EP0048505A1 - Process and apparatus for continuously covering a solid-state electrolyte with a catalytically active metal - Google Patents
Process and apparatus for continuously covering a solid-state electrolyte with a catalytically active metal Download PDFInfo
- Publication number
- EP0048505A1 EP0048505A1 EP81200856A EP81200856A EP0048505A1 EP 0048505 A1 EP0048505 A1 EP 0048505A1 EP 81200856 A EP81200856 A EP 81200856A EP 81200856 A EP81200856 A EP 81200856A EP 0048505 A1 EP0048505 A1 EP 0048505A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- roller
- solid electrolyte
- felt
- carbon
- rollers
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Definitions
- the invention relates to a method for the continuous coating of a solid electrolyte according to the preamble of claim 1 and a device according to the preamble of claim 4.
- aqueous electrolysis especially in the production of hydrogen by water decomposition, more and more solid electrolytes based on organic plastics are being used. It proves necessary to coat such solid electrolytes, which are usually in the form of foils, with a suitable electrocatalyst, usually a platinum metal.
- a coating method which is based on electrolytic deposition of the metal in question, and a corresponding apparatus is known from DE-OS 28 21 271.
- the plastic film to be coated is first impregnated with an aqueous metal salt solution and then inserted into a sandwich electrolysis cell and subjected to electrolysis, the metal being deposited on the cathode side.
- the invention is based on the object of specifying a method and a device for the continuous coating of a solid electrolyte with a catalytically active metal, as a result of which a flawless and uniform deposition is ensured in a simple and economical manner even on large-area foils will.
- rollers can also be realized by other arrangements.
- the rollers can also be arranged vertically or obliquely (at an angle to the horizontal).
- a dried film made of solid electrolyte 1 (base: perfluorinated sulfonic acid: trade name "Nafion” from DuPont de Nemours) with a square area of 250 mm side length and a thickness of 0.2 mm was in a solution of 0.5 wt .-% Pt (NH 3) 2 (N0 2) 2 (Diamminplatindinitrit) impregnated min in distilled water at 90 0 C during the 30th After impregnation, the film was removed from the solution and rinsed with distilled water. The film in the device according to FIG. 2 was then subjected to an electrolysis process in that it was carried out between the rollers 4 and 5.
- the metallic platinum layer was deposited on the cathode side under the following conditions:
- the solid electrolyte film was boiled in 1 N hydrochloric acid to remove the unreacted platinum complex salt.
- the density of the deposited platinum layer was approximately 0.5 mg / cm.
- the method is not limited to the aforementioned example.
- all catalytically active metals from suitable salt solutions can be continuously deposited on the surface of a solid electrolyte in this way.
- this can also be done with the device according to FIG. 3 achievable methods are used.
- the method and the device according to the invention enable the continuous and large-area coating of solid electrolytes with catalytically active metals, in particular noble metals, with firmly adhering surface layers of great uniformity being obtained.
Abstract
Grossflächige Folien aus Feststoffelektrolyt (3) werden in gleichmässiger Weise kontinuierlich mit katalytisch aktiven Metallen beschichtet, indem sie zunächst mit einer wässerigen Lösung des betreffenden Metalls imprägniert und anschliessend in einem Wasserbad (2) zwischen zwei als Elektroden wirkenden Walzen (4,5) unter Zwischenschaltung eines kathodenseitig angeordneten Filzes (6) aus Kohlenstoff hindurchgeführt und dabei einem Elektrolyseprozess unterworfen werden. Large-area foils made of solid electrolyte (3) are coated in a uniform manner continuously with catalytically active metals by first impregnating them with an aqueous solution of the metal in question and then in a water bath (2) between two rollers (4,5) acting as electrodes, with interposition a felt (6) made of carbon arranged on the cathode side is passed through and subjected to an electrolysis process.
