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TWI724674B - Melting Al-Zn-Mg-Si-Sr coated steel sheet and manufacturing method thereof - Google Patents

Melting Al-Zn-Mg-Si-Sr coated steel sheet and manufacturing method thereof Download PDF

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TWI724674B
TWI724674B TW108144608A TW108144608A TWI724674B TW I724674 B TWI724674 B TW I724674B TW 108144608 A TW108144608 A TW 108144608A TW 108144608 A TW108144608 A TW 108144608A TW I724674 B TWI724674 B TW I724674B
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TW202033791A (en
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飛山洋一
三宅英徳
大居利彦
岩野純久
菅野史嵩
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日商杰富意鋼板股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
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    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12Aluminium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
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    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26After-treatment
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C18/00Alloys based on zinc
    • C22C18/04Alloys based on zinc with aluminium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C21/00Alloys based on aluminium
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    • C23COATING 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
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    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06Zinc or cadmium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C23C2/28Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29Cooling or quenching
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    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34Hot-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
    • C23C2/36Elongated material
    • C23C2/40Plates; Strips

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Abstract

本發明的目的在於提供一種具有良好的表面外觀性、並且平板部及加工部的耐蝕性優異的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板。為了達成所述目的,本發明的特徵在於:鍍覆層含有Al:40質量%~70質量%、Si:0.6質量%~5質量%、Mg:0.1質量%~10質量%及Sr:0.001質量%~1.0質量%,且具有剩餘部分包含Zn及不可避免的雜質的組成,所述鍍覆層包含存在於與基底鋼板的界面的界面合金層、及存在於所述合金層上的主層,於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2 Si中,自所述主層的表面至50%為止的厚度範圍內所存在的Mg2 Si的面積比例為50%以上,且自所述主層的表面起延伸至到達所述界面合金層為止的Mg2 Si的面積比例為50%以下。The object of the present invention is to provide a molten Al-Zn-Mg-Si-Sr coated steel sheet having good surface appearance and excellent corrosion resistance of the flat portion and the processed portion. In order to achieve the objective, the present invention is characterized in that the plating layer contains Al: 40% by mass to 70% by mass, Si: 0.6% by mass to 5% by mass, Mg: 0.1% by mass to 10% by mass, and Sr: 0.001% by mass % To 1.0% by mass, with the remainder including Zn and unavoidable impurities, the plating layer includes an interface alloy layer existing at the interface with the base steel sheet, and a main layer existing on the alloy layer, In the Mg 2 Si observed in the cross section in the thickness direction of the plating layer, the area ratio of Mg 2 Si existing in the thickness range from the surface of the main layer to 50% is 50% or more, And the area ratio of Mg 2 Si extending from the surface of the main layer to reaching the interface alloy layer is 50% or less.

Description

熔融Al-Zn-Mg-Si-Sr鍍覆鋼板及其製造方法Melting Al-Zn-Mg-Si-Sr coated steel sheet and manufacturing method thereof

本發明是有關於一種具有良好的表面外觀性、並且平板部及加工部的耐蝕性優異的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板及其製造方法。 The present invention relates to a molten Al-Zn-Mg-Si-Sr plated steel sheet having good surface appearance and excellent corrosion resistance of the flat portion and the processed portion, and a manufacturing method thereof.

熔融Al-Zn系鍍覆鋼板可兼顧Zn的犧牲防蝕性與Al的高耐蝕性,因此於熔融鍍鋅鋼板中亦顯示出高的耐蝕性。例如,於專利文獻1中揭示出一種在鍍覆層中含有25質量%~75質量%的Al的熔融Al-Zn系鍍覆鋼板。而且,熔融Al-Zn鍍覆鋼板由於其優異的耐蝕性,因此以長期暴露於室外的房頂或牆壁等建材領域、護欄(guardrail)、配線配管、隔音牆等土木建築領域為中心,近年來需求擴大。 The molten Al-Zn-based coated steel sheet can take into account the sacrificial corrosion resistance of Zn and the high corrosion resistance of Al, so it also shows high corrosion resistance in the hot-dip galvanized steel sheet. For example, Patent Document 1 discloses a molten Al-Zn-based coated steel sheet containing 25% by mass to 75% by mass of Al in the coating layer. Moreover, because of its excellent corrosion resistance, molten Al-Zn coated steel sheets have been exposed to long-term outdoor building materials such as roofs or walls, guardrails, wiring piping, sound insulation walls and other civil engineering fields. In recent years, Demand is expanding.

熔融Al-Zn系鍍覆鋼板的鍍覆層包含主層、及存在於基底鋼板與主層的界面的界面合金層,主層主要包含:含有Zn的Al進行枝晶(dendrite)凝固的部分(α-Al相的枝晶部分)、以及以Zn為主成分的剩餘的枝晶間隙的部分(枝晶間),且具有將α-Al相在鍍覆層的膜厚方向上積層多個而成的結構。藉由此種特徵性的皮膜結構,來自表面的腐蝕行進路徑變得複雜,因此腐蝕難以容易地到達基底鋼板,熔融Al-Zn系鍍覆鋼板與鍍覆層厚相同的 熔融鍍鋅鋼板相比,可實現優異的耐蝕性。 The coating layer of the molten Al-Zn-based plated steel sheet includes a main layer and an interface alloy layer existing at the interface between the base steel sheet and the main layer. The main layer mainly includes: the part where Al containing Zn undergoes dendrite solidification ( The dendrite part of the α-Al phase) and the remaining part of the dendrite gap (interdendritic) mainly composed of Zn, and the α-Al phase is laminated in the thickness direction of the coating layer. Into the structure. With this characteristic film structure, the corrosion path from the surface becomes complicated, so it is difficult for corrosion to reach the base steel sheet easily. The molten Al-Zn-based coated steel sheet has the same thickness as the coating layer. Compared with hot-dip galvanized steel sheet, it can achieve superior corrosion resistance.

另外,已知有藉由在熔融Al-Zn系鍍覆鋼板的鍍覆層中含有Mg,而旨在進一步提升耐蝕性的技術。作為關於含有Mg的熔融Al-Zn系鍍覆鋼板(熔融Al-Zn-Mg-Si鍍覆鋼板)的技術,例如於專利文獻2中揭示了一種如下的Al-Zn-Mg-Si鍍覆鋼板,其包含在鍍覆層中含有Mg的Al-Zn-Si合金,該Al-Zn-Si合金為含有45重量%~60重量%的元素鋁、37重量%~46重量%的元素鋅及1.2重量%~2.3重量%的元素矽的合金,該Mg的濃度為1重量%~5重量%。 In addition, there is known a technique aimed at further improving corrosion resistance by including Mg in the plating layer of the molten Al-Zn-based plated steel sheet. As a technology for molten Al-Zn-based coated steel sheet containing Mg (fused Al-Zn-Mg-Si coated steel sheet), for example, Patent Document 2 discloses the following Al-Zn-Mg-Si coated steel sheet , Which contains the Al-Zn-Si alloy containing Mg in the coating layer, the Al-Zn-Si alloy contains 45% to 60% by weight of element aluminum, 37% to 46% by weight of element zinc, and 1.2 An alloy of elemental silicon with a weight% to 2.3 weight %, and the Mg concentration is 1 weight% to 5 weight %.

其中,關於引用文獻2中所揭示的含有Mg的熔融Al-Zn系鍍覆鋼板,存在如下問題:雖然具有優異的耐蝕性,但容易產生由在鍍覆層的表面所生成的氧化物層引起的數mm~數百mm左右長度的褶皺狀的缺陷(以下,稱為「褶皺狀缺陷」),並損害鍍覆層表面的外觀。 Among them, the molten Al-Zn coated steel sheet containing Mg disclosed in Citation 2 has the following problem: Although it has excellent corrosion resistance, it is likely to be caused by an oxide layer formed on the surface of the coating layer. Wrinkle-like defects (hereinafter referred to as "wrinkle-like defects") with a length of about several mm to several hundred mm (hereinafter referred to as "wrinkle-like defects") impair the appearance of the coating surface.

因此,例如於專利文獻3中,關於熔融Al-Zn-Mg系鍍覆鋼板,揭示了一種藉由使鍍覆層中含有Sr來實現表面外觀性的提升的技術。 Therefore, for example, in Patent Document 3, regarding a molten Al-Zn-Mg-based plated steel sheet, a technique for improving the surface appearance by including Sr in the plating layer is disclosed.

另外,於專利文獻4中,關於熔融Al-Zn-Mg系鍍覆鋼板,揭示了一種藉由使鍍覆層中含有Sr來實現加工性的提升的技術。 In addition, in Patent Document 4, regarding the molten Al-Zn-Mg-based plated steel sheet, a technique for improving the workability by including Sr in the plating layer is disclosed.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

專利文獻1:日本專利特公昭46-7161號公報 Patent Document 1: Japanese Patent Publication No. 46-7161

專利文獻2:日本專利5020228號公報 Patent Document 2: Japanese Patent No. 5020228

專利文獻3:日本專利3983932號公報 Patent Document 3: Japanese Patent No. 3983932

專利文獻4:日本專利6368730號公報 Patent Document 4: Japanese Patent No. 6368730

所述專利文獻3及專利文獻4的熔融Al-Zn-Mg系鍍覆鋼板由於在鍍覆層中含有Sr,因此可抑制褶皺狀缺陷的產生,從而實現表面外觀性的提升。 The molten Al-Zn-Mg-based plated steel sheets of Patent Document 3 and Patent Document 4 contain Sr in the coating layer, so that the generation of wrinkle-like defects can be suppressed, and the surface appearance can be improved.

然而,關於引用文獻3及引用文獻4的含有Sr的熔融Al-Zn-Mg系鍍覆鋼板,藉由含有Sr,而鍍覆層表面附近的Mg2Si的含量減少,作為其結果,有耐蝕性降低之虞。 However, regarding the molten Al-Zn-Mg coated steel sheet containing Sr in Citation 3 and Citation 4, by containing Sr, the content of Mg 2 Si near the surface of the coating layer is reduced. As a result, there is corrosion resistance. The risk of decreased sex.

另外,於專利文獻2及專利文獻3中所揭示的熔融Al-Zn系鍍覆鋼板中,雖然於鍍覆層中所生成的Mg2Si發揮耐蝕性的提升效果,但進行彎曲加工時鍍覆層破裂而產生裂紋,結果有加工部的耐蝕性(加工部耐蝕性)差的問題。 In addition, in the molten Al-Zn-based plated steel sheets disclosed in Patent Document 2 and Patent Document 3, although Mg 2 Si formed in the plating layer exhibits the effect of improving the corrosion resistance, the plating is performed during bending. The layer is broken and cracks are generated. As a result, there is a problem that the corrosion resistance of the processed part (corrosion resistance of the processed part) is poor.

本發明鑒於所述情況,目的在於提供一種具有良好的表面外觀性、並且平板部及加工部的耐蝕性優異的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板、以及平板部及加工部的耐蝕性優異的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法。 In view of the above-mentioned circumstances, the present invention aims to provide a molten Al-Zn-Mg-Si-Sr plated steel sheet with good surface appearance and excellent corrosion resistance of the flat part and the processed part, as well as the flat part and the processed part. A method for manufacturing molten Al-Zn-Mg-Si-Sr coated steel sheet with excellent corrosion resistance.

本發明者等人為了解決所述課題而進行了研究,結果著眼於:由含有Mg所帶來的耐蝕性提升效果是藉由當鍍覆層腐蝕 時,存在於鍍覆層中的Mg2Si優先溶解,且溶解於在鍍覆層表面所生成的腐蝕產物中的Mg發生濃化而發現,因此,鍍覆層的表面附近所存在的Mg2Si更重要。而且,進一步反覆進行了努力研究,結果發現:藉由將構成鍍覆層的主層(以後,有時亦稱為「鍍覆主層」或「主層」)中所含有的Mg2Si中的大部分集中於鍍覆主層的表面附近,即便於使鍍覆層中含有Sr的情況下,亦於鍍覆層表面存在充分的Mg2Si,因此,不僅可抑制褶皺狀缺陷的產生,亦可實現優異的耐蝕性。 The inventors of the present invention conducted studies to solve the above-mentioned problems, and as a result, they focused on the improvement effect of corrosion resistance brought about by the inclusion of Mg due to the presence of Mg 2 Si in the plating layer when the plating layer is corroded. Mg that is preferentially dissolved and dissolved in corrosion products formed on the surface of the plating layer is found to be concentrated. Therefore, Mg 2 Si present near the surface of the plating layer is more important. In addition, further studies have been carried out repeatedly, and as a result, it has been found that the Mg 2 Si contained in the main layer (hereinafter, sometimes referred to as "plating main layer" or "main layer") constituting the plating layer Most of it is concentrated near the surface of the main plating layer. Even when Sr is contained in the plating layer, there is sufficient Mg 2 Si on the surface of the plating layer. Therefore, it not only suppresses the occurrence of wrinkle defects, but also It can also achieve excellent corrosion resistance.

