JPH04318102A - Rare-earth alloy powder and its production - Google Patents
Rare-earth alloy powder and its productionInfo
- Publication number
- JPH04318102A JPH04318102A JP3108322A JP10832291A JPH04318102A JP H04318102 A JPH04318102 A JP H04318102A JP 3108322 A JP3108322 A JP 3108322A JP 10832291 A JP10832291 A JP 10832291A JP H04318102 A JPH04318102 A JP H04318102A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- rare earth
- alloy powder
- alloy
- calcium
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 25
- 239000000956 alloy Substances 0.000 title claims abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 14
- 150000002910 rare earth metals Chemical class 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 8
- 239000001110 calcium chloride Substances 0.000 claims abstract description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000009792 diffusion process Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 230000005496 eutectics Effects 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 6
- 239000012071 phase Substances 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910000767 Tm alloy Inorganic materials 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 235000011148 calcium chloride Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000828 alnico Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 101100083507 Caenorhabditis elegans acl-2 gene Proteins 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/0553—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 obtained by reduction or by hydrogen decrepitation or embrittlement
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】この発明は、磁気特性に優れるだ
けでなく、耐食性および温度特性にも優れる希土類−遷
移金属系磁石用の原料合金粉末およびその製造方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a raw material alloy powder for rare earth-transition metal magnets that has not only excellent magnetic properties but also excellent corrosion resistance and temperature characteristics, and a method for producing the same.
【０００２】0002
【従来の技術】現在、製造されている代表的な永久磁石
材料としては、アルニコ磁石、フェライト磁石及び希土
類磁石などが挙げられる。アルニコ磁石は歴史的に古い
が、安価なフェライト磁石あるいはさらにより高い磁気
特性を持つ希土類磁石の開発により、需要は低下しつつ
ある。一方フェライト磁石は、酸化物を主原料としてい
ることから化学的に安定で、かつ低コストであるため、
現在でも磁石材料の主流を占めているが、最大エネルギ
ー積が小さいという欠点があった。2. Description of the Related Art Typical permanent magnet materials currently manufactured include alnico magnets, ferrite magnets, and rare earth magnets. Alnico magnets have a long history, but demand is declining due to the development of cheaper ferrite magnets or even rare earth magnets with even higher magnetic properties. On the other hand, ferrite magnets are chemically stable and low cost because they are made of oxide as the main raw material.
Although it still occupies the mainstream of magnetic materials today, it has the drawback of having a small maximum energy product.
【０００３】その後、希土類イオンの持つ磁気異方性と
遷移金属元素の持つ磁気モーメントとを組合わせたＳｍ
−Ｃｏ系磁石が出現し、従来の最大エネルギー積を大幅
に更新した。しかしながら、Ｓｍ−Ｃｏ系磁石は資源的
に乏しいＳｍとＣｏを主成分としているために高価な磁
石とならざるを得なかった。[0003] After that, Sm, which combines the magnetic anisotropy of rare earth ions and the magnetic moment of transition metal elements, was developed.
-Co-based magnets have appeared and have significantly updated the conventional maximum energy product. However, since Sm--Co magnets mainly contain Sm and Co, which are scarce in terms of resources, they have had to be expensive magnets.
【０００４】そこでＳｍ−Ｃｏ系磁石に代わる、安価で
かつ高磁気特性を有する磁石合金の開発が進められ、そ
の結果佐川らは、焼結法により三元系で安定なＮｄ−Ｆ
ｅ−Ｂ系磁石（特公昭６１−３４２４２号公報および特
開昭５９−１３２１０４号公報） を開発し、その最大
エネルギー積はＳｍ−Ｃｏ系磁石のそれを超えるもので
ある。しかしながらＮｄ−Ｆｅ−Ｂ系磁石は、成分とし
て非常に活性の高いＮｄなどの軽希土類元素及び錆び易
いＦｅに富むことから、耐食性に劣り、その結果、磁気
特性が劣化して工業材料としての信頼性に欠けるという
欠点があった。[0004] Therefore, development of a magnet alloy that is inexpensive and has high magnetic properties to replace the Sm-Co magnet has been progressed, and as a result, Sagawa et al.
