CN106029933A - 用于生产具有最佳擦拭的ZnAlMg涂覆的金属板材的方法和相应的金属板材 - Google Patents

用于生产具有最佳擦拭的ZnAlMg涂覆的金属板材的方法和相应的金属板材 Download PDF

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CN106029933A
CN106029933A CN201380081782.XA CN201380081782A CN106029933A CN 106029933 A CN106029933 A CN 106029933A CN 201380081782 A CN201380081782 A CN 201380081782A CN 106029933 A CN106029933 A CN 106029933A
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CN106029933B (zh
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让-米歇尔·马泰格纳
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Abstract

在这种方法(I)中：并且(其中)(I)，其中Z为金属板材(1)与喷嘴(17)之间沿着主喷射方向(E)的距离，Z以m表示，为受限区24中氧气的体积分数，d为喷嘴(17)的出口(25)沿着喷嘴(17)前方的金属板材(1)的行进方向(S)的平均高度，d以m表示，V为喷嘴(17)前方的金属板材(1)的行进速度，V以m.s‑1表示，P为喷嘴(17)中擦拭气体相对于大气压的超压，P以N.m‑2表示。

Description

用于生产具有最佳擦拭的ZnAlMg涂覆的金属板材的方法和相应的 金属板材
本发明涉及用于生产板材的方法，所述板材包含由钢制成的基底，其至少一个表面涂覆有包含Al和Mg的金属涂层，所述金属涂层的其余部分由Zn、不可避免的杂质和可能的一种或更多种附加元素组成，所述附加元素选自Si、Sb、Pb、Ti、Ca、Mn、Sn、La、Ce、Cr、Zr或Bi，所述金属涂层中的每一种附加元素的含量按重量计小于0.3％，所述金属涂层具有按重量计0.5％至8％的Al含量和按重量计0.3％至3.3％的Mg含量，所述方法包括至少以下步骤：
-提供所述基底；
-通过将所述基底浸渍在浴中来在所述基底的至少一个表面上沉积金属涂层，以获得所述板材；
-通过至少一个喷嘴经由至少一个出口向所述金属涂层上喷射擦拭气体来擦拭所述金属涂层，所述板材在所述喷嘴前方行进，擦拭气体沿着主喷射方向从所述喷嘴喷出，限制盒界定了在所述擦拭气体于所述板材上的碰撞区的至少下游的受限区；
-使所述金属涂层凝固。
这样的板材特别旨在用于制造陆用机动车辆(例如汽车)的车体部件。
然后将所述板材切割和变形以生产构成部件，其被组装以形成车体部件或车身外壳。
然后用漆膜(或漆系统)涂覆该车身外壳，这提供了好的表观，并且与锌基金属涂层一起参与确保防腐。
这些板材中的一些在上漆之前可能具有肉眼可见的缺陷。
这些缺陷由金属涂层外表面上交替的暗区域和亮区域组成。这些区域沿着板材的纵向，也就是说对应于在其生产过程中板材运动方向的方向而交替。
无光泽区域的长度通常为亮区域的2倍。
即使在上漆过程后已经满足了汽车制造商的要求，这些肉眼可见的缺陷也对汽车制造商对于板材品质的感知具有不利影响。
此外，对于其中板材不经受上漆的应用，这些缺陷甚至更有问题。
