EP0194432A1 - Bain de dépôt galvanique de couches d'alliage d'or-étain - Google Patents
Bain de dépôt galvanique de couches d'alliage d'or-étain Download PDFInfo
- Publication number
- EP0194432A1 EP0194432A1 EP86101083A EP86101083A EP0194432A1 EP 0194432 A1 EP0194432 A1 EP 0194432A1 EP 86101083 A EP86101083 A EP 86101083A EP 86101083 A EP86101083 A EP 86101083A EP 0194432 A1 EP0194432 A1 EP 0194432A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tin
- gold
- bath
- oxalic acid
- acid
- 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
- 229910001128 Sn alloy Inorganic materials 0.000 title claims abstract description 8
- 238000000576 coating method Methods 0.000 title claims description 11
- 230000008021 deposition Effects 0.000 title description 2
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical group [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 title 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 37
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010931 gold Substances 0.000 claims abstract description 26
- 229910052737 gold Inorganic materials 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910001020 Au alloy Inorganic materials 0.000 claims abstract description 8
- JGLCONSOSSTGDG-UHFFFAOYSA-N gold(3+);tetracyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-].N#[C-] JGLCONSOSSTGDG-UHFFFAOYSA-N 0.000 claims abstract description 7
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical class [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004070 electrodeposition Methods 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 45
- 229910052718 tin Inorganic materials 0.000 claims description 32
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910002065 alloy metal Inorganic materials 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229940071182 stannate Drugs 0.000 claims description 3
- 239000000337 buffer salt Substances 0.000 claims 1
- 125000005402 stannate group Chemical group 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- GSMCZRMXOTVCGF-UHFFFAOYSA-N 2-bromo-1-(5-methyl-1,2-oxazol-3-yl)ethanone Chemical compound CC1=CC(C(=O)CBr)=NO1 GSMCZRMXOTVCGF-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003353 gold alloy Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- WOFVPNPAVMKHCX-UHFFFAOYSA-N N#C[Au](C#N)C#N Chemical compound N#C[Au](C#N)C#N WOFVPNPAVMKHCX-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010938 white gold Substances 0.000 description 1
- 229910000832 white gold Inorganic materials 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 bath for the electrodeposition of gold / tin alloy coatings at pH values less than 3, consisting of 1 to 20 g / 1 gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.1 to 10 g / 1 Tin in the form of a water-soluble tin salt, optionally 0.005 to 1 g / 1 of a further alloy metal in the form of a water-soluble salt, an acid and a buffer or conductive salt.
- the galvanic co-deposition of tin from gold baths is of interest for decorative and technical applications.
- decorative industrial gold are / tin - alloy baths for producing color gold coatings, especially white gold layers used, and in electrical engineering, the good corrosion resistance and solderability provides the tin in conjunction with Gold advantages over other alloy layers.
- Tin in combination with gold can only be separated from weakly acid baths, at pH values from 3.5 to 6, if it is divalent.
- the electrolytes contain the gold in the form of potassium dicyano-aurate (I), KAutCN) 2 _
- Such electrolytes are known from DE-OS 1 960 047 and DE-AS 25 23 510.
- these baths are not stable since divalent tin is oxidized relatively easily to tetravalent, which is no longer deposited under the given conditions.
- Protective substances such as complexing agents, sulfonic acids or soluble tin anodes cannot adequately prevent oxidation.
- DE-OS 26 58 003 and DE-PS 30 12 999 the co-deposition of tin from strongly acidic gold electrolytes at pH values less than 3 is known, which the gold in the form of the tetracyanoaurate (III) complex Au (CN) 4 included. In these baths, the tin is separated from the divalent and tetravalent oxidation stage.
- DE-OS 26 58 003 describes a galvanic bath which contains 1 to 30 g / 1 gold as a gold (III) cyanide complex and 1 to 150 g / 1 tin as a halogen stannate (IV) complex Adjustment of the pH value and to stabilize the complex of hydrogen halide acids, which lead to considerable corrosion damage to the galvanic systems. In addition, poisonous halogen is developed at the anode during electrolysis, which escapes in gaseous form under the given working conditions.
- a bath for the electrodeposition of gold / tin alloy layers at pH values less than 3 consisting of 1 to 20 g / 1 gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.1 to 10 g / 1 tin in the form of a water-soluble tin salt, optionally
- the bath contains the tin in the form of a tin (IV) oxalato complex.
- V or preferably it contains the complex in the form of potassium oxalatostannate (IV).
- oxalato tin (IV) acid can also be used, for example.
- oxalic acid or oxalic acid and ammonium sulfate are used as buffer or conductive salts. 10 to 50 g / 1 oxalic acid or mixtures of 10 to 50 g / l oxalic acid and 10 to 100 g / 1 ammonium sulfate are preferably used.
- the bath can additionally contain 0.005 to 1 g / l of a further alloy metal in the form of a water-soluble nickel or cobalt salt.
- the pH of the bath is advantageously adjusted to 0.5 to 2.5 using sulfuric acid or oxalic acid.
- the bath is normally used at temperatures between 20 and 60 ° C, preferably at 40 to 55 ° C, and current densities of 0.2 to 5 A / dm 2 , preferably 1 to 4 A / dm 2 .
- Oxalato tin (IV) acid is produced, for example, by dissolving tin in oxalic acid with the addition of hydrogen peroxide, potassium oxalate stannate (IV) by reacting tin (IV) chloride with potassium oxalate. Thanks to the use of tin in grade 4 and in a complex bond, the bath is stable against oxidation. No tin acid is excreted.
