CN112639153A - 耐蚀性和加工性优异的热浸镀钢板及其制造方法 - Google Patents

耐蚀性和加工性优异的热浸镀钢板及其制造方法 Download PDF

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CN112639153A
CN112639153A CN201880097006.1A CN201880097006A CN112639153A CN 112639153 A CN112639153 A CN 112639153A CN 201880097006 A CN201880097006 A CN 201880097006A CN 112639153 A CN112639153 A CN 112639153A
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steel sheet
corrosion resistance
hot
alloy plating
plating layer
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金洙永
权纹栽
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Posco Holdings Inc
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Posco Co Ltd
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    • 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
    • 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
    • B32B15/012—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 aluminium or an aluminium alloy
    • 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
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    • 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
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    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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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    • Y10T428/265—1 mil or less

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)

Abstract

本发明涉及一种可以用于建筑材料、家电、汽车等的各种目的的镀覆钢板，更详细地涉及一种耐蚀性和加工性优异的热浸镀钢板及其制造方法。

Description

耐蚀性和加工性优异的热浸镀钢板及其制造方法
技术领域
本发明涉及一种可以用于建筑材料、家电、汽车等的各种目的的镀覆钢板，更详细地，涉及一种耐蚀性和加工性优异的热浸镀钢板及其制造方法。
背景技术
与电镀、干镀等工艺相比，通过连续热浸镀工艺对钢板进行镀覆的工艺的制造成本低，而且可以确保优异的质量，因此作为建筑、船舶、家电产品、汽车内板和外板等的材料的使用范围正在扩大。
另外，近年来，由于包含锌的原材料的价格急剧上升，正在积极地开发一种镀覆附着量少但具有优异的耐蚀性的新型镀覆系，以可以代替现有的镀锌钢板。
与此相关，如下的合金镀覆钢板呈上升趋势，通过在现有的镀锌系中添加铝、镁，所述合金镀覆钢板在附着量少的情况下也具有优异的耐蚀性。
与镀锌系相比，锌-铝-镁系镀浴与钢板的润湿性低，并且凝固区间宽，因此重要的是在镀覆后控制冷却的技术。
以往，以日本为中心开发的锌-铝-镁系合金镀覆钢板(专利文献1和专利文献2)的钢板表面形成易于被氧化的铝组织和镁组织时，由于不均匀的氧化，容易变色，并且随着时间的经过，表面变黑，因此显著降低表面质量。为了改善这些问题，存在一种向镀浴中添加高品质的合金元素的方法，但缺点在于引发以下问题，如增加成本并增加镀浴副反应产物等。
最近以欧洲为中心开发的锌铝镁合金镀覆钢板(专利文献3)是以应用于汽车为最终目标，铝和镁的总添加量少于日本开发的锌-铝-镁合金镀覆钢板，因此存在无法充分确保耐蚀性的问题。
(专利文献1)日本公开公报第1999-140615号
(专利文献2)日本公开公报第2000-104154号
(专利文献3)欧洲公开专利1621645A1
