CN105531389A - 外观性和镀层密合性优良的热镀锌钢板和合金化热镀锌钢板以及它们的制造方法 - Google Patents
外观性和镀层密合性优良的热镀锌钢板和合金化热镀锌钢板以及它们的制造方法 Download PDFInfo
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- CN105531389A CN105531389A CN201480049859.XA CN201480049859A CN105531389A CN 105531389 A CN105531389 A CN 105531389A CN 201480049859 A CN201480049859 A CN 201480049859A CN 105531389 A CN105531389 A CN 105531389A
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- steel
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- coating
- steel plate
- steel sheet
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 157
- 239000010959 steel Substances 0.000 title claims abstract description 157
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 15
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 15
- 238000007747 plating Methods 0.000 title abstract description 35
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims description 64
- 238000000576 coating method Methods 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 52
- 239000011701 zinc Substances 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 43
- 230000006978 adaptation Effects 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052725 zinc Inorganic materials 0.000 claims description 30
- 238000005246 galvanizing Methods 0.000 claims description 27
- 238000005275 alloying Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 15
- 238000005097 cold rolling Methods 0.000 claims description 9
- 238000005098 hot rolling Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 229910000859 α-Fe Inorganic materials 0.000 abstract 4
- 238000005262 decarbonization Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 55
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 238000000137 annealing Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000004686 fractography Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/34—Methods of heating
