JPH04137702A - Manufacture of sm-co rare earth permanent magnet - Google Patents
Manufacture of sm-co rare earth permanent magnetInfo
- Publication number
- JPH04137702A JPH04137702A JP2261647A JP26164790A JPH04137702A JP H04137702 A JPH04137702 A JP H04137702A JP 2261647 A JP2261647 A JP 2261647A JP 26164790 A JP26164790 A JP 26164790A JP H04137702 A JPH04137702 A JP H04137702A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- earth permanent
- permanent magnet
- acid
- grinding
- 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
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 49
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000227 grinding Methods 0.000 claims abstract description 59
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 27
- 239000000843 powder Substances 0.000 abstract description 10
- 238000011282 treatment Methods 0.000 abstract description 10
- 238000010306 acid treatment Methods 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001291 vacuum drying Methods 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 230000005484 gravity Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- -1 Sm = 26 wt% Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000003141 lower extremity Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 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
- H01F1/0551—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0552—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes with a protective layer
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
イ１発明の目的
〔産業上の利用分野〕
本発明は５ｓ−Ｃｏ希土類永久磁石の研削屑を永久磁石
の原料としての再活用することによるＳｍ−Ｃｏ希土類
永久磁石の製造方法に関するものである。Detailed Description of the Invention A1 Object of the Invention [Field of Industrial Application] The present invention is directed to the production of Sm-Co rare-earth permanent magnets by reusing grinding waste of 5s-Co rare-earth permanent magnets as a raw material for permanent magnets. This relates to a manufacturing method.
従来、５ａｄ−Ｃｏ系希土類磁石の研削屑を原料として
使用することはマグネットメーカーにとっては長い間の
懸案事項であった。Ｓｍ−Ｃｏ系希土類永久磁石の研削
屑は主に５１２０３等の酸化物が形成されて、５１２０
３等の酸化物が多くなって、主成分のＳ！１２ｃＯ１Ｔ
中に入ってしまうと比重もさがり、なにより磁気特性を
さげてしまうので、５Ｉｌ−Ｃｏ系希土類永久磁石の研
削屑は原料として使用することは５１２０３等の酸化物
を除去しないかぎり困難であった。またＳｍの微粉が研
磨中の加熱で着火して燃えてしまうので、Ｓｓの微粉の
含んだ研削屑は扱い注意であり、研削屑を原料として使
用するには５１２０３の除去が重要であった。このＳｍ
、０３の除去する方法や処理に難点があって、以前より
カルシウム還元法や酸処理方法等が行われていたが、手
軽な方法として用いることは出来ず、不充分であった。Conventionally, the use of grinding waste from 5ad-Co rare earth magnets as a raw material has been a long-standing concern for magnet manufacturers. Grinding waste of Sm-Co rare earth permanent magnets mainly consists of oxides such as 51203, and 5120
The number of 3rd grade oxides increases, and the main component is S! 12cO1T
If it gets inside, the specific gravity decreases, and above all, the magnetic properties decrease, so it was difficult to use the grinding debris of 5Il-Co rare earth permanent magnets as a raw material unless oxides such as 51203 were removed. . Furthermore, since the Sm fine powder ignites and burns due to heating during polishing, grinding waste containing Ss fine powder must be handled with care, and in order to use the grinding waste as a raw material, it was important to remove 51203. This Sm
, 03 has some drawbacks in its removal methods and treatments, and although calcium reduction methods and acid treatment methods have been used for some time, they have not been able to be used as easy methods and have been insufficient.
カルシウム還元法は５１２０３にＣｏ３Ｏ４やＣａＦを
加えて反応させてＳｍやＣｏを還元して抽出する法で、
すでに特許になっている。The calcium reduction method is a method in which Co3O4 and CaF are added to 51203 and reacted to reduce and extract Sm and Co.
It's already patented.
また酸洗による酸処理方法は強酸となると法律上の取扱
いが厳しくコストがかかり、 Ｓｍ、 Ｃｏ、 Ｆｅ。In addition, the acid treatment method by pickling is difficult to handle legally and is expensive when it comes to strong acids.
