EP0119424B1 - Verfahren zum Abscheiden von niederkarätigen, glänzenden Gold-Silber-Legierungsüberzügen - Google Patents
Verfahren zum Abscheiden von niederkarätigen, glänzenden Gold-Silber-Legierungsüberzügen Download PDFInfo
- Publication number
- EP0119424B1 EP0119424B1 EP84101158A EP84101158A EP0119424B1 EP 0119424 B1 EP0119424 B1 EP 0119424B1 EP 84101158 A EP84101158 A EP 84101158A EP 84101158 A EP84101158 A EP 84101158A EP 0119424 B1 EP0119424 B1 EP 0119424B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gold
- silver
- tellurium
- carat
- 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.)
- Expired
Links
- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 18
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 title claims description 18
- 230000008021 deposition Effects 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 9
- 238000000576 coating method Methods 0.000 title abstract description 12
- 239000010931 gold 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
- 239000003513 alkali Substances 0.000 claims abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 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 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 3
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940098221 silver cyanide Drugs 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 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 11
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 4
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 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
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 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
- 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
- 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 a method for the deposition of low-carat, shiny alloys which are stable in a wide range of working areas.
- 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-PS98 698), condensation products of polyalkyleneimines and alkylene polyamines (DE-PS 2713 507).
- DD-PS98 698 triphenylmethane dyes
- DE-PS 2713 507 condensation products of 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 rate, in particular on the current density and the bath temperature. These are dependencies. disadvantageous for a practical bath operation for the deposition of low-carat gold-silver alloys with a constant carat content.
- an electrolytic bath consisting of an aqueous solution of 0.5 to 25 g / l gold in the form of alkali gold cyanide, 0.25 to 15 g / l silver in the form of alkali silver cyanide and 10 to 200 g / 1 alkali cyanide and an additional 0.000 5 to 5 g / l tellurium in the form of a water-soluble tellurium compound and possibly a wetting agent.
- the electrolyte preferably contains 0.001 to 1 g / l tellurium in the form of a water-soluble tellurium compound, it being possible for the tellurium to be in the oxidation stage 11, IV or VI.
- tellurium-containing bath additives are tellurium dioxide (Te0 2 ), tellurium trioxide (Te0 3 ), telluric acid and its derivatives, such as tellurite and higher-condensed molecular complexes, telluric acid and its derivatives, tellurium-halogen compounds and tellurides.
- tellurites and / or tellurates in the bathroom has proven to be the best.
- This effect is particularly advantageous for the practical use of the bathroom.
- these baths allow low-carat, shiny gold-silver alloy layers with layer thicknesses over 100 microns to be produced in a single deposition process without intermediate treatment.
- the approx. 100 ⁇ m thick, low-carat gold-silver alloy layers also show an excellent shine 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 / l gold in the form of potassium gold cyanide, 1 to 6 g / l silver in the form of potassium silver cyanide and 50 to 150 g / l 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 of 0.5-5 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 .
