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

• an object of this invention to provide an electroplating process whereby bright, level and adherent nickel electrodeposits can be obtained free from the disadvantageous effects of hydrogen evolution at the cathode which substantially reduces the corrosion protection desired for the base metal.
• Another object of this invention is to provide an additive for nickel plating baths from which bright, level, ductile and adherent nickel deposits may be obtained.
• a further object of this invention is to provide an additive for nickel plating baths which is a cathode depolarizer and a process wherein the additive is employed to reduce the evolution of hydrogen at the cathode so as to produce on the base metal a porous free deposit having increased corrosion protection characteristics.
• Yet another object of this invention is to provide a nickel plating bath incorporating an imidazol type brightener as disclosed in my copending application Serial No. 239,329, filed November 21, 1962, now US. Patent 3,130,135, to produce a coating possessing good ductility and improved corrosion resistance properties by a more economical method.
• R is selected from the group consisting of alkenyl, alkynyl, alkenoyl or alkynoyl radicals having 1 to 6 carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic or aromatic groups; R, is an aliphatic bridge containing from 1 to carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• the novel brightener of this invention is generally used in amounts between 0.001 and 5 millimoles per liter of bath solution and preferably between 0.001 to 1 millimole per liter of solution.
• the process of the invention involves operating a bath at conventional nickel plating temperatures ranging from about 30 C. to as high as C. with a range of 4065 C. being especially desirable.
• the pH of the plating bath can range from around 1.5 to 5.0 with 3.0 to 5.0 being found especially suitable in the majority of cases.
• Practically all baths for electroplating nickel contain nickel sulfate, a chloride, usually nickel chloride, a buffering agent, usually boric acid and a wetting agent.
• Such types of baths include the well-known Watts-type bath and high chloride type bath.
• the Watts bath solution to which the novel brightener of this invention can be added typically comprises around 300 grams per liter of nickel sulfate, 60 grams per liter of nickel chloride and 40 grams per liter of boric acid.
• the foregoing bath composition and specified operating conditions are not critical in the basic Watts bath solution and the particular temperature and pH thereof may vary within the indicated ranges without adverse effects.
• Considerable latitude is also permissible in respect to the types and concentrations of the nickel salts employed, for instance, as the source of nickel, a combination of nickel fluoborate with nickel sulfate and nickel chloride, or a combination of nickel fluoborate with nickel chloride can be used.
• the nickel plating bath solution can contain, in addition to the novel brightener of this invention, a brightener of the first class which is, preferably, an aromatic sulfur compound such as p-toluene 'sulfonamide, oabenzoyl :sulfimide, benzene sulfonarnide, naphthalene sulfonic acid, benzene sulphonic acid, Z-butyne, 1,4-disulphonic acid, allyl sulphonic acid together with Z-butyne, 1,4-dioxyethanesulphonic acid or sodium saccharate.
• an aromatic sulfur compound such as p-toluene 'sulfonamide, oabenzoyl :sulfimide, benzene sulfonarnide, naphthalene sulfonic acid, benzene sulphonic acid, Z-butyne, 1,4-disulphonic acid, allyl
• the novel brightener of the invention is generally employed in amounts ranging between 0.025 to 2.5 millimoles per liter of solution while the brightener of the first class advantageously is employed in amounts ranging from 0.05 to 15 grams per liter of solution.
• a mirror bright deposit of high luster is obtained when using this combination of brighteners.
• novel brighteners of this invention are employed with an imidazol compound disclosed in my copending application Serial No. 239,329, filed November 21, 1962, and incorporated herein by reference, having the formula wherein R is selected from the group consisting of hydrogen and -AR A being an aliphatic bridge and R being selected from the group consisting of unsaturated and saturated aliphatic and cyclic radicals and aromatic radicals; wherein R and R are selected from the group consisting of hydrogen, aliphatic and cyclic, saturated and unsaturated hydrocarbon radicals, and wherein R is selected from the group consisting of hydrogen and A-R A being an aliphatic bridge and R being se lected from the group consisting of aliphatic and cyclic, saturated and unsaturated hydrocarbon radicals and aliphatic radicals bearing at least one amino group, and alkoxy groups; at least one of R and R being an unsaturated radical.
