JP2006199982A - Method for producing metallic fine powder - Google Patents
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- JP2006199982A JP2006199982A JP2005010439A JP2005010439A JP2006199982A JP 2006199982 A JP2006199982 A JP 2006199982A JP 2005010439 A JP2005010439 A JP 2005010439A JP 2005010439 A JP2005010439 A JP 2005010439A JP 2006199982 A JP2006199982 A JP 2006199982A
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- platinum
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- 239000000843 powder Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010306 acid treatment Methods 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 239000010931 gold Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- 239000010948 rhodium Substances 0.000 claims abstract description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 26
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 26
- 150000004692 metal hydroxides Chemical class 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 15
- 229910001111 Fine metal Inorganic materials 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 239000010419 fine particle Substances 0.000 claims description 9
- 239000002923 metal particle Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N hydroxylamine hydrochloride Substances Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 3
- WCYJQVALWQMJGE-UHFFFAOYSA-M hydroxylammonium chloride Chemical compound [Cl-].O[NH3+] WCYJQVALWQMJGE-UHFFFAOYSA-M 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 33
- 239000000243 solution Substances 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract 2
- 239000011260 aqueous acid Substances 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000013528 metallic particle Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003058 platinum compounds Chemical class 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 ammonia compound Chemical class 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WIDMMNCAAAYGKW-UHFFFAOYSA-N azane;palladium(2+);dinitrate Chemical compound N.N.N.N.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O WIDMMNCAAAYGKW-UHFFFAOYSA-N 0.000 description 1
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
- WPEJSSRSFRWYJB-UHFFFAOYSA-K azanium;tetrachlorogold(1-) Chemical compound [NH4+].[Cl-].[Cl-].[Cl-].[Cl-].[Au+3] WPEJSSRSFRWYJB-UHFFFAOYSA-K 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Abstract
Description
本発明は、金属微粉末の製造方法、とりわけ電子工業で使用される導電性ペースト、粉末冶金材料などに好適な金属微粉末の製造方法に関するものである。 The present invention relates to a method for producing a metal fine powder, particularly a method for producing a metal fine powder suitable for a conductive paste, powder metallurgy material and the like used in the electronics industry.
近年、電子機器の小型化に伴い、これらに使用される電子部品は益々小型化が要求され、なかでもセラミックを使用したインダクター、コンデンサーなどの機能部品は、多積層構造により小型化とともに特性の向上が図られるようになってきた。このような積層部品は、金属微粉末を有機バインダーを含む有機溶剤に分散させた導電性ペーストにして、セラミックスグリーンシート上に印刷し、積層、圧着及び切断する工程を経た後、焼成され、さらに外部電極を形成することにより製造される。 In recent years, with the miniaturization of electronic devices, electronic components used in these devices are increasingly required to be miniaturized. Among them, functional components such as inductors and capacitors using ceramics are miniaturized and improved in characteristics due to the multi-layer structure. Has come to be planned. Such a laminated part is made into a conductive paste in which metal fine powder is dispersed in an organic solvent containing an organic binder, printed on a ceramic green sheet, subjected to lamination, pressure bonding, and cutting, and then fired. Manufactured by forming external electrodes.
金属粉末は、気相化学反応法、沈殿還元法、熱還元法など種々の方法で製造されるが、導電ペーストに用いられる金属粉末は、粒径が数ミクロン以下で、均一球状であると金属粒子がよく充填されて好ましい。 Metal powder is manufactured by various methods such as gas phase chemical reaction method, precipitation reduction method, thermal reduction method, etc. The metal powder used in the conductive paste has a particle size of several microns or less and is a metal having a uniform spherical shape. It is preferable that the particles are well packed.
例えば、白金を例に挙げれば、白金化合物を水溶液にしてヒドラジンなどで還元するとき、アンモニア化合物を添加して球形で、かつ粒度が均一な白金粉末とする方法〔特許文献1参照〕、さらに、白金化合物を水溶液にして、還元して得られた平均粒径が0.2〜3μmの球形白金粉末を、酸化雰囲気中で球形が変形しない範囲で熱処理する球形状白金粉末の製造方法〔特許文献2参照〕などが提案されている。しかし、これらの方法では白金化合物水溶液から還元されて析出するときに、粒子の粒度分布が広くなるといった問題があった。 For example, when platinum is taken as an example, when a platinum compound is converted into an aqueous solution and reduced with hydrazine or the like, a method of adding an ammonia compound to obtain a platinum powder having a spherical shape and a uniform particle size (see Patent Document 1), A method for producing a spherical platinum powder in which a spherical platinum powder having an average particle size of 0.2 to 3 μm obtained by reducing a platinum compound into an aqueous solution is heat-treated in an oxidizing atmosphere within a range in which the spherical shape is not deformed [Patent Literature 2)] has been proposed. However, these methods have a problem that the particle size distribution of the particles becomes wide when reduced and precipitated from the platinum compound aqueous solution.
