WO2022269021A1 - Method for producing a flat steel product having a zinc- or aluminium-based metal coating and corresponding flat steel product - Google Patents
Method for producing a flat steel product having a zinc- or aluminium-based metal coating and corresponding flat steel product Download PDFInfo
- Publication number
- WO2022269021A1 WO2022269021A1 PCT/EP2022/067307 EP2022067307W WO2022269021A1 WO 2022269021 A1 WO2022269021 A1 WO 2022269021A1 EP 2022067307 W EP2022067307 W EP 2022067307W WO 2022269021 A1 WO2022269021 A1 WO 2022269021A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- flat steel
- zinc
- tin
- aluminum
- steel base
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 221
- 239000010959 steel Substances 0.000 title claims abstract description 221
- 238000000576 coating method Methods 0.000 title claims abstract description 123
- 239000011248 coating agent Substances 0.000 title claims abstract description 116
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 73
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000004411 aluminium Substances 0.000 title claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 title abstract description 8
- 239000002184 metal Substances 0.000 title abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 144
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 140
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- 239000011701 zinc Substances 0.000 claims description 32
- 229910052742 iron Inorganic materials 0.000 claims description 25
- -1 zinc-aluminum-magnesium Chemical compound 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 13
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 6
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 6
- 230000007423 decrease Effects 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 3
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 48
- 238000000137 annealing Methods 0.000 description 27
- 230000008569 process Effects 0.000 description 20
- 238000000151 deposition Methods 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- 238000005246 galvanizing Methods 0.000 description 9
- 238000005275 alloying Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000003618 dip coating Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910005382 FeSn Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 1
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910017091 Fe-Sn Inorganic materials 0.000 description 1
- 229910005391 FeSn2 Inorganic materials 0.000 description 1
- 229910017142 Fe—Sn Inorganic materials 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 1
- 235000005487 catechin Nutrition 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229950001002 cianidanol Drugs 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000001995 intermetallic alloy Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 229940032330 sulfuric acid Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0257—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
-
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
Definitions
- the invention relates to a method for producing a flat steel product, in particular a high-strength flat steel product, with a flat steel base and a zinc- or aluminum-based metallic coating on at least one surface of the flat steel base, in which the flat steel base is made of a steel that contains one or more of the elements with an affinity for oxygen contains in % by weight: Al: more than 0.01, Cr: more than 0.1, Mn: more than 1.0, Si: more than 0.05, with a tin-containing metallic surface being applied to the surface—which may have been cleaned beforehand layer is applied, after which the flat steel base is annealed with the metallic layer and then the flat steel base thus coated and annealed is hot-dip coated with the zinc- or aluminum-based metallic coating.
- the invention further relates to a steel flat product with a flat steel base and a zinc- or aluminum-based metallic coating on at least one surface of the flat steel base, in which the flat steel base is made of a steel containing one or more of the elements with an affinity for oxygen in % by weight: AI: more than 0.01, Cr: more than 0.1, Mn: more than 1.0, Si: more than 0.05 and wherein the zinc- or aluminum-based metallic coating is a hot-dip zinc- or aluminum-based metallic coating.
- a zinc- or aluminum-based metallic coating is usually used to protect against corrosion and is usually applied to the flat steel product in a hot-dip hot-dip process in a continuous process.
- a zinc-based metallic coating is typically a zinc alloy which, in addition to a base of zinc and unavoidable impurities, consists of up to 8% by weight Mg, up to 8% by weight Al and no more than 2.0% by weight Fe in the molten bath .
- one or more additional elements such as Pb, Sb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni, Zr or Bi can be added up to 0.2% by weight per alloying element.
- An aluminum-based metallic coating is, for example, an AlSi alloy.
- zinc- or aluminum-based means that zinc or aluminum forms the main component of the metallic coating, i.e. no other component has a higher proportion of the metallic coating Has.
- flat steel products are referred to as high-strength flat steel products whose flat steel bases - usually steel strips - have yield points of at least 260 MPa and tensile strengths of at least 450 MPa.
- the usual elongation at break A80 for these steels is at least 5%.
- Typical thicknesses of these flat steel bases are around 0.45 mm to 3.0 mm for cold-rolled flat steel products and around 1.8 mm to 4.0 mm for hot-rolled flat steel products.
