CN103582531A - 可热成型的带材、片材或坯料，其生产方法、热成型产品的方法和热成型的产品 - Google Patents

可热成型的带材、片材或坯料，其生产方法、热成型产品的方法和热成型的产品 Download PDF

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CN103582531A
CN103582531A CN201280027154.9A CN201280027154A CN103582531A CN 103582531 A CN103582531 A CN 103582531A CN 201280027154 A CN201280027154 A CN 201280027154A CN 103582531 A CN103582531 A CN 103582531A
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R·布里克
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Tata Steel Ijmuiden BV
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Abstract

本发明涉及可热成型带材、片材或坯料，其在600℃或高于600℃的温度下是可成型的，其包含涂覆有腐蚀防护涂层的可热成型钢的基材。根据本发明，该经涂覆的钢被硅氧烷层覆盖。本发明还涉及用来生产该带材、片材或坯料的方法，使用该带材、片材或坯料的用于将产品热成型的方法和使用该带材、片材或坯料热成型的产品。

Description

可热成型的带材、片材或坯料,其生产方法、热成型产品的方法和热成型的产品
本发明涉及在600℃或高于600℃的温度下可成型的可热成型的带材、片材或坯料，其包含涂覆有腐蚀防护涂层的可热成型钢的基材。本发明还涉及生产该带材、片材或坯料的方法，热成型产品的方法和由其制造的热成型产品。
该经涂覆的带材、片材或坯料可从EP0971044A1知悉，其涉及涂覆Al-Si的硼钢；该热成型涂覆锌的硼钢的方法可从例如EP1143029A1知悉。
已知在模具中热成型步骤之前的热处理期间未涂覆的硼钢将形成Fe氧化物，由此在表面上形成松散和厚的氧化物层，其可污染和损害该模具的表面。而且，该氧化物层在所形成的产品的随后使用期间干扰焊接过程，且也污染随后的涂漆过程。因此，在该未涂覆的钢产品的热成型过程之后必须去除该氧化物层，这是低效和耗费成本的。
为了克服以上问题且改善该钢的腐蚀性能，已开发了涂覆的硼钢，且该硼钢已覆盖有金属涂层，例如Al-Si涂层或Zn基涂层。但是已经发现在热成型过程期间，由于热成型过程所需要的高温，该涂层被氧化物层覆盖，该氧化物层由涂层材料形成。氧化锌层使其难以将热成型的产品点焊。在使用热成型部件的汽车工业中需要良好的点焊性能。
本发明的目的是提供适用于热成型的经涂覆的带材、片材或坯料，其在热成型之后具有良好的点焊性能。
本发明进一步的目的是提供适用于热成型的经涂覆的带材、片材或坯料，其对于生产为经济的。
本发明的另一个目的是提供满足上文中的一个或多个目的的带材、片材或坯料的生产方法。
本发明的进一步的目的是提供用于热成型产品的方法和具有良好的点焊性能的热成型产品。
根据本发明，采用用于在Ac1温度或高于Ac1的温度下热成型的钢带材、片材或坯料满足了一个或多个以上目的，其包含涂覆有腐蚀防护涂层的可热成型的钢的基材，其中该经涂覆的钢基材被硅氧烷层覆盖。
本发明人已经发现，该硅氧烷层适于在涂覆有腐蚀防护涂层的钢带材、片材和坯料的热成型期间降低氧化的程度。由于蒸发，该硅氧烷层也降低了锌的损失。当热成型时，该涂覆硅氧烷的材料将被氧化而留下薄的粘附的氧化硅层，其具有低的接触电阻和因此良好的焊接性能。因为该腐蚀防护涂层减少的氧化，所以该硅氧烷层也改善了用于该钢的腐蚀防护的涂层的有效性。该钢基材用于在Ac1温度或高于Ac1温度下的热成型。可将该钢基材用于该热成型的产品的热成型和淬火，其通常提供了1500MPa或更高的拉伸强度。