因此，本发明的一个目的是提供用于生产板材的方法，所述板材包含基底，其至少一个表面涂覆有或浸渍有锌基金属涂层材料，所述锌基金属涂层材料包含按重量计0.5％至8％的Al和按重量计0.5％至3.3％的Mg，金属涂层的外表面具有改善的美学外观。
为此，本发明的目的涉及权利要求1所要求保护的方法。
所述方法还可以包括权利要求2至9的独特特征，这些特征单独考虑或组合考虑。
本发明的目的还涉及根据权利要求10的板材。
所述板材还可以包括权利要求11至16的独特特征，这些特征单独考虑或组合考虑。
将参考附图通过说明书实例来例示本发明，提供这些实例仅用于提供信息而不是进行限制，其中：
-图1是示出了根据本发明的板材的结构的示意性截面图，
-图2是示出了用于生产图1所示板材的槽和擦拭喷嘴的示意性侧视图，
-图3是图2的画圈部分III的局部示意性放大图，
-图4是沿图3的箭头IV得到的示意图，示出了图3所示喷嘴的出口的形成形状，以及
-图5是具有上文之前提到的缺陷的板材的照片。
图1中所示的板材1包括由钢制成的基底3，在其两个表面5上各自涂覆有金属涂层7。
应注意的是，基底3与涂覆其的不同层的相对厚度未体现在图1中，以有助于它们的表示。
存在于两个表面5上的涂层7是类似的，随后将仅详细描述一个。作为变化方案(未示出)，仅一个表面5具有涂层7。
涂层7的厚度通常小于或等于25μm，旨在保护基底3免于腐蚀。
涂层7包含锌、铝和镁。
金属涂层7中按重量计铝的含量占0.5％至8％，优选4.4％至5.6％，更优选0.5％至4.5％，更优选0.5％至3.9％，更优选1.0％至3.9％，更优选1.5％至3.9％，甚至更优选2％至3.9％。金属涂层7中按重量计镁的含量占0.3％至3.3％，优选0.3％至1.5％，更优选0.3％至0.7％，更优选0.5％至3.3％，更优选1.0％至3.3％，更优选1.5％至3.3％，更优选2％至3.3％，甚至更优选2.5％至3.3％。
这些重量含量水平对应于用于产生涂层7的浴的那些水平，其将在随后进行描述。
这些重量含量水平是可以在金属涂层7的表面上和块中测量的那些，例如通过辉光放电光谱测定。这些含量水平不考虑涂层7和基底3之间界面的组成，其中金属间化合物的形成导致铝含量的局部增加。
因此，为了测量根据该本文件要求保护的重量含量水平，规定不使用化学溶解技术，其将导致同时溶解金属涂层7和这些金属间化合物，并因此将导致根据金属涂层7的厚度按重量计铝的含量被高估约0.05％至0.5％。
为了生产板材1，进行的合适方式可以如下文所述。
使用条带形式的基底3，所述条带例如通过热轧然后冷轧获得。
优选地，对于冷轧，首先将基底3以通常为60％至85％的压下率冷轧，以这样的方式来获得厚度为例如0.2至2mm的基底3。
然后使冷轧基底3经受退火过程，所述退火过程在还原气氛下在退火炉中以常规方式进行，目的是在其于冷轧操作期间经受的冷加工和硬化之后使其重结晶。
重结晶退火还用于活化基底3的表面5，以有利于随后浸渍操作所需的化学反应。
根据钢等级，在650℃至900℃的温度进行重结晶退火达钢重结晶和表面5活化所需的一段时间。
随后将基底3冷却到接近于槽15中包含的浴13的温度。
浴13的组合物是锌基的，并且包含：
-按重量计0.5％至8％的铝，优选4.4％至5.6％，更优选0.5％至4.5％，更优选0.5％至3.9％，更优选1.0％至3.9％，更优选1.5％至3.9％，甚至更优选2％至3.9％，
-按重量计0.3％至3.3％的镁，优选0.3％至1.5％，更优选0.3％至0.7％，更优选0.5％至3.3％，更优选1％至3.3％，更优选1.5％至3.3％，更优选2％至3.3％，甚至更优选2.5％至3.3％。
一般情况下，上文指出的每一个铝含量范围可以与每一个镁含量范围组合使用，以形成浴13。
