US3734840A - Electrodeposition of nickel - Google Patents

Electrodeposition of nickel Download PDF

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Publication number
US3734840A
US3734840A US00747098A US3734840DA US3734840A US 3734840 A US3734840 A US 3734840A US 00747098 A US00747098 A US 00747098A US 3734840D A US3734840D A US 3734840DA US 3734840 A US3734840 A US 3734840A
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Prior art keywords
nickel
brightener
compound
primary
electroplating
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US00747098A
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F Passal
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M&T Chemicals Inc
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M&T Chemicals Inc
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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
    • C25D3/12—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
    • C25D3/18—Heterocyclic compounds
    • 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

Definitions

  • This invention relates to novel compositions and to an improved process for electroplating bright nickel which comprises electrodepositing nickel from an aqueous nickel electroplating bath containing (a) as a first primary brightener an effective amount of a water-soluble acetylenic compound, (b) a secondary brightener, and (c) as a second cooperating primary brightener an effective amount of:
  • Y is CN or and salts thereof.
  • This invention relates to a process for nickel plating. More specifically this invention relates to a process for bright nickel plating characterized by outstanding coverage in low current density areas. This invention also relates to novel compositions and compounds.
  • a particular object of this invention is to provide processes and compositions which may be used to provide improved bright nickel plated articles.
  • a further object of this invention is to provide an improved process for the electrodeposition of bright and smooth nickel deposits.
  • the novel process of this invention for electroplating nickel comprises electrodepositing nickel from an aqueous nickel electroplating bath containing (a) as a first primary brightener an effective amount of a water-soluble acetylenic compound, (b) a secondary brightener, and (c) as a second cooperating primary brightener an effective amount of:
  • X is selected from the group consisting of H, NH and HI ICHzOHzON and Y is ON or and salts thereof.
  • Addition agents useful as brighteners in nickel plating baths may be divided into two classes (designated primary and secondary brighteners) on the basis of their predominate function.
  • Primary brighteners are materials used in low or relatively low concentrations, typically 0.0020.2 gram per liter, which by themselves may or may not produce visible brightening action. Those primary brighteners which may exhibit some brightening effects when used alone generally also produce deleterious side-effect such as reduced cathode efliciency, poor deposit color, deposit brittleness and exfoliation, very narrow bright plate range, or failure to plate at all on low current density areas.
  • Secondary brighteners may be materials which are ordinarily used in combination with primary brighteners but in appreciably higher concentrations than those of the primary brighteners, typically 1 gram per liter to grams per liter. These secondary brighteners may be aromatic sulfonates, sulfonamides or sulfimides (wherein the sulfur atom is bonded directly to the aromatic nucleus) which compounds may be used singly or in combination. These materials, themselves, may produce some brightening or grain-refining effects, but the deposits are not usually mirror-bright and the rate of brightening is usually inadequate.
  • auxiliary secondary brighteners such as olefinic or acetylenic aliphatic or aromatic sulfonates, which may be necessary for optimum results when using some prior art primary brighteners.
  • auxiliary secondary brighteners such as olefinic or acetylenic aliphatic or aromatically substituted aliphatic sulfonates is not essential, such additives may be used if desired to impart certain desirable characteristics as anti-pitting action, etc.
  • the rate of brightening and leveling may vary in degree depending on the particular additives chosen and their actual and relative concentrations. A high degree of rate of brightening and leveling is generally desirable, particularly where maximum luster is desired with minimum nickel thicknesses.
  • the concentrations of the secondary brighteners may usually vary within fairly wide limits. The concentrations of the primary brighteners must usually be maintained Within fairly narrow limits in order to maintain desirable properties including good ductility, adequate coverage over low current density areas, etc.
  • Any bright nickel system which can be rendered more tolerant to fluctuations in primary brightener concentrations will have obvious advantages, particularly since the low concentration of primary brighteners and the intrinsic chemical nature of some make strict control by chemical analysis difficult.
  • a primary brightener which can be used over a wide range of concentration is of great value in bright nickel plating.
  • the basis metals which may be electroplated in accordance with the process of this invention may include copper or copper alloys; ferrous metals including steel, iron, etc.; zinc and its alloys including zinc-base die castings; nickel, etc.
