EP0198998A1 - Bain de dépôt galvanique d'un revêtement d'un alliage d'or-indium - Google Patents

Bain de dépôt galvanique d'un revêtement d'un alliage d'or-indium Download PDF

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Publication number
EP0198998A1
EP0198998A1 EP86100721A EP86100721A EP0198998A1 EP 0198998 A1 EP0198998 A1 EP 0198998A1 EP 86100721 A EP86100721 A EP 86100721A EP 86100721 A EP86100721 A EP 86100721A EP 0198998 A1 EP0198998 A1 EP 0198998A1
Authority
EP
European Patent Office
Prior art keywords
indium
gold
acid
bath
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.)
Granted
Application number
EP86100721A
Other languages
German (de)
English (en)
Other versions
EP0198998B1 (fr
Inventor
Werner Kuhn
Wolfgang Zilske
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
Publication of EP0198998A1 publication Critical patent/EP0198998A1/fr
Application granted granted Critical
Publication of EP0198998B1 publication Critical patent/EP0198998B1/fr
Expired 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
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold

Definitions

  • the invention relates to a bath for the electrodeposition of gold-indium alloy coatings at pH values less than 3, consisting of 1 to 20 g / l gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.5 to 50 g / 1 Indium in the form of a water-soluble indium salt, an acid and a buffer or conductive salt.
  • the co-deposition of indium from galvanic gold electrolytes leads to light yellow gold layers, which are mainly used in the decorative industry for the gold plating of watch cases, bracelets, glasses or jewelry.
  • the coatings have a particularly good resistance to creep corrosion of silver sulfide compared to other gold alloy coatings.
  • the gold-indium alloy coatings e.g. DE-PS 11 11 897
  • the gold-indium alloy coatings that can be deposited from weakly acid baths at pB 3.5 - 5 are characterized by great brittleness and tend to crack, which greatly impairs the corrosion resistance.
  • Indium is therefore deposited together with other metals such as nickel or cobalt, which affects the resistance to creep corrosion of silver sulfide.
  • the indium content in the coating is only about 1%.
  • the co-deposition of indium from a strongly acidic gold electrolyte is based on Potassium tetracyanoaurate (III) possible. Ductile, but no glossy coatings with indium contents of 2-3% are obtained under the specified conditions. The addition of a nickel or cobalt salt to the electrolyte makes it possible to deposit shiny coatings, which, however, appear relatively strongly gray. A light yellow shade is not achieved. The resistance to creep corrosion is also reduced here.
  • baths contain 1 to 20 g / 1 gold in the form of tetracyanoaurate (III), a water-soluble alloy metal salt, an acid and a complexing agent at pH values between 0.4 and 2.5.
  • This object is achieved in that it additionally contains 0.5 to 10 mg / 1 selenium and / or tellurium in the form of selenium or telluric acid and / or alkali selenite or tellurium.
  • the bath preferably contains the indium in the form of indium sulfate and sulfuric acid as the acid. Furthermore, it has proven to be advantageous if ammonium sulfate, sulfamic acid, aliphatic and / or aromatic sulfonic acids are used as buffer or conductive salts. Mixtures of 10 to 150 g / 1 ammonium sulfate with 10 to 150 g / 1 sulfamic acid, toluenesulfonic acid and / or 2-hydroxyethanesulfonic acid have proven particularly useful.
  • the bath is preferably operated at pH values between 0.4 and 2.5, temperatures between 20 and 70 ° C. and current densities of 0.2 to 5 A / dm 2 , in particular at temperatures between 50 and 60 ° C. and current densities between 1 and 3 A / dm 2 .
  • the selenium or tellurium compounds contained in the bath not only cause the deposition of high-gloss coatings, but also have an unexpectedly positive effect on other bath and coating properties. This makes it possible to deposit gold-indium alloy coatings with at least 10% by weight indium, which are light yellow and lie between 0 and 1N in the color scale according to DIN 8238.
  • the coatings are very ductile and can be isolated as stable foils.
  • silver sulfide i.e. with silver or a silver layer as a base, silver sulfide does not spread on the overlying gold-indium layer.
  • a suitable sulfonic acid has an advantageous effect. Compared to a pure sulfate bath, glossy coatings are obtained in a wider current density range.
  • a bath is made up of the following components:
  • the pH is adjusted to 1.0 and the bath is heated to 60 ° C.
  • a 2.8 ⁇ m thick shiny gold alloy layer containing 11% by weight indium is deposited on a bright nickel-plated copper sheet at a current density of 3 A / dm 2 in 5 minutes.
  • the pH is adjusted to 1.3.
  • a bath temperature of 50 ° C. a 2.7 ⁇ m thick, shiny gold alloy layer containing 9.1% indium is deposited on a cathode made of bright nickel-plated copper sheet at a current density of 1 A / dm 2 in 10 minutes.