- C21D1/52—Methods of heating with flames
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/76—Adjusting the composition of the atmosphere
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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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
- C21D8/0205—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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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- 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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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
- C21D9/561—Continuous furnaces for strip or wire with a controlled atmosphere or vacuum
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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Abstract
本发明的目的在于提供以Si含量高的钢板作为母材、不存在表面缺陷、具有漂亮外观的镀层密合性优良的热镀锌钢板和合金化热镀锌钢板以及它们的制造方法。一种外观性和镀层密合性优良的热镀锌钢板,其特征在于,具有以质量%计含有C:0.08%以上且低于0.20%、Si:0.1~3.0%、Mn:0.5~3.0%、P:0.001%~0.10%、Al:0.01%~3.00%、S:0.200%以下且余量由Fe和不可避免的杂质构成的成分组成,从钢基与锌镀层的界面起在钢基侧具有厚度为5μm以下的内部氧化层,且从钢基与锌镀层的界面起在钢基侧具有厚度为20μm以下的脱碳层,而且所述内部氧化层以面积率计含有50%以上的由Fe2XMn2-2XSiOY表示的含有Fe和/或Mn的Si氧化物。在此,X=0~1,Y=3或4。
Description
技术领域
本发明涉及以含Si钢板作为母材的外观性和镀层密合性优良的热镀锌钢板和合金化热镀锌钢板以及它们的制造方法。
背景技术
近年来,在汽车、家电、建材等领域中,使用对原材钢板赋予了防锈性的表面处理钢板,其中,使用防锈性优良的热镀锌钢板、合金化热镀锌钢板。
一般而言,热镀锌钢板通过以下的方法来制造。首先,使用对板坯实施了热轧、冷轧或热处理的薄钢板,在预处理工序中对钢板表面进行脱脂和/或酸洗来进行清洗,或者省略预处理工序而在预热炉内将钢板表面的油分燃烧除去,然后,在非氧化性气氛中或还原性气氛中进行加热,由此进行再结晶退火。然后,在非氧化性气氛中或还原性气氛中将钢板冷却至适合于镀覆的温度,在不与大气接触的情况下浸渍到添加有微量Al(约0.1质量%~约0.2质量%)的熔融锌浴中。由此,钢板表面被镀覆而得到热镀锌钢板。另外,合金化热镀锌钢板通过在热镀锌后在合金化炉内对钢板进行热处理而得到。
近年来,在汽车领域中,在原材钢板的高性能化的同时促进轻量化。用于弥补原材钢板的轻量化所伴随的强度降低的钢板的高强度化通过添加Si、Mn等固溶强化元素来实现。其中,Si具有能够在不损害钢的延展性的情况下进行高强度化的优点,含Si钢板有望作为高强度钢板。另一方面,在想要以钢中含有大量Si的高强度钢板作为母材来制造热镀锌钢板和合金化热镀锌钢板的情况下,存在以下的问题。
