晶温度548℃を融点とする。液相が生じる温度まで加熱することで、アルミニウム粉末から液相が滲み出し、液相同士が接触することでアルミニウム粉末同士が金属的に結合する。
焼結体中の支持粉末の除去は、支持粉末を水に溶出させて行う方法が好適に用いられる。焼結体を十分な量の水浴または流水浴に浸漬する等の方法により、支持粉末を容易に溶出することができる。支持粉末として水溶性塩を用いる場合には、これを溶出させる水は、イオン交換水や蒸留水等、不純物の少ないものが好ましいが、水道水でも特に問題は無い。浸漬時間は、通常、数時間~24時間程度の範囲で適宜選択される。浸漬中の焼結体に超音波等によって振動を与えることにより、支持粉末の溶出を促進することができる。
アルミニウム粉末として、粒径の異なる下記純アルミニウム粉末(A1、A2、A6)、合金粉末(A4)、およびA1とA4を重量比で4:1で混合した粉末(A5)を用いた。支持粉末として、粒径の異なる塩化ナトリウム粉末(B1~B3)、ならびに、粒径605μmの塩化カリウム粉末(C1)を用いた。なお、支持粉末については、下記に示すふるい目開き中央値の粒径が得られるように分級して粒径を揃えた。表1及び2に示すように、純アルミニウム粉末と支持粉末を所定の体積割合で混合し、混合粉末を調製した。この混合粉末を12mm×30mmの穴を有する金型に充填し、表1、2に示す圧力で加圧成形した。混合物の充填量は加圧成形体の厚さが1mmとなる重量とした。この加圧成形体を最大到達圧力が1×10-2Pa以下の雰囲気下において表1、2に示す温度と時間で熱処理することで焼結体を作製した。得られた焼結体を20℃の流水(水道水)中に6時間浸漬して支持粉末を溶出させ、多孔質アルミニウム試料(幅12mm×長さ30mm×厚さ1mm)を作製した。
A1:メジアン径3μm(融点:660℃)
A2:メジアン径7μm(融点:660℃)
A3:メジアン径17μm(融点:660℃)
A6:メジアン径1μm(融点:660℃)
A4:Al-7.5%Si-1%Mg、メジアン径27μm(融点:557℃)
A5:A1(融点:660℃)とA4(融点:557℃)を重量比4:1で混合した粉末、メジアン径8μm
B1:粒径605μm(ふるい目開き中央値)(融点:800℃)
B2:粒径400μm(ふるい目開き中央値)(融点:800℃)
B3:粒径120μm(ふるい目開き中央値)(融点:800℃)
<塩化カリウム粉末>
C1:粒径605μm(ふるい目開き中央値)(融点:776℃)
(支持粉末の残留性)
ICP-AES(誘導結合プラズマ発光分光分析法)を用いて、塩酸に溶解した多孔質アルミニウム試料中のナトリウム、カリウムの含有量を測定した。支持粉末が塩化ナトリウム単独の場合はナトリウム含有量を、支持粉末が塩化カリウム単独の場合はカリウム含有量を、支持粉末が塩化ナトリウムと塩化カリウムの混合系の場合は、ナトリウム含有量とカリウム含有量を測定した。単独の場合は、ナトリウム含有量又はカリウム含有量が、0.1質量%未満のものを合格(○)とし、0.1%以上0.5%未満のものも合格(△)とし、0.5%以上ものは不合格(×)とした。一方、混合系の場合は、ナトリウム含有量とカリウム含有量の合計が、0.1質量%未満のものを合格(○)とし、0.1%以上0.5%未満のものも合格(△)とし、0.5%以上ものは不合格(×)とした。
熱処理時において、融解したアルミニウムの滲み出しの有無を目視観察により評価した。滲み出しが生じなかったものを合格(○)、生じたものを不合格(×)とした。
焼結体から支持粉末を除去した際に結合金属粉末壁が崩壊したか否かを、多孔質アルミニウム試料の形状変化の目視観察により評価した。多孔質アルミニウム試料の形状が変化しなかったものを合格(○)、変化したものを不合格(×)とた。
上記支持粉末の残留性、外観性及び形状性の評価に合格した多孔質アルミニウム試料に対し、図1に示す強度測定用治具を用いてその荷重維持性を調べた。図に示すように、支持用ローラ2、2(ローラ間の長さL=25.0±0.2mm)上に載置した多孔質アルミニウム試料3の上から荷重用ローラ1を押し付けて、この荷重用ローラ1を一定速度で降下させた際の荷重を測定した。折れ易い試料は、荷重が最大値に達した後に急激に荷重が低下する。そこで、最大荷重に達した点から更に荷重用ローラ1を2mm降下させた時点における荷重が最大荷重の60%以上だったものを合格(○)、50%以上60%未満だったものを合格(△)、50%未満であったものを不合格(×)とした。荷重用ローラ1の降下速度は1mm/minとした。
比較例2では、アルミニウム粉末の体積割合が少な過ぎたために多孔質アルミニウムの結合金属粉末壁が非常に薄くなって崩壊し、形状性が不合格であった。
比較例3では、加圧成形圧力が低過ぎたためにアルミニウム粉末の新生面の露出が不十分となり、熱処理時に融解アルミニウムの滲み出しが生じて外観性が不合格であった。
比較例4では、熱処理温度が低過ぎたため焼結が十分に進行せず、荷重維持性が不合格であった。
比較例5では、熱処理温度が高過ぎたために、融解アルミニウムの滲み出しが生じて外観性が不合格であった。
