US3833486A - Cyanide-free electroplating - Google Patents
Cyanide-free electroplating Download PDFInfo
- Publication number
- US3833486A US3833486A US00345041A US34504173A US3833486A US 3833486 A US3833486 A US 3833486A US 00345041 A US00345041 A US 00345041A US 34504173 A US34504173 A US 34504173A US 3833486 A US3833486 A US 3833486A
- Authority
- US
- United States
- Prior art keywords
- baths
- metal
- electroplating
- bath
- cyanide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000009713 electroplating Methods 0.000 title abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 abstract description 27
- 239000007800 oxidant agent Substances 0.000 abstract description 16
- 239000000654 additive Substances 0.000 abstract description 13
- 239000002738 chelating agent Substances 0.000 abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 abstract description 9
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000006872 improvement Effects 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- -1 aromatic alkyl sulfonates Chemical class 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229940024606 amino acid Drugs 0.000 description 5
- 235000001014 amino acid Nutrition 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000001455 metallic ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 3
- 229960002218 sodium chlorite Drugs 0.000 description 3
- QIJRTFXNRTXDIP-UHFFFAOYSA-N (1-carboxy-2-sulfanylethyl)azanium;chloride;hydrate Chemical compound O.Cl.SCC(N)C(O)=O QIJRTFXNRTXDIP-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229960001305 cysteine hydrochloride Drugs 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 231100000206 health hazard Toxicity 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 229960001471 sodium selenite Drugs 0.000 description 2
- 239000011781 sodium selenite Substances 0.000 description 2
- 235000015921 sodium selenite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- XHAZMZWXAOBLQG-UHFFFAOYSA-N (1-hydroxy-1-phosphonopropyl)phosphonic acid Chemical compound CCC(O)(P(O)(O)=O)P(O)(O)=O XHAZMZWXAOBLQG-UHFFFAOYSA-N 0.000 description 1
- DZKRDHLYQRTDBU-UPHRSURJSA-N (z)-but-2-enediperoxoic acid Chemical compound OOC(=O)\C=C/C(=O)OO DZKRDHLYQRTDBU-UPHRSURJSA-N 0.000 description 1
- OWWOMIFQTFZNGK-UHFFFAOYSA-N 1-phosphonobutylphosphonic acid Chemical compound CCCC(P(O)(O)=O)P(O)(O)=O OWWOMIFQTFZNGK-UHFFFAOYSA-N 0.000 description 1
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- ULQQGOGMQRGFFR-UHFFFAOYSA-N 2-chlorobenzenecarboperoxoic acid Chemical compound OOC(=O)C1=CC=CC=C1Cl ULQQGOGMQRGFFR-UHFFFAOYSA-N 0.000 description 1
- ROPQINLWRARCTM-UHFFFAOYSA-N 2-phosphonopropan-2-ylphosphonic acid Chemical compound OP(=O)(O)C(C)(C)P(O)(O)=O ROPQINLWRARCTM-UHFFFAOYSA-N 0.000 description 1
- BFUXVNFVPPCFIT-UHFFFAOYSA-N 3,4-difluoropyridazine Chemical compound FC1=CC=NN=C1F BFUXVNFVPPCFIT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CRZLGDXUWJLYRZ-UHFFFAOYSA-N COP(OC)(=O)C.NCCC(O)CN Chemical compound COP(OC)(=O)C.NCCC(O)CN CRZLGDXUWJLYRZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical class Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000537 White brass Inorganic materials 0.000 description 1
- 229910000581 Yellow brass Inorganic materials 0.000 description 1
- YUUKIOKWOBAUSK-UHFFFAOYSA-L [OH-].[OH-].[Cu+2].NCCN Chemical compound [OH-].[OH-].[Cu+2].NCCN YUUKIOKWOBAUSK-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
- 125000001931 aliphatic group Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- KNSWNNXPAWSACI-UHFFFAOYSA-N chlorine pentafluoride Chemical compound FCl(F)(F)(F)F KNSWNNXPAWSACI-UHFFFAOYSA-N 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- ZIOUHCMXEAFYSA-UHFFFAOYSA-N chlorodifluoroamine Chemical compound FN(F)Cl ZIOUHCMXEAFYSA-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- ULFHSQLFQYTZLS-UHFFFAOYSA-N difluoroamine Chemical compound FNF ULFHSQLFQYTZLS-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- AXCBHWGTRNNXKG-UHFFFAOYSA-N fluorochlorane oxide Chemical class FCl=O AXCBHWGTRNNXKG-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- DKPHLYCEFBDQKM-UHFFFAOYSA-H hexapotassium;1-phosphonato-n,n-bis(phosphonatomethyl)methanamine Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)CN(CP([O-])([O-])=O)CP([O-])([O-])=O DKPHLYCEFBDQKM-UHFFFAOYSA-H 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229960005337 lysine hydrochloride Drugs 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HHQJWDKIRXRTLS-UHFFFAOYSA-N n'-bromobutanediamide Chemical compound NC(=O)CCC(=O)NBr HHQJWDKIRXRTLS-UHFFFAOYSA-N 0.000 description 1
- PWBJWDKDPAPGED-UHFFFAOYSA-N n'-chlorobutanediamide Chemical compound NC(=O)CCC(=O)NCl PWBJWDKDPAPGED-UHFFFAOYSA-N 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical class FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940091258 selenium supplement Drugs 0.000 description 1
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 1
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 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
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- GFADZIUESKAXAK-UHFFFAOYSA-N tetrafluorohydrazine Chemical compound FN(F)N(F)F GFADZIUESKAXAK-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YVDPOVXIRVBNAL-UHFFFAOYSA-J tetrapotassium;phosphonatooxy phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OOP([O-])([O-])=O YVDPOVXIRVBNAL-UHFFFAOYSA-J 0.000 description 1
- KWXLCDNSEHTOCB-UHFFFAOYSA-J tetrasodium;1,1-diphosphonatoethanol Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P(=O)([O-])C(O)(C)P([O-])([O-])=O KWXLCDNSEHTOCB-UHFFFAOYSA-J 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- ABSTRACT Improved cyanide-free aqueous electroplating baths for plating metals, the baths containing water soluble phosphonate chelating agents combined with at least one chelatable metal ion and containing as an additive at least one strong oxidizing agent, and electroplating processes employing said baths. Additional materials may also be added for further improvements.
