US3268423A - Process of electrodepositing a corrosion resistant nickel-chromium coating - Google Patents

Process of electrodepositing a corrosion resistant nickel-chromium coating Download PDF

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US3268423A
US3268423A US262200A US26220063A US3268423A US 3268423 A US3268423 A US 3268423A US 262200 A US262200 A US 262200A US 26220063 A US26220063 A US 26220063A US 3268423 A US3268423 A US 3268423A
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nickel
plate
liter
grams
bright
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Thaddens W Tomaszewski
Brown Henry
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OMI International Corp
Udylite Corp
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Udylite Corp
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Priority to GB1051685D priority Critical patent/GB1051685A/en
Application filed by Udylite Corp filed Critical Udylite Corp
Priority to US262199A priority patent/US3268308A/en
Priority to US262200A priority patent/US3268423A/en
Priority to US262191A priority patent/US3268307A/en
Priority to US302739A priority patent/US3268424A/en
Priority to DE1521063A priority patent/DE1521063C3/de
Priority to FR965672A priority patent/FR92001E/fr
Priority to NL6402091A priority patent/NL6402091A/xx
Priority to ES297129A priority patent/ES297129A2/es
Priority to NL6409430A priority patent/NL6409430A/xx
Priority to DE1521065A priority patent/DE1521065C3/de
Priority to FR985299A priority patent/FR92105E/fr
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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.
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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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12069—Plural nonparticulate metal components
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12069—Plural nonparticulate metal components
    • Y10T428/12076—Next to each other
    • 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
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    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12069—Plural nonparticulate metal components
    • Y10T428/12076—Next to each other
    • Y10T428/12083—Nonmetal in particulate 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
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    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12139—Nonmetal particles in particulate 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
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12181—Composite powder [e.g., coated, etc.]
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    • 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
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    • 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
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    • 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
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    • 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
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    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component
    • Y10T428/12854—Next to Co-, Fe-, or Ni-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
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    • 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 is for improvements in or relating to decorative nickel electroplating, and more particularly relates to (l) the electrodeposition of sub-microscopic satin-textured to microscopic satin-textured fine-grained nickel plate from semi-bright and bright nickel plating baths containing dispersed therein fine bath-insoluble particles, and (2) to the exceptional corrosion resistance of these textured deposits when over-laid with a thin chromium plate.
  • the decorative fine-grained nickel deposits of this in vention have various degrees of brightness, or of uniform smokiness, depending mainly on the concentration and particle size of the dispersed fine powders in the semibrig-ht or bright nickel electroplating baths, the concentration of the nickel brighteners, the degree of agitation of the cathode or the solution, the brightness and smoothness of the metal surface plated upon, and the thickness of the plate applied, and these decorative nickel plates of various degrees of sub-microscopic and microscopic satin texture and luster when over-laid with a final thin chromium plate provide exceptionally outstanding corrosion protection to the underlying metal.
  • the average particle diameter (herein sometimes referred to as particle size) of the finely powdered in- 3,268,423 Patented August 23, 1966 soluble materials should not be greater than 5 microns. As some roughness, especially on shelf areas where particies can settle may result from the use of materials of particle size greater than about 5 microns, the use of material of particle size less than 5 microns are preferred and are advantageous, with the most preferred particle size averaging about 0.02 to 0.5 micron as determined with the electron microscope. Some agglomerated particles may have larger particle size than 5 microns but with agitation in the nickel bath the larger agglomerates may be reduced to 5 microns and under. Agitation is usually necessary to keep the [fine powder suspended in the baths during plating.
  • Air agitation of the baths can be used. With concentrations of 0.5 to 5 grams/liter of the finest powders, as low as about 0.01% to 0.05% by weight is present in the nickel plate. Microscopic examination of the surface of the plates shows an extremely uniform finely pitted surface which consists of micro-inclusions and micro pits. Calculations and microscopic examinations indicate that the number of micro-inclusions and micro-pits per sq. cm.
  • the fine bath-insoluble powders plate out as uniform dispersions in the semi-bright and brig-ht nicked plate and thereby cause sub-microscopic (with the finest particles of 0.01 to about 0.05 micron size) to microscopic-inclusions and sub-microscopic to microscopic-pitting in the surface of the nickel plate. That is, at any given instant the surface of the semi-bright or bright nickel plate has distributed over its surface multitudin-ous fine particles in various stages of being imbedded in the surface and causing sub-microscopic and microscopic pitting, and with the thinnest plates (flashes or strikes) the pitting is mostly sub-microscopic becoming more microscopically visible with thicker plating.
