CN101583734A - 磷酸盐处理性优异的高强度合金化熔融镀锌钢板 - Google Patents
磷酸盐处理性优异的高强度合金化熔融镀锌钢板 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 89
- 239000010959 steel Substances 0.000 title claims abstract description 89
- 239000011701 zinc Substances 0.000 title abstract description 6
- 229910052725 zinc Inorganic materials 0.000 title abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 21
- 239000011572 manganese Substances 0.000 abstract 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000010703 silicon Substances 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
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- 238000007254 oxidation reaction Methods 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 29
- 238000007747 plating Methods 0.000 description 27
- 239000013078 crystal Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 16
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 238000005275 alloying Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 229910001335 Galvanized steel Inorganic materials 0.000 description 7
- 239000008397 galvanized steel Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
- 210000000981 epithelium Anatomy 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 238000002485 combustion reaction Methods 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 230000006698 induction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000005554 pickling Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
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- 230000035899 viability Effects 0.000 description 1
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Abstract
本发明提供一种稳定显示出良好的磷酸盐处理性的合金化熔融镀锌钢板。是一种至少在基材钢板的单面具有Fe-Zn合金镀层的高强度合金化熔融镀锌钢板,所述基材钢板分别含有C:0.03~0.3%、Si:0.5~3.0%、Mn:0.5~3.5%,余量由铁和不可避免的杂质构成,所述Fe-Zn合金镀层,设作为氧化物存在的Si浓度为[Si](质量%),设作为氧化物存在的Mn浓度为[Mn](质量%)时,其满足下式(1)和(2)的关系。[Si]≤0.25…(1),[Mn]/[Si]≤3.0…(2)。
Description
技术领域
