EP0005674A2 - Process of manufacturing a dimensionally stable anode - Google Patents
Process of manufacturing a dimensionally stable anode Download PDFInfo
- Publication number
- EP0005674A2 EP0005674A2 EP79400313A EP79400313A EP0005674A2 EP 0005674 A2 EP0005674 A2 EP 0005674A2 EP 79400313 A EP79400313 A EP 79400313A EP 79400313 A EP79400313 A EP 79400313A EP 0005674 A2 EP0005674 A2 EP 0005674A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- core
- electrolytic bath
- high temperature
- coating
- metal
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
Definitions
- the present invention relates, in general, to electrolysis cells and relates more particularly to an anode electrode stable in dimensions, of the type comprising a core of electroconductive material and an electrocatalytic conductive coating.
- the invention also relates to a method of manufacturing such an electrode.
- electrolytic cells in which the anode is constituted by a core of a metal called stop metal, of the type used for rectifiers with stop layer are expensive and require difficult and expensive machining.
- stop metals which include in particular titanium, tantalum, columbium, zirconium, moybdenum and tungsten, are expensive and require difficult and expensive machining.
- the core of the anode can also be produced from oxides of stop metals.
- the anode electrodes of the aforementioned type consisting almost entirely of stop metals, noble metals or oxides of these metals, are particular stable in size over time.
- a drawback results from the difficulty of treatment, in particular of mechanical treatment, of such materials.
- One of the aims of the present invention consists precisely in making it possible to produce anodes at a reduced cost and in a simplified manner, while offering the possibility of improving the shape of the anodes constructed, without appreciably affecting their electrical properties.
- an anode electrode stable in dimensions of the type comprising a core of electroconductive material and an electrocatalytic conductive coating, characterized in that an electroconductive core is first produced by molding. starting from a common metal melting at high temperature, such as iron, an iron alloy, aluminum, copper, in that said core is then introduced into a first electrolytic bath melted at high temperature, temperature, consisting of a mixture of alkali halides and stop metal halides, to form a first conductive coating on the core, and in that said core provided with its first coating is then introduced into a second electrolytic bath comprising noble metals to form a second electrocatalytic conductive coating on the core provided with its first conductive coating.
- a common metal melting at high temperature such as iron, an iron alloy, aluminum, copper
- the second electrolytic bath can advantageously be constituted by a molten electrolytic bath at high temperature, consisting of a mixture of halides alkali and noble metal halides or a mixture of alkali halides and noble metal halides and stop metals.
- the second electrolytic bath can also optionally consist of an aqueous solution of noble metal, such as platinum, ruthenium, iridium, palladium.
- noble metal such as platinum, ruthenium, iridium, palladium.
- the core is made of iron or ferrous alloy, aluminum or aluminum alloy, copper or copper alloy, a coating of stop metals or metal oxides d 'stop, then a second coating of noble metals such as platinum or oxides of these noble metals or noble metals associated with stop metals such as titanium, the mechanical and electrical qualities of the anode remain excellent compared to anode electrodes, the core of which is made entirely of stop metal such as titanium or tantalum.
- the advantageous characteristic is the formation of the molded core based on iron or ferrous alloy by molding molten metals.
- the second electrocatalytic conductive coating can be produced from a mixture of alkali halides and either halides of a noble metal or of several noble metals, or halides of noble metals and stop metals.
- stop metal is meant a metal of the type used for rectifiers with a stop layer. Titanium, tantalum, columbium, zirconium, molybdenum and tungsten belong to this family.
- the operations of coating the electroconductive core are carried out in an inert atmosphere such as an argon or helium atmosphere.
- the temperature of the molten electrolytic baths is between 300 and 1000 ° C, this temperature naturally depending on the type of core and the metals to be treated.
- the electrode provided with its two coatings is then subjected to an oxidation heat treatment.
- an anode core is produced by melting and molding inexpensive common metals, such as iron or an iron alloy, aluminum, copper or alloys of these metals.
- the core could also be made from a metal such as. iron, for example semi-worked.
