EP0119424A1 - Process for the deposition of low carat brilliant gold-silver alloy coatings - Google Patents
Process for the deposition of low carat brilliant gold-silver alloy coatings Download PDFInfo
- Publication number
- EP0119424A1 EP0119424A1 EP84101158A EP84101158A EP0119424A1 EP 0119424 A1 EP0119424 A1 EP 0119424A1 EP 84101158 A EP84101158 A EP 84101158A EP 84101158 A EP84101158 A EP 84101158A EP 0119424 A1 EP0119424 A1 EP 0119424A1
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- EP
- European Patent Office
- Prior art keywords
- gold
- silver
- carat
- tellurium
- cyanide
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 24
- 238000000576 coating method Methods 0.000 title claims abstract description 17
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 title claims description 26
- 230000008021 deposition Effects 0.000 title description 6
- 238000000034 method Methods 0.000 title 1
- 239000010931 gold Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 13
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 150000003498 tellurium compounds Chemical class 0.000 claims abstract description 6
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 claims abstract description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 4
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940098221 silver cyanide Drugs 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims description 9
- 239000000080 wetting agent Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 13
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910004273 TeO3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- SWLJJEFSPJCUBD-UHFFFAOYSA-N tellurium tetrachloride Chemical compound Cl[Te](Cl)(Cl)Cl SWLJJEFSPJCUBD-UHFFFAOYSA-N 0.000 description 1
- IIXQANVWKBCLEB-UHFFFAOYSA-N tellurium trioxide Chemical compound O=[Te](=O)=O IIXQANVWKBCLEB-UHFFFAOYSA-N 0.000 description 1
- -1 titanate ester Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 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
Definitions
- the invention relates to an electrolytic bath for depositing low-carat, shiny gold-silver alloy coatings, consisting of an aqueous solution of 0.5-25 g / 1 gold in the form of alkali gold cyanide, 0.25-15 g / 1 silver in the form of Alkali silver cyanide and 10 - 200 g / 1 alkali cyanide.
- organic substances and / or foreign metals, which are not separated, to the electrolyte shiny coatings can be deposited.
- organic brighteners are e.g. B. triphenylmethane dyes (DD-PS 98 698), condensation Products from polyalkyleneimines and alkylene polyamines (DE-PS 27 13 507).
- DD-PS 98 698 triphenylmethane dyes
- DE-PS 27 13 507 condensation Products from polyalkyleneimines and alkylene polyamines
- CH-PS 629 260 a water-soluble indium compound is described together with an organic aliphatic amine as a gloss additive, in US Pat. No.
- the gold content in the coating largely depends on the Au / Ag ratio in the bath and on the selected operating parameters for the deposition, in particular on the current density and the bath temperature. These dependencies are disadvantageous for a practical bathroom operation for the deposition of low-carat gold-silver alloys with a constant carat content.
- an object of the present invention to provide an electrolytic bath for depositing low-carat, shiny gold-silver alloy coatings, consisting of an aqueous solution of 0.5 to 25 g / 1 gold in the form of alkali gold cyanide, 0.25-15 g / 1 silver in the form of alkali silver cyanide and 10 to 200 g / 1 alkali cyanide, from which consistently low-carat layers largely independent of the operating parameters, such as current density and Bath temperature, and the gold-silver ratio in the bath can be deposited in layers over 25 ⁇ m glossy and as ductile as possible.
- the bath additionally contains 0.005 to 5 g / 1 tellurium in the form of a water-soluble tellurium compound.
- the electrolyte preferably contains 0.001 to 1 g / 1 tellurium in the form of a water-soluble tellurium compound, it being possible for the tellurium to be present in the oxidation stage II, IV or VI.
- tellurium-containing bath additives are tellurium dioxide (Te02), tellurium trioxide (Te03), telluric acid and its derivatives, such as tellurite and higher-condensed molecular complexes, telluric acid and its derivatives, tellurium-halogen compounds and tellurides.
- a 12-carat, shiny gold-silver alloy deposit is achieved that is accurate to one carat.
- Practical deviations from other working parameters, such as temperature, pH, gold, silver and KCN content, from the specified bath operating values hardly change the composition and quality of the deposited alloys.