一方、粒度分布を狭くするための方策として、白金ブラックと、アルカリ塩またはアルカリ土類金属塩の塩とを湿式混合した後、乾燥、粉砕し、その粉砕体を焼成してガスを除去後希酸によって塩を溶解させて水洗除去し、これを乾燥させてPt粉末を得る方法。〔特許文献3参照〕、白金微粉末と炭酸カルシウム粉末とを混合し、加熱処理して炭酸カルシウム粉末を熱分解させて酸化カルシウムとし、この酸化カルシウム介在下で白金微粉末を粒成長させ、次いで水に接触させて酸化カルシウムを水酸化カルシウムに変化させ、しかる後に酸処理して水酸化カルシウムを水洗除去して白金粉末を製造する方法。〔特許文献4参照〕などの提案がされている。しかし、この方法では、白金の微粉末を出発原料としていることから操作上の扱い難さがあった。 On the other hand, as a measure for narrowing the particle size distribution, platinum black and alkali salt or alkaline earth metal salt salt are wet mixed, dried and pulverized, and the pulverized product is baked to remove the gas and diluted. A method of obtaining a Pt powder by dissolving a salt with an acid, removing it by washing with water, and drying it. [See Patent Document 3], platinum fine powder and calcium carbonate powder are mixed, heat-treated to thermally decompose the calcium carbonate powder to calcium oxide, and the platinum fine powder is grown in the presence of this calcium oxide, A method of producing platinum powder by contacting with water to change calcium oxide into calcium hydroxide, and then treating with acid to remove the calcium hydroxide by washing with water. [See Patent Document 4]. However, this method is difficult to handle because it uses platinum fine powder as a starting material.
上記問題点に鑑み、本発明の目的は、白金、金、ロジウム、パラジウム、銀、銅、ニッケルから選ばれる1種以上の金属微粉末の製造方法において、比較的安価で、かつ取扱いの容易なそれぞれの水溶性金属化合物を原料として、複雑な工程を経ずに、粒子形状が揃い、しかも粒径が均一な相当する金属微粉末を製造する方法を提供することにある。 In view of the above problems, an object of the present invention is to provide a method for producing one or more metal fine powders selected from platinum, gold, rhodium, palladium, silver, copper and nickel, which is relatively inexpensive and easy to handle. An object of the present invention is to provide a method for producing a corresponding fine metal powder having a uniform particle shape and a uniform particle size without using complicated steps, using each water-soluble metal compound as a raw material.
かかる目的を達成すべく請求項1に係る発明は、白金、金、ロジウム、パラジウム、銀、銅、ニッケルから選ばれる1種以上の金属微粉末の製造方法であり、金属の水溶性化合物をpH4以下の水溶液にする金属化合物水溶液調製工程;pH4以下の水溶液に、水酸化カルシウム、水酸化マグネシウム、水酸化バリウムから選ばれる1種以上の周期律表2A元素金属〔以降、単に「2A金属」と記す〕水酸化物の粉体および/またはその水系スラリーを混合してpH10以上にする反応工程;反応工程終了後の不溶解固体を分別、乾燥する第1分離工程;分別した不溶解固体を、不活性ガスあるいは水素ガス雰囲気下で、800℃以上でありかつ選ばれた前記金属のうち最も低い融点より100℃以上高くならない温度範囲で加熱する加熱処理工程;加熱処理後の固体を、酸水溶液中に浸漬してpHを4以下に保持する酸処理工程;酸処理後における酸水溶液中の金属粒子を分別、洗浄、乾燥する第2分離工程;の各工程を含んでなっている。 In order to achieve this object, the invention according to claim 1 is a method for producing one or more fine metal powders selected from platinum, gold, rhodium, palladium, silver, copper, and nickel, and the metal water-soluble compound is adjusted to pH 4 Metal compound aqueous solution preparation step to make the following aqueous solution; one or more periodic table 2A element metals selected from calcium hydroxide, magnesium hydroxide and barium hydroxide in an aqueous solution having a pH of 4 or less [hereinafter simply referred to as “2A metal” The reaction step of mixing the hydroxide powder and / or its aqueous slurry to a pH of 10 or higher; the first separation step of separating and drying the insoluble solid after completion of the reaction step; the separated insoluble solid; Heating treatment in an inert gas or hydrogen gas atmosphere at a temperature not lower than 800 ° C. and not higher than the lowest melting point of the selected metal by not less than 100 ° C. A step; an acid treatment step in which the solid after the heat treatment is immersed in an acid aqueous solution to maintain the pH at 4 or less; a second separation step in which the metal particles in the acid aqueous solution after the acid treatment are separated, washed and dried; Each step is included.
