CN106661707B - 经表面处理的钢板及其制造方法 - Google Patents

经表面处理的钢板及其制造方法 Download PDF

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CN106661707B
CN106661707B CN201580044607.2A CN201580044607A CN106661707B CN 106661707 B CN106661707 B CN 106661707B CN 201580044607 A CN201580044607 A CN 201580044607A CN 106661707 B CN106661707 B CN 106661707B
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nickel
steel sheet
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corrosion protection
protection layer
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帕特里克·库恩
马丁·诺登
阿克塞尔·施罗滕
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ThyssenKrupp Steel Europe AG
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Abstract

本发明涉及一种经表面处理的钢板、优选冷轧的薄钢板，其具有金属防腐蚀保护层，其另外含有铝和铁，其中，该防腐蚀保护层的铝含量大于40重量％、优选大于45重量％、特别优选大于50重量％。因此防腐蚀保护层具有良好的可成型性、特别是可冷成型性并由此在成型过程中具有显著改善的附着性，按照本发明该防腐蚀保护层还含有镍，其中，特别在防腐蚀保护层向钢板的基本材料的过渡上形成含镍相，防腐蚀保护层的镍含量在5至30重量％、优选10至25重量％的范围内。另外还描述了用于制造这种经表面处理的钢板的方法。按照本发明方法的特征在于，扁钢产品、优选冷轧的薄钢板作为扁钢产品在热浸镀有液态熔体铝或液态熔体的基于铝的合金之前先设置有一个镍层。

