CN101146923A - 钢带镀层方法以及设有所述镀层的钢带 - Google Patents

钢带镀层方法以及设有所述镀层的钢带 Download PDF

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CN101146923A
CN101146923A CNA2006800059386A CN200680005938A CN101146923A CN 101146923 A CN101146923 A CN 101146923A CN A2006800059386 A CNA2006800059386 A CN A2006800059386A CN 200680005938 A CN200680005938 A CN 200680005938A CN 101146923 A CN101146923 A CN 101146923A
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steel band
coating
steel
aluminium lamination
aforesaid right
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CN100577843C (zh
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哈拉尔德·霍夫曼
曼弗雷德·莫伊雷尔
贝恩德·舒马赫尔
斯拉夫乔·托帕尔斯基
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ThyssenKrupp Steel Europe AG
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ThyssenKrupp Stahl AG
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • 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
    • B32B15/012—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 aluminium or an aluminium alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
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Abstract

本发明涉及镀覆钢带的方法，所述钢带以重量％计包含C：≤1.6％、Mn：6－30％、Al：≤10％、Ni：≤10％、Cr：≤10％、Si：≤8％、Cu：≤3％、Nb：≤0.6％、Ti：≤0.3％、V：≤0.3％、P：≤0.1％、B：≤0.01％，余量为铁和不可避免的杂质。本发明的目的是开发一种对迄今为止尚不能被充分镀覆的钢带进行镀覆的方法，从而使该钢带获得表现出优异的耐腐蚀性和优良焊接性能的金属镀层。为了达到该目的，在最终退火之前将铝层施加到所述钢带上，随后将金属层施加到所述铝层上。本发明还公开一种通过本发明的方法形成的钢带或钢板。

Description

钢带镀层方法以及设有所述镀层的钢带
本发明涉及一种用于镀覆钢带的方法，所述钢带以重量％计含有C：≤1.6％、Mn：6-30％、Al：≤10％、Ni：≤10％、Cr：≤10％、Si：≤8％、Cu：≤3％、Nb：≤0.6％、Ti：≤0.3％、V：≤0.3％、P：≤0.1％、B：≤0.01％、N：≤1.0％，余量为铁和不可避免的杂质，其中对所述钢带进行最终退火处理，然后镀以由熔融金属构成的镀层。此外，本发明涉及一种钢带，该钢带具有相应组成的基材和施加于其上的金属镀层。根据上述镀层所需的特性，金属镀层尤其由铝/硅合金、纯铝、纯锌或锌合金构成。
