WO2001038609A1 - PROCEDE DE PRODUCTION D'UN REVETEMENT EN ALLIAGE AuCuGa PAR ELECTROLYSE, ET ALLIAGES PRODUITS AU MOYEN D'UN TEL PROCEDE - Google Patents

PROCEDE DE PRODUCTION D'UN REVETEMENT EN ALLIAGE AuCuGa PAR ELECTROLYSE, ET ALLIAGES PRODUITS AU MOYEN D'UN TEL PROCEDE Download PDF

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Publication number
WO2001038609A1
WO2001038609A1 PCT/US2000/030153 US0030153W WO0138609A1 WO 2001038609 A1 WO2001038609 A1 WO 2001038609A1 US 0030153 W US0030153 W US 0030153W WO 0138609 A1 WO0138609 A1 WO 0138609A1
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WO
WIPO (PCT)
Prior art keywords
gallium
copper
gold
aucuga
producing
Prior art date
Application number
PCT/US2000/030153
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English (en)
Inventor
Stéphanie Dimpre
Philippe Marcus
Pierre Lalanne
Jacques Biau
Original Assignee
Enthone-Omi Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Enthone-Omi Inc. filed Critical Enthone-Omi Inc.
Priority to AU17551/01A priority Critical patent/AU1755101A/en
Publication of WO2001038609A1 publication Critical patent/WO2001038609A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold

Definitions

  • the present invention relates to a method of producing gold-copper-gallium alloys (AuCuGa) using an electrolysis process, having the requisite qualities as to ductility, brightness, and which is particularly suitable for applications in jewelry and goldsmith's trade.
  • AuCuGa gold-copper-gallium alloys
  • AuCuCd gold- copper- cadmium
  • the coating of an alloy based on gold- copper- cadmium is well known in the art of jewellery and goldsmith's trade because of its qualities relating to ductility and brightness.
  • AuCuCd gold- copper- cadmium
  • gold is 75% in weight
  • copper is 18% in weight
  • cadmium is 7% in weight, which corresponds, respectively, to 52.4%, 39% and 8.6% in atomic percent.
  • This type of alloy coating has the desirable brightness and hardness (about 400 Vickers) and ductility which makes it attractive and thus has been widely used since the last century.
  • the co-deposition of gold, copper and cadmium is well known in the art of jewellery and goldsmith's trade because of its qualities relating to ductility and brightness.
  • gold is 75% in weight
  • copper is 18% in weight
  • cadmium is 7% in weight, which corresponds, respectively, to 52.4%, 39% and 8.6% in atomic percent.
  • AuCuCd using an electrolysis process
  • Many electrolysis process use different types of electrolytes such as cyanide acid, basic, neutral or sulfuric electrolytes, so as to obtain an AuCuCd alloy coating, insofar as potentials needed with the electrodeposition of the gold, copper and cadmium cations are all in the same range when using the above mentioned electrolytic baths.
  • US patent application No 72/237513 discloses a coating method and an electrolytic bath for depositing a low-carat (14-19 carats) thick AuCuCd coating (20-40 ⁇ m) , which consists of electrodepositing an AuCuCd alloy from an alkaline aqueous bath containing a soluble gold cyanide complex, a soluble copper cyanide, a soluble cadmium compound, free cyanide and a water-soluble polyoxyalcoylenic brightening agent.
  • a low-carat alloy i.e. having a low concentration of gold and a high concentration of copper and cadmium
  • the use of brightness agents allows to obtain a final thick coating which has the desired brightness.
  • a bulk alloy of AuCuGa is used in the field of dentistry, however, this bulk alloy is produced by melting together gold, copper and gallium into ingot, such producing method not being applicable in jewellery applications .
  • the main object of the present invention is to provide an AuCuGa alloy coating whose brightness and ductility qualities are similar to those of AuCuCd alloy coatings, thus allowing such AuCuGa alloy coating to be used as an alternative to AuCuCd alloy coating, in particular for jewellery applications.
  • This object is achieved by providing a method of producing a gold-copper-gallium (AuCuGa) alloy coating by electrodeposition on a substrate, using an aqueous electrolytic bath, characterized in that said aqueous electrolytic bath comprises potassium aurocyanide (KAu(CN) 2 ), copper cyanide (CuCN) , potassium cyanide (KCN) or sodium cyanide (NaCN) , and a soluble gallium compound.
  • KAu(CN) 2 potassium aurocyanide
  • CuCN copper cyanide
  • KCN potassium cyanide
  • NaCN sodium cyanide
  • the above mentioned soluble gallium compound may be at least one of, or a mixture of the following gallium salts, gallium sulfate (Ga 2 (S0 4 ) 3 ), gallium (III) ' chloride (GaCl 3 ) , gallium(III) -2 , 3 -naphthalocyanine chloride (2,3- naphthalocyanine gallium(III) monochloride salt) (C 48 H 24 ClGaN B ) , gallium (III) nitrate nonahydrate (Ga(N0 3 ) 3 .9H 2 0) , gallium(III) nitrate hydrate (Ga (N0 3 ) 3 .
  • gallium nitride (GaN) gallium (III) oxide (Ga 2 0 3 ) , Gallium phosphide (GaP) , and gallium(III) phthalocyanine chloride (Phthalocyanine gallium(III) monochloride salt) (C 32 H 16 ClGaN 8 ) .
  • the molar concentration of gold cations ([Au + ]) , copper cations ([Cu + ]) and gallium cations ([Ga 3+ ]) in .- the electrolytic bath is respectively comprised within the following ranges: 0,19 g/1 ⁇ [Au + ] ⁇ 2,17 g/1 (0,1.10 ⁇ 2 mol/1 ⁇ [Au + ] ⁇ 1,1.10 '2 mol/1); 0,31 g/1 ⁇ [Cu + ] ⁇ 1,59 g/1 (0,5.10 " mol/1 ⁇ [Cu + ] ⁇ 2,5.10 "2 mol/1); and 0,69 g/1 ⁇ [Ga 3+ ] ⁇ 2,79 g/1 (1.10 -2 mol/1 ⁇ [Ga 3+ ] ⁇ 4.10 "2 mol/1).
  • the mole concentration of potassium cyanide in the electrolytic bath has to be at least about 1,5 the mole concentration of copper cyanide.
  • the pH of the electrolytic bath is in. the range of 7 to 13, advantageously superior or equal to 10 (more preferably 12), the temperature of the electrolytic bath is in the range of 15 to 80°C, and preferably 50 to 70°C, or about 60°C, and the current density during the electrolysis is in the range of 1.1 to 1.8 A/dm 2 (preferably 1.4 A/dm 2 ) .
