EP0194432B1 - Bain de dépôt galvanique de couches d'alliage d'or-étain - Google Patents

Bain de dépôt galvanique de couches d'alliage d'or-étain Download PDF

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Publication number
EP0194432B1
EP0194432B1 EP86101083A EP86101083A EP0194432B1 EP 0194432 B1 EP0194432 B1 EP 0194432B1 EP 86101083 A EP86101083 A EP 86101083A EP 86101083 A EP86101083 A EP 86101083A EP 0194432 B1 EP0194432 B1 EP 0194432B1
Authority
EP
European Patent Office
Prior art keywords
tin
bath
gold
oxalic acid
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
Application number
EP86101083A
Other languages
German (de)
English (en)
Other versions
EP0194432A1 (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 EP0194432A1 publication Critical patent/EP0194432A1/fr
Application granted granted Critical
Publication of EP0194432B1 publication Critical patent/EP0194432B1/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 / tin 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), 0.1 to 10 g / l Tin in the form of a water-soluble tin salt, optionally 0.005 to 1 g / l of a further alloy metal in the form of a water-soluble salt, an acid and a buffer or conductive salt.
  • the galvanic co-deposition of tin from gold baths is of interest for decorative and technical applications.
  • gold / tin alloy baths are used to produce colored gold coatings, especially white gold layers, and in electrical engineering, the good corrosion resistance and solderability of tin combined with gold offers advantages over other alloy layers.
  • DE-OS 26 58 003 describes a galvanic bath which contains 1 to 30 g / l gold as gold (III) cyanide complex and 1 to 150 g / l tin as halogen stannate (IV) complex, the pH being adjusted -Values and to stabilize the complex of halogen halide acids, which lead to considerable corrosion damage to the galvanic systems.
  • poisonous halogen is developed at the anode during electrolysis, which escapes in gaseous form under the given working conditions.
  • an aqueous solution of 1 to 20 g / l gold in the form of alkali and / or Ammonium tetracyanoaurate (III) 0.1 to 10 g / I tin in the form of a water-soluble tin salt, optionally 0.005 to 1 g / I
  • the bath contains the tin in the form of a tin (IV) oxalato complex.
  • oxalato tin (IV) acid can also be used, for example.
  • oxalic acid or oxalic acid and ammonium sulfate are used as buffer or conductive salts.
  • 10 to 50 g / l oxalic acid or mixtures of 10 to 50 g / l oxalic acid and 10 to 100 g / l ammonium sulfate are used.
  • the bath can additionally contain 0.005 to 1 g / l of a further alloy metal in the form of a water-soluble nickel or cobalt salt.
  • the pH of the bath is advantageously adjusted to 0.5 to 2.5 using sulfuric acid or oxalic acid.
  • the bath is normally used at temperatures between 20 and 60 ° C, preferably at 40 to 55 ° C, and current densities of 0.2 to 5 A / dm 2 , preferably 1 to 4 A / dm 2 .
  • Oxalato tin (IV) acid is used e.g. B. by dissolving tin in oxalic acid with the addition of hydrogen peroxide, potassium oxalatostannate (IV) by reacting tin (IV) chloride with potassium oxalate.
  • the additional co-deposition of cobalt or nickel can influence the color and the technological properties, such as hardness and mechanical abrasion resistance, of the coatings.
  • the current yield then drops to values of 40 to 50%.
  • the very low content of non-metallic impurities in the coatings is also surprising. At less than 0.1%, it is far below that of comparable gold alloy coatings.
  • the coatings are also very ductile despite their high hardness (HV or .015 approx. 230).
  • the elongation at break measured on 10 ⁇ m thick layers on a copper foil is around 20% in the order of that of fine gold layers.
  • the pH is adjusted to 1.0 with sulfuric acid.
  • a 1.5 ⁇ m thick, shiny gold layer containing 0.4% tin is deposited on a bright nickel-plated cathode made of polished copper sheet at a current density of 1 A / dm 2 in 10 minutes.
  • cobalt in the form of cobalt sulfate is dissolved in the bath.
  • the pH is adjusted to 0.8 with sulfuric acid.
  • the baths are stable over a long period of time.

