EP0597582B1 - Matériau en poudre pour aimant à base de terre-rare - Google Patents

Matériau en poudre pour aimant à base de terre-rare Download PDF

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Publication number
EP0597582B1
EP0597582B1 EP19930307756 EP93307756A EP0597582B1 EP 0597582 B1 EP0597582 B1 EP 0597582B1 EP 19930307756 EP19930307756 EP 19930307756 EP 93307756 A EP93307756 A EP 93307756A EP 0597582 B1 EP0597582 B1 EP 0597582B1
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EP
European Patent Office
Prior art keywords
powder
magnet
grain size
anisotropic
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.)
Expired - Lifetime
Application number
EP19930307756
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German (de)
English (en)
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EP0597582A1 (fr
Inventor
Ryoji C/O Chuo-Kenkyusho Nakayama
Takuo C/O Chuo-Kenkyusho Takeshita
Yoshinari C/O Chuo-Kenkyusho Ishii
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Publication of EP0597582A1 publication Critical patent/EP0597582A1/fr
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    • 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
    • H01F1/0573—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 obtained by reduction or by hydrogen decrepitation or embrittlement
    • 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
    • H01F1/0572—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 with a protective layer

Definitions

  • the present invention relates to a rare-earth magnet powder material excellent in an isotropy, which comprises any of the rare-earth elements including Y (hereinafter referred to as "R”), Fe or a component in which part of the Fe is substituted by Co (hereinafter referred to as "T”) and B as the main components, and further containing one or more of Si, Ga, Zr, Nb, Mo, Hf, Ta, W, Al, Ti and V (hereinafter referred to as "M”) in an amount of from 0.001 to 5.0 atomic %, of which the main phase is an R 2 T 14 B-type intermetallic compound phase.
  • R rare-earth elements
  • T Co
  • M Ti and V
  • EP-A-0 304 054 describes the preparation of rare earth-iron-boron magnet powders having an average particle size of 2.0 to 500 ⁇ m and which powders contain a recrystallized grain structure containing a R 2 Fe 14 B intermetallic compound phase where R represents a rare-earth element, the average crystal grain size of the recrystallised grains being of 0.05 ⁇ m to 50 ⁇ m.
  • the powder may also further comprise elements M as described herein.
  • the grain size of anisotropic R-Fe-B-M magnet powders having the recrystallized fine aggregate structure of the R 2 T 14 B-type intermetallic compound phase of an average recrystallization grain size of from 0.05 to 20 ⁇ m obtained through conventional H 2 occlusion and dehydrogenation exerts an important effect on the magnetic properties of bonded magnets and full-density magnets made from them.
  • the present invention was developed on the basis of these discoveries and provides an ansiotropic magnet powder material having the recrystallized fine aggregate structure of an R 2 T 14 B-type intermetallic compound phase, which comprises any of the rare-earth elements including Y (herein referred to as "R”), Fe or a component in which part of the Fe is substituted by Co (herein referred to as "T”), and B as the main components and which components have an average recrystallized grain size of from 0.05 to 20 ⁇ m the powder comprising one or more of Si, Ga, Zr, Nb, Mo, Hf, Ta, W, Al, Ti and V (herein referred as "M”) characterised in that the material contains a total amount of 0.001 to 5.0 atomic percent of M and the average grain size of the powder is within the range from 5 to 200 ⁇ m.
  • R rare-earth elements
  • T Co
  • B the main components and which components have an average recrystallized grain size of from 0.05 to 20 ⁇ m
  • the powder comprising one
  • the powder should have an average grain size of from 5 to 200 ⁇ m because an average grain size of under 5 ⁇ m is not desirable as it leads to a lower iHc of bond magnets and full-density magnets made and an average grain size of over 200 ⁇ m results on the other hand in a lower magnetic anisotropy in such magnets.
  • part of Fe may be substituted by Cr.
  • Mn, Ni, Cu or Zn, and part of B may be substituted by C, N or O.
  • an alloy having a chemical composition comprising 11.6% Nd, 0.5% Pr, 11.8% Co, 6.5% B, 0.1% Zr and the balance Fe (atomic %) was melted in an Ar gas atmosphere, and cast into an ingot.
  • This ingot was homogenized in an Ar atmosphere by holding it at a temperature of 1,130°C for 30 hours, and then crushed to blocks each having a side of up to 20 mm.
  • the block was caused to occlude hydrogen by heating it from room temperature to 750° C in an hydrogen atmosphere under 1 atm.
  • Hydrogen occlusion was caused by holding the block at 750°C for one hour while maintaining the hydrogen atmosphere of 1 atm. to accelerate phase transformation.
  • the block was further heated to 850°C. held at 850°C for one hour, and was forcedly caused to release hydrogen until a 1 x 10 -1 vacuum atmosphere was achieved to accelerate phase transformation.
  • the block was then cooled in Ar gas.
