US3343930A - Ferrous metal article coated with an aluminum zinc alloy - Google Patents
Ferrous metal article coated with an aluminum zinc alloy Download PDFInfo
- Publication number
- US3343930A US3343930A US382595A US38259564A US3343930A US 3343930 A US3343930 A US 3343930A US 382595 A US382595 A US 382595A US 38259564 A US38259564 A US 38259564A US 3343930 A US3343930 A US 3343930A
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- United States
- Prior art keywords
- coating
- aluminum
- zinc
- strip
- ferrous
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims description 36
- 229910052751 metal Inorganic materials 0.000 title description 18
- 239000002184 metal Substances 0.000 title description 18
- 229910001297 Zn alloy Inorganic materials 0.000 title description 4
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 title description 3
- 238000000576 coating method Methods 0.000 claims description 97
- 239000011248 coating agent Substances 0.000 claims description 79
- 229910052782 aluminium Inorganic materials 0.000 claims description 56
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052725 zinc Inorganic materials 0.000 claims description 29
- 239000011701 zinc Substances 0.000 claims description 29
- 230000001464 adherent effect Effects 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- 239000010703 silicon Substances 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 15
- 239000010959 steel Substances 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000001996 bearing alloy Substances 0.000 description 8
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 7
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- 239000010953 base metal Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001327 Rimmed steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910000648 terne Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- 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
-
- 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
- C23C2/12—Aluminium or alloys based thereon
-
- 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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/38—Wires; Tubes
-
- 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
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
-
- 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
- This invention relates to zinc-aluminum coatings on ferrous surfaces, and more particularly to zinc-aluminum protective coatings on steel surfaces which coatings are ductile, corrosion resistant and tightly adherent to said surfaces.
- metals have been used in the past as a protective coating for ferrous surfaces, such metals including tin, zinc, terne metal, nickel, chromium, cadmium, copper, aluminum, bronze and lead.
- One of the most commonly used coating metals is zinc, partly because of its relatively low cost, and partly because of its higher position in the electromotive series relative to iron.
- Zinc coatings do not have adequate resistance to corrosion. The search for metallic coatings which will combine high protective power, ductility, adherence, good appearance and low cost is a continuing one.
- Another object of this invention is to provide metallic coatings on ferrous base stock, which coatings are metallurgically bonded to the base stock.
- Another object of this invention is to provide a ferrous base which has a metallic coating thereon and in which the iron-bearing alloy layer at the interface between coating and base metal is thin and uniform.
- a further object is to provide a ferrous base having a metallic coating thereon characterized by good appearance and formability.
- An additional object is to provide a ferrous base with a metallic coating which is ductile and firmly adherent.
- Another object is to provide a method for producing said coated product.
- Our product is characterized by the fact that the ironbearing alloy layer at the interface of the ferrous base and the coating is thin and uniform.
- the method by which our new product is obtained broadly comprises applying to a ferrous base, such as strip, the surface of which is substantially free from oxides and other contaminants, a coating consisting essentially of 25% to 70% aluminum, balance zinc, the coating being applied in such a manner as to result in a thin and uniform iron-bearing alloy layer at the interface between the base and the coating.
- This invention has particular applicability for the coating of steel strip and wire.
- Heavy alloying at the interface of steel strip and a non-ferrous protective coating metal promotes cracks in the coating upon subsequent deformation of the coated product.
- heavy alloying of coating metal with iron of the 3,343,930 Patented Sept. 26, 1967 strip results in a large proportionate loss of base metal, thus weakening the base metal itself. Then too, heavy alloying at the interface at times results in an uneven coating, the surface appearance of which leaves much to be desired.
- FIG. 1 is a reproduction of a photomicrograph of a cross section of a coated steel strip embodying our invention, the coating containing approximately 25% aluminum, and approximately 74% zinc.
- FIG. 2 is a reproduction of a photomicrograph of a cross section of a coated steel strip embodying our invention, the coating containing approximately 35% aluminum, and approximately 64% zinc.
- FIG. 3 is a reproduction of a photomicrograph of a cross section of a coated steel strip embodying our invention, the coating containing approximately 54% aluminum, and approximately 44.5% zinc.
- FIG. 4 is a reproduction of a photomicrograph of a cross section of a coated steel strip embodying our invention, the coating containing approximately 70% aluminum, and approximately 28% zinc.
- FIG. 5 is a diagrammatic side elevation of a preferred embodiment of apparatus for producing the product of this invention.
- a preferred method of coating a ferrous base is as follows.
- the strip is first passed through a cleaning solution which removes grease and dirt from the surface thereof.
- the cleaned strip is then introduced into a furnace and heated to a temperature approximately that of the coating bath.
- the strip is then passed through a protective atmosphere directly into a bath of molten metal consisting essentially of 25 to 70% aluminum, balance zinc.
- the temperature of the bath is maintained slightly above the melting point of the metal, the exact temperature depending, of course, upon the relative amounts of aluminum and zinc in the bath.
