CN116324034A - 多层***、部件和用于生产这种多层***或部件的方法 - Google Patents

多层***、部件和用于生产这种多层***或部件的方法 Download PDF

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CN116324034A
CN116324034A CN202180068234.8A CN202180068234A CN116324034A CN 116324034 A CN116324034 A CN 116324034A CN 202180068234 A CN202180068234 A CN 202180068234A CN 116324034 A CN116324034 A CN 116324034A
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layer
metal
protection layer
multilayer system
wear protection
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理查德·恩里克·布鲁那拉
纳兹利姆·巴吉凡
埃德加·舒尔茨
马库斯·施梅尔瓦塞尔
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Schaeffler Technologies AG and Co KG
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  • Organic Chemistry (AREA)
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Abstract

本发明涉及一种多层***(1；1′；1″；1″′)，所述多层***包括至少一个防腐层(2)以及磨损保护层(3)，其中，所述防腐层(2)通过至少包含钛和镁作为金属的金属氮化物或金属碳氮化物形成，其中，所述金属氮化物或所述金属碳氮化物还包括至少一种稀土金属，并且所述磨损保护层(3)由至少一个类金刚石无金属碳层形成。本发明还涉及一种具有这种多层***(1；1′；1″；1″′)的部件(8)和用于生产所述多层***(1；1′；1″；1″′)或所述部件(8)的方法。