通常将硅氧烷层用作代替铬酸盐的钝化处理或用作代替磷酸盐或铬酸盐的转变处理以改善与粘结剂或涂料的粘结。其在通过辊涂、浸渍/挤压或喷射/挤压施加的最终也含有醇的水基硅烷膜的固化之后形成，且其含有与氧原子和/或烃基以及与烃和/或烃基的碳原子结合的硅原子。烃和/或烃基的碳原子可相互或与中间体胺或羰基和/或硫原子结合。
根据优选的实施方案，该硅氧烷层源自含有使得C/Si≤1的碳的量的二硅烷。由于几乎没有二氧化碳的形成，这导致了几乎无孔隙的、均匀的氧化硅层，因此该硅氧烷层向该钢的防护添加了优化性，其显示提供了用于热成型产品的最好的焊接可能性。
根据优选的实施方案，该硅氧烷层的厚度使得在热成型之后最多200mg Si/m2，优选为20-100mg Si/m2，且优选为40-100mg Si/m2保留在氧化硅层中。本发明人已发现，金属磷酸盐层的厚度应该为最多200mg Si/m2，因为更高的厚度下，该氧化硅层自身将阻碍经点焊的材料的接触电阻。而且，层的成本也变得过高。因此，优选较薄的层。
根据优选的实施方案，该腐蚀防护层为锌或锌合金层。锌或锌合金的涂层向该钢基材提供了良好的、活化的腐蚀防护。
根据优选的实施方案，该锌或锌合金层为含有至多70重量%的Fe，且优选含有8-12重量%的Fe的镀锌退火层。已发现在该类涂层上的如上所述的硅氧烷层将提供良好的点焊性能。使用该电镀的锌或锌合金层也使其较易于将该经涂覆的钢热成型。
根据实施方案，该锌或锌合金层为含有至多70重量%的Fe且优选含有1-5重量%的Fe的镀锌退火层。
该锌合金可由0.3-2.3重量%的镁和0.6-2.3重量%的铝、任选的小于0.2重量%的一种或多种添加元素，余量为锌和不可避免的杂质组成。可以少量添加的，小于0.2重量%的任选元素可为Pb或Sb、Ti、Ca、Mn、Sn、La、Ce、Cr、Ni、Zr或Bi。通常添加Pb、Sn、Bi和Sb以形成锌花（spangle）。该类涂层具有与通常的锌层相比改善的抗腐蚀性。
优选该腐蚀防护涂层具有2-25μm的厚度。该厚度适用于生产热成型部件用于汽车目的。
根据优选的实施方案，该热成型的钢基材为具有以下重量%组成的钢基材：
0.04-0.5%的C
0.5-3.5%的Mn
小于2.0%的Si
小于1.0%的Cr
小于0.2%的Ti
小于2.0%的Al
小于0.5%的Mo
小于0.1%的P
小于0.015%的N
小于0.05%的S
小于0.015%的B
余量为Fe和不可避免的杂质。
这些钢类型适用于热成型，其中还可在极限内选择合金化元素。通常，该硼的量为0.001-0.005重量%。
优选可热成型的钢基材为具有以下重量%组成的钢基材：
0.04-0.5%的C
0.5-3.5%的Mn
小于2.0%的Si
小于1.0%的Cr
小于0.2%的Ti
小于2.0%的Al
小于0.5%的Mo
小于0.1%的P
小于0.1%的Nb
小于0.015%的N
小于0.05%的S
小于0.015%的B
余量为Fe和不可避免的杂质。
当添加Nb时，这些钢类型具有更好的机械性能。而且在该实施方案中，硼的量通常为0.001-0.005重量%。
优选该可热成型的钢基材为具有以下重量%组成的钢基材：
0.04-0.5%的C
0.5-3.5%的Mn
小于2.0%的Si
小于1.0%的Cr
小于0.2%的Ti
小于2.0%的Al
小于0.5%的Mo
小于0.1%的P
小于0.015%的N
小于0.05%的S
小于0.015%的B
小于0.3%的W
余量为Fe和不可避免的杂质。
当添加W时这些钢类型具有更好的机械性能。而且，在该实施方案中，硼的量通常为0.001-0.005重量%。
优选该钢基材具有0.5-3.0mm的厚度。在汽车工业中使用该厚度。
