JPH036309A - Manufacture of amorphous alloy fine particles - Google Patents
Manufacture of amorphous alloy fine particlesInfo
- Publication number
- JPH036309A JPH036309A JP14065589A JP14065589A JPH036309A JP H036309 A JPH036309 A JP H036309A JP 14065589 A JP14065589 A JP 14065589A JP 14065589 A JP14065589 A JP 14065589A JP H036309 A JPH036309 A JP H036309A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- metal ion
- alloy fine
- amorphous alloy
- aqueous solution
- 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.)
- Pending
Links
- 239000010419 fine particle Substances 0.000 title claims abstract description 54
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 51
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- -1 boron hydride compound Chemical class 0.000 claims abstract description 13
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910001427 strontium ion Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910010277 boron hydride Inorganic materials 0.000 abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052796 boron Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 4
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 26
- 239000000956 alloy Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 14
- 229910000521 B alloy Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241001459693 Dipterocarpus zeylanicus Species 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 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
- 238000000746 purification Methods 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、金属イオン水溶液と半金属含有化合物水溶液
との反応により非晶質合金微粒子を製造する際、粒径の
ばらつきの小さいものを工業的に高収率で安価に製造す
る方法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention provides an industrial method for producing amorphous alloy fine particles with small variation in particle size by the reaction between a metal ion aqueous solution and a semimetal-containing compound aqueous solution. It relates to a method for producing it at a high yield and at low cost.
（従来技術）
非晶質合金微粒子は、リボン材やワイヤー材に比べ、成
形性、表面特性、複合化、混合化に優れており、最近の
同化技術の進歩に伴って微粒子状態のみならず、バルク
状非晶貿体の作製原料として工業的な重要度も増大しで
いる。例えば、微粒子状態での使用は、磁性材料や触媒
材料などであるが、強度材料やセラミックス、塗料など
の混合剤としての耐食材料など固化して使用する分野で
の原料として注目されている。(Prior art) Amorphous alloy fine particles are superior in formability, surface properties, compositing, and mixing compared to ribbon materials and wire materials. Its industrial importance as a raw material for producing bulk amorphous materials is also increasing. For example, it is used in the form of fine particles in magnetic materials, catalytic materials, etc., but it is attracting attention as a raw material in fields where it is used in solidified form, such as strength materials, ceramics, and corrosion-resistant materials as mixtures for paints.
従来、この非晶質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法、溶融合金を
微小すき間の２本の高速回転ロールの間に噴出させて、
ロール間で生じる溶融合金のキャビテーションにより霧
化、急冷するキャビテーション法、または溶融合金を回
転液中に噴出させて急冷する回転液中噴出法などにより
行なわれている。Conventionally, mass production of amorphous alloy particles has been carried out using the atomization method, in which molten raw materials are atomized using gas pressure and rapidly cooled, or the molten alloy is jetted between two high-speed rotating rolls with a small gap between them.
This is carried out by a cavitation method in which the molten alloy is atomized and rapidly cooled by cavitation generated between rolls, or by an injection method in a rotating liquid in which the molten alloy is jetted into a rotating liquid and rapidly cooled.
しかし、これらの方法は、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。ま
た、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。さらに、低
温での成形性（焼結性）は粒径が小さい程良好になるが
、前記方法で得られる粒子は、粒径が大きく、しがも不
均一であり、比較的ばらつきの小さなものでも１〜５０
μ箱の範囲であった。このため、使用１こあたっＣは分
級、精製を必要としていた。However, all of these methods require large equipment and
In addition, it is inferior in mass productivity, resulting in high manufacturing costs. Furthermore, since the method involves melting the alloy and rapidly cooling it, the higher the melting point of the alloy, the more difficult it is to manufacture. Furthermore, the smaller the particle size, the better the formability (sinterability) at low temperatures; however, the particles obtained by the above method have large particle sizes, are non-uniform, and have relatively small variations. But 1-50
It was in the μ box range. For this reason, the 1 koatat C used required classification and purification.
