US2852449A - Electrodeposition of nickel - Google Patents
Electrodeposition of nickel Download PDFInfo
- Publication number
- US2852449A US2852449A US683721A US68372157A US2852449A US 2852449 A US2852449 A US 2852449A US 683721 A US683721 A US 683721A US 68372157 A US68372157 A US 68372157A US 2852449 A US2852449 A US 2852449A
- Authority
- US
- United States
- Prior art keywords
- nickel
- dioxane
- sulfonimides
- liter
- benzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 59
- 229910052759 nickel Inorganic materials 0.000 title claims description 29
- 238000004070 electrodeposition Methods 0.000 title description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 24
- -1 NAPHTHALENE SULFONIC ACIDS Chemical class 0.000 claims description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical class C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 229940124530 sulfonamide Drugs 0.000 claims description 8
- 150000003456 sulfonamides Chemical class 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical group C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 238000013019 agitation Methods 0.000 description 8
- 150000000093 1,3-dioxanes Chemical class 0.000 description 5
- OOXMQACSWCZQLX-UHFFFAOYSA-N 3,9-bis(ethenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OC(C=C)OCC21COC(C=C)OC2 OOXMQACSWCZQLX-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 150000008331 benzenesulfonamides Chemical class 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- PMCYAZIDOVWKAH-UHFFFAOYSA-N but-2-yne-1,4-disulfonic acid Chemical compound OS(=O)(=O)CC#CCS(O)(=O)=O PMCYAZIDOVWKAH-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CGLHFJGXOBNMGI-UHFFFAOYSA-N 1,5-diphenylcyclohexa-2,4-diene-1-sulfonic acid Chemical compound C1(=CC=CC=C1)C1(CC(=CC=C1)C1=CC=CC=C1)S(=O)(=O)O CGLHFJGXOBNMGI-UHFFFAOYSA-N 0.000 description 1
- MBUIVAAHRBEDCW-UHFFFAOYSA-N 2-ethenyl-1,3-dioxane Chemical compound C=CC1OCCCO1 MBUIVAAHRBEDCW-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- PXACTUVBBMDKRW-UHFFFAOYSA-N 4-bromobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Br)C=C1 PXACTUVBBMDKRW-UHFFFAOYSA-N 0.000 description 1
- LTSOENFXCPOCHG-GQCTYLIASA-N 4-chloro-6-[[(e)-3-oxobut-1-enyl]amino]-1-n-prop-2-enylbenzene-1,3-disulfonamide Chemical compound CC(=O)\C=C\NC1=CC(Cl)=C(S(N)(=O)=O)C=C1S(=O)(=O)NCC=C LTSOENFXCPOCHG-GQCTYLIASA-N 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 125000003047 N-acetyl group Chemical group 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- PWHVEHULNLETOV-UHFFFAOYSA-N Nic-1 Natural products C12OC2C2(O)CC=CC(=O)C2(C)C(CCC2=C3)C1C2=CC=C3C(C)C1OC(O)C2(C)OC2(C)C1 PWHVEHULNLETOV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 206010042618 Surgical procedure repeated Diseases 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229950007019 ambuside Drugs 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FJCOPDAKOAJJRG-UHFFFAOYSA-N benzenesulfonamidomethanesulfonic acid Chemical compound OS(=O)(=O)CNS(=O)(=O)C1=CC=CC=C1 FJCOPDAKOAJJRG-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- UNYWISZSMFIKJI-UHFFFAOYSA-N prop-2-ene-1-sulfonamide Chemical compound NS(=O)(=O)CC=C UNYWISZSMFIKJI-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- RRLOOYQHUHGIRJ-UHFFFAOYSA-M sodium;ethyl sulfate Chemical compound [Na+].CCOS([O-])(=O)=O RRLOOYQHUHGIRJ-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000011282 treatment Methods 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
Definitions
- This invention relates to the electrodeposition of nickel and more particularly it relates to the electrodeposition of bright ductile nickel from aqueous acidic nickel electroplating baths.
