US3677912A - Nickel electroplating and electrolytes therefor - Google Patents

Nickel electroplating and electrolytes therefor Download PDF

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Publication number
US3677912A
US3677912A US76987A US7698770A US3677912A US 3677912 A US3677912 A US 3677912A US 76987 A US76987 A US 76987A US 7698770 A US7698770 A US 7698770A US 3677912 A US3677912 A US 3677912A
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United States
Prior art keywords
nickel
bromide
alkyl
butyne
dibromopropenyl
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Expired - Lifetime
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US76987A
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English (en)
Inventor
Frank Passal
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M&T Chemicals Inc
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M&T Chemicals Inc
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Publication date
Priority to GB47180/67A priority Critical patent/GB1192036A/en
Priority to CH1447667A priority patent/CH526640A/de
Priority to ES346165A priority patent/ES346165A0/es
Priority to DE1621116A priority patent/DE1621116C3/de
Priority to NL6714151A priority patent/NL6714151A/xx
Priority to FR124847A priority patent/FR1541348A/fr
Priority to DK516467AA priority patent/DK136960B/da
Application filed by M&T Chemicals Inc filed Critical M&T Chemicals Inc
Priority to US76987A priority patent/US3677912A/en
Application granted granted Critical
Publication of US3677912A publication Critical patent/US3677912A/en
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Expired - Lifetime legal-status Critical Current

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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
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds

Definitions

  • the novel process of this invention for electroplating nickel may comprise electrodepositing nickel from an aqueous nickel electroplating bath containing (a) as a first primary brightener an effective amount of a Water-soluble acetylenic compound, and (b) as a second primary brightener, an effective amount of a compound having as cation:
  • R* is a substituent selected from the group consisting of alkyl, preferably having l-4 carbon atoms, hydroxy-alkyl preferably having 1-4 carbon atoms, halogen, alkoxy, carboxyl, carbalkoxy, acetyl, benzyl, sulfo, carboxamido, and cyano.
  • the present invention relates to a process for nickel plating. More particularly it relates to a process for bright nickel plating characterized by outstanding coverage in low current density areas.
  • the novel process of this invention for electroplating nickel may comprise electrodepositing nickel from an aqueous nickel electroplating bath containing (a) as a first primary brightener an effective amount of a water-soluble acetyleriic compound, and (b) as a second primary brightener, an effective amount of a compound having as cation:
  • X is an active halide; and
  • -R* is a substituent selected from the group consistwherein 3,677,912 Patented July 18, 1972 ing of alkyl, preferably, having 1-4 carbon atoms, hydroxy-alkyl preferably having 1-4 carbon atoms, halogen, alkoxy, carboxyl, carbalkoxy, acetyl, benzyl, sulfo, carboxarnido, and cyano.
  • 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 bear a plate of copper and of semi-bright nickel before being subjected 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 plating baths include those containing, as a source of nickel, nickel fluoborate with nickel chloride, nickel sulfamate with nickel chloride, etc.
  • the nickel chloride is metered as the hexahydrate NiCl -6H O, and the nickel sulfate as the heptahydrate NiSO -7H O.
  • Other compounds e.g. boric acid are metered 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 3.5-5 electrometric, and preferably 3.8-4.5, cathode current density of 1-10 amps. per sq. dm.
  • Typical preferred current density of the baths of Table I may be 4-6 amps. per sq. dm. Agitation may be preferred while plating.
  • the first primary brightener which may be employed 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 he 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 having the formula in which 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 carbony
  • the acetylenic compound may be termed an u,a'- disubstituted acetylenic compounds, since both carbon atoms vicinal to the same acetylenic bond contain either the same or a dilferent functional group.
  • the first primary brightener may be present in the bath in elfective amounts of 0.002 g./l.-0.S g./l., preferably 0.005 g./l.0.l0 g./l., say 0.01 g./1.0.05 g./l.
  • the second primary brightener which may be employed in practice of this invention may include nitrogen heterocyclic compounds having as cation Its-9+4: Hn-A.
  • a is 0-5;
  • X is an active halide;
  • R* is a substituent selected from the group consisting of alkyl preferably having 1-4 carbon atoms, hydroxyalkyl preferably having 14 carbon atoms, halogen, alkoxy, carboxyl, carbal-koxy, acetyl, benzyl, sulfo, carboxamido, and
  • the second primary brightener may be a compound wherein n/CHz-A. R,- N
  • X is a bath-soluble, bath-compatible anion, typically bromide, chloride, iodide, fluoride, acetate, sulfate, methosulfate, ethosulfate, citrate, chloroacetate, perchlorate, etc.
  • X may be halide including fluoride, chloride, bromide, and iodide.
  • compound (II) will preferably be prepared by the reaction of compound (111) infra with bromine e.g. reaction of 2,6-dimethyl, N-propargyl pyridinium bromide with bromine to form 2,6-dimethyl, N-2,3-dibromo propenyl pyridinium bromide.
  • Formula Il may include, in addition to simple pyridine, quinoline, and isoquinoline derivatives, other compounds including those formed from eg 4,4'-dipyridine: such as N,N bis-Z-propynyl-4,4'-dipyridinium dibromide formed by the reaction 4,4'-dipyridine and propynyl bromide; or N,N' bis-2,3-dichloropropynyl, 4,4'-dipyridinium dichloride formed by the reaction of 4,4'-dipyridine and 2,3- dichloropropenyl chloride.
  • 4,4'-dipyridine such as N,N bis-Z-propynyl-4,4'-dipyridinium dibromide formed by the reaction 4,4'-dipyridine and propynyl bromide; or N,N' bis-2,3-dichloropropynyl, 4,4'-dipyridinium dichloride formed by the reaction of 4,4'-d
  • R* be alkyl or hydroxyalkyl, and a be an integer -5.
  • a is 2-5, there may be both alkyl and hydroxyalkyl groups on the molecule.
  • R* may typically be methyl, ethyl, propyl, ipropyl, n-butyl, i-butyl, t-butyl, n-amyl, n-hexyl, n-octyl, Z-ethylhexyl, etc., hydroxymethyl, S-hydroxyethyl, gamma-hydroxypropyl, fi-dihydroxypropyl, etc.
  • Typical compounds which may fall within the scope of Formula III may be:
  • Typical compounds which may fall within the scope of Formula IV may include:
  • the total amount of primary brightener, including the first and second primary brightener may be 0.004 g./l.0.6 g./l., more preferably 0.007 g./l.-0.l5 g./l., say 0.02 g./l.
  • the preferred nickel electroplating baths of this invention may include secondary brighteners, present in typical amounts of 1 g./l.75 g./l., preferably 1 g./l.-20 g./l., such as the sulfo-oxygen compounds typical of which may be saccharin and sodium benzene monosulfonate.
  • the latter secondary brightener may be preferred because of its higher degree of zinc-tolerance, i.e. its ability to tolerate higher concentrations of zinc as contaminant without giving striations in the low current density areas.
  • saccharin or the sodium salt of sulfonated dibenzothiophene dioxide it may be preferred to use saccharin or the sodium salt of sulfonated dibenzothiophene dioxide. Naphthalene sulfonates may be found to be of little or no efiectivity in the process of this invention.
  • Secondary auxiliary brighteners typically present in amount of 2 g./l.30 g./l., preferably 2 g./l.-10 g./l., say 4 g./l., may include unsaturated hydrocarbon sulfonates such as sodium 3-chloro-2-butene sulfonate; sodium 2- propen-l-sulfonate; sodium 1-phenylether-2-sulfonate; sodium 3-methyl-1-buten-3-ol-l-sulfonate; sodium 3-hydroxy-l-propen-l-sulfonate; etc.
  • unsaturated hydrocarbon sulfonates such as sodium 3-chloro-2-butene sulfonate; sodium 2- propen-l-sulfonate; sodium 1-phenylether-2-sulfonate; sodium 3-methyl-1-buten-3-ol-l-sulfonate; sodium 3-hydroxy-l-propen-l-sulfonate; etc.
  • 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.
  • coverage in the low current density region is substantially increased.
  • the Watts Bath contained:
  • Acetylenic Primary Brighteners used were:
  • N-heterocyclic Primary Brighteners used were: TABLE VIII 0 g, 3-3; (A) N-2,3-dichloropropenyl pyridinium chloride 7 g, (B') N-2,3-dibromopropenyl-2,4,6 trimethyl pyridinium bromide 11 3'8? ((3') N-2-propynyl-2,4,6-trimethyl pyridinium bromide Z, (D') N,N'bis-2-propynyl-4,4-dipyridinium dibromide A (E') N,Nbis-2,3-dichloropropenyl-4,4' dipyridininm di- 12 B 0. 0s chloride Si" 4
  • the secondary Brighteners used were: Am
  • the Anti-pitting Agents used were: 81', 0 (A"") Sodium lauryl sulfate B," 3 Sodium di-n-hexyl sulfosuccinate 17 C 01 A 0 01
  • the baths used were Watts Baths for 2; 7.5 Examples 1-19; High Chloride Baths for Examples 20-26; 0 and Sulfamate Baths for Examples 27-34.
  • the additives 18 D 0,0 were present in the amount indicated. All runs were made 1, using highly polished brass cathodes with the cathode cur- B rent densities averaging 5 a.s.d. at a temperature of 60 19 C.
  • the nickel plate was characterized by a high degree of leveling, ductility, and rate of brightening.
  • the combination of primary brighteners gave extremely high leveling, ductility, rate of brightening, and substantial improvement in coverage in the low current density area. Improved coverage in low current density areas may be particularly outstanding when saccharin is used as the secondary brightener.
  • EXAMPLE 37 The system formulated under Example 36 (above) was found to be somewhat sensitive to zinc contamination when sodium allyl sulfonate was substituted for sodium 3-chlorobutene sulfonate. On adding 2-butyne-1,4-diol as an additional cooperating primary brightener, the sensitivity towards zinc contamination was remarkably reduced and a highly successful process resulted.
  • X is an actvie halide; and
  • R* is a substituent selected from the group consisting of alkyl, hydroxyalkyl, halogen, alkoxy, carboxyl, carbalkoxy, acetyl, benzyl, sulfo, carboxamido, and cyano.