- Steel flat products or their flat steel bases can be available both as a strip and as a sheet metal section.
- One of the challenges in the production of a flat steel product which has a flat steel base with oxygen-affinity alloying elements and a zinc- or aluminum-based metallic coating on at least one surface of this flat steel base, is to ensure adequate adhesion of the zinc- or aluminum-based metallic coating on the flat steel base.
- the concentration and ratio between these alloying elements can prevent galvanizing with good coating adhesion. Therefore, there are a number of well-known ways to improve the galvanizability in a typical hot-dip galvanizing process with in-line intercritical annealing. These include oxidation/reduction processes, flash coating and alloying the steel substrate with surface-active elements. With the various methods, either the proportion of surface oxides on the direct surface is reduced or the morphology of the surface oxides is optimized. The aim of changing the morphology of the oxides is always the change from a flat oxide to a lens-shaped or spherical morphology. In principle, however, all of these options have their individual advantages and weaknesses.
- the publication US 2018 / 0 119263 A1 describes a method for producing a flat steel product in the form of a cold-rolled steel strip with a base steel strip which has an Mn content of between 1% by weight and 6% by weight and a C content of less than 0.3% by weight. %, and a zinc-based metallic coating on at least one surface of the base steel strip.
- the base steel strip is electroplated with a layer of pure iron, then the iron layer is oxidized to an iron oxide layer using an annealing process at a temperature between 600 °C and 800 °C, and then at a temperature between 750 °C and 900 °C in an atmosphere with 1 to 20% by volume hydrogen reduced.
- a zinc-based metallic coating is then applied by means of hot-dip coating.
- this publication also describes a corresponding steel strip with a base steel strip and a zinc-based metallic coating on at least one surface of this base steel strip, which has an Mn content of between 1% by weight and 6% by weight and a C content of less than 0.3% by weight. has and in which the zinc-based metallic coating is applied by hot dipping.
- the document CN 109477 191 A discloses another cold- or hot-rolled coated steel strip with a base steel strip and a coating on this base steel strip.
- the base steel strip has 0.08 to 0.3% by weight of C, 3.1 to 8.0% by weight of Mn, 0.01 to 2.0% by weight of Si, 0.001 to 0.5% by weight of Al.
- the coating consists of a layer based on iron and a metallic coating of zinc, zinc-iron, zinc-aluminium or zinc-aluminium-magnesium applied thereto by means of hot-dip coating.
- the publication WO 2019/123033 A1 describes a method for producing a flat steel product with a flat steel base and a zinc- or aluminum-based metallic coating on at least one surface of the flat steel base, in which the flat steel base is made of a steel that contains one or more of the elements with an affinity for oxygen % by weight contains: Al: more than 0.01, Cr: more than 0.1, Mn: more than 1.0 and Si: more than 0.05, with a tin layer being applied to the surface, then the Flat steel base is annealed with the tin layer and thereafter the thus coated and annealed flat steel base is hot dip coated with the zinc or aluminum based metallic coating.
- this publication describes a corresponding flat steel product with a flat steel base and a zinc- or aluminum-based metallic coating applied by means of hot-dipping to at least one surface of the flat steel base, with a border area containing tin extending into the flat steel base at an imaginary boundary between the flat steel base and the metallic coating.
- the publication JP 2001 200351 A describes a comparable method and the publication EP 2631 320 A2 describes a comparable flat steel product.
- the object of the invention is to specify relatively simple measures for providing a flat steel product which has a flat steel base hot-dip coated with a metallic coating and in which sufficient adhesion of this zinc- or aluminum-based coating to the flat steel base is uniformly ensured over a large area.
- the flat steel base is made of a steel containing one or more of the oxygen-affine elements in % by weight: AI : more than 0.01, Cr: more than 0.1, Mn: more than 1.0, Si: more than 0.05, with a tin-containing metallic layer being applied to the surface - optionally cleaned beforehand - and then the flat steel base is annealed with the metallic layer and then the flat steel base coated and annealed in this way is hot-dip coated with the zinc- or aluminum-based metallic coating, it is provided that a tin-iron alloy layer with a tin content of > 5% by weight and ⁇ 81% by weight is used.
