US3586614A - Method of improving corrosion resistance of steel surfaces and resulting product - Google Patents

Method of improving corrosion resistance of steel surfaces and resulting product Download PDF

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Publication number
US3586614A
US3586614A US733307A US3586614DA US3586614A US 3586614 A US3586614 A US 3586614A US 733307 A US733307 A US 733307A US 3586614D A US3586614D A US 3586614DA US 3586614 A US3586614 A US 3586614A
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United States
Prior art keywords
aluminum
corrosion resistance
film
coating
steel
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Expired - Lifetime
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US733307A
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William E Boggs
Robert H Kachik
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United States Steel Corp
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United States Steel Corp
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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021Reactive sputtering or evaporation
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/938Vapor deposition or gas diffusion
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583Component contains compound of adjacent metal
    • Y10T428/1259Oxide
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736Al-base component
    • Y10T428/1275Next to Group VIII or IB metal-base component
    • Y10T428/12757Fe

Definitions

  • This invention relates to a method of improving the corrosion resistance of steel surfaces and to the resulting product.
  • a steel surface can be made more resistant to corrosion by applying a thin coating of aluminum.
  • One method of application is by a vapor-deposition process conducted in a vacuum, as shown for example in Smith Pat. No. 3,277,865 and the prior art cited therein.
  • the usual aluminum coating is extremely thin and does not afford as much corrosion resistance as would be desirable.
  • a protective film of silica as described fo rexample in Gartner et al. Pat. No. 3,177,134. Such film improves the resistance to corrosion over a coating of aluminum alone, but still does not afford maximum protection.
  • An object of our invention is to provide a method of improving the corrosion resistance of an aluminumcoated steel surface by applying over the aluminum coating a mixed oxide film which afi'ords greater protection than a single-oxide film.
  • a more specific object is to effect such improvement by applying a surface film composed of mixed oxides of silicon and aluminum in critical ratios.
  • a further object is to provide, as an article of manufacture, a steel product which has an aluminum coating plus a surface film of mixed oxides of silicon and aluminum.
  • a coating of aluminum we may use any conventional vapor deposition process to apply this coating.
  • the oxide film consists of about 30 to 60 percent by weight silica and the remainder oxides of aluminum. We prefer about equal parts of each.
  • the minimum efiective coating thickness (aluminum plus oxides) is about 0.25 micron. It is essential that we apply the two oxides simultaneously; the corrosion resistance is not nearly as good when we apply the two oxides separately one over the other.
  • our invention affords an effective method for improving the corrosion resistance of aluminum-coated steel, as well as a product which has improved corrosion resistance.
  • the method is simple and easily carried out in conventional equipment for vapor-deposition coating of steel.
  • a method of improving the corrosion resistance of a steel surface comprising applying to the surface a coating of aluminum, and applying over the aluminum coating a film of mixed oxides of silicon and aluminum, said coating and film having a minimum thickness together of about 0.25 micron, said film consisting of about 30 to 60 percent by weight silica and the remainder aluminum oxide.
  • a steel body which has a coating of aluminum and an oxide film overlying said coating, said film consisting of a mixture of about 30 to 60 percent by weight silicon oxide and the remainder aluminum oxides, the two oxides being deposited simultaneously on said coating, said coating and said film together having a minimum thickness of about 0.25 micron.

Abstract

METHOD OF INCREASING CORROSION RESISTANCE OF STEEL SURFACE IN WHICH THE SURFACE IS COATED WITH ALUMINUM, AND A FILM OF MIXED OXIDES OF SILICON AND ALUMINUM IS DEPOSITED OVER THE ALUMINUM-COATED SURFACE.

