EP1983077B1 - Electrolyte and method for electrolytic deposition of gold-copper alloys - Google Patents

Electrolyte and method for electrolytic deposition of gold-copper alloys Download PDF

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Publication number
EP1983077B1
EP1983077B1 EP07007963.7A EP07007963A EP1983077B1 EP 1983077 B1 EP1983077 B1 EP 1983077B1 EP 07007963 A EP07007963 A EP 07007963A EP 1983077 B1 EP1983077 B1 EP 1983077B1
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EP
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Prior art keywords
acid
electrolyte
gold
nitrilo
copper
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EP07007963.7A
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German (de)
French (fr)
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EP1983077A1 (en
Inventor
Guy Desthomas
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MacDermid Enthone Inc
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Enthone Inc
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Priority to EP07007963.7A priority Critical patent/EP1983077B1/en
Priority to EP16197251.8A priority patent/EP3170924A1/en
Priority to CN2008100934716A priority patent/CN101289756B/en
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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
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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

  • This invention relates to an electrolyte as well as a method for the electrolytic deposition of a gold-copper alloy on a substrate surface.
  • alloy layers which can be varied in respect of their physical properties like brightness, hardness, wear resistance or colour. These properties are influenced by the composites of the alloys, e. g. the metals co-plated, as well as by the composition of the bath used for the deposition of the alloy, e. g. the electrolyte. Further, also the method and the plating parameters like temperature and current density are influencing the plating result in important ways.
  • U.S. patent 5,006,208 discloses a galvanic gold alloying bath which contains beneath gold and copper in form of cyanide compounds a selenium compound.
  • the deposit achieved from this galvanic bath is soft, light yellow and matt.
  • the gold-alloy containing is constituted by 14 - 18 carat.
  • European patent EP 0 384 679 B1 discloses a bath for the electrolytic deposition of gold-copper alloy as well as a method for electroplating articles using such a bath.
  • An electrolyte is disclosed which contains gold in form of a cyanide compound, copper in the form of a cyanide compound as well as tellurium or bismuth in the form of watersoluble compounds.
  • European patent application EP 0 566 054 A1 discloses a solution for electroplating gold-copper alloys.
  • an electrolyte comprising a soluble gold compound present as a gold cyanide complex, a soluble copper compound present as a copper cyanide complex as well as a soluble divalent sulfur compound in an amount sufficient to brighten the alloys.
  • the brightening additive may be a thiocyanate, thiomalic acid, imidazolidinethione, a sulfite or thiobarbituric acid.
  • Further patent documents disclosing the deposition of gold-copper alloys are for instance EP 0 193 848 A1 , GB 1 375 611 A and GB 2 053 276 A .
  • an electrolyte for the electrolytic deposition of a gold-copper alloy on a substrate surface wherein the electrolyte comprises beneath a source of gold and copper potassium cyanide (KCN) in a concentration capable to maintain a copper to KCN ratio in the range of 3 to 7, and at least one complexing agent of the group consisting of ethylenediamine tetraacetic acid [EDTA], diethylenetriamine pentaacetic acid and nitrilo-triacetic acid [NTA] hydroxyethyl imino diacetic acid [HEIDA], nitrilo propionic diacetic acid [NPDA], imino diacetic acid [IDA], nitrilo trimethylphosphoric acid [NTMA, Dequest 2000], triethanol amine [FEA].
  • EDTA ethylenediamine tetraacetic acid
  • NDA nitrilo-triacetic acid
  • HEIDA hydroxyethyl imino diacetic acid
  • NPDA nitri
  • the electrolyte according to the invention can comprise gold in a concentration between 2 to 20 g/l and copper in a concentration between 10 to 50 g/l.