本发明还涉及生产如上所述的可热成型的带材、片材或坯料的方法，其中涂覆有腐蚀防护涂层的该可热成型的钢的基材被硅烷溶液覆盖，之后将该带材、片材或坯料加热以形成硅氧烷层。以此方式，可提供具有如上例示的硅氧烷层的钢基材。
根据优选的实施方案，通过喷射或浸渍和随后挤压或通过辊涂，以具有1-10ml/m2厚度的湿膜将该硅烷溶液施加到经涂覆的钢带材、片材或坯料上，优选在涂覆生产线的最后进行，且将该湿膜在70-200℃，优选70-100℃的温度下干燥和固化。易于进行施加该湿膜的方法，且其提供了在经涂覆的基材上均匀的湿层，将其以通常的方式（例如在炉中）干燥和固化。
优选该经覆盖有硅氧烷的腐蚀防护涂覆的基材包括以上例示的该带材、片材或坯料的一个或多个特征。
本发明还涉及使用如上所述的坯料或使用由如上所述的带材或片材成型的坯料来热成型产品的方法，其中将坯料或由该坯料成型的预制件加热至Ac1温度或高于Ac1温度，在热成型模具中热成型该坯料或预制件，且将该热成型的产品淬火。这为通常的热成型方法，其现在使用根据本发明的坯料或由根据本发明的带材或片材所生产的坯料来进行。使用具有根据本发明的硅氧烷层的坯料，所成型的产品具有良好的焊接性能。
本发明还涉及使用如上所述的带材、片材或坯料或根据上述方法所生产的热成型产品，其中涂覆的热成型的基材具有低于1毫欧的接触电阻。根据在DVS2929:2007中所述的方法来测量接触电阻，但不同的是使用了7.5kN的力和300mm的电极半径。低于1毫欧的接触电阻代表良好的焊接性能。
通过参考一些背景信息和下文中显示于附图中的大量实验可阐明本发明。
图1.显示了对于两种不同的硅氧烷层厚度以及用于获得良好的焊接性能所需的预期硅氧烷层厚度，经加热的涂覆锌的钢的接触电阻(<1毫欧)。
图2A显示了在加热之后不进行后续处理的涂覆锌的基材。
图2B.显示了在加热之后具有硅氧烷层的相同的基材。
由于在热成型期间的高温，因此涂覆锌的材料迅速氧化。由于所形成的氧化物的性质，该材料的接触电阻将上升。总体上，具有大于1毫欧的接触电阻的热成型的材料被视为不可焊接的。在900℃的炉中6分钟的通常使用的热处理之后，接触电阻通常大于5毫欧。通过较低的炉温和/或在炉中较短的停留时间可减少氧化物的量，但这会严重影响热成型过程的稳健性。低的炉温使该材料易于形成铁素体，这将降低最终的材料强度。短的停留时间将该过程的灵活性最小化，因为有时由于在炉后的压制站处的技术任务，该样品不得不在炉中保持较长的时间周期。
发明人的意见是，应该降低氧化物的量（而不降低炉温或缩短最大的炉停留时间），以保持非常稳健的热成型过程。因此，他们研究了在可比较的加热循环时会将氧化的总量最小化的几种后处理。
选择了一种硅烷，即双-（三甲氧基甲硅烷基）乙烷(BTSE)（其为可商业获得的）用于研究。通过辊涂将该硅烷以两种不同浓度的水基溶液施加，即0.5重量%和3重量%，导致了约10ml/m2的湿膜厚度，从而在炉中干燥之后分别给出了2和12mg Si/m2的硅氧烷涂层重量。该基材为涂覆有锌涂层的22MnB5钢基材，该锌涂层具有额外的热处理以在涂层中具有12%的Fe。
下表1显示了在箱式炉中加热至880℃，6分钟的热循环后对于不同后处理后发明人所获得的结果。清楚的是，所施加的硅氧烷层提高了保留在片材中的锌量，对更好的腐蚀防护有贡献，且减少了降低接触电阻的氧化锌的量。但是，两种浓度之间的差异太小以致不能发现浓度的明显作用。但是，清楚的是，通过使用较高的硅烷浓度我们将实现所需要的低于1毫欧的接触电阻（这在汽车工业中的的热成型部件提供良好的焊接是需要的）。
图1告诉我们当我们推算结果（点划线）时，考虑到偏差，为了实现低于1毫欧的接触电阻，我们至少必须施加含有＞20mg Si/m2且优选>40mg Si/m2的硅氧烷层。
Figure BDA0000428552520000071
表1
图2显示了未经过后处理（图2A）和具有硅氧烷层（图2B）的涂覆锌的基材之间的差异。由该图清楚的是，硅氧烷层的使用使在锌涂层中形成的氧化物层最小化，这是由于经硅氧烷处理的涂覆锌的钢的加热。

