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US2795540A - Electrodeposition of nickel - Google Patents

Electrodeposition of nickel Download PDF

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Publication number
US2795540A
US2795540A US421180A US42118054A US2795540A US 2795540 A US2795540 A US 2795540A US 421180 A US421180 A US 421180A US 42118054 A US42118054 A US 42118054A US 2795540 A US2795540 A US 2795540A
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United States
Prior art keywords
nickel
coumarin
alkoxy
liter
bath
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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
US421180A
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English (en)
Inventor
Brown Henry
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Udylite Research Corp
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Udylite Research Corp
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Filing date
Publication date
Application filed by Udylite Research Corp filed Critical Udylite Research Corp
Priority to US421180A priority Critical patent/US2795540A/en
Priority to GB9989/55A priority patent/GB774614A/en
Priority to FR1162531D priority patent/FR1162531A/fr
Priority to DEU3290A priority patent/DE1003531B/de
Application granted granted Critical
Publication of US2795540A publication Critical patent/US2795540A/en
Anticipated expiration legal-status Critical
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
    • C25D3/18—Heterocyclic compounds

Definitions

  • the present invention relates to the electrodeposition of nickel from an aqueous acidic bath, and more particularly relates to the production of nickel plate having superior ductility, and brightness in comparison to that of heretofore known nickel plate.
  • alkoxy coumarins namely alkoxy coumarins having not more than two carbon atoms in the alkoxy group and being positioned on the coumarin nucleus in a position numbered at least as high as 6 by conventional nomenclature, in the bath causes the plate which is electrodeposited therefrom to be very fine-grained even though it may be cloudy and milky in appearance, and to show marked increasing luster with continued plating.
  • the 6-, 7-, or 8-position substituted mono-methoxy or mono-ethoxy coumarins impart exceptional luster and marked increasing luster with increased thickness of nickel plate when used alone in the warm acidic nickel baths of the Watts type and similar types.
  • the improvement in luster and brightness and the marked increasing luster and brightness with increased thickness of nickel-plate is amazing when compared to other substituted coumarins, for example, hydroxy coumarins (7-hydroxy coumarin, i. e., umbelliferone of U. '8. 2,635,076, April 14, 1953) or, for that 'matter,- carboxy coumarins, or chloro, or methyl substituted coumarins.
  • the improvement is. greater than formaldehyde (n-( i-H) compared with hydroxy-formaldehyde Patented June 11, 1957 i. e.
  • the 6-, 7- or 8-mono-methoxy or mono-ethoxy coumarins do not cause oily efiects (streaks and bunched pitsin the nickel plate) in the nickel baths operated-at temperatures of from 60 C. to C. even when concentrations higher than about 1 gram per liter are used.
  • the cathode reduction product formed during plat ing from baths containing the additives of this invention is much less harmful to the nickel plate than that formedwith coumarin or the hitherto suggested derivatives of coumarin in the bath, and for this reason nickel plating baths containing the alkoxy coumarins of this invention require carbon treatment less often, and give brighter plate.
  • an increased rate of brightening in the middle current density ranges may be obtained by adding to the bath a small amount of about 0.001 gram/liter to 0.4 gram/liter of one of the compounds of Table l of United States Patents 2,647,866, 2,648,628 and 2,654,704.
  • aryl sulfones (sulfonamides, sulfonic acids), in general do not have a critical concentration range in the bath, and they produce practically no further improvement after their optimum concentration is reached.
  • sulfonamides, sulfonic acids in general do not have a critical concentration range in the bath, and they produce practically no further improvement after their optimum concentration is reached.
  • alkoxy coumarin of' Table III there is preferential reduction of the unsaturated compound with respectto the nickel ion, whereas with the aryl sul-.
  • the nickelion is reduced preferentially.
  • the vari ation Qfth-e reduction with the variation of the potentials between adjacent high and low points will account for the rate of brightening or smoothening out effect.