- Strip speeds and bath immersion times are similar to those used in continuous galvanizing.
- the cleaning solution was maintained at a temperature of approximately 200 F.
- the cleaned strip was scrubbed at scrubbers 5, and rinsed in tank 6 with water rinse 7. From the rinse tank 6, the strip was led through rubber squeegee rolls 8, over rolls 9 and downwardly through a furnace 10, where the strip was heated to a temperature of approximately 1200 F.
- the furnace was heated by the products of combustion of natural gas and air in the ratio of 1 to 8. From the furnace, the strip was led around positioning roll 11, through a holding chamber 12 where its temperature fell to approximately 800 F. An atmosphere of 99% hydrogen was maintained in the holding chamber 12 to protect the strip from oxidation prior to its entry into the coating pot 13. After entering pot 13, the strip was passed through a molten bath 14, by way of sinker rolls 15 and 15. This bath was maintained at a temperature of 1060 F. Upon leaving the bath, the strip was passed between a pair of smooth low carbon steel exit rolls 16. An air-blast 17 was used to chill the coating as the strip passed vertically to roll 18, and then take-up reel 19. The speed of the strip was approximately 45 feet per minute and the time of immersion in the coating bath was about 4 seconds. The total coating thickness, which includes the coating on the two sides of the thus-coated strip, averaged 0.00197 inch.
- the zinc employed for the molten mixture had a specified zinc purity of better than 99.99%.
- Silicon was added to the bath in the form of an aluminum alloy. This material analyzed as follows:
- FIG. 2 A photomicrograph taken at 500 magnifications, of a cross section of the coated product, made by the method of the example, is reproduced in FIG. 2.
- the alloy layer between the coating and base metal is so thin as to be almost indistinguishable at 500 magnifications.
- FIG. 1 is a reproduction of a photomicrograph, also at 500 magnifications, of a cross section of another coated product of our invention wherein carbon steel strip was coated by the process above described in a bath analyzing approximately 25 aluminum, 74% zinc and 0.77% silicon. In this sample, there is no distinguishable alloy formation of iron with coating metal.
- FIG. 3 is a photomicrograph, at 500 magnifications, of a cross section of a similar steel, coated by the process above described.
- the bath, from which the coated product was made analyzed approximately 54% aluminum, 44.5% zinc and 1.5% silicon
- the coating bath had an analysis of approximately 70% aluminum, 28% zinc and 2% silicon.
- thin iron-bearing alloy layer is meant a layer at the interface having an average thickness not greater than about 0.25 mil, excluding localized projections.
- our invention in its broad aspects, is not limited to an alloy layer of this thinness, for in some applications it may be possible to tolerate a layer of greater thickness.
- uniform is meant a layer surface which is substantially flat (for a flat substrate) but which may include localized projections into the zinc-aluminum coating, as shown, for example, in FIGS. 3 and 4.
- the operating temperature of the molten coating bath will ordinarily range from about 975 F. to 1220 F., depending on the amount of aluminum in the alloy, the temperature increasing with increasing aluminum content.
- the coated products of this invention show an advantage over continuously galvanized products in the salt spray test of the order of approximately 3 to 1, up to 8 to 1.
- the salt spray test is performed according to A.S.T.M. Method B117-62.
- the coated products of the invention exhibit a small spangle. This property is highly desirable in many operations, where additional surface treatment, such as the application of paint, is required. In the coating range of from about 25% to 45% aluminum content, the surface of the product has an exceptionally smooth, white lustre.
- the muffier test referred to is that known as Mufiier Condensate Test.
- coated specimens 2 inches by 4 inches, are dipped into an aqueous solution of 0.05 normal sulfuric acid and 0.01 normal hydrobromic acid for 8 seconds at a solution temperature of F.
- the specimens are removed at the end of the 8 second immersion period, and suspended in the vapors of the immersion solution for the remainder of one hour.
- the procedure is repeated every hour for 20 hours, after which the specimens are heated in a laboratory furnace for 2 hours at 500 F. to complete what is referred to as a one-day cycle.
- Specimens are examined visually after each one-day cycle for start of rusting (disregarding the rusting of the sheared edges of the specimens).
- the complete test comprises 13 one-day cycles.
- the products of our invention in the entire range from 25% to 70% aluminum in the coating, meet A.S.T.M. Specification No. A9359T for bend test requirements. Further, in the demanding fiat lockseam test, the products of our invention showed no fiaking at any aluminum concentration in the coating of from 25 to 45%. The 70% aluminum coating showed slight localized flaking.
- the ductility and adherence of the coatings of the products of our invention, over the entire range of aluminum content (25 to 70% aluminum) are such that the said products can withstand commercial forming such as corrugating, bending, etc. without significant cracking or flaking.
- Our improved coating may also be applied by What may be referred to as a roll-bonding procedure.
