US3697391A - Electroplating processes and compositions - Google Patents

Electroplating processes and compositions Download PDF

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Publication number
US3697391A
US3697391A US55959A US3697391DA US3697391A US 3697391 A US3697391 A US 3697391A US 55959 A US55959 A US 55959A US 3697391D A US3697391D A US 3697391DA US 3697391 A US3697391 A US 3697391A
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Prior art keywords
nickel
cobalt
sulfonate
plating
brightener
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Frank Passal
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M&T Chemicals Inc
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M&T Chemicals Inc
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    • 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
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

Definitions

  • This invention relates to improved processes and compositions for the electrodeposition of nickel, cobalt, and alloys thereof. More particularly, this invention relates to the use of new additives to improve the tolerance of nickel, cobalt, and alloy plating baths containing nickel and/or cobalt to the adverse effects of both metallic impurities and relatively high concentrations of primary brighteners.
  • the impurities may be introduced when commercial grade salts are used to prepare the bath composition, or the metallic impurities may occur as a result of dissolution of parts which may fall into the plating bath composition during the plating process.
  • a special object of this invention is to provide processes and compositions for the production of sound electrodeposits containing nickel and/or cobalt over a wide range of concentrations of primary brighteners and/or metallic impurities.
  • this invention relates to a process for the preparation of an electrodeposit which contains at least one metal selected from the group consisting of nickel and cobalt which comprises passing current from an anode to a cathode through an aqueous plating solution containing a member selected from the group consisting of cobalt compounds and nickel compounds providing cobalt or nickel ions for electrodepositing cobalt or nickel and containing in combination an effective amount of:
  • the substrates on which the nickel-containing, cobaltcontaining, or nickel-cobalt-containing electrodeposits of this invention may be applied may be metal or metal alloys such as are commonly electrodeposited and used in the art of electroplating such as nickel, cobalt, nickelcobalt, copper, tin, brass, etc.
  • Basis metal substrates may have a variety of surface finishes depending on the final appearance desired, which in turn depends on such factors as luster, brilliance, leveling, thickness, etc. of the cobalt or nickel containing electroplate applied on such substrates.
  • Typical substrate basis metals include ferrous metals such as steel; copper; tin; alloys of copper such as brass, bronze, etc.; zinc, particularly in the form of (l) N-l,2-dichloropropenyl pyridinium chloride (2) 2,4,-6-trimethyl N-propargyl pyridinium bromide (3) N-allyl quinaldinium bromide (4) Q-butyne-lA-diol ('5) bis-fi-hydroxyethyl ether of 2-butyne-l,4-diol (6) propargyl alcohol (7) 2-methyl-3-butyn-2-ol (8) thiodipropionitrile CHzCHzCN :i CHzClHgcN (10) phenosafranin 11 fuchsin.
  • a primary brightener When used alone or in combination, a primary brightener may produce. no visual effect on the electrodeposit, or may produce semi-lustrous, fine-grained deposits. However, best results are obtained when primary brighteners are used with either a secondary brightener, a secondary auxiliary brightener, or both in order to provide optimum deposit luster, rate of brightening, leveling, bright plate current density range, low current density coverage, etc.
  • secondary brightener as used herein is meant to include aromatic sulfonates, sulfonamides, sulfonimides, sulfinates, etc. Specific examples of such plating additives are:
  • thiourea (1) saccharin (2). trisodium 1,3,6-naphthalene trisulfonate (3) sodium benzene monosulfonate (4) dibenzene sulfonimide sodium benzene monosulfinate.
  • Such plating additive compounds which may be used singly or in suitable combinations, have one or more of the following functions:
  • secondary auxiliary brightener as used hereinis meant to include aliphatic or aromatic-aliphatic olefinically or acetylenically unsaturated sulfonates, sulfonamides, or sulfonimides, etc. Specific examples of such plating additives are:
  • Such compounds which may be used singly (usual) or in combination have all of the functions given for the secondary brighteners and in addition may have one or more of the following functions:
  • primary brightener (2) secondary brightener; and (3) secondary auxiliary brightener used either alone or in combination.
  • secondary auxiliary brighteners one may also include ions or compounds of certain metals and metalloids such as zinc, cadmium, selenium, etc. which,.
  • compositions of the invention may be especially effective to counteract the effects of excessive primary brighteners.
  • anti-pitting agent as used herein is meant to include a material (different from and in addition to the secondary auxiliary brightener) which functions to prevent or minimize gas-pitting.
  • An anti-pitting agent may also function to make the baths more compatible with contaminants such as oil, grease, etc. by their emulsifying, dispersing, solubilizing, etc. action on such contaminants and thereby promote attaining of sounder deposits.
  • Anti-pitting agents are optional additives which may or may not be used in combination with one or more members selected from the group consisting of a primary brightener, a secondary brightener, and a secondary auxiliary brightener.
  • hydroxy-sulfonate additive compounds of the invention may be prepared according to the following general reaction:
