JPH11273920A - R-tm-b permanent magnet - Google Patents
R-tm-b permanent magnetInfo
- Publication number
- JPH11273920A JPH11273920A JP10095477A JP9547798A JPH11273920A JP H11273920 A JPH11273920 A JP H11273920A JP 10095477 A JP10095477 A JP 10095477A JP 9547798 A JP9547798 A JP 9547798A JP H11273920 A JPH11273920 A JP H11273920A
- Authority
- JP
- Japan
- Prior art keywords
- phase
- grain boundary
- interface
- boundary phase
- permanent magnet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000005291 magnetic effect Effects 0.000 claims abstract description 73
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910000767 Tm alloy Inorganic materials 0.000 claims abstract description 12
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 90
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 230000005307 ferromagnetism Effects 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 102100031383 Fibulin-7 Human genes 0.000 abstract 3
- 101000846874 Homo sapiens Fibulin-7 Proteins 0.000 abstract 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 304
- 238000000034 method Methods 0.000 description 86
- 238000012937 correction Methods 0.000 description 42
- 238000005245 sintering Methods 0.000 description 27
- 229910045601 alloy Inorganic materials 0.000 description 26
- 239000000956 alloy Substances 0.000 description 26
- 239000000843 powder Substances 0.000 description 24
- 230000005294 ferromagnetic effect Effects 0.000 description 23
- 230000005415 magnetization Effects 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 230000008859 change Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 13
- 230000005540 biological transmission Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000005381 magnetic domain Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 8
- 238000010899 nucleation Methods 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 8
- 238000010791 quenching Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910000521 B alloy Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005090 crystal field Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 238000000992 sputter etching Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004836 empirical method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013598 vector Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 101100425901 Rattus norvegicus Tpm1 gene Proteins 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、R-TM-B系永久磁石
(R:Yを含む希土類元素、TM:遷移金属)に関し、R-TM-B系
永久磁石原料、R-TM-B系永久磁石中間体及び最終製品で
あるR-TM-B系永久磁石に関する。TECHNICAL FIELD The present invention relates to an R-TM-B permanent magnet
(R: rare earth element containing Y, TM: transition metal), R-TM-B-based permanent magnet raw material, R-TM-B-based permanent magnet intermediate and R-TM-B-based permanent magnet as final product .
【０００２】[0002]
【従来の技術】R-TM-B系永久磁石は優れた磁気特性を持
ち、様々な用途に使用されている。R-TM-B系永久磁石に
は種々の製造方法があるが、代表的な製造方法としては
焼結法と超急冷法がある。焼結法は、例えば特開昭59-4
6008号に開示されているように、特定組成を持つインゴ
ットを平均粒径数μmの単結晶微粉末に粉砕し、これを
磁界中で配向しながら任意の形状に成形した後、焼結し
てバルク状の磁石を得る方法である。超急冷法は、例え
ば特開昭60-9852号に開示されているように、特定組成
を持つ合金を、ロール急冷法などの方法で超急冷してア
モルファス状態にし、ついで熱処理を行うことで微細な
結晶粒を析出させる方法である。超急冷法で得られた磁
石合金は通常粉末状であり、一般的にこれを樹脂と混合
して成形することによりボンド磁石の形態で使用する。
さらに、急冷薄板を粉砕して焼結する方法も用いられて
いる。2. Description of the Related Art R-TM-B permanent magnets have excellent magnetic properties and are used for various purposes. There are various manufacturing methods for R-TM-B permanent magnets, and typical manufacturing methods include a sintering method and a super-quenching method. The sintering method is described in, for example, JP-A-59-4
As disclosed in No. 6008, an ingot having a specific composition is pulverized into a single crystal fine powder having an average particle size of several μm, formed into an arbitrary shape while being oriented in a magnetic field, and then sintered. This is a method of obtaining a bulk magnet. The super-quenching method is, for example, as disclosed in Japanese Patent Application Laid-Open No. 60-9852, an alloy having a specific composition is ultra-quenched into an amorphous state by a method such as a roll quenching method, and then subjected to a heat treatment. This is a method of precipitating a fine crystal grain. The magnet alloy obtained by the rapid quenching method is usually in the form of a powder, and is generally used in the form of a bonded magnet by mixing and molding with a resin.
Further, a method of pulverizing and sintering a quenched thin plate has also been used.
【０００３】[0003]
【発明が解決しようとする課題】このような従来技術で
は、試料作成及び評価を繰り返し行うことにより、磁石
の製造工程の各種の条件を最適化し、経験的に磁石の磁
気特性を向上させている。しかし、このような経験的な
方法では、飛躍的な磁気特性向上を達成することが困難
である。また、永久磁石の組成が異なる場合、それぞれ
試料作成及び評価を繰り返し行う必要がある。In such a prior art, various conditions in the magnet manufacturing process are optimized by repeatedly performing sample preparation and evaluation, and the magnetic properties of the magnet are empirically improved. . However, with such an empirical method, it is difficult to achieve a dramatic improvement in magnetic characteristics. Further, when the composition of the permanent magnet is different, it is necessary to repeatedly perform sample preparation and evaluation.
【０００４】本発明は、高い磁気性能を有するR-TM-B系
永久磁石を設計するための指針を提供することを課題と
する。An object of the present invention is to provide guidelines for designing an R-TM-B permanent magnet having high magnetic performance.
【０００５】[0005]
【課題を解決するための手段】従来、磁石の磁気特性、
なかでも保磁力を決定する主相（磁性相）、粒界相間の
界面の構造が未知であった。このため、従来技術では、
磁石の製造工程の各種の条件を最適化することで、経験
的に磁石の磁気特性を向上させている。このような経験
的な手法は、試料作成及び評価のための時間及び費用が
かかる上に、磁石特性の向上には限界がある。Means for Solving the Problems Conventionally, the magnetic properties of a magnet,
Above all, the structure of the interface between the main phase (magnetic phase) that determines the coercive force and the grain boundary phase was unknown. For this reason, in the prior art,
By optimizing various conditions in the magnet manufacturing process, the magnetic properties of the magnet are empirically improved. Such an empirical method takes time and expense for sample preparation and evaluation, and has a limit in improving magnet properties.
【０００６】そこで、本発明者らは、経験的な手法に依
拠せず、理想的な界面の構造はどうあるべきかという根
本的な問題を探求した結果、核生成型の保磁力発生機構
を示す種々の磁石材料において、核生成の容易さが磁石
相の最外殻近傍における結晶磁気異方性の大きさに依存
しており、最外殻近傍の異方性定数K1の値を少なくとも
内部と同等、もしくはそれ以上に制御することにより核
生成が抑制され、磁石の保磁力を高めることができるこ
とを見出し、さらに鋭意研究を進めた結果、本発明を完
成するに至ったものである。The present inventors have investigated the fundamental problem of what the ideal interface structure should be, without relying on an empirical method. As a result, the present inventors have developed a nucleation-type coercive force generation mechanism. in various magnetic materials, ease of nucleation depends on the size of the crystal magnetic anisotropy in the outermost shell near the magnet phases, the value of the anisotropy constant K 1 of the outermost shell near at least showing It has been found that nucleation can be suppressed and the coercive force of the magnet can be increased by controlling it to be equal to or more than the inside, and as a result of further intensive research, the present invention has been completed.
【０００７】本発明は第１の視点において次の要素を有
する。結晶構造が正方晶であるR2TM14B金属間化合物(R:
Yを含む希土類元素、TM:遷移金属)から主としてなる磁
性相。R3TM合金から主としてなる粒界相。磁性相と粒界
相の界面近傍における粒界相の結晶構造が斜方晶構造で
あること。磁性相と粒界相が整合していること。第２の
視点においては、R2TM14B金属間化合物において、R中の
NdとPrの合計が50at%以上。TMはFeまたはCoでTM中のFe
が50at%以上。 R3TM合金において、Rが90at%以上。第３
の視点においては、R2TM14B金属間化合物において、TM
中のFeが50at%以上。TM中のCoが0.1at%以上。R3TM金属
間化合物において、TM中のCoが90at%以上。第４の視点
においては、前記第１の視点に基づき磁性相と粒界相の
界面近傍における結晶学的方位関係が、下記の少なくと
も一組で表されること。方位関係のずれの角度が5°以
内であること。[0007] The first aspect has the following elements. R 2 TM 14 B intermetallic compound having a tetragonal crystal structure (R:
A magnetic phase mainly composed of a rare earth element containing Y (TM: transition metal). Grain boundary phase mainly composed of R 3 TM alloy. The crystal structure of the grain boundary phase near the interface between the magnetic phase and the grain boundary phase is an orthorhombic structure. The magnetic phase and the grain boundary phase must match. In a second aspect, in the R 2 TM 14 B intermetallic compound,
The sum of Nd and Pr is 50at% or more. TM is Fe or Co and Fe in TM
Is 50at% or more. R is 90at% or more in R 3 TM alloy. Third
From the viewpoint of R 2 TM 14 B intermetallic compound, TM
Fe inside is 50at% or more. Co in TM is 0.1at% or more. In the R 3 TM intermetallic compound, Co in the TM is 90 at% or more. In a fourth aspect, the crystallographic orientation relationship near the interface between the magnetic phase and the grain boundary phase is represented by at least one of the following sets based on the first aspect. The misalignment angle of the azimuth relationship must be within 5 °.
【０００８】[0008]
【化２】 Embedded image
【０００９】第５の視点においては、結晶構造が正方晶
である磁性相を含むこと。磁性相との界面近傍における
結晶構造が斜方晶である粒界相を含むこと。磁性相と粒
界相が界面を挟んで整合していること。第６の視点にお
いては、強磁性を発揮するR2TM14B金属間化合物(R:Yを
含む希土類元素、TM:遷移金属)源と、R3TM合金源を用い
ること。R2TM14B正方晶を析出すること。R2TM14B正方晶
相の周囲（周囲の一部又は全部）にR3TM斜方晶を析出す
ること。R2TM14B正方晶相とR3TM斜方晶相を整合させ、
整合した界面近傍のR2TM14B正方晶相の結晶磁気異方性
を高めること。According to a fifth aspect, a magnetic phase having a tetragonal crystal structure is included. The crystal structure near the interface with the magnetic phase includes a grain boundary phase that is orthorhombic. The magnetic phase and the grain boundary phase are aligned across the interface. In a sixth aspect, an R 2 TM 14 B intermetallic compound (R: a rare earth element including Y, TM: transition metal) source exhibiting ferromagnetism, and an R 3 TM alloy source are used. Precipitating R 2 TM 14 B tetragonal crystals. Precipitating R 3 TM orthorhombic around (part of or all around) R 2 TM 14 B tetragonal phase. Match the R 2 TM 14 B tetragonal phase and the R 3 TM orthorhombic phase,
Enhancing the magnetocrystalline anisotropy of the R 2 TM 14 B tetragonal phase near the aligned interface.
【００１０】ここで、R2TM14B金属間化合物の（好まし
くは単結晶体）からなる主相（強磁性相）と、R3TM合金
からなる粒界相とから主として構成されるR-TM-B系永久
磁石を例として、本発明の原理を説明する。なお、R-TM
-B系永久磁石中には上述の主相、粒界相以外にもB-rich
相(R1+ αTM4B4)、R-TM準安定相、工程中で不可避的に形
成される酸化物、および炭化物などが存在することが知
られているが、これらの相が該永久磁石の磁気特性に及
ぼす影響は該主相、該粒界相の二相と比べて副次的であ
る。Here, an R-TM-B-based permanent magnet mainly composed of a main phase (ferromagnetic phase) composed of a R2TM14B intermetallic compound (preferably a single crystal) and a grain boundary phase composed of an R3TM alloy As an example, the principle of the present invention will be described. In addition, R-TM
In addition to the main phase and grain boundary phase described above, B-rich
Phase (R 1+ α TM 4 B 4 ), R-TM meta-stable phase, oxides are inevitably formed during the process, and the like carbides that are known to exist, these phases the The effect on the magnetic properties of the permanent magnet is secondary compared to the two phases of the main phase and the grain boundary phase.
