CN105209668B - 改善高锰钢带的可焊性的方法和经涂覆的钢带 - Google Patents

改善高锰钢带的可焊性的方法和经涂覆的钢带 Download PDF

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CN105209668B
CN105209668B CN201480017086.7A CN201480017086A CN105209668B CN 105209668 B CN105209668 B CN 105209668B CN 201480017086 A CN201480017086 A CN 201480017086A CN 105209668 B CN105209668 B CN 105209668B
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highest
zinc
protective layer
manganese
weight
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CN105209668A (zh
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K.克勒
M.德博克斯
F.卢特
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Salzgitter Flachstahl GmbH
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Abstract

本发明涉及改善高锰钢带的可焊性的方法，所述钢带含有（以重量%计）6至30%的锰、最高1%的碳、最高15%的铝、最高6%的硅、最高6.5%的铬、最高4%的铜以及添加的总计最高0.7%的钛和锆和总计最高0.5%的铌和钒，余量的铁和不可避免的钢伴生元素，其用含锌腐蚀保护层涂覆。

Description

改善高锰钢带的可焊性的方法和经涂覆的钢带
本发明涉及改善经锌涂覆的高锰钢带的可焊性的方法，所述钢带（以重量%计）除了6至30%的锰之外可以含有最高1%的碳、最高15%的铝、最高6%的硅、最高6.5%的铬、最高4%的铜以及添加的总计最高0.7%的钛和锆和总计最高0.5%的铌和钒，余量的铁和不可避免的钢伴生元素。
由于它们有利的伸长率和强度方面的性能，具有高含量的锰、铝和/或硅的钢，尤其已知为HSD®钢（高强度和延展性），适合用于运输车辆建造，特别是用于汽车建造。
高锰钢（例如HSD®钢）与常见的钢相比的特征在于明显更低的比重，从而在车身建造中使用这些轻型结构钢有利于显著的重量减轻。
例如从DE 199 00 199 A1中获知了具有7至27重量%的高的锰含量的钢，并且从DE10 2004 061 284 A1中获知了具有9至30重量%锰的钢；这些钢制成的平面产品在具有高强度的同时具有高的均匀伸长率。
但是，具有较高的锰含量的钢倾向于点蚀和表面腐蚀，并且在不添加铝和/或硅的情况下对于氢诱导的应力腐蚀开裂具有小的抵抗力。因此已建议以已知方式将由高锰钢制成的平面产品配备有保护钢免受腐蚀进攻的金属涂层。
在对于耐腐蚀性的相应要求下，已知将由锌或锌合金制成的腐蚀保护层施加到待涂覆的高锰钢带上。
高锰钢带可以处于经冷轧和热轧的状态，其中锌层或锌合金层通常通过电解或以热浸镀法来施加。
从DE 199 00 199 A1中获知，将平面产品的表面用铝富集和/或涂覆。在WO 2007/075006 A1中建议了高锰钢，其中以已知方式由其产生的平面产品在最后的最终退火之后可选地通过电解或通过热浸镀用锌层涂覆。
但是在一系列已知的高锰钢中迄今未解决的是其在镀锌的状态下不足的可焊性的问题，其特征在于在该材料的焊接区域中出现液体金属诱导的裂纹形成。
在下文中，焊接理解为所有的电阻焊接法以及熔焊法或电子束焊接法（Strahlschweißverfahren），其中除了基体之外，锌涂层也局部液化。
由于在焊接过程中的热作用，在基体中由于来自涂层的液化的锌而出现晶界渗透。该渗透导致基体在焊接区域周围以这样的程度丧失其强度和延展性，以致焊接接头或紧邻该焊接接头的基体不再满足所设的机械要求，并且由于裂纹形成而提高了焊接接头过早失效的风险。这种形式的应力腐蚀开裂称为液体金属脆化（LME），因为腐蚀性介质在这种情况下是液体金属。
为了改善经热浸涂覆的高锰轻型结构钢的可焊性，在DE 10 2005 008 410 B3中建议在最终退火之前通过PVD（物理气相沉积）向冷轧带钢上施加铝层。在最后的退火之后向其上施加腐蚀保护涂层。由于热处理而形成的Al/Fe-扩散层应防止熔融液态的锌在焊接过程中进入到基础材料中并因此防止液体金属脆化。但是，在这种情况下的缺点是与此相关的方法所致的高成本支出。
为了避免镀锌的高锰钢的液体金属诱导的裂纹形成，在DE 10 2009 053 260 A1中建议在含N2/H2的气氛中的退火处理，其导致在钢表面上形成氮化铝。这些表面附近的氮化铝层应防止锌进入该材料并因此防止脆化。在这种情况下的缺点在于需要高的氮化温度，这可能导致基础材料的机械性能变差。
基于所阐述的现有技术，本发明的目的在于在避免已知方法的缺点的情况下提供替代和更成本有利的方法，用其一方面能够有效地保护高锰钢免受腐蚀，且另一方面能够避免焊接时液体金属诱导的裂纹形成的问题。此外应提供相应的经涂覆的钢板。