  • M is a cation having a valence of 1-2; preferably M is an alkali metal or alkaline earth metal cation or ammonium; k is an integer 1-2 corresponding to the valence of M; and R is hydrogen or a monovalent aliphatic group of 1-16 carbon atoms.
  • R may be an aliphatic radical preferably selected from the group consisting of alkyl, alkenyl, alkynyl, cycloal'kyl, including such radicals when inertly substituted.
  • R When R is alkyl, it may typically be straight chain alkyl or branched alkyl, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertbutyl, n-amyl, neopentyl, isoamyl, n-hexyl, isohexyl, heptyls, octyls, decyls, dodecyls, tetradecyl, octadecyl, etc.
  • Preferred alkyl includes lower alkyl i.e. having less than about 8 carbon atoms i.e.
  • R alkenyl
  • R alkenyl
  • R alkenyl
  • it may typically be vinyl, allyl, l-propenyl, methallyl, buten-l-yl, buten-Z-yl, buten-3-yl, penten-l-yl, hexenyl, heptenyl, octenyl, decenyl, dodecenyl, tetradecenyl, octadecenyl, etc.
  • R alkynyl
  • it may typicallybe acetylenyl, 2i-propynyl, 3-butynyl, etc.
  • R When R is cycloalkyl, it may typically be cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. R may be inertly substitutedeg. may bear a non-reactive substituent such as alkyl, cycloalkyl, alkenyl, ether, halogen, ester,
  • %O C COOM (wherein M is as previously defined), carboxyl (-COOH), hydroxyl, sulfonate, hydroxy-sulfonate M such as SO H, SOgNa, $0 K, etc.), or other inert or bath-compatible groups, etc.
  • Typical substituted alkyls include 3-hydroxypropyl, 3-chloropropyl, 2-ethoxyethyl, carboethoxymethyl, etc.
  • Substituted alkenyls include 4-hydroxy, 4-chlorobutenyl, -phenylpropenyl, chloroallyl, etc.
  • Substituted alkynyls include 4-hydroxy-3- butynyl, :propargyl, amine, etc.
  • Substituted cycloalkyls include 4-methylcyclohexyl, 4-chlorocyclohexyl, etc.
  • reaction is generally carried out in aqueous media and the reaction products may be left in the form of aqueous stock solutions or the salts may be separated out in crystalline form by evaporation and crystallization or by using organic solvents.
  • Typical examples of this method of preparing the hydroXy-sulfonate additives of the invention herein include the following:
  • the hydroxy-sulfonate additives of the invention may be used in aqueous nickel, cobalt, and nickel-cobalt electroplating bath compositions in combination with one or more'other additives as disclosed herein over fairly wide concentration ranges, typically 0.1-5 g./l. or higher. Preferably, when used with the additives described herein the concentration is about 0.5-2 g./l. While concentrations up to saturation may be used, there is no special advantage obtained thereby and the use of excess amounts generally adds to the operating costs of the bath composition.
  • the hydroxy-sulfonate additives of the invention may be added either as solids or in the form of aqueous stock solutions.
  • Typical nickel-containing, cobalt-containing, and nickelcobalt-containing bath compositions which may be used in combination with effective amounts of about 0.5-5 g./l. of the hydroxy-sulfonate additive compounds and effective amounts of about 0.0050.2 g./l. of the primary brighteners, with about 1.0-30 g./l. of the secondary brightener, with about 0.5-1() g./l. of the secondary auxiliary brightener, and with about 0.05-1 g./l. of anti-pitting agent, described herein are summarized below.
  • Typical aqueous nickel-containing electroplating baths (which may be used in combination with effective amounts of the hydroxy-sulfonate and cooperating additives) include the following wherein all concentrations are in grams per liter (g./l.) unless otherwise indicated:
  • a typical sulfamate-type nickel plating bath which may be used in practice of this invention may include the following components:
  • a typical fluoborate-type nickel plating bath which may be used in the practice of the invention may include the following components:
  • a typical chloride-free sulfamate-type nickel plating bath which may be used in practice of this invention may include the following components:
  • aqueous cobalt-containing and cobalt-nickel-containing electroplating baths in which the combination of elfective amounts of one or more hydroxysulfonates and cooperating additives according to this invention will result in improving the tolerance of the.
  • an iodide ion concentration of 0.5-5 g./l. may be used.
  • 0001:.6Hz0 H B containing compositions maybe maintained during plating at pH values of 2.5 to 5.0, and preferably from about 3.5 to 4.5.
  • the pH may normally tend to rise and may be adjusted with acids such as bydrochloric acidor sulfuric acid, etc.
  • acids such as bydrochloric acidor sulfuric acid, etc.
  • Other buifering components in addition to or in place of boric acid such as formates, citrates, etc. may also be used for buffering if necessary or desirable.
  • a nickel electroplating bath composition was prepared by combining in water the following ingredients to provide the indicated concentrations (in g./l. unless indicated otherwise).
  • a polished brass panel was cleaned and plated in a 267 ml. Hull Cell at 2 amperes cell current for 10] minutes at a temperature of 50 C. and using magnetic stirring.
  • the resulting deposit was uniformly fine-grained, glossy in appearance, with excellent ductility and a uniform milky haze.
  • the equivalent of 0.08 g./1. p.p.m.) of Zn++ as a solution of zinc sulfate and repeating the plating test, the low current density end of the range from about 0 to 1.6 a.s.d. (amperes per square decimeter) was badly striated and dark in color with scattered areas which were very thin in thickness and dark, i.e. where the deposit thickness was substantially lower than on adjacent elevated thicker deposits.
  • Example 1 was repeated using 1 g./l.additive of disodium 1 hydroxy 1,3 propane disultonate in place of additive sodium hydroxymethyl sulfonate with substantially identical beneficial effects attained, the bath being again rendered zinc-tolerant after contamination with zinc ions had previously rendered the bath unsatisfactory for further plating.