We have developed e-B magnets (Japanese Patent Publication No. 61-34242 and Japanese Unexamined Patent Publication No. 59-132104), whose maximum energy product exceeds that of Sm-Co magnets. However, Nd-Fe-B magnets have poor corrosion resistance because they are rich in light rare earth elements such as Nd, which is highly active, and Fe, which rusts easily.As a result, their magnetic properties deteriorate, making them unreliable as industrial materials. It had the disadvantage of lacking sex.
【０００５】従って耐食性の改善のために、たとえば焼
結磁石については表面処理（特開昭６３−７７１０３号
公報）を施すなどの対策が講じられているが、いずれも
長期間にわたって有効な防錆処理とはいえず、また処理
のためコスト高となり、さらには保護膜による磁束のロ
スなどの問題もあった。[0005] Therefore, measures have been taken to improve corrosion resistance, such as applying surface treatment to sintered magnets (Japanese Patent Application Laid-open No. 77103/1983), but none of these measures are effective against corrosion over a long period of time. It cannot be said that it is a treatment, and the cost is high due to the treatment.Furthermore, there are problems such as loss of magnetic flux due to the protective film.
【０００６】上記の問題の解決策として、発明者らは先
に特開平２−４９３９号公報において、Ｎｄ−Ｆｅ−Ｂ
系磁石のＦｅをＣｏおよびＮｉで高濃度に複合置換した
希土類−遷移金属−ボロン系磁石合金を提案し、表面処
理を施さずとも耐食性に優れ、しかもキュリー点の高い
永久磁石を実現した。As a solution to the above problem, the inventors previously proposed Nd-Fe-B in Japanese Unexamined Patent Publication No. 2-4939.
We proposed a rare earth-transition metal-boron-based magnet alloy in which Fe in the system magnet was replaced with Co and Ni at a high concentration, and achieved a permanent magnet with excellent corrosion resistance and a high Curie point without surface treatment.
【０００７】さらに発明者らは、上記のＮｄ−（Ｆｅ，
Ｃｏ， Ｎｉ）−Ｂ系磁石を発展させ、残留磁束密度
の高い ＲＥ２ＴＭ１４Ｂ１相（以下主相と略す。なお
ＴＭは、Ｆｅ， Ｃｏ及びＮｉのうちから選んだ一種ま
たは二種以上）を主体とする粉末と、焼結性を上げ、ま
た主相粒界のクリーニング作用を持ち、さらには電気化
学的にも貴な組成になる低融点のＲＥ−ＴＭ相（ここで
ＴＭは、Ｎｉ又は （Ｎｉ＋Ｆｅ） 又は （Ｎｉ＋Ｃ
ｏ） ）を主体とする粉末とを出発材料として、両粉末
を混合した後、成形、液相焼結を行って得られる二相混
合組織になる耐食性希土類−遷移金属系永久磁石を開発
し、特願平２−２６９６３５号明細書において開示した
。Furthermore, the inventors discovered that the above Nd-(Fe,
Co, Ni)-B system magnet is developed, and the RE2TM14B1 phase (hereinafter abbreviated as main phase) with high residual magnetic flux density (TM is one or more selected from Fe, Co, and Ni) is the main component. powder and a low-melting-point RE-TM phase (here TM is Ni or (Ni+Fe)) that improves sinterability, has a cleaning effect on the main phase grain boundaries, and has an electrochemically noble composition. or (Ni+C
We have developed a corrosion-resistant rare earth-transition metal based permanent magnet that has a two-phase mixed structure obtained by mixing both powders, molding and liquid phase sintering, using powder mainly consisting of o) ). This was disclosed in Japanese Patent Application No. 2-269635.
【０００８】[0008]
【発明が解決しようとする課題】上記した二相混合磁石
の原料として有用な低融点ＲＥ−ＴＭ系合金は、通常、
熱還元法、電解法などにより精製された純度９９．５％
以上の希土類金属と純度９９．９％以上の電解ニッケル
、電解コバルト、電解鉄などの高純度の原料を用いて作
製されるが、これらのうち特に希土類金属原料の分離精
製は高度な技術を要するため、工業原料としては極めて
高価なものとなっている。[Problems to be Solved by the Invention] The low melting point RE-TM alloy useful as a raw material for the above-mentioned two-phase mixed magnet is usually
Purity 99.5% purified by thermal reduction method, electrolytic method, etc.