- the molding technique makes it easier to produce anodes of very different geometries.
- the core of the anode then receives a cathodic electrolytic deposit of a stop metal, such as titanium, tantalum or tungsten.
- a stop metal such as titanium, tantalum or tungsten.
- This deposit makes it possible to coat the core of the anode with a layer of stop metal, the thickness of which can be very reduced, for example less than 3 mm.
- stop metal used are thus very reduced, although the electrode is coated over its entire surface and therefore has interesting electrical and mechanical qualities.
- the molten electrolytic bath allowing the deposition of a stop metal is a high temperature bath comprising a mixture of alkali chlorides, such as sodium chloride, potassium chloride, lithium chloride, or alkaline fluorides, such that sodium florure and potassium fluoride or fluorides and chlorides of stop metals or compounds of stop metals, such as tungsten compounds.
- alkali chlorides such as sodium chloride, potassium chloride, lithium chloride, or alkaline fluorides, such that sodium florure and potassium fluoride or fluorides and chlorides of stop metals or compounds of stop metals, such as tungsten compounds.
- Anodic corrosion of the stop metal and of the mixture of molten chlorides can thus take place with the intervention of tetrachloride of the stop metal and the intervention of fluorinated compounds of the stop metal.
- the coating of the iron-based core is carried out in an inert atmosphere of rare gases such as argon or helium.
- the melting temperature of the electrolytic bath can be between approximately 300 and 1000 ° C.
- the density of the anode currents can reach 10 kA / m 2 using for the cathodic deposition of stop metal a soluble anode having the same composition as that of the stop metal to be deposited.
- the deposit is obtained at anode and cathode potentials controlled and at anode and cathode current density always controlled with cell voltages between 0 and 7 volts.
- the current densities can be, for example, from 100 to 700 A / m 2 at the cathode and from 10 to 90 A / m 2 at the anode.
- the second coating can be carried out using the same technique as for the first coating, that is to say using a molten electrolytic bath at high temperature, a mixture of alkali halides and noble metal halides, which may optionally be combined with stop metal halides.
- the noble metal can still be deposited by aqueous baths, ie galvanic.
- the present invention lends itself well to the manufacture of anodes of very diverse shapes, in particular of anodes provided with several electrode connections coupled to the anode barrier, since in particular the molding technique makes it possible to form cores with the most varied shapes. .
- An anode produced according to the present invention has excellent mechanical and chemical resistance, especially to corrosion, including for temperatures above normal.
Abstract
Description
La présente invention se rapporte, d'une manière générale, aux cellules d'électrolyse et concerne plus particulièrement une électrode anodique stable en dimensions, du type comprenant une âme en matière électroconductrice et un revêtement conducteur électrocatalytique. L'invention concerne également un procédé de fabrication d'une telle électrode.The present invention relates, in general, to electrolysis cells and relates more particularly to an anode electrode stable in dimensions, of the type comprising a core of electroconductive material and an electrocatalytic conductive coating. The invention also relates to a method of manufacturing such an electrode.
On connait, à côté de cellules électrolytiques classiques mettant en oeuvre des anodes en graphite, des cellules électrolytiques dans lesquelles l'anode est constituée par une âme en un métal dit métal d'arrêt, du type utilisé pour les redresseurs à couche d'arrêt. De tels métaux d'arrêt, qui comprennent notamment le titane, le tantale, le colombium, le zirconium, le moybdène et le tungstène, sont d'un prix élevé et nécessitent un usinage difficile et couteux. L'âme de l'anode peut encore être réalisée à partir d'oxydes de métaux d'arrêt.We know, next to conventional electrolytic cells using graphite anodes, electrolytic cells in which the anode is constituted by a core of a metal called stop metal, of the type used for rectifiers with stop layer . Such stop metals, which include in particular titanium, tantalum, columbium, zirconium, moybdenum and tungsten, are expensive and require difficult and expensive machining. The core of the anode can also be produced from oxides of stop metals.
