JP3029711B2 - Rare earth magnet manufacturing method - Google Patents
Rare earth magnet manufacturing methodInfo
- Publication number
- JP3029711B2 JP3029711B2 JP3208659A JP20865991A JP3029711B2 JP 3029711 B2 JP3029711 B2 JP 3029711B2 JP 3208659 A JP3208659 A JP 3208659A JP 20865991 A JP20865991 A JP 20865991A JP 3029711 B2 JP3029711 B2 JP 3029711B2
- Authority
- JP
- Japan
- Prior art keywords
- magnet
- water
- powder
- rare earth
- solvent
- 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.)
- Expired - Lifetime
Links
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
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
Description
【０００１】[0001]
【産業上の利用分野】この発明は、Ｒ−Ｃｏ系磁石ある
いはＲ−Ｆｅ−Ｂ系磁石等の希土類磁石粉末を、有毒の
有機溶媒を使用しない湿式微粉砕にて製造する希土類磁
石の製造方法に係り、水を溶媒として用いて湿式微粉砕
するに際して、水に特定量の錯形成剤と還元剤を添加し
て微粉砕後の粉末中の不溶性不純物量を０．１ｐｐｍ以
下にし、永久磁石の磁石特性の劣化及び腐食を防止した
希土類磁石の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a rare earth magnet for producing a rare earth magnet powder such as an R--Co magnet or an R--Fe--B magnet by wet pulverization without using a toxic organic solvent. In connection with, when performing wet pulverization using water as a solvent, a specific amount of a complexing agent and a reducing agent are added to water to reduce the amount of insoluble impurities in the powder after pulverization to 0.1 ppm or less, The present invention relates to a method for manufacturing a rare earth magnet in which deterioration and corrosion of magnet properties are prevented.
【０００２】[0002]
【従来の技術】従来、Ｒ−Ｃｏ系磁石の製造に用いる磁
石粉末は、Ｃａ還元法あるいは粉砕法にて原料粉末を得
ていた。また、Ｒ−Ｆｅ−Ｂ系磁石等の希土類磁石の製
造に用いる磁石粉末は、電解により還元された希土類原
料を用いて、溶解して鋳型に鋳造し所要磁石組成の合金
塊を作成し、これを粉砕して所要粒度の合金粉末とする
溶解・粉砕法（特開昭６０−６３３０４号公報、特開昭
６０−１１９０７０１号公報）がある。この溶解・粉砕
法は、鋳塊の粗粉砕工程で容易に酸化防止が可能な粉砕
ができるため、比較的低含有酸素量の合金粉末が得られ
る。2. Description of the Related Art Conventionally, as a magnetic powder used for producing an R-Co magnet, a raw material powder has been obtained by a Ca reduction method or a pulverization method. In addition, magnet powder used for manufacturing rare earth magnets such as R-Fe-B magnets is melted and cast into a mold using a rare earth raw material reduced by electrolysis to form an alloy lump having a required magnet composition. And pulverization to obtain an alloy powder having a required particle size (JP-A-60-63304, JP-A-60-1190701). This melting and pulverization method can easily perform oxidation-preventive pulverization in the ingot coarse pulverization step, so that an alloy powder having a relatively low oxygen content can be obtained.
【０００３】かかる希土類磁石用磁石粉末は、所要粒度
にするためいずれも機械粉砕により粗粉砕後、さらにト
ルエン、メタノール、ヘキサン等の有機溶媒を用いて、
アトライター等内にて湿式微粉砕することが一般的であ
る。[0003] Such a rare earth magnet powder is roughly pulverized by mechanical pulverization in order to obtain a required particle size, and then further treated with an organic solvent such as toluene, methanol or hexane.
It is common to carry out wet pulverization in an attritor or the like.