- the vinyl substituted saturated ring, m-dioxane, compounds of Table I give far superior brightening results than when the vinyl group is attached to an aromatictype ring such as benzene or pyridine. This is thought to be due to the fact that in the compounds of Table I the vinyl group is, in fact, an allylic group with the terminal, i. e. farthest from thedouble bond carbon atom of the allylic group as part of the dioxane ring.
- the compounds of Table I are efiective in very low concentrations, and when fast agitation is used (air or mechanical, or hydraulic), concentrations as low as about two or three milligrams per liter show beneficial brightening effects. In general, however, concentrations of about 0.01 to 0.06 gram/liter are preferred, though much higher concentrations can be used, for example, up to about 0.2 gram/liter and in some cases as high as 0.5 gram/liter.
- Sulfomethyl benzene sulfonamide 0, 1-6 10. Benzene sultonamide m-carboxylic 0. 1-3 11. 7-Aldehydo o-benzoyl sulfilnide 0.1-3 12. N-acetyl benzene sulfonimide. 0.1-2 18. Methoxy benzene sulionamides 0.1-1 14. Hydroxymethyl benzene sulf0namide 0. 1-2 15. Allyl sulfonamide 0. 4-12 16. Benzene sulionie acids (mono-, di-, and tri 1-15 17. p-Brom benzene sulfonic acid 3-6 18. Benzaldehyde sultonie acids (0, m, p) 2-6 19.
- Di-benzene sulfonimide- 0. 1-3 30.
- Di-toluene sulf0nimide 0.1-3 31.
- Z-Butyne- 1,4-disulionie acid. 5-20 32.
- 4-Hydr0xy-2-butyne-1-su1fonic acid 0.2-2 33.
- 2-butene-1A-disulfonic acid .03-5 36.
- fluoborate, and sulfamate baths and mixtures of these various nickel salts may be present, also ammonium ions, though the latter should preferably be kept below about 7 grams per liter for maximum ductility and brightness.
- Boric acid is the preferred buffer.
- the best pH range is from about 2.8 to 4.5, though pH values of 2 to 6 may be used.
- the temperature of' 3 the bath may be from room to 190 F., though in general 120 F.l60 F. is preferred.
- a suitable surface-active agent such as sodium lauryl sulfate, sodium Z-ethyl hexyl sulfate or sulfonate, octyl sulfonic acid, etc.
- a surface-active agent such as sodium lauryl sulfate, sodium Z-ethyl hexyl sulfate or sulfonate, octyl sulfonic acid, etc.
- sodium 2-ethyl sulfate can be used which does not foam excessively, or otherwise a more powerful surface-active agent such as sodium lauryl sulfate can be used in conjunction with an anti-foam such as a silicone oil or a tallow alcohol.
- the compounds of Table II can be used in amounts between about 0.1 gram/liter and saturation and the preferred organic sultan-compounds to be used with the compounds of Table I are the benzene sulfonamides and sulfonimides (0.1 gram/liter to saturation) especially when used in conjunction with allyl sulfonic acid (0.6-2 grams/liter) or Z-butyne disulfonic acid (3-10 grams/ liter).
- the preferred compound of Table I is Example 2, which is 3,9-divinyl spirobi (m-dioxane), in a concentration of 0.01 to 0.05 gram/liter.
- the baths containing compounds of Table I and Table II are not very sensitive to giving poor adhesion due to broken electrical contacts or to small excesses of these compounds, and therefore these compounds do not readily cause double or laminated plates.
- the compounds of Table I in conjunction with those of Table II give excellent results in bulk, tumble or barrel plating, as well as in the rack plating of steel, zinc diecast, aluminum and brass articles. Especially superior results (brightness and ductility) are obtained with rapid agitation (air agitation or hydraulic agitation).
- the conjunctive use of the compounds of Table I with the compounds of Table II does not greatly reduce the excellent properties which are characteristic of all of the organic sulfon-compounds of Table II with respect to the low sensitivity of nickel baths containing the latter organic sulfon-compounds to poor adhesion from broken electrical contacts or delayed electrical contacts or from reverse or anodic currents as in periodic current reversals, or in anodic activation of the nickel plate for re-plate. Delays of as long as one minute before electrical contact is made, or anodic currents for as long as one minute in many cases, do not cause poor adhesion.
