JPH02232308A - Manufacture of amorphous alloy fine particles - Google Patents
Manufacture of amorphous alloy fine particlesInfo
- Publication number
- JPH02232308A JPH02232308A JP5136089A JP5136089A JPH02232308A JP H02232308 A JPH02232308 A JP H02232308A JP 5136089 A JP5136089 A JP 5136089A JP 5136089 A JP5136089 A JP 5136089A JP H02232308 A JPH02232308 A JP H02232308A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- reducing agent
- metal ion
- fine particles
- alloy fine
- 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 45
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 55
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 38
- -1 boron hydride compound Chemical class 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910010277 boron hydride Inorganic materials 0.000 claims abstract description 6
- 229910001428 transition metal ion 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 69
- 150000002500 ions Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 31
- 229910045601 alloy Inorganic materials 0.000 abstract description 17
- 239000000956 alloy Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000001556 precipitation Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000085 borane Inorganic materials 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000007423 decrease Effects 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 230000003247 decreasing effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910000521 B alloy Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910020674 Co—B Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 241000277269 Oncorhynchus masou Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 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
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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、高品質
の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 Field of Application) The present invention provides an industrial method for producing high-quality amorphous alloy fine particles by the reaction between an aqueous solution of metal ions and an aqueous solution of a semimetal-containing compound. The present invention relates to a method of manufacturing at a high yield and at low cost.
（従米技術）
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、混合化に優れているので、近
年磁性材料、触媒材料、強度材料、耐食材料などの分野
で注目されている．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開の２本の高速回転ロール
の間に噴出させで、ロール間で生じる溶融合金のキャビ
テーシッンにより霧化、急冷するキャビテーン３ン法、
または溶融合金をｌｉｌｉ１転液中に噴出させで急冷す
る回転液中噴出法などにより行なわれている。(Jumei technology) Amorphous alloy particles have superior formability, surface properties, composites, and mixability compared to ribbon materials and wire materials, so in recent years they have been used for magnetic materials, catalytic materials, strength materials, corrosion-resistant materials, etc. It is attracting attention in the field. Conventionally, the mass production of amorphous alloy fine 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 ejected between two high-speed rotating rolls with a minute gap between them. The cavitane method involves atomizing and rapidly cooling the molten alloy produced by cavitation,
Alternatively, the molten alloy is jetted into a rotating liquid and quenched, such as by a jetting method in a rotating liquid.
しかし、これらの方法は、いずれも装置が大型になワ、
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
、萌記方法で得られる粒子は、粒径が大きく、しかも不
均一であり、比較的ばらつきの小さなものでも０．１〜
５０μ１轟の範囲であった．このため、使用にあたって
は分級、ＭＳｌ！を必要としていた。However, all of these methods require large equipment;
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 Moeki method have large particle sizes and are non-uniform, even if they have relatively small variations. 0.1～
It was in the range of 50μ1 roar. For this reason, when using the MSl! was needed.
そこで、本発明者らは、かか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
たはアミンポラン誘導体の水溶液中１： Ｆｅ， Ｃｏ
， Ｎｉイオンのｉｌｌ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種以上を添加した水溶液を混合して反応さ
せる方法を提案した（特願昭６ ２ − ２ ２ １
５ ６ ７号）．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、粒径が１０μ請以下で、ばらつ島が小さく、しか
も、ホウ素成分を従末法より高くすることら可能な非晶
質合＝ｋ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。Therefore, the present inventors developed a method for producing amorphous alloy fine particles that solved this problem by first preparing 1: Fe, Co in an aqueous solution of a boron hydride compound or an amineporane derivative.
, proposed a method of reacting by mixing an aqueous solution containing an ill or two or more types of Ni ions, or an aqueous solution containing one or more types of transition metal ions added to this metal ion aqueous solution (Patent Application No. 62 -2 2 1
5 6 No. 7). This method uses a borohydride 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 them with boron. This is a method of precipitating boron-containing amorphous alloy fine particles with a particle size of 10 μm or less, a small scattering island, and a higher boron content than the conventional method. It has the characteristic that it can be mass-produced at nearby temperatures.
