CN103764865A - 金属镀覆钢带 - Google Patents

金属镀覆钢带 Download PDF

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Publication number
CN103764865A
CN103764865A CN201380001290.5A CN201380001290A CN103764865A CN 103764865 A CN103764865 A CN 103764865A CN 201380001290 A CN201380001290 A CN 201380001290A CN 103764865 A CN103764865 A CN 103764865A
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Prior art keywords
steel band
alloy layer
master alloy
alloy
metal plating
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CN201380001290.5A
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CN103764865B (zh
Inventor
刘启阳
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BlueScope Steel Ltd
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BlueScope Steel Ltd
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Priority claimed from AU2012903281A external-priority patent/AU2012903281A0/en
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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
    • 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
    • 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
    • B32B15/08—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 synthetic resin
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/003—Apparatus
    • C23C2/0034—Details related to elements immersed in bath
    • C23C2/00342—Moving elements, e.g. pumps or mixers
    • C23C2/00344—Means for moving substrates, e.g. immersed rollers or immersed bearings
    • 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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    • C23C2/004—Snouts
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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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    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
    • 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
    • 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
    • C23C2/12—Aluminium or alloys based thereon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18—Removing excess of molten coatings from elongated material
    • C23C2/20—Strips; Plates
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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    • 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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    • 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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

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

Abstract

一种金属镀覆钢带，所述金属镀覆钢带包含钢带和处于所述钢带至少一侧之上的金属镀层。所述金属镀层包含Al-Zn-Mg-Si覆盖合金层以及位于所述钢带与所述覆盖合金层之间的中间合金层。中间合金层的组成以重量计为：4.0%-12.0%Zn、6.0%-17.0%Si、20.0%-40.0%Fe、0.02%-0.50%Mg以及余量的Al和不可避免的杂质。

Description

金属镀覆钢带
技术领域
本发明涉及金属带材、特别是钢带的生产，该带材具有耐腐蚀金属镀层，所述镀层含有铝-锌-硅-锰作为主要元素，且在镀层合金中并非必然只有这些元素；基于此，下面称为“Al-Zn-Si-Mg合金”。
特别是，本发明涉及在带材上形成金属镀层的热浸镀覆方法，所述方法包括将未镀覆带材浸入熔融Al-Zn-Si-Mg合金浴中，在带材上形成所述合金的镀层。
通常，熔融Al-Zn-Si-Mg合金的组成包含具有如下范围（以wt%计）的Al、Zn、Si和Mg元素：
Zn：30%-60%
Si：0.3%-3%
Mg：0.3%-10%
余量的Al和不可避免的杂质。
更通常，熔融Al-Zn-Si-Mg合金的组成包含具有如下范围（以wt%计）的Al、Zn、Si和Mg元素：
Zn：35%-50%
Si：1.2%-2.5%
Mg：1.0%-3.0%
余量的Al和不可避免的杂质。
熔融Al-Zn-Si-Mg合金的组成可含有作为有意添加的合金添加剂或作为不可避免的杂质存在于熔融合金中的其它元素。因此，短语“Al-Zn-Si-Mg合金”在本文中应理解为涵盖包含这类其它元素（作为有意添加的合金添加剂或不可避免的杂质）的合金。举例来说，所述其它元素可包括Fe、Sr、Cr和V中的任意ー种或多种。
根据最终用途，可在金属镀覆带材的ー个或两个表面上涂覆例如聚合物涂料。就这一点而言，所述金属镀覆带材本身可作为最终产品出售，或者可具有施用至其ー个或两个表面上的涂料层并作为经涂覆的最终产品出售。
本发明具体但不排他地涉及钢带，该钢带具有由上述熔融Al-Zn-Si-Mg合金组成形成的金属镀层，并且任选涂覆有涂料，之后冷成型（例如轧制成型）为最终用途产品、例如建筑产品（例如型材壁和屋顶板）。
背景技术
在澳大利亚和其它地方广泛用于建筑产品、尤其是型材壁和屋顶板的ー种耐腐蚀金属镀覆浴组成为同时含有Si的55%A1-Zn合金镀层组成。该型材板通常通过将经涂覆的金属合金镀覆带材冷成型而制成。通常，通过将经涂覆的带材轧制成型制造该型材板。