  • Example 1 was repeated using 1 g./l. of disodium-asulfo-glycolate additive in place of additive sodium hydroxymethyl sulfonate with substantially identical beneficial effects attained.
  • the regenerated bath composition was rendered zinc-tolerant after addition of 1 g./l. of disodiurn-a-sulfo-glycolate and the bath rendered capable of substantially increased bath life.
  • Example 1 was repeated using 1 g./l. of sodium 1- glycerol sulfonate in place of additive sodium hydroxymethyl sulfonate with substantially identical beneficial results attained.
  • the regenerated bath composition was rendered zinc-tolerant after addition of 1 g./l. of sodium l-glycerol sulfonate.
  • a nickel electroplating bath composition was prepared by combining in water the following ingredients to provide the indicated concentrations (in g./l. unless otherwise indicated).
  • the resulting nickel electrodeposit was brilliant, highly leveled, with excellent ductility and low current density coverage (as evidenced by the extent of the nickel electrodeposit coverage on the back of the panel away from the nickel anode).
  • the plating test was then repeated using an identical clean, polished, brass panel and employing the same plating conditions used prior to contamination of the nickel electroplating bath with zinc ions.
  • the resulting nickel electroplated panel had a dark, thin, and badly striated electrodeposit on the low current density areas of the panel and it was apparent that the low current density coverage had been drastically reduced due to the presence of zinc ion as contaminant.
  • the restored plating bath compositions were heated at 50 for an average of eight hours per day with continuous stirring for a time period of five days. Frequent plating tests using the same conditions and identical panels were carried out with the contaminated restored plating baths to determine the operational characteristics of each restored bath composition. All of the additives showed excellent restoration for at least two days and sodium hydroxymethyl sulfonate was still efiective at the end of the five day period with the restored bath composition still showing excellent zinc tolerance.
  • a nickel electroplating bath composition was prepared by combining in water the following ingredients to provide the indicated concentrations (in g./l. unless otherwise indicated).
  • Example 2 Using the plating conditions set forth in Example 1, a brilliant, well-leveled ductile deposit was obtained, but an area in the low current density end of the panel (corresponding to a current density of from about 0 to 0.8 a.s.d.) was generally thin, dark, non-uniform, and partially striated.
  • the amounts of the last three primary brightener-type additives used were about a 50% excess over optimum'for disulfonate, disodium-a-sulfoglycolate, or sodium l-glycerol sulfonate, resulted in an excellent deposit in the low current density end of the range characterized by excellent luster, coverage, color and uniformity of deposit with the complete absence of thin, dark, striated areas.
  • EXAMPLE 7 A cobalt electroplating bath composition was prepared by combining in water the following ingredients to provide the indicated concentrations (in g./l. unless indicated other-wise) Ingredient: Concentration CoSO -7H O 300 CoC1 -6H O 60 H BO 45 Sodium saccharinate (0.6 mole H O) 3.8
  • EXAMPLE 8 1 A nickel-cobalt alloy electroplating bath was prepared by combining in water the following ingredients to provide the indicated concentrations.
  • M is a cation having a valence of 1-2; k is an integer 1-2 corresponding to the valence of M; and R is hydrogen or a monovalent aliphatic group of 1-16 carbon atoms; for a time period sufiicient to form a metal electroplate upon said cathode surface.
  • M is an alkali metal or alkaline earth metal cation.
  • organic hydroxy-sulfonate compound is selected from the group consisting of sodium hydroxymethyl sulfonate, disodium 1-hydroxy-1,3-propane disulfonate, disodium-a-sulfo-glycolate, and sodium l-glycerol sulfonate.
  • a process for regenerating an aqueous electroplating bath containing at least one member selected from the group consisting of cobalt compounds and nickel compounds providing cobalt or nickel ions for electrodepositing cobalt or nickel which comprises adding an organic hydroxy-sulfonate compound of the formula:
  • M is a cation having a valence of 1-2; k is an integer 1-2 corresponding to the valence of M; and R is hydrogen or a monovalent aliphatic group of 1-16 carbon atoms; in an amount to regenerate said aqueous electroplating bath.
  • an aqueous plating acidic solution containing a member selected from the group consisting of cobalt compounds and nickel compounds providing cobalt or nickel ions for electrodepositing cobalt or nickel and containing an effective amount of at least one additive; the improvement comprising the presence of 0.1 gram per liter to 5 grams per liter of an organic hydroxy-sulfonate compound wherein M is a cation having a valence of 1-2, k is an integer 1-2 corresponding to the valence of M; and R is hydrogen or a monovalent aliphatic group of 1-16 carbon atoms.
  • composition as claimed in claim 6 wherein the organic hydroxy-sulfonate compound is selected from the group consisting of sodium hydroxymethyl sulfonatc, disodium 1-hydroxy-l,3-propane disulfonate, disodium-asulfo-glycolate, and sodium l-glycerol sulfonate.
  • composition as claimed in claim 6 wherein the organic hydroxy-sulfonate is a compound of the formula:
  • M is an alkali metal or ammonium.
  • composition as claimed in claim 6 wherein the organic hydroxy-sulfonate is a compound of the formula:
  • M is an alkali metal or ammonium.
  • composition as claimed in claim 6 wherein the organic hydroxy-sulfonate is a compound of the formula:
  • a regenerated plating bath composition containing at least one member selected from the group consisting of cobalt compounds and nickel compounds providing cobalt or nickel ions for electrodepositing cobalt or nickel which contains an organic hydroxy-sulfonate compound of the formula:

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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)
US55959A 1970-07-17 1970-07-17 Electroplating processes and compositions Expired - Lifetime US3697391A (en)

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JP (1) JPS564635B1 (enExample)
BE (1) BE769960A (enExample)
BR (1) BR7104498D0 (enExample)
CA (1) CA995619A (enExample)
CH (1) CH557887A (enExample)
DE (1) DE2134457C2 (enExample)
FR (1) FR2099425B1 (enExample)
GB (2) GB1366713A (enExample)
NL (1) NL7109852A (enExample)
SE (1) SE7408254L (enExample)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3878123A (en) * 1973-10-10 1975-04-15 Us Agriculture Odor free hydroxymethanesulfonic acid
US3905776A (en) * 1973-07-05 1975-09-16 Nico Magnetics Inc Method of making a thin, ferro-magnetic memory layer and article made thereby
US3922209A (en) * 1974-08-20 1975-11-25 M & T Chemicals Inc Electrode position of alloys of nickel, cobalt or nickel and cobalt with iron and electrolytes therefor
US3969399A (en) * 1970-07-17 1976-07-13 M & T Chemicals Inc. Electroplating processes and compositions
DE2943028A1 (de) * 1978-11-01 1980-05-08 M & T Chemicals Inc Galvanisches nickelbad
US4430171A (en) 1981-08-24 1984-02-07 M&T Chemicals Inc. Electroplating baths for nickel, iron, cobalt and alloys thereof
US20050173254A1 (en) * 2004-02-05 2005-08-11 George Bokisa Nickel cobalt boron ternary alloys
US20050173255A1 (en) * 2004-02-05 2005-08-11 George Bokisa Electroplated quaternary alloys
US20070221506A1 (en) * 2006-03-27 2007-09-27 C. Uyemura & Co., Ltd. Electroplating method

