EP0149830B1 - 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
EP0149830B1
EP0149830B1 EP19840115879 EP84115879A EP0149830B1 EP 0149830 B1 EP0149830 B1 EP 0149830B1 EP 19840115879 EP19840115879 EP 19840115879 EP 84115879 A EP84115879 A EP 84115879A EP 0149830 B1 EP0149830 B1 EP 0149830B1
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.)
Expired
Application number
EP19840115879
Other languages
English (en)
French (fr)
Other versions
EP0149830A3 (en
EP0149830A2 (de
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(B1) "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 ⁇ ) 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 auricyanide KAu (CN) 2 , to which different 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 yellow AuCN gold cyanide and a hydrocyanic acid HCN.
  • 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 a galvanic chromium plating, a chemical nickel plating or a coating of molybdenum-manganese alloy.
  • compositions such as those 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 purpose of this invention is therefore to provide an electrolytic bath on the deposition of thin layers (of the order of ⁇ C 5. 1L) of pure gold (24cts) on passive surfaces, which perfectly adhere 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 chosen from the group comprising sulfuric acid, sulfamic acid, pyrophosphoric acid , monochloroacetic, dichloroacetic and trichloroacetic acids, malic acid, and 1-hydroxy-1,1-ethy) idene-diphosphonic, hydroxy-methyl-phosphonic and amino-tris (methylene-phosphonic) acids, and mixtures of these.
  • the acid is chosen from the group comprising sulfuric acid, sulfamic acid, pyrophosphoric acid , monochloroacetic, dichloroacetic and trichloroacetic acids, malic acid, and 1-hydroxy-1,1-ethy) idene-diphosphonic
  • 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 / l at saturation, which is reached for a concentration of approximately 150 g / l 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 / 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 nor 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 wafer was treated in this bath, at room temperature, with a current density of 4 A / dmz 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 current density 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 / 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)
  • Electroplating Methods And Accessories (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Claims (9)

1. Elektrolytbad zur Aufbringung von dünnen Schichten von reinem Gold auf passive Oberflächen, das es von 0,5 bis 20 g/I Gold in Form eines Alkalimetallcyanoaurats, in dem das Gold dreiwertig ist, und mindestens eine Säure in einer ausreichenden Menge zur Einstellung des pH-Wertes des Bads auf höchstens 0,4, enthält, dadurch gekennzeichnet, dass die Säure unter Schwefelsäure, Sulfamidsäure, Pyrophosphorsäure, Monochlor-, Dichlor- une Trichloressigsäure, Apfelsaüre, 1-Hydroxy-1, 1-ethylidendiphosphonsäure, Hydroxy-methylphosphonsäure und Aminotris(methylenphosphonsäure) sowie ihren Gemischen ausgewählt wird.
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/l vorhanden ist.
4. Bad nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es zusätzlich mindestens einen organischen Komplexbildner enthält.
5. Bad nach Anspruch 4, dadurch gekennzeichnet, dass der organische Komplexbildner unter den Alkalimetallsalzen von Diethylentriamin-penta(methylenphosphonsäure), Ethylen-diamin-tetra(methylenphosphonsäure), Hexamethylen-diamin-tetra(methylenphosphonsäure) und Ethylen-diamintetra (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-Carboxymethyl-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 imgb0012
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
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 EP0149830A2 (de) 1985-07-31
EP0149830A3 EP0149830A3 (en) 1986-10-15
EP0149830B1 true 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
EP0149830A3 (en) 1986-10-15
DE3477588D1 (en) 1989-05-11
DE149830T1 (de) 1985-10-24
CH665656A5 (fr) 1988-05-31
EP0149830A2 (de) 1985-07-31
EP0149830B2 (de) 1992-05-13

Similar Documents

Publication Publication Date Title
TW200902758A (en) Electroless gold plating bath, electroless gold plating method and electronic parts
US3230098A (en) Immersion plating with noble metals
EP0193848A1 (de) Galvanisches Bad für das Elektroplattieren von Goldlegierungen
CH622829A5 (de)
EP1423557B1 (de) Elektrolytisches bad zum elektrochemischen abscheiden von gold und goldlegierungen
EP2730682B1 (de) Alkalische, cyanidfreie lösung zur elektroplattierung von goldlegierungen, verfahren zur elektroplattierung und substrat mit einer heller, korrosionsfreien ablagerung einer goldlegierung
US3928147A (en) Method for electroplating
EP0149830B1 (de) Elekrolytisches Bad für das Abscheiden dünner Schichten reinen Goldes
US5194139A (en) Pretreating solution for silver plating and silver plating treating process using the solution
US4316779A (en) Process for electroplating palladium on articles comprising copper
NL7907967A (nl) Samenstelling en werkwijze voor het elektrolytisch afzetten van metallisch zilver.
JP3148428B2 (ja) 無電解金めっき液
US4615774A (en) Gold alloy plating bath and process
US4253920A (en) Composition and method for gold plating
JP4078977B2 (ja) 無電解金めっき液及び無電解金めっき方法
EP0480876A2 (de) Elektrolytisch erzeugter Überzug in Form einer Kupfer und Zink enthaltender Goldlegierung sowie Verfahren zu dessen Herstellung
CA2133134C (en) Chemical etchant for palladium
JP2000345359A (ja) 無電解金めっき液
FR2639654A1 (fr) Bain de dorure autocatalytique et son procede d'utilisation
JPH0219473A (ja) 無電解金沈積
JP3373356B2 (ja) 銅又は銅合金の変色防止液及び変色防止方法並びにそれを適用してなる電子部品材料
JP7740879B2 (ja) 電解銀めっき浴およびこれを用いた電解銀めっき方法
EP0384679A1 (de) Elektroplattierung von Gold enthaltenden Legierungen
EP1520063A1 (de) Bad für galvanischen goldniederschlag
JP2000345400A (ja) 銀の電解剥離剤及び電解剥離方法

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