US3438754A - Zinc-coated steel with vapor-deposited aluminum overlay and method of producing same - Google Patents

Zinc-coated steel with vapor-deposited aluminum overlay and method of producing same Download PDF

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US3438754A
US3438754A US433710A US3438754DA US3438754A US 3438754 A US3438754 A US 3438754A US 433710 A US433710 A US 433710A US 3438754D A US3438754D A US 3438754DA US 3438754 A US3438754 A US 3438754A
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zinc
aluminum
coating
vapor
steel
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George A Shepard
Carl F Brooker
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Republic Steel Corp
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Republic Steel Corp
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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
    • C23C28/02—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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • Y10S428/9335—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
    • 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
    • Y10S428/938—Vapor deposition or gas diffusion
    • 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
    • Y10S428/939—Molten or fused coating
    • 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
    • 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
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • a zinc-coated steel article with a vapor-deposited aluminum overlay is produced by applying to a steel surface an adherent coating of zinc, and thereafter applying a coating of aluminum to the zinc-coated steel surface by depositing aluminum vapor thereon.
  • This invention relates to the manufacture of zinc-coated steel articles.
  • it is directed to methods of producing on a steel surface a zinc coating having improved corrosion resistance, and also to the resulting articles, such as steel sheet carrying an adherent corrosionresistant coating.
  • Zinc-coated steel sheet meaning strip or other sheet of steel, whether cold rolled or hot rolled, has distinct advantages in many fields of use, particularly in avoiding or reducing corrosion or like deterioration of the steel surface.
  • zinc protects steel galvanically, i.e., in a corroding medium the zinc will preferentially corrode; in any given corroding medium the protection which the zinc affords the steel is a function of its thickness.
  • An object of the present invention is to improve the resistance to corrosion of zinc-coated steel articles and in particular to increase the duration of effective protection against corrosion afforded by zinc coatings on steel surfaces. Another object is to provide methods of producing zinc coatings on steel, affording coatings having improved corrosion resistance. A further object is to provide zinccoated steel articles having superior corrosion-resistant properties.
  • the method of the invention in a broad sense contemplates establishing an adherent coating of zinc on a steel substrate, e.g., in conventional mannet, and thereafter applying to the zinc-coated surface a further, thin coating or overlay of aluminum by depositing aluminum vapor thereon. It is found that zinc-coated steel articles thus produced, i.e., having a thin vapor-deposited aluminum overlay, exhibit greatly enhanced resistance to corrosion and in particular that the duration of effective protection against corrosion afforded by the zinc coating is very materially increased, as compared to that afforded by conventional zinc coatings of equivalent thickness. This improvement in corrosion resistance is presently believed to be due to some effect of the aluminum overlay in sealing the pores which exist in zinc coatings and/ or otherwise serving to make the zinc surface less active thereby to retard the consumption of zinc under corrosive conditions.
  • the step of applying the zinc coating may itself, as stated, be entirely conventional.
  • the zinc coating may be established on the steel substrate by hotdip galvanizing or by electroplating.
  • hot-dip galvanizing the steel surface, suitably cleaned, is immersed in a body of molten zinc to establish on the surface a zinc layer that solidifies (after the surface is withdrawnfrom the zinc bath) as a coating adherent thereto.
  • Electroplating of zinc involves immersing the steel surface (after thorough cleaning thereof) in an appropriate electrolytic bath, e.g., containing zinc sulfate, and passing direct electric current through the bath, to plate an adherent coating of zinc onto the surface.
  • the resultant zinc coating as prepared by either procedure may be wholly conventional in character, e.g., a conventional hot-dip galvanized or electroplated zinc coating on steel, and may have a thickness (for example) of the order of 20 to 1,500 microinches (one microinch being 10* inch), or more depending upon conditions of operation of a zinc-applying step.
  • a thickness for example
  • Both hot-dip galvanizing and electroplating operations as contemplated herein, including surface precleaning steps and selection of conditions to produce a desired coating thickness, are wellknown in the art and accordingly need not be described in detail.
