US3009236A - Protective and decorative coatings containing nickel - Google Patents

Protective and decorative coatings containing nickel Download PDF

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US3009236A
US3009236A US700352A US70035257A US3009236A US 3009236 A US3009236 A US 3009236A US 700352 A US700352 A US 700352A US 70035257 A US70035257 A US 70035257A US 3009236 A US3009236 A US 3009236A
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nickel
layer
chromium
composite
coating
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Waclaw A Wesley
Burton B Knapp
Robert J Mckay
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Huntington Alloys Corp
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International Nickel Co Inc
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Priority to NL233860D priority Critical patent/NL233860A/xx
Application filed by International Nickel Co Inc filed Critical International Nickel Co Inc
Priority to US700352A priority patent/US3009236A/en
Priority to GB38324/58A priority patent/GB852673A/en
Priority to SE1105858A priority patent/SE205488C1/sv
Priority to FR780754A priority patent/FR1283812A/fr
Priority to DEM39818A priority patent/DE1188897B/de
Priority to NL233860A priority patent/NL111002C/nl
Priority to CH6694058A priority patent/CH382511A/fr
Priority to BE583671A priority patent/BE583671A/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/44—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • 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
    • 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.]
    • Y10T428/12736—Al-base component
    • Y10T428/1275—Next to Group VIII or IB 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
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-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
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component

