US2823139A - Method of increasing the scaling resistance of metallic objects - Google Patents

Method of increasing the scaling resistance of metallic objects Download PDF

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Publication number
US2823139A
US2823139A US355869A US35586953A US2823139A US 2823139 A US2823139 A US 2823139A US 355869 A US355869 A US 355869A US 35586953 A US35586953 A US 35586953A US 2823139 A US2823139 A US 2823139A
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Prior art keywords
chromium
coating
scaling
oxide
lithium
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Expired - Lifetime
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US355869A
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Schulze Herbert
Schriewer Hans
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Vereinigte Deutsche Metallwerke AG
Ver Deutsche Metallwerke AG
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Ver Deutsche Metallwerke AG
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Classifications

    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • 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
    • Y10S428/937—Sprayed metal
    • 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.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y10T428/1259—Oxide
    • 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
    • Y10T428/12903—Cu-base component
    • Y10T428/12917—Next to Fe-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
    • Y10T428/12951—Fe-base component
    • Y10T428/12958—Next to Fe-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
    • Y10T428/12951—Fe-base component
    • Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]

Definitions

  • the present invention relates to a process for imparting high scaling resistance to metallic objects especially those of steel of all kinds.
  • oven parts and also hardening and smelting crucibles, troughs and other vessels for salt baths; and in addition casting molds and other casting apparatus; annealing boxes, carburizing boxes, parts of smelting and roasting furnaces; superheaters; protective tubes or in general tubes and plates and many other articles used in industrial installations are often exposed to conditions giving rise to scaling.
  • the latter coating materials can be applied in a number of ways. -A simple procedure is to mix such materials in powder form with a lacquer or paint, preferably a bituminous base paint and then applying such lacquer or paint upon the sprayed metal coating.
  • the lithium compounds, aluminum oxide and magnesium oxide either singly or in admixture in water and applying such suspension to the sprayed metal coating.
  • the quantity of lithium compound, preferably lithium carbonate amounts to to 20% and the remainder is aluminum oxide and magnesium oxide.
  • the preferred ratio of um compound, particularly, lithium carbonate, to the um oxide and/or magnesium oxide is between Patented Feb. 11, 1958 Of the chromium and nickel containing alloys suitable for the first coating applied to the metal objects to be protected, chromiumnickel-iron alloys containing 18 to 30% of nickel, about 18 to 25% of chromium, up to 3% of silicon, and the remainder iron; or 60 to 65% nickel, 12 to 20% of chromium, up to 3% of silicon, and
  • chromium-nickel alloys containing to of nickel, 15 to 20% of chromium, and up to 2% of silicon, have given best results.
  • the alloys mentioned can in addition contain up to 10%, of tungsten and/or molybdenum.
  • their resistance to heat may be improved in known manner by additions of alkaline earths, rare earths, thorium, zirconium, uranium, either singly or several together, while of each of the elements mentioned contents of from 0.02 to 0.5% may be present.
  • the thickness of the sprayed metal coating to be applied is about 0.25 to 0.40 mm.
  • Example 1 A coating of an alloy composed of 20% chromium, 30% nickel and the remainder essentially iron was sprayed on the articles to be protected and therafter an admixture of finely ground lithium carbonate powder with bituminous paint, was painted over the sprayed on metal coating.
  • the quantity of lithium carbonate mixed with the bituminous paint was such that the mixture could easily be applied with a brush.
  • Example 2 A coating of an alloy composed of 20% chromium, 30% nickel and the remainder essentially iron was sprayed on the articles to be protected and thereafter a suspension of 20% lithium carbonate and 80% A1 0, in water was painted over the sprayed on metal coating.
  • Example 3 temperatures above 800' C. in the presence of corrosive gases of a metal article coated witha scaling resistant chromlum-and-nickel containing alloy which comprises applying to said coated metal article a coating consisting essentiallyof a material selected from the group consisting of chromium oxide, aluminum oxide, lithium oxide, lithium hydroxide and lithium carbonate.
  • a method of improving the scaling resistance at temperatures above 800' C. in the presence of corrosive gases of a metal article coated with a scaling resistant chromium-and-nickel containing alloy which comprises applying to said coated metal article a coating in the form of an aqueous suspension of finely divided lithium carbomb.
  • a method of improving the scaling resistance at temperatures above 800 C. in the presence of corrosive gases of a metal article coated with a scaling resistant chromium-andnickel containing alloy which comprises applying to said coated metal article a coating in the form of an aqueous suspension of finely divided aluminum-oxide.
  • a method of improving the scaling resistance at temperatures above 800' C. in the presence of corrosive gases of a metal article coated with a scaling resistant chromium-and-nickelcontaining alloy which comprises applying to said coated metal article a coating in the form of an aqueous suspension of finely divided lithium carbonate and aluminum oxide.
  • a method of improving the scaling resistance at temperatures above 800 C. in the presence of corrosive gases of a metal article coated with a scaling resistant chromium-and-nickel containing alloy which comprises applying to said coated metal article a coatingin the form of an aqueous suspension of finely divided lithium carbonate and magnesium oxide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)

