CN101160416A - 热浸镀锌方法 - Google Patents

热浸镀锌方法 Download PDF

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CN101160416A
CN101160416A CNA2006800128831A CN200680012883A CN101160416A CN 101160416 A CN101160416 A CN 101160416A CN A2006800128831 A CNA2006800128831 A CN A2006800128831A CN 200680012883 A CN200680012883 A CN 200680012883A CN 101160416 A CN101160416 A CN 101160416A
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CN101160416B (zh
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石塚清和
西村一实
菊池郁夫
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Abstract

本发明提供一种在热轧钢板、冷轧钢板或各种成分的镀覆原板上都不产生未镀缺陷的热浸镀锌方法,其中,将镀覆原板进行表面清洁化后,实施预镀Ni,在无氧化或还原性气氛中以20℃/秒以上的升温速度快速加热到板温度430~500℃之后,在镀锌浴中进行热浸镀时,a)在镀覆原板为酸洗过的热轧钢板,钢板成分中Si为0.2%以上的场合,将预镀Ni量规定为0.5g/m2以上;b)在镀覆原板为酸洗过的热轧钢板,钢板成分中Si小于0.2%的场合,将预镀Ni量规定为0.2g/m2以上;c)在镀覆原板为退火过的冷轧钢板,钢板成分中Si为0.2%以上的场合,将预镀Ni量规定为0.3g/m2以上;d)在镀覆原板为退火过的冷轧钢板,钢板成分中Si小于0.2%的场合,将预镀Ni量规定为0.05g/m2以上。