  • a further coating, of aluminum metal is applied to the zinc-coated steel surface by vapor deposition.
  • This vapor deposition step may be performed in accordance with conventional vacuum metalizing techniques for depositing aluminum from vapor on a metal substrate.
  • the deposition may take place in a standard vacuum system for the vapor deposition of metals having a vacuum chamber, into which the steel is passed after coating with zinc.
  • the zinc-coated steel surface as introduced to the chamber must be thoroughly clean and dry; accordingly, between the steps of applying the zinc and aluminum coatings, the surface may be cleaned or rinsed and dried, again in accordance with conventional procedures for preparing metal substrates for vacuum metalizing.
  • the vacuum chamber is evacuated and maintained at a relatively high vacuum, of the order of a half micron or less of mercury, and aluminum from a clean and uncontaminated source is evaporated, by heating the source, to produce aluminum vapor in the chamber.
  • the vapor condenses or deposits on the zinc-coated surface as an adherent solid film of aluminum overlying the zinc coating, the thickness of this film being determined by the rate of vapor deposition and duration of exposure of the surface thereto.
  • a vacuum-metalizing technique suitable for use in depositing the aluminum coating in the present method, is that described in United States Patent No. 2,959,494 as employed to deposit aluminum from vapor on a bare steel substrate.
  • This procedure may be performed in a vacuum system consisting of a vacuum metallizer and a vacuum chamber.
  • the vacuum chamber is evacuated prior to aluminum deposition by a four stage procedure which includes a first step of rough pumping to a vacuum of 200 microns of mercury.
  • the vacuum is then further reduced by the use of diffusion pumps.
  • the residual atmosphere remaining after a pump-down must not contain organic vapors.
  • a high voltage discharge step provides good adherence of the aluminum coating on the substrate; this is effected while the vacuum chamber is being evacuated with the diffusion pumps.
  • the surface of the substrate is degassed by a high voltage discharge.
  • the fourth step of the pump-down procedure carries the vacuum to about 0.5 micron of pressure.
  • Aluminum is then vaporized from a suitably heated surface to which metallic aluminum is supplied.
  • the aluminum may be vaporized by means of an electron beam, e.g.
  • the aluminum source is positioned in a vacuum chamber in the path of a beam of electrons from a suitable electron source with appropriate voltage applied between the electron source and the aluminum source, so that the electron beam vaporizes aluminum from the latter source for deposition on the substrate to be coated.
  • the product of the invention is a zinc-coated steel article (of sheet, strip or other form) having a thin, continuous vapordeposited outer coating of aluminum.
  • the integrity of the zinc coating is maintained through the aluminum deposition step; i.e. in the final product the zinc layer has integrity as a zinc coating and indeed is itself a conventional adherent coating of zinc as heretofore employed for protection of steel surfaces against corrosion.
  • the vapordeposited aluminum coating overlies this zinc coating and adheres thereto.
  • a presently preferred range of values of thickness for the vapor-deposited aluminum overlay is between about 5 microinches and about 100 microinches, a thickness of at least about microinches being presently considered particularly advantageous and a range of between about and about 60 microinches being especially preferred.
  • the aluminum coating thickness may exceed 100 microinches if desired, the latter value representing a preferred upper limit from the standpoint of economy.
  • the coated steel surface may, if desired, optionally be treated with a chromite solution, in accordance with conventional procedures as presently used for treating zinc coatings to prevent white rust, and for treating aluminum coatings to promote paint adherence.
  • a chromite solution is well-known in the art and commercially available; by way of specific example, the zinc-coated steel surface bearing the aluminum overlay may be treated with Iridite Solution 149, which is manufactured by Allied Research Products, Inc., and is believed to be basically a potassium dichromate solution. This chromate treatment in certain instances appears to enhance the corrosion resistance of the coated surface to some extent, but is not necessary to the attainment of the advantages of the invention and thus may be omitted.