锰含量高的钢由于同时具有以下两方面的有利特性而使其在特定程度上基本适合用于车辆制造工业(特别是汽车制造工业)中，所述特性为：一方面具有达1,400MPa的高强度，另一方面具有极高的伸长率(均匀伸长率高达70％，断裂伸长率高达90％)。特别适合于这种具体应用、并且具有7重量％到30重量％这样的高Mn含量的钢可从(例如)德国专利文献DE 102 59 230 A1、DE 197 27 759 C2或DE 199 00 199 A1中得知。由这些钢制得的平型制品具有各向同性的形变行为以及高强度，并且在低温下还是可延展的。
然而，与这些优点相对的是，锰含量较高的钢易于发生点状腐蚀，并且难于被钝化。与低合金钢相比，这种属于高合金钢板材料系列的钢在氯离子浓度增加的情况下易于出现部位有限、但强烈被腐蚀的倾向，因而，使其难于使用。此外，高锰含量的钢易于发生表面腐蚀，这也会限制其使用范围。
因此，人们也已提出要提供这样的平型钢制品，该平型钢制品由高锰含量的钢制备，并具有由原来已知方式形成的金属镀层，这种金属镀层会保护钢免受腐蚀侵害。为了达到这个目的，人们尝试通过电解向钢材上施加锌镀层。虽然这些努力最终会得到其基材在各情况中都可由高合金钢(通过施加于其上的金属镀层来保护该高合金钢免受腐蚀)构成的镀锌钢带，但已经表明，当对这类金属板进行焊接时，在焊接区域会产生在工业上以术语“焊接脆化”相称的问题。由于焊接，使得镀层中的锌材料液化而渗入基底金属的晶界中。这种渗透使得焊接区域周围范围内的材料失去强度和延展性，以至于达到焊缝和/或与焊缝相邻的金属板在负荷条件下不再能完全满足稳定性的要求这种程度。
通过已知的热浸镀法来制备具有足够的耐腐蚀性、同时具有优良的焊接性能的金属板的尝试仍然没有成功，这是因为高合金钢带(尤其是锰含量高于6重量％的钢带)在经历为了达到有效地热浸镀金属而必需进行的退火处理后，易于出现严重的表面氧化现象。以这种方式被氧化的金属板表面再也不能被金属镀料浸润到所需的均匀程度和完整程度，以至于用这种方法不能达到使整个表面区域防腐蚀的目的。
由高合金化而锰含量较低的钢系列得知的、通过施加Fe或Ni类的中间层来增强可浸润性的各种可能的方法在锰含量至少为6重量％的钢板的情况中尚未取得所期望的成功。
基于上述的现有技术，本发明的目的包括描述一种方法，该方法使得这类迄今为止还不能被完全镀覆的钢带也可以获得确保使其具有优异的耐腐蚀性及优良的焊接性能的金属镀层。此外，应当指出这样一种镀层钢带：其可以容易地被焊接，而不会出现焊接脆化的风险。
就这种方法而言，上述目的是通过以下方式而达到的：在对钢带进行镀层时，对所述钢带进行最终退火处理，随后镀以由熔融金属构成的镀层，根据本发明，在最终退火前将铝层施加于钢带上，在最终退火后，将镀层施加于所述铝层上，其中，所述钢带包含(以重量％计)C：≤1.6％、Mn：6-30％、Al：≤10％、Ni：≤10％、Cr：≤10％、Si：≤8％、Cu：≤3％、Nb：≤0.6％、Ti：≤0.3％、V：≤0.3％、P：≤0.1％、B：≤0.01％，余量为铁和不可避免的杂质。
根据本发明，在施加用于形成实际的防腐蚀层的金属镀层之前，将薄的铝层施加干作为基材的钢带上
在熔融金属镀层之前所必需的退火处理的过程中，钢带中的铁扩散到根据本发明施加的铝中，从而在该退火过程中，钢带上形成了基本由Al和Fe构成的金属沉积物，该金属沉积物随后与由钢带构成的基材紧密结合。附着在钢带上的铝会防止钢带表面在熔融金属镀层之前的退火过程中发生氧化。随后，铝层会起到一种助粘剂的作用，使得由熔融金属形成的镀层牢固地附着在钢带的整个表面区域上，即使在钢带本身由于合金化而产生对此不利的条件时也会如此。