  • samples of the invention Nos. 1 to 7
  • comparative samples of anisotropic magnet material powder hereinafter referred to as "comparative samples”.
  • each of these samples of the invention Nos. 1 to 7 and comparative samples Nos. 1 and 2 was compression-formed in a magnetic field into pressurized powder.
  • This pressurized powder was set on a hot press to conduct hot pressing in vacuum at 790°C for ten minutes under a pressure of 1 ton/cm 2 so that the direction of application of the magnetic field agreed with the direction of compression, and rapidly cooled in Ar gas to prepare an anisotropic full-density magnet.
  • the magnetic properties of the resulting anisotropic full-density magnets are shown in Table 1.
  • Table 1 reveal that the bonded magnets manufactured from the samples of the invention Nos. 1 to 7 having an average grain size within a range of from 5 to 200 ⁇ m show better magnetic properties than those of the bonded magnets manufactured from the comparative samples Nos. 1 and 2 having an average grain size outside the range of from 5 to 200 ⁇ m.
  • an alloy having a chemical composition comprising 12.2% Nd, 17.2% Co, 7.0% B, 0.1% Zr, 0.5% Ga and the balance Fe (atomic %) was melted in an Ar gas atmosphere, and cast into an ingot.
  • This ingot was homogenized in an Ar atmosphere by holding it at a temperature of 1,120°C for 40 hours, and then crushed to blocks each having a side of up to 10 mm.
  • the block was caused to occlude hydrogen by heating it from the room temperature to 760°C in a hydrogen atmosphere under 1 atm.
  • Hydrogen occlusion was caused by holding the block at 760°C for one hour while maintaining the hydrogen atmosphere of 1 atm. to accelereate phase transformation.
  • the block was further heated to 820°C, held at 820°C for one hour, and was forcedly caused to release hydrogen until a 1 x 10 -1 vacuum atmosphere is achieved to accelerate phase transformation.
  • the block was then cooled in Ar gas.
  • the ingot after hydrogen occlusion and release had a recrystallized fine aggregate structure of the R 2 T 14 B-type intermetallic compound phase having an average recrystallization grain size of 0.3 ⁇ m.
  • samples of the magnet powder of the present invention ion Nos. 8 and 9 were prepared.
  • a sample of comparative magnet powder No. 3 was prepared.
  • the prepared samples of the invention Nos. 8 and 9 had a coercive force, iHc, of 14,2 kOe, and the comparative sample No. 3 had a coercive force, iHc , of 14.6 kOe.
  • Each of the samples of the invention Nos. 8 and 9 and the comparative sample No. 3 was mixed with 2.7 wt.% epoxy resin and compression-formed while making adjustment so as to give a density of 6.0 g/cm 3 in an oriented magnetic field in to a pressurized powder.
  • This pressurized powder was thermoset at 130°C for one hour to prepare an anisotropic bonded magnet.
  • the magnetic properties of the prepared anisotropic bonded magnets are represented in a graph as shown in Fig.
  • H F is the oriented magnetic field during forming in the magnetic field; and iHc is the coercive force of the powder
  • B r /B r70 where B r is the remanent magnetization; and B r70 is the remanent magnetization in a magnetized field of 70 kOe
  • each of these samples of the invention Nos. 8 and 9 and the comparative sample No. 3 was compression-formed in an oriented magnetic field into pressurized powder.
  • the pressurized powder was set on a hot press and hot-pressed under vacuum at 800°C for ten minutes under a pressure of 1 ton/cm 2 so that the direction of application of the magnetic field agreed with the direction of compression.
  • the hot-pressed powder was then rapidly cooled in Ar gas to prepare an anisotropic full-density magnet.
  • the magnetic properties of the prepared anisotropic full-density magnet are represented in a graph as shown in Fig. 2, with H F /iHc on the abscissa and B r /B r70 on the ordinate.
  • Figs. 1 and 2 suggest that use of the samples of the invention Nos. 8 and 9 having an average grain size of 50 ⁇ m and 150 ⁇ m, respectively, improves the degree of orientation in a low-orientation magnetic field having an iHc of up to 1.5 times and permits preparation of an anisotropic bond magnet and an anisotropic full-density magnet having sufficiently high properties, whereas use of the comparative sample No. 3 having an average grain size of 300 ⁇ m does not improve the degree of orientation in an oriented magnetic field having an iHc of up to 1.5 times, and does not give an anisotropic bonded magnet or an anisotropic full-density magnet having sufficiently high properties.
  • the rare-earth magnet material powder excellent in anisotropy of the present invention having an average grain size within a range of from 5 to 200 ⁇ m, the degree of orientation in a low-orientation magnetic field of a coercive force, iHc, of up to 1.5 times is improved, and it is possible to manufacture an anisotropic rare-earth magnet having better magnetic properties than those of conventional ones in a low magnetic field output, thus providing industrially useful effects.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Hard Magnetic Materials (AREA)
  • Powder Metallurgy (AREA)