Description
Die Erfindung geht aus von einem Verfahren zur kontinuierlichen Beschichtung eines Feststoffelektrolyten nach der Gattung des Anspruchs 1 und einer Vorrichtung nach der Gattung des Anspruchs 4.The invention relates to a method for the continuous coating of a solid electrolyte according to the preamble of
In der wässerigen Elektrolyse, insbesondere bei der Herstellung von Wasserstoff durch Wasserzersetzung werden immer mehr Feststoffelektrolyte auf der Basis organischer Kunststoffe eingesetzt. Es erweist sich als notwendig, derartige Feststoffelektrolyte, welche in der Regel als Folien vorliegen, mit einem geeigneten Elektrokatalysator, meist einem Platinmetall zu beschichten. Ein derartiges Beschichtungsverfahren, welches auf einer elektrolytischen Abscheidung des betreffenden Metalls beruht, sowie eine entsprechende Apparatur ist aus der DE-OS 28 21 271 bekannt. Dabei wird die zu beschichtende Kunststoff-Folie zunächst mit einer wässerigen Metallsalzlösung imprägniert und dann in eine Sandwich-Elektrolysezelle eingesetzt und einer Elektrolyse unterworfen, wobei das Metall kathodenseitig abgeschieden wird.In aqueous electrolysis, especially in the production of hydrogen by water decomposition, more and more solid electrolytes based on organic plastics are being used. It proves necessary to coat such solid electrolytes, which are usually in the form of foils, with a suitable electrocatalyst, usually a platinum metal. Such a coating method, which is based on electrolytic deposition of the metal in question, and a corresponding apparatus is known from DE-OS 28 21 271. The plastic film to be coated is first impregnated with an aqueous metal salt solution and then inserted into a sandwich electrolysis cell and subjected to electrolysis, the metal being deposited on the cathode side.
Verfahren und Apparatur der beschriebenen Art genügen wohl Laboratoriumszwecken und kleineren Abmessungen. Bei der Beschichtung grossflächiger Folien und grosser Mengen ergeben sich Schwierigkeiten, vor allem bezüglich Einhaltung der Badtemperatur und Gleichmässigkeit des Elektrolyseprozesses. Zudem wäre eine derartige Methode wenig wirtschaftlich. Es besteht daher ein Bedürfnis, das Verfahren zu verbessern und eine geeignetere Apparatur vorzuschlagen.The method and apparatus of the type described are probably sufficient for laboratory purposes and of smaller dimensions. Difficulties arise when coating large-area foils and large quantities, especially with regard to maintaining the bath temperature and uniformity of the electrolysis process. In addition, such a method would not be very economical. There is therefore a need to improve the process and to propose more suitable equipment.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren sowie eine Vorrichtung zur kontinuierlichen Beschichtung eines Feststoffelektrolyten mit einem katalytisch aktiven Metall anzugeben, wodurch eine einwandfreie und gleichmässige Abscheidung auch auf grossflächigen Folien in einfacher und wirtschaftlicher Weise gewährleistet wird.Es soll dadurch insbesondere eine industrielle Grossproduktion ermöglicht werden.The invention is based on the object of specifying a method and a device for the continuous coating of a solid electrolyte with a catalytically active metal, as a result of which a flawless and uniform deposition is ensured in a simple and economical manner even on large-area foils will.
Diese Aufgabe wird erfindungsgemäss durch die Merkmale der Ansprüche 1 und 4 gelöst.According to the invention, this object is achieved by the features of
Die Erfindung wird anhand der nachfolgenden, durch Figuren erläuterten Ausführungsbeispiele beschrieben.The invention is described on the basis of the following exemplary embodiments explained by figures.
Dabei zeigt:
- Fig. 1 einen schematischen Querschnitt durch eine Ausführung der Vorrichtung,
- Fig. 2 einen halbschematischen Längsschnitt durch eine Ausführung der Vorrichtung,
- Fig. 3 einen schematischen Querschnitt durch eine andere Ausführung der Vorrichtung.
