JPH10289811A - Rare-earth magnet material, method of manufacturing the same and rare-earth bonded magnet by the method - Google Patents
Rare-earth magnet material, method of manufacturing the same and rare-earth bonded magnet by the methodInfo
- Publication number
- JPH10289811A JPH10289811A JP9098611A JP9861197A JPH10289811A JP H10289811 A JPH10289811 A JP H10289811A JP 9098611 A JP9098611 A JP 9098611A JP 9861197 A JP9861197 A JP 9861197A JP H10289811 A JPH10289811 A JP H10289811A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- magnet material
- gas
- earth magnet
- rare
- 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
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 58
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000000034 method Methods 0.000 title abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 53
- 229910045601 alloy Inorganic materials 0.000 claims description 51
- 239000000956 alloy Substances 0.000 claims description 51
- 238000011282 treatment Methods 0.000 claims description 49
- 239000007789 gas Substances 0.000 claims description 44
- 238000005121 nitriding Methods 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000354 decomposition reaction Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000005215 recombination Methods 0.000 claims description 14
- 230000006798 recombination Effects 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- 238000000265 homogenisation Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 230000005291 magnetic effect Effects 0.000 description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 150000004767 nitrides Chemical class 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000006247 magnetic powder Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000005415 magnetization Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000000465 moulding Methods 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 229910001172 neodymium magnet Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910017086 Fe-M Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910001199 N alloy Inorganic materials 0.000 description 1
- 229910021141 Sm—F Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Powder Metallurgy (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はＲ3（Ｆｅ，Ｍ，
Ｂ）29Ｎy主相を含む希土類磁石材料およびその製造方
法ならびにそれを用いた希土類ボンド磁石に関する。The present invention relates to R 3 (Fe, M,
B) A rare earth magnet material containing a 29 Ny main phase, a method for producing the same, and a rare earth bonded magnet using the same.
【０００２】[0002]
【従来の技術】従来より、等方性希土類ボンド磁石用磁
粉として超急冷したＮｄ-Ｆｅ-Ｂ系磁粉が多用されてい
るが、キュリー温度が３００℃前後と低く、固有保磁力
（以後ｉＨｃと記す）の温度係数が大きいために高温で
の使用が制限されてきた。最近、Ｓｍ2Ｆｅ17化合物が
窒素を吸蔵することによりＮｄ2Ｆｅ14Ｂ化合物よりも
１６０℃も高い４７０℃というキュリー温度を示し、そ
の異方性磁界もＮｄ2Ｆｅ14Ｂ化合物の異方性磁界（７
５ｋＯｅ）を大きく上回る２６０ｋＯｅになることが報
告され、ボンド磁石用磁粉として工業化が検討されてい
る。Ｓｍ2Ｆｅ17の窒化物Ｓｍ2Ｆｅ17Ｎxは例えばガス
窒化法等で作製されるが粒径を単磁区粒子（数μｍ）程
度にしないと５ｋＯｅ以上の高いｉＨｃが得られないと
ともに、この粒径の磁粉は容易に酸化して磁気特性が劣
化し、かつ急激な酸化による発火の危険性を伴うので現
在のところ実用化が困難である。このようにＳｍ2Ｆｅ
17Ｎx磁粉は粒径が数μｍであるのでボンド磁石に圧縮
成形する際、成形体密度を上げることができず最大エネ
ルギー積の高い希土類ボンド磁石を得られない。また、
成形性が非常に悪く作業効率を著しく低下させるという
問題がある。また、メカニカルアロイング法などの特殊
な製造方法で高いｉＨｃが得られることが報告されてい
るが、この方法は実験室規模の少量生産に適するもの
の、コストパーフォーマンスの点で劣るため量産に至っ
ていない。さらに、Ｓｍ2Ｆｅ17Ｎx窒化物以外にもＴｈ
Ｍｎ12型の結晶構造を有したＮｄ（Ｆｅ，Ｍ）12Ｎx合
金（ＭはＶ、Ｔｉ、Ｍｎ、Ｍｏ等の遷移金属）や、Ｔｂ
Ｃｕ7型の結晶構造を有したＳｍＦｅ7Ｎx合金等が提案
されているが、磁気特性の点で不十分であったり生産性
が悪く高コストになる等の理由で実用化されていない。2. Description of the Related Art Conventionally, ultra-quenched Nd-Fe-B-based magnetic powders have been frequently used as magnetic powders for isotropic rare-earth bonded magnets, but the Curie temperature is as low as about 300 ° C., and the intrinsic coercive force (hereinafter iHc The use at high temperatures has been limited due to the large temperature coefficient of Recently, the Sm 2 Fe 17 compound has a Curie temperature of 470 ° C., which is 160 ° C. higher than that of the Nd 2 Fe 14 B compound, due to the storage of nitrogen, and its anisotropic magnetic field is also anisotropic of the Nd 2 Fe 14 B compound. Magnetic field (7
It is reported to be 260 kOe, which is much higher than 5 kOe), and industrialization as a magnetic powder for bonded magnets is being studied. Nitride Sm 2 Fe 17 N x of Sm 2 Fe 17 together with it is produced by, for example, a gas nitriding method or the like can not be obtained and not the 5kOe or more high iHc particle size to a degree single domain particles (a few [mu] m), this Magnetic powder having a particle size is easily oxidized to deteriorate magnetic properties and is accompanied by a risk of ignition due to rapid oxidation. Thus, Sm 2 Fe
Since 17 N x magnetic powder has a particle size of several μm, it is not possible to increase the density of the compact and to obtain a rare earth bonded magnet having a high maximum energy product when compression molded into a bonded magnet. Also,
There is a problem that the moldability is very poor and the working efficiency is significantly reduced. It has been reported that high iHc can be obtained by a special manufacturing method such as a mechanical alloying method. However, this method is suitable for small-scale production on a laboratory scale, but is inferior in cost performance, leading to mass production. Not in. In addition to Thm other than Sm 2 Fe 17 N x nitride,
Nd (Fe, M) 12 N x alloy (M is a transition metal such as V, Ti, Mn, Mo) having a Mn 12 type crystal structure, Tb
Although an SmFe 7 N x alloy having a Cu 7 type crystal structure has been proposed, it has not been put to practical use because of insufficient magnetic properties, poor productivity and high cost.
【０００３】Collocottらによって最初にProc. 12th In
t.Workshop on RE Magnets and Applications, Canber
a, pp.437-444,1992 (unpublished)に報告されたＲ
3（Ｆｅ，Ｍ）29合金もその窒化物Ｒ3（Ｆｅ，Ｍ）29Ｎ
yが一軸磁気異方性を示すことから永久磁石材料として
有望であることが示唆されている。この合金系のＳｍ3
（Ｆｅ，Ｔｉ）29Ｎy合金をボールミルで平均粒径１５
μｍまで微粉砕することによって保磁力を高められるこ
とがBo-Ping Hu et al.(J.Phys.:Condens.Matter 6(199
4)L197-L200)によって報告されている。しかし、このも
のも平均粒径が１５μｍと小さいため成形体密度の不足
や成形性が悪い等の理由でボンド磁石用磁粉として実用
化することは難しい。一方、Margarian et al.は、J.Ap
pl.Phys.76(1994)6135-6155においてこのＲ3（Ｆｅ，
Ｍ）29合金は非常に不安定で９００〜１０００℃より低
温では他の相に分解してしまうと報告している。このＲ
3（Ｆｅ，Ｍ）29合金の単相を得ることは非常に難し
く、ＴｈＭｎ12型やＴｈ2Ｚｎ17型の結晶構造を有する
Ｒ-（Ｆｅ,Ｍ）合金やＦｅ-Ｍ合金が生成し易い。[0003] Proc. 12th In
t.Workshop on RE Magnets and Applications, Canber
a, pp. 437-444, 1992 (unpublished)
The 3 (Fe, M) 29 alloy also has its nitride R 3 (Fe, M) 29 N
Since y shows uniaxial magnetic anisotropy, it is suggested that it is promising as a permanent magnet material. Sm 3 of this alloy
(Fe, Ti) 29 Ny alloy is ball milled to have an average particle size of 15
Bo-Ping Hu et al. (J. Phys .: Condens. Matter 6 (199
4) Reported by L197-L200). However, these powders also have a small average particle size of 15 μm, so that it is difficult to put them into practical use as magnetic powders for bonded magnets because of insufficient compact density and poor moldability. On the other hand, Margarian et al.
pl.Phys. 76 (1994) 6135-6155, this R 3 (Fe,
M) 29 alloy is reported to be very unstable and decompose to other phases below 900-1000 ° C. This R
3 (Fe, M) 29 alloy it is very difficult to obtain a single phase, has a crystal structure of 12-type and Th 2 Zn 17 type ThMn R- (Fe, M) tends to produce an alloy or Fe-M alloy .
【０００４】また、特開平８-１１１３０５ではこのＲ3
（Ｆｅ，Ｍ）29合金に対してアンモニアガスによる窒化
処理あるいはメタンガスによる浸炭処理を行ってＮまた
はＣを導入することにより１０〜２００μｍの粗粉末で
高い保磁力が得られることを開示している。しかし、Ｒ
3（Ｆｅ，Ｍ）29母合金を窒化または浸炭したものの結
晶粒径と磁気特性の相関については何ら検討されていな
い。磁石合金の結晶粒径制御を目的として、水素による
相変態を利用して高い保磁力を有した磁石合金を作製す
る方法が日本応用磁気学会誌、Ｖｏｌ.１７、Ｎｏ．
１、１９９３、Ｐ２５−３１に記載のＮｄ-Ｆｅ-Ｂ系合
金に開示されているが、ｉＨｃの温度係数は−０．５３
と悪く高温減磁が大きな問題となっていた。さらにＮｄ
-Ｆｅ-Ｂ系合金は水素吸収時に大量の熱を発生しまた再
結晶時に大量の熱を吸収する性質を有しており、量産設
備において上記水素による相変態を利用して磁気特性を
担うＮｄ−Ｆｅ−Ｂ系磁石の主相組織を高い保磁力の得
られる結晶粒径範囲に微細化するためには精密な温度制
御を必要とするものであった。これらのことが、上記の
水素による相変態を利用した高保磁力のＮｄ-Ｆｅ-Ｂ系
合金の工業化を妨げている最大の問題である。In Japanese Patent Application Laid-Open No. Hei 8-111305, this R 3
It discloses that a high coercive force can be obtained with a coarse powder of 10 to 200 μm by introducing N or C by performing nitriding treatment with ammonia gas or carburizing treatment with methane gas on (Fe, M) 29 alloy. . But R
No correlation has been studied between the crystal grain size and magnetic properties of the 3 (Fe, M) 29 mother alloy nitrided or carburized. For the purpose of controlling the crystal grain size of a magnet alloy, a method of producing a magnet alloy having a high coercive force using phase transformation by hydrogen is disclosed in Journal of the Japan Society of Applied Magnetics, Vol.
1, 1993, P25-31, the temperature coefficient of iHc is -0.53.
