EP4373989A1 - Sheet metal having a znaimg coating and improved flexibility and corresponding production method - Google Patents
Sheet metal having a znaimg coating and improved flexibility and corresponding production methodInfo
- Publication number
- EP4373989A1 EP4373989A1 EP14795864.9A EP14795864A EP4373989A1 EP 4373989 A1 EP4373989 A1 EP 4373989A1 EP 14795864 A EP14795864 A EP 14795864A EP 4373989 A1 EP4373989 A1 EP 4373989A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal coating
- weight
- bath
- magnesium
- aluminum
- 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.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 110
- 239000011248 coating agent Substances 0.000 title claims abstract description 98
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 95
- 239000002184 metal Substances 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 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 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 9
- 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
- 238000010422 painting 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 5
- 238000010791 quenching Methods 0.000 claims abstract description 5
- 230000000171 quenching effect Effects 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229920000728 polyester Polymers 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 11
- 230000008023 solidification Effects 0.000 claims description 11
- 238000005238 degreasing Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 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
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 230000004075 alteration Effects 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
- 238000005246 galvanizing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 230000009471 action Effects 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
- 238000005336 cracking Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005496 eutectics Effects 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
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling 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
- 230000007717 exclusion Effects 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000006872 improvement 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
- 239000002923 metal 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007670 refining Methods 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
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- -1 zinc-aluminum-magnesium Chemical compound 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C2/04—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
- C23C2/26—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
-
- 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
-
- 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
Definitions
- the present invention relates to a sheet comprising a substrate of which at least one face is coated with a metal coating comprising Al and Mg, the remainder of the metal coating being Zn, unavoidable impurities and optionally one or more additional elements. selected from Si, Ti, Ca, Mn, La, Ce and Bi, the weight content of each additional element in the metal coating being less than 0.3%.
- Galvanized metal coatings consisting essentially of zinc and 0.1 to 0.4% by weight of aluminum are traditionally used for their good protection against corrosion.
- Such metal coatings will generally be referred to herein as zinc-aluminum-magnesium or ZnAIMg coatings.
- magnesium significantly increases the corrosion resistance of steels coated with a metal coating, which can reduce the thickness of the metal coating or increase the guarantee of protection against corrosion over time at constant thickness .
- These sheets coated with a ZnAIMg coating are for example intended for the automotive field, household electrical appliance or construction.
- JP2010255084 it is known from JP2010255084 to improve the resistance to cracking by adding from 0.005 to 0.2% by weight of nickel to a metal coating comprising moreover 1 to 10% by weight of aluminum and 0.2 to 1% by weight. magnesium weight.
- the Nickel thus added has the characteristic of being
- Nickel migration at the steel-metal interface is difficult to perform and introduces additional manufacturing constraints.
- the present invention aims to overcome the aforementioned problems by proposing a ZnAIMg sheet whose metal coating crack less on severe folds, while retaining the advantages of ZnAIMg coating in terms of corrosion resistance.
- the invention firstly relates to a method for producing a prepainted sheet comprising at least the steps of:
- a metal coating on at least one face by quenching the substrate in a bath consisting of 4.4% to 5.6% by weight of aluminum and 0.3% to 0.56% by weight of magnesium, the remainder of the bath being exclusively zinc, unavoidable impurities related to the process and optionally one or more additional elements selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, the content by weight of each additional element in the metal coating being less than 0.3%, the presence of nickel being excluded,
- the method according to the invention may also comprise the following optional characteristics, taken alone or in combination:
- the bath comprises from 4.75 to 5.25% by weight of aluminum, the bath comprises from 0.44 to 0.56% by weight of magnesium,
- the bath is at a temperature of between 370 ° C. and 470 ° C.
- the solidification of the metal coating is carried out at a cooling rate of the metal coating between the beginning of the solidification and the end of the solidification greater than or equal to 15 ° C / s,
- the cooling rate is between 15 and 35 ° C / s
- the surface preparation comprises a step chosen from a rinsing, a degreasing and a conversion treatment,
- the degreasing is carried out at a pH of between 12 and 13,
- the conversion treatment is based on hexafluorotitanic acid
- the painting of the metallic coating is carried out by means of a paint comprising at least one polymer chosen from the group consisting of melamine-crosslinked polyesters, isocyanate-crosslinked polyesters, polyurethanes and halogenated derivatives of vinyl polymers, exclusion of cataphoretic paints.
- the solution to the technical problem consists in combining a paint film and a metal coating having a particular composition. Surprisingly, it has been found by the inventors that this combination has an action synergy so that the ZnAIMg coating according to the invention has fewer cracks on the severe folds when it is covered with a film of paint than when he is naked.
- a second subject of the invention consists of a pre-painted sheet comprising a steel substrate of which at least one face is coated with a metal coating consisting of 4.4% to 5.6% by weight of aluminum and 0.3% 0.56% by weight of magnesium, the remainder of the metal coating being exclusively zinc, unavoidable impurities related to the process and optionally one or more additional elements selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, the weight content of each additional element in the metal coating being less than 0.3%, the presence of nickel in the metal coating being excluded, the metal coating being covered with at least one paint film.
- the sheet according to the invention may also comprise the following optional characteristics, taken alone or in combination:
- the metal coating comprises from 4.75 to 5.25% by weight of aluminum
- the metal coating comprises from 0.44 to 0.56% by weight of magnesium
- the metal coating does not include any additional element
- the paint film comprises at least one polymer chosen from the group consisting of melamine-crosslinked polyesters, isocyanate-crosslinked polyesters, polyurethanes and halogenated derivatives of vinyl polymers, with the exception of cataphoretic paints,
- a conversion layer comprising titanium is located at the interface between the metal coating and the paint film.
- the sheet comprises a steel substrate coated on at least one of its faces with a metal coating, itself covered with at least one paint film.
- the metal coating generally has a thickness of less than or equal to 25 ⁇ m and is intended to protect the substrate against corrosion.
- the metal coating consists of aluminum and magnesium, the remainder of the metal coating being exclusively zinc, unavoidable impurities related to the deposition process of the metal coating and optionally one or more additional elements selected from Si, Ti, Ca, Mn, La, Ce and Bi, the weight content of each additional element in the metal coating being less than 0.3%, the presence of nickel being excluded.
- the weight content of aluminum of the metal coating is between 4.4 and 5.6%. This range of aluminum weight content promotes the formation of Zn / Al binary eutectic in the microstructure of the metal coating. This eutectic is particularly ductile and promotes the obtaining of a flexible metal coating.
- the content by weight of aluminum is between 4.75 and
- the content by weight of aluminum is measured without taking into account the aluminum-rich intermetallic located at the interface substrate-metal coating. Such a measurement can for example be carried out by glow discharge spectrometry. A measurement by chemical dissolution would lead to the simultaneous dissolution of the metal coating and intermetallic and give an over-estimated aluminum content by weight of the order of 0.05 to 0.5% depending on the thickness of the metal coating.
- the weight content of magnesium metal coating is between 0.3 and 0.56%. Below 0.3%, the improvement in the resistance to corrosion provided by magnesium is no longer sufficient. Above 0.56%, the synergistic action of the paint film and the metal coating according to the invention is no longer observed.
- the weight content of magnesium is between 0.44 and 0.56%, which constitutes the best compromise in terms of corrosion resistance and flexibility.
- the unavoidable impurities come from the feed ingots of the molten zinc bath or result from the passage of the substrate in the bath.
- the most common unavoidable impurity resulting from the passage of the substrate in the bath is iron which may be present at a content of up to 0.8% by weight of the metal coating, generally less than or equal to 0.4% and generally between 0.1 and 0.4% by weight.
- the unavoidable impurities from the ingots are generally lead (Pb), present at a content of less than 0.01% by weight, Cadmium (Cd), present at a content of less than 0.005% by weight and tin (Sn), present at a content of less than 0.001% by weight. It should be noted here that nickel is not an unavoidable impurity related to the galvanizing process.
- the various additional elements may make it possible, inter alia, to improve the ductility or adhesion of the metal coating to the substrate.
- the metal coating does not include nickel as an additional element, nickel having the drawbacks mentioned above.
- the metal coating does not include any additional elements. This simplifies the management of the galvanizing bath and minimizes the number of phases formed in the metal coating.
- the sheet finally includes a paint film.
- the paint films are generally based on polymers and comprise at least one layer of paint.
- they comprise at least one polymer selected from the group consisting of melamine-crosslinked polyesters, isocyanate-crosslinked polyesters, polyurethanes and halogenated derivatives of vinyl polymers, with the exception of cataphoretic paints.
- These polymers have the characteristic of being particularly flexible, which promotes the synergistic action of the paint film and the metal coating.
- the paint film may be formed for example of two layers of successive paints, namely a primer layer and a topcoat which is generally the case for producing the film applied to the upper face of the sheet, or a layer of single paint, which is generally the case for making the film applied to the lower face of the sheet. Other numbers of layers may be used in certain variants.