在这种已知组成的55%A1-Zn-Si合金镀层组成中添加Mg已经于多年前在专利文献中提出，参见例如以Nippon Steel Corporation的名义申请的美国专利6,635,359，但在澳大利亚市场上，具有Al-Zn-Si-Mg镀层的钢带尚无法商购。
已经证实，当在55%A1-Zn-Si合金镀层组成中含有Mg时，Mg为产品性能带来一定的有益效果，例如改善了割边防护（cut-edge protection)。
本申请人进行了大量与带材（例如钢带）上的A1-Zn-Si-Mg合金镀层相关的研发工作。本发明是所述研发工作的部分结果。
上述讨论不应视为在澳大利亚或其它地区承认的公知常识。
发明内容
本发明基于本申请人在如下研发工作过程中的发现：在钢带上形成A1-Zn-Si-Mg合金镀层，从而在A1-Zn-Si-Mg合金镀层覆盖层和钢带之间存在具有选定组成以及优选的选定晶体结构的中间合金层，这样能够改善镀覆带材的腐蚀性能。所述研发工作还发现：能够改善镀覆带材腐蚀性能的中间合金层的选定组成和优选晶体结构并不是对用于热浸镀覆浴的A1-Zn-Si-Mg合金组成进行选择的必然结果，多种因素（例如但不限于：熔融A1-Zn-Si-Mg合金浴组成和热浸工艺条件、通常的带材浸渍时间和镀覆锅温度）均为形成具有所需组成和优选晶体结构的中间合金层的相关因素。
本发明提供了金属镀覆钢带，所述金属镀覆钢带包含钢带和处于该钢带至少一侧之上的金属镀层，所述金属镀层包含Al-Zn-Si-Mg覆盖合金层以及位于该钢带与该覆盖合金层之间的中间合金层，其中，该中间合金层的组成以重量计为：4.0%-12.0%Zn、6.0%-17.0%Si、20.0%-40.0%Fe、0.02%-0.50%Mg以及余量的Al和不可避免的杂质。
中间合金层可作为熔融Al-Zn-Mg-Si合金组成和钢带中的元素的金属间相形成。
或者，中间合金层和Al-Zn-Mg-Si覆盖合金层可作为单独的层形成。
中间合金层以重量计可包含：5.0%-10.0%Zn、7.0%-14.0%Si（通常为6.5%-14.0%Si）、25.0%-37.0%Fe、0.03%-0.25%Mg以及余量的Al和不可避免的杂质。
中间合金层以重量计可包含：6.0%-9.0%Zn、8.0%-12.0%Si、28.0%-35.0%Fe、0.05%-0.15%Mg以及余量的铝和不可避免的杂质。
中间合金层以重量计可包含0.01%-0.2%Ca。
中间合金层以重量计可包含0.1%-3.0%Cr。
中间合金层以重量计可包含0.1%-13.0%Mn。
中间合金层以重量计可包含0.1%-2.0%V。
中间合金层可具有0.1μm-5.0μm的厚度，所述厚度在贯穿镀层厚度的横截面上进行测量。
中间合金层可具有0.3μm-2.0μm的厚度，所述厚度在贯穿镀层厚度的横截面上进行测量。
中间合金层可具有0.5μm-1.0μm的厚度，所述厚度在贯穿镀层厚度的横截面上进行测量。
中间合金层可包含短径（short diameter）为50nm-1000nm的实质上为柱状的晶体，所述短径在贯穿镀层厚度的横截面上进行测量。
中间合金层可包含长径（long diameter）为50nm-4000nm的实质上为等轴的晶体，所述长径在贯穿镀层厚度的横截面上进行测量。
中间合金层可包含柱状晶体和等轴晶体的混合物。
中间合金层可包含体心立方晶体。
中间合金层的Al、Zn、Si和Fe的浓度可符合式Fe10Al32Si5Zn3。
中间合金层的Al、Zn、Si和Fe的浓度可符合式Fe10Al34Si4Zn2。
带材可为经钝化的带材，例如使用含有Cr或不含Cr的钝化体系。
带材可包含在Al-Zn-Mg-Si合金镀层的暴露表面上的树脂涂层。
用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含多于0.3wt%的Mg。
用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含多于1.0wt%的Mg。
用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含多于1.3wt%的Mg。
用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含多于1.5wt%的Mg。
