CN111527232A - 加工后耐蚀性优异的镀锌合金钢材及其制造方法 - Google Patents

加工后耐蚀性优异的镀锌合金钢材及其制造方法 Download PDF

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Publication number
CN111527232A
CN111527232A CN201880084547.0A CN201880084547A CN111527232A CN 111527232 A CN111527232 A CN 111527232A CN 201880084547 A CN201880084547 A CN 201880084547A CN 111527232 A CN111527232 A CN 111527232A
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corrosion resistance
plating bath
plating
zinc alloy
layer
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孙一领
金泰喆
金钟常
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Posco Holdings Inc
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Posco Co Ltd
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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
    • 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
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    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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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    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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    • C—CHEMISTRY; METALLURGY
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    • Y10T428/12958—Next to Fe-base component
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
    • Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]

Abstract

本发明涉及一种可以用于汽车、家电、建筑材料等的镀覆钢材，更详细地，涉及一种加工后耐蚀性优异的镀锌合金钢材及其制造方法。

Description

加工后耐蚀性优异的镀锌合金钢材及其制造方法
技术领域
本发明涉及一种可以用于汽车、家电、建筑材料等的镀覆钢材，更详细地，涉及一种加工后耐蚀性优异的镀锌合金钢材及其制造方法。
背景技术
通过阴极防蚀抑制铁的腐蚀的镀锌法具有优异的防蚀性能和经济性，因此广泛用于制造具有高耐蚀特性的钢材。尤其，与电镀锌钢材相比，将钢材浸入熔融锌中而形成镀层的热浸镀锌钢材的制造工艺简单，产品价格低廉，因此在汽车、家电产品和建筑材料等所有产业中的需求正在增加。
