EP0596385A1 - Procédé pour la fabrication d'alliages de terres rares du type RE2Fe17-xTMxNy - Google Patents

Procédé pour la fabrication d'alliages de terres rares du type RE2Fe17-xTMxNy Download PDF

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Publication number
EP0596385A1
EP0596385A1 EP93117318A EP93117318A EP0596385A1 EP 0596385 A1 EP0596385 A1 EP 0596385A1 EP 93117318 A EP93117318 A EP 93117318A EP 93117318 A EP93117318 A EP 93117318A EP 0596385 A1 EP0596385 A1 EP 0596385A1
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EP
European Patent Office
Prior art keywords
temperature
alloy
mixture
reaction mixture
hydrogen
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.)
Ceased
Application number
EP93117318A
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German (de)
English (en)
Inventor
Horst Eggert
Michael Dr. Steinhorst
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.)
Evonik Operations GmbH
Original Assignee
TH Goldschmidt AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TH Goldschmidt AG filed Critical TH Goldschmidt AG
Publication of EP0596385A1 publication Critical patent/EP0596385A1/fr
Ceased legal-status Critical Current

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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
    • H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
    • H01F1/0596—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2 of rhombic or rhombohedral Th2Zn17 structure or hexagonal Th2Ni17 structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/013—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/02—Nitrogen