用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含少于3wt%的Mg。
用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含少于2.5wt%的Mg。
用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含多于1.2wt%的Si。
用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含少于2.5wt%的Si。
用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含具有如下范围（以wt%计）的元素Al、Zn、Si和Mg：
Zn：30%-60%
Si：0.3%-3%
Mg：0.3%-10%
余量的Al和不可避免的杂质。
特别是，用于形成金属镀层的熔融Al-Zn-Si-Mg合金可包含具有如下范围（以wt%计）的元素Al、Zn、Si和Mg：
Zn：35%-50%
Si：1.2%-2.5%
Mg：1.0%-3.0%
余量的Al和不可避免的杂质。
所述钢可为低碳钢。
本发明还提供了在钢带上形成金属镀层，从而形成上述的金属镀覆钢带的方法，所述方法包括：将钢带浸入熔融Al-Zn-Si-Mg合金浴中，以及在该钢带的暴露表面上形成所述合金的金属镀层；并且所述方法包括对熔融合金浴的组成、熔融合金浴的温度和钢带在熔融合金浴中的浸渍时间三者中的任意一种或多种进行控制，从而在钢带和Al-Zn-Mg-Si覆盖合金层之间形成中间合金层。
熔融Al-Zn-Si-Mg合金可具有上述组成。例如，熔融Al-Zn-Si-Mg合金可包含具有如下范围（以wt%计）的元素Al、Zn、Si和Mg：
Zn：30%-60%
Si：0.3%-3%
Mg：0.3%-10%
余量的Al和不可避免的杂质。
附图说明
例如，通过参考如下附图对本发明作进ー步说明，其中：
图1为示出用于根据本发明方法生产Al-Zn-Si-Mg合金镀覆钢带的连续作业线的一个实施方式的示意图；
图2为已知的钢带上Al-Zn-Si合金镀层和本发明所述的钢带上Al-Zn-Si-Mg合金镀层的样品的Q-Fog寿命（以小时计，至5%表面红锈的时间）的图；
图3显示了针对已知的钢带上Al-Zn-Si合金镀层和本发明所述的钢带上Al-Zn-Si-Mg合金镀层的样品进行进一步实验工作的结果；
图4显示了针对本发明所述的钢带上Al-Zn-Si-Mg合金镀层的样品进行进一步实验工作的结果；
图5显示了针对本发明所述的钢带上的Al-Zn-Si-Mg合金镀层和Al-Zn-Si-Mg-Cr合金镀层的样品进行进一步实验工作的结果；
图6为示出锅温对中间合金层的组成以及转而对镀覆有相同Al-Zn-Si-Mg合金的样品的Q-Fog质量损失的影响的图；
图7为实验结果的图，该图示出了Al-Zn-Si-Mg合金镀覆浴组成中的Mg和Si对本发明所述的金属镀覆带材样品的中间合金层质量的影响；
图8为相对于在用于形成在样品上的镀层的镀覆浴中的浸渍时间而言，本发明所述金属镀覆带材样品和其它金属镀覆钢带样品的中间合金层厚度的图；以及
图9为相对于样品上的覆盖合金层厚度而言，本发明所述的金属镀覆带材样品的中间合金层厚度的图。
具体实施方式
参考图1中概括示出的用于镀覆钢带的连续作业线，在使用中，在开卷工段1将冷轧低碳钢带卷开卷，然后通过焊接机2将连续开卷长度的带材头尾焊接以形成连续长度的带材。
然后，所述带材连续通过积累器3、带材清洁段4和炉组件5。所述炉组件5包含预热器、预热还原炉和还原炉。
通过控制工艺变量，在炉组件5中对带材进行热处理，所述工艺变量包括：（i）炉中的温度曲线；（ii）炉中的还原气体浓度；（iii）通过炉的气体流量；以及（iv）带材在炉中的停留时间（即线速度）。
控制炉组件5中的工艺变量，使得从带材表面去除氧化铁残余物并从带材表面清除残余的油和铁屑。
然后，使经过热处理的带材向下通过出口炉嘴，通入并且穿过装在镀覆锅6中的包含Al-Zn-Si-Mg合金的熔融浴，使带材镀覆有熔融Al-Zn-Si-Mg合金。通过使用加热感应器（未示出）或其它合适的加热选项，使Al-Zn-Si-Mg合金在选定温度下于镀覆锅中保持熔融。在浴内，带材绕着处于浴中的浸入导辊（未示出）并从浴中向上穿出。所选定的线速度为带材在镀覆浴中提供选定的浸渍时间。在带材穿过浴时，它的两个表面均镀覆熔融Al-Zn-Si-Mg合金。
