CN108138308B - 镀覆钢材 - Google Patents

镀覆钢材 Download PDF

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Publication number
CN108138308B
CN108138308B CN201680056510.8A CN201680056510A CN108138308B CN 108138308 B CN108138308 B CN 108138308B CN 201680056510 A CN201680056510 A CN 201680056510A CN 108138308 B CN108138308 B CN 108138308B
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plating layer
quasi
phase
steel material
plating
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CN108138308A (zh
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小林亚畅
德田公平
下田信之
后藤靖人
松村贤一郎
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Nippon Steel Corp
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Nippon Steel Corp
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • 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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    • B32B15/00—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
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    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/021—Cleaning or etching treatments
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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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    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
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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

一种镀覆钢材，其具备钢材、被覆于上述钢材的表面的镀层和形成于上述钢材及上述镀层的边界的界面合金层，上述镀层的组成以质量％计含有Zn：20～83％及Al：2.5～46.5％，剩余部分包含Mg及杂质，且Mg含量为10％以上，上述镀层的组织包含准结晶相、MgZn2相和剩余部分组织，上述准结晶相的面积分率为30～60％，90个数％以上的准结晶相为将其长轴方向的粒径设定为0.05～1.0μm的准结晶相，上述镀层的厚度为0.1μm以上，上述界面合金层的厚度为500nm以下。

Description

镀覆钢材
技术领域
本公开涉及镀覆钢材。
背景技术
一直以来，进行了在钢材的表面被覆Zn等金属而改善钢材的耐蚀性。目前还生产了镀覆有Zn、Zn-Al、Zn-Al-Mg、Al-Si等的钢材。对于钢材的被覆，除了要求耐蚀性以外，还要求耐磨性或加工后密合性的情况也多。作为钢材的被覆方法，最广泛使用适于大量生产的热浸镀。
对钢材的被覆所要求的耐蚀性逐年变高，因此，近年来还提出了如以下的专利文献1及专利文献2中所示那样的将Mg含量提高至以往以上的镀覆。然而，若想要将Mg提高至以往以上，则有可能在热浸镀浴的制作时金属没有溶解，因浴组成和加热条件而产生浮渣等。
此外，热浸镀皮膜根据镀覆组成有可能通过界面合金层的生成而皮膜的加工后密合性降低，加工法受到制约。特别是在使非平衡相、金属间化合物析出的皮膜中该倾向强，专利文献1及专利文献2中所示的方案也同样地有可能加工法受到制约。