  • the at least one complexing agent of the group mentioned above is comprised in the inventive electrolyte in a concentration between 0,05 to 0,6 mol/l. It is believed that the strong chelating agents beneath functioning as complexing agent will contribute to the conductivity of the electrolyte.
  • the inventive electrolyte may further comprise one of at least one metal of the group consisting of Sb, Se, Ag,Pt, Ni and Zn.
  • Zinc and nickel can function as grain refiner as well as stabilizerto the free KCN.
  • Gold is believed to function as efficiency booster to yield in higher plating velocity and carat.
  • the metals mentioned above can be comprised in the inventive electrolyte in an amount between 0,1 mg/l and 10 g/l. It is within the scope of the invention that the electrolyte can comprise further additive metals to influence the physical properties of the deposit.
  • the inventive electrolyte can further comprise a surface active agent or wetting agent which will function as brightener.
  • a capable surface active agent which can be comprised in the electrolyte is for example sodium-lauryl-etherphosphate.
  • commercially available products known by name of nonionic, cationic, or amphoteric surfactants can be employed single or in combinations.
  • the amount of the surface active agent in the inventive electrolyte may vary in a range of 0,1 ti 5 ml/l.
  • the electrolyte can comprise secondary brightener and/or stabilizing agents.
  • secondary brightener and/or stabilizing agents are pyridin sulfonic acid and ammonium hydrogene difluoride.
  • the amount of these secondary brightener and/or stabilizing agents may vary in a range between 0,1 g/l to 10 g/l.
  • the pH-value of the inventive electrolyte may vary in a range of pH 8 to pH 13, with a preferred pH-value of about 11.
  • the inventive electrolyte may comprise alkaline hydroxide or alkaline earth hydroxide.
  • the current density conducted between the substrate and the anode may vary in a range of 0,2 to 2 A/dm 2 .
  • the temperature of the electrolyte is in the range of 70° C to 90° C.
  • the inventive electrolyte together with the inventive method permits to produce a large range of carat suitable for plating and electroforming producing accurate value of carat between 18 and 14.
  • the value of carat can be controlled by measurement of efficiency in Mg/A.nm. According to the relationship of temperature and current density disclosed above, the right efficiency for an adequate value of carat is obtained by tuning the current density and temperature respectively.
  • a further advantage of the deposit yield by the inventive electrolyte and the inventive method is the possibility to heat-treat the deposited alloys in order to get an optimum ductility for a gold alloy. This is advantageously for both decorative and functional applications.
  • heat-treating the alloys deposited a relatively high hardness is achieved. Relatively high in these terms means higher than that of the metallurgical alloy.
  • the hardness rises from 280 HV to 380 HV while the aspect of surface isn't changed by oxidation.
  • a further advantage of the deposits obtained from the inventive electrolyte is the good solder ability of the alloys. This characteristic is especially important in electroforming when it is necessary to close holes done to empty the mandrels and for further artistic work.
  • the electrolyte Due to the strong complexing power of the complexing agent used according to this invention, the electrolyte is relatively none-sensitive to possible contaminations from various metals like Sn, Zn, Ag, Ni or Cr coming from different sources like drag ins from pre-treatment, mandrels composition or replenishment products. Generally, such types of contamination create an instability of the relation between current density and efficiency which may cause problems during electroforming processes. So, the non-sensity of the electrolyte to this contaminations is a further advance of this invention.
  • gold-copper alloy deposits on substrate surfaces are obtainable showing a thickness of > 20 microns and a carat in the range of 12 to 19 carat.
  • gold-copper alloy deposits on substrate surfaces are obtainable showing a thickness of > 20 microns and a carat in the range of 12 to 19 carat.
  • electroforming at a thickness of 200 microns and more is possible.
  • inventive electrolyte is also of high economic interest since it shows a minimum turn-over of 0,25 kg/l.