（発明が解決しようとする問題点）
しかし、この方法は、化学反応を利用して！！遣する方
法であるため、反応条件により組成、収率、構造に差異
が生じてしまう．このため、高品質の非晶質合金微粒子
を工業的に高収率で安価に！！！造するには、反応条件
を確立することが急務であった．
本発明は、この反応条件を確立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．（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組成、収率、構造な
どに影響を与える還元剤と金属イオンの濃度、還元剤水
溶液の温度およびｐｌｌについて検討した結果、還元剤
と金属イオンの濃度については、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／４ｒ属イオン≧
１に、還元剤水溶液の温度については８０℃以下に、さ
らに、還元剤水ｆ！液のρ１１については１３．５以下
にすればよいことを見出だし、本発明を完成した．
本発明者らは、まず、還元剤と金属イオンの濃度が非晶
質合金微粒子の組成、収率、構造に与える影響を調査す
べく、種々の濃度の還元剤水溶液を準備して、この水溶
液中に金属イオン濃度が一定の水溶液を同量滴下混合し
、析出物の組成、収率、構造を調査した．
その結果、析出物の組成については、還元剤とｅ属イオ
ンの濃度をモル濃度比で還元剤／金属イオン≧１にすれ
ばほぼ一定にできることを確認した．
また、析出量については、モル濃度比を還元剤／金属イ
オン≦５にすると減少する傾向が認められ、モル濃度比
を２にすると、モル濃度比が１０の場合の５０％に減少
することが確認された．さらに、補遺については、モル
濃度比を２以下にすると、酸化物と思われる赤褐色の析
出物が認められ、モル濃度比が１での析出物をＸＡ１回
折してみると、非晶質特有のブロードなピークに混じっ
て酸化物のピークも認められた．
以上の結果から、還元剤である水素化ホウ素化合物また
はアミンボラン誘導体と金属イオンの濃度は、モル濃度
比で前者／後者≧１にすることが必要であると認められ
た．
次に、上記結果より還元剤／金属イオンモル濃度比が１
以上で、モル濃度がともに等しい還元剤水溶液と金属イ
オン水溶液を１４製して、還元剤水溶液中に金属イオン
水溶液を滴下により同！混合し、還元剤水溶液の温度が
組成、収率、構造に及ぼす影響を調査した．
その結果、還元剤水ｔ８液の温度が８０℃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−
１ｔ微粒子の組成に大きな変化が認められなかった。し
かし、８０℃より高くすると、ホウ素成分量には大きな
変化が認められなかったが、金属成分の組成がＳ．激に
変化し、それとともに赤褐色の金属酸化物と考えられる
析出物が認められた．
析出量は、一般の化学反応と同様に、反応温度が高い程
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
る場合の還元剤酸化が懸念された．また、構造は、９５
℃以下であれば、非晶質であった．
以上の結果より還元剤水溶液の温度は８０℃以下に制御
することが必要であった．この還元剤水溶液の温度は、
還元削水溶液中に温度の異なる金属イオン水溶液を滴下
混合しても、その滴下速度が急激でなければ、還元剤水
溶液の温度はほとんど変化しないので、実質的には還元
剤と金属イオンとの反応温度である．
最後に、上記還元剤水溶液の適性温度調査の場合と同様
の還元剤水溶液および金属イオン水溶液をＷ！４！Ｌて
、還元剤水溶液のｐｕをアルカリ溶液添加により変化さ
せ、還元剤水溶液ｐｌｌが組成、収率、構造に及ぼす影
響を調査した。(Problem to be solved by the invention) However, this method uses a chemical reaction! ! Since this is a method that relies on the use of a chemical compound, there are differences in composition, yield, and structure depending on the reaction conditions. Therefore, high quality amorphous alloy particles can be produced industrially at high yields and at low cost! ! ! In order to produce this, it was urgently necessary to establish reaction conditions. The present invention provides a method for producing amorphous alloy particles in which these reaction conditions are established. (Means for solving the problem) The present inventors investigated the concentration of the reducing agent and metal ions, the temperature of the reducing agent aqueous solution, and the PLL, which affect the composition, yield, structure, etc. of amorphous alloy fine particles. As a result, regarding the concentration of reducing agent and metal ion, the molar concentration ratio of boron hydride compound or amine borane derivative/4r group ion ≧
1. The temperature of the reducing agent aqueous solution should be kept below 80°C, and the reducing agent water f! They discovered that the ρ11 of the liquid should be 13.5 or less, and completed the present invention. The present inventors first prepared reducing agent aqueous solutions with various concentrations in order to investigate the effects of the reducing agent and metal ion concentrations on the composition, yield, and structure of amorphous alloy fine particles. The composition, yield, and structure of the precipitate were investigated by dropping the same amount of an aqueous solution with a constant metal ion concentration into the solution. As a result, it was confirmed that the composition of the precipitate can be kept almost constant by setting the concentration of reducing agent and group e ions to a molar concentration ratio of reducing agent/metal ion ≧1. In addition, the amount of precipitation tends to decrease when the molar concentration ratio is reduced to reducing agent/metal ion ≦5, and when the molar concentration ratio is set to 2, it decreases to 50% of the amount when the molar concentration ratio is 10. confirmed. Furthermore, regarding the appendix, when the molar concentration ratio is 2 or less, reddish brown precipitates that are thought to be oxides are observed, and when the precipitates at a molar concentration ratio of 1 are subjected to XA1 diffraction, they are found to be characteristic of amorphous. Oxide peaks were also observed mixed with the broad peaks. From the above results, it was recognized that the concentrations of the borohydride compound or amine borane derivative as a reducing agent and the metal ion must be set to a molar concentration ratio of former/latter≧1. Next, from the above results, the reducing agent/metal ion molar concentration ratio is 1.
