US20210156012A1 - Steel strip, sheet or blank for producing a hot formed part, part, and method for hot forming a blank into a part - Google Patents
Steel strip, sheet or blank for producing a hot formed part, part, and method for hot forming a blank into a part Download PDFInfo
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- US20210156012A1 US20210156012A1 US16/633,198 US201816633198A US2021156012A1 US 20210156012 A1 US20210156012 A1 US 20210156012A1 US 201816633198 A US201816633198 A US 201816633198A US 2021156012 A1 US2021156012 A1 US 2021156012A1
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 139
- 239000010959 steel Substances 0.000 title claims abstract description 139
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 claims description 40
- 238000001816 cooling Methods 0.000 claims description 29
- 238000005452 bending Methods 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 13
- 229910000734 martensite Inorganic materials 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910001563 bainite Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 description 18
- 239000011651 chromium Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 10
- 239000010955 niobium Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910001566 austenite Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000712 Boron steel Inorganic materials 0.000 description 2
- 229910000885 Dual-phase steel Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000007656 fracture toughness test Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910001562 pearlite Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000169624 Casearia sylvestris Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000161 steel melt Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- 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
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
-
- 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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- 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
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- 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
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- 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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- 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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- 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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- 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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- 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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- 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
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- 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
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—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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- 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
- B21D22/02—Stamping using rigid devices or tools
- B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
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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
- 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
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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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
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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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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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
- 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
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- 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
Definitions
- the present invention relates to a steel strip, sheet or blank for producing a hot formed part; a hot formed part; and a method for producing a hot formed part.
- a steel typically used for hot-forming is 22MnB5 steel.
- This boron steel can be furnace-heated and is usually austenitized between 870-940° C., transferred from furnace to forming tool, and stamped into the desired part geometry, while the part is at the same time cooled.
- the advantage of such boron steel parts produced this way is that they display a high ultimate tensile strength for anti-intrusive crashworthiness due to their fully martensitic microstructure, but at the same time they display a low ductility and bendability which in turn results in a limited toughness and thus a poor impact-energy absorptive crashworthiness.
- Fracture toughness measurement is an useful tool to indicate the crash energy absorption of steels. When the fracture toughness parameters are high, generally a good crash behavior is obtained.
- Yet another object of the present invention is to provide a method for hot-forming a steel blank into a part.
- the present invention relates to a steel strip, sheet or blank for producing hot formed parts having the following composition in weight %:
- the hot formed part produced from the steel strip, sheet or blank in accordance with the present invention displays an improved combination of tensile strength, ductility and bendability, and thereby impact toughness when compared to conventional hot-formed boron steels.
- the two steel blanks are joined by laser welding before hot stamping and then the hybrid blank is stamped into the B-pillar.
- the invented higher strength steel can replace the lower strength steel of the lower part with a higher energy absorption capability.
- the steel strip, sheet or blank for producing hot formed parts as described above has the following composition in weight %:
- Mn 1.0-2.1, preferably 1.2-1.8, and/or
- Nb 0.02-0.08, preferably 0.03-0.07, and/or
- N 0.001-0.008, preferably 0.002-0.005
- Si ⁇ 0.1, preferably ⁇ 0.05
- Al ⁇ 0.1, preferably ⁇ 0.05,
- Cu ⁇ 0.1, preferably ⁇ 0.05
- V ⁇ 0.15, preferably ⁇ 0.05
- Carbon is added for securing good mechanical properties.
- C is added in an amount of 0.03 wt % or more to achieve high strength and to increase the hardenability of the steel. When too much carbon is added there is the possibility that the toughness and weldability of the steel sheet will deteriorate.
- the C amount used in accordance with the invention is therefore in the range of from 0.03-0.17 wt %, preferably in the range of from 0.05-0.17 wt %, and more preferably in the range of from 0.07-0.15 wt %.
- Mn is used because it promotes hardenability and gives solid solution strengthening.
- the Mn content is at least 0.65 wt % to provide adequate substitutional solid solution strengthening and adequate quench hardenability, while minimising segregation of Mn during casting and while maintaining sufficiently low carbon equivalent for automotive resistance spot-welding techniques.
- Mn is an element that is useful in lowering the Ac 3 temperature. A higher Mn content is advantageous in lowering the temperature necessary for hot press forming. When the Mn content exceeds 2.5 wt %, the steel sheet may suffer from poor weldability and poor hot and cold rolling characteristics that affect the steel processability.
