EP0193848A1 - Galvanisches Bad für das Elektroplattieren von Goldlegierungen - Google Patents
Galvanisches Bad für das Elektroplattieren von Goldlegierungen Download PDFInfo
- Publication number
- EP0193848A1 EP0193848A1 EP86102442A EP86102442A EP0193848A1 EP 0193848 A1 EP0193848 A1 EP 0193848A1 EP 86102442 A EP86102442 A EP 86102442A EP 86102442 A EP86102442 A EP 86102442A EP 0193848 A1 EP0193848 A1 EP 0193848A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- amino
- acid
- gold
- cyanide
- copper
- 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
- 229910001020 Au alloy Inorganic materials 0.000 title claims description 4
- 239000003353 gold alloy Substances 0.000 title claims description 4
- 238000004070 electrodeposition Methods 0.000 title 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 49
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052737 gold Inorganic materials 0.000 claims abstract description 19
- 239000010931 gold Substances 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 16
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract 3
- 230000002999 depolarising effect Effects 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 7
- 159000000011 group IA salts Chemical group 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 5
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- IYOSFCQQBJPCTM-UHFFFAOYSA-N [Zn].[Cd].[Cu].[Au] Chemical group [Zn].[Cd].[Cu].[Au] IYOSFCQQBJPCTM-UHFFFAOYSA-N 0.000 claims description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229940073608 benzyl chloride Drugs 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000007859 condensation product Substances 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 235000001968 nicotinic acid Nutrition 0.000 claims description 3
- 229960003512 nicotinic acid Drugs 0.000 claims description 3
- 239000011664 nicotinic acid Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- DLPNNXVXJKWJTK-UHFFFAOYSA-M sodium;hydroxy-(4-methoxyphenyl)methanesulfonate Chemical compound [Na+].COC1=CC=C(C(O)S([O-])(=O)=O)C=C1 DLPNNXVXJKWJTK-UHFFFAOYSA-M 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- PNEBXWLVOMLIPS-UHFFFAOYSA-N benzyl pyridine-2-carboxylate Chemical compound C=1C=CC=NC=1C(=O)OCC1=CC=CC=C1 PNEBXWLVOMLIPS-UHFFFAOYSA-N 0.000 claims description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical class CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 150000003566 thiocarboxylic acids Chemical class 0.000 claims description 2
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- CKLJMWTZIZZHCS-UHFFFAOYSA-N Aspartic acid Chemical compound OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 claims 1
- COTCLZIUSPWWJJ-UHFFFAOYSA-M [Na+].[O-]S(=O)=S Chemical compound [Na+].[O-]S(=O)=S COTCLZIUSPWWJJ-UHFFFAOYSA-M 0.000 claims 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims 1
- 235000003704 aspartic acid Nutrition 0.000 claims 1
- 150000001509 aspartic acid derivatives Chemical class 0.000 claims 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 235000013922 glutamic acid Nutrition 0.000 claims 1
- 239000004220 glutamic acid Substances 0.000 claims 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 abstract description 2
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 abstract description 2
- NHMJUOSYSOOPDM-UHFFFAOYSA-N cadmium cyanide Chemical compound [Cd+2].N#[C-].N#[C-] NHMJUOSYSOOPDM-UHFFFAOYSA-N 0.000 abstract 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 229910002058 ternary alloy Inorganic materials 0.000 description 7
- 150000002825 nitriles Chemical class 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910000925 Cd alloy Inorganic materials 0.000 description 2
- 229910004866 Cd-Zn Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 229910002059 quaternary alloy Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical class [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- YIDQSPNFDRTCBE-UHFFFAOYSA-N C(CC)CN(C)ON(C)CCCC Chemical class C(CC)CN(C)ON(C)CCCC YIDQSPNFDRTCBE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 241001331845 Equus asinus x caballus Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- OVKMDTVKFLNYRN-UHFFFAOYSA-N [Cd].[Cu].[Au] Chemical compound [Cd].[Cu].[Au] OVKMDTVKFLNYRN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KXAVXHYIOCQWIB-UHFFFAOYSA-N n-(dimethylaminooxy)-n-methylmethanamine Chemical class CN(C)ON(C)C KXAVXHYIOCQWIB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 oxycarbonyl-ethyl-amino Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
Definitions
- the present invention relates to new gold alloys, as well as to galvanic baths for the electrolytic deposition of these alloys.