当按重量计铝的含量为4.4％至5.6％时，按重量计镁的含量优选为0.3％至1.5％。
当按重量计铝的含量为1.5％％至3.9％时，按重量计镁的含量优选为1.0％至3.3％。
浴13的组合物还可以包含按重量计至多0.3％的任选的附加元素，例如Si、Sb、Pb、Ti、Ca、Mn、Sn、La、Ce、Cr、Ni、Zr或Bi。
除了其他方面外，这些不同元素可用于使得例如，能够改善涂层的耐腐蚀性，或者确实在其易碎性或粘合性方面提供增强。
知道其对涂层特性的影响的本领域技术人员将知道根据期望的额外目的来使用它们。还已经证实这些元素不干扰由根据本发明的方法获得的沉积波的控制。
最后，浴13可以包含来源于槽的进料锭或甚至来自浴13中基底3的穿过的不可避免的杂质。在这种情况下，特别地可提到铁。
在穿过浴13后，基底3在其两个表面5上涂覆有涂层7，以获得板材1。
如图2所示，随后通过喷嘴17对板材1进行擦拭处理，所述喷嘴17设置在板材1的两侧上并且向涂层7的外表面21喷射擦拭气体，优选惰性气体。擦拭气体沿着主喷射方向E从每个喷嘴17喷出。每个喷嘴17的主喷射方向E在图2和3中实质上由虚线示出。
在所示实例中，方向E是水平的并且与板材1正交。在另一些实施方案中，方向E可相对于板材1具有其他倾斜度。
在所使用的生产线上并因此在喷嘴17前方行进的基底3的运动速度V通常为80m/分钟至300m/分钟，优选大于120m/分钟，或甚至大于150m/分钟。
为了限制涂层7的氧化，所述方法提供了限制盒23，以限制板材1的在擦拭气体于该板材1上的撞击区I的至少下游周围的气氛。在本文中使用的术语“下游”应理解为相对于在喷嘴17前方行进的板材1的运动方向S而言。
作为变化方案，限制盒23可以在上游方向延伸直至浴13的表面或者直到喷嘴17和浴13表面之间的中间位置为止。
限制盒23限定了受限区24，所述受限区24包封擦拭气体于金属板材1上的碰撞区I并且从所述区域在至少下游方向延伸。
在上文所述的实例中，喷嘴17具有类似的结构和相对于板材I的定位规格，并且其功能具有类似的设置。因此，下文将参考图3仅描述图2右侧的喷嘴17。还应注意的是，图3中仅示出了右侧的喷嘴17。
作为变化方案，喷嘴17可具有不同结构、不同位置和/或具有不同设置的功能。还可以仅在板材1的一侧提供喷嘴。
喷嘴17具有出口25，擦拭气体通过所述出口25喷向面对其布置的涂层7的外表面21。可以为喷嘴17设想多种不同的外部形式。
喷嘴17的出口25设置为沿着主喷射方向E离板材1距离Z处。
当E不与板材1正交时，Z因此不是板材1和喷嘴17之间的最小距离。如图4所示，出口25通常呈现狭缝形式，其正交于方向L和图3的平面延伸宽度L，宽度L至少等于板材1的宽度。
通常，出口25的高度，即其平行于在喷嘴17前方行进的板材1的运动方向S的尺寸，是恒定的，如图4中所示。虽然如此，但是在一些变化实施方案中，该高度可以在出口25的宽度上变化。因此，出口25可以例如具有朝向其端部稍微外扩的形状(蝴蝶结形状)。
为了将高度上的这些可能变化以及多种不同的可能实施方案考虑在内，随后将考虑出口25在其宽度L上的平均高度。
与大气压相比喷嘴17中的擦拭气体的超压表示为P。受限区24中氧气的体积分数表示为换言之，P是喷嘴17内的擦拭气体的压力与大气压之差。
根据本发明
和(A)，其中
其中：
Z以m表示
d以m表示
V以ms-1表示
P以Nm-2表示
通常，参数V由基底3的等级和基底3的重结晶退火区中的热容量施加。选择高度d用于生产行进。这使得只是调节Z、P和以满足上文列举的要求。
例如在区24取样后测量。
通常，这样的取样在相对接近碰撞区I的距离处进行，所述距离例如小于或等于3Z，从而代表碰撞区I水平下的氧体积分数。
