US2648627A - Bright nickel plating composition and process - Google Patents
Bright nickel plating composition and process Download PDFInfo
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- US2648627A US2648627A US164040A US16404050A US2648627A US 2648627 A US2648627 A US 2648627A US 164040 A US164040 A US 164040A US 16404050 A US16404050 A US 16404050A US 2648627 A US2648627 A US 2648627A
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- Prior art keywords
- acid
- bath
- nickel
- nickel plating
- beta
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 47
- 229910052759 nickel Inorganic materials 0.000 title claims description 23
- 238000007747 plating Methods 0.000 title claims description 22
- 238000000034 method Methods 0.000 title description 6
- 239000000203 mixture Substances 0.000 title description 2
- -1 ISOTHIOUREIDO Chemical class 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 15
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000006172 buffering agent Substances 0.000 claims description 2
- IQSKZUZFUMDBAG-UHFFFAOYSA-N 3-thioureidopropionic acid Chemical compound NC(=S)NCCC(O)=O IQSKZUZFUMDBAG-UHFFFAOYSA-N 0.000 description 10
- 150000002815 nickel Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- IBFFOIPJYGMHMW-UHFFFAOYSA-N 2-(carbamothioylamino)acetamide Chemical compound NC(=O)CNC(N)=S IBFFOIPJYGMHMW-UHFFFAOYSA-N 0.000 description 2
- YHEWKWZSKSRYGE-UHFFFAOYSA-N 2-(carbamothioylamino)propanoic acid Chemical compound OC(=O)C(C)N=C(N)S YHEWKWZSKSRYGE-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- REMPXLPRFHAIQD-UHFFFAOYSA-N 2h-oxatriazine Chemical compound N1OC=CN=N1 REMPXLPRFHAIQD-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- 241000534000 Berula erecta Species 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- JSJWCHRYRHKBBW-UHFFFAOYSA-N N-carbamoyl-beta-alanine Chemical compound NC(=O)NCCC(O)=O JSJWCHRYRHKBBW-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CALQKRVFTWDYDG-UHFFFAOYSA-N butan-1-amine;hydroiodide Chemical compound [I-].CCCC[NH3+] CALQKRVFTWDYDG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- MVYQJCPZZBFMLF-UHFFFAOYSA-N hydron;propan-1-amine;bromide Chemical compound [Br-].CCC[NH3+] MVYQJCPZZBFMLF-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- WIAVVDGWLCNNGT-UHFFFAOYSA-M lithium;butanoate Chemical compound [Li+].CCCC([O-])=O WIAVVDGWLCNNGT-UHFFFAOYSA-M 0.000 description 1
- 150000002646 long chain fatty acid esters Chemical class 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKOQQFDCCBKROY-UHFFFAOYSA-N n,n-diethylpropanamide Chemical compound CCN(CC)C(=O)CC YKOQQFDCCBKROY-UHFFFAOYSA-N 0.000 description 1
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000008601 oleoresin Substances 0.000 description 1
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
Definitions
- This invention relates to the electrodeposition of nickel and is more particularly concerned with a bright uickel plating bath, having, as an additive, therein a compound containing an isothioureido radical, and with a process utilizing such a bath.
- a further object of the present invention is to provide a group of compounds which accomplishes the herein-described results without decomposition of the agent, in situ.
- Still another object of the present invention is to provide an addition agent fora nickel plating bath which has an isothicureido nucleus contained therein.
- Additaments of the present invention are at least partially water-soluble organic compounds containing an isothioureido nucleus, having an organic radical attached to the sulphur atom of the nucleus, and have the following formula:
- R1 is an alkanoic acid, amide, substituted amide, ester, acid salt, alkanol, alkylamine acid addition salt, or alkylamine quaternary ammonium salt
- R2 and R3 are hydrogen or an organic radical, and wherein R2 and R3 may be the same, different, or joined together to form a heterocyclic ring-structure.
- R1 may be a radical such as, for example, acetic acid, propionic acid, butyric acid, acetamide, propionamide, N,N-dimethylacetamide, N,N-diethylpropionamide, methyl acetate, ethyl propionate, propyl butyrate, ethyl acetate, benzyl acetate, sodium acetate, potassium propionate, calcium acetate, lithium butyrate, ethanol, isopropanol, propanol, methanol, n-butanol, isobutanol, tertiary butanol, pentanol, ethyl amine hydrochloride, propylamine hydrobromide, butylamine hydriodide, N,N-dimethy1ethylamide methobromide, et cetera, while R2 and R3 may be hydrogen atoms, or similar or dissimilar organic radicals, such as
- radicals may have one or more of their hydrogen atoms substituted with other elements or groups as halogen, hydroxyl, nitro, sulfo, et cetera.
