JPH0778709A - Manufacture of r-fe-b permanent magnet material - Google Patents
Manufacture of r-fe-b permanent magnet materialInfo
- Publication number
- JPH0778709A JPH0778709A JP5246365A JP24636593A JPH0778709A JP H0778709 A JPH0778709 A JP H0778709A JP 5246365 A JP5246365 A JP 5246365A JP 24636593 A JP24636593 A JP 24636593A JP H0778709 A JPH0778709 A JP H0778709A
- Authority
- JP
- Japan
- Prior art keywords
- phase
- alloy
- atom
- alloy powder
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000000463 material Substances 0.000 title claims description 20
- 239000000843 powder Substances 0.000 claims abstract description 126
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 101
- 239000000956 alloy Substances 0.000 claims abstract description 101
- 230000005291 magnetic effect Effects 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 40
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005266 casting Methods 0.000 claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 abstract description 15
- 230000007423 decrease Effects 0.000 abstract description 9
- 229910000521 B alloy Inorganic materials 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 154
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 105
- 239000000203 mixture Substances 0.000 description 31
- 238000010298 pulverizing process Methods 0.000 description 27
- 239000013078 crystal Substances 0.000 description 19
- 239000002994 raw material Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000003825 pressing Methods 0.000 description 12
- 230000004907 flux Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000006356 dehydrogenation reaction Methods 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 7
- 229910052692 Dysprosium Inorganic materials 0.000 description 6
- 229910052777 Praseodymium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 230000005415 magnetization Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 230000005294 ferromagnetic effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 230000002706 hydrostatic effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- -1 tetragonal compound Chemical class 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 101100083446 Danio rerio plekhh1 gene Proteins 0.000 description 1
- 229910000722 Didymium Inorganic materials 0.000 description 1
- 241000224487 Didymium Species 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium 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
- H01F1/057—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
- H01F1/0575—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 pressed, sintered or bonded together
- H01F1/0577—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 pressed, sintered or bonded together sintered
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】この発明は、Ｒ（但しＲはＹを含
む希土類元素のうち、少なくとも１種を含有）、Ｆｅ、
Ｂを主成分とする永久磁石材料の製造方法に係り、Ｒ、
Ｆｅ、Ｂを主成分とする合金溶湯をロールを用いたスト
リップ・キャスティング法にてＲ2Ｆｅ14Ｂ相を主相と
する主相系合金鋳片を得、また、同様に特定組成のＲ2
Ｆｅ17相含む調整用合金鋳片を得、これを当該合金のＨ
2吸蔵性を利用して鋳片を自然崩壊させ、さらに脱Ｈ2処
理して安定化させて、効率よい微粉砕を可能にし、配合
混合した微粉末にパルス磁界をかけて配向させた後、成
形して焼結することにより、磁石特性の１つである最大
エネルギー積値（ＢＨ）ｍａｘ（ＭＧＯｅ）；Ａと保磁
力ｉＨｃ（ｋＯｅ）の特性値；Ｂの合計値Ａ＋Ｂが５９
以上の値を有し、角型性｛（Ｂｒ2／４）／（ＢＨ）ｍ
ａｘ｝が１．０１〜１．０４５の値を示す高性能Ｒ−Ｆ
ｅ−Ｂ系永久磁石を得ることを特徴とするＲ−Ｆｅ−Ｂ
系永久磁石材料の製造方法に関する。The present invention relates to R (provided that R contains at least one rare earth element including Y), Fe,
A method for manufacturing a permanent magnet material containing B as a main component,
Fe, B give the main phase alloy billet to main phase R 2 Fe 14 B phase alloy melt mainly by the strip casting method using a roll, also similarly specific composition R 2
An adjustment alloy slab containing the Fe 17 phase was obtained, and this was used as H of the alloy.
2 The slab is naturally collapsed by utilizing its occlusion property, further de-H 2 treated and stabilized to enable efficient fine pulverization, and after applying a pulse magnetic field to the fine powder mixed and mixed, it is oriented. By forming and sintering, the maximum energy product value (BH) max (MGOe), which is one of the magnet characteristics; the characteristic value of A and the coercive force iHc (kOe);
Has a value greater than or equal squareness {(Br 2/4) / (BH) m
ax} is a high-performance RF that shows a value of 1.01 to 1.045
R-Fe-B characterized by obtaining an e-B system permanent magnet
The present invention relates to a method for manufacturing a permanent magnet material.
【０００２】[0002]
【従来の技術】今日、高性能永久磁石として代表的なＲ
−Ｆｅ−Ｂ系永久磁石（特開昭５９−４６００８号）
は、三元系正方晶化合物の主相とＲ−ｒｉｃｈ相を有す
る組織にて高い磁石特性が得られ、一般家庭の各種電器
製品から大型コンピュータの周辺機器まで幅広い分野で
使用され、用途に応じた種々の磁石特性を発揮するよう
種々の組成のＲ−Ｆｅ−Ｂ系永久磁石が提案されてい
る。しかしながら、電気、電子機器の小型、軽量化なら
びに高機能化の要求は強く、Ｒ−Ｆｅ−Ｂ系永久磁石の
より一層の高性能化とコストダウンが要求されている。2. Description of the Related Art Today, R is a typical high-performance permanent magnet.
-Fe-B system permanent magnet (JP-A-59-46008)
Is a magnet with a structure that has a ternary tetragonal compound main phase and an R-rich phase, and is used in a wide range of fields from various household electrical appliances to large computer peripherals. Various R-Fe-B based permanent magnets having various compositions have been proposed so as to exhibit various magnetic properties. However, there are strong demands for smaller and lighter electric and electronic devices as well as higher functionality, and further higher performance and cost reduction of R—Fe—B permanent magnets are required.
【０００３】一般にＲ−Ｆｅ−Ｂ系焼結磁石の残留磁束
密度（Ｂｒ）は以下の（１）式で表すことができる。 Ｂｒ∝（Ｉｓ・β）・ｆ・｛ρ／ρ0・（１−α）｝2/3 （１）式 但し、Ｉｓ：飽和磁化 β：飽和磁化の温度依存性 ｆ：配向度 ρ：焼結体の密度 ρ0：理論密度 α：粒界相（非磁性相の体積割合） 従って、Ｒ−Ｆｅ−Ｂ系焼結磁石の残留磁束密度（Ｂ
ｒ）を高めるためには、 １）強磁性相であり、主相のＲ2Ｆｅ14Ｂ相の存在量を
多くすること、２）焼結体の密度を理論密度まで高める
こと、３）さらに主相結晶粒の、磁化容易軸方向の配向
度を高めることが要求される。Generally, the residual magnetic flux density (Br) of an R-Fe-B system sintered magnet can be expressed by the following equation (1). Br∝ (Is · β) · f · {ρ / ρ 0 · (1-α)} 2/3 Equation (1) where Is: Saturation magnetization β: Temperature dependence of saturation magnetization f: Orientation degree ρ: Burnt Density of aggregate ρ 0 : Theoretical density α: Grain boundary phase (volume ratio of non-magnetic phase) Therefore, the residual magnetic flux density of the R—Fe—B system sintered magnet (B
In order to increase r), 1) increase the abundance of the main phase R 2 Fe 14 B phase that is a ferromagnetic phase, 2) increase the density of the sintered body to the theoretical density, 3) further It is required to increase the degree of orientation of the main phase crystal grains in the easy magnetization axis direction.
【０００４】すなわち、前記１）項の達成のためには、
磁石の組成を上記Ｒ2Ｆｅ14Ｂの化学量論的組成に近づ
けることが重要であるが、上記組成の合金を溶解し、鋳
型に鋳造した合金塊を、出発原料としてＲ−Ｆｅ−Ｂ系
焼結磁石を作製しようとすると、合金塊に晶出したα−
Ｆｅや、Ｒ−ｒｉｃｈ相が局部的に偏在していることな
どから、特に微粉砕時に粉砕が困難となり、組成ずれを
生ずる等の問題があった。詳述すると、前記合金塊をＨ
2吸蔵、脱Ｈ2処理して機械的微粉砕を行う場合（特開昭
６０−６３３０４号、特開昭６３−３３５０５号）、合
金塊に晶出したα−Ｆｅはそのまま粉砕時に残留し、そ
の展延性の性質のために粉砕を妨げ、又局部的に偏在し
たＲ−ｒｉｃｈ相はＨ2吸蔵処理によって、水素化物を
生成し、微細な粉末となるため、機械的な微粉砕時に酸
化が促進されたり、またジェットミルを用いた粉砕では
優生的に飛散することにより組成ずれを生ずる。That is, in order to achieve the above item 1),
It is important to bring the composition of the magnet close to the stoichiometric composition of the above R 2 Fe 14 B, but the alloy ingot having the above composition melted and cast in a mold is used as a starting material in the R—Fe—B system. When trying to make a sintered magnet, α-
Since Fe and the R-rich phase are locally unevenly distributed, it becomes difficult to pulverize particularly during fine pulverization, and there is a problem that composition shift occurs. To be more specific,
2 When occluding and dehydrogenating H 2 and performing mechanical pulverization (JP-A-60-63304, JP-A-63-33505), α-Fe crystallized in the alloy lump remains as it is during pulverization, The R-rich phase, which hinders pulverization due to its spreadability property and is locally unevenly distributed, produces a hydride by the H 2 occlusion treatment and becomes a fine powder, so that oxidation during mechanical fine pulverization occurs. Acceleration, and in the pulverization using a jet mill, compositional deviation occurs due to scattering in a dominant manner.
【０００５】また、前記１）項の達成のためＲ2Ｆｅ14
Ｂの化学量論的組成に近づけた合金粉末を用いて焼結体
を作製しようとすると、焼結体の作製工程において不可
避な酸化により、液相焼結を引き起こすためのＮｄ−ｒ
ｉｃｈ相が酸化物を生成し、消費されて焼結できなかっ
たり、上記Ｒ2Ｆｅ14Ｂ相の存在量を増加によって必然
的に、Ｎｄ−ｒｉｃｈ相やＢリッチ相の存在量が減少す
るので、焼結体の製造をより一層困難なものにしてい
た。しかも、永久磁石材料の安定性を示す指標の１つで
あり、かつ、重要な性質の１つである保磁力（ｉＨｃ）
が低下してしまうことになった。さらに、前記３）項に
ついては、通常Ｒ−Ｆｅ−Ｂ系永久磁石の製造方法にお
いて、主相結晶粒の磁化容易軸方向を揃えるために、磁
界中でプレス成形する方法が採用されている。その際、
磁界の印加方向とプレス加圧する方向とによって、残留
磁束密度（Ｂｒ）値並びに角型性｛（Ｂｒ2／４）／
（ＢＨ）ｍａｘ｝の値が変化したり、また、印加磁界の
強度によっても影響を受けることが知られている。Further, in order to achieve the above item 1), R 2 Fe 14
When an attempt is made to produce a sintered body by using an alloy powder having a stoichiometric composition of B, Nd-r for causing liquid phase sintering due to unavoidable oxidation in the production process of the sintered body.
Since the ich phase produces an oxide and is consumed and cannot be sintered, or the abundance of the R 2 Fe 14 B phase increases, the abundance of the Nd-rich phase and the B rich phase inevitably decreases. , Making the production of sintered bodies even more difficult. Moreover, the coercive force (iHc), which is one of the indexes showing the stability of the permanent magnet material, and one of the important properties.
Will be reduced. Further, regarding the item 3), in the method of manufacturing an R-Fe-B system permanent magnet, a method of press molding in a magnetic field is adopted in order to align the easy-axis directions of the main phase crystal grains. that time,
By the direction in which pressure application direction and press-magnetic field, the residual magnetic flux density (Br) value and the squareness {(Br 2/4) /
It is known that the value of (BH) max} changes and is also influenced by the strength of the applied magnetic field.