相对于这些，对于浸渍镀覆(热浸镀)、喷镀、蒸镀等方法，从即使是加工后的制品也能够被覆的观点出发，其作为能够被覆难加工性的合金等的方法而被已知。它们中，蒸镀法由于不将钢材浸渍于熔融金属中，所以具有对钢材的热影响少、能够被覆的金属、合金系的熔点容许范围广等优点。
为了提高钢材的耐蚀性，与镀层的形成同样地在镀层中添加Zn成为基本，但相对于许多用途就仅Zn添加的皮膜而言成为耐蚀性不充分的皮膜的情况较多。
因此，提出了如专利文献3中记载的那样的含Mg皮膜的蒸镀法。其是蒸镀包含5％～30％的Mg、0.5～5％的选自Al、Cr、Co、Mn、Ti及Ni中的1种或2种以上、剩余部分为Zn的合金皮膜的方法，是耐蚀性优异的镀覆皮膜。此外，如专利文献4中所示的那样，提出了在通过蒸镀而层叠镀覆单层后通过热处理而制作Zn-Mg镀覆的技术。
此外，在专利文献5中，提出了“一种耐蚀性及加工性优异的锌合金镀覆金属材，其特征在于，其是在金属器材的表面形成有含有Al：5～70％(重量％的意思，以下相同)、以及合计0.5～5％的选自Cr、Co、Ti、Ni、Mg中的1种或2种以上(其中，Ti、Mg低于5％)、剩余部分实质上包含Zn的蒸镀镀层的金属材”。
专利文献1：日本特开2008-255464号公报
专利文献2：日本特开2011-190507号公报
专利文献3：日本特开平1-021066号公报
专利文献4：日本特开平7-268604号公报
专利文献5：日本特开平1-21064号公报
发明内容
发明所要解决的问题
在现有技术中，像这些这样提出了各种合金蒸镀镀覆被覆，但在任一种现有技术中，均存在能够生成的镀覆皮膜的耐蚀性(特别是加工后的耐蚀性)、碱耐蚀性、耐磨性、加工后密合性不能说是充分的问题。
本公开的一方式是鉴于上述的背景而进行的，其目的是提供具有耐蚀性(特别是加工后的耐蚀性)、碱耐蚀性及耐磨性优异、加工后的镀覆密合性也优异的镀层的镀覆钢材。
用于解决问题的手段
本公开基于以上的背景而进行，包含以下的方式。
[1]一种镀覆钢材，其具备钢材、被覆于上述钢材的表面的镀层和形成于上述钢材及上述镀层的边界的界面合金层，
上述镀层的组成以质量％计含有Zn：20～83％及Al：2.5～46.5％，剩余部分包含Mg及杂质，且Mg含量为10％以上，
上述镀层的组织包含准结晶(也可称为准晶，quasicrystalline)相、MgZn2相和剩余部分组织，上述准结晶相的面积分率为30～60％，90个数％以上的上述准结晶相为将其长轴方向的粒径设定为0.05～1.0μm的准结晶相，
上述镀层的厚度为0.1μm以上，上述界面合金层的厚度为500nm以下。
[2]根据[1]所述的镀覆钢材，其中，上述剩余部分组织的面积分率为40％以下。
[3]根据[1]或[2]所述的镀覆钢材，其中，上述镀层的厚度为0.1～10μm。
[4]根据[1]～[3]中任一项所述的镀覆钢材，其中，上述镀层为蒸镀镀层。
[5]根据[1]～[4]中任一项所述的镀覆钢材，其中，上述界面合金层为Al-Fe合金层。
[6]根据[1]～[5]中任一项所述的镀覆钢材，其中，上述镀层含有C、Ca、Si、Ti、Cr、Fe、Co、Ni、V、Nb、Cu、Sn、Mn、Sr、Sb、Pb、Y、Cd及La中的1种或2种以上的选择元素，且上述选择元素的合计含量以质量％计为0～0.5％。
发明效果
根据本公开的一方式，能够提供一种镀覆钢材，其通过在镀层中具有准结晶相，从而与以往的含Mg镀覆钢材相比耐蚀性(特别是加工后的耐蚀性)及碱耐蚀性优异，通过为高硬度的微细的准晶均匀地分布于镀层中而耐磨性优异。进而，能够提供由于镀层和钢材的界面合金层薄所以加工后的镀覆密合性优异的镀覆钢材。
此外，通过本公开的一方式能够对于对钢材实施了加工的压花品等也赋予相同功能，能够通过实现部件的长寿命化而有助于产业的发展。
附图说明
图1是表示本公开的实施方式所述的镀覆钢材的侧截面图。
图2是表示温度与金属的蒸气压的关系的图表。
图3是准结晶相的TEM电子射线衍射图像。
具体实施方式
通过本发明人们的研究发现，使高Mg的Zn-Mg-Al系中含有准结晶相的镀层显示高的耐蚀性。同时还发现，形成有包含该准结晶相的Zn-Mg-Al系镀层的钢材具有极高的硬度，耐磨性优异。
可是，对于将上述的组成的镀液稳定化有一些难，使用该组成域的镀液进行操作并不简单。
因而，对于在不使用上述的组成的镀液的情况下对钢材实施上述的高含Mg的Zn-Mg-Al系镀覆进行了研究，结果达成了本公开。
以下，对本公开的实施方式所述的镀覆钢材进行说明。
另外，在本说明书中使用“～”表示的数值范围是指将记载于“～”的前后的数值作为下限值及上限值而包含在内的范围。
在本说明书中，表示成分(元素)的含量的“％”是指“质量％”。
实施方式所述的被覆有含Mg的Zn合金镀层的镀覆钢材1如图1的截面结构(沿镀层厚度方向切断的截面结构)中所示的那样，包含钢板、钢管、土木建筑材料(护栏、挡水墙、波纹管等)、家电部件(空调的室外机的框体等)、汽车部件(行走部件等)等钢材2和通过蒸镀而形成于钢材2的表面的镀层(蒸镀镀层)3。此外，在钢材2与镀层3的界面形成有薄的界面合金层(Fe-Al合金层)4。
