JPH1092616A - Manufacture of rare-earth permanent magnet - Google Patents
Manufacture of rare-earth permanent magnetInfo
- Publication number
- JPH1092616A JPH1092616A JP8246104A JP24610496A JPH1092616A JP H1092616 A JPH1092616 A JP H1092616A JP 8246104 A JP8246104 A JP 8246104A JP 24610496 A JP24610496 A JP 24610496A JP H1092616 A JPH1092616 A JP H1092616A
- Authority
- JP
- Japan
- Prior art keywords
- phase
- intermetallic compound
- permanent magnet
- earth permanent
- rare earth
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
-
- 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
- H01F1/0579—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B with exchange spin coupling between hard and soft nanophases, e.g. nanocomposite spring magnets
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Power Engineering (AREA)
- Hard Magnetic Materials (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は優れた磁気特性を有
する希土類永久磁石およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rare earth permanent magnet having excellent magnetic properties and a method for producing the same.
【０００２】[0002]
【従来の技術】Ｎd-Ｆe-Ｂ系焼結磁石は45MGOeを超える
高い磁気特性を有し、またＳm 系磁石に比較して低原料
コストであることから需要が増大している。さらにより
高性能な次世代磁石の探索が行われている中で、近年ナ
ノコンポジット磁石が注目を集めている（IEEE Trans.
Magn. 27 (1991),p.3588他）。これはハード磁性相中に
数十nmオーダーのソフト磁性相が微細に分散した組織か
らなり、両相の磁化が交換相互作用で結び付くことによ
ってソフト相の磁化は容易に反転せず、全体として単一
相のように振る舞うものであり、既存原料の組み合わせ
によっても保磁力を損なうことなく、より高い飽和磁化
が得られる可能性があり、計算ではＳm2Ｃo17 Ｎ3 ／Ｆ
e-Ｃo においてBHmax ＝137MGOe の値が報告（J. Phys.
Rev. 48(1993),p.15812）されている。これまで実際に
Ｎd2Ｆe14 Ｂ／Ｆe3Ｂ（J. de Phys. 49(1988),C8-669
）やＳm2Ｃo17 Ｎ3 ／Ｆe （J. Magn, Magn. Mater. 1
24(1993),L1）等の組合せが実験報告されてきた。これ
らの研究で行われている微細分散組織の作製方法として
は、メトルスパン法やメカニカルアロイング（ＭＡ）法
により得られた合金薄帯や粉末を熱処理して微結晶化す
る手段がとられている。しかしこれらの方法では、熱処
理条件により結晶粒径が制御できる半面、磁気的に等方
性のものしか得られず、異方性Ｎd-Ｆe-Ｂ焼結磁石の磁
気特性には及ばない。また高温焼結すると粒径が粗大化
して磁気特性が劣化するために、現在のところボンド磁
石としての用途しか期待できないという問題点があっ
た。2. Description of the Related Art Demand is increasing for Nd-Fe-B sintered magnets because they have high magnetic properties exceeding 45 MGOe and have lower raw material costs than Sm magnets. In search of higher performance next-generation magnets, nanocomposite magnets have recently attracted attention (IEEE Trans.
Magn. 27 (1991), p.3588, etc.). This consists of a microstructure in which a soft magnetic phase of the order of several tens of nanometers is finely dispersed in a hard magnetic phase.The magnetization of the soft phase is not easily reversed by the exchange interaction of the two phases, and the whole is simply unitary. It behaves like a single phase, and a higher saturation magnetization may be obtained without losing the coercive force even with a combination of existing raw materials. The calculation shows that Sm 2 Co 17 N 3 / F
A value of BH max = 137MGOe was reported in e-Co (J. Phys.
Rev. 48 (1993), p.15812). Until now, Nd 2 Fe 14 B / Fe 3 B (J. de Phys. 49 (1988), C8-669)
) And Sm 2 Co 17 N 3 / Fe (J. Magn, Magn. Mater. 1
24 (1993), L1) and other combinations have been reported experimentally. As a method of producing a finely dispersed structure used in these studies, a method of heat-treating an alloy ribbon or powder obtained by a metrological spanning method or a mechanical alloying (MA) method to microcrystallize is used. . However, in these methods, although the crystal grain size can be controlled by the heat treatment conditions, only a magnetically isotropic one can be obtained, which does not reach the magnetic properties of the anisotropic Nd-Fe-B sintered magnet. In addition, when sintering at a high temperature, the particle size becomes coarse and the magnetic properties deteriorate, so that there is a problem that only use as a bonded magnet can be expected at present.
【０００３】[0003]
【発明が解決しようとする課題】このように従来の作製
方法では、Ｎd-Ｆe-Ｂ焼結磁石を超える磁気特性を得る
ことは難しい。本発明は従来と異なる新規な方法を用
い、磁気的異方性を有するナノコンポジット組織を作製
することにより、より磁気特性の高いＮd-Ｆe-Ｂ系希土
類永久磁石を提供しようとするものである。As described above, it is difficult to obtain magnetic properties exceeding those of a sintered Nd-Fe-B magnet by the conventional manufacturing method. The present invention intends to provide a Nd-Fe-B-based rare earth permanent magnet having higher magnetic properties by producing a nanocomposite structure having magnetic anisotropy by using a novel method different from the conventional method. .
【０００４】[0004]
【課題を解決するための手段】本発明者等は、かかる課
題を解決するために微細分散析出方法を種々検討した結
果、Ｎd とＦe から成る金属間化合物を出発原料とし、
この相にＢ元素を拡散させると共に、Ｎd2Ｆe14 Ｂ相生
成反応を行わせることによって微細分散組織が得られる
ことを見出し、諸条件を確立して本発明を完成させた。
その要旨は、Ｎd、Ｆe、Ｂの元素から成り、かつその主相
であるＮd2Ｆe14 Ｂ相中にＦe またはＦe を含む合金も
しくは金属間化合物が微細に分散した組織から成る希土
類永久磁石の製造方法において、式 Ｎd2Ｆe17 で表さ
れる金属間化合物を原料とし、該金属間化合物相にＢ元
素を拡散させて、磁気的異方性および前記微細分散組織
を有する主相Ｎd2Ｆe14 Ｂを得ることを特徴とする希土
類永久磁石の製造方法である。請求項２は、Ｂ、Ｂ2 Ｏ
3 または硼酸の内の１種以上、金属間化合物Ｎd2Ｆe17
および金属Ｃa から成る混合粉体を熱処理して、ＢをＮ
d-Ｆe 金属間化合物中に拡散させることを特徴とする請
求項１に記載の希土類永久磁石の製造方法である。請求
項３は、Ｎd2Ｆe14 Ｂ主相中にＦe またはＦe を含む合
金もしくは金属間化合物が微細に分散した組織を主相と
する磁石が、磁気的異方性を有していることを特徴とす
る希土類永久磁石の製造方法である。Means for Solving the Problems The present inventors have studied various methods for finely dispersing and precipitating in order to solve the above-mentioned problems. As a result, an intermetallic compound composed of Nd and Fe was used as a starting material.
The inventors have found that a finely dispersed structure can be obtained by diffusing the element B into this phase and causing a Nd 2 Fe 14 B phase formation reaction, and established various conditions to complete the present invention.
The gist of the invention is that a rare-earth permanent magnet composed of elements of Nd, Fe, and B and having a structure in which Fe or an alloy or an intermetallic compound containing Fe is finely dispersed in its main phase, Nd 2 Fe 14 B phase. In the production method, an intermetallic compound represented by the formula Nd 2 Fe 17 is used as a raw material, and element B is diffused into the intermetallic compound phase to form a main phase Nd 2 Fe having magnetic anisotropy and the finely dispersed structure. A method for producing a rare earth permanent magnet, characterized by obtaining 14B . Claim 2 is B, B 2 O
3 or one or more of boric acids, an intermetallic compound Nd 2 Fe 17
And heat treatment of the mixed powder comprising Ca and B
The method for producing a rare earth permanent magnet according to claim 1, wherein the permanent magnet is diffused in d-Fe intermetallic compound. A third aspect of the present invention is that a magnet having a main phase of a structure in which Fe or an alloy or an intermetallic compound containing Fe is finely dispersed in a main phase of Nd 2 Fe 14 B has magnetic anisotropy. This is a method for producing a rare earth permanent magnet.