- the two nitrogen atoms of the isthioureido radical may be joined with other atoms to form a heterocyclic radical, such as pyrazole, imidazole, oxatriazine, oxadidiazine, et cetera.
- Representative compounds which are contemplated within the scope of the above-mentioned formula.
- beta-isothioureidopropionic acid include, among others, beta-isothioureidopropionic acid, isothioureidoacetamide, ethyl alpha-(N-methyl-N-phenylisthioureido)butyrat e, sodium N-benzyl-N'- heXyl-beta-isothioureidopropanol, S-(2-pyrimido) beta--mercaptopropionic acid, sodium S-2- pyrimido) -mercaptoacetate, S- (4-methyl-5-ethyl-2-pyrimido) -beta-mercaptopropionamide, et cetera.
- a Watts type bath is particularly adaptable to this additament.
- nickel chloride and nickel sulfate are used as the source of metallic ions.
- a wetting agent such as sodium lauryl sulfate, benzene sulfonic acid, sulfonated long-chain fatty acid esters, et cetera, may be used in an amount of less than one percent, andpreferably about 0.01 percent.
- a bufier such as boric acid, et cetera, in an amount sufficient to maintain the pH of the bath in the range of 2.5 to 5.5 is also employed.
- the temperature may be varied between 60 and 175 degrees Fahrenheit with satisfactory results', however, temperature between 140 and 160 degrees Fahrenheit are preferred. Although a current density between 50 and 75 amperes per square foot is apparently the most desirable, densities between 25 and 100 amperes per square foot may be used satisfactorily.
- Example 1 Watts type bath A solution was prepared containing 33.5 ounces of nickel sulfate hexahydrate, 6.4 ounces of nickel chloride, 4.6 ounces of b'or'ic acid, and 0.025 ounce of beta-isothioureidopropionic acid per gallon. The temperature of the bath was raised to about 15.0 degrees Fahrenheit, the pH maintained at abeut; 5 and varying current densities passed thretlirough. Lustrous, bright panels were obtairied at current densities up to and through the 120ainp eres per square foot range. This result may be'contras'ted to the electro-deposited coatin'gs obtained when no additive is employed, which are dark grey and hazy at current densities above 15' amperes per square foot.
- beta isothioureidopropionic acid of the bath in Example 1 alpha-isothioureidopropionic acid, sodium beta-isothioureidopropionate, potassium alpha-isothioureidopropionate, methyl-gammais0thioureidobutyrate, alpha-isothioureidoacetamide, beta-isothioureidoacetamide, beta-isothioureidopropionamide, beta- [N-methyl-N- (paramethoxyphenyl).
- Example 1 The bath was tested "in a manner exactlysimilar tothat of Example 1'. Test panels obtained were lustrous, bright through the 100 amperes per square foot range.-
- Test panels obtained were lustrous bright through the amperes per square foot range.
- Example 5 Other additaments which have been tested and found as satisfactory as those described above include ethyl beta-isothioureidopropionate and beta isothioureidopropionamide.
- An acid aqueous nickel plating bath con.- taining nickel salts, an acid buffering agent, and an at least partially water-soluble. organic com.- pound containing an isothioureido. nucleus and having an organic radical attachedv to. the sulphur atom of the nucleus, said organic compound being dissolved in said bath in sufiicient quan.-- tity to produce bright nickel plating therefrom.
- the method which includes: electrodepositing nickel from an aqueous, acid. nickel salt s0- lution having dissolved thereinan at least par.-
- Theprocess whichincludes: electrodepositing nickel from an aqueous, acidnickel salt solution, having dissolved therein between 0.01 percent and 0.1 percent of betaisothioureidopropionic acid.
- An acid nickel plating bath comprising: an aqueous solution of nickel salts and between 0.01 percent and 0.1 percent beta-isothioureido-r propionic acid.
- a Watts type nickel plating bath contain: ing as an additive therein, between 0.01 and 0.1 percent beta-isothioureidopropionic acid.
