EP0416342A1 - Galvanic gold alloy bath - Google Patents

Galvanic gold alloy bath Download PDF

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Publication number
EP0416342A1
EP0416342A1 EP90115670A EP90115670A EP0416342A1 EP 0416342 A1 EP0416342 A1 EP 0416342A1 EP 90115670 A EP90115670 A EP 90115670A EP 90115670 A EP90115670 A EP 90115670A EP 0416342 A1 EP0416342 A1 EP 0416342A1
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EP
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Prior art keywords
potassium
cyanide
copper
gold
silver
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EP90115670A
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German (de)
French (fr)
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EP0416342B1 (en
Inventor
Werner Dipl.-Ing. Kuhn
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 a galvanic gold alloy bath containing 1 to 15 g / l gold as potassium gold (I) cyanide, 5 to 50 g / l copper as potassium copper (I) cyanide, 0.05 to 5 g / l silver as potassium silver ( I) cyanide, free alkali cyanide, dipotassium hydrogen phosphate, as well as a selenium compound and a pH of 8.5 to 11.
  • the galvanic deposition of gold alloys has become particularly important for decorative and technical purposes.
  • the soft, cell yellow, matt pure gold layers can be characterized by the deposition of other metals in their properties, e.g. change in gloss, hardness, wear resistance or color in many ways.
  • a substantial proportion of the deposited gold alloy coatings have 14 - 18 carat, yellow or rose-colored coatings, which contain copper as an alloy metal to lighten the resulting red color, a white-coloring metal such as cadmium, silver or zinc.
  • Such coatings are used, for example, in the jewelry and eyewear industry, where double layers have been largely replaced by galvanic coatings. Such coatings are also used in electrical engineering when low contact resistance is not required, such as with slip ring and rotary contacts.
  • the galvanic deposition of gold / copper / silver alloy coatings causes considerable difficulties due to the potential position of the metals in the electrolyte and has so far only been solved unsatisfactorily.
  • the basis for the joint deposition are aqueous solutions of the cyano complexes of the three metals. In the alkaline range, in which these baths are only stable, the potential of silver is much more noble than that of gold and copper, so that silver is preferentially deposited and therefore only coatings, depending on the silver content, with whitish-yellow or greenish-yellow color are obtained .
  • DE-PS 801 312 therefore tries to shift the potential of the silver to less noble values by using the lowest possible pH.
  • DD-PS 59022 also works in neutral and tries to achieve glossy layers by applying current changes with a low concentration of free alkali metal cyanide, which in practice often leads to coatings with a non-uniform color.
  • the gloss formation of the coatings can also be achieved with chemical compounds.
  • DE-PS 750 185 the deposition of silver or copper coatings from an alkaline cyanide bath has a shine or tellurium effect.
  • It was therefore an object of the present invention to develop a galvanic gold alloy bath which contains 1 to 15 g / l gold as potassium gold (I) cyanide, 5 to 50 g / l copper as potassium copper (I) cyanide, 0.05 to 5 g / l of silver as potassium silver (I) cyanide, free alkali metal cyanide dipotassium hydrogen phosphate, and also contains a selenium compound and has a pH of 8.5 to 11, which is stable and shiny without expensive aids and, depending on the copper content and current density, yellow to supplies rose gold-copper-silver alloy plating.
  • This object is achieved in that the content of free alkali metal cyanide is at most 10 g / l and that it contains 0.1 to 1 mg / l selenium as potassium selenocyanate.
  • the bath preferably additionally contains 0.1 to 5 ml / l of a surfactant from the group of nonionic wetting agents of the ethylene oxide adduct type and their phosphate esters.
  • a surfactant from the group of nonionic wetting agents of the ethylene oxide adduct type and their phosphate esters.
  • alkyl polyglycol ether butyl or nonylphenol polyglycol ether and their phosphate esters can be used.
  • the galvanic gold alloy baths according to the invention are preferably composed as follows: 1 - 15 g / l gold as KAu (CN) 2 5 - 50 g / l copper as K2Cu (CN) 3 0.05 - 5 g / l silver as KAg (CN) 2 0.1-10 g / l of free alkali metal cyanide 1 - 10 g / l di-potassium hydrogen phosphate 0.1 - 5 m / l surfactant 0.1-1 mg / l Be as KSeCN
  • a phosphate ester such as, for example, nonylphenol polyglycol ether phosphate ester, is suitable as the surfactant which supports the formation of gloss.
  • the bath has a pH between 8.5 and 11 and is preferably operated at a bath temperature of 60 - 75 o C and current densities of 0.2 - 2.5 A / dm2.
  • the following bath composition is preferably used for the most commonly deposited 14-18 carat yellow or rose-colored gold alloy coatings in practice: 3 - 5 g / l gold as KAu (CN) 2 20-25 g / l copper as K2Cu (CN) 3 0.2 - 0.5 g / l silver as KAg (CN) 2 2-4 g / l free alkali cyanide 2-4 g / l di-potassium hydrogen phosphate 0.1 - 1 ml / l surfactant 0.1, 0.5 mg / l Be as KSeCN.
  • the bath is preferably at a pH of 9 - 70 operated o C - 10 and a bath temperature 60 seconds. Shiny coatings are obtained in the current density range between 0.3 and 1.5 A / dm2, the carat content of the layers decreasing with increasing current density. The deposited layers are very ductile and even low-carat coatings have good corrosion resistance in the copper chloride test.
  • the pH is adjusted to 9 with potassium hydroxide.
  • the bath is now heated to 65 o C and a prepared, shiny nickel-plated copper sheet with a surface area of 0.25 dm2 is gilded with 2.5 amine at a current density of 0.5 A / dm2.
  • the result is a glossy coating with a weak rose color, which has a carat content of 17.2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Cosmetics (AREA)
  • Dental Preparations (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Yellow to rose-colored gold alloy coatings with copper and silver are obtained from stable galvanic baths with a pH of 8.5 to 11 containing, 1 to 15 g/liter gold as potassium gold (I) cyanide, 5 to 50 g/liter copper as potassium copper (I) cyanide, 0.05 to 5 g/liter silver as potassium silver (I) cyanide and dipotassium hydrogenphosphate as well as alkali cyanides in amounts of up to 10 g/liter and 0.1-1 mg/liter potassium selenocyanate.

