JPH06251915A - Manufacture of rare earth element magnet - Google Patents
Manufacture of rare earth element magnetInfo
- Publication number
- JPH06251915A JPH06251915A JP3208659A JP20865991A JPH06251915A JP H06251915 A JPH06251915 A JP H06251915A JP 3208659 A JP3208659 A JP 3208659A JP 20865991 A JP20865991 A JP 20865991A JP H06251915 A JPH06251915 A JP H06251915A
- Authority
- JP
- Japan
- Prior art keywords
- water
- magnet
- solvent
- rare earth
- ppm
- 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.)
- Granted
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
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Hard Magnetic Materials (AREA)
- Disintegrating Or Milling (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
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 rare earth magnets, such as R-Co magnets or R-Fe-B magnets, by wet pulverization without using a toxic organic solvent. Therefore, when wet pulverizing 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 finely pulverized powder to 0.1 ppm or less. The present invention relates to a method for manufacturing a rare earth magnet that prevents deterioration and corrosion of magnet characteristics.
【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 magnet powder used for producing an R--Co magnet, a raw material powder has been obtained by a Ca reduction method or a pulverization method. Further, the magnet powder used for the production of rare earth magnets such as R-Fe-B magnets is prepared by melting and casting a rare earth raw material reduced by electrolysis into a mold to prepare an alloy lump of a required magnet composition. There is a melting and pulverizing method (JP-A-60-63304 and JP-A-60-1190701) for pulverizing the powder into alloy powder having a required particle size. In this melting and pulverizing method, crushing capable of easily preventing oxidation can be carried out in the coarse crushing step of the ingot, 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。In order to obtain the required particle size, all the magnet powders for rare earth magnets are roughly pulverized by mechanical pulverization, and then an organic solvent such as toluene, methanol or hexane is used,
Wet pulverization is generally performed 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Since the organic solvent used for the wet pulverization is toxic and highly dangerous and has a problem of pollution, a wet pulverization method using water as a solvent has recently been proposed. However, using 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, the amount of O 2 contained in water is generally 10 ppm to
Since it contains 20 ppm, when water is used as a solvent at the time of fine pulverization to apply to the production of rare earth magnets, particularly Nd-Fe-B magnets, the finely pulverized powder produced is corroded by O 2 in the solvent water. And Nd (OH) 3 , in the solvent water,
There is a problem that insoluble impurities such as FeOOH are generated, which causes deterioration and corrosion of the magnetic properties of the permanent magnet obtained from this finely pulverized powder, making it difficult to put into practical use.
【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 is an R-Co type magnet or an R-Co type magnet.
For the purpose of providing a method for producing a rare earth magnet in which a rare earth magnet powder such as an Fe-B magnet is produced by wet fine pulverization without using a toxic organic solvent, it is permanent when wet finely pulverized using water as a 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 characteristics of the magnet and the amount of impurities that cause corrosion.
【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 the fine pulverization step during the production of a rare earth magnet, the amount of O 2 contained in the water is reduced and the precipitation of insoluble impurities in the solution is generated. As a result of various investigations to prevent the formation of insoluble precipitates of Fe and R (especially Nd), which are eluted in the solution as a result of the reduction of the O 2 content in water, water was used as a solvent. By adding an amount of a complexing agent and a reducing agent, or by bubbling by blowing an inert gas into the water, the amount of O 2 contained in water in the solvent is reduced and the insoluble precipitate is dissolved in the solution. When collecting finely pulverized powder by filtration after fine pulverization,
It has been completed by discovering 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。That is, according to the present invention, R
In a method for producing a rare earth magnet, which obtains rare earth magnet powder such as —Co magnet or R—Fe—B magnet, 0.001 to 1 mol / l of a complexing agent and 10 g / l of a reducing agent are used.
