CN114787411B - 弯曲加工性和耐蚀性优异的热浸镀锌钢板及其制造方法 - Google Patents

弯曲加工性和耐蚀性优异的热浸镀锌钢板及其制造方法 Download PDF

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CN114787411B
CN114787411B CN202080084257.3A CN202080084257A CN114787411B CN 114787411 B CN114787411 B CN 114787411B CN 202080084257 A CN202080084257 A CN 202080084257A CN 114787411 B CN114787411 B CN 114787411B
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steel sheet
mgzn
dip galvanized
plating
corrosion resistance
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CN114787411A (zh
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金成周
金兴润
金明守
姜大荣
金龙珠
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Posco Holdings Inc
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Posco Co Ltd
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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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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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Abstract

本发明提供一种弯曲加工性和耐蚀性优异的热浸镀锌钢板及其制造方法。本发明的热浸镀锌钢板包括：基础钢板；Zn‑Mg‑Al系镀层，其设置在所述基础钢板的至少一面，并且相对于除了从基础钢板扩散的铁(Fe)之外的剩余成分，以重量％计，所述Zn‑Mg‑Al系镀层包含Al：5.1‑25％、Mg：4.0‑10％、余量的Zn及其它不可避免的杂质；以及界面合金层，其形成在所述基础钢板和所述镀层之间，并且所述界面合金层具有Fe‑Al‑Zn组成，其中，所述界面合金层的厚度为0.5‑2μm并具有树枝状形态，所述Zn‑Mg‑Al系镀层具有包含Zn‑Al‑MgZn2三元系共晶组织、Zn‑MgZn2二元系共晶组织、Zn固溶的Al单相组织及Zn单相组织中的一种以上的组织，并且MgZn2组织中包含团聚的Al。

Description

弯曲加工性和耐蚀性优异的热浸镀锌钢板及其制造方法
技术领域
本发明涉及一种弯曲加工性和耐蚀性优异的热浸镀锌钢板及其制造方法。
背景技术
镀锌的热浸镀锌钢板具有暴露在腐蚀环境中时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腐蚀的特性。此外，镀层的锌被氧化而在钢材表面形成致密的腐蚀产物，使钢材与氧化气氛隔绝，从而提高钢材的耐腐蚀性。由于如上所述的有利的特性，近年来，热浸镀锌钢板在家电产品和汽车用钢板的应用范围正在扩大。