As described above, 14 reducing agent aqueous solutions and metal ion aqueous solutions with equal molar concentrations were prepared, and the metal ion aqueous solution was dropped into the reducing agent aqueous solution to achieve the same result! The effects of the temperature of the reducing agent aqueous solution on the composition, yield, and structure were investigated. As a result, as long as the temperature of the reducing agent water T8 liquid is 80°C or lower, even if the aqueous solution contains two or more types of metal ions, the metal ions will not be combined.
No major change was observed in the composition of the 1t fine particles. However, when the temperature was raised above 80°C, no significant change was observed in the amount of boron, but the composition of the metal components increased to S. A drastic change occurred, and along with this, reddish-brown precipitates thought to be metal oxides were observed. As with general chemical reactions, the higher the reaction temperature, the faster the reaction progresses and the shorter the precipitation time, but if the amount is too high, the reducing agent may decompose in an aqueous solution or reduce when reacting in air. There was a concern about agent oxidation. Also, the structure is 95
If the temperature was below ℃, it was amorphous. From the above results, it was necessary to control the temperature of the reducing agent aqueous solution to below 80°C. The temperature of this reducing agent aqueous solution is
Even if metal ion aqueous solutions with different temperatures are mixed dropwise into the reducing water cutting solution, the temperature of the reducing agent aqueous solution will hardly change unless the dropping speed is rapid, so the reaction between the reducing agent and the metal ions will actually occur. It is temperature. Finally, add the same reducing agent aqueous solution and metal ion aqueous solution as in the case of the appropriate temperature investigation of the reducing agent aqueous solution to W! 4! Then, the pu of the reducing agent aqueous solution was changed by adding an alkaline solution, and the influence of the reducing agent aqueous solution pll on the composition, yield, and structure was investigated.
水素化ホウ素化合物またはアミンボラン誘導体を水溶液
とした場合の１｝１■は１０〜１１で、これらの化合物
はアルカξノ性で安定している。このため、水溶液がア
ルカリ性の場合、反応に寄与する還元削の量は減少する
と考えられるが、反応速度を制御して、良質の合金微粒
子を製造するのには適している．
しかし、組成に大きな変化が認められな（１のは、水溶
［ｐｌｌが１３，５以下の場合で、これより大きくする
と、ホウ素成分の急激な減少が認められた．また、析出
量もｐｉ＝１３から減少が認められ、ｐｌ！＝１３．５
になるとｐＨ＝１２のときの約５０％も減少してしまっ
た．構造はｐＨを大きくしてもすべて非晶質で、ｐ｝ｌ
＝ １ ２以上では粒子がｉｔ細化する傾向があった．
これらの結果より工業的製造にはｐｌｌを１３．５以下
にする必要があった．（実施例）
実施例１
種々の濃度の水素化ホウ素カリウム（Ｋ旧１４）水溶液
およびノメチルアミンボラン（ＤＨＡＩＩ）水溶液を各
１００ｍｌずっと、濃度０ ． １ ｍｏｌ／ｇの硫酸
第一鉄（ＦｅＳＯ４）水溶液１００ｍｌを調製して、前
者の還元剤水溶液温度を１０℃にして攪拌しながら、そ
の中に後者の金属イオン水溶液を全量滴下混合し、生じ
た析出物をろ過、洗浄してＦｅ−Ｂ系合金徴粒ｆを製造
した．第１図、第２図に各還元剤の濃度と微粒子のＭ成
および構造の関係を示す．なお、ｍ成は化学分析により
、構造はＸ線回折によった．いずれの還元剤とも濃度が
０ ． ３ ｍｏｌ／ｇ以上ではＦｅ， Ｂの組成はほ
ぼ一定であったが、濃度がこれ以下になると徐々に減少
をはじめ、０ ． １ ｍｏｌ／Ｃ以下では急激に減少
し、しかも、この濃度では析出物中に鉄の酸化物と思わ
れる赤褐色の粉末が混合し、良質な微粒子が得られなか
った．また、還元削濃度が０ ．１ ｍｏＩｉｅ以上で
は非晶質単相、それ以上では非晶質に酸化物と思われる
結晶相のピークが表れた．
第３図に上記条件で得られた合金微粒子の収率を示す．
ＷＬ紬は還元剤濃度であるが、縦軸のＷ／Ｗ，は、本実
施例での析出量（Ｗ）と還元剤の基準濃度であるｌｍｏ
ｌ／ｅの水Ｓ液を用いたときの析出量（Ｗ１）の比であ
る．還元削濃度が０ ， ３ ｍｏｌ／ＪＢまではほぼ
Ｗ／Ｗ，は１に近いが、それ以下では減少をはじめ、０
． １ ｍｏｌ７９以下では約０．５となった。When a borohydride compound or an amine borane derivative is used as an aqueous solution, 1}1■ is 10 to 11, and these compounds are stable due to their alkaline nature. Therefore, if the aqueous solution is alkaline, the amount of reduction cutting that contributes to the reaction is thought to decrease, but it is suitable for controlling the reaction rate and producing high-quality alloy particles. However, no significant change was observed in the composition (No. 1 is when the water solubility [pll is less than 13.5; when it is larger than this, a rapid decrease in the boron component is observed. Also, the amount of precipitation is also A decrease was observed from 13, pl!=13.5
In this case, the pH value decreased by about 50% compared to when pH = 12. The structure is entirely amorphous even when the pH is increased, and p}l
= 12 or more, the particles tended to become thinner.
