US20160251761A1 - ZnAlMg-Coated Metal Sheet with Improved Flexibility and Corresponding Manufacturing Process - Google Patents
ZnAlMg-Coated Metal Sheet with Improved Flexibility and Corresponding Manufacturing Process Download PDFInfo
- Publication number
- US20160251761A1 US20160251761A1 US15/028,249 US201415028249A US2016251761A1 US 20160251761 A1 US20160251761 A1 US 20160251761A1 US 201415028249 A US201415028249 A US 201415028249A US 2016251761 A1 US2016251761 A1 US 2016251761A1
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- US
- United States
- Prior art keywords
- metallic coating
- weight
- manufacturing process
- bath
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 title claims description 4
- 239000002184 metal Substances 0.000 title claims description 4
- 238000000576 coating method Methods 0.000 claims abstract description 122
- 239000011248 coating agent Substances 0.000 claims abstract description 108
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 238000010422 painting Methods 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 239000003973 paint Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 13
- 229920000728 polyester Polymers 0.000 claims description 12
- 238000005238 degreasing Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 238000007711 solidification Methods 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 230000007717 exclusion Effects 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 21
- 238000005260 corrosion Methods 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 13
- 238000007792 addition Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000004075 alteration Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid 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
- 238000004090 dissolution Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- -1 zinc-aluminum-magnesium Chemical compound 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23C2/26—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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/265—After-treatment by applying solid particles to the molten coating
-
- 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
-
- 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
- C23C2/40—Plates; Strips
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
Definitions
- This invention relates to a metal sheet comprising a substrate, at least one face of which is coated with a metallic coating comprising Al and Mg, the remainder of the metallic coating being Zn, unavoidable impurities and optionally one or more additional elements selected from among Si, Ti, Ca, Mn, La, Ce and Bi, wherein the content by weight of each additional element in the metallic coating is less than 0.3%.
- Galvanized metallic coatings comprising essentially zinc and 0.1 to 0.4% by weight aluminum are conventionally used because of the effective protection they provide against corrosion.
- Coatings that are currently competitors with these metallic coatings comprise in particular zinc and additions of magnesium and aluminum, in proportions that can respectively be as high as up to 10% and up to 20% by weight.
- Metallic coatings of this type are referred to overall in this application by the term zinc-aluminum-magnesium or ZnAlMg coatings.
- magnesium significantly improves the corrosion resistance of steels coated with a metallic coating which can make it possible to reduce the thickness of the metallic coating or, with a constant thickness, to increase the guarantee of protection against corrosion over time.
- These sheets coated with a ZnAlMg coating are intended, for example, for use in the automobile sector, electric household appliances or construction.
- JP2010255084 It is known from JP2010255084 that the cracking resistance can be improved by adding from 0.005 to 0.2% by weight nickel to a metallic coating that also contains 1 to 10% by weight aluminum and 0.2 to 1% by weight magnesium.
- the nickel thus added has the characteristic that the majority of the element is located at the interface between the steel and the metallic coating, which contributes to inhibiting the formation of cracks in the deformed zones.
- the addition of nickel has several disadvantages:
- An object of the present invention is to mitigate the problems mentioned above by making available a ZnAlMg sheet, the metallic coating of which cracks less on severe bends, while retaining the advantages of the ZnAlMg coating in terms of corrosion resistance.
- the present invention provides a process for the manufacture of a pre-painted sheet comprising at least the following steps:
- the process according to the present invention may also comprise the following optional characteristics, considered individually or in combination:
- the solution to the technical problem posed consists of combining a paint film and a metallic coating that have a particular composition. Surprisingly, it has been found by the inventors that this combination has a synergy such that the ZnAlMg coating according to the invention has fewer cracks in the severe bends when it is covered by a paint film than when it is bare.
- the present invention further provides a pre-painted sheet comprising a steel substrate, at least one face of which is coated by a metallic coating constituted by 4.4% to 5.6% by weight aluminum and 0.3°/o to 0.56% by weight magnesium, the remainder of the metallic coating being exclusively zinc, unavoidable impurities resulting from the process and optionally one or more additional elements selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, wherein the content by weight of each additional element in the metallic coating is less than 0.3%, wherein the presence of nickel in the metallic coating is excluded and the metallic coating is covered by at least one paint film.
- the sheet according to the present invention can also have the following optional characteristics, considered individually or in combination:
- the sheet comprises a steel substrate covered on at least one of its faces with a metallic coating, which is itself covered by at least one paint film.
