CN110914473B - 经涂覆的金属基材及制造方法 - Google Patents

经涂覆的金属基材及制造方法 Download PDF

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CN110914473B
CN110914473B CN201880031008.0A CN201880031008A CN110914473B CN 110914473 B CN110914473 B CN 110914473B CN 201880031008 A CN201880031008 A CN 201880031008A CN 110914473 B CN110914473 B CN 110914473B
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metal substrate
coating
coated metal
substrate
intermediate coating
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CN110914473A (zh
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亚采克·戈尼亚科夫斯基
蒂·哈·灵·莱
克洛迪娜·诺格拉
雅克·朱皮耶
雷米·拉扎里
让-米歇尔·马泰涅
阿列克谢·科利佐夫
雷米·卡瓦洛蒂
丹尼尔·沙莱
卢切·加乌亚
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Centre National de la Recherche Scientifique CNRS
Sorbonne Universite
ArcelorMittal SA
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Centre National de la Recherche Scientifique CNRS
Sorbonne Universite
ArcelorMittal SA
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    • C—CHEMISTRY; METALLURGY
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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Abstract

经涂覆的金属基材及制备方法。本发明涉及经涂覆的金属基材，其包括至少：一个氧化物层，这样的层顶部上直接为中间涂层，所述中间涂层包含Fe、Ni、Cr和Ti，其中Ti的量大于或等于5重量％，并且其中满足以下方程式：8重量％<Cr+Ti<40重量％，余量为Fe和Ni，这样的中间涂层顶部上直接为作为抗腐蚀金属涂层的涂层。

Description

经涂覆的金属基材及制造方法
本发明涉及经涂覆的金属基材及其制造方法。经涂覆的金属基材特别适合于机动车辆的制造。
钢板通常覆盖有金属涂层，所述金属涂层的组成根据钢板的最终用途而不同。例如，该涂层可以为锌、铝、镁或其合金，可以包括一个或更多个层，并且可以使用本领域技术人员已知的不同涂覆技术(例如，如真空沉积法、热浸涂或电沉积)来施加。
通常，通过热浸涂来沉积金属涂层，由此该工艺通常包括以下步骤：
–在惰性或还原性气氛下在钢板通过炉时对其进行退火以限制板表面的氧化；
–在板通过液态的金属浴或金属合金浴时对其进行热浸涂，使得当板离开浴时，其涂覆有金属/金属合金；
–在板离开液体浴之后，通过在表面上喷射气体来擦拭金属/金属合金层以保证该层的厚度均匀且规则。
