US3152973A - Electrodeposition of lustrous nickel - Google Patents

Electrodeposition of lustrous nickel Download PDF

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Publication number
US3152973A
US3152973A US45287A US4528760A US3152973A US 3152973 A US3152973 A US 3152973A US 45287 A US45287 A US 45287A US 4528760 A US4528760 A US 4528760A US 3152973 A US3152973 A US 3152973A
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Prior art keywords
nickel
plate
fine
bath
satin
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US45287A
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Thaddeus W Tomaszewski
Brown Henry
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Occidental Chemical Corp
Udylite Corp
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Udylite Corp
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Priority to NL267500D priority Critical patent/NL267500A/xx
Priority to NL267501D priority patent/NL267501A/xx
Priority to NL125958D priority patent/NL125958C/xx
Priority to NL267502D priority patent/NL267502A/xx
Priority to NL125957D priority patent/NL125957C/xx
Priority to NL125956D priority patent/NL125956C/xx
Priority to US45287A priority patent/US3152973A/en
Priority to US45286A priority patent/US3152972A/en
Priority to US45285A priority patent/US3152971A/en
Application filed by Udylite Corp filed Critical Udylite Corp
Priority to GB26619/61A priority patent/GB936172A/en
Priority to DEU8210A priority patent/DE1248413B/de
Priority to SE7619/61A priority patent/SE307713B/xx
Priority to FR868990A priority patent/FR1299814A/fr
Priority to SE7618/61A priority patent/SE301742B/xx
Priority to SE7620/61A priority patent/SE307714B/xx
Application granted granted Critical
Publication of US3152973A publication Critical patent/US3152973A/en
Anticipated expiration legal-status Critical
Assigned to HOOKER CHEMICALS & PLASTICS CORP. reassignment HOOKER CHEMICALS & PLASTICS CORP. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: OXY METAL INDUSTRIES CORPORATION
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.
Expired - Lifetime legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02Combined electrolytic and electrophoretic processes with charged materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/923Physical dimension
    • Y10S428/924Composite
    • Y10S428/926Thickness of individual layer specified
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9265Special properties
    • Y10S428/927Decorative informative
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/934Electrical process
    • Y10S428/935Electroplating
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12479Porous [e.g., foamed, spongy, cracked, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12639Adjacent, identical composition, components
    • Y10T428/12646Group VIII or IB metal-base
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266O, S, or organic compound in metal component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266O, S, or organic compound in metal component
    • Y10T428/12667Oxide of transition metal or Al
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708Sn-base component
    • Y10T428/12722Next to Group VIII metal-base component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12778Alternative base metals from diverse categories
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771Transition metal-base component
    • Y10T428/12861Group VIII or IB metal-base component
    • Y10T428/12944Ni-base component