- a gold-silver alloy cryptokarätigen a bath temperature of 40 0 C and a pH of 11.5, the bath temperature to i 5 ° C may be at a current density of approximately 0.9 A / dm 2 during the deposition, or change the pH between 10.5 and 12.5 without the composition of the deposited 12-carat alloy fluctuating by more than ⁇ 1 carat.
- these baths allow low-carat, shiny gold-silver alloy layers with layer thicknesses over 100 ⁇ m to be produced in a single deposition process without intermediate treatment. Also the approx. 100 ⁇ m thick, low-carat gold-silver alloy layers still show an excellent gloss and a strikingly constant alloy composition over the entire layer thickness.
- Such gold-silver alloy baths are therefore also suitable for the galvanoplastic production of 12-14 carat gold-silver moldings.
- a known electrolyte which contains gold, silver and free potassium cyanide dissolved in an aqueous solution, and a tellurium-containing compound is added to it, which is either soluble in water or reacts with water to form a soluble compound.
- the bath is preferably prepared with potassium salts, but sodium salts or ammonium salts can also be used, or other reaction products of AuCN and AgCN with alkali cyanides. Baths containing 5 to 10 g / 1 gold in the form of potassium gold cyanide, 1 to 6 g / 1 silver in the form of potassium silver cyanide and 50 to 150 g / 1 potassium cyanide have proven successful.
- wetting agents such as B. partially esterified forms of phosphoric acid
- the quality of the coatings can be improved.
- Such wetting agents are preferably used in the concentration range from 0.5 to 5 ml / l.
- the bath is maintained at an alkaline pH, preferably between 10.5 and 12.5. Suitable bath temperatures are between 25 ° C and 70 ° C. The higher the bath temperature, the higher the current density required for the deposition of qualitatively perfect low-carat Au / Ag alloys.
- a gold-silver alloy of 12 carat ⁇ 1 carat is obtained at a bath temperature of 40 ° C in a current density range of 0.6 to 1.2 A / dm 2 .
- the same alloy composition is obtained in a current density range of 2.2 to 3.0 A / dm 2 .
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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)
- Physical Vapour Deposition (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
Elektrolytisches Bad zum Abscheiden von niederkarätigen, glänzenden Gold-Silber-LegierungsüberzügenElectrolytic bath for depositing low-carat, shiny gold-silver alloy coatings
Die Erfindung betrifft ein elektrolytisches Bad zum Abscheiden von niederkarätigen, glänzenden Gold-Silber-Legierungsüberzügen, bestehend aus einer wässrigen Lösung von 0,5 - 25 g/1 Gold in Form von Alkaligoldzyanid, 0,25 - 15 g/1 Silber in Form von Alkalisilberzyanid und 10 - 200 g/1 Alkalizyanid.The invention relates to an electrolytic bath for depositing low-carat, shiny gold-silver alloy coatings, consisting of an aqueous solution of 0.5-25 g / 1 gold in the form of alkali gold cyanide, 0.25-15 g / 1 silver in the form of Alkali silver cyanide and 10 - 200 g / 1 alkali cyanide.
Die galvanische Abscheidung von Gold-Silber-Legierungsüberzügen ist schon viele Jahre bekannt. Bei Stromdichten von 0,1 bis 1 A/dm2 können dabei Legierungsschichten mit Gehalten von 29 bis 79 % Gold abgeschieden werden. Mit abnehmendem Goldgehalt und zunehmender Schichtdicke wächst jedoch die Sprödigkeit der Überzugschicht. Außerdem sind diese Überzüge wenig glänzend.The electroplating of gold-silver alloy coatings has been known for many years. With current densities of 0.1 to 1 A / dm 2 , alloy layers with contents of 29 to 79% gold can be deposited. However, as the gold content decreases and the layer thickness increases, the brittleness of the coating layer increases. In addition, these coatings are not very shiny.
