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EP0149830B2 - Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes - Google Patents
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EP0149830B2 - Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes - Google Patents

Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes Download PDF

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Publication number
EP0149830B2
EP0149830B2 EP19840115879 EP84115879A EP0149830B2 EP 0149830 B2 EP0149830 B2 EP 0149830B2 EP 19840115879 EP19840115879 EP 19840115879 EP 84115879 A EP84115879 A EP 84115879A EP 0149830 B2 EP0149830 B2 EP 0149830B2
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EP
European Patent Office
Prior art keywords
acid
methylene
phosphonic
bath
complexing agent
Prior art date
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Application number
EP19840115879
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English (en)
French (fr)
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EP0149830A3 (en
EP0149830B1 (de
EP0149830A2 (de
Inventor
Heinz Emmenegger
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H E Finishing SA
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H E Finishing SA
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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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold

Definitions

  • the present invention relates to an electrolytic bath for depositing thin layers (of the order of at least 0.5 ⁇ ) of pure gold on passive surfaces (for example stainless steel, Ti, Mo, alloys based on Cr and of Ni).
  • passive surfaces for example stainless steel, Ti, Mo, alloys based on Cr and of Ni.
  • the baths used for the galvanic deposition of gold are generally prepared from solutions of potassium aurocyanide KAu (CN) 2 , to which various salts, acids or alkaline products are added, according to the methods, to improve the electrical conductivity of the bath and the crystallization conditions of the metal.
  • the aurocyanide is only stable up to a pH of around 3 and, below this value, it decomposes into insoluble yellow CN gold cyanide and hydrocyanic acid HCN.
  • very low pH baths is especially essential to deposit a thin layer of adherent pure gold on objects whose surface is highly passive, that is to say, for example stainless steel, alloys containing a high proportion of chromium and nickel, in titanium, in molybdenum, or on surfaces having previously undergone a galvanic chromium plating, a chemical nickel plating or a coating of molybdenum-manganese alloy.
  • compositions as disclosed in the examples of US Pat. No. 4,168,214 are in practice unusable for obtaining electrolytic baths having a pH of less than about 0.4.
  • these baths have the drawback, in particular with regard to environmental protection, of containing alkaline cyanides.
  • the object of this invention therefore consists in providing an electrolytic bath on the deposit of thin layers (of the order of ⁇ C, 5, ⁇ ) of pure gold (24cts) on passive surfaces, which adhere perfectly to said passive surfaces and can be used as a bonding layer for the subsequent deposition of thicker layers of a gold alloy, this bath having a pH of at most 0.4.
  • the electrolytic bath according to the invention contains from 0.5 to 20 g / I of gold in the form of an auricyanide of an alkali metal, in which the gold is trivalent, and at least an acid present in sufficient concentration for the pH of this bath to be at most 0.4 and is characterized in that the acid is at least one organic acid chosen from the group comprising sufamic acid, monochloroacetic acids, dichlo - racetic and trichloroacetic, malic acid, and 1-hydroxy-1, 1-ethylidene-diphosphoric, hydroxy-methyl-phosphoric and amino-tris (methylene-phosphonic) acids, and mixtures thereof, or else sulfuric acid in combination with at least one organic complexing agent chosen from the alkaline salts of diethylene-triamine-penta- (methylene-phosphonic), ethylene-diamine-tetra (methylene-phosphonic), hexamethylene-diamine-tetra acids - (
  • this bath may contain the auricyanide in the form of potassium auricyanide KAu (CN) 4 or sodium auricyanide NaAu (CN) 4 , and its pH is preferably between 0.1 and 0.3.
  • the acid concentration being relatively high, it does not prove necessary to add conductive salts, the solution being sufficiently electrically conductive.
  • These acids can be used either alone or mixed with each other, in concentrations of 40 to 500 g / l, except for sulfamic acid, the solubility of which in water is limited and which can be present in 100 g / I at saturation, which is reached for a concentration of approximately 150 g / I at room temperature.
  • complexing agents as well as other complexing agents such as amino-carbonic acids (see for example DE 3,012,999), cannot be used in large quantities because they risk precipitating.
  • other compounds mentioned below can be introduced into the electrolytic bath according to the invention, therefore having a pH of less than 0.4, as complexing agents and without precipitating, in quantities at least greater than 20 g / I.
  • These compounds are N-carboxymethyl-aspartic and N, N-bis (carboxymethyl) aspartic acids having the following formulas: or the salts thereof, as well as the compound represented by the following formula, where R is an alkyl or alkylene group having 1 to 5 C atoms, or the salts thereof.
  • the baths are generally used at room temperature, with platinum titanium or graphite anodes.
  • platinum titanium or graphite anodes For certain applications, in particular for coating particularly passive surfaces, it is possible to raise the working temperature of these baths up to 80 ° C.
  • the chemicals which enter into their composition not being volatile, and having a perfect stability at this temperature, there does not follow any loss or any change in the behavior of the bath during electrolysis.
  • a stainless steel wafer was treated in the bath, at room temperature, with a current density of 3 Aldm 2 for 5 minutes.
  • the pure gold deposit obtained is both perfectly adherent to the substrate and brilliant.
  • a stainless steel plate was treated in this bath, at room temperature, with a current density of 4 Aldm 2 for 4 minutes.
  • the deposit obtained is both perfectly adherent and shiny.
  • a stainless steel plate was treated in this bath, at room temperature, with a current density of 4 Aldm 2 for 3 minutes.
  • the deposit obtained is both perfectly adherent and shiny.
  • This bath was intentionally polluted with 50 mg / I of iron.
  • the addition of 4 g / l of EDTA makes it possible to obtain, under the same electrolysis conditions, a deposit of pure yellow and shiny gold.
  • the stainless steel plate treated in this bath at a current density of 5 A / dm 2 for 5 minutes, had an adherent and shiny gold layer of 0.2 to 0.3 ⁇