Definitions

  • FIGURE 4 WACLAW ANDREW WESLEY BURTON BOWER KNAPP ROBERT JAMES McKAY INVENTORS BYQ. W ATTORNEY United States Patent 7 3,009,236 PROTECTIVE AND DECORATIVE COATINGS CONTAINING NICKEL Waclaw A. Wesley, Plainfield, and Burton B. Knapp, Westfield, N.J., and Robert J. McKay, Onancock, Va., assignors to The International Nickel Company, Inc., New York, N.Y., a corporation of Delaware Filed Dec. 3, 1957, Ser. No. 700,352 11 Claims. (Cl.
  • the present invention relates to the provision of decorative and protective metallic coatings and, more particularly, to the provision on metallic surfaces of bright composite electrodeposited coatings which have substantially improved resistance to the destructive influences of industrial and marine atmospheres and which exhibit an attractive and decorative surface appearance for long periods of time during use.
  • Electrodeposited chromium is pleasing in appearance and offers a degree of resistance to corrosive atmospheres but fails to provide sufficient protection for underlying metals, e.g., ferrous metals, chiefly on account of the inherent porosity characterizing chromium electrodeposits. Electrodeposited nickel may also have a bright and pleasing appearance but nickel deposits on basis metals are characterized by fogging in industrial atmospheres and then by pitting at myriads of points on the surface.
  • chromium reducesthe fogging tendency of nickel but the chromium layer is thin and not impervious to atmospheric and other corrosive effects and, as a consequence thereof, exposure to atmospheres containing detrimental and corrosive substances, e.g., sulfur dioxide, leads to pitting and/or perforation of the composite coating.
  • detrimental and corrosive substances e.g., sulfur dioxide
  • the protective value of conventional composite nickel-chromium coatings increases with increasing thickness of the nickel deposit, but commercially this has not proved to be a panacea for rust spotting of the plated metal, e.g., steel, exposed to weather.
  • Another object of the invention is to provide metallic surfaces including metals and/ or alloys with composite electrodeposited coatings characterized by a high degree of resistance to corrosion when subjected to weathering and which retain a decorative and pleasing surface appearance for relatively long periods of time during use.
  • the invention also contemplates providing bright, decorative and protective composite electrodeposited coatings on metallic surfaces including metals and/ or alloys which, when compared to conventional composite coatings of comparable thickness, manifest an improved order of resistance to perforation by corrosive atmospheres, better protection of the metallic surface from corrosion and longer retention of a decorative and pleasing surface appearance during use.
  • the invention further contemplates providing a process for accomplishing the foregoing objects.
  • FIGURE 1 is a reproduction of a photograph taken at about /2 size depicting a comparison of a series of four test panels having composite electroplated coatings within the invention prepared using layers of gray or Watts-type nickel with a control panel having a conventional electrodeposited coating containing a single layer of Watts-type nickel (the left-hand panel in the top row of three panels) after exposure to the atmosphere for eleven months in an industrial location. All the panels were given a final chromium decorative plate before exposure;
  • FIGURE 2 is a reproduction of a phonograph taken at about A2 size depicting a comparison of a series of test panels similar to those of FIGURE 1 within the invention with a control panel having a single nickel layer similar to that of FIGURE 1 (the left-hand panel in the top row of three panels) after exposure to the atmosphere for ten months in a marine location;
  • FIGURE 3 is a reproduction of a photograph taken a! about /2 size depicting a comparison of a series of four test panels having composite electroplated coatings within the invention prepared using layers of bright nickel with a control panel having a conventional single-layer coating containing a single layer of bright nickel (the left-hand panel in the top row of three panels) after exposure to the atmosphere for eleven months in an industrial location. All the panels were given a final chromium decorative plate before exposure; and
  • FIGURE 4 is a reproduction of a photograph taken at about /2 size depicting a comparison of a series of four test panels similar to those of FIGURE 3 having a composite coating within the invention with a control panel having a single layer of bright nickel similar to that of FIGURE 3 (the left-hand panel in the top row of three panels) after exposure to the atmosphere for ten months in a marine location.
  • the composite electrodeposited coatings provided in accordance with the present invention are comprised of a plurality of nickel layers and a layer of electrodeposited chromium interposed between said layers of nickel.
  • a relatively thin layer of chroinium having a thickness of about to 20* micro-inches is advantageously deposited on the outermost layer of nickel.
