WO2018179976A1 - 金属粉末の製造方法 - Google Patents
金属粉末の製造方法 Download PDFInfo
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- WO2018179976A1 WO2018179976A1 PCT/JP2018/005545 JP2018005545W WO2018179976A1 WO 2018179976 A1 WO2018179976 A1 WO 2018179976A1 JP 2018005545 W JP2018005545 W JP 2018005545W WO 2018179976 A1 WO2018179976 A1 WO 2018179976A1
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- metal
- metal powder
- oxide
- powder
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 137
- 239000002184 metal Substances 0.000 title claims abstract description 137
- 239000000843 powder Substances 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 23
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- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 7
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 20
- 239000002923 metal particle Substances 0.000 abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 66
- 239000002245 particle Substances 0.000 description 33
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- 229910052759 nickel Inorganic materials 0.000 description 10
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- 239000003985 ceramic capacitor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 229930008380 camphor Natural products 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
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- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- B22F1/16—Metallic particles coated with a non-metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- 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
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/25—Oxide
Definitions
- One embodiment of the present invention relates to a method for producing a metal powder such as nickel, copper, or silver suitable for various uses such as a conductive paste filler, a titanium material bonding material, and a catalyst used in electronic parts.
- the present invention relates to a method for producing metal powder suitable for heat treatment by uniformly coating metal powder with an oxide.
- Conductive metal powders such as Ni, Cu, and Ag are useful for forming internal electrodes of multilayer ceramic capacitors.
- nickel powder has recently attracted attention in such applications.
- nickel ultrafine powder produced by a dry production method is considered promising in the above applications.
- the particle size of 0.1 ⁇ m or less is required as well as the particle size of 0.1 ⁇ m or less due to the demands for thinning the internal electrode and reducing the resistance as the capacitor becomes smaller and larger in capacity.
- ultrafine powder having a particle size of 5 ⁇ m or less, and further having a particle size of 0.3 ⁇ m or less.
- the manufacturing process of a multilayer ceramic capacitor there is a step of performing heat treatment to crystallize the dielectric layer.
- the sintering temperature of the dielectric layer is higher than the sintering temperature of the nickel powder, The temperature is excessive. Further, the sintering temperature of the nickel powder tends to decrease due to the above-described ultrafine pulverization of the nickel powder.
- the heat treatment causes the nickel powder to sinter and cause thermal shrinkage, which causes the delamination and cracks of the internal electrodes, thereby degrading the performance of the multilayer ceramic capacitor.
- Patent Document 1 describes a method of mixing a dielectric with nickel powder.
- Patent Document 2 Japanese Patent Application Laid-Open No. 11-124602 shows that an oxide or a hydroxide is generated by hydrolysis of a metal salt, and the oxide generated in the liquid is adsorbed to the metal powder. ing.
- Japanese Patent Publication “JP 2000-282102 A” (published on October 10, 2000)
- Japanese Patent Publication “Japanese Patent Laid-Open No. 11-124602” Japanese Patent Laid-Open No. 11-124602” (published on May 11, 1999)
- Patent Document 1 is a method of suppressing the sintering of the metal powder by the dielectric, but as the metal powder is atomized, it becomes difficult to mix the metal powder and the dielectric, and the metal powder and the dielectric. There is a problem that the body separates.
- Patent Document 2 has a problem that the metal powder cannot be uniformly coated because the oxide formed with a high hydrolysis rate of the metal salt forms an aggregate.
- an object of one embodiment of the present invention is to provide a method for producing an oxide-coated metal powder capable of uniformly coating metal particles with an oxide and preventing the formation of oxide aggregates. There is to do.
- the inventors of the present invention have made extensive studies on the coating of metal particles with oxides. As a result, metal alkoxide is stabilized by a complexing agent and mixed with water containing an acid or alkali to increase the surface coverage of the oxide. And the inventors have found that oxide aggregates can be prevented from being generated, and completed one embodiment of the present invention.
- one embodiment of the present invention is a manufacturing method for manufacturing a metal powder in which at least a part of a surface is coated with an oxide,
- the surface of the metal powder is mixed with an oxide generated from the metal complex by mixing a dispersion containing the metal powder and a metal complex having a ligand represented by Formula 1 and water containing an acid or an alkali. It is characterized by covering at least a part of.
- R 1 and R 2 each represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and may be the same or different from each other, and R 1 and R 2 are bonded to each other to form a ring; May be formed.