【０００５】請求項４は、希土類元素Ｒ（ＲはＹを含む
希土類元素の内１種以上４種以下）、元素Ｍ（ＭはＲ、
Ｂを除くＣo、Ｎi、Ａl、Ｓi、Ｇa、Ａg、Ａu、Ｃu、Ｖ、 Ｃr、Ｍ
n、Ｓc 、 Ｍo、Ｗ、 Ｔi、Ｈf、Ｔa、Ｎb、Ｚr、Ｐd、Ｐt、Ｚn、Ｇ
e、Ｓb、Ｓn およびＩn から選択される１種以上５種以下
の元素で、少なくともＦe を含む）およびＢを含む３種
以上の元素から成り、かつその主相であるＲ2 Ｍ14Ｂ相
中にＦe またはＦe を含む合金もしくは金属間化合物が
微細に分散した組織から成る希土類永久磁石の製造方法
において、式 Ｒm Ｆen で表される金属間化合物（こ
こにm、n は正の整数で、原子比 n/m＞7.0 とする）を原
料とし、該金属間化合物相にＢ元素を拡散させて、磁気
的異方性および前記微細分散組織を有する主相Ｒ2 Ｍ14
Ｂを得ることを特徴とする希土類永久磁石の製造方法で
ある。請求項５は、Ｂ、Ｂ2 Ｏ3 または硼酸の内１種以
上、金属間化合物Ｒm Ｍn （ここにm、n は正の整数で、
原子比 n/m＞7.0 とする）および金属Ｃa から成る混合
粉体を熱処理して、ＢをＲとＭから成る金属間化合物中
に拡散させることを特徴とする希土類永久磁石の製造方
法である。請求項６は、Ｒ2 Ｍ14Ｂ主相中にＦe または
Ｆe を含む合金もしくは金属間化合物が微細に分散した
組織を主相とする磁石が、磁気的異方性を有しているこ
とを特徴とする希土類永久磁石の製造方法である。[0005] Claim 4 describes a rare earth element R (R is one or more and four or less of rare earth elements including Y), an element M (M is R,
Except for B, Co, Ni, Al, Si, Ga, Ag, Au, Cu, V, Cr, M
n, Sc, Mo, W, Ti, Hf, Ta, Nb, Zr, Pd, Pt, Zn, G
e, Sb, Sn, and In at least one element and no more than five elements selected from the group consisting of at least Fe, and three or more elements containing B, and the main phase of the R 2 M 14 B phase the method of manufacturing a rare earth permanent magnet alloy or intermetallic compound containing Fe or Fe is a fine dispersed organizations in the formula R m Fe intermetallic compound represented by n (here m, n is a positive integer The atomic ratio n / m> 7.0) is used as a raw material, and the element B is diffused into the intermetallic compound phase to obtain a main phase R 2 M 14 having magnetic anisotropy and the finely dispersed structure.
B is a method for producing a rare-earth permanent magnet. Claim 5 relates to one or more of B, B 2 O 3 and boric acid, and an intermetallic compound R m M n (where m and n are positive integers,
Atomic ratio n / m> 7.0) and heat treating a mixed powder of metal Ca to diffuse B into the intermetallic compound of R and M, thereby producing a rare earth permanent magnet. . According to a sixth aspect of the present invention, the magnet whose main phase is a structure in which Fe or an alloy or intermetallic compound containing Fe is finely dispersed in the R 2 M 14 B main phase has magnetic anisotropy. This is a method for producing a rare earth permanent magnet.
【０００６】[0006]
【発明の実施の形態】以下、本発明の実施の形態を詳細
に説明する。本発明のＮd-Ｆe-Ｂ系希土類永久磁石は、
ハード磁性相の主相中にソフト磁性相が極めて微細に分
散した組織から成っている。一般に母相中に析出物が微
細分散した組織を得るためによく用いられるのは、過飽
和固溶体の熱処理による析出である。アモルファス急冷
薄帯やＭＡ粉体からの微結晶化もこの方法の一種と見做
せる。しかしこれらの方法では磁化容易軸が特定方向に
向かないため等方性のものしか得られない。もしＮd2Ｆ
e14 Ｂ相（以下、Ｎd2Ｆe14 Ｂ相またはＲ2 Ｍ14Ｂ相を
2-14-1相という）にＦe の固溶域があるならば、結晶方
位を揃えたままＦe を析出させることも可能であるが、
報告されている状態図から明らかなように、Ｆe はほと
んど固溶しない。そこで本発明では新たな製造方法を種
々検討した結果、Ｎd2Ｆe17 もしくは原子比が n/m＞7.
0 なるＲm Ｍn 金属間化合物を原料とし、この金属間化
合物相にＢ元素を拡散させると共に、2-14-1相生成反応
を行わせることによって上記微細分散組織が得られるこ
とを見出した。Embodiments of the present invention will be described below in detail. The Nd-Fe-B rare earth permanent magnet of the present invention
It is composed of a structure in which the soft magnetic phase is very finely dispersed in the main phase of the hard magnetic phase. In general, precipitation of a supersaturated solid solution by heat treatment is often used to obtain a structure in which precipitates are finely dispersed in a matrix. Amorphous quenched ribbons and microcrystallization from MA powder can be considered as a kind of this method. However, in these methods, since the axis of easy magnetization does not point in a specific direction, only an isotropic one can be obtained. If Nd 2 F
e 14 B phase (hereinafter referred to as Nd 2 Fe 14 B phase or R 2 M 14 B phase)
If there is a solid solution region of Fe in the (2-14-1 phase), it is possible to precipitate Fe with the crystal orientation aligned.
As is evident from the reported phase diagram, Fe hardly forms a solid solution. Therefore, in the present invention, as a result of studying various new production methods, Nd 2 Fe 17 or an atomic ratio of n / m> 7.
It has been found that the above finely dispersed structure can be obtained by using the Rm Mn intermetallic compound as a raw material and diffusing the element B into the intermetallic compound phase and performing a 2-14-1 phase formation reaction.
【０００７】Ｎd2Ｆe17 金属間化合物を原料とした場
合、この反応は以下のように表せる。 Ｎd2Ｆe17 ＋ Ｂ ─→ Ｎd2Ｆe14 Ｂ ＋ ３Ｆe また、Ｒm Ｍn 金属間化合物の一例として、Ｎd Ｆe11
Ｔi を用いた場合は、次のように示される。 ２Ｎd Ｆe11 Ｔi ＋５Ｂ─→ Ｎd2Ｆe14 Ｂ ＋ ８Ｆ
e ＋ ２Ｔi Ｂ2 Ｎd 原子とＦe 原子はＮd2Ｆe17 もしくはＲm Ｍn 相内
で元々均質に存在しているので、Ｂが均一に拡散すれば
2-14-1相も相内で均一に反応生成し、同時に余剰のＦe
が極めて微細に分散して排出される。熱処理条件を最適
化することによって、これらの余剰Ｆe が数十nm以下の
粒径で2-14-1相中に分散した組織を得ることができる。
このとき2-14-1相がハード磁性相、Ｆe がソフト磁性相
に対応する。このような反応をさせるには、出発原料の
Ｒm Ｍn 金属間化合物が n/m＞7.0 である必要がある。
n/m が7.0 以下のときは余剰Ｆe が形成されないために
このような分散析出は起こらない。またこの反応は出発
原料であるＮd2Ｆe17 もしくはＲm Ｍn 相へのＢ拡散に
よって行われるため、形成される2-14-1相の結晶方位は
元の相の方位に束縛され、磁化容易軸が一方向に揃って
いる。When the Nd 2 Fe 17 intermetallic compound is used as a raw material, this reaction can be expressed as follows. Nd 2 Fe 17 + B─ → Nd 2 Fe 14 B + 3Fe Further, as an example of the Rm Mn intermetallic compound, Nd Fe 11
When Ti is used, it is expressed as follows. 2Nd Fe 11 Ti + 5B─ → Nd 2 Fe 14 B + 8F
Since e + 2Ti B 2 Nd atoms and Fe atoms are present in originally homogeneous Nd 2 Fe 17 or R m M n Aiuchi, if B is uniformly diffused
2-14-1 The phase also reacts uniformly in the phase, and at the same time, excess Fe
Are very finely dispersed and discharged. By optimizing the heat treatment conditions, it is possible to obtain a structure in which the excess Fe is dispersed in the 2-14-1 phase with a particle size of several tens nm or less.
