JPH04289107A - Production of fine alloy particles - Google Patents
Production of fine alloy particlesInfo
- Publication number
- JPH04289107A JPH04289107A JP7581491A JP7581491A JPH04289107A JP H04289107 A JPH04289107 A JP H04289107A JP 7581491 A JP7581491 A JP 7581491A JP 7581491 A JP7581491 A JP 7581491A JP H04289107 A JPH04289107 A JP H04289107A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- metal ion
- reducing agent
- metal
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 50
- 239000002245 particle Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 230000000737 periodic effect Effects 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 45
- 239000010419 fine particle Substances 0.000 claims description 43
- -1 amine borane derivative Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 abstract 2
- 150000001412 amines Chemical class 0.000 abstract 1
- 229910000085 borane Inorganic materials 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 18
- 229910000521 B alloy Inorganic materials 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910010277 boron hydride Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003018 M(BH4)n Inorganic materials 0.000 description 1
- 229910052781 Neptunium Inorganic materials 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002737 metalloid compounds Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Abstract
Description
【００１】001
【産業上の利用分野】本発明は、周期律表１Ｂ族、２Ｂ
族に属する金属のイオンまたはこの金属イオンのほかに
遷移金属のイオンを含む金属イオン溶液と半金属化合物
溶液とを混合して、水溶液反応により両溶液に含まれる
金属の合金微粒子を製造する方法に関する。[Industrial Application Field] The present invention relates to group 1B and 2B of the periodic table.
A method for producing fine alloy particles of metals contained in both solutions by mixing a metalloid compound solution with a metal ion solution containing ions of metals belonging to the group or ions of transition metals in addition to the metal ions. .
【００２】002]
【従来技術】合金微粒子は、通常のバルク状合金材料に
比べて成形性、表面特性、複合化、混合化に優れており
、最近の固化技術の進歩に伴って微粒子状での応用に限
らず、固化成形体の原料として工業的な重要度が増大し
ている。[Prior Art] Fine alloy particles have superior formability, surface properties, compositing, and mixing properties compared to ordinary bulk alloy materials, and with recent advances in solidification technology, their applications are not limited to fine particles. , is becoming increasingly important industrially as a raw material for solidified molded bodies.
【００３】この合金微粒子の量産的製造は、溶融原料を
ガス圧で霧化して急冷するアトマイズド法、真空あるい
は減圧不活性ガス中で金属または合金を蒸発させる蒸発
法、水素雰囲気中でのア−クプラズマによる活性水素と
溶融金属との反応により行われていた。[003] Mass production of these fine alloy particles can be carried out by an atomized method in which a molten raw material is atomized by gas pressure and rapidly cooled, an evaporation method in which the metal or alloy is evaporated in a vacuum or a reduced pressure inert gas, and an arborization method in a hydrogen atmosphere. It was carried out by the reaction between active hydrogen and molten metal due to plasma.
【００４】しかし、これらの方法では、いずれも装置が
大型になり、また、量産性にも劣るため、製造コストが
高くなるものであった。また、ほとんどが合金を溶融さ
せて、急冷させる方法であるため、合金の融点が高くな
る程製造が難しくなるものであった。さらに、これらの
方法で製造したものは、一般に粒子にばらつきのある場
合があるため、使用にあたっては分級、精製を必要とし
ていた。[004] However, in all of these methods, the apparatus becomes large in size and is also poor in mass productivity, resulting in high manufacturing costs. Furthermore, since most methods involve melting the alloy and rapidly cooling it, the higher the melting point of the alloy, the more difficult it is to manufacture. Furthermore, products produced by these methods generally have particles that vary, and therefore require classification and purification before use.