From these results, it was necessary to reduce pll to 13.5 or less for industrial production. (Example) Example 1 100 ml each of potassium borohydride (K old 14) aqueous solution and nomethylamine borane (DHAII) aqueous solution of various concentrations were added to the solution at a concentration of 0. Prepare 100 ml of a 1 mol/g ferrous sulfate (FeSO4) aqueous solution, set the temperature of the former reducing agent aqueous solution to 10°C, and dropwise mix the entire amount of the latter metal ion aqueous solution into it while stirring. The precipitate was filtered and washed to produce Fe-B alloy grain f. Figures 1 and 2 show the relationship between the concentration of each reducing agent and the M composition and structure of fine particles. The composition was determined by chemical analysis, and the structure was determined by X-ray diffraction. The concentration of both reducing agents is 0. At concentrations above 3 mol/g, the compositions of Fe and B remained almost constant, but when the concentration decreased below this level, they began to gradually decrease until 0.5 mol/g. Below 1 mol/C, it decreased rapidly, and at this concentration, reddish-brown powder, which was thought to be iron oxide, was mixed into the precipitate, making it impossible to obtain fine particles of good quality. In addition, the reduction concentration is 0. At 1 moIie or more, an amorphous single phase appeared, and at more than that, a peak of a crystalline phase that appeared to be an amorphous oxide appeared. Figure 3 shows the yield of alloy fine particles obtained under the above conditions.
WL Tsumugi is the reducing agent concentration, and W/W on the vertical axis is the precipitation amount (W) in this example and lmo, which is the standard concentration of the reducing agent.
This is the ratio of precipitation amount (W1) when using l/e water S solution. W/W is close to 1 when the reduction concentration is 0.3 mol/JB, but below that it begins to decrease and decreases to 0.
．． At 1 mol79 or less, it was about 0.5.
実施例２
濃度１曽ｏｆ／ｅの水素化ホウ素ナトリウム（Ｎａ１３
１１．）水溶液１００ｍｌと、硫Ｎ！第一鉄（ＦｅＳＯ
ｉ）と塩化コハルト（ＣｏＣＩ２）をＦｅ２＋／Ｃｏ”
＝ ７ ／ ３になるように混合し、その合計イオン
濃度を０ ． １ ｍｏｌ／ｅとした金属イオン水溶９
１００ｍｌを調製して、前者の還元剤水溶液の温度を２
℃から９５℃に変化させながら、その水溶液中に後者の
金属イオン水溶液を全量滴下混合し、Ｆｅ−Ｃｏ−Ｂ系
合４ｒ微粒子を製造した．混合は実施例１と同様に攪拌
下に行い、析出物もろ過、洗浄した。ｆ：ｔＳＪ図に還
元剤濃度と微粒子組成の関係を示す．
Ｆｅ， Ｃｏの金属組成は、４０゛Ｃ以下ではほぼ一定
であったが、それ以上では徐々に減少をはじめ、８５“
Ｃでは急激に減少をはじめた．Ｂは、８０゜Ｃ付近まで
ほぼ一定であったが、８０℃以上で析出させた微粒子に
は金属の酸化物と思われる赤褐色の粉末が若モ混合して
いた．
