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

• This invention relates to the electrodeposition of nickel and more specifically to a process of electrodepositing nickel, and to a solution for use in a process for electrodepositing nickel.
• the invention has to do with the discovery of cooperating brightening agents suitable for use in aqueous acid nickel plating solutions where the solution contains a nickel electrolyte selected from nickel sulfate and nickel chloride and mixtures thereof.
• nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures of nickel sulfate and nickel chloride if the solution also contains an effective amount of each of two cooperating addition agents.
• One of the cooperating addition agents has an internal sulfur atom in the organic molecule and is characterized by a solubility in the plating solution of at least 0.00.05 gram per liter and the following characteristic structure:
• X is a member selected from the group consisting of and n and m are integers from 1 to 4, and A is a member selected from the group consisting of H, CN--, CN-(CH O-, where p is an integer from 1 to 4, CN-(CH X-, where p is an integer from 1 to 4 and Where X is a member selected from the group consisting of and B is a member selected from the group consisting of --CN, CN(CH -O, where p is an integer from 1 to 4 and CN(CH -X, where p is an integer from 1 to 4 and X is a member selected from the group consisting of
• the preferred types are the symmetrical forms NC-(OH --X-(CH ),,CN
• X is a member selected from the group consisting of O, and S-- and n is an integer from 1 to 4, which may be called sulfonylalkylene uitriles and sulfinylalkyleue nitriles.
• brighteners The addition agents falling within this classification will hereafter be referred to as brighteners.
• Typical brighteners according to the invention are indicated in Table I.
• the optimum range of each brightener which should be dissolved in the plating solution is also indicated in Table I in grams of brightener per liter of plating solution. They may be used in the plating solution in concentration from 0.0005 to 0.10 gram per liter.
• NCCH2CHzS-CH2CH2CN NCCH2CHzS-CH2CH2CN (4) B-cyanoethyl propyl sulioxide 0. 008-0. 05
• NC--CH1CHz-OCH1CH2fiCHzCHzO-CH:CH2CN carrier is dissolved in the plating solution in amounts from about 2 to about 5 grams per liter.
• the organic sulfonates, sulfimides and sulfonamides comprise aromatic and unsaturated aliphatic sulfonates, sulfonamides, and sulfimides.
• aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides are included the acids and their salts such as the sodium, potassium, nickel, cobalt, and iron salts thereof.
• the class includes aryl and unsaturated alkyl sulfonates, sulfimides and sulfonarnides, and the foregoing salts thereof wherein the number of carbon atoms in any aryl nucleus is from 6 to 10 and in any unsaturated alkyl group is from 1 to 10, and substitution products of the foregoing wherein the substituents are chosen fromthe class of alkyl groups having 1 to 4 carbon atoms, chlorine, CH0 and phenyl.
• organic sulfonamides, sulfimides, and sulfonates are frequently referred to as carriers or control agents in the art of nickel plating, and accordingly, are sometimes so-called herein. These carriers produce a degree of brightness without a cooperating brightener. Nevertheless, they do not produce suflicient brightness when uti-' lized as the sole brightening additive in acid nickel plating solutions to be considered as producing a full, bright plate.
• the carriers or control agents constituting this second class of addition agents have a minimum solubility in the plating solution (for example, in a solution consisting of 240 grams of NiSO .6H O, 37.5 grams of NiCl .6H 0, 37.5 grams of H BO and water to make a liter) to the extent of at least 0.05 gram per liter.
• Typical compounds illustrating the aryl and unsaturated alkyl sulfonamides, sulfimides and sulfonates are set forth in Table II. With respect to the aromatic sulfonic acids and sulfonamides and sulfimides various substituents in the ring structure are evident in the formulas in-' dicated.
• the brightening addition agent should be dissolved in.
• the constituents of the plating bath are (1) water, (2) nickel sulfate, nickel chloride, or a mixture of nickel sulfate and nickel chloride, (3) the brightener, (4) a sulfonate, a sulfonamide, a sulfimide, or one or more sulfonates, sulfonamides, sulfimides or mixtures thereof of the type previously indicated, and (5) and a wetting agent (optional).
• An additional ingredient of the solution which is desirable is a buffering agent such as boric acid, formic acid, or the like.
• the essential novel feature of the invention is the use of an acid nickel plating solution having one or more nickel electrolytes selected from nickel sulfate and nickel chloride and additionally containing cooperating brightening agents, one of which is at least one carrier selected from the group consisting of unsaturated aliphatic sulfonamides, unsaturated aliphatic sulfimides, unsaturated aliphatic sulfonates, aromatic sulfonamides, aromatic sulfimides and aromatic sulfonates, and the other of which is a small amount of a brightener of the type heretofore indicated.