【００５】本発明者らは、かかる問題のない合金微粒子
製造法として、水素化ホウ素化合物またはアミンボラン
誘導体を含む還元剤溶液中に、（１）Ｆｅ、Ｃｏ、Ｎｉ
イオンの１種または２種以上を含む金属イオン溶液、ま
たは、（２）Ｆｅ、Ｃｏ、Ｎｉイオンの１種または２種
以上と遷移金属イオンの１種または２種以上とを含む金
属イオン溶液、あるいは（３）Ｆｅ、Ｃｏ、Ｎｉイオン
の１種または２種以上と遷移金属イオンの１種または２
種以上および周期律表２Ａ族、３Ｂ族、４Ｂ族、５Ｂ族
に属する金属イオンの１種または２種以上とを含む金属
イオン溶液を混合して、反応させる方法を先に提案した
（特開昭６４−６５２０６号、特開平２−２３２３０８
号、特開平３−６３０９号）。これらの方法は、水素化
ホウ素化合物またはアミンボラン誘導体を還元剤に用い
、この水溶液中に金属イオン溶液を滴下混合して、水溶
液反応により滴下液の金属イオンを還元すると同時にそ
の還元金属を還元剤の分解により生成したホウ素と化合
させて合金微粒子を析出させる方法で、（Ｆｅ、Ｃｏ、
Ｎｉ）−Ｂ系、（Ｆｅ、Ｃｏ、Ｎｉ）−遷移金属−Ｂ系
、（Ｆｅ、Ｃｏ、Ｎｉ）−遷移金属−（２Ａ族、３Ｂ族
、４Ｂ族、５Ｂ族金属）−Ｂ系合金微粒子のように周期
律表の鉄族金属を主成分とする均一な粒径の合金微粒子
を安価に製造することができる。The present inventors have proposed a method for producing fine alloy particles free from such problems by adding (1) Fe, Co, and Ni to a reducing agent solution containing a boron hydride compound or an amine borane derivative.
(2) a metal ion solution containing one or more types of ions, or (2) a metal ion solution containing one or more types of Fe, Co, and Ni ions and one or more types of transition metal ions; or (3) one or more Fe, Co, and Ni ions and one or two transition metal ions.
We have previously proposed a method in which metal ion solutions containing one or more metal ions belonging to Groups 2A, 3B, 4B, and 5B of the Periodic Table are mixed and reacted. No. 64-65206, JP-A-2-232308
No., Japanese Patent Publication No. 3-6309). These methods use a borohydride compound or an amine borane derivative as a reducing agent, drop a metal ion solution into this aqueous solution, reduce the metal ions in the dropped solution through an aqueous reaction, and simultaneously transfer the reduced metal to the reducing agent. This is a method of precipitating alloy fine particles by combining with boron generated by decomposition.
Ni)-B system, (Fe, Co, Ni)-transition metal-B system, (Fe, Co, Ni)-transition metal-(2A group, 3B group, 4B group, 5B group metal)-B system alloy fine particles As shown in the figure, alloy fine particles of uniform particle size mainly composed of metals from the iron group of the periodic table can be produced at low cost.
【００６】006]
【発明が解決しようとする問題点】しかしながら、近年
は、合金微粒子の用途の拡大に伴い、溶融性、導電性、
化学的特性などが鉄族金属を主成分とするものより優れ
たもの、例えば、銅や亜鉛などを主成分とするものが要
求されるようになってきた。そこで、本発明は、かかる
要望を充たすため、周期律表１Ｂ族、２Ｂ族を主成分と
する合金微粒子の製造方法を提供するものである。[Problems to be solved by the invention] However, in recent years, with the expansion of uses for alloy fine particles, meltability, conductivity,
There is a growing demand for materials that have better chemical properties than those whose main components are iron group metals, such as those whose main components are copper, zinc, etc. Therefore, in order to satisfy such a need, the present invention provides a method for producing fine alloy particles whose main components are Groups 1B and 2B of the periodic table.
【００７】007]
【問題点を解決するための手段】本発明は、水素化ホウ
素化合物またはアミンボラン誘導体を含む還元剤溶液中
に、周期律表１Ｂ族、２Ｂ族に属する金属のイオンを１
種または２種以上を含む金属イオン溶液またはこの溶液
中に遷移金属のイオンの１種または２種以上を添加した
金属イオン溶液を混合して、反応させることにより合金
微粒子を製造するようにした。[Means for Solving the Problems] The present invention provides for adding ions of metals belonging to groups 1B and 2B of the periodic table to a reducing agent solution containing a borohydride compound or an amine borane derivative.
Fine alloy particles are produced by mixing a metal ion solution containing one or more species or a metal ion solution to which one or more transition metal ions is added and reacting.