At this time, the phase 2-14-1 corresponds to the hard magnetic phase, and Fe corresponds to the soft magnetic phase. To such a reaction, it is necessary R m M n intermetallic starting material is n / m> 7.0.
When n / m is 7.0 or less, such dispersion precipitation does not occur because no excess Fe is formed. Since this reaction performed by B diffusion into Nd 2 Fe 17 or R m M n-phase as a starting material, the crystal orientation of the 2-14-1 phase formed is bound to the orientation of the original phase, the magnetization Easy axes are aligned in one direction.
【０００８】n/m＞7.0 なるＲm Ｍn 金属間化合物と
は、例えばＮd2Ｆe17、Ｎd2( Ｆe,Ｃo)17、Ｎd2( Ｆe,Ａ
l)17、Ｎd2( Ｆe,Ｓi)17、Ｎd2( Ｆe,Ｃo,Ｇa)17、Ｎd2
( Ｆe,Ｃo,Ｔa)17、Ｎd2( Ｆe,Ｃo,Ｚr)17、Ｎd2( Ｆe,
Ｃo,Ｎb)17、Ｎd2( Ｆe,Ｃo,Ｈf)17、( Ｎd,Ｐr,Ｄy)
2(Ｆe,Ｃo,Ｔa)17、( Ｎd,Ｐr,Ｄy)2(Ｆe,Ｃo,Ｚr)17、
(Ｎd,Ｐr,Ｄy)2(Ｆe,Ｃo,Ｎb)17、( Ｎd,Ｐr、Ｄy)2(Ｆ
e,Ｃo,Ｈf)17、( Ｎd,Ｐr,Ｄy)2(Ｆe,Ｃo,Ｔi)17、( Ｎ
d,Ｐr、Ｄy)2(Ｆe,Ｃo,Ｖ)17 等一般に2-17相と呼ばれて
いるＴh2Ｚn17 型化合物や、Ｎd(Ｆe,Ｔi)12、Ｎd(Ｆe,
Ｃr)12、Ｎd(Ｆe,Ｍo)12、Ｎd(Ｆe,Ｗ)12 、Ｎd(Ｆe,Ｓ
i)12、Ｎd(Ｆe,Ｖ)12 、Ｎd(Ｆe,Ｃo,Ｔi)12、Ｎd(Ｆe,
Ｃo,Ｃr)12、Ｎd(Ｆe,Ｃo,Ｍo)12、Ｎd(Ｆe,Ｃo,Ｗ)
12 、Ｎd(Ｆe,Ｃo,Ｓi)12、Ｎd(Ｆe,Ｃo,Ｖ)12 、( Ｎ
d,Ｐr,Ｄy)( Ｆe,Ｃo,Ｔi)12、( Ｎd,Ｐr,Ｄy)( Ｆe,Ｃ
o,Ｃr)12、( Ｎd,Ｐr,Ｄy)( Ｆe,Ｃo,Ｍo)12、( Ｎd,Ｐ
r,Ｄy)( Ｆe,Ｃo,Ｗ)12 、( Ｎd,Ｐr,Ｄy)( Ｆe,Ｃo,Ｓ
i)12、( Ｎd,Ｐr,Ｄy)2(Ｆe,Ｃo,Ｖ)12 等の１-12 金属
間化合物、Ｎd3( Ｆe,Ｔi)29、Ｎd3( Ｆe,Ｃr)29、Ｎd3
( Ｆe,Ｍo)29、Ｎd3( Ｆe,Ｗ)29 、Ｎd3( Ｆe,Ｓi)29、
Ｎd3( Ｆe,Ｖ)29 、Ｎd3( Ｆe,Ｃo,Ｔi)29、Ｎd3( Ｆe,
Ｃo,Ｃr)29、Ｎd3( Ｆe,Ｃo,Ｍo)29、Ｎd3( Ｆe,Ｃo,
Ｗ)29 、Ｎd3( Ｆe,Ｃo,Ｓi)29、Ｎd3( Ｆe,Ｃo,Ｖ)
29 、( Ｎd,Ｐr,Ｄy)3(Ｆe,Ｃo,Ｔi)29、( Ｎd,Ｐr,Ｄ
y)3(Ｆe,Ｃo,Ｃr )29 、( Ｎd,Ｐr,Ｄy)3(Ｆe,Ｃo,Ｍo)
29、 ( Ｎd,Ｐr,Ｄy)3(Ｆe,Ｃo,Ｗ)29、( Ｎd,Ｐr,Ｄy)
3(Ｆe,Ｃo,Ｓi)29、 ( Ｎd,Ｐr,Ｄy)3(Ｆe,Ｃo,Ｖ)29 等
の３-29 金属間化合物が挙げられるが、これらに限定さ
れるものではない。[0008] n / m> 7.0 becomes R m M A n intermetallic compounds, for example, Nd 2 Fe 17, Nd 2 ( Fe, Co) 17, Nd 2 (Fe, A
l) 17 , Nd 2 (Fe, Si) 17 , Nd 2 (Fe, Co, Ga) 17 , Nd 2
(Fe, Co, Ta) 17 , Nd 2 (Fe, Co, Zr) 17 , Nd 2 (Fe,
(Co, Nb) 17 , Nd 2 (Fe, Co, Hf) 17 , (Nd, Pr, Dy)
2 (Fe, Co, Ta) 17 , (Nd, Pr, Dy) 2 (Fe, Co, Zr) 17 ,
(Nd, Pr, Dy) 2 (Fe, Co, Nb) 17 , (Nd, Pr, Dy) 2 (F
e, Co, Hf) 17 , (Nd, Pr, Dy) 2 (Fe, Co, Ti) 17 , (N
d, Pr, Dy) 2 ( Fe, Co, V) 17 or the like and generally 2-17 phase and is called Th 2 Zn 17 type compounds, Nd (Fe, Ti) 12 , Nd (Fe,
Cr) 12 , Nd (Fe, Mo) 12 , Nd (Fe, W) 12 , Nd (Fe, S)
i) 12 , Nd (Fe, V) 12 , Nd (Fe, Co, Ti) 12 , Nd (Fe,
Co, Cr) 12 , Nd (Fe, Co, Mo) 12 , Nd (Fe, Co, W)
12 , Nd (Fe, Co, Si) 12 , Nd (Fe, Co, V) 12 , (N
d, Pr, Dy) (Fe, Co, Ti) 12 , (Nd, Pr, Dy) (Fe, C
o, Cr) 12 , (Nd, Pr, Dy) (Fe, Co, Mo) 12 , (Nd, P
r, Dy) (Fe, Co, W) 12 , (Nd, Pr, Dy) (Fe, Co, S
i) 12, (Nd, Pr , Dy) 2 (Fe, Co, V) 1-12 intermetallic compounds such as 12, Nd 3 (Fe, Ti ) 29, Nd 3 (Fe, Cr) 29, Nd 3
(Fe, Mo) 29 , Nd 3 (Fe, W) 29 , Nd 3 (Fe, Si) 29 ,
Nd 3 (Fe, V) 29 , Nd 3 (Fe, Co, Ti) 29 , Nd 3 (Fe, V)
Co, Cr) 29 , Nd 3 (Fe, Co, Mo) 29 , Nd 3 (Fe, Co,
W) 29 , Nd 3 (Fe, Co, Si) 29 , Nd 3 (Fe, Co, V)
29 , (Nd, Pr, Dy) 3 (Fe, Co, Ti) 29 , (Nd, Pr, D
y) 3 (Fe, Co, Cr) 29 , (Nd, Pr, Dy) 3 (Fe, Co, Mo)
29 , (Nd, Pr, Dy) 3 (Fe, Co, W) 29 , (Nd, Pr, Dy)
Examples thereof include, but are not limited to, 3-29 intermetallic compounds such as 3 (Fe, Co, Si) 29 and (Nd, Pr, Dy) 3 (Fe, Co, V) 29 .