そこで、本発明者らは、かがる問題を解決した非晶質合
金微粒子の製造方法として、先に水素化ホウ素化合物ま
たはアミンボラン誘導体の水溶液中にＦｅ、 Ｃｏ、旧
イオンの１種または２種以上を含む水溶液またはこの金
属イオン水溶液中にさらに遷移金属イオンの１種または
２種以上を添加した一
水溶液を混合して反応させる方法を提案した（特開昭６
４−６５２０６号）。Therefore, the present inventors developed a method for manufacturing amorphous alloy fine particles that solved this problem by first adding one or two of Fe, Co, and old ions to an aqueous solution of a boron hydride compound or an amine borane derivative. We proposed a method of mixing and reacting an aqueous solution containing the above metal ions or an aqueous solution in which one or more transition metal ions were further added to this metal ion aqueous solution (Japanese Patent Application Laid-Open No. 1983-1993).
No. 4-65206).
この方法は、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水溶液
を滴下混合して、水溶液反応により鉄族金属や遷移金属
のイオンを還元すると同時に分解したホウ素と化合させ
てホウ素含有非晶質合金微粒子を析出させる方法で、ホ
ウ素が非晶質形成能を高め、しかも、反応が極めて急激
に進行するので、析出微粒子は非晶質となる。この方法
での粒径は、１０μｍ以下で、ばらつきが小さく、しか
も、ホラ素成分を従来法より高くすることも可能な非晶
質合金微粒子を常温付近の温度で量産できるという特徴
を有している。This method uses a boron hydride compound or an amine borane derivative as a reducing agent, drops an aqueous metal ion solution into this aqueous solution, reduces iron group metal and transition metal ions through an aqueous reaction, and simultaneously combines the decomposed boron and In this method, boron-containing amorphous alloy fine particles are precipitated, boron increases the ability to form an amorphous state, and the reaction proceeds extremely rapidly, so that the precipitated fine particles become amorphous. This method has the characteristics that the particle size is 10 μm or less, with small variations, and that amorphous alloy fine particles can be mass-produced at a temperature near room temperature, and the hora element content can be increased higher than that of conventional methods. There is.
（発明が解決しようとする問題点）
しかし、この方法での粒径は、従来法での１〜５０μｍ
ｎに比較すると、１０μ＋ｎ以下と小さく、ばらつきも
小さいが、まだ粒径やそのばらつきが大きいという問題
があった。(Problem to be solved by the invention) However, the particle size in this method is 1 to 50 μm compared to the conventional method.
Compared to n, the particle size is smaller than 10μ+n and the variation is also small, but there is still a problem that the particle size and its variation are large.
本発明は、この粒径やそのばらつきを小さくした非晶質
合金微粒子の製造方法を提供するものである。The present invention provides a method for producing amorphous alloy fine particles in which the particle size and its variation are reduced.
（問題点を解決するための手段）
本発明者らは、非晶質合金微粒子の粒径を小さくする方
法を種々検討した結果、金属イオン水溶液に周期律表２
Ａ族、３Ｂ族、４Ｂ族、５Ｂ族に属する金属イオンの１
種または２種以上添加して還元剤水溶液中に混合すれば
良いことを見出だした。(Means for Solving the Problems) As a result of various studies on methods for reducing the particle size of amorphous alloy fine particles, the present inventors found that metal ion aqueous solution was
A metal ion belonging to Group A, Group 3B, Group 4B, Group 5B
It has been found that it is sufficient to add a species or two or more species and mix them into an aqueous reducing agent solution.
本発明により得られる合金微粒子のばらつきは、０．０
２〜０．１０μｍと小さく、粒径も極めて微細である。The variation in alloy fine particles obtained by the present invention is 0.0
The particle size is as small as 2 to 0.10 μm, and the particle size is also extremely fine.
本発明では、還元剤水溶液を攪拌しながら、そこに金属
イオン水溶液を滴下混合して合金微粒子を製造するので
あるが、合金微粒子は、反応条件により組成、収率、構
造が若干変化する。In the present invention, alloy fine particles are produced by dropping an aqueous metal ion solution into an aqueous reducing agent solution while stirring, but the composition, yield, and structure of the alloy fine particles vary slightly depending on the reaction conditions.