另外,本發明者等人著眼於:所述鍍覆主層中的Mg2Si雖然具有耐蝕性提升效果,但在彎曲加工時成為於界面合金層內產生的裂紋朝鍍覆主層表面傳播的路徑,使加工性降低,因此無法獲得所期望的加工部的耐蝕性。而且發現:藉由減少自界面合金層起到達鍍覆主層表面為止般的Mg2Si的量,可抑制在鋼板加工時以界面合金層為起點而產生的裂紋貫穿鍍覆主層並傳播至鍍覆主層表面為止,因此,關於加工部的耐蝕性,亦能夠得到提升。 In addition, the inventors of the present invention focused on that although the Mg 2 Si in the main plating layer has a corrosion resistance improvement effect, cracks generated in the interface alloy layer propagate to the surface of the main plating layer during bending. The route reduces the workability, and therefore the desired corrosion resistance of the processed part cannot be obtained. It was also discovered that by reducing the amount of Mg 2 Si from the interface alloy layer to the surface of the main plating layer, cracks generated from the interface alloy layer as a starting point during steel sheet processing can be prevented from penetrating the main plating layer and propagating to the main plating layer. Since the surface of the main layer is plated, the corrosion resistance of the processed part can also be improved.

本發明是基於以上見解而完成者,其主旨如下。 The present invention was completed based on the above knowledge, and its gist is as follows.

1.一種熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,其特徵在於:鍍覆層含有Al:40質量%~70質量%、Si:0.6質量%~5質量%、Mg:0.1質量%~10質量%及Sr:0.001質量%~1.0質量%,且具有剩餘部分包含Zn及不可避免的雜質的組成,所述鍍覆層包含存在於與基底鋼板的界面的界面合金層、及存在於該界面合金層上的主層, 於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中,自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例為50%以上,且自所述界面合金層至所述主層表面為止於枝晶間部連續存在(以下,有時稱為「延伸」)的Mg2Si的面積比例為50%以下。 1. A molten Al-Zn-Mg-Si-Sr coated steel sheet, characterized in that the coating layer contains Al: 40% by mass to 70% by mass, Si: 0.6% by mass to 5% by mass, and Mg: 0.1% by mass ~10% by mass and Sr: 0.001% by mass to 1.0% by mass, with the remainder including Zn and unavoidable impurities, and the plating layer includes an interface alloy layer present at the interface with the base steel sheet, and master alloy layer on the interface layer, the Mg 2 Si in the cross-sectional direction of the plate thickness of the coating was observed in, from the inner surface of the main layer to a thickness range of up to 50% of present Mg 2 The area ratio of Si is 50% or more, and the area ratio of Mg 2 Si that continuously exists in the interdendritic portion from the interface alloy layer to the surface of the main layer (hereinafter, sometimes referred to as "stretching") is 50 %the following.

2.如所述1所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,其特徵在於:於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中,自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例為60%以上,且自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例為50%以下。 2. The molten Al-Zn-Mg-Si-Sr coated steel sheet as described in the above 1, characterized in that: in the Mg 2 Si observed in the cross section in the thickness direction of the coating layer, from The area ratio of Mg 2 Si existing in the thickness range from the surface of the main layer to 50% is 60% or more, and it extends from the surface of the main layer to the Mg 2 Si that reaches the interface alloy layer. The area ratio is less than 50%.

3.如所述2所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,其特徵在於:於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中,自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例為60%以上,且自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例為40%以下。 3. The molten Al-Zn-Mg-Si-Sr coated steel sheet according to the above 2, characterized in that: in the Mg 2 Si observed in the cross section in the thickness direction of the coating layer, The area ratio of Mg 2 Si existing in the thickness range from the surface of the main layer to 50% is 60% or more, and it extends from the surface of the main layer to the Mg 2 Si that reaches the interface alloy layer. The area ratio is less than 40%.

4.如所述1至3中任一項所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,其特徵在於:關於在所述鍍覆層的厚度方向的剖面中所觀察到的Si相,相對於在所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si及Si相的面積率的合計而言的Si相的面積率的比例為30%以下。 4. The molten Al-Zn-Mg-Si-Sr coated steel sheet according to any one of 1 to 3, characterized by The ratio of the area ratio of the Si phase to the total area ratio of the Mg 2 Si and Si phase observed in the cross section in the thickness direction of the plating layer is 30% or less.

5.如所述1至4中任一項所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,其特徵在於:所述主層具有α-Al相的枝晶部分,該枝 晶部分的平均枝晶臂(dendrite arm)間距離、與所述鍍覆層的厚度滿足以下式(1)。 5. The molten Al-Zn-Mg-Si-Sr coated steel sheet according to any one of 1 to 4, wherein the main layer has an α-Al phase dendrite portion, and the dendrite The average distance between dendrite arms of the crystal part and the thickness of the plating layer satisfy the following formula (1).

t/d≧1.5…(1) t/d≧1.5…(1)

t:鍍覆層的厚度(μm)、d:平均枝晶臂間距離(μm) t: thickness of plating layer (μm), d: average distance between dendrite arms (μm)

6.一種熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法,其特徵在於:使用鍍覆浴,所述鍍覆浴含有Al:40質量%~70質量%、Si:0.6質量%~5質量%、Mg:0.1質量%~10質量%及Sr:0.001質量%~1.0質量%,且具有剩餘部分包含Zn及不可避免的雜質的組成,且浴溫為585℃以下,對鋼板實施熔融鍍覆時,將進入所述鍍覆浴時的鋼板溫度(進入板溫)設為自所述鍍覆浴的浴溫加上20℃所得的溫度(鍍覆浴溫+20℃)以下。 6. A method for manufacturing a molten Al-Zn-Mg-Si-Sr coated steel sheet, characterized in that a coating bath is used, and the coating bath contains Al: 40% by mass to 70% by mass and Si: 0.6% by mass ~5 mass%, Mg: 0.1 mass% to 10 mass%, and Sr: 0.001 mass% to 1.0 mass%, and the remainder contains Zn and inevitable impurities, and the bath temperature is 585°C or less, which is applied to the steel plate At the time of hot-dip coating, the temperature of the steel sheet when entering the coating bath (entering plate temperature) is set to the temperature (coating bath temperature + 20°C) obtained by adding 20°C to the bath temperature of the coating bath.

7.如所述6所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法,其特徵在於:所述鋼板的進入板溫為所述鍍覆浴的浴溫以下。 7. The method for manufacturing a molten Al-Zn-Mg-Si-Sr plated steel sheet according to the above 6, characterized in that the entry temperature of the steel sheet is equal to or lower than the bath temperature of the coating bath.

8.如所述6或7所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法,其特徵在於:對所述鋼板實施熔融鍍覆後,以10℃/s以上的平均冷卻速度將所述鋼板冷卻至板溫成為自所述鍍覆浴的浴溫減去150℃所得的溫度(鍍覆浴溫-150℃)為止。 8. The method for manufacturing a molten Al-Zn-Mg-Si-Sr coated steel sheet according to 6 or 7, characterized in that: after the steel sheet is subjected to hot-dip coating, an average temperature of 10°C/s or more Cooling rate The steel sheet is cooled until the plate temperature becomes a temperature obtained by subtracting 150°C from the bath temperature of the coating bath (plating bath temperature-150°C).

根據本發明,可提供一種具有良好的表面外觀性、並且平板部及加工部的耐蝕性優異的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板、以及具有良好的表面外觀性、並且平板部及加工部的耐蝕性優異的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法。 According to the present invention, it is possible to provide a molten Al-Zn-Mg-Si-Sr plated steel sheet having good surface appearance and excellent corrosion resistance of the flat part and the processed part, and the flat part having good surface appearance And a method for manufacturing a molten Al-Zn-Mg-Si-Sr plated steel sheet with excellent corrosion resistance of the processed part.

A-B:區間 A-B: interval

L:距離 L: distance

圖1(a)是關於熔融Al-Zn-Mg系鍍覆鋼板而表示腐蝕前後的狀態的圖,圖1(b)是關於熔融Al-Zn系鍍覆鋼板而表示腐蝕前後的狀態的圖。 Fig. 1(a) is a diagram showing the state before and after corrosion of the molten Al-Zn-Mg-based plated steel sheet, and Fig. 1(b) is a diagram showing the state before and after the corrosion of the molten Al-Zn-based plated steel sheet.

圖2(a)是本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的藉由掃描電子顯微鏡的能量分散型X射線分光法(Scanning Electron Microscope-Energy Dispersive X-Ray Analysis,SEM-EDX)來表示各元素的狀態的圖,圖2(b)是關於圖2(a)所示的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的一部分,對用以觀察Mg2Si及Si相的方法進行說明的圖。 Figure 2 (a) is the energy dispersive X-ray spectroscopy (Scanning Electron Microscope-Energy Dispersive X-Ray Analysis, SEM-) of the molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention. EDX) to show the state of each element, Figure 2 (b) is about a part of the molten Al-Zn-Mg-Si-Sr plated steel sheet shown in Figure 2 (a), to observe the Mg 2 Si and A diagram explaining the method of the Si phase.

圖3是用以對算出在鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中自主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例的方法進行說明的圖。 3 is a method for calculating the area ratio of Mg 2 Si present in the thickness range of the surface of the main layer to 50% in the Mg 2 Si observed in the cross section in the thickness direction of the plating layer Figure.

圖4是用以對算出在鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中自主層的表面起延伸至到達界面合金層為止的Mg2Si的面積比例的方法進行說明的圖。 FIG. 4 is used for extending from the surface of the Mg 2 Si is calculated in a cross-sectional direction of the plate thickness of the coating observed to autonomously layer area ratio of Mg 2 Si process until the interfacial alloy layer to be described in FIG. .

圖5是用以說明枝晶臂間距離的測定方法的圖。 Fig. 5 is a diagram for explaining a method of measuring the distance between dendrite arms.

圖6是用以說明日本汽車標準的複合循環試驗(日本汽車標準組織-循環腐蝕試驗(Japanese Automobile Standards Organization-Cyclic Corrosion Test,JASO-CCT))的流程的圖。 FIG. 6 is a diagram for explaining the flow of the combined cycle test (Japanese Automobile Standards Organization-Cyclic Corrosion Test (JASO-CCT)) of the Japanese Automobile Standards.

(熔融Al-Zn-Mg-Si-Sr鍍覆鋼板) (Molten Al-Zn-Mg-Si-Sr coated steel sheet)

作為本發明的對象的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板於鋼板表面具有鍍覆層,該鍍覆層包含:存在於與基底鋼板的界面的界面合金層、及存在於該合金層上的主層。另外,所述鍍覆層含有Al:40質量%~70質量%、Si:0.6質量%~5質量%、Mg:0.1質量%~10質量%及Sr:0.001質量%~1.0質量%,且具有剩餘部分包含Zn及不可避免的雜質的組成。 The molten Al-Zn-Mg-Si-Sr coated steel sheet that is the object of the present invention has a coating layer on the surface of the steel sheet, and the coating layer includes: an interface alloy layer existing at the interface with the base steel sheet, and the alloy The main floor above the floor. In addition, the plating layer contains Al: 40% by mass to 70% by mass, Si: 0.6% by mass to 5% by mass, Mg: 0.1% by mass to 10% by mass, and Sr: 0.001% by mass to 1.0% by mass, and has The remainder contains Zn and unavoidable impurities.