Description

多层***、部件和用于生产这种多层***或部件的方法
技术领域
本发明涉及包括至少一个防腐层和一个磨损保护层的多层***。本发明还涉及包括具有表面的金属基底和多层***的部件。此外，本发明涉及用于生产这种多层***或部件的方法。
背景技术
硬铬层目前在汽车工业中用作防腐层和磨损保护层以保护所使用的钢铁免受腐蚀和机械磨损。这种硬铬层通常利用包含铬(VI)的电解质浴生产，从环境的角度看，这些硬铬层现在被归类为有问题的，并且其使用越来越受到法律限制。因此，需要用可以以更环境友好的方式生产的涂层来替代硬铬层。
包括至少一个防腐层和一个磨损保护层的多层***已经在DE 10 2013209 030A1中已知。其中描述了用于金属部件的腐蚀保护，该腐蚀保护包括呈以化学、电的形式或借助于PCD/PACVD过程形成的层的形式的至少一个磨损保护层，该磨损保护层形成在金属部件上。磨损保护层上布置有借助于ALD(＝原子层沉积)过程形成的至少一个防腐层。然而，ALD过程不是非常适合在汽车工业中大量使用。
DE 10 2004 044 919A描述了基于难熔金属氮化镁来保护基底免受腐蚀、磨损和氧化的装饰涂层以及用于生产该装饰涂层的方法。
发明内容
本发明的目的是提供替代性多层***，该多层***提供更可靠的腐蚀和磨损保护并且可以大量制造。此外，本发明的目的是提供一种具有这种多层***的部件并且公开一种用于生产这种多层***或部件的方法。
该目的通过包括至少一个防腐层以及磨损保护层的多层***实现，其中，防腐层由至少包含钛和镁作为金属的金属氮化物或金属碳氮化物形成，其中，金属氮化物或金属碳氮化物还包括至少一种稀土金属，并且磨损保护层由至少一个类金刚石无金属碳层形成。
多层***确保对于金属基底的有效的腐蚀和磨损保护。由于磨损保护层直接或间接保护防腐层并承受机械载荷，所以多层***可以承受机械和腐蚀的双重侵蚀。磨损保护层优选地相对于在摩擦***中与其摩擦接触的接触配对件具有摩擦减小的性能。
多层***还可以以低生产成本大量生产，使得其适合于在汽车工业中使用。
防腐层特别地具有10at％至40at％的钛和/或15at％至50at％的镁。防腐层中的至少一种稀土金属的浓度优选地在0.1at％至15at％的范围内。
优选地，用于形成防腐层的金属氮化物或金属碳氮化物还形成为包括选自由铝、铬、锆、铪组成的组的至少一种金属。这些金属在防腐层中的浓度优选地在10at％至40at％的范围内。
特别优选地，金属氮化物或金属碳氮化物包括作为稀土金属的钆或铈或镧或所述元素中的两种或三种元素的混合物。
特别地，防腐层形成为包括TiMgGdN或TiMgGdCN或TiMgCeN或TiMgCeCN或TiMgLaN或TiMgLaCN。
基于金属氮化物比如TiMgREN(RE＝稀土)的防腐层及其腐蚀行为基于已经在下述公开中描述：“Corrosion and wear protection of mild steel substrates byinnovative PVD coatings(创新性PVD涂层对低碳钢基底的腐蚀和磨损保护)”，HolgerHoche、Casper Pusch、Matthias Oechsner，Surface&Coatings Technology 391(2020)，参见：https://doi.org/10.1016/j.surfcoat.2020.125659
已经证明有利的是，防腐层在其背离磨损保护层的侧面上邻近金属粘附促进层。特别地，金属粘附促进层由铬或钛或锆或镁或钆或所述金属中的两种或三种金属的混合物形成。粘附促进层用于改善多层***与金属基底的机械结合。
防腐层优选地在其面向磨损保护层的侧面上邻近中间层，该中间层由掺杂硅的金属氮化物或金属碳氮化物、特别是掺杂硅的金属碳氮化物形成。中间层用于改善防腐层与磨损保护层的机械结合。
呈至少一个类金刚石无金属碳层(＝DLC——类金刚石涂层)形式的磨损保护层优选地包括：a-C或a-C:H或ta-C或ta-C:Si或ta-C:H:O:Si或a-C:H:Si或a-C:H:O:Si或a-C:H:N类型的至少一个层或至少两个这种碳层的组合。相同组成的若干碳层可以形成为一个在另一个的顶部上，或者不同组成的碳层可以交替或一个跟随另一个以形成磨损保护层。
防腐层优选地具有在0.5μm至10μm的范围内、特别地在0.5μm至5μm的范围内的厚度。磨损保护层优选地具有在0.1μm至10μm的范围内、特别地在0.1μm至5μm的范围内的厚度。
该目的进一步由下述部件实现，该部件包括具有表面的金属基底和根据本发明的多层***，其中，该多层***在基底的表面上至少部分地形成为使得磨损保护层形成背离基底的覆盖层。从金属基底开始，顺序将因此是：
-可选的金属粘附促进层
-防腐层
-可选的中间层
-磨损保护层(＝覆盖层)
特别地，金属基底由钢形成。钢种100Cr6、42CrMo4或16MnCr5在该方面是特别优选的。
磨损保护层优选地相对于与其摩擦接触的接触配对件具有摩擦减小的性能。
位于金属基底、特别是钢上的以下多层***是特别优选的，并且在此仅通过示例的方式提及：
多层***1：
粘附促进层： 无
防腐层： TiMgGdN
中间层： 无
磨损保护层： a-C:H
多层***2：
粘附促进层： 无
防腐层： TiMgGdN
