JPH04329804A - Production of rare earth alloy powder - Google Patents
Production of rare earth alloy powderInfo
- Publication number
- JPH04329804A JPH04329804A JP12534091A JP12534091A JPH04329804A JP H04329804 A JPH04329804 A JP H04329804A JP 12534091 A JP12534091 A JP 12534091A JP 12534091 A JP12534091 A JP 12534091A JP H04329804 A JPH04329804 A JP H04329804A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- alloy
- earth alloy
- hydrogen
- electrolyte 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.)
- Withdrawn
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 124
- 239000000956 alloy Substances 0.000 title claims abstract description 124
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 72
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 71
- 239000000843 powder Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008151 electrolyte solution Substances 0.000 claims description 23
- 238000010298 pulverizing process Methods 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 19
- 238000005868 electrolysis reaction Methods 0.000 abstract description 9
- 150000002431 hydrogen Chemical class 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 229940021013 electrolyte solution Drugs 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003860 storage Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 229910001172 neodymium magnet Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 which is the cathode Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、Ｎｄ−Ｆｅ−Ｂ系永久
磁石等の希土類合金の粉末を製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing powder of rare earth alloys such as Nd-Fe-B permanent magnets.
【０００２】0002
【従来の技術】高性能でしかも安価な希土類磁石として
、Ｎｄ−Ｆｅ−Ｂ系磁石が知られている。Ｎｄ−Ｆｅ−
Ｂ系磁石を焼結法により製造する場合、従来のＳｍ−Ｃ
ｏ系の粉末冶金プロセス（溶解→鋳造→インゴット粗粉
砕→微粉砕→プレス→焼結→磁石）を適用でき、しかも
高い磁石特性が得られる。しかし、インゴット粉砕に手
間がかかるため生産性が低い。インゴットの粉砕を容易
に行なうために、従来、水素吸蔵粉砕が利用されている
。水素吸蔵粉砕では、まず、インゴットを扱い易い大き
さ、例えば３０ｍｍ角程度に粉砕して原料合金塊とし、
これを密閉容器内に封入する。次いで、容器内を排気し
た後、合金を加熱することにより表面を活性化して水素
を吸蔵し易い状態とし、さらに大気圧程度の水素ガスを
導入して水素を吸蔵させる。水素を吸蔵した合金にはク
ラックが生じ、粉末化する。その後、真空中または不活
性ガス雰囲気中で熱処理を施し、水素を一部除去すると
共に安定なＮｄ水素化物を形成する。BACKGROUND OF THE INVENTION Nd--Fe--B magnets are known as high-performance and inexpensive rare earth magnets. Nd-Fe-
When manufacturing B-based magnets by the sintering method, conventional Sm-C
O-based powder metallurgy process (melting→casting→rough ingot grinding→fine grinding→pressing→sintering→magnet) can be applied, and high magnetic properties can be obtained. However, productivity is low because it takes time and effort to crush the ingot. Conventionally, hydrogen storage pulverization has been used to easily pulverize ingots. In hydrogen storage pulverization, first, an ingot is pulverized into a size that is easy to handle, for example, about 30 mm square, to obtain a raw material alloy lump.
This is sealed in an airtight container. Next, after the inside of the container is evacuated, the alloy is heated to activate its surface to make it easier to absorb hydrogen, and hydrogen gas at about atmospheric pressure is introduced to absorb hydrogen. Cracks occur in alloys that absorb hydrogen and turn into powder. Thereafter, heat treatment is performed in vacuum or in an inert gas atmosphere to partially remove hydrogen and form a stable Nd hydride.
【０００３】しかし、このような水素吸蔵粉砕法には、
以下に示すような問題がある。■水素ガスは爆発性があ
り、厳重な安全管理が必要である。■水素吸蔵の前に合
金を加熱する前処理工程が必要である。■水素吸蔵の際
にも合金を加熱する必要がある。■真空装置が必要であ
り、真空装置の保安や保守が極めて面倒である。[0003] However, in this hydrogen storage pulverization method,
There are problems as shown below. ■Hydrogen gas is explosive and requires strict safety management. ■A pretreatment step is required to heat the alloy before hydrogen storage. ■It is necessary to heat the alloy when storing hydrogen. ■A vacuum device is required, and the safety and maintenance of the vacuum device is extremely troublesome.
【０００４】また、Ｎｄ−Ｆｅ−Ｂ系磁石の他にも、例
えばＳｍ−Ｃｏ系磁石などの各種希土類合金を粉砕する
ために、簡易かつ安全な粉砕方法が望まれている。In addition to Nd--Fe--B magnets, a simple and safe pulverization method is desired for pulverizing various rare earth alloys such as Sm--Co magnets.
