WO1995002252A1 - Procede de preparation de poudres magnetiques de type terres rares-cobalt contenant du fluor et aimants permanents densifies correspondants - Google Patents

Procede de preparation de poudres magnetiques de type terres rares-cobalt contenant du fluor et aimants permanents densifies correspondants Download PDF

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Publication number
WO1995002252A1
WO1995002252A1 PCT/FR1994/000838 FR9400838W WO9502252A1 WO 1995002252 A1 WO1995002252 A1 WO 1995002252A1 FR 9400838 W FR9400838 W FR 9400838W WO 9502252 A1 WO9502252 A1 WO 9502252A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
ppm
rare earth
cobalt
permanent magnets
Prior art date
Application number
PCT/FR1994/000838
Other languages
English (en)
French (fr)
Inventor
Armand Gabriel
Henri Lemaire
Fernand Vial
Original Assignee
Ugimag S.A.
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 Ugimag S.A. filed Critical Ugimag S.A.
Priority to EP94921696A priority Critical patent/EP0707739B1/de
Priority to DE69402551T priority patent/DE69402551T2/de
Publication of WO1995002252A1 publication Critical patent/WO1995002252A1/fr

Links

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
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • 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
    • H01F1/0551—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0552—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes with a protective layer
    • 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
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered

Definitions

  • This invention relates to a method of protecting magnetic powders and permanent magnets of the transition metal-rare earth metal type against oxidation and atmospheric corrosion by the introduction of gaseous fluorine during the treatment of powders. It applies more particularly to powders and magnets of the transition metal - rare earth family, where the metal is essentially cobalt, and the rare earth essentially of samarium and / or neodymium and / or praseodymium and / or cerium. .
  • Fluorine gas is preferably used. With other experimental conditions, it can be replaced by other donors such as hydrofluoric acid HF or nitrogen trifluoride NF; but the former is much more aggressive and difficult to control, the latter is much more expensive. It was noted that: - below 600 ppm, there are not enough neutralized active sites when handling large quantities of fine powders, the process is unstable; - above 3000 ppm, there is too much active fluorine, which transforms into samarium fluoride, - thus displacing the local metallurgical composition by depletion in samarium.
  • Figure 1 shows the known ranges of oxygen uptake in the classic manufacture of Sm Co_ magnets.
  • the oxygen contents are established on the LECO commercial apparatus equipped with the appropriate furnace.
  • the process steps are as follows: (1) raw materials; (2) coarse pre-grinding (50 Uni); (3) fine grinding (5 ”m); (4) intermediate storage; (5) after sintering.
  • FIG. 2 gives the results of the magnetic characteristics (remanence Br, induction coercivity H, limiting stiffness field Hk) and the density p as a function of the rare earth content of the powder mixture and of the sintering temperature (A 1115 ° C; x: 1125 ° C; o: 1135 ° C) according to the prior art.
  • FIG. 3 shows schematically an example of technical embodiment of the invention.
  • FIG. 4 illustrates, by comparison with FIG. 2, the significant slip obtained according to the invention towards higher optima lying towards lower rare earth contents, in particular below 36% for the compositions of Sm Co type, ..
  • FIG. 5 illustrates a similar gain obtained in the Sm Co family, in particular on the rectangularity of the curve (gain in field of stiffness limit Hk), Hk corresponding to the demagnetizing field reducing the induction to 90% of Br.
  • the curve (1) is representative of the prior art
  • the curve (2) is representative of the invention.
  • Example 2 Before being compressed, the finely ground products of Example 2 were homogenized by stirring under an N atmosphere containing 200 ppm of fluorine. A slight gain on the oxygen content was noted, since its content fell to 3000 ppm. This is not enough to have a significant effect on the final properties. However, the wet air resistance could be increased from a few hours to a few days.
  • Example 2 the preparation was repeated from an alloy basic Sm Co_. 33% substituted with praseodymium. The same advantages have been obtained, as Table I illustrates for the remanence (in isostatic compression).
  • Example 5 (according to the invention) The method was also applied to alloys of the S Co family. For this, we chose a composition rich in Fe and poor in Sm with the hope of increasing the afterglow.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Hard Magnetic Materials (AREA)
PCT/FR1994/000838 1993-07-08 1994-07-07 Procede de preparation de poudres magnetiques de type terres rares-cobalt contenant du fluor et aimants permanents densifies correspondants WO1995002252A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP94921696A EP0707739B1 (de) 1993-07-08 1994-07-07 Ein seltener erd-cobalttyp fluorenthaltender magnetpuder und verdichtete dauermagneten daraus und deren herstellungsverfahren
DE69402551T DE69402551T2 (de) 1993-07-08 1994-07-07 Ein seltener erd-cobalttyp fluorenthaltender magnetpuder und verdichtete dauermagneten daraus und deren herstellungsverfahren