本发明涉及作为汽车车体用钢板使用的高强度合金化熔融镀锌钢板(high-strength hot-dip galvannealed steel sheet),特别是涉及作为涂装基底处理的磷酸盐处理性(phosphatability)良好的高强度合金化熔融镀锌钢板。
背景技术
合金化熔融镀锌钢板(以下省略为“GA钢板”),是通过加热熔融镀锌钢板(GI钢板)而使基材钢板中的Fe向镀层扩散,从而使Fe和Zn合金化,由此而获得。GA钢板因为强度、焊接性、涂装后的耐腐蚀性等优异,所以作为例如汽车车体用钢板而使用。
这样的GA钢板被用于上述用途时,虽然会实施涂装,但在进行涂装时,作为其基底处理一般会对GA钢板表面实施磷酸盐处理。而且,为了进行该磷酸盐处理,要形成良好磷酸盐结晶皮膜(Phosphate crystalcoating),这在确保良好的涂膜附着性(coating adhesion)和耐腐蚀性等涂装性能上是重要的要件。
历来,已知GA钢板发挥着优异的磷酸盐处理性。这是由于,镀层表面由与磷酸盐处理液反应性良好的Zn-Fe合金构成,几乎不含杂质。
另一方面,在汽车业界,以碰撞安全性的提高、轻量化带来的燃油效率提高为目的而通用高张力钢板。进行钢板的高张力化时,虽然含有Si、Al、Mn、P、Cr、Mo、Ti等强化元素,但以含有这些元素的钢板为基材钢板而进行合金化熔融镀锌时,上述各元素在镀敷后的合金化处理时与Fe一起扩散到镀层中,在镀层中作为杂质被含有。而且,历来显示出良好的磷酸盐处理性的GA钢板,会发生因镀敷中包含的各种元素而导致磷酸盐处理性不稳定这样的问题。
可是,作为用于得到高张力钢板的强化元素,主要使用的是Si和Mn,但对于含有这些元素的钢板表面实施镀敷时,为了防止不镀而稳定确保良好的外观品质,已知有效的是在使钢板表面氧化后,在含有氢的气氛中进行退火(还原退火),进行熔融镀敷的方法(以下将该方法称为“氧化还原镀敷法(oxidation-reduction galvanizing method)”)(例如专利文献1)。
在上述这样的氧化还原镀敷法中,氧化时在钢板表面的Fe被氧化的同时,钢板中的Si和Mn也被氧化,虽然在后续的还原工序中Fe被还原,但Si和Mn却未被还原,而是维持在氧化物的状态下,因此在其后的镀敷、合金化工序中该氧化物也将与Fe一起混入并分散在镀层中。然后,Si氧化物和Mn氧化物的生成的程度会根据氧化的条件而变动,向镀层中的分散量也发生变化。
还有,也已知公开有关于在镀层中包含氧化物的GA钢板的技术(专利文献2、3)。然而,这些技术中虽然记载在镀层中含有氧化物,但并未提及其含量,另外其制造方法是关于镀前的基材钢板的酸洗,和还原炉内部的水蒸气和氢分压的调整的方法,与上述氧化还原镀敷法基本上是不同的。而且,这些技术分别改善的是镀敷附着性和合金化处理性,而对于磷酸盐处理性未做考虑。即,实际情况是,在镀层中包含氧化物的GA钢板中,有关用于使磷酸盐处理性良好的技术尚未确立。
专利文献1:特开昭55-122865号公报
专利文献2:特开2004-204280号公报
专利文献3:特开2004-315960号公报
发明内容
本发明在这一状况之下而做,其目的在于,提供一种稳定显示出良好的磷酸盐处理性的合金化熔融镀锌钢板。
为了达成所述目的,本发明的合金化熔融镀锌钢板,是至少在基材钢板的单面具有Fe-Zn合金镀层的高强度合金化熔融镀锌钢板,
所述基材钢板分别含有C:0.03~0.3%、Si:0.5~3.0%、Mn:0.5~3.5%,余量由铁和不可避免的杂质构成,
所述Fe-Zn镀敷钢板,设作为氧化物存在的Si浓度为[Si](质量%),设作为氧化物存在的Mn浓度为[Mn](质量%)时,其满足下式(1)和(2)的关系。
[Si]≤0.25 …(1)
[Mn]/[Si]≤3.0 …(2)
在本发明的合金化熔融镀锌钢板中,优选(a)镀层中的Al含量为0.35%以上,和(b)Fe浓度为7~15%。另外,作为本发明使用的基材钢板,除上述成分以外,还含有(c)Cr:0.001~1.0%,(d)Al:0.005~3.0%等也有用。
在本发明中,通过适当规定镀层中作为氧化物存在的Si和Mn的浓度和它们的比,能够实现磷酸盐处理性优异的合金化熔融镀锌钢板,这样的合金化熔融镀锌钢板作为汽车车体用钢板等的原材有用。
具体实施方式
本发明者们以发挥出良好的磷酸盐处理性的GA钢板的实现为目标而反复研究。其结果得到如下发现。即,基本上应用如上述的氧化还原镀敷法时,虽然Si和Mn以外的元素也会混入镀层中,但作为基材钢板的基本的强化元素的Si和Mn的氧化物(Si氧化物、Mn氧化物和Si与Mn的复合氧化物)的影响最大,通过适当规定这些元素的氧化物量,能够得到良好磷酸盐处理性。而且发现如果加以控制而使之满足上述(1)式和(2)式,则良好的磷酸盐处理性得到发挥,从而完成本发明。以下对于本发明规定的各要件进行说明。