  • the basis metal may also bear a plate of copper and of semi-bright nickel before being subjected to the process of this invention.
  • the term bright nickel plate is meant to include bright alloy plates containing nickel as well as other metals (i.e. cobalt, iron, cobalt-iron, etc.).
  • alloy deposits containing nickel may be obtained according to the process of this invention.
  • the primary brighteners of the present invention may be useful with e.g. Watts-type baths, high chloride-type baths, and sulfamate-type baths, including those typified by the illustrative baths of Tables I, II, and III.
  • Nickel sulfamate-type baths Nickel sulfamate g./l 330 to 600 Nickel chloride g./l 15 to 60 Boric acid g./l 35 to 55 Temperature C 30 to 55 pH 3.5 to 5.0 electrometric with agitation (either mechanical, air, or solution circulation by pumping).
  • nickel plating baths may include those containing as a source of nickel, nickel fluoborate with nickel chloride.
  • nickel chloride is given as the hexahydrate NiCl -6H O
  • nickel sulfate as the heptahydrate NiSO -7H O
  • Other compounds, e.g. boric acid and nickel sulfamate, are given on an anhydrous basis.
  • the plating conditions for electrodeposition from the aforementioned baths may, for example, include temperature of 30 C.65 C., pH of 3.5- electrometric, and preferably 3.8-4.5 and cathode current density of 1-10 amps. per square decimeter.
  • Typical preferred current density of the baths of Table I may be 4-6 amps. per square decimeter. Agitation may be preferred while plating.
  • the first primary brightener employed in practice of this invention is selected from Water-soluble acetylenic compounds.
  • Water-soluble acetylenic compounds employed in this invention are characterized by a highly nucleophilic triple bond which is free from steric hindrance and thus has a clear and unimpeded path in approaching the cathode.
  • the preferred water-soluble acetylenic compounds which may be employed in the process of this invention to produce nickel deposits may include tat-substituted acetylenic compounds exhibiting the structural formula in which each of R and R may be substituents selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, hydroxy-substituted and alkoxy-substituted alkyl, alkenyl, and alkynyl groups, and R and R may together be a carbonyl oxygen; R may be a substituent of the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxy-substituted and alkoxy-substituted alkenyl and alkynyl groups, and substituted-alkyl groups hav ing the formula:
  • each of R and R may be substituents selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, and hydroxy-substituted and alkoxy-substituted alkyl, alkenyl, and alkynyl groups, and when R and R together are carbonyl oxygen, R may be an aryl group, including hydroxy and alkoxy and alkyl-substituted aryl; each of R, and R, may be substituents selected from the group consisting of hydroxy, alkoxy, carboxy-substituted alkoxy, formoxy, alkanoxy, halogen and polyoxy groups.
  • the acetylenic compound may be termed an a, a-disubstituted acetylenic compound, since both carbon atoms vicinal to the same acetylenic bond contain either the same or a different functional group.
  • the first primary brightener may be present in the bath in eifective amounts of 0.002 g./l.0.5 g./l., preferably in effective amounts of 0.005 g./l.-0.10 g./l.
  • the preferred nickel electroplating baths of this invention include secondary brighteners, present in typical amounts of 1 g./l.80 g./l., preferably 1 g./l.-20 g./1., such as the sulfo-oxygen compounds typical of which is saccharin.
  • the additional cooperating primary brightener employed in the practice of this invention is:
  • Suitable salts include alkali metal salts (e.g. Na, K, Li, etc.), ammonium, and alkaline metal salts (Ca, Mg, etc.).
  • Preferred second primary brighteners used in the practice of this invention include those selected from the group consisting of monocyanoethylated Z-thiohydantoin, di' cyanoethylated Z-thiohydantoin, tn'cyanoethylated 2-thiohydantoin, monocyanoethylated cysteine, dicyanoethylated ethylene thiourea, and [3,;3'-thiodipropionitrile.
  • Thiohydantoin (I) may be cyanoethylated as herein disclosed to produce 4-mono-B-cyanoethyl thiohydantoin (II), 3,4-di-fi-cyanoethyl thiohydantoin (III), and 3,4,4- tri-fi-cyanoethyl thiohydantoin (W).
  • Reaction is effected by mixing the components in appropriate mole ratios, preferably in the presence of a reaction medium and preferably accompanied by vigorous agitation.
  • the position and number of the cyanoethyl groups may be readily confirmed by inspection of the infrared spectrum of the compounds, by the Sodium Azide-Iodine Test, elemental analysis, etc.
  • the temperature during the reaction is controlled to fall in the range of 0 to 70 C.
  • Lower temperatures e.g. 0 C.35 C. favor lower degrees of cyanoethylation, while higher temperatures, e.g. 35 C.70 C. favor higher degrees of cyanoethylation.
  • the time of reaction depending on the specific compounds reacted, may be from a few minutes, e.g. 5 minutes, to several hours. Commonly it may be 30-60 minutes.
  • the excess of the acrylonitrile may be removed by volatilization techniques (by heating to C. or higher) or by distillation under vacuum at lower temperatures.
  • Alkali-insoluble products will precipitate on removal of the excess unreacted acrylonitrile.