Description

经表面处理的钢板及其制造方法
技术领域
本发明涉及一种经表面处理的钢板、优选冷轧的薄钢板，其具有金属的防腐蚀保护层，该防腐蚀保护层另外含有铝和铁，其中，防腐蚀保护层的铝含量大于40重量％、优选大于45重量％、特别优选大于50重量％。另外，本发明还涉及用于制造通过金属的防腐蚀保护层表面处理的钢板的方法，其中，扁钢产品、优选冷轧的薄钢板通过热浸镀层而覆有铝或者基于铝的合金。
背景技术
未涂层的碳素钢、特别是硼合金化的调质钢由于较差的耐腐蚀性而设置有金属的防腐蚀保护层。在现有技术中这通常通过热浸镀有基于锌和铝的金属熔体而进行。火镀锌的薄钢板使锌的突出的耐腐蚀性与钢的强度相结合。火镀铝的薄钢板使突出的耐腐蚀性与热负荷性能相结合。另外优点在于铝的视觉外观与钢的强度相结合。已知的特别是薄钢板，其通过热浸镀层设置有铝硅涂层。
热浸镀处理后的薄钢板特别是用在汽车制造中，其中通过由薄板裁切成的扁坯的成型制成三维形成的车身部件以及底盘部件。
为了减小汽车重量或者降低燃油消耗而越来越多得使用调质钢，该调质钢的特征在于在加热的状态下良好的可成型性以及在热成型之后通过快速的冷却(加压硬化)具有特别高的强度。已知的调质钢为钢种22MnB5。该钢种的突出的强度性能除了碳和锰之外特别还通过较少含量的硼而实现。
但是已知的铝硅涂层(例如其大量地在热成型中使用)具有这样的缺点，即，其仅受限地适用于冷成型。因此，当例如在热成型应用之前要求设置在先的冷成型时，不能使用该涂层。因为已显示，在具有这种涂层的钢板的冷成型的过程中会导致在部件的要求变形的区域中的涂层的剥落并使得在这些裸露的位置上失去了防腐蚀保护。
发明内容
由此出发，本发明的目的在于，得到一种开头所述类型的钢板，其防腐蚀保护层实现了良好的可成型性、特别是可冷成型性并且具有在成型过程中明显改善的附着。这种钢板应优选也适用于热成型(加压硬化)。
按照本发明的钢板设置具有金属的防腐蚀保护层，该防腐蚀保护层含有铝、镍和铁，其中，该防腐蚀保护层的铝含量为大于40重量％、优选大于45重量％、特别优选大于50重量％，而该防腐蚀保护层的镍含量处于5至30重量％的范围内、优选10至25重量％的范围内，而且其中，特别在防腐蚀保护层向钢板的基本材料的过渡上形成含镍相。
相应地，按照本发明的方法的特征在于，所涉及的扁钢产品、优选冷轧的薄钢板在热浸镀层之前首先设置有一个镍层。
在申请人方的企业内部试验已经得出，按照本发明的防腐蚀保护层相对于已知的铝和铝硅热浸镀层具有在冷成型过程中显著提高的延展性和附着性。特别是这些试验已得出，由硼合金化的调质钢组成的、具有按照本发明的防腐蚀保护层的钢板也适用于热成型(加压硬化)。
镍层的涂覆优选借助电解的涂层过程进行。
根据按照本发明的方法的有利的设计，为了使扁钢产品或冷轧的薄钢板预涂覆有镍的涂层过程、优选电解的涂层过程这样实施，即，由此涂覆的镍层具有在1至5μm范围内、优选3至5μm范围内的层厚度。由此可以进一步提高或优化按照本发明的防腐蚀保护层的延展性和附着性。
根据按照本发明的方法的另一个设计，通过为电解的涂层过程而使用镍电解液，可以可靠且经济地在扁钢产品或冷轧的薄钢板上涂覆镍层，其中镍电解液基于硫酸镍和氯化镍。
按照本发明的方法的另一个有利的设计的特征在于，设置有镍层的扁钢产品在热浸镀层之前在保护气体下进行重结晶的退火处理。由此改善可成型性、特别是扁钢产品的可冷成型性。重结晶的退火处理包括在特定的温度下保持经过特定的持续时间和在达到期望的性能之后受控的冷却。优选将设置有镍层的经退火的扁钢产品冷却至这样的温度，该温度位于熔池的温度以上并且与熔池温度的差距不大于20℃。退火后的扁钢产品的冷却以特定的速度进行，以使得不对所达到的性能产生负面的影响。通过在保护气体中的退火防止了设置有镍层的扁钢产品在热浸镀层之前氧化或者防止进行其他不期望的表面反应。
随后的热浸镀层优选这样实施，即，所产生的含有铝、铁和镍的防腐蚀保护层具有在8至20μm范围内、优选10至15μm范围内、特别优选10至12μm范围内的层厚度。由此可以以经济的方式通过防腐蚀保护层在涂层的扁钢产品的冷成型过程中理想的附着性而实现非常可靠的防腐蚀保护。
在按照本发明的方法中为了热浸镀层而使用熔池，该熔池优选除了不可避免的杂质之外含有纯的铝熔体。在按照本发明的方法中也可以替代性的使用这样的熔池，其含有具有最大10重量％的硅的铝熔体。但申请人一方的试验已得出，按照本发明的防腐蚀保护层在使用基本上纯铝熔体的情况下具有在冷成型过程中最优的附着性。
