EP0126921A2 - Bain de dépôt galvanique d'alliages d'or - Google Patents
Bain de dépôt galvanique d'alliages d'or Download PDFInfo
- Publication number
- EP0126921A2 EP0126921A2 EP84103995A EP84103995A EP0126921A2 EP 0126921 A2 EP0126921 A2 EP 0126921A2 EP 84103995 A EP84103995 A EP 84103995A EP 84103995 A EP84103995 A EP 84103995A EP 0126921 A2 EP0126921 A2 EP 0126921A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- bismuth
- aqueous bath
- complex compound
- bath according
- 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
- 239000003353 gold alloy Substances 0.000 title claims abstract description 7
- 230000008021 deposition Effects 0.000 title claims abstract description 5
- 229910001020 Au alloy Inorganic materials 0.000 title description 4
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- -1 alkali metal cyanide Chemical class 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 229910000960 colored gold Inorganic materials 0.000 claims abstract description 3
- 238000009736 wetting Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 5
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001414 amino alcohols Chemical class 0.000 claims description 3
- KYFPQEXWASPFBN-UHFFFAOYSA-N 1,2,3,4-tetrahydroxybutane-1,1,4-tricarboxylic acid Chemical compound OC(=O)C(O)C(O)C(O)C(O)(C(O)=O)C(O)=O KYFPQEXWASPFBN-UHFFFAOYSA-N 0.000 claims description 2
- SWFYIOVXCUTUOB-UHFFFAOYSA-N 2,3-dihydroxypropylphosphonic acid Chemical compound OCC(O)CP(O)(O)=O SWFYIOVXCUTUOB-UHFFFAOYSA-N 0.000 claims description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 claims description 2
- DSLZVSRJTYRBFB-UHFFFAOYSA-N Galactaric acid Natural products OC(=O)C(O)C(O)C(O)C(O)C(O)=O DSLZVSRJTYRBFB-UHFFFAOYSA-N 0.000 claims description 2
- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940049676 bismuth hydroxide Drugs 0.000 description 2
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001273 Polyhydroxy acid Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRCWHGIUHLWZBK-UHFFFAOYSA-K bismuth;trifluoride Chemical compound F[Bi](F)F BRCWHGIUHLWZBK-UHFFFAOYSA-K 0.000 description 1
- VDQDGCAHVVNVDM-UHFFFAOYSA-K bismuth;triperchlorate Chemical compound [Bi+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O VDQDGCAHVVNVDM-UHFFFAOYSA-K 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000000080 wetting agent Substances 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 aqueous bath for the electrodeposition of uniform rose to violet-colored gold alloys containing an alkali metal or ammonium dicyanoaurate-I, alkali copper cyanide, alkali metal cyanide, a bismuth compound and optionally organic wetting and brightening agents.
- Bismuth-containing baths are already known, from which two- or three-substance alloys can be galvanically deposited.
- Bismuth trifluoride or bismuth triperchlorate or alkali bismuth mutates are generally used as bismuth compounds, of which the former can only be used in the acidic range and the latter only in the strongly alkaline range, since these compounds are sparingly soluble in the pH range from 6 to 13.
- Baths of this composition are of no technical importance since they are unstable and deposit coatings with only a low gloss.
- the object of the present invention is to provide a stable bismuth-containing gold alloy bath, which enables the deposition of shiny ternary gold alloys with a high bismuth content.
- an aqueous bath of the type mentioned at the outset which is characterized in that it contains a water-soluble complex compound of bismuth as the bismuth compound.
- the bath according to the invention is outstandingly suitable for the deposition of shiny rose-colored to violet-colored ternary gold alloys on decorative objects, such as jewelry, watches and glasses, which is not possible with the known baths of similar composition. It is of particular technical importance that the bismuth can be incorporated into the alloys with extremely high contents up to 30 percent by weight and higher, which opens up further areas of application.
- the bath according to the invention is surprisingly also suitable for the refinement of electronic components, such as plug-in connections, since the precipitates deposited therewith are particularly hard and have good electrical conductivity and excellent abrasion resistance.
- Suitable complex compounds according to the invention are in particular those of bismuth with organic phononic acids, carboxylic acids or amino alcohols.
- Suitable phosphonic acids for the formation of the water-soluble complex compounds of bismuth according to the invention are, for example, those of the general formula in which R 'is hydrogen or a C 1 -C 3 alkyl group, such as methyl, ethyl or propyl, R is a C 1 -C 3 alkylene group, such as methylene, ethylene or trimethylene, and n is an integer from 1 to 3.
