US2724687A - Baths for the deposit of gold alloys by electroplating - Google Patents

Baths for the deposit of gold alloys by electroplating Download PDF

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Publication number
US2724687A
US2724687A US300127A US30012752A US2724687A US 2724687 A US2724687 A US 2724687A US 300127 A US300127 A US 300127A US 30012752 A US30012752 A US 30012752A US 2724687 A US2724687 A US 2724687A
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bath
acid
gold
baths
salt
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US300127A
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Spreter Victor
Mermillod Jean
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    • 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • 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 present invention relates to a bath for the deposition of gold alloys by electroplating, which is not subject to ageing, that is to say, the yield of which, computed on the basis of the current consumed as compared to the weight of the metal deposited, measured when the bath has just been prepared, remains constant during the whole life of the bath.
  • This bath contains the gold intended for plating in the form of alkaline aurocyanide. It is characterized by the fact that, apart from the said aurocyanide, it is free from any other cyanide and by the fact that it contains an organo metallic compound of the metal to be alloyed with gold, soluble in water and hav: ing a low dissociation constant.
  • this organo-metallic compound other than a cyanide, which supplies the metal to be alloyed with the gold at the time of formation of the gold alloy deposit.
  • the metal of this compound may thus be copper, nickel, cadmium, zinc. It has been found that when the metal to be alloyed with gold. is introduced into the bath in a form other than cyanide, the bath does not age.
  • the said organo-rnetallic compound may include in its molecule the group -N(CH2COO--)2. It may be a salt of an organic acid and of the metal to be alloyed with gold, insofar as this salt has a low dissociation constant. Among the salts fulfilling this condition, one may. mention those of the acids presenting in their molecule the above mentioned group, such as those of imido-diacetic acid and its derivatives, for instance ethylene-diaminotetraacetic acid, nitrilo-tri'a'cetic acid, :anthranilic-diacetic acid, uranil-diacetic acid, aminomalonic-diacetic acid.
  • conducting s'al'ts such as phosphates and sulphites can be completely omitted from the bath and replaced by the potassium and sodium salts of the organo-n1etallic compound above referred to.
  • the bath does not contain any free cyanide.
  • EXAMPLE 1 Bath for the deposition of thick coatings (pink colour) g. per litre Gold (as potassium aurocyanide) a 12 Cu (as copper salt of ethylene-diamino-tetraacetic acid) 2.5 Zn (as Zinc salt of ethylene-diamino-tetraacetic acid) 2 Ni (as nickel salt of ethylene-diamino-tetraacetic acid) 2 Potassium salt of ethylene-diamino-tetraacetic acid- 5 EXAMPLE 2 Bath for the deposition of thin gold coatings (yellow and pale yellow colours) g.
  • a bath for the deposition of an alloy of gold with at least one metal selected from the group consisting of copper, nickel, cadmium and zinc said bath containing exclusively an alkaline aurocyanide and at least one organometallic compound selected from the group consisting of the copper, nickel, cadmium and zinc salts of ethylene-diamino-tetraacetic acid, nitrilo-triacetic acid, anthranilic-diacetic acid, uranil-diacetic acid and aminomalonic-diacetic acid, characterized by the yield, computed on 4- the basis of the current consumed as compared tothe Weight of metal deposited, remains constant during the whole life of the bath.

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  • 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)