９５゜Ｃ以下の温度で析出させた微粒子にはＸ＠回折で
結晶相を示すピークは認められなかった．実施例３
濃度１ ｍｏｌ／ｅの水素化ホウ素カリウム（ＫＯＪＩ
４）水溶［１００ｍｌと、硫酸第一鉄（ＦｅＳＯ＜）と
塩化ニッケル（旧Ｃ１２）をＦｅ２＋／Ｎｉ” ＝ ７
／ ３になるように混合し、その合計イオン濃度を０
． １ ｎｏｔ／９とした金属イオン水溶液１００ｍ
ｌを調製して、この水溶液をＩ】１１を種々変化させた
還元剤水溶液に全量滴下混合し、Ｆｅ一旧一Ｂ系合金微
粒子を製造した。なお、金属イオン水溶液の調製時のｐ
Ｈは１０．５であったので、水酸化ナトリウム（Ｎａ．
０１１）を添加して・）Ｈを変化させた．第５図に還元
剤水溶液のｐＨと微粒子組成の関係を示す．
還元剤水溶液のｐＨが１３以下ではＦｅＳＮｉ， Ｂの
Ｍ成に大きな変化は見られなかったが、ｐＨが１３を越
えると、ＦＣ， Ｎｉの成分が減少した．第６図は、還
元剤水溶液の！】１１と析出量との関係を示すもので、
縦軸のＷ／Ｗ．は、本実施例での析出量（Ｗ）とｆｌｉ
ｔ！Ｊ！Ｌたままの還元剤水溶液を用いたと一の析出量
（Ｗ，）との比である．析出量は、ｐＨが１３を越えた
あたりから急激に減少し、ｐ１１＝１３．５ではＷ／Ｗ
．は約０．３に減少した．一方、ｐ＋１が１３以下では
Ｗ／Ｗ．＝０．７〜１．０となり、析出量が多かった，
実施例４
硫酸ニッケル（ＮｉＳＯ４）と硫酸銅（ＣｕＳＯ４）を
Ｎｉ” ／Ｃｕ” ＝ ７ ／ ３になるように混合し
、その合計イオン濃度を０ ， １ ｍｏｌ／ｇ Ｌた
金属イオン水溶液１００ｍｌを調製しで、この水溶液を
種々の濃度のツメチルアミンボラン（ＤＨ八Ｂ）水溶液
１００ｍｌに全量滴下混合し、実施例１と同要領でＮｉ
−Ｃｕ−Ｂ系合金微粒子を製造した．第７図にＤＭ八〇
濃度と微粒子組成の関係を示した．
Ｎｉ， Ｃｕ成分は、ＤＮＡＢ濃度０．１ − ０．２
ｍｏｌ／ｇ付近で減少をはじめ、０ ． １ ｍｏｌ／
ｇで急激に減少した．Ｂ成分は、旧、Ｃｕ戊分に比べ減
少がやや少なかった．
折出ｍｃｗ＞には実施例１とほぼ同じ傾向が認められ、
ＤＭＡＢの基準濃度１ｍｏｌ／ｅの水溶液を用いたとき
の析出１１＜Ｗ，）との比は、０ ， ５ ｍｏｌ／ｇ
？Ｗ／Ｗ，＝０．７０、０ ． ３ ｍｏｌ／ｅ−ｃ
”ｗ／ｗ ，＝ ０ ， Ｇ Ｏ、０ ． １ ｍｏｌ
／ｅ″ｃＷ／Ｗ，＝ ０ ．４ ０であった。Example 2 Sodium borohydride (Na13
11. ) 100 ml of aqueous solution and sulfur N! First iron (FeSO
i) and cohalt chloride (CoCI2) as Fe2+/Co”
= 7/3, and the total ion concentration was 0. 1 mol/e metal ion water solution 9
Prepare 100ml and adjust the temperature of the former reducing agent aqueous solution to 2.
While changing the temperature from .degree. C. to 95.degree. C., the entire amount of the latter metal ion aqueous solution was added dropwise to the aqueous solution to produce Fe-Co-B composite 4r fine particles. Mixing was performed under stirring in the same manner as in Example 1, and the precipitate was also filtered and washed. The f:tSJ diagram shows the relationship between reducing agent concentration and fine particle composition. The metal composition of Fe and Co was almost constant below 40°C, but began to gradually decrease above 85°C.
In C, it began to decrease rapidly. B was almost constant up to around 80°C, but the fine particles precipitated at temperatures above 80°C contained a small amount of reddish-brown powder, which was thought to be a metal oxide. No peak indicating a crystalline phase was observed in X@ diffraction in the fine particles precipitated at temperatures below 95°C. Example 3 Potassium borohydride (KOJI) at a concentration of 1 mol/e
4) Water solution [100 ml, ferrous sulfate (FeSO<) and nickel chloride (formerly C12)] Fe2+/Ni” = 7
/ 3, and the total ion concentration is 0.
