17-4PH钢表面沉积Ti-DLC梯度功能膜及其组织性能研究

发布时间：2018-07-01 08:38

  本文选题：类金刚石薄膜 + 微观组织结构　； 参考：《哈尔滨工业大学》2017年硕士论文

【摘要】：类金刚石(Diamond-like carbon,DLC)薄膜具有优异的力学(高的硬度和弹性模量、低摩擦系数)、电磁学、光学性能(增透减反)、生物相容性和化学稳定性等,已成为一种重要的新型功能膜。但是研究发现其主要存在内应力较大和热稳定性较差这两大问题。本文将采用闭合场非平衡磁控溅射离子镀(UBMS)技术制备不同钛含量掺杂的DLC梯度功能膜以期解决这两大问题,并探究钛含量对类金刚石薄膜微观组织结构和性能影响规律和机理。研究结果表明:所制备的Ti-DLC薄膜表面光滑平坦、膜层致密和颗粒均匀细小,其粗糙度Rq在8.45nm~21.6nm范围内。且钛靶电流从0.4A增大到0.8A,表面粗糙度升高。GXRD分析可知,Ti-DLC薄膜均在44.5°附近均出现了碳衍射峰,且都生成TiO和TiO_2纳米晶,此外钛靶电流为0.4A试样还形成了TiN_(0.3)纳米晶。XPS分析可知Ti-DLC薄膜表层元素主要以Ti-O和Ti-N键合形式存在,分别对应化合物是TiO、TiO_2和TiN_(0.3)。此外,C 1s XPS谱峰可分为sp~3 C峰、sp~2 C峰和C-O峰,通过对各键合面积积分求出不同钛靶电流的Ti-DLC薄膜sp~3C含量在49.03%~53.31%。研究发现较高的钛靶电流有利于sp~3 C成键,且随着钛靶电流从0.3A增加到1.0A,钛含量从0.82at.%增加到1.97at.%。较高的钛靶电流促使sp~3 C峰位向高位偏移和半高宽减小。Raman光谱分析可知除了钛靶电流为1.0A的Ti-DLC薄膜,其它薄膜D峰和G峰位置偏移很小,并求出ID/IG(RI)在1.1~1.7。纳米压痕分析可知,钛靶电流为0.4A的Ti-DLC薄膜具有最大的硬度(50.697GPa)和弹性模量(368.185GPa)。钛含量从0.82at.%增大到1.1at.%,其纳米硬度与弹性模量均增加;随后则出现相反的趋势。摩擦磨损性能分析可知,未处理基体发生了严重氧化磨损和黏着磨损,其磨痕宽度和深度分别约为700μm和100μm;而Ti-DLC薄膜只发生轻微的磨粒磨损,其磨痕宽度和深度分别约为80μm和0.1μm。与未处理基体相比,其摩擦系数最大降低了96.15%,磨损率最大降低了99.10%。综合考虑,钛靶电流为0.3A的Ti-DLC薄膜耐摩擦磨损性能最好。腐蚀性能分析可知,未处理基体表面腐蚀坑大而密(直径约为440μm),其微区元素主要为Cu、Fe和Cr,而Ti-DLC薄膜表面腐蚀坑小而疏(直径约为1μm),其微区元素仍以C和Ti元素为主。与未处理基体相比,镀膜试样具有更宽钝化区。其中钛靶电流为0.3A试样具有最低自腐蚀电流,0.4A试样具有最高点蚀电位和最宽钝化区,0.6A试样具有最高自腐蚀电位。综上所述,最佳的工艺为钛靶电流0.3A到0.5A。
[Abstract]:Diamond-like carbon (DLC) thin films with excellent mechanical properties (high hardness and elastic modulus, low friction coefficient), electromagnetics, optical properties (antireflection), biocompatibility and chemical stability have become an important new functional film. However, it is found that there are two main problems: high internal stress and poor thermal stability. In this paper, DLC gradient functional films doped with different titanium content will be prepared by closed field unbalanced magnetron sputtering ion plating (UBMS) in order to solve these two problems, and the effect of titanium content on microstructure and properties of diamond-like carbon films is investigated. The results show that the surface of Ti-DLC thin film is smooth and flat, the film is compact and fine, and its roughness RQ is in the range of 8.45nm~21.6nm. When the current of Ti target increases from 0.4A to 0.8A, the surface roughness increases. GXRD analysis shows that all Ti-DLC films have carbon diffraction peaks near 44.5 掳, and both TIO and TiO-2 nanocrystals are formed. In addition, TiN0.3 nanocrystalline. XPS analysis shows that the surface elements of Ti-DLC films mainly exist in the form of Ti-O and Ti-N bonding, and the corresponding compounds are TiOO _ 2O _ 2 and TiN _ (0.3) respectively. In addition, the peaks of C 1s XPS spectra can be divided into sp~3 C peaks and C O peaks. Through the integration of each bonding area, the content of SSP 3C of Ti-DLC thin films with different Ti target currents is 49.03 and 53.31. It is found that the higher titanium target current is beneficial to the bonding of sp~3 C, and the titanium content increases from 0.82at.% to 1.97at.with the titanium target current increasing from 0.3A to 1.0 A. The high Ti target current causes the sp~3 C peak to shift to a high position and the half-maximum width to decrease. Raman spectra show that, except for Ti-DLC thin films with 1.0 A Ti target current, the shift of D and G peaks in other films is very small, and the IDR / IG (RI) is found to be 1.1 ~ 1.7. Nano indentation analysis shows that Ti-DLC film with 0.4A target current has the highest hardness (50.697GPa) and elastic modulus (368.185GPa). When the titanium content increased from 0.82at.% to 1.1at.its nanohardness and elastic modulus increased, and then the reverse trend was observed. According to the analysis of friction and wear properties, serious oxidation wear and adhesion wear occurred in untreated substrate, the width and depth of wear mark were about 700 渭 m and 100 渭 m, respectively, while that of Ti-DLC film was only slightly abrasive wear, the width and depth of wear trace were about 80 渭 m and 0.1 渭 m, respectively. Compared with the untreated matrix, the maximum friction coefficient and wear rate are reduced 96.15 and 99.10% respectively. Considering the friction and wear resistance of Ti-DLC thin films with target current of 0.3A, the friction and wear resistance of Ti-DLC thin films is the best. The corrosion performance analysis shows that the corrosion pits on the surface of untreated substrates are large and dense (about 440 渭 m), in diameter), and the microelements are mainly Cu Fe and Cr, while the corrosion pits on the surface of Ti-DLC films are small and sparse (about 1 渭 m), in diameter). Compared with the untreated substrate, the coated sample has a wider passivation zone. The titanium target current of 0.3A has the lowest self-corrosion current of 0.4A and the highest pitting potential of 0.4A and the highest self-corrosion potential of 0.6A with the widest passivation region. To sum up, the best process is titanium target current 0.3A to 0.5A.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TG174.45
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本文编号：2087197