对于成为镀覆的基底的钢材2的材质没有特别限制。钢材2能够适用例如一般钢、Ni预镀钢、Al镇静钢、一部分高合金钢。对于钢材2的形状也没有特别限制，也可以实施成型加工。
钢材2不限于图1的平板状，也可以使用弯曲成L字型的成型钢材等。此外，也可以在通过加压加工、辊轧成形、弯曲加工等各种塑性加工方法而加工成目标形状的钢材2上形成镀层3。
以下，对镀层3和界面合金层4的组织、组成等进行说明。
在镀层3与钢材2的边界部分，形成有例如厚度为500nm以下的界面合金层4。镀层3由厚度为0.1～10μm的Zn-Mg-Al合金层形成。界面合金层4由Al-Fe合金层构成。另外，界面合金层4根据镀层3的制造条件有时成为几乎无法确认的程度的薄的层。
界面合金层4的厚度由于受镀层3的蒸镀条件的左右，所以对于界面合金层4的厚度的下限没有特别限定，但例如从镀层3的密合性的观点出发，优选为300nm以上。若界面合金层4的厚度超过500nm，则镀层3的密合性降低，若对钢材2进行塑性加工，则镀层3变得容易从钢材2的表面剥离。
镀层3的厚度低于0.1μm时，难以得到充分的耐蚀性。此外，虽然10μm以上的厚度的镀层3能够制作，但是在以连续通板进行生产的情况下有时生产率差。因此，镀层3的厚度为0.1μm以上，优选为0.1～10μm，更优选为0.5～5μm。特别是若将镀层3的厚度设定为0.5～5μm，则镀覆后的耐蚀性和镀覆的密合性得以兼顾。
其中，镀层3及界面合金层4的厚度如下那样测定。通过SEM(扫描型电子显微镜)，进行镀层3及界面合金层4的截面观察(在沿镀层3及界面合金层4的厚度方向被切断的截面中，在与镀层3及界面合金层4平行的方向上相当于2.5mm长度的区域的观察)。在该区域中，求出在至少三个视野(倍率为1万倍)中观察到的各镀层3及各界面合金层4的任意的5处(至少各计15处)的厚度的平均值。以该平均值作为镀层3及界面合金层4的厚度。
另外，用于截面观察的样品调整方法只要通过公知的树脂埋入或截面研磨方法进行即可。
镀层3中析出准结晶相。即，在镀层3中，包含多个准结晶相。并且，在镀层3中析出的多个准结晶相中的90个数％以上的准结晶相优选为将其长轴方向的粒径设定为0.05～1.0μm的准结晶相。此外，也可以在镀层3的表面形成极薄的氧化皮膜。
界面合金层4是形成于钢材2的表面，例如Fe浓度的范围成为10％以上且90％以下的层。即，在界面合金层4中包含Fe3Al、FeAl3、Fe2Al5、FeAl3、以及Fe及Al的一部分置换成Zn的金属间化合物等中的任一种以上。
另外，界面合金层4例如平均组成含有Fe：30～50％、Al：50～70％、Zn：2～10质量％及剩余部分：杂质。
由于在镀层3中含有许多Al及Zn，所以镀层3中的Al与钢材2的Fe反应而在钢材2的表面形成Al3Fe相。此外，镀层3的成分的Zn必然被摄入，成为摄入有一部分Zn的形态，生成Al3Fe相和使性质有些不同的界面合金层4。
由于成为以Al3Fe相作为主体的包含Al-Fe合金的界面合金层4，所以例如合金层的Fe浓度的平均值必然成为30～50％。Al浓度的平均值成为50～70％。
在通过蒸镀法来制作镀层3时，关于Zn-Mg-Al合金的镀层3的成分组成，基本通过蒸镀源金属的制膜速度而决定的成分组成比率在镀层3中也被保持。由界面合金层4的生成引起的Zn-Mg-Al合金层的Al成分、Zn成分的减少通常很少。这是由于界面合金层4的形成极薄。
本发明人们仔细研究了通过蒸镀镀覆法得到准结晶相的组成范围，结果发现，在以下的组成范围内准结晶相在Zn-Mg合金层内以必要的面积分率含有。
即，镀层3的组成以质量％计含有Zn：20～83％及Al：2.5～46.5％，剩余部分包含Mg及杂质，且Mg含量为10％以上。
关于镀层3的组成，对优选的范围和其理由进行说明。
“Zn(锌)：20～83％”
为了得到准结晶相作为镀层3的金属组织，必须含有上述范围的Zn。因此，将镀层的Zn含量设定为20～83％。Zn含量低于20％时，变得难以在镀层3中生成准结晶相。此外同样地Zn含量超过83％时，变得难以在镀层3中生成准结晶相。
此外，为了使准晶优选生成而使耐蚀性进一步提高，更优选将Zn含量设定为60％以上(即60～83％)。若设定为60％以上，则成为准结晶相容易作为初晶而生长的组成范围，Mg相变得难以作为初晶生长。即，能够增多镀层3中的准结晶相的相量(面积分率)，同时能够极力减少使耐蚀性劣化的Mg相。
“Al(铝)：2.5～46.5％”
Al是使镀层3的平面部的耐蚀性提高的元素。此外，Al是促进准结晶相的生成的元素。为了得到这些效果，将镀层3的Al含量设定为2.5％以上。为了将准结晶相的平均当量圆直径控制在优选的范围，优选将Al含量设定为3％以上，更优选设定为5％以上。