- Zinc ions or cadmium ions can be present in most of the nickel baths, especially in high chloride baths, in concentrations of at least 0.05 to 0.1 gram per liter and also not aifect the adhesion during delayed electrical contacts or periodic current reversals.
- the zinc or cadmium present in the nickel plate causes a more shallow type of corrosion pit to occur in the nickel when chromium plated and exposed to a corrosive atmosphere (for example the atmosphere in industrial areas).
- the relative insensitivity of such baths to passivity from anodic current makes possible the use of periodic current reversal in its sacrificial form which tends to promote leveling and to improve the corrosion protection afiorded to the underlying metal.
- a sacrificial periodic current reversal cycle of ten or more seconds anodic current preferably at low anodic current (5 to 10 amps/sq. ft.) with about 1 to 5 seconds cathodic current can be used for periods of about 1 to 2 or more minutes and then the procedure repeated until the desired thickness of plate is obtained.
- the benzene sulfonamides and sulfonimides and o-benzoyl sulfimide together with small concentrations of the compounds of Table I represent preferred combinations of the compounds of this invention for the periodic current reversal treatments.
- Example I NiSO .6H O "grams/liter" 200-300 NiCl .6H O do 30-80 H3803 d0 N-aBF do 0-0.S
- Example 2 of Table I (3,9-divinyl spirobi (m-dioxane) grams/liter 0.01-0.04 Sodium allyl sulfonate do 0.6-2 Benbene sulfonamide do 1-2 o-Benzoyl sulfimide do 0-2 Temperature F 120-160 pH 3.2-4.8
- Example II NiCl .6H- O grarns/liter -200 -d0 H 30 do 30-50
- Example 2 of Table I (3,9-divinyl spirobi (m-dioxane) grams/liter- 0.01-0.04 Sodium allyl sulfonate do 0.6-2 o-Benzoyl sulfimide do 1-2 Benzene sulfonamide do 1-2 Temperature F -160 pH 3.2-4.8
- Example III NiSO .6H O grams/liter 200-300 NiC1 .6H O do 30-100 H3B03 ..d0
- Example I of Table I (vinyl-m-dioxane) grams/liter 0.01-0.05 o-Benzoyl sulfimide do 0.1-2 Temperature F 120-160 pH 3.2-4.8
- Example IV NiS0 .6H O grams/liter 200-300 NiCl .6H O do 30-80 H BO do 30-50 NaBF o 0-0.5
- Example 2 of Table I (3,9-divinyl spirobi (m-dioxane) grams/1iter 0.01-0.04 2-Butyne 1,4-disulfonic acid Na, K, or Ni salt) grams/liter- 3-10 Benzene sultonamide do 1-2 o-Benzoyl sulfimide do 0-2 Temperature F 120-160 pH 3.2-4.8
- a bath for electrodepositing bright, ductile nickel plate which comprises an aqueous acidic solution containing at least one electrolyte selected from the group consisting of nickel sulfate, nickel chloride, nickel fluoborate and nickel sulfamate, and having dissolved therein about 0.1 gram/ liter to saturation of at least one organic sulfon- .compound selected from the class consisting of benzene, biphenyl and naphthalene sulfonic acids, sulfonamides and sulfonimides and the mixed phenyl, biphenyl and naphthyl sulfonamides and the mono-, di-, tri-, and tetrasulfonimides thereof, and dibenzene sulfonimides and the halogen, methyl, and aldehydo derivatives of said sulfonic acids, sulfonamides and sulfonimides, and beta unsaturated alkene and al
- a bath in accordance with claim 1 wherein said vinyl substituted m-dioxane compound is 3,9-divinyl spirobi (m-dioxane) and is present in a concentration in the bath of 0.005 to about 0.2 gram/liter.
- a bath in accordance with claim 1 wherein the vinyl substituted m-dioxane is 3-viny1' m-dioxane and is dissolved in the said nickel bath in a concentration of 0.005 to about 0.2 gram/ liter.