【０００６】[0006]
【発明が解決しようとする課題】最近、鋳塊粉砕法によ
るＲ−Ｆｅ−Ｂ系合金粉末の欠点たる結晶粒の粗大化、
α−Ｆｅの残留、偏析を防止するために、Ｒ−Ｆｅ−Ｂ
系合金溶湯を双ロール法により、特定厚の鋳片となし、
前記鋳片を通常の粉末冶金法に従って、鋳片をスタンプ
ミル・ジョークラッシャーなどで粗粉砕後、さらにディ
スクミル、ボールミル、アトライター、ジェットミルな
ど機械的粉砕法により平均粒径が３〜５μｍの粉末に微
粉砕後、磁場中プレス、焼結時効処理する製造方法が提
案（特開昭６３−３１７６４３号公報）されている。し
かし、前記方法では従来の鋳型に鋳造した鋳塊粉砕法の
場合に比し、微粉砕時の粉砕能率の飛躍的な向上は望め
ず、また微粉砕時、粒界粉砕のみならず、粒内粉砕も起
こるため、磁気特性の大幅の向上も達成できず、また、
Ｒ−ｒｉｃｈ相が酸化に対して安定なＲＨ2相になって
いないため、また、Ｒ−ｒｉｃｈ相が微細で表面積が大
きいため、耐酸化性に劣り、工程中に酸化が進行し、高
特性を得ることができない。Recently, coarsening of crystal grains, which is a defect of the R-Fe-B alloy powder by the ingot crushing method,
In order to prevent α-Fe from remaining and segregating, R-Fe-B
The molten alloy is made into a slab with a specific thickness by the twin roll method,
The slab is coarsely crushed by a stamp mill / jaw crusher according to a usual powder metallurgy method, and then mechanically crushed by a disc mill, a ball mill, an attritor, a jet mill or the like to have an average particle diameter of 3 to 5 μm. A manufacturing method has been proposed (Japanese Patent Laid-Open No. 63-317643) in which a powder is finely pulverized, followed by pressing in a magnetic field and sintering aging treatment. However, in the above method, compared with the case of the ingot crushing method of casting in a conventional mold, it is not possible to expect a dramatic improvement in the pulverization efficiency during fine pulverization, and during fine pulverization, not only grain boundary pulverization but also intragranular Since crushing also occurs, it is not possible to achieve a significant improvement in magnetic properties, and
Since the R-rich phase is not a stable RH 2 phase against oxidation, and because the R-rich phase is fine and has a large surface area, it is inferior in oxidation resistance, and oxidation progresses during the process, resulting in high characteristics. Can't get
【０００７】最近益々、Ｒ−Ｆｅ−Ｂ系永久磁石材料に
対するコストダウンの要求が強く、効率よく高性能永久
磁石を製造することが、極めて重要になっている。この
ため、極限に近い特性を引き出すための製造条件の改良
が必要となっている。発明者らは、効率よくＲ−Ｆｅ−
Ｂ系焼結磁石を製造でき、しかも、磁気特性を向上させ
る方法について種々検討を重ねてきた。Ｒ−Ｆｅ−Ｂ系
焼結磁石の残留磁束密度（Ｂｒ）を高めるためには、強
磁性相であり主相のＲ2Ｆｅ14Ｂ相の含有率を多くする
ことにより達成される。すなわち、磁石の組成をＲ2Ｆ
ｅ14Ｂの化学量論的組成に近づけることが重要となる。
しかしながら、上記組成の合金を溶解し、鋳型に鋳造し
た合金塊を出発原料としてＲ2Ｆｅ14Ｂ系焼結磁石を作
製しようとすると、合金塊に晶出したα−ＦｅやＲ−ｒ
ｉｃｈ相が局部的に偏在していることなどから、特に微
粉砕時に粉砕が困難となり、かつまた、組成ずれを生じ
るなどの問題があった。Recently, there has been a strong demand for cost reduction of R-Fe-B type permanent magnet materials, and it has become extremely important to efficiently produce high-performance permanent magnets. Therefore, it is necessary to improve the manufacturing conditions to bring out the characteristics that are close to the limit. The inventors have efficiently used R-Fe-
Various studies have been conducted on a method for producing a B-based sintered magnet and improving the magnetic characteristics. In order to increase the residual magnetic flux density (Br) of the R—Fe—B system sintered magnet, it is achieved by increasing the content of the R 2 Fe 14 B phase, which is the ferromagnetic phase and is the main phase. That is, the composition of the magnet is R 2 F
It is important to approach the stoichiometric composition of e 14 B.
However, if an alloy ingot having the above composition is melted and an alloy ingot cast in a mold is used as a starting material to produce an R 2 Fe 14 B system sintered magnet, α-Fe or R-r crystallized in the alloy ingot is produced.
Since the ich phase is locally unevenly distributed, there are problems that pulverization becomes difficult, especially when finely pulverizing, and compositional deviation occurs.
【０００８】また、直接還元拡散法で、上記組成の合金
粉末を作製しようとすると、未反応のＦｅ粒子が残存し
たり、また、これを消滅させるために、還元温度を高め
ると、今度は粒子同志が焼結して成長し、しかも還元剤
として添加したＣａやその酸化物などがかみ込まれて不
純物が増加するなどの問題が新たに発生した。そこで、
これら合金原料の製造にかかわる問題点の改善について
種々検討した結果、ストリップ・キャスティング法を用
いて、合金溶湯を急冷凝固させることにより、α−Ｆｅ
の晶出を抑制でき、微細でしかも均質な組成を有する合
金鋳片を製造できることを見出した。Further, when an alloy powder having the above composition is produced by the direct reduction diffusion method, unreacted Fe particles remain, and if the reduction temperature is raised in order to eliminate them, the particles will be removed. A new problem has arisen, in which the comrades sinter and grow, and moreover, Ca added as a reducing agent and its oxide are bitten into it and impurities increase. Therefore,
As a result of various studies on the improvement of the problems associated with the production of these alloy raw materials, α-Fe was obtained by rapidly solidifying the molten alloy using the strip casting method.
It has been found that the alloy slab having a fine and uniform composition can be produced by suppressing the crystallization of aluminum.
【０００９】一方、Ｒ−Ｆｅ−Ｂ系焼結磁石は液相焼結
反応を用いて、焼結が行われている。すなわち、磁石内
には主相で強磁性相のＲ2Ｆｅ14Ｂ相のほかに、Ｂ−ｒ
ｉｃｈ相及び粒界相としてＲ−ｒｉｃｈ相が存在し、こ
れらの相が焼結時に反応して液相が生成し、液相出現に
ともなって、緻密化反応が進行する。従って、Ｂ−ｒｉ
ｃｈ相やＲ−ｒｉｃｈ相は、Ｒ−Ｆｅ−Ｂ系焼結磁石の
製造上、必須な構成相である。しかし、磁石特性を向上
させるためには、主相で強磁性相のＲ2Ｆｅ14Ｂ相の存
在量を極力高めることが必要であり、これを実現するた
めには、Ｒ2Ｆｅ14Ｂ相の化学量論組成に近い合金粉末
をいかに高密度化させるかに集約される。On the other hand, the R-Fe-B system sintered magnet is sintered by using a liquid phase sintering reaction. That is, in addition to the R 2 Fe 14 B phase, which is the main phase and the ferromagnetic phase, in the magnet, B-r
An R-rich phase exists as an ich phase and a grain boundary phase, and these phases react during sintering to generate a liquid phase, and the densification reaction proceeds with the appearance of the liquid phase. Therefore, B-ri
The ch phase and the R-rich phase are essential constituent phases in the production of the R-Fe-B system sintered magnet. However, in order to improve the magnet characteristics, it is necessary to increase the existing amount of the R 2 Fe 14 B phase, which is the main phase and the ferromagnetic phase, as much as possible, and in order to realize this, the R 2 Fe 14 B phase is required. It is summarized how to densify the alloy powder close to the stoichiometric composition.
【００１０】この発明は、上述したＲ−Ｆｅ−Ｂ系永久
磁石材料の製造方法における問題点を解消し、効率よい
微粉砕を可能にし、かつ耐酸化性に優れ、しかも磁石の
結晶粒の微細化により高いｉＨｃを発現し、さらに各結
晶粒の磁化容易方向の配向度を高めて、（ＢＨ）ｍａｘ
値（ＭＧＯｅ）；Ａと、ｉＨｃ値（ｋＯｅ）；Ｂの合計
値、Ａ＋Ｂ≧５９の値を有し、角型性｛（Ｂｒ2／４）
／（ＢＨ）ｍａｘ｝が１．０１〜１．０４５の値を示す
高性能Ｒ−Ｆｅ−Ｂ系永久磁石材料の提供を目的として
いる。この発明は、前述の液相焼結反応にＲ−Ｆｅ−Ｂ
系永久磁石特性の高性能化を阻害する磁石構成相のＢ−
ｒｉｃｈ相及びＲ−ｒｉｃｈ相と反応して主相のＲ2Ｆ
ｅ14Ｂ相を生成してＢ−ｒｉｃｈ相及びＲ−ｒｉｃｈ相
を低減し、さらに合金粉末中の含有酸素量を低減でき、
種々の磁石特性に応じた組成の合金粉末を製造性よく容
易に提供できるＲ−Ｆｅ−Ｂ系永久磁石材料の製造方法
の提供を目的としている。The present invention solves the above-mentioned problems in the method for producing an R-Fe-B system permanent magnet material, enables efficient fine pulverization, is excellent in oxidation resistance, and has a fine crystal grain of the magnet. By increasing the degree of iHc, and further increasing the degree of orientation of each crystal grain in the easy magnetization direction, (BH) max
Value (MGOe); and A, iHc value (kOe); the sum of B, has a value of A + B ≧ 59, squareness {(Br 2/4)
The objective is to provide a high-performance R-Fe-B based permanent magnet material exhibiting a value of / (BH) max} of 1.01 to 1.045. This invention is based on R-Fe-B in the liquid phase sintering reaction described above.
Of the constituent phase of the magnet that hinders the improvement of the performance of the permanent magnet system
R 2 F of the main phase by reacting with the rich phase and the R-rich phase
e 14 B phase can be generated to reduce the B-rich phase and the R-rich phase, and further the oxygen content in the alloy powder can be reduced,
An object of the present invention is to provide a method for producing an R-Fe-B based permanent magnet material, which can easily provide alloy powders having compositions according to various magnet characteristics with good productivity.
【００１１】[0011]
【課題を解決するための手段】この発明は、ストリップ
・キャスト法により得られたＲ2Ｆｅ14Ｂ相を主相とす
るＲ−Ｆｅ−Ｂ系合金粉末に、全量の６０％以下のスト
リップ・キャスト法により得られたＮｄ2Ｆｅ17相を含
む調整用合金粉末を添加配合することにより、調整用合
金粉末中のＮｄ2Ｆｅ17相と主相系Ｒ−Ｆｅ−Ｂ系合金
粉末中のＢ−ｒｉｃｈ相及びＮｄ−ｒｉｃｈ相との反応
により、新たにＮｄ2Ｆｅ14Ｂ相が生成されるため、永
久磁石の磁石特性を劣化させるＢ−ｒｉｃｈ相及びＮｄ
−ｒｉｃｈ相の量を調整低減でき、得られる磁石の高性
能化を図ることができ、さらに合金粉末中の含有酸素量
を低減でき、種々の磁石特性に応じた組成の合金粉末を
容易に提供できる。According to the present invention, an R-Fe-B system alloy powder having an R 2 Fe 14 B phase as a main phase, which is obtained by a strip casting method, is used in an amount of 60% or less of the total strip. by adding blended adjusting alloy powder containing the Nd 2 Fe 17 phase obtained by casting, the adjustment alloy Nd 2 Fe 17 phase and the main phase system R-Fe-B alloy powder in the powder B A new Nd 2 Fe 14 B phase is generated by the reaction with the -rich phase and the Nd-rich phase, so that the B-rich phase and the Nd phase that deteriorate the magnet characteristics of the permanent magnet are deteriorated.
-The amount of rich phase can be adjusted and reduced, the performance of the obtained magnet can be improved, the oxygen content in the alloy powder can be reduced, and alloy powder having a composition according to various magnet characteristics can be easily provided. it can.