另一方面，若大量含有Al，则碱耐蚀性降低，进而准结晶相变得难以生成而耐蚀性降低。因此，将Al含量设定为46.5％以下，优选设定为20％以下。
因而，镀层3的Al含量设定为2.5～46.5％，优选设定为3～20％，更优选设定为5～20％。
“Mg(镁)：剩余部分”
Mg与Zn及Al同样地是构成镀层3的主要的元素，进而，是使牺牲保护防蚀性提高的元素。此外，Mg是促进准结晶相的生成的重要的元素。因此，作为剩余部分的Mg含量设定为10％以上，优选为10～43％的范围，更优选为15～35％的范围。由于若将Mg含量设定为10％以上，则稳定地形成准结晶相，所以若是仅以准结晶相的生成作为目的则不需要热处理。另外，Mg的含有是必须的，但抑制所含有的Mg在镀层3中作为Mg相析出是为了耐蚀性提高而优选的。
此外，镀层3也可以含有C、Ca、Si、Ti、Cr、Fe、Co、Ni、V、Nb、Cu、Sn、Mn、Sr、Sb、Pb、Y、Cd及La中的1种或2种以上的选择元素。其中，这些选择元素的合计含量设定为0～0.5％。
这些元素能够在镀层3中含有，但上述合计含量的范围为能够在不阻碍准结晶相的形成、不会使镀层的性能劣化的情况下添加的组成范围。若超过上述合计含量的范围，则准结晶相变得难以形成。
其中，镀层3的组成、以及镀层3及界面合金层4的厚度的测定方法如下所述。
首先，通过发烟硝酸将界面合金层4(Fe-Al层)钝化而仅将上层的镀层3剥离，对该溶液通过ICP-AES(Inductively Coupled Plasma Atomic Emission Spectrometry，电感耦合等离子体原子发射光谱)或ICP-MS(Inductively Coupled Plasma MassSpectrometry，电感耦合等离子体质谱)测定镀层3的组成。
接着，对镀层的组织进行说明。
镀层3的组织包含准结晶相、MgZn2相和剩余部分组织，上述准结晶相的面积分率为30～60％，多个准结晶相中的90个数％以上的准结晶相为将其长轴方向的粒径设定为0.05～1.0μm的准结晶相(以下，也将粒径为0.05～1.0μm的准结晶相的粒径称为“准结晶相的90％以上的粒径”。)。
在镀层3的组织中，通过具有以面积分率计30％以上的硬质的准结晶相，耐磨性提高。此外，通过具有准结晶相，耐蚀性也见到效果。然而，由于准结晶相硬，所以若准结晶相的面积分率超过60％，则在加工时产生裂纹，使加工后的镀覆密合性降低。因此，准结晶相的面积分率优选为30～60％，更优选为35～50％。
MgZn2相也与准结晶同样地使耐磨性、耐蚀性、碱耐蚀性提高。虽然MgZn2相也使各性能提高，但是其程度还是准结晶相的效果较大。另一方面，关于加工后的镀覆密合性，与准结晶相相比降低的程度较小。因此，担保加工后的镀层3的密合性、并且提高耐蚀性、碱耐蚀性及耐磨性较佳。从该观点出发，准结晶相及MgZn2相的合计的面积分率优选为60％≤准结晶相+MgZn2相≤90％，更优选为70％≤准结晶相+MgZn2相≤85％。
此外，剩余部分组织的面积分率优选为40％以下，更优选为30％以下。这是由于，通过降低剩余部分组织的面积分率、且使准结晶相及MgZn2相的合计的面积分率增加，从而担保加工后的镀层3的密合性，且提高耐蚀性、碱耐蚀性、耐磨性。但是，剩余部分组织的面积分率也可以为0％，但从加工后的镀覆密合性的方面出发，设定为10％以上较佳。
其中，在镀层3中，准结晶相作为准结晶相中包含的Mg含量、Zn含量及Al含量以原子％计满足0.5≤Mg/(Zn+Al)≤0.83的准结晶相被定义。即，作为Mg原子与Zn原子及Al原子的合计的比即Mg：(Zn+Al)成为3：6～5：6的准结晶相被定义。作为理论比，认为Mg：(Zn+Al)为4：6。
准结晶相的化学成分优选通过利用TEM-EDX(Transmission ElectronMicroscope-Energy Dispersive X-ray Spectroscopy，透射电子显微镜-能量色散型X射线光谱)的定量分析、或利用EPMA(Electron Probe Micro-Analyzer，电子探针显微分析仪)映射的定量分析而算出。另外，将准晶如金属间化合物那样以正确的化学式定义并不容易。这是由于，准结晶相无法如晶体的单位晶格那样定义重复的晶格单位，进而，特定Zn、Mg的原子位置也困难。
此外，镀层3除准结晶相以外还包含MgZn2相及剩余部分组织，但剩余部分组织为除准结晶相及MgZn2相以外的组织，且包含Mg51Zn20相、Mg32(Zn、Al)49相、MgZn相、Mg2Zn3相、Zn相、Al相。
准结晶相是在1982年由Daniel Shechtman最初发现的晶体结构，具有正20面体(icosahedron)的原子排列。该晶体结构作为在通常的金属、合金中不能得到的具有特异的旋转对称性、例如5次对称性的非周期性晶体结构、且与以3维彭罗斯拼图(Penrosepattern)为代表的非周期性结构等价的晶体结构而被已知。为了鉴定该金属物质，通常通过利用TEM观察的电子射线观察，通过由相得到起因于正20面体结构的放射状的正10角形的电子射线衍射图像来确认。例如，后述的图3中所示的电子射线衍射图像仅由准晶得到，不会由其他任意的晶体结构得到。
