US2392708A - Method of making sulphur-containing nickel anodes electrolytically - Google Patents

Method of making sulphur-containing nickel anodes electrolytically Download PDF

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US2392708A
US2392708A US406115A US40611541A US2392708A US 2392708 A US2392708 A US 2392708A US 406115 A US406115 A US 406115A US 40611541 A US40611541 A US 40611541A US 2392708 A US2392708 A US 2392708A
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nickel
sulphur
anode
anodes
cathode
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Tschop Harry Edwin
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Huntington Alloys Corp
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International Nickel Co 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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • 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

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  • the present invention relates to nickel plating anodes and, more particularly, to electrodeposited nickel plating anodes containing sulphur and a process therefor.
  • the metal should be clean when etched and examined under the microscope, or, if it is not absolutely clean, the
  • Nickel anodes for use in the electrodeposition of these thin films of nickel for protective, and/or decorative purposes generally have a thickness of at least about 5 inch and in many instances a thickness of the order of an inch.
  • the passivposes the thin film or nickel is supported by the base metal and consequently the physical characteristics of the film of nickel do not play such an important part.
  • Nickel anodes on the other hand, must have suflicient strength to support their ownweight and must withstand the usual stresses encountered in shipping and in handling the anodes in and out of the electroplating bath.
  • Nickel anodes therefore of themselves must not be brittle to the degree that the anodes would shatter and become useless during the usual vicissitudes of commercial handling. Furthermore, the problems of depositing thick coatings of nickel are recognized and the experts in the art readily understand and agreethat beyond a certain thickness many problems arise which have not been solved. (Kugel U. 5. Patent No. 665,: 915.)
  • the characteristics of a nickel anode which are of primary importance to the electroplater but do not enter into an evaluation of nickel electrodeposits for decorative and/or protective purposes are the activity of the anode at highpI-I, the character of the corrosion, the amount of sludge, the character of the sludge and the tendency of the sludge from some anodes to become detached from the corroding anode in small pieces which float or migrateto the work'being plated. It will be readily appreciated that the producer of articles electroplated with nickel for protective or decorative purposes usually is not interested in the, foregoing characteristics of the protective or decorative plating.
  • the anode should be soluble in the bath under the plating conditions used-and have a high anode efliciency which means that the pH of the electrolyte can be easily maintained. In maintaining the operating pH of a nickel electroplating bath. it is always desirable "to do this by adding sulphuric acid to the bath seem, therefore, that cathode.
  • a nickel anode must dissolve with a minimum amount of sludge remaining and the I nature of the sludge should be such that all of it can be retained by an anode bag. If bags are not being used, the sludge should adhere to the anode and build up in sufficient thickness in order to entrap any small particles of loose metallics which may come from the anode.
  • a nickel anode should be free from metallurgi cal defects, such as longitudinal or-transverse cracks, commonly termed fire cracks, and slag pockets or gas holes.
  • a. nickel anode should have a size and shape so that a maximum amount of surface is exposed and at the same time require only a small amount of tank space.
  • the shape and size should also notedastobeeasilyhandledandtobe attached to the anode bus bar by means of anode hooks.
  • a' nickel anode' should have a good, clean surface and be free from mechanical and metallurgical defects in the as purchased" condition.
  • the surface layer of an anode should be prepared. either by pickling or “deskinning (ac- I tivating) so that it begins to dissolve immediately when placed in the plating circuit.
  • nickel anodes for use in the production of protective and/0r decorative nickel electroplate have contained addition agents and have not been 0 the highest nickel content possible.
  • the present invention also contemplates a novel nickel electrolyte from'which nickel containing sulphur can be electrodeposited.
  • Figure 1 is a photomicrograph of a transverse section of conventional electrolytic nickel and Figure 2 is a photomicrograph of a transverse section of novel sulphur-containing active electrolytic nickel.
  • the present invention contemplates incorporating in the usual or con ventional or standard or other electrolytic bath for the production of electrolytically deposited nickel anodes, i. e., cathode-nickel anodes, an electrolyte soluble substance containing sulphur which during the electrodeposition of nickel will deposit sulphur with the nickel.
  • nickel anodes i. e., cathode-nickel anodes
  • an electrolyte soluble substance containing containing sulphur which during the electrodeposition of nickel will deposit sulphur with the nickel.