【０００５】[0005]
【発明が解決しようとする課題】本発明はこのような事
情からなされたものであり、希土類合金を簡易な手段で
安全に粉砕できる方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for safely pulverizing rare earth alloys using simple means.
【０００６】[0006]
【課題を解決するための手段】このような目的は、下記
（１）〜（４）の本発明により達成される。[Means for Solving the Problems] Such objects are achieved by the present invention as described in (1) to (4) below.
【０００７】（１） 希土類合金を電解質溶液に浸漬
し、前記希土類合金を陰極として前記電解質溶液中の水
を電気分解することにより、前記希土類合金表面で水を
還元して水素を発生させ、この水素を前記希土類合金に
吸蔵させることにより前記希土類合金を粉砕する工程を
有することを特徴とする希土類合金粉末の製造方法。(1) A rare earth alloy is immersed in an electrolyte solution, and water in the electrolyte solution is electrolyzed using the rare earth alloy as a cathode to reduce water on the surface of the rare earth alloy and generate hydrogen. A method for producing rare earth alloy powder, comprising the step of pulverizing the rare earth alloy by occluding hydrogen in the rare earth alloy.
【０００８】（２） 前記希土類合金を回転する容器
中に入れて水の電気分解を行なう上記（１）に記載の希
土類合金粉末の製造方法。(2) The method for producing rare earth alloy powder according to (1) above, wherein the rare earth alloy is placed in a rotating container and water is electrolyzed.
【０００９】（３） 前記電解質溶液のｐＨが５以上
である上記（１）または（２）に記載の希土類合金粉末
の製造方法。(3) The method for producing rare earth alloy powder according to (1) or (2) above, wherein the electrolyte solution has a pH of 5 or more.
【００１０】（４） 前記希土類合金が、Ｎｄ、Ｆｅ
およびＢを含有する永久磁石である上記（１）ないし（
３）のいずれかに記載の希土類合金粉末の製造方法。(4) The rare earth alloy is Nd, Fe,
and (1) to ((1) above, which are permanent magnets containing B).
3) The method for producing rare earth alloy powder according to any one of 3).
【００１１】[0011]
【作用】本発明では、希土類合金を電解質溶液に浸漬し
、希土類合金を陰極として電解質溶液中の水を電気分解
する。このとき、陰極である希土類合金表面で水が還元
されて水素が発生し、この水素は希土類合金に吸蔵され
て、希土類合金の結晶粒界およびその周辺部にクラック
を生じさせるため、希土類合金は粉砕される。[Operation] In the present invention, a rare earth alloy is immersed in an electrolyte solution, and water in the electrolyte solution is electrolyzed using the rare earth alloy as a cathode. At this time, water is reduced on the surface of the rare earth alloy, which is the cathode, and hydrogen is generated. This hydrogen is occluded in the rare earth alloy and causes cracks in the grain boundaries and surrounding areas of the rare earth alloy. Shattered.
【００１２】従来の水素吸蔵粉砕法では、水素ガスを希
土類合金に接触させることにより吸蔵させているため、
希土類合金表面の活性化のための熱処理や吸蔵時の合金
加熱が必要であったが、本発明では水の還元により希土
類合金表面に生じた水素を直接希土類合金に吸蔵させる
ので、加熱が不要であり、また、真空装置も不要である
。[0012] In the conventional hydrogen storage pulverization method, hydrogen gas is stored by bringing it into contact with a rare earth alloy.
Heat treatment to activate the rare earth alloy surface and alloy heating during occlusion were necessary, but in the present invention, hydrogen generated on the rare earth alloy surface by water reduction is directly absorbed into the rare earth alloy, so no heating is required. There is also no need for a vacuum device.
【００１３】[0013]
【具体的構成】以下、本発明の具体的構成を詳細に説明
する。[Specific Structure] The specific structure of the present invention will be explained in detail below.
【００１４】本発明では、少なくともＮｄおよびＦｅを
含有する希土類合金を電解質溶液に浸漬し、希土類合金
を陰極として電解質溶液中の水を電気分解する。水は希
土類合金表面で還元されて水素となり、この水素が合金
に吸蔵され、合金にはクラックが発生して粉砕される。
合金に吸蔵されなかった水素はガス化し、気泡となって
合金塊表面に付着し、また、溶液表面に向って浮上する
。一方、合金塊の対極である陽極では、酸素が発生する
。In the present invention, a rare earth alloy containing at least Nd and Fe is immersed in an electrolyte solution, and water in the electrolyte solution is electrolyzed using the rare earth alloy as a cathode. Water is reduced to hydrogen on the surface of the rare earth alloy, and this hydrogen is occluded in the alloy, causing cracks and pulverization of the alloy. Hydrogen that is not occluded by the alloy gasifies and forms bubbles that adhere to the surface of the alloy lump and float toward the surface of the solution. On the other hand, oxygen is generated at the anode, which is the opposite electrode of the alloy lump.