热浸镀锌钢材暴露在腐蚀环境时，具有氧化还原电位低于铁的锌先被腐蚀而抑制钢材的腐蚀的牺牲防蚀(Sacrificial Corrosion Protection)的特性，而且镀层的锌被氧化并在钢材表面形成致密的腐蚀产物，使钢材与氧化气氛隔离，从而提高钢材的耐腐蚀性。
但是，随着产业高度化，大气污染和腐蚀环境的恶化正在增加，并且由于对节约资源和能源的严格管制，开发比现有的镀锌钢材具有更优异的耐蚀性的钢材的需求正在增加。作为其中一个部分，对通过在镀锌浴中添加铝(Al)和镁(Mg)等元素来提高钢板的耐蚀性的镀锌合金系钢材的制造技术进行了各种研究。作为代表性的镀锌合金系钢材，正在积极进行与Zn-Al镀覆组成系中进一步添加Mg的制造Zn-Al-Mg系镀覆钢材的技术相关的研究(专利文献1)。
另外，对镀锌钢材进行加工成型时镀层产生裂纹时，镀层阻断腐蚀的效果减弱，并且产生裂纹的部位的镀层的牺牲防蚀快速进行，因此缩短镀层的寿命，导致耐腐蚀性降低。尤其，汽车等的镀锌合金钢材的情况下，通过各种成型加工来制造部件并使用，因此对可以减少加工后耐蚀性的降低的方案的需求越来越高。
(专利文献1)日本公开专利公报第2002-332555号
发明内容
要解决的技术问题
本发明的一个方面的目的在于提供一种镀锌合金钢材及其制造方法，所述镀锌合金钢材确保优异的耐蚀性，而且通过减少加工时镀层裂纹的产生而防止耐蚀性降低，因此可以确保优异的加工后耐蚀性。
本发明要解决的技术问题并不限定于以上提及的问题，本领域技术人员可以通过以下记载明确理解没有提及的其它问题。
技术方案
本发明的一个实施方案涉及一种加工后耐蚀性优异的镀锌合金钢材，所述镀锌合金钢材包括：基材铁；锌合金镀层，形成在所述基材铁上；以及抑制层(Inhibition layer)，形成在所述基材铁和所述锌合金镀层之间，以重量％计，所述锌合金镀层包含：Mg：0.5-3.5％、Al：0.5-11.0％、Si：10-350ppm、余量的Zn和不可避免的杂质，所述抑制层中包括Si富集层。
本发明的另一个实施方案涉及一种制造加工后耐蚀性优异的镀锌合金钢材的方法，所述方法包括以下步骤：准备晶粒尺寸为1-100μm的热轧钢材；将所述热轧钢材进行冷轧，从而制造具有0.2-1.0μm的表面粗糙度和0.2-1.2μm的陡度的冷轧钢材；将作为所述冷轧钢材的基材铁浸入镀浴中进行镀覆，以重量％计，所述镀浴包含：Mg：0.5-3.5％、Al：0.5-11.0％、Si：10-350ppm、余量的Zn和不可避免的杂质；将经过所述镀覆的热浸镀锌合金钢材进行擦拭并冷却。
有益效果
根据本发明，可以提供一种加工后耐蚀性优异的Zn-Al-Mg系镀锌合金钢材及其制造方法。由此，具有可以将应用领域扩大至以往使用受到限制的领域的优点。
附图说明
图1是分析根据本发明的一个具体实施方案制造的镀锌合金钢材的抑制层(inhibition layer)的成分的照片。
图2是观察本发明的实施例中的发明例3的镀层截面的照片。
图3是观察本发明的实施例中的比较例3的镀层截面的照片。
最佳实施方式
常规的镀锌是凝固成Zn单相，但Zn-Al-Mg系镀锌合金中共存Zn相、Mg和Zn的合金相、Al相等。随着根据镀浴中的微量元素和制造工艺等的基材铁表面的物理状态和化学状态，该镀覆组织形成非常复杂的镀覆结构。
Zn-Al-Mg系锌合金镀层(以下，锌合金镀层或镀层)的镀覆组织中，Zn和Mg的合金相可以由MgZn2、Mg2Zn11等各种金属间化合物组成，它们的硬度达到Hv 250-300。并且，所述镀层和基材铁的界面上可以形成由Fe和Al的金属间化合物组成的抑制层(InhibitionLayer)。所述Fe和Al的金属间化合物有Fe4Al13、Fe2Al5等。这些金属间化合物也具有高的脆性，因此物理变形时镀层容易产生裂纹。
因此，作为通过减少加工镀锌合金钢材时镀层裂纹的产生而可以在加工后确保优异的耐蚀性的方案，本发明人研究出了坚固并均匀地形成所述抑制层的方案，并完成了本发明。以下，对本发明进行详细说明。
本发明的镀锌合金钢材包括：基材铁；锌合金镀层，形成在所述基材铁上；以及抑制层(Inhibition Layer)，形成在所述基材铁和锌所述合金镀层之间。