- a bath in accordance with claim 1 wherein said organic sulfon-compound is allyl sulfonate.
- a bath in accordance with claim 1 wherein said organic sulfon-compound is 2-butyne-1,4-disulfonate.
- a method of electrodepositing bright, ductile nickel plate which comprises electrolyzing an aqueous acidic solution comprising at least one nickel salt selected from the group consisting of nickel sulfate, nickel .chloride, nickel fluoborate and nickel sulfamate, said bath containing dissolved therein about 0.1 gram/liter to saturation of at least one organic sulfon-compound selected from the group consisting of benzene, biphenyl and naphthalene sulfonic acids, sulfonamides and sulfonim-ides and the mixed phenyl, biphenyl and naphthyl sulfonamides and the mono-, di-, tri-, and tetrasulfonimides thereof, and dibenzene sulfonimides and the halogen, methyl, and aldehydo derivatives of said sulfonic acids, sulfonamides and sulfonimides, and beta unsaturated al
- said vinyl Substituted m-dioxane compound is 3,9-divinyl spirobi (m-dioxane) and is present in a concentration in the bath of 0.005 to about 0.2 gram/liter.
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Description
- United States Patent ELECTRODEPOSITION OF NICKEL Donald H. Becking, Birmingham, and Henry Brown, Huntington Woods, Mich., assignors to The Udylite Research Corporation, Detroit, Mich., a corporation of Michigan No Drawing. Application September 13, 1957 Serial No. 683,721
Claims. (Cl. 204-49) This invention relates to the electrodeposition of nickel and more particularly it relates to the electrodeposition of bright ductile nickel from aqueous acidic nickel electroplating baths.
In accordance with this invention, it has been found that certain vinyl substituted m-dioxane compounds, such as those illustrated in Table I, containing the O. CHFCH-Cfi grouping I when used in very small concentrations in aqueous acidic nickel baths in conjunction with the well-known organic sulfon-compounds (as illustrated in Table II) make possible the production of brilliant ductile nickel plate.
While numerous unsaturated compounds have been used in the art in conjunction with sulfon-compounds to obtain bright ductile nickel plate, the number of highly satisfactory unsaturated vinyl substituted compounds have been very few. For example, 2-vinyl pyridine is actually far inferior to pyridine as a nickel brightener when used in conjunction with an aryl sulfoncompound and vinyl benzene is insoluble in a Watts-type nickel bath.
The vinyl substituted saturated ring, m-dioxane, compounds of Table I give far superior brightening results than when the vinyl group is attached to an aromatictype ring such as benzene or pyridine. This is thought to be due to the fact that in the compounds of Table I the vinyl group is, in fact, an allylic group with the terminal, i. e. farthest from thedouble bond carbon atom of the allylic group as part of the dioxane ring.
TABLE I..-Continued Optimum Oonc., Grams/liter CHz=CH-C CHOCHax' 0.01 to 0.06
OCz
7. OCH2 CH2=CHC /CHOC2H5 0. 01 to 0.06
O-CHg 8. O C H: g CHz=OH-C\ CHO(C2H4O),.H 0.01 to 0.06
The compounds of Table I are efiective in very low concentrations, and when fast agitation is used (air or mechanical, or hydraulic), concentrations as low as about two or three milligrams per liter show beneficial brightening effects. In general, however, concentrations of about 0.01 to 0.06 gram/liter are preferred, though much higher concentrations can be used, for example, up to about 0.2 gram/liter and in some cases as high as 0.5 gram/liter.