在离开镀覆浴6后，带材垂直通过气刮工段（未示出），带材的镀覆表面在该工段处受到刮擦气体的喷射，以控制镀层的厚度。
然后，镀覆带材通过冷却段7并且受到强制冷却。
冷却的镀覆带材通过轧制段8，精整镀覆带材的表面。
之后在卷取工段10处卷取所述镀覆带材。
如上文所讨论，本申请人进行了大量的与钢带上的A1-Zn-Si-Mg合金镀层相关的研发工作，并发现：形成包含覆盖合金层和中间合金层的金属镀层能够改善金属镀覆带材的腐蚀性能，所述中间合金层在覆盖层和钢带之间，具有选定的组成以及优选的选定晶体结构。
所述研发工作包括用下述熔融合金组成对钢带样品进行热浸镀覆的工作：（a）已知的Al-Zn-Si合金（以下称为“AZ”）；（b）本发明所述的Al-Zn-Si-Mg合金（以下称为“MAZ”）；以及（c）本发明所述的MAZ合金加上0.1wt%的Cr；各合金具有下述熔融合金组成（以wt%计）：
·AZ：55Al-43Zn-1.5Si-0.45Fe-附带的杂质。
·MAZ：53Al-43Zn-2Mg-1.5Si-0.45Fe-附带的杂质。
·MAZ+0.1wt%Cr-附带的杂质。
以125g/m2和150g/m2的双侧镀层质量，将熔融合金镀覆至钢带样品的暴露表面。一组样品在本申请人的Wollongong工厂的金属镀覆线（“MCL”）上生产；另一组样品由本申请人在Wollongong的研究设施中的热浸工艺模拟机（“HDPS”）上生产。实验工作主要在HDPS上进行。HDPS是由Iwatani International Corp(Europe)GmbH根据本申请人的技术要求而建造的最先进的装置。该HDPS装置包括熔融金属锅炉、红外加热炉、气刮喷嘴、除渣结构、气体混合和露点控制模块、以及计算机化的自动控制系统。该HDPS装置能够模拟传统金属镀覆线上的常见的热浸循环（hot dip cycle）。
对镀覆样品进行耐腐蚀性测试（Q-Fog循环腐蚀测试性能），并使用扫描电子显微镜和其它分析仪器进行微结构分析。
图2为下列样品的Q-Fog寿命（以小时计，至5%表面红锈的时间）的图：
·MCL AZ150——金属镀覆线上生产的双侧镀层质量为150g/m2的AZ合金镀层。
·MCL MAZ125——金属镀覆线上生产的双侧镀层质量为125g/m2的MAZ合金镀层。
·HDPS MAZ125——在热浸工艺模拟机上生产的双侧镀层质量为125g/m2的MAZ合金镀层。
·HDPS MAZ125+0.1%Cr——在热浸工艺模拟机上生产的双侧镀层质量为125g/m2的MAZ+0.1%Cr合金镀层。
由图2可明显看出，MAZ合金镀层样品具有显著更长的Q-Fog寿命，因此相比于AZ合金镀层样品具有显著更好的耐腐蚀性，而MAZ+0.1%Cr样品在所有样品中具有最佳的性能。
图2阐明了由于向AZ中添加Mg形成MAZ合金，耐腐蚀性得以改善。图2还阐明了向MAZ合金中少量添加0.1%Cr，在耐腐蚀性方面产生了进一步的显著改善。
图3进一步阐明了与AZ合金镀层相比，Mg对MAZ合金镀层在抗腐蚀性方面改善的贡献。图3中示出的结果是对下列样品进行的实验工作的结果：
·MCL AZ150——金属镀覆线上生产的双侧镀层质量为150g/m2的AZ合金镀层。
·MCL MAZ125——金属镀覆线上生产的双侧镀层质量为125g/m2的MAZ合金镀层。
图3的左侧是两幅贯穿两个样品厚度的截面的SEM背散射电子图像。图3的右侧是样品的Q-Fog寿命（以小时计，至5%表面红锈的时间）图。两个样品在相同的金属镀覆线上生产。所述SEM图像显示出，由于MAZ合金中Mg的存在，样品具有不同的镀层微结构。所述SEM图像还显示出，两个样品的镀层均包含覆盖合金层11以及在钢带13（在附图中称为“基底钢”）和所述覆盖层11之间的中间合金层12（在该图和其它图中称为“合金层”）。中间合金层是由熔融合金浴和钢带中的元素形成的金属间层（intermetallic layer）。右图显示出，MAZ合金镀层样品具有显著更长的Q-Fog寿命，因此比起AZ合金镀层样品具有显著更好的耐腐蚀性；这可能是由于在MAZ合金镀层覆盖层的微结构中存在Al/Zn/MgZn2共晶体和Mg2Si相，但中间层可能也会对腐蚀性能的差异有贡献。