以重量％计，所述锌合金镀层优选包含：镁(Mg)：0.5-3.5％、铝(Al)：0.5-11.0％、硅(Si)：10-350ppm、余量的Zn和不可避免的杂质。以下，对各成分进行详细说明。
所述Mg对提高镀锌系钢材的耐蚀性起到非常重要的作用，在腐蚀环境下，在镀层表面形成致密的氢氧化锌系腐蚀产物，因此可以有效防止镀锌系钢材的腐蚀。为此，Mg的含量优选为0.5重量％以上，更优选为0.8重量％以上。但是，当Mg的含量过多时，镀浴表面的Mg氧化物浮渣剧增，因此添加微量元素所带来的抗氧化效果被抵消。为了防止这种问题，Mg优选包含3.5重量％以下，更优选包含2.0重量％以下。
所述Al抑制镀浴内Mg氧化物浮渣的形成，并且与镀浴内的Zn和Mg反应形成Zn-Al-Mg系金属间化合物，从而提高镀覆钢材的耐腐蚀性。在本发明中，为了获得上述效果，Al优选包含0.5重量％以上，更优选包含0.8重量％以上。但是，当Al的含量过多时，镀覆钢材的焊接性和磷酸盐处理性可能会变差。在防止这种问题的方面，Al优选为11.0重量％以下，更优选为6.0重量％以下。
所述Si是形成锌合金镀层的抑制层(Inhibition layer)时固溶在Fe-Al化合物中而赋予延展性。所述Si富集在抑制层中而没有析出为Mg2Si时，有利于提高镀层的粘附性和断裂韧性。为了上述效果，Si优选包含10重量ppm以上。但是，当Si的量增加时，钢板表面的粗糙度或形状不均匀的情况下，在镀层和基材铁的界面上形成粗大的具有脆性的Mg2Si析出物，因此反而因外部应力而引发裂纹。因此，所述Si优选不超过350重量ppm。
余量包含锌(Zn)和不可避免的杂质。
另外，镀浴的一部分Fe可以包含在镀层中，但所述Fe主要存在于镀层和基材铁的界面的所述抑制层(inhibition layer)中。
所述锌合金镀层包含Mg和Zn的合金相、Zn相、Al相等，所述Mg和Zn的合金相包含MgZn2相和Mg2Zn11相。在凝固时，最先凝固的是Zn相，并且其内部固溶有少量的Al。初晶Zn凝固之后，Zn和MgZn2以层状凝固，最终Zn和MgZn2以及Al的三元相凝固。当冷却速度相对慢时，除了MgZn2之外，可能会形成Mg2Zn11。与Zn相相比，MgZn2或Mg2Zn11的硬度高，因此在施加外部应力时可能会成为产生裂纹的起点，但可以通过包含Mg来提高耐蚀性。
所述抑制层包括富集有Si的层(Si富集层)。尤其，所述Si富集层优选位于所述抑制层的底部。所述Si富集层是指Si固溶在由Fe-Al系化合物组成的抑制层中，并包含在所述抑制层的底部。所述抑制层包括Si富集层，所述Si富集层是Si固溶的形态，因此即使向抑制层赋予诸如外部应力的机械韧性，从抑制层就可以减少机械破损，从而可以防止裂纹扩展到镀层。为了均匀地形成所述抑制层并使Si均匀地分布在抑制层中，需要对镀浴的成分、基材铁表面的金属组织、表面结构和板形状进行控制。当这种控制不足时，Si以粗大的Mg2Si合金相形成在基材铁和锌合金镀层之间，并且施加外部应力时在所述Mg2Si合金相发生应力集中现象，因此可能会促进裂纹的产生和生长。因此，在基材铁和锌合金镀层之间，每100μm的界面长度中，优选形成5个以下的具有直径超过1000nm的尺寸的Mg2Si合金相。更优选地，形成5个以下的具有直径超过500nm的尺寸的Mg2Si合金相。如图3所示，可以在抑制层的正上方观察到所述Mg2Si合金相。
当所述抑制层均匀地形成时，Si也可以沿着抑制层均匀地固溶。但是，当钢表面的形状不均匀和因所述形状不均匀而导致存在于钢表面的氧化物无法顺利分解时，抑制层的厚度可能变得不均匀或者有些部分可能不会形成抑制层。这种情况下，可能会形成粗大的Mg2Si。因此，优选地，基材铁和锌合金镀层之间均匀地形成抑制层。