就耐蝕性與操作方面的平衡而言,所述鍍覆層中的Al含量設為40質量%~70質量%,較佳為45質量%~65質量%。若所述鍍覆層的主層的Al含量為40質量%以上,則可確保良好的耐蝕性。所述主層主要包含:過飽和地含有Zn且Al進行枝晶凝固的部分(α-Al相的枝晶部分)、及剩餘的枝晶間隙的部分(枝晶間部分),且可實現該枝晶部分於鍍覆層的膜厚方向上積層的耐蝕性優異的結構。另外,所述α-Al相的枝晶部分越多地積層,則腐蝕行進路徑變得越複雜,腐蝕越難以容易地到達基底鋼板,因此耐蝕性提升。就同樣的觀點而言,所述鍍覆層中的Al含量較佳為設為45質量%以上。另一方面,若所述鍍覆層中的Al含量超過70質量%,則對Fe具有犧牲防蝕作用的Zn的含量變少,耐蝕性劣 化。因此,所述鍍覆層中的Al含量設為70質量%以下。另外,若所述鍍覆層中的Al含量為65質量%以下,則鍍覆的附著量變少,即便於基底鋼板容易露出的情況下,亦對Fe具有犧牲防蝕作用,獲得充分的耐蝕性。因此,鍍覆主層的Al含量較佳為設為65質量%以下。 In terms of the balance between corrosion resistance and operation, the Al content in the plating layer is set to 40% by mass to 70% by mass, preferably 45% to 65% by mass. If the Al content of the main layer of the plating layer is 40% by mass or more, good corrosion resistance can be ensured. The main layer mainly includes: a part where Zn is supersaturated and Al undergoes dendrite solidification (a-Al phase dendrite part), and a part of the remaining dendrite gaps (interdendritic part), and the dendrite can be realized. The crystal portion is laminated in the thickness direction of the plating layer and has a structure excellent in corrosion resistance. In addition, the more dendrite portions of the α-Al phase are layered, the more complicated the corrosion path becomes, and the more difficult it is for the corrosion to reach the base steel sheet, so the corrosion resistance is improved. From the same viewpoint, the Al content in the plating layer is preferably set to 45% by mass or more. On the other hand, if the Al content in the plating layer exceeds 70% by mass, the content of Zn, which has a sacrificial anticorrosion effect on Fe, decreases, resulting in poor corrosion resistance. 化. Therefore, the Al content in the plating layer is set to 70% by mass or less. In addition, if the Al content in the plating layer is 65% by mass or less, the adhesion amount of the plating decreases, and even when the base steel sheet is easily exposed, it has a sacrificial anticorrosion effect on Fe, and sufficient corrosion resistance is obtained. Therefore, the Al content of the plating main layer is preferably set to 65% by mass or less.

所述鍍覆層中的Si是為了抑制在與基底鋼板的界面生成的界面合金層的成長,為了提升耐蝕性或加工性而添加於鍍覆浴中,必然包含於所述主層中。於為本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的情況下,若使鍍覆浴中含有Si而進行熔融鍍覆處理,則在基底鋼板浸漬於鍍覆浴中的同時,鋼板表面的Fe與浴中的Al或Si發生合金化反應,而生成包含Fe-Al系及/或Fe-Al-Si系的化合物的合金。藉由所述Fe-Al-Si系界面合金層的生成,可抑制界面合金層的成長。而且,於所述鍍覆層中的Si含量為0.6質量%以上的情況下,可充分抑制所述界面合金層的成長。另一方面,於鍍覆層的Si含量超過5質量%的情況下,於鍍覆層中使加工性降低,成為陰極部位的Si相容易析出。所述Si相的析出如後述般可藉由增加Mg含量並使Si含量與Mg含量之間具有一定關係而加以抑制,但該情況下,會導致製造成本上升、或由Mg2Si的量變多所引起的加工性的降低,另外,使鍍覆浴的組成管理變得更困難。因此,鍍覆層中的Si含量設為5質量%以下。進而,另外若考慮到可更確實地抑制界面合金層的成長及Si相析出的方面、或可應對作為Mg2Si而消耗了Si的情況的方面,則較佳為將所述 鍍覆層中的Si含量設為超過2.3質量%~3.5質量%。 The Si in the plating layer is to suppress the growth of the interface alloy layer generated at the interface with the base steel sheet, and is added to the plating bath to improve corrosion resistance or workability, and is inevitably included in the main layer. In the case of the molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention, if Si is contained in the coating bath and the hot-dip coating treatment is performed, the base steel sheet is immersed in the coating bath at the same time, Fe on the surface of the steel sheet undergoes an alloying reaction with Al or Si in the bath to form an alloy containing Fe-Al-based and/or Fe-Al-Si-based compounds. The formation of the Fe-Al-Si-based interface alloy layer can suppress the growth of the interface alloy layer. Furthermore, when the Si content in the plating layer is 0.6% by mass or more, the growth of the interface alloy layer can be sufficiently suppressed. On the other hand, when the Si content of the plating layer exceeds 5% by mass, the workability in the plating layer is reduced, and the Si phase serving as the cathode portion is likely to precipitate. The precipitation of the Si phase can be suppressed by increasing the Mg content and having a certain relationship between the Si content and the Mg content as described later. However, in this case, the manufacturing cost will increase or the amount of Mg 2 Si will increase. The resulting decrease in workability also makes the composition management of the plating bath more difficult. Therefore, the Si content in the plating layer is set to 5% by mass or less. Furthermore, considering that the growth of the interfacial alloy layer and the precipitation of the Si phase can be suppressed more reliably, or that it can cope with the case where Si is consumed as Mg 2 Si, it is preferable to add The Si content of is set to exceed 2.3% by mass to 3.5% by mass.

所述鍍覆層含有0.1質量%~10質量%的Mg。當所述鍍覆層的主層腐蝕時,於腐蝕產物中包含Mg,腐蝕產物的穩定性提升,腐蝕的行進延遲,結果獲得耐蝕性提升的效果。更具體而言,所述鍍覆層的主層中所存在的Mg與所述Si鍵結,生成Mg2Si。所述Mg2Si如圖1(a)所示,於鍍覆鋼板腐蝕時,在初期溶解,因此Mg包含於腐蝕產物中。所述腐蝕產物中所含的Mg具有使腐蝕產物緻密化的效果,可提升腐蝕產物的穩定性及對外來腐蝕因子的阻隔性。另一方面,於鍍覆層中不含Mg的情況下,如圖1(b)所示,不會於腐蝕產物中含有Mg,無法獲得所期望的耐蝕性。 The plating layer contains 0.1% to 10% by mass of Mg. When the main layer of the plating layer is corroded, Mg is contained in the corrosion product, the stability of the corrosion product is improved, the progress of the corrosion is delayed, and as a result, the effect of improving the corrosion resistance is obtained. More specifically, Mg present in the main layer of the plating layer is bonded to the Si to generate Mg 2 Si. As shown in Fig. 1(a), the Mg 2 Si dissolves in the initial stage when the plated steel sheet is corroded, so Mg is included in the corrosion product. The Mg contained in the corrosion product has the effect of densifying the corrosion product, and can improve the stability of the corrosion product and the barrier property of external corrosion factors. On the other hand, when Mg is not contained in the plating layer, as shown in FIG. 1(b), Mg is not contained in the corrosion product, and the desired corrosion resistance cannot be obtained.

此處,將所述鍍覆層的Mg含量設為0.1質量%以上的原因在於:於所述鍍覆層以所述濃度範圍含有Si的情況下,藉由將Mg濃度設為0.1質量%以上,可生成Mg2Si,可獲得腐蝕延遲效果。就同樣的觀點而言,所述鍍覆層的Mg含量較佳為1質量%以上,更佳為3質量%以上。另一方面,將所述鍍覆層的Mg的含量設為10質量%以下的原因在於:於所述鍍覆層的Mg的含量超過10質量%的情況下,除了耐蝕性的提升效果飽和以外,亦有製造成本上升與鍍覆浴的組成管理變困難。就同樣的觀點而言,所述鍍覆層的Mg含量較佳為6質量%以下。 Here, the reason why the Mg content of the plating layer is 0.1% by mass or more is that when the plating layer contains Si in the concentration range, the Mg concentration is set to 0.1% by mass or more. , Mg 2 Si can be generated, and the corrosion delay effect can be obtained. From the same viewpoint, the Mg content of the plating layer is preferably 1% by mass or more, more preferably 3% by mass or more. On the other hand, the reason for setting the Mg content of the plating layer to 10% by mass or less is that when the Mg content of the plating layer exceeds 10% by mass, in addition to the saturation of the corrosion resistance improvement effect As a result, the manufacturing cost has risen and the composition management of the plating bath has become difficult. From the same viewpoint, the Mg content of the plating layer is preferably 6% by mass or less.

另外,藉由將所述鍍覆層中的Mg含量設為1質量%以上,亦能夠改善塗裝後耐蝕性。若不含Mg的先前的熔融Al-Zn系鍍覆鋼板的鍍覆層與大氣接觸,則於α-Al相的周圍立刻形成緻 密且穩定的Al2O3的氧化膜,藉由所述氧化膜所帶來的保護作用,α-Al相的溶解性與枝晶間中的富Zn相的溶解性相比變得非常低。其結果,將先前的Al-Zn系鍍覆鋼板用於基底的塗裝鋼板於塗膜中產生損傷的情況下,以損傷部為起點在塗膜/鍍覆界面引起富Zn相的選擇腐蝕,向塗裝完成部的深處行進而引起大的塗膜膨脹,因此塗裝後耐蝕性差。因此,就獲得優異的塗裝後耐蝕性的觀點而言,較佳為將所述鍍覆層中的Mg含量設為1質量%以上,更佳為設為3質量%以上。 In addition, by setting the Mg content in the plating layer to 1% by mass or more, the corrosion resistance after coating can also be improved. If the coating layer of the previous molten Al-Zn-plated steel sheet that does not contain Mg is in contact with the atmosphere, a dense and stable Al 2 O 3 oxide film is immediately formed around the α-Al phase. The protective effect brought by the film, the solubility of the α-Al phase is very low compared to the solubility of the Zn-rich phase in the dendrite. As a result, when the coated steel sheet using the conventional Al-Zn-based coated steel sheet as the base is damaged in the coating film, selective corrosion of the Zn-rich phase occurs at the coating/plating interface starting from the damaged part, and Going deep into the painted area causes large swelling of the coating film, so the corrosion resistance after painting is poor. Therefore, from the viewpoint of obtaining excellent corrosion resistance after coating, the Mg content in the plating layer is preferably 1% by mass or more, and more preferably 3% by mass or more.

另一方面,於為使用了在所述鍍覆層中含有Mg的熔融Al-Zn系鍍覆鋼板的塗裝鋼板的情況下,於枝晶間中析出的Mg2Si相或Mg-Zn化合物(MgZn2、Mg32(Al,Zn)49等)在腐蝕的初期階段溶出,而於腐蝕產物中混入Mg。含有Mg的腐蝕產物非常穩定,藉此,腐蝕於初期階段得到抑制,因此可抑制於為將先前的Al-Zn系鍍覆鋼板用於基底的塗裝鋼板的情況下成為問題的由富Zn相的選擇腐蝕所引起的大的塗膜膨脹。其結果,於鍍覆層中含有Mg的熔融Al-Zn系鍍覆鋼板顯示出優異的塗裝後耐蝕性。於所述鍍覆層中的Mg未滿1質量%的情況下,有腐蝕時溶出的Mg的量少,塗裝後耐蝕性不提升之虞。再者,於所述鍍覆層中的Mg含量超過10質量%的情況下,不僅效果飽和,而且會強烈地產生Mg化合物的腐蝕,鍍覆層整體的溶解性過度上升,結果,即便使腐蝕產物穩定化,其溶解速度亦變大,因此有產生大的膨脹寬度,塗裝後耐蝕性劣化之虞。因此,為了穩定地獲得優異的塗裝後耐蝕性, 較佳為將所述鍍覆層中的Mg含量設為10質量%以下。 On the other hand, in the case of a coated steel sheet using a molten Al-Zn-based coated steel sheet containing Mg in the coating layer, the Mg 2 Si phase or Mg-Zn compound precipitated in the dendrite (MgZn 2 , Mg 32 (Al, Zn) 49, etc.) are eluted in the initial stage of corrosion, and Mg is mixed in the corrosion products. Corrosion products containing Mg are very stable, whereby corrosion is suppressed in the initial stage. Therefore, it is possible to suppress the Zn-rich phase that has become a problem when the Al-Zn-based coated steel sheet is used as a base for the coated steel sheet. Large film expansion caused by selective corrosion. As a result, the molten Al-Zn-based coated steel sheet containing Mg in the coating layer exhibits excellent corrosion resistance after coating. When the Mg in the plating layer is less than 1% by mass, the amount of Mg eluted during corrosion is small, and the corrosion resistance after coating may not improve. Furthermore, when the Mg content in the plating layer exceeds 10% by mass, not only the effect is saturated, but the corrosion of the Mg compound is strongly generated, and the solubility of the entire plating layer is excessively increased. As a result, even if the corrosion is The product is stabilized, and its dissolution rate is also increased. Therefore, a large expansion width may occur, and the corrosion resistance may deteriorate after coating. Therefore, in order to stably obtain excellent corrosion resistance after coating, it is preferable to set the Mg content in the plating layer to 10% by mass or less.