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)

Claims (6)

1. Bain pour la précipitation galvanique de revêtements d'alliage Or/Etain à des valeurs de pH inférieures à 3, consistant en une solution aqueuse à 1 à 20 g/I d'or sous forme d'auri (III) tétracyanure alcalin ou d'Ammonium, à 0,1 à 10 g/I d'étain sous forme d'un sel d'étain soluble dans l'eau, à éventuellement 0,005 à 1 g/I d'un autre métal d'alliage sous forme d'un sel soluble dans l'eau, en un acide et en un sel tampon conducteur, caractérisé en ce qu'il contient l'étain sous la forme d'un complexe Oxalatostannique (IV).
2. Bain selon la revendication 1, caractérisé en ce qu'il contient le complexe d'étain sous la forme d'oxalatostannate (IV) de potassium.
3. Bain selon la revendication 1 ou 2, caractérisé en ce qu'on utilise comme sel conducteur ou tampon, l'acide oxalique, ou l'acide oxalique et le sulfate d'Ammonium.
4. Bain selon la revendication 1 à 3, caractérisé en ce qu'il contient de 10 à 50 g/I d'acide oxalique ou de 10 à 50 g/I d'acide oxalique et de 10 à 100 g/l de sulfate d'Ammonium.
5. Bain selon la revendication 1 à 4, caractérisé en ce qu'il renferme en outre de 0,005 à 1 g/I de Cobalt ou de Nickel sous la forme d'un sel soluble dans l'eau.
6. Bain selon la revendication 1 à 5, caractérisé en ce qu'il manifeste une valeur de pH de 0,5 à 2,5 et que l'ajustement de la valeur du pH s'effectue avec de l'acide sulfurique ou de l'acide oxalique.
EP86101083A 1985-03-15 1986-01-28 Bain de dépôt galvanique de couches d'alliage d'or-étain Expired EP0194432B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3509367A DE3509367C1 (de) 1985-03-15 1985-03-15 Bad und Verfahren zur galvanischen Abscheidung von Gold/Zinn-Legierungsueberzuegen
DE3509367 1985-03-15

Publications (2)

Publication Number Publication Date
EP0194432A1 EP0194432A1 (fr) 1986-09-17
EP0194432B1 true EP0194432B1 (fr) 1988-06-15

Family

ID=6265335

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86101083A Expired EP0194432B1 (fr) 1985-03-15 1986-01-28 Bain de dépôt galvanique de couches d'alliage d'or-étain

Country Status (7)

Country Link
US (1) US4634505A (fr)
EP (1) EP0194432B1 (fr)
JP (1) JPH0684553B2 (fr)
BR (1) BR8601029A (fr)
DE (2) DE3509367C1 (fr)
HK (1) HK58191A (fr)
ZA (1) ZA86309B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH680370A5 (fr) * 1989-12-19 1992-08-14 H E Finishing Sa
DE4406434C1 (de) * 1994-02-28 1995-08-10 Heraeus Gmbh W C Bad zum galvanischen Abscheiden von Gold-Zinn-Legierungen
US20060237324A1 (en) * 2003-05-21 2006-10-26 Fred Hayward Pulse plating process for deposition of gold-tin alloy
WO2005110287A2 (fr) * 2004-05-11 2005-11-24 Technic, Inc. Solution galvanoplastique pour alliage eutectique or-etain
WO2006078549A1 (fr) * 2005-01-21 2006-07-27 Technic, Inc. Procede de placage par impulsions pour depot d'un alliage or/etain
CN114759182B (zh) * 2022-05-25 2023-04-07 昆明理工大学 石墨烯包覆草酸锡负极材料及其制备方法、电池

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3475290A (en) * 1965-05-07 1969-10-28 Suwa Seikosha Kk Bright gold plating solution and process
GB1442325A (en) * 1972-07-26 1976-07-14 Oxy Metal Finishing Corp Electroplating with gold and gold alloys
US4013523A (en) * 1975-12-24 1977-03-22 Oxy Metal Industries Corporation Tin-gold electroplating bath and process
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
GB2153386B (en) * 1984-02-01 1987-08-26 Omi Int Corp Gold alloy plating bath

Also Published As

Publication number Publication date
HK58191A (en) 1991-08-02
DE3660313D1 (en) 1988-07-21
JPH0684553B2 (ja) 1994-10-26
US4634505A (en) 1987-01-06
DE3509367C1 (de) 1986-08-14
JPS61223194A (ja) 1986-10-03
BR8601029A (pt) 1986-11-25
ZA86309B (en) 1986-08-27
EP0194432A1 (fr) 1986-09-17

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