CN115244208B - 热冲压用镀覆钢板 - Google Patents

热冲压用镀覆钢板 Download PDF

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Publication number
CN115244208B
CN115244208B CN202180019692.2A CN202180019692A CN115244208B CN 115244208 B CN115244208 B CN 115244208B CN 202180019692 A CN202180019692 A CN 202180019692A CN 115244208 B CN115244208 B CN 115244208B
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Prior art keywords
layer
zinc
steel sheet
content
plating
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CN115244208A (zh
Inventor
竹林浩史
秋叶浩二郎
仙石晃大
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/02—Stamping using rigid devices or tools
    • B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20—Deep-drawing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • 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
    • 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
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • 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
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    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/285—Thermal after-treatment, e.g. treatment in oil bath for remelting the coating
    • 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
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • 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
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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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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
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Abstract

一种热冲压用镀覆钢板，其具备母材和在母材的表面形成的镀锌层，其中，镀锌层从母材侧起依次具有合金化锌层、凝固锌层以及含有Al的氧化物层，凝固锌层中的Zn含量(g/m2)相对于镀锌层中的Zn含量(g/m2)的比例为10％～95％。

Description

热冲压用镀覆钢板
技术领域
本发明涉及一种热冲压用镀覆钢板。
背景技术
对于构成汽车的车身的各种汽车部件，根据该部件的用途而要求多种多样的性能。例如，在A柱加强件、B柱加强件、保险杠加强件、通道加强件、侧梁加强件、车顶加强件或地板横梁等汽车部件中，要求仅各个汽车部件中的特定部位具有比除该特定部位之外的一般部位高的强度。因此，一部分采用仅对汽车部件中的相当于需要加强的特定部位的部分进行热冲压成形而制成热冲压构件的工艺。
此时，若使用未实施表面处理的冷轧钢板，则在加热中在钢板表面产生铁的氧化皮。该氧化皮不仅在成形中剥离而损耗模具，而且成为在钢板表面产生瑕疵的原因。另外，如果在成形后的钢板表面残留氧化皮，则有时成为之后的焊接工序中的焊接不良、或涂装工序中的涂装的密合性不良的原因。
因此，为了防止氧化皮的生成，如专利文献1所记载的那样，有时使用锌系等的镀覆钢板。通过使用锌系的镀覆钢板，锌比铁先被少量氧化，从而能够抑制铁的氧化，大幅改善焊接性和涂装性。
进而，近年来，对这些部件也要求耐腐蚀性，例如，在专利文献2～5中，开发了如下技术：使加热前的钢板的镀覆附着量为厚单位面积重量，在加热后的镀覆表面残留Zn含量为约70％且剩余部分以Fe为主要成分的镀覆，提高耐腐蚀性。
现有技术文献
专利文献
专利文献1：日本特开2003-126921号公报
专利文献2：日本特开2005-240072号公报
专利文献3：日本特开2006-022395号公报
专利文献4：日本特开2007-182608号公报
专利文献5：日本特开2011-117086号公报
发明内容
发明要解决的问题
然而，在以连续生产线形成镀层的情况下，为了抑制镀浴中的Zn与母材中的Fe反应而过度地合金化，需要使镀浴中含有少量的Al。
特别是，在使用厚单位面积重量的含Al的Zn镀覆时，有时在加热成形后产生蜘蛛网状的表面缺陷。该蜘蛛网状的表面缺陷为凸状缺陷，在进行汽车用的涂装后有时也会在表面浮出，因此在品质上不优选。
因而，需要抑制该蜘蛛网状的缺陷。然而，实际情况是，其产生机理、抑制其的方法都不是很清楚。
本发明的目的在于解决上述问题，提供一种在使用了含Al的Zn镀覆的情况下，能够抑制蜘蛛网状的表面缺陷的热冲压用镀覆钢板。
用于解决问题的方案
本发明是为了解决上述课题而完成的，其要旨在于下述热冲压用镀覆钢板。
(1)一种热冲压用镀覆钢板，其具备母材和在所述母材的表面形成的镀锌层，其中，
所述镀锌层从所述母材侧起依次具有合金化锌层、凝固锌层以及含有Al的氧化物层，
所述凝固锌层中的Zn含量(g/m2)相对于所述镀锌层中的Zn含量(g/m2)的比例为10％～95％。
(2)根据上述(1)所述的热冲压用镀覆钢板，其中，
所述氧化物层的化学组成满足下述(i)式：
3.0≤Zn/Al≤6.0…(i)
其中，上述式中的Zn和Al分别为所述氧化物层中所含有的Zn和Al的含量(g/m2)。
(3)根据上述(1)或(2)所述的热冲压用镀覆钢板，其中，
所述氧化物层的平均厚度为1.0μm以下。
(4)根据上述(1)～(3)中任一项所述的热冲压用镀覆钢板，其中，
所述镀锌层的Zn含量为65g/m2～150g/m2。
(5)根据上述(1)～(4)中任一项所述的热冲压用镀覆钢板，其中，
所述镀锌层的Fe含量以质量％计小于7％。
发明的效果
根据本发明，能够得到一种在使用了含Al的Zn镀覆的情况下，能够抑制蜘蛛网状的表面缺陷的热冲压用镀覆钢板。
具体实施方式
本发明人等对蜘蛛网状的表面缺陷产生的原因进行了调查，结果得到了以下的见解。
(a)在镀浴中含有Al的情况下，在镀层的表面形成薄的含有Al的氧化物层。特别是在厚单位面积重量的情况下，通过热冲压时的加热，镀层成为液相而流动，由于与此相伴的应力而在氧化物层产生细小的裂纹。
(b)镀覆中的Zn、Mn等流入因氧化物层的裂纹而产生的间隙，这些氧化物填充，从而成为蜘蛛网状，表面性状恶化。
本发明的发明人等对抑制氧化物层的裂纹的方法进行了专心研究，进而得到了以下的见解。
(c)通过将镀层适度地合金化而形成合金化锌层，并控制在其上层形成的锌凝固层的比例，能够抑制镀覆液相的流动。
(d)进而，通过对氧化物层进行改性，使氧化物层中的Zn含量相对于Al含量相对地增加，从而氧化物层变得软质，更不易产生裂纹。
(e)对于氧化物层的改性，擦拭条件的最佳化是有效的。
本发明是基于上述的见解而完成的。以下，详细地说明本发明的各要件。
(A)整体结构
