CN115053009B - Hot-pressed member, method for producing same, and plated steel sheet for hot pressing - Google Patents
Hot-pressed member, method for producing same, and plated steel sheet for hot pressing Download PDFInfo
- Publication number
- CN115053009B CN115053009B CN202080095524.7A CN202080095524A CN115053009B CN 115053009 B CN115053009 B CN 115053009B CN 202080095524 A CN202080095524 A CN 202080095524A CN 115053009 B CN115053009 B CN 115053009B
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- hot
- steel sheet
- plating layer
- alloy plating
- phase
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 88
- 239000010959 steel Substances 0.000 title claims abstract description 88
- 238000007731 hot pressing Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000007747 plating Methods 0.000 claims abstract description 96
- 229910018134 Al-Mg Inorganic materials 0.000 claims abstract description 55
- 229910018467 Al—Mg Inorganic materials 0.000 claims abstract description 55
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 55
- 239000000956 alloy Substances 0.000 claims abstract description 55
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 11
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 230000005855 radiation Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 230000009466 transformation Effects 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 abstract description 65
- 238000000576 coating method Methods 0.000 abstract description 65
- 230000007797 corrosion Effects 0.000 abstract description 43
- 238000005260 corrosion Methods 0.000 abstract description 43
- 239000000126 substance Substances 0.000 abstract description 41
- 238000011282 treatment Methods 0.000 abstract description 41
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052726 zirconium Inorganic materials 0.000 abstract description 30
- 238000004070 electrodeposition Methods 0.000 abstract description 29
- 229910020679 Co—K Inorganic materials 0.000 abstract description 4
- 229910001566 austenite Inorganic materials 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 120
- 239000012071 phase Substances 0.000 description 57
- 229910000861 Mg alloy Inorganic materials 0.000 description 17
- 239000011701 zinc Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 238000007739 conversion coating Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZARVOZCHNMQIBL-UHFFFAOYSA-N oxygen(2-) titanium(4+) zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4] ZARVOZCHNMQIBL-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- 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
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0242—Flattening; Dressing; Flexing
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/20—Deep-drawing
-
- 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
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
- 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
- C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
-
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
-
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
-
- 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
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- 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
- C21D1/62—Quenching devices
- C21D1/673—Quenching devices for die quenching
-
- 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
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
-
- 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
-
- 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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Coating With Molten Metal (AREA)
- Chemical Treatment Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electroplating Methods And Accessories (AREA)
- Shaping Metal By Deep-Drawing, Or The Like (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention provides a hot-pressed part which has excellent film adhesion and corrosion resistance after coating when electro-deposition coating is performed after zirconium-based chemical conversion treatment. The hot-pressed member of the present invention is characterized by comprising a base steel sheet, an Fe-Zn-Al-Mg alloy plating layer formed on at least one surface of the base steel sheet and containing an alpha-Fe phase and a gamma-Fe phase in an adhesion amount of 40 to 400g/m 2 per surface, and an oxide layer formed on the Fe-Zn-Al-Mg alloy plating layer and containing Zn, al and Mg, wherein the oxide layer is formed by Co-K alpha (wavelength at an incident angle of 25 DEG) The ratio (IΓ/Iα) of the intensity (IΓ) of a diffraction peak of a (411) crystal plane of a gamma-phase present at 41.5 DEG-2 theta-43.0 DEG to the intensity (Iα) of a diffraction peak of a (110) crystal plane of an alpha-Fe phase present at 51.0 DEG-2 theta-52.0 DEG, obtained by X-ray diffraction of a radiation source, is 0.5 or less, and the sum of the Al concentration and the Mg concentration of the oxide layer is 28 atomic% or more.
Description
Technical Field
The present invention relates to a hot-pressed member, a method for producing the same, and a plated steel sheet for hot pressing.
Background
Conventionally, chassis members, body structural members, and the like of automobiles are often manufactured by press working steel plates having predetermined strength. In recent years, from the viewpoint of global environmental protection, weight reduction of automobile bodies has been desired, and there is an ongoing effort to increase the steel sheet used and reduce the sheet thickness thereof. However, as the strength of the steel sheet increases, the press workability thereof decreases, and therefore, it is difficult to process the steel sheet into a desired component shape.
In order to solve such a problem, a processing technique called hot pressing has been proposed in which a heated steel sheet is processed with a die composed of a die and a punch, and quenched, thereby achieving both ease of processing and high strength. Since a plating layer having a lower electrochemical corrosion potential than the base steel sheet remains after heating, a Zn alloy-plated steel sheet has been attracting attention as a steel sheet for hot pressing having high rust resistance, and a hot-pressed member using the Zn alloy-plated steel sheet and a method for producing the same have been proposed.
Patent document 1 describes a hot-press plated steel sheet in which the Al concentration { Al } in the plating layer is in the range of 0.2 to 1.0g/m 2 and the relationship between the Mg concentration { Mg } (mass%) in the plating layer and the Al concentration satisfies 0.10 ++mg/{ Al +.5, and a hot-press member obtained by heating and hot-pressing the hot-press plated steel sheet
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2006-265706
Disclosure of Invention
Patent document 1 describes that the hot-pressed member described in patent document 1 is excellent in post-coating corrosion resistance when electro-deposition coating is performed after zinc phosphate chemical conversion treatment. In recent years, zirconium-based chemical conversion treatments have been spreading instead of the conventional zinc phosphate-based chemical conversion treatments. Therefore, there is also a demand for film adhesion and post-coating corrosion resistance in the case of electrodeposition coating after zirconium-based chemical conversion treatment is performed on hot-pressed parts. However, the inventors of the present invention have found that the hot-pressed member disclosed in patent document 1 is excellent in corrosion resistance after the zinc phosphate chemical conversion coating and the electrodeposition coating, but insufficient in adhesion of the coating film and corrosion resistance after the zirconium chemical conversion coating.