出人意料的是，此外还表明，根据本发明施加在钢带和镀层之间的铝层除了以上提到的效果外，还具有这样的优点：在对根据本发明镀覆的金属板进行焊接时，它会对现有技术中所担心的焊接脆化问题起到抑制作用。因此，所述铝层与随后施加的镀层相结合会避免出现金属镀层材料在焊接过程中向钢材结构中渗透而使其强度和延展性受到持久性削弱的问题。本发明用于镀覆钢带的方法还可以提供这样一种钢带，该钢带用已知方法是不能完全镀覆的，并且该钢带具有金属类的防腐蚀表层。
优选的是，通过原来已知的PVD镀层法(PVD：物理气相沉积法)施加铝中间层，其中，使铝蒸发，并且挥发的铝蒸气在真空条件下凝结在被镀覆的钢带上，从而使铝以薄层的形式沉积于钢带上。在这种情况下，可以由铝蒸气的量来调节通过PVD镀层法施加在钢带上的铝层的厚度。
本发明的方法同样适合用于镀覆处于热轧或冷轧条件下的钢带。
如果铝中间层的厚度为50nm到1,000nm，则可以始终确保本发明的镀层具有足够的效果。
本发明的镀层方法尤其适用于高合金钢这样的钢带，以确保使其具有高强度和高伸长率的特性。因此，根据本发明，通过以下方式实现了上文针对具有钢基材和施加于其上的金属镀层的钢带所述的目的：使基本由Al和Fe构成的中间层位于基材和金属镀层之间，其中，所述钢基材包含(以重量％计)C：≤1.6％、Mn：6-30％、Al：≤10％、Ni：≤10％、Cr：≤10％、Si：≤8％、Cu：≤3％、Nb：≤0.6％、Ti：≤0.3％、V：≤0.3％、P：≤0.1％、B：≤0.01％，余量为铁和不可避免的杂质。按此方法制造的镀层钢板制品具有最佳的耐腐蚀性，同时还具有优良的焊接性能。
在这种情况下，如果中间层的厚度为50nm到1,000nm，则尤其能够确保通过本发明而达到的效果。
当对锰含量至少为6重量％的高合金钢带进行镀层时，通过本发明达到的效果会尤其有利。在这方面，已经表明，如果预先通过本发明的方法为钢基材设置铝中间层，则可以特别顺利地向其上镀以防腐蚀层，其中，所述钢基材包含(以重量％计)C：≤1.00％、Mn：20.0-30.0％、Al：≤0.5％、Si：≤0.5％、B：≤0.01％、Ni：≤3.0％、Cr：≤10.0％、Cu：≤3.0％、N：≤0.6％、Nb：≤0.3％、Ti：≤0.3％、V：≤0.3％、P：<0.1％，余量为铁和不可避免的杂质。如果将含有(以重量％计算)C：≤1.00％、Mn：7.00-30.00％、Al：1.00-10.00％、Si：>2.50-8.00％(其中，Al和Si的总含量>3.50-12.00％)、B：<0.01％、Ni：<8.00％、Cu：<3.00％、N：<0.60％、Nb：<0.30％、Ti：<0.30％、V：<0.30％、P：<0.0 1％、以及余量的铁和不可避免的杂质的钢用作基材，则同样是如此。
实际上，对于这种锰含量高的钢带，本发明公开了一种可以以经济的方式保护这些钢带免受腐蚀的方法，通过该方法使得这些钢带可在车辆制造工业(尤其是汽车制造工业)中用于生产车身，其中，这些钢带在正常使用时是暴露于特别具有腐蚀性的介质中的。
如在常规热浸镀层的情况中一样，通过本发明的方法对热轧钢带和冷轧钢带均可进行镀层。
具体而言，如果打算通过本发明的方法对高锰含量的钢带进行镀层，那么已证实的是，在施加中间层后进行退火处理时，退火温度为高于680℃到不超过900℃是有利的。在此温度范围内，所期望的钢带中的铁向预先施加的镀层中的扩散是肯定会发生的，从而使得镀层紧密结合在由钢带形成的基材上这种效果同样是肯定会实现的。已证实的是，如果通过PVD镀层法来施加中间层，则该温度范围是特别有利的。