图1是分析根据本发明的一个具体实施方案制造的镀锌合金钢材的抑制层(inhibition layer)的照片。分析抑制层的成分的方法可以利用将镀层溶解在盐酸溶液中进行分析的湿式分析方法、利用GDOES和GDMS等等离子体源进行分析的方法或者利用TEM直接分析成分的方法等，所述图1是利用其中的TEM对成分进行分析的。如图1所示，可知所述镀锌合金钢材的抑制层中形成Si富集在抑制层底部的层。图1的(a)是对抑制层进行观察的照片，可知抑制层12形成在基材铁11上。另外，附图标记13表示用于TEM观察的保护膜。图1的(b)至(d)中示出对所述抑制层中的Al、Fe和Si的成分分别进行分析的照片。尤其，通过图1的(d)，可知Si富集在抑制层中。
以下，对本发明的制造镀锌合金钢材的方法的一个具体实施方案进行详细说明。本发明的制造镀锌合金钢材的方法包括以下过程：准备基材铁，将准备的基材铁浸入镀浴中进行镀覆，然后通过擦拭来调节镀层厚度，并进行冷却。
在准备所述基材铁时，优选地，首先使热轧钢材的金属组织均匀。所述热轧钢材的晶粒优选是表层部(从表面到总厚度的1/8以内)。当发生热轧钢材的组织的不均匀，特别是发生表面组织的不均匀时，由于冷轧时表面形状不均匀以及形成抑制层时所必要的从基材铁扩散的Fe不均匀，无法形成均匀的抑制层且无法使Si均匀地富集，而且容易局部地形成粗大的Mg2Si合金相。为此，所述热轧钢材的晶粒的平均尺寸优选为1-100μm。晶粒的尺寸更优选为1-50μm，或进一步优选为5-30μm。
当所述热轧钢材的晶粒小于1μm时，有利于确保强度，但冷轧时，由于晶粒，表面粗糙度可能增加。此外，当所述热轧钢材的晶粒超过100μm时，在形状均质化方面有利，但由于热轧温度的过度上升，可能导致氧化皮缺陷，并且还增加产品的制造成本。作为用于获得所述热轧钢材的晶粒尺寸的方案中的一个实例有以下方法，即将热轧温度设为最低800℃以上，或者热轧后的收卷温度设为550℃以上。
将所述热轧钢材进行冷轧而制造冷轧钢材时，优选制造成冷轧钢材的表面粗糙度(Ra)为0.2-1.0μm，陡度为0.2-1.2。
所述表面粗糙度取决于辊对材料进行轧制时的辊的压力和辊的表面形状。当所述表面粗糙度超过1.0μm时，粗糙度增加，因此形成镀层时可能形成不均匀的抑制层，并且具有难以均匀地形成Si富集层的问题。另一方面，当所述表面粗糙度小于0.2μm时，表面摩擦系数减小，因此钢材可能在辊上打滑。
所述陡度的测量是使用如下方法，即将宽度方向上为1m以上且长度方向上为2m以上的钢材放置在平坦的平板上，以使表面可以很好地粘附，然后测量钢材的弯曲程度。所述陡度是以弯曲的高度(H)除以波长(P)后乘以100的值来表示。即，所述陡度是以高度(H)/波长(P)×100的式来表示。陡度越小，表示钢材的平坦程度越优异。当所述陡度超过1.2时，钢材的弯曲程度大，钢材通过镀浴时，表面流动发生偏差，从而对抑制层的形成和镀层均质化产生负面影响。所述陡度越低越有利，但为了将陡度控制为小于0.2，需要过多的工艺成本，因此不优选。
将所述粗糙度和陡度控制在适当范围的方法并不受限于任一种方法。在冷轧的最后步骤的轧制中，压下率优选设为2-5％的范围。在轧制过程中需要对钢板施加适当的张力。此外，作为用于赋予表面粗糙度的一个实例，可以在钢表面上进行等离子处理。即，所述冷轧时，由最后的轧辊决定最终形状，因此压下率优选为5％以下。但是，厚度为0.5mm的薄板的情况下，为了减少剪切轧制的过负荷，所述压下率优选为2％以上。
另外，根据需要可以在600-850℃的温度下，将如上所述的冷轧材料进行退火热处理。所述退火时的炉内气氛优选使用包含氮气(N2)和1-10体积％的氢气(H2)的气体。当所述氢气浓度小于1体积％时，难以还原钢表面的氧化物，当所述氢气浓度超过10体积％时，制造成本增加，因此优选包含1-10体积％的所述氢气。
随着所述退火时的气氛中的露点温度不同，在基材铁表面上形成的氧化薄膜的组成成分的比例不同，而且内部氧化比例不同，因此所述露点温度优选控制为-60℃至-10℃。当所述露点温度小于-60℃时，控制原料气体的纯度方面可能会产生过多的成本，因此不优选。另一方面，当所述露点温度超过-10℃时，可能无法很好地还原基材铁表面的污染物，并且形成包含在钢中的微量元素或作为杂质的B、Mn等的氧化薄膜，因此存在阻碍镀覆润湿性的风险。
