CN114555838A - 模压淬火方法 - Google Patents

模压淬火方法 Download PDF

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Publication number
CN114555838A
CN114555838A CN202080072982.9A CN202080072982A CN114555838A CN 114555838 A CN114555838 A CN 114555838A CN 202080072982 A CN202080072982 A CN 202080072982A CN 114555838 A CN114555838 A CN 114555838A
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steel sheet
equal
coating
oxide
atmosphere
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CN114555838B (zh
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赖莎·格里戈里耶娃
佛罗林·杜米尼克
卜拉欣·纳比
帕斯卡尔·德里耶
蒂埃里·斯图雷尔
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ArcelorMittal SA
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Abstract

本发明涉及模压淬火方法,所述模压淬火方法包括以下步骤:A.提供用于热处理的钢板,所述钢板任选地预涂覆有基于锌或基于铝的预涂层,B.以10nm至550nm的厚度沉积包含铬并且不包含镍的氢屏障预涂层,C.对预涂覆钢板进行切割以获得坯件,D.在具有氧化力等于或高于包含1体积%氧气的气氛的氧化力并且等于或小于包含50体积%氧气的气氛的氧化力的气氛中,在1分钟至12分钟的保留时间期间,在800℃至970℃的炉温度下对坯件进行热处理,这样的气氛的露点为‑30℃至+30℃,E.将坯件转移到压制工具中,F.在600℃至830℃的温度下将坯件热成形以获得部件,G.将以步骤E)获得的部件冷却以在钢中获得以下显微组织:所述显微组织为马氏体或马氏体‑贝氏体,或者由以体积分数计至少75%的等轴铁素体、5体积%至20体积%的马氏体和量小于或等于10体积%的贝氏体构成。

Description

模压淬火方法
本发明涉及模压淬火方法,所述模压淬火方法包括提供用于热处理的涂覆有屏障涂层的钢板。该氢屏障预涂层更好地抑制氢吸附并且增强耐延迟断裂性。本发明特别好地适合于制造机动车辆。
用于模压淬火的涂覆钢板有时被称为“预涂覆的”,这个前缀表示预涂层性质的转变将在冲压之前的热处理期间发生。可以具有多于一种预涂层。本发明公开了一种预涂层,任选地两种预涂层。
已知某些应用(尤其在机动车领域中)要求金属结构在受到冲击的情况下进一步减轻和加强,并且具有良好的可拉拔性。为此,通常使用具有改善的机械特性的钢,这样的钢通过冷冲压和热冲压来成形。
然而,已知在某些冷成形或热成形操作之后,对延迟断裂的敏感性随机械强度而增加,因为在变形之后容易留存高残余应力。与可能存在于钢板中的原子氢结合,这些应力容易导致延迟断裂:在变形本身之后一定时间发生的开裂。氢可以通过扩散到晶格缺陷(例如基体/夹杂物界面、孪晶间界和晶界)中而逐渐地累积。在后面的缺陷中,当氢在一定时间之后达到临界浓度时其可能变得有害。该延迟由残余应力分布区域以及氢扩散的动力学造成,室温下的氢扩散系数低。此外,位于晶界处的氢削弱它们的内聚力并有利于延迟的晶间裂纹的出现。