此外，由镀层3的组成得到的准结晶相简易地示出作为Mg32(Zn、Al)49相通过X射线衍射能够以JCPDS卡片：PDF#00-019-0029、或#00-039-0951鉴定的衍射峰。
准结晶相为耐蚀性极优异的物质，若在镀层3(Zn-Mg-Al层)中含有则耐蚀性提高。特别是若以面积分率计在蒸镀镀层中含有5％以上，则存在在腐蚀初期阶段抑制白锈产生的倾向。若以更高的面积分率计例如含有30％以上，则增加该效果。即形成于镀层3(Zn-Mg-Al层)的表面上的准结晶相相对于腐蚀因子具有高的阻挡效果。
接着，对镀层3的准结晶相、MgZn2相及剩余部分组织的面积分率的测定方法进行说明。
通过SEM-反射电子图像拍摄镀层3的任意的截面(沿镀层厚度方向切断的截面)的至少3个视野以上(在与镀层3平行的方向上相当于500μm长度的区域以倍率5千倍且至少3个视野以上)。由另外通过TEM观察得到的实验结果，特定SEM-反射电子图像中的准结晶相、MgZn2相及剩余部分组织。在规定的视野中，把握成分映射图像，特定与镀层3中的准结晶相、MgZn2相及剩余部分组织相同的成分组成部位，通过图像处理，特定镀层3中的准结晶相、MgZn2相及剩余部分组织。通过图像解析装置，准备在准结晶相、MgZn2相及剩余部分组织的各区域进行了范围选择的图像，测定镀层3中所占的准结晶相、MgZn2相及剩余部分组织的比例。将由同样地处理的3个视野的平均值设定为镀层3中的准结晶相、MgZn2相及剩余部分组织的面积分率。
镀层3的各相的鉴定在将镀层3的截面(沿镀层厚度方向切断的截面)实施FIB(聚焦离子束)加工后，通过TEM(透射型电子显微镜)的电子衍射图像进行。
此外，若在腐蚀促进试验等中准结晶相发生腐蚀，则形成阻挡效果高的腐蚀产物，将基底金属长期防腐蚀。阻挡效果高的腐蚀产物与准结晶相中包含的Zn-Mg-Al成分比率有关。在镀层3(Zn-Mg-Al合金层)的成分组成中，Zn＞Mg+Al(式中，元素记号表示元素的含量(质量％))成立时，腐蚀产物的阻挡效果高。一般在耐蚀性方面，优选准结晶相的面积分率较高。若以准结晶相的面积分率计为80％以上则该效果特别大。这些效果在包含盐水喷雾循环(SST)的复合循环腐蚀试验中，该效果较大地出现。
对于MgZn2相及Mg2Zn3相，与准结晶相比较，虽然由含有带来的耐蚀性提高效果小，但仍具有一定的耐蚀性，且由于含有许多Mg所以碱耐蚀性优异。即使是这些单独的金属间化合物也通过在镀层3中含有而得到碱耐蚀性，但若与准结晶相并存，则准结晶相的高碱环境(pH13～14)中的镀层3的表层的氧化皮膜稳定化，显示特别高的耐蚀性。因此，准结晶相优选在镀层3中以面积分率计含有30％以上。
另一方面，在镀层3的组织中，若准结晶相的90个数％以上的粒径变得大于1.0μm，则通过加工从晶界传播龟裂，加工后的镀层3的密合性降低。即，若多个准结晶相的90％以上的粒径成为1.0μm以下，则加工后的镀层3的密合性提高，此外，通过粒细微地分散而耐磨性也提高。若准结晶相的90个数％以上的粒径变得低于0.05μm，则耐磨性没有充分地发挥。因此，准结晶相的90％个数以上的粒径优选为0.1～0.5μm，更优选为0.1～0.3μm。
此外，粒径为0.05～1.0μm的准结晶相的比例优选为90个数％以上，更优选为95个数％以上。
准结晶相的粒径(准结晶相的长轴方向的粒径)、粒径为0.05～1.0μm的准结晶相的比例通过以下所示的方法测定。
通过与上述准结晶相的面积分率的测定方法同样的方法拍摄镀层3的任意的截面(沿镀层厚度方向切断的截面)的至少3个视野(在与镀层3平行的方向上相当于500μm长度的区域以倍率5千倍且至少3个视野以上)以上，数出镀层3中的准结晶相的粒子数。此外，测定准结晶相的长轴方向的长度(即准结晶相的直径成为最长的直线的长度)作为粒径。并且，算出粒径为0.05～1.0μm的准结晶相相对于所数出的准结晶相的全部粒子数的比例。
接着，对本实施方式的镀覆钢材的制造方法进行详细说明。
钢材2在蒸镀镀层3前优选供于表面清洁(盐酸酸洗、水洗、干燥)。生成于钢材2的表层的牢固的氧化被膜通过例如在10％盐酸中浸渍10分钟以上进行剥离。酸洗后，进行水洗，使用干燥机或干燥炉除掉表面的水分。
为了在钢材2的表面形成镀层3，作为一个例子采用使用了真空腔室的蒸镀法。另外，在以下的说明中对通过封闭体系形成镀层3的情况进行说明，但通过连续通板的体系也可得到同样的结果。
真空蒸镀通常在10-2～10-5Pa的压力下进行，此时的平均自由行程为数十cm～数十m。因此，由蒸镀金属源气化的材料几乎没有碰撞地到达钢材2的表面。此外，由于蒸发粒子的能量非常小，所以几乎不会对钢材2的表面给予损害。另一方面，存在镀层3容易变成多孔、密度低、强度不足的倾向。这是由于蒸发粒子的能量小，所以粒子无法从到达钢材表面的位置移动。
