CN116194694A - 滑动元件，特别是活塞环 - Google Patents

滑动元件，特别是活塞环 Download PDF

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CN116194694A
CN116194694A CN202180063677.8A CN202180063677A CN116194694A CN 116194694 A CN116194694 A CN 116194694A CN 202180063677 A CN202180063677 A CN 202180063677A CN 116194694 A CN116194694 A CN 116194694A
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carbon
sliding element
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格雷戈尔·恩格贝格
马库斯·肯尼迪
尤里·伊凡诺夫
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Federal Mogul Burscheid GmbH
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Abstract

根据本发明的滑动元件、特别是活塞环包括涂层，该涂层从内到外具有以下层：粘合剂层、含碳功能层和非晶DLC外部层。含碳功能层的层厚度为涂层的总层厚度的至少70％、优选至少80％，并且含碳功能层与外部非晶DLC层的杨氏模量比率为1.2或更大。

Description

滑动元件，特别是活塞环
技术领域
本发明涉及一种具有涂层的滑动元件，特别是活塞环。
滑动元件(诸如，例如活塞环)具有运行面(running surface)，在该运行面上它们与摩擦副(friction partner)滑动接触。摩擦学系统是复杂的，并且主要由摩擦副的材料配对(material pairing)和环境条件(诸如，例如压力、温度和周围介质)决定。尤其是在现代发动机中，在活塞环上存在特别高的负荷。为了确保和延长部件的功能性和寿命，可以特别地优化滑动元件的运行面性能。
背景技术
这种优化通常包括通过例如热喷涂工艺、电镀工艺或薄层技术工艺来施加或多或少复杂的层系统。这些层的主要目的是防止磨损，并且首先通常以层的高硬度为目标。类金刚石碳层(类金刚石碳(diamond-like carbon)，DLC)已经被证明是特别硬且坚固的层。这些类金刚石碳层可以以许多方式改变它们的性能，例如通过改变它们的C-C键合特性、碳的不同键合分数以及通过存在或不存在氢和金属。通常在这些磨损保护层下方施加粘合剂层，该粘合剂层认为是确保高应变磨损保护层与滑动元件的基底材料的特别坚固和牢固的结合。
然而，仅使用非常硬的DLC层导致一些技术问题。一方面，这些层的表面必须非常光滑，使得在较高的表面压力下，表面上不会发生破裂，并且使得层系统不会失效。此外，例如，可以看出，环磨损和内衬磨损随着磨损保护层的粗糙度而明显增加。因此，在使用前必须使磨损保护层的表面尽可能光滑，然而这涉及大量的技术工作并且是非常昂贵的。例如，EP1 829 986B1描述了一种如何通过刷毛状或板状元件来加工这种硬质碳系层的方法。此外，非常硬的磨损保护层具有不利的磨合行为。由于其高硬度，磨合以摩擦副为代价而发生，在磨合阶段中摩擦副经历增加的磨损，另外可能发生划痕和/或烧痕的形成。
考虑到磨合行为，在磨损保护层上设置磨合层是有利的。这些层的目的是产生一种摩擦学“平衡”，即，磨合层在与摩擦副第一次接触时被剥离，并且在这样做时，它执行摩擦副的相互调整。在磨合阶段之后，摩擦磨损减慢并稳定，并且随后硬的磨损保护层确保长期有利的摩擦性能以及使用寿命的耐久性。
DE10 2005 063 123 B3描述了一种滑动元件上的层系统，该层系统从内向外由磨损保护层、粘合剂层和Me-C:H型的磨合层组成，其中还含有硬质材料颗粒，例如WC。
由DE10 2008 042 747 A1可知一种具有涂层的滑动元件，该涂层从内向外具有粘合剂层、PVD层、任选的a-C:H:W型的碳系层、a-C:H型的碳系层和另外的a-C:H型碳系层。可以设想，外部碳层比下面的碳层更软。
