EP0025694A1 - Bright nickel plating bath and process and composition therefor - Google Patents
Bright nickel plating bath and process and composition therefor Download PDFInfo
- Publication number
- EP0025694A1 EP0025694A1 EP80303183A EP80303183A EP0025694A1 EP 0025694 A1 EP0025694 A1 EP 0025694A1 EP 80303183 A EP80303183 A EP 80303183A EP 80303183 A EP80303183 A EP 80303183A EP 0025694 A1 EP0025694 A1 EP 0025694A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sulfonated
- nickel
- acetylenic compound
- compound
- per liter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 23
- 238000007747 plating Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 title claims abstract description 11
- 230000008569 process Effects 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940081974 saccharin Drugs 0.000 claims abstract description 13
- 235000019204 saccharin Nutrition 0.000 claims abstract description 13
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 238000009713 electroplating Methods 0.000 claims description 21
- 239000002659 electrodeposit Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000002816 nickel compounds Chemical group 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- OKIRJGABGVSQPK-UHFFFAOYSA-N but-1-yne-1-sulfonic acid Chemical compound CCC#CS(O)(=O)=O OKIRJGABGVSQPK-UHFFFAOYSA-N 0.000 claims description 3
- SLLLYZXUBOVDDR-UHFFFAOYSA-N but-2-yne-1-sulfonic acid Chemical compound CC#CCS(O)(=O)=O SLLLYZXUBOVDDR-UHFFFAOYSA-N 0.000 claims description 3
- FOJYSNPZWXIZOG-UHFFFAOYSA-N pent-1-yne-1-sulfonic acid Chemical compound CCCC#CS(O)(=O)=O FOJYSNPZWXIZOG-UHFFFAOYSA-N 0.000 claims description 3
- FYHLDUXIKXBAAT-UHFFFAOYSA-N prop-1-yne-1-sulfonic acid Chemical compound CC#CS(O)(=O)=O FYHLDUXIKXBAAT-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- 229910001453 nickel ion Inorganic materials 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 5
- 238000004070 electrodeposition Methods 0.000 abstract description 3
- 150000001721 carbon Chemical group 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- -1 aromatic sulfonates Chemical class 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004512 die casting Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical class OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- RFRQQNJDUQXAAS-UHFFFAOYSA-M 1-(2,3-dichloroprop-2-enyl)pyridin-1-ium;chloride Chemical compound [Cl-].ClC=C(Cl)C[N+]1=CC=CC=C1 RFRQQNJDUQXAAS-UHFFFAOYSA-M 0.000 description 1
- GJIDTCUGAGQFOW-UHFFFAOYSA-N 1-[4-(2-hydroxybut-3-enoxy)but-2-ynoxy]but-3-en-2-ol Chemical compound C=CC(O)COCC#CCOCC(O)C=C GJIDTCUGAGQFOW-UHFFFAOYSA-N 0.000 description 1
- PBYMYAJONQZORL-UHFFFAOYSA-N 1-methylisoquinoline Chemical compound C1=CC=C2C(C)=NC=CC2=C1 PBYMYAJONQZORL-UHFFFAOYSA-N 0.000 description 1
- LDCXMYWPEGQFTM-UHFFFAOYSA-N 1-prop-1-ynoxyethanesulfonic acid Chemical class C(#CC)OC(C)S(=O)(=O)O LDCXMYWPEGQFTM-UHFFFAOYSA-N 0.000 description 1
- KLCKMAMMLDRAQP-UHFFFAOYSA-M 1-prop-2-enylpyridin-1-ium;bromide Chemical compound [Br-].C=CC[N+]1=CC=CC=C1 KLCKMAMMLDRAQP-UHFFFAOYSA-M 0.000 description 1
- GZCWLCBFPRFLKL-UHFFFAOYSA-N 1-prop-2-ynoxypropan-2-ol Chemical compound CC(O)COCC#C GZCWLCBFPRFLKL-UHFFFAOYSA-N 0.000 description 1
- SPKKUSPQPHBCEZ-UHFFFAOYSA-M 2,4,6-trimethyl-1-prop-2-ynylpyridin-1-ium;bromide Chemical compound [Br-].CC1=CC(C)=[N+](CC#C)C(C)=C1 SPKKUSPQPHBCEZ-UHFFFAOYSA-M 0.000 description 1
- GLVJUCAUVKPSTL-UHFFFAOYSA-N 2-[4-(2-sulfoethoxy)but-2-ynoxy]ethanesulfonic acid Chemical compound OS(=O)(=O)CCOCC#CCOCCS(O)(=O)=O GLVJUCAUVKPSTL-UHFFFAOYSA-N 0.000 description 1