- the paint films typically have thicknesses of between 1 and 200 ⁇ m.
- the interface between the metal coating and the paint film includes one or more characteristics to be selected from an alteration of the naturally occurring aluminum oxide / hydroxide layer on the surface metal coating, an alteration of the magnesium oxide / hydroxide layer naturally occurring on the surface of the metal coating and a conversion layer characterized by its chromium layer weight (in case of chromate conversion treatment) or by its weight of titanium layer (in case of conversion treatment without chromium).
- the installation used may comprise a single line or, for example, two different lines for producing respectively the metal coatings and the painting.
- two different lines may be located on the same site or on separate sites. In the remainder of the description, for example, a variant in which two distinct lines are used is considered.
- a steel substrate obtained for example by hot rolling then cold.
- the substrate is in the form of a strip which is passed through a bath to deposit the metal coating by hot quenching.
- the bath is a molten zinc bath containing 4.4 to 5.6% by weight of aluminum and 0.3 to 0.56% by weight of magnesium.
- the bath may also contain unavoidable process-related impurities, such as impurities from the bath feed ingots, and / or one or more additional members selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, the weight content of each additional element in the metal coating being less than 0.3%, the presence of nickel being excluded.
- the most common unavoidable impurity resulting from the passage of the substrate in the bath is iron which may be present at a content of 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 from the ingots are generally lead (Pb), present at a content of less than 0.01% by weight, Cadmium (Cd), present at a content of less than 0.005% by weight and tin (Sn), present at a content of less than 0.001% by weight.
- Pb lead
- Sn tin
- nickel is not an unavoidable impurity related to the galvanizing process.
- the bath has a temperature between 350 ° C and 510 ° C, preferably between 370 ° C and 470 ° C.
- the substrate is for example spun by means of nozzles throwing a gas on either side of the substrate, so as to adjust the thickness of the coatings.
- the wringing gas does not comprise particles or solutions such as, for example, those comprising a magnesium phosphate and / or a magnesium silicate.
- a brushing may be performed to remove the coating deposited on one side so that only one side of the sheet will ultimately be coated.
- the coatings are then allowed to cool in a controlled manner to solidify.
- the controlled cooling of the or each coating is carried out by means of a cooling box or any other suitable means and is provided at a speed preferably between 2 ° C / sec, corresponding approximately to a natural convection, and 35 ° C / sec between the onset of solidification (ie, when the coating reaches a temperature just below that of the liquidus) and the end of solidification (that is, when the coating reaches the temperature solidus). It was found that cooling rates above 35 ° C / sec did not improve the results further.
- the cooling is provided at a speed greater than or equal to 15 ° C / sec which contributes to refining the microstructure of the metal coating and thus to avoid the formation on the metal coating of a visible flowering to the naked eye and which remains apparent after painting. More preferably, the cooling rate is between 15 and 35 ° C / sec.
- the strip thus treated can then be subjected to a so-called skin-pass step which allows it to be hardened so as to erase the level of elasticity, to fix the mechanical characteristics and to give it a roughness adapted to the stamping operations and the quality of the painted surface that one wishes to obtain.
- the band may optionally be wound before being sent to a prelacing line.
- the outer surfaces of the coatings are subjected to a surface preparation step.
- a preparation comprises at least one step chosen from a rinsing, a degreasing and a conversion treatment.
- Rinsing is intended to remove loose dirt, possible residues of conversion solutions, soaps eventually formed and present a clean and reactive surface.
- degreasing is to clean the surface by removing all traces of organic dirt, metal particles and dust from the surface. This step also makes it possible to alter the oxide / aluminum hydroxide and magnesium oxide / hydroxide layers that may be present on the surface of the metal coating, without however unduly modifying the chemical nature of the surface. Such tampering improves the quality of the metal coating / paint film interface which improves the corrosion resistance and adhesion of the paint film.
- the degreasing is carried out in an alkaline medium. More preferably, the pH of the degreasing solution is between 12 and 13.
- the conversion treatment step comprises applying to the metal coating a conversion solution that chemically reacts with the surface and thereby forming conversion layers on the metal coating. These conversion coats increase the adhesion of the paint and the corrosion resistance.
- the conversion treatment is an acid solution not containing chromium. More preferably, the conversion treatment is based on hexafluorotitanic acid or hexafluorozirconic acid.
- the possible stages of degreasing and conversion treatment may include other sub-stages of rinsing, drying ...
- the surface preparation may also include a step of altering the magnesium oxide and magnesium hydroxide layers formed on the surface of the metal coating.
- This alteration can in particular, the application of an acidic solution before application of the conversion solution, or the application of an acidified conversion solution at a pH of between 1 and 5 or else the application of mechanical stresses on the area.
- the painting is carried out by deposition of paint layers by means of, for example, roller coaters.
- Each deposit of a paint layer is generally followed by baking in an oven so as to crosslink the paint and / or evaporate the possible solvents and thus obtain a dry film.
- prepainted sheet The sheet thus obtained, called prepainted sheet, can be rewound before being cut, possibly shaped and assembled with other sheets or other elements by users.
- the propensity to crack of a ZnAIMg sheet, prepainted or not, is evaluated as follows:
- a T-bend fold is made on a specimen of a sheet according to the EN 13523-7 standard of April 2001,
- T-bend 2T and 3T folds were then made on both the bare sheets and those coated and analyzed.
- T-bend 2T and 3T plies were also on bare or coated sheet including other types of ZnAIMg coating.
- Tables 1 and 2 summarize the results obtained, respectively ZnAIMg bare sheets and zinc coated ZnAIMg sheets. The comparison of the 1 and 2 show that, very surprisingly, the cracks in the ZnAIMa coating thickness according to the invention are significantly less numerous.
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Abstract
The invention relates mainly to a method for the production of pre-painted sheet metal, comprising at least the steps of: supplying a steel substrate; depositing a metal coating on at least one face by quenching the substrate in a bath formed by 4.4 to 5.6 wt.-% aluminium and 0.3 to 0.56 wt.-% magnesium, the remainder of the bath being exclusively zinc, inevitable impurities linked to the method and optionally one or more additional elements selected from the group containing Si, Ti, Ca, Mn, La, Ce and Bi, the weight concentration of each additional element in the metal coating being less than 0.3 %, the presence of nickel being excluded; solidifying the metal coating; preparing the surface of the metal coating; and painting the metal coating. The invention also relates to the associated sheet metal.
Description
Tôle à revêtement ZnAIMg à flexibilité améliorée et procédé de réalisation correspondant ZnAIMg coated sheet with improved flexibility and method of making same
La présente invention est relative à une tôle comprenant un substrat dont au moins une face est revêtue par un revêtement métallique comprenant de l'Ai et du Mg, le reste du revêtement métallique étant du Zn, des impuretés inévitables et éventuellement un ou plusieurs éléments additionnels choisis parmi Si, Ti, Ca, Mn, La, Ce et Bi, la teneur en poids de chaque élément additionnel dans le revêtement métallique étant inférieure à 0,3%. The present invention relates to a sheet comprising a substrate of which at least one face is coated with a metal coating comprising Al and Mg, the remainder of the metal coating being Zn, unavoidable impurities and optionally one or more additional elements. selected from Si, Ti, Ca, Mn, La, Ce and Bi, the weight content of each additional element in the metal coating being less than 0.3%.
Les revêtements métalliques galvanisés comprenant essentiellement du zinc et de 0,1 à 0,4% en poids d'aluminium sont traditionnellement utilisés pour leur bonne protection contre la corrosion. Galvanized metal coatings consisting essentially of zinc and 0.1 to 0.4% by weight of aluminum are traditionally used for their good protection against corrosion.
Ces revêtements métalliques sont à présent concurrencés notamment par les revêtements comprenant du zinc et des ajouts de magnésium et d'aluminium, pouvant aller respectivement jusqu'à 10% et jusqu'à 20% en poids. These metal coatings are now in competition with, in particular, coatings comprising zinc and additions of magnesium and aluminum, which may be up to 10% and up to 20% by weight, respectively.
De tels revêtements métalliques seront globalement désignés ici sous le terme de revêtements zinc-aluminium-magnésium ou ZnAIMg. Such metal coatings will generally be referred to herein as zinc-aluminum-magnesium or ZnAIMg coatings.
L'ajout de magnésium augmente nettement la résistance à la corrosion des aciers revêtus d'un revêtement métallique, ce qui peut permettre de réduire l'épaisseur du revêtement métallique ou d'augmenter la garantie de protection contre la corrosion dans le temps à épaisseur constante. The addition of magnesium significantly increases the corrosion resistance of steels coated with a metal coating, which can reduce the thickness of the metal coating or increase the guarantee of protection against corrosion over time at constant thickness .