- a roll-bonding procedure As an example of this method, the surface of a low carbon steel sheet was roughened by acid etching. A thin layer of tridecyl alcohol was applied to the surface of the sheet. The sheet was then coated with a mixture comprising zinc powder (75%) and aluminum powder (25 the alcohol serving to promote initial adherence of the powder to the sheet. The sheet, with the powder coating thereon, was passed through pressure rolls to compact the powder on the sheet, and was then heated at 750 F. for a period of about five minutes to bond the coating to the sheet. This method is described more fully in an application by Edward H. Mayer and Hilton N. Rahn, filed concurrently herewith.
- silicon is required in producing the product of our invention by the hot dip process.
- the presence of silicon in the bath promotes the formation of an adherent coating, suppresses the formation of an iron-bearing alloy layer at the interface between the strip and the coating, and assures that the alloy layer which is formed is thin and uniform.
- the silicon content of the bath should be not less than 0.5 and preferably about 3%, of the aluminum content. More silicon may be used if desired. Silicon will also be present in the coating. However, the silicon content of the coating does not, so far as we can determine, have any effect on the corrosion resistance of the coated product. Silicon is not essential to the roll bonding process.
- Examples of articles, other than steel strip, for which the above-described zinc-aluminum coatings would find ready application are steel wire, hardware and structural shapes.
- the coatings of the products of our invention consist essentially of the metals zinc and aluminum, other substances which do not materially detract from the novel and basic properties of our invention may be present either as impurities or as deliberate additions.
- the coating may contain up to 0.3% chromium for control of intergranular corrosion.
- a ferrous base having a ductile, adherent, corrosion-resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 70% aluminum, balance zinc.
- a ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 45 aluminum, balance zinc.
- a ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 40% to 60% aluminum, balance zinc.
- a ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 70% aluminum, silicon in an amount not less than 0.5% of the aluminum content, balance zinc.
- a ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 45 aluminum, silicon in an amount not less than 0.5 of the aluminum content, balance zinc.
- a ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 40% to 60% aluminum, silicon in an amount not less than 0.5 of the aluminum content, balance zinc.
- a ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25% to 70% aluminum, balance zinc, the iron-bearing alloy layer at the interface between the ferrous base and the coating being thin and uniform.
- a ferrous base having an adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 45 aluminum, balance zinc, the iron-bearing alloy layer at the interface between the ferrous base and the coating being thin and uniform.
- a ferrous base having an adherent, corosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 40% to 60% aluminum, balance zinc, the iron-bearing alloy layer at the interface between the ferrous base and the coating being thin and uniform.
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Description
Sept. 26, 1967 A. R. BORZILLO ETAL 3,343,930
FERROUS METAL ARTICLE COATED WITH AN ALUMINUM ZINC ALLOY Filed July 14, 1964 3 Sheets-Sheet 1 INVENTORS Ange/0 R. Borz/l/o James B. Horton Sept. 26, l A. R. BORZILLO ETAL 3,343,930
FERROUS METAL ARTICLE COATED WITH AN ALUMINUM ZINC ALLOY Filed July 14, 1964 3 Sheets-Sheet 2 INVENTORS Ange/0 R. Borz/l/o James B. Horton p 1967 A. R. BORZILLO ETAL 3,343,930
FERROUS METAL ARTICLE COATED WITH ANALUMINUM ZINC ALLOY I INVENTORS Ange/0 R. 50/2/7/0 James B. Hor/on United States Patent 3,343,930 FERROUS METAL ARTICLE CGATED WITH AN ALUMINUM ZlNC ALLOY Angelo R. Borzillo, Allentown, and James B. Horton,
Bethlehem, Pa., assignors to Bethlehem Steel Company, a corporation of Pennsylvania Filed July 14, 1964, Ser. No. 382,595 9 Claims. (Cl. 29-1962) This invention relates to zinc-aluminum coatings on ferrous surfaces, and more particularly to zinc-aluminum protective coatings on steel surfaces which coatings are ductile, corrosion resistant and tightly adherent to said surfaces.
In the protection of ferrous surfaces from corrosive media, it is common practice to coat the ferrous metal surface with a non-ferrous metal, by immersion in a molten bath of the coating metal or by other methods. These coatings should not only be protective, but they should be ductile and tightly adherent as well, and should have a smooth, pleasing appearance.
Many metals have been used in the past as a protective coating for ferrous surfaces, such metals including tin, zinc, terne metal, nickel, chromium, cadmium, copper, aluminum, bronze and lead. One of the most commonly used coating metals is zinc, partly because of its relatively low cost, and partly because of its higher position in the electromotive series relative to iron. However, for many applications, Zinc coatings do not have adequate resistance to corrosion. The search for metallic coatings which will combine high protective power, ductility, adherence, good appearance and low cost is a continuing one.
Accordingly it is an object of this invention to provide a ferrous base having thereon a metallic coating which is highly corrosion-resistant.
Another object of this invention is to provide metallic coatings on ferrous base stock, which coatings are metallurgically bonded to the base stock.