  • some complexing agents such as chelating agents or some mixtures thereof, may be added to the aqueous electrolytic bath.
  • said at least one chelating agent is an organophosphate chelating agent or an aminocarboxy or aminopolycarboxy acid, and, in particular, an ethylenediamine tetraacetic acid (EDTA) , a nitrilotriacetic acid (NTA) , and/or a 2-aminoethanesulfonic acid (taurine) .
  • EDTA ethylenediamine tetraacetic acid
  • NTA nitrilotriacetic acid
  • taurine 2-aminoethanesulfonic acid
  • the present invention also concerns any AuCuGa alloys produced by such a method.
  • figure 1 represents an exemplary galvanostatic assembly suitable for the method of producing an 18-carat AuCuGa alloy coating according to an embodiment of the present invention.
  • an exemplary galvanostatic assembly comprises a tank 3 containing an electrolytic bath in which an anode 1 and a cathode 2 are submerged, a motor 4 for rotationally driving cathode 2, and a current generator 5 connected to both anode 1 and cathode 2.
  • a thermocouple 6 is coupled to an electrical heating device 7 for maintaining a predetermined temperature of the electrolytic bath.
  • a magnetic agitator 8 maintains a stable homogeneity of the electrolytic bath before and during the electrolysis.
  • cathode 2 is a copper plate covered with a thin gold film which is in the range of 0,1 to 0,2 ⁇ m thick and which is used as an underlayer. This plate is hung from a copper wire and is rotationally driven by motor 4 at 7,5 rp .
  • the cathode may be made of any other electrically conductive material such as, for instance, nickel, and may be covered with any other suitable underlayer.
  • Anode 1 is made of a platinum- coated titanium (Ti-Pt) , and magnetic agitator 8 is driven at 125 rpm to obtain the desired agitation.
  • the thermocouple maintains the bath temperature at 60 °C.
  • the substrate of cathode 2 is prepared by skimming off any grease on the substrate so as to dissolve emulsified grease, and by carrying out an activation and a rising process using ultrasounds for removing impurities, followed by rinsing the substrate with distilled water.
  • gallium (III) sulfate anhydrous (Ga 2 (S0 4 ) 3 ) is used so as to provide the electrolytic bath with gallium cations.
  • gallium salts or mixtures of these salts, may be used, as, for instance, galliu ⁇ n(III) chloride (GaCl 3 ) , gallium (III) -2 , 3 -naphthalocyanine chloride (2, 3 -naphtha locyanine gallium(III) monochloride salt) (C 48 H 24 ClGaN 8 ) , gallium(III) nitrate nonahydrate (Ga (N0 3 ) 3 , 9H 2 0) , gallium.
  • the agitation of the bath and the rotation of the cathode facilitate the diffusion of the cations by opposing the exhaustion of the diffusion layer.
  • the stronger the agitation the more the current density required for maintaining the electrolysis is high, and accordingly . the quickest the coating is achieved.
  • the agitation and rotation conditions advantageously further assist in eliminating any hydrogen bubbles which may occur at the surface of the cathode when the water reduces, such hydrogen bubbles normally disturbing the co-deposition of the three metal cations and thus impairing the properties of the final alloy coating.
  • the gallium reduction occurs beyond the water reduction (the reduction potential of H 2 0 is about -2 V) , it is necessary to provide a operating potential greater than -2 V so as to reduce the three metals.
  • the operating potential is about -2.75 V.
  • the above-mentioned deposition conditions are.. maintained for a certain period of time depending on the desired thickness of the coating. In the present embodiment, a thickness of 4 ⁇ m is obtained after a 10 minutes lasting application of the mentioned current density. A larger thickness may be obtained by increasing the time period of applying the potential between the anode and the cathode .
  • the final alloy coating is a 18-carat ternary AuCuGa alloy with a chemical composition, in atomic percent, of 62% of Au, 27.3% of Cu and 10.7% of Ga .
  • This alloy has a hardness which is suitable for applications to jewellery and goldsmith's trade.
  • the measured average grain size is about 0.3 ⁇ m, which results in a brightness of the AuCuGa alloy coating similar to that of prior art AuCuCd alloy coatings.
  • the surface is no more rough, this also constitutes an advantage due to an increased resistance to corrosion.
  • the color of the AuCuGa alloy coating according to the invention is slightly less golden than the prior art AuCuCd alloy. Further, the aging tests which have been conducted on the AuCuGa alloy coating according to the invention, have shown that it is not sensitive to corrosion and tarnishment caused by air, sweat and/or acetic acid.