Definitions

  • nickel plating baths normal- 1y designated as bright nickel baths, or semi-bright nickel baths can be modified to plate a fine-grained lustrous satin nickel deposit, by incorporating in these baths certain quantities or concentrations of certain finely divided bath insoluble compounds, and plating while these pow dered mat erials are maintained in agitation in these baths.
  • the method .of the invention also includes the step-of removing from the plated surface any excess powdery material clinging to the plate prior to additional treating steps, such as the preferred final stepof chromium plating.
  • the class of bath insoluble fine powders which when added to "agitated bright nickelor semi-bright nickel platingbaths in concentrations from 10 to 500 grams per liter produce a pleasing fine-grained lustrous satin nickel directly from the bath, is the sulfates, carbonates, phosphates and oxalates of the alkaline earth metals, barium, strontium and calcium. Not all of the compounds produce exactly equal effects, for example barium sulfate is superior to calcium oxalate. All of the carbonates are aboutequal, though barium carbonate and strontium carbonates are easier to use because they cause less caking problems. However, barium carbonate, as well as phosphate and oxalate are toxic powders.
  • barium sulfate is preferred over the other mentioned barium compounds, because it is'not toxic.
  • Barium chromate fine powder did not give, rise to the satin nickel plate, and in high concentrations actually stopped the nickelplating. Since the carbonate powders of calcium, strontium and barium will react with acid they tend to neutralize the nicketb'ath to pH values of .Ofto 6.0 and partially form insoluble sulfates of these metals as well as some, insoluble nickel hydroxide and carbonate In fact, fine I 3,152,973 Patented Oct. 13, 1964 nickel carbonate powder or basic nickel carbonate powder can be used to raise the pH of'the nickel bath to 5.0 to 5.2 before adding barium carbonate.
  • nickel carbonate or basicnickel carbonate powder by itself at bath pH values of about 5.0 to 6.0 also produced the fine-grained lustrous v satin finish when present in concentrations of to 500 grams per liter in agitated bright nickel or semi-bright nickel baths.
  • Especiallydesirable results from a decorative as well as a corrosion resistant standpoint are obtained by the addition of very fine powders of barium sulfate, strontium sulfate, or calcium carbonate in concentrations of about 30 to 200 grams per liter to air-agitated bright nickel plating baths such as those described in US. 2,647,866, issued August 4, 1953; 2,800,440 and 2,800,442, issued July 23, 1957.
  • Superfine barium sulfate powder is especially outstanding in performance.
  • the nickel plate obtained from these agitated bright plating baths containing, for example, about 150 grams per liter of superfine barium sulfate powder, has a semi-bright microscopically-fine pitted surface with a satin smooth sheen of very pleasing appearance.
  • the fine suspended powders such as those of calcium carbonate, strontium sulfate, barium sulfate, tend to cling to the nickel plate, and this effect and the specific physical structure, particle size and shape, amorphous texture, etc., and the chemical structure of the powder apparently causes the microscopically-fine pitting effect which converts the normally bright or semi-bright surface to a satin smooth sheen.
  • the uniformity of the sheen is unusual and especially noteworthy in that a 0.2 mil to a 2 mil thick or thicker plate can have the same satin appearance.
  • Air agitation or mechanical agitation including ultra-sonic agitation of the baths can be used.
  • the faster or more powerful the agitation and the finer the particle size down to colloidal dimensions, the lower the concentration of fine powder that is necessary, and concentrations as low as 10 grams per liter may be used to obtain a smoky satin finish by using strong agitation and powders having a size of about 0.1 to 0.3 micron or ultrafine particles having a size of 0.03 to 0.04 micron.
  • Agitation is necessary to keep the fine powder suspended in the bath during plating. In general, however, it is preferred to use from about 50 to 200 grams per liter of very fine powder having a size less than 5 microns and preferably less than 2 microns in air-agitated baths.
  • barium sulfate to agitated plain dull nickel baths such as the Watts bath, makes the dull nickel plate obtained even duller and more unsightly in appearance.
  • the throwing power and covering power of the agitated bright nickel baths withfthe suspended powders is about the same as without the fine powders present. It was found that in plating articles with recessed areas and with shelf areas that no roughness was obtained on the areas on which settling can occur and this was quite unexpected particularly with the high density powders such obtained where brush or polishing lines are desired in a satin finish, by using coarse polishing grit such as 120 emery on the basis metal The original coarse polishing lines are diminished by the high levelingsatin nickel plate of this invention and though diminished are still visible. In this way, a highly corrosion resistant scratch brush finish satin nickel is obtained without having to resort to scratch brushing a final nickel plate and thus decreasing its corrosion protection.
  • the carbonates of barium, strontium and calcium also form to a certain extent the insoluble sulfates when they react with the acidity of the Watts nickel bath.
  • a mixed insoluble powder is formed, and this in some cases changes somewhat the texture of the satin finish obtained.
  • fine calcium carbonate powder 50-150 grams/liter
  • bright nickel baths of the Watts type or those containing some sulfate ions are preferred over the all chloride type.