【０００９】また磁気特性や相安定性をさらに向上させ
るために、上記以外にもＮd の一部または全部をＹを含
む他の希土類元素、即ちＬa、Ｃe、Ｐr、Ｓm、Ｅu、Ｇd、Ｔb、
Ｄy、Ｈo、Ｅr、Ｔm、Ｙb およびＬu から成る群から選択さ
れる１種以上３種、具体的にはＰr、Ｐr-Ｄy、Ｃe-Ｄy、Ｐ
r-Ｔb、Ｃe-Ｔb 、 Ｐr-Ｔb-Ｄy、Ｐr-Ｃe-Ｄy 等で置換し
たり、Ｆe の一部をＣo、Ｎi、Ａl、Ｓi、Ｇa、Ａg、Ａu、Ｃu、
Ｖ、 Ｃr、Ｍn、Ｓc 、 Ｍo、Ｗ、 Ｔi、Ｈf、Ｔa、Ｎb、Ｚr、Ｐd、
Ｐt、Ｚn、Ｇe、Ｓb、Ｓn、Ｉn その他１種以上その他１種以
上４種以下の元素で置換してもよい。具体的には、例え
ば、Ｃo、Ｎi、Ｔi、Ｍo、Ｃo-Ａl、Ｃo-Ｓi、Ｃo-Ｇa、Ｃo-Ｃ
u、Ｃo-Ｖ、 Ｃo-Ｃr、Ｃo-Ｍn、Ｃo-Ｍo、Ｃo-Ｗ、 Ｃo-Ｔi、
Ｃo-Ｈf、Ｃo-Ｔa、Ｃo-Ｎb、Ｃo-Ｚr、Ｃo-Ｎi、Ｃo-Ｔi-Ａ
l、Ｃo-Ｔi-Ｇa、Ｃo-Ｔi-Ｓi、Ｃo-Ｔi-Ｚr、Ｃo-Ｔi-Ｎb、
Ｃo-Ｔi-Ｈf、Ｃo-Ｔi-Ｔa、Ｃo-Ｍo-Ａl、Ｃo-Ｍo-Ｇa、Ｃ
o-Ｍo-Ｓi、Ｃo-Ｍo-Ｚr、Ｃo-Ｍo-Ｎb、Ｃo-Ｍo-Ｈf、Ｃo-
Ｍo-Ｔa、Ｃo-Ｔi-Ａl-Ｇa、Ｃo-Ｔi-Ａl-Ｚr、Ｃo-Ｔi-Ａ
l-Ｎb、Ｃo-Ｔi-Ａl-Ｈf、Ｃo-Ｔi-Ａl-Ｔa、Ｃo-Ｍo-Ａl-
Ｇa、Ｃo-Ｍo-Ａl-Ｚr、Ｃo-Ｍo-Ａl-Ｎb、Ｃo-Ｍo-Ａl-Ｈ
f、Ｃo-Ｍo-Ａl-Ｔa、Ｃo-Ｔi-Ｓi-Ｇa、Ｃo-Ｍo-Ｓi-Ｚr
等の組み合わせが例示される。In order to further improve the magnetic characteristics and phase stability, other rare earth elements containing Nd partially or wholly containing Y, ie, La, Ce, Pr, Sm, Eu, Gd, Tb, other than those described above, are used. ,
At least one selected from the group consisting of Dy, Ho, Er, Tm, Yb and Lu, specifically Pr, Pr-Dy, Ce-Dy, P
r-Tb, Ce-Tb, Pr-Tb-Dy, Pr-Ce-Dy, etc., or a part of Fe is Co, Ni, Al, Si, Ga, Ag, Au, Cu,
V, Cr, Mn, Sc, Mo, W, Ti, Hf, Ta, Nb, Zr, Pd,
Pt, Zn, Ge, Sb, Sn, In and the like may be substituted with one or more other elements and one or more and four or less elements. Specifically, for example, Co, Ni, Ti, Mo, Co-Al, Co-Si, Co-Ga, Co-C
u, Co-V, Co-Cr, Co-Mn, Co-Mo, Co-W, Co-Ti,
Co-Hf, Co-Ta, Co-Nb, Co-Zr, Co-Ni, Co-Ti-A
l, Co-Ti-Ga, Co-Ti-Si, Co-Ti-Zr, Co-Ti-Nb,
Co-Ti-Hf, Co-Ti-Ta, Co-Mo-Al, Co-Mo-Ga, C
o-Mo-Si, Co-Mo-Zr, Co-Mo-Nb, Co-Mo-Hf, Co-
Mo-Ta, Co-Ti-Al-Ga, Co-Ti-Al-Zr, Co-Ti-A
l-Nb, Co-Ti-Al-Hf, Co-Ti-Al-Ta, Co-Mo-Al-
Ga, Co-Mo-Al-Zr, Co-Mo-Al-Nb, Co-Mo-Al-H
f, Co-Mo-Al-Ta, Co-Ti-Si-Ga, Co-Mo-Si-Zr
And the like.
【００１０】この時、形成されるハード相はＮd2Ｆe14
Ｂに限定されず、（Ｎd,Ｐr)2(Ｆe,Ｃo)14Ｂ、( Ｎd,Ｄ
y)2(Ｆe,Ａl)14Ｂ、（Ｎd,Ｐr,Ｄy)2(Ｆe,Ｃo,Ｓi)14Ｂ
等Ｎd、Ｆe の各々が他元素で置換され得るし、ソフト相
もＦe に限らずＦe-Ｂ、 Ｆe-Ｃo、Ｆe-Ｎi、Ｆe-Ａl、Ｆe-
Ｓi、Ｆe-Ｇa、Ｆe-Ａg、Ｆe-Ａu、Ｆe-Ｃu、Ｆe-Ｖ、 Ｆe-Ｃ
r、Ｆe-Ｍo、Ｆe-Ｗ、 Ｆe-Ｔi、その他の組合せからなるＦ
e 基合金や化合物であってよい。ただしソフト相の条件
としては、飽和磁化がハード相よりも大きいことが必要
である。ソフト相の飽和磁化は大きい程好ましいので、
より望ましくはＦe、Ｆe-Ｃ、 Ｆe-Ｂ、 Ｆe-Ｎ、 Ｆe-Ｃo
、 Ｆe-Ａl、Ｆe-Ｓi 等の金属、合金や化合物がよい。
Ｒm Ｍn 化合物のn/m の比は7.0 を超えるのがよく、7.
