DE1188895B - Process for the production of a composite material of titanium and a metal of the platinum group by plating - Google Patents

Process for the production of a composite material of titanium and a metal of the platinum group by plating

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Publication number
DE1188895B
DE1188895B DED39673A DED0039673A DE1188895B DE 1188895 B DE1188895 B DE 1188895B DE D39673 A DED39673 A DE D39673A DE D0039673 A DED0039673 A DE D0039673A DE 1188895 B DE1188895 B DE 1188895B
Authority
DE
Germany
Prior art keywords
metal
titanium
composite material
platinum
platinum group
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.)
Pending
Application number
DED39673A
Other languages
German (de)
Inventor
Dipl-Chem Dr Erwin Rossberger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Priority to DED39673A priority Critical patent/DE1188895B/en
Priority claimed from DEV24779A external-priority patent/DE1202255B/en
Publication of DE1188895B publication Critical patent/DE1188895B/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48Silver or gold
    • B01J23/50Silver
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48Silver or gold
    • B01J23/52Gold
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892Nickel and noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/54Treatment of refractory metals or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90Regeneration or reactivation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. Cl.:Int. Cl .:

C23cC23c

Deutschem.: 48 b-5/00German: 48 b-5/00

Nummer: 1188 895Number: 1188 895

Aktenzeichen: D 39673 VI b/48 bFile number: D 39673 VI b / 48 b

Anmeldetag: 23. August 1962Filing date: August 23, 1962

Auslegetag: 11. März 1965Opening day: March 11, 1965

Die Erfindung bezieht sich auf ein Verfahren zur Herstellung eines Verbundwerkstoffes aus Titan und einem Metall der Platingruppe, der insbesondere zur Verwendung als Elektrodenwerkstoff für elektrochemische Prozesse geeignet ist.The invention relates to a method for producing a composite material from titanium and a metal of the platinum group, which is particularly suitable for use as an electrode material for electrochemical Processes is suitable.

Es ist bekannt, aus Titan und einem Metall der Platingruppe, wie Platin, Rhodium, Ruthenium und Iridium, Verbundwerkstoffe herzustellen, die insbesondere als Elektroden für elektrochemische Prozesse, z. B. für die Chloralkalielektrolyse oder die Herstellung von Perverbindungen, geeignet sind. Die Aufbringung der relativ dünnen Edelmetalldeckschichten kann hierbei auf galvanischem Wege oder auf chemischem Wege oder aus sogenannten Glanz-Platinlösungen, wie sie zur Herstellung von Platinschichten auf keramischem Material gebraucht werden, erfolgen. _It is known to be made from titanium and a platinum group metal such as platinum, rhodium, and ruthenium Iridium, to produce composite materials, which are used in particular as electrodes for electrochemical processes, z. B. for chlor-alkali electrolysis or the production of per compounds are suitable. The application The relatively thin noble metal cover layers can be galvanically or chemically Ways or from so-called gloss platinum solutions, such as those used for the production of platinum layers are used on ceramic material. _

Bei der praktischen Verwendung derartiger Elektroden zeigt es sich jedoch, daß die Korrosionsrate des Platins, d. h. die Abtragung des Platins in Abhängigkeit von der durch die Elektrode übertragenen Strommenge, bei den meisten bekannten Verfahren ungünstiger ist als bei Elektroden, die aus reinem Platinmetall in Form von Blechen hergestellt sind.In the practical use of such electrodes, however, it has been found that the corrosion rate of the Platinum, d. H. the removal of platinum as a function of the amount of current transmitted through the electrode, in most known processes is less favorable than in electrodes made of pure platinum metal are made in the form of sheets.

Es ist weiterhin bekannt, Metallbleche durch Schweißen oder Löten mit einer Grundschicht aus Titan zu verbinden. Dieser Herstellungsprozeß ist jedoch bei den in Betracht kommenden geringen Dicken der Oberflächenschicht in der Größe von einigen μΐη äußerst schwierig und führt häufig nicht zu einwandfreien Produkten.It is also known to make metal sheets with a base layer by welding or soldering Connect titanium. However, this manufacturing process is among the minor ones under consideration Thickness of the surface layer in the size of a few μΐη extremely difficult and often does not lead to flawless products.

