US3152971A - Electrodeposition of fine-grained lustrous nickel - Google Patents

Electrodeposition of fine-grained lustrous nickel Download PDF

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Publication number
US3152971A
US3152971A US45285A US4528560A US3152971A US 3152971 A US3152971 A US 3152971A US 45285 A US45285 A US 45285A US 4528560 A US4528560 A US 4528560A US 3152971 A US3152971 A US 3152971A
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Prior art keywords
nickel
fine
plate
oxide
bath
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Expired - Lifetime
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US45285A
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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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Filing date
Publication date
Priority to NL125957D priority Critical patent/NL125957C/xx
Priority to NL267501D priority patent/NL267501A/xx
Priority to NL125956D priority patent/NL125956C/xx
Priority to NL267500D priority patent/NL267500A/xx
Priority to NL267502D priority patent/NL267502A/xx
Priority to NL125958D priority patent/NL125958C/xx
Priority to US45285A priority patent/US3152971A/en
Priority to US45287A priority patent/US3152973A/en
Priority to US45286A priority patent/US3152972A/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 SE7620/61A priority patent/SE307714B/xx
Priority to FR868990A priority patent/FR1299814A/fr
Priority to SE7618/61A priority patent/SE301742B/xx
Application granted granted Critical
Publication of US3152971A publication Critical patent/US3152971A/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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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/923—Physical dimension
    • Y10S428/924—Composite
    • Y10S428/926—Thickness of individual layer specified
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9265—Special properties
    • Y10S428/927—Decorative informative
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/934—Electrical process
    • Y10S428/935—Electroplating
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12639—Adjacent, identical composition, components
    • Y10T428/12646—Group VIII or IB metal-base
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component
    • Y10T428/12667—Oxide of transition metal or Al
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12722—Next to Group VIII metal-base component
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12778—Alternative base metals from diverse categories
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component