关于该方法，通过钢带解决所设的目的，其含有（以重量%计）6至30%的锰、最高1%的碳、最高15%的铝、最高6%的硅、最高6.5%的铬、最高4%的铜以及添加的总计最高0.7%的钛和锆和总计最高0.5%的铌和钒，余量的铁和不可避免的钢伴生元素，其用含锌的腐蚀保护层涂覆，其特征在于为了防止该钢带在焊接过程中的液体金属脆化，向该钢带上施加锌/锰、锌/钴或锌/铁合金作为含锌腐蚀保护层。
有利地，该钢带（热轧或冷轧带钢）具有（以重量%计）至少0.04%的碳含量和各至少0.05%的硅含量和铝含量，以便一方面实现对于氢诱导的应力腐蚀开裂的提高的抵抗力，并在另一方面通过锰、碳、硅和铝的共同作用来抑制由变形诱导的马氏体形成和与此相关的硬化。
在试验中令人惊讶地证实了，用除了锌之外还含有锰、钴或铁的层涂覆材料除了优异的腐蚀保护之外还对于防止液体金属脆化具有特别有利的影响。以下将该方案称为单层的实施方案。
此外对此已证明，当向首先施加到钢带上的锌/锰、锌/钴或锌/铁的薄层上施加基于锌的层作为第二层时，这时还有效地防止液体金属诱导的裂纹形成。以下将这种方案称为多层的实施方案。根据本发明，含锌的腐蚀保护层因此特别地执行阻挡层的任务，而通过基于锌的第二层进行实际的阴极腐蚀保护。
根据本发明施加到钢带上的含锌腐蚀保护层的抑制脆化的作用一方面可以归因于在接合过程中形成了表面附近的氧化产物（例如在锌/锰合金的情况下形成了氧化锰）。由此阻隔了锌在晶界处的扩散路线，从而防止锌进入并最终防止材料脆化。
另一方面，将锌层用锰、钴或铁制合金导致该层的熔点提高，从而减少了接合时该涂层的熔融。
为了确保足够的腐蚀保护以及抑制液体金属脆化的作用，根据本发明既在单层也在多层的实施方案中设定，该含锌腐蚀保护层中的各合金元素的含量（以重量%计）应为至少1%。为了实现可焊性的显著改善，被证明有利的是各自5至25%的最低含量。如有必要，该含量可以提高至50%或更高。
在单层的实施方案中根据对于腐蚀保护的要求，涂层厚度可以为0.5微米至50微米。在电解镀锌的情况下，1至12微米的层厚度被证明是有利的，并且在热镀锌的情况下，5至35微米的层厚度被证明是有利的。
在多层的实施方案的情况下，直接施加到钢基底上的含锌腐蚀保护层由0.1至5微米厚的除锌之外还含有锰、钴或铁并执行扩散阻挡层任务的层和施加在其上的基本上确保阴极腐蚀保护的基于锌的第二层构成。在锌合金作为第二层的情况下，其除了锌作为主要元素之外可以含有铝和/或硅和/或锰和/或铁作为其它元素，以满足表面外观、可涂漆性、腐蚀保护等方面的特定的消费者需求。
所述第二层的厚度可以根据要求为0.5微米至50微米。
在单层和多层的实施方案中，根据本发明优选地通过电镀来涂覆所述高锰钢板；但是也可以借助替代的方法，例如通过从气相中的沉积来施加该涂层。
本发明的方法同样适合于涂覆经热轧或冷轧的钢带。
本发明方法的优点一方面在于相比于仅用锌涂覆的高锰钢而言明显提高的对于液体金属诱导的裂纹形成的抵抗力。另一方面在单层或多层的方案的情况下，可以成本有利地用已知和存在的工业大规模的装置通过电解或借助替代的方法，例如从气相中的沉积（例如PVD）来实现本发明涂层的施加。
实施例的描述：
在由DE 10 2004 061 284 A1已知的带式浇铸设备上，将组成为X70Mn-Al-Si-15-1.5-2.5、余量的铁和不可避免的钢伴生元素的钢浇铸成薄带钢，并然后轧制成热轧带钢。随后将该热轧带钢以常规方式酸洗、冷轧和退火。此后清洁该带钢以及施以表面活化（去氧化皮处理），然后用本发明的含锌腐蚀保护层和基于锌的第二层通过电解来涂覆（多层的实施方案）。
施加到钢带上的含锌腐蚀保护层分别在12个样品中具有77/23、64/36、30/70和40/60的锌/锰-比（以重量%计），并分别在5个样品中具有28/72、89/11和91/9的锌/钴-比（以重量%计）。单层实施方案中的层厚度为1至5微米。在多层实施方案中，第一层的厚度为0.5至1微米，且第二层的厚度为1至4微米。为了检测对于液体金属诱导的裂纹形成的敏感性，在电阻点焊方法中接合样品。
所有48个具有锌/锰-层的样品以及所有15个具有锌/钴-层的焊接样品均是无裂纹的。焊接试验的结果也汇总在表1和2中。对于本发明的锌/铁-层也证实了类似好的结果。
在图1中在左侧部分图中示意性展示了具有多层结构的腐蚀保护涂层的一个本发明实施方案。向高锰钢基底上首先通过电解施加本发明的含锌腐蚀保护层，并随后通过电解施加由锌制成的第二层（ZE）。在该实施方案中，含锌腐蚀保护层的厚度可以为0.1微米至50微米，而基于锌的层的厚度可以为0.5微米至50微米。
图1中的右侧部分图展示了具有单层结构的第二实施方案。在这样的结构中，将厚度为0.5微米至50微米的含锌腐蚀保护层施加到高锰钢基底上。
图2和3展示了经电阻点焊的样品的图。
图2展示了常规的经锌涂覆的（ZE）高锰钢样品，其在电阻点焊方法中接合。锌层厚度为大约3.5微米。该样品在热作用区域中显示出液体金属诱导的裂纹。
图3展示了高锰钢样品，其通过电解用本发明的厚度为2微米并含有23重量%锰的锌合金层涂覆，并随后在电阻点焊方法中接合。该样品完全不具有裂纹。
表1：在具有不同组成的锌/锰-腐蚀保护涂层的板上的焊接试验的结果
表2：在具有不同组成的锌/钴-腐蚀保护涂层的板上的焊接试验的结果。