如上所述,热镀锌钢板在镀覆前在还原气氛中进行退火。但是,钢中的Si与氧的亲和力高,因此,即使在还原气氛中也被选择性地氧化,在钢板表面形成氧化物。这些氧化物使钢板表面的润湿性降低,因此,在镀覆时,成为不上镀缺陷的原因。另外,即使在未达到不上镀的情况下,也存在使镀层密合性降低的问题。
此外,这些氧化物在热镀锌后的合金化过程中使合金化速度显著降低。结果,合金化热镀锌钢板的生产率大幅降低。另一方面,为了确保生产率而在高温下进行合金化处理时,还存在抗粉化性降低的问题,难以兼顾高效的生产率和良好的抗粉化性。另外,高温下的合金化处理使残余γ相不稳定,因此会损害添加Si所带来的优点。可见,制造兼顾机械特性和镀层品质的高强度热镀锌钢板是非常困难的。
针对这样的问题,公开了若干技术。在专利文献1中公开了如下技术:首先,在氧化气氛中在钢板表面形成氧化铁,然后,通过还原退火在钢板表面形成还原铁层,由此改善与熔融锌的润湿性。另外,在专利文献2中公开了通过控制预热中的氧浓度等气氛来确保良好的镀层品质的技术。另外,在专利文献3中公开了如下技术:将加热区划分为A~C区这3个阶段,将各加热区控制为适当的温度和氧浓度,由此抑制压痕(押し疵)产生,制造不存在不上镀的外观漂亮的热镀锌钢板。
现有技术文献
专利文献
专利文献1:日本特开平4-202630号公报
专利文献2:日本特开平6-306561号公报
专利文献3:日本特开2007-291498号公报
发明内容
发明所要解决的问题
在专利文献1、2那样的应用氧化还原技术对Si含量高的钢进行热镀锌处理的方法中,不上镀缺陷得到改善,但另一方面,存在产生压痕这样的氧化还原技术特有的缺陷的问题。另外,在专利文献3那样的分别对A~C加热区的温度和氧浓度进行控制的方法中,能够提供不存在不上镀、压痕这样的表面缺陷的热镀锌钢板。但是,由于钢板的氧化物量因制造条件(制造计划)而产生偏差,因此存在难以提供稳定的钢板的问题。即,即使将加热区的温度控制为相同,有时也会因制造条件(制造计划)而导致钢板的氧化物量不足,从而产生不上镀缺陷。
本发明是鉴于上述情况而完成的,其目的在于提供以Si含量高的钢板作为母材、不存在表面缺陷、具有漂亮外观的镀层密合性优良的热镀锌钢板和合金化热镀锌钢板以及它们的制造方法。
用于解决问题的方法
已知在直火型加热炉中利用直火燃烧器对钢板进行加热的情况下,形成在钢板表面的氧化物量受到炉内温度或可燃性气体与助燃性气体的混合比的影响。另外还已知:在升温过程中在钢基(以下有时将钢板称为钢基)表面形成外部氧化物;从钢基与外部氧化物的界面起在内侧形成内部氧化物。外部氧化物为FexMn1-xO、Fe3XMn3-3XO4、Fe2XMn2-2XO3等,X为0~1的范围。内部氧化物为SiO2、由Fe2XMn2-2XSiOY表示的含有Fe和/或Mn的Si氧化物,X为0~1的范围,Y为3或4。作为由Fe2XMn2-2XSiOY表示的含有Fe和/或Mn的Si氧化物,可以举出例如Fe2SiO4、FeMnSiO4、Mn2SiO4、FeSiO3或MnSiO3等。需要说明的是,为了与SiO2相区分,以下有时将由Fe2XMn2-2XSiOY表示的含有Fe和/或Mn的Si氧化物简称为含有Fe和/或Mn的Si氧化物。
在此,所形成的外部氧化物在之后的退火中被还原,在钢板表面形成还原Fe层,因此,具有改善与Zn镀层的润湿性、抑制不上镀的效果。另外,SiO2、含有Fe和/或Mn的Si氧化物等内部氧化物具有降低钢中的Si活度、抑制退火中的Si表面富集、抑制不上镀的效果。
本发明人对于除了炉内温度和气体混合比以外给Si含量高的钢板的氧化行为带来影响的因素进行了研究。结果发现,在钢板中含有碳且燃烧气氛中的碳势低的情况下,与氧化同时在钢板内部发生的脱碳反应会导致钢板内部的氧势降低。结果,从钢基与外部氧化物的界面起在内侧促进从SiO2向Fe2XMn2-2XSiOY所表示的含有Fe和/或Mn的Si氧化物的反应。
SiO2与含有Fe和/或Mn的Si氧化物相比,氧化物中的离子扩散慢,因此,可抑制Fe离子、Mn离子的向外扩散。因此,通过Fe和Mn与氧的反应生成的FexMn1-xO、Fe3XMn3-3XO4、Fe2XMn2-2XO3之类的外部氧化物的形成减少。即,在利用直火燃烧器的加热这样的短时间升温中,难以确保用于抑制不上镀所需要的外部氧化物量。另外,在退火后的钢板表面,在未被还原Fe层覆盖的部分,氧化时形成的SiO2等内部氧化物露出于表面。存在于表面的SiO2排斥熔融锌而成为不上镀的起点,因此,使锌镀层表面外观显著下降。