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热浸镀钢板及其制造方法，通过优化合金镀覆系的组分并优化经镀覆的钢材的冷却工艺，所述热浸镀钢板不仅具有高耐蚀性，而且具有良好的表面外观和优异的加工性。
本发明要解决的技术问题并不受限于上述内容。本说明书的全部内容中记载了本发明的附加技术问题，本发明所属技术领域的技术人员在由本说明书中记载的内容理解本发明的附加技术问题方面没有任何困难。
技术方案
本发明的一个方面提供一种耐蚀性和加工性优异的热浸镀钢板，所述热浸镀钢板包括基础钢板和所述基础钢板的至少一面上的Zn-Al-Mg系合金镀层，以重量％计，所述Zn-Al-Mg系合金镀层包含：铝(Al)：20-30％、镁(Mg)：3-5％、余量的Zn和其它不可避免的杂质，所述Zn-Al-Mg系合金镀层的表层组织由Zn相、Zn-Al相、MgZn2相和Zn-Al-MgZn2相组成，内部组织包含Fe-Al合金相。
本发明的另一个方面提供一种制造耐蚀性和加工性优异的热浸镀钢板的方法，所述方法包括以下步骤：准备合金镀浴，以重量％计，所述合金镀浴包含：铝(Al)：20-30％、镁(Mg)：3-5％、余量的Zn和其它不可避免的杂质；将基础钢板浸入所述合金镀浴中并进行镀覆，以制造镀覆钢板；以及将所述镀覆钢板以8-30℃/秒的冷却速度进行冷却，其中，所述镀覆是将进入镀浴的温度调节为500-550℃，将镀浴温度调节为480-550℃，并通过镀覆槽。
有益效果
根据本发明，可以提供一种合金镀覆钢板，通过微细且均匀地形成合金镀层的截面组织来改善所述合金镀层的粘附性，从而可以提高耐蚀性，并且所述合金镀覆钢板具有良好的表面质量和优异的加工性。
附图说明
图1是示出观察本发明的一个实施例的镀覆钢板的镀覆外观的照片。
图2是示出用SEM观察上述图1的镀覆钢板的合金镀层的截面的照片。
图3是示出用SEM观察本发明的一个实施例的比较例1(左侧)和发明例2(右侧)的合金镀层内的组织的照片。
最佳实施方式
为了获得Zn-Al-Mg系合金镀覆钢板，在镀覆Zn-Al-Mg合金时，合金镀层的凝固的开始取决于铝和镁的含量，在凝固的末期最终含有Zn-Al-Mg的共晶相凝固并完成镀层的凝固反应。但是，在完成Zn-Al-Mg三元共晶组织的凝固之前，容易发生由于Mg的强氧化性引起的流痕形状表面缺陷，因此Mg的使用受到限制。
尽管如此，为了提高Zn-Al-Mg合金镀覆钢板的耐蚀性，必须添加一定量以上的Mg，本发明人确认了随着这种Mg含量的增加，氧化引起的流痕形状缺陷增加的问题，并对可以通过一定量以上的Mg来确保耐蚀性并确保良好的表面质量的方法进行了深入研究。
具体地，确认了在Zn-Al-Mg合金镀覆系的情况下，在镀浴中的侵蚀性强，并且凝固区间宽，而且通过优化Zn-Al-Mg合金镀覆系的合金组成和冷却工艺来控制合金镀层的组织。
其结果，确认了可以提供一种具有耐蚀性、良好的表面质量和优异的加工性的Zn-Al-Mg系合金镀覆钢板，从而完成了本发明。
以下，对本发明进行详细的说明。
本发明的一个方面的热浸镀钢板包括基础钢板和所述基础钢板的至少一面上的Zn-Al-Mg系合金镀层，以重量％计，所述Zn-Al-Mg系合金镀层可以包含：铝(Al)：20-30％、镁(Mg)：3-5％、余量的Zn和其它不可避免的杂质。
所述Zn-Al-Mg系合金镀层具有如上所述的合金组成，可以由含有Al、Mg和Zn的合金镀浴形成。
具体地，所述合金镀浴中的Al是确保热浸镀钢板的高耐蚀性的主要元素，当Al的含量小于20％时，难以确保Zn-Al-Mg系合金镀层的充分的耐蚀性。另一方面，当Al的含量超过30％时，镀浴中的浮渣的产生增加，因此最终产品的表面质量变差。
所述合金镀浴中的Mg是为了提高合金镀层和镀层截面的耐蚀性而添加的元素，当Mg的含量小于3％时，提高耐蚀性的效果甚微，另一方面，当Mg的含量超过5％时，由于镀浴的氧化而导致浮渣的产生大幅增加。
所述Al和Mg均是提高镀层的耐蚀性的元素，随着这些元素之和增加，可以进一步提高耐蚀性，因此本发明中可以将所述Al和Mg的含量之和限制为25％以上。
另外，所述合金镀浴中的组分实质上与合金镀层中的组分相同。
具有上述合金组成的所述Zn-Al-Mg系合金镀层可以具有微细且均匀的组织，具体地，所述Zn-Al-Mg系合金镀层的表层组织优选由Zn相、Zn-Al相、MgZn2相和Zn-Al-MgZn2相组成，内部组织优选包含Fe-Al合金相。
本发明中通过在合金镀层的表面(表层)上形成微细的Zn-Al相、MgZn2相和Zn-Al-MgZn2相作为所述Zn-Al-Mg系合金镀层的镀覆组织，可以提高耐蚀性。
另外，本发明中通过在合金镀层内部(内部组织)均匀地形成在现有的Zn-Al-Mg系合金镀覆钢板的界面(基础钢板与镀层的界面)形成的Fe-Al系金属间化合物(Fe-Al合金相)，具有确保良好的表面外观的效果。
另外，所述Zn-Al-Mg系合金镀层可以具有3-40μm的厚度，这种Zn-Al-Mg系合金镀层中的表层组织可以对应于从所述合金镀层的表面到厚度方向的1/3t至1/2t(其中，t表示合金镀层的厚度(μm))的区域。除了对应于上述区域的表层组织以外的其余部分可以称为内部组织。
本发明的热浸镀钢板中形成不同的Zn-Al-Mg系合金镀层的表层组织和内部组织，此时，如上所述形成所述表层组织，因此与现有的热浸镀锌钢板相比，耐蚀性显著优异，并且具有表面外观精美的优点。
