CN104870679B - 高锰热镀锌钢板及其制造方法 - Google Patents
高锰热镀锌钢板及其制造方法 Download PDFInfo
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- CN104870679B CN104870679B CN201380067419.2A CN201380067419A CN104870679B CN 104870679 B CN104870679 B CN 104870679B CN 201380067419 A CN201380067419 A CN 201380067419A CN 104870679 B CN104870679 B CN 104870679B
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 113
- 239000010959 steel Substances 0.000 title claims abstract description 113
- 239000011572 manganese Substances 0.000 title claims abstract description 60
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 47
- 238000005246 galvanizing Methods 0.000 title claims abstract description 45
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 106
- 238000000576 coating method Methods 0.000 claims abstract description 106
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000005097 cold rolling Methods 0.000 claims abstract description 13
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 5
- 230000004907 flux Effects 0.000 claims 1
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- 230000008569 process Effects 0.000 abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 229910052700 potassium Inorganic materials 0.000 description 19
- 239000011591 potassium Substances 0.000 description 19
- 238000005275 alloying Methods 0.000 description 18
- 239000011651 chromium Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910000734 martensite Inorganic materials 0.000 description 12
- 238000000137 annealing Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
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- 239000011701 zinc Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 238000004220 aggregation Methods 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229910001566 austenite Inorganic materials 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 5