在退火步骤期间，在钢板进入金属浴(在本文的以下部分中，术语“金属浴”和“金属层”还用于指任何金属合金浴和相应的金属合金层)之前，通常将板在直焰式或辐射管式退火炉中加热。然而，尽管采取了大量措施(例如控制惰性气氛)，但是使用这些炉来加热钢板仍可能导致在表面上形成金属氧化物，所述金属氧化物妨碍液体金属在钢板表面上的适当润湿性并且在板表面上引起未经涂覆的区域的出现。
当钢的组成包括显著量的易被氧化的元素(例如Si、Mn、Al、Cr、B、P等)时尤其会遇到这种问题。例如，包含0.2重量％Mn、0.02重量％Si和5ppm B的IF(Interstitial-Free，无间隙)钢由于存在B而已遭受这些润湿性问题，B快速扩散至板的表面并使Mn、B和Si的混合氧化物以连续膜的形式沉淀，从而导致差的润湿。
更一般地，在所有高强度钢中也遇到由液体金属引起的差润湿的风险，因为它们包含比铁更易于氧化的这些元素中的至少一者，所述高强度钢为例如双相钢(Dual Phasesteel)、TRIP(相变诱发塑性(Transformation Induced Plasticity))钢、TWIP(孪生诱发塑性(TWinning-Induced Plasticity))钢、电工钢等。
对于双相钢，Mn的量通常小于3重量％，并且Cr、Si或Al的添加量通常小于1重量％。对于TRIP钢，与最大2重量％的Si或Al联合，Mn的量通常小于2重量％。对于TWIP钢，与Al或Si(最大3重量％)组合，Mn的量可以高达25重量％。
还可以通过电沉积来施加金属涂层。通常，在电沉积工艺之前，钢板必须经历酸洗步骤以除去表面上存在的金属氧化物。事实上，为了使电解工艺有效，介质必须一定为导体，如果待涂覆钢板的表面上存在金属氧化物，则不是这种情况。此外，金属氧化物的存在可能影响涂覆沉积并因此导致涂层的粘附和品质问题(显微组织、密度等)。
还可以通过真空沉积来施加金属涂层。除了其他方面之外，根据用于形成气相的方式而进行不同类型的真空沉积的区分。如果气相由化学反应或分子分解产生，则该工艺称为CVD或化学气相沉积。另一方面，如果该气相通过纯物理现象(例如热蒸镀或离子溅射)产生，则该工艺为物理气相沉积或PVD。PVD沉积工艺包括溅射、离子注入和真空蒸镀。
然而，通常，无论所使用的真空沉积技术如何，都需要准备表面使得待涂覆的钢板的表面没有金属氧化物，以保证金属涂层的适当粘附并由此防止涂层层离的问题。
无论所使用的涂覆方法如何，在涂覆之前钢带的表面状态都是最终涂层的品质的重要因素。待涂覆的钢板的表面上存在金属氧化物妨碍待施加的涂层的适当粘附，并且可能产生其中最终产品上没有涂层的区域或者与涂层层离有关的问题。这些金属氧化物可能在钢板表面上以连续膜的形式或者以不连续点的形式存在。金属氧化物还可能在工艺的不同步骤期间形成，并且其组成根据制成所讨论的板的钢的级别而不同。这种类型的氧化物包括，例如铁氧化物FeOx、Fe3O4、Fe2O3和铁氢氧化物；铝氧化物Al2O3和铝氢氧化物；硅氧化物(SiOx)；以及混合氧化物MnSixOy、AlSixOy或MnBxOy。
除去这些金属氧化物需要进行另外的过程步骤，即酸洗。在本说明书的剩余部分中，酸洗意指导致除去由下面的金属层的氧化而形成的金属氧化物使得该金属层显现在表面上的任何方法，与例如擦亮法相比，虽然擦亮法是除去金属氧化物的工艺，但是其仅旨在除去金属氧化物的表面层而不使下面的金属层暴露。
这种金属氧化物的除去可以例如通过经由磁控管粉碎(也称为蚀刻)的真空酸洗来实现。还可以通过使带材经过一个或更多个连续的强酸(例如盐酸或硫酸)浴来对其进行酸洗。最后，可以通过机械作用例如通过使用其中金属氧化物被除去的喷丸工艺来除去所有或部分金属氧化物层。然而，这些方法总是难以控制并且难以实现工业规模。
一种已知的表面处理允许避免除去存在于金属基材上的氧化物层。实际上，专利申请WO2015/150850公开了一种基材，其包括复数个层，其中至少一者包含金属氧化物，并且顶部上直接为金属涂层，所述金属涂层包含至少8重量％的镍和至少10重量％的铬，其余为铁、由制造过程产生的另外的元素和杂质，该金属涂层本身顶部上直接为抗腐蚀涂层。例如，该金属涂层为包含16重量％至18重量％的Cr和10重量％至14重量％的Ni、余量为Fe的316不锈钢。该金属涂层改善了后续涂层在基材上的粘附，并且不需要用于消除存在于表面上的氧化物的步骤。
