EP0149830A2 - Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes - Google Patents

Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes Download PDF

Info

Publication number
EP0149830A2
EP0149830A2 EP84115879A EP84115879A EP0149830A2 EP 0149830 A2 EP0149830 A2 EP 0149830A2 EP 84115879 A EP84115879 A EP 84115879A EP 84115879 A EP84115879 A EP 84115879A EP 0149830 A2 EP0149830 A2 EP 0149830A2
Authority
EP
European Patent Office
Prior art keywords
acid
bath
bath according
gold
complexing agent
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
EP84115879A
Other languages
English (en)
French (fr)
Other versions
EP0149830B1 (de
EP0149830A3 (en
EP0149830B2 (de
Inventor
Heinz Emmenegger
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.)
H E Finishing SA
Original Assignee
H E Finishing SA
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=4317752&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0149830(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by H E Finishing SA filed Critical H E Finishing SA
Publication of EP0149830A2 publication Critical patent/EP0149830A2/de
Publication of EP0149830A3 publication Critical patent/EP0149830A3/fr
Publication of EP0149830B1 publication Critical patent/EP0149830B1/de
Application granted granted Critical
Publication of EP0149830B2 publication Critical patent/EP0149830B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 p) of pure gold on passive surfaces (for example stainless steel, Ti, Mo, alloys based on Cr and Ni, etc.).
  • passive surfaces for example stainless steel, Ti, Mo, alloys based on Cr and Ni, etc.
  • the baths used for the galvanic deposition of gold are generally prepared from potassium auricyanide solutions 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 conditions of crystallization of the metal.
  • the aurocyanide is only stable up to a pH of around 3 and, below this value, it decomposes into insoluble and yellow AuCN gold cyanide. HCN hydrocyanic acid.
  • baths with very low pH 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 galvanic chromium plating, chemical nickel plating or a coating of molybdenum-manganese alloy.
  • the object of this invention therefore consists in providing an electrolytic bath for the deposition of thin layers (of the order of ⁇ C, 5 p) of pure gold (24cts) on passive surfaces, which adhere perfectly to said passive surfaces and can serve as a bonding layer for the subsequent deposition of thicker layers of a gold alloy.
  • the electrolytic bath according to the invention aimed at achieving the above-mentioned aim, is characterized in that it contains from 0.5 to 20 g / 1 of gold in the form of the auricyanide of an alkali metal and at least one acid. present in sufficient concentration for the pH of this bath to be at most 0.4.
  • this bath can contain the auricocyanide 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 / 1 at saturation, which is reached for a concentration of approximately 150 g / 1 at room temperature.
  • organic complexing agents for example sodium, potassium, ammonium or amine salts, diethylene-triamine-penta (methylene-phosphonic), ethylene- diamine-tetra (methylene-phosphonic) and ethylene-diamine-tetra-acetic (EDTA), which are preferably used in concentrations of 1 to 20 g / l.
  • 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 / 1.
  • These compounds are N-carboxymethyl-aspartic acids and N, N-bis (carboxymethyl) aspartic having the formulas following:
  • 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 g phite anodes.
  • platinum titanium or g phite 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 o C.
  • the chemicals that go into their composition are not volatile, and having perfect stability at this temperature, there does not result 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 A / dm 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 A / dm 2 for 4 minutes.
  • the deposit obtained is both perfectly adherent and shiny.
  • the deposit obtained is both perfectly adherent and shiny.
  • a stainless steel plate was treated in this bath, at room temperature, with a density current of 4 A / dm 2 for 3 minutes.
  • the deposit obtained is both perfectly adherent and shiny.
  • This bath was intentionally polluted with 50 mg / 1 of iron.
  • the addition of 4 g / 1 of EDTA makes it possible to obtain, under the same electrolysis conditions, a deposit of pure yellow and shiny gold.
  • the stainless steel wafer 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 p.