．． 1 not/9 metal ion aqueous solution 100m
The entire amount of this aqueous solution was added dropwise to a reducing agent aqueous solution containing various modifications of I]11 to produce Fe-old-B alloy fine particles. In addition, when preparing the metal ion aqueous solution, p
H was 10.5, so sodium hydroxide (Na.
011) was added to change .)H. Figure 5 shows the relationship between the pH of the reducing agent aqueous solution and the fine particle composition. When the pH of the reducing agent aqueous solution was below 13, no significant change was observed in the M composition of FeSNi and B, but when the pH exceeded 13, the FC and Ni components decreased. Figure 6 shows the reducing agent aqueous solution! ] This shows the relationship between 11 and the amount of precipitation,
W/W on the vertical axis. is the precipitation amount (W) and fli in this example
T! J! This is the ratio of the amount of precipitation (W,) when using the reducing agent aqueous solution as it is. The amount of precipitation decreases rapidly when the pH exceeds 13, and at p11 = 13.5, W/W
．． decreased to about 0.3. On the other hand, if p+1 is 13 or less, W/W. = 0.7 to 1.0, and the amount of precipitation was large. Example 4 Nickel sulfate (NiSO4) and copper sulfate (CuSO4) were mixed so that Ni"/Cu" = 7/3, and the total ion Prepare 100 ml of a metal ion aqueous solution with a concentration of 0 and 1 mol/g L, dropwise mix the entire amount of this aqueous solution with 100 ml of trimethylamine borane (DH8B) aqueous solutions of various concentrations, and add Ni in the same manner as in Example 1.
-Cu-B alloy fine particles were manufactured. Figure 7 shows the relationship between DM80 concentration and fine particle composition. Ni and Cu components have a DNAB concentration of 0.1-0.2
It started to decrease around mol/g and started to decrease around 0. 1 mol/
It decreased rapidly at g. The decrease in the B component was slightly smaller than that of the old Cu component. Almost the same tendency as in Example 1 was observed for the deposited mcw>,
When using an aqueous solution with a standard concentration of DMAB of 1 mol/e, the ratio of precipitation 11<W,) is 0.5 mol/g
? W/W,=0.70, 0. 3 mol/e-c
”w/w,=0,G O,0.1 mol
/e″cW/W, = 0.40.
実施例５
実施例２において、金属イオン水溶液として、塩化コバ
ルトの代わりに塩化クロム（ＣｒＣｈ）を同モル溶解さ
せたＦｅ． Ｃｒイオン水溶液を用いてＦｅ−Ｃｒ −
Ｂ系合金微粒子を製造した．第８図に還元Ｍ濃度と微
粒子組成変化の関係を示す． Ｆｅ， Ｃｒは８０℃以
下ではほぼ一定であったが、それ以上では急激に減少し
た．Ｂは９０℃までほぼ一定で、それ以上では減少した
．実施例６
実充例３において、金属イオン水溶液として、塩化ニッ
ケルの代わりに塩化マンがン（ＭｎＣｌ２）ヲ同モル溶
解させたＦｅ， Ｎｎイオン水溶液を用いて、Ｆｅ−）
４ｎ−Ｂ系合計微粒子を製造した．水酸化ナトリウム未
添加のｒｉｌｌ！ｌたままの還元剤水溶ＱｐＨは１０．
５で、実施例３の場合と同じであった．第９図に還元剤
水溶液ｐｕと微粒子組成の関係を示す．ｐＨが１３．０
以下ではＦｅ， Ｈｎｓ Ｂの組成には大きな差異はな
かったが、１３．０を越えるとＦｅ、Ｍｎの組成は急激
に減少し、Ｂ成分も若モ減少した。Example 5 In Example 2, Fe. Fe-Cr − using Cr ion aqueous solution
B-based alloy fine particles were manufactured. Figure 8 shows the relationship between reduced M concentration and changes in fine particle composition. Fe and Cr were almost constant below 80°C, but decreased rapidly above that. B remained almost constant up to 90°C and decreased above that point. Example 6 In Practical Example 3, instead of nickel chloride, an Fe and Nn ion aqueous solution in which the same mole of manganese chloride (MnCl2) was dissolved was used as the metal ion aqueous solution.
4n-B type total fine particles were produced. Rill without sodium hydroxide added! The aqueous reducing agent solution QpH is 10.
5, which was the same as in Example 3. Figure 9 shows the relationship between reducing agent aqueous solution PU and fine particle composition. pH is 13.0
Below, there was no big difference in the composition of Fe and Hns B, but when it exceeded 13.0, the composition of Fe and Mn rapidly decreased, and the B component also decreased slightly.
析出速度もｐ＋＋が１３．０を越えると若干遅くなる傾
向があった。The precipitation rate also tended to become slightly slower when p++ exceeded 13.0.
