JPH0718366A - Production of r-fe-b permanent magnet material - Google Patents
Production of r-fe-b permanent magnet materialInfo
- Publication number
- JPH0718366A JPH0718366A JP19288693A JP19288693A JPH0718366A JP H0718366 A JPH0718366 A JP H0718366A JP 19288693 A JP19288693 A JP 19288693A JP 19288693 A JP19288693 A JP 19288693A JP H0718366 A JPH0718366 A JP H0718366A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- permanent magnet
- magnetic field
- treatment
- powder
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、Ｒ（但しＲはＹを含
む希土類元素のうち、少なくとも１種を含有）、Ｆｅ、
Ｂを主成分とする永久磁石材料の製造方法に係り、Ｒ、
Ｆｅ、Ｂを主成分とする合金溶湯を単ロール法あるいは
双ロール法等のストリップキャスティング法にて特定板
厚のＲリッチ相が微細に分離した均質組織を有する鋳片
を得、これをＲ含有Ｆｅ合金のＨ2吸蔵性を利用して鋳
片を自然崩壊させ、さらに脱Ｈ2処理して安定化させ
て、効率よい微粉砕を可能にし、微粉末にパルス磁界を
かけて配向させた後、成形して焼結することにより、磁
石特性の１つである最大エネルギー積値（ＢＨ）ｍａｘ
（ＭＧＯｅ）；Ａと保磁力ｉＨｃ（ｋＯｅ）の特性値；
Ｂの合計値Ａ＋Ｂが５９以上の値を示す高性能Ｒ−Ｆｅ
−Ｂ系永久磁石を得る製造方法に関する。The present invention relates to R (provided that R contains at least one rare earth element including Y), Fe,
A method for manufacturing a permanent magnet material containing B as a main component,
A molten alloy containing Fe and B as a main component is obtained by a strip casting method such as a single roll method or a twin roll method to obtain a slab having a homogeneous structure in which an R-rich phase having a specific plate thickness is finely separated, and containing the R content. After the slab is naturally disintegrated by utilizing the H 2 occlusion property of the Fe alloy and further stabilized by de-H 2 treatment, efficient pulverization is enabled, and fine powder is oriented by applying a pulse magnetic field. , The maximum energy product value (BH) max which is one of the magnet characteristics by molding and sintering
(MGOe); A and coercive force iHc (kOe) characteristic value;
High-performance R-Fe showing a total value A + B of B of 59 or more
-A manufacturing method for obtaining a B-based permanent magnet.
【０００２】[0002]
【従来の技術】今日、高性能永久磁石として代表的なＲ
−Ｆｅ−Ｂ系永久磁石（特開昭５９−４６００８号）
は、三元系正方晶化合物の主相とＲリッチ相を有する組
織にて高い磁石特性が得られ、一般家庭の各種電器製品
から大型コンピュータの周辺機器まで幅広い分野で使用
され、用途に応じた種々の磁石特性を発揮するよう種々
の組成のＲ−Ｆｅ−Ｂ系永久磁石が提案されている。し
かしながら、電気・電子機器の小型・軽量化ならびに高
機能化の要求は強く、Ｒ−Ｆｅ−Ｂ系永久磁石のより一
層の高性能化とコストダウンが要求されている。2. Description of the Related Art Today, R is a typical high-performance permanent magnet.
-Fe-B system permanent magnet (JP-A-59-46008)
Has high magnet characteristics due to the structure of the ternary tetragonal compound having the main phase and the R-rich phase, and is used in a wide range of fields from various household electrical appliances to large computer peripherals, depending on the application. R-Fe-B based permanent magnets of various compositions have been proposed so as to exhibit various magnet characteristics. However, there are strong demands for smaller and lighter electric and electronic devices and for higher functionality, and further higher performance and cost reduction of R-Fe-B based permanent magnets are required.
【０００３】Ｒ−Ｆｅ−Ｂ系焼結磁石の残留磁束密度
（Ｂｒ）を高めるためには、１）強磁性相であり、主相
のＲ2Ｆｅ14Ｂ相の存在量を多くすること、２）焼結体
の密度を主相の理論密度まで高めること、３）さらに主
相結晶粒の、磁化容易軸方向の配向度を高めることが要
求される。すなわち、前記１）項の達成のためには、磁
石の組成を上記Ｒ2Ｆｅ14Ｂの化学量論的組成に近づけ
ることが重要であるが、上記組成の合金を溶解し、鋳型
に鋳造した合金塊を、出発原料としてＲ−Ｆｅ−Ｂ系焼
結磁石を作製しようとすると、合金塊に晶出したα−Ｆ
ｅや、Ｒ−ｒｉｃｈ相が局部的に遍在していることなど
から、特に微粉砕時に粉砕が困難となり、組成ずれを生
ずる等の問題があった。詳述すると、前記合金塊をＨ2
吸蔵、脱Ｈ2処理して機械的微粉砕をおこなう場合（特
開昭６０−６３３０４号、特開昭６３−３３５０５
号）、合金塊に晶出したα−Ｆｅはそのまま粉砕時に残
留し、その展延性の性質のために粉砕を妨げ、又局部的
に遍在したＲ−ｒｉｃｈ相はＨ2吸蔵処理によって、水
素化物を生成し、微細な粉末となるため、機械的な微粉
砕時に酸化が促進されたり、またジェットミルを用いた
粉砕では優生的に飛散することにより組成ずれを生ず
る。In order to increase the residual magnetic flux density (Br) of the R-Fe-B system sintered magnet, 1) increase the abundance of the R 2 Fe 14 B phase, which is a ferromagnetic phase and is the main phase, 2) It is required to increase the density of the sintered body to the theoretical density of the main phase, and 3) to further increase the degree of orientation of the main phase crystal grains in the easy axis direction of magnetization. That is, in order to achieve the above item 1), it is important to bring the composition of the magnet close to the stoichiometric composition of R 2 Fe 14 B, but the alloy having the above composition is melted and cast into a mold. When an alloy mass was used as a starting material to produce an R-Fe-B system sintered magnet, α-F crystallized in the alloy mass was produced.
Since e and the R-rich phase are locally ubiquitous, there is a problem that pulverization becomes difficult especially during fine pulverization and compositional deviation occurs. More specifically, the alloy ingot is treated with H 2
In the case of occluding and dehydrogenating H 2 and performing mechanical pulverization (Japanese Patent Laid-Open No. 63-63304, Japanese Patent Laid-Open No. 63-33505)
No.), α-Fe crystallized in the alloy lump remains as it is at the time of crushing, and because of its spreadability, it hinders crushing, and the locally ubiquitous R-rich phase is hydrogenated by H 2 occlusion treatment. Compounds are formed into fine powders, so that oxidation is promoted during mechanical fine pulverization, and in the pulverization using a jet mill, compositional deviation occurs due to euphoric scattering.
【０００４】また、前記１）項の達成のためＲ2Ｆｅ14
Ｂの化学量論的組成に近づけた合金粉末を用いて焼結体
を作製しようとすると、焼結体の作製工程において不可
避な酸化により、液相焼結を引き起こすためのＮｄ−ｒ
ｉｃｈ相が酸化物を生成するため消費されて焼結できな
かったり、上記Ｒ2Ｆｅ14Ｂ相の存在量を増加によって
必然的に、Ｎｄ−ｒｉｃｈ相やＢ−ｒｉｃｈ相の存在量
が減少するので、焼結体の製造をより一層困難なものに
していた。さらに、前記３）項については、通常Ｒ−Ｆ
ｅ−Ｂ系永久磁石の製造方法において、主相結晶粒の磁
化容易軸方向を揃えるために、磁界中でプレス成形する
方法が採用されている。その際、磁界の印加方向とプレ
ス加圧する方向とによって、残留磁束密度（Ｂｒ）値が
変化したり、また、印加磁界の強度によっても影響を受
けることが知られている。In order to achieve the above item 1), R 2 Fe 14
When an attempt is made to produce a sintered body by using an alloy powder having a stoichiometric composition of B, Nd-r for causing liquid phase sintering due to unavoidable oxidation in the production process of the sintered body.
The ich phase is consumed because it forms an oxide and cannot be sintered, or the abundance of the R 2 Fe 14 B phase is increased, which inevitably reduces the abundance of the Nd-rich phase and the B-rich phase. Therefore, the production of the sintered body has been made more difficult. Further, regarding the above item 3), the normal R-F
In the manufacturing method of the e-B permanent magnet, a method of press molding in a magnetic field is adopted in order to align the easy-axis directions of the main phase crystal grains. At that time, it is known that the residual magnetic flux density (Br) value changes depending on the direction in which the magnetic field is applied and the direction in which the press is applied, and is also influenced by the strength of the applied magnetic field.