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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

  • This invention relates to an electrolyte as well as a method for the electrolytic deposition of a gold-copper alloy on a substrate surface.
  • It is a well-known technique in the art to plate the surfaces of articles with alloys of gold for decorative or functional purposes. Especially for application in jewellery or in the field of electro-technical devices, there is a need for alloy layers which can be varied in respect of their physical properties like brightness, hardness, wear resistance or colour. These properties are influenced by the composites of the alloys, e. g. the metals co-plated, as well as by the composition of the bath used for the deposition of the alloy, e. g. the electrolyte. Further, also the method and the plating parameters like temperature and current density are influencing the plating result in important ways.
  • In the state of the art, there has been a number of proposals to deposit alloy layers of gold-copper alloys.
  • For example, U.S. patent 5,006,208 discloses a galvanic gold alloying bath which contains beneath gold and copper in form of cyanide compounds a selenium compound. The deposit achieved from this galvanic bath is soft, light yellow and matt. The gold-alloy containing is constituted by 14 - 18 carat.
  • European patent EP 0 384 679 B1 discloses a bath for the electrolytic deposition of gold-copper alloy as well as a method for electroplating articles using such a bath. An electrolyte is disclosed which contains gold in form of a cyanide compound, copper in the form of a cyanide compound as well as tellurium or bismuth in the form of watersoluble compounds.
  • Also, European patent application EP 0 566 054 A1 discloses a solution for electroplating gold-copper alloys. Here, an electrolyte is disclosed comprising a soluble gold compound present as a gold cyanide complex, a soluble copper compound present as a copper cyanide complex as well as a soluble divalent sulfur compound in an amount sufficient to brighten the alloys. The brightening additive may be a thiocyanate, thiomalic acid, imidazolidinethione, a sulfite or thiobarbituric acid. Further patent documents disclosing the deposition of gold-copper alloys are for instance EP 0 193 848 A1 , GB 1 375 611 A and GB 2 053 276 A .
  • All of these have drawbacks when the deposition of a thick deposit is needed. So, Au/Cu/Ag-processes can produce thick deposits as a coat but the deposition of silver creates a strong nodulation not acceptable for thick deposits. Further, some of these processes known from the state of the art comprise cadmium, which is deemed to be toxic and may be banned for application.
  • It is therefore an object of the invention to provide an improved electrolyte as well as an improved method for the electrolytic deposition of gold-copper alloy.
  • In view of the electrolyte, this object is solved by an electrolyte for the electrolytic deposition of a gold-copper alloy on a substrate surface, wherein the electrolyte comprises beneath a source of gold and copper potassium cyanide (KCN) in a concentration capable to maintain a copper to KCN ratio in the range of 3 to 7, and at least one complexing agent of the group consisting of ethylenediamine tetraacetic acid [EDTA], diethylenetriamine pentaacetic acid and nitrilo-triacetic acid [NTA] hydroxyethyl imino diacetic acid [HEIDA], nitrilo propionic diacetic acid [NPDA], imino diacetic acid [IDA], nitrilo trimethylphosphoric acid [NTMA, Dequest 2000], triethanol amine [FEA].
  • The electrolyte according to the invention can comprise gold in a concentration between 2 to 20 g/l and copper in a concentration between 10 to 50 g/l. The at least one complexing agent of the group mentioned above is comprised in the inventive electrolyte in a concentration between 0,05 to 0,6 mol/l. It is believed that the strong chelating agents beneath functioning as complexing agent will contribute to the conductivity of the electrolyte.