图4示出了针对MAZ合金镀层进行进一步实验工作的结果，所述结果着眼于下列样品的中间合金层12的贡献，所述中间合金层12位于钢带13和覆盖合金层11之间：
·MCL MAZ125——金属镀覆线上生产的双侧镀层质量为125g/m2的MAZ合金镀层。
·HDPS MAZ125——在热浸工艺模拟机上生产的双侧镀层质量为125g/m2的MAZ合金镀层。
图4的左侧是两幅贯穿两个样品厚度的截面的SEM背散射电子图像。图4的右侧是样品的Q-Fog寿命（以小时计，至5%表面红锈的时间）的图。两个样品均用相同的熔融合金组成-MAZ合金进行镀覆。一个样品在金属镀覆线上生产，而另一样品在热浸工艺模拟机上生产。两个样品具有实质上相同的镀层厚度（约18微米）。右图显示出，HDPS MAZ125合金镀层样品具有显著更长的Q-Fog寿命，因此比起MCL MAZ125合金镀层样品具有显著更好的耐腐蚀性。所述SEM图像显示出，由于更长的浸渍时间（在HDPS上为2.5秒，而在MCL上为1.0秒），HDPS MAZ125镀层样品具有比MCL MAZ125镀层样品更厚的中间合金层。图4说明，中间合金层12有助于HDPS MAZ125镀层样品具有更佳的耐腐蚀性，即，更厚的中间合金层12提供了更长的Q-Fog寿命。
图5示出了进一步实验工作的结果，该实验工作着眼于下列样品中的Cr对腐蚀性能的贡献：
·HDPS MAZ125+0.1%Cr——在热浸工艺模拟机上生产的双侧镀层质量为125g/m2的MAZ+0.1%Cr合金镀层。
·HDPS MAZ125——在热浸工艺模拟机上生产的双侧镀层质量为125g/m2的MAZ合金镀层。
图5的左侧是贯穿两个样品厚度的截面的两幅SEM背散射电子图像和两幅SEM-EDS元素分布图，显示了截面的微结构和Cr在整个截面中的分布。图5的右侧是样品的Q-Fog寿命（以小时计，至5%表面红锈的时间）的图。两个样品均在热浸工艺模拟机上生产。两个样品具有实质上相同的镀层厚度和实质上相同的中间合金层厚度。实际上，样品间的唯一差别是其中一个样品含有0.1%的Cr。由右图可明显看出，Cr使得HDPS MAZ125+0.1%Cr合金镀层样品具有显著更长的Q-Fog寿命，因此比起HDPS MAZ125合金镀层样品而言具有显著更好的耐腐蚀性。由所述SEM-EDS分布图也可明显看出，HDPS MAZ125+0.1%Cr合金镀层样品的中间合金层中具有更高浓度的Cr。由此可知，HDPS MAZ125+0.1%Cr镀层样品的中间合金层中的Cr有助于改善该样品的耐腐蚀性。
研发工作包括：为了确定中间合金层借助于中间金属层的组成、或借助于中间合金层的晶体结构，对Al-Zn-Si-Mg合金镀层耐腐蚀性的贡献而进行的大量工作。
该工作认定，中间合金层的下列组成范围（以重量计）提供了最佳的Al-Zn-Si-Mg合金镀层腐蚀性能：
Zn：4.0%-12.0%；
Si：6.0%-17.0%；
Fe:20.0%-40.0%；
Mg：0.02%-0.50%；
余量的Al和不可避免的杂质。
在镀层的中间合金层的上述组成范围之外，Al-Zn-Si-Mg合金镀层的腐蚀性能较差。
中间合金层的上述组成范围通过钢样品上的Al-Zn-Si-Mg合金镀层的大量测试（包括但不限于，通过Q-Fog测试和室外暴露得到镀层腐蚀、通过T弯曲测试得到镀层延展性等）而得以确定；所述测试在AZ+0-5.0%Si、0-5.0%Mg、0-0.1%Cr、0-0.4%Mn、0-0.1%V和0-0.1%Ca范围内的熔融合金浴组成、在0.3-20秒的带材浸渍时间和595℃-640℃的锅温下进行，从而认定提供所期望性能的样品。使用不同的分析技术，从而（a）研究中间合金层的化学组成、厚度和晶体结构，并且（b）增进对于影响最终镀覆产品性能的中间合金层的关键性质的理解。图2至图9是该研发工作结果的样本。
研发工作还发现，中间合金层的上述组成范围并不是对熔融A1-Zn-Si-Mg合金浴组成进行选择的必然结果，并发现一些因素（例如但不限于，熔融A1-Zn-Si-Mg合金组成和热浸工艺条件、通常的带材浸渍时间和镀覆锅温度）均为形成具有所需组成的中间合金层的相关因素。特别是，虽然对本领域技术人员来说不一定显而易见，但是附图中所示的中间合金层的化学组成、厚度和晶体结构相互关联，并作为整体而有助于镀覆带材的性能。
