WO2022180650A1 - Process for galvanic electrodeposition and associated galvanic bath - Google Patents
Process for galvanic electrodeposition and associated galvanic bath Download PDFInfo
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- WO2022180650A1 WO2022180650A1 PCT/IT2021/000006 IT2021000006W WO2022180650A1 WO 2022180650 A1 WO2022180650 A1 WO 2022180650A1 IT 2021000006 W IT2021000006 W IT 2021000006W WO 2022180650 A1 WO2022180650 A1 WO 2022180650A1
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- grams per
- aqueous solution
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 35
- 239000000956 alloy Substances 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000010931 gold Substances 0.000 claims abstract description 22
- 229910052737 gold Inorganic materials 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000010930 yellow gold Substances 0.000 claims abstract description 21
- 229910001097 yellow gold Inorganic materials 0.000 claims abstract description 21
- 229910052738 indium Inorganic materials 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 19
- 239000011701 zinc Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 cyanide compound Chemical class 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 229910001020 Au alloy Inorganic materials 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003353 gold alloy Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 238000005323 electroforming Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- NHMJUOSYSOOPDM-UHFFFAOYSA-N cadmium cyanide Chemical compound [Cd+2].N#[C-].N#[C-] NHMJUOSYSOOPDM-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940071240 tetrachloroaurate Drugs 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/02—Alloys based on gold
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/02—Tubes; Rings; Hollow bodies
-
- 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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/005—Jewels; Clockworks; Coins
Definitions
- the present invention relates to a process for galvanic electrodeposition and to the associated galvanic bath, and also to a yellow gold alloy and to a use thereof.
- the process provides an electrolytic reaction in a tank (galvanic bath), in which the object to be coated (which acts as a cathode) is immersed in an aqueous solution of the metal to be deposited.
- the anode can be constituted by the metal itself to be deposited or also by an inert metal or by graphite.
- a potential difference to the two electrodes by applying a potential difference to the two electrodes, a flow of ions of the metal to be deposited is generated and the metal progressively accumulates on the cathode, forming indeed the desired layer.
- Yellow gold alloys are also known which comprise gold, copper and silver (and therefore lack cadmium); however, these alloys are soft and therefore unsuitable for uses in the field of electroforming. Moreover, it is substantially impossible to obtain a production with a constant gold fineness and therefore they are not used in commerce.
- the aim of the present invention is to solve the problems described above, by providing a process for galvanic electrodeposition and/or a galvanic bath that allow to provide layers made of a 1N-3N yellow gold alloy, which have good solderability and high mechanical strength.
- an object of the invention is to provide a process for galvanic electrodeposition and/or a galvanic bath that allow to obtain by electroforming shells or self-supporting objects made of a 1N-3N yellow gold alloy, with adequate metallic properties.
- Another object of the invention is to provide a 1N-3N yellow gold alloy that can be used to provide shells or self-supporting objects obtained by electroforming.
- Another object of the invention is to provide a process for galvanic electrodeposition and/or a galvanic bath that allow to obtain by electroforming shells or self-supporting objects made of a 1N-3N yellow gold alloy without resorting to silver and without using cadmium or other toxic substances.
- Another object of the invention is to provide a process for galvanic electrodeposition and/or a galvanic bath that ensure high reliability in operation.
- Another object of the invention is to provide an alloy and propose a process for preparing said alloy that can be obtained and executed easily starting from commonly commercially available elements and materials.
- Another object of the invention is to provide an alloy and a process for preparing said alloy that have low costs and are safe in application.
- the galvanic electrodeposition process comprises a step in which at least one object immersed in a galvanic bath which in turn comprises an aqueous solution is coated with a layer of yellow gold alloy.
- the process is performed by applying a potential difference to two electrodes immersed in the bath: one electrode, the cathode, is constituted by the object to be coated, while the other one, the anode, can be constituted by the metal to be deposited, by an inert metal, by graphite, or others.
- the flow of ions of the metal generated by the application of the potential difference causes the accumulation of said ions on the object, so as to obtain progressively the forming of the desired coating layer.
- the possibility is provided to immerse a number of objects at will (of any shape and size), insofar as allowed by the dimensions of the tank filled with the aqueous solution and by the limitations and the technical requirements of each specific situation.
- the process according to the invention can be used to deposit a protective layer intended to constitute an external layer or an underlayer (substrate) of the finished product that one wishes to obtain.