【００８】008
【作用】本発明で使用する水素化ホウ素化合物を含む還
元剤溶液は、従来のように、一般式Ｍ（ＢＨ４）ｎ（但
し、ｎは整数）において、ＭがＬｉ、Ｎａ、Ｋ、Ｂｅ、
Ｍｇ、Ｚｎ、Ｃｄ、Ｃｕ、Ａｇ、Ｇａ、Ｔｉ、Ｚｒ、Ｈ
ｆ、Ｔｈ、Ｕ、Ｎｐ、Ｐｕなどの化合物を溶媒に溶解し
たものでよい。また、アミンボラン誘導体を含む還元剤
溶液もＢＨ３−ＮＨｘＲｙ（但し、Ｒはアルキル基、ｘ
、ｙは整数）などのようなアミンボランアルキル誘導体
を溶媒に溶解したものでよい。溶媒は、有機溶媒でもよ
いが、生産性、製造コストなどから水が好ましい。[Operation] The reducing agent solution containing the boron hydride compound used in the present invention has the general formula M(BH4)n (where n is an integer), where M is Li, Na, K, Be,
Mg, Zn, Cd, Cu, Ag, Ga, Ti, Zr, H
A compound such as f, Th, U, Np, Pu, etc. dissolved in a solvent may be used. In addition, a reducing agent solution containing an amine borane derivative is also BH3-NHxRy (where R is an alkyl group, x
, y is an integer), etc., dissolved in a solvent. The solvent may be an organic solvent, but water is preferable from the viewpoint of productivity, manufacturing cost, etc.
【００９】周期律表１Ｂ族、２Ｂ族に属する金属のイオ
ンを１種または２種以上を含む金属イオン溶液は、１Ｂ
族、２Ｂ族に属する金属の水溶性塩、例えば、硫酸塩、
塩化物、硝酸塩などを水に溶解したものでよい。[009] A metal ion solution containing one or more metal ions belonging to Groups 1B and 2B of the Periodic Table is 1B.
Water-soluble salts of metals belonging to Group 2B, such as sulfates,
A solution of chloride, nitrate, etc. in water may be used.
【０１０】還元剤溶液への金属イオン溶液の混合は、前
者の溶液を撹拌しながら後者の溶液を徐々に滴下して、
反応させる方法によればよいが、合金微粒子は、混合の
際の反応条件により組成、収率、粒径などが若干変化す
る。[010] The metal ion solution is mixed into the reducing agent solution by gradually dropping the latter solution while stirring the former solution.
Any reaction method may be used, but the composition, yield, particle size, etc. of the alloy fine particles may vary slightly depending on the reaction conditions during mixing.
【０１１】例えば、還元剤水溶液の水素化ホウ素化合物
またはアミンボラン誘導体濃度と金属イオン溶液の１Ｂ
族、２Ｂ族の金属イオン濃度とは、前者の濃度を後者の
濃度よりもモル濃度で前者／後者≧１と高くすると、組
成が均一な合金微粒子を高収率で析出させることができ
る。For example, the concentration of the borohydride compound or amine borane derivative in the reducing agent aqueous solution and 1B in the metal ion solution
When the metal ion concentration of Group 2B and Group 2B metal ions is made higher than the latter concentration in terms of molar concentration (former/latter≧1), fine alloy particles having a uniform composition can be precipitated at a high yield.
【０１２】また、反応温度は、高温程反応速度が大きく
なり、析出時間の短縮、粒径の微細化を図ることができ
るが、あまり高くすると、還元剤の分解、空気中で反応
させる場合の析出合金微粒子の酸化などが懸念されるの
で、８０℃以下にするのが好ましい。この温度以下であ
れば、溶液中に１Ｂ族、２Ｂ族の金属イオンが２種以上
含まれていても、合金微粒子の組成には大きな変化が認
められない。反応温度の調節は、還元剤溶液の温度を調
節することにより行えばよい。[012] Also, as for the reaction temperature, the higher the reaction rate, the higher the reaction rate, which can shorten the precipitation time and make the particle size finer. However, if the reaction temperature is too high, the reducing agent may decompose, and when the reaction is carried out in air, Since there is a concern about oxidation of the precipitated alloy fine particles, the temperature is preferably 80° C. or lower. If the temperature is below this temperature, no major change will be observed in the composition of the alloy fine particles even if the solution contains two or more metal ions of Group 1B and Group 2B. The reaction temperature may be adjusted by adjusting the temperature of the reducing agent solution.
【０１３】さらに、還元剤水溶液のｐＨは、１３．５以
下であれば、この範囲でｐＨが変化しても、合金微粒子
組成に大きな変化がなく、析出量も多い。前記のような
還元剤化合物の水溶液は、化合物を水に溶解したままの
状態で、ｐＨ＝１０〜１１を示すので、ｐＨを特別に調
節する必要はない。Furthermore, if the pH of the reducing agent aqueous solution is 13.5 or less, even if the pH changes within this range, the composition of the alloy fine particles will not change significantly and the amount of precipitation will be large. Since the aqueous solution of the reducing agent compound as described above has a pH of 10 to 11 while the compound remains dissolved in water, there is no need to particularly adjust the pH.
【０１４】本発明において、合金微粒子の耐食性や強度
などをさらに向上させたい場合には、金属イオン溶液中
にＣｒ、Ｍｏ、Ｆｅ、Ｃｏ、Ｎｉ、Ｗ、Ｖ、Ｎｂ、Ｔａ
、Ｔｉ、Ｚｒなどの遷移金属イオンを１種または２種以
上添加することにより向上させることができる。この場
合、遷移金属イオンは、硫酸塩、硝酸塩、塩化物のよう
な水溶性塩を添加すればよい。In the present invention, when it is desired to further improve the corrosion resistance and strength of the alloy fine particles, Cr, Mo, Fe, Co, Ni, W, V, Nb, Ta, etc. are added to the metal ion solution.
It can be improved by adding one or more types of transition metal ions such as , Ti, and Zr. In this case, the transition metal ion may be added as a water-soluble salt such as sulfate, nitrate, or chloride.
【０１５】析出した合金微粒子は、ろ過した後水や有機
溶剤で洗浄すればよい。本発明により得られる合金微粒
子は、粒径が０．０２〜０．２０μｍと極めて小さく、
また、粒度分布の幅も小さい。[015] The precipitated alloy fine particles may be filtered and then washed with water or an organic solvent. The alloy fine particles obtained by the present invention have an extremely small particle size of 0.02 to 0.20 μm,
Furthermore, the width of the particle size distribution is also small.
【０１６】016]
【実施例】実施例１
濃度がそれぞれ１〜２ｍｏｌ／ｌである水素化ホウ素カ
リウム（ＫＢＨ４）、水素化ホウ素ナトリウム（ＮａＢ
Ｈ４）、ジメチルアミンボラン（ＤＭＡＢ）の各還元剤
水溶液を撹拌しながら、その中に濃度が０．１〜０．２
ｍｏｌ／ｌである周期律表１Ｂ族、２Ｂ族の金属イオン
を１種または２種以上含む金属イオン水溶液を滴下混合
して反応させ、析出した黒色沈澱物をろ過、洗浄した。
第１表に得られた合金微粒子の組成、結晶構造、粒径を
示す。なお、還元剤水溶液の調製は、還元剤を蒸留水に
溶解したままのもの（ｐＨ＝１０〜１１）を用い、還元
剤水溶液の還元剤濃度と金属イオン水溶液の金属イオン
濃度とのモル濃度比は、いずれも前者／後者＝１０にし
、反応温度２０℃で行った。また、合金微粒子の組成お
よび結晶構造の決定は、それぞれ化学分析およびＸ線回
折で行い、粒径は透過電子顕微鏡で測定した。[Example] Example 1 Potassium borohydride (KBH4) and sodium borohydride (NaB) each have a concentration of 1 to 2 mol/l.
H4) and dimethylamine borane (DMAB) with a concentration of 0.1 to 0.2 while stirring.