- the Mn amount used in accordance with the invention is in the range of from 0.65-2.5 wt %, preferably in the range of from 1.0-2.1 wt %, and more preferably in the range of from 1.2-1.8 wt %.
- Chromium improves the hardenability of the steel and facilitates avoiding the formation of ferrite and/or pearlite during press quenching. In this respect it is observed that the presence of ferrite and/or pearlite in the microstructure is detrimental to mechanical properties for the targeted microstructure in this invention.
- the amount of Cr used in the invention is in the range of from 0.2-2.0 wt %, preferably in the range of from 0.5-1.7 wt %, more preferably in the range of 0.8-1.5 wt %.
- manganese and chromium are used in such an amount that Mn+Cr ⁇ 2.7, preferably Mn+Cr is in the range of from 0.5-2.5, and more preferably Mn+Cr is in the range of from 2.0-2.5.
- Titanium is added to form TiN precipitates to scavenge out N at high temperatures while the steel melt cools. Formation of TiN prohibits formation of B 3 N 4 at lower temperatures so that B, which is also an essential element for this invention, becomes more effective. Stoichiometrically, the ratio of Ti to N (Ti/N) addition should be >3.42.
- the amount of titanium is in the range of from 0.01-0.1 wt %, preferably in the range of from 0.015-0.07 wt %, and more preferably in the range of from 0.025-0.05 wt %.
- Niobium has the effect of forming strengthening precipitates and refining microstructure.
- Nb increases the strength by means of grain refinement and precipitation hardening. Grain refinement results in a more homogeneous microstructure improving the hot-forming behavior, in particular when high localized strains are being introduced. A fine, homogeneous microstructure also improves the bending behavior.
- the amount of Nb used in the invention is in the range of from 0.01-0.1 wt %, preferably in the range of from 0.02-0.08 wt %, and more preferably in the range of from 0.03-0.07 wt %.
- Boron is an important element for increasing the hardenability of steel sheets and for further increasing the effect of stably guaranteeing strength after quenching.
- B is present in an amount in the range of from 0.0005-0.005 wt %, preferably in the range of from 0.0005-0.004 wt %, more preferably in the range of from 0.001-0.003 wt %.
- N has an effect similar to C.
- N is suitably combined with titanium to form TiN precipitates.
- the amount of N according to the invention is at most 0.01 wt %.
- the amount of N is in the range of 0.001-0.008 wt %.
- N is present in an amount in the range of from 0.002-0.005 wt %.
- Mn, Cr and B are used in such amounts that (B ⁇ 1000)/(Mn+Cr) is in the range of from 0.185-2.5, preferably in the range of from 0.2-2.0, and more preferably in the range of from 0.5-1.5.
- the (B ⁇ 1000)/(Mn+Cr) ratio as applied in accordance with the present invention establishes an adequate hardenability of the steel.
- Silicon is also added to promote hardenability and adequate substitutional solid solution strengthening.
- the Si amount used in the invention is at most 0.1 wt %, preferably at most 0.5 wt %.
- Aluminium is added to deoxidize the steel.
- the Al amount is at most 0.1 wt %, preferably at most 0.05 wt %.
- Molybdenum is added to improve the hardenability of the steel and facilitate the formation of bainite.
- the Mo amount used in accordance with the invention is at most 0.1 wt %, preferably at most 0.05 wt %.
- Copper is added to improve hardenability and increase strength of the steel. If present, Cu is used in accordance with the invention in an amount of at most 0.1 wt %, preferably at most 0.05 wt %.
- P is known to widen the intercritical temperature range of a steel. P is also an element useful for maintaining desired retained austenite. However, P may deteriorate the workability of the steel. In accordance with the invention P should be present in an amount of at most 0.03 wt %, preferably at most 0.015 wt %.
- the amount of sulphur needs to be minimised to reduce harmful non-metallic inclusions.
- S forms a sulfide based inclusions such as MnS, which initiates crack, and deteriorates processability. Therefore, it is desirable to reduce the S amount as much as possible.
- the amount of S is at most 0.025 wt %, preferably an amount of at most 0.01 wt %.
- the amount of 0 is at most 0.01 wt %, preferably at most 0.005 wt %.
- Vanadium may be added to form V(C, N) precipitates to strengthen the steel product.
- the amount of vanadium, if any, is at most 0.15 wt %, preferably at most 0.05 wt %.
- Nickel may be added in an amount of at most 0.15 wt %. Ni can be added to increase the strength and toughness of the steel.