- the object of this invention aims to remedy the aforementioned drawbacks of known alloys and baths, consists of an alloy containing between 40 and 92% by weight of gold, 4 to 12% by weight of cadmium and 0.1 at 1% by weight of zinc, the remainder consisting of copper.
- another object of this invention consists of a galvanic bath for the electrolytic deposition of these Au-Cu-Cd-Zn alloys, which is characterized by the fact that it contains a cyanide complex of gold, a cyanide complex of copper, a cyanide complex of cadmium and a cyanide complex of zinc, and at least one complexing agent and a surfactant.
- the bath operates in the presence or absence of free cyanide.
- the concentration of free potassium cyanide must be between 22 and 32 g / l, otherwise the deposit becomes hazy and pitted. . If the concentration of free cyanide is increased, the deposition of copper is slowed down and the deposit becomes too white. If this concentration is reduced, the deposit becomes too pink and not very resistant to corrosion.
- the copper-cyanide ratio is very important, because if the concentration of copper decreases by half, that is 30 g / l, the concentration of free cyanide should also decrease by half; in this case, the working margin is therefore further reduced. This is why, in traditional baths, it is preferred to work with very high copper concentrations, of the order of 60 to 70 g / l. This allows for greater tolerance in the concentration of free cyanide.
- this fourth metal namely zinc
- the amount of total cyanide must increase proportionally.
- the amount of free cyanide can vary within a range of 0 to 30 g / l for 10 g / l of zinc. The higher the zinc content, the larger this range.
- the copper concentration must be reduced and can be between 5 and 70 g / l, while that of zinc can vary from 0.5 to 50 g / l. With, for example, 35 g / l of copper and 5 g / l of zinc, there is in fact 20 g / l of cyanide linked loosely to the zinc complex. If we add another 5 g / l of free cyanide, we have in total 25 g / l of total cyanide. This provides excellent deposits.
- Gold and copper are introduced into the bath in the form of cyanide complexes KAu (CN) 2 and K 2 Cu (CN) 3 .
- Cadmium and zinc can also be introduced in the form of cyanide complexes.
- amino-carboxylates for example amino-carboxylates; hydroxy-alkyl-amino-carboxylic, poly-amino-carboxylic, hydroxy-alkyl-poly-amino-carboxylic, amino-phosphonic, poly-amino-phosphonic, phosphpnic acids or amino-carboxylic acids- phosphonic acids, which belong to different classes of chemical compounds, but whose molecule always contains one or more nitrogen atoms linked to various groups, such as those of methly-phosphonic acids or also alkyl, carboxy-alkyl and hydroxy-alkyl .
- R represents an alkyl group whose number of atoms
- carbon can be used in isolation is between 1 and 4, or acids or in combinations of the commercially available products- nitrilo-tri-acetic (NTA ), oxycarbonyl-ethyl-amino, known by the names of non-diacetic, N-carboxy-methyl-aspartic, N, N-bis- (carboxyionic, anionic, cationic or amphoteric) surfactants.
- NTA nitrilo-tri-acetic
- oxycarbonyl-ethyl-amino known by the names of non-diacetic, N-carboxy-methyl-aspartic, N, N-bis- (carboxyionic, anionic, cationic or amphoteric) surfactants.
- methyl) -asparftic, aspartic, glutamic and imino-specific can advantageously be used amidodiacetics, etc.
- All of these acids are preferably used propyl-dimethyl-amino-oxides of saturated fatty acids, for- in the form of soluble salts, that is to say in the form of general mule salts: sodium, potassium, ammonium or amines.
- the fatty acid or alkyl groups can also be ethoxylated.
- Phosphorus esters of ethylene oxide chains linked to an aliphatic chain can also be used as surfactants: monoester, or diester
- n a number between 8 and 18
- x represents a number between 6 and 15 and M a sodium or potassium ion.
- the concentrations of the various organic adducts can vary within a relatively large range, from 5 to 200 g / l for the complexing agents and from 0.01 to 50 ml / l for the surfactants.
- inorganic shine means soluble salts, therefore alkali metals, ammonium or amines, or complex salts of certain elements, capable of influencing the crystallization of the galvanic deposit so that it appears shiny.