- a protective layer intended to constitute an external layer or an underlayer (substrate) of the finished product that one wishes to obtain.
- the process according to the invention is intended to be performed in the field of the technique also known as electroforming, according to which the object (core) that is coated during the process is subsequently removed, leaving a sort of self-supporting shell (electroformed product) which is indeed the actual goal of the process.
- process according to the invention is intended to be have a preferred application in the field of fashion, leatherwear or jewelry, although other uses, which are in any case within the protective scope claimed herein, to provide finished products (or intermediate products) intended for other product markets are not excluded.
- the aqueous solution comprises at least gold in a quantity comprised between 1 gram and 10 gram per liter of solution, in the form of alkaline cyanide.
- the gold is preferably in the form of a potassium dicyanoaurate complex, but other practical choices (tetrachloroaurate, potassium tetracyanoaurate, or others still) are not excluded.
- the aqueous solution comprises at least copper in a quantity comprised between 30 grams and 70 gram per liter of solution, in the form of an alkaline cyanide compound (and preferably in the form of cuprous cyanide).
- the copper is preferably in the form of cuprous cyanide, but other practical choices (cuprous chloride, copper iodide, copper carbonate) are not excluded.
- the aqueous solution comprises indium in a quantity comprised between 100 milligrams and 2 gram per liter of solution, in the form of a soluble compound (and preferably in the form of a soluble complex).
- the aqueous solution comprises at least zinc in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound (and preferably in the form of a zinc complex).
- the bath (and therefore the aqueous solution) is kept at a constant temperature comprised between 50°C and 80°C.
- the solution is kept at a pH between 8 and 12.
- the current density that is applied is comprised between 0,2 A/dm 2 e 1,5 A/dm 2 .
- the bath (the aqueous solution) can be enriched with various other additives, some of which are mentioned by way of non-limiting example. With reference to these additives, it is specified that the solution can provide just one or several types among the ones that will be identified hereinafter, and that within the same type one or more different substances among the ones listed (or others still) might be present.
- the aqueous solution can comprise free cyanide in a quantity comprised between 10 grams and 50 grams per liter of solution.
- the aqueous solution can furthermore comprise a complexing agent, preferably in a quantity comprised between 5 grams and 30 grams per liter of solution.
- a complexing agent is chosen from the group constituted by a carboxylic acid, an amino acid, a polyamine, an amine, and a phosphonic acid.
- the aqueous solution can furthermore comprise a conducting salt, preferably in a quantity comprised between 10 grams and 100 grams per liter of solution.
- the conducting salt is chosen in the group constituted by a citrate, a tartrate, an oxalate, a gluconate, a carbonate, a phosphate, and a sulfate.
- the aqueous solution may furthermore comprise a wetting agent, preferably in a quantity comprised between 0.05 grams and 10 grams per liter of solution.
- the wetting agent is chosen preferably in the group constituted by lauryl sulfate and a quaternary ammonium salt.
- the aqueous solution can furthermore comprise also a grain refiner and/or a brightener.
- the grain refiner and/or the brightener are preferably chosen from the group constituted by zirconium, iridium, selenium, antimony, tin, gallium, tellurium, germanium, bismuth, titanium, and silver.
- the aqueous solution may furthermore comprise additional metals or elements in traces, which derive from the technical products used for its provision and preferably comprised in the group constituted by: silver, arsenic, selenium, germanium, and gallium.
- a subject matter of the present description is also a galvanic bath intended for the execution of a galvanic electrodeposition process (of the type just described).
- This galvanic bath comprises an aqueous solution and is adapted to coat with a layer of yellow gold alloy at least one object immersed in said solution.
- the aqueous solution comprises at least:
- the bath according to the invention can comprise one or more of the specifications related to the bath itself and to the aqueous solution described in the preceding paragraphs in relation to the galvanic electrodeposition process.
- the aqueous solution thus comprises: gold in a quantity equal to 5 grams per liter of solution, copper in a quantity equal to 55 grams per liter of solution, indium and zinc in quantities (each) equal to 0.5 grams per liter of solution. Furthermore, in the electrodeposition process which uses a galvanic bath with the formulation indicated above said bath is kept at a constant temperature equal to 60 °C, the solution is kept at pH 10.5, and a current density equal to 0.5 A/dm 2 is applied. Moreover, said formulation is enriched with:
- the present description also relates to a yellow gold alloy, which (preferably but not necessarily) is obtained indeed by means of the process and/or the bath described in the preceding pages.