另外,所述鍍覆層含有0.001質量%~1.0質量%的Sr。藉由在所述鍍覆層中含有Sr,可抑制褶皺狀缺陷的產生,並提升本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的表面外觀性。 In addition, the plating layer contains 0.001% by mass to 1.0% by mass of Sr. By containing Sr in the coating layer, the occurrence of wrinkle defects can be suppressed, and the surface appearance of the molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention can be improved.

所謂所述褶皺狀缺陷,為於所述鍍覆層的表面所形成的成為褶皺狀凹凸的缺陷,於所述鍍覆層表面,作為發白的條紋而被觀察到。此種條紋狀缺陷於向所述鍍覆層中添加了大量Mg的情況下容易產生。因此,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,藉由使所述鍍覆層中含有Sr,而於所述鍍覆層表層使Sr相較於Mg而優先氧化,抑制Mg的氧化反應,藉此能夠抑制所述條紋狀缺陷的產生。 The wrinkle-shaped defect is a wrinkle-shaped asperity formed on the surface of the plating layer, and it is observed as whitish streaks on the surface of the plating layer. Such streak defects are easily generated when a large amount of Mg is added to the plating layer. Therefore, in the molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention, by making the coating layer contain Sr, the surface layer of the coating layer causes Sr to be oxidized more preferentially than Mg , Suppressing the oxidation reaction of Mg, thereby being able to suppress the occurrence of the streak-shaped defects.

關於所述鍍覆層中的Sr含量,要求為0.001質量%以上。原因在於獲得抑制所述條紋狀缺陷產生的效果。就同樣的觀點而言,所述鍍覆層中的Sr含量較佳為0.005質量%以上,更佳為0.01質量%以上,特佳為0.05質量%以上。另一方面,關於所述鍍覆層中的Sr含量,要求為1.0質量%以下。原因在於:若Sr的含量變得過多,則抑制條紋狀缺陷產生的效果飽和,故於成本方面不利。就同樣的觀點而言,所述鍍覆層中的Sr含量較佳為0.7質量%以下,更佳為0.5質量%以下,特佳為0.3質量%以下。 Regarding the Sr content in the plating layer, it is required to be 0.001% by mass or more. The reason is to obtain the effect of suppressing the generation of the streak-shaped defect. From the same viewpoint, the Sr content in the plating layer is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. On the other hand, the Sr content in the plating layer is required to be 1.0% by mass or less. The reason is that if the content of Sr becomes too large, the effect of suppressing the occurrence of streak defects is saturated, which is disadvantageous in terms of cost. From the same viewpoint, the Sr content in the plating layer is preferably 0.7% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

再者,所述鍍覆層包含:於鍍覆處理中因鍍覆浴與基底鋼板的反應而混入至鍍覆層中的基底鋼板成分、或對鍍覆浴進行建浴時使用的鑄錠(ingot)中所含有的不可避免的雜質。作為混 入至所述鍍覆層中的基底鋼板成分,有時含有數%左右的Fe。作為鍍覆浴中不可避免的雜質的種類,例如,作為基底鋼板成分,可列舉:Fe、Mn、P、S、C、Nb、Ti、B等。另外,作為鑄錠中的雜質,可列舉:Fe、Pb、Sb、Cd、As、Ga、V等。再者,關於所述鍍覆層中的Fe,無法對自基底鋼板中混入的Fe與鍍覆浴中所存在的Fe進行區分定量。所述不可避免的雜質的總含量並無特別限定,但就維持鍍覆的耐蝕性與均勻的溶解性的觀點而言,較佳為除Fe以外的不可避免的雜質量合計為1質量%以下。 Furthermore, the plating layer includes: the base steel sheet component mixed into the plating layer due to the reaction between the plating bath and the base steel sheet during the plating process, or the ingot used when the plating bath is bathed ( ingot) unavoidable impurities contained in. As a mess The base steel sheet component incorporated in the plating layer may contain Fe in the order of several %. As the types of impurities that are unavoidable in the plating bath, for example, as the base steel sheet component, Fe, Mn, P, S, C, Nb, Ti, B, etc. can be cited. In addition, examples of impurities in the ingot include Fe, Pb, Sb, Cd, As, Ga, and V. In addition, with regard to Fe in the plating layer, it is impossible to distinguish and quantify Fe mixed from the base steel sheet and Fe present in the plating bath. The total content of the unavoidable impurities is not particularly limited, but from the viewpoint of maintaining the corrosion resistance and uniform solubility of the plating, the total amount of the unavoidable impurities other than Fe is preferably 1% by mass or less. .

另外,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,所述鍍覆層亦能夠以各元素未滿1質量%的含量更含有在Zn-Al系鍍覆鋼板中作為腐蝕產物的穩定元素而已知的選自Cr、Ni、Co、Mn、Ca、V、Ti、B、Mo、Sn、Zr、Li、Ag等中的至少一種以上。若該些元素各自的含有率未滿1質量%,則不阻礙本發明中所揭示的效果,且藉由腐蝕產物穩定效果而實現耐蝕性的進一步提升。 In addition, in the molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention, the coating layer can also be contained in the Zn-Al based coated steel sheet at a content of less than 1% by mass of each element. The stable element of the corrosion product is known to be at least one or more selected from Cr, Ni, Co, Mn, Ca, V, Ti, B, Mo, Sn, Zr, Li, Ag, and the like. If the content of each of these elements is less than 1% by mass, the effect disclosed in the present invention is not hindered, and the corrosion resistance is further improved by the corrosion product stabilization effect.

再者,關於所述界面合金層,為所述鍍覆層中存在於與基底鋼板的界面的層,如上所述,為鋼板表面的Fe與浴中的Al或Si發生合金化反應而必然生成的Fe-Al系及/或Fe-Al-Si系的化合物。所述界面合金層由於硬且脆,因此若厚厚地成長,則會成為加工時的裂紋產生的起點,因此較佳為減薄。 Furthermore, regarding the interface alloy layer, it is a layer that exists at the interface with the base steel sheet in the plating layer. As described above, Fe on the surface of the steel sheet and Al or Si in the bath are inevitably formed by the alloying reaction. Fe-Al-based and/or Fe-Al-Si-based compounds. Since the interface alloy layer is hard and brittle, if it grows thickly, it becomes a starting point for cracks during processing, so it is preferably thinned.

而且,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,特徵在於:於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中,自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面 積比例為50%以上,且自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例為50%以下。 Furthermore, in the molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention, it is characterized in that in the Mg 2 Si observed in the cross section in the thickness direction of the coating layer, from the main layer surface area ratio to a thickness range of up to 50% of Mg 2 Si is present in 50% or more, and from the surface of the primary layer extends from an area ratio reaches up to the interface of the alloy layer of Mg 2 Si Less than 50%.

藉此,可實現良好的表面外觀性,並且關於平板部及加工部的耐蝕性,亦能夠得到提升。 With this, good surface appearance can be achieved, and the corrosion resistance of the flat plate portion and the processed portion can also be improved.

於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中,自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例設為50%以上。藉由所述鍍覆層中含有Mg2Si,而於鍍覆層腐蝕時,所述Mg2Si優先溶解,且溶解於在鍍覆層表面所生成的腐蝕產物中的Mg發生濃化,藉此能夠表現出優異的耐蝕性。但於為了抑制褶皺狀缺陷等而使所述鍍覆層中含有Sr的情況下,存在如下問題:於所述鍍覆層主層的表面不存在充分的Mg2Si,難以使Mg於所述腐蝕產物中濃化,從而使耐蝕性降低。因此,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,藉由將所述鍍覆主層中所含有的Mg2Si中的大部分(具體而言為50%以上)集中於鍍覆主層的表面附近,即便於使鍍覆層中含有Sr的情況下,亦可於主層表面存在充分的Mg2Si,因此,於腐蝕時使足夠量的Mg2Si溶解,可使Mg於腐蝕產物中濃化,結果可抑制褶皺狀缺陷的產生,並且亦可實現優異的耐蝕性。 In the molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention, in the Mg 2 Si observed in the cross section in the thickness direction of the coating layer, from the surface of the main layer to 50% The area ratio of Mg 2 Si existing in the thickness range up to this point is set to 50% or more. Because the plating layer contains Mg 2 Si, when the plating layer is corroded, the Mg 2 Si is preferentially dissolved, and the Mg dissolved in the corrosion products generated on the surface of the plating layer is concentrated, by This can exhibit excellent corrosion resistance. However, when Sr is contained in the plating layer in order to suppress wrinkle-like defects, etc., there is a problem that sufficient Mg 2 Si does not exist on the surface of the plating layer main layer, and it is difficult to make Mg in the plating layer. The corrosion products are concentrated, thereby reducing the corrosion resistance. Therefore, in the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention, most of the Mg 2 Si contained in the main plating layer (specifically, 50% or more) Concentrated in the vicinity of the surface of the plating main layer, even when Sr is contained in the plating layer, sufficient Mg 2 Si can be present on the surface of the main layer. Therefore, a sufficient amount of Mg 2 Si is dissolved during corrosion. Mg can be concentrated in corrosion products, and as a result, the generation of wrinkle-like defects can be suppressed, and excellent corrosion resistance can also be achieved.

即,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,由於自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例大(為50%以上),因此,腐蝕時主層表面所存在的Mg2Si 的大部分發生溶解,於腐蝕後的鍍覆層表面所形成的腐蝕產物的Mg濃度變高。因此,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,可抑制褶皺狀缺陷的產生,並且亦可實現優異的耐蝕性。 That is, in the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention, the area ratio of Mg 2 Si existing in the thickness range from the surface of the main layer to 50% is large (50%). % Or more), therefore, most of the Mg 2 Si present on the surface of the main layer is dissolved during corrosion, and the Mg concentration of the corrosion product formed on the surface of the plating layer after corrosion becomes higher. Therefore, in the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention, the generation of wrinkle-like defects can be suppressed, and excellent corrosion resistance can also be achieved.

另一方面,先前的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板由於自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si少(未滿50%),因此,腐蝕時溶解的Mg2Si的量並不充分,腐蝕後的鍍覆層表面的腐蝕產物的Mg濃度相對變低。因此,於先前的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,雖然可抑制褶皺狀缺陷的產生,但耐蝕性降低。 On the other hand, the conventional molten Al-Zn-Mg-Si-Sr plated steel sheet contains less Mg 2 Si (less than 50%) in the thickness range from the surface of the main layer to 50%. , The amount of Mg 2 Si dissolved during corrosion is insufficient, and the Mg concentration of corrosion products on the surface of the plating layer after corrosion is relatively low. Therefore, in the conventional molten Al-Zn-Mg-Si-Sr plated steel sheet, although the generation of wrinkle-like defects can be suppressed, the corrosion resistance is reduced.

再者,所述Mg2Si的面積比例(自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例)的導出例如可使用掃描型電子顯微鏡並利用能量分散型X射線分光法(SEM-EDX)來進行。 Further, the area ratio of Mg 2 Si is derived (area ratio from an inner surface of the main layer to a thickness range of up to 50% of the Mg 2 Si is present) may be, for example, using a scanning electron microscope and energy dispersive Type X-ray spectroscopy (SEM-EDX).

例如,如圖2(a)所示,於獲取所述鍍覆層的厚度方向的剖面狀態後,如圖2(b)所示,對Mg及Si分別進行映射(mapping)(Mg由紅表示,Si由藍表示)。其後,於已映射的Mg及Si中,可將該些於相同位置重疊的部分(圖2(b)中由紫表示的部分)設為Mg2Si。 For example, as shown in FIG. 2(a), after obtaining the cross-sectional state of the plating layer in the thickness direction, as shown in FIG. 2(b), Mg and Si are respectively mapped (mapping) (Mg is represented by red , Si is represented by blue). After that, in the mapped Mg and Si, the part (the part indicated by purple in FIG. 2(b)) that overlaps at the same position can be set as Mg 2 Si.

此處,關於所得到的Mg2Si,如圖3所示,測定Mg2Si相對於所述鍍覆層的主層整體面積的面積率(A%)。其後,將所述主層於厚度方向上分割為兩半,測定相對於所述主層整體面積而言的自表面至50%為止的厚度範圍內所存在的Mg2Si的面積率 (B%)。而且,藉由算出相對於所述鍍覆層的主層整體的Mg2Si的面積率(A%)而言的自主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積率(B%)的比例((B%)/(A%)×100%),可得到於觀察視場中所存在的Mg2Si中,自主層的表面至50%為止的厚度範圍內所存在的Mg2Si所占的面積比例(X%)。 Here, regarding the obtained Mg 2 Si, as shown in FIG. 3, the area ratio (A%) of Mg 2 Si with respect to the entire area of the main layer of the plating layer was measured. Thereafter, the main layer was divided into two halves in the thickness direction, and the area ratio of Mg 2 Si existing in the thickness range from the surface to 50% relative to the entire area of the main layer was measured (B %). Further, with respect to the Mg 2 Si was calculated area within the thickness range of up to customize the surface layer of the entire main layer of the plated layer area ratio of Mg 2 Si is (A%) to 50% in terms of the present The ratio ((B%)/(A%)×100%) of the rate (B%) can be obtained in the Mg 2 Si present in the observation field of view. The thickness of the surface of the autonomous layer is within the range of 50%. The proportion of the area occupied by the existing Mg 2 Si (X%).