  • the composite coatings of the present invention are electrodeposited on a metallic base, including metals and/ or alloys, it has been found that the coatings are more resistant to atmospheric and other corrosive effects and retain a pleasing protective surface appearance longer during use than do known bright coatings of the same order of thickness, e.g., the conventional nickel-chromium and copper-nickel-chromium electrodeposits containing a single nickel layer. It is important within the concepts of the presentinvention in order to insure the attainment of highly satisfactory results that the respective thicknesses of each of the electrodeposited metal layers comprising the composite coating be controlled within the following ranges:
  • the thickness of the intermediate chromium layer within the range of 0.001 to about 0.03 mil.
  • superior results are obtained using a basis nickel layer having a thickness of about 0.1 to 1 mil' and an outer nickel layer having a thickness of about 0.1 to 2 mils.
  • thicker outer nickel layers should be employed when the basis nickel layer has a thickness in the lower portion of the range described.
  • the outer nickel layer should be at least about 0.5 mil, or more advantageously about 0.6 or 0.75 or 1 mil thick.
  • the total thickness of nickel in the two layers should be at least about 0.5 mil but most advantageously is about 1 mil, particularly when the coating is to be subjected to outdoor exposure.
  • composite coatings having layer thicknesses within the foregoing preferred ranges are employed, we have found that the results obtained are not only markedly superior to the results obtained utilizing conventional composites, e. g., nickel-chromium composites, of comparable thickness, e.g., about 1 mil, but are comparable and often superior to conventional composites, e.g., nickel-chromium, of twice the thickness, e.g., about 2 mils.
  • the effectiveness of the chromium intermediate layer is greatest when the thickness thereof is maintained in the range of 0.005 to 0.015 mil.
  • the nickel layers contemplated by the invention may be made of electrodeposited nickel obtained from sulfatechloride plating baths of the conventional Watts-type, or may be made of nickel deposited from the all-chloride bath or the all-sulfate bath, or may be made of bright nickel deposited from baths containing the usual brighteners or levelers for enhancing the appearance of the nickel electrodeposit.
  • Nickel plating baths for producing nickel deposits satisfactory for use in the present invention contain up to 400 grams per liter of nickel sulfate (NiSO .7H O), up to 400 grams per liter of nickel chloride (NiCl .6H O) and up to 50 grams per liter (preferably 10 to 40 grams per liter) of a buffer such as boric acid.
  • the essential ingredients of the Watts-type nickel plating bath are nickel sulfate (NiSO .7H O) and nickel chloride (NiCl .6H O) which may be present in the bath in amounts of about to about 400 grams per liter and of about 10 to about 60 grams per liter, respectively.
  • the bath is operated in the pH range of about 1.5 to 6.
  • a buffering agent such as boric acid is included in the bath in an amount of up to about 50 grams per liter, e.g., about 10 to about 40 grams of boric acid per liter.
  • a small amount (e.g., about 0.2 gram per liter) of a wetting agent such as a sodium lauryl sulfate is usually included in the bath to prevent undesirable pitting.
  • Electrode current densities of about 20 to about 100 amperes per square foot are usually employed and the operating range of bath temperatures is about to about 160 F.
  • Nickel deposited from the Watts-type bath generally will require buffing before application of the final chromium plate to insure a fully bright appearance.
  • Plating baths for plating bright nickel are of generally similar composition to the Watts-type bath, and may, for example, contain about 25 to 300 grams per liter of nickel sulfate (NiSO .7H O) and 30 to 225 grams per liter of nickel chloride (NiCl 6H O), with up to 50 grams per liter of boric acid as a buffer.
  • Bright nickel baths include combinations of addition agents for producing a more lustrous and brighter deposit than is obtainable with the Watts-type bath. These addition agents generally include a combination of a wetting agent, a leveling and/ or smoothing agent, a luster-producing agent and a stress-reducing agent. Bright nickel plating baths are discussed in Modern Electroplating, John Wiley and Sons, Inc., New York, 1953, at pages 311 to 318 and in many US. patents, including, e.g., Patents No. 2,191,813, No. 2,389,135, No. 2,524,619, No. 2,647,866 and No. 2,648,628.
  • Plating baths for producing semi-bright nickel are generally similar in composition to Watts-type baths and bright nickel baths and contain a leveling agent, such as coumarin and derivatives thereof, which contributes a leveling and scratch-covering property to the plate without introducing a high level of stress therein as may be the case with bright nickel.
  • Semi-bright nickel plates are not as bright as the bright nickel plates, but are more easily buffed than conventional Watts-type plates, and are characterized by a high degree of smoothness.
  • Nickel electrodeposits from the Watts-type bath generally have a hardness of about to Vickers, while bright nickel electrodeposits generally have a higher hardness which may be as high as about 500 Vickers.
  • a particular embodiment of the invention wherein a satisfactory composite coating upon an underlying metal, e.g., steel, is provided without any mechanical polishing operation, e.g., bufiing, includes the following steps:
  • outer nickel layer may advantageously comprise a layer of semi-bright nickel applied over the intermediate layer in suflicient thickness to provide a good leveling action, e.g., about 0.5 mil, and a layer thereover of bright nickel to provide a bright finish upon which the final chromium layer may be applied.
  • layers of bright nickel may be employed in accordance with the invention.
  • the invention also contemplates multi-layer coatings havings a plurality of electrodeposited intermediate layers of the kind and thickness described hereinbefore and having a plurality of electrodeposited nickel layers having thicknesses as aforedescribed.
  • a multilayer composite on steel comprising a layer on the steel of electrodeposited nickel 0.1 mil thick, a layer thereon of electrodeposited chromium 0.01 mil thick, another layer of nickel 0.1 mil thick, a further layer of chromium 0.01 mil thick, and an outer layer of nickel 1 mil thick, with a decorative coating of chromium micro-inches thick is a satisfactory multi-layer composite in accordance with the invention.
  • test specimens for the most part were electrodeposited upon panels of polished SAE 1010 steel in the form of /8" x 4" x 6" plates.
  • One of the sets of test specimens comprised foils which were made by electrodepositin'g coatings to be tested on a highly polished cobalt-chromium alloy starting sheet from which electrodeposited foils could easily be stripped.
  • Conventional cleaning and plating methods well known to those skilled in the art were employed in the preparation of the test panels and foils.
  • the steel panels were prepared for plating according to the following procedure:
  • the panels were examined to compare the corrosion resistance of the coatings deposited thereon with each other and with the nickel-chromium control panels of the conventional type.
  • the examination comprised a visual inspection wherein the panels were given a merit rating designating the relative order and the appearance of each panel, with the panel exhibiting the best appearance being designated by the numeral 1.
  • the panels were rated according to the method recommended by the American Society for Testing Materials Committee B8, Subcommittee II, described in the Proceedings of the A.S.T.M., vol. 49, 1949, at pages 220 et seq.
  • the [following comparison of percentage corrosion-afiected area and rating numbers was employed in evaluating the panels described in Tables I to VII hereinafter:
  • Table VI tests wherein a chromium intermediate layer 0.01 mil thick was positioned closer to the basis metal (panels 36 I and M) were also included.
  • FIGURE 1 of the drawing comprises reproductions of photographs of certain of the panels made using the Watts-type nickel which were included in Table VI after the panels were exposed in an industrial atmosphere. Coatings 1 mil thick were originally plated on these panels.
  • the upper left-hand panel is panel 37 I and the remaining panels (proceeding from panel 37 I in order from left to right) are panels 32 I, 28 I, 29 I and 30 I.
  • the control panel panel (panel 37 I) exhibited much heavy rust stain accompanied by much crater rusting.
  • Panel 32 I represents an improvement over the control panel and the crater-type of rusting was not as severe. This panel could be more readily restored to a decorative appearance than could the control panel.
  • the further improvement represented by panels 28 I, 29 I and 30 I having composite coatings within the invention as compared to the control panel, which had a single nickel layer, is readily apparent from the drawmg.
  • FIGURE 2 of the drawing comprises reproductions of photographs of similar panels made using Watts nickel and included in Table VI after the panels were exposed in a marine atmosphere.
  • the upper left-hand panel is the control panel (panel 37 M), which had a single nickel layer, and the remaining panels (proceeding from panel 37 M from left to right) are panels 32 M, 28 M, 29 M and 30 M.
  • the control panel (panel 37 .M) was badly cratered and its decorative value was destroyed.
  • the panels having composite coatings within the present invention retained a high proportion of their original decorative and protective value.
  • Panel 28 M which had an intermediate layer of chromium 0.01 mil thick, was affected only very slightly by the exposure.
  • FIGURE 3 of the drawing comprises reproductions of photographs of certain of the panels made using bright nickel which were included in Table VII after the panels were exposed in an industrial atmosphere. Coatings 1 mil thick were originally plated on these panels.
  • the up per left-hand panel is the control panel having a singlelayer nickel coating (panel 49 I).
  • the remaining panels had composite coatings within the invention and, proceeding from panel 49 I from left to right, these panels are, respectively, panels 42 I, 43 I, 44 I and 45 I.
  • the improvement in the protective and decorative value represented by the composite coatings provided in accordance with the invention as compared to the control panel is readily evident from the drawing.
  • FIGURE 4 of the drawing comprises reproductions of photographs of panels similar to those of FIGURE 3 and made using bright nickel. These panels are also included in Table VII.
  • the control panel having a single nickel layer (panel 49 M) is again at the upper lefthand corner.
  • the panels having composite coatings within the invention are, proceeding from left to right from the control panel, panels 42 M, 43 M, 44 M and 45 M.