【００１１】R-TM-B系永久磁石において、TM中にCoを含
有させるとキュリー温度が高まったり，耐食性が向上す
ることが知られており、これらの目的でR-TM-B系永久磁
石中に適当な量のCoを添加することは公知の技術であ
る。上述の方法以外にも、メカニカルアロイング法、ホ
ットプレス法、熱間圧延法、HDDR法など様々な公知の製
造方法がある。しかし、すべてのR-TM-B系永久磁石は、
その製造方法の如何に関わらず、R2TM14B金属間化合物
の単結晶体からなる主相と，R3TM金属間化合物からなる
粒界相の少なくとも二相で構成される。In R-TM-B permanent magnets, it is known that the inclusion of Co in TM increases the Curie temperature and improves corrosion resistance. For these purposes, R-TM-B permanent magnets are known. It is a known technique to add an appropriate amount of Co therein. In addition to the above methods, there are various known manufacturing methods such as a mechanical alloying method, a hot press method, a hot rolling method, and an HDR method. However, all R-TM-B permanent magnets
Regardless of the manufacturing process, the main phase made of a single crystal of R 2 TM 14 B intermetallic compound, composed of at least two phases of grain boundary phase composed of R 3 TM intermetallic compound.
【００１２】粒界相の存在は磁石の保磁力の発現に必要
であり、一般に磁石の組成中に粒界相の形成に必要なR
成分が不足してくると保磁力は低下する。これは、R成
分の不足によってR2TM14B相とR3TM相の二相が平衡状態
で共存できなくなり、かわりにR2TM17相などの強磁性相
がR2TM14B相の粒界に析出し、そこが逆磁区発生の起点
となり、容易に磁化反転して保磁力が低下するためと考
えられている。The presence of the grain boundary phase is necessary for the development of the coercive force of the magnet.
If the components become insufficient, the coercive force decreases. This is because the R 2 TM 14 B phase and the R 3 TM phase cannot coexist in an equilibrium state due to the lack of the R component, and instead, the ferromagnetic phase such as the R 2 TM 17 phase replaces the R 2 TM 14 B phase. It is thought that it precipitates at the grain boundary, and this becomes the starting point of the generation of the reverse magnetic domain, which causes the magnetization to be easily inverted and the coercive force to be reduced.
【００１３】また、焼結法で作製したR-TM-B系永久磁石
に実用上十分な保磁力を与えるためには主相と粒界相と
が格子欠陥のないスムーズな界面で接していることが必
要であることが、透過電子顕微鏡による該界面のミクロ
な観察で明らかにされている。この理由は、界面に格子
欠陥などが存在すると、そこが逆磁区発生の起点とな
り、容易に磁化反転して保磁力が低下するためと説明さ
れている。In order to provide a practically sufficient coercive force to the R-TM-B permanent magnet produced by the sintering method, the main phase and the grain boundary phase are in contact at a smooth interface free from lattice defects. It is clear from the microscopic observation of the interface with a transmission electron microscope that this is necessary. The reason is described as follows: if a lattice defect or the like is present at the interface, this becomes the starting point of the generation of a reverse magnetic domain, and the magnetization is easily inverted to lower the coercive force.
【００１４】本発明者らは、上記の従来技術によるR-TM
-B系永久磁石の持つ優れた磁気特性を発現させる上で、
該永久磁石を構成する粒界相の好ましい形態について以
下の問題点があることを知見した。すなわち、従来の技
術ではR3TM粒界相が存在する組成領域や、主相と粒界相
との界面の欠陥の有無についての知見は得られていたも
のの、R3TM粒界相の結晶構造と、その主相との好ましい
方位関係については知られていなかった。このため、特
定の組成を持つR-TM-B系永久磁石のミクロな構造を制御
して優れた磁気特性を発現させることは不可能であっ
た。そのかわりに、従来技術では、磁石の製造工程の各
種の条件を最適化することで、経験的に磁石の磁気特性
を向上させていた。The present inventors have proposed the above-mentioned prior art R-TM.
-To express the excellent magnetic properties of B-based permanent magnets,
It has been found that the preferred form of the grain boundary phase constituting the permanent magnet has the following problems. That is, in the prior art, although knowledge was obtained about the composition region where the R 3 TM grain boundary phase exists and the presence or absence of defects at the interface between the main phase and the grain boundary phase, the crystal of the R 3 TM grain boundary phase was No known orientation relation between the structure and its main phase was known. For this reason, it has not been possible to control the microstructure of the R-TM-B permanent magnet having a specific composition to develop excellent magnetic properties. Instead, in the prior art, the magnetic properties of the magnet were empirically improved by optimizing various conditions in the magnet manufacturing process.
【００１５】すなわち、磁石の磁気特性、なかでも保磁
力を決定する主相、粒界相間の界面の構造が未知であっ
たため、界面の構造を変化させると思われるさまざまな
処理(例えば熱処理など)を磁石に施して、界面の状態は
ブラックボックスのまま磁石特性を制御していたことに
なる。このようなやり方は、個々の組成の磁石の製造条
件を最適化する上では支障がなかったが、理想的な界面
の構造はどうあるべきかという材料開発上の指針がない
ままでは、磁石特性をさらに向上させるのは極めて困難
であった。In other words, since the magnetic properties of the magnet, particularly the structure of the interface between the main phase and the grain boundary phase that determine the coercive force, are unknown, various treatments (such as heat treatment) that are thought to change the structure of the interface Is applied to the magnet, and the state of the interface is controlled as a black box while the magnet characteristics are controlled. Such a method did not hinder the optimization of the manufacturing conditions for magnets of individual compositions, but without the guidelines for material development on what the ideal interface structure should be, the magnet properties Was extremely difficult to further improve.
【００１６】本発明者らは、透過電子顕微鏡(TEM)を用
いて、種々のR-TM-B系永久磁石の粒界相のミクロな解析
を行った結果、Coを含有するすべてのR-TM-B系永久磁石
の粒界に斜方晶の結晶構造を持つR3TM金属間化合物(TM
中のCoが90at%以上)からなる粒界相が存在し、主相と粒
界相が互いに界面で接しているときに優れた磁気特性が
得られることを知見した。The present inventors conducted a microscopic analysis of the grain boundary phase of various R-TM-B-based permanent magnets using a transmission electron microscope (TEM). R 3 TM intermetallic compound (TM) with an orthorhombic crystal structure at the grain boundaries of TM-B permanent magnets
It was found that excellent magnetic properties were obtained when the main phase and the grain boundary phase were in contact with each other at the interface.
【００１７】また、本発明者らは、上記の斜方晶構造を
もつR3TM粒界相が存在するR-TM-B系永久磁石の粒界相と
主相(R2TM14B相)との界面の構造について、高分解能透
過電子顕微鏡(HR-TEM)や走査トンネル顕微鏡などで詳細
に観察した結果、主相と粒界相とが界面近傍において特
定の結晶学的方位関係を持つようにミクロ組織が制御さ
れ、両相が整合しているつときに磁気特性が最も高くな
ることを見出したものである。Further, the present inventors have proposed that the grain boundary phase and the main phase (R 2 TM 14 B phase) of the R-TM-B permanent magnet in which the R 3 TM grain boundary phase having the above-described orthorhombic structure exists. As a result of detailed observation of the structure of the interface with) using a high-resolution transmission electron microscope (HR-TEM) or scanning tunneling microscope, the main phase and the grain boundary phase have a specific crystallographic orientation relationship near the interface Thus, it has been found that the magnetic properties are maximized when the microstructure is controlled and both phases are matched.
【００１８】図１、図２（Ａ）及び（Ｂ）を参照して、
主相（強磁性相）と粒界相がその界面で整合している場
合と、整合していない場合とで、界面近傍における結晶
磁気異方性の分布の相違を説明する。図１又は図２
（Ａ）及び（Ｂ）において、横軸の"最外殻"とは主相の
最も外側の原子層の位置を示し、"第２層"、"第３層"と
はそれぞれ最外殻位置から内部に向かって数えて２番
目、３番目の原子層の位置を示す。第ｎ層とは最外殻か
らの距離が遠く、界面からの影響が無視できる位置を示
す。図１のグラフ中、縦軸は主相の一軸異方性定数K
1（結晶磁気異方性の強さを示す）の大きさを示し、K1
の値が大きいほど主相の自発磁化の向きは磁化容易軸
（ｃ軸）の方向で安定化する。また、図１中、実施例
（本発明）は図２（Ａ）に示すように主相と粒界相が界
面で整合している条件でのK1の計算値を示し、比較例は
図２（Ｂ）に示すように粒界相の欠落などによって界面
の不整合などがある場合のK1の計算値を示している。Referring to FIGS. 1, 2A and 2B,
The difference in the distribution of magnetocrystalline anisotropy near the interface between the case where the main phase (ferromagnetic phase) and the grain boundary phase match at the interface and the case where they do not match will be described. FIG. 1 or FIG.
In (A) and (B), the “outermost shell” on the horizontal axis indicates the position of the outermost atomic layer of the main phase, and the “second layer” and “third layer” indicate the outermost shell positions, respectively. The positions of the second and third atomic layers counted from the inside toward the inside are shown. The n-th layer indicates a position where the distance from the outermost shell is long and the influence from the interface can be ignored. In the graph of FIG. 1, the vertical axis represents the uniaxial anisotropy constant K of the main phase.
1 (indicating the strength of crystal magnetic anisotropy), and K 1
Is larger, the direction of the spontaneous magnetization of the main phase is stabilized in the direction of the axis of easy magnetization (c-axis). In FIG. 1, the example (the present invention) shows the calculated value of K 1 under the condition that the main phase and the grain boundary phase are matched at the interface as shown in FIG. 2 (A). As shown in FIG. 2B, the calculated value of K1 in the case where there is an interface mismatch due to a lack of a grain boundary phase or the like is shown.
【００１９】図１を参照して、比較例においては、界面
からの距離によって異方性定数K1の大きさが大きく変化
し、最外殻におけるK1の値が内部に比べて著しく低下し
ている。一方、実施例においては、界面からの距離によ
って異方性定数K1の大きさがあまり変化せず、むしろ最
外殻相において異方性定数K1が上昇している。従って、
比較例によれば、最外殻において逆磁区の核生成に要す
るエネルギーが局所的に低下して核生成と磁化反転が容
易になるため、磁石の保磁力が低下する。一方、実施例
によれば、最外殻におけるK1がむしろ内部より高いた
め、界面における逆磁区の核生成が抑制され、その結果
磁石の保磁力が増加する。[0019] Referring to FIG. 1, in the comparative example, vary greatly in size of the anisotropy constant K 1 by the distance from the interface, the value of K1 is significantly lower than that inside the outermost shell I have. On the other hand, in the embodiment, without much change in the magnitude of the anisotropy constant K 1 by the distance from the interface, the anisotropy constant K 1 is increased in the outermost shell phase rather. Therefore,
According to the comparative example, the energy required for nucleation of the reverse magnetic domain in the outermost shell is locally reduced, and nucleation and magnetization reversal are facilitated, so that the coercive force of the magnet is reduced. On the other hand, according to the embodiment, since K 1 in the outermost shell is rather higher than that in the inner part, nucleation of reverse magnetic domains at the interface is suppressed, and as a result, the coercive force of the magnet increases.
【００２０】[0020]
【発明の実施の形態】本発明の好ましい実施の形態につ
いて、焼結法を例にとって説明する。他の公知のR-TM-B
系永久磁石の製造方法においても、好ましい界面の構造
を発現する具体的な方法については焼結法と同様であ
る。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described by taking a sintering method as an example. Other known R-TM-B
In the method for producing a permanent magnet, a specific method of developing a preferable interface structure is the same as that of the sintering method.
【００２１】原料として、特開昭59-46008号に開示され
ているような公知の組成のR-TM-B合金を用いることがで
きる。R中のNdとPrの合計が50at%未満だと、得られる磁
石の保磁力と残留磁化が著しく低下するので、R中のNd
とPrの合計は50at%以上が好ましく、また、保磁力を向
上させるためにNdの一部をDyやTbで置換することも好ま
しい。TMはFe、またはCoであるが、TM中のFeが50at%未
満だと得られる磁石の保磁力と残留磁化が低下するの
で、TM中のFeは50at%以上が好ましい。また、キュリー
温度を高め、耐食性を向上する目的で、TM中のCoを0.1a
t%以上とすることが好ましい。この他、さまざまな目的
で上記以外の添加元素を添加することも可能である。As a raw material, an R-TM-B alloy having a known composition as disclosed in JP-A-59-46008 can be used. If the total of Nd and Pr in R is less than 50 at%, the coercive force and remanent magnetization of the obtained magnet will be significantly reduced, so the Nd in R
The total of Pr and Pr is preferably at least 50 at%, and it is also preferable to partially replace Nd with Dy or Tb in order to improve the coercive force. TM is Fe or Co. However, if the content of Fe in the TM is less than 50 at%, the coercive force and the residual magnetization of the obtained magnet are reduced. Therefore, the content of Fe in the TM is preferably 50 at% or more. In addition, to increase the Curie temperature and improve corrosion resistance, Co in TM is reduced to 0.1a.