Definitions

  • the invention relates to a process for producing alloys of the type SE 2 Fe 17-x TM x N y ,
  • SE rare earth metal, including Y, or a mixture of these metals
  • TM Co, Ni, Cu, Zr, Ga, Hf, Ta, Nb, Ti, Si, Al, V, Mo, Cr, Zn or Sn or a mixture of these metals
  • x 0 to 10
  • y > 0 to 5
  • the alloys preferably having a magnetic anisotropy in the direction of c -Axes have, by calciothermic reduction of a finely divided, homogeneous mixture of the alloy components, at least one of which is in the form of an oxide, subsequent diffusion of the alloy components, subsequent nitriding by the action of nitrogen or NH 3 and removal of the calcium oxide formed and any excess calcium.
  • This method is the starting point of the present invention.
  • Alloys of the type SE 2 Fe 17-x TM x N y are known from the prior art. They have the advantage of a higher Curie temperature than the base alloy.
  • the Curie temperature of the Sm 2 Fe 17 alloy is 130 ° C
  • EP-OS 0 453 270 also deals with the hard magnetic properties of nitrides of the composition mentioned.
  • Sm 2 Fe 17 N y For the preparation of Sm 2 Fe 17 N y , for example, a single-phase Sm 2 Fe 17 is required as a preliminary product, in order to then convert it into the desired nitride by nitriding.
  • the Sm 2 Fe 17 is often alloyed with various elements in order to improve the nitriding behavior or, for example, the magnetic properties of the nitride produced subsequently.
  • Nb intermetallic Laves phase of the composition NbFe 2 (AE Platts, 1st R.
  • an Sm 2 Fe 17-x TM x N y is formed after nitriding, which is made from a multi-phase master alloy, but which is essentially based on the intermetallic phase Sm 2 Fe 17 .
  • a second way of obtaining Sm 2 Fe 17 is to set a nanocrystalline structure.
  • Schnitzke et al. K. Schnitzke, L. Schultz, J. Wecker, M. Katter, submitted to Appl. Phys. Lett.
  • X-ray analysis of the powder showed only an amorphous phase and crystalline a-Fe.
  • the intermetallic phase Sm 2 Fe 17 only forms during a subsequent heat treatment, which is then converted to the Sm 2 Fe 17 N y compound by nitriding.
  • a disadvantage of this production process is that only isotropic Sm 2 Fe 17 N y alloys can be produced.
  • thermodynamically preferred reactions when nitriding Sm2 Fe17 are: These reactions are affected by the nitriding temperature and the duration of the nitriding. With increasing temperature and / or duration of nitration, an increased formation of SmN and a-Fe is observed. The nitriding can be accelerated by reducing the grain size of the Sm 2 Fe 17 used due to a smaller diffusion path.
  • the influencing parameters grain size and duration and temperature of the nitriding must be coordinated with one another in preliminary tests in order to be able to produce the required nitride in the desired purity.
  • the feature a4) of the method according to the invention is optional and serves to accelerate the subsequent nitriding.
  • the decomposition temperature of the Sm 2 Fei 7 Hz which is formed should not be exceeded. This temperature is known from the literature or can be measured in a differential thermal analysis (DTA) carried out beforehand.
  • DTA differential thermal analysis
  • the decomposition temperature of the nitride SE 2 Fe 17 - x TM x Ny which forms in process stage b) must not be exceeded even during the nitriding according to feature b).
  • a minimum temperature of 473 K is required in order to be able to carry out the nitriding in a reasonable time.
  • N 2 a mixture of N 2 / H 2 or NH 3 can be used as the nitriding atmosphere.
  • the hydrogen is preferably removed by applying a vacuum before the nitration.
  • an alloy with a grain size of 5 to 100 ⁇ m is selected for process step b).
  • the reason for this is to be seen in the fact that the duration of the nitration in the same atmosphere at constant pressure and at a constant temperature depends on the diffusion path to be covered, i.e. depends on the grain size. The smaller the grain size, the faster the nitriding takes place.
  • the grain size of the raw materials mentioned - except Ca - is below 75 ⁇ m.
  • Fig. 3 shows the associated temperature profile of the furnace and in the reaction mixture.
  • the critical melting temperature of the Sm 2 Fe 17 of 1553 K is not reached or exceeded at any time during the reduction and diffusion process.
  • the mixture is cooled to 773 K.
  • N 2 is introduced. Under the given conditions, a nitriding time of approx. 19 hours is required, then a saturation is observed in the N 2 uptake - FIG. 4.
  • reaction product is then cooled to room temperature under N 2 and the CaO and excess Ca formed are removed in H 2 0.
  • the N 2 uptake can be significantly accelerated by prior hydrogenation.
  • the reaction mixture After the reaction mixture has been tempered, it is cooled to a temperature of 523 K and, in the isothermal state, H 2 is introduced into the crucible and the reaction mixture is loaded with H 2 for 1 hour.
  • H 2 According to X-ray diffraction studies, a compound of the general composition Sm 2 Fe 17 H x is formed during the hydrogenation. Decomposition according to the reaction equation: could not be proven.
  • the crucible is then flooded with N 2 and heated to 773 K.
  • the reaction mixture is then nitrided under isothermal conditions within less than 10 hours to saturation (Fig. 5 and 6).
  • Table 2 shows the chemical composition typically set after the reduction, diffusion, hydrogenation and nitration process:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Hard Magnetic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Powder Metallurgy (AREA)
EP93117318A 1992-11-05 1993-10-26 Procédé pour la fabrication d'alliages de terres rares du type RE2Fe17-xTMxNy Ceased EP0596385A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4237346A DE4237346C1 (de) 1992-11-05 1992-11-05 Verfahren zur Herstellung von Legierungen der Seltenen Erden des Typs SE¶2¶Fe¶1¶¶7¶¶-¶¶x¶M¶x¶N¶y¶
DE4237346 1992-11-05

Publications (1)

Publication Number Publication Date
EP0596385A1 true EP0596385A1 (fr) 1994-05-11

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ID=6472157

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93117318A Ceased EP0596385A1 (fr) 1992-11-05 1993-10-26 Procédé pour la fabrication d'alliages de terres rares du type RE2Fe17-xTMxNy

Country Status (6)