Description

METHOD OF INCREASING THE SCALING RESISTANCE F METALLIC OBJECTS Herbert Schulze and Hans Schriewer, Altena, Germany,
assignors to Vereinigte Deutsche Metallwerke Aktiengeselischaft, Frankfurt am Main, Germany No Drawing. Application May 18, 1953 Serial No. 355,869
Claims priority, application Germany May 23, 1952 11 Claims. (Cl. 117-71) The present invention relates to a process for imparting high scaling resistance to metallic objects especially those of steel of all kinds.
Many metal objects, especially those of iron, steel, copper or alloys thereof are frequently exposed to high temperatures as well as to the influence of corrosive gases, particularly gases which have a strong oxidizing action. The life of such metal objects is consequently relatively short and this necessitates undesirable frequent replacement of the scale encrusted parts, as, for example, in the case of grate bars, boiler plates or other parts of furnaces. Furthermore, other oven parts and also hardening and smelting crucibles, troughs and other vessels for salt baths; and in addition casting molds and other casting apparatus; annealing boxes, carburizing boxes, parts of smelting and roasting furnaces; superheaters; protective tubes or in general tubes and plates and many other articles used in industrial installations are often exposed to conditions giving rise to scaling.
It has already been proposed to reduce the scaling resistance of objects of structural steel or boiler plates by applying a protective coating of a chromium and nickel containing iron alloy and then spraying" on a coating of aluminum containing paint. Investigations, however, have shown that such protective coatings would not hinder extremely intense scaling of the objects when they were subjected to temperatures over 1000' C. after 235 hours.
It was unexpectedly found according to the invention, that excellent scaling resistance can be achieved against the corrosive influence of hot gases at temperatures over 800 C. and up to about 1100' C. if the metal objects are firstspray coated with chromium-nickel-iron or chromium-nickel alloys and such coatings are then provided with a coating of chromium oxide (C30,), lithium com pounds, especially lithium carbonate, lithium oxide and lithium hydroxide, or aluminum oxide.
The latter coating materials can be applied in a number of ways. -A simple procedure is to mix such materials in powder form with a lacquer or paint, preferably a bituminous base paint and then applying such lacquer or paint upon the sprayed metal coating.
It is also possible to suspend the lithium compounds, aluminum oxide and magnesium oxide either singly or in admixture in water and applying such suspension to the sprayed metal coating. Preferably, when the abovementioned materials are mixed the quantity of lithium compound, preferably lithium carbonate, amounts to to 20% and the remainder is aluminum oxide and magnesium oxide.
Mixtures of lithium carbonate with the aluminum oxide and/or magnesium oxide can also be applied in admixture with a lacquer. When suspensions in water are employed, care should be taken in preparing such suspensions so that a good coating can be obtained there- I with by painting it with a brush. The preferred ratio of um compound, particularly, lithium carbonate, to the um oxide and/or magnesium oxide is between Patented Feb. 11, 1958 Of the chromium and nickel containing alloys suitable for the first coating applied to the metal objects to be protected, chromiumnickel-iron alloys containing 18 to 30% of nickel, about 18 to 25% of chromium, up to 3% of silicon, and the remainder iron; or 60 to 65% nickel, 12 to 20% of chromium, up to 3% of silicon, and