然而，由于产业升级导致大气污染增加，腐蚀环境逐渐恶化，并且由于对资源和节能的严格管制，对开发与现有的镀锌钢材相比具有更优异的耐蚀性的钢材的需求正在增加。
为了改善该问题，对通过在锌镀浴中添加铝(Al)和镁(Mg)等元素来提高钢材的耐蚀性的锌合金系镀覆钢材的制造技术进行了各种研究。作为代表性的锌合金系镀覆材料，目前正积极研究在Zn-Al镀覆组成系中进一步添加Mg的Zn-Mg-Al系锌合金镀覆钢板的制造技术。
然而，与镀锌钢板相比，Zn-Mg-Al系锌合金镀覆钢板虽然具有显著的耐腐蚀性，但具有弯曲加工性差的缺点。即，所述锌合金镀覆钢板的镀层内包含大量的通过Zn、Al及Mg的热力学相互反应形成的Zn-Al-Mg系金属间化合物，这种金属间化合物的硬度高，因此在弯曲加工时会在镀层内引起裂纹，因此具有降低弯曲加工性的缺点。这种裂纹成为损害弯曲加工部的外观或降低耐蚀性的原因。
对这种加工时的裂纹的形成产生影响的因素有很多种，但在材料的物理性能方面，已知镀层的硬度和界面合金层会产生影响。为此，为了可以抑制Zn-Al-Mg系金属间化合物中硬度最高的MgZn2相的局部粗大化并均匀地分布在镀层内，正在尝试各种工艺变化。
然而，到目前为止，在包含大量Mg的Mg-Al-Zn成分系中不能从根本上避免MgZn2相的局部粗大化，为了最大限度地减少弯曲加工时的裂纹的形成，正在尝试通过在Zn-Mg-Al镀覆系中添加微量Si来抑制在镀层与基材铁之间形成的Fe-Al界面合金相的生长。已知这种Fe-Al界面合金相通常生长为Fe2Al5相，当粗大地生长为层(layer)状时，由于硬度高，加工时容易发生界面断裂。然而，这种添加微量Si的技术通常精细地调整为0.1-0.2重量％，但添加过多的Si时，镀层内可能会形成粗大的Mg2Si形式的附加的合金相。因此，可以认为持续地确保弯曲加工性是与成型的稳定性和加工后的耐蚀性相关的非常重要的特性。
[现有技术文献]
[专利文献]
(专利文献1)日本专利公开JP2003-155549号
发明内容
要解决的技术问题
本发明是为了解决上述现有技术的问题而提出的，本发明的目的在于提供一种可以通过减少弯曲加工成型时的镀层内的裂纹来确保优异的弯曲加工性和耐蚀性的具有Zn-Al-Mg系镀层的热浸镀锌钢板及其制造方法。
本发明的技术问题并不受限于上述内容。本发明所属技术领域的技术人员可以从本发明的说明书的全部内容容易地理解本发明的附加技术问题。
技术方案
本发明的一个方面涉及一种弯曲加工性和耐蚀性优异的热浸镀锌钢板，其特征在于，包括：基础钢板；Zn-Mg-Al系镀层，其设置在所述基础钢板的至少一面，并且相对于除了从基础钢板扩散的铁(Fe)之外的剩余成分，以重量％计，所述Zn-Mg-Al系镀层包含Al：5.1-25％、Mg：4.0-10％、余量的Zn及其它不可避免的杂质；以及界面合金层，其形成在所述基础钢板和所述镀层之间，并且所述界面合金层具有Fe-Al-Zn组成，其中，所述界面合金层的厚度为0.5-2μm并具有树枝状形态，所述Zn-Mg-Al系镀层具有包含Zn-Al-MgZn2三元系共晶组织、Zn-MgZn2二元系共晶组织、Zn固溶的Al单相组织及Zn单相组织中的一种以上的组织，并且MgZn2组织中包含团聚的Al。
本发明中，所述Al和所述Mg的含量可以确定为位于Mg-Al-Zn三元系相图的MgZn2和Al的二共晶线。
包括所述基础钢板的镀层的90度弯曲和0T弯曲加工时形成的弯曲裂纹的宽度分别可以为30μm以下和100μm以下。
此外，本发明涉及一种制造弯曲加工性和耐蚀性优异的热浸镀锌钢板的方法，其特征在于，包括以下步骤：准备基础钢板；在镀浴中对所述基础钢板进行热浸镀锌，以重量％计，所述镀浴包含Al：5.1-25％、Mg：4.0-10％、余量的Zn及其它不可避免的杂质；以及利用惰性气体，将镀覆钢板以5-30℃/秒的冷却速度进行冷却，从所述镀浴的表面开始冷却至上辊(Top roll)区间，从而制造在所述基础钢板上依次形成界面合金层和Zn-Mg-Al系镀层的热浸镀锌钢板，其中，将所述基础钢板浸入具有温度(T)的镀浴中进行镀覆，所述温度(T)使由以下关系式1定义的所述界面合金层的厚度(H)可以满足0.5-2μm的范围。
[关系式1]
H(μm)＝170.53+0.0008T2-0.7376T
所述Zn-Mg-Al系镀层可以具有包含Zn-Al-MgZn2三元系共晶组织、Zn-MgZn2二元系共晶组织、Zn固溶的Al单相组织及Zn单相组织中的一种以上的组织，并且MgZn2组织中可以包含团聚的Al。
可以将所述镀浴的温度保持在470-520℃的范围。
所述镀浴中的Al和Mg的含量可以确定为位于Mg-Al-Zn三元系相图的MgZn2和Al的二共晶线。
所述基础钢板浸入所述镀浴中的入浴时间可以为1-5秒。
所述惰性气体可以为N、Ar及He中的一种。
有益效果
根据本发明的热浸镀锌钢板具有弯曲加工性和耐蚀性优异的优点。此外，根据本发明，对具有镀层的热浸镀锌钢板进行90度弯曲加工试验而测量的裂纹的宽度低至30μm以下的水平，所述镀层包含Al：5.1-25重量％、Mg：4.0-10重量％并且不包含Si，因此可以提供一种具有优异的弯曲加工性且加工后也具有优异的耐蚀性的热浸镀锌钢板。
附图说明
图1是用场发射扫描电子显微镜(Field Emission Scanning ElectronMicroscope，以下称作“FE-SEM”)观察(倍率为×2000倍)作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板的截面的照片。
图2是用FE-SEM观察(倍率为×10000倍)作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板的界面合金层表面的照片。
图3是用TEM-EDS观察对作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板的界面合金层的截面进行研磨而获取的复制品(replica)样品的Fe、Al、Zn成分的映射(mapping)照片。
图4是对作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板的界面合金层沿着图3中标出的黄色线进行检测的重量百分比(重量％)。
图5是用FE-SEM观察(倍率为×100倍、×200倍、×300倍)对作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板进行90度弯曲加工后形成在弯曲加工顶部的裂纹的照片。
图6是用FE-SEM观察(倍率为×100倍、×200倍、×300倍)对比较例1的热浸镀锌钢板进行90度弯曲加工后形成在弯曲加工顶部的裂纹的照片。
图7是用FE-SEM观察(倍率为×2000倍)比较例4的截面的照片。
图8是用FE-SEM观察(倍率为×2000倍)比较例5的截面的照片。
图9是用FE-SEM观察(倍率为×2000倍)比较例6的截面的照片。
最佳实施方式
以下，对本发明进行说明。
如上所述，通常作为最大限度地减少包含大量Mg的Mg-Al-Zn镀覆钢板的弯曲加工时的裂纹的形成的方法，提出了一种通过在镀浴中添加微量Si来抑制形成在镀层和基材铁之间的高硬度的界面合金相的粗大化的方法。然而，这种方法的局限性在于，在镀层内可能会形成粗大的Mg2Si形式的附加的合金相。
因此，本发明人为了保持作为包含大量Mg的锌系合金镀覆钢板的优点的优异的耐蚀性的同时使弯曲加工时产生的裂纹最小化，对根据是否添加Si的界面合金相的成分、形状及弯曲加工时产生的裂纹进行了详细的研究，并基于其结果完成了本发明。
这种本发明的热浸镀锌钢板包括：基础钢板；Zn-Mg-Al系镀层，其设置在所述基础钢板的至少一面，并且相对于除了从基础钢板扩散的铁(Fe)之外的剩余成分，以重量％计，所述Zn-Mg-Al系镀层包含Al：5.1-25％、Mg：4.0-10％、余量的Zn及其它不可避免的杂质；以及界面合金层，其形成在所述基础钢板和所述镀层之间，并且所述界面合金层具有Fe-Al-Zn组成。
此外，所述界面合金层的厚度为0.5-2μm并具有树枝状形态，所述Zn-Mg-Al系镀层具有包含Zn-Al-MgZn2三元系共晶组织、Zn-MgZn2二元系共晶组织、Zn固溶的Al单相组织及Zn单相组织中的一种以上的组织，并且MgZn2组织中包含团聚的Al。
首先，根据本发明的一个方面的热浸镀锌钢板可以包括：基础钢板；Zn-Mg-Al系镀层，其设置在所述基础钢板的至少一面；以及Fe-Al-Zn界面合金层，其形成在所述基础钢板和所述镀层之间。
所述基础钢板的至少一面上可以设置由Zn-Mg-Al系合金形成的镀层。所述镀层可以仅形成在基础钢板的一面，也可以形成在基础钢板的两面。
本发明中，相对于除了从基础钢板扩散的少量的铁(Fe)之外的剩余成分，以重量％计，所述Zn-Mg-Al系镀层可以包含Al：5.1-25％、Mg：4.0-10％、余量的Zn及其它不可避免的杂质。
Al：5.1-25％、Mg：4.0-10％
镀层中的Mg是起到提高镀覆钢材的耐蚀性的作用的元素，Mg均匀地形成腐蚀产物，由此形成的腐蚀产物不再进行腐蚀，因此最终提高耐蚀性。
通常，当添加小于1.0％的Mg时，提高耐蚀性的效果微乎其微，当添加超过2.0％的Mg时，镀浴内Mg的氧化导致镀浴浮渣的产生增加，需要经常去除浮渣，因此发生操作性变差的问题。因此，在现有技术中，在Zn-Mg-Al系锌合金镀覆的情况下，添加1.0％以上的Mg，但Mg含量的上限设定在3.0％左右。
然而，本发明中镀层内Mg的含量可以为4.0％以上，并且为了抑制锌合金镀浴内的Mg氧化物浮渣，可以添加5.1％以上的Al。另外，Al还可以与Zn和Mg组合而起到提高镀覆钢板的耐腐蚀性的作用。
另外，如上所述，已知在Zn-Mg-Al三元系合金镀覆中，Mg起到进一步稳定Zn的腐蚀产物的形成的辅助作用，但Mg含量超过10％时，Mg自身的腐蚀速度比稳定Zn的腐蚀产物的速度更快，镀覆钢板的耐腐蚀性反而可能会变差，因此可以将镀层中Mg含量的上限限制为10％以下。
此外，Mg含量为4.0-10％的情况下，当添加超过25％的Al时，熔点变成480℃以上，考虑到通常将镀浴的温度设为比镀覆组成系的熔点高40-60℃，由于过高的镀浴的温度，可能会发生引起镀浴结构体的侵蚀和钢材的变性的问题，因此考虑到这一点，Al含量可以限制为25％以下。
而且，Al和Mg的含量可以确定为位于Mg-Al-Zn三元系相图的MgZn2和Al的二共晶线。其中，确定为位于二共晶线的情况包括确定为准确地位于所述二共晶线的情况和确定为略微偏离所述二共晶线而位于所述二共晶线附近的情况。
除了上述镀层的组成之外，余量可以是Zn和其它不可避免的杂质。不可避免的杂质是在常规的热浸镀锌钢板的制造工艺中不可避免地混入的杂质，因此不能完全排除，只要是本领域的技术人员可以容易地理解该含义。
另外，通常在热浸镀锌钢板上容易出现被称作锌花(spangle)的特有的镀覆组织形状。这种锌花是由于锌的凝固反应的特性而产生的。即，锌凝固时树枝状的树枝状晶体(dendrite)以凝固核为起点生长，从而形成镀覆组织的骨架，并且该树枝状晶体之间残留的未凝固的熔融锌池(pool)最终凝固，从而镀层完成凝固。如果Al与MgZn2分离而形成为初晶组织，则Al初晶组织生长为树枝状晶体形式，随着镀覆附着量增加或凝固速度变慢，这种Al树枝状晶体形式加剧。当如上所述的树枝状晶体形式的Al初晶组织生长过大时，镀层的弯曲加剧，对表面外观产生不利的影响，并且氧化反应性优异的Al过多地暴露在表面，可能会发生镀覆钢板的氧化稳定性变差的问题。
然而，本发明中，Al和Mg的含量确定为位于Mg-Al-Zn三元系相图的MgZn2和Al的二共晶线，从而可以消除这种问题。