Another object of this invention is to provide a ferrous base which has a metallic coating thereon and in which the iron-bearing alloy layer at the interface between coating and base metal is thin and uniform.
A further object is to provide a ferrous base having a metallic coating thereon characterized by good appearance and formability.
An additional obiect is to provide a ferrous base with a metallic coating which is ductile and firmly adherent.
Another object is to provide a method for producing said coated product.
We have discovered that the foregoing objects can be attained by providing a ferrous base which has metallurgically bonded thereto a coating consisting essentially of from 25% to 70% aluminum, with the balance substantially zinc.
Our product is characterized by the fact that the ironbearing alloy layer at the interface of the ferrous base and the coating is thin and uniform.
Briefly, the method by which our new product is obtained broadly comprises applying to a ferrous base, such as strip, the surface of which is substantially free from oxides and other contaminants, a coating consisting essentially of 25% to 70% aluminum, balance zinc, the coating being applied in such a manner as to result in a thin and uniform iron-bearing alloy layer at the interface between the base and the coating.
This invention has particular applicability for the coating of steel strip and wire. Heavy alloying at the interface of steel strip and a non-ferrous protective coating metal promotes cracks in the coating upon subsequent deformation of the coated product. In addition, with strip of thin gages, heavy alloying of coating metal with iron of the 3,343,930 Patented Sept. 26, 1967 strip results in a large proportionate loss of base metal, thus weakening the base metal itself. Then too, heavy alloying at the interface at times results in an uneven coating, the surface appearance of which leaves much to be desired.
The coated product of our invention and a preferred method, by which the coating may be applied to a ferrous base, will be described with reference to the following drawings.
FIG. 1 is a reproduction of a photomicrograph of a cross section of a coated steel strip embodying our invention, the coating containing approximately 25% aluminum, and approximately 74% zinc.
FIG. 2 is a reproduction of a photomicrograph of a cross section of a coated steel strip embodying our invention, the coating containing approximately 35% aluminum, and approximately 64% zinc.
FIG. 3 is a reproduction of a photomicrograph of a cross section of a coated steel strip embodying our invention, the coating containing approximately 54% aluminum, and approximately 44.5% zinc.
FIG. 4 is a reproduction of a photomicrograph of a cross section of a coated steel strip embodying our invention, the coating containing approximately 70% aluminum, and approximately 28% zinc.
FIG. 5 is a diagrammatic side elevation of a preferred embodiment of apparatus for producing the product of this invention.
A preferred method of coating a ferrous base, e.g. steel strip, is as follows. The strip is first passed through a cleaning solution which removes grease and dirt from the surface thereof. The cleaned strip is then introduced into a furnace and heated to a temperature approximately that of the coating bath. The strip is then passed through a protective atmosphere directly into a bath of molten metal consisting essentially of 25 to 70% aluminum, balance zinc. The temperature of the bath is maintained slightly above the melting point of the metal, the exact temperature depending, of course, upon the relative amounts of aluminum and zinc in the bath.
Strip speeds and bath immersion times are similar to those used in continuous galvanizing.
Following is a specific example of our preferred method.
Referring to FIG. 5, a strip 1 of 28 gage rimmed steel, having a carbon content of 0.06%, a manganese content of 0.31%, and other elements customarily found in rimmed strip steel, was fed from pay-off reel 2 to cleaning tank 3 containing an aqueous solution 4 (approximately 4 oz./ gal.) of Pennsalt No. 30, a standard alkaline cleaning solution for steel strip. The cleaning solution was maintained at a temperature of approximately 200 F. The cleaned strip was scrubbed at scrubbers 5, and rinsed in tank 6 with water rinse 7. From the rinse tank 6, the strip was led through rubber squeegee rolls 8, over rolls 9 and downwardly through a furnace 10, where the strip was heated to a temperature of approximately 1200 F. The furnace was heated by the products of combustion of natural gas and air in the ratio of 1 to 8. From the furnace, the strip was led around positioning roll 11, through a holding chamber 12 where its temperature fell to approximately 800 F. An atmosphere of 99% hydrogen was maintained in the holding chamber 12 to protect the strip from oxidation prior to its entry into the coating pot 13. After entering pot 13, the strip was passed through a molten bath 14, by way of sinker rolls 15 and 15. This bath was maintained at a temperature of 1060 F. Upon leaving the bath, the strip was passed between a pair of smooth low carbon steel exit rolls 16. An air-blast 17 was used to chill the coating as the strip passed vertically to roll 18, and then take-up reel 19. The speed of the strip was approximately 45 feet per minute and the time of immersion in the coating bath was about 4 seconds. The total coating thickness, which includes the coating on the two sides of the thus-coated strip, averaged 0.00197 inch.
In preparing the molten bath, 99.50% minimum Al grade aluminum was used. This material had the following analysis:
Percent Aluminum 99.65 Iron 0.19 Silicon 0.13 Manganese 0.01 Zinc 0.01 Vanadium 0.01 Cadmium 0.02 Sodium 0.001
The zinc employed for the molten mixture had a specified zinc purity of better than 99.99%.