In view of the above problems, an object of the present invention is to provide a hot-pressed member excellent in film adhesion and corrosion resistance after coating in electrodeposition coating after zirconium-based chemical conversion treatment, and a preferred method for producing the same.
The present invention also aims to provide a plated steel sheet for hot pressing which is suitable as a blank for obtaining such a hot-pressed member.
The present inventors have conducted intensive studies to solve the above problems, and have found the following findings.
In the Fe-Zn-Al-Mg alloy plating layer of the hot-pressed member, precipitation of a gamma phase composed of an intermetallic compound having a low electrochemical corrosion potential such as Fe3Zn10 is restricted, and the total of Al concentration and Mg concentration is increased in the Zn-Al-Mg-containing oxide layer formed on the plating layer, whereby film adhesion and corrosion resistance after coating can be improved when electrodeposition coating is performed after zirconium-based chemical conversion treatment is performed.
In order to produce a hot-pressed member having the fe—zn—al—mg alloy plating layer with a small amount of precipitation of Γ phase and an oxide layer with a large total of Al concentration and Mg concentration as described above, it is necessary to heat a hot-pressed plated steel sheet having a zn—al—mg alloy plating layer with a predetermined Al amount and Mg amount and a liquidus temperature of 400 ℃ or less to a low temperature and then to perform hot-pressing.
The gist of the present invention completed based on the above findings is as follows.
[1] A hot-pressed member is characterized by comprising a base steel sheet, an Fe-Zn-Al-Mg alloy plating layer, and an oxide layer,
The Fe-Zn-Al-Mg alloy plating layer is formed on at least one surface of the base steel sheet in an adhesion amount of 40-400 g/m 2 per surface, and contains an alpha-Fe phase and a gamma-I phase,
The oxide layer is formed on the Fe-Zn-Al-Mg alloy plating layer and contains Zn, al and Mg,
From Co-K alpha (wavelength at an angle of incidence of 25 DEG) The ratio I Γ/Iα of the intensity I Γ of the diffraction peak of the (411) crystal face of the gamma-phase existing at 41.5 DEG-2 theta-43.0 DEG to the intensity I α of the diffraction peak of the (110) crystal face of the alpha-Fe phase existing at 51.0 DEG-2 theta-52.0 DEG obtained by X-ray diffraction of a radiation source is 0.5 or less,
The sum of the Al concentration and the Mg concentration of the oxide layer is 28 atomic% or more.
[2] A method for producing a hot-pressed member, characterized in that a hot-pressed plated steel sheet is heated to a temperature in the range of Ac 3 transformation point to 1000 ℃ and then hot-pressed,
The hot-press coated steel sheet has a base steel sheet and a Zn-Al-Mg alloy plating layer,
The Zn-Al-Mg alloy plating layer is formed on at least one surface of the base steel sheet with an adhesion amount of 30-180 g/m 2 per surface, and contains Al in mass%: 3-10% and Mg:0.2 to 0.8 percent, and the balance of Zn and unavoidable impurities, wherein the liquidus temperature in the atmosphere is below 400 ℃.
[3] The method for producing a hot-pressed member according to the above [2], wherein the component composition of the Zn-Al-Mg alloy plating layer further contains at least one selected from Ca, sr, mn, V, cr, mo, ti, ni, co, sb, zr and B in a total amount of 1% by mass or less.
[4] A hot-pressed coated steel sheet comprising a base steel sheet and a Zn-Al-Mg alloy plating layer,
The Zn-Al-Mg alloy plating layer is formed on at least one surface of the base steel sheet with an adhesion amount of 30-180 g/m 2 per surface, and contains Al in mass%: 3-10% and Mg:0.2 to 0.8 percent, and the balance of Zn and unavoidable impurities, wherein the liquidus temperature in the atmosphere is below 400 ℃.
[5] The hot-press coated steel sheet according to the above [4], wherein the composition of the Zn-Al-Mg alloy plating layer further contains at least one selected from Ca, sr, mn, V, cr, mo, ti, ni, co, sb, zr and B in a total amount of 1% by mass or less.
The hot-pressed member of the present invention is excellent in film adhesion and corrosion resistance after coating when electrodeposition coating is performed after zirconium-based chemical conversion treatment. Further, according to the method for producing a hot-pressed member of the present invention, a hot-pressed member excellent in film adhesion and corrosion resistance after coating can be produced when electrodeposition coating is performed after zirconium-based chemical conversion treatment.
The hot-press coated steel sheet of the present invention is suitable for use as a blank for producing a hot-press member excellent in film adhesion and corrosion resistance after coating in electrodeposition coating after zirconium-based chemical conversion treatment.
Drawings
FIG. 1 is a cross-sectional SEM image of a Fe-Zn-Al-Mg alloy plating layer of a hot-pressed article of No.2, which is represented by an inventive example.
FIG. 2 is a cross-sectional SEM image of a Fe-Zn-Al-Mg alloy plating layer of a hot-pressed member of No.8, which is represented by a comparative example.
Detailed Description
(Hot pressing part)
A hot press member according to one embodiment of the present invention includes a base steel sheet Fe-Zn-Al-Mg alloy plating layer formed on at least one surface of the base steel sheet and an oxide layer formed on the Fe-Zn-Al-Mg alloy plating layer.
[ Base Steel sheet ]
The base steel sheet in the hot-pressed member of the present embodiment is not particularly limited, and a steel sheet having a composition described in one of the hot-pressed plated steel sheets to be described later is preferably used in order to set the tensile strength TS of the hot-pressed member to 1470MPa or more.
[ Fe-Zn-Al-Mg alloy plating ]
The Fe-Zn-Al-Mg alloy plating layer in the hot-pressed member of the present embodiment contains an α -Fe phase and a Γ phase, and is preferably composed of the α -Fe phase and the Γ phase.
