EP0468903B1 - Herstellungsverfahren von Seltenerdübergangsmetall-Bortyp-Magnetpulver für korrosionsfeste Magnete - Google Patents

Herstellungsverfahren von Seltenerdübergangsmetall-Bortyp-Magnetpulver für korrosionsfeste Magnete Download PDF

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Publication number
EP0468903B1
EP0468903B1 EP91420269A EP91420269A EP0468903B1 EP 0468903 B1 EP0468903 B1 EP 0468903B1 EP 91420269 A EP91420269 A EP 91420269A EP 91420269 A EP91420269 A EP 91420269A EP 0468903 B1 EP0468903 B1 EP 0468903B1
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EP
European Patent Office
Prior art keywords
patm
log
magnets
rare earth
under
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
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EP91420269A
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English (en)
French (fr)
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EP0468903A1 (de
Inventor
Armand Gabriel
Masato Sagawa
Philippe Tenaud
Pierre Turillon
Fernand Vial
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Ugimag SA
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Ugimag SA
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Priority to AT91420269T priority Critical patent/ATE101451T1/de
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Classifications

    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/023—Hydrogen absorption
    • 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

Definitions

  • the invention relates to a method for obtaining, in divided form, magnetic materials of the TR Fe B type which are brittle and relatively inert with respect to air and which lead to magnets with improved corrosion resistance.
  • TR Fe B By magnetic materials type TR Fe B is meant materials essentially consisting of a magnetic tetragonal phase T1, analogous to TR2 Fe14 B, TR designating one (or more) rare earth (s), including Yttrium, Iron and Boron can be partially substituted, as is known, by other elements such as cobalt, with or without the addition of metals such as aluminum, copper, gallium, or refractory metals. See EP-A-101552, EP-A-106948, EP-A-344542, and French patent applications Nos 89-16731 and 89-16732.
  • rare earth is constituted by Neodymium, which can be partly replaced by praseodymium and dysprosium.
  • the magnets of this family have to date, the most efficient magnetic properties in particular with regard to the residual induction (Br), the intrinsic coercivity (H cJ ) and the specific energy [( BH) max ].
  • the classic method of manufacturing magnets of this type consists in obtaining a fine powder, possibly compressing it under magnetic field and sintering it before various finishes and final magnetization.
  • hydrogen decrepitation is meant a process for dividing an alloy consisting in subjecting an alloy in pieces to a hydrogen atmosphere under temperature and pressure conditions dependent on the alloy and allowing the conversion at least partially. into a hydride and then subjecting it to different conditions of temperature and pressure such that the hydride decomposes.
  • This cycling often leads to a noisy fragmentation of the alloy, which is said to "decrepitate”.
  • GB 1 313 272 and GB 1 554 384 for binary combinations of a rare earth and a transition metal, mainly cobalt, combinations for which this process has not provided 'major advantages over conventional grinding methods, and therefore has not received notable industrial applications.
  • the powders Although the grinding, compression and sintering operations can be carried out under protective atmospheres, the powders partially oxidize during their transformation before densification (sintering) by reaction with the residual O2 and / or H2O contents of said atmospheres. This oxidation is particularly strong when the developed surface of the material is large, for example in the stages of pre-grinding, grinding, storage, compression of the powders, and during the rise in sintering temperature. As the Applicant has observed for itself, the method of decrepitation with hydrogen does not make it possible, in the art described above, to resolve these drawbacks.
  • the applicant has sought a method considerably reducing the reactivity of these materials with respect to atmospheres, in particular those containing oxygen and / or water vapor, and leading to sintered magnets increased resistance to corrosion.
  • the process according to the invention consists in treating the material (crushed ingot or granules resulting from reduction of oxides) in a reactor where hydrogen is introduced under specific conditions of temperature (T) and pressure (P) defined below, at least in a final phase.
  • the temperature T is chosen between 350 ° C and 550 ° C and in particular between 350 and 500 ° C if P ⁇ Patm. and the conditions 350 + 100 log P / Patm. ⁇ T ⁇ 550 + 100 log (P / Patm.) and in particular 350 + 100 log (P / Patm.) ⁇ T ⁇ 500 + 100 log (P / Patm.) if P> Patm. More preferably, the temperature is kept above 400 ° C.
  • reaction kinetics it is preferable to operate with a pressure P greater than or equal to 50.6 kPa (0.5 atm.); in addition, for reasons of safety and simplicity of construction of the treatment enclosure, in particular with regard to its sealing, it is preferable to operate below 101.3 kPa (1 atm.).
  • hydrogen pressure P is meant its absolute pressure in the case of a gas atmosphere alone, or its partial pressure in the case of a mixture of gases containing hydrogen or of a body providing nascent hydrogen such as ammonia NH3.