  • The inventive electrolyte may further comprise one of at least one metal of the group consisting of Sb, Se, Ag,Pt, Ni and Zn.
  • Those metals will influence the physical properties of the alloy deposit. For example, selenium functions as brightener for the deposit. The same is true fortellurium and antimony.
  • Platinum is believed to result in better homogenity of the alloy for high carat and thickness.
  • Zinc and nickel can function as grain refiner as well as stabilizerto the free KCN.
  • Gold is believed to function as efficiency booster to yield in higher plating velocity and carat.
  • The metals mentioned above can be comprised in the inventive electrolyte in an amount between 0,1 mg/l and 10 g/l. It is within the scope of the invention that the electrolyte can comprise further additive metals to influence the physical properties of the deposit.
  • The inventive electrolyte can further comprise a surface active agent or wetting agent which will function as brightener. A capable surface active agent which can be comprised in the electrolyte is for example sodium-lauryl-etherphosphate. Further, commercially available products known by name of nonionic, cationic, or amphoteric surfactants can be employed single or in combinations.
  • The amount of the surface active agent in the inventive electrolyte may vary in a range of 0,1 ti 5 ml/l.
  • It is further within the scope of the invention that the electrolyte can comprise secondary brightener and/or stabilizing agents. Examples for such a secondary brightener and/or stabilizing agents are pyridin sulfonic acid and ammonium hydrogene difluoride. The amount of these secondary brightener and/or stabilizing agents may vary in a range between 0,1 g/l to 10 g/l.
  • The pH-value of the inventive electrolyte may vary in a range of pH 8 to pH 13, with a preferred pH-value of about 11. To influence the pH-value, the inventive electrolyte may comprise alkaline hydroxide or alkaline earth hydroxide.
  • Beneath the inventive electrolyte, with this invention a method for depositing a gold-copper alloy layer on a substrate surface is provided, wherein the method comprises the steps:
    • pretreating the substrate surface to be plated;
    • contacting the substrate surface to be plated with the inventive electrolyte; and
    • conducting a current between the substrate and an anode.
  • According to the inventive method, the current density conducted between the substrate and the anode may vary in a range of 0,2 to 2 A/dm2.
  • According to the inventive method, during contacting the substrate surface with the inventive electrolyte and applying a current the temperature of the electrolyte is in the range of 70° C to 90° C.
  • Surprisingly, it was found that there is a relationship between temperature and current density applied to the substrate as following:
    • Temperature increases: efficiency increases (and opposite)
    • Current density increases: efficiency decreases (and opposite).
  • It is a main advantage of the invention to offer the possibility of thick and bright gold alloy layers on substrate surfaces without addition of toxic metal like cadmium. The inventive electrolyte together with the inventive method permits to produce a large range of carat suitable for plating and electroforming producing accurate value of carat between 18 and 14. Surprisingly, it was found that the value of carat can be controlled by measurement of efficiency in Mg/A.nm. According to the relationship of temperature and current density disclosed above, the right efficiency for an adequate value of carat is obtained by tuning the current density and temperature respectively.