（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？ｌ
ｇ液を滴下混合して非晶質合金微粒子を工業的に製造す
る際の反応条件が確立できた。(Effects of the Invention) As described above, according to the present invention, metal ion water is present in an aqueous solution of a borohydride compound or an amine borane derivative. l
The reaction conditions for industrial production of amorphous alloy fine particles by dropwise mixing of liquid g were established.
従って、安価な非晶質合２ｔ微粒子の供給が待ち望まれ
ている用途、例えば、磁性流体、磁気シールド材、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、７Ｋ極なとの化学装置部品
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に供給できる．Therefore, the supply of inexpensive amorphous 2t fine particles is expected for applications such as magnetic fluids, magnetic shielding materials, small transformer iron cores, sensor materials, motor cores, and other magnetic materials, chemical reaction catalysts, and 7K poles. It can be used as a mixing or dispersing agent for materials that require chemical properties and corrosion resistance, such as chemical equipment parts and equipment parts, as well as ceramics, paints, dissimilar metals, plastics, etc.
第１〜３図は、実施例１でＦｅ−Ｂ系合金を製造した場
合の反応条件非晶質と合金微粒子特性の関係を示すもの
で、第１図、ｖＩ１２図は、還元剤水溶液濃度と合金微
粒子組成および構造の関係をグラフ、第３図は、還元剤
濃度と析出量比の関係を示すグラフである。第４図は、
実施例２でＦｅ−Ｃｏ−Ｂ系非晶質合金微粒子を製造し
た場合の還元削水ｆ＃液温度と合金微粒子組成の関係を
示すグラフである。第５図、第６図は、実施例３でＦｅ
−Ｎｉ−Ｂ系非晶質合金微粒子を製造した場合の反応条
件と合金微粒子特性の関係を示すもので、第５図は還元
剤水溶液ｐｌ１と合金微粒子組成の関係を示すグラフ、
第６図は還元剤水溶１ｐＨと析出量比の関係を示すグラ
フである．第７図は、実施例４でＮｉ Ｃｕ−ＢＸ％
非晶質合金微粒子を製造した場合の還元剤水溶液濃度と
合金微粒子組成の関係を示水溶液グラフである。第８図
は、実施例５でＦｅ−ＣｒＢ系非晶質合金微粒子を製造
した場合の還元剤水溶液温度と合金微粒子ＭＬｔとの関
係を示すグラフである。第９図は、実施例６でＦｅ−Ｎ
ｏ−Ｂ系非晶質合金微粒子を製造した場合の還元剤水溶
ｉｐＨと合金微粒子組成の関係を示すグラフである。
特許出願人 口新製鋼株式会社
増 本 健
代 理 人 進 藤 満第１図
第２図
第９図
第３図
第４図
ＫＢＨ４水溶液ｐ｝４
組成（涼子％）
系且万交（漂子％）
手続補正書
平成１年３月２９８
平成１年特許願第５ １ ３６０号
２．発明の名称
非晶質合金微粒子の製造方法
３．補正をする者
事件との関係 特許出願人
住 所 東京都千代田区丸の内三丁目４番１号名 称
（４５８） 日新９１鋼株式会社（外１名）代表取締
役 甲 斐 幹
４．代 理 人 （〒１０３）
住 所 東京都中央区日本橋堀留町２丁目３番３グラン
ドメゾン日本橋堀留７０４号室
電話 ０３（６６１）６０８０
自 発
６．補正の対象
娶任状および明繍芽の発明の詳細な説明の欄７，補正の
内容
絹成Ｃ原子％）
析出量比（ Ｗ／ Ｗｏ）
■、明細書の発明の詳細な説明を下記のように訂正する
．
（１）明細書２真上から５行目の「する際、」の次に［
不純物が少なく、非晶質性に優れた」を加入する．（２
）同ＩＦ６真上から９行目の「必要であると認められた
．」の次に「またモル濃度比で前者／後者≧２０として
も収率、構造、組成等に大きな変化はなく、従って、最
適濃度比は、モル濃度比で１≦前者／後者≦２０とした
時であることが判明した．」を加入する．（３）同書７
真上から９行目の「品質であった。」の次に「従って、
反応温度を０℃以上、８０℃以下とすることが最適な条
件である．」を加入する．（５）同書８真下から４行目
の「ｐＨを」の次に「全＜ｐ整しないｐｌｌＩＯ以上が
ら」を加入する．以 上Figures 1 to 3 show the relationship between the amorphous reaction conditions and the characteristics of the alloy fine particles when Fe-B alloy was produced in Example 1. Figures 1 and 12 show the relationship between the concentration of the reducing agent aqueous solution and FIG. 3 is a graph showing the relationship between alloy fine particle composition and structure, and FIG. 3 is a graph showing the relationship between reducing agent concentration and precipitation amount ratio. Figure 4 shows
3 is a graph showing the relationship between the reduced water cutting f# liquid temperature and the alloy fine particle composition when Fe-Co-B-based amorphous alloy fine particles were manufactured in Example 2. 5 and 6 show Fe in Example 3.