Description

Die Erfindung betrifft ein galvanisches Goldlegierungsbad, das 1 bis 15 g/l Gold als Kalium­gold(I)-cyanid, 5 bis 50 g/l Kupfer als Kaliumkupfer(I)-cyanid, 0,05 bis 5 g/l Silber als Kaliumsilber(I)cyanid, freies Alkalicyanid, Dikaliumhydrogenphosphat, sowie eine Selenverbindung und einen pH-Wert von 8,5 bis 11 aufweist.The invention relates to a galvanic gold alloy bath containing 1 to 15 g / l gold as potassium gold (I) cyanide, 5 to 50 g / l copper as potassium copper (I) cyanide, 0.05 to 5 g / l silver as potassium silver ( I) cyanide, free alkali cyanide, dipotassium hydrogen phosphate, as well as a selenium compound and a pH of 8.5 to 11.

Die galvanische Abscheidung von Goldlegierungen hat für dekorative und technische Zwecke besondere Bedeutung erlangt. Die weichen, zellgelben, matten Reingoldschichten lassen sich durch die Mitabscheidung anderer Metalle in ihren Eigenschaften, z.B. hinsichtlich Glanz, Härte, Verschleißfestigkeit oder Farbe in vielfältiger Weise verändern. Einen erheblichen Anteil an den abgeschiedenen Goldlegierungsüberzügen haben 14 - 18 karätige, gelbe oder rosefarbene Überzüge, die neben Kupfer als Legierungsmetall zur Aufhellung des dadurch bedingten roten Farbtons ein weißfärbendes Metall wie Cadmium, Silber oder Zink enthalten.The galvanic deposition of gold alloys has become particularly important for decorative and technical purposes. The soft, cell yellow, matt pure gold layers can be characterized by the deposition of other metals in their properties, e.g. change in gloss, hardness, wear resistance or color in many ways. A substantial proportion of the deposited gold alloy coatings have 14 - 18 carat, yellow or rose-colored coatings, which contain copper as an alloy metal to lighten the resulting red color, a white-coloring metal such as cadmium, silver or zinc.

Anwendung finden solche Überzüge z.B. in der Schmuck­und Brillenindustrie, wo Double-Schichten weitgehend durch galvanische Beschichtungen ersetzt wurden. Aber auch in der Elektrotechnik werden solche Überzüge verwendet, wenn kein niedriger Kontaktwiderstand erforderlich ist, wie z.B. bei Schleifring- und Drehkontakten.Such coatings are used, for example, in the jewelry and eyewear industry, where double layers have been largely replaced by galvanic coatings. Such coatings are also used in electrical engineering when low contact resistance is not required, such as with slip ring and rotary contacts.

