US3723260A - Acid nickel electroplating - Google Patents

Acid nickel electroplating Download PDF

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Publication number
US3723260A
US3723260A US00226543A US3723260DA US3723260A US 3723260 A US3723260 A US 3723260A US 00226543 A US00226543 A US 00226543A US 3723260D A US3723260D A US 3723260DA US 3723260 A US3723260 A US 3723260A
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United States
Prior art keywords
acid
alkyl
acrylate monomer
carbon atoms
nickel
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Expired - Lifetime
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US00226543A
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English (en)
Inventor
J Rushmere
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • C09D5/4411—Homopolymers or copolymers of acrylates or methacrylates
    • 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

  • R is methyl or hydrogen
  • n is a positive whole integer of 1 to 3 inclusive
  • R is alkyl of 1 to 4 carbon atoms
  • -R" is alkyl of 1 to 4 carbon atoms
  • a copolymer of said acrylate monomer With at least one ethylenically unsaturated monomer selected from the group consisting of an a,,9-ethylenically unsaturated monocarboxylic acid, an alkyl ester of said acid wherein the alkyl group is from 1 to 4 carbon atoms, acrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl sulfone and vinyl pyridine, the molar ratio of said acrylate monomer to said unsaturated monomer being within the range of 0.9:(11 to 0.1 :0.9.
  • This invention relates to acid nickel electroplating baths and processes.
  • Prior art 3,723,260 Patented Mar. 27, 1973 are generally divided into two classes on the basis of their predominant function.
  • Primary brighteners are materials used in relatively low concentration which by themselves may or may not produce visible brightening action. However, some primary brighteners, when used alone, also produce some deletrious side eifects such as deposit brittleness, narrow bright plate range and skip plating at low current densities.
  • Secondary brighteners are materials which are usually used in combination with primary brighteners, but at a higher concentration. Secondary brighteners, by themselves, may produce some brightening action, but the deposits are usually not mirror bright and the rate of brightening is usually inadequate.
  • US. Pat. 2,647,866 (issued to Henry Brown on Aug. 4, 1953) discloses the use of various pyridinium compounds, e.g., N-allyl pyridinium bromide as primary additives for bright nickel plating.
  • This patent also teaches the use of the pyridinium compounds in conjunction with organic sulfonic, sulfonamide and sulfonirnide compounds which are the subjects of US. Pats. 2,191,813 and 2,466,677 also issued to Henry Brown.
  • the use of various acetylenic compounds, e.g., 2-butyne-1,4- diol, as primary brighteners again used in conjunction with aromatic sulfur compounds is the subject of U.S.. Pat.
  • esters of unsaturated monocarboxylic acids e.g., methyl acrylate used as primary brighteners is the subject of US. Pat. 2,690,996 (issued to Henry Brown on Oct. 5, 1954)..
  • an aqueous acid nickel electroplating bath comprising an aqueous solution of a nickel salt, said solution maintained at a pH in the range of about 3 to 5 and having dissolved therein as primary brightener in an elfective amount, an acrylate selected from the group consisting of (1) an acrylate monomer of the formula:
  • R is methyl or hydrogen
  • n is a positive whole integer of 1 to 3 inclusive
  • R' is alkyl of 1 to 4 carbon atoms
  • the invention pertains to the electro-deposition of nickel from aqueous, acidic nickel electroplating baths known to those skilled in the art. These baths are usually formed by the dissolution of at least one nickel salt in an aqueous, acid solution. Conventional baths and processes for electroplating bright nickel are described in Principles of Electroplating and Electroforming, Blum and Hogaboom, pages 362-381, revised third edition, 1949, McGraw-Hill, Inc., New York; and in Modern Electroplating, edited by A. G. Gray, The Electrochemical Society, 1953, pages 299-355. Operating conditions disclosed, including pH, temperature, current density and the concentration of bath ingredients are applicable to the present invention.