- said alloy comprises at least:
- the yellow gold alloy comprises:
- the alloy comprises:
- the present description also relates to the use of a gold alloy as described in the preceding paragraphs to provide self-supporting shells which can be used in particular in the fields of clothing, jewelry, costume jewelry, shoes and leatherwear (and other sectors such as fashion, faucets, eyewear and also electronics).
- the process provides, according to per se traditional manners, for applying a potential difference to the electrodes immersed in the galvanic bath, wherein the object (each object) to be coated with a protective layer acts as a cathode.
- the object each object to be coated with a protective layer acts as a cathode.
- One of the particularities of the invention which allows to overcome the limitations of known processes, is indeed the composition of the aqueous solution of the bath (in which the object to be coated is indeed immersed).
- aqueous solution of which comprises (in the indicated ranges) gold and copper in the form of alkaline cyanides, indium and zinc in the form of soluble compounds in fact allows to deposit a layer of quaternary gold alloy (comprising gold, copper, indium and zinc) with high mechanical strength, both with low thicknesses and with high thicknesses, so as to be able to constitute a self-supporting shell (but also, if so desired, an effective coating layer).
- quaternary gold alloy comprising gold, copper, indium and zinc
- zinc in the form of a soluble complex is of extreme practical interest.
- the obtained layer has high solderability, understood indeed as the capacity to withstand successive soldering treatments (which are for example necessary to close the openings provided in order to remove the internal core and indeed obtain the self-supporting shell).
- the deposited layer is free from residual tensions, proving itself resilient (not fragile) and therefore capable of withstanding impacts and stresses without generating cracks and failures.
- the invention is furthermore very versatile and allows to obtain yellow gold alloys with a number of carats comprised between for example 8 and 23.
- the chosen composition ensures the capability to keep the fineness constant, as a further assurance of the reliability and repeatability of the process and of the strength of the alloy obtained.
- the invention allows to obtain the results described above without using and without resorting to silver (except in traces or as a grain refiner or brightener) and especially without cadmium or other metals and substances that are potentially toxic, thereby revealing itself to be of extreme practical interest.
- the materials used, as well as the dimensions, may be any according to the requirements and the state of the art.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
A galvanic electrodeposition process, comprising a step of coating with a layer of yellow gold alloy at least one object immersed in a galvanic bath which comprises an aqueous solution. The aqueous solution comprises at least: - gold in a quantity comprised between 1 gram and 10 grams per liter of solution, in the form of alkaline cyanide, - copper in a quantity comprised between 30 grams and 70 grams per liter of solution, in the form of an alkaline cyanide compound, - indium in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound, - zinc in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound.
Description
PROCESS FOR GALVANIC ELECTRODEPOSITION AND ASSOCIATED GALVANIC BATH
The present invention relates to a process for galvanic electrodeposition and to the associated galvanic bath, and also to a yellow gold alloy and to a use thereof.
As is known, by means of a galvanic electrodeposition process it is possible to deposit a more or less thin metallic layer on an object, for decorative purposes, protective purposes, or others. In some cases the finished product is constituted by the very object coated by the electrodeposited layer. In others, which are in any case of considerable practical interest, the deposited metallic layer is subsequently detached from the object, allowing to obtain a sort of self-supporting shell (which is internally empty) which considers the actual goal of the process: in this case, the process takes the name of "electroforming" and the finished product is also known as "electroformed".
In any case, according to methods which are by now well established, the process provides an electrolytic reaction in a tank (galvanic bath), in which the object to be coated (which acts as a cathode) is immersed in an aqueous solution of the metal to be deposited. In this context, the anode can be constituted by the metal itself to be deposited or also by an inert metal or by graphite. In any case, by applying a potential difference to the two electrodes, a flow of ions of the metal to be deposited is generated and the metal progressively accumulates on the cathode, forming indeed the desired layer.
Among the various metals commonly used, in the field of fashion and jewelry it is customary to deposit metallic layers made of gold alloy, intended indeed to constitute a decorative (and/or protective) coating or a self-supporting shell. In particular, in this context yellow gold alloys which the reference standard (UNI EN ISO 8654) identifies with the codes IN (which corresponds to pale yellow), 2N (light yellow), and 3N (yellow) are
well-known.