0 以下では2-14-1相の生成反応において余剰のＦe また
はＭが排出されないため、本発明の目的である微細分散
組織が形成されない。またこの時、同時にＴi Ｂ2、Ｍo
Ｂ、 Ｃr Ｂ2 等の非磁性第３相が析出する場合もある。
これは単位体積当りの磁化を減少させるものの、耐食性
を向上させる等の効果も考えられ、少量ならば特に問題
はない。At this time, the formed hard phase is Nd 2 Fe 14
Not limited to B, (Nd, Pr) 2 (Fe, Co) 14 B, (Nd, D
y) 2 (Fe, Al) 14 B, (Nd, Pr, Dy) 2 (Fe, Co, Si) 14 B
Each of Nd and Fe can be replaced by another element, and the soft phase is not limited to Fe but Fe-B, Fe-Co, Fe-Ni, Fe-Al, Fe-
Si, Fe-Ga, Fe-Ag, Fe-Au, Fe-Cu, Fe-V, Fe-C
F consisting of r, Fe-Mo, Fe-W, Fe-Ti, and other combinations
An e-base alloy or compound may be used. However, the condition of the soft phase requires that the saturation magnetization be larger than that of the hard phase. The larger the saturation magnetization of the soft phase, the better,
More preferably, Fe, Fe-C, Fe-B, Fe-N, Fe-Co
Metals, alloys and compounds such as Fe-Al and Fe-Si are preferred.
The ratio of n / m of R m M n compounds may from exceeding 7.0, 7.
Below 0, excessive Fe or M is not discharged in the 2-14-1 phase formation reaction, so that the finely dispersed structure, which is the object of the present invention, is not formed. At this time, Ti B 2 and Mo
B, there is a case where non-magnetic third phase such as Cr B 2 is precipitated.
Although this reduces the magnetization per unit volume, it is also considered to have an effect of improving corrosion resistance, etc., and there is no particular problem if the amount is small.
【００１１】以上のような反応を行わせるためには、ま
ずＮd2Ｆe17 やＲm Ｍn 化合物中にＢを均一に拡散させ
る工程が必要である。拡散が不十分な場合は、局所的に
未反応部分が残ったり、Ｂ過剰な相が形成されたりして
磁気特性が劣化する。この拡散方法として、例えばＣa
を用いた還元拡散法を応用する。還元拡散法については
いくつかの提案（特開昭59-219404 号、特開昭62-26000
8 号参照）がなされているが、従来より提示されてきた
還元拡散法の要点は、原料として希土類の酸化物を用い
ることにある。一方本発明がＣa を採択した理由は、Ｎ
d2Ｆe17 やＲm Ｍn 化合物中のＢ拡散を促進させるため
にＣa 液相を利用している点にある。従って本発明では
原料として希土類酸化物ではなく、希土類−Ｆe 化合物
を使用しており、従来の還元拡散法とは根本的に異なる
方法である。In [0011] order to perform the above reactions, it is necessary step for first Nd 2 Fe 17 or R m M n uniformly diffuse into the compound B is. If the diffusion is insufficient, unreacted portions remain locally or a B-excess phase is formed, resulting in deterioration of magnetic properties. As this diffusion method, for example, Ca
Apply the reduction diffusion method using. Several proposals have been made for the reduction diffusion method (JP-A-59-219404, JP-A-62-26000).
However, the key point of the reduction diffusion method that has been proposed in the past is that a rare earth oxide is used as a raw material. On the other hand, the reason why the present invention adopted Ca is that N
The point is that a Ca liquid phase is used to promote B diffusion in d 2 Fe 17 and R mm M n compounds. Therefore, in the present invention, a rare earth-Fe compound is used as a raw material instead of a rare earth oxide, which is a fundamentally different method from the conventional reduction diffusion method.
【００１２】以下、Ｎd2Ｆe17 を例に説明すると、本発
明の希土類永久磁石の製造工程は、粗粉砕されたＮd2Ｆ
e17 化合物、Ｂ2 Ｏ3 粉末、金属Ｃa 粒を混合・プレス
して不活性ガス雰囲気中高温で熱処理する。Ｂ2 Ｏ3 の
代わりに金属Ｂや硼酸等の粉末を用いてもよい。Ｂ2 Ｏ
3 のＮd2Ｆe17 合金に対する混合比は、生成するソフト
相の種類によって異なるが、例としてＦe を生成する場
合はＮd2Ｆe17 のＮdが全て2-14-1相を形成するのに必
要なＢ当量の0.8 倍から1.5 倍、Ｆe2Ｂを生成する場合
は2-14-1相とＦe2Ｂ相を形成するのに必要なＢ当量を供
給するだけのＢ2 Ｏ3 量の0.8 倍から1.5 倍、とすれば
よい。また金属Ｃa の混合比は、Ｂ2 Ｏ3 を還元する必
要当量のままでは全てのＣa がＣa Ｏとなって液相がな
くなってしまうので、必要量の1.5 〜５倍、好ましくは
２〜４倍当量とする。Ｂ2 Ｏ3 から還元されたＢは、溶
融Ｃa を通ってＮd2Ｆe17 相中へ拡散する。液相を媒介
とするので迅速かつ均一な拡散が行える。またＣa はＮ
d2Ｆe17 粉末表面で酸化されたＮd を還元する役割も果
たす。熱処理温度の上限は2-14-1相の融点（Ｎd2Ｆe14
Ｂの場合1155℃、Ｎd2Ｆe17 相の場合1185℃）の内低い
方の温度とする。この温度を超えると溶融反応を生じて
Ｆe 等の粗大粒が形成され、数十nm以下の微細分散組織
とすることが難しい。熱処理下限温度はＣa 融点（ 839
℃）であるが、添加元素により融点が低下した場合はそ
の温度まで下げることが可能である。熱処理後は通常の
還元拡散法と同様Ｃa の水洗、乾燥を行うことにより目
的とする微細分散組織から成る主相合金が得られる。Ｒ
m Ｍn 金属間化合物を用いる場合も、同様にして行えば
よい。In the following, a description will be given of Nd 2 Fe 17 as an example. The manufacturing process of the rare earth permanent magnet of the present invention is carried out by roughly pulverized Nd 2 F 17.
e 17 Compound, B 2 O 3 powder, a metal Ca particles by mixing and pressing a heat treatment at a high temperature in an inert gas atmosphere. Powder such as metal B or boric acid may be used instead of B 2 O 3 . B 2 O
The mixing ratio of 3 to the Nd 2 Fe 17 alloy depends on the type of soft phase to be formed. For example, when Fe is formed, Nd of Nd 2 Fe 17 is necessary to form the 2-14-1 phase. 0.8 to 1.5 times the equivalent B equivalent, and when producing Fe 2 B, the B 2 O 3 amount of 0.8 is sufficient to supply the B equivalent required to form the 2-14-1 phase and the Fe 2 B phase. Double to 1.5 times. Also, the mixing ratio of metal Ca is 1.5 to 5 times, preferably 2 to 4 times the required amount, because if all necessary Ca for reducing B 2 O 3 remains at the required equivalent, all Ca becomes CaO and the liquid phase disappears. Double equivalent. B reduced from B 2 O 3 diffuses through the molten Ca into the Nd 2 Fe 17 phase. Because of the liquid phase, rapid and uniform diffusion can be achieved. Ca is N
It also plays a role in reducing Nd oxidized on the surface of the d 2 Fe 17 powder. The upper limit of the heat treatment temperature is the melting point of the 2-14-1 phase (Nd 2 Fe 14
B, 1155 ° C, and Nd 2 Fe 17 phase, 1185 ° C). If the temperature is exceeded, a melting reaction occurs to form coarse particles such as Fe, and it is difficult to obtain a finely dispersed structure of several tens nm or less. The lower limit temperature of the heat treatment is Ca melting point (839
° C), but when the melting point is lowered by the added element, it can be lowered to that temperature. After the heat treatment, Ca is washed with water and dried in the same manner as in the ordinary reduction diffusion method to obtain a desired main phase alloy having a finely dispersed structure. R
In the case of using the MMn intermetallic compound, the same operation may be performed.