A metal ion aqueous solution containing one or more metal ions of Groups 1B and 2B of the periodic table in mol/l was mixed dropwise and reacted, and the precipitated black precipitate was filtered and washed. Table 1 shows the composition, crystal structure, and particle size of the obtained alloy fine particles. The reducing agent aqueous solution is prepared by using the reducing agent dissolved in distilled water (pH = 10 to 11), and determining the molar concentration ratio of the reducing agent concentration in the reducing agent aqueous solution and the metal ion concentration in the metal ion aqueous solution. In both cases, the former/latter ratio was set to 10, and the reaction temperature was 20°C. Further, the composition and crystal structure of the alloy fine particles were determined by chemical analysis and X-ray diffraction, respectively, and the particle size was measured by a transmission electron microscope.
【０１７】実施例２
実施例１と同一製造条件で水素化ホウ素カリウム還元剤
水溶液に周期律表１Ｂ族、２Ｂ族の金属イオンと遷移金
属イオンとを含む金属イオン水溶液を滴下混合して、合
金微粒子を製造した。第２表に得られた合金微粒子を示
す。Example 2 A metal ion aqueous solution containing metal ions of groups 1B and 2B of the periodic table and transition metal ions was added dropwise to an aqueous solution of a potassium borohydride reducing agent under the same manufacturing conditions as in Example 1 to form an alloy. Microparticles were produced. Table 2 shows the alloy fine particles obtained.
【０１８】018]
【第１表】[Table 1]
【０１９】019]
【第２表】[Table 2]
【０２０】実施例３
濃度が０．１ｍｏｌ／ｌのＣｕイオン水溶液を種々の濃
度の水素化ホウ素カリウム水溶液中に滴下混合して、Ｃ
ｕ−Ｂ系合金微粒子を製造した。反応温度はいずれも２
０℃にし、還元剤水溶液は、水素化ホウ素カリウムを蒸
留水に溶解したままのものを用い、ｐＨは調整しなかっ
た。
図１にＫＢＨ４／Ｃｕイオンのモル濃度比と合金微粒子
組成（原子％）との関係を、図２に析出量との関係を示
す。なお、図２の縦軸におけるＷ／Ｗ１０は、ＫＢＨ４
濃度が金属イオン濃度の１０倍である場合の析出量を基
準析出量Ｗ１０とし、この析出量に対して本実施例での
析出量Ｗが何％析出したかを示すように規格化したもの
である。図４の析出量Ｗ／Ｗ１０も同じである。Example 3 An aqueous solution of Cu ions with a concentration of 0.1 mol/l was mixed dropwise into an aqueous solution of potassium borohydride with various concentrations.
u-B alloy fine particles were manufactured. The reaction temperature is 2 in both cases.
The temperature was 0° C., the reducing agent aqueous solution used was potassium borohydride dissolved in distilled water, and the pH was not adjusted. FIG. 1 shows the relationship between the molar concentration ratio of KBH4/Cu ions and the alloy fine particle composition (atomic %), and FIG. 2 shows the relationship with the amount of precipitation. In addition, W/W10 on the vertical axis of FIG. 2 is KBH4
The precipitation amount when the concentration is 10 times the metal ion concentration is defined as the standard precipitation amount W10, and the precipitation amount W in this example is standardized to indicate what percentage of this precipitation amount. be. The precipitation amount W/W10 in FIG. 4 is also the same.
【０２１】実施例４
実施例３においてＣｕイオン水溶液の代わりに金属イオ
ンの量比がＣｕ２＋：Ｆｅ２＋：Ｚｎ２＋＝７：２：１
で、合計イオン濃度が０．１ｍｏｌ／ｌの複合金属イオ
ン水溶液を用いて、Ｃｕ−Ｆｅ−Ｚｎ−Ｂ系合金微粒子
を製造した。図３にＫＢＨ４／金属イオンのモル濃度比
と合金微粒子組成（原子％）との関係を、図４に析出量
との関係を示す。Example 4 In Example 3, the amount ratio of metal ions was Cu2+:Fe2+:Zn2+=7:2:1 instead of the Cu ion aqueous solution.
Cu-Fe-Zn-B alloy fine particles were manufactured using a composite metal ion aqueous solution having a total ion concentration of 0.1 mol/l. FIG. 3 shows the relationship between the KBH4/metal ion molar concentration ratio and the alloy fine particle composition (atomic %), and FIG. 4 shows the relationship with the precipitation amount.