- Calcium may be present in an amount of up to 0.05 wt %, preferably up to 0.01 wt %. Ca is added to spheroidize the sulphur containing inclusions and to minimize the amount of elongated inclusions. However, the presence of CaS inclusions will still lead to inhomogeneities in the matrix; it is thus best to reduce the amount of S.
- 1000*B divided by the sum of Mn and Cr has to be between 0.185 and 2.5, preferably between 0.5 and 1.5. This limitation improves the hardenability of the steel.
- the steel strip, sheet or blank is provided with a zinc based coating, an aluminium based coating or an organic based coating.
- a zinc based coating reduces oxidation and/or decarburization during a hot forming process.
- the zinc based coating is a coating containing 0.2-5.0 wt % Al, 0.2-5.0 wt % Mg, optionally at most 0.3 wt % of one or more additional elements, the balance being zinc and unavoidable impurities.
- the additional elements can be selected from the group comprising Pb or Sb, Ti, Ca, Mn, Sn, La, Ce, Cr, Ni, Zr or Bi. Pb, Sn, Bi and Sb are usually added to form spangles.
- the total amount of additional elements in the zinc alloy is at most 0.3 wt. %. These small amounts of an additional element do not alter the properties of the coating nor the bath to any significant extent for the usual applications.
- each is preferably present in an amount of at most 0.03 wt %, preferably each is present in an amount of at most 0.01 wt %. Additional elements are usually only added to prevent dross forming in the bath with molten zinc alloy for the hot dip galvanizing, or to form spangles in the coating layer.
- the hot formed part produced from a steel strip, sheet or blank in accordance with the present invention has a microstructure comprising at most 60% bainite, the remainder being martensite.
- the microstructure comprises at most 50 vol. % of bainite, the remainder being martensite. More preferably, the microstructure comprises at most 40 vol. % of bainite, the remainder being martensite.
- the martensite provides a high strength, whereas the softer bainite improves the ductility. The small strength difference between martensite and bainite helps in maintaining a high bendability due to lack of weak phase interfaces.
- the hot formed part in accordance with the present invention displays excellent mechanical properties.
- the part has a tensile strength (TS) of at least 750 MPa, preferably of at least 800 MPa, more preferably of at least 900 MPa, and further has a tensile strength of at most 1400 MPa.
- TS tensile strength
- the part suitably has a total elongation (TE) of at least 5%, preferably 5.5%, more preferably at least 6% and most preferably at least 7%, and/or a bending angle (BA) at 1.0 mm thickness of at least 100°, preferably at least 115°, more preferably at least 130° and most preferably at least 140°.
- TE total elongation
- BA bending angle
- the present invention also relates to the use of hot formed parts as described above, as structural part in the body-in-white of a vehicle.
- Such parts are made of the present steel strip, sheet or blank. These parts have a high strength, high ductility and a high bendability.
- parts in the form of structural parts of vehicles are very attractive since they exhibit excellent crash energy absorption and in turn, down-gauging and lightweighting opportunities based on crashworthiness compared to the use of conventional hot-formed boron steels and cold-formed multiphase steels.
- the present invention also relates to a method for producing a part in accordance with the present invention.
- the present invention also relates to a method for hot-forming a steel blank or a preformed part into an part comprising the steps of:
- the part After the cooling of the part to a temperature below the Mf temperature, the part can for instance be further cooled to room temperature in air, or can be forcibly cooled to room temperature.
- the blank to be heated in step (a) is provided as an intermediate for the subsequent steps.
- the steel strip or sheet from which the blank is produced can be obtained by standard casting processes.
- the steel strip or sheet is cold-rolled.
- the steel strip or sheet can suitably be cut to a steel blank.
- a preformed steel part may also be used. The preformed part may be partially or entirely formed into the desired geometry, preferably at ambient temperature.
- the steel blank is heated in step (a) to a temperature T 1 for a time period t 1 .
- the temperature T 1 is 50-100° C. higher than the Ac 3 temperature of the steel, and/or the temperature T 2 is above the Ar 3 temperature.
- T 1 is 50-100° C. above the Ac 3 temperature
- the steel is fully or almost fully austenitized within the time period t 1 , and the cooling during step (b) is easily possible.
- the microstructure is a homogenous austenitic microstructure the formability is enhanced.
- the time period t 1 is at least 1 minute and at most 7 minutes. Too long a time period t 1 may result in coarse austenitic grains, which will deteriorate the final mechanical properties
- the heating apparatus to be used in step (a) may for instance be an electric or gas powered furnace, electrical resistance heating device, infra-red induction heating device.
- step (b) the heated steel blank or preformed part is transferred to a hot-forming tool during a transport time t 2 during which the temperature of the heated steel blank or preformed part decreases from temperature T 1 to a temperature T 2 , wherein the transport time t 2 is at most 20 seconds.
- Time t 2 is the time needed to transport the heated blank from the heating apparatus to the hot-forming tool (e.g. press) and till the hot-forming apparatus is closed.
- the transfer of the blank or preformed part may cool from temperature T 1 to temperature T 2 by the act of natural air-cooling and/or any other available cooling method.
- the heated blank or preformed part may be transferred from the heating apparatus to the forming tool by an automated robotic system or any other transfer method.
- Time t 2 may also be chosen in combination with T 1 , t 1 and T 2 in order to control the microstructural evolution of steel at the commencement of forming and quenching.
- t 2 is equal or less than 12 seconds, preferably t 2 is equal or less than 10 s, more preferably t 2 is equal or less than 8 s, and most preferably equal or less than 6 s.
- the blank or preformed part can be cooled from temperature T 1 to a temperature at a cooling rate V 2 of at least 10° C./s.
- V 2 is preferably in the range of from 10-15° C./s.
- the cooling rate should be higher, for instance at least 20° C./s, up to 50° C./s or more.
- step (c) a heated blank or preformed part is formed into a part having the desired geometry.
- the formed part is preferably a structural part of a vehicle.
- step (d) the formed part in the hot-forming tool is cooled to a temperature below the Mf temperature of the steel with a cooling rate V 3 of at least 30° C./s.
- the cooling rate V 3 in step (d) is in the range of from 30-150° C./s, more preferably in the range of from 30-100° C./s.
- the present invention provides an improved method of introducing during hot-forming operation the desired bainitic phase into the steel microstructure.
- the present method enables the production of hot formed steel parts displaying an excellent combination of high strength, high ductility and high bendability.
- One or more steps of the method according to the present invention may be conducted in a controlled inert atmosphere of hydrogen, nitrogen, argon or any other inert gas in order to prevent oxidation and/or decarburisation of said steel.
- FIG. 1 shows a schematic representation of an embodiment of the method according to the invention.
- FIG. 2 shows a cross-section through a drop tower for axial crash tests.
- the horizontal axis represents the time t
- the vertical axis represents the temperature T.
- the time t and temperature T are indicated diagrammatically in FIG. 1 . No values can be derived from FIG. 1 .
- a steel blank or preformed part is (re)heated up to the austenitizing temperature above Ac 1 at a particular (re)heating rate. Once the Ac 1 has been exceeded the (re)heating rate is lowered until the blank or preformed part has reached a temperature higher than the Ac 3 . Then the strip, sheet or blank is held at this particular temperature for a period of time. Subsequently, the heated blank is transferred from the furnace to the hot forming tool, during which cooling of the blank by air occurs to some extent. The blank or preformed part is then hot-formed into a part and cooled down (or quenched) at a cooling rate of at least 30° C./s. After reaching a temperature below the Mf temperature of the steel, the hot-forming tool is opened and the formed article is cooled down to room temperature.
- Steel blanks with dimensions of 220 mm ⁇ 110 mm ⁇ 1.5 mm were prepared from a cold-rolled steel sheet having the composition as shown in Table 1. These steel blanks were subjected to hot forming thermal cycles in a hot dip annealing simulator (HDAS) and an SMG press. The HDAS was used for slower cooling rates (30-80° C./s) whereas the SMG press was used for fastest cooling rate (200° C./s). The steel blanks were reheated to a T 1 of respectively 900° C. (36° C. above Ac 3 ) and 940° C. (76° C. above Ac 3 ), soaked for 5 min. in nitrogen atmosphere to minimize surface degradation. The blanks were then subjected to transfer cooling for a drop in temperature of 120° C.
- HDAS hot dip annealing simulator
- SMG press was used for fastest cooling rate (200° C./s).
- the steel blanks were reheated to a T 1 of respectively 900° C. (36° C. above Ac 3 )
- the samples with bending axis parallel to the rolling direction were identified as longitudinal (L) bending specimens whereas those with bending axis perpendicular to the rolling direction were denoted as perpendicular (T) bending specimens.
- J-integral fracture toughness and drop tower axial crash tests were conducted.
- Compact tension specimens according to NFMT76J standard were prepared from both longitudinal and transverse directions for fracture toughness tests.
- the specimens were tested according to ASTM E1820-09 standard at room temperature.
- the pre-cracks were introduced by fatigue loading.
- the final tests were done with tensile loading with anti-buckle plates to keep the stress in plane for sheet material.
- CTOD is the Crack Tip Opening Displacement and is a measure of how much the crack opens at either failure (if brittle) or maximum load.
- J is the J-integral and is a measure of toughness that takes account of the energy, so it is calculated from the area under the curve up to failure or maximum load.
- K q is the value of stress intensity factor measured at load P q , where P q is determined by taking the elastic slope of the loading line, then taking a line with 5% less slope and defining P q as the load where this straight line intersects the loading line.
- Drop tower axial crash tests were done in SMG-pressed condition with a load of 200 kg and a loading speed of 50 km/hour for the load to hit the crash boxes having a closed top hat geometry ( FIG. 2 ) with 500 mm height (transverse to the rolling direction).
- the back plates of 100 mm width were spot-welded to the profiles to prepare the crash boxes.
- Table 3 the yield strength (YS), ultimate tensile strength (UTS), uniform elongation (UE), and total elongation (TE) are shown for steel composition A after a variety of cooling rates V 3 .
- Table 3 shows the microstructure in terms of martensite (M) and bainite (B). It will be clear from Table 3 that an ultimate tensile strength of greater than 800 MPa was achieved at the different cooling rates V 3 .
- the high and improved crash behavior of hot formed steel composition A in accordance with the present invention when compared to the conventional steel products of similar strength is due to the higher bending angle and higher fracture toughness properties.
- the steel component need to fold which is determined by its bendability, whereas on the other hand the energy absorption capability before failure is determined by its fracture toughness parameters.
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Applications Claiming Priority (5)
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EP17183092.0 | 2017-07-25 | ||
EP17183092 | 2017-07-25 | ||
EP17186911 | 2017-08-18 | ||
EP17186911.8 | 2017-08-18 | ||
PCT/EP2018/069939 WO2019020575A1 (fr) | 2017-07-25 | 2018-07-23 | Bande, tôle ou ébauche en acier pour la fabrication d'une pièce formée à chaud, et procédé de formage à chaud d'une ébauche pour former une pièce |
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US20210156012A1 true US20210156012A1 (en) | 2021-05-27 |
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US16/633,198 Abandoned US20210156012A1 (en) | 2017-07-25 | 2018-07-23 | Steel strip, sheet or blank for producing a hot formed part, part, and method for hot forming a blank into a part |
Country Status (8)
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US (1) | US20210156012A1 (fr) |
EP (1) | EP3658692B1 (fr) |
JP (1) | JP7326247B2 (fr) |
KR (2) | KR20240142610A (fr) |
BR (1) | BR112020000917A2 (fr) |
ES (1) | ES2899238T3 (fr) |
MX (1) | MX2020000928A (fr) |
WO (1) | WO2019020575A1 (fr) |
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KR20220013393A (ko) * | 2019-05-28 | 2022-02-04 | 타타 스틸 이즈무이덴 베.뷔. | 열간-스탬프 부품을 생산하기 위한 강철 스트립, 시트 또는 블랭크, 열간-스탬프 부품, 및 블랭크를 부품으로 열간-스탬핑하는 방법 |
KR20220102651A (ko) * | 2020-01-16 | 2022-07-20 | 닛폰세이테츠 가부시키가이샤 | 핫 스탬프 성형체 |
KR102345608B1 (ko) * | 2020-12-23 | 2021-12-30 | 현대제철 주식회사 | 핫 스탬핑 부품, 및 이의 제조 방법 |
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SE435527B (sv) | 1973-11-06 | 1984-10-01 | Plannja Ab | Forfarande for framstellning av en detalj av herdat stal |
FR2735148B1 (fr) | 1995-06-08 | 1997-07-11 | Lorraine Laminage | Tole d'acier laminee a chaud a haute resistance et haute emboutissabilite renfermant du niobium, et ses procedes de fabrication. |
JP4449795B2 (ja) * | 2005-03-22 | 2010-04-14 | 住友金属工業株式会社 | 熱間プレス用熱延鋼板およびその製造方法ならびに熱間プレス成形部材の製造方法 |
JP5586008B2 (ja) | 2007-02-23 | 2014-09-10 | タタ、スティール、アイモイデン、ベスローテン、フェンノートシャップ | 強度が非常に高い最終製品の熱機械的成形方法およびその方法により製造された製品 |
DK2434027T3 (en) | 2009-05-22 | 2015-12-07 | Jfe Steel Corp | Steel materials for welding with high heat input |
MX2012014594A (es) | 2010-06-14 | 2013-02-21 | Nippon Steel & Sumitomo Metal Corp | Articulo moldeado y estampado en caliente, proceso para produccion de placa de acero para estampado en caliente, y proceso para produccion de un articulo moldeado y estampado en caliente. |
MX359051B (es) * | 2010-10-22 | 2018-09-13 | Nippon Steel & Sumitomo Metal Corp | Proceso para producir un artículo moldeado por estampación en caliente, y artículo moldeado por estampación en caliente. |
WO2013149734A1 (fr) | 2012-04-05 | 2013-10-10 | Tata Steel Ijmuiden B.V. | Bande d'acier ayant une faible teneur en si |
DE102013009232A1 (de) | 2013-05-28 | 2014-12-04 | Salzgitter Flachstahl Gmbh | Verfahren zur Herstellung eines Bauteils durch Warmumformen eines Vorproduktes aus Stahl |
CA2924812A1 (fr) * | 2013-09-19 | 2015-03-26 | Tata Steel Ijmuiden B.V. | Acier pour le formage a chaud |
EP2851440A1 (fr) * | 2013-09-19 | 2015-03-25 | Tata Steel IJmuiden BV | Acier pour formage à chaud |
JP6303580B2 (ja) * | 2014-02-19 | 2018-04-04 | 新日鐵住金株式会社 | 熱処理用鋼板およびその製造方法 |
WO2015144318A1 (fr) | 2014-03-28 | 2015-10-01 | Tata Steel Ijmuiden B.V. | Procédé de formage à chaud d'une pièce brute d'acier enduit |
TWI563101B (en) * | 2014-05-15 | 2016-12-21 | Nippon Steel & Sumitomo Metal Corp | Hot-formed steel sheet member |
CA2979923A1 (fr) * | 2015-03-16 | 2016-09-22 | Tata Steel Ijmuiden B.V. | Acier pour formage a chaud |
WO2017006144A1 (fr) | 2015-07-09 | 2017-01-12 | Arcelormittal | Acier pour trempe à la presse et pièce trempée à la presse fabriquée à partir d'un tel acier |
JP6606897B2 (ja) * | 2015-07-16 | 2019-11-20 | 日本製鉄株式会社 | 熱処理用鋼板およびその製造方法と、ホットスタンプ成形品 |
JP2018532045A (ja) | 2015-09-22 | 2018-11-01 | タタ、スティール、アイモイデン、ベスローテン、フェンノートシャップTata Steel Ijmuiden Bv | 優れた伸びフランジ成形性を有するロール成形可能な高強度熱間圧延鋼板、および該鋼の製造方法 |
KR20170075046A (ko) * | 2015-12-22 | 2017-07-03 | 주식회사 포스코 | 내식성이 우수한 열간 프레스 성형품 및 그 제조방법 |
-
2018
- 2018-07-23 MX MX2020000928A patent/MX2020000928A/es unknown
- 2018-07-23 WO PCT/EP2018/069939 patent/WO2019020575A1/fr active Search and Examination
- 2018-07-23 JP JP2020503872A patent/JP7326247B2/ja active Active
- 2018-07-23 EP EP18740258.1A patent/EP3658692B1/fr active Active
- 2018-07-23 KR KR1020247031235A patent/KR20240142610A/ko unknown
- 2018-07-23 BR BR112020000917-2A patent/BR112020000917A2/pt not_active Application Discontinuation
- 2018-07-23 ES ES18740258T patent/ES2899238T3/es active Active
- 2018-07-23 KR KR1020207001858A patent/KR20200035259A/ko not_active IP Right Cessation
- 2018-07-23 US US16/633,198 patent/US20210156012A1/en not_active Abandoned
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JP2020528963A (ja) | 2020-10-01 |
JP7326247B2 (ja) | 2023-08-15 |
EP3658692A1 (fr) | 2020-06-03 |
BR112020000917A2 (pt) | 2020-07-21 |
KR20240142610A (ko) | 2024-09-30 |
WO2019020575A1 (fr) | 2019-01-31 |
EP3658692B1 (fr) | 2021-11-10 |
KR20200035259A (ko) | 2020-04-02 |
MX2020000928A (es) | 2020-07-22 |
ES2899238T3 (es) | 2022-03-10 |
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