- In Fig. 1 ist eine zur Durchführung des Verfahrens geeignete erste Vorrichtung schematisch dargestellt. In einer
rechteckigen Wanne 1, welche beispielsweise aus Polypropylen bestehen kann, befindet sich ein Wasserbad 2 (destilliertes, bzw. vollentsalztes Wasser). Als Elektroden dienen die beidenWalzen 4 und 5, wobei diese zweckmässigerweise horizontalachsig angeordnet sind. Die als Anode dienendeuntere Walze 4, welche bevorzugt aus platiniertem Titan besteht, wird vomWasserbad 2 vollständig überflutet, während die als Kathode wirkendeobere Walze 5, die vorteilhafterweise aus korrosionsbeständigem Stahl besteht, nur im Elektrolysebereich in das Wasser eintaucht. Der zubeschichtende Feststoffelektrolyt 3, welcher als Folie vorliegt, befindet sich unter Zwischenschaltung einesFilzes 6 aus Kohlenstoff zwischen den beidenWalzen 4 und 5. DerFilz 6 ist auf der Kathodenseite angeordnet und umhüllt im vorliegenden Beispiel dieWalze 5 koaxial. Er ist mit letzterer beispielsweise mittels Kunststoffkleber (Epoxyharz) fest verbunden. Die Anpresskraft ist durch einen vertikalen Pfeil F angedeutet. - Fig. 2 stellt einen halbschematischen Längsschnitt durch eine Ausführung der Vorrichtung dar. In einer
rechteckförmigen Wanne 1 aus Polypropylen ist ein Rahmen 7 des Walzengerüstes eingebaut, in welchem eine als Anode dienendeuntere Walze 4 aus platiniertem Titan fest gelagert ist. Sie wird über einenAntriebsmotor 10 angetrieben. Eine als Kathode dienendeobere Walze 5 aus rostfreiem Stahl, welche einenFilz 6 aus Kohlenstoff als fest mit Kunstharz aufgeklebte Ummantelung besitzt, ist vertikal verschiebbar inisolierten Lagern 8 gelagert, welche sich ihrerseits überFedern 9 auf dem Rahmen 7 abstützen. Der Anpressdruck derWalze 5 kann durch Wahl der Federvorspannung, welche über die Befestigungsschrauben eingestellt werden kann, den jeweiligen Verhältnissen optimal angepasst werden. Die Federkraft ist durch vertikal nach unten gerichtete Pfeile F angedeutet. Die 4, 5 sind mitWalzen 11, 12 versehen. 3 stellt den Querschnitt des zu beschichtenden Feststoffelektrolyten in Form einer Folie dar. Das Niveau des Wasserbades 2 (destilliertes bzw. vollentsalztes Wasser) ist nicht wesentlich. Das Wasser kann die obere Walze teilweise oder ganz bedecken. Die Apparatur ist nicht masstäblich gezeichnet. Insbesondere kann die Walzenbreite im Verhältnis zur Darstellung ein Vielfaches betragen und richtet sich nach der Breite der zu beschichtenden Folie.Stromzuführungen - Fig. 3 zeigt einen schematischen Querschnitt durch eine andere Ausführung der Vorrichtung. Die
Wanne 1, dasWasserbad 2, der als Folievorliegende Feststoffelektrolyt 3 sowie die als Anode (positiver Pol) dienendeuntere Walze 4 entsprechen weitgehend der Anordnung gemäss Fig. l. Die obere, als Kathodewirkende Walze 5 trägt jedoch keine Ummanzelung, sondern derFilz 6 aus Kohlenstoff wird lediglich lcse zwischenFeststoffelektrolyt 3 undWalze 5 kathodenseitig hineingelegt und im Bereich der Walzen planparallel zumFeststoffelektrolyten 3 geführt. Diese Anordnung erlaubt ein rasches Auswechseln desFilzes 6, falls die Umstände es erfordern (andere Dimensionen, z.B..Dicke, physikalisch-chemische Beschaffenheit, Abnutzung etc.).
- 1 shows a schematic cross section through an embodiment of the device,
- 2 shows a semi-schematic longitudinal section through an embodiment of the device,
- Fig. 3 shows a schematic cross section through another embodiment of the device.