Ces tôles revêtues d'un revêtement ZnAIMg sont par exemple destinées au domaine de l'automobile, au domaine électroménager ou à la construction. These sheets coated with a ZnAIMg coating are for example intended for the automotive field, household electrical appliance or construction.
Il est connu que l'ajout de Magnésium dans les revêtements métalliques provoque un durcissement du revêtement et que cela conduit à l'apparition de fissures dans l'épaisseur du revêtement lorsque la tôle revêtue est sévèrement pliée. It is known that the addition of magnesium in metal coatings causes a hardening of the coating and that this leads to the appearance of cracks in the thickness of the coating when the coated sheet is severely folded.
Il est connu de JP2010255084 d'améliorer la résistance à la fissuration en ajoutant de 0,005 à 0,2% en poids de Nickel à un revêtement métallique comprenant par ailleurs 1 à 10% en poids d'Aluminium et 0,2 à 1% en poids de Magnésium. Le Nickel ainsi ajouté présente la caractéristique de se situer It is known from JP2010255084 to improve the resistance to cracking by adding from 0.005 to 0.2% by weight of nickel to a metal coating comprising moreover 1 to 10% by weight of aluminum and 0.2 to 1% by weight. magnesium weight. The Nickel thus added has the characteristic of being
CONFIRMATION C0PY
majoritairement à l'interface acier-revêtement métallique, ce qui contribue à inhiber la formation de fissures dans les zones déformées. Cependant l'ajout de Nickel présente plusieurs inconvénients : CONFIRMATION C0PY mainly at the steel-metal interface, which helps to inhibit the formation of cracks in deformed areas. However, adding Nickel has several disadvantages:
la présence de Nickel à la surface du revêtement métallique accélère la corrosion par couplage, the presence of nickel on the surface of the metal coating accelerates coupling corrosion,
L'accroissement du nombre d'éléments dans le bain rend la gestion du bain d'autant plus délicate, The increase in the number of elements in the bath makes the management of the bath all the more delicate,
La migration du Nickel à l'interface acier-revêtement métallique est délicate à réaliser et introduit des contraintes supplémentaires de fabrication. Nickel migration at the steel-metal interface is difficult to perform and introduces additional manufacturing constraints.
La présente invention a pour but de pallier aux problèmes précités en proposant une tôle ZnAIMg dont le revêtement métallique fissure moins sur les plis sévères, tout en conservant les avantages du revêtement ZnAIMg en terme de résistance à la corrosion. The present invention aims to overcome the aforementioned problems by proposing a ZnAIMg sheet whose metal coating crack less on severe folds, while retaining the advantages of ZnAIMg coating in terms of corrosion resistance.
A cet effet, l'invention a pour premier objet un procédé de réalisation d'une tôle prélaquée comprenant au moins les étapes de : For this purpose, the invention firstly relates to a method for producing a prepainted sheet comprising at least the steps of:
- Fourniture d'un substrat en acier, - Supply of a steel substrate,
- Dépôt d'un revêtement métallique sur au moins une face par trempe du substrat dans un bain constitué de 4,4% à 5,6% en poids d'aluminium et 0,3% à 0,56% en poids de magnésium, le reste du bain étant exclusivement du zinc, des impuretés inévitables liées au procédé et éventuellement un ou plusieurs éléments additionnels choisis dans le groupe constitué de Si, Ti, Ca, Mn, La, Ce et Bi, la teneur en poids de chaque élément additionnel dans le revêtement métallique étant inférieure à 0,3%, la présence de nickel étant exclue, Depositing a metal coating on at least one face by quenching the substrate in a bath consisting of 4.4% to 5.6% by weight of aluminum and 0.3% to 0.56% by weight of magnesium, the remainder of the bath being exclusively zinc, unavoidable impurities related to the process and optionally one or more additional elements selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, the content by weight of each additional element in the metal coating being less than 0.3%, the presence of nickel being excluded,
- Solidification du revêtement métallique, - Solidification of the metal coating,
- Préparation de surface du revêtement métallique, - Surface preparation of the metal coating,
- Mise en peinture du revêtement métallique. - Painting the metal coating.
Le procédé selon l'invention peut également comprendre les caractéristiques optionnelles suivantes, prises isolément ou en combinaison : The method according to the invention may also comprise the following optional characteristics, taken alone or in combination:
- le bain comprend de 4,75 à 5,25% en poids d'aluminium,
- le bain comprend de 0,44 à 0,56% en poids de magnésium, the bath comprises from 4.75 to 5.25% by weight of aluminum, the bath comprises from 0.44 to 0.56% by weight of magnesium,
- le bain ne comprend aucun élément additionnel, - the bath does not include any additional element,
- le bain est à une température comprise entre 370°C et 470°C, the bath is at a temperature of between 370 ° C. and 470 ° C.,
- la solidification du revêtement métallique est effectuée à une vitesse de refroidissement du revêtement métallique entre le début de la solidification et la fin de la solidification supérieure ou égale à 15°C/s, the solidification of the metal coating is carried out at a cooling rate of the metal coating between the beginning of the solidification and the end of the solidification greater than or equal to 15 ° C / s,
- la vitesse de refroidissement est comprise entre 15 et 35°C/s, the cooling rate is between 15 and 35 ° C / s,
- la préparation de surface comprend une étape choisie parmi un rinçage, un dégraissage et un traitement de conversion, the surface preparation comprises a step chosen from a rinsing, a degreasing and a conversion treatment,
- le dégraissage est effectué à un pH compris entre 12 et 13, the degreasing is carried out at a pH of between 12 and 13,
- le traitement de conversion est à base d'acide hexafluorotitanique, the conversion treatment is based on hexafluorotitanic acid,
- la mise en peinture du revêtement métallique est réalisée au moyen d'une peinture comprenant au moins un polymère choisi dans le groupe constitué des polyesters à réticulation mélamine, des polyesters à réticulation isocyanate, des polyuréthanes et des dérivés halogénés de polymères vinyliques, à l'exclusion des peintures cataphorétiques. the painting of the metallic coating is carried out by means of a paint comprising at least one polymer chosen from the group consisting of melamine-crosslinked polyesters, isocyanate-crosslinked polyesters, polyurethanes and halogenated derivatives of vinyl polymers, exclusion of cataphoretic paints.
On comprendra donc que la solution au problème technique posé consiste à combiner un film de peinture et un revêtement métallique présentant une composition particulière. De façon surprenante, il a été constaté par les inventeurs que cette combinaison présentait une synergie d'action de sorte que le revêtement ZnAIMg selon l'invention présente moins de fissures sur les plis sévères lorsqu'il est recouvert d'un film de peinture que lorsqu'il est nu. It will therefore be understood that the solution to the technical problem consists in combining a paint film and a metal coating having a particular composition. Surprisingly, it has been found by the inventors that this combination has an action synergy so that the ZnAIMg coating according to the invention has fewer cracks on the severe folds when it is covered with a film of paint than when he is naked.
Un second objet de l'invention est constitué par une tôle prélaquée comprenant un substrat en acier dont au moins une face est revêtue par un revêtement métallique constitué de 4,4% à 5,6% en poids d'aluminium et 0,3% à 0,56% en poids de magnésium, le reste du revêtement métallique étant exclusivement du zinc, des impuretés inévitables liées au procédé et éventuellement un ou plusieurs éléments additionnels choisis dans le groupe constitué de Si, Ti, Ca, Mn, La, Ce et Bi, la teneur en poids de chaque élément additionnel dans le revêtement métallique étant inférieure à 0,3%, la présence de
nickel dans le revêtement métallique étant exclue, le revêtement métallique étant recouvert d'au moins un film de peinture. A second subject of the invention consists of a pre-painted sheet comprising a steel substrate of which at least one face is coated with a metal coating consisting of 4.4% to 5.6% by weight of aluminum and 0.3% 0.56% by weight of magnesium, the remainder of the metal coating being exclusively zinc, unavoidable impurities related to the process and optionally one or more additional elements selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, the weight content of each additional element in the metal coating being less than 0.3%, the presence of nickel in the metal coating being excluded, the metal coating being covered with at least one paint film.
La tôle selon l'invention peut également comprendre les caractéristiques optionnelles suivantes, prises isolément ou en combinaison : The sheet according to the invention may also comprise the following optional characteristics, taken alone or in combination:
- le revêtement métallique comprend de 4,75 à 5,25% en poids d'aluminium, the metal coating comprises from 4.75 to 5.25% by weight of aluminum,
- le revêtement métallique comprend de 0,44 à 0,56% en poids de magnésium, the metal coating comprises from 0.44 to 0.56% by weight of magnesium,
- le revêtement métallique ne comprend aucun élément additionnel, - the metal coating does not include any additional element,
- le film de peinture comprend au moins un polymère choisi dans le groupe constitué des polyesters à réticulation mélamine, des polyesters à réticulation isocyanate, des polyuréthanes et des dérivés halogénés de polymères vinyliques, à l'exclusion des peintures cataphorétiques,the paint film comprises at least one polymer chosen from the group consisting of melamine-crosslinked polyesters, isocyanate-crosslinked polyesters, polyurethanes and halogenated derivatives of vinyl polymers, with the exception of cataphoretic paints,
- une couche de conversion comprenant du Titane est située à l'interface entre le revêtement métallique et le film de peinture. - A conversion layer comprising titanium is located at the interface between the metal coating and the paint film.