【０００４】[0004]
【発明が解決しようとする課題】この湿式微粉砕に用い
る前記有機溶媒は有毒で危険性が高く、また公害上の問
題があるため、最近、水を溶媒とした湿式微粉砕法が提
案されており、水を溶媒として用いることは安全性及び
コストの点で有機溶媒に対してすぐれているThe above-mentioned organic solvent used for the wet pulverization is toxic and dangerous, and has a problem of pollution. Therefore, a wet pulverization method using water as a solvent has recently been proposed. Use of water as a solvent is superior to organic solvents in terms of safety and cost
【０００５】しかし、水には一般にＯ2量１０ｐｐｍ〜
２０ｐｐｍを含有するため、微粉砕時に溶媒に水を用い
て、希土類磁石、特にＮｄ−Ｆｅ−Ｂ系磁石の製造に適
用する場合、溶媒の水中のＯ2により、生成された微粉
砕粉が腐食され、また、溶媒の水中にＮｄ（ＯＨ）3、
ＦｅＯＯＨ等の不溶性不純物が生成し、この微粉砕粉か
ら得られる永久磁石の磁石特性の劣化及び腐食を招来す
る問題があり、実用化が困難であった。However, water generally has an O 2 content of 10 ppm or less.
To contain 20 ppm, using water as a solvent during milling, when applied rare earth magnet, especially production of Nd-Fe-B magnets, the O 2 in water solvent, the generated finely pulverized powder corrosion And Nd (OH) 3 ,
Insoluble impurities such as FeOOH are generated, and there is a problem that the magnet properties of the permanent magnet obtained from the finely pulverized powder are deteriorated and corroded, so that practical use has been difficult.
【０００６】この発明は、Ｒ−Ｃｏ系磁石あるいはＲ−
Ｆｅ−Ｂ系磁石等の希土類磁石粉末を、有毒の有機溶媒
を使用しない湿式微粉砕にて製造する希土類磁石の製造
方法の提供を目的とし、水を溶媒に用いて湿式微粉砕し
た際に永久磁石の磁石特性の劣化及び腐食させる不純物
量を低減できる希土類磁石の製造方法の提供を目的とし
ている。The present invention relates to an R-Co magnet or an R-Co magnet.
The purpose of the present invention is to provide a method for producing a rare earth magnet in which a rare earth magnet powder such as an Fe-B based magnet is produced by wet pulverization without using a toxic organic solvent. It is an object of the present invention to provide a method for manufacturing a rare earth magnet that can reduce the deterioration of the magnet properties of the magnet and the amount of impurities to be corroded.
【０００７】[0007]
【課題を解決するための手段】この発明は、希土類磁石
の製造時、微粉砕工程において、溶媒として水を用いた
場合、水中に含まれるＯ2量の低減と共に溶液中の不溶
性不純物の生成沈殿を防止するため、種々検討した結
果、水中に含まれるＯ2量の低減と共に溶液中に溶出す
るＦｅ、Ｒ（特にＮｄ）の不溶性沈殿物の生成を防止す
る方法として、溶媒としての水に特定量の錯形成剤と還
元剤を添加し、あるいはさらに前記水中に不活性ガスを
吹き込みバブリングすることにより、溶媒中の水に含ま
れるＯ2量の低減と共に、前記不溶性沈殿物を溶液中に
溶存させ、微粉砕後の濾過により微粉砕粉回収の際に、
不純物を濾過液として系外に除去できることを知見し完
成したものである。According to the present invention, when water is used as a solvent in a pulverization step in the production of a rare earth magnet, the amount of O 2 contained in the water is reduced and the generation of insoluble impurities in the solution is reduced. As a result of various investigations to prevent the formation of insoluble precipitates of Fe and R (especially Nd) that elute in the solution together with the reduction of the amount of O 2 contained in the water, water was specified as water as a solvent. by adding an amount of complexing agent and reducing agent, or even bubbling blowing an inert gas into the water, along with the reduction of O 2 content in the water in the solvent, the insoluble precipitate in the solution of dissolved At the time of fine powder recovery by filtration after fine pulverization,
It has been found out that impurities can be removed outside the system as a filtrate.
【０００８】すなわち、この発明は、湿式微粉砕にてＲ
−Ｃｏ系磁石あるいはＲ−Ｆｅ−Ｂ系磁石等の希土類磁
石粉末を得る希土類磁石の製造方法において、錯形成剤
を０．００１〜１ｍｏｌ／ｌ及び還元剤として１０ｇ／
ｌ以下のＮａ2ＳＯ3を添加した水、あるいはさらに前記
水中に不活性ガスを噴射して水中のＯ2量を１ｐｐｍ以
下に低減した水を溶媒に用いて湿式微粉砕し、微粉砕後
の濾過分離した粉末中の不溶性不純物量を０．１ｐｐｍ
以下にすることを特徴とする希土類磁石の製造方法であ
る。[0008] That is, the present invention provides a wet fine pulverizing method.
