EP0041208B1 - Alkaline bath for the electrodeposition of pink to yellow coloured layers of gold alloys with low carat weight - Google Patents

Alkaline bath for the electrodeposition of pink to yellow coloured layers of gold alloys with low carat weight Download PDF

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Publication number
EP0041208B1
EP0041208B1 EP81103982A EP81103982A EP0041208B1 EP 0041208 B1 EP0041208 B1 EP 0041208B1 EP 81103982 A EP81103982 A EP 81103982A EP 81103982 A EP81103982 A EP 81103982A EP 0041208 B1 EP0041208 B1 EP 0041208B1
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EP
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Prior art keywords
gold
alkaline bath
pink
cyanide
zinc
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Expired
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EP81103982A
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German (de)
French (fr)
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EP0041208A1 (en
Inventor
Franz Dr. Dipl.-Chem. Simon
Werner Huth
Bernd Dr. Dipl.-Chem. Dorbath
Wolfgang Dipl.Chem. Zilske
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Evonik Operations GmbH
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Degussa GmbH
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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
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold

Definitions

  • the invention relates to an alkaline bath for the electrodeposition of low-carat rosabis yellow-colored gold alloy layers containing soluble gold cyanide, soluble copper cyanide and potassium carbonate or potassium hydrogen carbonate. Corrosion-resistant layers in the range of 13 to 18 carats are deposited.
  • Baths which contain cadmium and chelating agents in addition to complex gold and copper cyanides have been used to produce low-carat pink and yellow-colored gold alloy coatings (DE-AS 22 21 159).
  • Such baths generally operate in a pH range of 7.5-12 and also contain free cyanide, conductive salts, such as. B. carbonates, and buffer salts, such as. B. Phosphates. They provide glossy pink or yellow alloy deposits of good quality in favorable working conditions.
  • these baths have the serious disadvantage that they contain cadmium, which is not physiologically harmless and must be replaced by other substances.
  • Gold baths which, in addition to gold, also contain zinc and other alloy metals, in particular copper, as soluble salts. With such galvanic baths, however, no pink or yellow low-carat gold alloy layers have so far been produced, but only high-quality or non-colored layers.
  • DE-OS2342691 describes a cyanidic alkaline white gold bath which, in addition to potassium gold cyanide and potassium zinc cyanide, contains potassium nickel cyanide and dipotassium hydrogen phosphate at pH values of 9-13. However, low-carat gold alloy layers cannot be produced with these baths.
  • a galvanic gold alloy bath which, in addition to potassium gold cyanide, can also contain copper sulfate and optionally a zinc salt.
  • these baths which operate at pH values of 3-10 and contain aldehydes, diamines and arsenic acid as essential components, no low-carat gold alloy layers are obtained.
  • DE-OS 27 54 207 describes a gold alloy bath which contains potassium gold cyanide, zinc sulfate and sodium carbonate and is operated at pH 4.9. Green precipitates are separated from this bath.
  • a gold alloy bath is known (DE-AS1033987) which contains potassium gold cyanide, copper, zinc and nickel in the form of their ethylenediaminetetradic acid salts. At pH 8 and a temperature of 60 ° C, 19-carat alloy coatings are obtained, which are grayish.
  • Baths containing gold as alkali gold cyanide and copper as alkali copper cyanide have proven successful.
  • Such baths preferably contain 10-30 g / l of zinc as K 2 (Zn (CN) 4 ),
  • Baths containing 0.2-1.5 g / l of a selenium and / or arsenic compound have also proven useful as a gloss additive.
  • the addition of chelating agents, such as ethylenediaminetetracid or other aminocarboxylic acids, in amounts of 5-20 g / l is also recommended in some cases.
  • the range from 50 to 75 ° C., in particular 60-75 ° C., and the pH range from 8-12, in particular 9-10, has proven to be the working temperature.
  • the baths according to the invention make it possible, despite different carat contents of the layers of 13-18 carats, depending on the bath composition and working conditions, to produce a constant, uniform pink or yellow color. Even with a fineness of 14 kt, a pleasant pink color (3-4 N) is achieved with copper contents of 30 to 40% by weight, which is surprising at these high copper contents. Even with a strongly fluctuating gold content in the bath between 3 and 10 g / l and a zinc content between 2 and 15% in the coating, an almost constant pink color is delivered. The deposited layers have good ductility.