【０００５】[0005]
【発明が解決しようとする課題】最近、鋳塊粉砕法によ
るＲ−Ｆｅ−Ｂ系合金粉末の欠点たる結晶粒の粗大化、
α−Ｆｅの残留、偏析を防止するために、Ｒ−Ｆｅ−Ｂ
系合金溶湯を双ロール法により、特定板の鋳片となし、
前記鋳片を通常の粉末冶金法に従って、鋳片をスタンン
プミル・ジョークラッシャーなどで粗粉砕後、さらにデ
ィスクミル、ボールミル、アトライター、ジェットミル
など機械的粉砕法により平均粒径が３〜５μｍの粉末に
微粉砕後、磁場中プレス、焼結時効処理する製造方法が
提案（特開昭６３−３１７６４３号公報）されている。
しかし、前記方法では従来の鋳型に鋳造した鋳塊粉砕法
の場合に比し、微粉砕時の粉砕能率の飛躍的な向上は望
めず、また微粉砕時、粒界粉砕のみならず、粒内粉砕も
起こるため、磁気特性の大幅の向上も達成できなかっ
た。また、Ｒ−ｒｉｃｈ相が酸化に対して安定なＲＨ2
になっていないため、さらにＲ−ｒｉｃｈ相の微細で表
面積が大きいために耐酸化性に劣り、工程中に酸化が進
み高磁石特性が得られない。また、Ｒ−Ｆｅ−Ｂ系永久
磁石材料に対するコストダウンの要求が強く、効率よく
高性能永久磁石を製造することが、極めて重要になって
いる。このため、極限に近い特性を引き出すための製造
条件の改良が必要となっている。Recently, coarsening of crystal grains, which is a defect of the R-Fe-B alloy powder by the ingot crushing method,
In order to prevent α-Fe from remaining and segregating, R-Fe-B
The molten alloy is made into a slab of a specific plate by the twin roll method,
The slab is roughly pulverized by a standard powder metallurgy method with a stamp mill, jaw crusher, etc., and then mechanically pulverized with a disc mill, a ball mill, an attritor, a jet mill or the like to obtain a powder having an average particle size of 3 to 5 μm. In Japanese Patent Application Laid-Open No. 63-317643, there is proposed a manufacturing method in which after pulverization, pressing in a magnetic field and sintering aging treatment are performed.
However, in the above method, as compared with the case of the ingot crushing method of casting in a conventional mold, it is not possible to expect a dramatic improvement in the pulverization efficiency during fine pulverization, and during fine pulverization, not only grain boundary pulverization but also intragranular Since crushing also occurs, it was not possible to achieve a significant improvement in magnetic properties. In addition, the R-rich phase is RH 2 which is stable against oxidation.
In addition, since the R-rich phase is fine and has a large surface area, the oxidation resistance is poor, and oxidation progresses during the process, and high magnet characteristics cannot be obtained. Further, there is a strong demand for cost reduction of R-Fe-B based permanent magnet materials, and it has become extremely important to efficiently produce high-performance permanent magnets. Therefore, it is necessary to improve the manufacturing conditions to bring out the characteristics that are close to the limit.
【０００６】この発明は、上述したＲ−Ｆｅ−Ｂ系永久
磁石材料の製造方法における問題点を解消し、効率よい
微粉砕を可能にし、かつ耐酸化性に優れ、しかも磁石の
結晶粒の微細化により高いｉＨｃを発現し、さらに各結
晶粒の磁化容易方向の配向度を高めて、（ＢＨ）ｍａｘ
値（ＭＧＯｅ）；Ａと、ｉＨｃ値（ｋＯｅ）；Ｂの合計
値、Ａ＋Ｂ≧５９の値を示す高性能Ｒ−Ｆｅ−Ｂ系永久
磁石材料の製造方法の提供を目的としている。The present invention solves the above-mentioned problems in the method for producing an R-Fe-B system permanent magnet material, enables efficient fine pulverization, is excellent in oxidation resistance, and has fine crystal grains of the magnet. By increasing the degree of iHc, and further increasing the degree of orientation of each crystal grain in the easy magnetization direction, (BH) max
The object of the present invention is to provide a method for producing a high-performance R-Fe-B-based permanent magnet material exhibiting a total value (MGOe); A and an iHc value (kOe); B and a value of A + B ≧ 59.
【０００７】[0007]
【課題を解決するための手段】発明者らは、まずＲ−Ｆ
ｅ−Ｂ系合金を出発原料として微粉砕能率の向上、かつ
耐酸化性にすぐれ、磁石合金の磁気特性、特にｉＨｃの
向上を目的に、粉砕方法について種々検討した結果、組
織が微細かつ均等なＲ−Ｆｅ−Ｂ系合金を水素吸蔵させ
た後、脱Ｈ2処理して安定化させた合金粉末を微粉砕し
た場合、微粉砕能は従来の約２倍にも向上し、且つ微粉
末にパルス磁界をかけて配向させた後、成形して焼結す
ることにより、（ＢＨ）ｍａｘ値とｉＨｃ値の合計値が
５９以上の値を有し、かつ焼結磁石のｉＨｃが向上する
ことを知見した。すなわち、ストリップキャスティング
された特定板厚のＲリッチ相が微細に分離した組織を有
する特定組成のＲ−Ｆｅ−Ｂ系合金にＨ2吸蔵させる
と、微細に分散されたＲリッチ相が水素化物を生成して
体積膨張することにより、前記合金を自然崩壊させるこ
とができ、その結果、微粉砕により、合金塊を構成して
いる主相の結晶粒を細分化することが可能となり、粒度
分布が均一な粉末を作製することができる。The inventors of the present invention firstly investigated the R-F.
As a result of various studies on the pulverization method using the e-B alloy as the starting material, the fine pulverization efficiency was improved, the oxidation resistance was excellent, and the magnetic properties of the magnet alloy, particularly iHc, were studied. after the R-Fe-B alloy is a hydrogen absorbing, when finely pulverized alloy powder is stabilized by removing H 2 treatment, milling ability is improved to about twice that of conventional, and a fine powder By orienting by applying a pulsed magnetic field, shaping and sintering, the total value of (BH) max value and iHc value has a value of 59 or more, and iHc of the sintered magnet is improved. I found out. That is, when H 2 is occluded in an R-Fe-B-based alloy having a specific composition having a structure in which the strip-cast R-rich phase having a specific plate thickness is finely separated, the finely dispersed R-rich phase converts a hydride. By generating and expanding the volume, the alloy can be spontaneously collapsed, and as a result, it becomes possible to finely pulverize the crystal grains of the main phase constituting the alloy lump, resulting in a particle size distribution. A uniform powder can be produced.
【０００８】特に、この際Ｒリッチ相が微細に分散さ
れ、しかもＲ2Ｆｅ14Ｂ相が微細であることが重要であ
る。しかも通常の鋳型を用いて合金塊を溶製する方法で
は、合金組成をＲ2Ｆｅ14Ｂの化学量論的組成に近づけ
た場合、Ｆｅ初晶の晶出が避け難く、次工程の微粉砕能
を大きく低下させる要因になってしまう。そのため、合
金塊を均質化させる目的で熱処理を加えて、α−Ｆｅを
消失させる手段がとられるが、主相結晶粒の粗大化と、
Ｒリッチ相の偏析も進むため、焼結磁石のｉＨｃ向上を
図ることが困難となる。また、主相結晶粒の磁化容易軸
方向を揃える、すなわち、配向度を高めることも高Ｂｒ
化を達成するための必須条件である。そのため、粉末冶
金的手法で製造される永久磁石材料、たとえば、ハード
フェライト磁石、Ｓｍ−Ｃｏ磁石ならびにＲ−Ｆｅ−Ｂ
磁石では、その粉末を磁界中でプレスする方式が採られ
ている。In this case, it is particularly important that the R-rich phase is finely dispersed and the R 2 Fe 14 B phase is fine. Moreover, in the method of smelting an alloy ingot by using an ordinary mold, when the alloy composition is brought close to the stoichiometric composition of R 2 Fe 14 B, crystallization of Fe primary crystal is difficult to avoid and fine pulverization in the next step is performed. It becomes a factor that greatly reduces the performance. Therefore, heat treatment is applied for the purpose of homogenizing the alloy ingot, and a means for eliminating α-Fe is taken, but with the coarsening of the main phase crystal grains,
Since segregation of the R-rich phase also progresses, it is difficult to improve the iHc of the sintered magnet. In addition, it is also possible to align the easy magnetization axis directions of the main phase crystal grains, that is, to increase the degree of orientation with high Br
Is an essential condition to achieve Therefore, permanent magnet materials manufactured by powder metallurgical methods, such as hard ferrite magnets, Sm-Co magnets, and R-Fe-B.
The magnet employs a method of pressing the powder in a magnetic field.