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252619A (en) * 1979-10-24 1981-02-24 Oxy Metal Industries Corporation Brightener for zinc electroplating solutions and process
DK422181A (da) * 1980-10-23 1982-04-24 Hooker Chemicals Plastics Corp Bad og fremgangsmaade til hoejhastigheds-nikkelelektroplettering
DE3726518A1 (de) * 1987-08-10 1989-03-09 Hille & Mueller Kaltband mit elektrolytisch aufgebrachter nickelbeschichtung hoher diffusionstiefe und verfahren zur herstellung des kaltbandes
US5049286A (en) * 1989-12-22 1991-09-17 Omi International Corporation Process for purification of nickel plating baths
DE10025552C1 (de) 2000-05-19 2001-08-02 Atotech Deutschland Gmbh Saures galvanisches Nickelbad und Verfahren zum Abscheiden eines satinglänzenden Nickel- oder Nickellegierungsüberzuges
DE10222962A1 (de) 2002-05-23 2003-12-11 Atotech Deutschland Gmbh Saurer galvanischer Badelektrolyt und Verfahren zur elektrolytischen Abscheidung satinglänzender Nickelniederschläge

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3506548A (en) * 1966-09-23 1970-04-14 Allied Res Prod Inc Electrodeposition of nickel

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3969399A (en) * 1970-07-17 1976-07-13 M & T Chemicals Inc. Electroplating processes and compositions
US3905776A (en) * 1973-07-05 1975-09-16 Nico Magnetics Inc Method of making a thin, ferro-magnetic memory layer and article made thereby
US3878123A (en) * 1973-10-10 1975-04-15 Us Agriculture Odor free hydroxymethanesulfonic acid
US3922209A (en) * 1974-08-20 1975-11-25 M & T Chemicals Inc Electrode position of alloys of nickel, cobalt or nickel and cobalt with iron and electrolytes therefor
DE2537065A1 (de) * 1974-08-20 1976-03-04 M & T Chemicals Inc Verfahren zur elektrolytischen abscheidung von legierungen von nickel, kobalt oder nickel und kobalt mit eisen
DE2943028A1 (de) * 1978-11-01 1980-05-08 M & T Chemicals Inc Galvanisches nickelbad
US4430171A (en) 1981-08-24 1984-02-07 M&T Chemicals Inc. Electroplating baths for nickel, iron, cobalt and alloys thereof
US20050173254A1 (en) * 2004-02-05 2005-08-11 George Bokisa Nickel cobalt boron ternary alloys
US20050173255A1 (en) * 2004-02-05 2005-08-11 George Bokisa Electroplated quaternary alloys
US20070221506A1 (en) * 2006-03-27 2007-09-27 C. Uyemura & Co., Ltd. Electroplating method

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BE769960A (fr)
BR7104498D0 (pt) 1973-07-10
FR2099425B1 (enExample) 1977-01-21
GB1366713A (en) 1974-09-11
DE2134457C2 (de) 1982-06-03
JPS564635B1 (enExample) 1981-01-31
FR2099425A1 (enExample) 1972-03-17
NL7109852A (enExample) 1972-01-19
SE7408254L (enExample) 1974-06-24
CH557887A (de) 1975-01-15
DE2134457A1 (de) 1972-01-20
GB1366714A (en) 1974-09-11
CA995619A (en) 1976-08-24

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