Il est également connu de revêtir une anode du type précité à l'aide d'une couche conductrice électrocatalytique constituée par exemple par un mélange d'oxydes métalliques de métaux nobles ou de métaux d'arrêt.It is also known to coat an anode of the aforementioned type using an electrocatalytic conductive layer constituted for example by a mixture of metallic oxides of noble metals or of stop metals.
Les électrodes anodiques du type précité, constituées pratiquement intégralement de métaux d'arrêt, métaux nobles ou oxydes de ces métaux, sont particulièrement stables en dimensions au cours du temps. Toutefois, outre le coût élevé du matériau de base constituant de telles anodes, un inconvénient résulte de la difficulté de traitement, notamment de traitement mécanique, de tels matériaux. Or, pour que les anodes résistent, au cours du fonctionnement de l'électrolyse, aux tensions notamment thermiques et mécaniques, il est essentiel que la configuration géométrique des anodes soit déterminée avec précision. Les anodes du type connu ne permettent pas de réaliser facilement des configurations géométriques complexes.The anode electrodes of the aforementioned type, consisting almost entirely of stop metals, noble metals or oxides of these metals, are particular stable in size over time. However, in addition to the high cost of the base material constituting such anodes, a drawback results from the difficulty of treatment, in particular of mechanical treatment, of such materials. However, for the anodes to resist, during the operation of the electrolysis, in particular thermal and mechanical voltages, it is essential that the geometrical configuration of the anodes is determined with precision. Anodes of the known type do not allow complex geometric configurations to be easily carried out.
Un des buts de la présente invention consiste précisément à permettre la réalisation d'anodes à un coût réduit et de façon simplifiée, tout en offrant la possibilité d'améliorer la forme des anodes construites, sans affecter sensiblement leurs propriétés électriques.One of the aims of the present invention consists precisely in making it possible to produce anodes at a reduced cost and in a simplified manner, while offering the possibility of improving the shape of the anodes constructed, without appreciably affecting their electrical properties.
Ces buts sont atteints grâce à un procédé de fabrication d'une électrode anodique stable en dimensions, du type comprenant une âme en matière électroconductrice et un revêtement conducteur électrocatalytique, caractérisé en ce que l'on réalise d'abord une âme électroconductrice, par moulage à partir d'un métal commun fondant à haute température, tel que du fer, un alliage de fer, de l'aluminium, du cuivre, en ce que l'on introduit ensuite ladite âme dans un premier bain électrolytique fondu à haute., température, constitué d'un mélange d'halogénures alcalins et d'halogénures de métaux d'arrêt, pour former un premier revêtement conducteur sur l'âme, et en ce que l'on introduit ensuite ladite âme munie de son premier revêtement dans un second bain électrolytique comprenant des métaux nobles pour former un second revêtement conducteur électrocatalytique sur l'âme munie de son premier revêtement conducteur.These objects are achieved by a method of manufacturing an anode electrode stable in dimensions, of the type comprising a core of electroconductive material and an electrocatalytic conductive coating, characterized in that an electroconductive core is first produced by molding. starting from a common metal melting at high temperature, such as iron, an iron alloy, aluminum, copper, in that said core is then introduced into a first electrolytic bath melted at high temperature, temperature, consisting of a mixture of alkali halides and stop metal halides, to form a first conductive coating on the core, and in that said core provided with its first coating is then introduced into a second electrolytic bath comprising noble metals to form a second electrocatalytic conductive coating on the core provided with its first conductive coating.
Le second bain électrolytique peut avantageusement être constitué par un bain électrolytique fondu à haute température, constitué d'un mélange d'halogénures alcalins et d'halogénures de métaux nobles ou d'un mélange d'halogénures alcalins et d'halogénures de métaux nobles et de métaux d'arrêt.The second electrolytic bath can advantageously be constituted by a molten electrolytic bath at high temperature, consisting of a mixture of halides alkali and noble metal halides or a mixture of alkali halides and noble metal halides and stop metals.
