CN112534084A - 特别是用于配气机构系统的部件以及生产这种部件的方法 - Google Patents

特别是用于配气机构系统的部件以及生产这种部件的方法 Download PDF

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CN112534084A
CN112534084A CN201980051468.4A CN201980051468A CN112534084A CN 112534084 A CN112534084 A CN 112534084A CN 201980051468 A CN201980051468 A CN 201980051468A CN 112534084 A CN112534084 A CN 112534084A
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protective layer
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里卡多·恩里克·布鲁尼亚拉
纳兹勒姆·巴格西万
埃德加·舒尔茨
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Schaeffler Technologies AG and Co KG
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Abstract

本发明涉及一种部件(100)，特别是用于配气机构系统的部件，该部件包括衬底(3)和至少部分地施加到衬底(3)上的层系统(1)，其中层系统(1)包括用于形成部件表面的减少摩擦和减少磨损的保护层(2)，其中保护层(2)具有由掺杂的四面体非晶碳制成的至少一个第一子层(4，4a)，该掺杂的四面体非晶碳包含摩尔分数为至少50％的sp3杂化碳，其中第一子层(4，4a)包含浓度为0.1原子％～3.0原子％的氧和浓度为0.1原子％～15原子％的氢，并且其中第一子层(4，4a)具有浓度为0.03原子％～15原子％的以下掺杂物中的一种或多种掺杂物：铬、钼、钨、硅、铜、铌、锆、钒、镍、铁、银、铪、氟、硼、以及氮。本发明还涉及生产这种部件(100)的方法。

Description

特别是用于配气机构系统的部件以及生产这种部件的方法
技术领域
本发明涉及特别是用于配气机构系统的部件，该部件包括衬底和至少部分地施加到该衬底上的层系统，其中该层系统包括用于形成部件表面的减少摩擦和减少磨损的保护层。本发明还涉及用于生产这种部件的方法。
背景技术
在多种实施方案中，从现有技术已知用于受摩擦应力的表面的涂层。在技术上至关重要的应用领域是减少内燃发动机中的摩擦和磨损。动力传动装置中涉及的部件及其相对彼此滑动的表面上的高动态负载需要具有高硬度和耐久性的极高性能涂层。在这方面，非晶碳层已被证明是一类特别有利的层系统。特别地，所谓的类金刚石碳(DLC)层成功地用于柴油发动机中的曲柄传动系统、气门控制系统或燃料喷射系统的零件的涂层中。
相比于由sp2杂化碳原子的结晶层构成的石墨，以及四面体配位的sp3杂化碳的晶体金刚石，非晶碳具有sp2杂化碳原子和sp3杂化碳原子的混合物，其中一些碳可以与其他元素键合，特别是与氢键合。就机械特性而言，非晶碳相可以被视作具有以下三种不同键类型的混合物的碳原子的非晶网络：两个sp2杂化碳原子之间的键(“类石墨”键)、sp3杂化碳原子之间的键(“类金刚石”键)和碳氢键。如果存在显著比例的sp3杂化碳，则相关碳层被称为“金刚石型”，其中名称“金刚石型碳”(也称为“类金刚石碳”)用作范围广泛的不同碳涂层的集合术语(有关分类和命名，请参见VDI指南2840“碳层-基础、层类型和特性”，2012年6月([VDI guideline 2840“Carbon layers—basics,layer types and properties”],June2012)。这些层的金刚石型特征，特别是高硬度和高弹性模量，是由于sp3碳-碳键的比例导致的。在高比例的sp3杂化碳的情况下，存在特殊形式的DLC，其被称为四面体非晶碳。就涂层而言，四面体无氢非晶碳层(缩写为ta-C)和四面体含氢非晶碳层(ta-C:H)之间存在区别(请参见上面提及的VDI指南2840)。