In a method for producing a rare-earth magnet for obtaining a rare-earth magnet powder such as a -Co-based magnet or an R-Fe-B-based magnet, a complex-forming agent is used in an amount of 0.001 to 1 mol / l and a reducing agent of 10 g /
1 or less of Na 2 SO 3 or water in which an inert gas is injected into the water to reduce the amount of O 2 in the water to 1 ppm or less as a solvent. 0.1 ppm of insoluble impurities in powder separated by filtration
A method for manufacturing a rare earth magnet, characterized in that:
【０００９】[0009]
【作用】詳述するとこの発明は、希土類磁石の製造時の
湿式微粉砕工程前に、溶媒となる水に錯形成剤を０．０
０１〜１ｍｏｌ／ｌ、還元剤として１０ｇ／ｌ以下のＮ
ａ2ＳＯ3を添加して、あるいはさらにＡｒガス又はＮ2
ガス等不活性ガスを吹き込んでバブリングして、溶媒の
水中のＯ2量を１ｐｐｍ以下に低減した後、前記処理水
を溶媒として湿式微粉砕した際の溶液中の不溶性不純物
量を０．１ｐｐｍ以下にすることにより、微粉砕後の濾
過時に不純物を濾過液として系外に除去し、濾過分離し
た粉末中の不溶性不純物量を０．１ｐｐｍ以下にするこ
とができ、得られる希土類磁石の磁石特性の劣化及び腐
食防止に多大な効果を発揮する。More specifically, the present invention provides a method of manufacturing a rare-earth magnet, which comprises adding a complexing agent to water as a solvent before the wet pulverization step at the time of manufacturing the rare-earth magnet.
01 to 1 mol / l, N of 10 g / l or less as a reducing agent
a 2 SO 3 is added, or Ar gas or N 2
After bubbling by blowing an inert gas such as a gas to reduce the amount of O 2 in the solvent water to 1 ppm or less, the amount of insoluble impurities in the solution when wet-milling using the treated water as a solvent is 0.1 ppm or less. By doing so, impurities can be removed from the system as a filtrate during filtration after pulverization, and the amount of insoluble impurities in the powder separated by filtration can be reduced to 0.1 ppm or less. It has a great effect on deterioration and corrosion prevention.
【００１０】この発明において、溶媒としての水には、
中性あるいはアルカリ性の水が好ましく、アルカリ性の
水としては、濃アンモニアを３００ｍｌ／ｌ以下、Ｎａ
ＯＨ、ＫＯＨ、Ｃａ（ＯＨ）2、ＫＨ2ＰＯ4、ＮａＨＰ
Ｏ4、ＮａＨＣＯ3、ＮａＣＨ3ＣＯＯ １００ｍｌ／ｌ
以下等のうち少なくとも１種を添加して得られる。ま
た、溶媒としてアルカリ性の水を使用することにより、
酸性、中性溶液よりもＮｄ、Ｆｅ等の溶出を低減でき、
原料粉末の腐食による磁石特性劣化の防止及び耐食性の
改善向上を図ることができる。In the present invention, water as a solvent includes:
Neutral or alkaline water is preferable. As the alkaline water, concentrated ammonia is 300 ml / l or less,
OH, KOH, Ca (OH) 2, KH 2 PO 4, NaHP
O 4 , NaHCO 3 , NaCH 3 COO 100 ml / l
It is obtained by adding at least one of the following. Also, by using alkaline water as a solvent,
Elution of Nd, Fe, etc. can be reduced more than acidic and neutral solutions,
It is possible to prevent deterioration of the magnet properties due to corrosion of the raw material powder and to improve and improve the corrosion resistance.
【００１１】さらに、水道水等の使用が可能であり、水
道水としては電導率２００μｓ／ｃｍ・２５℃以下、不
純物はＣｌ４０ｐｐｍ以下、Ｓｉ１５ｐｐｍ以下、Ｃａ
４０ｐｐｍ以下、Ｍｇ１０ｐｐｍ以下が好ましく、さら
にイオン交換、蒸留等の処理により電導率を１μｓ／ｃ
ｍ・２５℃以下に低減した方がよい。Further, tap water or the like can be used. Conductivity of tap water is 200 μs / cm · 25 ° C. or less, impurities are 40 ppm or less of Cl, 15 ppm or less of Si,
40 ppm or less, Mg 10 ppm or less is preferable, and the conductivity is set to 1 μs / c by treatment such as ion exchange and distillation.