【０００９】しかしながら、磁界を発生させるために通
常のプレス装置（油圧プレス、機械プレス）に配置され
ているコイルおよび電源では、高々１０ｋＯｅ〜２０ｋ
Ｏｅの磁界しか発生することしかできず、より高い磁界
を発生させるためには、コイルの巻数を多くする必要が
あり、また高い電源を必要とするための装置の大型化を
必要とする。本発明者らは、プレス時の磁界強度と焼結
体のＢｒとの関係を解析したところ、磁界強度を高くす
ればする程、高Ｂｒ化でき、瞬間的に強磁界を発生させ
ることの可能なパルス磁界を用いることによって、より
一層高Ｂｒ化できることを知見した。さらに、パルス磁
界を用いる方法においては、一旦パルス磁界で瞬間的に
配向させることが重要で、さらに、粉末を静水圧プレス
によって成形することが可能であり、パルス磁界と電磁
石による静磁界との組み合せによって、磁界中プレス成
形することも可能であることを知見した。However, in the coil and the power source arranged in the usual press device (hydraulic press, mechanical press) for generating the magnetic field, at most 10 kOe to 20 k.
Only the magnetic field of Oe can be generated, and in order to generate a higher magnetic field, it is necessary to increase the number of turns of the coil, and it is necessary to increase the size of the device that requires a high power supply. The present inventors analyzed the relationship between the magnetic field strength during pressing and Br of the sintered body, and the higher the magnetic field strength, the higher the Br and the instantaneous generation of a strong magnetic field. It was found that the Br can be further increased by using a different pulse magnetic field. Furthermore, in the method using a pulsed magnetic field, it is important to momentarily orientate once with the pulsed magnetic field, and it is possible to shape the powder by a hydrostatic press, and the combination of the pulsed magnetic field and the static magnetic field by an electromagnet can be combined. It was found that it is also possible to perform press molding in a magnetic field.
【００１０】この発明は、Ｒ（但しＲはＹを含む希土類
元素のうち、少なくとも１種）１０ａｔ％〜３０ａｔ
％、Ｂ２ａｔ％〜２８ａｔ％、残部Ｆｅ（但しＦｅの１
部をＣｏ、Ｎｉの１種または２種にて置換できる）及び
不可避的不純物からなる合金溶湯をストリップキャステ
ィング法にて板厚０．０３ｍｍ〜１０ｍｍの薄板でＲリ
ッチ相が５μｍ以下に微細に分離した組織を有する鋳片
に鋳造後、前記鋳片を吸排気可能な容器に収容し、該容
器内の空気をＨ2ガスにて置換した後、該容器内に２０
０Ｔｏｒｒ〜５０ｋｇ／ｍｍ2のＨ2ガスを供給して得ら
れた崩壊合金粉を脱Ｈ2処理した後、不活性ガス気流中
で微粉砕して得た平均粒径が１〜１０μｍの微粉末をモ
ールド内に充填密度１．４〜３．０ｇ／ｃｍ3に充填
し、瞬間的に１０ｋＯｅ以上のパルス磁界をかけて配向
させた後、成形し、焼結、時効処理することを特徴とす
るＲ−Ｆｅ−Ｂ系永久磁石材料の製造方法である。ま
た、この発明は、上記の構成において、水素吸蔵により
得られた崩壊合金粉末を１００℃〜７５０℃に加熱して
脱Ｈ2処理することを特徴とするＲ−Ｆｅ−Ｂ系永久磁
石材料の製造方法を併せて提案する。According to the present invention, R (where R is at least one of rare earth elements including Y) is 10 at% to 30 at.
%, B2 at% to 28 at%, balance Fe (however, Fe of 1
Part can be replaced with 1 or 2 kinds of Co and Ni) and an alloy melt consisting of unavoidable impurities is finely separated by strip casting method into a thin plate with a plate thickness of 0.03 mm to 10 mm and an R-rich phase of 5 μm or less. After casting into a slab having the above structure, the slab is housed in a container capable of sucking and exhausting air, and the air in the container is replaced with H 2 gas.
After removing H 2 processes the resulting collapse alloy powder by supplying H 2 gas of 0Torr~50kg / mm 2, the fine powder having an average particle size obtained by finely pulverized in an inert gas flow is 1~10μm Is filled in a mold at a packing density of 1.4 to 3.0 g / cm 3 , and is momentarily applied with a pulse magnetic field of 10 kOe or more for orientation, followed by molding, sintering, and aging treatment. It is a method for producing an R-Fe-B based permanent magnet material. Further, the present invention provides an R-Fe-B based permanent magnet material, characterized in that, in the above-mentioned constitution, the collapsed alloy powder obtained by hydrogen absorption is heated to 100 ° C to 750 ° C to perform H 2 removal treatment. A manufacturing method is also proposed.
【００１１】この発明によるＲ−Ｆｅ−Ｂ系永久磁石の
磁気特性は、ＢＨ（ｍａｘ）が５０ＭＧＯｅ以上の場合
は、ｉＨｃは１０ｋＯｅ以上であり、又ＢＨ（ｍａｘ）
が４５ＭＧＯｅ以上の場合は、ｉＨｃは１５ｋＯｅ以上
で、組成、製造条件等を適宜選択することにより所要の
磁気特性を得ることができる。The magnetic characteristics of the R-Fe-B system permanent magnet according to the present invention are such that iHc is 10 kOe or more when BH (max) is 50 MGOe or more, and BH (max).
Is 45 MGOe or more, iHc is 15 kOe or more, and the required magnetic characteristics can be obtained by appropriately selecting the composition, manufacturing conditions and the like.
【００１２】この発明の特定組成のＲリッチ相が微細に
分離した組織を有する磁石材料の鋳片は、特定組成の合
金溶湯を単ロール法、あるいは双ロール法によるストリ
ップキャスティング法にて製造される。得られた鋳片は
板厚が０．０３ｍｍ〜１０ｍｍの薄板材であり、所望の
鋳片板厚により、単ロール法と双ロール法を使い分ける
が、板厚が厚い場合は双ロール法を、また板厚が薄い場
合は単ロール法を採用したほうが好ましい。鋳片の板厚
を０．０３ｍｍ〜１０ｍｍに限定した理由は、０．０３
ｍｍ未満では急冷効果が大となり、結晶粒径が３μｍよ
り小となり、粉末化した際に酸化しやすくなるため、磁
気特性の劣化を招来するので好ましくなく、また１０ｍ
ｍを超えると、冷却速度が遅くなり、α−Ｆｅが晶出し
やすく、結晶粒径が大となり、Ｎｄリッチ相の偏在も生
じるため、磁気特性が低下するので好ましくないことに
よる。The cast slab of the magnetic material having the structure in which the R-rich phase of the specific composition is finely separated according to the present invention is produced by the alloy casting of the specific composition by the strip casting method by the single roll method or the twin roll method. . The obtained slab is a thin plate material having a plate thickness of 0.03 mm to 10 mm, and the single roll method and the twin roll method are used properly depending on the desired slab plate thickness, but when the plate thickness is thick, the twin roll method is used. Further, when the plate thickness is thin, it is preferable to adopt the single roll method. The reason for limiting the plate thickness of the cast slab to 0.03 mm to 10 mm is 0.03
If it is less than 10 mm, the rapid cooling effect becomes large, the crystal grain size becomes smaller than 3 μm, and it becomes easy to oxidize when pulverized, resulting in deterioration of magnetic properties, which is not preferable.
If it exceeds m, the cooling rate becomes slow, α-Fe is likely to crystallize, the crystal grain size becomes large, and the Nd-rich phase is unevenly distributed, which deteriorates the magnetic properties, which is not preferable.
【００１３】この発明のストリップキャスティング法に
より得られた特定組成のＲ−Ｆｅ−Ｂ系合金の断面組織
は主相のＲ2Ｆｅ14Ｂ結晶が従来の鋳型に鋳造して得ら
れた鋳塊のものに比べて、約１／１０以上も微細であ
り、例えば、その短軸方向の寸法は０．１μｍ〜５０μ
ｍ、長軸方向は５μｍ〜２００μｍの微細結晶であり、
かつその主相結晶粒を取り囲むようにＲリッチ相が微細
に分散されており、局部に遍在している領域において
も、その大きさは２０μｍ以下である。Ｒリッチ相が５
μｍ以下に微細に分離することによって、Ｈ2吸蔵処理
時にＲリッチ相が水素化物を生成した際の体積膨張が均
一に発生して細分化されるため、微粉砕にて主相の結晶
粒が細分化されて粒度分布が均一な微粉末が得られる。
前記鋳片はそのままでＨ2吸蔵処理してもよいが、所要
の大きさに破断して、金属面を露出させてＨ2吸蔵処理
したほうが好ましい。The cross-sectional structure of the R-Fe-B type alloy having a specific composition obtained by the strip casting method of the present invention is that of the ingot obtained by casting the main phase R 2 Fe 14 B crystal in a conventional mold. The size is about 1/10 or more finer than that of the one, and for example, the dimension in the minor axis direction is 0.1 μm to 50 μm.
m, the long axis direction is a fine crystal of 5 μm to 200 μm,
In addition, the R-rich phase is finely dispersed so as to surround the main phase crystal grains, and the size is 20 μm or less even in the locally ubiquitous region. R-rich phase is 5
By finely separating to less than μm, volume expansion when the R-rich phase forms a hydride is uniformly generated during the H 2 occlusion treatment, and the R-rich phase is finely divided. A fine powder having a uniform particle size distribution is obtained.