模压淬火被认为对于氢吸附是关键的,所述氢吸附增加对延迟断裂的敏感性。在奥氏体化热处理(其为热压成形本身之前的加热步骤)下可能发生吸附。至钢中的氢的吸附实际上依赖于冶金相。此外,在高温下,炉中的水在钢板的表面分解成氢气和氧气。
WO2017/187255公开了具有特别是在热成形之前的热处理期间,防止氢吸附的屏障的效果的预涂层。该氢屏障预涂层包含镍和铬,其中重量比Ni/Cr为1.5至9。该专利申请公开了为惰性气氛或者包含空气的气氛的热处理的气氛。所有实施例均在由氮气组成的气氛中进行。
根据WO2020/070545,热成形之前的热处理可以在具有以下氧化力的气氛中发生:所述氧化力等于或高于包含1体积%氧气的气氛的氧化力并且等于或小于包含50体积%氧气的气氛的氧化力,这样的气氛的露点为-30℃至30℃,以进一步减少氢吸附。
在两个专利申请中,虽然奥氏体化热处理期间的氢吸附得到改善,但是不足以获得具有优异的耐延迟断裂性的部件。实际上,即使预涂覆屏障减少氢吸附,少数氢分子也仍然被钢板吸附。
因此,本发明的目的是提供其中防止氢吸附至钢板中的模压淬火方法。本发明旨在使得可获得可通过包括热成形的所述模压淬火方法获得的具有优异的耐延迟断裂性的部件。
该目的通过提供包括以下步骤的模压淬火方法来实现:
A.提供用于热处理的钢板,所述钢板任选地预涂覆有基于锌或基于铝的预涂层,
B.以10nm至550nm的厚度沉积包含铬并且不包含镍的氢屏障预涂层,
C.对预涂覆钢板进行切割以获得坯件,
D.在具有氧化力等于或高于包含1体积%氧气的气氛的氧化力并且等于或小于包含50体积%氧气的气氛的氧化力的气氛中,在1分钟至12分钟的保留时间期间,在800℃至970℃的炉温度下对坯件进行热处理,这样的气氛的露点为-30℃至+30℃,
E.将坯件转移到压制工具中,
F.在600℃至830℃的温度下将坯件热成形以获得部件,
G.将以步骤E)获得的部件冷却以在钢中获得以下显微组织:所述显微组织为马氏体或马氏体-贝氏体,或者由以体积分数计至少75%的等轴铁素体、5体积%至20体积%的马氏体和量小于或等于10体积%的贝氏体构成。
实际上,发明人出乎意料地发现,当用包含铬并且不包含镍的氢屏障预涂层对钢板进行预涂覆时以及当在以上气氛中进行奥氏体化热处理时,预涂层的这种屏障效果得到进一步改善,从而防止甚至更多的氢吸附至钢板中。与在奥氏体化热处理期间由选择性氧化物的较薄的层通过其形成在氢屏障预涂层的表面上的氮气组成的气氛相反,认为以低动力学在屏障预涂层的表面上形成热力学上稳定的氧化物。
在特定的以上气氛中,认为包含铬并且不包含镍的氢屏障预涂层允许比包含镍和铬的氢屏障预涂层更高的氢吸附减少。实际上,认为铬形成了比由镍和铬形成的氧化物层更厚的氧化物层。不希望受任何理论束缚,认为包含铬并且不包含镍的氢屏障预涂层可以防止水在氢屏障预涂层表面分解并且还通过氢屏障预涂层来防止氢扩散。在具有氧化力等于或高于包含1体积%氧气的气氛的氧化力并且等于或小于包含50体积%氧气的气氛的氧化力的气氛的情况下,认为为热力学上稳定的氧化物进一步抑制水分解。
根据本发明的方法的本质特征之一在于选择具有氧化力等于或高于包含1体积%氧气的气氛的氧化力并且等于或小于包含50体积%氧气的气氛的氧化力的气氛。
在步骤A)中,所使用的钢板由如欧洲标准EN 10083中描述的用于热处理的钢制成。其在热处理之前或之后可以具有高于500MPa、有利地为500MPa至2000MPa的抗拉强度(tensile resistance)。
