US2678910A - Electroplating of nickel - Google Patents

Electroplating of nickel Download PDF

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Publication number
US2678910A
US2678910A US179873A US17987350A US2678910A US 2678910 A US2678910 A US 2678910A US 179873 A US179873 A US 179873A US 17987350 A US17987350 A US 17987350A US 2678910 A US2678910 A US 2678910A
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United States
Prior art keywords
nickel
bath
ester
acid
unsaturated
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Expired - Lifetime
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US179873A
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English (en)
Inventor
Brown Henry
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Udylite Corp
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Udylite Corp
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Publication date
Priority to BE505242D priority Critical patent/BE505242A/xx
Priority to NL80234D priority patent/NL80234C/xx
Application filed by Udylite Corp filed Critical Udylite Corp
Priority to US179873A priority patent/US2678910A/en
Priority to DEU1284A priority patent/DE900037C/de
Priority to FR1048418D priority patent/FR1048418A/fr
Priority to GB19207/51A priority patent/GB704185A/en
Application granted granted Critical
Publication of US2678910A publication Critical patent/US2678910A/en
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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

Definitions

  • My invention relates to improvements in the electrodeposition of nickel from aqueous acidic baths. It is particularly concerned with the utilization of certain addition agents for the purpose of decreasing grain size and increasing the luster of the nickel plate or deposit, and it is especially concerned with the production of electrodeposits of brilliant, highly lustrous, ductile nickel plates.
  • the grain size of electrodeposits may be decreased and the luster of the nickel deposit increased, all in an effective manner, by the utilization of certain bath-soluble organic compounds, specifically, certain aliphatic esters of unsaturated aliphatic polycarboxylic acids, the unsaturation of which acids is due solely to double bonds.
  • certain bath-soluble organic compounds specifically, certain aliphatic esters of unsaturated aliphatic polycarboxylic acids, the unsaturation of which acids is due solely to double bonds.
  • Particularly satisfactory are the methyl and ethyl esters of unsaturated aliphatic polycarboxylic acids containing from 4 to 8 carbon atoms although excellent results are also obtained through the utilization of certain alkoxy valkyl esters of such unsaturated aliphatic polycarboxylic acids.
  • the esters Whose utilization is contemplated by my present invention are those wherein all of the carboxyl groups of the unsaturated aliphatic polycarboxylic acids are esterified.
  • esters whose use is contemplated in accordance with the present invention must be soluble in the aqueous acidic nickel electroplating bath to a degree sufiicient to enable such esters to exert :the effect of decreasing the grain sizeof the electroplate of nickel and increasing the luster thereof.
  • Di-(Z-methoxy ethyl) Iumarate Dimethyl maleata... l. Diethyl maleate Dimethyl chlorornaleate Dl-(Z-methoxy ethyl) maleate (Di-Methyl Cellosolve" maleate) Di-(Z-ethoxy ethyDmaleate (Di-Oe1losolve” Maleate) Dimcthyl itaconatel Diethyl itaconate l Di-(2-methoxy ethyl) itaconate Di-(Z-(B methoxyethoxy)ethyhitaconate Dimethyl methylene malonate Dimothyl glutaconate Dimethyl mesaconate.
  • Dimethyl citraconate Dimethyl crot Methyl ethyl mal ate Methyl, 2-metl1oxy ethyl fumarate.
  • Di-(2-ethoxy ethyhitaconate we w were tWt t OOOQOOOOOOQOOD O OOQODQQ Esters of Unsaturated Tricarboxylic Acids ES; mm,
  • Trimethyl ethylenetricarboxylate....v 0. 2-2 Trimethyl a propylene, a,o,'y tricarboxylate 0. 2-2 3. Trimethyl iso-aconitate (trimethyl a propylene 0,7,7 tricarboxylate) l 0. 2-2 4. Trimethyl aconitate (trimethyl a propylene M8, tricarboxylate) 0. 2-2 5. Trimethyl allenetricarboxylata l. 0. 2-2 6. Trimethyl oxalocitraconate 0. 2-2 7. Tri-(Z-methoxy ethyDaconitate 0. 2-2 8. 'lri-(2-methoxy ethyl)ethylenetricarboxylate. 0. 2-2
  • esters of 2- methoxy ethanol; 2-ethoxy ethanol as, for example, di- (2-methoxy ethyl) iumarate; til-(2- methexy ethyll-maleate; tri-(Z-methoxy ethyl) aconitate; di-(Z-ethoxy ethyDmaIeate; di-(2- ethoxy ethyl) fumarate; and also the methyl esters such as dimethyl maleate, dimethyl fumarate, trimethyl aconitate, and dimethyl itaconate, used either alone, or in mixtures with one another, or in conjunction with organic sulphurcontaining brighteners, as described hereafter.
  • Benzene sulfonamidc m-carboxylic am 0.1-3 ll. 7-Aldchydo o-benzoyl sulfimlde. 0.1-3 l2.
