EP0360104B1 - Procédés et dispositifs pour obtenir des fils en alliages métalliques amorphes - Google Patents
Procédés et dispositifs pour obtenir des fils en alliages métalliques amorphes Download PDFInfo
- Publication number
- EP0360104B1 EP0360104B1 EP89116705A EP89116705A EP0360104B1 EP 0360104 B1 EP0360104 B1 EP 0360104B1 EP 89116705 A EP89116705 A EP 89116705A EP 89116705 A EP89116705 A EP 89116705A EP 0360104 B1 EP0360104 B1 EP 0360104B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- jet
- gas
- alloy
- nozzle
- cooling liquid
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 5
- 238000009434 installation Methods 0.000 title abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 45
- 239000000956 alloy Substances 0.000 claims abstract description 45
- 239000000110 cooling liquid Substances 0.000 claims abstract description 10
- 230000003019 stabilising effect Effects 0.000 claims abstract 3
- 239000007789 gas Substances 0.000 claims description 40
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000005300 metallic glass Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims 2
- 238000007712 rapid solidification Methods 0.000 claims 2
- 238000011144 upstream manufacturing Methods 0.000 claims 2
- 239000000470 constituent Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000010410 layer Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 18
- 241001417494 Sciaenidae Species 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 241001080024 Telles Species 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 229910052845 zircon Inorganic materials 0.000 description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940082150 encore Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/01—Continuous casting of metals, i.e. casting in indefinite lengths without moulds, e.g. on molten surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/005—Continuous casting of metals, i.e. casting in indefinite lengths of wire
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
Definitions
- the invention relates to wires of amorphous metal alloys and in particular the methods and devices making it possible to obtain wires of amorphous metal alloys by rapid cooling in a liquid medium, these alloys being in particular based on iron.
- the projected jet tends to resolve in drops, which causes either a discontinuity of the jet leading to the impossibility of having a continuous wire, or to the formation of a continuous wire whose section is irregular.
- the patent US-A-3 845 805 describes a fixed system for producing metallic filaments by casting a jet in a cooling liquid which is circulated by passing it through a tube.
- the jet passes through a gas which can possibly promote the formation of a stabilizing skin on the jet.
- the thickness of this gas is very small, of the order of 0.2 cm.
- the object of the invention is to remedy these drawbacks, by proposing the method according to claim 1 and the device according to claim 7, the preambles of these claims being based on the aforementioned US-A-4,523,626 patent.
- the amorphous threads obtained with the process or the device according to the invention can be used, for example, to reinforce plastic or rubber articles, in particular tire casings.
- FIG. 3 is a side view and Figure 4 is a section taken along a plane passing through the axis of rotation xx ′ and by the point of contact 0 of the jet 7 with the layer 8, this section being shown schematically by the segments in a straight line IV-IV in FIG. 3.
- a part of the installation 21 is shown in detail in FIG. 5, this FIG. 5 being a section made along a plane passing through the axis yy ′ of the installation 21, the section of FIG. 5 being shown diagrammatically by the straight line segments VV in FIG. 4.
- the installation 21 is arranged outside the drum 11.
- This installation 21 comprises a reservoir 22 constituted by a ceramic crucible, for example made of zircon or alumina.
- the crucible 22 rests on the insulating spacer 23 made for example of aluminous refractory concrete.
- Around the crucible 22 is arranged a cylindrical jacket 24 made for example of zircon.
- a stuffing 25 in the form of compacted powder of alumina.
- the jacket 24 is surrounded by the induction coil 26 capable of melting the amorphizable alloy 4 based on iron by passage of electric current.
- the assembly of the crucible 22, the spacer 23, the jacket 24 and the packing 25 is surrounded by an enclosure 27 comprising two walls 28, 29, made of steel, a coolant 30, for example water, being disposed between these walls 28, 29.
- a part 31, in the form of an inverted cup, is disposed in the opening 32 passing through the bottom 33 of the crucible 22 and the bottom 34 of the enclosure 27.
- the spacer 23 and the jacket 24 rest directly on the bottom 34 of the enclosure 27.
- the cup 31 is made for example of zircon.
- the top 35 of the cup 31 is crossed by a nozzle 36, made for example of zirconia or alumina, the part 31 therefore serving as a support for the nozzle 36.
- the opening 37 of this nozzle 36 is disposed along the axis yy ′ which is the axis of the opening 32 and the axis of the installation 21.
- the installation 21 also comprises a device 38 comprising the flange 39 which makes it possible to apply this device against the enclosure 27.
- the device 38 also comprises the cylindrical enclosure 40, and the annular rim 41 on which is applied a part 42 in the form of an inverted cup, the top 43 of which has an opening 44 situated under the opening 37 of the nozzle 36 and having the axis yy ′.
- the flange 39, the cylinder 40 and the flange 41 are made for example of steel and the part 42 is made of ceramic, for example of zircon.
- the internal volume 45 of the cylinder 40, under the rim 41, and the internal volume 46 of the cup 42 communicate with each other through the opening 47 and together constitute the enclosure 48.