- GDMJHPRLSACEJC-UHFFFAOYSA-M 2-methyl-1-prop-2-enylquinolin-1-ium;bromide Chemical compound [Br-].C1=CC=CC2=[N+](CC=C)C(C)=CC=C21 GDMJHPRLSACEJC-UHFFFAOYSA-M 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- GHGCQQRMJCSIBQ-UHFFFAOYSA-N 2-prop-2-ynoxyethanol Chemical compound OCCOCC#C GHGCQQRMJCSIBQ-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
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
- VBARYRPUABJYGW-UHFFFAOYSA-N 5-(dimethylamino)-2-methylpent-3-yn-2-ol Chemical compound CN(C)CC#CC(C)(C)O VBARYRPUABJYGW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 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
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- YDPWVAMKZSUTGO-UHFFFAOYSA-N benzenesulfonamide;sodium Chemical compound [Na].NS(=O)(=O)C1=CC=CC=C1 YDPWVAMKZSUTGO-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
- 238000005282 brightening Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- CICQKHNSTQLPCW-UHFFFAOYSA-N dimethyl sulfate;2-methylquinoline Chemical compound COS(=O)(=O)OC.C1=CC=CC2=NC(C)=CC=C21 CICQKHNSTQLPCW-UHFFFAOYSA-N 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- YGSZNSDQUQYJCY-UHFFFAOYSA-L disodium;naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1S([O-])(=O)=O YGSZNSDQUQYJCY-UHFFFAOYSA-L 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical class CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JZJXKEWVUBVOEH-UHFFFAOYSA-N n,n-diethylprop-2-yn-1-amine Chemical compound CCN(CC)CC#C JZJXKEWVUBVOEH-UHFFFAOYSA-N 0.000 description 1
- UPPLSUDJSIYVTG-UHFFFAOYSA-N n,n-dimethylbut-2-yn-1-amine Chemical compound CC#CCN(C)C UPPLSUDJSIYVTG-UHFFFAOYSA-N 0.000 description 1
- OVQABVAKPIYHIG-UHFFFAOYSA-N n-(benzenesulfonyl)benzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NS(=O)(=O)C1=CC=CC=C1 OVQABVAKPIYHIG-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
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SOUHUMACVWVDME-UHFFFAOYSA-N safranin O Chemical compound [Cl-].C12=CC(N)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SOUHUMACVWVDME-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- MNCGMVDMOKPCSQ-UHDJGPCESA-M sodium;(e)-2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)\C=C\C1=CC=CC=C1 MNCGMVDMOKPCSQ-UHDJGPCESA-M 0.000 description 1
- YSJZWXFVNXMVCR-UHFFFAOYSA-M sodium;3-chlorobut-2-ene-1-sulfonate Chemical compound [Na+].CC(Cl)=CCS([O-])(=O)=O YSJZWXFVNXMVCR-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- NJPKYOIXTSGVAN-UHFFFAOYSA-K trisodium;naphthalene-1,3,6-trisulfonate Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(S([O-])(=O)=O)=CC2=CC(S(=O)(=O)[O-])=CC=C21 NJPKYOIXTSGVAN-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 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
- C25D3/16—Acetylenic compounds
-
- 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
Definitions
- Class I brighteners as used herein, and as described in Modern Electroplating, Third Edition, F. Lowenheim, Editor, is meant to include aromatic sulfonates, sulfonamides, sulfonimides, etc., as well as aliphatic or aromatic-aliphatic olefinically unsaturated sulfonates, sulfonamides, sulfonimides, etc. Specific examples of such plating additives are:
- solution agitation may be employed. Air agitation, mechanical stirring, pumping, cathode rod and other means of solution agitation are all satisfactory. Additionally, the solutions may be operated without agitation.
- the average cathode current density may range from about 0.5 to 12 amperes per square decimeter, with 3 to 6 amperes per square decimeter providing an optimum range.