【００１３】従来のＮd-Ｆe-Ｂ焼結磁石は2-14-1主相、
Ｎd-rich相、Ｂ-rich 相の３相からなり、低融点Ｎd-ri
ch相が液相焼結の焼結助剤として必要不可欠である。こ
のため溶融時の組成は３相共存域内にある。本発明にお
いては上記方法によって作製した微細分散組織粉体を2-
14-1単相の代わりに主相合金粉体とするが、これだけで
はＮd-rich相、Ｂ-rich 相が得られないため、これらの
後２相に相当する組成粉末を別途用意しておき、主相合
金粉体と混合する。後２相に相当する合金は、希土類元
素：20〜40at％、Ｂ：０〜10at％、残部がＦe またはＭ
なる組成範囲からなり、鋳造法、液体急冷法、Ｒ＆Ｄ法
等を用いて製造する。その後の工程は従来のＮd-Ｆe-Ｂ
焼結磁石と同様に、該混合粉体を微粉砕した後、磁場中
配向プレス、焼結する。焼結工程においてＮd-rich相は
液化して主相表面をクリーニングすると共に粒成長、密
度化を促進し、保磁力を増大させる。前述のように1100
℃程度の焼結温度においても、分散したソフト相は2-14
-1相内を拡散し難いため、上記微細分散組織はその構造
を保持している。The conventional Nd-Fe-B sintered magnet has a 2-14-1 main phase,
It consists of three phases, Nd-rich phase and B-rich phase, and has a low melting point Nd-ri
The ch phase is indispensable as a sintering aid for liquid phase sintering. Therefore, the composition at the time of melting is within the three-phase coexistence region. In the present invention, the finely dispersed tissue powder produced by the above method is
14-1 The main phase alloy powder is used instead of the single phase. However, the Nd-rich phase and the B-rich phase cannot be obtained with this alone, so the composition powders corresponding to the latter two phases are separately prepared. , Mixed with the main phase alloy powder. The alloys corresponding to the latter two phases are rare earth elements: 20 to 40 at%, B: 0 to 10 at%, and the balance Fe or M
It is manufactured by a casting method, a liquid quenching method, an R & D method, or the like. The subsequent process is the same as the conventional Nd-Fe-B
Like the sintered magnet, the mixed powder is finely pulverized, and then orientation-pressed and sintered in a magnetic field. In the sintering process, the Nd-rich phase is liquefied to clean the surface of the main phase, promote grain growth and density, and increase coercive force. 1100 as described above
Even at a sintering temperature of about ℃, the dispersed soft phase is 2-14
-1 Since it is difficult to diffuse in the phase, the finely dispersed structure retains its structure.
【００１４】本発明の作用は、Ｎd2Ｆe17 もしくはＲm
Ｍn 化合物中へのＢの還元拡散にＣa 液相を使用するこ
とによって、拡散が促進されかつ均一微細分散組織を発
達させたことにある。The effect of the present invention is that Nd 2 Fe 17 or R m
The use of the Ca liquid phase for the reductive diffusion of B into the Mn compound promotes the diffusion and develops a uniform finely dispersed structure.
【実施例】以下、本発明の実施の形態を実施例を挙げて
具体的に説明するが、本発明はこれらに限定されるもの
ではない。 （実施例１）Ｎd メタル、Ｆe メタルを原子百分比で
２：17になるように秤量し、高周波溶解炉にてＡr 雰囲
気下に溶解した。得られた試料を1100℃×10hr加熱して
溶体化処理を行ったのち粗粉砕して、粒径40mesh以下の
Ｎd2Ｆe17 原料粉末を得た。上記原料粉を粒径 150mesh
以下のＢ2 Ｏ3 とＶミキサーにて混合した後、さらに金
属Ｃa 粒を加えて混合し、プレスした。Ｎd2Ｆe17 ：Ｂ
2 Ｏ3 ：Ｃa の秤量割合は分子モル比で２：１：９とし
た。Ｂ2 Ｏ3 は還元後のＢがＮd2Ｆe17 全てをＮd2Ｆe
14 Ｂとするのに必要な量、Ｃa はＢ2 Ｏ3 をすべてＢ
に還元するのに必要な量の３倍に相当する。プレスした
試料をＡr 雰囲気下熱処理炉内で 900℃×１hr熱処理し
冷却した。炉から取り出した試料は 100μｍ程度に粉砕
した後、弱アルカリ水溶液中で水洗し、Ｃa 及びＣa Ｏ
を除去してから真空乾燥した。以上の工程により目的と
するＮd2Ｆe14 Ｂ／Ｆe 微細分散組織を有する主相粉体
が得られた。これとは別にＮd-30−Ｆe-20−Ｃo-10−Ｂ
-40 原子％なる平均組成を持つ合金粉末を高周波溶解に
より作製した。これを上記主相粉体とともにＶミキサー
にて混合後、ジェットミルで平均粒径３〜４μｍまで微
粉砕した。さらにこの粉末を15kOe 磁場中で磁場方向に
配向させながら圧力0.7Ton/cm2でプレス成形した。成形
体をＡr 雰囲気中で1100℃×１hr焼結し、室温冷却して
から 500〜 650℃×１hrの時効処理を行った。上記工程
により作製された焼結磁石の磁気特性を表１に示す。The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these. (Example 1) Nd metal and Fe metal were weighed in an atomic percentage ratio of 2:17, and were melted in an Ar atmosphere in a high-frequency melting furnace. The obtained sample was heated at 1100 ° C. for 10 hours to perform a solution treatment, and then coarsely pulverized to obtain a Nd 2 Fe 17 raw material powder having a particle size of 40 mesh or less. The above raw material powder has a particle size of 150mesh
After mixing with the following B 2 O 3 using a V mixer, metal Ca particles were further added, mixed and pressed. Nd 2 Fe 17 : B
The weighing ratio of 2 O 3 : Ca was 2: 1: 9 in terms of molecular molar ratio. B 2 O 3 is obtained by reducing B to convert all Nd 2 Fe 17 to Nd 2 Fe.
The amount required to make 14 B, Ca is B 2 O 3
3 times the amount required to reduce The pressed sample was heat-treated at 900 ° C. for 1 hour in a heat treatment furnace in an Ar atmosphere and cooled. The sample taken out of the furnace was pulverized to about 100 μm, washed with a weak alkaline aqueous solution, and washed with Ca and CaO.
And vacuum dried. Through the above steps, a target main phase powder having a desired Nd 2 Fe 14 B / Fe fine dispersion structure was obtained. Apart from this, Nd-30-Fe-20-Co-10-B
An alloy powder having an average composition of -40 atomic% was prepared by high frequency melting. This was mixed with the main phase powder by a V mixer, and then finely pulverized by a jet mill to an average particle size of 3 to 4 μm. Further, this powder was press-formed at a pressure of 0.7 Ton / cm 2 while orienting in a magnetic field direction in a 15 kOe magnetic field. The molded body was sintered at 1100 ° C for 1 hour in an Ar atmosphere, cooled at room temperature, and then subjected to an aging treatment at 500 to 650 ° C for 1 hour. Table 1 shows the magnetic properties of the sintered magnet manufactured by the above steps.
【００１５】[0015]
【表１】 [Table 1]
【００１６】（実施例２）Ｂ2 Ｏ3 の代わりに粒径325m
esh 以下のＢ粉末を用い、混合比をモル比でＮd2 Ｆe17:
Ｂ: Ｃa ＝１: １: ９とした他は実施例１と同様の条件
で作製し、磁気特性を表１に併記した。(Embodiment 2) BTwo OThree Instead of particle size 325m
Using B powder below esh, the mixing ratio is Nd in molar ratio.Two Fe17:
B: Same conditions as in Example 1 except that Ca = 1: 1: 9
And the magnetic properties are also shown in Table 1.