  • N-Acetyl benzene su1ionimlde 0.1-2 13.
  • Hydroxyrnethyl benzene sulionamide 0.1-2 15.
  • Benzene sulfonic acids (mono-, di-, and tri-) 1-15 18.
  • Benzaldehydc sulionie acids (0, m, p). 2-6 20. Dlphenyl sulfonc sulionic acid 1-8 21. Naphthalene snlfonic acids (mono-, dl-, and tri-) 1-8 22. Benzene sulfohydroxamic acid 23. p-Ohlor benzene sullonic acid. 1-15 24. Diphenyl snlfonlc acid 1-5 25. nJ-Diphenyl benzene sulionic acid 1-4 26. Z-Chloro-5-sulfobenzaldehydc l-5 27. m-Benzene disnlfonamide. 0.5-1 28.
  • Allyl sulfonic acid 4-12 may be utilized in their acid form or in the form of salts as, for example, nickel, sodium, potassium or other salts.
  • sulfonic brighteners may be utilized in their acid form or in the form of salts as, for example, nickel, sodium, potassium or other salts.
  • Especially satisfactory, for use in the practice of my present invention are the compounds of Table II corresponding to numbers 1, 2, 3; 18, 19, 21 and 28, the latter particularly in the form of their nickel salts.
  • the salts thereof are likewise included.
  • the compounds of Table II produce bright and mirror-like deposits on buffed metals such as buffed brass. However, at least in the ordinary case, they do not accomplish the same results on steel polished with emery or on matte (but unburnt) copper plate of 0.0063"-0.0005" thickness but, rather generally yield plates of somewhat dull and gray appearance in these cases.
  • the compounds of Table I in the usual case, give a different type of plate than that produced by the compounds of Table II.
  • the plates produced with the compounds of Table I are generally cloudy and milky on buffed or matte metal. The rate of improvement of luster of the base or basis metal is much more rapid with the compounds of Table I, per se, than with the compounds of Table II, per se. If, however, the two difierent types of compounds represented in Tables I and II are used together in the baths, as I have indicated above, a brilliant mirror-like deposit is obtained even over a matte surface.
  • the compounds of Table I tend to be consumed at a faster rate during the electroplating process than the compounds of Table II.
  • the compounds of Table I in general, have a faster rate of reduction at the nickel cathode with respect to the nickel ion, whereas the compounds of Table II, in general, have'a slower rate, that is, the nickel ion is reduced preferentially in the latter case.
  • the concentration of the Table I compounds in the bath may range from about 0.2 gram to about 3 grams per liter. For optimum results, a range of about 0.6 gram to 2 grams per liter usually is approximately correct. In certain, and perhaps most, cases, these concentrations are close to saturation for the particular esters utilized. Continuous filtration and the use of surface active agents to prevent pitting tend to aid in solubilizing at least to a certain extent the compounds of Table I and such procedures are, therefore, recommended in at least most cases. Where the esters of Table I which are selected for use hav an appreciable vapor pressure at the temperature at which the bath is operated, suitable ventilation should be provided.
  • the baths can be operated at temperatures ranging from about room temperature to almost boilin but, in general, the preferred temperature is in the range of about 46 degrees C. to 65 degrees C. Where the baths are operated at somewhat elevated. temperatures, it will be understood that theesters of the unsaturated aliphatic polycarboxylic selected should be those which are stable at the bath temperatures.
  • the baths can be operated at pH values ranging from about 2 to about 5.5 but, in the ordinary case, the preferred p l-l values are from 3.0 to 4.8.
  • the cathode current density ranges are quite variable, a range or" about to several hundred amperes per square foot being utilizable, the optimum depending upon agitation, temperature, and concentration and type of nickel salts utilized in the bath.
  • a good working rang is about to about 80 amperes per square foot.
  • Most of the compounds of Table I function optimumly at pH values of about 3.8 to 4.5 and at bath temperatures of about degrees C. to degree C. Generally speaking, the lower the temperature of the bath, the higher the pl-l value at which the bath should be operated for obtainin optimum results.
  • esters of Table I may serve best for the accomplishment of the reduction of grain size and the production of a ductile, lustrous though milky deposit when used. alone, such esters are not necessarily the best ones to achieve, in conjunction with utilization of the organic sulfur-containing brighteners, the production of bright mirror-like deposits over matte metal surfaces.