Definitions

  • This invention relates to the electrodeposition of nickel with a satin-like appearance directly from aqueous acidic nickel baths. More particularly this invention provides a method for obtaining a fine-grained lustrous satin nickel plate of exceptional corrosion resistance directly from the plating bath.
  • Satin or brushed finished nickel or chromium plate is normally more expensive than the bright nickel finishes which are obtained with high-leveling, bright nickel plating which require no further polishing or bufling.
  • dull nickel or dull chromium plate is most often employed, and is subsequently brush finished to obtain the satin lustre. This latter step is expensive, and also decreases the corrosion protection afforded by'the satin plate because the brush marks or polishing scratches penetrate appreciably in the plate especially in recessed areas where the plate is thin. For these reasons, that is, expense, and decreased corrosion resistance, satin finished nickel or chromium are not usually used for exterior parts of automobiles or boats.
  • nickel plating baths normally designated as bright nickel baths, or semi-bright nickel baths can be modified to plate a fine-grained lustrons satin nickel deposit, by incorporating in these baths certain quantities or concentrations of certain finely divided bath insoluble compounds, and plating while these powdered materials 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 step of chromium platmg.
  • the bath insoluble fine powders which when added to agitated bright nickel or semibright nickel plating baths in concentrations from to 500 grams per liter produce a pleasing fine-grained lustrous satin nickel directly from the bath, are certain oxides, carbides, silicides, nitrides, fluorides and sulfides of the group consisting of silicon carbide, boron carbide, titanium carbide, silicon dioxide, manganese oxide, titanium oxide, zirconium oxide, aluminum oxide, ceric oxide, ferric oxide, chromic oxide, boron nitride, calcium fluoride, strontium fluoride, barium fluoride, stronium fluoride, barium fluoride, zinc sulfide, cadmium sulfide, and iron silicide.
  • the preferred particle size is from about 0.02 to 0.5 micron average diameter, and when used in concentrations of about 10 to 200 grams per liter in agitated bright or semi-bright nickel plating baths produce a smooth fine-grained lustrous satin nickel deposit.
  • the surface of the satin nickel plate obtained under these conditions has approximately 20 million micro-pits per sq. in. as determined by microscopic evaluation at 250x magnification. If the powders are from 0.02 to 0.05 micron ultra-fine particle size, concentrations can be used of about 10 to about grams per liter. If the particle size is about 0.1 to 0.4 micron, then concentrations of about 50 to 200 grams per liter give the best results.
  • the fine suspended powders tend to cling to the nickel plate, and this eiiect and the specific physical structure, particle size and shape, 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 2 mil thick or thicker plate can have the same satin appearance.
  • contoured articles such as camera parts, ornaments, grilles, automobile dashboards, door handles, marine hardware, etc.
  • the satin appearance of the plate in the recessed areas is the same as the plate in the higher current density areas.
  • 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 ultra-fine particles having a size of 0.02 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 2 microns in air-agitated baths.
  • the throwing power and covering power of the agitated bright nickel baths with the suspended powders is about the same as without the fine powders present. It
  • the leveling of the bright nickel plate is' not decreased by the presence of these fine insoluble powders in the bath. In fact, the leveling seems definitely improved in most cases.
  • the satin nickel plate obtained from bright or semibright nickel plating baths containing these fine powders can easily be polished or bulfed to a high lustre, thus, as already mentioned beautiful two-tone effects can readily be obtained by buffing raised or accessible portions of the satin nickel plated object.
  • a brush satin finish this can be accomplished by using, for example, 120 or 150 emery polish on the basis metal, then these coarse polishing lines can be seen in the satin sheen nickel, despite the bi h leveling characteristics of the baths. That is, the coarse polishing lines are only partially smoothened out.
  • an excellent brush type satin finish is obtained of higher corrosion protection than when a nickel plate is brushed after plating.
  • Cadmium tends to whiten the plate somewhat.
  • the presence of sodium and magnesium salts are not harmful.
  • Ammonium salts in' concentrations higher than about 15 grams per liter is in general not desirable because of reduction of the limiting cathode current density.
  • bright or semi-bright nickel plating baths of the Watts, high chloride, sulfarnate and fiuoborate baths or mixtures can be used.
  • other buffers besides boric acid may be used, such as formates, citrates, etc.
  • the pH of the baths may be from about 2 to 6, though the preferred pH values are from about 3.5 to 5.2.
  • 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.
  • the use of these fine insoluble powders 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.
  • the best addition agents or brighteners to achieve the semi-bright and bright nickel plating conditions necessary to obtain satin nickel after the addition to the bath of the aforementioned powders in concentrations of about 10 to 500 grams per liter are the following: the brighteners of the class of organic Salton-compounds including aromatic and unsaturated aliphatic sulfonic acids, sulfonamides .and sulfonimides, such as benzene sulfonic acids, naphthalene sulfonic acids, p-toluene sulfonamide, benzene sulfonamide, o-benzoyl sulfimide, allyl sulfonic acid, 2-butyne-1,4-dis