- 1 schematically shows a first device suitable for carrying out the method. In a
rectangular tub 1, which may consist of polypropylene, for example, there is a water bath 2 (distilled or fully demineralized water). The two 4 and 5 serve as electrodes, and these are expediently arranged with a horizontal axis. Therollers lower roller 4 serving as an anode, which preferably consists of platinized titanium, is completely flooded by thewater bath 2, while theupper roller 5, which advantageously acts of corrosion-resistant steel and acts as a cathode, is only immersed in the water in the electrolysis area. Thesolid electrolyte 3 to be coated, which is in the form of a film, is located with the interposition of a felt 6 made of carbon between the two 4 and 5. Therollers felt 6 is arranged on the cathode side and in the present example envelops theroller 5 coaxially. It is firmly connected to the latter, for example by means of plastic adhesive (epoxy resin). The contact pressure is indicated by a vertical arrow F. - Fig. 2 shows a semi-schematic longitudinal section through an embodiment of the device. In a
rectangular trough 1 made of polypropylene, a frame 7 of the roll stand is installed, in which alower roll 4 serving as an anode is made of platinum-coated titanium. It is driven by adrive motor 10. Anupper roller 5 made of stainless steel, which serves as a cathode and which has a felt 6 made of carbon as a sheath firmly bonded with synthetic resin, is vertically displaceably mounted in insulatedbearings 8, which in turn are supported on the frame 7 bysprings 9. The contact pressure of theroller 5 can by the choice of the spring preload, which can be adjusted using the fastening screws can be optimally adapted to the respective conditions. The spring force is indicated by arrows F pointing vertically downwards. The 4, 5 are provided withrollers 11, 12. 3 shows the cross section of the solid electrolyte to be coated in the form of a film. The level of the water bath 2 (distilled or demineralized water) is not essential. The water can partially or completely cover the upper roller. The apparatus is not drawn to scale. In particular, the roller width can be a multiple in relation to the representation and depends on the width of the film to be coated.power supplies - Fig. 3 shows a schematic cross section through another embodiment of the device. The
tub 1, thewater bath 2, thesolid electrolyte 3 present as a film and thelower roller 4 serving as an anode (positive pole) largely correspond to the arrangement according to FIG. 1. However, theupper roller 5, which acts as a cathode, does not have a sheathing, but thefelt 6 made of carbon is merely inserted between thesolid electrolyte 3 and theroller 5 on the cathode side and guided in the area of the rollers parallel to thesolid electrolyte 3. This arrangement allows the felt 6 to be replaced quickly if circumstances so require (other dimensions, e.g. thickness, physico-chemical nature, wear, etc.).
Die Erfindung ist nicht auf die in den Figuren dargestellten Ausführungen beschränkt. Das Prinzip der Walzen lässt sich auch durch andere Anordnungen verwirklichen. Beispielsweise können die Walzen auch vertikalachsig oder schief (unter einem Winkel zur Horizontalen) angeordnet sein.The invention is not restricted to the embodiments shown in the figures. The principle of the rollers can also be realized by other arrangements. For example, the rollers can also be arranged vertically or obliquely (at an angle to the horizontal).
Eine getrocknete Folie aus Feststoffelektrolyt 1 (Basis: perfluorierte Sulfosäure: Handelsname "Nafion" von DuPont de Nemours) mit einer quadratischen Fläche von 250 mm Seitenlänge und einer Dicke von 0,2 mm wurde in einer Lösung von 0,5 Gew.-% Pt (NH3)2 (N02)2 (Diamminplatindinitrit) in destilliertem Wasser bei 900C während 30 min imprägniert. Nach der Imprägnierung wurde die Folie aus der Lösung entfernt und mit destilliertem Wasser abgespült. Daraufhin wurde die Folie in der Vorrichtung gemäss Fig. 2 einem Elektrolyseprozess unterworfen, indem sie zwischen den Walzen 4 und 5 durchgeführt wurde. Die Abscheidung der metallischen Platinschicht auf der Kathodenseite erfolgte unter folgenden Bedingungen:A dried film made of solid electrolyte 1 (base: perfluorinated sulfonic acid: trade name "Nafion" from DuPont de Nemours) with a square area of 250 mm side length and a thickness of 0.2 mm was in a solution of 0.5 wt .-% Pt (NH 3) 2 (N0 2) 2 (Diamminplatindinitrit) impregnated min in distilled water at 90 0 C during the 30th After impregnation, the film was removed from the solution and rinsed with distilled water. The film in the device according to FIG. 2 was then subjected to an electrolysis process in that it was carried out between the
Stromstärke: 30 A Umdrehungsgeschwindigkeit der unteren Walze: 0,17/min Entsprechende Vorschubgeschwindigkeit der Folie: 1,6 cm/min Wasserbadtemperatur: 250cCurrent: 30 A rotation speed of the lower roller: 0.17 / min Corresponding feed speed of the film: 1.6 cm / min water bath temperature: 250c
Nach beendetem Abscheidungsprozess wurde die Feststoffelektrolyt-Folie zwecks Entfernung des nicht umgesetzten Platinkomplexsalzes in 1 N Salzsäure ausgekocht. Die Belegungsdichte der abgeschiedenen Platinschicht betrug ca. 0,5 mg/cm .After the deposition process was complete, the solid electrolyte film was boiled in 1 N hydrochloric acid to remove the unreacted platinum complex salt. The density of the deposited platinum layer was approximately 0.5 mg / cm.