10 2013 200 846 A1描述了一种具有涂层的滑动元件，该涂层从内向外具有第一粘合剂层、硬质无氢DLC层、第二粘合剂层、软质含氢DLC层、含金属DLC层和/或含金属碳化物DLC层、以及硬质含氢DLC层，其中软质含氢DLC层比硬质无氢DLC层更软，硬质含氢DLC层比软质含氢DLC层更硬。
发明内容
在这种背景下，本发明基于制作一种具有最佳的机械和摩擦学性能的滑动元件、尤其是用于内燃机的活塞环的目的。特别地，目的是提供这样的滑动元件，该滑动元件的表面具有有利的磨合行为，即缩短的磨合时间、减少的相对本体磨损、以及磨合期间较少的燃料和油消耗。
该目的通过专利的权利要求1中描述的滑动元件来解决。
因此，所述滑动元件包括涂层，该涂层从内到外具有以下层：粘合剂层、含碳功能层和外部非晶DLC层(amorphous DLC layer)，其中含碳功能层的层厚度为涂层的总层厚度的至少70％，并且含碳功能层与外部非晶DLC层的杨氏模量比率为1.2或更大。
本发明基于以下发现：一方面，通过增加杨氏模量(或DLC层中的sp3含量)可以实现含碳功能层的改善的耐热性，但是另一方面，具有增加的杨氏模量使得层平滑明显变得更困难，因此不经济。根据本发明解决了这个难题，首先，提供了含碳功能层，该含碳功能层相对于外部DLC层具有高的杨氏模量，并且承载了最大比例的涂层，即总厚度的至少70％。因此，上述含碳功能层明显有助于改善耐热性。其次，相对于含碳功能层更薄且具有明显更低的杨氏模量的外部非晶DLC层确保了低粗糙度。后一层因此也确保了改善的磨合行为。
根据一个有利的实施方案，外部非晶DLC层的杨氏模量比含碳功能层的杨氏模量低至少50GPa、优选至少70GPa。优选地，滑动元件的涂层仅由上述部分层构成。
根据本发明的粘合剂层优选由多个层构成。
如果含碳功能层由多个部分层构成，则杨氏模量的值在本公开的上下文中指含碳功能层的最外部分层。
根据本发明的滑动元件的优选改进在另外的权利要求中描述。
优选地，滑动元件具有至少5μm的总层厚度、优选地在5μm与40μm之间。
有利地，含碳功能层与外部非晶DLC层的硬度比率为1.2或更大，优选硬度比率在1.2至6的范围内。
还发现含碳功能层的杨氏模量有利地为至少200GPa、优选至少350GPa、特别优选在250GPa至600GPa的范围内。
根据优选的实施方案，外部非晶DLC层的杨氏模量也是至多500GPa、优选至多350GPa、更优选杨氏模量在100GPa至350GPa的范围内。
优选地，外部非晶DLC层的硬度为至多5000HV 0.02，特别优选的硬度范围为1000HV 0.02至3500HV 0.02。
有利地，外部非晶DLC层的碳含量为至少90at.％、优选至少97at.％。
含碳功能层和/或外部非晶DLC层优选具有小于3at.％、优选小于0.5at.％的氢含量。特别地，即使在缺乏润滑条件下，在高应变摩擦学系统中，无氢DLC层(在此上下文中，无氢对应于小于3at.％的氢含量)在降低摩擦和磨损方面具有高潜力。
根据本发明的有利的实施方案，含碳功能层优选从内向外具有以下层：AxCy层，C代表碳，A代表金属，x和y各包括1-99的值；和/或含金属碳内部部分层(inner metal-containing carbon partial layer)和含晶体碳外部部分层的含晶体碳层(crystalline-containing carbon layer)；和/或至少一个非晶碳层，该至少一个非晶碳层具有比外部非晶DLC层更高的杨氏模量。这种类型的涂层系统的特征在于特别有利的摩擦学性能。
有利地，粘合剂层包含金属，并且AxCy层中的金属A对应于含金属粘合剂层中的金属，金属A优选选自钨、钛、铬或其它的过渡金属。
根据本发明的滑动元件的另一实施方案设想，含碳功能层具有多个非晶碳层，且非晶碳层的杨氏模量从内向外减少。替代地或另外地，含碳功能层可以包括至少一个非晶碳层，该非晶碳层具有从内向外以渐变方式(in agraded manner)减少的杨氏模量。
优选地，滑动元件在AxCy层与含晶体碳层之间具有过渡层，该过渡层由AxCy层和含晶体碳层的混合相(mixed phase)构成，并且优选地具有1nm至25nm的厚度。
有利地，AxCy层具有3nm至10nm、优选地4nm至8nm的厚度。
含晶体碳层优选还具有不大于50nm的厚度。
优选地，该涂层的触觉测量粗糙度(tactilely measured roughness)满足Rk＜1.4μm且Rpk＜0.3μm、特别优选Rk＜0.9μm且Rpk＜0.2μm的条件。
此外，该涂层的光学测量粗糙度优选满足Rk＜2.0μm且Rpk＜0.5μm、特别优选Rk＜1.5μm和Rpk＜0.4μm的条件。
根据本发明的一个有利的实施方案，涂层的各个层中的至少一者通过PVD方法制备。
具体实施方式
在本发明的范围内，与两个参照实施例相比，测试了根据本发明的层结构的影响。所有实施例具有总层厚度为约23μm的涂层。两个比较实施例在滑动元件的最外周具有含碳功能层，而根据本发明的实施例另外在含碳功能层上具有层厚度为约4μm的外部非晶DLC层。第一比较实施例和第二比较实施例主要在含碳功能层的杨氏模量方面不同：尽管第一比较实施例在这方面具有相对低的杨氏模量(具有200GPa至290GPa)，但在第二比较实施例中的杨氏模量(具有350GPa至450GPa)明显较高。根据本发明的实施例在含碳功能层也具有相对高的杨氏模量(具有350GPa至500GPa)；外部非晶DLC层中的杨氏模量(具有200GPa至350GPa)也是相对低的。对于根据本发明的实施方案，从含碳功能层到外部层的杨氏模量比率＞1.2。在没有专用附加的外部层的情况下，在比较实施例中不能测定杨氏模量比率。实施例之间的差异可以在下表中示出：
表1：
Figure BDA0004129506390000051
在加工所得涂层之后，测量粗糙度Rk和Rpk。表1中所示的值证实，与最外部层中具有相对高的杨氏模量的涂层(如比较实施例2中)相比，最外部层中具有相对低的杨氏模量的涂层(如比较实施例1和根据本发明的实施例)在加工后表现出明显改善的粗糙度。在此背景下，对磨损行为的研究已经表明，粗糙度参数Rk和Rpk对于在气缸的环和工作面的配对中的摩擦和磨损行为是决定性的。如果达到或超过粗糙度参数Rk＝1.5μm和Rpk＝0.4μm，则与优选的最大粗糙度参数Rk＝0.9μm和Rpk＝0.2μm(在350℃下的层稳健性(robustness)测试之前在各种情况下光学测量的值)相比，气缸的运行面的磨损增加超过75％。因此，比较实施例2显示出不允许的高粗糙度。
随后，在测试中研究涂层的耐热性。耐热性的评价是通过在大气中、350℃下老化该层24小时、且随后与初始状态相比的比较光学粗糙度测量来执行的。如果在这个过程中，Rk或Rpk参数的粗糙度与初始状态相比增加超过30％，则认为不满足所谓的30％规定。换句话说，粗糙度在热负荷下恶化到不可接受的程度。在本研究中，这适用于比较实施例1，参见表1。
随后在发动机外部在真实的环区段上进行涂层的摩擦学研究，这些真实的环区段在完全润滑条件下、在振荡摩擦计中抵靠气缸的运行面的真实区段移动并且经受法向力。如上所述，将测试的层预先在大气下、350℃老化24小时。在发动机外部的摩擦学测试之后，光学测量气缸的环和运行面的磨损。表1中所列的结果表明，比较实施例1和2显示出不允许的高内衬磨损，比较实施例1还显示出不允许的高环磨损。
上述研究表明，提供根据本发明的外部非晶DLC层令人惊讶地导致即使在高温下也具有优异的耐磨性。
在本公开的范围内提及的参数的测量如下执行：对于杨氏模量的测量，从待测量层的表面到深度范围对层执行研磨。杨氏模量的测定使用纳米压痕仪进行。所应用的硬度测试方法是使用压痕法的显微硬度测试。选择测量点，使得它们位于平台上，不接触任何凹陷，并且彼此之间的距离是压痕对角线(Berkovich试样)宽度的三倍。研磨后样品的穿透深度必须不超过待测涂层区域厚度的10％。根据Oliver和Pharr(Oliver,W.C.,Pharr,G.M.,“An improved technique for determining hardness and elastic modulus usingload and displacement sensing indentation experiments”,J.Mat.Res.,7(6),June1992,pages 1564to 1583)的方法限定计算。
从Mahr，Hommel等商购的表面测量设备用于粗糙度的触觉测量。并且，使用以下参数：
表2：
Figure BDA0004129506390000061
*由于该层非常硬，所以规定了10μm的探针尖端半径和减小的测量力。所推荐的探针尖端几何形状确保了探针尖端的实际使用寿命。探针尖端必须使用探针尖端参考标准(例如Hall KNT 4050:01)定期检查。
**推荐的滤光器之间的参数差异在个位数nm范围内。
白光共聚焦显微镜(NanoFocusμsurf)用于粗糙度的光学测量。并且，使用以下参数：
表3：
Figure BDA0004129506390000071
粗糙度值是测量点内的评估的测量轨迹的平均值。