  • 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 at least 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 plating baths possessing good leveling as those illustrated in Examples 1, 2 below.
  • Less satin lustre for example that of Example 3, is obtained when the nickel baths contain only the carrier type brightener such as benzene sulfonic acids, naphthalene sulfonic acids, p-toluene sulfonamide, benzene sulfonamide, o-benzoyl sulfimide, etc. In the latter cases the satin lustre is flatter. This is also true when the semi-bright sulfur-free type of addition agent such as formaldehyde, chloral hydrate, or bromal,
  • 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 improvement in leveling with the semi-bright sulfur-free addition agents when these ultra-fine particle size powders are used.
  • 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 tinnickel (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, gold, 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-free nickel. This would be for the most severe outdoor exposure as for marine hardware.
  • the corrosion protection to steel, aluminum, magnesium, brass and zinc of the satin nickel with the usual final chromium plate (0.01 mil) even from baths containing organic sulfon-compounds is remarkably superior to the fully bright nickel obtained from the same baths without the fine powders present.
  • the cathode current density is from 10 to amps/sq. ft.
  • Mixtures of powders may be used, such as zirconium'oxide with titanium oxide, aluminum oxide with nickel carbonate, barium fluoride with titanium oxide, .etc. It is important that the powders are clean and wetted by the aqueous nickel bath.
  • Example I Conc., grams/liter Zirconium oxide fine powder (0.03 to 0.3 micron particle size) 40-150 NiSO 6H O 15 0-300 NiCl 6H O 30-100 H 80 30-40 p-Toluene sulfonamide 1-2 o-Benzoylsulfimide 0.1-2 Allyl sulfonic acid 0.5-6 N-allyl quinaldinium bromide 0.002-0.01
  • Example II Cone, grams/liter Titanium oxide superfine powder (0.03 to 0.5
  • Example IV Conc. grams/liter Zirconium oxide ultra-fine powder, 0.02-0.04
  • the satin nickel plate of this invention has about 10 million to about 50 million micro-pits per square inch, as determined by microscopic evaluation at 250 Xmagnification, and in all cases the plate contains a sufficient number of micro-pits to give the plate a microscopic satin appearance.
  • a method for electrodepositing a fine-grained lustrous plate which is essentially nickel comprising the step of electrolyzing an aqueous acidic solution of at least one nickel salt selected from the group consisting of nickel sulfate, nickel chloride, nickel fluoborate, 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 sulfamates of cobalt and iron and at least one soluble organic addition agent capable of producing said fine-grained lustrous plate, said bath containing dispersed therein about 10 to about 500 grams per liter of at least one material selected from the group consisting of silicon carbide, boron carbide, titanium carbide, silicon dioxide, manganese oxide, titanium oxide, zirconium oxide, aluminum oxide, ceric oxide, ferric oxide, chromic oxide, boron nitride, calcium fluoride, strontium fluoride, barium
  • a method for electrodepositing a fine-grained lustrons nickel plate comprising the step of electrolyzin-g an aqueous acidic solution of at least one nickel salt and at least one soluble organic addition agent capable of producing said fine-grained lustrous plate, said bath containing dispersed therein about $10 to about 500 grams per liter of at leastone material selectedfrom the group consisting of silicon carbide, boron carbide, titanium carbide, silicon dioxide, manganese oxide, titanium oxide, zirconium oxide, aluminum oxide, ceric oxide, ferric oxide, 'chromic oxide, boron nitride, calcium fluoride, strontium fluoride, barium fluoride, zinc sulfide, cadmium sulfide and iron silicide, said material in said bath being in the form of a fine powder, the size of which is less than about 2 microns average diameter, continuing said electrolysis until an adherent decorative nickel plate is formed on said surface, and thereafter electrodepositing thereon an overlayer of a metal selected from
  • a method for electrodepositing a fine-grained lustrous nickel plate comprising the step of electrolyzing 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 addition agent capable of producing said fine-grained lustrous plate, said bath containing dispersed therein about 10 to about 500 grams per liter of at least one material selected from the group consisting of silicon carbide, boron carbide, titanium carbide, s licon dioxide, manganese oxide, titanium oxide, zirconium oxide, aluminum oxide, ceric oxide, ferric oxide, chromic oxide, boron nitride, calcium fluoride, strontium fluoride, barium fluoride, zinc sulfide, cadmium sulfide and iron silicide, said material in said bath being in the form of a fine powder, the size of which is less than about 2 microns average diameter, and
  • 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 electrodeposited 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 in said bath at least one type of bath insoluble inorganic non-metallic particles the average diameter of the individual particles thereof being less than about 2 microns, an electrodeposited over-lay plate of a metal selected from the group consisting of chromium, rhodium, silver, tin, brass, bronze, copper, gold and an alloy consisting of about 65% tin and about 35 nickel on said nickel plate said over-lay plate being less than about 5 microns in thickness, said type of particles in said nickel bath being selected from the group consisting of silicon carbide, boron carbide, titanium carbide, silicon dioxide, manganese oxide, titanium oxide, zirconium oxide,'aluminum oxide, ceric oxide, ferric oxide, chromic oxide
  • a composite electroplate in accordance with claim 10 wherein said dissolved organic nickel brightener is selected from the group consisting of aromatic and unsaturated aliphatic sulfonic acids, sulfonamides and sulfonimides.
  • a method in accordance with claim 1 said overlayer is chromium.