此外，本发明中，Zn-Mg-Al系镀层具有包含Zn-Al-MgZn2三元共晶组织、Zn-MgZn2二元共晶组织、Zn固溶的Al单相组织及Zn单相组织中的一种以上的微细组织。而且，MgZn2组织中包含团聚的Al，因此可以消除如上所述的产生锌花的问题。
此外，本发明的热浸镀锌钢板中，在所述基础钢板和镀层之间可以形成由Fe-Al-Zn的金属间化合物形成的Fe-Al-Zn界面合金层。所述界面合金层可以由镀覆初期从基础钢板扩散的Fe和镀浴的Al、Zn形成，所述界面合金层可以起到提高基础钢板和镀层的粘附性的作用，并且可以起到防止Fe从基础钢板进一步扩散到镀层的抑制层的作用。
本发明中，所述界面合金层具备具有Fe-Al-Zn组成的树枝状形态的形状，这种树枝状形态的界面合金相引发投锚效果(锚固效果)，因此非常有利于减少弯曲加工时的裂纹。
本发明中，将所述Fe-Al-Zn界面合金层的厚度限制为0.5μm以上且2μm以下的范围。当所述厚度小于0.5μm时，界面合金相的形状不能充分地生长为树枝状形态，不能引发基础钢板和镀层之间的投锚效果，并且弯曲加工性会变差。另外，当所述厚度超过2μm时，基础钢板方向的界面合金相的下部生长为厚厚的层状，加工时可能容易发生界面断裂。
如上所述构成的本发明的热浸镀锌钢板中，镀层由上述的合金组成和微细组织组成，从而与现有的含有约3.0％以内的Mg的锌系合金镀覆钢板相比，可以提供优异的耐蚀性，并且可以使弯曲加工时的裂纹的宽度最小化。
接下来，对根据本发明的另一个方面的制造热浸镀锌钢板的方法进行详细说明。
本发明的制造热浸镀锌钢板的方法包括以下步骤：准备基础钢板；在镀浴中对所述基础钢板进行热浸镀锌，以重量％计，所述镀浴包含Al：5.1-25％、Mg：4.0-10％、余量的Zn及其它不可避免的杂质；以及利用惰性气体，将镀覆钢板以5-30℃/秒的冷却速度进行冷却，从所述镀浴的表面开始冷却至上辊区间，从而制造在所述基础钢板上依次形成界面合金层和Zn-Mg-Al系镀层的热浸镀锌钢板。并且，将所述基础钢板浸入具有温度(T)的镀浴中进行镀覆，所述温度(T)使由关系式1定义的所述界面合金层的厚度(H)可以满足0.5-2μm的范围。
首先，本发明中准备基础钢板，本发明中所述基础钢板的具体种类不受限制。例如，可以不受限制地利用作为普通碳钢的冷轧钢板或热轧钢板。
接下来，本发明中将所述基础钢板浸入镀浴中进行热浸镀锌，以重量％计，所述镀浴包含Al：5.1-25％、Mg：4.0-10％、余量的Zn及其它不可避免的杂质。
本发明的镀浴不包含Si，通过制造以重量％计包含Al：5.1-25％、Mg：4.0-10％、余量的Zn及其它不可避免的杂质的镀浴来准备。为了制造上述组成的镀浴，可以使用含有规定的Zn、Al、Mg的复合钢锭或含有单独成分的Zn-Mg、Zn-Al钢锭。此外，所述镀浴中的Al和Mg的含量可以确定为位于Mg-Al-Zn三元系相图的MgZn2和Al的二共晶线。
本发明中，将基础钢板浸入如上所述的组成的镀浴中进行热浸镀。
此时，本发明的特征在于，考虑形成最终制造的镀覆钢板的界面合金层的厚度来确定所述镀浴的温度。具体地，其特征在于，浸入具有温度(T)的镀浴中进行镀覆，所述温度(T)使由以下关系式1定义的所述界面合金层的厚度(H)可以满足0.5-2μm的范围。因此，可以将形成所制造的热浸镀钢板的Fe-Al-Zn组成的界面合金层的形状制造成树枝状形态。如上所述，这种树枝状形态的界面合金相引发投锚效果(锚固效果)，因此非常有利于减少弯曲加工时的裂纹。
[关系式1]
H(μm)＝170.53+0.0008T2-0.7376T
当镀浴温度过低时，钢锭的熔解非常慢，并且镀浴的粘性大，因此可能难以确保优异的镀层表面质量。另一方面，当镀浴温度过高时，由于Zn的蒸发，可能会发生在镀覆表面上引发灰(Ash)性缺陷的问题。最重要的是，在未添加Si时，过高的镀浴温度诱导Fe从基础钢板向镀层过度溶出，从而可能会引发成为镀层的剥离原因的突出(Outburst)。