Description

United States Patent No Drawing. Application tltriyil, 1952,
Serial No. 300,127
Claims priority, application SwitzerlandMay 8,1952 6 Claims. (Cl. 204-43) Baths for electrogilding, irrespective of the .gold alloy colour which they serve to obtain, have almost identical compositions. Indeed, ;gold,.copper, silver, nickel, cadmium or zinc are, contained therein as soluble cyanides, that is to say alkaline metal-cyanides. in addition these baths contain, according to case,"phosphates,sulphites,
carbonates and free 'cyanid'es, ith'ese jsalts being intended for improving either the electric conductivity or the penetrating power of thebath, or the brilliance of the deposits obtained.
When such a bath has just been prepared, it is found that, for a given temperature and current density, its yield (considered from the point of view of the metal deposited, as compared to the current consumed), through being lower than 100%, is the highest found in the above mentioned operating conditions. Indeed Whether the bath is used or not, it is found that the yield compared to the current consumed regularly falls with time and may go down to nearly 10% after a certain number of days: .the bath is said to have aged.
The consequences of such ageing are disastrous: when thick gilding is involved. (over 1 or 2 microns), the necessary duration for obtaining such gilding considerably increases as time passes and finally becomes unacceptable; if light gilding is involved (colour setting), the ageing state of the bath is one more variable which must be reckoned with in the already ticklish bath working in order to keep constant the colour of the deposited alloy.
The present invention relates to a bath for the deposition of gold alloys by electroplating, which is not subject to ageing, that is to say, the yield of which, computed on the basis of the current consumed as compared to the weight of the metal deposited, measured when the bath has just been prepared, remains constant during the whole life of the bath.
This bath, as those already known, contains the gold intended for plating in the form of alkaline aurocyanide. It is characterized by the fact that, apart from the said aurocyanide, it is free from any other cyanide and by the fact that it contains an organo metallic compound of the metal to be alloyed with gold, soluble in water and hav: ing a low dissociation constant.
It is this organo-metallic compound, other than a cyanide, which supplies the metal to be alloyed with the gold at the time of formation of the gold alloy deposit. The metal of this compound may thus be copper, nickel, cadmium, zinc. It has been found that when the metal to be alloyed with gold. is introduced into the bath in a form other than cyanide, the bath does not age.
The said organo-rnetallic compound may include in its molecule the group -N(CH2COO--)2. It may be a salt of an organic acid and of the metal to be alloyed with gold, insofar as this salt has a low dissociation constant. Among the salts fulfilling this condition, one may. mention those of the acids presenting in their molecule the above mentioned group, such as those of imido-diacetic acid and its derivatives, for instance ethylene-diaminotetraacetic acid, nitrilo-tri'a'cetic acid, :anthranilic-diacetic acid, uranil-diacetic acid, aminomalonic-diacetic acid.
On the other hand, conducting s'al'ts such as phosphates and sulphites can be completely omitted from the bath and replaced by the potassium and sodium salts of the organo-n1etallic compound above referred to. The bath does not contain any free cyanide.
Baths in accordance with the present invention and the organo-metallic compound of which is a salt of ethylene-diamino-tetraacetic acid, are remarkable for their following properties:
They do not age, thatis to say that their yield,.computed on the basis of the current consumed under given electrolysis conditions, remains constant during their whole life;
They give brilliant gold alloy deposits, the assay of which may be adjusted by changing the electrolysis factors; They make it possible to obtain a very quick increase of the thickness of the deposits (ten times more quickly than with the baths usedhitherto). A current density of 2 to 3 amperes per sq. decimeter (18.5 to 28 amperes .per sq. foot) at the cathode gives excellent deposits;
Their penetrating power into the cavities of the object placed at the cathode far exceeds that of ordinary cyanide baths;
They remain extremeiy limpid during use;
Their content of copper salt (being the one most generally present in these baths) may be adjusted very easily by colorimetry owing to the blue tint of said salt.
The following examples give the composition of baths, in conformity with the present invention, and the manner of using them:
EXAMPLE 1 Bath for the deposition of thick coatings (pink colour) g. per litre Gold (as potassium aurocyanide) a 12 Cu (as copper salt of ethylene-diamino-tetraacetic acid) 2.5 Zn (as Zinc salt of ethylene-diamino-tetraacetic acid) 2 Ni (as nickel salt of ethylene-diamino-tetraacetic acid) 2 Potassium salt of ethylene-diamino-tetraacetic acid- 5 EXAMPLE 2 Bath for the deposition of thin gold coatings (yellow and pale yellow colours) g. per litre Gold (as potassium aurocyanide) 1 Ni (as nickel salt of ethylene-diamino-tetraacetic acid) 2 Potassium salt of ethylene-diamino-tetraacetic acid 5 By using this bath at a temperature of 60 C. with a stainless steel anode, one may, when adjusting the cathode current density between 0.3 and 0.8 amp. per sq. decimeter (2.8 and7.5 amp. per sq. foot), obtain any gold tint, from the 24 carats yellow to very pale yellow, and all intermediate tints iii-between. This bath has an absolutely remarkable penetrating power and stability;
I maintaining the colour of the deposit from one operation to another is very easy. i
By using this bath at a temperature of 60 C. with a stainless steel anode, one may, by adjusting the cathode current density between 0.3 and 0.5 amp. per sq. decimeter (2.8 and 4.65 amp. per sq. foot), obtain all the tints of green colour gold.
What we claim is:
1. A bath for the deposition of an alloy of gold with at least one metal selected from the group consisting of copper, nickel, cadmium and zinc, said bath containing exclusively an alkaline aurocyanide and at least one organometallic compound selected from the group consisting of the copper, nickel, cadmium and zinc salts of ethylene-diamino-tetraacetic acid, nitrilo-triacetic acid, anthranilic-diacetic acid, uranil-diacetic acid and aminomalonic-diacetic acid, wehreby the yield, computed on 4- the basis of the current consumed as compared tothe Weight of metal deposited, remains constant during the whole life of the bath.
2. A bath according to claim 1, in which the said organo-metallic compound is a salt of ethylene-diaminotetraacetic acid.
3. A bath according to claim 1, in which the said organo-metallic compound is a salt of nitrilo-triacetic acid.
4. A bath according to claim 1, in which the said organo-metallic compound is a salt of anthranilic-diacetic acid.
5. A bath according to claim 1, in which the said organo-metallic compound is a salt'of uranil-diacetic acid.
6. A bath according to claim 1, in which the said organo-metallic compound is a salt of aminomalonicdiacetic acid.
OTHER REFERENCES Thews: Metal Finishing, September 1951, page 83.