【００１５】希土類合金の電位は、水素が発生可能な電
位であれば特に制限はない。水の分解電圧は、温度や電
解質溶液の抵抗などの種々の条件によって異なるので、
これらの条件に応じて電位を適宜設定すればよい。具体
的には、まず、図１に示されるような希土類合金の電位
とそのときの電流密度との関係を表わすグラフを作成す
る。このとき、温度等の各条件は、本発明を実施すると
きの条件と同じとする。グラフには、電位を卑側（マイ
ナス側）に増加させても電流密度が殆ど変化しない電位
範囲が存在する。この電位範囲より卑側の電位を希土類
合金に与えた場合、水が還元されて水素が発生する。実
用的な速度で水素吸蔵粉砕を行なうための条件は、実験
的に定めればよい。なお、本発明を工業的に適用する場
合には、水素が発生する電位範囲にて定電流制御により
電気分解を行なうことが好ましい。The potential of the rare earth alloy is not particularly limited as long as hydrogen can be generated. The decomposition voltage of water varies depending on various conditions such as temperature and resistance of the electrolyte solution, so
The potential may be appropriately set according to these conditions. Specifically, first, a graph showing the relationship between the potential of the rare earth alloy and the current density at that time as shown in FIG. 1 is created. At this time, each condition such as temperature is the same as the conditions when implementing the present invention. In the graph, there is a potential range in which the current density hardly changes even if the potential is increased to the base side (minus side). When a potential on the base side of this potential range is applied to the rare earth alloy, water is reduced and hydrogen is generated. Conditions for carrying out hydrogen storage pulverization at a practical speed may be determined experimentally. In addition, when the present invention is applied industrially, it is preferable to carry out electrolysis by constant current control in a potential range in which hydrogen is generated.
【００１６】希土類合金の対極（陽極）には、電圧印加
により溶解しない材質を用いることが好ましく、例えば
、Ｐｔなどを用いることが好ましい。また、電解質溶液
の容器を対極として用いることもできる。[0016] For the rare earth alloy counter electrode (anode), it is preferable to use a material that does not dissolve when voltage is applied, and for example, it is preferable to use Pt or the like. Moreover, a container of electrolyte solution can also be used as a counter electrode.
【００１７】水素を吸蔵させる希土類合金の寸法および
形状に特に制限はないが、好ましくは合金インゴットを
５〜１００ｍｍ角程度まで粉砕した合金塊を用いる。こ
の粉砕は、ジョークラッシャー等により行なえばよい。Although there are no particular restrictions on the dimensions and shape of the rare earth alloy for storing hydrogen, it is preferable to use an alloy ingot obtained by crushing an alloy ingot to about 5 to 100 mm square. This crushing may be performed using a jaw crusher or the like.
【００１８】電解質溶液中に浸漬する合金塊は１個だけ
でもよいが、生産性を高くするためには複数の合金塊を
溶液中に浸漬し、これらの合金塊に同時に電圧を印加す
ることが好ましい。この場合、合金塊が互いに接触する
ように溶液中に浸漬して合金塊群中に陰極を挿入する構
成としてもよいが、電気めっき法などにおいて用いられ
ているバレルめっき槽の構成を利用することが好ましい
。[0018] Only one alloy ingot may be immersed in the electrolyte solution, but in order to increase productivity, it is possible to immerse a plurality of alloy ingots in the solution and apply voltage to these alloy ingots at the same time. preferable. In this case, a configuration may be used in which the alloy ingots are immersed in a solution so as to be in contact with each other and a cathode is inserted into the group of alloy ingots, but the configuration of a barrel plating bath used in electroplating methods etc. may be used. is preferred.
