EP0253841B1 - Process for producing transition metal powders by electrolysis in baths of molten salts - Google Patents
Process for producing transition metal powders by electrolysis in baths of molten salts Download PDFInfo
- Publication number
- EP0253841B1 EP0253841B1 EP87900658A EP87900658A EP0253841B1 EP 0253841 B1 EP0253841 B1 EP 0253841B1 EP 87900658 A EP87900658 A EP 87900658A EP 87900658 A EP87900658 A EP 87900658A EP 0253841 B1 EP0253841 B1 EP 0253841B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- bath
- electrolysis
- process according
- voltage
- 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 16
- 239000000843 powder Substances 0.000 title claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 7
- 150000003839 salts Chemical class 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract 3
- 150000004820 halides Chemical class 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 3
- 150000001340 alkali metals Chemical class 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052719 titanium Inorganic materials 0.000 abstract description 8
- 239000010936 titanium Substances 0.000 abstract description 8
- 229910052735 hafnium Inorganic materials 0.000 abstract description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000000737 periodic effect Effects 0.000 abstract description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 1
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004845 hydriding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
Definitions
- the present invention relates to the preparation of powders of transition metals by electrolysis of their halides in baths of molten salts.
- the studies undertaken for the development of the invention were carried out in a cell comprising, on the one hand a metal tank containing the molten bath, on the other hand a also metallic cover ensuring the sealing of the system and having various orifices allowing, among other things, the sealed and isolated passage of the anode and cathode devices immersed in the bath, the supply of this bath with the halide of the metal to be produced and the extraction of the halogen released at the anode.
- the fluorine / metal ratio is between 3 and 20. However, preferably, the best results are obtained with the range of values between 6 and 12.
- the anode device further comprises a diaphragm which separates the bath into two compartments, an anode compartment which contains only traces of Titanium in solution, and a cathode compartment in which the content of dissolved Titanium is kept constant by a continuous supply device.
- the bath consists of an equimolecular mixture of potassium chlorides and sodium molten at 750 ° C.
- the halide introduced is titanium tetrachloride.
- the content of titanium dissolved in the bath is 4%.
- the deposition voltage of titanium measured by drawing the voltage / current curve, is 2.15 V.
- the easiest to reduce of the alkali in this case, the sodium is 3.2 V.
- the deposits collected on the cathode are in the form of well crystallized dendrites which can reach several centimeters and which meet the following analysis in ppm:
- the electrical efficiency is greater than 90%.
- the electrical efficiency is greater than 85%.
- This example relates to Hafnium.
- the halide introduced this time being hafnium tetrachloride, at the content of 25%, under normal conditions.
- electrolysis i.e. with a current density of 1.0 A / cm 2
- the deposition voltage of Hafnium is 2.2 V. and deposits are obtained in the form of relatively massive dendrites ( cauliflower appearance) with an electrical efficiency greater than 95%.
- F- ions are introduced into the bath by means of the addition of sodium fluoride for example, so that the fluorine / Hafnium molecular ratio is equal to 12, under the same electrolysis conditions, the voltage of Hafnium deposit goes to 2.90 V and after washing the deposit, a powder is obtained which passes almost entirely through a sieve of 200 microns opening and which meets the following analysis in ppm:
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Length Measuring Devices By Optical Means (AREA)
Abstract
Description
La présente invention est relative à l'élaboration de poudres des métaux de transition par électrolyse de leurs halogénures en bains de sels fondus.The present invention relates to the preparation of powders of transition metals by electrolysis of their halides in baths of molten salts.
Dans ce qui va suivre:
- 1. on entend par métaux de transition, tout métal appartenant aux collones IVa, Va, Via de la classification périodique des éléments.
- 2. on entend par poudre, une substance solide, finement divisée et comportant des grains de dimension allant de quelques fractions de micron à 200 microns environ.
- 1. transition metals are understood to mean any metal belonging to the columns IVa, Va, Via of the periodic table.
- 2. powder means a solid substance, finely divided and containing grains ranging in size from a few micron fractions to about 200 microns.
L'application des méthodes de mise en forme de la métallurgie des poudres, en raison des importantes économies de matières qu'elles permettent, suscite le plus haut intérêt pour des métaux coûteux tels que les métaux de transition. La difficulté principale rencontrée pour cette application est celle de l'élaboration de poudres de qualité convenable.The application of powder metallurgy shaping methods, because of the significant material savings they allow, arouses the greatest interest in expensive metals such as transition metals. The main difficulty encountered for this application is that of developing powders of suitable quality.
Les procédés utilisés actuellement dans ce but sont divers.The methods currently used for this purpose are diverse.
On peut citer:
- à partir des métaux massifs:
- 1. le procédé par hydruration, broyage et déshydruration.
- 2. les procédés par fusion à l'arc ou au faisceau d'électrons et pulvérisation par centrifugation. à partir d'un oxyde ou d'un sel:
- from solid metals:
- 1. the hydriding, grinding and dehydrating process.
