EP0198998B1 - Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsüberzügen - Google Patents

Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsüberzügen Download PDF

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Publication number
EP0198998B1
EP0198998B1 EP86100721A EP86100721A EP0198998B1 EP 0198998 B1 EP0198998 B1 EP 0198998B1 EP 86100721 A EP86100721 A EP 86100721A EP 86100721 A EP86100721 A EP 86100721A EP 0198998 B1 EP0198998 B1 EP 0198998B1
Authority
EP
European Patent Office
Prior art keywords
bath
indium
acid
gold
coating
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
Application number
EP86100721A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0198998A1 (de
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/de
Application granted granted Critical
Publication of EP0198998B1 publication Critical patent/EP0198998B1/de
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 / I 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 which can be deposited from weakly acidic baths at pH 3.5-5 (e.g. DE-PS-1 111 897) are extremely brittle and tend to crack, which greatly impairs 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 genalt in the coating is only about 1%.
  • 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 / l 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 buffers or conductive salts. Mixtures of 10 to 150 g / l ammonium sulfate with 10 to 150 g / l sulfamic acid, toluenesulfonic acid and / or 2-hydroxyethanesulfonic acid have proven particularly useful.
  • the bath is preferably operated at pH values between 0.5 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 1 N in the color scale according to DIN 8238.
  • silver sulfide i.e. in the case of silver or a silver layer as a base, silver sulfide does not spread on the gold layer above.
  • 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 by dissolving the following components:
  • indium sulfate 9.1 g of indium sulfate are dissolved in about 100 ml of water and 12 ml of sulfuric acid (98%) by heating. After dilution to about 500 ml, 50 g of ammonium sulfate and hydroxiethanesulfonic acid Na salt and 3.2 mg of selenic acid are added and dissolved.
  • Example 1 a bath is made up of the following components: The pH is adjusted to 1.0 and the bath is heated to 600C. 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 in 5 minutes.
  • a bath is produced from the following components: The pH is adjusted to 1.3. At 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 / dm2 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 Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsüberzügen Expired EP0198998B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3505473 1985-02-06
DE3505473A DE3505473C1 (de) 1985-02-16 1985-02-16 Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsueberzuegen

Publications (2)

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

Family

ID=6262777

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86100721A Expired EP0198998B1 (de) 1985-02-16 1986-01-21 Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsüberzügen

Country Status (7)

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

Families Citing this family (12)

* 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
GB8903818D0 (en) * 1989-02-20 1989-04-05 Engelhard Corp Electrolytic deposition of gold-containing alloys
CH680370A5 (pt) * 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
SG127854A1 (en) 2005-06-02 2006-12-29 Rohm & Haas Elect Mat Improved gold electrolytes
US20090104463A1 (en) 2006-06-02 2009-04-23 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes
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
EP2031098B1 (en) * 2007-08-28 2019-05-29 Rohm and Haas Electronic Materials LLC Composition and corresponding method for the electrodeposition of indium composites
EP2848714B1 (en) * 2008-04-22 2016-11-23 Rohm and Haas Electronic Materials LLC Method of replenishing indium ions in indium electroplating compositions
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 (de) * 2018-04-03 2019-11-13 Supro GmbH Mehrschichtige oberflächenbeschichtung

Family Cites Families (8)

* 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
CH418085A (fr) * 1964-08-19 1966-07-31 Pilot Pen Co Ltd Electrolyte pour le dépôt galvanique d'alliages d'or
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
DE3012999C2 (de) * 1980-04-03 1984-02-16 Degussa Ag, 6000 Frankfurt Bad und Verfahren zur galvanischen Abscheidung von hochglänzenden und duktiler Goldlegierungsüberzügen
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
DE3309397A1 (de) * 1983-03-16 1984-09-20 Degussa Ag, 6000 Frankfurt Elektrolytisches bad zum abscheiden von niederkaraetigen, glaenzenden gold-silber-legierungsueberzuegen

Also Published As

Publication number Publication date
EP0198998A1 (de) 1986-10-29
HK58091A (en) 1991-08-02
JPS61190089A (ja) 1986-08-23
DE3660353D1 (en) 1988-08-04
DE3505473C1 (de) 1986-06-05
ZA86305B (en) 1986-08-27
US4617096A (en) 1986-10-14
BR8600414A (pt) 1986-10-14

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