Description

热浸镀锌方法
技术领域
本发明涉及在以热轧钢板和冷轧钢板为镀覆原板的利用预镀镍法的热浸镀锌方法中,任何一种镀覆原板都不发生未镀缺陷的热浸镀锌方法。
背景技术
实施了热浸镀锌的钢板由于耐腐蚀性优异,因此被用于汽车、家电、建材等各种用途。过去建材用途是主流,但由于操作技术的进步,粘渣类的外观缺陷大幅度地减轻,因此在外观品位要求严格的汽车、家电上也大量地使用起来。其结果,所适用的镀覆原板的种类也变得多种多样。另外,将实施了热浸镀锌的钢板进行加热处理而成的合金化热浸镀锌的钢板,与实施了热浸镀锌的钢板相比,焊接性良好,因此尤其是以汽车为中心正在被大量使用。
日本专利第2517169号公报公开了利用预镀镍法制造镀层粘附性、加工部耐腐蚀性优异的实施热浸镀锌的钢板的方法,但这里,并未对如上述那样宽范围的镀覆原板的任何一种均提供最佳镀覆条件。
发明内容
因此,本发明的目的在于,提供采用预镀镍法的、即使是任何一种的镀覆原板都不发生未镀缺陷、在制造成本上也有利的热浸镀锌方法。
本发明者们经研究结果弄清了以下情况:在以热轧钢板和冷轧钢板为镀覆原板的利用预镀镍法的热浸镀锌方法中,相应于镀覆原板调整预镀镍量在进行不发生未镀缺陷的热浸镀锌上是必要的。更详细地讲,一种热浸镀锌方法,是将酸洗过的热轧钢板和退火过的冷轧钢板作为镀覆原板的热浸镀锌方法,上述镀覆原板经表面清洁化后,实施预镀镍,在无氧化或还原性气氛中以20℃/秒以上的升温速度进行快速加热到板温度430-500℃后,在镀锌浴中进行热浸镀时,为了实施不发生未镀缺陷的热浸镀锌,以下几项是必需的:
1)在镀覆原板是酸洗过的热轧钢板,作为钢板成分,Si为0.2%以上的场合,将预镀镍量规定为0.5g/m2以上。
2)在镀覆原板是酸洗过的热轧钢板,作为钢板成分,Si小于0.2%的场合,将预镀镍量规定为0.2g/m2以上。
3)在镀覆原板是退火过的冷轧钢板,作为钢板成分,Si为0.2%以上的场合,将预镀镍量规定为0.3g/m2以上。
4)在镀覆原板是退火过的冷轧钢板,作为钢板成分,Si小于0.2%的场合,将预镀镍量规定为0.05g/m2以上。
该方法也可适用于含有锌的各种的合金镀覆。
根据本发明,对于热轧钢板、冷轧钢板及各种成分的任何一种镀覆原板均可进行不发生未镀缺陷的热浸镀锌。
附图说明
图1是表示本发明中镍预镀附着量的优选范围的图。
具体实施方式
本发明以热轧钢板、冷轧钢板二者为镀覆原板。热轧钢板不是表层上残留氧化皮的状态的热轧钢板(所谓的黑皮材料),而是以通过酸洗处理除去了氧化皮的钢板为对象。冷轧钢板中,冷轧后未退火材料、冷轧后退火过的材料均可适用,但如后述,因为本发明的热浸镀锌的前处理,不能将未退火材料退火,因此冷轧后未退火材料除了有特殊的必要性的场合,作为本发明的对象没有意义。作为冷轧、退火过的材料,可以是采用公知的方法制造的任何一种材料,但经过所谓的气水冷却等的利用水的冷却的钢板,由于在表层上残留氧化皮,因此优选是酸洗除去了氧化皮的钢板。
根据本发明,对于以上的任何一种的镀覆原板通过调节预镀镍量,可实施不发生未镀缺陷的良好的热浸镀锌。作为本发明中的预镀镍的前处理,必须是除去表面的污物、氧化膜等的清洁化处理。作为该方法,优选顺序地实施碱脱脂和酸洗处理。
本发明中,根据镀覆原板不同而使预镀镍量不同,以下对此具体地进行说明。首先,镀覆原板是酸洗过的热轧钢板的场合,预镀镍量必须是0.2g/m2以上,小于0.2g/m2时会变得未镀。此外,热轧钢板中,钢中含有0.2%以上的Si的钢板,更容易发生未镀,作为预镀镍量必须是0.5g/m2以上。其次,冷轧钢板的场合,预镀镍量必须是0.05g/m2以上,小于0.05g/m2时会变得未镀。此外,冷轧钢板钢中,钢中含有0.2%以上的Si的钢板,更容易发生未镀,作为预镀镍量必须为0.3g/m2以上。关于预镀镍量的上限没有特殊限制,但从成本的方面考虑优选低的预镀镍量,因此考虑预镀镍设备的能力,优选将不低于上述的下限值的条件作为上限。举一个例子,若是通常的电镀设备,则能够以0.3g/m2左右的幅度充分控制,因此若将下限定为0.05g/m2,则可控制在0.05-0.35g/m2左右。另外,若将下限定为0.5g/m2,则可控制在0.5-0.8g/m2左右。这样,也考虑了成本方面的本发明中的最有利的形态示于图1。图1是表示各种镀覆原板的预镀镍量的优选范围的图。
预镀镍后,在无氧化或还原性气氛中,以20℃/秒以上的升温速度进行快速加热到板温度430-500℃。为了确保热浸镀覆的润湿性、和镀层粘附性该处理是必要的。该加热后进行热浸镀锌,通过擦拭来进行单位表面积的重量的调整。
作为热浸镀锌浴,也包括含有锌的合金镀浴,公知的各种镀浴可同样地使用。举出具体例,使热浸镀锌浴含有0.05-1.0%的Al,通过铝的作用可制造镀层粘附性良好的热浸镀锌钢板。另外,通过使该浴中进一步含有0.01-1.0%的Mg,可制造耐腐蚀性良好的热浸镀锌钢板。也可以向该浴中以0.001-0.1%左右的微量进一步添加Ni、Co、Ti、Pb、Bi、Sb、Sn、Si等。另外,若采用公知的方法对以上那样制造的热浸镀锌钢板进行加热处理,则也可制造合金化热浸镀锌钢板。
另外,使热浸镀锌浴中含有1-15%的Al,可制造耐腐蚀性良好的Zn-Al合金热浸镀锌钢板。使上述浴中进一步含有1.0-5.0%的Mg,可制造耐腐蚀性更好的Zn-Al-Mg合金热浸镀锌钢板。另外,使之进一步含有0.01-1.0%的Si,可制造耐腐蚀性更好的Zn-Al-Mg-Si合金热浸镀锌钢板。
