EP2730682A1 - Solution alcaline sans cyanure pour l'électrodéposition d'alliages d'or, procédé d'électrodéposition et substrat comprenant un dépôt anticorrosion brillant d'un alliage d'or - Google Patents
Solution alcaline sans cyanure pour l'électrodéposition d'alliages d'or, procédé d'électrodéposition et substrat comprenant un dépôt anticorrosion brillant d'un alliage d'or Download PDFInfo
- Publication number
- EP2730682A1 EP2730682A1 EP12192458.3A EP12192458A EP2730682A1 EP 2730682 A1 EP2730682 A1 EP 2730682A1 EP 12192458 A EP12192458 A EP 12192458A EP 2730682 A1 EP2730682 A1 EP 2730682A1
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- EP
- European Patent Office
- Prior art keywords
- electroplating
- gold
- electroplating solution
- deposit
- ions
- 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.)
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- 238000009713 electroplating Methods 0.000 title claims abstract description 86
- 239000000758 substrate Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910001020 Au alloy Inorganic materials 0.000 title description 5
- 239000003353 gold alloy Substances 0.000 title description 5
- 239000010931 gold Substances 0.000 claims abstract description 50
- 229910052737 gold Inorganic materials 0.000 claims abstract description 44
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 24
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005260 corrosion Methods 0.000 claims abstract description 8
- 230000007797 corrosion Effects 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- 239000011701 zinc Substances 0.000 claims description 33
- 229910052725 zinc Inorganic materials 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 239000008139 complexing agent Substances 0.000 claims description 16
- -1 gold ions Chemical class 0.000 claims description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 13
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 11
- 229940091173 hydantoin Drugs 0.000 claims description 11
- 229910001449 indium ion Inorganic materials 0.000 claims description 11
- 239000000600 sorbitol Substances 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 10
- 239000006172 buffering agent Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 150000005846 sugar alcohols Chemical class 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 235000001014 amino acid Nutrition 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 235000014633 carbohydrates Nutrition 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 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
- 150000003464 sulfur compounds Chemical class 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 31
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 231100000167 toxic agent Toxicity 0.000 abstract description 4
- 238000004070 electrodeposition Methods 0.000 abstract description 3
- 150000002825 nitriles Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 58
- 229910001369 Brass Inorganic materials 0.000 description 23
- 239000010951 brass Substances 0.000 description 23
- 239000011550 stock solution Substances 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- 229910052738 indium Inorganic materials 0.000 description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 238000007747 plating Methods 0.000 description 10
- 239000002738 chelating agent Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229910002065 alloy metal Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 7
- 150000004699 copper complex Chemical class 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000005282 brightening Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 5
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- SXKZZFLSYPUIAN-UHFFFAOYSA-N [Cu].[Zn].[Au] Chemical compound [Cu].[Zn].[Au] SXKZZFLSYPUIAN-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000019798 tripotassium phosphate Nutrition 0.000 description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 4
- 235000019801 trisodium phosphate Nutrition 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 238000005494 tarnishing Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- WNDUPUMWHYAJOR-SADXPQEKSA-K (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;2-hydroxypropane-1,2,3-tricarboxylate;iron(3+) Chemical compound [Fe+3].OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WNDUPUMWHYAJOR-SADXPQEKSA-K 0.000 description 1
- QWPBWIRUYTZEFI-UHFFFAOYSA-N 2-pyridin-2-ylprop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CC=N1 QWPBWIRUYTZEFI-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical class O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
Images
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
-
- 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
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
Definitions
- the present invention relates to an electroplating solution which is free of cyanides and toxic compounds for the electrodeposition of bright deposits of gold-copper alloys.
- substrates are provided which comprise a bright gold-copper alloy deposit which is corrosion resistant according to NFS 80772, ISO 4538 and/or ISO 9227 and has 14 to 22 karats of gold in the alloy.
- the inventive electroplating solution allows electroplating of gold-copper alloy deposits which have a color matching the Swiss standard ISO 8654 from 0.5 N to 5 N.