the remainder iron; or chromium-nickel alloys containing to of nickel, 15 to 20% of chromium, and up to 2% of silicon, have given best results. The alloys mentioned can in addition contain up to 10%, of tungsten and/or molybdenum. Moreover, their resistance to heat may be improved in known manner by additions of alkaline earths, rare earths, thorium, zirconium, uranium, either singly or several together, while of each of the elements mentioned contents of from 0.02 to 0.5% may be present. The thickness of the sprayed metal coating to be applied is about 0.25 to 0.40 mm.
The following examples will serve to illustrate the process according to the invention.
Example 1 A coating of an alloy composed of 20% chromium, 30% nickel and the remainder essentially iron was sprayed on the articles to be protected and therafter an admixture of finely ground lithium carbonate powder with bituminous paint, was painted over the sprayed on metal coating. The quantity of lithium carbonate mixed with the bituminous paint was such that the mixture could easily be applied with a brush.
Example 2 A coating of an alloy composed of 20% chromium, 30% nickel and the remainder essentially iron was sprayed on the articles to be protected and thereafter a suspension of 20% lithium carbonate and 80% A1 0, in water was painted over the sprayed on metal coating.
Example 3 temperatures above 800' C. in the presence of corrosive gases of a metal article coated witha scaling resistant chromlum-and-nickel containing alloy which comprises applying to said coated metal article a coating consisting essentiallyof a material selected from the group consisting of chromium oxide, aluminum oxide, lithium oxide, lithium hydroxide and lithium carbonate.
2. A method according to claim 1 in which the thickness of the scaling resistant chromium-and-nickel containing alloy on the metal article is 0.25 to 0.40 mm.
3. A method according to claim 1 inwhich said coating on the chromium-and-nickel containing alloy coated article is applied in the form of-a bituminous paint.
4. A method according to claim 1 in which said coating applied to chromium-and-nickel containing alloy coated article contains lithium carbonate.
5. A method of improving the scaling resistance at temperatures above 800' C. in the presence of corrosive gases of a metal article coated with a scaling resistant chromium-and-nickel containing alloy which comprises applying to said coated metal article a coating in the form of an aqueous suspension of finely divided lithium carbomb.
6. A method of improving the scaling resistance at temperatures above 800 C. in the presence of corrosive gases of a metal article coated with a scaling resistant chromium-andnickel containing alloy which comprises applying to said coated metal article a coating in the form of an aqueous suspension of finely divided aluminum-oxide.
7; A method of improving the scaling resistance at temperatures above 800' C. in the presence of corrosive gases of a metal article coated with a scaling resistant chromium-and-nickelcontaining alloy which comprises applying to said coated metal article a coating in the form of an aqueous suspension of finely divided lithium carbonate and aluminum oxide.
8. A, process in accordance with claim 7 in which said lithium carbonate and aluminum oxide are present'in a proportion of from 1: 10 to 1': 1.
9. A method of improving the scaling resistance at temperatures above 800 C. in the presence of corrosive gases of a metal article coated with a scaling resistant chromium-and-nickel containing alloy which comprises applying to said coated metal article a coatingin the form of an aqueous suspension of finely divided lithium carbonate and magnesium oxide.
10. Aprocess in accordance with claim 9 in which said lithium carbonate and magnesium oxide are present a proportion'of from 1:10 to.1:1.
References Cited in the file of this patent. UNITED STATES PATENTS 1,8965041: Ruben Ian. 31, 1933 2,300,400 Axline June 26, 1940 2,457,515 Aker Dec. 28, 1948 2,697,670 Gaudenzi Dec. 21, 1954 2,730,458 Schultz Jan. 10, 1956 FOREIGN PATENTS 505,634 Belgium Sept. 29, 1951 OTHER REFERENCES T-upholme as a Protective Coating, News Edition orindustrial and,;,E g neering Chemistry, May 20, 1936; vol. 14, No; 10,195;