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

Priority Applications (15)

Application Number Priority Date Filing Date Title
NL125956D NL125956C (ru) 1960-07-26
NL267500D NL267500A (ru) 1960-07-26
NL267502D NL267502A (ru) 1960-07-26
NL125958D NL125958C (ru) 1960-07-26
NL125957D NL125957C (ru) 1960-07-26
NL267501D NL267501A (ru) 1960-07-26
US45287A US3152973A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous nickel
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
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 (ru) 1960-07-26 1961-07-25
SE7620/61A SE307714B (ru) 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 (ru) 1960-07-26 1961-07-25

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
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

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US3152971A true US3152971A (en) 1964-10-13

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US45285A Expired - Lifetime US3152971A (en) 1960-07-26 1960-07-26 Electrodeposition of fine-grained lustrous nickel
US45286A Expired - Lifetime US3152972A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous satin nickel
US45287A Expired - Lifetime US3152973A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous nickel

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US45286A Expired - Lifetime US3152972A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous satin nickel
US45287A Expired - Lifetime US3152973A (en) 1960-07-26 1960-07-26 Electrodeposition of lustrous nickel

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US (3) US3152971A (ru)
DE (1) DE1248413B (ru)
FR (1) FR1299814A (ru)
GB (1) GB936172A (ru)
NL (6) NL125956C (ru)
SE (3) SE307713B (ru)

Cited By (20)

* 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
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
US3407050A (en) * 1965-05-04 1968-10-22 Trapp Gloria Worthington Duplex nickel material
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
US3617363A (en) * 1967-01-18 1971-11-02 Gen Am Transport Process for electroless metallizing incorporating wear-resisting particles
US3652236A (en) * 1965-10-23 1972-03-28 Res Holland Nv An article having a layer containing nonconductive organic fibers and method of producing
US3657080A (en) * 1968-09-25 1972-04-18 M & T Chemicals Inc Mist suppression in electroplating solutions
US3760143A (en) * 1972-01-03 1973-09-18 Warren Fastener Corp Welding stud
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
FR2616452A1 (fr) * 1987-06-12 1988-12-16 Peugeot Procede de revetement d'une piece quelconque par voie chimique ou electrolytique et piece obtenue par ce procede
FR2617510A1 (fr) * 1987-07-01 1989-01-06 Snecma Procede de codeposition electrolytique d'une matrice nickel-cobalt et de particules ceramiques et revetement obtenu
US4960653A (en) * 1988-06-09 1990-10-02 Kanto Kasei Co., Ltd. Method of copper-nickel-cromium bright electroplating which provides excellent corrosion resistance and plating film obtained by the method
EP0748883A1 (de) * 1995-06-12 1996-12-18 ABB Management AG Teil mit einer galvanisch aufgebrachten Beschichtung und Verfahren zur Herstellung von galvanischen Schichten
US5935407A (en) * 1997-11-06 1999-08-10 Chromalloy Gas Turbine Corporation Method for producing abrasive tips for gas turbine blades
WO2007045688A1 (de) * 2005-10-20 2007-04-26 Wolf-Dieter Franz Herstellung seidenmatter metalloberflächen
CN111455420A (zh) * 2020-06-01 2020-07-28 蒙春英 一种用于复杂形状金属零件表面镀覆锌镍合金的电镀液
CN111876797A (zh) * 2020-07-08 2020-11-03 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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US3825478A (en) * 1972-10-30 1974-07-23 Oxy Metal Finishing Corp Electrolyte and method for electrodepositing microporous chromium-nickel composite coatings
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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
JPS5839236B2 (ja) * 1979-03-30 1983-08-29 住友金属工業株式会社 合金電気メッキ方法
JPH03153896A (ja) * 1989-11-09 1991-07-01 Kanto Kasei Kogyo Kk ニッケルめっき液、そのめっき液を用いた耐食性に優れた銅‐ニッケル‐クロム光沢電気めっき方法並びにそれにより得られためっき皮膜
FR2848219B1 (fr) * 2002-12-09 2006-12-01 Centre Nat Rech Scient Materiau composite utilisable comme revetement lubrifiant
ES2312834T3 (es) * 2002-12-10 2009-03-01 Dompe S.P.A. Arilcetonas quirales en el tratamiento de enfermedades inflamatorias dependientes de neutrofilos.
AT413097B (de) * 2004-06-29 2005-11-15 Hirtenberger Automotive Safety Beschichtung, insbesondere für die zündbrücke eines zünders
DE102011102205A1 (de) * 2011-05-21 2012-11-22 Mahle International Gmbh Verfahren zum Bearbeiten einer Oberfläche eines Bauteils sowie Bauteil
CN107829115B (zh) * 2017-02-23 2020-05-22 常州华威新材料有限公司 一种背涂模具珍珠镍的电镀工艺与用途
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
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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US1163911A (en) * 1915-09-08 1915-12-14 Clarence A Hall Electrolysis.
AU1731328A (en) * 1928-12-11 1929-07-02 Metallgesellschaft Ag Process of obtaining smooth and dense electrolytic metallic deposits
GB513963A (en) * 1938-04-23 1939-10-26 Eaton Mfg Co Improvements in or relating to the electrodeposition of nickel
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
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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
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Cited By (27)