钢板的重量组成优选如下:0.03%≤C≤0.50%;0.3%≤Mn≤3.0%;0.05%≤Si≤0.8%;0.015%≤Ti≤0.2%;0.005%≤Al≤0.1%;0%≤Cr≤2.50%;0%≤S≤0.05%;0%≤P≤0.1%;0%≤B≤0.010%;0%≤Ni≤2.5%;0%≤Mo≤0.7%;0%≤Nb≤0.15%;0%≤N≤0.015%;0%≤Cu≤0.15%;0%≤Ca≤0.01%;0%≤W≤0.35%,余量为铁和来自钢的制造的不可避免的杂质。
例如,钢板为具有以下组成的22MnB5:0.20%≤C≤0.25%;0.15%≤Si≤0.35%;1.10%≤Mn≤1.40%;0%≤Cr≤0.30%;0%≤Mo≤0.35%;0%≤P≤0.025%;0%≤S≤0.005%;0.020%≤Ti≤0.060%;0.020%≤Al≤0.060%;0.002%≤B≤0.004%,余量为铁和来自钢的制造的不可避免的杂质。
钢板可以为具有以下组成的
Figure BDA0003601386240000031
0.24%≤C≤0.38%;0.40%≤Mn≤3%;0.10%≤Si≤0.70%;0.015%≤Al≤0.070%;0%≤Cr≤2%;0.25%≤Ni≤2%;0.020%≤Ti≤0.10%;0%≤Nb≤0.060%;0.0005%≤B≤0.0040%;0.003%≤N≤0.010%;0.0001%≤S≤0.005%;0.0001%≤P≤0.025%;应理解,钛和氮的含量满足Ti/N>3.42;以及碳、锰、铬和硅的含量满足:
Figure BDA0003601386240000032
组成任选地包含以下中的一者或更多者:0.05%≤Mo≤0.65%;0.001%≤W≤0.30%;0.0005%≤Ca≤0.005%,余量为铁和来自钢的制造的不可避免的杂质。
例如,钢板为具有以下组成的
Figure BDA0003601386240000033
0.040%≤C≤0.100%;0.80%≤Mn≤2.00%;0%≤Si≤0.30%;0%≤S≤0.005%;0%≤P≤0.030%;0.010%≤Al≤0.070%;0.015%≤Nb≤0.100%;0.030%≤Ti≤0.080%;0%≤N≤0.009%;0%≤Cu≤0.100%;0%≤Ni≤0.100%;0%≤Cr≤0.100%;0%≤Mo≤0.100%;0%≤Ca≤0.006%,余量为铁和来自钢的制造的不可避免的杂质。
钢板可以根据期望的厚度(其可以为例如0.7mm至3.0mm)通过热轧和任选地冷轧来获得。
在步骤A)中,出于抗腐蚀目的,钢板的顶部可以直接被基于锌或基于铝的预涂层覆盖。在一个优选的实施方案中,基于锌或基于铝的预涂层基于铝并且包含小于15%的Si、小于5.0%的Fe、任选地0.1%至8.0%的Mg和任选地0.1%至30.0%的Zn,剩余部分为Al。例如,基于锌或基于铝的预涂层为
Figure BDA0003601386240000041
在另一个优选的实施方案中,基于锌或基于铝的预涂层基于锌并且包含小于6.0%的Al、小于6.0%的Mg,剩余部分为Zn。例如,基于锌或基于铝的预涂层为锌涂层,以获得以下产品:
Figure BDA0003601386240000042
GI。
基于锌或基于铝的预涂层还可以包含按重量计含量高至5.0%,优选为3.0%的杂质和残余元素例如铁。
任选地,在步骤A)中,氢屏障预涂层包含选自Sr、Sb、Pb、Ti、Ca、Mn、Sn、La、Ce、Cr、Zr或Bi中的元素,各个另外的元素按重量计的含量小于0.3重量%。
在一个优选的实施方案中,在步骤A)中,氢屏障预涂层不包含选自Al、Fe、Si、Zn和N中的元素中的至少一者。实际上,不希望受任何理论束缚,存在以下风险:这些元素中的至少一者的存在降低氢预涂层的屏障效果。