Silicon was added to the bath in the form of an aluminum alloy. This material analyzed as follows:
Percent Silicon 12.00 Iron 0.3 3 Aluminum Balance These ingredients were combined in such proportions that the bath analyzed approximately 35 aluminum, 64% zinc, and 1% silicon.
A photomicrograph taken at 500 magnifications, of a cross section of the coated product, made by the method of the example, is reproduced in FIG. 2. The alloy layer between the coating and base metal is so thin as to be almost indistinguishable at 500 magnifications.
FIG. 1 is a reproduction of a photomicrograph, also at 500 magnifications, of a cross section of another coated product of our invention wherein carbon steel strip was coated by the process above described in a bath analyzing approximately 25 aluminum, 74% zinc and 0.77% silicon. In this sample, there is no distinguishable alloy formation of iron with coating metal.
As the aluminum content in the coating is increased above 35%, there is evidence of a small amount of interfacial alloy layer. But even when the aluminum represents 70% of the alloy coating, the iron-bearing alloy at the interface is uniform and thin. The thinness and uniformity of the interfacial alloy occurring with the higher ranges of aluminum can be observed in FIGURES 3 and 4, each of which is a photomicrograph, at 500 magnifications, of a cross section of a similar steel, coated by the process above described. In FIG. 3, the bath, from which the coated product was made, analyzed approximately 54% aluminum, 44.5% zinc and 1.5% silicon, While in FIG. 4 the coating bath had an analysis of approximately 70% aluminum, 28% zinc and 2% silicon.
All of the samples shown in FIGURES l-4 were etched in a solution of 95% amyl alcohol, 5% nitric acid, for five seconds.
By thin iron-bearing alloy layer is meant a layer at the interface having an average thickness not greater than about 0.25 mil, excluding localized projections. However, our invention, in its broad aspects, is not limited to an alloy layer of this thinness, for in some applications it may be possible to tolerate a layer of greater thickness.
By uniform is meant a layer surface which is substantially flat (for a flat substrate) but which may include localized projections into the zinc-aluminum coating, as shown, for example, in FIGS. 3 and 4.
The operating temperature of the molten coating bath will ordinarily range from about 975 F. to 1220 F., depending on the amount of aluminum in the alloy, the temperature increasing with increasing aluminum content.
Specific examples of preferred bath temperatures for varying aluminum contents are set forth in the following examples:
Approximate bath Aluminum (percent): temperature F.) 25 995 Coatings made as above described are metallurgically bonded to the ferrous base.
Our coated products have many favorable properties, as Will be apparent from the following data based on coatings produced by the method above described.
In the entire coating range of 25% to 70% aluminum, the coated products of this invention show an advantage over continuously galvanized products in the salt spray test of the order of approximately 3 to 1, up to 8 to 1. The salt spray test is is performed according to A.S.T.M. Method B117-62.
Typical results (average of four 4" x 6" test specimens with protected edges) for salt spray tests are set forth in the following table for a galvanized steel sheet, and for steel sheets coated with zinc-aluminum coatings according to the invention.
TABLE I Hours to first (1%) rust per Type of coating: mil of coating thickness (1) Continuous galvanized 325 (2) Zinc-aluminum coating containing approximately 25 Al 2290 (3) Same as (2) with approximately 35 Al 3234 (4) Same as (2) with approximately 45% A1 1 3805 (5) Same as (2) with 54% Al 1 3405 (6) Same as (2) with 70% Al 940 1 Tests not completed.
Appearancewise, the coated products of the invention exhibit a small spangle. This property is highly desirable in many operations, where additional surface treatment, such as the application of paint, is required. In the coating range of from about 25% to 45% aluminum content, the surface of the product has an exceptionally smooth, white lustre.
In the so-called muffier test, the corrosion resistance of the products of our invention, within the coating range of 25 to 70% aluminum content, is far and above that which can be met with galvanized products.
The muffier test referred to is that known as Mufiier Condensate Test. In the test, coated specimens, 2 inches by 4 inches, are dipped into an aqueous solution of 0.05 normal sulfuric acid and 0.01 normal hydrobromic acid for 8 seconds at a solution temperature of F. The specimens are removed at the end of the 8 second immersion period, and suspended in the vapors of the immersion solution for the remainder of one hour. The procedure is repeated every hour for 20 hours, after which the specimens are heated in a laboratory furnace for 2 hours at 500 F. to complete what is referred to as a one-day cycle. Specimens are examined visually after each one-day cycle for start of rusting (disregarding the rusting of the sheared edges of the specimens). The complete test comprises 13 one-day cycles.
Test results from the mufiler test are shown in Table II, which follows:
(3) Same as (2) with approximately 35% TABLE IIContinued Cycles for start of rusting of Type of coating: steel base (4) Same as (2) with approximately 45% Al l3 (5) Same as (2) with approximately 54% Al 13 (6) Same as (2) with approximately 70% Rusting of sheared edges of specimens disregarded.
