[go: up one dir, main page]

EP0521950B1 - Process for depositing silver/graphite dispersion-hardened coatings - Google Patents

Process for depositing silver/graphite dispersion-hardened coatings Download PDF

Info

Publication number
EP0521950B1
EP0521950B1 EP91906474A EP91906474A EP0521950B1 EP 0521950 B1 EP0521950 B1 EP 0521950B1 EP 91906474 A EP91906474 A EP 91906474A EP 91906474 A EP91906474 A EP 91906474A EP 0521950 B1 EP0521950 B1 EP 0521950B1
Authority
EP
European Patent Office
Prior art keywords
process according
silver
wetting agent
graphite
conducting salt
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
Application number
EP91906474A
Other languages
German (de)
French (fr)
Other versions
EP0521950A1 (en
Inventor
Ursula Michelsen-Mohammadein
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.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of EP0521950A1 publication Critical patent/EP0521950A1/en
Application granted granted Critical
Publication of EP0521950B1 publication Critical patent/EP0521950B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials

Definitions

  • the invention relates to a method for applying silver-graphite dispersion coatings with an alkali metal silver cyanide, conductive salt, graphite, wetting agent and an electrolyte containing a gloss additive.
  • a method of this type is known from DE 25 43 082 C3.
  • potassium cyanide is used as the free salt as the conductive salt.
  • Turkish red oil, sulfonated oleate ester and fatty alcohol sulfonate are suitable as wetting agents for the known process.
  • the known method is intended for rack electroplating at current densities of 1 to 5 A / dm2.
  • the invention is based on the object of proposing a method for applying silver-graphite dispersion coatings which manages with an electrolyte free of free cyanide and enables work with relatively high current densities for rapid deposition.
  • the silver-graphite dispersion coatings are applied with an electrolyte with a conductive salt free of free cyanide in a method of the type mentioned at the outset.
  • An advantage of the method according to the invention is that it is carried out with an electrolyte without free cyanide. Another advantage is the fact that a higher current density can be achieved with rack electroplating. An additional advantage is that insoluble anodes are used.
  • the silver-graphite dispersion coatings advantageously applied with a surge or spray plating process in a continuous system.
  • a surge or spray electroplating partial coating of parts to be coated is possible.
  • the method according to the invention can be carried out with relatively high current densities, which enables rapid deposition.
  • Various salts can be used as the conductive salt without free cyanide. It is considered particularly advantageous if di-potassium hydrogen phosphate, potassium diphosphate or an alkali salt of organic acids is used as the conductive salt; These alkali salts can be potassium citrate, potassium malate or sodium acetate.
  • anionic wetting agents with a concentration of 0.5 to 30 ml / l are advantageously used as wetting agents in the process according to the invention.
  • Such wetting agents are advantageously alkali salts of alkyl sulfates or sulfonates with a straight-chain or branched alkyl chain length of C4 to C14, or an alkali salt of a highly sulfated fatty acid.
  • an electrolyte of the following composition Potassium silver cyanide K [Ag (CN) 2] 120 g / l di-potassium hydrogen phosphate K2HPO4 90 g / l graphite C. 100 g / l Potassium selenium cyanate KSeCN 10 mg / l Sodium 2-ethylhexyl sulfate (40% active ingredient) 2 ml / l PH value 8.5 temperature 30 ° C Current density 5 A / dm2 10 A / dm2 Graphite content of the coating 1.8% by weight 1.4% by weight
  • metal objects are in one.
  • Silver-graphite dispersion coatings are applied to metal objects after customary pretreatment with an electrolyte of the following composition under the following conditions: Potassium silver cyanide K [Ag (CN) 2] 120 g / l tri-potassium citrate monohydrate C6H5K3O7.H2O 100 g / l Boric acid H3BO3 30 g / l graphite C. 100 g / l Selenium acid H2SeO3 2 g / l Sodium n-octyl sulfate (42% active ingredient) 5 ml / l PH value 8th temperature 30 ° C Current density 5 A / dm2 Graphite content in the coating 1.5% by weight

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Paints Or Removers (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

Abstract

A prior art process for depositing silver/graphite dispersion coatings uses an electrolyte containing potassium silver cyanide, conducting salt, graphite, wetting agents and a brightener. In order to produce silver/graphite dispersion coatings using an electrolyte not containing free cyanide and using relatively high current densities, the deposition of the coating is carried out with an electrolyte containing a conducting salt which contains no free cyanide. The process enables silver/graphite dispersion coatings with graphite contents of 1-2.5 % to be produced.