Ｃｕ、 Ｚｒ等をとかしてしまう難点があり、実用化の
段階として、酸処理がもっとも手軽であり、酸処理によ
って５ｌ−Ｃｏ系希土類永久磁石の原料として研削屑を
使用出来れば、これにこしたことはない。It has the disadvantage of combing out Cu, Zr, etc., and acid treatment is the easiest at the stage of practical application. Never.
しかしながらどのような条件で酸処理するのか、その手
軽な最適条件はつかまれてはいない。またＳｍ−Ｃｏ希
土類永久磁石の研削屑は、切断加工や研磨加工である加
工工程において発生し、この研削屑から溶媒抽出法など
の化学的元素分離方法により高価な元素である、Ｓｔ
Ｃｏの２種類の元素の分離抽出が行われている。しかし
ながら、抽出された高価な２種類のＳｍ、ＣＯの両元素
のみでは、２−１７型Ｓｍ−Ｃｏ希土類永久磁石の原料
にすることは出来ず、再度２−１７型Ｓｍ−Ｃｏ系希土
類永久磁石原料とする為にＳｓとＣｏ以外のＣｕ、 Ｆ
ｅ及びＺｒ等を加え、通常の２−１７型Ｓｍ−Ｃｏ系希
土類永久磁石の原料の製造方法である溶解の段階から再
生を行わねばならず、工程及びコストが増大してしまう
という重大な欠点があった。However, the optimum conditions for acid treatment have not yet been determined. In addition, grinding waste from Sm-Co rare earth permanent magnets is generated during processing steps such as cutting and polishing.
Two types of elements, Co, are being separated and extracted. However, the extracted two expensive elements Sm and CO alone cannot be used as raw materials for the 2-17 type Sm-Co rare earth permanent magnet, and the 2-17 type Sm-Co rare earth permanent magnet cannot be used again. Cu and F other than Ss and Co are used as raw materials.
A serious disadvantage is that it is necessary to add e, Zr, etc. and regenerate from the melting stage, which is the manufacturing method of the raw material of the normal 2-17 type Sm-Co rare earth permanent magnet, which increases the process and cost. was there.
本発明は以上の様な欠点を改善するために、この研削屑
へＰＨが３．５〜５．５の弱い酸による処理を施すこと
により、研削屑を２−１７型Ｓ層−〇〇系希土類永久磁
石原料としてそのまま新規原料と配合し使用して工程及
びコストの増大無く、２−１７型５ｓ−Ｃｏ系希土類永
久磁石の原料として使用して、２−１７型Ｓｍ−Ｃｏ系
希土類永久磁石を製造することを目的とする。In order to improve the above-mentioned drawbacks, the present invention treats the grinding waste with a weak acid with a pH of 3.5 to 5.5, thereby removing the grinding waste from the 2-17 type S layer-〇〇 system. A 2-17 type Sm-Co rare earth permanent magnet can be used as a raw material for a 2-17 type 5s-Co rare earth permanent magnet without increasing the process or cost by blending it with a new raw material as it is as a raw material for a rare earth permanent magnet. The purpose is to manufacture.
口１発明の構成
〔課題を解決するための手段〕
本発明は、Ｓ■−Ｃｏ希土類永久磁石の研削屑の表面に
存在する５Ｉ２０３等の酸化物を除去するために、ＰＨ
が３．５〜５．５の酸溶液中で、該研削屑を酸洗処理し
、再生することを特徴とする。1. Structure of the Invention [Means for Solving the Problems] The present invention uses PH
It is characterized in that the grinding waste is pickled and regenerated in an acid solution having a pH of 3.5 to 5.5.