TABLE II Optimum Sulfur-Containing Brighteners Cone, grams/ liter 1. Benzene sulfonamide 0.1-3 2. Toluene sulionamides (oand p-) 0. 1-2 3. o-Benzoyl sulfimide 0. 1-2 4. N-Benzoyl benzene sultonimide. 0.1-1 5. p-Toluene sultonchloramide. 0. 1-1 6. p-Brom benzene sulonamide 0. 1-1 7. G-Chlor o-benzoyl sulfirnide. 0, 1-1 8. m-Aldebydo benzene snlfonami 0.1-1 9. Sulfomethyl benzene sulfonamide 0, 1-6 10. Benzene sultonamide m-carboxylic 0. 1-3 11. 7-Aldehydo o-benzoyl sulfilnide 0.1-3 12. N-acetyl benzene sulfonimide. 0.1-2 18. Methoxy benzene sulionamides 0.1-1 14. Hydroxymethyl benzene sulf0namide 0. 1-2 15. Allyl sulfonamide 0. 4-12 16. Benzene sulionie acids (mono-, di-, and tri 1-15 17. p-Brom benzene sulfonic acid 3-6 18. Benzaldehyde sultonie acids (0, m, p) 2-6 19. Diphenyl sulfone sulfonic acid 1-8 20. Naphthalene sulfonic acids (mono-, di-, and tr) 1-8 21. Benzene snliohydroxamic acid 1-5 22. p-Chlor benzene sultonic acid- 1-15 23. Diphenyl sulfonic acid 1-5 24. m-Diphenyl benzene sulfonic acid. 1-4 25. 2-0hloro-5-sulfobenzaldehyde 1-5 26. m-Benzene disulfonamide. 0. 5-1 27. Ally] sulionic acid 0. 4-12 28. DichlOrOb'enzene sulfonic a 0. 5-8 29. Di-benzene sulfonimide- 0. 1-3 30. Di-toluene sulf0nimide 0.1-3 31. Z-Butyne- 1,4-disulionie acid. 5-20 32. 4-Hydr0xy-2-butyne-1-su1fonic acid 0.2-2 33. z-Butyne-i-sultonic acid 0. 05-1. 5 34. 3Cl1lor0-2-pr0pyne-1-sulf0nic acid. 0. 05-1. 5 35. 2-butene-1A-disulfonic acid .03-5 36. 2-cl1l0ro butene-4-su1fonic acid- 0. 3-5 37. 2-cl1l0ro propene sulfonic acid 0.1-1. 5 38. Cinnamyl sulionic acid; 0. 1-3. 0 39. 3-Phenyl-2-propyne-1-sulf0nic acid. 0.3-3.0 40. 4-Methoxy-2-butyne-1-sult0nic acid 0.2-2
The combination of the compounds of Table I with those of Table II can be used in all types of acidic nickel baths that give good ductile gray nickel deposits without the additives, such as Watts nickel baths, high chloride,
fluoborate, and sulfamate baths and mixtures of these various nickel salts. Sodium, potassium, and lithium ions may be present, also ammonium ions, though the latter should preferably be kept below about 7 grams per liter for maximum ductility and brightness. Boric acid is the preferred buffer.
The best pH range is from about 2.8 to 4.5, though pH values of 2 to 6 may be used. The temperature of' 3 the bath may be from room to 190 F., though in general 120 F.l60 F. is preferred.
When no air agitation or strong mechanical or hydraulic agitation is used, it is preferred to use a suitable surface-active agent such as sodium lauryl sulfate, sodium Z-ethyl hexyl sulfate or sulfonate, octyl sulfonic acid, etc., to prevent gas-pitting. With air agitation, it is usually not necessary to use a surface-active agent but if desired, sodium 2-ethyl sulfate can be used which does not foam excessively, or otherwise a more powerful surface-active agent such as sodium lauryl sulfate can be used in conjunction with an anti-foam such as a silicone oil or a tallow alcohol.
The compounds of Table II can be used in amounts between about 0.1 gram/liter and saturation and the preferred organic sultan-compounds to be used with the compounds of Table I are the benzene sulfonamides and sulfonimides (0.1 gram/liter to saturation) especially when used in conjunction with allyl sulfonic acid (0.6-2 grams/liter) or Z-butyne disulfonic acid (3-10 grams/ liter). The preferred compound of Table I is Example 2, which is 3,9-divinyl spirobi (m-dioxane), in a concentration of 0.01 to 0.05 gram/liter.