  • anickel anode to provide the good corrosion and activity during subsequent electroplating
  • I have found that certain sulphur-containing materials give satisfactory results whereas others do not.
  • sodium pyrosulphate among the inorganic sulphur-containing compounds which are inefiective is sodium pyrosulphate.
  • sodium thiosulphate is effective.
  • organic substances which are ineffective although containing sulphur are trional and
  • nickel deposited at low pH and high current density from an electrolyte containing sodium sulphite contains no sulphur whereas nickel deposited at high pH and low current density from an electrolyte containing sodium sulphite contains about 0.015% sulphur.
  • nickel electrodeposited at low pH and high cathode currentdensity and nickel electrodeposited at high pH and low cathode current density from nickel electrolytes containing sodium pyrosulphate contain practically no sul-' phur and corroded .unsatisfactorily at pH 4.0 (quinhydrone).
  • sulphur is not deposited with equal facility from all sulphur containing Nor is the mere presence of sulphur an assurance that the nickel deposit containing the sulphur will corrode anodically in a satisfactory manner.
  • sulphur-containing compounds which may be employed for the purpose of introducing into cathode nickel sufllcient sulphur to ensure that the cathode nickel when employed as anode for electroplating for protective and decorative purposes at high pH such as pH 5.5 (quinhydrone) will have good activity are 5 types of sulphur-containing compounds. These sulphur compounds may be classified as (1) sulphonamides or substituted'sulphonamides having the type formula II R- S --NH:
  • R is an aromatic radical such as that of benzene and its homologues and naphthalene and its homologues.
  • These phosphorus and sulphur containing addition agents may be prepared from substances containing a hydroxyl group, such as alcohols or phenols or from substances containing carboxyl groups (COOH) the aldehyde group, (COH) or the ketone group. (C0).
  • the sulphurcontent of the cathode nickel increases first rather rapidly with theconcentration until the concentration of soluble sulphonamide in the electrolyte reaches a value of about 0.35 gram per liter. Thereafter the sulphur content of the cathode nickel increases quite slowly with increased concentration of sulphonamide.
  • the sulphur content of cathode nickel is affected ne ligibly by the cathode current density when this class of sulphur bearing compound is employed.
  • the sulphur content of cathode nickel varies with the pH being high at low pH and low at high pH when sulphonamides or substitutedsulphonamides are employed. In the presence of sulphonamides or substituted sulphonamides the sulphur content of cathode nickel increases with decrease in temperature.
  • the sulphur content of cathode nickel produced in electrolytes containing sodium thiosulphate (1) varies directly with the concentration
  • sulphur-bearing cathodic nickel can be electrodeposited from conventional nickel electrolytes such as electrolytes containing about 84 grams of nickel per liter, about 13 to 14 grams of chloride per liter and about 14 to 15 grams of boric acid per liter and containing about 0.2 of a gram to .about 1 gram per liter of sulphur-bearing electrolyte soluble compound.
  • the electrodeposition' of the novel sulphur-bearing cathodic nickel can be carried out at a pH of about 1.7 to about 5.5 at a temperature of about 20 to about 50 C.
  • the novel sulphur-bearing cathodic nickel or electrolytic nickel'produced in accordance with the foregoing'disclosure has a novel microstructure which readily enables experts in the art to differentiate this novel sulphur-containingelec-f "of regular conventional sulphur-free electrolytic or cathodic nickel and is a typical specimen of regular or conventional sulphur-free electrolytic nickel. Fig.
  • the regular 'or conventional sulphur-free electrolytid'or cathodic nickel was electrodeposited from'a bath containing about 40 grams per liter of nickel, about 35 grams per liter of Na2SO4 and about grams per liter of boric acid at a pH of about 5.0(Q) at a temperature of about 57 C. and a current density of about 12 amperes per square foot.
  • the novel active sulphur-bearing electrolytic or cathodic nickel of Figure 2 can be produced in an electrolyte having about the same composition as the foregoing, but containing about 1 gram per liter of ortho benzoyl sulphonamide.
  • the novel active sulphur-bearing cathodic nickel of Figure 2 had the following analysis:
  • the novel active sulphur-bearing cathodic nickelproduced in accordance with the foregoing disclosure contains about 0.030%
  • FIGs. 1 and 2 A comparison of Figs. 1 and 2 makes manifest the differences in microstructure which exist between regular sulphur-free electrolytic nickel and the novel active sulphur-bearing electrolytic nickel of the present invention.