Die galvanische Abscheidung von Gold/Kupfer/Silber-­Legierungsüberzügen bereitet aufgrund der Potentiallage der Metalle im Elektrolyten erhebliche Schwierigkeiten und ist bis heute nur unbefriedigend gelöst. Basis für die gemeinsame Abscheidung sind wäßrige Lösungen der Cyanokomplexe der drei Metalle. Im alkalischen Bereich, in dem diese Bäder nur stabil sind, ist das Potential des Silbers wesentlich edler als das von Gold und Kupfer, so daß bevorzugt Silber abgeschieden wird und deshalb nur Überzüge, je nach Silbergehalt, mit weißlichgelber oder grünlich-gelber Farbe erhalten werden. In der DE-PS 801 312 wird deshalb versucht, durch Anwendung eines möglichst niedrigen pH-Wertes das Potential des Silbers zu unedleren Werten zu verschieben. Doch ist bei dem angegebenen pH von 7 das zur Stabilisierung der Cyanokomplexe der drei Metalle erforderliche freie Alkalicyanid nicht mehr stabil, die Konzentration ändert sich ständig, wodurch sich auch eine ständige Änderung in der Zusammensetzung der abgeschiedenen Legierung ergibt. In der DD-PS 59022 wird ebenfalls im Neutralen gearbeitet und versucht, durch Anwendung von Stromwechsel bei geringer Konzentration an freiem Alkalicyanid glänzende Schichten zu erzielen, was in der Praxis häufig zu Überzügen mit nicht gleichmäßiger Farbe führt.The galvanic deposition of gold / copper / silver alloy coatings causes considerable difficulties due to the potential position of the metals in the electrolyte and has so far only been solved unsatisfactorily. The basis for the joint deposition are aqueous solutions of the cyano complexes of the three metals. In the alkaline range, in which these baths are only stable, the potential of silver is much more noble than that of gold and copper, so that silver is preferentially deposited and therefore only coatings, depending on the silver content, with whitish-yellow or greenish-yellow color are obtained . DE-PS 801 312 therefore tries to shift the potential of the silver to less noble values by using the lowest possible pH. However, at the stated pH of 7, the free alkali metal cyanide required to stabilize the cyano complexes of the three metals is no longer stable, the concentration changes constantly, which also results in a constant change in the composition of the deposited alloy. DD-PS 59022 also works in neutral and tries to achieve glossy layers by applying current changes with a low concentration of free alkali metal cyanide, which in practice often leads to coatings with a non-uniform color.

In alkalischen Bädern kann die Glanzbildung der Überzüge auch mit chemischen Verbindungen erzielt werden. Nach der DE-PS 750 185 wirken bei der Abscheidung von Silber- oder Kupfer-Überzügen aus einem alkalisch cyanidischen Bad Seien- oder Tellurverbindungen glanzbildend.In alkaline baths, the gloss formation of the coatings can also be achieved with chemical compounds. According to DE-PS 750 185, the deposition of silver or copper coatings from an alkaline cyanide bath has a shine or tellurium effect.

Es war daher Aufgabe der vorliegenden Erfindung, ein galvanisches Goldlegierungsbad zu entwickeln, das 1 bis 15 g/l Gold als Kaliumgold(I)-cyanid, 5 bis 50 g/l Kupfer als Kaliumkupfer (I)-cyanid, 0, 05 bis 5 g/l Silber als Kaliumsilber(I)-cyanid, freies Alkalicyanid Dikaliumhydrogenphosphat, sowie eine Selenverbindung enthält und einen pH-Wert von 8,5 bis 11 aufweist, das stabil ist und ohne aufwendige Hilfsmittel glänzende, und je nach Kupfergehalt und Stromdichte gelbe bis rosefarbene Gold-Kupfer-Silber-Legierungsüberzüge liefert.It was therefore an object of the present invention to develop a galvanic gold alloy bath which contains 1 to 15 g / l gold as potassium gold (I) cyanide, 5 to 50 g / l copper as potassium copper (I) cyanide, 0.05 to 5 g / l of silver as potassium silver (I) cyanide, free alkali metal cyanide dipotassium hydrogen phosphate, and also contains a selenium compound and has a pH of 8.5 to 11, which is stable and shiny without expensive aids and, depending on the copper content and current density, yellow to supplies rose gold-copper-silver alloy plating.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß der Gehalt an freiem Alkalicyanid höchstens 10 g/l beträgt und daß es 0, 1 bis 1 mg/l Selen als Kaliumselenocyanat enthält.This object is achieved in that the content of free alkali metal cyanide is at most 10 g / l and that it contains 0.1 to 1 mg / l selenium as potassium selenocyanate.