Claims (14)

1.用于在Ac1温度或高于Ac1温度下热成型的钢带材、片材或坯料，其包含涂覆有腐蚀防护涂层的可热成型的钢基材，其特征在于该经涂覆的钢基材被硅氧烷层覆盖。
2.根据权利要求1的带材、片材或坯料，其中该硅氧烷层源自含有使得C/Si≤1的碳量的二硅烷。
3.根据前述权利要求中任一项的带材、片材或坯料，其中在热成型之后硅氧烷层的厚度使得最多200mg Si/m2，优选20-100mg Si/m2，且更优选40-100mg Si/m2保留在硅层中。
4.根据前述权利要求中任一项的带材、片材或坯料，其中该腐蚀防护层为锌或锌合金层。
5.根据权利要求4的带材、片材或坯料，其中该锌或锌合金层为镀锌退火层，其含有至多70重量%的Fe，且优选含有8重量%-12重量%的Fe。
6.根据前述权利要求中任一项的带材、片材或坯料，其中所述腐蚀防护层具有2-25μm的厚度。
7.根据前述权利要求中任一项的带材、片材或坯料，其中可热成型的钢基材为具有以下重量%组成的钢基材：
0.04-0.5%的C
0.5-3.5%的Mn
小于2.0%的Si
小于1.0%的Cr
小于0.2%的Ti
小于2.0%的Al
小于0.5%的Mo
小于0.1%的P
小于0.015%的N
小于0.05%的S
小于0.015%的B
余量为Fe和不可避免的杂质。
8.根据前述权利要求中任一项的带材、片材或坯料，其中该可热成型的钢基材为具有以下重量%组成的钢基材：
0.04-0.5%的C
0.5-3.5%的Mn
小于2.0%的Si
小于1.0%的Cr
小于0.2%的Ti
小于2.0%的Al
小于0.5%的Mo
小于0.1%的P
小于0.1%的Nb
小于0.015%的N
小于0.05%的S
小于0.015%的B
余量为Fe和不可避免的杂质。
9.根据前述权利要求中任一项的带材、片材或坯料，其中该可热成型的钢基材为具有以下重量%组成的钢基材：
0.04-0.5%的C
0.5-3.5%的Mn
小于2.0%的Si
小于1.0%的Cr
小于0.2%的Ti
小于2.0%的Al
小于0.5%的Mo
小于0.1%的P
小于0.015%的N
小于0.05%的S
小于0.015%的B
小于0.3%的W
余量为Fe和不可避免的杂质。
10.根据前述权利要求中任一项的带材、片材或坯料，其中该钢基材具有0.5-3.0mm的厚度。
11.用于生产根据前述权利要求中任一项的可热成型的带材、片材或坯料的方法，其中涂覆有腐蚀防护涂层的可热成型的钢的基材被硅烷溶液覆盖，之后将该带材、片材或坯料加热以形成硅氧烷层。
12.根据权利要求11的方法，其中通过喷射或浸渍以及随后挤压或通过辊涂将硅烷溶液以具有1-10ml/m2厚度的湿膜施加到经涂覆的钢带材片材或坯料上，优选在涂覆生产线的最后进行，且将该湿膜在70-200℃，优选70-100℃的温度下干燥和固化。
13.使用根据权利要求1-10中任一项的带材、片材或坯料热成型产品的方法，其中将该带材、片材或坯料或由该坯料成型的预制件加热至Ac1温度或高于Ac1温度，将该坯料或预制件在热成型模中热成型，且将该热成型的产品淬火。
14.使用根据权利要求1-10中任一项或根据权利要求13生产的热成型产品，其具有低于1毫欧的接触电阻。
CN201280027154.9A 2011-06-07 2012-06-06 可热成型的带材、片材或坯料，其生产方法、热成型产品的方法和热成型的产品 Pending CN103582531A (zh)

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