  • the penetration of the corrosion pits toward the underlying basis metal is very greatly diminished.
  • There is also some evidence of extremely fine stress-cracking of the chromium around the micro-inclusions which is also favorable to forming micro-cathodes and anodes.
  • These textured nickel deposits give the best appearance and corrosion protection results when plated on top of semi-bright sulfur-free nickel or bright nickel deposits. It is best and also simpler to use the regular semi-bright or bright nickel plating baths for most of the plate and to use the minimum of the textured nickel plate required to obtain the desired appearance and corrosion resistance, because the textured nickel plating bath requires added control due to the presence of the dispersed particles, and also because the best corrosion protection results are obtained in this way.
  • bright or semi-bright nickel plating baths of the Watts, sulfate, high chloride, sulfam'ate or fluoborate type, or mixtures can be used. While boric acid is the buffer usually used, other buffers, such as formates, acetates, succinates or citrates may be also employed.
  • the temperature of the barths can be from room temperature to at least 70 C., though in general a temperature of about 55 C. to about 65 C. is preferred.
  • the best addition agent or brighteners to achieve the semi-bright and bright nickel plating conditions necessary to obtain the lustrous textured nickel after the addition to the bath of the aforementioned powders are the following: the sulfur-containing brighteners including aromatic and unsaturated aliphatic sulfonic acids, sul-fonamides and sulfonimides, such as the benzeneor naphthalene-sulfonic acids, p-toluene sultonarnide, ben zene sulfonamide, o-benzoyl sulfimide, vinyl sulfonic acid, allyl sulfonic acid, 2-hutyne l, 4-disulfonic acid, sulfobenzaldehyde, etc., the addition agents which produce semi-bright sulfur-free nickel plate such as formaldehyde, chloral hydrate, bromal hydrate, coumarin, butyne diol, adducts of butyne dio
  • Cobalt and iron can be present in the nickel bath as cobalt or ferrous sulfates, chlorides, bromides, sulfamates or fluoborates in concentrations as high as at least grams/liter, yielding nickel alloy plates containing concentrations of cobalt and/ or iron up to or more and it is to be understood that, except when the context requires otherwise, the expression nickel plate as used herein covers such nickel alloy plates.
  • Surface active agents may be present in the baths, but are not usually necessary in the air agitated baths.
  • the maximum increase in lustrous sheen is obtained when the fine powders are used in the agitated full brig-ht nickel plating baths such as the air-agitated bright nickel plating baths possessing good leveling properties. Less luster is obtained when the nickel baths contain only a carrier type brightener such as a benzene or naphthalene sulfonic acid, p-toluene sulfonarnide, benzene sulfonamide or o-benzoyl sulfimide. In the latter cases the luster is flatter.
  • a carrier type brightener such as a benzene or naphthalene sulfonic acid, p-toluene sulfonarnide, benzene sulfonamide or o-benzoyl sulfimide. In the latter cases the luster is flatter.
  • the sub-microscopic and microscopic satin-textured nickel plate accepts chromium plate like regular nickel plate, and in general only the usual thicknesses of final chromium layer need be used, that is 0.25 microns though thicknesses of 2.5 or 5 microns may be used.
  • the decorative nickel finish as such, or with the usual final chromium finish the microscopic to macroscopic satin textured nickel plate can be given a rhodium, silver, tin, brass, bronze, copper, gold, or tin-nickel 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 or brass coatings. Chromium, rhodium, and tin-nickel alloy plate do not need these organic coatings.
  • Excellent corrosion protection results after the usual final thin chromium plate are obtained by using mixtures of fine powders, for example, barium chromate at 0.05 to 1 gram/liter with 1 to 5 grams/liter of lead phosphate or thorium phosphate or lead chromate.
  • Thorium phosphate used in total concentrations of 0.1 to about 20 grams/liter in conjunction with about 1 to 50 grams/liter of very fine silica powder also gives ex cellent results.
  • Example II Lead phosphate and/or thorium phosphate 0.02-5 micron av. particle size 0.1- NiSO .6H O 200-300 NiCl .6H O 40-80 H BO 40 Benzene sulfonamide 1-3 Allyl sulfonic acid 1-3 2-butynoxy-1, 4-diethane sulfionic acid 0.050.2
  • Air agitation or mechanical agitation Air agitation or mechanical agitation.
  • Example III Thorium phosphate 0.02-3 micron av. particle size 0.1-5 Ultra-fine silica powder 0.02-0.05 micron ultimate particle size (Quso) 1-50 NiSO .6H O 50-200 NiCl .6H O 200-100 H BO 40 o-Benzoyl sulfimide 2-4 p-Toluene sulfonamide 1-2 Allyl sulfonic acid 1-3 2-butynoxy-l, 4-diethane sulfonic acid 0.05-0.2
  • inorganic bath compositions can be used and other nickel brighteners, but it is preferred to use at least one organic sulfon-compound as one of the brighteners.
  • the ultra-fine particles of about 0.01 to 0.05 micron size particles are used in the semi-bright and bright nickel electroplating bath, it is diflicult to see the included particles in cross-section of the nickel plate even at the highest magnification of the light microscope.
  • the surface of the plate using strong light it is possible to just see the microscopic pitting effect of these submicroscopic particles. The thinner the plate that is deposited on a bright surface, the more difficult is it to distinguish any difference between the appearance of the textured deposit and the bright plate obtained without the particles present.
  • the nickel brighteners that produce very high leveling and brilliance as, for eXample, those given in US. 2,647,866 (Aug. 4, 1953) and U.S. 2,800,440 and 2,800,- 442 (July 23, 1957) will produce the highest brilliance with the powders dispersed in these bright nickel baths.