The α -Fe phase is a solid solution phase mainly composed of Fe and containing Zn, al, and Mg. When hot-pressing a hot-press coated steel sheet having a Zn-Al-Mg alloy plating layer, zn, al and Mg in the plating layer diffuse into a base steel sheet, and a solid solution phase (α -Fe phase) mainly composed of Fe and containing Zn, al and Mg is formed in the diffusion region. It can be explained that the α -Fe phase is formed so as to erode the surface layer portion of the base steel sheet in the plated steel sheet, but generally constitutes a part of the fe—zn—al—mg alloy plating layer located on the base steel sheet in the hot-pressed member.
The Γ phase is a phase composed of an intermetallic compound mainly composed of Zn and containing Al, mg, and Fe, and is mainly composed of an Fe3Zn10 phase. In addition, since the Γ1 phase has a crystal structure similar to that of the Γ phase, it is difficult to distinguish it by X-ray diffraction, and "Γ phase" in this specification also includes Γ1 phase. Examples of intermetallic compounds constituting the Γ phase include Fe4Zn9, feZn4, and Fe5Zn 21. In hot pressing, fe diffused from a base steel sheet is introduced into a Zn-Al-Mg alloy plating layer which remains without contributing to the diffusion of the base steel sheet, whereby a gamma phase composed of an intermetallic compound is formed, and a part of the Fe-Zn-Al-Mg alloy plating layer is formed in a hot-pressed member.
Here, the α -Fe phase and Γ phase are distinguishable from each other because they have significantly different contrasts in the cross-sectional SEM images of the fe—zn—al—mg alloy plating layer of the hot-pressed member. Referring to fig. 1 and 2, a portion appearing bright in the surface layer portion of the hot-pressed member is a Γ phase, and a portion appearing dark is an α -Fe phase. In addition, the α -Fe phase and Γ phase may pass through Co-K α (wavelength) Is determined for X-ray diffraction of the radiation source.
The Γ phase in the fe—zn—al—mg alloy plating layer has a significantly lower potential than the base steel sheet and the α -Fe phase, and therefore is preferentially corroded when exposed to a corrosive environment. That is, the Γ phase exhibits a sacrificial corrosion protection against the base steel sheet, the α -Fe phase.
Here, the zinc phosphate-based chemical conversion coating film has an excellent function as a corrosion inhibitor for Zn-based alloys. Therefore, even if a part obtained by performing electrodeposition coating after zinc phosphate chemical conversion treatment on a hot-pressed part obtained by hot-pressing a Zn-Al-Mg alloy-plated steel sheet is in a sacrificial corrosion-resistant state due to the defects of the substrate steel sheet being reached through the coating film, the chemical conversion coating film and the plating layer, the corrosion rate of the Γ phase is small, the corrosion rate under the coating film is sufficiently small, and the corrosion resistance after coating is not a problem in an actual use environment.
In contrast, the zirconium oxide-based chemical conversion coating film does not have a corrosion inhibition function for the Zn-based alloy. Therefore, the corrosion rate of Γ phase is high after the sacrificial corrosion-resistant state is reached, and as a result, the corrosion rate under the coating film is increased. Further, when the amount of the Γ phase is large and the Γ phase is continuously present in the fe—zn—al—mg alloy plating layer without being broken, corrosion of the Γ phase in the environment under the coating film propagates in-plane when the corrosion-preventing state is achieved, and the appearance defects such as expansion of the coating film can be visually recognized. Therefore, when the zirconium-based chemical conversion treatment is applied, it is important to limit the amount of Γ phase in order to secure corrosion resistance after coating.
Therefore, in the present embodiment, as one of the requirements for improving the post-coating corrosion resistance when the hot-pressed member is subjected to the zirconium-based chemical conversion treatment and then to the electrodeposition coating, it is important to restrict precipitation of Γ phase composed of intermetallic compounds having a low electrochemical corrosion potential such as Fe3Zn 10. In particular, it is important to obtain a light-emitting device composed of Co-K alpha (wavelength) The ratio I Γ/Iα of the intensity I Γ of the diffraction peak of the (411) crystal face of the gamma-phase existing at 41.5 DEG.ltoreq.2θ.ltoreq.43.0 DEG to the intensity I α of the diffraction peak of the (110) crystal face of the alpha-Fe phase existing at 51.0 DEG.ltoreq.2θ.ltoreq.52.0 DEG obtained by X-ray diffraction of a radiation source is 0.5 or less. If I Γ/Iα exceeds 0.5, the hot-pressed member is subjected to zirconium-based chemical conversion treatment and then is subjected to electrodeposition coating, and the post-coating corrosion resistance becomes insufficient. If I Γ/Iα is 0.5 or less, the gamma phase in the Fe-Zn-Al-Mg alloy plating layer is sufficiently broken by the alpha-Fe phase, and excellent post-coating corrosion resistance can be obtained when the hot-pressed member is subjected to the zirconium-based chemical conversion treatment and then subjected to the electrodeposition coating.
The lower limit is not particularly limited since the smaller the value of I Γ/Iα is, as described above, the value of I Γ/Iα detected when measured by X-ray diffraction is usually 0.01 or more.
The conditions for measuring the incident angle and the X-ray diffraction other than the radiation source do not affect the ratio I Γ/Iα, and the conditions described in examples described below can be used.
Adhesion amount per side: 40-400 g/m 2
By setting the adhesion amount of the Fe-Zn-Al-Mg alloy plating layer of the hot-pressed member to 40 to 400g/m 2, a hot-pressed member excellent in corrosion resistance can be obtained. When the adhesion amount is less than 40g/m 2, a hot-pressed part having a desired corrosion resistance cannot be obtained. When the adhesion amount exceeds 400g/m 2, the number of cracks crossing the plating layer becomes significantly large under the influence of solidification shrinkage of the plating layer after hot pressing, and the adhesion in the plating layer becomes significantly poor. The adhesion amount of the plating layer of the hot-pressed member is preferably 50g/m 2 or more, more preferably 60g/m 2 or more. The adhesion amount of the plating layer of the hot-pressed member is preferably 350g/m 2 or less, more preferably 300g/m 2 or less.