- the invention provides a method for electroplating a gold-copper alloy deposit on a substrate.
- the inventive electroplating solution may be used for electroplating a substrate selected from the group consisting of decorative substrates, jewelry, watches and eyeglass trade.
- Japanese Patent publication No. 2005-256072 discloses a different complex discovered few years ago, using hydantoin compounds as chelating agent and starting from trivalent gold compounds e.g. gold hydroxide salt or chloroaurate gold.
- this gold complex was found to be unstable regarding the electroless deposit that occurs after a month when complexed gold and conductive salts were in the same bath.
- the object of the present invention was to provide a cyanide-free and toxic compounds free solution for electroplating of a gold-copper alloy which meets the characteristics cited above.
- the solution to the problem is provided with the alkaline, cyanide-free solution for electroplating of a gold-copper alloy according to claim 1, the method for electroplating a gold-copper alloy deposit on a substrate according to claim 11, the substrate comprising a bright, electroplated deposit of a gold-copper alloy according to claim 12 and the use according to claim 15.
- the dependent claims show advantageous embodiments.
- the present invention provides an alkaline, cyanide-free electroplating solution for electroplating a gold-copper alloy, comprising
- the inventive electroplating solution is suitable for electroplating a gold-copper alloy deposit on a substrate, wherein the deposit has the following characteristics:
- the inventive alkaline, cyanide-free electroplating solution must comprise a sulfite salt concentration of at least 60 g/L, preferably in the range of 60 to 200 g/L. At this concentration, the sulfite salt may prevent deposit of gold on tank walls over time.
- the concentration of the sulfite salt may be 65 to 160 g/L, preferably 70 to 120 g/L, more preferably 75 to 100 g/L. Especially at concentrations ⁇ 70 g/L, it was discovered that the stability of the electroplating solution over time is significantly improved.
- Sulfite salts which may be comprised in the inventive solution are sodium sulfite and/or potassium sulfite.
- the gold ions in the inventive solution are at least partially complexed by hydantoin or its derivatives.
- the molar ratio between gold ions and hydantoin, a salt or a derivative thereof is 1:2 to 1:6, preferably 1:2.5 to 1:5, more preferably 1:3 to 1:4.
- a ratio in this range is favorable for complexing gold ions by hydantoin and thus increasing the stability of the electroplating solution.
- the concentration of the copper ions may be 0.2 to 10 g/L more preferably 0.5 to 7.5 g/L and most preferably 1 to 5 g/L.
- the electroplating solution according to the present invention may further comprise ions of metals which can improve the final characteristics of the plated gold-copper alloy deposit.
- ions of metals which can improve the final characteristics of the plated gold-copper alloy deposit.
- zinc, iron and/or indium ions are comprised in the inventive alkaline plating solution, the final gold-copper alloy deposit has an improved brightness.
- the addition of said metal ions allows to selectively regulate the color of the deposit which is produced after electroplating.
- a suitable concentration range of the zinc, iron and/or indium ions is 10 mg/L to 3 g/L, preferably 20 mg/L to 1 g/L, more preferably 50 mg/L to 500 mg/L.
- the brightness of the electrode or substrate which is electroplated with the inventive solution can be further improved if all three metal ions i.e. zinc, iron as well as indium ions are comprised in the solution.
- the electroplating solution comprises a brightening agent.
- Suitable brightening agents increase the codeposition of zinc, iron and/or indium metal in the deposit.
- the addition of a brightening agent allows obtaining a 1 N color when zinc ions are comprised in the inventive solution.
- Examples for brightening agents according to the invention are pyridine sulfonic acid, trans pyridyl acrylic acid, nicotinic acid and/or antimony.
- Antimony may be in the form of KSb(OH) 6 . Antimony was found to be suitable for significantly improving the brightness of the deposit.
- the concentration of the brightening agent will be comprised between 0.01 to 1 g/L more preferably between 10 and 500 mg/L.