請求項2に係る金属微粉末の製造方法は、請求項1における反応工程において、さらに還元剤を加えて行うことにある。 The method for producing a metal fine powder according to claim 2 is that the reaction step in claim 1 is performed by further adding a reducing agent.
請求項3に係る金属微粉末の製造方法は、請求項2における還元剤が、ヒドラジン、ホルマリン、ブドウ糖、ハイドロキノン、塩化ヒドロキシルアンモニウムから選ばれる1種以上である In the method for producing fine metal powder according to claim 3, the reducing agent according to claim 2 is at least one selected from hydrazine, formalin, glucose, hydroquinone, and hydroxylammonium chloride.
請求項4に係る金属微粉末の製造方法は、請求項1の反応工程における2A金属水酸化物が、金属化合物の金属原子に対し2〜20倍当量過剰に加えられることにある。
請求項5に係る金属微粉末の製造方法は、金属が、白金、金からの1種以上であるとき、酸処理工程における酸水溶液が、塩酸、硝酸、酢酸から選ばれる1種以上である。
The method for producing fine metal powder according to claim 4 is that the 2A metal hydroxide in the reaction step of claim 1 is added in an excess of 2 to 20 times equivalent to the metal atom of the metal compound.
In the method for producing metal fine powder according to claim 5, when the metal is one or more from platinum and gold, the acid aqueous solution in the acid treatment step is one or more selected from hydrochloric acid, nitric acid and acetic acid.
請求項6に係る金属微粉末の製造方法は、金属微粉末の金属が、ロジウム、パラジウム、銀、銅、ニッケルからの1種以上を含むとき、酸処理工程における酸水溶液は、酢酸である。 In the method for producing fine metal powder according to claim 6, when the metal of the fine metal powder contains one or more of rhodium, palladium, silver, copper, and nickel, the acid aqueous solution in the acid treatment step is acetic acid.
本発明の効果として白金、金、ロジウム、パラジウム、銀、銅、ニッケルについて、安価で、取扱いの容易な原料から、複雑な工程を経ずに、粒子形状が揃い、しかも粒径が均一な金属微粉末を製造することができる。 As an effect of the present invention, platinum, gold, rhodium, palladium, silver, copper, and nickel are made of inexpensive, easy-to-handle raw materials with a uniform particle shape and a uniform particle size without complicated processes. A fine powder can be produced.
本発明が対象とする金属微粉末は、白金、金、ロジウム、パラジウム、銀、銅、ニッケルから選ばれる1種以上の金属である。 The metal fine powder targeted by the present invention is one or more metals selected from platinum, gold, rhodium, palladium, silver, copper, and nickel.
本発明の金属微粉末の製造方法を実施する第1の工程は、金属化合物水溶液調製工程であり、それぞれ相当する金属化合物を水に溶解し、pH4以下とする。 The 1st process which enforces the manufacturing method of the metal fine powder of this invention is a metal compound aqueous solution preparation process, melt | dissolves each corresponding metal compound in water, and sets it to pH 4 or less.
金属化合物の具体例を挙げれば、白金化合物として、ヘキサクロロ白金(IV)酸、テトラクロロ白金(II)酸、テトラアンミン白金(II)酸などがあり、金化合物として、塩化金(III)酸、テトラクロロ金(III)酸、テトラクロロ金(III)酸アンモニウムなどがあり、ロジウムの化合物として硝酸ロジウム(III)、ヘキサクロロロジウム(III)酸アンモニウムなどがあり、パラジウムの化合物として硝酸パラジウム(II)、テトラアンミンパラジウム(II)硝酸塩などがあり、銀化合物として、硝酸銀などがあり、銅化合物として、硝酸銅、塩化銅などがあり、ニッケル化合物として、硝酸ニッケル、塩化ニッケルなどがある。 Specific examples of the metal compound include hexachloroplatinic (IV) acid, tetrachloroplatinic (II) acid, tetraammineplatinum (II) acid and the like as the platinum compound, and gold compounds such as gold (III) chloride and tetrachloride. There are chloroauric (III) acid, ammonium tetrachloroaurate (III), etc., rhodium compound such as rhodium (III) nitrate, hexachlororhodium (III) ammonium etc., palladium compound as palladium (II) nitrate, Examples thereof include tetraamminepalladium (II) nitrate, silver compounds such as silver nitrate, copper compounds such as copper nitrate and copper chloride, and nickel compounds such as nickel nitrate and nickel chloride.