- These inorganic brighteners contain selenium, tellurium, vanadium, arsenic, antimony, thallium, bismuth, titanium, germanium, zirconium, tantalum and / or niobium elements. These inorganic brighteners are used at low concentrations, ie from 0.01 to 100 mg / l.
- alkaline salts such as carbonates, phosphates or sulfites, in amounts of 5 to 30 g / l. They also act as pH regulators.
- the electrolytic baths which are the subject of the present invention are preferably used at a pH of 8 to 11, with a current density of 0.6 to 2.5 A / dm 2 and at a temperature of 40 to 75 ° C.
- a steel plate was subjected to electrolysis in this bath at a current density of 0.8 A / dm 2 and at the temperature of 60 ° C.
- the alloy deposited has the following composition: The deposit is uniform, shiny and pale yellow in color 1 N 14.
- a steel plate was subjected to electrolysis in this bath at a current density of 1 A / dm 2 and at the temperature of 60 ° C.
- the deposited alloy has the following composition: The deposit is uniform, shiny and pale yellow in color 1 N 14.
- the deposition rate is regulated, on the one hand by the current density allowed, on the other hand by the amount of organic complexing agent added to the bath.
- the current density allowed, on the other hand by the amount of organic complexing agent added to the bath.
- copper deposits little compared to gold and cadmium and the alloy is yellow.
- high current density it is an excess of copper which must be avoided by regulating the concentration of free cyanide and maintaining the organic complexing agent at relatively low concentrations.
- the baths of quaternary alloys which are the subject of the present invention, allow a greater margin of current densities than the usual baths of ternary alloys. They allow, in particular to obtain excellent deposits at high current densities, admitting a deposition rate of 1 micron in one to two minutes, which is much higher than that of generally used baths, which require at least three minutes to deposit 1 micron.
- the usual baths of ternary alloys allow, for deposits, a gold content of 14 to 18 carats, or 58 to 75% of gold. Outside these limits, the deposits have neither a good appearance, nor good mechanical characteristics and corrosion resistance.
- baths B1 to B5 were used to obtain deposits of Au-Cu-Cd-Zn alloys, working at a temperature of 60 ° C and with a current density of 0.7 A / dm 2 for the baths B1 and B2, 0.8 A / dm 2 for the B3 bath, and 0.75 A / dm 2 for the B4 bath.
- Bath B5 was used with a current density of 1.0 A / dm 2 - (B5a), then 1.25 A / dm 2 (B5b).
- the deposits obtained are all pale yellow in color, ductile, shiny and perfectly resistant to corrosion.
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- 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 |
|---|---|---|---|
| CH944/85 | 1985-03-01 | ||
| CH944/85A CH662583A5 (fr) | 1985-03-01 | 1985-03-01 | Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0193848A1 true EP0193848A1 (de) | 1986-09-10 |
| EP0193848B1 EP0193848B1 (de) | 1989-08-16 |
Family
ID=4198804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86102442A Expired EP0193848B1 (de) | 1985-03-01 | 1986-02-25 | Galvanisches Bad für das Elektroplattieren von Goldlegierungen |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4687557A (de) |
| EP (1) | EP0193848B1 (de) |
| CH (1) | CH662583A5 (de) |
| DE (2) | DE193848T1 (de) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0304315A1 (de) * | 1987-08-21 | 1989-02-22 | Engelhard Limited | Bad für das Elektroplattieren einer Gold-Kupfer-Zink-Legierung |
| EP1983077A1 (de) * | 2007-04-19 | 2008-10-22 | Enthone, Inc. | Elektrolyt und Verfahren zur elektrolytischen Ablagerung von Gold-Kupfer-Legierungen |