然而，这种包括在金属基材上添加包含镍、铬和铁的金属涂层的表面处理是唯一已知的表面处理，并因此是在市场上可获得的不需要用于消除存在于基材表面上的氧化物的步骤的表面处理。
因此，本发明的目的是提供另一种表面处理方法，所述方法使得可以改善后续涂层在基材上的粘附，并且不需要用于消除存在于表面上的氧化物的步骤等。
该目的通过提供根据权利要求1所述的经涂覆的金属基材来实现。所述方法还可以包括根据权利要求2至19所述的特征。
该目的还通过提供根据权利要求20所述的用于制造经涂覆的金属基材的方法来实现。所述方法还可以包括根据权利要求21至24所述的特征。
最后，通过提供根据权利要求25所述的经涂覆的金属基材的用途来实现目的。
根据本发明的以下详细描述，本发明的其他特征和优点将变得明显。
为了说明本发明，将特别地参照以下附图对非限制性实施例的多个实施方案和试验进行描述：
图1是本发明的第一实施方案中的基材的示意图。
图2是本发明的第二实施方案中的基材的示意图。
图3是本发明的第三实施方案中的基材的示意图。
在所有的图中，所表示的层的厚度仅用于说明的目的，并且不可以被视为是不同层按比例的表示。
将定义以下术语：
-所有的百分比(％)均以重量定义。
名称“钢”或“钢板”包括所有已知级别的钢，并且可以为例如以下级别中的一者：HSS(高强度钢，通常为450MPa至900MPa)或AHSS(先进高强度钢，通常大于900MPa)、包含大量可氧化元素的钢：
-无间隙元素的钢(IF-无间隙)，其可以包含高达0.1重量％的Ti；
-双相钢，例如DP 500钢直至DP 1200钢，其可以包含与高达1重量％的Si、Cr和/或Al联合的高达3重量％的Mn；
-TRIP(相变诱发塑性)钢，例如TRIP 780，其包含例如约1.6重量％的Mn和1.5重量％的Si；
-含磷的TRIP或双相钢；
-TWIP(孪生诱发塑性)钢，具有高含量的Mn(通常为17重量％至25重量％)的钢；
-低密度钢，例如Fe-Al钢，其可以包含例如高达10重量％的Al；
-不锈钢，其具有与其他合金元素(Si、Mn、Al等)联合的高含量的铬(通常为13重量％至35重量％)。
为了这个目的，本发明提供了经涂覆的金属基材，其包含至少：一个氧化物层，这样的层顶部上直接为中间涂层，所述中间涂层包含Fe、Ni、Cr和Ti，其中Ti的量大于或等于5重量％，并且其中满足以下方程式：8重量％<Cr+Ti<40重量％，余量为Fe和Ni，这样的中间涂层顶部上直接为作为抗腐蚀金属涂层的涂层。
不希望受任何理论的束缚，似乎根据本发明的包含Fe、Ni、Cr和Ti的中间涂层改善了后续涂层的粘附性，并且不需要除去存在于金属基材上的天然氧化物层。实际上，认为存在于中间层中的铬氧化物或钛氧化物导致存在于金属基材上的天然氧化物与抗腐蚀金属涂层之间的界面处的强连接。
认为当Ti量以重量计低于5重量％时，存在包含Fe、Ni、Cr和Ti的中间涂层无法很好地粘附在氧化物层上的风险。此外，当Cr和Ti的量低于8重量％时，存在氧化物层没有在钢板表面上充分覆盖，从而导致抗腐蚀金属涂层的不良粘附性的风险。最后，当Cr+Ti的量高于40重量％时，存在粘附性降低的风险，原因是在中间层中，在被氧化的钛与Cr-Ti金属层之间出现弱连接，从而导致抗腐蚀金属涂层在金属基材表面上的差粘附。
图1示出了根据本发明的第一实施方案。在该实例中，金属基材为在其至少一个表面上包括氧化物层2的钢板1。该氧化物层2在钢表面1上可以是连续的或不连续的，并且可以包含来自包括以下的组的金属氧化物：铁氧化物、铬氧化物、锰氧化物、铝氧化物、硅氧化物、硼氧化物或者包含钢合金元素的一种或更多种混合氧化物例如混合Mn-Si或Al-Si或Mn-B氧化物。该第一金属氧化物层2的厚度通常可以例如在3nm至约60nm变化，并且优选在3nm至约20nm变化。
