US3220940A - Electrodeposition of nickel - Google Patents

Electrodeposition of nickel Download PDF

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US3220940A
US3220940A US171566A US17156662A US3220940A US 3220940 A US3220940 A US 3220940A US 171566 A US171566 A US 171566A US 17156662 A US17156662 A US 17156662A US 3220940 A US3220940 A US 3220940A
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nickel
sulfonic acid
saturation
baths
compounds
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US171566A
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Brown Henry
Donald H Becking
Richard M Stevenson
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OMI International Corp
Udylite Research Corp
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Udylite Research Corp
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Priority to GB1646/63A priority patent/GB1010567A/en
Priority to DEU9555A priority patent/DE1237870B/en
Priority to FR923789A priority patent/FR1348066A/en
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Assigned to HOOKER CHEMICALS & PLASTICS CORP. reassignment HOOKER CHEMICALS & PLASTICS CORP. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: OXY METAL INDUSTRIES CORPORATION
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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
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
    • 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

  • This invention relates to the electrodeposition of nickel from aqueous acidic baths.
  • the object of this invention is the production of semibright low stress, fine-grained nickel plate.
  • concentrations of zinc ion may reach values as high as about 0.2 gram per liter without any darkness in the low current density areas.
  • Table I are listed a number of representative examples of these new compounds which are encompassed by the following formula (or the Ni, Co, Na, K, Li, Mb, etc., isulfonate salts) wherein R is selected from the substituents H, OH, Cl, Br, 80 1-1, and CH n is an integer from 1 to 4 inclusive, n is 0 or 1, n is zero, 1, or 2, and when n is 0, n is 0.
  • the concentration of bone acid or its I (o)"1 i SO3H equivalent should be above about grams per l1ter
  • the baths may include various supplemental in which the symbols R and m, n and n are as previously agents, such as anti-pitting agents, which are now condefined. 10 ventionally employed in this art, and as more particularly In Table II are listed some representative examples suggester hereinafter. of these compounds. Besides the use of these compounds 1n acidic nickel TABLE II Useful Concentration grams/liter on CHzCHCHzSOsH I 1 SOz-NC 0.1-saturation.
  • this invention consists of the use in acidic nickel baths of the sulfonic and/or sulfonates covered by the more general formula n is zero, 1 or 2, and when n is zero then n is zero.
  • A may be separate rings or a single ring, for example, in the N-substituted compounds of Table I, the A substituent attached to SO and CO is a common substituent, namely a single benzene ring.
  • the aqueous nickel plating baths which are improved by the use of the addition agents of this invention may be of various types but, in all cases, are acidic in character.
  • the preferred baths are those of the Watts type or modifications thereof.
  • the nickel salts may comprise nickel sulfate, nickel chloride, nickel fluoborate and nickel sulfamate, or other nickel salts or mixtures of any two or more of said nickel salts, preferably in conjunction with buffer materials as, for example, boric acid, the preferred buffer.
  • nickel salts which may be employed are quantities which are now conventional in plating baths to give low stress or compressively stressed, fine-grained, semi-bright nickel plate which is useful in decorative plating where a satin or a semi-bright finish is desired, there are also many engineering uses, such as in electroforming, magnetic films, printed circuits, etc., where low stress and fine-grained plate is important. Additionally, there is the important use of these new sulfonic acid compounds together with strongly unsaturated compounds or amines to produce brilliant, high leveling nickel plate from acidic nickel plating baths.