| EP2312021A1 (de) * | 2009-10-15 | 2011-04-20 | The Swatch Group Research and Development Ltd. | Verfahren zum Erhalten einer gelben Goldlegierungsablagerung durch Galvanoplastik ohne Verwendung von giftigen Metallen |
| US9683303B2 (en) | 2007-09-21 | 2017-06-20 | The Swatch Group Research And Development Ltd | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids |
| EP3356579B1 (de) | 2015-09-30 | 2020-03-11 | Coventya S.p.A. | Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd-legierung, verfahren zur elektrochemischen abscheidung von dieser legierung, substrat mit dieser legierung und verwendung des substrats |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8903818D0 (en) * | 1989-02-20 | 1989-04-05 | Engelhard Corp | Electrolytic deposition of gold-containing alloys |
| DE3929569C1 (de) * | 1989-09-06 | 1991-04-18 | Degussa Ag, 6000 Frankfurt, De | |
| GB9522591D0 (en) * | 1995-11-03 | 1996-01-03 | Enthone Omi Suisse S A | Electroplating processes compositions and deposits |
| ATE220736T1 (de) * | 1995-11-03 | 2002-08-15 | Enthone Omi Inc | Elektroplattierungsverfahren, zusammensetzungen und überzügen |
| FR2828889B1 (fr) * | 2001-08-24 | 2004-05-07 | Engelhard Clal Sas | Bain electrolytique pour le depot electrochimique de l'or et de ses alliages |
| CH714243B1 (fr) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Procédé d'électroformage et pièce ou couche obtenue par ce procédé. |
| US7534289B1 (en) | 2008-07-02 | 2009-05-19 | Rohm And Haas Electronic Materials Llc | Electroless gold plating solution |
| EP2143820B1 (de) * | 2008-07-11 | 2012-03-07 | Rohm and Haas Electronic Materials LLC | Stromfreie Goldplattierungslösung |
| CN101634021B (zh) * | 2008-07-24 | 2012-11-07 | 罗门哈斯电子材料有限公司 | 无电镀金液 |
| CH706336B1 (fr) * | 2012-04-02 | 2016-03-31 | Haute Ecole Arc | Bain galvanique pour le dépôt électrolytique d'un matériau composite. |
| 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. |
| IT201900001769A1 (it) * | 2019-02-07 | 2020-08-07 | Italfimet Srl | Lega d'oro rosa, procedimento di realizzazione ed uso. |
| CN116917549A (zh) | 2021-02-23 | 2023-10-20 | 意大利菲美特有限公司 | 用于电镀电沉积的方法以及相关的电镀池 |
| CN114836794B (zh) * | 2021-06-25 | 2024-01-30 | 深圳市铭轩珠宝首饰有限公司 | 一种金-铜合金电铸工艺及其应用 |
| WO2023126257A1 (en) | 2021-12-29 | 2023-07-06 | Basf Se | Alkaline composition for copper electroplating comprising a grain refiner |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1572525A (de) * | 1967-05-11 | 1969-06-27 | ||
| GB2012306A (en) * | 1978-01-16 | 1979-07-25 | Oxy Metal Industries Corp | Zinc electroplating bath and process |
| AT353071B (de) * | 1977-10-06 | 1979-10-25 | Oxy Metal Industries Corp | Cyanidfreies, basisches sulfitbad zur elektrolytischen faellung von gold-zink- legierungen |
| US4179344A (en) * | 1973-07-02 | 1979-12-18 | Lea-Ronal, Inc. | Gold alloy plating compositions and method |
| EP0140832A2 (de) * | 1983-09-01 | 1985-05-08 | H. E. Finishing SA | Galvanisches Bad für das elekrolytische Absetzen einer Goldlegierung und galvanisches Verfahren für die Verwendung dieses Bads |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL130011C (de) * | 1960-04-23 | |||
| CH418085A (fr) * | 1964-08-19 | 1966-07-31 | Pilot Pen Co Ltd | Electrolyte pour le dépôt galvanique d'alliages d'or |
| CH522740A (de) * | 1968-06-28 | 1972-06-30 | Degussa | Verfahren zur galvanischen Abscheidung von Gold-Kupfer-Cadmium-Legierungsüberzügen |
| CH529843A (fr) * | 1971-07-09 | 1972-10-31 | Oxy Metal Finishing Europ S A | Bain pour le dépôt électrolytique d'alliages d'or et son utilisation en galvanoplastie |
| CH556916A (fr) * | 1972-03-23 | 1974-12-13 | Lea Ronal Inc | Procede pour le depot electrolytique d'alliages d'or. |