High temperature demagnetization became a serious problem. Further Nd
-Fe-B alloys have the property of generating a large amount of heat when absorbing hydrogen and absorbing a large amount of heat during recrystallization. Precise temperature control was required in order to refine the main phase structure of the Fe-B based magnet to a crystal grain size range in which a high coercive force could be obtained. These are the biggest problems that hinder the industrialization of the high coercive force Nd-Fe-B-based alloy utilizing the above-described phase transformation by hydrogen.
【０００５】また特開平８−３７１２２にはＲ−Ｔ−Ｍ
−Ｎ系異方性ボンド磁石の製造方法において、Ｔｈ2Ｚ
ｎ17型構造またはＴｂＣｕ7型構造を有する合金を異方
性化する手段として水素を用いた相変態を利用する方法
を開示している。しかし、Ｒ3（Ｆｅ，Ｍ，Ｂ）29化合
物については全く開示がない。Japanese Patent Application Laid-Open No. 8-37122 discloses an RTM
-N-based anisotropic bonded magnet manufacturing method, wherein Th 2 Z
A method utilizing a phase transformation using hydrogen as a means for anisotropizing an alloy having an n 17 type structure or a TbCu 7 type structure is disclosed. However, there is no disclosure of the R 3 (Fe, M, B) 29 compound.
【０００６】[0006]
【発明が解決しようとする課題】ボンド磁石の耐熱性を
向上するためにはｉＨｃの絶対値を高くするとともにｉ
Ｈｃの温度係数を小さくする必要があるので、異方性磁
界が大きいとともにキュリー温度が高い希土類磁石粉末
が必要である。前述したようにＲ-Ｆｅ-Ｎ系合金は従来
のＮｄ-Ｆｅ-Ｂ系合金よりも異方性磁界が大きくかつキ
ュリー温度が高いことからｉＨｃの温度係数の小さい材
料として期待されているが、Ｒ-Ｆｅ-Ｎ系合金で５ｋＯ
ｅ以上の高いｉＨｃを得るには上記の通り数μｍの微粉
状にする必要があり、この微粉末は通常工業生産で用い
られている６〜１０ｔｏｎ／ｃｍ2程度の成形圧力では
ボンド磁石の成形体密度を十分に上げることができず最
大エネルギー積の高いものが得られないとともに、酸化
し易く不安定でさらに成形性が非常に悪いものである。
上記従来の問題を踏まえて、本発明の課題はｉＨｃが大
きいとともに従来に比べてｉＨｃの温度係数が小さく熱
安定性に優れたＲ3（Ｆｅ，Ｍ，Ｂ）29Ｎy主相を含む希
土類磁石材料およびその製造方法ならびにそれを用いた
希土類ボンド磁石を提供することである。In order to improve the heat resistance of the bonded magnet, the absolute value of iHc must be increased and i
Since it is necessary to reduce the temperature coefficient of Hc, a rare-earth magnet powder having a large anisotropic magnetic field and a high Curie temperature is required. As described above, the R-Fe-N-based alloy is expected to be a material having a small temperature coefficient of iHc because of its larger anisotropic magnetic field and higher Curie temperature than the conventional Nd-Fe-B-based alloy. 5kO with R-Fe-N alloy
In order to obtain a high iHc of e or more, it is necessary to form a fine powder of several μm as described above. This fine powder can be formed into a bonded magnet at a molding pressure of about 6 to 10 ton / cm 2 which is usually used in industrial production. In addition to the fact that the body density cannot be sufficiently increased and a product having a high maximum energy product cannot be obtained, it is liable to be oxidized, is unstable, and has very poor moldability.
In view of the above conventional problems, an object of the present invention is to provide a rare earth element containing a main phase of R 3 (Fe, M, B) 29 Ny having a large iHc and a small temperature coefficient of iHc as compared with the conventional, and having excellent thermal stability. An object of the present invention is to provide a magnet material, a method of manufacturing the same, and a rare-earth bonded magnet using the same.
【０００７】[0007]
【課題を解決するための手段】本発明者らはボンド磁石
の成形工程における成形容易性およびそれに用いる希土
類磁石材料粉末の高い磁気特性を確保する目的で、平均
粒径が２０μｍ以上の粗粉において高いｉＨｃと飽和磁
化、および低いｉＨｃの温度係数（η）を有したＲーＦ
ｅーＮ系磁石粉末を得るために種々のプロセスを鋭意検
討した結果、Ｒ−Ｆｅ−Ｍ−Ｂ−Ｎ系磁石材料において
水素を用いた特定の条件下で水素化、分解、脱水素、再
結合の順で相変態反応を起こさせ、その後窒化処理する
ことにより微細結晶のＲ3（Ｆｅ，Ｍ，Ｂ）29Ｎy主相が
得られ上記課題を解決できることを見出し本発明に想到
した。すなわち、本発明は、成分組成がＲαＦｅ100-
(α+β+γ+δ)ＭβＢγＮδで表され、単斜晶および／
または六方晶の結晶構造を有し平均結晶粒径が０．０５
〜１．０μｍであるＲ3（Ｆｅ，Ｍ，Ｂ）29Ｎy主相を含
み、前記ＲはＹを含めた希土類元素のいずれか１種また
は２種以上であり、前記ＭはＡｌ、Ｔｉ、Ｖ、Ｃｒ、Ｍ
ｎ、Ｃｕ、Ｇａ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、Ｔａ、Ｗの
いずれか１種または２種以上であり、前記α、β、γ、
δは原子百分率で下記の範囲にあることを特徴とする希
土類磁石材料である。 ５≦α≦１８ １≦β≦５０ ０．１≦γ≦５ ４≦δ≦３０ 上記希土類元素ＲとしてはＹ、Ｌａ、Ｃｅ、Ｐｒ、Ｎ
ｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔ
ｍ、Ｙｂ、Ｌｕのいずれか１種または２種以上を含めば
よく、ミッシュメタルやジジム等の２種以上の希土類元
素の混合物を用いてもよい。好ましい希土類元素Ｒとし
てはＹ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、Ｄｙ、Ｅｒの
いずれか１種または２種以上であり、さらに好ましくは
Ｙ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍのいずれか１種または２種
以上であり、特に好ましいのはＳｍである。Ｒ成分の５
０原子％以上さらには７０原子％以上がＳｍである場合
に際だって高い保磁力が得られる。ここで、希土類元素
Ｒは工業的生産により入手可能な純度でよく、製造上混
入が避けられないＯ、Ｈ、Ｃ、Ａｌ、Ｓｉ、Ｎａ、Ｍ
ｇ、Ｃａ等の不純物元素が含有されていてもよい。本発
明の希土類磁石材料はＲ成分を５〜１８原子％含有す
る。Ｒ成分が５原子％未満になると鉄成分を多く含む軟
磁性相の析出を促進してｉＨｃが低下し、１８原子％を
越えると非磁性のＲリッチ化合物が析出して飽和磁束密
度を低下させるので好ましくない。さらに好ましいＲ成
分範囲は６〜１２原子％である。Means for Solving the Problems In order to ensure the ease of molding in the molding step of the bonded magnet and the high magnetic properties of the rare-earth magnet material powder used in the method, the present inventors have proposed a method for producing a coarse powder having an average particle diameter of 20 μm or more. RF with high iHc and saturation magnetization, and low iHc temperature coefficient (η)
As a result of intensive studies on various processes for obtaining an eN-based magnet powder, hydrogenation, decomposition, dehydrogenation, and re-generation under specific conditions using hydrogen in an R-Fe-MBN-based magnet material were performed. The present inventors have found out that the above-mentioned problem can be solved by causing a phase transformation reaction in the order of bonding and then performing a nitriding treatment to obtain a fine crystal R 3 (Fe, M, B) 29 Ny main phase and solve the above-mentioned problems. That is, in the present invention, the component composition is RαFe100-
(α + β + γ + δ) MβBγNδ, monoclinic and / or
Or having a hexagonal crystal structure and an average crystal grain size of 0.05
A main phase of R 3 (Fe, M, B) 29 N y of 1.0 to 1.0 μm, wherein R is one or more of rare earth elements including Y, and M is Al, Ti , V, Cr, M
n, Cu, Ga, Zr, Nb, Mo, Hf, Ta, W or any one or more of the above, α, β, γ,
δ is a rare earth magnet material characterized by the following atomic percentage in the following range. 5 ≦ α ≦ 18 1 ≦ β ≦ 50 0.1 ≦ γ ≦ 54 4 ≦ δ ≦ 30 As the rare earth element R, Y, La, Ce, Pr, N
d, Sm, Eu, Gd, Tb, Dy, Ho, Er, T
Any one or more of m, Yb, and Lu may be included, and a mixture of two or more rare earth elements such as misch metal and dymium may be used. Preferred rare earth elements R are any one or more of Y, Ce, Pr, Nd, Sm, Gd, Dy, and Er, and more preferably any one of Y, Ce, Pr, Nd, and Sm. Alternatively, two or more kinds are preferable, and Sm is particularly preferable. R component 5
A remarkably high coercive force is obtained when Sm is at least 0 atomic% and further at least 70 atomic%. Here, the rare earth element R may have a purity that can be obtained by industrial production, and O, H, C, Al, Si, Na, and M, which are unavoidable in production.
An impurity element such as g or Ca may be contained. The rare earth magnet material of the present invention contains 5 to 18 atomic% of the R component. When the R component is less than 5 atomic%, the precipitation of a soft magnetic phase containing a large amount of iron component is promoted to lower iHc. When the R component exceeds 18 atomic%, a non-magnetic R-rich compound is precipitated to lower the saturation magnetic flux density. It is not preferable. A more preferable range of the R component is 6 to 12 atomic%.
【０００８】また、上記希土類磁石材料は粉体の平均粒
径を２０μｍ以上５００μｍ以下とすると好ましい。２
０μｍ未満では酸化による品質劣化および成形性劣化が
顕著となり、５００μｍを超えると通常の窒化条件では
窒素の拡散距離が粒子径の大きな粉末粒子に対して不十
分となり易く粉末粒子内にほぼ均一に窒化物が形成され
ない不具合を生じて好ましくない。より好ましい粉体の
平均粒径の範囲は３０〜４００μｍである。It is preferable that the rare earth magnet material has a powder having an average particle diameter of 20 μm or more and 500 μm or less. 2
If it is less than 0 μm, quality deterioration and formability deterioration due to oxidation become remarkable, and if it exceeds 500 μm, under normal nitriding conditions, the diffusion distance of nitrogen tends to be insufficient for powder particles having a large particle diameter, and nitriding is almost uniform in powder particles. It is not preferable because a problem that a product is not formed occurs. A more preferable range of the average particle size of the powder is 30 to 400 μm.
【０００９】また、本発明ではＲ3（Ｆｅ，Ｍ，Ｂ）29
Ｎy相の結晶粒内にＭ元素またはＭ化合物が析出してい
る場合に高いｉＨｃと低いｉＨｃの温度係数（η）が得
られている。In the present invention, R 3 (Fe, M, B) 29
When the M element or the M compound is precipitated in the crystal grains of the N y phase, a temperature coefficient (η) of high iHc and low iHc is obtained.