Durch Zusatz von organischen Substanzen und/oder Fremdmetalle, die nicht mitabgeschieden werden, zum Elektrolyten lassen sich glänzende Überzüge abscheiden. Bekannt sind beispielsweise Verbindungen von Nickel, Antimon, Titan und Indium als Glanzzusätze bei elektrolytischen Gold-Silber-Bädern. Bekannt als organische Glanzbildner sind z. B. Triphenylmethanfarbstoffe (DD-PS 98 698), Kondensationsprodukte aus Polyalkyleniminen und Alkylenpolyaminen (DE-PS 27 13 507). In der CH-PS 629 260 wird als Glanzzusatz eine wasserlösliche Indiumverbindung zusammen mit einem organischen aliphatischen Amin beschrieben, in der US-PS 4 121 982 die Kombination einer selenhaltigen Verbindung mit einem Polyäthylenamin und in der DE-PS 12 13 196 die Kombination einer selenhaltigen Verbindung und eines mit Aminoalkoholen stabilisierten Titanatesters. Alle diese bekannten Glanzzusätze haben jedoch den Nachteil, daß ein befriedigender Glanz nur bis Schichtdicken von ca. 25jam erhalten werden kann und gegebenenfalls organische Substanzen in die Schicht eingebaut werden. Die Sprödigkeit der Überzüge können sie nicht vermindern.By adding organic substances and / or foreign metals, which are not separated, to the electrolyte, shiny coatings can be deposited. For example, compounds of nickel, antimony, titanium and indium are known as gloss additives in electrolytic gold-silver baths. Known as organic brighteners are e.g. B. triphenylmethane dyes (DD-PS 98 698), condensation Products from polyalkyleneimines and alkylene polyamines (DE-PS 27 13 507). In CH-PS 629 260 a water-soluble indium compound is described together with an organic aliphatic amine as a gloss additive, in US Pat. No. 4,121,982 the combination of a selenium-containing compound with a polyethylene amine and in DE-PS 12 13 196 the combination of a selenium-containing one Compound and a titanate ester stabilized with amino alcohols. However, all these known gloss additives have the disadvantage that a satisfactory gloss can only be obtained up to layer thicknesses of approximately 25 μm and, if appropriate, organic substances are incorporated into the layer. They cannot reduce the brittleness of the coatings.
Bei den bekannten Gold-Silber-Legierungsbädern ist der Goldgehalt im Überzug weitgehend abhängig vom Au/Ag-Verhältnis im Bad und von den gewählten Betriebsparametern bei der Abscheidung, insbesondere von der Stromdichte und der Badtemperatur. Diese Abhängigkeiten sind nachteilig für einen praktischen Badbetrieb zur Abscheidung niederkarätiger Gold-Silberlegierungen mit einem gleichbleibendem Karatgehalt.In the known gold-silver alloy baths, the gold content in the coating largely depends on the Au / Ag ratio in the bath and on the selected operating parameters for the deposition, in particular on the current density and the bath temperature. These dependencies are disadvantageous for a practical bathroom operation for the deposition of low-carat gold-silver alloys with a constant carat content.
Es war daher Aufgabe der vorliegenden Erfindung, ein elektrolytisches Bad zum Abscheiden von niederkarätigen, glänzenden Gold-Silber-Legierungsüberzügen zu schaffen, bestehend aus einer wässrigen Lösung von 0,5 bis 25 g/1 Gold in Form von Alkaligoldzyanid, 0,25 - 15 g/1 Silber in Form von Alkalisilberzyanid und 10 bis 200 g/1 Alkalizyanid, aus dem gleichbleibend niederkarätige Schichten weitgehend unabhängig von den Betriebsparametern, wie Stromdichte und Badtemperatur, und dem Gold-Silber-Verhältnis im Bad auch in Schichtdicken über 25 µm glänzend und möglichst duktil abgeschieden werden können.It was therefore an object of the present invention to provide an electrolytic bath for depositing low-carat, shiny gold-silver alloy coatings, consisting of an aqueous solution of 0.5 to 25 g / 1 gold in the form of alkali gold cyanide, 0.25-15 g / 1 silver in the form of alkali silver cyanide and 10 to 200 g / 1 alkali cyanide, from which consistently low-carat layers largely independent of the operating parameters, such as current density and Bath temperature, and the gold-silver ratio in the bath can be deposited in layers over 25 µm glossy and as ductile as possible.