本发明的一实施方式的热冲压用镀覆钢板具备母材和在母材的表面形成的镀锌层。以下详细说明镀锌层的结构。
(B)镀锌层
本发明中的镀锌层从母材侧起依次具有合金化锌层、凝固锌层以及含有Al的氧化物层。关于镀锌层的单位面积重量，没有特别限制，例如Zn含量能够设为30g/m2～180g/m2。另外，越是厚单位面积重量，耐腐蚀性越提高。
此外，越是厚单位面积重量，越容易产生蜘蛛网状的表面缺陷。因此，在镀锌层的单位面积重量以Zn含量计为65g/m2以上的情况下，可显著地发挥本发明的效果。另一方面，从抑制蜘蛛网状的表面缺陷的观点出发，镀锌层的单位面积重量以Zn含量计优选为150g/m2以下。
另外，在一般的合金化热浸镀钢板的情况下，需要使镀锌层完全合金化，因此镀锌层中的Fe含量为7％以上。另一方面，在本发明中，如后所述，不使镀锌层完全合金化。因此，镀锌层中整体的平均Fe含量以质量％计优选小于7％，更优选为6％以下。
(C)合金化锌层
合金化锌层是通过镀浴中的Zn与母材中的Fe反应而金属间化合物化而形成的层。通过以适度的量形成合金化锌层，能够控制后述的凝固锌层的比例，抑制热冲压时的镀覆液相的流动。
(D)凝固锌层
凝固锌层是热浸镀锌浴凝固而成的层，通常也被称为η层。并且，在本发明中，相对于镀锌层中的Zn含量(g/m2)，将凝固锌层中的Zn含量(g/m2)的比例设为10％～95％。
在利用连续生产线制造的未合金化的通常的热浸镀锌钢板的情况下，通过镀浴中含有的Al，镀浴中的Zn与母材中的Fe的反应被抑制。因此，镀锌层的大部分为凝固锌层，例如，凝固锌层中的Zn含量的比例超过95％。
如上所述，在厚单位面积重量的情况下，通过热冲压时的加热，凝固锌层成为液相而流动，因此，在本发明中，使凝固锌层的比例适度减少。具体而言，通过使凝固锌层中的Zn含量的比例相对于镀锌层中的Zn含量为95％以下，能够抑制镀覆液相的流动。为了抑制镀覆液相的流动，凝固锌层中的Zn含量的比例优选为85％以下或75％以下，更优选为65％以下或55％以下。
另一方面，在通常的合金化热浸镀锌钢板的情况下，通过使镀锌层完全合金化而制成合金化锌层。即，凝固锌层中的Zn含量的比例大致为0％。但是，若极端地降低凝固锌层的比例，则耐腐蚀性劣化。因此，在本发明中，需要使凝固锌层中的Zn含量的比例相对于镀锌层中整体的Zn含量为10％以上。为了保持镀锌层的耐腐蚀性，凝固锌层中的Zn含量的比例优选为20％以上，更优选为30％以上。
(E)氧化物层
在镀锌层的表面形成有含有Al的氧化物层。由于含有Al的氧化物层比较硬质，因此在加热时凝固锌层成为液相而流动，由此有可能产生裂纹。
如上所述，通过降低凝固锌层的比例，能够抑制镀覆液相的流动，抑制裂纹。除此之外，通过使氧化物层软质化，能够进一步有效地抑制裂纹的产生。因此，使Zn在氧化物层中相对富集，使Zn/Al的值为3.0以上是有效的。另外，通过使Zn/Al的值为6.0以下，能够抑制Zn系的氧化物的比率过度增加，在热冲压后在汽车用途等中实施的涂装时，可得到优异的涂装密合性。因此，氧化物层的化学组成优选满足下述(i)式。
3.0≤Zn/Al≤6.0…(i)
其中，上述式中的Zn和Al分别是氧化物层中所含有的Zn和Al的含量(g/m2)。
进而，氧化物层的平均厚度优选为1.0μm以下。通过将平均厚度设为1.0μm以下，氧化物的刚度变小，即使发生镀浴的流动，也会被细小地破碎，由此不会产生大而明显的裂纹，因此能够抑制明显的蜘蛛网状的缺陷。氧化物层的平均厚度更优选为0.8μm以下，进一步优选为0.6μm以下。
氧化物层的平均厚度越薄越理想，因此无需设置下限。但是，如上所述，在镀浴中含有Al的情况下，无法避免氧化物层的形成，因此氧化物层的平均厚度实质上超过0μm。
(F)测定方法
在本发明中，对于镀锌层的整体和各层的化学组成、厚度等，按照以下的步骤进行测定。
首先，将镀覆钢板浸渍于10％铬酸水溶液，仅将氧化物层溶解。然后，通过对溶解液进行ICP发射光谱分析，测定Al和Zn的含量，将其作为氧化物层中的含量。
接下来，在氯化铵150g/L的水溶液中，以4mA/cm2进行恒定电流电解。此时，将银-氯化银电极作为参比电极。然后，对于以-0.95V以下溶解的溶解液，通过ICP发射光谱分析测定Zn含量，作为凝固锌层的Zn含量。
