CN108026625B - 含有Mg的Zn合金被覆钢材 - Google Patents

含有Mg的Zn合金被覆钢材 Download PDF

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CN108026625B
CN108026625B CN201680052897.XA CN201680052897A CN108026625B CN 108026625 B CN108026625 B CN 108026625B CN 201680052897 A CN201680052897 A CN 201680052897A CN 108026625 B CN108026625 B CN 108026625B
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coating layer
metal coating
phase
steel material
quasi
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CN108026625A (zh
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下田信之
德田公平
松村贤一郎
后藤靖人
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/068—Flake-like particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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    • B32—LAYERED PRODUCTS
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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
    • B32B15/012—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
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    • B32B15/00—Layered products comprising a layer of metal
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
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    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
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    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Powder Metallurgy (AREA)

Abstract

一种含有Mg的Zn合金被覆钢材，其具备钢材和配置于上述钢材的表面的金属被覆层，上述金属被覆层为粒径为5～100μm、厚度为0.5～30μm的扁平形状的金属粒子的层叠结构体，上述金属粒子的组成以质量％计包含Zn：11～80％、Al：3～80％、Mg：8～45％、Ca：1～5％，剩余部分包含杂质，且Zn的含量、Al的含量及Mg的含量以质量％计满足Zn+Al＞Mg，上述金属粒子包含准结晶相、MgZn2相和剩余部分组织，上述准结晶相与上述MgZn2相的合计面积分率为45％以上，上述剩余部分组织的面积分率为0～55％，上述准结晶相的面积分率为20％以上，上述MgZn2相的面积分率为3％以上。

Description

含有Mg的Zn合金被覆钢材
技术领域
本公开涉及含有Mg的Zn合金被覆钢材。
背景技术
主要在建材用途领域中被要求的具有高耐蚀性能的含有Mg的Zn合金镀覆极硬且脆。因此，在成形加工时镀覆组织在镀层及镀层与钢材的界面处容易开裂、产生剥离等破坏，结果是，观察到镀层大大缺损的被称为粉化的现象。若产生粉化，则结果是导致镀覆钢材的耐蚀性本身大大下降。
一直以来，在钢材的表面被覆Zn等金属来改善钢材的耐蚀性是众所周知的，目前也大量生产了被覆有Zn、Zn-Al、Zn-Al-Mg、Al-Si等的钢材。对于这些被覆钢材，除耐蚀性以外，大多还要求耐磨性等许多功能。作为被覆方法，热浸镀被最广泛地使用。
这是由于，热浸镀适于大量生产，通过实施弯曲、拉深、焊接等加工，能够制造许多制品。
对被覆钢材所要求的耐蚀性逐年增高，因此近年来也提出了以下的专利文献1及专利文献2中所示那样的将Mg含量提高至以往以上水平的镀覆。这些镀覆具有以下特征：1)包含以往的镀覆以上水平的Mg、2)通过组织控制可得到以往以上水平的平面部的耐蚀性、3)可得到端面等的耐蚀性、4)即使是在碱气氛等以往的锌系或铝系镀覆最不擅长的气氛中耐蚀性也高等。
与对钢板的连续热浸镀不同，浸渍镀覆(热浸镀)、喷镀、蒸镀等方法从被覆于加工后的制品上的观点出发，是能够被覆难加工性的合金等的方法。它们中，喷镀法由于是不浸渍于熔融金属中的被覆方法，所以具有对钢材的热影响少、对钢材的大小制约少、能够被覆的金属或合金系的熔点容许范围广等优点。
为了在镀覆中提高耐蚀性，在镀覆中包含Zn成为基本，但对于许多的用途通过仅包含Zn的镀覆很多情况下耐蚀性不充分。因此，提出了专利文献3中记载那样的含有Mg的喷镀被覆。