- phosphonic acids examples include ethylenediaminetetramethylphosphonic acid, 1-hydroxyrelihiphiphonic acid and 2,3-dihydroxy propylphosphonic acid.
- carboxylic acids can also be used, for example the following general formulas or where X is the group represents, with R 1 in the meaning of hydrogen, C 1 -C 3 alkyl, such as methyl, ethyl or propyl, and n is an integer from 1 to 3.
- carboxylic acids examples include nitrilotriacetic acid, 4-oxyphenylmalonic acid and 1,2-diaminocyclohexanetetraacetic acid.
- carboxylic acids are also polyhydroxy acids, such as d-sugar acid, d-mannosugaric acid, mucic acid, 1,2,3,4-tetrahydroxy-butane-1,1,4-tricarboxylic acid and 3,4,5-trihydroxybenzoic acid.
- suitable amino alcohols for the complexation are those of the general formula wherein R 2 is hydrogen or C 1 -C 3 alkyl, such as methyl, ethyl or propyl, and n represent the numbers 1 or 2.
- a particularly suitable alcohol is, for example, ethylenediaminotetraisopropyl alcohol.
- the soluble complex compounds of bismuth can be prepared before their use according to the invention, for example by the complexing agent with bismuth hydroxide or bismuth nitrate in aqueous solution in a molar ratio of 1 mol bismuth to 1 to 4 mol complexing agent are reacted at room temperature.
- the complexing agent with bismuth hydroxide or bismuth nitrate in aqueous solution in a molar ratio of 1 mol bismuth to 1 to 4 mol complexing agent are reacted at room temperature.
- An aqueous solution which contains alkali metal or ammonium dicyanoaurate-I, alkali copper cyanide, alkali metal cyanide and the water-soluble complex compound of bismuth is generally used as the bath.
- the preferred concentrations are:
- Sodium and potassium salts are advantageously used as the alkali salt.
- the bath can contain customary non-ionic, cationic or anionic wetting agents. These substances can also act as brighteners, in concentrations of 0.01 to 20 g / liter.
- the pH can be from 6 to 13 and, if desired, is adjusted by adding alkali metal hydroxide.
- the bath is expediently operated at temperatures of 20 to 70 ° C., current densities of 0.1 to 3 A / dm preferably being used.
- the pH of 11.5 is adjusted with potassium hydroxide.
- a rose-colored coating with a fineness of 750/000 is deposited at an average current density of 0.4 A / dm 2 .
- the coatings have a hardness of HK 420.
- Precipitation with a purity of 850/000 is separated from this electrolyte.
- the coatings have an unexpectedly high resistance to corrosion and behave excellently in the wear test.
- Precipitation with a purity of 650/000 is deposited from this electrolyte.
- the solderability is excellent.
- the corrosion resistance is good because the coatings are pore-free after only 1 ⁇ m.
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)
- Cosmetics (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833319772 DE3319772A1 (de) | 1983-05-27 | 1983-05-27 | Bad fuer die galvanische abscheidung von goldlegierungen |
| DE3319772 | 1983-05-27 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0126921A2 true EP0126921A2 (fr) | 1984-12-05 |
| EP0126921A3 EP0126921A3 (en) | 1985-01-30 |
| EP0126921B1 EP0126921B1 (fr) | 1989-01-18 |
Family
ID=6200354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84103995A Expired EP0126921B1 (fr) | 1983-05-27 | 1984-04-10 | Bain de dépôt galvanique d'alliages d'or |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4517060A (fr) |
| EP (1) | EP0126921B1 (fr) |
| JP (1) | JPS59232289A (fr) |
| AT (1) | AT383148B (fr) |
| DE (2) | DE3319772A1 (fr) |
| ES (1) | ES532837A0 (fr) |
| HK (1) | HK74389A (fr) |
| IE (1) | IE56353B1 (fr) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0384679A1 (fr) * | 1989-02-20 | 1990-08-29 | Engelhard Corporation | Dépôt électrolytique d'alliages d'or |