• Wetting agent e.g. sodium lauryl sulfate
• Wetting agent 0 to 0.5 grams, preferably 0.05 to 0.2 H20 to make 1000 cc.
• ALL CHLORIDE Wetting agent e.g. sodium lauryl sulfate
• Wetting agent 0 to 0.5 grams, preferably 0.05 t 0.2 120 to make 1000 cc.
• Wetting agent e.g. sodium sulfate derivative of 'I-ethyl- 2-methyl-undecanol-4) 0 to 0.5 gram, preferably 0.025 to 0.2 gram. H20 to make 1000 cc.
• the plating solutions above identified may be operated under conditions of pH, temperature, and cathode current density which are customarily employed therewith.
• the cooperating brightening agents of the invention are dissolved in the plating solutions in the amount previously indicated, bright, ductile deposits Will be obtained upon electrolysis of the solution.
• Typical operating conditions for the basic solutions are as follows:
• electroplating solutions containing different cooperating brighteners and carriers are illustrated in. Table III.
• the operating conditions for obtaining bright ductile nickel deposits are also set forth in the table.
• a bright nickel deposit of from .05 to about 1 mil thick or thicker may be secured by electrolyzing the electroplating solution between an anode and a buffed brass cathode. Similar results may be secured on other types of cathodes conventionally employed in acid nickel plating processes utilizing solutions of the type indicated herein.
• substituents are alkylv or acyl groupsnot exceeding 4' carbon atoms, halogen, hydroxy or carboxy groups maybe employed.
• Typical examples of substituted coumarins are 4-methyl coumarin, 6-chloro coumarin, 3- acetyl coumarin, coumarin-3-carboxylic acid, 4,8-dimethyl coumarin, 7-hydroxy coumarin, 6-carboxy coumarin, 3- chloro coumarin, 3-bromo coumarin, and 3-methyl coumarin.
• coumarin or its said derivatives may be dissolved .in the nickel plating solutions containing the cooperating brightening agents and found to exert a leveling or smoothing action such that bright, ductile, nickel deposits of excellent smoothness are obtained.
• Nickel Chloride g./l Boric Acid, g./l Allyl Sulfonic Acid, g./l
• Dibenzenesulfonamide ether g./1 Sacoharin (sodium salt), g./l Toluene sulfonamide, g./l -t Bis(B-cyanoethyl)sulione, g./l 1,4-Bis(B-cyanoethylsulfonyl) butane, a ll Bis(B-cyanoethy1) sulfoxide, g./l
• B-cyanoethyl propyl sulfoxide g./l
• B-cyanoethyl B-cyanoethoxyethyl sulfone, g./l
• Nickel Sulfate g./l Nickel Fluoborate, g./l
• Dibenzenesulfonamide ether g./l 3 Saccharin (sodium salt), g./l 2 Toluene sulfonamide, g./l Bis(B-cyanoethyl)sulfone, ll
• X is a member selected from the group consisting of and n and m are integers from 1 to 4, and A is a member selected from the group consisting of H, CN, CN(CH O-, where p is an integer from 1 to 4, CN(CH -X, where p is an integer from 1 to 4 and where X is a member selected from the group consisting of and B is a member selected from the group consisting of --CN, CN-(C z) Where p is an integer from 1 to 4, and CN(CH Where p is an integer from 1 to 4 and X is a member selected from the group consisting of i -s 0 II ll 0 and -S the first said brightening addition agent being present in said solution to the extent of from .05 to 20 grams perliter and the second said brightening addition agent being present in said solution to the extent of from 0.0005 to 0.10 gram per liter. l
• a nickel electroplating bath comprising an aqueous solution of a nickel electrolyte selected from the group] j consisting of nickel sulfate, nickel chloride, and mixtures thereof, said solution'also containing cooperatingbright: H
• one of said brightening addition agents being at least one organic compound selected from the group consisting of aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides and the second of" said agents being a compound of the formula 8.. of said brightening addition agents being a compound of the formula wherein n is an integer from 1 to 4, the first said brightening addition agent being present in said solution to the extent of from .05 to 20 grams per liter and the second said brightening addition agent being present in said solution to the extent of from 0.0005 to 0.10 gram per liter.
• a nickel electroplating bath comprising an aqueous solution of a nickel electrolyte selected from the group consisting of nickel sulfate, nickel chloride, and mixtures thereof, said solution also containing cooperating brightening addition agents, one of said brightening addition agents being at least one organic compound selected from the group consisting of aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides and the second of said brightening addition agents being a compound of the formula wherein n is an integer from 1 to 4, the first said brightening addition agent being present in said solution to the extent of from .05 to 20 grams per liter and the second said brightening addition agent being present in said solution to the extent of from 0.0005 to 0.10 gram per liter.
