【作者】 张琦；

【导师】 冷永祥；

【作者基本信息】 西南交通大学 ， 材料学， 2007， 硕士

【摘要】 本论文采用非平衡磁控溅射技术制备出不同成分、结构和性能的Ti-N，Ti／TiN多层膜和SiNx薄膜。利用AMBIOS XP-2台阶仪测量薄膜的厚度。使用X射线衍射（XRD）、X射线光电子能谱（XPS）、红外吸收光谱（FTIR）、扫描电镜（SEM）对薄膜的结构和成分进行了表征。采用CSEM球盘摩擦磨损实验机、HXD-1000 knoop显微硬度仪、WS-92划痕试验机等研究了薄膜的机械性能。由于薄膜的应用场合不同，不同的薄膜采用不同的方法评价其耐腐蚀性能。重点研究了氮气和氩气分压比(P_N2／P_Ar)和基体偏压的变化对Ti-N薄膜结构和性能的影响；调制周期对Ti／TiN多层膜结构和性能的影响；氮气和氩气分压比(P_N2／P_Ar)的变化对SiNx薄膜结构和性能的影响。不同氮气和氩气分压比(P_N2／P_Ar)和基体偏压下制备出了不同结构和性能的氮化钛薄膜，结果表明，采用非平衡磁控溅射技术制备出了致密的氮化钛薄膜，当P_N2／P_Ar较小时，氮化钛薄膜中存在Ti₂N相，随着P_N2／P_Ar的增大氮化钛薄膜中Ti₂N相逐渐减少，主要以TiN相存在。Ti₂N相的存在有效提高了氮化钛薄膜的硬度和耐磨损性能。由于TiN具有高硬度，出色的耐磨损性和化学稳定性而被广泛应用于机械工程方面，但是采用物理气相沉积技术制备的TiN薄膜往往存在明显的柱状晶结构，这些柱状晶之间的分界处容易导致TiN薄膜的失效。多层膜结构可以解决这个问题，因为多层膜结构中的界面可以有效阻止柱状晶的生长。调制周期是影响多层薄膜性能的最主要的因素。本文采用非平衡磁控溅射技术制备了100nm～350nm调制周期的Ti／TiN多层薄膜。结果显示，不同调制周期下制备的Ti／TiN多层薄膜呈现出了很好的周期性。随着调制周期的减小，Ti／TiN多层薄膜的生长变得更加致密，晶粒更加细小。Ti／TiN多层薄膜的显微硬度和耐磨损性能也随调制周期的减小而增强。3％NaCl溶液中的电化学腐蚀实验显示在不锈钢基体表面制备Ti／TiN多层薄膜可以提高基体的耐腐蚀性能。高温水蒸气循环实验结果表明，Ti／TiN多层薄膜的耐腐蚀性能随着调制周期的减小而减弱。非平衡磁控溅射技术在钛合金（Ti₆Al₄V）表面沉积SiNx薄膜，研究结果表明，随着P_N2／P_Ar的增加，Si-N键的含量增加，吸收峰(870～930cm^-1)向高波数偏移，吸收峰(475～490cm^-1)的峰强增加。SiNx薄膜的显微硬度、耐磨性随着P_N2／P_Ar的增加而增加，当P_N2／P_Ar增加到0.25时，薄膜硬度、耐磨性开始随着P_N2／P_Ar的增加有下降趋势。薄膜与基体之间的膜／基结合力的测试结果表明薄膜与基体结合力较好，薄膜的脆性随着P_N2／P_Ar的增加而增加。更多还原

【Abstract】 Titanium nitride, Ti/TiN multilayer films and silicon nitride with different composition, microstructure, mechanical and corrosion resistance properties were synthesized by unbalanced magnetron sputtering. The films thickness was tested by AMBIOS Xp-2 profile meter. The microstructure and composition were characterized with X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, Fourier Transform Infrared Spectroscopy （FTIR） spectroscopy and scanning electron microscopy （SEM）. The mechanical properties, such as microhardness, wear resistance and the adhesion strength between films and substrate, were characterized with HXD～1000 microhardness meter, CSEM pin-on-disk wear test apparatus and WS-97 scratch tester. The corrosion resistance of films was characterized with different method because of the different application of the films.The effect of the N₂ and Ar partial pressure ratio (P_N2/P_Ar and bias voltage on Ti-N film microstructure and properties were studied; the effect of the periods on the Ti/TiN multilayer films were analyzed; the effect of the N₂ and Ar partial pressure ratio (P_N2/P_Ar) on Si-N film microstructure and properties were studied.The titanium nitride films with different microstructure and properties were synthesized at different N₂ and Ar partial pressure ratio (P_N2/P_Ar) and bias voltage by unbalanced magnetron sputtering. The results showed that Ti-N films deposited by unbalance magnetron sputtering were compact. The Ti₂N phases were found in the Ti-N films, and Ti₂N dexreased with N₂ and Ar partial pressure ratio (P_N2/P_Ar) increasing. The Ti₂N existed in the films can significantly improve the microhardness and wear resistance of the Ti-N films.Titanium nitride films have been widely applied in mechanical engineering due to their high hardness, excellent wear resistance and good chemical stability. However, monolayer films of TiN deposition by PVD techniques, generally have a columnar microstructure, and these columnar grain boundaries always result in failure of TiN films.It has been reported that the multilayered structure can be used to overcome this problem since the interfaces between the layers can periodically interrupt the growth of columnar grain. The properties of the multilayer films were mostly influenced by the periods. In this paper Ti/TiN multilayer films with periods from 100nm to 350nm were synthesized by unbalanced magnetron sputtering. The SEM images demonstrate that the Ti/TiN multilayer films with different periods were produced at an excellent periodicity. The crystal grain of the Ti/TiN multilayer films became more compact as the decrease of the period. The micro-hardness and wear resistance of the multilayer films increased with the periods decreasing. The potentiodynamic polarization scans in 3% NaCl solution showed that the Ti/TiN multilayer films can be used to significantly improve the corrosive resistance of the stainless steel.The thermal humid exposure showed that the corrosion resistance of the multilayer films decreased with the period decreasing.It is indicated that all the SiN_x films synthesized at different N₂ and Ar partial pressure ratio (P_N2/P_Ar) by unbalanced magnetron sputtering. The results showed that the absorption band observed at 870～930cm^-1 corresponds to Si-N /Si-O was shifted to left because of having more Si-N bonds with increasing the N₂ and Ar partial pressure ratio (P_N2/P_Ar). Besides, the additional absorption bands correspond to Si-N observed at 475～490cm^-1 became obvious when the P_N2/P_Ar increasing. Micro-hardness test and wear resistance test results showed that the hardness and wear resistance increased when the P_N2/P_Ar increasing, then decreased slightly when the P_N2/P_Ar increasing. The adhesion strength between films and substrate was well, and the brittleness of the Si-N films increased when the P_N2/P_Ar increasing.更多还原