It is better to reduce the temperature to m · 25 ° C. or less.
【００１２】この発明の特徴である水に添加する錯形成
剤としては、原料粉末の構成元素と錯形成するカルボン
酸系配位子又はアミン系配位子何れでもよいが、カルボ
ン酸系配位子としてはコハク酸、マレイン酸等が好まし
く、またアミン系配位子としてはＥＤＴＡ、ＤＴＰＡ等
が好ましい。錯形成剤の添加量は水１ｌに対して０．０
０１〜１ｍｏｌが好ましく、錯形成剤量が０．００１ｍ
ｏｌ／ｌ未満では錯形成が十分でなく、１ｍｏｌ／ｌを
超えると効果上は問題ないが経済上好ましくない。The complexing agent to be added to water, which is a feature of the present invention, may be either a carboxylic acid ligand or an amine ligand which forms a complex with the constituent elements of the raw material powder. As the ligand, succinic acid, maleic acid and the like are preferable, and as the amine-based ligand, EDTA and DTPA are preferable. The addition amount of the complexing agent is 0.0
The amount is preferably from 1 to 1 mol, and the amount of the complexing agent is 0.001 m.
When it is less than ol / l, complex formation is not sufficient, and when it exceeds 1 mol / l, there is no problem in effect, but it is economically unfavorable.
【００１３】この発明は、錯形成剤の添加と共に還元剤
としてＮａ2ＳＯ3を１０ｇ／ｌ以下添加することを特徴
とするが、１０ｇ／ｌを超える添加では効果の向上は認
められず、経済的に好ましくない。The present invention is characterized in that Na 2 SO 3 is added as a reducing agent in an amount of not more than 10 g / l together with the addition of a complexing agent. Is not preferred.
【００１４】さらに、この発明において、湿式微粉砕す
る前に錯形成剤と還元剤を含有する溶媒の水中にＡｒ、
Ｎ2ガス等の不活性ガスを噴射、バブリングすることに
より溶媒の水中に含まれるＯ2量を低減し、得られる微
粉砕粉の腐食を低減することができる。Further, in the present invention, Ar or Ar is added to a solvent containing a complexing agent and a reducing agent before the wet pulverization.
By jetting and bubbling an inert gas such as N 2 gas, the amount of O 2 contained in the solvent water can be reduced, and the corrosion of the obtained finely pulverized powder can be reduced.
【００１５】この発明において、Ａｒガス、Ｎ2ガス等
の不活性ガスによるバブリング条件としてはガス圧力
１．０〜３．０ｋｇ／ｃｍ2、吹き込み時間１０分〜６
０分、ガス流量３〜２０ｌ／ｍｉｎが好ましい。ガス圧
力が１．０ｋｇ／ｃｍ2未満では十分なガス導入ができ
ず、３．０ｋｇ／ｃｍ2を超えると水の飛散があり好ま
しくない。また、吹き込み時間が１０分未満ではＯ2除
去が十分でなく、６０分を超えると経済的でない。ま
た、ガス流量として３ｌ／ｍｉｎ未満では十分なＯ2除
去ができず、２０ｌ／ｍｉｎを超えると経済的に好まし
くない。In the present invention, bubbling conditions with an inert gas such as an Ar gas or a N 2 gas include a gas pressure of 1.0 to 3.0 kg / cm 2 and a blowing time of 10 minutes to 6 minutes.
The gas flow rate is preferably 3 to 20 l / min for 0 minute. When the gas pressure is less than 1.0 kg / cm 2 , sufficient gas cannot be introduced. When the gas pressure exceeds 3.0 kg / cm 2 , water is scattered, which is not preferable. If the blowing time is less than 10 minutes, the removal of O 2 is not sufficient, and if it exceeds 60 minutes, it is not economical. Further, if the gas flow rate is less than 3 l / min, it is not possible to sufficiently remove O 2 , and if it exceeds 20 l / min, it is not economically preferable.