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- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000005098 hot rolling Methods 0.000 description 4
- 229910017083 AlN Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 229910018137 Al-Zn Inorganic materials 0.000 description 2
- 229910018573 Al—Zn Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 241001279158 Silonia silondia Species 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- 230000008520 organization Effects 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- -1 boron oxide compound Chemical class 0.000 description 1
- 239000010882 bottom ash Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 210000000981 epithelium Anatomy 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 238000005554 pickling Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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- C—CHEMISTRY; METALLURGY
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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
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C—ALLOYS
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C—CHEMISTRY; METALLURGY
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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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
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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
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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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- 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
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- 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
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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
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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
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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
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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.]
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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
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- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Abstract
本发明提供一种具有优异的涂镀性和超高强度的高锰热镀锌钢板的制造方法及用该方法制造的高锰热镀锌钢板。所述方法包括:对热轧钢板进行冷轧以形成冷轧钢板,所述热轧钢板,以重量%计,包括:C:0.3~1%、Mn:8~25%、Si:0.1~3%、Al:0.01~8%、Cr:0.1~2%、Ti:0.01~0.2%、B:0.0005~0.01%、Ni:0.01~2%、Sn:0.06~0.2%、余量Fe和不可避免的杂质;加热所述冷轧钢板;将所述加热的钢板冷却至450~500℃或保持所述加热的钢板;以及通过将所述冷却的或保持温度的钢板浸渍在热镀锌液中,对所述冷却的或保持温度的钢板进行热镀锌工艺。
Description
技术领域
本发明涉及一种具有优异的涂镀性和超高强度的高锰热镀锌钢板的制造方法及用该方法制造的高锰热镀锌钢板。
背景技术
热镀锌钢板具有优异的耐蚀性、焊接性及涂装性,因此多用作汽车钢板。并且,从由汽车的轻量化带来的燃料效率的提高以及乘客的安全性方面考虑,要求汽车车体以及构件具有高强度,为此,开发出了很多汽车用高强度钢。
然而,为适用于汽车,需要钢具有高强度的同时,还能够进行冲压加工或滚压成型,可是大部分钢材不具备这样的特性,因此实际上根据不同的用途使用不同种类的钢。即,为进行冲压加工,使用因具有低屈服比和大加工硬化率而具有高强度的同时确保均匀的延性和深加工性的二相组织钢(DP钢,硬质相变组织细分在铁素体母相中的复合组织钢),为进行滚压成型,需要具有高屈服强度以及优异的强度和弯曲性均衡,因此使用马氏体单相钢。
因此,近来,为解决具有高强度的同时能够解决冲压加工性和滚压成型加工性的问题,进行了广泛的研究,比如在专利文献1至4中提出了一种在钢材中含有5~35%的锰的奥氏体高锰钢,通过在钢中含有锰,钢材塑性变形时诱导双晶(TWIN)的形成,从而具有高强度的同时能够大幅提高延展性。
然而,具有奥氏体组织的高锰钢很难将抗张强度提高到1200Mpa以上,因此难以制造成超高强度的钢。即,为将抗张强度提高至1200Mpa以上,还需进一步添加Mn、Si、Cr、V等合金元素。
然而,如果添加上述能够使高锰钢超高强度化的合金元素,则会导致热镀锌性能进一步劣化,因此不优选。更加具体地,对于将高锰钢用作涂镀材料的热镀锌钢板,为确保材质以及表面活性化(还原),主要在包含氢的氮氛围下进行退火处理,这对于涂镀材料基础铁(Fe)来说是还原性氛围,相反对于高锰钢中含有的Mn、Si、Al、Cr等易氧化的元素来说是氧化性氛围。因此,如果在这样的氛围条件下对含有大量的Mn以及Al、Si等元素的高锰钢进行退火处理,则合金元素因氛围中的少量的水分或氧气而被选择性地氧化(选择氧化),在材料(涂镀材料)表面产生Mn、Al、Si等的表面氧化物,进行涂镀时因表面氧化物而发生未涂镀的现象,即使已涂镀,在加工时也会发生涂镀层剥离的问题。
即,在一般的作业条件下,为使钢具有超高强度而在高锰钢中进一步添加合金元素时几乎无法确保涂镀性,而且添加这些高价合金元素使制造成本大幅增加。
现有技术文献
专利文献
(专利文献1)日本专利公开公报特开平4-259325
(专利文献2)国际专利公开公报WO 93/013233
(专利文献3)国际专利公开公报WO 99/001585
(专利文献4)国际专利公开公报WO 02/101109
发明内容
(一)要解决的技术问题
本发明的目的在于提供一种高锰热镀锌钢板的制造方法及用该方法制造的高锰热镀锌钢板,在没有添加高价合金元素或者进行高温退火处理的情况下,具有超高强度的同时不发生未涂镀或者涂镀剥离等涂镀表面缺陷,且具有优异的涂镀性。
(二)技术方案