Vorliegende Erfindung bezieht sich auf ein Verfahren zur Herstellung eines derartigen Verbundwerkstoffes, der nahezu die gleichen Eigenschaften bei gewissen elektrolytischen Prozessen wie Bleche oder Drähte aus dem reinen Metall besitzt.The present invention relates to a method for producing such a composite material, which has almost the same properties as sheet metal in certain electrolytic processes or has wires made of the pure metal.

Entscheidend für die Qualität des Verbundwerkstoffes ist die Haft- und Bindefestigkeit der Platinauflage auf dem Grundmetall Titan.The adhesive and bonding strength of the platinum layer is decisive for the quality of the composite material on the base metal titanium.

Es wurde nun gefunden, daß hierfür nicht jede der bekannten Beizprozesse, z. B. in flußsäurehaltigen Beizlösungen, geeignet ist. Es ist vielmehr notwendig, in fiuoridfreien Lösungen vorzubehandeln. Auch auf einem durch Beizen in verdünnter Salzsäure vorbehandelten Titan, wobei eine metallisch blanke Oberfläche entsteht, ist es nicht möglich, ein Platinblech haftfest aufzuwalzen; dieses rollt sich dabei von der Unterlage ab.It has now been found that not each of the known pickling processes such. B. in hydrofluoric acid Pickling solutions, is suitable. Rather, it is necessary to pre-treat in fluoride-free solutions. On too a titanium pretreated by pickling in dilute hydrochloric acid, with a metallic bright Surface arises, it is not possible to roll on a platinum sheet firmly; this is rolling from the document.

Es war nun überraschend, daß eine sehr gute Haftung der aufgewalzten Platinauflage erreicht werden konnte, daß das Titan-Unterlagemetall in Lösungen, die mehr als lOnormal an H+- und Cl-Ionen sind, Verfahren zur Herstellung eines
Verbundwerkstoffes aus Titan und einem Metall der Platingruppe durch Plattieren
It was now surprising that a very good adhesion of the rolled-on platinum coating could be achieved, that the titanium base metal in solutions that are more than 10 normal in H + and Cl ions, a process for producing a
Composite of titanium and a platinum group metal by plating

Anmelder:Applicant:

Deutsehe Gold- und Silber-ScheideanstaltGerman gold and silver refinery

vormals Roessler,formerly Roessler,

Frankfurt/M., Weißfrauenstr. 9Frankfurt / M., Weißfrauenstr. 9

Als Erfinder benannt:Named as inventor:

Dipl.-Chem. Dr. Erwin Rossberger, Hanau/M.Dipl.-Chem. Dr. Erwin Rossberger, Hanau / M.

vorzugsweise in konzentrierter Salzsäure, gebeizt ao wurde, und zwar während 6 bis 20 Stunden bei 20° C oder während 4 bis 10 Stunden bei 60° C, wobei eine dunkelgraue Oberflächenschicht entsteht. In den ersten Stunden dieses Beizprozesses bildet sich eine graue, pulverartige Oberflächenschicht von Titanas hydrid, die sich leicht abwischen läßt. In den darauffolgenden Stunden entsteht dann eine fest haftende Schicht, welche für die Haftfestigkeit der aufgewalzten Platinauflage verantwortlich ist.preferably in concentrated hydrochloric acid, pickled ao, for 6 to 20 hours at 20 ° C or for 4 to 10 hours at 60 ° C., a dark gray surface layer being formed. In the In the first few hours of this pickling process, a gray, powder-like surface layer of titania forms hydride that can be easily wiped off. In the following hours, a firmly adhering one develops Layer that is responsible for the adhesive strength of the rolled-on platinum layer.