  • the sulfonic acid compounds of this invention can be used in low concentrations of about 0.05 gram per liter with improved results in the low current density plating ranges. In general for the Widest plating range, about 0.1 g./l. to 3 grams per liter is the optimum concentration range for these sulfonic compounds. These sulfonic compounds have, however, no critical upper limit of concentration, and can be used up to saturation concentration values. They are completely compatible in the nickel baths with other organic sulfon-compounds such as those shown in Table II of US. 2,800,442, issued July 23, 1957. They are usually prepared as the sodium salt or the nickel salt, and after adding the compounds to the acidic nickel baths, they are present mainly as the nickel salt and the free acid.
  • Concentrations of ferrous salts such as ferrous sulfate, chloride, or fluoborate may be as high as at least 40 grams per liter ithout harmful effect on the appearance of the plate, and the alloy plates electrodeposited therefrom contain at least 40% of iron. Even higher concentrations of similar cobalt salts may be used in the nickel bath and the appearance of the plate is excellent even when the cobalt is at least 50% of the alloy plate. Moreover, mixtures of cobalt and iron salts can be used to give ternary alloy plates of excellent appearance and properties even when the nickel present in the alloy plate is as low as about 50%.
  • the baths as exemplified by A, B, and C can be operated with or without air agitation. It is preferred to use agitation when feasible whether it is air agitation or cathode rod agitation. With very rapid agitation, very high current densities can be used, for example, at least 500 to 1,000 amps/sq. ft. (approximately 50 to 100 amps/ sq. dm.). With air agitation, a low foaming wetting agent such as sodium 2-ethylhexyl sulfate or n-octyl sulfate or a mixture may be used. Without air agitation the longer chain surface-active agents, such as sodium lauryl sulfate, are preferred.
  • Example C Grams/liter NiSO .6H O 150-400 NiCl .6H O 30-100 H BO 40-45 (])H CHgCHCHgSOaH I a Q- -Q pH 1.5 to 6.0, temp. room to 75 C. Av. cathode current density, 0.5 to 10 amps/ sq. dm.
  • Example D Grams/liter NiSO .6H O -400 NiCl .6H O 250-30 H BO 40-50 pH to 2.8 to 5, temp. 50 to 70 C.
  • the compounds of Tables I and II give further improved fine-grained plate when used in conjunction with about 0.3 to 4 grams per liter of allyl sulfonic acid.
  • an unsaturated compound such as N-allyl quinaldinium bromide, polyalkylene amine, or butynoxy ethane sulfonic acid is also added to the nickel bath, a very bright, ductile plate is obtained over a very Wide plating range.
  • a bath for electrodepositing fine-grained nickel plate 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 sulfamate, and containing dissolved in said nickel plating solution in a concentration of about 0.05 gram per liter to saturation, an organic sulfonic acid compound in accordance with the formula Ii 3.
  • a bath for electrodepositing fine-grained nickel plate in accordance with claim 1, and wherein said sulfonic acid compound is CH2CHOHCH2SO3H 5.
  • a method for electrodepositing fine-grained nickel comprising the step of electrodepositing nickel from an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fiuoborate, and nickel sulfamate, and containing dissolved in said nickel plating solution in a concentration of about 0.05 gram per liter to saturation, an organic sulfonic acid compound in accordance with the formula 09 i S i N-CgHaSOaH 7.
  • a method for electrodepositing fine-grained nickel comprising the step of electrodepositing nickel from an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fluoborate, and nickel sulfamate, and containing dissolved in said nickel plating solution in a concentration of about 0.05 gram per liter to saturation, an organic sulfonic acid compound in accordance with the formula References Cited by the Examiner FOREIGN PATENTS 8/1939 Canada. 3/1954 Germany.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Description