- This invention relates broadly to the electroplating of metals and metal alloys from cyanide-free aqueous plating baths. More specifically, this invention relates to improved cyanide-free aqueous electroplating baths containing a stable metal chelate formed from a water soluble phosphonate chelating agent combined'with at least one chelatable metal ion and containing as an additional additive at least one strong oxidizing agent. It is also contemplated to add certain other selected classes of materials to the improved baths in order to achieve further advantageous results.
- Alkaline electroplating baths containing cyanides are widely used in industrial metal electroplating operations for the plating of certain metals. For many applications these cyanide-containing baths produce excellent results.
- the conventional electroplating baths consist essentially of aqueous alkaline solutions of the cyanide salt of the metal to be electrodeposited.
- additives may be included to improve the quality of the electro-deposits obtained therefrom. These additives can be used to produce grain refining, brightness, improve the bright plating range, or in general to impart desirable characteristics to the deposit or the operation of the bath.
- Typical examples of commonly employed additives are aromatic alkyl sulfonates which improve the luster of the plated metal surface and increase the uniformity of the plating baths to increase the amount of plating current density and hence plating speed which may be utilized without a roughening or burning of the plated surface. Further additives are employed to improve the throwing power of the electroplating bath, i.e., the ability of the bath to deposit a uniform thickness of plating metal in the recesses of a base metal object.
- Alkaline pyrophosphate electroplating baths are also in use today. These baths, however, have been found to be extremely sensitive to organic contamination and require periodic dilutions as the concentration of orthophosphate in the bath increases due to the hydrolysis of the pyrophosphate ion. Thus, the effective concentrations in the bath at any one time may be somewhat uncertain.
- electroplating solutions which contain a salt of the metal which is to be deposited and a phosphonic acid derivative as the chelating agent for the metal to be plated.
- Such plating solutions are described in French Pat. No. 1,458,492 to Monsanto Co. and in US. Pat. No. 3,475,293 to Haynes and Langguth assigned to Monsanto Co. as well as in copending US. application Ser. No. 825,067 of Nobel and Ostrow, assigned to Lea- Ronal, Inc., now abandoned.
- These patents describe electroplating baths containing a complex consisting of a divalent metal ion and an organophosphorous ligand of the formula: i
- n is an integer of from 2 to 3, incl.
- M is a member selected from the group consisting of a hydrogen ion, ammonium, lower alkyl amine or an alkali metal cation and Z is a connecting radical equal in valence to n and containing not more than about 12 carbon atoms exclusive of hydrogen in chemicalcombination and is selected from the group consisting of (1) an aliphatic radical (2) an N-substituted aliphatic radical containing from 2 to 3 alkyl groups in which the connecting radical has a carbon atom linked to a phosphorus atom in the ligand.
- polyamine phosphonate compounds are described in aforementioned US. Pat. application Ser. No. 825,067 in conjunction with electroplating baths containing in addition to the polyamine phosphonate, a chelatable metal ion.
- chlorites are long lived as effective additives to the solutions and give superior results.
- the improvement caused by the addition and periodic replenishment of the oxidizing agents makes the chlorite containing bath a practical plating bath.
- Particularly useful compounds include:
- Potassium peroxymonosulfate Ammonium persulfate Sodium or potassium perborate Sodium chlorite Sodium hypochlorite Hydrogen peroxide Potassium permanganate Potassium perchlorate Potassium peroxydiphosphate N-bromosuccinamide N-chlorosuccinamide Chloroperbenzoic acid Dimethyl sulfoxide Perbenzoic acid Potassium periodate Peracetic acid Permaleic acid Pyridine N-oxide
- certain inorganic high energy oxidizers such as the fluoronitrogen compounds examples of which are nitrogen trifluoride, difluorodiazine, tetrafluorohydrazine, difluoramine, chlorodifluoroamine, and fluorine and fluorohalogen compounds including chlorine trifluoride and derivatives, chlorine pentafluoride, chlorine fluoride oxides, oxygen fluorides and related compounds, and chlorine oxides and related compounds.
- the amount of the selected oxidizing agent required varies somewhat with the particular oxidizing agent selected to be used and the amount of electrolysis the bath has undergone. Sufficient oxidizing agent is used to overcome the bad effects produced by continuation of electrolysis.
- the amount of sodium chlorite, the preferred material, required is about 0.25 g/l in most baths.
- the range of use for the oxidizing agents is from about 0.01 g/l up to about g/l, but in all cases the minimum amount necessary to produce good results should be employed.
- the amount required can readily be determined by a Hull cell test, which is a plating test cell used by all plating laboratories.
- chelating agents which may be used as the basic ingredient of these baths include diethylene triamine pentamethylphosphonate acid, triethylene tetramine hexamethylphosphonate acid, tetraethylene pentamine heptamethylphosphonate acid and their alkali'metal or ammonium salts. Further examples of useful chelating agents are ethylene diamine tetramethylphosphonic acid, hexamethylene diamine tetramethylphosphonic acid, aminoethyl ethanolamine trimethylphosphonic acid, aminoethyl piperazine trimethylphosphonic acid, diamino pyridine tetramethylphosphonic acid, and their alkali metal or ammonium salts. Chelating agents also useful are hydrazine tetramethylphosphonic acid and its alkali metal or ammonium salts.
- X is selected from hydrogen, hydroxyl or a lower alkyl group containing from about one to about four carbon atoms and Y is a member selected from the group consisting of hydrogen, hydroxyl and lower alkyl containing from about one to about four carbon atoms,
- organophosphorus ligand when Z is an N-substituted aliphatic connecting radical containing 3 alkyl groups the organophosphorus ligand will have the formula:
- Lower alkylidene diphosphonic acid compounds falling within the scope of the above general formula include methylene diphosphonic acid, ethylidene diphosphonic acid, isopropylidene diphosphonic acid, 1- hydroxyethylidene diphosphonic acid, 1- hydroxypropylidene diphosphonic acid, butylidene diphosphonic acid and the like.
- M in the above formula may be among others, a hydrogen ion or an alkali metal cation. It is preferred that M be an alkali metal cation such as sodium, potassium and lithium.