还可能必要的是延伸限制盒23或者改变其，以改善密闭并且满足方程(A)。
如下文将详细描述的，符合上述条件提供了在涂层7凝固之后以及可能进行上漆之前获得改善的美学外观的能力。
随后使涂层7以受控的方式冷却以使其凝固。
当涂层7完全冷却后，板材1可以经受表皮光轧操作，以赋予涂层7的外表面21以有助于板材1后续成形的织构。
事实上，表皮光轧操作起到向板材1的涂层7的外表面21转移足够的粗糙度的目的，需要所述粗糙度以在其成形之前通过促进施加到板材1上的油的良好保留来确保成形在良好条件下进行。表皮光轧操作期间板材1的伸长率通常为0.5％至2％。
通常对旨在用于制造机动车辆的车体部件的板材1进行表皮光轧操作。
当板材1旨在用于制造例如家用电器时，不需要进行该额外操作。
无论是否通过表皮光轧处理，随后可以将板材1切割然后成形，例如通过深拉延、弯曲或仿形切削以生产部件，所述部件随后可以经受上漆以在每个涂层7上形成漆膜(或漆系统)。
在部件用于家用电器的情况下，还可以最终通过本身已知的物理和/或化学手段对漆膜进行退火处理。
为此目的，所述处理可以涉及使上漆部件通过热风炉或感应炉，或甚至在紫外灯或在散布电子束的装置下通过。
对于汽车应用，在磷酸盐化后，将每个构成部件浸渍在阳离子电泳浴中，然后连续施加底漆涂层、基础漆层和可能的顶涂层清漆层。
在构成部件上施加阳离子电泳层之前，将其预先脱脂，然后以一定方式磷酸盐化，例如以确保阳离子电泳处理物的粘附性。
因此，阳离子电泳涂层提供了具有额外的腐蚀防护层的构成部件。通常用喷枪施加的底漆层使构成部件为其最终外观做好准备并且保护其免于碎裂和UV射线。基础漆涂层为构成部件提供了其颜色和其最终外观。清漆层为构成部件的表面提供了良好的机械耐受性、侵蚀性化学剂耐受性和良好表面外观。
通常，磷酸盐层的重量为1.5g/m2至5g/m2。
用于保护构成部件并且确保其具有最佳表面外观的漆膜包括例如，厚度为15μm至25μm的阳离子电泳涂层，厚度为35μm至45μm的底漆涂层，以及厚度为40μm至50μm的基础漆涂层。
在漆膜额外包含清漆涂层的情况下，多种不同漆涂层的厚度通常如下：
阳离子电泳漆涂层：15μm至25μm，优选小于20μm，
底漆涂层：小于45μm，
基础漆涂层：小于20μm，以及
清漆涂层：小于55μm。
漆膜也可以可能不包含任何阳离子电泳漆层，并且可以仅包含一个底漆涂层和一个基础漆涂层，以及可能的一个清漆涂层。
优选地，漆膜的总厚度小于120μm，或甚至小于100μm。
现在将通过说明性测试例示本发明，所述测试用于提供信息而不是进行限制。
下文的表I详细说明了利用Z、d、V、P和的多个不同值进行的一系列测试的条件。
在这些测试中，涂层7中按重量计的铝的含量水平为约3.7％，按重量计镁的含量水平为约3.1％。其厚度为约10μm。用于产生这些涂层7的浴的温度为约420℃。所使用的擦拭气体为基于氮的，涂层7直到其凝固为止的冷却速率为14℃/s至15℃/s。
最右边的列表明，对于每个测试来说，参数是否满足方程式(A)并且指出了上文之前提到的缺陷是否存在(字母Y)或者是否不可观测到(字母N)。
图5示出了存在这些缺陷的测试。
于是可以在涂层7的外表面上视觉上观察到暗区域31和亮区域33的交替图案。
如上表I所示，满足条件并且满足方程式(A)提供了避免出现这些缺陷并因此改善金属板1的涂层7的美学外观的能力。

Claims (16)

1.一种用于生产板材(1)的方法，所述板材(1)包括由钢制成的基底(3)，所述基底(5)的至少一个表面(5)涂覆有包含Al和Mg的金属涂层(7)，所述金属涂层(7)的其余部分由Zn、不可避免的杂质和可能的一种或更多种附加元素组成，所述附加元素选自Si、Sb、Pb、Ti、Ca、Mn、Sn、La、Ce、Cr、Zr或Bi，所述金属涂层(7)中的每一种附加元素的按重量计含量小于0.3％，所述金属涂层(7)具有按重量计0.5％至8％的Al含量和按重量计0.3％至3.3％的Mg含量，所述方法包括至少以下步骤：