- the metallic coating generally has a thickness less than or equal to 25 ⁇ m and has the purpose of protecting the substrate against corrosion.
- the metallic coating is constituted by aluminum and magnesium, the remainder of the metallic coating being exclusively zinc, unavoidable impurities resulting from the metallic coating deposition process and optionally one or more additional elements selected among Si, Ti, Ca, Mn, La, Ce and Bi, wherein the percentage by weight of each additional element in the metallic coating is less than 0.3%, wherein the presence of nickel is excluded.
- the content by weight of aluminum in the metallic coating is between 4.4 and 5.6%. This range of content by weight of aluminum promotes the formation of the binary eutectic Zn/Al in the microstructure of the metallic coating. This eutectic system is particularly ductile and promotes the achievement of a flexible metallic coating.
- the aluminum content is preferably between 4.75 and 5.25% by weight.
- the content of aluminum by weight is measured without taking into account the intermetallic that is rich in aluminum and is located at the interface of the substrate and the metallic coating.
- a measurement of this type can be taken, for example, by glow discharge spectrometry.
- a measurement by chemical dissolution would lead to the simultaneous dissolution of the metallic coating and the intermetallic and would overestimate the content by weight of aluminum on the order of 0.05 to 0.5% as a function of the thickness of the metallic coating.
- the content by weight of magnesium in the metallic coating is between 0.3 and 0.56%. Below 0.3%, the improvement in the resistance to corrosion provided by the magnesium is no longer sufficient. Above 0.56%, the synergy of the paint film and of the metallic coating according to the invention is no longer observed.
- the content by weight of magnesium is between 0.44 and 0.56%, which is the best compromise in terms of corrosion resistance and flexibility.
- the unavoidable impurities originate from the ingots used to feed the molten zinc bath or result from the passage of the substrate in the bath.
- the most common unavoidable impurity that results from the passage of the substrate in the bath is iron, which can be present in an amount up to 0.8% by weight of the metallic coating, generally less than or equal to 0.4% and generally between 0.1 and 0.4% by weight.
- the unavoidable impurities originating from the ingots used to feed the bath are generally lead (Pb), which is present in a content less than 0.01% by weight, cadmium (Cd), which is present in a content less than 0.005% by weight, and tin (Sn), which is present in a content less than 0.001% by weight.
- Pb lead
- Cd cadmium
- Sn tin
- the metallic coating does not include nickel as an additional element, because nickel has the disadvantages described above.
- the metallic coating does not contain any additional element. That makes it possible to simplify the management of the galvanizing bath and to minimize the number of phases formed in the metallic coating.
- the sheet comprises a paint film.
- the paint films are generally polymer-based and comprise at least one layer of paint. They preferably comprise at least one polymer selected from the group consisting of melamine cross-linked polyesters, isocyanate cross-linked polyesters, polyurethanes and halogenated derivatives of vinyl polymers, with the exclusion of cataphoretic paints. These polymers have the characteristic that they are particularly flexible, which promotes the synergy of the paint film with the metallic coating.
- the paint film can be formed, for example, by two successive layers of paints, namely a primer layer and a finish layer, which is generally the case in creating the film applied to the top face of the sheet, or a single layer of paint, which is generally the case in creating the film applied to the bottom face of the sheet.
- a primer layer and a finish layer which is generally the case in creating the film applied to the top face of the sheet
- a single layer of paint which is generally the case in creating the film applied to the bottom face of the sheet.
- Other numbers of layers can be used in certain variants.
- the paint films typically have thicknesses between 1 and 200 ⁇ m.
- the interface between the metallic coating and the paint film comprises one or more characteristics selected among an alteration of the aluminum oxide/hydroxide layer naturally present on the surface of the metallic coating, an alteration of the magnesium oxide/hydroxide layer naturally present on the surface of the metallic coating and a conversion layer characterized by its chromium layer weight (in the case of chromate conversion treatment) or by its titanium layer weight (in case of a conversion treatment without chromium).
- the installation can comprise a single line or, for example, two different lines for the application of the metallic coatings and the painting respectively. If two different lines are used, they can be located on the same site or in different sites. The following description considers, by way of example, a variant where two separate lines are used.
- a steel substrate is used that is obtained, for example, by hot rolling followed by cold rolling.
- the substrate is in the form of a strip that is passed through a bath to deposit the metallic coating by hot dipping.