- organophosphorus ligands employed in the form of a divalent transitional metal ion complex include for example, pentapotassium amino(- trimethylene phosphonate), tetrapotassium lhydroxyethylidene diphosphonate, pentasodium aminotri(methylene phosphonate), tetrasodium 1- hydroxyethylidene diphosphonate.
- the plating baths of the present invention may be prepared for instance by forming an aqueous solution of a suitable metal compound and a phosphonate chelating agent of the present invention.
- Another method for-preparing the baths disclosed herein is to form an aqueous mixture of a metal chelate salt which has been previously prepared, e.g., by thereaction of a chelatable metal carbonate, hydroxide or oxide with a phos-,
- a suitable alkaline compound such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, or the alkali metal carbonates.
- the oxidizing agent of the invention is then added in the required small but effective concentration quantity.
- any water soluble metal compound which will form chelates with the above-described chelating agents may be used for the plating solutions of this invention including soluble compounds of iron, cobalt, nickel, zinc, silver, copper, cadmium and tin.
- the metal compounds employed in making up the baths may be (1) ionic metal salts which when solubilized release a chelatable metal ion, e.g., copper sulfate, or (2) complex salts which, when solubilized, will supply a chelatable metal ion, e.g., sodium zincate, or (3) metal salts, such as the carbonates which will react withphosphonic acid chelating agent to form a metal chelate salt.
- alloys can be achieved by the invention through the use of two or more different chelatable metals in the proper proportions.
- alloys which have been plated by the present invention are copper-nickel alloy, and copper-zinc yellow brass alloy and copper-zinc white brass alloy. 7 I
- essentially neutral electroplating solution of 6 to 9 pH is preferable, but higher pH ranges, up to 13 as well as lower ranges to about 3 or 4 can also be used.
- certain metallic additives when added to the plating baths of the invention, improve significantly the brightness of the deposits, provided the bath is stabilized with the oxidizing agent.
- These metals are thallium, lead and cadmium. The amounts used is about 0.01 to 0.5 g/l or a sufficient amount to give the brightness desired.
- These metals may be added as the soluble metal salt such sulfate, acetate, tartrate, citrate, chloride, and the like.
- Other metallic ions which can also be used include arsenic, antimony and bismuth and the amounts used are about 0.01 to 1 g/l or a sufficient amount to give the brightness desired.
- the ions can be added as the soluble salt such as tartrate. Of the metallics above listed bismuth has been found to be preferred.
- selenium and tellurium can be advantageously used in the stabilized bath. They may be added as the sodium selenite or tellurite. The amounts that are useful are about 0.1 g/l or an amount sufficient to improve brightness.
- amino acids can be used to improve the brightness of metallic deposits.
- Amino acids that are useful as additives to the plating baths are lysine hydrochloride, cysteine hydrochloride, alanine, methionine, glycine, l-tyrosine, and the like.
- the preferred amino acid additive is glycine.
- the amount re quired is about 0.01 to 5 g/l or an amount sufficient to produce the desired effect.
- Amino acids increase the ability of the plating solution to withstand prolonged electrolysis without plating dull.
- metal additives can be used with the amino acids, i.e., bismuth ions with glycine with achievement of good results.
- the plating baths were prepared by dissolving in water the indicated quantity of the compound of the metal to be electrodeposited and the indicated phosphonate chelating agent. An alkali metal hydroxide was added to the solution to adjust the pH to the selected value.
- the examples illustrate the different metal compounds which can be used in the invention and which when solubilized release a metallic ion.
- the electroplating of the metal was conducted in a 267 ml. Hull cell, in a conventional manner at a temperature in the range of from room temperature to 140F. and at a current of l ampere.
- Various brighteners which are described as further features of this invention were added to the bath as specific embodiments of the invention.
- the pH of the mixture was adjusted to 8.0 with potassium hydroxide and the deposition temperature was F.
- the copper deposit was uniformly bright with a narrow burn in the high current area.
- Potassium hydroxide was used to adjust the pH to 10.3 and the metal was deposited at a temperature of 140F. The resulting deposit was completely bright except at the high current area.
- the pH was adjusted to 10.3 with sodium hydroxide and the temperature was 140F.
- the resulting deposit was completely bright except in the area of high current.
- Potassium hydroxide was added to adjust the pH to 5.0. A temperature of F. was used and the metal deposit was uniformly bright even after electrolyzing for ampere minutes.
- a process for producing deposits of metal which comprises electrodepositing metal from a cyanide-free aqueous solution containing an effective amount of a complex formed of a water soluble phosphonate chelating agent and at least one chelatable metal ion of a metal to be electrodeposited and capable of producing electrodeposits, the improvement which comprises including in the electroplating solution from about 0.01 to about 5.0 g/l of at least one oxidizing agent selected from the group consisting of peroxides, chlorites, perchlorates, hypochlorites, permanganates and sulfoxides.
- metal undergoing electrodeposition is selected from the group consisting of iron, cobalt, nickel, zinc, silver, copper, cadmium and tin.
Abstract
Improved cyanide-free aqueous electroplating baths for plating metals, the baths containing water soluble phosphonate chelating agents combined with at least one chelatable metal ion and containing as an additive at least one strong oxidizing agent, and electroplating processes employing said baths. Additional materials may also be added for further improvements.
Description
United States Patent 1191 Nobel et al.
[451 Sept. 3, 1974 CYANIDE-FREE ELECTROPLATING [75] Inventors: Fred 1. Nobel, Roslyn; Lazaro C.
Yoen, Brooklyn, both of N.Y.
[7 3] Assignee: Lea-Rona], Inc., Freeport, N.Y.
[22] Filed: Mar. 26, 1973 [21] Appl. No.: 345,041
[56] I References Cited UNITED STATES PATENTS 3,475,293 10/1969 Haynes et al. 204/48 FOREIGN PATENTS OR APPLICATIONS 2,023,304 11/1970 Germany 204 45 R OTHER PUBLICATIONS Frederick A. Lowenheim, Modern Electroplating, pp. 178-185 & 293-294, (1968), TS 670 E46 C.2.