  • the pH will be in the range of 3 to and usually 3.5 to 4.5, while the temperature will be in the range of 40 to 70 C. and usually 55 to 65 C.
  • Practically all baths for electroplating bright nickel contain nickel sulfate; a chloride, usually nickel chloride; a buffering agent, usually boric acid; and optionally a wetting agent.
  • Such baths include the well-known Watts bath and the high chloride bath.
  • Other baths may contain, 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.
  • Typical Watts baths and high chloride baths are as follows:
  • the primary brighteners of the present invention may be used in concentrations ranging between about 0.001 to 5 g./l., preferably between about 0.002 to 2 g./l., the particular concentration used depending on the types and concentrations of secondary and secondary auxiliary brighteners used. Other factors to be considered are concentrations of the bath ingredients, bath operating conditions and the degree and rate of brightening and leveling desired.
  • the primary brighteners of this invention are certain quaternized dialkylaminoalkylacrylate monomers and more particularly homopolymers of these monomers or copolymers of these monomers with other ethylenically unsaturated monomers.
  • the quaternized dialkylaminoalkylacrylates used in this invention have the general formula:
  • R is methyl or hydrogen
  • n is a positive whole integer of l to 3 inclusive
  • R is alkyl of 1 to 4 carbon atoms
  • Z-methacryloxyethyl, dimethyl propargyl ammonium bromide which may be prepared by the addition of propargyl bromide to dimethylaminoethyl methacrylate in a suitable solvent.
  • This monomer may be readily polymerized in aqueous solution under the action of a peroxide initiator and a temperature of 60 to C. to give a homopolymer which shows enhanced brightening-leveling characteristics over the monomer but which also inhibits plating at low current densities, i.e., less than 10 amps/ft
  • the problem of low current density skipping, while retaining brightening-leveling characteristics, is overcome by copolymerizing the quaternized dialkylaminoalkylacrylates with at least one other ethylenically unsaturated monomer such as an a,fi-ethylenically unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, an alkyl ester of said acid wherein the alkyl group is from 1 to 4 carbon atoms, methacrylamide, acrylamide, acrylonitrile, vinyl acetate, vinyl sulfone, and vinyl pyridine.
  • the molar ratios of the acrylate monomer to the other monomer can vary between about 0.9/0.1 to 0.1/0.9.
  • this capacity is the copolymer formed between: Z-methacryloxyethyl trimethyl ammonium methyl sulfate and methacrylic acid CH: CHa
  • the above copolymer is preferably used with molar ratios of n/m varying between 0.7/0.3 to 0.3/0.7, although maximum benefits are obtained at ratios of n/m about 0.7/O.3.
  • the invention includes terpolymers, tetrapolymers and other copolymers.
  • Secondary brighteners usually used at a concentration of 1 to 20 g./l., may consist typically of aromatic sulfonates, sulfonamides or sulfimides such as sodium or potassium salts of saccharin, 1,3,6-naphthalene trisulfonate p-toluene sulfonamide, benzene sulfonic acid (usually in form of sodium or potassium salt).
  • the secondary brighteners are generally characterized by having at least one sulfone or sulfonic acid group attached to a nuclear carbon of a homocyclic aromatic ring. These maproximately a mole for mole basis the quaternizing agent to the dimethylaminoethylmethacrylate in a suitable solvent, and found to have a brightening-leveling ability.
  • terials have a brightening elfect on the nickel deposits but, more importantly, impart ductility.
  • sulfonated unsaturated hydrocarbons such as sodium allyl sulfonate and sodium-3-chloro-2-butene-l-sulfonate may be added to the bath as auxiliary secondary brighteners to further improve the brightness range and ductility of the nickel deposits.
  • auxiliary secondary brighteners as well as the secondary brighteners are well-known to those skilled in the art.
  • EXAMPLE 1 Z-methacryloxyethyl, carboxamidomethyl, dimethyl ammonium chloride (B) was prepared by standing together 9.4 g. of chloroacetamide and 8 g. dimethylaminoethylmethacrylate in g. dimethyl formamide for 12 days. After this time, a few white solids had appeared. On pouring the solution into methyl ethyl ketone, considerable white crystalline solids precipitated. They contained Cl: 13.92%. Theory for C1: 14.18%.