- the bath is a molten zinc bath containing from 4.4 to 5.6% by weight aluminum and from 0.3 to 0.56% by weight magnesium.
- the bath can also contain unavoidable impurities resulting from the process, such as impurities originating from the ingots used to supply the bath, and/or one or more additional elements selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, wherein the content by weight of each additional element in the metallic coating is less than 0.3%, the presence of nickel being excluded.
- the most common unavoidable impurity that results from the passage of the substrate through the bath is iron, which can be present in a content up to 0.8% by weight, generally less than or equal to 0.4% and generally between 0.1 and 0.4% by weight.
- the unavoidable impurities originating from the ingots used to feed the bath are generally lead (Pb), which is present in a content less than 0.01% by weight, cadmium (Cd), which is present in a content less than 0.005% by weight, and tin (Sn), which is present in a content less than 0.001% by weight.
- Pb lead
- Cd cadmium
- Sn tin
- the bath is at a temperature between 350° C. and 510° C., preferably between 370° C. and 470° C.
- the substrate is wiped, for example, by means of nozzles that project a gas onto both sides of the substrate to adjust the thickness of the coatings.
- the wiping gas comprises neither particles nor solutions such as, for example, those comprising a magnesium phosphate and/or a magnesium silicate.
- These wiping gas additions modify the solidification of the metallic coating and therefore its microstructure, which would contribute to a degradation of the proper flexibility of the pre-painted sheet according to the invention.
- a brushing can be performed to remove the coating deposited on one face so that only one of the faces of the sheet will ultimately be covered by a coating.
- the coatings are then allowed to cool in a controlled manner so that they solidify.
- the controlled cooling of the coating or of each coating is performed by means of a cooling section or by other appropriate means, and is performed at a rate preferably between 2° C./sec, which corresponds approximately to natural convection, and 35° C./sec between the start of solidification (i.e. when the coating reaches a temperature just below the liquidus temperature) and the end of solidification (i.e. when the coating reaches the solidus temperature). It has been found that cooling rates greater than 35° C./sec do not improve the results any further.
- the cooling is performed at a rate greater than or equal to 15° C./sec, which contributes to refining the microstructure of the metallic coating and also to preventing the formation on the metallic coating of a spangle visible to the naked eye and that remains visible after painting. More preferably, the cooling rate is between 15 and 35° C./sec.
- the strip treated in this manner can then be subjected to a skin-pass step, which work hardens it in order to reduce elasticity, to fix the mechanical characteristics and to give it a roughness appropriate to the stamping operations and the quality of the painted surface that is to be obtained.
- the strip can optionally be coiled before being sent to a pre-painting line.
- This type of preparation comprises at least one step selected among rinsing, degreasing and a conversion treatment.
- the purpose of the rinsing is to eliminate the loose particles of dirt, potential residues of conversion solutions, soaps that may have formed and to achieve a clean and reactive surface.
- the purpose of the degreasing is to clean the surface by removing all traces of organic dirt, metallic particles and dust from the surface.
- This step also makes it possible to alter the aluminum oxide/hydroxide layers and magnesium oxide/hydroxide layers that may be present on the surface of the metallic coating although without otherwise modifying the chemical nature of the surface.
- An alteration of this type makes it possible to improve the quality of the interface between the metallic coating and the paint film, which improves the corrosion resistance and the adherence of the paint film.
- the degreasing is performed in an alkaline environment. More preferably, the pH of the degreasing solution is between 12 and 13.
- the conversion treatment step includes the application to the metallic coating of a conversion solution that reacts chemically with the surface and thereby makes it possible to form conversion layers on the metallic coating. These conversion layers increase the adherence of the paint and the corrosion resistance.
- the conversion treatment is preferably an acid solution that does not contain chromium. More preferably, the conversion treatment is based on hexafluorotitanic or hexafluorozirconic acid.
- the potential degreasing and conversion treatment steps can include other sub-steps of rinsing, drying etc.
- the surface preparation can also include a step altering the magnesium oxide and magnesium hydroxide layers formed on the surface of the metallic coating.
- This alteration can consist among other things of the application of an acid solution before the application of the conversion solution, or the application of an acidified conversion solution with a pH between 1 and 5, or also of the application of mechanical forces to the surface.
- the painting is performed by the deposition of layers of paint, by means of roll coaters, for example.
- Each deposition of a paint layer is generally followed by a curing in a furnace to cross-link the paint and/or to evaporate any solvents and thereby obtain a dry film.