【００１０】本発明の希土類磁石材料は単斜晶および／
または六方晶の結晶構造を有したＲ3（Ｆｅ，Ｍ，Ｂ）
29Ｎy相単相のものが理想的であるが、この主相の他に
磁石特性に寄与しない他の化合物（以後副相と呼ぶ）を
含有することができる。この副相としてＴｈ2Ｚｎ
17型、ＴｂＣｕ7型、ＴｈＭｎ12型などの結晶構造を有
するＲ-Ｆｅ-Ｍ-Ｂ-Ｎ系磁性化合物を含んでいてもよい
が、本発明ではＲ3（Ｆｅ，Ｍ，Ｂ）29Ｎy主相の含有比
率は６０体積％以上が好ましく、７５体積％以上がより
好ましい。The rare earth magnet material of the present invention is monoclinic and / or
Or R 3 (Fe, M, B) having a hexagonal crystal structure
A single phase of 29 N y phase is ideal, but may contain other compounds that do not contribute to the magnetic properties (hereinafter referred to as sub-phases) in addition to the main phase. Th 2 Zn as this subphase
R-Fe-MBN-based magnetic compounds having a crystal structure such as 17- type, TbCu 7- type, and ThMn 12- type may be included, but in the present invention, R 3 (Fe, M, B) 29 N The content ratio of the y main phase is preferably at least 60% by volume, more preferably at least 75% by volume.
【００１１】本発明の希土類磁石材料は、粉末状態で２
５℃におけるｉＨｃが６ｋＯｅ以上であり、２５〜１０
０℃におけるｉＨｃの温度係数（η）が−０．４５以上
である高い磁気特性を有している。[0011] The rare earth magnet material of the present invention can be used in powder form.
IHc at 5 ° C. is 6 kOe or more, and 25 to 10
It has high magnetic properties with the temperature coefficient (η) of iHc at 0 ° C. being −0.45 or more.
【００１２】上記希土類磁石材料の粉末を、高分子重合
体、純金属、合金のいずれかのバインダーで結合した希
土類ボンド磁石は高いｉＨｃと低いｉＨｃの温度係数
（η）を有している。前記ボンド磁石の２５℃における
ｉＨｃは６ｋＯｅ以上であり、２５〜１００℃における
ｉＨｃの温度係数（η）が−０.４５以上である等方性
の希土類ボンド磁石を提供できる。A rare earth bonded magnet in which the powder of the above rare earth magnet material is bound with a binder of a polymer, a pure metal, or an alloy has a high iHc and a low iHc temperature coefficient (η). It is possible to provide an isotropic rare earth bonded magnet in which the bond magnet has an iHc at 25 ° C. of 6 kOe or more and a temperature coefficient (η) of iHc at 25 to 100 ° C. of −0.45 or more.
【００１３】Ｆｅは４７原子％以上を含有することが好
ましい。Ｆｅが４７原子％未満では飽和磁化が小さくな
り好ましくない。It is preferable that Fe contains 47 atomic% or more. If Fe is less than 47 atomic%, the saturation magnetization is undesirably small.
【００１４】上記Ｍ元素はＲ3（Ｆｅ，Ｍ，Ｂ）29主相
の安定性を向上させる役割を果たしている。高い磁気特
性を有するレベルにＲ3（Ｆｅ，Ｍ，Ｂ）29相を生成さ
せるに要するＭ元素の添加量はＭ元素の種類毎に異な
る。Ｍ元素のいずれでも５０原子％を越えて添加すると
ＴｈＭｎ12型の結晶構造を有するＲ（Ｆｅ，Ｍ，Ｂ）12
相の生成率が大きくなりｉＨｃが顕著に低下する。Ｍ元
素が１原子％未満ではＴｈ2Ｚｎ17型の結晶構造を有す
るＲ2（Ｆｅ，Ｍ，Ｂ）17相の生成率が大きくなりＲ
3（Ｆｅ，Ｍ，Ｂ）29相の存在比率が相対的に低下す
る。よってＭ元素の好ましい添加量は１〜５０原子％で
ある。Ｍ元素のうちでより好ましい元素はＴｉ、Ｍｎ、
Ｃｒ、Ｚｒ、Ｖのいずれか１種または２種以上である。The above-mentioned M element plays a role of improving the stability of the R 3 (Fe, M, B) 29 main phase. The addition amount of the M element required to generate the R 3 (Fe, M, B) 29 phase at a level having high magnetic characteristics differs depending on the type of the M element. When any of the M elements is added in excess of 50 atomic%, R (Fe, M, B) 12 having a ThMn 12 type crystal structure
The formation rate of the phase is increased, and iHc is significantly reduced. If the M element is less than 1 atomic%, the generation rate of the R 2 (Fe, M, B) 17 phase having a Th 2 Zn 17 type crystal structure increases, and the R
The proportion of the 3 (Fe, M, B) 29 phase is relatively reduced. Therefore, the preferable addition amount of the element M is 1 to 50 atomic%. Among the M elements, more preferred elements are Ti, Mn,
Any one or more of Cr, Zr, and V.
【００１５】ＢはＭ元素が共存することにより母合金相
中におけるＲ3（Ｆｅ，Ｍ，Ｂ）29相の構成比率を高め
る効果、母合金の均質化処理温度を広い温度域とし結果
として低温度域での均質化処理を選択できることにより
Ｓｍの蒸発量を少なくする効果、窒化処理時にＲ3（Ｆ
ｅ，Ｍ，Ｂ）29相の分解を抑制する効果等を有する。ま
た、水素によるより低温域での相変態反応すなわち水素
化、分解、脱水素、再結合反応を可能にしこの反応時に
おけるＳｍの蒸発を抑制し組成ずれを防ぐ効果も認めら
れる。本発明においてＢの好ましい含有量は０．１〜５
原子％である。Ｂが０．１原子％未満および５原子％を
越えるとＲ3（Ｆｅ，Ｍ，Ｂ）29Ｎy窒化物相が不安定と
なり他の相へ分解し易くなり好ましくない。すなわち、
Ｒ3（Ｆｅ，Ｍ，Ｂ）29Ｎy相を安定化する作用は上記Ｂ
添加量の範囲にあるときに発揮される。B has the effect of increasing the composition ratio of the R 3 (Fe, M, B) 29 phase in the master alloy phase due to the coexistence of the M element, and the homogenization temperature of the master alloy is set to a wide temperature range, resulting in a low temperature. effect of reducing the amount of evaporation of Sm by can select a homogenization treatment at a temperature range, R 3 during the nitriding treatment (F
e, M, B) It has an effect of suppressing decomposition of the 29 phase. In addition, an effect is also recognized that enables a phase transformation reaction by hydrogen at a lower temperature range, that is, hydrogenation, decomposition, dehydrogenation, and recombination reactions, suppresses evaporation of Sm during this reaction, and prevents a composition deviation. In the present invention, the preferable content of B is 0.1 to 5
Atomic%. If B is less than 0.1 atomic% or more than 5 atomic%, the R 3 (Fe, M, B) 29 N y nitride phase becomes unstable and is easily decomposed into another phase, which is not preferable. That is,
The effect of stabilizing the R 3 (Fe, M, B) 29 Ny phase is described in the above B
It is exhibited when it is within the range of the addition amount.
【００１６】Ｒ3（Ｆｅ，Ｍ，Ｂ）29相に導入される窒
素Ｎは４〜３０原子％とすることが好ましい。窒素Ｎが
４原子％未満では磁化が低くなるとともに、３０原子％
を越えると保磁力を向上させることが困難である。より
好ましい窒素Ｎの含有量は１０〜２０原子％である。The nitrogen N introduced into the R 3 (Fe, M, B) 29 phase is preferably 4 to 30 atomic%. If the nitrogen N content is less than 4 at%, the magnetization becomes low and
If it exceeds, it is difficult to improve the coercive force. More preferably, the content of nitrogen N is 10 to 20 atomic%.
【００１７】また、Ｆｅの０.０１〜３０原子％をＣｏ
および／またはＮｉで置換することが好ましく、Ｃｏお
よび／またはＮｉの導入によりキュリー温度が上昇する
とともにｉＨｃの温度係数（η）を向上する効果があ
る。しかし、３０原子％を越えると飽和磁束密度および
ｉＨｃの顕著な低下を招来するとともに、０．０１原子
％未満ではＣｏおよび／またはＮｉの添加効果が認めら
れない。Ｃｏおよび／またはＮｉによるＦｅ置換量のよ
り好ましい範囲は１〜２０原子％である。Further, 0.01 to 30 atomic% of Fe is Co
And / or Ni is preferable, and the introduction of Co and / or Ni has an effect of increasing the Curie temperature and improving the temperature coefficient (η) of iHc. However, if it exceeds 30 atomic%, the saturation magnetic flux density and iHc are remarkably reduced, and if it is less than 0.01 atomic%, the effect of adding Co and / or Ni is not recognized. A more preferred range of the amount of Fe replaced by Co and / or Ni is 1 to 20 atomic%.
【００１８】また、本発明は、成分組成がＲαＦｅ100-
(α+β+γ+δ)ＭβＢγＮδで表され、単斜晶および／
または六方晶の結晶構造を有したＲ3（Ｆｅ，Ｍ，Ｂ）
29Ｎy主相を含み、前記ＲはＹを含めた希土類元素のい
ずれか１種または２種以上であり、前記ＭはＡｌ、Ｔ
ｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｕ、Ｇａ、Ｚｒ、Ｎｂ、Ｍｏ、
Ｈｆ、Ｔａ、Ｗのいずれか１種または２種以上であり、
前記α、β、γ、δが原子百分率で下記の範囲にある希
土類磁石材料の製造方法において、前記組成の合金を鋳
造後、均質化処理を行い、続いて粗粉砕したものを、
０．１〜１０ａｔｍのＨ2ガス中またはＨ2ガス分圧を有
した不活性ガス（Ｎ2ガスを除く）中で７００〜９００
℃×０．５〜８時間保持する水素化、分解反応処理を行
い、続いてさらに好ましくは１×１０-2〜１×１０-6Ｔ
ｏｒｒの真空中に７００〜９００℃×０．５〜８時間保
持する脱水素、再結合反応処理を行った後、窒化処理を
行うことを特徴とする希土類磁石材料の製造方法であ
る。 ５≦α≦１８ １≦β≦５０ ０．１≦γ≦５ ４≦δ≦３０ また、鋳造後に、７００〜１２５０℃×０.５〜１００
時間の均質化処理を行うことが高い磁気特性を安定に得
るために好ましい。また、窒化処理後に、真空中あるい
は不活性ガス中（Ｎ２ガスを除く）で３００〜６００℃
×０.５〜５０時間の熱処理を行うとさらに高いｉＨｃ
が得られ易いので好ましい。また、０．２〜１０ａｔｍ
のＮ2ガス、Ｈ2が１〜９５モル％で残部Ｎ2からなるＨ2
とＮ2の混合ガス、ＮＨ3のモル％が１〜５０％で残部Ｈ
2からなるＮＨ3とＨ2の混合ガスのうちのいずれかの雰
囲気中で３００〜６５０℃×０．１〜３０時間保持する
ガス窒化処理が実用性に富む窒化処理方法である。Further, according to the present invention, the component composition is RαFe100-
(α + β + γ + δ) MβBγNδ, monoclinic and / or
Or R 3 (Fe, M, B) having a hexagonal crystal structure
29 N y main phase, wherein R is one or more of rare earth elements including Y, and M is Al, T
i, V, Cr, Mn, Cu, Ga, Zr, Nb, Mo,
One or more of Hf, Ta, and W;
In the method for producing a rare earth magnet material in which the α, β, γ, and δ are in the following range in atomic percentage, after casting an alloy having the above composition, a homogenization treatment is performed, and then a roughly pulverized material is obtained.