The baths containing compounds of Table I and Table II are not very sensitive to giving poor adhesion due to broken electrical contacts or to small excesses of these compounds, and therefore these compounds do not readily cause double or laminated plates. For these reasons, the compounds of Table I in conjunction with those of Table II give excellent results in bulk, tumble or barrel plating, as well as in the rack plating of steel, zinc diecast, aluminum and brass articles. Especially superior results (brightness and ductility) are obtained with rapid agitation (air agitation or hydraulic agitation).
In the following examples typical bath compositions and conditions are illustrated for obtaining the bright nickel deposits in accordance with this invention, but it is to be understood that they are representative only, and that the compounds of Table I can be used in such bath compositions with each compound or combinations of the compounds of Table II or other organic sulfoncompounds similar to those of Table II such as those carrying di-, tri-, or tetra-sulfonimide groups of phenyl, biphenyl, naphthyl, or mixed phenyl, biphenyl etc., di-, tri-, and tetra-sulfonimides, such as in the approximate proportions indicated in Table II. Furthermore, the conjunctive use of the compounds of Table I with the compounds of Table II does not greatly reduce the excellent properties which are characteristic of all of the organic sulfon-compounds of Table II with respect to the low sensitivity of nickel baths containing the latter organic sulfon-compounds to poor adhesion from broken electrical contacts or delayed electrical contacts or from reverse or anodic currents as in periodic current reversals, or in anodic activation of the nickel plate for re-plate. Delays of as long as one minute before electrical contact is made, or anodic currents for as long as one minute in many cases, do not cause poor adhesion. Zinc ions or cadmium ions can be present in most of the nickel baths, especially in high chloride baths, in concentrations of at least 0.05 to 0.1 gram per liter and also not aifect the adhesion during delayed electrical contacts or periodic current reversals. As a matter of fact, the zinc or cadmium present in the nickel plate causes a more shallow type of corrosion pit to occur in the nickel when chromium plated and exposed to a corrosive atmosphere (for example the atmosphere in industrial areas). The relative insensitivity of such baths to passivity from anodic current, makes possible the use of periodic current reversal in its sacrificial form which tends to promote leveling and to improve the corrosion protection afiorded to the underlying metal. For
example, after the initial deposition of a thin nickel plate (0.1 to 0.2 mil), a sacrificial periodic current reversal cycle of ten or more seconds anodic current preferably at low anodic current (5 to 10 amps/sq. ft.) with about 1 to 5 seconds cathodic current can be used for periods of about 1 to 2 or more minutes and then the procedure repeated until the desired thickness of plate is obtained. The benzene sulfonamides and sulfonimides and o-benzoyl sulfimide together with small concentrations of the compounds of Table I represent preferred combinations of the compounds of this invention for the periodic current reversal treatments.
Example I NiSO .6H O "grams/liter" 200-300 NiCl .6H O do 30-80 H3803 d0 N-aBF do 0-0.S Example 2 of Table I (3,9-divinyl spirobi (m-dioxane) grams/liter 0.01-0.04 Sodium allyl sulfonate do 0.6-2 Benbene sulfonamide do 1-2 o-Benzoyl sulfimide do 0-2 Temperature F 120-160 pH 3.2-4.8
Example II NiCl .6H- O grarns/liter -200 -d0 H 30 do 30-50 Example 2 of Table I (3,9-divinyl spirobi (m-dioxane) grams/liter- 0.01-0.04 Sodium allyl sulfonate do 0.6-2 o-Benzoyl sulfimide do 1-2 Benzene sulfonamide do 1-2 Temperature F -160 pH 3.2-4.8
Example III NiSO .6H O grams/liter 200-300 NiC1 .6H O do 30-100 H3B03 ..d0 Example I of Table I (vinyl-m-dioxane) grams/liter 0.01-0.05 o-Benzoyl sulfimide do 0.1-2 Temperature F 120-160 pH 3.2-4.8
Example IV NiS0 .6H O grams/liter 200-300 NiCl .6H O do 30-80 H BO do 30-50 NaBF o 0-0.5 Example 2 of Table I (3,9-divinyl spirobi (m-dioxane) grams/1iter 0.01-0.04 2-Butyne 1,4-disulfonic acid Na, K, or Ni salt) grams/liter- 3-10 Benzene sultonamide do 1-2 o-Benzoyl sulfimide do 0-2 Temperature F 120-160 pH 3.2-4.8
The above baths gave brilliant ductile nickel deposits that were remarkably adherent even when electrical contact was not instantly made. Exceptionally good results Were obtained with air agitation, especially in baths of Examples I, II and IV.