另外,使热浸镀锌浴中以15-80%大量地含有Al,可制造耐腐蚀性更好的Zn-Al合金热浸镀锌钢板。使之进一步含有0.01-1.0%的Si,可制造耐腐蚀性更好的Zn-Al-Si合金热浸镀锌钢板。
实施例
使用表1所表示的7种镀覆原板。镀覆原板1-4是退火过的冷轧钢板,镀覆原板5-6是酸洗过的热轧钢板。在实施表2所示的前处理之后,在表3所示的镀浴中通过电镀(浴温60℃,电流密度30A/dm2)进行预镀镍。然后,在3%H2+N2的气氛中,以50℃/秒的升温速度加热到460℃,立即浸渍在保温在450℃的热浸镀Zn浴中保持3秒钟后,进行擦拭,从而调节单位表面积的重量。单位表面积的重量为60g/m2
在此,实施例1和比较例1、2,作为热浸镀浴使用添加了0.2%Al的镀浴。预镀Ni量,在实施例1中如表4所示那样,在各镀覆原板上使之不同。在比较例1和比较例2中如表4所示那样,在各镀覆原板上为相同的预镍Ni量。
在实施例2中,作为热浸镀浴,使用添加了0.2%Al和0.5%Mg的镀浴,预镀Ni量如表4所示那样在各镀覆原板上使之不同。
在实施例3中,作为热浸镀浴,使用添加了10%Al和3%Mg及0.2%Si的镀浴,预镀Ni量如表4所示那样在各镀覆原板上使之不同。
在实施例4中,作为热浸镀浴,使用添加了55%Al和0.2%Si的镀浴,预镀Ni量如表4所示那样在各镀覆原板上使之不同。
目视观察各样品镀覆后的外观,确认有无未镀等异常情况。
表1试验原板
原板   钢板种类                           钢成分(质量%)
  C   Si   Mn   P   S   Ti
  原板1   冷轧   0.002   0.01   0.15   0.014   0.006   0.03
  原板2   冷轧   0.002   0.09   1.08   0.015   0.012   0.007
  原板3   冷轧   0.14   0.24   1.4   0.017   0.008   -
  原板4   冷轧   0.07   0.45   1.87   0.015   0.006   -
  原板5   热轧   0.045   0.015   0.21   0.16   0.009   -
  原板6   热轧   0.07   0.69   2.38   0.007   0.001   -
  原板7   热轧   0.2   1.58   1.59   0.009   0.001   -
表2前处理条件
碱脱脂处理     NaOH  50g/l液温  65℃浸渍  10秒
酸洗处理     H2SO4 90g/l液温  60℃浸渍  5秒
表3预镀镍条件
    成分     浓度
    NiSO4·6H2OH3BO3Na2SO4pH     300g/l40g/l100g/l2.7
表4评价结果
热浸镀浴 原板   预镀镍量g/m2 镀层外观
实施例 1 Zn-0.2%Al 原板1     0.05     ○
原板2     0.05     ○
原板3     0.3     ○
原板4     0.3     ○
原板5     0.2     ○
原板6     0.5     ○
原板7     0.5     ○
比较例 1 Zn-0.2%Al 原板1     0.1     ○
原板2     ″     ○
原板3     ″     ×
原板4     ″     ×
原板5     ″     ×
原板6     ″     ×
原板7     ″     ×
比较例 2 Zn-0.2%Al 原板1     0.2     ○
原板2     ″     ○
原板3     ″     ×
原板4     ″     ×
原板5     ″     ○
原板6     ″     ×
原板7     ″     ×
实施例 2 Zn-0.2%Al-0.5%Mg 原板1     0.05     ○
原板2     0.05     ○
原板3     0.3     ○
原板4     0.3     ○
原板5     0.2     ○
原板6     0.5     ○
原板7     0.5     ○
实施例 3 Zn-10%Al-3%Mg-0.2%Si 原板1     0.05     ○
原板2     0.05     ○
原板3     0.3     ○
原板4     0.3     ○
原板5     0.2     ○
原板6     0.5     ○
原板7     0.5     ○
实施例 4 Zn-55%Al-0.2%Si 原板1     0.05    ○
原板2     0.05    ○
原板3     0.3    ○
原板4     0.3    ○
原板5     0.2    ○
原板6     0.5    ○
原板7     0.5    ○
如表4所示,根据本发明的条件,对任何一种镀覆原板均可实施良好的热浸镀锌。
工业实用性
本发明可在采用预镀Ni法的热浸镀锌设备中应用,对于在汽车、家电、建材等各种用途中使用的多种多样的任何一种镀覆原板均可适用。

