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EP0521950A1 - METHOD FOR APPLYING SILVER GRAPHITE DISPERSION COATINGS. - Google Patents

METHOD FOR APPLYING SILVER GRAPHITE DISPERSION COATINGS.

Info

Publication number
EP0521950A1
EP0521950A1 EP91906474A EP91906474A EP0521950A1 EP 0521950 A1 EP0521950 A1 EP 0521950A1 EP 91906474 A EP91906474 A EP 91906474A EP 91906474 A EP91906474 A EP 91906474A EP 0521950 A1 EP0521950 A1 EP 0521950A1
Authority
EP
European Patent Office
Prior art keywords
graphite
silver
wetting agent
conductive salt
free
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
Application number
EP91906474A
Other languages
German (de)
French (fr)
Other versions
EP0521950B1 (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 provided for electroplating at current densities of 1 to 3 A / dm.
  • 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 which enables work with relatively high current densities for cutting 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 that a higher current density can be achieved with rack galvanizing. 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 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 a cutting separation.
  • 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.
  • 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.
  • alkyl sulfate of an alkali salt has the following
  • a branched alkyl sulfate of an alkali salt has the following structure, for example:
  • Wetting agents also use protein fat urekondensate and protein hydrolyzate.
  • metal objects to be provided with a silver-graphite dispersion coating are coated in an electrolyte of the following composition: _.
  • metal objects are provided with a dispersion coating in an electrolyte of the following composition under the specified conditions: potassium silver cyanide ⁇ [aeg (CN) 2 J. 120 g / 1
  • Silver-graphite dispersion coatings are applied to metal objects after customary pretreatment with an electrolyte of the following composition under the following conditions:

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  • 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

Dans le cas d'un procédé connu pour l'application de dépôts d'argent-graphite, on utilise un électrolyte avec du cyanure d'argent de potassium, du sel conducteur, du graphite, un agent mouillant et un additif brillanteur. Afin de pouvoir produire avec un électrolyte exempt de cyanure libre, à des densités de courant relativement élevées, des dépôts électrolytiques d'argent-graphite durcis par dispersion, l'application de tels dépôts se fait au moyen d'un électrolyte avec un sel conducteur exempt de cyanure libre. Le présent procédé permet l'application de dépôts électrolytiques d'argent-graphite durcis par dispersion avec une teneur en graphite de 1 à 2,5 %.In the case of a known process for the application of silver-graphite deposits, an electrolyte with potassium silver cyanide, conductive salt, graphite, a wetting agent and a brightener additive is used. In order to be able to produce with an electrolyte free from free cyanide, at relatively high current densities, dispersion-hardened silver-graphite electrolytic deposits, the application of such deposits is carried out by means of an electrolyte with a conductive salt free from free cyanide. The present process allows the application of dispersion hardened silver-graphite electroplated deposits with a graphite content of 1 to 2.5%.

Description

Verfahren zum Aufbringen von Silber-Graphit-Dispersions- überzügenProcess for applying silver-graphite dispersion coatings

Die Erfindung bezieht sich auf ein Verfahren zum Aufbringen von Silber-Graphit-Dispersionsüberzügen mit einem Alkalimetall- silbercyanid, 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 Dispersions¬ überzügen wird als Leitsalz Kaliumcyanid als freies Cyanid verwendet. Als Netzmittel sind für das bekannte Verfahren unter anderem Türkischrotöl, sulfoniertes Oleatester und Fettalko- holsulfonat geeignet. Das bekannte Verfahren ist zur Ge¬ sstteellllggaalvanisierung bei Stromdichten von 1 bis 3 A/dm vor- gesehen.A method of this type is known from DE 25 43 082 C3. In this known method 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 provided for electroplating at current densities of 1 to 3 A / dm.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zum Aufbringen von Silber-Graphit-Dispersionsüberzügen vorzuschla- gen, das mit einem von freiem Cyanid freien Elektrolyten auskommt und ein Arbeiten mit verhältnismäßig hohen Strom¬ dichten zur Schneilabscheidung 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 which enables work with relatively high current densities for cutting deposition.

Zur Lösung dieser Aufgabe wird bei einem Verfahren der eingangs angegebenen Art erfindungsgemäß das Aufbringen der Silber-Gra- phit-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 Gestellgal- vanisierung eine höhere Stromdichte erzielbar ist. Ein zusätz¬ licher Vorteil besteht darin, daß mit unlöslichen Anoden ge¬ arbeitet 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 that a higher current density can be achieved with rack galvanizing. 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 Durchlauf¬ anlage aufgebracht. Infolge der Schwall- oder Spritzgalva- nisierung ist eine partielle Beschichtung von mit Überzügen zu versehenden Teilen möglich. Darüber hinaus läßt sich das erfin¬ dungsgemäße Verfahren mit relativ hohen Stromdichten durch¬ führen, wodurch eine Schneilabscheidung ermöglicht ist.In the process 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 plating, a 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 a cutting separation.