• Imidazol compounds representative of the aforedescri'bed compounds are, for instance, 3-pr0- 3 pynyl-amino-ethyl-imidazol, 3-propynyl-imidazole, 2-propynyl-3-(beta hydroxyethyl)-imidazol, 2-propenyl-imidazol and 2-propynyl-3-diethylenediamine-imidazol.
• the novel brightener of this invention is employed in synergistic amounts ranging from about 0.1 to 0.5 millimole per liter of solution while the imidazol compound is effectively used in amounts from about 0.005 to 0.01 millimole per liter of solution although an amount of the novel brightener of this invention ranging from 0.05 to 5 millimoles per liter and an amount of the imidazol ranging from 0.001 to 1 millimole per liter can be eifectively used.
• This combination of brightener additives results in a more economical deposition of nickel coating and results in the reduction of break-down product formation which in turn results in longer cycles between filtering and/or purification of the nickel plating bath solution.
• wetting agents can be used in association with the novel plating bath compositions of this invention such as sodium lauryl sulfate, sodium lauryl ether sulfate and 7-ethyl-2-methyl-4 undecanol, it has been found that particularly advantageous results are produced when a wetting agent is employed having, preferably, the following formula and used in amounts of about 0.5 to 5 g./l.
• R is an alkanoyl group having 8 to 10 carbon atoms
• R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals
• R is and R is selected from the group consisting of hydrogen and alkali metals.
• Representative wetting agents of this type are sodium octanoyl methyl taurate, potassium nonanoyl methyl taurate, sodium decanoyl methyl taurate, sodium octanoyl cyclohexyl taurate, sodium nonanoyl methyl phenyl taurate, sodium decanoyl phenyl taurate, sodium octanoyl cyclopropyl taurate,.
• octanoyl hexyl amino propylene sulfonic acid sodium salt of decanoyl cyclobutyl amino butylene sulfonic acid, and octanoyl tauric acid.
• oleoyl methyl taurate as a wetting or surface active agent.
• This wetting agent produces a billowy foam.
• this type of wetting agent is employed in situations utilizing mechanical rather than air agitation means.
• a sequestering agent having the following formula may be employed,
• R is an alkanoyl radical containing 1 to 6 carbon atoms
• R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals
• R is an aliphatic bridge containing from 1 to 5 carbon atoms
• R is selected from the group consisting of hydrogen and alkali metals.
• sequestering agents of this type are sodium methyl formyl taurate, potassium methyl glyoxyl taurate, sodium methyl heptahydroxyhexanoyl taurate, sodium formyl cyclohexyl taurate, sodium glyoxyl methyl phenyl taurate, sodium butanoyl cyclopropyl taurate, sodium hexanoyl hexyl taurate, pentanoyl hexyl amino propylene sulfonic acid, sodium salt of formyl cyclobutylamino butylene :sulfonic acid and heptahydroxyhexanoyl tauric acid.
• the sequestering agent is employed in amounts of about 0.1 to 5 grams per liter of bath solution.
• an aqueous acidic nickelcontaining bath was made up with the specified components. Electro-deposition was carried out by passing electric current through an electric circuit comprising an anode and a sheet metal or rod cathode, both immersed in the bath. The baths were agitated, usually by a moving cathode although in certain instances air agitation was employed.
• the examples utilizing the novel brighteners of this invention resulted in a nickel coating with improved leveling effects and corrosion resistance properties.
• a brightener of the first class i.e. an aromatic sulfur compound
• the resulting sulfur-containing nickel coating also exhibited mirror bright characteristics as well as stress-free properties. High brightness and improved ductility properties were achieved in those examples where in combination with the novel brighteners of this invention, an imidazol compound was employed.