因此，对于利用蒸镀的成膜(镀覆)，若不使蒸镀粒子向钢材2中的入射频率充分大于腔室内的残留气体向基板中的入射频率，则残留气体被摄入镀层3中。残留气体的最多的成分为H2O。若H2O被摄入镀层3中，则在镀层3中出现空隙，成为多孔且脆的镀层。
为了对其进行改善，将钢材2加热而进行蒸镀镀覆是有效的。若钢材2的温度高，则残留气体向钢材2的附着概率减少，被摄入镀层3中的量减少。此外，吸附于钢材2上的蒸镀金属变得容易通过热能而运动，附着于不稳定的部位的蒸镀金属可以向稳定的部位移动，镀层3的密度也提高。
为了镀层3具有准结晶相和ZnMg相，而且确保镀层3的加工后密合性，优选在蒸镀中加热钢材。钢材2的温度优选为50～400℃。在低于50℃的温度下蒸镀于钢材2的表面的金属原子无法充分形成结晶相而成为空隙多的镀层3，不能充分得到耐蚀性。将钢材2的温度设定为400℃以上，并且用长时间进行蒸镀镀覆时，界面合金层4较厚地生长，成为镀层3的加工后密合性降低的要因。因此，在优选150～350℃、进一步优选200～300℃下，优选边将钢材2的表面加热边进行蒸镀(成膜)。
蒸镀镀层3时的蒸镀速率通过以下的内容来决定。
“1”通过蒸镀金属源的温度和此时的金属源的蒸气压来决定。
“2”通过蒸镀金属源的表面积、容量来决定。
“3”通过从蒸镀金属源到钢材2的距离、腔室内的大小来决定。
此外，蒸镀镀层3的方法中的加热方法可以选择以下例示的方法中的任一种。
(1)电阻加热。(2)电子射线加热。(3)高频感应加热。(4)激光加热。
优选根据蒸镀的金属的特性来分开使用蒸镀方法。
对于电阻加热，对高熔点金属或各种发热体材料的两端施加电压并流过电而产生焦耳热。能够在该电阻加热的试样台上设置蒸镀金属源并使其溶解。
对于电线加热，将通过将钨等丝进行电阻加热而产生的热电子以高电压加速，对金属蒸镀源进行照射。通过电子的动能碰撞而转换成热，能够将金属蒸镀源溶解。
对于高频感应加热，是通过由高频感应引起的涡流损耗和磁滞损耗将材料加热蒸发的方法。对按照将放入了材料的坩埚包围的方式设置的线圈投入高频电力而进行加热，能够使金属蒸镀溶解。
对于激光加热，将高输出激光用于加热蒸发。激光一般从窗户导入真空容器中，通过透镜、凹镜面等进行聚光而能够将蒸镀金属源加热并溶解。
[镀层的形成]
腔室的抽真空完成后，在对蒸镀金属源的上面盖上盖子的状态下将蒸镀金属加热至熔点附近。此时若将蒸镀金属过度加热，则熔融金属的表面变动而无法进行均匀的蒸镀镀覆。此外，若加热温度过低，则金属没有充分地气化。蒸镀量由于大致由加热温度下的蒸气压决定，所以由温度、蒸气压和此时的腔室内的真空度决定。
图2是表示各种金属的温度(K)与蒸气压(Pa)的关系的图表，只要由图2中所示的关系把握分别使用作为蒸镀源的Al、Mg、Zn时的温度与蒸气压的关系来决定各蒸镀源的加热温度即可。
蒸镀金属的加热完成后，取下蒸镀金属源上的盖子而开始镀覆。在进行镀覆的腔室小且金属蒸镀源与钢材2为止的距离短时，优选使钢材2或者蒸镀金属源旋转而能够均匀地镀覆各元素。
蒸发的金属元素飞到钢材2的表面并作为皮膜生成，根据钢材2的温度而结晶粒径或与钢材2的界面合金层4的厚度发生变化。
从蒸镀源蒸发的金属在大致急冷状态下被覆于钢材2的表面。由于根据钢材2的温度而吸附的金属的迁移率发生变化，所以由此各结晶粒径发生变化。
镀覆于钢材2上的金属按照成为含有Zn：20～83％及Al：2.5～46.5％、剩余部分包含Mg及杂质、且Mg含量为10％以上的镀层3的组成的方式，调整各蒸镀金属的保持温度和蒸镀腔室内的压力。
镀覆后，使用N2等不活泼气体使腔室内的真空度接近大气而取出钢材2。
被覆有具有以上说明的组成及组织的镀层3的镀覆钢材1具有相对于盐水的耐蚀性、碱耐蚀性优异、加工后密合性优异、耐磨性也优异的特征。
此外，本公开在镀覆钢材的制作中，也可以在形成镀层后实施后处理。
作为后处理，可列举出对镀覆钢板的表面进行处理的各种处理，有实施上层镀覆的处理、铬酸盐处理、非铬酸盐处理、磷酸盐处理、润滑性提高处理、焊接性提高处理等。此外，作为镀覆后的后处理，还有通过辊涂装、喷雾涂装、帘式流动涂装、浸渍涂装、膜层压法(例如层叠丙烯酸树脂膜等树脂膜时的膜层压法)等方法涂装树脂系涂料(例如聚酯树脂系、丙烯酸树脂系、氟树脂系、氯乙烯树脂系、聚氨酯树脂系、环氧树脂系等)而形成涂料膜的处理。
实施例
接着基于实施例对本公开进一步进行说明。
首先，在镀层的蒸镀时，将设置在腔室内的蒸镀金属(Al、Mg、Zn)通过电子射线单独地分别进行加热。也可以将这些元素的合金进行加热而使其蒸镀，但由于这些金属各自的熔点及蒸气压不同，所以若使用合金进行蒸镀，则镀层的相对于深度方向的组成分布的控制变得困难，因此使用每种元素的单独蒸镀源。另外，蒸镀条件如下所述。
·装置容量(腔室内容量)：0.6m3、
·从蒸镀金属源到钢板(基板)为止的距离：0.6m、