Le second bain électrolytique peut encore éventuellement être constitué par une solution aqueuse de métal noble, tel que le platine, le ruthénium, l'iridium, le palladium.The second electrolytic bath can also optionally consist of an aqueous solution of noble metal, such as platinum, ruthenium, iridium, palladium.
Ainsi, contrairement aux anodes stabilisées en dimensions de type classique, on utilise, pour le coeur de l'anode, un métal ou un alliage de métaux peu couteux et facilement travaillable par moulage. Le coût de fabrication est ainsi très réduit, tandis que la souplesse de fabrication est grandement améliorée.Thus, unlike anodes stabilized in dimensions of the conventional type, an inexpensive metal or metal alloy which is easily worked by molding is used for the core of the anode. The manufacturing cost is thus very reduced, while the manufacturing flexibility is greatly improved.
De façon surprenante, si l'on réalise sur l'à- me en fer ou alliage ferreux, en aluminium ou alliage d'aluminium, en cuivre ou alliage de cuivre, un revêtement de métaux d'arrêt ou d'oxydes de métaux d'arrêt, puis un second revêtement de métaux nobles tels que du platine ou des oxydes de ces métaux nobles ou de métaux nobles associés à des métaux d'arrêt tels que le titane, les qualités mécaniques et électriques de l'anode restent excellentes par rapport aux électrodes anodiques dont le coeur est réalisé entièrement en métal d'arrêt tel que le titane ou le tantale.Surprisingly, if the core is made of iron or ferrous alloy, aluminum or aluminum alloy, copper or copper alloy, a coating of stop metals or metal oxides d 'stop, then a second coating of noble metals such as platinum or oxides of these noble metals or noble metals associated with stop metals such as titanium, the mechanical and electrical qualities of the anode remain excellent compared to anode electrodes, the core of which is made entirely of stop metal such as titanium or tantalum.
La formation de l'âme moulée à base de fer ou d'alliage ferreux par un moulage de métaux fondus constitue une caractéristique avantageuse.The advantageous characteristic is the formation of the molded core based on iron or ferrous alloy by molding molten metals.
Le second revêtement conducteur électrocatalytique peut être réalisé à partir d'un mélange d'halogénures alcalins et soit d'halogénures d'un métal noble ou de plusieurs métaux nobles, soit d'halogénures de métaux nobles et de métaux d'arrêt.The second electrocatalytic conductive coating can be produced from a mixture of alkali halides and either halides of a noble metal or of several noble metals, or halides of noble metals and stop metals.
Par métal d'arrêt, il faut comprendre un métal du type utilisé pour des redresseurs à couche d'arrêt. Le titane, le tantale, le colombium, le zirconium, le molybdène et le tungstène appartiennent à cette famille.By stop metal is meant a metal of the type used for rectifiers with a stop layer. Titanium, tantalum, columbium, zirconium, molybdenum and tungsten belong to this family.
Selon une caractéristique de l'invention, les opérations de revêtement de l'âme électroconductrice sont réalisées dans une atmosphère inerte telle qu'une atmosphère d'argon ou d'hélium. La température des bains électrolytiques fondus est comprise entre 300 et 1000°C cette température dépendant naturellement du type d'âme et des métaux à traiter. On soumet ensuite l'électrode munie de ses deux revêtements à un traitement thermique d'oxydation.According to a characteristic of the invention, the operations of coating the electroconductive core are carried out in an inert atmosphere such as an argon or helium atmosphere. The temperature of the molten electrolytic baths is between 300 and 1000 ° C, this temperature naturally depending on the type of core and the metals to be treated. The electrode provided with its two coatings is then subjected to an oxidation heat treatment.
Un exemple particulier de réalisation non limitatif sera décrit ci-dessous pour mieux expliciter l'invention.A particular non-limiting example of embodiment will be described below to better explain the invention.