另外,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,藉由將自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例設為50%以下,關於加工部的耐蝕性,亦能夠大幅提升。所述鍍覆主層中所含的Mg2Si雖然具有耐蝕性提升效果,但如所述般,成為於界面合金層產生的裂紋的傳播路徑,使加工性降低,因此,於先前的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,未能獲得充分的加工性以及加工部的耐蝕性。因此,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,藉由減少自所述界面合金層起到達所述鍍覆主層表面為止般的Mg2Si的量(將Mg2Si的面積比例設為50%以下),當對鋼板進行加工時,即便於硬的界面合金層產生了裂紋的情況下,該裂紋的大部分亦僅於界面合金層附近傳播,不到達所述鍍覆層的主層表面。其結果,可確保良好的加工性以及加工後的耐蝕性。 In addition, in the molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention, the area ratio of Mg 2 Si extending from the surface of the main layer to reaching the interface alloy layer is set to Below 50%, the corrosion resistance of the processed part can also be greatly improved. Although the Mg 2 Si contained in the main plating layer has the effect of improving the corrosion resistance, as described above, it becomes the propagation path of cracks generated in the interface alloy layer and reduces the workability. -In the Zn-Mg-Si-Sr plated steel sheet, sufficient workability and corrosion resistance of the processed part cannot be obtained. Therefore, in the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention, by reducing the amount of Mg 2 Si from the interface alloy layer to the surface of the main plating layer (the Mg 2 The area ratio of Si is set to 50% or less). When the steel sheet is processed, even if cracks occur in the hard interface alloy layer, most of the cracks only propagate in the vicinity of the interface alloy layer and do not reach the entire surface. The surface of the main layer of the plating layer. As a result, good workability and corrosion resistance after processing can be ensured.

另一方面,於先前的熔融Al-Zn-Mg系鍍覆鋼板中,於以所述界面合金層為起點而產生了裂紋的情況下,該些裂紋的大部分到達鍍覆主層的表面為止,因此無法獲得充分的加工部的耐蝕性。 On the other hand, in the previous molten Al-Zn-Mg-based plated steel sheet, when cracks occur from the interface alloy layer as a starting point, most of these cracks reach the surface of the main plating layer Therefore, sufficient corrosion resistance of the processed part cannot be obtained.

另外,關於所述Mg2Si的面積比例(自主層的表面起延 伸至到達所述界面合金層為止的Mg2Si的面積比例)的導出,例如亦可使用掃描型電子顯微鏡並利用能量分散型X射線分光法(SEM-EDX)來進行。 Further, with respect to the area ratio 2 Si Mg (independent from the surface layer extends to the area ratio of Mg 2 Si in the alloy layer until reaching the interface) is derived, for example, can also be used by using a scanning electron microscope and energy dispersive X-ray spectroscopy (SEM-EDX) is performed.

如上所述,於獲取所述鍍覆層的厚度方向的剖面狀態後(圖2(a)),對Mg及Si分別進行映射(圖2(b))。其後,於已映射的Mg及Si中,可將該些於相同位置重疊的部分設為Mg2Si(圖2(b))。 As described above, after acquiring the cross-sectional state of the plating layer in the thickness direction (FIG. 2(a)), Mg and Si are respectively mapped (FIG. 2(b)). After that, in the mapped Mg and Si, the overlapping portions at the same position can be referred to as Mg 2 Si (FIG. 2(b)).

此處,關於所得到的Mg2Si,如圖4所示,測定Mg2Si相對於所述鍍覆層的主層整體面積的面積率(A%)。其後,測定於觀察視場中所存在的Mg2Si粒子中,自主層的表面起延伸至到達界面合金層為止的Mg2Si粒子(圖4中由箭頭表示的粒子)相對於所述鍍覆層的主層整體的面積率(C%)。而且,藉由算出相對於所述鍍覆層的主層整體的Mg2Si的面積率(A%)而言的所述鍍覆層的主層整體的自主層的表面起延伸至到達界面合金層為止的Mg2Si的面積率(C%)的比例((C%)/(A%)×100%),可得到於觀察視場中所存在的Mg2Si粒子中,自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例(Y%)。 Here, regarding the obtained Mg 2 Si, as shown in FIG. 4, the area ratio (A%) of Mg 2 Si with respect to the entire area of the main layer of the plating layer was measured. Thereafter, the Mg 2 Si particles measured in field of view as in the present, independent from the surface layer extends to the Mg 2 Si particles (particles represented by an arrow in FIG. 4) until reaching an interface with respect to the alloy plating layer The area ratio (C%) of the entire main layer of the cladding layer. Furthermore, by calculating the area ratio (A%) of Mg 2 Si of the entire main layer of the plating layer, the surface of the autonomous layer of the entire main layer of the plating layer extends to reach the interface alloy The ratio ((C%)/(A%)×100%) of the area ratio (C%) of Mg 2 Si up to the layer can be obtained from the Mg 2 Si particles present in the observation field. The area ratio (Y%) of Mg 2 Si extending from the surface of the layer to reaching the interface alloy layer.

再者,關於本發明中的所述Mg2Si「自主層的表面起延伸至到達界面合金層為止」的方面,不僅是所述Mg2Si自主層的表面起延伸至到達(接觸)所述界面合金層為止,而且所述Mg2Si的下端與所述界面合金層的上端的距離非常小,實質上亦包括到達所述界面合金層的情況(例如,於所述鍍覆層的厚度方向的剖 面中觀察時的、所述Mg2Si的下端與所述界面合金層的上端的距離為1.0μm以下的情況)。原因在於:該情況下,於以所述界面合金層為起點而產生了裂紋的情況下,該些裂紋的大部分亦到達鍍覆主層的表面為止。 Furthermore, regarding the Mg 2 Si "extends from the surface of the autonomous layer to the interface alloy layer" in the present invention, it is not only that the Mg 2 Si extends from the surface of the autonomous layer to reach (contact) the The distance between the lower end of the Mg 2 Si and the upper end of the interface alloy layer is very small, and the distance between the lower end of the Mg 2 Si and the upper end of the interface alloy layer is very small. When the distance between the lower end of the Mg 2 Si and the upper end of the interface alloy layer is 1.0 μm or less when viewed in the cross section of ). The reason is that in this case, when cracks are generated starting from the interface alloy layer, most of these cracks also reach the surface of the main plating layer.

關於在所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si,就可實現更優異的耐蝕性的觀點而言,較佳為自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例為60%以上。 Regarding the Mg 2 Si observed in the cross section in the thickness direction of the plating layer, from the viewpoint of achieving more excellent corrosion resistance, it is preferably a thickness from the surface of the main layer to 50% The area ratio of Mg 2 Si existing in the range is 60% or more.

另外,關於在所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si,就可實現更優異的加工部的耐蝕性的觀點而言,較佳為自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例為40%以下。 In addition, with regard to the Mg 2 Si observed in the cross section in the thickness direction of the plating layer, from the viewpoint of achieving more excellent corrosion resistance of the processed part, it is preferably from the surface of the main layer The area ratio of Mg 2 Si extending to the interface alloy layer is 40% or less.

進而,關於在所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si,就可實現更優異的耐蝕性及加工部的耐蝕性的觀點而言,更佳為:自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例為60%以上,且自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例為40%以下。 Furthermore, with regard to the Mg 2 Si observed in the cross section in the thickness direction of the plating layer, from the viewpoint of achieving more excellent corrosion resistance and corrosion resistance of the processed part, it is more preferable that: the ratio of the area of the inner surface layer to a thickness in the range up to 50% of Mg 2 Si is present in 60% or more, and extends from the main surface layer to reach the interface area until the Mg 2 Si alloy layer ratio It is less than 40%.

此處,關於在所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si的面積比例,為將於鍍覆層的隨機選擇的10個部位的剖面中所觀察到的Mg2Si的面積比例加以平均所得者。 Here, the area ratio of the cross section in the thickness direction of the plated coating of observed Mg 2 Si, the randomly selected cross-section will be plated coating 10 places the observed Mg 2 Si The area ratio is averaged.

再者,由於所述鍍覆層中含有Si作為組成成分,因此如上所述,根據鍍覆層中的Si、Mg的組成,有時於鍍覆層中形成 Si相。然而,就進一步提高耐蝕性及加工性的觀點而言,較佳為儘可能抑制所述Si相的形成。 Furthermore, since the plating layer contains Si as a constituent, as described above, depending on the composition of Si and Mg in the plating layer, it may be formed in the plating layer. Si phase. However, from the viewpoint of further improving corrosion resistance and workability, it is preferable to suppress the formation of the Si phase as much as possible.

特別是於本發明中發現,提升耐蝕性的Mg2Si與於鍍覆層腐蝕時成為陰極部位而使耐蝕性劣化的Si相的含有比率是重要的。即,本發明的本質在於,即便使耐蝕性提升的Mg2Si的絕對量多,若使耐蝕性劣化的Si相的量多,則亦無法確保良好的耐蝕性,因此,將其比例控制於一定值以下。 In particular, it has been found in the present invention that the content ratio of Mg 2 Si that improves corrosion resistance and the Si phase that becomes a cathode site when the plating layer is corroded and deteriorates corrosion resistance is important. That is, the essence of the present invention is that even if the absolute amount of Mg 2 Si that improves corrosion resistance is large, if the amount of Si phase that deteriorates corrosion resistance is large, good corrosion resistance cannot be ensured. Therefore, the ratio is controlled to Below a certain value.

因此,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中,藉由以下所示的方法測定出的相對於在所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si及Si相的面積率的合計而言的在所述鍍覆層的厚度方向的剖面中所觀察到的Si相的面積率(Si相的面積率/Mg2Si及Si相的合計面積率)較佳為30%以下,更佳為10%以下。 Therefore, in the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention, the measurement by the method shown below is relative to the Mg observed in the cross section in the thickness direction of the coating layer. 2 The total area ratio of Si and Si phase is the area ratio of Si phase observed in the cross section in the thickness direction of the plating layer (area ratio of Si phase/ total area of Mg 2 Si and Si phase Rate) is preferably 30% or less, more preferably 10% or less.

再者,關於導出所述Si相的面積率的方法,例如與所述Mg2Si同樣地,可使用掃描型電子顯微鏡並利用能量分散型X射線分光法(SEM-EDX)來進行。 In addition, the method of deriving the area ratio of the Si phase can be performed by using a scanning electron microscope and energy dispersive X-ray spectroscopy (SEM-EDX) as in the case of the Mg 2 Si, for example.

如上所述,於獲取所述鍍覆層的厚度方向的剖面狀態後(圖2(a)),對Mg及Si分別進行映射(圖2(b))。其後,於已映射的Mg及Si中,可將於存在Si的位置不存在Mg的圖2(b)中由藍色表示的部分視為Si相。可由所觀察的視場中的該藍色部分的面積總和與鍍覆層的面積之比算出Si相的面積率(D%)。進而,相對於Mg2Si及Si相的面積率的合計而言的在所述鍍覆層的厚度方向的剖面中所觀察到的Si相的面積率(Si相的面積率/Mg2Si及 Si相的合計面積率)可作為(D%/(A%+D%)×100%)而算出。 As described above, after acquiring the cross-sectional state of the plating layer in the thickness direction (FIG. 2(a)), Mg and Si are respectively mapped (FIG. 2(b)). After that, in the mapped Mg and Si, the portion indicated by blue in FIG. 2(b) where Si does not exist in the position where Si is present can be regarded as the Si phase. The area ratio (D%) of the Si phase can be calculated from the ratio of the total area of the blue part to the area of the plating layer in the observed field of view. Furthermore, the area ratio of the Si phase observed in the cross section in the thickness direction of the plating layer relative to the total area ratio of the Mg 2 Si and Si phases (area ratio of the Si phase/Mg 2 Si and The total area ratio of the Si phase) can be calculated as (D%/(A%+D%)×100%).