Ein auf diesem Wege hergestellter Verbundwerkstoff besitzt nach dem Abwälzen in der Kälte eine glatte, dichte Oberfläche, die für die Verwendung in gewissen elektrolytischen Prozessen die gleichen Eigenschaften wie kompaktes, durch einen Walzprozeß bearbeitetes Metall aufweist. Es lassen sich hierbei Verbundwerkstoffe erzeugen, bei denen die Oberflächenschicht eine äußerst geringe Dicke besitzt, so daß der Aufwand an Metall nicht größer ist als bei den galvanisch oder chemisch erzeugten Verbundwerkstoffen. Die Lebensdauer von Elektroden, die nach dem erfindungsgemäßen Verfahren hergestellt sind, beträgt ein Mehrfaches von solchen, die eine gleich dicke, z. B. galvanisch abgeschiedene Oberflächenschicht besitzen.A composite material produced in this way has a after rolling in the cold smooth, dense surface that is the same for use in certain electrolytic processes Has properties such as compact metal worked by a rolling process. It can be produce composite materials in which the surface layer has an extremely small thickness, so that the cost of metal is not greater than that of the galvanically or chemically produced composite materials. The service life of electrodes produced by the method according to the invention are, is a multiple of those that have an equally thick, z. B. electrodeposited surface layer own.

Die Herstellung erfolgt beispielsweise folgendermaßen: Ein Titanblech von 5 mm Stärke wird 16 Stunden in kalter konzentrierter Salzsäure gebeizt. Auf seiner Oberfläche hat sich dabei eine dunkelgraue Schicht gebildet. Nach sorgfältigem Spülen wird bei 110° C getrocknet und ein Platinblech von 50 μΐη durch Abwälzen auf 2 mm verbunden. Nun wird etwa 10 Minuten bei 700° C im Vakuum oder unter Schutzgas geglüht. Man erhält dabei. eineProduction takes place as follows, for example: A titanium sheet 5 mm thick is used Pickled in cold concentrated hydrochloric acid for 16 hours. A dark gray layer has formed on its surface. After careful rinsing is dried at 110 ° C and a platinum sheet of 50 μΐη connected by rolling to 2 mm. so is annealed for about 10 minutes at 700 ° C in a vacuum or under protective gas. One receives thereby. one

509 518/374509 518/374

Grenzschicht zwischen Titan und Platin, in welcher PfTi8 röntgenographisch nachzuweisen ist. Nach dieser Diffusionsglühung kann noch weiter abgewalzt werden, z. B. auf ein Blech von 1 mm Stärke, wobei die Platinauflage dann eine Stärke von 10 μΐη besitzt.Boundary layer between titanium and platinum, in which PfTi 8 can be proven by X-ray. After this diffusion annealing, further rolling can be carried out, e.g. B. on a sheet of 1 mm thickness, the platinum layer then has a thickness of 10 μΐη.

Die Erzeugung einer PtTig-Zwischenschicht durch Diffusionsglühung kann unterbleiben, wenn man beispielsweise folgendermaßen verfährt: Ein Titanblech von 2 mm Stärke wird wie oben gebeizt und mit Platinfolienstreifen von 5 μΐη Stärke belegt. Es wird kalt und auf 1 mm abgewalzt. Der erhaltene Verbundwerkstoff besitzt eine sehr gute Haftfestigkeit zwischen Unterlage und Platinauflage, die in dem angeführten Beispiel etwa 2,5 μΐη beträgt. Dieser Verbundwerkstoff kann auch verformt werden, ohne daß die Platinauflage abreißt oder aufsteht. Zum Beispiel kann man aus einem Blech von 1 mm Titan mit 2,5 um Platinauflage Streckmetall herstellen. Dieses Material ist besonders geeignet als Anodenwerkstoff bei Prozessen, bei welchen Chlor erzeugt wird, ao oder als Anodenwerkstoff, beispielsweise in Chrombädern. The production of a PtTig intermediate layer by diffusion annealing can be omitted if one proceeds, for example, as follows: A titanium sheet 2 mm thick is pickled as above and covered with platinum foil strips 5 μm thick. It is rolled out cold and to 1 mm. The composite material obtained has very good adhesive strength between the base and the platinum coating, which in the example given is about 2.5 μm. This composite material can also be deformed without the platinum layer tearing off or standing up. For example, one can produce expanded metal from a sheet of 1 mm titanium with 2.5 μm platinum coating. This material is particularly suitable as anode material in processes in which chlorine is produced, ao or as an anode material, for example, in chromium baths.