- the copper ions or the zinc, iron and/or indium ions may be complexed in solution by a complexing agent.
- the complexing agent may be selected from the group consisting of carbohydrates, amino acids, sulfur compounds and sugar alcohols, preferably selected from the group consisting of sorbitol, mannitol, gluconate, erithrytol, xylitol, nitrilotriacetic acid, cysteine.
- Said complexing agents were found to be perfectly suited for complexing e.g. copper, zinc, iron and/or indium ions.
- the complexing agent may have a concentration of 0.1 to 60 g/L, preferably 0.5 to 40 g/L, more preferably 1 to 20 g/L, most preferably 1.5 to 10 g/L.
- a concentration in these ranges is sufficient for complexing the copper ions which are comprised in the inventive alkaline electroplating solution as well as optionally zinc, iron and/or indium ions.
- a concentration of complexing agent above 75 g/L was found to be detrimental for some type of metal ions. For example, for copper ions, a concentration of a chelating agent above 75 g/L will lead to the reduction of copper (II) into copper (0) and lead to the formation of a brick-red copper precipitate.
- the concentration of the complexing agent is dependent on the concentration of the copper ions or optionally the zinc, iron and/or indium ions.
- the ratio of the chelating agent concentration to the concentration of alloy metal ions ranges from 1 : 0.25 to 1:1. This range was found to be sufficient for suitable complexation of the alloy metal ions.
- the electroplating solution according to the present invention may further comprise a buffering agent, preferably a buffering agent which is selected from the group consisting of phosphate (e.g. K 3 PO 4 , HK 2 PO 4 , H 2 KPO 4 , or the corresponding sodium phosphate salt), formiate (e.g. sodium formiate), pyrophosphate (e.g. tetrapotassium pyrophosphate) and citrate (e.g. sodium citrate).
- phosphate e.g. K 3 PO 4 , HK 2 PO 4 , H 2 KPO 4 , or the corresponding sodium phosphate salt
- formiate e.g. sodium formiate
- pyrophosphate e.g. tetrapotassium pyrophosphate
- citrate e.g. sodium citrate
- the buffering agent may have a concentration of 30 to 300 g/L, preferably 40 to 200 g/L, more preferably 50 to 100 g/L. A concentration in this range is suitable for keeping the pH of the inventive electroplating solution constant for many turnovers (TOs) of the electroplating solution.
- TOs turnovers
- the pH of the alkaline electroplating solution may be pH 10 to 14, preferably pH 11 to 13, more preferably pH 12 to 13. It was discovered that a pH in this range was found to improve the bath stability and brightness of the deposits. This is especially true for a pH above pH 11. Importantly, it was discovered that the copper complex in the electroplating solution becomes unstable at a pH ⁇ 11. In terms of long term stability of components which contact the inventive solution, a pH lower or equal to 13 is beneficial compared to a pH which is higher than pH 13 since the corrosive potential (concentration of the OH - ions) of the solution is higher at pH > 13 and the aspect of the deposit becomes drabber.
- the electroplating solution may be at a temperature of 20 to 80 °C, preferably 30 to 70 °C, more preferably 40 to 60 °C. This temperature range was found to be the best compromise between bath stability and process efficiency during electroplating. This is especially true for a temperature in the range of 40 to 60 °C,
- the inventive electroplating solution can further comprise a wetting agent.
- a wetting agent in the electroplating solution is that hydrogen formation during electroplating is reduced.
- Preferred wetting agents are selected from the group consisting of cocamido propyl betaine, ethoxy ester phosphate and sodium lauryl ether sulfate.
- the invention further provides a method for electroplating a gold alloy deposit on an electrode or substrate, the method comprising electroplating the electrode or substrate with the inventive electroplating solution for 5 to 30 minutes at a current density of 0.1 to 4 A/dm 2 , characterized in that the electroplating solution is kept at a constant temperature of 20 to 80 °C.