Primary Examiner-G. L. Kaplan Attorney, Agent, or Firm-Lawrence Rosen; E. Janet Berry [5 7] ABSTRACT Improved cyanide-free aqueous electroplating baths for plating metals, the baths containing water soluble phosphonate chelating agents combined with at least one chelatable metal ion and containing as an additive at least one strong oxidizing agent, and electroplating processes employing said baths. Additional materials may also be added for further improvements.
3 Claims, No Drawings 1 CYANIDE-FREE ELECTROPLATING This invention relates broadly to the electroplating of metals and metal alloys from cyanide-free aqueous plating baths. More specifically, this invention relates to improved cyanide-free aqueous electroplating baths containing a stable metal chelate formed from a water soluble phosphonate chelating agent combined'with at least one chelatable metal ion and containing as an additional additive at least one strong oxidizing agent. It is also contemplated to add certain other selected classes of materials to the improved baths in order to achieve further advantageous results.
It is one object of this invention to provide improvements in cyanide-free plating baths for electroplating metals.
It is another object'to add strong oxidizing agents to electroplating baths to improve the brightness characteristics of the metal deposits therefrom.
It is a further object to improve the life of phosphonate chelate-containing, cyanide-free electroplating baths by the addition thereto of at least one strong oxidizing agent and, as an additional feature, other property-improving additives.
Other and further objects of the invention will become apparent from the more detailed description of the invention set forth below.
Alkaline electroplating baths containing cyanides are widely used in industrial metal electroplating operations for the plating of certain metals. For many applications these cyanide-containing baths produce excellent results. The conventional electroplating baths consist essentially of aqueous alkaline solutions of the cyanide salt of the metal to be electrodeposited. In addition to these salts, additives may be included to improve the quality of the electro-deposits obtained therefrom. These additives can be used to produce grain refining, brightness, improve the bright plating range, or in general to impart desirable characteristics to the deposit or the operation of the bath. Typical examples of commonly employed additives are aromatic alkyl sulfonates which improve the luster of the plated metal surface and increase the uniformity of the plating baths to increase the amount of plating current density and hence plating speed which may be utilized without a roughening or burning of the plated surface. Further additives are employed to improve the throwing power of the electroplating bath, i.e., the ability of the bath to deposit a uniform thickness of plating metal in the recesses of a base metal object.
While excellent results can be obtained by using the above described cyanide-containing baths, the extreme toxicity of these solutions as the result of the presence of large quantities of cyanide presents disadvantages and makes their use undesirable. In addition to the inherent health hazards to personnel in the vicinity of the plating solution, a further problem is created by the need to destroy all of the cyanide before it is allowed to enter any stream or sewer system. The presence of even trace amounts of these chemicals in streams or sewers presents a severe health hazard and highly dangerous pollution problem; The chemical destruction of cyanides, on the other hand, is both cumbersome and expensive. Also, if the pH of an alkaline cyanide plating bath inadvertently becomes neutral or acidic, lethal hydrogen cyanide gas may form, creatinga distinct hazard to all those in the vicinity.
Alkaline pyrophosphate electroplating baths are also in use today. These baths, however, have been found to be extremely sensitive to organic contamination and require periodic dilutions as the concentration of orthophosphate in the bath increases due to the hydrolysis of the pyrophosphate ion. Thus, the effective concentrations in the bath at any one time may be somewhat uncertain.
Attempts to overcome the difficulties described in cyanide electroplating and other above mentioned plating baths while retaining the advantages thereof have been made. For instance, electroplating solutions have been developed which contain a salt of the metal which is to be deposited and a phosphonic acid derivative as the chelating agent for the metal to be plated. Such plating solutions are described in French Pat. No. 1,458,492 to Monsanto Co. and in US. Pat. No. 3,475,293 to Haynes and Langguth assigned to Monsanto Co. as well as in copending US. application Ser. No. 825,067 of Nobel and Ostrow, assigned to Lea- Ronal, Inc., now abandoned. These patents describe electroplating baths containing a complex consisting of a divalent metal ion and an organophosphorous ligand of the formula: i
0 0M I (ll/ z- P Qua .EQM L where n is an integer of from 2 to 3, incl., M is a member selected from the group consisting of a hydrogen ion, ammonium, lower alkyl amine or an alkali metal cation and Z is a connecting radical equal in valence to n and containing not more than about 12 carbon atoms exclusive of hydrogen in chemicalcombination and is selected from the group consisting of (1) an aliphatic radical (2) an N-substituted aliphatic radical containing from 2 to 3 alkyl groups in which the connecting radical has a carbon atom linked to a phosphorus atom in the ligand.
In addition, polyamine phosphonate compounds are described in aforementioned US. Pat. application Ser. No. 825,067 in conjunction with electroplating baths containing in addition to the polyamine phosphonate, a chelatable metal ion.
Initially, the cyanide-free baths prepared in accordance with these improved processes of the prior art patents and the patent application aforementioned are semibright to lustrous. However, these so-called improved electroplating solutions are not commercially practicable because as the electroplating process proceeds, the metallic deposit tends to become continually duller and more granular, particularly in the low current density areas.
For example, 267 ml. of the following plating solu- I tion was prepared 1 hydroxyethylidene diphosphonic acid I g/l Copper metal as the hydroxide 15 g/l Ethylenediamine tetramethylphosphonic acid 4 g/l Potassium hydroxide to pH I0 3 The resulting solution was electrolyzed for 5 minutes at l ampere. The deposit was uniformly lustrous or semibright. However, continued electrolysis for an additional ampere minutes (1 ampere for 120 minutes) the deposit became dull and granular, particularly It has now been found that oxidizing agents may be used with the water soluble phosphonate chelating agents to alleviate the problem of poor luster. Their use results in a greatly improved deposit. In general it has been found thatth'e stronger oxidizing agents such as the peroxides, chlorites, perchlorates, hypochlorites,
' permanganates, sulfoxides, and the like are most beneficial. In particular, it was found that chlorites are long lived as effective additives to the solutions and give superior results. The improvement caused by the addition and periodic replenishment of the oxidizing agents makes the chlorite containing bath a practical plating bath. Particularly useful compounds include:
Potassium peroxymonosulfate Ammonium persulfate Sodium or potassium perborate Sodium chlorite Sodium hypochlorite Hydrogen peroxide Potassium permanganate Potassium perchlorate Potassium peroxydiphosphate N-bromosuccinamide N-chlorosuccinamide Chloroperbenzoic acid Dimethyl sulfoxide Perbenzoic acid Potassium periodate Peracetic acid Permaleic acid Pyridine N-oxide Also useful are certain inorganic high energy oxidizers such as the fluoronitrogen compounds examples of which are nitrogen trifluoride, difluorodiazine, tetrafluorohydrazine, difluoramine, chlorodifluoroamine, and fluorine and fluorohalogen compounds including chlorine trifluoride and derivatives, chlorine pentafluoride, chlorine fluoride oxides, oxygen fluorides and related compounds, and chlorine oxides and related compounds. t
The amount of the selected oxidizing agent required varies somewhat with the particular oxidizing agent selected to be used and the amount of electrolysis the bath has undergone. Sufficient oxidizing agent is used to overcome the bad effects produced by continuation of electrolysis. The amount of sodium chlorite, the preferred material, required is about 0.25 g/l in most baths. The range of use for the oxidizing agents is from about 0.01 g/l up to about g/l, but in all cases the minimum amount necessary to produce good results should be employed. The amount required can readily be determined by a Hull cell test, which is a plating test cell used by all plating laboratories.
