EP0041208B1 - Alkalisches Bad zum galvanischen Abscheiden niederkarätiger rosa- bis gelbfarbener Goldlegierungsschichten - Google Patents
Alkalisches Bad zum galvanischen Abscheiden niederkarätiger rosa- bis gelbfarbener Goldlegierungsschichten Download PDFInfo
- Publication number
- EP0041208B1 EP0041208B1 EP81103982A EP81103982A EP0041208B1 EP 0041208 B1 EP0041208 B1 EP 0041208B1 EP 81103982 A EP81103982 A EP 81103982A EP 81103982 A EP81103982 A EP 81103982A EP 0041208 B1 EP0041208 B1 EP 0041208B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gold
- alkaline bath
- pink
- cyanide
- zinc
- 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
- 239000003353 gold alloy Substances 0.000 title claims description 15
- 229910001020 Au alloy Inorganic materials 0.000 title description 9
- 238000004070 electrodeposition Methods 0.000 title description 3
- 239000011701 zinc Substances 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 19
- 239000010931 gold Substances 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 6
- 229910000960 colored gold Inorganic materials 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 5
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 4
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001495 arsenic compounds Chemical class 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- -1 alkali metal salt Chemical class 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 239000013522 chelant Substances 0.000 claims 1
- 229940065287 selenium compound Drugs 0.000 claims 1
- 150000003343 selenium compounds Chemical class 0.000 claims 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 4
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 229910003597 H2SeO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OJDHPAQEFDMEMC-UHFFFAOYSA-N N#C[Cu]C#N Chemical class N#C[Cu]C#N OJDHPAQEFDMEMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- YLZGVPCTROQQSX-UHFFFAOYSA-N [K].[Ni](C#N)C#N Chemical compound [K].[Ni](C#N)C#N YLZGVPCTROQQSX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 239000000337 buffer salt Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PRHQIYUXRPSWQZ-UHFFFAOYSA-N potassium;zinc;tricyanide Chemical compound [K+].[Zn+2].N#[C-].N#[C-].N#[C-] PRHQIYUXRPSWQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910001112 rose gold Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229910000832 white gold Inorganic materials 0.000 description 1
- 239000010938 white gold Substances 0.000 description 1
- 229910001097 yellow gold Inorganic materials 0.000 description 1
- 239000010930 yellow gold Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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 alkaline bath for the electrodeposition of low-carat rosabis yellow-colored gold alloy layers containing soluble gold cyanide, soluble copper cyanide and potassium carbonate or potassium hydrogen carbonate. Corrosion-resistant layers in the range of 13 to 18 carats are deposited.
- Baths which contain cadmium and chelating agents in addition to complex gold and copper cyanides have been used to produce low-carat pink and yellow-colored gold alloy coatings (DE-AS 22 21 159).
- Such baths generally operate in a pH range of 7.5-12 and also contain free cyanide, conductive salts, such as. B. carbonates, and buffer salts, such as. B. Phosphates. They provide glossy pink or yellow alloy deposits of good quality in favorable working conditions.
- these baths have the serious disadvantage that they contain cadmium, which is not physiologically harmless and must be replaced by other substances.
- Gold baths which, in addition to gold, also contain zinc and other alloy metals, in particular copper, as soluble salts. With such galvanic baths, however, no pink or yellow low-carat gold alloy layers have so far been produced, but only high-quality or non-colored layers.
- DE-OS2342691 describes a cyanidic alkaline white gold bath which, in addition to potassium gold cyanide and potassium zinc cyanide, contains potassium nickel cyanide and dipotassium hydrogen phosphate at pH values of 9-13. However, low-carat gold alloy layers cannot be produced with these baths.
- a galvanic gold alloy bath which, in addition to potassium gold cyanide, can also contain copper sulfate and optionally a zinc salt.
- these baths which operate at pH values of 3-10 and contain aldehydes, diamines and arsenic acid as essential components, no low-carat gold alloy layers are obtained.
- DE-OS 27 54 207 describes a gold alloy bath which contains potassium gold cyanide, zinc sulfate and sodium carbonate and is operated at pH 4.9. Green precipitates are separated from this bath.
- a gold alloy bath is known (DE-AS1033987) which contains potassium gold cyanide, copper, zinc and nickel in the form of their ethylenediaminetetradic acid salts. At pH 8 and a temperature of 60 ° C, 19-carat alloy coatings are obtained, which are grayish.
- Baths containing gold as alkali gold cyanide and copper as alkali copper cyanide have proven successful.
- Such baths preferably contain 10-30 g / l of zinc as K 2 (Zn (CN) 4 ),
- Baths containing 0.2-1.5 g / l of a selenium and / or arsenic compound have also proven useful as a gloss additive.
- the addition of chelating agents, such as ethylenediaminetetracid or other aminocarboxylic acids, in amounts of 5-20 g / l is also recommended in some cases.
- the range from 50 to 75 ° C., in particular 60-75 ° C., and the pH range from 8-12, in particular 9-10, has proven to be the working temperature.
- the baths according to the invention make it possible, despite different carat contents of the layers of 13-18 carats, depending on the bath composition and working conditions, to produce a constant, uniform pink or yellow color. Even with a fineness of 14 kt, a pleasant pink color (3-4 N) is achieved with copper contents of 30 to 40% by weight, which is surprising at these high copper contents. Even with a strongly fluctuating gold content in the bath between 3 and 10 g / l and a zinc content between 2 and 15% in the coating, an almost constant pink color is delivered. The deposited layers have good ductility.