将如上所述准备的基材铁浸入镀浴中，从而制造镀锌合金钢材。以重量％计，所述镀浴包含：Mg：0.5-3.5％、Al：0.5-11.0％、Si：10-350ppm、余量的Zn和不可避免的杂质。对于所述各成分，与上述对锌合金镀层进行说明的内容相同。
另外，所述镀浴可以进一步包含10-80重量ppm的铁(Fe)。所述Fe主要从基材铁溶解并包含在镀浴中。超过可固溶在镀浴中的极限的Fe与Al结合形成FeAl系化合物。此外，镀浴中的一部分Si也被镀浴中形成的FeAl吸收。这种镀浴中形成的FeAl系化合物以称为浮渣的固相形态存在，在制造镀层时混入镀层内部，从而可能引发缺陷。此外，所述浮渣吸收镀浴中的Si，从而起到降低镀浴中可溶Si的浓度的作用。在这种情况下，Si无法均匀地富集在抑制层中。因此，镀浴中Fe的总含量优选不超过80重量ppm。作为将所述镀浴中的Fe的含量控制为80ppm以下的方案的一个实例，将惰性气体注入镀浴底部，使惰性气体将由镀浴中的Fe和Al形成的化合物向上部上浮，从而可以降低镀浴中的Fe的浓度。Fe的含量少也不会产生问题，但将Fe控制在过低的含量时需要过多的工艺成本，因此10ppm以上即可。
另外，基于镀层的组成来确定所述镀浴的Al、Mg和Zn的量。所述镀覆时的镀浴的温度优选为镀浴组成的熔点+10℃以上且镀浴组成的熔点+90℃以下。当镀浴的温度没有达到镀浴熔点+10℃以上时，镀浴的流动性降低，并且阻碍均匀的镀覆附着量。另外，当所述镀浴的温度超过镀浴熔点+90℃时，由于镀浴内Mg的氧化，镀浴表面的氧化物可能增加，并且可能会发生由Al和Mg引起的镀浴耐火物的沉淀。
浸入所述镀浴中的基材铁的温度为镀浴温度以上时，在表面氧化物的分解和Al富集方面是有利的。为了使这种效果极大化，引入到镀浴中的基材铁的温度优选比镀浴温度高5℃以上，更优选为高10℃以上。但是，引入到镀浴中的基材铁的温度过高时，可能难以控制镀槽的温度，并且基材铁的成分可能过度溶出到镀浴中，因此基材铁的温度优选低于镀浴温度+30℃，更优选低于镀浴温度+20℃。
将在镀浴中经过镀覆的所述镀锌合金钢材进行气体擦拭来调节镀覆附着量，并进行冷却。
具体实施方式
以下，对本发明的实施例进行详细说明。下述实施例仅用于理解本发明，并不限定本发明的权利范围。
(实施例)
准备具有下表1中示出的平均晶粒尺寸的热轧钢板，然后进行冷轧，以此准备下表1的基础钢板。所述冷轧时，调节钢板的张力和压下率等，从而制造具有下表1中示出的表面粗糙度(Ra)和陡度的基础钢板。以重量％计，所述基础钢板的组成包含：C：0.03％、Si：0.02％、Mn：0.15％、P：0.01％、S：0.01％、余量的Fe和不可避免的杂质。
将准备的所述基础钢板浸入镀锌合金浴中，然后调节至单面为50g/m2的附着量后进行冷却，从而制造Zn-Al-Mg系镀锌合金钢板。此时，对制造的镀锌合金钢板的Al、Mg、Si成分进行测量，并示于表1中，测量镀浴中的Fe含量并一起示于表1中。所述Fe含量是取从镀浴的底部至镀浴表面之间的1/2位置处的镀浴液进行分析的。
检查所述镀锌合金钢板的镀层截面，对形成在锌合金镀层和基材铁之间的抑制层(inhibition layer)中的Si富集层的形成、Mg2Si合金相的尺寸和数量进行测量，并将其结果一起示于表1中。通过SEM观察镀层的截面后，测量所述Si富集层的形成、Mg2Si合金相的尺寸和数量。
此外，为了评价镀锌合金钢板的加工后的耐蚀性，将所述镀锌合金钢板切割成直径为100mm的圆形，然后利用直径为50mm的冲头，加工成杯状。此时，冲头的边缘曲率为5mm，拉延比(drawing ratio)为2.0。
对经过加工的所述杯状试片进行ISO TC 156中规定的盐水复合腐蚀试验(循环腐蚀试验(Cyclic corrosion test))。将所述杯状试片的底部朝上的方式放入腐蚀试验机中并进行试验，每个腐蚀周期(cycle)检查试片是否产生红锈，并将其结果一起示于表1中。
[表1]
Figure BDA0002558566260000091
Figure BDA0002558566260000101