It is manufactured using the above rare earth metals and high purity raw materials such as electrolytic nickel, electrolytic cobalt, and electrolytic iron with a purity of 99.9% or more, but the separation and purification of rare earth metal raw materials requires particularly advanced technology. Therefore, it is extremely expensive as an industrial raw material.
【０００９】また、粉末冶金原料として考えた場合、Ｒ
Ｅ−ＴＭ系合金は概して剪断強度が大きく、微粉化が困
難という問題を抱えている。[0009] Furthermore, when considered as a raw material for powder metallurgy, R
E-TM alloys generally have a problem of high shear strength and difficulty in pulverization.
【００１０】この発明は、上記の問題を有利に解決する
もので、安価な希土類酸化物とＴＭ粉末とを原料として
、これらを還元剤と共に加熱し、還元・拡散反応によっ
て、工業的規模でのＲＥ−ＴＭ合金を安価ならしめると
共に、得られたＲＥ−ＴＭ合金粉末を水素脆化後、粉砕
することによって、ＲＥ−ＴＭ合金の微粉化も容易なら
しめた希土類合金粉末およびその製造方法を提案するこ
とを目的とする。[0010] This invention advantageously solves the above-mentioned problems, and uses inexpensive rare earth oxides and TM powder as raw materials, heats them together with a reducing agent, and performs a reduction/diffusion reaction on an industrial scale. We propose a rare earth alloy powder that makes RE-TM alloy less expensive and also makes it easier to pulverize the RE-TM alloy by crushing the obtained RE-TM alloy powder after hydrogen embrittlement, and a method for producing the same. The purpose is to
【００１１】[0011]
【課題を解決するための手段】この発明の要旨構成は次
のとおりである。
１） ＲＥ：１５ａｔ％以上、９０ａｔ
％以下、ここでＲＥ：Ｙ，Ｓｃおよびランタノイドのう
ちから選んだ一種または二種以上
を含み、残部は実質的にＴＭ（ただしＴＭは、Ｎｉ又は
ＮｉとＦｅもしくはＣｏとの混合物）になる、ＲＥ−Ｔ
Ｍ系金属間化合物又はＲＥ−ＴＭ系共晶組成の合金から
なる希土類合金粉末（第１発明）。[Means for Solving the Problems] The gist of the present invention is as follows. 1) RE: 15at% or more, 90at
% or less, where RE: contains one or more selected from Y, Sc and lanthanoids, and the remainder is substantially TM (however, TM is Ni or a mixture of Ni and Fe or Co). RE-T
A rare earth alloy powder comprising an M-based intermetallic compound or an alloy having a RE-TM eutectic composition (first invention).
【００１２】２）一種又は二種以上のＲＥの酸化物とＴ
Ｍ粉末とを混合した原料粉末に、金属カルシウム及び／
又は水素化カルシウムと塩化カルシウムとを混合したの
ち、不活性雰囲気において加熱して還元・拡散反応を進
行させ、ついで得られた反応生成物を水及び／又はアル
コールと接触させ、該反応生成物中に含有される水溶性
物質を溶出させることにより、ＲＥ−ＴＭ粉末を採取す
ることからなる希土類合金粉末の製造方法（第２発明）
。2) One or more RE oxides and T
Metallic calcium and/or
Alternatively, after mixing calcium hydride and calcium chloride, the mixture is heated in an inert atmosphere to advance the reduction/diffusion reaction, and then the resulting reaction product is brought into contact with water and/or alcohol. A method for producing rare earth alloy powder (second invention) comprising collecting RE-TM powder by eluting water-soluble substances contained in
.