- the present invention it is possible to coat more uniformly than the conventional oxide-coated metal powder, so that the heat resistance can be increased as compared with the conventional one and oxide aggregates are formed. Can be prevented.
- FIG. 2 is a STEM photograph and an EDS mapping image of the SiO 2 coated nickel powder obtained in Example 1.
- FIG. 4 is a STEM photograph and an EDS mapping image of the TiO 2 coated nickel powder obtained in Example 2.
- FIG. 4 is a STEM photograph and an EDS mapping image of the ZrO 2 -coated nickel powder obtained in Example 3. It is a STEM photograph and EDS mapping image of the Al 2 O 3 coated nickel powder obtained in Example 4. It is a STEM photograph and EDS mapping image of La 2 O 3 coated nickel powder obtained in Example 5. It is a STEM photograph and EDS mapping image of the TiO 2 coating nickel powder obtained in Comparative Example.
- a dispersion of metal powder and water containing acid or alkali are mixed.
- the dispersion of the metal powder contains a metal alkoxide and a complexing agent.
- the surface of the metal particles is coated with an oxide obtained by hydrolyzing the metal alkoxide and the metal complex formed from the metal alkoxide and the complexing agent.
- the metal powder is an aggregate of metal particles, and the metal constituting the metal particles includes nickel, copper, silver, aluminum, titanium, iron, cobalt, tungsten, molybdenum, and alloys of these metals. Is mentioned. Among these, the metal constituting the metal particles is more preferably nickel, copper, and silver. These metal powders are suitably used for various applications such as paste fillers, titanium composites, or catalysts. For example, nickel, copper, silver, and the like are suitably used for paste fillers.
- the average particle diameter of the metal particles is not particularly limited, but is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, further preferably 0.3 ⁇ m or less, further preferably 0.2 ⁇ m or less, and further preferably 0.1 ⁇ m or less.
- the metal powder having such an average particle diameter can be suitably produced by, for example, a gas phase reduction method or a liquid phase reduction method.
- the advantage of the production method according to one aspect is that the surface of the metal particles produced by the gas phase reduction method or the liquid phase reduction method, in which the average particle size is 1 ⁇ m or less, can be uniformly coated with the oxide. It is one of.
- a metal powder having such a fine average particle diameter can form a uniform film, and the 5% shrinkage temperature and sintering temperature of the metal powder than before.
- a metal powder having high heat resistance that is, high heat resistance can be obtained. Therefore, when the metal powder is used as the internal electrode of the multilayer capacitor, it is possible to prevent the occurrence of cracks and delamination when the multilayer capacitor is fired. Since such a metal powder can be uniformly coated, it is possible to prevent the internal electrode from being short-circuited by generating a coarse metal powder due to the metal powder being connected to form a film. it can.
- “oxide-coated metal powder” which is a metal powder whose particle surface is coated with an oxide may be simply referred to as “metal powder” for convenience.
- An organic solvent may be included in the dispersion liquid in which the metal powder before being coated with the oxide is dispersed.
- the organic solvent is not particularly limited as long as it can dissolve the metal alkoxide and the complexing agent.
- alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, ethylene glycol, and propylene glycol, dioxane , Ethers such as tetrahydrofuran, 2-methoxyethanol, and diethylene glycol, and solvents such as aromatics such as toluene and xylene can be used.
- the organic solvent may be ketones such as acetone, methyl ethyl ketone, and cyclohexane, and esters such as ethyl acetate, isopropyl acetate, and butyl acetate.
- the organic solvent is more preferably an alcohol from the viewpoint of ease of handling.
- the dispersion contains a metal alkoxide.
- the metal alkoxide generates an oxide while being inhibited from being hydrolyzed by the complexing agent, and the oxide covers the surface of the metal particle.
- a metal alkoxide of the following formula 2 can be preferably used.
- M (OR 3 ) P (Formula 2) (Wherein M is one metal selected from the group consisting of Si, Ti, Zr, Al, La, Cr, and Ba, and R 3 is a linear alkyl group having 1 to 4 carbon atoms, And a branched alkyl group having 3 to 4 carbon atoms, p is determined by the type of M and is an integer of 2 to 4.)
- examples of the linear alkyl group represented by R 3 include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
- examples of the branched alkyl group having 3 to 4 carbon atoms include isopropyl group, isobutyl group, and t-butyl group.
- One type of metal alkoxide may be used, or two or more types may be used simultaneously.