以下，对本发明的另一个方面的制造耐蚀性和加工性优异的热浸镀钢板的方法进行详细的说明。
本发明的制造耐蚀性和加工性优异的热浸镀钢板的方法可以包括以下步骤：准备具有上述的合金组成的合金镀浴；将基础钢板浸入所述合金镀浴中并进行镀覆，以制造镀覆钢板；以及将所述镀覆钢板进行冷却。
将基础钢板浸入满足本发明中提出的合金组成的合金镀浴中并进行镀覆时，优选将进入镀浴的温度调节为500-550℃，将镀浴温度调节为480-550℃，并通过镀覆槽。
当所述进入镀浴的温度小于500℃时，在形成的合金镀层的表面上发生未镀覆或者镀层的粘附性变差，另一方面，当所述进入镀浴的温度超过550℃时，存在镀层的粘附性变差的问题。
优选地，将如上所述进行镀覆而获得的镀覆钢板进行冷却，所述冷却优选以8-30℃/秒的冷却速度进行至300℃以下。
所述冷却时，当冷却速度小于8℃/秒时，镀层无法均匀地凝固，另一方面，当冷却速度超过30℃/秒时，存在镀层表面上产生流痕形状缺陷的问题。
此外，所述冷却可以在由4体积％以下(包括0％)的氢气(H2)和余量的氮气(N2)组成的气体气氛中进行，作为一个实例，可以利用空气喷射冷却器。
通过如上所述控制冷却工艺，可以在合金镀层的表面上先形成初晶Zn相、Zn-Al相，并且在所述表面下面的区域(指表面和内部合金层(内部组织)之间的区域)形成微细的Zn-Al相、MgZn2相和Zn-Al-MgZn2相。
最终，在合金镀层的表层形成均匀的组织，从而大幅提高平面部的耐蚀性，特别是可以获得通过Zn相和MgZn2相来改善截面部的牺牲防蚀性能的效果。
在冷却所述镀覆钢板之前，还可以包括气体擦拭处理的步骤，并且可以通过所述气体擦拭处理来调节镀覆附着量。
所述气体擦拭处理时使用的气体可以利用空气或氮气，其中，更优选利用氮气。这是因为使用空气时在镀层表面优先发生Mg的氧化，因此可能会引发镀层的表面缺陷。
另外，所述基础钢板可以是普通的碳钢(包括低碳钢)、不锈钢等冷轧材料，并不受特别限制。
对所述冷轧材料进行用于洗涤经轧制的钢板表面的轧制油的脱脂工艺后，可以进行退火热处理，以恢复轧制组织并确保材质。
所述退火热处理可以在700-850℃的温度范围内进行，但通常在低碳钢的情况下，可以在700-800℃的温度范围内进行退火热处理，在超低碳钢或高强度钢的情况下，可以在800-850℃下进行退火热处理。
所述冷轧材料可以具有0.3-1mm的厚度，但并不受限于此。
以下，通过实施例对本发明进行更具体的说明。但是，需要注意的是，以下实施例仅用于例示本发明以进行更详细的说明，并不用于限制本发明的权利范围。这是因为本发明的权利范围由权利要求书中记载的内容和由此合理推导出的内容决定。
具体实施方式
(实施例1)
对经冷轧的低碳钢(0.003％的C、0.15％的Mn、余量的Fe和其它不可避免的杂质)试片(厚度为0.7mm)进行脱脂，然后在780℃下进行退火热处理。所述退火热处理时，炉内气体气氛是还原性气体气氛，控制为4-20％的H2和余量的N2，并且露点温度为-40℃以下。
之后，根据下表1所示的各条件，对所述试片进行合金热浸镀。此时，以重量％计，利用组分为22.77％的Al、3.6％的Mg和余量的Zn的合金镀浴(Fe为0.027％)。
[表1]
Figure BDA0002953571260000071
对如上所述完成镀覆的各个镀覆钢板的镀覆外观进行观察的结果示于图1中，用SEM观察合金镀层的截面的照片示于图2中。
如图2所示，只有在对应于发明例1和发明例2的试片4和试片5中可以确认表层组织和内部组织被分离并均匀地形成。特别是可以确认在镀层的内部均匀地形成合金相。
另一方面，可以确认比较例1至比较例13的试片中Fe-Al合金相与Zn相、Zn-Al相等混合存在而形成。
此外，图3示出用SEM观察所述比较例1和发明例2的合金镀层组织的照片。
如图3所示，可以确认在比较例1的情况下，在镀覆钢板的表面未均匀地形成具有本发明期望的镀覆组织的合金镀层，另一方面，在发明例2中，在合金镀层内部形成Fe-Al合金层，并且在所述合金层上均匀地形成镀覆组织。
(实施例2)
对与实施例1相同的试片进行脱脂，即，对经冷轧的碳钢试片(厚度为0.7mm)进行脱脂，然后在750℃下进行退火热处理。所述退火热处理时，炉内气体气氛是还原性气体气氛，控制为4-20％的H2和余量的N2，并且露点温度为-40℃以下。
之后，根据下表2中示出的各条件，对所述试片进行合金热浸镀。
[表2]
Figure BDA0002953571260000081
为了对根据各条件完成镀覆的镀覆钢板的耐蚀性进行评价，通过盐水喷雾试验(符合KS-C-0223的盐水喷雾标准试验)进行加速腐蚀试验，然后测量直到镀层表面上产生的红锈的面积达到5％时所经过的时间。
此外，为了评价镀覆粘附性，在进行180度弯曲试验后通过目视观察弯曲面，并确认是否产生裂纹。
下表3中示出各结果。如下表3所示，可以确认与比较例A相比，发明例A的耐蚀性优异，并且未观察到未镀覆现象。特别地，发明例A的弯曲粘附性与热浸镀锌材料是同等水平。
[表3]
类别 盐水喷雾试验 弯曲面产生裂纹
比较例A 7-8周后产生红锈 ×
发明例A 11-12周后产生红锈 ×