即ち本発明は、Ｓ■−Ｃｏ系希土類永久磁石の研削屑を
ＰＨが３−５−５．５の弱い酸で酸処理し、該研削屑の
表面の酸化物を除去し、Ｓ■−Ｃｏ系希土類永久磁石用
の原料と配合して、前記研削屑をＳ鳳−Ｃｏ系希土類永
久磁石として性能が得られるように組成調整して、前記
研削屑をＳｍ−Ｃｏ系希土類永久磁石の原料とすること
を特徴とする５ａｄ−Ｃｏ系希土類永久磁石の製造方法
である。That is, in the present invention, grinding waste of an S■-Co rare earth permanent magnet is acid-treated with a weak acid having a pH of 3-5-5.5, oxides on the surface of the grinding waste are removed, and S■-Co The grinding waste is blended with a raw material for a Sm-Co rare earth permanent magnet, and the composition is adjusted so that the performance of the grinding waste is obtained as an Sm-Co rare earth permanent magnet. This is a method for manufacturing a 5ad-Co rare earth permanent magnet.
Ｓｍ−Ｃｏ系希土類永久磁石の研削屑はＳｍ−Ｃｏ系希
土類永久磁石の研磨した塊に５１１２０＋、Ｃｅ２Ｏ３
，ＣＯ２Ｏ３等の酸化物の微粉が付着して、研削屑のま
わりをこの酸化物の微粉でまぶしてくるんでν）る状態
にある。このような５１２０３、Ｃｅ２Ｏ３、ＣＯ２Ｏ
３等の酸化物は原料に入ると、比重をさげてしまうこと
より致命的欠陥である磁気特性をさげてしまうので、長
ν）間研削屑の原料としての再利用は重要な課題であっ
たことは前述した通りである。そこで研削屑の中の５Ｉ
２０３、Ｃｅ２Ｏ，＋等の酸化物の除去は手軽にやれる
と、その利用価値は太きＱＮ。研削屑を強酸である塩酸
や硫酸で処理すると、研削屑は表面積力で大きいので、
Ｆｅ、 Ｃｕ以外の主成分まで解けてしまう。The grinding waste of the Sm-Co rare earth permanent magnet is 51120+, Ce2O3, in the polished lump of the Sm-Co rare earth permanent magnet.
, CO2O3, and other oxide particles are attached to the ground, and the grinding debris is covered with the oxide particles. 51203 like this, Ce2O3, CO2O
When grade 3 oxides enter the raw material, they reduce the specific gravity, which is a fatal defect, and reduce the magnetic properties, so reusing long-term grinding waste as a raw material was an important issue. This is as stated above. There, 5I in the grinding waste
If oxides such as 203 and Ce2O,+ can be easily removed, their utility value is high QN. When grinding debris is treated with strong acids such as hydrochloric acid or sulfuric acid, the grinding debris is large due to surface area force, so
Main components other than Fe and Cu can be solved.
さらに強酸は法律的に使用する際は厳しし）管理下にお
かれ扱いにくく、さらにカセイソーダなど番こよって中
和しなければならず、強酸の酸処理は手数がかかりコス
ト的に不利である。このため、強酸の処理はさけ、ＰＨ
が７〜５．５までの酸では弱く、ここではＰＨが３．５
〜５．５になるようにうすめて酢酸を使用した。ＰＨが
３．５〜５．５の範囲であれば例えば酢酸でも、他の強
酸でもよいが、酢酸が扱いやすいから酢酸を選択して、
酢酸を使用したものである。Furthermore, strong acids are difficult to handle as they are subject to strict controls when used legally, and must be neutralized using caustic soda, making acid treatment of strong acids time-consuming and disadvantageous in terms of cost. For this reason, avoid treatment with strong acids, and avoid
It is weak in acids with a pH of 7 to 5.5, and here the pH is 3.5.
Acetic acid was diluted to ~5.5 and used. For example, acetic acid or other strong acids may be used as long as the pH is in the range of 3.5 to 5.5, but acetic acid is selected because it is easy to handle.
It uses acetic acid.
２−１７型Ｓｍ−Ｃｏ系希土類永久磁石の原料として配
合の目標値は、Ｓｍ＝２６冑ｔ％、Ｆｅ＝ １５ｗｔ％
。The target values for the raw materials for the 2-17 type Sm-Co rare earth permanent magnet are Sm = 26t%, Fe = 15wt%
.
Ｃｕ ＝ ４．５ｗｔ％、Ｚｒ＝ ３ ｗｔ％、Ｃｏ＝
Ｂａ１ｗｔ％である。Cu = 4.5 wt%, Zr = 3 wt%, Co =
Ba1wt%.