- the tin-containing metallic layer contains tin is preferred as a layer in the range from 80 mg/m 2 to 7 g/m 2 .
- tin-iron alloy layer with a tin content of ⁇ 81% by weight is clearly better than pure tin layers with a tin content of > 98% by weight, as this avoids the formation of liquid tin-rich phases during the annealing process.
- Iron as an alloy partner is particularly advantageous because it does not selectively oxidize during the annealing process and forms tin alloy phases with a higher melting point.
- no additional element is introduced into the system of the steel flat product by iron.
- Tin-iron alloy layers can still be classified as harmless to health. Furthermore, iron is comparatively cheap compared to other potential alloying partners.
- tin layer of less than 80 mg/m 2 there is no significant effect and with a tin layer of more than 7 g/m 2 with increased material use no additional improvement can be seen, with a tin layer of more than 7 g/m 2 also being noticeable in subsequent heat treatment processes Liquid metal embrittlement can occur during a subsequent annealing treatment and possibly during subsequent welding processes during the processing of the finished steel flat product.
- tin coatings greater than 7 g/m 2 part of the deposited metallic layer containing tin often remains in the connection area (interface) between the steel flat product and the coating after the annealing process on the hot-dip galvanizing or hot-dip aluminizing.
- the tin coating is therefore in a range from 0.1 g/m 2 to 3.5 g/m 2 .
- the tin coating is in a range from 0.1 g/m 2 to 1.5 g/m 2 .
- the lower limit of the tin coating according to the invention is selected from 0.35 g/m 2 or even from 0.5 g/m 2 , the increase in the lower limit results in an ever larger process window with regard to the process parameters when operating in the annealing furnace .
- 0.35 g/m 2 one can anneal longer, which corresponds to a lower line speed in the plants, for example, but still achieve good adhesion of the zinc or aluminum based metallic coating.
- An even larger process window results for a lower limit of 0.5 g/m 2 .
- the mechanism on which the invention is based ie the change in surface morphology, is known in principle for the galvanizing of steel containing surface-active elements such as Sn, Bi and Sb. Also, the fact is known that the galvanizing of such steel with surface-active elements - compared to the corresponding steel without such surface-active elements - is significantly better.
- surface-active elements are understood to mean elements which, during annealing processes in a given atmosphere in a steel matrix, tend to diffuse to the grain boundaries and the surface and are then present there metallically or unoxidized in an intermetallic alloy.
- the decisive point in the procedure according to the invention is that steel, which does not have these surface-active elements or only in very small and therefore insufficient amounts for the mechanism, can be prepared by applying the tin-containing metallic layer with the said tin coating so that a correspondingly better galvanizability respectively aluminability is achieved.
- the quantity of surface-active elements necessary for the underlying mechanism is only required in a zone of the steel product close to the surface with a relatively small layer thickness.
- the required total amount of surface-active elements is significantly reduced.
- the method provides for the surfaces on both sides of the flat steel base to be provided with a tin-containing metallic layer and the zinc-based or aluminum-based metallic coating.
- a tin-iron alloy layer with a tin content of >35% by weight and ⁇ 68% by weight is used.
- the applied layer particularly preferably contains a tin content of >35% by weight and ⁇ 59% by weight.
- the thermodynamically stable intermetallic compounds FeSn 2 , FeSn, Fe 3 Sn 2 and Fe 5 Sn 3 are known.
- Pure tin has a very low melting point of 232°C.
- the reaction of a tin-containing metallic layer with the steel substrate to form FeSn2 is diffusion-controlled according to a parabolic growth law.
- a parabolic growth law When using pure tin layers with a tin content of > 98% by weight, sufficient mixing by diffusion from the deposited layer to the substrate before the melting point is reached is not always guaranteed at the usual heating rates of 1 K/s to 100 K/s.
- the possible compounds in the binary iron-tin phase system FeSn 2 , FeSn, Fe 3 Sn 2 and Fe 3 Sn 3 decompose peritectic into iron-rich phases and tin with dissolved iron.
- the peritectic decomposition temperature increases with increasing iron content of the intermetallic tin-iron phases from 513 °C to 910 °C.