D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description qui va suivre. Other characteristics and advantages of the invention will appear on reading the description which follows.
L'invention sera mieux comprise à la lecture de la description qui suit, donnée à titre explicatif mais non limitatif. The invention will be better understood on reading the description which follows, given for explanatory but not limiting.
La tôle comprend un substrat en acier recouvert sur au moins une de ses faces d'un revêtement métallique, lui-même recouvert d'au moins un film de peinture. The sheet comprises a steel substrate coated on at least one of its faces with a metal coating, itself covered with at least one paint film.
Le revêtement métallique a généralement une épaisseur inférieure ou égale à 25 pm et vise à protéger le substrat contre la corrosion. The metal coating generally has a thickness of less than or equal to 25 μm and is intended to protect the substrate against corrosion.
Le revêtement métallique est constitué d'aluminium et de magnésium, le reste du revêtement métallique étant exclusivement du zinc, des impuretés inévitables liées au procédé de dépôt du revêtement métallique et éventuellement un ou plusieurs éléments additionnels choisis parmi Si, Ti, Ca, Mn, La, Ce et Bi, la teneur en poids de chaque élément additionnel dans le revêtement métallique étant inférieure à 0,3%, la présence de nickel étant exclue.
La teneur en poids d'aluminium du revêtement métallique est comprise entre 4,4 et 5,6%. Cette gamme de teneur en poids d'aluminium favorise la formation d'eutectique binaire Zn/AI dans la microstructure du revêtement métallique. Cet eutectique est particulièrement ductile et favorise l'obtention d'un revêtement métallique flexible. The metal coating consists of aluminum and magnesium, the remainder of the metal coating being exclusively zinc, unavoidable impurities related to the deposition process of the metal coating and optionally one or more additional elements selected from Si, Ti, Ca, Mn, La, Ce and Bi, the weight content of each additional element in the metal coating being less than 0.3%, the presence of nickel being excluded. The weight content of aluminum of the metal coating is between 4.4 and 5.6%. This range of aluminum weight content promotes the formation of Zn / Al binary eutectic in the microstructure of the metal coating. This eutectic is particularly ductile and promotes the obtaining of a flexible metal coating.
De préférence, la teneur en poids d'aluminium est comprise entre 4,75 et Preferably, the content by weight of aluminum is between 4.75 and
5,25%. 5.25%.
On notera ici que la teneur en poids d'aluminium est mesurée sans prendre en compte l'intermétallique riche en Aluminium situé à l'interface substrat- revêtement métallique. Une telle mesure peut par exemple être réalisée par spectrométrie à décharge luminescente. Une mesure par dissolution chimique conduirait quant à elle à la dissolution simultanée du revêtement métallique et de l'intermétallique et donnerait une teneur en poids d'aluminium sur-estimée de l'ordre de 0,05 à 0,5% en fonction de l'épaisseur du revêtement métallique. It should be noted here that the content by weight of aluminum is measured without taking into account the aluminum-rich intermetallic located at the interface substrate-metal coating. Such a measurement can for example be carried out by glow discharge spectrometry. A measurement by chemical dissolution would lead to the simultaneous dissolution of the metal coating and intermetallic and give an over-estimated aluminum content by weight of the order of 0.05 to 0.5% depending on the thickness of the metal coating.
La teneur en poids de magnésium du revêtement métallique est comprise entre 0,3 et 0,56%. En dessous de 0,3%, l'amélioration de la résistance à la corrosion apportée par le magnésium n'est plus suffisante. Au-dessus de 0,56%, la synergie d'action du film de peinture et du revêtement métallique selon l'invention n'est plus observée. The weight content of magnesium metal coating is between 0.3 and 0.56%. Below 0.3%, the improvement in the resistance to corrosion provided by magnesium is no longer sufficient. Above 0.56%, the synergistic action of the paint film and the metal coating according to the invention is no longer observed.
De préférence, la teneur en poids de magnésium est comprise entre 0,44 et 0,56%, ce qui constitue le meilleur compromis en termes de résistance à la corrosion et de flexibilité. Preferably, the weight content of magnesium is between 0.44 and 0.56%, which constitutes the best compromise in terms of corrosion resistance and flexibility.
Les impuretés inévitables proviennent des lingots d'alimentation du bain de zinc fondu ou résultent du passage du substrat dans le bain. L'impureté inévitable la plus courante et résultant du passage du substrat dans le bain est le fer qui peut être présent à une teneur allant jusqu'à 0,8% en poids du revêtement métallique, généralement inférieure ou égale à 0,4% et généralement comprise entre 0,1 et 0,4% en poids. Les impuretés inévitables provenant des lingots d'alimentation sont généralement le plomb (Pb), présent à une teneur inférieure à 0,01 % en poids, le Cadmium (Cd), présent à une teneur inférieure à 0,005% en poids et l'étain (Sn),
présent à une teneur inférieure à 0,001% en poids. Il est à noter ici que le nickel n'est pas une impureté inévitable liée au procédé de galvanisation. The unavoidable impurities come from the feed ingots of the molten zinc bath or result from the passage of the substrate in the bath. The most common unavoidable impurity resulting from the passage of the substrate in the bath is iron which may be present at a content of up to 0.8% by weight of the metal coating, generally less than or equal to 0.4% and generally between 0.1 and 0.4% by weight. The unavoidable impurities from the ingots are generally lead (Pb), present at a content of less than 0.01% by weight, Cadmium (Cd), present at a content of less than 0.005% by weight and tin (Sn), present at a content of less than 0.001% by weight. It should be noted here that nickel is not an unavoidable impurity related to the galvanizing process.
Les différents éléments additionnels peuvent permettre, entre autres, d'améliorer la ductilité ou l'adhésion du revêtement métallique sur le substrat. L'homme du métier qui connaît leurs effets sur les caractéristiques des revêtements métalliques saura les employer en fonction du but complémentaire recherché. Dans le cadre de l'invention, le revêtement métallique ne comprend pas de nickel en tant qu'élément additionnel, le nickel présentant les inconvénients cités précédemment. De préférence, le revêtement métallique ne comprend aucun élément additionnel. Ceci permet de simplifier la gestion du bain de galvanisation et de minimiser le nombre de phases formées dans le revêtement métallique. The various additional elements may make it possible, inter alia, to improve the ductility or adhesion of the metal coating to the substrate. Those skilled in the art who know their effects on the characteristics of metal coatings will be able to use them according to the complementary aim sought. In the context of the invention, the metal coating does not include nickel as an additional element, nickel having the drawbacks mentioned above. Preferably, the metal coating does not include any additional elements. This simplifies the management of the galvanizing bath and minimizes the number of phases formed in the metal coating.
La tôle comprend enfin un film de peinture. The sheet finally includes a paint film.
Les films de peinture sont généralement à base de polymères et comprennent au moins une couche de peinture. De préférence, ils comprennent au moins un polymère choisi dans le groupe constitué des polyesters à réticulation mélamine, des polyesters à réticulation isocyanate, des polyuréthanes et des dérivés halogénés de polymères vinyliques, à l'exclusion des peintures cataphorétiques. Ces polymères présentent la caractéristique d'être particulièrement flexibles, ce qui favorise la synergie d'action du film de peinture et du revêtement métallique. The paint films are generally based on polymers and comprise at least one layer of paint. Preferably, they comprise at least one polymer selected from the group consisting of melamine-crosslinked polyesters, isocyanate-crosslinked polyesters, polyurethanes and halogenated derivatives of vinyl polymers, with the exception of cataphoretic paints. These polymers have the characteristic of being particularly flexible, which promotes the synergistic action of the paint film and the metal coating.
Le film de peinture peut être formé par exemple de deux couches de peintures successives, à savoir une couche de primaire et une couche de finition ce qui est généralement le cas pour réaliser le film appliqué en face supérieure de la tôle, ou d'une couche de peinture unique, ce qui est généralement le cas pour réaliser le film appliqué en face inférieure de la tôle, D'autres nombres de couches peuvent être utilisés dans certaines variantes. The paint film may be formed for example of two layers of successive paints, namely a primer layer and a topcoat which is generally the case for producing the film applied to the upper face of the sheet, or a layer of single paint, which is generally the case for making the film applied to the lower face of the sheet. Other numbers of layers may be used in certain variants.
Les films de peinture ont typiquement des épaisseurs comprises entre 1 et 200 pm. The paint films typically have thicknesses of between 1 and 200 μm.