Claims (2)

Patentansprüche:Patent claims: 1. Verfahren zur Herstellung eines Verbundwerkstoffes aus Titan und einem Metall der Platingruppe, insbesondere zur Verwendung als Elektrodenwerkstoff für elektrochemische Prozesse, durch Plattieren, dadurch gekennzeichnet, daß das Grundmetall aus Titan in einer Lösung, die mindestens lOnormal an H+- Ionen und lOnormal an Cl-Ionen ist, vorzugsweise in konzentrierter Salzsäure so lange gebeizt wird, bis sich eine nicht abwischbare, dunkelgraue Deckschicht bildet, und auf diese ein Metall der Platingruppe durch Kaltschweißen, insbesondere durch Kaltwalzen, mit wenigstens 25% Dickenabnahme haftfest aufplattiert wird.1. A method for producing a composite material from titanium and a metal of the platinum group, in particular for use as an electrode material for electrochemical processes, by plating, characterized in that the base metal is made of titanium in a solution containing at least 10 normal H + ions and 10 normal Cl ions are pickled, preferably in concentrated hydrochloric acid, until a dark gray top layer that cannot be wiped off is formed, and a platinum group metal is adhered to this by cold welding, in particular by cold rolling, with a reduction in thickness of at least 25%. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der durch Aufwalzen erzeugte Verbundwerkstoff in inerter Atmosphäre bei Temperaturen zwischen 600 und 1000° C während 2 bis 30 Minuten, vorzugsweise 5 bis 10 Minuten, bei 700° C geglüht wird.2. The method according to claim 1, characterized in that the generated by rolling Composite material in an inert atmosphere at temperatures between 600 and 1000 ° C during 2 to 30 minutes, preferably 5 to 10 minutes, is calcined at 700 ° C. 509 518/374 3.65 © Bnndesdruckerei Berlin509 518/374 3.65 © Bnndesdruckerei Berlin
DED39673A 1962-08-23 1962-08-23 Process for the production of a composite material of titanium and a metal of the platinum group by plating Pending DE1188895B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DED39673A DE1188895B (en) 1962-08-23 1962-08-23 Process for the production of a composite material of titanium and a metal of the platinum group by plating

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DED39673A DE1188895B (en) 1962-08-23 1962-08-23 Process for the production of a composite material of titanium and a metal of the platinum group by plating
DEV24779A DE1202255B (en) 1963-10-30 1963-10-30 Process for the production of catalysts for the activation of hydrogen or oxygen

Publications (1)

Publication Number Publication Date
DE1188895B true DE1188895B (en) 1965-03-11

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ID=25971479

Family Applications (1)

Application Number Title Priority Date Filing Date
DED39673A Pending DE1188895B (en) 1962-08-23 1962-08-23 Process for the production of a composite material of titanium and a metal of the platinum group by plating

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1671422A1 (en) * 1967-02-10 1971-06-16 Chemnor Ag Electrode and coating for the same
US4137370A (en) * 1977-08-16 1979-01-30 The United States Of America As Represented By The Secretary Of The Air Force Titanium and titanium alloys ion plated with noble metals and their alloys
US4181590A (en) * 1977-08-16 1980-01-01 The United States Of America As Represented By The Secretary Of The Air Force Method of ion plating titanium and titanium alloys with noble metals and their alloys
EP0350895A1 (en) * 1988-07-13 1990-01-17 Peroxid-Chemie GmbH Valve metal/platinum composite electrode

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1671422A1 (en) * 1967-02-10 1971-06-16 Chemnor Ag Electrode and coating for the same
US4137370A (en) * 1977-08-16 1979-01-30 The United States Of America As Represented By The Secretary Of The Air Force Titanium and titanium alloys ion plated with noble metals and their alloys
US4181590A (en) * 1977-08-16 1980-01-01 The United States Of America As Represented By The Secretary Of The Air Force Method of ion plating titanium and titanium alloys with noble metals and their alloys
EP0350895A1 (en) * 1988-07-13 1990-01-17 Peroxid-Chemie GmbH Valve metal/platinum composite electrode
US4995550A (en) * 1988-07-13 1991-02-26 Peroxid-Chemie Gmbh Valve metal/platinum composite electrode

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