【００１９】バレルめっき槽の構成を利用する場合、バ
スケット状の導電性容器に複数の合金塊を入れて電解質
溶液中に浸漬し、容器に電位を与えて容器および合金塊
を陰極とし、容器を回転させながら電気分解を行なう方
法を用いることができる。また、バスケット状の絶縁性
容器に複数の合金塊を入れ、合金塊群中に陰極を挿入し
て合金塊を陰極とし、容器を回転させながら電気分解を
行なう方法を用いてもよい。あるいは、導電性容器中に
電解質溶液および複数の合金塊を入れ、容器に電位を与
えて容器および合金塊を陰極とし、容器を回転させなが
ら電気分解を行なう方法を用いてもよい。When using a barrel plating bath configuration, a plurality of alloy ingots are placed in a basket-shaped conductive container, immersed in an electrolyte solution, and a potential is applied to the container to use the container and the alloy ingot as a cathode. A method of performing electrolysis while rotating can be used. Alternatively, a method may be used in which a plurality of alloy ingots are placed in a basket-shaped insulating container, a cathode is inserted into the group of alloy ingots, the alloy ingot is used as the cathode, and electrolysis is performed while rotating the container. Alternatively, a method may be used in which an electrolyte solution and a plurality of alloy ingots are placed in a conductive container, a potential is applied to the container, the container and the alloy ingots are used as cathodes, and electrolysis is performed while rotating the container.
【００２０】なお、導電性の容器および合金塊群中に挿
入する電極には、電気分解中に溶解しない材質を用いる
ことが好ましい。Note that it is preferable to use a material that does not dissolve during electrolysis for the conductive container and the electrodes inserted into the alloy ingot group.
【００２１】合金塊は水素と接触する表面付近にクラッ
クを生じ、表面から徐々に粉末化して崩落するが、上記
したようなバレルめっき槽の構成を利用すれば、回転す
る容器内の合金塊は互いに衝突したり容器の壁に衝突し
て衝撃を受けるので、粉末化した部分の崩落が加速され
る。このため、粉砕が迅速に進行する。また、各合金塊
が常に位置を変えることになるので、各合金塊に電気量
をほぼ均等に与えることができ、効率よく粉砕すること
ができる。また、合金塊表面に付着した水素の気泡が剥
れるので、反応が迅速に進行する。[0021] The alloy lump will develop cracks near the surface where it comes into contact with hydrogen, and will gradually turn into powder and collapse from the surface. However, if the configuration of the barrel plating bath as described above is used, the alloy lump in the rotating container will The particles collide with each other and against the walls of the container, accelerating the disintegration of the powdered parts. For this reason, crushing progresses rapidly. Moreover, since each alloy lump constantly changes its position, the amount of electricity can be applied to each alloy lump almost equally, and it can be pulverized efficiently. Furthermore, since the hydrogen bubbles adhering to the surface of the alloy lump are peeled off, the reaction progresses rapidly.
【００２２】本発明において希土類合金が浸漬される電
解質溶液の組成は特に限定されず、通常の水の電気分解
に用いられる各種電解質溶液から適宜選択すればよい。
例えば、電解質としては、Ｋ２ ＳＯ４ 、ＫＣｌＯ４
、Ｎａ２ ＳＯ２ 、ＮａＣｌＯ４ などから選択す
ればよい。In the present invention, the composition of the electrolyte solution in which the rare earth alloy is immersed is not particularly limited, and may be appropriately selected from various electrolyte solutions commonly used for electrolysis of water. For example, as an electrolyte, K2 SO4, KClO4
, Na2SO2, NaClO4, etc.
【００２３】溶液のｐＨは特に限定されないが、通常、
ｐＨ５以上であることが好ましく、特に、ｐＨ５〜１０
であることが好ましい。ｐＨが５未満であると、希土類
合金が酸化し易く、ｐＨが１０を超える溶液中では希土
類合金が水素を吸蔵しにくくなる。[0023] The pH of the solution is not particularly limited, but usually
It is preferable that the pH is 5 or more, especially the pH 5 to 10.
It is preferable that When the pH is less than 5, the rare earth alloy is easily oxidized, and in a solution with a pH of more than 10, the rare earth alloy becomes difficult to absorb hydrogen.
【００２４】また、電解質溶液の温度に特に制限はなく
、電解質溶液が凝固しない温度から沸騰しない温度まで
の間から適宜選択すればよい。電解質溶液の温度が高い
ほど電解反応は迅速に進行するが、陰極と陽極の電位差
を制御することにより、電解質溶液の温度が室温付近で
あっても実用上十分な速度で粉砕が可能である。[0024] The temperature of the electrolyte solution is not particularly limited and may be appropriately selected from a temperature at which the electrolyte solution does not coagulate to a temperature at which it does not boil. The higher the temperature of the electrolyte solution, the faster the electrolytic reaction proceeds, but by controlling the potential difference between the cathode and anode, it is possible to grind at a speed sufficient for practical use even when the temperature of the electrolyte solution is around room temperature.