  • dispersing agents, peptizing agents in conjunction with the fine powders is often helpful, especially with some powders such as calcium sulfate which tend to cake. It is also helpf'ul'to process the dispersion with high energy dispersion machines such as the Cowles Dissolver which accomplishes practically complete dispersion into ultimate particle size but while helpful, this treatment is not necessary, for obtaining excellent satin nickel plate. Such procedures help in reducing the need for usingthe higher concentrations of powder in the bath such as the to 200'grams per liter concentrations. However, concentrations of 100 to200 grams per-liter of a commercial fine powder such as Merck U.S.P.
  • X-ray grade barium sulfate gives excellent satin" nickel plate when used as purchased in regular air agitated bright nickel "platingbalhs. There'are no particular operating troubles because concentrations of 150 grams per liter or higher of this powder are used in the bath instead of, for example, 40 to 50grams per liter of 0.1 to 0.35 micron particle size.
  • concentrations of 150 grams per liter or higher of this powder are used in the bath instead of, for example, 40 to 50grams per liter of 0.1 to 0.35 micron particle size.
  • the powders of extremely fine or ultra fine'particle size of 0.03 to 0.04 micron or less are generally more expensive, that is, if. the great percentage of the particles are of these ultra-fine diameters, however, lower concentration can be usedtoobtain equivalent effects.
  • Cadmium tends to whiten the plate somewhat. Copper carbonate is surprisingly not harmful inhigh concentrations. The presence of sodium and magnesium salts are not harmful. Ammonium salts in concentrations higher than about 15 grains per liter is in general not desirable because of reduction of the limiting. cathode current density.
  • the pH of the baths may be from about 2 to 6,
  • the pH isautomatically raised to about 5.2 andeven to about 5.5.
  • the pH of the baths can be raised with nickel carbonate powder, preferably finely precipitated powder, and the nickel carbonate powder can be left in the bath in high'concentration.
  • the temperature of the baths can be from room to at least 170 F., though in general a temperature of about F. to about F. is preferred.
  • Barium sulfate fine powder produced the best satin finish from the agitatedbright and semi-bright nickel plating baths. Barium carbonate, strontium sulfate and carbonate are next in order of preference.
  • the use of these fine powders of bariumsulfate or calcium carbonate, etc. does not create a satin sheen nickel plate when added to plain nickel baths that normally produce dull nickel deposits such as the Watts nickel bath.
  • the nickel "bath must be a semi-bright or bright nickel plating bath.
  • sulfonicacids naphthalene sulfonic acids, p-toluene sulfonamide, benzene sulfonamide, o-benzoyl sulfimide, allyl.
  • Cobalt and iron can be present in the nickel bath as the cobalt or ferrous sulfates, chlorides, sulfamates or fluoborates in concentrations as high as at least 40 grams per liter, yielding nickel alloy plates containing concentrations of cobalt and /or iron as high as 50%.
  • Surface active agents may be present in the baths, but are not usually necessary in the air agitated baths.
  • the maximum increase in satin sheen is obtained when the fine powders are used in the agitated full, bright nickel plating baths such as the air-agitated bright nickel in t plating baths possessing good levelingas those illustrated in Examples 1,2 and below.
  • the semi-bright sulfur-free type of addition agent such as formaldehyde, chloral hydrate or brornal, is used solely with the fine powders, and with these sulfurfree semi-bright addition agents suchas those mentioned,
  • the ultra-fine particle size powders of less than 0.2 micron particle size, and preferably less than 0.05 micron particle size as determined with the electron microscope. There seems to be a definite improvementin leveling with the semi-bright sulfur-free addition agents when these ultra-fine particle size powders are used.
  • chromium plate barium tsequeste ring agents
  • a very thin plate from a zinc cyanide bath for example, about 1 to 3 minutes plating followed by an'acid or alkaline dip toremove the zinc, also removed the tightly clinging barium sulfate particles.
  • theparticles on the work look like a fine dust or talc and are not really too unsightly even if left on, and-they do not hurt the chromium plate; They are readily wiped off with a cloth, or can be removed to a certain extent by ultra-sonic cleaning.
  • the satin nickel plate accepts chromium plate like regular nickel plate, and in general only the usual thicknesses of final chromium need be used, that is, 0.01 mil, though thicknesses of 0.1 mil or 0.2 mil may be used.
  • the satin nickel plate can be given a rhodium, silver, tin, brass, bronze, copper, gold, or tin-nickel (65-35) alloy or other final thin coating.
  • Thin wax, or soluble-wax, films or clear lacquers greatly decrease finger marking of the final coatings, such as nickel, bronze, silver, brass, etc. Chromium, rhodium, and tin-nickel alloy plate do not need these organic coatings.
  • satin nickel coatings of only 0.2 to 0.5 mil thickness are needed.
  • thicknesses 1 to 1.5 mils should be used.
  • the satin nickel can be used as the top layer of a double layered or duplex nickel coating, with the undercoat consisting of at least 0.7 mil of semi-bright sulfur freenickel. This would be for the most severe outdoor exposure as for marine hard ware.
  • the corrosion protection to steel, aluminum, magnesium, brass and zinc of the satin nickel with the usual final chromium plate (0.01
  • the cathode current density is from about 10 to at least 100 amps/sq. ft.
  • Barium and strontium sulfate powder is preferred over calcium sulfate; and barium and strontium carbonate over calcium carbonate, mainly because of the excessivecaking tendency of these calcium compounds in the absence of agitation, e.g., when the bath is not in use. For this reason, mechanical agitation is preferred for these calcium compounds insteadof air agitation. When the agitation is turned off, the fine powders settle and the clear nickel solution can be subjected to ordinary filtration treatments'.