在本发明中,伴随氧势的降低,从SiO2向含有Fe和/或Mn的Si氧化物的反应得到促进。含有Fe和/或Mn的Si氧化物与SiO2相比,与熔融锌的润湿性良好,因此,在露出于表面的情况下也不易成为不上镀的起点。
进而,本发明人对于在利用直火加热型加热炉的加热和还原气氛中的退火加热这一系列热处理工序中用于稳定地形成含有Fe和/或Mn的Si氧化物的加热条件进行了考察。结果查明,对于碳浓度为0.08质量%以上且低于0.20质量%的钢板,在使可燃性气体中的CO和烃气体的浓度为60体积%以下、使助燃性气体中的O2浓度为20~50体积%的气氛下中将钢板表面的到达温度加热至600~800℃后,在氢气浓度为3~25体积%、水蒸气浓度为0.070体积%以下且余量为N2和不可避免的杂质的气氛中,在630~850℃的均热温度下对钢板进行加热,由此能够从钢基与锌镀层的界面起在钢基侧稳定地形成面积率为50%以上的含有Fe和/或Mn的Si氧化物。此外还查明,在该条件下得到的钢板内部的内部氧化层的厚度为5μm以下、脱碳层的厚度为20μm以下。需要说明的是,本发明中,内部氧化层是指在钢基内部观察到内部氧化物的区域,是检测到相对于深度50~60μm的氧峰的平均值为2倍以上的氧峰的区域。另外,本发明中,脱碳层是指从钢基与锌镀层的界面起存在于钢基侧的贫碳层,是与母材中相比碳浓度为一半以下的区域。
本发明是基于上述见解而完成的,其主旨如下所述。
[1]一种外观性和镀层密合性优良的热镀锌钢板,其特征在于,
具有以质量%计含有C:0.08%以上且低于0.20%、Si:0.1~3.0%、Mn:0.5~3.0%、P:0.001%~0.10%、Al:0.01%~3.00%、S:0.200%以下且余量由Fe和不可避免的杂质构成的成分组成,
从钢基与锌镀层的界面起在钢基侧具有厚度为5μm以下的内部氧化层,且从钢基与锌镀层的界面起在钢基侧具有厚度为20μm以下的脱碳层,而且所述内部氧化层以面积率计含有50%以上的由Fe2XMn2-2XSiOY表示的含有Fe和/或Mn的Si氧化物,
在此,X=0~1,Y=3或4。
[2]如[1]所述的外观性和镀层密合性优良的热镀锌钢板,其特征在于,以质量%计,进一步含有Mo:0.01~1.00%和/或Cr:0.01~1.00%。
[3]如[1]或[2]所述的外观性和镀层密合性优良的热镀锌钢板,其特征在于,以质量%计,进一步含有Nb:0.005~0.20%、Ti:0.005~0.20%、Cu:0.01~0.50%、Ni:0.01~1.00%、B:0.0005~0.010%中的至少一种以上。
[4]如[1]~[3]中任一项所述的外观性和镀层密合性优良的合金化热镀锌钢板,其特征在于,锌镀层为合金化锌镀层。
[5]一种外观性和镀层密合性优良的热镀锌钢板的制造方法,其特征在于,
对具有[1]~[3]中任一项所述的成分组成的钢进行热轧后,
进行冷轧,
接着,在具备直火燃烧器的直火加热型加热炉中进行热处理,所述热处理中,使CO和烃气体的合计浓度为60体积%以下且余量为H2、N2和不可避免的杂质的可燃性气体与O2浓度为20~50体积%且余量为N2和不可避免的杂质的助燃性气体燃烧,将钢板表面的到达温度加热至600~800℃的范围,
然后,在氢气浓度为3~25体积%、水蒸气浓度为0.070体积%以下且余量为N2和不可避免的杂质的气氛中,在630~850℃的均热温度下对钢板进行加热,
然后,实施热镀锌处理。
[6]如[5]所述的外观性和镀层密合性优良的合金化热镀锌钢板的制造方法,其特征在于,在热镀锌处理后,对锌镀层进行合金化处理。
发明效果
根据本发明,能够稳定地制造以Si含量高的钢板作为母材、不存在不上镀之类的表面缺陷、具有漂亮外观的镀层密合性优良的热镀锌钢板。需要说明的是,本发明在以通常被认为难以进行热镀锌处理的含有0.1%以上的Si的钢板、即Si含量高的钢板作为母材的情况下是有效的,可以说是作为显著改善Si含量高的热镀锌钢板的制造中的成品率的方法有用的发明。
附图说明
图1是表示本发明的热镀锌钢板中的钢基内部的碳浓度和氧浓度的分布的一例的图。
图2是对实施例的表2的结果进行归纳的图,图2(a)是表示表面外观的结果的图,图2(b)是表示镀层密合性的结果的图。
具体实施方式
以下,具体地对本发明进行说明。