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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)
US76987A 1966-10-18 1970-09-30 Nickel electroplating and electrolytes therefor Expired - Lifetime US3677912A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
ES346165A ES346165A0 (es) 1966-10-18 1967-10-17 Procedimiento para galvanoplastia de niquel.
GB47180/67A GB1192036A (en) 1966-10-18 1967-10-17 Improvements in or relating to Nickel Electroplating
CH1447667A CH526640A (de) 1966-10-18 1967-10-17 Verfahren zum galvanischen Glanzvernickeln
NL6714151A NL6714151A (de) 1966-10-18 1967-10-18
DE1621116A DE1621116C3 (de) 1966-10-18 1967-10-18 Glanznickelbad
FR124847A FR1541348A (fr) 1966-10-18 1967-10-18 Procédé perfectionné de nickelage
DK516467AA DK136960B (da) 1966-10-18 1967-10-18 Fremgangsmåde til elektroplettering med nikkel og bad til anvendelse derved.
US76987A US3677912A (en) 1966-10-18 1970-09-30 Nickel electroplating and electrolytes therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US58739366A 1966-10-18 1966-10-18
US76987A US3677912A (en) 1966-10-18 1970-09-30 Nickel electroplating and electrolytes therefor

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US3677912A true US3677912A (en) 1972-07-18

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US (1) US3677912A (de)
CH (1) CH526640A (de)
DE (1) DE1621116C3 (de)
DK (1) DK136960B (de)
ES (1) ES346165A0 (de)
FR (1) FR1541348A (de)
GB (1) GB1192036A (de)
NL (1) NL6714151A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297177A (en) * 1980-09-19 1981-10-27 American Chemical & Refining Company Incorporated Method and composition for electrodepositing palladium/nickel alloys
EP0132165A1 (de) * 1983-06-13 1985-01-23 EASTMAN KODAK COMPANY (a New Jersey corporation) Adsorbierbar Alkynyl substituierte heterocyclische quaternarische Ammoniumsalze und deren Anwendung in der Halogensilberphotographie
US20110114498A1 (en) * 2009-11-18 2011-05-19 Tremmel Robert A Semi-Bright Nickel Plating Bath and Method of Using Same
US20110155582A1 (en) * 2009-11-18 2011-06-30 Tremmel Robert A Semi-Bright Nickel Plating Bath and Method of Using Same
CN110759856A (zh) * 2019-11-27 2020-02-07 南方科技大学 一种电致变色化合物及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993015241A1 (de) * 1992-01-25 1993-08-05 Basf Aktiengesellschaft Verfahren zur herstellung vernickelter formteile

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297177A (en) * 1980-09-19 1981-10-27 American Chemical & Refining Company Incorporated Method and composition for electrodepositing palladium/nickel alloys
EP0132165A1 (de) * 1983-06-13 1985-01-23 EASTMAN KODAK COMPANY (a New Jersey corporation) Adsorbierbar Alkynyl substituierte heterocyclische quaternarische Ammoniumsalze und deren Anwendung in der Halogensilberphotographie
US20110114498A1 (en) * 2009-11-18 2011-05-19 Tremmel Robert A Semi-Bright Nickel Plating Bath and Method of Using Same
US20110155582A1 (en) * 2009-11-18 2011-06-30 Tremmel Robert A Semi-Bright Nickel Plating Bath and Method of Using Same
CN110759856A (zh) * 2019-11-27 2020-02-07 南方科技大学 一种电致变色化合物及其制备方法和应用
CN110759856B (zh) * 2019-11-27 2023-05-23 南方科技大学 一种电致变色化合物及其制备方法和应用

Also Published As

Publication number Publication date
DK136960B (da) 1977-12-19
DK136960C (de) 1978-05-29
DE1621116C3 (de) 1979-10-31
CH526640A (de) 1972-08-15
ES346165A0 (es) 1970-12-01
NL6714151A (de) 1968-04-19
GB1192036A (en) 1970-05-13
DE1621116A1 (de) 1971-06-03
FR1541348A (fr) 1968-10-04
DE1621116B2 (de) 1979-03-08

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