  • To control the plating process it is within the scope of the invention that all operating conditions are controlled by an adequate computer system to get an adequate value of carat.
  • Surprisingly, it was found that a further advantage of the deposits resulting from the inventive- electrolyte and the inventive method showing a good resistance to nitric acid stripping even with a carat value of 14. This is especially useful for electroforming processes in jewellery when nitric acid stripping is necessary to clean the inside of pieces.
  • A further advantage of the deposit yield by the inventive electrolyte and the inventive method is the possibility to heat-treat the deposited alloys in order to get an optimum ductility for a gold alloy. This is advantageously for both decorative and functional applications. By heat-treating the alloys deposited, a relatively high hardness is achieved. Relatively high in these terms means higher than that of the metallurgical alloy.
  • For example, after a heat-treatment at 500° C for 10 minutes under controlled atmosphere nitrogen or cracking ammonia, the hardness rises from 280 HV to 380 HV while the aspect of surface isn't changed by oxidation.
  • A further advantage of the deposits obtained from the inventive electrolyte is the good solder ability of the alloys. This characteristic is especially important in electroforming when it is necessary to close holes done to empty the mandrels and for further artistic work.
  • Due to the strong complexing power of the complexing agent used according to this invention, the electrolyte is relatively none-sensitive to possible contaminations from various metals like Sn, Zn, Ag, Ni or Cr coming from different sources like drag ins from pre-treatment, mandrels composition or replenishment products. Generally, such types of contamination create an instability of the relation between current density and efficiency which may cause problems during electroforming processes. So, the non-sensity of the electrolyte to this contaminations is a further advance of this invention.
  • By the inventive electrolyte as well as the inventive method gold-copper alloy deposits on substrate surfaces are obtainable showing a thickness of > 20 microns and a carat in the range of 12 to 19 carat. By the invention, also electroforming at a thickness of 200 microns and more is possible.
  • Furthermore, the inventive electrolyte is also of high economic interest since it shows a minimum turn-over of 0,25 kg/l.
  • The following embodiments are describing the invention in terms of examples, while the invention is not limited to this embodiments.
    • Examples:
  • The following electrolytes for gold-copper-alloy deposition are embodiments for the invention
    Au/Cu alloys
    Bath no 1 2 3 4 5
    Gold 4 8 6 6 5
    Copper 20 10 20 30 20
    Free KCN 5 2 10 10 7
    Potassium carbonate 10
    Potassium sodium tart rate 10
    Di Potassium hydrogen phosphate 10
    Au/Cu alloys (* not according the invention)
    Bath no 1 2 3* 4 5
    Gold 4 8 6 6 5
    Copper 20 10 20 30 20
    Free KCN 5 2 10 10 7
    Ratio Cu/KCN 4 5 2 3 3
    Potassium carbonate 10
    Potassium sodium tartrate 10
    Di Potassium hydrogen phosphate 10
    EDTA 5 5
    HEIDA 5
    NTA 10 50
    NPDA 5
    IDA 20
    NTMA 50
    TEA 10 50
    PSA 2 2
    Ammonium Hydrogen difluoride 5 2
    Sb mg/l 0.5 10 2 1
    Zn g/l 0.5
    Pt g/l
    Ag mg/l
    Wetting agent 0.1 to 5 g/l or ml/l
    KOH to adjust pH to 10/12
    Pre-treatment
    Product Temperature Time CD Brass Stainless Steel
    Electroless cleaner Enprep 100 60°C 2mn x x
    Rince water x x
    Electrolytic cleaner Enprep 285 40°C 1 mn 3A/dm2 x x
    Rince water x x
    Neutralisation actane 345 room 30 sec x x
    Rince water x x
    Gold flash Aurobond XDA 40°C 2 mn 4A/dm2 x
    Rince water x
    Gold flash Aurobond TN 50°C 30 sec 1 A/dm2 x x
    Rince water x x
    Acide gold Karatclad Omega 30°C 10 mn 1 A/dm2 x x