因此，氧化物层2未被除去，并且由中间涂层3覆盖，所述中间涂层3包含Fe、Ni、Cr和Ti，其中Ti的量大于或等于5重量％，并且其中满足以下方程式：8重量％<Cr+Ti<40重量％，余量为Fe和Ni。例如，该涂层3可以包含27重量％的Ni、10重量％的Cr、10重量％的Ti，余量为Fe。Fe-Ni-Cr-Ti金属涂层3由抗腐蚀金属涂层4覆盖。
根据本发明，优选地，中间涂层包含15重量％至42重量％，更优选22重量％至40重量％，并且有利地25重量％至30重量％的Ni。
优选地，中间涂层包含10重量％至60重量％，更优选30重量％至60重量％的铁。
有利地，中间涂层包含5重量％至30重量％，优选5重量％至20重量％的Ti。
优选地，中间涂层包含5重量％至30重量％，更优选5重量％至20重量％的Cr。
在一个优选实施方案中，中间涂层的厚度为1nm至100nm，优选1nm至50nm，并且更优选1nm至20nm。
在另一个优选实施方案中，金属基材直接涂覆有抗腐蚀层，这样的抗腐蚀层顶部上直接为氧化物层。
优选地，抗腐蚀涂层包含选自以下的金属：锌、铝、铜、镁、硅、铁、钛、镍、铬、锰及其合金。
更优选地，抗腐蚀涂层为基于铝的涂层，所述基于铝的涂层包含小于15％的Si、小于5.0％的Fe、任选的0.1％至8.0％的Mg和任选的0.1％至30.0％的Zn，剩余部分为Al。
在另一个优选实施方案中，抗腐蚀涂层为基于锌的涂层，所述基于锌的涂层包含0.01％至8.0％的Al、任选的0.2％至8.0％的Mg，剩余部分为Zn。
金属基材可以选自：铝基材、钢基材、不锈钢基材、铜基材、铁基材、铜合金基材、钛基材、钴基材或镍基材。优选地，金属基材为钢板。
图2示出了本发明的第二实施方案。在该实施方案中，基材为钢板21。该钢板21涂覆有抗腐蚀涂层25，例如，如包含9重量％至12重量％的Si的基于铝的涂层。该基于铝的涂层25的厚度可以为例如10μm至30μm。该基于铝的涂层25顶部上为金属氧化物层22。该层22在所讨论的基于铝的涂层25的表面上可以是连续的或不连续的，并且可以包含铝氧化物和/或混合的铝氧化物，例如铝硅氧化物。该金属氧化物层22的厚度通常可以在3纳米至约60纳米变化，优选在3nm至约20nm变化。
因此，该氧化物层22未被除去并且被中间涂层23覆盖，所述中间涂层23包含Fe、Ni、Cr和Ti，其中Ti的量大于或等于5重量％，并且其中满足以下方程式：8重量％<Cr+Ti<40重量％，余量为Fe和Ni。例如，该涂层23包含29重量％的Ni、12重量％的Cr、22重量％的Ti，余量为Fe。
该第二实施方案中的该金属涂层23顶部上为抗腐蚀金属涂层24，例如为基于锌的涂层。在这种情况下，优选地，基于锌的涂层为包含0.01％至0.2％的Al、1.0％至5％的Mg、余量为Zn的Zn-Mg合金抗腐蚀涂层。
图3示出了本发明的第三实施方案。在该第三实施方案中，基材为在其至少一个表面上包括第一氧化物层32的钢板31。
氧化物层32未被除去并且被中间涂层33覆盖，所述中间涂层33包含Fe、Ni、Cr和Ti，其中Ti的量大于或等于5重量％并且其中满足以下方程式：8重量％<Cr+Ti<40重量％，余量为Fe和Ni以及由制造过程产生的杂质。
在该实施方案中，Fe-Ni-Cr-Ti金属涂层33被第一抗腐蚀金属涂层34覆盖。该第一抗腐蚀金属涂层34可以包含例如纯锌，或锌合金例如Zn-Al、Zn-Al-Mg、Zn-Mg或Zn-Ni。其还可以包含铝、铜、镁、钛、镍、铬、纯锰(包含由制造过程中产生的潜在杂质)或其合金，例如，如Al-Si或Mg-Al。
在该第三实施方案中，第一抗腐蚀金属涂层34顶部上为第二金属氧化物层36。该层36在抗腐蚀金属涂层34的表面上可以是连续的或不连续的，并且可以包含氧化物，其组成取决于抗腐蚀金属涂层34的构成材料。例如，这些氧化物可以为锌氧化物、铝氧化物或混合的Al-Si、Zn-Mg或Zn-Al氧化物。该金属氧化物层36的厚度通常可以在例如3nm至约60nm变化，并且优选在3nm至约20nm变化。