  • Fig. 2 the presence of large amounts of nickel sulphide is plainly revealed and the photomicrograph shows that the nickel sulphide is mainly concentrated in the grain boundaries.
  • the photomicrograph shows that the nickel sulphide is mainly concentrated in the grain boundaries.
  • an inspection of the microstructure of the novel active sulphur-bearing electrolytic nickel of the prespurpose an inspection of the microstructure of the novel active sulphur-bearing electrolytic nickel of the prespurpose.
  • the anodes were deposited from a bath substantially equivalent to the conventional electrolyte commonly employed in the industry for this That is to say, an electrolyte was employed containing about 84.46 grams per liter of nickel, about 13.85 grams per liter. of chloride, and about 14.96 grams per' liter of boric acid. In other words, the electrolyte contained a source of nickel, an anode corroding agent and a buffer.
  • anode corroding agent When an insoluble anode is used the anode corroding agent need not be present. Under such conditions conventional salts such as sodium sulphate may be incorporated to increase the con- To this electrolyte ductivity of the electrolyte.
  • the distance from the anode to the cathode was about 2- inches.
  • the temperature during electrodeposition was between about 40 and about 45 C.
  • a low pH of about 1.8 to about 3.0 was employed and the electrolyte was agitated by an air liftpump, An anode current density of 8 amperes per square foot and a high cathode current density of 27 amperes per square foot was employed.
  • An electrodeposit of nickel weighing about 130 grams was obtained.
  • this cathodic nickel was deposited from a bath containing sodium thiosulphate had satisfactory activity andsatisfactory corrosion characteristics.
  • Corrosion at pH 5.5 (Q) showed that after 18 hours the metal of the anode was still hard and firm, the anode had satisfactory activity and satisfactory corrosion properties.
  • the anode produced cathodically in the bath containing sodium thiosulphate contained about 0.11% of sulphur practically all of which was present in a form reacting with HCl to form H28.
  • anode current density of about 15 amperes per square foot and a cathode current density of about 4 amperes per squarefoot in an electrolyte containing 81.70 grams per liter of nickel, 13.12 grams per liter of chloride and 40.10 grams per liter of boric acid.
  • the pH during the corrosion ranged from 4.0 to 4.3 (Q) and the anode lost about-38 grams during a corrosion of about 22 hours.
  • the surface of the anode was covered completely with a. thin black film of sludge.
  • the anodic metal was hard and firm at all points.
  • the corrosion of the face of the anode was smooth and the anode was highly active. From all technical considerations this anode was highly satisfactory.
  • This anode likewise was tested for corrosion characteristics in a hot Watts type test solution having a pH of about 5.5 (Q) at the initiation of the corrosion. After 22 hours of corrosion the anode was still active, was completely covered with a thin black film of sludge, the metal was hard and firm at all points and the corrosion of the face was smooth. Thus, this anode is considered to be highly active at high pHs above pH 4.0 (Q). The sulphur content of this anode was 0.054%.
  • the bath containing methylene blue was then corroded in a hot Watts type electrolyte having a pH of about 5.5 (Q) at the start of the corrosion. After 22 hours of corrosion, the anode was covered with sludge but was still active. It is manifest therefore, that cathodic nickel electrodeposited from an electrolyte, containing methylene blue has good activity and is satisfactory for use as an anode in the electrodeposition of protective, decorative or utilitarian films of nickel.
  • the electrodeposited nickel produced in the bath containing methylene blue contained about 0.104% sulphur.
  • EXAMPLE IV A second anode was prepared by cathodic deposition of nickel from a standard electrolyte containing 0.25 gram per liter of methylene blue.
  • the cathodic nickel so obtained contained about 0.023 gram of sulphur present principally as the sulphide.
  • This cathodic nickel upon corrosion at pH 4.0 and pH 5.5 (Q) made it manifest that such cathodic nickel is suitable for use as plating anodes in the deposition of protective, decorative and/or utilitarian films of nickel.
  • This second methylene blue anode had good activity, satisfactory corrosion and only produced amounts .of sludge which are acceptable to the art.