该技术是将包含0.3％～15％的Mg的Zn合金喷镀于钢材表面的技术，是耐蚀性和耐损伤性优异的喷镀皮膜。此外，如专利文献4及专利文献5中所示的那样，提出了虽然限定于焊接部，但作为使耐蚀性提高的技术的喷镀法。这些专利文献4及专利文献5所述的技术是包含Zn、Al、Mg、Si等的多层系的喷镀被覆。
除此以外，在专利文献6中，公开了“一种喷镀时的防爆性及喷镀部的耐蚀性优异的喷镀材料，其特征在于，以质量％计含有Al：13～78％、Ca：1～5％，且Al及Ca的合计量为79％以下，剩余部分包含Mg及不可避免的杂质”。
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：日本专利第3305573号公报
专利文献4：日本特开2014-208880号公报
专利文献5：日本特开2012-107324号公报
专利文献6：日本专利4757692号公报
发明内容
发明所要解决的问题
然而，热浸镀皮膜有可能根据镀覆组成而加工性下降、厚膜化困难、或者加工法上受到制约等。特别是对于包含非平衡相、金属间化合物的皮膜，该倾向强，专利文献1及专利文献2中所示的提案也同样。有可能因加工部的皮膜脱落而钢材的耐蚀性大幅下降。
专利文献3中记载的喷镀被覆虽然耐蚀性、耐损伤性优异，但是特别是在碱区域中的耐蚀性不充分。专利文献4及专利文献5中记载的喷镀被覆原本是由于以往技术的被覆在焊接中丧失而对其进行补充的技术，耐蚀性、耐磨性并不能说是充分的。对于专利文献6，现状也是还有改善的余地。
本公开的一方式是解决上述那样的问题，提供具备与以往技术相比具有进一步的高耐蚀性及高耐磨性、且耐损伤性优异的金属被覆层的钢材。
用于解决问题的手段
本公开是基于以上的背景而进行的，包含以下的方式。
[1]一种含有Mg的Zn合金被覆钢材，其具备钢材和配置于上述钢材的表面的金属被覆层，上述金属被覆层为粒径为5～100μm、厚度为0.5～30μm的扁平形状的金属粒子的层叠结构体，
上述金属被覆层的组成以质量％计满足Zn：11～80％、Al：3～80％、Mg：8～45％、Ca：1～5％及Zn+Al＞Mg，
上述金属被覆层包含准结晶(也可称为准晶，quasicrystalline)相、MgZn2相和剩余部分组织，上述准结晶相与上述MgZn2相的合计面积分率为45％以上，上述剩余部分组织的面积分率为0～55％，上述准结晶相的面积分率为20％以上，上述MgZn2相的面积分率为3％以上。
[2]根据[1]所述的含有Mg的Zn合金被覆钢材，其中，上述Al的含量以质量％计为3％以上且低于13％。
[3]根据[1]或[2]所述的含有Mg的Zn合金被覆钢材，其具有覆盖上述金属粒子的表面的膜厚为1nm～1000nm的氧化皮膜。
[4]根据[1]～[3]中任1项所述的含有Mg的Zn合金被覆钢材，其中，上述金属被覆层为喷镀被覆层。
[5]根据[1]～[4]中任1项所述的含有Mg的Zn合金被覆钢材，其中，上述金属被覆层的组成以质量％计含有Y：0％～3.5％、La：0％～3.5％、Ce：0％～3.5％、Si：0％～3.5％、Ti：0％～0.5％、Cr：0％～0.5％、Co：0％～0.5％、Ni：0％～0.5％、V：0％～0.5％、Nb：0％～0.5％、Cu：0％～0.5％、Sn：0％～0.5％、Mn：0％～0.2％、Sr：0％～0.5％、Sb：0％～0.5％、Pb：0％～0.5％、C：0％～0.5％、Fe：0％～0.5％及Cd：0％～0.5％中的1种或2种以上，且满足下述式(A)及下述式(B)，
·式(A)：Ca+Y+La+Ce≤3.5％
·式(B)：Ti+Cr+Co+Ni+V+Nb+Cu+Sn+Mn+Sr+Sb+Pb+C+Fe+Cd≤0.5％
式(A)及式(B)中，元素符号表示以质量％计的各元素的含量。
发明效果
根据本公开的一方式，能够提供耐蚀性及耐磨性极优异、且耐损伤性优异的含有Mg的Zn合金被覆钢材。通过这样，能够提供可广泛应用于汽车用途、建筑用途、住宅用途等的钢材，通过对构件寿命的提高、资源的有效利用、环境负荷的降低、维修的劳力、成本的降低等有益，大大有助于产业的发展。
此外，通过将本公开的一方式的技术应用于加工构件、钢管等，能够提供具有超过以往的含Mg被覆的耐蚀性、且碱区域的耐蚀性也优异的高硬度的含有Mg的Zn合金被覆钢材。
附图说明
图1是表示本公开的实施方式所述的被覆钢材的截面图。
图2是实施例中得到的金属被覆层的准结晶相中的TEM电子射线衍射图像。
具体实施方式
本发明人们发现，作为耐蚀性被覆层，使Zn-Mg-Al-Ca系中含有准结晶相的金属被覆层显示高的耐蚀性及耐磨性，并且也显示耐损伤性，对该系的金属被覆层的加工性进行了研究，结果达成了本公开。其基于发现了以下见解：包含准结晶相的组织是对耐蚀性、耐磨性及耐损伤性的提高极有效的组织，通过喷镀法而形成包含该准结晶相的组织。
以下，对本公开的实施方式所述的耐蚀性、耐磨性及耐损伤性优异的含有Mg的Zn合金被覆钢材进行说明。
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％”。
本公开的实施方式所述的含有Mg的Zn合金被覆钢材1如例如图1的截面结构(沿被覆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)、家电构件(空调的室外机的框体等)、汽车部件(行走构件等)等钢材2和通过喷镀而形成于钢材2的表面的金属被覆层(喷镀被覆层)3。金属被覆层3包含比金属被覆层3薄、且具有自身的厚度的数倍左右的粒径的扁平状的多个金属粒子5的层叠结构体。在金属被覆层3中，例如，金属粒子5沿着钢材2的表面在其面方向上按照没有间隙地覆盖钢材2的表面的方式配置有多个，并且在钢材2的表面的上方沿钢材2的厚度方向按照没有间隙的方式沉积有多个。即，金属被覆层3由例如扁平状的多个金属粒子5沉积成石墙状的结构体构成。