在本发明的GA钢板中,设Fe-Zn合金镀层中作为氧化物存在的Si浓度为[Si](质量%)时,需要满足下式(1)的关系。
[Si]≤0.25 …(1)
若上述Si浓度[Si]超过0.25(质量%),则磷酸盐结晶粗大化,涂装附着性的劣化,以及由于涂装后表面的凹凸的增大而招致外观品质的劣化。之所以在不满足上式(1)时磷酸盐结晶粗大化,被认为是由于随着Si浓度[Si]增加,Si氧化物被覆镀层表面的比例增大,这会阻碍磷酸盐处理时的晶核(crystal nucleus)的生成。
在本发明的GA钢板中,设作为氧化物存在的Si浓度为[Si](质量%),设作为氧化物存在的Mn浓度为[Mn](质量%)时,还需要其满足下式(2)的关系。
[Mn]/[Si]≤3.0 …(2)
随着上述比([Mn]/[Si])增加,磷酸盐结晶的晶面比(plane ratio,后述)上升,若其比值超过3.0,则不能稳定确保耐水附着性(wet dahesion)。另外随着([Mn]/[Si])增加,磷酸盐结晶的晶面比上升的原因被认为是由于,随着氧化物变成富Mn(Mn rich),磷酸盐处理时的处理液中的氧化物皮膜的溶解量增加,其对磷酸盐结晶的析出造成影响。
在本发明的GA钢板中,通过适当控制作为氧化物存在的Si浓度[Si](质量%)、作为氧化物存在的Mn浓度[Mn](质量%)的量和它们的比([Mn]/[Si]),则能够成成上述目的,但优选将镀层中的Al浓度和Fe浓度也调整到适当的范围。
关于Fe-Zn合金镀层中的Al浓度,优选为0.35%以上。适用氧化还原法而制造GA钢板时,为了稳定防止不镀,提高镀层中的Al浓度有用。即,在通常的还原后实施镀敷而制造GA钢板的方法中,虽然镀层中的Al浓度处于0.15~0.3%左右,但在氧化还原法中,通过防止氧化时使钢板表面氧化,从而防止退火时(还原退火时)使Si和Mn等易氧化性元素在表面作为氧化物稠化,并且通过促进镀液中钢板表面与镀液中Al的反应,提高镀层中的Al浓度,能够稳定防止不镀。从这一观点出发,优选镀层中的Al浓度至少为0.35%以上,更优选为0.40%以上,进一步优选为0.45%以上。
但是,若镀层中的Al浓度过剩,则镀敷后的合金化不容易进行,因此优选为0.8%以下,更优选为0.7%以下。还有,为了提高镀层中的Al浓度,可以在退火前的氧化时充分确保Fe的氧化量或提高镀液中的Al浓度。
优选Fe-Zn合金镀层中的Fe浓度为7~15%左右。若镀层中的Fe浓度低于7%,则至镀层表面合金化不推进,成为表面有金属光泽的外观。另外,若镀层中的Fe浓度超过15%,则抗粉化性(anti-powdering)劣化。
还有,在Fe-Zn合金镀层中,除上述Si、Mn、Al以外,也可以含有P、Cr、Ni、Mo、Ti、Cu、B、C等和它们的氧化物。
本发明的GA钢板,至少在基材钢板的单面具有上述这样结构的Fe-Zn合金镀层。在本发明的GA钢板中,对镀敷附着量没有特别限定,但如果考虑耐腐蚀性,则优选为30g/m2以上(更优选为40g/m2以上)。另外,若过剩则加工时的镀敷剥离(粉化)显著,因此优选为70g/m2以下(更优选为60g/m2以下)。
本发明使用的基材钢板,具有如下化学成分:分别含有C:0.03~0.3%、Si:0.5~3.0%、Mn:0.5~3.5%,余量由铁和不可避免的杂质构成,这些各成分的限定理由如下。
(C:0.03~0.3%)
C是用于确保钢板的强度所需要的元素,为了发挥其效果,C含量需要为0.03%以上,优选为0.05%以上。然而,若C含量过剩,则焊接性降低,因此需要为0.3%以下,优选为0.25%以下。
(Si:0.5~3.0%)
Si固溶强化能大,是不会使延性降低而能够提高强度的元素。为了充分发挥这样的效果,Si含量需要为0.5%以上,优选为0.7%以上。然而,若Si含量过剩,则强度变得过高而轧制负荷增大,而且在热轧时发生Si氧化皮,也使钢板的表面性状恶化,因此需要在3.0%以下,优选为2.5%以下。
(Mn:0.5~3.5%)
Mn是用于钢板的强度确保有效的元素,另外对于促进残留奥氏体的生成而提高加工性也是有效的元素。为了发挥这样的效果,需要使之含有0.5%以上,优选为1.0%以上。然而,若超过3.5%而过剩地含有,则延性和焊接性劣化。优选为3.0%以下。
基材钢板的优选的基本成分如上所述,余量是铁和不可避免的杂质。作为不可避免的杂质,可列举例如P、S、N等。
