US20130209833A1 - Hot-rolled or cold-rolled steel plate, method for manufacturing same, and use thereof in the automotive industry - Google Patents
Hot-rolled or cold-rolled steel plate, method for manufacturing same, and use thereof in the automotive industry Download PDFInfo
- Publication number
- US20130209833A1 US20130209833A1 US13/880,929 US201113880929A US2013209833A1 US 20130209833 A1 US20130209833 A1 US 20130209833A1 US 201113880929 A US201113880929 A US 201113880929A US 2013209833 A1 US2013209833 A1 US 2013209833A1
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- rolled
- plate
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- rolling
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000010960 cold rolled steel Substances 0.000 title claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 47
- 239000010959 steel Substances 0.000 claims description 47
- 230000007797 corrosion Effects 0.000 claims description 37
- 238000005260 corrosion Methods 0.000 claims description 37
- 238000000137 annealing Methods 0.000 claims description 13
- 239000011265 semifinished product Substances 0.000 claims description 13
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 238000005097 cold rolling Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 238000005098 hot rolling Methods 0.000 claims description 6
- 238000010586 diagram Methods 0.000 claims description 5
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 238000005482 strain hardening Methods 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910002551 Fe-Mn Inorganic materials 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 150000004767 nitrides Chemical class 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910000734 martensite Inorganic materials 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 iron carbides Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004881 precipitation hardening Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- 229910000720 Silicomanganese Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- 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
-
- 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
- C21D8/0226—Hot rolling
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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
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0421—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
- C21D8/0426—Hot rolling
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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
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0421—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
- C21D8/0436—Cold rolling
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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
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0447—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment
- C21D8/0463—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment following hot rolling
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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
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0447—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment
- C21D8/0473—Final recrystallisation annealing
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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
- C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
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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
- C22C38/001—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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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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
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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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
- C22C38/16—Ferrous alloys, e.g. steel alloys containing 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
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- C—CHEMISTRY; METALLURGY
- 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
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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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
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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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
- C21D2211/001—Austenite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- the invention relates to metallurgy, and more particularly to hot-rolled or cold-rolled metal plates in iron-manganese steel which may be used in the automotive industry.
- Austenitic Fe-Mn-C steels are used in the automotive industry for making structural parts with very high strength, notably in the form of hot-rolled or cold-rolled plates. They have the advantage, as compared with carbon steels used for the same uses, of being more lightweight, which allows appreciable energy savings during the use of the vehicle.
- This family of steels is also called ⁇ TWIP (Twinning Induced Plasticity) steels ⁇ .
- Their mechanical strength is high (tensile strength Rm >1,000 MPa) and their ductility is considerable (elongation at break A>50%). They have excellent formability and a large capacity in absorbing energy in the case of impacts. This makes them particularly suitable for the manufacturing of safety and structural parts of vehicles.
- Their Mn content is of at least 10%, often of the order of 15 to 35%, their C content may range for example up to 1.5%, and other elements such as Al, Si, Cu, Ti, W, Mo, Cr, Ni, Nb, V . . . may be present in significant amounts. These contents are given as weight percentages as will be all the contents mentioned in the subsequent text.
- the stack fault energy of the steels is sufficiently low for having mechanical twinning compete with the slipping of dislocations.
- the twinning density increasing with deformation, the free path of dislocations rapidly drops. It is this mechanism by which the favorable mechanical properties mentioned above may be obtained.
- EP-A-1 067 203 describes Fe-Mn plates manufactured by direct casting of thin strips.
- the described compositions are very wide, in particular the Al content may range up to 6%, the Cu content up to 5%, the Si content up to 2.5%, but low Si, Al and Cu contents are preferred.
- These steels have remarkable mechanical properties when their elaboration method (casting in thin strips with possible hot-rolling, preferably in line with casting, cold-rolling and recrystallization annealing) is observed. But casting in thin strips is a method difficult to apply and not very adapted to mass production as this would be desirable for products intended for automobiles.
- WO-A-03/025240 describes Fe-Mn plates with high strength for welded tubes, including 10 to 40% of Mn, up to 2% of C, up to 5% of Si, up to 5% of Al, up to 5% of Cu. Many other alloy elements may also be present. However, low Al contents (less than 0.1% and preferably 0.01% at most), low contents of Cu (less than 1%), of Si (less than 1%, preferably less than 0.5%) are preferred, in particular for Al which, at high contents, risks forming nitrides and thereby promoting formation of cracks during hot transformations. Low Si contents are also preferred, since Si may promote the formation of martensite during cold deformation, and is unfavorable for pickling the material and the weldability thereof.
- WO-A-2005/019483 describes hot-rolled FeC-Mn steel plates with Rm greater than 900 MPa and high elongation at break (Rm ⁇ A%>45,000).
- the C content is narrowed down to 0.5-0.7% and the Mn content to 17-24%.
- the Al content is maintained at a very low level, 0.050% at most, there again in order to avoid formation of Al nitrides.
- the significant presence of Si and Cu is possible, but not particularly desired.
- WO-A-2006/056670 describes plates comparable with those of the previous documents with C contents a little greater (0.85-1.05%) and more narrowed Mn contents from 16 to 19%. Their strength Rm is greater than 1,200 MPa and its product with A% is greater than 65,000 MPA %. But these high properties are obtained on hot-rolled plates only at the expense of a total absence of precipitated iron carbides and of an average grain size of at most 10 ⁇ m. Fast quenching after hot rolling followed by winding at low temperature ( ⁇ 400° C.) is required for this purpose. And if the composition and treatment conditions are not well observed, there is a risk of forming cementite in the segregated areas and in the grain boundaries, whence insufficiently homogeneous properties in the product.
- WO-A-2006/077301 describes hot-rolled and then cold-rolled and then annealed Fe—C—Mn steel plates, intended to resist deferred cracking, i.e. to the occurrence of cracks after their shaping.
- element(s) which will be used as hydrogen traps are introduced into the steel, preventing this element of being concentrated at the austenitic grain boundaries.
- V, Ti, Nb, Cr and Mo may be used, together or separately, for this purpose. V is particularly effective.
- the composition of the steel and the heat treatments are adjusted for obtaining the desired high mechanical properties and resistance to deferred cracking, in particular with the purpose of obtaining carbides for which the average size is from 5 to 25 nm and located in majority in an intragranular position.
- WO-A-2008/007192 describes plates comparable with those of the previous document, which further may be coated with Zn or a Zn alloy under conditions allowing the formation of a layer rich in Fe and Mn at the metal/coating interface.
- Documents WO-A-95/26423, WO-A-97/24467 describes comparable plates. Other elements may be present in the very vast ranges of contents, for example up to 5% Cu.
- WO-A-2007/074994 describes comparable steels (which may however only contain 5% Mn) intended to be galvanized in order to improve their resistance to corrosion in a saline medium.
- WO-A-2008/078962 describes Fe-Mn plates containing up to only 0.5% of C, and other elements among which possibly Cu up to 10%. They contain residual austenite and martensite. They have good toughness but their tensile strength, although relatively high, and their elongation at break, are however less than those of the materials described earlier.
- WO-A-2007/075006 describes hot-rolled or cold-rolled Fe-Mn plates, intended to be coated and having good surface quality. They contain 0.2-1.5% of C, 10-25% of Mn, 0.01-3% of Al and 0.005-2% of Si.
- WO-A-2008/078904 describes hot-rolled or cold-rolled Fe-Mn plates with high mechanical properties and good surface quality, containing 0.2-1.5% of C, 10-25% of Mn, 0.3-3.0% of Al and no Si.
- WO-A-2008/078940 describes hot-rolled or cold-rolled Fe-Mn plates with high mechanical properties and good surface quality, containing 0.2-1.5% of C, 10-25% of Mn, 0.3-3.0% of Al, and at least one element from among Si, Ti and Nb. They are distinguished by good capacity in absorbing impacts.
- the purpose of the invention is to provide the users, notably automobile manufacturers, with Fe—Mn steels in the form of hot-rolled or cold-rolled plates, and optionally electro-galvanized, not only having the desired high mechanical properties, such as tensile strength Rm greater than or equal to 850 MPa and an elongation at break greater than or equal to 50% on a hot-rolled or annealed crude plate, and a large capacity in plastic deformation, but also having high resistance to corrosion under stress both in an aqueous medium and in a saline medium.
- the object of the invention is a hot-rolled or cold-rolled steel plate characterized in that its composition is, in weight percentages:
- the average size of its grains is less than or equal to 5 ⁇ m.
- the surface fraction of its precipitated carbides is less than or equal to 1.5%.
- It may include a Zn or Zn alloy coating obtaining by electro-galvanization.
- the object of the invention is also a method for manufacturing a steel plate, characterized in that:
- said wound hot-rolled plate is unwound and at least one cold-rolling/annealing cycle is applied to it in order to obtain a cold-rolled plate.
- cold deformation at a reduction rate of less than or equal to 30% may be applied to said cold-rolled plate.
- Said cold deformation may be achieved with a method selected from work-hardening rolling, tensile leveling with alternating flexure and simple drawing.
- the object of the invention is also a use in the automotive industry of a hot-rolled or cold-rolled plate having the previous composition.
- Said plate may be used under conditions which may cause corrosion under stress.
- the invention consists of finding a balance between the contents of the main elements Fe, Mn, Al and Cu with which it is possible to ensure both well adapted mechanical properties to the customary uses of TWIP steels and greater resistance to corrosion under stress than those of the steels of this family known up to now.
- Al—Cu and Al—Si pairs have particular relevance for solving this problem.
- FIG. 1 shows a diagram showing the influence of the temperature at the end of hot-rolling and of the delay between the end of hot-rolling and the beginning of subsequent fast quenching on the recrystallized fraction after winding, for steels according to the invention.
- the sensitivity to corrosion under stress is measured with two conventional methods, so-called ⁇ cup tests>> and ⁇ creep tests>>.
- the cup test consists of starting with a circular flat blank for example with a diameter of 55 mm, and of pressing it by means of a punch for example with a diameter of 33 mm in order to form a cup, according to methods described in WO-A-2006/077301.
- the factor ⁇ which determines the severity of the test, and is determined by the ratio between the diameter of the flat blank and of the punch diameter, is 1.67.
- the cup which has internal stresses following the deformation of the metal, is then immersed in pure or saline water, or in a saline mist depending on the medium, the influence of which is intended to be tested, and the number of days is measured after which cracks appear.
- the steels according to the invention should have the customary mechanical properties for this type of targeted use: a tensile strength Rm of at least 850 MPa and A% of at least 50% on a hot-rolled or cold-rolled and annealed crude plate.
- the minimum duration for resistance to corrosion of the cups is 90 days (tests under water) and of 13 days (tests in a saline mist).
- the corrosion test under stress in salty water it is considered that a minimum duration of resistance to corrosion of 4 days should be observed.
- the experiment shows that the size criteria for grains and precipitates only have a relatively minor influence on the resistance to corrosion under stress of these steels according to the invention, the composition of which is the main characteristic.
- the size of the precipitates has no effect on the corrosion under stress, but only on deferred cracking.
- the presence of large grains may possibly be beneficial for corrosion under stress, but it will prevent obtaining the desired mechanical properties.
- the method for producing the steels of the invention allowing them to be provided with the desired mechanical properties, it may be fundamentally identical with those of customary practice on known Fe—Mn steels.
- the function of observing this delay is to guarantee that recrystallization of the austenite of at least 75% of the product (if it is located in the ABCD′E′F′A area) or even 100% of the product (if it is located in the ABCDEFA area) is obtained. It is at this condition that a structure of the final product is obtained, guaranteeing the desired mechanical properties, and notably a great deformation capacity.
- the hot plate obtained at 580° C. or at a lower temperature for avoiding precipitation of iron carbides is wound.
- the thereby obtained hot-rolled plate has a thickness comprised between 0.5 and 5 mm, notably depending on the casting method used.
- the smallest thicknesses generally correspond to the cases when the semi-finished product was cast with a method for continuous casting of thin slabs or of thin strips directly from liquid metal.
- cold-rolling followed by batch-annealing or continuous annealing is applied to the hot-rolled plate after its unwinding.
- the annealing and following quenching conditions should however avoid the growth of grains and precipitation of iron carbides in proportions which would compromise the obtaining of the targeted mechanical properties.
- continuous annealing carried out at 600-900° C. for 10 to 500 seconds followed by quenching at a rate of 0.5° C./s or more is well adapted to this purpose. It is also possible to carry out several of such cold-rolling/annealing cycles, in particular when small final thicknesses are desired for cold-rolled plate.
- the cold-rolled plate obtained typically has a thickness of the order of 0.2 mm to a few mm.
- the manufacturing method should aim at minimizing the amount of hydrogen present at the end of the treatment, in order to reduce the risk of deferred cracking, in particular when micro-alloying is practiced by adding V, Ti, Nb, Mo, W or Cr within the prescribed limits for forming adequate carbides, nitrides and/or carbonitrides.
- V, Ti, Nb, Mo, W or Cr within the prescribed limits for forming adequate carbides, nitrides and/or carbonitrides.
- a batch-annealing carried out on the wound strip is particularly adapted for this purpose.
- the plate may also undergo a coating operation with Zn or a Zn alloy, by galvanization or electrodeposition, at a moment of the production compliant with customary practice, for example before the last annealing aiming at removing hydrogen.
- the contents of the different elements required by the invention will now be accounted for.
- the C content is comprised between 0.6 and 0.9% and the Mn content between 17 and 22%. With this pair of contents it is possible to obtain the sought stable austenitic microstructures, determining the mechanical properties of the plate. In particular, excessive formation of iron carbides is avoided if C does not exceed 0.9%, and the formation of martensitic phases which would degrade the plate deformation capability is avoided or strongly limited if Mn exceeds 17%.
- the upper limit of 22% for Mn is explained by reasons related to the ductility of the plate at room temperature and to the cost of the material.
- Al content is comprised between 0.2 and 0.9%, preferably between 0.4 and 0.8%.
- Al is a deoxidizing element, the addition of which to Fe—C—Mn steels is common in highly variable proportions which may attain several %, but it may also be limited to a few tens of thousandths of % or even less, as this is seen in the documents from the prior art mentioned in the introduction.
- the nitrogen content should simultaneously be limited to 0.1%.
- Al is favorable to the increase in the stack fault energy, which reduces the risk of forming deformation martensite.
- Al has a negative influence on the corrosion under stress in salty water.
- the optimum for Al is located at about 0.4%.
- the Si content is comprised between 0.2 and 1.1%, preferably between 0.20 and 0.6%. Si is also used for de-oxidation of steel (although in the present case, when the Mn and Al contents are always high, its role is minor from this point of view), and also for hardening the metal.
- the minimum content of 0.2% is that which is necessary so that Si begins having its effects felt on the mechanical characteristics on the one hand, is on the other hand of the order of that which will inevitably be found in the metal following addition of Mn, when the latter is achieved in the form of a silico-manganese as this is conventional (this material being less expensive and more available than ferro-manganese which may also be used for this purpose).
- a content of about 1% leads to optimum resistance to corrosion under stress in water, but is not very effective in a saline medium.
- a content comprised between 0.2 and 0.6% is the best compromise between the different requirements which may have to be satisfied by products during use, notably in the automotive field. Beyond 1.1%, there is a risk of forming martensite which would be unfavorable for the sought mechanical properties.
- the Cu content is comprised between 1.2 and 1.9%. Customarily, it is possible to add contents thereof up to several % in order to obtain precipitation hardening, with however the risk of promoting the occurrence of surface defects on the hot-rolled products. It is found that a content from 1.2 to 1.9%, combined with the aforementioned Al and Si contents for which it is found (especially for Si) that they provide a synergistic effect with Cu for reducing corrosion under stress of the relevant Fe—C—Mn steels, is the optimum range for solving the aforementioned technical problems.
- the presence of Cu also gives the possibility of keeping a sufficiently low elastic limit so as to provide the steel with a low Re/Rm ratio, the sign of a great capacity of retaining a deformation, without any elastic return.
- the precipitation hardening effect usually provided by very high Cu contents is not sought here.
- the S content is limited to 0.030% at most in order to avoid embrittlement of the grain boundaries and therefore deterioration of the ductility.
- the P content is limited to 0.080% for the same reason.
- the N content is less than or equal to 0.1%. Significant and uncontrolled formation of nitrides is actually detrimental to the sought mechanical properties.
- the steel may also contain the following elements.
- This element may contain Cr, the content of which is limited to at most 2%, preferably at most 1%.
- This element may increase resistance to corrosion in aqueous media, but it also tends to reduce the stack fault energy and therefore the stability of the austenite under deformation, therefore the capability of the steel of being deformed.
- Ni may contain Ni, the content of which is limited to 2% at most. It also increases the resistance to corrosion in aqueous media. It also contributes to obtaining a significant elongation at break and increases toughness. However, its addition proves to be unnecessarily expensive beyond 2%.
- Ti may contain Ti, the content of which is limited to 0.5% at most.
- This element has a hardening action by the precipitation of carbonitrides which it causes and which trap hydrogen, but in an excessive amount, these carbonitrides will reduce toughness, which is not desired.
- Ti is present at a content from 0.040 to 0.5%.
- V may be added, up to 0.5% and preferably between 0.05 and 0.5% for the same reasons as for Ti.
- Nb may be added, up to 0.25%, preferably between 0.070 and 0.25%, for the same reasons as for Ti.
- Some B may be added, up to 0.010% and, preferably between 0.0005 and 0.010%. This element segregates at the grain boundaries and increases their cohesion. Surprisingly, the inventors noticed that addition of B in this range leads to a decrease of the order of 2.5 MPa per ppm on the elasticity limit and on the strength. Without intending to be bound to a theory, it is believed that this leads to a reduction in the residual stresses after shaping by pressing, and to better resistance to corrosion under stress of the thereby shaped parts.
- the other elements present are iron and impurities resulting from production, at their usual contents for this type of steels.
- Corrosion tests under stress were carried out on the cups of various compositions, either complying or not with the invention, as described in Table 1.
- the cups having a 3 factor of 1.67 were made with the method described earlier, from cold-rolled and annealed plates having undergone a treatment compliant with the one described above and with a thickness comprised between 1.2 and 1.5 mm.
- the creep specimens intended for determining the resistance to corrosion under traction in salted water were sampled in non-annealed cold-rolled steel plates.
- the body of the specimens had a width of 4mm and a useful length of 40 mm.
- the results of the mechanical and corrosion tests are summarized in Table 2.
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| FRPCT/FR2010/052254 | 2010-10-21 | ||
| PCT/FR2010/052254 WO2012052626A1 (fr) | 2010-10-21 | 2010-10-21 | Tole d'acier laminee a chaud ou a froid, don procede de fabrication et son utilisation dans l'industrie automobile |
| PCT/FR2011/052451 WO2012052689A1 (fr) | 2010-10-21 | 2011-10-20 | Tôle d'acier laminée à chaud ou à froid, son procédé de fabrication et son utilisation dans l'industrie automobile |
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- 2011-10-20 HU HUE11787726A patent/HUE027094T2/en unknown
- 2011-10-20 CN CN201180060810.0A patent/CN103261464B/zh active Active
- 2011-10-20 US US13/880,929 patent/US20130209833A1/en not_active Abandoned
- 2011-10-20 MX MX2013004337A patent/MX346491B/es active IP Right Grant
- 2011-10-20 WO PCT/FR2011/052451 patent/WO2012052689A1/fr not_active Ceased
- 2011-10-20 MA MA35831A patent/MA34613B1/fr unknown
- 2011-10-20 CA CA2815018A patent/CA2815018C/fr active Active
- 2011-10-20 KR KR1020137011951A patent/KR20130126612A/ko not_active Ceased
- 2011-10-20 UA UAA201306247A patent/UA107519C2/uk unknown
- 2011-10-20 EP EP20110787726 patent/EP2630269B1/fr active Active
- 2011-10-20 KR KR1020187013084A patent/KR102134524B1/ko active Active
- 2011-10-20 PL PL11787726T patent/PL2630269T3/pl unknown
- 2011-10-20 BR BR112013009694-2A patent/BR112013009694B1/pt active IP Right Grant
- 2011-10-20 RU RU2013123061/02A patent/RU2554264C2/ru active
- 2011-10-20 JP JP2013534371A patent/JP6250398B2/ja active Active
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2019
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11155905B2 (en) * | 2013-03-15 | 2021-10-26 | Exxonmobil Research And Engineering Company | Enhanced wear resistant steel and methods of making the same |
| US20180258515A1 (en) * | 2013-03-15 | 2018-09-13 | Exxonmobil Research And Engineering Company | Enhanced wear resistant steel and methods of making the same |
| WO2015088523A1 (en) * | 2013-12-11 | 2015-06-18 | ArcelorMittal Investigación y Desarrollo, S.L. | Cold rolled and annealed steel sheet |
| US10597745B2 (en) | 2013-12-11 | 2020-03-24 | Arcelormittal | High strength steel and manufacturing method |
| WO2015087224A1 (fr) | 2013-12-11 | 2015-06-18 | Arcelormittal Investigacion Y Desarrollo, S.L. | Acier à haute résistance et procédé de fabrication |
| WO2015195062A1 (en) * | 2014-06-16 | 2015-12-23 | Hayat Fatih | Steel with superior ductility and high strength and its manufacturing method |
| WO2016198906A1 (fr) | 2015-06-10 | 2016-12-15 | Arcelormittal | Acier a haute résistance et procédé de fabrication |
| US10697052B2 (en) | 2015-06-10 | 2020-06-30 | Arcelormittal | High strength steel and production method |
| US20180274056A1 (en) * | 2015-12-18 | 2018-09-27 | Posco | Wear resistant steel material excellent in toughness and internal quality, and method for manufacturing same |
| RU2707002C1 (ru) * | 2016-05-24 | 2019-11-21 | Арселормиттал | Листовая сталь с пластичностью, наведенной двойникованием, имеющая аустенитную матрицу |
| US10995381B2 (en) | 2016-05-24 | 2021-05-04 | Arcelormittal | Method for producing a TWIP steel sheet having an austenitic microstructure |
| RU2706252C1 (ru) * | 2016-05-24 | 2019-11-15 | Арселормиттал | Листовая твип-сталь, включающая аустенитную матрицу |
| WO2017203314A1 (en) * | 2016-05-24 | 2017-11-30 | Arcelormittal | Twip steel sheet having an austenitic matrix |
| WO2017203342A1 (en) * | 2016-05-24 | 2017-11-30 | Arcelormittal | Twip steel sheet having an austenitic matrix |
| WO2017203309A1 (en) * | 2016-05-24 | 2017-11-30 | Arcelormittal | Twip steel sheet having an austenitic matrix |
| US12188102B2 (en) | 2016-05-24 | 2025-01-07 | Arcelormittal | Method for producing a TWIP steel sheet having an austenitic microstructure |
| US11486017B2 (en) | 2016-05-24 | 2022-11-01 | Arcelormittal | Cold rolled and annealed steel sheet, method of production thereof and use of such steel to produce vehicle parts |
| WO2017203348A1 (en) * | 2016-05-24 | 2017-11-30 | Arcelormittal | Twip steel sheet having an austenitic matrix |
| US11414721B2 (en) | 2016-05-24 | 2022-08-16 | Arcelormittal | Method for the manufacture of TWIP steel sheet having an austenitic matrix |
| US11192165B2 (en) * | 2016-11-23 | 2021-12-07 | Outokumpu Oyj | Method for manufacturing a complex-formed component |
| AU2017364162B2 (en) * | 2016-11-23 | 2023-07-27 | Outokumpu Oyj | Method for manufacturing a complex-formed component |
| WO2018188766A1 (de) * | 2017-04-11 | 2018-10-18 | Thyssenkrupp Steel Europe Ag | Kaltgewalztes, haubengeglühtes stahlflachprodukt und verfahren zu dessen herstellung |
| US11634800B2 (en) | 2017-12-24 | 2023-04-25 | Posco Co., Ltd | High-strength austenite-based high-manganese steel material and manufacturing method for same |
| EP3730650A4 (en) * | 2017-12-24 | 2021-03-03 | Posco | HIGH MANGANESE, AUSTENITE BASED, HIGH STRENGTH STEEL MATERIAL AND ITS MANUFACTURING PROCESS |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2815018A1 (fr) | 2012-04-26 |
| ES2544607T3 (es) | 2015-09-02 |
| KR20180051679A (ko) | 2018-05-16 |
| HUE027094T2 (en) | 2016-08-29 |
| KR20130126612A (ko) | 2013-11-20 |
| MA34613B1 (fr) | 2013-10-02 |
| CN103261464A (zh) | 2013-08-21 |
| RU2554264C2 (ru) | 2015-06-27 |
| BR112013009694B1 (pt) | 2018-07-10 |
| CA2815018C (fr) | 2019-05-07 |
| RU2013123061A (ru) | 2014-11-27 |
| EP2630269A1 (fr) | 2013-08-28 |
| MX2013004337A (es) | 2013-05-20 |
| EP2630269B1 (fr) | 2015-05-20 |
| CN103261464B (zh) | 2016-04-27 |
| MX346491B (es) | 2017-03-22 |
| BR112013009694A2 (pt) | 2016-07-19 |
| KR102134524B1 (ko) | 2020-07-16 |
| WO2012052689A1 (fr) | 2012-04-26 |
| JP6250398B2 (ja) | 2017-12-20 |
| US20190211428A1 (en) | 2019-07-11 |
| WO2012052626A1 (fr) | 2012-04-26 |
| UA107519C2 (uk) | 2015-01-12 |
| PL2630269T3 (pl) | 2015-10-30 |
| US11131011B2 (en) | 2021-09-28 |
| JP2013544968A (ja) | 2013-12-19 |
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