In H 2 gas 0.1~10atm or H 2 (except for N 2 gas) gas partial inert gas having a pressure in 700-900
Hydrogenation and decomposition reaction treatment are performed at a temperature of 0.5 ° C. × 0.5 to 8 hours, and then more preferably 1 × 10 −2 to 1 × 10 −6 T
This is a method for producing a rare-earth magnet material, which comprises performing a dehydrogenation / recombination reaction treatment at 700 to 900 ° C. × 0.5 to 8 hours in an orr vacuum, followed by a nitriding treatment. 5 ≦ α ≦ 18 1 ≦ β ≦ 50 0.1 ≦ γ ≦ 54 4 ≦ δ ≦ 30 Also, after casting, 700 to 1250 ° C. × 0.5 to 100
It is preferable to perform a time homogenization treatment in order to stably obtain high magnetic characteristics. After the nitriding treatment, 300 to 600 ° C. in vacuum or in an inert gas (excluding N 2 gas).
× 0.5 to 50 hours heat treatment for higher iHc
Is preferred because it is easily obtained. Also, 0.2 to 10 atm
H 2 to the N 2 gas, H 2 is the balance N 2 with 1 to 95 mol%
Remainder H and a mixed gas of N 2, in mole percent of NH 3 1 to 50%
Gas nitriding of holding 300 to 650 ° C. × 0.1 to 30 hours in one atmosphere of NH 3 and a mixed gas of H 2 consisting of 2 are nitriding method rich in practicability.
【００１９】本発明ではＲ3（Ｆｅ，Ｍ，Ｂ）29相を主
相とする化合物を上記加熱条件でＨ2と反応させる水素
化、分解反応処理により希土類元素Ｒの水素化物ＲＨ
ｘ、αＦｅ−Ｍ（Ｂ）相などに分解する。さらにこの状
態から上記加熱条件で水素成分を強制的に取り除く脱水
素、再結合反応処理によりＲ3（Ｆｅ，Ｍ，Ｂ）29相の
微細な再結合組織（平均結晶粒径が０．０５〜１．０μ
ｍの再結晶組織であり、各結晶粒子はランダム方向に配
向している。）が得られる。この水素化、分解反応では
Ｈ2ガスの単独またはＮ2ガスを除く不活性ガスとＨ2ガ
スとの混合ガス中での加熱に際し、Ｈ2分圧が０．１ａ
ｔｍ未満では上記分解反応が十分に起こらず、１０ａｔ
ｍを越えると処理設備が大型化しコスト高を招来するの
で好ましくない。よってＨ2分圧の好ましい範囲は０．
１〜１０ａｔｍであり、０．５〜２．０ａｔｍがより好
ましい。また、この水素化、分解反応の加熱条件は７０
０℃×０．５時間未満ではＲ−Ｆｅ−Ｍ−Ｂ系化合物が
Ｈ2を吸収するのみでＲＨx、αＦｅ-Ｍ(Ｂ)、Ｆｅ-Ｂ
(Ｍ)相などへの分解がほとんど起こらず、また９００℃
×８時間を越えると脱水素後のＲ3（Ｆｅ，Ｍ，Ｂ）29
相の結晶粒径が粗大化してこのものを窒化処理して得ら
れるＲ3（Ｆｅ，Ｍ，Ｂ）29Ｎy相の結晶粒径が粗大化し
ｉＨｃが顕著に低下するので７００〜９００℃×０．５
〜８時間が好ましく、上記の分解反応を十分に行わせる
ためには７２５〜８７５℃×０．５〜１０時間がより好
ましい。脱水素、再結合処理時のＨ2分圧が１ｘ１０-2
Ｔｏｒｒよりも低いと処理に長時間を要し好ましくな
く、１ｘ１０-6Ｔｏｒｒを越えた高真空とすると真空排
気装置のコストが増大するので実用的でない。脱水素、
再結合処理時の加熱保持条件が７００℃×０．５時間未
満ではＲＨｘ等の分解がほとんど進行せず、また９００
℃×１０時間を越えると得られたＲ3(Fe,M,B)29相の再
結晶組織が粒成長のため粗大結晶粒化し易く高いｉＨｃ
を得ることが困難である。したがって脱水素、再結合反
応処理は７００〜９００℃×０．５〜１０時間が好まし
く、ＲＨｘ等の分解反応およびＲ3（Ｆｅ,Ｍ,Ｂ）29相
の再結晶反応を微細結晶組織を保持しながら十分に行わ
せるためには７２５〜８７５℃×０．５〜１０時間の加
熱保持を行うことがより好ましい。上記の通り、本発明
の製造方法の特長は水素化、分解反応処理により母合金
結晶を十分に分解し、続いて行う脱水素、再結合反応処
理により再結合反応処理後のものおよび窒化処理後の主
相の結晶組織をランダム方位に微細化するものであり、
高いｉＨｃを安定に得られる実用性に富む製法である。In the present invention, a compound having a main phase of R 3 (Fe, M, B) 29 is reacted with H 2 under the above-mentioned heating conditions, and a hydride RH of a rare earth element R is obtained by a decomposition reaction treatment.
Decomposes into x, αFe-M (B) phase and the like. Further, from this state, a fine recombined structure of R 3 (Fe, M, B) 29 phase (average crystal grain size of 0.05 to less) is obtained by dehydrogenation and recombination reaction treatment for forcibly removing the hydrogen component under the above heating conditions. 1.0μ
m, and each crystal grain is oriented in a random direction. ) Is obtained. In this hydrogenation and decomposition reaction, when H 2 gas is heated alone or in a mixed gas of an inert gas excluding N 2 gas and H 2 gas, the H 2 partial pressure is 0.1 a.
If it is less than tm, the above decomposition reaction does not sufficiently occur and 10 atm
Exceeding m is not preferable because the processing equipment becomes large and the cost is increased. Therefore, the preferable range of the H 2 partial pressure is 0.1.
1 to 10 atm, preferably 0.5 to 2.0 atm. The heating conditions for this hydrogenation and decomposition reaction are 70
When the temperature is less than 0 ° C. × 0.5 hours, the R-Fe-MB compound only absorbs H 2 and RHx, αFe-M (B), Fe-B
Decomposition into (M) phase etc. hardly occurs, and 900 ° C
If over 8 hours, R 3 (Fe, M, B) after dehydrogenation 29
The crystal grain size of the R 3 (Fe, M, B) 29 Ny phase obtained by nitriding the crystal grain of the phase is coarsened and iHc is remarkably reduced. 0.5
-8 to 8 hours, more preferably 725 to 875 ° C. × 0.5 to 10 hours in order to sufficiently perform the above decomposition reaction. H 2 partial pressure at the time of dehydrogenation and recombination treatment is 1 × 10 -2
If the pressure is lower than Torr, it takes a long time for the treatment, which is not preferable. If a high vacuum exceeding 1 × 10 −6 Torr is used, the cost of the vacuum pumping device increases, which is not practical. Dehydrogenation,
If the heating and holding conditions during the recombination treatment are less than 700 ° C. × 0.5 hours, the decomposition of RHx and the like hardly proceeds,
When the temperature exceeds 10 ° C. × 10 hours, the recrystallized structure of the obtained R 3 (Fe, M, B) 29 phase tends to become coarse grains due to grain growth, and high iHc
Is difficult to obtain. Therefore, the dehydrogenation and recombination reaction treatment is preferably performed at a temperature of 700 to 900 ° C. for 0.5 to 10 hours, and the decomposition reaction such as RHx and the recrystallization reaction of the R 3 (Fe, M, B) 29 phase maintain a fine crystal structure. It is more preferable to perform heating and holding at 725 to 875 ° C. × 0.5 to 10 hours in order to perform the heating sufficiently. As described above, the features of the production method of the present invention are that the mother alloy crystal is sufficiently decomposed by hydrogenation and decomposition reaction treatment, and subsequently dehydrogenation and recombination reaction treatment are performed after the recombination reaction treatment and after nitriding treatment. To refine the crystal structure of the main phase into random orientations,
This is a highly practical production method capable of stably obtaining high iHc.
【００２０】窒化処理後の磁性粉の平均結晶粒径を０．
０５〜１．０μｍに限定した理由は０．０５μｍ未満の
平均結晶粒径のものを安定に量産することが困難であ
り、また１．０μｍを越えると磁性粉のｉＨｃが顕著に
減少するからである。より好ましい平均結晶粒径は０．
１〜０．５μｍである。本発明において窒化処理を行う
前に必要に応じて粉砕、分級を行い粉末の粒径を調整す
ることは均一な窒化処理を行う上から好ましい。ガス窒
化法を採用する場合には、窒化処理時のＮ2単独ガスま
たはＮ2を含有したガスの圧力を０．２〜１０ａｔｍに
することが好ましい。０．２ａｔｍ未満では窒化反応が
遅く、１０ａｔｍを越えると高圧ガスの設備に多大のコ
ストを要する。より好ましいＮ2圧力範囲は１〜１０ａ
ｔｍである。ガス窒化の加熱条件は３００〜６５０℃×
０．１〜３０時間が好ましい。３００℃×０．１時間未
満では窒化がほとんど進行せず、６５０℃×３０時間を
越えるとＲ3（Ｆｅ，Ｍ，Ｂ）Ｎ2 9主相がほとんどＲＮ
とＦｅ−Ｍ(Ｂ)に分解しｉＨｃが顕著に低下するので好
ましくない。より好ましいガス窒化の加熱条件は４００
〜５５０℃×０．５〜３０時間であり、４００〜５５０
℃×１〜１０時間が特に好ましい。The average crystal grain size of the magnetic powder after nitriding is set to 0.1.
The reason for limiting to 0.5 to 1.0 μm is that it is difficult to stably mass-produce those having an average crystal grain size of less than 0.05 μm, and if it exceeds 1.0 μm, the iHc of the magnetic powder is significantly reduced. is there. A more preferred average crystal grain size is 0.1.