与已知的热浸镀法相似，通过本发明的方法进行镀层的钢带所经历的退火处理应当在连续输送的条件下进行。在此情况下，退火炉可为原来已知的热浸镀设备的一部分。
优选的是，在惰性气氛下进行退火，以便在这一方面同样将氧化的几率降至最低程度。
根据可利用的设备技术和在各情况中所选用的退火温度，如果在施加中间层后进行退火处理，则为了使Fe由钢带向镀层中的扩散达到特别期望的程度，退火时间应为30秒到250秒。已证实的是，如果通过PVD镀层法来施加中间层，则该退火时间是特别有利的。
关于防腐蚀性和焊接性能，已经表明的是，如果施加于根据本发明的铝中间层上的熔融金属层由Al/Si合金、纯铝、纯锌和/或锌合金构成，则本发明的方法是特别有利的。
用于增强铝中间层对钢带的附着作用的本发明的又一实施方案的特征在于：施加铝中间层之前，对钢带表面进行清洗。
在进行熔融金属镀层后，为了优化镀层钢带的表面质量和粗糙程度，可用目前已知的方法进行表皮光轧。
以下将基于示出示例性实施方案的附图对本发明进行详细说明。这些附图在各情况下都是以示意性和局部的方式示出的：
图1为通过本发明的方法镀层的钢带样品的剖视图；
图2为根据图1的镀层钢带样品的俯视图；
图3为图1所示的镀层钢带样品在根据铁钢测试表SEP 1931进行落球冲击试验之后的俯视图；
图4为按照常规方法进行热浸镀之后的钢带样品的俯视图。
将高强度的钢(其除了含有铁和不可避免的杂质外，还包含为了满足其特性所必需的元素(以重量％计)：20％的Mn、2.7％的Al和2.7％的Si)浇铸成厚板并按常规方法将其精轧成热轧钢带，随后将此热轧钢带打卷。所得热轧钢带的抗拉强度Rm为720 MPa，且其伸长率A80为60％。
然后在第一阶段以30％的应变将按此方法得到的热轧钢带冷轧成冷轧钢带。然后，在900℃下对该冷轧钢带进行中间退火。在中间退火后，在下一阶段以40％的应变将由此方法所得的钢带S冷轧至最终厚度。
冷轧后，在进入PVD镀层设备之前，对冷轧钢带的表面进行化学清洗。
在PVD镀层设备中，通过在真空状态下将含铝的蒸气输送到钢带S的表面并使之沉积在所述表面上，从而将厚度为0.5 μm的铝层施加在钢带S上。
在通过PVD法对钢带镀以铝层后，继续输送钢带，从而在惰性气氛(由5％的H2和余量的N2组成)下于800℃的退火炉中对其进行退火，钢带通过时间(transit time)为60秒。在该第一次退火阶段后，继续输送钢带，从而在退火炉内并且在冷却到660℃的惰性气氛下对其进行退火，其中，钢带S在此温度下进入由铝硅合金构成的热浸金属浴中。
在进行退火处理过程中，铁由钢带S中的钢材料扩散到通过PVD镀层法施加到钢带表面的铝层中，从而形成基本上由Al和Fe构成的AlFe层，该AlFe层与钢带S紧密结合并牢固地附着在钢带S上(图1)。
在热浸金属浴中，将具有AlFe层的钢带S镀以AlSi层。由于在热浸镀过程中发生扩散，结果，在这种情况下，形成了基本由Al、Fe和Si构成的AlFeSi中间镀层。该AlFeSi中间镀层的厚度大于直接附着在钢带S表面上的AlFe层的厚度，但是却实质性地小于基本由Al和Si构成的外附AlSi层的厚度(图1)。
在将按此方法进行镀层之后的钢带S从热浸金属浴中移出后，采用已知的方法通过喷射刮料系统(jet stripping system)对镀层厚度进行调整。随后，将镀层钢带S冷却，并且为了优化表面光洁度而对其进行表皮光轧。随后将所得到的钢带S上油，并卷绕成卷，以待发运。
图2示出了通过上述的本发明方法制得的镀层钢板的局部俯视图。从中可清晰地看出所施加的镀层整体上是致密而均匀的。
最后，图3示出了在钢板S上进行的落球冲击试验的结果。结果表明由AlFe层、AlFeSi层和AlSi层构成的镀层结构对钢带S具有优异的附着性。因此，不会观测到镀层出现剥落或者类似的破损的情况。