  • EXAMPLE V The same standard electrolyte was employed as employed in Example 1 to which was added nickel so produced was corroded at about pH 4.0 (Q) employing an anode current density of about 15 amperes per square foot. was completely covered with a thin black film of sludge indicating uniform corrosion. A similar portion of cathodic nickel produced from a bath containing 0.25 gram per liter of thio-urea was EXAMPLE VI Cathodic nickel was deposited under the aforedescribed conditions at low pH and high current density from a standard electrolyte containing initially about 0.25 gram of a dithiophosphate sold under the trade name of Sodium Aerofloat.
  • EXAMPLE VII know, Thioflavine S is a methyl derivative of sulphonated primuline, and usually comes on the market as the sodium salt of the sulphonate.
  • cathodic nickel produced in a bath containing thioflavine S is corroded anodically at pHs 4.0 and 5.5 (Q), it is manifest that such metal is suitable for use as anode in nickel elec-.
  • This nickel is active at both pH 4.0 and 5.5 and the anode becomes covered with a black sludge.
  • thiofiavine T Similar sulphur-containing materials derived from dehydro-thio-para-toluidine such as thiofiavine T may likewise be employed with equally satisfactory results.
  • the anode produced cathodically in the bath containing thiofiavine S contained about 0.078% copper and about 0.033% sulphur, the sulphur being present principally as a sulphide.
  • the anodes produced as described hereinbefore had a thickness of about 0.2 centimeter or, in other words, about 0.08 inch.
  • Such deposits are many times the thickness of the average film of nickel deposited for protective, decorative and/or 0.25 gram per liter of thio-urea;
  • the cathodic utilitarian purposes and considerably thicker The anode than even the thickest films produced by the prior art for protective, decorative and/or utilitarian purposes.
  • cathodic nickel suitable for use as anodes in plating conventional gray nickel or in electrodepositing "bright" nickel may be produced employing standard nickel electrolytes as the basic bath and operating at pHs of about 1.5 to about 6.0(Q).
  • cathodic nickel may be carried out at temperatures of about 20 F. to about 200 F., preferably with agitation of the electrolyte.
  • the conventional process for producing nickel anodes comprising producing electrolytic nickel substan tially devoid of sulphur, melting the electrolytic nickel and adding sulphur to the molten nickel and finally casting the nickel containing sulphur as an ingot from which nickel anodes may be produced is no longer necessary, since it is now possible by means'of the present invention to produce cathode nickel containing sulphur or cathode nickel containing copper and sulphur directly in the electro-recovering bath.
  • composition of the novel anodes is illustrated by the followingexamples:
  • Nickel including incidental amounts of cobalt V "fore, may contain up to about 0.1% copper.
  • dithiophosphates is to be understood to include those phosphorus and sulphur-containing organic substances which-are included in the type formula.
  • R1 and R may be the hydrocarbon residues of aliphatic alcohols, carboxylic acids, aldehydes and ketones as well as the hydrocarbon residues of such members of the, aromatic series as cresols, xylenols, 'naphthols and the like. .It is' likewise to be understood that as the sulphur content of the electrolyte decreases during the deposition of the electrolytic nickel containing sulphur, further amounts of the sulphur-containing addition agent as defined hereinbefore may be added to the fundamental nickel electrolyte if desirable. Furthermore, electrolytic nickel anodes as produced under the.
  • electrolyte soluble as applied to sulphur-bearing substances suitable for use in the aforedescribed process means sulphur-bearing compounds which are soluble in the electrolyte at the pH at which electrodeposition of the cathodic nickel takes place.
  • the reduction potential at unit activity may be employed as a further means of defining the electrolyte soluble sulphur-bearing substances suitable for use in the aforedescribed process.
  • elec- Balance 'trolyte soluble sulphur-'bearingsubstances capable of ionizing to sulphur-containing radicals having a reduction potential to hydrogen sulphide at unit activity of not more than that of thiosulphate, for example, not more than about 0.64
  • volt may be employed.
  • present invention has been described in conjunction with conventional nickel electrolytes containing a source of nickel, an anode corroding agent and a buifer'for use in conjunction with nickel anodes, those skilled in the art willappreciate that when insoluble anodes are employedand the electrolyte is the sole source of nickel, an anode corroding agent is not incorporated in the bath.
  • a suitable electrolyte is one containing about 40 'to about 84 grams of nickel per liter in the form taining sulphur which comprises immersing an anode and a starting sheet as cathode in an aqueous electrolyte comprising essentially nickel ions, sulphate ions, chloride ions, borate ions and about 0.05 to 0.25 gram per liter of alkali metal thiosulphate, said electrolyte being characterized by of the entire bath present solely as alkali metal thiosulphate.