Ｓ塵が一般に高値で、８膳の原料を購入するとＣｅが入
ってくる。そこで５１２ＣＯ１７型よりＣｅの含んだ（
Ｓｌｏ、 ５ｃｅｏ、 ５）２ＣＯ１□の希土類永久磁
石を選択することが多い。この（Ｓ■ｏ、 ５Ｃｅｏ、
５）２ＣＯ１７の希土類永久磁石の配合の目標値とし
てはＳｍ＝ １１．８ｗｔ％、Ｃｅ＝ １１．８ｗｔ％
、 Ｆｅ＝ １５ｗｔ％、 Ｃｕ＝４．５ｗｔ％、Ｚｒ
＝ ３．０ｗｔ％、Ｃｏ＝ Ｂａ１ｗｔ％がＳｍ＋Ｃｅ
＝ ２３．６％であるから有利である。しかしここでは
Ｓｍ＝２６ｗｔ％、Ｆｅ＝１５ｗｔ％、Ｃｕ＝ ４．５
ｗｔ％、ｚｒ＝ ３ ｗｔ％、Ｃｏ＝Ｂａ１ｗｔ％、で
配合した例である。研削屑の中のＳｍ２Ｏ３、Ｃｅ２Ｏ
３とＣＯ２Ｏ３では圧倒的にＳｌ２Ｏ３、Ｃｅ２０ｒが
多く生成され、研削屑を酸処理するために研削屑の重量
［ｋｇ］とＰＨが３．５〜５．５の２体積％酢酸溶液量
［１］の比率が１＝６の比率で、酸溶液中に研削屑を投
入し、酸溶液中で、２０〜３０分間攪拌し酸洗処理し、
酸洗処理の回数は１〜５回である。この際酢酸と５Ｉ２
０３、Ｃｅ２Ｏ３の微粉は次の反応する。S dust is generally expensive, and if you purchase 8 batches of raw materials, Ce will be included. Therefore, the 512CO17 type contains more Ce (
Slo, 5ceo, 5) Rare earth permanent magnets of 2CO1□ are often selected. This (S■o, 5Ceo,
5) Target values for the composition of 2CO17 rare earth permanent magnet are Sm = 11.8wt%, Ce = 11.8wt%
, Fe=15wt%, Cu=4.5wt%, Zr
= 3.0wt%, Co=Ba1wt% is Sm+Ce
= 23.6%, which is advantageous. However, here Sm=26wt%, Fe=15wt%, Cu=4.5
This is an example in which Co is mixed in wt%, zr=3 wt%, and Co=Ba1 wt%. Sm2O3, Ce2O in grinding waste
3 and CO2O3, an overwhelmingly large amount of Sl2O3 and Ce20r are generated, and in order to acid-treat the grinding waste, the weight of the grinding waste [kg] and the amount of 2 volume % acetic acid solution with a pH of 3.5 to 5.5 [1] The grinding chips are put into an acid solution with a ratio of 1=6, and the grinding chips are stirred and pickled in the acid solution for 20 to 30 minutes,
The number of times of pickling treatment is 1 to 5 times. At this time, acetic acid and 5I2
03, Ce2O3 fine powder undergoes the following reaction.
Ｓ■２０３＋Ｃ■３Ｃ００Ｈ＝Ｓ■２ （ＣＬＣＯＯ）
３ ＋ ＣＯ２＋Ｈ２０ＣｅｚＯ３＋ＣＨ３ＣＯ０Ｈ
＝ Ｃｅｚ （ＣＨ３ＣＯＯ） ３ ＋ ＣＯ２＋Ｈ２
０酢酸サマリウム塩５１１２ （ＣＨ３ＣＯＯ） ３と
酢酸セリウム塩Ｃｅ２（ＣＨ３ＣＯＯ） ３は酸洗で、
洗われて流れて、残るのは求める５１２−Ｃｏ系希土類
永久磁石の粉末である。S■203+C■3C00H=S■2 (CLCOO)
3 + CO2+H20CezO3+CH3CO0H
= Cez (CH3COO) 3 + CO2+H2
0 samarium acetate 5112 (CH3COO) 3 and cerium acetate Ce2 (CH3COO) 3 are acid-washed,
After being washed away, what remains is the desired 512-Co rare earth permanent magnet powder.
