CN103032566A - 带有dlc 涂层的滑动件 - Google Patents

带有dlc 涂层的滑动件 Download PDF

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CN103032566A
CN103032566A CN2012102384543A CN201210238454A CN103032566A CN 103032566 A CN103032566 A CN 103032566A CN 2012102384543 A CN2012102384543 A CN 2012102384543A CN 201210238454 A CN201210238454 A CN 201210238454A CN 103032566 A CN103032566 A CN 103032566A
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dlc coating
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CN103032566B (zh
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马卡斯·肯尼迪
迈克尔·津纳鲍尔德
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Federal Mogul Burscheid GmbH
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F5/00—Piston rings, e.g. associated with piston crown
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    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/06—Compressing powdered coating material, e.g. by milling
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
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    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials
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Abstract

本发明涉及一种滑动件，特别是在基材上带有DLC涂层(12)的活塞环。根据本发明的滑动件的特征在于，在DLC涂层(12)的表面埋入了比DLC更软的材料(14)，所述滑动件将通过所述DLC涂层的表面与滑动配合件接触，并承靠其而滑动。

Description

带有DLC 涂层的滑动件
技术领域
本发明涉及滑动件，特别是在基材上带有DLC涂层的活塞环。 
背景技术
基本上，用于高压发动机的活塞环必须具有尽可能抗磨损的工作表面涂层，这就是经常使用基于硬质材料的PVD涂层和DLC涂层的原因。尽管PVD涂层相对抗磨损，但是其不能提供必要的低摩擦系数，而该低摩擦系数将导致在发动机中目前所需的最低摩擦损失，以及因此导致目前所需的最小燃料消耗。为此，通常优选使用DLC涂层。 
DLC涂层是“类金刚石碳”的缩写，意指无定形的类金刚石碳，其特征是特殊的性能，例如良好的抗磨蚀和粘着磨损性、防止表面层裂性、化学稳定性以及良好的导热性和机械性能（硬度和弹性模量）。特别是对于DLC层系统，通过大比率的sp3-杂化的碳原子获得了高硬度，所述碳原子的摩尔分数大于60%。这种物质也称为四面体接合的无定形碳(ta-C)。然而，此外也使用具有较低比率的sp3-杂化的碳原子且硬度低于ta-C层系统的DLC涂层，例如含氢和/或含金属的DLC系统。 
用于活塞环的具有高硬度的已知DLC涂层的缺点在于其弹性和塑性，并且因此与相对软的层相比其吸收剪切力的能力非常低。这意味着特别是在发动机的所谓磨合期内，滑动件或运转配合件的表面上的甚至非常小的不平整可导致涂层表面的层裂，并因此导致DLC涂层的破裂，甚至在低表面压力下也是如此。 
另一方面，软的DLC层具有过低的抗磨损性的缺点，使得在相对短的服务寿命后，DLC层容易磨损，并且不能再保持由此产生的低摩擦系数。 
发明内容
因此，本发明的目的是提供一种在基材上带有DLC涂层的滑动件，其具有低摩擦系数和高抗磨损性，并且因此也可容许运转配合件表面上的小的不平整而不会由此被显著地破坏。 
通过权利要求1的主题和根据权利要求6的方法实现了这种目的。在从属权利要求中公开了本发明的其他有利的实施方案。 
根据本发明，在基材上带有DLC涂层的滑动件、特别是活塞环的特征在于，在与滑动配合件形成滑动接触的DLC涂层的表面内埋入了比DLC更软的材料。这里，滑动配合件是指滑动件将承靠在其上而滑动的零件，例如在活塞环的情况中，其为配属于相关活塞的气缸壁。 
由于在DLC涂层的表面内埋入了较软的材料，因此尤其是可以没有损伤地完成可形成所谓的第三体的活塞环的重要的磨合过程。所谓的第三体理解为在活塞环承靠汽缸壁的磨合期间所形成的在DLC涂层内的层。特别是，可从WO 2010/009862A1中获得该第三体的性能。也可在除活塞环以外的滑动件中获得形成第三体的作用。 
在一个优选的实施方案中，较软的材料包括比DLC涂层更软的金属或金属氧化物，特别是铁或铁铬化合物或其氧化物。该实施方案是优选的，特别是如果气缸的工作表面即滑动件的滑动配合件具有相应的金属或金属氧化物的涂层。在基于铁的内燃机部分中，热涂覆的缸膛越来越多地用作活塞环的滑动配合件，其包括铁碳合金或铁铬合金等。也可通过具有适当调整的参数的热喷涂工艺来将金属氧化物结合到涂层中，以改进磨损行为。从这种优选实施方案的意义上来说，滑动件的形成意味着能够预期到在磨合过程期间发生的在滑动件的DLC涂层和滑动配合件之间的材料传递，并且因此可实施磨合过程而没有任何损坏或危险。 