【００１３】３）上記した第２発明によって製造したＲ
Ｅ−ＴＭ粉末を、水素を含む不活性ガス中で乾燥・脆化
したのち、粉砕することからなる希土類合金粉末の製造
方法（第３発明）。3) R produced according to the second invention described above
A method for producing rare earth alloy powder (third invention), which comprises drying and embrittling E-TM powder in an inert gas containing hydrogen, and then pulverizing it.
【００１４】さて上記合金粉末は、以下の工程で得られ
る。すなわち希土類酸化物とＴＭ粉末を所望の組成にな
るように混合し、この混合粉に、還元剤としてモル比に
して酸化物の還元に必要な量の２〜３倍の金属カルシウ
ム及び／又は水素化カルシウムと、還元反応の促進剤と
して塩化カルシウムとを添加し、ついで不活性雰囲気中
において ８６０〜１１００℃程度の温度で１〜３時間
程度の還元・拡散処理を施したのち、室温まで冷却する
。ついで好ましくはハンマークラッシャー等で１０ｍｍ
以下の粒子に粉砕したのち、水及び／又はアルコール中
に入れ、不活性雰囲気中で２〜３時間程度混合すること
により、還元反応生成物であるＣａＯ， ＣａＯ・２Ｃ
ａＣｌ２及びＣａ（ＯＨ）２ あるいは未反応で残存す
る金属Ｃａなどを溶出させ、除去する。その後、合金粉
末をとり出し、不活性ガスと水素ガスとの混合ガス中で
室温〜３５０ ℃で１〜１０時間程度の乾燥・脆化処理
を施す。そして得られた乾燥粗粉を、シクロヘキサン中
でボールミルやジェットミル等により微粉砕するのであ
る。The above-mentioned alloy powder can be obtained through the following steps. That is, a rare earth oxide and TM powder are mixed to have a desired composition, and metallic calcium and/or hydrogen are added as a reducing agent to the mixed powder in an amount 2 to 3 times the molar ratio required for reducing the oxide. Calcium chloride and calcium chloride as a reduction reaction accelerator are added, and then reduction/diffusion treatment is performed in an inert atmosphere at a temperature of about 860 to 1100°C for about 1 to 3 hours, and then cooled to room temperature. . Then, preferably with a hammer crusher etc., 10 mm
After pulverizing into the following particles, they are placed in water and/or alcohol and mixed for about 2 to 3 hours in an inert atmosphere to produce the reduction reaction products CaO, CaO・2C.
aCl2 and Ca(OH)2, unreacted remaining metal Ca, etc. are eluted and removed. Thereafter, the alloy powder is taken out and subjected to drying and embrittlement treatment for about 1 to 10 hours at room temperature to 350° C. in a mixed gas of inert gas and hydrogen gas. Then, the obtained dry coarse powder is pulverized in cyclohexane using a ball mill, jet mill, etc.
【００１５】[0015]
【作用】まず第１発明において、ＲＥ−ＴＭ合金の成分
組成を上記の範囲に限定した理由について説明する。二
相混合磁石の焼結助剤として有効な第１発明に係る合金
粉末は、ＲＥ：１５ａｔ％以上、９０ａｔ％以下を含み
、残部は、ＴＭから成るＲＥ−ＴＭ合金粉末である。こ
こにＲＥは、Ｙ，Ｓｃおよびランタノイドのうちから選
んだ一種または二種以上であり、かかるＲＥが１５ａｔ
％に満たないと、形成されるＲＥ−ＴＭ相は、融点が高
く、二相混合磁石の焼結助剤として不適当であり、一方
ＲＥが９０ａｔ％を超えるとＲＥ−ＴＭ相はＲＥに富み
すぎ、これを原料とした二相混合磁石では耐食性が著し
く劣化するので、ＲＥは１５〜９０ａｔ％の範囲に限定
した。またＴＭは、Ｎｉ又は （Ｎｉ＋Ｆｅ） 又は
（Ｎｉ＋Ｃｏ） であり、ここにＦｅ， Ｃｏの含有量
はＴＭ中、 ９２ ａｔ％以下程度とするのが好ましい
。なおＴＭ中のＮｉの効果は、ＲＥ−ＴＭ相の融点を下
げ、二相磁石の焼結助剤としての効果を向上させると共
に、耐食性の改善に有効に作用することである。[Operation] First, in the first invention, the reason why the composition of the RE-TM alloy is limited to the above range will be explained. The alloy powder according to the first invention, which is effective as a sintering aid for a two-phase mixed magnet, is an RE-TM alloy powder containing RE: 15 at% or more and 90 at% or less, and the remainder being TM. Here, RE is one or more selected from Y, Sc and lanthanoids, and such RE is 15at
If the RE is less than 90 at%, the RE-TM phase formed has a high melting point and is unsuitable as a sintering aid for a two-phase mixed magnet. On the other hand, if the RE exceeds 90 at%, the RE-TM phase is rich in RE. RE is limited to a range of 15 to 90 at% because the corrosion resistance of a two-phase mixed magnet using this as a raw material deteriorates significantly. Moreover, TM is Ni or (Ni+Fe) or
(Ni+Co), where the content of Fe and Co in the TM is preferably about 92 at% or less. Note that the effect of Ni in TM is to lower the melting point of the RE-TM phase, improve the effect as a sintering aid for a two-phase magnet, and work effectively to improve corrosion resistance.