此處,關於在所述鍍覆層的厚度方向的剖面中所觀察到的相對於Mg2Si及Si相的合計面積而言的Si相的面積比例,為將於鍍覆層的隨機選擇的10個部位的剖面中所觀察到的Si相的面積比例加以平均所得者。 Here, the area ratio of the Si phase with respect to the total area of the Mg 2 Si and Si phase observed in the cross section in the thickness direction of the plating layer is a random selection of the plating layer The area ratio of the Si phase observed in the cross section of 10 locations is averaged.

另外,於所述鍍覆層的厚度方向的剖面中所觀察到的Si相的面積率(觀察視場中的Si相的面積比例:D%)較佳為10%以下,更佳為3%以下。 In addition, the area ratio of the Si phase observed in the cross section in the thickness direction of the plating layer (the area ratio of the Si phase in the observation field: D%) is preferably 10% or less, more preferably 3% the following.

此處,關於在所述鍍覆層的厚度方向的剖面中所觀察到的Si相的面積率,為將於鍍覆層的隨機選擇的10個部位的剖面中所觀察到的Si相的面積率加以平均所得者。 Here, the area ratio of the Si phase observed in the cross section in the thickness direction of the plating layer is the area of the Si phase observed in the cross section of 10 randomly selected locations of the plating layer The rate is averaged.

進而,就進一步提高鍍覆鋼板的初期耐蝕性的觀點而言,於所述鍍覆層的表面所觀察到的Si相的面積率(觀察視場中的Si相的面積比例)較佳為1%以下,更佳為0.5%以下。此處,關於導出所述鍍覆層表面的Si相的面積率的方法,與觀察剖面的情況相同,可使用掃描型電子顯微鏡並利用能量分散型X射線分光法(SEM-EDX)來進行。面積率的求出方法可依據剖面觀察法來進行,可設為將於鍍覆層的隨機選擇的10個部位的表面中所觀察到的Si相的面積率加以平均所得者。 Furthermore, from the viewpoint of further improving the initial corrosion resistance of the plated steel sheet, the area ratio of the Si phase observed on the surface of the plating layer (the area ratio of the Si phase in the observation field) is preferably 1 % Or less, more preferably 0.5% or less. Here, the method for deriving the area ratio of the Si phase on the surface of the plating layer is the same as in the case of observing the cross section, and can be performed by using a scanning electron microscope and energy dispersive X-ray spectroscopy (SEM-EDX). The method of obtaining the area ratio can be based on the cross-sectional observation method, and it can be an average of the area ratios of the Si phases observed on the surface of 10 randomly selected locations of the plating layer.

進而,另外同樣就進一步提高初期耐蝕性的觀點而言,相對於在所述鍍覆層的表面中所觀察到的Mg2Si及Si相的合計面積而言的在所述鍍覆層的厚度方向的剖面中所觀察到的Si相的面 積比例(Si相的面積/Mg2Si及Si相的合計面積)較佳為20%以下,更佳為10%以下。實際的觀察方法、面積率的求出方法依據所述剖面觀察法。 Furthermore, from the viewpoint of further improving the initial corrosion resistance, the thickness of the plating layer is relative to the total area of the Mg 2 Si and Si phases observed on the surface of the plating layer. The area ratio of the Si phase observed in the cross section in the direction (the area of the Si phase/ the total area of the Mg 2 Si and the Si phase) is preferably 20% or less, more preferably 10% or less. The actual observation method and the calculation method of the area ratio are based on the cross-sectional observation method described above.

再者,當藉由掃描型電子顯微鏡來觀察所述鍍覆層的主層或所述界面合金層時,於對鍍覆層的剖面或表面進行研磨及/或蝕刻之後進行觀察。剖面或表面的研磨方法或蝕刻方法有幾種,若為通常觀察鍍覆層剖面或表面時所使用的方法,則無特別限定。另外,利用掃描型電子顯微鏡的觀察條件例如若為加速電壓5kV~20kV、且於二次電子束圖像或反射電子圖像中為500倍~5000倍左右的倍率,則能夠清晰地觀察所述鍍覆層的剖面。另外,於利用EDX進行映射的情況下,亦能夠藉由以相同的倍率進行分析來求出之前的面積率。 Furthermore, when observing the main layer of the plating layer or the interface alloy layer by a scanning electron microscope, the observation is performed after polishing and/or etching the cross section or surface of the plating layer. There are several methods of polishing or etching the cross section or surface, and there are no particular limitations as long as it is a method used when observing the cross section or surface of the plating layer. In addition, if the observation conditions with a scanning electron microscope are, for example, an acceleration voltage of 5kV to 20kV, and a magnification of about 500 to 5000 times in the secondary electron beam image or the reflected electron image, the observation can be clearly observed. Section of the plating layer. In addition, in the case of mapping using EDX, the previous area ratio can also be obtained by analyzing at the same magnification.

另外,所述鍍覆層的主層具有α-Al相的枝晶部分,該枝晶部分的平均枝晶臂間距離、與所述鍍覆層的厚度較佳為滿足以下式(1)。 In addition, the main layer of the plating layer has an α-Al phase dendrite portion, and the average interdendritic arm distance of the dendrite portion and the thickness of the plating layer preferably satisfy the following formula (1).

t/d≧1.5…(1) t/d≧1.5…(1)

t:鍍覆層的厚度(μm)、d:平均枝晶臂間距離(μm) t: thickness of plating layer (μm), d: average distance between dendrite arms (μm)

藉由滿足所述(1)式,可相對地減小所述包含α-Al相的枝晶部分的臂,將優先被腐蝕的枝晶間的路徑確保得長,藉此可進一步提升耐蝕性。 By satisfying the formula (1), the arms of the dendrite portion containing the α-Al phase can be relatively reduced, and the path between the dendrites that are preferentially corroded can be ensured long, thereby further improving the corrosion resistance .

再者,所謂所述枝晶部分的枝晶臂間距離,是指鄰接的枝晶臂間的中心距離(枝晶臂間距)。本發明中,例如如圖5所示,使用掃描型電子顯微鏡(SEM)等對鍍覆層主層的表面進行放大觀察(例如以200倍觀察),於隨機選擇的視場中,如以下般測定間隔第二寬的枝晶臂(二次枝晶臂)的間隔。選擇二次枝晶臂排列3條以上的部分(圖5中,選擇A-B區間的3條),沿著臂所排列的方向測定距離(圖5中為距離L)。其後,將所測定的距離除以枝晶臂的條數(圖5中為L/3),算出枝晶臂間距離。關於該枝晶臂間距離,於一個視場中測定3個部位以上,算出分別所得的枝晶臂間距離的平均並將所算出的平均值作為平均枝晶臂間距離。 In addition, the distance between the dendrite arms of the dendrite portion refers to the center distance between adjacent dendrite arms (dendrite arm pitch). In the present invention, for example, as shown in FIG. 5, a scanning electron microscope (SEM) or the like is used to magnify and observe the surface of the main layer of the plating layer (for example, observation at 200 times), in a randomly selected field of view, as follows The interval of the second widest dendrite arm (secondary dendrite arm) is measured. Select the part where three or more secondary dendrite arms are arranged (in FIG. 5, select three in the A-B interval), and measure the distance along the direction in which the arms are arranged (distance L in FIG. 5). After that, the measured distance was divided by the number of dendrite arms (L/3 in FIG. 5) to calculate the distance between dendrite arms. Regarding the distance between the dendrite arms, three or more locations were measured in one field of view, and the average of the distance between the dendrite arms was calculated, and the calculated average value was used as the average distance between the dendrite arms.

再者,就以高水準兼顧加工性與耐蝕性的觀點而言,所述鍍覆層的膜厚較佳為10μm~30μm,更佳為20μm~25μm。原因在於:於所述鍍覆層為10μm以上的情況下,可確保充分的耐蝕性,於所述鍍覆層為30μm以下的情況下,可充分確保加工性。 Furthermore, from the viewpoint of achieving both processability and corrosion resistance at a high level, the thickness of the plating layer is preferably 10 μm to 30 μm, and more preferably 20 μm to 25 μm. The reason is that when the plating layer is 10 μm or more, sufficient corrosion resistance can be ensured, and when the plating layer is 30 μm or less, sufficient workability can be ensured.

進而,本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板亦可製成於其表面更包括化學轉化處理皮膜及/或塗膜的表面處理鋼板。 Furthermore, the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention can also be made into a surface-treated steel sheet that further includes a chemical conversion treatment film and/or a coating film on its surface.

(熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法) (Method for manufacturing molten Al-Zn-Mg-Si-Sr coated steel sheet)

繼而,對本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法進行說明。 Next, the manufacturing method of the molten Al-Zn-Mg-Si-Sr plated steel sheet of this invention is demonstrated.

本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法的特徵在於:使用鍍覆浴,所述鍍覆浴含有Al:40質量%~70質量%、Si: 0.6質量%~5質量%、Mg:0.1質量%~10質量%及Sr:0.001質量%~1.0質量%,且具有剩餘部分包含Zn及不可避免的雜質的組成,且浴溫為585℃以下,對鋼板實施熔融鍍覆時,將進入所述鍍覆浴時的鋼板溫度(進入板溫)設為自所述鍍覆浴的浴溫加上20℃所得的溫度(鍍覆浴溫+20℃)以下。 The manufacturing method of the molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention is characterized by using a coating bath containing Al: 40% by mass to 70% by mass, Si: 0.6 mass% to 5 mass%, Mg: 0.1 mass% to 10 mass%, and Sr: 0.001 mass% to 1.0 mass%, and the remainder contains Zn and inevitable impurities, and the bath temperature is 585°C or less, When hot-dip coating is applied to the steel sheet, the temperature of the steel sheet when entering the coating bath (entry plate temperature) is set to the temperature obtained by adding 20°C to the bath temperature of the coating bath (plating bath temperature + 20°C )the following.

藉由所述製造方法所得的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板具有良好的表面外觀性,並且平板部及加工部的耐蝕性亦優異。 The molten Al-Zn-Mg-Si-Sr plated steel sheet obtained by the manufacturing method has good surface appearance, and the flat plate portion and the processed portion are also excellent in corrosion resistance.

於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法中,雖無特別限定,但就製造效率或品質穩定性的觀點而言,通常採用連續式熔融鍍覆設備。 In the manufacturing method of the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention, although not particularly limited, from the viewpoint of manufacturing efficiency and quality stability, continuous hot-dip coating equipment is generally used.

再者,關於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中所使用的基底鋼板的種類,並無特別限定。例如可使用:經酸洗除鏽的熱軋鋼板或鋼帶、或將該些進行冷軋而得的冷軋鋼板或鋼帶。 In addition, the kind of base steel sheet used in the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention is not particularly limited. For example, hot-rolled steel sheets or steel strips that have been pickled and derusted, or cold-rolled steel sheets or steel strips obtained by cold-rolling these can be used.

另外,關於所述預處理步驟及退火步驟的條件,亦無特別限定,可採用任意方法。 In addition, the conditions of the pretreatment step and the annealing step are not particularly limited, and any method can be adopted.

於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法中,所述鍍覆浴含有Al:40質量%~70質量%、Si:0.6質量%~5質量%、Mg:0.1質量%~10質量%及Sr:0.001質量%~1.0質量%,且具有剩餘部分包含Zn及不可避免的雜質的組成。 In the method for manufacturing a molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention, the coating bath contains Al: 40% by mass to 70% by mass, Si: 0.6% by mass to 5% by mass, and Mg: 0.1% by mass to 10% by mass and Sr: 0.001% by mass to 1.0% by mass, and the balance includes Zn and unavoidable impurities.

藉此,可獲得所期望的組成的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板。再者,關於所述鍍覆浴中所含有的各元素的種類或含量、作用,於所述本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板中進行了說明。 Thereby, the molten Al-Zn-Mg-Si-Sr plated steel sheet of the desired composition can be obtained. In addition, the type, content, and function of each element contained in the coating bath are described in the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention.

再者,藉由本發明的製造方法所得的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板整體上與鍍覆浴的組成大致同等。因此,對所述主層的組成的控制可藉由控制鍍覆浴組成而精度佳地進行。 In addition, the molten Al-Zn-Mg-Si-Sr plated steel sheet obtained by the production method of the present invention is substantially the same as the composition of the coating bath as a whole. Therefore, the control of the composition of the main layer can be performed accurately by controlling the composition of the plating bath.

另外,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法中,所述鍍覆浴中的Mg及Si的含量較佳為滿足以下式(2)。 In addition, in the manufacturing method of the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention, the content of Mg and Si in the coating bath preferably satisfies the following formula (2).