Als Leitsalz ohne freies Cyanid kommen verschiedene Salze in Frage. Als besonders vorteilhaft wird es angesehen, wenn als Leitsalz di-Kaliu hydrogenphosphat, Kaliumdiphosphat oder ein Alkalisalz organischer Säuren verwendet wird; bei diesen Alkalisalzen kann es sich um Kaliumeitrat, 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 % Gra-To achieve silver-graphite coatings with 1 to 2.5% graphite

2 phit bei Stromstärken bis zu 20 A/dm werden bei dem erfin¬ dungsgemäßen Verfahren als Netzmittel vorteilhafterweise an- ionaktive Netzmittel mit einer Konzentration von 0,5 bis 30 ml/1 verwendet.2 phit at currents up to 20 A / dm, in the process according to the invention, anionic wetting agents with a concentration of 0.5 to 30 ml / l are advantageously used as wetting agents.

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 geradkettigesSuch 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

Alkylsulfat eines Alkalisalzes hat beispielsweise folgendenFor example, alkyl sulfate of an alkali salt has the following

Aufbau:Construction:

CH, J - (CH,,)n- 0 - SO,_?" Na+ oder K+ n = 3 ... 9 Ein verzweigtes Alkylsulfat eines Alkalisalzes hat z. B. den folgenden Aufbau:CH, J - (CH ,,) n- 0 - SO, _? " Na + or K + n = 3 ... 9 A branched alkyl sulfate of an alkali salt has the following structure, for example:

CH,3 - (CH2)„n2 - " Na+ oder K+ CH, 3 - (CH2) "n2 - " Na + or K +

nl = 0 ... 3 n2 = 0 . . . 7 nl = 0 ... 3 n2 = 0. , , 7

Als ein Beispiel für Alkylsulfonate eines Alkalisalzes wird folgender Aufbau angegeben:The following structure is given as an example of alkyl sulfonates of an alkali salt:

CH3 - (CH2)n - S03 "Na+ n = 4 ... 13CH 3 - (CH 2 ) n - S0 3 " Na + n = 4 ... 13

Mit Vorteil lassen sich bei dem erfindungsgemäßeπ Verfahren alsAdvantageously, in the method according to the invention

Netzmittel auch Eiweißfetts urekondensate und Eiweißhydrolysate verwenden.Wetting agents also use protein fat urekondensate and protein hydrolyzate.

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 Zusammen¬ setzung beschichtet: _.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: _.

Kaliumsilbercyanid K|AG (CN.J 120 g/1 di-Kaliumhydrogenphosphat K2HP04 90 g/1 Graphit c 100 g/1Potassium silver cyanide K | AG (CN.J 120 g / 1 di-potassium hydrogen phosphate K 2 HP0 4 90 g / 1 graphite c 100 g / 1

Kaliumselenocyanat KSeCN 10 mg/1Potassium selenocyanate KSeCN 10 mg / 1

Natrium 2-Ethylhexylsulfat (40% Wirkstoff) 2 ml/1 pH-Wert 8,5Sodium 2-ethylhexyl sulfate (40% active ingredient) 2 ml / 1 pH 8.5

Temperatur 30 βC Stromdichte 5 A/dm2 110 A/dm2 Temperature 30 β C current density 5 A / dm 2 110 A / dm 2

Graphitgehalt des Überzugs 1,8 Gew.% 1,4 Gew.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 angege¬ benen Bedingungen mit einem Dispersionsüberzug versehen: Kaliumsilbercyanid κ[Äg(CN)2J. 120 g/1After the usual pretreatment, metal objects are provided with a dispersion coating in an electrolyte of the following composition under the specified conditions: potassium silver cyanide κ [aeg (CN) 2 J. 120 g / 1

Kaliumdiphosphat K4P2°7 80 g/1Potassium diphosphate K 4 P 2 ° 7 80 g / 1

Graphit ' C 100 g/1 Kaliumselenocyanat KSeCN 10 mg/1Graphite ' C 100 g / 1 potassium selenocyanate KSeCN 10 mg / 1

Natriumalkylsulfonat (40% Wirkstoff) 5 ml/1 pH-Wert Temperatur Stromdichte Graphitgehalt im Überzug Sodium alkyl sulfonate (40% active ingredient) 5 ml / 1 pH value temperature current density graphite content in the coating