例えば、還元剤と金属イオンの濃度については、均一な
組成の合金微粒子を高収率で析出させ、しかも、構造を
非晶質にするため、モル濃度比で水素化ホウ素化合物ま
たはアミンボラン誘導体／金一
属イオン≧１にするのが好ましい。For example, regarding the concentration of the reducing agent and metal ions, in order to precipitate fine alloy particles with a uniform composition in high yield and to have an amorphous structure, the molar concentration ratio of borohydride compound or amine borane derivative/gold It is preferable that ions of one group ≧1.
また、反応温度については、温度が高い程反応が速く進
行し、析出時間を短縮できるが、あまり高くすると、水
溶液中での還元剤分解や空気中で反応させる場合の析出
微粒子の酸化が懸念されるので、８０℃以下にするのが
好ましい。この温度以下であれば、水溶液中に金属イオ
ンが２種以上含まれていても、合金微粒子の組成に大き
な変化が認められない。反応温度の調節は、還元剤水溶
液の温度を調節することにより行えば良い。Regarding the reaction temperature, the higher the temperature, the faster the reaction will proceed and the precipitation time can be shortened, but if it is too high, there are concerns that the reducing agent will decompose in the aqueous solution and the precipitated fine particles will be oxidized when the reaction is carried out in the air. Therefore, it is preferable to keep the temperature below 80°C. If the temperature is below this temperature, no major change will be observed in the composition of the alloy fine particles even if the aqueous solution contains two or more types of metal ions. The reaction temperature may be adjusted by adjusting the temperature of the reducing agent aqueous solution.
さらに、還元剤水溶液のｐｌ＋については、ｐｌ＋１３
．５以下にすれば、組成に大きな変化が認められず、析
出量も多い。水素化ホウ素化合物またはアミンボラン誘
導体の水溶液は、調製したままの状態であればｐｌ＝
１０〜１１であるので、そのまま使用することができる
。Furthermore, for pl+ of the reducing agent aqueous solution, pl+13
．． When the value is 5 or less, no major change is observed in the composition and the amount of precipitation is large. If an aqueous solution of a borohydride compound or an amine borane derivative is as prepared, pl=
Since it is 10 to 11, it can be used as is.
（実施例）
実施例１
水素化ホウ素カリウム（ＫＢＨ，）、水素化ホウ素ナト
リウム（Ｎａｌｌｌｌ＋）またはジメチルアミンボラン
（ＤＨ八へ）の還元剤水溶液を攪拌しながら、その中に
Ｆｅ、 Ｃｏ、 Ｎｉイオンの１種または２種以上と、
周期律表２Ａ族、３Ｂ族、４Ｂ族、５Ｂ族に属する金属
イオンとを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。(Example) Example 1 While stirring a reducing agent aqueous solution of potassium borohydride (KBH), sodium borohydride (Nallll+), or dimethylamine borane (DH8), Fe, Co, and Ni ions were added therein. one or more types of
An aqueous metal ion solution containing metal ions belonging to Groups 2A, 3B, 4B, and 5B of the Periodic Table 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.
なお、混合は、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を前者／後者＝
１０にし、反応温度を２０℃にして行った。また、還元
剤水溶液は、還元剤を溶解したままの状態（ＩＩＨＩＯ
〜１１）で使用した。合金微粒子の組成および構造の決
定はそれぞれ化学分析およびＸ線回折法により、粒径は
透過型電子顕微鏡によった。For mixing, 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 is defined as former/latter =
10, and the reaction temperature was set to 20°C. In addition, the reducing agent aqueous solution is in a state where the reducing agent remains dissolved (IIHIO
~11). The composition and structure of the alloy fine particles were determined by chemical analysis and X-ray diffraction, respectively, and the particle size was determined by a transmission electron microscope.
７−
実施例２
実施例１と同一の製造条件で水素化ホウ素カリウム（Ｋ
ＢＩｌ、）水溶液にＦｅ５Ｃｏ、旧イオンの１種または
２種以上と、遷移金属イオンおよび周期律表２Ａ族、３
Ｂ族、４Ｂ族、５Ｂ族に属する金属イオンとを含む金属
イオン水溶液を滴下混合した。得られた合金微粒子の性
状を第２表に示す。7- Example 2 Potassium borohydride (K
BIl,) Fe5Co in an aqueous solution, one or more old ions, transition metal ions, and groups 2A and 3 of the periodic table.