在发动机元件(诸如喷嘴、铲斗挺杆或活塞销)上使用此类涂层向部件提供优异的摩擦特性、低粘合性、高表面硬度，并且提供增强的抗磨损保护。与金刚石层的生长需要非常高的温度相比，非晶碳层还具有可以在较低温度下生产的优点，因此更经济。相比之下，非晶碳层的缺点包括低机械韧性和高残余压应力。后者特别构成例如层厚度的限制因素，并且还使得难以以稳定的方式将非晶碳层施加到弯曲表面上。
由DE 10 2004 041 235 A1已知一种由无氢四面体非晶碳制成的耐磨涂层。WO2017/148582描述了一种具有无氢非晶碳层和由锆制成的粘合层的涂层。文献DE 10 2004043 550 A1描述了一种具有含无氢四面体非晶碳的功能层的涂层，并且实用新型AT 14701U1描述了一种由掺杂碳组成的涂层来源或涂层靶材(供体材料)。
在该背景技术下，本发明的目的是提供具有层系统的部件，该层系统具有低摩擦系数、高耐磨性和低内应力，并且适用于涂覆弯曲表面，特别是发动机部件。
该目的通过下述部件来实现：该部件包括衬底和至少部分地施加到该衬底上的层系统，其中该层系统包括用于形成部件表面的减少摩擦和减少磨损的保护层，其中该保护层具有由掺杂的四面体非晶碳制成的至少一个第一子层，该掺杂的四面体非晶碳包含摩尔分数为至少50％的sp3杂化碳，其中该第一子层包含浓度为0.1原子％～3.0原子％的氧和浓度为0.1原子％～15原子％的氢，并且其中该第一子层具有浓度为0.03原子％～15原子％的以下掺杂物中的一种或多种掺杂物：铬、钼、钨、硅、铜、铌、锆、钒、镍、铁、银、铪、氟、硼、以及氮。
为了由掺杂的四面体非晶碳生产第一子层，必须生产高比例的sp3杂化碳原子。通过引入能量来激发杂化所需的电子转移，其中通过与高能粒子的相互作用将该能量提供给碳，这些高能粒子例如通过电弧蒸发或溅射沉积，使用离子辅助涂覆工艺或基于等离子体的工艺来提供。然而，这些高能粒子的作用同时导致碳网络结构变形并产生高机械残余压应力，这特别是层厚度的限制因素。此外，受机械应力的层对衬底的粘合性降低，原因是应力倾向于使该层变形，因此该层在摩擦负载下可能变得分离或撕裂。由于衬底的几何形状而在层上施加预定的变形，这一事实使得将该层施加到弯曲的部件表面上变得更加困难。通过将氢和氧掺入四面体非晶碳中，可以实现残余压应力的显著降低，并且可以增加第一子层的弹性，从而可以生产也可以以足够大的层厚度和良好的粘合强度用于弯曲表面上的层系统。
掺入氢和氧还产生了第一子层，当该第一子层与钢滑动接触时，其摩擦系数仅因水分而发生可忽略不计的降低。此外，用氢和氧形成的四面体非晶碳层具有增加的热稳定性。
特别地，已证明用金属对第一子层进行附加掺杂是用于降低残余压应力的另一有效措施。除了降低残余压应力之外，通过适当选择的掺杂元素可以有针对性地改善第一子层、因而保护层的其他特性。特别地，掺杂氟、硅和/或铜导致四面体非晶碳层的摩擦学特性出现相当大的改善。用硅掺杂产生保护层，当该保护层与钢滑动接触时，其摩擦系数仅因水分而发生可忽略不计的降低。此外，与硅混合的四面体非晶碳层具有增加的热稳定性。用硼连同氟一起掺杂产生示出高硬度和疏水特性的组合的保护层，并且添加钨可以导致摩擦的显著降低。另一种可能的掺杂物是氮，以便使保护层具有较低的摩擦系数和较长的使用寿命。
发明内容