【００１６】[0016]
【実施例】実施例１ 溶解・粉砕法により得られた３５．５ｗｔ％Ｎｄ−６
３．４ｗｔ％Ｆｅ−１．１ｗｔ％Ｂ組成の磁石用原料粉
末を、内容積１００ｌのアトライター内に１２ｍｍ直径
の鋼製ボールと共に入れ、さらに錯形成剤として酒石酸
０．０２ｍｌ／ｌ、還元剤のＮａ2ＳＯ3を５ｇ／ｌ含有
し、Ｏ2含有量が１．３ｐｐｍの水を所要量溶媒として
用い、これを回転数８０ｒｐｍ、３時間回転させる微粉
砕を行い、粉砕完了後に濾過して平均粒径３．４μｍの
微粉砕粉末を得た。得られた微粉砕粉末中のＲ，Ｆｅ等
の不溶性不純物量は、ＩＣＰ測定法により測定したとこ
ろ０．０３ｐｐｍであった。EXAMPLES obtained in Example 1 dissolved and pulverizing method 35.5 w t% Nd-6
3.4 w t% Fe-1.1 w t% a raw material powder for a magnet B composition, put together steel ball 12mm diameter in attritor having an inner volume of 100l, further tartrate as complexing agent 0.02 ml / 1, water containing 5 g / l of reducing agent Na 2 SO 3 and O 2 content of 1.3 ppm was used as a required solvent, and this was rotated at 80 rpm for 3 hours to perform fine grinding, and grinding was completed. Thereafter, the mixture was filtered to obtain a finely pulverized powder having an average particle size of 3.4 μm. The amount of insoluble impurities such as R and Fe in the obtained finely pulverized powder was 0.03 ppm as measured by an ICP measurement method.
【００１７】また、この微粉砕粉末を金型に装入し、約
１０ｋＯｅの磁界中で配向し、磁界に直角方向に約１．
５ｔｏｎ／ｃｍ2 の圧力で成型し、１５ｍｍ×２０ｍ
ｍ×８ｍｍの成型体を作成した。この成型体を１１００
℃×２時間のＡｒ雰囲気中条件で焼結し、引き続いて６
００℃×２時間の時効処理を行った。得られた試験片磁
石の磁石特性を表１に示す。Further, this finely pulverized powder is charged into a mold, oriented in a magnetic field of about 10 kOe, and placed in a direction perpendicular to the magnetic field for about 1.10 kOe.
Molded at a pressure of 5 ton / cm 2 , 15mm x 20m
A molded body of mx 8 mm was prepared. 1100
Sintering in an Ar atmosphere at 2 ° C. × 2 hours.
An aging treatment was performed at 00 ° C. for 2 hours. Table 1 shows the magnet properties of the obtained test piece magnets.
【００１８】実施例２ 溶解・粉砕法により得られた３５．５ｗｔ％Ｎｄ−６
３．４ｗｔ％Ｆｅ−１．２ｗｔ％Ｂ組成の磁石用原料粉
末を、内容積１００ｌのアトライター内に９．５ｍｍ直
径の鋼製ボールと共に入れ、さらに錯形成剤と還元剤を
含有した水を所要量溶媒として用い、これを回転数８０
ｒｐｍ、３時間回転させる微粉砕を行い、粉砕完了後に
濾過して平均粒径３．４μｍの微粉砕粉末を得た。な
お、溶媒の水は、事前に酒石酸０．０２ｍｌ／ｌ、ＤＴ
ＰＡ０．０２ｍｌ／ｌ並びにＮａ2ＳＯ3２ｇ／ｌを添加
し、ＮａＯＨにてｐＨを１１に調整し、さらに水中にＡ
ｒガスをガス圧力２．０ｋｇ／ｃｍ2、ガス流量５ｌ／
ｍｉｎ、吹き込み時間１時間の条件でバブリングして、
Ｏ2含有量を０．５ｐｐｍに低減した。溶媒の水のＯ 2 含
有量は未添加時に１２ｐｐｍであった。[0018] obtained in Example 2 dissolved and pulverizing method 35.5 w t% Nd-6
The 3.4 w t% Fe-1.2 w t% B raw material powder for a magnet composition, put together steel balls 9.5mm diameter in the attritor having an inner volume of 100l, a further complexing agent and reducing agent The contained water is used as a required amount of solvent,
After the pulverization was completed, the mixture was filtered after completion of the pulverization to obtain a finely pulverized powder having an average particle size of 3.4 μm. The solvent water was previously prepared with tartaric acid 0.02 ml / l, DT
0.02 ml / l of PA and 2 g / l of Na 2 SO 3 were added, the pH was adjusted to 11 with NaOH, and
r gas at a gas pressure of 2.0 kg / cm 2 and a gas flow rate of 5 l /
min, bubbling under the condition of blowing time 1 hour,
The O 2 content was reduced to 0.5 ppm. Contains O 2 in water of solvent
The content was 12 ppm when not added .