【００１７】（実施例３）Ｂ2 Ｏ3 の代わりに硼酸Ｈ3
ＢＯ3 を用い、混合比をＮd2Ｆe17:Ｈ3 ＢＯ3:Ｃa ＝
１: １: ９としたた他は実施例１と同様の条件で作製
し、磁気特性を表１に併記した。[0017] (Example 3) boric acid H 3 instead of B 2 O 3
Using BO 3 , the mixing ratio was Nd 2 Fe 17 : H 3 BO 3 : Ca =
Except that the ratio was set to 1: 1: 9, it was manufactured under the same conditions as in Example 1, and the magnetic characteristics are also shown in Table 1.
【００１８】（実施例４）Ｎd メタル、Ｆe メタル、Ｃ
o メタルを原子百分率で２:12:５となるように秤量し溶
解した他は実施例１と同様の条件で作製し、磁気特性を
表１に併記した。(Embodiment 4) Nd metal, Fe metal, C
o A metal was prepared under the same conditions as in Example 1 except that the metal was weighed and dissolved in an atomic percentage of 2: 12: 5, and the magnetic properties are also shown in Table 1.
【００１９】（実施例５）Ｎd メタル、Ｐr メタル、Ｆ
e メタルを原子百分率（以下、同じ）で1.5:0.5:17とな
るように秤量し溶解した他は実施例１と同様の条件で作
製し、磁気特性を表１に併記した。(Embodiment 5) Nd metal, Pr metal, F
e Metal was prepared under the same conditions as in Example 1 except that the metal was weighed and dissolved in an atomic percentage (hereinafter the same) to be 1.5: 0.5: 17, and the magnetic characteristics were also shown in Table 1.
【００２０】（実施例６）Ｎd メタル、Ｆe メタル、Ｔ
i メタルを１:11:１となるように秤量し溶解したＮd Ｆ
e11 Ｔi 原料粉を用い、Ｎd Ｆe11 Ｔi:Ｂ: Ｃa ＝２：
５：９とした他は実施例２と同様の条件で作製し、磁気
特性を表１に併記した。(Embodiment 6) Nd metal, Fe metal, T
i Nd F dissolved and weighed so that metal becomes 1: 11: 1
Using e 11 Ti raw material powder, NdFe 11 Ti: B: Ca = 2:
Except that the ratio was set to 5: 9, it was manufactured under the same conditions as in Example 2, and the magnetic characteristics are also shown in Table 1.
【００２１】（実施例７）Ｎd メタル、Ｆe メタル、Ｃ
o メタル、Ｔi メタルを１：９：２：１となるように秤
量し溶解した他は実施例６と同様の条件で作製し、磁気
特性を表１に併記した。(Embodiment 7) Nd metal, Fe metal, C
o Metal and Ti metal were prepared under the same conditions as in Example 6 except that they were weighed and dissolved in a ratio of 1: 9: 2: 1, and the magnetic characteristics were also shown in Table 1.
【００２２】（実施例８）Ｎd メタル、Ｆe メタル、Ｍ
o メタルを１：11.5：0.5 となるように秤量し溶解した
原料粉を用い、Ｎd Ｆe11.5 Ｍo0.5 :Ｂ: Ｃa ＝２：
５：９とした他は実施例２と同様の条件で作製し、磁気
特性を表１に併記した。(Embodiment 8) Nd metal, Fe metal, M
The o Metal 1: 11.5: using a raw material powder weighed and dissolved at a 0.5, Nd Fe 11.5 Mo 0.5: B: Ca = 2:
Except that the ratio was set to 5: 9, it was manufactured under the same conditions as in Example 2, and the magnetic characteristics are also shown in Table 1.
【００２３】（実施例９）Ｎd メタル、Ｆe メタル、Ｃ
o メタル、Ｍo メタルを１:9.4:2.1:0.5となるように秤
量し溶解した他は実施例８と同様の条件で作製し、磁気
特性を表１に併記した。(Embodiment 9) Nd metal, Fe metal, C
o Metal and Mo metal were prepared under the same conditions as in Example 8 except that they were weighed and dissolved so as to be 1: 9.4: 2.1: 0.5, and the magnetic characteristics were also shown in Table 1.
【００２４】（実施例１０）混合比をＮd2Ｆe17:Ｂ2 Ｏ
3:Ｃa ＝２：1.5 ：９とした他は実施例１と同様の条件
で作製し、磁気特性を表１に併記した。Example 10 The mixing ratio was Nd 2 Fe 17 : B 2 O
Except that 3 : Ca = 2: 1.5: 9, it was produced under the same conditions as in Example 1, and the magnetic characteristics are also shown in Table 1.
【００２５】（実施例１１）混合比をＮd2Ｆe17:Ｂ: Ｃ
a ＝１：1.3 ：９とした他は実施例２と同様の条件で作
製し、磁気特性を表１に併記した。Example 11 The mixing ratio was Nd 2 Fe 17 : B: C
Except that a = 1: 1.3: 9, it was produced under the same conditions as in Example 2, and the magnetic properties are also shown in Table 1.
【００２６】（比較例）Ｎd メタル、Ｆe メタル及びＦ
e-Ｂ合金を原子比でＮd:Ｆe:Ｂ＝15：77：８となるよう
に秤量し、高周波溶解炉にてＡr 雰囲気下に溶解した。
得られた試料を1100℃×10hr加熱して溶体化処理を行っ
た後、粒径３μｍ以下に粉砕した。さらにこの粉末を15
kOe 磁場中で磁場方向に配向させながら圧力 0.7ton/cm
2 でプレス成形した。成形体をＡr 雰囲気中で1100℃×
１hr焼結し、室温まで冷却してから 600℃×１hrの時効
処理を行った。作製された焼結磁石の磁気特性を表１に
併記する。(Comparative Example) Nd metal, Fe metal and F
The e-B alloy was weighed so that the atomic ratio Nd: Fe: B = 15: 77: 8, and was melted in an Ar atmosphere in a high-frequency melting furnace.
The obtained sample was heated at 1100 ° C. for 10 hours to perform a solution treatment, and then pulverized to a particle size of 3 μm or less. Add 15 more of this powder
Pressure 0.7ton / cm while orienting in the direction of the magnetic field in the kOe magnetic field
Press-molded in 2 . The molded body is heated at 1100 ℃ in Ar atmosphere.
After sintering for 1 hour and cooling to room temperature, aging treatment was performed at 600 ° C for 1 hour. Table 1 also shows the magnetic properties of the manufactured sintered magnet.