Description

Die Erfindung bezieht sich auf ein Verfahren zum Aufbringen Von Silber-Graphit-Dispersionsüberzügen mit einem Alkalimetallsilbercyanid, Leitsalz, Graphit, Netzmittel und einen Glanzzusatz enthaltenden Elektrolyten.The invention relates to a method for applying silver-graphite dispersion coatings with an alkali metal silver cyanide, conductive salt, graphite, wetting agent and an electrolyte containing a gloss additive.

Ein Verfahren dieser Art ist aus der DE 25 43 082 C3 bekannt. Bei diesem bekannten Verfahren zum Aufbringen von Dispersionsüberzügen wird als Leitsalz Kaliumcyanid als freies Cyanid verwendet. Als Netzmittel sind für das bekannte Verfahren unter anderem Türkischrotöl, sulfoniertes Oleatester und Fettalkoholsulfonat geeignet. Das bekannte Verfahren ist zur Gestellgalvanisierung bei Stromdichten von 1 bis 5 A/dm² vorgesehen.A method of this type is known from DE 25 43 082 C3. In this known process for applying dispersion coatings, potassium cyanide is used as the free salt as the conductive salt. Turkish red oil, sulfonated oleate ester and fatty alcohol sulfonate are suitable as wetting agents for the known process. The known method is intended for rack electroplating at current densities of 1 to 5 A / dm².

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zum Aufbringen von Silber-Graphit-Dispersionsüberzügen vorzuschlagen, das mit einem von freiem Cyanid freien Elektrolyten auskommt und ein Arbeiten mit verhältnismäßig hohen Stromdichten zur Schnellabscheidung ermöglicht.The invention is based on the object of proposing a method for applying silver-graphite dispersion coatings which manages with an electrolyte free of free cyanide and enables work with relatively high current densities for rapid deposition.

Zur Lösung dieser Aufgabe wird bei einem Verfahren der eingangs angegebenen Art erfindungsgemäß das Aufbringen der Silber-Craphit-Dispersionsüberzüge mit einem Elektrolyten mit einem von freiem Cyanid freien Leitsalz vorgenommen.To achieve this object, according to the invention, the silver-graphite dispersion coatings are applied with an electrolyte with a conductive salt free of free cyanide in a method of the type mentioned at the outset.

Ein Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß es mit einem Elektrolyten ohne freies Cyanid durchgeführt wird. Ein weiterer Vorteil ist darin zu sehen, daß bei Gestellgalvanisierung eine höhere Stromdichte erzielbar ist. Ein zusätzlicher Vorteil besteht darin, daß mit unlöslichen Anoden gearbeitet wird.An advantage of the method according to the invention is that it is carried out with an electrolyte without free cyanide. Another advantage is the fact that a higher current density can be achieved with rack electroplating. An additional advantage is that insoluble anodes are used.

Bei dem erfindungsgemäßen Verfahren werden die Silber-Graphit-Dispersionsüberzüge vorteilhafterweise mit einem Schwall- oder Spritzgalvanisierverfahren in einer Durchlaufanlage aufgebracht. Infolge der Schwall- oder Spritzgalvanisierung ist eine partielle Beschichtung von mit Überzügen zu versehenden Teilen möglich. Darüber hinaus läßt sich das erfindungsgemäße Verfahren mit relativ hohen Stromdichten durchführen, wodurch eine Schnellabscheidung ermöglicht ist.In the method according to the invention, the silver-graphite dispersion coatings advantageously applied with a surge or spray plating process in a continuous system. As a result of the surge or spray electroplating, partial coating of parts to be coated is possible. In addition, the method according to the invention can be carried out with relatively high current densities, which enables rapid deposition.

