CN111279007A - 用于制造镀锌扩散退火钢板的方法 - Google Patents

用于制造镀锌扩散退火钢板的方法 Download PDF

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CN111279007A
CN111279007A CN201880069224.4A CN201880069224A CN111279007A CN 111279007 A CN111279007 A CN 111279007A CN 201880069224 A CN201880069224 A CN 201880069224A CN 111279007 A CN111279007 A CN 111279007A
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steel sheet
zinc
coating
iron
nickel
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CN111279007B (zh
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阿尼尔班·查克拉博蒂
哈桑·卡西米-阿马基
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ArcelorMittal SA
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Abstract

本发明涉及用于制造镀锌扩散退火钢板的方法。

Description

用于制造镀锌扩散退火钢板的方法
本发明涉及用于制造镀锌扩散退火钢板的方法。本发明特别适用于机动车辆的制造。
基于锌的涂层因为其因屏障保护和阴极保护而能够实现抗腐蚀保护而被广泛使用。屏障作用通过在钢表面上施加金属涂层而获得。因此，金属涂层防止钢与腐蚀性气氛之间的接触。屏障作用与涂层和基材的性质无关。相反，牺牲阴极保护基于这样的事实：锌是不如钢优质的金属。因此，如果发生腐蚀，则锌与钢相比被优先消耗。阴极保护在钢直接暴露于腐蚀性气氛的区域(例如切割边缘，其中周围的锌先于钢被消耗)中是必需的。
然而，当对这样的经锌涂覆的钢板进行加热步骤，例如热压制硬化或焊接时，在钢中观察到从钢/涂层界面扩展的裂纹。事实上，有时，由于以上操作之后在涂覆的钢板中存在裂纹，因此存在金属机械特性的降低。这些裂纹随着以下条件出现：高温；除了存在拉伸应力之外，还与具有低熔点的液态金属(例如，锌)接触；熔融金属对基材晶粒和晶界的不均匀扩散。这种现象的名称被称为液态金属脆化(LME，liquid metal embrittlement)，也被称为液态金属辅助开裂(LMAC，liquid metal assisted cracking)
有时，使经锌涂覆的钢板在高温下合金化以获得镀锌扩散退火钢板。该钢板与经锌涂覆的钢板相比是更加抗LME性的，因为与纯的锌相比，所形成的包含Fe和Zn的合金具有更高的熔点，并且在点焊期间形成较少的液体。
然而，尽管镀锌扩散退火钢板是更加抗LME性的，但是当进行加热步骤时，由于抗LME性并不足够充分，因此可能出现一些裂纹。
因此，本发明的目的是提供不存在LME问题的镀锌扩散退火钢板。其目的是进行可实现的尤其是易于实施的方法，以获得在成形和/或焊接之后不存在LME问题的组合件。
该目的通过提供根据权利要求1所述的方法来实现。所述方法还可以包括根据权利要求2至18所述的任何特征。
另一个目的通过提供根据权利要求19所述的钢板来实现。所述钢板还可以包括根据权利要求20至26所述的任何特征。
又一个目的通过提供根据权利要求27所述的点焊接头来实现。所述点焊接头还可以包括根据权利要求30所述的特征。