Diese Aufgabe wurde erfindungsgemäß dadurch gelöst, daß das Bad zusätzlich 0,005 bis 5 g/1 Tellur in Form einer wasserlöslichen Tellurverbindung enthält. Vorzugsweise enthält der Elektrolyt 0,001 bis 1 g/1 Tellur in Form einer wasserlöslichen Tellurverbindung, wobei das Tellur in der Oxydationsstufe II, IV oder VI vorliegen kann. Beispiele für solche tellurhaltigen Badzusätze sind das Tellurdioxid (Te02), das Tellurtrioxid (Te03), die tellurige Säure und ihre Derivate, wie Tellurite und höherkondensierte molekulare Komplexe, die Tellursäure und ihre Derivate, Tellur-Halogen-Verbindungen und Telluride. Am besten bewährt hat sich die Anwesenheit von Telluriten und/oder Telluraten im Bad. Bereits bei Anwesenheit von geringen Mengen der wasserlöslichen Tellurverbindungen im Bad erhält man glänzende, niederkarätige Gold-Silber-Legierungsüberzüge, ohne sonstige organische oder anorganische Verbindungen zur Glanzbildung zusetzen zu müssen. Die Überzüge enthalten kein nachweisbares Tellur.This object was achieved in that the bath additionally contains 0.005 to 5 g / 1 tellurium in the form of a water-soluble tellurium compound. The electrolyte preferably contains 0.001 to 1 g / 1 tellurium in the form of a water-soluble tellurium compound, it being possible for the tellurium to be present in the oxidation stage II, IV or VI. Examples of such tellurium-containing bath additives are tellurium dioxide (Te02), tellurium trioxide (Te03), telluric acid and its derivatives, such as tellurite and higher-condensed molecular complexes, telluric acid and its derivatives, tellurium-halogen compounds and tellurides. The presence of tellurites and / or tellurates in the bathroom has proven to be the best. Even in the presence of small amounts of the water-soluble tellurium compounds in the bath, shiny, low-carat gold-silver alloy coatings are obtained without having to add other organic or inorganic compounds to form a gloss. The coatings contain no detectable tellurium.
Man erhält aus den erfindungsgemäßen Bädern hervorragend glänzende, brillante Gold-Silber-Legierungsüberzüge, die sich nicht nur durch ihren Glanz auszeichnen, sondern auch durch ihre relativ geringe Anlaufespfindlichkeit und ihre Duktilität.Outstandingly brilliant, brilliant gold-silver alloy coatings are obtained from the baths according to the invention, which are not only distinguished by their gloss, but also by their relatively low sensitivity to tarnishing and their ductility.
Außerdem wird durch den Tellurzusatz die bekannte deutliche Abhängigkeit der Legierungszusammensetzung in den niederkarätigen Au/Ag-Legierungsschichten von den Arbeitsparametern des Bades, wie Stromdichte, Badtemperatur und Metallgehalte, erheblich abgeschwächt. Mit einem solchen Bad erhält man in wesentlich breiteren Arbeitsbereichen eine gleichmäßige Legierungszusammensetzung. Dieser Effekt ist vor allem für die praktische Anwendung des Bades von besonderem Vorteil.In addition, the well-known significant dependence of the alloy composition in the low-carat Au / Ag alloy layers on the working parameters of the bath, such as current density, bath temperature and metal content, is considerably weakened by the tellurium addition. With such a bath you get a uniform alloy composition in much wider working areas. This effect is particularly advantageous for the practical use of the bathroom.