Examples of chelating agents which may be used as the basic ingredient of these baths include diethylene triamine pentamethylphosphonate acid, triethylene tetramine hexamethylphosphonate acid, tetraethylene pentamine heptamethylphosphonate acid and their alkali'metal or ammonium salts. Further examples of useful chelating agents are ethylene diamine tetramethylphosphonic acid, hexamethylene diamine tetramethylphosphonic acid, aminoethyl ethanolamine trimethylphosphonic acid, aminoethyl piperazine trimethylphosphonic acid, diamino pyridine tetramethylphosphonic acid, and their alkali metal or ammonium salts. Chelating agents also useful are hydrazine tetramethylphosphonic acid and its alkali metal or ammonium salts.
In the hereinbefore described formula I for the organophosphorus ligand when Z is an aliphatic radical containing from one to 12 carbon atoms the ligand will preferablyhave the formula:
wherein X is selected from hydrogen, hydroxyl or a lower alkyl group containing from about one to about four carbon atoms and Y is a member selected from the group consisting of hydrogen, hydroxyl and lower alkyl containing from about one to about four carbon atoms,
and M is as hereinbefore described.
' In the above formula I when Z is an N-substituted aliphatic connecting radical containing 3 alkyl groups the organophosphorus ligand will have the formula:
' i Ii/ (III) phonic acid) mono(isopropylidene phosphonic acid),
aminomono(methylene phosphonic acid) di(ethylidene phosphonic acid), aminomono(methylene phosphonic acid) diis'opropylidene phosphonic acid and the like.
Lower alkylidene diphosphonic acid compounds falling within the scope of the above general formula include methylene diphosphonic acid, ethylidene diphosphonic acid, isopropylidene diphosphonic acid, 1- hydroxyethylidene diphosphonic acid, 1- hydroxypropylidene diphosphonic acid, butylidene diphosphonic acid and the like.
As stated hereinbefore M in the above formula may be among others, a hydrogen ion or an alkali metal cation. It is preferred that M be an alkali metal cation such as sodium, potassium and lithium.
Particularly preferred organophosphorus ligands employed in the form of a divalent transitional metal ion complex include for example, pentapotassium amino(- trimethylene phosphonate), tetrapotassium lhydroxyethylidene diphosphonate, pentasodium aminotri(methylene phosphonate), tetrasodium 1- hydroxyethylidene diphosphonate.
The plating baths of the present invention may be prepared for instance by forming an aqueous solution of a suitable metal compound and a phosphonate chelating agent of the present invention. Another method for-preparing the baths disclosed herein is to form an aqueous mixture of a metal chelate salt which has been previously prepared, e.g., by thereaction of a chelatable metal carbonate, hydroxide or oxide with a phos-,
phonic acid of the present invention, then neutralizing and adjusting the pH with a suitable alkaline compound such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, or the alkali metal carbonates.
The oxidizing agent of the invention is then added in the required small but effective concentration quantity.
It may be added initially or only after the bath has reached a stage in which it is not producing a satisfactory bright deposit.
Any water soluble metal compound which will form chelates with the above-described chelating agents may be used for the plating solutions of this invention including soluble compounds of iron, cobalt, nickel, zinc, silver, copper, cadmium and tin. The metal compounds employed in making up the baths may be (1) ionic metal salts which when solubilized release a chelatable metal ion, e.g., copper sulfate, or (2) complex salts which, when solubilized, will supply a chelatable metal ion, e.g., sodium zincate, or (3) metal salts, such as the carbonates which will react withphosphonic acid chelating agent to form a metal chelate salt. The plating of alloys can be achieved by the invention through the use of two or more different chelatable metals in the proper proportions. Examples of alloys which have been plated by the present invention are copper-nickel alloy, and copper-zinc yellow brass alloy and copper-zinc white brass alloy. 7 I
For best results, essentially neutral electroplating solution of 6 to 9 pH is preferable, but higher pH ranges, up to 13 as well as lower ranges to about 3 or 4 can also be used.
A number of other and further features have been discovered as improvements in the invention. These generally are selected metallic and non-metallic ions and organic compounds which can be added to improve further the brightness obtained;
For example, it has been discovered that certain metallic additives, when added to the plating baths of the invention, improve significantly the brightness of the deposits, provided the bath is stabilized with the oxidizing agent. These metals are thallium, lead and cadmium. The amounts used is about 0.01 to 0.5 g/l or a sufficient amount to give the brightness desired. These metals may be added as the soluble metal salt such sulfate, acetate, tartrate, citrate, chloride, and the like. Other metallic ions which can also be used include arsenic, antimony and bismuth and the amounts used are about 0.01 to 1 g/l or a sufficient amount to give the brightness desired. The ions can be added as the soluble salt such as tartrate. Of the metallics above listed bismuth has been found to be preferred.
It has also been found that selenium and tellurium can be advantageously used in the stabilized bath. They may be added as the sodium selenite or tellurite. The amounts that are useful are about 0.1 g/l or an amount sufficient to improve brightness.