- This shows the relationship between the reaction conditions and the properties of the alloy fine particles when Ni-B based amorphous alloy fine particles are produced, and FIG. 5 is a graph showing the relationship between the reducing agent aqueous solution pl1 and the alloy fine particle composition.
Figure 6 is a graph showing the relationship between the pH of the reducing agent aqueous solution and the precipitation amount ratio. FIG. 7 shows Ni Cu-BX% in Example 4.
It is an aqueous solution graph showing the relationship between reducing agent aqueous solution concentration and alloy fine particle composition when amorphous alloy fine particles are manufactured. FIG. 8 is a graph showing the relationship between the temperature of the reducing agent aqueous solution and the alloy fine particles MLt when Fe-CrB-based amorphous alloy fine particles were produced in Example 5. FIG. 9 shows Fe-N in Example 6.
It is a graph showing the relationship between the reducing agent aqueous solution ipH and the composition of alloy fine particles when o-B type amorphous alloy fine particles are manufactured. Patent Applicant Masu Kushin Steel Co., Ltd. Kenyo Moto Susumu Fuji Mitsuru ) Procedural Amendment March 1999 298 1999 Patent Application No. 5 1 360 2. Name of the invention Method for producing amorphous alloy fine particles 3. Relationship with the case of the person making the amendment Patent applicant address 3-4-1 Marunouchi, Chiyoda-ku, Tokyo Name
(458) Nisshin 91 Steel Co., Ltd. (1 other person) Representative Director Miki Kai 4. Agent (103) Address: Room 704, Grand Maison Nihonbashi Horidome, 2-3-3 Nihonbashi Horidome-cho, Chuo-ku, Tokyo Telephone: 03 (661) 6080 Self-initiated 6. Subject of amendment Column 7: Detailed explanation of the invention of the letter of intent and light bud Correct it as follows. (1) On the 5th line from the top of the specification 2, after “when doing so,” [
Added ``low impurities and excellent amorphousness''. (2
) In the 9th line from the top of IF6, next to ``Recognized as necessary.'', ``Also, even if the molar concentration ratio of the former/latter is ≥20, there will be no major change in yield, structure, composition, etc. , it was found that the optimum concentration ratio is when the molar concentration ratio is 1≦former/latter≦20.'' is added. (3) Ibid. 7
In the 9th line from the top, after “It was quality.”, “Therefore,
The optimal condition is to keep the reaction temperature between 0°C and 80°C. ”. (5) In the fourth line from the bottom of 8 of the same book, after "pH", add "all < pllIO or more". that's all
Claims (3)
溶解した還元剤水溶液中に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滴下混合して非晶質合金微粒
子を製造する際、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
特徴とする非晶質合金微粒子の製造方法。(1) Fe, Co, and Ni ions are added to an aqueous solution of a reducing agent in which a borohydride compound or an amine borane derivative is dissolved.
When producing amorphous alloy fine particles by dropwise mixing a metal ion aqueous solution containing one or more types of metal ions, or a metal ion aqueous solution containing one or more transition metal ions added to the metal ions, the reducing agent aqueous solution A method for producing amorphous alloy fine particles, characterized in that the concentration of the boron hydride compound or amine borane derivative in the above and the metal ion concentration of the metal ion aqueous solution are set to a molar concentration ratio of former/latter≧1.
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) The method for producing amorphous alloy fine particles according to claim 1, characterized in that the temperature of the reducing agent aqueous solution is set to 80° C. or lower.
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) The method for producing amorphous alloy fine particles according to claim 1, 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 |
|---|---|---|---|
| JP5136089A JPH02232308A (en) | 1989-03-03 | 1989-03-03 | Manufacture of amorphous alloy fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5136089A JPH02232308A (en) | 1989-03-03 | 1989-03-03 | Manufacture of amorphous alloy fine particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02232308A true JPH02232308A (en) | 1990-09-14 |
Family
ID=12884772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5136089A Pending JPH02232308A (en) | 1989-03-03 | 1989-03-03 | Manufacture of amorphous alloy fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02232308A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2013033980A (en) * | 2012-09-20 | 2013-02-14 | Seiko Epson Corp | Metal powder for magnetic fluid |
-
1989
- 1989-03-03 JP JP5136089A patent/JPH02232308A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2013033980A (en) * | 2012-09-20 | 2013-02-14 | Seiko Epson Corp | Metal powder for magnetic fluid |
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