In the present specification, the "adhesion amount per one surface of the Fe-Zn-Al-Mg alloy plating layer" of the hot-pressed member was determined by the following method. The hot-pressed member to be evaluated was punched out, and 3 samples of 48mm phi were taken. Then, the non-evaluation surface on the side opposite to the one on which the adhesion amount was evaluated was masked for each sample. First, each sample was immersed in a 20% aqueous solution of chromium (VI) oxide at room temperature for 10 minutes to dissolve the oxide layer, and each sample was measured. Next, each sample was immersed in a solution of 1L of a 500mL solution of 35% aqueous hydrochloric acid added with 3.5g of hexamethylenetetramine for 120 minutes to dissolve the fe—zn—al—mg alloy plating layer, and each sample was measured again. The amount of adhesion per unit area in each sample was calculated from the difference in mass of the Fe-Zn-Al-Mg alloy plating layer before and after dissolution. Then, the average value of 3 samples was used as the amount of adhesion per one side.
[ Oxide layer ]
The oxide layer in the hot-pressed member of the present embodiment is formed on the fe—zn—al—mg alloy plating layer, and contains Zn, al, and Mg. When hot-pressing a hot-press coated steel sheet having a Zn-Al-Mg alloy plating layer, zn, al and Mg in the plating layer are bonded to oxygen present in a heating atmosphere to form an oxide layer containing Zn, al and Mg. The oxide layer mainly contains Al oxide, contains Zn and Mg contained in the plating layer, and may further contain elements constituting the base steel sheet, such as Fe, mn, and Cr.
In the present embodiment, as a further necessary condition for improving the post-coating corrosion resistance when the hot-pressed member is subjected to the zirconium-based chemical conversion treatment and then to the electrodeposition coating, it is important that the sum of the Al concentration and the Mg concentration of the oxide layer is 28 at% or more. When the sum of the Al concentration and Mg concentration of the oxide layer is less than 28 atomic%, even if the I Γ/Iα is 0.5 or less, the hot-pressed member is subjected to the zirconium-based chemical conversion treatment and then to electrodeposition coating, the post-coating corrosion resistance becomes insufficient. This is presumably because, when the Zn concentration constituting the oxide layer is high, the reaction between the chemical conversion treatment solution and the oxide layer becomes uneven, and the thickness of the zirconium-based chemical conversion coating film formed on the surface of the oxide layer becomes uneven. That is, it is assumed that the adhesion between the oxide layer and the formation treatment film or between the formation treatment film and the coating film is reduced or the coating of the formation treatment film becomes incomplete due to the easy formation of the formation treatment film thinning position. On the other hand, if the sum of the Al concentration and Mg concentration of the oxide layer is 28 atomic% or more, a sound zirconium-based chemical conversion coating film is formed, and therefore excellent post-coating corrosion resistance can be obtained when the hot-pressed member is subjected to the zirconium-based chemical conversion treatment and then electrodeposition coating is performed.
In addition, when the sum of the Al concentration and Mg concentration of the oxide layer is less than 28 atomic%, the oxide layer becomes brittle, and thus the film adhesion becomes insufficient when the hot-pressed member is subjected to the zirconium-based chemical conversion treatment and then the electrodeposition coating is performed. On the other hand, if the sum of the Al concentration and Mg concentration of the oxide layer is 28 atomic% or more, the oxide layer has sufficient strength, and thus the film adhesion becomes good when the hot-pressed member is subjected to the zirconium-based chemical conversion treatment and then the electrodeposition coating is performed.
The upper limit of the sum of the Al concentration and the Mg concentration of the oxide layer is not particularly limited. However, an oxide layer containing Al and Mg at too high concentrations may be chemically stable in an acidic environment such as a chemical conversion treatment liquid for a coating substrate treatment, and may prevent formation of a chemical conversion treatment film. Therefore, the sum of the Al concentration and the Mg concentration of the oxide layer is preferably 50 at% or less.
In this embodiment, since the oxide layer is formed extremely thinly on the fe—zn—al—mg alloy plating layer, as shown in fig. 1, the oxide layer may not be visually recognized in a cross-sectional SEM image. However, the oxide layer can be determined as a region where oxygen is detected by measuring a cross section of a surface layer portion of the hot-pressed member by energy dispersive X-ray analysis (EDX) combined with SEM and performing element mapping. In the present specification, "Al concentration and Mg concentration of the oxide layer" are values measured by the following method. That is, a test piece for cross-section observation was taken from the flat portion of the hot-pressed member. The cross section of the Fe-Zn-Al-Mg alloy plating layer and the oxide layer containing the test piece was observed at 10000 times using a Scanning Electron Microscope (SEM) with an acceleration voltage of 15kV, and the composition of the oxide layer was measured at any 3 places by energy dispersive X-ray analysis (EDX). The average value of the addition of the Al concentration and the Mg concentration at 3 was taken as "Al concentration of oxide layer" and "Mg concentration of oxide layer", respectively.
(Method for manufacturing Hot-pressed Member)
The method for manufacturing a hot-pressed member according to one embodiment of the present invention is characterized in that a hot-pressed plated steel sheet according to one embodiment of the present invention, which will be described later, is heated to a temperature in the range of Ac 3 transformation point to 1000 ℃.