United States Patent Ofi 3,220,940 Patented Nov. 30, 1965 3,220,940 ELECTRODEPOSITION OF NICKEL Henry Brown, Huntington Woods, Donald H. Becking, Birmingham, and Richard M. Stevenson, Grosse Pointe Woods, Mich., assignors to The Udylite Research Corporation, Detroit, Mich., a corporation of Michigan No Drawing. Filed Feb. 7, 1962, Ser. No. 171,566
Claims. (Cl. 204-49) This invention relates to the electrodeposition of nickel from aqueous acidic baths.
The object of this invention is the production of semibright low stress, fine-grained nickel plate.
While many aryl sulfonic acids and aryl sulfon-compounds have been found to produce fine-grained semibright nickel plate from Watts baths, there is nevertheless need for improved results. For example, while 0- benzoyl sulfimide, is one of the best, if not the best, of the aryl sulfon-compounds, in producing semi-bright finegrained ductile nickel, it nevertheless makes the Watts bath sensitive to quite low concentrations (0.03 gram per liter) of dissolved zinc impurity, causing dark streaks in the low current density areas.
We have now found that by replacing the imide hydrogen of o-benzoyl sulfimide with a short chain aliphatic sulfonic acid radical, the sensitivity of the Watts bath to low concentrations of zinc ions is eliminated. Thus the nickel baths containing these new derivatives of o-benzoyl sulfimide can be used much more effectively in the plating of zinc die castings or other zinc surfaces, which are first copper, brass or nickel plated from an alkaline bath, without serious problems arising from concentrations of zinc impurity accumulating in the Watts bath to values higher than about 0.03 gram per liter. Actually with these new improved sulfonic acid compounds, concentrations of zinc ion may reach values as high as about 0.2 gram per liter without any darkness in the low current density areas. In Table I are listed a number of representative examples of these new compounds which are encompassed by the following formula (or the Ni, Co, Na, K, Li, Mb, etc., isulfonate salts) wherein R is selected from the substituents H, OH, Cl, Br, 80 1-1, and CH n is an integer from 1 to 4 inclusive, n is 0 or 1, n is zero, 1, or 2, and when n is 0, n is 0.
TABLE IC0ntinued Useful Concentration grams/liter 2 S 11 3 NCH2OHCH2SO3H 0.1-saturation.
C ll 0 4 N0I-IzCH2OH2SO3H (ll-saturation.
C H O 5 NC2H4O Cali-1803B: 0.1-saturation.
O H O O 2 S (I31 6 NC H2 C I-I-C HgS O N2; (ll-saturation.
C II 0 Not only is the effectiveness of o-benzoyl sulfimide in Watts nickel baths improved by the above substitution of the short chain aliphatic sulfonic acid radical for the imide hydrogen, but also improved by similar imide hydrogen substitution are the following very slightly bath soluble compounds designated by the formula QQ Q 3 are much more effective in the acidic nickel baths when the imide hydrogen is replaced by the aliphatic sulfonic radical represented by the following formula this art for such baths. Other buffers of acidic character may be employed, however, such as, for example, formic acid, fluoboric acid and the like, and such may be used either in place of or in conjunction with boric acid. For
B J 5 optimum results, the concentration of bone acid or its I (o)"1 i SO3H equivalent should be above about grams per l1ter,
H a particularly when the baths are operated at elevated temperatures. The baths may include various supplemental in which the symbols R and m, n and n are as previously agents, such as anti-pitting agents, which are now condefined. 10 ventionally employed in this art, and as more particularly In Table II are listed some representative examples suggester hereinafter. of these compounds. Besides the use of these compounds 1n acidic nickel TABLE II Useful Concentration grams/liter on CHzCHCHzSOsH I 1 SOz-NC 0.1-saturation.
C2H4SO3H I I i 2 C1 SO2-NC 0.1-saturation.
CZHGSOQH l t 3 CH3C -SO2NC 0.1-saturation.
CzH4O C2H4SO3H l i 4 SO2NCC1 0.1-saturation.
sioarr OH CH-CI-I2SO H I i 5 SO2NO 0.1-saturation.
Thus, this invention consists of the use in acidic nickel baths of the sulfonic and/or sulfonates covered by the more general formula n is zero, 1 or 2, and when n is zero then n is zero.
The dotted line signifies that A may be separate rings or a single ring, for example, in the N-substituted compounds of Table I, the A substituent attached to SO and CO is a common substituent, namely a single benzene ring.
The aqueous nickel plating baths which are improved by the use of the addition agents of this invention may be of various types but, in all cases, are acidic in character. The preferred baths are those of the Watts type or modifications thereof. The nickel salts may comprise nickel sulfate, nickel chloride, nickel fluoborate and nickel sulfamate, or other nickel salts or mixtures of any two or more of said nickel salts, preferably in conjunction with buffer materials as, for example, boric acid, the preferred buffer. The amounts of such nickel salts which may be employed are quantities which are now conventional in plating baths to give low stress or compressively stressed, fine-grained, semi-bright nickel plate which is useful in decorative plating where a satin or a semi-bright finish is desired, there are also many engineering uses, such as in electroforming, magnetic films, printed circuits, etc., where low stress and fine-grained plate is important. Additionally, there is the important use of these new sulfonic acid compounds together with strongly unsaturated compounds or amines to produce brilliant, high leveling nickel plate from acidic nickel plating baths.