为了防止这种现象的同时形成Fe-Al-Zn组成的树枝状形态的界面合金相，所述镀浴的温度(T)应设定在470-520℃范围的条件，并且与所述界面合金层厚度(H)的关系满足所述关系式1。
此外，浸入镀浴时的基础钢板的温度优选具有比镀浴的温度高5℃以上且不超过10℃的范围，并且优选以1-5秒的入浴时间浸入镀浴中。
之后，本发明中，利用惰性气体，将镀覆钢板以5-30℃/秒的冷却速度进行冷却，从所述镀浴的表面开始冷却至上辊区间，从而制造在所述基础钢板上依次形成界面合金层和Zn-Mg-Al系镀层的热浸镀锌钢板。
即，将镀覆钢板取出，并利用惰性气体以5-30℃/秒的速度进行冷却，从镀浴表面开始冷却至上辊区间。所述惰性气体可以是N、Ar及He中的一种，在降低制造成本方面，更优选使用N。
此时，当镀浴表面到上辊区间之间的冷却速度为5℃/秒以下时，MgZn2组织过于粗大地发达，因此镀层的表面弯曲可能会加剧。此外，形成宽的Zn-MgZn2二元系共晶组织，因此可能不利于确保均匀的耐蚀性和加工性。另一方面，当镀浴表面到上辊区间之间的冷却速度超过30℃/秒时，在热浸镀过程中开始从液相凝固为固相，在液相全部转变为固相期间的温度范围60-100℃的固液区间发生急剧的凝固，并且不能形成均匀的合金组织，因此可能会显示出局部不均匀的耐蚀性结果。此外，Fe-Al-Zn相的扩散不足，界面合金相的形成被过度抑制而不能生长为树枝状形态，因此加工性可能会变差。此外，为了过快的冷却速度，氮气的使用量增加，因此可能会增加制造成本。
具体实施方式
以下，通过实施例对本发明进行更详细的说明。需要注意的是，下述实施例仅用于理解本发明，并不用于限定本发明的权利范围。
(实施例)
首先，准备冷轧钢板作为基础钢板，所述冷轧钢板含有C：0.018％、Mn：0.2％、Si：0.001％、P：0.009％、Al：0.022％且余量由Fe及不可避免的杂质组成。之后，对所述冷轧钢板进行热浸镀锌，以使所述冷轧钢板的单面的镀覆附着量为140g/m2，然后以15℃/秒的速度从镀浴表面开始冷却至上辊，从而获得Zn-Mg-Al系合金镀覆钢板。
此时，所述镀液的组成中，以重量％计，将Al改变为2.8-13％，将Mg改变为2.2-5.1％。镀浴中除了不可避免地存在的成分之外的剩余成分是Zn。镀层的成分分析通过将镀层浸入5％的盐酸中完全溶解后对该溶液进行湿法分析来进行，并将其结果示于表1中。作为参考，下表1中的镀层的成分中的Fe是在热浸镀锌过程中从基础钢板扩散的。
另外，在表2的镀浴温度下，将具有下表1的镀层组成的钢板浸入镀浴中制造镀覆钢板，此时，对最终制造的热浸镀锌钢板的界面合金层的厚度进行测量并示于下表2中。此外，为了进行比较，通过关系式1并根据镀浴温度计算的目标界面合金层厚度也示于下表2中。
[表1]
[表2]
从所述表1至表2可知，发明例1至发明例2是在满足本发明中提出的镀覆成分系和镀浴温度范围的条件下进行镀覆的情况。此外，比较例1至比较例2表示Mg含量少于本发明中提出的范围的4.0％并添加Si的情况，并且比较例3表示利用Mg和Al的含量均少的镀浴制造镀覆钢板的情况。此外，比较例4至比较例6表示虽然满足本发明中提出的镀覆的Al和Mg的成分系，但与发明例1至发明例2不同，镀浴温度范围高达530℃以上，导致镀层和基础钢板之间发生过度的合金化，并且镀层中含有7.1-8.7％的水平的Fe成分的情况。
所述表2中示出根据镀浴温度并通过关系式1计算的界面合金层的厚度和最终的界面合金层的平均厚度。发明例1至发明例2满足本发明中提出的470-520℃的镀浴温度范围，并且可以确认通过关系式1计算的界面合金层的厚度和最终的界面合金层的厚度相似。另一方面，比较例1至比较例3是镀覆成分系不在本发明中提出的范围内的情况，比较例1至比较例2的情况下，可以确认是含有抑制基础钢板和镀层之间的合金化的成分Si的成分系，界面合金层的厚度小于0.1μm。另外，比较例4至比较例6是分别以530℃、540℃及570℃的镀浴温度进行而不在可应用于关系式1的镀浴温度范围内的情况。