【００１２】すなわち、この発明は、Ｒ（但しＲはＹを
含む希土類元素のうち少なくとも１種）１１原子％〜２
０原子％、Ｂ４原子％〜１５原子％、残部Ｆｅ（但しＦ
ｅの１部をＣｏ、Ｎｉの１種または２種にて置換でき
る）及び不可避的不純物からなる合金溶湯をストリップ
・キャスティング法にてＲ2Ｆｅ14Ｂ相を主相とする主
相系鋳片に鋳造後、また、Ｒ（但しＲはＹを含む希土類
元素のうち少なくとも１種）２０原子％以下、残部Ｆｅ
（但しＦｅの１部をＣｏ、Ｎｉの１種または２種にて置
換できる）及び不可避的不純物からなる合金溶湯をスト
リップ・キャスティング法にてＲ2Ｆｅ17相を含む調整
用合金鋳片に鋳造後、各鋳片を吸排気可能な容器に収容
し、該容器内の空気をＨ2ガスにて置換し、Ｈ2ガスを供
給してＨ2吸蔵処理にて得られた崩壊合金粉を脱Ｈ2処理
した後、不活性ガス気流中で微粉砕して平均粒径が１μ
ｍ〜１０μｍの主相系合金粉末と調整用合金粉末とな
し、前記主相系合金粉末に調整用合金粉末を配合混合し
た後、この混合合金粉末をモールド内に充填して瞬間的
に１０ｋＯｅ以上のパルス磁界をかけて配向させた後、
成形し、焼結、時効処理し、（ＢＨ）ｍａｘ値；Ａ（Ｍ
ＧＯｅ）とｉＨｃ値；Ｂ（ｋＯｅ）の合計値Ａ＋Ｂが５
９以上の値を有し、角型性｛（Ｂｒ2／４）／（ＢＨ）
ｍａｘ｝が１．０１〜１．０４５の値を有する永久磁石
材料を得るＲ−Ｆｅ−Ｂ系永久磁石材料の製造方法であ
る。また、この発明は、上記の構成において、主相系合
金溶湯がＲ（但しＲはＹを含む希土類元素のうち少なく
とも１種）１３原子％〜１６原子％、Ｂ６原子％〜１０
原子％、残部Ｆｅ（但し、Ｆｅの１部をＣｏ，Ｎｉの１
種又は２種にて置換できる）及び不可避的不純物からな
ることを特徴とするＲ−Ｆｅ−Ｂ系永久磁石材料の製造
方法を合わせて提案する。That is, according to the present invention, R (provided that R is at least one of rare earth elements including Y) is 11 atomic% to 2
0 atomic%, B4 atomic% to 15 atomic%, balance Fe (however, F
Main phase cast slab with R 2 Fe 14 B phase as main phase by strip casting method with molten alloy containing unavoidable impurities (part of e can be replaced by Co or Ni 1 or 2) After casting, 20 atomic% or less of R (where R is at least one of rare earth elements including Y) and the balance Fe
(Although one part of Fe can be replaced with one or two kinds of Co and Ni) and inevitable impurities, the molten alloy is cast by a strip casting method into an alloy casting alloy slab containing the R 2 Fe 17 phase. after, each slab is accommodated in the intake and exhaust can container, the air in the vessel was replaced with H 2 gas, disintegration alloy powder obtained by supplying H 2 gas at H 2 adsorption process de After H 2 treatment, finely pulverize in an inert gas stream to obtain an average particle size of 1μ
m to 10 μm main phase alloy powder and adjusting alloy powder, and after mixing and mixing the adjusting alloy powder with the main phase alloy powder, the mixed alloy powder is filled in a mold and instantaneously 10 kOe or more. After orienting by applying the pulsed magnetic field of
Molded, sintered, aged, (BH) max value; A (M
GOe) and iHc value; sum of B (kOe) A + B is 5
Have 9 or more, squareness {(Br 2/4) / (BH)
It is a method for producing an R-Fe-B based permanent magnet material for obtaining a permanent magnet material having a value of max1 of 1.01 to 1.045. Further, according to the present invention, in the above-mentioned constitution, the main phase alloy melt is R (where R is at least one of rare earth elements including Y) 13 atom% to 16 atom%, B6 atom% to 10 atom%.
Atomic%, balance Fe (however, 1 part of Fe is 1 of Co, 1 of Ni
(Or can be substituted by two or more kinds) and unavoidable impurities, and a method for producing an R—Fe—B based permanent magnet material is also proposed.
【００１３】以下に、この発明におけるＲ−Ｆｅ−Ｂ系
永久磁石材料用の主相系合金及び調整用合金の組成の限
定理由を説明する。この発明のにおけるＲ−Ｆｅ−Ｂ系
永久磁石材料用の主相系合金及び調整用合金に含有され
る希土類元素Ｒはイットリウム（Ｙ）を包含し、軽希土
類及び重希土類を包含する希土類元素である。Ｒとして
は、軽希土類をもって足り、特にＮｄ，Ｐｒが好まし
い。また通常Ｒのうち１種もって足りるが、実用上は２
種以上の混合物（ミッシユメタル、ジジム等）を入手上
の便宜等の理由により用いることができ、Ｓｍ，Ｙ，Ｌ
ａ，Ｃｅ，Ｇｄ等は他のＲ、特にＮｄ，Ｐｒ等との混合
物として用いることができる。なお、このＲは純希土類
元素でなくてもよく、工業上入手可能な範囲で製造上不
可避な不純物を含有するものでも差し支えない。Ｒ2Ｆ
ｅ17相を含む調整用合金粉末を添加混合するＲ2Ｆｅ14
Ｂ相を主相とする主相系合金粉末を得るには、Ｒが１１
原子％未満では、Ｒ、Ｂの拡散しない残留鉄部の増加と
なり、２０原子％を超えるとＲ−ｒｉｃｈ相が増加して
粉砕時に含有酸素量が増えるため、Ｒは１１原子％〜２
０原子％とする。より好ましいＲ量は１３原子％〜１６
原子％である。Ｂは、４原子％未満では高い保磁力（ｉ
Ｈｃ）が得られず、１２原子％を超えると残留磁束密度
（Ｂｒ）が低下するため、すぐれた永久磁石が得られな
いため、Ｂは４原子％〜１２原子％とする。より好まし
いＢ量は６原子％〜１０原子％である。残部はＦｅ及び
不可避的不純物からなり、Ｆｅは６５原子％〜８２原子
％の範囲が好ましい。Ｆｅは６５原子％未満では相対的
に希土類元素及びＢが−ｒｉｃｈとなりＲ−ｒｉｃｈ
相、Ｂ−ｒｉｃｈ相が増加し、８２原子％を超えると相
対的に希土類元素及びＢが少なくなり、残留Ｆｅ部が増
加し不均一な合金粉末となるため好ましくない。より好
ましいＦｅ量は７４原子％〜８１原子％である。主相系
合金粉末中のＣｏとＮｉの１種または２種は、Ｒ2Ｆｅ
14Ｂ主相中のＦｅと置換されて保磁力を低下させるた
め、Ｃｏは１０原子％以下、Ｎｉは３原子％以下とす
る。ただし、上述のＣｏまたはＮｉでＦｅの一部を置換
した場合、Ｆｅは５５原子％〜７２原子％の範囲であ
る。The reasons for limiting the compositions of the main phase alloy and the adjusting alloy for the R—Fe—B system permanent magnet material in the present invention will be explained below. The rare earth element R contained in the main phase alloy and the adjusting alloy for the R—Fe—B system permanent magnet material in the present invention includes yttrium (Y) and is a rare earth element including light rare earth and heavy rare earth. is there. As R, a light rare earth element is sufficient, and Nd and Pr are particularly preferable. Usually, one of R is enough, but in practice it is 2
Mixtures of two or more species (Missille metal, didymium, etc.) can be used for reasons of availability, Sm, Y, L
a, Ce, Gd and the like can be used as a mixture with other R, especially Nd, Pr and the like. It should be noted that this R does not have to be a pure rare earth element, and may contain impurities that are unavoidable in production within the industrially available range. R 2 F
R 2 Fe 14 to which the alloy powder for adjustment containing the e 17 phase is added and mixed
To obtain a main phase alloy powder containing the B phase as the main phase, R is 11
If it is less than atomic%, the residual iron portion in which R and B do not diffuse increases, and if it exceeds 20 atomic%, the R-rich phase increases and the oxygen content increases during pulverization, so that R is 11 atomic% to 2
It is 0 atomic%. More preferable R amount is 13 atom% to 16
It is atomic%. B has a high coercive force (i
Hc) cannot be obtained, and if it exceeds 12 atom%, the residual magnetic flux density (Br) decreases, and an excellent permanent magnet cannot be obtained. Therefore, B is 4 atom% to 12 atom%. A more preferable B content is 6 atom% to 10 atom%. The balance consists of Fe and inevitable impurities, and Fe is preferably in the range of 65 atom% to 82 atom%. If Fe is less than 65 atomic%, the rare earth element and B become -rich and R-rich.
Phase and B-rich phase increase, and when it exceeds 82 atomic%, the rare earth elements and B relatively decrease, the residual Fe portion increases, and a non-uniform alloy powder is formed, which is not preferable. A more preferable Fe amount is 74 at% to 81 at%. One or two of Co and Ni in the main phase alloy powder is R 2 Fe.
In order to reduce the coercive force by substituting Fe in the 14 B main phase, Co is set to 10 atom% or less and Ni is set to 3 atom% or less. However, when a part of Fe is replaced by Co or Ni described above, Fe is in the range of 55 atom% to 72 atom%.
【００１４】Ｒ2Ｆｅ17相を含む調整用合金粉末を得る
には、Ｒが２０原子％を超えると合金粉末の作製時にＲ
−ｒｉｃｈな相が増加して酸化等の問題があり好ましく
なく、Ｒの好ましい量は５〜１５原子％である。さら
に、残部はＦｅ及び不可避的不純物からなり、Ｆｅは８
５原子％〜９５原子％の範囲が好ましい。In order to obtain the alloy powder for adjustment containing the R 2 Fe 17 phase, when R exceeds 20 atomic%, R is added when the alloy powder is produced.
There is a problem of oxidation due to an increase in -rich phase, which is not preferable, and the preferable amount of R is 5 to 15 atom%. Further, the balance consists of Fe and inevitable impurities, and Fe is 8
The range of 5 at% to 95 at% is preferable.
【００１５】さらに、Ｒ2Ｆｅ14Ｂ相を主相とする合金
粉末および／またはＲ2Ｆｅ17相を含む調整用合金粉末
に、９．５原子％以下のＡｌ、４．５原子％以下のＴ
ｉ、９．５原子％以下のＶ、８．５原子％以下のＣｒ、
８．０原子％以下のＭｎ、５原子％以下のＢｉ、１２．
５原子％以下のＮｂ、１０．５原子％以下のＴａ、９．
５原子％以下のＭｏ、９．５原子％以下のＷ、２．５原
子％以下のＳｂ、７原子％以下のＧｅ、３．５原子％以
下のＳｎ、５．５原子％以下のＺｒ、５．５原子％以下
のＨｆのうち少なくとも１種添加含有させることによ
り、得られる永久磁石合金の高保磁力が可能になる。Further, in the alloy powder having the R 2 Fe 14 B phase as a main phase and / or the adjusting alloy powder containing the R 2 Fe 17 phase, 9.5 atomic% or less of Al and 4.5 atomic% or less of T
i, V of 9.5 atomic% or less, Cr of 8.5 atomic% or less,
8.0 atomic% or less Mn, 5 atomic% or less Bi, 12.
Nb of 5 atomic% or less, Ta of 10.5 atomic% or less, 9.
Mo of 5 atomic% or less, W of 9.5 atomic% or less, Sb of 2.5 atomic% or less, Ge of 7 atomic% or less, Sn of 3.5 atomic% or less, Zr of 5.5 atomic% or less, By adding at least one of Hf of 5.5 atomic% or less, a high coercive force of the obtained permanent magnet alloy becomes possible.
【００１６】この発明において、特定組成のＲ2Ｆｅ14
Ｂ相、Ｒ−ｒｉｃｈ相が微細に分離した組織を有する磁
石材料の鋳片は、特定組成の合金溶湯を単ロール法、あ
るいは双ロール法等によるストリップ・キャスティング
法にて製造される。所望の鋳片板厚により、単ロール法
と双ロール法を使い分けるが、板厚が厚い場合は双ロー
ル法を、また板厚が薄い場合は単ロール法を採用したほ
うが好ましい。また、ストリップ・キャスティング法に
より得られた主相系合金粉末及び調整用合金粉末の結晶
粒は、従来の鋳型に鋳造して得られた鋳塊のものに比べ
て、約１／１０以上も微細であり、例えば、その短軸方
向の寸法は０．１μｍ〜５０μｍ、長軸方向は５μｍ〜
２００μｍの微細結晶であり、かつその主相結晶粒を取
り囲むようにＲ−ｒｉｃｈ相が微細に分散されており、
局部に偏在している領域においても、その大きさは２０
μｍ以下である。Ｒ−ｒｉｃｈ相が５μｍ以下に微細に
分離することによって、Ｈ2吸蔵処理時にＲ−ｒｉｃｈ
相が水素化物を生成した際の体積膨張が均一に発生して
細分化されるため、微粉砕にて主相の結晶粒が細分化さ
れて粒度分布が均一な微粉末が得られる。In the present invention, R 2 Fe 14 having a specific composition is used.
A slab of a magnetic material having a structure in which the B phase and the R-rich phase are finely separated is manufactured by a strip casting method such as a single roll method or a twin roll method using a molten alloy having a specific composition. The single roll method and the twin roll method are selectively used according to the desired thickness of the slab, but it is preferable to use the twin roll method when the plate thickness is thick and the single roll method when the plate thickness is thin. In addition, the crystal grains of the main phase alloy powder and the adjusting alloy powder obtained by the strip casting method are about 1/10 or more finer than those of the ingot obtained by casting in the conventional mold. For example, the dimension in the short axis direction is 0.1 μm to 50 μm, and the dimension in the long axis direction is 5 μm to
It is a fine crystal of 200 μm, and the R-rich phase is finely dispersed so as to surround the main phase crystal grains,
Even in the localized area, the size is 20
μm or less. By finely separating the R-rich phase to 5 μm or less, the R-rich phase is separated during the H 2 occlusion treatment.