  • the concentration of'the methoxyand ethQxy-coumarins which may be advantageously employed is not critical in any concentration up to saturation and these materials may be used at concentrations between about 0.05 gram per liter to about 2 grains/liter, the preferred concentrationbeing 0.1 gram/liter.to 1.0 gram/liter.
  • the best cathode .film buffer is boric acid and it is important to keep its concentration high (over 30 grams/ liter), especiallyin the warm baths.
  • Other buffers may beu sed preferably in small amounts (1 to 5 grams/liter) with the boric :acid withr-beneficialjeifects, such as formic, citric, fiuobor ic acids, etc., but they are not recommended to be used alone, except in the caseof nickel fiuoboratc for high speed plating.
  • ammonium salts should be kept at a minimum.
  • concentration of zinc and copper ions in the bath should also be kept as low as possible. This is especially desirable where the concentration of benzene sulfonic acids or-benzene sulfonamides is low in the bath or the latter compounds are absent.
  • .Soft, sulfur-free plate and increased brightness, especially in the middle current density range may be obtained by using an admixture of the 6-, 7- or 8-methoxy or ethoxy coumarin in an amount between about 0.05 gram/liter to saturation with about 0.05 to 0.4 gram/ liter of at least one of the group consisting of chloral hydrate, bromal hydrate .and formaldehyde.
  • the baths may be operated at pH values ranging from 2.0 to 5.5 and temperatures ranging from 20 degrees C. to 70 degrees C. and even higher, and the preferred current density ranges may be from 5 to l50-amps./sq. ft. depending on the agitation, the temperature of the bath and the concentration and the type of nickel salts.
  • the 6-, 7- or S-methoxy or ethoxy coumarins of this invention function better at the higher pH values of the nickel bath, that is, 3.0 to 5.5 and the best operating range has been found to be between about 4.2 and 4.5.
  • methoxy and ethoxy coumarins of this invention resides in their ability to function in the lower pH range of 3.0 ton-3.5 in comparison to heretofore known high leveling baths which usually require a pH of 4.0 to 4.5. At these lower pH values the precipitation of ferric hydroxide is avoided which in the higher pH baths results in roughness and pitting unless a very rapid rate of filtration is employed.
  • the benzene sulfonamides and sulfonimides may be used etfectively in concentrations of from 0.05 gram/liter to saturation.
  • Example 3 NiSO4.6HzO "grams/liter" 200-300 NiCl2.6H2O do 40-75 HsBOa "do"-.. 40 8-rnethoxyco1unarin do 0.l-0.2 Chloral hydrate do 0.1-0.2 P V 3.0-4.5 Temperature F 110-140
  • Example 4 NiS04.6HzO grams/ 1iter 200-300 Niflo d-o 40-75 H3Bna dO .40 Ni(BF4)2 do .14 S-methoxycoumarin do 0.3-1.5 o-Benzoyl sulfimide do L 0.1 03 P AM:
  • Example 7 V Nicnsrno grams/liter.... 100 HsBO do 45-50 7-methoxycoumarin (in (1144 H 3.8-4.8 Temperature F 140
  • Example 8 NiCl2.6Hz0 "grams/liter" 100 H3BO3 do 45 8-methoxycoumarin do 0 1 0 pl-I 4.2
  • Example 9 NiClz.6I-I2O grams/liter 100 H3BO1 dn 45 8-eth0xycoumarin -c do 0.1-0.2 pH 4.2 Chloral hydrate grams/liter -0.1-0. Temperature F..
  • the superiority lies not only in the brighter plate obtained from the standpoint of the fast rate of brightening, but also in the wider range of current density over which the rate of brightening is superior (especially the middle and lower current densities in which coumarin and its hydroxy, alkyl and carboxy derivatives are poor), and the lower frequency of needing activated carbon treatments.
  • chloral or bromal hydrate in a concentration of 0.1-0.2 gram per liter is a distinct advantage in conjunction with any coumarin derivative.
  • 2,321,182 is also beneficial in obtaining smooth fine-grained ductile plate from the baths containing an alkoxy coumarin of this invention. Furthermore, the semi-bright (cloudy lustrous) plates obtained from the chloride-type baths containing the aldehydes as well as the alkoxy coumarin as in Examples 9 and 10, can be most safely transferred to full bright nickel baths without loss of adhesion compared to Watts type baths.
  • 5-alkoxy coumarin is also intended to be included although the 5-alkoxy coumarins are more ditli-cult to prepare.
  • a bath for electrodepositing lustrous nickel comprising an aqueous acidic solution consisting essentially of an electrolyte selected from the group consisting of nickel sulfate, nickel chloride and mixtures thereof in the presence of an alkoxy coumarin having not more than 2 carbon atoms in the alkoxy group, said alkoxy group being in a position on the coumarin nucleus numbered at least as high as 5, said alkoxy coumarin being present in the amount of about 0.05 gram/liter to saturation.
