WO2009084793A1 - Tôle d'acier revêtue à haute teneur en manganèse à résistance et ductilité élevées, et son procédé de fabrication - Google Patents
Tôle d'acier revêtue à haute teneur en manganèse à résistance et ductilité élevées, et son procédé de fabrication Download PDFInfo
- Publication number
- WO2009084793A1 WO2009084793A1 PCT/KR2008/004536 KR2008004536W WO2009084793A1 WO 2009084793 A1 WO2009084793 A1 WO 2009084793A1 KR 2008004536 W KR2008004536 W KR 2008004536W WO 2009084793 A1 WO2009084793 A1 WO 2009084793A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- less
- steel sheet
- slab
- temperature
- high manganese
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 82
- 239000010959 steel Substances 0.000 title claims abstract description 82
- 239000011572 manganese Substances 0.000 title claims abstract description 60
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000005098 hot rolling Methods 0.000 claims abstract description 24
- 238000007747 plating Methods 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 238000005554 pickling Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000005246 galvanizing Methods 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 14
- 239000010955 niobium Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 238000005244 galvannealing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910018657 Mn—Al Inorganic materials 0.000 claims description 4
- 238000009751 slip forming Methods 0.000 claims description 2
- 229910007570 Zn-Al Inorganic materials 0.000 claims 1
- 239000012071 phase Substances 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 15
- 229910001566 austenite Inorganic materials 0.000 description 11
- 239000010953 base metal Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 229910000617 Mangalloy Inorganic materials 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910000734 martensite Inorganic materials 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000008397 galvanized steel Substances 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000010960 cold rolled steel Substances 0.000 description 5
- 238000003618 dip coating Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910002551 Fe-Mn Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000017066 negative regulation of growth Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips 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
- 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
- C21D8/041—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 involving a particular fabrication or treatment of ingot or slab
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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
- C21D8/041—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 involving a particular fabrication or treatment of ingot or slab
- C21D8/0415—Rapid solidification; Thin strip casting
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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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- 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
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- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/40—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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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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
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- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
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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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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
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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
- C21D2211/004—Dispersions; Precipitations
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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
Definitions
- the present invention relates to a high manganese galvanized steel sheet having high ductility and strength as well as excellent corrosion resistance and workability, in which high manganese steel containing 15 to 30 wt% manganese (Mn) is plated with zinc (Zn) so as to form a single galvanized layer or a plated layer composed of 5 wt% or less Mn, 5 to 15 wt% iron (Fe), balance Zn, and inevitable impurities introduced from a base metal when plated.
- Mn manganese steel containing 15 to 30 wt% manganese
- Zn zinc
- an embodiment of the present invention is directed to provide a plating method for endowing high manganese steel, a kind of high-quality steel, with corrosion resistance. Disclosure of Invention Technical Problem
- Embodiments of the present invention provide high manganese steel containing a great deal of Mn through an optimum alloy design, and a galvanizing and/or gal- vannealing method as a processing technique suitable for the high manganese steel.
- a high manganese plated steel sheet which contains, by weight, 0.3% to 0.9% carbon (C), 15% to 30% manganese (Mn), 0.1% to 5.0% aluminum (Al), 0.04% or less nitrogen (N), 0.03% or less sulfur (S), 0.1% or less phosphor (P), one or two or more selected from the group consisting of 1.0% or less chrome (Cr), 1.0% or less molybdenum (Mo), 0.5% or less copper (Cu), 5.0% or less silicon (S), 0.0005% to 0.04% boron (B), 2.0% or less nickel (M), 0.5% or less niobium (Nb), 0.5% of less vanadium (V), 0.005% to 0.1% antimony (Sb), 0.001% to 0.3% titanium (Ti), 0.0005% to 0.04% lanthanum (La), 0.0005% to 0.04% cesium (Ce), 0.005% to 0.10% zirconium (Zr), and 0.0005% to 0.03
- An oxide film of Zn alone or Zn-Fe-Mn composite may be formed on a surface of the steel sheet.
- the oxide film of Zn-Fe-Mn composite contains, by weight, 5% or less Mn, and 5% to 15% Fe, inevitable impurities, and balance Zn on a basis of the oxide film.
- a method of manufacturing a high manganese plated steel sheet includes: a heating step of heating a continuously cast slab at a temperature of 1050 0 C to 1300 0 C, the continuously cast slab containing, by weight, 0.3% to 0.9% carbon (C), 15% to 30% manganese (Mn), 0.1% to 5.0% aluminum (Al), 0.04% or less nitrogen (N), 0.03% or less sulfur (S), 0.1% or less phosphor (P), one or two or more selected from the group consisting of 1.0% or less chrome (Cr), 1.0% or less molybdenum (Mo), 0.5% or less copper (Cu), 5.0% or less silicon (S), 0.0005% to 0.04% boron (B), 2.0% or less nickel (M), 0.5% or less niobium (Nb), 0.5% of less vanadium (V), 0.005% to 0.1% antimony (Sb), 0.001% to 0.3% titanium (Ti), 0.0005% to 0.04%
- the method may further include a galvannealing step so as to introduce Mn, Fe, etc. of base metal into the plated layer to form a stable composite oxide plated layer, thereby providing the high manganese plated steel sheet having high strength and toughness and improving corrosion resistance.