Claims (8)

1.改善高锰钢带的可焊性的方法，所述钢带以重量%计含有6至30%的锰、最高1%的碳、最高15%的铝、最高6%的硅、最高6.5%的铬、最高4%的铜以及添加的总计最高0.7%的钛和锆和总计最高0.5%的铌和钒、余量的铁和不可避免的钢伴生元素，其用含锌腐蚀保护层涂覆，其特征在于为了防止焊接过程中的液体金属脆化，施加第一含锌腐蚀保护层，该腐蚀保护层为锌/锰、锌/钴或锌/铁合金，并向所述第一含锌腐蚀保护层上施加厚度为1微米至12微米的第二含锌层，其中所述第一含锌腐蚀保护层的厚度为0.1微米至5微米，所述第二含锌层除了锌之外含有铝和/或硅和/或锰和/或铁作为其它元素。
2.根据权利要求1的方法，其特征在于所述第一含锌腐蚀保护层的锌含量为30-99重量%。
3.根据权利要求1或2的方法，其特征在于所述第一含锌腐蚀保护层的锌含量为75-95重量%。
4.根据权利要求1或2的方法，其特征在于所述第一和/或第二含锌层通过电解或通过从气相中的沉积来施加。
5.具有改善的可焊性的由高锰钢制成的经涂覆的钢带，其以重量%计含有6至30%的锰、最高1%的碳、最高15%的铝、最高6%的硅、最高6.5%的铬、最高4%的铜以及添加的总计最高0.7%的钛和锆和总计最高0.5%的铌和钒，余量的铁和不可避免的钢伴生元素，并具有含锌腐蚀保护层，其特征在于为了防止焊接过程中的液体金属脆化，所述钢带具有第一含锌腐蚀保护层，该腐蚀保护层为锌/锰、锌/钴或锌/铁合金，并且所述第一含锌腐蚀保护层上施加有厚度为1微米至12微米的第二含锌层，其中所述第一含锌腐蚀保护层的厚度为0.1微米至5微米，所述第二含锌层除了锌之外含有铝和/或硅和/或锰和/或铁作为其它元素。
6.根据权利要求5的钢带，其特征在于所述第一含锌腐蚀保护层的锌含量为30-99重量%。
7.根据权利要求5或6的钢带，其特征在于所述第一含锌腐蚀保护层的锌含量为75-95重量%。
8.根据权利要求5或6的钢带，其特征在于所述钢带具有至少0.04重量%的碳含量、分别至少0.05重量%的硅含量和/或铝含量、0.02至4重量%的铜含量和0.05至6.5重量%的铬含量。
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EP2976442B1 (de) 2018-11-28
WO2014146638A2 (de) 2014-09-25
EP2976442A2 (de) 2016-01-27
KR102196078B1 (ko) 2020-12-29
KR20150132182A (ko) 2015-11-25
US20160281252A1 (en) 2016-09-29
RU2015145062A (ru) 2017-05-03
DE102013005301A1 (de) 2014-09-25
RU2675437C2 (ru) 2018-12-19
CN105209668A (zh) 2015-12-30
WO2014146638A3 (de) 2015-03-12

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