  • a bath as claimed in claim 1 wherein the alkoxy coumarin is S-methoxy coumarin.
  • a bath as claimed in claim 1 wherein the alkoxy coumarin is 7-methoxy coumarin.
  • a bath as claimed in claim 1 wherein the alkoxy coumarin is 7-ethoxy coumarin.
  • a method for electrodepositing bright nickel consisting of electrodepositing nickel from an aqueous acidic nickel solution consisting essentially of an electrolyte selected from the group consisting of nickel sulfate, nickel chloride and mixtures thereof in the presence of an alkoxy coumarin having not more than 2 carbon atoms in the alkoxy group, said alkoxy group being in a position on the coumarin nucleus numbered at least as high as 5, and being present in an amount of about 0.05 gram/liter to saturation.
  • a bath for electrodepositing lustrous nickel comprising an aqueous acidic solution consisting essentially of an electrolyte selected from the group consisting of nickel sulfate, nickel chloride and mixtures thereof in the presence of an organic compound dissolved in the aqueous acidic nickel solution in a concentration of alkoxy about 0.05 gram/liter to saturation and selected from the 7 group consisting of benzene sulfonic acids, sulfonamides and sulfonimides, and about 0.05 gram/liter to saturation of an alkoxy coumarin having not more than 2 carbon atoms in the alkoxy group, said alkoxy group being in a position on the coumarin nucleus numbered at least as high 5.
  • a bath as claimed in claim 11 wherein the alkoxy coumarin is S-methoxy coumarin.
  • a bath as claimed in claim 11 wherein the alkoxy coumarin is 7-methoxy coumarin.
  • a bath as claimed in claim 11 wherein the alkoxy coumarin is 6-methoxy coumarin.
  • a bath as claimed in claim 11 wherein the alkoxy coumarin is 8-ethoxy coumarin.
  • a bath as claimed in claim 11 wherein the alkoxy coumarin is 7-ethoxy coumarin.
  • a bath for electrodepositing lustrous nickel comprising an aqueous acidic solution consisting essentially of at least one nickel salt selected from the group consisting of nickel sulfate and nickel chloride, in the presence of about .05 gram/liter to saturation of an alkoxy coumarin having not more than 2 carbon atoms in the alkoxy group, said alkoxy group being in a position on the coumarin nucleus numbered at least as high as 5, and
  • a method for electrodepositing lustrous nickel consisting of electrodepositing nickel from an aqueous acidic nickel solution consisting essentially of at least one nickel salt selected from the group consisting of nickel sulfate and nickel chloride in the presence of about .05 gram/ liter to saturation of an alkoxy coumarin having not more than 2 carbon atoms in the alkoxy group, said alkoxy group being in a position on the coumarin nucleus numbered at least as high as '5, and about 0.05 to about 0.2 gram/liter of at least one material selected from the group consisting of chloral hydrate, bromal hydrate and formaldehyde.
  • a bath for electrodepositing lustrous nickel corn prising an aqueous acidic solution consisting essentially of at least one nickel salt selected from the group consisting of niekel'sulfate' and nickelchloride in the presence of about 0.05 gram/liter to saturation of an alkoxy coumarin having not more than two carbon atoms in the alkoxy group, said alkoxy group being in a position on the cournarin nucleus numbered 'at least as high as 5, about 0.05 to about 0.2 gram per liter of at least one material selected from the group consisting of chloral hydrate, bromal hydrate and formaldehyde, and about 0.1 to about 1 gram/liter of at least one material selected from the group consisting of trirnethyl aconitate and di-' (methy C l ow v m t t 20..
  • a method for electrodepositinglustrous nickel consisting ofelectrodepositing nickel from an aqueous acidic nickel solution consisting essentially of at least one nickel salt selected from the group consisting of nickel sulfate and nickel chloride in the presence of about 0.05 gram/- liter to saturation of an alkoxy cournarin having not more than two carbon atoms in the alkoxy group, said alkoxy group being in a positiqnon thecoumarin nucleus numbered at least as high as 5, about 0,05 to about 0.2 gram per liter of at least one material selected from the group consisting of chloral hydrate, brornal hydrate and formaldehyde, "and about 0.1 .to abouttl gram/liter of at least one material selected from the group consisting of trimethyl aconitate and di(methyl Cellosolve) maleate.