金属化合物は、1種単独でもよく、または同じ金属からなる2種以上の金属化合物を組合せてもよい。また、白金、金、ロジウム、パラジウム、銀、銅、ニッケルから選ばれる2種以上の金属についてそれらの金属化合物を組合せることにより、合金または金属混合物の金属微粉末とすることもできる。 The metal compound may be used alone or in combination of two or more metal compounds made of the same metal. Moreover, it can also be set as the metal fine powder of an alloy or a metal mixture by combining those metal compounds about 2 or more types of metals chosen from platinum, gold | metal | money, rhodium, palladium, silver, copper, and nickel.
金属化合物は水に溶解しただけでpHが4以下となるものもあるが、必要により酸を加えてpHを4以下とする。このとき、使用される酸は、金属化合物の水への溶解性を高め、またはpHを4以下に調整できるものであればよく、塩酸、硝酸などの無機酸、酢酸、蟻酸などの有機酸である。硫酸を用いてもよいが、生成した金属微粒子の使用目的によっては硫黄原子が混入する可能性を極度に避けることがあるので、その面からは好ましくないことがある。 Some metal compounds have a pH of 4 or less when dissolved in water, but an acid is added to adjust the pH to 4 or less if necessary. At this time, the acid used is not particularly limited as long as it can increase the solubility of the metal compound in water or the pH can be adjusted to 4 or less, and may be an inorganic acid such as hydrochloric acid or nitric acid, or an organic acid such as acetic acid or formic acid. is there. Sulfuric acid may be used, but depending on the intended use of the generated metal fine particles, the possibility of mixing sulfur atoms may be extremely avoided, which may not be preferable from this aspect.
次いで、反応工程で、上記のpH4以下とした金属化合物水溶液と、2A金属水酸化物を混合してpHを10以上にする。ここで2A金属水酸化物は、水酸化カルシウム、水酸化マグネシウム、水酸化バリウムから選ばれる1種以上である。 Next, in the reaction step, the aqueous metal compound solution having a pH of 4 or less and the 2A metal hydroxide are mixed to adjust the pH to 10 or more. Here, the 2A metal hydroxide is at least one selected from calcium hydroxide, magnesium hydroxide, and barium hydroxide.
2A金属水酸化物は、粉体を使用して金属化合物水溶液に粉体のまま加えてもよく、あるいは粉体を予め水系スラリーとして加えてもよい。粉体は、一次粒子が2μm以下、好ましくは1μm以下のものを用いるのがよい。最も好ましい実施の形態は、一次粒子が1μm以下の粒子を水系スラリーとして、これをボールミル、ローラーミルなど機械的に粉砕、混練して粒子の会合を解いておくのがよい。また、このとき界面活性剤などを加えて粒子の分散を促進させることがあるが、本発明はこれらの粉砕処理について何ら限定をするものではない。 The 2A metal hydroxide may be added as a powder to the aqueous metal compound solution using powder, or the powder may be added in advance as an aqueous slurry. As the powder, one having primary particles of 2 μm or less, preferably 1 μm or less is used. In the most preferred embodiment, particles having primary particles of 1 μm or less are used as an aqueous slurry, and this is mechanically pulverized and kneaded, such as a ball mill or a roller mill, to release the association of the particles. At this time, a surfactant or the like may be added to promote particle dispersion, but the present invention does not limit these pulverization treatments.
金属化合物水溶液と2A金属水酸化物との混合方法は特に限定するものではないが、混合の仕方により最終的に製造される金属微粉末の粒子径中央値、粒子径分布が変ることがある。最も好ましい実施の形態は、金属化合物水溶液と2A金属水酸化物の水系スラリーをそれぞれ別個に準備し、金属化合物水溶液を攪拌しつつこの中に2A金属水酸化物の水系スラリーを徐々に注ぎ込むことである。この方法により、反応を円滑に進め、生成物の状態を均一にすることができる。反応は、室温で充分早く進行するが、必要により60℃程度にして反応の進行を促進してもよい。 The mixing method of the metal compound aqueous solution and the 2A metal hydroxide is not particularly limited, but the median particle diameter and particle diameter distribution of the metal fine powder finally produced may vary depending on the mixing method. In the most preferred embodiment, the aqueous metal compound solution and the aqueous slurry of 2A metal hydroxide are separately prepared, and the aqueous slurry of 2A metal hydroxide is gradually poured into this while stirring the aqueous metal compound solution. is there. By this method, the reaction can proceed smoothly and the product state can be made uniform. The reaction proceeds sufficiently quickly at room temperature, but if necessary, the reaction may be promoted at about 60 ° C.