  • Alkali-soluble products may be recovered by acidification, e.g. with dilute sulfuric acid. In either case, the product can then be removed by filtration or decantation depending on whether it is crystalline or liquid. Further purification of the crystalline product may be by recrystallization from aqueous solutions or organic solvents or mixtures thereof. Purification of liquid products may be eifected by fractional distillation or solvent extraction.
  • the additional cooperating primary brightener should be present in the bath in an effective amount of 0.0005 gram per liter to 0.05 gram per liter, preferably 0.001 gram per liter to 0.03 gram per liter.
  • additives which may be used include antipitting agents which may be exemplified by sodium lauryl sulfate and sodium di-N-hexylsulfosuccinate.
  • Plating of nickel by the novel process of this invention permits attainment of a brilliant, ductile, highly leveled deposit of bright nickel over a wide range of current density.
  • the basis metals which may be electroplated in accordance with the process of this invention include copper or copper alloys; ferrous metals, including steel, iron, etc.; zinc and its alloys including zinc-base die castings; nickel, etc.
  • the basis metal bears a plate of copper and of semi-bright nickel before being subjected to the process of this invention.
  • the first primary brighteners acetylenic used were: A 2-butyne-1,4-diol B bis-p-hydroxyethyl ether of Z-butyne, 1,4-diol C 3-methyl-l-butyne-3-ol D phenylpropiolamide
  • the second cooperating primary brighteners used were:
  • the secondary brightener used was: A" saccharin (Na salt)
  • the secondary auxiliary brighteners used were:
  • the anti-pitting agents used were:
  • A" sodium lauryl sulfate B" sodium di-N-hexyl-sulfo succinate Brilliant, ductile, highly-leveled deposits with compressive internal stress were obtained after prolonged or extended electrolysis (with periodic primary brightener replenishment) in all cases where the word Good is used in the Results column.
  • the word Poor denotes the attaining of permanent hazy or milky deposits in any part of the current density range after prolonged electrolysis even with periodic primary brightener replenishment.
  • Examples 1-28 the electrolyte baths used were Watts baths; high chloride baths were used for Examples 29-35; and sulfamate baths were used for Examples 36-42. In Examples 43-47 cobalt-nickel baths were employed.
  • the additives were present in the amounts indicated. All runs were made using highly polished brass cathodes with the cathode current densities averaging a.s.d. at a temperature of 60 C. for the Watts and sulfamate baths, and 6 a.s.d. at a temperature of 65 C. for the high chloride bath. The plating time was 30 minutes. To evaluate the degree of leveling the brass cathodes were scratched before plating with a single pass of 4/0 grit emery paper.
  • EXAMPLE 48 Preparation of monocyanoethyl cysteine A solution of 17. 6-grams of cysteine monohydrochloride in one hundred milliliters of water was mixed with a solution of 9.0 grams (C.'P.) of sodium hydroxide pellets in 25 milliliters of water (at a pH of 11) and stirred magnetically. The volume of the resulting mixture was adjusted to 200 milliliters by the addition of water.
  • EXAMPLE 49 Preparation of dicyanoethyl cysteine To the second 100 milliliter aliquot prepared in Example 48, 5.5 grams of acrylonitrile at 10 C. were added in drop-sized increments over a 25 minute time interval; the temperature was increased to 15 C. and the reaction mixture stirred at room temperature three hours after which said reaction mixture was acidified to a pH of 2 10 with concentrated hydrochloric acid. A colorless precipitate was obtained. The precipitate was filtered and dried. A yield of 6.8 grams of dicyanoethyl cysteine (60%) exhibiting a melting point of 212 C. to 214 C. was observed (Fisher-Johns apparatus).
  • the process for electroplating bright nickel which comprises electrodepositing nickel from an aqueous acidic nickel electroplating bath containing (a) as a first primary brightener 0.002 gram per liter to 0.5 gram per liter of a water-soluble acetylenic compound, having no terminal unsaturation (b) 1 gram per liter to grams per liter of at least one sulfo-oxygen secondary brightener selected from the group consisting of aromatic sulfonates, sulfonamides, sulfimides and derivatives thereof, and (c) as a second cooperating primary brightener 0.0005 grams per liter to 0.05 grams per liter of:
  • the process for electroplating bright nickel which comprises electroplating nickel from an aqueous nickel electroplating bath containing as a first primary brightener 0.002 gram per liter to 0.5 gram per liter of Z-butyne- 1,4-diol, 1.0 gram per liter to 80 grams per liter of a secondary brightener selected from the group consisting of at least one member of the group consisting of aromatic sulfonates, sulfonamides, sulfimides and derivatives thereof, and as a second cooperating primary brightener 0.0005 gram per liter to 0.05 gram per liter tricyanoethylated-Z-thiohydantoin.
  • An aqueous electrolytic bath for electroplating bright nickel containing (a) as a first primary brightener 0.002 gram per liter to 0.5 gram per liter of a water-soluble acetylenic compound, having no terminal unsaturation (b) 1 gram per liter to 80 grams per liter of at least one sulfooxygen secondary brightener selected from the group consisting of aromatic sulfonates, sulfonamides, sulfimides and derivatives thereof, and (c) as a second cooperating primary brightener 0.0005 gram per liter to 0.05 gram per liter of:

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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)
US00747098A 1968-07-24 1968-07-24 Electrodeposition of nickel Expired - Lifetime US3734840A (en)

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US (1) US3734840A (enrdf_load_stackoverflow)
AT (1) AT288810B (enrdf_load_stackoverflow)
BR (1) BR6910570D0 (enrdf_load_stackoverflow)
CA (1) CA947228A (enrdf_load_stackoverflow)
CH (1) CH521448A (enrdf_load_stackoverflow)
DE (1) DE1936248A1 (enrdf_load_stackoverflow)
ES (1) ES369801A1 (enrdf_load_stackoverflow)
FR (1) FR2013574A1 (enrdf_load_stackoverflow)
GB (1) GB1257935A (enrdf_load_stackoverflow)
NL (1) NL6911223A (enrdf_load_stackoverflow)
SE (1) SE359574B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985784A (en) * 1972-07-10 1976-10-12 Oxy Metal Industries Corporation Thioether sulfonates for use in electroplating baths
US9812331B2 (en) 2014-05-12 2017-11-07 Samsung Electronics Co., Ltd. Apparatus for and method of processing substrate
US20210403334A1 (en) * 2018-11-05 2021-12-30 Pacific Industrial Development Corporation Method of making aei-type zeolites having a high silica to alumina molar ratio (sar)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985784A (en) * 1972-07-10 1976-10-12 Oxy Metal Industries Corporation Thioether sulfonates for use in electroplating baths
US9812331B2 (en) 2014-05-12 2017-11-07 Samsung Electronics Co., Ltd. Apparatus for and method of processing substrate
US20210403334A1 (en) * 2018-11-05 2021-12-30 Pacific Industrial Development Corporation Method of making aei-type zeolites having a high silica to alumina molar ratio (sar)
US12319582B2 (en) * 2018-11-05 2025-06-03 Pacific Industrial Development Corporation Method of making AEI-type zeolites having a high silica to alumina molar ratio (SAR)

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ES369801A1 (es) 1971-12-01
SE359574B (enrdf_load_stackoverflow) 1973-09-03
DE1936248A1 (de) 1970-08-20
CA947228A (en) 1974-05-14
FR2013574A1 (enrdf_load_stackoverflow) 1970-04-03
NL6911223A (enrdf_load_stackoverflow) 1970-01-27
CH521448A (de) 1972-04-15
GB1257935A (enrdf_load_stackoverflow) 1971-12-22
AT288810B (de) 1971-03-25
BR6910570D0 (pt) 1973-04-10

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