CN110168141A - 多层结构的镀覆钢板及其制造方法 - Google Patents

多层结构的镀覆钢板及其制造方法 Download PDF

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Publication number
CN110168141A
CN110168141A CN201780080312.XA CN201780080312A CN110168141A CN 110168141 A CN110168141 A CN 110168141A CN 201780080312 A CN201780080312 A CN 201780080312A CN 110168141 A CN110168141 A CN 110168141A
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China
Prior art keywords
layers
steel sheet
coated steel
layer
multilayered structure
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CN201780080312.XA
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Inventor
高景弼
南庆勋
金兑烨
李东烈
郑勇华
郑宇城
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Posco Holdings Inc
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Posco Co Ltd
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Publication of CN110168141A publication Critical patent/CN110168141A/zh
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
    • 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
    • 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
    • B32B15/04—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
    • 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
    • B32B15/04—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
    • 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
    • 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
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • C—CHEMISTRY; METALLURGY
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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
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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
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Abstract

本发明涉及一种多用于车辆、家用电器、建筑用等材料的镀覆钢板，更具体地，涉及一种多层结构的镀覆钢板及其制造方法。

Description

多层结构的镀覆钢板及其制造方法
技术领域
本发明涉及一种多用于车辆、家用电器、建筑用等材料的镀覆钢板，更具体地，涉及一种多层结构的镀覆钢板及其制造方法。
背景技术
以车辆材料、家用电器产品、建筑材料等用途使用的钢板产品表面为了提高耐腐蚀性和耐久性通过电镀或热浸镀覆等方式执行镀锌。相比未经处理的一般钢板产品，这种镀锌处理的产品因锌的牺牲腐蚀保护性而耐腐蚀性显著提高，因此应用于整个产业中。
但是，近年来，在相关产业领域，对耐腐蚀性更优异、轻量且经济的镀覆产品的需求在增加，因此正在积极地开发与此相关的技术。并且，作为所述镀锌钢板的镀层的主要原料的锌的价格急剧上升，因此正在持续地进行通过减少锌的含量来降低镀覆量或者用其他元素代替锌的研究。
首先，以往提出了一种减少镀覆钢板的镀覆量的技术，但是，镀覆量是对金属的防腐蚀和长期防锈性产生很大影响的因素，因此镀覆量越增加，产生红锈所需的时间就会越增加，从而提高耐腐蚀性。因此，由于耐腐蚀性降低的问题而无法减少镀覆量。
另一方面，进行了各种使用锌与其他物质结合的合金化研究。典型的例子为，由于Zn-Mg合金镀覆表现出比镀锌(Zn)更优异的耐腐蚀性，开发出大量的诸如Zn-Mg合金或Zn-Mg-X(X＝Al、Ni、Cr、Pb、Cu等)合金的包含第三元素的多种产品。
但是，Zn-Mg合金镀覆所形成的合金相(phase)均为金属间化合物Mg2Zn11、MgZn2、MgZn、Mg7Zn3等，因此具有比Zn或Mg脆(brittle)的特性，从而在钢板的加工步骤中产生多个裂纹或剥离(peel-off)，因此实际上几乎无法应用。即，相比镀纯锌，Zn-Mg合金镀覆具有坚硬且容易脆裂的特性，因此镀层在微小的变形中也会产生裂纹(crack)而容易脱落，镀覆粘附力显著降低。
另外，由于Zn-Mg镀层中的Mg的活性非常高，在湿润的气氛中产品表面与水分进行反应而变黑的黑变现象的产生会降低产品的质量。用于防止所述黑变现象的努力的技术有专利文献1和2。
现有技术文献
(专利文献1)日本公开专利特开平9-241828号
(专利文献2)日本公开专利特开2005-146340号
发明内容
(一)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层的耐腐蚀性优异、防止表面的黑变现象的抗黑变性优异、镀层的粘附力优异的Zn/Mn/Zn多层结构的镀覆钢板及其制造方法。
本发明所要解决的技术问题并不局限于以上提及的问题，本发明所属技术领域的普通技术人员可以通过以下的记载清楚地理解未提及的其它问题。
(二)技术方案
本发明的一个方面提供一种多层结构的镀覆钢板，所述镀覆钢板包含：基材钢板；第一Zn层，形成在所述基材钢板上；第二Mg层，形成在所述第一Zn层上；以及第三Zn层，形成在所述第二Mg层上，其中，所述第二Mg层为非晶相。
本发明的另一方面提供一种多层结构的镀覆钢板的制造方法，所述镀覆钢板的制造方法包括以下步骤：准备基材钢板；在所述基材钢板上形成第一Zn层；在所述第一Zn层上形成第二Mg层；以及在所述第二Mg层上形成第三Zn层，其中，所述第二Mg层和所述第三Zn层通过真空沉积方形成，基材钢板的温度为50～120℃。
(三)有益效果
根据本发明，可以提供具有优异的耐腐蚀性的同时镀覆粘附性优异并且不会发生表面黑变现象的Zn/Mg/Zn结构的多层镀覆钢板及其制造方法。
附图说明
图1是示出根据本发明的一个实施例的Zn/Mg/Zn多层镀覆钢板的透射电子显微镜(TEM)照片。
图2是拍摄根据本发明的一个实施例的Zn/Mg/Zn多层镀覆钢板中第二Mg层的TEM衍射图案的照片。
图3的(a)和(b)分别是评价发明例8和比较例8的耐腐蚀性的照片。
图4的(a)和(b)分别是对发明例8和比较例10的镀覆粘附性进行评价(OT bendingtest(OT弯曲试验))的照片。
最佳实施方式
下面，对本发明进行详细说明。
在本发明的一个实施例中，在基材钢板表面形成第一Zn层、第二Mg层和第三Zn层的多层结构，通过控制各层的厚度，调节第三Zn层向第二Mg层内部的扩散，并且第二Mg层自身的非晶化来显著提高耐腐蚀性，防止形成结晶化的Zn-Mg合金层，从而可以确保镀覆粘附力，并且对上部Zn层进一步进行镀覆以防止黑变现象。
首先，对本发明的多层镀覆钢板进行详细说明。如图1所示，本发明的多层镀覆钢板包含：第一Zn层，形成在基材钢板上；第二Mg层，形成在所述第一Zn层上；以及第三Zn层，形成在所述第二Mg层上。
