EP0037535B1 - Bain galvanique pour le dépôt de revêtements d'or et d'alliages d'or - Google Patents

Bain galvanique pour le dépôt de revêtements d'or et d'alliages d'or Download PDF

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Publication number
EP0037535B1
EP0037535B1 EP81102316A EP81102316A EP0037535B1 EP 0037535 B1 EP0037535 B1 EP 0037535B1 EP 81102316 A EP81102316 A EP 81102316A EP 81102316 A EP81102316 A EP 81102316A EP 0037535 B1 EP0037535 B1 EP 0037535B1
Authority
EP
European Patent Office
Prior art keywords
gold
bath
acid
potassium
alloy
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
EP81102316A
Other languages
German (de)
English (en)
Other versions
EP0037535A2 (fr
EP0037535A3 (en
Inventor
Wolfgang Dipl.Chem. Zilske
Werner Chem. Ing. Kuhn
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
Priority to AT81102316T priority Critical patent/ATE6527T1/de
Publication of EP0037535A2 publication Critical patent/EP0037535A2/fr
Publication of EP0037535A3 publication Critical patent/EP0037535A3/de
Application granted granted Critical
Publication of EP0037535B1 publication Critical patent/EP0037535B1/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 gold bath for the electrodeposition of high-gloss and ductile gold alloy coatings based on potassium cyanoaurate (III), which contains an acid, at least one of the alloy metals cobalt, nickel, indium, tin, zinc or cadmium in the form of water-soluble salts and a complexing agent contains a pH of less than 3.
  • III potassium cyanoaurate
  • the majority of gold coatings are deposited today from weakly acidic electrolytes that operate in the pH range from 3.5 to 5. They contain the gold in the form of potassium dicyanoaurate (I), KAu (CN), and as a buffer salts of weak inorganic or organic acids such as phosphates, citrates or phosphonates.
  • the properties of the deposited layers are strongly influenced by adding metal salts, especially nickel, cobalt or indium. These baths are obtained under conditions in which 0.2 to 0.5% of Ni or Co are also deposited, coatings which are shiny, have a hardness of 150 to 180 HV and have good resistance to mechanical abrasion. From about 5 ⁇ m, these coatings are practically non-porous. They are characterized by good electrical conductivity and low contact resistance.
  • the coatings from these baths also have considerable disadvantages.
  • Your ductility is low. With slight mechanical deformation, cracks form. They contain a relatively large amount (approx. 1%) of non-metallic impurities, which presumably lead to malfunctions in low-voltage electrical contacts. Presumably also because of these impurities, the contact resistance does not remain constant during thermal loading and affects the function of electrical devices.
  • the content of the alloy metal in the coating is strongly dependent on the current density and the pH value, so that the working conditions must be kept within narrow limits in order to obtain coatings of constant quality.
  • the average current density is limited to about 1 A / dm l , the bath temperature must not be higher than 40 ° C, and in most baths the pH must be kept between 3.5 and 4.
  • the layers are often only milky or matt. It is not possible to work at pH values below 3.5, since the KAu (CN) 2 disintegrates at pH 3 with the excretion of gold cyanide, AuCN. Nevertheless, attempts were made to use such baths at pH values below 3 (for example DE-AS No. 1262723, US Pat. No. 2978390), but the results were unsatisfactory.
  • No. 3,598,706 describes a process for the preparation of tetracyano gold (III) acid and a bath on this basis.
  • No. 4168214 describes a hydrochloric acid bath for the pre-gilding of stainless steel, the tetracyano gold (III) complex being formed by reaction of gold (III) chloride with potassium cyanide in the bath and a pH between 0.1 and 1. 5 is set.
  • This bath also contains alloy metals such as nickel, cobalt, tin or indium, and ethylenediamine hydrochloride as a complexing agent.
  • a pure alloy bath for the deposition of gold / tin coatings based on KAu (CN) 4 in the hydrochloric acid medium is claimed in DE-OS No. 2658003.
  • Baths in which the trivalent gold is present have the disadvantage compared to baths based on monovalent gold salts that only a third of the amount of gold is deposited due to the differences in value with the same current densities and times.