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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

Die Erfindung betrifft ein alkalisches Bad zum galvanischen Abscheiden niederkarätiger rosabis gelbfarbener Goldlegierungsschichten mit einem Gehalt an löslichem Goldzyanid, löslichem Kupferzyanid und Kaliumkarbonat bzw. Kaliumhydrogenkarbonat. Dabei werden korrosionsbeständige Schichten im Bereich von 13 bis 18 Karat abgeschieden.The invention relates to an alkaline bath for the electrodeposition of low-carat rosabis yellow-colored gold alloy layers containing soluble gold cyanide, soluble copper cyanide and potassium carbonate or potassium hydrogen carbonate. Corrosion-resistant layers in the range of 13 to 18 carats are deposited.

Zur Herstellung niederkarätiger rosa- und gelbfarbener Goldlegierungsüberzüge wurden bisher Bäder verwendet, die neben komplexen Gold-und Kupferzyaniden noch Kadmium und Chelatbildner enthalten (DE-AS 22 21 159). Solche Bäder arbeiten im allgemeinen in einem pH-Bereich von 7,5-12 und enthalten außerdem freies Zyanid, leitfähige Salze, wie z. B. Karbonate, und Puffersalze, wie z. B. Phosphate. Sie liefern bei günstigen Arbeitsbedingungen glänzende rosafarbene oder gelbe Legierungsniederschläge guter Qualität. Diese Bäder haben jedoch den gravierenden Nachteil, daß sie Kadmium enthalten, das physiologisch nicht unbedenklich ist und durch andere Stoffe ersetzt werden muß.Baths which contain cadmium and chelating agents in addition to complex gold and copper cyanides have been used to produce low-carat pink and yellow-colored gold alloy coatings (DE-AS 22 21 159). Such baths generally operate in a pH range of 7.5-12 and also contain free cyanide, conductive salts, such as. B. carbonates, and buffer salts, such as. B. Phosphates. They provide glossy pink or yellow alloy deposits of good quality in favorable working conditions. However, these baths have the serious disadvantage that they contain cadmium, which is not physiologically harmless and must be replaced by other substances.

Bekannt sind auch Goldbäder, die neben Gold noch Zink und andere Legierungsmetalle, insbesondere auch Kupfer, als lösliche Salze enthalten. Mit solchen galvanischen Bädern lassen sich bisher jedoch keine rosafarbenen oder gelben niederkarätigen Goldlegierungsschichten herstellen, sondern nur hochkarätige bzw. mißfarbige Schichten.Gold baths are also known which, in addition to gold, also contain zinc and other alloy metals, in particular copper, as soluble salts. With such galvanic baths, however, no pink or yellow low-carat gold alloy layers have so far been produced, but only high-quality or non-colored layers.

In der DE-OS2342691 wird ein zyanidisches alkalisches Weißgoldbad beschrieben, das neben Kaliumgoldzyanid und Kaliumzinkzyanid Kaliumnickelzyanid und Dikaliumhydrogenphosphate bei pH-Werten von 9-13 enthält. Mit diesen Bädern lassen sich jedoch keine niederkarätigen Goldlegierungsschichten herstellen.DE-OS2342691 describes a cyanidic alkaline white gold bath which, in addition to potassium gold cyanide and potassium zinc cyanide, contains potassium nickel cyanide and dipotassium hydrogen phosphate at pH values of 9-13. However, low-carat gold alloy layers cannot be produced with these baths.

Aus der DE-OS2244434 ist ein galvanisches Goldlegierungsbad bekannt, das neben Kaliumgoldzyanid noch Kupfersulfat und gegebenenfalls ein Zinksalz enthalten kann. Man erhält jedoch auch mit diesen Bädern, die bei pH-Werten von 3-10 arbeiten und Aldehyde, Diamine und arsenige Säure als essentielle Bestandteile enthalten, keine niederkarätigen Goldlegierungsschichten.From DE-OS2244434 a galvanic gold alloy bath is known which, in addition to potassium gold cyanide, can also contain copper sulfate and optionally a zinc salt. However, even with these baths, which operate at pH values of 3-10 and contain aldehydes, diamines and arsenic acid as essential components, no low-carat gold alloy layers are obtained.