【００２５】なお、対極（陽極）には、通常の水の電気
分解において使用される各種の陽極を用いればよいが、
消費電力量を少なくするためには酸素を発生させるため
の過電圧が小さい電極を用いることが好ましい。このよ
うな電極としては、例えばＰｔ／Ｔｉ電極、ＩｒＯ２
／Ｔｉ電極、ＲｕＯ２ ／Ｔｉ電極などが挙げられる。[0025] As the counter electrode (anode), various types of anodes used in ordinary water electrolysis may be used.
In order to reduce power consumption, it is preferable to use an electrode with a small overvoltage for generating oxygen. Such electrodes include, for example, Pt/Ti electrodes, IrO2
/Ti electrode, RuO2 /Ti electrode, etc.
【００２６】電解質溶液中には、ヒドラジンなどが必要
に応じて添加されてもよい。ヒドラジンは、溶存酸素の
除去のために添加される。[0026] Hydrazine or the like may be added to the electrolyte solution as necessary. Hydrazine is added for removal of dissolved oxygen.
【００２７】なお、粉砕時間、すなわち水を電気分解し
て希土類合金に水素を吸蔵させる時間は特に限定されず
、通常、希土類合金の粉砕が終了するまで行なえばよい
。この時間は、希土類合金の寸法や組成などの各種条件
によって大きく異なるが、通常、０．５〜３時間程度で
ある。The pulverization time, ie, the time for electrolyzing water to absorb hydrogen into the rare earth alloy, is not particularly limited, and the pulverization may normally be continued until the end of the pulverization of the rare earth alloy. This time varies greatly depending on various conditions such as the dimensions and composition of the rare earth alloy, but is usually about 0.5 to 3 hours.
【００２８】また、水素吸蔵粉砕後、合金から水素を除
去するため、あるいは水素の一部を除去して安定な希土
類金属水素化物を形成するために、必要に応じて熱処理
を施してもよい。[0028] Further, after the hydrogen storage pulverization, heat treatment may be performed as necessary to remove hydrogen from the alloy or to remove a part of the hydrogen to form a stable rare earth metal hydride.
【００２９】本発明は、希土類合金製造時の粉砕工程に
適用される。本発明が適用される希土類合金の組成に特
に制限はないが、特にＮｄ−Ｆｅ−Ｂ系永久磁石に対し
て本発明は有効である。また、例えばＳｍＣｏ５ やＳ
ｍ２ Ｃｏ１７等のＳｍ−Ｃｏ系永久磁石など、他の希
土類磁石にも本発明は適用でき、さらに、Ｔｂ−Ｆｅや
Ｓｍ−Ｆｅ等の希土類金属−遷移金属からなる磁歪材料
や、水素吸蔵合金などにも本発明は適用可能である。The present invention is applied to the crushing process during the production of rare earth alloys. Although there is no particular restriction on the composition of the rare earth alloy to which the present invention is applied, the present invention is particularly effective for Nd-Fe-B permanent magnets. Also, for example, SmCo5 and S
The present invention can also be applied to other rare earth magnets such as Sm-Co permanent magnets such as m2Co17, and magnetostrictive materials made of rare earth metal-transition metals such as Tb-Fe and Sm-Fe, hydrogen storage alloys, etc. The present invention is also applicable to
【００３０】本発明が適用される粉砕工程に特に制限は
なく、希土類合金を粉砕する必要のある種々の工程に適
用可能である。例えば希土類合金を焼結法により製造す
る場合、合金粉末を成形して焼結するが、本発明は合金
粉末を得るための母合金インゴット粉砕工程に好適であ
る。There is no particular restriction on the pulverizing process to which the present invention can be applied, and the present invention can be applied to various processes that require pulverizing rare earth alloys. For example, when rare earth alloys are manufactured by a sintering method, alloy powder is shaped and sintered, and the present invention is suitable for the step of crushing a master alloy ingot to obtain alloy powder.
【００３１】以下、本発明が特に好ましく適用されるＮ
ｄ−Ｆｅ−Ｂ系永久磁石の製造方法について説明する。Hereinafter, N to which the present invention is particularly preferably applied
A method for manufacturing a d-Fe-B permanent magnet will be explained.
【００３２】Ｎｄ−Ｆｅ−Ｂ系永久磁石は、Ｎｄ２ Ｆ
ｅ１４Ｂ金属間化合物を主相とし、この主相は実質的に
正方晶系の結晶構造を有する。[0032] The Nd-Fe-B permanent magnet is Nd2F
The main phase is an e14B intermetallic compound, and this main phase has a substantially tetragonal crystal structure.