It has also been found that amino acids can be used to improve the brightness of metallic deposits. Amino acids that are useful as additives to the plating baths are lysine hydrochloride, cysteine hydrochloride, alanine, methionine, glycine, l-tyrosine, and the like. The preferred amino acid additive is glycine. The amount re quired is about 0.01 to 5 g/l or an amount sufficient to produce the desired effect. Amino acids increase the ability of the plating solution to withstand prolonged electrolysis without plating dull.
It has been found that metal additives can be used with the amino acids, i.e., bismuth ions with glycine with achievement of good results.
In order to illustrate the novel electroplating baths of this invention a series of baths are exemplified below. While particular embodiments of the invention are specifically shown, it will be understood that the invention is obviously subject to variations and modifications without departing from its broader aspects.
The plating baths were prepared by dissolving in water the indicated quantity of the compound of the metal to be electrodeposited and the indicated phosphonate chelating agent. An alkali metal hydroxide was added to the solution to adjust the pH to the selected value. The examples illustrate the different metal compounds which can be used in the invention and which when solubilized release a metallic ion. For each of the baths described below, the electroplating of the metal was conducted in a 267 ml. Hull cell, in a conventional manner at a temperature in the range of from room temperature to 140F. and at a current of l ampere. Various brighteners which are described as further features of this invention were added to the bath as specific embodiments of the invention.
BATH A Grams per liter Ethylenediamine tetrarnethylphosphonic acid Copper sulfate The pH of the mixture was adjusted to 10.3 with potassium hydroxide. The electroplating was conducted at 140F. The resulting copper deposit was of overall dull appearance with a burned portion in the high current area.
This is Bath A'with glycine added. One half the panel from the low current density is bright.
BATH C Grams per liter Ethylenediamine tetramethyl phosphonic acid Copper sulfate 60 Sodium selenite 0.02
The pH of the mixture was adjusted to 8.0 with potassium hydroxide and the deposition temperature was F. The copper deposit was uniformly bright with a narrow burn in the high current area.
BATH D Grams per liter l-Hydroxyethylidene-diphosphonic acid I80 Copper hydroxide 24 Cysteine hydrochloride 0.04
Potassium hydroxide was used to adjust the pH to 10.3 and the metal was deposited at a temperature of 140F. The resulting deposit was completely bright except at the high current area.
The pH was adjusted to 10.3 with sodium hydroxide and the temperature was 140F. The resulting deposit was completely bright except in the area of high current.
BATH F To BathE there was added 2 g/l of glycine. The overall brightness of the metal-deposited was improved.
BATH G Grams per liter l-Hydroxyethylidene diphosphonic acid Copper hydroxide Ethylenediamine tetramethyl Phosphonic acid 4 BATH H After the deposit became dull and granular, 0.5 g/l of sodium chlorite was added to Bath G. The deposit remained uniformly semibright throughout the entire period of electrolysis.
BATH 1 After thedeposit became dull and granular, 1 cc/l of dimethyl sulfoxide was added to Bath G. The deposit remained uniformly semibright throughout the entire period of electrolysis.
BATH J Grams per liter Ethylenediamine tetramethylphosphonic 180 acid Nickel sulfate Sodium chlorite 0.05
Potassium hydroxide was added to adjust the pH to 5.0. A temperature of F. was used and the metal deposit was uniformly bright even after electrolyzing for ampere minutes.
BATH K To Bath G there was added 1 cc/l of 30 percent hydrogen peroxide. A metal deposit of uniform brightness was obtained throughout the entire period of electrolysis.
BATH L To. Bath G there was added 0.5 g/l of potassium permanganate. Good results in brightness were obtained throughout the entire period of electrolysis.
BATl-l M v 8 ml/l of 7% sodium hypochlorite solution was added to' Bath G. Similar good results were obtained with metal electrodeposition.
The above data demonstrate that the addition of oxidizing agents to the plating baths led to markedly improved deposition results.
What is claimed is:
1. In a process for producing deposits of metal which comprises electrodepositing metal from a cyanide-free aqueous solution containing an effective amount of a complex formed of a water soluble phosphonate chelating agent and at least one chelatable metal ion of a metal to be electrodeposited and capable of producing electrodeposits, the improvement which comprises including in the electroplating solution from about 0.01 to about 5.0 g/l of at least one oxidizing agent selected from the group consisting of peroxides, chlorites, perchlorates, hypochlorites, permanganates and sulfoxides.
2. The process according to claim 1 in which the metal undergoing electrodeposition is selected from the group consisting of iron, cobalt, nickel, zinc, silver, copper, cadmium and tin.
3. The process of claim 2 in which the metal undergoing electrodeposition is copper.
Claims (2)
- 2. The process according to claim 1 in which the metal undergoing electrodeposition is selected from the group consisting of iron, cobalt, nickel, zinc, silver, copper, cadmium and tin.