  • (F) was polymerized by warming together 5 g. (F), 25 g. water, 0.05 g. potassium persulfate in a stirred vessel at C. for 1 hour. Poly (F) was precipitated as a white rubbery material on pouring into acetone. After drying at 60 C. under vacuum, brownish brittle solids, easily soluble in water, were obtained.
  • poly (F) in an amount of 0.04 g./l. of plating bath, poly (F) was found to be an excellent brightener-leveler above 40 a./ft. The nickel deposit was mirror bright with all scratches completely leveled. Lesser amounts of poly (F) in the plating bath permitted nickel deposition below 40 a./ft. but with some loss of leveling ability. Thus, at 0.008 g./l., bright nickel was obtained above 1 a./ft. but only slight leveling was observed.
  • R is methyl or hydrogen
  • R' is methyl or ethyl
  • An aqueous acid nickel electroplating bath comprising an aqueous solution of a nickel salt, said solution maintained at a pH in the range of about 3 to 5 and having dissolved therein as primary brightener an effective amount of an acrylate selected from the group consisting of (1) an acrylate monomer of the formula:
  • R is methyl or hydrogen
  • n is a positive whole integer of 1 to 3 inclusive
  • R is alkyl of 1 to 4 carbon atoms
  • R" is alkyl of 1 to 4 carbon atoms
  • R is as defined above, -CH CONH CH CN, --CH CH OH, CH CH COO or -CH2CH2'CHZSO3 and X is CH2SO4, C2H5SO4 Or is absent when R is CH CH COO- or CH CH CH SO (2) a homopolymer of said acrylate monomer, and (3) a copolymer of said acrylate monomer with at least one ethylenically unsaturated monomer selected from the group consisting of an a, fl-e'thylenically unsaturated monocarboxylic acid, an alkyl ester of said acid wherein the alkyl group is from 1 to 4 carbon atoms, acrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl sulfone and vinyl pyridine, the molar ratio of said acrylate monomer to said unsaturated monomer being within the range of 0.9101 to 0.1209.
  • ethylenically unsaturated monomer selected from the group consisting of an a, B-ethylenically unsaturated monocarboxylic acid, an alkyl ester of said acid wherein the alkyl group is from 1 to 4 carbon atoms, acrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl sulfone and vinyl pyridine, the copolymer having a molar ratio of said acrylate monomer to said unsaturated monomer being within the range of 0.7/0.3 to 0.3/0.7.
  • the acid electroplating bath of claim 2 wherein the pH of the bath is within the range of about 3.5 to 4.5 and the copolymer concentration is about 0.001 to 5 g./l.
  • copolymer is about 70 molar percent of Z-rnethacryloxyethyl, trimethyl ammonium methyl sulfate and about 30 molar percent of methacrylic acid.
  • R is methyl or hydrogen, R is methyl or ethyl, R" is alkyl of 1 to 4 carbon atoms,
  • the acid electroplating bath of claim 7 wherein the pH of the bath is within the range of about 3.5 to 4.5 and the acrylate monomer concentration is about 0.001 to 5 g./l.
  • R is methyl or hydrogen
  • n is a positive whole integer of 1 to 3 inclusive
  • R is alkyl of 1 to 4 carbon atoms
  • R" is alkyl of 1 to 4 carbon atoms
  • -CH CH 'CH OH CiEOH -CH C0OCH -CH COOC H CH COR
  • R is as defined above, CH CONH -CH CN, -CH CH OH, -CH CH COO* or CH CH CH SO and X- is CH SO C H SO halide or is absent when R" is -CH OH COO- or -OH CH CH SO
  • X is CH SO C H SO halide or is absent when R" is 01' CH2CH2CH2SO3 with at least one ethylenically unsaturated monomer selected from the group consisting of an ac, B-ethylenically unsaturated monocarboxylic acid, an alkyl ester of said acid wherein the alkyl group is from 1 to 4 carbon atoms, acrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl sulfone and vinyl pyridine, the copolymer having a molar ratio of said acrylate monomer to said unsaturated monomer within the range of 0.7/0.3 to 0.3/0.7 and the bath is at a temperature in the range of about 20 to 30 C.
  • copolymer is about 70 molar percent of 2-methacryloxyethyl, trimethyl ammonium methyl sulfate and about 30 molar percent of methacrylic acid.
  • R is methyl or hydrogen, R is methyl or ethyl,
  • the process of claim 14 wherein the acrylate is a homopolymer of an acrylate monomer of the general formula:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US00226543A 1972-02-15 1972-02-15 Acid nickel electroplating Expired - Lifetime US3723260A (en)