Vorzugsweise enthält das Bad zusätzlich noch 0,1 bis 5 ml/l eines Tensids aus der Gruppe der nichtionogenen Netzmittel vom Ethylenoxidaddukttyp und ihrer Phosphatester. Als Beispiele sind Alkylpolyglycolether Butyl- oder Nonylphenolpolyglycolether und ihre Phosphatester verwendbar.The bath preferably additionally contains 0.1 to 5 ml / l of a surfactant from the group of nonionic wetting agents of the ethylene oxide adduct type and their phosphate esters. As examples, alkyl polyglycol ether butyl or nonylphenol polyglycol ether and their phosphate esters can be used.

Überraschenderweise hat sich gezeigt, daß im schwach alkalischen Bereich bei Gehalten an freiem Alkalicyanid ≦ 10 g/l in Kombination mit dem Glanzbildner Kaliumselenocyanat nicht nur die Hitabscheidung einer ausreichenden Kupfermenge möglich ist und das Bad stabile Verhältnisse aufweist, sondern die Überzüge auch glänzend und duktil sind.Surprisingly, it has been shown that in the weakly alkaline range with free alkali metal cyanide ≦ 10 g / l in combination with the brightener potassium selenocyanate, not only is it possible to deposit a sufficient amount of copper and the bath has stable conditions, but the coatings are also glossy and ductile .

Die erfindungsgemäßen galvanischen Goldlegierungsbäder setzen sich vorzugsweise wie folgt zusammen:
1 - 15 g/l Gold als KAu(CN)₂
5 - 50 g/l Kupfer als K₂Cu(CN)₃
0,05 - 5 g/l Silber als KAg(CN)₂
0, 1 - 10 g/l freies Alkalicyanid
1 - 10 g/l di-Kaliumhydrogenphosphat
0,1 - 5 m/l Tensid
0,1 - 1 mg/l Seien als KSeCNThe galvanic gold alloy baths according to the invention are preferably composed as follows:
1 - 15 g / l gold as KAu (CN) ₂
5 - 50 g / l copper as K₂Cu (CN) ₃
0.05 - 5 g / l silver as KAg (CN) ₂
0.1-10 g / l of free alkali metal cyanide
1 - 10 g / l di-potassium hydrogen phosphate
0.1 - 5 m / l surfactant
0.1-1 mg / l Be as KSeCN

Als Tensid, das die Glanzbildung unterstützt, eignet sich ein Phosphatester, wie z.B. Nonylphenolpolyglycoletherphosphatester. Das Bad weist einen pH-Wert zwischen 8,5 und 11 auf und wird vorzugsweise bei einer Badtemperatur von 60 - 75o C und Stromdichten von 0,2 - 2,5 A/dm² betrieben.A phosphate ester, such as, for example, nonylphenol polyglycol ether phosphate ester, is suitable as the surfactant which supports the formation of gloss. The bath has a pH between 8.5 and 11 and is preferably operated at a bath temperature of 60 - 75 o C and current densities of 0.2 - 2.5 A / dm².

Für die in der Praxis am häufigsten abgeschiedenen 14-18 karätigen gelben oder rosefarbenen Goldlegierungsüberzüge wird bevorzugt folgende Badzusammensetzung benutzt:
3 - 5 g/l Gold als KAu(CN)₂
20- 25 g/l Kupfer als K₂Cu(CN)₃
0,2 - 0,5 g/l Silber als KAg(CN)₂
2 - 4 g/l freies Alkalicyanid
2 - 4 g/l di-Kaliumhydrogenphosphat
0,1 - 1 ml/l Tensid
0, 1 - 0,5 mg/l Seien als KSeCN.The following bath composition is preferably used for the most commonly deposited 14-18 carat yellow or rose-colored gold alloy coatings in practice:
3 - 5 g / l gold as KAu (CN) ₂
20-25 g / l copper as K₂Cu (CN) ₃
0.2 - 0.5 g / l silver as KAg (CN) ₂
2-4 g / l free alkali cyanide
2-4 g / l di-potassium hydrogen phosphate
0.1 - 1 ml / l surfactant
0.1, 0.5 mg / l Be as KSeCN.