本发明的一个实施方式提供一种高锰热镀锌钢板的制造方法,包括以下步骤:以30~60%的压下率对热轧钢板进行冷轧来得到冷轧钢板,所述热轧钢板,以重量%计,包括:C:0.3~1%、Mn:8~25%、Si:0.1~3%、Al:0.01~8%、Cr:0.1~2%、Ti:0.01~0.2%、B:0.0005~0.01%、Ni:0.01~2%、Sn:0.06~0.2%、余量Fe和其他杂质;将所述冷轧钢板在-30~-80℃的露点温度,450~650℃的温度条件下进行加热;将所述加热的钢板冷却至450~500℃或保持所述温度;以及将所述冷却或保持的钢板浸渍在包含0.13~0.25重量%的Al,温度为450~500℃的热镀锌液中,进行热镀锌。
本发明的另一个实施方式提供一种高锰热镀锌钢板,以重量%计,包括:C:0.3~1%、Mn:8~25%、Si:0.1~3%、Al:0.01~8%、Cr:0.1~2%、Ti:0.01~0.2%、B:0.0005~0.01%、Ni:0.01~2%、Sn:0.06~0.2%、余量Fe和其他杂质,在基础钢板的表面形成粒子状的氧化物,所述氧化物的厚度为10μm以下(0除外),而且未涂镀区域的平均直径小于1mm(0除外)。
(三)有益效果
根据本发明,能够提供一种高锰热镀锌钢板,在没有进一步添加高价合金元素或者进行高温退火处理的情况下,能够通过低温热处理,抑制合金元素的表面凝聚和氧化膜的形成,从而具有1200MPa以上的超高强度和优异的涂镀性。
具体实施方式
本发明的发明人对需进行滚压成型加工的保险杠(bumper beam)、侧水封(sealside)、座椅横挡(seat rail)以及冲撞部位的构件等部件的机械特性进行研究,结果发现这些部件需具有高屈服强度以及优异的强度和弯曲性均衡,但是对于延展性要求不高。即,当抗张强度为1200MPa以上,延伸率为7%以上时,进行构件的弯曲加工时,在不发生断裂的情况下能够进行滚压成型加工,为满足这样的材质特性,可以使用马氏体超高强度钢。但是,马氏体超高强度钢,为得到马氏体相变组织,需在进行退火后快速冷却至马氏体开始温度(Ms)以下,另外,虽然马氏体单相能够确保1200MPa以上的抗张强度,但是难以确保7%以上的延伸率,因此使用在马氏体组织中局部混合有铁素体或者贝氏体的混合组织,为此要进行800℃以上的高温退火处理。
将这种马氏体超高强度钢用作涂镀材料时,通过由高温退火造成的合金元素的表面凝聚及氧化,形成薄膜形状的表面氧化物,在一般的涂镀条件下进行涂镀时产生未涂镀和涂镀剥离的现象,因此需要进行如内部氧化法、Ni预涂覆,二次退火等涂镀前处理。
与此相反,发现奥氏体单相的高锰钢具有均匀的延展性和大的加工硬化率,因此即使在一般的压下率下进行轧制的冷轧材的材质也能够满足滚压成型加工的要求,而且在涂镀之前无需进行用于确保材质的高温退火处理,只通过在能够确保涂镀性的最低热处理温度下,即镀液温度以上,再结晶温度以下的温度范围内进行加热处理,能够确保涂镀性和优异的强度,从而完成了本发明。
下面,对本发明的制造方法进行说明。首先,对合金成分及组分范围的选定进行说明。只是,在没有特别进行说明的情况下,%表示重量%。
C:0.3~1%
所述碳(C)是有助于稳定奥氏体的元素,添加量越多越好,为实现添加效果,所述碳优选添加0.3%以上。但是,当所述C的含量超过1%时,奥氏体的稳定度过于增加,因此通过由滑动引起的变形行为的转变,加工性下降,因此其含量优选为0.3~1%。
Mn:8~25%
所述锰(Mn),通过稳定奥氏体相来进行塑性变形时诱导双晶的形成,因此是提高强度的同时能够大幅提高延展性的高锰钢的必不可少的元素。为实现这样的效果,所述锰优选添加至少8%以上。但是,当所述Mn的含量超过25%时,降低高温延展性,在铸造工序中产生断裂,在用于热轧的再加热工序中,发生急剧的高温氧化,从而降低产品的表面品质,在热涂镀之前进行的退火处理工序中,不仅因表面氧化(选择氧化)而妨碍涂镀性,而且由于添加大量的Mn,导致制造成本上升,因此所述Mn的含量优选为8~25%。
Si:0.1~3%
只添加单独的所述硅(Si)时,在热涂镀之前进行的退火工序中,因产生表面凝聚而形成很密致的薄膜(皮膜)形状的Si氧化物,导致热涂镀性能下降,因此优选不添加,但是,如本发明,与Mn一起复合添加时,薄膜形状的Si氧化物受Mn的约束而变成粒子型,还具有减小Mn氧化物厚度的效果。为实现如上所述的效果,将Si与Mn的添加量比优选为1/5倍以下(Si/Mn≤0.2),当添加量比为1/5倍以上时,会产生薄膜形状的Si氧化物和Mn氧化物,在进行热涂镀过程中,由于润湿性下降而产生未涂镀和涂镀剥离的现象,因此不优选。但是,当Si添加量为3%以上时,高锰钢的延性急剧下降,因此将Si添加量的上限限制在3%以下。并且,当Si添加量低于0.1%时,强度提高效果不明显,因此将Si添加量的下限限制在0.1%以上。
