EP0707739A1 - Herstellungsverfahren eines seltenen cobalttyp fluorenthaltendes magnetpuder und verdichtete dauermagneten daraus - Google Patents
Herstellungsverfahren eines seltenen cobalttyp fluorenthaltendes magnetpuder und verdichtete dauermagneten darausInfo
- Publication number
- EP0707739A1 EP0707739A1 EP94921696A EP94921696A EP0707739A1 EP 0707739 A1 EP0707739 A1 EP 0707739A1 EP 94921696 A EP94921696 A EP 94921696A EP 94921696 A EP94921696 A EP 94921696A EP 0707739 A1 EP0707739 A1 EP 0707739A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluorine
- ppm
- rare earth
- cobalt
- permanent magnets
- 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
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 25
- 239000011737 fluorine Substances 0.000 title claims abstract description 24
- 239000006247 magnetic powder Substances 0.000 title claims abstract description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract 7
- 238000000034 method Methods 0.000 title claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 title description 14
- 150000002910 rare earth metals Chemical class 0.000 title description 12
- 239000010941 cobalt Substances 0.000 title description 8
- 229910017052 cobalt Inorganic materials 0.000 title description 8
- 230000008569 process Effects 0.000 title description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 14
- 229910052772 Samarium Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 6
- 229910052777 Praseodymium Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 230000005415 magnetization Effects 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004581 coalescence Methods 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011090 industrial biotechnology method and process Methods 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- -1 iron Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005316 response function Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- OJIKOZJGHCVMDC-UHFFFAOYSA-K samarium(iii) fluoride Chemical compound F[Sm](F)F OJIKOZJGHCVMDC-UHFFFAOYSA-K 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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. |
| FR9308644 | 1993-07-08 | ||
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0707739A1 true EP0707739A1 (de) | 1996-04-24 |
| EP0707739B1 EP0707739B1 (de) | 1997-04-09 |
Family
ID=9449236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94921696A Expired - Lifetime EP0707739B1 (de) | 1993-07-08 | 1994-07-07 | Ein seltener erd-cobalttyp fluorenthaltender magnetpuder und verdichtete dauermagneten daraus und deren herstellungsverfahren |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0707739B1 (de) |
| DE (1) | DE69402551T2 (de) |
| FR (1) | FR2707192B1 (de) |
| WO (1) | WO1995002252A1 (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007032406B3 (de) * | 2007-07-10 | 2008-10-23 | Gkss-Forschungszentrum Geesthacht Gmbh | Herstellung von Legierungen auf Basis von Titanaluminiden |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6803121A (de) * | 1968-03-05 | 1969-09-09 | ||
| JPH02288306A (ja) * | 1989-04-28 | 1990-11-28 | Seiko Electronic Components Ltd | 希土類永久磁石の製造方法 |
-
1993
- 1993-07-08 FR FR9308644A patent/FR2707192B1/fr not_active Expired - Fee Related
-
1994
- 1994-07-07 EP EP94921696A patent/EP0707739B1/de not_active Expired - Lifetime
- 1994-07-07 WO PCT/FR1994/000838 patent/WO1995002252A1/fr not_active Ceased
- 1994-07-07 DE DE69402551T patent/DE69402551T2/de not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 10, no. 8 (E-373) 14 Janvier 1986 & JP-A-60 173 804 * |
| PATENT ABSTRACTS OF JAPAN vol. 9, no. 189 (E-333) 6 Août 1985 & JP-A-60 057 601 * |
| See also references of WO9502252A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69402551D1 (de) | 1997-05-15 |
| DE69402551T2 (de) | 1997-09-11 |
| WO1995002252A1 (fr) | 1995-01-19 |
| EP0707739B1 (de) | 1997-04-09 |
| FR2707192A1 (fr) | 1995-01-13 |
| FR2707192B1 (fr) | 1995-08-11 |
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