The products of our invention in the entire range from 25% to 70% aluminum in the coating, meet A.S.T.M. Specification No. A9359T for bend test requirements. Further, in the demanding fiat lockseam test, the products of our invention showed no fiaking at any aluminum concentration in the coating of from 25 to 45%. The 70% aluminum coating showed slight localized flaking.
Furthermore, the products of our invention having coatings in the range between 25 and 45% aluminum showed only slight cracking when bent 180 fiat on themselves.
The ductility and adherence of the coatings of the products of our invention, over the entire range of aluminum content (25 to 70% aluminum) are such that the said products can withstand commercial forming such as corrugating, bending, etc. without significant cracking or flaking.
Our improved coating may also be applied by What may be referred to as a roll-bonding procedure. As an example of this method, the surface of a low carbon steel sheet was roughened by acid etching. A thin layer of tridecyl alcohol was applied to the surface of the sheet. The sheet was then coated with a mixture comprising zinc powder (75%) and aluminum powder (25 the alcohol serving to promote initial adherence of the powder to the sheet. The sheet, with the powder coating thereon, was passed through pressure rolls to compact the powder on the sheet, and was then heated at 750 F. for a period of about five minutes to bond the coating to the sheet. This method is described more fully in an application by Edward H. Mayer and Hilton N. Rahn, filed concurrently herewith.
As far as is presently known, silicon is required in producing the product of our invention by the hot dip process. We have found that the presence of silicon in the bath promotes the formation of an adherent coating, suppresses the formation of an iron-bearing alloy layer at the interface between the strip and the coating, and assures that the alloy layer which is formed is thin and uniform. We have further found that the silicon content of the bath should be not less than 0.5 and preferably about 3%, of the aluminum content. More silicon may be used if desired. Silicon will also be present in the coating. However, the silicon content of the coating does not, so far as we can determine, have any effect on the corrosion resistance of the coated product. Silicon is not essential to the roll bonding process.
To recapitulate, we have found that our zinc-aluminum coated ferrous products, wherein the aluminum content represents from 25% to 70% of the total coating, exhibit corrosion resistance properties superior to those of continuously galvanized products. Within this broad range, coatings having an aluminum content between 25% and 45 of the total coatings are characterized by their ductility and freedom from flaking, when subjected to severe forming operations; while coatings having an aluminum content between 40% and 60% of the total coating are characterized by their remarkable corrosion resistance, which is far superior to that of galvanized coatings, although at some slight loss of formability at the high end of the aluminum ranges.
Examples of articles, other than steel strip, for which the above-described zinc-aluminum coatings would find ready application, are steel wire, hardware and structural shapes.
While the coatings of the products of our invention consist essentially of the metals zinc and aluminum, other substances which do not materially detract from the novel and basic properties of our invention may be present either as impurities or as deliberate additions. For example, the coating may contain up to 0.3% chromium for control of intergranular corrosion.
By the term consisting essentially of we do not wish to exclude the presence of such substances.
All percentages shown herein, which relate to bath or coating components, represent weight percent.
We claim:
1. A ferrous base having a ductile, adherent, corrosion-resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 70% aluminum, balance zinc.
2. A ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 45 aluminum, balance zinc.
3. A ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 40% to 60% aluminum, balance zinc.
4. A ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 70% aluminum, silicon in an amount not less than 0.5% of the aluminum content, balance zinc.
5. A ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 45 aluminum, silicon in an amount not less than 0.5 of the aluminum content, balance zinc.
6. A ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 40% to 60% aluminum, silicon in an amount not less than 0.5 of the aluminum content, balance zinc.
7. A ferrous base having a ductile, adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25% to 70% aluminum, balance zinc, the iron-bearing alloy layer at the interface between the ferrous base and the coating being thin and uniform.
8. A ferrous base having an adherent, corrosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 25 to 45 aluminum, balance zinc, the iron-bearing alloy layer at the interface between the ferrous base and the coating being thin and uniform.
9. A ferrous base having an adherent, corosion resistant coating metallurgically bonded thereto, said coating consisting essentially of 40% to 60% aluminum, balance zinc, the iron-bearing alloy layer at the interface between the ferrous base and the coating being thin and uniform.
References Cited UNITED STATES PATENTS 2,126,244 8/1938 Cook 29-196.5 2,196,034 4/1940 Schulzo -178.6 2,870,008 1/1959 Neu 75146 X 3,190,768 6/1965 Wright 29196.5 X
HYLAND BIZOT, Primary Examiner.
UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 3,343,930 September 26, 1967 Angelo R. Borzillo et 211.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
In the drawings, Sheet 1, strike out FIGS. 1 and 2 and insert instead the following:
in the heading to the printed specification, lines 4 to 6, for Angelo R. Borzillo, Allentown, and James B. Horton, Bethlehem, PEL, assignors to Bethlehem Steel Company, a corporation of Pennsylvania readAngelo R. Borzillo, Bethlehem, and James B. Horton, Allentown, Pa., assignors, by mesne assignments, to Bethlehem Steel Corporation, a corporation of Delaware.