之后，将制造的各镀覆钢板沿与长度方向垂直的方向进行切割，然后用FE-SEM以2000倍拍摄截面，并将其结果示于图1中。图1中示出用场发射扫描电子显微镜(以下称作“FE-SEM”)观察(倍率为×2000倍)作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板的截面的照片。并且，图2是用FE-SEM观察(倍率为×10000倍)作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板的界面合金层表面的照片。
如图1所示，可以确认发明例1的镀层包含Zn-Al-MgZn2三元系共晶组织和Zn-MgZn2二元系共晶组织，并且包含Zn固溶的Al单相组织、Zn单相组织及MgZn2组织。此外，可知以深色表示的Al组织位于MgZn2组织中。此外，如图2所示，还可以确认由Fe-Al-Zn形成的界面合金层形成为厚度为0.5μm以上且2μm以下的树枝状形态。
图3是用TEM-EDS观察对作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板的界面合金层的截面进行研磨而获取的复制品样品的Fe、Al、Zn成分的映射照片。图4是对作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板的界面合金层沿着图3中标出的黄色线进行检测的重量百分比(重量％)。
如图3至图4所示，可以确认界面合金层的成分中不含有Si，而是以Fe：20-35重量％、Al：15-30重量％、Zn：30-36重量％的组成范围形成了合金相。
另外，对于所述发明例1至发明例2和比较例1至比较例3，为了根据镀层成分的钢板的弯曲加工性和耐蚀性的评价，按照以下基准进行了物理性能的评价。此时，对于比较例4至比较例6，整个镀层被合金化，因此进行了除耐蚀性评价之外的物理性能的评价。
(1)耐蚀性的评价
将各镀覆钢板装入盐雾试验机中，并根据国际标准(ASTM B117-11)测量红锈产生时间。此时，利用了5％的盐水(温度为35℃，pH为6.8)，每小时喷洒2ml/80cm2的盐水。并且，为了排除镀覆附着量的差异造成的影响，将直至产生红锈所经过的时间(小时)除以镀覆附着量(g/m2)来表示为耐蚀性指数并进行评价。
○：超过50的情况
△：10至50的情况
×：小于10的情况
(2)弯曲加工性
以相同的材料厚度(1.2t)和相同的镀覆附着量(275-285g/m2)进行90度弯曲(弯曲直径：3R)、3T弯曲、1T弯曲、0T弯曲加工后，用SEM观察弯曲加工顶部的1mm的长度，然后观察弯曲裂纹的宽度并计算平均值来进行评价。
◎：弯曲裂纹的宽度为30μm以下
○：弯曲裂纹的宽度为超过30μm且60μm以下
△：弯曲裂纹的宽度为超过60μm且100μm以下
×：弯曲裂纹的宽度为超过100μm
[表3]
从所述表3中可以确认，镀层成分中的Mg和Al的组成不满足本发明的条件的比较例1至比较例3的情况下，与发明例1至发明例2相比，具有差的耐蚀性。特别地，比较例1至比较例2的情况下，可以确认弯曲加工性差，代表性地，90度弯曲和0T弯曲加工时形成的弯曲裂纹的宽度分别不能满足30μm以下和100μm以下范围的条件，并且从比90度弯曲加工更苛刻的条件的3T弯曲加工开始，与发明例1至发明例2相比，弯曲裂纹的宽度大幅增加。这种发明例1至发明例2的优异的弯曲加工特性被判断为是由于树枝状形态的界面合金相引发投锚效果(锚固效果)，从而有利于减少弯曲加工时的裂纹。此外，镀浴的组成成分在本发明的范围内但镀浴温度不在本发明的范围内的比较例4至比较例6的情况下，可以确认界面合金层不是本发明中提出的树枝状形态，并且整个镀层被合金化，从而弯曲裂纹的宽度超过100μm，并且弯曲加工性非常差。