  • This disadvantage can only be compensated for by using correspondingly high current densities.
  • Another major disadvantage is the high chloride content in these baths, which causes an unpleasant chlorine development at the anode. If the baths also contain hydrochloric acid, there are also corrosion problems on the systems.
  • potassium cyanoaurate (III) which contains an acid, at least one of the alloy metals cobalt, nickel, indium, tin, zinc or cadmium in the form of water-soluble salts and a complexing agent contains at a pH value of less than 3, which provides high-gloss and ductile coatings even at high current densities and at which no chlorine development occurs.
  • the electrolyte contains, in addition to an amine, an aminocarboxylic acid or phosphonic acid as complexing agent, 20 to 200 g / l of sulfuric acid, phosphoric acid, citric acid or mixtures thereof.
  • a pH range from 0.4 to 2.5 is particularly advantageous.
  • Baths containing 1 to 20 g / l gold in the form of catium cyanoaurate (III), 10 to 200 g / l sulfuric acid, phosphoric acid and / or citric acid, 0.1 to 20 g / l at least one of the alloy metals cobalt, nickel have proven successful , Indium, zinc, tin or cadmium in the form of water-soluble salts and 1 to 100 g / l of an amine, an aminocarboxylic acid or a phosphonic acid, which are able to form a complex with the alloy metal.
  • salts of the acids used such as, for example, potassium dihydrogen phosphate, potassium hydrogen sulfate or potassium citrate.
  • complex shiny gold layers can be deposited over a wide current density range from acidic electrolytes based on the tetracyanoaurate (III) if the baths contain alloy metals and at the same time suitable complexing agents and suitable acids.
  • Alloy metals can be Co, Ni, In, Sn, Zn or Cd.
  • Suitable complexing agents are amines, aminocarboxylic acids or phosphonic acids. If the alloy metals are only added in the form of simple salts, as in the baths known hitherto, the metal distribution in the coating is uneven, since in general the amount of the alloy metal deposited is strongly dependent on the current density.
  • the properties of the deposited layers from the bath according to the invention have particular advantages compared to the coatings from the so-called weakly acidic gold baths.
  • the layers are not only hard and wear-resistant, but also very ductile. They can be deposited in a thin layer with little pores.
  • the contact resistance is low and remains constant even during heat storage.
  • the content of non-metallic impurities is very low.
  • the bath according to the invention is advantageously used in the pH range from 0.4 to 2.5. Both significantly lower and significantly higher pH values lead to the decomposition of the gold complex with the separation of insoluble gold (I) cyanide.
  • the bath is preferably operated at pH values between 0.6 and 2.0.
  • the bath can be used at room temperature, but higher temperatures up to 60 ° C are advantageous to increase the deposition rate.
  • the applicable current density range is extremely wide. Shiny layers are achieved above all with current densities of 0.2 to at least 10 A / dm 2 .
  • the gold content is increased to 8 g / l, the bath is heated to 50 ° C. and the deposition is repeated at a current density of 8 A / dm 2 . 3 gm of gold are now deposited in 10 minutes. The cover is also light yellow and shiny. Approx. 0.5% cobalt is detected in both layers.
  • the copper base of the second sample is dissolved with 3: 1 dilute nitric acid. A ductile gold foil is obtained which does not break even when it is bent.
  • the cobalt complex solution used when preparing the bath becomes like prepared as follows: 47.8 g of CoSO 4 .7H 2 O, corresponding to 10 g of Co, are dissolved in about 600 ml of water with heating, 222 ml of 1-hydroxyethane-1,1-diphosphonic acid are added 60% and made up to 1 liter.
  • An adherent gold layer of 0.2 ⁇ m is deposited on a cathode made of 18Cr8Ni steel in 5 min at a current density of 2 A / dm 2 .
  • the pH is adjusted to 2.0 and the bath is heated to 40 ° C.
  • a current density of 5 A / dm l a 2.5 ⁇ m thick glossy gold layer is deposited on a copper sheet in 10 minutes.
  • Gold contains 0.4% Ni.
  • the pH of the bath is adjusted to 1.8.
  • a shiny, light yellow gold layer of 2 ⁇ m thickness is deposited on a nickel-plated copper sheet in 10 min.

