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US3898138A - Method and bath for the electrodeposition of nickel - Google Patents

Method and bath for the electrodeposition of nickel Download PDF

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Publication number
US3898138A
US3898138A US515130A US51513074A US3898138A US 3898138 A US3898138 A US 3898138A US 515130 A US515130 A US 515130A US 51513074 A US51513074 A US 51513074A US 3898138 A US3898138 A US 3898138A
Authority
US
United States
Prior art keywords
nickel
per liter
diol
grams per
bath
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US515130A
Other languages
English (en)
Inventor
Richard J Clauss
Roy W Klein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
OMI International Corp
Original Assignee
Oxy Metal Industries Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oxy Metal Industries Corp filed Critical Oxy Metal Industries Corp
Priority to US515130A priority Critical patent/US3898138A/en
Priority to CA219,108A priority patent/CA1045578A/en
Priority to FR7504079A priority patent/FR2288163A1/fr
Priority to DE2505499A priority patent/DE2505499C2/de
Priority to AU78178/75A priority patent/AU484928B2/en
Priority to JP50021396A priority patent/JPS5823477B2/ja
Priority to IT48268/75A priority patent/IT1029808B/it
Priority to NL7502531A priority patent/NL7502531A/xx
Priority to AR258478A priority patent/AR210076A1/es
Priority to BR3346/75A priority patent/BR7502634A/pt
Priority to GB22316/75A priority patent/GB1484227A/en
Application granted granted Critical
Publication of US3898138A publication Critical patent/US3898138A/en
Assigned to HOOKER CHEMICALS & PLASTICS CORP. reassignment HOOKER CHEMICALS & PLASTICS CORP. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: OXY METAL INDUSTRIES CORPORATION
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS CORP.
Assigned to OMI INTERNATIONAL CORPORATION reassignment OMI INTERNATIONAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OCCIDENTAL CHEMICAL CORPORATION
Assigned to MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF reassignment MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INTERNATIONAL CORPORATION, A CORP OF DE
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/12Electroplating: Baths therefor from solutions of nickel or cobalt