  • the settled powders can readily be removed by a slurry pump for any re-processing or milling if it is desired. Also, it is possible to filter with traveling screens to screen out the coarser powders. In general, precipitated-powders are preferred because of their very fine size, though any process for fine powder manufacture which produces the powder in clean form and with a high percentage of the powder less than about 2 micron particle size, and preferably of 0.02 to 0.5 micron particle size will accomplish the result. Powders containing large quantities of particles having diameters greater than about 5 microns tendto produce rougher plate and for most applications are preferably avoided.
  • Mixtures of powders may be used such asbarium sulfate and carbonate, barium sulfate and nickel carbonate, strontium sulfate and barium sulfate, barium carbonate, calcium carbonate and barium sulfate, etc.
  • Comparable particle size fluorides'of calcium, strontium and barium are also useful in about the same proportions and under similar conditions as the sulfates, carbonates, phosphates and oxalates described above in detail.
  • the satin nickel plate of this invention has about 10 million to about 50 million' micro-pits per square inch
  • Example IV Sr'CO or SrSO or BaCO or BaSO; ultra-fine powder or mixtures (0.03 to 0.04 micron) particle size conc. -200 NiSO .6H O 150-350 NiCl- .6H O 30-53 H BO 30-40 Chloral hydrate e 0.1 Formaldehyde 0.04
  • Temp. room to F. Mechanical agitation.
  • Example IX Nickel carbonate or basic nickel carbonate (less than 2 micron particle size) conc 30-150 Barium sulfate 0-100 NiSO .6H O 100-300 NiCl.6H O 30-150 H BO 30-40 Allyl sulfonic acid 0.5-3 p-Toluene sulfonamide 1-2 o-Benzoyl sulfimide 1-2 Z-butynoxy-l,4-diethoxyethane disulfonic acid" 0.1-2.2
  • a method for electrodepositing a fine-grained lustrous plate which is essentially nickel comprising the step of electrolyzing with externally applied current an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fiuoborate, nickel sulfamate and mixtures of at least one said nickel salt with up to about 40 grams per liter of at least one salt selected from the group consisting of the sulfates, chlorides, fluoborates and sulfamatesof cobalt and iron and at least one soluble organic addition agent capable of producing said finegrained lustrous plate, said bath containing about 10m ,-about 500 grams per liter of at least one material selected from the group consisting of the sulfates, carbonates,
  • a method for electrodepositing a fine-grained lustrous satin nickel plate comprising the step of electroylzing an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fiuorborate, and nickel sulfamate and at least onesoluble organic addition agent capable of producing said fine-grained lustrous plate, said bath containing about 10 to about 500 grams per liter of nickel carbonate, and having a pH in the range of about 5.0 to about 6.0; said nickel carbonate being in the form of fine powder dispersed in said bath and having a particle size which is less than about 5 microns average diameter, and
  • a method for electrodepositing a fine-grained lustrous nickel plate comprising the step of electrolyzing with an externally applied current 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 at least one soluble organic nickel brightener selected from the class consisting of aromatic and unsaturated aliphatic sulfonic acids, sulfonamides and sulfonimides, said bath containing about 10 to about 500 grams per'liter of at least one material selected from the group consisting of the sulfates, carbonates, phosphates and oxalates of barium, strontium and calcium, said material being in the form of fine pow der dispersed in said bath and having a particle-size which is less than about 5 microns average diameter; and thereafter plating on said surface an ove'rlayer of a metal selected from the group consisting of chromium, rhodium,
  • a composite electroplate on a metal surface susceptible to atmospheric corrosion which comprises a nickel plate with a metallic over-lay, said nickel plate having been electrodeposit ed from an acidic nickel plating bath containing, dissolved therein at least one organic nickel brightener capable of producing semi-bright to fully bright nickel plate and having dispersed therein at least 7 one type of bath insoluble inorganic non-metallic particles', the average diameter of the individual particles thereof being less than about 5 microns, an electrodeposited over-lay plate of a metal selected from the group consisting of chromium, rhodium, silver, tin, brass,
  • over-lay plate being less than about 5 microns in thickness
  • typeof particles being selected from the group consisting of the sulfates, carbonates, phosphates, and oxalates of barium, strontium and calcium, and said particles'in said nickel bath being present in an amount sufficient to produce a fine porosity pattern in the said over-lay plate.
  • a composite electroplate in accordance with claim 9 wherein said dissolved organic nickel brightener is selected from the class consisting of aromatic and unsaturated aliphatic sulfonic acids, sulfonamides and sulfonimides.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Paints Or Removers (AREA)
US45287A 1960-07-26 1960-07-26 Electrodeposition of lustrous nickel Expired - Lifetime US3152973A (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
NL125958D NL125958C (fr) 1960-07-26
NL267502D NL267502A (fr) 1960-07-26
NL125957D NL125957C (fr) 1960-07-26
NL125956D NL125956C (fr) 1960-07-26
NL267500D NL267500A (fr) 1960-07-26
NL267501D NL267501A (fr) 1960-07-26
US45286A US3152972A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous satin nickel
US45285A US3152971A (en) 1960-07-26 1960-07-26 Electrodeposition of fine-grained lustrous nickel
US45287A US3152973A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous nickel
GB26619/61A GB936172A (en) 1960-07-26 1961-07-21 Improvements in or relating to nickel plating
DEU8210A DE1248413B (de) 1960-07-26 1961-07-24 Saures galvanisches Nickelbad zur Herstellung von dekorativen UEberzuegen
SE7619/61A SE307713B (fr) 1960-07-26 1961-07-25
FR868990A FR1299814A (fr) 1960-07-26 1961-07-25 Procédé de nickelage, bains utilisés et produits obtenus
SE7618/61A SE301742B (fr) 1960-07-26 1961-07-25
SE7620/61A SE307714B (fr) 1960-07-26 1961-07-25