- the pH may normally tend to rise and may be adjusted with acids such as hydrochloric, acid, sulfuric acid, etc.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
- Paints Or Removers (AREA)
- Materials For Photolithography (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
- This invention relates to improved processes and compositions for the electrodeposition of nickel and alloys thereof.
- It has been found that the presence of zinc impurities tends to produce plating defects during the electrodeposition of nickel electroplates using compositions containing primary and secondary brighteners. The problem is especially acute during plating when the secondary brightener is saccharin (o-benzoyl sulfimide). In this case inadequate basis metal coverage may occur in low current density areas; unsightly striated (ribbed) deposits may occur; and dark, thin non-metallic appearing deposits may be produced which not only detract from the final appearance of the article being plated, but may also interfere with the receptivity, appearance, luster, etc. of subsequent deposits such as chromium plate.
- In order to overcome the deleterious effects of zinc in the presence of saccharin, the use of sulfinic acids or hydroxy-sulfonates has been used.
- While these compounds do reduce the problem, their use also reduces the overall brightness and levelling of the deposit. This results in having to use thicker nickel deposits or higher levels of the primary additives in order to obtain commercially acceptable deposits.
- An alternative approach has been to replace saccharin with another Class I additive, i.e., sodium benzene sulfonamide, sodium toluene sulfonate. These Class I additives while not as sensitive to zinc impurities as is saccharin, are inferior to saccharin with respect to stress reduction, luster building (in cooperation with Class II additives), sulfur contribution (especially important in duplex plating).
- It is an object of this invention to provide processes and compositions for depositing electrodeposits of nickel in the presence of saccharin and zinc impurities. It is also an object of this invention to accomplish this without affecting the brightness or levelling of the deposit.
- In accordance with certain of its aspects, this invention relates to an improved process and composition for the preparation of nickel or nickel alloy electrodeposits which comprises passing current from an anode to a cathode through an aqueous acidic electroplating solution containing:
- (1) at least one nickel compound
- (2) saccharin
- (3) zinc ions
-
- Examples of sulfonated acetylenics of this invention, but not restricted thereto, are
- 2-butyne-l,4-disulfonic acid
- 2-butyne sulfonic acid
- propyne sulfonic acid
- 1-butyne sulfonic acid
- 1-pentyne sulfonic acid
- The baths of this invention may also contain an effective amount of at least one member selected from the group consisting of:
- (a) other Class I brighteners in addition to saccharin
- (b) Class II brighteners
- (c) anti-pitting or wetting agents.
- The term "Class I brighteners" as used herein, and as described in Modern Electroplating, Third Edition, F. Lowenheim, Editor, is meant to include aromatic sulfonates, sulfonamides, sulfonimides, etc., as well as aliphatic or aromatic-aliphatic olefinically unsaturated sulfonates, sulfonamides, sulfonimides, etc. Specific examples of such plating additives are:
- (1) disodium 1,5-naphthalene disulfonate
- (2) trisodium 1,3,6-naphthalene trisulfonate
- (3) sodium benzene monosulfonate
- (4) dibenzene sulfonimide
- (5) sodium 3-chloro-2-butene-l-sulfonate
- (6) sodium β-styrene sulfonate
- (7) sodium allyl sulfonate
- (8) monoallyl sulfamide
- (9) diallyl sulfamide
- (10) allyl sulfonamide
- Such plating additive compounds, which may be used singly or in suitable combinations, are desirably employed in amounts ranging from about 0.5 to 10 grams per liter and provide the advantages described in the above reference and which are well known to those skilled in the art of nickel electroplating.
- The term "Class II brighteners" as used herein, and as described in Modern Electroplating, Third Edition, F. Lowenheim, Editor, is meant to include plating additive compounds such as reaction products of epoxides with alpha- hydroxy acetylenic alcohols such as diethoxylated 2-butyne-l,4-diol, N-heterocyclics, dye-stuffs, acetylenic amines, etc.