Claims (14)

  1. An electrolyte for the electrolytic deposition of a gold-copper alloy on a substrate surface, wherein the electrolyte comprises beneath a source of gold and copper free potassium cyanide (KCN) in a concentration in g/l capable to maintain a copper to free KCN ratio in the range of 3 to 7, and at least one complexing agent of the group consisting of ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, nitrilo-triacetic acid, ethylenediamine tetraacetic acid [EDTA], diethylenetriamine pentaacetic acid and nitrilo-triacetic acid [NTA] Hydroxyethyl imino diacetic acid [HEIDA], nitrilo propionic diacetic acid [NPDA], imino diacetic acid [IDA], nitrilo trimethylphosphoric acid [NTMA, Dequest 2000], triethanol amine [TEA], wherein the electrolyte is capable of depositing thick and bright gold alloy layers without addition of cadmium.
  2. The electrolyte according to claim 1, comprising gold in a concentration between 2 to 20 g/l and copper in a concentration between 10 to 50 g/l.
  3. An electrolyte according to one of the claims 1 or 2, wherein the at least one complexing agent of the group consisting of ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, nitrilo-triacetic acid, ethylenediamine tetraacetic acid [EDTA], diethylenetriamine pentaacetic acid and nitrilo-triacetic acid [NTA] Hydroxyethyl imino diacetic acid [HEIDA], nitrilo propionic diacetic acid [NPDA], imino diacetic acid [IDA], nitrilo trimethylphosphoric acid [NTMA, Dequest 2000], triethanol amine [TEA] comprised in a concentration between 0,05 to 0,6 mol/l.
  4. An electrolyte according to one of the claims 1 to 3, further comprising ions of at least on metal of the group consisting of Te, Sb, Se, Ag, Pt, Ni and Zn.
  5. An electrolyte according to claim 4, comprising the ions of at least on metal of the group consisting of Sb, Se, Ag, Pt, Ni and Zn in an amount between 0,1 mg/l and 10 g/l.
  6. An electrolyte according to one of the claims 1 to 5, further comprising a surface active agent.
  7. An electrolyte according to claim 6, wherein the surface active agent is a sodium-lauryl-etherphosphate.
  8. An electrolyte according to claim 7, comprising the surface active agent in an amount of 0.1 to 5 ml/l.
  9. An electrolyte according to one of the claims 1 to 8, further comprising secondary brightener and/or stabilizing agents.
  10. An electrolyte according to one of the claims 1 to 4, wherein the pH-value of the electrolyte is in the range of 8 to 13.
  11. A method for depositing a gold-copper-alloy layer on a substrate surface, wherein the method comprises the steps:
    pretreating the substrate surface to be plated;
    contacting the substrate surface to be plated with an electrolyte according to one of the claims 1 to 10; and
    conducting a current between the substrate and an anode.
  12. The method according to claim 11, wherein the current density conducted between the substrate and the anode is in the range of 0.2 to 2 A/dm2.
  13. The method according to claim 11 or 12, wherein the temperature of the electrolyte is in the range of 70 °C to 90 °C.
  14. A gold-copper alloy deposit on a substrate surface by a process according to one of the claims 11 to 13, wherein the thickness of the deposit is > 20 microns and the carat is in the range of 12 to 19 kt.
EP07007963.7A 2007-04-19 2007-04-19 Electrolyte and method for electrolytic deposition of gold-copper alloys Ceased EP1983077B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP07007963.7A EP1983077B1 (en) 2007-04-19 2007-04-19 Electrolyte and method for electrolytic deposition of gold-copper alloys
EP16197251.8A EP3170924A1 (en) 2007-04-19 2007-04-19 Electrolyte and method for electrolytic deposition of gold-copper alloys
CN2008100934716A CN101289756B (en) 2007-04-19 2008-04-21 Electrolyte composition and method for electrolytic deposition of gold-copper alloys

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07007963.7A EP1983077B1 (en) 2007-04-19 2007-04-19 Electrolyte and method for electrolytic deposition of gold-copper alloys

Related Child Applications (3)

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EP16197251.8A Division EP3170924A1 (en) 2007-04-19 2007-04-19 Electrolyte and method for electrolytic deposition of gold-copper alloys
EP16197251.8A Previously-Filed-Application EP3170924A1 (en) 2007-04-19 2007-04-19 Electrolyte and method for electrolytic deposition of gold-copper alloys
EP16197251.8A Division-Into EP3170924A1 (en) 2007-04-19 2007-04-19 Electrolyte and method for electrolytic deposition of gold-copper alloys

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EP1983077A1 EP1983077A1 (en) 2008-10-22
EP1983077B1 true EP1983077B1 (en) 2016-12-28