如果在使用含硅的铝熔体的条件下实施热浸镀层(该热浸镀层紧随着用于涂覆镍层的电解的涂层过程)，那么优选这样调整过程参数，即，相应的经表面处理的钢板的金属防腐蚀保护层具有小于8重量％、优选小于5重量％的Si含量。
通过以电解涂覆的镍层的形式的预涂层，抑制了铁从钢板(扁钢产品)向通过热浸镀层而涂覆的铝中的扩散。优选这样调整过程参数，即，在相应的经表面处理的钢板的金属的防腐蚀保护层的外侧的层半部分中，镍含量大于铁含量。
另外，优选这样调整过程参数，即，在按照本发明的防腐蚀保护层中产生或形成金属间的AlNi相。
作为用于制造按照本发明的钢板的基础材料优选使用可加压硬化的钢、例如钢种22MnB5。
附图说明
随后参照附带的附图借助实施例进一步说明本发明。其中：
图1示出了按照本发明涂层的钢板借助辉光放电光谱(Glimmentladungsspektroskopie(GDOES))确定的元素深度分布；并且
图2示出了冷冲的杯突，其中，左侧的杯突由具有常规的AlSi涂层的钢板制成而右侧的杯突由具有按照本发明的Al-Ni涂层的钢板制成。
具体实施方式
为了制造通过金属的防腐蚀保护层而表面处理的钢板，具有约1.25mm板厚的冷轧的薄板带在连续的电解涂层过程中设置有约3μm厚的镍层或在一个变体中设置有约1μm厚的镍层。为此，分别使用基于硫酸镍和氯化镍的所谓的Watt镍电解液。该涂层过程也可以称为电镀的涂层过程。作为冷轧的薄板带分别使用钢种22MnB5的钢带(基础材料)。
随后，电解镀镍的薄板带在一个连续加工的热浸镀层设备中进行退火处理。预设在涂层池之前的热浸镀层设备的连续炉中，预涂层有镍的薄板带在保护气体或氮氢混合气氛(约95％的氮气，5％的氢气，露点-30℃)下重结晶退火。在60秒的保持时间之后，在约800℃的温度下，将退火后的薄板带冷却至约705℃的池浸入温度并随后引导通过镀层池。在一个优选的变型中，该镀层池基本上由纯熔体液态的铝组成。在另一个变型中使用这样的镀层池，该镀层池由具有约10重量％的硅的铝熔体组成。这样涂覆的铝涂层或者AlSi涂层的层厚借助设置在涂层池上方的刮除喷嘴而这样调整，以使得由镍层和热浸镀涂层形成的金属防腐蚀层具有约10μm的层厚。该金属的防腐蚀保护层也可以称为铝镍合金层。
图1中借助元素深度分布示出了按照本发明在热浸镀层过程之后得到的、预镀镍的钢板的防腐蚀保护层的组成成分。虚线相对于金属防腐蚀保护层的深度示出了以重量％表示的镍含量。由左下方开始，直到近乎100重量％攀升的曲线相对于其深度示出了防腐蚀保护层的Fe含量，而第三条曲线为Al含量。
可以看出，在该实施例中，在靠近防腐蚀保护层的表面处的镍含量在10至12重量％的范围内。朝冷轧的薄板的方向上，约10μm厚的防腐蚀保护层的镍含量直到约6μm的深度增加至19至20重量％。防腐蚀保护层的镍含量随即朝涂层的薄板的方向逐渐下降。
防腐蚀保护层的铝含量在防腐蚀保护层的表面附近具有其最大值。在该实施例中，Al含量的最大值在约82至86重量％的范围内。通过镍涂层(镍预涂层)抑制了铝中的铁含量，由此使涂层比已知的AlSi涂层具有明显更低的脆性或明显更高的延展性。在图1中可以看出，在防腐蚀保护层的外侧的层半部分中，镍含量明显大于铁含量。
为了评价按照本发明的防腐蚀保护层的变形性能，对相应涂层的冷轧的22MnB5类型薄钢板进行冷成型，即，以圆杯突进行深冲，而且借助防腐蚀保护层的外观与已知的AlSi热浸镀涂层(作为参照)以及已知的Al热浸镀涂层比较涂层附着性(参见表格)。另外，通过制造不同厚度的镍层或试验不具有镍预涂层的样品，来变化样品制造。
表格示出了，在冷成型过程中，相对于已知的AlSi和Al热浸镀涂层(样品1和4)，通过足够厚的镍层可以显著地提高涂层(防腐蚀保护层)的延展性和附着性。图2中的图像更加说明了这一点。
图2中左侧的杯突通过对具有常规的AlSi涂层的薄钢板进行冷深冲而制成。相反地，右侧的杯突通过对于具有按照本发明的Al-Ni涂层的薄钢板进行冷深冲而制成。左侧的杯突在杯突要求变形的区域中具有明显的AlSi涂层的剥落，而在右侧的杯突上没有发现任何剥落。
按照本发明的防腐蚀保护层的特征在于在冷成型过程中明显提高的延展性和同时显著改善的附着性。按照本发明的防腐蚀保护层另外还具有防止氧化皮的特性，该特性使已知的AlSi涂层用于热成型。
按照本发明的防腐蚀保护层因此同样适用于热成型。本发明的优点特别是也能够在通过滚轧成型和随后的硬化而制造构件的过程中使用。
Figure GDA0002208745520000061
表格:涂层附着性/可冷成型性的对比。