  • temperature T to which H2 is introduced is meant the minimum temperature to which the product is brought by a heat source, independently of the heating which may result from the exothermic hydriding reaction; the actual temperature of the material is that reached by it during its transformation. The duration of treatment depends on the operating conditions used; the reaction is considered to be complete when the hydrogen pressure and the temperature have become constant.
  • the reactor containing the product is then brought back to the usual temperature, pressure and atmosphere conditions.
  • rare earth hydrides are not strict defined compounds, but the stoichiometry of which can vary within wide limits.
  • these hydrides, of formula TR Hx have a value of x which can vary continuously from 1.8 to 3.
  • TRH2 a TR hydride of formula TR Hx with x between 1.8 and 2.45 - designated here by "TRH2" - to the exclusion of all others; in particular, the formation of a hydride of the standard formula has not been detected under the conditions of the invention TR2 Fe14 B Hy or ⁇ -Fe or a more hydrogenated hydride such as NdH3.
  • the material at the end of the hydrogen treatment essentially consists of 3 main phases: TR2 Fe14 B, called T1, "TR H2", and a boron-rich phase already described in the prior art.
  • this rare earth-rich hydride is attributed to the appearance of appreciable friability of the stable and passive hydrogenated products, without creating the hydrated phase of T1.
  • this friability does not constitute a disadvantage for the health of the tablet during the rise in temperature towards the sintering, since this phase is a minority in volume opposite T1.
  • the Applicant has found that the hydrogen treatment also leads to brittle materials but comprising significant amounts of the hydride of T1, the hydride NdH3, or of ⁇ -Fe. These materials did not make it possible to obtain magnets resistant to corrosion, see the examples outside the invention.
  • Tests have been carried out on materials obtained by fusion, having the following composition (in at%), which is not limiting, which contains a low TR content in order to obtain the highest remanences. They made it possible to test the passivity of the materials obtained under different conditions according to the invention and outside the invention and the quality of corrosion resistance of the final magnets.
  • the method described in this invention has been successfully applied to other TR or B compositions, or comprising substitutions and / or additions described in the prior art (see EP-A-101552, EP-A-106558, EP-A-344542), or alternatively to granules coming from the so-called diffusion reduction process.
  • the friability was measured by the particle size spectrum (% by weight passing through the sieve, without external constraint) of the material obtained after the hydriding treatment.
  • the nature of the phases present in the hydrated material was determined by X-ray diffraction.
  • the magnetic characteristics - B r and H cJ - were determined on sintered magnets, prepared according to the process recalled in the introduction, and without extreme precautions for handling atmospheres.
  • the oxygen content of the magnets obtained is situated according to their composition in the most desirable range for the particular use thereof. It is known that the prior art recommends either relatively high oxygen contents in order to improve the resistance to corrosion, this is the case of US Pat. No. 4,588,439; or on the contrary very low rates, as in the patent. EP 0.197.712, if it is desired to achieve high magnetic properties (Br, (BH)).
  • the corrosion resistance of sintered magnets has been estimated by their service life in autoclave at 115 ° C, under 0.175 MPa at 100% relative humidity. In all cases, the magnets were coated before testing under identical conditions, with an epoxy resin after a surface preparation (phosphating). The resistance of the coating was estimated by visual examination (blisters) and by the cross-cutting test.
  • Examples 1, 6 and 7 relate to the prior art, or to conditions outside the invention, the other tests (Examples 2 to 5 and 8) relate to the invention.
  • Example 1 shows that under conditions close to those of the prior art (25 ° C. at around 0.1 MPa of H2), and for the composition exemplified a duration of 4 days is the maximum that the magnet coated in autoclave, before blistering occurs, sign of corrosion.
  • Example 2 shows that hydriding at 300 ° C under conditions representative of the invention leads to a considerably increased autoclave service life (+ 100%) compared to Example 1, which may be related to an improved compactness.
  • Example 6 shows that at 550 ° C, there is no longer any embrittlement. Mechanical pre-grinding is then necessary. Densification becomes difficult; the service lives in the autoclave are extremely short, as are the magnetic properties, no doubt due to the presence of numerous open porosities.
  • example 8 At 700 ° C. (example 8), the magnetic properties as well as the corrosion resistance are optimal, similar to those of example 2.

Landscapes

  • 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)
  • Dynamo-Electric Clutches, Dynamo-Electric Brakes (AREA)
  • Reciprocating, Oscillating Or Vibrating Motors (AREA)
  • Manufacturing Cores, Coils, And Magnets (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (6)