It is preferably at least t%. In addition, it is also possible to add additional elements other than the above for various purposes.
【００２２】さらに好ましい永久磁石は、結晶構造が正
方晶であるR2TM14B金属間化合物(R:Yを含む希土類元素
で、R中のNdとPrの合計が50at%以上、TM:FeおよびCo
で、TM中のFeが50at%以上，TM中のCoが0.1at%以上)の単
結晶体からなる主相と、結晶構造が斜方晶であるR3TM金
属間化合物(TM中のCoが90at%以上)を有する。A more preferred permanent magnet is a R 2 TM 14 B intermetallic compound having a tetragonal crystal structure (a rare earth element containing R: Y, wherein the total of Nd and Pr in R is at least 50 at%, TM: Fe And Co
And a main phase consisting of a single crystal having Fe in the TM of at least 50 at% and Co in the TM of at least 0.1 at%) and an R 3 TM intermetallic compound having an orthorhombic crystal structure (Co in the TM). Is 90 at% or more).
【００２３】永久磁石の平均の組成はR2TM14B相とR3TM
相(TM中のCoが90at%以上)の少なくとも二相が共存でき
る組成範囲であることが必要である。これには、組成範
囲をR:8〜30at%、B:2〜40at%、残部主としてTMとすれば
よい。好ましくは、組成範囲をR:8〜30at%、B:2〜40at
%、Fe:40〜90at%、Co:50at%以下とする。さらに、好ま
しくは組成範囲をR:11〜50at%、B:5〜40at%、残部主と
してTMとすればよい。より好ましくは、組成範囲をR:12
〜16at%、B:6.5〜9at%、残部主としてTMとすればよい。
一層好ましくは、組成範囲をR:12〜14at%、B:7〜8at%、
残部主としてTMとすればよい。また、用いるR-TM-B合金
は必ずしも単一の所要組成からなる必要はなく、異なる
組成の合金を粉砕した後、混合し所要組成に調整して用
いることもできる。The average composition of the permanent magnet is R 2 TM 14 B phase and R 3 TM
It is necessary that the composition range is such that at least two phases of phases (Co in the TM is 90 at% or more) can coexist. For this, the composition range may be R: 8 to 30 at%, B: 2 to 40 at%, and the balance is mainly TM. Preferably, the composition range is R: 8 to 30 at%, B: 2 to 40 at
%, Fe: 40 to 90 at%, Co: 50 at% or less. Further, the composition range is preferably R: 11 to 50 at%, B: 5 to 40 at%, and the balance is mainly TM. More preferably, the composition range is R: 12
Up to 16 at%, B: 6.5 to 9 at%, and the balance may be mainly TM.
More preferably, the composition range is R: 12 to 14 at%, B: 7 to 8 at%,
The remainder may be mainly TM. Further, the R-TM-B alloy to be used does not necessarily have to have a single required composition, and alloys having different compositions may be pulverized, mixed and adjusted to the required composition before use.
【００２４】また、主相において、Bの一部ないし大部
分をC，Si，P，などのいわゆる半金族元素で置換しても
よい。例えば、BをCで置換する場合、B1-xCx、但し好ま
しくはxは少なくとも0.8まで可である。In the main phase, part or most of B may be replaced with a so-called semi-metal group element such as C, Si, P, or the like. For example, if B is replaced by C, then B1-xCx, but preferably x can be at least 0.8.
【００２５】R-TM-B合金を粉末にする方法には、鋳造粉
砕法、急冷薄板粉砕法、超急冷法、直接還元拡散法、水
素含有崩壊法、アトマイズ法などの公知の方法を適宜選
択することができる。合金粉末の平均粒径を1μｍ以上
とすることにより、粉末が大気中の酸素などと反応しに
くく酸化しにくくなり、焼結後の磁気特性が向上する。
また、平均粒径を10μｍ以下とすることにより、焼結密
度が高くなり好ましい。より好ましい平均粒径の範囲は
1〜6μｍである。As a method of turning the R-TM-B alloy into a powder, a known method such as a casting pulverization method, a quenched thin plate pulverization method, a super-quenching method, a direct reduction diffusion method, a hydrogen-containing disintegration method, or an atomizing method is appropriately selected. can do. By setting the average particle size of the alloy powder to 1 μm or more, the powder hardly reacts with oxygen in the atmosphere and hardly oxidizes, and the magnetic properties after sintering are improved.
Further, by setting the average particle size to 10 μm or less, the sintering density is increased, which is preferable. A more preferable range of the average particle size is
1 to 6 μm.
【００２６】得られた合金粉末を金型中に給粉し、磁界
中で配向しながら圧縮成形する。この際に、例えば特開
平8-20801号に開示されているように、合金粉末の流動
成を高めて給粉を容易にする目的で合金粉末にバインダ
ーを添加してスプレー造粒を行うことも好ましい。ある
いは、特開平6-77028号に開示されているように、合金
粉末にバインダーを加えて金属射出成形法によって複雑
形状品の成形を行うことも可能である。これらバインダ
ーを用いた場合は、焼結前に成形体に含まれるバインダ
ーを熱分解によって除去することが好ましい。The obtained alloy powder is fed into a mold, and compression-molded while being oriented in a magnetic field. At this time, for example, as disclosed in JP-A-8-20801, spray granulation may be performed by adding a binder to the alloy powder for the purpose of increasing the fluidity of the alloy powder to facilitate powder supply. preferable. Alternatively, as disclosed in JP-A-6-77028, it is also possible to add a binder to the alloy powder and form a complex-shaped product by a metal injection molding method. When these binders are used, it is preferable to remove the binder contained in the molded body by thermal decomposition before sintering.
【００２７】得られた成形体は真空中、または窒素を除
く不活性ガス中で焼結する。焼結条件はR-TM-B合金粉末
の組成や粒径に応じて適宜選定されるが、例えば1000〜
1180℃で1〜4時間が好ましい。焼結後の冷却速度は粒界
相の結晶構造を制御する上で重要である。すなわち、焼
結温度では粒界相は液相になっており、焼結温度からの
冷却速度があまり早すぎると粒界相は格子欠陥を多く含
んだり、非晶質になったりして好ましくない。The obtained compact is sintered in a vacuum or in an inert gas except nitrogen. The sintering conditions are appropriately selected according to the composition and particle size of the R-TM-B alloy powder.
Preferred is 1180 ° C. for 1-4 hours. The cooling rate after sintering is important for controlling the crystal structure of the grain boundary phase. That is, at the sintering temperature, the grain boundary phase is in a liquid phase, and if the cooling rate from the sintering temperature is too fast, the grain boundary phase contains many lattice defects or becomes amorphous, which is not preferable. .
【００２８】粒界相が斜方晶構造をとるためには、焼結
温度からの冷却速度は10〜200℃/minの範囲内であるこ
とが好ましい。このように冷却に十分時間をかけること
により、液状の粒界相が過冷却にならずに、冷却時に規
則正しい結晶構造をとることが可能になる。粒界相が非
晶質ではなく斜方晶構造をとることにより、主相と粒界
相の界面における原子同士の位置関係が規則正しくな
り、両者の整合性が保たれる結果、界面が逆磁区発生の
起点となる可能性が減少し、高保磁力が実現する。より
好ましい焼結後の冷却速度の範囲は20〜100℃/minであ
る。In order for the grain boundary phase to have an orthorhombic structure, the cooling rate from the sintering temperature is preferably in the range of 10 to 200 ° C./min. By allowing sufficient time for cooling in this way, the liquid grain boundary phase does not become supercooled, but can take a regular crystal structure during cooling. Since the grain boundary phase has an orthorhombic structure instead of being amorphous, the positional relationship between atoms at the interface between the main phase and the grain boundary phase is regular, and the consistency between the two is maintained. The possibility of starting the occurrence is reduced, and a high coercive force is realized. A more preferable range of the cooling rate after sintering is 20 to 100 ° C./min.
【００２９】界面の整合性の効果を得るには、主相と粒
界相の界面近傍のたかだか数原子層の範囲で粒界相の結
晶構造が面心立方構造になっていればよい。また、主相
は一般に粒界相よりも早く形成されており、主相を構成
する結晶粒は単結晶になっているため、主相と粒界相が
整合していることにより、結晶粒内部から外殻に至るま
で結晶粒内の結晶磁気異方性が高くなり、高保磁力が得
られる。In order to obtain the effect of interface consistency, it is sufficient that the crystal structure of the grain boundary phase has a face-centered cubic structure in the range of at most several atomic layers near the interface between the main phase and the grain boundary phase. In addition, the main phase is generally formed earlier than the grain boundary phase, and the crystal grains constituting the main phase are single crystals. The crystal magnetic anisotropy in the crystal grains increases from the surface to the outer shell, and a high coercive force can be obtained.
【００３０】本発明において、強磁性結晶粒はその一部
又は全部が粒界相によって囲まれていることが好まし
い。主相の結晶粒径は10nm〜500μmの範囲にあることが
好ましい。より好ましい結晶粒径の範囲は、例えば焼結
法の場合は10〜30μm、超急冷法の場合は20〜100nmなど
と、それぞれの製法によって異なる。また、主相中に粒
界相を伴わない粒界や双晶粒界、あるいは析出物などが
存在すると磁石の保磁力が低下するため、主相は単結晶
であることが好ましい。In the present invention, the ferromagnetic crystal grains are preferably partially or entirely surrounded by a grain boundary phase. The crystal grain size of the main phase is preferably in the range of 10 nm to 500 μm. The more preferable range of the crystal grain size varies depending on the production method, for example, 10 to 30 μm in the case of the sintering method, and 20 to 100 nm in the case of the ultra-quench method. If the main phase contains a grain boundary without a grain boundary phase, a twin grain boundary, a precipitate, or the like, the coercive force of the magnet decreases. Therefore, the main phase is preferably a single crystal.
【００３１】上記の主相と粒界相の界面における原子同
士の位置関係をさらに理想的に制御するには、主相と粒
界相の結晶学的方位関係を限定することが必要である。
ここで、結晶学的記号の意味を説明する。記号"[hkl]"
はミラー指数がh、k、lで表される結晶面に垂直な法線の
方向を表す。また、記号"[hkl]"の右下に小さな文字で
書かれた"主相"、"粒界相"とは、それぞれの方向が主
相、または粒界相のものであることを示す。例えば、記
号"[001]主相"は主相であるR2TM14B相のｃ軸の方向を表
している。一組の方向指数の間に記された記号"//"は、
これらの方向ベクトルが互いに平行であることを示す。To more ideally control the positional relationship between atoms at the interface between the main phase and the grain boundary phase, it is necessary to limit the crystallographic orientation relationship between the main phase and the grain boundary phase.
Here, the meaning of the crystallographic symbols will be described. Symbol "[hkl]"
Represents the direction of the normal line perpendicular to the crystal plane represented by the Miller index h, k, l. The “main phase” and “grain boundary phase” written in small letters at the lower right of the symbol “[hkl]” indicate that the respective directions are those of the main phase or the grain boundary phase. For example, the symbol “[001] main phase” indicates the direction of the c-axis of the R 2 TM 14 B phase that is the main phase. The symbol "//" between a pair of direction indices
It shows that these direction vectors are parallel to each other.
【００３２】次に、記号"(hkl)"はミラー指数がh、k、lで
表される結晶面を表し、小文字で記された"主相"、"粒
界相"と、記号"//"の意味するところは方向の場合と同
じである。ここで、同一の相についての方向と結晶面の
表記においては、用いられるミラー指数は一般化された
指数ではなく、特定の結晶方向、ないし結晶面を示して
いる。Next, the symbol "(hkl)" represents a crystal plane whose Miller index is represented by h, k, l, and the "main phase", "grain boundary phase" and the symbol "/ The meaning of "/" is the same as for direction. Here, in the notation of the direction and the crystal plane for the same phase, the Miller index used is not a generalized index but indicates a specific crystal direction or crystal plane.