该第二氧化物层36未被消除并且被包含Fe-Cr-Ni-Ti的中间涂层覆盖。该金属涂层37的厚度可以为例如大于或等于2nm。
在该第三实施方案中，该金属涂层37顶部上为第二抗腐蚀金属涂层38。例如，可以给出这样的考虑：钢层31、第一铁氧化物层32、包含Fe-Cr-Ni-Ti的第一中间涂层33、由Al-Si合金组成的第一抗腐蚀金属涂层34、由混合的Al-Si氧化物组成的第二氧化物层36、包含Fe-Cr-Ni-Ti的第二中间涂层37和由Zn-Al-Mg合金组成的第二抗腐蚀金属涂层38。
本发明还涉及用于制造根据本发明的所述经涂覆的金属基材的方法，其包括以下步骤：
A.提供包括至少一个氧化物层的金属基材，
B.通过真空沉积或电沉积工艺沉积中间涂层，以及
C.沉积作为抗腐蚀金属涂层的涂层。
优选地，在步骤B)中，中间涂层的沉积通过磁控管阴极粉碎工艺或喷射气相沉积工艺进行。
优选地，在步骤C)中，涂层的沉积通过热浸涂、通过电沉积工艺或通过真空沉积来进行。当通过真空沉积来沉积涂层时，其可以通过磁控管阴极粉碎工艺或喷射气相沉积工艺来沉积。
优选地，该方法在沉积中间涂层之前不包括用于除去金属基材上的氧化物层的酸洗。
最后，本发明涉及经涂覆的金属基材用于制造机动车辆的部件的用途。
现在将基于仅为了说明的目的而进行并且不旨在限制的测试来说明本发明。
实施例1：粘附性
进行T-弯曲测试。该测试的目的是通过以180°的角度弯曲经涂覆的板来确定涂层的粘附。所施加的弯曲半径等于所使用的基材厚度的两倍(这相当于“2T”弯曲)。涂层的粘附通过施加粘合带来验证。如果在除去粘合带之后涂层仍保留在测试板上并且未出现在粘合带上，则将测试结果判断为肯定的。
在以下所述的测试中，用于进行该测试的粘合带为商业粘合剂，TESA4104。
用于样品的钢的组成为0.15％C、1.9％Mn、0.2％Si、0.2％Cr和0.013％Ti。百分比为重量百分比，其中剩余部分为铁和由制造产生的潜在杂质。
实验1至11为比较例。
实验1至9根据WO2015/150850准备。
对于实验10，包含Fe、Ni、Cr和Ti的中间涂层的组成如下：3重量％的Cr、15重量％的Ni、3重量％的Ti，余量为Fe。
对于实验11，包含Fe、Ni、Cr和Ti的中间涂层的组成为：3重量％的Cr、40重量％的Ni、47重量％的Ti，余量为Fe。
对于实验12，包含Fe、Ni、Cr和Ti的中间涂层的组成如下：3重量％的Cr、15重量％的Ni、6重量％的Ti，余量为Fe。
对于实验13，包含Fe、Ni、Cr和Ti的中间涂层的组成如下：3重量％的Cr、40重量％的Ni、10重量％的Ti，余量为Fe。
使实验10至13经受以下所述的步骤：
-将带材插入压力为P<10-3毫巴的真空室中。
-真空蒸镀沉积10nm的Fe-Ni-Cr-Ti涂层。
-真空蒸镀沉积5μm的锌层。
各个实验的特征呈现于下表中：
试样编号 擦亮 蚀刻 涂层
1 H2SO4 否 不锈钢316
2 H2SO4 是 否
3 H2SO4 否 否
4 H2SO4 否 Ti
5 HCOOH 否 不锈钢316
6 HCOOH 是 否
7 HCOOH 否 否
8 HCOOH 否 Ti
9 无 否 不锈钢316
10 无 无 Fe-3Cr-15Ni-3Ti
11 无 无 Fe-3Cr-40Ni-47Ti
12* 无 无 Fe-3Cr-15Ni-6Ti
13* 无 无 Fe-3Cr-40Ni-10Ti
*根据本发明
然后使所有这些试样经受上述T-弯曲。结果呈现于下表中。
试样编号 T-弯曲
1 肯定
2 肯定
3 否定
4 肯定
5 肯定
6 肯定
7 否定
8 肯定
9 肯定
10 否定
11 否定
12* 肯定
13* 肯定
根据本发明的实验12和13显示出如实验1、5和9的锌的良好粘附。

Claims (25)