1 or less of water to which Na 2 SO 3 was added, or water in which the amount of O 2 in water was reduced to 1 ppm or less by further injecting an inert gas into the water was used as a solvent for wet pulverization, and after pulverization, 0.1 ppm of insoluble impurities in the powder separated by filtration
The method for producing a rare earth magnet is characterized by the following.
【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。In detail, according to the present invention, a complexing agent is added to water as a solvent in an amount of 0.0
01 to 1 mol / l, 10 g / l or less N as a reducing agent
a 2 SO 3 is added, or further Ar gas or N 2 is added.
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-milled with the treated water as a solvent is 0.1 ppm or less By this, impurities can be removed from the system as a filtrate during filtration after fine pulverization, and the amount of insoluble impurities in the powder separated by filtration can be reduced to 0.1 ppm or less. Greatly effective in preventing deterioration and corrosion.
【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 is
Neutral or alkaline water is preferred. As alkaline water, concentrated ammonia is 300 ml / l or less, Na
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 and the like. Also, by using alkaline water as a solvent,
Elution of Nd, Fe, etc. can be reduced compared to acidic and neutral solutions,
It is possible to prevent deterioration of magnet characteristics due to corrosion of the raw material powder and to improve and improve 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. As tap water, the conductivity is 200 μs / cm · 25 ° C. or less, the impurities are 40 ppm or less, Si 15 ppm or less, and Ca.
40 ppm or less and Mg 10 ppm or less are preferable, and the electric conductivity is 1 μs / c by treatment such as ion exchange and distillation.
It is better to lower the temperature to 25 m 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 added to water, which is a feature of the present invention, may be either a carboxylic acid type ligand or an amine type ligand which forms a complex with the constituent elements of the raw material powder, but the carboxylic acid type coordination As the child, succinic acid, maleic acid and the like are preferable, and as the amine-based ligand, EDTA, DTPA and the like are preferable. The amount of complexing agent added is 0.0 with respect to 1 liter of water.
01 to 1 mol is preferable, and the amount of complexing agent is 0.001 m
If it is less than ol / l, complex formation is not sufficient, and if it exceeds 1 mol / l, there is no problem in terms of effect but it is not economically preferable.
【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 10 g / l or less together with the addition of a complexing agent. Unfavorable.
【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 in water of a solvent containing a complexing agent and a reducing agent is added before wet pulverization.
By injecting 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 finely pulverized powder obtained 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, as the bubbling conditions using an inert gas such as Ar gas and N 2 gas, gas pressure is 1.0 to 3.0 kg / cm 2 , and blowing time is 10 minutes to 6
A gas flow rate of 3 to 20 l / min for 0 minutes is preferable. If the gas pressure is less than 1.0 kg / cm 2 , sufficient gas cannot be introduced, and if it exceeds 3.0 kg / cm 2 , water is scattered, which is not preferable. Further, if the blowing time is less than 10 minutes, the removal of O 2 is insufficient, and if it exceeds 60 minutes, it is not economical. Further, if the gas flow rate is less than 3 l / min, sufficient O 2 cannot be removed, and if it exceeds 20 l / min, it is economically undesirable.
【００１６】[0016]
実施例１ 溶解・粉砕法により得られた３５．５ａｔ％Ｎｄ−６
３．４ａｔ％Ｆｅ−１．１ａｔ％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。Example 1 35.5 at% Nd-6 obtained by the melting and pulverizing method
A raw material powder for magnets having a composition of 3.4 at% Fe-1.1 at% B was put into an attritor having an internal volume of 100 l together with a steel ball having a diameter of 12 mm, and further tartaric acid was 0.02 ml / l as a complexing agent and a reducing agent. Of Na 2 SO 3 of 5 g / l and O 2 content of 1.3 ppm was used as a required amount of solvent, and this was pulverized by rotating at a rotation speed of 80 rpm for 3 hours, and filtered after pulverization was completed. A finely pulverized powder having an average particle size of 3.4 μm was obtained. The amount of insoluble impurities such as R and Fe in the obtained finely pulverized powder was 0.03 ppm when measured by the ICP measuring 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 was charged into a mold, oriented in a magnetic field of about 10 kOe, and about 1.