Al:0.01~8%
铝(Al)通常作为脱氧剂来添加,在本发明的高锰钢中,添加Al是为防止延迟断裂(delayed fracture)。Al是稳定铁素体相的成分,而且在钢的滑动面上增加堆垛层错能(stacking fault energy),抑制ε(艾普西隆)-马氏体相的生成,从而提高延展性,提高耐延迟断裂性能。不仅如此,即使Mn的添加量低的情况下,Al也能够抑制ε(艾普西隆)-马氏体相的产生,因此起到使Mn的添加量最少的作用。为在高锰钢中发挥这样的效果,Al优选添加1%以上。然而,当Al添加量超过8%时,抑制双晶的产生,从而降低延展性,不仅在连续铸造时使铸造性能变差,而且由于Al是易氧化的元素,因此在热涂镀之前进行的退火过程中发生表面氧化,妨碍与热锌之间的润湿性,因此将Al添加量的上限限制在8%以下。
Cr:0.1~2%
同Si一样,所述铬(Cr)在大气中形成钝化膜,具有防腐蚀的效果,在进行高温热轧时,防止钢中的碳发生脱碳,并且在钢板的表面抑制α′-马氏体相的生成,从而提高钢的成型性。因此,所述Cr优选添加0.1%以上。但是,当作为铁素体稳定化的元素的Cr的添加量超过2%时,反而会促进α′-马氏体相的生成,从而降低钢的延展性。并且,从涂镀的方面来说,添加Cr会在表面下方产生Cr氧化物,防止涂镀性差的Mn、Si及Al的表面凝聚和氧化,从而能够改善涂镀性,但是当Cr添加量过高时,形成以Cr氧化物为主体的较厚的复合氧化物,妨碍与热锌之间的润湿性,产生未涂镀或者涂镀剥离的现象,因此将Cr添加量的上限限制在2%。
Ti:0.01~0.2%
所述钛(Ti)固溶于柱状晶界,提高Al凝聚的低熔点化合物的熔化温度,在1300℃以下阻止液态膜的形成,并且与氮的亲和力高,用作导致柱状晶界脆化的粗大的氮化铝(AlN)析出核,从而强化柱状晶界。然而,当Ti的添加量低于0.01%时没有效果,超过0.2%时过量的Ti偏析在晶界,导致产生晶界脆化,因此所述Ti的含量优选为0.01~0.2%。
B:0.0005~0.01%
所述硼(B)在1000℃以上固溶于柱状晶界,抑制空孔的产生和移动,从而强化柱状晶界。然而,当所述硼的添加量低于0.0005%时没有效果,超过0.01%时,会产生大量的碳化物和氮化物,其用作氮化铝析出核,助长粗大的氮化铝的析出,从而使晶界脆化。并且,从涂镀性方面来说,当硼的添加量为0.01%以上时,在涂镀之前进行的退火工序中,因晶界凝聚和氧化而形成硼氧化物,从而产生未涂镀的现象,因此将硼的添加量限制在0.0005~0.01%。
Ni:0.01~2%
所述镍(Ni),其材质为提高奥氏体相的稳定度,从而抑制破坏成型性的α′-马氏体相的生成。因此,在常温下也具有奥氏体相的高锰钢中,促进双晶的形成,加工时起到提高强度和延展性的作用。并且,从涂镀性方面来说,由于Ni是稀有元素,因此在高温下Ni自身不会发生氧化,而是析出在表面上,从而抑制基础铁中的Al、Mn、Si等易氧化的元素的表面扩散,因此不仅减小表面氧化物的厚度,而且带来组分的变化,从而表现与热锌之间的优异的润湿性。为实现这样的效果,Ni添加量至少为0.01%以上,但是当Ni的添加量增加时,沿着晶界发生急剧的内部氧化,由此进行热轧时有可能产生断裂,而且成本也上升,因此将Ni添加量的上限限制在2%。
Sn:0.06~0.2%
所述锡(Sn)是稀有元素,在高温下Sn自身不会形成氧化膜,因此在热涂镀之前进行退化处理时,析出在材料表面,从而抑制Al、Si、Mn等亲氧化性元素扩散至表面而形成氧化物,具有改善涂镀性的效果。然而,当Sn的添加量为0.06%以下时,效果不明显,随着添加量的增加,虽然能够抑制选择氧化物的形成,但是当添加量为0.2%以上时,产生赤热脆性,妨碍热轧加工性,因此将Sn的添加量的上限限制在0.2%以下。
准备具有如上所述的合金成分和组分范围的热轧钢板,然后通过对所述热轧钢板进行冷轧来得到冷轧钢板。在将所述热轧钢板进行冷轧之前,为去除所述热轧钢板表面的杂质或氧化铁皮等,优选进行进一步的酸洗工序。进行所述冷轧时,压下率的范围优选为30~60%。根据本发明的发明人的研究结果,发现在不同的压下率下对含有大量的锰以及铝和硅的高锰钢热轧钢板进行冷轧时,材料随冷轧压下率发生变化。然而,本发明的高锰钢加工硬化率大,因此可适用的冷轧压下率的上限约为60%左右,而且此时的总延伸率为7%以上,因此在没有进一步的合金元素的热处理的情况下,能够确保滚压成型加工所需的材质。另一方面,在本发明中,为满足在汽车构件滚压成型加工所需的1200MPa以上的抗张强度和7%以上的延伸率,至少具有30%以上的压下率。因此,进行所述冷轧时,压下率的范围优选为30~60%。为确保更加优异的加工性,所述压下率的范围更加优选为30~45%,再更加优选为30~37%。