Claims (17)

1.一种滑动元件，特别是活塞环，所述滑动元件具有涂层，所述涂层从内向外具有以下层：
-粘合剂层
-含碳功能层，以及
-外部非晶DLC层，
其特征在于，
所述含碳功能层的层厚度为所述涂层的总层厚度的至少70％、优选至少80％，并且
所述含碳功能层与所述外部非晶DLC层的杨氏模量比率为1.2或更大、优选在1.2至6的范围内。
2.根据权利要求1所述的滑动元件，
其特征在于，
所述总层厚度为至少5μm、优选在5μm至40μm的范围内。
3.根据权利要求1或2所述的滑动元件，
其特征在于，
所述含碳功能层与所述外部非晶DLC层的硬度比率为1.2或更大、优选在1.2至6的范围内。
4.根据前述权利要求中任一项所述的滑动元件，
其特征在于，
所述含碳功能层的杨氏模量为至少200GPa、优选至少350GPa、特别优选在250GPa至600GPa的范围内。
5.根据前述权利要求中任一项所述的滑动元件，
其特征在于，
所述外部非晶DLC层的杨氏模量为至多500GPa、优选至多350GPa、优选在100GPa至350GPa的范围内。
6.根据前述权利要求中任一项所述的滑动元件，
其特征在于，
所述外部非晶DLC层的硬度为至多5000HV 0.02、优选在1000HV 0.02至3500HV 0.02的范围内。
7.根据前述权利要求中任一项所述的滑动元件，
其特征在于，
所述外部非晶DLC层的碳含量为至少90at％、优选至少97at％。
8.根据前述权利要求中任一项所述的滑动元件，
其特征在于，
所述含碳功能层和/或所述外部非晶DLC层具有小于3at.％、优选小于0.5at.％的氢含量。
9.根据前述权利要求中任一项所述的滑动元件，
其特征在于，
所述含碳功能层优选从内到外具有以下层：
-AxCy层，C代表碳，A代表金属，x和y各自包括1至99的值，和/或
-含金属碳内部部分层和含晶体碳外部部分层的含晶体碳层，和/或
-至少一个非晶碳层，所述至少一个非晶碳层具有比所述外部非晶DLC层更高的杨氏模量。
10.根据权利要求9所述的滑动元件，
其特征在于，
所述粘合剂层包含金属，并且所述AxCy层中的金属A对应于含金属的所述粘合剂层中的金属，所述金属A优选选自钨、钛、铬或其它的过渡金属。
11.根据权利要求9或10所述的滑动元件，
其特征在于，
所述含碳功能层具有多个非晶碳层，并且所述非晶碳层的杨氏模量从内向外减少，和/或所述含碳功能层包括至少一个非晶碳层，所述非晶碳层具有从内向外以渐变方式减少的杨氏模量。
12.根据权利要求9至11中任一项所述的滑动元件，
其特征在于，
所述滑动元件在所述AxCy层和所述含晶体碳层之间包括过渡层，所述过渡层由所述AxCy层和所述含晶体碳层的混合相来构成，并且所述过渡层优选具有1nm至25nm的厚度。
13.根据权利要求9至12中任一项所述的滑动元件，
其特征在于，
所述AxCy层具有3nm至10nm、优选4nm至8nm的厚度。
14.根据权利要求9至13中任一项所述的滑动元件，
其特征在于，
所述含晶体碳层具有不超过50nm的厚度。
15.根据前述权利要求中任一项所述的滑动元件，
其特征在于，
所述涂层的触觉测量粗糙度Rk＜1.4μm且Rpk＜0.3μm、优选Rk＜0.9μm且Rpk＜0.2μm。
16.根据前述权利要求中任一项所述的滑动元件，
其特征在于，
所述涂层的光学测量粗糙度Rk＜2.0μm且Rpk＜0.5μm、优选Rk＜1.5μm且Rpk＜0.4μm。
17.根据前述权利要求中任一项所述的滑动元件，
其特征在于，
所述涂层的各个层中的至少一者通过PVD方法制备。
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