Since volume expansion uniformly occurs when the phase forms a hydride, and the particles are subdivided into fine particles, the crystal grains of the main phase are subdivided by fine pulverization to obtain a fine powder having a uniform particle size distribution.
【００１７】この発明において、Ｈ2吸蔵処理には、例
えば、所定大きさに破断した０．０３ｍｍ〜１０ｍｍ厚
みの鋳片を原料ケース内に挿入し、上記原料ケースを蓋
を締めて密閉できる容器内に装入して密閉したのち、容
器内を十分に真空引きした後、２００Ｔｏｒｒ〜５０ｋ
ｇ／ｃｍ2の圧力のＨ2ガスを供給して、該鋳片にＨ2を
吸蔵させる。このＨ2吸蔵反応は、発熱反応であるた
め、容器の外周には冷却水を供給する冷却配管が周設し
て容器内の昇温を防止しながら、所定圧力のＨ2ガスを
一定時間供給することにより、Ｈ2ガスが吸収されて該
鋳片は自然崩壊して粉化する。さらに、粉化した合金を
冷却したのち、真空中で脱Ｈ2ガス処理する。前記処理
の合金粉末は粒内に微細亀裂が内在するので、ポール・
ミル、ジェットミル等で短時間で微粉砕され、１μｍ〜
８０μｍの所要粒度の合金粉末を得ることができる。こ
の発明において、上記処理容器内を予め不活性ガスで空
気を置換し、その後Ｈ2ガスで不活性ガスを置換しても
よい。また、鋳塊の破断大きさは、小さいほど、Ｈ2粉
砕の圧力を小さくでき、また、Ｈ2ガス圧力は、減圧下
でも破断した鋳塊はＨ2吸収し粉化されるが、圧力が大
気圧より高くなるほど、粉化されやすくなる。しかし、
２００Ｔｏｒｒ未満では粉化性が悪くなり、５０ｋｇ／
ｃｍ2を超えるとＨ2吸収による粉化の点では好ましい
が、装置や作業の安全性からは好ましくないため、Ｈ2
ガス圧力は２００Ｔｏｒｒ〜５０ｋｇ／ｃｍ2とする。
量産性からは、２ｋｇ／ｃｍ2〜１０ｋｇ／ｃｍ2が好ま
しい。 この発明において、Ｈ2吸蔵による粉化の処理時
間は、前記密閉容器の大きさ、破断塊の大きさ、Ｈ2ガ
ス圧力により変動するが、５分以上は必要である。In the present invention, H2An example of storage processing
For example, 0.03mm to 10mm thickness broken into a predetermined size
Insert only the slab into the raw material case and cover the raw material case.
After closing the container by inserting it into a container that can be sealed,
After fully vacuuming the chamber, 200 Torr-50k
g / cm2H of pressure2Gas is supplied to the slab to generate H2To
Let it occlude. This H2The occlusion reaction is an exothermic reaction.
For this reason, a cooling pipe for supplying cooling water is installed around the container.
To prevent the temperature inside the container from rising, and2Gas
By supplying for a certain period of time, H2Gas is absorbed
The slab naturally disintegrates and powders. In addition, powdered alloy
After cooling, remove H in vacuum2Gas treatment. The processing
In the alloy powder of, since there are fine cracks in the grains,
Finely pulverized in a short time with a mill, jet mill, etc.
An alloy powder with a required particle size of 80 μm can be obtained. This
In the invention of claim 1, the inside of the processing container is previously emptied with an inert gas.
Replace Qi, then H2Even if the inert gas is replaced with gas
Good. Further, the smaller the fracture size of the ingot, the higher the H2powder
Crushing pressure can be reduced and H2Gas pressure is under reduced pressure
But the broken ingot is H2Absorbs and is pulverized, but the pressure is large
The higher the atmospheric pressure, the easier the powder is to be pulverized. But,
If it is less than 200 Torr, the pulverization property becomes poor, and 50 kg /
cm2H is exceeded2It is preferable in terms of pulverization by absorption
However, it is not preferable from the viewpoint of safety of equipment and work, so H2
Gas pressure is 200 Torr to 50 kg / cm2And
2 kg / cm for mass production2-10kg / cm2Is preferred
Good In this invention, H2During pulverization by occlusion
In the space, the size of the closed container, the size of the broken mass, H2Moth
Depending on the pressure, it takes 5 minutes or more.
【００１８】Ｈ2吸蔵により粉化した合金粉末を冷却
後、真空中で１次の脱Ｈ2ガス処理する。さらに、真空
中またはアルゴンガス中において、粉化合金を１００℃
〜７５０℃に加熱し、０．５時間以上の２次脱Ｈ2ガス
処理すると、粉化合金中のＨ2ガスは完全に除去できる
とともに、長期保存に伴う粉末あるいはプレス成形体の
酸化を防止して、得られる永久磁石の磁気特性の低下を
防止できる。この発明による１００℃以上に加熱する脱
水素処理は、すぐれた脱水素効果を有しているために上
記の真空中での１次脱水素処理を省略し、崩壊粉を直接
１００℃以上の真空中またはアルゴンガス雰囲気中で脱
水素処理してもよい。すなわち、前述したＨ2吸蔵反応
用容器内でＨ2吸蔵・崩壊反応させた後、得られた崩壊
粉を続いて同容器の雰囲気中で１００℃以上に加熱する
脱水素処理を行うことができる。あるいは、真空中での
脱水素処理後、処理容器から取り出して崩壊粉を微粉砕
したのち、再度処理容器で１００℃以上に加熱するこの
発明の脱水素処理を施してもよい。上記の脱水素処理に
おける加熱温度は、１００℃未満では崩壊合金粉内に残
存するＨ2を除去するのに長時間を要して量産的でな
い。また、７５０℃を超える温度では液相が出現し、粉
末が固化してしまうため、微粉砕が困難になったり、プ
レス時の成形性を悪化させるので、焼結磁石の製造の場
合には好ましくない。また、焼結磁石の焼結性を考慮す
ると、好ましい脱水素処理温度は２００℃〜６００℃で
ある。また、処理時間は処理量によって変動するが０．
５時間以上は必要である。After cooling the alloy powder pulverized by H 2 occlusion, primary H 2 degassing treatment is performed in vacuum. Further, the powdered alloy is heated to 100 ° C. in vacuum or argon gas.
Was heated to to 750 ° C., preventing the two Tsugida' H 2 gas treatment over 0.5 hours, with H 2 gas in the pulverized alloy can be completely removed, the oxidation of the powder or pressed bodies due to long-term storage As a result, it is possible to prevent deterioration of the magnetic properties of the obtained permanent magnet. Since the dehydrogenation treatment of heating to 100 ° C. or higher according to the present invention has an excellent dehydrogenation effect, the above primary dehydrogenation treatment in vacuum is omitted, and the disintegrated powder is directly vacuumed at 100 ° C. or higher. You may perform a dehydrogenation process inside or in an argon gas atmosphere. That can be done with H 2 After absorption and degradation reactions, dehydrogenation treatment which subsequently resulting collapse powder is heated to above 100 ° C. in an atmosphere of the container in the container for H 2 occlusion reaction described above . Alternatively, after dehydrogenation treatment in a vacuum, the dehydrogenation treatment of the present invention may be carried out in which the disintegrated powder is taken out from the treatment container, finely crushed and then heated to 100 ° C. or higher in the treatment container. If the heating temperature in the above dehydrogenation treatment is less than 100 ° C., it takes a long time to remove H 2 remaining in the disintegrated alloy powder and is not mass-produced. Further, at a temperature of higher than 750 ° C., a liquid phase appears and the powder is solidified, which makes fine pulverization difficult and deteriorates the formability at the time of pressing. Therefore, it is preferable in the case of producing a sintered magnet. Absent. Further, considering the sinterability of the sintered magnet, the preferable dehydrogenation treatment temperature is 200 ° C to 600 ° C. Further, the processing time varies depending on the processing amount, but is 0.
At least 5 hours is required.
【００１９】次に微粉砕には、不活性ガス（例えば、Ｎ
2、Ａｒ）によるジェット・ミルにて微粉砕を行う。勿
論、有機溶媒（例えば、ベンゼンやトルエン等）を用い
たボールミルや、アトライター粉砕を用いることも可能
である。微粉砕での粉末の平均粒度は、１μｍ〜１０μ
ｍが好ましい。１μｍ未満になると粉砕した粉末が極め
て活性となり著しく酸化されやすく、発火等の恐れが生
ずる。また、１０μｍを超えると粉砕されない粗大粒子
が残存し、保磁力が低下したり、焼結の進行が遅く密度
の低下を引き起こすことになる。より好ましくは、２〜
４μｍの平均粒度の微粉末にすることである。Next, for fine pulverization, an inert gas (for example, N 2
2. Fine pulverize with a jet mill using Ar). Of course, it is also possible to use a ball mill using an organic solvent (for example, benzene, toluene, etc.) or attritor grinding. The average particle size of the finely pulverized powder is 1 μm to 10 μm.
m is preferred. If it is less than 1 μm, the pulverized powder becomes extremely active and is prone to be easily oxidized, which may cause ignition. On the other hand, if it exceeds 10 μm, coarse particles that are not crushed will remain, and the coercive force will decrease, or the progress of sintering will be slow, and the density will decrease. More preferably, 2
A fine powder having an average particle size of 4 μm.
【００２０】磁界を用いたプレスには、次の方法を提案
する。微粉砕した粉末を不活性ガス雰囲気中でモールド
に充填する。モールドは、非磁性の金属、酸化物から作
製したもののほか、プラスチックやゴム等の有機化合物
でも良い。粉末の充填密度は、その粉末の静止状態の嵩
密度（充填密度１．４ｇ／ｃｍ3）から、タッピング後
の固め嵩密度（充填密度３．０ｇ／ｃｍ3）の範囲が好
ましい。従って充填密度は１．４〜３．０ｇ／ｃｍ3に
限定する。これを、空心コイル、コンデンサー電源によ
るパルス磁界を加えて粉末の配向を行う。配向の際、上
下パンチを用いて圧縮を行いながら、繰り返し、パルス
磁界を加えてもよい。パルス磁界の強度は大きければ大
きい程良く、最低１０ｋＯｅ以上は必要とする。好まし
くは３０ｋＯｅ〜８０ｋＯｅである。パルス磁界の時間
は、図２の時間と磁界強さのグラフに示す如く、１μｓ
ｅｃ〜１０ｓｅｃが好ましく、さらには５μｓｅｃ〜１
００ｍｓｅｃが好ましく、パルス磁界の印加回数は１〜
１０回、さらに、好ましくは１〜５回である。配向後の
粉末は、静水圧プレスによって固めることができる。こ
の際、可塑性のあるモールドを使用した場合には、その
まま、静水圧プレスを行うことが可能である。静水圧プ
レス法による加圧力は０．５ｔｏｎ／ｃｍ2〜５ｔｏｎ
／ｃｍ2が望ましく、さらに好ましくは１ｔｏｎ／ｃｍ2
〜３ｔｏｎ／ｃｍ2である。また、パルス磁界による配
向とプレスとを連続的に行うためには、ダイス内部にパ
ルス磁界を発生させるコイルを埋め込み、パルス磁界を
用いて配向させた後、通常の磁界中プレス法で成形する
ことも可能である。磁界中プレス法による加圧力は０．
５ｔｏｎ／ｃｍ2〜５ｔｏｎ／ｃｍ2が望ましく、さらに
好ましくは１ｔｏｎ／ｃｍ2〜３ｔｏｎ／ｃｍ2である。The following method is proposed for pressing using a magnetic field. The finely pulverized powder is filled in a mold in an inert gas atmosphere. The mold may be made of non-magnetic metal or oxide, or may be an organic compound such as plastic or rubber. The packing density of the powder is preferably in the range of the bulk density of the powder in a static state (packing density 1.4 g / cm 3 ) to the solidified bulk density after tapping (packing density 3.0 g / cm 3 ). Therefore, the packing density is limited to 1.4 to 3.0 g / cm 3 . The powder is oriented by applying a pulsed magnetic field from an air-core coil or a condenser power supply. At the time of orientation, a pulsed magnetic field may be repeatedly applied while performing compression using upper and lower punches. The higher the strength of the pulsed magnetic field, the better, and at least 10 kOe or more is required. It is preferably 30 kOe to 80 kOe. The time of the pulse magnetic field is 1 μs as shown in the graph of time and magnetic field strength in FIG.
ec to 10 sec is preferable, and further 5 μsec to 1
00 msec is preferable, and the number of times the pulsed magnetic field is applied is 1 to
It is 10 times, more preferably 1 to 5 times. The powder after orientation can be hardened by isostatic pressing. At this time, when a plastic mold is used, the isostatic pressing can be performed as it is. The pressing force by the hydrostatic pressing method is 0.5 ton / cm 2 to 5 ton
/ Cm 2 is desirable, more preferably 1 ton / cm 2
~ 3 ton / cm 2 . Further, in order to continuously perform the orientation and the pressing by the pulsed magnetic field, a coil for generating the pulsed magnetic field is embedded in the die, the orientation is performed by using the pulsed magnetic field, and then the ordinary magnetic field pressing method is performed. Is also possible. The pressing force by the pressing method in the magnetic field is 0.