优选地,在步骤A)中,氢屏障预涂层以50重量%或75重量%或90重量%包含Cr。更优选地,氢屏障预涂层由铬组成,即,氢屏障预涂层仅包含Cr和另外的元素。
优选地,在步骤A)中,在步骤B)至F)之前没有另外的预涂层沉积在氢屏障预涂层上。
优选地,在步骤A)中,氢屏障预涂层的厚度为10nm至90nm或者150nm至250nm。例如,屏障预涂层的厚度为50nm、200nm或400nm。
不希望受任何理论束缚,似乎当屏障预涂层低于10nm时,由于屏障预涂层未充分覆盖钢板,因此存在氢吸附至钢中的风险。当屏障预涂层高于550nm时,似乎存在以下风险:屏障预涂层变得更脆,并且氢吸附由于屏障预涂层脆化而开始。
预涂层可以通过本领域技术人员已知的任何方法来沉积,例如热浸镀锌过程;辊涂;电镀锌过程;物理气相沉积,例如喷射气相沉积、磁控溅射或电子束诱导沉积。优选地,氢屏障预涂层通过电子束诱导沉积或辊涂来沉积。在预涂层的沉积之后,可以实现光整冷轧并且使预涂覆钢板加工硬化,并给予其便于后续成形的粗糙度。可以施加脱脂和表面处理以改善例如粘合剂粘结或耐腐蚀性。
在提供根据本发明的预涂覆有金属预涂层的钢板之后,对预涂覆的钢板进行切割以获得坯件。在炉中将热处理施加至坯件。优选地,热处理在800℃至970℃的温度下,在非保护性气氛下或保护性气氛下进行。更优选地,热处理在通常为840℃至950℃,优选为880℃至930℃的奥氏体化温度Tm下进行。有利地,所述坯件在1分钟至12分钟、优选地3分钟至9分钟的停留时间tm期间保持。在热成形之前的热处理期间,预涂层形成具有高的耐腐蚀性、耐磨性、抗磨性和抗疲劳性的合金层。
优选地,在步骤C)中,所述气氛具有这样的氧化力:所述氧化力等于或高于包含10体积%氧气的气氛的氧化力并且等于或小于包含30体积%氧气的气氛的氧化力。例如,所述气氛为空气,即,由约78%的N2、约21%的O2和其他气体例如稀有气体、二氧化碳和甲烷组成。
优选地,在步骤C)中,露点为-20℃至+20℃,并且有利地为-15℃至+15℃。实际上,不希望受任何理论束缚,认为当露点在以上范围内时,热力学上稳定的氧化物的层在热处理期间减少甚至更多的H2吸附。
所述气氛可以由以下构成:N2或Ar或者氮气或氩气和气体氧化剂例如氧气的混合物、CO和CO2的混合物或者H2和H2O的混合物。可以在不添加惰性气体的情况下使用CO和CO2的混合物或者H2和H2的混合物。
在热处理之后,然后将坯件转移至热成形工具,并将其在600℃至830℃的温度下热成形。热成形可以为热冲压或辊轧成形。优选地,将坯件热冲压。然后将部件在热成形工具中冷却或者在转移至特定的冷却工具之后冷却。
根据钢组成以这样的方式控制冷却速率:使得热成形之后的最终显微组织主要包含马氏体,优选包含马氏体、或者马氏体和贝氏体,或者由至少75%的等轴铁素体、5%至20%的马氏体和量小于或等于10%的贝氏体构成。
由此通过热成形获得根据本发明的具有优异的耐延迟断裂性的硬化部件。任选地,出于抗腐蚀目的,部件包括预涂覆有基于锌或基于铝的预涂层的钢板。优选地,部件包括这样的钢板:所述钢板预涂覆有包含铬并且不包含镍的氢屏障预涂层和包含热力学上稳定的铁氧化物、铬氧化物并且不包含镍氧化物的氧化物层,这样的氢屏障预涂层通过与钢板扩散而合金化。
更优选地,钢板的顶部直接被基于锌或基于铝的预涂层覆盖,该基于锌或基于铝的预涂层的顶部直接被包含铬并且不包含镍的氢屏障预涂层覆盖。氢屏障预涂层包括包含热力学上稳定的铁氧化物、铬氧化物并且不包含镍氧化物的氧化物层。氢屏障预涂层通过与基于锌或基于铝的预涂层扩散而合金化,基于锌或基于铝的预涂层还与钢板合金化。不希望受任何理论束缚,似乎来自钢的铁在热处理期间扩散至氢屏障预涂层的表面。在步骤C)的气氛的情况下,认为铁和铬缓慢地氧化形成热力学上稳定的氧化物,从而防止氢吸附至钢板中。