Das Bad wird bevorzugt bei einem pH von 9 - 10 und einer Badtemperatur von 60 - 70o C betrieben. Glänzende Überzüge werden im Stromdichtebereich zwischen 0,3 und 1 ,5 A/dm² erhalten, wobei mit steigender Stromdichte der Karatgehalt der Schichten abnimmt. Die abgeschiedenen Schichten sind sehr duktil und selbst niederkarätige Überzüge weisen im Kupferchloridtest eine gute Korrosionsbeständigkeit auf.The bath is preferably at a pH of 9 - 70 operated o C - 10 and a bath temperature 60 seconds. Shiny coatings are obtained in the current density range between 0.3 and 1.5 A / dm², the carat content of the layers decreasing with increasing current density. The deposited layers are very ductile and even low-carat coatings have good corrosion resistance in the copper chloride test.

Folgendes Beispiel soll das erfindungsgemäße galvanische Goldlegierungsbad näher erläutern:
The following example is intended to explain the galvanic gold alloy bath according to the invention in more detail:

Zur Herstellung von einem Liter Bad werden folgende Substanzen nacheinander in destilliertem Wasser aufgelöst:
2 g Kaliumcyanid, 69,2 g Kaliumkupfer(I)-cyanid, 7,5 g Kaliumdicyanoaurat(I), 2 g di-Kaliumhydrogenphosphat, 0,46 g Kaliumdicyanoargentat und 0,18 mg Kaliumselenocyanat. Dazu werden 0,1 ml Netzmittel Nonylphenolpolygglycoletherphosphatester in der Verdünnung 1 : 5 gegeben und zum Schluß wird mit Wasser auf 1 l aufgefüllt.To produce a liter of bath, the following substances are successively dissolved in distilled water:
2 g potassium cyanide, 69.2 g potassium copper (I) cyanide, 7.5 g potassium dicyanoaurate (I), 2 g di-potassium hydrogenphosphate, 0.46 g potassium dicyanoargentate and 0.18 mg potassium selenocyanate. For this, 0.1 ml of wetting agent nonylphenol polyglycol ether phosphate ester is added in a dilution of 1: 5, and the mixture is finally made up to 1 l with water.

Der pH-Wert wird mit Kaliumhydroxid auf 9 eingestellt. Das Bad wird nun auf 65o C erhitzt und ein vorbereitetes, glanzvernickeltes Kupferblech mit einer Oberfläche von 0,25 dm² wird 2,5 Amin bei einer Stromdichte von 0,5 A/dm² vergoldet. Es resultiert ein glänzender Überzug mit schwachem Rosefarbton, der einen Karatgehalt von 17,2 aufweist.The pH is adjusted to 9 with potassium hydroxide. The bath is now heated to 65 o C and a prepared, shiny nickel-plated copper sheet with a surface area of 0.25 dm² is gilded with 2.5 amine at a current density of 0.5 A / dm². The result is a glossy coating with a weak rose color, which has a carat content of 17.2.

Claims (2)

1. Galvanisches Goldlegierungsbad, das 1 bis 15 g/l Gold als Kaliumgold (I)-cyanid, 5 bis 50 g/l Kupfer als Kaliumkupfer(I)-cyanid, 0,05 bis 5 g/l Silber als Kaliumsilber(I)-cyanid, freies Alkalicyanid, Dikaliumhydrogenphosphat, sowie eine Selenverbindung enthält und einen pH-Wert von 8,5 bis 11 aufweist,
dadurch gekennzeichnet,
daß der Gehalt an freiem Alkalicyanid im Bad höchstens 10 g/l beträgt, und daß es 0,1 bis 1 mg/l Seien als Kaliumselenocyanat enthält.1. Galvanic gold alloy bath containing 1 to 15 g / l gold as potassium gold (I) cyanide, 5 to 50 g / l copper as potassium copper (I) cyanide, 0.05 to 5 g / l silver as potassium silver (I) contains cyanide, free alkali metal cyanide, dipotassium hydrogen phosphate and a selenium compound and has a pH of 8.5 to 11,
characterized,
that the content of free alkali cyanide in the bath is at most 10 g / l, and that it contains 0.1 to 1 mg / l of be as potassium selenocyanate. 2. Galvanisches Goldlegierungsbad nach Anspruch 1,
dadurch gekennzeichnet,
daß es zusätzlich 0, 1 bis 5 ml eines Tensids aus der Gruppe der nichtionogenen Netzmittel vom Ethylenoxidaddukttyp und ihrer Phosphatester enthält.2. Galvanic gold alloy bath according to claim 1,
characterized,
that it additionally contains 0.1 to 5 ml of a surfactant from the group of non-ionic wetting agents of the ethylene oxide adduct type and their phosphate esters.
EP90115670A 1989-09-06 1990-08-16 Galvanic gold alloy bath Expired - Lifetime EP0416342B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3929569A DE3929569C1 (en) 1989-09-06 1989-09-06
DE3929569 1989-09-06
SG79294A SG79294G (en) 1989-09-06 1994-06-16 Galvante gold alloy bath.