- the use of a tin-iron alloy layer completely avoids the formation of liquid tin-rich phases during the annealing process.
- the occurrence of a liquid phase during the annealing can lead to a contamination of the furnace rollers with tin up to a failure of the furnace rollers.
- the tin coating on the steel strip is reduced locally.
- liquid phases can occur in tin layers with a tin content > 81% by weight.
- roller contact of liquid phases with the rollers in such tin layers with a tin content > 81% by weight must be avoided as far as possible by means of a suitable process control. This could be achieved, for example, with a low heating rate of up to 232 °C, or by adjusting the belt speed in the furnace.
- the tin-containing metallic layer has an average thickness of 0.02 to 1.0 ⁇ m.
- a layer thickness in the lower range of the range specified here is provided, with a tin-containing metallic layer with a tin content of 5% by weight to 15% by weight a layer thickness in the upper part of the range specified here.
- the tin-containing metallic layer is deposited in particular electrolytically or by deposition from the gas phase. Both types of separation are established.
- An electrolytic deposition of tin-containing layers with a tin content of ⁇ 98% by weight is possible from acidic tin(II) solutions as well as from alkaline tin(IV) solutions.
- Suitable acidic electrolytes are, in particular, those based on sulfuric acid, methanesulfonic acid, phenolsulfonic acid or tetrafluoroboric acid. These are preferably operated at temperatures from room temperature up to 65 °C.
- Alkaline stannate electrolytes are particularly suitable as alkaline electrolytes. These should preferably be operated above 55 °C.
- tin-iron alloy layers takes place, for example, from sulfuric acid or chloridic electrolytes containing tin(II) and iron(II) species at temperatures of up to 65 °C.
- complexing agents such as gluconate,
- Tartrate, nitrilotriacetate, ethylenediaminetetraacetate or citrate or their corresponding acids can be used.
- a conductive salt can optionally be added to the electrolyte for the deposition of layers containing tin.
- other additives such as surfactants to improve wetting, substances for smoothing and grain refinement (e.g. peptone, gelatine, 2-naphthol), antioxidants (e.g. catechin, hydroquinone), or defoamers makes sense in some cases.
- the electrolytic deposition takes place at current densities which, independently of the respective strip speed, result in a layer of the deposited tin-containing metallic layer which is homogeneous over the strip length and a composition which is as constant as possible. Furthermore, the necessary current density depends on the anode length in the direction of strip travel and the strip width. Typical values are between 1 and 120 A/dm 2 per hinge side. Below 1 A/dm 2 too long treatment lengths are required, which means that the process cannot be operated economically. At current densities above 120 A/dm 2 , homogeneous deposition is made significantly more difficult by burning, dendrite formation and excessive decomposition of organic additives. Current densities of up to 90 A/dm 2 are advantageously used. The deposition time depends on the length of treatment, the current density, the current yield and the desired layer coverage.
- the steel strip surface is rinsed and preferably dried in order to prevent an undefined entry of water into the annealing furnace atmosphere.
- the tin-containing metallic layer preferably contains tin in the range from 0.1 g/m 2 to 3.5 g/m 2 , particularly preferably in the range from 0.1 g/m 2 to 1.5 g/m 2 .
- the proportion by weight of aluminum differs from the proportion by weight of magnesium, in particular higher than the proportion by weight of magnesium in the material of the coating.
- the flat steel base is made of a steel containing one or more of the elements with an affinity for oxygen in % by weight: AI: more than 0 .02, Cr: more than 0.1, Mn: more than 1.3, Si: more than 0.1 and wherein the zinc- or aluminum-based metallic coating is a zinc- or aluminum-based metallic coating applied by hot dipping is provided that at an imaginary border between the flat steel base and the metallic coating a layered tin-containing border area is formed, which extends with a partial area into the flat steel base.
- This distribution of tin content into the flat steel base is typical for a flat steel product in which the tin is introduced “from the outside” during the manufacturing process and does not come from inside the flat steel base. In this way, the amount of tin can be carefully adjusted to the amount required to improve adhesion.
- the constant basic value of the relative tin content per volume unit in the steel of the flat steel base is reached at the latest from a depth T G of 5 ⁇ m starting from the corresponding surface of the flat steel base.