  • esters for era le. 2. better conjoint effect is produced through the utilization of di-(Z-methoxy ethyl) maleate in conjunction with o-benzoyl sulfimide than with dimethyl fumarate in conjunction with o-bensoyl sulfimide.
  • the di-(Z-methoxy ethylhnalcate has the practical advantage over the dimethyl fumarate in that it is less volatile and is easier to handle in relation to odors, eiiects on the skin and the like.
  • a bath for the electrcdeposition of nickel comprising an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel chloride, nickel sulfate, nickel iluoborate and. nickel sulfamate, said also containing, in solution, not more than about .5 of at least one bath-soluble fully esterified aliphatic ester of an unsaturated aliphatic polycarboxylic acid, said ester being unsaturated and the unsaturation of which is due solely to double bonds in the said acid.
  • a bath for the electrocleposition of nickel comprising an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel chloride, nickel sulfate nickel fluoborate and nickel suliamate, said bath also containing, in solution, not more than about (3.5% of at least one bath-scluble fully esteriiled aliphatic ester of an unsaturated aliphatic polycarboxylic acid, said polycarboxylicacid containing from 4 to 8 carbon atoms and the unsaturation of which is due solely to double bonds, and said ester being unsaturated and the unsaturation of said ester being due solely to double bonds in the said acid.
  • a bath for the electrodeposition of nickel comprising an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fluoborate and nickel sulfarnate, said bath also containing, in solution, not more than about .5% at least one bath-soluble fully esterified aliphatic ester of an unsaturated aliphatic polycarboxylic acid, said ester being unsaturated and the unsaturation of which is due solely to double bonds in said acid, and of at least one brightener selected from the group consisting of organic sulfonamides, sulionirnides, and sulionic acids.
  • a bath for the electrocleposition of nickel comprising an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel chloride, nickel sulfate, nickel fluoborate and nickel sulfamate, said bath also containing, in solution, not more than about 0.5% of at least one bath-soluble fully esterified aliphatic ester of an unsaturated aliphatic polycarboxylic acid, said polycarboxylic acid containing from 4 to 8 carbon atoms and the unsaturation of which is due solely to double bonds, said ester being unsaturated and the unsaturation of said ester being due solely to double bonds in the said acid, and not more than about 0.5% of at least one brightener selected from the group consisting of organic sulfonamides, sulfonimides, and sulfonic acids.
  • ester is at least one selected from the group consisting of dimethyl esters of maleic acid, fumaric acid, and itaconic acid.
  • a bath in accordance with claim 18, wherein the brightener is o-benzoyl sulfimide.
  • a method of electrodepositing nickel to obtain a fine-grained deposit which comprises electrolyzing an aqueous acidic bath containing at least one nickel salt selected from the group consisting of nickel chloride, nickel sulfate, nickel fluoborate and nickel sulfamate, said bath also containing, in solution, not more than about of at least one bath-soluble fully esterified aliphatic ester of an unsaturated aliphatic polycarboxylic acid, said ester being unsaturated and the unsaturation of which is due solely to double bonds in said acid.
  • nickel salt selected from the group consisting of nickel chloride, nickel sulfate, nickel fluoborate and nickel sulfamate
  • a method of electrodepositing nickel to obtain a fine-grained deposit which comprises electrolyzing an aqueous acidic bath containing at least one nickel salt selected from the group consisting of nickel chloride, nickel sulfate, nickel fiuoborate and nickel sulfarnate, said bath also containing, in solution, not more than about 0.5% of at least one bath-soluble fully esterified aliphatic ester of an unsaturated aliphatic polyoarboxylic acid, said polycarboxylic acid containing from 4 to 8 carbon atoms and the unsaturation of which is due solely to double bonds, said ester being unsaturated and the unsaturation of said ester being due solely to double bonds in the said acid.
  • nickel salt selected from the group consisting of nickel chloride, nickel sulfate, nickel iluoborate and nickel sulfamate
  • sulfonic acids and, in addition, a bath-soluble fully esterified aliphatic ester of an unsaturated aliphatic polycarboxylic acid, said polycarboxylic acid containing from 4 to 8 carbon atoms and the unsaturation of which is due solely to double bonds and said ester being unsaturated and the unsaturation of said ester being due solely to double bonds in the said acid.