·蒸镀中的真空度：5.0E-3～2.0E-5Pa、
·蒸镀金属源用坩埚的容量：40ml、内径：
·蒸镀方法：电子射线、
·电子射线照射条件：电压10V(固定)、电流0.7～1.5A、
·钢板温度：50～600℃、
·钢板旋转速度：15rpm。
其中，将蒸镀金属(Al、Mg、Zn)通过电子射线照射进行加热而进行蒸镀时，将相对于各金属的电子射线照射的电流控制在上述范围(0.7～1.5A的范围)内。通过该电流控制而金属的温度发生变化，可以使形成于钢板上的镀层的组成发生变化。蒸镀金属源的温度通过热电偶来测定。
例如，在No.14的试验片的情况下，在将钢板的平均温度升温至423.15K(150℃)的状态下，将各蒸镀金属源的温度平均设定为Mg：640K、Al：1280K、Zn：585K，将腔室内的平均真空度设定为7×10-4Pa，将蒸镀时间设定为6min。
并且，以No.14的试验片的镀层的组成和图2中所示的温度与金属的蒸气压的关系作为大致目标，按照成为目标镀层的组成的方式，使各金属的温度发生变化。此外，控制蒸镀时间而制成所期望的镀层的膜厚。
另外，镀层的组织通过镀层的组成和钢板的平均温度来控制。
控制以上说明的蒸镀条件，制造以具有表1中所示的准结晶相的粒径、界面合金层的厚度、组成的各镀层被覆表面的钢板试验片(尺寸：纵为200mm、横为200mm、厚度为0.8mm)，进行所得到的各试验片的耐蚀性评价、加工后耐蚀性评价、碱耐蚀性评价、加工后镀覆密合性的评价(弯曲试验)、耐磨性评价。将这些结果一并记于以下的表1、表2中。准结晶相的粒径测定其长轴方向的粒径。
<各相的面积分率＞
按照已经叙述的方法测定准结晶相、MgZn2相、剩余部分组织的面积分率。
<准结晶相的长轴方向的粒径＞
按照已经叙述的方法测定准结晶相的长轴方向的粒径。
在表1中，在“粒径(长轴方向的长度)为0.05～1μm的准结晶相的粒子数”/“总准结晶相的粒子数”≥0.9时，表1中记载准结晶相的平均粒径(平均长轴方向的长度)，在“粒径(长轴方向的长度)为0.05～1μm的准结晶相的粒子数”/“总准结晶相的粒子数”＜0.9时，表1中记载“NG”，将准结晶相的平均粒径(平均长轴方向的长度)记载于括号内。
另外，在“NG”的试验片中，有镀层的整面成为准结晶相的试验片，对于无法测定准结晶相的粒径的试验片记载为“-”。
<耐磨性评价＞
蒸镀镀层的耐磨性使用HEIDON公司制、直线滑动试验机而测定。接触部分设定为钢球(20R：材质SKD11)，设定为载荷500g、滑动距离40mm、速度1200mm/min。往返10次后，通过目视观察试验片(镀覆钢板)的表面，进行评价。试验后在镀层的表面见到明显的伤痕或缺口的情况评价为“D”，在试验后镀覆表面的非试验部与试验部相比颜色清楚地发生变化的情况评价为“C”，在试验后镀覆表面的非试验部与试验部相比颜色稍微有点变化的情况评价为“B”，将外观与试验前几乎没有变化的情况评价为“A”。将这些结果一并记于表1、表2中。
但是，对于“C”的评价，以“C-”、“C”及“C+”这3个阶段进行评价，表示按照“C-”、“C”及“C+”的顺序，颜色的变化的程度小。
<耐蚀性评价＞
蒸镀镀层的耐蚀性通过依据JASO M-609-91的复合循环腐蚀试验(CCT)来评价。将由5次循环中的试验片(镀覆钢板)的镀层产生了60％以上红锈的试样评价为“D”，将产生了50％以上且低于60％红锈的试样评价为“C-”。将产生了40％以上且低于50％红锈的试样评价为“C”。将产生了30％以上且低于40％红锈的试样评价为“C+”。将产生了超过10％且低于30％红锈的试样评价为“B”，将红锈产生量为10％以下的试样评价为“A”。将这些结果一并记于表1、表2中。
<加工后耐蚀性评价＞
蒸镀镀层的加工后耐蚀性除了在实施上述耐蚀性评价前，在对试验片(镀覆钢板)实施2R、60°V弯曲加工后，将试验片的端面及背面用胶带被覆以外，与上述耐蚀性评价同样地操作而进行评价。
并且，将由10次循环中的试验片(镀覆钢板)的镀层产生了80％以上红锈的试样评价为“D”。将产生了70％以上且低于80％红锈的试样评价为“C-”。将产生了60％以上且低于70％红锈的试样评价为“C”。将产生了50％以上且低于60％红锈的试样评价为“C+”。将产生了超过30％且低于50％红锈的试样评价为“B”。将红锈产生量为30％以下的试样评价为“A”。将这些结果一并记于表1、表2中。
<碱耐蚀性评价＞
蒸镀镀层的碱耐蚀性是在经pH缓冲装置管理的苛性钠水中浸渍镀覆钢板，评价经过规定时间后的腐蚀减量。在0.5％NaCl水溶液(2升)(pH13)中，在使长度为3cm搅拌棒以100rpm旋转的水中将端面被密封的试验片(镀覆钢板)浸渍6小时，测定试验片(镀覆钢板)的减重。