Definitions

  • metasulfobenzoic acid or its salts are (1) metasulfobenzoic acid or its salts; (2) butynediol or hexyne diol; and (3) butene diol and butenol alcohols.
  • Aldehydesy such as chloral hydrate and formaldehyde, may be added to assist in grain refinement and in reducing the sulfur content of the bath.
  • nickel bromide and nickel chloride The nickel salts are present in amounts conventional in the art, e.g., up to about 100 grams per liter of NiCl .6I-I O).
  • the patent discloses the addition to such baths of a specific aryl sulfon compound, namely metasulfobenzoic acid or its derivatives, such as Ni-carboxy benzene sulfonic acid can be utilized.
  • aldehyde such as chloral hydrate or formaldehyde
  • An aldehyde may be added to the patented bath for grain refinement and to reduce the sulfur content of the bath.
  • the general purpose of nickel electroplating is to yield a semi-bright deposit having the desirable characteristics of ductility, uniformly fine grained appearance, and good leveling characteristics. Normally, these objectives are met by the use of coumarin and other additives.
  • the deposit from a nickel solution containing coumarin generally deteriorates during use due to the gradual accumulation of the degradation products of the coumarin itself. These degradation products, such as melilotic acid and related compounds, are detrimental to the leveling and ductility of the deposit. As a result, these deposits must be removed by batch carbon treatments at periodic intervals, adding to the expense of the operation and normally resulting in time consuming, shortened scheduled production runs.
  • the present invention utilizes a specific combination of compounds which results in nickel deposits which are fine grained, lustrous, and ductile and which have markedly improved leveling characteristics. Although the leveling characteristics of the bath of the present invention are not quite as good as those obtained through the use of coumarin, the present invention does permit continuous use of the nickel solution without the accumulation of those deleterious degradation products which are developed in coumarin solutions.
  • the deposits from the solutions of the present invention generally contain less than about 0.005% sulfur.
  • the present invention is directed to the addition to baths such as those defined in U.S. Pat. No. 3,264,200 of a combination of three specific compositions or compounds.
  • the nickel-containing and pl-l-controlling elements of the bath are conventional and may be of any desired type, as defined in the noted patent.
  • the bath of the present invention may be of the Watts or modified Watts type containing nickel sulfate; of the sulfamate type; of the nickel fluoborate type; of the nickel bromide type; or of the nickel chloride type.
  • the pH of the bath is controlled by the use of boric acid (H 30 and an aldehyde, such as formaldehyde and/or chloral hydrate may be added, as above explained.
  • boric acid H 30 and an aldehyde, such as formaldehyde and/or chloral hydrate may be added, as above explained.
  • alkyne diol specifically butyne diol (l-IOH CC 5 CCH OH) or 3-l-Iexyne 2, 5 diol CH CH(OH)C 2 CCH(OH) CH being present in an amount ranging from about 0.05 to about 0.5 grams per liter of the bath; and
  • an important object of the present invention to provide a bath for the electrodeposition of nickel plate from an aqueous acidic nickel plating bath containing dissolved therein an aryl sulfon, an alkyne diol and a short chain alkene alcohol.
  • Another important object of the present invention is the provision of a method of electrodeposition of duetile, low-stress nickel plate having good leveling characteristics and including the step of electrodepositing semi-bright ductile nickel from an aqueous acidic nickel plating bath containing metasulfobenzoic acid or its salts, and a combination of at least one alkyne diol and at least one alkene alcohol containing four carbon atoms.
  • Another object of the present invention is the provision of a method of electrodepositing ductile low-stress nickel plate from an aqueous acidic nickel plating bath containing at least one nickel salt and metasulfobenzoic acid or its salts, residing in the improvement of incorporating in the bath a mixture of an alkene diol selected from the group consisting of butyne diol and hexyne diol, and an alkene alcohol selected from the group consisting of butene diol, butenol, and isomeric forms of butenol.
  • the present invention constitutes an improvement upon the invention disclosed and claimed in US. Pat. No. 3,264,200, assigned to the assignee of the present invention.
  • This improvement resides in the discovery of the synergistic effect which can be obtained from the incorporation of a specific mixture of specific unsaturated alcohols into the aqueous acidic nickel plating baths proposed in said earlier patent.
  • the earlier patent proposes the incorporation of metasulfobenzoic acid or the nickel salt of the compound into a bath for the electrodeposition of ductile, semibright nickel plate.
  • the mentioned patent discloses the incorporation of from 0.1 to about 10 grams per liter of metasulfobenzoic acid.
  • the metasulfobenzoic acid is usually neutralized with nickel hydroxide or nickel carbonate and is added to the bath as a nickel salt. It, however, can be added as the free acid, or as sodium or magnesium salt. If too high a concentration of the free acid is added to the nickel bath at one time, the pH of the bath will be substantially reduced. Therefore, the nickel salt of the acid is the preferred form, where additions of concentrations greater than about one gram per liter are added at one time. It should be understood that when metasulfobenzoic acid is referred to herein, this expression includes the nickel salt of the compound. Even where the free acid is added to the nickel bath, the metasulfobenzoic acid is generally in the form of the nickel salt, or the ionized nickel salt.
  • the acetylenic diols which are added are preferably in the simple unreacted diol form, since it has been found that the derivatives thereof, such as the epichlorohydrin adduct of butyne diol are not very effective.
  • the two preferred alkyne diols are butyne 1, 4 diol, HOCH CC CCH OH or 3-hexyne 2, 5 diol CH CH(OI-I)C E CCI-I(OH)CH This ingredient is added in an amount ranging from about 0.05 to about 0.5 grams per liter of the solution. Short chained alkene alcohols are used in conjunction with the alkyne diols.
  • the alkene alcohols uniformly contain four carbon atoms and, as above noted, are effective whereas other specific unsaturated alcohols do not work in the combination, for example, allyl alcohol (CI-I :CI-ICH Ol-I) is ineffective.
  • concentration of the alkyne alcohol and the concentration of the alkene alcohol is defined as falling within the same broad range. It has been found that it is not necessary to use equal amounts of the two compounds, nor is the utilization of a specific combination of compounds within a defined group essential.
  • any suitable type of semi-bright nickel plating bath can be utilized, and the herein disclosed, three component combination is effective in sulfamate, fluoborate, bromide, and low chloride (less than 100 grams per liter NiC1 .6H O) baths.
  • the preferred pH range is from about 2.8 to about 4.5, and the preferred bath temperature may range from 130 to 140F.
  • the cathode current density may be an average of 40 to 60 amps per square foot with air agitation.
  • the Examples yielded lustrous, ductile, very low-stressed semi-bright nickel deposits which contain less than about 0.005% sulfur, and which have remarkedly good leveling characteristics.
  • the deposit which was obtained had improved leveling characteristics over the corresponding baths of US. Pat. No. 3,264,200.
  • a bath for the electrodeposition of ductile, lowstress nickel plate from an aqueous acidic nickel plating bath containing at least one nickel salt selected from the group consisting of nickel sulfate, nickel sulfamate, nickel fluoborate, nickel bromide and nickel chloride, and containing dissolved therein from about 01 to about grams per liter of metsulfobenzoic acid, from about 0.05 to about 0.5 grams per liter of an alkyne diol selected from the group consisting of butyne diol and hexyne diol, and from about 0.05 to about 0.5- grams per liter of an alkene alcohol selected from the group consisting of butene diol, butenol and isomers of buteno].
  • a bath for the electrodeposition of ductile low- Ill stress nickel plate from an aqueous acidic nickel plating bath said bath containing at least one nickel salt selected from the group consisting of nickel sulfate, nickel sulfamate, nickel fluoborate, nickel bromide and nickel chloride and containing dissolved therein from about 0.1 to about 10 grams per liter of metasulfobenzoic acid, the improvement of incorporating into said bath a combination of from about 0.05 to about 0.5 grams per liter of an alkyne diol and from about 0.05 to about 0.5 grams per liter of a butene alcohol.
  • a method for the electrodeposition of ductle lowstress nickel plate exhibiting improved leveling characteristics comprising the step of electrodepositing semibright ductile nickel from an aqueous acidic nickel plating bath containing at least one nickel salt selected from the group consisting of nickel sulfate, nickel sulfamate, nickel fluoborate, nickel bromide and nickel chloride and having dissolved therein from about 0.1 to about 10 grams per liter of metasulfobenzoic acid, from about 0.05 to about 0.5 grams per liter of an alkyne diol selected from the group consisting of butyne diol and hexyne diol, and from about 0.05 to about 0.5 grams per liter of an alkene alcohol selected from the group consisting of butyne diol, butenol and isomers of butenol.