最后，再一个目的通过提供根据权利要求31所述的钢板或组合件的用途来实现。
本发明的其他特征和优点将由以下对本发明的详细描述而变得明显。
表述“钢”或“钢板”意指具有允许零部件实现高达2500MPa并且更优选地高达2000MPa的拉伸强度的组成的钢板、卷材、板材。例如，所述拉伸强度大于或等于500MPa，优选地大于或等于980MPa，有利地大于或等于1180MPa并且甚至大于或等于1470MPa。
本发明涉及用于制造镀锌扩散退火钢板的方法，包括以下步骤：
A.提供涂覆有包含铁和镍的第一涂层的预涂覆的钢板，这样的钢板具有按重量百分比计的以下化学组成：
0.10％<C<0.40％，
1.5％<Mn<3.0％，
0.7％<Si<2.0％，
0.05％<Al<1.0％，
0.75％<(Si+Al)<3.0％，
以及在完全任选的基础上，诸如以下的一种或更多种元素：
Nb≤0.5％，
B≤0.005％，
Cr≤1.0％，
Mo≤0.50％，
Ni≤1.0％，
Ti≤0.5％，
所述组成的剩余部分由铁和由加工产生的不可避免的杂质构成，
B.在600℃至1000℃的温度下对这样的预涂覆的钢板进行热处理，
C.用基于锌的第二涂层对在步骤B)中获得的所述钢板进行热浸镀，以及
D.进行合金化处理以形成镀锌扩散退火钢板。
不希望受任何理论的束缚，似乎在热处理期间，在一方面，Ni向钢板扩散而提供Fe-Ni合金层。另一方面，在钢与涂层界面之间的界面处仍然存在一定量的Ni，这防止在任何加热步骤例如焊接期间液态锌渗入至钢中。此外，在第一涂层中铁的存在允许在步骤D)期间形成Fe-Zn合金。
包含铁和镍的第一涂层通过本领域技术人员已知的任何沉积方法来沉积。可以通过真空沉积或电镀法来沉积。优选地，通过电镀法来沉积。
优选地，在步骤A)中，第一涂层包含10重量％至75重量％，更优选地25重量％至65重量％，并且有利地40重量％至60重量％的铁。
优选地，在步骤A)中，第一涂层包含25.0重量％至90重量％，优选地35重量％至75重量％，并且有利地40重量％至60重量％的镍。
在一个优选实施方案中，在步骤A)中，第一涂层由铁和镍组成。
优选地，在步骤A)中，第一涂层的厚度等于或大于0.5μm。更优选地，第一涂层的厚度为0.8μm至5.0μm，并且有利地为1.0μm至2.0μm。
优选地，在步骤B)中，热处理为连续退火。例如，连续退火包括加热、均热和冷却步骤。其还可以包括预热步骤。
有利地，热处理在露点为-10℃至-60℃的包含1％至30％的H2的气氛中进行。例如，气氛包含1％至10％的H2，露点为-40℃至-60℃。
有利地，在步骤C)中，第二层包含大于70％，更优选地大于80％的锌，并且有利地大于85％的锌。第二层可以通过本领域技术人员已知的任何沉积方法来沉积。可以通过热浸镀、通过真空沉积或通过电镀锌来进行。
例如，基于锌的涂层包含0.01重量％至0.18重量％的Al，任选地0.2重量％至8.0重量％的Mg，剩余部分的Zn。
优选地，基于锌的涂层通过热浸镀锌方法来沉积。在该实施方案中，熔浴还可以包含不可避免的杂质以及来自进给锭料或来自钢板通过熔浴的残留元素。例如，任选的杂质选自Sr、Sb、Pb、Ti、Ca、Mn、Sn、La、Ce、Cr、Zr或Bi，每种另外的元素按重量计的含量低于0.3重量％。来自进给锭料或来自钢板通过熔浴的残留元素可以为含量高至5.0重量％，优选地3.0重量％的铁。
在一个优选实施方案中，第二层由锌组成。在这种情况下，当通过热浸镀锌来沉积涂层时，浴中铝的百分比为0.10重量％至0.18重量％。
优选地，在步骤D)中，通过在460℃至550℃的温度下将在步骤C)中获得的涂覆的钢板加热5秒至40秒来进行合金化处理。例如，步骤D在500℃下进行20秒。
利用根据本发明的方法，获得了这样的镀锌扩散退火钢板，所述镀锌扩散退火钢板具有包含铁和镍的第一层，所述第一层被基于锌的第二层直接覆盖，第一层和第二层通过扩散而合金化使得第二合金层包含5重量％至15重量％的铁、0重量％至15重量％并且优选地1重量％至15重量％的镍、余量的锌。