【００３３】[0033]
【化３】 Embedded image
【００３４】界面における特定の結晶方位関係が磁石の
磁気特性を向上させる理由は以下の通りである。すなわ
ち、主相の界面近傍では、主相の結晶磁気異方性を決め
ているR原子の周囲の結晶場が、隣接する粒界相の原子
配列の影響を受けて変化する。R3TM粒界相の結晶方位が
下記の(Ａ)〜(Ｄ)の組み合わせのいずれかの方位になっ
ている場合は、R3TM粒界相のR原子と、主相中のR原子と
が上記の結晶磁気異方性を強める位置関係にあるため、
主相の界面近傍での結晶磁気異方性が高まる。その結
果、粒界近傍での逆磁区発生が困難となり、容易に磁化
反転することができないため保磁力が向上すると考えら
れる。The reason why the specific crystal orientation relationship at the interface improves the magnetic properties of the magnet is as follows. That is, in the vicinity of the interface of the main phase, the crystal field around the R atom that determines the magnetocrystalline anisotropy of the main phase changes under the influence of the atomic arrangement of the adjacent grain boundary phase. When the crystal orientation of the R 3 TM grain boundary phase is one of the following combinations of (A) to (D), the R atom of the R 3 TM grain boundary phase and the R atom of the main phase Are in a positional relationship that enhances the crystal magnetic anisotropy described above,
The magnetocrystalline anisotropy near the interface of the main phase increases. As a result, it is considered that the generation of a reverse magnetic domain near the grain boundary becomes difficult, and the magnetization reversal cannot be easily performed, so that the coercive force is improved.
【００３５】[0035]
【化４】 Embedded image
【００３６】上記の説明において、主相中のR原子の結
晶場に影響を与える粒界相の原子は、主相に隣接する界
面の近傍の原子である。したがって、本発明において、
粒界相の結晶構造上記の主相と粒界相の方位関係は両相
の界面の近傍のたかだか数原子層の範囲で成立していれ
ばよい。In the above description, the atoms in the grain boundary phase that affect the crystal field of R atoms in the main phase are atoms near the interface adjacent to the main phase. Therefore, in the present invention,
Crystal Structure of Grain Boundary Phase The above-mentioned orientation relationship between the main phase and the grain boundary phase may be established within a range of at most several atomic layers near the interface between the two phases.
【００３７】粒界相を特定の結晶方位関係で出現させる
方法としては、焼結後の冷却速度を制御する方法があ
る。すなわち、R3TM粒界相が液相状態である800℃以上
から、原子の拡散が極めて遅くなる300℃以下までの温
度範囲を、10〜200℃/minの冷却速度で冷却することに
より、主相と整合性のある特定の結晶方位関係を持った
粒界相を主相との界面近傍に析出させることができる。
これは、固体状態の主相の表面に、表面エネルギーが最
も低い結晶方位を持つ界面を形成するように斜方晶構造
の粒界相が成長するためである。より好ましい冷却速度
は20〜100℃/minである。As a method of causing the grain boundary phase to appear in a specific crystal orientation relationship, there is a method of controlling a cooling rate after sintering. That is, by cooling the temperature range from 800 ° C. or higher where the R 3 TM grain boundary phase is in a liquid state to 300 ° C. or lower where diffusion of atoms is extremely slow, at a cooling rate of 10 to 200 ° C./min, A grain boundary phase having a specific crystal orientation compatible with the main phase can be precipitated near the interface with the main phase.
This is because a grain boundary phase having an orthorhombic structure grows on the surface of the main phase in a solid state so as to form an interface having a crystal orientation with the lowest surface energy. A more preferred cooling rate is 20 to 100 ° C / min.
【００３８】この際に、主相と粒界相の成分元素、ある
いは組成の違いによって両相の格子定数の比率が異なる
ために、結晶方位が若干ずれることもある。しかし、こ
のずれの角度はたかだか5°以内であるため、たとえず
れたとしても主相中のR原子の結晶場に与える影響は少
なく、所期の効果を発現することができる。At this time, since the ratio of the lattice constants of the main phase and the grain boundary phase differs depending on the component elements or the composition of the two phases, the crystal orientation may be slightly shifted. However, since the angle of this shift is at most 5 °, even if the angle is shifted, the effect on the crystal field of the R atoms in the main phase is small, and the desired effect can be exhibited.
【００３９】高温からの冷却速度の制御の他に、焼結法
や超急冷法などで一旦得られた磁石を、粒界相中の原子
の拡散が容易な融点以下の300〜800℃の温度域で熱処理
を行うことも、界面構造の制御に有効である。この場合
も、界面のエネルギーが駆動力となり、主相との界面近
傍で粒界相の結晶構造の並び替えが起こり、整合性のあ
る界面が実現する。熱処理後の好ましい冷却速度は10〜
200℃/minである。In addition to controlling the cooling rate from a high temperature, the magnet once obtained by a sintering method, a super-quenching method, or the like is heated to a temperature of 300 to 800 ° C. below the melting point at which atoms in the grain boundary phase can easily diffuse. Heat treatment in the region is also effective in controlling the interface structure. Also in this case, the energy of the interface becomes the driving force, the crystal structure of the grain boundary phase is rearranged near the interface with the main phase, and a consistent interface is realized. Preferred cooling rate after heat treatment is 10 ~
200 ° C / min.
【００４０】以上、主として焼結法を例にとって実施の
形態を説明してきたが、他のR-TM-B系永久磁石の製造方
法においても、好ましい界面の構造の発現方法に関して
は焼結法と全く同様である。Although the embodiment has been described mainly with reference to the sintering method as an example, other methods of producing the R-TM-B-based permanent magnet also have a favorable interface structure. It is exactly the same.
【００４１】上記の方法で得られた優れた磁気特性をも
つ永久磁石材料は、焼結体なとのバルク磁石の場合に
は、研削加工等により所定の寸法精度を与えた後、必要
な表面処理を施し、着磁をして用いることができる。こ
の際に、加工歪みの影響を緩和するために、加工後に熱
処理を行うことも好ましい実施形態である。ボンド磁石
の場合は、得られた磁粉を樹脂と混合し、成形を行った
後、必要であれば表面処理を施し、着磁をして用いるこ
とができる。The permanent magnet material having excellent magnetic properties obtained by the above-described method is, in the case of a bulk magnet such as a sintered body, provided with a predetermined dimensional accuracy by grinding or the like, and then having a required surface. It can be used after being treated and magnetized. At this time, it is also a preferable embodiment to perform a heat treatment after the processing in order to reduce the influence of the processing distortion. In the case of a bonded magnet, the obtained magnetic powder is mixed with a resin, molded, then, if necessary, subjected to a surface treatment and magnetized before use.
【００４２】［異方性定数］本発明に基づく永久磁石に
おいて、強磁性相の最外殻近傍の異方性定数K1の値は内
部と同等、もしくはそれ以上であることが好ましい。こ
の場合の同等とは、内部での値の少なくとも50%以上で
ある。強磁性粒子の最外殻部における結晶磁気異方性
が、粒界相が存在しない場合の該強磁性粒子の最外殻部
の結晶磁気異方性に比べて強められることが好ましい。[Anisotropy Constant] In the permanent magnet according to the present invention, the value of the anisotropy constant K1 near the outermost shell of the ferromagnetic phase is preferably equal to or greater than that of the inside. Equivalence in this case is at least 50% or more of the internal value. It is preferable that the magnetocrystalline anisotropy in the outermost shell of the ferromagnetic particles be enhanced as compared with the magnetocrystalline anisotropy of the outermost shell of the ferromagnetic particles in the absence of the grain boundary phase.
【００４３】［結晶磁気異方性の分布］また、非晶質で
ない特定の結晶構造を持ち、かつ室温において強磁性体
である金属、合金、または金属間化合物の少なくとも１
種の結晶粒からなる永久磁石において、該結晶粒の最外
殻位置での結晶磁気異方性が、結晶粒外部の影響が無視
できる結晶粒内部（中心部）と同等であるか、もしくは
向上し、内部に比べて大きく減少することのないことが
好ましい。実用的な保磁力を得るために、結晶粒の最外
殻位置での結晶磁気異方性は、結晶粒外部の影響が無視
できる内部の結晶磁気異方性の半分以上であることが好
ましい。[Distribution of Crystalline Magnetic Anisotropy] In addition, at least one of a metal, alloy, or intermetallic compound having a specific crystal structure that is not amorphous and being ferromagnetic at room temperature
In a permanent magnet composed of seed crystal grains, the crystal magnetic anisotropy at the outermost shell position of the crystal grains is equal to or improved within the crystal grains (center portion) where the influence of the crystal grains outside can be ignored. However, it is preferable that it does not greatly decrease compared to the inside. In order to obtain a practical coercive force, the crystal magnetic anisotropy at the outermost shell position of the crystal grain is preferably at least half of the internal crystal magnetic anisotropy where the influence of the crystal grain outside can be ignored.
【００４４】［囲まれた主相、離隔構造］非晶質でない
特定の結晶構造を持ち、かつ室温において強磁性体であ
る金属、合金、または金属間化合物からなる主相と，金
属、合金、または金属間化合物からなり、かつ主相の周
囲を取り囲む形で存在する粒界相の少なくとも２相で構
成されることが好ましい。粒界相は、主相を構成する強
磁性相（強磁性粒子）の一部ないし全部を囲むことによ
り保磁力向上が見られる。強磁性相（強磁性粒子）が粒
界相によって半分以上囲まれていることが好ましい。[Enclosed Main Phase, Separated Structure] A main phase composed of a metal, alloy, or intermetallic compound having a specific non-amorphous crystal structure and being ferromagnetic at room temperature, and a metal, alloy, Alternatively, it is preferable to be composed of at least two phases of a grain boundary phase which are made of an intermetallic compound and exist around the main phase. The grain boundary phase can improve the coercive force by surrounding a part or all of the ferromagnetic phase (ferromagnetic particles) constituting the main phase. It is preferable that the ferromagnetic phase (ferromagnetic particles) is surrounded by a grain boundary phase by half or more.
【００４５】［主相と粒界相の好ましい組み合わせ］本
発明において、主相として好ましい金属、合金または金
属間化合物は、永久磁石の主相として優れた性質を有す
るものがよく、具体的には、飽和磁化が高く、キュリー
温度が室温以上で十分に高いものがよい。[Preferred Combination of Main Phase and Grain Boundary Phase] In the present invention, the metal, alloy or intermetallic compound preferable as the main phase preferably has excellent properties as the main phase of the permanent magnet. , A material having a high saturation magnetization and a sufficiently high Curie temperature at room temperature or higher.
【００４６】本発明において、粒界相として好ましい金
属、合金、または金属間化合物は、室温よりも高く、か
つ主相の融点、または分解速度よりも低い融点、または
分解速度を有し、熱処理によって主相の周りに拡散させ
ることが容易なものがよい。また、粒界相を構成する原
子は主相の最外殻原子に対して陽イオンとしてふるま
い、主相の結晶磁気異方性を高めるものが好ましい。特
に、少なくとも強磁性粒子に隣接する粒界相部分に陽イ
オン源を含む結晶を析出し、強磁性相に隣接する粒界相
の結晶構造において、強磁性粒子の最外殻に位置する希
土類元素イオンの4f電子雲が伸びている方向に陽イオン
を位置させることが好ましい。R3TM中のRの他、合金上
記の条件を満たす金属を例示すれば、Be、Mg、Ca、Sr、
Ba、すべての遷移金属元素（Zn、Cdを含む）、Al、Ga、
In、Ta、Sn、Pbなどの一種以上などである。また、Be、
Mg、Al、Si、P、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、
Cu、Zn、Ga、Sr、Zr、Nb、Mo、Cd、In、Sn、Ba、Hf、T
a、Ir、Pbの一種以上である。また、これらの金属同士
の合金、または金属間化合物も粒界相となり得るが、以
上に挙げた例は本発明の適用範囲を限定するものではな
い。In the present invention, the metal, alloy or intermetallic compound preferable as the grain boundary phase has a melting point or decomposition rate higher than room temperature and lower than the melting point or decomposition rate of the main phase. A material that can be easily diffused around the main phase is preferable. Further, it is preferable that the atoms constituting the grain boundary phase behave as cations with respect to the outermost shell atoms of the main phase to enhance the crystal magnetic anisotropy of the main phase. In particular, a crystal containing a cation source is precipitated at least in a grain boundary phase portion adjacent to the ferromagnetic particles, and in the crystal structure of the grain boundary phase adjacent to the ferromagnetic phase, a rare earth element located in the outermost shell of the ferromagnetic particles It is preferable to position the cation in the direction in which the 4f electron cloud of the ion extends. In addition to R in R 3 TM, alloys that satisfy the above conditions for alloys include Be, Mg, Ca, Sr,
Ba, all transition metal elements (including Zn and Cd), Al, Ga,
One or more of In, Ta, Sn, Pb, and the like. Also, Be,
Mg, Al, Si, P, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga, Sr, Zr, Nb, Mo, Cd, In, Sn, Ba, Hf, T
a, Ir, or Pb. In addition, alloys of these metals or intermetallic compounds can also be the grain boundary phase, but the examples given above do not limit the scope of the present invention.