The above-described Fe-Zn-Al-Mg alloy plating layer having an α -Fe phase and a Γ phase and an oxide layer having a predetermined Al concentration and Mg concentration can be obtained by setting the heating temperature of the hot-press steel sheet before hot-pressing to Ac 3 transformation point to 1000 ℃. When the heating temperature is lower than the Ac 3 transformation point, the I Γ/Iα of the Fe-Zn-Al-Mg alloy plating layer exceeds 0.5 after hot pressing. As a result, the hot-pressed member is not sufficiently resistant to corrosion after the electrodeposition coating after the zirconium-based chemical conversion treatment. When the heating temperature exceeds 1000 ℃, a desired oxide layer cannot be obtained, and coating film adhesion and corrosion resistance after coating become insufficient when electrodeposition coating is performed after zirconium-based chemical conversion treatment is performed on the hot-pressed member. The term "heating temperature" as used herein refers to the highest reached temperature of the steel sheet. In the present specification, the "Ac 3 transformation point" is a value calculated by the following formula based on the composition of the steel sheet.
Ac 3 transformation point (C) =910-203C 1/2 +44.7si-4mn+11cr
The symbol of the right element in the formula represents the content of each element, and cr=0 when Cr is not contained.
The holding time after the temperature is raised to the heating temperature is not limited, but is preferably 30 seconds or longer from the viewpoint of eliminating Γ phase and avoiding embrittlement cracking of the liquid metal at the time of hot pressing. The holding time is preferably 5 minutes or less, more preferably 3 minutes or less, and even more preferably 2 minutes or less, from the viewpoint of avoiding hydrogen permeation by water vapor introduced into the furnace during the holding time.
The method for heating the steel sheet for hot pressing is not limited, and examples thereof include furnace heating by an electric furnace or a gas furnace, electric heating, induction heating, high-frequency heating, flame heating, and the like.
In hot pressing, the hot-press coated steel sheet heated as described above is simultaneously press-formed and quenched using a forming die to obtain a hot-pressed member of a predetermined shape. The conditions of the hot pressing are not particularly limited, and a conventional method can be adopted.
(Hot-pressed plated Steel sheet)
The hot-press coated steel sheet according to one embodiment of the present invention is characterized by comprising a base steel sheet and a Zn-Al-Mg alloy plating layer formed on at least one surface of the base steel sheet in an adhesion amount of 30 to 180g/m 2 per one surface, the hot-press coated steel sheet comprising, in mass%, al: 3-10% and Mg:0.2 to 0.8 percent, and the balance of Zn and unavoidable impurities, wherein the liquidus temperature in the atmosphere is below 400 ℃.
[ Base Steel sheet ]
In order to obtain a hot-pressed member having a tensile strength TS of 1470MPa or more, for example, a steel sheet having a composition containing, in mass%, C:0.20 to 0.35 percent of Si:0.1 to 0.5 percent of Mn:1.0 to 3.0 percent, P:0.1% or less, S: less than 0.05%, al:0.1% or less, N: less than 0.01%, and the balance of Fe and unavoidable impurities. The base steel sheet may be either a cold-rolled steel sheet or a hot-rolled steel sheet. The reason for limiting each component element will be described below.
C：0.20～0.35％
C improves strength by forming martensite or the like as a steel structure. In order to obtain TS of 1470MPa or more, the C content is required to be 0.20% or more. On the other hand, when the C content exceeds 0.35%, the toughness of the spot welded portion is deteriorated. Therefore, the C content is preferably 0.20 to 0.35%.
Si：0.1～0.5％
Si is an element effective for strengthening steel to obtain a good material. Therefore, the Si content needs to be 0.1% or more. On the other hand, if the Si content exceeds 0.5%, ferrite stabilizes, and thus hardenability decreases. Therefore, the Si content is preferably 0.1 to 0.5%.
Mn：1.0～3.0％
Mn is an element effective for increasing the strength of steel. In order to secure mechanical properties and strength, the Mn content needs to be 1.0% or more. On the other hand, when the Mn content exceeds 3.0%, surface enrichment increases during annealing, and it is difficult to secure plating adhesion. Therefore, the Mn content is preferably 1.0 to 3.0%.
P: less than 0.1%
If the amount of P exceeds 0.1%, P segregates to austenite grain boundaries during casting, which causes grain boundary embrittlement, and deterioration of local ductility reduces balance between strength and ductility. Therefore, the amount of P is preferably 0.1% or less. In addition, the amount of P is preferably 0.01% or more from the viewpoint of steel-making cost.
S: less than 0.05%
S becomes an inclusion such as MnS, and causes deterioration of impact resistance and cracks in a metal flow along a welded portion. Therefore, the S content is preferably as small as possible, and preferably 0.05% or less. In order to ensure good stretch flangeability, the S content is more preferably 0.01% or less. In addition, from the viewpoint of steel-making cost, the S amount is preferably 0.002% or more.
Al: less than 0.1%
When the Al content exceeds 0.1%, the blanking workability and hardenability of the base steel sheet are lowered. Therefore, the Al content is preferably 0.1% or less. In addition, from the viewpoint of securing the effect as a deoxidizing material, the Al amount is preferably 0.01% or more.
N: less than 0.01%
If the N content exceeds 0.01%, alN is generated during hot rolling and during heating before hot rolling, and punching workability and hardenability of the base steel sheet are lowered. Therefore, the amount of N is preferably 0.01% or less. In addition, the amount of N is preferably 0.001% or more from the viewpoint of steel-making cost.
The remainder other than the above elements is Fe and unavoidable impurities. However, for the following reasons, it may be appropriately contained in mass% as required selected from Nb: less than 0.05%, ti: less than 0.05%, B:0.0002 to 0.005 percent of Cr:0.1 to 0.3 percent of Sb:0.003 to 0.03%.
Nb: less than 0.05%
Nb is an effective component for strengthening steel, but when it is contained in excess, shape freezing property is lowered. Therefore, when Nb is contained, the Nb content is 0.05% or less.
Ti: less than 0.05%
Ti is also effective for strengthening steel as in Nb, but when it is contained in excess, shape freezing property is lowered. Therefore, when Ti is contained, the Ti content is 0.05% or less.