Optionnellement, l'interface entre le revêtement métallique et le film de peinture comprend une ou plusieurs caractéristiques à choisir parmi une altération de la couche d'oxyde/hydroxyde d'aluminium présente naturellement à la surface
du revêtement métallique, une altération de la couche d'oxyde/hydroxyde de magnésium présente naturellement à la surface du revêtement métallique et une couche de conversion caractérisée par son poids de couche en chrome (en cas de traitement de conversion chromaté) ou par son poids de couche en titane (en cas de traitement de conversion sans chrome). Optionally, the interface between the metal coating and the paint film includes one or more characteristics to be selected from an alteration of the naturally occurring aluminum oxide / hydroxide layer on the surface metal coating, an alteration of the magnesium oxide / hydroxide layer naturally occurring on the surface of the metal coating and a conversion layer characterized by its chromium layer weight (in case of chromate conversion treatment) or by its weight of titanium layer (in case of conversion treatment without chromium).
Pour réaliser la tôle selon l'invention, on peut par exemple procéder comme suit. To achieve the sheet according to the invention, one can for example proceed as follows.
L'installation utilisée peut comprendre une seule et même ligne ou par exemple deux lignes différentes pour réaliser respectivement les revêtements métalliques et la mise en peinture. Dans le cas où deux lignes différentes sont utilisées, elles peuvent être situées sur le même site ou sur des sites distincts. Dans la suite de la description, on considéra à titre d'exemple une variante où deux lignes distinctes sont utilisées. The installation used may comprise a single line or, for example, two different lines for producing respectively the metal coatings and the painting. In the case where two different lines are used, they may be located on the same site or on separate sites. In the remainder of the description, for example, a variant in which two distinct lines are used is considered.
Dans une première ligne de réalisation des revêtements métalliques, on utilise un substrat en acier obtenu par exemple par laminage à chaud puis à froid. Le substrat est sous forme d'une bande que l'on fait défiler dans un bain pour déposer le revêtement métallique par trempe à chaud. In a first embodiment of metal coatings, use is made of a steel substrate obtained for example by hot rolling then cold. The substrate is in the form of a strip which is passed through a bath to deposit the metal coating by hot quenching.
Le bain est un bain de zinc fondu contenant de 4,4 à 5,6% en poids d'aluminium et de 0,3 à 0,56% en poids de magnésium. Le bain peut également contenir des impuretés inévitables liées au procédé, telles que des impuretés provenant des lingots d'alimentation du bain, et/ou un ou plusieurs éléments additionnels choisis dans le groupe constitué de Si, Ti, Ca, Mn, La, Ce et Bi, la teneur en poids de chaque élément additionnel dans le revêtement métallique étant inférieure à 0,3%, la présence de nickel étant exclue. The bath is a molten zinc bath containing 4.4 to 5.6% by weight of aluminum and 0.3 to 0.56% by weight of magnesium. The bath may also contain unavoidable process-related impurities, such as impurities from the bath feed ingots, and / or one or more additional members selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, the weight content of each additional element in the metal coating being less than 0.3%, the presence of nickel being excluded.
L'impureté inévitable la plus courante et résultant du passage du substrat dans le bain est le fer qui peut être présent à une teneur allant jusqu'à 0,8% en poids, généralement inférieure ou égale à 0,4% et généralement comprise entre 0,1 et 0,4% en poids. Les impuretés inévitables provenant des lingots d'alimentation sont généralement le plomb (Pb), présent à une teneur inférieure à 0,01% en poids, le Cadmium (Cd), présent à une teneur inférieure à 0,005% en poids et l'étain (Sn), présent à une teneur inférieure à 0,001 % en poids. Il est à
noter ici que le nickel n'est pas une impureté inévitable liée au procédé de galvanisation. The most common unavoidable impurity resulting from the passage of the substrate in the bath is iron which may be present at a content of 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 from the ingots are generally lead (Pb), present at a content of less than 0.01% by weight, Cadmium (Cd), present at a content of less than 0.005% by weight and tin (Sn), present at a content of less than 0.001% by weight. He is at note here that nickel is not an unavoidable impurity related to the galvanizing process.
Le bain a une température comprise entre 350°C et 510°C, de préférence entre 370°C et 470°C. The bath has a temperature between 350 ° C and 510 ° C, preferably between 370 ° C and 470 ° C.
Après dépôt du revêtement métallique, le substrat est par exemple essoré au moyen de buses projetant un gaz de part et d'autre du substrat, de sorte à ajuster l'épaisseur des revêtements. De préférence, le gaz d'essorage ne comprend ni particules, ni solutions telles que, par exemple, celles comprenant un phosphate de magnésium et/ou un silicate de magnésium. Ces ajouts au gaz d'essorage modifient la solidification du revêtement métallique et donc sa microstructure, ce qui contribuerait à dégrader le bon comportement en flexibilité de la tôle prélaquée selon l'invention. En variante, un brossage peut être effectué pour enlever le revêtement déposé sur une face de sorte qu'une seule des faces de la tôle sera en définitive revêtue par un revêtement. After deposition of the metal coating, the substrate is for example spun by means of nozzles throwing a gas on either side of the substrate, so as to adjust the thickness of the coatings. Preferably, the wringing gas does not comprise particles or solutions such as, for example, those comprising a magnesium phosphate and / or a magnesium silicate. These additions to the spin gas modify the solidification of the metal coating and therefore its microstructure, which would contribute to degrade the good flexibility behavior of the prelacked sheet according to the invention. Alternatively, a brushing may be performed to remove the coating deposited on one side so that only one side of the sheet will ultimately be coated.
On laisse ensuite refroidir les revêtements de façon contrôlée pour qu'ils se solidifient. Le refroidissement contrôlé du ou de chaque revêtement est réalisé au moyen d'un caisson de refroidissement ou de tout autre moyen adapté et est assuré à une vitesse de préférence comprise entre 2°C/sec, correspondant approximativement à une convection naturelle, et 35°C/sec entre le début de la solidification (c'est-à-dire lorsque le revêtement atteint une température juste inférieure à celle du liquidus) et la fin de la solidification (c'est-à-dire lorsque le revêtement atteint la température du solidus). Il a été constaté que des vitesses de refroidissement supérieures à 35°C/sec ne permettaient pas d'améliorer davantage les résultats. The coatings are then allowed to cool in a controlled manner to solidify. The controlled cooling of the or each coating is carried out by means of a cooling box or any other suitable means and is provided at a speed preferably between 2 ° C / sec, corresponding approximately to a natural convection, and 35 ° C / sec between the onset of solidification (ie, when the coating reaches a temperature just below that of the liquidus) and the end of solidification (that is, when the coating reaches the temperature solidus). It was found that cooling rates above 35 ° C / sec did not improve the results further.
De préférence, le refroidissement est assuré à une vitesse supérieure ou égale à 15°C/sec ce qui contribue à affiner la microstructure du revêtement métallique et à ainsi éviter la formation sur le revêtement métallique d'un fleurage visible à l' il nu et qui reste apparent après mise en peinture. De façon plus préférentielle, la vitesse de refroidissement est comprise entre 15 et 35°C/sec. Preferably, the cooling is provided at a speed greater than or equal to 15 ° C / sec which contributes to refining the microstructure of the metal coating and thus to avoid the formation on the metal coating of a visible flowering to the naked eye and which remains apparent after painting. More preferably, the cooling rate is between 15 and 35 ° C / sec.
La bande ainsi traitée peut ensuite être soumise à une étape dite de skin- pass qui permet de l'écrouir de sorte à effacer le palier d'élasticité, à fixer les
caractéristiques mécaniques et à lui conférer une rugosité adaptée aux opérations d'emboutissage et à la qualité de surface peinte que l'on souhaite obtenir. The strip thus treated can then be subjected to a so-called skin-pass step which allows it to be hardened so as to erase the level of elasticity, to fix the mechanical characteristics and to give it a roughness adapted to the stamping operations and the quality of the painted surface that one wishes to obtain.
La bande peut éventuellement être bobinée avant d'être envoyée vers une ligne de prélaquage. The band may optionally be wound before being sent to a prelacing line.
Les surfaces extérieures des revêtements y sont soumises à une étape de préparation de surface. Une telle préparation comprend au moins une étape choisie parmi un rinçage, un dégraissage et un traitement de conversion. The outer surfaces of the coatings are subjected to a surface preparation step. Such a preparation comprises at least one step chosen from a rinsing, a degreasing and a conversion treatment.
Le rinçage a pour but d'éliminer les salissures décollées, les éventuels résidus de solutions de conversion, les savons éventuellement formés et de présenter une surface propre et réactive. Rinsing is intended to remove loose dirt, possible residues of conversion solutions, soaps eventually formed and present a clean and reactive surface.