- the metal alkoxide that forms a metal complex with the complexing agent is not particularly limited as long as it hydrolyzes to generate an oxide.
- a part of the metal alkoxide is included in the dispersion as an oligomer. Also good.
- the metal alkoxide is an alkyl bonded to the metal part. It preferably has no organic group such as a group and an allyl group.
- One type of metal alkoxide may be used, or two or more types may be used simultaneously.
- the metal element (metal part M) contained in the metal alkoxide may also be referred to as a coating element.
- the coating element may be the same type of metal as the metal powder, or another type of metal.
- the amount of the metal alkoxide blended in the dispersion may be adjusted as appropriate according to the amount of the metal powder dispersed in the organic solvent and the particle size of the metal powder.
- the amount of the metal powder contained is preferably 100% by weight, and preferably 0.5% by weight or more and 5% by weight or less based on the metal powder. Thereby, the metal powder whose surface coverage of the metal particle by an oxide is 80% or more and 100% or less can be manufactured suitably.
- the complexing agent slows the hydrolysis rate of the metal alkoxide by forming a metal complex with the metal part of the metal alkoxide.
- generated from a metal alkoxide and the said metal alkoxide can be made fine. Therefore, the oxide can be uniformly attached to the surface of the metal particles.
- any complexing agent can be used as long as it can coordinate to the metal part of the metal alkoxide.
- a ⁇ -diketone represented by the following formula 1 can be used. (Wherein R 1 and R 2 each represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and may be the same or different from each other, and R 1 and R 2 are bonded to each other to form a ring; May be formed.)
- R 1 and R 2 in Formula 1 are, for example, a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms. If R 1 and R 2 are the groups listed above, the hydrolysis rate of the metal alkoxide can be suitably reduced.
- the linear alkyl group of R 1, R 2 having 1 to 5 carbon atoms, a methyl group, an ethyl group, n- propyl group, n- butyl group, and n- pentyl.
- Examples of the branched alkyl group having 3 to 5 carbon atoms of R 1 and R 2 include isopropyl group, isobutyl group, t-butyl group, isopentyl group, and neopentyl group.
- R 1, R 2 is a linear alkyl - 1 carbon atoms in the case of group 3, when the branched alkyl group Preferably it has 3 carbon atoms, more preferably the complexing agent is acetylacetone.
- the amount of the complexing agent to be added is not limited, but it is preferably 1 to 3 times the total number of moles of the added metal alkoxide.
- the hydrolysis rate of the metal alkoxide is optimized. Therefore, the formation of oxide aggregates is suppressed by the fact that oxide growth does not occur rapidly. Thereby, a uniform coating of metal particles can be realized by forming fine oxides to coat the metal particles.
- the metal complex is a metal complex that forms an oxide by hydrolysis, and more specifically, the metal complex can have a structure represented by the following formula 3 or formula 4, for example.
- M 1 (OR 3 ) q X r (Formula 3)
- M 1 is one metal selected from the group consisting of Si, Ti, and Zr
- X is a ligand represented by Formula 1, and when q is 0, r is 4.
- M 2 X s (Formula 4) (Wherein M 2 is one metal selected from the group consisting of Al, La, Cr, and Ba, X is a ligand shown in Formula 1, and s is a kind of M 2 Depending on 2 or 3.)
- the metal complex as shown in the above formula 3 or 4 is preferably generated by, for example, coordination of a complexing agent with the metal part of the metal alkoxide.
- it will replace with producing
- the said Formula 3 or the said which was previously manufactured by the other method No. 4 metal complex may be added to the dispersion.
- the metal compound is hydrolyzed to produce an oxide.
- the pH of water is adjusted by acid or alkali so that the surface charge of the metal powder is opposite to the surface charge of the oxide generated by hydrolysis of the metal compound.
- the water whose pH has been adjusted is also referred to as pH-adjusted water.
- the oxide can have a surface charge opposite to that of the metal powder, so that the oxide can be uniformly coated on the metal powder by electrostatic attraction.
- the amount of pH-adjusted water to be mixed with the dispersion may be at least an amount capable of completely hydrolyzing the metal alkoxide and metal complex.
- the temperature at the time of mixing the dispersion and pH adjusting water may be not less than the freezing point of the dispersion, pH adjusting water and the mixture, and is preferably 0 to 25 ° C.