Applications Claiming Priority (2)

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US22654372A 1972-02-15 1972-02-15
US22654272A 1972-02-15 1972-02-15

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US00226542A Expired - Lifetime US3723262A (en) 1972-02-15 1972-02-15 Acid zinc electroplating

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US (2) US3723260A (forum.php)
JP (1) JPS4892235A (forum.php)
BE (1) BE795359A (forum.php)
DE (1) DE2307520A1 (forum.php)
FR (1) FR2172222B1 (forum.php)
IT (1) IT979117B (forum.php)
NL (1) NL7301796A (forum.php)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4077855A (en) * 1976-05-04 1978-03-07 Francine Popescu Bright nickel electroplating bath and process
US6106940A (en) * 1998-03-17 2000-08-22 3M Innovative Properties Company Adhesive compositions with zwitterionic tackifiers and plasticizers
US6133391A (en) * 1998-03-17 2000-10-17 3M Innovative Properties Company Adhesive compositions and adhesive tapes comprising zwitterionic copolymers, and novel zwitterionic copolymers

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2310424A1 (fr) * 1975-05-06 1976-12-03 Popescu Francine Bain de nickelage electrolytique brillant
JPS5856037B2 (ja) * 1975-07-17 1983-12-13 ソニー株式会社 酸性Ｎｉ電気メッキ浴
JPS52111820A (en) * 1976-03-18 1977-09-19 Furukawa Electric Co Ltd:The Electro-deposition of zinc
US4176017A (en) * 1979-01-31 1979-11-27 Oxy Metal Industries Corporation Brightening composition for acid zinc electroplating bath and process
US4425198A (en) 1981-06-16 1984-01-10 Omi International Corporation Brightening composition for zinc alloy electroplating bath and its method of use
DE3640804A1 (de) * 1986-11-28 1988-06-09 Basf Lacke & Farben Durch protonierung mit saeure wasserverduennbare bindemittel
JP2538646B2 (ja) * 1988-07-05 1996-09-25 花王株式会社 新規カチオン化合物、それを含有する漂白剤組成物及び漂白洗浄剤組成物
DE10100954A1 (de) * 2001-01-11 2002-07-18 Raschig Gmbh Verwendung von Polyolefinen mit basischen, aromatischen Substituenten als Hilfsmittel zur elektrolytischen Abscheidung von metallischen Schichten
WO2012051446A2 (en) * 2010-10-14 2012-04-19 Freeport-Mcmoran Corporation Improved electrowinning process
JP6498617B2 (ja) * 2016-02-18 2019-04-10 奥野製薬工業株式会社 電気ニッケルめっき用光沢剤、電気ニッケルめっき液、電気めっき方法、めっき製品及びニッケル溶出防止方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA759424A (en) * 1967-05-23 Nakanishi Kunihiko Metal electroplating bath
US2798040A (en) * 1955-09-15 1957-07-02 Dow Chemical Co Electrowinning of metals

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4077855A (en) * 1976-05-04 1978-03-07 Francine Popescu Bright nickel electroplating bath and process
US6106940A (en) * 1998-03-17 2000-08-22 3M Innovative Properties Company Adhesive compositions with zwitterionic tackifiers and plasticizers
US6133391A (en) * 1998-03-17 2000-10-17 3M Innovative Properties Company Adhesive compositions and adhesive tapes comprising zwitterionic copolymers, and novel zwitterionic copolymers

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FR2172222A1 (forum.php) 1973-09-28
JPS4892235A (forum.php) 1973-11-30
FR2172222B1 (forum.php) 1977-02-04
US3723262A (en) 1973-03-27
DE2307520A1 (de) 1973-08-30
BE795359A (fr) 1973-05-29
NL7301796A (forum.php) 1973-08-17
IT979117B (it) 1974-09-30

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