【００３３】本発明は、例えば、Ｎｄ−Ｆｅ−Ｂ系永久
磁石を焼結法により製造する際の母合金インゴットの粉
砕に好適である。また、例えば、本発明はボンディッド
磁石製造の際にも有用である。ボンディッド磁石は、通
常、溶湯状の母合金を冷却基体に衝突させて薄帯状等の
急冷合金を作製し、この急冷合金を粉砕して樹脂や金属
等のバインダで結合して製造されるが、本発明は、急冷
合金の粉砕に好適である。The present invention is suitable, for example, for crushing a master alloy ingot when producing Nd-Fe-B permanent magnets by a sintering method. For example, the present invention is also useful in manufacturing bonded magnets. Bonded magnets are usually manufactured by colliding a molten master alloy against a cooling base to create a rapidly solidified alloy in the form of a ribbon, then crushing this rapidly solidified alloy and bonding it with a binder such as resin or metal. The present invention is suitable for crushing rapidly solidified alloys.
【００３４】Ｎｄ−Ｆｅ−Ｂ系永久磁石を本発明により
粉砕して磁石粉末とした場合、磁石粉末に熱処理を施す
ことが好ましい。この熱処理は、磁石粉末から水素の一
部を除去して、安定な水素化物を形成するために行なわ
れる。この熱処理時の雰囲気は真空または不活性ガス雰
囲気とすることが好ましい。また、熱処理の保持温度お
よび保持時間は特に限定されないが、通常、２００〜８
００℃程度にて０．５〜５時間程度とすることが好まし
い。When a Nd-Fe-B permanent magnet is ground into magnet powder according to the present invention, it is preferable to subject the magnet powder to heat treatment. This heat treatment is performed to remove some of the hydrogen from the magnet powder to form a stable hydride. The atmosphere during this heat treatment is preferably a vacuum or an inert gas atmosphere. In addition, the holding temperature and holding time of the heat treatment are not particularly limited, but usually 200 to 800
It is preferable to set it as about 0.5 to 5 hours at about 00 degreeC.
【００３５】なお、電解質溶液中における水素吸蔵粉砕
は１回だけに限らず、上記熱処理を挟んで複数回行なっ
てもよい。[0035] The hydrogen storage pulverization in the electrolyte solution is not limited to one time, but may be performed multiple times with the above heat treatment in between.
【００３６】熱処理後、磁石粉末は必要に応じてさらに
粉砕される。水素吸蔵粉砕後の磁石粉末を構成する合金
粒子の平均粒径は２０〜１０００μｍ 程度であるが、
必要に応じてさらに粉砕される。この粉砕は、機械的粉
砕手段により行なう。この場合の粉砕手段に特に制限は
なく、ジェットミル、アトライター、ボールミル等の通
常の粉砕機により行なうことができる。焼結磁石の原料
粉末とする場合、平均粒径１〜１０μｍ 程度にまで粉
砕することが好ましい。After the heat treatment, the magnet powder is further pulverized if necessary. The average particle size of the alloy particles constituting the magnet powder after hydrogen storage pulverization is about 20 to 1000 μm,
Further grinding is performed if necessary. This pulverization is performed by mechanical pulverization means. There is no particular restriction on the pulverizing means in this case, and a conventional pulverizer such as a jet mill, attritor, or ball mill can be used. When used as raw material powder for sintered magnets, it is preferable to grind the powder to an average particle size of about 1 to 10 μm.
【００３７】本発明が適用される場合、磁石全体の組成
は特に限定されず、焼結法や急冷法等の製造方法に応じ
て、あるいは要求される磁気特性等に応じて適宜組成を
選択すればよいが、通常、５．５原子％≦Ｎｄ≦３０原
子％、４２原子％≦Ｆｅ≦９０原子％および２原子％≦
Ｂ≦２８原子％程度とされる。[0037] When the present invention is applied, the composition of the entire magnet is not particularly limited, and the composition may be selected as appropriate depending on the manufacturing method such as sintering method or quenching method, or depending on the required magnetic properties, etc. Usually, 5.5 atom%≦Nd≦30 atom%, 42 atom%≦Fe≦90 atom%, and 2 atom%≦
B≦28 atomic % or so.