今まで３１２０３やＣｅ２Ｏ：＋の微粉があって、これ
が磁石の組成としては不要で、しかも磁気特性を悪くす
るので、研削屑が原料として使用出来なかった理由であ
る。このＳｌ２Ｏ３とＣｅ２Ｏ３を酢酸で酸洗すること
で酢酸サマリウム塩Ｓ１２ （ＣＨ３ＣＯＯ） ３、酢
酸セリウム塩Ｃｅ２（ＣＨ３ＣＯＯ） ３として処理し
て、除去することによって研削屑が原料として使用出来
ることがわかった。Up until now, there have been fine powders of 31203 and Ce2O:+, which are unnecessary in the composition of magnets and deteriorate magnetic properties, which is why grinding waste could not be used as a raw material. It was found that the grinding waste could be used as a raw material by treating and removing the Sl2O3 and Ce2O3 as samarium acetate salt S12 (CH3COO) 3 and cerium acetate salt Ce2 (CH3COO) 3 by pickling with acetic acid.
本発明を以下の実施例に基づき、詳細に説明する。 The present invention will be explained in detail based on the following examples.
５ｓ−Ｃｏ希土類永久磁石の研削屑を研削屑の状態のま
ま再利用する為に以下の様な、ＰＨが３．５〜５．５の
酸処理を該研削屑に施した。該研削屑を酸処理するため
に研削屑重量［ｋｇ］とＰＨが３．５〜５．５の酸溶液
量［１］の比率が１：６の比率で２体積パーセント酢酸
を使用し、ＰＨ＝ ３．５〜５，５の酸溶液中に投入し
、酸溶液中に於て、２０〜３０分間攪拌し酸洗処理を行
った。酸洗処理の回数は１〜５回行った。その後肢研削
屑中に残留した酸を取り除くために、純水による洗浄を
１〜３回行った。該洗浄の攪拌時間は５〜１５分間とし
た。その後、該純水中に研削屑を放置すると、酸処理に
より酸化物がはがされ、活性化した研削屑が再度、純水
中の酸素と反応し、８膳の酸化物を形成するため、アル
コールで１〜４回洗浄を行った。該攪拌時間は２０〜３
０分間とした。In order to reuse the grinding waste of the 5s-Co rare earth permanent magnet in the state of grinding waste, the grinding waste was subjected to the following acid treatment with a pH of 3.5 to 5.5. In order to acid-treat the grinding waste, 2 volume percent acetic acid was used at a ratio of 1:6 between the weight of the grinding waste [kg] and the amount of acid solution [1] with a pH of 3.5 to 5.5. = 3.5 to 5.5, and stirred in the acid solution for 20 to 30 minutes to perform pickling treatment. The pickling treatment was performed 1 to 5 times. Washing with pure water was performed 1 to 3 times to remove residual acid in the hindlimb grinding debris. The stirring time for this washing was 5 to 15 minutes. After that, when the grinding waste is left in the pure water, the oxide is removed by acid treatment, and the activated grinding waste reacts with oxygen in the pure water again to form eight oxides. Washing with alcohol was performed 1 to 4 times. The stirring time is 20-3
The duration was 0 minutes.
その後Ｎ２加圧及び真空乾燥によりこの研削屑を乾燥粉
末状態にした。Thereafter, this grinding waste was made into a dry powder state by applying N2 pressure and vacuum drying.