  • the decorative value of the control panel was destroyed by the exposure and deep crater rusting is evident as a result of the exposure.
  • the composite coatings within the invention retained their decorative value to a greatly improved extent, as is evident from the drawing.
  • FIGURES 1 and 3 Comparison of FIGURES 1 and 3 with the corres' ponding FIGURES 2 and 4 strikingly demonstrates the variation in the manner of corrosive attack displayed in the industrial atmosphere as compared to that displayed in the marine atmosphere. This comparison also indicates the complicated nature of the problems involved in providing improved decorative and protective coatings containing nickel layers.
  • the panels were examined in the as-exposed condition since this condition represents the appearance of the panels as they would be in use. Many of the panels were also cleaned and examined again. Cleaning improved the appearance of the panels but it was noted that, on re-exposure for a relatively short time, the conventional nickel-chromium control panels exhibited a much greater amount of rust staining than was the case with the composite coatings containing an intermediate layer embedded in the nickel. The diite-rence was particularly marked when the control panels were compared to the composite coated panels having an intermediate chromium layer.
  • Brightening agent (a mixture of saccharin, benzene sulfonamide and paratoluene sulfonamide) g.p.l. 6 Luster-producing agent containing pyridinium and quinolinium compounds mL/l. 1.25
  • Wetting agent (a mixture of agents exemplified by a sodium salt of lauryl sulfoacetate and a sodium salt of monolauryl ether of ethylene glycol monosulfate) ml./l. Plating conditions:
  • the present invention is particularly applicable for the purpose of providing composite electrodeposited coatings on structural metals which are susceptible to atmospheric attack when exposed by themselves.
  • foundation metals include copper, zinc, aluminum, brass, etc., and alloys such as steel, e.g., carbon steels and low alloy steels containing phases associated with alpha iron, etc.
  • the composite electrodeposits of the invention are suitable for use in both industrial and marine atmospheres.
  • the preferred composite or sandwichtype electrodeposited coatings described hereinbefore are useful in, and satisfactory for, the usual commercial applications such as automotive bumpers and trim where a decorative and/or protective coating resistant to atmospheric corrosive effects is required.
  • Other applications include trim and outer shells for electrical appliances and the like, and including refrigerators, toasters, stoves, etc.; metal furniture; plumbing fixtures; household hardware; industrial hardware; etc., where a bright, attractive metal finish which is durable in service is required.
  • the outer chromium coating described hereinbefore is generally required where stain resistance to atmospheric corrosive efiects is a criterion.
  • nickel and chromium coatings contemplated in accordance with the invention advantageously are produced by electrodeposition.
  • chemically deposited nickel coatings such as those described in the Brenner et al. U.S. Patent No. 2,532,283, coatings produced by high vacuum vaporizing, and coatings produced by thermal decomposition of metal carbonyls, e.g., nickel carbonyl, may also be employed to produce metal layers in accordance with the invention.
  • a metal article having firmly bonded to the surface thereof a protective and decorative composite metal coating, said coating comprising a foundation layer of nickel about 0.1 to about 2 mils thick deposited on said surface, an electron deposited layer of chromium about 0.005 to about 0.015 mil thick applied to said nickel layer, and an outer layer of nickel about 0.1 to 2 mils thick applied to said chromium layer, said composite coating being characterized by an improved decorative and protective effect as compared to a coating having a single nickel layer of the same thickness.
  • a metal article having firmly bonded to the surface thereof a protective and decorative composite metal coating, said coating comprising a foundation layer of nickel about 0.1 to about 2. mils thick deposited on said surface, an electrodeposited layer of chromium about 0.001 mil to about 0.03 mil thick applied to said nickel layer, and a layer of nickel about 0.1 to about 2 mils thick applied to said chromium layer, said composite coating having an improved decorative and protective effect as compared to a coating having a single nickel layer of the same thickness.
  • an article of metal from the class consisting of copper, brass, zinc, aluminum and steel having firmly bonded to the surface thereof a protective and decorative composite metal coating, said coating comprising a foundation layer of nickel about 0.1 to 2 mils thick deposited on said surface, an electrodeposited layer of chromium about 0.005 to about 0.015 mil thick applied to said nickel layer, and an outer layer of nickel about 0.1 to 2 mils thick applied to said chromium layer, said composite coating being characterized by an improved decorative and protective effect as com pared to a coating having a single nickel layer of the same thickness.