Claims (1)

1. A BATH FOR THE DEPOSITION OF AN ALLOY OF GOLD WITH AT LEAST ONE METAL SELECTED FROM THE GROUP CONSISTING OF COPPER, NICKEL, CADMIUM AND ZINC, SAID BATH CONTAINING EXCLUSIVELY AN ALKALINE AUROCYANIDE AND AT LEAST ONE ORGANOMETALLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE COPPER, NICKEL, CADMIUM AND ZINC SALTS OF ETHYLENE-DIAMINO-TETRAACETIC ACID, NITRILO-TRIACETIC ACID, ANTHRANILIC-DIACETIC ACID, URANIL-DIACETIC ACID AND AMINOMALONIC-DIACETIC ACID, WEHREBY THE YIELD, COMPUTED ON THE BASIS OF THE CURRENT CONSUMED AS COMPARED TO THE WEIGHT OF METAL DEPOSITED, REMAINS CONSTANT DURING THE WHOLE LIFE OF THE BATH.
US300127A 1952-05-08 1952-07-21 Baths for the deposit of gold alloys by electroplating Expired - Lifetime US2724687A (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2812299A (en) * 1949-05-05 1957-11-05 Birle & Co K G Electrolytic deposition of gold and gold alloys
US2905601A (en) * 1957-08-13 1959-09-22 Sel Rex Corp Electroplating bright gold
US3056733A (en) * 1960-04-23 1962-10-02 Degussa Process for electrolytic deposition of gold-copper-cadmium alloys
US3057789A (en) * 1959-02-26 1962-10-09 Paul T Smith Gold plating bath and process
US3149058A (en) * 1959-12-31 1964-09-15 Technic Bright gold plating process
US3149057A (en) * 1959-04-27 1964-09-15 Technic Acid gold plating
US3373094A (en) * 1964-08-26 1968-03-12 Sel Rex Corp Gold and gold alloy electroplating
US3380814A (en) * 1965-06-18 1968-04-30 Sel Rex Corp Electrolyte and method for coating articles with a gold-copper-antimony alloy and article thereof
US3380898A (en) * 1965-06-18 1968-04-30 Sel Rex Corp Electrolyte and method for electrodepositing a pink gold alloy
US3530049A (en) * 1968-10-02 1970-09-22 Technic Gold and ruthenium plating baths
US3902977A (en) * 1973-12-13 1975-09-02 Engelhard Min & Chem Gold plating solutions and method
DE2829979A1 (en) * 1977-07-08 1979-01-18 Systemes Traitements Surfaces ELECTROLYSIS BATH FOR THE DEPOSITION OF GOLD-COPPER-CADMIUM ALLOYS AND ITS APPLICATION IN GALVANO TECHNOLOGY
US4358351A (en) * 1980-05-31 1982-11-09 Degussa Aktiengesellschaft Alkaline bath for the electrolytic deposition of low carat yellow colored gold alloy layers
US4465564A (en) * 1983-06-27 1984-08-14 American Chemical & Refining Company, Inc. Gold plating bath containing tartrate and carbonate salts
US6576114B1 (en) 1995-11-03 2003-06-10 Enthone Inc. Electroplating composition bath
WO2008040761A3 (en) * 2006-10-03 2008-11-06 Swatch Group Res & Dev Ltd Electroforming method and part or layer obtained using said method
US20100206739A1 (en) * 2007-09-21 2010-08-19 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US20110089040A1 (en) * 2009-10-15 2011-04-21 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1111897B (en) * 1957-08-13 1961-07-27 Sel Rex Corp Bath for the galvanic deposition of shiny gold alloy coatings
DE1262723B (en) * 1964-12-16 1968-03-07 Philippi & Co K G Galvanic gold or gold alloy bath
DE102006032634A1 (en) 2006-07-13 2008-01-17 Evonik Degussa Gmbh Process for the preparation of L-amino acids