- the depth T G at which the constant basic value is reached, depends on the annealing conditions, alloy concepts of the flat steel basis, as well as the layer weight and the composition of the tin-containing metallic layer.
- the flat steel product configured in this way is in particular the product of the above-mentioned method for producing a steel product.
- the flat steel product is made of a steel comprising the following composition in % by weight:
- Si more than 0.05 to 3.0, optional
- V 0.005 to 0.3
- the steel preferably consists essentially of the aforementioned alloy components, in particular it consists of the aforementioned alloy components.
- the imaginary boundary corresponds to a real boundary where the flat steel base is immediately adjacent to the zinc or aluminum base metallic coating, or that
- an intermediate layer system is arranged at the imaginary border, which has at least one intermediate layer and is directly adjacent to the flat steel base on one side and directly to the zinc- or aluminum-based metallic coating on its other side, with each of the layers of the intermediate layer system having a tin content of ⁇ 81% by weight.
- the layered border area containing tin also extends, in particular, into the zinc-based or aluminum-based metallic coating.
- an intermetallic intermediate layer containing iron and aluminum is arranged between the flat steel product and the metallic coating in the layered border area containing tin. This has formed during the contact between the tin-enriched steel surface and the molten bath that occurs during hot dipping.
- This intermetallic intermediate layer containing iron and aluminum also contains more or less tin.
- this intermetallic intermediate layer containing iron and aluminum is also known to the person skilled in the art as the so-called inhibition layer.
- a gap in the inhibition layer is an indication of insufficient adhesion of the hot-dip coating.
- the embodiment according to the invention includes a certain amount of metallic iron on the substrate surface before it is immersed in the molten bath, so that the desired inhibition layer forms to a sufficient extent even in the case of steel alloys with a high alloy content.
- an intermediate layer is considered sufficient if it achieves a coating adhesion for the entire coating in accordance with SEP1931 with a rating of 1 - 2. This means that no zinc flaking is detected after testing in accordance with standards.
- the zinc- or aluminum-based metallic coating is a coating of zinc (Z/Gl), zinc-aluminum (ZA, Galfan), zinc-aluminum-iron (ZF/GA), zinc-magnesium-aluminum (ZM) or aluminum-zinc (AZ). All of these coatings are established coatings for corrosion protection.
- the proportion by weight of aluminum in the material of the coating is higher than the proportion by weight of magnesium.
- the ratio of aluminum to magnesium content (in weight %) is ⁇ 1.3.
- the invention further relates to the use of a flat steel product produced as described above or of a flat steel product described above for the production of parts for motor vehicles.
- FIG. 1 shows a schematic sectional view of a flat steel product with a flat steel base and a zinc- or aluminum-based metallic coating according to a preferred embodiment of the invention
- FIG. 2 shows a diagram which qualitatively reproduces the relative tin content in the flat steel base of the flat steel product shown in FIG. 1 from the surface of the flat steel base provided with the metallic coating into the flat steel base,
- FIG. 3 shows an exemplary course of the tin signal intensity as a GDOES depth profile of annealed samples without precoating and with a tin layer
- FIG. 4 shows a near-surface area of the GDOES depth profile from FIG.
- Fig. 1 shows a schematic sectional view of one side of a flat steel product 10 with a flat steel base 12 and a zinc- or aluminum-based metallic coating 14 created by a hot-dip process on at least one surface 16 of the flat steel base 12.
- the flat steel base 12 is a steel strip 18, which (Not shown here) is provided on both sides with a zinc- or aluminum-based metallic coating 14.
- a layered tin-containing boundary region 22 is formed, which extends into the flat steel base 12 with a portion 24, the relative Tin content per unit volume in this sub-area - starting from the surface 16 of the flat steel base - continuously decreases into the flat steel base 12 up to a constant basic value of the relative tin content per unit volume. Details of this depth distribution of relative tin content are discussed in connection with FIG.
- the surfaces 16 on both sides of the flat steel base 12 are each provided with a zinc- or aluminum-based metallic coating 14 as a rule.
- the zinc- or aluminum-based metallic coating 14 is an aluminum-containing coating, ie, for example, a coating of zinc-aluminum, zinc-aluminum-iron, zinc-magnesium-aluminum or aluminum-zinc.