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Application Number Priority Date Filing Date Title
US45285A US3152971A (en) 1960-07-26 1960-07-26 Electrodeposition of fine-grained lustrous nickel
US45286A US3152972A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous satin nickel
US45287A US3152973A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous nickel

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US45285A Expired - Lifetime US3152971A (en) 1960-07-26 1960-07-26 Electrodeposition of fine-grained lustrous nickel
US45287A Expired - Lifetime US3152973A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous nickel

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US45285A Expired - Lifetime US3152971A (en) 1960-07-26 1960-07-26 Electrodeposition of fine-grained lustrous nickel

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DE (1) DE1248413B (fr)
FR (1) FR1299814A (fr)
GB (1) GB936172A (fr)
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SE (3) SE301742B (fr)

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US3282810A (en) * 1961-11-27 1966-11-01 Res Holland Nv Method of electrodepositing a corrosion resistant nickel-chromium coating and products thereof
US3298802A (en) * 1962-02-23 1967-01-17 Res Holland S Hertogenbosch Nv Method for covering objects with a decorative bright-nickel/chromium coating, as well as objects covered by applying this method
US3342566A (en) * 1963-12-24 1967-09-19 Adolf E Schwedhelm Process for the electrodeposition of a decorative corrosion resistant nickel-chromium coating and products thereof
US3356467A (en) * 1964-12-28 1967-12-05 Udylite Corp Article coated with a coelectrodeposit of nickel and plastic particles, an overlayerthereon, and method of making said article
US3449223A (en) * 1962-05-30 1969-06-10 Jules Marie Odekerken Method for covering objects with a decorative bright nickel/chromium coating,as well as objects covered by applying this method
US3471271A (en) * 1965-08-16 1969-10-07 Udylite Corp Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate
US3652236A (en) * 1965-10-23 1972-03-28 Res Holland Nv An article having a layer containing nonconductive organic fibers and method of producing
US4010005A (en) * 1973-06-23 1977-03-01 Mitsui-Anaconda Electro Copper Sheet Co., Ltd. Copper foil having bond strength
FR2452531A1 (fr) * 1979-03-30 1980-10-24 Sumitomo Metal Ind Procede de placage electrolytique d'un alliage sur une bande d'acier
US5160423A (en) * 1989-11-09 1992-11-03 Kanto Kasei Co., Ltd. Nickel plating solution, nickel-chromium electroplating method and nickel-chromium plating film
EP0748883A1 (fr) * 1995-06-12 1996-12-18 ABB Management AG Pièce munie d'un revêtement électrolytique et procédé de réalisation de couches par électrodéposition
CN113046794A (zh) * 2021-02-24 2021-06-29 兰州理工大学 一种利用三氯化铈细化电沉积镍晶粒的方法