Beispielsweise erzielt man im Stromdichtebereich von 0,6 - 1,2 A/dm2 eine auf ein Karat genaue, 12-karätige, glänzende Gold-Silber-Legierungsabscheidung. Auch praxisnahe Abweichungen anderer Arbeitsparameter, wie Temperatur, pH-Wert, Gold-, Silber- und KCN-Gehalt, von den festgelegten Badbetriebswerten verändern die Zusammensetzung und Qualität der abgeschiedenen Legierungen kaum. Zum Beispiel können sich bei der Abscheidung einer niederkarätigen Gold-Silber-Legierung bei einer Stromdichte von ca. 0,9 A/dm2, einer Badtemperatur von 400 C und einem pH-Wert von 11,5 die Badtemperatur um i 5° C oder der pH-Wert zwischen 10,5 und 12,5 ändern, ohne daß die Zusammensetzung der abgeschiedenen 12-karätigen Legierung um mehr als ± 1 Karat schwankt.For example, in the current density range of 0.6 - 1.2 A / dm 2, a 12-carat, shiny gold-silver alloy deposit is achieved that is accurate to one carat. Practical deviations from other working parameters, such as temperature, pH, gold, silver and KCN content, from the specified bath operating values hardly change the composition and quality of the deposited alloys. For example, a gold-silver alloy niederkarätigen a bath temperature of 40 0 C and a pH of 11.5, the bath temperature to i 5 ° C may be at a current density of approximately 0.9 A / dm 2 during the deposition, or change the pH between 10.5 and 12.5 without the composition of the deposited 12-carat alloy fluctuating by more than ± 1 carat.
Auch für den Gehalt an freiem KCN und KAg(CN)2sind relativ große Konzentrationsschwankungen möglich, ohne daß sich Zusammensetzung und Qualität der niederkarätigen Gold-Silber-Überzüge wesentlich verändern. Dabei sollte aber das Verhältnis Gold zu Silber einen Wert von 4:1 möglichst nicht überschreiten und einen Wert von 1:2 möglichst nicht unterschreiten.Relatively large concentration fluctuations are also possible for the content of free KCN and KAg (CN) 2 , without the composition and quality of the low-carat gold-silver coatings changing significantly. However, the ratio of gold to silver should not exceed a value of 4: 1 and should not fall below a value of 1: 2 if possible.
Außerdem erlauben es diese Bäder, daß niederkarätige, glänzende Gold-Silber-Legierungsschichten mit Schichtdicken über 100 um in einem einzigen Abscheidevorgang ohne Zwischenbehandlung erzeugt werden können. Auch die ca. 100 µm dicken, niederkarätigen Gold-Silber-Legierungsschichten zeigen noch einen hervorragenden Glanz und eine auffallend gleichbleibende Legierungszusammensetzung über die gesamte Schichtdicke. Daher eignen sich solche Gold-Silber-Legierungsbäder auch für die galvanoplastische Erzeugung von 12 - 14-karätigen Gold-Silber-Formteilen.In addition, these baths allow low-carat, shiny gold-silver alloy layers with layer thicknesses over 100 µm to be produced in a single deposition process without intermediate treatment. Also the approx. 100 µm thick, low-carat gold-silver alloy layers still show an excellent gloss and a strikingly constant alloy composition over the entire layer thickness. Such gold-silver alloy baths are therefore also suitable for the galvanoplastic production of 12-14 carat gold-silver moldings.
Üblicherweise verwendet man einen bekannten Elektrolyten, der in einer wässrigen Lösung Gold, Silber und freies Kaliumzyanid gelöst enthält, und setzt ihm eine tellurhaltige Verbindung zu, die entweder in Wasser löslich ist oder sich mit Wasser zu einer löslichen Verbindung umsetzt. vorzugsweise wird das Bad mit Kaliumsalzen angesetzt, jedoch können auch Natriumsalze oder Ammoniumsalze verwendet werden, bzw. sonstige Umsetzungsprodukte von AuCN und AgCN mit Alkalizyaniden. Bewährt haben sich Bäder, die 5 bis 10 g/1 Gold in Form von Kalium-Goldzyanid, 1 bis 6 g/1 Silber in Form von Kaliumsilberzyanid und 50 bis 150 g/1 Kaliumzyanid enthalten.Usually, a known electrolyte is used which contains gold, silver and free potassium cyanide dissolved in an aqueous solution, and a tellurium-containing compound is added to it, which is either soluble in water or reacts with water to form a soluble compound. the bath is preferably prepared with potassium salts, but sodium salts or ammonium salts can also be used, or other reaction products of AuCN and AgCN with alkali cyanides. Baths containing 5 to 10 g / 1 gold in the form of potassium gold cyanide, 1 to 6 g / 1 silver in the form of potassium silver cyanide and 50 to 150 g / 1 potassium cyanide have proven successful.