What is claimed is:
1. A bath for electrodepositing bright, ductile nickel plate which comprises an aqueous acidic solution containing at least one electrolyte selected from the group consisting of nickel sulfate, nickel chloride, nickel fluoborate and nickel sulfamate, and having dissolved therein about 0.1 gram/ liter to saturation of at least one organic sulfon- .compound selected from the class consisting of benzene, biphenyl and naphthalene sulfonic acids, sulfonamides and sulfonimides and the mixed phenyl, biphenyl and naphthyl sulfonamides and the mono-, di-, tri-, and tetrasulfonimides thereof, and dibenzene sulfonimides and the halogen, methyl, and aldehydo derivatives of said sulfonic acids, sulfonamides and sulfonimides, and beta unsaturated alkene and alkyne sulfonic acids having 4-2 carbon atoms, and about 0.002 to about 0.5 gram/ liter of a compound selected from the group consisting of vinyl substituted m-dioxane, and di-vinyl substituted bi(m-dioxane), and derivatives thereof, in which derivatives the m-dioxane ring is substituted with a radical selected from the group consisting of chloro, bromo, hydroxy, methoxy, ethoxy and hydroxy-ethoxy radicals.
2. A bath in accordance with claim 1 wherein said vinyl substituted m-dioxane compound is 3,9-divinyl spirobi (m-dioxane) and is present in a concentration in the bath of 0.005 to about 0.2 gram/liter.
3. A bath in accordance with claim 1 wherein the vinyl substituted m-dioxane is 3-viny1' m-dioxane and is dissolved in the said nickel bath in a concentration of 0.005 to about 0.2 gram/ liter.
4. A bath in accordance with claim 1 wherein said organic sulfon-compound is allyl sulfonate.
5. A bath in accordance with claim 1 wherein said organic sulfon-compound is 2-butyne-1,4-disulfonate.
6. A method of electrodepositing bright, ductile nickel plate which comprises electrolyzing an aqueous acidic solution comprising at least one nickel salt selected from the group consisting of nickel sulfate, nickel .chloride, nickel fluoborate and nickel sulfamate, said bath containing dissolved therein about 0.1 gram/liter to saturation of at least one organic sulfon-compound selected from the group consisting of benzene, biphenyl and naphthalene sulfonic acids, sulfonamides and sulfonim-ides and the mixed phenyl, biphenyl and naphthyl sulfonamides and the mono-, di-, tri-, and tetrasulfonimides thereof, and dibenzene sulfonimides and the halogen, methyl, and aldehydo derivatives of said sulfonic acids, sulfonamides and sulfonimides, and beta unsaturated alkene and alkyne sulfonic acids having 4-2 carbon atoms, and about 0.002 to about 0.5 gram/ liter of a compound selected from the group consisting of vinyl substituted m-dioxane, and divinyl substituted bi(m-dioxane), and derivatives thereof, in which derivatives the m-dioxane ring is substituted with a radical selected from the group consisting of chloro, bromo, hydroxy, methoxy, ethoxy and hydroxy-ethoxy radicals.
7. A method in accordance with claim 6 wherein said vinyl Substituted m-dioxane compound is 3,9-divinyl spirobi (m-dioxane) and is present in a concentration in the bath of 0.005 to about 0.2 gram/liter.
8. A method in accordance with claim 6 wherein the vinyl substituted m-dioxane is 3-vinyl m-dioxane and is dissolved in the said nickel bath in a concentration of 0.005 to about 0.2 gram/liter.