另外，图2是观察所述发明例3的镀层截面的照片，图3是观察所述比较例3的镀层截面的照片。可以确认所述图2中形成在镀层22和基材铁21之间的抑制层均匀地形成，但图3中镀层32和基材铁31之间的抑制层中形成大量的Mg2Si 33。
从所述表1、图2和图3的结果可知，在满足本发明的条件的发明例中，可以确认加工后也具有优异的耐蚀性。与此相比，在不满足本发明的条件的比较例中，可以确认具有差的加工后耐蚀性。

Claims (10)

1.一种加工后耐蚀性优异的镀锌合金钢材，其包括：
基材铁；
锌合金镀层，形成在所述基材铁上；以及
抑制层，形成在所述基材铁和所述锌合金镀层之间，
以重量％计，所述锌合金镀层包含：Mg：0.5-3.5％、Al：0.5-11.0％、Si：10-350ppm、余量的Zn和不可避免的杂质，
所述抑制层中包括Si富集层。
2.根据权利要求1所述的加工后耐蚀性优异的镀锌合金钢材，其中，在所述锌合金镀层和所述基材铁之间，每100μm中直径超过1000nm的Mg2Si合金相的数量为5个以下。
3.根据权利要求1所述的加工后耐蚀性优异的镀锌合金钢材，其中，在所述锌合金镀层和所述基材铁之间，每100μm中直径超过500nm的Mg2Si合金相的数量为5个以下。
4.一种制造加工后耐蚀性优异的镀锌合金钢材的方法，其包括以下步骤：
准备晶粒尺寸为1-100μm的热轧钢材；
将所述热轧钢材进行冷轧，从而制造具有0.2-1.0μm的表面粗糙度和0.2-1.2μm的陡度的冷轧钢材；
将作为所述冷轧钢材的基材铁浸入镀浴中进行镀覆，以重量％计，所述镀浴包含：Mg：0.5-3.5％、Al：0.5-11.0％、Si：10-350ppm、余量的Zn和不可避免的杂质；
将经过所述镀覆的热浸镀锌合金钢材进行擦拭并冷却。
5.根据权利要求4所述的制造加工后耐蚀性优异的镀锌合金钢材的方法，其中，所述镀浴进一步包含10-80ppm的Fe。
6.根据权利要求4所述的制造加工后耐蚀性优异的镀锌合金钢材的方法，其中，所述镀浴的温度是镀浴熔点+10℃至镀浴熔点+90℃。
7.根据权利要求4所述的制造加工后耐蚀性优异的镀锌合金钢材的方法，其中，所述镀覆时的基材铁的温度是镀浴温度+5℃至镀浴温度+30℃。
8.根据权利要求4所述的制造加工后耐蚀性优异的镀锌合金钢材的方法，其中，所述方法进一步包括在600-850℃的温度下，对所述冷轧钢材进行退火热处理的步骤。
9.根据权利要求8所述的制造加工后耐蚀性优异的镀锌合金钢材的方法，其中，所述退火热处理的炉内气氛使用1-10体积％的氢气(H2)且余量为氮气(N2)的气体。
10.根据权利要求8所述的制造加工后耐蚀性优异的镀锌合金钢材的方法，其中，所述退火热处理的露点温度为-60℃至-10℃。
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102590172B1 (ko) * 2020-04-21 2023-10-19 닛폰세이테츠 가부시키가이샤 용융 도금 강판, 및 그 제조 방법
EP4170056A1 (en) * 2020-06-19 2023-04-26 POSCO Co., Ltd Plated steel sheet having excellent corrosion resistance, workability and surface quality and method for manufacturing same
KR102395455B1 (ko) * 2020-08-27 2022-05-09 현대제철 주식회사 용융아연도금 강판의 제조 방법
KR102381828B1 (ko) * 2020-12-18 2022-04-01 주식회사 포스코 내식성 및 표면 품질이 우수한 도금 강판 및 이의 제조방법
KR102453010B1 (ko) * 2020-12-21 2022-10-12 주식회사 포스코 내식성 및 내열성이 우수한 도금 강판 및 이의 제조방법
KR102453008B1 (ko) * 2020-12-21 2022-10-12 주식회사 포스코 내식성, 가공성 및 표면 품질이 우수한 도금 강판 및 이의 제조방법