Beispiel 3Example 3

Silber-Graphit-Dispersionsüberzügen werden auf Metallgegen¬ stände nach üblicher Vorbehandlung mit einem Elektrolyten nachstehender Zusammensetzung unter den nachstehend angegebenen Bedingungen aufgebracht:Silver-graphite dispersion coatings are applied to metal objects after customary pretreatment with an electrolyte of the following composition under the following conditions:

Kaliumsilbercyanid tri-Kaliumcitrat-MonohydratPotassium silver cyanide tri-potassium citrate monohydrate

Borsäure GraphitBoric acid graphite

Selenige SäureSelenium acid

Natrium n-Octylsulfat (42% Wirkstoff) pH-WertSodium n-octyl sulfate (42% active ingredient) pH

Temperatur StromdichteTemperature current density

Graphitgehalt im Überzug Graphite content in the coating

Claims

Patentansprüche Claims 1. Verfahren zum Aufbringen von Silber-Graphit-Dispersions- überzügen mit einem Alkalimetallsilbercyanid, Leitsalz, Graphit, Netzmittel und einen Glanzzusatz enthaltenden Elektrolyten, d a d u r c h g e k e n n z e i c h n e t , daß das Aufbringen der Silber-Graphit-Dispersionsüberzüge mit einem Elektrolyten mit einem von freiem Cyanid freien Leitsalz vorgenommen wird.1. 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, characterized in that the application of the silver-graphite dispersion coatings is carried out with an electrolyte with a conductive salt free of free cyanide becomes. 2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t , daß das Aufbringen der Silber-Graphit-Überzüge mit einem Schwall- oder Spritzgalvanisierverfahren in einer' Durchlaufanlage vorgenommen wird.2. The method according to claim 1, characterized in that the application of the silver-graphite coatings is carried out with a surge or spray plating process in a ' continuous system. 3. Verfahren nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t , daß als Leitsalz di-Kaliumhydrogenphosphat verwendet wird.3. The method according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that di-potassium hydrogen phosphate is used as the conductive salt. 4. Verfahren nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t , daß als Leitsalz Kaliumdiphosphat verwendet wird.4. The method of claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that potassium diphosphate is used as the conductive salt. 5. Verfahren nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t , daß als Leitsalz ein Alkalisalz organischer Säuren verwendet wird,5. The method of claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that an alkali metal salt of organic acids is used as the conductive salt, 6. Verfahren nach einem der vorangehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , daß als Netzmittel ein anionaktives Netzmittel mit einer Kon¬ zentration von 0,5 bis 30 ml/1 verwendet wird.6. The method according to any one of the preceding claims, d a d u r c h g e k e n n z e i c h n e t that an anionic wetting agent with a concentration of 0.5 to 30 ml / 1 is used as wetting agent. 7. Verfahren nach Anspruch 6 d a d u r c h g e k e n n z e i c h n e t , daß als Netzmittel Alkali-Salze von Alkylsulfaten bzw. -sulfonaten mit einer geradkettigen oder verzweigten Alkylkettenlänge von C4 bis C14 verwendet wird.7. The method according to claim 6, characterized in that alkali salts of alkyl sulfates or sulfonates with a straight-chain or branched alkyl chain length of C4 to C14 are used as wetting agents. 8. Verfahren nach Anspruch 6, d a d u r c h g e k e n n z e i c h n e t , daß als Netzmittel ein Alkali-Salz einer hochsulfatierten Fettsäure verwendet wird.8. The method of claim 6, d a d u r c h g e k e n n z e i c h n e t that an alkali salt of a highly sulfated fatty acid is used as a wetting agent. 9. Verfahren nach Anspruch 6, d a d u r c h g e k e n n z e i c h n e t , daß als Netzmittel ein Eiweißfettsäurekondensat verwendet wird.9. The method of claim 6, d a d u r c h g e k e n n z e i c h n e t that a protein fatty acid condensate is used as a wetting agent. 10. Verfahren nach Anspruch 6, d a d u r c h g e k e n n z e i c h n e t , daß als Netzmittel ein Eiweißhydrolysat verwendet wird. 10. The method of claim 6, d a d u r c h g e k e n n z e i c h n e t that a protein hydrolyzate 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 true EP0521950A1 (en) 1993-01-13
EP0521950B1 EP0521950B1 (en) 1995-03-08

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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)

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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

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WO1991014808A1 (en) 1991-10-03
JPH05505853A (en) 1993-08-26
EP0521950B1 (en) 1995-03-08
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

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