  • a bath suitable for the electro-deposition of nickel electro-plating anodes at least about 0.08 inch thick and containing sulphur within the range of 0.007 to 0.11% which comprises an aqueous electrolyte comprising essentially nickel'ions, sulphate ions, chloride ions, borate ions and about 0.05 to 0.25 gram per liter of alkali metal thiosulphate, said bath having a pH of about 1.9 to 5.5 and characterized by having the thiosulphate content of the entire bath present-solely as alkali metal thiosulphate.
  • a bath suitable forthe electro-depositlon of nickel anodes at least about 0.08 inch thick and containing sulphur within the range of 0.007 to 0.11% which comprises an aqueous electrolyte comprising essentially nickel ions, sulphate ions. chloride ions, borate ions and about 0.1 to 0.2 gram per liter of sodium thiosulphate, said bath having a pH of about 2.5 to 4.5 and characterized by having the thiosulphate content of the entire bath present solely as sodium thiosulphate.
  • a process for producing nickel anodes containing sulphur which comprises immersing an anode and a starting sheet as cathode in an aqueous electrolyte comprising-essentially nickel ions, sulphate ions, chloride ions, borate ions and about 0.05 to 0.25 gram per liter of alkali metal thiosulphate, maintaining said bath at pH of about 1.9 to 5.5, and passing electric current at a cathode current density of about 10 to about 50 am-' peres per square foot between said anode and cathodeuntil a cathodic electro-deposit at least about 0.08 inch thickand containing about 0.007 to 0.11% sulphur is obtained, said cathodic electro-deposit being suitable in the as-deposited condition for subsequent use as an anode.
  • taining sulphur which comprises immersing an 'anodeand a starting sheet as cathode in an aqueous electrolyte comprising essentially nickel ions, sulphate ions, chloride ions, borate ions and about 0.1 to 0.2 gram per liter of sodium thiosulphat'e, maintaining saidbath at pH of about 2.5 to 4.5, and passing electric current at a cathode current density of about 10 to 50 amperes per square foot between said anode and cathode until a cathodic electro-deposit at least about 0.08 inch thick and containing about 0.007 to 0.11% sulphur is obtained, said cathodic electro-deposit being suitable in the as-deposited condition for subsequent use as an anode.

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2453757A (en) * 1943-06-12 1948-11-16 Int Nickel Co Process for producing modified electronickel
US2623848A (en) * 1943-06-12 1952-12-30 Int Nickel Co Process for producing modified electronickel
US3437571A (en) * 1964-07-20 1969-04-08 Int Nickel Co Production of electrolytic nickel
US3715286A (en) * 1971-03-11 1973-02-06 Int Nickel Co Electrorefined nickel of controlled size
US3943048A (en) * 1973-02-26 1976-03-09 The International Nickel Company, Inc. Powder anode
US4087339A (en) * 1976-07-02 1978-05-02 The International Nickel Company, Inc. Electrowinning of sulfur-containing nickel
CN109023440A (zh) * 2018-09-04 2018-12-18 中国科学院兰州化学物理研究所 利用无碳携硫剂制备含硫镍材料的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1178610B (de) * 1961-03-10 1964-09-24 Internat Nickel Company Of Can Verfahren zum Raffinieren von Nickel durch Elektrolyse

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2453757A (en) * 1943-06-12 1948-11-16 Int Nickel Co Process for producing modified electronickel
US2623848A (en) * 1943-06-12 1952-12-30 Int Nickel Co Process for producing modified electronickel
US3437571A (en) * 1964-07-20 1969-04-08 Int Nickel Co Production of electrolytic nickel
US3715286A (en) * 1971-03-11 1973-02-06 Int Nickel Co Electrorefined nickel of controlled size
US3943048A (en) * 1973-02-26 1976-03-09 The International Nickel Company, Inc. Powder anode
US4087339A (en) * 1976-07-02 1978-05-02 The International Nickel Company, Inc. Electrowinning of sulfur-containing nickel
CN109023440A (zh) * 2018-09-04 2018-12-18 中国科学院兰州化学物理研究所 利用无碳携硫剂制备含硫镍材料的方法

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DE818301C (de) 1951-12-13
FR938689A (fr) 1948-10-21

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