  • the textured decorative nickel plate of this invention on complex shaped articles such as many zinc die-cast articles, for example, rear view mirror holders, intricate light housings, steel bumpers, hub caps, and grilles, it is best to use duplex or dual nickel underneath the textured nickel deposit.
  • the total nickel deposit would consist of semi-bright sulfur-free nickel followed by regular bright nickel followed by a thin textured nickel deposit of this invention. The latter being used as thin plate (0.01 to about 0.1 mil) if the highest brilliance is desired.
  • the copper plate When ductile copper plate is used under nickel plate that has a final coating of the textured decorative nickel plate of this invention, then the copper plate also helps in the total corrosion resistance unlike the case when copper is used as a substitute for part of the bright nickel thickness in deposits of copper-bright nickel and the usual 0.01 mil thick final chromium. It is believed that this beneficial effect of copper is also due to the tiny cathode areas developed in the final thin chromium plate, which in turn is due to the fine favorable porosity pattern developed in the thin final chromium plate as a result of its being deposited over a decorative nickel surface containing multitudinous sub-micro to micro-inclusions and sub-micro to micro-pits of the order of 10 per sq. cm.
  • the nickel hydroxide powder can be formed in the bath as a colloid by adding alkalis, such as sodium hydr-oxide or barium hydroxide, to the nickel bath.
  • alkalis such as sodium hydr-oxide or barium hydroxide
  • the preferred phosphates of thorium and of lead are the orthophosphates, that is, the preferred phosphates are the most Water-insoluble ones.
  • the preferred oxides of nickel and cobalt are the divalent ones, and dead burnt ones.
  • the oxides and hydroxides of nickel and cobalt seem to acquire a positive charge by adsorption of hydrogen ions and nickel ions in the nickel baths at pH values of about 5.2-6.0 and this seems to occur with the other types of precipitated powders such as the water-insoluble stannates, for example, calcium, barium and strontium stannates, as well as lead and barium chromates, and thorium and lead phosphates.
  • the acquiring of a positive charge by adsorption appears to the main mechanism by which these particles plate out into the nickel cathode from the semi-bright and bright nickel plating baths.
  • the best of the water-insoluble stannate powders to use are those of strontium and barium, with calcium, thorium, cerium next, and lead, antimony, bismuth, magnesium, cobalt, nickel and iron next. In some cases higher than 20 grams/liter concentration can be used, but for lead, antimony, and bismuth it is preferred to use the lower concentration values.
  • the hypophosphate of thorium is nearly as insoluble as the thorium orthophosphate and gives very good results in concentrations of 0.1 to about 50 grams/liter.
  • the water-insoluble oxalates of thorium and lead give very similar results to the phosphates of thorium and lead in the concentrations of 0.1 to about 20 grams/liter, with the thorium oxalate giving superior results both from the standpoint of uniform decorative appearance and corrosion protection results after the final thin chromium plate.
  • lead oxalate just like lead stannate should be used at the lower concentration values of 0.1 to about 3 grams/liter for best results. At the higher concentration values these lead salts introduce too much free lead ions in the baths which tend to darken the low current density plate, and to decrease the adhesion of the plate. It is also preferred for this reason to use the lead salts in the sulfate type of bright nickel, e.g., bright nickel baths based on the Watts bath inorganic formulation.
  • a method for electrodepositing a decorative nickel plate which comprises 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 semi-bright to fully bright nickel plate, said solution containing dispersed therein about 0.1 to about 50 grams/ liter of at least one water-insoluble material selected from the group consisting of the phosphates of lead, about 0.1 to 20 grams/liter of lead chromate, and lead oxalate, 0.1 to about 5 grams/liter of barium chromate, 1 to about '50 grams/liter of the oxides and hydroxides of cobalt and nickel, and 0.1 to about 20 grams/liter of the stannates of calcium, strontium, barium, magnesium, lead, nickel, cobalt, iron, antimony and bismuth, said material being in the form of a particulate dispersion the particles of which having
  • said dissolved organic nickel brightener is selected from the group consisting of aromatic and unsaturated 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)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
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US262200A 1963-03-01 1963-03-01 Process of electrodepositing a corrosion resistant nickel-chromium coating Expired - Lifetime US3268423A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
GB1051685D GB1051685A (enrdf_load_stackoverflow) 1963-03-01
US262199A US3268308A (en) 1963-03-01 1963-03-01 Electrodeposition of a corrosion resistant decorative nickel-chromium coating and products thereof
US262200A US3268423A (en) 1963-03-01 1963-03-01 Process of electrodepositing a corrosion resistant nickel-chromium coating
US262191A US3268307A (en) 1963-03-01 1963-03-01 Process of electrodepositing a corrosion resistant nickel-chromium coating and products thereof
US302739A US3268424A (en) 1963-03-01 1963-08-16 Method of depositing a corrosion resistant composite nickel electroplate
FR965672A FR92001E (fr) 1963-03-01 1964-02-29 Procédé de nickelage, bains utilisés et produits obtenus
DE1521063A DE1521063C3 (de) 1963-03-01 1964-02-29 Saures galvanisches Nickelbad zum Abscheiden dekorativer feinkörniger, satinbis hochglänzender Überzüge mit verbesserter Korrosionsfestigkeit
ES297129A ES297129A2 (es) 1963-03-01 1964-03-02 Metodo de galvanizado de niquel mediante electrodeposito deuna placa de niquel desde un bano.
NL6402091A NL6402091A (enrdf_load_stackoverflow) 1963-03-01 1964-03-02
NL6409430A NL6409430A (enrdf_load_stackoverflow) 1963-03-01 1964-08-14
DE1521065A DE1521065C3 (de) 1963-03-01 1964-08-14 Saures galvanisches Nickelbad zum Abscheiden dekorativer feinkörniger, satin- bis hochglänzender Überzüge mit verbesserter Korrosionsfestigkeit
FR985299A FR92105E (fr) 1963-03-01 1964-08-14 Procédé de nickelage, bains utilisés et produits obtenus