- an intermediate layer system with an intermetallic intermediate layer 26 containing iron and aluminum is arranged between the flat steel base 12 and the zinc- or aluminum-based metallic coating 14 .
- this intermediate layer is at the level of the imaginary boundary 20.
- Such an intermediate layer 26 is also known as a so-called inhibition layer in connection with readily wettable steels.
- the layered tin-containing border region 22 also extends into the zinc- or aluminum-based metallic coating 14 with a further partial region 28 .
- the intermetallic intermediate layer 26 containing iron and aluminum has a tin content of ⁇ 81% by weight.
- the steel of the flat steel base 12 has one or more of the following oxygen-affinity elements: (i) Al: more than 0.02% by weight, (ii) Cr: more than 0.1% by weight, (iii) Mn : more than 1.3% by weight, (iv) Si: more than 0.1% by weight.
- the flat steel base 12 (the steel substrate) for the steel flat product 10 has the following composition in % by weight in the example:
- V 0.005 to 0.3
- the manufacturing process for producing such a steel flat product 10 first comprises cleaning the surface 16 of the flat steel base 12 and applying a metallic layer containing tin to the cleaned surface 16 of the flat steel base 12, the metallic layer containing tin containing tin in the range from 80 mg/m 2 to 7 g/m 2 contains.
- This coating with the tin-containing metallic layer is referred to below as pre-coating, since this is followed by hot-dip coating, in which the pre-coated flat steel base 12 is provided with the zinc-based or aluminum-based coating 14 .
- a tin-iron alloy layer with a tin content of >5% by weight and ⁇ 81% by weight is used as the metallic layer containing tin.
- the manufacturing method also includes an annealing treatment of the flat steel base 12 provided with the tin-containing metallic layer, ie correspondingly precoated, in a continuous annealing furnace.
- This furnace can be a combination of a furnace part with open combustion (DFF, Direct Fired Furnace / NOF, Non-Oxidizing Furnace) and a radiant tube furnace (RTF, Radiation Tube Furnace) arranged after it, or in an all radiant tube furnace (All Radiant Tube Furnace). take place.
- DFF Direct Fired Furnace / NOF, Non-Oxidizing Furnace
- RTF Radiation Tube Furnace
- the flat steel base 12 precoated in this way is annealed at an annealing temperature of 550° C. to 880° C.
- the flat steel base 12 is then cooled to a temperature above the coating melt bath temperature and subsequently coated with the metallic coating 14 .
- the flat steel base 12 can be cooled to a so-called overaging temperature between 200° C. and 600° C. and kept at this temperature for up to 500 s.
- the flat steel base 12 can be heated before entering the melt bath, for example by inductive heating to a temperature above the melt bath temperature of between 400 ° C and 750 °C so that the cold flat steel base does not extract heat from the weld pool.
- the use of the tin-containing coating according to the invention makes an additional introduction of water vapor to increase the dew point during the annealing process, as is customary in the previously known methods, unnecessary. It is crucial for the process to ensure reductive conditions by means of a suitable annealing gas atmosphere for the tin-containing layer in order to obtain a predominantly metallic, tin-containing layer on the surface before the steel strip is immersed in the molten bath. Depending on the annealing temperature, the layer thickness and the tin content of the tin-containing coating, as well as the steel alloy, the activity of the tin and thus the oxidation behavior is influenced.
- the oxidation behavior of the furnace atmosphere can be controlled via the ratio of hydrogen and water vapor.
- the oxidizing capacity of the atmosphere is determined by the following chemical equilibrium with the equilibrium constant Kw.
- Dew point set between -35 °C and -70 °C and set in a particularly preferred variant between -45 °C and -70 °C.
- An exemplary advantageous process sequence for the production of a flat steel product 10 with improved adhesion of a zinc-based coating 14 provides, in the example of the steel strip, that a hot-rolled steel strip (hot strip) is first pickled, then cold-rolled and then in a so-called hot dip galvanizing line (hot dip galvanizing line). ) is provided with the zinc-based coating 14.
- a hot-rolled steel strip hot strip
- hot dip galvanizing line hot dip galvanizing line
- the strip goes through a pre-cleaning section, after pre-cleaning the strip goes through further strip activation (pickling/pickling) and then an electrolysis unit, in which the tin-containing metallic layer is deposited.