Selbstverständlich ist das Verfahren nicht auf das vorgenannte Beispiel beschränkt. Grundsätzlich können alle katalytisch aktiven Metalle aus geeigneten Salzlösungen auf diese Art und Weise kontinuierlich auf der Oberfläche eines Feststoffelektrolyten abgeschieden werden. Dabei kann als Variante auch das mit der Vorrichtung gemäss Fig. 3 erzielbare Verfahren zur Anwendung kommen.Of course, the method is not limited to the aforementioned example. In principle, all catalytically active metals from suitable salt solutions can be continuously deposited on the surface of a solid electrolyte in this way. As a variant, this can also be done with the device according to FIG. 3 achievable methods are used.
Durch das erfindungsgemässe Verfahren und die erfindungsgemässe Vorrichtung wird die kontinuierliche und grossflächige Beschichtung von Feststoffelektrolyten mit katalytisch aktiven Metallen, insbesondere Edelmetallen ermöglicht, wobei fest haftende Oberflächenschichten grosser Gleichmässigkeit erhalten werden.The method and the device according to the invention enable the continuous and large-area coating of solid electrolytes with catalytically active metals, in particular noble metals, with firmly adhering surface layers of great uniformity being obtained.
- 1 Wanne1 tub
- 2 Wasserbad2 water bath
- 3 Feststoffelektrolyt (Folie)3 solid electrolyte (foil)
- 4 Untere Walze (Anode)4 lower roller (anode)
- 5 Obere Walze (Kathode)5 upper roller (cathode)
- 6 Filz aus Kohlenstoff6 carbon felt
- 7 Rahmen des Walzengerüstes7 frame of the roll stand
- 8 Isoliertes Lager der oberen Walze8 Insulated upper roller bearing
- 9 Feder9 spring
- 10 Antriebsmotor10 drive motor
- 11 Stromzuführung zur unteren Walze (positiver Pol)11 power supply to the lower roller (positive pole)
- 12 Stromzuführung zur oberen Walze (negativer Pol)12 power supply to the upper roller (negative pole)
Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH704980 | 1980-09-19 | ||
CH7049/80 | 1980-09-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0048505A1 true EP0048505A1 (en) | 1982-03-31 |
EP0048505B1 EP0048505B1 (en) | 1984-05-30 |
Family
ID=4319140
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81200856A Expired EP0048505B1 (en) | 1980-09-19 | 1981-07-30 | Process and apparatus for continuously covering a solid-state electrolyte with a catalytically active metal |
Country Status (3)
Country | Link |
---|---|
US (1) | US4396469A (en) |
EP (1) | EP0048505B1 (en) |
DE (1) | DE3163881D1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3413303A1 (en) * | 1983-05-06 | 1984-11-08 | BBC Aktiengesellschaft Brown, Boveri & Cie., Baden, Aargau | CATHODIC, GAS AND LIQUID TRANSFERABLE ELECTRIC COLLECTOR |
EP0151954A1 (en) * | 1984-01-26 | 1985-08-21 | BBC Brown Boveri AG | Process for the continuous coating of a solid electrolyte with a catalytic active metal |
US4756819A (en) * | 1983-11-21 | 1988-07-12 | Elf France | Process for the thermal treatment of hydrocarbon charges in the presence of additives which reduce coke formation |
US4867160A (en) * | 1985-09-18 | 1989-09-19 | Biotronik Mess- Und Therapiegerate Gmbh & Co. | Cardiac pacemaker |
WO1998053515A1 (en) * | 1997-05-16 | 1998-11-26 | Forschungszentrum Jülich GmbH | Production of electrolyte units by electrolytic deposition of a catalyst |
CN102383159A (en) * | 2011-08-09 | 2012-03-21 | 长春一汽富维高新汽车饰件有限公司 | Coarsening production and trivalent chromium electrolysis process incorporating device and method |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4661213A (en) * | 1986-02-13 | 1987-04-28 | Dorsett Terry E | Electroplate to moving metal |