Le dégraissage a pour but de nettoyer la surface en enlevant toute trace de salissure organique, de particules métalliques et de poussière de la surface. Cette étape permet également d'altérer les couches d'oxyde/hydroxyde d'aluminium et d'oxyde/hydroxyde de Magnésium éventuellement présentes à la surface du revêtement métallique, sans toutefois modifier outre mesure la nature chimique de la surface. Une telle altération permet d'améliorer la qualité de l'interface revêtement métallique/film de peinture ce qui améliore la résistance à la corrosion et l'adhérence du film de peinture. De préférence, le dégraissage est réalisé en milieu alcalin. Plus préférentiellement, le pH de la solution de dégraissage est compris entre 12 et 13. The purpose of degreasing is to clean the surface by removing all traces of organic dirt, metal particles and dust from the surface. This step also makes it possible to alter the oxide / aluminum hydroxide and magnesium oxide / hydroxide layers that may be present on the surface of the metal coating, without however unduly modifying the chemical nature of the surface. Such tampering improves the quality of the metal coating / paint film interface which improves the corrosion resistance and adhesion of the paint film. Preferably, the degreasing is carried out in an alkaline medium. More preferably, the pH of the degreasing solution is between 12 and 13.
L'étape de traitement de conversion comprend l'application sur le revêtement métallique d'une solution de conversion qui réagit chimiquement avec la surface et permet ainsi de former sur le revêtement métallique des couches de conversion. Ces couches de conversion augmentent l'adhérence de la peinture et la résistance à la corrosion. De préférence, le traitement de conversion est une solution acide ne contenant pas de chrome. Plus préférentiellement, le traitement de conversion est à base d'acide hexafluorotitanique ou hexafluorozirconique. The conversion treatment step comprises applying to the metal coating a conversion solution that chemically reacts with the surface and thereby forming conversion layers on the metal coating. These conversion coats increase the adhesion of the paint and the corrosion resistance. Preferably, the conversion treatment is an acid solution not containing chromium. More preferably, the conversion treatment is based on hexafluorotitanic acid or hexafluorozirconic acid.
Les éventuelles étapes de dégraissage et de traitement de conversion peuvent comprendre d'autres sous-étapes de rinçage, de séchage.... The possible stages of degreasing and conversion treatment may include other sub-stages of rinsing, drying ....
Optionnellement, la préparation de surface peut également comprendre une étape d'altération des couches d'oxyde de magnésium et d'hydroxyde de magnésium formées à la surface du revêtement métallique. Cette altération peut
notamment consister en l'application d'une solution acide avant application de la solution de conversion, ou en l'application d'une solution de conversion acidifiée à pH compris entre 1 et 5 ou encore en l'application d'efforts mécaniques sur la surface. Optionally, the surface preparation may also include a step of altering the magnesium oxide and magnesium hydroxide layers formed on the surface of the metal coating. This alteration can in particular, the application of an acidic solution before application of the conversion solution, or the application of an acidified conversion solution at a pH of between 1 and 5 or else the application of mechanical stresses on the area.
La mise en peinture est réalisée par dépôt de couches de peinture au moyen, par exemple, de vernisseuses à rouleaux. The painting is carried out by deposition of paint layers by means of, for example, roller coaters.
Chaque dépôt d'une couche de peinture est généralement suivi d'une cuisson dans un four de sorte à réticuler la peinture et/ou évaporer les éventuels solvants et ainsi obtenir un film sec. Each deposit of a paint layer is generally followed by baking in an oven so as to crosslink the paint and / or evaporate the possible solvents and thus obtain a dry film.
La tôle ainsi obtenue, dite tôle prélaquée, peut à nouveau être bobinée avant d'être découpée, éventuellement mise en forme et assemblée avec d'autres tôles ou d'autres éléments par des utilisateurs. The sheet thus obtained, called prepainted sheet, can be rewound before being cut, possibly shaped and assembled with other sheets or other elements by users.
Afin d'illustrer l'invention, des essais ont été réalisés et vont être décrits à titre d'exemples non limitatifs. In order to illustrate the invention, tests have been carried out and will be described by way of non-limiting examples.
Synergie d'action du revêtement métallique ZnAIMq selon l'invention et du film de peinture - Diminution de la fissuration Synergy of action of ZnAIMq metal coating according to the invention and of the paint film - Decrease of cracking
La propension à fissurer d'une tôle ZnAIMg, prélaquée ou non, est évaluée de la façon suivante : The propensity to crack of a ZnAIMg sheet, prepainted or not, is evaluated as follows:
- un pli T-bend est réalisé sur une éprouvette d'une tôle conformément à la norme EN 13523-7 d'Avril 2001 , a T-bend fold is made on a specimen of a sheet according to the EN 13523-7 standard of April 2001,
- on réalise dans l'épaisseur du pli une coupe transversale à l'axe de pliage, in the thickness of the fold, a cross section is made at the bending axis,
- la section du pli est observée au microscope optique à fort grossissement et on note : the section of the fold is observed under a high magnification optical microscope and we note:
o le nombre de fissures atteignant l'acier sur l'ensemble de la section du pli, o the number of cracks reaching the steel over the entire crease section,
o la largeur moyenne de ces fissures (en μιη) o the average width of these cracks (in μιη)
o la somme des largeurs de ces fissures (en pm) o the sum of the widths of these cracks (in pm)
Le cas échéant, on distingue les fissures dans l'épaisseur du revêtement métallique ZnAIMg et les fissures dans l'épaisseur du film de peinture.
Plusieurs tôles ZnAIMg présentant des compositions variables obtenues par trempe d'un substrat métallique d'épaisseur variable dans de zinc fondu contenant du magnésium et de l'aluminium si refroidissement alternativement sous convection naturelle ou à une vi refroidissement de 30°C/sec. Les tôles ZnAIMg ont ensuite été prélaqué le protocole suivant : Where appropriate, there are cracks in the thickness of the ZnAIMg metal coating and cracks in the thickness of the paint film. Several ZnAIMg sheets having variable compositions obtained by quenching a metal substrate of variable thickness in molten zinc containing magnesium and aluminum if cooling alternately under natural convection or at a cooling of 30 ° C / sec. The ZnAIMg sheets were then prepainted with the following protocol:
- dégraissage alcalin, - alkaline degreasing,
- application du traitement de conversion Granodine® 1455 de IJ Henkel®, - application of Granodine® 1455 conversion treatment from IJ Henkel®,
- application d'une couche de primaire de type polyester/n contenant des pigments anti-corrosion d'épaisseur nominale ί film sec), - application of a primer layer of polyester / n type containing anti-corrosion pigments of nominal thickness ί dry film),
- application d'une couche de finition de type polyester/n d'épaisseur nominale 20pm (sur film sec). - Application of a polyester / n type topcoat with a nominal thickness of 20 μm (on dry film).
Des plis T-bend 2T et 3T ont ensuite été réalisés tant sur les tôles nues que sur celles prélaquées puis analysés. T-bend 2T and 3T folds were then made on both the bare sheets and those coated and analyzed.
A titre de comparaison, des plis T-bend 2T et 3T ont également été sur des tôles nues ou prélaquées comprenant d'autres types de revé ZnAIMg. For comparison, T-bend 2T and 3T plies were also on bare or coated sheet including other types of ZnAIMg coating.
Les tableaux 1 et 2 résument les résultats obtenus, respectiver tôles ZnAIMg nues et sur tôles ZnAIMg prélaquées. La comparaison des 1 et 2 montrent que, de façon très étonnante, les fissures dans l'épaii revêtement ZnAIMa selon l'invention sont sianificativement moins nombr
Tables 1 and 2 summarize the results obtained, respectively ZnAIMg bare sheets and zinc coated ZnAIMg sheets. The comparison of the 1 and 2 show that, very surprisingly, the cracks in the ZnAIMa coating thickness according to the invention are significantly less numerous.
Les résultats après un an d'exposition naturelle, repris au tableau 3, montrent que les tôles ZnAIMg prélaquées selon l'invention conservent les avantages du revêtement ZnAIMg en terme de résistance à la corrosion. The results after one year of natural exposure, shown in Table 3, show that the ZnAIMg sheets coated according to the invention retain the advantages of the ZnAIMg coating in terms of corrosion resistance.