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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)
US179873A 1950-08-16 1950-08-16 Electroplating of nickel Expired - Lifetime US2678910A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE505242D BE505242A (enrdf_load_stackoverflow) 1950-08-16
NL80234D NL80234C (enrdf_load_stackoverflow) 1950-08-16
US179873A US2678910A (en) 1950-08-16 1950-08-16 Electroplating of nickel
DEU1284A DE900037C (de) 1950-08-16 1951-08-07 Galvanische Vernicklung
FR1048418D FR1048418A (fr) 1950-08-16 1951-08-09 Dépôt électrolytique du nickel
GB19207/51A GB704185A (en) 1950-08-16 1951-08-15 Improvement in electroplating of nickel

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US179873A US2678910A (en) 1950-08-16 1950-08-16 Electroplating of nickel

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BE (1) BE505242A (enrdf_load_stackoverflow)
DE (1) DE900037C (enrdf_load_stackoverflow)
FR (1) FR1048418A (enrdf_load_stackoverflow)
GB (1) GB704185A (enrdf_load_stackoverflow)
NL (1) NL80234C (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2773818A (en) * 1954-05-20 1956-12-11 Harshaw Chem Corp Alkaline nickel plating solution
US2795540A (en) * 1954-04-05 1957-06-11 Udylite Res Corp Electrodeposition of nickel
US2900707A (en) * 1954-08-06 1959-08-25 Udylite Corp Metallic protective coating
US3376207A (en) * 1965-05-17 1968-04-02 Patent Serm Ag Electrodeposition of nickel and electrolytes therefor
US3498893A (en) * 1967-03-27 1970-03-03 Ian H S Henderson Anodization of a nickel body which has a coating of partially electronically insulating material
US3639220A (en) * 1970-07-27 1972-02-01 Udylite Corp Electrodeposition of nickel
CN109642098A (zh) * 2016-07-26 2019-04-16 Ppg工业俄亥俄公司 包含1,1-二活化的乙烯基化合物的可电沉积的涂料组合物

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1032056B (de) * 1954-08-09 1958-06-12 Metal & Thermit Corp Glanzvernickelungsbad
US2800441A (en) * 1955-10-04 1957-07-23 Udylite Res Corp Electrodeposition of nickel
NL263657A (enrdf_load_stackoverflow) * 1960-04-22

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2466677A (en) * 1945-08-27 1949-04-12 Udylite Corp Electrodeposition of nickel from an acid bath
US2523161A (en) * 1947-11-28 1950-09-19 Allied Chem & Dye Corp Electrodeposition of nickel

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2466677A (en) * 1945-08-27 1949-04-12 Udylite Corp Electrodeposition of nickel from an acid bath
US2523161A (en) * 1947-11-28 1950-09-19 Allied Chem & Dye Corp Electrodeposition of nickel

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2795540A (en) * 1954-04-05 1957-06-11 Udylite Res Corp Electrodeposition of nickel
US2773818A (en) * 1954-05-20 1956-12-11 Harshaw Chem Corp Alkaline nickel plating solution
US2900707A (en) * 1954-08-06 1959-08-25 Udylite Corp Metallic protective coating
US3376207A (en) * 1965-05-17 1968-04-02 Patent Serm Ag Electrodeposition of nickel and electrolytes therefor
US3498893A (en) * 1967-03-27 1970-03-03 Ian H S Henderson Anodization of a nickel body which has a coating of partially electronically insulating material
US3639220A (en) * 1970-07-27 1972-02-01 Udylite Corp Electrodeposition of nickel
CN109642098A (zh) * 2016-07-26 2019-04-16 Ppg工业俄亥俄公司 包含1,1-二活化的乙烯基化合物的可电沉积的涂料组合物
US20190153244A1 (en) * 2016-07-26 2019-05-23 Ppg Industries Ohio, Inc. Electrodepositable Coating Compositions Containing 1,1-Di-Activated Vinyl Compounds
US10961403B2 (en) * 2016-07-26 2021-03-30 Ppg Industries Ohio, Inc. Electrodepositable coating compositions containing 1,1-di-activated vinyl compounds

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DE900037C (de) 1953-12-17
NL80234C (enrdf_load_stackoverflow)
BE505242A (enrdf_load_stackoverflow)
GB704185A (en) 1954-02-17
FR1048418A (fr) 1953-12-22

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