9. A method in accordance with claim 6 wherein said organic sulfon-compound is allyl sulfonate.
10. A method in accordance with claim 6 wherein said organic sulfon-compound is Z-butyne-l,4-disulfonate.
No references cited.
Claims (1)
1. A BATH FOR ELECTRODEPOSITING BRIGHT, DUCTILE NICKEL PLATE WHICH COMPRISES AN AQUEOUS ACIDIC SOLUTION CONTAINING AT LEAST ONE ELECTROCLYTE SELECTED FROM THE GROUP CONSISTING OF NICKEL SULFATE, NICKEL CHLORIDE, NICKEL FLUOBORATE AND NICKEL SULFAMATE, AND HAVING DISSOLVED THEREIN ABOUT 0.1 GRAM/LITER TO SATURATION OF AT LEAST ONE ORGANIC SULFONCOMPOUND SELECTED FROM THE CLASS CONSISTING OF BENZENE, BIPHENYL AND NAPHTHALENE SULFONIC ACIDS, SULFONOMIDES AND SULFONIMIDES AND THE MIXED PHENYL, BIPHENYL AND NAPHTHYL SULFONIMIDES AND THE MONO-, DI-, TRI, AND TETRASULFONIMIDES THEREOF, AND DIBENZENE SULFONIMIDES AND THE HALOGEN, MEYTHYL, AND ALDEHYDO DERIVATIVES OF SAID SULFONIC ACIDS, SULFONAMIDES AND SULFONIMIDES, AND BETA UNSATURATED ALKENE AND ALKYNE SULFONIC ACIDS HAVING 4-2 CARBON ATOMS, AND ABOUT 0.002 TO ABOUT 0.5 GRAM/ITER OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF VINYL SUBSTITUTED M-DIOXANE, AND D-VINYL SUBSTITUTED BI(M-DIOXANE), AND DERIVATIVES THEREOF, IN WHICH DERIVATIVES THE M-DIOXANE RING IS SUBSTITUTED WITH A RADICAL SELECTED FROM THE GROUP CONSISTING OF CHLORO, BROMO, HYDROXY, METHOXY, ETHOXY AND HYDROXY-ETHOXY RADICALS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US683721A US2852449A (en) | 1957-09-13 | 1957-09-13 | Electrodeposition of nickel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US683721A US2852449A (en) | 1957-09-13 | 1957-09-13 | Electrodeposition of nickel |
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| US2852449A true US2852449A (en) | 1958-09-16 |
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| US683721A Expired - Lifetime US2852449A (en) | 1957-09-13 | 1957-09-13 | Electrodeposition of nickel |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2986500A (en) * | 1959-04-21 | 1961-05-30 | Metal & Thermit Corp | Electrodeposition of bright nickel |
| US3075898A (en) * | 1961-05-29 | 1963-01-29 | Udylite Res Corp | Electrodeposition of nickel |
| US3305462A (en) * | 1965-09-02 | 1967-02-21 | Barnet D Ostrow | Acid nickel electroplating bath |
| US4764262A (en) * | 1979-09-13 | 1988-08-16 | M&T Chemicals Inc. | High quality, bright nickel plating |
| US6045682A (en) * | 1998-03-24 | 2000-04-04 | Enthone-Omi, Inc. | Ductility agents for nickel-tungsten alloys |
-
1957
- 1957-09-13 US US683721A patent/US2852449A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2986500A (en) * | 1959-04-21 | 1961-05-30 | Metal & Thermit Corp | Electrodeposition of bright nickel |
| US3075898A (en) * | 1961-05-29 | 1963-01-29 | Udylite Res Corp | Electrodeposition of nickel |
| US3305462A (en) * | 1965-09-02 | 1967-02-21 | Barnet D Ostrow | Acid nickel electroplating bath |
| US4764262A (en) * | 1979-09-13 | 1988-08-16 | M&T Chemicals Inc. | High quality, bright nickel plating |
| US6045682A (en) * | 1998-03-24 | 2000-04-04 | Enthone-Omi, Inc. | Ductility agents for nickel-tungsten alloys |
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