【００１６】次に、第２発明における、還元剤、反応促
進剤の効果を述べる。還元剤として加える金属カルシウ
ム（融点 ８５１℃）又は水素化カルシウム（融点 ８
１７℃）は、 ８６０〜１１００℃に加熱されることに
よって溶融し、希土類酸化物及び原料ＴＭ粉を包み込み
、まず酸化物を還元すると共に、ＴＭ粉表面を活性にし
、速かにＲＥ−ＴＭ化合物と酸化カルシウム（ＣａＯ）
等を生成する。なお加熱温度が ８６０℃に満たない
と上記の反応が速かに進まず、一方１１００℃を超える
と生成したＲＥ−ＴＭの多くは気化し、最終的な収量の
減少を招くので、加熱温度は ８６０〜１１００℃程度
とするのが好ましい。またＣａＣｌ２ を加えるのは、
生成したＣａＯ にこれを配位結合させ ＣａＯ・２Ｃ
ａＣｌ２とし、後続の水中及び／又はアルコール中での
分解を一層速かにするためである。ここに還元生成物の
分解は、水中及び／又はアルコール中で行うことができ
るが、とくにアルコールを５０ ｖｏｌ％以上添加した
水中で行うことが望ましい。
というのはかかる混合液での処理が、未反応の金属カル
シウムの分解を穏かに進める上で効果的だからである。Next, the effects of the reducing agent and reaction accelerator in the second invention will be described. Calcium metal (melting point 851℃) or calcium hydride (melting point 851℃) added as a reducing agent
(17℃) is heated to 860-1100℃, melts it, envelops the rare earth oxide and the raw TM powder, first reduces the oxide, activates the TM powder surface, and quickly converts the RE-TM compound. and calcium oxide (CaO)
etc. Note that if the heating temperature is less than 860°C, the above reaction will not proceed quickly, while if it exceeds 1100°C, much of the RE-TM produced will vaporize, resulting in a decrease in the final yield, so the heating temperature should be adjusted accordingly. The temperature is preferably about 860 to 1100°C. Also, adding CaCl2 is
Coordinate this to the generated CaO and CaO・2C
This is to make the subsequent decomposition in water and/or alcohol more rapid. The reduction product can be decomposed in water and/or alcohol, but it is particularly desirable to decompose it in water to which 50 vol% or more of alcohol has been added. This is because treatment with such a mixed solution is effective in gently progressing the decomposition of unreacted metallic calcium.
【００１７】さらに粉末冶金原料として微粉化が必要な
場合、第３発明に従い、生成したＲＥ−ＴＭ粉を、不活
性ガス及び水素の混合ガス中に曝し、乾燥・脆化させる
。二相混合磁石の焼結助剤として効果のあるＲＥ−ＴＭ
相は、概して剪断応力が大きく、微粉化が困難であるが
、予め水素を吸収させ脆化させておくと、粉末冶金初期
工程の微粉化が容易になる。Furthermore, when pulverization is required as a raw material for powder metallurgy, according to the third invention, the produced RE-TM powder is exposed to a mixed gas of an inert gas and hydrogen to dry and embrittle it. RE-TM is effective as a sintering aid for two-phase mixed magnets
Phases generally have large shear stress and are difficult to pulverize, but if they are made brittle by absorbing hydrogen in advance, pulverization in the initial step of powder metallurgy becomes easier.