Description

United States Patent Oflice 3,586,614 Patented June 22, 1971 3,586,614 METHOD OF IMPROVING CORROSION RESIST- ANCE OF STEEL SURFACES AND RESULTING PRODUCT William E. Boggs, Monroeville Borough, and Robert H. Kachik, Washington Township, Westmoreland County, Pa., assignors to United States Steel Corporation No Drawing. Filed May 31, 1968, Ser. No. 733,307 Int. Cl. C22f 13/00 US. Cl. 204-148 3 Claims ABSTRACT OF THE DISCLOSURE Method of increasing corrosion resistance of steel surface in which the surface is coated with aluminum, and a film of mixed oxides of silicon and aluminum is deposited over the aluminum-coated surface.
This invention relates to a method of improving the corrosion resistance of steel surfaces and to the resulting product.
It is known that a steel surface can be made more resistant to corrosion by applying a thin coating of aluminum. One method of application is by a vapor-deposition process conducted in a vacuum, as shown for example in Smith Pat. No. 3,277,865 and the prior art cited therein. The usual aluminum coating is extremely thin and does not afford as much corrosion resistance as would be desirable. It is also known to apply to an aluminumcoated steel surface a protective film of silica, as described fo rexample in Gartner et al. Pat. No. 3,177,134. Such film improves the resistance to corrosion over a coating of aluminum alone, but still does not afford maximum protection.
An object of our invention is to provide a method of improving the corrosion resistance of an aluminumcoated steel surface by applying over the aluminum coating a mixed oxide film which afi'ords greater protection than a single-oxide film.
A more specific object is to effect such improvement by applying a surface film composed of mixed oxides of silicon and aluminum in critical ratios.
A further object is to provide, as an article of manufacture, a steel product which has an aluminum coating plus a surface film of mixed oxides of silicon and aluminum.
In accordance with our invention, We first apply to the surface of a steel body, such as a sheet or a continuous strip, a coating of aluminum. We may use any conventional vapor deposition process to apply this coating. Next We apply to the aluminum-coated surface a film of mixed oxides of silicon and aluminum. Again we use known techniques. For example, we may follow a procedure similar to that described in the aforementioned Gartner et al. patent for applying a film of silica alone. We vaporize silicon and aluminum from separate crucibles in a vacuum chamber, to which we admit a small volume of oxygen. The vapors oxidize and a mixture of the oxides deposits on the aluminum-coated surface. By using separate crucibles and separate vaporizing means, we are able to control the rate at which both substances vaporize and thus control the ratio of their oxides in the film. The oxide film consists of about 30 to 60 percent by weight silica and the remainder oxides of aluminum. We prefer about equal parts of each. The minimum efiective coating thickness (aluminum plus oxides) is about 0.25 micron. It is essential that we apply the two oxides simultaneously; the corrosion resistance is not nearly as good when we apply the two oxides separately one over the other.
As a test to determine the corrosion resistance of dif ferent samples, we exposed samples alternately to one hour of simulated dew and one hour of artificial sunlight in a Model XWR Weatheromcter. We inspected each sample at least once daily (12 cycles). We considered a sample as having failed when approximately 30 percent of its surface was covered with rust. A l00-cycle exposure is regarded as equivalent to a one-year outdoor exposure in Florida.
In such tests we observed a five-fold increase in the life of a steel sample coated with aluminum to a thickness of 0.1 micron plus a 0.9 micron film of equal parts oxides of silicon and aluminum, compared with a sample coated with aluminum alone to a thickness of 1 micron. The sample coated with aluminum alone failed in 200 cycles, while the other withstood 1000 cycles. Other tests gave results as follows:
From the foregoing description it is seen that our invention affords an effective method for improving the corrosion resistance of aluminum-coated steel, as well as a product which has improved corrosion resistance. The method is simple and easily carried out in conventional equipment for vapor-deposition coating of steel.
We claim:
1. A method of improving the corrosion resistance of a steel surface comprising applying to the surface a coating of aluminum, and applying over the aluminum coating a film of mixed oxides of silicon and aluminum, said coating and film having a minimum thickness together of about 0.25 micron, said film consisting of about 30 to 60 percent by weight silica and the remainder aluminum oxide.
2. A method as defined in claim 1 in which the oxide film is applied by vaporizing silicon and aluminum simultaneously from separate sources in the presence of oxygen, and depositing the vapors on the aluminum-coated surface.
3. As an article of manufacture, a steel body which has a coating of aluminum and an oxide film overlying said coating, said film consisting of a mixture of about 30 to 60 percent by weight silicon oxide and the remainder aluminum oxides, the two oxides being deposited simultaneously on said coating, said coating and said film together having a minimum thickness of about 0.25 micron.
References Cited UNITED STATES PATENTS 2,490,978 12/1949 Osterheld 204-197 2,774,686 12/1956 Hodge 117114C 2,788,289 4/1957 Deuble 1l7114C 2,873,209 2/ 1959 Gage 117-1140 3,177,134 4/1965 Gartner et al. 204192 TA-HSUNG TUNG, Primary Examiner US. Cl. X.R.
29-l95, 196.2; 1l7--7l, 106, 107; 204-192, 197
US733307A 1968-05-31 1968-05-31 Method of improving corrosion resistance of steel surfaces and resulting product Expired - Lifetime US3586614A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3708322A (en) * 1969-10-09 1973-01-02 British Steel Corp Method of producing a coated ferrous substrate
US4591417A (en) * 1983-12-27 1986-05-27 Ford Motor Company Tandem deposition of cermets
US4594137A (en) * 1983-09-09 1986-06-10 Ppg Industries, Inc. Stainless steel overcoat for sputtered films
US4596189A (en) * 1984-03-01 1986-06-24 Surface Science Corp. Lithographic printing plate
US4842959A (en) * 1986-10-17 1989-06-27 The Furukawa Electric Co., Ltd. Aluminum enamel board
DE4322465A1 (en) * 1993-07-06 1995-04-06 Fraunhofer Ges Forschung Corrosion-protected steel sheet
US10823199B2 (en) 2016-08-12 2020-11-03 General Electric Company Galvanic corrosion resistant coating composition and methods for forming the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3708322A (en) * 1969-10-09 1973-01-02 British Steel Corp Method of producing a coated ferrous substrate
US4594137A (en) * 1983-09-09 1986-06-10 Ppg Industries, Inc. Stainless steel overcoat for sputtered films
US4591417A (en) * 1983-12-27 1986-05-27 Ford Motor Company Tandem deposition of cermets
US4596189A (en) * 1984-03-01 1986-06-24 Surface Science Corp. Lithographic printing plate
US4842959A (en) * 1986-10-17 1989-06-27 The Furukawa Electric Co., Ltd. Aluminum enamel board
DE4322465A1 (en) * 1993-07-06 1995-04-06 Fraunhofer Ges Forschung Corrosion-protected steel sheet
US10823199B2 (en) 2016-08-12 2020-11-03 General Electric Company Galvanic corrosion resistant coating composition and methods for forming the same

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