  • the present invention is not limited to the above exemplary described preferred embodiment.
  • many different types of AuCuGa alloys having different carat contents e.g. from 8 to about 24 carats
  • similar properties in terms of brightness may be obtained by using the method according to the invention.
  • the molar concentration of the different cations in the electrolytic- bath may be comprised within the following ranges : 0,19 g/1 ⁇ [Au + ] ⁇ 2,17 g/1 (0,1.10 "2 mol/1 ⁇ [Au + ] ⁇ 1,1.10 "2 mol/1); 0,31 g/1 ⁇ [Cu + ] ⁇ 1,59 g/1 (0,5.10 "2 mol/1 ⁇ [Cu + ] ⁇ 2,5.10 "2 mol/1); and 0,69 g/1 ⁇ [Ga 3+ ] ⁇ 2,79 g/1 (1.10 "2 mol/1 ⁇ [Ga 3+ ] ⁇ 4.10 "2 mol/1).
  • the electrolysis may be carried out in an aqueous electrolytic bath having a pH value equal to or greater than 10.
  • the pH value of the electrolytic bath may be varied to influence the yield of the electrolysis (mg/A.min.) as well as the hardness of the coating .
  • the temperature of the electrolytic bath may be comprised in the range of 50 to 70°C. By increasing of the temperature, it is possible to increase the admissible maximum current density, the viscosity will then decrease, and accordingly the electrochemical reaction and diffusion speed increase. Therefore, the electrolytic deposition may be made with electrolytes of a higher concentration.
  • the operating current density may be in the range of 1.1 to 1.8 A/dm 2 .
  • AuCuGa alloy coating according to the invention with the above mentioned properties, have- been checked by analyzing the final alloy with different well-known chemical and structural characterization techniques such as the Electron Spectroscopy for Chemical Analysis (ESCA) , the Energy Dispersive X-Ray Spectroscopy (EDXS) , the atomic absorption spectroscopy or the X-ray diffraction and by using Scanning Electron Microscopy (SEM) .
  • ESA Electron Spectroscopy for Chemical Analysis
  • EDXS Energy Dispersive X-Ray Spectroscopy
  • SEM Scanning Electron Microscopy
  • the experimental implementation of different depositions under variable potentials controlled by ESCA has allowed to determine the correct ranges of the parameters.
  • the ESCA analysis has shown the order in the reduction of the cations (for potentials more and more negative: gold, copper, then gallium) and the EDXS has allowed to determine the chemical composition of the final alloys having a thickness of 1 to 4 ⁇ m.
  • the EDXS analysis has allowed to determine the surface composition of the alloys. For thicker alloys, i.e. greater than 4 ⁇ m, the chemical composition of the whole deposition was analyzed by atomic absorption spectroscopy.
  • the analysis of the X- ray diffraction diagram established the existence of a periodical structure in the electro-deposit according to the invention.
  • the copper content may be controlled by either increasing the copper concentration of the electrolytic bath (resulting in significant changes) , or by increasing the current density (resulting in slight changes) .
  • the gallium content of the alloy does not change in a simple manner when increasing the current density.
  • the increase of the current facilitates the co-deposition of gallium and copper. Therefore, another advantage of the present invention is that the change in gold content (number of carats or the content of copper and gallium) may be controlled by adjusting the current density between both electrodes.
  • Some additives may be added to the electrolytic bath according to the invention, so as to improve the yield or to modify the co-deposition structure and improve the brightness and/or color of the AuCuGa coating.
  • some polyoxyalcoylenic compounds may be used as brightness agents and some chelating agents like organophosphate chelating agents or aminocarboxy acids (or aminopolycarboxy acids) may be used.
  • EDTA ethylenediamine tetraacetic acid
  • NTA nitrilotriacetic acid
  • molar concentrations in the range of 0,1 to 2 mol/1 may improve the brightness and give a rosy, color to the coating.
  • EDTA ethylenediamine tetraacetic acid
  • NTA nitrilotriacetic acid
  • taurine (2-amino ethanesulfonic acid, NH 2 CH 2 CH 2 S0 3 H) to the electrolytic bath makes it possible to get AuCuGa ternary alloys under current densities of about 1 A/dm 2 , and to increase the cathodic efficiency of the method.
  • taurine lowers the reduction of gold and increases the reduction of gallium and copper.
  • the increasing in current density slightly increases the reduction of copper.
  • the alloy according to the invention is particularly suitable for 15-carats to 24-carats coating applications for jewelry or goldsmith's trade, and is also suitable for any other application which requires the use of such an alloy, as for instance, in the microelectronic techniques.