【００１８】上記の工程で得られた乾燥・脆化済みのＲ
Ｅ−ＴＭ粉は、ボールミル、ジェットミル等で粉砕する
ことにより、５μｍ 以下に容易に微粉化される。そし
てかかる微粉を他の方法で製造され粉砕されたＲＥ２Ｔ
Ｍ１４Ｂ１ 粉末と混合すれば、より均一に混合される
ため、焼結時に、ＲＥ−ＴＭ液相が効果的にＲＥ２ＴＭ
１４Ｂ１ 粒間に回り込み、焼結性が向上するので、高
磁気特性の二相混合磁石が得られるのである。[0018] The dried and embrittled R obtained in the above process
E-TM powder can be easily pulverized to 5 μm or less by pulverization using a ball mill, jet mill, or the like. and RE2T produced by other methods and pulverized from such fine powder.
When mixed with M14B1 powder, the RE-TM liquid phase is effectively mixed with RE2TM during sintering because it is mixed more uniformly.
14B1 wraps around between the grains and improves sinterability, making it possible to obtain a two-phase mixed magnet with high magnetic properties.
【００１９】[0019]
実施例１
ＲＥ２Ｏ３， ＴＭ， 金属Ｃａ及びＣａＣｌ２ を表
１に示す割合で混合し、Ａｒ雰囲気の密閉容器中にて
８６０℃で２時間加熱したのち、室温にまで冷却した。
ついでハンマークラッシャーにて５ｍｍ以下に粉砕した
のち、過剰の５０ ｖｏｌ％エタノール水溶液中に投入
し、１時間の撹拌後、エタノール溶液を交換し、同じ操
作を２回繰り返した。次に得られたスラリーをろ過し、
Ａｒガス中にて室温で６時間乾燥させ、さらにボールミ
ルで微粉砕してＲＥ−ＴＭ粉末を得た。
これとは別に ＲＥ２ＴＭ１４Ｂ１合金を高周波溶解に
より作製したのち、均一化熱処理−ハンマークラッシャ
ーによる粗粉砕処理−ボールミルによる微粉砕処理を施
してＲＥ２ＴＭ１４Ｂ１ 粉末を得た。Example 1 RE2O3, TM, metallic Ca and CaCl2 were mixed in the proportions shown in Table 1, and the mixture was heated in a closed container in an Ar atmosphere.
After heating at 860°C for 2 hours, it was cooled to room temperature. Next, the mixture was crushed to 5 mm or less using a hammer crusher, and then poured into an excess 50 vol% ethanol aqueous solution. After stirring for 1 hour, the ethanol solution was replaced, and the same operation was repeated twice. The resulting slurry was then filtered and
It was dried in Ar gas at room temperature for 6 hours and further pulverized in a ball mill to obtain RE-TM powder. Separately, RE2TM14B1 alloy was produced by high-frequency melting, and then subjected to homogenization heat treatment, coarse crushing with a hammer crusher, and fine crushing with a ball mill to obtain RE2TM14B1 powder.
【００２０】ついで得られたＲＥ−ＴＭ粉末及び ＲＥ
２ＴＭ１４Ｂ１粉末を表１に示す種々の割合で混合した
のち、磁場中プレス、焼結を経て永久磁石とした。かく
して得られた希土類−遷移金属系磁石の磁気特性及び耐
食性について調べた結果を表１に示す。ここに耐食性は
、温度：７０℃、湿度：９５％の環境に４８ｈ曝した後
における発錆面積率で評価した。なお比較のため、純Ｒ
Ｅと電解ＴＭを出発原料として、これらを高周波溶解に
より溶解ＲＥ−ＴＭ合金とした場合についての調査結果
を表１に併せて示す。[0020] Then, the obtained RE-TM powder and RE
After mixing 2TM14B1 powder in various proportions shown in Table 1, the mixture was pressed in a magnetic field and sintered to form a permanent magnet. Table 1 shows the results of investigating the magnetic properties and corrosion resistance of the rare earth-transition metal magnet thus obtained. Corrosion resistance was evaluated by the rusted area ratio after being exposed to an environment of temperature: 70° C. and humidity: 95% for 48 hours. For comparison, pure R
Table 1 also shows the results of an investigation in which E and electrolytic TM were used as starting materials to form a melted RE-TM alloy by high-frequency melting.