根据本发明，第一子层包含浓度为0.03原子％～15原子％的掺杂物。相应的浓度优选地在0.2原子％～10原子％的范围内，并且特别优选地在0.2原子％～5原子％的范围内。
根据本发明的另一有利的实施方案，层系统具有粘合层，其中该粘合层布置在衬底与保护层之间，并且其中该粘合层具有铬和/或钛和/或钨和/或锆和/或钼和/或氮化铬和/或氮化钛和/或氮化钨和/或氮化钼和/或氮化锆。为了防止保护层由于四面体非晶碳层的残余压应力而分离，可以使用在衬底与保护层之间以这种方式选择的粘合层来提高对衬底的粘合性。通过施加由前述材料制成的粘合层，保护层在衬底上的粘合强度可以显著提高，并且因此开发用于经受摩擦负载的部件中。
金属粘合层(优选地由钛或铬制成)可以特别显著地提高对钢的粘合性。
根据本发明的另一有利的实施方案，粘合层具有在从0.001μm至2.0μm范围内的层厚度。该层厚度优选地在从0.001μm至1.0μm的范围内，特别优选地在从0.001μm至0.5μm的范围内。
根据本发明的另一有利的实施方案，层系统具有中间层，其中该中间层布置在粘合层与保护层之间并且具有金属或过渡金属的至少一种碳化物以及/或者金属或过渡金属和/或非金属的碳氮化物。
中间层的层厚度优选地在从0.001μm至1.0μm的范围内。特别地，中间层的层厚度在从0.001μm至0.5μm的范围内，特别优选地在从0.001μm至0.05μm的范围内。中间层可以有利地提高保护层与粘合层之间的粘合性。中间层可以在单独的生长步骤中沉积，或者例如可以通过在粘合层与碳层之间的界面处形成碳化物来生产，因为碳被注入到粘合层的自由表面中。
根据本发明的另一有利的实施方案，保护层由单个第一子层组成，该第一子层由掺杂的四面体非晶碳制成。在该实施方案中，由掺杂的四面体非晶碳制成的第一子层被直接施加到衬底上，并且该层系统没有附加的粘合层或中间层。以这种方式，可以有利地实现特别简单的工艺控制，而不需要用于不同层的单独生长步骤来生产保护层。
根据本发明的另一有利的实施方案，保护层具有由掺杂的四面体非晶碳制成的一个或多个第一子层和由未掺杂的四面体非晶碳制成的一个或多个第二子层，其中第一子层和第二子层彼此交替。由于掺杂的第一子层和未掺杂的第二子层的该交替结构，因此可以通过一些实验有针对性地积极影响保护层的机械特性。在这种层状结构中，例如，材料裂纹的扩展被抑制，并且保护层的韧性被提高。该多层结构的特性可以进一步受到掺杂程度以及第一子层和第二子层的数量和厚度的影响。
根据本发明的另一有利的实施方案，保护层具有大于40GPa的硬度。硬度规格涉及根据DIN EN ISO 14577-4(2017年4月)使用纳米压痕技术进行的测量。
该部件特别是滑动轴承部件或滚柱轴承部件，或者指轮从动件或摇臂或泵挺杆或滚柱挺杆的部件。特别地，层系统以与相邻接触部件滚动接触和/或减摩接触和/或滑动接触的方式布置在该部件上。
特别地，该部件是滚动元件，特别是凸轮滚柱，例如凸轮从动件，其中层系统形成在滚动元件的跑合表面上和/或滚动元件的一个或多个侧表面上。这种类型的滚动元件用在内燃发动机的配气机构中，例如作为滚柱指轮从动件的一部分。在内燃发动机中，指轮从动件被用作凸轮与推杆之间的传动元件。在滚柱指轮从动件的情况下，凸轮经由凸轮滚柱或凸轮从动件拾取。通过将根据本发明的层系统施加到表面上，由于滚柱表面的摩擦负载引起的磨损现象可以有利地减轻并且摩擦损失得以减小。
然而，该部件也可以有利地是减摩轴承的外环、内环或减摩体，或者滑动轴承的外环或内环。
本发明还涉及用于生产根据本发明的部件的方法，其中施加由掺杂的四面体非晶碳制成的至少一个第一子层，因为该第一子层是通过借助于电弧蒸发(特别是电弧法)而进行的物理气相沉积和/或通过高功率脉冲磁控溅射(高功率脉冲磁控溅射HiPIMS，或高功率脉冲式磁控溅射HPPMS)来施加，其中至少一种掺杂物经由气相和/或使用由掺杂的碳制成的靶材材料(供体材料)被引入到第一子层中和/或至少一种掺杂物通过共溅射被掺入保护层中。