Molded at a pressure of 5 ton / cm 2 , 15 mm x 20 m
A m × 8 mm molded body was prepared. This molded body is 1100
Sintering in Ar atmosphere for 2 hours at ℃, followed by 6
Aging treatment was performed at 00 ° C for 2 hours. Table 1 shows the magnetic properties of the obtained test piece magnets.
【００１８】実施例２ 溶解・粉砕法により得られた３５．５ａｔ％Ｎｄ−６
３．４ａｔ％Ｆｅ−１．２ａｔ％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１２ｐｐｍから０．５ｐｐｍに低減してあ
る。Example 2 35.5 at% Nd-6 obtained by the melting and pulverizing method
A magnet raw material powder having a composition of 3.4 at% Fe-1.2 at% B was placed in an attritor having an internal volume of 100 l together with a steel ball having a diameter of 9.5 mm, and water containing a complexing agent and a reducing agent was further added. Used as a required amount of solvent
Fine pulverization was carried out by rotating at 3 rpm for 3 hours, and after pulverization was completed, filtration was performed to obtain fine pulverized powder having an average particle size of 3.4 μm. The solvent water is tartaric acid 0.02 ml / l, DT in advance.
PA 0.02 ml / l and Na 2 SO 3 2 g / l were added, and the pH was adjusted to 11 with NaOH.
r gas at a gas pressure of 2.0 kg / cm 2 and a gas flow rate of 5 l /
Bubbling under the condition of min and blowing time of 1 hour,
The O 2 content is reduced from 12 ppm to 0.5 ppm.
【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 and Fe in the obtained finely pulverized powder was 0.
It was 02 ppm. Further, in the same manner as in Example 1, the magnet characteristics of the magnet obtained by molding, sintering and magnetizing are shown in Table 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 finely pulverized into powder in the same production process except that water containing a solvent complexing agent and a reducing agent was not bubbled in the fine pulverization process. The amount of insoluble impurities such as R and Fe in the obtained finely pulverized powder is
It was 0.07 ppm when measured by the P measuring method. Further, in the same manner as in Example 1, the magnet characteristics of the magnet obtained by molding, sintering and magnetizing are shown in Table 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 into powder in the same production process except that the reducing agent was not added to the solvent water in the fine pulverization step. The amount of insoluble impurities such as R and Fe was 0.08 ppm when measured by the ICP measuring method. Further, in the same manner as in Example 1, the magnet characteristics of the magnet obtained by molding, sintering and magnetizing are shown in Table 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 and powdered in the same manufacturing process except that the complexing agent and the reducing agent were not added to the solvent water in the pulverizing process. The amount of insoluble impurities such as R and Fe in the finely pulverized powder was 5000 ppm as measured by the ICP measuring method. Further Example 1
Table 1 shows the magnetic properties of the magnets obtained by molding, sintering, and magnetizing in the same manner as in.
【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 finely pulverized and powdered in the same manufacturing process except that cyclohexane was used as the organic solvent in place of water as the solvent in the finely pulverizing step. The amount of insoluble impurities such as R and Fe in the ground powder was 3.0 ppm as measured by the ICP measuring method. Further, in the same manner as in Example 1, the magnet characteristics of the magnet obtained by molding, sintering and magnetizing are shown in Table 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。INDUSTRIAL APPLICABILITY According to the present invention, water containing a specific amount of a complex-forming agent and a reducing agent added thereto, or water bubbling with an inert gas is used as a solvent for wet pulverization. As compared with the pulverization method, it was possible to obtain a rare earth magnet having high safety, low cost, and magnet characteristics equal to or higher than those of magnets using a conventional organic solvent.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成３年７月３１日[Submission date] July 31, 1991
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の詳細な説明[Name of item to be amended] Detailed explanation of the invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【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, containing 5 g / l of reducing agent Na 2 SO 3 and using O 2 content of 1.3 ppm as a required amount of water as a solvent, and rotating this at a rotation speed of 80 rpm for 3 hours to carry out fine pulverization to complete pulverization. After that, it 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 when measured by the ICP measuring method.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の詳細な説明[Name of item to be amended] Detailed explanation of the invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【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Ｏ2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 Use the contained water as a required amount of solvent,
Fine pulverization was carried out by rotating at 3 rpm for 3 hours, and after pulverization was completed, filtration was performed to obtain fine pulverized powder having an average particle size of 3.4 μm. The solvent water is tartaric acid 0.02 ml / l, DT in advance.