金属化合物水溶液と2A金属水酸化物を反応させるときの媒体となる水の量は、全体が攪拌できる程度であればよい。通常、混合した後の固体分が10〜30重量%となるようにする。従って、金属化合物水溶液、2A金属水酸化物の水系スラリーそれぞれに充分な水を入れておくのが好ましいが、必要により後でさらに追加的に加えてもよい。金属化合物と2A金属水酸化物との反応は、室温で混合することで速やかに進行するが、60℃程度に温度を高めても差し支えない。 The amount of water used as a medium when the metal compound aqueous solution and the 2A metal hydroxide are reacted may be such that the whole can be stirred. Usually, the solid content after mixing is 10 to 30% by weight. Accordingly, it is preferable to add sufficient water to each of the aqueous slurry of the metal compound aqueous solution and the 2A metal hydroxide, but it may be added later if necessary. The reaction between the metal compound and the 2A metal hydroxide proceeds rapidly by mixing at room temperature, but the temperature may be increased to about 60 ° C.
2A金属水酸化物は、金属化合物水溶液とが混合されたとき最終的にpHが10以上になる量あれよいが、好ましくは金属化合物の金属原子に対し2〜20倍当量、さらに好ましくは5〜10倍当量過剰とする。2A金属水酸化物の量は、最終的に製造される金属微粉末と関連して、2A金属水酸化物の量が大きくなるに従い最終的に生成される金属微粉末の粒子径が小さくなる。 The 2A metal hydroxide may be added in an amount such that the final pH becomes 10 or more when mixed with the aqueous metal compound solution, but is preferably 2 to 20 times equivalent, more preferably 5 to 5 metal atoms of the metal compound. 10-fold equivalent excess. The amount of the 2A metal hydroxide is related to the metal fine powder to be finally produced, and the particle diameter of the metal fine powder finally produced becomes smaller as the amount of the 2A metal hydroxide becomes larger.
また、反応工程は、さらに還元剤を加えて行うことができる。還元剤は、後述の金属微粉末としたときに金属微粉末表面の純度を上げる上で有利である。還元剤の添加は、2A金属水酸化物を水系スラリーとしたときはその水系スラリー中に添加しておき、還元剤含有2A金属水酸化物水系スラリーとして金属化合物水溶液と混合するのが好ましい。あるいは、金属化合物水溶液と2A金属水酸化物を反応させた後で、混合液の中に添加する。還元剤を金属化合物水溶液に添加してもよいが、金、白金、銅では金属化合物の金属原子価を変えるなど、生成した金属微粒子の均一性を損なうことがある。 Further, the reaction step can be performed by further adding a reducing agent. The reducing agent is advantageous in increasing the purity of the surface of the metal fine powder when the metal fine powder described later is used. When the 2A metal hydroxide is used as an aqueous slurry, the reducing agent is preferably added to the aqueous slurry and mixed with the aqueous metal compound solution as a reducing agent-containing 2A metal hydroxide aqueous slurry. Or after making a metal compound aqueous solution and 2A metal hydroxide react, it adds in a liquid mixture. Although a reducing agent may be added to the aqueous metal compound solution, gold, platinum, and copper may impair the uniformity of the generated metal fine particles, such as changing the metal valence of the metal compound.
ここで使用される還元剤は、特にpHが10以上で還元作用を示し、かつ水溶性のものがよく、好ましい具体例を挙げれば、ヒドラジン、ホルマリン、ブドウ糖、ハイドロキノン、塩化ヒドロキシルアンモニウムである。水硫化ナトリウム、チオ硫酸ナトリウムなども効果はあるが、生成した金属微粒子の使用目的によっては硫黄原子が混入する可能性を極度に避けることがあるので、その面からは好ましくないことがある。添加された還元剤は、その一部が金属化合物と2A金属水酸化物との反応したときの生成物中に取り込まれるのみであるので、反応論的に過剰が用いられるのがよく、金属化合物を原子価0に還元するに要する理論量に対し2〜20倍当量程度とするのが好ましい。 The reducing agent used here is particularly preferably one having a reducing action at a pH of 10 or more and water-soluble. Preferred examples include hydrazine, formalin, glucose, hydroquinone, and hydroxylammonium chloride. Although sodium hydrosulfide, sodium thiosulfate, and the like are effective, depending on the intended use of the generated metal fine particles, the possibility of sulfur atoms being mixed may be extremely avoided, which may not be preferable from that aspect. Since a part of the added reducing agent is only taken into the product when the metal compound reacts with the 2A metal hydroxide, it is preferable to use an excess in terms of reaction. Is preferably about 2 to 20 times equivalent to the theoretical amount required to reduce the valence to zero.