この段階に於ては分析した結果、この研削屑の組成がＳ
ｍ＝２５〜３８ｗｔ％、Ｆｅ＝ Ｏ〜１６ｗｔ％、Ｃｕ
＝０〜４．５ｗｔ％、 Ｚｒ＝ Ｏ〜３．Ｏｗｔ％、
Ｃｏ＝ ５０〜６５ｗｔ％である。２−１７型５ｒｓ−
Ｃｏ系希土類永久磁石の目標の組成の配合はＳｍ＝ ２
６ｗｔ％、Ｆｅ＝１５ｗｔ％、Ｃｕ＝ ４．５ｗｔ％、
Ｚｒ＝ ３ ｗｔ％、Ｃｏ＝ Ｂａ１ｗｔ％であるので
研削屑を分析して、研削屑の成分を鑑み、２−１７型Ｓ
鳳−Ｃｏ系希土類永久磁石としての性能が得られる上記
の目標の組成に、組成調成する。溶解法により製造され
た組成調整用の２−１７型Ｓ■−Ｃｏ系希土類永久磁石
の原料を、酸洗処理後この研削屑と５：５の比率で混合
し、２−１７型Ｓｍ−Ｃｏ系希土類永久磁石の原料粉末
として２−１７型５ｓ−Ｃｏ系希土類永久磁石の原料と
して使用する。At this stage, analysis revealed that the composition of the grinding debris was S.
m=25~38wt%, Fe=O~16wt%, Cu
=0~4.5wt%, Zr=O~3. Owt%,
Co=50 to 65 wt%. 2-17 type 5rs-
The target composition of the Co-based rare earth permanent magnet is Sm=2
6wt%, Fe=15wt%, Cu=4.5wt%,
Since Zr = 3 wt% and Co = Ba 1 wt%, the grinding waste was analyzed and, considering the components of the grinding waste, type 2-17 S was selected.
The composition is adjusted to the above-mentioned target composition that provides the performance as an Otori-Co rare earth permanent magnet. The raw material for a 2-17 type S■-Co rare earth permanent magnet for composition adjustment manufactured by the melting method is mixed with this grinding waste at a ratio of 5:5 after pickling treatment to form a 2-17 type Sm-Co rare earth magnet. The powder is used as a raw material powder for a 2-17 type 5s-Co rare earth permanent magnet.
その後、以上により作製した２−１７型Ｓ鳳−Ｃｏ系希
土類永久磁石の原料の粉末を、磁界中で圧縮成形し、焼
結溶体処理を行った。焼結は不活性ガス雰囲気あるいは
真空雰囲気中で１１８０〜ｂ
間で保持し、１１００〜１２１０℃Ｘ０．５〜３時間時
間化処理を施した後急冷する。その後時効処理とじて８
００℃×１〜４０時間保持し、５０〜１５０（℃／待時
間で徐冷後、３００℃以下で急冷する。Thereafter, the raw material powder of the 2-17 type S-Co rare earth permanent magnet produced as described above was compression molded in a magnetic field and subjected to sintering solution treatment. The sintering is performed by maintaining the temperature between 1180°C and 1210°C in an inert gas atmosphere or vacuum atmosphere, and subjecting the material to temperature treatment at 1100°C to 1210°C for 0.5 to 3 hours, followed by rapid cooling. After that, the aging process is completed 8
Hold at 00°C for 1 to 40 hours, slowly cool at 50 to 150°C/waiting time, and then rapidly cool to 300°C or less.
以上により得られた比重の関係と磁気特性の関係を第１
図に示す。The relationship between the specific gravity and the magnetic properties obtained above is the first
As shown in the figure.
第１図に示すように、第１図は研削屑と２−１７型Ｓ鵬
−Ｃｏ希土類永久磁石の原料５：５の配合したときの諸
特性の関係を求めたグラフである。第１図（ａ）は比重
との関係を求めたグラフで酸処理により酸化物が完全に
取り除かれないためか、焼結密度ρが８．０５〜８．０
９ｇ／ｃｍ３（通常ｐ ＝ ８．２〜８．４ｇ／ｃｍ３
）と多少低かった。As shown in FIG. 1, FIG. 1 is a graph showing the relationship between various properties when grinding waste and raw materials for a 2-17 type S-Co rare earth permanent magnet are mixed in a ratio of 5:5. Figure 1 (a) is a graph showing the relationship with specific gravity. Perhaps because oxides are not completely removed by acid treatment, the sintered density ρ is 8.05 to 8.0.
9g/cm3 (usually p = 8.2-8.4g/cm3
) was somewhat low.