1.一种经涂覆的金属基材，包括至少：一个氧化物层，这样的层顶部上直接为中间涂层，所述中间涂层包含Fe、Ni、Cr和Ti，其中Ti的量大于或等于5重量％，并且其中满足以下方程式：8重量％<Cr+Ti<40重量％，余量为Fe和Ni，这样的中间涂层顶部上直接为作为抗腐蚀金属涂层的涂层。
2.根据权利要求1所述的经涂覆的金属基材，其中所述中间涂层包含15重量％至42重量％的Ni。
3.根据权利要求2所述的经涂覆的金属基材，其中所述中间涂层包含22重量％至40重量％的Ni。
4.根据权利要求1至3中任一项所述的经涂覆的金属基材，其中所述中间涂层包含25重量％至30重量％的Ni。
5.根据权利要求1至3中任一项所述的经涂覆的金属基材，其中所述中间涂层包含10重量％至60重量％的铁。
6.根据权利要求1至3中任一项所述的经涂覆的金属基材，其中所述中间涂层包含30重量％至60重量％的铁。
7.根据权利要求1至3中任一项所述的经涂覆的金属基材，其中所述中间涂层包含5重量％至30重量％的Ti。
8.根据权利要求7所述的经涂覆的金属基材，其中所述中间涂层包含5重量％至20重量％的Ti。
9.根据权利要求1至3中任一项所述的经涂覆的金属基材，其中所述中间涂层包含5重量％至30重量％的Cr。
10.根据权利要求9所述的经涂覆的金属基材，其中所述中间涂层包含5重量％至20重量％的Cr。
11.根据权利要求1至3中任一项所述的经涂覆的金属基材，所述中间涂层的厚度为1nm至100nm。
12.根据权利要求11所述的经涂覆的金属基材，所述中间涂层的厚度为1nm至50nm。
13.根据权利要求12所述的经涂覆的金属基材，所述中间涂层的厚度为1nm至20nm。
14.根据权利要求1至3中任一项所述的经涂覆的金属基材，其中所述金属基材直接涂覆有抗腐蚀层，这样的抗腐蚀层顶部上直接为所述氧化物层。
15.根据权利要求1至3中任一项所述的经涂覆的金属基材，其中所述抗腐蚀金属涂层包含选自以下的金属：锌、铝、铜、硅、铁、镁、钛、镍、铬、锰及其合金。
16.根据权利要求15所述的经涂覆的金属基材，其中所述抗腐蚀金属涂层为基于铝的涂层，所述基于铝的涂层包含小于15％的Si、小于5.0％的Fe、任选的0.1％至8.0％的Mg和任选的0.1％至30.0％的Zn，剩余部分为Al。
17.根据权利要求15所述的经涂覆的金属基材，其中所述抗腐蚀金属涂层为基于锌的涂层，所述基于锌的涂层包含0.01％至8.0％的Al、任选的0.2％至8.0％的Mg，剩余部分为Zn。
18.根据权利要求1至3中任一项所述的经涂覆的金属基材，其中所述金属基材选自：铝基材、钢基材、不锈钢基材、铜基材、铁基材、铜合金基材、钛基材、钴基材或镍基材。
19.根据权利要求18所述的经涂覆的金属基材，其中所述金属基材为钢板。
20.一种用于制造根据权利要求1至18中任一项所述的经涂覆的金属基材的方法，包括以下步骤：
A.提供包括至少一个氧化物层的金属基材，
B.通过真空沉积或电沉积工艺沉积根据权利要求1至13中任一项所述的中间涂层，
C.沉积作为根据权利要求1至17中任一项所述的抗腐蚀金属涂层的涂层。
21.根据权利要求20所述的用于制造经涂覆的金属基材的方法，其中在步骤B中，所述中间涂层的沉积通过磁控管阴极粉碎工艺或喷射气相沉积工艺进行。
22.根据权利要求20或21所述的用于制造经涂覆的金属基材的方法，其中在步骤C中，所述涂层的沉积通过热浸涂、通过电沉积工艺或通过真空沉积来进行。
23.根据权利要求20至21中任一项所述的用于制造经涂覆的金属基材的方法，其中在步骤C中，所述涂层的沉积通过磁控管阴极粉碎工艺或喷射气相沉积工艺来进行。
24.根据权利要求20至21中任一项所述的方法，其中所述方法在沉积所述中间涂层之前不包括用于除去所述金属基材上的所述氧化物层的酸洗。
25.根据权利要求1至19中任一项所述的经涂覆的金属基材或者能够由根据权利要求20至24中任一项所述的方法获得的经涂覆的金属基材用于制造机动车辆的部件的用途。
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