Publications (2)

Publication Number Publication Date
EP0416342A1 true EP0416342A1 (en) 1991-03-13
EP0416342B1 EP0416342B1 (en) 1994-03-16

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Country Status (13)

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US (1) US5006208A (en)
EP (1) EP0416342B1 (en)
JP (1) JPH03100194A (en)
AT (1) ATE103018T1 (en)
BR (1) BR9004378A (en)
DD (1) DD297668A5 (en)
DE (2) DE3929569C1 (en)
DK (1) DK0416342T3 (en)
ES (1) ES2050317T3 (en)
FI (1) FI93661C (en)
HK (1) HK67794A (en)
NO (1) NO903868L (en)
SG (1) SG79294G (en)

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EP2312021A1 (en) * 2009-10-15 2011-04-20 The Swatch Group Research and Development Ltd. Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals
EP2505691A1 (en) * 2011-03-31 2012-10-03 The Swatch Group Research and Development Ltd. Process for obtaining a gold alloy deposit of 18 carat 3N
WO2015027982A1 (en) * 2013-08-29 2015-03-05 Harting Kgaa Contact element with gold coating
EP1983077B1 (en) 2007-04-19 2016-12-28 Enthone, Inc. Electrolyte and method for electrolytic deposition of gold-copper alloys
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

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DE10354760A1 (en) * 2003-11-21 2005-06-23 Enthone Inc., West Haven Process for depositing nickel and chromium (VI) free metallic matte layers
SG127854A1 (en) * 2005-06-02 2006-12-29 Rohm & Haas Elect Mat Improved gold electrolytes
US20090104463A1 (en) 2006-06-02 2009-04-23 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes
JP4711227B2 (en) * 2005-11-09 2011-06-29 央 澤栗 Bath gas dissolution production equipment
CH714243B1 (en) * 2006-10-03 2019-04-15 Swatch Group Res & Dev Ltd Electroforming process and part or layer obtained by this method.
CN112663095A (en) * 2020-11-10 2021-04-16 杭州科尔贵金属有限公司 Improved 3D hard gold electroforming liquid medicine formula and preparation process

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WO2002065953A1 (en) * 2001-02-19 2002-08-29 Implantcast Gmbh Endoprothesis with galvanised silver layer
US7018411B2 (en) 2001-02-19 2006-03-28 Implantcast Gmbh Endoprothesis with galvanised silver layer
EP1983077B1 (en) 2007-04-19 2016-12-28 Enthone, Inc. Electrolyte and method for electrolytic deposition of gold-copper alloys
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
EP2312021A1 (en) * 2009-10-15 2011-04-20 The Swatch Group Research and Development Ltd. Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals
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
EP2505691A1 (en) * 2011-03-31 2012-10-03 The Swatch Group Research and Development Ltd. Process for obtaining a gold alloy deposit of 18 carat 3N
US10053789B2 (en) 2011-03-31 2018-08-21 The Swatch Group Research And Development Ltd Method of obtaining a 18 caracts 3N gold alloy
US10793961B2 (en) 2011-03-31 2020-10-06 The Swatch Group Research And Development Ltd Method of obtaining a 18 carats 3N gold alloy
WO2015027982A1 (en) * 2013-08-29 2015-03-05 Harting Kgaa Contact element with gold coating

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HK67794A (en) 1994-07-22
NO903868D0 (en) 1990-09-05
JPH03100194A (en) 1991-04-25
DD297668A5 (en) 1992-01-16
FI93661C (en) 1995-05-10
EP0416342B1 (en) 1994-03-16
ES2050317T3 (en) 1994-05-16
ATE103018T1 (en) 1994-04-15
US5006208A (en) 1991-04-09
SG79294G (en) 1994-10-14
FI904377A0 (en) 1990-09-05
FI93661B (en) 1995-01-31
DK0416342T3 (en) 1994-04-05
NO903868L (en) 1991-03-07
DE59004996D1 (en) 1994-04-21
BR9004378A (en) 1991-09-03
DE3929569C1 (en) 1991-04-18

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