接下来，对于剩余的镀层，在母材钢板的电位即-0.5V附近进行恒定电流电解直至显示均匀的电位。然后，对于在此期间得到的溶解液，通过ICP发射光谱分析测定Zn含量，作为合金化锌层的Zn含量。
另外，对于从与上述样品相邻的位置切取的其他镀覆钢板，利用朝日化学工业制IBIT 700BK等含有抑制剂的10％盐酸水溶液，将镀锌层全部溶解。对于所得到的溶解液，通过ICP发射光谱分析测定Zn、Al以及Fe的含量，求出Fe在镀锌层整体中所占的含量。
进而，对于相邻的其他镀覆钢板，利用辉光放电发光分析法(GDS)，一边从表面向深度方向溅射一边进行成分分析，获取Al的浓度分布。然后，将Al浓度从表面起定量而首次低于0.1质量％的深度的1/2定义为氧化物层的厚度。测定装置例如为Rigaku公司制：GDA-750，测定条件为900V-20mA，测定直径4mmφ。从1个材料测定任意的10点，将其平均值作为该材料的测定值。在材料表面附着有涂油或污垢的情况下，用有机溶剂等脱脂后进行测定。
(G)制造方法
在制造本实施方式的热冲压用镀覆钢板的工序中，包括制造母材的工序和在母材的表面形成镀锌层的工序。以下，对各工序进行详细说明。
[母材制造工序]
在母材制造工序中，制造热冲压用镀覆钢板的母材。例如，制造具有预定的化学组成的钢水，使用该钢水，通过铸造法制造板坯，或者通过铸锭法制造铸锭。接下来，通过对板坯或铸锭进行热轧，得到母材(热轧板)。
需要说明的是，也可以将对上述热轧板进行酸洗处理、对酸洗处理后的热轧板进行冷轧而得到的冷轧板作为母材。进而，也可以对上述酸洗处理后的热轧板或冷轧板实施退火，将得到的热轧退火板或冷轧退火板作为母材。
[镀覆处理工序]
在镀覆处理工序中，在上述母材表面形成镀锌层，制造热冲压用镀覆钢板。镀锌层例如能够通过进行热浸镀处理而形成。
例如，基于热浸镀处理的镀锌层的形成例如以下所述。即，将母材浸渍于由Zn、Al以及杂质构成的热浸镀锌浴中，使镀锌层附着于母材表面。热浸镀锌浴的化学组成以Zn为主体。具体而言，Zn含量为90质量％以上。另外，Al含量优选为0.05％～1.00％，更优选为0.10％～0.50％，进一步优选为0.12％～0.30％。此外，也可以含有Mg、Pb、Si等，但它们的合计含量优选为10质量％以下。
接下来，将附着有镀锌层的母材从镀浴提起。将钢板从镀浴提起后，通过向镀覆钢板的表面吹送气体的气体擦拭来控制镀锌层的厚度。
此时，通过气体的吹送，在镀锌层的表面出现新生面，从该瞬间开始镀覆表面的氧化，形成新的氧化物层。在气体擦拭后，进行后述的合金化热处理，但发现将从气体擦拭到合金化热处理为止的冷却及加热的条件最优化，对镀覆表面的氧化物层的控制、进而对之后的热冲压后的蜘蛛网状图案的抑制是有效的。更具体而言，发现重要的是，通过使擦拭时的气体的温度和流量最优化，在从镀浴中提起到进行合金化热处理为止的期间，不使镀覆凝固。
通常，热浸镀锌浴的温度一般为450℃～470℃。刚镀覆钢板后的镀层大致与镀浴温度相同，为熔融状态。之后，逐渐冷却，特别是吹送的气体的温度低，进而流量多时，镀覆的温度急剧下降。由于锌镀覆的凝固温度约为419℃，因此若镀膜成为其以下，则镀覆急剧凝固。
可知形成于镀锌层表面的氧化物层在镀覆为熔融状态下比较软质，与此相对，如果镀覆凝固，则其表面的氧化物层变得非常牢固，Zn/Al浓度也变小，在之后的热冲压时容易产生蜘蛛网状图案。
因此，适当调整擦拭时的气体的温度和流量，使得在从镀浴中提起起至进行合金化热处理为止的期间，镀锌层的表面温度不会降低至419℃以下。
另外，由于气体擦拭后的镀覆表面的氧化物层每时每刻都生长，因此若从气体擦拭到合金化热处理中达到最高温度为止的时间超过30s，则氧化物层牢固地形成，因此其间的时间优选设为30s以下，更优选设为20s以下，进一步优选设为15s以下。
需要说明的是，气体擦拭大多使用空气或氮等，但从抑制氧化的观点出发，期望的是，吹送尽量降低了氧浓度的气体。由此，在气体擦拭中使用的气体中，在使用空气的情况下，有时也能够通过之后的加热之前的加热模式使氧化为最小限度，但使用氧分压优选控制为15％以下、更优选控制为10％以下的氮分压高的空气或氮气等是有效的。
之后，进行用于形成合金化锌层的合金化热处理。对于合金化热处理的条件没有特别限制，优选将加热温度设为440℃～600℃或460℃～550℃，加热时间根据加热温度进行调节，优选设为1s～30s、1s～15s、1s～10s或1s～5s。