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2660554A (en) * 1950-11-10 1953-11-24 Barnet D Ostrow Bright gold and gold alloy plating baths

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE732102C (en) * 1937-01-12 1943-02-26 Schallband Syndikat Ag Process for the serial production of sound films with mechanical sound writing

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2660554A (en) * 1950-11-10 1953-11-24 Barnet D Ostrow Bright gold and gold alloy plating baths

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2812299A (en) * 1949-05-05 1957-11-05 Birle & Co K G Electrolytic deposition of gold and gold alloys
US2905601A (en) * 1957-08-13 1959-09-22 Sel Rex Corp Electroplating bright gold
US3057789A (en) * 1959-02-26 1962-10-09 Paul T Smith Gold plating bath and process
US3149057A (en) * 1959-04-27 1964-09-15 Technic Acid gold plating
US3149058A (en) * 1959-12-31 1964-09-15 Technic Bright gold plating process
US3056733A (en) * 1960-04-23 1962-10-02 Degussa Process for electrolytic deposition of gold-copper-cadmium alloys
US3373094A (en) * 1964-08-26 1968-03-12 Sel Rex Corp Gold and gold alloy electroplating
US3380814A (en) * 1965-06-18 1968-04-30 Sel Rex Corp Electrolyte and method for coating articles with a gold-copper-antimony alloy and article thereof
US3380898A (en) * 1965-06-18 1968-04-30 Sel Rex Corp Electrolyte and method for electrodepositing a pink gold alloy
US3530049A (en) * 1968-10-02 1970-09-22 Technic Gold and ruthenium plating baths
US3902977A (en) * 1973-12-13 1975-09-02 Engelhard Min & Chem Gold plating solutions and method
DE2829979A1 (en) * 1977-07-08 1979-01-18 Systemes Traitements Surfaces ELECTROLYSIS BATH FOR THE DEPOSITION OF GOLD-COPPER-CADMIUM ALLOYS AND ITS APPLICATION IN GALVANO TECHNOLOGY
DE2829979C3 (en) * 1977-07-08 1990-06-21 Systemes Traitements Surfaces AQUEOUS BATH FOR GALVANIC DEPOSITION OF GOLD COPPER CADMIUM ALLOYS
US4358351A (en) * 1980-05-31 1982-11-09 Degussa Aktiengesellschaft Alkaline bath for the electrolytic deposition of low carat yellow colored gold alloy layers
US4465564A (en) * 1983-06-27 1984-08-14 American Chemical & Refining Company, Inc. Gold plating bath containing tartrate and carbonate salts
US6576114B1 (en) 1995-11-03 2003-06-10 Enthone Inc. Electroplating composition bath
WO2008040761A3 (en) * 2006-10-03 2008-11-06 Swatch Group Res & Dev Ltd Electroforming method and part or layer obtained using said method
US20100024930A1 (en) * 2006-10-03 2010-02-04 The Swatch Group Research And Development Ltd. Electroforming method and part or layer obtained via the method
KR101326883B1 (en) * 2006-10-03 2013-11-11 더 스와치 그룹 리서치 앤 디벨롭먼트 엘티디 Electroforming method and part or layer obtained using said method
US20100206739A1 (en) * 2007-09-21 2010-08-19 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US9683303B2 (en) 2007-09-21 2017-06-20 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US10233555B2 (en) 2007-09-21 2019-03-19 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US10619260B2 (en) 2007-09-21 2020-04-14 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US20110089040A1 (en) * 2009-10-15 2011-04-21 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
US9567684B2 (en) 2009-10-15 2017-02-14 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials

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FR1067620A (en) 1954-06-17
DE1033987B (en) 1958-07-10
CH286123A (en) 1952-10-15
GB718574A (en) 1954-11-17

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