优选地，钢板具有包含1％至50％的残余奥氏体、1％至60％的马氏体以及任选地选自贝氏体、铁素体、渗碳体和珠光体中的至少一种成分的显微组织。在这种情况下，马氏体可以为回火的或未回火的。
在一个优选实施方案中，钢板具有包含5％至25％的残余奥氏体的显微组织。
优选地，钢板具有包含1％至60％并且更优选10％至60％的回火马氏体的显微组织。
有利地，钢板具有包含10％至40％的贝氏体的显微组织，这样的贝氏体包含10％至20％的下贝氏体、0％至15％的上贝氏体和0％至5％的无碳化物贝氏体。
优选地，钢板具有包含1％至25％的铁素体的显微组织。
优选地，钢板具有包含1％至15％的未回火的马氏体的显微组织。
在制造钢板之后，为了生产车辆的某些零部件，已知的是通过对两个金属板进行焊接来组装。因此，在对至少两个金属板进行焊接期间形成点焊接头，所述点是所述至少两个金属板之间的连接物。
为了生产根据本发明的点焊接头，在有效强度(effective intensity)为3kA至15kA并且施加在电极上的力为150daN至850daN(其中所述电极活性面(active face)直径为4mm至10mm)的情况下进行焊接。
因此，获得了包括根据本发明的涂覆的钢板的至少两个金属板的点焊接头，这样的所述接头包含少于3个尺寸大于100μm的裂纹，并且其中最长的裂纹的长度小于400μm。
优选地，第二金属板为钢板或铝板。更优选地，第二金属板为根据本发明的钢板。
在另一个实施方案中，点焊接头包括第三金属板，所述第三金属板为钢板或铝板。例如，第三金属板为根据本发明的钢板。
根据本发明的钢板或点焊接头可以用于制造机动车辆用零部件。
现在将在仅用于提供信息而进行的试验中说明本发明。它们是非限制性的。
实施例
对于所有样品，所使用的钢板具有按重量百分比计的以下组成：C＝0.37重量％、Mn＝1.9重量％、Si＝1.9重量％、Cr＝0.35重量％、Al＝0.05重量％和Mo＝0.1重量％。
通过沉积包含55％和75％的Ni、余量的Fe的第一涂层来制备试验1至4。然后，在露点为-45℃的包含5％的H2和95％的N2的气氛中进行连续退火。将预涂覆的钢板在900℃的温度下加热。通过热浸镀锌来沉积锌涂层，锌浴包含0.2％的Al。浴温度为460℃。最后，在500℃下进行合金化处理20秒以获得镀锌扩散退火钢板。
出于比较目的，在使以上钢板连续退火之后，通过经由电镀锌沉积锌涂层来制备试验5。
评估试验1至5的抗LME性。为此，对于每个试验，通过电阻点焊将两个涂覆的钢板焊接在一起。电极类型为直径为16mm的ISO B型；电极的力为5kN，以及水的流量为1.5g/分钟。在表1中记录循环的焊接周期。
表1.焊接工艺
焊接时间 脉冲 脉冲(周波) 冷却时间(周波) 维持时间(周波)
周期 2 12 2 10
然后，使用光学以及SEM(扫描电子显微镜)评估大于100μm的裂纹的数量，如表2中所记录。
表2.点焊之后的LME裂纹详情(二层堆叠条件)
Figure BDA0002463917330000051
Figure BDA0002463917330000061
*：根据本发明。
与试验5相比，根据本发明的试验显示出优异的抗LME性。实际上，与试验5相比，根据本发明的试验的裂纹的数量非常低，甚至不存在。
对于每个试验，还在三层堆叠配置下通过电阻点焊将三个涂覆的钢板焊接在一起。然后使用光学以及SEM(扫描电子显微镜)评估大于100μm的裂纹的数量，如表3中所记录。
表3.点焊之后的LME裂纹详情(三层堆叠条件)
Figure BDA0002463917330000062
*：根据本发明。
与试验5相比，根据本发明的试验显示出优异的抗LME性。
最后，接着将试验1至4以90°角弯曲。然后施加粘合剂带并移除以验证与基材钢的涂层粘附性。这些试验的涂层粘附性优异。

