Superlubricity Behavior and Mechanism of MoS2-C Heterostructure Composite Films in Vacuum
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摘要:
采用闭合场非平衡磁控溅射技术制备了MoS2-C异质复合薄膜，利用多环境可控摩擦试验机测试了薄膜在真空环境中的摩擦学性能，通过拉曼光谱仪(Raman)、X射线衍射仪(XRD)和透射电子显微镜(TEM)等表征手段分析了薄膜摩擦前后结构的变化，探讨了超润滑机理. 结果表明：复合薄膜呈现致密的“纳米晶/非晶”结构，在真空中具有优异的摩擦学性能，保持了超低摩擦系数(0.006~0.009)和磨损率[1.026×10-7 mm3/(N·m)]，达到了超润滑状态. 摩擦过程中碳选择性转移到钢球表面形成非晶碳转移层，薄膜磨痕表面形成有序的MoS2 (002)晶面，摩擦发生在MoS2有序晶体和非晶碳转移膜之间，形成非公度异质接触，降低摩擦系数实现超润滑. 钢球/MoS2-Ti、a-C:H/MoS2-Ti摩擦配副在相同条件下的不同摩擦行为，也证明了上述超润滑机理.
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关键词:
- MoS2-C复合薄膜 /
- 超润滑 /
- 真空 /
- 摩擦学性能 /
- 非公度接触
Abstract:Molybdenum disulfide (MoS2) shows excellent lubricating properties in high vacuum condition due to its unique layered structure. But passivation to oxygen atmosphere like ambient air makes tribological performance lower. Although the a-C:H films exhibit super-low friction coefficient and wear rate in N2 condition, the long duration for super-low friction seems to be an important issue for its application in high vacuum. This paper aimed to combine MoS2 and a-C:H films to meet the requirements of high vacuum condition and super-low friction coefficient and long wear life under practical working conditions. Based on this, firstly, MoS2-C composite films were deposited by closed field unbalanced magnetron sputtering technology. The tribological properties of the films were tested by HVTRB in vacuum condition. The structure changes of the film before and after friction were analyzed by Raman, XRD, TEM and other analytical techniques. And the superlubricity mechanism was investigated in this study. It suggested that the composite films exhibit a dense "nanocrystalline/amorphous" microstructure, which maintain super-low friction coefficient (0.006~0.009) and wear rate [1.026×10-7 mm3/(N·m)], reaching a superlubricity state. The wear tracks and wear scars were observed by a three-dimensional profiler. It revealed that the contact area was covered with thin transfer film, while a small amount of wear debris distributed around. Furthermore, different from the as-deposited films, it was observed by
Raman that MoS2 peak around 380 cm-1 and 410 cm-1 of the wear track was obviously enhanced. A broad peak at 1 200~1 600 cm-1, indentified as amorphous carbon, was observed on the wear scar. During the friction process, C was selectively transferred to the surface of the steel ball to form an amorphous carbon transfer film. Meanwhile, the relatively disordered structure became more ordered, resulting in the presence of well aligned MoS2 in the interface, which was prone to shear the basal plane oriented along the sliding direction. The friction occurred between the ordered MoS2 crystal and the amorphous carbon transfer film. The heterostructure leaded to incommensurate contact between the frictional interfaces, resulting in establishing superlow friction during the friction period. In addition, MoS2-Ti film and a-C:H film were deposited. The friction behaviors of steel /MoS2-Ti and a-C:H/MoS2-Ti were very different under the same condition. For steel/MoS2-Ti friction pair, it was found that the transformation of amorphous MoS2 into re-ordered MoS2 on the wear track after friction. The MoS2 crystal was transferred to the steel ball. Consequently, the friction occurred between MoS2 and MoS2, which cannot achieve superlubricity. For a-C:H/MoS2-Ti friction pair, the crystallinity of MoS2 on the wear track became better after friction. The ordered MoS2 formed incommensurate contact with the a-C:H film on the steel ball, which achieved superlubricity. The above-mentioned superlubricity mechanism was proved by the different experiments.