1 to 0.5 μm. In the present invention, it is preferable to adjust the particle size of the powder by performing pulverization and classification as necessary before performing the nitriding treatment from the viewpoint of performing a uniform nitriding treatment. When the gas nitriding method is employed, it is preferable that the pressure of the N 2 gas alone or the gas containing N 2 during the nitriding treatment is set to 0.2 to 10 atm. If it is less than 0.2 atm, the nitridation reaction is slow, and if it exceeds 10 atm, enormous cost is required for high-pressure gas equipment. A more preferable N 2 pressure range is 1 to 10a.
tm. Heating conditions for gas nitriding are 300-650 ° C x
0.1 to 30 hours is preferred. At less than 300 ° C. × 0.1 hours hardly proceed nitride, exceeds 650 ° C. × 30 h R 3 (Fe, M, B ) N 2 9 main phase is almost RN
And Fe-M (B), which is not preferable because iHc is remarkably reduced. More preferred heating conditions for gas nitriding are 400
５550 ° C. × 0.5〜30 hours, 400〜550
C. x 1 to 10 hours are particularly preferred.
【００２１】[0021]
【発明の実施の形態】以下本発明を詳説する。Ｒ3（Ｆ
ｅ，Ｍ，Ｂ）29Ｎy主相は、理想的には母合金全部また
は母合金を主に構成するＲ3（Ｆｅ，Ｍ，Ｂ）29相の結
晶格子間に窒素が侵入してその結晶格子が膨張すること
によって得られるが、その結晶構造はＲ3（Ｆｅ，Ｍ，
Ｂ）29相とほぼ同じ対称性を有する。例えば母合金粉末
として原子％表示でＳｍ9.4Ｆｅ84.0Ｂ2.0Ｖ4.5の組成
のものを選んだ場合、窒素を導入することによって結晶
磁気異方性が面内異方性から一軸異方性に変化し永久磁
石材料として好適なものになる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. R 3 (F
e, M, B) 29 N y major phase, the ideally penetrate nitrogen between crystal lattice of R 3 (Fe, M, B ) 29 phase which mainly constitute the matrix alloy whole or master alloy to The crystal structure is obtained by expanding the crystal lattice, and its crystal structure is represented by R 3 (Fe, M,
B) It has almost the same symmetry as the 29 phase. For example, when a mother alloy powder having a composition of Sm9.4Fe84.0B2.0V4.5 in atomic% is selected, the introduction of nitrogen changes the crystal magnetic anisotropy from in-plane anisotropy to uniaxial anisotropy. It changes and becomes suitable as a permanent magnet material.
【００２２】本発明にかかる希土類ボンド磁石は、上記
希土類磁石材料を高分子重合体、純金属、合金等のいず
れかのバインダーで固めてなるものであるが、高分子重
合体としてはエポキシ樹脂やフェノール樹脂等に代表さ
れる熱硬化樹脂またはポリアミド樹脂やＥＥＡ樹脂等の
熱可塑性樹脂または合成ゴムや天然ゴム等の公知のもの
を用い得る。また、純金属または合金としては亜鉛や錫
などの公知の低融点金属や低融点合金を用いることがで
きる。また、希土類ボンド磁石の成形方法としては圧縮
成形や射出成形などの公知の成形方法を採用できる。The rare-earth bonded magnet according to the present invention is obtained by solidifying the above-mentioned rare-earth magnet material with a binder such as a polymer, a pure metal or an alloy. A thermosetting resin represented by a phenol resin, a thermoplastic resin such as a polyamide resin or an EEA resin, or a known resin such as a synthetic rubber or a natural rubber can be used. In addition, as the pure metal or alloy, a known low melting point metal or alloy such as zinc or tin can be used. Further, as a molding method of the rare earth bonded magnet, a known molding method such as compression molding or injection molding can be adopted.
【００２３】本発明によれば、Ｒ3（Ｆｅ，Ｍ，Ｂ）29
Ｎy主相の平均結晶粒径を０．０５〜１．０μｍとした
希土類磁石材料を容易かつ安定に作製できるので、キュ
リー温度が約４８０±２０℃と高く、また粉末粒子の平
均粒径で２０〜５００μｍの幅広い粒径にわたって略一
定の高いｉＨｃと低いｉＨｃの温度係数（η）を有した
耐熱性に優れた希土類磁石粉末を提供できると同時に、
耐熱性に富む高い磁気特性の等方性ボンド磁石を容易に
提供できる。According to the present invention, R 3 (Fe, M, B) 29
Since the N y main phase rare earth magnet materials with average 0.05~1.0μm the crystal grain size of easily and stably be produced, the Curie temperature is as high as about 480 ± 20 ° C., and in the average particle size of the powder particles It is possible to provide a rare-earth magnet powder excellent in heat resistance having a substantially constant high iHc and a low iHc temperature coefficient (η) over a wide range of particle diameters of 20 to 500 μm,
An isotropic bonded magnet having high magnetic properties and high heat resistance can be easily provided.
【００２４】次に、本発明の代表的な製造工程を説明す
る。Next, a typical manufacturing process of the present invention will be described.
【００２５】（母合金の調整）Ｒ-Ｆｅ-Ｍ-Ｂ系母合金
は例えば高周波溶解法、アーク溶解法、超急冷法、スト
リップキャスト法、ガスアトマイズ法、還元拡散法、メ
カニカルアロイング法等のいずれかを用いて合金化され
る。ここで、高周波溶解法またはアーク溶解法を用いた
場合には上記合金が凝固する際にαＦｅを主成分とする
軟磁性相が析出し易いが、この軟磁性相は窒化処理後も
残留しｉＨｃを低下させる要因となるので好ましくな
い。この軟磁性相の生成を抑えるには溶製した母合金を
真空中またはアルゴンガス雰囲気で７００〜１２５０℃
×０．５〜１００時間の加熱条件で均質化処理すること
が望ましい。(Adjustment of Master Alloy) The R-Fe-MB base alloy is prepared by, for example, a high-frequency melting method, an arc melting method, a super-quenching method, a strip casting method, a gas atomizing method, a reduction diffusion method, a mechanical alloying method, or the like. Alloyed using either. Here, when the high frequency melting method or the arc melting method is used, when the above alloy is solidified, a soft magnetic phase containing αFe as a main component is likely to precipitate, but this soft magnetic phase remains after the nitriding treatment, and iHc It is not preferable because it causes a reduction in In order to suppress the formation of this soft magnetic phase, the melted mother alloy is heated to 700 to 1250 ° C. in a vacuum or an argon gas atmosphere.
It is desirable to perform the homogenization treatment under heating conditions of × 0.5 to 100 hours.
【００２６】（粉砕）上記方法で溶製した母合金塊を直
接窒化することも可能であるが、窒化処理物のサイズが
大きいと窒化処理時間が長くなるので粗粉砕を行って平
均粉末粒径で２０〜５００μｍに粗粉砕後窒化すること
が望ましい。粗粉砕は例えばディスクミル、バンタムミ
ル、ジョークラッシャー、ボールミルなどの粉砕機を用
いて行うことができる。また母合金に水素を吸蔵させた
後に上記粉砕機で粗粉砕する方法や、水素の吸蔵と放出
とを繰り返して粗粉砕する方法を用いてもよい。さらに
粗粉砕の後、篩で分級し窒化すると母合金中に均質な窒
化物の主相を形成できるので好ましく、例えば、窒化処
理前に２０μｍ〜１００μｍ未満、１００μｍ〜２００
μｍ未満、２００μｍ〜３００μｍ未満、３００μｍ〜
４００μｍ未満、４００μｍ〜５００μｍ未満というよ
うに篩分すると窒化処理後の磁石粉末がこれらの篩分粒
径になっており、上記の均質な窒化物形成効果とともに
ボンド磁石形状に応じて要求される成形性の難易に合わ
せて適宜粒径分布の希土類磁石粉末を採用できるので実
用性に富むものである。さらに、粗粉砕後、アルゴンガ
ス雰囲気または真空中で５００〜１０００℃×０．５〜
１００時間熱処理すると磁気特性がより向上するが、こ
の効果は粗粉砕により導入された歪みが緩和されるため
と考えられる。(Pulverization) Although it is possible to directly nitride the ingot of the mother alloy melted by the above method, if the size of the nitrided product is large, the nitridation treatment time becomes long. It is desirable to nitride after coarse pulverization to 20 to 500 μm. Coarse pulverization can be performed using a pulverizer such as a disc mill, a bantam mill, a jaw crusher, and a ball mill. Further, a method in which hydrogen is occluded in the master alloy and then coarsely pulverized by the above pulverizer or a method in which hydrogen is occluded and released repeatedly to coarsely pulverize may be used. Further, after coarse pulverization, classification and nitriding with a sieve are preferable because a homogeneous main phase of the nitride can be formed in the mother alloy. For example, before the nitriding treatment, 20 to less than 100 μm, 100 to 200 μm
less than 200 μm, less than 300 μm, less than 300 μm
When sieved to a size of less than 400 μm or less than 400 μm to less than 500 μm, the magnet powder after nitriding has these sieved particle sizes, and together with the above-mentioned uniform nitride forming effect, the molding required according to the bond magnet shape Therefore, it is possible to employ a rare-earth magnet powder having a particle size distribution as appropriate according to the difficulty of the properties, and therefore, it is highly practical. Furthermore, after coarse pulverization, in an argon gas atmosphere or a vacuum, 500 to 1000 ° C. × 0.5 to
The magnetic properties are further improved by heat treatment for 100 hours. This effect is considered to be because the strain introduced by the coarse pulverization is reduced.
【００２７】（窒化）本発明では公知の窒化処理方法
（例えば、ガス窒化法、イオン窒化法等。）を採用でき
る。一例として、ガス窒化法について説明する。ガス窒
化法は窒素ガス、アンモニアガス、窒素ガスと水素ガス
の混合ガス、アンモニアガスと水素ガスの混合ガス等の
いずれかを上記母合金塊または上記母合金の粗粉砕粉に
接触させて結晶格子内に窒素を導入する工程である。窒
化反応は上記のようなガス種を選ぶこと、加熱温度、加
熱時間、ガス圧力により制御できる。このうち加熱温度
は母合金組成によって異なるが３００〜６５０℃が好ま
しい。母合金の種類によらず３００℃未満であると窒化
がほとんど進行せず、また６５０℃を超えると一旦生成
した窒化物が分解してαＦｅなどの軟磁性相が顕著に生
成するので好ましくない。窒化後にさらに窒素ガスを含
有しないアルゴン等の不活性ガス中あるいは真空中ある
いは水素ガス中で３００〜６００℃×０．５〜５０時間
熱処理すると保磁力、ｉＨｃ、飽和磁化等が向上する場
合がある。これは熱処理により窒素が母合金の結晶粒子
内にさらに拡散して主相の窒化物相の割合が増加するこ
とや粉末粒子内により均一に窒化物が形成されて行くた
めと思われる。(Nitriding) In the present invention, a known nitriding method (for example, a gas nitriding method, an ion nitriding method, etc.) can be adopted. As an example, a gas nitriding method will be described. In the gas nitriding method, any one of nitrogen gas, ammonia gas, a mixed gas of nitrogen gas and hydrogen gas, a mixed gas of ammonia gas and hydrogen gas, or the like is brought into contact with the above-mentioned mother alloy mass or the coarsely pulverized powder of the above-mentioned mother alloy to form a crystal lattice. This is a step of introducing nitrogen into the inside. The nitriding reaction can be controlled by selecting the above gas species, heating temperature, heating time, and gas pressure. Among these, the heating temperature varies depending on the mother alloy composition, but is preferably 300 to 650 ° C. Regardless of the type of the mother alloy, if the temperature is lower than 300 ° C., nitriding hardly proceeds, and if the temperature is higher than 650 ° C., the nitride once formed is decomposed and a soft magnetic phase such as αFe is notably formed, which is not preferable. After nitriding, heat treatment in an inert gas such as argon containing no nitrogen gas, in a vacuum or in a hydrogen gas at 300 to 600 ° C. for 0.5 to 50 hours may improve coercive force, iHc, saturation magnetization and the like. . This is presumably because nitrogen is further diffused into the crystal grains of the mother alloy by the heat treatment to increase the ratio of the main phase nitride phase, and nitrides are more uniformly formed in the powder particles.