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)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803020765 DE3020765A1 (de) | 1980-05-31 | 1980-05-31 | Alkalisches bad zum galvanischen abscheiden niederkaraetiger rosa- bis gelbfarbener goldlegierungsschichten |
| DE3020765 | 1980-05-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0041208A1 EP0041208A1 (de) | 1981-12-09 |
| EP0041208B1 true EP0041208B1 (de) | 1984-01-18 |
Family
ID=6103696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81103982A Expired EP0041208B1 (de) | 1980-05-31 | 1981-05-23 | Alkalisches Bad zum galvanischen Abscheiden niederkarätiger rosa- bis gelbfarbener Goldlegierungsschichten |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4358351A (enrdf_load_stackoverflow) |
| EP (1) | EP0041208B1 (enrdf_load_stackoverflow) |
| JP (1) | JPS5723089A (enrdf_load_stackoverflow) |
| DE (1) | DE3020765A1 (enrdf_load_stackoverflow) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0140832B1 (fr) * | 1983-09-01 | 1988-01-13 | H. E. Finishing SA | Bain pour le dépôt électrolytique d'alliage d'or et procédé galvanique utilisant ce bain |
| DE3345794A1 (de) * | 1983-12-17 | 1985-07-04 | LPW-Chemie GmbH, 4040 Neuss | Elektrolyt fuer die abscheidung einer niedrigkaraetigen gelb- bis rose-gefaerbten gold-kupfer-zink-legierung |
| DE3345795A1 (de) * | 1983-12-17 | 1985-07-04 | LPW-Chemie GmbH, 4040 Neuss | Elektrolyt zur galvanischen abscheidung niedrigkaraetiger gold-kupfer-zink-legierungen |
| CH662583A5 (fr) * | 1985-03-01 | 1987-10-15 | Heinz Emmenegger | Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc. |
| DE3601559A1 (de) * | 1986-01-21 | 1987-07-23 | Lpw Chemie Gmbh | Verfahren zur einstellung der "goldfarbe" bei der galvanischen abscheidung niedrigkaraetiger gold-kupfer-zink-legierungen |
| EP0304315B1 (en) * | 1987-08-21 | 1993-03-03 | Engelhard Limited | Bath for electrolytic deposition of a gold-copper-zinc alloy |
| US5085744A (en) * | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
| CA2235408A1 (en) | 1995-11-03 | 1997-05-15 | Enthone-Omi, Inc. | Electroplating processes compositions and deposits |
| GB9522591D0 (en) * | 1995-11-03 | 1996-01-03 | Enthone Omi Suisse S A | Electroplating processes compositions and deposits |
| CH714243B1 (fr) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Procédé d'électroformage et pièce ou couche obtenue par ce procédé. |
| CH710184B1 (fr) | 2007-09-21 | 2016-03-31 | Aliprandini Laboratoires G | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques. |
| EP2312021B1 (fr) * | 2009-10-15 | 2020-03-18 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques |
| 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. |
| CN104233384A (zh) * | 2014-09-17 | 2014-12-24 | 朱忠良 | 一种无氰电镀金镀液及使用其的电镀工艺 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH286123A (fr) * | 1952-05-08 | 1952-10-15 | Spreter Victor | Bain pour le dépôt par voie galvanique d'alliages d'or. |
| DE2121150C3 (de) * | 1971-04-24 | 1980-08-21 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Verfahren zur galvanischen Abscheidung von Goldlegierungen |
| CH542934A (fr) * | 1972-03-23 | 1973-11-30 | Lea Ronal Inc | Procédé de dépôt d'un alliage d'or-cuivre-cadmium |
| ZA734253B (en) * | 1972-07-10 | 1975-02-26 | Degussa | Electrolytic bath |
| JPS4965341A (enrdf_load_stackoverflow) * | 1972-08-24 | 1974-06-25 | ||
| DE2244434C3 (de) * | 1972-09-06 | 1982-02-25 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Wäßriges Bad zur galvanischen Abscheidung von Gold und Goldlegierungen |
| CH626410A5 (en) * | 1977-09-07 | 1981-11-13 | Metaux Precieux Sa | Bath for the electrolytic deposition of gold or gold alloys and use of this bath |
| JPS5662984A (en) * | 1979-10-25 | 1981-05-29 | Seiko Epson Corp | Gold plating constitution of external parts for watch |
-
1980
- 1980-05-31 DE DE19803020765 patent/DE3020765A1/de active Granted
-
1981
- 1981-05-22 US US06/266,148 patent/US4358351A/en not_active Expired - Fee Related
- 1981-05-23 EP EP81103982A patent/EP0041208B1/de not_active Expired
- 1981-05-28 JP JP8020481A patent/JPS5723089A/ja active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3020765A1 (de) | 1981-12-10 |
| DE3020765C2 (enrdf_load_stackoverflow) | 1988-03-31 |
| JPS5723089A (en) | 1982-02-06 |
| US4358351A (en) | 1982-11-09 |
| EP0041208A1 (de) | 1981-12-09 |
| JPS648076B2 (enrdf_load_stackoverflow) | 1989-02-13 |
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