Als Leitsalz ohne freies Cyanid kommen verschiedene Salze in Frage. Als besonders vorteilhaft wird es angesehen, wenn als Leitsalz di-Kaliumhydrogenphosphat, Kaliumdiphosphat oder ein Alkalisalz organischer Säuren verwendet wird; bei diesen Alkalisalzen kann es sich um Kaliumcitrat, Kaliummalat oder Natriumazetat handeln.Various salts can be used as the conductive salt without free cyanide. It is considered particularly advantageous if di-potassium hydrogen phosphate, potassium diphosphate or an alkali salt of organic acids is used as the conductive salt; These alkali salts can be potassium citrate, potassium malate or sodium acetate.

Zur Erzielung von Silber-Graphit-überzügen mit 1 bis 2,5 % Graphit bei Stromstärken bis zu 20 A/dm² werden bei dem erfindungsgemäßen Verfahren als Netzmittel vorteilhafterweise anionaktive Netzmittel mit einer Konzentration von 0,5 bis 30 ml/l verwendet.To achieve silver-graphite coatings with 1 to 2.5% graphite at currents up to 20 A / dm², anionic wetting agents with a concentration of 0.5 to 30 ml / l are advantageously used as wetting agents in the process according to the invention.

Als solche Netzmittel kommen vorteilhafterweise Alkali-Salze von Alkylsulfaten bzw. -sulfonaten mit einer geradkettigen oder verzweigten Alkylkettenlänge von C4 bis C14 in Frage, oder ein Alkali-Salz einer hochsulfatierten Fettsäure. Ein geradkettiges Alkylsulfat eines Alkalisalzes hat beispielsweise folgenden Aufbau:



        CH₃ - (CH₂)n- O - SO₃⁻ Na⁺ oder K⁺



n = 3 ... 9
Ein verzweigtes Alkylsulfat eines Alkalisalzes hat z. B. den folgenden Aufbau:

Figure imgb0001

oder K⁺
n1 = 0 ... 3
n2 = 0 ... 7
Als ein Beispiel für Alkylsulfonate eines Alkalisalzes wird folgender Aufbau angegeben:



        CH₃ - (CH₂)n - SO₃⁻Na⁺



n = 4 ... 13
Mit Vorteil lassen sich bei dem erfindungsgemäßen Verfahren als Netzmittel auch Eiweißfettsäurekondensate und Eiweißhydrolysate verwenden.Such wetting agents are advantageously alkali salts of alkyl sulfates or sulfonates with a straight-chain or branched alkyl chain length of C4 to C14, or an alkali salt of a highly sulfated fatty acid. A straight-chain alkyl sulfate of an alkali salt has the following structure, for example:



CH₃ - (CH₂) n - O - SO₃⁻ Na⁺ or K⁺



n = 3 ... 9
A branched alkyl sulfate of an alkali salt has e.g. B. the following structure:
Figure imgb0001
or K⁺
n1 = 0 ... 3
n2 = 0 ... 7
The following structure is given as an example of alkyl sulfonates of an alkali salt:



CH₃ - (CH₂) n - SO₃⁻Na⁺



n = 4 ... 13
Protein fatty acid condensates and protein hydrolyzates can also advantageously be used as wetting agents in the process according to the invention.

Zur Erläuterung der Erfindung werden nachfolgend Beispiele angegeben.Examples are given below to illustrate the invention.