图6为示出镀覆锅温度对两种Al-Zn-Si-Mg合金镀层的中间合金层组成以及转而对Q-Fog质量损失的影响的图。在两个不同的锅温（分别为600℃和620℃）下，使用相同的镀覆浴熔融Al-Zn-Si-Mg合金和相同的浸渍温度（1秒）制备样品。对镀覆样品进行分析，以确定中间合金层的组成。中间合金层的组成在图6中的柱状图下方的表中示出。在该表中还给出了中间合金层的厚度。对样品进行相同的Q-Fog腐蚀测试程序。图6显示出600℃和620℃的锅温产生了不同的中间合金层组成。在620℃的锅温下，中间金属层的组成处于本发明的组成范围（特别是，Si<6%）以外。因此，尽管具有更大的中间合金层厚度（如果该中间合金层的组成与600℃锅温下的组成相同、或处于本发明的范围内，这将是有利的），但是Al-Zn-Si-Mg合金镀层的腐蚀性能受损。使用电感耦合等离子体光谱（ICP）技术对中间合金层的组成进行分析。根据这一技术，首先通过将样品浸于受亚砷酸钠（9g/升）抑制的1:9HCl水溶液中来移除Al-Zn-Si-Mg合金镀层覆盖层；然后，使用抑制的HCl溶液溶解中间合金层；再通过ICP对所得到的溶液进行分析。
图7为相对于用于形成样品镀层的Al-Zn-Si-Mg合金镀覆浴中的Mg和Si的浓度而言，在本发明所述的相同的热浸工艺条件（在600℃的锅温下，浸渍时间为1秒）下获得的金属镀覆钢带样品的中间合金层的质量的图。图7显示出：随着镀覆浴中的Mg和Si的浓度增高，中间合金层的质量降低。
图8为相对于在用于形成样品镀层的镀层合金镀覆浴中的浸渍时间而言，本发明所述的金属镀覆带材样品的中间合金层的厚度的图。图8给出了针对3种不同的熔融合金浴组成的工作结果。一种熔融合金是已知的Al-Zn-Si合金（图中的“AZ”合金）。另一种熔融合金是本发明所述的还含有Ca的Al-Zn-Si-Mg合金（图中的“AMCa合金”）。第三种熔融合金是已知的具有5.0%Mg和4.0%Si的Al-Zn-Si-Mg合金（图中的“5.0%Mg4.0%Si”合金）。图8显示出：熔融合金浴组成和在熔融合金浴中的浸渍时间均会影响镀覆钢带的中间合金层的厚度。
图9为相对于样品镀层的覆盖合金层厚度而言，本发明所述的金属镀覆带材样品镀层的中间合金层厚度的图。图9显示出：中间合金层厚度随覆盖合金层厚度的增加而增加。由图9可知，为此希望使整个镀覆带材表面的任何镀层质量变化最小化，以维持均匀的腐蚀性能。
除了中间合金层借助于该中间合金层的组成和/或厚度对Al-Zn-Si-Mg合金镀层的腐蚀性能所作出的直接贡献外，申请人还发现，中间合金层的晶体结构可通过裂痕间接地影响整个MAZ合金镀层的腐蚀性能。申请人发现，当对Al-Zn-Mg-Si合金镀覆带材进行高应变操作（例如轧制成型）时，中间合金层是产生裂痕的一个重要来源。粗糙的中间合金层晶体结构导致更宽范围和更多数量的裂痕侵入镀层的覆盖合金层，Al-Zn-Mg-Si合金镀覆带材的腐蚀性能变差。虽然中间合金层可包含等轴晶体、柱状晶体、或等轴晶体和柱状晶体的混合物，但是为了使裂痕最少化，希望控制柱状晶体的尺寸在短径方面不大于1000nm（针对贯穿镀层厚度的横截面进行测量）；和/或等轴晶体的尺寸在长径方面不大于4000nm（针对贯穿镀层厚度的横截面进行测量）。
从腐蚀性能的角度来看，虽然期望存在实在的中间合金层（或不薄于0.1μm），但是如果中间合金层过厚（或厚于5μm）是不利的，因为中间合金层过厚会引发裂痕并损害镀覆带材的可轧制成型性。
在不背离本发明精神和范围的情况下，可对上述的本发明作出各种修改。
举例来说，尽管与图2至图9相关的上述研发工作着眼于由特定的Al-Zn-Si-Mg合金的镀覆浴形成的镀层，但是本发明并不限于这些特定的合金。

Claims (26)

1.一种金属镀覆钢带，所述金属镀覆钢带包含钢带和处于所述钢带至少一侧之上的金属镀层，所述金属镀层包含Al-Zn-Mg-Si覆盖合金层以及位于所述钢带和所述覆盖合金层之间的中间合金层，其中，所述中间合金层的组成以重量计为：4.0%-12.0%Zn、6.0%-17.0%Si、20.0%-40.0%Fe、0.02%-0.50%Mg以及余量的Al和不可避免的杂质。