【０２２】実施例５
濃度が１ｍｏｌ／ｌのジメチルアミンボラン（ＤＭＡＢ
）水溶液に金属イオンの量比がＣｕ２＋：Ｎｉ２＋＝７
：３で、合計イオン濃度が０．１ｍｏｌ／ｌの複合金属
イオン水溶液を滴下して、反応温度を２〜９５℃の範囲
で変化させながらＣｕ−Ｎｉ−Ｂ系合金微粒子を製造し
た。図５に反応温度と合金微粒子組成（原子％）との関
係を示す。Example 5 Dimethylamine borane (DMAB) with a concentration of 1 mol/l
) The amount ratio of metal ions in the aqueous solution is Cu2+:Ni2+ = 7
:3, a composite metal ion aqueous solution having a total ion concentration of 0.1 mol/l was added dropwise to produce Cu-Ni-B alloy fine particles while changing the reaction temperature in the range of 2 to 95°C. FIG. 5 shows the relationship between reaction temperature and alloy fine particle composition (atomic %).
【０２３】実施例６
実施例５において、Ｃｕ、Ｎｉ複合金属イオン水溶液の
代わりに金属イオンの量比がＣｕ２＋：Ｚｎ２＋：Ａｕ
３＋：Ｆｅ２＋＝７：２：０．５：０．５で、合計イオ
ン濃度が０．１ｍｏｌ／ｌの複合金属イオン水溶液を用
いて、Ｃｕ−Ｚｎ−Ａｕ−Ｆｅ−Ｂ系合金微粒子を製造
した。図６に反応温度と合金微粒子組成（原子％）との
関係を示す。Example 6 In Example 5, the metal ion amount ratio was Cu2+:Zn2+:Au instead of the Cu, Ni composite metal ion aqueous solution.
Cu-Zn-Au-Fe-B based alloy fine particles were produced using a composite metal ion aqueous solution with 3+:Fe2+=7:2:0.5:0.5 and a total ion concentration of 0.1 mol/l. . FIG. 6 shows the relationship between reaction temperature and alloy fine particle composition (atomic %).
【０２４】実施例７
濃度が１ｍｏｌ／ｌの水素化ホウ素カリウム水溶液中に
水酸化ナトリウムを添加して、種々のｐＨの還元剤水溶
液を調製し、これにＣｕイオン水溶液を滴下混合して、
Ｃｕ−Ｂ系合金微粒子を製造した。なお、反応温度はい
ずれも２０℃とした。図７にｐＨと、合金微粒子組成（
原子％）との関係を示す。Example 7 Sodium hydroxide was added to a potassium borohydride aqueous solution with a concentration of 1 mol/l to prepare reducing agent aqueous solutions with various pHs, and a Cu ion aqueous solution was added dropwise and mixed therein.
Cu-B alloy fine particles were manufactured. Note that the reaction temperature was 20°C in all cases. Figure 7 shows the pH and alloy fine particle composition (
(atomic%).
【０２５】実施例８
実施例７において、Ｃｕイオン水溶液の代わりに金属イ
オンの量比がＣｕ２＋：Ｚｎ２＋：Ｆｅ２＋＝７：１．
５：１．５で、合計イオン濃度が０．１ｍｏｌ／ｌの複
合金属イオン水溶液を用いて、Ｃｕ−Ｚｎ−Ｆｅ−Ｂ系
合金微粒子を製造した。
図８にｐＨと合金微粒子組成（原子％）との関係を示す
。Example 8 In Example 7, instead of the Cu ion aqueous solution, the amount ratio of metal ions was Cu2+:Zn2+:Fe2+=7:1.
Cu-Zn-Fe-B based alloy fine particles were manufactured using a composite metal ion aqueous solution with a ratio of 5:1.5 and a total ion concentration of 0.1 mol/l. FIG. 8 shows the relationship between pH and alloy fine particle composition (atomic %).