| DE2251285C3 (de) * | 1972-10-14 | 1981-01-22 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Alkalisches Bad für die galvanische Abscheidung von Goldlegierungen |
| CH621367A5 (en) * | 1977-07-08 | 1981-01-30 | Systemes Traitements Surfaces | Electrolytic bath for plating gold-copper-cadmium alloys and its use in galvanoplasty |
| CH632533A5 (fr) * | 1979-06-14 | 1982-10-15 | Aliprandini P | Procede pour le depot galvanoplastique d'un alliage d'or. |
| DE3020765A1 (de) * | 1980-05-31 | 1981-12-10 | Degussa Ag, 6000 Frankfurt | Alkalisches bad zum galvanischen abscheiden niederkaraetiger rosa- bis gelbfarbener goldlegierungsschichten |
| US4486275A (en) * | 1983-02-07 | 1984-12-04 | Heinz Emmenegger | Solution for electroplating a gold-copper-cadmium alloy |
-
1985
- 1985-03-01 CH CH944/85A patent/CH662583A5/fr not_active IP Right Cessation
-
1986
- 1986-02-24 US US06/832,087 patent/US4687557A/en not_active Expired - Lifetime
- 1986-02-25 DE DE198686102442T patent/DE193848T1/de active Pending
- 1986-02-25 EP EP86102442A patent/EP0193848B1/de not_active Expired
- 1986-02-25 DE DE8686102442T patent/DE3665078D1/de not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1572525A (de) * | 1967-05-11 | 1969-06-27 | ||
| US4179344A (en) * | 1973-07-02 | 1979-12-18 | Lea-Ronal, Inc. | Gold alloy plating compositions and method |
| AT353071B (de) * | 1977-10-06 | 1979-10-25 | Oxy Metal Industries Corp | Cyanidfreies, basisches sulfitbad zur elektrolytischen faellung von gold-zink- legierungen |
| GB2012306A (en) * | 1978-01-16 | 1979-07-25 | Oxy Metal Industries Corp | Zinc electroplating bath and process |
| EP0140832A2 (de) * | 1983-09-01 | 1985-05-08 | H. E. Finishing SA | Galvanisches Bad für das elekrolytische Absetzen einer Goldlegierung und galvanisches Verfahren für die Verwendung dieses Bads |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0304315A1 (de) * | 1987-08-21 | 1989-02-22 | Engelhard Limited | Bad für das Elektroplattieren einer Gold-Kupfer-Zink-Legierung |
| US4980035A (en) * | 1987-08-21 | 1990-12-25 | Engelhard Corporation | Bath for electrolytic deposition of a gold-copper-zinc alloy |
| EP1983077A1 (de) * | 2007-04-19 | 2008-10-22 | Enthone, Inc. | Elektrolyt und Verfahren zur elektrolytischen Ablagerung von Gold-Kupfer-Legierungen |
| EP3170924A1 (de) * | 2007-04-19 | 2017-05-24 | Enthone, Inc. | Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen |
| US9683303B2 (en) | 2007-09-21 | 2017-06-20 | The Swatch Group Research And Development Ltd | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids |
| US10233555B2 (en) | 2007-09-21 | 2019-03-19 | The Swatch Group Research And Development Ltd. | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids |
| US10619260B2 (en) | 2007-09-21 | 2020-04-14 | The Swatch Group Research And Development Ltd. | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids |
| EP2312021A1 (de) * | 2009-10-15 | 2011-04-20 | The Swatch Group Research and Development Ltd. | Verfahren zum Erhalten einer gelben Goldlegierungsablagerung durch Galvanoplastik ohne Verwendung von giftigen Metallen |
| US9567684B2 (en) | 2009-10-15 | 2017-02-14 | The Swatch Group Research And Development Ltd | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials |
| EP3356579B1 (de) | 2015-09-30 | 2020-03-11 | Coventya S.p.A. | Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd-legierung, verfahren zur elektrochemischen abscheidung von dieser legierung, substrat mit dieser legierung und verwendung des substrats |
Also Published As
| Publication number | Publication date |
|---|---|
| DE193848T1 (de) | 1986-12-18 |
| DE3665078D1 (en) | 1989-09-21 |
| US4687557A (en) | 1987-08-18 |
| CH662583A5 (fr) | 1987-10-15 |
| EP0193848B1 (de) | 1989-08-16 |
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