金属化合物水溶液と2A金属水酸化物が混合されpHが10以上になると、直ちに反応生成物が析出し、過剰量分の2A金属水酸化物が不溶解物のまま残り、従って反応工程が終わったとき、反応生成物と過剰量分の2A金属水酸化物が混合状態で媒体である水中にスラリー状になっている。 When the aqueous metal compound solution and the 2A metal hydroxide were mixed and the pH reached 10 or more, the reaction product immediately precipitated, and the excess amount of the 2A metal hydroxide remained undissolved, and thus the reaction process was completed. When the reaction product and an excess amount of 2A metal hydroxide are mixed, they are in a slurry state in the medium water.
次いで、第1分離工程で、反応工程終了後のスラリーから、不溶解固体を分別、乾燥する。分別は、通常ろ過で行われ、その後100〜150で乾燥して不溶解固体に付着した水分を除く。 Next, in the first separation step, the insoluble solid is separated from the slurry after completion of the reaction step and dried. Fractionation is usually performed by filtration, and then dried at 100 to 150 to remove moisture adhering to the insoluble solid.
加熱処理工程は、乾燥された固体を、不活性ガスあるいは水素ガス雰囲気下で、800℃以上で、かつ選ばれた金属のうち最も低融点金属の融点より100℃以上高くならない温度で加熱する工程である。この加熱処理により、金属化合物と2A金属水酸化物との反応生成物は、熱分解して金属化合物由来の金属が原子価0の状態となる。一方、共存する2A金属水酸化物は熱分解して2A金属酸化物となる。形態的には、金属化合物由来の金属は原子価0の状態で半融状態となり凝集していくが、熱的に安定な固体である2A金属酸化物に囲まれて凝集が妨げられ、凝集金属の周囲を取囲むように2A金属酸化物が配置された状態になる。結果的に、2A金属酸化物の介在量により金属粒子径が決まることになる。すなわち、2A金属酸化物の介在量が相対的に多い程金属粒子の成長が阻害され、金属粒子径は小さくなる。従って、上記した2A金属水酸化物の過剰量は、この観点から決められるものである。 The heat treatment step is a step of heating the dried solid in an inert gas or hydrogen gas atmosphere at a temperature not lower than 800 ° C. and not higher than 100 ° C. higher than the melting point of the lowest melting metal among the selected metals. It is. By this heat treatment, the reaction product of the metal compound and the 2A metal hydroxide is thermally decomposed so that the metal derived from the metal compound has a valence of zero. On the other hand, the coexisting 2A metal hydroxide is thermally decomposed into a 2A metal oxide. Formally, the metal derived from the metal compound becomes a semi-molten state and aggregates in the state of zero valence, but the aggregation is prevented by being surrounded by the thermally stable solid 2A metal oxide. 2A metal oxide is placed so as to surround the periphery of the substrate. As a result, the metal particle diameter is determined by the amount of the 2A metal oxide interposed. That is, as the amount of 2A metal oxide present is relatively large, the growth of metal particles is inhibited, and the metal particle diameter becomes smaller. Therefore, the excess amount of the 2A metal hydroxide described above is determined from this viewpoint.
また、金属粒子が自由に成長し得ない環境にすることで金属粒子径が均一に揃えられ、粒径分布の狭い金属粒子が得られることになる。この工程の雰囲気は、酸素が存在すると金属によっては酸化するので、窒素、アルゴン、ヘリウムなどの不活性ガス雰囲気、または水素など還元性ガス雰囲気とするのがよい。加熱処理時間は、金属の種類、2A金属水酸化物の量、加熱温度などにより異なり、一律に決めることができないが、通常30分〜2時間である。30分より短い時間では、充分に目的が達せられないことがある。2時間以上行うことは、金属微粒子生成において悪い影響を及ぼすことはないが、特別に利点もなく、経済的にみて不利になることがある。 In addition, by setting the environment in which the metal particles cannot grow freely, the metal particle diameters can be made uniform and metal particles with a narrow particle size distribution can be obtained. The atmosphere in this step is oxidized depending on the metal in the presence of oxygen. Therefore, an inert gas atmosphere such as nitrogen, argon or helium, or a reducing gas atmosphere such as hydrogen is preferable. The heat treatment time varies depending on the type of metal, the amount of 2A metal hydroxide, the heating temperature, etc., and cannot be determined uniformly, but is usually 30 minutes to 2 hours. If the time is shorter than 30 minutes, the purpose may not be sufficiently achieved. Performing for 2 hours or more does not adversely affect the production of metal fine particles, but has no particular advantage and may be disadvantageous from an economical viewpoint.