| DE3905705A1 (de) * | 1989-02-24 | 1990-08-30 | Degussa | Bad zur galvanischen abscheidung von feingoldueberzuegen |
| 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 |
| DE112021008234T5 (de) | 2021-09-16 | 2024-07-11 | P & S, Galvasols | Hochgeschwindigkeits-elektroformungs- /elektroplattierungsbad für reines gold |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2309032A (en) * | 1996-01-11 | 1997-07-16 | Procter & Gamble | Bismuth salts and complexes with nitrogen-free organic diphosphonic acids |
| DE10110743A1 (de) * | 2001-02-28 | 2002-09-05 | Wieland Dental & Technik Gmbh | Bad zur galvanischen Abscheidung von Gold und Goldlegierungen sowie dessen Verwendung |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2032280A1 (fr) * | 1968-11-28 | 1970-11-27 | Sel Rex Corp | |
| FR2053770A5 (en) * | 1969-07-17 | 1971-04-16 | Radiotechnique Compelec | Electrolytic deposition of gold-bismuth - alloys |
| FR2353656A1 (fr) * | 1976-06-01 | 1977-12-30 | Systemes Traitements Surfaces | Composition d'addition pour bains electrolytiques de placage d'or et d'alliages d'or et son utilisation pour ameliorer ceux-ci |
| FR2405312A1 (fr) * | 1977-10-10 | 1979-05-04 | Oxy Metal Industries Corp | Bains electrolytiques pour le depot d'alliages d'or |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199416A (en) * | 1977-05-03 | 1980-04-22 | Johnson, Matthey & Co., Limited | Composition for the electroplating of gold |
| JPS5951058B2 (ja) * | 1977-07-20 | 1984-12-12 | 松下電器産業株式会社 | 磁気記録再生装置 |
| JPS609117B2 (ja) * | 1980-06-19 | 1985-03-07 | セイコーエプソン株式会社 | 金合金メッキ浴 |
-
1983
- 1983-05-27 DE DE19833319772 patent/DE3319772A1/de active Granted
-
1984
- 1984-04-10 EP EP84103995A patent/EP0126921B1/fr not_active Expired
- 1984-04-10 DE DE8484103995T patent/DE3476225D1/de not_active Expired
- 1984-05-22 IE IE1268/84A patent/IE56353B1/en not_active IP Right Cessation
- 1984-05-22 AT AT0168784A patent/AT383148B/de not_active IP Right Cessation
- 1984-05-25 JP JP59104892A patent/JPS59232289A/ja active Granted
- 1984-05-25 ES ES532837A patent/ES532837A0/es active Granted
- 1984-05-29 US US06/615,471 patent/US4517060A/en not_active Expired - Lifetime
-
1989
- 1989-09-14 HK HK743/89A patent/HK74389A/xx not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2032280A1 (fr) * | 1968-11-28 | 1970-11-27 | Sel Rex Corp | |
| FR2053770A5 (en) * | 1969-07-17 | 1971-04-16 | Radiotechnique Compelec | Electrolytic deposition of gold-bismuth - alloys |
| FR2353656A1 (fr) * | 1976-06-01 | 1977-12-30 | Systemes Traitements Surfaces | Composition d'addition pour bains electrolytiques de placage d'or et d'alliages d'or et son utilisation pour ameliorer ceux-ci |
| FR2405312A1 (fr) * | 1977-10-10 | 1979-05-04 | Oxy Metal Industries Corp | Bains electrolytiques pour le depot d'alliages d'or |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0384679A1 (fr) * | 1989-02-20 | 1990-08-29 | Engelhard Corporation | Dépôt électrolytique d'alliages d'or |
| DE3905705A1 (de) * | 1989-02-24 | 1990-08-30 | Degussa | Bad zur galvanischen abscheidung von feingoldueberzuegen |
| 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 |
| DE112021008234T5 (de) | 2021-09-16 | 2024-07-11 | P & S, Galvasols | Hochgeschwindigkeits-elektroformungs- /elektroplattierungsbad für reines gold |
Also Published As
| Publication number | Publication date |
|---|---|
| US4517060A (en) | 1985-05-14 |
| IE56353B1 (en) | 1991-07-03 |
| AT383148B (de) | 1987-05-25 |
| EP0126921B1 (fr) | 1989-01-18 |
| ES8502741A1 (es) | 1985-02-01 |
| HK74389A (en) | 1989-09-22 |
| ATA168784A (de) | 1986-10-15 |
| DE3476225D1 (en) | 1989-02-23 |
| DE3319772C2 (fr) | 1991-05-16 |
| ES532837A0 (es) | 1985-02-01 |
| JPH0565598B2 (fr) | 1993-09-20 |
| DE3319772A1 (de) | 1984-11-29 |
| IE841268L (en) | 1984-11-27 |
| JPS59232289A (ja) | 1984-12-27 |
| EP0126921A3 (en) | 1985-01-30 |
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