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR93/08644 1993-07-08
FR9308644A FR2707192B1 (fr) 1993-07-08 1993-07-08 Procédé de préparation de poudres magnétiques de type terres rares-cobalt contenant du fluor et aimants permanents densifiés correspondants.

Publications (1)

Publication Number Publication Date
WO1995002252A1 true WO1995002252A1 (fr) 1995-01-19

Family

ID=9449236

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR1994/000838 WO1995002252A1 (fr) 1993-07-08 1994-07-07 Procede de preparation de poudres magnetiques de type terres rares-cobalt contenant du fluor et aimants permanents densifies correspondants

Country Status (4)

Country Link
EP (1) EP0707739B1 (de)
DE (1) DE69402551T2 (de)
FR (1) FR2707192B1 (de)
WO (1) WO1995002252A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2185738B1 (de) * 2007-07-10 2012-02-22 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH Herstellung von legierungen auf basis von titanuluminiden

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1908943A1 (de) * 1968-03-05 1969-09-25 Philips Nv Verfahren zum Erhoehen der Koerzitivkraft und/oder der Remanenz eines magnetischen Pulvers
JPS6057601A (ja) * 1983-09-08 1985-04-03 Sumitomo Special Metals Co Ltd 永久磁石材料の製造方法
JPS60173804A (ja) * 1984-02-17 1985-09-07 Seiko Instr & Electronics Ltd 希土類コバルト磁石の製造方法
JPH02288306A (ja) * 1989-04-28 1990-11-28 Seiko Electronic Components Ltd 希土類永久磁石の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1908943A1 (de) * 1968-03-05 1969-09-25 Philips Nv Verfahren zum Erhoehen der Koerzitivkraft und/oder der Remanenz eines magnetischen Pulvers
JPS6057601A (ja) * 1983-09-08 1985-04-03 Sumitomo Special Metals Co Ltd 永久磁石材料の製造方法
JPS60173804A (ja) * 1984-02-17 1985-09-07 Seiko Instr & Electronics Ltd 希土類コバルト磁石の製造方法
JPH02288306A (ja) * 1989-04-28 1990-11-28 Seiko Electronic Components Ltd 希土類永久磁石の製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 10, no. 8 (E - 373) 14 January 1986 (1986-01-14) *
PATENT ABSTRACTS OF JAPAN vol. 15, no. 62 (E - 1033) 14 February 1991 (1991-02-14) *
PATENT ABSTRACTS OF JAPAN vol. 9, no. 189 (E - 333) 6 August 1985 (1985-08-06) *
See also references of EP0707739A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2185738B1 (de) * 2007-07-10 2012-02-22 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH Herstellung von legierungen auf basis von titanuluminiden

Also Published As

Publication number Publication date
EP0707739A1 (de) 1996-04-24
EP0707739B1 (de) 1997-04-09
DE69402551D1 (de) 1997-05-15
DE69402551T2 (de) 1997-09-11
FR2707192B1 (fr) 1995-08-11
FR2707192A1 (fr) 1995-01-13

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