有利地是，DLC涂层包括四面体接合的无定形碳(ta-C)，这是由于其特征为特别高的硬度和抗磨损性。 
在一个更优选的实施方案中，DLC涂层的表面包括以其面积计算 在50到60%、优选为20到40%的量的较软的材料。这种较软的材料、特别是金属或金属氧化物的面积含量产生了最佳可能的磨损值和摩擦值。在发动机外和发动机内进行的研究中发现，过高含量的较软材料会增加微焊接和由此带来的刮伤的风险，以及DLC涂层破裂的危险，这是由于较软材料的过快磨损，导致磨损增加以及甚至层的层裂。另一方面，DLC涂层的表面中过低含量的较软材料意味着提高DLC涂层的弹性和塑性的所需效果以及因此提高吸收剪切力的能力不足，这是由于不能再保证最适宜的确保涂层服务寿命的磨合。已经证明，上文提及的面积比率在这两个方面是特别有利的。 
埋有较软材料的DLC涂层的区域优选地在DLC涂层中从表面向下延伸1μm的深度，优选为向下延伸0.5μm的深度。较软的材料在DLC涂层中的埋入深度导致DLC涂覆的活塞环的最佳磨合行为，这是由于可以最大程度地保持DLC涂层的低磨损速率以及低摩擦系数。 
此外，表面优选地具有尽可能低的粗糙度，其可定义为小于2μm、优选小于1μm的平均粗糙深度RZ，和/或小于0.15μm、优选小于0.1μm的最小峰高RPK。这样，可将发生高表面压力点的数量保持为尽可能低，这会导致特别好的滑动性能。 
在一个优选的实施方案中，在包含较软材料的区域外的DLC涂层的硬度为10到70GPa，优选为15到50GPa。这种硬度提供了DLC涂层的低磨损，不会抵消改进弹性的作用，并且因此提高了对表面缺陷引起的剪切力的承受度。DLC涂层优选地包括氢，并且相应于类型a-C:H、a-C:H:Me、ta-C:H或a-C:H:X。这里，Me为优选地选自铬、钨和钛的金属，并且X为优选地选自硅、氧、氮和硼的非金属。 
作为替代，DLC涂层优选地相应于类型ta-C或a-C，并且不含有氢。 
滑动件的上述两种优选的变体提供了良好的硬度和耐磨损性，以及同时低的摩擦系数。 
在一个优选的实施方案中，滑动件包括处在基材和DLC涂层之间的优选为含金属的粘结层，其尤其是具有0.1μm到1.0μm的厚度。这种粘结层改进了DLC涂层与基材的粘结性，并且此外改进了滑动 件的耐用性。 
基材优选地由铸铁或钢形成，这是由于这些材料的强度和弹性特别适合用作活塞环或类似的滑动件。 
一种用于生产上述滑动件的根据本发明的方法的特征是，将比DLC更软的材料结合到将与滑动配合件接触的滑动件的DLC涂层的表面中。在已经将DLC涂层施加到基材上之后，将较软的材料结合到DLC涂层中，所述较软的材料优选为金属或金属氧化物，特别是铁或铁铬化合物或其氧化物。 
关于这一方面，优选地可通过涂覆或引入(working in)来将较软的材料结合到DLC涂层的表面中。合适的引入方法是使用钢刷的机械刷涂、钢带抛光处理或磨光。基材的涂覆例如可通过喷涂、溅射或PVD电弧过程来实现。 
本发明的一个独立方面是使用上述方法中之一以提供带有存在于内燃机汽缸壁中的材料的活塞环，当根据指示使用时，活塞环承靠所述汽缸壁而滑动。这种使用应当与仅涉及机加工DLC涂层的表面的方法相区别，这是由于根据本发明，结合到DLC层的表面中的材料与滑动件的其他滑动配合件、特别是活塞环相匹配。 
通过如上概述的发明，能够降低在活塞环和汽缸壁、或更一般地是滑动件和滑动配合件之间的摩擦，这特别是在带有降低的燃料消耗的内燃机中有重要意义，并且因此这是非常需要的。同时，根据本发明的滑动件可抗磨损，并且能容许滑动配合件表面上的不平整，使得例如在内燃机的磨合期间不存在活塞环表面层裂的危险。 
通过全部权利要求和下面的附图说明可得到本发明的其他优点、特征和有利的改进。 
附图说明
图1显示了优选的DLC涂覆表面的SEM照片。 
图2显示了结合有金属和金属氧化物的DLC涂层的元素深度曲线。 
图3显示了两种DLC涂层的磨损值的对比。 
图4显示了带有和不带有金属结合物的DLC涂覆的活塞环的力曲线图和摩擦曲线图。 
具体实施方式
图1显示了在12μm厚的初始层内的带有金属/金属氧化物结合物14的DLC涂层12的表面的SEM图像。在这种情况中，金属/金属氧化物结合物14的面积比率为39%。对多个具有金属/金属氧化物结合物的试样进行了测试，其中所述结合物的面积比率在27.8到39%之间变化。 
具有金属/金属氧化物结合物的试样在摩擦和磨损测试中表现出比未处理的DLC涂层明显更好的性能。这可从在下文中简单讨论的图3和4中看出。 
图2显示了DLC涂层的主要组成的深度曲线，在所述涂层的表面中结合入了铁和铁氧化物。沿Y轴描绘了三种主要组成碳(C)、氧(O)和铁(Fe)各自的比率，沿X轴描绘了DLC层的表面朝下1μm的层深度。 
从该图中可看出，铁和铁氧化物的可测量的埋入比率仅向下延伸0.5μm。在此深度以下，DLC涂层表现出没有相应的铁或铁氧化物的埋入。 
基于发动机测试发现，金属/金属氧化物埋入0.5μm的深度是特别有效的。另一方面，在超过240小时的具有0.7到1.0μm的环形磨损的发动机测试之后，检测不到DLC涂层内的金属比率。 
图3显示了不带有金属/金属氧化物结合物和带有这种结合物的DLC涂层的相对磨损。在图3的左侧显示了带有结合物的DLC涂层。该图显示了带有金属/金属氧化物结合物的DLC涂层的磨损仅为不带有结合物的DLC涂层的磨损的约20%。 
在所谓的振动摩擦磨损测试中检测了磨损，在所述测试中，滑动件通过恒定的载荷并以恒定的速率相对于经润滑的对应件而振动。 
图4最终显示了进一步的图，在其中相对于时间描绘了带有和不带有金属/金属氧化物结合物的DLC涂覆的活塞环的力的行为和摩擦 行为。 
这里，连续曲线显示了不带有金属/金属氧化物结合物的DLC涂层的摩擦行为，虚线曲线显示了带有金属/金属氧化物结合物的DLC涂层的摩擦行为，以及连续点曲线显示了随时间时间的力行为。 
从图4中可看出，在表面中带有金属/金属氧化物结合物的DLC涂层比不带有这种结合物的涂层表现出更低的磨损程度，这是由于在10-12分钟的短期磨合之后，不带有结合物的DLC涂层的摩擦会增大，但是带有结合物的DLC涂层的摩擦几乎为恒定的。 