首先,对本发明中使用的钢板的成分组成进行说明。需要说明的是,只要没有特别说明,则表示成分的量的%是指质量%。
C:0.08%以上且低于0.20%
为了通过脱碳反应所引起的氧势的降低来充分地促进含有Fe和/或Mn的Si氧化物的形成,需要含有0.08%以上的C。另一方面,通过使C低于0.20%,加工性优良。因此,C设定为0.08%以上且低于0.20%。另外,C优选为0.08%以上,更优选为0.10%以上。
Si:0.1~3.0%
Si在改善钢板的机械特性的方面是最重要的元素,因此,需要含有0.1%以上。但是,Si超过3.0%时,难以抑制钢基与氧化物的界面上的SiO2系氧化物的生成,难以确保抑制不上镀所需要的氧化物量。因此,Si设定为0.1~3.0%。
Mn:0.5~3.0%
Mn为固溶强化元素,对于实现钢板的高强度化是有效的,因此,需要含有0.5%以上。另一方面,Mn超过3.0%时,焊接性、镀层密合性降低,而且难以确保强度延展性平衡。因此,Mn设定为0.5~3.0%。
P:0.001~0.10%
P使渗碳体的析出延迟从而使相变的进行减慢,因此设定为0.001%以上。另一方面,P超过0.10%时,焊接性和镀层密合性劣化。此外还会使合金化延迟,因此合金化温度升高,延展性劣化。因此,P设定为0.001~0.10%。
Al:0.01~3.00%
Al是与Si互补地添加的元素。Al在炼钢过程中不可避免地混入,因此,Al的下限值为0.01%。另一方面,Al超过3.00%时,难以抑制外部氧化物的生成,镀层的密合性降低。因此,Al设定为0.01~3.00%。
S:0.200%以下
S是在炼钢过程中不可避免地含有的元素。但是,大量含有时,焊接性劣化。因此,S设定为0.200%以下。
在本发明中,除了上述的成分组成以外,可以进一步含有Mo和/或Cr。
Mo:0.01~1.00%
Mo是控制强度与延展性的平衡的元素,可以含有0.01%以上。另外,Mo具有促进Si、Al的内部氧化、抑制表面富集的效果。另一方面,Mo超过1.00%时,有时导致成本升高。因此,在含有Mo的情况下,优选为0.01~1.00%。
Cr:0.01~1.00%
Cr是控制强度与延展性的平衡的元素,可以含有0.01%以上。另外,Cr与Mo同样地具有促进Si、Al的内部氧化、抑制表面富集的效果。另一方面,Cr浓度超过1.00%时,Cr富集在钢板表面,因此镀层密合性和焊接性劣化。因此,在含有Cr的情况下,优选为0.01~1.00%。
在本发明中,除了上述的成分组成以外,可以根据所期望的特性含有以下的元素。
Nb:0.005~0.20%
Nb是控制强度与延展性的平衡的元素,可以含有0.005%以上。另一方面,Nb超过0.20%时,有时导致成本升高。因此,在含有Nb的情况下,优选为0.005~0.20%。
Ti:0.005~0.20%
Ti是控制强度与延展性的平衡的元素,可以含有0.005%以上。另一方面,Ti超过0.20%时,有时会使镀层密合性降低。因此,在含有Ti的情况下,优选为0.005~0.20%。
Cu:0.01~0.50%
Cu是促进残余γ相形成的元素,可以含有0.01%以上。另一方面,Cu超过0.5%时,有时导致成本升高。因此,在含有Cu的情况下,优选为0.01~0.50%。
Ni:0.01~1.00%
Ni是促进残余γ相形成的元素,可以含有0.01%以上。另一方面,Ni超过1.00%时,有时导致成本升高。因此,在含有Ni的情况下,优选为0.01~1.00%。
B:0.0005~0.010%
B是促进残余γ相形成的元素,可以含有0.0005%以上。另一方面,B超过0.010%时,有时镀层密合性劣化。因此,在含有B的情况下,优选为0.0005~0.010%。
上述以外的余量为Fe和不可避免的杂质。
接着,对本发明中最重要的从钢基与锌镀层的界面起存在于钢基侧的内部氧化物和脱碳层进行说明。
本发明的特征在于,从钢基与锌镀层的界面起在钢基侧具有厚度为5μm以下的内部氧化层和厚度为20μm以下的脱碳层,而且内部氧化物层含有面积率为50%以上的含有Fe和/或Mn的Si氧化物。
在实施热镀锌处理之前,将冷轧后的钢板在直火加热型加热炉中进行加热后,在还原气氛中进行加热。在此,在直火加热型加热炉中利用直火燃烧器对钢板表面进行加热。此时,在钢板中充分含有碳的情况下,在通过利用直火燃烧器的加热产生的钢板表面氧化的同时,在钢板内部发生下式(1)所示的脱碳反应。通过该脱碳反应,钢板内部的氧势降低。