It is preferably 5 ton / cm 2 to 5 ton / cm 2 , and more preferably 1 ton / cm 2 to 3 ton / cm 2 .
【００２１】この発明にて得られるＲ−Ｆｅ−Ｂ系永久
磁石の好ましい組成並びにその性状の限定理由を説明す
る。Ｒは、Ｒ−Ｆｅ−Ｂ系永久磁石の必須元素であっ
て、１２原子％未満では高磁気特性、特に高保磁力が得
られず、１６原子％を越えると残留磁束密度（Ｂｒ）が
低下して、すぐれた特性の永久磁石が得られない。よっ
て、Ｒは１２原子％〜１６原子％の範囲とするが、最適
のＲの範囲は１２．５原子％〜１４原子％である。Ｂ
は、Ｒ−Ｆｅ−Ｂ系永久磁石の必須元素であって、４原
子％未満では高い保磁力（ｉＨｃ）は得られず、８％原
子を越えると残留磁束密度（Ｂｒ）が低下するため、す
ぐれた永久磁石が得られない。よって、Ｂは４原子％〜
８原子％とするが、最適のＢの範囲は５．８原子％〜７
原子％である。Ｆｅは７６原子％未満では残理磁束密度
（Ｂｒ）が低下し、８４原子％を超えると高い保磁力が
得られないため、Ｆｅは７６〜８４原子％に限定する。
また、Ｆｅの一部をＣｏ、Ｎｉの１種又は２種で置換す
る理由は、永久磁石の温度特性を向上させる効果及び耐
食性を向上させる効果が得られるためであるが、Ｃｏ、
Ｎｉの１種又は２種はＦｅの５０％を越えると高い保磁
力が得られず、すぐれた永久磁石が得られない。よっ
て、Ｃｏ、ＮｉはＦｅの５０％を上限とする。Ｏ2を５
０００ｐｐｍ以下に限定した理由は、５０００ｐｐｍを
越えるとＲリッチ相が酸化し、焼結時に十分な液相を生
成できなくなり、密度が低下してしまうため、高い磁束
密度が得られなくなり、耐候性も劣化するので好ましく
なく、Ｏ2の最適範囲は２００〜３０００ｐｐｍであ
る。また、永久磁石材料の見かけ密度が７．４５ｇ／ｃ
ｍ3未満では高い磁束密度が得られず、本発明の特徴た
る（ＢＨ）ｍａｘ値；Ａ（ＭＧＯｅ）とｉＨｃ値；Ｂ
（ｋＯｅ）の合計値Ａ＋Ｂが５９以上の磁石材料が得ら
れないので好ましくない。The preferable composition of the R-Fe-B system permanent magnet obtained by the present invention and the reason for limiting its properties will be described. R is an essential element of the R-Fe-B system permanent magnet. If it is less than 12 atomic%, high magnetic properties, particularly high coercive force cannot be obtained, and if it exceeds 16 atomic%, the residual magnetic flux density (Br) decreases. Therefore, a permanent magnet with excellent characteristics cannot be obtained. Therefore, R is set in the range of 12 atom% to 16 atom%, but the optimum range of R is 12.5 atom% to 14 atom%. B
Is an essential element of the R-Fe-B system permanent magnet, and a high coercive force (iHc) cannot be obtained at less than 4 atom%, and a residual magnetic flux density (Br) decreases at more than 8% atom. You cannot get a good permanent magnet. Therefore, B is 4 atomic% ~
8 atomic%, but the optimum range of B is 5.8 atomic% to 7
It is atomic%. When Fe is less than 76 atomic%, the residual magnetic flux density (Br) is lowered, and when it exceeds 84 atomic%, a high coercive force cannot be obtained, so Fe is limited to 76 to 84 atomic%.
The reason for substituting a part of Fe with one or two of Co and Ni is that the effect of improving the temperature characteristics of the permanent magnet and the effect of improving corrosion resistance can be obtained.
When one or two kinds of Ni exceeds 50% of Fe, a high coercive force cannot be obtained, and an excellent permanent magnet cannot be obtained. Therefore, the upper limit of Co and Ni is 50% of Fe. O 2 to 5
The reason for limiting the content to 000 ppm or less is that if the content exceeds 5000 ppm, the R-rich phase oxidizes, a sufficient liquid phase cannot be generated during sintering, and the density decreases, so that a high magnetic flux density cannot be obtained and the weather resistance is also high. Since it deteriorates, it is not preferable, and the optimum range of O 2 is 200 to 3000 ppm. Moreover, the apparent density of the permanent magnet material is 7.45 g / c.
If it is less than m 3 , a high magnetic flux density cannot be obtained, and the characteristic (BH) max value of the present invention; A (MGOe) and iHc value; B
A magnet material having a total value A + B of (kOe) of 59 or more cannot be obtained, which is not preferable.
【００２２】この発明のＲ−Ｂ−Ｆｅ系永久磁石におい
て、結晶相の主相のＲ2Ｆｅ14Ｂ相が９０％以上、好ま
しくは９４％以上存在することが不可欠である。現在大
量生産されているＲ−Ｆｅ−Ｂ系焼結磁石は前記Ｒ2Ｆ
ｅ14Ｂ相が最高で９０％であり、９０％未満では本発明
のＡ＋Ｂ値が５９以上の高磁気特性は得られない。この
発明の磁石の配向度は前記１）式から算出したものであ
り、磁石の配向度が８５％以上有することが、Ａ＋Ｂ値
を５９以上保持するために必須であり、配向度が８５未
満では減磁曲線の角型性が低下して、高い残留磁束密度
（Ｂｒ）が低下するため、（ＢＨ）ｍａｘ値は低下する
ので好ましくない。好ましい配向度は９２％以上であ
る。また、角型性｛（Ｂｒ2／４）／（ＢＨ）ｍａｘ｝
は理論的な場合１．００の値を示すものであるが、実際
の永久磁石材料においては、上述の配向度の乱れが必然
的に生じるため、従来、種々の改善を実施しても１．０
５まで到達するのが限界であったが、前述した特定の製
造方法にて得られたこの発明による永久磁石材料は、角
型性の値が１．０１〜１．０４５となる。In the R—B—Fe system permanent magnet of the present invention, it is essential that the main phase of the crystal phase, R 2 Fe 14 B phase, is 90% or more, preferably 94% or more. The R-Fe-B system sintered magnets currently mass-produced are R 2 F
The e 14 B phase is 90% at the maximum, and if it is less than 90%, the high magnetic property of A + B value of 59 or more of the present invention cannot be obtained. The degree of orientation of the magnet of the present invention is calculated from the equation 1), and it is essential that the degree of orientation of the magnet be 85% or more in order to maintain the A + B value of 59 or more. Since the squareness of the demagnetization curve is lowered and the high residual magnetic flux density (Br) is lowered, the (BH) max value is lowered, which is not preferable. The preferred degree of orientation is 92% or more. Further, squareness {(Br 2/4) / (BH) max}
Shows a value of 1.00 in a theoretical case, but in an actual permanent magnet material, the above-mentioned disorder of the degree of orientation inevitably occurs, and therefore, even if various improvements have been conventionally made, 1. 0
Although the limit was to reach 5, the squareness value of the permanent magnet material according to the present invention obtained by the above-mentioned specific manufacturing method is 1.01 to 1.045.
【００２３】[0023]
【作用】発明者らは、まずＲ−Ｆｅ−Ｂ系合金を出発原
料として微粉砕能率の向上、かつ耐酸化性にすぐれ、磁
石合金の磁気特性、特にｉＨｃの向上を目的に、粉砕方
法について種々検討した結果、組織が微細かつ均等なＲ
−Ｆｅ−Ｂ系鋳片をストリップ・キャスティング法にて
製造し、水素吸蔵させた後、脱Ｈ2処理して安定化させ
た合金粉末を微粉砕した場合、微粉砕能は従来の約２倍
にも向上し、且つ微粉末にパルス磁界をかけて配向させ
た後、成形して焼結、時効処理することにより、（Ｂ
Ｈ）ｍａｘ値とｉＨｃ値の合計値が５９以上の値を有
し、角型性｛（Ｂｒ2／４）／（ＢＨ）ｍａｘ｝が１．
０１〜１．０４５の値を示しかつ焼結磁石のｉＨｃが向
上することを知見した。すなわち、ストリップ・キャス
ティングされた特定厚みのＲ−ｒｉｃｈ相が微細に分離
した組織を有する特定組成のＲ−Ｆｅ−Ｂ系合金にＨ2
吸蔵させると、微細に分散されたＲ−ｒｉｃｈ相が水素
化物を生成して体積膨張することにより、前記合金を自
然崩壊させることができ、その結果、微粉砕により、合
金塊を構成している結晶粒を細分化することが可能とな
り、粒度分布が均一な粉末を作製することができる。The inventors of the present invention firstly conducted a pulverization method using an R-Fe-B alloy as a starting material for the purpose of improving the fine pulverization efficiency and the oxidation resistance, and improving the magnetic characteristics of the magnet alloy, particularly iHc. As a result of various examinations, R with a fine and uniform structure
The -fe-B-based slab prepared by strip casting method, after hydrogen occlusion, when the pulverized alloy powder is stabilized by removing H 2 treatment, twice milling capacity of conventional In addition, by applying a pulse magnetic field to the fine powder to orient it, and then shaping, sintering and aging treatment, (B
The total value of H) max value and iHc value has 59 or more values, squareness {(Br 2/4) / (BH) max} is 1.
It was found that the value was 01 to 1.045 and the iHc of the sintered magnet was improved. That is, H 2 is added to the R-Fe-B-based alloy having a specific composition having a structure in which the strip-cast R-rich phase having a specific thickness is finely separated.
When occluded, the finely dispersed R-rich phase forms a hydride and volume-expands, whereby the alloy can spontaneously disintegrate, and as a result, an alloy lump is formed by fine pulverization. It becomes possible to subdivide the crystal grains, and it is possible to produce a powder having a uniform particle size distribution.
【００２４】特に、この際Ｒ−ｒｉｃｈ相が微細に分散
され、しかもＲ2Ｆｅ14Ｂ相が微細であることが重要で
ある。しかも通常の鋳型を用いて合金塊を溶製する方法
では、合金組成をＲ2Ｆｅ14Ｂ相の化学量論的組成に近
づけた場合、Ｆｅ初晶の晶出が避け難く、次工程の微粉
砕能を大きく低下させる要因になってしまう。そのた
め、合金塊を均質化させる目的で熱処理を加えて、α−
Ｆｅを消失させる手段がとられるが、主相結晶粒の粗大
化と、Ｒ−ｒｉｃｈ相の偏析も進むため、焼結磁石のｉ
Ｈｃ向上を図ることが困難となる。また、主相結晶粒の
磁化容易軸方向を揃える、すなわち、配向度を高めるこ
とも高Ｂｒ化、角型性の向上を達成するための必須条件
であり、そのため、粉末を磁界中でプレスする方式が採
られている。In this case, it is particularly important that the R-rich phase is finely dispersed and the R 2 Fe 14 B phase is fine. Moreover, in the method of smelting an alloy ingot by using an ordinary template, when the alloy composition is brought close to the stoichiometric composition of the R 2 Fe 14 B phase, crystallization of Fe primary crystal is difficult to avoid, and the fineness of the next step is small. It becomes a factor that greatly reduces the crushing ability. Therefore, heat treatment is added for the purpose of homogenizing the alloy ingot, and α-
Although a means for eliminating Fe is taken, since the coarsening of the main phase crystal grains and the segregation of the R-rich phase also proceed, i of the sintered magnet is
It becomes difficult to improve Hc. Further, aligning the easy-axis directions of the main phase crystal grains, that is, increasing the degree of orientation is also an essential condition for achieving high Br and improvement in squareness, and therefore the powder is pressed in a magnetic field. The method is adopted.