E = exemple selon l'invention ; CE = contre-exemple
E = example according to the invention; CE = counterexample
E = exemple selon l'invention ; CE = contre-exemple
E = example according to the invention; CE = counterexample
% en % en Epaisseur % in% in Thickness
Délamination sur Delamination on
Essai poids poids revêtement Test weight weight coating
tranche (mm) Al Mg (μηη/face) slice (mm) Al Mg (μηη / face)
E1 5,0 0,5 10 0,9 E1 5.0 0.5 10 0.9
CE3 1,0 1,00 16 1,1 CE3 1.0 1.00 16 1.1
CE4 1,6 1,60 11 1 CE4 1.6 1.60 11 1
CE6 3,7 3,0 10 1 CE6 3.7 3.0 10 1
Tableau 3 Table 3
E = exemple selon l'invention ; CE = contre-exemple
E = example according to the invention; CE = counterexample
Claims
REVENDICATIONS
1) Procédé de réalisation d'une tôle prélaquée comprenant au moins les étapes de : 1) Process for producing a prelacquered sheet comprising at least the steps of:
- Fourniture d'un substrat en acier, - Supply of a steel substrate,
- Dépôt d'un revêtement métallique sur au moins une face par trempe du substrat dans un bain constitué de 4,4% à 5,6% en poids d'aluminium et 0,3% à 0,56% en poids de magnésium, le reste du bain étant exclusivement du zinc, des impuretés inévitables liées au procédé et éventuellement un ou plusieurs éléments additionnels choisis dans le groupe constitué de Si, Ti, Ca, Mn, La, Ce et Bi, la teneur en poids de chaque élément additionnel dans le revêtement métallique étant inférieure à 0,3%, la présence de nickel étant exclue, Depositing a metal coating on at least one face by quenching the substrate in a bath consisting of 4.4% to 5.6% by weight of aluminum and 0.3% to 0.56% by weight of magnesium, the remainder of the bath being exclusively zinc, unavoidable impurities related to the process and optionally one or more additional elements selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, the content by weight of each additional element in the metal coating being less than 0.3%, the presence of nickel being excluded,
- Solidification du revêtement métallique, - Solidification of the metal coating,
- Préparation de surface du revêtement métallique, - Surface preparation of the metal coating,
- Mise en peinture du revêtement métallique. - Painting the metal coating.
2) Procédé de réalisation selon la revendication 2 pour lequel le bain comprend de 4,75 à 5,25% en poids d'aluminium. 2) The method of embodiment of claim 2 wherein the bath comprises from 4.75 to 5.25% by weight of aluminum.
3) Procédé de réalisation selon l'une quelconque des revendications précédentes pour lequel le bain comprend de 0,44 à 0,56% en poids de magnésium. 3) Process according to any one of the preceding claims wherein the bath comprises 0.44 to 0.56% by weight of magnesium.
4) Procédé de réalisation selon l'une quelconque des revendications précédentes pour lequel le bain ne comprend aucun élément additionnel. 4) A method of realization according to any one of the preceding claims for which the bath comprises no additional element.
5) Procédé de réalisation selon l'une quelconque des revendications précédentes pour lequel le bain est à une température comprise entre 370°C et 470°C.
6) Procédé de réalisation selon l'une quelconque des revendications précédentes pour lequel la solidification du revêtement métallique est effectuée à une vitesse de refroidissement du revêtement métallique entre le début de la solidification et la fin de la solidification supérieure ou égale à 15eC/s. 5) Process according to any one of the preceding claims wherein the bath is at a temperature between 370 ° C and 470 ° C. 6) A production method according to any one of the preceding claims wherein the solidification of the metal coating is performed at a cooling rate of the metal coating between the onset of solidification and the end of the solidification greater than or equal to 15 e / s.
7) Procédé de réalisation selon la revendication 6 pour lequel la vitesse de refroidissement est comprise entre 15 et 35°C/s. 7) The method of embodiment of claim 6 wherein the cooling rate is between 15 and 35 ° C / s.
8) Procédé de réalisation selon l'une quelconque des revendications précédentes pour lequel la préparation de surface comprend une étape choisie parmi un rinçage, un dégraissage et un traitement de conversion. 8) A method of manufacture according to any one of the preceding claims wherein the surface preparation comprises a step selected from a rinse, a degreasing and a conversion treatment.
9) Procédé de réalisation selon la revendication 8 pour lequel le dégraissage est effectué à un pH compris entre 12 et 13. 9) The method of embodiment of claim 8 wherein the degreasing is carried out at a pH between 12 and 13.
10) Procédé de réalisation selon la revendication 8 pour lequel le traitement de conversion est à base d'acide hexafluorotitanique. 10) A production method according to claim 8 wherein the conversion treatment is based on hexafluorotitanic acid.
11 ) Procédé de réalisation selon l'une quelconque des revendications précédentes pour lequel la mise en peinture du revêtement métallique est réalisée au moyen d'une peinture comprenant au moins un polymère choisi dans le groupe constitué des polyesters à réticulation mélamine, des polyesters à réticulation isocyanate, des polyuréthanes et des dérivés halogénés de polymères vinyliques, à l'exclusion des peintures cataphorétiques. 11) A production method according to any one of the preceding claims wherein the painting of the metal coating is performed by means of a paint comprising at least one polymer selected from the group consisting of melamine-crosslinked polyesters, crosslinked polyesters isocyanate, polyurethanes and halogenated derivatives of vinyl polymers, excluding cataphoretic paints.
12) Tôle prélaquée comprenant un substrat en acier dont au moins une face est revêtue par un revêtement métallique constitué de 4,4% à 5,6% en poids d'aluminium et 0,3% à 0,56% en poids de magnésium, le reste du revêtement métallique étant exclusivement du zinc, des impuretés inévitables liées au procédé et éventuellement un ou plusieurs éléments additionnels choisis dans le groupe constitué de Si, Ti, Ca, Mn, La, Ce et
Bi, la teneur en poids de chaque élément additionnel dans le revêtement métallique étant inférieure à 0,3%, la présence de nickel dans le revêtement métallique étant exclue, le revêtement métallique étant recouvert d'au moins un film de peinture. 12) Coated sheet comprising a steel substrate of which at least one side is coated with a metal coating consisting of 4.4% to 5.6% by weight of aluminum and 0.3% to 0.56% by weight of magnesium the remainder of the metal coating being exclusively zinc, unavoidable impurities related to the process and optionally one or more additional elements selected from the group consisting of Si, Ti, Ca, Mn, La, Ce and Bi, the weight content of each additional element in the metal coating being less than 0.3%, the presence of nickel in the metal coating being excluded, the metal coating being covered with at least one paint film.
13) Tôle selon la revendication 12 pour laquelle le revêtement métallique comprend de 4,75 à 5,25% en poids d'aluminium. 13) Sheet according to claim 12 wherein the metal coating comprises from 4.75 to 5.25% by weight of aluminum.
14) Tôle selon les revendications 12 ou 13 pour laquelle le revêtement métallique comprend de 0,44 à 0,56% en poids de magnésium. 14) Sheet according to claims 12 or 13 wherein the metal coating comprises 0.44 to 0.56% by weight of magnesium.
15) Tôle selon l'une quelconque des revendications 12 à 14 pour laquelle le revêtement métallique ne comprend aucun élément additionnel. 15) Sheet according to any one of claims 12 to 14 wherein the metal coating comprises no additional element.
16) Tôle selon l'une quelconque des revendications 12 à 15 pour laquelle le film de peinture comprend au moins un polymère choisi dans le groupe constitué des polyesters à réticulation mélamine, des polyesters à réticulation isocyanate, des polyuréthanes et des dérivés halogénés de polymères vinyliques, à l'exclusion des peintures cataphorétiques. 16) A sheet according to any one of claims 12 to 15 wherein the paint film comprises at least one polymer selected from the group consisting of melamine-crosslinked polyesters, isocyanate-crosslinked polyesters, polyurethanes and halogenated derivatives of vinyl polymers , excluding cataphoretic paints.
17) Tôle selon l'une quelconque des revendications 12 à 16 comprenant une couche de conversion comprenant du Titane à l'interface entre le revêtement métallique et le film de peinture.