此外，例如，在钢材2的表面与最下层的金属粒子5的界面部分(钢材2与金属被覆层3的界面部分)中形成有Fe-Al合金层2A。由于金属粒子5在附着于钢板表面后，在极短时间内凝固，所以该Fe-Al合金层2A与一般的热浸镀的情况不同，具有非常薄且与后述的金属粒子5表面的氧化皮膜同等以下的厚度。
此外，在各金属粒子5的表面形成有氧化皮膜，如图1中所示的那样在各金属粒子间形成有明确的界面5b。形成于各金属粒子5的表面的氧化皮膜是在喷镀时熔融状态的金属液滴在大气中飞来而沉积在钢材2的表面，并在固化时生成的氧化皮膜。该覆盖金属粒子5的表面的氧化皮膜的膜厚为例如1nm～1000nm左右的膜厚。即，具有覆盖金属粒子的表面的膜厚为1nm～1000nm的氧化皮膜表示通过喷镀而形成有金属被覆层3。
对于钢材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。
Fe-Al合金层2A形成于钢材2的表面，例如，作为组织，包含Al3Fe相和Zn相，且平均组成包含Fe：30～50％、Al：50～70％、Zn：2～10％及剩余部分：杂质。Fe-Al合金层2A由于如后述那样在金属粒子5中包含许多Al及Zn，所以通过在喷镀时熔融的金属粒子的液滴与钢材2的表面的Fe的反应而生成。Fe-Al合金层2A中包含的Al和Zn是构成金属粒子5的Zn-Mg-Al合金中包含的Al和Zn一部分扩散的结果所包含的Al和Zn。
以下，对金属粒子5的大小及组织、以及金属被覆层3的组织及组成等进行说明。
金属粒子5包含准结晶相5a、MgZn2相和剩余部分组织。在层叠有金属粒子5的金属被覆层3中，准结晶组织与MgZn2相的合计面积分率为45％以上，剩余部分组织的面积分率为0～55％，准结晶相的面积分率为20％以上，MgZn2相的面积分率为3％以上。
另外，金属粒子5没有必要具有上述的面积分率，只要是作为层叠结构体的金属被覆层3为上述的面积分率的范围即可。因而，若单独看多个金属粒子5，则即使有一部分不包含准结晶相5a的金属粒子5，也只要在其他金属粒子5中存在准结晶相5a，且在金属被覆层3的整体中存在20％以上的准结晶相5a即可。因此，图1中按照在一部分金属粒子5中不存在准结晶相5a的方式进行描绘。
即，金属被覆层3的组织包含准结晶相、MgZn2相和剩余部分组织，且准结晶相与MgZn2相的合计面积分率为45％以上，剩余部分组织的面积分率为0～55％，准结晶相的面积分率为20％以上，MgZn2相的面积分率为3％以上。
其中，准结晶组织与MgZn2相的合计面积分率更优选为50％以上。另一方面，准结晶组织与MgZn2相的合计面积分率从工业上的生产率的方面出发，优选为80％以下。
剩余部分组织的面积分率从耐蚀性的方面出发，更优选为0～20％。
准结晶相的面积分率从耐蚀性的方面出发，更优选为25％以上。另一方面，准结晶相的面积分率从工业上的生产率的方面出发，优选为45％以下。
MgZn2相的面积分率从耐蚀性的方面出发，更优选为20％以上。另一方面，MgZn2相的面积分率从工业上的生产率的方面出发，优选为40％以下。
构成金属被覆层3的金属粒子5的粒径及厚度通过喷镀前的金属粒子的大小和喷镀条件而大致决定。金属粒子5以最表层熔融的半熔融状态以高速碰撞到钢材2表面，发生变形而在极短时间内凝固。由于金属粒子5的平行方向(与钢材2的表面平行的方向)的大小变得大于喷镀前的金属粒子5的粒径，且金属粒子5的厚度变得小于喷镀前的金属粒子5的粒径，所以金属粒子5的形状成为所谓扁平状的形状。此外，由于经由上述那样的生成过程，所以金属粒子5的平面形状很少成为完全的圆，因此金属粒子5的粒径设定为粒子的直径成为最长的直线的长度。金属粒子5的厚度设定为与粒子的直径成为最长的直线垂直、且成为最长的直线的长度。
金属粒子5的粒径优选为5～100μm，厚度优选为0.5～30μm。此外，金属粒子5的粒径更优选为20～80μm，厚度更优选为1～15μm。
金属粒子5的长宽比(厚度/粒径)优选为0.5/100～30/100，更优选为1/80～15/80。
另外，确认形成金属被覆层3的金属粒子5的形状及尺寸是否满足本公开的构成只要通过金属被覆层3的截面观察(沿被覆层厚度方向切断的截面观察)来确认即可。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。
具体而言，金属粒子5的粒径及厚度如下那样测定。通过光学显微镜或SEM(扫描型电子显微镜)，进行金属被覆层3的截面观察(在沿金属被覆层3的厚度方向切断的截面中，在与金属被覆层3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500倍)中观察到的各金属粒子的粒径及厚度的平均值。将该平均值作为金属粒子5的粒径及厚度。并且，金属粒子的长宽比设定为由该平均值的金属粒子的粒径及厚度算出的值。
此外，被覆金属粒子的表面的氧化皮膜的厚度如下那样测定。通过SEM(扫描型电子显微镜)，进行金属被覆层3的截面观察(在沿金属被覆层3的厚度方向切断的截面中，观察在与金属被覆层3平行的方向上相当于2.5mm长度的区域)。在该区域中，在至少三个视野(倍率为1万倍)中观察到的各金属粒子5中，在每一个视野中选择3个金属粒子5。并且，每各粒子在任意的3处测定将所选择的3个(至少合计9个)各金属粒子5的表面被覆的氧化皮膜的厚度，求出其平均值。将该平均值作为氧化皮膜的厚度。