C+1/2O2→CO…(1)
伴随该氧势的降低,在外部氧化物与钢基的界面,从SiO2生成含有Fe和/或Mn的Si氧化物的平衡反应得到促进(例如参考下式(2))。
如此,在本发明中,氧势因脱碳反应而降低,由此促进式(2)的反应,结果,有效地促进含有Fe和/或Mn的Si氧化物的形成。含有Fe和/或Mn的Si氧化物中的离子扩散速度与SiO2相比极为快速,因此,即使在直火燃烧器那样的短时间加热中也能够确保抑制不上镀所需要的氧化物量。SiO2成为离子扩散的屏障,因此,在直火燃烧器加热那样的短时间升温中,难以确保用于抑制不上镀所需要的外部氧化物量。在本发明中,在钢基与外部氧化物的界面,通过脱碳反应来促进从SiO2向含有Fe和/或Mn的Si氧化物的反应,确保用于抑制不上镀所需要的量的外部氧化物量。
在退火后的钢板表面,在未被还原Fe层覆盖的部分,氧化时形成的内部氧化物露出于表面。存在于表面的SiO2排斥熔融锌而成为不上镀的起点,因此,使锌镀层表面外观显著下降。在本发明中,伴随氧势的降低,从SiO2向含有Fe和/或Mn的Si氧化物的反应得到促进。含有Fe和/或Mn的Si氧化物与SiO2相比,与熔融锌的润湿性良好,因此,在露出于表面的情况下也不易成为不上镀的起点。结果,能够抑制不上镀。
另外,钢板内部的过剩量的内部氧化物使Zn镀层的密合性降低。这是因为,内部氧化物与钢基的热膨胀率不同,因此,在制造过程中在内部氧化物与钢基的界面产生空隙而成为裂纹传播的起点。在此,与SiO2相比,含有Fe和/或Mn的Si氧化物的热膨胀率与Fe接近,因此,不易在内部氧化物与钢基之间产生空隙。即,与SiO2相比,Zn镀层密合性得到改善。
从钢基与锌镀层的界面起在钢基侧以5μm以下的厚度形成内部氧化物层。超过5μm时,在断面观察中有时产生被称为黑斑的内部缺陷。此外,过剩量的内部氧化会导致Zn镀层密合性降低。另外,从钢基与锌镀层的界面起在钢基侧以20μm以下的厚度形成脱碳层。超过20μm时,难以形成残余γ相,会损害由Si添加带来的机械特性的优点。
另外,内部氧化层的特征在于,以面积率计含有50%以上的含有Fe和/或Mn的Si氧化物。面积率小于50%时,无法充分得到通过促进含有Fe和/或Mn的Si氧化物的形成而带来的镀覆性外观和密合性改善。需要说明的是,图1为本发明的热镀锌钢板中的钢基内部的碳浓度和氧浓度的分布的一例。
含有Fe和/或Mn的Si氧化物可以通过在SEM观察的断面组织中利用EDX进行氧化物中的Si、Mn、Fe的组成分析来鉴定。此外,也可以利用基于EPMA的元素分布像或基于TEM的电子射线衍射图像来进行鉴定。需要说明的是,本发明中的面积率是指整个内部氧化层中的含有Fe和/或Mn的Si氧化物的比例。另外,面积率的求法如下:利用断面组织的EPMA元素分布像分别鉴定存在于钢基内的内部氧化物中存在的Si、Mn、Fe浓度,将Si的比例为95%以上的氧化物作为SiO2,将Si的比例小于95%的氧化物作为含有Fe和/或Mn的Si氧化物。另外,本发明的内部氧化层、脱碳层、含有Fe和/或Mn的Si氧化物的面积率可以通过退火条件、钢中C量和钢中Si量来进行控制。
接着,对本发明的热镀锌钢板的制造方法进行说明。
对具有上述成分组成的钢进行热轧后,进行冷轧而制成钢板,接着,在设有具备直火燃烧器的直火加热型加热炉的连续式热镀锌设备中进行退火和热镀锌处理。另外,可以根据需要在热镀锌处理后进行合金化处理。
热轧
热轧可以在通常进行热轧的条件下进行。
酸洗
热轧后,优选进行酸洗处理。在酸洗工序中,将表面上生成的黑色氧化皮除去,然后进行冷轧。需要说明的是,酸洗条件没有特别限定。
冷轧
冷轧优选以30~90%以下的压下率进行。压下率低于30%时,再结晶延迟,因此机械特性容易劣化。另一方面,压下率超过90%时,不仅轧制成本升高,退火时的表面富集也增加,因此镀层特性劣化。
接着,对形成本发明中最重要的内部氧化物和脱碳层的退火条件进行说明。退火是在直火加热型加热炉中加热后在还原气氛中进行加热的一系列热处理工序。
在含有CO和烃气体的浓度为60体积%以下的可燃性气体与O2浓度为20体积%以上且50体积%以下的助燃性气体的气氛中将钢板表面的到达温度加热至600~800℃