图5是用FE-SEM观察(倍率为×100倍、×200倍、×300倍)对作为本发明的一个优选实施方案的发明例1的热浸镀锌钢板进行90度弯曲加工后形成在弯曲加工顶部的裂纹的照片。
图6是用FE-SEM观察(倍率为×100倍、×200倍、×300倍)对比较例1的热浸镀锌钢板进行90度弯曲加工后形成在弯曲加工顶部的裂纹的照片。
从图5至图6可知，与比较例1相比，发明例1的弯曲加工特性更优异，并且镀层内没有粗大化的Al、MgZn2组织，因此具有与弯曲加工性优异的比较例3同等的水平。
另外，图7是用FE-SEM观察(倍率为×2000倍)比较例4的截面的照片。并且，图8是用FE-SEM观察(倍率为×2000倍)比较例5的截面的照片，图9是用FE-SEM观察(倍率为×2000倍)比较例6的截面的照片。
如图7至图9所示，可以确认比较例4至比较例6均在整个镀层中与基础钢板进行合金化，因此由Fe-Al-Zn形成的界面合金层的厚度超过2μm。
本发明并不受限于所述具体实施方案和实施例，本发明可以通过不同的各种形式制造，并且本发明所属技术领域的技术人员可以理解在不改变本发明的技术思想或必要特征的情况下可以通过其他具体的实施方案进行。因此，应理解为上述的具体实施方案和实施例在所有方面都是示例性的，而不是限定性的。

Claims (5)

1.一种弯曲加工性和耐蚀性优异的热浸镀锌钢板，其特征在于，包括：
基础钢板；
Zn-Mg-Al系镀层，其设置在所述基础钢板的至少一面，并且相对于除了从基础钢板扩散的铁(Fe)之外的剩余成分，以重量％计，所述Zn-Mg-Al系镀层包含Al：5.1-25％、Mg：4.0-10％、余量的Zn及其它不可避免的杂质；以及
界面合金层，其形成在所述基础钢板和所述镀层之间，并且所述界面合金层具有Fe-Al-Zn组成，
其中，所述界面合金层的厚度为0.5-2μm并具有树枝状形态，所述Zn-Mg-Al系镀层具有包含Zn-Al-MgZn2三元系共晶组织、Zn-MgZn2二元系共晶组织、Zn固溶的Al单相组织及Zn单相组织中的一种以上的组织，并且MgZn2组织中包含团聚的Al。
2.根据权利要求1所述的弯曲加工性和耐蚀性优异的热浸镀锌钢板，其特征在于，所述Al和所述Mg的含量确定为位于Mg-Al-Zn三元系相图的MgZn2和Al的二共晶线。
3.根据权利要求1所述的弯曲加工性和耐蚀性优异的热浸镀锌钢板，其特征在于，包括所述基础钢板的镀层的90度弯曲和0T弯曲加工时形成的弯曲裂纹的宽度分别为30μm以下和100μm以下。
4.一种制造弯曲加工性和耐蚀性优异的热浸镀锌钢板的方法，其特征在于，包括以下步骤：
准备基础钢板；
在镀浴中对所述基础钢板进行热浸镀锌，以重量％计，所述镀浴包含Al：5.1-25％、Mg：4.0-10％、余量的Zn及其它不可避免的杂质；以及
利用惰性气体，将镀覆钢板以5-30℃/秒的冷却速度进行冷却，从所述镀浴的表面开始冷却至上辊区间，从而制造在所述基础钢板上依次形成界面合金层和Zn-Mg-Al系镀层的热浸镀锌钢板，
其中，将所述基础钢板浸入具有温度T的镀浴中进行镀覆，所述温度T使由以下关系式1定义的所述界面合金层的厚度H可以满足0.5-2μm的范围，
将所述镀浴的温度保持在470-520℃的范围，
所述Zn-Mg-Al系镀层具有包含Zn-Al-MgZn2三元系共晶组织、Zn-MgZn2二元系共晶组织、Zn固溶的Al单相组织及Zn单相组织中的一种以上的组织，并且MgZn2组织中包含团聚的Al，
[关系式1]
H(μm)＝170.53+0.0008T2-0.7376T。
5.根据权利要求4所述的制造弯曲加工性和耐蚀性优异的热浸镀锌钢板的方法，其特征在于，所述镀浴中的Al和Mg的含量确定为位于Mg-Al-Zn三元系相图的MgZn2和Al的二共晶线。
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