- 3. The process of claim 2 in which the metal undergoing electrodeposition is copper.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00345041A US3833486A (en) | 1973-03-26 | 1973-03-26 | Cyanide-free electroplating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00345041A US3833486A (en) | 1973-03-26 | 1973-03-26 | Cyanide-free electroplating |
Publications (1)
Publication Number | Publication Date |
---|---|
US3833486A true US3833486A (en) | 1974-09-03 |
Family
ID=23353213
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00345041A Expired - Lifetime US3833486A (en) | 1973-03-26 | 1973-03-26 | Cyanide-free electroplating |
Country Status (1)
Country | Link |
---|---|
US (1) | US3833486A (en) |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4048024A (en) * | 1975-03-27 | 1977-09-13 | International Lead Zinc Research Organization, Inc. | Bright levelling zinc plating |
DE3347593A1 (en) * | 1983-01-03 | 1984-07-05 | Omi International Corp., Warren, Mich. | AQUEOUS ALKALINE CYANIDE-FREE COPPER ELECTROLYTE AND METHOD FOR GALVANICALLY DEPOSITING A GRAIN-REFINED DUCTILE AND ADHESIVE COPPER LAYER ON A CONDUCTIVE SUBSTRATE |
US4469569A (en) * | 1983-01-03 | 1984-09-04 | Omi International Corporation | Cyanide-free copper plating process |
US4765871A (en) * | 1981-12-28 | 1988-08-23 | The Boeing Company | Zinc-nickel electroplated article and method for producing the same |
DE4023444A1 (en) * | 1989-07-24 | 1991-01-31 | Omi Int Corp | Cyanide-free copper plating process - where a portion of the plating bath is electrolysed by an independently-controlled insol. anode to reduce bath impurities |
US5057228A (en) * | 1990-04-16 | 1991-10-15 | Baker Hughes Incorporated | Metal ion complexes for use as scale inhibitors |
US5108554A (en) * | 1990-09-07 | 1992-04-28 | Collis, Inc. | Continuous method for preparing steel parts for resin coating |
US5207919A (en) * | 1990-04-16 | 1993-05-04 | Baker Hughes Incorporated | Metal ion complexes for use as scale inhibitors |
US5266212A (en) * | 1992-10-13 | 1993-11-30 | Enthone-Omi, Inc. | Purification of cyanide-free copper plating baths |
US5516414A (en) * | 1992-09-15 | 1996-05-14 | Atr Wire & Cable Co., Inc. | Method and apparatus for electrolytically plating copper |
US5607570A (en) * | 1994-10-31 | 1997-03-04 | Rohbani; Elias | Electroplating solution |
US7033463B1 (en) * | 1998-08-11 | 2006-04-25 | Ebara Corporation | Substrate plating method and apparatus |
US20060231409A1 (en) * | 2005-03-31 | 2006-10-19 | Tdk Corporation | Plating solution, conductive material, and surface treatment method of conductive material |
WO2008098666A1 (en) * | 2007-02-14 | 2008-08-21 | Umicore Galvanotechnik Gmbh | Copper-tin electrolyte and method for depositing bronze layers |
US20090071836A1 (en) * | 2007-09-17 | 2009-03-19 | International Business Machines Corporation | Method of electrodepositing germanium compound materials on a substrate |
DE102008032398A1 (en) * | 2008-07-10 | 2010-01-14 | Umicore Galvanotechnik Gmbh | Improved copper-tin electrolyte and process for depositing bronze layers |
US20100137970A1 (en) * | 2005-02-10 | 2010-06-03 | Srivastava Suresh C | Method of electroplating a conversion electron emitting source on implant |
US7947163B2 (en) | 2006-07-21 | 2011-05-24 | Novellus Systems, Inc. | Photoresist-free metal deposition |
WO2012022689A1 (en) * | 2010-08-17 | 2012-02-23 | Umicore Galvanotechnik Gmbh | Electrolyte and process for the deposition of copper-tin alloy layers |
US8236160B2 (en) | 2000-08-10 | 2012-08-07 | Novellus Systems, Inc. | Plating methods for low aspect ratio cavities |
CN103866355A (en) * | 2014-04-03 | 2014-06-18 | 苏州大学 | Cyanide-free silver-electroplating solution and electroplating method thereof |
KR20140130546A (en) * | 2012-04-19 | 2014-11-10 | 딥솔 가부시키가이샤 | Copper-nickel alloy electroplating bath and plating method |
US11661666B2 (en) * | 2019-10-10 | 2023-05-30 | The Boeing Company | Electrodeposited zinc and iron coatings for corrosion resistance |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3475293A (en) * | 1964-09-22 | 1969-10-28 | Monsanto Co | Electrodeposition of metals |
DE2023304A1 (en) * | 1969-05-15 | 1970-11-19 | Lea-Ronal, Inc., Freeport, N.Y. (V.St.A.) | Cyanide-free galvanic baths |
-
1973
- 1973-03-26 US US00345041A patent/US3833486A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3475293A (en) * | 1964-09-22 | 1969-10-28 | Monsanto Co | Electrodeposition of metals |
DE2023304A1 (en) * | 1969-05-15 | 1970-11-19 | Lea-Ronal, Inc., Freeport, N.Y. (V.St.A.) | Cyanide-free galvanic baths |
Non-Patent Citations (1)
Title |
---|
Frederick A. Lowenheim, Modern Electroplating, pp. 178 185 & 293 294, (1968), TS 670 E46 C.2. * |
Cited By (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4048024A (en) * | 1975-03-27 | 1977-09-13 | International Lead Zinc Research Organization, Inc. | Bright levelling zinc plating |
US4765871A (en) * | 1981-12-28 | 1988-08-23 | The Boeing Company | Zinc-nickel electroplated article and method for producing the same |
DE3347593A1 (en) * | 1983-01-03 | 1984-07-05 | Omi International Corp., Warren, Mich. | AQUEOUS ALKALINE CYANIDE-FREE COPPER ELECTROLYTE AND METHOD FOR GALVANICALLY DEPOSITING A GRAIN-REFINED DUCTILE AND ADHESIVE COPPER LAYER ON A CONDUCTIVE SUBSTRATE |
US4469569A (en) * | 1983-01-03 | 1984-09-04 | Omi International Corporation | Cyanide-free copper plating process |
DE4023444A1 (en) * | 1989-07-24 | 1991-01-31 | Omi Int Corp | Cyanide-free copper plating process - where a portion of the plating bath is electrolysed by an independently-controlled insol. anode to reduce bath impurities |
US5207919A (en) * | 1990-04-16 | 1993-05-04 | Baker Hughes Incorporated | Metal ion complexes for use as scale inhibitors |
US5057228A (en) * | 1990-04-16 | 1991-10-15 | Baker Hughes Incorporated | Metal ion complexes for use as scale inhibitors |
US5108554A (en) * | 1990-09-07 | 1992-04-28 | Collis, Inc. | Continuous method for preparing steel parts for resin coating |