优选地,热力学上稳定的铬氧化物和铁氧化物可以包括Cr2O3、FeO、Fe2O3和/或Fe3O4或其混合物。
如果存在基于锌的预涂层,则氧化物还可以包括ZnO。如果存在基于铝的预涂层,则氧化物还可以包括Al2O3
对于机动车应用,在磷酸盐处理步骤之后,将部件浸入电涂覆浴中。通常,磷酸盐层的厚度为1μm至2μm,以及电涂覆层的厚度为15μm至25μm,优选小于或等于20μm。电泳层确保另外的抗腐蚀保护。在电涂覆步骤之后,可以沉积其他涂料层,例如,涂料的底漆涂层、底涂层和顶涂层。
在对部件施加电涂覆之前,将部件预先脱脂并进行磷酸盐处理以确保电泳的附着性。
现在将以仅用于信息性而进行的试验对本发明进行说明。所述试验不是限制性的。
实施例
对于所有样品,所使用的钢板为22MnB5。钢的组成如下:C=0.2252%;Mn=1.1735%;P=0.0126%,S=0.0009%;N=0.0037%;Si=0.2534%;Cu=0.0187%;Ni=0.0197%;Cr=0.180%;Sn=0.004%;Al=0.0371%;Nb=0.008%;Ti=0.0382%;B=0.0028%;Mo=0.0017%;As=0.0023%以及V=0.0284%。
一些钢板预涂覆有下文中称为
Figure BDA0003601386240000071
的为抗腐蚀预涂层的第一预涂层。该预涂层包含9重量%的硅、3重量%的铁,余量为铝。其通过热浸镀锌来沉积。
一些钢板涂覆有通过磁控溅射沉积的第二预涂层。
实施例1:氢测试:
该测试用于确定在模压淬火方法的奥氏体化热处理期间所吸附的氢的量。
试验品为预涂覆有为
Figure BDA0003601386240000072
(25μm)的第一预涂层和包含80%的Ni和20%的Cr或者由Cr组成的第二预涂层的钢板。
在预涂层的沉积之后,对经涂覆的试验品进行切割以获得坯件。然后在5分钟至10分钟不等的保留时间期间,在900℃的温度下将坯件加热。热处理期间的气氛为露点为-15℃至+15℃的空气或氮气。将坯件转移至压制工具中并且热冲压以获得具有Ω形状的部件。然后,通过将试验品浸入温水中将部件冷却以通过马氏体转变获得硬化。
最后,通过使用热解吸分析仪或TDA的热解吸来测量在热处理期间被试验品吸附的氢量。为此,将各个试验品放置在石英室中并在氮气流下在红外炉中缓慢加热。通过检漏器拾取所释放的混合物氢气/氮气并通过质谱仪测量氢气浓度。
结果示于下表1中:
Figure BDA0003601386240000081
*:根据本发明的实施例。
与比较例相比,根据本发明的试验品4释放非常低量的氢气。
在热处理和热成形之后,已经分析了试验品4的表面。其在表面上包含以下氧化物:Cr2O3、Fe2O3、Fe3O4和Al2O3
从钢板至外表面,试验品4的部件包括以下层:
·相互扩散层,所述相互扩散层包含来自钢板的铁,铝、硅和其他元素,厚度为10μm至15μm,
·合金化层,所述合金化层包含比下面的层更少的量的铝、硅和来自钢板的铁、以及其他元素,厚度为20μm至35μm,
·薄层,所述薄层包含比下面的层更少的铁和更多的氧化物,厚度为100nm至300nm,
·更薄的层,所述更薄的层包含与下面的层相比最高量的氧化物尤其是Cr氧化物和Al氧化物并且直接位于所述表面的下面,厚度为50nm至150nm。

Claims (15)

1.一种模压淬火方法,包括以下步骤:
A.提供用于热处理的钢板,所述钢板任选地预涂覆有基于锌或基于铝的预涂层,
B.以10nm至550nm的厚度沉积包含铬并且不包含镍的氢屏障预涂层,
C.对预涂覆的钢板进行切割以获得坯件,