【００２８】（磁場成形）上記のようにして作成した本
発明の希土類磁石材料粉末を用いて等方性ボンド磁石を
作製するには、その磁石粉末と熱硬化性樹脂または低融
点金属（低融点合金）のバインダーとを適正比率で混合
した後、磁場無しで成形体を形成し、その後加熱硬化処
理を行えばよい。(Magnetic field molding) In order to produce an isotropic bonded magnet using the rare earth magnet material powder of the present invention prepared as described above, the magnet powder and a thermosetting resin or a low melting point metal (low melting point metal) are used. Alloy) and a binder in an appropriate ratio, a compact is formed without a magnetic field, and then a heat-curing treatment may be performed.
【００２９】（着磁）上記のボンド磁石に十分な磁力を
付与するための着磁作業は室温で好ましくは１５ｋＯｅ
以上、より好ましくは２０ｋＯｅ以上の着磁磁場で行う
ことが一般的である。(Magnetization) The magnetizing operation for imparting a sufficient magnetic force to the above-mentioned bonded magnet is performed at room temperature, preferably at 15 kOe.
As described above, more preferably, the magnetization is performed with a magnetizing magnetic field of 20 kOe or more.
【００３０】次に評価方法について具体的に説明する。 （磁気特性の測定）上記磁石材料の２５℃におけるｉＨ
ｃと飽和磁化（σ）、および２５〜１００℃におけるｉ
Ｈｃの温度係数（η）はその磁石粉末の所定量を樹脂に
混ぜて銅容器に詰め込み、振動試料型磁力計（東英工業
（株）製のＶＳＭ-３型）を用いて測定した。ボンド磁
石の２５℃におけるｉＨｃとＢｒと（ＢＨ）ｍａｘ、お
よび２５〜１００℃におけるｉＨｃの温度係数（η）は
自記磁束計（東英工業（株）製ＴＲＦ-５Ｈ）を用いて
測定した。 （窒素量の分析）不活性ガス融解法によって上記希土類
磁石粉末に含有した窒素量を分析した。分析には堀場製
作所（株）製のガス分析装置：ＥＭＧＡ１３００型を用
いた。 （主相の平均結晶粒径の測定）作成した平均結晶粒径測
定用試料の任意断面を顕微鏡観察して、Ｒ3（Ｆｅ，
Ｍ，Ｂ）29Ｎy主相において任意に選んだ４０個の結晶
粒の各最大粒径を測定し、この４０個の測定値を加算平
均して平均結晶粒径とした。Next, the evaluation method will be specifically described. (Measurement of magnetic properties) iH of the above magnet material at 25 ° C
c and saturation magnetization (σ), and i at 25 to 100 ° C.
The temperature coefficient (η) of Hc was measured by mixing a predetermined amount of the magnet powder in a resin, filling the mixture in a copper container, and using a vibrating sample magnetometer (VSM-3 manufactured by Toei Kogyo Co., Ltd.). The iHc, Br and (BH) max of the bonded magnet at 25 ° C. and the temperature coefficient (η) of iHc at 25 to 100 ° C. were measured using a self-recording magnetometer (TRF-5H manufactured by Toei Kogyo Co., Ltd.). (Analysis of nitrogen amount) The amount of nitrogen contained in the rare earth magnet powder was analyzed by an inert gas melting method. For the analysis, a gas analyzer manufactured by Horiba Ltd .: EMGA1300 was used. (Measurement of Average Crystal Grain Size of Main Phase) An arbitrary cross section of the prepared sample for measuring the average crystal grain size was observed with a microscope, and R 3 (Fe,
M, B) 29 N y measures each maximum particle size of the arbitrarily selected 40 pieces of grains in the main phase, and the average crystal grain size of the 40 measurements averaged to.
【００３１】次に、本発明を実施例により説明するがこ
れらにより本発明が限定されるものではない。 （実施例１〜７）Ｒ3（Ｆｅ，Ｍ，Ｂ）29Ｎy主相の平均
結晶粒径（ｄｃ）、磁石粉末の平均粒径（ｄｐ）と、希
土類磁石粉末の２５℃における飽和磁化の強さ（σ）お
よびｉＨｃ、２５〜１００℃におけるｉＨｃの温度係数
（η）との相関を下記のようにして評価した。なお、以
降の各実施例、各比較例の測定は全て上記条件で行っ
た。まず、純度９９.９％のＳｍ、Ｆｅ、ＶおよびＢを
用いて表１の実施例１〜７の窒化物磁石粉末に対応した
母合金組成になるように各々配合し、アルゴンガス雰囲
気の高周波溶解炉で溶解して実施例１〜７に対応した各
母合金を溶製した。その後、アルゴンガス雰囲気中で１
１５０℃×２０時間の均質化処理を行い、続いてジョー
クラッシャーとディスクミルを用いて平均粉末粒径２０
μｍ以上に粉砕した。これらの母合金粉体のＸ線回折を
Ｃｕ-Ｋα線を用いて行ったところ回折線はすべてＲ
3（Ｆｅ，Ｍ，Ｂ）29相として指数付けできることを確
認した。このＳｍ-Ｆｅ-Ｖ-Ｂ系磁性粉を１ａｔｍの水
素ガス中に８００℃×１時間加熱保持する水素化、分解
反応処理を行った後、さらに水素分圧（真空中）５〜８
×１０-2Ｔｏｒｒに８００℃×１時間保持する脱水素、
再結合反応処理を行った。次に前記各粉体を１ａｔｍの
窒素ガス中に４５０℃×５時間保持するガス窒化処理を
行い冷却した。続いてＡｒガス気流中で４００℃×３０
分間熱処理して得られた実施例１〜７の窒化物磁石粉末
の主相の平均結晶粒径（ｄｃ）、粉末の平均粒径ｄｐ、
組成、飽和磁化の強さ（σ）、ｉＨｃ、ｉＨｃの温度係
数（η）の測定結果を表１に示した。この磁石粉末を電
子顕微鏡で観察したところＳｍ3（Ｆｅ，Ｖ,Ｂ）29Ｎy
主相内に数十ｎｍの大きさのＶリッチなセル構造が認め
られた。Next, the present invention will be described with reference to examples, but the present invention is not limited by these examples. (Examples 1 to 7) Average grain size (dc) of R 3 (Fe, M, B) 29 Ny main phase, average grain size (dp) of magnet powder, and saturation magnetization of rare earth magnet powder at 25 ° C. And the temperature coefficient (η) of iHc at 25 to 100 ° C. were evaluated as follows. The measurements in the following examples and comparative examples were all performed under the above conditions. First, using Sm, Fe, V, and B having a purity of 99.9%, each was blended so as to have a mother alloy composition corresponding to the nitride magnet powders of Examples 1 to 7 in Table 1, and a high-frequency gas in an argon gas atmosphere was used. Each mother alloy corresponding to Examples 1 to 7 was melted by melting in a melting furnace. Then, in an argon gas atmosphere,
A homogenization treatment at 150 ° C. × 20 hours was performed, and subsequently, an average powder particle size of 20
It was pulverized to at least μm. X-ray diffraction of these mother alloy powders was performed using Cu-Kα radiation.
3 (Fe, M, B) It was confirmed that indexing was possible as 29 phases. This Sm-Fe-VB-based magnetic powder is subjected to a hydrogenation and decomposition reaction treatment by heating and holding at 800 ° C. × 1 hour in 1 atm of hydrogen gas, and then a hydrogen partial pressure (in vacuum) of 5-8.
Dehydrogenation at 800 ° C. × 1 hour at × 10 −2 Torr,
Recombination reaction treatment was performed. Next, each powder was subjected to a gas nitriding treatment in which the powder was held at 450 ° C. for 5 hours in a nitrogen gas of 1 atm and cooled. Subsequently, at 400 ° C. × 30 in an Ar gas stream.
Average grain size (dc) of the main phase of the nitride magnet powders of Examples 1 to 7 obtained by heat treatment for
Table 1 shows the measurement results of the composition, the saturation magnetization strength (σ), iHc, and the temperature coefficient (η) of iHc. Observation of this magnet powder with an electron microscope revealed that Sm 3 (Fe, V, B) 29 N y
A V-rich cell structure with a size of several tens nm was observed in the main phase.
【００３２】（比較例１〜６）Ｍ元素を含有しない場合
の比較例１〜４およびＭ元素としてＶを含有した比較例
５、６とした以外は実施例１と同様にして評価した結果
を表１に併記した。これら各比較例の合金の生成相は、
Ｖを含有しない比較例１〜４およびＶ量が少ない比較例
５の場合はＴｈ2Ｚｎ17型のＳｍ2Ｆｅ17相およびαＦｅ
相であり、含有量が過多の比較例６の場合はＴｈ2Ｚｎ
17型のＳｍ2（Ｆｅ,Ｖ,Ｂ）17相、αＦｅ相、Ｆｅ-Ｂ相
およびＦｅ-Ｖ相であった。(Comparative Examples 1 to 6) The results evaluated in the same manner as in Example 1 except that Comparative Examples 1 to 4 in the case where the element M was not contained and Comparative Examples 5 and 6 in which V was contained as the element M were used. Also shown in Table 1. The generated phases of the alloys of these comparative examples are:
For Comparative Examples 1 to 4 and V comparison small amount Example 5 not containing V Th 2 Zn 17 type Sm 2 Fe 17 phase and αFe
Th 2 Zn in the case of Comparative Example 6 which is
17 type Sm 2 (Fe, V, B) 17 phase, αFe phase, Fe-B phase and Fe-V phase.
【００３３】[0033]
【表１】 [Table 1]
【００３４】表１よりＲ3（Ｆｅ,Ｍ,Ｂ）29合金に対す
る水素を用いた相変態処理の効果が明らかである。すな
わち主相の平均結晶粒径が０．６５μｍである実施例１
〜７では磁石材料粉末の平均粒径２０〜５００μｍにわ
たって９ｋＯｅ以上の高いｉＨｃが得られ、ｉＨｃの温
度係数（η）も−０．３９以上で良好な耐熱性を有して
いることがわかる。一方、元素Ｖを含まないかあるいは
Ｖが有効含有量より少ない比較例１〜５と、Ｖが過剰に
多い比較例６の場合は、いずれもｉＨｃが３ｋＯｅ未満
でありまたｉＨｃの温度係数（η）も−０.５９以下で
あり耐熱性に劣ることがわかる。From Table 1, the effect of the phase transformation treatment using hydrogen on the R 3 (Fe, M, B) 29 alloy is clear. That is, Example 1 in which the average crystal grain size of the main phase was 0.65 μm.
7 shows that high iHc of 9 kOe or more was obtained over an average particle size of the magnet material powder of 20 to 500 μm, and that the temperature coefficient (η) of iHc was -0.39 or more, indicating that the material had good heat resistance. On the other hand, in Comparative Examples 1 to 5 containing no element V or containing less than the effective content of V and Comparative Example 6 containing too much V, iHc is less than 3 kOe and the temperature coefficient of iHc (η ) Is -0.59 or less, indicating that the heat resistance is inferior.