- the current density preferably ranges from 0.8 A/dm 2 to 2.2 A/dm 2 , more preferably 1.0 A/dm 2 to 2.0 A/dm 2 . It was discovered that a current density lower than 1 A/dm 2 leads to a satin aspect and with more than 2 A/dm 2 , the deposit is burned.
- the electroplating solution is kept at a constant temperature of 30 to 70 °C, more preferably at a temperature of 40 to 60°C.
- an electrode or substrate comprising a bright, electroplated deposit of a gold-copper alloy is provided, characterized in that the deposit has 14 to 22 karats of gold in the alloy and is corrosion resistant according to NFS 80772, ISO 4538 and/or ISO 9227.
- the electrode or substrate has a color matching the Swiss standard ISO 8654 from 0.5 N to 5 N and/or has excellent stability.
- the color of the electrode or substrate matching the Swiss standard ISO 8654 may be regulated by varying the ratio of alloy metal ions to gold ions in the inventive solution and may e.g. be 0,5 N, 1 N, 1.5 N, 2 N, 2.5 N, 3 N, 3.5 N, 4 N, 4.5 N or 5 N, or any value in between said values. Stability of the color is excellent i.e. the color is stable for at least 6 months without modification of the Lab color coordinates.
- the inventive electrode or substrate is producible by the inventive method.
- the inventive electroplating solution may be used for electroplating an electrode or substrate selected from the group consisting of decorative substrates, jewelry, watches and eyeglass trade.
- a complex of gold and hydantoin is obtained after a reaction between trivalent gold coming from HAuCl 4 and an hydantoin-based compound, preferably 5,5 dimethylhydantoin.
- the complex is stabilized by adding a sulfite salt to the solution, preferably Na 2 SO 3 or K 2 SO 3 .
- the solution is kept between pH 12 and 13.
- a complex of copper ions with a complexing agent is to be produced.
- the copper ions remain equimolar or in a molar excess to the sugar alcohol, preferably equimolar to a 4-fold molar excess.
- a base e.g. NaOH
- an alkaline pH pH ⁇ 14
- This copper complex solution is then mixed with the solution obtained in Example 1 to produce an alkaline, cyanide-free solution for electroplating of a gold-copper alloy.
- the cyanide-free solution comprises up to 3 g/L of zinc, iron and/or indium ions, the brightness and the color tone of the gold alloy deposit obtained with the present invention is improved. If desired, the amount or type of chelating agent in the cyanide-free solution may be adjusted. In order to achieve excellent brightness and color tone, certain molar ratios or molarities of chelating agents dependent on the type of ions [Fe 3+ , Zn 2+ or In 3+ ) were found to be beneficial (see Tables 1 and 2).
- the conductive substrate to be treated in the first case a substrate made of brass, was prepared using the Coventya S.A.S. brass substrate preparation product PRESOL 7073 as cleaner and PICKLANE 33 as activator of the surface.
- the electroplating was performed with the following alkaline, cyanide-free electroplating solution: - Gold (as Au(5,5-dimethylhydantoin) 3 ): 3 g/L - Copper (as Cu 2 (sorbitol)): 2 g/L - Zinc (as Zn 2 (sorbitol)): 50 mg/L - Potassium or Sodium Phosphate tri basic: 100 g/L - Sodium sulfite: 75 g/L (Comprising ca. 9.75 g/L from the gold stock solution) pH is adjusted to pH 12 (with phosphoric acid)
- the gold complex comes from the gold stock solution prepared as described in example 1
- the copper complex comes from the copper stock solution prepared as described in example 2
- the zinc complex comes from the zinc stock solution prepared as described in example 3, table 1.
- the electroplating was performed at 50 °C, since this temperature turned out to be the best compromise between the electrolyte efficiency and the zinc deposition which is disturbed by high temperature.
- the same electrolyte solution was employed for electroplating a brass substrate having a white bronze under layer and a brass substrate having a nickel under layer.
- the same electroplating parameters were used (1 A/dm 2 for 10 min.).