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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)

Abstract

La présente invention concerne un procédé de production d'un revêtement en alliage or-cuivre-gallium (AuCuGa) par électrodéposition sur un substrat (2), dans lequel on utilise un bain électrolytique aqueux. Le procédé se caractérise en ce que le bain électrolytique aqueux renferme de l'aurocyanure de potassium (KAu(CN)2), du cyanure de cuivre (CuCN), du cyanure de potassium (KCN) ou du cyanure de sodium (NaCN), et un sel de gallium (par exemple du sulfate de gallium Ga2(SO43). De manière plus spécifique, la concentration molaire des cations or ([Au+]), des cations cuivre ([Cu+]) et des cations gallium ([Ga3+]) dans le bain électrolytique se situe respectivement dans les limites suivantes: 0,19 g/l ≤ [Au+] ≤ 2,17 g/l (0,1.10-2 mol/l ≤ [Au+] ≤ 1,1.10-2 mol/l; 0,31 g/l ≤ [Cu+] ≤ 1,59 g/l (0,5.10-2 mol/l ≤ [Cu+] ≤ 2,5.10-2 mol/l); et 0,69 g/l ≤ [Ga3+] ≤ 2,79 g/l (1.10-2 mol/l ≤ [Ga3+] ≤ 4.10-2 mol/l). Un tel procédé permet de produire un revêtement en alliage AuCuGa dont les propriétés de brillance et de ténacité sont équivalentes à celles des revêtements en alliage AuCuCd de l'art antérieur.
PCT/US2000/030153 1999-11-29 2000-11-22 PROCEDE DE PRODUCTION D'UN REVETEMENT EN ALLIAGE AuCuGa PAR ELECTROLYSE, ET ALLIAGES PRODUITS AU MOYEN D'UN TEL PROCEDE WO2001038609A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU17551/01A AU1755101A (en) 1999-11-29 2000-11-22 Method of producing aucuga alloy coating using electrolysis, and alloys producedby such a method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP99402969.2 1999-11-29
EP99402969A EP1103637A1 (fr) 1999-11-29 1999-11-29 Procédé de fabrication d'une couche en alliage AuCuGa en utilisant l'électrolyse et les alliages obtenus par ce procédé

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WO2001038609A1 true WO2001038609A1 (fr) 2001-05-31

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EP (1) EP1103637A1 (fr)
AU (1) AU1755101A (fr)
TW (1) TW546418B (fr)
WO (1) WO2001038609A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7507321B2 (en) * 2006-01-06 2009-03-24 Solopower, Inc. Efficient gallium thin film electroplating methods and chemistries
US7892413B2 (en) * 2006-09-27 2011-02-22 Solopower, Inc. Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films
EP3170924A1 (fr) 2007-04-19 2017-05-24 Enthone, Inc. Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre
US8425753B2 (en) 2008-05-19 2013-04-23 Solopower, Inc. Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3056733A (en) * 1960-04-23 1962-10-02 Degussa Process for electrolytic deposition of gold-copper-cadmium alloys
US3892564A (en) * 1972-10-03 1975-07-01 Johnson Matthey Co Ltd Dental alloys
US3904493A (en) * 1972-08-10 1975-09-09 Oxy Metal Industries Corp Gold sulfite baths containing organophosphorus compounds
JPS55103298A (en) * 1979-02-01 1980-08-07 Sankin Kogyo Kk Gold braze alloy for dental
US4486275A (en) * 1983-02-07 1984-12-04 Heinz Emmenegger Solution for electroplating a gold-copper-cadmium alloy
US5330592A (en) * 1993-02-23 1994-07-19 International Business Machines Corporation Process of deposition and solid state reaction for making alloyed highly conductive copper germanide
US5338378A (en) * 1992-09-29 1994-08-16 Kyushu University Dental gold alloy with age-hardenability at intraoral temperature

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
GB1594011A (en) * 1977-10-06 1981-07-30 Oxy Metal Industries Corp Gold alloy plating bath
FR2405312A1 (fr) * 1977-10-10 1979-05-04 Oxy Metal Industries Corp Bains electrolytiques pour le depot d'alliages d'or

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3056733A (en) * 1960-04-23 1962-10-02 Degussa Process for electrolytic deposition of gold-copper-cadmium alloys
US3904493A (en) * 1972-08-10 1975-09-09 Oxy Metal Industries Corp Gold sulfite baths containing organophosphorus compounds
US3892564A (en) * 1972-10-03 1975-07-01 Johnson Matthey Co Ltd Dental alloys
JPS55103298A (en) * 1979-02-01 1980-08-07 Sankin Kogyo Kk Gold braze alloy for dental
US4486275A (en) * 1983-02-07 1984-12-04 Heinz Emmenegger Solution for electroplating a gold-copper-cadmium alloy
US5338378A (en) * 1992-09-29 1994-08-16 Kyushu University Dental gold alloy with age-hardenability at intraoral temperature
US5330592A (en) * 1993-02-23 1994-07-19 International Business Machines Corporation Process of deposition and solid state reaction for making alloyed highly conductive copper germanide

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Publication number Publication date
EP1103637A1 (fr) 2001-05-30
TW546418B (en) 2003-08-11
AU1755101A (en) 2001-06-04

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