- the pre-coated strip then runs through rinsing and drying.
- the strip then enters the furnace section of the galvanizing line, is annealed and provided with the zinc-based coating 14.
- the result of this manufacturing process is the flat steel product 10 shown in Fig. 1.
- the annealing treatment described and the hot dip coating of the flat steel base pre-coated with the tin-containing metallic layer result in the layered tin-containing border area 22, which with its tin-containing partial area 24 extends into a zone near the surface of the flat steel base 12 extends into it and in which the relative tin content per unit volume in this portion 24 - starting from the corresponding surface 16 of the flat steel base - in the flat steel base 12 continuously up to a constant basic value of the relative tin content per Unit volume as indicated in the diagram of FIG. 2 decreases. According to the literature, this basic value should generally be well below 0.01% by weight.
- the intermediate layer system of the flat steel product can also have a further intermediate layer (not shown) in addition to the intermetallic intermediate layer 26 containing iron and aluminum shown, which consists of a remaining residue of the tin-iron alloy layer with a tin content of > 5% by weight and ⁇ 81% by weight formed tin-containing metallic layer.
- the tin content of this further intermediate layer is ⁇ 81% by weight.
- Fig. 2 shows a diagram which qualitatively reproduces the relative tin content/tin proportion A in the flat steel base 12 of the flat steel product 10 shown in Fig. 1, starting from the surface 16 of the flat steel base 12 provided with the metallic coating, perpendicularly into the flat steel base 12.
- the basic salary is given deep inside, i.e. in the mass (the bulk), of the flat steel base.
- the zone close to the surface is shown on the left, which extends into the interior of the flat steel base 12 to a maximum depth T of 5 ⁇ m.
- the relative tin content per unit volume decreases—starting from the surface 16 of the flat steel base—into the interior of the flat steel base 12 continuously up to the constant basic value of the relative tin content per unit volume drawn on the right (for the bulk).
- the constant basic value of the relative tin content per volume unit in the steel of the flat steel base 12 can be assumed from a depth T G of 5 ⁇ m, starting from the corresponding surface of the flat steel base.
- Fig. 3 shows an exemplary course of the tin signal intensity determined by means of glow discharge spectroscopy (GDOES: Glow Discharge Optical Emission Spectroscopy) as a depth profile of annealed samples (a) with tin coating (see dotted line) and (b) without pre-coating (see solid line). ) in a chart.
- GDOES glow discharge spectroscopy
- a count rate c corresponding to the tin intensity is plotted against the time in seconds t/s. 300 s correspond to about 10 pm sputtering depth.
- FIG. 4 shows a section of the GDOES depth profile close to the surface of sample (b) without precoating from FIG.
- the local minimum is a signal profile that clearly stands out compared to the signal noise.
- Table 1 gives exemplary characteristics and parameters for the deposition of tin-iron alloy layers and Table 2, as a reference, exemplary characteristics and parameters for the deposition of pure tin layers as part of the coating of the corresponding flat steel base 12 with a zinc- or aluminum-based metallic coating 14.
- Table 3 gives the characteristics of exemplary implementations of the coating processes on the hot-dip dip simulator. It is found that in the examples (according to the invention) consistently good zinc adhesion grades (according to SEP1931) are achieved, while in the counter-examples (not according to the invention) both good and bad zinc adhesion grades occur.
- Table 4 indicates which steels were used for the example tests on the hot-dip simulator (named A, B, C in Table 3).
- One aspect of the present invention can -possibly as an independent idea- also be extended to a metallic layer containing tin, in which a tin layer with a tin content of >98% by weight is also used, namely the design of the flat steel product 10 with a flat steel base 12 and zinc or aluminium-based metallic coating 14, in which the imaginary boundary 20 corresponds to a real boundary at which the flat steel base 12 directly adjoins the zinc- or aluminium-based metallic coating 14.
- the imaginary boundary 20 corresponds to a real boundary at which the flat steel base 12 directly adjoins the zinc- or aluminium-based metallic coating 14.
