US3795594A - Electroplating - Google Patents

Electroplating Download PDF

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Publication number
US3795594A
US3795594A US00243827A US3795594DA US3795594A US 3795594 A US3795594 A US 3795594A US 00243827 A US00243827 A US 00243827A US 3795594D A US3795594D A US 3795594DA US 3795594 A US3795594 A US 3795594A
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Prior art keywords
carbon atoms
zinc
liter
group
optionally
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US00243827A
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English (en)
Inventor
J Hartenstein
M Nee
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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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  • 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)
  • Cosmetics (AREA)
US00243827A 1971-04-16 1972-04-13 Electroplating Expired - Lifetime US3795594A (en)

Applications Claiming Priority (1)

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DE2118512A DE2118512C3 (de) 1971-04-16 1971-04-16 Saures galvanisches Glanzzinkbad

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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)

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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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