In greater detail, in the decorative field of plating, methods are known which are adapted to produce deposits of yellow gold (with a fineness greater than or equal to 12 carats), which are ductile to a thickness of 10 microns and highly resistant to the loss of luster. These deposits are obtained by electrolysis in an alkaline galvanic bath which contains, in addition to gold and copper compounds, cadmium in the form of alkaline cadmium cyanide. Cadmium facilitates the deposition of thick layers (between 1 and 800 pm) and allows to obtain the yellow coloring, reducing the quantity of copper contained in the alloy; however, this is an extremely toxic element, the use of which is by now forbidden in several countries.
Yellow gold alloys are also known which comprise gold, copper and silver (and therefore lack cadmium); however, these alloys are soft and therefore unsuitable for uses in the field of electroforming. Moreover, it is substantially impossible to obtain a production with a constant gold fineness and therefore they are not used in commerce.
Other known alloys which in any case avoid resorting to cadmium are those which comprise gold, copper and indium. In this case, if one maintains a sufficiently high percentage of indium (4%), one obtains an alloy that is fragile (before and after thermal treatment) and scarcely solderable, compromising the possibility to move on to subsequent treatments. Vice versa, when working with a lower indium percentage (2%), the resulting alloys ensure better performance but do not allow to obtain the desired INSIST yellow color.
The aim of the present invention is to solve the problems described above, by providing a process for galvanic electrodeposition and/or a galvanic bath that allow to provide layers made of a 1N-3N yellow gold alloy, which have good solderability and high mechanical strength.
Within this aim, an object of the invention is to provide a process for galvanic electrodeposition and/or a galvanic bath that allow to obtain by
electroforming shells or self-supporting objects made of a 1N-3N yellow gold alloy, with adequate metallic properties.
Another object of the invention is to provide a 1N-3N yellow gold alloy that can be used to provide shells or self-supporting objects obtained by electroforming.
Another object of the invention is to provide a process for galvanic electrodeposition and/or a galvanic bath that allow to obtain by electroforming shells or self-supporting objects made of a 1N-3N yellow gold alloy without resorting to silver and without using cadmium or other toxic substances.
Another object of the invention is to provide a process for galvanic electrodeposition and/or a galvanic bath that ensure high reliability in operation.
Another object of the invention is to provide an alloy and propose a process for preparing said alloy that can be obtained and executed easily starting from commonly commercially available elements and materials.
Another object of the invention is to provide an alloy and a process for preparing said alloy that have low costs and are safe in application.
This aim and these and other objects which will become better apparent hereinafter are achieved by a process according to claim 1, a galvanic bath according to claim 10, a yellow gold alloy according to claim 11, and a use of a yellow gold alloy according to claim 14.
Further characteristics and advantages of the invention will become better apparent from the description of a preferred but not exclusive embodiment of the process, of the bath and of the alloy according to the invention, illustrated by way of non-limiting example in the paragraphs that follow.
The galvanic electrodeposition process comprises a step in which at least one object immersed in a galvanic bath which in turn comprises an aqueous solution is coated with a layer of yellow gold alloy.
According to per se known methods, the process is performed by applying a potential difference to two electrodes immersed in the bath: one electrode, the cathode, is constituted by the object to be coated, while the other one, the anode, can be constituted by the metal to be deposited, by an inert metal, by graphite, or others. In any case, the flow of ions of the metal generated by the application of the potential difference causes the accumulation of said ions on the object, so as to obtain progressively the forming of the desired coating layer. The possibility is provided to immerse a number of objects at will (of any shape and size), insofar as allowed by the dimensions of the tank filled with the aqueous solution and by the limitations and the technical requirements of each specific situation.
So far, in any case, these are traditional practices, which are well- known in the art and to the person skilled in the art, and therefore these aspects will not be dwelt upon further.
The process according to the invention can be used to deposit a protective layer intended to constitute an external layer or an underlayer (substrate) of the finished product that one wishes to obtain. At the same time, and as will be specified further hereinafter, in the preferred application (which enhances the particularities described in the paragraphs that follow) the process according to the invention is intended to be performed in the field of the technique also known as electroforming, according to which the object (core) that is coated during the process is subsequently removed, leaving a sort of self-supporting shell (electroformed product) which is indeed the actual goal of the process.
It is specified furthermore that the process according to the invention is intended to be have a preferred application in the field of fashion, leatherwear or jewelry, although other uses, which are in any case within the protective scope claimed herein, to provide finished products (or intermediate products) intended for other product markets are not excluded.