- Specific examples of such plating additives are:
- (1) 1,4-di-(S-hydroxyethoxy)-2-butyne
- (2) 1,4-di-(S-hydroxy-y-chloropropoxy)-2-butyne
- (3) 1,4-di-(β-,γ-epoxypropoxy)-2-butyne
- - (4) 1,4-di-(β-hydroxy-γ-butenoxy)-2-butyne
- (5) 1,4-di(2'-hydroxy-4'-oxa-6'-heptenoxy)-2-butyne
- (6) N-(2,3-dichloro-2-propenyl)-pyridinium chloride
- (7) 2,4,6-trimethyl N-propargyl pyridinium bromide
- (8) N-allylquinaldinium bromide
- (9) 2-butyne-1,4-diol
- (10) propargyl alcohol
- (11) 2-methyl-3-butyn-2-ol
- (12) quinaldyl-N-propanesulfonic acid betaine
- (13) butynoxy ethane sulfonic acids
- (14) propynoxy ethane sulfonic acids
- (15) quinaldine dimethyl sulfate
- (16) N-allylpyridinium bromide
- (17) isoquinaldyl-N-propanesulfonic acid betaine
- (18) isoquinaldine dimethyl sulfate
- (19) N-allylisoquinaldine bromide
- (20) 1,4-di-(β-sulfoethoxy)-2-butyne
- (21) 3-(β-hydroxyethoxy)-propyne
- (22) 3-(β-hydroxypropoxy)-propyne
- (23) 3-(S-sulfoethoxy)-propyne
- (24) phenosafranin
- (25) fuchsin
- (26) propargyl amine
- (27) 1-diethylamino-2-propyne
- (28) 5-dimethylamino-2-methyl-3-pentyn-2- ol
- (29) l-dimethylamino-2-pentyne
- (30) 1-dimethylamino-2-butyne
- When used alone or in combination, desirably in amounts ranging from about 5 to 1000 milligrams per liter, a Class II brightener may produce no visual effect on the electrodeposit, or may produce semi-lustrous, fine-grained deposits. However, best results are obtained when Class II brighteners are used with one or more Class I brighteners in order to provide optimum deposit luster, rate of brightening, leveling, bright plate current density range, low current density coverage, etc.
- . The term "anti-pitting or wetting agents" as used herein is meant to include a material which functions to prevent or minimize gas pitting. An anti-pitting agent, when used alone or in combination, desirably in amounts ranging from about 0.05 to 1 gram per liter, may also function to make the baths more compatible with contaminants, such as oil, grease, etc. by their emulsifying, dispersing, solubilizing, etc. action on such contaminants and thereby promote attaining of sounder deposits. Preferred anti-pitting agents may include sodium lauryl sulfate, sodium lauryl ether-sulfate and sodium dialkylsulfosuccinates.
- The nickel compounds employed for electrodepositing nickel are typically added as the sulfate, chloride,.sulfamate, or fluoborate salts. The sulfate, chloride, sulfamate and fluoborate salts of nickel are employed in concentrations sufficient to provide nickel in the electroplating solutions of this invention in concentrations ranging from about 10 to 150 grams per liter.
- The nickel electroplating baths of this invention additionally may contain from about 30 to 60 grams per liter, preferably about 45 grams per liter of boric acid or other buffering agents to control the pH (e.g.; from about 3.0-5.0, preferably 4.0) and to prevent high current density burning.
- In order to prevent "burning" of high current density areas, and provide for more even temperature control of the solution, solution agitation may be employed. Air agitation, mechanical stirring, pumping, cathode rod and other means of solution agitation are all satisfactory. Additionally, the solutions may be operated without agitation.
- The operating temperature of the electroplating baths of this invention may range from about 40°C to about 70°C, preferably from about 50°C to 62°C.
- The average cathode current density may range from about 0.5 to 12 amperes per square decimeter, with 3 to 6 amperes per square decimeter providing an optimum range.
-
- - 8-During bath operation, the pH may normally tend to rise and may be adjusted with acids such as hydrochloric, acid, sulfuric acid, etc.
- Anodes used-in the above baths may be electrolytic or sulfur containing nickel bars, strips or small chunks in titanium baskets. All anodes are usually suitably covered with cloth or plastic bags of desired porosity to minimize introduction into the bath of metal particles, anode slime, etc. which may migrate to the cathode either mechanically or electrophoretically to give roughness in cathode deposits.
- The substrates on which the nickel electrodeposits of this invention may be applied may be metal or metal alloys such as are commonly electrodeposited and used in the art of electroplating such as nickel, cobalt, nickel-cobalt, copper, tin, brass, etc. Other typical substrate basis metals from which articles to be plated are manufactured may include ferrous metals such as iron, steel, alloy steels, copper, tin and alloys thereof such as with lead, alloys of copper such as brass, bronze, etc., zinc, particularly in the form of zinc-base die castings; all of which may bear plates of other metals, such as copper, etc. Basis metal substrates may have a variety of surface finishes depending on the final appearance desired, which in turn depends on such factors as luster, brilliance, leveling, thickness, etc. of the nickel electroplate applied on such substrates.