【００２７】[0027]
【発明の効果】本発明によれば、最大エネルギー積ＢＨ
max が大きく、磁気的異方性を持つＮd-Ｆe-Ｂ系希土類
永久磁石が得られ、かつ還元拡散剤に金属Ｃa を使用す
るので原料コストの低減が図れる等、産業上その利用価
値は極めて高い。According to the present invention, the maximum energy product BH
Nd-Fe-B rare earth permanent magnets with large max and magnetic anisotropy can be obtained, and the use of metal Ca as a reducing and diffusing agent can reduce raw material costs. high.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 徳永 勝志 神奈川県川崎市高津区坂戸３丁目２番１号 信越化学工業株式会社コーポレートリサ ーチセンター内 (72)発明者 伊藤 卓 福井県武生市北府２丁目１番５号 信越化 学工業株式会社磁性材料研究所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Katsushi Tokunaga 3-2-1 Sakado, Takatsu-ku, Kawasaki City, Kanagawa Prefecture Inside the Corporate Research Center Shin-Etsu Chemical Co., Ltd. (72) Inventor Taku Ito 2-chome Kitafu, Takefu City, Fukui Prefecture No. 1-5 Shin-Etsu Kagaku Kogyo Co., Ltd. Magnetic Materials Research Laboratory
Claims (6)
であるＮd2Ｆe14 Ｂ相中にＦe またはＦe を含む合金も
しくは金属間化合物が微細に分散した組織から成る希土
類永久磁石の製造方法において、式 Ｎd2Ｆe17 で表さ
れる金属間化合物を原料とし、該金属間化合物相にＢ元
素を拡散させて、磁気的異方性および前記微細分散組織
を有する主相Ｎd2Ｆe14 Ｂを得ることを特徴とする希土
類永久磁石の製造方法。1. A rare earth permanent magnet composed of elements of Nd, Fe, and B and having a structure in which Fe or an alloy or intermetallic compound containing Fe is finely dispersed in a main phase of Nd 2 Fe 14 B phase. In the production method, the intermetallic compound represented by the formula Nd 2 Fe 17 is used as a raw material, and element B is diffused into the intermetallic compound phase to form a main phase Nd 2 having magnetic anisotropy and the finely dispersed structure. A method for producing a rare earth permanent magnet, wherein Fe 14 B is obtained.
金属間化合物Ｎd2Ｆe17 および金属Ｃa から成る混合粉
体を熱処理して、ＢをＮd-Ｆe 金属間化合物中に拡散さ
せることを特徴とする請求項１に記載の希土類永久磁石
の製造方法。2. One or more of B, B 2 O 3 or boric acid,
2. The method for producing a rare earth permanent magnet according to claim 1, wherein the mixed powder composed of the intermetallic compound Nd 2 Fe 17 and the metal Ca is heat-treated to diffuse B into the Nd-Fe intermetallic compound.
作製したＮd2Ｆe14 Ｂ主相中にＦe またはＦe を含む合
金もしくは金属間化合物が微細に分散した組織を主相と
する磁石が、磁気的異方性を有していることを特徴とす
る希土類永久磁石の製造方法。3. A magnet whose main phase is a structure in which Fe or an alloy or an intermetallic compound containing Fe is finely dispersed in the Nd 2 Fe 14 B main phase produced by the production method according to claim 1 or 2. And a method of manufacturing a rare earth permanent magnet having magnetic anisotropy.
内１種以上４種以下）、元素Ｍ（ＭはＲ、Ｂを除くＣo、
Ｎi、Ａl、Ｓi、Ｇa、Ａg、Ａu、Ｃu、Ｖ、 Ｃr、Ｍn、Ｓc 、 Ｍo、
Ｗ、 Ｔi、Ｈf、Ｔa、Ｎb、Ｚr、Ｐd、Ｐt、Ｚn、Ｇe、Ｓb、Ｓn お
よびＩn から選択される１種以上５種以下の元素で、少
なくともＦe を含む）およびＢを含む３種以上の元素か
ら成り、かつその主相であるＲ2 Ｍ14Ｂ相中にＦe また
はＦe を含む合金もしくは金属間化合物が微細に分散し
た組織から成る希土類永久磁石の製造方法において、式
Ｒm Ｆen で表される金属間化合物（ここにm、n は正
の整数で、原子比 n/m＞7.0 とする）を原料とし、該金
属間化合物相にＢ元素を拡散させて、磁気的異方性およ
び前記微細分散組織を有する主相Ｒ2 Ｍ14Ｂを得ること
を特徴とする希土類永久磁石の製造方法。4. A rare earth element R (R is one or more and four or less rare earth elements including Y), an element M (M is R, Co other than B,
Ni, Al, Si, Ga, Ag, Au, Cu, V, Cr, Mn, Sc, Mo,
And at least one element selected from W, Ti, Hf, Ta, Nb, Zr, Pd, Pt, Zn, Ge, Sb, Sn and In, including at least Fe, and B In a method for manufacturing a rare-earth permanent magnet composed of the above elements and having a structure in which Fe or an alloy or an intermetallic compound containing Fe is finely dispersed in the main phase of the R 2 M 14 B phase, the formula R m Fe Using an intermetallic compound represented by n (where m and n are positive integers and an atomic ratio of n / m> 7.0) as a raw material, element B is diffused into the intermetallic compound phase, and the A method for producing a rare earth permanent magnet, comprising obtaining a main phase R 2 M 14 B having anisotropy and the finely dispersed structure.
属間化合物Ｒm Ｍn （ここにm、n は正の整数で、原子比
n/m＞7.0 とする）および金属Ｃa から成る混合粉体を
熱処理して、ＢをＲとＭから成る金属間化合物中に拡散
させることを特徴とする請求項４に記載の希土類永久磁
石の製造方法。5. B, B 2 O 3 or one or more of boric acid, the intermetallic compound R m M n (here m, n are positive integers, the atomic ratio
5. The rare-earth permanent magnet according to claim 4, wherein the mixed powder composed of n / m> 7.0) and metal Ca is heat-treated to diffuse B into the intermetallic compound composed of R and M. Production method.
作製したＲ2 Ｍ14Ｂ主相中にＦe またはＦe を含む合金
もしくは金属間化合物が微細に分散した組織を主相とす
る磁石が、磁気的異方性を有していることを特徴とする
希土類永久磁石の製造方法。6. A magnet mainly composed of a structure in which Fe or an alloy or an intermetallic compound containing Fe is finely dispersed in an R 2 M 14 B main phase produced by the production method according to claim 4 or 5. And a method of manufacturing a rare earth permanent magnet having magnetic anisotropy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24610496A JP3247839B2 (en) | 1996-09-18 | 1996-09-18 | Manufacturing method of rare earth permanent magnet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24610496A JP3247839B2 (en) | 1996-09-18 | 1996-09-18 | Manufacturing method of rare earth permanent magnet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1092616A true JPH1092616A (en) | 1998-04-10 |
| JP3247839B2 JP3247839B2 (en) | 2002-01-21 |
Family
ID=17143550
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24610496A Expired - Fee Related JP3247839B2 (en) | 1996-09-18 | 1996-09-18 | Manufacturing method of rare earth permanent magnet |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1191552A2 (en) * | 2000-09-26 | 2002-03-27 | Nissan Motor Co., Ltd. | Bulk exchange-spring magnet, device using the same, and method of producing the same |
| CN102310196A (en) * | 2011-01-23 | 2012-01-11 | 四川大学 | Method for manufacturing micro parts by sintering under electric field action |
| KR101354138B1 (en) * | 2013-07-30 | 2014-01-27 | 한국기계연구원 | A manufacturing method of powder of nd-fe-b alloy |
| CN105081338A (en) * | 2014-05-08 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Method for preparing mono-dispersed NdFeB nano particles |
-
1996
- 1996-09-18 JP JP24610496A patent/JP3247839B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1191552A2 (en) * | 2000-09-26 | 2002-03-27 | Nissan Motor Co., Ltd. | Bulk exchange-spring magnet, device using the same, and method of producing the same |
| EP1191552A3 (en) * | 2000-09-26 | 2003-02-26 | Nissan Motor Co., Ltd. | Bulk exchange-spring magnet, device using the same, and method of producing the same |
| US6736909B2 (en) | 2000-09-26 | 2004-05-18 | Nissan Motor Co., Ltd. | Bulk exchange-spring magnet, device using the same, and method of producing the same |
| CN102310196A (en) * | 2011-01-23 | 2012-01-11 | 四川大学 | Method for manufacturing micro parts by sintering under electric field action |
| KR101354138B1 (en) * | 2013-07-30 | 2014-01-27 | 한국기계연구원 | A manufacturing method of powder of nd-fe-b alloy |
| CN105081338A (en) * | 2014-05-08 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Method for preparing mono-dispersed NdFeB nano particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3247839B2 (en) | 2002-01-21 |
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