Claims (31)

1.一种用于制造镀锌扩散退火钢板的方法，包括以下步骤：
A.提供涂覆有包含铁和镍的第一涂层的预涂覆的钢板，这样的钢板具有按重量百分比计的以下化学组成：
0.10％<C<0.40％，
1.5％<Mn<3.0％，
0.7％<Si<2.0％，
0.05％<Al<1.0％，
0.75％<(Si+Al)<3.0％，
以及在完全任选的基础上，诸如以下的一种或更多种元素：
Nb≤0.5％，
B≤0.005％，
Cr≤1.0％，
Mo≤0.50％，
Ni≤1.0％，
Ti≤0.5％，
所述组成的剩余部分由铁和由加工产生的不可避免的杂质构成，
B.在600℃至1000℃的温度下对这样的预涂覆的钢板进行热处理，
C.用基于锌的第二涂层对在步骤B)中获得的所述钢板进行热浸镀，以及
D.进行合金化处理以形成镀锌扩散退火钢板。
2.根据权利要求1所述的方法，其中在步骤A)中，所述第一涂层包含10重量％至75重量％的铁。
3.根据权利要求2所述的方法，其中在步骤A)中，所述第一涂层包含25.0重量％至65.0重量％的铁。
4.根据权利要求1至3中任一项所述的方法，其中在步骤A)中，所述第一涂层包含40重量％至60重量％的铁。
5.根据权利要求1或2中任一项所述的方法，其中在步骤A)中，所述第一涂层包含25重量％至90重量％的镍。
6.根据权利要求1或3所述的方法，其中在步骤A)中，所述第一涂层包含35重量％至75重量％的镍。
7.根据权利要求1或4所述的方法，其中在步骤A)中，所述第一涂层包含40重量％至60重量％的镍。
8.根据权利要求1至7中任一项所述的方法，其中在步骤A)中，所述第一涂层由铁和镍组成。
9.根据权利要求1至8中任一项所述的方法，其中在步骤A)中，所述第一涂层的厚度等于或大于0.5μm。
10.根据权利要求9所述的方法，其中在步骤A)中，所述第一涂层的厚度为0.8μm至5.0μm。
11.根据权利要求10所述的方法，其中在步骤A)中，所述第一涂层的厚度为1.0μm至2.0μm。
12.根据权利要求1至11中任一项所述的方法，其中在步骤C)中，第二层包含大于70％的锌。
13.根据权利要求12所述的方法，其中在步骤C)中，所述第二层包含大于80％的锌。
14.根据权利要求13所述的方法，其中在步骤C)中，所述第二层包含大于85％的锌。
15.根据权利要求14所述的方法，其中在步骤C)中，所述第二层由锌组成。
16.根据权利要求1至15中任一项所述的方法，其中在步骤B)中，所述热处理为连续退火。
17.根据权利要求1至16中任一项所述的方法，其中在步骤B)中，所述热处理在露点为-30℃至-60℃的包含1％至10％的H2的气氛中进行。
18.根据权利要求1至17中任一项所述的方法，其中在步骤D)中，所述合金化处理通过在460℃至550℃的温度下加热在步骤C)中获得的涂覆的钢板来进行。
19.一种能够由根据权利要求1至18中任一项所述的方法获得的镀锌扩散退火钢板，所述镀锌扩散退火钢板涂覆有包含铁和镍的第一层，所述第一层被基于锌的第二层直接覆盖，所述第一层和所述第二层通过扩散而合金化使得第二合金层包含5重量％至15重量％的铁、0重量％至15重量％的镍、余量的锌。
20.根据权利要求19所述的镀锌扩散退火钢板，其中所述第二合金层包含1重量％至15重量％的镍。
21.根据权利要求20所述的镀锌扩散退火钢板，其中所述钢的显微组织包含1％至50％的残余奥氏体，1％至60％的马氏体和任选地选自贝氏体、铁素体、渗碳体和珠光体中的至少一种成分。
22.根据权利要求21所述的镀锌扩散退火钢板，其中所述显微组织包含5％至25％的残余奥氏体。
23.根据权利要求21或22所述的镀锌扩散退火钢板，其中所述显微组织包含1％至60％的回火马氏体。
24.根据权利要求21至23中任一项所述的镀锌扩散退火钢板，其中所述显微组织包含10％至40％的贝氏体。
25.根据权利要求21至24中任一项所述的镀锌扩散退火钢板，其中所述显微组织包含1％至25％的铁素体。
26.根据权利要求21至25中任一项所述的镀锌扩散退火钢板，其中所述显微组织包含1％至15％的未回火的马氏体。
27.一种至少两个金属板的点焊接头，所述至少两个金属板至少包括根据权利要求19至26中任一项所述的钢板、或者能够由根据权利要求1至18中任一项所述的方法获得的钢板，所述接头包含少于3个尺寸大于100μm的裂纹，并且其中最长的裂纹的长度小于400μm。
28.根据权利要求27所述的点焊接头，其中第二金属板为钢板或铝板。
29.根据权利要求28所述的点焊接头，其中所述第二金属板为根据权利要求20至26中任一项所述的钢板、或者能够由根据权利要求1至19所述的方法获得的钢板。
30.根据权利要求27至29中任一项所述的点焊接头，包括第三金属板，所述第三金属板为钢板或铝板。
31.根据权利要求19至26中任一项所述的镀锌扩散退火钢板或根据权利要求27至30中任一项所述的点焊接头用于制造机动车辆的用途。
CN201880069224.4A 2017-10-24 2018-10-19 用于制造镀锌扩散退火钢板的方法 Active CN111279007B (zh)

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