- the deposit produced was very bright, with a 5 N color (regarding the ISO 8654 standard) and an excellent resistance to tarnishing. Yet, the tarnishing resistance was better with a white under layer. Furthermore, the deposits were free of any faults such as pitting or stress cracking and demonstrated an excellent resistance to corrosion.
- the conductive substrate to be treated in the first case a substrate made of brass, was prepared using the Coventya S.A.S. brass substrate preparation product PRESOL 7073 as cleaner and PICKLANE 33 as activator of the surface.
- the electroplating was performed with the following alkaline, cyanide-free electroplating solution: - Gold (as Au(5,5-dimethylhydantoin) 3 ): 3 g/L - Copper (as Cu 2 (sorbitol)): 2 g/L - Zinc (as Zn 2 (sorbitol)): 350 mg/L - Antimony (as KSb(OH) 6 ): 500 mg/L - Potassium or Sodium Phosphate tri basic: 100 g/L - Sodium sulfite: 75 g/L (Comprising ca. 9.75 g/L from the gold stock solution) pH is adjusted to pH 12 (with phosphoric acid)
- the gold complex comes from the gold stock solution prepared as described in example 1
- the copper complex comes from the copper stock solution prepared as described in example 2
- the zinc complex comes from the zinc stock solution prepared as described in example 3, table 1.
- the electroplating was performed at 50 °C, since this temperature turned out to be the best compromise between the electrolyte efficiency and the zinc deposition which is disturbed by high temperature.
- the same electrolyte solution was employed for electroplating a brass substrate having a white bronze under layer and a brass substrate having a nickel under layer.
- the same electroplating parameters were used (1 A/dm 2 for 10 min.).
- the deposit produced was very bright, with a 1 N color (regarding the ISO 8654 standard) and an excellent resistance to tarnishing. Furthermore, the deposits were free of any faults such as pitting or stress cracking and demonstrated an excellent resistance to corrosion.
- the conductive substrates to be treated were brass hull cells.
- the brass hull cells were prepared using the Coventya S.A.S. brass substrate preparation product PRESOL 7073 as cleaner and PICKLANE 33 as activator of the surface.
- the electroplating was performed with the following alkaline, cyanide-free electroplating solutions, comprising different alloy metals and complexing agents, respectively (see Figure 1 ): - Gold (as Au(5,5-dimethylhydantoin) 3 ): 3 g/L - Copper (as Cu 2 (sorbitol)): 2 g/L - Alloy metal type and concentration: 50 - 200 mg/L - Complexing agent type and concentration: see Table 4 - Potassium or Sodium Phosphate tri-basic: 100 g/L - Sodium sulfite: 75 g/L (Comprising ca. 9.75 g/L from the gold stock solution) pH is adjusted to pH 12 (with phosphoric acid)
- the gold complex comes from the gold stock solution prepared as described in example 1 and the copper complex comes from the copper stock solution prepared as described in example 2.
- Plating was performed with a current density of 1 A/dm 2 for 10 minutes. Characteristics of the deposits after electroplating are highlighted in Figure 1 .
- the conductive substrate to be treated was brass hull cells.
- the brass hull cells were prepared using the Coventya S.A.S. brass substrate preparation product PRESOL 7073 as cleaner and PICKLANE 33 as activator of the surface.
- the electroplating was performed with the following alkaline, cyanide-free electroplating solutions comprising different amounts of copper as alloy metal: - Gold (as Au(5,5-dimethylhydantoin) 3 ): 3 g/L - Copper (as Cu 2 (sorbitol)): 1-4 g/L - Zinc (as Zn 2 (sorbitol)): 25 - 150 mg/L - Potassium or Sodium Phosphate tri-basic: 100 g/L - Sodium sulfite: 75 g/L (Comprising ca. 9.75 g/L from the gold stock solution) pH is adjusted to pH 12 (with phosphoric acid)
- the gold complex comes from the gold stock solution prepared as described in example 1
- the copper complex comes from the copper stock solution prepared as described in example 2
- the zinc complex comes from the zinc stock solution prepared as described in example 3, table 1.