- the sheet thus obtained can be recoiled before being cut, optionally shaped and assembled with other sheets or other elements by the users.
- a plurality of ZnAlMg sheets having variable compositions were obtained by hot-dip galvanizing a metallic substrate of variable thickness in a molten zinc bath containing magnesium and aluminum followed by a cooling, alternatively under natural convection or at a cooling rate of 30° C./sec.
- the ZnAlMg sheets were then pre-painted according to the following protocol:
- 2T and 3T T-bends were also made in bare or pre-painted sheets comprising other types of ZnAlMg coatings.
- Tables 1 and 2 summarize the results obtained respectively on bare ZnAlMg sheets and on pre-painted ZnAlMg sheets.
- the comparison of tables 1 and 2 shows that, very surprisingly, the cracks in the thickness of the ZnAlMg coating according to the invention are significantly less numerous and less wide when the sheet is pre-painted.
- the combination of a ZnAlMg coating according to the invention and a paint film makes it possible to divide the sum of the crack widths of the metallic coating by a factor of 2.5 to 11; only the ZnAlMg coatings according to the invention exhibit this particularity.
- the corrosion resistance of pre-painted sheets is evaluated by natural exposure, in compliance with EN13523-19 and EN13523-21, in a class C5-M site on steel that meets the requirements of ISO 12944-2.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemically Coating (AREA)
- Coating With Molten Metal (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Chemical Treatment Of Metals (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IB2013/002239 WO2015052546A1 (fr) | 2013-10-09 | 2013-10-09 | Tôle à revêtement znaimg à flexibilité améliorée et procédé de réalisation correspondant |
| IBPCT/IB2013/002239 | 2013-10-09 | ||
| PCT/IB2014/002059 WO2015052572A1 (fr) | 2013-10-09 | 2014-10-09 | Tôle à revêtement znaimg à flexibilité améliorée et procédé de réalisation correspondant |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2014/002059 A-371-Of-International WO2015052572A1 (fr) | 2013-10-09 | 2014-10-09 | Tôle à revêtement znaimg à flexibilité améliorée et procédé de réalisation correspondant |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US17/347,868 Continuation US20210310129A1 (en) | 2013-10-09 | 2021-06-15 | ZnAlMg-Coated Metal Sheet with Improved Flexibility and Corresponding Manufacturing Process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20160251761A1 true US20160251761A1 (en) | 2016-09-01 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US15/028,249 Abandoned US20160251761A1 (en) | 2013-10-09 | 2014-10-09 | ZnAlMg-Coated Metal Sheet with Improved Flexibility and Corresponding Manufacturing Process |
| US17/347,868 Pending US20210310129A1 (en) | 2013-10-09 | 2021-06-15 | ZnAlMg-Coated Metal Sheet with Improved Flexibility and Corresponding Manufacturing Process |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US17/347,868 Pending US20210310129A1 (en) | 2013-10-09 | 2021-06-15 | ZnAlMg-Coated Metal Sheet with Improved Flexibility and Corresponding Manufacturing Process |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US20160251761A1 (ja) |
| EP (1) | EP4373989A1 (ja) |
| JP (1) | JP6279723B2 (ja) |
| KR (2) | KR20160067943A (ja) |
| CN (1) | CN105829568B (ja) |
| AU (1) | AU2014333502B2 (ja) |
| BR (1) | BR112016006159B1 (ja) |
| CA (1) | CA2926564C (ja) |
| EA (1) | EA030933B1 (ja) |
| MX (1) | MX2016004415A (ja) |
| UA (1) | UA119543C2 (ja) |
| WO (2) | WO2015052546A1 (ja) |
| ZA (1) | ZA201601734B (ja) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106929708A (zh) * | 2017-04-27 | 2017-07-07 | 甘肃酒钢集团宏兴钢铁股份有限公司 | 一种含Zn‑Al‑Mg‑Si‑Ni‑Ce的热浸镀用高耐蚀锌基铸造合金的制备方法 |