之后,将通过所述冷轧后得到的冷轧钢板,在-30~-80℃的露点温度为,450~650℃的温度条件下进行加热。进行所述加热时,如果露点温度超过-30℃,实际会形成氧化性氛围,从而形成内部氧化物的同时形成厚的表面氧化物,因此产生未涂镀和涂镀剥离的现象。相反,如果露点温度为-30℃以下,会形成还原氛围,从而防止Mn、Al、Si等合金元素的表面扩散和氧化。尤其是,当高锰钢的露点温度越低时,越能够防止Mn的表面凝聚,因此露点温度越低越好,但是为了将露点温度保持在低于-80℃的温度,需要去除气体的氧气和水分,这需要很多净化装置,因此不优选。因此,露点温度的范围优选为-30~-80℃。
另一方面,将高强度高锰钢用作涂镀材料进行热镀锌时,在一般的涂镀条件下,在涂镀之前需进行750℃以上的高温退火处理,由此因Mn、Al、Si等合金元素的表面凝聚和氧化,形成厚的表面氧化物,从而在进行涂镀时与热锌之间的润湿性下降,导致产生未涂镀和涂镀剥离的现象。然而,根据本发明的发明人的研究发现,将超高强度高锰钢,如一般的退火工序一样,在高温下进行热处理时,反而会产生未涂镀和涂镀剥离的现象,而在低温下进行加热时能够解决上述的未涂镀和涂镀剥离的问题。更为具体地,当加热温度超过650℃时,合金元素的表面凝聚增加,在表面上形成薄膜形状的厚的氧化膜,从而产生未涂镀和涂镀剥离的现象,而且抗张强度和屈服强度也降至很低,失去超高强度钢的材质特性,相反,在650℃以下的温度下进行热处理时,易氧化的合金元素的表面凝聚减少,表面氧化物的形状为不连续的粒子状,而且厚度也薄,10μm以下,因此在进行涂镀时不会产生未涂镀和涂镀剥离的现象,能够确保1200MPa的抗张强度和7%以上的延伸率,从而具有优异的材质特性。如上所述,本发明的加热温度的范围低于一般的退火温度,而且温度越低时效果越好。只是,当加热温度低于450℃时,表面氧化物非常薄,且呈粒子形状,因此可预想到其具有优异的涂镀性,但是由于钢板的温度(钢板引入温度)低于涂镀液的温度,因此与热锌之间的润湿性和反应下降,从而具有产生未涂镀或者因表面抑制层(inhibition layer)的形成很微弱而产生涂镀剥离的缺点。因此,加热温度的范围优选为450~650℃。为提高钢板的强度和涂镀性,所述加热温度的范围更加优选为450~600℃,再更加优选为450~550℃。
之后,将所述加热的钢板冷却至450~500℃或保持所述温度。所述冷却或保持工序是用于提高所述钢板的涂镀润湿性的工序,在引入涂镀液之前如果钢板的温度低于450℃,则由于钢板温度低于涂镀液而与热锌之间的润湿性和反应下降,有可能产生未涂镀,或者因表面抑制层(inhibition layer)的形成微弱而有可能产生涂镀剥离。相反,如果钢板的温度超过500℃,则从基础铁熔析余量的Fe,与涂镀液的Zn或Al产生反应,从而产生Fe-Zn底渣(botto m dross)和Fe-Al浮渣(floating dross),所述渣的一部分混入于涂镀层,妨碍表面外观,因此不优选。
接着,将如上述的被冷却或者保持的钢板浸渍在含有0.13~0.25重量%的Al,温度为450~500℃的热镀锌液中,进行热镀锌。如果将经过加热处理的钢板浸渍在涂镀液,涂镀液中的Al首先与钢板产生反应,从而还原钢板表面的氧化膜,形成作为表面抑制层的Fe-Mn-Al-Zn膜,其起到抑制脆弱的Zn-Fe金属间化合物生长的作用。此时所述Al的含量越高时越有利,但是当涂镀液中的Al浓度超过25%时,容易产生作为Fe-Al氧化物的浮渣,产生涂镀层流下的流动花纹,因此Al浓度优选为具有0.25%以下的范围。由于超高强度高锰钢在进行低温加热处理时不会发生合金元素的表面凝聚和氧化现象,因此即使在低于通常的Al浓度,即在0.13%的浓度下也能够形成具有延展性的表面抑制层Fe-Mn-Al-Zn膜,因此所述涂镀液中的Al浓度的范围优选为0.13~0.25重量%。另一方面,所述Al浓度低于0.13%时,形成不均匀的表面抑制层,导致产生未涂镀或者涂镀剥离的现象,因此不优选。
另一方面,所述涂镀液的温度低于450℃时,热锌的流动性急剧下降,有可能产生流动花纹等的表面缺陷,当涂镀液的温度超过500℃时,涂镀液的热锌和铝与氧气产生反应,产生过量的作为Zn-Al氧化物的上部渣,而且产生的氧化物附着在涂镀的钢板上,引起表面缺陷,因此不优选。因此,所述涂镀液的温度范围优选为450~500℃。