Beispiel 1example 1

Nach einer in der Galvanotechnik üblichen Vorbehandlung werden mit einem Silber-Graphit-Dispersionsüberzug zu versehende Metallgegenstände in einem Elektrolyten folgender Zusammensetzung beschichtet: Kaliumsilbercyanid K[Ag (CN)₂] 120 g/l di-Kaliumhydrogenphosphat K₂HPO₄ 90 g/l Graphit C 100 g/l Kaliumselencyanat KSeCN 10 mg/l Natrium 2-Ethylhexylsulfat (40% Wirkstoff) 2 ml/l pH-Wert 8,5 Temperatur 30°C Stromdichte 5 A/dm² 10 A/dm² Graphitgehalt des Überzugs 1,8 Gew.% 1,4 Gew.% After a pretreatment customary in electroplating, metal objects to be provided with a silver-graphite dispersion coating are coated in an electrolyte of the following composition: Potassium silver cyanide K [Ag (CN) ₂] 120 g / l di-potassium hydrogen phosphate K₂HPO₄ 90 g / l graphite C. 100 g / l Potassium selenium cyanate KSeCN 10 mg / l Sodium 2-ethylhexyl sulfate (40% active ingredient) 2 ml / l PH value 8.5 temperature 30 ° C Current density 5 A / dm² 10 A / dm² Graphite content of the coating 1.8% by weight 1.4% by weight

Beispiel 2Example 2

Nach der üblichen Vorbehandlung werden Metallgegenstände in einem. Elektrolyten folgender Zusammensetzung unter den angegebenen Bedingungen mit einem Dispersionsüberzug versehen: Kaliumsilbercyanid K [Ag(CN)₂] 120 g/l Kaliumdiphosphat K₄P₂O₇ 80 g/l Graphit C 100 g/l Kaliumselenocyanat KSeCN 10 mg/l Natriumalkylsulfonat (40% Wirkstoff) 5 ml/l pH-Wert 9,0 Temperatur 20 °C Stromdichte 5 A/dm² Graphitgehalt im Überzug 1,3 Gew.% After the usual pretreatment, metal objects are in one. Provide electrolytes of the following composition with a dispersion coating under the specified conditions: Potassium silver cyanide K [Ag (CN) ₂] 120 g / l Potassium diphosphate K₄P₂O₇ 80 g / l graphite C. 100 g / l Potassium selenocyanate KSeCN 10 mg / l Sodium alkyl sulfonate (40% active ingredient) 5 ml / l PH value 9.0 temperature 20 ° C Current density 5 A / dm² Graphite content in the coating 1.3% by weight

Beispiel 3Example 3

Silber-Graphit-Dispersionsüberzügen werden auf Metallgegenstände nach üblicher Vorbehandlung mit einem Elektrolyten nachstehender Zusammensetzung unter den nachstehend angegebenen Bedingungen aufgebracht: Kaliumsilbercyanid K [Ag(CN)₂] 120 g/l tri-Kaliumcitrat-Monohydrat C₆H₅K₃O₇.H₂O 100 g/l Borsäure H₃BO₃ 30 g/l Graphit C 100 g/l Selenige Säure H₂SeO₃ 2 g/l Natrium n-Octylsulfat (42% Wirkstoff) 5 ml/l pH-Wert 8 Temperatur 30 °C Stromdichte 5 A/dm² Graphitgehalt im Überzug 1,5 Gew.% Silver-graphite dispersion coatings are applied to metal objects after customary pretreatment with an electrolyte of the following composition under the following conditions: Potassium silver cyanide K [Ag (CN) ₂] 120 g / l tri-potassium citrate monohydrate C₆H₅K₃O₇.H₂O 100 g / l Boric acid H₃BO₃ 30 g / l graphite C. 100 g / l Selenium acid H₂SeO₃ 2 g / l Sodium n-octyl sulfate (42% active ingredient) 5 ml / l PH value 8th temperature 30 ° C Current density 5 A / dm² Graphite content in the coating 1.5% by weight

Claims (10)