Claims (4)

  1. Matériau en poudre anisotrope pour aimant, ayant la structure globale fine recristallisée d'une phase de composé intermétallique du type R2T14B, qui comprend l'un quelconque des éléments des terres rares y compris Y, désigné ci-après par le symbole "R", du fer ou un composant dans lequel une partie du fer est remplacée par du cobalt, désigné ci-après par le symbole "T", et du bore comme composants principaux, ces composants ayant un diamètre de grain moyen à l'état recristallisé de 0,05 à 20 µm, cette poudre comprenant en outre l'un ou plusieurs des éléments Si, Ga, Zr, Nb, Mo, Hf, Ta, W, Al, Ti et V, désignés ci-après par le symbole "M", matériau caractérisé en ce qu'il contient une quantité totale de 0,001 à 5,0 pour cent, en proportion atomique, de M et en ce que la poudre a un diamètre des grains moyens dans la plage de 5 à 200 µm.
  2. Matériau en poudre suivant la revendication 1, dans lequel une partie du fer est remplacée en outre ou en variante par du chrome, du manganèse, du nickel, du cuivre ou du zinc.
  3. Matériau en poudre suivant la revendication 1 ou la revendication 2, dans lequel une partie du bore est remplacée par du carbone, de l'azote ou de l'oxygène.
  4. Utilisation de la poudre suivant l'une quelconque des revendications précédentes dans la fabrication d'aimants liés ou pressés à chaud.
EP19930307756 1992-11-13 1993-09-30 Matériau en poudre pour aimant à base de terre-rare Expired - Lifetime EP0597582B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4328805A JPH06151137A (ja) 1992-11-13 1992-11-13 異方性に優れた希土類磁石材料粉末
JP328805/92 1992-11-13

Publications (2)

Publication Number Publication Date
EP0597582A1 EP0597582A1 (fr) 1994-05-18
EP0597582B1 true EP0597582B1 (fr) 1997-12-17

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EP19930307756 Expired - Lifetime EP0597582B1 (fr) 1992-11-13 1993-09-30 Matériau en poudre pour aimant à base de terre-rare

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EP (1) EP0597582B1 (fr)
JP (1) JPH06151137A (fr)
DE (2) DE69315807D1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5480471A (en) * 1994-04-29 1996-01-02 Crucible Materials Corporation Re-Fe-B magnets and manufacturing method for the same
US6004407A (en) * 1995-09-22 1999-12-21 Alps Electric Co., Ltd. Hard magnetic materials and method of producing the same
DE10255604B4 (de) 2002-11-28 2006-06-14 Vacuumschmelze Gmbh & Co. Kg Verfahren zum Herstellen eines anisotropen Magnetpulvers und eines gebundenen anisotropen Magneten daraus
CN113593799B (zh) * 2020-04-30 2023-06-13 烟台正海磁性材料股份有限公司 一种细晶、高矫顽力烧结钕铁硼磁体及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1012477B (zh) * 1987-08-19 1991-05-01 三菱金属株式会社 稀土-铁-硼磁体粉末及其制备方法
US5228930A (en) * 1989-07-31 1993-07-20 Mitsubishi Materials Corporation Rare earth permanent magnet power, method for producing same and bonded magnet

Also Published As

Publication number Publication date
DE69315807T4 (de) 1999-04-22
DE69315807D1 (de) 1998-01-29
EP0597582A1 (fr) 1994-05-18
JPH06151137A (ja) 1994-05-31
DE69315807T2 (de) 1998-07-16

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