  • the effect of the aluminum overlay on the corrosionresistant properties of zinc-coated steel has been ascertained by testing, for resistance to corrosion under exposure to salt spray, zinc-coated steel panels (including both hot-dip galvanized and electroplated zinc-coated panels) prepared and coated with a vapor-deposited overlay of aluminum in accordance with the invention.
  • the samples tested included panels having aluminum coatings 15, 30, and 60 microinches thick, deposited over zinc coatings of various thicknesses ranging from less than microinches to more than 950 microinches. Some of these panels were treated, i.e. before testing, with a chromate solution as described above; others were untreated. Results of the tests were compared with results of similar tests on panels having conventional hot-dip galvanized or electroplated zinc coatings of like thickness but no aluminum overlay.
  • the testing procedure used was a standard ASTM test method (specification No. 8117-62) for resistance to corrosion under salt spray, wherein the panel under test is continuously exposed to salt spray until red rust develops on the panel surface, the resistance to corrosion being determined by the duration of exposure and the proportion of the panel surface covered with red rust as appraised by visual inspection.
  • each of the panels was exposed to salt spray until 10% of the panel surface was covered with red rust; the exposure time required to produce this 10% red rust condition served as a measure of the resistance of the panel to corrosion.
  • the longest exposure times (900 1,200 hours) in this series were achieved with panels having a zinc thickness of between about 450 and 650 microinches and an aluminum thickness of 30 to 60 microinches, treated with chromate before testing, although exposure times well above 600 hours were also achieved With panels having an aluminum thickness (over zinc) in the latter range, Without chromate treatment.
  • a principal advantage of the present invention is in greatly enhancing the protection against corrosion afforded by zinc coatings on steel.
  • the duration of effective protection afforded by the coating can be increased by 100 to several hundred hours, i.e. in many cases by a factor of two, three or even more over the duration of protection afforded by zinc coatings Without aluminum overlay.
  • vapor-deposited flash of aluminum (3 microinches) were found to exhibit improved resistance to corrosion in a humidity cabinet, over samples coated with an equal thickness of zinc but having no aluminum overlay.
  • the method of the invention has been described above as including the application of a zinc coating by conventional electroplating or hot-dip galvanizing procedures, other operations for applying zinc coatings to steel surfaces may also be employed, followed by vapor-deposition of aluminum, with like advantages in improving the corrosion resistance of such zinc coatings.
  • the zinc coating may itself be applied to the steel surface by vapor deposition.
  • One especially elfective procedure for depositing zinc on steel from vapor is described in the copending application of the present applicants, Ser. No. 423,249, filed Jan. 4, 1965, and now abandoned.
  • the steel surface (after appropriate cleaning) is first coated with a thin adherent layer of copper or other metal selected from a specific class of metals in the upper range of the electromotive force series, namely gold, silver and copper, brass being also deemed a member of the named group in that the latter is an alloy consisting essentially of copper and zinc wherein copper predominates.
  • This coating may be applied e.g. by ionic deposition from an aqueous medium or by electroplating and is followed by a vacuum metalizing deposition of zinc from vapor on the treated surface.
  • the first-mentioned coating serves to enhance the adherence of the vapor-deposited zinc, which may be applied for example by directing zinc vapor onto the surface in a vacuum chamber.
  • the zinc vapor may be produced in any convenient manner, for example by electronbeam vaporization as described above for vaporization of aluminum.
  • the steel article bearing the vapordeposited zinc'coating is subjected to a further vacuum metalizing step for deposition of aluminum from vapor to provide an aluminum overlay, in the same manner as described above.
  • this aluminum overlay is found to afford the aforementioned advantages in providing far superior resistance to corrosion of the .vapor deposited zinc coating.
  • the body of the steel sheet 10, which may be cold rolled strip is first coated, e.g. by hot-dip galvanizing, electroplating, or vapor deposition, with an adherent layer of zinc ll, 11' on its opposite faces.
  • aluminum coatings 12, 12' are applied by vapor deposition of aluminum in a vacuum.