The sulfonic acid compounds of this invention can be used in low concentrations of about 0.05 gram per liter with improved results in the low current density plating ranges. In general for the Widest plating range, about 0.1 g./l. to 3 grams per liter is the optimum concentration range for these sulfonic compounds. These sulfonic compounds have, however, no critical upper limit of concentration, and can be used up to saturation concentration values. They are completely compatible in the nickel baths with other organic sulfon-compounds such as those shown in Table II of US. 2,800,442, issued July 23, 1957. They are usually prepared as the sodium salt or the nickel salt, and after adding the compounds to the acidic nickel baths, they are present mainly as the nickel salt and the free acid. Concentrations of ferrous salts, such as ferrous sulfate, chloride, or fluoborate may be as high as at least 40 grams per liter ithout harmful effect on the appearance of the plate, and the alloy plates electrodeposited therefrom contain at least 40% of iron. Even higher concentrations of similar cobalt salts may be used in the nickel bath and the appearance of the plate is excellent even when the cobalt is at least 50% of the alloy plate. Moreover, mixtures of cobalt and iron salts can be used to give ternary alloy plates of excellent appearance and properties even when the nickel present in the alloy plate is as low as about 50%.
In the absence of secondary brightening agents such as amines, unsaturated comlpounds, etc., high concentrations of such cations as Na+, Li+, K NH Mg++, may also be present in the nickel baths and good plate can be obtained in the presence of the sulfonic acid compounds of this invention.
The baths as exemplified by A, B, and C can be operated with or without air agitation. It is preferred to use agitation when feasible whether it is air agitation or cathode rod agitation. With very rapid agitation, very high current densities can be used, for example, at least 500 to 1,000 amps/sq. ft. (approximately 50 to 100 amps/ sq. dm.). With air agitation, a low foaming wetting agent such as sodium 2-ethylhexyl sulfate or n-octyl sulfate or a mixture may be used. Without air agitation the longer chain surface-active agents, such as sodium lauryl sulfate, are preferred.
Example A Grams/liter NiSO .6H O 150-400 NiCl .6H O 30-50 H BO 40-45 NC H SOaI-I 0.05-3
pH 2.0 to 5.5, temp. room to 70 C. Av. cathode current density, 0.5 to arnps/ sq. dm.
Example B Grams/liter NiSO .6H O 50-40'0 NiCl .6H O 200- H BO -45 NaBR, 1-6
N-CH CH CH SO H 0.1-4
pH 2.0 to 5.5, temp. room to 70 C. Av. cathode current density, 0.5 to 10 amps/ sq. dm.
Example C Grams/liter NiSO .6H O 150-400 NiCl .6H O 30-100 H BO 40-45 (])H CHgCHCHgSOaH I a Q- -Q pH 1.5 to 6.0, temp. room to 75 C. Av. cathode current density, 0.5 to 10 amps/ sq. dm.
Example D Grams/liter NiSO .6H O -400 NiCl .6H O 250-30 H BO 40-50 pH to 2.8 to 5, temp. 50 to 70 C. Av. Cathode current density, 2 to 10 :amps/ sq. dm.
In particular, the compounds of Tables I and II give further improved fine-grained plate when used in conjunction with about 0.3 to 4 grams per liter of allyl sulfonic acid. In addition, if an unsaturated compound such as N-allyl quinaldinium bromide, polyalkylene amine, or butynoxy ethane sulfonic acid is also added to the nickel bath, a very bright, ductile plate is obtained over a very Wide plating range.
What is claimed is:
1. A bath for electrodepositing fine-grained nickel plate 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 sulfamate, and containing dissolved in said nickel plating solution in a concentration of about 0.05 gram per liter to saturation, an organic sulfonic acid compound in accordance with the formula Ii 3. A bath for electrodepositing fine-grained nickel plate in accordance with claim 1 and wherein said sulfonic acid compound is N-CsHeSOaH 4. A bath for electrodepositing fine-grained nickel plate in accordance with claim 1, and wherein said sulfonic acid compound is CH2CHOHCH2SO3H 5. A method for electrodepositing fine-grained nickel comprising the step of electrodepositing nickel from an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fiuoborate, and nickel sulfamate, and containing dissolved in said nickel plating solution in a concentration of about 0.05 gram per liter to saturation, an organic sulfonic acid compound in accordance with the formula 09 i S i N-CgHaSOaH 7. A method for electrodepositing fine-grained nickel in accordance with claim 5, and wherein said sulfonic acid compound is 0 ll 0 8. A method for electrodepositing fine-grained nickel in accordance with claim 5, and wherein said sulfonic acid compound is OHzCHOHOH2S0aH 9. A bath for electrodepositing fine-grained nickel plate 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 4 3 sulfamate, and containing dissolved in said nickel plating solution in a concentration of about 0.05 gram per liter to saturation, an organic sulfonic acid compound in accordance with the formula wherein A is selected from the group consisting of the benzene, biphenyl and naphthalene rings, R is selected from the group consisting of H, OH, Cl, Br, SO H and CH n is an integer from 1 to 4 inclusive, n is 0 to 1, n is zero, 1 or 2, and when n is zero then n is zero, and allyl sulfonic acid in a concentration in the range of about 0.3 to 4 grams per liter.
10. A method for electrodepositing fine-grained nickel comprising the step of electrodepositing nickel from an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fluoborate, and nickel sulfamate, and containing dissolved in said nickel plating solution in a concentration of about 0.05 gram per liter to saturation, an organic sulfonic acid compound in accordance with the formula References Cited by the Examiner FOREIGN PATENTS 8/1939 Canada. 3/1954 Germany.
JOHN H. MACK, Primary Examiner.
MURRAY TILLMAN, Examiner.