- the procedure of mixing the pH-adjusted water into the dispersion composed of metal powder, metal alkoxide and complexing agent can be both a method of adding pH-adjusted water to the dispersion and a method of adding the dispersion to pH-adjusted water
- the method of adding pH-adjusted water to the dispersion is more preferable because the metal particles can be more uniformly coated with the oxide.
- any acid or alkali can be used as long as the acid or alkali added to control the pH can be adjusted.
- an acid is used.
- hydrochloric acid and sulfuric acid are preferable, and when alkali is used, aqueous ammonia and sodium hydroxide are preferable.
- the obtained metal powder is filtered, washed and dried to make a product.
- a method for filtering, washing and drying known methods can be used. For example, filtration may be performed by vacuum filtration, pressure filtration, or the like, and drying may be performed using a box-type dryer or an air dryer.
- nickel powder is dispersed in an organic solvent, and the nickel powder is made into a slurry.
- nickel powder obtained by a method such as a liquid phase reduction method or a gas phase reduction method can be used
- nickel powder obtained by a gas phase reduction method is preferable from the viewpoint of uniformity of particle size distribution.
- the nickel powder may have an average particle size of 0.03 ⁇ m to 1.0 ⁇ m and a CV value of particle size distribution of 50% or less.
- the average particle diameter of the nickel powder is obtained by taking a photograph of the nickel powder particles before coating with a scanning electron microscope, and using the image analysis software from the photograph, measuring the particle diameter of 500 or more nickel powders, The number average particle size is calculated from the particle size distribution of the obtained nickel powder. At this time, the particle diameter is the diameter of the smallest circle that encloses the particles.
- the CV value of the particle size distribution indicates the standard deviation of the particle size distribution / number average particle size.
- metal alkoxide and complexing agent are dissolved is added to the metal powder slurry.
- the metal alkoxide used at this time can use the metal alkoxide shown above. Any complexing agent can be used as long as it can coordinate with the metal part of the metal alkoxide.
- a ⁇ -diketone represented by Formula 1 can be used.
- the pH of the water added at this time is pH 1.5 to 14 when coating with SiO 2 , 6 to 10 when coating with TiO 2 , pH 9 to 10 when coating with ZrO 2 , and coating with Al 2 O 3 .
- the pH is preferably 8 to 11, and in the case of coating with La 2 O 3 , the pH is preferably 1.5 to 10. If the pH is within the above range in each case, the coating can be performed more uniformly.
- the generated oxide has a surface charge opposite to that of the metal powder, and is therefore adsorbed on the surface of the metal particles by electrostatic attraction.
- the size of the oxide particles formed from the metal alkoxide and the metal complex is very small, and is uniformly adsorbed on the surface of the metal particles.
- the acid and alkali added to control the pH of water can be used with any acid and alkali as long as the pH can be adjusted. From the viewpoint of convenience in use and economy, the acid may be hydrochloric acid or sulfuric acid.
- the alkali is preferably aqueous ammonia or sodium hydroxide.
- the obtained oxide-coated metal powder is filtered, washed and dried to make a product.
- An oxide-coated metal powder was produced. Details will be described below.
- the average particle size of the metal powder is obtained by taking a picture of the metal powder particles with a scanning electron microscope (trade name JSM-7800F, manufactured by JEOL Ltd.), and imaging the particle size of about 1,000 particles. The average value was calculated using analysis software (manufactured by Mountec Co., Ltd., trade name: MacView 4.0). The particle diameter was the diameter of the smallest circle enclosing the particles.
- the obtained oxide-coated nickel powder was sprinkled on a carbon support film, and photographs of the nickel powder were taken with a scanning transmission electron microscope (STEM) at a magnification of 1,000,000 to 1,500,000 times in several fields of view. Further, element mapping was performed by an EDS (Energy Dispersive X-ray Spectrometry) detector provided in the scanning transmission electron microscope.
- STEM scanning transmission electron microscope
- the thermal shrinkage was measured with a thermomechanical analyzer (TMA).
- TMA thermomechanical analyzer
- the measurement conditions were temperature range: room temperature to 1350 ° C., rate of temperature increase: 5 ° C./min, atmosphere: 2% H 2 , 98% N 2 300 mL / min.
- the temperature at which the shrinkage rate reached 5% was read as the 5% shrinkage temperature.