Unterschiedliche tellurhaltige Verbindungen erfordern zur Erzielung des gleichen Effektes unterschiedliche Konzentrationen. Beispielsweise reichen beim Zusatz von K2TeO3 bereits 5 - 30 mg/1 für eine gleichmäßige Abscheidung einer niederkarätigen Gold-Silber-Legierungsabscheidung. Bei Verwendung von Tellursäure muß man zum Erreichen des gleichen Effektes hingegen im Grammbereich, bezogen auf die Tellursäure, arbeiten. Der Tellurgehalt des Bades läßt sich dabei analytisch leicht überwachen.Different compounds containing tellurium require different concentrations to achieve the same effect. For example, when K 2 TeO 3 is added , 5 - 30 mg / 1 is already sufficient for uniform deposition of a low-carat gold-silver alloy deposit. When using telluric acid, however, one must work in the gram range, based on telluric acid, to achieve the same effect. The tellurium content of the bath can be easily monitored analytically.
Durch Zusatz von Benetzungsmitteln, wie z. B. teilveresterter Formen der Phosphorsäure, kann die Qualität der Überzüge verbessert werden. Vorzugsweise verwendet man solche Netzmittel im Konzentrationsbereich von 0,5 - 5 ml/1. Das Bad wird auf einen alkalischen pH-Wert gehalten, vorzugsweise zwischen 10,5 und 12,5. Die geeignete Badtemperaturen liegen zwischen 25° C und 70° C. Je höher die Badtemperatur, desto höher liegt auch die für die Abscheidung qualitativ einwandfreier niederkarätiger Au/Ag-Legierungen notwendige Stromdichte.By adding wetting agents such. B. partially esterified forms of phosphoric acid, the quality of the coatings can be improved. Such wetting agents are preferably used in the concentration range from 0.5 to 5 ml / l. The bath is maintained at an alkaline pH, preferably between 10.5 and 12.5. Suitable bath temperatures are between 25 ° C and 70 ° C. The higher the bath temperature, the higher the current density required for the deposition of qualitatively perfect low-carat Au / Ag alloys.
Beispielsweise erhält man bei einer Badtemperatur von 40° C in einem Stromdichtebereich von 0,6 bis 1,2 A/dm2 eine Gold-Silber-Legierung von 12 Karat ± 1 Karat. Bei einer Badtemperatur von 70° C erhält man die gleiche Legierungszusammensetzung in einem Stromdichtebereich von 2,2 bis 3,0 A/dm2.For example, a gold-silver alloy of 12 carat ± 1 carat is obtained at a bath temperature of 40 ° C in a current density range of 0.6 to 1.2 A / dm 2 . At a bath temperature of 70 ° C, the same alloy composition is obtained in a current density range of 2.2 to 3.0 A / dm 2 .
Folgende Beispiele sollen das erfindungsgemäße Bad näher charakterisieren:
- 1. Aus einem wässrigen Elektrolyten, der 9 g/1 KAu(CN)2, 4,5 g/1 KAg(CN)2, 1 ml/l Netzmittel und 80 g/1 KCN gelöst enthält, kann man bei 40° C und pH 11 im Stromdichtebereich von 0,6 bis 1,0 grünlich-gelbe, matte ca. 18-karätige Gold-Silber-Legierungsüberzüge abscheiden. Gibt man diesem Bad 20 mg/1 K2TeO3 zu, so erhält man unter den gleichen Bedingungen in einem Stromdichtebereich von 0,6 bis 1,2 A/dm2 glänzende, gelblich-weiße, ca. 12-karätige Gold-Silber-Legierungsüberzüge.
- 2. Ein wäßriger Elektrolyt enthält 3 g/1 KAu(CN)2, 1 g/1 RAg(CN)2. 20 g/l freies KCN, 0,05 ml/l Netzmittel und 2 g/1 Tellursäure. Bei einem pH-Wert von 11 und einer Badtemperatur von 40° C erhält man bei 0,6; 0,8; 1,0 A/dm2 glänzende ca. 12 - 14-karätige Gold-Silber-Legierungsabscheidungen.