US4959132A (en) * | 1988-05-18 | 1990-09-25 | North Carolina State University | Preparing in situ electrocatalytic films in solid polymer electrolyte membranes, composite microelectrode structures produced thereby and chloralkali process utilizing the same |
DE19908920A1 (en) * | 1999-03-02 | 2000-09-07 | Buna Sow Leuna Olefinverb Gmbh | Process for the production of electrically conductive films based on starch esters |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2647108A1 (en) * | 1976-10-19 | 1978-04-20 | Felten & Guilleaume Carlswerk | Continuous metallising of glass fibre - using four bath system for pretreatment, silvering and copper coating with intermediate washes |
DE2821271A1 (en) * | 1978-04-14 | 1979-10-25 | Bbc Brown Boveri & Cie | PROCESS FOR ELECTROLYTIC DEPOSITION OF METALS |
FR2438692A1 (en) * | 1978-10-12 | 1980-05-09 | Sumitomo Electric Industries | Continuous mfr. of porous metal strip - where porous organic or inorganic strip is provided with electrically conducting surface and is then electroplated |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US936472A (en) * | 1909-06-18 | 1909-10-12 | Wilhelm Pfanhauser | Mechanical arrangement for electroplating objects. |
US2540602A (en) * | 1946-07-03 | 1951-02-06 | Lockheed Aircraft Corp | Method and apparatus for the surface treatment of metals |
US3806441A (en) * | 1972-09-11 | 1974-04-23 | Norton Co | Flap belt electroplating apparatus |
-
1981
- 1981-07-30 EP EP81200856A patent/EP0048505B1/en not_active Expired
- 1981-07-30 DE DE8181200856T patent/DE3163881D1/en not_active Expired
- 1981-09-17 US US06/302,986 patent/US4396469A/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2647108A1 (en) * | 1976-10-19 | 1978-04-20 | Felten & Guilleaume Carlswerk | Continuous metallising of glass fibre - using four bath system for pretreatment, silvering and copper coating with intermediate washes |
DE2821271A1 (en) * | 1978-04-14 | 1979-10-25 | Bbc Brown Boveri & Cie | PROCESS FOR ELECTROLYTIC DEPOSITION OF METALS |
FR2438692A1 (en) * | 1978-10-12 | 1980-05-09 | Sumitomo Electric Industries | Continuous mfr. of porous metal strip - where porous organic or inorganic strip is provided with electrically conducting surface and is then electroplated |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3413303A1 (en) * | 1983-05-06 | 1984-11-08 | BBC Aktiengesellschaft Brown, Boveri & Cie., Baden, Aargau | CATHODIC, GAS AND LIQUID TRANSFERABLE ELECTRIC COLLECTOR |
US4756819A (en) * | 1983-11-21 | 1988-07-12 | Elf France | Process for the thermal treatment of hydrocarbon charges in the presence of additives which reduce coke formation |
EP0151954A1 (en) * | 1984-01-26 | 1985-08-21 | BBC Brown Boveri AG | Process for the continuous coating of a solid electrolyte with a catalytic active metal |
CH663221A5 (en) * | 1984-01-26 | 1987-11-30 | Bbc Brown Boveri & Cie | METHOD FOR CONTINUOUSLY COATING A SOLID ELECTROLYTE WITH A CATALYTICALLY ACTIVE METAL. |
US4867160A (en) * | 1985-09-18 | 1989-09-19 | Biotronik Mess- Und Therapiegerate Gmbh & Co. | Cardiac pacemaker |
WO1998053515A1 (en) * | 1997-05-16 | 1998-11-26 | Forschungszentrum Jülich GmbH | Production of electrolyte units by electrolytic deposition of a catalyst |
CN102383159A (en) * | 2011-08-09 | 2012-03-21 | 长春一汽富维高新汽车饰件有限公司 | Coarsening production and trivalent chromium electrolysis process incorporating device and method |
Also Published As
Publication number | Publication date |
---|---|
DE3163881D1 (en) | 1984-07-05 |
EP0048505B1 (en) | 1984-05-30 |
US4396469A (en) | 1983-08-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2217879C3 (en) | Process and electroplating cell for the continuous electrolytic production of an iron foil | |