本发明使用的基材钢板,除上述基本元素以外,根据需要,作为其他元素还含有(c)Cr:0.001~1.0%,(d)Al:0.005~3.0%等也有用,根据所含有的成分,基材钢板(即,高强度合金化熔融镀锌钢板)的特性得到进一步改善。含有这些元素时的优选的范围及其限定理由如下。
(Cr:0.001~1.0%)
Cr是提高钢板的淬火性,在低温相变生成相之中促进马氏体的生成的元素,对钢板的高强度化有效地发挥着作用。为了发挥这样的效果,优选使Cr含量为0.001%以上,但即使过剩使之含有,其效果也是饱和,造成高成本,因此优选在1.0%以下。
(Al:0.005~3.0%)
为了脱氧优选使Al至少含有0.005%以上。然而,若Al含量过剩,则招致钢板的脆化和成本升高,因此优选为3.0%以下。
本发明的GA钢板,在使用具有规定的化学成分组成的钢板,在氧化带使钢板表面加热氧化,接着在还原带对其还原退火后,将钢板浸渍在Zn镀液中的方法(氧化还原镀敷法)中,能够通过调节氧化还原条件而制造。另外从生产性的观点出发,优选以连续热镀锌线(CGL)进行氧化还原镀敷法。
当应用这样的氧化还原镀敷法时,重要的要件是,氧化时以氧化炉(OF)对基材钢板直接喷射火焰而急速进行氧化,并且调整氧化量。
现有的CGL中以代表性的将空燃比控制得很低的弱氧化性气氛的无氧炉(No oxygen furnace,NOF)调整空燃比而进行氧化的方法也能够实施镀敷,但这一方法氧化速度慢,钢板会长时间滞留在氧化性的气氛中,因此在其间Si、Mn的氧化进行,另外调整各元素的氧化的程度困难。另外,因为氧化速度缓慢,所以难以充分确保用于使镀层中的Al量处于优选的范围所需要的Fe氧化量。
用氧化炉(OF)对钢板直接喷射火焰而进行急速氧化时,优选采用利用在钢板的上面和下面朝向喷嘴而配置的燃烧器,特别是在钢板的宽度方向延伸的缝式燃烧器的直火方式。使钢板通过火焰的氧化区域时的Fe系氧化物层的成长速度(每秒层厚增大的速度)优选调整为若成长速度低于则不能快速形成充分的厚度的Fe系氧化物层,反之若超过则Fe系氧化物层的厚度的控制变得困难,有可能不能形成均一的层。
在本发明中,通过氧化还原法实施镀敷,并且氧化时,调整氧化炉输出功率和氧化炉输出侧板温,以免使氧化过剩使Si量过大。由此要满足前式(1)。还有,氧化炉输出功率越大,氧化的程度就越大,另外氧化炉输出侧板温越高,即使氧化炉输出功率一定,氧化的程度也越大。此外,在本发中,急速加热而不要使Mn/Si的比率过大,即不是以无氧炉进行氧化,而是以氧化炉进行氧化。据此满足前式(2)。
在表2中没有使用OF,意思是没有实施利用OF内的直火燃烧器喷射进行的氧化,这种情况下,钢板也是通过燃烧器没有点火的OF内。然而,没有使用OF的情况下,所说的OF进入侧温度、输出侧温度,是与使用OF(对OF内的燃烧器点火)时相同位置,以同一温度计测定的温度。
通过燃烧器的火焰喷射对钢板进行氧化时,根据需要,能够向燃烧器的燃烧空气中投入氧和/或水蒸气,以提高Fe系氧化物层的成长速度。但是,即使过剩的投入氧和/或水蒸气,其结果也是饱和,另外会花费效用费用,因此优选相对于燃烧空气量,以20体积%以下的流量投入氧、以40体积%以下的流量投入水蒸气。
氧化后的退火,优选在含有H2为25体积%以上,露点为-20℃以下的N2-H2气氛中使板温达到750℃以上而使Fe系氧化物皮膜被还原。
本发明的GA钢板,磷酸盐处理性良好,在其后的涂装处理中,能够确保良好的涂膜附着性和耐腐蚀性等的涂装性能,能够优选用作汽车车体的原材。
实施例
以下,列举实施例更具体地说明本发明,但本发明当然不受以下的实施例限制,在能够符合前述后的宗旨的范围内当然也可以适当加以变更实施,这些均包含在本发明的技术范围内。
(实施例1)
以在无氧炉(NOF)和退火炉之间设置有氧化炉(OF)的CGL(continuous hot-dip galvanizing line),采用下述表1所示的化学成分的基材钢板(板厚:均为1.4mm),按以下所示的条件制造GA钢板。
[表1]
※1余量:铁和不可避免的杂质
[合金化熔融镀锌钢板(GA钢板)的制造]
(1)线速度:40m/分
(2)无氧化炉(NOF)
直火燃烧器(direct-flame burner)设置型
空燃比:0.95(不使用氧化炉,以NOF实施氧化时,空燃比设定为1.20)
滞留时间:28秒
(3)氧化炉(OF)
燃烧器类型:直火燃烧器
燃烧器个数:在钢板表面侧、背面侧,沿钢板行进方向2阶段(计4个)设置垂直向钢板喷射火焰的燃烧器
炉长:4m
空燃比:1.42
氧、水蒸气投入:无