- Anacid nickel plating bath comprising: an aqueous solution of nickel salts and. between 0.01 percent and 0.1 percent ethyl beta-.isothioe ureidopropionate.
- Anacid nickel plating bath comprising: an aqueous solution of nickel salts and between 0.01 percent and 0.1 percent beta-isothioureidopropionamide.
- the method which includes: electrodepositing nickel from an aqueous, acid nickel salt solution, having a pH between about 2.5 and about 5.5, maintained at a temperature between about 60 and about degrees Fahrenheit, and containing dissolved therein between 0.01 and 0.1 percent of an at leastv partially water-soluble organic compound containing an isothioureido nucleus having an organic radical attached to the sulphur atom of the nucleus, by passing a current having a density between about 25 and about '100 amperes per squarefoot.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
Patented Aug. 11, 1953 BRIGHT NICKEL PLATING COMPOSITION AND PROCESS Harold George Donnelly, Dearborn, Mich., as-
signor to Wagner Brothers, Inc., Detroit, Mich., a corporation of Michigan No Drawing. Application May 24, 1950, Serial No. 164,040
11 Claims. (01. 2o4 49) This invention relates to the electrodeposition of nickel and is more particularly concerned with a bright uickel plating bath, having, as an additive, therein a compound containing an isothioureido radical, and with a process utilizing such a bath.
' It has been proposed that various agents be added to nickel plating baths to avoid pitting and brittleness in the nickel coating. Among these may be mentioned arylsulfonic acids, arylnaphthalenic acids, gum tragacanth, sulfonated resins, oleo resins, et cetera. By introducing such agents into the bath, hydrogen atoms formed by hydrolysis are more quickly loosened from the surface of the metal thereby affording a smooth plating surface. However, the addition of such agents to the bath has not satisfactorily overcome the problem of brittleness and leaves much to be desired from the standpoint of brightness.
It is therefore a principal object of the present invention to provide a novel group of addition agents for a nickel plating bath which allows the bath, under specified conditions, to plate out a bright, non-brittle, non-pitted, coat of nickel. A further object of the present invention is to provide a group of compounds which accomplishes the herein-described results without decomposition of the agent, in situ. Still another object of the present invention is to provide an addition agent fora nickel plating bath which has an isothicureido nucleus contained therein. Other objects will become apparent hereinafter.
I have now found that the addition of a compound, as hereinafter described, to a conventional nickel plating bath, not only greatly enhances the quality, particularly the brightness and ductility, of a plate resulting from the use thereof, but the agent is apparently not decomposed by electrolysis, thereby avoiding the necessity of frequent replacement. Additaments of the present invention are at least partially water-soluble organic compounds containing an isothioureido nucleus, having an organic radical attached to the sulphur atom of the nucleus, and have the following formula:
wherein R1 is an alkanoic acid, amide, substituted amide, ester, acid salt, alkanol, alkylamine acid addition salt, or alkylamine quaternary ammonium salt, wherein R2 and R3 are hydrogen or an organic radical, and wherein R2 and R3 may be the same, different, or joined together to form a heterocyclic ring-structure.
Thus, R1 may be a radical such as, for example, acetic acid, propionic acid, butyric acid, acetamide, propionamide, N,N-dimethylacetamide, N,N-diethylpropionamide, methyl acetate, ethyl propionate, propyl butyrate, ethyl acetate, benzyl acetate, sodium acetate, potassium propionate, calcium acetate, lithium butyrate, ethanol, isopropanol, propanol, methanol, n-butanol, isobutanol, tertiary butanol, pentanol, ethyl amine hydrochloride, propylamine hydrobromide, butylamine hydriodide, N,N-dimethy1ethylamide methobromide, et cetera, while R2 and R3 may be hydrogen atoms, or similar or dissimilar organic radicals, such as, for example, alkyl as methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl, secondary butyl, normal-pentyl, isopentyl, secondary pentyl, tertiary pentyl, et cetera; alkenyl as vinyl, allyl, methallyl, crotyl, et ectera; aryl as phenyl, naphthyl, dipropyl-naphthyl, benzyl, naphthyl-butyl, et cetera; aralkenyl as vinylphenyl, crotonyl-naphthyl, methallyl-phenyl, naphthyl-allyl, et cetera; cycloparafiinic as cyclopentyl, ethyl-cyclohexyl, tributyl-cyclohexyl, et cetera; cyclo-olefinic as cyclopentenyl, cyclohexenyl, et cetera; heterocyclic as thienyl, pyrrolyl, furyl, et cetera. These radicals may have one or more of their hydrogen atoms substituted with other elements or groups as halogen, hydroxyl, nitro, sulfo, et cetera. Further, the two nitrogen atoms of the isthioureido radical may be joined with other atoms to form a heterocyclic radical, such as pyrazole, imidazole, oxatriazine, oxadidiazine, et cetera. Representative compounds which are contemplated within the scope of the above-mentioned formula. include, among others, beta-isothioureidopropionic acid, isothioureidoacetamide, ethyl alpha-(N-methyl-N-phenylisthioureido)butyrat e, sodium N-benzyl-N'- heXyl-beta-isothioureidopropanol, S-(2-pyrimido) beta--mercaptopropionic acid, sodium S-2- pyrimido) -mercaptoacetate, S- (4-methyl-5-ethyl-2-pyrimido) -beta-mercaptopropionamide, et cetera.