Claims (9)

1.一种滑动件，特别是活塞环，其中在基材上带有DLC涂层(12)，其特征在于，在所述DLC涂层(12)的表面中埋入了相比于DLC较软的材料(14)，其中所述滑动件通过所述DLC涂层的表面与滑动配合件形成接触，并承靠着所述滑动配合件而滑动。
2.根据权利要求1所述的滑动件，其特征在于，所述较软的材料(14)包括比所述DLC涂层(12)更软的金属或金属氧化物，特别是铁或铁铬化合物或其氧化物。
3.根据上述权利要求中任一项所述的滑动件，其特征在于，所述DLC涂层(12)的表面包括以面积计为15-60%、优选为20-40%的量的较软的材料(14)。
4.根据上述权利要求中任一项所述的滑动件，其特征在于，埋入了较软的材料(14)的DLC涂层(12)的区域在所述DLC涂层(12)中从所述表面向下延伸1μm的深度，优选为向下延伸0.5μm的深度。
5.根据上述权利要求中任一项所述的滑动件，其特征在于，所述表面具有小于2μm、优选小于1μm的平均粗糙度RZ，和/或小于0.15μm、优选小于0.1μm的最小峰高RPK。
6.根据上述权利要求中任一项所述的滑动件，其特征在于，还包括处在基材和DLC涂层之间的金属，优选为铬、钛或钨的粘结层。
7.一种生产根据权利要求1到6中任一项所述的滑动件的方法，其特征在于，将相比于DLC较软的材料结合到所述滑动件的DLC涂层的表面中，其中所述滑动件与滑动配合件接触，并承靠所述滑动配合件而滑动。
8.根据权利要求7所述的方法，其特征在于，将比DLC涂层更软的金属或金属氧化物，特别是铁或铁铬化合物或其氧化物作为所述较软的材料结合到DLC涂层的表面中。
9.根据权利要求8所述的方法，其特征在于，通过涂覆或引入将所述较软的材料结合到DLC涂层的表面中。
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