  • an article of metal from the class consisting of copper, brass, zinc, aluminum and steel having-firmly bonded to the surface thereof a composite metal coating at least about 0.25 mil up to about 4 mils thick, said coating comprising a plurality of nickel layers and at least one intermediate chromium layer about 0.005 mil to about 0.015 mil thick, and said composite coating having an improved decorative and protective effect as compared to a coating having a single nickel layer of the same thickness.
  • a metal article having firmly bonded to the surface thereof a composite metal coating at least about 0.25 to about 4 mils thick, said composite metal coating comprising a plurality of nickel layers and at least one intermediate chromium layer about 0.001 mil to about 0.03 mil thick, and said composite coating being characterized by an improved decorative and protective effect as compared to a coating having a single nickel layer of the same thickness.
  • a metal article having firmly bonded to the surface thereof a composite metal coating at least about 0.25 to about 4 mils thick, said composite metal coating comprising a plurality of nickel layers and at least one intermediate chromium layer about 0.001 mil to about 0.1 mil thick, and said composite coating being characterized by an improved decorative and protective eifect as compared to a coating having a single nickel layer of the same thickness.
  • the improvement for providing a metal coating having an enhanced protective and decor-ative effect which comprises depositing an adherent nickel layer upon said metal article, depositing upon said nickel layer a chromium layer about 0.001 mil to about 0.03 mil thick, and depositing an adherent nickel layer upon said chromium layer to produce a composite protective metal coating about 0.25 mil to about 4 mils thick, said composite metal coating being characterized by an enhanced protective efiect as compared to a coating having a single nickel layer of the same thickness.
  • the improvement for providing a metal coating having an enhanced protective and decorative effect which comprises depositing an adherent nickel layer upon said metal article, depositing upon said nickel layer a chromium layer about 0.001 mil to about 0.1 mil thick, and depositing an adherent nickel layer upon said chromium layer to produce a composite protective metal coating about 0.25 mil to about 4 mils thick, said composite metal coating being characterized by an enhanced protective effect as compared to a coating having a single nickel layer of the same thickness.
  • the improvement for providing a metal coating having an enhanced protective and decorative effect which comprises depositing an adherent nickel layer upon at least a portion of said metal article, depositing upon said nickel layer an adherent chromium layer about 0.005 mil to about 0.015 mil thick, and depositing an adherent nickel layer upon said chromium layer to produce a protective metal coating at least about 0.25 mil to about 4 mils thick, said composite metal coating being characterized by an enhanced protective eifect as compared to a coating having a single nickel layer of the same thickness.
  • the improvement for providing a metal coating having an enhanced decorative and protective effect which comprises depositing an adherent nickel layer about 0.1 to about 2 mils thick upon at least a portion of said metal article, electrodepositing an adherent chromium layer about 0.001 mil to about 0.03 mil thick upon said nickel layer, depositing an adherent nickel layer about 0.1 to about 2 mils thick upon said chromium layer, and electrodepositing an outer chromium layer upon said article to provide a composite metal coating having an enhanced decorative and protective effect as compared to a coating having a single nickel layer of the same thickness.
  • the improvement for providing a metal coating having an enhanced decorative and protective effect which comprises depositing an adherent nickel layer about 0.1 to about 2 mils thick upon at least a portion of said metal article, electrodepositing an adherent chromium layer about 0.005 mil to about 0.015 mil thick upon said nickel layer, depositing an adherent nickel layer about 0.1 to about 2 mils thick upon said chromium layer, and electrodepositing an outer chromium layer upon said article to provide a composite metal coating having an enhanced decorative and protective elfect as compared to a coating having a single nickel layer of the same thickness.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Physical Vapour Deposition (AREA)
US700352A 1957-12-03 1957-12-03 Protective and decorative coatings containing nickel Expired - Lifetime US3009236A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
NL233860D NL233860A (pt) 1957-12-03
US700352A US3009236A (en) 1957-12-03 1957-12-03 Protective and decorative coatings containing nickel
GB38324/58A GB852673A (en) 1957-12-03 1958-11-27 Improvements relating to composite metal coatings
SE1105858A SE205488C1 (sv) 1957-12-03 1958-11-28 Ferrometallartikel med sammansatt beläggning
FR780754A FR1283812A (fr) 1957-12-03 1958-12-02 Perfectionnements relatifs à des revêtements métalliques composites
DEM39818A DE1188897B (de) 1957-12-03 1958-12-02 Mit mehreren Metallschichten ueberzogener Metallgegenstand
NL233860A NL111002C (nl) 1957-12-03 1958-12-03 Werkwijze ter berscherming van in hoofdzaak uit ijzer bestaande voorwerpen, en aldus beschermende voorwerpen
CH6694058A CH382511A (fr) 1957-12-03 1958-12-03 Objet métallique et procédé pour sa fabrication
BE583671A BE583671A (fr) 1957-12-03 1959-10-15 Perfectionnements relatifs à des revêtements métalliques composites