- the high manganese plated steel sheet has Zn-Fe-Mn composite hot-dip galvanized layer that secures high ductility and strength and that has corrosion resistance better than existing hot-dip galvanized steel. Best Mode for Carrying out the Invention
- Exemplary embodiments of the present invention provide a high manganese galvanized steel sheet having high ductility and strength as well as excellent corrosion resistance and workability, in which high manganese steel containing 15 to 30 wt% of manganese (Mn) is plated with zinc (Zn) so as to form a single galvanized layer or a galvannealed layer composed of 5 wt% or less Mn, 5 to 15 wt% iron (Fe), balance Zn, and inevitable impurities introduced from a base metal during plating, and a method of manufacturing the same.
- Mn manganese
- Zn zinc
- Snce C contributes to stabilization of an austenite phase, it is favorable to increase an added amount of C.
- the added amount of C is less than 0.3%, austenite stability is not maintained, and thus the fraction of a ferrite phase or an ⁇ - martensite phase other than the austenite phase is increased.
- the added amount of C exceeds 0.9%, the austenite stability is greatly increased, and thus workability is reduced by transition of a deformation behavior caused by slip deformation.
- the added amount of C is limited to a range of 0.3% to 0.9%.
- Mn Manganese (Mn): 15% to 30%
- Mn is an essential element that stabilizes an austenite phase as well as an important element that serves as a source that supplies Mn from a base metal to a plated layer in a galvannealing process during plating, and is added to a level of 15% to 30% for high manganese steel to which an embodiment of the present invention is applied.
- Mn is added at an amount less than 15%, the fraction of a ferrite phase or an ⁇ - martensite phase other than the austenite phase is increased.
- Mn is added at an amount exceeding 30%, high-temperature oxidation sharply occurs in a reheating process for hot rolling due to a high content of Mn, and thus deteriorates a quality of surface of a final product. Further, since a great deal of expensive Mn is added to increase production costs of the steel sheet, the added amount of Mn has an upper limit of 30%.
- Al is typically added for deoxidation of steel, but for improvement of ductility in an embodiment of the present invention.
- Al is an element for stabilizing a ferrite phase, but increases stacking fault energy in a slip plane, thereby inhibiting creation of an ⁇ -martensite phase to improve the ductility.
- Mn when the added amount of Mn is low, Al inhibits the creation of the ⁇ -martensite phase. As such, Al goes far toward minimizing the added amount of Mn and improving formability.
- Al is added at an amount of 0.1% or more.
- the added amount of Al when the added amount of Al is more than 5.0%, creation of twins is inhibited to reduce ductility and continuous castability, and surface oxidation becomes serious to deteriorate the surface quality of a product when hot rolling.
- the added amount of Al has an upper limit of 5.0%.
- S is typically known that, when added excessively, S forms a S oxide layer on a surface of steel to degrade hot dip coating characteristics.
- Mn- enriched steel when S is added at an appropriate amount, the S oxide layer is formed on the surface of the steel to inhibit oxidation in air.
- the steel sheet after cold-rolled, the steel sheet can be prevented from forming a thick Mn oxide layer.
- the cold rolled steel sheet After annealed, the cold rolled steel sheet can be prevented from corrosion, and thus the surface quality of the cold rolled steel sheet, particularly the base steel sheet, can be improved. Snce the thick Mn oxide layer is inhibited from being formed when hot dip coating is carried out, the hot dip coating characteristics are greatly improved.
- the added amount of S has an upper limit of 5.0%.
- S has a content of 0.04% or more in the steel, a desired purpose can be accomplished without separately adding S in an embodiment of the present invention.
- Cr has an effect of forming a passivation film in air to inhibit corrosion.
- Cr prevents decarburization of the steel, thereby inhibiting creation of an a - martensite phase from the surface of the steel sheet to improve formability of steel.
- an added amount of Cr, a ferrite stabilizing element is increased, the creation of the a -martensite phase is accelerated to reduce ductility of steel. For this reason, the added amount of Cr has an upper limit of 1.0%.
- Cu is a component added to increase corrosion resistance and strength. When an added amount of Cu exceeds 0.5%, red brittleness occurs to damage hot workability. Thus, the added amount of Cu is preferably limited to 0.5% or less.
- M increases stability of an austenite phase to inhibit creation of an ⁇ '-martensite phase damaging formability, and thus is favorable in terms of improving workability of steel.
- M is expensive.
- the added amount of M is limited to 2.0% or less.
- Mo is an element added to improve secondary working embrittlement resistance and platability. However, when an added amount of Mo exceeds 1.0%, Mo reduces the improving effect and is made economically unfavorable. Thus, the added amount of Mo is limited to 1.0% or less.
- Nb and/or V are components added to increase strength. When an added amount of
- Nb is more than 0.5%
- Nb causes cracks during hot working.
- V creates a low-melting-point compound to damage hot workability.
- the added amounts of Nb and V are each limited to 0.5% or less.
- N precipitates fine nitride in austenite grains in reaction with Al in the solidification process, thereby facilitating generating twins to improve strength and ductility when the steel sheet is formed.
- an added amount of N exceeds 0.04%, the nitride is excessively precipitated to reduce hot workability and elongation.
- the added amount of N is limited to 0.04% or less.
- S is an element that is inevitably added on manufacturing steel. Thus, an added amount of S is limited to 0.03% or less. Particularly, S forms coarse Mn sulfide (MnS) to generate defects such as flange cracks, and reduces stretch flangability (hole expandability). Thus, the added amount of S is preferably limited to 0.03% or less.
- MnS coarse Mn sulfide
- P has a significant role in improving pickling characteristics of a hot rolled steel sheet.
- P is an element that causes interfacial precipitation, and forms scales and chemically unstable Fe-P compounds precipitated on interfaces of the steel sheet to facilitate removal of the scales when pickling is carried out.
- a content of P increases, a superficial shape becomes uniform, and the pickling characteristics are improved.
- the added amount of P is preferably limited to 0.1% or less.
- B is resolved in columnar grain boundaries at a temperature of 1000 0 C or more, and thus inhibits creation and movement of vacancies to strengthen the columnar grain boundaries.
- B has little effect.
- B creates a large quantity of carbide and nitride to act as a nucleus for precipitation of Al nitride, thereby promoting the precipitation of coarse Al nitride to embrittle the grain boundaries.
- the proper added amount of B ranges from 0.0005% to 0.040%.
- Ti is an element that is effective for an increase in strength of steel and grain refinement. When a content of Ti is less than 0.001%, it is difficult to obtain this effect. In contrast, when the content of Ti exceeds 0.3%, manufacturing costs are increased, and ductility of ferrite can be reduced due to excessive precipitates. Thus, the content of Ti is preferably limited to a range from 0.001% to 0.3%.
- Zr is resolved in columnar grain boundaries, thereby increasing a melting temperature of an Al-enriched low-melting-point compound to prevent a liquid phase film from being formed at a temperature of 1300 0 C. Further, Zr has high affinity for nitrogen (N) to act as a nucleus for precipitation of coarse Al nitride that is attributable to embrittlement of the columnar grain boundaries, thereby strengthening the columnar grain boundaries.
- N nitrogen
- Zr is less than 0.005%, these effects are insignificant.
- the added amount of Zr exceeds 0.10%, Zr is segregated in the grain boundaries, thereby causing embrittlement of the grain boundaries.
- the added amount of Zr is limited to a range from 0.005% to 0.10%.
- La and Ce are rare earth elements that serve to create a nucleus of a dendrite structure when molten steel is solidified, thereby refining a dendrite to inhibit growth of a columnar grain structure and facilitate creation of an equiaxed grain structure.
- La and CE reduces size and amount of columnar grains attributable to grain boundary embrittlement, and increases an amount of equiaxed grains having excellent high-temperature ductility to improve hot workability.
- La and Ce form compounds with P and S which are segregated in the grain boundaries to reduce rupture strength of a grain boundary, thereby reducing adverse influence of P and S.
- added amounts of La and Ce are less than 0.0005%, this effect is insignificant.
- La and Ce exceed 0.040%, La and Ce are saturated.
- the added amounts of La and Ce are preferably limited to a range from 0.0005% to 0.040%.
- Ca forms compounds with non-metallic inclusions such as Al O , MnO, MnS, etc. in molten steel to spheroidize the non-metallic inclusions, thereby increasing rupture strength of a columnar grain boundary, releasing sensitivity of generating flange cracks from the steel sheet, and increasing stretch flangability (hole expandability) of the steel sheet.
- non-metallic inclusions such as Al O , MnO, MnS, etc.
- Sb contributes to inhibition of growth of various sub-scales generated in a hot-rolling process. Alloy elements such as S, Mn, Al, etc. show a selective oxidation behavior along an interface of the surface of the hot-rolled steel sheet, whereas Sb is segregated at the interfaces or the surface of the steel sheet without oxidation in a hot-rolling process, thereby effectively inhibiting growth of sub-scales.
- Sb is excessively added, an amount of Sb precipitated from the interfaces is increased, and there is a possibility of the interfaces being mechanically weakened.
- an added amount of Sb is less than 0.005%, it is difficult to produce a desired effect.
- Sb exceeds 0.1% there is a possibility of causing working embrittlement of material.
- the added amount of Sb is limited to a range from 0.005% to 0.1%.
- a hot-rolled steel sheet of high manganese steel is manufactured using continuous casting as in the process of manufacturing ordinary steel sheet.
- Steel melted with the above-mentioned composition is homogenized at a temperature of 1050 0 C to 1300 0 C similar to typical conditions, and a homogenized sample is subjected to finish hot rolling at a temperature of 85O 0 C to 95O 0 C under typical conditions, hot rolling for coiling at a temperature of 65O 0 C or less, and pickling.
- the heating temperature of a continuously cast slab is set to 1300 0 C as its upper limit. This is because a trace of alloy element strengthening a columnar grain boundary is added to increase the melting point of a low-melting-point compound of the columnar grain boundary up to about 1300 0 C.
- a liquid phase film is generated from the columnar gain boundary of the continuously cast slab, and thus cracks occur during hot rolling.
- the heating temperature is set to 1050 0 C as its lower limit.
- a typical finish rolling temperature is about 900 0 C in a hot rolling process.
- the steel sheet according to an embodiment of the present invention is subjected to hot rolling at this temperature.
- a rolling load is increased, which not only overloads a rolling mill but also exerts a bad influence on a quality of the interior of the steel sheet.
- Hot Rolling and Coiling temperature 750 c or less
- the coiling temperature of the hot rolled steel sheet is preferably low.
- the coiling temperature is limited to 75O 0 C or less that is a sufficiently low temperature.
- the steel sheet After the hot rolling, the steel sheet is subjected to pickling in a solution of HCl in order to remove oxidized scales formed on the surface thereof. If necessary, the steel sheet is subjected to cold rolling in order to adjust shape and thickness thereof.
- the pickling is preferably carried out at HCl concentration of 5% to 25% within a range from 6O 0 C to 9O 0 C for 20 seconds or more.
- the annealing temperature is limited to 600 0 C or more. Snce the high manganese steel according to an embodiment of the present invention is austenite steel free of phase transformation, workability can be sufficiently secured when the steel is heated at a recrystallization temperature or more. As such, the annealing is carried out under typical annealing conditions.
- the hot galvanizing bath is a typical galvanizing bath based on a composition of Zn-
- the plating is carried out in a plating bath of Zn-0.013%Al by weight.
- the plated layer does not undergo a great change in physical properties and corrosion resistance.
- the steel sheet is subjected to galvannealing at a temperature of 44O 0 C to 58O 0 C, thereby forming a galvannealed layer.
- the galvannealed layer is created in such a manner that Mn, Fe or the other components contained in base metal during galvannealing are diffused to react with a plating element of Zn.
- a composition of the galvannealed layer includes, by weight, 5% or less Mn, 5% to 15% Fe, balance Zn, and a trace of other impurities introduced in the plating process among constituent elements of steel.
- a oxide film formed after annealing The oxide film consit of Al alone or Mn-Al composite. An average thickness of the oxide film is 500 nm or less. Further, the oxide film is required not to continuously formed 10/M (micrometer) or more when its thickness is 50nm or more. [96] [97] Now, the high manganese galvanized steel sheet according to Examples of the present invention will be described in detail. [98]
- Plating was performed in the following two methods.
- the cold rolled steel sheet was annealed under N -10%H atmosphere at a temperature of 62O 0 C to 88O 0 C, and was immersed into Zn-0.021%Al bath maintained at a temperature of 46O 0 C, thereby forming a zinc plated layer on a surface thereof.
- the cold rolled steel sheet was annealed under N -10%H atmosphere at a temperature
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Abstract
L'invention porte sur un procédé de fabrication d'une tôle d'acier plaquée à haute teneur en manganèse. Le procédé consiste à chauffer une brame de coulée continue à une température de 1050°C à 1300°C ; à effectuer un laminage à chaud de finition sur la brame à une température de 850°C à 950°C ; à effectuer un laminage à chaud et un bobinage sur la brame à une température de 750°C ou moins ; à décaper la brame dans une solution de HCl ayant une concentration de 5 % à 25 % pendant 20 secondes ou plus ; à recuire la brame à une température de recristallisation de 600°C ; à immerger la brame dans un bain de galvanisation par immersion à chaud de façon à créer une couche plaquée sur une surface de la tôle d'acier.
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KR10-2007-0138538 | 2007-12-27 | ||
KR1020070138538A KR20090070509A (ko) | 2007-12-27 | 2007-12-27 | 고연성 및 고강도를 가지는 고망간 도금강판 및 그제조방법 |
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