17) Sheet according to any one of claims 12 to 16 comprising a conversion layer comprising titanium at the interface between the metal coating and the paint film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IB2013/002239 WO2015052546A1 (en) | 2013-10-09 | 2013-10-09 | Sheet metal having a znaimg coating and improved flexibility and corresponding production method |
| PCT/IB2014/002059 WO2015052572A1 (en) | 2013-10-09 | 2014-10-09 | Sheet metal having a znaimg coating and improved flexibility and corresponding production method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4373989A1 true EP4373989A1 (en) | 2024-05-29 |
Family
ID=49780095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP14795864.9A Pending EP4373989A1 (en) | 2013-10-09 | 2014-10-09 | Sheet metal having a znaimg coating and improved flexibility and corresponding production method |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US20160251761A1 (en) |
| EP (1) | EP4373989A1 (en) |
| JP (1) | JP6279723B2 (en) |
| KR (2) | KR20160067943A (en) |
| CN (1) | CN105829568B (en) |
| AU (1) | AU2014333502B2 (en) |
| BR (1) | BR112016006159B1 (en) |
| CA (1) | CA2926564C (en) |
| EA (1) | EA030933B1 (en) |
| MX (1) | MX2016004415A (en) |
| UA (1) | UA119543C2 (en) |
| WO (2) | WO2015052546A1 (en) |
| ZA (1) | ZA201601734B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106929708A (en) * | 2017-04-27 | 2017-07-07 | 甘肃酒钢集团宏兴钢铁股份有限公司 | A kind of preparation method of the anticorrosive zinc base casting alloy used for hot dip galvanizing high of the Mg of Al containing Zn Si Ni Ce |
| MX2019014034A (en) * | 2017-05-25 | 2020-02-05 | Tata Steel Ijmuiden Bv | Method of manufacturing a continuous hot dip coated steel strip and hot dip coated steel sheet. |
| PL3456864T3 (en) * | 2017-09-18 | 2020-05-18 | Henkel Ag & Co. Kgaa | Two stage pre-treatment of aluminium, in particular aluminium casting alloys, comprising a pickle and a conversion treatment |
| KR102031466B1 (en) | 2017-12-26 | 2019-10-11 | 주식회사 포스코 | Zinc alloy coated steel having excellent surface property and corrosion resistance, and method for manufacturing the same |
| RU2727391C1 (en) * | 2020-02-03 | 2020-07-21 | Публичное Акционерное Общество "Новолипецкий металлургический комбинат" | Method of producing corrosion-resistant painted rolled steel with zinc-aluminum-magnesium coating |
| EP3858495A1 (en) * | 2020-02-03 | 2021-08-04 | Public Joint-Stock Company NOVOLIPETSK STEEL | Method for production of corrosion-resistant steel strip |
| JPWO2023166858A1 (en) * | 2022-03-04 | 2023-09-07 |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4291074A (en) * | 1978-11-09 | 1981-09-22 | Laminoirs De Strasbourg | Process for producing a sheet or strip which is lightly galvanized on one or both sides and products obtained by said process |
| JPS58177447A (en) * | 1982-04-08 | 1983-10-18 | Nisshin Steel Co Ltd | Manufacture of galvanized steel plate with superior corrosion resistance and coatability |
| US5059455A (en) * | 1988-03-08 | 1991-10-22 | Cyclops Corporation | Method for galvanizing perforated steel sheet |
| TW272206B (en) * | 1993-12-24 | 1996-03-11 | Nippon Paint Co Ltd | |
| JPH11158657A (en) * | 1997-11-26 | 1999-06-15 | Nippon Steel Corp | Surface-treated steel excellent in corrosion resistance |
| US6465114B1 (en) * | 1999-05-24 | 2002-10-15 | Nippon Steel Corporation | -Zn coated steel material, ZN coated steel sheet and painted steel sheet excellent in corrosion resistance, and method of producing the same |
| JP2001020049A (en) * | 1999-07-06 | 2001-01-23 | Nippon Steel Corp | HOT DIP Zn-Al-Mg PLATED STEEL EXCELLENT IN CORROSION RESISTANCE UNDER NONCOATING AND AFTER COATING AND ITS PRODUCTION |
| JP3465688B2 (en) * | 2001-01-17 | 2003-11-10 | 住友金属工業株式会社 | Hot-dip Zn-Al-based alloy-coated steel sheet excellent in workability and method for producing the same |
| JP2002285312A (en) * | 2001-03-27 | 2002-10-03 | Nippon Steel Corp | Galvanized steel sheet having excellent formability and production method therefor |
| US6555231B2 (en) * | 2001-07-03 | 2003-04-29 | Basf Corporation | Waterborne coating composition and a paint system thereof having improved chip resistance |
| JP2006328445A (en) * | 2005-05-23 | 2006-12-07 | Nippon Parkerizing Co Ltd | Water-based surface treating agent for precoat metal material, surface treating method and method for manufacturing precoat metal material |
| JP5194465B2 (en) * | 2006-03-08 | 2013-05-08 | Ｊｆｅスチール株式会社 | Painted steel sheet, processed product, thin panel for TV, and method for producing painted steel sheet |
| JP2007292288A (en) * | 2006-03-31 | 2007-11-08 | Akebono Brake Ind Co Ltd | Brake member and bonding method |
| EP1857567B1 (en) * | 2006-05-15 | 2017-04-05 | ThyssenKrupp Steel Europe AG | Method of manufacturing a flat steel product coated with a corrosion protection system |
| JP4829298B2 (en) * | 2006-06-15 | 2011-12-07 | 新日本製鐵株式会社 | Coated steel plate |
| JP2008000910A (en) * | 2006-06-20 | 2008-01-10 | Jfe Steel Kk | Highly anticorrosive surface treated steel sheet and its manufacturing method |
| JP5101249B2 (en) * | 2006-11-10 | 2012-12-19 | Ｊｆｅ鋼板株式会社 | Hot-dip Zn-Al alloy-plated steel sheet and method for producing the same |
| ES2391870T3 (en) * | 2007-02-12 | 2012-11-30 | Henkel Ag & Co. Kgaa | Procedure to treat metal surfaces |
| JP2009113389A (en) * | 2007-11-07 | 2009-05-28 | Jfe Galvanizing & Coating Co Ltd | Precoated steel sheet |
| JP2009191317A (en) * | 2008-02-14 | 2009-08-27 | Sumitomo Metal Ind Ltd | Method for manufacturing hot dip galvanized steel sheet having excellent degreasing property |
| US20100035080A1 (en) * | 2008-02-29 | 2010-02-11 | Gm Global Technology Operations, Inc. | Corrosion resistant laminated steel |
| EP2119804A1 (en) * | 2008-05-14 | 2009-11-18 | ArcelorMittal France | Method of manufacturing a covered metal strip with improved appearance |
| JP5600398B2 (en) | 2009-04-28 | 2014-10-01 | Ｊｆｅ鋼板株式会社 | Hot-dip galvanized steel sheet |
| WO2010130884A1 (en) * | 2009-05-14 | 2010-11-18 | Arcelormittal Investigacion Y Desarrollo Sl | Method for producing a coated metal band having an improved appearance |
| TWI452094B (en) * | 2010-09-02 | 2014-09-11 | Nippon Steel & Sumitomo Metal Corp | Conductive, excellent corrosion resistance of the coated metal plate |
| JP5649179B2 (en) * | 2011-05-30 | 2015-01-07 | Ｊｆｅ鋼板株式会社 | Hot-dip Zn-Al alloy-plated steel sheet with excellent corrosion resistance and workability and method for producing the same |
-
2013
- 2013-10-09 WO PCT/IB2013/002239 patent/WO2015052546A1/en active Application Filing
-
2014
- 2014-10-09 KR KR1020167011963A patent/KR20160067943A/en active Application Filing
- 2014-10-09 CA CA2926564A patent/CA2926564C/en active Active
- 2014-10-09 US US15/028,249 patent/US20160251761A1/en not_active Abandoned
- 2014-10-09 JP JP2016521699A patent/JP6279723B2/en active Active
- 2014-10-09 UA UAA201604963A patent/UA119543C2/en unknown
- 2014-10-09 CN CN201480055353.XA patent/CN105829568B/en active Active
- 2014-10-09 MX MX2016004415A patent/MX2016004415A/en unknown
- 2014-10-09 EA EA201690733A patent/EA030933B1/en not_active IP Right Cessation
- 2014-10-09 EP EP14795864.9A patent/EP4373989A1/en active Pending
- 2014-10-09 BR BR112016006159-4A patent/BR112016006159B1/en active IP Right Grant
- 2014-10-09 AU AU2014333502A patent/AU2014333502B2/en active Active
- 2014-10-09 WO PCT/IB2014/002059 patent/WO2015052572A1/en active Application Filing
- 2014-10-09 KR KR1020187003953A patent/KR102089879B1/en active IP Right Grant
-
2016
- 2016-03-14 ZA ZA2016/01734A patent/ZA201601734B/en unknown
-
2021
- 2021-06-15 US US17/347,868 patent/US20210310129A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015052546A1 (en) | 2015-04-16 |
| CA2926564C (en) | 2018-11-27 |
| AU2014333502A1 (en) | 2016-04-28 |
| CN105829568B (en) | 2018-11-23 |
| KR102089879B1 (en) | 2020-03-17 |
| US20160251761A1 (en) | 2016-09-01 |
| WO2015052572A9 (en) | 2015-08-20 |
| CN105829568A (en) | 2016-08-03 |
| BR112016006159B1 (en) | 2021-07-06 |
| KR20160067943A (en) | 2016-06-14 |
| AU2014333502B2 (en) | 2018-02-15 |
| MX2016004415A (en) | 2016-07-05 |
| BR112016006159A2 (en) | 2017-08-01 |
| JP2016540885A (en) | 2016-12-28 |
| EA030933B1 (en) | 2018-10-31 |
| US20210310129A1 (en) | 2021-10-07 |
| ZA201601734B (en) | 2020-07-29 |
| UA119543C2 (en) | 2019-07-10 |
| JP6279723B2 (en) | 2018-02-14 |
| BR112016006159A8 (en) | 2020-02-18 |
| EA201690733A1 (en) | 2016-08-31 |
| KR20180017240A (en) | 2018-02-20 |
| CA2926564A1 (en) | 2015-04-16 |
| WO2015052572A1 (en) | 2015-04-16 |
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