  • the zinc layer may be, for example, from 20x10" inch to 1,500 inch or more in thickness, while the aluminum overlay may be, for example from 5 10- inch to 100 1()- inch in thickness.
  • one of the aluminum coatings may be omitted, as by simply directing vapor onto one face of the sheet during its passage through the vacuum chamber, and also one of the zinc coatings may be omitted, to provide a steel sheet having only one coated surface.
  • the sheet may be coated with thicker coatings on one side than on theother for use where the two surfaces of the product are exposed to dilfering corrosion conditions, e.g. as in automobile bodies wherein one side of the sheet is painted and the other is exposed to corrosive material such as salt splashed up from roadways.
  • Example I Each of a series of cold-rolled steel panels was alkali cleaned in a solution containing 40 g./liter of sodium carbonate, 30 g./liter of trisodium phosphate and 20 g./liter of sodium hydroxide. The temperature of the cleaner was maintained at 200 F. and the steel panels were cleaned cathodically at 50 amperes per square foor for one minute. The panels were then rinsed, pickled in muriatic acid for 30 seconds, rinsed again and zinc plated in a bath containing g./liter of zinc (as sulfate) and 30 g./liter (NHQ $0 the bath having a pH of 3.0 and a temperature of 80 F., at a current density of 2t) amp./ft.
  • Plating times were adjusted to give zinc coatings of 25, 50, and microinches on different panels. After zinc plating the samples were rinsed and dried. Thereafter, some of the samples were placed in a vacuum chamber, the air was evacuated, and these samples were plated with vapor deposited aluminum. The aluminum was deposited under a vacuum (i.e. pressure) of 0.1 micron by placing an aluminum clip on a tungsten filament and heating the filament to vaporize the aluminum, the aluminum being evaporated at a temperature of about 1370 C. The thickness of the aluminum overlay thus produced, on various samples, was 15 and 30 microinches.
  • samples of zinc coated steel without aluminum overlay having zinc thickness up to microinches reached a condition of 10% or greater coverage with red rust in six hours, or 20% in twelve hours.
  • Samples of aluminum-coated steel without zinc reached a condition of 25% to 50% red rust coverage in six to twelve hours.
  • the samples prepared in accordance with the present invention, having an aluminum overlay on a zinc coating attained only 10% to 20% red rust coverage in 48 to 114 hours, i.e. these latter samples exhibited very markedly improved resistance to corrosion.
  • a Zinc coated panel without aluminum having zinc thickness of 165 microinches reached 20% red rust in 12 hours
  • an aluminum coated panel without zinc having an aluminum thickness of 15 microinches reached 50% red rust in six hours
  • a panel coated with 150 microinches of zinc and 15 microinches of vapor deposited aluminum reached only 20% red rust in 48 hours.
  • a panel having a 100 microinch zinc coating and a 30 microinch aluminum coating reached only 10% red rust in 114 hours
  • a panel having a 115 microinch thick zinc coating without aluminum reached 10% red rust in six hours and a panel bearing 30 microinches of aluminum without zinc reached 25% red rust in twelve hours.
  • Example II Five zinc-coated steel panels prepared by hot dip galvanizing and having a zinc coating thickness of 800 microinches were cleaned with an alkaline scrubber-type cleaning line and thereafter further coated with 45 microinches of aluminum by vapor deposition over the zinc surfaces.
  • the aluminum was deposited under a vacuum (i.e. pressure) of 0.1 micron at a rate of 0.03 lb./ft. per minute, the aluminum being evaporated at a temperature of about 1370 C.
  • the average exposure time required to reach 10% red rust was 264 hours; for the five panels having the aluminum layer, the average time required to reach 10% red rust condition was 840 hours.
  • a method of producing a zinc-coated steel article with a vapor deposited aluminum overlay comprising applying to a steel surface an adherent coating of zinc, and thereafter applying a coating of aluminum to the zinccoated steel surface by depositing aluminum vapor thereon.
  • step of applying said Zinc coating comprises electroplating zinc on the steel surface.