附图说明
下面将参照附图中所示的示例性实施方案说明本发明的更多细节和优点。在附图中：
图1a在示意性图示中示出了根据本发明的在衬底上具有层系统的部件的示例性实施方案；
图1b在示意性图示中示出了根据本发明的在衬底上具有层系统的部件的示例性实施方案；
图2a在示意性图示中示出了根据本发明的在衬底上具有包括粘合层的层系统的部件的示例性实施方案；
图2b在示意性图示中示出了根据本发明的在衬底上具有包括粘合层的层系统的部件的示例性实施方案；
图3a在示意性图示中示出了根据本发明的在衬底上具有包括中间层的层系统的部件的示例性实施方案；
图3b在示意性图示中示出了根据本发明的在衬底上具有包括中间层的层系统的部件的示例性实施方案；
图4a在示意性图示中示出了根据本发明的在衬底上具有包括粘合层和中间层的层系统的部件的示例性实施方案；
图4b在示意性图示中示出了根据本发明的在衬底上具有包括粘合层和中间层的层系统的部件的示例性实施方案；
图5在示意性图示中示出了根据本发明的为滚动元件形式的部件的示例性实施方案；
具体实施方式
在图1a所示的根据本发明的具有层系统1的部件100的示例性实施方案中，该实施方案由保护层2组成，该保护层由直接施加到衬底3上的掺杂的四面体非晶碳的单个均质的第一子层4形成。
在图1b所示的示例性实施方案中，部件100包括保护层2，该保护层由多个第一子层4a和第二子层5的序列形成，其中由掺杂的四面体非晶碳制成的第一子层4a首先被直接施加到衬底3上，该第一子层上继而布置由未掺杂的四面体非晶碳制成的第二子层5。掺杂的第一子层4a和未掺杂的第二子层5的这种交替一直持续到顶部的第二子层5。
在此以及在图2b、图3b和图4b中示出的层系统1是示例性的表示。掺杂的第一子层4a和未掺杂的第二子层5的该序列在原则上可以包含任意数量的第一子层4a和第二子层5。
在图2a中所示的部件100的示例性实施方案中，粘合层6布置在衬底3与保护层2之间，这改善了保护层2与衬底3的结合，并且连同保护层2一起形成层系统1。
在图2b所示的部件100的示例性实施方案中，在保护层2与衬底3之间布置有粘合层6，该保护层包括由掺杂的四面体非晶碳制成的第一子层4a和由未掺杂的四面体非晶碳制成的第二子层5的交替序列。
在图3a所示的部件100的示例性实施方案中，中间层7连同保护层2一起形成层系统1，该中间层布置在衬底3与仅包括由掺杂的四面体非晶碳制成的第一子层4a的保护层2之间。
在图3b所示的部件100的示例性实施方案中，中间层7布置在保护层2之间，该保护层具有由掺杂的四面体非晶碳制成的第一子层4a和由未掺杂的四面体非晶碳制成的第二子层5的交替序列，并且该中间层连同第一子层4a和第二子层5一起形成施加到衬底3上的层系统1。
在图4a中所示的部件100的示例性实施方案中，粘合层6和中间层7布置在衬底3与呈由掺杂的四面体非晶碳制成的第一子层4的形式的保护层2之间，并且连同保护层2一起形成层系统1。粘合层6改善了中间层7与衬底3的结合，而中间层7进而起到粘合层6与保护层2之间的粘合促进剂的作用。在制造过程期间，中间层7可以在粘合层6之后和保护层2之前单独地沉积，或者，例如可以通过粘合层6与保护层2之间的反应或通过将碳注入到粘合层6中而形成。
在图4b所示的部件100的示例性实施方案中，粘合层6和中间层7被布置在保护层2之间，该保护层具有由掺杂的四面体非晶碳制成的第一子层4a和由未掺杂的四面体非晶碳制成的第二子层5的交替序列，并且类似于图4a，改善了与衬底3的结合。
当图5中所示的部件100是滚动元件8的形式时，滚动元件8的跑合表面9设有层系统1，以利用保护层2的减少摩擦和减少磨损的特性，以将滚动元件8用作内燃发动机的气门控制的一部分。任选地，滚动元件8的侧表面10、11也可以设有层系统1。