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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)
US515130A 1974-10-16 1974-10-16 Method and bath for the electrodeposition of nickel Expired - Lifetime US3898138A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US515130A US3898138A (en) 1974-10-16 1974-10-16 Method and bath for the electrodeposition of nickel
CA219,108A CA1045578A (en) 1974-10-16 1975-01-31 Method and bath for the electrodeposition of nickel
FR7504079A FR2288163A1 (fr) 1974-10-16 1975-02-10 Bains de depot electrolytique de nickel ductile et procedes utilisant ces bains
DE2505499A DE2505499C2 (de) 1974-10-16 1975-02-10 Wäßriges saures Bad für die galvanische Abscheidung von duktilem Nickel
AU78178/75A AU484928B2 (en) 1975-02-13 Method and bath forthe electrodeposition of nickel
JP50021396A JPS5823477B2 (ja) 1974-10-16 1975-02-20 ニツケルノデンキトキンホウホウ オヨビ トキンヨク
IT48268/75A IT1029808B (it) 1974-10-16 1975-02-20 Bagno e metodo per elettrodepositare nickel
NL7502531A NL7502531A (nl) 1974-10-16 1975-03-04 Werkwijze voor het electrolytisch neerslaan van nikkel.
AR258478A AR210076A1 (es) 1974-10-16 1975-04-23 Un bano para la electrodeposicion de niquelado
BR3346/75A BR7502634A (pt) 1974-10-16 1975-04-30 Banho para eletrodeposicao de revestimento de niquel e processo para eletrodeposicao de revestimento de niquel
GB22316/75A GB1484227A (en) 1974-10-16 1975-05-22 Method and bath for the electrodeposition of nickel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US515130A US3898138A (en) 1974-10-16 1974-10-16 Method and bath for the electrodeposition of nickel

Publications (1)

Publication Number Publication Date
US3898138A true US3898138A (en) 1975-08-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
US515130A Expired - Lifetime US3898138A (en) 1974-10-16 1974-10-16 Method and bath for the electrodeposition of nickel