US5516414A (en) * | 1992-09-15 | 1996-05-14 | Atr Wire & Cable Co., Inc. | Method and apparatus for electrolytically plating copper |
US5266212A (en) * | 1992-10-13 | 1993-11-30 | Enthone-Omi, Inc. | Purification of cyanide-free copper plating baths |
US5607570A (en) * | 1994-10-31 | 1997-03-04 | Rohbani; Elias | Electroplating solution |
US7033463B1 (en) * | 1998-08-11 | 2006-04-25 | Ebara Corporation | Substrate plating method and apparatus |
US20060144714A1 (en) * | 1998-08-11 | 2006-07-06 | Akihisa Hongo | Substrate plating method and apparatus |
US8236160B2 (en) | 2000-08-10 | 2012-08-07 | Novellus Systems, Inc. | Plating methods for low aspect ratio cavities |
US8114264B2 (en) * | 2005-02-10 | 2012-02-14 | Brookhaven Science Associates | Method of electroplating a conversion electron emitting source on implant |
US20100137970A1 (en) * | 2005-02-10 | 2010-06-03 | Srivastava Suresh C | Method of electroplating a conversion electron emitting source on implant |
US20060231409A1 (en) * | 2005-03-31 | 2006-10-19 | Tdk Corporation | Plating solution, conductive material, and surface treatment method of conductive material |
US8500985B2 (en) | 2006-07-21 | 2013-08-06 | Novellus Systems, Inc. | Photoresist-free metal deposition |
US7947163B2 (en) | 2006-07-21 | 2011-05-24 | Novellus Systems, Inc. | Photoresist-free metal deposition |
EP1961840A1 (en) * | 2007-02-14 | 2008-08-27 | Umicore Galvanotechnik GmbH | Copper-tin electrolyte and method for depositing bronze layers |
US20100147696A1 (en) * | 2007-02-14 | 2010-06-17 | Klaus Bronder | Copper-tin electrolyte and method for depositing bronze layers |
WO2008098666A1 (en) * | 2007-02-14 | 2008-08-21 | Umicore Galvanotechnik Gmbh | Copper-tin electrolyte and method for depositing bronze layers |
CN101622379B (en) * | 2007-02-14 | 2011-05-25 | 尤米科尔电镀技术有限公司 | Copper-tin electrolyte and method for depositing bronze layers |
US8211285B2 (en) * | 2007-02-14 | 2012-07-03 | Umicore Galvanotechnik Gmbh | Copper-tin electrolyte and method for depositing bronze layers |
US7918984B2 (en) | 2007-09-17 | 2011-04-05 | International Business Machines Corporation | Method of electrodepositing germanium compound materials on a substrate |
US20090071836A1 (en) * | 2007-09-17 | 2009-03-19 | International Business Machines Corporation | Method of electrodepositing germanium compound materials on a substrate |
US20110174631A1 (en) * | 2008-07-10 | 2011-07-21 | Umicore Galvanotechnik Gmbh | Copper-tin electrolyte and process for the deposition of bronze layers |
DE102008032398A1 (en) * | 2008-07-10 | 2010-01-14 | Umicore Galvanotechnik Gmbh | Improved copper-tin electrolyte and process for depositing bronze layers |
WO2012022689A1 (en) * | 2010-08-17 | 2012-02-23 | Umicore Galvanotechnik Gmbh | Electrolyte and process for the deposition of copper-tin alloy layers |
CN103069054A (en) * | 2010-08-17 | 2013-04-24 | 尤米科尔电镀技术有限公司 | Electrolyte and process for the deposition of copper-tin alloy layers |
CN103069054B (en) * | 2010-08-17 | 2016-08-10 | 尤米科尔电镀技术有限公司 | For depositing electrolyte and the method for copper-tin alloy layers |
KR20140130546A (en) * | 2012-04-19 | 2014-11-10 | 딥솔 가부시키가이샤 | Copper-nickel alloy electroplating bath and plating method |
US20150090600A1 (en) * | 2012-04-19 | 2015-04-02 | Dipsol Chemicals Co., Ltd. | Copper-nickel alloy electroplating bath and plating method |
KR101649435B1 (en) | 2012-04-19 | 2016-08-19 | 딥솔 가부시키가이샤 | Copper-nickel alloy electroplating bath and plating method |
TWI580822B (en) * | 2012-04-19 | 2017-05-01 | 迪普索股份有限公司 | Copper-nickel alloy electroplating bath and electroplating method |
US9828686B2 (en) * | 2012-04-19 | 2017-11-28 | Dipsol Chemicals Co., Ltd. | Copper-nickel alloy electroplating bath and plating method |
CN103866355A (en) * | 2014-04-03 | 2014-06-18 | 苏州大学 | Cyanide-free silver-electroplating solution and electroplating method thereof |
US11661666B2 (en) * | 2019-10-10 | 2023-05-30 | The Boeing Company | Electrodeposited zinc and iron coatings for corrosion resistance |
US20230304182A1 (en) * | 2019-10-10 | 2023-09-28 | The Boeing Company | Electrodeposited zinc and iron coatings for corrosion resistance |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3833486A (en) | Cyanide-free electroplating | |
US3706635A (en) | Electrochemical compositions and processes | |
EP0611840B1 (en) | Cyanide-free plating solutions for monovalent metals | |
EP1009869B1 (en) | Cyanide-free monovalent copper electroplating solutions | |
US4591415A (en) | Plating baths and methods for electro-deposition of gold or gold alloys | |
US4469569A (en) | Cyanide-free copper plating process | |
US3980531A (en) | Bath and process for the electrolytic separation of rare metal alloys | |
US4687557A (en) | Gold alloys and galvanic bath for the electrolytic deposit thereof | |
US3902977A (en) | Gold plating solutions and method | |
US4715935A (en) | Palladium and palladium alloy plating | |
JPH06173074A (en) | Electroplated alloy of gold, copper and silver | |
US3914162A (en) | Compositions and process for the electrodeposition of metals | |
EP0304315B1 (en) | Bath for electrolytic deposition of a gold-copper-zinc alloy | |
US3879270A (en) | Compositions and process for the electrodeposition of metals | |
US4462874A (en) | Cyanide-free copper plating process | |
US4478692A (en) | Electrodeposition of palladium-silver alloys | |
US4265715A (en) | Silver electrodeposition process | |
GB2046794A (en) | Silver and gold/silver alloy plating bath and method | |
US3440151A (en) | Electrodeposition of copper-tin alloys | |
JPS609116B2 (en) | Electrodeposition method for palladium and palladium alloys | |
US4521282A (en) | Cyanide-free copper electrolyte and process | |
US4048023A (en) | Electrodeposition of gold-palladium alloys | |
US3990954A (en) | Sulfite gold plating bath and process | |
US4297179A (en) | Palladium electroplating bath and process | |
GB2151661A (en) | Deposition of gold-copper-zinc alloys |