Although the addition of the additives abovedescribed to the plating bath enhances the plating ability of any type of bright nickel bath, a Watts type bath is particularly adaptable to this additament. Usually, both nickel chloride and nickel sulfate are used as the source of metallic ions. A wetting agent, such as sodium lauryl sulfate, benzene sulfonic acid, sulfonated long-chain fatty acid esters, et cetera, may be used in an amount of less than one percent, andpreferably about 0.01 percent. A bufier such as boric acid, et cetera, in an amount sufficient to maintain the pH of the bath in the range of 2.5 to 5.5 is also employed. The temperature may be varied between 60 and 175 degrees Fahrenheit with satisfactory results', however, temperature between 140 and 160 degrees Fahrenheit are preferred. Although a current density between 50 and 75 amperes per square foot is apparently the most desirable, densities between 25 and 100 amperes per square foot may be used satisfactorily.
It is to be understood that various other additives known to the art, in addition to those compounds herein-described, may also be employed, however, I have found that such additives do not greatly enhance the plating ability of the bath, and a preferred embodiment of the present invention includes only those above-mentioned. An isot'hioureido compound, as defined hereinbefore, is usually employed in an amount between about 0.01 and about 0.1 percent, while 0.025 percent is the preferred amount.
The following examples are given to illustrate the practice of the present invention, but are not to be construed as limiting.
Example 1. Watts type bath A solution was prepared containing 33.5 ounces of nickel sulfate hexahydrate, 6.4 ounces of nickel chloride, 4.6 ounces of b'or'ic acid, and 0.025 ounce of beta-isothioureidopropionic acid per gallon. The temperature of the bath was raised to about 15.0 degrees Fahrenheit, the pH maintained at abeut; 5 and varying current densities passed thretlirough. Lustrous, bright panels were obtairied at current densities up to and through the 120ainp eres per square foot range. This result may be'contras'ted to the electro-deposited coatin'gs obtained when no additive is employed, which are dark grey and hazy at current densities above 15' amperes per square foot.
Eirample 2 The following additaments may be used in place of. beta isothioureidopropionic acid of the bath in Example 1: alpha-isothioureidopropionic acid, sodium beta-isothioureidopropionate, potassium alpha-isothioureidopropionate, methyl-gammais0thioureidobutyrate, alpha-isothioureidoacetamide, beta-isothioureidoacetamide, beta-isothioureidopropionamide, beta- [N-methyl-N- (paramethoxyphenyl). isothioureidol N,N-dimethylpropionamide, beta-isothioureidopropanol, betaisothioureidopropylamide hydrochloride, betaisothioureidopropyl dimethylamine methiodide. The results obtained all represent an improvement overthea'rt, with the efficacies of the particul'ar compounds varying.
Edtample 3. Combined type bath A solution was prepared containing:
I Ounces/gallon Ni-SQQBHtO 25.1 nioi2 6H o l 20.9 Berle acid 3.9 Betaisothioureidopropionic acid 0.033 pI-I (l tl'olnti'ioji Q; 5.0
The bath was tested "in a manner exactlysimilar tothat of Example 1'. Test panels obtained were lustrous, bright through the 100 amperes per square foot range.-
4 Example 4. All chloride bath A solution was prepared containing:
Ounces/gallon NiClz-SHzO 35.9 Boric acid l 3.1 Beta-isothioureidopropionic acid 0.038 pI-I (electrometric) 5.0
The bath was tested in a manner exactly similar to that of Example 1. Test panels obtained were lustrous bright through the amperes per square foot range.
Example 5 Other additaments which have been tested and found as satisfactory as those described above include ethyl beta-isothioureidopropionate and beta isothioureidopropionamide.
Various modifications may be made in the method of the present invention without departing from the spirit or. scopethereof, and it is to be understood that I limit myself only as defined in theappended claims.
I claim:
1. An acid aqueous nickel plating bath. con.- taining nickel salts, an acid buffering agent, and an at least partially water-soluble. organic com.- pound containing an isothioureido. nucleus and having an organic radical attachedv to. the sulphur atom of the nucleus, said organic compound being dissolved in said bath in sufiicient quan.-- tity to produce bright nickel plating therefrom.
2. The method which includes: electrodepositing nickel from an aqueous, acid. nickel salt s0- lution having dissolved thereinan at least par.-
tially water. soluble organic compound containing an. isothioureido. nucleus and having an organic radical attached. to the sulphur. atom of the nucleus, said organic compound being dissolved in said bathin sufficient quantity to.pro-. duce bright. nickel plating therefrom.
3. Theprocess whichincludes: electrodepositing nickel from an aqueous, acidnickel salt solution, having dissolved therein between 0.01 percent and 0.1 percent of betaisothioureidopropionic acid.
1. An acid nickel plating bath, comprising: an aqueous solution of nickel salts and between 0.01 percent and 0.1 percent beta-isothioureido-r propionic acid.
5. A Watts type nickel plating bath contain: ing as an additive therein, between 0.01 and 0.1 percent beta-isothioureidopropionic acid.
6. Anacid nickel plating bath, comprising: an aqueous solution of nickel salts and. between 0.01 percent and 0.1 percent ethyl beta-.isothioe ureidopropionate.
7. Anacid nickel plating bath, comprising: an aqueous solution of nickel salts and between 0.01 percent and 0.1 percent beta-isothioureidopropionamide.
8. The method which includes: electrodepositing nickel from an aqueous, acid nickel salt solution, having a pH between about 2.5 and about 5.5, maintained at a temperature between about 60 and about degrees Fahrenheit, and containing dissolved therein between 0.01 and 0.1 percent of an at leastv partially water-soluble organic compound containing an isothioureido nucleus having an organic radical attached to the sulphur atom of the nucleus, by passing a current having a density between about 25 and about '100 amperes per squarefoot. 7 V V A ic e p a n ath, o taining olu e nickel salts; 'tufiiient boric acid to buffer the solution at a pH of between about 2.5 and about 5.5, and between about 0.01 and 0.1 percent betaisothioureidopropionic acid.
10. A nickel plating bath containing nickel salts, sufiicient boric acid to buffer the solution at a pH of between about 2.5 and about 5.5, and between about 0.01 and 0.1 percent of an at least partially water-soluble organic compound containing an isothioureido nucleus and having an organic radical attached to the sulphur atom of the nucleus.
11. A nickel plating bath containing nickel chloride and nickel sulfate ions, less than about one percent of a Wetting agent, an acid bufier sufficient to maintain the pH of the bath in the 6 range between about 2.5 and about 5.5 and between 0.01 percent and 0.1 percent beta-isothioureidopropionic acid.
HAROLD GEORGE DONNELLY.
OTHER REFERENCES Raub et a1., Metal Finishing, June 1940, pp. 315-17.
Claims (1)
1. AN ACID AQUEOUS NICKEL PLATING BATH CONTAINING NICKEL SALTS, AN ACID BUFFERING AGENT, AND AN AT LEAST PARTIALLY WATER-SOLUBLE ORGANIC COMPOUND CONTAINING AN ISOTHIOUREIDO NUCLEUS AND HAVING AN ORGANIC RADICAL ATTACHED TO THE SULPHUR ATOM OF THE NUCLEUS, SAID ORGANIC COMPOUND BEING DISSOLVED IN SAID BATH IN SUFFICIENT QUANTITY TO PRODUCE BRIGHT NICKEL PLATING THEREFROM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US164040A US2648627A (en) | 1950-05-24 | 1950-05-24 | Bright nickel plating composition and process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US164040A US2648627A (en) | 1950-05-24 | 1950-05-24 | Bright nickel plating composition and process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2648627A true US2648627A (en) | 1953-08-11 |
Family
ID=22592721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US164040A Expired - Lifetime US2648627A (en) | 1950-05-24 | 1950-05-24 | Bright nickel plating composition and process |
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| Country | Link |
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| US (1) | US2648627A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1000204B (en) * | 1954-03-13 | 1957-01-03 | Dehydag Gmbh | Process for the production of galvanic copper coatings |
| US2781305A (en) * | 1953-08-14 | 1957-02-12 | Udylite Res Corp | Electrodeposition of nickel |
| US2849351A (en) * | 1953-09-19 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| US2892760A (en) * | 1954-10-28 | 1959-06-30 | Dehydag Gmbh | Production of metal electrodeposits |
| US2937978A (en) * | 1953-08-13 | 1960-05-24 | Dehydag Gmbh | Electroplating of nickel |
| DE1235101B (en) * | 1959-08-21 | 1967-02-23 | Langbein Pfanhauser Werke Ag | Electrolyte with gloss additive for galvanic deposition of mirror-glossy, leveled, ductile nickel deposits |
| US3498893A (en) * | 1967-03-27 | 1970-03-03 | Ian H S Henderson | Anodization of a nickel body which has a coating of partially electronically insulating material |
| US3876513A (en) * | 1972-06-26 | 1975-04-08 | Oxy Metal Finishing Corp | Electrodeposition of bright cobalt plate |
| US20120234428A1 (en) * | 2009-09-18 | 2012-09-20 | Toyo Kohan Co., Ltd. | Nickel-Plated Steel Sheet for Manufacturing Pipe Having Corrosion Resistance Against Fuel Vapors, Pipe Which Uses the Steel Sheet,and Fuel Supply Pipe Which Uses the Steel Sheet |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB553781A (en) * | 1942-09-02 | 1943-06-04 | Int Nickel Co | Improvements relating to the production of nickel anodes |
-
1950
- 1950-05-24 US US164040A patent/US2648627A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB553781A (en) * | 1942-09-02 | 1943-06-04 | Int Nickel Co | Improvements relating to the production of nickel anodes |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2937978A (en) * | 1953-08-13 | 1960-05-24 | Dehydag Gmbh | Electroplating of nickel |
| US2781305A (en) * | 1953-08-14 | 1957-02-12 | Udylite Res Corp | Electrodeposition of nickel |
| US2849351A (en) * | 1953-09-19 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| DE1207177B (en) * | 1953-09-19 | 1965-12-16 | Hydrierwerke G M B H Deutsche | Process for the production of shiny galvanic metal coatings |
| DE1000204B (en) * | 1954-03-13 | 1957-01-03 | Dehydag Gmbh | Process for the production of galvanic copper coatings |
| US2892760A (en) * | 1954-10-28 | 1959-06-30 | Dehydag Gmbh | Production of metal electrodeposits |
| DE1235101B (en) * | 1959-08-21 | 1967-02-23 | Langbein Pfanhauser Werke Ag | Electrolyte with gloss additive for galvanic deposition of mirror-glossy, leveled, ductile nickel deposits |
| US3498893A (en) * | 1967-03-27 | 1970-03-03 | Ian H S Henderson | Anodization of a nickel body which has a coating of partially electronically insulating material |
| US3876513A (en) * | 1972-06-26 | 1975-04-08 | Oxy Metal Finishing Corp | Electrodeposition of bright cobalt plate |
| US20120234428A1 (en) * | 2009-09-18 | 2012-09-20 | Toyo Kohan Co., Ltd. | Nickel-Plated Steel Sheet for Manufacturing Pipe Having Corrosion Resistance Against Fuel Vapors, Pipe Which Uses the Steel Sheet,and Fuel Supply Pipe Which Uses the Steel Sheet |
| US9194530B2 (en) * | 2009-09-18 | 2015-11-24 | Toyo Kohan Co., Ltd. | Nickel-plated steel sheet for manufacturing pipe having corrosion resistance against fuel vapors, pipe which uses the steel sheet, and fuel supply pipe which uses the steel sheet |
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