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US28219963A 1963-03-01 1963-03-01
US262199A US3268308A (en) 1963-03-01 1963-03-01 Electrodeposition of a corrosion resistant decorative nickel-chromium coating and products thereof
US262200A US3268423A (en) 1963-03-01 1963-03-01 Process of electrodepositing a corrosion resistant nickel-chromium coating
US262191A US3268307A (en) 1963-03-01 1963-03-01 Process of electrodepositing a corrosion resistant nickel-chromium coating and products thereof
US302739A US3268424A (en) 1963-03-01 1963-08-16 Method of depositing a corrosion resistant composite nickel electroplate

Publications (1)

Publication Number Publication Date
US3268423A true US3268423A (en) 1966-08-23

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US262200A Expired - Lifetime US3268423A (en) 1963-03-01 1963-03-01 Process of electrodepositing a corrosion resistant nickel-chromium coating
US262199A Expired - Lifetime US3268308A (en) 1963-03-01 1963-03-01 Electrodeposition of a corrosion resistant decorative nickel-chromium coating and products thereof
US262191A Expired - Lifetime US3268307A (en) 1963-03-01 1963-03-01 Process of electrodepositing a corrosion resistant nickel-chromium coating and products thereof
US302739A Expired - Lifetime US3268424A (en) 1963-03-01 1963-08-16 Method of depositing a corrosion resistant composite nickel electroplate