On réalise d'abord une âme d'anode par fusion et moulage de métaux communs peu coûteux, tels que le fer ou un alliage de fer, l'aluminium, le cuivre ou des alliages de ces métaux. L'âme pourrait être également réalisée à partir d'un métal tel que le. fer, par exemple semi- travaillé. Toutefois, la technique du moulage permet de réaliser plus facilement des anodes de géométries très diverses.First an anode core is produced by melting and molding inexpensive common metals, such as iron or an iron alloy, aluminum, copper or alloys of these metals. The core could also be made from a metal such as. iron, for example semi-worked. However, the molding technique makes it easier to produce anodes of very different geometries.
L'âme de l'anode reçoit alors un dépôt électrolytique cathodique d'un métal d'arrêt, tel que le titane, le tantale ou le tungstène.The core of the anode then receives a cathodic electrolytic deposit of a stop metal, such as titanium, tantalum or tungsten.
Ce dépôt permet de revêtir l'âme de l'anode d'une couche de métal d'arrêt dont l'épaisseur peut être très réduite, par exemple inférieure à 3mm.This deposit makes it possible to coat the core of the anode with a layer of stop metal, the thickness of which can be very reduced, for example less than 3 mm.
Les quantités de métal d'arrêt utilisées sont ainsi très réduites, bien que l'électrode soit revêtue sur toute sa surface et présente donc des qualités électriques et mécaniques intéressantes.The quantities of stop metal used are thus very reduced, although the electrode is coated over its entire surface and therefore has interesting electrical and mechanical qualities.
Le bain électrolytique fondu permettant le dépôt d'un métal d'arrêt est un bain à haute température comprenant un mélange de chlorures alcalins, tels que le chlorure de sodium, le chlorure de potassium, le chlorure de lithium, ou de fluorures alcalins, tels que le florure de sodium et le fluorure de potassium ou des fluorures et chlorures de métaux d'arrêt ou de composés de métaux d'arrêt, tels que des composés du tungstène.The molten electrolytic bath allowing the deposition of a stop metal is a high temperature bath comprising a mixture of alkali chlorides, such as sodium chloride, potassium chloride, lithium chloride, or alkaline fluorides, such that sodium florure and potassium fluoride or fluorides and chlorides of stop metals or compounds of stop metals, such as tungsten compounds.
Il peut ainsi intervenir une corrosion anodique du métal d'arrêt et du mélange de chlorures fondus avec intervention de tétrachlorure du métal d'arrêt et intervention de composés fluorés du métal d'arrêt.Anodic corrosion of the stop metal and of the mixture of molten chlorides can thus take place with the intervention of tetrachloride of the stop metal and the intervention of fluorinated compounds of the stop metal.
L'opération de revêtement de l'àme à base de fer est réalisée dans une ambiance inerte de gaz rares tels que l'argon ou l'hélium.The coating of the iron-based core is carried out in an inert atmosphere of rare gases such as argon or helium.
La température de fusion du bain électrolytique peut être comprise entre environ 300 et 1000°C.The melting temperature of the electrolytic bath can be between approximately 300 and 1000 ° C.
La densité des courants anodiques peut attein- dre 10kA/m2 en utilisant pour le dépôt cathodique de métal d'arrêt une anode soluble ayant la même composition que celle du métal d'arrêt à déposer.The density of the anode currents can reach 10 kA / m 2 using for the cathodic deposition of stop metal a soluble anode having the same composition as that of the stop metal to be deposited.
Le dépôt s'obtient à potentiels anodiques et cathodiques contrôlés et à densité de courant anodique et cathodique toujours contrôlée avec des tensions de cellule comprises entre 0 et 7 volts. Les densités de courant peuvent être, par exemple, de 100 à 700 A/m2 à la cathode et de 10 à 90 A/m2 à l'anode.The deposit is obtained at anode and cathode potentials controlled and at anode and cathode current density always controlled with cell voltages between 0 and 7 volts. The current densities can be, for example, from 100 to 700 A / m 2 at the cathode and from 10 to 90 A / m 2 at the anode.