【００２５】しかしながら、磁界を発生させるために通
常のプレス装置（油圧プレス、機械プレス）に配置され
ているコイルおよび電源では、高々１０ｋＯｅ〜２０ｋ
Ｏｅの磁界しか発生することしかできず、角型性｛（Ｂ
ｒ2／４）／（ＢＨ）ｍａｘ｝も１．０５以上の値にな
ってしまい、Ｂｒ値から期待される理論的な（ＢＨ）ｍ
ａｘ値（この場合、上記角型性｛（Ｂｒ2／４）／（Ｂ
Ｈ）ｍａｘ｝は１．００）への到達は困難であった。そ
こでより高い磁界中で成形することを試みたが、より高
い磁界を発生させるためには、コイルの巻数を多くする
必要があり、また高い電源を必要とするための装置の大
型化を必要とする。本発明者らは、プレス時の磁界強度
と焼結体のＢｒとの関係を解析したところ、磁界強度を
高くすればするほど、高Ｂｒ化でき、角型性が向上し、
瞬間的に強磁界を発生させることの可能なパルス磁界を
用いることによって、より一層高Ｂｒ化、高角型性化で
きることを知見した。さらに、パルス磁界を用いる方法
においては、一旦パルス磁界で瞬間的に配向させること
が重要で、さらに、粉末を静水圧プレスによって成形す
ることが可能であり、パルス磁界と電磁石による静磁界
との組み合せによって、磁界中プレス成形することも可
能であることを知見した。However, with a coil and a power source arranged in a usual press device (hydraulic press, mechanical press) for generating a magnetic field, at most 10 kOe to 20 k.
Only the magnetic field of Oe can be generated, and the squareness {(B
r 2/4) / (BH ) max} also becomes 1.05 or more values, theoretical expected from Br value (BH) m
ax value (in this case, the squareness of {(Br 2/4) / (B
It was difficult to reach H) max} of 1.00). Therefore, we tried molding in a higher magnetic field, but in order to generate a higher magnetic field, it is necessary to increase the number of turns of the coil, and it is also necessary to increase the size of the device that requires a high power supply. To do. The present inventors analyzed the relationship between the magnetic field strength during pressing and Br of the sintered body, and as the magnetic field strength was increased, the Br could be increased and the squareness was improved.
It has been found that by using a pulsed magnetic field capable of instantaneously generating a strong magnetic field, higher Br and higher squareness can be achieved. Furthermore, in the method using a pulsed magnetic field, it is important to momentarily orientate once with the pulsed magnetic field, and it is possible to shape the powder by a hydrostatic press, and the combination of the pulsed magnetic field and the static magnetic field by an electromagnet can be combined. It was found that it is also possible to perform press molding in a magnetic field.
【００２６】一方、Ｒ−Ｆｅ合金、例えばＮｄ−Ｆｅ合
金中、Ｎｄ2Ｆｅ17相はキュリー点が室温付近で、Ｃ面
内に容易磁化方向を有する金属間化合物であり、従来、
Ｒ−Ｆｅ−Ｂ系焼結永久磁石において、Ｂ量が６原子％
より少ない場合は、磁石内に例えばＮｄ2Ｆｅ17相が生
成して保磁力が低下するとされてきた。しかし、発明者
は種々検討の結果、Ｒ2Ｆｅ14Ｂ相を主相とするＲ−Ｆ
ｅ−Ｂ系合金粉末にＲ2Ｆ17相、例えばＮｄ2Ｆｅ17相を
含むＲ−Ｆｅ系合金粉末を特定量添加配合した原料粉末
は、粒界相のＮｄ−ｒｉｃｈ相中のＮｄとＲ−Ｆｅ系合
金粉末中のＮｄ2Ｆｅ17相との共晶温度６９０℃付近に
おいて、例えば、 Ｎｄ＋Ｎｄ2Ｆｅ17相←→液相 の
反応が起こることにより、この低融点の液相がＲ−Ｆｅ
−Ｂ系合金粉末の焼結を促進することを知見した。さら
に、Ｎｄ2Ｆｅ17相を含む調整用合金粉末とＲ2Ｆｅ14Ｂ
相を主相とするＲ−Ｆｅ−Ｂ系合金粉末は、焼結中に下
記反応を起こし、主相であるＲ2Ｆｅ14Ｂ相を増加させ
る作用がある。 １３／１７Ｎｄ2Ｆｅ17＋１／４Ｎｄ1.1Ｆｅ4Ｂ4＋１３
３／６８００Ｎｄ→Ｎｄ2Ｆｅ14Ｂ すなわち、発明者は上記の反応式において、調整用合金
粉末中のＮｄ2Ｆｅ17相と主相系Ｒ−Ｆｅ−Ｂ系合金粉
末中のＢ−ｒｉｃｈ相及びＮｄ−ｒｉｃｈ相との反応に
より、新たにＮｄ2Ｆｅ14Ｂ相が生成されることになる
ので、従来法のＲ2Ｆｅ14Ｂ相を主相とする合金粉末の
みで得られた永久磁石では磁石特性を劣化させる要因の
一つであるＢ−ｒｉｃｈ相及びＮｄ−ｒｉｃｈ相の量を
焼結反応時に低減できることを知見した。On the other hand, in R-Fe alloys such as Nd-Fe alloys, the Nd 2 Fe 17 phase is an intermetallic compound having a Curie point near room temperature and having an easy magnetization direction in the C-plane.
In the R-Fe-B system sintered permanent magnet, the B content is 6 atom%.
When the amount is smaller than that, it has been said that, for example, an Nd 2 Fe 17 phase is generated in the magnet to lower the coercive force. However, as a result of various studies, the inventor has found that R-F containing the R 2 Fe 14 B phase as a main phase.
e-B based alloy powder to R 2 F 17 phases, for example, Nd raw powder specific amount added blended R-Fe alloy powder containing 2 Fe 17 phase, Nd and R in Nd-rich phase in the grain boundary phase In the vicinity of the eutectic temperature of 690 ° C. with the Nd 2 Fe 17 phase in the —Fe alloy powder, for example, the reaction of Nd + Nd 2 Fe 17 phase ← → liquid phase occurs, so that the low melting point liquid phase becomes R-Fe.
It was found that it promotes the sintering of the B-based alloy powder. Furthermore, the alloy powder for adjustment containing Nd 2 Fe 17 phase and R 2 Fe 14 B
The R-Fe-B based alloy powder having a phase as a main phase has the action of causing the following reactions during sintering to increase the R 2 Fe 14 B phase as the main phase. 13 / 17Nd 2 Fe 17 + 1 / 4Nd 1.1 Fe 4 B 4 +13
3/6800 Nd → Nd 2 Fe 14 B That is, the inventor in the above reaction formula, the Nd 2 Fe 17 phase in the adjustment alloy powder, the B-rich phase in the main phase R-Fe-B alloy powder, and the Since a new Nd 2 Fe 14 B phase is generated by the reaction with the Nd-rich phase, in the permanent magnet obtained by only the alloy powder having the R 2 Fe 14 B phase as the main phase in the conventional method, It was found that the amount of the B-rich phase and the Nd-rich phase, which is one of the factors that deteriorate the magnet characteristics, can be reduced during the sintering reaction.
【００２７】この発明において、主相系合金粉末ならび
に調整用合金粉末をストリップ・キャスティング法で得
た合金から製造するのは、ストリップ・キャスティング
によると、主相系合金粉末では、Ｒ2Ｆｅ14Ｂ主相が微
細で、かつ、Ｂ−ｒｉｃｈ相やＮｄ−ｒｉｃｈ相がよく
分散した合金鋳片から主相系合金粉末を得ることがで
き、しかも、Ｆｅ初晶の晶出を抑制でき、また調整用合
金粉末ではＲ2Ｆｅ17相が均一に分散された合金鋳片か
ら調整用合金粉末を得ることができる。特に、主相系原
料粉末中のＲ2Ｆｅ14Ｂ相が微細でかつＢ−ｒｉｃｈ相
やＮｄ−ｒｉｃｈ相が均一に分散されていると、磁石製
造時に微粉砕能が極めて向上し、かつ粒度分布が均一な
粉末を製造できる。さらに、磁石を製造した際、結晶が
微細であるため、高い保磁力が得られる。In the present invention, the main phase alloy powder and the adjusting alloy powder are produced from the alloy obtained by the strip casting method. According to strip casting, the main phase alloy powder is R 2 Fe 14 B A main phase alloy powder can be obtained from an alloy slab in which the main phase is fine and in which the B-rich phase and the Nd-rich phase are well dispersed, and moreover, the crystallization of Fe primary crystals can be suppressed and adjusted. As the alloy powder for use, the adjusting alloy powder can be obtained from an alloy slab in which the R 2 Fe 17 phase is uniformly dispersed. In particular, if the R 2 Fe 14 B phase in the main phase raw material powder is fine and the B-rich phase and the Nd-rich phase are uniformly dispersed, the fine pulverizing ability during magnet production is significantly improved, and the particle size is improved. A powder with a uniform distribution can be produced. Further, when the magnet is manufactured, a high coercive force is obtained because the crystal is fine.
【００２８】さらに、前記Ｒ2Ｆｅ17相を含む調整用合
金粉末をストリップ・キャスティング法で製造する利点
は、前記Ｒ2Ｆｅ17相を微細にでき、主相系合金粉末と
の混合時によく分散できるため、前記反応を均一に行う
ことができることによる。すなわち、通常の鋳型を用い
た合金溶製法では、得られた合金塊にα−Ｆｅや他のＲ
−Ｆｅ（Ｃｏ）化合物相が晶出するため、安定な原料合
金粉末とするためには、前記合金塊を熱処理して均質化
する必要があり、合金粉末の製造コストアップの要因と
なると共にＲ2Ｆｅ17相が大きく成長してしまう。さら
に、調整用合金粉末を直接還元拡散法にて製造した場
合、未反応のＦｅ粒子が残留したり、また、個々の粒子
の組成が異なるなどの問題を生じ、合金粉末全体を均質
化することは極めて困難となること等の問題を解消でき
る。Further, the advantage of producing the adjusting alloy powder containing the R 2 Fe 17 phase by the strip casting method is that the R 2 Fe 17 phase can be made fine and well dispersed when mixed with the main phase alloy powder. Therefore, the reaction can be carried out uniformly. That is, in the alloy melting method using a usual mold, α-Fe and other R
Since the —Fe (Co) compound phase crystallizes out, it is necessary to heat-treat the alloy ingot to homogenize it in order to obtain a stable raw material alloy powder, which causes an increase in the manufacturing cost of the alloy powder and R 2 Fe 17 phase grows large. Furthermore, when the alloy powder for adjustment is produced by the direct reduction diffusion method, problems such as unreacted Fe particles remaining and the composition of individual particles differ, and the alloy powder as a whole is homogenized. Can solve problems such as becoming extremely difficult.
【００２９】この発明によるＲ−Ｆｅ−Ｂ系永久磁石の
磁気特性は、最大エネルギー積（ＢＨ）ｍａｘ値；Ａ
（ＭＧＯｅ）と保磁力ｉＨｃ値（ｋＯｅ）；Ｂの合計値
をＡ＋Ｂが５９以上を有し、ＢＨ（ｍａｘ）が５０ＭＧ
Ｏｅ以上の場合は、ｉＨｃは９ｋＯｅ以上であり、又Ｂ
Ｈ（ｍａｘ）が４５ＭＧＯｅ以上の場合は、ｉＨｃは１
４ｋＯｅ以上で、角型性｛（Ｂｒ2／４）／（ＢＨ）ｍ
ａｘ｝の値１．０１〜１．０４５を有し、組成、製造条
件等を適宜選定することにより所要の磁気特性を得るこ
とができる。The magnetic characteristics of the R-Fe-B system permanent magnet according to the present invention have a maximum energy product (BH) max value;
(MGOe) and coercive force iHc value (kOe); A + B has a total value of 59 or more, and BH (max) is 50 MG.
When it is Oe or more, iHc is 9 kOe or more, and B
IHc is 1 when H (max) is 45 MGOe or more
Above 4 kOe, squareness {(Br 2/4) / (BH) m
ax} has a value of 1.01 to 1.045, and the required magnetic characteristics can be obtained by appropriately selecting the composition, manufacturing conditions, and the like.
【００３０】[0030]
実施例１ 主相系合金粉末のストリップ・キャスティング法による
原料は、 純度９９％のＮｄメタル ３４０ｇ、 純度９９％のＤｙメタル ８ｇ、 Ｂ含有量２０．０％のＦｅ−Ｂ合金 ６５．５ｇ、 純度９９％の電解鉄 ６００ｇ を用い、所定の組成の合金が得られるようにＡｒ雰囲気
中で溶解し、次いでＣｕ製のロール２本を併設した双ロ
ールによるストリップ・キャスティング法で、板厚約２
ｍｍの鋳片を得た。前記鋳片を５０ｍｍ角以下に破断
後、吸排気可能な密閉容器内に収容し、前記容器内にＮ
2ガスを３０分間流入して、空気と置換した後、該容器
内に３ｋｇ／ｃｍ2のＨ2ガスを２時間供給してＨ2吸臓
により鋳片を自然崩壊させて、その後真空中で５００℃
に５時間保持して脱Ｈ2処理した後、室温まで冷却し、
さらに１００メッシュまで粗粉砕した。次いで、前記粗
粉砕を採取した８００ｇをジェットミルで微粉砕して平
均粒度１０μｍの合金粉末を得た。得られた粉末はＮｄ
１４原子％、Ｐｒ０．１原子％、Ｄｙ０．５原子％、Ｂ
８．０原子％、残部Ｆｅからなり、Ｘ線回折ＥＰＭＡで
観察したところ、大部分がＲ2Ｆｅ14Ｂ相であることを
確認した。また、含有酸素量は約８００ｐｐｍであっ
た。なお、鋳片の組織についてもＥＰＭＡで観察したと
ころ、Ｒ2Ｆｅ14Ｂ主相が、その短軸方向で約５μｍ、
長軸方向２０〜８０μｍであり、さらにＲ−ｒｉｃｈ相
は主相を取り囲むように微細に分散していた。Example 1 Raw materials of the main phase alloy powder by the strip casting method were: Nd metal with a purity of 99%, 340 g, Dy metal with a purity of 99%, 8 g, Fe-B alloy with a B content of 20.0%, 65.5 g, and purity. Using 600 g of 99% electrolytic iron, melting it in an Ar atmosphere so as to obtain an alloy with a predetermined composition, and then using a twin-roll strip casting method with two Cu rolls, a plate thickness of about 2
A mm slab was obtained. After breaking the slab to 50 mm square or less, it is housed in a closed container capable of sucking and exhausting, and N is put in the container.