【０２６】026]
【発明の効果】以上のように、本発明によれば、周期律
表１Ｂ族、２Ｂ族に属する金属を主成分とする合金微粒
子を製造できる。従って、導電用ペ−スト材料、導電ろ
う接用材料、電極のように溶融性や導電性を特に必要と
する電気部品、化学反応触媒のような化学特性を必要と
する材料、そらには、セラミックス、塗料、異種金属、
プラスチックなどとの混合分散剤などに利用できる。As described above, according to the present invention, fine alloy particles containing metals belonging to Groups 1B and 2B of the Periodic Table as a main component can be produced. Therefore, conductive paste materials, conductive soldering materials, electrical parts that require meltability and conductivity such as electrodes, materials that require chemical properties such as chemical reaction catalysts, etc. ceramics, paints, dissimilar metals,
It can be used as a mixing dispersant with plastics, etc.
【図１】実施例３でＣｕ−Ｂ系合金微粒子を製造した場
合のＫＢＨ４／Ｃｕイオンのモル濃度比と合金微粒子組
成（原子％）との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the molar concentration ratio of KBH4/Cu ions and the alloy fine particle composition (atomic %) when Cu-B alloy fine particles were produced in Example 3.
【図２】実施例３でＣｕ−Ｂ系合金微粒子を製造した場
合のＫＢＨ４／Ｃｕイオンのモル濃度比と析出量との関
係を示すグラフである。FIG. 2 is a graph showing the relationship between the molar concentration ratio of KBH4/Cu ions and the precipitation amount when Cu-B alloy fine particles were produced in Example 3.
【図３】実施例４でＣｕ−Ｆｅ−Ｚｎ−Ｂ系合金微粒子
を製造した場合のＫＢＨ４／金属イオンのモル濃度比と
合金微粒子組成（原子％）との関係を示すグラフである
。FIG. 3 is a graph showing the relationship between the KBH4/metal ion molar concentration ratio and the alloy fine particle composition (atomic %) when Cu-Fe-Zn-B alloy fine particles were produced in Example 4.
【図４】実施例４でＣｕ−Ｆｅ−Ｚｎ−Ｂ系合金微粒子
を製造した場合のＫＢＨ４／金属イオンのモル濃度比と
析出量との関係を示すグラフである。FIG. 4 is a graph showing the relationship between the molar concentration ratio of KBH4/metal ion and the precipitation amount when Cu-Fe-Zn-B alloy fine particles were produced in Example 4.
【図５】実施例５でＣｕ−Ｎｉ−Ｂ系合金微粒子を製造
した場合の反応温度と合金微粒子組成（原子％）との関
係を示すグラフである。FIG. 5 is a graph showing the relationship between reaction temperature and alloy fine particle composition (atomic %) when Cu-Ni-B alloy fine particles were produced in Example 5.
【図６】実施例６でＣｕ−Ｚｎ−Ａｕ−Ｆｅ−Ｂ系合金
微粒子を製造した場合の反応温度と合金微粒子組成（原
子％）との関係を示すグラフである。FIG. 6 is a graph showing the relationship between reaction temperature and alloy fine particle composition (atomic %) when Cu-Zn-Au-Fe-B alloy fine particles were produced in Example 6.
【図７】実施例７でＣｕ−Ｂ系合金微粒子を製造した場
合のｐＨと合金微粒子組成（原子％）との関係を示すグ
ラフである。FIG. 7 is a graph showing the relationship between pH and alloy fine particle composition (atomic %) when Cu-B alloy fine particles were produced in Example 7.
【図８】実施例８でＣｕ−Ｚｎ−Ｆｅ−Ｂ系合金微粒子
を製造した場合のｐＨと合金微粒子組成（原子％）との
関係を示すグラフである。FIG. 8 is a graph showing the relationship between pH and alloy fine particle composition (atomic %) when Cu-Zn-Fe-B alloy fine particles were produced in Example 8.
Claims (7)
誘導体を含む還元剤溶液中に、周期律表１Ｂ族、２Ｂ族
に属する金属のイオンを１種または２種以上を含む金属
イオン溶液を混合して、反応させることを特徴とする合
金微粒子の製造方法。1. A metal ion solution containing one or more metal ions belonging to Groups 1B and 2B of the Periodic Table is mixed in a reducing agent solution containing a borohydride compound or an amine borane derivative, A method for producing alloy fine particles characterized by a reaction.