L'anode à base d'un métal bon marché, tel que du fer, de l'aluminium, du cuivre, munie de son premier revêtement de métal d'arrêt, reçoit ensuite un second revêtement électrocatalytique constitué de métaux nobles ou d'un mélange de métaux nobles et de métaux d'arrêt, ou de composés intermétalliques de métaux nobles et de métaux d'arrêt ou encore de composés de métaux d'arrêt tels que le carbure de tungstène. Le deuxième revêtement peut être effectué à l'aide de la même technique que pour le premier revêtement, c'est à dire à l'aide d'un bain électrolytique fondu à haute température, d'un mélange d'halogénures alcalins et d'halogénures de métaux nobles, auxquels peuvent être éventuellement associés des halogénures de métaux d'arrêt.The anode based on a cheap metal, such as iron, aluminum, copper, provided with its first coating of stop metal, then receives a second electrocatalytic coating consisting of noble metals or a mixture of noble metals and stop metals, or intermetallic compounds of noble metals and stop metals or also of stop metal compounds such as tungsten carbide. The second coating can be carried out using the same technique as for the first coating, that is to say using a molten electrolytic bath at high temperature, a mixture of alkali halides and noble metal halides, which may optionally be combined with stop metal halides.
Le métal noble peut encore être déposé par des bains aqueux, c'est à dire galvaniques.The noble metal can still be deposited by aqueous baths, ie galvanic.
On notera également que, selon une variante de réalisation, après le dépôt par électrolyse, au moyen d'un bain fondu d'un premier revêtement conducteur élec- trocathodique ou électroanodique en métal d'arrêt, tel que le titane, sur une base en métal commun, tel que de l'acier, il est possible de réaliser par électrolyse selon la même technique, un second revêtement conducteur en métal d'arrêt, tel que du tungstène, puis de réaliser à haute température une carburation de ce dernier revêtement, auquel cas il n'est pas alors nécessaire de déposer de métal noble.It will also be noted that, according to an alternative embodiment, after the electrolytic deposition, by means of a molten bath of a first electrocathodic or electroanodic conductive coating of stop metal, such as titanium, on a base common metal, such as steel, it is possible to produce, by electrolysis according to the same technique, a second conductive coating of stop metal, such as tungsten, then to carry out at high temperature a carburation of this latter coating, in which case it is not then necessary to deposit a noble metal.
La présente invention se prête bien à la fabrication d'anodes de formes très diverses, notamment d'anodes munies de plusieurs branchements d'électrode couplés à la barrière anodique, puisque notamment la technique du moulage permet de former des âmes aux formes les plus variées.The present invention lends itself well to the manufacture of anodes of very diverse shapes, in particular of anodes provided with several electrode connections coupled to the anode barrier, since in particular the molding technique makes it possible to form cores with the most varied shapes. .
Une anode réalisée selon la présente invention présente une excellente résistance mécanique et chimique, notamment à la corrosion, y compris pour des températures supérieures à la normale.An anode produced according to the present invention has excellent mechanical and chemical resistance, especially to corrosion, including for temperatures above normal.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7814920 | 1978-05-19 | ||
| FR7814920A FR2426095A1 (en) | 1978-05-19 | 1978-05-19 | ANODIC ELECTRODE STABLE IN DIMENSIONS AND MANUFACTURING PROCESS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0005674A2 true EP0005674A2 (en) | 1979-11-28 |
| EP0005674A3 EP0005674A3 (en) | 1979-12-12 |
| EP0005674B1 EP0005674B1 (en) | 1983-02-16 |
Family
ID=9208470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79400313A Expired EP0005674B1 (en) | 1978-05-19 | 1979-05-18 | Process of manufacturing a dimensionally stable anode |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0005674B1 (en) |