【００３５】（実施例８〜１１）平均結晶粒径ｄｃ、Ｂ
量と磁気特性との相関を見るために、表２に示した磁石
粉末組成、平均結晶粒径ｄｃにするとともに磁石材料の
粉末平均粒径ｄｐを７０μｍとした以外は上記実施例１
と同様な操作によって表２に示した磁石粉末を製作する
とともに飽和磁化（σ）、ｉＨｃ，ｉＨｃの温度係数
（η）を測定した。これらの母合金粉体のＸ線回折をＣ
ｕ-Ｋα線を用いて行ったところ回折線はすべて強い回
折ピークのＲ3（Ｆｅ，Ｖ，Ｂ）29相と弱い回折ピーク
のＲ3（Ｆｅ，Ｖ）29相として指数付けできることを確
認した。 （比較例７〜９）合金組成をＢが０．１未満または５ａ
ｔ％より多くし、平均結晶粒径ｄｃを変えた以外は実施
例８と同様にして表２の窒化物磁石粉末を作製し評価し
た。これらの磁石粉末に生成した相はＳｍ3（Ｆｅ,Ｖ,
Ｂ）29相以外に、Ｔｈ2Ｚｎ17型のＳｍ2（Ｆｅ,Ｖ,Ｂ）
17相およびαＦｅ相であった。(Examples 8 to 11) Average grain size dc, B
In order to see the correlation between the amount and the magnetic characteristics, the above-mentioned Example 1 was repeated except that the magnet powder composition and the average crystal grain diameter dc shown in Table 2 were set and the powder average particle diameter dp of the magnet material was 70 μm.
The magnet powders shown in Table 2 were produced by the same operation as described above, and the saturation magnetization (σ) and the temperature coefficient (η) of iHc and iHc were measured. X-ray diffraction of these mother alloy powders
diffraction lines was performed using the u-K [alpha line was confirmed that all be indexed as a strong diffraction peak of R 3 (Fe, V, B ) 29 phase and the weak diffraction peak R 3 (Fe, V) 29 phase . (Comparative Examples 7 to 9) The alloy composition was changed so that B was less than 0.1 or 5a.
The nitride magnet powder of Table 2 was prepared and evaluated in the same manner as in Example 8, except that the amount was larger than t% and the average crystal grain size dc was changed. The phase formed in these magnet powders is Sm 3 (Fe, V,
B) In addition to the 29 phase, Th 2 Zn 17 type Sm 2 (Fe, V, B)
17 phases and αFe phase.
【００３６】[0036]
【表２】 [Table 2]
【００３７】表２から平均結晶粒径が０．０５〜１．０
０μｍであり、Ｂを０．１〜５原子％の範囲にすること
により高いｉＨｃと低いｉＨｃの温度係数（η)が得ら
れることがわかる。また比較例７〜９に示したようにＢ
が０．０５原子％または７原子％以上のときにはｉＨｃ
が低下していた。From Table 2, it can be seen that the average grain size is 0.05 to 1.0.
It can be seen that the temperature coefficient (η) of high iHc and low iHc can be obtained by setting B to be in the range of 0.1 to 5 atomic%. Further, as shown in Comparative Examples 7 to 9, B
Is 0.05 atomic% or 7 atomic% or more, iHc
Had declined.
【００３８】（実施例１２〜３０）主相の平均結晶粒径
が０．０６〜０．９５μｍであり、Ｒ成分含有量および
Ｒ成分の種類を変化させた場合、窒素含有量を変化させ
た場合、Ｆｅの一部をＣｏおよび／またはＮｉで置換し
た場合、Ｍ元素の種類および含有量を変化させた場合の
磁石特性との相関を各々見るために、平均粉末粒径１１
０μｍの表３の磁石粉末とした以外は上記実施例１と同
様な操作によって飽和磁化（σ）、ｉＨｃ，ｉＨｃの温
度係数（η）を測定した。 （比較例１０〜１７）表４の磁石粉末とした以外は実施
例１２と同様にして評価した。(Examples 12 to 30) When the average crystal grain size of the main phase was 0.06 to 0.95 μm and the content of the R component and the type of the R component were changed, the nitrogen content was changed. In the case where a part of Fe was replaced by Co and / or Ni, the average powder particle size was 11
The saturation magnetization (σ) and the temperature coefficient (η) of iHc and iHc were measured by the same operation as in Example 1 except that the magnet powder of Table 3 was 0 μm. (Comparative Examples 10 to 17) Evaluations were made in the same manner as in Example 12 except that the magnet powder shown in Table 4 was used.
【００３９】[0039]
【表３】 [Table 3]
【００４０】[0040]
【表４】 [Table 4]
【００４１】表３、表４より、平均結晶粒径が０．０５
〜１．００μｍであり、Ｒ成分中のＳｍ比率が５０原子
％以上でかつＲ成分が５〜１８原子％であり、窒素が４
〜３０原子％のときに高いｉＨｃと低いｉＨｃの温度係
数（η）が得られることがわかる。またＦｅの成分の
０．０１〜３０原子％をＣｏおよび／またはＮｉで置換
することによりｉＨｃの温度係数（η）がさらに改善さ
れている。また、実施例１２〜３０において、Ｍ元素と
してＴｉ、Ｍｎ、Ｃｒのいずれかを各々選択した場合に
も高いｉＨｃと低いｉＨｃの温度係数（η）が得られる
ことを確認した。また、実施例２９、３０の主相の微細
結晶組織を電子顕微鏡で観察したところ、数１０ｎｍの
セル構造のＭ元素が析出した組織が観察された。これに
対し、平均結晶粒径が１．００μｍを越えている比較例
１０〜１２、窒素含有量の少ない比較例１３および窒素
過多の比較例１４およびＣｏ置換量過多の比較例１６、
Ｃｒ含有量過多の比較例１７のものは上記実施例に比べ
て各特性が劣っていた。また、Ｃｏ置換量の少ない比較
例１５ではＣｏの添加効果が認められない。According to Tables 3 and 4, the average crystal grain size was 0.05.
1.00 μm, the Sm ratio in the R component is 50 atomic% or more, the R component is 5 to 18 atomic%, and the nitrogen content is 4%.
It can be seen that a high iHc and a low iHc temperature coefficient (η) can be obtained at の 30 atomic%. Further, the temperature coefficient (η) of iHc is further improved by substituting 0.01 to 30 atomic% of the Fe component with Co and / or Ni. Further, in Examples 12 to 30, it was confirmed that the temperature coefficient (η) of high iHc and low iHc was obtained even when any one of Ti, Mn, and Cr was selected as the M element. When the fine crystal structure of the main phase in each of Examples 29 and 30 was observed with an electron microscope, a structure in which an M element having a cell structure of several tens nm was precipitated was observed. On the other hand, Comparative Examples 10 to 12 in which the average crystal grain size exceeds 1.00 μm, Comparative Example 13 with a low nitrogen content, Comparative Example 14 with an excessive nitrogen content, and Comparative Example 16 with an excessive Co substitution amount,
In the case of Comparative Example 17 in which the Cr content was excessive, the properties were inferior to those of the above-mentioned Examples. In Comparative Example 15 in which the amount of Co substitution is small, the effect of adding Co is not recognized.
【００４２】（実施例３２〜４０）純度９９.９％のＳ
ｍ、Ｆｅ、Ｃｒ、Ｂを用いて下記の窒化物粉末に対応し
た母合金組成に配合後、アルゴンガス雰囲気下で高周波
溶解炉し鋳造合金を得た。前記鋳造塊を５０ｍｍ角以下
に破断後、雰囲気熱処理炉に仕込み１ａｔｍの水素ガス
を供給するとともに５００℃まで加熱し水素を吸収させ
た後真空にすることにより脱水素を行う工程を繰り返し
平均粒径１００μｍまで粗粉砕した。このＳｍ-Ｆｅ-Ｂ
-Ｃｒ系磁性粉を表５に示した条件で水素化、分解反応
させる処理と、それに続いた脱水素、再結合反応処理を
行った。水素化、分解反応処理時の水素ガス圧は１ａｔ
ｍとした。脱水素、再結合反応処理時の水素分圧は５〜
７×１０-2Ｔｏｒｒとした。この処理を終えたＳｍ-Ｆ
ｅ-Ｂ-Ｃｒ系磁性粉を次いで雰囲気熱処理炉に仕込み４
６０℃においてアンモニア分圧０.３５ａｔｍ、水素ガ
ス０.６５ａｔｍの混合気流中で７時間保持する窒化処
理を行った。続いて水素ガス気流中で４００℃×３０分
間熱処理を行いＳｍ9.2ＦｅbalＢ1.0Ｃｒ6.0Ｎ12.3（原
子％）の組成を有した各磁石粉末を得た。 （比較例１８〜２５）表５の水素化、分解処理条件およ
び脱水素、再結合処理条件とした以外は実施例３１と同
様にしてσ、ｉＨｃを評価した。(Examples 32 to 40) S having a purity of 99.9%
After mixing m, Fe, Cr, and B into a mother alloy composition corresponding to the following nitride powder, a high frequency melting furnace was used in an argon gas atmosphere to obtain a cast alloy. After the cast ingot is fractured to 50 mm square or less, a process of charging the atmosphere heat treatment furnace, supplying 1 atm of hydrogen gas, heating to 500 ° C. to absorb hydrogen, and then applying vacuum to repeat dehydrogenation is repeated. It was coarsely pulverized to 100 μm. This Sm-Fe-B
A treatment for hydrogenating and decomposing the -Cr magnetic powder under the conditions shown in Table 5, followed by a dehydrogenation and recombination reaction treatment. Hydrogen gas pressure during hydrogenation and decomposition reaction treatment is 1 at
m. Hydrogen partial pressure during dehydrogenation and recombination reaction treatment is 5 to 5.
7.times.10.sup.- 2 Torr. Sm-F after this process
e-B-Cr-based magnetic powder is then charged into an atmosphere heat treatment furnace 4
A nitriding treatment was performed at 60 ° C. for 7 hours in a mixed gas flow of an ammonia partial pressure of 0.35 atm and a hydrogen gas of 0.65 atm. Subsequently, heat treatment was performed at 400 ° C. for 30 minutes in a hydrogen gas stream to obtain each magnet powder having a composition of Sm9.2FebalB1.0Cr6.0N12.3 (atomic%). (Comparative Examples 18 to 25) σ and iHc were evaluated in the same manner as in Example 31 except that the hydrogenation, decomposition treatment conditions, dehydrogenation, and recombination treatment conditions in Table 5 were used.
【００４３】[0043]
【表５】 [Table 5]
【００４４】表５から水素化、分解処理を７００〜９０
０℃×０．５〜８時間とし、さらに脱水素、再結合処理
を７００〜９００℃×０．５〜１０時間とすることによ
り高いｉＨｃが得られ、各実施例の主相の平均結晶粒径
は０．０５〜１．０μｍの範囲に分布していた。これに
対し、比較例１８〜２５のものはｉＨｃが低く、主相の
平均結晶粒径は０．０５〜１．０μｍの範囲を外れてい
た。Table 5 shows that the hydrogenation and decomposition treatments were 700-90.