Signed and sealed this 11th day of March 1969.
[SEAL] Attest:
EDWARD M. FLETCHER, JR. Attesti'ng Oflicer.
EDWARD J. BRENNER,
Commissioner 0 f Patents.
Claims (1)
1. A FERROUS BASE HAVING A DUCTILE, ADHERENT, CORROSION-RESISTANT COATING METALLURGICALLY BONDED THERETO, SAID COATING CONSISTING ESSENTIALLY OF 25% TO 70% ALUMINUM, BALANCE ZINC.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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US382595A US3343930A (en) | 1964-07-14 | 1964-07-14 | Ferrous metal article coated with an aluminum zinc alloy |
GB22715/65A GB1115673A (en) | 1964-07-14 | 1965-05-28 | Zinc-aluminum coated products and methods therefor |
SE7130/65A SE315460B (en) | 1964-07-14 | 1965-06-01 | |
DE19651796353 DE1796353C2 (en) | 1964-07-14 | 1965-07-09 | Ferrous metal article with a zinc-aluminum alloy coating and method for its manufacture |
DE19651521148 DE1521148C3 (en) | 1964-07-14 | 1965-07-09 | Ferrous metal article with an aluminum-zinc alloy coating and method for its manufacture |
LU49050D LU49050A1 (en) | 1964-07-14 | 1965-07-12 | |
FR24793A FR1441918A (en) | 1964-07-14 | 1965-07-15 | Zinc and aluminum coatings and their application process |
US627207A US3393089A (en) | 1964-07-14 | 1967-03-30 | Method of forming improved zinc-aluminum coating on ferrous surfaces |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US382595A US3343930A (en) | 1964-07-14 | 1964-07-14 | Ferrous metal article coated with an aluminum zinc alloy |
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US3343930A true US3343930A (en) | 1967-09-26 |
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US382595A Expired - Lifetime US3343930A (en) | 1964-07-14 | 1964-07-14 | Ferrous metal article coated with an aluminum zinc alloy |
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US3808031A (en) * | 1968-05-31 | 1974-04-30 | Chromalloy American Corp | Multi-metal corrosion-resistant diffusion coatings |
US4053663A (en) * | 1972-08-09 | 1977-10-11 | Bethlehem Steel Corporation | Method of treating ferrous strand for coating with aluminum-zinc alloys |
US3952120A (en) * | 1974-05-31 | 1976-04-20 | Bethlehem Steel Corporation | Aluminum-zinc coated low-alloy ferrous product and method |
US3958994A (en) * | 1974-08-26 | 1976-05-25 | American Hoechst Corporation | Photosensitive diazo steel lithoplate structure |
US4036600A (en) * | 1975-06-05 | 1977-07-19 | Kawasaki Steel Corporation | Steel substrate electroplated with Al powder dispersed in Zn |
US4350539A (en) * | 1979-11-08 | 1982-09-21 | Bethlehem Steel Corporation | Method of improving the ductility of the coating of an aluminum-zinc alloy coated ferrous product |
US4287008A (en) * | 1979-11-08 | 1981-09-01 | Bethlehem Steel Corporation | Method of improving the ductility of the coating of an aluminum-zinc alloy coated ferrous product |
US4264684A (en) * | 1979-12-17 | 1981-04-28 | Bethlehem Steel Corporation | Zinc-alloy coated ferrous product resistant to embrittlement |
EP0037143B1 (en) * | 1980-03-25 | 1985-03-20 | CENTRE DE RECHERCHES METALLURGIQUES CENTRUM VOOR RESEARCH IN DE METALLURGIE Association sans but lucratif | Hot dip coating process |
WO1981002748A1 (en) * | 1980-03-25 | 1981-10-01 | S Radtke | Zinc-aluminum alloys and coatings |
US4358887A (en) * | 1980-04-04 | 1982-11-16 | Creps John A | Method for galvanizing and plastic coating steel |
US4330598A (en) * | 1980-06-09 | 1982-05-18 | Inland Steel Company | Reduction of loss of zinc by vaporization when heating zinc-aluminum coatings on a ferrous metal base |
US4390377A (en) * | 1981-01-12 | 1983-06-28 | Hogg James W | Novel continuous, high speed method of galvanizing and annealing a continuously travelling low carbon ferrous wire |
US4479832A (en) * | 1981-06-15 | 1984-10-30 | Bethlehem Steel Corporation | Method of producing light absorptive surface on aluminum zinc alloy coated product |
US4389463A (en) * | 1981-07-23 | 1983-06-21 | United Technologies Corporation | Zinc-aluminum hot dip coated ferrous article |
US4456663A (en) * | 1981-12-02 | 1984-06-26 | United States Steel Corporation | Hot-dip aluminum-zinc coating method and product |