- 2. the processes by arc or electron beam fusion and sputtering by centrifugation. from an oxide or a salt:
le procédé par réduction par hydrogène à très haute température. Ces procédés nécessitent, en général, des installations importantes, complexes et coûteuses: par ailleurs, ils ne conduisent pas toujours à des poudres convenables, soit du point de vue purété, soit du point de vue granulométrie ou forme des grains.the process by reduction by hydrogen at very high temperature. These processes generally require large, complex and costly installations: moreover, they do not always lead to suitable powders, either from the purity point of view, or from the particle size or grain form point of view.
Les études entreprises pour la mise au point de l'invention ont été effectuées dans une cellule comportant, d'une part une cuve métallique contenant le bain fondu, d'autre part un couvercle également métallique assurant l'étanchéité du système et présentant divers orifices permettant, entre autre, le passage étanche et isolé des dispositifs anodiques et cathodiques plongeant dans le bain, l'alimentation de ce bain en halogénure du métal à produire et l'extraction de l'halogène dégagé à l'anode.The studies undertaken for the development of the invention were carried out in a cell comprising, on the one hand a metal tank containing the molten bath, on the other hand a also metallic cover ensuring the sealing of the system and having various orifices allowing, among other things, the sealed and isolated passage of the anode and cathode devices immersed in the bath, the supply of this bath with the halide of the metal to be produced and the extraction of the halogen released at the anode.
En général, dans le bain, le rapport fluor/métal est compris entre 3 et 20. Mais, de préférence, les meilleurs résultats sont obtenus avec la fourchette de valeurs comprise entre 6 et 12.In general, in the bath, the fluorine / metal ratio is between 3 and 20. However, preferably, the best results are obtained with the range of values between 6 and 12.
Les exemples suivants ilustrent l'application du procédé suivant les deux modes décrits ci-dessus.The following examples illustrate the application of the method according to the two modes described above.
Cet exemple est relatif au Titane. Dans ce cas, le dispositif anodique comporte en outre un diaphragme qui sépare le bain en deux compartiemnts, un compartiment anodique qui ne contient que des traces de Titane en solution, et un compartiment cathodique dans lequel la teneur en Titane dissous est maintenue constante grâce à un dispositif d'alimentation continue.This example relates to Titanium. In this case, the anode device further comprises a diaphragm which separates the bath into two compartments, an anode compartment which contains only traces of Titanium in solution, and a cathode compartment in which the content of dissolved Titanium is kept constant by a continuous supply device.
Le bain est constitué par un mélange équimoléculaire de chlorures de potassium et de sodium fondu à 750°C.The bath consists of an equimolecular mixture of potassium chlorides and sodium molten at 750 ° C.
L'halogénure introduit est le tétrachlorure de titane.The halide introduced is titanium tetrachloride.
Dans les conditions habituelles d'électrolyse, la teneur en titane dissous dans le bain est de 4%.Under the usual electrolysis conditions, the content of titanium dissolved in the bath is 4%.
Avec une densité de courant cathodique initiale de 1,0 A/cm2, la tension de dépôt du titane, mesurée par tracé de la courbe tension/courant est de 2,15 V., celle de l'alcalin le plus facile à réduire, en l'occurence, le sodium, est de 3,2 V.With an initial cathodic current density of 1.0 A / cm 2 , the deposition voltage of titanium, measured by drawing the voltage / current curve, is 2.15 V. The easiest to reduce of the alkali , in this case, the sodium is 3.2 V.
Les dépôts recueillis sur la cathode se présentent sous forme de dendrites bien cristallisées pouvant atteindre plusieurs centimètres et répondant à l'analyse suivante en ppm:
Le rendement électrique est supérieur à 90%.The electrical efficiency is greater than 90%.
Si l'on abaisse la teneur en titane dans le compartiment cathodique à 0,1 %, dans les mêmes conditions de densité de courant, la tension de dépôt du titane passe à 2,9 V, celle de l'alcalin restant égale à 3,2 V et l'on recueille à la cathode une sorte de feutre gris constitué de fines dendrites entremêlées qui donne finalement après lavage à l'eau une poudre passant pratiquement entièrement au tamis de 100 microns d'ouverture de maille et répondant à l'analyse suivante en ppm:
Le rendement électrique est supérieure à 85%.The electrical efficiency is greater than 85%.