| DE (1) | DE2964788D1 (en) |
| FR (1) | FR2426095A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0079055A1 (en) * | 1981-11-09 | 1983-05-18 | Diamond Shamrock Corporation | Titanium clad copper electrode and method for making |
| US4657652A (en) * | 1986-02-28 | 1987-04-14 | Pennwalt Corporation | Electrolytic cell and anode for brine electrolytes |
| EP0384194A2 (en) * | 1989-02-18 | 1990-08-29 | Bayer Ag | Dimensionally stable anodes and their use in the production of alkalidichromates and chromic acid |
| FR2735386A1 (en) * | 1995-06-15 | 1996-12-20 | Electricite De France | Long life high potential electrochemical anode |
| DE10029837A1 (en) * | 2000-06-16 | 2002-01-03 | Degussa Galvanotechnik Gmbh | Process for the production of one-sided platinum-plated plates and expanded metal grids from refractory metals |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE913768C (en) * | 1951-12-31 | 1954-06-21 | Degussa | Insoluble electrode |
| FR1116396A (en) * | 1954-01-19 | 1956-05-07 | Titan Gmbh | Process for treating metals |
| US3547789A (en) * | 1968-05-07 | 1970-12-15 | Us Interior | Electrodeposition of thick coatings of palladium |
| FR2067802A5 (en) * | 1969-11-18 | 1971-08-20 | Paris Rene | Metal boride electrodes |
-
1978
- 1978-05-19 FR FR7814920A patent/FR2426095A1/en active Granted
-
1979
- 1979-05-18 DE DE7979400313T patent/DE2964788D1/en not_active Expired
- 1979-05-18 EP EP79400313A patent/EP0005674B1/en not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE913768C (en) * | 1951-12-31 | 1954-06-21 | Degussa | Insoluble electrode |
| FR1116396A (en) * | 1954-01-19 | 1956-05-07 | Titan Gmbh | Process for treating metals |
| US3547789A (en) * | 1968-05-07 | 1970-12-15 | Us Interior | Electrodeposition of thick coatings of palladium |
| FR2067802A5 (en) * | 1969-11-18 | 1971-08-20 | Paris Rene | Metal boride electrodes |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0079055A1 (en) * | 1981-11-09 | 1983-05-18 | Diamond Shamrock Corporation | Titanium clad copper electrode and method for making |
| US4657652A (en) * | 1986-02-28 | 1987-04-14 | Pennwalt Corporation | Electrolytic cell and anode for brine electrolytes |
| EP0384194A2 (en) * | 1989-02-18 | 1990-08-29 | Bayer Ag | Dimensionally stable anodes and their use in the production of alkalidichromates and chromic acid |
| JPH02247392A (en) * | 1989-02-18 | 1990-10-03 | Bayer Ag | Anode with dimensional stability and its use for producing bichromate and chromic acid of alkalic metal |
| EP0384194A3 (en) * | 1989-02-18 | 1991-06-05 | Bayer Ag | Dimensionally stable anodes and their use in the production of alkalidichromates and chromic acid |
| US5128000A (en) * | 1989-02-18 | 1992-07-07 | Bayer Aktiengesellschaft | Dimensionally stable anodes and their use in the preparation of alkali metal dichromates and chromic acid |
| FR2735386A1 (en) * | 1995-06-15 | 1996-12-20 | Electricite De France | Long life high potential electrochemical anode |
| DE10029837A1 (en) * | 2000-06-16 | 2002-01-03 | Degussa Galvanotechnik Gmbh | Process for the production of one-sided platinum-plated plates and expanded metal grids from refractory metals |
| EP1170401A2 (en) * | 2000-06-16 | 2002-01-09 | Degussa Galvanotechnik GmbH | Process for the manufacture of one side platinised panels and expanded mesh sheets made of refractory metals |
| EP1170401A3 (en) * | 2000-06-16 | 2004-01-28 | Degussa Galvanotechnik GmbH | Process for the manufacture of one side platinised panels and expanded mesh sheets made of refractory metals |
| DE10029837B4 (en) * | 2000-06-16 | 2005-02-17 | Degussa Galvanotechnik Gmbh | Process for the production of unilaterally platinated plates and expanded metal gratings of refractory metals |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2426095B1 (en) | 1980-11-07 |
| DE2964788D1 (en) | 1983-03-24 |
| FR2426095A1 (en) | 1979-12-14 |
| EP0005674B1 (en) | 1983-02-16 |
| EP0005674A3 (en) | 1979-12-12 |
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