2 gas was flowed in for 30 minutes to replace air, and then 3 kg / cm 2 H 2 gas was supplied into the container for 2 hours to spontaneously disintegrate the cast piece by H 2 sucker, and then in vacuum. 500 ° C
After 5 hours of de-H 2 treatment, cool to room temperature,
Further coarsely pulverized to 100 mesh. Next, 800 g of the coarsely pulverized sample was finely pulverized with a jet mill to obtain an alloy powder having an average particle size of 10 μm. The obtained powder is Nd
14 atom%, Pr 0.1 atom%, Dy 0.5 atom%, B
It consisted of 8.0 atomic% and the balance Fe, and when observed by X-ray diffraction EPMA, it was confirmed that most of it was the R 2 Fe 14 B phase. The oxygen content was about 800 ppm. The structure of the cast slab was also observed by EPMA to find that the R 2 Fe 14 B main phase was about 5 μm in the minor axis direction.
The major axis direction was 20 to 80 μm, and the R-rich phase was finely dispersed so as to surround the main phase.
【００３１】また、調整用合金粉末のＲ2Ｆｅ17相を含
むストリップ・キャスティング法による原料は、 純度９９％のＮｄメタル １２５ｇ 純度９９％のＤｙメタル ５ｇ 純度９９％の電解鉄 ３７５ｇ を用い、主相系合金と同様にストリップ・キャスティン
グ法で板厚約２ｍｍの鋳片を得た。さらに、主相系合金
と同様の処理により粉末を作製した。得られた粉末の組
成はＮｄ１１．０原子％、Ｐｒ０．０５原子％、Ｄｙ
０．４原子％、残部Ｆｅであった。ＥＰＭＡで鋳片の組
織を確認したところ、Ｒ2Ｆｅ17相および一部Ｒ2Ｆｅ14
Ｂ、さらにＮｄ−ｒｉｃｈ相からなり、α−Ｆｅの存在
は認められなかった。なお、平均粒径１０μｍの含有酸
素量は７００ｐｐｍであった。Further, as a raw material by the strip casting method containing the R 2 Fe 17 phase of the alloy powder for adjustment, 125 g of Nd metal having a purity of 99%, 5 g of Dy metal having a purity of 99% and 375 g of electrolytic iron having a purity of 99% were mainly used. A strip having a plate thickness of about 2 mm was obtained by the strip casting method in the same manner as the phase-based alloy. Further, powder was produced by the same treatment as for the main phase alloy. The composition of the obtained powder was Nd 11.0 at%, Pr 0.05 at%, Dy
The content was 0.4 atomic% and the balance Fe. When the structure of the slab was confirmed by EPMA, the R 2 Fe 17 phase and a part of the R 2 Fe 14
B, and Nd-rich phase, and the presence of α-Fe was not recognized. The oxygen content with an average particle size of 10 μm was 700 ppm.
【００３２】上記２種類の原料粉末を用いて、主相系合
金粉末に２５％の調整用合金粉末を配合・混合した。こ
の原料粉末をジェット・ミルなどの粉砕機に装入して、
約３μｍまで微粉砕し、得られた微粉末をゴム質のモー
ルドに原料粉末を充填し、パルス磁界６０ｋＯｅを瞬間
的に付加して配向させた後、静水圧プレス装置にて２．
５Ｔ／ｃｍ2の圧力で静水圧プレスし、８ｍｍ×１５ｍ
ｍ×１０ｍｍの成型体を作製した。この成型体を１１０
０℃×３時間のＡｒ雰囲気中条件で焼結し、５５０℃×
１時間の時効処理を行って永久磁石を得た。得られた永
久磁石の磁石特性及び密度、結晶粒径、配向度、角型
性、主相量、含有Ｏ2量を表１、表２に表す。Using the above two kinds of raw material powder, 25% of the alloy powder for adjustment was mixed and mixed with the main phase alloy powder. Charge this raw material powder into a crusher such as a jet mill,
After finely pulverizing to a size of about 3 μm, the fine powder thus obtained was filled with a raw material powder in a rubber mold, and a pulsed magnetic field of 60 kOe was momentarily applied to orient it, followed by a hydrostatic pressing device.
Hydrostatically pressed at a pressure of 5 T / cm 2 , 8 mm x 15 m
A m × 10 mm molded body was produced. This molded body is 110
Sintered under conditions of 0 ° C. × 3 hours in Ar atmosphere, 550 ° C. ×
A permanent magnet was obtained by performing an aging treatment for 1 hour. Tables 1 and 2 show the magnet characteristics and density, crystal grain size, orientation degree, squareness, main phase amount, and O 2 content of the obtained permanent magnet.
【００３３】実施例２ 前記実施例１で得た配合原料粉末を図１に示す如く、上
下パンチ１，２の外周部に静磁界用コイル３，４を配置
し、ダイス５内にパルス磁界用コイル６を配設して、原
料粉末７にパルス磁界と通常の静磁界とを併用して作用
させることができるプレス装置を用いて、まず、約３０
ｋＯｅのパルス磁界で配向させた後、約１２ｋＯｅの磁
界中でプレス成形した。その後、成形体は実施例１と同
一の条件で、焼結、時効処理を行った。得られた永久磁
石の磁石特性及び密度、結晶粒径、配向度、角型性、主
相量、含有Ｏ2量、密度を表１、表２に示す。Example 2 As shown in FIG. 1, the mixed raw material powders obtained in Example 1 were arranged with static magnetic field coils 3 and 4 on the outer peripheral portions of the upper and lower punches 1 and 2, and a pulse magnetic field was formed in the die 5. A coil 6 is provided, and a pressing device capable of acting on the raw material powder 7 in combination with a pulsed magnetic field and a normal static magnetic field is used.
After orientation with a pulsed magnetic field of kOe, press molding was performed in a magnetic field of about 12 kOe. Thereafter, the molded body was sintered and aged under the same conditions as in Example 1. Tables 1 and 2 show the magnetic properties and density, crystal grain size, orientation degree, squareness, main phase amount, O 2 content, and density of the obtained permanent magnet.
【００３４】比較例１ 主相系合金粉末は実施例１で得られたものと同組成の合
金を鉄製鋳型に鋳込み、実施例１と同様の方法で平均粒
径約１０μｍの粉末を得た。組成は、Ｎｄ１４原子％、
Ｐｒ０．１原子％、Ｄｙ０．５原子％、Ｂ８原子％、残
部Ｆｅからなり、含有酸素量は約９００ｐｐｍであり、
組織をＥＰＭＡで観察したところ、Ｒ2Ｆｅ14Ｂ主相は
短軸方向約５０μｍ、長軸方向約５００μｍであり、Ｒ
−ｒｉｃｈ相が局部的に５０μｍにもわたって、偏在し
ていた。さらに主相には一部５〜１０μｍのα−Ｆｅが
存在していた。また、Ｒ2Ｆｅ17相を含む調整用合金粉
末は、Ｎｄ2Ｏ3（純度９８％）２８０ｇ、Ｄｙ2Ｏ3（純
度９９％）１２ｇ、純度９９％の鉄粉７５０ｇを用い
て、これに純度９９％の金属Ｃａを１５０ｇ無水ＣａＣ
ｌ2を２５ｇ混合して、ステンレス容器内に装入し、Ａ
ｒ気流中に９５０℃×８時間の条件にて、直接還元拡散
法で作製し、成分はＮｄ１１．０原子％、Ｐｒ０．０５
原子％、Ｄｙ０．９原子％、残部Ｆｅ、含有酸素量１５
００ｐｐｍであった。上記２種類の原料粉末を用いて、
主相系合金粉末に２５％の調整用合金粉末を配合・混合
し、ジェット・ミルなどの粉砕機に装入して約３μｍま
で微粉砕し、得られた微粉末を約１０ｋＯｅの磁界中で
配向し、磁界に直角方向に約１．５ｔｏｎ／ｃｍ2の圧
力で成型し、８ｍｍ×１５ｍｍ×１０ｍｍの成型体を作
製した。この成型体を１１００℃×３時間のＡｒ雰囲気
中条件で焼結し、５５０℃×１時間の時効処理を行っ
た。得られた磁石の磁石特性を表１、表２に合わせて示
した。Comparative Example 1 As the main phase alloy powder, an alloy having the same composition as that obtained in Example 1 was cast into an iron mold, and a powder having an average particle size of about 10 μm was obtained by the same method as in Example 1. The composition is 14 atomic% Nd,
Pr 0.1 atom%, Dy 0.5 atom%, B 8 atom%, balance Fe, and oxygen content is about 900 ppm.
When the structure was observed by EPMA, the R 2 Fe 14 B main phase was about 50 μm in the minor axis direction and about 500 μm in the major axis direction.
-Rich phase was locally unevenly distributed over 50 μm. Further, a part of 5 to 10 μm of α-Fe was present in the main phase. Further, the alloy powder for adjustment containing the R 2 Fe 17 phase was prepared by using 280 g of Nd 2 O 3 (purity 98%), 12 g of Dy 2 O 3 (purity 99%), and 750 g of iron powder of 99% purity. 150g of metallic Ca with a purity of 99% anhydrous CaC
25 g of l 2 was mixed and charged into a stainless steel container,
It was prepared by the direct reduction diffusion method under the condition of 950 ° C. × 8 hours in an air flow, and the components were Nd 11.0 atomic% and Pr0.05.
Atomic%, Dy 0.9 atomic%, balance Fe, oxygen content 15
It was 00 ppm. Using the above two types of raw material powder,
25% of the alloy powder for adjustment is mixed and mixed with the main phase alloy powder, charged into a pulverizer such as a jet mill and pulverized to about 3 μm, and the obtained fine powder is subjected to a magnetic field of about 10 kOe. It was oriented and molded in a direction perpendicular to the magnetic field at a pressure of about 1.5 ton / cm 2 to prepare a molded body of 8 mm × 15 mm × 10 mm. This molded body was sintered under the conditions of 1100 ° C. for 3 hours in an Ar atmosphere and subjected to an aging treatment at 550 ° C. for 1 hour. The magnet characteristics of the obtained magnet are also shown in Tables 1 and 2.
【００３５】比較例２ 主相系の合金粉末は比較例１のものを使用し、調整用合
金粉末は、 純度９９％のＮｄメタル ３５０ｇ 純度９９％のＤｙメタル １０ｇ 純度９９％の電解鉄 ７５０ｇ をＡｒ雰囲気中で溶解し、鉄製鉄型に鋳造した。得られ
た合金塊の組織を観察したところ、α−Ｆｅが多量に晶
出していたため、１０００℃×１２時間の均質化処理を
行った。その後、実施例１と同様の手法で成分分析を行
ったところ、Ｎｄ１１．０原子％、Ｐｒ０．０５原子
％、Ｄｙ０．４原子％、残部Ｆｅであった。上記２種類
の原料粉末を用いて、主相系合金粉末に２５％の調整用
合金粉末を配合・混合し、比較例１と同様に磁石を作製
した。得られた磁石の磁石特性を表１、表２に合わせて
示した。Comparative Example 2 The main phase alloy powder used is that of Comparative Example 1, and the alloy powder for adjustment is Nd metal with a purity of 99% 350 g, Dy metal with a purity of 99% 10 g, and electrolytic iron with a purity of 99% 750 g. It was melted in an Ar atmosphere and cast into an iron mold. Observation of the structure of the obtained alloy lump revealed that a large amount of α-Fe was crystallized out, so a homogenization treatment was performed at 1000 ° C for 12 hours. After that, a component analysis was performed in the same manner as in Example 1. As a result, Nd was 11.0 atomic%, Pr was 0.05 atomic%, Dy was 0.4 atomic%, and the balance was Fe. A magnet was produced in the same manner as in Comparative Example 1 by mixing and mixing 25% of the adjusting alloy powder with the main phase alloy powder using the above two kinds of raw material powders. The magnet characteristics of the obtained magnet are also shown in Tables 1 and 2.