According to the invention, the aqueous solution comprises at least
gold in a quantity comprised between 1 gram and 10 gram per liter of solution, in the form of alkaline cyanide. In particular, the gold is preferably in the form of a potassium dicyanoaurate complex, but other practical choices (tetrachloroaurate, potassium tetracyanoaurate, or others still) are not excluded.
Furthermore, according to the invention, the aqueous solution comprises at least copper in a quantity comprised between 30 grams and 70 gram per liter of solution, in the form of an alkaline cyanide compound (and preferably in the form of cuprous cyanide). In particular, the copper is preferably in the form of cuprous cyanide, but other practical choices (cuprous chloride, copper iodide, copper carbonate) are not excluded.
Furthermore, according to the invention, the aqueous solution comprises indium in a quantity comprised between 100 milligrams and 2 gram per liter of solution, in the form of a soluble compound (and preferably in the form of a soluble complex).
Furthermore, according to the invention, the aqueous solution comprises at least zinc in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound (and preferably in the form of a zinc complex).
Usefully, during the execution of the process according to the invention the bath (and therefore the aqueous solution) is kept at a constant temperature comprised between 50°C and 80°C.
Advantageously, furthermore, during the execution of the process the solution is kept at a pH between 8 and 12.
In a solution of considerable practical interest, which in any case does not limit the application of the invention, during the electrodeposition step the current density that is applied is comprised between 0,2 A/dm2 e 1,5 A/dm2.
In addition to the four components cited above (gold, copper, zinc and indium), the bath (the aqueous solution) can be enriched with various
other additives, some of which are mentioned by way of non-limiting example. With reference to these additives, it is specified that the solution can provide just one or several types among the ones that will be identified hereinafter, and that within the same type one or more different substances among the ones listed (or others still) might be present.
Favorably, therefore, the aqueous solution can comprise free cyanide in a quantity comprised between 10 grams and 50 grams per liter of solution.
In one solution of great practical interest, the aqueous solution can furthermore comprise a complexing agent, preferably in a quantity comprised between 5 grams and 30 grams per liter of solution. Preferably, said complexing agent is chosen from the group constituted by a carboxylic acid, an amino acid, a polyamine, an amine, and a phosphonic acid.
Positively, the aqueous solution can furthermore comprise a conducting salt, preferably in a quantity comprised between 10 grams and 100 grams per liter of solution. Preferably, the conducting salt is chosen in the group constituted by a citrate, a tartrate, an oxalate, a gluconate, a carbonate, a phosphate, and a sulfate.
Usefully, the aqueous solution may furthermore comprise a wetting agent, preferably in a quantity comprised between 0.05 grams and 10 grams per liter of solution. In particular, the wetting agent is chosen preferably in the group constituted by lauryl sulfate and a quaternary ammonium salt.
Advantageously, the aqueous solution can furthermore comprise also a grain refiner and/or a brightener. In greater detail, the grain refiner and/or the brightener are preferably chosen from the group constituted by zirconium, iridium, selenium, antimony, tin, gallium, tellurium, germanium, bismuth, titanium, and silver.
Furthermore, it is specified that the aqueous solution may furthermore comprise additional metals or elements in traces, which derive from the technical products used for its provision and preferably comprised in the
group constituted by: silver, arsenic, selenium, germanium, and gallium.
Like the electrodeposition process, a subject matter of the present description is also a galvanic bath intended for the execution of a galvanic electrodeposition process (of the type just described). This galvanic bath comprises an aqueous solution and is adapted to coat with a layer of yellow gold alloy at least one object immersed in said solution.
According to the invention, and by analogy with what has been described in the preceding paragraphs, the aqueous solution comprises at least:
- gold in a quantity comprised between 1 gram and 10 grams per liter of solution, in the form of alkaline cyanide,
- copper in a quantity comprised between 30 grams and 70 grams per liter of solution, in the form of an alkaline cyanide compound,
- indium in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound,
- zinc in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound.
Furthermore, the bath according to the invention can comprise one or more of the specifications related to the bath itself and to the aqueous solution described in the preceding paragraphs in relation to the galvanic electrodeposition process.
Merely by way of example, one possible formulation of the aqueous solution of the galvanic bath, which has been found to be of extreme practical interest and maximally effective in achieving the goals that will be described in the pages that follow, is described hereinafter.