KR102499192B1 (ko) * 2021-09-27 2023-02-16 순천대학교 산학협력단 Zn-Al-Mg-Si계 합금도금강판의 제조방법 및 Zn-Al-Mg-Si계 합금도금강판
CN114645231A (zh) * 2022-02-11 2022-06-21 河钢股份有限公司承德分公司 一种热基板双面锌层镀锌板的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06306461A (ja) * 1993-04-28 1994-11-01 Nippon Steel Corp 外観性に優れた合金化溶融亜鉛めっき鋼板の製造法
KR20150070841A (ko) * 2013-12-17 2015-06-25 동부제철 주식회사 고내식 도금강판 및 그 제조방법
CN105483547A (zh) * 2015-12-03 2016-04-13 武汉钢铁(集团)公司 家电用深冲耐指纹电镀锌板及其制备方法

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2783453B2 (ja) * 1990-10-09 1998-08-06 新日本製鐵株式会社 溶融Ｚｎ−Ｍｇ−Ａｌめっき鋼板及びその製造方法
JP2000265255A (ja) * 1999-03-16 2000-09-26 Nisshin Steel Co Ltd 耐熱性を改善した溶融Ｚｎ−Ａｌ系合金めっき鋼板およびその製造法
JP2001295015A (ja) * 2000-02-09 2001-10-26 Nisshin Steel Co Ltd 高Ａｌ含有溶融Ｚｎ−Ａｌ−Ｍｇ系めっき鋼板
JP2001355055A (ja) 2000-04-11 2001-12-25 Nippon Steel Corp 未塗装加工部ならびに塗装端面部の耐食性に優れた溶融Ｚｎ−Ａｌ−Ｍｇ−Ｓｉめっき鋼材
JP3684135B2 (ja) * 2000-04-11 2005-08-17 新日本製鐵株式会社 耐食性の優れたＳｉ含有高強度溶融亜鉛めっき鋼板とその製造方法
JP2002113502A (ja) 2000-10-05 2002-04-16 Nkk Corp 鋼帯の製造方法及びその装置
JP4683764B2 (ja) 2001-05-14 2011-05-18 日新製鋼株式会社 耐食性に優れた溶融Ｚｎ−Ａｌ−Ｍｇ系合金めっき鋼材
US6677058B1 (en) * 2002-07-31 2004-01-13 Nisshin Steel Co., Ltd. Hot-dip Zn plated steel sheet excellent in luster-retaining property and method of producing the same
NZ539228A (en) * 2002-10-28 2006-09-29 Nippon Steel Corp High corrosion-resistant hot dip coated steel product excellent in surface smoothness and formability, and method for producing hot dip coated steel product
JP5208502B2 (ja) 2004-06-29 2013-06-12 タタ、スティール、アイモイデン、ベスローテン、フェンノートシャップ 溶融亜鉛合金めっき鋼板およびその製造方法
JP4546884B2 (ja) * 2004-07-07 2010-09-22 新日本製鐵株式会社 加工部耐食性に優れる表面処理めっき鋼板
JP4757581B2 (ja) 2005-09-20 2011-08-24 新日本製鐵株式会社 溶接性に優れる高耐食性溶融めっき鋼板とその製造方法