腐蚀减量为10g/m2以上或者镀层溶解而钢板露出的试样的评价设定为“D”。腐蚀减量为8.5g/m2以上且低于10g/m2的试样的评价设定为“C-”。腐蚀减量为7.5g/m2以上且低于8.5g/m2的试样的评价设定为“C”。腐蚀减量为6g/m2以上且低于7.5g/m2的试样的评价设定为“C+”。腐蚀减量低于6g/m2的试样的评价设定为“B”。腐蚀减量低于3g/m2的试样的评价设定为“A”。在表1、表2中记载各自的评价。
<加工后镀覆密合性的评价(弯曲试验)＞
为了评价试验片(镀覆钢板)的加工性，进行JIS H 8504镀覆的密合性试验法中的(j)弯曲试验法。其后进一步使用JIS Z 1522粘接胶带进行(g)剥离试验方法中的(1)胶带试验方法，评价试验片(镀覆钢板)的镀覆密合性。
在弯曲试验片(镀覆钢板)的阶段镀层剥离的试样的情况下将评价判断为“D”。在试样的弯曲部粘贴胶带，在剥离时一部分镀覆附着的情况下将评价判断为“C”。在镀覆没有通过胶带而剥离、在弯曲恢复时镀覆一部分剥离的情况下将评价判断为“B”。在镀覆没有通过胶带而剥离、在弯曲恢复时镀覆也没有剥离的情况下将评价判断为“A”。并且，将这些各评价记载于表1、表2中。
但是，对于“C”的评价，以“C-”、“C”及“C+”这3个等级进行评价，表示按照“C-”、“C”及“C+”的顺序，镀覆的附着的程度小。
Figure GDA0001786772840000171
Figure GDA0001786772840000181
由表1及表2中所示的结果获知，No.14、21、22、25、26、30、32、33、37～38的试样的耐蚀性、加工后耐蚀性、碱耐蚀性、加工后镀覆密合性、耐磨性优异。
此外，若基板的温度高，则存在界面合金层生长、加工后镀覆密合性降低的倾向，由于通过温度高而晶粒也生长，所以存在结晶粒径也变大的倾向。
图3通过表1的No.34的试验片的截面TEM观察，鉴定准结晶相的部分，示出该部分的电子射线衍射图像。如图3中所示的那样，由于能够得到起因于正20面体结构的放射状的正10角形的电子射线衍射图像，所以确认了在该试样中准结晶相析出。
产业上的可利用性
根据本公开的上述方式，能够提供在建材、汽车、家电领域等中使用时耐蚀性(特别是加工后的耐蚀性)、碱耐蚀性、耐磨性飞跃地提高的镀覆钢材。因此，与以往的表面处理钢材相比能够实现部件的长寿命化。
另外，日本专利申请第2015-191856号的公开的整体通过参照被引入到本说明书中。
关于本说明书中记载的所有文献、专利申请以及技术规格，通过参照而引入各文献、专利申请以及技术规格的情况与具体且分别记载的情况同等程度地引入本说明书中。

Claims (12)

1.一种镀覆钢材，其具备钢材、被覆于所述钢材的表面的镀层和形成于所述钢材及所述镀层的边界的界面合金层，
所述镀层的组成以质量％计含有Zn：20～83％及Al：2.5～46.5％，剩余部分包含Mg及杂质，且Mg含量为10％以上，
所述镀层的组织包含准结晶相、MgZn2相和剩余部分组织，所述准结晶相的面积分率为30～60％，90个数％以上的所述准结晶相为将其长轴方向的粒径设定为0.05～1.0μm的准结晶相，
所述镀层的厚度为0.1μm以上，所述界面合金层的厚度为500nm以下。
2.根据权利要求1所述的镀覆钢材，其中，所述剩余部分组织的面积分率为40％以下。
3.根据权利要求1或权利要求2所述的镀覆钢材，其中，所述镀层的厚度为0.1～10μm。
4.根据权利要求1或权利要求2所述的镀覆钢材，其中，所述镀层为蒸镀镀层。
5.根据权利要求3所述的镀覆钢材，其中，所述镀层为蒸镀镀层。
6.根据权利要求1或权利要求2所述的镀覆钢材，其中，所述界面合金层为Al-Fe合金层。
7.根据权利要求3所述的镀覆钢材，其中，所述界面合金层为Al-Fe合金层。
8.根据权利要求4所述的镀覆钢材，其中，所述界面合金层为Al-Fe合金层。
9.根据权利要求1或权利要求2所述的镀覆钢材，其中，所述镀层含有C、Ca、Si、Ti、Cr、Fe、Co、Ni、V、Nb、Cu、Sn、Mn、Sr、Sb、Pb、Y、Cd及La中的1种或2种以上的选择元素，且所述选择元素的合计含量以质量％计为0～0.5％。
10.根据权利要求3所述的镀覆钢材，其中，所述镀层含有C、Ca、Si、Ti、Cr、Fe、Co、Ni、V、Nb、Cu、Sn、Mn、Sr、Sb、Pb、Y、Cd及La中的1种或2种以上的选择元素，且所述选择元素的合计含量以质量％计为0～0.5％。
11.根据权利要求4所述的镀覆钢材，其中，所述镀层含有C、Ca、Si、Ti、Cr、Fe、Co、Ni、V、Nb、Cu、Sn、Mn、Sr、Sb、Pb、Y、Cd及La中的1种或2种以上的选择元素，且所述选择元素的合计含量以质量％计为0～0.5％。
12.根据权利要求5所述的镀覆钢材，其中，所述镀层含有C、Ca、Si、Ti、Cr、Fe、Co、Ni、V、Nb、Cu、Sn、Mn、Sr、Sb、Pb、Y、Cd及La中的1种或2种以上的选择元素，且所述选择元素的合计含量以质量％计为0～0.5％。
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