在本发明中,在冷轧后在直火型加热炉中对钢板进行加热。具体而言,利用具备直火燃烧器的直火加热型加热炉对钢板表面进行加热。此时,以使钢板表面的到达温度为600~800℃的范围的方式进行加热。钢板表面的到达温度为600℃以下时,抑制不上镀所需要的氧化物量不足。另一方面,钢板表面的到达温度为800℃以上时,氧化物量过多,在表面产生称为压痕的缺陷。因此,将钢板表面的到达温度设定为600~800℃。
另外,在直火型加热炉中进行加热时,在低碳和低氧势气氛下进行。具体而言,在具备直火燃烧器的直火加热型加热炉中,使CO和烃气体的合计浓度为60体积%以下且余量为H2、N2和不可避免的杂质的可燃性气体与O2浓度为20~50体积%且余量为N2和不可避免的杂质的助燃性气体燃烧来进行加热。偏离上述条件时,无法充分促进由脱碳反应引起的钢基与氧化物的界面的氧势的降低。
在氢气浓度为3~25体积%、水蒸气浓度为0.070体积%以下且余量为N2和不可避免的杂质的气氛中在630~850℃的均热温度下对钢板进行加热
接着,在利用直火燃烧器进行加热后,在氢气浓度为3~25体积%、水蒸气浓度为0.070体积%以下且余量为N2和不可避免的杂质的气氛中,在630~850℃的均热温度下对钢板进行加热(退火)。这是为了对钢板表面进行还原处理而进行的。为了得到充分的还原能力,氢气浓度需要为3体积%以上。另一方面,氢气浓度为25体积%以上时,操作成本升高。另外,水蒸气浓度为0.070体积%以上时,在退火中促进由H2O引起的脱碳反应,因此,脱碳层的厚度变得比20μm更厚。脱碳层过厚时,难以形成残余γ相,会损害Si添加所带来的优点。基于以上理由,将退火气氛设定为氢气浓度为3~25体积%和水蒸气浓度为0.070体积%以下的气氛。
在上述的气氛下,在630~850℃的均热温度下对钢板进行加热,进行还原退火。钢板的到达温度为630℃以下时,再结晶延迟,因此机械特性劣化。钢板的到达温度超过850℃时,Si等的表面富集被促进,因此发生不上镀。
退火后,实施热镀锌处理。另外,在热镀锌处理后,可以根据需要实施合金化处理。
作为热镀锌处理和合金化处理中的Zn浴的浴温,优选使用浴温为440~550℃的Zn浴。浴温低于440℃时,浴内部的温度不均大,可能发生Zn的凝固,因此不适合。另一方面,浴温超过550℃时,Zn浴成分的蒸发剧烈,产生操作成本或Zn浴蒸发导致的操作环境劣化的问题。此外,在钢板浸渍时进行合金化,因此容易形成过合金。
作为不伴有合金化处理时的浴中Al浓度,优选为0.14~0.24质量%。低于0.14质量%时,在镀覆时进行Fe-Zn合金化反应,成为外观不均的原因。另一方面,Al浓度超过0.24质量%时,在镀覆处理时在锌镀层与钢基的界面较厚地形成的Fe-Al合金层,因此焊接性劣化。另外,由于浴中Al浓度高,因此,在钢板表面附着大量Al氧化覆膜,表面外观也显著受损。
作为伴有合金化处理时的浴中Al浓度,优选为0.10~0.20质量%。低于0.10质量%时,在镀覆时在锌镀层与钢基的界面生成硬且脆的Fe-Zn合金层,因此镀层密合性劣化。另一方面,Al浓度超过0.20质量%时,在浴浸渍后立即在锌镀层与钢基的界面较厚地形成Fe-Al合金层,因此焊接性劣化。
另外,为了提高耐腐蚀性,可以在Zn浴中添加Mg。
在根据需要在热镀锌处理后进行合金化处理的情况下,合金化温度优选为460℃以上且低于570℃。合金化温度为460℃以下时,合金化反应慢。另一方面,合金化温度为570℃以上时,在镀层/钢基界面较厚地形成硬且脆的Fe-Zn合金层,因此镀层特性劣化。镀层附着量没有特别限定。但是,从耐腐蚀性和镀层附着量控制的方面考虑,优选为10g/m2以上,从加工性和经济性的观点出发,优选为120g/m2以下。
实施例1
以下,基于实施例具体地对本发明进行说明。
将表1所示的钢组成的板坯在加热炉中在1260℃下加热60分钟,接着实施热轧至2.8mm,然后,在540℃下进行卷取。接着,通过酸洗除去黑色氧化皮后,以50%的压下率实施冷轧至1.4mm。然后,使用具有直火加热(DFF)型加热区的CGL,在表2所示的条件下实施热处理(退火)。接着,使钢板浸渍到460℃的含Al的Zn浴中来实施热镀锌处理,得到热镀锌钢板(镀层种类:GI)。对于一部分钢板,在热镀锌处理后实施合金化处理,由此得到合金化热镀锌钢板(镀层种类:GA)。需要说明的是,浴中Al浓度调节为0.10~0.20质量%,镀覆附着量通过气体擦拭而调节为45g/m2。另外,合金化处理在550~560℃下进行。