2.如权利要求1所述的钢带，其中，所述中间合金层以重量计含有0.01%-0.2%Ca。
3.如权利要求1或2所述的钢带，其中，所述中间合金层以重量计含有0.1%-3.0%Cr。
4.如前述权利要求中任一项所述的钢带，其中，所述中间合金层以重量计含有0.1%-13.0%Mn。
5.如前述权利要求中任一项所述的钢带，其中，所述中间合金层以重量计含有0.1%-2.0%V。
6.如前述权利要求中任一项所述的钢带，其中，所述中间合金层具有0.1μm-5.0μm的厚度，所述厚度在贯穿所述镀层厚度的横截面上进行测量。
7.如权利要求6所述的钢带，其中，所述中间合金层具有0.3μm-2.0μm的厚度，所述厚度在贯穿所述镀层厚度的横截面上进行测量。
8.如权利要求7所述的钢带，其中，所述中间合金层具有0.5μm-1.0μm的厚度，所述厚度在贯穿所述镀层厚度的横截面上进行测量。
9.如前述权利要求中任一项所述的钢带，其中，所述中间合金层包含短径为50nm-1000nm的实质上为柱状的晶体，所述短径在贯穿所述镀层厚度的横截面上进行测量。
10.如权利要求1-8中任一项所述的钢带，其中，所述中间合金层包含长径为50nm-4000nm的实质上为等轴的晶体，所述长径在贯穿所述镀层厚度的横截面上进行测量。
11.如权利要求1-8中任一项所述的钢带，其中，所述中间合金层包含柱状晶体和等轴晶体的混合物。
12.如权利要求1-8中任一项所述的钢带，其中，所述中间合金层包含体心立方晶体。
13.如前述权利要求中任一项所述的钢带，其中，所述中间合金层的Al、Zn、Si和Fe的浓度符合式Fe10Al32Si5Zn3。
14.如前述权利要求中任一项所述的钢带，其中，所述中间合金层的Al、Zn、Si和Fe的浓度符合式Fe10Al34Si4Zn2。
15.如前述权利要求中任一项所述的钢带，其中，所述钢带是使用含Cr或不含Cr的钝化体系进行钝化后的钢带。
16.如前述权利要求中任一项所述的钢带，所述钢带包含位于所述金属镀层的暴露表面上的树脂涂层。
17.如前述权利要求中任一项所述的钢带，其中，用于形成所述金属镀层的熔融Al-Zn-Si-Mg合金包含多于0.3wt%的Mg。
18.如前述权利要求中任一项所述的钢带，其中，用于形成所述金属镀层的熔融Al-Zn-Si-Mg合金包含多于1.0wt%的Mg。
19.如前述权利要求中任一项所述的钢带，其中，用于形成所述金属镀层的熔融Al-Zn-Si-Mg合金包含多于1.3wt%的Mg。
20.如前述权利要求中任一项所述的钢带，其中，用于形成所述金属镀层的熔融Al-Zn-Si-Mg合金包含多于1.5wt%的Mg。
21.如前述权利要求中任一项所述的钢带，其中，用于形成所述金属镀层的熔融Al-Zn-Si-Mg合金包含少于3wt%的Mg。
22.如前述权利要求中任一项所述的钢带，其中，用于形成所述金属镀层的熔融Al-Zn-Si-Mg合金包含少于2.5wt%的Mg。
23.如前述权利要求中任一项所述的钢带，其中，用于形成所述金属镀层的熔融Al-Zn-Si-Mg合金包含多于1.2wt%的Si。
24.如前述权利要求中任一项所述的钢带，其中，用于形成所述金属镀层的熔融Al-Zn-Si-Mg合金包含以重量百分比计具有如下范围的元素Al、Zn、Si和Mg：
Zn：30%-60%
Si：0.3%-3%
Mg：0.3%-10%
余量的Al和不可避免的杂质。
25.如前述权利要求中任一项所述的钢带，其中，用于形成所述金属镀层的熔融Al-Zn-Si-Mg合金包含以重量百分比计具有如下范围的元素Al、Zn、Si和Mg：
Zn：35%-50%
Si：1.2%-2.5%
Mg：1.0%-3.0%
余量的Al和不可避免的杂质。
26.一种在钢带上形成金属镀层，从而形成前述权利要求中任一项所述的金属镀覆钢带的方法，所述方法包括将钢带浸入熔融Al-Zn-Si-Mg合金的浴中，在所述钢带的暴露表面上形成所述合金的金属镀层；并且所述方法包括对所述熔融合金浴的组成、所述熔融合金浴的温度和所述钢带在所述熔融合金浴中的浸渍时间三者中的任意一种或多种进行控制，从而在所述钢带和所述Al-Zn-Mg-Si覆盖合金层之间形成所述中间合金层。
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