- It is in the electroplating of zinc base die castings that the application of this invention is very useful, as die castings fall into the electroplating solution and cause high levels of zinc impurities. These impurities in the presence of saccharin cause the unsightly electrodeposits mentioned previously and can result in high operating costs.
- The addition or inclusion of specified amounts of a sulfonated acetylenic compound or salts thereof, where the acetylenic bond and the sulfonate radical are connected by a carbon chain where C=1-6, to an aqueous acidic nickel electroplating containing saccharin and zinc impurities, will result in a bright, well leveled deposit free from the previously mentioned defects.
-
- The conditions for plating the panels from the above aqueous nickel electroplating compositions were as follows:
- A zinc coated steel test panel was stripped in 50% hydrochloric acid, rinsed and then scribed with a horizontal single pass of 4/0 grit emery polishing paper and another scribe in a similar manner with #2 grit emery polishing paper. The cleaned panel was then plated in a 267 ml Hull Cell using the aforementioned compositions for 10 minutes at 2 amps. cell current, using cathode rod agitation.
-
- Panel 1 - Shows a bright, well leveled deposit, with low current density skip plate, severe darkness and striations.
- Panel 2 - Shows a bright, well leveled deposit, free from defects, over the entire current density range.
- Panel 3 - Shows a bright, well leveled deposit with only a very small amount of low current density darkness.
- Although this invention has been illustrated by reference to specific embodiments, modifications thereof which are clearly within the scope of the invention will be apparent to those skilled in the art.
the improvement comprising the presence of a sulfonated acetylenic compound or salts thereof, where the acetylenic bond and the sulfonate radical are connected by a carbon chain of at least one carbon atom and not more than 6 carbon atoms.
Claims (13)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT80303183T ATE6873T1 (en) | 1979-09-13 | 1980-09-10 | BRIGHT NICKEL PLATING BATH AND METHOD AND COMPOSITION THEREOF. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7495379A | 1979-09-13 | 1979-09-13 | |
US74953 | 1987-07-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0025694A1 true EP0025694A1 (en) | 1981-03-25 |
EP0025694B1 EP0025694B1 (en) | 1984-03-28 |
Family
ID=22122633
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80303183A Expired EP0025694B1 (en) | 1979-09-13 | 1980-09-10 | Bright nickel plating bath and process and composition therefor |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0025694B1 (en) |
JP (1) | JPS5647583A (en) |
AT (1) | ATE6873T1 (en) |
AU (1) | AU532948B2 (en) |
BR (1) | BR8005852A (en) |
DE (1) | DE3067275D1 (en) |
ES (1) | ES8205437A1 (en) |
HK (1) | HK80384A (en) |
MX (1) | MX153967A (en) |
NZ (1) | NZ194923A (en) |
ZA (1) | ZA805658B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2189258B (en) * | 1986-04-15 | 1991-01-16 | Omi Int Corp | Zinc-nickel alloy electrolyte and process |
WO2018015168A1 (en) | 2016-07-18 | 2018-01-25 | Basf Se | Composition for cobalt plating comprising additive for void-free submicron feature filling |
EP3680366A4 (en) * | 2017-09-06 | 2021-06-09 | Kanto Denka Kogyo Co., Ltd. | Electrode and production method therefor, and production method for regenerated electrode |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3632514A1 (en) * | 1986-09-22 | 1988-03-24 | Schering Ag | (ALPHA) -HYDROXI PROPINE SULPHONIC ACID AND ITS SALTS, ACID NICKELBEDER CONTAINING THESE COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3884773A (en) * | 1973-08-17 | 1975-05-20 | Metalux Corp | Electrodeposition of nickel |