【００４７】上記の主相と粒界相の組み合わせは、例え
ばSmCo5主相とY粒界相のように、両相がある温度域で平
衡に共存するものが好ましい。また、例えばSm2Fe17N３
主相とZn相の反応で金属間化合物相（Γ-FeZn）が形成
されるように、主相と第２相とが反応することにより粒
界に好ましい第３相を形成してもよい。後者の場合に
は、第３相が本発明でいうところの粒界相となる。As the combination of the main phase and the grain boundary phase, it is preferable that both phases coexist in equilibrium in a certain temperature range, such as the SmCo5 main phase and the Y grain boundary phase. Also, for example, Sm2Fe17N3
The main phase and the second phase may react with each other to form a preferred third phase at the grain boundary, such that an intermetallic compound phase (Γ-FeZn) is formed by the reaction between the main phase and the Zn phase. In the latter case, the third phase is the grain boundary phase in the present invention.
【００４８】［微量添加元素の範囲］本発明において、
主相と粒界相との整合性を高めるためにないし磁気特性
を高めるために、主として金属元素又は半金属元素を微
量に添加することは好ましい実施形態である。上記の微
量添加元素は、粒界相に濃縮偏在して界面の濡れ性を高
めたり、あるいは界面の不整合な位置に拡散して粒界相
の格子定数を調整して界面エネルギーを下げ、界面の整
合性を高める効果があり、その結果として磁石の保磁力
が向上する。[Range of trace addition element] In the present invention,
It is a preferred embodiment to mainly add a small amount of a metal element or a metalloid element in order to enhance the consistency between the main phase and the grain boundary phase or to enhance the magnetic properties. The above-mentioned trace added elements are concentrated and unevenly distributed in the grain boundary phase to enhance the wettability of the interface, or diffuse to an inconsistent position of the interface to adjust the lattice constant of the grain boundary phase to lower the interface energy, Has the effect of improving the coherence of the magnet, and as a result, the coercive force of the magnet improves.
【００４９】上記の働きをする微量添加元素としては、
粒界相中に固溶しうる元素が好ましく、例えば、C、N、
Al、Si、P、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、
Zr、Nb、Mo、これら以外の上述の金属元素などがある
が、以上に挙げた例は本発明の適用範囲を限定するもの
ではない。上記の目的で添加する元素の添加量は、磁石
全体に対する割合で1.0wt%以下で良好な磁石の残留磁束
密度が得られ、0.05wt%以上で所定の効果が得られるの
で、添加量の範囲は0.05〜1.0wt%が好ましい。より好ま
しい範囲は0.1〜0.5wt%である。微量添加元素の添加方
法は、母合金に初めから含有させる、粉末冶金的手法で
後から添加するなど、磁石の製造方法に応じて適宜選択
できる。[0049] Examples of the trace addition elements that function as described above include:
Elements that can form a solid solution in the grain boundary phase are preferred, for example, C, N,
Al, Si, P, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga,
There are Zr, Nb, Mo, the above-mentioned metal elements other than these, and the like, but the above-mentioned examples do not limit the applicable range of the present invention. The addition amount of the element to be added for the above purpose is 1.0% by weight or less with respect to the whole magnet to obtain a good residual magnetic flux density of the magnet, and the predetermined effect is obtained at 0.05% by weight or more. Is preferably 0.05 to 1.0 wt%. A more preferred range is from 0.1 to 0.5 wt%. The addition method of the trace addition element can be appropriately selected according to the manufacturing method of the magnet, such as adding it to the mother alloy from the beginning or adding it later by a powder metallurgy technique.
【００５０】［磁性相と粒界相の結晶構造］粒界相の結
晶構造は、磁性相の結晶構造と似ていることが好まし
い。さらに、粒界相の結晶構造と磁性相の結晶構造とが
特定の方位関係にあることが好ましい。これによって、
粒界相側の特定原子と主相側の特定原子の整合性が高ま
る。正方晶R2TM14B金属間化合物(R:Yを含む希土類元
素、TM:FeまたはCo）からなる主相と、特にR3TM合金か
らなる粒界相から構成される永久磁石においては、該主
相と該粒界相の界面近傍における該粒界相の結晶構造が
斜方晶構造であることが好ましい。さらに、面指数と方
位指数に関して、該主相と該粒界相との界面近傍におけ
る結晶学的方位関係が上記(A)〜(D)の組み合わせのいず
れかであることが好ましい。[Crystal Structure of Magnetic Phase and Grain Boundary Phase] The crystal structure of the grain boundary phase is preferably similar to that of the magnetic phase. Further, it is preferable that the crystal structure of the grain boundary phase and the crystal structure of the magnetic phase have a specific orientation relationship. by this,
The consistency between the specific atom on the grain boundary phase side and the specific atom on the main phase side is enhanced. In a permanent magnet composed of a main phase composed of tetragonal R 2 TM 14 B intermetallic compound (R: a rare earth element including Y, TM: Fe or Co), and in particular, a grain boundary phase composed of an R 3 TM alloy, The crystal structure of the grain boundary phase near the interface between the main phase and the grain boundary phase is preferably an orthorhombic structure. Further, with respect to the plane index and the orientation index, it is preferable that the crystallographic orientation relationship in the vicinity of the interface between the main phase and the grain boundary phase is any of the combinations of the above (A) to (D).
【００５１】また、正方晶R2TM14B金属間化合物(R:Yを
含む希土類元素、TM:FeまたはCo）からなる主相と、R-T
M合金からなる粒界相から構成される永久磁石において
は、該主相と該粒界相の界面近傍における該粒界相の結
晶構造が面心立方構造であることが好ましい。さらに、
方向ベクトルと面指数に関して、該主相と該粒界相との
界面近傍における結晶学的方位関係が下記(Ｅ)〜(Ｇ)の
組み合わせのいずれかであることが好ましい。Further, a main phase composed of a tetragonal R 2 TM 14 B intermetallic compound (a rare earth element containing R: Y, TM: Fe or Co);
In a permanent magnet composed of a grain boundary phase made of an M alloy, the crystal structure of the grain boundary phase near the interface between the main phase and the grain boundary phase is preferably a face-centered cubic structure. further,
Regarding the direction vector and the plane index, the crystallographic orientation relationship near the interface between the main phase and the grain boundary phase is preferably one of the following combinations (E) to (G).
【００５２】[0052]
【化５】 Embedded image
【００５３】R3TM合金からなる粒界相とR-TM合金からな
る粒界相とが共存する場合、それぞれの結晶学的方位関
係は、上記(A)〜(D)の組み合わせのいずれか、上記(Ｅ)
〜(Ｇ)の組み合わせのいずれかであることが好ましい。When the grain boundary phase composed of the R 3 TM alloy and the grain boundary phase composed of the R-TM alloy coexist, the respective crystallographic orientation relations are any of the combinations of the above (A) to (D). , Above (E)
To (G).
【００５４】粒界相は、その主相との界面近傍（高々数
原子層）の原子が主相側と整合であればよく、非晶質、
部分的に非晶質、ほとんどが非晶質であってもよい。主
相も同様である。また、界面の一部が整合であることに
よって効果が得られるが、界面の半分以上が整合である
ことが好ましい。また、主相と粒界相は、その界面近傍
に格子欠陥がなく連続性が維持され規則的であることが
好ましいが、一部格子欠陥があってもよい。なお、界面
において、主相と粒界相が50%以上整合していることが
好ましい。The grain boundary phase may be any one as long as atoms near the interface with the main phase (at most several atomic layers) match the main phase.
It may be partially amorphous and mostly amorphous. The same applies to the main phase. Although the effect can be obtained when a part of the interface is matched, it is preferable that half or more of the interface is matched. The main phase and the grain boundary phase preferably have regularity without lattice defects near the interface and maintain continuity, but may have some lattice defects. Note that it is preferable that the main phase and the grain boundary phase match at least 50% at the interface.
【００５５】本発明に基づく永久磁石において、強磁性
相はある条件下で実用的な保磁力を示すものであればよ
く、金属、合金、金属間化合物、半金属、その他の化合
物の一種以上から構成することが可能である。また、本
発明の原理は、永久磁石原料から中間体さらに最終製品
としての永久磁石及びそれらの製造方法まで適用され
る。例えば、永久磁石原料としては、鋳造粉砕法、急冷
薄板粉砕法、超急冷法、直接還元法、水素含有崩壊法、
アトマイズ法によって得られる粉末がある。中間体とし
ては、粉砕されて粉末冶金法の原料とする急冷薄板、熱
処理されて一部又は全部が結晶化する非晶質体（一部又
は全部）がある。最終製品である永久磁石としては、そ
れらの粉末を焼結又はボンド等によってバルク化した磁
石、鋳造磁石、圧延磁石、さらに、スパッタリング法、
イオンプレーティング法、ＰＶＤ法又はＣＶＤ法などに
よる薄膜磁石などがある。さらに、永久磁石原料又は最
終製品として永久磁石の製造方法として、メカニカルア
ロイング法、ホットプレス法、ホットフォーミング法、
熱間・冷間圧延法、HDDR法、押出法、ダイアップセット
法などがあり、特に限定されない。本発明に基づくR-TM
-B系永久磁石は、モーター、医療用MRI装置、スピーカ
ーなどに用いられる。In the permanent magnet according to the present invention, the ferromagnetic phase only needs to exhibit a practical coercive force under certain conditions, and may be formed of one or more of metals, alloys, intermetallic compounds, semimetals and other compounds. It is possible to configure. In addition, the principle of the present invention is applied to permanent magnet raw materials, intermediates, permanent magnets as final products, and methods for producing them. For example, as raw materials for permanent magnets, casting and pulverization methods, quenched thin plate pulverization methods, ultra-quench methods, direct reduction methods, hydrogen-containing collapse methods,
There is a powder obtained by an atomizing method. Examples of the intermediate include a quenched thin plate that is pulverized and used as a raw material for the powder metallurgy method, and an amorphous body (part or all) that is partially or wholly crystallized by heat treatment. As permanent magnets as final products, magnets made by bulking these powders by sintering or bonding, cast magnets, rolled magnets, further sputtering method,
There is a thin film magnet by an ion plating method, a PVD method, a CVD method, or the like. Furthermore, as a method of manufacturing a permanent magnet as a permanent magnet raw material or a final product, a mechanical alloying method, a hot pressing method, a hot forming method,
There are a hot / cold rolling method, an HDR method, an extrusion method, a die upset method, and the like, and there is no particular limitation. R-TM based on the present invention
-B-based permanent magnets are used in motors, medical MRI equipment, speakers, etc.
【００５６】[0056]
【実施例】［実施例１］Nd13.0at%、Co3.0at%、B6.5at
%、残部Fe、および不可避的不純物からなる原料を、φ
0.3mmのオリフィス径を持つ石英管中に装填し、Arガス
雰囲気中で高周波溶解して、溶湯をロール周速度20m/s
で回転する銅製ロールの表面に噴射して急冷し、超急冷
薄帯を得た。これを目の開き300μmのメッシュを全量通
るまで粗く粉砕した後、Ar雰囲気中で600℃、30minの熱
処理を行い、100℃/minの冷却速度で室温まで冷却し
た。得られた磁石粉末の小片をサンプリングし、Ar中の
イオンミリングによって透過電子顕微鏡用の試料を作製
し、観察した結果、平均の結晶粒径は78nm、粒界相は厚
み4nmの斜方晶構造のNd3Co合金であった。得られた磁石
粉末の着磁後の磁気特性を表1に示す。[Example 1] Nd13.0at%, Co3.0at%, B6.5at
%, The balance of the raw material consisting of Fe and unavoidable impurities is φ
Charged into a quartz tube with an orifice diameter of 0.3 mm, melted by high frequency in an Ar gas atmosphere, and rolled the molten metal at a peripheral speed of 20 m / s
And rapidly quenched by spraying onto the surface of a copper roll rotating at to obtain a super-quenched ribbon. This was roughly pulverized until the entire amount of the mesh having a mesh size of 300 μm passed, and then heat-treated at 600 ° C. for 30 minutes in an Ar atmosphere and cooled to room temperature at a cooling rate of 100 ° C./min. A small piece of the obtained magnet powder was sampled, a sample for a transmission electron microscope was prepared by ion milling in Ar, and as a result of observation, the average crystal grain size was 78 nm, and the grain boundary phase was a 4 nm thick orthorhombic structure. Nd 3 Co alloy. Table 1 shows the magnetic properties of the obtained magnet powder after magnetization.