酸処理工程は、上記加熱処理が終った本発明の対象である金属微粒子と2A金属酸化物の混合物から、金属微粒子を残し、2A金属酸化物だけを溶解させる工程である。 The acid treatment step is a step in which only the 2A metal oxide is dissolved while leaving the metal fine particles from the mixture of the metal fine particles and the 2A metal oxide, which are objects of the present invention after the heat treatment.
すなわち、加熱処理工程を終了した固体を、酸水溶液中に浸漬してpHを4以下に保持する。このとき使用される酸は、目的の金属微粒子は溶解せず、2A金属酸化物のみ水に溶解させることができるものであればよく、好ましい具体例を挙げれば、金属が、白金、金からの1種以上であるとき、塩酸、硝酸、酢酸から選ばれる1種以上であり、金属が、ロジウム、パラジウム、銀、銅、ニッケルからの1種以上を含むとき、酢酸である。 That is, the solid after the heat treatment step is immersed in an acid aqueous solution to maintain the pH at 4 or less. The acid used at this time may be any acid that does not dissolve the target metal fine particles but can dissolve only the 2A metal oxide in water. When it is at least one, it is at least one selected from hydrochloric acid, nitric acid, and acetic acid, and when the metal contains at least one from rhodium, palladium, silver, copper, and nickel, it is acetic acid.
酸の量は、2A金属酸化物と反応するに充分な量であればよいが、実際上は酸が大過剰となる酸水溶液に浸漬し、pHが4以下に維持できるようにして行う。この工程は、2A金属酸化物の白色スラリーが溶解し、黒色の金属微粒子が沈降してくる外観を観察していけばよい。酸処理工程は、攪拌を行いつつ実施するのが好ましく、温度が室温〜60℃で、所要時間は、酸の量、温度などにより異なるが30分〜1時間程度である。 The amount of the acid may be an amount sufficient to react with the 2A metal oxide, but in practice, the acid is immersed in an acid aqueous solution in which the acid is excessively large so that the pH can be maintained at 4 or less. In this step, it is only necessary to observe the appearance in which the white slurry of 2A metal oxide is dissolved and the black metal fine particles are precipitated. The acid treatment step is preferably carried out while stirring, and the temperature is from room temperature to 60 ° C., and the required time is about 30 minutes to 1 hour, although it varies depending on the amount of acid, temperature and the like.
最後に、第2分離工程において、酸処理工程で沈降した金属粒子を分別、洗浄、乾燥して金属微粉末を得る。 Finally, in the second separation step, the metal particles precipitated in the acid treatment step are separated, washed and dried to obtain a metal fine powder.
塩化白金酸水溶液(白金含有量;16.4重量%)276gを攪拌しつつ、この中に水酸化カルシウム(平均粒径;2μm)150gを脱イオン水750gに入れたスラリー〔特殊機化工業(株)製、「ホモミキサー−MARKII−20」(商品型番)を使用して製造〕を注ぎ入れ、pHが11となった。5%ヒドラジン水溶液300gを加え、20℃で10分間攪拌した。不溶解物をろ別し、水洗した。120℃で乾燥した後、窒素雰囲気下で1200℃で1時間熱処理した。次いで、1Lの脱イオン水に入れ、硝酸でpH1以下として、熱処理物が溶解し、代りに黒色沈降物が生成するまで充分時間を置いた。容器底に沈降した黒色粒子をろ別し、水洗、120℃で乾燥した。収量42g。 While stirring 276 g of an aqueous chloroplatinic acid solution (platinum content: 16.4% by weight), 150 g of calcium hydroxide (average particle size: 2 μm) was put in 750 g of deionized water [special machine industry ( Manufactured by “Homomixer-MARKII-20” (product model number)] was poured, and the pH was 11. 300 g of 5% hydrazine aqueous solution was added and stirred at 20 ° C. for 10 minutes. The insoluble material was filtered off and washed with water. After drying at 120 ° C., heat treatment was performed at 1200 ° C. for 1 hour in a nitrogen atmosphere. Next, it was put in 1 L of deionized water, adjusted to pH 1 or less with nitric acid, and sufficient time was allowed until the heat-treated product was dissolved and a black precipitate was formed instead. The black particles settled on the bottom of the container were filtered off, washed with water and dried at 120 ° C. Yield 42g.