中间层： 无
磨损保护层： a-C:H:Si
多层***3：
粘附促进层： TiMg
防腐层： TiMgGdN
中间层： 无
磨损保护层： a-C:H
多层***4：
粘附促进层： 钛
防腐层： TiMgGdN
中间层： TiSiN
磨损保护层： a-C:H:Si
多层***5：
粘附促进层： 钛
防腐层： TiMgCrGdN
中间层： CrSiN
磨损保护层： a-C:H:Si
多层***6：
粘附促进层： 无
防腐层： TiMgGdCN
中间层： 无
磨损保护层： a-C:H:Si
多层***7：
粘附促进层： TiMg
防腐层： TiMgGdCN
中间层： 无
磨损保护层： a-C:H:Si
多层***8：
粘附促进层： TiMg
防腐层： TiMgLaCN或TiMgCeCN或TiMgLaN或TiMgCeN
中间层： 无
磨损保护层： a-C:H:Si
多层***9：
粘附促进层： TiMgGd
防腐层： TiMgGdN
中间层： 无
磨损保护层： 下述类型的至少一个层
a-C:H和/或a-C:H:Si
多层***10：
粘附促进层： TiMgGd
防腐层1： TiMgGdN
防腐层2： TiMgGdCN
中间层： 无
磨损保护层： 下述类型的至少一个层
a-C:H和/或a-C:H:Si
多层***11：
粘附促进层： TiMgGd
防腐层： TiMgGdCN
中间层： 无
磨损保护层： 下述类型的至少一个层
a-C:H和/或a-C:H:Si
多层***12：
粘附促进层： TiMgGd
防腐层： TiMgGdCN
中间层： 无
磨损保护层： 下述类型的至少一个层
ta-C:Si和/或ta-C:H:O:Si
多层***13：
粘附促进层： TiMgGd
防腐层1： TiMgGdN
防腐层2： TiMgGdCN
中间层： TiCN或TiSiCN
磨损保护层： 下述类型的至少一个层
ta-C:Si和/或ta-C:H:O:Si
根据本发明的部件特别地是滚动轴承部件或滑动轴承部件或用于与腐蚀性介质摩擦接触的部件。特别地，在操作中老化的水基润滑油、水介质和烃基润滑油在此被认为是腐蚀性介质。
该目的进一步通过一种用于生产根据本发明的多层***或根据本发明的部件的方法实现，其中，多层***借助于PVD过程和/或PACVD过程形成。这些方法在大规模生产中以及在汽车环境中使用时都具有成本效益。
附图说明
图1至图6旨在通过示例的方式解释本发明。在附图中：
图1示出了包括防腐层和磨损保护层的第一多层***；
图2示出了包括防腐层、中间层和磨损保护层的第二多层***；
图3示出了包括粘附促进层、防腐层、中间层和磨损保护层的第三多层***；
图4示出了包括粘附促进层、防腐层和磨损保护层的第四多层***；
图5示出了具有根据图3的多层***的部件；并且
图6示出了呈滚动轴承环形式的部件。
具体实施方式
图1以垂直于层平面的截面图示出了包括防腐层2和磨损保护层3的第一多层***1。防腐层2由至少包含钛和镁作为金属的金属氮化物或金属碳氮化物形成，其中，金属氮化物或金属碳氮化物还包括至少一种稀土金属。磨损保护层3由至少一个类金刚石无金属碳层(DLC)形成。
图2以垂直于层平面的截面图示出了包括防腐层2、中间层4和磨损保护层3的第二多层***1′。防腐层2由至少包含钛和镁作为金属的金属氮化物或金属碳氮化物形成，其中，金属氮化物或金属碳氮化物还包括至少一种稀土金属。磨损保护层3由至少一个类金刚石无金属碳层(DLC)形成。中间层4由掺杂硅的金属氮化物或金属碳氮化物、特别是掺杂硅的金属碳氮化物形成。
图3以垂直于层平面的截面图示出了包括粘附促进层5、防腐层2、中间层4和磨损保护层3的第三多层***1″。防腐层2由至少包含钛和镁作为金属的金属氮化物或金属碳氮化物形成，其中，金属氮化物或金属碳氮化物还包括至少一种稀土金属。磨损保护层3由至少一个类金刚石无金属碳层(DLC)形成。中间层4由掺杂硅的金属氮化物或金属碳氮化物、特别是掺杂硅的金属碳氮化物形成。金属粘附促进层5优选地由铬或钛或锆或镁或钆或所述金属中的两种或三种金属的混合物形成。特别地，粘附促进层5在此由TiMg形成。
图4以垂直于层平面的截面图示出了包括粘附促进层5、防腐层2和磨损保护层3的第四多层***1″′。防腐层2由至少包含钛和镁作为金属的金属氮化物或金属碳氮化物形成，其中，金属氮化物或金属碳氮化物还包括至少一种稀土金属。磨损保护层3由至少一个类金刚石无金属碳层(DLC)形成。金属粘附促进层5优选地由铬或钛或锆或镁或钆或所述金属中的两种或三种金属的混合物形成。
图5以垂直于多层***的层平面的截面图示出了包括具有表面6a的金属基底6和根据图3的第三多层***1″的部件8，其中，第三多层***1″在基底6的表面6a上部分地形成为使得磨损保护层3形成背离基底6的覆盖层7。
图6以三维图示出了呈滚动轴承环形式的部件8。部件8包括环形金属基底6，该环形金属基底用根据图1的多层***1覆盖在其筒形侧表面和其端面上。当然替代性地，在这方面也可以使用根据本发明的其他多层***。
此外，根据存在的腐蚀侵蚀和具体的磨损条件，多层***可以完全覆盖基底或仅在某些区域中在表面上覆盖基底。
附图标记列表
1、1′、1″、1″′ 多层***
2 防腐层
3 磨损保护层
4 中间层
5 粘附促进层
6 基底
6a 表面
7 覆盖层
8 部件。