若金属粒子5的粒径超过100μm，则在晶粒内容易产生龟裂且成为耐蚀性的下降或皮膜的脱离的原因。具有低于5μm的粒径的粒子以极低速到达钢板，有可能变形少，有可能密合性下降。此外，若减小初期的金属粒子的粒径，则由于送给性下降、生产率下降，所以不优选。
若金属粒子5的厚度超过30μm，则容易在晶粒内产生龟裂且成为耐蚀性的下降或皮膜的脱离的原因。或者也有可能因为变形小而密合性下降。具有低于0.1μm的厚度的粒子以极低速到达钢板，有可能变形少，有可能密合性下降。
接着，对金属被覆层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-反射电子图像拍摄金属被覆层3的任意的截面(沿被覆层厚度方向切断的截面)的至少3个视野以上(在与金属被覆层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，特定与金属被覆层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，特定金属被覆层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，测定金属被覆层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个视野的平均值作为金属被覆层3中的准结晶相、MgZn2相及剩余部分组织的面积分率。
金属被覆层3的各相的鉴定在将金属被覆层3的截面(沿被覆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。
金属被覆层3的组成优选以质量％计满足Zn：11～80％、Al：3～80％、Mg：8～45％、Ca：1～5％及Zn+Al＞Mg。具体而言，金属被覆层3的除氧以外的组成更优选以质量％计包含Zn：11～80％、Al：3～80％、Mg：8～45％、Ca：1～5％及剩余部分：杂质，且Zn含量、Al含量及Mg含量满足Zn+Al＞Mg(Zn含量及Al含量的合计＞Mg含量)。
另外，所谓杂质是指原材料中包含的成分、或在制造的工序中混入的成分，不是有意含有的成分。
首先，对于金属被覆层3的组成，对数值限定范围和其限定理由进行说明。
“Zn(锌)：11～80％”
为了得到准结晶相作为金属被覆层3(即，构成金属被覆层3的金属粒子5)的金属组织，含有上述范围的Zn。因此，将金属被覆层3的Zn含量设定为11～80％。Zn含量低于11％时，无法在金属被覆层3中生成准结晶相。此外同样地，Zn含量超过80％时，无法在金属被覆层3中生成准结晶相。
此外，为了使准结晶优选地生成而使耐蚀性进一步提高，在金属被覆层3中优选将Zn含量设定为33％以上。若设定为33％以上，则成为作为初晶的准结晶相容易生长的组成范围，Mg相变得难以作为初晶生长。即，能够增多金属被覆层3中的准结晶相的相量(面积分率)，并且能够极力减少使耐蚀性劣化的Mg相。更优选将金属被覆层3中的Zn含量设定为35％以上。通常，若在该组成范围内且通过喷镀法形成金属被覆层3，则Mg相几乎不存在。
“Al(铝)：3～80％”
Al是使被覆钢材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，将金属被覆层3的Al含量设定为3％以上。另一方面，若在金属被覆层3中大量地含有Al，则变得容易产生红锈，并且准结晶相变得难以生成而耐蚀性下降。因而，将金属被覆层3的Al含量的上限设定为80％。此外，为了使准结晶相的生成容易，Al含量优选设定为3％以上且低于13％，更优选设定为5％以上且50％以下。另外，Al是在形成Fe-Al界面合金层2A方面优选含有的元素。
这里，本发明人们调查了Fe-Al合金层2A的厚度与成分的关系，结果是，若金属被覆层3的Al含量成为13％以上，则存在Fe-Al合金层2A的厚度变大的倾向。由于过厚的Fe-Al合金层2A除了引起金属被覆层3中的Al含量的减少，变得难以形成准结晶相以外，还使金属被覆层3的耐蚀性或性能劣化，所以优选避免。因而，从将Fe-Al合金层2A薄膜化的方面出发，Al含量也优选设定为3％以上且低于13％，更优选设定为5％以上且50％以下。
另外，本来Mg与Fe没有反应性，并降低Zn及Al的活度，具有适度的与基底金属的反应性。因此，适合作为金属被覆层3用的合金。另一方面，当Al浓度高时，谋求不会使金属被覆层3与基底金属的反应性过度地进行那样的喷镀时间的短时间化、喷镀速度的高速化等热处理条件较佳。
“Mg(镁)：8～45％”
Mg与Zn及Al同样地是构成金属被覆层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。
即，Mg含量只要设定为8％以上且45％以下即可，优选设定为15％以上且35％以下。另一方面，抑制所含有的Mg在金属被覆层3中作为Mg相析出由于使耐蚀性提高而优选。即，由于Mg相使耐蚀性劣化，所以所含有的Mg优选形成为准结晶相、或其他的金属间化合物的构成物。
“Ca：1～5％”
Ca是改善喷镀法的操作性的元素。在喷镀法中，将喷镀后的氧化性高的熔融Mg合金在大气中保持。因此，优选采取一些Mg的抗氧化手段。Ca与Mg相比容易氧化，以熔融状态在金属粒子5上形成稳定的氧化皮膜而防止金属粒子5中的Mg的氧化。因而，将金属被覆层3的Ca含量设定为1～5％。
由于若含有1质量％以上的Ca，则能够将Mg含量高的金属被覆层3在大气中不发生氧化地保持，所以优选。另一方面，由于Ca容易氧化，有时对耐蚀性造成不良影响，所以优选将上限设定为5％。
此外，金属被覆层3也可以含有Y：0％～3.5％、La：0％～3.5％及Ce：0％～3.5％中的1种或2种以上。其中，满足式(A)：Ca+Y+La+Ce≤3.5％(式中，元素符号表示各元素的含量(质量％)。)较佳。