上述滚动元件8特别是凸轮滚柱8，其中层系统1的实施方案形成在滚动元件8的跑合表面9上和/或滚动元件8的一个或多个侧表面10、11上。
上述部件100和上述滚动元件8可以使用根据本发明的方法的实施方案来生产，其中包括掺杂的四面体非晶碳的至少一个第一子层4a的保护层2被施加到衬底3或跑合表面9和/或侧表面10、11上，其中保护层2通过借助于电弧蒸发而进行的物理气相沉积和/或通过高功率脉冲磁控溅射来施加，其中至少一种掺杂物经由气相和/或使用由掺杂的碳制成的靶材被引入到至少一个第一子层4a中和/或至少一种掺杂物通过共溅射被引入到至少一个第一子层4a中。
附图标记列表
1 层系统
2 保护层
3 衬底
4、4a 由掺杂的四面体非晶碳制成的第一子层
5 由未掺杂的四面体非晶碳制成的第二子层
6 粘合层
7 中间层
8 滚动元件
9 跑合表面
10 第一侧表面
11 第二侧表面
100 部件

Claims (10)

1.一种部件(100)，特别是用于配气机构系统的部件，所述部件包括衬底(3)和至少部分地施加到所述衬底(3)上的层系统(1)，其中所述层系统(1)包括用于形成部件表面的减少摩擦和减少磨损的保护层(2)，其中所述保护层(2)具有由掺杂的四面体非晶碳制成的至少一个第一子层(4，4a)，所述掺杂的四面体非晶碳包含摩尔分数为至少50％的sp3杂化碳，其中所述第一子层(4，4a)包含浓度为0.1原子％～3.0原子％的氧和浓度为0.1原子％～15原子％的氢，并且其中所述第一子层(4，4a)具有浓度为0.03原子％～15原子％的以下掺杂物中的一种或多种掺杂物：铬、钼、钨、硅、铜、铌、锆、钒、镍、铁、银、铪、氟、硼、以及氮。
2.根据权利要求1所述的部件(100)，其中所述层系统(1)具有粘合层(6)，其中所述粘合层(6)布置在所述衬底(3)与所述保护层(2)之间，并且其中所述粘合层(6)具有铬和/或钛和/或钨和/或锆和/或钼和/或氮化铬和/或氮化钛和/或氮化钨和/或氮化钼和/或氮化锆。
3.根据权利要求2所述的部件(100)，其中所述粘合层(6)具有在从0.001μm至2.0μm范围内的层厚度。
4.根据权利要求2或3中任一项所述的部件(100)，其中所述层系统(1)具有中间层(7)，其中所述中间层(7)布置在所述粘合层(6)与所述保护层(2)之间并且具有金属或过渡金属和/或非金属的至少一种碳化物和/或碳氮化物。
5.根据权利要求4所述的部件(100)，其中所述中间层(7)具有在从0.001μm至1.0μm范围内的层厚度。
6.根据权利要求1至5中任一项所述的部件(100)，其中所述保护层(2)具有由所述掺杂的四面体非晶碳制成的一个或多个第一子层(4，4a)，并且还具有由未掺杂的四面体非晶碳制成的一个或多个第二子层(5)，其中所述第一子层和所述第二子层(4，4a；5)彼此交替。
7.根据前述权利要求中任一项所述的部件(100)，其中所述保护层(2)具有大于40GPa的硬度。
8.根据权利要求1至7中任一项所述的部件(100)，其中所述部件是滑动轴承部件或滚柱轴承部件，或者指轮从动件或摇臂或泵挺杆或滚柱挺杆的部件。
9.根据权利要求8所述的部件(100)，其中所述层系统(1)与相邻接触部件的接触方式为滚动接触和/或减摩接触和/或滑动接触。
10.一种用于生产根据权利要求1至9中任一项所述的部件(100)的方法，其中施加由掺杂的四面体非晶碳制成的所述至少一个第一子层(4，4a)，因为所述第一子层(4，4a)是通过借助于电弧蒸发而进行的物理气相沉积和/或高功率脉冲磁控溅射来施加，其中所述至少一种掺杂物经由气相和/或由掺杂的碳制成的靶材被引入到所述至少一个第一子层(4，4a)中和/或所述至少一种掺杂物通过共溅射被引入到至少一个第一子层(4，4a)中。
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