A high iHc is obtained by setting the temperature to 0 ° C. × 0.5 to 8 hours and the dehydrogenation and recombination treatment to 700 to 900 ° C. × 0.5 to 10 hours. The diameter was distributed in the range of 0.05 to 1.0 μm. In contrast, those of Comparative Examples 18 to 25 had low iHc, and the average crystal grain size of the main phase was out of the range of 0.05 to 1.0 μm.
【００４５】（実施例４１〜４６）ボンド磁石特性を評
価するために主相の平均結晶粒径ｄｃが０．０５〜１．
００μｍにある表６に示す組成の磁石粉末を作製し、こ
れらをエポキシ樹脂と混合した後、１０ｋＯｅの磁場中
でプレス圧１０ｔｏｎ／ｃｍ2で圧縮成形し、さらに硬
化のため１４０℃、１時間の熱処理を施して等方性ボン
ド磁石を作製した。これらの等方性ボンド磁石の磁気特
性を表６に示した。(Examples 41 to 46) In order to evaluate the properties of the bonded magnet, the average crystal grain size dc of the main phase was 0.05 to 1.0.
A magnet powder having a composition shown in Table 6 and having a composition of 00 μm was prepared, mixed with an epoxy resin, and then compression-molded at a press pressure of 10 ton / cm 2 in a magnetic field of 10 kOe and further cured at 140 ° C. for 1 hour. Heat treatment was performed to produce an isotropic bonded magnet. Table 6 shows the magnetic properties of these isotropic bonded magnets.
【００４６】[0046]
【表６】 [Table 6]
【００４７】表６から本発明の等方性ボンド磁石が良好
な磁石特性を有していることがわかる。Table 6 shows that the isotropic bonded magnet of the present invention has good magnet properties.
【００４８】上記各実施例の磁石粉末のキュリー温度は
いずれも４８０±２０℃という良好な値を有していた。The Curie temperature of each of the magnetic powders of the above examples had a good value of 480 ± 20 ° C.
【００４９】[0049]
【発明の効果】Ｒ3（Ｆｅ，Ｍ，Ｂ）29Ｎy主相の平均結
晶粒径が０．０５〜１．０μｍである場合に粉体の平均
粒径で２０〜５００μｍにわたって高いｉＨｃと低いｉ
Ｈｃの温度係数（η）を有した希土類磁石粉末を安定し
て提供できるとともに、この粉末を用いることで良好な
耐熱性を有した希土類ボンド磁石を容易に提供でき、工
業的に非常に有用なものである。According to the present invention, when the average crystal grain size of the R 3 (Fe, M, B) 29 Ny main phase is 0.05 to 1.0 μm, the iHc is high over the range of 20 to 500 μm in average powder size. Low i
A rare earth magnet powder having a temperature coefficient of Hc (η) can be stably provided, and by using this powder, a rare earth bonded magnet having good heat resistance can be easily provided, which is industrially very useful. Things.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｆ 1/08 Ｈ０１Ｆ 1/08 Ａ (72)発明者 徳永 雅亮 埼玉県熊谷市三ケ尻5200番地日立金属株式 会社磁性材料研究所内──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI H01F 1/08 H01F 1/08 A (72) Inventor Masaaki Tokunaga 5200 Mikajiri, Kumagaya-shi, Saitama Pref.
Claims (10)
ＭβＢγＮδで表され、単斜晶および／または六方晶の
結晶構造を有し平均結晶粒径が０．０５〜１．０μｍで
あるＲ3（Ｆｅ，Ｍ，Ｂ）29Ｎy主相を含み、前記ＲはＹ
を含めた希土類元素のいずれか１種または２種以上であ
り、前記ＭはＡｌ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｕ、Ｇ
ａ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、Ｔａ、Ｗのいずれか１種
または２種以上であり、前記α、β、γ、δは原子百分
率で下記の範囲にあることを特徴とする希土類磁石材
料。 ５≦α≦１８ １≦β≦５０ ０．１≦γ≦５ ４≦δ≦３０1. The composition of the composition is RαFe100- (α + β + γ + δ).
An R 3 (Fe, M, B) 29 N y main phase represented by MβBγNδ, having a monoclinic and / or hexagonal crystal structure and having an average crystal grain size of 0.05 to 1.0 μm; R is Y
And at least one of rare earth elements, including M, wherein M is Al, Ti, V, Cr, Mn, Cu, G
a rare earth magnet material, wherein at least one of a, Zr, Nb, Mo, Hf, Ta, and W is used, and the α, β, γ, and δ are in the following ranges in atomic percentage. . 5 ≦ α ≦ 18 1 ≦ β ≦ 50 0.1 ≦ γ ≦ 5 4 ≦ δ ≦ 30
とを特徴とする請求項１に記載の希土類磁石材料。2. The rare earth magnet material according to claim 1, wherein 50% by atom or more of the R component is Sm.
μｍ以上５００μｍ以下であることを特徴とする請求項
１または２に記載の希土類磁石材料。3. An average particle diameter of the rare earth magnet material powder is 20.
The rare earth magnet material according to claim 1, wherein the rare earth magnet material has a thickness of not less than μm and not more than 500 μm.
にＭ元素またはＭ化合物が析出していることを特徴とす
る請求項１乃至３のいずれかに記載の希土類磁石材料。4. The rare earth element according to claim 1, wherein the M element or the M compound is precipitated in the crystal grains of the R 3 (Fe, M, B) 29 Ny phase. Magnet material.
Ｍ，Ｂ）29Ｎy主相の構成比率が６０体積％以上である
ことを特徴とする請求項１乃至４のいずれかに記載の希
土類磁石材料。5. R 3 (Fe,
The rare earth magnet material according to any one of claims 1 to 4, wherein the composition ratio of the (M, B) 29 Ny main phase is 60% by volume or more.
類磁石材料の粉体粒子を、高分子重合体、純金属、合金
のいずれかのバインダーで結合したことを特徴とする希
土類ボンド磁石。6. A rare earth bonded magnet, wherein the powder particles of the rare earth magnet material according to any one of claims 1 to 5 are bonded with a binder of a polymer, a pure metal, or an alloy. .
ＭβＢγＮδで表され、単斜晶および／または六方晶の
結晶構造を有したＲ3（Ｆｅ，Ｍ，Ｂ）29Ｎy主相を含
み、前記ＲはＹを含めた希土類元素のいずれか１種また
は２種以上であり、前記ＭはＡｌ、Ｔｉ、Ｖ、Ｃｒ、Ｍ
ｎ、Ｃｕ、Ｇａ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、Ｔａ、Ｗの
いずれか１種または２種以上であり、前記α、β、γ、
δが原子百分率で下記の範囲にある希土類磁石材料の製
造方法において、 前記組成の合金を鋳造後、均質化処理を行い、続いて粗
粉砕したものを、０．１〜１０ａｔｍのＨ2ガス中また
はＨ2ガス分圧を有した不活性ガス（Ｎ2ガスを除く）中
で７００〜９００℃×０．５〜８時間保持する水素化、
分解反応処理を行い、続いて１×１０-2Ｔｏｒｒ以上の
真空中に７００〜９００℃×０．５〜１０時間保持する
脱水素、再結合反応処理を行った後、窒化処理を行うこ
とを特徴とする希土類磁石材料の製造方法。 ５≦α≦１８ １≦β≦５０ ０．１≦γ≦５ ４≦δ≦３０7. A composition comprising RαFe100- (α + β + γ + δ)
Represented by Emubetabiganmaenuderuta, monoclinic and / or R 3 having a hexagonal crystal structure (Fe, M, B) comprises a 29 N y main phase, wherein R is any one of rare earth elements including Y Or two or more kinds, wherein M is Al, Ti, V, Cr, M
n, Cu, Ga, Zr, Nb, Mo, Hf, Ta, W or any one or more of the above, α, β, γ,
In a method for producing a rare earth magnet material in which δ is in the following range in atomic percentage, an alloy having the above composition is cast, homogenized, and then roughly pulverized in H 2 gas of 0.1 to 10 atm. Or hydrogenation maintained at 700 to 900 ° C. × 0.5 to 8 hours in an inert gas (excluding N 2 gas) having a H 2 gas partial pressure;
After performing a decomposition reaction treatment, and subsequently performing a dehydrogenation and recombination reaction treatment at 700 to 900 ° C. for 0.5 to 10 hours in a vacuum of 1 × 10 −2 Torr or more, a nitriding treatment is performed. A method for producing a rare earth magnet material. 5 ≦ α ≦ 18 1 ≦ β ≦ 50 0.1 ≦ γ ≦ 5 4 ≦ δ ≦ 30
〜１００時間の均質化処理を行うことを特徴とする請求
項７に記載の希土類磁石材料の製造方法。8. After casting, the temperature is 700 to 1250 ° C. × 0.5.
The method for producing a rare earth magnet material according to claim 7, wherein the homogenization treatment is performed for 100 hours.
ス中（Ｎ2ガスを除く）で３００〜６００℃×０.５〜５
０時間の熱処理を行うことを特徴とする請求項７乃至９
のいずれかに記載の希土類磁石材料の製造方法。9. After the nitriding treatment, in a vacuum or in an inert gas (excluding N 2 gas), 300 to 600 ° C. × 0.5 to 5 ° C.
10. The heat treatment for 0 hours is performed.
The method for producing a rare earth magnet material according to any one of the above.
１〜９５モル％で残部Ｎ2からなるＨ2とＮ2の混合ガ
ス、ＮＨ3のモル％が１〜５０％で残部Ｈ2からなるＮＨ
3とＨ2の混合ガスのうちのいずれかの雰囲気中で３００
〜６５０℃×０．１〜３０時間保持する窒化処理を行う
ことを特徴とする請求項７乃至９のいずれかに記載の希
土類磁石材料の製造方法。10. A mixed gas of H 2 and N 2 consisting of 0.2 to 10 atm of N 2 gas, H 2 of 1 to 95 mol% and the balance N 2 , and NH 3 of 1 to 50 mol% of the balance NH consisting of H 2
300 in any atmosphere of the mixed gas of 3 and H 2
The method for producing a rare-earth magnet material according to any one of claims 7 to 9, wherein a nitriding treatment is performed at a temperature of 650C for 0.1 to 30 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9098611A JPH10289811A (en) | 1997-04-16 | 1997-04-16 | Rare-earth magnet material, method of manufacturing the same and rare-earth bonded magnet by the method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9098611A JPH10289811A (en) | 1997-04-16 | 1997-04-16 | Rare-earth magnet material, method of manufacturing the same and rare-earth bonded magnet by the method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10289811A true JPH10289811A (en) | 1998-10-27 |
Family
ID=14224397
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9098611A Pending JPH10289811A (en) | 1997-04-16 | 1997-04-16 | Rare-earth magnet material, method of manufacturing the same and rare-earth bonded magnet by the method |
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| Country | Link |
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| JP (1) | JPH10289811A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002289443A (en) * | 2001-03-23 | 2002-10-04 | Nec Tokin Corp | Inductor component |
-
1997
- 1997-04-16 JP JP9098611A patent/JPH10289811A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002289443A (en) * | 2001-03-23 | 2002-10-04 | Nec Tokin Corp | Inductor component |
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