  • a method according to claim 1, wherein said step of applying said zinc coating comprises immersing said steel surface in molten zinc.
  • step of applying said zinc coating comprises directing zinc vapor onto said steel surface to establish an adherent vapor-deposited zinc coating thereon.
  • a method of producing a zinc-coated steel article with a vapor deposited aluminum overlay comprising applying to a steel surface an adherent coating of zinc and thereafter applying a coating of aluminum to the zinccoated steel surface by depositing aluminum vapor thereon in sufficient amount to provide an aluminum coating of at least about 5 10 inch in thickness.
  • a method of producing a zinc-coated steel article with a vapor deposited aluminum overlay comprising applying to a steel surface an adherent coating of zinc to a thickness of at least about 10 inch, and thereafter applying a coating of aluminum to the zinc-coated steel surface by depositing aluminum vapor thereon in vacuum in sufiicient amount to produce an aluminum coating of between about 5X10 inch and about x10" inch in thickness.
  • a Zinc-coated steel article with a vapor deposited aluminum overlay consisting essentially of a steel base having a surface carrying a layer of zinc in adherence to said steel surface, said zinc layer having integrity as a zinc coating upon said steel surface, and an adherent coating of aluminum applied over said zinc coating by vapor deposition.
  • a zinc-coated steel article with a vapor deposited aluminum overlay consisting essentially of a steel base having a surface carrying a layer of zinc, having a thickness of at least about 20X 10- inch, in adherence to said steel surface, said zinc layer having integrity as a zinc coating upon said steel surface, and an adherent coating of aluminum applied over said zinc coating by vapor deposition.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Physical Vapour Deposition (AREA)
  • Coating With Molten Metal (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)
US433710A 1965-02-18 1965-02-18 Zinc-coated steel with vapor-deposited aluminum overlay and method of producing same Expired - Lifetime US3438754A (en)

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BE (1) BE676723A (enrdf_load_stackoverflow)
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532609A (en) * 1965-11-09 1970-10-06 Nippon Kokan Kk Process for the preliminary treatment adapted for the electrolytic formation of aluminum coatings on metallic surfaces in molten salt bath
US3642457A (en) * 1968-05-31 1972-02-15 Chromalloy American Corp Multimetal corrosion-resistant diffusion coatings
US3652321A (en) * 1970-08-17 1972-03-28 Continental Oil Co Deposition of aluminum on a galvanized surface
US3690043A (en) * 1968-11-25 1972-09-12 Bodo Futterer Electrofilter for gases
US3765955A (en) * 1970-07-30 1973-10-16 Nippon Steel Corp Surface treated steel sheet for use in a forming operation
US4257549A (en) * 1978-03-14 1981-03-24 H. H. Robertson Company Method of making aluminum-base metal clad galvanized steel laminate
US4647714A (en) * 1984-12-28 1987-03-03 Sohwa Laminate Printing Co., Ltd. Composite sheet material for magnetic and electronic shielding and product obtained therefrom
US4680908A (en) * 1980-04-14 1987-07-21 Amoco Corporation Refractory anchor
US4774825A (en) * 1984-12-10 1988-10-04 N.V. Bekaert S.A. Method for cladding a wire-shaped steel element with an aluminum coating, as well as aluminum-coated wire-shaped steel element
JPH02205412A (ja) * 1988-04-14 1990-08-15 Illinois Tool Works Inc <Itw> 改良されたねじ切り締結具
EP1624091A1 (de) * 2004-08-04 2006-02-08 Aluminal Oberflächentechnik GmbH & Co. KG Mit einer Aluminium/Magnesium-Legierung oder Aluminium beschichtete Werkstücke mit Zink-Zwischenschicht