In this possible formulation, the aqueous solution thus comprises: gold in a quantity equal to 5 grams per liter of solution, copper in a quantity equal to 55 grams per liter of solution, indium and zinc in quantities (each) equal to 0.5 grams per liter of solution. Furthermore, in the electrodeposition process which uses a galvanic bath with the formulation
indicated above said bath is kept at a constant temperature equal to 60 °C, the solution is kept at pH 10.5, and a current density equal to 0.5 A/dm2 is applied. Moreover, said formulation is enriched with:
- tetraethylenepentamine (1 milliliter per liter of solution),
- (2-hydroxy ethyl)iminodiacetic acid (10 grams per liter of solution),
- sodium glucoheptonate (20 grams per liter of solution),
- free potassium cyanide (25 grams per liter of solution).
In addition to the process and to the bath already described, the present description also relates to a yellow gold alloy, which (preferably but not necessarily) is obtained indeed by means of the process and/or the bath described in the preceding pages.
According to the invention, said alloy comprises at least:
- gold in a quantity by weight comprised between 30% and 95%,
- copper in a quantity by weight comprised between 1% and 65%,
- indium in a quantity by weight comprised between 2% and 6%,
- zinc in a quantity by weight comprised between 0.01% and 3%.
In particular, in an embodiment of considerable practical interest, the yellow gold alloy comprises:
- gold in a quantity by weight comprised between 33% and 92%,
- copper in a quantity by weight comprised between 3% and 60%,
- indium in a quantity by weight comprised between 2% and 6%,
- zinc in a quantity by weight comprised between 0.5% and 1.5%.
Even more particularly, in a preferred embodiment option, which is in any case mentioned by way of non-limiting example of the invention, the alloy comprises:
- gold in a quantity by weight equal to 75%,
- copper in a quantity by weight equal to 19%,
- indium in a quantity by weight equal to 5%,
- zinc in a quantity by weight equal to 1%.
The present description also relates to the use of a gold alloy as described in the preceding paragraphs to provide self-supporting shells which can be used in particular in the fields of clothing, jewelry, costume jewelry, shoes and leatherwear (and other sectors such as fashion, faucets, eyewear and also electronics).
It should be specified in any case that the protective scope claimed herein is extended to processes and baths (and alloys) which have the particularities described in the preceding pages, but independently of the specific field of application, which therefore may be any.
The use of the bath and of the alloy and in general the execution of the process and of the invention are in fact evident from what has been described so far.
It has in fact been shown that the process provides, according to per se traditional manners, for applying a potential difference to the electrodes immersed in the galvanic bath, wherein the object (each object) to be coated with a protective layer acts as a cathode. One of the particularities of the invention, which allows to overcome the limitations of known processes, is indeed the composition of the aqueous solution of the bath (in which the object to be coated is indeed immersed).
The choice to resort to a bath the aqueous solution of which comprises (in the indicated ranges) gold and copper in the form of alkaline cyanides, indium and zinc in the form of soluble compounds, in fact allows to deposit a layer of quaternary gold alloy (comprising gold, copper, indium and zinc) with high mechanical strength, both with low thicknesses and with high thicknesses, so as to be able to constitute a self-supporting shell (but also, if so desired, an effective coating layer). In this regard, especially resorting to zinc in the form of a soluble complex is of extreme practical interest.
The specific combination of components (copper, gold, indium and especially zinc) in the indicated ranges also allows to obtain a yellow (IN-
3N) deposit.
In greater detail, in addition to mechanical strength, the obtained layer has high solderability, understood indeed as the capacity to withstand successive soldering treatments (which are for example necessary to close the openings provided in order to remove the internal core and indeed obtain the self-supporting shell).
Furthermore, at the end of the galvanic electrodeposition process the deposited layer is free from residual tensions, proving itself resilient (not fragile) and therefore capable of withstanding impacts and stresses without generating cracks and failures.
The invention is furthermore very versatile and allows to obtain yellow gold alloys with a number of carats comprised between for example 8 and 23.
The chosen composition (and in particular the use of cyanides) ensures the capability to keep the fineness constant, as a further assurance of the reliability and repeatability of the process and of the strength of the alloy obtained.
Similar remarks can be developed in relation to the gold alloy according to the invention, wherein said alloy indeed has a peculiar quaternary formulation, which comprises at least (in the indicated ranges) gold and copper, zinc and indium as bonding metals. Said 1N-3N yellow gold quaternary alloy indeed has a high mechanical strength and solderability in addition to the other benefits illustrated earlier.