A metal ion aqueous solution containing metal ions belonging to Group B, Group 4B, and Group 5B was added dropwise and mixed. Table 2 shows the properties of the obtained alloy fine particles.
１
１２一
実施例３
金属イオン量比がＦｅ２＋：Δ１３＋＝７：３で、その
合計イオン濃度を０ 、１ ｍｏｌ／ｇとした金属イオ
ン水溶液を種々の濃度の叶へＢ還元剤水溶液に滴下混合
して、Ｆｅ−＾１−Ｂ系合金微粒子を製造した。なお、
反応温度は２０℃にし、還元剤水溶液の１）ＩＩは調整
しなかった。第１図の（Ａ）にＤＭ八へと金属イオンの
濃度比による合金微粒子組成変化を、第１図（Ｂ）に析
出量を示す。なお、第１図の（Ｂ）の縦軸での析出量Ｗ
／ Ｗ ＋ ｏは、ＤＨ八へ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ＷＩＧとし、こ
の析出量Ｗ、。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である（実施例４の場合
も同じ）。1 12-Example 3 A metal ion aqueous solution with a metal ion amount ratio of Fe2+:Δ13+=7:3 and a total ion concentration of 0 and 1 mol/g was dropped and mixed with a B reducing agent aqueous solution on leaves of various concentrations. In this way, Fe-^1-B alloy fine particles were manufactured. In addition,
The reaction temperature was 20° C., and 1) II of the reducing agent aqueous solution was not adjusted. FIG. 1(A) shows the change in alloy fine particle composition depending on the metal ion concentration ratio from DM8 to DM8, and FIG. 1(B) shows the amount of precipitation. In addition, the amount of precipitation W on the vertical axis in (B) of FIG.
/ W + o is the standard precipitation amount WIG, which is the precipitation amount when the concentration of DH8 is 10 times the metal ion concentration, and this precipitation amount W. The precipitation amount W in this example is standardized to show what percentage of precipitation (the same applies to Example 4).
実施例４
実施例３において、金属イオン水溶液として、金属イオ
ン量比が旧２＋：（：、２＋：＾Ｉ’＝７：１．５：１
．５で、それらの合計イオン濃度が０．１ ｍｏｌ／ｇ
であるものを用いてＮｉ−Ｃｕ−へｌ−Ｂ系合金微粒子
を製造した。第２図の（Ａ）にＤＭ八へと金属イオンの
濃度比による合金微粒子組成変化を、第２図の（Ｂ）に
析出量を示す。Example 4 In Example 3, as a metal ion aqueous solution, the metal ion amount ratio was 2+:(:, 2+:^I'=7:1.5:1
．． 5, and their total ion concentration is 0.1 mol/g
Ni-Cu-I-B alloy fine particles were produced using the following. FIG. 2(A) shows the change in alloy fine particle composition depending on the metal ion concentration ratio from DM8 to DM8, and FIG. 2(B) shows the amount of precipitation.
実施例５
濃度１ｍｏｌ／ｇの水素化ホウ素ナトリウム（ＮａＢＩ
Ｉ−）水溶液に金属イオン量比がＮｉ”：＾１３＋＝７
：３で、それらの合計イオン濃度が０ 、１ ｍｏｌ／
ｅである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からＮｉ−へｌ−Ｂ系合金微
粒子を製造した。また、同様にして金属イオン量比が旧
” ：Ｃｒ” ：八１３＋ ＝ ７ ：１．５ ：１．
５で、それらの合計イオン濃度が０．１ ｍｏｌ／ｅで
ある金属イオン水溶液を滴下して、Ｎｉ−Ｃｒ−へｌ−
Ｂ系合金微粒子を製造した。なお、還元剤水溶液のｐｉ
はＷＩ４整しなかった。第３図の（Ａ）に旧−へｔ−Ｂ
系合金微粒子の場合の反応温度による組成変化を、第３
図の（Ｂ）にＮｉ−Ｃｒ−＾１−Ｂ系合金微粒子の場合
の反応温度による組成変化を示す。Example 5 Sodium borohydride (NaBI) at a concentration of 1 mol/g
I-) Metal ion amount ratio in aqueous solution is Ni”:^13+=7
:3, and their total ion concentration is 0, 1 mol/
Add the metal ion aqueous solution (e) dropwise to raise the reaction temperature to 2~
Ni- to l-B alloy fine particles were produced by changing the temperature within a range of 95°C. Similarly, the metal ion content ratio was 7:1.5:1.