• Example 1 Sodium propargyl methyl taurate mmol/l 2
• Example 2 Sodium propargyl methyl taurate mmol/l"
• Sodium naphthalene tri-sulfonic acid m.mol/l '10
• Example 3 Sodium propargyl cyclohexyl taurate mmol/1 1.0 Sodium saccharate 'g./1 1.5 Sodium octanoyl methyl taurate (air agitated g./l 0.5
• Example 4 Sodium propenyl methyil taurate mmol/l 2.0 Sodium sacch-arate g./l 1.5 Sodium heptahydroxyhexanoyl taurate (air agitated) g./l 2.0
• Example 5 Sodium propenylmethyl taurate mmol/l 0.5 Sodium saccharate 'g./l 1.5 P'ropargylaminoethylene imidazol *mmol/l 0.01 Sodium octanoylmethyl taurate (air agitated) g./l 0.2
• Example 6 Sodium hydroxy butynyl taurate I1'1II10ll/l 1.0 Sodium saccharate g./l 1.5 Z-propenyl-Lamino i-midazol mmol/l 0.01 Sodium octanoylmethyl taurate (air agitated) I -g./l 0.2
• Example 7 Sodium propargylmethyl taurate mmol/l" 1.0 Sodium saccharate g./ 1.5 Proparagylaminoethylene imidazol mmol/l 0.001 Sodium methy l oleoyl taurate g./l 0.2
• Example 8 Sodium vinyl methylphenyl taurate mmol/l 0.5 3-propynylaminoethyl imidazol mmol/l 0.01
• Example 10 Sodium isopropenyl taurate mimol/l" 0.3 2-popynyl-3-diethy-lenediamine irnidazol m:m-ol/l 0.08 Sodium octanoyll cyclopropyl taurate g./l 0.5
• Example 12 2-butenyl tauric acid rnmol/l 2 p-toluene sul-fonamide g./l 10
• Example 14 Sodium salt of Z-butynyl cyclopropylam-ino butyl-ene sulfonic acid mmol/l 10 o-Benzoyl sulfamide -g./l 5
• Example 17 Sodium crotonyl propyl taurate mmol/l 10
• Example 18 2-pentenoyl hexylarnino propylene sulfonic acid mmol/l 0.05 3-ipropynyl imidazo-l mml/l 0.001
• Example 19 Potassium vinylacetyl methyl taurate mmorl/l 1.0 Sodium saccharate 'g./l 1.5 Sodium octanoyl cyclo b utyl taur-ate (air agitation) 'g./l 0.5
• Example 20 Sodium propiolyl pentyl taurate mmol/l 10 Sodium octanoylmethyl taurate g./l 0.2
• Example 21 Sodium salt of butynoyl cyclobutylamino butylene sulfonic acid mmo1/L
• Example 22 Sodium hydroxy butynoyl ethylphenyl taurate mrnol/l 0.5 2-propynyl-3-(beta hydroxyethyl) imidazol mrnol/l 0.01 Sodium saccharate g./l 1.5 Potassium methyl glyoxyl taurate g./l 5
• Example 23 Sodium pentynoyl hexyl taurate mmol/l 5 Z-butyne, 1,4-disulphonic acid g./l 1.5 Sodium butanoyl cyclopropyl taurate g./1 0.5
• An aqueous acidic bath solution for electroplating nickel containing at least one nickel salt as a source of nickel which plating solution includes a brightener having the structural formula wherein R is selected from the group consisting of alkenyl, alkynyl, alkenoyl and alkynoyl radicals having 1 to 6 carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• the nickel plating solution of claim 1 which includes a Wetting agent having the formula wherein R is an alkenoyl radical having 8 to 10 carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consistnig of hydrogen and alkali metal.
• a Wetting agent having the formula wherein R is an alkenoyl radical having 8 to 10 carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consistnig of hydrogen and alkali metal.
• the nickel plating solution of claim 1 which includes a sequestering agent having the formula Rrr- TI-RWSOSRN wherein R is an alkanoyl radical having 1 to 6 carbon atoms, R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• a sequestering agent having the formula Rrr- TI-RWSOSRN wherein R is an alkanoyl radical having 1 to 6 carbon atoms, R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• the nickel plating solution of claim 1 which includes sodium methyl oleoyl taurate.
• An aqueous acidic bath solution for electroplating nickel containing at least one nickel salt as a source of nickel which plating solution includes a first brightener having the structural formula wherein R is selected from the group consisting of alkenyl, alkynyl, alkenoyl and alkynoyl radicals having 1 to 6 carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal together with an aromatic sulfur compound as a second brightener of the first class.