B：0.0002～0.005％
B has an effect of inhibiting the formation and growth of ferrite from austenite grain boundaries. Therefore, the amount of B is preferably 0.0002% or more. On the other hand, when B is added in an excessive amount, moldability is greatly impaired. Therefore, when B is contained, the amount of B is 0.005% or less.
Cr：0.1～0.3％
Cr is useful for improving the strengthening and hardenability of steel. In order to exhibit such an effect, the Cr amount is preferably 0.1% or more. On the other hand, in the case of containing Cr, the amount of Cr is 0.3% or less from the viewpoint of alloy cost.
Sb：0.003～0.03％
Sb has an effect of suppressing decarburization of the surface layer of the steel sheet during hot pressing. In order to exhibit such effects, the Sb amount is preferably 0.003% or more. On the other hand, if the Sb amount exceeds 0.03%, the rolling load increases, and the productivity decreases. Therefore, when Sb is contained, the Sb amount is 0.03% or less.
[ Zn-Al-Mg alloy plating ]
In this embodiment, the Zn-Al-Mg alloy plating layer of the hot-press plated steel sheet has the following composition: contains Al in mass%: 3-10% and Mg:0.2 to 0.8 percent, the rest is Zn and unavoidable impurities, and the liquidus temperature under the atmosphere is below 400 ℃.
Al：3～10％
When the Al content is less than 3%, I Γ/Iα of the fe—zn—al—mg alloy plating layer exceeds 0.5 after hot pressing, and the sum of the Al concentration and Mg concentration of the oxide layer is less than 28 atomic%. As a result, the hot-pressed member is not sufficiently provided with coating film adhesion and corrosion resistance after the electrodeposition coating after the zirconium-based chemical conversion treatment. When the Al content is less than 3%, the liquidus temperature described later cannot be set to 400 ℃ or less by the Mg content. On the other hand, when the Al content exceeds 10%, the liquidus temperature to be described later cannot be set to 400℃or lower, and the I Γ/Iα of the Fe-Zn-Al-Mg alloy plating layer after hot pressing becomes more than 0.5. As a result, the hot-pressed member is not sufficiently resistant to corrosion after the electrodeposition coating after the zirconium-based chemical conversion treatment. Therefore, the Al content is 3 to 10%.
Mg：0.2～0.8％
When the Mg content is less than 0.2%, I Γ/Iα of the fe—zn—al—mg alloy plating layer after hot pressing may exceed 0.5. As a result, the hot-pressed member is not sufficiently resistant to corrosion after the electrodeposition coating after the zirconium-based chemical conversion treatment. Therefore, the Mg content is 0.2% or more, preferably 0.3% or more, and more preferably 0.4% or more. On the other hand, when the Mg content exceeds 0.8%, the sum of the Al concentration and the Mg concentration of the oxide layer after hot pressing becomes less than 28 atomic%. As a result, the hot-pressed member is not sufficiently provided with coating film adhesion and corrosion resistance after the electrodeposition coating after the zirconium-based chemical conversion treatment. Therefore, the Mg content is 0.8% or less, preferably 0.7% or less, and more preferably 0.6% or less.
Liquidus temperature under atmospheric atmosphere: 400 ℃ below
In the present embodiment, it is important to properly control the Al content and Mg content so that the liquidus temperature of the zn—al—mg alloy plating layer in the atmosphere is 400 ℃. When the liquidus temperature exceeds 400 ℃, the I Γ/Iα of the Fe-Zn-Al-Mg alloy plating layer exceeds 0.5 after hot pressing. As a result, the hot-pressed member is not sufficiently resistant to corrosion after the electrodeposition coating after the zirconium-based chemical conversion treatment. The lower limit of the liquidus temperature is not particularly limited, and the liquidus temperature is about 380 ℃ or higher in the above-mentioned range of the Al content and the Mg content. The liquidus temperature of the Zn-Al-Mg alloy layer in the atmosphere can be obtained by calculation using a database by using thermodynamic calculation software Thermo Calc.
The unavoidable impurities contained in the zn—al—mg alloy plating layer include a base steel sheet component introduced into the plating layer by a reaction between the plating bath and the base steel sheet in the plating process, and unavoidable impurities in the plating bath. As a base steel sheet component to be incorporated into the plating layer, fe is contained in an amount of about 0.01% to several%. Examples of the type of unavoidable impurities in the plating bath include Fe, cr, cu, mo, ni, zr. As for Fe in the plating layer, fe introduced from the base steel sheet cannot be distinguished from Fe introduced from the plating bath for quantification. The total content of the unavoidable impurities is not particularly limited, and the total amount of the unavoidable impurities other than Fe is preferably 1 mass% or less in view of uniformly melting the plating layer in the hot pressing step.
The component composition of the Zn-Al-Mg alloy plating layer may further contain at least one selected from Ca, sr, mn, V, cr, mo, ti, ni, co, sb, zr and B in a total amount of 1% by mass or less.
Adhesion amount per side: 30-180 g/m 2
By setting the adhesion amount of the Zn-Al-Mg alloy plating layer to 30 to 180g/m 2, a hot-pressed part excellent in corrosion resistance and resistance to liquid metal embrittlement cracking at the time of hot pressing can be obtained. When the adhesion amount is less than 30g/m 2, a hot-pressed part having a desired corrosion resistance cannot be obtained. If the adhesion amount exceeds 180g/m 2, the alloying may not be completed in the heating step before hot pressing, and a liquid phase may remain, resulting in brittle cracking of the liquid metal. The amount of Zn-Al-Mg alloy plating layer attached is preferably 45g/m 2 or more, more preferably 55g/m 2 or more. The amount of the Zn-Al-Mg alloy plating layer to be deposited is preferably 120g/m 2 or less, more preferably 100g/m 2 or less.