The slab may be subjected to H 2 occlusion treatment as it is, but it is preferable to break it into a desired size and expose the metal surface to perform H 2 occlusion treatment.
【００１４】Ｈ2吸蔵処理には、例えば、所定大きさに
破断した０．０３ｍｍ〜１０ｍｍ厚みの鋳片を原料ケー
ス内に挿入し、上記原料ケースを蓋を締めて密閉できる
容器内に装入して密閉したのち、容器内を十分に真空引
きした後、２００Ｔｏｒｒ〜５０ｋｇ／ｃｍ2の圧力の
Ｈ2ガスを供給して、該鋳片にＨ2を吸蔵させる。このＨ
2吸蔵反応は、発熱反応であるため、容器の外周には冷
却水を供給する冷却配管が周設して容器内の昇温を防止
しながら、所定圧力のＨ2ガスを一定時間供給すること
により、Ｈ2ガスが吸収されて該鋳片は自然崩壊して粉
化する。さらに、粉化した合金を冷却したのち、真空中
で脱Ｈ2ガス処理する。前記処理の合金粉末は粒内に微
細亀裂が内在するので、ポール・ミル、ジェットミル等
で短時間で微粉砕され、１μｍ〜８０μｍの所要粒度の
合金粉末を得ることができる。For H 2 occlusion treatment, for example, a slab of 0.03 mm to 10 mm in thickness, which is broken into a predetermined size, is inserted into a raw material case, and the raw material case is inserted into a container which can be closed by closing a lid. Then, the inside of the container is sufficiently evacuated, and then H 2 gas having a pressure of 200 Torr to 50 kg / cm 2 is supplied to occlude H 2 in the slab. This H
(2) Since the occlusion reaction is an exothermic reaction, a cooling pipe for supplying cooling water is provided around the outer periphery of the container to prevent the temperature inside the container from rising and to supply H 2 gas at a predetermined pressure for a certain period of time. As a result, H 2 gas is absorbed, and the slab is spontaneously disintegrated and pulverized. Further, after cooling the powdered alloy, it is subjected to H 2 degassing treatment in vacuum. Since the alloy powder of the above treatment has fine cracks in the grains, it can be pulverized in a short time by a pole mill, a jet mill or the like to obtain an alloy powder having a required grain size of 1 μm to 80 μm.
【００１５】この発明において、上記処理容器内を予め
不活性ガスで空気を置換し、その後Ｈ2ガスで不活性ガ
スを置換してもよい。また、鋳塊の破断大きさは、小さ
いほど、Ｈ2粉砕の圧力を小さくでき、また、Ｈ2ガス圧
力は、減圧下でも破断した鋳塊はＨ2吸収し粉化される
が、圧力が大気圧より高くなるほど、粉化されやすくな
る。しかし、２００Ｔｏｒｒ未満では粉化性が悪くな
り、５０ｋｇ／ｃｍ2を超えるとＨ2吸収による粉化の点
では好ましいが、装置や作業の安全性からは好ましくな
いため、Ｈ2ガス圧力は２００Ｔｏｒｒ〜５０ｋｇ／ｃ
ｍ2とする。量産性からは、２ｋｇ／ｃｍ2〜１０ｋｇ／
ｃｍ2が好ましい。 この発明において、Ｈ2吸蔵による粉
化の処理時間は、前記密閉容器の大きさ、破断塊の大き
さ、Ｈ2ガス圧力により変動するが、５分以上は必要で
ある。In the present invention, the inside of the processing container is previously
Replace the air with an inert gas, then H2Inert gas
May be replaced. In addition, the fracture size of the ingot is small
How much H2The crushing pressure can be reduced, and H2Gas pressure
The force is H2Absorbed and powdered
However, as the pressure becomes higher than atmospheric pressure, it becomes easier to be pulverized.
It However, if it is less than 200 Torr, the powderability is poor.
50 kg / cm2H is exceeded2Points of pulverization by absorption
However, it is not preferable from the viewpoint of safety of equipment and work.
Because, H2Gas pressure is 200 Torr to 50 kg / c
m2And 2 kg / cm for mass production2-10kg /
cm2Is preferred. In this invention, H2Powder by occlusion
The processing time for liquefaction depends on the size of the closed container and the size of the broken mass.
H2It depends on the gas pressure, but it takes more than 5 minutes
is there.
【００１６】Ｈ2吸蔵により粉化した合金粉末を冷却
後、真空中で１次の脱Ｈ2ガス処理する。さらに、真空
中またはアルゴンガス中において、粉化合金を１００℃
〜７５０℃に加熱し、０．５時間以上の２次脱Ｈ2ガス
処理すると、粉化合金中のＨ2ガスは完全に除去できる
とともに、長期保存に伴う粉末あるいはプレス成形体の
酸化を防止して、得られる永久磁石の磁気特性の低下を
防止できる。この発明による１００℃以上に加熱する脱
水素処理は、すぐれた脱水素効果を有しているために上
記の真空中での１次脱水素処理を省略し、崩壊粉を直接
１００℃以上の真空中またはアルゴンガス雰囲気中で脱
水素処理してもよい。すなわち、前述したＨ2吸蔵反応
用容器内でＨ2吸蔵・崩壊反応させた後、得られた崩壊
粉を続いて同容器の雰囲気中で１００℃以上に加熱する
脱水素処理を行うことができる。あるいは、真空中での
脱水素処理後、処理容器から取り出して崩壊粉を微粉砕
したのち、再度処理容器で１００℃以上に加熱するこの
発明の脱水素処理を施してもよい。上記の脱水素処理に
おける加熱温度は、１００℃未満では崩壊合金粉内に残
存するＨ2を除去するのに長時間を要して量産的でな
い。また、７５０℃を超える温度では液相が出現し、粉
末が固化してしまうため、微粉砕が困難になったり、プ
レス時の成形性を悪化させるので、焼結磁石の製造の場
合には好ましくない。また、焼結磁石の焼結性を考慮す
ると、好ましい脱水素処理温度は２００℃〜６００℃で
ある。また、処理時間は処理量によって変動するが０．
５時間以上は必要である。After cooling the alloy powder pulverized by the H 2 occlusion, the primary H 2 degassing treatment is performed in a vacuum. Further, the powdered alloy is heated to 100 ° C. in vacuum or argon gas.
Was heated to to 750 ° C., preventing the two Tsugida' H 2 gas treatment over 0.5 hours, with H 2 gas in the pulverized alloy can be completely removed, the oxidation of the powder or pressed bodies due to long-term storage As a result, it is possible to prevent deterioration of the magnetic properties of the obtained permanent magnet. Since the dehydrogenation treatment of heating to 100 ° C. or higher according to the present invention has an excellent dehydrogenation effect, the above primary dehydrogenation treatment in vacuum is omitted, and the disintegrated powder is directly vacuumed at 100 ° C. or higher. You may perform a dehydrogenation process inside or in an argon gas atmosphere. That can be done with H 2 After absorption and degradation reactions, dehydrogenation treatment which subsequently resulting collapse powder is heated to above 100 ° C. in an atmosphere of the container in the container for H 2 occlusion reaction described above . Alternatively, after dehydrogenation treatment in a vacuum, the dehydrogenation treatment of the present invention may be carried out in which the disintegrated powder is taken out from the treatment container, finely crushed and then heated to 100 ° C. or higher in the treatment container. If the heating temperature in the above dehydrogenation treatment is less than 100 ° C., it takes a long time to remove H 2 remaining in the disintegrated alloy powder and is not mass-produced. Further, at a temperature of higher than 750 ° C., a liquid phase appears and the powder is solidified, which makes fine pulverization difficult and deteriorates the formability at the time of pressing. Therefore, it is preferable in the case of producing a sintered magnet. Absent. Further, considering the sinterability of the sintered magnet, the preferable dehydrogenation treatment temperature is 200 ° C to 600 ° C. Further, the processing time varies depending on the processing amount, but is 0.
At least 5 hours is required.