US20110006491A1 (en) * 2008-01-15 2011-01-13 Arcelormittal France Process for manufacturing stamped products, and stamped products prepared from the same
US20150013409A1 (en) * 2010-12-17 2015-01-15 Arcelormittal Investigación Y Desarrollo Sl Steel Sheet including a Multilayer Coating and Methods
US20180044774A1 (en) * 2015-02-19 2018-02-15 Arcelormittal Method of producing a phosphatable part from a sheet coated with an aluminum-based coating and a zinc coating

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JPH0621348B2 (ja) * 1986-07-22 1994-03-23 日新製鋼株式会社 合金化亜鉛メツキ鋼板とその製造法
IT1197806B (it) * 1986-08-01 1988-12-06 Metalvuoto Films Spa Procedimento ed apparecchiatura per la realizzazione di pellicole metallizzate per condesatori elettrici e prodotti cosi' ottenuti
DE19527515C1 (de) * 1995-07-27 1996-11-28 Fraunhofer Ges Forschung Verfahren zur Herstellung von korrosionsgeschütztem Stahlblech
DE102013104678A1 (de) * 2013-05-07 2014-11-13 Butzkies Windprojekt Gmbh & Co. Kg Verfahren zum Herstellen von Stahlbauelementen mit einer bei deren Verbindung miteinander einen hohen Reibungskoeffizienten aufweisenden Beschichtung

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US3532609A (en) * 1965-11-09 1970-10-06 Nippon Kokan Kk Process for the preliminary treatment adapted for the electrolytic formation of aluminum coatings on metallic surfaces in molten salt bath
US3642457A (en) * 1968-05-31 1972-02-15 Chromalloy American Corp Multimetal corrosion-resistant diffusion coatings
US3690043A (en) * 1968-11-25 1972-09-12 Bodo Futterer Electrofilter for gases
US3765955A (en) * 1970-07-30 1973-10-16 Nippon Steel Corp Surface treated steel sheet for use in a forming operation
US3652321A (en) * 1970-08-17 1972-03-28 Continental Oil Co Deposition of aluminum on a galvanized surface
US4257549A (en) * 1978-03-14 1981-03-24 H. H. Robertson Company Method of making aluminum-base metal clad galvanized steel laminate
US4680908A (en) * 1980-04-14 1987-07-21 Amoco Corporation Refractory anchor
US4774825A (en) * 1984-12-10 1988-10-04 N.V. Bekaert S.A. Method for cladding a wire-shaped steel element with an aluminum coating, as well as aluminum-coated wire-shaped steel element
US4647714A (en) * 1984-12-28 1987-03-03 Sohwa Laminate Printing Co., Ltd. Composite sheet material for magnetic and electronic shielding and product obtained therefrom
JPH02205412A (ja) * 1988-04-14 1990-08-15 Illinois Tool Works Inc <Itw> 改良されたねじ切り締結具
EP1624091A1 (de) * 2004-08-04 2006-02-08 Aluminal Oberflächentechnik GmbH & Co. KG Mit einer Aluminium/Magnesium-Legierung oder Aluminium beschichtete Werkstücke mit Zink-Zwischenschicht
US20110006491A1 (en) * 2008-01-15 2011-01-13 Arcelormittal France Process for manufacturing stamped products, and stamped products prepared from the same
US8733142B2 (en) * 2008-01-15 2014-05-27 Arcelormittal France Process for manufacturing stamped products, and stamped products prepared from the same
US20150013409A1 (en) * 2010-12-17 2015-01-15 Arcelormittal Investigación Y Desarrollo Sl Steel Sheet including a Multilayer Coating and Methods
US9670576B2 (en) * 2010-12-17 2017-06-06 Arcelormittal Investigación Y Desarrollo Sl Steel sheet including a multilayer coating and methods
US20180044774A1 (en) * 2015-02-19 2018-02-15 Arcelormittal Method of producing a phosphatable part from a sheet coated with an aluminum-based coating and a zinc coating

Also Published As

Publication number Publication date
DE1621321A1 (de) 1970-07-23
DE1621321B2 (de) 1971-10-28
BE676723A (enrdf_load_stackoverflow) 1966-08-18
LU50489A1 (enrdf_load_stackoverflow) 1966-04-18
FR1469396A (fr) 1967-02-10
GB1082031A (en) 1967-09-06

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