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 (8)

1. Bain d'or pour le dépôt par électrolyse de revêtements d'alliages d'or très brillants et ductiles à base de cyanoaurate (III) de potassium, contenant un acide, au moins un des métaux d'alliage cobalt, nickel, indium, étain, zinc ou cadmium sous forme de sels solubles à l'eau, et un formateur de complexe, à un pH inférieur à 3, caractérisé en ce que l'électrolyte contient - en plus d'une amine, d'un acide aminocarboxylique ou d'un acide phosphonique comme formateurs de complexe -, comme acide, 20 à 200 g/I d'acide sulfurique, d'acide phosphorique ou d'acide citrique ou de leurs mélanges.
2. Bain d'or suivant la revendication 1, caractérisé en ce que le bain contient, en plus des acides, leurs sels, tels que le dihydrophosphate de potassium, l'hydrosulfate de potassium ou le citrate de potassium.
3. Bain d'or suivant l'une des revendications 1 ou 2, caractérisé en ce que le bain présente un pH qui se situe entre 0,4 et 2,5.
4. Bain d'or suivant l'une des revendications 1 à 3, caractérisé en ce que le bain contient 1 à 20 g/I d'or sous la forme de cyanoaurate (III) de potassium.
5. Bain d'or suivant l'une des revendications 1 à 4, caractérisé en ce que le bain contient 0,1 à 20 g/I d'au moins un des métaux d'alliage cobalt, nickel, indium, étain, zinc ou cadmium sous forme de sels solubles dans l'eau.
6. Bain d'or suivant l'une des revendications 1 à 5, caractérisé en ce que le bain contient 1 à 100 g/I d'une amine, d'un acide aminocarboxylique ou d'acide phosphonique, qui soit capable de former un complexe avec le métal d'alliage.
7. Bain d'or suivant l'une des revendications 1 à 6, pour déposer des revêtements d'or très brillants et ductiles, caractérisé en ce qu'il est utilisé à des températures de 40 à 60°C.
8. Bain d'or suivant l'une des revendications 1 à 7, caractérisé en ce qu'on opère avec des intensités de courant de 0,1 à 20 A/dm2.
EP81102316A 1980-04-03 1981-03-27 Bain galvanique pour le dépôt de revêtements d'or et d'alliages d'or Expired EP0037535B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81102316T ATE6527T1 (de) 1980-04-03 1981-03-27 Galvanisches bad zur abscheidung von gold- und goldlegierungsueberzuegen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3012999 1980-04-03
DE3012999A DE3012999C2 (de) 1980-04-03 1980-04-03 Bad und Verfahren zur galvanischen Abscheidung von hochglänzenden und duktiler Goldlegierungsüberzügen

Publications (3)

Publication Number Publication Date
EP0037535A2 EP0037535A2 (fr) 1981-10-14
EP0037535A3 EP0037535A3 (en) 1981-11-04
EP0037535B1 true EP0037535B1 (fr) 1984-03-07

Family

ID=6099206

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81102316A Expired EP0037535B1 (fr) 1980-04-03 1981-03-27 Bain galvanique pour le dépôt de revêtements d'or et d'alliages d'or

Country Status (6)

Country Link
US (1) US4391679A (fr)
EP (1) EP0037535B1 (fr)
JP (1) JPS56152989A (fr)
AT (1) ATE6527T1 (fr)
DE (1) DE3012999C2 (fr)
HK (1) HK30986A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4040526A1 (de) * 1989-12-19 1991-06-20 H E Finishing Sa Bad zur galvanischen abscheidung von goldlegierungen