【００３６】比較例３ 原料として、 純度９９％のＮｄメタル ３００ｇ、 純度９９％のＤｙメタル １３ｇ、 Ｂ含有量２０．０％のＦｅ−Ｂ合金 ５０ｇ、 純度９９％の電解鉄 ６４５ｇ を用い、所定の組成の合金が得られるようにＡｒ雰囲気
中で溶解し、次いでＣｕ製のロールによるストリップ・
キャスティング法で、板厚約２ｍｍの鋳片を得た。さら
にこの鋳片を水素吸蔵処理にて粗粉砕後、ジョークラッ
シャー、ディスクミルなどにより微粉砕して、平均粒径
約１０μｍの粉末８００ｇを得た。得られた粉末はＮｄ
１３．３原子％、Ｐｒ０．１原子％、Ｄｙ０．５原子
％、Ｂ６原子％、残部Ｆｅからなり、含有酸素量は約８
００ｐｍであった。なお、鋳片の組織についてもＥＰＭ
Ａで観察したところ、Ｒ2Ｆｅ14Ｂ主相が、その短軸方
向で約０．３〜１５μｍ、長軸方向約５〜９０μｍであ
り、さらにＲ−ｒｉｃｈ相は主相をより囲むように微細
に存在していた。このストリップ・キャスティング法に
よる合金粉末を用いて、比較例１と同様に磁石を作製し
た。得られた磁石の磁石特性を表１、表２に合わせて示
した。Comparative Example 3 As raw materials, 300 g of Nd metal having a purity of 99%, 13 g of Dy metal having a purity of 99%, 50 g of Fe-B alloy having a B content of 20.0%, and 645 g of electrolytic iron having a purity of 99% were used. Melted in an Ar atmosphere to obtain an alloy having the composition
A cast piece having a plate thickness of about 2 mm was obtained by the casting method. Further, this slab was roughly pulverized by hydrogen storage treatment and then finely pulverized by a jaw crusher, a disc mill or the like to obtain 800 g of powder having an average particle size of about 10 μm. The obtained powder is Nd
13.3 atomic%, Pr 0.1 atomic%, Dy 0.5 atomic%, B6 atomic%, balance Fe, and the oxygen content is about 8
It was 00 pm. Note that the structure of the slab is also EPM
When observed in A, the R 2 Fe 14 B main phase is about 0.3 to 15 μm in the minor axis direction and about 5 to 90 μm in the major axis direction, and the R-rich phase further surrounds the main phase. It was finely present. A magnet was produced in the same manner as in Comparative Example 1 using the alloy powder obtained by the strip casting method. The magnet characteristics of the obtained magnet are also shown in Tables 1 and 2.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【表２】 [Table 2]
【００３９】[0039]
【発明の効果】この発明は、主相系合金粉末ならびに調
整用合金粉末をストリップ・キャスティング法で製造す
ることにより、主相系合金粉末はＲ2Ｆｅ14Ｂ主相が微
細でかつＢ−ｒｉｃｈ相やＮｄ−ｒｉｃｈ相がよく分散
し磁石製造時に微粉砕能が極めて向上し、かつ粒度分布
が均一な粉末を製造でき、しかもＦｅ初晶の晶出を抑制
でき、また、Ｒ2Ｆｅ17相を微細にでき、主相系合金粉
末との混合時によく分散できるため、Ｂ−ｒｉｃｈ相及
びＮｄ−ｒｉｃｈ相の量を焼結反応時に低減できる反応
を均一に行うことができ、さらに、パルス磁界を用いて
配向後プレスして磁石化することにより、耐酸化性にす
ぐれ、磁石合金の磁気特性、特に、最大エネルギー積値
（ＢＨ）ｍａｘ（ＭＧＯｅ）；Ａと保磁力ｉＨｃ（ｋＯ
ｅ）の特性値；Ｂの合計値Ａ＋Ｂが５９以上の値を有
し、角型性｛（Ｂｒ2／４）／（ＢＨ）ｍａｘ｝が１．
０１〜１．０４５の値を示す高性能Ｒ−Ｆｅ−Ｂ系永久
磁石が得られる。According to the present invention, by producing the main phase alloy powder and the adjusting alloy powder by the strip casting method, the main phase alloy powder has a fine R 2 Fe 14 B main phase and B-rich. Phase and Nd-rich phase are well dispersed, the fine pulverizing ability during magnet production is extremely improved, and a powder having a uniform particle size distribution can be produced, and the crystallization of Fe primary crystals can be suppressed, and the R 2 Fe 17 phase can be suppressed. Of the B-rich phase and Nd-rich phase can be reduced during the sintering reaction because the amount of the B-rich phase and the Nd-rich phase can be reduced during the sintering reaction. The resulting alloy has excellent oxidation resistance by being pressed and magnetized after being oriented, and the magnetic properties of the magnet alloy, in particular, the maximum energy product value (BH) max (MGOe); A and the coercive force iHc (kO
characteristic values of e); sum A + B and B has 59 or more values, squareness {(Br 2/4) / (BH) max} is 1.
A high performance R-Fe-B based permanent magnet showing a value of 01 to 1.045 is obtained.
【図１】パルス磁界と通常の静磁界とを併用して作用さ
せることができるプレス装置の説明図である。FIG. 1 is an explanatory diagram of a press device that can act by using a pulse magnetic field and a normal static magnetic field together.
【図２】パルス磁界の時間と磁界強さとの関係を示すグ
ラフである。FIG. 2 is a graph showing a relationship between time of a pulsed magnetic field and magnetic field strength.
１，２ パンチ ３，４ 静磁界用コイル ５ ダイス ６ パルス磁界用コイル ７ 原料粉末 1, 2 Punch 3, 4 Static magnetic field coil 5 Die 6 Pulse magnetic field coil 7 Raw material powder
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｆ 1/053 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location H01F 1/053
Claims (2)
少なくとも１種）１１原子％〜２０原子％、Ｂ４原子％
〜１５原子％、残部Ｆｅ（但しＦｅの１部をＣｏ、Ｎｉ
の１種または２種にて置換できる）及び不可避的不純物
からなる合金溶湯をストリップ・キャスティング法にて
Ｒ2Ｆｅ14Ｂ相を主相とする主相系鋳片に鋳造後、ま
た、Ｒ（但しＲはＹを含む希土類元素のうち少なくとも
１種）２０原子％以下、残部Ｆｅ（但しＦｅの１部をＣ
ｏ、Ｎｉの１種または２種にて置換できる）及び不可避
的不純物からなる合金溶湯をストリップ・キャスティン
グ法にてＲ2Ｆｅ17相を含む調整用合金鋳片に鋳造後、
各鋳片を吸排気可能な容器に収容し、該容器内の空気を
Ｈ2ガスにて置換し、Ｈ2ガスを供給してＨ2吸蔵処理に
て得られた崩壊合金粉を脱Ｈ2処理した後、不活性ガス
気流中で微粉砕して平均粒径が１μｍ〜１０μｍの主相
系合金粉末と調整用合金粉末となし、前記主相系合金粉
末に調整用合金粉末を配合混合した後、この混合合金粉
末をモールド内に充填して瞬間的に１０ｋＯｅ以上のパ
ルス磁界をかけて配向させた後、成形し、焼結、時効処
理し、（ＢＨ）ｍａｘ値；Ａ（ＭＧＯｅ）とｉＨｃ値；
Ｂ（ｋＯｅ）の合計値Ａ＋Ｂが５９以上の値を有し、角
型性｛（Ｂｒ2／４）／（ＢＨ）ｍａｘ｝が１．０１〜
１．０４５の値を有する永久磁石材料を得るＲ−Ｆｅ−
Ｂ系永久磁石材料の製造方法。1. R (where R is at least one of rare earth elements including Y) 11 atom% to 20 atom%, B4 atom%
-15 atom%, balance Fe (however, part of Fe is Co, Ni
(Which can be replaced by one or two of the above) and inevitable impurities are cast by a strip casting method into a main phase slab having the R 2 Fe 14 B phase as the main phase, and R ( However, R is 20 atomic% or less of at least one of rare earth elements including Y and the balance Fe (however, part of Fe is C
o, Ni can be replaced by one or two kinds) and unavoidable impurities, and the cast alloy alloy slab containing the R 2 Fe 17 phase is cast by the strip casting method.
Each slab is accommodated in the intake and exhaust can container, the air in the vessel was replaced with H 2 gas, by supplying the H 2 gas H 2 occlusion processing the resulting collapse alloy powder with desalted H 2 After the treatment, the powder was finely pulverized in an inert gas stream to form a main phase alloy powder having an average particle size of 1 μm to 10 μm and an adjustment alloy powder, and the main phase alloy powder was mixed and mixed with the adjustment alloy powder. After that, this mixed alloy powder was filled in a mold and momentarily applied with a pulsed magnetic field of 10 kOe or more to be oriented, then molded, sintered and aged, and (BH) max value; A (MGOe) iHc value;
B sum A + B of the (kOe) has a 59 or more values, squareness {(Br 2/4) / (BH) max} is 1.01
R-Fe- to obtain a permanent magnet material with a value of 1.045
A method for manufacturing a B-based permanent magnet material.
希土類元素のうち少なくとも１種）１３原子％〜１６原
子％、Ｂ ６原子％〜１０原子％、残部Ｆｅ（但し、Ｆ
ｅの１部をＣｏ，Ｎｉの１種又は２種にて置換できる）
及び不可避的不純物からなることを特徴とする請求項１
に記載のＲ−Ｆｅ−Ｂ系永久磁石材料の製造方法。2. The main phase alloy melt is R (where R is at least one of rare earth elements including Y) 13 atom% to 16 atom%, B 6 atom% to 10 atom%, balance Fe (however, F
(Part of e can be replaced with one or two of Co and Ni)
And inevitable impurities.
The method for producing the R-Fe-B based permanent magnet material as described in 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24636593A JP3157661B2 (en) | 1993-09-06 | 1993-09-06 | Method for producing R-Fe-B permanent magnet material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24636593A JP3157661B2 (en) | 1993-09-06 | 1993-09-06 | Method for producing R-Fe-B permanent magnet material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0778709A true JPH0778709A (en) | 1995-03-20 |
| JP3157661B2 JP3157661B2 (en) | 2001-04-16 |
Family
ID=17147472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24636593A Expired - Lifetime JP3157661B2 (en) | 1993-09-06 | 1993-09-06 | Method for producing R-Fe-B permanent magnet material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3157661B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0924717A2 (en) * | 1997-12-22 | 1999-06-23 | Shin-Etsu Chemical Co., Ltd. | Rare earth-iron-boron permanent magnet and method for the preparation thereof |
| WO2002061769A1 (en) | 2001-01-30 | 2002-08-08 | Sumitomo Special Metals Co., Ltd. | Method for preparation of permanent magnet |
| JP2017043850A (en) * | 2016-09-06 | 2017-03-02 | アップル インコーポレイテッド | Amorphous alloy powder feedstock processing process |
| US9987685B2 (en) | 2012-03-23 | 2018-06-05 | Apple Inc. | Continuous moldless fabrication of amorphous alloy pieces |
-
1993
- 1993-09-06 JP JP24636593A patent/JP3157661B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0924717A2 (en) * | 1997-12-22 | 1999-06-23 | Shin-Etsu Chemical Co., Ltd. | Rare earth-iron-boron permanent magnet and method for the preparation thereof |
| EP0924717A3 (en) * | 1997-12-22 | 1999-11-24 | Shin-Etsu Chemical Co., Ltd. | Rare earth-iron-boron permanent magnet and method for the preparation thereof |
| WO2002061769A1 (en) | 2001-01-30 | 2002-08-08 | Sumitomo Special Metals Co., Ltd. | Method for preparation of permanent magnet |
| EP1365422A1 (en) * | 2001-01-30 | 2003-11-26 | Sumitomo Special Metals Company Limited | Method for preparation of permanent magnet |
| US7244318B2 (en) | 2001-01-30 | 2007-07-17 | Neomax Co., Ltd. | Method for preparation of permanent magnet |
| EP1365422A4 (en) * | 2001-01-30 | 2008-12-31 | Hitachi Metals Ltd | Method for preparation of permanent magnet |
| US9987685B2 (en) | 2012-03-23 | 2018-06-05 | Apple Inc. | Continuous moldless fabrication of amorphous alloy pieces |
| JP2017043850A (en) * | 2016-09-06 | 2017-03-02 | アップル インコーポレイテッド | Amorphous alloy powder feedstock processing process |
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| JP3157661B2 (en) | 2001-04-16 |
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