Claims (12)

1.一种多层***(1；1′；1″；1″′)，包括至少一个防腐层(2)以及磨损保护层(3)，其中，所述防腐层(2)由至少包含钛和镁作为金属的金属氮化物或金属碳氮化物形成，其中，所述金属氮化物或所述金属碳氮化物还包括至少一种稀土金属，并且所述磨损保护层(3)由至少一个类金刚石无金属碳层形成。
2.根据权利要求1所述的多层***(1；1′；1″；1″′)，其中，所述金属氮化物或所述金属碳氮化物还形成为包括选自由铝、铬、锆、铪组成的组的至少一种金属。
3.根据权利要求1或2中的任一项所述的多层***(1；1′；1″；1″′)，其中，钆或铈或镧或所述元素中的两种或三种元素的混合物作为所述稀土金属存在。
4.根据权利要求1至3中的任一项所述的多层***(1；1′；1″；1″′)，其中，所述防腐层(2)形成为包括TiMgGdN或TiMgGdCN或TiMgCeN或TiMgCeCN或TiMgLaN或TiMgLaCN。
5.根据权利要求1至4中的任一项所述的多层***(1″；1″′)，其中，所述防腐层(2)在其背离所述磨损保护层(3)的侧面上邻近金属粘附促进层(5)。
6.根据权利要求5所述的多层***(1″；1″′)，其中，所述金属粘附促进层(5)由铬或钛或锆或镁或钆或所述金属中的两种或三种金属的混合物形成。
7.根据权利要求1至6中的任一项所述的多层***(1′；1″)，其中，所述防腐层(2)在其面向所述磨损保护层(3)的侧面上邻近中间层(4)，所述中间层由掺杂硅的金属氮化物或掺杂硅的金属碳氮化物形成。
8.根据权利要求1至7中的任一项所述的多层***(1；1′；1″；1″′)，其中，所述磨损保护层(3)包括a-C或a-C:H或ta-C或ta-C:Si或ta-C:H:O:Si或a-C:H:Si或a-C:H:O:Si或a-C:H:N类型的至少一个类金刚石无金属碳层或至少两个这种碳层的组合。
9.根据权利要求1至8中的任一项所述的多层***(1；1′；1″；1″′)，其中，所述防腐层(2)具有在0.5μm至10μm的范围内的厚度，并且/或者其中，所述磨损保护层(3)具有在0.1μm至10μm的范围内的厚度。
10.一种包括具有表面(6a)的金属基底(6)和根据权利要求1至9中的一项所述的多层***(1；1′；1″；1″′)的部件(8)，其中，所述多层***(1；1′；1″；1″′)在所述表面(6a)上至少部分地形成为使得所述磨损保护层(3)形成背离所述基底(6)的覆盖层(7)。
11.根据权利要求10所述的部件(8)，其中，所述部件是滚动轴承部件或滑动轴承部件或用于摩擦接触并进一步与腐蚀性介质接触的部件。
12.一种用于生产根据权利要求1至9中的任一项所述的多层***(1；1′；1″；1″′)或根据权利要求10或11中的任一项所述的部件(8)的方法，其中，所述多层***(1；1′；1″；1″′)借助于PVD过程和/或PACVD过程形成。
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JP5227782B2 (ja) 2008-12-26 2013-07-03 株式会社日立製作所 摺動部材
EP2628817B1 (en) 2012-02-15 2016-11-02 IHI Hauzer Techno Coating B.V. A coated article of martensitic steel and a method of forming a coated article of steel
DE102013209030A1 (de) 2013-05-15 2014-12-04 Schaeffler Technologies Gmbh & Co. Kg Korrosionsschutz für ein metallisches Bauteil und Verfahren zum Aufbringen des Korrosionsschutzes

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US20230407464A1 (en) 2023-12-21
DE102021123832A1 (de) 2022-04-07
EP4225972A1 (de) 2023-08-16

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