【００１９】得られた微粉砕粉末中のＲ，Ｆｅ等の不溶
性不純物量は、ＩＣＰ測定法により測定したところ０．
０２ｐｐｍであった。さらに実施例１と同様方法で、成
形、焼結、磁石化して得た磁石の磁石特性を表１に示
す。The amount of insoluble impurities such as R, Fe, etc. in the obtained finely pulverized powder was determined by ICP measurement method to be 0.1%.
It was 02 ppm. Further, Table 1 shows the magnet properties of the magnet obtained by molding, sintering, and magnetizing in the same manner as in Example 1.
【００２０】実施例３ 微粉砕工程で溶媒の錯形成剤及び還元剤を添加した水に
バブリングを施さない以外は、実施例２と同一の原料粉
末を同一の製造工程で微粉砕粉末化したところ、得られ
た微粉砕粉末中のＲ，Ｆｅ等の不溶性不純物量は、ＩＣ
Ｐ測定法により測定したところ０．０７ｐｐｍであっ
た。さらに実施例１と同様方法で、成形、焼結、磁石化
して得た磁石の磁石特性を表１に示す。Example 3 The same raw material powder as in Example 2 was pulverized in the same production step except that bubbling was not performed on water to which a complexing agent and a reducing agent were added in the pulverization step. The amount of insoluble impurities such as R and Fe in the obtained finely pulverized powder is determined by IC
It was 0.07 ppm when measured by the P measurement method. Further, Table 1 shows the magnet properties of the magnet obtained by molding, sintering, and magnetizing in the same manner as in Example 1.
【００２１】比較例１ 微粉砕工程で溶媒の水に還元剤を添加しない以外は、実
施例１と同一の原料粉末を同一の製造工程で微粉砕粉末
化したところ、得られた微粉砕粉末中のＲ，Ｆｅ等の不
溶性不純物量は、ＩＣＰ測定法により測定したところ
０．０８ｐｐｍであった。さらに実施例１と同様方法
で、成形、焼結、磁石化して得た磁石の磁石特性を表１
に示す。Comparative Example 1 The same raw material powder as in Example 1 was pulverized in the same production process except that the reducing agent was not added to the solvent water in the pulverization step. The amount of insoluble impurities such as R, Fe and the like was 0.08 ppm as measured by an ICP measurement method. Table 1 shows the magnet properties of the magnet obtained by molding, sintering, and magnetizing in the same manner as in Example 1.
Shown in
【００２２】比較例２ 微粉砕工程で溶媒の水に錯形成剤及び還元剤を添加しな
い以外は、実施例１と同一の原料粉末を同一の製造工程
で微粉砕粉末化したところ、得られた微粉砕粉末中の
Ｒ，Ｆｅ等の不溶性不純物量は、ＩＣＰ測定法により測
定したところ５０００ｐｐｍであった。さらに実施例１
と同様方法で、成形、焼結、磁石化して得た磁石の磁石
特性を表１に示す。Comparative Example 2 The same raw material powder as in Example 1 was pulverized into powder by the same production process except that the complexing agent and the reducing agent were not added to the solvent water in the pulverization process. The amount of insoluble impurities such as R and Fe in the finely pulverized powder was 5000 ppm as measured by an ICP measurement method. Example 1
Table 1 shows the magnet properties of the magnets obtained by molding, sintering, and magnetizing in the same manner as described above.