同様にして、水酸化カルシウムの添加量、水酸化カルシウムの平均粒径、塩化白金酸水溶液と水酸化カルシウムスラリーの混合温度を変えて行った。表1にその条件を示し、図1〜7に得られた粒子のSEM写真を示す。 Similarly, the addition amount of calcium hydroxide, the average particle diameter of calcium hydroxide, and the mixing temperature of the chloroplatinic acid aqueous solution and the calcium hydroxide slurry were changed. Table 1 shows the conditions, and FIGS. 1 to 7 show SEM photographs of the obtained particles.
硝酸銀30gを脱イオン水200gに溶解し、これを攪拌しつつこの中に水酸化カルシウム(平均粒径;2.2μm)150gを脱イオン水250gに入れたスラリー〔特殊機化工業(株)製、「ホモミキサー−MARKII−20」(商品型番)を使用して製造〕を注ぎ入れ、pHを11として、室温で10分間攪拌した。120℃で乾燥した後、窒素雰囲気下900℃で30分間熱処理した。次いで、50%酢酸水溶液1Lに入れ、pH4以下にして、熱処理物が溶解し、代りに沈降物が生成するまで充分時間を置いた。容器底に沈降した粒子をろ別し、水洗、120℃で乾燥して目的の銀粒子を得た。収量165g。 30 g of silver nitrate was dissolved in 200 g of deionized water, and while stirring the slurry, 150 g of calcium hydroxide (average particle size: 2.2 μm) was put in 250 g of deionized water [manufactured by Tokushu Kika Kogyo Co., Ltd. , “Manufactured using“ Homomixer-MARKII-20 ”(product model number)” was poured, the pH was set to 11, and the mixture was stirred at room temperature for 10 minutes. After drying at 120 ° C., heat treatment was performed at 900 ° C. for 30 minutes in a nitrogen atmosphere. Then, it was put in 1 L of 50% aqueous acetic acid solution, adjusted to pH 4 or less, and sufficient time was allowed until the heat-treated product was dissolved and a precipitate was formed instead. The particles settled on the bottom of the container were filtered off, washed with water and dried at 120 ° C. to obtain the intended silver particles. Yield 165g.
本発明による白金、金、ロジウム、パラジウム、銀、銅、ニッケルの金属微粉末は、安価で、取扱いの容易な原料から、複雑な工程を経ずに、粒子形状が揃い、しかも粒径が均一に製造することができ、電子工業で使用される導電性ペースト、粉末冶金材料などに好適である。 The fine metal powders of platinum, gold, rhodium, palladium, silver, copper, and nickel according to the present invention are inexpensive and easy to handle from raw materials without any complicated process, and with a uniform particle size. It is suitable for conductive pastes, powder metallurgy materials, etc. used in the electronics industry.
Claims (6)
前記金属の水溶性化合物をpH4以下の水溶液にする金属化合物水溶液調製工程;
前記pH4以下の水溶液に、水酸化カルシウム、水酸化マグネシウム、水酸化バリウムから選ばれる1種以上の周期律表2A元素金属水酸化物の粉体および/またはその水系スラリーを混合してpH10以上にする反応工程;
前記反応工程終了後の不溶解固体を分別、乾燥する第1分離工程;
前記分別した不溶解固体を、不活性ガスあるいは水素ガス雰囲気下で、800℃以上でありかつ選ばれた前記金属のうち最も低い融点より100℃以上高くならない温度範囲で加熱する加熱処理工程;
前記加熱処理後の固体を、酸水溶液中に浸漬してpHを4以下に保持する酸処理工程;
前記酸処理後における酸水溶液中の金属粒子を分別、洗浄、乾燥する第2分離工程;
の各工程を含んでなることを特徴とする金属微粉末の製造方法。 A method for producing one or more fine metal powders selected from platinum, gold, rhodium, palladium, silver, copper, and nickel;
A metal compound aqueous solution preparation step for converting the metal water-soluble compound into an aqueous solution having a pH of 4 or less;
The aqueous solution having a pH of 4 or less is mixed with at least one type of periodic table 2A element metal hydroxide powder selected from calcium hydroxide, magnesium hydroxide, and barium hydroxide and / or an aqueous slurry thereof to have a pH of 10 or more. Reaction steps to
A first separation step of separating and drying the insoluble solid after completion of the reaction step;
A heat treatment step of heating the separated insoluble solid in an inert gas or hydrogen gas atmosphere at a temperature range of 800 ° C. or higher and not higher than 100 ° C. above the lowest melting point of the selected metal;
An acid treatment step of immersing the solid after the heat treatment in an acid aqueous solution to maintain the pH at 4 or less;
A second separation step of separating, washing and drying the metal particles in the acid aqueous solution after the acid treatment;
A process for producing a fine metal powder comprising the steps of:
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