  1. Process for depositing silver graphite composite coatings using an electrolyte containing an alkali metal silver cyanide, a conducting salt, graphite, a wetting agent and a brightener, characterised in that the deposition of silver graphite composite coatings is performed using an electrolyte containing a conducting salt that is free of free cyanide.
  2. Process according to claim 1,
    characterised in that the deposition of silver graphite composite coatings is performed by a flow or spray electrodeposition process in a continuous plant.
  3. Process according to claim 1 or 2,
    characterised in that dibasic potassium phosphate is used as a conducting salt.
  4. Process according to claim 1 or 2,
    characterised in that potassium pyrophosphate is used as a conducting salt.
  5. Process according to claim 1 or 2,
    characterised in that an alkali salt of organic acids is used as a conducting salt.
  6. Process according to one of the preceding claims, characterised in that an anion-active wetting agent in a concentration of from 0.5 to 30 ml/l is used as a wetting agent.
  7. Process according to claim 6,
    characterised in that alkali salts of alkyl sulphates or of sulphonates having a straight-chain or branched alkyl chain length of from C4 to C14 are used as wetting agents.
  8. Process according to claim 6, characterised in that an alkali salt of a highly sulphated fatty acid is used as a wetting agent.
  9. Process according to claim 6,
    characterised in that a protein fatty acid condensate is used as a wetting agent.
  10. Process according to claim 6,
    characterised in that a protein hydrolysate is used as a wetting agent.
EP91906474A 1990-03-28 1991-03-18 Process for depositing silver/graphite dispersion-hardened coatings Expired - Lifetime EP0521950B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4010346 1990-03-28
DE4010346A DE4010346A1 (en) 1990-03-28 1990-03-28 METHOD OF APPLYING SILVER GRAPHITE DISPERSION OVERLAYS
PCT/DE1991/000241 WO1991014808A1 (en) 1990-03-28 1991-03-18 Process for depositing silver/graphite dispersion-hardened coatings

Publications (2)

Publication Number Publication Date
EP0521950A1 EP0521950A1 (en) 1993-01-13
EP0521950B1 true EP0521950B1 (en) 1995-03-08

Family

ID=6403453

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91906474A Expired - Lifetime EP0521950B1 (en) 1990-03-28 1991-03-18 Process for depositing silver/graphite dispersion-hardened coatings

Country Status (7)

Country Link
US (1) US5290422A (en)
EP (1) EP0521950B1 (en)
JP (1) JPH05505853A (en)
CA (1) CA2079210A1 (en)
DE (2) DE4010346A1 (en)
ES (1) ES2069286T3 (en)
WO (1) WO1991014808A1 (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4783954B2 (en) 2004-06-21 2011-09-28 Ｄｏｗａメタルテック株式会社 Composite plating material and method for producing the same
JP4806808B2 (en) * 2005-07-05 2011-11-02 Ｄｏｗａメタルテック株式会社 Composite plating material and method for producing the same
JP4669967B2 (en) * 2005-07-05 2011-04-13 Ｄｏｗａメタルテック株式会社 Manufacturing method of composite plating material
JP4862192B2 (en) * 2005-09-29 2012-01-25 Ｄｏｗａメタルテック株式会社 Manufacturing method of composite plating material
JP2008127641A (en) * 2006-11-22 2008-06-05 Dowa Metaltech Kk Method for producing composite plated material
JP5625166B2 (en) * 2011-01-05 2014-11-19 Ｄｏｗａメタルテック株式会社 Composite plating material and method for producing the same
CN105297095A (en) * 2015-12-14 2016-02-03 南昌航空大学 Functional coating of pure silver layer/pure-graphite composite layer and preparation method of functional coating
CN105386091A (en) * 2015-12-24 2016-03-09 南昌航空大学 Graphite dispersion composite additive
CN106757199A (en) * 2016-12-22 2017-05-31 唐恩(厦门)电气有限公司 One kind prepares high pressure and separates the silver-colored graphite coating process of switch
DE102018005352A1 (en) 2018-07-05 2020-01-09 Dr.-Ing. Max Schlötter GmbH & Co KG Silver electrolyte for the deposition of dispersion silver layers and contact surfaces with dispersion silver layers
CN109267124B (en) * 2018-10-19 2019-11-19 西安西电电气研究院有限责任公司 A kind of silver coated graphite composite deposite and preparation method thereof
JP7233991B2 (en) * 2019-03-18 2023-03-07 Ｄｏｗａメタルテック株式会社 Composite plated material and its manufacturing method
JP6804597B1 (en) 2019-08-01 2020-12-23 Ｄｏｗａメタルテック株式会社 Composite plating material and its manufacturing method
DE102021118820A1 (en) 2021-07-21 2023-01-26 Umicore Galvanotechnik Gmbh silver electrolyte