【００１７】次に微粉砕には、不活性ガス（例えば、Ｎ
2、Ａｒ）によるジェット・ミルにて微粉砕を行う。勿
論、有機溶媒（例えば、ベンゼンやトルエン等）を用い
たボールミルや、アトライター粉砕を用いることも可能
である。微粉砕での粉末の平均粒度は、１μｍ〜１０μ
ｍが好ましい。１μｍ未満になると粉砕した粉末が極め
て活性となり著しく酸化されやすく、発火等の恐れが生
ずる。また、１０μｍを超えると粉砕されない粗大粒子
が残存し、保磁力が低下したり、焼結の進行が遅く密度
の低下を引き起こすことになる。より好ましくは、２〜
４μｍの平均粒度の微粉末にすることである。Next, for fine pulverization, an inert gas (for example, N 2
2. Fine pulverize with a jet mill using Ar). Of course, it is also possible to use a ball mill using an organic solvent (for example, benzene, toluene, etc.) or attritor grinding. The average particle size of the finely pulverized powder is 1 μm to 10 μm.
m is preferred. If it is less than 1 μm, the pulverized powder becomes extremely active and is prone to be easily oxidized, which may cause ignition. On the other hand, if it exceeds 10 μm, coarse particles that are not crushed will remain, and the coercive force will decrease, or the progress of sintering will be slow, and the density will decrease. More preferably, 2
A fine powder having an average particle size of 4 μm.
【００１８】磁界を用いたプレスには、つぎの方法を提
案する。微粉砕した粉末を不活性ガス雰囲気中でモール
ドに充填する。モールドは、非磁性の金属、酸化物から
作製したもののほか、プラスチックやゴム等の有機化合
物でも良い。粉末の充填密度は、その粉末の静止状態の
嵩密度（充填密度１．４ｇ／ｃｍ3）から、タッピング
後の固め嵩密度（充填密度３．０ｇ／ｃｍ3）の範囲が
好ましい。従って充填密度は１．４〜３．０ｇ／ｃｍ3
に限定する。これを、空心コイル、コンデンサー電源に
よるパルス磁界を加えて粉末の配向を行う。配向の際、
上下パンチを用いて圧縮を行いながら、繰り返し、パル
ス磁界を加えてもよい。パルス磁界の強度は大きければ
大きい程良く、最低１０ｋＯｅ以上は必要とする。パル
ス磁界の時間は、図２の時間と磁界強さのグラフに示す
如く、１μｍｓｅｃ〜１０ｓｅｃが好ましく、さらには
５μｍｓｅｃ〜１００ｍｍｓｅｃが好ましく、パルス磁
界の印加回数は１〜１０回、さらに、好ましくは１〜５
回である。配向後の粉末は、静水圧プレスによって固め
ることができる。この際、可塑性のあるモールドを使用
した場合には、そのまま、静水圧プレスを行うことが可
能である。また、パルス磁界による配向とプレスとを連
続的に行うためには、ダイス内部にパルス磁界を発生さ
せるコイルを埋め込み、パルス磁界を用いて配向させた
後、通常の磁界中プレス方法で成形することも可能であ
る。For pressing using a magnetic field, the following method is proposed. The finely pulverized powder is filled in a mold in an inert gas atmosphere. The mold may be made of non-magnetic metal or oxide, or may be an organic compound such as plastic or rubber. The packing density of the powder is preferably in the range of the bulk density of the powder in a static state (packing density 1.4 g / cm 3 ) to the solidified bulk density after tapping (packing density 3.0 g / cm 3 ). Therefore, the packing density is 1.4 to 3.0 g / cm 3.
Limited to The powder is oriented by applying a pulsed magnetic field from an air-core coil or a condenser power supply. During orientation,
A pulse magnetic field may be repeatedly applied while performing compression using the upper and lower punches. The higher the strength of the pulsed magnetic field, the better, and at least 10 kOe or more is required. The time of the pulse magnetic field is preferably 1 μmsec to 10 sec, more preferably 5 μmsec to 100 mmsec as shown in the graph of time and magnetic field strength in FIG. 2, and the pulse magnetic field is applied 1 to 10 times, more preferably 1 ~ 5
Times. The powder after orientation can be hardened by isostatic pressing. At this time, when a plastic mold is used, the isostatic pressing can be performed as it is. In order to continuously perform the orientation and the pressing by the pulsed magnetic field, a coil for generating the pulsed magnetic field is embedded in the die, the orientation is performed by using the pulsed magnetic field, and then the ordinary magnetic field pressing method is used for molding. Is also possible.
【００１９】以下に、この発明における、希土類・ボロ
ン・鉄系永久磁石合金用鋳塊の組成限定理由を説明す
る。この発明の永久磁石合金用鋳塊に含有される希土類
元素Ｒはイットリウム（Ｙ）を包含し、軽希土類及び重
希土類を包含する希土類元素である。Ｒとしては、軽希
土類をもって足り、特にＮｄ，Ｐｒが好ましい。また通
常Ｒのうち１種もって足りるが、実用上は２種以上の混
合物（ミッシユメタル、ジジム等）を入手上の便宜等の
理由により用いることができ、Ｓｍ，Ｙ，Ｌａ，Ｃｅ，
Ｇｄ等は他のＲ、特にＮｄ，Ｐｒ等との混合物として用
いることができる。なお、このＲは純希土類元素でなく
てもよく、工業上入手可能な範囲で製造上不可避な不純
物を含有するものでも差し支えない。Ｒは、Ｒ−Ｆｅ−
Ｂ系永久磁石を製造する合金鋳塊の必須元素であって、
１０原子％未満では高磁気特性、特に高保磁力が得られ
ず、３０原子％を越えると残留磁束密度（Ｂｒ）が低下
して、すぐれた特性の永久磁石が得られない。よって、
Ｒは１０原子％〜３０原子％の範囲とし、特に好ましい
範囲はＲは１２〜１５ａｔ％である。The reasons for limiting the composition of the ingot for rare earth / boron / iron-based permanent magnet alloy in the present invention will be described below. The rare earth element R contained in the ingot for permanent magnet alloy of the present invention is a rare earth element including yttrium (Y) and including light rare earth and heavy rare earth. As R, a light rare earth element is sufficient, and Nd and Pr are particularly preferable. Usually, one kind of R is sufficient, but in practice, a mixture of two or more kinds (Missille metal, didymium, etc.) can be used for the reason of convenience of acquisition, Sm, Y, La, Ce,
Gd and the like can be used as a mixture with other R, especially Nd and Pr. It should be noted that this R does not have to be a pure rare earth element, and may contain impurities that are unavoidable in production within the industrially available range. R is R-Fe-
Is an essential element of the alloy ingot for producing the B-based permanent magnet,
If it is less than 10 atom%, high magnetic properties, particularly high coercive force, cannot be obtained, and if it exceeds 30 atom%, the residual magnetic flux density (Br) is lowered and a permanent magnet having excellent characteristics cannot be obtained. Therefore,
R is in the range of 10 atom% to 30 atom%, and a particularly preferable range of R is 12 to 15 at%.
【００２０】Ｂは、Ｒ−Ｆｅ−Ｂ系永久磁石を製造する
合金鋳塊の必須元素であって、２原子％未満では高い保
磁力（ｉＨｃ）は得られず、２８％原子を越えると残留
磁束密度（Ｂｒ）が低下するため、すぐれた永久磁石が
得られない。よって、Ｂは２原子％〜２８原子％の範囲
と特に好ましい範囲は４〜８ａｔ％である。B is an essential element of the alloy ingot for producing the R-Fe-B system permanent magnet. If it is less than 2 atom%, a high coercive force (iHc) cannot be obtained, and if it exceeds 28% atom, it remains. Since the magnetic flux density (Br) decreases, an excellent permanent magnet cannot be obtained. Therefore, B is in the range of 2 at% to 28 at% and a particularly preferable range is 4 to 8 at%.
【００２１】Ｆｅは４２原子％未満では残理磁束密度
（Ｂｒ）が低下し、８８原子を超えると高い保磁力が得
られないため、Ｆｅは７７〜８４ａｔ％が好ましく。さ
らに好ましくはＦｅ７７原子％〜８４原子％である。ま
た、Ｆｅの一部をＣｏ、Ｎｉの１種又は２種で置換する
理由は、永久磁石の温度特性を向上させる効果及び耐食
性を向上させる効果が得られるためであるが、Ｃｏ、Ｎ
ｉの１種又は２種はＦｅの５０％を越えると高い保磁力
が得られず、すぐれた永久磁石が得られない。よって、
ＣｏはＦｅの５０％を上限とする。When Fe is less than 42 atomic%, the residual magnetic flux density (Br) is lowered, and when it exceeds 88 atom, a high coercive force cannot be obtained. Therefore, Fe is preferably 77 to 84 at%. More preferably, it is Fe 77 atomic% -84 atomic%. The reason for substituting a part of Fe with one or two of Co and Ni is that the effect of improving the temperature characteristics of the permanent magnet and the effect of improving corrosion resistance can be obtained.
If 1 or 2 of i exceeds 50% of Fe, a high coercive force cannot be obtained, and an excellent permanent magnet cannot be obtained. Therefore,
Co has an upper limit of 50% of Fe.