即ち、５１２ＣＯ１７中研削層になる過程でもっとも変
動するのはＳｌであるから８膳の重量％を横軸にとって
、その変動を調べ、そのときに第１図（ａ）は比重、第
１図（ｂ）磁気特性である残留磁束密度Ｂｒ、角形比と
して第１図（ｃ）はＨｘ／＋Ｈｃ、第１図（ｄ）はエネ
ルギー積として（ＢＨ）膳ａＸ、抗磁力Ｈｅとして第１
図（ｅ）はＢＨＣ１第１図（ｆ）は１トの諸特性をみた
グラフである。In other words, since it is Sl that fluctuates the most in the process of forming the 512CO17 medium grinding layer, we examine its fluctuations by taking the weight percent of 8 pieces on the horizontal axis. b) Residual magnetic flux density Br, which is a magnetic property, Hx/+Hc in Figure 1(c) as a squareness ratio, Hx/+Hc in Figure 1(d) as an energy product, and 1 as a coercive force He.
Figure (e) is a graph showing various characteristics of BHC1. Figure 1 (f) is a graph showing various characteristics of BHC1.
グラフ中、Ａは本実施例のグラフであり、Ｂは比較例と
して、成分が研削屑を使用しない新規原料を使用した目
標通りに入ったＳｍ＝２６ｗｔ％、Ｆｅ＝１５ｗｔ％、
Ｃｕ＝ ４．５ｗｔ％、 Ｚｒ＝ ３ ｗｔ％、Ｃ
ｏ＝残ｗｔ％のときのＡと対応する諸特性である。In the graph, A is a graph of the present example, and B is a comparative example, in which the components were as expected using a new raw material that does not use grinding waste, Sm = 26 wt%, Fe = 15 wt%,
Cu = 4.5 wt%, Zr = 3 wt%, C
These are various characteristics corresponding to A when o=remaining wt%.
しかしながらＡの印はこのように酸処理をした研削屑を
使用したときの分析値でねらいをＳ鵬で２６％にしたに
もかかわらず２５．５〜２５．９ｗｔ％とばらつき、比
較例としたＢの黒い丸印は殆どばらつきがなく、２５．
９ｗｔ％に分析値が入っているので、全て生の原料を使
用した方が目標の成分値にばらつきが少なく配合出来る
ことを示しているといえる。However, the mark A indicates the analysis value when using acid-treated grinding waste, and although the aim was 26% with Sho, it varied from 25.5 to 25.9 wt%, and was used as a comparative example. There is almost no variation in the black circles in B, and 25.
Since the analytical value is at 9wt%, it can be said that it is possible to blend the target component values with less variation if all raw materials are used.
第１図をみるかぎりでは磁気特性に於ては、２−１７型
Ｓ■−Ｃｏ系希土類永久磁石合金としては、十分２−１
７型Ｓ層−Ｃｏ系希土類永久磁石の性能を持っているの
で、研削屑は原料として使用出来る。As far as we can see from Figure 1, in terms of magnetic properties, 2-1 is sufficient as a 2-17 type S■-Co rare earth permanent magnet alloy.
Since it has the performance of a 7 type S layer-Co rare earth permanent magnet, the grinding waste can be used as a raw material.
従って、実質的な工程及びコストの増大無しに、該研削
屑を２−１７型５ｌ−Ｃｏ希土類永久磁石合金として再
利用できる永久磁石が製造可能となった。Therefore, it has become possible to manufacture a permanent magnet in which the grinding waste can be reused as a 2-17 type 5l-Co rare earth permanent magnet alloy without substantial increase in process and cost.
以下余白
ハ１発明の効果
〔発明の効果〕
以上述べたごとく本発明によれば、５厘−Ｃｏ希土類永
久磁石合金研削屑を工程及びコストの増大が無く再生可
能であるという利点を持つため、最終的な原料コストの
低減が計れ、通常に比べ安価な２−１７型５ｉｎ−Ｃｏ
希土類永久磁石合金の提供が可能となった。1. Effects of the Invention [Effects of the Invention] As described above, the present invention has the advantage that 5-Co rare earth permanent magnet alloy grinding waste can be recycled without increasing the process or cost. 2-17 type 5in-Co which can reduce the final raw material cost and is cheaper than usual
It is now possible to provide rare earth permanent magnet alloys.