In Step 5, a metal ion aqueous solution with a total ion concentration of 0.1 mol/e was added dropwise to the Ni-Cr-
B-based alloy fine particles were manufactured. In addition, pi of the reducing agent aqueous solution
was not fixed in WI4. Figure 3 (A) shows the old-t-B
The compositional change due to reaction temperature in the case of alloy fine particles is explained in the third section.
Part (B) of the figure shows the composition change depending on the reaction temperature in the case of Ni-Cr-^1-B alloy fine particles.
実施例６
濃度１ｍｏｌ／ｇの水素化ホウ素カリウム（ＫＢＨ，）
水溶液に水酸化ナトリウムを添加して、種々のＩＩＨの
１３
４−
水溶液を調製し、この水溶液に金属イオン量比がＣｏ”
：＾１８＋＝７：３で、合計イオン濃度が０．１ｍ。Example 6 Potassium borohydride (KBH,) at a concentration of 1 mol/g
Sodium hydroxide is added to the aqueous solution to prepare various 134- aqueous solutions of IIH, and this aqueous solution has a metal ion content ratio of Co''.
:^18+=7:3, total ion concentration is 0.1m.
ｌｅである金属イオン水溶液を滴下混合することにより
Ｃｏ−ＡＩ−Ｂ系合金微粒子を製造した。同様に金属イ
オン量比がＣｏ２＋ ：Ｃｕ２＋ ：＾ｌ”＝７：１．
５：１．５で、それらの合計イオン濃度が０ 、１ ＋
ｎｏｌ／８である金属イオン水溶液を滴下混合して、Ｃ
ｏ−Ｃｕ−＾ｌ−Ｂ系合金微粒子を製造した。なお、反
応温度は２０℃とした。＠４図の（Ａ）にＣｏ−へＩ−
Ｂ系合金微粒子の水素化ホウ素カリウム水溶液の１〕１
１によるｍ成変化を、第４図の（Ｂ）にＣｏ−Ｃｕ−Ａ
Ｉ−Ｂ系合金微粒子の場合の同様のｉ成変化を示す−（
発明の効果）
以上のように、本発明によれば、水素化ホウ素化合物ま
たはアミンボラン誘導体の水溶液中に金属イオン水溶液
を滴下混合して非晶質合金微粒子をｇｉ造する際、粒径
やそのばらつトを小さくできる。Co-AI-B alloy fine particles were produced by dropwise mixing an aqueous metal ion solution of le. Similarly, the metal ion amount ratio is Co2+:Cu2+:^l"=7:1.
5:1.5, and their total ion concentration is 0, 1 +
A metal ion aqueous solution of nol/8 was added dropwise and mixed, and C
o-Cu-^l-B based alloy fine particles were manufactured. Note that the reaction temperature was 20°C. @4 (A) in Figure 4 to Co- to I-
1]1 of potassium borohydride aqueous solution of B-based alloy fine particles
Figure 4 (B) shows the change in m composition due to Co-Cu-A
-(
Effects of the Invention) As described above, according to the present invention, when producing amorphous alloy fine particles by dropwise mixing an aqueous metal ion solution into an aqueous solution of a boron hydride compound or an amine borane derivative, the particle size and its variation are can be made smaller.
従って、非晶質合金微粒子をそのままの状態または圧縮
成形体として使用する用途、例えば、磁性流体、磁気シ
ールド祠、小型トランス鉄芯、センサー材、モーターコ
アなどの磁性材料、あるいは化学反応触媒、電極などの
化学装置部品や機器部品のごとき化学的特性、耐食性を
必要とする材料、さ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もしくは分散剤などに高
品質のものを供給できる。Therefore, applications where amorphous alloy fine particles are used as they are or as compression molded bodies, such as magnetic materials such as magnetic fluids, magnetic shield shrines, small transformer cores, sensor materials, motor cores, chemical reaction catalysts, electrodes, etc. We can supply high-quality materials for materials that require chemical properties and corrosion resistance, such as chemical equipment parts and equipment parts, as well as for mixing or dispersing agents with ceramics, paints, dissimilar metals, plastics, etc.