• An acid nickel electroplating solution comprising in addition to Water, nickel sulfate equivalent to from 100 to 400 grams per liter of NiSO -7H O, nickel C1110? ride equivalent to from 10 to 60 grams per liter of NiCl -6H O, a buffering agent and cooperating, brighten ing addition agents, one of said brightening addition agents being a compound selected from the group consisting of aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides and the second of said brightening addition agents being Bis(B-cyanoethyl) sulfone, the first said brightening addition agent being present in said solution to the extent of from 0.05 to 20 grams per liter and the second said brightening addition agent being present in said solution to the extent of from 0.005 to 0.03 gram per liter.
• An acid nickel electroplating solution comprising in addition to water, nickel sulfate equivalent to from 100 to 400 grams per liter of NiSO -7H O, nickel chlo- Q ride equivalent to from 10 to 60 grams per liter of NiCl -6H O, a buffering agent and cooperating, brightening addition agents, one of said brightening addition and n is an integer from 1 to 4, the first said brightening addition agent being present in said solution to the extent of from .05 to 20 grams per liter and the second said brightening addition agent being present in said solution a to the extent of from 0.0005 to 0.10 gram per liter.
• a nickel electroplating bath comprising an aqueous '7 solution of a nickel electrolyte selected from the group consisting of nickel sulfate, nickel chloride, and mixtures thereof, said solution also containing cooperating'brightening addition agents, one of said brightening addition agents being at least one organic compound selected from the group consisting of aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides and t e second agents being a compound selected from the group consisting of aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides and the second of said brightening addition agents being a 1,4-Bis(B-cyanoethy1- sulfonyl) butane, the first said brightening addition agent being present in said solution to the extent of from 0.05 to 20 grams per liter and the second said brightening addition agent being present in said solution to the extent of from 0.005 to 0.03
• An acid nickel electroplating solution comprising in addition to Water, nickel sulfate equivalent to from to 400 grams per liter of NiSO -7H O, nickel chlo ride equivalent to from 10 to 60 grams per liter of NiCl -6H O, a buffering agent and cooperating, brightening addition agents, one of said brightening addition agents being a compound selected from the group consisting of aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides and the second of said brightening addition agents being a Bis(B-cyanoethyl) sulfoxide, the first said brightening addition agent being present in said solution to the extent of from 0.05 to 20 grams per liter and the second said brightening addition agent being prment in said solution to the extent Of from 0.0005 to 0.006 gram per liter.
• An acid nickel electroplating solution comprising in addition to water, nickel sulfate equivalent to from 100 to 400 grams per liter of NiSO -7H O, nickel chloride equivalent to from to 60 grams per liter of NiCl -6H O, a buffering agent and cooperating, brightening addition agents, one of said brightening addition agents being a compound selected from the group consisting of aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides and the second of said brightening addition agents being a B-cyanoethyl propyl sulfoxide, the first said brightening addition agent being present in said solution to the extent of from 0.05 to 20 grams per liter and the second said brightening addition agent being present in said solution to the extent of from 0.0005 to 0.006 gram per liter.
• An acid nickel electroplating solution comprising in addition to water, nickel sulfate equivalent to from 100 to 400 grams per liter of NiSO -7H O, nickel chloride equivalent to from 10 to 60 grams per liter of NiCl -6H O, a bufiering agent and cooperating, brightening addition agents, one of said brightening addition agents being a compound selected from the group consisting of aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides and the second of said brightening addition agents being a B-cyanoethyl B-cyanoethoxyethyl sulfone, the first said brightening addition 10 agent being present in said solution to the extent of from 0.05 to 20 grams per liter and the second said brightening addition agent being present in said solution to the extent of from 0.0005 to 0.006 gram per liter.
• An acid nickel electroplating solution comprising in addition to water, nickel sulfate equivalent to from 100 to 400 grams per liter of NiSO -7H O, nickel chloride equivalent to from 10 to grams per liter of NiCl -6H O, a buffering agent and cooperating, brightening addition agents, one of said brightening addition agents being a compound selected from the group consisting of aromatic and unsaturated aliphatic sulfonates, sulfonamides and sulfimides and the second of said brightening addition agents being a Bis(B-cyanoethoxyethyl) sulfone, the first said brightening addition agent being present in said solution to the extent of firom 0.05 to 20 grams per liter and the second said brightening addition agent being present in said solution to the extent of from 0.0005 to 0.006 gram per liter.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Electroplating And Plating Baths Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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  • NL NL263657D patent/NL263657A/xx unknown
  • NL NL126849D patent/NL126849C/xx active
• 1960
  • 1960-04-22 US US23900A patent/US2994648A/en not_active Expired - Lifetime
• 1961
  • 1961-04-04 GB GB12042/61A patent/GB898774A/en not_active Expired
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