与此形成对比的是，为了进行对照，图4示出了采用与钢带S完全相同的方法合金化的钢带V的俯视图。对钢带V也采用与钢带S相同的方法进行处理，直到通过PVD法施加铝层的阶段为止。然而，从图4中可明显的看出，钢带V在处理步骤完成后实质上不具有镀层。

Claims (14)

1.一种镀覆钢带的方法，所述钢带以重量％计包含C：≤1.6％、Mn：6-30％、Al：≤10％、Ni：≤10％、Cr：≤10％、Si：≤8％、Cu：≤3％、Nb：≤0.6％、Ti：≤0.3％、V：≤0.3％、P：≤0.1％、B：≤0.01％、N：≤1.0％，余量为铁和不可避免的杂质，其中，对所述钢带进行最终退火，随后镀以由熔融金属构成的镀层，所述方法的特征在于，在最终退火之前将铝层施加于所述钢带上，在最终退火之后，将所述镀层施加于所述铝层上。
2.根据权利要求1的方法，其特征在于所述铝层的厚度为50nm到1,000nm。
3.根据上述权利要求中的任何一项的方法，其特征在于在施加所述铝层之后所进行的最终退火的过程中，退火温度高于680℃并且不超过900℃。
4.根据上述权利要求中的任何一项的方法，其特征在于在最终退火过程中退火时间为30秒到250秒。
5.根据上述权利要求中的任何一项的方法，其特征在于所述熔融金属是通过热浸镀法施加的。
6.根据上述权利要求中的任何一项的方法，其特征在于在最终退火后施加的所述熔融金属是由Al/Si合金、Al以及/或者锌或锌合金构成的。
7.根据上述权利要求中的任何一项的方法，其特征在于在施加所述镀层之前对所述钢带的表面进行清洗。
8.根据上述权利要求中的任何一项的方法，其特征在于所述铝层是通过PVD镀层法施加的。
9.一种钢带，该钢带具有钢基材和施加在所述钢基材上的金属镀层，其中，所述钢基材以重量％计包含C：≤1.6％、Mn：6-30％、Al：≤10％、Ni：≤10％、Cr：≤10％、Si：≤8％、Cu：≤3％、Nb：≤0.6％、Ti：≤0.3％、V：≤0.3％、P：≤0.1％、B：≤≤0.01％、N：≤1.0％，余量为铁和不可避免的杂质，所述钢带的特征在于，一种大体上由Al和Fe构成的中间层位于所述基材和所述镀层之间。
10.根据权利要求9的钢带，其特征在于所述中间层的厚度被限定为50nm到不超过1,000nm。
11.根据权利要求9或10的钢带，其特征在于所述镀层是由Al/Si合金、Al、Zn或Zn合金形成的。
12.根据权利要求9到11中的任何一项的钢带，其特征在于所述基材以重量％计含有以下成分：
C：≤1.00％，
Mn：20.0-30.0％，
Al：≤0.5％，
Si：≤0.5％，
B：≤0.01％，
Ni：≤3.0％，
Cr：≤10.0％，
Cu：≤3.0％，
N：＜0.6％，
Nb：＜0.3％，
Ti：＜0 3％，
V：＜0.3％，
P：＜0.1％，
余量为铁和不可避免的杂质。
13.根据权利要求9到11中的任何一项的钢带，其特征在于所述基材以重量％计含有以下成分：
C：≤1.00％，
Mn：7.00-30.00％，
Al：1.00-10.00％，
Si：＞2.50-8.00％，
其中，Al+Si的总含量＞3.50-12.00％，
B：＜0.01％，
Ni：＜8.00％，
Cu：＜3.00％，
N：＜0.60％，
Nb：＜0.30％，
Ti：＜0.30％，
V：＜0.30％，
P：＜0.01％，
余量为铁和不可避免的杂质。
14.根据权利要求9到13中的任何一项的钢带，该钢带是采用根据权利要求1到8中的任何一项开发的方法制备而成的。
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