  1. Verfahren zur Herstellung eines bröckligen und relativ inerten magnetischen Materials des Fe-Seltenerd-B-Typs in unterteilter Form, das wenigstens die Phase T1, Nd₂ Fe₁₄-B und ein Seltenerdhydrid, TR Hx mit x im Bereich von 1,8 bis 2,45 enthält, wobei die Herstellung gesinterter Dauermagnete ermöglicht wird, die gut gegen die Korrosion in einer Wasserstoff enthaltenden Atmosphäre beständig sind, dadurch gekennzeichnet, daß die Bedingungen absoluten Drucks (P) und der Temperatur T (°C) die folgenden sind:
       wenn P ≦ P atm, 250 < T < 550 °C
       wenn P > P atm, 250 + 100 log (P/P atm) < T < 550 + 100 log (P/P atm),
    in welchen Formeln P atm den atmosphärischen Druck und log den Logarithmus mit Basis 10 bedeuten.
  2. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß:
       wenn P ≦ P atm, 350 < T < 550 °C
       wenn P > P atm, 350 + 100 log (P/P atm) < T < 550 + 100 log (P/P atm).
  3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß:
       wenn P ≦ P atm, 350 < T < 500 °C
       wenn P > P atm, 350 + 100 log (P/P atm) < T < 500 + 100 log (P/P atm).
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Temperatur > 400 °C ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Druck P über 50,6 kPa (0,5 at) ist.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß der Druck P unter 101,3 kPa (1 at) ist.
EP91420269A 1990-07-25 1991-07-23 Herstellungsverfahren von Seltenerdübergangsmetall-Bortyp-Magnetpulver für korrosionsfeste Magnete Expired - Lifetime EP0468903B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT91420269T ATE101451T1 (de) 1990-07-25 1991-07-23 Herstellungsverfahren von seltenerduebergangsmetall-bortyp-magnetpulver fuer korrosionsfeste magnete.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR909009722A FR2665295B1 (fr) 1990-07-25 1990-07-25 Methode d'obtention sous forme divisee d'un materiau magnetique de type terre-rare - metaux de transition - bore pour des aimants resistant a la corrosion.
FR9009722 1990-07-25

Publications (2)

Publication Number Publication Date
EP0468903A1 EP0468903A1 (de) 1992-01-29
EP0468903B1 true EP0468903B1 (de) 1994-02-09

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EP91420269A Expired - Lifetime EP0468903B1 (de) 1990-07-25 1991-07-23 Herstellungsverfahren von Seltenerdübergangsmetall-Bortyp-Magnetpulver für korrosionsfeste Magnete

Country Status (12)

Country Link
US (1) US5221368A (de)
EP (1) EP0468903B1 (de)
JP (1) JP2933293B2 (de)
AT (1) ATE101451T1 (de)
CA (1) CA2046478A1 (de)
DE (1) DE69101155T2 (de)
ES (1) ES2050519T3 (de)
FI (1) FI107303B (de)
FR (1) FR2665295B1 (de)
HK (1) HK39195A (de)
IE (1) IE66827B1 (de)
SG (1) SG29795G (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5788782A (en) * 1993-10-14 1998-08-04 Sumitomo Special Metals Co., Ltd. R-FE-B permanent magnet materials and process of producing the same
JP2881409B2 (ja) * 1996-10-28 1999-04-12 愛知製鋼株式会社 異方性磁石粉末の製造方法
JP3452254B2 (ja) 2000-09-20 2003-09-29 愛知製鋼株式会社 異方性磁石粉末の製造方法、異方性磁石粉末の原料粉末およびボンド磁石

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60119701A (ja) * 1983-12-01 1985-06-27 Sumitomo Special Metals Co Ltd 希土類・ボロン・鉄系永久磁石用合金粉末の製造方法
JPS6390104A (ja) * 1986-10-03 1988-04-21 Tdk Corp 希土類−鉄−ホウ素系永久磁石の製造方法
GB2201426B (en) * 1987-02-27 1990-05-30 Philips Electronic Associated Improved method for the manufacture of rare earth transition metal alloy magnets
JPS6448403A (en) * 1987-08-19 1989-02-22 Mitsubishi Metal Corp Rare earth-iron-boron magnet powder and manufacture thereof
DE3850001T2 (de) * 1987-08-19 1994-11-03 Mitsubishi Materials Corp Magnetisches Seltenerd-Eisen-Bor-Puder und sein Herstellungsverfahren.
JP2564492B2 (ja) * 1987-10-13 1996-12-18 三菱マテリアル株式会社 希土類−Ｆｅ−Ｂ系鋳造体永久磁石の製造法
US5091020A (en) * 1990-11-20 1992-02-25 Crucible Materials Corporation Method and particle mixture for making rare earth element, iron and boron permanent sintered magnets

Also Published As

Publication number Publication date
EP0468903A1 (de) 1992-01-29
JP2933293B2 (ja) 1999-08-09
IE66827B1 (en) 1996-02-07
FI913546A0 (fi) 1991-07-24
ATE101451T1 (de) 1994-02-15
SG29795G (en) 1995-08-18
DE69101155D1 (de) 1994-03-24
FR2665295B1 (fr) 1994-09-16
US5221368A (en) 1993-06-22
DE69101155T2 (de) 1994-06-01
HK39195A (en) 1995-03-24
FI913546A (fi) 1992-01-26
IE912607A1 (en) 1992-01-29
JPH06120015A (ja) 1994-04-28
FR2665295A1 (fr) 1992-01-31
FI107303B (fi) 2001-06-29
ES2050519T3 (es) 1994-05-16
CA2046478A1 (fr) 1992-01-26

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