EP0698676A1 - Bain d'électrodéposition d'alliages cuivre-étain - Google Patents

Bain d'électrodéposition d'alliages cuivre-étain Download PDF

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Publication number
EP0698676A1
EP0698676A1 EP95104355A EP95104355A EP0698676A1 EP 0698676 A1 EP0698676 A1 EP 0698676A1 EP 95104355 A EP95104355 A EP 95104355A EP 95104355 A EP95104355 A EP 95104355A EP 0698676 A1 EP0698676 A1 EP 0698676A1
Authority
EP
European Patent Office
Prior art keywords
tin
bath
copper
cyanide
potassium
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
EP95104355A
Other languages
German (de)
English (en)
Other versions
EP0698676B1 (fr
Inventor
Otto Camus
Thomas Frey
Wolfgang Hempel
Günter Dr. Herklotz
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.)
WC Heraus GmbH and Co KG
Original Assignee
WC Heraus GmbH and Co KG
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 WC Heraus GmbH and Co KG filed Critical WC Heraus GmbH and Co KG
Publication of EP0698676A1 publication Critical patent/EP0698676A1/fr
Application granted granted Critical
Publication of EP0698676B1 publication Critical patent/EP0698676B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Definitions

  • the invention relates to a bath for the electrodeposition of copper-tin alloys, which consists of water, copper cyanide, tin (IV) compound, alkali metal cyanide, alkali metal hydroxide, a complexing agent and optionally an alkali metal phosphate.
  • the bath known from DE 33 39 541 C2 for the electrodeposition of copper-tin alloy coatings contains 1-60 g / l copper as copper cyanide, 7-30 g / l tin as alkali metal stannate, 0.1-100 g / l one or more Complexing agents from the group of phosphate, polyphosphate, phosphonate and polyoxycarboxylic acids, 1-50 g / l alkali metal cyanide, 1-50 g / l alkali metal hydroxide, 0-50 g / l alkali metal carbonate and 0.05-5 g / l of one or more additives from the Groups of fatty acid amido alkyl dialkylamine oxides, dialkylamine betaines and ethoxylated naphthols.
  • the coatings deposited from this bath are bare. In order to obtain glossy coatings too, brighteners have to be added to the bath.
  • DE 33 46 721 A1 describes an alkaline, cyanide-containing bath for the electrodeposition of high-gloss coatings (bronzing) from copper and tin, as well as other alloy metals - namely zinc, molybdenum, cadmium, mercury, lead, zirconium, vanadium, beryllium and / or cobalt - Containing alloys described.
  • the other alloy metals are present in the bath in the form of organic complexes or chelates, including at least one aminopolycarboxy complexing agent, and hydroxide complexes.
  • tartrates, citrates, acetates, pyrophosphates, glycerophosphates, thione phosphates and / or carbonates may also be present.
  • the aim of the invention is to create a bath of the type described in the introduction, from which shiny copper-tin alloy layers can be deposited without the need for additional brighteners.
  • the bathroom should be as simple as possible, which means that it does not require any additional additives, and should be easy to monitor and maintain.
  • the composition of the deposited copper-tin alloys should be as independent as possible from fluctuations in the current density.
  • the bath according to the invention is characterized in that it contains the potassium salt of gluconic acid, glucaric acid and / or glucuronic acid as a complexing agent and has a pH of 8-14.
  • the bathroom has proven itself as a preparation from water and 5 - 20 g / l Copper (I) cyanide, 10 - 150 g / l Tin (IV) compound, 50-100 g / l Potassium cyanide, 1 - 80 g / l Potassium hydroxide and 50-150 g / l Potassium salt of gluconic acid, glucaric acid and / or glucuronic acid.
  • Copper (I) cyanide 10 - 150 g / l Tin (IV) compound
  • 50-100 g / l Potassium cyanide 1 - 80 g / l Potassium hydroxide
  • 50-150 g / l Potassium salt of gluconic acid, glucaric acid and / or glucuronic acid 5 - 20 g / l Copper (I) cyanide, 10 - 150 g / l Tin (IV) compound, 50-100 g / l Potassium
  • the bath is preferably a preparation of water and 10 - 15 g / l Copper (I) cyanide, 30-100 g / l Tin (IV) compound, 50 - 70 g / l Potassium cyanide, 5 - 50 g / l Potassium hydroxide and 80-120 g / l Potassium salt of gluconic acid, glucaric acid and / or glucuronic acid.
  • Alkaline metal stannates especially potassium stannate
  • tin (IV) halides especially tin (IV) chloride
  • tin (IV) compound Alkaline metal stannates, especially potassium stannate, and tin (IV) halides, especially tin (IV) chloride, are preferred as the tin (IV) compound.
  • the potassium salt of gluconic acid has proven particularly useful as a complexing agent.
  • an alkali metal phosphate is present in the bath, an amount of 50-100 g / l has proven to be favorable.
  • the bath can be operated at temperatures of 20-70 ° C., preferably at 50-70 ° C., and with current densities of 0.1-10 A / dm, preferably 2-6 A / dm.
  • the copper-tin alloys separated from the bath are characterized by a high gloss.
  • the additional use of gloss agents is not necessary.
  • All of the components forming the bath contribute to the good properties which characterize the bath according to the invention.
  • the potassium hydroxide and the potassium salt of gluconic acid, glucaric acid and glucuronic acid are of particular importance.
  • the bath can be used for electroplating small parts as well as tapes and wires and enables the deposition of copper alloys with a tin content of up to 60% by weight.
  • the deposition of alloys with a tin content of 30-60% by weight is preferred.
  • the alloys are bronze to silver-colored and are suitable for technical and decorative purposes. They are particularly important as a substitute for nickel, which is a potential allergen.
  • a faster deposition of the alloys can be achieved by increasing the current density and the bath temperature without major fluctuations in the composition of the deposited alloys - given the copper and tin content of the bath.
  • the bath obtained in this way is turned into a shiny, silver-colored copper-tin alloy of 68% by weight copper and 32% by weight at a bath temperature of 65 ° C. and with current densities of 0.1-5 A / dm (Hull cell). Tin deposited.
  • the bathroom is stable; There is no precipitation.
  • the bath obtained in this way is turned into a shiny, silver-colored copper-tin alloy of 60% by weight copper and 40% by weight at a bath temperature of 65 ° C. and with current densities of 0.1-5 A / dm (Hull cell). Tin deposited.
  • the bathroom is stable; There is no precipitation.
  • a shiny, silver-colored copper-tin alloy composed of 51% by weight of tin and 49% by weight of copper is deposited from the bath thus obtained at a bath temperature of 60 ° C. and with current densities of 1-5 A / dm (Hull cell) .
  • the bathroom is stable; There is no precipitation.
  • a shiny, silver-colored copper-tin alloy composed of 53% by weight of tin and 47% by weight of copper is deposited from the bath thus obtained at a bath temperature of 60 ° C. and with current densities of 1-5 A / dm (Hull cell) .
  • the bathroom is stable; There is no precipitation.
  • a shiny, silver-colored copper-tin alloy composed of 51% by weight of tin and 49% by weight of copper is deposited from the bath thus obtained at a bath temperature of 60 ° C. and with current densities of 1-5 A / dm (Hull cell) .
  • the bathroom is stable; There is no precipitation.
  • a shiny, silver-colored copper-tin alloy composed of 30% by weight of tin and 70% by weight of copper is deposited from the bath thus obtained at a bath temperature of 65 ° C. and with current densities of 1-10 A / dm (Hull cell) .
  • the bathroom is stable; There is no precipitation.
  • the addition of the baths necessary in the course of the separation is carried out in a simple manner by adding the substances used for the preparation of the baths.
  • a continuous one It is not necessary to determine the concentration of the potassium salt of gluconic acid, glucaric acid and glucuronic acid; based on the addition of tin (IV) compound, it is added in a ratio of 1: 1.