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4470886A (en) * 1983-01-04 1984-09-11 Omi International Corporation Gold alloy electroplating bath and process
DE3347594A1 (de) * 1983-01-04 1984-07-12 Omi International Corp., Warren, Mich. Bad zur galvanischen abscheidung einer verschleissfesten goldlegierung und verfahren zur abscheidung einer verschleissfesten goldlegierung unter verwendung dieses bades
US4559121A (en) * 1983-09-12 1985-12-17 Vac-Tec Systems, Inc. Method and apparatus for evaporation arc stabilization for permeable targets
US4448659A (en) * 1983-09-12 1984-05-15 Vac-Tec Systems, Inc. Method and apparatus for evaporation arc stabilization including initial target cleaning
US4559125A (en) * 1983-09-12 1985-12-17 Vac-Tec Systems, Inc. Apparatus for evaporation arc stabilization during the initial clean-up of an arc target
CH665656A5 (fr) * 1983-12-29 1988-05-31 Heinz Emmenegger Bain d'or acide et utilisation de ce bain en electroplastie.
DE3505473C1 (de) * 1985-02-16 1986-06-05 Degussa Ag, 6000 Frankfurt Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsueberzuegen
DE3509367C1 (de) * 1985-03-15 1986-08-14 Degussa Ag, 6000 Frankfurt Bad und Verfahren zur galvanischen Abscheidung von Gold/Zinn-Legierungsueberzuegen
CA2365749A1 (fr) * 2001-12-20 2003-06-20 The Governors Of The University Of Alberta Un procede d'electrodeposition et un materiau composite multicouche ainsi obtenu
JP2007537358A (ja) * 2004-05-11 2007-12-20 テクニック・インコーポレイテッド 金−スズ共晶合金のための電気めっき用溶液
JP4945193B2 (ja) * 2006-08-21 2012-06-06 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． 硬質金合金めっき液
JP5317433B2 (ja) * 2007-06-06 2013-10-16 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． 酸性金合金めっき液
US20090114345A1 (en) * 2007-11-07 2009-05-07 Sumitomo Metal Mining Co., Ltd. Method for manufacturing a substrate for mounting a semiconductor element
DE102011114931B4 (de) 2011-10-06 2013-09-05 Umicore Galvanotechnik Gmbh Verfahren zur selektiveren, elektrolytischen Abscheidung von Gold oder einer Goldlegierung

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2978390A (en) * 1957-07-22 1961-04-04 Bell Telephone Labor Inc Gold plating solutions
DE1262723B (de) * 1964-12-16 1968-03-07 Philippi & Co K G Galvanisches Gold- oder Goldlegierungsbad
US3598706A (en) * 1967-12-11 1971-08-10 Trifari Krussman And Fishel In Acid gold plating baths
ZA734253B (en) * 1972-07-10 1975-02-26 Degussa Electrolytic bath
US3989800A (en) * 1973-12-26 1976-11-02 Motorola, Inc. Alkali metal gold cyanide method
US4073700A (en) * 1975-03-10 1978-02-14 Weisberg Alfred M Process for producing by electrodeposition bright deposits of gold and its alloys
JPS5224132A (en) * 1975-08-05 1977-02-23 Dowa Mining Co Rigid alloy plating method
US4013523A (en) * 1975-12-24 1977-03-22 Oxy Metal Industries Corporation Tin-gold electroplating bath and process
US4168214A (en) * 1978-06-14 1979-09-18 American Chemical And Refining Company, Inc. Gold electroplating bath and method of making the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4040526A1 (de) * 1989-12-19 1991-06-20 H E Finishing Sa Bad zur galvanischen abscheidung von goldlegierungen
DE4040526C3 (de) * 1989-12-19 1998-05-20 H E Finishing Sa Bad zur galvanischen Abscheidung von Goldlegierungen

Also Published As

Publication number Publication date
EP0037535A2 (fr) 1981-10-14
DE3012999A1 (de) 1981-10-15
EP0037535A3 (en) 1981-11-04
ATE6527T1 (de) 1984-03-15
HK30986A (en) 1986-05-09
JPS56152989A (en) 1981-11-26
DE3012999C2 (de) 1984-02-16
US4391679A (en) 1983-07-05
JPH0146597B2 (fr) 1989-10-09

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