- Example 1 metallic nickel powder (average particle size 100 nm) was produced according to the method described in JP-A-10-219313. Ethanol was added to the metal nickel powder to make a 10 wt% slurry. On the other hand, apart from the slurry, when the metallic nickel powder contained in the slurry was 100% by weight, an amount of tetraethylorthosilicate (hereinafter also referred to as TEOS) corresponding to 2% by weight was dissolved in ethanol. Furthermore, acetylacetone as a complexing agent was added so as to have a double mole relative to the Si element.
- TEOS tetraethylorthosilicate
- the metallic nickel powder slurry was mixed with an ethanol solution of TEOS and acetylacetone and stirred for 1 hour to prepare 200 mL of a dispersion containing nickel powder. Thereafter, 100 mL of water whose pH was adjusted to 8-9 with aqueous ammonia was added at once and stirred for 2 hours. Thereafter, suction filtration was performed, and the target SiO 2 -coated nickel powder was obtained by drying in the atmosphere at 120 ° C. for 1 hour.
- the STEM photograph and STEM-EDS mapping image of the nickel powder obtained in Example 1 are shown in FIG. Table 1 shows the surface coverage and 5% shrinkage temperature.
- Example 2 Titanium tetraisopropoxide was used as the metal alkoxide, and the treatment was carried out in the same manner as in Example 1 except that the addition amount was the same as the volume of SiO 2 of 2 wt% to obtain TiO 2 coated nickel powder.
- the STEM photograph and STEM-EDS mapping image of the obtained nickel powder are shown in FIG. Table 1 shows the surface coverage and 5% shrinkage temperature.
- Example 3 A ZrO 2 -coated nickel powder was obtained in the same manner as in Example 1 except that zirconium tetraisopropoxide as the metal alkoxide and the amount added were the same as the volume of 2 wt% SiO 2 .
- the STEM photograph and STEM-EDS mapping image of the obtained nickel powder are shown in FIG. Table 1 shows the surface coverage and 5% shrinkage temperature.
- Example 4 Treatment was performed in the same manner as in Example 1 except that aluminum tri-n-butoxide was added as the metal alkoxide, and the addition amount was the same as the volume of SiO 2 of 2 wt% to obtain Al 2 O 3 coated nickel powder.
- the STEM photograph and STEM-EDS mapping image of the obtained nickel powder are shown in FIG. Table 1 shows the surface coverage and 5% shrinkage temperature.
- Example 5 La 2 O 3 coating was performed in the same manner as in Example 1 except that lanthanum triisopropoxide was used as the metal alkoxide, 2-propanol as the organic solvent, and the addition amount was the same as the volume of 2 wt% SiO 2.
- Nickel powder was obtained. The STEM photograph and STEM-EDS mapping image of the obtained nickel powder are shown in FIG. Table 1 shows the surface coverage and 5% shrinkage temperature.
- Example 2 The same treatment as in Example 2 was performed except that acetylacetone was not added to obtain a TiO 2 coated nickel powder.
- the STEM photograph and STEM-EDS mapping image of the obtained nickel powder are shown in FIG. Table 1 shows the surface coverage and 5% shrinkage temperature.
- Example 2 the surface coverage is better than that of the comparative example, and the coverage is improved by the complexing agent. Moreover, in each Example, the surface coverage is 80% or more, and as can be seen from FIG. 1, it can be seen that the surface coverage is more uniform than the comparative example. It can be seen that the 5% shrinkage temperature is increased in each example as compared to the reference example and the comparative example.
- the present invention can be used as an internal electrode of a multilayer ceramic capacitor.