如前所述,根据本发明提出的高锰热镀锌钢板的制造方法,在没有进一步添加高价合金元素或者进行高温退火的情况下,能够通过低温热处理,抑制合金元素的表面凝聚和氧化膜的形成,从而能够提供确保1200MPa以上的超高强度和7%以上的延伸率的同时具有优异的涂镀性的高锰热镀锌钢板。
例如,提供一种高锰热镀锌钢板,其包括前述的成分,即,以重量%计,包括:C:0.3~1%、Mn:8~25%、Si:0.1~3%、Al:0.01~8%、Cr:0.1~2%、Ti:0.01~0.2%、B:0.0005~0.01%、Ni:0.01~2%、Sn:0.06~0.2%、余量Fe和其他杂质,在基础钢板的表面形成粒子状的氧化物,所述氧化物的厚度为10μm以下(0除外),而且未涂镀区域的平均直径小于1mm。所述粒子状的氧化物的厚度更加优选为5μm以下,再更加优选为3μm,最优选为1μm以下。所述未涂镀区域的平均直径更加优选为0.5mm以下,再更加优选为0.3mm以下。最优选为不产生未涂镀区域。如上所述,由于在基础钢板形成薄的表面氧化物,因此与现有的形成厚的具有薄膜(膜)形状的表面氧化物的钢板相比,能够解决未涂镀和涂镀剥离的问题,因此具有优异的涂镀性。另一方面,所述表面氧化物越薄时越能够提高涂镀性,因此并不限制其下限。并且,所述热镀锌钢板能够确保1200MPa以上的抗张强度和7%以上的延伸率,从而能够优选适用于汽车的支撑构件等。
下面,通过实施例对本发明进行更加详细说明。只是,下面的实施例仅仅是为更加详细地说明本发明而示例的,本发明的权利范围并不限定于此。
(实施例1)
将包含0.55%C、15%Mn、0.1%Si、1.9%Al、0.28%Cr、0.09%Ti、0.001%B、0.25%Ni、0.06%Sn的高锰钢,通过连续铸造来制造钢坯,在1100℃下对所述钢坯进行加热,然后在950℃下进行热终轧,然后在450℃下进行卷取,由此制造厚度为2.81mm热轧钢板。将所述热轧钢板在15%的盐酸水溶液中进行酸水处理,然后,如下表1中记载,在不同的压下率下进行冷轧,由此制造冷轧钢板。对于通过所述方式制造的冷轧钢板,制造JIS5号拉伸试片,然后测量试片的屈服强度、抗张强度以及延伸率,并将其结果表示在以下表1中。
表1
如上述表1所示,本发明提出的满足压下率范围的发明例1至发明例7,因奥氏体单相和大的加工硬化而能够确保1200MPa以上的抗张强度和7%以上的延伸率。
与此相反,本发明提出的不满足压下率范围的比较例1至比较例5,因加工硬化不足而无法确保超高强度钢的材质。
(实施例2)
在通过实施例1制造的冷轧钢板中,对于采用51%压下率的冷轧钢板,在氢为5%、其余为氮、露点温度为-40℃的还原性氛围下,如以下表2所示,在不同的加热温度下,进行40秒的加热处理,然后冷却至480℃,然后在涂镀液中的Al中浓度为0.23重量%、温度为450℃的热镀锌液中浸渍5秒来进行涂镀,然后用气刀进行控制,使一面的涂镀附着量达到60g/m2,由此制造热镀锌钢板。对于如此制造的热镀锌钢板,测量表面氧化物的厚度和形状,并按照如下标准评价其涂镀品质,并将其结果表示在以下表2中。并且,对于所述热镀锌钢板,制造JIS5号拉伸试片,然后测量试片的屈服强度、抗张强度以及延伸率,并将其结果表示在以下表2中。
对于未涂镀程度,在进行热镀锌后将其表面外观进行图像化处理后测量未涂镀部分的大小,并按照如下的基准分等级。
一等:不存在未涂镀缺陷
二等:未涂镀平均直径小于1mm
三等:未涂镀平均直径为1mm以上,小于2mm
四等:未涂镀平均直径为2mm以上,小于3mm
五等:未涂镀平均直径为3mm以上
另外,对于热镀锌钢板的涂镀附着性,在进行0T弯曲试验后,对弯曲外圈部进行敲击测试,然后按照如下的标准对涂镀层的剥离产生情况进行了评价。
一等:没有剥离
二等:剥离低于5%
三等:剥离5~10%
四等:剥离10~30%
五等:剥离30%以上
表2
如上述表2所示,本发明提出的满足加热温度范围等的发明例8至发明例12,由于进行低温加热处理,形成薄的具有粒子形状的表面氧化物,因此不发生未涂镀和涂镀剥离等表面缺陷。并且,因没有再结晶,能够确保1200MPa以上的抗张强度和7%以上的延伸率。
与此相反,比较例6虽然机械物理性质优异,但是加热温度不足,因此,钢板的温度低于涂镀液的温度,与热锌之间的润湿性和反应下降,从而产生未涂镀,而且表面抑制层的形成微弱,因此产生涂镀剥离。