Claims (1)

1. A METHOD OF IMPROVING THE SCALING RESISTANCE AT TEMPERATURES ABOVE 800*C. IN THE PRESENCE OF CORROSIVE GASES OF A METAL ARTICLE COATED WITH A SCALING RESISTANT CHROMIUM-AND-NICKEL CONTAINING ALLOY WHICH COMPRISES APPLYING TO SAID COATED METAL ARTICLE A COATING CONSISTING ESSENTIALLY OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OF CHROMIUM OXIDE, ALUMINUM OXIDE, LITHIUM OXIDE, LITHIUM HYDROXIDE AND LITHIUM CARBONATE.
US355869A 1952-05-23 1953-05-18 Method of increasing the scaling resistance of metallic objects Expired - Lifetime US2823139A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3031331A (en) * 1959-10-23 1962-04-24 Jr William L Aves Metal-ceramic laminated skin surface
US3047420A (en) * 1958-11-03 1962-07-31 Inland Steel Co Aluminizing of ferrous metal base
US3054694A (en) * 1959-10-23 1962-09-18 Jr William L Aves Metal-ceramic laminated coating and process for making the same
US3055769A (en) * 1958-12-08 1962-09-25 Bendix Corp High temperature antifriction seal, material, and method of manufacture
US3362842A (en) * 1963-10-31 1968-01-09 Navy Usa Method of providing refractory metals with protective coatings and resulting article
US3481715A (en) * 1967-02-03 1969-12-02 Ford Motor Co Sealing member for high temperature applications and a process of producing the same
US4788410A (en) * 1985-09-17 1988-11-29 Mankiewicz Gebr. & Co. (Gmbh & Co.) Process for controlling and/or guiding the weld seam during arc welding and a paint therefor
US5346563A (en) * 1991-11-25 1994-09-13 United Technologies Corporation Method for removing sulfur from superalloy articles to improve their oxidation resistance
US5543183A (en) * 1995-02-17 1996-08-06 General Atomics Chromium surface treatment of nickel-based substrates
US20030172678A1 (en) * 2000-11-27 2003-09-18 Yoshihiro Iizawa Glass lining application method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE505634A (en) *
US1896041A (en) * 1931-05-02 1933-01-31 Vega Manuf Insulated wire
US2300400A (en) * 1940-06-26 1942-11-03 Metallizing Engineering Compan Heat corrosion resistant metallic material
US2457515A (en) * 1941-11-13 1948-12-28 Bell Telephone Labor Inc Insulating coating compositions and method of making
US2697670A (en) * 1952-07-28 1954-12-21 Bbc Brown Boveri & Cie Ceramic coated chromium steel
US2730458A (en) * 1950-10-03 1956-01-10 Ver Dentsche Metallwerke Ag Method of increasing the scaling resistance of metallic objects

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE505634A (en) *
US1896041A (en) * 1931-05-02 1933-01-31 Vega Manuf Insulated wire
US2300400A (en) * 1940-06-26 1942-11-03 Metallizing Engineering Compan Heat corrosion resistant metallic material
US2457515A (en) * 1941-11-13 1948-12-28 Bell Telephone Labor Inc Insulating coating compositions and method of making
US2730458A (en) * 1950-10-03 1956-01-10 Ver Dentsche Metallwerke Ag Method of increasing the scaling resistance of metallic objects
US2697670A (en) * 1952-07-28 1954-12-21 Bbc Brown Boveri & Cie Ceramic coated chromium steel

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3047420A (en) * 1958-11-03 1962-07-31 Inland Steel Co Aluminizing of ferrous metal base
US3055769A (en) * 1958-12-08 1962-09-25 Bendix Corp High temperature antifriction seal, material, and method of manufacture
US3031331A (en) * 1959-10-23 1962-04-24 Jr William L Aves Metal-ceramic laminated skin surface
US3054694A (en) * 1959-10-23 1962-09-18 Jr William L Aves Metal-ceramic laminated coating and process for making the same
US3362842A (en) * 1963-10-31 1968-01-09 Navy Usa Method of providing refractory metals with protective coatings and resulting article
US3481715A (en) * 1967-02-03 1969-12-02 Ford Motor Co Sealing member for high temperature applications and a process of producing the same
US4788410A (en) * 1985-09-17 1988-11-29 Mankiewicz Gebr. & Co. (Gmbh & Co.) Process for controlling and/or guiding the weld seam during arc welding and a paint therefor
US5346563A (en) * 1991-11-25 1994-09-13 United Technologies Corporation Method for removing sulfur from superalloy articles to improve their oxidation resistance
US5543183A (en) * 1995-02-17 1996-08-06 General Atomics Chromium surface treatment of nickel-based substrates
US6134972A (en) * 1995-02-17 2000-10-24 Rosemount Aerospace, Inc. Air data sensing probe with chromium surface treatment
US20030172678A1 (en) * 2000-11-27 2003-09-18 Yoshihiro Iizawa Glass lining application method
EP1354978A1 (en) * 2000-11-27 2003-10-22 Ikebukuro Horo Kogyo Co. Ltd. Glass lining application method
US6815013B2 (en) 2000-11-27 2004-11-09 Ikebukuro Horo Kogyo Co., Ltd. Glass lining application method

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