【００３８】そして、Ｎｄの一部を、他の希土類元素、
例えば、Ｐｒ、Ｈｏ、Ｔｂ、Ｌａ、Ｓｍ、Ｃｅ、Ｇｄ、
Ｅｒ、Ｅｕ、Ｐｍ、Ｔｍ、Ｙｂ、Ｙ等の１種以上で置換
してもよい。Ｎｄに対するこれらの元素の置換率は、２
０％以下であることが好ましい。[0038] A part of Nd is replaced with other rare earth elements,
For example, Pr, Ho, Tb, La, Sm, Ce, Gd,
It may be substituted with one or more of Er, Eu, Pm, Tm, Yb, Y, and the like. The substitution rate of these elements for Nd is 2
It is preferably 0% or less.
【００３９】また、温度特性の改善のために、Ｆｅの一
部をＣｏで置換してもよい。Ｆｅに対するＣｏの置換率
は、５０％以下とすることが好ましい。Further, in order to improve the temperature characteristics, a part of Fe may be replaced with Co. The substitution ratio of Co to Fe is preferably 50% or less.
【００４０】また、これらの元素の他、Ｃａ、Ｃ、Ｐ、
Ｓ、Ｃｕ、Ａｌ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｂｉ、Ｎｂ、
Ｔａ、Ｍｏ、Ｗ、Ｓｂ、Ｇｅ、Ｓｎ、Ｚｒ、Ｎｉ、Ｓｉ
、Ｈｆ等の１種以上が含有されていてもよい。これらの
元素の含有率は、通常、総計で１０原子％以下とするこ
とが好ましい。[0040] In addition to these elements, Ca, C, P,
S, Cu, Al, Ti, V, Cr, Mn, Bi, Nb,
Ta, Mo, W, Sb, Ge, Sn, Zr, Ni, Si
, Hf, etc. may be contained. The content of these elements is usually preferably 10 atomic % or less in total.
【００４１】[0041]
【実施例】以下、本発明の具体的実施例を示し、本発明
をさらに詳細に説明する。EXAMPLES Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in more detail.
【００４２】原子百分率で１４．５％Ｎｄ、０．６％Ｄ
ｙ、６．７％Ｂ、７８．２％Ｆｅの組成を有する母合金
インゴットを鋳造により作製した。[0042] 14.5% Nd, 0.6% D in atomic percentage
A master alloy ingot having a composition of y, 6.7% B, and 78.2% Fe was produced by casting.
【００４３】この母合金インゴットから直方体状の合金
塊を切りだし、この合金塊をポリエステル樹脂中に封入
した。封入後、樹脂を研磨し、合金塊の一端面を樹脂外
に露出させた。このときの合金塊の露出面の寸法は縦１
０ｍｍ、横１０ｍｍであり、合金塊の高さは８ｍｍであ
った。[0043] A rectangular parallelepiped alloy ingot was cut out from this mother alloy ingot, and this alloy ingot was encapsulated in a polyester resin. After encapsulation, the resin was polished to expose one end surface of the alloy ingot to the outside of the resin. At this time, the dimension of the exposed surface of the alloy ingot is 1
0 mm, width 10 mm, and height of the alloy ingot was 8 mm.
【００４４】この合金塊を３０℃の０．２Ｍ Ｋ２ Ｓ
Ｏ４（ｐＨ６．１）溶液中に浸漬して電圧を印加し、飽
和カロメル電極に対する電位と電流密度との関係を調べ
た。
なお、対極にはＰｔ電極を、参照電極には飽和カロメル
電極を用いた。結果を図１に示す。図１において、合金
塊の電位は飽和カロメル電極に対する電位（対ＳＣＥ）
である。[0044] This alloy ingot was heated to 0.2M K2 S at 30°C.
The electrode was immersed in an O4 (pH 6.1) solution and a voltage was applied to examine the relationship between the potential and current density for a saturated calomel electrode. Note that a Pt electrode was used as a counter electrode, and a saturated calomel electrode was used as a reference electrode. The results are shown in Figure 1. In Figure 1, the potential of the alloy ingot is the potential relative to the saturated calomel electrode (vs. SCE)
It is.
【００４５】合金塊の電位が−１．１Ｖ から卑側であ
った場合、すなわち、電位の変化に対して電流密度が殆
ど変化しない電位範囲よりも卑な電位であった場合、合
金塊表面からの水素ガス発生と、合金塊表面からの粉末
の崩落が認められた。具体的には、電流密度１００Ａ／
ｄｍ２ のとき、１時間の通電で合金塊表面から２ｍｍ
の深さまでの領域が粉末化して崩落した。また、対極か
らは酸素ガスの発生が認められた。[0045] When the potential of the alloy lump is on the base side from -1.1V, that is, when the potential is lower than the potential range in which the current density hardly changes with respect to a change in potential, the potential of the alloy lump is Hydrogen gas generation and powder collapse from the surface of the alloy lump were observed. Specifically, the current density is 100A/
dm2, 2mm from the surface of the alloy ingot after 1 hour of energization
Areas up to a depth of Furthermore, generation of oxygen gas was observed from the counter electrode.