以下，通过实施例更具体地说明本发明，但本发明并不限定于这些实施例。
实施例
对于厚度为1.0mm且具有以质量％计为C：0.21％、Si：0.2％、Mn：2.0％、P：0.01％、S：0.007％、Cr：0.2％、Ti：0.02％、B：0.003％、余量为Fe和杂质的化学组成的冷轧钢板，通过连续热浸镀锌生产线实施退火，接着，在表1所示的条件下实施镀覆。然后，之后在表1所示的条件下进行合金化热处理，由此制成镀覆钢板。
需要说明的是，将钢板从镀浴提起后，为了不发生镀层的凝固，谋求了气体擦拭条件的优化。在表1的气体擦拭条件下，将镀层未发生凝固的情况设为○，将发生了凝固的情况设为×。另外，在所有的例子中，将从气体擦拭至达到合金加热处理时的最高温度为止的时间设为10s，气体擦拭时的气体中的氧浓度为15％，剩余部分为氮。而且，镀浴组成为Al浓度：0.13质量％，剩余部分：Zn，镀浴温度设为460℃。
[表1]
表1
通过上述方法进行所得到的镀覆钢板的镀锌层的化学组成的测定。进而，通过GDS测定氧化物层的厚度。将这些测定结果一并示于表1。需要说明的是，如表1所示，在试验No.1中，凝固锌层的比例为98％，相当于未合金化的一般的热浸镀锌钢板。另外，在试验No.32～35中，完全合金化而凝固锌层的比例成为0％，相当于一般的合金化热浸镀锌钢板。
之后，对于各试验例的镀覆钢板，切成100mm见方的尺寸后，将大气气氛的电炉加热至900℃，在其中加热3分钟后取出，迅速地夹持于内置有水冷配管的平板压力机中进行骤冷，得到热冲压高强度材料。观察该材料的表面，评价是否没有蜘蛛网状的缺陷。关于评价基准，将在材料表面非常清楚地看到蜘蛛网状的缺陷的情况设为F，将看起来很薄但在化学转化电沉积后也能看到蜘蛛网状的缺陷的情况设为C，将稍微看到蜘蛛网状的缺陷但在化学转化电沉积后看不到蜘蛛网状的缺陷的情况设为B，将在化学转化电沉积前的状态下也看不到蜘蛛网状的缺陷的情况设为A。
另外，耐腐蚀性通过基于温盐水浸渍的涂膜密合性试验进行评价。对热冲压加热后的供试材料用日本帕卡濑精株式会社制PBL-3080通过通常的化学转化处理条件进行磷酸锌处理后，将关西涂料制电沉积涂料GT-10通过电压200V的斜坡通电进行电沉积涂装，在烧结温度150℃下烧结涂装20分钟。涂膜厚度为20μm。将该样品在50℃的5％NaCl水溶液中浸渍500小时后，对涂装进行胶带剥离试验，将发生5％以上的剥离的情况设为F，将发生1％以上且小于5％的剥离的情况设为B，将小于1％的情况设为A。
将以上的评价结果一并示于表1。由表1的结果可知，在满足本发明的规定的情况下，能够抑制蜘蛛网状的缺陷，而且耐腐蚀性也优异。特别是，在氧化物层中的Zn/Al的值为3.0～6.0的例子中，几乎或完全没有产生蜘蛛网状的缺陷。
产业上的可利用性
根据本发明，在使用含Al的Zn镀覆的情况下，能够得到能够抑制蜘蛛网状的表面缺陷的热冲压用镀覆钢板。

Claims (5)

1.一种热冲压用镀覆钢板，其具备母材和在所述母材的表面形成的镀锌层，其中，
所述镀锌层从所述母材侧起依次具有合金化锌层、凝固锌层以及含有Al的氧化物层，
所述凝固锌层中的Zn含量相对于所述镀锌层中的Zn含量的比例为10％～95％，其中所述凝固锌层中的Zn含量和所述镀锌层中的Zn含量的单位为g/m2，
所述氧化物层的化学组成满足下述(i)式：
3.0≤Zn/Al≤6.0…(i)
其中，上述式中的Zn和Al分别为所述氧化物层中所含有的Zn和Al的含量，其中，所述Zn和Al的含量的单位为g/m2，
所述合金化锌层是通过镀浴中的Zn与母材中的Fe反应而金属间化合物化而形成的层，
所述凝固锌层是热浸镀锌浴凝固而成的层。
2.根据权利要求1所述的热冲压用镀覆钢板，其中，
所述氧化物层的平均厚度为1.0μm以下。
3.根据权利要求1或权利要求2所述的热冲压用镀覆钢板，其中，
所述镀锌层的Zn含量为65g/m2～150g/m2。
4.根据权利要求1或权利要求2所述的热冲压用镀覆钢板，其中，
所述镀锌层的Fe含量以质量％计小于7％。
5.根据权利要求3所述的热冲压用镀覆钢板，其中，
所述镀锌层的Fe含量以质量％计小于7％。
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