Claims (9)

1.一种耐蚀性和加工性优异的热浸镀钢板，其包括基础钢板和所述基础钢板的至少一面上的Zn-Al-Mg系合金镀层，
以重量％计，所述Zn-Al-Mg系合金镀层包含：铝(Al)：20-30％、镁(Mg)：3-5％、余量的Zn和其它不可避免的杂质，所述Zn-Al-Mg系合金镀层的表层组织由Zn相、Zn-Al相、MgZn2相和Zn-Al-MgZn2相组成，内部组织包含Fe-Al合金相。
2.根据权利要求1所述的耐蚀性和加工性优异的热浸镀钢板，其中，所述Zn-Al-Mg系合金镀层包含含量之和为25重量％以上的铝(Al)和镁(Mg)。
3.根据权利要求1所述的耐蚀性和加工性优异的热浸镀钢板，其中，所述Zn-Al-Mg系合金镀层具有3-40μm的厚度。
4.根据权利要求1所述的耐蚀性和加工性优异的热浸镀钢板，其中，所述Zn-Al-Mg系合金镀层的表层组织是从所述合金镀层的表面到厚度方向的1/3t至1/2t的区域，其中，t表示合金镀层的厚度(μm)。
5.一种制造耐蚀性和加工性优异的热浸镀钢板的方法，其包括以下步骤：
准备合金镀浴，以重量％计，所述合金镀浴包含：铝(Al)：20-30％、镁(Mg)：3-5％、余量的Zn和其它不可避免的杂质；
将基础钢板浸入所述合金镀浴中并进行镀覆，以制造镀覆钢板；以及
将所述镀覆钢板以8-30℃/秒的冷却速度进行冷却，
其中，所述镀覆是将进入镀浴的温度调节为500-550℃，将镀浴温度调节为480-550℃，并通过镀覆槽。
6.根据权利要求5所述的制造耐蚀性和加工性优异的热浸镀钢板的方法，其中，所述冷却进行至300℃以下。
7.根据权利要求5所述的制造耐蚀性和加工性优异的热浸镀钢板的方法，其中，所述冷却在由4体积％以下且包括0％的氢气(H2)和余量的氮气(N2)组成的气体气氛中进行。
8.根据权利要求5所述的制造耐蚀性和加工性优异的热浸镀钢板的方法，其中，在所述冷却之前，还包括对所述镀覆钢板进行气体擦拭处理的步骤。
9.根据权利要求5所述的制造耐蚀性和加工性优异的热浸镀钢板的方法，其中，所述基础钢板是进行脱脂并在700-850℃的温度范围内进行退火热处理的冷轧材料。
CN201880097006.1A 2018-08-31 2018-12-10 耐蚀性和加工性优异的热浸镀钢板及其制造方法 Pending CN112639153A (zh)

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