Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
  • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
  • C25D3/16—Acetylenic compounds

Definitions

• the uppermost layer or coatingv of the composite has an electrode potential lower than the lowermost layer or coating, i.e., the coating next adjacent the basis metal to be protected.
• intermediate layers of differing electrode potential have also been provided but like the known double layer systems the uppermost layer has an electrode potential lower than the layer nextadjacent to it.
• a nickel composite coating having a high luster and corrosion resistance is obtained by employing a lowermost layer of electrodeposited nickel having an electrode potential sufficiently great to reduce corrosion effected in industrial atmospheres.
• the lowermost nickel-containing layer is obtained by using a nickel in which A and A are selected from the group consisting 3,180,803 i atented Apr. 27, 1%65 of lower alkyl radicals and 31:0-1, R and R are selected from the group consisting of H, OH,
• X is selected from the group consisting of hydrogen and a halogen
• n is an'integer equal to the number of quaternary N atoms in' R and R with the proviso that the compound contain at least one quaternary N atom.
• the novel brightener of this invention is generally used in amounts between 0.1 to 10 millimoles per liter of bath solution and preferably between 0.2 to 2.0 millimoles 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 40-65 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, 21 chloride, usually nickel chloride; a budering agent, usually boric acid; and a wetting agent, e.g., sodium lauryl sulfate, sodium lauryl ether sulfate, and 7-ethyl-2-methyl-4 undecanol sulfate.
• Such types of baths include the well-known Watts-type bath and high chloride type bath.
• the Watts bath solution to which the brightener of the second class of this invention can be added typically comprises around 300 grams per liter of nickel sulfate, 60 grams per later 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 effect.
• Considerable latitude is also permissible in respect to the types and concentrations of the nickel salts employed, for instance, as the source of the nickel, a combination of nickel iluoborate with nickel sulfate and nickel chloride, or a combination of nickel fluoborate with nickel chloride can be used.
• the upper nickel layer of the composite coating may be deposited from a basic bath similar to the ones used for plating the lowermost layer but it should include a brightener of the first class preferably an organic sulfoncompound such as p-tolucne sulfonamide, o-benzoyl sulfimide, benzene sulfonamide, naphthalene sulphonic acid, benzene sulphonic acid, Z-butyne, 1,4-disulphonic acid, or allyl sulphonic acid together with Z-butyne 1,4-dioxyethanesulphonic acid.
• the organic sulphoncompound will be present in amounts ranging from 1 to 10 grams per liter of solution.
• the upper nickel layer of the composite coating can contain a second brightener of the second class, i.e., one which is different from the novel secondary brighteners of this invention provided in the lower nickel layer.
• a second brightener of the second class are: l-propargyl amino ethylene imidazol, Z-propenyl imidazol, Z-ethynyl imidazol, 2-vinyl imidazol, 2-propenyl-3-diethylene-diauxin-imidazol, 2-(5- phenylethenyl)-3-(fl-hydroxyethyl) imidazol, 3-propynyl imidazol, 2-propenyl-3-(fl-hydroxyethyl) imidazol, 3- propenyl imidazol, 2-propenyl-3-arnino ethyl imidazol, 2- propenyl-3-butyl imidazol, 2 propenyl 4,5 dimethylimida
• novel brightener of the second class of this invention advantageously is used to produce a lowermost coating on a base metal, the lowermost coating being superimposed by one or more coatings preferably of bright nickel to effect a composite coating, it can also advantageously be employed as a single coating to produce a ductile and corrosion resistant sulphur-free coating for a basis metal having a chemical resistance generally about 2.5 times greater than that exhibited by conventional semi-bright coatings.
• a brightener of the first class can be provided to the plating bath containing the novel brighteners of the second class of this invention and especially effective brighteners of the first class are aromatic sulphonic acid compounds which when so included produce a sulphur-containing nickel coating possessing favorable stress-free properties as well as good ductility and corrosion resistance characteristics.
• aromatic sulphonic acid compounds which when so included produce a sulphur-containing nickel coating possessing favorable stress-free properties as well as good ductility and corrosion resistance characteristics.
• the addition of the sodium salt of naphthalene trisulphonic acid for example, is quite effective.
• Other triand dinaphthalene sulphonics may likewise be employed.
• Such other agents include naphthol and sulphonic acids, naphthalamine sulphonic acids, toluidine sulphonic acids and tolidine sulphonic acids or their salts.
• aromatic sulphonic acid compounds can be employed in amounts ranging from 0.5 to 25 grams per liter of bath solution.
• an aqueous acidic nickelcontaining bath was made up with the specified components. Electrodeposition 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.
• the examples utilizing the novel brighteners of the second class of this invention resulted in a nickel coating with favorable ductility and corrosion resistance properties.
• a brightener of the first class i.e., an aromatic sulphonic compound
• the resulting sulphur-containing nickel coating also exhibited favorable stress-free properties.