- the seal at the flange 39 is ensured by an O-ring 49, for example made of rubber.
- the operation of the device 20 is as follows: The passage of electric current through the induction coil 26 allows the amorphizable alloy 4 placed in the crucible 22 to be melted. This molten alloy 4 allows the upper part of a steel ferrule 50 previously disposed around the support to be melted 31 between this support 31 on the one hand and the crucible 22, the enclosure 27 and the spacer 23 on the other hand. This partial melting of the ferrule 50 forms the steel seal 51 between the support 31 and the crucible 22. This seal 51 combined with the O-ring 49 ensures good sealing of the installation 21.
- the argon 5 under pressure, placed in the crucible 22 above the alloy 4 allows the extrusion of this alloy, through the nozzle 36, in the form of a jet 7 which passes through the opening 44 of the part 42 along the axis yy ′ and crosses the interior volumes 46 and 45, that is to say the enclosure 48 to finally leave the installation 21 and reach the layer 8 of water 9 where it solidifies very quickly to give the wire 12.
- the speed quenching is, in known manner, of the order of 105 ° C / second, the water 9 being cooled by a known refrigeration system arranged around the drum 11, this system not being shown in the drawing for the purpose of simplification.
- a small amount of hydrogen 52 is made to arrive through the opening 53 made in the cylinder 40 above the rim 41.
- the hydrogen 52 thus fills the space 54 which is outside the cup 42 between it ci and the support 31, the cylinder 40 and the rim 41.
- the hydrogen 52 is thus thus in contact with the nozzle 36.
- the jet 7 In order for the jet 7 to be able to undergo very rapid quenching in the layer 8 so as to obtain an amorphous wire 12, it is essential that the jet 7 remains liquid throughout the entire length L, that is to say that the jet 7 must be at a temperature higher than the melting temperature of the alloy 4 during the impact of the jet 7 with water 9.
- the hydrogen 52 and the oxidizing gas mixture 55 must therefore not significantly cool the jet 7, the solidification being carried out only within the layer 8.
- the alloy 4 contains silicon and the stabilization of the jet 7 is carried out by oxidation of the silicon, the silicon content in the alloy being greater than 0.2% ( % atomic).
- the jet 7 flows for example from top to bottom, as in the device 20 described above, in a vertical direction, and the axis xx 'of the drum 11, and therefore the generatrices of the water cylinder 80 limiting the layer 8 in the direction of the axis xx ', make an angle of 40 to 70 ° with the vertical.
- the jet 7 it is possible to envisage causing the jet 7 to flow in other directions, at the outlet of the installation 21, for example horizontally or from bottom to top.
- the jet 7 is continuous throughout its journey from the nozzle 36 to the layer 8, without the formation of drops.
- This combined with the very rapid cooling achieved thanks to the layer 8, makes it possible to obtain an amorphous wire 12 whose circular section with a diameter of 160 ⁇ m has a regular shape over its length.
- the crucible 22 has been shown as a tank in which the alloy 4 is fused, but one could use a tank supplied with alloy 4 previously melted, this supply being for example continuous.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Continuous Casting (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Wire Processing (AREA)
- Metal Extraction Processes (AREA)
- Soft Magnetic Materials (AREA)
- Coating With Molten Metal (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Ropes Or Cables (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT89116705T ATE92805T1 (de) | 1988-09-21 | 1989-09-09 | Verfahren und vorrichtungen zum erzeugen von draehten aus amorphen metallegierungen. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8812423A FR2636552B1 (fr) | 1988-09-21 | 1988-09-21 | Procedes et dispositifs pour obtenir des fils en alliages metalliques amorphes |
| FR8812423 | 1988-09-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0360104A1 EP0360104A1 (fr) | 1990-03-28 |
| EP0360104B1 true EP0360104B1 (fr) | 1993-08-11 |
Family
ID=9370293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89116705A Expired - Lifetime EP0360104B1 (fr) | 1988-09-21 | 1989-09-09 | Procédés et dispositifs pour obtenir des fils en alliages métalliques amorphes |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5000251A (es) |
| EP (1) | EP0360104B1 (es) |
| JP (1) | JPH02117752A (es) |