In der DE-OS 27 54 207 wird ein Goldlegierungsbad beschrieben, das Kaliumgoldzyanid, Zinksulfat und Natriumkarbonat enthält und bei pH 4,9 betrieben wird. Aus diesem Bad werden grüne Niederschläge abgeschieden.DE-OS 27 54 207 describes a gold alloy bath which contains potassium gold cyanide, zinc sulfate and sodium carbonate and is operated at pH 4.9. Green precipitates are separated from this bath.

Weiterhin ist (DE-AS1033987) ein Goldlegierungsbad bekannt, das Kaliumgoldzyanid, Kupfer, Zink und Nickel in Form ihrer Äthylendiaminteträssigsäuresalze enthält. Bei pH 8 und einer Temperatur von 60 °C erhält man 19-karätige Legierungsüberzüge, die graustichig sind.Furthermore, a gold alloy bath is known (DE-AS1033987) which contains potassium gold cyanide, copper, zinc and nickel in the form of their ethylenediaminetetradic acid salts. At pH 8 and a temperature of 60 ° C, 19-carat alloy coatings are obtained, which are grayish.

Mit keinem der hier angeführten galvanischen Goldlegierungsbäder auf der Basis Gold, Kupfer, Zink war es bisher möglich, niederkarätige rosabis gelbfarbene Schichten zu erzeugen.With none of the galvanic gold alloy baths based on gold, copper, zinc mentioned here, it has so far been possible to produce low-carat rosabis yellow-colored layers.

Es war daher Aufgabe der vorliegenden Erfindung, ein alkalisches Bad zum galvanischen Abscheiden niederkarätiger rosa- bis gelbfarbener Goldlegierungsschichten mit einem Gehalt an löslichem Goldzyanid, löslichem Kupferzyanid und Kaliumkarbonat bzw. Kaliumhydrogenkarbonat zu finden, das korrosionsbeständige, physiologisch unbedenkliche Schichten von 13-18 Karat liefert.It was therefore an object of the present invention to find an alkaline bath for the electrodeposition of low-carat pink to yellow-colored gold alloy layers containing soluble gold cyanide, soluble copper cyanide and potassium carbonate or potassium hydrogen carbonate, which provides corrosion-resistant, physiologically acceptable layers of 13-18 carats.

Diese Aufgabe wurde erfindungsgemäß dadurch gelöst, daß das Bad 3-10 g/I Gold, 5-35 g/I Kupfer, 2,5-20 g/I Kaliumkarbonat und/oder Kalium hydrogenkarbonat und 7,5-40 g/I Zink als komplexes Zyanid enthält.This object was achieved in that the bath 3-10 g / l gold, 5-35 g / l copper, 2.5-20 g / l potassium carbonate and / or potassium hydrogen carbonate and 7.5-40 g / l zinc contains as complex cyanide.

Bewährt haben sich Bäder, die das Gold als Alkaligoldzyanid und das Kupfer als Alkalikupferzyanid enthalten. Vorzugsweise enthalten solche Bäder 10-30 g/I Zink als K2(Zn(CN)4),Baths containing gold as alkali gold cyanide and copper as alkali copper cyanide have proven successful. Such baths preferably contain 10-30 g / l of zinc as K 2 (Zn (CN) 4 ),

Zur Herstellung rosafarbener Goldlegierungsschichten werden den Bädern vorteilhafterweise noch 5-25 g/I eines Alkalisalzes einer Phosphor-und/oder Phosphonsäure zugesetzt, zur Herstellung gelber Goldlegierungsschichten 0,5-5 g/I Ammoniak und/oder ein Amin.For the production of pink gold alloy layers, 5-25 g / l of an alkali salt of a phosphoric and / or phosphonic acid are advantageously added to the baths, for the production of yellow gold alloy layers 0.5-5 g / l ammonia and / or an amine.