The invention allows to obtain the results described above without using and without resorting to silver (except in traces or as a grain refiner or brightener) and especially without cadmium or other metals and substances that are potentially toxic, thereby revealing itself to be of extreme practical interest.
The further additives and substances that can enrich the aqueous solution, described in the preceding pages, increase and further enhance the
particularities described above.
The invention thus conceived is susceptible of numerous modifications and variations, all of which are within the scope of the appended claims; all the details may furthermore be replaced with other technically equivalent elements.
In the exemplary embodiments shown, individual characteristics, given in relation to specific examples, may actually be interchanged with other different characteristics that exist in other exemplary embodiments.
In practice, the materials used, as well as the dimensions, may be any according to the requirements and the state of the art.
Claims
1. A galvanic electrodeposition process, comprising a step of coating with a layer of yellow gold alloy at least one object immersed in a galvanic bath which comprises an aqueous solution, characterized in that the aqueous solution comprises at least:
- gold in a quantity comprised between 1 gram and 10 grams per liter of solution, in the form of alkaline cyanide,
- copper in a quantity comprised between 30 grams and 70 grams per liter of solution, in the form of an alkaline cyanide compound,
- indium in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound,
- zinc in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound.
2. The process according to claim 1, characterized in that the bath is kept at a constant temperature comprised between 50°C and 80°C.
3. The process according to claim 1 or 2, characterized in that the solution is kept at a pH between 8 and 12.
4. The process according to one or more of the preceding claims, characterized in that during the electrodeposition step the current density that is applied is comprised between 0.2 A/dm2 and 1.5 A/dm2.
5. The process according to one or more of the preceding claims, characterized in that the aqueous solution comprises free cyanide in a quantity comprised between 10 grams and 50 grams per liter of solution.
6. The process according to one or more of the preceding claims, characterized in that the aqueous solution furthermore comprises a complexing agent, preferably in a quantity comprised between 5 grams and 30 grams per liter of solution, the complexing agent being chosen preferably in the group constituted by a carboxylic acid, an amino acid, a polyamine, an amine, and a phosphonic acid.
7. The process according to one or more of the preceding claims,
characterized in that the aqueous solution furthermore comprises a conducting salt, preferably in a quantity comprised between 10 grams and 100 grams per liter of solution, the conducting salt being chosen preferably in the group constituted by a citrate, a tartrate, an oxalate, a gluconate, a carbonate, a phosphate, and a sulfate.
8. The process according to one or more of the preceding claims, characterized in that the aqueous solution furthermore comprises a wetting agent, preferably in a quantity comprised between 0.05 grams and 10 grams per liter of solution, the wetting agent been chosen preferably from the group constituted by lauryl sulfate and a quaternary ammonium salt.
9. The process according to one or more of the preceding claims, characterized in that the aqueous solution furthermore comprises a grain refiner and/or a brightener, the grain refiner and/or the brightener being chosen preferably from the group constituted by zirconium, iridium, selenium, antimony, tin, gallium, tellurium, germanium, bismuth, titanium, and silver.
10. A galvanic bath for performing a galvanic electrodeposition process, comprising an aqueous solution and adapted to coat with a layer of yellow gold alloy at least one object immersed in said solution, characterized in that said aqueous solution comprises at least:
- gold in a quantity comprised between 1 gram and 10 grams per liter of solution, in the form of alkaline cyanide,
- copper in a quantity comprised between 30 grams and 70 grams per liter of solution, in the form of an alkaline cyanide compound,
- indium in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound,
- zinc in a quantity comprised between 100 milligrams and 2 grams per liter of solution, in the form of a soluble compound.
11. A yellow gold alloy, obtainable by means of a process according to one or more of claims 1-9 and/or by means of a bath according to claim
10, characterized in that it comprises:
- gold in a quantity by weight comprised between 30% and 95%,
- copper in a quantity by weight comprised between 1% and 65%,
- indium in a quantity by weight comprised between 2% and 6%, - zinc in a quantity by weight comprised between 0.01% and 3%.
12. The yellow gold alloy according to claim 11, characterized in that it comprises:
- gold in a quantity by weight comprised between 33% and 92%,
- copper in a quantity by weight comprised between 3% and 60%, - indium in a quantity by weight comprised between 2% and 6%,
- zinc in a quantity by weight comprised between 0.5% and 1.5%.