【００５７】［比較例1］実施例1で得られた超急冷薄帯
の粗粉砕粉の小片をそのままサンプリングし、透過電子
顕微鏡で観察した結果、平均の結晶粒径は74nm、粒界相
は厚み3nmの非晶質Nd-Fe-Co合金であった。得られた磁
石粉末の着磁後の磁気特性を表1に示す。Comparative Example 1 A small piece of the coarsely crushed powder of the ultra-quenched ribbon obtained in Example 1 was directly sampled and observed with a transmission electron microscope. As a result, the average crystal grain size was 74 nm, and the grain boundary phase was It was an amorphous Nd-Fe-Co alloy having a thickness of 3 nm. Table 1 shows the magnetic properties of the obtained magnet powder after magnetization.
【００５８】[0058]
【表１】 [Table 1]
【００５９】表1の結果から明らかなように、結晶粒径
がほぼ同一で粒界相の結晶構造が非晶質、または斜方晶
構造のR-TM-B系永久磁石の磁気特性を比較すると、斜方
晶構造のものが保磁力の面で特に優れた磁気特性を発現
することがわかる。As is clear from the results in Table 1, the magnetic properties of R-TM-B permanent magnets having substantially the same crystal grain size and having an amorphous or orthorhombic structure in the grain boundary phase were compared. Then, it can be seen that the orthorhombic structure exhibits particularly excellent magnetic properties in terms of coercive force.
【００６０】［実施例2］Nd14.0at%、Co3.0at%、B7.0at
%、残部Fe、および不可避的不純物からなる原料を、Ar
ガス雰囲気中で高周波溶解して、合金を溶製した。次
に、該合金を粗粉砕した後、ジョークラッシャー、およ
び、ディスクミルにより420μm以下に粉砕し、さらに、
ジェットミル粉砕して平均粒径3μmの粉末を得た。得ら
れた微粉末を縦15mm、横20mmのダイス中に給粉し、11kO
eの磁界中で配向しながら、深さ方向に1.5Ton/cm2の圧
力を加えて成形した。成形体を取り出した後、真空中で
1100℃まで昇温し、2時間保持する焼結を行い、さら
に、焼結完了後、200℃/minの速度で800℃まで冷却し、
その後、100℃/minの速度で300℃まで冷却し、ついでAr
を導入して室温まで冷却して焼結磁石を得た。得られた
焼結体の寸法は収縮によって成形体よりも減少したが、
ワレ、ヒビ、変形などは全く見られなかった。次に、焼
結後の磁石を真空中、500℃で2h保持した後、20℃/min
の速度で室温まで冷却した。得られた焼結磁石の着磁後
の磁気特性を表2に示す。Example 2 Nd 14.0at%, Co3.0at%, B7.0at
%, The balance of Fe, and the raw material consisting of unavoidable impurities
The alloy was melted by high frequency melting in a gas atmosphere. Next, after coarsely pulverizing the alloy, jaw crusher, and pulverized to 420μm or less by a disc mill, further,
Jet mill pulverization was performed to obtain a powder having an average particle size of 3 μm. The obtained fine powder was fed into a 15 mm long, 20 mm wide die, and 11 kO
While orienting in the magnetic field of e, molding was performed by applying a pressure of 1.5 Ton / cm2 in the depth direction. After removing the molded body, in vacuum
Perform sintering by raising the temperature to 1100 ° C and holding for 2 hours.After sintering is completed, cool to 800 ° C at a rate of 200 ° C / min.
Then, it is cooled to 300 ° C at a rate of 100 ° C / min, and then Ar
And cooled to room temperature to obtain a sintered magnet. Although the size of the obtained sintered body was smaller than that of the molded body due to shrinkage,
No cracks, cracks or deformations were seen at all. Next, after holding the magnet after sintering at 500 ° C. for 2 hours in a vacuum, 20 ° C./min.
At room temperature. Table 2 shows the magnetic properties of the obtained sintered magnet after magnetization.
【００６１】また、得られた磁石の小片をサンプリング
し、Ar中のイオンミリングによって透過電子顕微鏡用の
試料を作製し、観察した結果、平均の結晶粒径は12μ
m、粒界相は厚み120nmの斜方晶構造のNd3Co金属間化合
物であった。また、主相との界面付近の粒界相の結晶方
位を制限視野電子線回折像で解析した結果、ほとんどの
観察部位で、上記(A)〜(D)のいずれかの方位関係を持っ
ていることがわかった。Further, a small piece of the obtained magnet was sampled, a sample for a transmission electron microscope was prepared by ion milling in Ar, and observed. As a result, the average crystal grain size was 12 μm.
m, the grain boundary phase was a 120 nm thick Nd 3 Co intermetallic compound having an orthorhombic structure. In addition, as a result of analyzing the crystal orientation of the grain boundary phase near the interface with the main phase with a selected area electron beam diffraction image, most of the observed sites have the orientation relationship of any of the above (A) to (D). I knew it was there.
【００６２】［比較例2］実施例2で得られた焼結後の磁
石を、熱処理せずにサンプリングし、透過電子顕微鏡用
で観察した結果、平均の結晶粒径は12μm、粒界相は厚
み120nmの斜方晶構造のNd3Co金属間化合物であった。し
かし、主相との界面付近の粒界相の結晶方位を制限視野
電子線回折像で解析した結果、特定の方位関係は見いだ
せなかった。得られた焼結磁石の着磁後の磁気特性を表
2に示す。Comparative Example 2 The sintered magnet obtained in Example 2 was sampled without heat treatment and observed with a transmission electron microscope. As a result, the average crystal grain size was 12 μm, and the grain boundary phase was It was an Nd 3 Co intermetallic compound having a thickness of 120 nm and an orthorhombic structure. However, as a result of analyzing the crystal orientation of the grain boundary phase near the interface with the main phase using a selected area electron beam diffraction image, no specific orientation relationship was found. The magnetic properties of the obtained sintered magnet after magnetization are shown.
See Figure 2.
【００６３】[0063]
【表２】 [Table 2]
【００６４】表２の結果から明らかなように、結晶粒径
がほぼ同一で粒界相の結晶構造が同じ斜方晶構造のR-TM
-B系永久磁石の磁気特性を比較すると、主相とその近傍
の粒界相とに特定の方位関係がある場合、保磁力の面で
特に優れた磁気特性を発現することがわかる。As is evident from the results in Table 2, R-TM having an orthorhombic structure having almost the same crystal grain size and the same crystal structure of the grain boundary phase.
Comparing the magnetic properties of the -B-based permanent magnets, it can be seen that when the main phase and the grain boundary phase in the vicinity have a specific orientation relationship, particularly excellent magnetic properties are exhibited in terms of coercive force.
【００６５】[0065]
【発明の効果】本発明によれば、高磁気性能（特に保磁
力）を有するR-TM-B系永久磁石を設計するため指針が提
供される。従来、保磁力を決定する主相と粒界相間の界
面の構造が未知であったが、本発明によって、保磁力を
向上させるための理想的な界面の構造が明らかにされた
ことにより、新たなR-TM-B系永久磁石の開発の指針が提
供されると共に、既存のR-TM-B系永久磁石の保磁力のさ
らなる向上が可能となる。この結果、新規な磁石材料の
発見が容易となり、今まで保磁力が低いため実用されて
いないR-TM-B系永久磁石の実用化も可能となる。According to the present invention, a guide is provided for designing an R-TM-B-based permanent magnet having high magnetic performance (particularly coercive force). Conventionally, the structure of the interface between the main phase and the grain boundary phase that determines the coercive force was unknown, but the present invention has revealed a new ideal interface structure for improving the coercive force. In addition to providing guidance for the development of an R-TM-B permanent magnet, the coercive force of existing R-TM-B permanent magnets can be further improved. As a result, it is easy to find a new magnet material, and it is possible to commercialize an R-TM-B-based permanent magnet that has not been used because of its low coercive force.
【００６６】本発明によるR-TM-B系永久磁石は、主相と
粒界相の界面における原子同士の位置関係が規則正しく
なり、両者の整合性が保たれる結果、界面が逆磁区発生
の起点となる可能性が減少し、高保磁力を得ることがで
きる。また、本発明によるR-TM-B系永久磁石は、強磁性
相と粒界相とに特定の結晶方位関係を持たせ、界面近傍
の主相中のR原子の結晶場を強めることにより主相の界
面近傍での結晶磁気異方性を高め、その結果、粒界近傍
での逆磁区発生を困難ならしめ、容易に磁化反転するこ
とができないため保磁力が向上した、優れた磁気特性を
持つ磁石材料である。In the R-TM-B-based permanent magnet according to the present invention, the positional relationship between atoms at the interface between the main phase and the grain boundary phase becomes regular, and as a result of maintaining the consistency between the two, the interface causes the generation of reverse magnetic domains. The possibility of starting points is reduced, and a high coercive force can be obtained. Further, the R-TM-B permanent magnet according to the present invention has a specific crystal orientation relationship between the ferromagnetic phase and the grain boundary phase, and strengthens the crystal field of R atoms in the main phase near the interface. The crystal magnetic anisotropy near the phase interface is increased, and as a result, it is difficult to generate reverse magnetic domains near the grain boundaries, and the magnetization reversal cannot be easily performed. It has a magnet material.
【図面の簡単な説明】[Brief description of the drawings]
【図１】界面からの距離と結晶磁気異方性の関係を説明
するための図であって、白丸が実施例の一軸異方性定数
K1、黒丸が比較例の一軸異方性定数K1を示す。FIG. 1 is a diagram for explaining a relationship between a distance from an interface and crystal magnetic anisotropy, in which a white circle indicates a uniaxial anisotropy constant of an example.
K 1 and black circles indicate the uniaxial anisotropy constant K 1 of the comparative example.
【図２】（Ａ）は主相と粒界相が整合している様子を示
すモデル図、（Ｂ）主相と粒界相が整合していない様子
を示すモデル図である。FIG. 2A is a model diagram showing a state where a main phase and a grain boundary phase match, and FIG. 2B is a model diagram showing a state where a main phase and a grain boundary phase do not match.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年５月１３日[Submission date] May 13, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１０】ここで、Ｒ２ＴＭ１４Ｂ金属間化合物の
（好ましくは単結晶体）からなる主相（強磁性相）と、
Ｒ３ＴＭ合金からなる粒界相とから主として構成される
Ｒ−ＴＭ−Ｂ系永久磁石を例として、本発明の原理を説
明する。なお、Ｒ−ＴＭ−Ｂ系永久磁石中には上述の主
相、粒界相以外にもＢ−ｒｉｃｈ相（Ｒ１＋αＴＭ４Ｂ
４）、Ｒ−ＴＭ準安定相、工程中で不可避的に形成され
る酸化物、および炭化物などが存在することが知られて
いるが、これらの相が該永久磁石の磁気特性に及ぼす影
響は該主相、該粒界相の二相と比べて副次的である。Here, a main phase (ferromagnetic phase) composed of (preferably a single crystal) of R 2 TM 14 B intermetallic compound;
The principle of the present invention will be described using an R-TM-B-based permanent magnet mainly composed of a grain boundary phase composed of an R 3 TM alloy as an example. In the R-TM-B-based permanent magnet, in addition to the main phase and the grain boundary phase, a B-rich phase (R 1 + α TM 4 B
4 ) It is known that there are R-TM metastable phase, oxides and carbides inevitably formed in the process, and the influence of these phases on the magnetic properties of the permanent magnet is known. It is secondary compared to the two phases of the main phase and the grain boundary phase.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１８】図１、図２（Ａ）及び（Ｂ）を参照して、
主相（強磁性相）と粒界相がその界面で整合している場
合と、整合していない場合とで、界面近傍における結晶
磁気異方性の分布の相違を説明する。図１又は図２
（Ａ）及び（Ｂ）において、横軸の”最外殻”とは主相
の最も外側の原子層の位置を示し、”第２層”、”第３
層”とはそれぞれ最外殻位置から内部に向かって数えて
２番目、３番目の原子層の位置を示す。第ｎ層とは最外
殻からの距離が遠く、界面からの影響が無視できる位置
を示す。図１のグラフ中、縦軸は主相の一軸異方性定数
Ｋ１（結晶磁気異方性の強さを示す）の大きさを示し、
Ｋ１の値が大きいほど主相の自発磁化の向きは磁化容易
軸（ｃ軸）の方向で安定化する。また、図１中、実施例
（本発明）は図２（Ａ）に示すように主相と粒界相が界
面で整合している条件でのＫ１の計算値を示し、比較例
は図２（Ｂ）に示すように粒界相の欠落などによって界
面の不整合などがある場合のＫ１の計算値を示してい
る。Referring to FIGS. 1, 2A and 2B,
The difference in the distribution of magnetocrystalline anisotropy near the interface between the case where the main phase (ferromagnetic phase) and the grain boundary phase match at the interface and the case where they do not match will be described. FIG. 1 or FIG.