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)
  • Electroplating Methods And Accessories (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
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
CH696183A CH665656A5 (fr) 1983-12-29 1983-12-29 Bain d'or acide et utilisation de ce bain en electroplastie.
CH6961/83 1983-12-29

Publications (4)

Publication Number Publication Date
EP0149830A2 true EP0149830A2 (de) 1985-07-31
EP0149830A3 EP0149830A3 (en) 1986-10-15
EP0149830B1 EP0149830B1 (de) 1989-04-05
EP0149830B2 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) DE3477588D1 (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
DE3477588D1 (en) 1989-05-11
EP0149830B1 (de) 1989-04-05
EP0149830A3 (en) 1986-10-15
CH665656A5 (fr) 1988-05-31
DE149830T1 (de) 1985-10-24
EP0149830B2 (de) 1992-05-13

Similar Documents

Publication Publication Date Title
FR2699556A1 (fr) Bains pour former un dépôt électrolytique de cuivre et procédé de dépôt électrolytique utilisant ce bain.
FR2672306A1 (fr) Solutions perfectionnees de zincate pour le traitement de l'aluminium et des alliages d'aluminium.
TW200902758A (en) Electroless gold plating bath, electroless gold plating method and electronic parts
FR2502184A1 (fr) Bain de revetement non-electrolytique en or
FR2658536A1 (fr) Compositions et procedes d'electrodeposition.
EP1272691B1 (de) Elektrolytische lösung zur elektrochemischen abscheidung von palladium oder dessen legierungen
EP1423557B1 (de) Elektrolytisches bad zum elektrochemischen abscheiden von gold und goldlegierungen
EP0180523A1 (de) Verfahren zur Beschichtung mit Zinkphosphaten, Aktivierungs- und Schichtverfeinerungsbad für dieses Verfahren und Konzentrat dafür
EP1268347B1 (de) Komplexes palladiumsalz und seine verwendung zur anpassung der palladiumkonzentration in elektrolytischen bädern bestimmt für die abscheidung von palladium oder einer seiner legierungen
US5194139A (en) Pretreating solution for silver plating and silver plating treating process using the solution
FR2493349A1 (fr) Procede d'obtention de revetements d'or, resistant a la corrosion, sur un substrat et revetements d'or durci notamment par du cobalt ainsi obtenus
EP0149830B1 (de) Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes
EP1520063B1 (de) Bad für galvanischen goldniederschlag
EP0480876A2 (de) Elektrolytisch erzeugter Überzug in Form einer Kupfer und Zink enthaltender Goldlegierung sowie Verfahren zu dessen Herstellung
FR2538815A1 (fr) Procede pour former, par electrolyse, un revetement de cuivre sur un substrat, a partir d'un bain exempt de cyanure, et anode pour la mise en oeuvre de ce procede
JP4078977B2 (ja) 無電解金めっき液及び無電解金めっき方法
FR2639654A1 (fr) Bain de dorure autocatalytique et son procede d'utilisation
JP3422595B2 (ja) アルミニウム合金用亜鉛置換処理浴
JPH0219473A (ja) 無電解金沈積
EP0140832B1 (de) Galvanisches Bad für das elekrolytische Absetzen einer Goldlegierung und galvanisches Verfahren für die Verwendung dieses Bads
JPH0124231B2 (de)
FR2539145A1 (fr) Procede pour former a grande vitesse, par electrolyse, une couche de revetement en palladium sur un substrat et bain pour la mise en oeuvre de ce procede
EP2505691A1 (de) Verfahren zur Erhaltung einer Beschichtung aus einer Goldlegierung 18 Karat 3N
EP0121492A1 (de) Galvanisches Bad für das Elektroplattieren einer Gold-Kupfer-Cadmiumlegierung, Verfahren zur Verwendung dieses Bades und aus diesem Verfahren resultierender Gegenstand
FR2558853A1 (fr) Bain exempt de citrate pour deposer, par electrolyse, des alliages d'or et son procede d'utilisation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

ITCL It: translation for ep claims filed

Representative=s name: ING. ENRICO LORENZONI

AK Designated contracting states

Designated state(s): CH DE FR GB IT LI

DET De: translation of patent claims
PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE FR GB IT LI

17P Request for examination filed

Effective date: 19861224

17Q First examination report despatched

Effective date: 19871211

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB IT LI

REF Corresponds to:

Ref document number: 3477588

Country of ref document: DE

Date of ref document: 19890511

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: DEGUSSA AG, FRANKFURT - ZWEIGNIEDERLASSUNG WOLFGAN

Effective date: 19900105

ITTA It: last paid annual fee
PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19920513

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): CH DE FR GB IT LI

REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

ITF It: translation for a ep patent filed
GBTA Gb: translation of amended ep patent filed (gb section 77(6)(b)/1977)
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20031124

Year of fee payment: 20

Ref country code: DE

Payment date: 20031124

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20031126

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20040301

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20041219

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20041219

Ref country code: CH

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20041219

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL