US3795594A - Electroplating - Google Patents

Electroplating Download PDF

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Publication number: US3795594A
Authority: US; United States
Prior art keywords: carbon atoms; zinc; liter; group; optionally
Prior art date: 1971-04-16
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired - Lifetime

Application number

US00243827A

Other languages

English (en)

Inventor

J Hartenstein

M Nee

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Henkel AG and Co KGaA

Original Assignee

Henkel AG and Co KGaA

Priority date (The priority date 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 date listed.)

1971-04-16

Filing date

1972-04-13

Publication date

1974-03-05

1972-04-13 Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA

1974-03-05 Application granted granted Critical

1974-03-05 Publication of US3795594A publication Critical patent/US3795594A/en

1991-03-05 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

238000009713 electroplating Methods 0.000 title abstract description 22
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 44
239000011701 zinc Substances 0.000 abstract description 43
229910052725 zinc Inorganic materials 0.000 abstract description 43
239000000080 wetting agent Substances 0.000 abstract description 15
239000002253 acid Substances 0.000 abstract description 14
238000000034 method Methods 0.000 abstract description 11
UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical class NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 9
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
239000003795 chemical substances by application Substances 0.000 abstract description 6
229910052760 oxygen Inorganic materials 0.000 abstract description 6
239000001301 oxygen Substances 0.000 abstract description 6
150000003839 salts Chemical class 0.000 abstract description 6
229930194542 Keto Natural products 0.000 abstract description 5
229910052739 hydrogen Inorganic materials 0.000 abstract description 3
239000001257 hydrogen Substances 0.000 abstract description 3
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 8
CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract 2
KJDGFQJCHFJTRH-YONAWACDSA-N 16-Ketoestradiol Chemical group OC1=CC=C2[C@H]3CC[C@](C)([C@H](C(=O)C4)O)[C@@H]4[C@@H]3CCC2=C1 KJDGFQJCHFJTRH-YONAWACDSA-N 0.000 abstract 1
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
150000001728 carbonyl compounds Chemical class 0.000 abstract 1
ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical group O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 abstract 1
229920006395 saturated elastomer Polymers 0.000 abstract 1
125000004432 carbon atom Chemical group C* 0.000 description 32
-1 aromatic carbonyl compound Chemical class 0.000 description 27
JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 20
NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 14
125000000217 alkyl group Chemical group 0.000 description 11
239000007788 liquid Substances 0.000 description 11
235000005074 zinc chloride Nutrition 0.000 description 10
239000011592 zinc chloride Substances 0.000 description 10
NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 10
229960001763 zinc sulfate Drugs 0.000 description 10
229910000368 zinc sulfate Inorganic materials 0.000 description 10
125000002947 alkylene group Chemical group 0.000 description 9
125000003118 aryl group Chemical group 0.000 description 8
150000003751 zinc Chemical class 0.000 description 8
235000019270 ammonium chloride Nutrition 0.000 description 7
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
150000003585 thioureas Chemical class 0.000 description 6
GMEHFXXZSWDEDB-UHFFFAOYSA-N N-ethylthiourea Chemical compound CCNC(N)=S GMEHFXXZSWDEDB-UHFFFAOYSA-N 0.000 description 5
238000000576 coating method Methods 0.000 description 5
239000000203 mixture Substances 0.000 description 5
KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
125000002768 hydroxyalkyl group Chemical group 0.000 description 4
125000000468 ketone group Chemical group 0.000 description 4
239000002932 luster Substances 0.000 description 4
SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
159000000000 sodium salts Chemical class 0.000 description 4
HXUIDZOMTRMIOE-UHFFFAOYSA-N 3-oxo-3-phenylpropionic acid Chemical compound OC(=O)CC(=O)C1=CC=CC=C1 HXUIDZOMTRMIOE-UHFFFAOYSA-N 0.000 description 3
QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 3
BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 3
239000004439 Isononyl alcohol Substances 0.000 description 3
VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
239000004327 boric acid Substances 0.000 description 3
239000000460 chlorine Substances 0.000 description 3
125000000753 cycloalkyl group Chemical group 0.000 description 3
150000002191 fatty alcohols Chemical class 0.000 description 3
150000008040 ionic compounds Chemical class 0.000 description 3
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
229920001515 polyalkylene glycol Polymers 0.000 description 3
229920001451 polypropylene glycol Polymers 0.000 description 3
239000001632 sodium acetate Substances 0.000 description 3
235000017281 sodium acetate Nutrition 0.000 description 3
BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 3
239000002351 wastewater Substances 0.000 description 3
DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
125000001931 aliphatic group Chemical group 0.000 description 2
150000001412 amines Chemical class 0.000 description 2
150000001449 anionic compounds Chemical class 0.000 description 2
239000011260 aqueous acid Substances 0.000 description 2
125000003710 aryl alkyl group Chemical group 0.000 description 2
150000001875 compounds Chemical class 0.000 description 2
238000002425 crystallisation Methods 0.000 description 2
230000008025 crystallization Effects 0.000 description 2
SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 2
239000006185 dispersion Substances 0.000 description 2
125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
125000004494 ethyl ester group Chemical group 0.000 description 2
125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
229920001223 polyethylene glycol Polymers 0.000 description 2
150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
108010010803 Gelatin Proteins 0.000 description 1
UHGKYJXJYJWDAM-UHFFFAOYSA-N Propylthiourea Chemical compound CCCNC(N)=S UHGKYJXJYJWDAM-UHFFFAOYSA-N 0.000 description 1
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
239000000654 additive Substances 0.000 description 1
125000005907 alkyl ester group Chemical group 0.000 description 1
229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
150000008052 alkyl sulfonates Chemical class 0.000 description 1
ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 1
AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
125000004429 atom Chemical group 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
GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
229910052794 bromium Inorganic materials 0.000 description 1
DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical class NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
229910052801 chlorine Inorganic materials 0.000 description 1
125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
239000007857 degradation product Substances 0.000 description 1
238000001784 detoxification Methods 0.000 description 1
235000014113 dietary fatty acids Nutrition 0.000 description 1
125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
229930195729 fatty acid Natural products 0.000 description 1
239000000194 fatty acid Substances 0.000 description 1
150000004665 fatty acids Chemical class 0.000 description 1
230000002349 favourable effect Effects 0.000 description 1
229920000159 gelatin Polymers 0.000 description 1
235000019322 gelatine Nutrition 0.000 description 1
235000011852 gelatine desserts Nutrition 0.000 description 1
229910052736 halogen Inorganic materials 0.000 description 1
150000002367 halogens Chemical class 0.000 description 1
238000012986 modification Methods 0.000 description 1
230000004048 modification Effects 0.000 description 1
239000008164 mustard oil Substances 0.000 description 1
125000001624 naphthyl group Chemical group 0.000 description 1
125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
230000002265 prevention Effects 0.000 description 1
125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
108090000623 proteins and genes Proteins 0.000 description 1
102000004169 proteins and genes Human genes 0.000 description 1
230000017854 proteolysis Effects 0.000 description 1
150000003871 sulfonates Chemical class 0.000 description 1
125000000472 sulfonyl group Chemical group *S(*)(=O)=O 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc

Definitions

novel aqueous acid electroplatic baths of the invention contain a water-soluble zinc salt, usual lustering agents and wetting agents, optionally an additional conducting salt, a thiourea derivative of the formula wherein R is selected from the group consisting of alkyl of 6 to 22 carbon atoms, a monoor polynuclear aryl which may optionally be substituted with an aliphatic or aromatic group, arylalkyl and cycloalkyl, R is selected from the group consisting of hydrogen and hydroxyalkyl of 2 to 6 carbon atoms which may optionally be interrupted by an ether oxygen and R is hydroxyalkyl of 2 to 6 carbon atoms which may be optionally interrupted by an ether oxygen, and an aromatic carbonyl compound selected from the group consisting of wherein R is aryl, A is selected from the group consisting of saturated alkylene with 1 to 7 carbon atoms and unsaturated alkylene with 2 to 7 carbon atoms, and R is lower alkyl with 1 to 7
R is alkyl of 6 to 22 carbon atoms, phenyl or naphthyl which may be further substituted with alkyl of 1 to 10 carbon atoms such as methyl or nonyl, halogens such as chlorine or bromine, sulfonyl or phenyl, cycloalkyl of 5 to 12 carbon atoms such as cyclopentyl, cyclohexyl, menthyl or bornyl and phenyl lower alkyl such as benzyl or phenethyl.
R is aryl, preferably phenyl which may be optionally substituted with a lower alkyl of l to 7 carbon atoms.
A is a saturated oiunsaturated alkylene of 1 to 7 carbon atoms, preferably 1 to 3 carbon atoms, such as methyl, ethyl, propyl, vinylene, etc.
R is preferably a lower alkyl of 1 to 7 carbon atoms, optionally substituted with keto, carboxy, and carbalkoxy of 1 to 7 carbon atoms, such as methyl, methylcarboxy, and methylcarbethoxy.
aromatic carbonyl compounds examples include acetophenone, benzoyl-acetic acid, alkyl esters of benzoylacetic acid, such as the ethyl ester, benzoyl-acetone, benzal acetone and a-acetyl naphthalene.
Examples of suitable compounds of Formula I are N-hexyl-N'-(' -hydroxyethoxy)-ethyl-, N-octyl-N'- ('y-hydroxy-ethoxy -propyl', N-dodecyl-N'- ('y-hydroxyethoxy) -ethyl-, N-octadecyl-N-( -hydroxyethoxy) -ethyl-, N-phenyl-N'- 'y-hydroxy-ethoxy -ethyl-, N-diphenyl-N'- ('y-hydroxyethoxy) -propyl-,
the thioureas of Formula I can be prepared by known methods by reacting a mustard oil of the formula R-N-CS with an amine of the formula wherein R, R and R have the above definitions or by reacting a thiourea of the formula R-NH--CS--NH with a lower alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.
the concentration of the thiourea derivatives of Formula I in the zinc electroplating baths may be between 0.01 to 10 gm. per liter, preferably between 0.1 to 5.0 gm. per liter, of bath liquid.
the current density used for the electroplating method is between 0.5 to 8 a./dm. at a bath operating temperature of 10 to 40 C. preferably 15 to 30 C.
the pH of the acid baths is generally in the range of 3 to 5.
the concentration of the aromatic carbonyl compounds in the zinc electroplating baths may be between 0.01 to 10 gm. per .liter of bath liquid, preferably between 0.1 to 5 gm. per liter, of bath liquid.
the water-soluble zinc salt may be any of the usual zinc salts such as zinc chloride or zinc sulfate or mixtures thereof.
the acid baths contain 25 to 450 gm. per liter of bath liquid of the zinc salt.
the additional conducting salt which may be present in the bath is preferably a water-soluble aluminum salt such as its chloride or sulfate. The amount of said additional conducting salt is 1 to 50 gm. per liter of bath liquid.
Various wetting agents can be added to the acid baths in amounts of 0.5 to gm. per liter of bath liquid.
non-ionic wetting agents by the adducts of an alkylene oxide such as ethylene oxide and/or propylene oxide and high molecular weight aliphatic alcohols or alkyl phenols such as the adducts of 2 to 100 moles of ethylene oxide and 1 mole of a straight or branched chain aliphatic alcohol of 8 to 22 carbon atoms and mixtures thereof or to alkylphenols such as nonylphenol, fatty amines, fatty acid amides or fatty mercaptans.
the wetting agents are preferably anionic compounds such as fatty alcohol sulfates or fatty alcohol ether sulfates, alkyl sulfonates or al kylaryl sulfonates or non-ionic compounds of the polyalkylene glycol type.
anionic compounds such as fatty alcohol sulfates or fatty alcohol ether sulfates, alkyl sulfonates or al kylaryl sulfonates or non-ionic compounds of the polyalkylene glycol type.
suit able additives of these types are sulfates or ether sulfates of fatty alcohols of 8 to 18 carbon atoms and polyethylene glycols and polypropylene glycols with a molecular weight of 200 to 600.
Suitable lustering agents are thiourea,
N-phenyl-N'- -hydroxyethyl) -ethyl-thiourea N-benzyl-N- ('y-hydroxyethyl) ethyl-thiourea, N-octyl-N'- 'y-hydroxyethoxy propyl-thiourea, N-a-naphthyl-N- -hydroxyethoxy) ethyl-thiourea, N-cyclohexyl-N'- -hydroxyethoxy) -propyl-thiourea, N-benzyl-N'-bisy-hydroxyethyl -thiourea.
customary lustering agents for acidic zinc baths include protein, gelatins, protein degradation products, polyimines, and dithiocarbamic acid derivatives.
the preferred wetting agents for acid zinc chloride baths are non-ionic compounds of the type of adducts ethylene oxide and high molecular aliphatic alcohols or alkylphenols, such as adducts of from 2 to mol of ethylene oxide and 1 mol of straight chain or branched chain aliphatic alcohols of 8 to 22 carbon atoms and mixtures thereof, or to nonylphenol.
wetting agents are anionic compounds such as fatty alcohol sulfates or fatty alcohol ether sulfates type such as C -C fatty alcohol sulfates or C -C fatty alcohol ether sulfates or non-ionic compounds of the polyalkylene glycol type, such as polyethyleneand polypropylene glycols having a molecular weight of 200-600.
Particularly favorable results with respect to covering capacity and degree of luster may be obtained in the acid zinc chloride bath with the aromatic carbonyl compounds to be used in the inventions, when the zinc chloride bath contains adducts of ethylene oxide and isononyl alcohol as the wetting agent.
the quantity of wetting agent used in the bath is generally0.5-10 g./l. of bath liquid.
An aqueous Zinc electroplating bath was prepared with the following composition: gm./liter of crystalline zinc chloride (ZnCl 6H O), 175 gm./ liter of ammonium chloride, 0.5 gm./liter of N-phenyl-N'-(q hydroxyethyl)- ethyl-thiourea and 5 grrL/liter of the adduct of 17 moles of ethylene oxide and 1 mole of isononyl alcohol.
the bath had a pH of 4.6.
the electroplating bath provided lustrous, ductile zinc deposits with a good covering power at an operating temperature of 15 to 30 C. over a current density range of 2 to 5 a./dm.
EXAMPLE II An aqueous zinc electroplating bath containing 100 gm./liter of crystalline zinc chloride (ZnCl -6H O), 50 gm./ liter of crystalline aluminum chloride (AlCl -6H O), gm./liter of ammonium chloride, 2 gm./liter of N- benzyl-N-('y-hydroxyethyl)ethyl-thiourea and 4 gm./liter of 'the adduct of 20 moles of ethylene oxide and one mole of nonylphenol with a pH of 3 was operated at temperatures of 15 to 30 C. over a current density range of 0.3 to 5.0 a./dm. and provided bright to lustrous ductile Zinc deposits with a good covering power.
ZnCl -6H O crystalline zinc chloride
AlCl -6H O crystalline aluminum chloride
Ammonium chloride 2 gm./liter of N- benzyl-N-
EXAMPLE III An aqueous zinc bath containing 400 g./liter of crystalline zinc sulfate (ZnSO -7H O), 15 g./liter of ammonium chloride, 30 g./liter of boric acid, 0.7 g./liter of N-octyl-N- ('y-hydroxyethoxy)-propyl-thiourea and 5 g./ liter of sodium salt of the C C -fatty alcohol sulfate and having a pH of 3.5 was operated at a temperature of 15 to 30 C. over a current density range of 0.5 to 3 a./dm. to obtain bright, ductile zinc coatings with satisfactory covering power.
ZnSO -7H O crystalline zinc sulfate
ammonium chloride 15 g./liter
boric acid 0.7 g./liter of N-octyl-N- ('y-hydroxyethoxy)-propyl-thiourea
EXAMPLE IV An aqueous zinc bath containing 240 g./liter of crystalline zinc sulfate (ZnSO -7H O), 30 g./liter of crystalline aluminum sulfate (Al (SO -18H O), l5 g./liter of sodium acetate, 0.2 g./liter of N-a-naphthyl-N'-('y-hydroxyethoxy)-ethyl-thi0urea and 4 g./liter of' sodium salt of the C -C -fatty alcohol sulfate and having a pH of 4.0 was operated at at temperature of 15 to 30 C. over a current density range of 0.5 to 5 a./dm. to provide bright, ductile zinc coatings with excellent covering power.
ZnSO -7H O crystalline zinc sulfate
Al (SO -18H O) crystalline aluminum sulfate
Al (SO -18H O) l5 g./liter of sodium
EXAMPLE v An aqueous zinc bath containing 400 g./liter of crystalline zinc sulfate (ZnSO -7H O), g./ liter of ammonium chloride, 30 g./liter of boric acid, 1 g./liter of N-cyclohexyl-N'-('y-hydroxyethoxy)-propyl-thiourea, 5 g./liter of sodium lauryl ether sulfate having a pH of 3.5 was operated at a temperature of 15 to 30 C. over a current density range of 0.5 to 5 a./dm. to obtain lustrous, ductile zinc coatings with satisfactory covering power.
ZnSO -7H O crystalline zinc sulfate
boric acid 30 g./liter
Na lauryl ether sulfate sodium lauryl ether sulfate having a pH of 3.5
EXAMPLE VI An aqueous zinc bath containing 240 g./liter of crystalline zinc sulfate ZnSO -7H O, 30 g./liter of crystalline aluminum sulfate [Al (SO *18H O], 15 g./liter of sodium acetate, 1 g./liter of N-benzyl-N'-bis-('y-hydroxyethyl)thiourea and 5 g./liter of sodium lauryl ether sulfate having a pH of 4.0 was operated at a temperature of 15 to 30 C. over a current density range of 0.5 to 5 a./dm. to provide bright, ductile zinc coatings with satisfactory covering power.
EXAMPLE VII An aqueous zinc electroplating bath containing 110 gm./ liter of zinc chloride free from water of crystallization, 175 gm./liter of ammonium chloride, 0.5 gm./liter of N-phenyl-N'-('y-hydroxyethoxy-)-ethyl-thiourea, 0.2 gm./ liter of benzalacetone, and 5 gm./1iter of the adduct of 17 moles of ethylene oxide and 1 mole of isononyl alcohol having a pH of 4.6 was operated at temperatures of 15 to 30 C. over a current density range of 1 to 6 a./dm. to provide high-gloss, ductile zinc coatings with a good covering power.
EXAMPLE VIII An aqueous zinc electroplating bath containing 100 gm./liter of zinc chloride free from water of crystallization, 50 gm./ liter of crystalline aluminum chloride 150 gm./liter of ammonium chloride, 1 gm./liter of N- benzyl-N-(' -hydroxyethoxy-) ethyl-thiourea, 0.1 gm./ liter of acetophenone, and 6 gm./ liter of the adduct of moles of ethylene oxide and 1 mole of nonylphenol having a pH of 3.0 was operated at temperatures of 15 to 30 C. over a current density range of 1 to S a./dm. to provide bright, ductile zinc deposits with a good covering power.
EXAMPLE IX An aqueous zinc electroplating bath containing 400 gm./liter of crystalline zinc sulfate ZnSO -7H O, 15 gm./liter of ammonium chloride, 30 gm./liter of boric acid, 0.7 gm./liter of N-octy1-N'-( -hydroxyethoxyd ethyl-thiourea, 0.3 gm./ liter of the ethyl ester of benzoylacetic acid and 5 gm./ liter of a sodium salt of the C -C fatty alcohol sulfate mixture with a pH of 3.5 was operated at temperatures of 15 to 30 C. over a current density range of 0.5 to 3 a./dm. to provide bright, ductile Zinc deposits with a satisfactory covering capacity.
EXAMPLE X EXAMPLE XI An aqueous zinc electroplating bath containing 240 gm./ liter of crystalline zinc sulfate ZnSO -7H O, 30 gm./
an acid aqueous electroplating bath for forming lustrous zinc deposits comprising a bath containing a water-soluble zinc salt, usual lustering agents and wet ting agents, optionally an additional conducting salt, a thiourea derivative of the formula wherein R is selected from the group consisting of alkyl of 6 to 22 carbon atoms, a monoor polynuclear aryl which may optionally be substituted with an aliphatic or aromatic group, arylalkyl and cycloalkyl, R is selected from the group consisting of hydrogen and hydroxyalkyl of 2 to 6 carbon atoms which may optionally be interrupted by an ether oxygen and R is hydroxyalkyl of 2 to 6 carbon atoms which may be optionally interrupted by an ether oxygen, the improvement comprising incorporating in the bath from 0.01 to 10 gm.
an aromatic carbonyl compound selected from the group consisting of wherein R is aryl, A is selected from the group consisting of saturated alkylene with 1 to 7 carbon atoms and unsaturated alkylene with 2 to 7 carbon atoms and R is lower alkyl with 1 to 7 canbon atoms optionally substituted with a member selected from the group consisting of keto, carboxy, and carbal'koxy of 1 to 7 carbon atoms.
the bath of claim 4 wherein the zinc salt is zinc chloride and the bath further contains a wetting agent selected from the group consisting of adducts of ethylene oxide with an alkyl phenol and adducts of ethylene oxide with aliphatic alcohol of 8 to 22 carbon atoms.
a wetting agent selected from the group consisting of adducts of ethylene oxide with an alkyl phenol and adducts of ethylene oxide with aliphatic alcohol of 8 to 22 carbon atoms.
the wetting agent is selected from the group consisting of sulfates of fatty alcohols of 8 to 18 carbon atoms, ether sulfates of fatty alcohols of 8 to 18 carbon atoms and polyethylene glycols and polypropylene glycols with a molecular weight of 200 to 600.

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Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Electrochemistry (AREA)
Materials Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
Electroplating And Plating Baths Therefor (AREA)
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US00243827A 1971-04-16 1972-04-13 Electroplating Expired - Lifetime US3795594A (en)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
DE2118512A DE2118512C3 (de)	1971-04-16	1971-04-16	Saures galvanisches Glanzzinkbad

Publications (1)

Publication Number	Publication Date
US3795594A true US3795594A (en)	1974-03-05

Family

ID=5804913

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
US00243827A Expired - Lifetime US3795594A (en)	1971-04-16	1972-04-13	Electroplating

Country Status (7)

Country	Link
US (1)	US3795594A (2)
JP (1)	JPS5427302B1 (2)
BR (1)	BR7202257D0 (2)
DE (1)	DE2118512C3 (2)
FR (1)	FR2133780B2 (2)
GB (1)	GB1354078A (2)
IT (1)	IT1013522B (2)

1971
- 1971-04-16 DE DE2118512A patent/DE2118512C3/de not_active Expired
1972
- 1972-04-12 IT IT7219/72A patent/IT1013522B/it active
- 1972-04-13 JP JP3653372A patent/JPS5427302B1/ja active Pending
- 1972-04-13 US US00243827A patent/US3795594A/en not_active Expired - Lifetime
- 1972-04-14 GB GB1720972A patent/GB1354078A/en not_active Expired
- 1972-04-14 BR BR002257/72A patent/BR7202257D0/pt unknown
- 1972-04-14 FR FR7213286A patent/FR2133780B2/fr not_active Expired

Also Published As

Publication number	Publication date
FR2133780A2 (2)	1972-12-01
JPS5427302B1 (2)	1979-09-08
IT1013522B (it)	1977-03-30
DE2118512B2 (de)	1979-04-12
DE2118512A1 (de)	1972-10-26
DE2118512C3 (de)	1979-12-20
GB1354078A (en)	1974-06-05
BR7202257D0 (pt)	1973-05-10
FR2133780B2 (2)	1977-12-23

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