Claims (15)

1.一种经表面处理的钢板，其具有金属的防腐蚀保护层，所述防腐蚀保护层限定所述经表面处理的钢板的表面并且含有铝和铁，所述防腐蚀保护层的铝含量为大于40重量％，金属的防腐蚀保护层另外还含有镍，其中，在防腐蚀保护层向钢板的基本材料的过渡上形成含镍相，其特征在于，所述防腐蚀保护层的镍含量处于10至30重量％的范围内，在所述金属的防腐蚀保护层的外侧的层半部分中，镍含量大于铁含量，并且所述金属的防腐蚀保护层具有在8至15μm范围内的厚度。
2.根据权利要求1所述的经表面处理的钢板，其特征在于，所述金属的防腐蚀保护层除了镍、铁和铝之外还包含硅。
3.根据权利要求1或2所述的经表面处理的钢板，其特征在于，所述金属的防腐蚀保护层的硅含量为小于8重量％。
4.根据权利要求1所述的经表面处理的钢板，其特征在于，所述经表面处理的钢板的基础材料是经冷轧的薄钢板。
5.根据权利要求1所述的经表面处理的钢板，其特征在于，所述经表面处理的钢板的基础材料是可加压硬化的钢。
6.根据权利要求1所述的经表面处理的钢板，其特征在于，在所述金属的防腐蚀保护层中形成金属间的AlNi相。
7.根据权利要求1所述的经表面处理的钢板，其特征在于，所述金属的防腐蚀保护层具有在10至15μm范围内的厚度。
8.一种用于制造通过金属的防腐蚀保护层表面处理的钢板的方法，其中，扁钢产品通过热浸镀层而涂覆有铝或者基于铝的合金，所述扁钢产品在热浸镀层之前首先设置有一个镍层，其特征在于，用于施加所述镍层的涂层过程这样实施，以使得由此涂覆的镍层具有在1至5μm范围内的层厚度，并且所述热浸镀层这样实施，使得所产生的含有铝、铁和镍的防腐蚀保护层具有在8至15μm范围内的层厚度，并且这样调整过程参数，即，在相应的经表面处理的钢板的金属的防腐蚀保护层的外侧的层半部分中，镍含量大于铁含量。
9.根据权利要求8所述的方法，其特征在于，用于施加所述镍层的涂层过程这样实施，以使得由此涂覆的镍层具有在3至5μm范围内的层厚度。
10.根据权利要求 8或9所述的方法，其特征在于，所述镍层借助电解的涂层过程而涂覆。
11.根据权利要求10所述的方法，其特征在于，为了电解的涂层过程而使用镍电解液，所述镍电解液基于硫酸镍和氯化镍。
12.根据权利要求8所述的方法，其特征在于，设置有镍层的扁钢产品在热浸镀层之前在保护气体下进行重结晶的退火处理。
13.根据权利要求8所述的方法，其特征在于，所述热浸镀层这样实施，即，所产生的含有铝、铁和镍的防腐蚀保护层具有在10至15μm范围内的层厚度。
14.根据权利要求8所述的方法，其特征在于，为了热浸镀层而使用熔池，所述熔池除了不可避免的杂质之外含有纯的铝熔体。
15.根据权利要求8所述的方法，其特征在于，为了热浸镀层而使用熔池，所述熔池含有具有最大10重量％的硅的铝熔体。
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