In (A) and (B), the “outermost shell” on the horizontal axis indicates the position of the outermost atomic layer of the main phase, and “second layer”, “third layer”.
The “layer” indicates the position of the second and third atomic layers counted from the outermost shell position toward the inside. The nth layer is far from the outermost shell, and the influence from the interface is negligible. 1, the vertical axis indicates the magnitude of the uniaxial anisotropy constant K 1 (indicating the strength of the crystalline magnetic anisotropy) of the main phase,
Spontaneous magnetization direction of higher values of K 1 is large main phase is stabilized in the direction of easy magnetization (c axis). Further, in FIG. 1, Example (the invention) shows the calculated values of K 1 in the condition where the main phase and a grain boundary phase as shown in FIG. 2 (A) is aligned at the interface, the comparative example FIG. such as by 2 (B) lack of grain boundary phase, as shown in shows the calculated values of K 1 in the case where there is such an interface mismatch.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１９】図１を参照して、比較例においては、界面
からの距離によって異方性定数Ｋ１の大きさが大きく変
化し、最外殻におけるＫ１の値が内部に比べて著しく低
下している。一方、実施例においては、界面からの距離
によって異方性定数Ｋ１の大きさがあまり変化せず、む
しろ最外殻相において異方性定数Ｋ１が上昇している。
従って、比較例によれば、最外殻において逆磁区の核生
成に要するエネルギーが局所的に低下して核生成と磁化
反転が容易になるため、磁石の保磁力が低下する。一
方、実施例によれば、最外殻におけるＫ１がむしろ内部
より高いため、界面における逆磁区の核生成が抑制さ
れ、その結果磁石の保磁力が増加する。Referring to FIG. 1, in the comparative example, the magnitude of the anisotropy constant K 1 greatly changes depending on the distance from the interface, and the value of K 1 in the outermost shell is significantly lower than that in the interior. ing. On the other hand, in the embodiment, without much change in the magnitude of the anisotropy constant K 1 by the distance from the interface, the anisotropy constant K 1 is increased in the outermost shell phase rather.
Therefore, according to the comparative example, the energy required for nucleation of the reverse magnetic domain in the outermost shell is locally reduced to facilitate nucleation and magnetization reversal, so that the coercive force of the magnet is reduced. On the other hand, according to the embodiment, since higher internal rather is K 1 in the outermost shell, the nucleation of reverse magnetic domains at the interface is suppressed, so that the coercive force of the magnet is increased.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４２[Correction target item name] 0042
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４２】［異方性定数］本発明に基づく永久磁石に
おいて、強磁性相の最外殻近傍の異方性定数Ｋ１の値は
内部と同等、もしくはそれ以上であることが好ましい。
この場合の同等とは、内部での値の少なくとも５０％以
上である。強磁性粒子の最外殻部における結晶磁気異方
性が、粒界相が存在しない場合の該強磁性粒子の最外殻
部の結晶磁気異方性に比べて強められることが好まし
い。[0042] The permanent magnet that is based on the anisotropy constant present invention, it is preferred values of the anisotropy constant K 1 of outermost vicinity of the ferromagnetic phase is inside the same, or more.
Equivalent in this case is at least 50% or more of the internal value. It is preferable that the magnetocrystalline anisotropy in the outermost shell of the ferromagnetic particles be enhanced as compared with the magnetocrystalline anisotropy of the outermost shell of the ferromagnetic particles in the absence of the grain boundary phase.
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４７[Correction target item name] 0047
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４７】上記の主相と粒界相の組み合わせは、例え
ばＳｍＣｏ５主相とＹ粒界相のように、両相がある温度
域で平衡に共存するものが好ましい。また、例えばＳｍ
２Ｆｅ１７Ｎ３主相とＺｎ相の反応で金属間化合物相
（Γ−ＦｅＺｎ）が形成されるように、主相と第２相と
が反応することにより粒界に好ましい第３相を形成して
もよい。後者の場合には、第３相が本発明でいうところ
の粒界相となる。It is preferable that the combination of the main phase and the grain boundary phase coexist in equilibrium in a certain temperature range, for example, a SmCo 5 main phase and a Y grain boundary phase. Also, for example, Sm
The main phase and the second phase react with each other to form a preferred third phase at the grain boundary, such that an intermetallic compound phase (Γ-FeZn) is formed by the reaction between the 2 Fe 17 N 3 main phase and the Zn phase. May be. In the latter case, the third phase is the grain boundary phase in the present invention.
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００５６[Correction target item name] 0056
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００５６】[0056]
【実施例】［実施例１］Ｎｄ１３．０ａｔ％、Ｃｏ３．
０ａｔ％、Ｂ６．５ａｔ％、残部Ｆｅ、および不可避的
不純物からなる原料を、φ０．３ｍｍのオリフィス径を
持つ石英管中に装填し、Ａｒガス雰囲気中で高周波溶解
して、溶湯をロール周速度２０ｍ／ｓで回転する銅製ロ
ールの表面に噴射して急冷し、超急冷薄帯を得た。これ
を目の開き３００μｍのメッシュを全量通るまで粗く粉
砕した後、Ａｒ雰囲気中で６００℃、３０ｍｉｎの熱処
理を行い、１００℃／ｍｉｎの冷却速度で室温まで冷却
した。得られたＲ２ＴＭ１４Ｂ系磁石粉末の小片をサン
プリングし、Ａｒ中のイオンミリングによって透過電子
顕微鏡用の試料を作製し、観察した結果、平均の結晶粒
径は７８ｎｍ、粒界相は厚み４ｎｍの斜方晶構造のＮｄ
３Ｃｏ合金であった。得られた磁石粉末の着磁後の磁気
特性を表１に示す。[Example 1] Nd 13.0 at%, Co3.
A raw material comprising 0 at%, B 6.5 at%, balance Fe, and unavoidable impurities is charged into a quartz tube having an orifice diameter of φ0.3 mm, and is melted by high frequency in an Ar gas atmosphere, and the molten metal is rolled at a peripheral speed of the roll. It was jetted onto the surface of a copper roll rotating at 20 m / s and quenched to obtain a super-quenched ribbon. This was roughly pulverized until the whole amount passed through a mesh having an opening of 300 μm, and then heat-treated at 600 ° C. for 30 minutes in an Ar atmosphere, and cooled to room temperature at a cooling rate of 100 ° C./min. A small piece of the obtained R 2 TM 14 B-based magnet powder was sampled, a sample for a transmission electron microscope was prepared by ion milling in Ar, and observed. As a result, the average crystal grain size was 78 nm, and the grain boundary phase was thick. 4 nm orthorhombic Nd
3 Co alloy. Table 1 shows the magnetic properties of the obtained magnet powder after magnetization.
【手続補正７】[Procedure amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００６０[Correction target item name] 0060
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００６０】［実施例２］Ｎｄ１４．０ａｔ％、Ｃｏ
３．０ａｔ％、Ｂ７．０ａｔ％、残部Ｆｅ、および不可
避的不純物からなる原料を、Ａｒガス雰囲気中で高周波
溶解して、合金を溶製した。次に、該合金を粗粉砕した
後、ジヨークラッシャー、および、ディスクミルにより
４２０μｍ以下に粉砕し、さらに、ジェットミル粉砕し
て平均粒径３μｍの粉末を得た。得られた微粉末を縦１
５ｍｍ、横２０ｍｍのダイス中に給粉し、１１ｋＯｅの
磁界中で配向しながら、深さ方向に１．５ｔｏｎ／ｃｍ
２の圧力を加えて成形した。成形体を取り出した後、真
空中で１１００℃まで昇温し、２時間保持する焼結を行
い、さらに、焼結完了後、２００℃／ｍｉｎの速度で８
００℃まで冷却し、その後、１００℃／ｍｉｎの速度で
３００℃まで冷却し、ついでＡｒを導入して室温まで冷
却してＲ２ＴＭ１４Ｂ系焼結磁石を得た。得られた焼結
体の寸法は収縮によって成形体よりも減少したが、ワ
レ、ヒビ、変形などは全く見られなかった。次に、焼結
後の磁石を真空中、５００℃で２ｈ保持した後、２０℃
／ｍｉｎの速度で室温まで冷却した。得られた焼結磁石
の着磁後の磁気特性を表２に示す。 ─────────────────────────────────────────────────────
Example 2 Nd 14.0 at%, Co
A raw material consisting of 3.0 at%, 7.0 at% B, the balance Fe, and unavoidable impurities was subjected to high frequency melting in an Ar gas atmosphere to produce an alloy. Next, after roughly pulverizing the alloy, the alloy was pulverized to 420 μm or less by a joke crusher and a disc mill, and further pulverized by a jet mill to obtain a powder having an average particle diameter of 3 μm. The obtained fine powder is
Powder is fed into a 5 mm, 20 mm horizontal die, and oriented in a magnetic field of 11 kOe, while 1.5 ton / cm in the depth direction.
Molding was performed by applying a pressure of 2 . After taking out the molded body, the temperature is raised to 1100 ° C. in vacuum and sintering is performed for 2 hours, and after sintering is completed, the sintering is performed at a rate of 200 ° C./min.
The mixture was cooled to 00 ° C., and then cooled to 300 ° C. at a rate of 100 ° C./min. Then, Ar was introduced and cooled to room temperature to obtain an R 2 TM 14 B-based sintered magnet. Although the size of the obtained sintered body was smaller than that of the molded body due to shrinkage, cracks, cracks, deformation and the like were not observed at all. Next, after holding the magnet after sintering at 500 ° C. for 2 hours in a vacuum,
/ Min at room temperature. Table 2 shows the magnetic properties of the obtained sintered magnet after magnetization. ────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年１２月２２日[Submission date] December 22, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２４[Correction target item name] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２４】また、主相において、Ｂの一部ないし大部
分をＣ，Ｓｉ，Ｐ，などのいわゆる半金族元素で置換し
てもよい。例えば、ＢをＣで置換する場合、Ｂ １−ｘ Ｃ
ｘ 、但し好ましくはｘは少なくとも０．８まで可であ
る。In the main phase, part or most of B may be replaced by a so-called semi-metal group element such as C, Si, P, or the like. For example, when replacing B with C, B 1−x C
x , but preferably x can be at least 0.8.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３１[Correction target item name] 0031
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３１】上記の主相と粒界相の界面における原子同
士の位置関係をさらに理想的に制御するには、主相と粒
界相の結晶学的方位関係を限定することが必要である。
ここで、結晶学的記号の意味を説明する。記号”［ｈｋ
ｌ］”はミラー指数がｈ、ｋ、ｌで表される結晶面に垂
直な法線の方向を表す。また、記号”［ｈｋｌ］”の添
字”主相”、”粒界相”とは、それぞれの方向が主相、
または粒界相のものであることを示す。例えば、記号”
［００１］主相”は主相であるＲ２ＴＭ１４Ｂ相のＣ軸
の方向を表している。一組の方向指数の間に記された記
号”／／”は、これらの方向ベクトルが互いに平行であ
ることを示す。To more ideally control the positional relationship between atoms at the interface between the main phase and the grain boundary phase, it is necessary to limit the crystallographic orientation relationship between the main phase and the grain boundary phase.