Country Link
US (1) US5482572A (fr)
EP (1) EP0596385A1 (fr)
JP (1) JPH06212342A (fr)
CA (1) CA2108736A1 (fr)
DE (1) DE4237346C1 (fr)
FI (1) FI934885A7 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100513015C (zh) * 1997-12-25 2009-07-15 日亚化学工业株式会社 Sm-Fe-N系列合金粉末及其制造方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3234741B2 (ja) * 1995-04-25 2001-12-04 昭和電工株式会社 希土類磁石用合金及びその製造方法
JP3304726B2 (ja) * 1995-11-28 2002-07-22 住友金属鉱山株式会社 希土類−鉄−窒素系磁石合金
CN1044648C (zh) * 1997-05-22 1999-08-11 南开大学 共沉淀还原扩散法制备钕铁硼永磁合金
US6328825B1 (en) 1997-11-12 2001-12-11 Showa Denko K.K. Alloy used for production of a rare-earth magnet and method for producing the same
JP4481949B2 (ja) * 2006-03-27 2010-06-16 株式会社東芝 磁気冷凍用磁性材料
CN105723476B (zh) * 2014-09-19 2018-03-27 株式会社东芝 永磁体、电动机及发电机
EP3226262B1 (fr) * 2014-11-28 2020-11-04 Kabushiki Kaisha Toshiba Aimant permanent, moteur et génératrice
WO2017150557A1 (fr) * 2016-03-04 2017-09-08 国立研究開発法人産業技術総合研究所 Poudre d'alliage de samarium-fer-azote et son procédé de production
CN111370194B (zh) * 2019-12-16 2021-02-09 横店集团东磁股份有限公司 一种铁硅铝软磁粉末的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0369097A1 (fr) * 1988-11-14 1990-05-23 Asahi Kasei Kogyo Kabushiki Kaisha Matériaux magnétiques contenant des éléments en terres rares, du fer, du nitrogène et de l'hydrogène
EP0453270A2 (fr) * 1990-09-04 1991-10-23 The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin Matériaux magnétiques à base de terres rares, procédé de fabrication et utilisation
EP0468317A2 (fr) * 1990-07-25 1992-01-29 Siemens Aktiengesellschaft Procédé de fabrication de matériau magnétique à base du système de substances Sm-Fe-N
EP0470476A2 (fr) * 1990-08-09 1992-02-12 Siemens Aktiengesellschaft Procédé de fabrication d'un matériau magnétique anisotrope à base du système de substances Sm-Fe-N
EP0540898A2 (fr) * 1991-10-22 1993-05-12 Th. Goldschmidt AG Procédé de préparation de phases intermétalliques mono-phasiques qui fondent de façon incongrue

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3826696A (en) * 1971-08-16 1974-07-30 Gen Electric Rare earth intermetallic compounds containing calcium
US4769063A (en) * 1986-03-06 1988-09-06 Sumitomo Special Metals Co., Ltd. Method for producing rare earth alloy
US4760966A (en) * 1987-08-28 1988-08-02 The United States Of America As Represented By The Secretary Of The Army Method of comminuting rare earth magnet alloys into fine particles
DE4204173A1 (de) * 1992-02-13 1993-08-19 Goldschmidt Ag Th Verfahren zur herstellung einphasiger, inkongruent schmelzender intermetallischer phasen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0369097A1 (fr) * 1988-11-14 1990-05-23 Asahi Kasei Kogyo Kabushiki Kaisha Matériaux magnétiques contenant des éléments en terres rares, du fer, du nitrogène et de l'hydrogène
EP0468317A2 (fr) * 1990-07-25 1992-01-29 Siemens Aktiengesellschaft Procédé de fabrication de matériau magnétique à base du système de substances Sm-Fe-N
EP0470476A2 (fr) * 1990-08-09 1992-02-12 Siemens Aktiengesellschaft Procédé de fabrication d'un matériau magnétique anisotrope à base du système de substances Sm-Fe-N
EP0453270A2 (fr) * 1990-09-04 1991-10-23 The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin Matériaux magnétiques à base de terres rares, procédé de fabrication et utilisation
EP0540898A2 (fr) * 1991-10-22 1993-05-12 Th. Goldschmidt AG Procédé de préparation de phases intermétalliques mono-phasiques qui fondent de façon incongrue

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
IEEE TRANSACTIONS ON MAGNETICS Bd. 23(5), September 1987, Seiten 3098 - 3100 HIGANO, YAMAGATA, TOKORO ET AL. 'Magnetic Properties of RE-TM-N system' *
PATENT ABSTRACTS OF JAPAN vol. 9, no. 287 (C-314)14. November 1985 & JP-A-60 131 949 ( HITACHI KINZOKU KK ) 13. Juli 1985 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100513015C (zh) * 1997-12-25 2009-07-15 日亚化学工业株式会社 Sm-Fe-N系列合金粉末及其制造方法

Also Published As

Publication number Publication date
FI934885A7 (fi) 1994-05-06
DE4237346C1 (de) 1993-12-02
US5482572A (en) 1996-01-09
JPH06212342A (ja) 1994-08-02
CA2108736A1 (fr) 1994-05-06
FI934885A0 (fi) 1993-11-04

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