| US20200208273A1 (en) * | 2017-09-18 | 2020-07-02 | Henkel Ag & Co. Kgaa | Two-stage pretreatment of aluminum, in particular aluminum casting alloys, comprising pickle and conversion treatment |
| US11332816B2 (en) | 2017-12-26 | 2022-05-17 | Posco | Zinc alloy plated steel material having excellent surface quality and corrosion resistance |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3635156A1 (en) * | 2017-05-25 | 2020-04-15 | Tata Steel IJmuiden B.V. | Method of manufacturing a continuous hot dip coated steel strip and hot dip coated steel sheet |
| EP3858495A1 (en) * | 2020-02-03 | 2021-08-04 | Public Joint-Stock Company NOVOLIPETSK STEEL | Method for production of corrosion-resistant steel strip |
| RU2727391C1 (ru) * | 2020-02-03 | 2020-07-21 | Публичное Акционерное Общество "Новолипецкий металлургический комбинат" | Способ производства коррозионностойкого окрашенного стального проката с цинк-алюминий-магниевым покрытием |
| WO2023166858A1 (ja) * | 2022-03-04 | 2023-09-07 | Ｊｆｅスチール株式会社 | 溶融Ａｌ－Ｚｎ系めっき鋼板、その製造方法、表面処理鋼板及び塗装鋼板 |
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- 2014-10-09 WO PCT/IB2014/002059 patent/WO2015052572A1/fr active Application Filing
- 2014-10-09 EP EP14795864.9A patent/EP4373989A1/fr active Pending
- 2014-10-09 MX MX2016004415A patent/MX2016004415A/es unknown
- 2014-10-09 BR BR112016006159-4A patent/BR112016006159B1/pt active IP Right Grant
- 2014-10-09 CA CA2926564A patent/CA2926564C/fr active Active
- 2014-10-09 CN CN201480055353.XA patent/CN105829568B/zh active Active
- 2014-10-09 US US15/028,249 patent/US20160251761A1/en not_active Abandoned
- 2014-10-09 JP JP2016521699A patent/JP6279723B2/ja active Active
- 2014-10-09 KR KR1020187003953A patent/KR102089879B1/ko active IP Right Grant
- 2014-10-09 AU AU2014333502A patent/AU2014333502B2/en active Active
- 2014-10-09 EA EA201690733A patent/EA030933B1/ru not_active IP Right Cessation
- 2014-10-09 UA UAA201604963A patent/UA119543C2/uk unknown
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106929708A (zh) * | 2017-04-27 | 2017-07-07 | 甘肃酒钢集团宏兴钢铁股份有限公司 | 一种含Zn‑Al‑Mg‑Si‑Ni‑Ce的热浸镀用高耐蚀锌基铸造合金的制备方法 |
| US20200208273A1 (en) * | 2017-09-18 | 2020-07-02 | Henkel Ag & Co. Kgaa | Two-stage pretreatment of aluminum, in particular aluminum casting alloys, comprising pickle and conversion treatment |
| US11499237B2 (en) * | 2017-09-18 | 2022-11-15 | Henkel Ag & Co. Kgaa | Two-stage pretreatment of aluminum, in particular aluminum casting alloys, comprising pickle and conversion treatment |
| US11332816B2 (en) | 2017-12-26 | 2022-05-17 | Posco | Zinc alloy plated steel material having excellent surface quality and corrosion resistance |
| US11643714B2 (en) | 2017-12-26 | 2023-05-09 | Posco Co., Ltd | Method for manufacturing zinc alloy plated steel material having excellent surface quality and corrosion resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015052546A1 (fr) | 2015-04-16 |
| BR112016006159B1 (pt) | 2021-07-06 |
| JP2016540885A (ja) | 2016-12-28 |
| CA2926564C (fr) | 2018-11-27 |
| KR102089879B1 (ko) | 2020-03-17 |
| EP4373989A1 (fr) | 2024-05-29 |
| BR112016006159A2 (pt) | 2017-08-01 |
| ZA201601734B (en) | 2020-07-29 |
| JP6279723B2 (ja) | 2018-02-14 |
| CN105829568B (zh) | 2018-11-23 |
| EA201690733A1 (ru) | 2016-08-31 |
| AU2014333502B2 (en) | 2018-02-15 |
| KR20160067943A (ko) | 2016-06-14 |
| MX2016004415A (es) | 2016-07-05 |
| CN105829568A (zh) | 2016-08-03 |
| KR20180017240A (ko) | 2018-02-20 |
| WO2015052572A1 (fr) | 2015-04-16 |
| AU2014333502A1 (en) | 2016-04-28 |
| US20210310129A1 (en) | 2021-10-07 |
| UA119543C2 (uk) | 2019-07-10 |
| BR112016006159A8 (pt) | 2020-02-18 |
| WO2015052572A9 (fr) | 2015-08-20 |
| EA030933B1 (ru) | 2018-10-31 |
| CA2926564A1 (fr) | 2015-04-16 |
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