Family Applications After (3)

Application Number Title Priority Date Filing Date
US262199A Expired - Lifetime US3268308A (en) 1963-03-01 1963-03-01 Electrodeposition of a corrosion resistant decorative nickel-chromium coating and products thereof
US262191A Expired - Lifetime US3268307A (en) 1963-03-01 1963-03-01 Process of electrodepositing a corrosion resistant nickel-chromium coating and products thereof
US302739A Expired - Lifetime US3268424A (en) 1963-03-01 1963-08-16 Method of depositing a corrosion resistant composite nickel electroplate

Country Status (4)

Country Link
US (4) US3268423A (enrdf_load_stackoverflow)
DE (2) DE1521063C3 (enrdf_load_stackoverflow)
GB (1) GB1051685A (enrdf_load_stackoverflow)
NL (2) NL6402091A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US3428441A (en) * 1965-07-28 1969-02-18 Kewanee Oil Co Article coated with a composite particulate,microporous chromium coating and method of producing said article
US3652236A (en) * 1965-10-23 1972-03-28 Res Holland Nv An article having a layer containing nonconductive organic fibers and method of producing
US3866289A (en) * 1969-10-06 1975-02-18 Oxy Metal Finishing Corp Micro-porous chromium on nickel-cobalt duplex composite plates
US4470897A (en) * 1983-09-20 1984-09-11 Bethlehem Steel Corp. Method of electroplating a corrosion-resistant zinc-containing deposit
US20110038577A1 (en) * 2007-12-14 2011-02-17 Peter Horling Bearing Arrangement for a Tension Roller

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3471271A (en) * 1965-08-16 1969-10-07 Udylite Corp Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate
US3488263A (en) * 1968-04-22 1970-01-06 Gen Electric Codeposition of metallics and non-metallics
US3625821A (en) * 1968-06-26 1971-12-07 Westinghouse Electric Corp Fuel-element coating containing burnable poison
US3657080A (en) * 1968-09-25 1972-04-18 M & T Chemicals Inc Mist suppression in electroplating solutions
GB1282373A (en) * 1969-10-15 1972-07-19 A I C Approvvigionamenti Ind C Nickel-chromium electroplating
GB1404855A (en) * 1971-07-28 1975-09-03 Mitsui Mining & Smelting Co Catalytic purification of exhaust gases
US3812566A (en) * 1972-07-03 1974-05-28 Oxy Metal Finishing Corp Composite nickel iron electroplate and method of making said electroplate
DE2236443C3 (de) * 1972-07-25 1978-05-24 Elektroschmelzwerk Kempten Gmbh, 8000 Muenchen Wäßriges Bad zur Herstellung von metallischen Überzügen, die nichtmetallische, feinverteilte Feststoffe eingelagert enthalten
US3825478A (en) * 1972-10-30 1974-07-23 Oxy Metal Finishing Corp Electrolyte and method for electrodepositing microporous chromium-nickel composite coatings
JPS5618080B2 (enrdf_load_stackoverflow) * 1973-08-14 1981-04-25
US4182412A (en) * 1978-01-09 1980-01-08 Uop Inc. Finned heat transfer tube with porous boiling surface and method for producing same
IT1224259B (it) * 1984-10-05 1990-10-04 Baj Ltd Perfezionamento nei rivestimenti metallici di protezione e procedimento di preparazione
JPH0772360B2 (ja) * 1987-07-10 1995-08-02 日本鋼管株式会社 Ｚｎ系複合電気めつき鋼板
US6045682A (en) * 1998-03-24 2000-04-04 Enthone-Omi, Inc. Ductility agents for nickel-tungsten alloys
WO2006082218A1 (de) * 2005-02-04 2006-08-10 Siemens Aktiengesellschaft Oberfläche mit einer die benetzbarkeit vermindernden mikrostruktur und verfahren zu deren herstellung
PL2145986T3 (pl) * 2008-07-15 2010-09-30 Atotech Deutschland Gmbh Roztwór i sposób elektrochemicznego osadzania metalu na substracie
DE102010055968A1 (de) 2010-12-23 2012-06-28 Coventya Spa Substrat mit korrosionsbeständigem Überzug und Verfahren zu dessen Herstellung
WO2013025352A1 (en) 2011-08-18 2013-02-21 Apple Inc. Anodization and plating surface treatments
KR20130126233A (ko) * 2012-05-11 2013-11-20 현대자동차주식회사 음각처리를 이용한 도금방법
GB201308473D0 (en) * 2013-05-10 2013-06-19 Authentix Inc Plating of articles
CN109107559B (zh) * 2018-08-31 2021-08-03 四川文理学院 一种电沉积制备钛酸钙的方法及其应用
CN111926354A (zh) * 2020-10-12 2020-11-13 江西科技学院 一种计算机数据处理装置用电气元件及其制造方法
CN116005157B (zh) * 2022-12-13 2023-12-19 苏州圆格电子有限公司 一种钕铁硼表面预处理方法和系统
EP4488408A1 (de) * 2023-07-06 2025-01-08 Dr.Ing. Max Schlötter GmbH & Co. KG Dispersionselektrolyt und chemisches bad für partikelhaltige nickel- und nickellegierungsschichten