【００２２】この発明の合金鋳塊において、高い残留磁
束密度と高い保磁力を共に有するすぐれた永久磁石を得
るためには、Ｒ１２原子％〜１５原子％、Ｂ４原子％〜
８原子％、Ｆｅ７７原子％〜８４原子％が好ましい。ま
た、この発明による合金鋳塊は、Ｒ、Ｂ、Ｆｅの他、工
業的生産上不可避的不純物の存在を許容できるが、Ｂの
一部を４．０原子％以下のＣ、３．５原子％以下のＰ、
２．５原子％以下のＳ、３．５原子％以下のＣｕのうち
少なくとも１種、合計量で４．０原子％以下で置換する
ことにより、磁石合金の製造性改善、低価格化が可能で
ある。さらに、前記Ｒ、Ｂ、Ｆｅ合金あるいはＣｏを含
有するＲ−Ｆｅ−Ｂ合金に、９．５原子％以下のＡｌ、
４．５原子％以下のＴｉ、９．５原子％以下のＶ、８．
５原子％以下のＣｒ、８．０原子％以下のＭｎ、５原子
％以下のＢｉ、１２．５原子％以下のＮｂ、１０．５原
子％以下のＴａ、９．５原子％以下のＭｏ、９．５原子
％以下のＷ、２．５原子％以下のＳｂ、７原子％以下の
Ｇｅ、３５原子％以下のＳｎ、５．５原子％以下のＺ
ｒ、５．５原子％以下のＨｆのうち少なくとも１種添加
含有させることにより、永久磁石合金の高保磁力が可能
になる。この発明のＲ−Ｂ−Ｆｅ系永久磁石において、
結晶相は主相が正方晶であることが不可欠であり、特
に、微細で均一な合金粉末を得て、すぐれた磁気特性を
有する焼結永久磁石を作成するのに効果的である。In order to obtain an excellent permanent magnet having both a high residual magnetic flux density and a high coercive force in the alloy ingot of the present invention, R12 atom% to 15 atom% and B4 atom% to
8 atomic% and Fe77 atomic% -84 atomic% are preferable. Further, the alloy ingot according to the present invention can tolerate the presence of impurities unavoidable in industrial production in addition to R, B and Fe, but a part of B is 4.0 atom% or less of C, 3.5 atom or less. % Or less P,
By substituting at least one of S of 2.5 atomic% or less and Cu of 3.5 atomic% or less with a total amount of 4.0 atomic% or less, the manufacturability of the magnet alloy can be improved and the cost can be reduced. Is. Further, in the R, B, Fe alloy or the R-Fe-B alloy containing Co, 9.5 atomic% or less of Al,
4.5 atomic% or less Ti, 9.5 atomic% or less V, 8.
5 atomic% or less Cr, 8.0 atomic% or less Mn, 5 atomic% or less Bi, 12.5 atomic% or less Nb, 10.5 atomic% or less Ta, 9.5 atomic% or less Mo, W of 9.5 atomic% or less, Sb of 2.5 atomic% or less, Ge of 7 atomic% or less, Sn of 35 atomic% or less, Z of 5.5 atomic% or less.
High coercive force of the permanent magnet alloy becomes possible by adding and containing at least one of Hf of r and 5.5 at% or less. In the RB-Fe based permanent magnet of the present invention,
It is essential that the main phase of the crystal phase is a tetragonal crystal, and it is particularly effective for obtaining a fine and uniform alloy powder and producing a sintered permanent magnet having excellent magnetic properties.
【００２３】この発明による合金の微粉砕粉末の粒度
は、平均粒度８０μｍを越えると、永久磁石の作成時に
すぐれた磁気特性、とりわけ高い保磁力が得られず、ま
た、平均粒度が１μｍ未満では、焼結磁石とした場合の
製作工程、すなわち、プレス成形、焼結、時効処理工程
における酸化が著しく、すぐれた磁気特性が得られない
ため、１〜８０μｍの平均粒度とする。さらに、すぐれ
た磁気特性を得るには、平均粒度２〜１０μｍの合金粉
末が最も望ましい。If the particle size of the finely pulverized powder of the alloy according to the present invention exceeds the average particle size of 80 μm, excellent magnetic properties, especially high coercive force, cannot be obtained when producing a permanent magnet, and if the average particle size is less than 1 μm, The average particle size is 1 to 80 μm because oxidation is remarkable in the manufacturing process of a sintered magnet, that is, in the press molding, sintering, and aging processes, and excellent magnetic properties cannot be obtained. Further, in order to obtain excellent magnetic properties, alloy powder having an average particle size of 2 to 10 μm is most desirable.
【００２４】[0024]
【作用】この発明は、ストリップキャスティングされた
特定板厚の特定組成を有するＲ−Ｆｅ−Ｂ系合金にＨ2
吸蔵させることにより、微細に分散されたＲリッチ相が
水素化物を生成して体積膨張させて前記合金を自然崩壊
させ、その後微粉砕にて合金塊を構成している主相の結
晶粒を細分化することが可能となり、粒度分布が均一な
粉末を作製することができ、この際Ｒリッチ相が微細に
分散され、かつＲ2Ｆｅ14Ｂ相も微細化され、脱Ｈ2処理
して安定化させた合金粉末を微粉砕した場合、微粉砕能
は従来の約２倍にも向上するため、製造効率が大幅に向
上するともに、パルス磁界を用いて瞬間的に配向した
後、プレス成形、焼結することにより、Ｂｒ、ＢＨ（ｍ
ａｘ）及びｉＨｃを著しく改善向上したＲ−Ｆｅ−Ｂ系
永久磁石が得られる。According to the present invention, H 2 is added to an R-Fe-B type alloy having a specific composition with a specific plate thickness which has been strip cast.
By the occlusion, the finely dispersed R-rich phase produces a hydride and volume-expands to spontaneously collapse the alloy, and then finely pulverizes the crystal grains of the main phase constituting the alloy lump to subdivide them. It is possible to produce a powder having a uniform particle size distribution, in which case the R-rich phase is finely dispersed, and the R 2 Fe 14 B phase is also finely divided, and stable after de-H 2 treatment. When finely pulverized alloyed alloy powder is finely pulverized, the fine pulverization ability is about twice as high as the conventional one. Therefore, the production efficiency is significantly improved, and after instantaneously orienting using a pulse magnetic field, press molding, By sintering, Br, BH (m
It is possible to obtain an R-Fe-B based permanent magnet with significantly improved ax) and iHc.
【００２５】[0025]
実施例１ 高周波溶解炉にて溶解して得られたＮｄ１３．４−Ｂ
６．０−Ｆｅ８０．６組成の合金溶湯を直径２００ｍｍ
の銅製ロール２本を併設した双ロール式ストリップキャ
スターを用い、板厚約１ｍｍの薄板状鋳片を得た。前記
鋳片内の結晶粒径は短軸方向の寸法０．５μｍ〜１５μ
ｍ、長軸方向寸法は５μｍ〜８０μｍであり、Ｒリッチ
相は主相を取り囲むように３μｍ程度に微細に分離して
存在する。前記鋳片を５０ｍｍ角以下に破断後、前記破
断片１０００ｇを吸排気可能な密閉容器内に収容し、前
記容器内にＮ2ガスを３０分間流入して、空気と置換し
た後、該容器内に３ｋｇ／ｃｍ2のＨ2ガスを２時間供給
してＨ2吸臓により鋳片を自然崩壊させて、その後真空
中で５００℃に５時間保持して脱Ｈ2処理した後、室温
まで冷却し、さらに１００メッシュまで粗粉砕した。次
いで、前記粗粉砕を採取した８００ｇをジェットミルで
粉砕して平均粒度３．５μｍの合金粉末を得た。得られ
た合金粉末を用いて、ゴム質のモールドに原料粉末を充
填し、パルス磁界６０ｋＯｅを瞬間的に付加して、配向
させた後、静水圧プレス装置にて２．５Ｔ／ｃｍ2の圧
力で静水圧プレスした。モールドから取り出した成形体
を１０９０℃で３時間の条件にて焼結し、６００℃で１
時間の時効処理を行って、永久磁石を得た。得られた永
久磁石の磁石特性を表１に表す。Example 1 Nd13.4-B obtained by melting in a high frequency melting furnace
200-mm diameter molten alloy of 6.0-Fe80.6 composition
Using a twin roll type strip caster provided with two copper rolls, a thin plate-shaped cast piece having a plate thickness of about 1 mm was obtained. The crystal grain size in the slab is 0.5 μm to 15 μm in the short axis direction.
m, the dimension in the major axis direction is 5 μm to 80 μm, and the R-rich phase is present in a finely separated state of about 3 μm so as to surround the main phase. After breaking the slab into 50 mm square or less, 1000 g of the broken piece was housed in a closed container capable of sucking and exhausting, and N 2 gas was allowed to flow into the container for 30 minutes to be replaced with air, and then, inside the container. 3kg / cm 2 of H 2 gas was supplied for 2 hours to spontaneously disintegrate the slab by the H 2 sucker, and then it was kept at 500 ° C. for 5 hours in vacuum to remove H 2 and then cooled to room temperature. And further crushed to 100 mesh. Next, 800 g of the coarsely pulverized sample was pulverized with a jet mill to obtain an alloy powder having an average particle size of 3.5 μm. Using the obtained alloy powder, a raw material powder was filled in a rubber mold, and a pulsed magnetic field of 60 kOe was momentarily applied and oriented, and then a pressure of 2.5 T / cm 2 was applied by a hydrostatic press machine. It was hydrostatically pressed. The molded body taken out from the mold is sintered at 1090 ° C. for 3 hours, and then sintered at 600 ° C. for 1 hour.