Bewährt haben sich auch Bäder, die 0,2-1,5 g/I einer Selen- und/oder Arsenverbindung als Glanzzusatz enthalten. Der Zusatz von Chelatbildnern, wie Äthylendiaminteträssigsäure oder anderer Aminokarbonsäuren, in Mengen von 5-20 g/I, ist in manchen Fällen ebenfalls empfehlenswert. Als Arbeitstemperatur hat sich der Bereich von 50 bis 75 °C, insbesondere 60-75°C, und als pH-Wert der Bereich von 8-12, insbesondere 9-10 bewährt.Baths containing 0.2-1.5 g / l of a selenium and / or arsenic compound have also proven useful as a gloss additive. The addition of chelating agents, such as ethylenediaminetetracid or other aminocarboxylic acids, in amounts of 5-20 g / l is also recommended in some cases. The range from 50 to 75 ° C., in particular 60-75 ° C., and the pH range from 8-12, in particular 9-10, has proven to be the working temperature.

Die erfindungsgemäße Bäder ermöglichen es, trotz verschiedenen Karatgehalts der Schichten von 13-18 Karat, je nach Badzusammensetzung und Arbeitsbedingungen, einen konstanten gleichmäßigen Rosafarbton oder Gelbfarbton zu erzeugen. Selbst bei einem Feingehalt von 14 kt wird bei Kupfergehalten von 30 bis 40 Gew.% ein angenehmer rosa Farbton (3-4 N) erzielt, der bei diesen hohen Kupfergehalten überraschend ist. Auch bei stark schwankendem Goldgehalt im Bad zwischen 3 und 10 g/I und einem Zinkgehalt zwischen 2 und 15 % im Überzug wird ein nahezu konstanter Rosafarbton geliefert. Die abgeschiedenen Schichten weisen dabei eine gute Duktilität auf.The baths according to the invention make it possible, despite different carat contents of the layers of 13-18 carats, depending on the bath composition and working conditions, to produce a constant, uniform pink or yellow color. Even with a fineness of 14 kt, a pleasant pink color (3-4 N) is achieved with copper contents of 30 to 40% by weight, which is surprising at these high copper contents. Even with a strongly fluctuating gold content in the bath between 3 and 10 g / l and a zinc content between 2 and 15% in the coating, an almost constant pink color is delivered. The deposited layers have good ductility.

Es ist überraschend, daß durch die Mitabscheidung von Zink aus galvanischen zyanidischen Gold-/Kupferbädern ein Rosafarbton bzw. auch ein gelber Farbton erzielt werden kann, nachdem allgemein bekannt ist, daß die Mitabscheidung von Zink in größeren Mengen aus Gold-/ Kupferbädern zu mißfarbenen, graustichigen und extrem spröden Schichten führt, im Gegensatz zu Kadmium.It is surprising that the co-deposition of zinc from galvanic cyanide gold / copper baths can result in a pink color or a yellow color, since it is generally known that the co-deposition of zinc in large quantities from gold / copper baths results in mis-colored, grayish and extremely brittle layers, in contrast to cadmium.

Die folgenden Beispiele sollen das erfindungsgemäße Bad näher erläutern :