调整为OF燃烧器输出功率:MAX(COG气体流量:50Nm3/h/喷嘴)和MAX的60%(COG气体流量:30Nm3/h/喷嘴)的2个阶段。
(其中,Nm3的N是normal的意思,指在298K、105Pa下的体积)
OF输出侧板温:710~810℃
氧化炉滞留时间:6秒
氧化炉的条件显示在下述表2中。
[表2]
※2从NOF输出,进入OF前的钢板温度由放射温度计测定
※3从OF输出的钢板温度由放射温度计测定
(4)还原炉
气氛:N2-15体积%H2
露点:-30℃
钢板温度:800~860℃
滞留时间:50秒
(5)镀敷
镀液组成:Zn-0.10质量%Al(Al:有效浓度)
液温:460℃
侵入钢板温度:460℃
滞留时间:3.8秒
(6)合金化炉
直火加热型
合金化炉温度:800~1100℃
合金化温度:480~580℃
滞留时间:20秒
对于如前述这样得到的GA钢板,以EPMA(电子射线显微分析仪)观察镀层截面,观察是否含有含Si、Mn的氧化物(Si氧化物、Mn氧化物、含Si和Mn的复合氧化物),作为氧化物存在的区域以外是否存在Si、Mn。另外,将镀层溶解在盐酸中,根据溶解前后的质量变化求得镀敷附着量,并且以ICP(高频感应耦合等离子体发射光谱分析)分析溶解有镀层的盐酸,求得镀层中的Si、Mn的浓度和Al浓度。测定结果显示在下述表3中。
还有,表3中的Si浓度和Mn浓度是分别作为氧化物存在的Si浓度、Mn浓度的意思。
[表3]
另一方面,磷酸盐处理性按以下步骤评价。首先,在制造的GA钢板上涂抹防锈剂“ノックスラスト(NOX-RUST)550HN”(パ一カ興産社(Parker Industries,Inc.)制),以此钢板作为供试材,将其浸渍于加温至40℃的碱性脱脂剂“サ一フクリ一ナ一(SURF CLEANER)SD400A”(日本ペィント社(Nippon Paint Co.,Ltd.)制)的2%水溶液中2分钟进行脱脂,在水洗、表面调整后,浸渍于加温至45℃的磷酸盐处理液“サ一フダィン(SURF DINE)DP4000”(日本ペィント社制)中2分钟,形成磷酸锌系皮膜。然后,对于所形成的磷酸锌皮膜,测定结晶尺寸和磷酸锌结晶(020)面的晶面比,评价磷酸盐皮膜的健全性。
(结晶尺寸的评价方法)
结晶尺寸是用SEM(Scanning Electronic Microscope,扫描型电子显微镜)以1000倍的倍率观察表面,对视野内尺寸大的5个结晶尺寸进行平均,并在5个视野中加以实施,通过平均化求得结晶尺寸,按以下的标准评价优良与否。
(评价标准)
○:结晶尺寸≤20μm
△:20μm<结晶尺寸≤25μm
×:25μm<结晶尺寸
关于晶面比,在靶上使用铜进行磷酸盐皮膜的X射线衍射,将磷酸锌结晶(020)面((020)plane)的X射线衍射强度相对于(151)面、(241)面的X射线衍射强度的比率作为晶面比(plane ratio)进行测定,按以下的标准评价优良与否。
○:晶面比≤4
△:4<晶面比≤5
×:5<晶面比
测定结果显示在下述表4中,可知其中满足本发明规定的要件的(GA钢板No.1、2、6~11、17、19、20)能够得到良好的磷酸盐性,相对于此,不满足本发明规定的要件的(GA钢板No.3~5、12~16、18、21、22)磷酸盐处理性差。
[表4]
Claims (5)
1.一种磷酸盐处理性优异的高强度合金化熔融镀锌钢板,是至少在基材钢板的单面上具有Fe-Zn合金镀层的高强度合金化熔融镀锌钢板,其特征在于,
所述基材钢板以质量%计含有C:0.03~0.3%、Si:0.5~3.0%、Mn:0.5~3.5%,余量是铁和不可避免的杂质,
所述Fe-Zn合金镀层中,在将以氧化物形式存在的Si的浓度设为[Si](质量%),将以氧化物形式存在的Mn的浓度设为[Mn](质量%)时,满足下式(1)和(2)的关系,
[Si]≤0.25…(1)
[Mn]/[Si]≤3.0…(2)。
2.根据权利要求1所述的高强度合金化熔融镀锌钢板,其特征在于,所述Fe-Zn合金镀层中的Al含量以质量%计为0.35%以上。
3.根据权利要求1所述的高强度合金化熔融镀锌钢板,其特征在于,所述Fe-Zn合金镀层中的Fe浓度以质量%计为7~15%。
4.根据权利要求1所述的高强度合金化熔融镀锌钢板,其特征在于,所述基材钢板以质量%计还含有Cr:0.001~1.0%
5.根据权利要求1所述的高强度合金化熔融镀锌钢板,其特征在于,所述基材钢板以质量%计还含有Al:0.005~3.0%。
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