【００４６】一方、合金塊の電位が−１．１Ｖ を超え
て貴であった場合、希土類合金の粉末化は認められなか
った。On the other hand, when the potential of the alloy ingot was higher than -1.1V, no powdering of the rare earth alloy was observed.
【００４７】以上の実施例の結果から、本発明の効果が
明らかである。From the results of the above examples, the effects of the present invention are clear.
【００４８】[0048]
【発明の効果】本発明によれば、希土類合金を陰極とし
て水の電気分解を行なうという簡易で安全な方法より、
希土類合金を水素吸蔵粉砕することができる。このため
水素ガスおよび真空装置を準備する必要がなく、希土類
合金の加熱も不要である。また、従来行なう必要のあっ
た希土類合金表面活性化のための真空中熱処理も不要で
ある。[Effects of the Invention] According to the present invention, water electrolysis is performed using a rare earth alloy as a cathode, which is a simple and safe method.
Rare earth alloys can be pulverized to absorb hydrogen. Therefore, there is no need to prepare hydrogen gas and a vacuum device, and there is no need to heat the rare earth alloy. Further, heat treatment in vacuum for activating the surface of the rare earth alloy, which has conventionally been necessary, is not necessary.
【図１】飽和カロメル電極に対する希土類合金の電位と
、そのときの電流密度との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the potential of a rare earth alloy with respect to a saturated calomel electrode and the current density at that time.
Claims (4)
記希土類合金を陰極として前記電解質溶液中の水を電気
分解することにより、前記希土類合金表面で水を還元し
て水素を発生させ、この水素を前記希土類合金に吸蔵さ
せることにより前記希土類合金を粉砕する工程を有する
ことを特徴とする希土類合金粉末の製造方法。Claim 1: A rare earth alloy is immersed in an electrolyte solution, and water in the electrolyte solution is electrolyzed using the rare earth alloy as a cathode, thereby reducing water on the surface of the rare earth alloy to generate hydrogen. A method for producing a rare earth alloy powder, comprising the step of pulverizing the rare earth alloy by occluding the rare earth alloy into the rare earth alloy.
れて水の電気分解を行なう請求項１に記載の希土類合金
粉末の製造方法。2. The method for producing rare earth alloy powder according to claim 1, wherein the rare earth alloy is placed in a rotating container and water is electrolyzed.
請求項１または２に記載の希土類合金粉末の製造方法。3. The method for producing rare earth alloy powder according to claim 1, wherein the electrolyte solution has a pH of 5 or more.
Ｂを含有する永久磁石である請求項１ないし３のいずれ
かに記載の希土類合金粉末の製造方法。4. The method for producing rare earth alloy powder according to claim 1, wherein the rare earth alloy is a permanent magnet containing Nd, Fe, and B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12534091A JPH04329804A (en) | 1991-04-26 | 1991-04-26 | Production of rare earth alloy powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12534091A JPH04329804A (en) | 1991-04-26 | 1991-04-26 | Production of rare earth alloy powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04329804A true JPH04329804A (en) | 1992-11-18 |
Family
ID=14907698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12534091A Withdrawn JPH04329804A (en) | 1991-04-26 | 1991-04-26 | Production of rare earth alloy powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04329804A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015203080A (en) * | 2014-04-15 | 2015-11-16 | 株式会社フジミインコーポレーテッド | polishing composition |
| CN115768909A (en) * | 2020-07-01 | 2023-03-07 | 耶达研究与发展有限公司 | Recovery of rare earth metals from ferromagnetic alloys |
-
1991
- 1991-04-26 JP JP12534091A patent/JPH04329804A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015203080A (en) * | 2014-04-15 | 2015-11-16 | 株式会社フジミインコーポレーテッド | polishing composition |
| CN115768909A (en) * | 2020-07-01 | 2023-03-07 | 耶达研究与发展有限公司 | Recovery of rare earth metals from ferromagnetic alloys |
| JP2023533386A (en) * | 2020-07-01 | 2023-08-02 | イエダ リサーチ アンド ディベロプメント カンパニー リミテッド | Recovery of rare earth metals from ferromagnetic alloys |
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