对所述基材钢板的种类不作特别限制，诸如热轧钢板、冷轧钢板等只要可以在本发明所属技术领域中使用的钢板即可。
在所述基材钢板上形成第一Zn层。所述第一Zn层可以通过热浸镀锌、电镀锌、真空沉积等方法形成，并且对所述第一Zn层的镀层的组成成分不作特别限定，可以适用一般的热浸镀锌、电镀锌、真空沉积等的镀层组成成分。
所述第一Zn层的厚度优选为1～3μm。当所述第一Zn层的厚度小于1μm时，根据基础铁的粗糙度，镀覆的厚度偏差严重，从而镀覆效果可能降低。另一方面，本发明的多层结构的整个镀覆钢板的耐腐蚀性主要取决于第二Mg层，当第一Zn层的厚度超过3μm时，耐腐蚀性的增加效果不大，但是时间和成本增加，因此存在效率低的问题。
在所述第一Zn层上形成第二Mg层，在所述第二Mg层上形成第三Zn层。优选地，分别使用纯Mg和Zn金属并通过真空沉积方法来形成所述第二Mg层和第三Zn层。
所述第二Mg层内部可以是从第三Zn层扩散的Zn混合的一种固溶相(solidsolution)，随着Zn扩散，Mg结晶结构发生变化，结果第二Mg层伴随着晶格畸变(latticedistortion)而无法进行正常的结晶化(crystallization)。另外，扩散的Zn阻碍Mg晶粒的生长，最终第二Mg层生长为非晶相(amorphous phase)。对于所述第二Mg层的非晶相与否可以通过透射电子显微镜(Transmission Electron Microscope，TEM)来确认。即，如图2所示，可以知道，第二Mg层不呈现衍射图案呈晶体结构的斑点(spot)形状的图案，这说明所述第二Mg层生长为非晶相。
另一方面，所述第二Mg层为非晶相，在内部可以包含由Mg和扩散的Zn反应而形成的微细的Zn-Mg非晶相或纳米晶形态的Zn-Mg合金相。所述纳米晶Zn-Mg合金相具有最大几十nm的尺寸，因此，与一般的结晶化的合金相不同地，通过X射线衍射(X-ray diffraction，XRD)或TEM观察时也会显示为非晶相。即，具有在非晶相第二Mg层内所述Zn-Mg非晶相或纳米晶形态的Zn-Mg合金相占一部分的结构。
所述Zn-Mg非晶相或纳米晶Zn-Mg合金相在第二Mg层内部与第二Mg层的非晶化一同在增加耐蚀性方面表现出协同效应。一般来说，与晶体相比，非晶的电阻率(resistivity)大而导电性降低，因此，不会发生电化学反应，可以更好地抵抗腐蚀反应。因此，如上所述的Zn-Mg非晶相除了非晶效果之外作为一种合金相大大有助于耐腐蚀性。另外，扩散的Zn在第二Mg层内部中在纳米单位的微小的区域中合金化而形成的纳米晶Zn-Mg合金相虽然难以期待整个镀层形成为合金相的MgxZny程度的耐腐蚀性，但是可以期待腐蚀特性至少比以纯Mg或Zn存在的镀层大大改善。
Zn向所述第二Mg层的内部扩散而形成的所述第二Mg层内的Zn-Mg非晶相或纳米晶形态的Zn-Mg合金相中包含的Zn的含量优选为20至60重量％。但是当扩散的Zn含量小于20重量％时，可能对Mg的生长影响不大，并且Mg晶格畸变也不大，从而可能无法顺利发生非晶化。另外，当扩散的Zn含量超过60重量％时，由于受基板温度的影响很大而扩散得多，随着基板温度的增加而扩散的Zn通过热驱动力与部分Mg合金化，从而开始形成一部分结晶化的Zn-Mg合金相。所述Zn-Mg合金相是结晶相而不是非晶相，并且如在背景技术所述是高脆性区域，对镀覆粘附性产生不好的影响的同时产生黑变现象。因此，扩散到第二Mg层内部的Zn的含量优选为最大60重量％。
所述第二Mg层的厚度优选为0.5～1.5μm。当第二Mg层的厚度小于0.5μm时，即使在内部形成基于Zn的扩散的非晶化和纳米晶Mg-Zn合金相，由于厚度薄，有助于提高耐蚀性的效果可能降低，当第二Mg层的厚度超过1.5μm时，厚度达到Zn可扩散的厚度以上，由纯Mg构成的镀层区间变宽，形成无助于提高耐腐蚀性的不必要的镀层，从而不经济，并且即使镀覆第三Zn层，随着时间的经过，可能引起黑变现象。
如上所述，所述第三Zn层供应可扩散到第二Mg层内部的Zn的同时可以起到第二Mg层暴露在表面时防止发生黑变现象的一种保护膜或阻挡(barrier)层的作用。所述第三Zn层的厚度可以是1～3μm。当第三Zn层的厚度小于1μm时，为了防止第二Mg层的黑变现象而镀覆的Zn层无法充分阻断外部湿气等侵入镀膜内部，因此难以期待充分的抗黑变性，当第三Zn层的厚度超过3μm时，抗黑变性的提高效果不会有进一步大的改善，并且形成不必要的镀层，因此不经济。