比较例7至比较例11因高温退火而形成厚的薄膜(膜)形状的表面氧化物,产生未涂镀,即使完成涂镀,在加工期间产生涂镀剥离。并且,抗张强度和屈服强度很低,失去了超高强度钢的材质特性。
Claims (12)
1.一种高锰热镀锌钢板的制造方法,包括以下步骤:
以30~60%的压下率对热轧钢板进行冷轧来得到冷轧钢板,所述热轧钢板,以重量%计,包括:C:0.3~1%、Mn:8~25%、Si:0.1~3%、Al:0.01~8%、Cr:0.1~2%、Ti:0.01~0.2%、B:0.0005~0.01%、Ni:0.01~2%、Sn:0.06~0.2%、余量Fe和其他杂质;
将所述冷轧钢板在-30~-80℃的露点温度,450~650℃的温度条件下进行加热;
将所述加热的钢板冷却至450~500℃或保持所述温度;以及
将所述冷却或保持的钢板浸渍在含有0.13~0.25重量%的Al,温度为450~500℃的热镀锌液中,进行热镀锌。
2.根据权利要求1所述的高锰热镀锌钢板的制造方法,所述压下率为30~45%。
3.根据权利要求2所述的高锰热镀锌钢板的制造方法,所述压下率为30~37%。
4.根据权利要求1所述的高锰热镀锌钢板的制造方法,所述加热温度为450~600℃。
5.根据权利要求4所述的高锰热镀锌钢板的制造方法,所述加热温度为450~550℃。
6.通过权利要求1所述方法制备的高锰热镀锌钢板,以重量%计,包括:C:0.3~1%、Mn:8~25%、Si:0.1~3%、Al:0.01~8%、Cr:0.1~2%、Ti:0.01~0.2%、B:0.0005~0.01%、Ni:0.01~2%、Sn:0.06~0.2%、余量Fe和其他杂质,在基础钢板的表面形成粒子状的氧化物,所述氧化物的厚度为10μm以下,0除外,而且未涂镀区域的平均直径小于1mm,0除外。
7.根据权利要求6所述的高锰热镀锌钢板,所述粒子状的氧化物的厚度为5μm以下。
8.根据权利要求7所述的高锰热镀锌钢板,所述粒子状的氧化物的厚度为3μm以下。
9.根据权利要求6所述的高锰热镀锌钢板,所述未涂镀区域的平均直径为0.5mm以下。
10.根据权利要求7所述的高锰热镀锌钢板,所述未涂镀区域的平均直径为0.3mm以下。
11.根据权利要求6所述的高锰热镀锌钢板,所述钢板的抗张强度为1200Mpa以上。
12.根据权利要求6所述的高锰热镀锌钢板,所述钢板的延伸率为7%以上。
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- 2013-12-19 JP JP2015549262A patent/JP6152427B2/ja not_active Expired - Fee Related
- 2013-12-19 EP EP13864152.7A patent/EP2937436B1/en not_active Not-in-force
- 2013-12-19 CN CN201380067419.2A patent/CN104870679B/zh not_active Expired - Fee Related
- 2013-12-19 WO PCT/KR2013/011900 patent/WO2014098503A1/ko active Application Filing
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Publication number | Publication date |
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JP6152427B2 (ja) | 2017-06-21 |
EP2937436A1 (en) | 2015-10-28 |
CN104870679A (zh) | 2015-08-26 |
US20150329951A1 (en) | 2015-11-19 |
KR20140081602A (ko) | 2014-07-01 |
US10087511B2 (en) | 2018-10-02 |
EP2937436B1 (en) | 2019-08-14 |
EP2937436A4 (en) | 2016-04-13 |
JP2016508183A (ja) | 2016-03-17 |
KR101510505B1 (ko) | 2015-04-08 |
WO2014098503A1 (ko) | 2014-06-26 |
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