In the present specification, the "amount of adhesion per one surface of the Zn-Al-Mg alloy plating layer" was determined by the following method. The Zn-Al-Mg alloy-plated steel sheet to be evaluated was subjected to punching, 3 samples of 48mm phi were taken, and each sample was measured. Then, the non-evaluation surface on the side opposite to the one on which the adhesion amount was evaluated was masked for each sample. Then, each sample was immersed in a solution of 1L in which 3.5g of hexamethylenetetramine was added and the volume was fixed with 500mL of 35% aqueous hydrochloric acid for 10 minutes, thereby dissolving the Zn-Al-Mg alloy plating layer, and each sample was measured again. The amount of adhesion per unit area in each sample was calculated from the difference in mass of the Zn-Al-Mg alloy plating layer before and after dissolution. Then, the average value of 3 samples was used as the amount of adhesion per one side.
In the present embodiment, a separate coating may be provided on the lower layer or the upper layer of the zn—al—mg alloy plating layer as required within a range that does not affect the operational effect of the present invention. As the lower coating film, a nickel pre-coating film can be exemplified. Examples of the upper layer film include a formation treatment film containing zirconium oxide or zirconium-titanium oxide.
Examples
As the base steel sheet, a cold-rolled steel sheet (Ac 3 =814℃) having a sheet thickness of 1.4mm with a composition containing, in mass%, C:0.23%, si:0.25%, mn:1.2%, P:0.005%, S:0.001%, al:0.03%, N:0.004%, nb:0.02%, ti:0.02%, B:0.002%, cr:0.2% and Sb:0.008%, the remainder being Fe and unavoidable impurities.
The cold-rolled steel sheet was immersed in a zn—al—mg hot dip coating bath having a predetermined composition and bath temperature using a hot dip plating apparatus, and then, was subjected to nitrogen wiping to produce hot press coated steel sheets of levels nos. 1 to 14 shown in table 1. Table 1 shows the Al content, the Mg content, the content of other elements, and the liquidus temperature in the atmosphere in the Zn-Al-Mg alloy plating layer. The content of each element and the liquidus temperature are controlled by adjusting the composition of the plating bath. The content of each element in the plating layer was obtained by quantitatively analyzing each component contained in the hydrochloric acid stripping solution of the plating layer by ICP-AES. The liquidus temperature of the plating layer was obtained by the method described above. Table 1 also shows the amount of adhesion per surface of the zn—al—mg alloy plating layer obtained by the above-described method. The plating deposit amount is controlled by adjusting the flow rate and linear velocity of the wiping gas.
Next, the hot-pressing steel sheet is hot-pressed. That is, 150mm×300mm test pieces were collected from the obtained steel sheet for hot pressing, and heat-treated with an electric furnace. The heat treatment conditions (heating temperature, holding time) are shown in table 1. The test piece after the heat treatment was taken out of the electric furnace, and immediately hot-pressed using a cap die at a molding start temperature of 700 ℃. The shape of the obtained hot-pressed member was 100mm in length of the flat portion on the upper surface, 50mm in length of the flat portion on the side surface, and 50mm in length of the flat portion on the lower surface. The bending radius R of the die was 7R at both shoulders of the upper surface and both shoulders of the lower surface.
(Evaluation of Fe-Zn-Al-Mg alloy coating/oxide layer of Hot-pressed Member)
A test piece for cross-section observation was taken from a flat portion of the upper surface of the obtained hot-pressed member, and SEM observation was performed on the cross section of the Fe-Zn-Al-Mg alloy plating layer. The α -Fe phase and Γ phase have significantly different contrast in the cross-sectional SEM image at each level and can therefore be identified separately. Fig. 1 shows a cross-sectional SEM image of the fe—zn—al—mg alloy plating layer of the hot-pressed member of No.2 as represented by an inventive example, and fig. 2 shows a cross-sectional SEM image of the fe—zn—al—mg alloy plating layer of the hot-pressed member of No.8 as represented by a comparative example. In fig. 1, precipitation of Γ phase is suppressed, and Γ phase is discontinuously dispersed in α -Fe phase. In contrast, in fig. 2, the Γ phase is largely precipitated, and the Γ phase exists in a continuous plane shape. In addition, co-K alpha (wavelength) with an incidence angle of 25 DEG) The intensities I Γ of the diffraction peak of the (411) crystal plane of the gamma-phase existing at 41.5.ltoreq.2θ.ltoreq.43.0° and the intensities I α of the diffraction peak of the (110) crystal plane of the alpha-Fe phase existing at 51.0.ltoreq.2θ.ltoreq.52.0° were measured for the X-ray diffraction of the radiation source, respectively, and the ratios I Γ/Iα are shown in Table 1. The X-ray diffraction was measured using a curved IPX-ray diffraction apparatus (RINT-RAPID II-R manufactured by Rigaku corporation) under conditions of a tube voltage of 45kV, a tube current of 160mA, an integration time of 600 seconds, and a collimator diameter of 3mm.
The Al concentration and Mg concentration of the oxide layer were measured by the methods described above at each level, and are shown in table 1. The amount of adhesion of each surface of the Fe-Zn-Al-Mg alloy plating layer was measured by the method described above, and is shown in Table 1.
(Evaluation 1: adhesion of coating film)
From the flat portion of the upper surface of the obtained hot-pressed member, a test piece of 70mm×150mm was cut, and zirconium-based chemical conversion treatment was performed on the test piece. Specifically, a commercially available chemical conversion treatment liquid (zirconium-based chemical conversion treatment: palmyna (pni 2100) manufactured by Nihon Parkerizing co.) was used at a bath temperature: 35 ℃, treatment time: the condition of 120 seconds is subjected to the formation process. Then, each test piece was subjected to energization using a commercial cationic electrodeposition paint for 30 seconds and held at a constant voltage for 150 seconds under a voltage condition that the thickness of the coating film after the sintering was 15 μm, and the sintering was performed in an electric furnace at an atmosphere temperature of 170℃for 20 minutes. As the cationic electrodeposition paint, ELECTRON GT to 100V-1 ash of Guangxi paint system was used.
The test pieces after electrodeposition coating were cut out with a cutter at 1mm intervals in the longitudinal and transverse directions to obtain 11 cuts reaching the base steel plate, respectively, to prepare 100 checkerboards. The Cellophane tape (registered trademark) was strongly pressed against the checkerboard portion, and one end of the tape was peeled off at a time at an angle of 45 °. The number of the coating films peeled from the test piece surface was measured, and the test piece was evaluated as good or good according to the following criteria. The evaluation results are shown in table 1.
And (3) the following materials: number of stripping grids=0
O: number of stripping grids=1
Delta: number of stripping grids=2 to 5
X: number of stripping grids is more than 5
(Evaluation 2: corrosion resistance after coating)
Test pieces were prepared by the same method as in evaluation 1, and the end of the evaluation surface was sealed with an adhesive tape of 7.5mm and the non-evaluation surface (back surface). Then, a cross cut having a length of 60mm and a center angle of 60 ° was applied to the center of the evaluation surface with a cutter until the depth of the base steel sheet was reached. The test piece was subjected to corrosion test (VDA 233-102) and evaluated according to the corrosion condition after 4 weeks.
The maximum expansion width at one side from the cross cut was measured, and the judgment was made according to the following criteria, and was evaluated as pass. The evaluation results are shown in table 1.
And (3) the following materials: the maximum expansion width of one side is less than 1.5mm
O: the maximum expansion width of the single side is less than or equal to 1.5mm and less than 3.0mm
Delta: the maximum expansion width of the single side is less than or equal to 3.0mm and less than 4.0mm
X: 4.0mm is less than or equal to the unilateral maximum expansion width
TABLE 1
The results in table 1 show that the hot-pressed member of the example of the present invention is excellent in film adhesion and corrosion resistance after coating when electrodeposition coating is performed after zirconium-based chemical conversion treatment.
Industrial applicability
The hot-pressed part of the present invention is suitable for chassis parts and body structural parts of automobiles.
Claims (3)
1. A hot-pressed member has a base steel sheet, an Fe-Zn-Al-Mg alloy plating layer, and an oxide layer,
The Fe-Zn-Al-Mg alloy plating layer is formed on at least one side of the base steel sheet in an adhesion amount of 40-400 g/m 2 per side and contains an alpha-Fe phase and a gamma-phase,
The oxide layer is formed on the Fe-Zn-Al-Mg alloy plating layer and contains Zn, al and Mg,
The ratio I Γ/Iα of the intensity I Γ of the diffraction peak of the (411) crystal face of the gamma-phase existing at 41.5 DEG.ltoreq.2θ.ltoreq.43.0 DEG obtained by X-ray diffraction with Co-Kα at an incident angle of 25 DEG as a radiation source to the intensity I α of the diffraction peak of the (110) crystal face of the alpha-Fe phase existing at 51.0 DEG.ltoreq.2θ.ltoreq.52.0 DEG is 0.5 or less, wherein the wavelength of Co-Kα is
The sum of the Al concentration and the Mg concentration of the oxide layer is 28 atomic% or more.
2. A method for producing a hot-pressed member, characterized by heating the hot-pressed coated steel sheet to a temperature in the range of Ac 3 transformation point to 1000 ℃ and hot-pressing to produce the hot-pressed member according to claim 1,
The hot-press coated steel sheet has a base steel sheet and a Zn-Al-Mg alloy plating layer,
The Zn-Al-Mg alloy plating layer is formed on at least one surface of the base steel sheet in an adhesion amount of 30-180 g/m 2 per surface, and contains, in mass%, al: 3-10% and Mg:0.2 to 0.8 percent, and the balance of Zn and unavoidable impurities, wherein the liquidus temperature in the atmosphere is below 400 ℃.
3. The method for producing a hot-pressed member according to claim 2, wherein the component composition of the Zn-Al-Mg alloy plating layer further contains at least one selected from Ca, sr, mn, V, cr, mo, ti, ni, co, sb, zr and B in a total amount of 1% by mass or less.
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| JP2020-036054 | 2020-03-03 | ||
| JP2020036054 | 2020-03-03 | ||
| PCT/JP2020/040696 WO2021176768A1 (en) | 2020-03-03 | 2020-10-29 | Hot-pressed member, method for manufacturing same, and plated steel sheet for hot pressing |
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| US (1) | US20230095166A1 (en) |
| EP (1) | EP4116457B1 (en) |
| JP (1) | JP7056799B2 (en) |
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- 2020-10-29 JP JP2021510138A patent/JP7056799B2/en active Active
- 2020-10-29 US US17/905,277 patent/US20230095166A1/en active Pending
- 2020-10-29 KR KR1020227023141A patent/KR102666358B1/en active IP Right Grant
- 2020-10-29 CN CN202080095524.7A patent/CN115053009B/en active Active
- 2020-10-29 WO PCT/JP2020/040696 patent/WO2021176768A1/en active Application Filing
- 2020-10-29 EP EP20923408.7A patent/EP4116457B1/en active Active
- 2020-10-29 MX MX2022010448A patent/MX2022010448A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| US20230095166A1 (en) | 2023-03-30 |
| EP4116457B1 (en) | 2024-05-08 |
| EP4116457A4 (en) | 2023-01-11 |
| CN115053009A (en) | 2022-09-13 |
| EP4116457A1 (en) | 2023-01-11 |
| JP7056799B2 (en) | 2022-04-19 |
| WO2021176768A1 (en) | 2021-09-10 |
| MX2022010448A (en) | 2022-09-19 |
| JPWO2021176768A1 (en) | 2021-09-10 |
| KR20220109459A (en) | 2022-08-04 |
| KR102666358B1 (en) | 2024-05-14 |
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