DE3603856C2 (en) | Method and device for galvanizing flat workpieces such as printed circuit boards | |
EP1688518B1 (en) | Process and apparatus for continuous electrochemical treatment of pieces | |
DE3236545A1 (en) | METHOD FOR ELECTROPLATING AND DEVICE FOR CARRYING OUT THE METHOD | |
DE1299608B (en) | Process and device for the electrolytic removal of traces of metals from non-metallic aqueous salt solutions | |
EP3666931A1 (en) | Process of fabricating a metal band having a chromium and chromium oxide coating using a trivalent chromium containing electrolyte | |
EP0048505B1 (en) | Process and apparatus for continuously covering a solid-state electrolyte with a catalytically active metal | |
DE4002700A1 (en) | ELECTROCHEMICALLY MACHINABLE WORKPIECE AND METHOD FOR ELECTROCHEMICALLY WORKING A METAL WORKPIECE | |
DE2355865A1 (en) | METHOD AND EQUIPMENT FOR CLEANING A SURFACE OF A METAL OBJECT | |
DE102016104031B4 (en) | Plating apparatus and plating method for forming a metal plating | |
DE60133819T2 (en) | GAS DIFFUSION ELECTRODE, METHOD OF MANUFACTURING THEREFOR AND THIS USING FUEL CELL | |
DE3246690A1 (en) | METHOD AND DEVICE FOR THE ELECTROLYTIC TREATMENT OF METAL RAILS | |
WO2014094998A1 (en) | Device and method for electrolytically coating an object | |
DE3317564A1 (en) | Apparatus and process for coating a metal strip | |
DE4417403A1 (en) | Process for producing a gas electrode | |
EP0151954B1 (en) | Process for the continuous coating of a solid electrolyte with a catalytic active metal | |
DE2008606A1 (en) | Apparatus for the continuous treatment of electrolytically influencing the metal wire and process for the continuous treatment of electrolytically influencing metal wires | |
DD206567A5 (en) | NETWORK ELECTRODE FOR THE RECONSTRUCTION OF METALLIONS AND METHOD FOR THE PRODUCTION THEREOF | |
DE102009038677B4 (en) | An electrode assembly for use in an electrodeposition process, and this electrodeposition process | |
DE2753936A1 (en) | METHOD OF FORMING AN IRON FOIL AT HIGH CURRENT DENSITY | |
EP4010517A1 (en) | Method and system for electroytically coating a steel strip by means of pulse technology | |
DE3903276C2 (en) | Process for the electrolytic surface treatment of aluminum substrates for planographic printing plates | |
DE2528942A1 (en) | PROCESS FOR ZONED ELECTROPOLATING THE INTERNAL SURFACE OF LARGE-SPACED CONTAINERS | |
DE102010003171B4 (en) | Manufacturing method for a fuel cell separator | |
EP0429748B1 (en) | Electrode for the recovery of metals from a solution containing metal-ions |
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 |
|
AK | Designated contracting states |
Designated state(s): CH DE FR IT |
|
17P | Request for examination filed |
Effective date: 19820724 |
|
ITF | It: translation for a ep patent filed |
Owner name: DE DOMINICIS & MAYER S.R.L. |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): CH DE FR IT LI |
|
REF | Corresponds to: |
Ref document number: 3163881 Country of ref document: DE Date of ref document: 19840705 |
|
ET | Fr: translation filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19841023 Year of fee payment: 4 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19880731 Ref country code: CH Effective date: 19880731 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19900615 Year of fee payment: 10 |
|
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19900924 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19920331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19920401 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |