TW201319267A - 合金化熔融鍍鋅鋼板 - Google Patents
合金化熔融鍍鋅鋼板 Download PDFInfo
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- TW201319267A TW201319267A TW101135892A TW101135892A TW201319267A TW 201319267 A TW201319267 A TW 201319267A TW 101135892 A TW101135892 A TW 101135892A TW 101135892 A TW101135892 A TW 101135892A TW 201319267 A TW201319267 A TW 201319267A
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- steel sheet
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- temperature
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 31
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 31
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 81
- 239000010959 steel Substances 0.000 claims abstract description 81
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 108
- 238000007747 plating Methods 0.000 claims description 108
- 229910052742 iron Inorganic materials 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000005275 alloying Methods 0.000 claims description 22
- 238000005246 galvanizing Methods 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000005096 rolling process Methods 0.000 claims description 17
- 238000005098 hot rolling Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005097 cold rolling Methods 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 230000036961 partial effect Effects 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000010960 cold rolled steel Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 238000004804 winding Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 229910001566 austenite Inorganic materials 0.000 abstract 1
- 229910001563 bainite Inorganic materials 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 229910000734 martensite Inorganic materials 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 26
- 238000001816 cooling Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- 238000005728 strengthening Methods 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000000137 annealing Methods 0.000 description 9
- 229910000905 alloy phase Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 238000005266 casting Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000029052 metamorphosis Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 241000282461 Canis lupus Species 0.000 description 1
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 1
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 210000002257 embryonic structure Anatomy 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910001568 polygonal ferrite Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- 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
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- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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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
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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
- 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
-
- 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
- C21D8/0478—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 surface treatment
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
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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
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
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Abstract
本發明係一種高強度合金化熔融鍍鋅鋼板,其係於高強度鋼板表面經施行有合金化熔融鍍鋅者,該鋼板含有主要成分,且以質量%計,變韌鐵及/或麻田散鐵以體積分率計係40%以上,含有8%以上~60%以下之殘留沃斯田鐵,且含有小於40%之肥粒鐵,並由剩餘之不可避免的組織所構成。前述合金化熔融鍍敷鋼板為合金化熔融鍍鋅層中之Γ1層與Γ層之合計厚度(Tγ1+Tγ)係2μm以下,且Γ1相與Γ相之厚度的比率(Tγ1/Tγ)係1以下,並可輕易地賦與抗拉強度980MPa以上,且鍍敷密著性優異,可抑制加工時之鍍敷剝離。
Description
本發明係有關於一種合金化熔融鍍鋅鋼板。更詳細而言,本發明係有關於一種可輕易地實現高強度(例如,980MPa以上之抗拉強度),且鍍敷密著性優異,可適合作為汽車領域、及家電領域、建材領域等構件使用的高強度合金化熔融鍍鋅鋼板。
以往,合金化熔融鍍鋅鋼板係主要使用於汽車領域,但於合金化熔融鍍鋅鋼板之鍍敷層中存在有延性較基質之鋼板低的Zn-Fe合金層。因此,例如,於要求抗拉強度980MPa以上時鍍敷密著性差、於壓機成形時等加工時鍍敷容易由鍍敷與基質之鋼板的界面剝離,容易成為壓疵等外觀不良,而成為問題。
因此,作為改善鍍敷密著性之方法,於專利文獻1中舉出了藉由增大鍍敷與基質鋼板界面之凹凸,即所謂之定錨效應(anchor effect),提升鍍敷密著性的方法。又,專利文獻2中記載著將鋼板加熱後進行酸洗處理,並於去除表面氧化物層後進行鍍敷,可改善密著性。
又,專利文獻3中揭示了一種以體積分率計,包含30~90%之肥粒鐵相、5%以上之變韌鐵、10%以下之麻田散鐵、及5~30%之殘留沃斯田鐵相的高強度高延性熔融鍍鋅
鋼板。專利文獻4中,揭示了一種鋼板所含之差排的密度係8×1011(個/mm2)以下,由應變速率0.0067(s-1)下之半靜力強度(FS1)與應變速率1000(s-1)下之動力強度(FS2)的比所構成之靜動力比(=FS2/FS1)係1.05以上的高強度冷軋鋼板。專利文獻5中,揭示了一種係Fe:8~12%,Al:0.05~0.25%,剩餘部分Zn的組成,且基質鐵界面之Γ相係1.0/μm以下,至少於單面具有鍍敷層表面未存在η相、ζ相之特定鍍敷層的合金化熔融鍍敷鋼板。
然而,於先前技術中,並未解決基本上鍍敷密著性之主要原因係鍍敷層與基質鋼板之延性的差,故於硬化加工時無法抑制鍍敷之剝離。
專利文獻1:日本專利特開2011-94215號公報
專利文獻2:日本專利特開2002-173756號公報
專利文獻3:日本專利特開2005-133201號公報
專利文獻4:日本專利特開2002-30403號公報
專利文獻5:日本專利特開昭64-68456號公報
本發明之目的係提供一種可抑制加工時之鍍敷剝離的高強度(例如,抗拉強度980MPa以上)之合金化熔融鍍鋅鋼板。
本發明之其他目的係提供一種鍍敷密著性優異之高強度合金化熔融鍍鋅鋼板。
本發明人等致力地檢討的結果,發現藉由控制鋼板組織,使鋼板本身之延性下降,並控制鍍敷相中之Γ1相與Γ相的量,使鍍敷本身之延性增加,可控制鍍敷剝離。
本發明人依據前述觀察所得知識更加重複研究之結果,亦發現藉使合金化熔融鍍鋅層中存在之Γ1相與Γ相的合計厚度為2μm以下,並使Zn-Fe合金相中延性最低之Γ1相的厚度較Γ相小,可更加提升鍍敷密著性。
據本發明人之觀察所得知識,可如以下地推測本發明中可得前述效果的機構。
換言之,本發明人發現,基本上即使提升鍍敷層之延性,欲使不可避免地生成於合金化熔融鍍鋅層中之鍍敷與基質鋼板之界面的Γ1相(Fe5Zn21,Fe含有率18%以上且小於24%)與Γ相(Fe3Zn10,Fe24%以上且32%以下)之延性較基質鋼板之延性大係為困難,故鍍敷無法追隨加工時之基質鋼板的變形,而產生鍍敷剝離。
相對於此,本發明人發現,於藉由控制鋼板組織,使鋼板本身之延性下降,並控制鍍敷相中之Γ1相與Γ相的量,使鍍敷本身之延性增加時,可抑制鍍敷剝離。本發明人更考量到藉由降低鋼板本身之延性,加工性將較以往下降,而於基質鋼板本身早期地產生破裂,甚至造成斷裂的可能性,但亦發現藉由於本發明中賦與控制有Γ1相與Γ相之量的
鍍敷,可抑制以往同等以上的破裂。
產生如此現象之理由尚未十分明確,但本發明人推測基質鋼板的破裂雖有早期產生的可能性,但藉於鋼板上存在延性優異之鍍敷,可抑制朝破裂部的應力集中。
換言之,本發明係伸長與鍍敷密著性優異之高強度合金化熔融鍍鋅鋼板。本發明可包含例如,以下之態樣。
[1]一種合金化熔融鍍鋅鋼板,其係以質量%計,含有:C:0.10%以上且0.4%以下、Si:0.01%以上且0.5%以下、Mn:1.0%以上且3.0%以下、O:0.006%以下、P:0.04%以下、S:0.01%以下、Al:0.1以上且3.0%以下、及N:0.01%以下,並由剩餘部分之Fe及不可避免的不純物所構成的鋼板;並且為於鋼板表面經施行有合金化熔融鍍鋅之合金化熔融鍍鋅鋼板,該鋼板之組織以體積分率計,變韌鐵與麻田散鐵之含有率合計係40%以上,含有8%以上~60%以下之殘留沃斯田鐵,且含有小於40%之肥粒鐵,並由剩餘部分之不可避免的組織所構成;前述合金化熔融鍍鋅層中之Γ1層的厚度Tγ1與Γ層之厚度Tγ的合計厚度係2μm以下,且Γ1相與Γ相之厚度的比率(Tγ1/Tγ)係1以下。
[2]如[1]記載之合金化熔融鍍鋅鋼板,其中前述合金化熔融鍍鋅層中之ζ層的厚度Tζ與δ層厚度Tδ之合計厚度,與Γ1層與Γ層之合計厚度的比率{(Tζ+Tδ)/(Tγ1+Tγ)}係1.5以上且90以下。
[3]如[1]或[2]記載之合金化熔融鍍鋅鋼板,其於鋼板中以質量%計,更含有:Cr:0.05%以上且1.0%以下、Ni:0.05%
以上且1.0%以下、Cu:0.05%以上且1.0%以下、Nb:0.005%以上且0.3%以下、Ti:0.005%以上且0.3%以下、V:0.005%以上且0.5%以下、B:0.0001%以上且0.01%以下、Ca:0.0005%以上且0.04%以下、Mg:0.0005%以上且0.04%以下、La:0.0005%以上且0.04%以下、Ce:0.0005%以上且0.04%以下、Y:0.0005%以上且0.04%以下之1種或2種以上的元素。
[4]一種合金化熔融鍍鋅鋼板之製造方法,係將以質量%計,含有:C:0.10%以上且0.4%以下、Si:0.01%以上且0.5%以下、Mn:1.0%以上且3.0%以下、O:0.006%以下、P:0.04%以下、S:0.01%以下、Al:0.1以上且3.0%以下、及N:0.01%以下,並由剩餘部分之Fe及不可避免的不純物所構成的鋼材,進行下述步驟:加熱至1100~1300℃,並於最後軋延溫度為Ar3溫度以上時施行熱軋處理;將前述熱軋後之鋼板於捲取溫度為700℃以下捲取,之後進行冷軋;將前述冷軋後之鋼板於最高加熱溫度為750℃~900℃下進行退火;將前述退火後之鋼板以於500~750℃之範圍中冷卻速度為3~200℃/秒冷卻至鍍敷浴浸漬溫度,之後,於350~500℃下保持10~1000秒;於進行鍍敷浴浸漬時的鋼板溫度係自較熔融鍍鋅浴溫度低40℃之溫度至較熔融鍍鋅浴溫度高50℃之溫度的溫度範圍下,將前述鋼板於氫分壓PH2、水蒸氣分壓PH2O之比的對數log(PH2O/PH2)的值係-5以上且-2以下,且氮含量係95質量%以上之氮環境氣體中,浸漬於Al濃度WAl、Fe濃度WFe以質量%計滿足下述關係式(1)、(2)的熔融
鍍鋅浴中,進行鍍敷處理:
0.01≦WFe≦0.05………(1)
0.07≦(WAl-WFe)≦0.30………(2)
之後,於進行合金化處理時,前述鋼板自出鍍敷浴後至進入合金化加熱爐為止的時間係於0.5秒以上且6秒以下的範圍;及前述鍍敷層之合金化加熱溫度係於440℃以上且600℃以下的範圍。
此處,Ar3=901-325×C+33×Si-92×(Mn+Ni/2+Cr/2+Cu/2+Mo/2),C、Si、Mn、Ni、Cr、Cu、Mo係顯示分別之成分的含量(質量%),而於未含有時為0。
依據本發明,可提供一種高強度(例如,抗拉強度980MPa以上)之鍍敷密著性優異之合金化熔融鍍鋅鋼板。本發明之高強度合金化熔融鍍鋅鋼板的製造亦可較輕易且穩定地實施。因此,該高強度合金化熔融鍍鋅鋼板特別適合使用於近年之以輕量化為目標的汽車用鋼板,產業上之價值極大。
圖1係顯示(Tγ1+Tγ)厚度、(Tγ1/Tγ)厚度比與鍍敷密著性之關係的圖表。
圖1中之記號係表示以下之意。
○:抗拉強度980Mpa以上、1.5≦{(Tζ+Tδ)/(Tγ1+Tγ)}≦90
△:抗拉強度980Mpa以上;{(Tζ+Tδ)/(Tγ1+Tγ)}<1.5、或{(Tζ+Tδ)/(Tγ1+Tγ)}>90
□:抗拉強度980Mpa以上、1.5≦{(Tζ+Tδ)/(Tγ1+Tγ)}≦90
×:抗拉強度小於980Mpa、1.5≦{(Tζ+Tδ)/(Tγ1+Tγ)}≦90
以下,依序說明本發明。
首先,說明成分之限定理由。另,%係質量%之意。
C:C係可提升鋼板強度之元素。然而,小於0.1%時,將不易兼具980MPa以上之抗拉強度與加工性。另一方面,大於0.40%時,確保點熔接性變得困難。因此,將其範圍設為0.1~0.40%。該C含量以0.13~0.3為佳,以0.19~0.28更佳。
Si:Si係強化元素,並有效提升鋼板之強度。又,因可抑制雪明碳鐵之析出,故需添加以有助於殘留沃斯田鐵的穩定化。小於0.01%時,高強度化之效果小,又,大於0.5%時,加工性下降。因此,Si含量係設為0.01~0.5%之範圍。Si含量以0.2~0.45%為佳,以0.25~0.42%更佳。
Mn:Mn係強化元素,係有效提升鋼板之強度。然而,小於1.0%時,欲得到980MPa以上之抗拉強度係為困難。反之,較多時將助長與P、S的共偏析,導致加工性之顯著劣化,故將上限設為3.0%。因此,將Mn含量設為1.0~3.0%之範圍。Mn含量以2.0~2.7%為佳,以2.1~2.45%更佳。
O:O因形成氧化物,使伸長、彎曲性或擴孔性劣化,故需抑制添加量。特別是,氧化物多作為夾雜物存在,存在於衝孔端面、或切截面時,將於端面形成缺口狀
之傷痕或粗大之凹坑,故於擴孔時或硬化加工時,將導致應力集中,成為龜裂形成的起點,造成大幅之擴孔性或彎曲性的劣化。這是因為於O大於0.006%時,該傾向將變得顯著,故將O含量之上限設為0.006%以下。換言之,O係作為不純物限制為0.006%以下。O含量以0.004%以下為佳,以0.003%以下更佳。另一方面,O含量小於0.0001%時,將導致成本過高,於經濟上不佳,故將其作為實質之下限。
P:P有於鋼板之板厚中央部偏析的傾向,使熔接部脆化。大於0.04%時,因熔接部之脆化變得顯著,故將其適當範圍設為0.04%以下。換言之,P係作為不純物限制為0.04%以下。P含量以0.03%以下為佳,以0.025%以下更佳。P之下限值並未特別限定,但小於0.0001%時,於經濟上係不利,以將該值作為下限值為佳。
S:S係對熔接性及鑄造時與熱軋時之製造性造成不良影響。因此,將其上限值設為0.01%以下。換言之,S係作為不純物限制為0.01%以下。S含量以0.008%以下為佳,以0.006%以下更佳。S之下限值並未特別限定,但小於0.0001%時,於經濟上係不利,故以將該值作為下限值為佳。又,S將與Mn連結形成粗大之MnS,使彎曲性或擴孔性劣化,故以儘量減少為佳。
Al:Al可促進肥粒鐵形成,提升延性,故亦可添加。又,亦可活用作為脫氧材。小於0.1%時,該效果係不充分。另一方面,過剩之添加將增大Al系之粗大夾雜物的個數,成為擴孔性劣化或表面傷痕的原因。因此,Al含量
設為0.1%以上、3.0%以下。Al含量以0.2~1.5%為佳,以0.3~1.0%更佳。
N:N將形成粗大之氮化物,使彎曲性或擴孔性劣化,故需抑制添加量。這是因為,於N大於0.01%時,該傾向將變得顯著,故將N含量之範圍設為0.01%以下。N含量以0.008%以下為佳,以0.006%以下更佳。由減少熔接時之氣孔產生的觀點來看,N含量以少為佳。下限不需特別限定即可發揮本發明之效果,但N含量小於0.0005%時,將導致製造成本的大幅增加,故其係實質之下限。
Cr:Cr係強化元素,對提升可硬化性係為重要。但,小於0.05%時,將無法得到該等之效果,故將下限值設為0.05%。反之,於含有大於1.0%時,因對製造時及熱軋時之製造性造成不良影響,故將上限值設為1.0%。Cr含量以0.5%以下為佳,以0.45%以下更佳。
Ni:Ni係強化元素,對提升可硬化性係為重要。但,小於0.05%時,將無法得到該等之效果,故將下限值設為0.05%。反之,於含有大於1.0%時,因對製造時及熱軋時之製造性造成不良影響,故將上限值設為1.0%。此外,因有助於提升熔融鍍敷之潤濕性或促進合金化反應,故亦可添加。Ni含量以0.6%以下為佳,以0.52%以下更佳。
Cu:Cu係強化元素,對提升可硬化性係為重要。但,小於0.05%時,將無法得到該等之效果,故將下限值設為0.05%。反之,於含有大於1.0%時,因對製造時及熱軋時之製造性造成不良影響,故將上限值設為1.0%。此外,因
有助於提升熔融鍍敷之潤濕性或促進合金化反應,故亦可添加。Cu含量以0.5%以下為佳,以0.35%以下更佳。
Nb:Nb係強化元素。於析出物強化、利用抑制肥粒鐵結晶粒之成長的細粒強化及透過抑制再結晶之差排強化中,有助於提升鋼板之強度。添加量小於0.005%時,因無法得到該等之效果,故將下限值設為0.005%。於含有大於0.3%時,因碳氮化物之析出變多,成形性劣化,故將上限值設為0.3%。Nb含量以0.005%~0.25%為佳,以0.005%~0.20%更佳。
Ti:Ti係強化元素。於析出物強化、利用抑制肥粒鐵結晶粒之成長的細粒強化及透過抑制再結晶之差排強化中,有助於提升鋼板之強度。添加量小於0.005%時,因無法得到該等之效果,故將下限值設為0.005%。於含有大於0.3%時,因碳氮化物之析出變多,成形性劣化,故將上限值設為0.3%。Ti含量以0.005~0.25%為佳,以0.005~0.20%更佳。
V:V係強化元素。於析出物強化、利用抑制肥粒鐵結晶粒之成長的細粒強化及透過抑制再結晶之差排強化中,有助於提升鋼板之強度。添加量小於0.005%時,因無法得到該等之效果,故將下限值設為0.005%。於含有大於0.5%時,因碳氮化物之析出變多,成形性劣化,故將上限值設為0.5%。V含量以0.005~0.4%為佳,以0.005~0.3%更佳。
B於添加0.0001%以上時係有助於粒界強化或鋼材之強度化,但其添加量大於0.01%時,不僅該效果達飽
和,亦使熱軋時之製造性下降,故將其上限設為0.01%。
選自於Ca、Mg、REM之1種或2種以上的元素可添加合計0.0005~0.04%。Ca、Mg及REM係用以脫氧之元素,以含有1種或2種以上合計0.0005%以上為佳。此處,REM係指Rare Earth Metal(稀土金屬)。然而,於Ca、Mg及REM之含量的合計大於0.04%時,將成為成形加工性惡化之原因。因此,將該含量之合計設為0.0005~0.04%。
另外,於本發明中,REM係多添加於稀土金屬合金,除了La或Ce以外,有複合地含有鑭系列之元素的情形。不可避免的不純物方面,即使包含該等La或Ce以外之鑭系列之元素亦可發揮本發明的效果。但,即便添加金屬La或Ce仍可發揮本發明之效果。
接著,說明鋼材之組織。
本鋼板中,變韌鐵與麻田散鐵之含量的合計,以體積分率計係40%以上。變韌鐵與麻田散鐵之含有率的合計係用以確保伸長與強度所需,將下限值設為40%。
又,本發明之鋼板需包含體積分率8%以上、60%以下的殘留沃斯田鐵。藉由包含殘留沃斯田鐵,可同時達成高強度化與更加提升延性。體積分率小於8%時,將不易得到該效果,故將其下限設為8%以上。將上限設為60%以下係因大於60%時,變韌鐵或麻田散鐵之體積分率將小於40%,無法確保充分之伸長與強度之故。殘留沃斯田鐵(γ)以9~40%為佳,以10~35%更佳。
又,肥粒鐵需小於40%。肥粒鐵雖可提升延性,
但40%以上時無法確保強度。肥粒鐵之形態,除了多邊形肥粒鐵以外,亦可包含粒狀肥粒鐵。
又,本發明中之剩餘不可避免的組織係指波來鐵組織。
另外,前述微觀組織之各相、肥粒鐵、麻田散鐵、變韌鐵、沃斯田鐵、波來鐵及剩餘部分組織的判別、存在位置之觀察及面積率的測定,可藉由硝太蝕劑試劑及日本專利特開59-219473號公報所揭示的試劑腐蝕鋼板軋延方向截面或與軋延方向成直角方向之截面,並利用1000倍之光學顯微鏡觀察及1000~100000倍之掃描式及穿透式電子顯微鏡定量化。進行各20視野以上之觀察,藉由計點法或影像解析可求得各組織的面積率。
接著,說明合金化熔融鍍鋅層之構造。
本發明之合金化熔融鍍鋅層中的Γ1相之厚度Tγ1與Γ相之厚度Tγ的合計,如圖1所示,需為2μm以下。Γ1相、Γ相雖均係於合金化熔融鍍鋅時不可避免的生成者,但其合計厚度大於2μm時,延性不充分,鍍敷密著性劣化。Γ1相與Γ相之厚度的合計以Tγ1+Tγ=0.1~1.9μm為佳,以0.1~1.5μm更佳。該Γ1相與Γ相越薄越佳,但為充分地抑制Γ1相及Γ之生成將使製造變得困難,故由實際製造上之觀點來看,Tγ1+Tγ之下限值以0.1μm為佳。
又,Γ1相與Γ相之厚度的比率(Tγ1/Tγ),如圖1所示,需為1以下。大於1時,對延性極差之Γ1相的影響變大,而無法抑制鍍敷剝離。該比率(Tγ1/Tγ)以0.9以下為佳,以
0.8以下更佳。該Γ1相與Γ相之厚度的比率(Tγ1/Tγ)越小對鍍敷密著性之提升越佳,但於充分地抑制Γ1相之生成的情形下,欲增大Γ相之厚度,於製造上係為困難,故由實際製造上之觀點來看,下限值以0.005為佳。
又,合金化熔融鍍鋅層中之ζ層(FeZn13)之厚度Tζ與δ層(FeZn7)之厚度Tδ的合計厚度,與Γ1層與Γ層之合計厚度(Tγ1+Tγ)的比率,即{(Tζ+Tδ)/(Tγ1+Tγ)},如圖1所示,以1.5以上、90以下為佳。小於1.5時,對延性差之Γ1相與Γ相的影響變大,鍍敷密著性稍差。大於90時,該效果係飽和,其控制於製造上的限制變大,故以90以下為佳。該比率{(Tζ+Tδ)/(Tγ1+Tγ)}以2~80為佳,以3~75更佳。
該等合金化熔融鍍鋅層中之各合金層之厚度的測定方法有各種方法,可舉「顯微鏡截面試驗法」(JIS H 8501)為例。這是於填入試料之截面並研磨後,視需要以腐蝕液蝕刻,以光學顯微鏡或掃描式電子顯微鏡(SEM)、電子探針顯微分析儀(EPMA)等分析研磨面,求得厚度的方法。
於本發明中,填入Technovit 4002(股份公司MARUTO社製),並依序以#240、#320、#400、#600、#800、#1000之研磨紙(JIS R 6001)研磨後,以硝太蝕劑液(0.5%硝酸乙醇溶液)浸泡研磨面10秒進行蝕刻,再以SEM觀察,求出各合金相之厚度。
但,此處之各合金相之厚度係指由互相距離1mm以上之任意10處的位置之鍍敷層分別求出各合金相之厚度,並將求出的合金相之厚度分別平均後的值。
又,合金相之ζ相(FeZn13),δ1相(FeZn7),Γ1相(Fe5Zn21),Γ相(Fe3Zn10)的組成、構造係分別相異,故以EPMA或X射線繞射法(XRD)、穿透式電子顯微鏡(TEM)等分析,可判別各合金相之種類。
於本發明中,以TEM分析判別各合金相之種類(例如,與Hong,M.N.,and Saka,H.;1998,Proc.4th Intern.Conf.On Zn and Zn Alloy Coated Steel Sheet,Galvatech‘98,p.248;或Kato,T.,Hong,M.H.,Nunome,K.,Sasaki,K.,Kuroda,K.,and Saka,H.;1998,Thin Solid Films,319,132記載者相同的分析)。因此,利用該TEM之分析方法的詳細內容,可視需要參照該等之文獻。
前述之合金化熔融鍍鋅相中的各層之厚度的測定方法,係使用「截面組織觀察法」,亦可測定各層之厚度。此處,「截面組織觀察法」係指於將試料填入研磨後,以腐蝕液,例如,添加有硝太蝕劑或抑制劑之0.5%鹽酸等蝕刻,由光學顯微鏡或掃描式電子顯微鏡觀察的組織求得之方法。各組織之厚度可係長度10mm之觀察範圍中任意10處之厚度的平均值。又,該等所觀察之組織係以EPMA或X射線繞射法、穿透式電子顯微鏡等調查組成或構造,可判別合金相之種類。於該截面組織觀察中,以EPMA調查其組織為佳。
接著,說明本發明之鍍敷密著性優異的高強度合金化熔融鍍鋅鋼板之製造方法。
熱軋前之製造方法並未特別限定。換言之,除了於利用豎爐或電爐等之熔製後接著進行各種2次熔煉,接著,利
用通常之連續鑄造、鑄錠法的鑄造以外,亦可使用薄扁鋼胚鑄造等方法鑄造。於連續鑄造時,在冷卻至低溫一次後,可於再度加熱後熱軋,亦可連續地熱軋鑄造扁鋼胚。亦可於原料中使用廢料。
熱軋扁鋼胚加熱溫度不需特別限定,即可發揮本發明之效果。然而,將加熱溫度設得過高時,於經濟上不佳,故加熱溫度之上限以小於1300℃為佳。又,過度低溫地加熱時,將不易使最後軋延溫度為Ar3溫度以上,故以將下限溫度設為1100℃為佳。
後軋延溫度成為沃斯田鐵+肥粒鐵之2相域時,鋼板內之組織不均一性變大,退火後之成形性劣化,故以Ar3溫度以上為佳。另,Ar3溫度係藉由以下式計算。
Ar3=901-325×C+33×Si-92×(Mn+Ni/2+Cr/2+Cu/2+Mo/2)
軋延後之冷卻並未特別規定,即使採用用以進行各目的之組織控制的冷卻模式,仍可得到本發明之效果。
捲取溫度需為700℃以下。大於700℃時,將於熱軋組織中存在粗大之肥粒鐵或波來鐵組織,殘留沃斯田鐵將不於本發明之範圍,而無法得到本發明之範圍的基質鋼板,退火後之組織不均一性變大,有最終製品之材質異向性變大的傾向。於本發明中,以使退火後之組織細微化,提升強度延性均衡為佳。又,以大於700℃之溫度捲取時,因形成於鋼板表面的氧化物之厚度過大,酸洗性差,故不佳。下限不需特別限定,即可發揮本發明之效果。然而,於室溫以下之溫度捲取以技術上來說係為困難,故將其作
為實質之下限。另,於熱軋時接合粗軋延板群連續地進行最後軋延亦佳。又,亦可暫時捲取粗軋延板。
熱軋後之鋼板,通常,係於酸洗處理去除表面的鏽皮。可進行一次之酸洗,亦可分複數次進行酸洗。
經酸洗之熱軋鋼板,通常係進行冷軋。軋縮率以40%以上且80%以下為佳。軋縮率小於40%時,不易保持形狀平坦,又,最終製品之延性變差。另一方面,大於80%之冷軋中,冷軋負載變得過大,冷軋變得困難。軋延道次(pass)之次數、各道次之各軋縮率不需特別限定,即可發揮本發明之效果。
經冷軋之鋼板,通常,係於連續退火鍍敷線進行退火及鍍敷。通過板時的加熱速度不需特別限定,即可發揮本發明之效果。然而,小於0.5℃/秒之加熱速度因生產性大幅地受損故不佳。另一方面,大於100℃時需過度之設備投資,於經濟上不佳。
最高加熱溫度(退火溫度)需為750℃以上且900℃以下。最高加熱溫度小於750℃時,熱軋時形成之碳化物再固溶將耗費過多時間,而殘留碳化物、或其一部分,故不易確保980MPa以上之強度,無法得到本發明範圍之基質鋼板。因此,將750℃設為最高加熱溫度之下限。另一方面,過度之高溫加熱將導致成本上升,故不僅於經濟上不佳,亦衍生高溫通過板時的板形狀變差、輥之壽命下降等問題,故將最高加熱溫度之上限設為900℃。
該溫度域下之熱處理時間並未特別限定,但為熔
解碳化物,以10秒以上之熱處理為佳。另一方面,熱處理時間大於600秒時,將導致成本上升,於經濟上不佳。熱處理方面,可於最高加熱溫度進行等溫保持,亦可進行傾斜加熱至到達最高加熱溫度後,立刻開始冷卻,均可發揮本發明之效果。
結束前述退火後,通常係冷卻至鍍敷浴浸漬溫度。由最高加熱溫度至750℃之平均冷卻速度,以0.1℃/秒以上且200℃/秒以下為佳。冷卻速度小於0.1℃/秒時,因生產性大幅受損,故不佳。過度地提高冷卻速度時,因將導致製造成本升高,故以將上限設為200℃/秒為佳。
500℃以上且750℃以下之範圍中的冷卻速度需為3℃/秒以上且200℃/秒以下。冷卻速度過小時,於冷卻過程中沃斯田鐵將變態成波來鐵組織,而不易確保8%以上之沃斯田鐵體積率,故將下限設為3℃/秒以上。即使加快冷卻速度,於材質上仍無問題,但過度地提高冷卻速度時,因將導致製造成本升高,故以將上限設為200℃/秒為佳。冷卻方法可使用輥冷卻、空氣冷卻、水冷卻及併用該等之任一方法。
之後,於350℃以上且500℃以下之範圍中,藉保持10秒以上且1000秒以下之範圍進行變韌鐵變態,穩定化殘留沃斯田鐵。將保持溫度之上限設為500℃係為於該溫度以下進行變韌鐵變態。另,於小於350℃之溫度下的保持中,因變韌鐵變態需長時間,設備將過大,生產性不佳。因此,保持溫度需為350℃以上且500℃以下之範圍。將下
限設為10秒係因,小於10秒之保持中變韌鐵變態之進行不充分,無法穩定化殘留沃斯田鐵,不易得到優異的成形性。另一方面,大於1000秒之保持中,因生產性下降故不佳。另,保持不僅指等溫保持,亦包含於該溫度域下之除冷或加熱。
鍍敷浴浸漬板溫度以設為自較熔融鍍鋅浴溫度低40℃之溫度至較熔融鍍鋅浴溫度高50℃之溫度的溫度範圍為佳。浴浸漬板溫度低於(熔融鍍鋅浴溫度-40)℃時,進入鍍敷浴浸漬時的熱傳遞大,熔融鋅之一部分將凝固,不僅有使鍍敷外觀劣化的情形,於基質鋼板與鍍敷之界面亦容易生成脆之Γ1相,故將下限設為(熔融鍍鋅浴溫度-40)℃。但,浸漬前之板溫度即使低於(熔融鍍鋅浴溫度-40)℃,只要於鍍敷浴浸漬前進行再加熱,使板溫度為(熔融鍍鋅浴溫度-40)℃以上地浸漬於鍍敷浴即可。另一方面,於鍍敷浴浸漬溫度大於(熔融鍍鋅浴溫度+50)℃時,於鍍敷與基質鋼板之界面生成厚之Fe-Al合金層,不僅賦與之後的合金化加熱負載,亦容易生成Γ1相與Γ相,無法得到具有本發明範圍之硬度的鍍敷。另,鍍敷浴除了純鋅以外,亦可含有Fe、Al、Mg、Mn、Si、Cr等。
將鋼板浸漬於鍍敷浴時之環境氣體係氫分壓PH2、水蒸氣分壓PH2O之對數log(PH2O/PH2)的值為-5以上且-2以下,氮含量為95體積%以上之氮環境氣體。log(PH2O/PH2)之值小於-5時,於經濟上不佳,且鋼板表面或鍍敷浴表面之反應性變高,之後的合金化處理步驟中將形成厚之Γ、
Γ1,無法得到本發明之範圍的鍍敷。另一方面,log(PH2O/PH2)之值大於-2時,於鍍敷浴面形成Zn之氧化物,因阻礙鍍敷層之Γ、Γ1的形成,無法得到本發明之範圍的鍍敷,且鍍敷未附著於鋼板,產生未鍍敷的情形。氮含量小於95體積%時,環境氣體中之水蒸氣與氫的比例變多,於經濟上及安全上不佳。環境氣體中氫之比例變多時,因鋼板脆化,延性下降故不佳。此處所提之將鋼板浸漬於鍍敷浴時的環境氣體係指,以將鋼板浸漬於鍍敷浴之時間作為基點,至少浸漬於鍍敷浴10s以上前之間爐內的環境氣體,最大範圍係指自連續退火鍍敷生產線之退火至浸漬於鍍敷浴之間的環境氣體全體。
為控制鍍敷層之特性,係鍍敷浴之Al濃度WAl、Fe濃度WFe以質量%計,滿足下述關係式(1)及(2)的熔融鍍鋅浴。
0.01≦WFe≦0.05………(1)
0.07≦(WAl-WFe)≦0.30………(2)
WFe小於0.01時,於鍍敷層與鋼板界面生成厚之Γ1相與Γ相,無法得到本發明之範圍的鍍敷。WFe大於0.05時,於鍍敷層與鋼板界面未能生成充分之Γ1相與Γ相,未能得到本發明之範圍的鍍敷,且於鍍敷浴中形成Fe2Al5之上浮渣,使鍍敷後之外觀下降。
將(WAl-WFe)設為0.07以上且0.30以下之理由,係因為(WAl-WFe)小於0.07時,將於鍍敷層與鋼板界面生成厚之Γ1相與Γ相,不僅賦與之後的合金化加熱負載,亦無法得到本
發明之範圍的鍍敷。另一方面,(WAl-WFe)大於0.30時,合金化變慢,不僅生產性變差,於將鍍敷全體加熱至合金化時,將於鍍敷層與鋼板界面生成厚之Γ1相與Γ相,無法得到具有本發明範圍之硬度的鍍敷。
鍍敷層之合金化加熱溫度係440℃以上且600℃以下。合金化處理溫度小於440℃時,合金化之進行變慢,不僅生產性變差,亦優先生成脆之Γ1相,無法得到本發明之範圍的鍍敷。大於600℃時,形成碳化物,沃斯田鐵體積率減少,不僅不易確保980MPa以上之抗拉最大強度與優異之延性,亦生成大於2μm的Γ1相與Γ相,無法得到本發明之範圍的鍍敷。以480℃以上且580℃以下之範圍為佳,較佳者係520℃以上且560℃以下。
又,鋼板自出鍍敷浴至進入合金化加熱爐之時間係0.5秒以上且6秒以下。大於6秒時,於鍍敷與基質鋼板之界面生成厚之Fe-Al合金層,不僅賦與之後的合金化加熱負載,亦容易生成脆之Γ1相,ζ相與δ相之生成量少,不易得到本發明之範圍的密著性佳的鍍敷。為抑制生成脆之Γ1相,以鋼板自出鍍敷浴至進入合金化加熱爐之時間越短越佳,小於0.5秒時,因製造上之負載大,故將下限設為0.5秒。較佳之範圍係上限為5秒以下,以4秒以下更佳。
本發明之鍍敷密著性優異的高強度合金化熔融鍍鋅鋼板之素材原則上係經通常之製鐵步驟中的精煉、製鋼、鑄造、熱軋、冷軋步驟所製造者,但即便是省略其一部分或全部所製造者,只要滿足本發明之條件,即可得到
本發明之效果。
接著,藉由實施例,詳細地說明本發明。
將具有表1所示之成分的扁鋼胚加熱至1200℃,並於水冷帶水冷後,以表2所示之溫度捲取。熱軋板之厚度係2~4.5mm之範圍。
於酸洗熱軋板後以預定之冷軋率進行冷軋,使冷軋後之板厚成1.2mm,作為冷軋板。
之後,於該等冷軋板以表2所示之條件於連續合金化熔融鍍鋅設備中,施行熱處理與熔融鍍鋅處理。以表2之冷卻速度進行冷卻,自退火溫度至500~750℃,之後,於350℃~500℃之溫度範圍進行5~300秒之保持後,浸漬於經控制於預定條件的鋅鍍敷浴,以各條件進行合金化處理,並冷卻至室溫。此時之目標量係兩面均約45g/m2。最後,以0.4%之軋縮率對所得的鋼板進行表皮輥軋(skin pass rolling)。
抗拉試驗係自1.2mm厚之板,於軋延方向之直角方向及平行方向上擷取JIS5號試驗片,評價抗拉特性。由所得之伸長的值算出於與軋延方向平行之方向進行抗拉試驗時的伸長(L-E1)與垂直之方向進行抗拉試驗時的伸長(C-E1)之差(△E1)。進行各5次抗拉試驗求得各值之平均值,由其平均值算出抗拉強度(TS)。另,關於材質之異向性大的鋼板,有伸長之值不均勻的傾向。
鍍敷密著性係將於任意位置、方向切斷40×100mm之鋼板進行折彎90度之彎曲(彎曲半徑R=1mm或3mm)後,回復平坦,於彎曲部貼附膠帶後,立刻剝除,測定附著於膠帶之鍍敷的剝離寬度,並以下述基準評價鍍敷密著性之好壞,以「○」與「△」作為合格。
○:無鍍敷剝離
△:僅些微鍍敷剝離(剝離寬度:大於0mm且於5mm以下)
×:鍍敷剝離大(剝離寬度:大於5mm)
於表2顯示經測定之抗拉特性、鍍敷性狀。可知本發明之鋼板均係鍍敷密著性優異。
依據本發明,可提供一種鍍敷密著性優異之高強度合金化熔融鍍鋅鋼板。該高強度合金化熔融鍍鋅鋼板之製造亦較容易,可穩定地實施。因此,本發明之高強度合金化熔融鍍鋅鋼板特別最適合作為近年以輕量化作為目標的汽車用鋼板,產業上之價值極大。
圖1係顯示(Tγ1+Tγ)厚度、(Tγ1/Tγ)厚度比與鍍敷密著性之關係的圖表。
圖1中之記號係表示以下之意。
○:抗拉強度980Mpa以上、1.5≦{(Tζ+Tδ)/(Tγ1+Tγ)}≦90
△:抗拉強度980Mpa以上;{(Tζ+Tδ)/(Tγ1+Tγ)}<1.5、或{(Tζ+Tδ)/(Tγ1+Tγ)}>90
□:抗拉強度980Mpa以上、1.5≦{(Tζ+Tδ)/(Tγ1+Tγ)}≦90
×:抗拉強度小於980Mpa、1.5≦{(Tζ+Tδ)/(Tγ1+Tγ)}≦90
Claims (4)
- 一種合金化熔融鍍鋅鋼板,其特徵在於,其係以質量%計,含有:C:0.10%以上且0.4%以下、Si:0.01%以上且0.5%以下、Mn:1.0%以上且3.0%以下、O:0.006%以下、P:0.04%以下、S:0.01%以下、Al:0.1以上且3.0%以下、及N:0.01%以下,並由剩餘部分之Fe及不可避免的不純物所構成的鋼板;並且為於鋼板表面經施行有合金化熔融鍍鋅之合金化熔融鍍鋅鋼板,該鋼板之組織以體積分率計,變韌鐵與麻田散鐵之含有率合計係40%以上,含有8%以上~60%以下之殘留沃斯田鐵,且含有小於40%之肥粒鐵,並由剩餘部分之不可避免的組織所構成;前述合金化熔融鍍鋅層中之Γ1層的厚度Tγ1與Γ層之厚度Tγ的合計厚度係2μm以下,且Γ1相與Γ相之厚度的比率(Tγ1/Tγ)係1以下。
- 如申請專利範圍第1項之合金化熔融鍍鋅鋼板,其中前述合金化熔融鍍鋅層中之ζ層的厚度Tζ與δ層厚度Tδ之合計厚度,與Γ1層與Γ層之合計厚度的比率{(Tζ+Tδ)/(Tγ1+Tγ)}係1.5以上且90以下。
- 如申請專利範圍第1或2項之合金化熔融鍍鋅鋼板,其於鋼板中以質量%計,更含有:Cr:0.05%以上且1.0%以下、Ni:0.05%以上且1.0%以下、Cu:0.05%以上且1.0%以下、Nb:0.005%以上且0.3%以下、Ti:0.005%以上且0.3%以下、V:0.005%以上且0.5%以下、B:0.0001%以上且0.01%以下、Ca:0.0005%以上且0.04%以下、Mg:0.0005%以上且0.04%以下、La:0.0005%以上且0.04%以下、Ce:0.0005%以上且0.04%以下、Y:0.0005%以上且0.04%以下之1種或2種以上的元素。
- 一種合金化熔融鍍鋅鋼板之製造方法,其特徵在於,其係將以質量%計,含有:C:0.10%以上且0.4%以下、Si:0.01%以上且0.5%以下、Mn:1.0%以上且3.0%以下、O:0.006%以下、P:0.04%以下、S:0.01%以下、Al:0.1以上且3.0%以下、及N:0.01%以下,並由剩餘部分之Fe及不可避免的不純物所構成的鋼材,進行下述步驟:加熱至1100~1300℃,並於最後軋延溫度為Ar3溫度以上時施行熱軋處理;將前述熱軋後之鋼板於捲取溫度為700℃以下捲取,之後進行冷軋; 將前述冷軋後之鋼板於最高加熱溫度為750℃~900℃下進行退火;將前述退火後之鋼板以於500~750℃之範圍中冷卻速度為3~200℃/秒冷卻至鍍敷浴浸漬溫度,之後,於350~500℃下保持10~1000秒;於進行鍍敷浴浸漬時的鋼板溫度為自較熔融鍍鋅浴溫度低40℃之溫度至較熔融鍍鋅浴溫度高50℃之溫度的溫度範圍下,將前述鋼板於氫分壓PH2、水蒸氣分壓PH2O之比的對數log(PH2O/PH2)的值係-5以上且-2以下,且氮含量係95質量%以上之氮環境氣體中,浸漬於Al濃度WAl、Fe濃度WFe以質量%計滿足下述關係式(1)、(2)的熔融鍍鋅浴中,進行鍍敷處理:0.01≦WFe≦0.05………(1),0.07≦(WAl-WFe)≦0.30………(2);之後,於進行合金化處理時,前述鋼板自出鍍敷浴後至進入合金化加熱爐為止的時間係於0.5秒以上且6秒以下的範圍;及前述鍍敷層之合金化加熱溫度係於440℃以上且600℃以下的範圍;此處,Ar3=901-325×C+33×Si-92×(Mn+Ni/2+Cr/2+Cu/2+Mo/2),C、Si、Mn、Ni、Cr、Cu、Mo係顯示分別之成分的含量(質量%),而於未含有時為0。
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JP5595010B2 (ja) | 2009-10-30 | 2014-09-24 | 株式会社神戸製鋼所 | めっき密着性に優れた合金化溶融亜鉛めっき高張力鋼板、およびその製造方法 |
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- 2012-09-28 PL PL12836371T patent/PL2762602T3/pl unknown
- 2012-09-28 US US14/348,247 patent/US9181598B2/en active Active
- 2012-09-28 CN CN201280047327.3A patent/CN103827343B/zh active Active
- 2012-09-28 KR KR1020147007330A patent/KR101609331B1/ko active IP Right Grant
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10113223B2 (en) | 2014-11-05 | 2018-10-30 | Nippon Steel & Sumitomo Metal Corporation | Hot-dip galvanized steel sheet |
US10507629B2 (en) | 2014-11-05 | 2019-12-17 | Nippon Steel Corporation | Hot-dip galvanized steel sheet |
US10822683B2 (en) | 2014-11-05 | 2020-11-03 | Nippon Steel Corporation | Hot-dip galvanized steel sheet |
US10822684B2 (en) | 2014-11-05 | 2020-11-03 | Nippon Steel Corporation | Hot-dip galvanized steel sheet |
Also Published As
Publication number | Publication date |
---|---|
EP2762602B1 (en) | 2018-06-06 |
ZA201402308B (en) | 2015-03-25 |
WO2013047810A1 (ja) | 2013-04-04 |
CN103827343B (zh) | 2016-01-27 |
RU2576567C2 (ru) | 2016-03-10 |
JPWO2013047810A1 (ja) | 2015-03-30 |
BR112014007543B1 (pt) | 2020-09-15 |
US9181598B2 (en) | 2015-11-10 |
ES2686569T3 (es) | 2018-10-18 |
CA2849286C (en) | 2015-12-01 |
RU2014117653A (ru) | 2015-11-10 |
EP2762602A4 (en) | 2015-09-02 |
TWI507535B (zh) | 2015-11-11 |
KR20140064893A (ko) | 2014-05-28 |
CA2849286A1 (en) | 2013-04-04 |
CN103827343A (zh) | 2014-05-28 |
MX2014003663A (es) | 2014-04-30 |
PL2762602T3 (pl) | 2018-11-30 |
EP2762602A1 (en) | 2014-08-06 |
KR101609331B1 (ko) | 2016-04-05 |
MX352497B (es) | 2017-11-28 |
JP5304966B1 (ja) | 2013-10-02 |
US20140255725A1 (en) | 2014-09-11 |
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