| KR (1) | KR0125762B1 (es) |
| CN (1) | CN1036570C (es) |
| AT (1) | ATE92805T1 (es) |
| AU (1) | AU616305B2 (es) |
| BR (1) | BR8904774A (es) |
| CA (1) | CA1336125C (es) |
| DE (1) | DE68908310T2 (es) |
| ES (1) | ES2042916T3 (es) |
| FR (1) | FR2636552B1 (es) |
| OA (1) | OA09092A (es) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2672522A1 (fr) * | 1991-02-08 | 1992-08-14 | Michelin & Cie | Procede et dispositif pour obtenir en continu un fil par extrusion dans un liquide. |
| FR2673551B1 (fr) * | 1991-03-05 | 1993-06-11 | Siderurgie Fse Inst Rech | Procede et dispositif de coulee continue de fil metallique de faible diametre directement a partir de metal liquide. |
| FR2676946A1 (fr) * | 1991-05-27 | 1992-12-04 | Michelin & Cie | Procede et dispositif pour obtenir un fil en alliage metallique amorphe a base de fer. |
| CN1073479C (zh) * | 1996-05-09 | 2001-10-24 | 冶金工业部包头稀土研究院 | 晶态和非晶态稀土金属合金细丝及其生产方法和装置 |
| KR20020000965A (ko) * | 2000-06-23 | 2002-01-09 | 신영주 | 안전밸브 |
| US7077186B2 (en) * | 2003-12-11 | 2006-07-18 | Novelis Inc. | Horizontal continuous casting of metals |
| US7589266B2 (en) * | 2006-08-21 | 2009-09-15 | Zuli Holdings, Ltd. | Musical instrument string |
| CN101532117B (zh) * | 2008-03-12 | 2010-12-15 | 中国科学院金属研究所 | 一种连续金属玻璃纤维的制备方法 |
| FR2956410B1 (fr) * | 2010-02-16 | 2012-01-27 | Snecma | Dispositif pour l'obtention de fibres ceramiques enduites par voie liquide d'une gaine metallique epaisse |
| KR102800631B1 (ko) * | 2023-04-27 | 2025-04-29 | (주)씨큐파이버 | 유리냉각을 통한 고융점 합금 비정질 와이어의 제조 방법 및 장치 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3845805A (en) * | 1972-11-14 | 1974-11-05 | Allied Chem | Liquid quenching of free jet spun metal filaments |
| FR2367563A1 (fr) * | 1976-10-15 | 1978-05-12 | Michelin & Cie | Procede et installation |
| FR2367562A1 (fr) * | 1976-10-15 | 1978-05-12 | Michelin & Cie | Perfectionnements a la fabrication de fil metallique par coulee continue dans un fluide refroidisseur |
| US4339255A (en) * | 1980-09-09 | 1982-07-13 | Energy Conversion Devices, Inc. | Method and apparatus for making a modified amorphous glass material |
| EP0039169B1 (en) * | 1980-04-17 | 1985-12-27 | Tsuyoshi Masumoto | Amorphous metal filaments and process for producing the same |
| JPS58173059A (ja) * | 1982-03-03 | 1983-10-11 | Unitika Ltd | 金属細線の製造方法 |
| JPS60247445A (ja) * | 1984-05-21 | 1985-12-07 | Unitika Ltd | 金属細線の連続製造方法及び装置 |
-
1988
- 1988-09-21 FR FR8812423A patent/FR2636552B1/fr not_active Expired - Fee Related
-
1989
- 1989-09-09 AT AT89116705T patent/ATE92805T1/de not_active IP Right Cessation
- 1989-09-09 EP EP89116705A patent/EP0360104B1/fr not_active Expired - Lifetime
- 1989-09-09 ES ES89116705T patent/ES2042916T3/es not_active Expired - Lifetime
- 1989-09-09 DE DE89116705T patent/DE68908310T2/de not_active Expired - Fee Related
- 1989-09-15 US US07/407,860 patent/US5000251A/en not_active Expired - Lifetime
- 1989-09-20 CN CN89107397A patent/CN1036570C/zh not_active Expired - Fee Related
- 1989-09-20 AU AU41533/89A patent/AU616305B2/en not_active Ceased
- 1989-09-21 KR KR1019890013561A patent/KR0125762B1/ko not_active Expired - Fee Related
- 1989-09-21 CA CA000612315A patent/CA1336125C/fr not_active Expired - Fee Related
- 1989-09-21 OA OA59648A patent/OA09092A/xx unknown
- 1989-09-21 BR BR898904774A patent/BR8904774A/pt not_active IP Right Cessation
- 1989-09-21 JP JP1246221A patent/JPH02117752A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR0125762B1 (ko) | 1997-12-26 |
| CA1336125C (fr) | 1995-07-04 |
| FR2636552A1 (fr) | 1990-03-23 |
| DE68908310T2 (de) | 1993-12-16 |
| OA09092A (fr) | 1991-10-31 |
| CN1036570C (zh) | 1997-12-03 |
| AU4153389A (en) | 1990-03-29 |
| DE68908310D1 (de) | 1993-09-16 |
| ATE92805T1 (de) | 1993-08-15 |
| BR8904774A (pt) | 1990-05-01 |
| AU616305B2 (en) | 1991-10-24 |
| FR2636552B1 (fr) | 1990-11-02 |
| US5000251A (en) | 1991-03-19 |
| JPH02117752A (ja) | 1990-05-02 |
| EP0360104A1 (fr) | 1990-03-28 |
| ES2042916T3 (es) | 1993-12-16 |
| CN1041302A (zh) | 1990-04-18 |
| KR900004435A (ko) | 1990-04-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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| 17P | Request for examination filed |
Effective date: 19890909 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
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| 17Q | First examination report despatched |
Effective date: 19911017 |
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| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
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