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Abstract
Description
本実施形態に係る金属粉末の製造方法では、金属粉末の分散液と、酸またはアルカリを含む水とを混合する。ここで、金属粉末の分散液は、金属アルコキシドおよび錯化剤を含んでいる。これによって、金属アルコキシド、および該金属アルコキシドと錯化剤とから生成される金属錯体とを加水分解させることにより得られた酸化物にて金属粒子の表面の少なくとも一部を被覆する。
金属粉末とは、金属粒子の集合体のことであり、該金属粒子を構成する金属としては、ニッケル、銅、銀、アルミニウム、チタン、鉄、コバルト、タングステン、およびモリブデンなど、並びにこれら金属の合金が挙げられる。これらの中でも、金属粒子を構成する金属は、ニッケル、銅、および銀であることがより好ましい。これら金属粉末は、ペーストフィラー、チタン材の複合材、または触媒などの各種用途に好適に使用され、例えば、ニッケル、銅、および銀などは、ペーストフィラーに好適に使用される。金属粒子の平均粒径は特に限定されないが、好ましくは1μm以下、より好ましくは0.5μm以下、さらに好ましくは0.3μm以下、さらに好ましくは0.2μm以下、さらに好ましくは0.1μm以下である。このような平均粒径を有している金属粉末は、例えば気相還元法または液相還元法によって好適に製造することができる。このように平均粒径が1μm以下であるという、気相還元法または液相還元法によって製造された金属粒子の表面に酸化物を均一に被覆することができることも一態様に係る製造方法の利点の1つである。
分散液には、金属アルコキシドが含まれている。金属アルコキシドは、錯化剤によって加水分解することを抑制されつつも、酸化物を生成し、当該酸化物は、金属粒子の表面を被覆する。
M(OR3)P・・・(式2)
(ここで、Mは、Si、Ti、Zr、Al、La、Cr、およびBaからなる群から選択される1つの金属であり、R3は、炭素数1~4の直鎖状アルキル基、および炭素数3~4の分岐アルキル基であり、pは、Mの種類によって決まり、2~4の整数である。)
錯化剤は、金属アルコキシドの金属部と金属錯体を形成することにより、該金属アルコキシドの加水分解速度を遅くする。これにより、金属アルコキシドおよび当該金属アルコキシドから生成される金属錯体によって生成される酸化物の粒子を細かくすることができる。よって、酸化物を均一に金属粒子の表面に付着させることができる。
金属錯体は、加水分解することによって酸化物を形成する金属錯体であって、より具体的には、金属錯体は、例えば、以下の式3または式4に示す構造を取り得る。
M1(OR3)qXr ・・・(式3)
(ここで、M1は、Si、Ti、Zrからなる群から選択される1つの金属であり、Xは、前記式1に示す配位子であり、qが0のとき、rは4であり、qが2のとき、rは2である。)
M2Xs ・・・(式4)
(ここで、M2は、Al、La、Cr、およびBaからなる群から選択される1つの金属であり、Xは、前記式1に示す配位子であり、sは、M2の種類によって決まり、2または3である。)
なお、上記式3または4に示すような金属錯体は、一例として、金属アルコキシドの金属部に錯化剤が配位することによって好適に生成される。また、一態様に係る製造方法では、上記式3または4に示すような金属錯体であれば、金属アルコキシドから金属錯体を生成することに代えて、予め他の方法によって製造された上記式3または4の金属錯体を分散液に配合してもよい。
金属粉末、および金属錯体の混合溶液に対し、酸またはアルカリを含む水を混合することで、金属化合物を加水分解させ酸化物を生じさせる。水は、酸またはアルカリにより、金属粉末の表面電荷が、金属化合物の加水分解により生じた酸化物の表面電荷と反対になるようにpHを調整されている。このようにpHを調整した水を、以下、pH調整水とも称する。金属粉末、および金属錯体の分散液に加えると、酸化物は金属粉末と表面電荷が反対にすることができ、これにより、酸化物を静電引力により金属粉末に均一に被覆することができる。
以下、酸化物被覆ニッケル粉末の製造例をもとに詳細に説明する。なお、本実施形態に係る金属粉末の製造方法によって被覆され得る金属粉末は、ニッケルに限定するものではない。
本発明の一態様により生成したニッケル粉末は、酸化物被膜の形状および厚み、化学状態、熱収縮率により品質を評価した。つぎにそれぞれの評価方法について説明する。
金属粉末の平均粒径は、走査型電子顕微鏡(日本電子株式会社製、商品名JSM-7800F)により金属粉末の粒子の写真を撮影し、その写真から粒子約1,000個の粒径を画像解析ソフト(株式会社マウンテック製、商品名MacView4.0)を使用して求め、その平均値を算出した。なお、粒径は粒子を包み込む最小円の直径とした。