-提供所述基底(3)；
-通过将所述基底(3)浸渍在浴中以在至少一个表面(5)上沉积金属涂层(7)，来获得所述板材(1)；
-通过经由至少一个出口(25)向所述金属涂层(7)上喷射擦拭气体的至少一个喷嘴(17)来擦拭所述金属涂层(7)，所述板材(1)在所述喷嘴前方行进，所述擦拭气体沿着主喷射方向(E)从所述喷嘴(17)喷出，限制盒(23)界定了在所述擦拭气体于所述板材(1)上的碰撞区(I)的至少下游的受限区(24)；
-使所述金属涂层(7)凝固，
在方法中，其中并且(A)，其中
Z为所述板材(1)与所述喷嘴(17)之间沿着所述主喷射方向(E)的距离，Z以m表示，为受限区(24)中氧气的体积分数，
d为所述喷嘴(17)的所述出口(25)沿着在所述喷嘴(17)前方行进的所述板材(1)的运动方向(S)的平均高度，d以m表示，
V为在所述喷嘴(17)前方行进的所述板材(1)的运动速度，V以ms-1表示，以及
P为所述喷嘴(17)中的所述擦拭气体与大气压相比的超压，P以Nm-2表示。
2.根据权利要求1所述的方法，其中所述方法包括在涂层沉积步骤之前的所述板材(1)的冷轧步骤。
3.根据前述权利要求中任一项所述的方法，其中所述方法包括在涂层凝固步骤之后的所述板材(1)的表皮光轧步骤。
4.根据前述权利要求中任一项所述的方法，其中所述金属涂层(7)中按重量计Al的含量为0.5％至3.9％。
5.根据权利要求4所述的方法，其中所述金属涂层(7)中按重量计Al的含量为1.5％至3.9％。
6.根据权利要求1至3中任一项所述的方法，其中所述金属涂层(7)中按重量计Al的含量为4.4％至5.6％。
7.根据前述权利要求中任一项所述的方法，其中所述金属涂层(7)中按重量计含Mg的量为1.0％至3.3％。
8.根据权利要求7所述的方法，其中所述金属涂层(7)中按重量计Mg的含量为2.5％至3.3％。
9.根据权利要求1至6中任一项所述的方法，其中所述金属涂层(7)中按重量计Mg的含量为0.3％至1.5％。
10.一种能够根据前述权利要求中任一项所述的方法获得的板材(1)，所述板材(1)包含由钢制成的基底(3)，所述基底(3)的至少一个表面(5)涂覆有包含Al和Mg的金属涂层(7)，所述金属涂层(7)的其余部分由Zn、不可避免的杂质和可能的一种或更多种附加元素组成，所述附加元素选自Si、Sb、Pb、Ti、Ca、Mn、Sn、La、Ce、Cr、Zr或Bi，所述金属涂层(7)中的每一种附加元素的含量按重量计小于0.3％，所述金属涂层(7)具有按重量计0.5％至8％的Al含量和按重量计0.3％至3.3％的Mg含量。
11.根据权利要求10所述的板材，其中所述金属涂层(7)中按重量计Al的含量为0.5％至3.9％。
12.根据权利要求11所述的板材，其中所述金属涂层(7)中按重量计Al的含量为1.5％至3.9％。
13.根据权利要求10所述的板材，其中所述金属涂层(7)中按重量计Al的含量为4.4％至5.6％。
14.根据权利要求10至13中任一项所述的板材，其中所述金属涂层(7)中按重量计Mg的含量为1.0％至3.3％。
15.根据权利要求14所述的板材，其中所述金属涂层(7)中按重量计Mg的含量为2.5％至3.3％。
16.根据权利要求10至13中任一项所述的板材，其中所述金属涂层(7)中按重量计Mg的含量为0.3％至1.5％。
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