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)
EP95104355A 1994-07-29 1995-03-24 Bain d'électrodéposition d'alliages cuivre-étain Expired - Lifetime EP0698676B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4426914 1994-07-29
DE4426914A DE4426914C1 (de) 1994-07-29 1994-07-29 Bad zum galvanischen Abscheiden von Kupfer-Zinn-Legierungen

Publications (2)

Publication Number Publication Date
EP0698676A1 true EP0698676A1 (fr) 1996-02-28
EP0698676B1 EP0698676B1 (fr) 1997-09-24

Family

ID=6524448

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95104355A Expired - Lifetime EP0698676B1 (fr) 1994-07-29 1995-03-24 Bain d'électrodéposition d'alliages cuivre-étain

Country Status (2)

Country Link
EP (1) EP0698676B1 (fr)
DE (2) DE4426914C1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104962959A (zh) * 2015-07-21 2015-10-07 深圳市新富华表面技术有限公司 电镀液
IT202100008084A1 (it) * 2021-03-31 2022-10-01 Bluclad S P A Soluzione elettrolitica per l’elettrodeposizione su substrato metallico di uno strato preparatore a base di rame e stagno

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3339541A1 (de) * 1983-11-02 1985-05-15 Degussa Ag, 6000 Frankfurt Alkalisch-cyanidisches bad zur galvanischen abscheidung von kupfer-zinn-legierungsueberzuegen
DE3346721A1 (de) * 1983-12-23 1985-06-27 Fa. Karl-Wilh. Hen, 5820 Gevelsberg Alkalisches bad zum aufbringen eines hochglaenzenden galvanischen ueberzugs auf einen traeger

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3339541A1 (de) * 1983-11-02 1985-05-15 Degussa Ag, 6000 Frankfurt Alkalisch-cyanidisches bad zur galvanischen abscheidung von kupfer-zinn-legierungsueberzuegen
DE3346721A1 (de) * 1983-12-23 1985-06-27 Fa. Karl-Wilh. Hen, 5820 Gevelsberg Alkalisches bad zum aufbringen eines hochglaenzenden galvanischen ueberzugs auf einen traeger

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104962959A (zh) * 2015-07-21 2015-10-07 深圳市新富华表面技术有限公司 电镀液
IT202100008084A1 (it) * 2021-03-31 2022-10-01 Bluclad S P A Soluzione elettrolitica per l’elettrodeposizione su substrato metallico di uno strato preparatore a base di rame e stagno

Also Published As

Publication number Publication date
DE4426914C1 (de) 1995-08-17
DE59500711D1 (de) 1997-10-30
EP0698676B1 (fr) 1997-09-24

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