Here, the meaning of the crystallographic symbols will be described. The symbol "[hk
l] "represents the direction of the normal line perpendicular to the crystal plane mirror indices h, k, is expressed by l. Furthermore, the symbol" Attachment of [hkl] "
The character “main phase” and “grain boundary phase” mean that each direction is the main phase,
Or it shows that it is of a grain boundary phase. For example, the symbol "
[001] The main phase represents the direction of the C-axis of the main phase R 2 TM 14 B phase. The symbol “//” written between a set of direction indices indicates that these direction vectors are Indicates that they are parallel to each other.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３２[Correction target item name] 0032
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３２】次に、記号”（ｈｋｌ）”はミラー指数が
ｈ、ｋ、ｌで表される結晶面を表し、添字”主相”、”
粒界相”と、記号”／／”の意味するところは方向の場
合と同じである。ここで、同一の相についての方向と結
晶面の表記においては、用いられるミラー指数は一般化
された指数ではなく、特定の結晶方向、ないし結晶面を
示している。 ─────────────────────────────────────────────────────
Next, the symbol "(hkl)" represents a crystal plane whose Miller index is represented by h, k, l, and the subscripts "main phase", "
The meaning of the "grain boundary phase" and the symbol "//" is the same as that of the direction. Here, the Miller index used in the description of the direction and the crystal plane for the same phase is generalized. Instead of an index, it indicates a specific crystal direction or crystal plane. ────────────────────
【手続補正書】[Procedure amendment]
【提出日】平成１０年１２月２４日[Submission date] December 24, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項２[Correction target item name] Claim 2
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００７】本発明は第１の視点において次の要素を有
する。結晶構造が正方晶であるＲ２ＴＭ１４Ｂ金属間化
合物（Ｒ：Ｙを含む希土類元素、ＴＭ：遷移金属）から
主としてなる磁性相。Ｒ３ＴＭ合金から主としてなる粒
界相。磁性相と粒界相の界面近傍における粒界相の結晶
構造が斜方晶構造であること。磁性相と粒界相が整合し
ていること。第２の視点においては、Ｒ２ＴＭ１４Ｂ金
属間化合物において、Ｒ中のＮｄとＰｒの合計が５０ａ
ｔ％以上。ＴＭはＦｅまたはＣｏでＴＭ中のＦｅが５０
ａｔ％以上。第３の視点においては、Ｒ２ＴＭ１４Ｂ金
属間化合物において、ＴＭ中のＦｅが５０ａｔ％以上。
ＴＭ中のＣｏが０．１ａｔ％以上。Ｒ３ＴＭ金属間化合
物において、ＴＭ中のＣｏが９０ａｔ％以上。第４の視
点においては、前記第１の視点に基づき磁性相と粒界相
の界面近傍における結晶学的方位関係が、下記の少なく
とも一組で表されること。方位関係のずれの角度が５°
以内であること。[0007] The first aspect has the following elements. A magnetic phase mainly composed of a R 2 TM 14 B intermetallic compound (R: rare earth element containing Y, TM: transition metal) having a tetragonal crystal structure. Grain boundary phase mainly composed of R 3 TM alloy. The crystal structure of the grain boundary phase near the interface between the magnetic phase and the grain boundary phase is an orthorhombic structure. The magnetic phase and the grain boundary phase must match. In the second viewpoint, in the R 2 TM 14 B intermetallic compound, the total of Nd and Pr in R is 50a.
t% or more. TM is Fe or Co and Fe in TM is 50
at% or more . In a third viewpoint, in the R 2 TM 14 B intermetallic compound, Fe in the TM is 50 at% or more.
0.1 at% or more of Co in TM. In the R 3 TM intermetallic compound, Co in TM is 90 at% or more. In a fourth aspect, the crystallographic orientation relationship near the interface between the magnetic phase and the grain boundary phase is represented by at least one of the following sets based on the first aspect. 5 ° misalignment angle
Within.
【手続補正書】[Procedure amendment]
【提出日】平成１０年１２月２５日[Submission date] December 25, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００６１[Correction target item name] 0061
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００６１】また、得られた磁石の小片をサンプリング
し、Ａｒ中のイオンミリングによって透過電子顕微鏡用
の試料を作製し、観察した結果、平均の結晶粒径は１２
μｍ、粒界相は厚み１２ｎｍの斜方晶構造のＮｄ３Ｃｏ
金属間化合物であった。また、主相との界面付近の粒界
相の結晶方位を制限視野電子線回折像で解析した結果、
ほとんどの観察部位で、上記（Ａ）〜（Ｄ）のいずれか
の方位関係を持っていることがわかった。A small piece of the obtained magnet was sampled, a sample for a transmission electron microscope was prepared by ion milling in Ar, and observed.
μm, and the grain boundary phase is Nd 3 Co having an orthorhombic structure with a thickness of 12 nm.
It was an intermetallic compound. In addition, as a result of analyzing the crystal orientation of the grain boundary phase near the interface with the main phase with a selected area electron beam diffraction image,
It was found that most of the observation sites had any of the orientation relationships (A) to (D) described above.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００６２[Correction target item name] 0062
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００６２】［比較例２］実施例２で得られた焼結後の
磁石を、熱処理せずにサンプリングし、透過電子顕微鏡
用で観察した結果、平均の結晶粒径は１２μｍ、粒界相
は厚み１２ｎｍの斜方晶構造のＮｄ３Ｃｏ金属間化合物
であった。しかし、主相との界面付近の粒界相の結晶方
位を制限視野電子線回折像で解析した結果、特定の方位
関係は見いだせなかった。得られた焼結磁石の着磁後の
磁気特性を表２に示す。Comparative Example 2 The sintered magnet obtained in Example 2 was sampled without heat treatment and observed under a transmission electron microscope. As a result, the average crystal grain size was 12 μm, and the grain boundary phase was It was a 12 nm-thick Nd 3 Co intermetallic compound having an orthorhombic structure. However, as a result of analyzing the crystal orientation of the grain boundary phase near the interface with the main phase using a selected area electron beam diffraction image, no specific orientation relationship was found. Table 2 shows the magnetic properties of the obtained sintered magnet after magnetization.
Claims (6)
合物(R:Yを含む希土類元素、TM:遷移金属)からなる主と
して磁性相と、R3TM合金からなる主として粒界相を含む
R-TM-B系永久磁石であって、 前記磁性相と該粒界相の界面近傍における該粒界相の結
晶構造が斜方晶構造であって、該磁性相と該粒界相が整
合しているR-TM-B系永久磁石。1. A magnetic phase mainly composed of an R 2 TM 14 B intermetallic compound (R: rare earth element containing Y, TM: transition metal) having a tetragonal crystal structure, and a grain boundary mainly composed of an R 3 TM alloy. Including phase
An R-TM-B-based permanent magnet, wherein the crystal structure of the grain boundary phase near the interface between the magnetic phase and the grain boundary phase is an orthorhombic structure, and the magnetic phase and the grain boundary phase match. R-TM-B permanent magnet.
NdとPrの合計が50at%以上、前記TMはFeまたはCoでTM中
のFeが50at%以上であり、 前記R3TM合金において、Rが90at%以上であることを特徴
とする請求項１記載のR-TM-B系永久磁石。2. In the above R 2 TM 14 B intermetallic compound,
The total of Nd and Pr is at least 50 at%, the TM is Fe or Co, and Fe in the TM is at least 50 at%, and R is at least 90 at% in the R 3 TM alloy. The R-TM-B permanent magnet described.
のFeが50at%以上、TM中のCoが0.1at%以上であり前記R3T
M金属間化合物において、TM中のCoが90at%以上であるこ
とを特徴とする請求項１記載のR-TM-B系永久磁石。3. The R 2 TM 14 B intermetallic compound, wherein Fe in the TM is at least 50 at%, Co in the TM is at least 0.1 at%, and the R 3 T
2. The R-TM-B permanent magnet according to claim 1, wherein in the M intermetallic compound, Co in the TM is 90 at% or more.
る結晶学的方位関係が、 【化１】 の少なくとも一組で表され、かつ該方位関係のずれの角
度が5°以内であることを特徴とする請求項１〜３のい
ずれか一に記載のR-TM-B系永久磁石。4. The crystallographic orientation relationship in the vicinity of the interface between the magnetic phase and the grain boundary phase is as follows: The R-TM-B-based permanent magnet according to any one of claims 1 to 3, wherein the R-TM-B-based permanent magnet is represented by at least one of the following, and the angle of the misalignment is within 5 °.
性層との界面近傍における結晶構造が斜方晶である粒界
相と、を含み、前記磁性相と前記粒界相が前記界面を挟
んで整合しているR-TM-B系永久磁石。5. A magnetic phase having a tetragonal crystal structure, and a grain boundary phase having an orthorhombic crystal structure near an interface with the magnetic layer, wherein the magnetic phase and the grain boundary phase are R-TM-B permanent magnet that is aligned across the interface.
Yを含む希土類元素、TM:遷移金属)源と、R3TM合金源を
原料として用い、 R2TM14B正方晶を析出し、さらに該R2TM14B正方晶相の周
囲にR3TM斜方晶相を析出して該R2TM14B正方晶相と該R3T
M斜方晶相を整合させ、整合した界面近傍の前記R2TM14B
正方晶相の結晶磁気異方性を高めたR-TM-B系永久磁石の
製造方法。6. An R 2 TM 14 B intermetallic compound exhibiting ferromagnetism (R:
Rare earth elements including Y, TM: transition metal) source, R 3 TM alloy source used as a starting material, R 2 TM 14 B tetragonal precipitates, further wherein R 2 TM 14 B tetragonal around the phase R 3 TM orthorhombic phase is precipitated to form the R 2 TM 14 B tetragonal phase and the R 3 T
M orthorhombic phase is aligned, and the R 2 TM 14 B
A method for producing an R-TM-B permanent magnet with enhanced crystal magnetic anisotropy of a tetragonal phase.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10095477A JPH11273920A (en) | 1998-03-23 | 1998-03-23 | R-tm-b permanent magnet |
| US09/265,669 US6511552B1 (en) | 1998-03-23 | 1999-03-10 | Permanent magnets and R-TM-B based permanent magnets |
| CNB991073118A CN1242426C (en) | 1998-03-23 | 1999-03-23 | Permanent magnet and R-TM-B series permanent magnet |
| EP06006902A EP1737001A3 (en) | 1998-03-23 | 1999-03-23 | Permanent magnets and methods for their production |
| KR1019990009794A KR100606156B1 (en) | 1998-03-23 | 1999-03-23 | Permanent Magnet and R-TM-V Permanent Magnet |
| CNB031016642A CN1242424C (en) | 1998-03-23 | 1999-03-23 | Permanent magnet and R-TM-B series permanent magnet |
| EP99105857A EP0945878A1 (en) | 1998-03-23 | 1999-03-23 | Permanent magnets and methods for their production |
| US10/256,193 US6821357B2 (en) | 1998-03-23 | 2002-09-27 | Permanent magnets and R-TM-B based permanent magnets |
| US10/256,166 US7025837B2 (en) | 1998-03-23 | 2002-09-27 | Permanent magnets and R-TM-B based permanent magnets |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10095477A JPH11273920A (en) | 1998-03-23 | 1998-03-23 | R-tm-b permanent magnet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11273920A true JPH11273920A (en) | 1999-10-08 |
Family
ID=14138713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10095477A Pending JPH11273920A (en) | 1998-03-23 | 1998-03-23 | R-tm-b permanent magnet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11273920A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005091315A1 (en) * | 2004-03-23 | 2005-09-29 | Japan Science And Technology Agency | R-Fe-B BASED THIN FILM MAGNET AND METHOD FOR PREPARATION THEREOF |
| US7087185B2 (en) | 1999-07-22 | 2006-08-08 | Seiko Epson Corporation | Magnetic powder and isotropic bonded magnet |
| JP2015135935A (en) * | 2013-03-28 | 2015-07-27 | Tdk株式会社 | Rare earth based magnet |
| JP2021034711A (en) * | 2019-08-16 | 2021-03-01 | 包頭天和磁気材料科技股▲ふん▼有限公司 | Sintered bodies, sintered permanent magnets and their manufacturing methods |
-
1998
- 1998-03-23 JP JP10095477A patent/JPH11273920A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7087185B2 (en) | 1999-07-22 | 2006-08-08 | Seiko Epson Corporation | Magnetic powder and isotropic bonded magnet |
| WO2005091315A1 (en) * | 2004-03-23 | 2005-09-29 | Japan Science And Technology Agency | R-Fe-B BASED THIN FILM MAGNET AND METHOD FOR PREPARATION THEREOF |
| JPWO2005091315A1 (en) * | 2004-03-23 | 2008-05-22 | 独立行政法人科学技術振興機構 | R-Fe-B system thin film magnet and method for manufacturing the same |
| US7790300B2 (en) | 2004-03-23 | 2010-09-07 | Japan Science And Technology Agency | R-Fe-B based thin film magnet and method for preparation thereof |
| JP4698581B2 (en) * | 2004-03-23 | 2011-06-08 | 独立行政法人科学技術振興機構 | R-Fe-B thin film magnet and method for producing the same |
| JP2015135935A (en) * | 2013-03-28 | 2015-07-27 | Tdk株式会社 | Rare earth based magnet |
| JP2021034711A (en) * | 2019-08-16 | 2021-03-01 | 包頭天和磁気材料科技股▲ふん▼有限公司 | Sintered bodies, sintered permanent magnets and their manufacturing methods |
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