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Keywords:
- MoS2-C composite films /
- superlubricity /
- vacuum /
- tribological properties /
- incommensurate contact
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图 1 MoS2-C复合薄膜的(a) XRD和(b)拉曼光谱
Figure 1. (a) XRD pattern and (b) Raman pattern of MoS2-C composite film
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图 2 MoS2-C薄膜截面FIB-TEM照片：(a)薄膜截面透射照片；(b)薄膜高倍截面形貌与相应的SEAD照片；(c)元素线扫描；(d) EDS能谱
Figure 2. FIB-TEM cross-sections of MoS2-C composite film: (a) film cross-sectional transmission photograph; (b) film high magnification cross-sectional morphology with corresponding SEAD pattern; (c) the elemental line distribution; (d) EDS spectra
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图 4 MoS2-C薄膜的表征：磨痕的(a)形貌SEM照片，(b)磨损深度和(c)拉曼光谱；磨斑的(d)形貌SEM照片和(e)拉曼光谱
Figure 4. The characterization of MoS2-C film: (a) SEM micrograph of morphology, (b) wear depth and (c) Raman spectrum of wear track; (d) SEM micrograph of morphology and (e) Raman spectrum of wear scar
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图 5 在真空中摩擦后MoS2-C薄膜上磨痕的截面FIB-HRTEM照片：(a~b)不同放大倍数形貌以及磨斑的截面FIB-HRTEM照片：(c~e)不同放大倍数形貌
Figure 5. Cross-sectional FIB-HRTEM mocrographs of wear track on MoS2-C film after friction in vacuum: (a~b) morphology at different magnification and FIB-HRTEM micrographs of the wear scar section: (c~e) the morphology at different magnifications
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图 6 a-C:H/MoS2-Ti和Steel/MoS2-Ti摩擦配副在真空中的摩擦曲线
Figure 6. Friction curves of a-C:H/MoS2-Ti and steel/MoS2-Ti in vacuum
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图 7 Steel/MoS2-Ti摩擦配副的表征：磨痕的(a) 形貌SEM照片，(b)磨损深度和(c)拉曼光谱；磨斑的(d) SEM照片和(e)拉曼光谱. (f) MoS2-Ti薄膜的拉曼光谱
Figure 7. Characterization of steel/MoS2-Ti friction pairs: (a) SEM micrograph, (b) wear depth and (c) Raman spectrum of wear track; (d) SEM micrograph and (e) Raman spectrum of wear scar. (f) Raman spectrum of MoS2-Ti films
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图 8 a-C:H/MoS2-Ti摩擦配副的表征：磨痕的(a)形貌SEM照片，(b)磨损深度和(c)拉曼光谱；磨斑的(d) SEM照片和(e)拉曼光谱. (f) MoS2-Ti薄膜的拉曼光谱
Figure 8. Characterization of a-C:H/MoS2-Ti friction pairs: (a) SEM micrograph, (b) wear depth and (c) Raman spectrum of wear track; (d) SEM micrograph and (e) Raman spectrum of wear scar. (f) Raman spectrum of MoS2-Ti films
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图 9 3种不同摩擦配副在真空中摩擦后薄膜的磨损率
Figure 9. Wear rates of films after the fiction of three different friction pairs in vacuum
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图 10 3种不同摩擦配副在真空中的摩擦机理图
Figure 10. Friction mechanism diagram of three different friction pairs in vacuum
表 1 3种薄膜的沉积参数
Table 1 Deposition parameters of the three films
Films Target current/A Deposition time/h Bias voltage/V Graphite MoS2 Ti MoS2-C 2 1.2 0 2 -40 а-C:H 7 0 0 2 -200 MoS2-Ti 0 1.2 0.4 2 -40 
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