第１図は、実施例３でＦｅ−Δｌ−Ｂ系合金微粒子を製
造した場合のＤＨ八へ／金属イオンの濃度による合金微
粒子の組成と析出量の変化を示すグラフで、（Δ）が組
成変化を、（Ｂ）が析出量変化を示している。
第２図は、実施例４でＮｉ−Ｃｕ−＾１−Ｂ系合金微粒
子を製造した場合のＤＨ八へ／金属イオンの濃度による
合金微粒子の組成と析出量の変化を示すグラフで、（Ａ
）が組成変化を、（Ｂ）が析出量変化を示している。
第３図は、実施例５で旧−へＩ−Ｂ系とＮｉ Ｃｒ−
Δ＋−１３系の合金微粒子を製造した場合の反応温度に
よる合金微粒子組成変化を示すグラフで、（Ａ）がＮｉ
−＾１−Ｂ系合金微粒子の場合を、（Ｂ）がＮｉ−Ｃｒ
−＾１−Ｂ系合金微粒子の場合を示している。
第４図は、実施例６でＣＯ−＾１−Ｂ系とＣｏ−Ｃｕ−
＾１−Ｂ系今金微粒子を製造した場合の還元剤水溶液９
１１による合金微粒子組成変化を示すグラフで、（Ａ）
がＣｏ−へＩ−Ｂ系合金微粒子の場合を、（Ｂ）がＣｏ
−Ｃｕ−＾１−Ｂ系合金微粒子の場合を示している。Figure 1 is a graph showing changes in the composition and precipitation amount of alloy fine particles depending on the concentration of DH8/metal ions when Fe-Δl-B alloy fine particles were produced in Example 3, where (Δ) is the composition of the fine alloy particles. (B) shows the change in precipitation amount. FIG. 2 is a graph showing changes in the composition and precipitation amount of alloy fine particles depending on the concentration of DH8/metal ions when Ni-Cu-^1-B alloy fine particles were produced in Example 4.
) shows the composition change, and (B) shows the precipitation amount change. Figure 3 shows the old I-B system and the Ni Cr- system in Example 5.
This is a graph showing changes in the composition of alloy fine particles depending on the reaction temperature when producing Δ+-13 series alloy fine particles.
-^1- In the case of B-based alloy fine particles, (B) is Ni-Cr
-^1-B alloy fine particles are shown. Figure 4 shows the CO-^1-B system and Co-Cu-
^1-Reducing agent aqueous solution 9 when producing B-based Imakane fine particles
(A) is a graph showing changes in alloy fine particle composition according to No. 11.
is Co- to I-B alloy fine particles, (B) is Co-
-Cu-^1-B alloy fine particles are shown.
Claims (8)
含む還元剤水溶液中にＦｅ、Ｃｏ、Ｎｉイオンの１種ま
たは２種以上を含む金属イオン水溶液またはこの金属イ
オン水溶液に遷移金属イオンの１種または２種以上を添
加した金属イオン水溶液を混合して反応させることによ
り非晶質合金微粒子を製造する方法において、前記各金
属イオン水溶液に周期律表２Ａ族、３Ｂ族、４Ｂ族、５
Ｂ族に属する金属イオンの１種または２種以上添加して
還元剤水溶液中に混合することを特徴とする非晶質合金
微粒子の製造方法。(1) A metal ion aqueous solution containing one or more of Fe, Co, and Ni ions in an aqueous reducing agent solution containing a borohydride compound or an amine borane derivative, or one or two transition metal ions in this metal ion aqueous solution In the method for producing amorphous alloy fine particles by mixing and reacting metal ion aqueous solutions to which the above-mentioned metal ion aqueous solutions are added, groups 2A, 3B, 4B, 5,
1. A method for producing amorphous alloy fine particles, which comprises adding one or more metal ions belonging to Group B and mixing them into an aqueous reducing agent solution.
、Ｓｒのイオンを添加することを特徴とする特許請求の
範囲第１項に記載の非晶質合金微粒子の製造方法。(2) As a metal ion belonging to Group 2A of the periodic table, Mg
, Sr ions are added to the amorphous alloy fine particles according to claim 1.