Aging treatment for time was performed to obtain a permanent magnet. Table 1 shows the magnetic properties of the obtained permanent magnets.
【００２６】実施例２ 実施例１で得られた粉末を、図１に示す如く、上下パン
チ１，２の外周部に静磁界用コイル３，４を配置し、ダ
イス５内にパルス磁界用コイル６を配設して、原料粉末
７にパルス磁界と通常の静磁界とを併用して作用させる
ことができるプレス装置を用いて、まず、約３０ｋＯｅ
のパルス磁界で配向させた後、約１２ｋＯｅの磁界中で
プレス成形した。その後、成形体は実施例１と同一の条
件で、焼結、時効処理を行った。得られた永久磁石の磁
石特性を第１表に示す。Example 2 As shown in FIG. 1, the powder obtained in Example 1 was replaced with static magnetic field coils 3 and 4 on the outer peripheral portions of the upper and lower punches 1 and 2, and a pulse magnetic field coil was placed in a die 5. 6 is provided and a pressing device capable of acting on the raw material powder 7 in combination with a pulse magnetic field and a normal static magnetic field is used.
After aligning with a pulsed magnetic field of, a press molding was performed in a magnetic field of about 12 kOe. Thereafter, the molded body was sintered and aged under the same conditions as in Example 1. Table 1 shows the magnetic properties of the obtained permanent magnets.
【００２７】実施例３ 実施例１と同様にＮｄ１３．０−Ｄｙ０．５−Ｂ６．５
−Ｃｏ１．０−Ｆｅ７の合金をストリップキャスティン
グし、薄板状鋳片を得た。これを５０ｍｍ角以下に破断
後、１０００ｇを実施例１と同様にＨ2吸蔵により自然
崩壊させた後、真空中で６時間の脱Ｈ2処理した。これ
を粗粉砕後、ジェットミル粉砕して、平均粒度３．５μ
ｍの粉末を得た。得られた粉末を実施例１と同様にパル
ス磁界配向、静水圧プレスして、成形体を作製し、同様
に焼結熱処理を行った。得られた永久磁石の磁石特性を
表１に示した。Example 3 Nd13.0-Dy0.5-B6.5 as in Example 1.
An alloy of -Co1.0-Fe7 was strip-cast to obtain a thin plate-shaped cast piece. After breaking this to 50 mm square or less, 1000 g was spontaneously disintegrated by H 2 occlusion in the same manner as in Example 1 and then subjected to H 2 removal treatment in vacuum for 6 hours. This is roughly crushed and then jet-milled to give an average particle size of 3.5μ.
m powder was obtained. The obtained powder was subjected to pulse magnetic field orientation and hydrostatic pressing in the same manner as in Example 1 to prepare a molded body, and similarly sintered and heat treated. Table 1 shows the magnetic properties of the obtained permanent magnets.
【００２８】比較例１ 実施例１で得られた粉末を通常の磁界中プレス装置で約
１２ｋＯｅの磁界中でプレス成形し、その後、実施例１
と同一条件で焼結・時効処理を行った。得られた永久磁
石の磁石特性を表１に示した。Comparative Example 1 The powder obtained in Example 1 was press-molded in a magnetic field of about 12 kOe by a usual magnetic field press machine, and then Example 1 was used.
Sintering and aging treatment were performed under the same conditions as above. Table 1 shows the magnetic properties of the obtained permanent magnets.
【００２９】比較例２ 高周波溶解炉にて溶解して得られたＮｄ１３．４−Ｂ
６．０−Ｆｅ８０．６組成の合金溶湯を鉄製鋳型に鋳造
した。得られた合金塊の組織を観察したところ、初晶Ｆ
ｅの晶出が認められたため、１０５０℃で１０時間熱処
理して均質化処理を行った。鋳塊の結晶粒径は、短軸方
向３０〜１５０μｍ、長軸方向１００〜数ｍｍにもな
り、Ｒ−リッチ相が局部的１５０μｍ程度の大きさで偏
析していた。この合金塊を粗砕後、実施例１と同様の方
法でＨ2吸蔵処理、脱Ｈ2処理して、粗粉末を得た。さら
に、実施例１と同一の条件でジエットミル粉砕し、平均
粒径約３．７μｍの合金で得られた粉末を約１２ｋＯｅ
の磁界中でプレス成形し、実施例１と同一の条件で、焼
結、熱処理を行った。得られた永久磁石の特性を表１に
示す。Comparative Example 2 Nd13.4-B obtained by melting in a high frequency melting furnace
A molten alloy having a composition of 6.0-Fe80.6 was cast in an iron mold. When the structure of the obtained alloy ingot was observed, primary crystal F
Since crystallization of e was observed, heat treatment was performed at 1050 ° C. for 10 hours to perform homogenization treatment. The crystal grain size of the ingot was 30 to 150 μm in the minor axis direction and 100 to several mm in the major axis direction, and the R-rich phase was locally segregated with a size of about 150 μm. After this alloy ingot was crushed, H 2 occlusion treatment and H 2 removal treatment were carried out in the same manner as in Example 1 to obtain a coarse powder. Further, the powder obtained by pulverizing with a jet mill under the same conditions as in Example 1 and having an average particle diameter of about 3.7 μm was about 12 kOe.
Press molding was performed in the magnetic field of No. 1, and sintering and heat treatment were performed under the same conditions as in Example 1. The properties of the obtained permanent magnet are shown in Table 1.
【００３０】比較例３ 実施例１と同一組成、同一板厚のストリップキャスティ
ング鋳片を５０ｍｍ以下に粗粉砕後、Ｈ2吸蔵処理、脱
Ｈ2処理することなく、前記粗粉砕粉１０００ｇをスタ
ンプミルにて１時間粉砕して１００メッシュの粗粉砕粉
となした後、ジェットミル粉砕し、平均粒径約３．８μ
ｍの合金粉末を得た。前記合金粉末を約１２ｋＯｅ磁界
中での磁界中プレス、焼結、時効処理を行って永久磁石
を得た。得られた永久磁石の磁気特性を表１に表す。Comparative Example 3 A strip casting slab having the same composition and the same plate thickness as in Example 1 was roughly crushed to 50 mm or less, and then 1000 g of the roughly crushed powder was stamp-milled without H 2 occlusion treatment and de-H 2 treatment. After crushing for 1 hour to make 100 mesh coarse crushed powder, crushed by jet mill, average particle diameter of about 3.8μ
m alloy powder was obtained. The alloy powder was pressed in a magnetic field in a magnetic field of about 12 kOe, sintered, and aged to obtain a permanent magnet. Table 1 shows the magnetic properties of the obtained permanent magnets.
【００３１】比較例４ Ｎｄ１３．０−Ｄｙ０．５−Ｂ６．５−Ｃｏ１．０−Ｆ
ｅ７９の組成の合金を比較例２と同様の手法で鋳造し
た。得られた合金塊には、Ｆｅ初晶が晶出していたた
め、１０５０℃×６Ｈｒの熱処理を行った。この合金塊
を粗粉砕後、実施例１と同時にＨ2吸蔵処理し、真空中
で脱Ｈ2処理を行った。これを粗粉砕後、ジェットミル
粉砕して、平均粒径約３．７μｍの粉末を得た。さら
に、約１２ｋＯｅの磁界中で磁界中プレスした後、実施
例１と同一条件で、焼結・熱処理を行った。得られた永
久磁石の磁気特性を表１に表す。Comparative Example 4 Nd13.0-Dy0.5-B6.5-Co1.0-F
An alloy having the composition of e79 was cast by the same method as in Comparative Example 2. Since primary Fe crystals had crystallized in the obtained alloy ingot, heat treatment was performed at 1050 ° C. × 6 Hr. After roughly crushing this alloy ingot, H 2 occlusion treatment was carried out at the same time as in Example 1, and H 2 removal treatment was performed in vacuum. This was roughly crushed and then crushed with a jet mill to obtain a powder having an average particle size of about 3.7 μm. Furthermore, after pressing in a magnetic field in a magnetic field of about 12 kOe, sintering and heat treatment were performed under the same conditions as in Example 1. Table 1 shows the magnetic properties of the obtained permanent magnets.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【発明の効果】この発明による製造方法は、特定組成を
有するＲ−Ｆｅ−Ｂ系合金溶湯をストリップキャスティ
ングにて特定板厚の鋳片となし、この鋳片にＨ2吸蔵さ
せて自然崩壊させることにより、その後、脱Ｈ2処理し
て安定化させた合金粉末を微粉砕にて合金塊を構成して
いる主相の結晶粒を細分化することが可能となり、粒度
分布が均一な粉末を、従来の約２倍程度の効率で作製す
ることができ、粉砕時にＲリッチ相とＲ2Ｆｅ14Ｂ相も
微細化され、パルス磁界を用いてプレスすることによ
り、磁石化すると耐酸化性にすぐれ、磁石合金の磁気特
性、特に最大エネルギー積値（ＢＨ）ｍａｘ（ＭＧＯ
ｅ）；Ａと保磁力ｉＨｃ（ｋＯｅ）の特性値；Ｂの合計
値Ａ＋Ｂが５９以上の値を示す高性能Ｒ−Ｆｅ−Ｂ系永
久磁石が得られる。According to the manufacturing method of the present invention, an R-Fe-B alloy melt having a specific composition is formed into a slab having a specific plate thickness by strip casting, and the slab is allowed to occlude H 2 and spontaneously disintegrate. by, then, it becomes possible to subdivide the crystal grains of the main phase constituting an alloy ingot alloy powder was stabilized by removing H 2 treated with finely ground, particle size distribution uniform powder , R-rich phase and R 2 Fe 14 B phase are also miniaturized at the time of crushing, and can be made magnetized by using a pulsed magnetic field to improve oxidation resistance. Excellent magnetic properties of magnetic alloys, especially maximum energy product value (BH) max (MGO
e); A high-performance R-Fe-B system permanent magnet having a characteristic value of A and coercive force iHc (kOe); B of which total value A + B is 59 or more is obtained.