【００２１】[0021]
【表１】[Table 1]
【００２２】同表より明らかなように、この発明に従う
ＲＥ−ＴＭ粉を用いた場合でも、磁気特性、耐食性とも
従来より優れた結果が得られた。従ってＲＥ酸化物を出
発原料とする本法は、高純度ＲＥを出発原料とする従来
法に比べてコスト的に有利となる。As is clear from the same table, even when the RE-TM powder according to the present invention was used, results superior to the conventional ones in both magnetic properties and corrosion resistance were obtained. Therefore, the present method using RE oxide as a starting material is more cost-effective than the conventional method using high-purity RE as a starting material.
【００２３】実施例２
Ｎｄ２Ｏ３， Ｄｙ２Ｏ３とＮｉとを、Ｎｄ＋ＤｙとＮ
ｉの原子比にして３：１の割合で混合し、式量比で Ｎ
ｄ２Ｏ３とＤｙ２Ｏ３ の総量の６倍の金属水素カルシ
ウムと、０．２５倍のＣａＣｌ２ を添加したのち、Ａ
ｒガス中において ８６０℃で２時間加熱し、引き続き
室温まで冷却したのち、ハンマークラッシャーで５ｍｍ
以下に粗粉砕した。ついで過剰の５０ ｖｏｌ％エタノ
ール水溶液中に投入し、不活性雰囲気中にて１時間の撹
拌後、エタノール水溶液を交換し、同じ操作を２回繰り
返した。次に得られた合金粉に、１０ｖｏｌ％Ｈ２＋Ａ
ｒ混合ガス中にて室温で３時間、 ３００℃で２時間の
乾燥・脆化処理を施したのち、真空中で ４５０℃，
１時間の加熱処理を施すことによって合金中の水素を排
気したのち、室温に戻してからシクロヘキサン中にてボ
ールミルで１２時間粉砕した。Example 2 Nd2O3, Dy2O3 and Ni, Nd+Dy and N
The atomic ratio of i is mixed at a ratio of 3:1, and the formula weight ratio is N
After adding 6 times the total amount of d2O3 and Dy2O3 and 0.25 times the amount of CaCl2, A
After heating at 860℃ for 2 hours in R gas and cooling to room temperature, it was crushed into 5mm pieces using a hammer crusher.
It was coarsely ground as below. Then, it was poured into an excess 50 vol% ethanol aqueous solution, and after stirring for 1 hour in an inert atmosphere, the ethanol aqueous solution was exchanged, and the same operation was repeated twice. Next, add 10 vol% H2+A to the obtained alloy powder.
After drying and embrittlement treatment in a mixed gas at room temperature for 3 hours and at 300℃ for 2 hours, it was dried at 450℃ in vacuum.
After heating the alloy for 1 hour to exhaust the hydrogen in the alloy, the alloy was returned to room temperature and then ground in cyclohexane in a ball mill for 12 hours.
【００２４】ボールミルでの粉砕時間と平均粒度との関
係について調べた結果を、図１に示す。なお比較のため
、上記のエタノール水溶液で処理して得られた合金粉を
、Ａｒ中で６時間乾燥したのち、シクロヘキサン中にて
ボールミルで１２時間粉砕したときの粉砕時間と平均粒
度との関係について調べた結果も、図１に併せて示す。FIG. 1 shows the results of an investigation into the relationship between the milling time in a ball mill and the average particle size. For comparison, the relationship between the grinding time and average particle size when the alloy powder obtained by processing with the above ethanol aqueous solution was dried in Ar for 6 hours and then ground in cyclohexane in a ball mill for 12 hours. The results of the investigation are also shown in Figure 1.