Landscapes
- 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)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT84101158T ATE27007T1 (de) | 1983-03-16 | 1984-02-04 | Verfahren zum abscheiden von niederkaraetigen, glaenzenden gold-silber-legierungsueberzuegen. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19833309397 DE3309397A1 (de) | 1983-03-16 | 1983-03-16 | Elektrolytisches bad zum abscheiden von niederkaraetigen, glaenzenden gold-silber-legierungsueberzuegen |
DE3309397 | 1983-03-16 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0119424A1 EP0119424A1 (de) | 1984-09-26 |
EP0119424B1 true EP0119424B1 (de) | 1987-05-06 |
Family
ID=6193635
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84101158A Expired EP0119424B1 (de) | 1983-03-16 | 1984-02-04 | Verfahren zum Abscheiden von niederkarätigen, glänzenden Gold-Silber-Legierungsüberzügen |
Country Status (7)
Country | Link |
---|---|
US (1) | US4487664A (enrdf_load_stackoverflow) |
EP (1) | EP0119424B1 (enrdf_load_stackoverflow) |
JP (1) | JPS59179794A (enrdf_load_stackoverflow) |
AT (1) | ATE27007T1 (enrdf_load_stackoverflow) |
BR (1) | BR8401131A (enrdf_load_stackoverflow) |
DE (2) | DE3309397A1 (enrdf_load_stackoverflow) |
HK (1) | HK102891A (enrdf_load_stackoverflow) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3505473C1 (de) * | 1985-02-16 | 1986-06-05 | Degussa Ag, 6000 Frankfurt | Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsueberzuegen |
JP2007537358A (ja) * | 2004-05-11 | 2007-12-20 | テクニック・インコーポレイテッド | 金−スズ共晶合金のための電気めっき用溶液 |
US20090104463A1 (en) | 2006-06-02 | 2009-04-23 | Rohm And Haas Electronic Materials Llc | Gold alloy electrolytes |
SG127854A1 (en) | 2005-06-02 | 2006-12-29 | Rohm & Haas Elect Mat | Improved gold electrolytes |
US9290311B2 (en) | 2012-03-22 | 2016-03-22 | Saint-Gobain Ceramics & Plastics, Inc. | Sealed containment tube |
JP6105039B2 (ja) | 2012-03-22 | 2017-03-29 | サン−ゴバン セラミックス アンド プラスティクス,インコーポレイティド | 焼結結合されたセラミック物品 |
CN104540796B (zh) | 2012-03-22 | 2017-02-22 | 圣戈本陶瓷及塑料股份有限公司 | 加长管结构 |
ITFI20120103A1 (it) | 2012-06-01 | 2013-12-02 | Bluclad Srl | Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni. |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1213196B (de) * | 1961-05-01 | 1966-03-24 | Sel Rex Corpooration | Bad zum galvanischen Abscheiden glaenzender 14 bis 23, 5 karaetiger Gold-Silberueberzuege |
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 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE750185C (de) * | 1939-07-08 | 1944-12-27 | Baeder zur elektrolytischen Abscheidung von glaenzenden Metallniederschlaegen | |
US3475292A (en) * | 1966-02-10 | 1969-10-28 | Technic | Gold plating bath and process |
JPS4410363Y1 (enrdf_load_stackoverflow) * | 1966-12-08 | 1969-04-25 | ||
GB1283024A (en) * | 1970-01-22 | 1972-07-26 | B J S Electro Plating Company | Electro-depositing silver alloys |
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/de not_active Withdrawn
-
1984
- 1984-02-04 EP EP84101158A patent/EP0119424B1/de not_active Expired
- 1984-02-04 DE DE8484101158T patent/DE3463528D1/de not_active Expired
- 1984-02-04 AT AT84101158T patent/ATE27007T1/de not_active IP Right Cessation
- 1984-03-13 BR BR8401131A patent/BR8401131A/pt not_active IP Right Cessation
- 1984-03-13 US US06/589,216 patent/US4487664A/en not_active Expired - Lifetime
- 1984-03-16 JP JP59049424A patent/JPS59179794A/ja active Granted
-
1991
- 1991-12-19 HK HK1028/91A patent/HK102891A/xx not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1213196B (de) * | 1961-05-01 | 1966-03-24 | Sel Rex Corpooration | Bad zum galvanischen Abscheiden glaenzender 14 bis 23, 5 karaetiger Gold-Silberueberzuege |
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 |
Also Published As
Publication number | Publication date |
---|---|
HK102891A (en) | 1991-12-27 |
BR8401131A (pt) | 1984-10-23 |
ATE27007T1 (de) | 1987-05-15 |
JPS59179794A (ja) | 1984-10-12 |
DE3309397A1 (de) | 1984-09-20 |
JPH0571673B2 (enrdf_load_stackoverflow) | 1993-10-07 |
EP0119424A1 (de) | 1984-09-26 |
US4487664A (en) | 1984-12-11 |
DE3463528D1 (en) | 1987-06-11 |
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