MMg/(MSi-0.6)≧1.0…(2) M Mg /(M Si -0.6)≧1.0…(2)

MMg:Mg的含量(質量%)、MSi:Si的含量(質量%) M Mg : Mg content (mass%), M Si : Si content (mass%)

藉由使所述鍍覆浴中的Mg及Si的含量滿足所述關係式,所形成的鍍覆層可抑制Si相的產生(例如,於鍍覆層的厚度方向的剖面中所觀察到的Si相的面積率成為10%以下,於鍍覆層的表面中所觀察到的Si相的面積率成為1%以下),並實現加工性及耐蝕性的進一步提升。 By making the contents of Mg and Si in the plating bath satisfy the relational expression, the formed plating layer can suppress the generation of Si phase (for example, as observed in the cross section in the thickness direction of the plating layer The area ratio of the Si phase becomes 10% or less, and the area ratio of the Si phase observed on the surface of the plating layer becomes 1% or less), and the workability and corrosion resistance are further improved.

就同樣的觀點而言,MMg/(MSi-0.6)更佳為2.0以上,進而佳為3.0以上。 From the same viewpoint, M Mg /(M Si -0.6) is more preferably 2.0 or more, and still more preferably 3.0 or more.

於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法中,所述鍍覆浴的浴溫為585℃以下,較佳為580℃以下。藉由該浴溫設定,可減少自所述鍍覆層的主層表面起到達界面合金層為止般的大的Mg2Si的量。另外,亦具有抑制界面合金層成長的效果。低浴溫化有效發揮作用的原因在於:能夠使鋼板於Mg2Si及 界面合金層成長的高溫區域停留的時間成為短時間。於所述鍍覆浴的浴溫超過585℃的情況下,即便在對於進入所述鍍覆浴時的鋼板溫度而言實現了合理化的情況下,自所述主層的表面起到達界面合金層為止般的大的Mg2Si的量亦變多,另外,由於界面合金層厚厚地成長,因此無法獲得所期望的加工性及加工部的耐蝕性。 In the method for manufacturing a molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention, the bath temperature of the coating bath is 585°C or less, preferably 580°C or less. With this bath temperature setting, the amount of Mg 2 Si that is large from the surface of the main layer of the plating layer to the interface alloy layer can be reduced. In addition, it also has the effect of suppressing the growth of the interface alloy layer. The reason why the low bath temperature effectively works is that the time for the steel sheet to stay in the high temperature region where the Mg 2 Si and the interface alloy layer grows can be shortened. In the case where the bath temperature of the coating bath exceeds 585°C, even if the steel sheet temperature when entering the coating bath is rationalized, it reaches the interface alloy layer from the surface of the main layer The amount of Mg 2 Si that has been so large has also increased, and since the interface alloy layer grows thickly, the desired workability and corrosion resistance of the processed part cannot be obtained.

另外,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法中,將進入所述鍍覆浴時的鋼板溫度(進入板溫)設為自所述鍍覆浴的浴溫加上20℃所得的溫度(鍍覆浴溫+20℃)以下。藉此,可減少自所述鍍覆層的主層表面起到達界面合金層為止般的大的Mg2Si的量。作為藉由降低進入板溫可減少大的Mg2Si的量的原因,與降低所述浴溫時的效果相同,原因在於:能夠使鋼板於Mg2Si及界面合金層成長的高溫區域停留的時間成為短時間。 In addition, in the manufacturing method of the molten Al-Zn-Mg-Si-Sr plated steel sheet of the present invention, the temperature of the steel sheet when entering the coating bath (entering plate temperature) is set as the bath from the coating bath The temperature obtained by adding 20°C (plating bath temperature + 20°C) or less. Thereby, it is possible to reduce the amount of Mg 2 Si that is large from the surface of the main layer of the plating layer to the interface alloy layer. The reason why the large amount of Mg 2 Si can be reduced by lowering the entering plate temperature is the same as the effect when lowering the bath temperature. The reason is that the steel sheet can stay in the high temperature region where Mg 2 Si and the interface alloy layer grows. Time becomes short time.

就同樣的觀點而言,所述鋼板的進入板溫較佳為自所述鍍覆浴的浴溫加上10℃所得的溫度(鍍覆浴溫+10℃)以下,更佳為所述鍍覆浴的浴溫以下。 From the same point of view, the entry temperature of the steel sheet is preferably a temperature (plating bath temperature + 10°C) obtained from the bath temperature of the coating bath plus 10°C or less, and more preferably the coating temperature Below the bath temperature of the covering bath.

進而,於本發明的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法中,較佳為對所述鋼板實施熔融鍍覆後,以10℃/s以上的平均冷卻速度將所述鋼板冷卻至板溫成為自所述鍍覆浴的浴溫減去150℃所得的溫度(鍍覆浴溫-150℃)為止。關於在所述鍍覆層中所形成的Mg2Si,已知其容易於自鍍覆浴的浴溫起至自鍍覆浴的浴溫減去150℃所得的溫度(鍍覆浴溫-150℃)為止的溫度區域內生成,藉由將該溫度區域內的冷卻速度加快為平均10℃/sec以上, 可抑制Mg2Si的成長,且減少自所述鍍覆層的主層表面起到達界面合金層為止般的大的Mg2Si的量。進而,藉由提高所述熔融鍍覆後的鋼板的冷卻速度,亦可抑制所述界面合金層的成長,結果,可實現優異的加工部的耐蝕性。 Furthermore, in the method for manufacturing a molten Al-Zn-Mg-Si-Sr coated steel sheet of the present invention, it is preferable that the steel sheet is subjected to hot-dip coating, and then the steel sheet is heated at an average cooling rate of 10°C/s or more. The steel plate is cooled until the plate temperature becomes the temperature obtained by subtracting 150°C from the bath temperature of the coating bath (coating bath temperature-150°C). Regarding the Mg 2 Si formed in the plating layer, it is known that it is easy to change from the bath temperature of the plating bath to the temperature obtained by subtracting 150°C from the bath temperature of the plating bath (plating bath temperature -150 ℃). By increasing the cooling rate in this temperature range to an average of 10℃/sec or more, the growth of Mg 2 Si can be suppressed and the arrival from the main layer surface of the plating layer can be reduced. The amount of Mg 2 Si is as large as the interface alloy layer. Furthermore, by increasing the cooling rate of the steel sheet after the hot-dip coating, the growth of the interface alloy layer can also be suppressed, and as a result, the excellent corrosion resistance of the processed part can be realized.

再者,關於所述平均冷卻速度,其是藉由求出直至鋼板成為自鍍覆浴溫減去150℃所得的溫度為止的時間並將150℃除以該時間而求出。 In addition, the said average cooling rate is calculated|required by calculating the time until the steel sheet reaches the temperature obtained by subtracting 150°C from the coating bath temperature and dividing 150°C by the time.

另外,藉由將所述溫度區域內的冷卻速度加快為平均10℃/sec以上,能夠將鍍覆主層的表面附近所存在的Mg2Si的量增加至整體的50%以上。其原因如下。所述界面合金層是藉由所述鍍覆浴中的固液反應(浴中的Al與鋼板的反應)而生成,於該反應時Si亦混入至界面合金層中。因此,枝晶間發生凝固時的界面合金層附近的Si濃度變得低於鍍覆主層的平均Si濃度,關於Mg2Si的分佈,與界面合金層側相比,鍍覆主層表面側變多。另一方面,於鍍覆後的冷卻過程中,所述鍍覆鋼板自表面起冷卻,因此,自表面起發生枝晶間的凝固。溫度越低,Zn中的Mg2Si的溶解度越小,於固液界面,Mg及Si於液相側被排出,從而濃縮於液體的枝晶間部。越接近平衡狀態,即冷卻速度越慢,該現象越顯著,因此,於冷卻速度慢的情況下,Mg2Si的分佈容易偏向存在於界面合金層附近。即,藉由使冷卻速度加快(為平均10℃/sec以上),關於所述Mg2Si的分佈,可抑制在界面合金層附近的偏向存在,並維持原本的Mg2Si的分佈。即,可將所述鍍覆層中的Mg2Si 的分佈確保為與所述界面合金層的附近相比,所述主層表面側更多的狀態。 In addition, by increasing the cooling rate in the temperature range to an average of 10° C./sec or more, the amount of Mg 2 Si present in the vicinity of the surface of the main plating layer can be increased to 50% or more of the whole. The reason is as follows. The interface alloy layer is formed by a solid-liquid reaction (a reaction between Al in the bath and the steel sheet) in the plating bath, and Si is also mixed into the interface alloy layer during the reaction. Therefore, the Si concentration near the interface alloy layer when solidification occurs between dendrites becomes lower than the average Si concentration of the main plating layer. Regarding the distribution of Mg 2 Si, the surface side of the main plating layer is compared with the interface alloy layer side. Become more. On the other hand, in the cooling process after plating, the plated steel sheet is cooled from the surface, and therefore, interdendritic solidification occurs from the surface. The lower the temperature, the lower the solubility of Mg 2 Si in Zn, and at the solid-liquid interface, Mg and Si are discharged on the liquid side and concentrated in the interdendritic part of the liquid. The closer to the equilibrium state, that is, the slower the cooling rate, the more significant this phenomenon is. Therefore, when the cooling rate is slow, the distribution of Mg 2 Si tends to exist in the vicinity of the interface alloy layer. That is, by increasing the cooling rate (average 10° C./sec or more), the distribution of the Mg 2 Si can suppress the presence of deviation in the vicinity of the interface alloy layer and maintain the original Mg 2 Si distribution. That is, the distribution of Mg 2 Si in the plating layer can be ensured in a state where there is more on the surface side of the main layer than the vicinity of the interface alloy layer.

就同樣的觀點而言,所述熔融鍍覆後的鋼板的冷卻更佳為以20℃/sec以上的平均冷卻速度進行,進而佳為以30℃/sec以上的平均冷卻速度進行,特佳為以40℃/sec以上的平均冷卻速度進行。 From the same point of view, the cooling of the hot-dip galvanized steel sheet is more preferably performed at an average cooling rate of 20°C/sec or more, more preferably performed at an average cooling rate of 30°C/sec or more, and particularly preferably Perform at an average cooling rate of 40°C/sec or more.

再者,於本發明的製造方法中,關於所述熔融鍍覆時的浴溫及進入板溫、以及熔融鍍覆後的冷卻條件以外的條件,並無特別限定,可依據常用方法來製造熔融Al-Zn-Mg-Si-Sr鍍覆鋼板。 Furthermore, in the manufacturing method of the present invention, there are no particular restrictions on the bath temperature and the entering plate temperature during the hot-dip coating, and the conditions other than the cooling conditions after the hot-dip coating. The molten metal can be manufactured according to common methods. Al-Zn-Mg-Si-Sr coated steel sheet.

藉由本發明的製造方法所得的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板亦可於其表面進而形成化學轉化處理皮膜(化學轉化處理步驟)、或者於另外的塗裝設備中進而形成塗膜(塗膜形成步驟)。 The molten Al-Zn-Mg-Si-Sr coated steel sheet obtained by the manufacturing method of the present invention can also form a chemical conversion treatment film (chemical conversion treatment step) on its surface, or form a coating in another coating equipment. Film (coating film forming step).

再者,關於所述化學轉化處理皮膜,例如可藉由鉻酸鹽處理或無鉻酸鹽化學轉化處理而形成,所述處理是塗佈鉻酸鹽處理液或無鉻酸鹽化學轉化處理液,不進行水洗而進行鋼板溫度成為80℃~300℃的乾燥處理。該些化學轉化處理皮膜可為單層亦可為多層,於為多層的情況下,只要依序進行多個化學轉化處理即可。 Furthermore, the chemical conversion treatment film may be formed by, for example, a chromate treatment or a chromate-free chemical conversion treatment, and the treatment is to coat a chromate treatment liquid or a chromate-free chemical conversion treatment liquid. , Without water washing, the steel plate temperature becomes 80 ℃ ~ 300 ℃ drying treatment. These chemical conversion treatment films may be a single layer or multiple layers. In the case of multiple layers, it is sufficient to perform a plurality of chemical conversion treatments in sequence.

另外,關於所述塗膜,可列舉:輥塗機塗裝、淋幕式塗裝、噴霧塗裝等形成方法。於塗裝含有有機樹脂的塗料後,可藉由熱風乾燥、紅外線加熱、感應加熱等方法進行加熱乾燥而形成塗膜。 Moreover, about the said coating film, the formation method, such as roll coater coating, curtain coating, and spray coating, can be mentioned. After coating the paint containing organic resin, it can be heated and dried by hot air drying, infrared heating, induction heating and other methods to form a coating film.