US8592049B2 (en) 2006-01-30 2013-11-26 Nippon Steel & Sumitomo Metal Corporation High strength hot dip galvanized steel sheet and high strength galvannealed steel sheet excellent in shapeability and plateability
JP5588112B2 (ja) 2008-03-27 2014-09-10 株式会社神戸製鋼所 耐食性に優れたクロメートフリー被覆溶融亜鉛めっき鋼板
KR101143180B1 (ko) * 2009-05-19 2012-05-08 주식회사 포스코 용융 아연합금 도금욕, 용융 아연합금 도금강재 및 그 제조방법
JP5499664B2 (ja) 2009-11-30 2014-05-21 新日鐵住金株式会社 疲労耐久性に優れた引張最大強度９００ＭＰａ以上の高強度冷延鋼板及びその製造方法、並びに、高強度亜鉛めっき鋼板及びその製造方法
JP5556186B2 (ja) 2010-01-15 2014-07-23 新日鐵住金株式会社 高耐食性溶融亜鉛めっき鋼板
US20130153077A1 (en) 2010-06-09 2013-06-20 Sanoh Kogyo Kabushiki Kaisha Metal pipe for vehicle piping and method of surface-treating the same
KR102099588B1 (ko) 2011-02-28 2020-04-10 닛테츠 닛신 세이코 가부시키가이샤 용융 Ｚｎ-Ａｌ-Ｍｇ계 도금 강판 및 제조방법
WO2013002358A1 (ja) 2011-06-30 2013-01-03 新日鐵住金株式会社 外観均一性に優れた高耐食性溶融亜鉛めっき鋼板およびその製造方法
JP5748829B2 (ja) 2013-12-03 2015-07-15 日新製鋼株式会社 溶融Ｚｎ合金めっき鋼板およびその製造方法
CN105940131A (zh) 2013-12-19 2016-09-14 日新制钢株式会社 加工性优异的热浸Zn-Al-Mg系镀层钢板及其制造方法
KR101714935B1 (ko) * 2014-12-24 2017-03-10 주식회사 포스코 용접성 및 가공부 내식성이 우수한 아연합금도금강재 및 그 제조방법
KR101726090B1 (ko) * 2015-12-22 2017-04-12 주식회사 포스코 표면품질 및 도금밀착성이 우수한 고강도 용융아연도금강판 및 그 제조방법
KR102075182B1 (ko) 2015-12-24 2020-02-10 주식회사 포스코 도금성이 우수한 고강도 용융 아연계 도금 강재 및 그 제조방법
JP6087461B1 (ja) 2016-04-26 2017-03-01 日本ペイント・インダストリアルコ−ティングス株式会社 表面処理鋼材

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06306461A (ja) * 1993-04-28 1994-11-01 Nippon Steel Corp 外観性に優れた合金化溶融亜鉛めっき鋼板の製造法
KR20150070841A (ko) * 2013-12-17 2015-06-25 동부제철 주식회사 고내식 도금강판 및 그 제조방법
CN105483547A (zh) * 2015-12-03 2016-04-13 武汉钢铁(集团)公司 家电用深冲耐指纹电镀锌板及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
西村一实等: "热轧钢板的表面状态对热镀锌反应的影响", 《武钢技术》 *

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