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US700352A US3009236A (en) 1957-12-03 1957-12-03 Protective and decorative coatings containing nickel

Publications (1)

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US3009236A true US3009236A (en) 1961-11-21

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US700352A Expired - Lifetime US3009236A (en) 1957-12-03 1957-12-03 Protective and decorative coatings containing nickel

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US (1) US3009236A (pt)
CH (1) CH382511A (pt)
DE (1) DE1188897B (pt)
FR (1) FR1283812A (pt)
GB (1) GB852673A (pt)
NL (2) NL111002C (pt)
SE (1) SE205488C1 (pt)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249409A (en) * 1963-01-23 1966-05-03 Du Pont Chromium plated metal structures
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
US3771972A (en) * 1971-12-16 1973-11-13 Battelle Development Corp Coated article
US4511631A (en) * 1984-04-13 1985-04-16 Toyo Kohan Co., Ltd. Metallic chromium-nickel-hydrated chromium oxide-coated tin free steel and process for the production thereof
US20180264782A1 (en) * 2015-05-07 2018-09-20 Hitachi, Ltd. Laminated body having corrosion-resistant coating, and method for manufacturing same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4383003A (en) * 1980-09-22 1983-05-10 General Electric Company Transfer lamination of copper thin sheets and films, method and product
US4563399A (en) * 1984-09-14 1986-01-07 Michael Ladney Chromium plating process and article produced
EP3094764A4 (en) 2014-01-15 2017-08-30 Savroc Ltd Method for producing chromium-containing multilayer coating and a coated object
JP6774135B2 (ja) 2014-01-15 2020-10-21 サヴロック リミテッド クロム被覆を製造する方法および被覆物体
CN106661749B (zh) 2014-07-11 2020-06-05 萨夫罗克有限公司 含铬涂层，其制备方法以及涂覆物体

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1802695A (en) * 1924-06-26 1931-04-28 Metropolitan Eng Co Bimetallic protective coating for iron tubes
US1991747A (en) * 1933-12-30 1935-02-19 Hanson Van Winkle Munning Co Electroplating sequence
US2188399A (en) * 1936-11-05 1940-01-30 Int Nickel Co Electric resistance element
US2336568A (en) * 1939-07-10 1943-12-14 Battelle Memorlal Inst Method of metal electroplating
US2428033A (en) * 1941-11-24 1947-09-30 John S Nachtman Manufacture of rustproof electrolytic coatings for metal stock
US2859158A (en) * 1957-01-31 1958-11-04 Glenn R Schaer Method of making a nickel-chromium diffusion alloy

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE646142C (de) * 1935-08-18 1937-06-17 Bernhard Berghaus Verfahren zur Erhoehung der Haftfestigkeit metallischer Schichten oder UEberzuege auf Gegenstaenden aus Metall oder anderen Stoffen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1802695A (en) * 1924-06-26 1931-04-28 Metropolitan Eng Co Bimetallic protective coating for iron tubes
US1991747A (en) * 1933-12-30 1935-02-19 Hanson Van Winkle Munning Co Electroplating sequence
US2188399A (en) * 1936-11-05 1940-01-30 Int Nickel Co Electric resistance element
US2336568A (en) * 1939-07-10 1943-12-14 Battelle Memorlal Inst Method of metal electroplating
US2428033A (en) * 1941-11-24 1947-09-30 John S Nachtman Manufacture of rustproof electrolytic coatings for metal stock
US2859158A (en) * 1957-01-31 1958-11-04 Glenn R Schaer Method of making a nickel-chromium diffusion alloy

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US3249409A (en) * 1963-01-23 1966-05-03 Du Pont Chromium plated metal structures
US3771972A (en) * 1971-12-16 1973-11-13 Battelle Development Corp Coated article
US4511631A (en) * 1984-04-13 1985-04-16 Toyo Kohan Co., Ltd. Metallic chromium-nickel-hydrated chromium oxide-coated tin free steel and process for the production thereof
US20180264782A1 (en) * 2015-05-07 2018-09-20 Hitachi, Ltd. Laminated body having corrosion-resistant coating, and method for manufacturing same
US10836138B2 (en) * 2015-05-07 2020-11-17 Hitachi, Ltd. Laminated body having corrosion-resistant coating, and method for manufacturing same

Also Published As

Publication number Publication date
FR1283812A (fr) 1962-02-09
DE1188897B (de) 1965-03-11
SE205488C1 (sv) 1966-06-14
CH382511A (fr) 1964-09-30
NL111002C (nl) 1965-04-15
NL233860A (pt) 1900-01-01
GB852673A (en) 1960-10-26

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