Dans la même cellule que dans l'exemple 1, mais sans diaphragme anodique, toujours avec le bain NaCI/KCI équimoléculaire, l'halogénure introduit étant cette fois le tétrachlorure de hafnium, à la teneur de 25%, dans les conditions normales d'électrolyse, c'est-à-dire avec une densité de courant de 1,0 A/cm2, la tension de dépôt du Hafnium est de 2,2 V. et l'on obtient des dépôts sous forme de dendrites relativement massives (aspect de chou-fleur) avec un rendement électrique supérieur à 95%.In the same cell as in Example 1, but without an anode diaphragm, still with the equimolecular NaCl / KCl bath, the halide introduced this time being hafnium tetrachloride, at the content of 25%, under normal conditions. electrolysis, i.e. with a current density of 1.0 A / cm 2 , the deposition voltage of Hafnium is 2.2 V. and deposits are obtained in the form of relatively massive dendrites ( cauliflower appearance) with an electrical efficiency greater than 95%.
L'analyse de ces dépôts donne les résultats suivants en ppm:
Si l'on introduit dans le bain des ions F- au moyen d'une addition de fluorure de sodium par exemple, de sorte que le rapport moléculaire fluor/Hafnium soit égal à 12, dans les mêmes conditions d'électrolyse, la tension de dépôt du Hafnium passe à 2,90 V et l'on obtient après lavage du dépôt, une poudre passant pratiquement entièrement au tamis de 200 microns d'ouverture et répondant à l'analyse suivante en ppm:
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8600390A FR2592664B1 (en) | 1986-01-06 | 1986-01-06 | PROCESS FOR THE PREPARATION OF TRANSITION METAL POWDERS BY ELECTROLYSIS IN MOLTEN SALT BATHS |
| FR8600390 | 1986-01-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0253841A1 EP0253841A1 (en) | 1988-01-27 |
| EP0253841B1 true EP0253841B1 (en) | 1990-05-23 |
Family
ID=9331054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87900658A Expired - Lifetime EP0253841B1 (en) | 1986-01-06 | 1987-01-05 | Process for producing transition metal powders by electrolysis in baths of molten salts |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4770750A (en) |
| EP (1) | EP0253841B1 (en) |
| JP (1) | JPS63500187A (en) |
| CA (1) | CA1287814C (en) |
| DE (1) | DE3762890D1 (en) |
| FR (1) | FR2592664B1 (en) |
| WO (1) | WO1987004193A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991001942A1 (en) * | 1989-08-01 | 1991-02-21 | Australian Copper Company Pty. Ltd. | Production of copper compounds |
| GB2376241B (en) * | 2000-02-22 | 2004-03-03 | Qinetiq Ltd | Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms |
| WO2005111272A1 (en) * | 2004-04-06 | 2005-11-24 | Iox Co., Ltd. | Process for producing microparticles by plasma-induced electrolysis |
| PL377451A1 (en) * | 2005-10-05 | 2007-04-16 | Instytut Wysokich Ciśnień PAN | Methods of reaction leading, chemical reactor |
| EP2794943B8 (en) | 2011-12-22 | 2019-07-10 | Universal Achemetal Titanium, LLC | A method for extraction and refining of titanium |
| US10400305B2 (en) | 2016-09-14 | 2019-09-03 | Universal Achemetal Titanium, Llc | Method for producing titanium-aluminum-vanadium alloy |
| RU2763465C2 (en) | 2017-01-13 | 2021-12-29 | ЮНИВЕРСАЛ АКЕМЕТАЛ ТИТАНИУМ, ЭлЭлСи | TITANIUM LIGATURE FOR ALLOYS BASED ON Ti-Al |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2951021A (en) * | 1952-03-28 | 1960-08-30 | Nat Res Corp | Electrolytic production of titanium |
| GB736567A (en) * | 1952-07-03 | 1955-09-07 | Horizons Titanium Corp | Improvements in production of metallic titanium |
| FR1265427A (en) * | 1960-06-03 | 1961-06-30 | Ciba Geigy | Process for the electrolytic production of the metals niobium and tantalum |
-
1986
- 1986-01-06 FR FR8600390A patent/FR2592664B1/en not_active Expired - Fee Related
-
1987
- 1987-01-05 DE DE8787900658T patent/DE3762890D1/en not_active Expired - Fee Related
- 1987-01-05 JP JP62500612A patent/JPS63500187A/en active Granted
- 1987-01-05 CA CA000526634A patent/CA1287814C/en not_active Expired - Lifetime
- 1987-01-05 US US07/099,317 patent/US4770750A/en not_active Expired - Fee Related
- 1987-01-05 WO PCT/FR1987/000001 patent/WO1987004193A1/en not_active Ceased
- 1987-01-05 EP EP87900658A patent/EP0253841B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| WO1987004193A1 (en) | 1987-07-16 |
| EP0253841A1 (en) | 1988-01-27 |
| DE3762890D1 (en) | 1990-06-28 |
| CA1287814C (en) | 1991-08-20 |
| JPH0312156B2 (en) | 1991-02-19 |
| JPS63500187A (en) | 1988-01-21 |
| US4770750A (en) | 1988-09-13 |
| FR2592664B1 (en) | 1990-03-30 |
| FR2592664A1 (en) | 1987-07-10 |
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