• a composite coating was produced which resulted in wholly electrochemical corrosion resistance in severe industrial atmospheres.
• Nickel sulfate g./l 300 Nickel chloride g./l 60 Boric acid g./1 40 Sodium lauryl sulfate g./l 0.2-0.5 pH 3.0-5.0 Temperature C 40-63 Current density amperes/dm. 1-10
• Example 1 Propargyl-hydroxy-ammonium bromide mmol/l 0.2
• Example 2 Propargyl-hydroxy-ammonium bromide mmol/l 0.5 Sodium salt of naphthalene trisulphonic acid g./l 10
• Example 3 Propargyl-dihydroxy-ammonium bromide -mmol/L- 0.5 Sodium salt of naphthalene trisulphonic acid g./l 10
• Example 4 1-hydroxy-2-butyne-N-hydroxy ammonium chloride mmol/l 0.2 Sodium salt of naphthalene trisulphonic acid g./l l
• Example 5 1-hydroxy-2-butyne-N-hydroxy ammonium chloride mmol/l 0.5 Sodium salt of naphthalene trisulphonic acid g./l 10
• Example 6 1-hydroxy-Z-butyne-N-dihydroxy ammonium chloride mmol/1 0.2
• Example 7 2-butyne, 1,4-N-hydroxy ammonium chloride mmol/l 0.5 Sodium salt of naphthalene trisulphonic acid g./l 10
• Example 8 4-nonyne, 1,9-N-dihydroxy ammonium chloride mmol/l 0.5
• Example 9 Propargyl dihydroxy ammonium chloride -mmol/L- 0.5 Sodium salt of naphthalene trisulphonic acid g./l 10
• Example 10 3-heptyne, 1,7-N-l1ydroxy ammonium chloride mmol/l 10
• Example 1 Propargyl dihydroxy ammonium hydroxide mmol/l 0.1 Sodium salt of naphthalene trisulphonic acid g./l 0.5
• Example 12 [BI-NICKEL PLATE] Lower plate: Propargyl hydroxy ammonium bromide mmol/l 0.5 Upper plate: Same basic bath as for lower plate except that 2 grams per liter of one or more of the following brighteners of the first class: p-toluene sulfonamide, o-benzoyl sulfimide, benzene sulfonamide, naphthalene sulphonic acid, benzene sulphonic acid together with 0.001 g./l of a brightener of the second class such as propargylaminoethylene imidazol are dissolved in the bath.
• a brightener of the second class such as propargylaminoethylene imidazol
• Example 13 [BI-NICKEL PLATE] Lower plate: Propargyl dihydroxy ammonium bromide mmol/l 10 Sodium salt of naphthalene trisulphonic acid g./l 10 Sodium saecarate -g./1 0.5
• Upper plate Same basic bath as for lower plate except that 10 grams per liter of one or more of the following brighteners of the first class: ptoluene sulfonamide, o-benzoyl sulfidide, benzene sulfonamide, naphthalene sulphonic acid and benzene sulphonic acid together with 0.001 g./l of a brightener of the second class such as S-propynyl imidazol are dissolved in the bath.
• a brightener of the second class such as S-propynyl imidazol
• An aqueous acid bath solution for electroplating nickel containing at least one nickel salt as a source of nickel which plating solution includes a brightener of the second class having the structural formula in which A and A are selected from the group consisting of lower alkyl radicals and y is equal to to 1; R and R are selected from the group consisting of H, OH, NH OH, NH(0H) X is selected from the group consisting of halogen and OH and n is an integer equal to the number of quaternary N atoms in R and K With the proviso that at least one of R and R contains a quaternary N atom.
• a nickel plating solution as defined in claim 1 which further includes an aromatic sulfonic acid compound in amounts sufiicient to provide stress-free properties to the electroplated nickel.
• An aqueous acid bath solution for electroplating nickel containing at least one nickel salt as a source of nickel, which plating solution includes a brightener of the second class having the structural formula:
• a and A are selected from the group consisting of lower alkyl radicals and y is equal to 0 to 1; R and R are selected from the group consisting of H, OH, NH OI-I, NH(OH) X is selected from the group consisting of halogen and OH and n is an integer equal to the number of quaternary N atoms in R and R with the proviso that at least one of R and R contains a quaternary N atom, said brightener of the second class being present in amounts from 0.1 to 10 mmols. per liter of solution and an aromatic sulfonic acid compound in amounts of 0.5 to 25 grams per liter of said solution.
• NH OH, NH(OH) X is selected from the group consisting of halogen and OH and n is an integer equal to the number of quaternary N atoms in R and R with the proviso that at least one of R and R contains a quaternary N atom.
• the process of producing nickel deposits of improved ductility and corrosion resistance characteristics on a metal base which comprises electroplating nickel from an aqueous acid bath containing nickel mainly in the form of a soluble inorganic salt, in the presence of a brightener of the second class having the formula in which A and A are selected from the group consisting of lower alkyl radicals and y is equal to 0 to 1; R and R are selected from the group consisting of H, OH, NH OH, NH(OH) X is selected from the group consisting of halogen and OH and n is an integer equal to the number of quaternary N atoms in R and R with the proviso that at least one of R and R contains a quaternary N atom, said brightener of the second class being present in amounts from 0.1 to 10 mmols. per liter of solution and an aromatic sulphonic acid compound in amounts of 0.5 to 25 grams per liter of solution.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
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Citations (6)

• 1963
  • 1963-05-28 SE SE5909/63A patent/SE302227B/xx unknown
  • 1963-11-29 US US327102A patent/US3180808A/en not_active Expired - Lifetime
• 1964
  • 1964-05-27 DE DE19641496802 patent/DE1496802A1/de active Pending
  • 1964-05-27 GB GB21978/64A patent/GB1068567A/en not_active Expired

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