得られた酸化物被覆ニッケル粉末をカーボン支持膜に振りかけ、走査型透過電子顕微鏡(STEM)によりニッケル粉末の写真を100万~150万倍の倍率で数視野の撮影を行った。また、走査型透過電子顕微鏡に備え付けられているEDS(Energy Dispersive X-ray Spectrometry)検出器により元素マッピングを行った。
得られた酸化物被膜ニッケル粉末をインジウム板(厚み0.5mm)に固定し、光電子分光装置(サーモフィッシャーサイエンティフィック社製、k-alpha+)により、ニッケル、およびコーティング元素の測定を行った。
得られた酸化物被覆ニッケル粉末に対して3wt%のショウノウを加えた後、アセトンによりショウノウを溶かし、アセトンが蒸発するまで良くかき混ぜた。酸化物被覆ニッケル粉末とショウノウの混合粉末をφ5mm、高さ2mmのペレットに加圧成形した。
STEM-EDSマッピング像において、金属粒子の周上から元素が検出されなかった領域の弧の長さを測定し、以下の式で表面被覆率を計算した。
=(L0-L1)/L0×100
L0:金属粒子の周長さ
L1:金属粒子の周上において元素が検出されなかった領域の弧の長さ
まず、金属ニッケル粉末(平均粒径100nm)を、特開平10-219313号公報に記載された方法に準じて製造した。該金属ニッケル粉末にエタノールを加え、10wt%のスラリーにした。一方、該スラリーとは別に、上記スラリーに含まれる金属ニッケル粉末を100重量%としたときに、2重量%に相当する量のテトラエチルオルトシリケート(以下、TEOSとも称する)をエタノールに溶かした。さらに、錯化剤としてアセチルアセトンを、Si元素に対して2倍モルになるように加えた。金属ニッケル粉スラリーと、TEOSおよびアセチルアセトンのエタノール溶液とを混合し、1時間撹拌を行い、ニッケル粉末を含む分散液200mLを作製した。その後、アンモニア水でpHを8~9に調整した水100mLを一時に加え、2時間撹拌した。その後、吸引濾過を行い、大気中で120℃1時間乾燥を行うことで目的とするSiO2被覆ニッケル粉を得た。実施例1で得られたニッケル粉末のSTEM写真およびSTEM-EDSマッピング像を図1に示す。また、表面被覆率、5%収縮温度を表1に示す。
金属アルコキシドとしてチタニウムテトライソプロポキシド、添加量を2wt%のSiO2の体積と同じになるようにした以外は実施例1と同様に処理を行い、TiO2被覆ニッケル粉末を得た。得られたニッケル粉末のSTEM写真およびSTEM-EDSマッピング像を図2に示す。また、表面被覆率、5%収縮温度を表1に示す。
金属アルコキシドとしてジルコニウムテトライソプロポキシド、添加量を2wt%のSiO2の体積と同じになるようにした以外は実施例1と同様に処理を行い、ZrO2被覆ニッケル粉末を得た。得られたニッケル粉末のSTEM写真およびSTEM-EDSマッピング像を図3に示す。また、表面被覆率、5%収縮温度を表1に示す。
金属アルコキシドとしてアルミニウムトリ-n-ブトキシド、添加量を2wt%のSiO2の体積と同じになるようにした以外は実施例1と同様に処理を行い、Al2O3被覆ニッケル粉末を得た。得られたニッケル粉末のSTEM写真およびSTEM-EDSマッピング像を図4に示す。また、表面被覆率、5%収縮温度を表1に示す。
金属アルコキシドとしてランタントリイソプロポキシド、有機溶剤として2-プロパノール、添加量を2wt%のSiO2の体積と同じになるようにした以外は実施例1と同様に処理を行い、La2O3被覆ニッケル粉末を得た。得られたニッケル粉末のSTEM写真およびSTEM-EDSマッピング像を図5に示す。また、表面被覆率、5%収縮温度を表1に示す。
アセチルアセトンを加えなかった以外は実施例2と同様の処理を行い、TiO2被膜ニッケル粉末を得た。得られたニッケル粉末のSTEM写真およびSTEM-EDSマッピング像を図6に示す。また、表面被覆率、及び5%収縮温度を表1に示す。
実施例1と同様に得た金属ニッケル粉末を、コーティング元素による被覆を行なわず、参考例として用いた。
Claims (5)
- 前記分散液が、金属アルコキシドを含むことを特徴とする請求項1に記載の金属粉末の製造方法。
- 前記金属錯体を、前記金属アルコキシドと前記配位子である錯化剤とを混合することで生成する工程を含むことを特徴とする請求項2に記載の金属粉末の製造方法。
- 前記配位子がアセチルアセトンであることを特徴とする請求項1~3のいずれか1項に記載の金属粉末の製造方法。
- 前記酸化物による表面被覆率が80%以上であることを特徴とする金属粉末を製造する請求項1~4のいずれか1項に記載の金属粉末の製造方法。
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