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US3407050A (en) * 1965-05-04 1968-10-22 Trapp Gloria Worthington Duplex nickel material
DE1621206B2 (de) * 1967-01-18 1971-12-16 Friedr. Blasberg Gmbh & Co, Kg, 5650 Solingen Verfahren zur beschichtung gleitend reibend auf verschleiss beanspruchter werkstuecke
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US3929596A (en) * 1972-10-02 1975-12-30 Toyo Kogyo Co Electrodeposition of wear resistant and oil retentive nickel coatings and article having such a coating
US3825478A (en) * 1972-10-30 1974-07-23 Oxy Metal Finishing Corp Electrolyte and method for electrodepositing microporous chromium-nickel composite coatings
JPS5948872B2 (ja) * 1978-02-20 1984-11-29 クロリンエンジニアズ株式会社 電解用陰極及びその製造法
FR2616452B1 (fr) * 1987-06-12 1991-08-16 Peugeot Procede de revetement d'une piece quelconque par voie chimique ou electrolytique et piece obtenue par ce procede
FR2617510B1 (fr) * 1987-07-01 1991-06-07 Snecma Procede de codeposition electrolytique d'une matrice nickel-cobalt et de particules ceramiques et revetement obtenu
JPH01309997A (ja) * 1988-06-09 1989-12-14 Kanto Kasei Kogyo Kk 耐食性に優れた銅−ニッケル−クロム光沢電気めっき方法およびそれにより得られためっき皮膜
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FR2848219B1 (fr) * 2002-12-09 2006-12-01 Centre Nat Rech Scient Materiau composite utilisable comme revetement lubrifiant
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AT413097B (de) * 2004-06-29 2005-11-15 Hirtenberger Automotive Safety Beschichtung, insbesondere für die zündbrücke eines zünders
ES2306023T3 (es) * 2005-10-20 2008-11-01 Wolf-Dieter Franz Produccion de superficies metalicas mates como la seda.
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CN107254699A (zh) * 2017-06-08 2017-10-17 合锋卫浴(厦门)有限公司 一种铝合金电镀粉雾镍复合镀层的方法
CN111455420B (zh) * 2020-06-01 2022-05-17 温州市展鑫新材料有限公司 一种用于复杂形状金属零件表面镀覆锌镍合金的电镀液
CN111876797B (zh) * 2020-07-08 2021-10-15 佛山亚特表面技术材料有限公司 一种高防腐中性镍镀液及中性镍打底工艺