13. The gold alloy according to claim 12, characterized in that it comprises:
- gold in a quantity by weight equal to 75%, - copper in a quantity by weight equal to 19%,
- indium in a quantity by weight equal to 5%,
- zinc in a quantity by weight equal to 1%.
14. Use of a gold alloy according to one or more of claims 11-13, for the provision of self-supporting shells, in particular in the fields of clothing, jewelry, costume jewelry, shoes and leatherwear.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IT2021/000006 WO2022180650A1 (en) | 2021-02-23 | 2021-02-23 | Process for galvanic electrodeposition and associated galvanic bath |
| EP21716861.6A EP4298270A1 (en) | 2021-02-23 | 2021-02-23 | Process for galvanic electrodeposition and associated galvanic bath |
| CN202180093742.1A CN116917549A (en) | 2021-02-23 | 2021-02-23 | Method for electroplating electrodeposition and related electroplating cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IT2021/000006 WO2022180650A1 (en) | 2021-02-23 | 2021-02-23 | Process for galvanic electrodeposition and associated galvanic bath |
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| Publication Number | Publication Date |
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| WO2022180650A1 true WO2022180650A1 (en) | 2022-09-01 |
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| PCT/IT2021/000006 WO2022180650A1 (en) | 2021-02-23 | 2021-02-23 | Process for galvanic electrodeposition and associated galvanic bath |
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| Country | Link |
|---|---|
| EP (1) | EP4298270A1 (en) |
| CN (1) | CN116917549A (en) |
| WO (1) | WO2022180650A1 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4687557A (en) | 1985-03-01 | 1987-08-18 | Heinz Emmenegger | Gold alloys and galvanic bath for the electrolytic deposit thereof |
| US5085744A (en) | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
| GB2279662A (en) * | 1993-07-10 | 1995-01-11 | Cookson Precious Metals Limite | Gold alloy |
| EP0904765A2 (en) * | 1997-09-25 | 1999-03-31 | Ivoclar Ag | Gold coloured dental alloy |
| EP1266974A1 (en) * | 2001-05-30 | 2002-12-18 | Leg.Or S.r.l | Gold alloys and master alloys for obtaining them |
| ITFI20120208A1 (en) * | 2012-10-12 | 2014-04-13 | Bluclad S R L | SOLUTION FOR THE ELECTROPLATE OF A GOLDEN LEAGUE AND THE LEAGUE DERIVING FROM IT. |
| US20160168741A1 (en) * | 2013-08-29 | 2016-06-16 | 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 |
-
2021
- 2021-02-23 WO PCT/IT2021/000006 patent/WO2022180650A1/en active Application Filing
- 2021-02-23 CN CN202180093742.1A patent/CN116917549A/en active Pending
- 2021-02-23 EP EP21716861.6A patent/EP4298270A1/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4687557A (en) | 1985-03-01 | 1987-08-18 | Heinz Emmenegger | Gold alloys and galvanic bath for the electrolytic deposit thereof |
| CH662583A5 (en) | 1985-03-01 | 1987-10-15 | Heinz Emmenegger | GALVANIC BATH FOR THE ELECTROLYTIC DEPOSITION OF GOLD-COPPER-CADMIUM-ZINC ALLOYS. |
| US5085744A (en) | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
| GB2279662A (en) * | 1993-07-10 | 1995-01-11 | Cookson Precious Metals Limite | Gold alloy |
| EP0904765A2 (en) * | 1997-09-25 | 1999-03-31 | Ivoclar Ag | Gold coloured dental alloy |
| EP1266974A1 (en) * | 2001-05-30 | 2002-12-18 | Leg.Or S.r.l | Gold alloys and master alloys for obtaining them |
| EP1983077B1 (en) | 2007-04-19 | 2016-12-28 | Enthone, Inc. | Electrolyte and method for electrolytic deposition of gold-copper alloys |
| ITFI20120208A1 (en) * | 2012-10-12 | 2014-04-13 | Bluclad S R L | SOLUTION FOR THE ELECTROPLATE OF A GOLDEN LEAGUE AND THE LEAGUE DERIVING FROM IT. |
| US20160168741A1 (en) * | 2013-08-29 | 2016-06-16 | Harting Kgaa | Contact element with gold coating |
Also Published As
| Publication number | Publication date |
|---|---|
| EP4298270A1 (en) | 2024-01-03 |
| CN116917549A (en) | 2023-10-20 |
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