• the nickel plating solution of claim 8 which includes a wetting agent having the formula wherein R is an alkanoyl radical having 8 to carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• the nickel plating solution of claim 8 which includes a sequestering agent having the formula wherein R is an alkanoyl radical having 1 to 6 carbon atoms, R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals, R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• the nickel plating solution of claim 8 which includes sodium methyl oleoyl taurate.
• An aqueous acid bath solution for electroplating nickel containing at least one nickel salt as a source of nickel which plating solution includes a first brightener having the structural formula wherein R is selected from the group consisting of alkenyl, alkynyl, alkenoyl and alkynoyl radicals having 1 to 6 carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals, R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal together with, as a second brightener, an imidazol compound having the formula wherein R is selected from the group consisting of hydrogen and AR A being an aliphatic bridge and R being selected from the group consisting of unsaturated and saturated aliphatic and cyclic radicals and aromatic radicals; R and R1 being selected from the group consisting of hydrogen, aliphatic and cyclic, saturated and unsaturated hydrocarbon radicals; and wherein R
• the nickel plating solution of claim 16 which includes as a third brightener of the first class an aromatic sulfur compound.
• the nickel plating solution of claim 16 which includes a wetting agent having the formula wherein R is an alkanoyl radical having 8 to 10 carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• the nickel plating solution of claim 16 which includes a sequestering agent having the formula R 5I lIRn S OGRtS wherein R is an alkanoyl radical having 1 to 6 carbon atoms, R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• a sequestering agent having the formula R 5I lIRn S OGRtS wherein R is an alkanoyl radical having 1 to 6 carbon atoms, R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• the nickel plating solution of claim 16 which includes sodium methyl oleoyl taurate.
• the process of producing nickel deposits of improved ductility and corrosion resistance characteristics on a metal base which comprises electro-depositing nickel from an aqueous acidic bath by passing a current from an anode to a cathode to be plated, said acidic bath containing nickel in the form of a soluble inorganic salt, in the presence of a brightener having the structural formula wherein R is selected from the group consisting of alkenyl, alkynyl, alkenoyl and alkynoyl radicals having 1 to 6 carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal.
• said bath includes as a second brightener an imidazol compound having the formula wherein R is selected from the group consisting of hydrogen and AR A being an aliphatic bridge and R being selected from the group consisting of unsaturated and saturated, aliphatic and cyclic radicals and aromatic radicals; R and R being selected from the group consisting of hydrogen, aliphatic and cyclic saturated and unsaturated hydrocarbon radicals; and wherein R is selected from the group consisting of hydrogen and AR A being an aliphatic bridge and R being selected from the group consisting of aliphatic and cyclic, saturated and unsaturated hydrocarbon radicals and aliphatic radicals bearing at least one amino group and alkoXy groups; at least one of R and R being an unsaturated radical.
• said bath includes a wetting agent having the formula wherein R is an alkanoyl radical having 8 to carbon atoms; R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R 14 is selected from the group consisting of hydrogen and alkali metal, said wetting agent being present in amounts of 0.5 to 5 g./l. of solution.
• said bath includes a sequestering agent having the formula R15 TlRr1SOaRm wherein R is a alkanoyl radical having 1 to 6 carbon atoms, R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal, said sequestering agent being present in amounts of 0.1 to 5 g./l. of solution.
• a sequestering agent having the formula R15 TlRr1SOaRm wherein R is a alkanoyl radical having 1 to 6 carbon atoms, R is selected from the group consisting of hydrogen, aliphatic, alicyclic and aromatic radicals; R is an aliphatic bridge containing from 1 to 5 carbon atoms and R is selected from the group consisting of hydrogen and alkali metal, said sequestering agent being present in amounts of 0.1 to 5 g./l.

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• 1963
  • 1963-12-17 SE SE14058/63A patent/SE307487B/xx unknown
• 1964
  • 1964-05-14 US US367592A patent/US3261772A/en not_active Expired - Lifetime

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