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739085A (en) * 1953-03-13 1956-03-20 Westinghouse Electric Corp Insulating coatings for magnetic sheets
US2771409A (en) * 1953-02-19 1956-11-20 Gen Motors Corp Method of making grid bearings
US3057048A (en) * 1958-11-06 1962-10-09 Horizons Inc Protection of niobium
US3061525A (en) * 1959-06-22 1962-10-30 Platecraft Of America Inc Method for electroforming and coating
US3090733A (en) * 1961-04-17 1963-05-21 Udylite Res Corp Composite nickel electroplate
US3132928A (en) * 1962-02-26 1964-05-12 Donald D Crooks Simultaneous brazing and corrosion protecting refractory metals

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2849353A (en) * 1955-02-08 1958-08-26 Hanson Van Winkle Munning Co Bright nickel plating

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2771409A (en) * 1953-02-19 1956-11-20 Gen Motors Corp Method of making grid bearings
US2739085A (en) * 1953-03-13 1956-03-20 Westinghouse Electric Corp Insulating coatings for magnetic sheets
US3057048A (en) * 1958-11-06 1962-10-09 Horizons Inc Protection of niobium
US3061525A (en) * 1959-06-22 1962-10-30 Platecraft Of America Inc Method for electroforming and coating
US3090733A (en) * 1961-04-17 1963-05-21 Udylite Res Corp Composite nickel electroplate
US3132928A (en) * 1962-02-26 1964-05-12 Donald D Crooks Simultaneous brazing and corrosion protecting refractory metals

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US3428441A (en) * 1965-07-28 1969-02-18 Kewanee Oil Co Article coated with a composite particulate,microporous chromium coating and method of producing said article
US3652236A (en) * 1965-10-23 1972-03-28 Res Holland Nv An article having a layer containing nonconductive organic fibers and method of producing
US3866289A (en) * 1969-10-06 1975-02-18 Oxy Metal Finishing Corp Micro-porous chromium on nickel-cobalt duplex composite plates
US4470897A (en) * 1983-09-20 1984-09-11 Bethlehem Steel Corp. Method of electroplating a corrosion-resistant zinc-containing deposit
EP0140564A3 (en) * 1983-09-20 1985-06-12 Bethlehem Steel Corporation Electroplated product and method
US20110038577A1 (en) * 2007-12-14 2011-02-17 Peter Horling Bearing Arrangement for a Tension Roller
US8672557B2 (en) 2007-12-14 2014-03-18 Aktiebolaget Skf Bearing arrangement for a tension roller

Also Published As

Publication number Publication date
DE1521065A1 (de) 1969-08-07
DE1521065C3 (de) 1974-11-07
DE1521063B2 (de) 1974-01-10
DE1521063C3 (de) 1974-08-29
GB1051685A (enrdf_load_stackoverflow)
DE1521065B2 (de) 1973-04-12
NL6409430A (enrdf_load_stackoverflow) 1965-02-17
US3268307A (en) 1966-08-23
US3268424A (en) 1966-08-23
US3268308A (en) 1966-08-23
DE1521063A1 (de) 1969-08-14
NL6402091A (enrdf_load_stackoverflow) 1964-09-02

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