  • 1. Aus einem Bad mit 8 g/I Gold als K(Au(CN)2), 30 g/I Kupfer als K2(Cu(CN)4), 40 g/I Zink als K2(Zn(CN)4), 5 g/l K2CO3, 0,3 g/l H2SeO3 und 8 g/l K2HPO4 werden bei 60°C, einem pH-Wert = 9 und Stromdichten von 0,6-1 A/dm2 rosafarbene Au/Cu/Zn-schichten mit einem Feingehalt von 13-15 kt abgeschieden.
  • 2. Aus einem Bad mit 5 g/I Gold, 7,5 g/I Kupfer und 20 g/I Zink als Kz(Zn(CN)4), das außerdem 5 g/l K2CO3, 0,3 g/l H2SeO3 und 16 g/l Kaliumtripolyphosphat enthält, werden bei 65 °C, pH = 9,5 und Stromdichten zwischen 1,2 und 1,8 A/dm2 18-karätige rosafarbene Schichten abgeschieden, die ca. 5 Gew.% Zink enthalten.
  • 3. Ein Bad mit 4 g/l Gold als K2/Au(CN)2), 20 g/l Kupfer als K2(Cu(CN)4), 20 g/I Zn als K2(Zn(CN)4), 13 g/l K2CO3, 18 g/l KHCO3 und 2 ml/l 24 %iger Ammoniak ermöglicht bei pH = 10, einer Temperatur von 60 °C und einer Stromdichte von 0,8-1,2 A/dm2 die Abscheidung von 18-karätigen, gelben (2N) Goldlegierungsüberzügen.
The following examples are intended to explain the bath according to the invention in more detail:
  • 1. From a bath with 8 g / I gold as K (Au (CN) 2 ), 30 g / I copper as K 2 (Cu (CN) 4 ), 40 g / I zinc as K 2 (Zn (CN) 4 ), 5 g / l K 2 CO 3 , 0.3 g / l H 2 SeO 3 and 8 g / l K 2 HPO 4 are at 60 ° C, a pH = 9 and current densities of 0.6-1 A / dm 2 pink Au / Cu / Zn layers with a fineness of 13-15 kt.
  • 2. From a bath with 5 g / l gold, 7.5 g / l copper and 20 g / l zinc as K z (Zn (CN) 4 ), which also contains 5 g / l K 2 CO 3 , 0.3 g / l H 2 SeO 3 and 16 g / l potassium tripolyphosphate, are deposited at 65 ° C, pH = 9.5 and current densities between 1.2 and 1.8 A / dm 2 18-carat pink layers, which approx. Contain 5% by weight zinc.
  • 3. A bath with 4 g / l gold as K 2 / Au (CN) 2 ), 20 g / l copper as K 2 (Cu (CN) 4 ), 20 g / I Zn as K 2 (Zn (CN) 4 ), 13 g / l K 2 CO 3 , 18 g / l KHCO 3 and 2 ml / l 24% ammonia enables at pH = 10, a temperature of 60 ° C and a current density of 0.8-1.2 A / dm 2 deposition of 18-carat, yellow (2N) gold alloy coatings.

Die Robustheit und Langzeitstabilität der erfindungsgemäßen Bäder erlaubt einen störungsfreien Betrieb in der Praxis, da auch schwankende Metallgehalte bei konstanten Stromdichten zu gleichbleibenden Schichten führen.The robustness and long-term stability of the baths according to the invention permit trouble-free operation in practice, since fluctuating metal contents lead to constant layers at constant current densities.

Claims (6)

1. An alkaline bath for the galvanic deposition of low-carat pink to yellow-coloured gold alloy layers having a content of soluble gold cyanide, soluble copper cyanide and potassium carbonate or potassium hydrogen carbonate, characterised in that it contains from 3 to 10 g/I of gold, from 5 to 35 g/I of copper, from 2.5 to 20 g/I of potassium carbonate and/or potassium hydrogen carbonate and from 7.5 to 40 g/l of zinc as complex zinc cyanide.
2. An alkaline bath according to claim 1, characterised in that it contains from 10 to 30 g/I of zinc as K2(Zn(CN)4).
3. An alkaline bath according to claims 1 and 2, characterised in that it also contains from 5 to 25 g/I of an alkali metal salt of a phosphoric acid and/or a phosphonic acid or from 0.5 to 5 g/I of ammonia and/or an amine.
4. An alkaline bath according to claims 1 to 3, characterised in that it also contains from 0.2 to 1.5 g/I of a selenium compound and/or an arsenic compound.
5. An alkaline bath according to claims 1 to 4, characterised in that it also contains from 5 to 20 g/I of a chelate former.
6. The use of an alkaline bath according to claims 1 to 5 for the galvanic deposition of low-carat pink to yellow-coloured gold alloy layers, characterised in that it is operated at a pH of from 8 to 12 and at a temperature of from 50 to 75 °C.
EP81103982A 1980-05-31 1981-05-23 Alkaline bath for the electrodeposition of pink to yellow coloured layers of gold alloys with low carat weight Expired EP0041208B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803020765 DE3020765A1 (en) 1980-05-31 1980-05-31 ALKALINE BATH FOR GALVANIC DEPOSITION OF LOW-CARAINE PINK TO YELLOW-COLORED GOLD ALLOY LAYERS
DE3020765 1980-05-31

Publications (2)

Publication Number Publication Date
EP0041208A1 EP0041208A1 (en) 1981-12-09
EP0041208B1 true EP0041208B1 (en) 1984-01-18