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)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (9)

1. Elektrolytbad zur Aufbringung von dünnen Schichten von reinem Gold auf passive Oberflächen, das es von 0.5 bis 20g/1 Gold in Form eines Alkalimetallcyanoaurats, in dem das Gold dreiwertig ist, und mindestens eine Säure in einer aureichenden Menge zur Einstellung des pH-Wertes des Bads auf höchstens 0.4 enthält, dadurch gekennzeichnet, dass die Säure mindestens eine organische Säure, die unter Sulfamidsäure, Monochlor-, Dichlor- und Trichloressigsäure, Apfelsäure, 1-Hydroxy-1, 1-ethylidendiphosphonsäure, Hydroxymethylphosphonsäure und Amino-tris(methylenphosphonsäure) sowie ihren Gemischen ausgewählt wird, oder die Schwefelsäure zusammen mit mindestens einem organischen Komplexbildner, der unter den Alkalimetallsalzen von Diehylentriaminpenta(methylenphosphonsäure), Ethylen-diamin-tetra (essigsäure) sowie ihren Gemischen ausgewählt wird, oder N-Carboxy-methyl-asparaginsäure oder N,N-Bis(carboxymethyl) asparaginsäure oder eines ihrer Salze, oder eine Verbindung der folgenden Formel :
Figure imgb0014
in der R Alkyl oder Alkylen mit 1 bis 5 Kohlenstoffatomen, oder eines ihrer Salze, ist.
2. Bad nach Anspruch 1, gekennzeichnet durch einen pH-Wert von 0,1 bis 0,3.
3. Bad nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass die Säure in einer Menge von 40 bis 500 g/I vorhanden ist.
4. Bad nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es, im Falle der Benutzung einer organischen Säure, zusätzlich mindestens einen organischen Komplexbildner enthält.
5. Bad nach Anspruch 4, dadurch gekennzeichnet, dass der organische Komplexbildner unter den Alkalimetallsalzen von Diethylentriamin-penta(methylenphosphonsäure), Ethylendiamin-tetra(methylenphosphon- säure), Hexamethylen-diamin-tetra(methylenphosphonsäure) und Ethylen-diamin-tetra (essigsäure) sowie ihren Gemischen ausgewählt wird.
6. Bad nach Anspruch 4, dadurch gekennzeichnet, dass der organische Komplexbildner in einer Menge von 1 bis 20 g/I vorhanden ist.
7. Bad nach Anspruch 4, dadurch gekennzeichnet, dass der organische Komplexbildner N-Carboxy-methyl-asparaginsäure oder N,N-Bis(carboxymethyl) asparaginsäure oder eines ihrer Salze ist.
8. Bad nach Anspruch 4, dadurch gekennzeichnet, dass der organische Komplexbildner eine Verbindung der folgenden Formel :
Figure imgb0015
in der R Alkyl oder Alkylen mit 1 bis 5 Kohlenstoffatomen, oder eines ihrer Salze, ist.
9. Bad nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass der organische Komplexbildner in einer Menge über 20 g/l vorhanden ist.
EP19840115879 1983-12-29 1984-12-20 Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes Expired - Lifetime EP0149830B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH6961/83 1983-12-29
CH696183A CH665656A5 (fr) 1983-12-29 1983-12-29 Bain d'or acide et utilisation de ce bain en electroplastie.

Publications (4)

Publication Number Publication Date
EP0149830A2 EP0149830A2 (de) 1985-07-31
EP0149830A3 EP0149830A3 (en) 1986-10-15
EP0149830B1 EP0149830B1 (de) 1989-04-05
EP0149830B2 true EP0149830B2 (de) 1992-05-13

Family

ID=4317752

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19840115879 Expired - Lifetime EP0149830B2 (de) 1983-12-29 1984-12-20 Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes

Country Status (3)

Country Link
EP (1) EP0149830B2 (de)
CH (1) CH665656A5 (de)
DE (2) DE149830T1 (de)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3902977A (en) * 1973-12-13 1975-09-02 Engelhard Min & Chem Gold plating solutions and method
AT353071B (de) * 1977-10-06 1979-10-25 Oxy Metal Industries Corp Cyanidfreies, basisches sulfitbad zur elektrolytischen faellung von gold-zink- legierungen
US4168214A (en) * 1978-06-14 1979-09-18 American Chemical And Refining Company, Inc. Gold electroplating bath and method of making the same
GB2038361B (en) * 1978-11-11 1983-08-17 Ibm Trivalent chromium plating bath
DE3012999C2 (de) * 1980-04-03 1984-02-16 Degussa Ag, 6000 Frankfurt Bad und Verfahren zur galvanischen Abscheidung von hochglänzenden und duktiler Goldlegierungsüberzügen
DE3021665A1 (de) * 1980-06-10 1981-12-17 Degussa Ag, 6000 Frankfurt Stark saures goldlegierungsbad

Also Published As

Publication number Publication date
DE149830T1 (de) 1985-10-24
DE3477588D1 (en) 1989-05-11
EP0149830A3 (en) 1986-10-15
EP0149830B1 (de) 1989-04-05
EP0149830A2 (de) 1985-07-31
CH665656A5 (fr) 1988-05-31

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