[實施例] [Example]

(樣品1~樣品25) (Sample 1~Sample 25)

將利用常用方法製造的板厚為0.5mm的冷軋鋼板用作基底 鋼板,於連續式熔融鍍覆設備中,進行樣品1~樣品25的熔融Al-Zn系鍍覆鋼板的製造。再者,關於製造中所使用的鍍覆浴的組成,與表1所示的各樣品的鍍覆層的組成大致相同,關於鍍覆浴的浴溫、鋼板的進入板溫以及至自鍍覆浴的浴溫減去150℃所得的溫度為止的冷卻速度,示於表1中。 Use a cold-rolled steel plate with a thickness of 0.5 mm manufactured by a common method as a base For the steel sheet, the molten Al-Zn-based coated steel sheet of sample 1 to sample 25 was manufactured in a continuous hot-dip coating equipment. In addition, the composition of the plating bath used in the manufacture is approximately the same as the composition of the plating layer of each sample shown in Table 1. The bath temperature of the plating bath, the entry temperature of the steel sheet, and the self-coating Table 1 shows the cooling rate up to the temperature obtained by subtracting 150°C from the bath temperature of the bath.

其後,關於所得的熔融Al-Zn系鍍覆鋼板的各樣品,使用掃描型電子顯微鏡並藉由能量分散型X射線分光法(SEM-EDX),於隨機的一個部位進行剖面觀察。 After that, with respect to each sample of the obtained molten Al-Zn-based plated steel sheet, a cross-sectional observation was performed at a random location by energy dispersive X-ray spectroscopy (SEM-EDX) using a scanning electron microscope.

而且,關於各樣品,測定或算出所形成的鍍覆層的各條件以及鍍覆的各製造條件,並示於表1中。 In addition, for each sample, each condition of the formed plating layer and each manufacturing condition of the plating were measured or calculated, and shown in Table 1.

(評價) (Evaluation)

對於如所述般獲得的熔融Al-Zn系鍍覆鋼板的各樣品,進行以下的評價。將評價結果示於表1中。 For each sample of the molten Al-Zn-based plated steel sheet obtained as described above, the following evaluations were performed. The evaluation results are shown in Table 1.

(1)表面外觀性 (1) Surface appearance

對於熔融Al-Zn系鍍覆鋼板的各樣品,於1000mm~1600mm左右的鋼板寬度×長度1000mm的觀察視場中,藉由目視來觀察鍍覆層的表面(各樣品的兩表面)。 For each sample of the molten Al-Zn-based coated steel sheet, the surface of the coating layer (both surfaces of each sample) was observed visually in an observation field of steel sheet width of about 1000 mm to 1600 mm × 1000 mm length.

而且,按照以下基準來評價觀察結果。 In addition, the observation results were evaluated according to the following criteria.

○:表面及背面中的任一者均完全未觀察到褶皺狀缺陷 ○: No wrinkle-like defects are observed on either the front surface or the back surface

×:於表面及背面中的至少一者中觀察到了褶皺狀缺陷 ×: A wrinkle-like defect is observed in at least one of the front surface and the back surface

(2)耐蝕性評價(平板部的耐蝕性) (2) Corrosion resistance evaluation (corrosion resistance of the flat part)

對於熔融Al-Zn系鍍覆鋼板的各樣品,進行日本汽車標準的 複合循環試驗(JASO-CCT)。關於JASO-CCT,為如圖6所示,於特定條件下將鹽水噴霧、乾燥及濕潤設為1個循環的試驗。 For each sample of the molten Al-Zn series coated steel sheet, the Japanese automobile standard Compound cycle test (JASO-CCT). Regarding JASO-CCT, it is a test in which salt water spraying, drying, and wetting are set as one cycle as shown in Fig. 6 under specific conditions.

對各樣品測定直至紅鏽產生為止的循環數,並按照以下基準進行評價。 The number of cycles until the occurrence of red rust was measured for each sample, and evaluated in accordance with the following criteria.

○:紅鏽產生循環數≧400個循環 ○: The number of cycles of red rust generation≧400 cycles

△:300個循環≦紅鏽產生循環數<400個循環 △: 300 cycles≦red rust generation cycles <400 cycles

×:紅鏽產生循環數<300個循環 ×: Red rust production cycle number <300 cycles

(3)彎曲加工部耐蝕性評價(加工部的耐蝕性) (3) Evaluation of the corrosion resistance of the bent part (corrosion resistance of the processed part)

對於熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的各樣品,於內側夾持3片相同板厚的板並實施180°彎曲的加工(3T彎曲)後,於彎曲的外側進行日本汽車標準的複合循環試驗(JASO-CCT)。關於JASO-CCT,為如圖6所示,於特定條件下將鹽水噴霧、乾燥及濕潤設為1個循環的試驗。 For each sample of the molten Al-Zn-Mg-Si-Sr plated steel sheet, 3 sheets of the same thickness were clamped on the inner side and subjected to a 180° bending process (3T bending), and then the Japanese automobile standard was performed on the outer side of the bend The combined cycle test (JASO-CCT). Regarding JASO-CCT, it is a test in which salt water spraying, drying, and wetting are set as one cycle under specific conditions as shown in Figure 6.

對各樣品的加工部測定直至紅鏽產生為止的循環數,並按照以下基準進行評價。 The number of cycles until the occurrence of red rust was measured for the processed part of each sample, and evaluated in accordance with the following criteria.

○:紅鏽產生循環數≧400個循環 ○: Number of cycles of red rust generation≧400 cycles

△:300個循環≦紅鏽產生循環數<400個循環 △: 300 cycles≦red rust generation cycle number <400 cycles

×:紅鏽產生循環數<300個循環 ×: Red rust production cycle number <300 cycles

[表1]

Figure 108144608-A0305-02-0031-2
[Table 1]
Figure 108144608-A0305-02-0031-2

根據表1可知,本發明例的各樣品與比較例的各樣品相比,表面外觀性、耐蝕性及加工部耐蝕性中的任一者均平衡性佳地優異。 From Table 1, it can be seen that each sample of the present invention example has a well-balanced and excellent surface appearance, corrosion resistance, and corrosion resistance of a processed part compared with each sample of the comparative example.

[產業上之可利用性] [Industrial availability]

根據本發明,可提供一種具有良好的表面外觀性、並且平板部及加工部的耐蝕性優異的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,以及具有良好的表面外觀性、並且平板部及加工部的耐蝕性優異的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法。 According to the present invention, it is possible to provide a fused Al-Zn-Mg-Si-Sr plated steel sheet with good surface appearance and excellent corrosion resistance of the flat part and the processed part, and the flat part with good surface appearance And a method for manufacturing a molten Al-Zn-Mg-Si-Sr plated steel sheet with excellent corrosion resistance of the processed part.

Claims (7)

一種熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,其特徵在於:鍍覆層含有Al:40質量%~70質量%、Si:0.6質量%~5質量%、Mg:0.1質量%~10質量%及Sr:0.001質量%~1.0質量%,且具有剩餘部分包含Zn及不可避免的雜質的組成,所述鍍覆層包含存在於與基底鋼板的界面的界面合金層、及存在於所述界面合金層上的主層,於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中,自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例為50%以上,且自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例為50%以下。 A molten Al-Zn-Mg-Si-Sr coated steel sheet, characterized in that the coating layer contains Al: 40% to 70% by mass, Si: 0.6% to 5% by mass, and Mg: 0.1% to 10% by mass Mass% and Sr: 0.001% to 1.0% by mass, with the remainder including Zn and inevitable impurities, and the plating layer includes an interface alloy layer present at the interface with the base steel sheet, and master alloy layer at the interface layer, Mg 2 Si in the cross-sectional direction of the plate thickness of the coating was observed in, from the inner surface of the main layer to a thickness range of up to 50% of Mg 2 Si is present The area ratio of Mg 2 Si is 50% or more, and the area ratio of Mg 2 Si extending from the surface of the main layer to the interface alloy layer is 50% or less. 如請求項1所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,其中於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中,自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例為60%以上,且自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例為50%以下。 The molten Al-Zn-Mg-Si-Sr coated steel sheet according to claim 1, wherein in the Mg 2 Si observed in the cross section in the thickness direction of the coating layer, from the surface of the main layer area proportion up to 50% of a thickness range of Mg 2 Si is present in 60% or more, and extends from the main surface layer to reach the interface area until the ratio of Mg 2 Si alloy layer is 50% the following. 如請求項1或請求項2所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,其中於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中,自所述主層的表面至50%為止的厚度範圍內所存在的Mg2Si的面積比例為60%以上,且自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例為40%以下。 The molten Al-Zn-Mg-Si-Sr coated steel sheet according to claim 1 or claim 2, wherein in the Mg 2 Si observed in the cross section in the thickness direction of the coating layer, from the 2 Mg Si area ratio of the inner surface of the main layer to a thickness range of up to 50% is present 60% or more, and extends from the main surface layer to reach the area of Mg 2 Si alloy layer until the interface The ratio is less than 40%. 如請求項1或請求項2所述的熔融Al-Zn-Mg-Si-Sr 鍍覆鋼板,其中關於在所述鍍覆層的厚度方向的剖面中所觀察到的Si相,相對於在所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si及Si相的面積率的合計而言的Si相的面積率的比例為30%以下。 The molten Al-Zn-Mg-Si-Sr coated steel sheet according to claim 1 or claim 2, wherein the Si phase observed in the cross section in the thickness direction of the coating layer is relative to the The ratio of the area ratio of the Si phase, which is the total of the area ratios of the Mg 2 Si and Si phases observed in the cross section in the thickness direction of the plating layer, is 30% or less. 如請求項1或請求項2所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板,其中所述主層具有α-Al相的枝晶部分,所述枝晶部分的平均枝晶臂間距離、與所述鍍覆層的厚度滿足以下式(1);t/d≧1.5…(1)t:鍍覆層的厚度(μm)、d:平均枝晶臂間距離(μm)。 The molten Al-Zn-Mg-Si-Sr coated steel sheet according to claim 1 or claim 2, wherein the main layer has a dendrite portion of an α-Al phase, and the average dendrite arm of the dendrite portion The distance and the thickness of the plating layer satisfy the following formula (1); t/d≧1.5...(1) t: thickness of the plating layer (μm), d: average distance between dendrite arms (μm). 一種熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法,其特徵在於:使用鍍覆浴,所述鍍覆浴含有Al:40質量%~70質量%、Si:0.6質量%~5質量%、Mg:0.1質量%~10質量%及Sr:0.001質量%~1.0質量%,且具有剩餘部分包含Zn及不可避免的雜質的組成,且浴溫為585℃以下,對鋼板實施熔融鍍覆時,將進入所述鍍覆浴時的鋼板溫度(進入板溫)設為所述鍍覆浴的浴溫以下,所形成的鍍覆層包含存在於與基底鋼板的界面的界面合金層、及存在於所述界面合金層上的主層,於所述鍍覆層的厚度方向的剖面中所觀察到的Mg2Si中,自所述主層的表面至50%為止 的厚度範圍內所存在的Mg2Si的面積比例為50%以上,且自所述主層的表面起延伸至到達所述界面合金層為止的Mg2Si的面積比例為50%以下。 A method for manufacturing a molten Al-Zn-Mg-Si-Sr coated steel sheet is characterized in that: a coating bath is used, and the coating bath contains Al: 40% by mass to 70% by mass, and Si: 0.6% by mass to 5 Mass%, Mg: 0.1% to 10% by mass and Sr: 0.001% to 1.0% by mass, and the remainder contains Zn and unavoidable impurities, and the bath temperature is 585°C or less. Hot-dip coating is applied to the steel sheet During coating, the temperature of the steel sheet when entering the coating bath (entering plate temperature) is set below the bath temperature of the coating bath, and the formed coating layer includes an interface alloy layer present at the interface with the base steel sheet, And the main layer existing on the interface alloy layer, in the Mg 2 Si observed in the cross section in the thickness direction of the plating layer, the thickness range from the surface of the main layer to 50% area ratio of Mg 2 Si is present in 50% or more, and extends from the main surface layer to reach the interface area until the ratio of Mg 2 Si alloy layer is 50% or less. 如請求項6所述的熔融Al-Zn-Mg-Si-Sr鍍覆鋼板的製造方法,其中對所述鋼板實施熔融鍍覆後,以10℃/s以上的平均冷卻速度將所述鋼板冷卻至板溫成為自所述鍍覆浴的浴溫減去150℃所得的溫度(鍍覆浴溫-150℃)為止。 The method for manufacturing a molten Al-Zn-Mg-Si-Sr coated steel sheet according to claim 6, wherein after the steel sheet is subjected to hot-dip coating, the steel sheet is cooled at an average cooling rate of 10°C/s or more Until the plate temperature becomes the temperature obtained by subtracting 150°C from the bath temperature of the plating bath (plating bath temperature-150°C).
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