下面，对本发明的多层镀覆钢板的制造方法进行详细说明。本发明的多层镀覆钢板的制造方法包括以下步骤：准备基材钢板；在准备的所述基材钢板上形成第一Zn层；在所述第一Zn层上形成第二Mg层；以及在所述第二Mg层上形成第三Zn层。
在准备所述基材钢板的过程中，可以包括去除形成在基材钢板表面的纳米程度的薄氧化膜(氧化皮)的过程。对用于去除所述氧化膜的方法不作特别限定，例如，可以通过利用离子束的等离子体蚀刻来去除所述氧化膜。如上所述，在去除氧化膜的基材钢板的表面上形成镀层。
如上所述，对在所述基材钢板上形成第一Zn层的方法不作特别限制，可以通过一般的热浸镀锌、电镀锌、真空沉积等方法来形成，并且对所述第一Zn层的镀层组成成分不作特别限制，只要是一般的热浸镀锌、电镀锌、真空沉积方法的镀锌方法即可。
优选地，所述第二Mg层和第三Zn层分别使用纯Mg和Zn金属并通过真空沉积方法来形成。此时，优选地，使用等离子体、离子束等来去除表面的异物或自然氧化膜。所述真空沉积方法可以采用电子束法、溅射法、热蒸发法、感应加热蒸发法、离子电镀法等，优选地，为了提高生产速度可以使用高速沉积，优选通过具有电磁搅拌效果(ElectromagneticStirring)的电磁悬浮感应加热方法形成。
在真空沉积所述第二Mg层和第三Zn层时，基材钢板的温度优选为50～120℃。当所述基材钢板的温度上升时，沉积的物质的原子移动顺利，可以增加物质的扩散迁移率。当基材钢板的温度达到50℃以上时，第三Zn层的Zn原子可以顺利地扩散到所述第二Mg层内部，但是当基材钢板的温度超过120℃时，扩散的Zn原子和第二Mg层内部的Mg原子之间开始进行合金化，从而可以形成一部分结晶化的Zn-Mg合金层。
所述Zn-Mg合金层的形成具有大大增加耐腐蚀性的效果，但是随着合金化的区域变大，脆性高的合金相的比率也会一起增加，因此，加工时镀层脱落，镀覆粘附性变差。基于上述理由，基材钢板的温度优选为50～120℃。
另一方面，在真空沉积所述第二Mg层和第三Zn层时，腔室内真空度优选为1×10-5～1×10-2毫巴(mbar)。当保持这样的真空度时，可以防止在形成薄膜的过程中由于氧化物的形成所导致的脆性增加或物理性质降低。
具体实施方式
下面，对本发明的实施例进行详细说明。以下实施例仅用于理解本发明，而并不限定本发明。
(实施例1)
作为基材钢板准备一般的冷轧钢板，然后通过普通的电镀锌方法形成第一Zn层。
然后，将所述钢板装入真空腔室内，并通过等离子体预处理来去除表面的异物和自然氧化膜，然后利用电磁悬浮感应加热沉积法形成第二Mg层和第三Zn层。将各层的厚度和沉积时的温度表示在表1中。在真空沉积第二Mg层和第三Zn层时，腔室内部的真空度保持在约2×10-2～9×10-4mbar之间。
针对如上所述制造的多层镀覆钢板，评价抗黑变性、镀覆粘附性、耐腐蚀性等并将其一起表示在表1中。
此时，对于抗黑变性评价，通过肉眼判断在温度为50℃和相对湿度为95％的恒温恒湿机内将镀覆钢板保持72小时前后的色差。
O：没有颜色变化，X：产生表面黑化
对于镀覆粘附性，利用一般使用的OT弯曲试验(OT bending test)进行评价，评价是否剥离，并且通过XRD分析来分析薄膜的相。所述薄膜的相分析针对整个镀层结构，表1中Zn+Mg表示分析来自第一Zn层和第三Zn层的Zn结晶相以及因第二Mg层没有非晶化而同时分析Mg结晶相。另一方面，Zn表示因第二Mg层非晶化而通过XRD没有观察到Mg结晶相，因此只分析来自第一Zn层和第三Zn层的Zn结晶相。
最后，对于耐腐蚀性评价，在5％的盐水浓度、35℃的温度、1kg/cm2的喷雾压力条件下进行盐水喷雾试验以测量产生5％的红锈的时间。耐腐蚀性评价的结果判断基准如下。
120小时以上：OK，少于120小时：NG
[表1]
可以确认，满足发明的条件的发明例1至7的情况下均可以经济地制造抗黑变性、镀覆粘附性和耐腐蚀性优异的镀覆钢板。
比较例1至3中没有形成第三Zn层，而仅形成由第一Zn层和第二Mg层构成的二层结构，并且Zn和Mg以单相构成各层，从而表现出耐腐蚀性非常差的特性，由于上部由Mg层覆盖，表现出黑变现象非常严重的结果。
在比较例4中，由于第三Zn层的扩散引起的第二Mg层非晶化以及在第二Mg层微小区域中进行非晶或纳米晶Zn-Mg合金化，耐腐蚀性提高，但是由于超出本发明的Mg层的厚度，而以不必要的镀层区域存在，因此不经济。
在比较例5中，镀覆的第三Zn层的厚度为本发明中提出的厚度以下，从而可扩散的Zn量的范围变小，因此扩散到第二Mg层内部的Zn量少，基于此的Mg以及部分Zn-Mg非晶化和纳米晶合金相的程度降低，因此表现出耐腐蚀性差的结果。
在比较例6中，镀覆的第三Zn层的厚度为本发明中提出的厚度以上，从而耐腐蚀性的提高效果不大，因此不经济，另外，随着第三Zn层变得过厚，表现出镀覆粘附性略微变差的结果。
在比较例7中，镀覆的第一Zn层的厚度为本发明中提出的厚度以上，从而本发明中所要求的特性的提高效果微弱，并且可能是以在经济上不必要的镀层区域存在的厚度。
(实施例2)
接着，以与实施例1相同的条件，将第一Zn层、第二Mg层、第三Zn层分别制造成1μm、1μm、3μm的厚度。但是，在真空沉积第二Mg层和第三Zn层时，使基板的温度从常温到160℃具有不同的温度，并调节第三Zn层的Zn扩散度，以制造镀覆钢板。
对于如上所述制造的镀覆钢板，以实施例1的方法评价抗黑变性、镀覆粘附性、耐腐蚀性和相分析，并将其结果表示在以下表2中。另外，对于扩散到第二Mg层内部的Zn重量比，将通过透射电子显微镜-能谱仪(TEM-EDS)点分析来分析第二Mg层截面部的结果一起表示在表2中。
[表2]
可以确认，满足本发明的条件的发明例8至10均具有优异的抗黑变性、镀覆粘附性、耐腐蚀性。
与此相比，在比较例8中，在没有进行单独的加热操作的情况下镀覆第二Zn层和第三Mg层时，几乎没有进行第三Zn层的Zn扩散，因此各镀层单独存在，并表现出耐腐蚀性非常差，在比较例9中，以30℃的温度加热，第三Zn层的Zn扩散程度小，在第二Mg层内部中存在的Zn量小于几％，因此，Mg层中也形成结晶化的Mg相，基于此的非晶化几乎没有发生，因此，表现出耐腐蚀性相对降低的结果。
在比较例10中，以160℃的温度加热，从而充分进行第三Zn层的Zn扩散的同时进入到发生一定程度的合金化的温度区域中，因此第二Mg层的Mg和扩散的Zn进行一定程度的合金化，部分地形成Zn-Mg合金相。对于所述Zn-Mg合金相，通过XRD测量结果确认为Mg2Zn11相，并且通过形成所述结晶化的合金相，耐腐蚀性得以充分显现，但是，随着Zn-Mg合金相特有的脆性增加，在镀覆粘附性方面，表现出发生部分剥离的现象的结果。
另一方面，图3的(a)和(b)分别是评价发明例8和比较例8的耐腐蚀性后观察表面产生的红锈的照片。如图3所示，可以知道，在本发明例(a)中，没有产生红锈，但是在比较例(b)中产生了红锈。另外，图4的(a)和(b)分别是示出发明例8和比较例10的OT弯曲试验结果的照片，可以知道，在发明例(a)中镀膜剥离不严重，但是在比较例(b)中镀膜剥离较差。

Claims (9)

1.一种多层结构的镀覆钢板，包含：
基材钢板；
第一Zn层，形成在所述基材钢板上；
第二Mg层，形成在所述第一Zn层上；以及
第三Zn层，形成在所述第二Mg层上，
其中，所述第二Mg层为非晶相。
2.根据权利要求1所述的多层结构的镀覆钢板，其中，
所述第二Mg层包含Zn-Mg非晶相和纳米晶形态的Zn-Mg合金相中的一种以上。
3.根据权利要求2所述的多层结构的镀覆钢板，其中，
在所述Zn-Mg非晶相和所述纳米晶形态的Zn-Mg合金相中包含的Zn的含量为20～60重量％。
4.根据权利要求1所述的多层结构的镀覆钢板，其中，
所述第一Zn层的厚度为1～3μm。
5.根据权利要求1所述的多层结构的镀覆钢板，其中，
所述第二Mg层的厚度为0.5～1.5μm。
6.根据权利要求1所述的多层结构的镀覆钢板，其中，
所述第三Zn层的厚度为1～3μm。
7.一种多层结构的镀覆钢板的制造方法，包括以下步骤：
准备基材钢板；
在所述基材钢板上形成第一Zn层；
在所述第一Zn层上形成第二Mg层；以及
在所述第二Mg层上形成第三Zn层，
所述第二Mg层和所述第三Zn层通过真空沉积法形成，基材钢板的温度为50～120℃。
8.根据权利要求7所述的多层结构的镀覆钢板的制造方法，其中，
所述第一Zn层通过选自热浸镀、电镀和真空沉积中的任一方法执行。
9.根据权利要求7所述的多层结构的镀覆钢板的制造方法，其中，
在真空沉积所述第二Mg层和所述第三Zn层时的腔室的真空度为1×10-5～1×10-2mbar。
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