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US942729A (en) * 1909-09-07 1909-12-07 Percy S Brown Electrolyte and method of electrodepositing nickel.
US970755A (en) * 1909-03-16 1910-09-20 Augustus Rosenberg Electroplating.
US1163911A (en) * 1915-09-08 1915-12-14 Clarence A Hall Electrolysis.
GB444464A (en) * 1934-10-26 1936-03-20 Schering Kahlbaum Ag Improvements in or relating to electroplating baths
US2119304A (en) * 1935-08-01 1938-05-31 Eaton Detroit Metal Company Electroplating
US2318592A (en) * 1940-02-24 1943-05-11 Du Pont Electrodeposition
US2483996A (en) * 1944-06-02 1949-10-04 Sk Wellman Co Method of reconditioning backing members having powdered material facings
US2637686A (en) * 1949-04-02 1953-05-05 Int Nickel Co Process of producing drawn articles
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US2728720A (en) * 1953-03-09 1955-12-27 Dow Chemical Co Method of producing an electroplate of nickel on magnesium and the magnesium-base alloys
US2756489A (en) * 1946-05-03 1956-07-31 Howard E Morris Metal alloy
US2767464A (en) * 1952-10-24 1956-10-23 Ohio Commw Eng Co Composite metallic bodies and method of producing the same
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GB513963A (en) * 1938-04-23 1939-10-26 Eaton Mfg Co Improvements in or relating to the electrodeposition of nickel
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US2992171A (en) * 1957-06-27 1961-07-11 Gen Dev Corp Method and composition for chromium plating
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US970755A (en) * 1909-03-16 1910-09-20 Augustus Rosenberg Electroplating.
US942729A (en) * 1909-09-07 1909-12-07 Percy S Brown Electrolyte and method of electrodepositing nickel.
US1163911A (en) * 1915-09-08 1915-12-14 Clarence A Hall Electrolysis.
GB444464A (en) * 1934-10-26 1936-03-20 Schering Kahlbaum Ag Improvements in or relating to electroplating baths
US2119304A (en) * 1935-08-01 1938-05-31 Eaton Detroit Metal Company Electroplating
US2318592A (en) * 1940-02-24 1943-05-11 Du Pont Electrodeposition
US2483996A (en) * 1944-06-02 1949-10-04 Sk Wellman Co Method of reconditioning backing members having powdered material facings
US2756489A (en) * 1946-05-03 1956-07-31 Howard E Morris Metal alloy
US2637686A (en) * 1949-04-02 1953-05-05 Int Nickel Co Process of producing drawn articles
US2658839A (en) * 1951-04-21 1953-11-10 Gen Am Transport Process of chemical nickel plating
US2767464A (en) * 1952-10-24 1956-10-23 Ohio Commw Eng Co Composite metallic bodies and method of producing the same
US2728720A (en) * 1953-03-09 1955-12-27 Dow Chemical Co Method of producing an electroplate of nickel on magnesium and the magnesium-base alloys
US2849353A (en) * 1955-02-08 1958-08-26 Hanson Van Winkle Munning Co Bright nickel plating
US2999798A (en) * 1955-12-09 1961-09-12 Daimler Benz Ag Method of producing a wear-resisting surface on a metal element
US3041254A (en) * 1959-01-30 1962-06-26 Nat Alloys Ltd Nickel plating
US3061525A (en) * 1959-06-22 1962-10-30 Platecraft Of America Inc Method for electroforming and coating

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282810A (en) * 1961-11-27 1966-11-01 Res Holland Nv Method of electrodepositing a corrosion resistant nickel-chromium coating and products thereof
US3298802A (en) * 1962-02-23 1967-01-17 Res Holland S Hertogenbosch Nv Method for covering objects with a decorative bright-nickel/chromium coating, as well as objects covered by applying this method
US3449223A (en) * 1962-05-30 1969-06-10 Jules Marie Odekerken Method for covering objects with a decorative bright nickel/chromium coating,as well as objects covered by applying this method
US3342566A (en) * 1963-12-24 1967-09-19 Adolf E Schwedhelm Process for the electrodeposition of a decorative corrosion resistant nickel-chromium coating and products thereof
US3356467A (en) * 1964-12-28 1967-12-05 Udylite Corp Article coated with a coelectrodeposit of nickel and plastic particles, an overlayerthereon, and method of making said article
US3471271A (en) * 1965-08-16 1969-10-07 Udylite Corp Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate
US3652236A (en) * 1965-10-23 1972-03-28 Res Holland Nv An article having a layer containing nonconductive organic fibers and method of producing
US4010005A (en) * 1973-06-23 1977-03-01 Mitsui-Anaconda Electro Copper Sheet Co., Ltd. Copper foil having bond strength
FR2452531A1 (fr) * 1979-03-30 1980-10-24 Sumitomo Metal Ind Procede de placage electrolytique d'un alliage sur une bande d'acier
US5160423A (en) * 1989-11-09 1992-11-03 Kanto Kasei Co., Ltd. Nickel plating solution, nickel-chromium electroplating method and nickel-chromium plating film
EP0748883A1 (fr) * 1995-06-12 1996-12-18 ABB Management AG Pièce munie d'un revêtement électrolytique et procédé de réalisation de couches par électrodéposition
CN113046794A (zh) * 2021-02-24 2021-06-29 兰州理工大学 一种利用三氯化铈细化电沉积镍晶粒的方法

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Publication number Publication date
FR1299814A (fr) 1962-07-27
US3152971A (en) 1964-10-13
GB936172A (en) 1963-09-04
SE301742B (fr) 1968-06-17
SE307713B (fr) 1969-01-13
NL267502A (fr)
DE1248413B (de) 1967-08-24
NL125958C (fr)
NL125956C (fr)
SE307714B (fr) 1969-01-13
US3152972A (en) 1964-10-13
NL267500A (fr)
NL267501A (fr)
NL125957C (fr)

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