Claims (1)

  1. 5. A METHOD FOR ELECTRODEPOSITING FINE-GRAINED NICKEL COMPRISING THE STEP OF ELECTRODEPOSITING NICKEL FROM AN AQUEOUS ACIDIC SOLUTION OF AT LEAST ONE NICKEL SALT SELECTED FROM THE GROUP CONSISTING OF NICKEL SULFATE, NICKEL CHLORIDE, NICKEL FLUOBORATE, AND NICKEL SULFAMATE, AND CONTAINING DISSOLVED IN SAID NICKEL PLATING SOLUTION IN A CONCENTRATION OF ABOUT 0.05 GRAM PER LITER TO SATURATION, AN ORGANIC SULFONIC ACID COMPOUND IN ACCORDANCE WITH THE FORMULA
US171566A 1962-02-07 1962-02-07 Electrodeposition of nickel Expired - Lifetime US3220940A (en)

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US171566A US3220940A (en) 1962-02-07 1962-02-07 Electrodeposition of nickel
GB1646/63A GB1010567A (en) 1962-02-07 1963-01-14 Improvements in or relating to the electrodeposition of nickel
DEU9555A DE1237870B (en) 1962-02-07 1963-02-04 Acid galvanic nickel bath
FR923789A FR1348066A (en) 1962-02-07 1963-02-05 Improvements to electrolytic nickel deposition baths

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3336658A (en) * 1963-12-06 1967-08-22 Rca Corp Superconductive articles
US3386897A (en) * 1964-09-15 1968-06-04 Barnet D. Ostrow Electroplasting bright nickel
US3655532A (en) * 1970-05-06 1972-04-11 Metalux Corp The Method for electroplating nickel
US4046647A (en) * 1976-06-17 1977-09-06 M&T Chemicals Inc. Additive for improved electroplating process
US4430171A (en) 1981-08-24 1984-02-07 M&T Chemicals Inc. Electroplating baths for nickel, iron, cobalt and alloys thereof
US5378720A (en) * 1991-12-19 1995-01-03 Sterling Winthrop Inc. Saccharin derivative proteolytic enzyme inhibitors
US6045682A (en) * 1998-03-24 2000-04-04 Enthone-Omi, Inc. Ductility agents for nickel-tungsten alloys

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5209899A (en) * 1990-10-25 1993-05-11 General Electric Company Composite spacer with inconel grid and zircaloy band

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA459339A (en) * 1949-08-30 The Udylite Corporation Electrodeposition of nickel from acid bath
DE907892C (en) * 1941-08-24 1954-03-29 Boehme Fettchemie G M B H Process for the production of sulfonates

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE528458A (en) * 1953-07-20

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA459339A (en) * 1949-08-30 The Udylite Corporation Electrodeposition of nickel from acid bath
DE907892C (en) * 1941-08-24 1954-03-29 Boehme Fettchemie G M B H Process for the production of sulfonates

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3336658A (en) * 1963-12-06 1967-08-22 Rca Corp Superconductive articles
US3386897A (en) * 1964-09-15 1968-06-04 Barnet D. Ostrow Electroplasting bright nickel
US3655532A (en) * 1970-05-06 1972-04-11 Metalux Corp The Method for electroplating nickel
US4046647A (en) * 1976-06-17 1977-09-06 M&T Chemicals Inc. Additive for improved electroplating process
US4430171A (en) 1981-08-24 1984-02-07 M&T Chemicals Inc. Electroplating baths for nickel, iron, cobalt and alloys thereof
US5378720A (en) * 1991-12-19 1995-01-03 Sterling Winthrop Inc. Saccharin derivative proteolytic enzyme inhibitors
US5466701A (en) * 1991-12-19 1995-11-14 Sterling Winthrop Inc. Saccharin derivative proteolytic enzyme inhibitors
US6045682A (en) * 1998-03-24 2000-04-04 Enthone-Omi, Inc. Ductility agents for nickel-tungsten alloys

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DE1237870B (en) 1967-03-30
GB1010567A (en) 1965-11-17

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