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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)
US421180A 1954-04-05 1954-04-05 Electrodeposition of nickel Expired - Lifetime US2795540A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US421180A US2795540A (en) 1954-04-05 1954-04-05 Electrodeposition of nickel
GB9989/55A GB774614A (en) 1954-04-05 1955-04-05 Improvements in or relating to the electrodeposition of nickel
FR1162531D FR1162531A (fr) 1954-04-05 1955-04-05 Perfectionnements apportés au dépôt électrolytique du nickel
DEU3290A DE1003531B (de) 1954-04-05 1955-04-05 Saures galvanisches Glanzvernickelungsbad

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DE (1) DE1003531B (de)
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GB (1) GB774614A (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2900707A (en) * 1954-08-06 1959-08-25 Udylite Corp Metallic protective coating
US2986501A (en) * 1959-07-27 1961-05-30 Mcgean Chem Co Inc Electrodeposition of nickel
US3116225A (en) * 1960-07-30 1963-12-31 Dehydag Gmbh Nickel electroplating baths
US3386897A (en) * 1964-09-15 1968-06-04 Barnet D. Ostrow Electroplasting bright nickel
US3486989A (en) * 1967-01-30 1969-12-30 M & T Chemicals Inc Semi-bright nickel plating
US3502550A (en) * 1965-11-01 1970-03-24 M & T Chemicals Inc Nickel electroplating electrolyte
US5034275A (en) * 1989-11-24 1991-07-23 Pearson James M Paint coated sheet material with adhesion promoting composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL133678C (de) * 1965-10-22

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635076A (en) * 1947-01-29 1953-04-14 Harshaw Chem Corp Bright nickel plating
US2678910A (en) * 1950-08-16 1954-05-18 Udylite Corp Electroplating of nickel
US2683115A (en) * 1948-07-24 1954-07-06 Harshaw Chem Corp Electrodeposition of nickel

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2195409A (en) * 1936-07-31 1940-04-02 Nat Aniline & Chem Co Inc Electrodeposition
US2427280A (en) * 1941-02-11 1947-09-09 Du Pont Nickel electroplating composition
GB634394A (en) * 1946-04-20 1950-03-22 Udylite Corp Improvements in electrodeposition of nickel from an acid bath
US2644789A (en) * 1951-08-02 1953-07-07 Harshaw Chem Corp Electrodeposition of nickel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635076A (en) * 1947-01-29 1953-04-14 Harshaw Chem Corp Bright nickel plating
US2683115A (en) * 1948-07-24 1954-07-06 Harshaw Chem Corp Electrodeposition of nickel
US2678910A (en) * 1950-08-16 1954-05-18 Udylite Corp Electroplating of nickel

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2900707A (en) * 1954-08-06 1959-08-25 Udylite Corp Metallic protective coating
US2986501A (en) * 1959-07-27 1961-05-30 Mcgean Chem Co Inc Electrodeposition of nickel
US3116225A (en) * 1960-07-30 1963-12-31 Dehydag Gmbh Nickel electroplating baths
US3386897A (en) * 1964-09-15 1968-06-04 Barnet D. Ostrow Electroplasting bright nickel
US3502550A (en) * 1965-11-01 1970-03-24 M & T Chemicals Inc Nickel electroplating electrolyte
US3486989A (en) * 1967-01-30 1969-12-30 M & T Chemicals Inc Semi-bright nickel plating
US5034275A (en) * 1989-11-24 1991-07-23 Pearson James M Paint coated sheet material with adhesion promoting composition

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Publication number Publication date
FR1162531A (fr) 1958-09-15
DE1003531B (de) 1957-02-28
GB774614A (en) 1957-05-15

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