- 3. Ein wäßriger Elektrolyt enthält 10 g/1 KAg(CN)2, 15 g/1 KAu(CN)2, 200 g/1 freies KCN und 5 ml/l Netzmittel. Nach Zugabe von 4 g/1 TeCl4 lassen sich zwischen 2,2 und 3,0 A/dm2 bei pH 11 und einer Badtemperatur von 70° C glänzende, 10 - 14-karätige Gold-SilberLegierungen erzeugen.
- 4. Aus einem Elektrolyten gemäß Beispiel 1 kann man bei einer Stromdichte von 1,0 A/dm2 auf ein 1 x 2 cm großes, poliertes und vernickeltes Messingblech eine 12-karätige, glänzende, 100µm dicke Gold-Silber-Legierungsschicht abscheiden. Bei einem pH-Wert von 11 und einer Badtemperatur von 40° C wird die 100µm dicke Au/Ag-Schicht ohne Zwischenbehandlung glänzend erhalten.
- 1. From an aqueous electrolyte containing 9 g / 1 KAu (CN) 2 , 4.5 g / 1 KAg (CN) 2 , 1 ml / l wetting agent and 80 g / 1 KCN dissolved, you can at 40 ° C. and pH 11 in the current density range of 0.6 to 1.0 greenish-yellow, matt approx. 18-carat gold-silver alloy coatings. If 20 mg / 1 K 2 TeO 3 is added to this bath, shiny, yellowish-white, approx. 12-carat gold-silver is obtained under the same conditions in a current density range of 0.6 to 1.2 A / dm 2 -Alloy covers.
- 2. An aqueous electrolyte contains 3 g / 1 KAu (CN) 2, 1 g / 1 RAg (CN). 2 20 g / l free KCN, 0.05 ml / l wetting agent and 2 g / 1 telluric acid. With a pH of 11 and a bath temperature of 40 ° C you get at 0.6; 0.8; 1.0 A / dm 2 shiny approx. 12 - 14 carat gold-silver alloy deposits.
- 3. An aqueous electrolyte containing 10 g / 1 KAg (CN) 2, 15 g / 1 KAu (CN) 2, 200 g / 1 free KCN and 5 ml / l wetting agent. After adding 4 g / 1 TeCl 4 , shiny, 10-14 carat gold-silver alloys can be produced between 2.2 and 3.0 A / dm 2 at pH 11 and a bath temperature of 70 ° C.
- 4. A 12-carat, shiny, 100 µm thick gold-silver alloy layer can be deposited from an electrolyte according to Example 1 at a current density of 1.0 A / dm 2 onto a 1 x 2 cm, polished and nickel-plated brass sheet. At a pH value of 11 and a bath temperature of 40 ° C, the 100 µm thick Au / Ag layer is obtained without intermediate treatment.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84101158T ATE27007T1 (en) | 1983-03-16 | 1984-02-04 | PROCESS FOR DEPOSITIONING LOW CARAITE BRIGHT GOLD-SILVER ALLOY COATINGS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3309397 | 1983-03-16 | ||
| DE19833309397 DE3309397A1 (en) | 1983-03-16 | 1983-03-16 | ELECTROLYTIC BATH FOR DEPOSITING LOW-CARAE, GLOSSY GOLD-SILVER ALLOY COATINGS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0119424A1 true EP0119424A1 (en) | 1984-09-26 |
| EP0119424B1 EP0119424B1 (en) | 1987-05-06 |
Family
ID=6193635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84101158A Expired EP0119424B1 (en) | 1983-03-16 | 1984-02-04 | Process for the deposition of low carat brilliant gold-silver alloy coatings |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4487664A (en) |
| EP (1) | EP0119424B1 (en) |
| JP (1) | JPS59179794A (en) |
| AT (1) | ATE27007T1 (en) |
| BR (1) | BR8401131A (en) |
| DE (2) | DE3309397A1 (en) |
| HK (1) | HK102891A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0198998A1 (en) * | 1985-02-16 | 1986-10-29 | Degussa Aktiengesellschaft | Bath for the galvanic deposition of a coating of a gold-indium alloy |
| US7465385B2 (en) | 2005-06-02 | 2008-12-16 | Rohm And Haas Electronic Materials Llc | Gold alloy electrolytes |