- these gold / tin alloy baths with oxalato complexes without special gloss additives, such as salts of semi-metals such as selenium or tellurium or organic compounds provide shiny coatings over a wide current density range with high current yields of approx. 90%.
- the additional co-deposition of cobalt or nickel can influence the color and the technological properties, such as hardness and mechanical abrasion resistance, of the coatings.
- the current yield then drops to values of 40 to 50%.
- the very low content of non-metallic impurities in the coatings is also surprising. At less than 0.1%, it is far below that of comparable gold alloy coatings.
- the coatings are also high hardness despite very ductile (HV 0th 015 230).
- the elongation at break measured at 10 ⁇ m thick layers on a copper foil is around 20% in the order of that of fine gold layers.
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 |
|---|---|---|---|
| DE3509367A DE3509367C1 (de) | 1985-03-15 | 1985-03-15 | Bad und Verfahren zur galvanischen Abscheidung von Gold/Zinn-Legierungsueberzuegen |
| DE3509367 | 1985-03-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0194432A1 true EP0194432A1 (fr) | 1986-09-17 |
| EP0194432B1 EP0194432B1 (fr) | 1988-06-15 |
Family
ID=6265335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86101083A Expired EP0194432B1 (fr) | 1985-03-15 | 1986-01-28 | Bain de dépôt galvanique de couches d'alliage d'or-étain |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4634505A (fr) |
| EP (1) | EP0194432B1 (fr) |
| JP (1) | JPH0684553B2 (fr) |
| BR (1) | BR8601029A (fr) |
| DE (2) | DE3509367C1 (fr) |
| HK (1) | HK58191A (fr) |
| ZA (1) | ZA86309B (fr) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH680370A5 (fr) * | 1989-12-19 | 1992-08-14 | H E Finishing Sa | |
| DE4406434C1 (de) * | 1994-02-28 | 1995-08-10 | Heraeus Gmbh W C | Bad zum galvanischen Abscheiden von Gold-Zinn-Legierungen |
| US20060237324A1 (en) * | 2003-05-21 | 2006-10-26 | Fred Hayward | Pulse plating process for deposition of gold-tin alloy |
| US7431817B2 (en) * | 2004-05-11 | 2008-10-07 | Technic, Inc. | Electroplating solution for gold-tin eutectic alloy |
| WO2006078549A1 (fr) * | 2005-01-21 | 2006-07-27 | Technic, Inc. | Procede de placage par impulsions pour depot d'un alliage or/etain |
| CN114759182B (zh) * | 2022-05-25 | 2023-04-07 | 昆明理工大学 | 石墨烯包覆草酸锡负极材料及其制备方法、电池 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4013523A (en) * | 1975-12-24 | 1977-03-22 | Oxy Metal Industries Corporation | Tin-gold electroplating bath and process |
| FR2538816A1 (fr) * | 1983-01-04 | 1984-07-06 | Omi Int Corp | Bain pour former, par electrolyse, un revetement en alliage d'or et procede d'utilisation de ce bain |
| FR2558853A1 (fr) * | 1984-02-01 | 1985-08-02 | Omi Int Corp | Bain exempt de citrate pour deposer, par electrolyse, des alliages d'or et son procede d'utilisation |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3475290A (en) * | 1965-05-07 | 1969-10-28 | Suwa Seikosha Kk | Bright gold plating solution and process |
| GB1442325A (en) * | 1972-07-26 | 1976-07-14 | Oxy Metal Finishing Corp | Electroplating with gold and gold alloys |
| DE3012999C2 (de) * | 1980-04-03 | 1984-02-16 | Degussa Ag, 6000 Frankfurt | Bad und Verfahren zur galvanischen Abscheidung von hochglänzenden und duktiler Goldlegierungsüberzügen |
-
1985
- 1985-03-15 DE DE3509367A patent/DE3509367C1/de not_active Expired
-
1986
- 1986-01-15 ZA ZA86309A patent/ZA86309B/xx unknown
- 1986-01-28 DE DE8686101083T patent/DE3660313D1/de not_active Expired
- 1986-01-28 EP EP86101083A patent/EP0194432B1/fr not_active Expired
- 1986-02-26 US US06/833,228 patent/US4634505A/en not_active Expired - Fee Related
- 1986-03-11 BR BR8601029A patent/BR8601029A/pt unknown
- 1986-03-14 JP JP61055187A patent/JPH0684553B2/ja not_active Expired - Lifetime
-
1991
- 1991-07-25 HK HK581/91A patent/HK58191A/xx unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4013523A (en) * | 1975-12-24 | 1977-03-22 | Oxy Metal Industries Corporation | Tin-gold electroplating bath and process |
| FR2538816A1 (fr) * | 1983-01-04 | 1984-07-06 | Omi Int Corp | Bain pour former, par electrolyse, un revetement en alliage d'or et procede d'utilisation de ce bain |
| FR2558853A1 (fr) * | 1984-02-01 | 1985-08-02 | Omi Int Corp | Bain exempt de citrate pour deposer, par electrolyse, des alliages d'or et son procede d'utilisation |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA86309B (en) | 1986-08-27 |
| EP0194432B1 (fr) | 1988-06-15 |
| DE3660313D1 (en) | 1988-07-21 |
| JPH0684553B2 (ja) | 1994-10-26 |
| BR8601029A (pt) | 1986-11-25 |
| JPS61223194A (ja) | 1986-10-03 |
| HK58191A (en) | 1991-08-02 |
| US4634505A (en) | 1987-01-06 |
| DE3509367C1 (de) | 1986-08-14 |
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