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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
CN105506686A (en) * 2015-12-23 2016-04-20 苏州市金星工艺镀饰有限公司 Electroplating method for decorative nickel-copper-gold ternary alloy electroplating bath
JP6690699B2 (en) * 2016-02-18 2020-04-28 日本製鉄株式会社 Method for extracting metal compound particles, method for analyzing metal compound particles, and electrolytic solution used therein
CN105671602A (en) * 2016-03-15 2016-06-15 大连理工大学 Cyanide-free sulfite Au-Cu alloy electroplating solution and application
CN109680310B (en) * 2019-01-04 2020-07-07 中国计量大学 Nickel-antimony electroplating solution and preparation method thereof
CN110699721B (en) * 2019-11-20 2021-08-20 长春黄金研究院有限公司 Cyanide-free gold-copper alloy electroplating solution and application thereof
CN111962104A (en) * 2020-08-21 2020-11-20 深圳国韵黄金文化有限公司 22K cyanide-free electroformed gold and preparation process thereof
CN114875456B (en) * 2021-06-25 2024-03-08 深圳市铭轩珠宝首饰有限公司 Copper-gold composite gold coating method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1375611A (en) 1972-03-28 1974-11-27
EP0304315A1 (en) 1987-08-21 1989-02-22 Engelhard Limited Bath for electrolytic deposition of a gold-copper-zinc alloy
EP0384679A1 (en) 1989-02-20 1990-08-29 Engelhard Corporation Electrolytic deposition of gold-containing alloys
EP0416342A1 (en) 1989-09-06 1991-03-13 Degussa Aktiengesellschaft Galvanic gold alloy bath
EP0566054A1 (en) 1992-04-15 1993-10-20 LeaRonal, Inc. Electroplated gold-copper-silver alloys
EP1103637A1 (en) 1999-11-29 2001-05-30 ENTHONE-OMI, Inc. Method of producing AuCuGa alloy coating using electrolysis, and alloys produced by such a method
EP1728898A2 (en) 2005-06-02 2006-12-06 Rohm and Haas Electronic Materials LLC Electrolytes for the deposition of gold alloys

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH632533A5 (en) * 1979-06-14 1982-10-15 Aliprandini P PROCESS FOR THE GALVANOPLASTIC DEPOSIT OF A GOLD ALLOY.
CH662583A5 (en) * 1985-03-01 1987-10-15 Heinz Emmenegger GALVANIC BATH FOR THE ELECTROLYTIC DEPOSITION OF GOLD-COPPER-CADMIUM-ZINC ALLOYS.

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1375611A (en) 1972-03-28 1974-11-27
EP0304315A1 (en) 1987-08-21 1989-02-22 Engelhard Limited Bath for electrolytic deposition of a gold-copper-zinc alloy
EP0384679A1 (en) 1989-02-20 1990-08-29 Engelhard Corporation Electrolytic deposition of gold-containing alloys
EP0416342A1 (en) 1989-09-06 1991-03-13 Degussa Aktiengesellschaft Galvanic gold alloy bath
EP0566054A1 (en) 1992-04-15 1993-10-20 LeaRonal, Inc. Electroplated gold-copper-silver alloys
EP1103637A1 (en) 1999-11-29 2001-05-30 ENTHONE-OMI, Inc. Method of producing AuCuGa alloy coating using electrolysis, and alloys produced by such a method
EP1728898A2 (en) 2005-06-02 2006-12-06 Rohm and Haas Electronic Materials LLC Electrolytes for the deposition of gold alloys

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
C. POHLANDT: "A critical evaluation of methods applicable for the determination of cyanides", JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY, January 1983 (1983-01-01), pages 11 - 19, XP055425861
H. P. ROTHBAUM: "The Composition of Copper Complexes in Cuprocyanide Solutions", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 104, no. 11, November 1957 (1957-11-01), pages 682 - 686, XP055425845
I.-M. MIHAESCU: "Cyanide Determination with a modified Ninhydrin Reagent using N- Acetyl Cysteine in the presence of Heavy Metal Ions", J. CHIL. CHEM. SOC., vol. 55, no. 4, 2010, pages 467 - 468, XP055425848
T. MICHALOWSKI: "Liebig-Deniges Method of Cyanide Determination: A comparative Study of Two Approaches", J. SOLUTION CHEM, vol. 41, 2012, pages 1224 - 1239, XP035094245

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022180650A1 (en) 2021-02-23 2022-09-01 Italfimet Srl Process for galvanic electrodeposition and associated galvanic bath

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CN101289756B (en) 2012-06-20
EP1983077A1 (en) 2008-10-22
CN101289756A (en) 2008-10-22

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