Y、La及Ce通过在喷镀粒子中含有一定的浓度，变得更容易形成准结晶相。另一方面，由于Ca浓度高时，或Ca、Y、La及Ce的浓度的合计高时，就变得突然不形成准结晶相，所以优选规定各自的上限浓度。
此外，金属被覆层3也可以含有Si：0％～3.5％、Ti：0％～0.5％、Cr：0％～0.5％、Co：0％～0.5％、Ni：0％～0.5％、V：0％～0.5％、Nb：0％～0.5％、Cu：0％～0.5％、Sn：0％～0.5％、Mn：0％～0.2％、Sr：0％～0.5％、Sb：0％～0.5％、Pb：0％～0.5％、C：0％～0.5％、Fe：0％～0.5％及Cd：0％～0.5％中的1种或2种以上。其中，满足式(B)：Ti+Cr+Co+Ni+V+Nb+Cu+Sn+Mn+Sr+Sb+Pb+C+Fe+Cd≤0.5％(式中，元素符号表示各元素的含量(质量％)。)较佳。
这些元素能够在金属被覆层3中含有，但式(B)是在不会阻碍准结晶相的形成、不会使金属被覆层3的性能劣化的情况下能够含有各元素的组成范围。若超过该式(B)的范围，则准结晶相变得难以形成。
Zn、Al及Mg由于是构成准结晶的元素，所以必定需要以上述的一定范围包含在金属被覆层3中，若成为上述的组成范围之外，则变得无法使金属被覆层3(Zn-Mg-Al合金层)中含有20％以上的准结晶相。
此外从准结晶相的形成的观点出发，金属被覆层3的组成更优选满足Zn：11～72％、Al：5～67％、Mg：10～35％、Ca：1～5％及Zn+Al＞Mg，进一步优选满足Zn：35～70％、Al：3～42％、Mg：15～25％、Ca：1.4～3％及Zn+Al＞Mg，特别优选满足Zn：35～70％、Al：5～13％、Mg：15～25％、Ca：1.4～3％及Zn+Al＞Mg。
金属被覆层3的组成是为上述的范围之外时变得基本上难以得到准结晶的组成。此外，金属被覆层3进而变得硬质，变得容易引起金属被覆层3的剥离，也可成为不适合作为金属被覆层3的组成的范围。
金属被覆层3的组成、以及金属被覆层3及Fe-Al合金层2A的厚度的测定方法的厚度的测定方法如下所述。
首先，通过发烟硝酸将Fe-Al合金层2A钝化而仅将上层的金属被覆层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)，测定金属被覆层3的组成。
其中，在金属被覆层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，将准结晶如金属间化合物那样以正确的化学式定义不容易。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，金属被覆层3除准结晶相以外还包含MgZn2相和剩余部分组织，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相等。
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2中所示的电子射线衍射图像仅由准结晶得到，不会由其他任意的晶体结构得到。
此外，由金属合金层3的化学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，若在金属合金层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金属合金层3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20％以上，则增加该效果。即形成于金属合金层3(Zn-Mg-Al合金层)的表面上的准结晶相相对于腐蚀因子具有高的阻挡效果。
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。在金属合金层3(Zn-Mg-Al合金层)的成分组成中，成立Zn＞Mg+Al+Ca(式中，元素符号表示元素的含量(质量％))的情况下，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。若准结晶相的面积分率为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，该效果较大地体现出来。
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可通过在金属被覆层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)中的金属被覆层3的表层的氧化皮膜稳定化，显示特别高的耐蚀性。因此，准结晶相需要在金属被覆层3中以面积分率计含有20％以上，更优选含有30％以上。
例如，在金属被覆层3中含有准结晶相的状态下，作为剩余相，含有MgZn2相、Mg2Zn3相，准结晶相、MgZn2相及Mg2Zn3的面积分率合计成为75％以上时，碱区域中的耐蚀性提高。例如，即使在强碱环境、氨水中、苛性钠中，腐蚀量也越几乎变成0则越能够得到优异的碱耐蚀性。
在得到准结晶相的组成的范围内，除准结晶以外，作为剩余部分组织，有时在金属被覆层3中混合存在Al相。Al相为非常软质的镀覆且具有塑性变形能，若含有这些相，则在金属被覆层3中产生塑性变形能。
若在金属被覆层3中以面积分率计含有50％以上的Al相、且与准结晶相的面积分率的合计超过75％，则在金属被覆层3中产生延展性，例如耐冲击性优异，若实施钢球冲击试验，则金属被覆层3的剥离量大幅减少。
“金属被覆层3的形成方法”