DE2460247A1 (en) * | 1973-12-27 | 1975-07-10 | Du Pont | PRIME GLOSS ADDITIVE FOR ACID NICKEL GALVANIZED TUBES |
GB1441972A (en) * | 1972-10-30 | 1976-07-07 | Oxy Metal Finishing Corp | Nickel electroplating baths and their use in forming corrosion protective metallic coatings containing electrodeposited nickel and microporous chrome |
GB1456583A (en) * | 1970-12-11 | 1976-11-24 | Oxy Metal Industries Corp | Electroplating composition and process |
US4016051A (en) * | 1975-05-02 | 1977-04-05 | Starlite Chemicals, Inc. | Additives for bright plating nickel, cobalt and nickel-cobalt alloys |
DE2654040A1 (en) * | 1975-12-04 | 1977-06-08 | Mcgean Chemical Co | PROCESS FOR DEPOSITING A GLOSSY LAYER BASED ON NICKEL ON A SUBSTRATE BY ELECTROPLATING |
-
1980
- 1980-09-10 AT AT80303183T patent/ATE6873T1/en not_active IP Right Cessation
- 1980-09-10 DE DE8080303183T patent/DE3067275D1/en not_active Expired
- 1980-09-10 EP EP80303183A patent/EP0025694B1/en not_active Expired
- 1980-09-11 NZ NZ194923A patent/NZ194923A/en unknown
- 1980-09-11 JP JP12661080A patent/JPS5647583A/en active Granted
- 1980-09-12 BR BR8005852A patent/BR8005852A/en unknown
- 1980-09-12 ZA ZA00805658A patent/ZA805658B/en unknown
- 1980-09-12 ES ES495007A patent/ES8205437A1/en not_active Expired
- 1980-09-12 MX MX183921A patent/MX153967A/en unknown
- 1980-09-12 AU AU62365/80A patent/AU532948B2/en not_active Ceased
-
1984
- 1984-10-25 HK HK803/84A patent/HK80384A/en not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1456583A (en) * | 1970-12-11 | 1976-11-24 | Oxy Metal Industries Corp | Electroplating composition and process |
GB1441972A (en) * | 1972-10-30 | 1976-07-07 | Oxy Metal Finishing Corp | Nickel electroplating baths and their use in forming corrosion protective metallic coatings containing electrodeposited nickel and microporous chrome |
US3884773A (en) * | 1973-08-17 | 1975-05-20 | Metalux Corp | Electrodeposition of nickel |
DE2460247A1 (en) * | 1973-12-27 | 1975-07-10 | Du Pont | PRIME GLOSS ADDITIVE FOR ACID NICKEL GALVANIZED TUBES |
US4016051A (en) * | 1975-05-02 | 1977-04-05 | Starlite Chemicals, Inc. | Additives for bright plating nickel, cobalt and nickel-cobalt alloys |
DE2654040A1 (en) * | 1975-12-04 | 1977-06-08 | Mcgean Chemical Co | PROCESS FOR DEPOSITING A GLOSSY LAYER BASED ON NICKEL ON A SUBSTRATE BY ELECTROPLATING |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2189258B (en) * | 1986-04-15 | 1991-01-16 | Omi Int Corp | Zinc-nickel alloy electrolyte and process |
WO2018015168A1 (en) | 2016-07-18 | 2018-01-25 | Basf Se | Composition for cobalt plating comprising additive for void-free submicron feature filling |
EP3885475A1 (en) | 2016-07-18 | 2021-09-29 | Basf Se | Composition for cobalt plating comprising additive for void-free submicron feature filling |
EP3680366A4 (en) * | 2017-09-06 | 2021-06-09 | Kanto Denka Kogyo Co., Ltd. | Electrode and production method therefor, and production method for regenerated electrode |
US11821099B2 (en) | 2017-09-06 | 2023-11-21 | Kanto Denka Kogyo Co., Ltd. | Electrode production method |
Also Published As
Publication number | Publication date |
---|---|
BR8005852A (en) | 1981-03-24 |
JPS5647583A (en) | 1981-04-30 |
ES495007A0 (en) | 1982-06-01 |
MX153967A (en) | 1987-03-03 |
ZA805658B (en) | 1982-03-31 |
AU532948B2 (en) | 1983-10-20 |
AU6236580A (en) | 1981-03-19 |
ATE6873T1 (en) | 1984-04-15 |
ES8205437A1 (en) | 1982-06-01 |
EP0025694B1 (en) | 1984-03-28 |
JPS6252035B2 (en) | 1987-11-02 |
HK80384A (en) | 1984-11-02 |
NZ194923A (en) | 1982-05-25 |
DE3067275D1 (en) | 1984-05-03 |
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