| US8142637B2 (en) | 2005-06-02 | 2012-03-27 | Rohm And Haas Electronic Materials Llc | Gold alloy electrolytes |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7431817B2 (en) * | 2004-05-11 | 2008-10-07 | Technic, Inc. | Electroplating solution for gold-tin eutectic alloy |
| EP2828222B1 (en) | 2012-03-22 | 2019-05-01 | Saint-Gobain Ceramics & Plastics Inc. | Extended length tube structures |
| US9290311B2 (en) | 2012-03-22 | 2016-03-22 | Saint-Gobain Ceramics & Plastics, Inc. | Sealed containment tube |
| EP2828221B1 (en) | 2012-03-22 | 2020-06-10 | Saint-Gobain Ceramics & Plastics Inc. | Sinter-bonded ceramic articles |
| ITFI20120103A1 (en) | 2012-06-01 | 2013-12-02 | Bluclad Srl | GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE750185C (en) * | 1939-07-08 | 1944-12-27 | Baeder for the electrolytic deposition of shiny metal deposits | |
| US3475292A (en) * | 1966-02-10 | 1969-10-28 | Technic | Gold plating bath and process |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL277803A (en) * | 1961-05-01 | |||
| JPS4410363Y1 (en) * | 1966-12-08 | 1969-04-25 | ||
| GB1283024A (en) * | 1970-01-22 | 1972-07-26 | B J S Electro Plating Company | Electro-depositing silver alloys |
| US3864222A (en) * | 1973-03-26 | 1975-02-04 | Technic | Baths for Electrodeposition of Gold and Gold Alloys and Method Therefore |
| US4121982A (en) * | 1978-02-03 | 1978-10-24 | American Chemical & Refining Company Incorporated | Gold alloy plating bath and method |
| CH629260A5 (en) * | 1978-02-22 | 1982-04-15 | Systemes Traitements Surfaces | Process for gold-silver electrolytic deposition, bath for its use and alloy thus obtained |
-
1983
- 1983-03-16 DE DE19833309397 patent/DE3309397A1/en not_active Withdrawn
-
1984
- 1984-02-04 EP EP84101158A patent/EP0119424B1/en not_active Expired
- 1984-02-04 DE DE8484101158T patent/DE3463528D1/en not_active Expired
- 1984-02-04 AT AT84101158T patent/ATE27007T1/en not_active IP Right Cessation
- 1984-03-13 US US06/589,216 patent/US4487664A/en not_active Expired - Lifetime
- 1984-03-13 BR BR8401131A patent/BR8401131A/en not_active IP Right Cessation
- 1984-03-16 JP JP59049424A patent/JPS59179794A/en active Granted
-
1991
- 1991-12-19 HK HK1028/91A patent/HK102891A/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE750185C (en) * | 1939-07-08 | 1944-12-27 | Baeder for the electrolytic deposition of shiny metal deposits | |
| US3475292A (en) * | 1966-02-10 | 1969-10-28 | Technic | Gold plating bath and process |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 73, Nr. 14, 5. Oktober 1970, Seite 444, Nr. 72575w, Columbus, Ohio, USA & JP-B-45 012963 (SUMITOMO METAL MINING CO., LTD.) 11.05.1970 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0198998A1 (en) * | 1985-02-16 | 1986-10-29 | Degussa Aktiengesellschaft | Bath for the galvanic deposition of a coating of a gold-indium alloy |
| US7465385B2 (en) | 2005-06-02 | 2008-12-16 | Rohm And Haas Electronic Materials Llc | Gold alloy electrolytes |
| US8142637B2 (en) | 2005-06-02 | 2012-03-27 | Rohm And Haas Electronic Materials Llc | Gold alloy electrolytes |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0119424B1 (en) | 1987-05-06 |
| DE3463528D1 (en) | 1987-06-11 |
| BR8401131A (en) | 1984-10-23 |
| JPH0571673B2 (en) | 1993-10-07 |
| DE3309397A1 (en) | 1984-09-20 |
| ATE27007T1 (en) | 1987-05-15 |
| JPS59179794A (en) | 1984-10-12 |
| US4487664A (en) | 1984-12-11 |
| HK102891A (en) | 1991-12-27 |
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