US4605598A (en) * | 1983-06-28 | 1986-08-12 | Fils Et Cables D'acier De Lens (Fical) | Steel wire having superposed coatings resisting corrosion |
US4721656A (en) * | 1984-09-17 | 1988-01-26 | Eltech Systems Corporation | Electroplating aluminum alloys from organic solvent baths and articles coated therewith |
US5091150A (en) * | 1986-07-14 | 1992-02-25 | Nuova Italsider Spa | Zinc-aluminium based alloy for coating steel products |
US4722871A (en) * | 1986-08-14 | 1988-02-02 | Cosmos Engineering, Inc. | Zinc-aluminum alloy coatings for steel |
US5308710A (en) * | 1991-11-29 | 1994-05-03 | Daido Steel Sheet Corp. | Al-Zn-Si base alloy coated product |
US5478600A (en) * | 1991-11-29 | 1995-12-26 | Daido Steel Sheet Corporation | Process for coating ferrous product with Al-Zn-Si alloy |
US6468674B2 (en) | 1999-10-07 | 2002-10-22 | Bethlehem Steel Corporation | Coating composition for steel—product, a coated steel product, and a steel product coating method |
US20040161629A1 (en) * | 1999-10-07 | 2004-08-19 | Mcdevitt Erin T. | Composition for controlling spangle size, a coated steel product, and a coating method |
US7041386B2 (en) | 1999-10-07 | 2006-05-09 | Isg Technologies Inc. | Composition for controlling spangle size, a coated steel product, and a coating method |
US6610422B1 (en) | 2001-01-31 | 2003-08-26 | Nkk Corporation | Coated steel sheet and method for manufacturing the same |
US8663807B2 (en) | 2001-10-02 | 2014-03-04 | Henkel Ag & Co. Kgaa | Article of manufacture and process for anodically coating aluminum and/or titanium with ceramic oxides |
US20090258242A1 (en) * | 2001-10-02 | 2009-10-15 | Henkel Ag & Co. Kgaa | Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating |
US20100000870A1 (en) * | 2001-10-02 | 2010-01-07 | Henkel Ag & Co. Kgaa | Article of manufacture and process for anodically coating aluminum and/or titanium with ceramic oxides |
US8361630B2 (en) | 2001-10-02 | 2013-01-29 | Henkel Ag & Co. Kgaa | Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating |
US20090142616A1 (en) * | 2005-09-01 | 2009-06-04 | Shiro Fujii | Hot-dip zn-al alloy-plated steel material with excellent bending workability and production method thereof |
US20070119715A1 (en) * | 2005-11-25 | 2007-05-31 | Sacks Abraham J | Corrosion Resistant Wire Products and Method of Making Same |
US11840763B2 (en) | 2008-03-13 | 2023-12-12 | Bluescope Steel Limited | Metal-coated steel strip |
US11807941B2 (en) | 2009-03-13 | 2023-11-07 | Bluescope Steel Limited | Corrosion protection with Al/Zn-based coatings |
US20100252241A1 (en) * | 2009-04-02 | 2010-10-07 | Mcdermott Chris | Ceramic coated automotive heat exchanger components |
US9701177B2 (en) * | 2009-04-02 | 2017-07-11 | Henkel Ag & Co. Kgaa | Ceramic coated automotive heat exchanger components |
US20120160233A1 (en) * | 2010-12-22 | 2012-06-28 | Yudie Yuan | Solar energy absorber unit and solar energy device containing same |
US9127860B2 (en) * | 2010-12-22 | 2015-09-08 | Novelis Inc. | Solar energy absorber unit and solar energy device containing same |
CN103045981A (en) * | 2013-01-29 | 2013-04-17 | 云南科力新材料有限公司 | Hot-dip aluminum and zinc alloy containing rare earth and magnesium and preparation method thereof |
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CN103045981B (en) * | 2013-01-29 | 2015-09-09 | 云南科力新材料股份有限公司 | A kind of hot-dip coating aluminium-zinc alloy containing rare earth and magnesium and preparation method thereof |
EP2873883A1 (en) * | 2013-11-18 | 2015-05-20 | Cave S.r.l. | Sliding bearing for structural engineering |
ITMI20131907A1 (en) * | 2013-11-18 | 2015-05-19 | Cave S R L | STRIPE BEARING FOR STRUCTURAL ENGINEERING |
WO2018104298A1 (en) | 2016-12-05 | 2018-06-14 | Onderzoekscentrum Voor Aanwending Van Staal N.V. | Method and system for manufacturing a steel product having a coating with spangles, and a steel product having a coating with spangles. |
US10913994B2 (en) | 2017-09-08 | 2021-02-09 | Nippon Steel Corporation | Zn—Al—Mg-based plated steel sheet |
WO2021228435A1 (en) * | 2020-05-12 | 2021-11-18 | Eaton Intelligent Power Limited | Grounding element and electrical installation component having a grounding element |
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