- Plating was performed with a current density of 1 A/dm 2 for 10 minutes.
- the relationship between copper concentration in the electrolyte and the karat of the deposit is highlighted in Table 3: Table 3 Cu content 1 g/L 2 g/L 3 g/L 4 g/L Zn content 25 mg/L 50 mg/L 75 mg/L 100 mg/L Karats 20 KT 18 KT 16 KT 14 KT
- Table 4 shows the dependency of the aspect and color of a deposit produced with variants of the inventive electroplating solutions.
- all deposits are bright if indium, iron or zinc ions were comprised in the inventive electroplating solution.
- the color of the deposit can be selectively regulated by the type of alloy ions (e.g. zinc, indium or iron) which are comprised in the electroplating solution.
- Example alloying metal complexing agent molar ratio of alloy metal : complexing agent alloy metal concentration aspect of the deposit color of the deposit 7 indium NTA 1:2 50 - 200 mg/L Bright From pink to grey as indium content increases 7 indium Sorbitol 1:5 50 - 200 mg/L Bright From pink to grey as indium content increases 7 indium Cysteine 1:4 50 - 200 mg/L Bright From pink to grey as indium content increases 7 iron Sorbitol 1:3 50 - 200 mg/L Bright From pink to 0.5 N color as iron content increases
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- Electroplating And Plating Baths Therefor (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES12192458.3T ES2685317T3 (es) | 2012-11-13 | 2012-11-13 | Solución alcalina, sin cianuro, para electrochapado de aleaciones de oro, un método para electrochapado y un sustrato que comprende un depósito brillante, sin corrosión, de una aleación de oro |
PT12192458T PT2730682T (pt) | 2012-11-13 | 2012-11-13 | Solução alcalina, sem cianeto, para eletrodeposição de ligas de ouro, um método para eletrodepositar e um substrato compreendendo um depósito brilhante e sem corrosão de uma liga de ouro |
PL12192458T PL2730682T3 (pl) | 2012-11-13 | 2012-11-13 | Alkaliczny, bezcyjankowy roztwór do galwanizacji stopami złota, sposób galwanizacji i podłoże zawierające błyszczący, wolny od korozji osad stopu złota |
TR2018/11860T TR201811860T4 (tr) | 2012-11-13 | 2012-11-13 | Altın alaşımlarını elektro kaplamaya yönelik alkali, siyanürsüz çözelti, elektro kaplamaya yönelik bir yöntem ve bir altın alaşımının bir parlak, aşınmayan birikimini içeren bir substrat. |
EP12192458.3A EP2730682B1 (fr) | 2012-11-13 | 2012-11-13 | Solution alcaline sans cyanure pour l'électrodéposition d'alliages d'or, procédé d'électrodéposition et substrat comprenant un dépôt anticorrosion brillant d'un alliage d'or |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12192458.3A EP2730682B1 (fr) | 2012-11-13 | 2012-11-13 | Solution alcaline sans cyanure pour l'électrodéposition d'alliages d'or, procédé d'électrodéposition et substrat comprenant un dépôt anticorrosion brillant d'un alliage d'or |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2730682A1 true EP2730682A1 (fr) | 2014-05-14 |