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EP81103982A Expired EP0041208B1 (en) 1980-05-31 1981-05-23 Alkaline bath for the electrodeposition of pink to yellow coloured layers of gold alloys with low carat weight

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US (1) US4358351A (en)
EP (1) EP0041208B1 (en)
JP (1) JPS5723089A (en)
DE (1) DE3020765A1 (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0140832B1 (en) * 1983-09-01 1988-01-13 H. E. Finishing SA Bath for the electrolytic deposition of a gold alloy and galvanic process using this bath
DE3345795A1 (en) * 1983-12-17 1985-07-04 LPW-Chemie GmbH, 4040 Neuss ELECTROLYTE FOR GALVANIC DEPOSITION OF LOW-CARAE GOLD-COPPER-ZINC ALLOYS
DE3345794A1 (en) * 1983-12-17 1985-07-04 LPW-Chemie GmbH, 4040 Neuss Electrolyte for depositing a low-carat yellow- to red-coloured gold/copper/zinc alloy
CH662583A5 (en) * 1985-03-01 1987-10-15 Heinz Emmenegger GALVANIC BATH FOR THE ELECTROLYTIC DEPOSITION OF GOLD-COPPER-CADMIUM-ZINC ALLOYS.
DE3601559A1 (en) * 1986-01-21 1987-07-23 Lpw Chemie Gmbh Method of adjusting the "gold colour" in the electrodeposition of low-carat gold/copper/zinc alloys
EP0304315B1 (en) * 1987-08-21 1993-03-03 Engelhard Limited Bath for electrolytic deposition of a gold-copper-zinc alloy
US5085744A (en) * 1990-11-06 1992-02-04 Learonal, Inc. Electroplated gold-copper-zinc alloys
ATE220736T1 (en) 1995-11-03 2002-08-15 Enthone Omi Inc ELECTROPLATTING METHODS, COMPOSITIONS AND COATINGS
GB9522591D0 (en) * 1995-11-03 1996-01-03 Enthone Omi Suisse S A Electroplating processes compositions and deposits
CH714243B1 (en) * 2006-10-03 2019-04-15 Swatch Group Res & Dev Ltd Electroforming process and part or layer obtained by this method.
CH710184B1 (en) 2007-09-21 2016-03-31 Aliprandini Laboratoires G Process for obtaining a yellow gold alloy deposit by electroplating without the use of toxic metals or metalloids.
EP2312021B1 (en) * 2009-10-15 2020-03-18 The Swatch Group Research and Development Ltd. Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals
ITFI20120103A1 (en) 2012-06-01 2013-12-02 Bluclad Srl GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS.
CN104233384A (en) * 2014-09-17 2014-12-24 朱忠良 Cyanide-free gold electroplating solution and electroplating process using same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH286123A (en) * 1952-05-08 1952-10-15 Spreter Victor Bath for the galvanic deposition of gold alloys.
DE2121150C3 (en) * 1971-04-24 1980-08-21 Schering Ag, 1000 Berlin Und 4619 Bergkamen Process for the electrodeposition of gold alloys
CH556916A (en) * 1972-03-23 1974-12-13 Lea Ronal Inc PROCESS FOR THE ELECTROLYTIC DEPOSIT OF GOLD ALLOYS.
ZA734253B (en) * 1972-07-10 1975-02-26 Degussa Electrolytic bath
JPS4965341A (en) * 1972-08-24 1974-06-25
DE2244434C3 (en) * 1972-09-06 1982-02-25 Schering Ag, 1000 Berlin Und 4619 Bergkamen Aqueous bath for the galvanic deposition of gold and gold alloys
CH626410A5 (en) * 1977-09-07 1981-11-13 Metaux Precieux Sa Bath for the electrolytic deposition of gold or gold alloys and use of this bath
JPS5662984A (en) * 1979-10-25 1981-05-29 Seiko Epson Corp Gold plating constitution of external parts for watch

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Publication number Publication date
EP0041208A1 (en) 1981-12-09
DE3020765C2 (en) 1988-03-31
JPS5723089A (en) 1982-02-06
US4358351A (en) 1982-11-09
DE3020765A1 (en) 1981-12-10
JPS648076B2 (en) 1989-02-13

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