ン誘導体を含む還元剤溶液中に、周期律表１Ｂ族、２Ｂ
族に属する金属のイオンを１種または２種以上と遷移金
属のイオンの１種または２種以上とを含む金属イオン溶
液を混合して、反応させることを特徴とする合金微粒子
の製造方法。2. In a reducing agent solution containing a borohydride compound or an amine borane derivative,
A method for producing fine alloy particles, which comprises mixing and reacting a metal ion solution containing one or more metal ions belonging to the group A and one or more transition metal ions.
する金属のイオンが銅イオンであることを特徴とする請
求項１または２に記載の合金微粒子の製造方法。3. The method for producing fine alloy particles according to claim 1, wherein the ions of a metal belonging to group 1B of the periodic table in the metal ion solution are copper ions.
する金属のイオンが亜鉛イオンであることを特徴とする
請求項１または２に記載の合金微粒子の製造方法。4. The method for producing fine alloy particles according to claim 1 or 2, wherein the ions of a metal belonging to group 2B of the periodic table in the metal ion solution are zinc ions.
はアミンボラン誘導体濃度と金属イオン溶液の金属イオ
ン濃度をモル濃度比で前者／後者≧１とすることを特徴
とする請求項１〜４に記載のいずれかの合金微粒子の製
造方法。5. The method according to claim 1, wherein the concentration of the borohydride compound or the amine borane derivative in the reducing agent solution and the metal ion concentration in the metal ion solution are such that the molar concentration ratio is former/latter≧1. A method for producing any alloy fine particles.
徴とする請求項１〜５に記載のいずれかの合金微粒子の
製造方法。6. The method for producing fine alloy particles according to claim 1, wherein the reaction temperature is 80° C. or lower.
ることを特徴とする請求項１〜６に記載のいずれかの合
金微粒子の製造方法。7. The method for producing fine alloy particles according to claim 1, wherein the pH of the reducing agent solution is set to 13.5 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7581491A JPH04289107A (en) | 1991-03-15 | 1991-03-15 | Production of fine alloy particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7581491A JPH04289107A (en) | 1991-03-15 | 1991-03-15 | Production of fine alloy particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04289107A true JPH04289107A (en) | 1992-10-14 |
Family
ID=13587025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7581491A Withdrawn JPH04289107A (en) | 1991-03-15 | 1991-03-15 | Production of fine alloy particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04289107A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023631A1 (en) * | 1998-10-16 | 2000-04-27 | Eurotungstene Poudres | Micronic pre-alloyed metal powder based on three-dimensional transition metal |
| JP2007063657A (en) * | 2005-09-02 | 2007-03-15 | Chiba Inst Of Technology | Permanent magnet material |
| JP2007533862A (en) * | 2004-04-22 | 2007-11-22 | 本田技研工業株式会社 | Metal and alloy nanoparticles and methods for their synthesis |
| JP2008019503A (en) * | 2006-07-10 | 2008-01-31 | Samsung Electro-Mechanics Co Ltd | Method for manufacturing copper nanoparticle, and copper nanoparticle obtained by the method |
| WO2021148973A1 (en) * | 2020-01-21 | 2021-07-29 | Universita' Degli Studi Di Padova | Multifunctional nanoparticles based on metallic nanoalloys for diagnostic and therapeutic use |
-
1991
- 1991-03-15 JP JP7581491A patent/JPH04289107A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023631A1 (en) * | 1998-10-16 | 2000-04-27 | Eurotungstene Poudres | Micronic pre-alloyed metal powder based on three-dimensional transition metal |
| JP2007533862A (en) * | 2004-04-22 | 2007-11-22 | 本田技研工業株式会社 | Metal and alloy nanoparticles and methods for their synthesis |
| JP2007063657A (en) * | 2005-09-02 | 2007-03-15 | Chiba Inst Of Technology | Permanent magnet material |
| JP2008019503A (en) * | 2006-07-10 | 2008-01-31 | Samsung Electro-Mechanics Co Ltd | Method for manufacturing copper nanoparticle, and copper nanoparticle obtained by the method |
| WO2021148973A1 (en) * | 2020-01-21 | 2021-07-29 | Universita' Degli Studi Di Padova | Multifunctional nanoparticles based on metallic nanoalloys for diagnostic and therapeutic use |
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