【００２５】同図より明らかなように、予め水素・アル
ゴン混合ガス中で脆化させたものの方が微粉化が顕著で
あり、また所要時間も短時間で済んだ。[0025] As is clear from the figure, the powder that had been embrittled in advance in a hydrogen/argon mixed gas was more conspicuously pulverized and required a shorter time.
【００２６】[0026]
【発明の効果】かくしてこの発明によれば、工業的規模
で安価に、希土類−遷移金属系合金粉末を得ることがで
き、さらに水素脆化させることにより、粉末の微粉化が
一層容易になる。Thus, according to the present invention, rare earth-transition metal alloy powder can be obtained on an industrial scale at low cost, and further, by hydrogen embrittlement, the powder can be further easily pulverized.
【図１】ボールミルでの粉砕時間と平均粒度との関係を
示したグラフである。FIG. 1 is a graph showing the relationship between milling time in a ball mill and average particle size.
Claims (3)
下、ここでＲＥ：Ｙ，Ｓｃおよびランタノイドのうちか
ら選んだ一種または二種以上 を含み、残部は実質的にＴＭ（ただしＴＭは、Ｎｉ又は
ＮｉとＦｅもしくはＣｏとの混合物）になる、ＲＥ−Ｔ
Ｍ系金属間化合物又はＲＥ−ＴＭ系共晶組成の合金から
なることを特徴とする希土類合金粉末。Claim 1: RE: 15 at% or more and 90 at% or less, where RE: contains one or more selected from Y, Sc and lanthanoids, and the remainder is substantially TM (however, TM is Ni or RE-T (a mixture of Ni and Fe or Co)
A rare earth alloy powder comprising an M-based intermetallic compound or an alloy having a RE-TM-based eutectic composition.
Ｍ粉末とを混合した原料粉末に、金属カルシウム及び／
又は水素化カルシウムと塩化カルシウムとを混合したの
ち、不活性雰囲気において加熱して還元・拡散反応を進
行させ、ついで得られた反応生成物を水及び／又はアル
コールと接触させ、該反応生成物中に含有される水溶性
物質を溶出させることにより、ＲＥ−ＴＭ粉末を採取す
ることを特徴とする希土類合金粉末の製造方法。[Claim 2] One or more RE oxides and T
Metallic calcium and/or
Alternatively, after mixing calcium hydride and calcium chloride, the mixture is heated in an inert atmosphere to advance the reduction/diffusion reaction, and then the resulting reaction product is brought into contact with water and/or alcohol. 1. A method for producing rare earth alloy powder, which comprises collecting RE-TM powder by eluting water-soluble substances contained in the powder.
−ＴＭ粉末を、水素を含む不活性ガス中で乾燥・脆化し
たのち、粉砕することを特徴とする希土類合金粉末の製
造方法。[Claim 3] RE produced by the method according to claim 2
- A method for producing rare earth alloy powder, which comprises drying and embrittling TM powder in an inert gas containing hydrogen, and then pulverizing it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3108322A JPH04318102A (en) | 1991-04-15 | 1991-04-15 | Rare-earth alloy powder and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3108322A JPH04318102A (en) | 1991-04-15 | 1991-04-15 | Rare-earth alloy powder and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04318102A true JPH04318102A (en) | 1992-11-09 |
Family
ID=14481773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3108322A Pending JPH04318102A (en) | 1991-04-15 | 1991-04-15 | Rare-earth alloy powder and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04318102A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108183010A (en) * | 2017-12-14 | 2018-06-19 | 浙江大学 | Method that is a kind of while improving neodymium ferrocerium boron sintered magnet magnetic property and corrosion resistance |
-
1991
- 1991-04-15 JP JP3108322A patent/JPH04318102A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108183010A (en) * | 2017-12-14 | 2018-06-19 | 浙江大学 | Method that is a kind of while improving neodymium ferrocerium boron sintered magnet magnetic property and corrosion resistance |
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