Edwards Camille, Lien Hsu-Ming, Molina Nicolás, Mangolini Filippo
Walker Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712, United States.
Texas Materials Institute, The University of Texas at Austin, Austin, Texas 78712, United States.
ACS Appl Mater Interfaces. 2024 Jun 5;16(22):29314-29323. doi: 10.1021/acsami.4c00677. Epub 2024 May 21.
Dopants and alloying elements are commonly introduced in amorphous carbon (a-C) materials to tailor their mechanical and tribological properties. While most published studies have focused on doping and alloying a-C coatings with metals or metalloids, doping a-C films with rare-earth elements has only recently been explored. Notably, our understanding of the shear-induced structural changes occurring in rare-earth-element-containing a-C films is still elusive, even in the absence of any liquid lubricants. Here, the friction response of Eu- and Gd-containing a-C films with low hydrogen content deposited by HiPIMS on silicon was evaluated in open air and at room temperature. The load-dependent friction measurements indicated that the introduction of Gd ((2.3 ± 0.1) at.%) and Eu ((2.4 ± 0.1) at.%) into the a-C matrix results in a significant reduction of the shear strength of the sliding interfaces ((41 ± 2) MPa for a-C, (16 ± 1) MPa for a-C:Gd, and (11 ± 2) MPa for a-C:Eu). NEXAFS spectromicroscopy experiments provided evidence that no stress-assisted sp-to-sp rehybridization of carbon atoms was induced by the sliding process in the near-surface region of undoped a-C, while the amount of sp-bonded carbon progressively increased in a-C:Gd and a-C:Eu upon increasing the applied normal load in tribological tests. The formation of an sp-bonded carbon-rich surface layer in a-C:Gd and a-C:Eu films was not only proposed to be the origin for the reduced duration of the running-in period in tribological test, but was also postulated to induce shear localization within the sp-carbon-rich layer and transfer film formation on the countersurface, thus decreasing the interfacial shear strength. These findings open the path for the use of Gd- and Eu-containing a-C even under critical conditions for nearly hydrogen-free a-C films (i.e., humid air).
掺杂剂和合金元素通常被引入非晶碳(a-C)材料中,以调整其机械和摩擦学性能。虽然大多数已发表的研究都集中在使用金属或类金属对a-C涂层进行掺杂和合金化,但用稀土元素掺杂a-C薄膜的研究直到最近才开始。值得注意的是,即使在没有任何液体润滑剂的情况下,我们对含稀土元素的a-C薄膜中由剪切引起的结构变化仍知之甚少。在此,通过高功率脉冲磁控溅射(HiPIMS)在硅上沉积的低氢含量含铕和钆的a-C薄膜在室温下的空气中的摩擦响应进行了评估。与载荷相关的摩擦测量表明,将钆((2.3 ± 0.1) 原子百分比)和铕((2.4 ± 0.1) 原子百分比)引入a-C基体中会导致滑动界面的剪切强度显著降低(a-C为(41 ± 2) 兆帕,a-C:Gd为(16 ± 1) 兆帕,a-C:Eu为(11 ± 2) 兆帕)。近边X射线吸收精细结构光谱显微镜实验提供的证据表明,在未掺杂的a-C近表面区域,滑动过程不会诱导碳原子发生应力辅助的sp-to-sp重新杂化,而在摩擦学测试中,随着施加的法向载荷增加,a-C:Gd和a-C:Eu中sp键合碳的数量逐渐增加。在a-C:Gd和a-C:Eu薄膜中形成富含sp键合碳的表面层不仅被认为是摩擦学测试中磨合阶段持续时间缩短的原因,还被假定会在富含sp碳的层内诱导剪切局部化,并在对偶表面形成转移膜,从而降低界面剪切强度。这些发现为即使在几乎无氢的a-C薄膜的关键条件下(即潮湿空气)使用含钆和铕的a-C开辟了道路。