アルミニウム粉末として上記A1~A3を、支持粉末としてB2を用いた。また、金属板として太陽金網株式会社製精密エキスパンドメタル(4AL8-4/0)を用いた。表3、4に示すように、純アルミニウム粉末と支持粉末を所定の体積割合で混合し、混合粉末を調製した。発明例19、21では、この混合粉末を12mm×30mmの穴を有する金型に充填し、混合粉末の厚さ方向の中央に金属板が位置するように配置して混合粉末と金属板を複合化した。一方、発明例20、22では、混合粉末のみで精密エキスパンドメタルを用いなかった。表3、4に示す圧力で加圧成形した。混合物の充填量は加圧成形体の厚さが1mmとなる重量とした。この加圧成形体を最高到達圧力が1×10-2Pa以下の減圧雰囲気下において表3、4に示す温度と時間で熱処理することで焼結体を作製した。得られた焼結体を20℃の流水(水道水)中に6時間浸漬して支持粉末を溶出させ、多孔質アルミニウム試料(幅12mm×長さ30mm×厚さ1mm)を作製した。
比較例7では、アルミニウム粉末の体積割合が多過ぎたために一部の塩化ナトリウム(支持粉末)が独立して存在し、この独立した支持粉末が水と接触できなかったために支持粉末の残留性が不合格であった。
比較例8では、加圧成形圧力が低過ぎたためにアルミニウム粉末の新生面の露出が不十分となり、熱処理時に融解アルミニウムの滲み出しが生じて外観性が不合格であった。
比較例9では、熱処理温度が高過ぎたために、融解アルミニウムの滲み出しが生じて外観性が不合格であった。
比較例10では、熱処理温度がアルミニウム粉末およびエキスパンドメタルの融点より低かったために焼結が進行せず、最大荷重測定時にエキスパンドメタルが挟まった部分で分離し、荷重測定ができなかった。
アルミニウム粉末として上記A1、A2、A4、A5を、支持粉末としてB1、B2を用いた。また、添加元素粉末として下記D1、D2を用いた。表5及び6に示すように各粉末を混合し、混合粉末を調製した。この混合物を12mm×30mmの穴を有する金型に充填し、表5及び表6に示す圧力で加圧成形した。混合物の充填量は加圧成形体の厚さが1mmとなる重量とした。この加圧成形体を最高到達圧力が1×10-2Pa以下の雰囲気下において表5、6に示す温度と時間で熱処理することで焼結体を作製した。得られた焼結体を20℃の流水(水道水)中に6時間浸漬して支持粉末を溶出させ、多孔質アルミニウム試料(幅12mm×長さ30mm×厚さ1mm)を作製した。
D1:珪素、メジアン径5μm
D2:銅、メジアン径5μm
比較例12では、アルミニウム粉末の体積割合が多過ぎたために一部の塩化ナトリウム(支持粉末)が独立して存在し、この独立した支持粉末が水と接触できなかったために支持粉末の残留性が不合格であった。
比較例13では、加圧成形圧力が低過ぎたためにアルミニウム粉末の新生面の露出が不十分となり、熱処理時に融解アルミニウムの滲み出しが生じて外観性が不合格であった。
比較例14では、熱処理温度が高過ぎたために、融解アルミニウムの滲み出しが生じて外観性が不合格であった。
比較例15では、熱処理温度がアルミニウムと珪素の共晶温度より低かったために焼結が進行せず、荷重維持性が不合格であった。
2・・支持用ローラ
3・・多孔質アルミニウム試料
L・・支持用ローラ間の長さ
Claims (6)
- アルミニウム粉末と支持粉末の混合粉末であって、当該混合粉末の全体に対するアルミニウム粉末の体積割合が5~30%の混合粉末を200MPa以上の圧力で加圧成形する工程と、加圧成形体を不活性雰囲気中でアルミニウム粉末の融点以上で、かつ、700℃未満の温度域で熱処理することにより焼結する工程と、焼結体から支持粉末を除去する工程と、を含む多孔質アルミニウムの製造方法。
- 前記混合粉末を金属板と複合化した状態で200MPa以上の圧力で加圧成形する工程と、加圧成形体を不活性雰囲気中でアルミニウム粉末の融点以上で、かつ、700℃未満の温度域で熱処理することにより焼結する工程と、焼結体から支持粉末を除去する工程と、を含む、請求項1に記載の多孔質アルミニウムの製造方法。
- 前記アルミニウム粉末の粒径と体積をそれぞれdal、Valとし、前記支持粉末の粒径と体積をそれぞれds、Vsとして規定されるアルミニウム粉末に覆われる支持粉末表面の被覆面積割合C={(Val×ds)/(4Vs×dal)}×100が70%以上である、請求項1又は2に記載の多孔質アルミニウムの製造方法。
- 前記支持粉末が、塩化ナトリウム、塩化カリウム又はこれらの混合物である、請求項1~3のいずれか一項に記載の多孔質アルミニウムの製造方法。
- 前記アルミニウム粉末が、純アルミニウム粉末とアルミニウム合金粉末の少なくとも一方を含有する、請求項1~4のいずれか一項に記載の多孔質アルミニウムの製造方法。
- 前記アルミニウム粉末が添加元素粉末を含有する、請求項5に記載の多孔質アルミニウムの製造方法。
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JP2016194117A (ja) * | 2015-03-31 | 2016-11-17 | 三菱マテリアル株式会社 | 多孔質アルミニウム焼結体、多孔質アルミニウム複合部材、多孔質アルミニウム焼結体の製造方法、多孔質アルミニウム複合部材の製造方法 |
JP2016194118A (ja) * | 2015-03-31 | 2016-11-17 | 三菱マテリアル株式会社 | 多孔質アルミニウム焼結体、多孔質アルミニウム複合部材、多孔質アルミニウム焼結体の製造方法、多孔質アルミニウム複合部材の製造方法 |
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