【図１】パルス磁界と通常の静磁界とを併用して作用さ
せることができるプレス装置の説明図である。FIG. 1 is an explanatory diagram of a press device that can act by using a pulse magnetic field and a normal static magnetic field together.
【図２】パルス磁界の時間と磁界強さとの関係を示すグ
ラフである。FIG. 2 is a graph showing a relationship between time of a pulsed magnetic field and magnetic field strength.
１，２ パンチ ３，４ 静磁界用コイル ５ ダイス ６ パルス磁界用コイル ７ 原料粉末 1, 2 Punch 3, 4 Static magnetic field coil 5 Dice 6 Pulse magnetic field coil 7 Raw material powder
Claims (2)
ち、少なくとも１種）１０ａｔ％〜３０ａｔ％、Ｂ２ａ
ｔ％〜２８ａｔ％、残部Ｆｅ（但しＦｅの１部をＣｏ、
Ｎｉの１種または２種にて置換できる）及び不可避的不
純物からなる合金溶湯をストリップキャスティング法に
て板厚０．０３ｍｍ〜１０ｍｍの薄板でＲリッチ相が５
μｍ以下に微細に分離した組織を有する鋳片に鋳造後、
前記鋳片を吸排気可能な容器に収容し、該容器内の空気
をＨ2ガスにて置換した後、該容器内に２００Ｔｏｒｒ
〜５０ｋｇ／ｍｍ2のＨ2ガスを供給して得られた崩壊合
金粉を脱Ｈ2処理した後、不活性ガス気流中で微粉砕し
て得た平均粒径が１〜１０μｍの微粉末をモールド内に
充填密度１．４〜３．０ｇ／ｃｍ3に充填し、瞬間的に
１０ｋＯｅ以上のパルス磁界をかけて配向させた後、成
形し、焼結、時効処理することを特徴とするＲ−Ｆｅ−
Ｂ系永久磁石材料の製造方法。1. R (provided that R is at least one of rare earth elements including Y) 10 at% to 30 at%, B2a
t% to 28 at%, balance Fe (however, a part of Fe is Co,
Ni alloy can be replaced by 1 type or 2 types of Ni) and unavoidable impurities, and a strip-casting method is used to form a thin plate having a plate thickness of 0.03 mm to 10 mm and an R-rich phase of 5
After casting into a slab having a finely divided structure of less than μm,
The slab was housed in a container capable of sucking and exhausting air, and the air in the container was replaced with H 2 gas, and then 200 Torr was stored in the container.
The collapsing alloy powder obtained by supplying H 2 gas of ˜50 kg / mm 2 is subjected to de-H 2 treatment and then pulverized in an inert gas stream to obtain fine powder having an average particle size of 1 to 10 μm. It is characterized in that it is filled in a mold to a packing density of 1.4 to 3.0 g / cm 3 , and is momentarily applied with a pulse magnetic field of 10 kOe or more for orientation, followed by molding, sintering and aging treatment. -Fe-
A method for manufacturing a B-based permanent magnet material.
１００℃〜７５０℃に加熱して脱Ｈ2処理することを特
徴とする請求項１に記載のＲ−Ｆｅ−Ｂ系永久磁石材料
の製造方法。2. The R—Fe—B based permanent magnet material according to claim 1, wherein the decay alloy powder obtained by hydrogen storage is heated to 100 ° C. to 750 ° C. for de-H 2 treatment. Production method.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19288693A JP3415208B2 (en) | 1993-07-06 | 1993-07-06 | Method for producing R-Fe-B permanent magnet material |
| EP93308184A EP0633581B1 (en) | 1993-07-06 | 1993-10-14 | R-Fe-B permanent magnet materials and process of producing the same |
| AT93308184T ATE165477T1 (en) | 1993-07-06 | 1993-10-14 | R-FE-B PERMANENT MAGNET MATERIALS AND THEIR PRODUCTION PROCESSES |
| RU93049098A RU2113742C1 (en) | 1993-07-06 | 1993-10-14 | Permanent-magnet materials and their manufacturing processes |
| DE69318147T DE69318147T2 (en) | 1993-07-06 | 1993-10-14 | R-Fe-B permanent magnet materials and their manufacturing processes |
| TW082108554A TW272293B (en) | 1993-07-06 | 1993-10-15 | |
| KR93021615A KR0131060B1 (en) | 1993-07-06 | 1993-10-15 | R-fe-b permanent magnet material & processing method |
| CN93115008A CN1076115C (en) | 1993-07-06 | 1993-10-15 | R-Fe-B permanent magnet materials and process of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19288693A JP3415208B2 (en) | 1993-07-06 | 1993-07-06 | Method for producing R-Fe-B permanent magnet material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0718366A true JPH0718366A (en) | 1995-01-20 |
| JP3415208B2 JP3415208B2 (en) | 2003-06-09 |
Family
ID=16298620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19288693A Expired - Lifetime JP3415208B2 (en) | 1993-07-06 | 1993-07-06 | Method for producing R-Fe-B permanent magnet material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3415208B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482353B1 (en) | 1999-11-12 | 2002-11-19 | Sumitomo Special Metals Co., Ltd. | Method for manufacturing rare earth magnet |
| US6527874B2 (en) | 2000-07-10 | 2003-03-04 | Sumitomo Special Metals Co., Ltd. | Rare earth magnet and method for making same |
| JP2006108591A (en) * | 2004-10-08 | 2006-04-20 | Tdk Corp | Rare-earth sintered magnet and manufacturing method therefor |
| US7141126B2 (en) | 2000-09-19 | 2006-11-28 | Neomax Co., Ltd. | Rare earth magnet and method for manufacturing the same |
| DE10119772B4 (en) * | 2000-04-21 | 2014-02-20 | Hitachi Metals, Ltd. | Powder press apparatus and method for producing a rare earth magnet using the same |
| US20150302960A1 (en) * | 2012-11-09 | 2015-10-22 | Xiamen Tungsten Co., Ltd. | Manufacturing method of a powder for compacting rare earth magnet and the rare earth magnet omitting jet milling process |
-
1993
- 1993-07-06 JP JP19288693A patent/JP3415208B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482353B1 (en) | 1999-11-12 | 2002-11-19 | Sumitomo Special Metals Co., Ltd. | Method for manufacturing rare earth magnet |
| DE10119772B4 (en) * | 2000-04-21 | 2014-02-20 | Hitachi Metals, Ltd. | Powder press apparatus and method for producing a rare earth magnet using the same |
| US6527874B2 (en) | 2000-07-10 | 2003-03-04 | Sumitomo Special Metals Co., Ltd. | Rare earth magnet and method for making same |
| US7141126B2 (en) | 2000-09-19 | 2006-11-28 | Neomax Co., Ltd. | Rare earth magnet and method for manufacturing the same |
| JP2006108591A (en) * | 2004-10-08 | 2006-04-20 | Tdk Corp | Rare-earth sintered magnet and manufacturing method therefor |
| US20150302960A1 (en) * | 2012-11-09 | 2015-10-22 | Xiamen Tungsten Co., Ltd. | Manufacturing method of a powder for compacting rare earth magnet and the rare earth magnet omitting jet milling process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3415208B2 (en) | 2003-06-09 |
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