EP2730682B1 EP2730682B1 (fr) | 2018-07-25 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP12192458.3A Active EP2730682B1 (fr) | 2012-11-13 | 2012-11-13 | Solution alcaline sans cyanure pour l'électrodéposition d'alliages d'or, procédé d'électrodéposition et substrat comprenant un dépôt anticorrosion brillant d'un alliage d'or |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2730682B1 (fr) |
ES (1) | ES2685317T3 (fr) |
PL (1) | PL2730682T3 (fr) |
PT (1) | PT2730682T (fr) |
TR (1) | TR201811860T4 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105132973A (zh) * | 2015-09-22 | 2015-12-09 | 太原工业学院 | 一种环保型无氰电镀铜锌合金溶液及其电镀铜锌合金工艺 |
CN110699713A (zh) * | 2019-11-21 | 2020-01-17 | 长春黄金研究院有限公司 | 一种无氰金合金电铸液及其使用方法 |
CN110699721A (zh) * | 2019-11-20 | 2020-01-17 | 长春黄金研究院有限公司 | 一种无氰镀金铜合金电镀液及其应用 |
CN114075680A (zh) * | 2020-08-21 | 2022-02-22 | 江苏澳光电子有限公司 | 一种耐腐蚀水封电镀液 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5340529A (en) * | 1993-07-01 | 1994-08-23 | Dewitt Troy C | Gold jewelry alloy |
US5750018A (en) * | 1997-03-18 | 1998-05-12 | Learonal, Inc. | Cyanide-free monovalent copper electroplating solutions |
US6511589B1 (en) * | 2001-08-17 | 2003-01-28 | Electroplating Engineers Of Japan Limited | Gold plating solution and gold plating method using thereof |
EP1321468A1 (fr) * | 2001-12-19 | 2003-06-25 | Tanaka Kikinzoku Kogyo K.K. | Complex d'or sur base d'hydantoine |
JP2005256072A (ja) | 2004-03-11 | 2005-09-22 | Tanaka Kikinzoku Kogyo Kk | 金錯体 |
EP1728898A2 (fr) * | 2005-06-02 | 2006-12-06 | Rohm and Haas Electronic Materials LLC | Electrolyte pour le dêpot des alliages à base d'or |
-
2012
- 2012-11-13 PL PL12192458T patent/PL2730682T3/pl unknown
- 2012-11-13 ES ES12192458.3T patent/ES2685317T3/es active Active
- 2012-11-13 TR TR2018/11860T patent/TR201811860T4/tr unknown
- 2012-11-13 EP EP12192458.3A patent/EP2730682B1/fr active Active
- 2012-11-13 PT PT12192458T patent/PT2730682T/pt unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5340529A (en) * | 1993-07-01 | 1994-08-23 | Dewitt Troy C | Gold jewelry alloy |
US5750018A (en) * | 1997-03-18 | 1998-05-12 | Learonal, Inc. | Cyanide-free monovalent copper electroplating solutions |
US6511589B1 (en) * | 2001-08-17 | 2003-01-28 | Electroplating Engineers Of Japan Limited | Gold plating solution and gold plating method using thereof |
EP1321468A1 (fr) * | 2001-12-19 | 2003-06-25 | Tanaka Kikinzoku Kogyo K.K. | Complex d'or sur base d'hydantoine |
JP2005256072A (ja) | 2004-03-11 | 2005-09-22 | Tanaka Kikinzoku Kogyo Kk | 金錯体 |
EP1728898A2 (fr) * | 2005-06-02 | 2006-12-06 | Rohm and Haas Electronic Materials LLC | Electrolyte pour le dêpot des alliages à base d'or |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105132973A (zh) * | 2015-09-22 | 2015-12-09 | 太原工业学院 | 一种环保型无氰电镀铜锌合金溶液及其电镀铜锌合金工艺 |
CN110699721A (zh) * | 2019-11-20 | 2020-01-17 | 长春黄金研究院有限公司 | 一种无氰镀金铜合金电镀液及其应用 |
CN110699713A (zh) * | 2019-11-21 | 2020-01-17 | 长春黄金研究院有限公司 | 一种无氰金合金电铸液及其使用方法 |
CN114075680A (zh) * | 2020-08-21 | 2022-02-22 | 江苏澳光电子有限公司 | 一种耐腐蚀水封电镀液 |
Also Published As
Publication number | Publication date |
---|---|
PL2730682T3 (pl) | 2018-12-31 |
TR201811860T4 (tr) | 2018-09-21 |
ES2685317T3 (es) | 2018-10-08 |
EP2730682B1 (fr) | 2018-07-25 |
PT2730682T (pt) | 2018-11-09 |
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