、Ｇａのイオンを添加することを特徴とする特許請求の
範囲第１項に記載の非晶質合金微粒子の製造方法。(3) As a metal ion belonging to Group 3B of the periodic table, Al
, Ga ions are added to the method for producing amorphous alloy fine particles according to claim 1.
イオンを添加することを特徴とする特許請求の範囲第１
項に記載の非晶質合金微粒子の製造方法。(4) As a metal ion belonging to Group 4B of the periodic table, Sn
Claim 1 characterized in that ions are added.
The method for producing the amorphous alloy fine particles described in 2.
イオンを添加することを特徴とする特許請求の範囲第１
項に記載の非晶質合金微粒子の製造方法。(5) As a metal ion belonging to Group 5B of the periodic table, Bi
Claim 1 characterized in that ions are added.
The method for producing the amorphous alloy fine particles described in 2.
ボラン誘導体濃度と金属イオン水溶液の金属イオン濃度
をモル濃度比で前者／後者≧１にすることを特徴とする
特許請求の範囲第１〜５項のいずれかに記載の非晶質合
金微粒子の製造方法。(6) Claims 1 to 5 characterized in that the concentration of the borohydride compound or amine borane derivative in the reducing agent aqueous solution and the metal ion concentration in the metal ion aqueous solution are set such that the former/latter≧1 in molar concentration ratio. Any method for producing amorphous alloy fine particles.
許請求の範囲第１〜５項のいずれかに記載の非晶質合金
微粒子の製造方法。(7) The method for producing amorphous alloy fine particles according to any one of claims 1 to 5, characterized in that the reaction temperature is 80°C or lower.
特徴とする特許請求の範囲第１〜５項のいずれかに記載
の非晶質合金微粒子の製造方法。(8) The method for producing amorphous alloy fine particles according to any one of claims 1 to 5, characterized in that the pH of the reducing agent aqueous solution is set to 13.5 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14065589A JPH036309A (en) | 1989-06-02 | 1989-06-02 | Manufacture of amorphous alloy fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14065589A JPH036309A (en) | 1989-06-02 | 1989-06-02 | Manufacture of amorphous alloy fine particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH036309A true JPH036309A (en) | 1991-01-11 |
Family
ID=15273693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14065589A Pending JPH036309A (en) | 1989-06-02 | 1989-06-02 | Manufacture of amorphous alloy fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH036309A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1120181A1 (en) * | 2000-01-21 | 2001-08-01 | Sumitomo Electric Industries, Ltd. | Method of producing alloy powders, alloy powders obtained by said method, and products applying said powders |
| JP2010261065A (en) * | 2009-04-30 | 2010-11-18 | Nec Tokin Corp | Amorphous soft magnetic alloy powder, dust core and inductor |
| WO2015093407A1 (en) * | 2013-12-18 | 2015-06-25 | 功平 田口 | Metal-based structure or nanoparticles containing hydrogen, and method for producing same |
-
1989
- 1989-06-02 JP JP14065589A patent/JPH036309A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1120181A1 (en) * | 2000-01-21 | 2001-08-01 | Sumitomo Electric Industries, Ltd. | Method of producing alloy powders, alloy powders obtained by said method, and products applying said powders |
| US6540811B2 (en) | 2000-01-21 | 2003-04-01 | Sumitomo Electric Industries, Ltd. | Method of producing alloy powders, alloy powders obtained by said method, and products applying said powders |
| JP2010261065A (en) * | 2009-04-30 | 2010-11-18 | Nec Tokin Corp | Amorphous soft magnetic alloy powder, dust core and inductor |
| WO2015093407A1 (en) * | 2013-12-18 | 2015-06-25 | 功平 田口 | Metal-based structure or nanoparticles containing hydrogen, and method for producing same |
| US10125019B2 (en) | 2013-12-18 | 2018-11-13 | Kohei Taguchi | Metal-based structure or nanoparticles containing hydrogen, and method for producing same |
| US20220127143A1 (en) * | 2013-12-18 | 2022-04-28 | Kohei Taguchi | Metal-based structure or nanoparticles containing hydrogen, and method for producing same |
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