【００２３】比較例３ 微粉砕工程で溶媒の水に代えて有機溶媒としてシクロヘ
キサンを用いる以外は、実施例１と同一の原料粉末を同
一の製造工程で微粉砕粉末化したところ、得られた微粉
砕粉末中のＲ，Ｆｅ等の不溶性不純物量は、ＩＣＰ測定
法により測定したところ３．０ｐｐｍであった。さらに
実施例１と同様方法で、成形、焼結、磁石化して得た磁
石の磁石特性を表１に示す。Comparative Example 3 The same raw material powder as in Example 1 was pulverized in the same production process except that cyclohexane was used as an organic solvent in place of water as the solvent in the pulverization process. The amount of insoluble impurities such as R and Fe in the pulverized powder was 3.0 ppm as measured by an ICP measurement method. Further, Table 1 shows the magnet properties of the magnet obtained by molding, sintering, and magnetizing in the same manner as in Example 1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】この発明は、特定量の錯形成剤と還元剤
を添加した水、あるいはさらに不活性ガスをバブリング
した水を溶媒にして湿式微粉砕するため、従来の有機溶
媒を用いた微粉砕法に対し、安全性が高く、且つ低コス
トで磁石特性も従来の有機溶媒を用いた場合の磁石と同
等以上の磁石特性の希土類磁石が得られた。According to the present invention, the wet pulverization is carried out using water to which a specific amount of a complexing agent and a reducing agent are added, or water in which an inert gas is bubbled, and thus a conventional fine powder using an organic solvent is used. Compared with the pulverization method, a rare-earth magnet having high safety, low cost, and magnet properties equal to or better than those of a magnet using a conventional organic solvent was obtained.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01F 1/06 B02C 23/06 B22F 9/04 C22C 38/00 303 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) H01F 1/06 B02C 23/06 B22F 9/04 C22C 38/00 303
Claims (2)
Ｒ−Ｆｅ−Ｂ系磁石等の希土類磁石粉末を得る希土類磁
石の製造方法において、錯形成剤を０．００１〜１ｍｏ
ｌ／ｌ及び還元剤として１０ｇ／ｌ以下のＮａ2ＳＯ3を
添加した水を溶媒に用いて湿式微粉砕し、微粉砕後の濾
過分離した粉末中の不溶性不純物量を０．１ｐｐｍ以下
にすることを特徴とする希土類磁石の製造方法。1. A method for producing a rare earth magnet for obtaining a rare earth magnet powder such as an R—Co magnet or an R—Fe—B magnet by wet pulverization.
Wet pulverization using l / l and water to which 10 g / l or less of Na 2 SO 3 as a reducing agent is added as a solvent to reduce the amount of insoluble impurities in the powder separated by filtration after the pulverization to 0.1 ppm or less. A method for producing a rare earth magnet, comprising:
Ｒ−Ｆｅ−Ｂ系磁石等の希土類磁石粉末を得る希土類磁
石の製造方法において、錯形成剤を０．００１〜１ｍｏ
ｌ／ｌ及び還元剤として１０ｇ／ｌ以下のＮａ2ＳＯ3を
添加し、かつ前記水中に不活性ガスを噴射して水中のＯ
2量を１ｐｐｍ以下に低減した水を溶媒に用いて湿式微
粉砕し、微粉砕後の濾過分離した粉末中の不溶性不純物
量を０．１ｐｐｍ以下にすることを特徴とする希土類磁
石の製造方法。2. A method for producing a rare earth magnet which obtains a rare earth magnet powder such as an R—Co magnet or an R—Fe—B magnet by wet pulverization.
l / l and 10 g / l or less of Na 2 SO 3 as a reducing agent are added, and an inert gas is injected into the water to reduce O 2 in the water.
2. A method for producing a rare-earth magnet, comprising: wet-pulverizing water, the amount of which has been reduced to 1 ppm or less, as a solvent, and reducing the amount of insoluble impurities in the finely-pulverized and filtered powder to 0.1 ppm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3208659A JP3029711B2 (en) | 1991-07-24 | 1991-07-24 | Rare earth magnet manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3208659A JP3029711B2 (en) | 1991-07-24 | 1991-07-24 | Rare earth magnet manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06251915A JPH06251915A (en) | 1994-09-09 |
| JP3029711B2 true JP3029711B2 (en) | 2000-04-04 |
Family
ID=16559921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3208659A Expired - Lifetime JP3029711B2 (en) | 1991-07-24 | 1991-07-24 | Rare earth magnet manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3029711B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0419935Y2 (en) * | 1987-07-02 | 1992-05-07 |
-
1991
- 1991-07-24 JP JP3208659A patent/JP3029711B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06251915A (en) | 1994-09-09 |
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