Country Status (10)

Country Link
US (1) US3898138A (es)
JP (1) JPS5823477B2 (es)
AR (1) AR210076A1 (es)
BR (1) BR7502634A (es)
CA (1) CA1045578A (es)
DE (1) DE2505499C2 (es)
FR (1) FR2288163A1 (es)
GB (1) GB1484227A (es)
IT (1) IT1029808B (es)
NL (1) NL7502531A (es)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2583070A1 (fr) * 1985-06-11 1986-12-12 Limburgs Galvano Tech Bedri Procede de protection contre l'usure et la corrosion de pieces en acier, en particulier de cylindres hydrauliques
US5269838A (en) * 1992-04-20 1993-12-14 Dipsol Chemicals Co., Ltd. Electroless plating solution and plating method with it
EP1300487A1 (en) * 2001-10-02 2003-04-09 Shipley Co. L.L.C. Plating bath and method for depositing a metal layer on a substrate
WO2008154722A1 (en) * 2007-06-18 2008-12-24 Vale Inco Limited Method for improving nickel cathode morphology
US20110155582A1 (en) * 2009-11-18 2011-06-30 Tremmel Robert A Semi-Bright Nickel Plating Bath and Method of Using Same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014207778B3 (de) * 2014-04-25 2015-05-21 Kiesow Dr. Brinkmann GmbH & Co. KG Verwendung einer Mischung zur Verwendung in einem galvanischen Bad oder eines galvanischen Bades zur Herstellung einer Glanznickelschicht sowie Verfahren zur Herstellung eines Artikels mit einer Glanznickelschicht

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264200A (en) * 1964-01-16 1966-08-02 Udylite Corp Electrodeposition of nickel

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1266377A (fr) * 1960-09-01 1961-07-07 Metal & Thermit Corp Dépôt électrolytique de nickel brillant

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264200A (en) * 1964-01-16 1966-08-02 Udylite Corp Electrodeposition of nickel

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2583070A1 (fr) * 1985-06-11 1986-12-12 Limburgs Galvano Tech Bedri Procede de protection contre l'usure et la corrosion de pieces en acier, en particulier de cylindres hydrauliques
US5269838A (en) * 1992-04-20 1993-12-14 Dipsol Chemicals Co., Ltd. Electroless plating solution and plating method with it
EP1300487A1 (en) * 2001-10-02 2003-04-09 Shipley Co. L.L.C. Plating bath and method for depositing a metal layer on a substrate
US6773573B2 (en) 2001-10-02 2004-08-10 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
WO2008154722A1 (en) * 2007-06-18 2008-12-24 Vale Inco Limited Method for improving nickel cathode morphology
US20110155582A1 (en) * 2009-11-18 2011-06-30 Tremmel Robert A Semi-Bright Nickel Plating Bath and Method of Using Same
WO2012121829A1 (en) * 2011-03-09 2012-09-13 Macdermid Acumen, Inc. Semi-bright nickel plating bath and method of using same
CN103415653A (zh) * 2011-03-09 2013-11-27 麦克德米德尖端有限公司 半光亮镍电镀浴及使用其的方法
EP2683853B1 (en) 2011-03-09 2017-10-11 MacDermid Acumen, Inc. Semi-bright nickel plating bath and method of using same

Also Published As

Publication number Publication date
AR210076A1 (es) 1977-06-30
FR2288163B1 (es) 1979-06-29
JPS5823477B2 (ja) 1983-05-16
DE2505499C2 (de) 1982-01-21
DE2505499A1 (de) 1976-04-29
GB1484227A (en) 1977-09-01
FR2288163A1 (fr) 1976-05-14
NL7502531A (nl) 1976-04-21
CA1045578A (en) 1979-01-02
IT1029808B (it) 1979-03-20
JPS5147538A (en) 1976-04-23
AU7817875A (en) 1976-08-19
BR7502634A (pt) 1976-08-31

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AS Assignment

Owner name: HOOKER CHEMICALS & PLASTICS CORP.

Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885

Effective date: 19801222

AS Assignment

Owner name: OCCIDENTAL CHEMICAL CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054

Effective date: 19820330

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827

Effective date: 19830915

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Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY

Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733

Effective date: 19830930