为了形成金属被覆层3，准备按照成为上述的组成的方式配合了各元素的喷镀材料的粉末或者线材。作为一个例子，为了得到粉末，按照成为目标组成的方式将各金属容纳于坩埚等耐热容器中并使其熔化、凝固。在将各金属熔化时，为了均匀混合，优选使用小的金属锭。对于加热熔化时的气氛，为了避免杂质的混入，优选为不活泼气体气氛，但优选采用例如氧浓度为1％以下的气氛。
在凝固时，可以使用利用了雾化法等的凝固手段，也可以在坩埚内凝固后，将凝固物粉碎而粉末化。
用于喷镀的粉末的粒径没有特别问题，但考虑所需要的金属被覆层3的面积、厚度等，可以选择随时优选的范围。例如可以选择50μm～200μm左右的粒径。
喷镀方法可以采用等离子体喷镀、电弧喷镀等。
上述优选的组成的合金由于非常脆，所以能够容易地通过粉碎法而粉末化，但由于在粒子形状、大小不一致的情况下，被覆效率下降，所以优选使用雾化法进行粉末化，其中优选采用表面的氧化少的气体雾化法。此外，优选使用将经粉末化的粒子进一步分级而一致为规定范围的粒径的粒子。
若将如以上说明的那样准备的粉末供给于喷镀枪中对钢材2的表面进行喷镀，形成喷镀层，则能够得到图1中所示的在钢材2的表面被覆有作为金属粒子5被多个层叠而成的结构体的金属被覆层3的含有Mg的Zn合金被覆钢材1。喷镀枪由于将喷镀材料熔融而作为微细的液滴进行喷射，所以若使该液滴的凝固物沉积在钢材2的表面则能够得到多个金属粒子5沉积而成的金属被覆层3。
为了控制金属被覆层3(构成金属被覆层3的金属粒子5)中的准结晶相的面积分率(即，上述金属被覆层3的组织中的各相的面积分率)，温度控制是有效的。由于500～350℃的温度域中最稳定的相为准结晶相，所以通过延长该温度域中的保持时间，能够使金属被覆层3(Zn-Al-Mg合金层)中的准结晶相的面积分率提高。更优选保持30秒以上、且低于5℃/秒的冷却速度。通过低于该冷却速度，能够最大限生成准结晶相的析出。例如，若将这个期间的冷却速度设定为5℃/秒以上，则存在本来得到的准结晶相的比例变得极端小的倾向。若过大，则在准结晶相析出前被一定程度冷却，准结晶相的含有变少。
另一方面，在低于350℃且250℃以下的温度域中，由于与准结晶相相比进入Mg2Zn3相、Mg相、MgZn相等金属间化合物相的稳定区域中，所以需要加快该温度域中的冷却速度。优选通过设定为10℃/秒以上的冷却速度，能够维持金属被覆层3(Zn-Al-Mg合金层)中的准结晶相的面积分率的最大值。
即，金属被覆层3是将目标成分组成的合金粉末供给于喷镀枪中而对钢材2的表面进行喷镀，形成喷镀层。之后，在冷却的过程中，优选在500℃以下且低于350℃的温度域中将冷却速度设定为低于5℃/秒且保持30秒以上，在低于350℃且250℃以下的温度域中将冷却速度设定为10℃/秒以上。
另外，低于250℃的温度域的冷却速度没有限定。这是由于，在该温度域中温度低且原子扩散变得不活跃，已经低于相的生成、分解所需要的温度。
得到该准结晶相的方法考虑了多种，但在喷镀的情况下，由于保留起始时的粉末的组织的也较多，所以喷镀前的粉末的预热处理是有效的。具体而言，例如，优选将喷镀前的粉末在100～200℃下进行预热处理。通过预先制成目标相结构，能够控制保留起始时的组织的喷镀粒子的组织。
此外，成为半熔融状态的粒子表面或成为完全熔融状态的粒子通过选择喷镀条件(层叠道次间隔、喷镀枪与钢材的距离、钢材的预热温度)，从而很好地控制后来层叠的粒子、喷镀电弧等的热、对钢材的除热，由此能够得到目标面积分率的准结晶相。
这里，通过进行热处理，生成Al-Fe合金层，钢材2与金属被覆层3的密合性提高。但是，过厚的Fe-Al合金层2A除了引起金属被覆层3中的Al含量的减少，变得难以形成准结晶相以外，而且使金属被覆层3的耐蚀性及性能劣化。因此，为了制成成为目标组成及组织的金属被覆层3，优选控制金属被覆层3的组成和热处理温度及时间，将Al-Fe合金层2A的厚度设定为1～1000nm。若与1000nm相比过厚，则引起金属被覆层3的Al含量的减少，准结晶相的形成变得困难。此外，在Al-Fe合金层2A为1nm以下时，有时金属被覆层3与钢材2的密合性变得不充分。Al-Fe合金层2A的厚度优选为100～500nm。
其中，Al-Fe合金层2A的厚度如下那样测定。通过SEM(扫描型电子显微镜)，进行Al-Fe合金层2A的截面观察(在沿Al-Fe合金层2A的厚度方向切断的截面中，在与Al-Fe合金层2A平行的方向上相当于2.5mm长度的区域的观察)。在该区域中，求出至少在三个视野(倍率为1万倍)中观察到的各Al-Fe合金层2A的任意的5处(至少计15处)的厚度的平均值。将该平均值作为Al-Fe合金层2A的厚度。
金属被覆层3的厚度也作为与Al-Fe合金层2A的厚度同样地测定的平均值。
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。
在基于上述的制造方法和冷却过程得到的金属被覆层3中，由包含规定比例的准结晶相的Zn-Al-Mg合金的金属粒子5的层叠结构体形成的金属被覆层3将钢材2的表面覆盖。因此，金属被覆层3硬，耐磨性优异，耐蚀性优异，碱区域中的耐蚀性也优异。因此，能够提供表面硬、耐磨性优异、耐蚀性优异、碱区域中的耐蚀性也优异的含有Mg的Zn合金被覆钢材1。
此外，在之前的实施方式中对在表面平滑的钢材2上被覆有金属被覆层3的结构进行了说明，但就在表面有凹凸的钢材、截面异形的钢材、折弯后的钢材等任一形状的钢材而言，也只要是能够喷镀的形状的钢材，则不限于钢材的形状或凹凸的有无，均能够适用本公开结构。因而本公开的技术能够不论钢材的形状如何而提供。
此外，本公开在含有Mg的Zn合金被覆钢材的制作中，也可以在形成金属被覆层后实施后处理。
作为后处理，可列举出对被覆钢材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，作为形成金属被覆层后的后处理，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详细说明。