第１図は本発明の酸洗処理した研削屑を原料として使用
したときの２−１７型Ｓ層−Ｃｏ系希土類永久磁石の比
重、残留磁束密度、Ｈｘ／＋Ｈｃ、エネルギー積、ＢＨ
Ｃ％ ＩＨＣの諸特性をみたグラフである。
第１図（ａ）はＳ■重量％と比重との関係のグラフ。
第１図（ｂ）はＳｍ重量％と残留磁束密度との関係のグ
ラフ。
第１図（ｃ）はＳｍ重量％とＨＫ／ＩＨＣ角型比との関
係のグラフ。
第１図（ｄ）はＳ厘重量％とエネルギー積との関係のグ
ラフ。
第１図（ｅ）はＳｍ重量％とＪＣとの関係のグラフ。
第１図（ｆ）は８１重量％とｒＨｃとの関係のグラ乙Ａ
は本発明の研削屑使用の２−１７型Ｓ−−Ｃｏ系希土類
永久磁石の特性のグラフ。
Ｂは新しい原料のみによって配合した２−１７型Ｓ履−
Ｃｏ系希土類永久磁石の特性のグラ乙Figure 1 shows the specific gravity, residual magnetic flux density, Hx/+Hc, energy product, and BH of a 2-17 type S-layer Co-based rare earth permanent magnet using the pickled grinding waste of the present invention as a raw material.
C% This is a graph showing various characteristics of IHC. FIG. 1(a) is a graph of the relationship between S■ weight % and specific gravity. FIG. 1(b) is a graph of the relationship between Sm weight % and residual magnetic flux density. FIG. 1(c) is a graph of the relationship between Sm weight % and HK/IHC squareness ratio. FIG. 1(d) is a graph of the relationship between S weight % and energy product. FIG. 1(e) is a graph of the relationship between Sm weight % and JC. Figure 1(f) shows the relationship between 81% by weight and rHc.
is a graph of the characteristics of a 2-17 type S--Co rare earth permanent magnet using grinding waste according to the present invention. B is a 2-17 type S shoe made with only new raw materials.
Characteristics of Co-based rare earth permanent magnets
Claims (1)
５〜５．５の弱い酸で酸処理し、該研削屑の表面の酸化
物を除去し、Ｓｍ−Ｃｏ系希土類永久磁石用の原料と配
合して、前記研削屑をＳｍ−Ｃｏ系希土類永久磁石とし
て性能が得られるように組成調整して、前記研削屑をＳ
ｍ−Ｃｏ系希土類永久磁石の原料とすることを特徴とす
るＳｍ−Ｃｏ系希土類永久磁石の製造方法。1. Grinding waste of Sm-Co rare earth permanent magnet has a pH of 3.
The grinding waste is treated with a weak acid of 5 to 5.5 to remove oxides on the surface of the grinding waste, and mixed with raw materials for Sm-Co rare earth permanent magnets. The composition is adjusted so that the performance as a magnet can be obtained, and the grinding waste is
A method for producing an Sm-Co rare earth permanent magnet, characterized in that the method is used as a raw material for an m-Co rare earth permanent magnet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2261647A JPH04137702A (en) | 1990-09-28 | 1990-09-28 | Manufacture of sm-co rare earth permanent magnet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2261647A JPH04137702A (en) | 1990-09-28 | 1990-09-28 | Manufacture of sm-co rare earth permanent magnet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04137702A true JPH04137702A (en) | 1992-05-12 |
Family
ID=17364810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2261647A Pending JPH04137702A (en) | 1990-09-28 | 1990-09-28 | Manufacture of sm-co rare earth permanent magnet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04137702A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002343616A (en) * | 2001-05-15 | 2002-11-29 | Tdk Corp | Method for manufacturing oxide containing rare earth element |
-
1990
- 1990-09-28 JP JP2261647A patent/JPH04137702A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002343616A (en) * | 2001-05-15 | 2002-11-29 | Tdk Corp | Method for manufacturing oxide containing rare earth element |
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