利用如下所示的方法对以上得到的热镀锌钢板的表面外观和镀层密合性进行评价。另外,将锌镀层剥离后,利用辉光放电发光表面分析装置(GDS)分析深度方向的组成,对内部氧化层和脱碳层的厚度进行评价。具体而言,将检测到相对于深度50~60μm的氧峰的平均值为2倍以上的氧峰的区域作为内部氧化层。另外,将检测到相对于深度50~60μm的碳峰的平均值为一半以下的碳峰的区域作为脱碳层。另外,利用断面EPMA元素分布像对含有Fe和/或Mn的Si氧化物的面积率进行评价。具体而言,分别对存在于钢基内的内部氧化物中存在的Si、Mn、Fe浓度进行鉴定,将Si的比例为95%以上的氧化物作为SiO2,将Si的比例低于95%的氧化物作为含有Fe和/或Mn的Si氧化物。
以下,示出表面外观和镀层密合性的评价基准。
(1)表面外观
关于表面外观,对300×300mm的范围进行目视观察,对照下述基准进行评价。
○:不存在不上镀或压痕
△:大致良好,但以低频率存在不上镀或压痕
×:存在不上镀或压痕,外观不良
(2)镀层密合性
在镀层表面粘贴玻璃纸带,对带面进行90℃弯曲和弯回,将宽度为24mm的玻璃纸带与弯曲加工部平行地压接到加工部的内侧(压缩加工侧)并将其剥离,对于附着于玻璃纸带的长度40mm的部分的锌量,利用荧光X射线法以Zn计数的形式测定每单位长度(1m)的剥离量,对照下述基准进行评价。需要说明的是,此时的掩模直径为30mm、荧光X射线的加速电压为50kV、加速电流为50mA、测定时间为20秒。
○:Zn计数为0以上且小于5000
△:Zn计数为5000以上且小于10000
×:Zn计数为10000以上
将所得到的结果示于表2。
将表2的结果总结于图2。图2的(a)为表面外观的结果,(b)为镀层密合性的结果。在钢板内部具有5μm以下的内部氧化层和20μm以下的脱碳层、而且上述内部氧化物层以面积率计含有50%以上的含有Fe和/或Mn的Si氧化物的热镀锌钢板的表面(实施例)均具有漂亮的外观,镀层密合性也优良。
产业上的可利用性
本发明的钢板的机械特性良好且镀层外观和密合性也优良,因此,可以预测其在以汽车、家电、建材等领域为中心的广泛用途中的使用。
Claims (6)
1.一种外观性和镀层密合性优良的热镀锌钢板,其特征在于,
具有以质量%计含有C:0.08%以上且低于0.20%、Si:0.1~3.0%、Mn:0.5~3.0%、P:0.001%~0.10%、Al:0.01%~3.00%、S:0.200%以下且余量由Fe和不可避免的杂质构成的成分组成,
从钢基与锌镀层的界面起在钢基侧具有厚度为5μm以下的内部氧化层,且从钢基与锌镀层的界面起在钢基侧具有厚度为20μm以下的脱碳层,而且所述内部氧化层以面积率计含有50%以上的由Fe2XMn2-2XSiOY表示的含有Fe和/或Mn的Si氧化物,
在此,X=0~1,Y=3或4。
2.如权利要求1所述的外观性和镀层密合性优良的热镀锌钢板,其特征在于,以质量%计,进一步含有Mo:0.01~1.00%和/或Cr:0.01~1.00%。
3.如权利要求1或2所述的外观性和镀层密合性优良的热镀锌钢板,其特征在于,以质量%计,进一步含有Nb:0.005~0.20%、Ti:0.005~0.20%、Cu:0.01~0.50%、Ni:0.01~1.00%、B:0.0005~0.010%中的至少一种以上。
4.如权利要求1~3中任一项所述的外观性和镀层密合性优良的合金化热镀锌钢板,其特征在于,锌镀层为合金化锌镀层。
5.一种外观性和镀层密合性优良的热镀锌钢板的制造方法,其特征在于,
对具有权利要求1~3中任一项所述的成分组成的钢进行热轧后,
进行冷轧,
接着,在具备直火燃烧器的直火加热型加热炉中进行热处理,所述热处理中,使CO和烃气体的合计浓度为60体积%以下且余量为H2、N2和不可避免的杂质的可燃性气体与O2浓度为20~50体积%且余量为N2和不可避免的杂质的助燃性气体燃烧,将钢板表面的到达温度加热至600~800℃的范围,
然后,在氢气浓度为3~25体积%、水蒸气浓度为0.070体积%以下且余量为N2和不可避免的杂质的气氛中,在630~850℃的均热温度下对钢板进行加热,
然后,实施热镀锌处理。
6.如权利要求5所述的外观性和镀层密合性优良的合金化热镀锌钢板的制造方法,其特征在于,在热镀锌处理后,对锌镀层进行合金化处理。
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