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)
EP86100721A 1985-02-16 1986-01-21 Bain de dépôt galvanique d'un revêtement d'un alliage d'or-indium Expired EP0198998B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3505473 1985-02-16
DE3505473A DE3505473C1 (de) 1985-02-16 1985-02-16 Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsueberzuegen

Publications (2)

Publication Number Publication Date
EP0198998A1 true EP0198998A1 (fr) 1986-10-29
EP0198998B1 EP0198998B1 (fr) 1988-06-29

Family

ID=6262777

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86100721A Expired EP0198998B1 (fr) 1985-02-16 1986-01-21 Bain de dépôt galvanique d'un revêtement d'un alliage d'or-indium

Country Status (7)

Country Link
US (1) US4617096A (fr)
EP (1) EP0198998B1 (fr)
JP (1) JPS61190089A (fr)
BR (1) BR8600414A (fr)
DE (2) DE3505473C1 (fr)
HK (1) HK58091A (fr)
ZA (1) ZA86305B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4916235A (en) * 1986-11-26 1990-04-10 University Of Dayton Resin systems derived from benzocyclobutene-maleimide compounds
US7465385B2 (en) 2005-06-02 2008-12-16 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes
US8142637B2 (en) 2005-06-02 2012-03-27 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8903818D0 (en) * 1989-02-20 1989-04-05 Engelhard Corp Electrolytic deposition of gold-containing alloys
CH680370A5 (fr) * 1989-12-19 1992-08-14 H E Finishing Sa
US6805786B2 (en) * 2002-09-24 2004-10-19 Northrop Grumman Corporation Precious alloyed metal solder plating process
JP5497261B2 (ja) 2006-12-15 2014-05-21 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． インジウム組成物
TWI400363B (zh) * 2007-08-28 2013-07-01 羅門哈斯電子材料有限公司 電化學沈積之銦複合材料
EP2848714B1 (fr) * 2008-04-22 2016-11-23 Rohm and Haas Electronic Materials LLC Procédé de régénération d'ions indium dans des compositions de dépôt électrique d'indium
US8840770B2 (en) * 2010-09-09 2014-09-23 International Business Machines Corporation Method and chemistry for selenium electrodeposition
US9145616B2 (en) * 2012-02-29 2015-09-29 Rohm and Haas Elcetronic Materials LLC Method of preventing silver tarnishing
EP3550057A3 (fr) * 2018-04-03 2019-11-13 Supro GmbH Revêtement de surface multicouche

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH418085A (fr) * 1964-08-19 1966-07-31 Pilot Pen Co Ltd Electrolyte pour le dépôt galvanique d'alliages d'or
EP0037535A2 (fr) * 1980-04-03 1981-10-14 Degussa Aktiengesellschaft Bain galvanique pour le dépôt de revêtements d'or et d'alliages d'or
FR2538816A1 (fr) * 1983-01-04 1984-07-06 Omi Int Corp Bain pour former, par electrolyse, un revetement en alliage d'or et procede d'utilisation de ce bain
EP0119424A1 (fr) * 1983-03-16 1984-09-26 Degussa Aktiengesellschaft Procédé pour le dépôt des couches en alliage or-argent brillantes de bas carat

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1111897B (de) * 1957-08-13 1961-07-27 Sel Rex Corp Bad zum galvanischen Abscheiden glaenzender Goldlegierungsueberzuege
US3990954A (en) * 1973-12-17 1976-11-09 Oxy Metal Industries Corporation Sulfite gold plating bath and process
JPS52108342A (en) * 1976-03-09 1977-09-10 Citizen Watch Co Ltd Gold alloy electroplating method
JPS53149132A (en) * 1977-06-01 1978-12-26 Citizen Watch Co Ltd Golddpalladiummcopper alloy plating liquid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH418085A (fr) * 1964-08-19 1966-07-31 Pilot Pen Co Ltd Electrolyte pour le dépôt galvanique d'alliages d'or
EP0037535A2 (fr) * 1980-04-03 1981-10-14 Degussa Aktiengesellschaft Bain galvanique pour le dépôt de revêtements d'or et d'alliages d'or
FR2538816A1 (fr) * 1983-01-04 1984-07-06 Omi Int Corp Bain pour former, par electrolyse, un revetement en alliage d'or et procede d'utilisation de ce bain
EP0119424A1 (fr) * 1983-03-16 1984-09-26 Degussa Aktiengesellschaft Procédé pour le dépôt des couches en alliage or-argent brillantes de bas carat

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4916235A (en) * 1986-11-26 1990-04-10 University Of Dayton Resin systems derived from benzocyclobutene-maleimide compounds
US7465385B2 (en) 2005-06-02 2008-12-16 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes
US8142637B2 (en) 2005-06-02 2012-03-27 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes

Also Published As

Publication number Publication date
DE3505473C1 (de) 1986-06-05
BR8600414A (pt) 1986-10-14
JPS61190089A (ja) 1986-08-23
US4617096A (en) 1986-10-14
EP0198998B1 (fr) 1988-06-29
HK58091A (en) 1991-08-02
DE3660353D1 (en) 1988-08-04
ZA86305B (en) 1986-08-27

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