Claims (11)

1.一种不发生未镀缺陷的热浸镀锌方法,是将酸洗过的热轧钢板和退火过的冷轧钢板作为镀覆原板的热浸镀锌方法,其特征在于,上述镀覆原板经表面清洁化后,实施预镀Ni,在无氧化或还原性气氛中以20℃/秒以上的升温速度进行快速加热到板温度430~500℃后,在镀锌浴中进行热浸镀时,相应于镀覆原板调整预镀Ni量。
2.如权利要求1所述的不发生未镀缺陷的热浸镀锌方法,其特征在于,
1)在镀覆原板为酸洗过的热轧钢板,作为钢板成分,Si为0.2%以上的场合,将预镀Ni量规定为0.5g/m2以上。
2)在镀覆原板为酸洗过的热轧钢板,作为钢板成分,Si小于0.2%的场合,将预镀Ni量规定为0.2g/m2以上。
3)在镀覆原板为退火过的冷轧钢板,作为钢板成分,Si为0.2%以上的场合,将预镀Ni量规定为0.3g/m2以上。
4)在镀覆原板为退火过的冷轧钢板,作为钢板成分,Si小于0.2%的场合,将预镀Ni量规定为0.05g/m2以上。
3.如权利要求1所述的不发生未镀缺陷的热浸镀锌方法,其特征在于,
1)在镀覆原板为酸洗过的热轧钢板,作为钢板成分,Si为0.2%以上的场合,将预镀Ni量规定为0.5g/m2~0.8g/m2
2)在镀覆原板为酸洗过的热轧钢板,作为钢板成分,Si小于0.2%的场合,将预镀Ni量规定为0.2g/m2~0.5g/m2
3)在镀覆原板为退火过的冷轧钢板,作为钢板成分,Si为0.2%以上的场合,将预镀Ni量规定为0.3g/m2~0.6g/m2
4)在镀覆原板为退火过的冷轧钢板,作为钢板成分,Si小于0.2%的场合,将预镀Ni量规定为0.05g/m2~0.35g/m2
4.如权利要求1~3的任一项所述的不发生未镀缺陷的热浸镀锌方法,其特征在于,热浸镀锌浴含有0.05-1.0%的Al。
5.如权利要求4所述的不发生未镀缺陷的热浸镀锌方法,其特征在于,进一步含有0.01-1.0%的Mg。
6.如权利要求1~3的任一项所述的不发生未镀缺陷的热浸镀锌方法,其特征在于,热浸镀锌浴含有1.0-15%的Al。
7.如权利要求6所述的不发生未镀缺陷的热浸镀锌方法,其特征在于,进一步含有1.0-5.0%的Mg。
8.如权利要求6或7所述的不发生未镀缺陷的热浸镀锌方法,其特征在于,进一步含有0.01-1.0%的Si。
9.如权利要求1~3的任一项所述的不发生未镀缺陷的热浸镀锌方法,其特征在于,热浸镀锌浴含有15-80%的Al。
10.如权利要求9所述的不发生未镀缺陷的热浸镀锌方法,其特征在于,进一步含有0.01-1.0%的Si。
11.如权利要求1~10的任一项所述的热浸镀锌方法,其特征在于,与热浸镀锌接续,实施加热合金化处理。
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