* 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
US3407050A (en) * 1965-05-04 1968-10-22 Trapp Gloria Worthington Duplex nickel material
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
US3617363A (en) * 1967-01-18 1971-11-02 Gen Am Transport Process for electroless metallizing incorporating wear-resisting particles
US3657080A (en) * 1968-09-25 1972-04-18 M & T Chemicals Inc Mist suppression in electroplating solutions
US3760143A (en) * 1972-01-03 1973-09-18 Warren Fastener Corp Welding stud
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
FR2616452A1 (fr) * 1987-06-12 1988-12-16 Peugeot Procede de revetement d'une piece quelconque par voie chimique ou electrolytique et piece obtenue par ce procede
FR2617510A1 (fr) * 1987-07-01 1989-01-06 Snecma Procede de codeposition electrolytique d'une matrice nickel-cobalt et de particules ceramiques et revetement obtenu
US4886583A (en) * 1987-07-01 1989-12-12 Societe Nationale D'etude Et De Construction De Moteurs D'aviation "S.N.E.C.M.A." Formation of protective coatings by electrolytic codeposition of a nickel-cobalt matrix and ceramic particles
US4960653A (en) * 1988-06-09 1990-10-02 Kanto Kasei Co., Ltd. Method of copper-nickel-cromium bright electroplating which provides excellent corrosion resistance and plating film obtained by the method
EP0431228A1 (en) * 1988-06-09 1991-06-12 Kanto Kasei Co., Ltd. Method of copper-nickel-chromium bright electroplating which provides excellent corrosion resistance and plating film obtained by the method
EP0748883A1 (de) * 1995-06-12 1996-12-18 ABB Management AG Teil mit einer galvanisch aufgebrachten Beschichtung und Verfahren zur Herstellung von galvanischen Schichten
US5935407A (en) * 1997-11-06 1999-08-10 Chromalloy Gas Turbine Corporation Method for producing abrasive tips for gas turbine blades
US6194086B1 (en) 1997-11-06 2001-02-27 Chromalloy Gas Turbine Corporation Method for producing abrasive tips for gas turbine blades
WO2007045688A1 (de) * 2005-10-20 2007-04-26 Wolf-Dieter Franz Herstellung seidenmatter metalloberflächen
EP1780311A1 (de) * 2005-10-20 2007-05-02 Wolf-Dieter Franz Herstellung seidenmatter Metalloberflächen
US20090211913A1 (en) * 2005-10-20 2009-08-27 Wolf-Dieter Franz Production of Silky Material of metal surfaces
US8105473B2 (en) 2005-10-20 2012-01-31 Wolf-Dieter Franz Production of satin metal surfaces
CN111455420A (zh) * 2020-06-01 2020-07-28 蒙春英 一种用于复杂形状金属零件表面镀覆锌镍合金的电镀液
CN111876797A (zh) * 2020-07-08 2020-11-03 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
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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FR1299814A (fr) 1962-07-27
NL267501A (ru)
NL267502A (ru)
SE307714B (ru) 1969-01-13
US3152973A (en) 1964-10-13
DE1248413B (de) 1967-08-24
NL267500A (ru)
NL125957C (ru)
GB936172A (en) 1963-09-04
SE301742B (ru) 1968-06-17
SE307713B (ru) 1969-01-13
NL125958C (ru)
NL125956C (ru)
US3152972A (en) 1964-10-13

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