以JIS G 3101(2010)规定SS400(第1钢材：长度为150mm、宽度为70mm、厚度为3.2mm)和JIS G 3101(2010)规定SS400(第2钢材：长度为180mm、宽度为70mm、厚度为1.6mm)作为试验片，用于以下的喷镀试验。但是，对于第2钢材，加工成将距离其一个端部30mm的位置以R2.0mm弯曲90°的弯曲试验片而用于以下的喷镀试验。另外，以下将没有实施弯曲加工的第1钢材的试验片称为“平面试验片”。
喷镀用粉末使用成为Zn-(15～45)质量％Mg-(3～15)质量％Al-(2～5)质量％Ca的组成比(Zn的质量％为剩余部分)且粒径为50～200μm的粉末。喷镀用粉末的粒形状大致为球形。
此外，作为比较用的喷镀粉末，分别准备市售的Al粉末(平均粒径为100μm)、Zn粉末(平均粒径为250μm)、Mg粉末(平均粒径为280μm)，根据试验分别单独使用或混合使用。
使用大气压等离子体电弧喷镀法，将目标喷镀用粉末通过氩气供给到将工作气体生成为Ar-H2气体的等离子体中。将喷镀枪与钢材(基材)的距离设定为100mm，通过按照基材的温度不超过500℃的方式使喷镀枪移动并重复喷镀，从而控制所形成的金属被覆层的厚度(与后述的评价试验相应的厚度)。并且，在表1中所示的预热温度下将喷镀用粉末喷镀后，由喷镀枪将喷镀用粉末喷镀，在平面试验片(第1钢材)的表面形成金属被覆层。
关于冷却条件，从凝固到350℃为止的冷却速度在3℃以上且低于5℃、且从350℃到250℃为止的冷却速度在10℃以上且低于15℃的范围内进行。
此外一部分试验片(符号Z的例子)将喷镀枪与基材的距离设定为150mm。
使用同等的喷镀枪，在上述的各个平面试验片(第1钢材)的表面形成成为比较的利用Al粉末、Zn粉末、或者它们的混合粉末的金属被覆层。
另一方面，在经折弯加工的弯曲试验片(第2钢材)的表面使用多轴喷镀机器人分别在弯曲部分的内侧、外侧利用喷镀形成金属被覆层。
将制造的金属被覆层的组成示于以下的表1中。另外，各相的面积分率按照已述的方法测定。
“热浸镀材的制造”
另外，作为比较用，制造了具有多种组成的利用热浸镀的金属被覆层的钢材(以下“平面热浸镀材”)。热浸镀用的基板使用由JIS G 3101(2010)规定SS400形成的长度为180mm、宽度为70mm、厚度为1.6mm的钢板。将利用热浸镀的金属被覆的组成示于表1中。利用热浸镀的金属被覆层的厚度设定为与利用喷镀的金属被覆层相同。
表1
Figure BDA0001595151990000181
“耐蚀性评价”
耐蚀性通过腐蚀促进试验来评价。腐蚀促进试验通过JIS Z2371中规定的使用了5％NaCl水溶液的盐水喷雾试验(SST)来进行。最大进行试验至6000Hrs，以在各个平面试验片及平面热浸镀材中产生红锈的时间进行比较。任一试验片均将端面、背面用胶带密封。金属被覆层的厚度全部设定为25μm。
另一方面，按照同样地操作，对弯曲试验片分别进行弯曲部的内侧评价和外侧评价。此外，对于在镀覆后对平面热浸镀材实施了将距离一个端部30mm的位置以R2.0mm弯曲90°的弯曲加工的弯曲热浸镀材，也分别进行弯曲部的内侧评价和外侧评价。
“耐磨性及耐损伤性评价”
耐磨性及耐损伤性使用HEIDON社制、直线滑动试验机。接触部分设定为钢球(20R：材质SKD11)，设定为载荷为500g、滑动距离为40mm、速度为1200mm/min。10次往复后，通过目视观察各个平面试验片及平面热浸镀材的表面。金属被覆层的厚度全部设定为12μm。
在试验后，对于各个平面试验片及平面热浸镀材的表面，看到明显的伤痕或缺口的情况设定为“G4”。非试验部与试验部相比颜色明确地发生变化的情况设定为“G3”。非试验部与试验部相比颜色稍微发生变化的情况设定为“G2”，将外观与试验前几乎没有变化的情况设定为“G1”。
将耐蚀性评价试验的结果示于以下的表2～表3中，将耐磨性及耐损伤性评价试验的结果示于以下的表4中。
表2
符号 试验片 钢材 红锈产生有无和时间 备注
1 A 平面 有：5000小时 EX
2 A 弯曲部外侧 有：5000小时 EX
3 A 弯曲部内侧 有：5000小时 EX
4 B 平面 无 EX
5 B 弯曲部外侧 无 EX
6 B 弯曲部内侧 无 EX
7 C 平面 无 EX
8 C 弯曲部外侧 无 EX
9 C 弯曲部内侧 无 EX
10 D 平面 无 EX
11 D 弯曲部外侧 无 EX
12 D 弯曲部内侧 无 EX
13 E 平面 有：5000小时 EX
14 E 弯曲部外侧 有：5000小时 EX
15 E 弯曲部内侧 有：5000小时 EX
16 F 平面 无 EX
17 F 弯曲部外侧 无 EX
18 F 弯曲部内侧 无 EX
19 G 平面 无 EX
20 G 弯曲部外侧 无 EX
21 G 弯曲部内侧 无 EX
22 H 平面 无 EX
23 H 弯曲部外侧 无 EX
24 H 弯曲部内侧 无 EX
25 I 平面 有：4000小时 CF
26 I 弯曲部外侧 有：4000小时 CF
27 I 弯曲部内侧 有：4000小时 CF
28 J 平面 有：2000小时 CF
29 J 弯曲部外侧 有：2000小时 CF
30 J 弯曲部内侧 有：2000小时 CF
31 K 平面 有：2000小时 CF
32 K 弯曲部外侧 有：2000小时 CF
33 K 弯曲部内侧 有：2000小时 CF
34 L 平面 有：5000小时 CF
35 L 弯曲部外侧 有：2500小时 CF
36 L 弯曲部内侧 有：1000小时 CF
37 M 平面 有：5000小时 CF