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2164050C3 (en) * 1971-12-23 1975-12-04 C. Uyemura & Co., Ltd., Osaka Electroplating bath of conventional composition for the joint deposition of metal and a permanently lubricating solid lubricant
US4024031A (en) * 1975-10-28 1977-05-17 Amp Incorporated Silver plating
CA1181715A (en) * 1980-11-10 1985-01-29 Yvonne Rymwid Composition and process for high speed bright silver plating

Also Published As

Publication number Publication date
WO1991014808A1 (en) 1991-10-03
JPH05505853A (en) 1993-08-26
ES2069286T3 (en) 1995-05-01
DE4010346A1 (en) 1991-10-02
DE59104898D1 (en) 1995-04-13
US5290422A (en) 1994-03-01
CA2079210A1 (en) 1991-09-29
EP0521950A1 (en) 1993-01-13

Similar Documents

Publication Publication Date Title
EP0521950B1 (en) Process for depositing silver/graphite dispersion-hardened coatings
DE2845439C2 (en) Bath for the galvanic deposition of coatings made of tin or tin alloys
DE3116743A1 (en) "METHOD FOR PRE-TREATING A NON-CONDUCTIVE SUBSTRATE FOR FOLLOWING GALVANIZATION"
EP1190118B1 (en) Bath system for galvanic deposition of metals
DE860300C (en) Electrolyte containing copper and tin salts for the production of copper-tin alloy coatings and a method for producing these coatings
DE1020845B (en) Bath and process for the galvanic deposition of an iron-zinc or iron-zinc-nickel alloy
DE112561T1 (en) AQUEOUS ELECTROPLATING SOLUTIONS AND METHOD FOR ELECTROPLATING PALLADIUM-SILVER ALLOYS.
GB1320373A (en) Copper electroplating in a citric acid bath
EP0149029A1 (en) Palladium bath
DE2032867C3 (en) Galvanic gold bath and process for the deposition of even, thick gold coatings
US3380814A (en) Electrolyte and method for coating articles with a gold-copper-antimony alloy and article thereof
DE2251285C3 (en) Alkaline bath for the galvanic deposition of gold alloys
DE3143225C2 (en) "Stable aqueous galvanic bath and process for the rapid deposition of silver coatings with a mirror finish"
DE1016527B (en) Bath and process for the galvanic production of leveling iron, iron-nickel or iron-nickel-zinc coatings
EP0046912B1 (en) Cyanide gold-baths and process for the galvanic deposition of gold-dispersion coatings that contain solid lubricant, and its application
DE3400139C2 (en)
DE3328067A1 (en) BATH AND METHOD FOR GALVANICALLY DEPOSITING DISPERSIONS CONTAINING PRECIOUS METAL AND METAL
DE4426914C1 (en) Bath for galvanically depositing copper@-tin@ alloys
DE1086508B (en) Acid galvanic copper bath
EP0384227B1 (en) Bath for the galvanic deposition of pure gold coatings
DE4040526C3 (en) Bath for the galvanic deposition of gold alloys
DE963389C (en) Bath for the production of galvanic nickel deposits
DE1796337C3 (en) Galvanic copper pyrophosphate baths
DE1696079C (en) Galvanic nickel bath
EP0081788A1 (en) Non-additive fast depositing galvanic palladium bath

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

Kind code of ref document: A1

Designated state(s): BE CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19920824

17Q First examination report despatched

Effective date: 19940422

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 59104898

Country of ref document: DE

Date of ref document: 19950413

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2069286

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950419

ITF It: translation for a ep patent filed
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
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970521

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19970620

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980211

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19980309

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19980311

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19980320

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19980325

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19980327

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990319

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990320

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990331

BERE Be: lapsed

Owner name: SIEMENS A.G.

Effective date: 19990331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991001

EUG Se: european patent has lapsed

Ref document number: 91906474.1

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991130

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19991001

EUG Se: european patent has lapsed

Ref document number: 91906474.1

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20010503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050318