- the tin-containing metallic layer applied to the surface 16 during production must have such a small thickness or such a low layer weight that its material after the subsequent Annealing treatment and hot-dip coating is fully diffused into the flat steel base 12 and / or the zinc or aluminum-based metallic coating 14.
- Table 2 Examples of the composition of electrolytes and operating conditions for the deposition of pure tin layers
Abstract
Description
Claims
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CN202280044745.0A CN117545863A (en) | 2021-06-24 | 2022-06-24 | Method for producing a flat steel product with a zinc-or aluminum-based metal coating and corresponding flat steel product |
KR1020247000642A KR20240025596A (en) | 2021-06-24 | 2022-06-24 | Method for manufacturing flat steel products with zinc or aluminum-based metal coating and corresponding flat steel products |
EP22738596.0A EP4359575A1 (en) | 2021-06-24 | 2022-06-24 | Method for producing a flat steel product having a zinc- or aluminium-based metal coating and corresponding flat steel product |
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DE102021116367.6A DE102021116367A1 (en) | 2021-06-24 | 2021-06-24 | Process for the production of a flat steel product with a zinc- or aluminum-based metallic coating and corresponding flat steel product |
DE102021116367.6 | 2021-06-24 |
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KR (1) | KR20240025596A (en) |
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Citations (6)
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US4388158A (en) * | 1978-11-27 | 1983-06-14 | Toyo Kohan Company, Ltd. | Acidic tinplating process and process for producing an iron-tin alloy on the surface of a steel sheet |
JP2001200351A (en) | 2000-01-21 | 2001-07-24 | Nippon Steel Corp | METHOD OF MANUFACTURING FOR HIGH TENSILE STRENGTH HOT- DIP ZN-Al ALLOY COATED STEEL SHEET |
EP2631320A2 (en) | 2010-10-21 | 2013-08-28 | Posco | Metal-coated steel sheet, galvannealed steel sheet, and method for manufacturing same |
US20180119263A1 (en) | 2011-12-28 | 2018-05-03 | Posco | High-strength hot-dip galvanized steel sheet having excellent plating surface quality and adhesion, and method of manufacturing the same |
CN109477191A (en) | 2016-07-07 | 2019-03-15 | Posco公司 | Resistance to crack expansibility and the excellent hot-forming component and its manufacturing method of ductility |
WO2019123033A1 (en) | 2017-12-19 | 2019-06-27 | Arcelormittal | A hot-dip coated steel substrate |
-
2021
- 2021-06-24 DE DE102021116367.6A patent/DE102021116367A1/en active Pending
-
2022
- 2022-06-24 CN CN202280044745.0A patent/CN117545863A/en active Pending
- 2022-06-24 WO PCT/EP2022/067307 patent/WO2022269021A1/en active Application Filing
- 2022-06-24 KR KR1020247000642A patent/KR20240025596A/en unknown
- 2022-06-24 EP EP22738596.0A patent/EP4359575A1/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US4388158A (en) * | 1978-11-27 | 1983-06-14 | Toyo Kohan Company, Ltd. | Acidic tinplating process and process for producing an iron-tin alloy on the surface of a steel sheet |
JP2001200351A (en) | 2000-01-21 | 2001-07-24 | Nippon Steel Corp | METHOD OF MANUFACTURING FOR HIGH TENSILE STRENGTH HOT- DIP ZN-Al ALLOY COATED STEEL SHEET |
EP2631320A2 (en) | 2010-10-21 | 2013-08-28 | Posco | Metal-coated steel sheet, galvannealed steel sheet, and method for manufacturing same |
US20180119263A1 (en) | 2011-12-28 | 2018-05-03 | Posco | High-strength hot-dip galvanized steel sheet having excellent plating surface quality and adhesion, and method of manufacturing the same |
CN109477191A (en) | 2016-07-07 | 2019-03-15 | Posco公司 | Resistance to crack expansibility and the excellent hot-forming component and its manufacturing method of ductility |
WO2019123033A1 (en) | 2017-12-19 | 2019-06-27 | Arcelormittal | A hot-dip coated steel substrate |
EP3728681A1 (en) * | 2017-12-19 | 2020-10-28 | ArcelorMittal | A hot-dip coated steel substrate |
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EP4359575A1 (en) | 2024-05-01 |
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