38 M 弯曲部外侧 有：2500小时 CF
39 M 弯曲部内侧 有：1000小时 CF
40 N 平面 有：5000小时 CF
41 N 弯曲部外侧 有：2500小时 CF
42 N 弯曲部内侧 有：1000小时 CF
表3
符号 试验片 钢材 红锈产生有无和时间 备注
43 O 平面 有：5000小时 CF
44 O 弯曲部外侧 有：2500小时 CF
45 O 弯曲部内侧 有：1000小时 CF
46 P 平面 无 EX
47 P 弯曲部外侧 无 EX
48 P 弯曲部内侧 无 EX
49 Q 平面 无 EX
50 Q 弯曲部外侧 无 EX
51 Q 弯曲部内侧 无 EX
52 R 平面 无 EX
53 R 弯曲部外侧 无 EX
54 R 弯曲部内侧 无 EX
55 S 平面 无 EX
56 S 弯曲部外侧 无 EX
57 S 弯曲部内侧 无 EX
58 T 平面 无 EX
59 T 弯曲部外侧 无 EX
60 T 弯曲部内侧 无 EX
61 U 平面 有：5000小时 EX
62 U 弯曲部外侧 有：5000小时 EX
63 U 弯曲部内侧 有：5000小时 EX
64 V 平面 有：5000小时 CF
65 V 弯曲部外侧 有：2500小时 CF
66 V 弯曲部内侧 有：1000小时 CF
67 W 平面 有：5000小时 CF
68 W 弯曲部外侧 有：2500小时 CF
69 W 弯曲部内侧 有：1000小时 CF
70 X 平面 有：2500小时 CF
71 X 弯曲部外侧 有：500小时 CF
72 X 弯曲部内侧 有：500小时 CF
73 Y 平面 有：3000小时 CF
74 Y 弯曲部外侧 有：1000小时 CF
75 Y 弯曲部内侧 有：1000小时 CF
76 Z 平面 无 EX
77 Z 弯曲部外侧 无 EX
78 Z 弯曲部内侧 无 EX
79 ZZ 平面 无 EX
80 ZZ 弯曲部外侧 有：5000小时 EX
81 ZZ 弯曲部内侧 有：5000小时 EX
表4
符号 试验片 结果 备注
1 A G2 EX
2 B G1 EX
3 C G1 EX
4 D G1 EX
5 E G3 EX
6 F G1 EX
7 G G1 EX
8 H G1 EX
9 I G4 CF
10 J G4 CF
11 K G4 CF
12 L G4 CF
13 M G4 CF
14 N G4 CF
15 O G4 CF
16 P G1 EX
17 Q G1 EX
18 R G1 EX
19 S G1 EX
20 T G1 EX
21 U G3 EX
22 V G4 CF
23 W G4 CF
24 X G4 CF
25 Y G4 CF
26 Z G3 EX
27 ZZ G3 EX
如表2中所示的那样本公开的具有利用喷镀的金属被覆层的钢材到SST6000小时为止，均没有红锈产生，显示高的耐蚀性。比较材中，一部分镀覆虽然在没有加工的部分耐蚀性良好，但通过加工有镀覆的脱落(粉化)，耐蚀性在加工部显著下降。此外，如表3中所示的那样本公开的具有利用喷镀的金属被覆层的钢材显示耐磨性及耐损伤性优异。
图2通过表1的符号(4)的试样的截面TEM观察，鉴定准结晶相的部分，表示该部分的电子射线衍射图像。如图2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，所以能够确认在该试样中准结晶相析出。
另外，日本专利申请第2015-191855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 (5)

1.一种含有Mg的Zn合金被覆钢材，其具备钢材和配置于所述钢材的表面的金属被覆层，所述金属被覆层为粒径为5～100μm、厚度为0.5～30μm的扁平形状的金属粒子的层叠结构体，
所述金属被覆层的组成以质量％计满足Zn：33～80％、Al：3～50％、Mg：8～45％、Ca：1～5％及Zn+Al＞Mg，
所述金属被覆层的组织包含准结晶相、MgZn2相和剩余部分组织，所述准结晶相与所述MgZn2相的合计面积分率为45％以上，所述剩余部分组织的面积分率为0～55％，所述准结晶相的面积分率为20％以上，所述MgZn2相的面积分率为10％以上。
2.根据权利要求1所述的含有Mg的Zn合金被覆钢材，其中，所述Al的含量以质量％计为3％以上且低于13％。
3.根据权利要求1或权利要求2所述的含有Mg的Zn合金被覆钢材，其中，具有覆盖所述金属粒子的表面的膜厚为1nm～1000nm的氧化皮膜。
4.根据权利要求1或权利要求2所述的含有Mg的Zn合金被覆钢材，其中，所述金属被覆层为喷镀被覆层。
5.根据权利要求1或权利要求2所述的含有Mg的Zn合金被覆钢材，其中，所述金属被覆层的组成以质量％计含有Y：0％～3.5％、La：0％～3.5％、Ce：0％～3.5％、Si：0％～3.5％、Ti：0％～0.5％、Cr：0％～0.5％、Co：0％～0.5％、Ni：0％～0.5％、V：0％～0.5％、Nb：0％～0.5％、Cu：0％～0.5％、Sn：0％～0.5％、Mn：0％～0.2％、Sr：0％～0.5％、Sb：0％～0.5％、Pb：0％～0.5％、C：0％～0.5％、Fe：0％～0.5％及Cd：0％～0.5％中的1种或2种以上，且满足下述式(A)及下述式(B)，
·式(A)：Ca+Y+La+Ce≤3.5％
·式(B)：Ti+Cr+Co+Ni+V+Nb+Cu+Sn+Mn+Sr+Sb+Pb+C+Fe+Cd≤0.5％
式(A)及式(B)中，元素符号表示以质量％计的各元素的含量。
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