PA 0.02 ml / l and Na 2 SO 3 2 g / l were added, and the pH was adjusted to 11 with NaOH.
r gas at a gas pressure of 2.0 kg / cm 2 and a gas flow rate of 5 l /
Bubbling under the condition of min and blowing time of 1 hour,
The O 2 content was reduced to 0.5 ppm. Solvent water containing O 2
The content was 12 ppm when not added .
【手続補正書】[Procedure amendment]
【提出日】平成６年５月１７日[Submission date] May 17, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１６[Correction target item name] 0016
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【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, containing 5 g / l of reducing agent Na 2 SO 3 and using O 2 content of 1.3 ppm as a required amount of water as a solvent, and rotating this at a rotation speed of 80 rpm for 3 hours to carry out fine pulverization to complete pulverization. After that, it 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 when measured by the ICP measuring method.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【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Ｏ2 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 Use the contained water as a required amount of solvent,
Fine pulverization was carried out by rotating at 3 rpm for 3 hours, and after pulverization was completed, filtration was performed to obtain fine pulverized powder having an average particle size of 3.4 μm. The solvent water is tartaric acid 0.02 ml / l, DT in advance.
PA 0.02 ml / l and Na 2 SO 3 2 g / l were added, and the pH was adjusted to 11 with NaOH.
r gas at a gas pressure of 2.0 kg / cm 2 and a gas flow rate of 5 l /
Bubbling under the condition of min and blowing time of 1 hour,
The O 2 content was reduced to 0.5 ppm. Solvent water containing O 2
The content was 12 ppm when not added .
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, which comprises obtaining a rare earth magnet powder such as an R—Co based magnet or an R—Fe—B based magnet by wet pulverization, wherein 0.001 to 1 mo of a complexing agent is used.
1 / l and water containing 10 g / l or less of Na 2 SO 3 as a reducing agent are used as a solvent for wet pulverization, and the amount of insoluble impurities in the powder separated by filtration after pulverization is adjusted to 0.1 ppm or less. A method for manufacturing a rare earth magnet, which is characterized by the above.
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 such as an R—Co based magnet or an R—Fe—B based magnet, which is obtained by wet pulverization, in a method for producing a rare earth magnet, wherein a complexing agent is added in an amount of 0.001 to 1 mo.
1 / l and 10 g / l or less of Na 2 SO 3 as a reducing agent were added, and an inert gas was injected into the water to produce O in water.
2. A method for producing a rare earth magnet, characterized in that the amount of insoluble impurities in the powder separated by filtration after wet pulverization is adjusted to 0.1 ppm or less by wet pulverization using water whose amount is reduced to 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 true JPH06251915A (en) | 1994-09-09 |
| JP3029711B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3820263A1 (en) * | 1987-07-02 | 1989-01-12 | Yazaki Corp | LEAD PROTECTOR AND LOCKING DEVICE THEREFOR |
-
1991
- 1991-07-24 JP JP3208659A patent/JP3029711B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3820263A1 (en) * | 1987-07-02 | 1989-01-12 | Yazaki Corp | LEAD PROTECTOR AND LOCKING DEVICE THEREFOR |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3029711B2 (en) | 2000-04-04 |
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