D.在具有氧化力等于或高于包含1体积%氧气的气氛的氧化力并且等于或小于包含50体积%氧气的气氛的氧化力的气氛中,在1分钟至12分钟的保留时间期间,在800℃至970℃的炉温度下对所述坯件进行热处理,这样的气氛的露点为-30℃至+30℃,
E.将所述坯件转移到压制工具中,
F.在600℃至830℃的温度下将所述坯件热成形以获得部件,
G.将以步骤E)获得的所述部件冷却以在钢中获得以下显微组织:所述显微组织为马氏体或马氏体-贝氏体,或者由以体积分数计至少75%的等轴铁素体、5体积%至20体积%的马氏体和量小于或等于10体积%的贝氏体构成。
2.根据权利要求1所述的模压淬火方法,其中在步骤B)中,所述氢屏障预涂层不包含选自Al、Fe、Si、Zn和N中的元素中的至少一者。
3.根据权利要求1或2中任一项所述的模压淬火方法,其中在步骤A)中,所述氢屏障预涂层由铬组成。
4.根据权利要求1至3中任一项所述的模压淬火方法,其中在步骤C与步骤G之间没有另外的预涂层沉积在所述氢屏障预涂层的顶部。
5.根据权利要求1至4中任一项所述的模压淬火方法,其中在步骤A)中,所述基于锌或基于铝的预涂层基于铝并且包含小于15%的Si、小于5.0%的Fe、任选地0.1%至8.0%的Mg和任选地0.1%至30.0%的Zn,剩余部分为Al。
6.根据权利要求1至4中任一项所述的模压淬火方法,其中在步骤A)中,所述基于锌或基于铝的预涂层基于锌并且包含小于6.0%的Al、小于6.0%的Mg,剩余部分为Zn。
7.根据权利要求1至6中任一项所述的模压淬火方法,其中步骤A)的所述氢屏障预涂层通过物理气相沉积、通过电镀锌或辊涂来沉积。
8.根据权利要求7所述的模压淬火方法,其中在步骤C)中,所述气氛具有这样的氧化力:所述氧化力等于或高于包含10体积%氧气的气氛的氧化力并且等于或小于包含30体积%氧气的气氛的氧化力。
9.根据权利要求8所述的模压淬火方法,其中在步骤C)中,所述气氛为空气。
10.根据权利要求9所述的模压淬火方法,其中在步骤C)中,所述热处理在840℃至950℃的温度下进行以在所述钢中获得完全奥氏体显微组织。
11.一种能够从根据权利要求1至10中任一项所述的方法中获得的部件,所述部件包括钢板;氢屏障预涂层,所述氢屏障预涂层包含铬并且不包含镍并且通过来自所述钢板的铁的扩散而合金化,并且顶部被包含来自所述钢板的铁氧化物、铬氧化物并且不包含来自所述氢屏障预涂层的镍氧化物的氧化物层覆盖。
12.一种能够从根据权利要求1至10中任一项所述的方法中获得的部件,所述部件包括钢板;基于锌的预涂层;氢屏障预涂层,所述氢屏障预涂层包含铬并且不包含镍并且通过来自所述钢板的铁的扩散和来自所述基于锌的预涂层的锌和其他元素的扩散而合金化,并且顶部被包含来自所述钢板的铁氧化物、来自所述基于锌的预涂层的锌氧化物、来自所述氢屏障预涂层的铬氧化物并且不包含镍氧化物的氧化物层覆盖。
13.一种能够从根据权利要求1至10中任一项所述的方法中获得的部件,所述部件包括钢板;基于铝的预涂层;氢屏障预涂层,所述氢屏障预涂层包含铬并且不包含镍并且通过来自所述钢板的铁的扩散和来自所述基于铝的预涂层的铝和其他元素的扩散而合金化,并且顶部被包含来自所述钢板的铁氧化物、来自所述基于铝的预涂层的铝氧化物例如Al2O3、来自所述氢屏障预涂层的铬氧化物并且不包含镍氧化物的氧化物层覆盖。
14.根据权利要求11至13中任一项所述的部件,其中热力学上稳定的铬氧化物和铁氧化物能分别包括Cr2O3、FeO、Fe2O3和/或Fe3O4或其混合物。
15.根据权利要求11至14中任一项所述的部件或者能够从根据权利要求1至10中任一项所述的方法中获得的部件用于制造机动车辆的用途。
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