退火温度对磁控溅射TiN/TiCN薄膜残余应力、结构及耐蚀性能的影响

doi:10.13251/j.issn.0254-6051.2021.05.027

摘要/Abstract

摘要： 采用反应磁控溅射在AZ31合金上制备了TiN/TiCN薄膜,并对沉积后的薄膜进行真空去应力退火。分别采用X射线荧光光谱仪(XRF)、扫描电镜(SEM)、掠入射X射线衍射(GIXRD)和电化学工作站对退火前后的薄膜进行表面化学成分、形貌结构、残余应力以及耐蚀性能分析。结果表明:薄膜由FCC结构的TiCN和TiN组成。退火后,薄膜的晶粒尺寸和结晶度增大,内部残余应力显著下降,电化学腐蚀区域的Ti、C、N元素含量下降,250 ℃退火薄膜的耐蚀性能与沉积态薄膜相当,300 ℃退火后薄膜的耐蚀性能下降。

关键词: 退火温度, TiN/TiCN薄膜, 磁控溅射, 残余应力, 结构, 耐蚀性

Abstract: TiN/TiCN film was prepared on AZ31 alloy by reactive magnetron sputtering and the deposited film was subjected to vacuum stress relief annealing. X-ray fluorescence spectrometer (XRF), scanning electron microscope (SEM), grazing incidence X-ray diffraction(GIXRD) and electrochemical workstation were used to analyze the surface chemical composition, surface morphology, residual stress and corrosion resistance of all the films before and after annealing. The results show that the films are composed of TiCN and TiN with FCC structure. After annealing, the grain size and crystallinity of the films increase, the residual stress decreases significantly, the content of Ti, C and N elements in the electrochemical corrosion area decreases, the corrosion resistance of the film annealed at 250 ℃ is equivalent to that of the deposited film, and the corrosion resistance of the film annealed at 300 ℃ decreases.

Key words: annealing temperature, TiN/TiCN films, magnetron sputtering, residual stress, structure, corrosion resistance

中图分类号:

TG178.2

云璐, 郝新. 退火温度对磁控溅射TiN/TiCN薄膜残余应力、结构及耐蚀性能的影响[J]. 金属热处理, 2021, 46(5): 166-170.

Yun Lu, Hao Xin. Effect of annealing temperature on residual stress, structure and corrosion resistance of magnetron sputtering TiN/TiCN film[J]. Heat Treatment of Metals, 2021, 46(5): 166-170.

参考文献

[1]Altun H, Sen S. The effect of PVD coatings on the corrosion behaviour of AZ91 magnesium alloy[J]. Materials and Design, 2006, 27: 1174-1178.
[2]Wu G S, Wang X M, Ding K J, et al. Corrosion behavior of Ti-Al-N/Ti-Al duplex coating on AZ31 magnesium alloy in NaCl aqueous solution[J]. Materials Characterization, 2009, 60(8): 803-807.
[3]刘瑞霞, 郭锋, 韩海鹏. 铬过渡层对氮化铬/镁合金膜基界面结合强度的影响[J]. 金属热处理, 2021, 46(1): 143-148.
Liu Ruixia, Guo Feng, Han Haipeng. Effect of chromium transition layer on interface bonding strength betweenchromium nitride film and magnesium alloy substrate[J]. Heat Treatment of Metals, 2021, 46(1): 143-148.
[4]肖璐, 潘复生. 含铈镁合金组织和性能的研究进展[J]. 金属热处理, 2019, 44(10): 230-235.
Xiao Lu, Pan Fusheng. Research status of microstructure and properties of magnesium alloys containing cerium[J]. Heat Treatment of Metals, 2019, 44(10): 230-235.
[5]吴劲峰, 何乃如, 邱孟柯, 等. N₂流量对中频非平衡磁控溅射TiAlN薄膜结构及性能的影响[J]. 功能材料, 2013, 44(1): 32-35.
Wu Jinfeng, He Nairu, Qiu Mengke, et al. Influence of nitrogen flows on structure and properties of TiAlN film prepared by mid-frequency unbalance magnetron sputtering[J]. Journal of Functional Materials, 2013, 44(1): 32-35.
[6]潘应晖, 许晓静. Ti₆Al₄V表面磁控溅射高硬SiC薄膜的摩擦磨损性能[J]. 材料工程, 2013(6): 63-66.
Pan Yinghui, Xu Xiaojing. Friction/wear properties of magnetron sputtered high-hard SiC films on Ti₆Al₄V alloy[J]. Materials Engineering, 2013(6): 63-66.
[7]Wu Guosong, Zeng Xiaoqin, Li Geyang, et al. Preparation and characterization of ceramic/metal duplex coatings deposited on AZ31 magnesium alloy by multi-magnetron sputtering[J]. Materials Letters, 2006, 60(5): 674-678.
[8]朱生发, 刘天伟, 吴艳萍, 等. 铀表面非平衡磁控溅射离子镀Ti基薄膜的组织结构与腐蚀性能[J]. 真空科学与技术学报, 2012, 32(3): 240-242.
Zhu Shengfa, Liu Tianwei, Wu Yanping, et al. Microstructures and corrosion resistance of Ti-based films deposited on depleted uranium[J]. Journal of Vacuum Science and Technology, 2012, 32(3): 240-242.
[9]万松峰, 丁佳伟. 退火对磁控溅射AlCrNbSiTiV高熵合金氮化薄膜性能的影响[J]. 电镀与涂饰, 2020, 39(5): 263-267.
Wan Songfeng, Ding Jiawei. Effect of annealing on properties of AlCrNbSiTiV high-entropy alloy nitride films prepared by magnetron sputtering[J]. Electroplating and Finishing, 2020, 39(5): 263-267.
[10]严永林, 郑勇, 于海军, 等. 氮碳化钛涂层制备技术的研究进展[J]. 材料导报, 2007, 21(7): 55-58.
Yan Yonglin, Zheng Yong, Yu Haijun, et al. Research development of the preparation technology of titanium carbonitride coating[J]. Materials Reports, 2007, 21(7): 55-58.
[11]汪蕾, 董师润, 尤建飞, 等. Ti(C, N)复合膜和TiN/Ti(C, N)多层膜组织和显微硬度[J]. 材料热处理学报, 2010, 31(2): 113-118.
Wang Lei, Dong Shirun, You Jianfei, et al. Microstructure and microhardness of Ti(C, N) and TiN/Ti(C, N) multilayer films[J]. Transactions of Materials and Heat Treatment, 2010, 31(2): 113-118.
[12]吴坤尧, 代闯, 惠晶, 等. 磁控溅射制备CrAlN薄膜的高温抗氧化性[J]. 金属热处理, 2019, 44(7): 186-189.
Wu Kunyao, Dai Chuang, Hui Jing, et al. High temperature oxidation resistance of CrAlN films prepared by magnetron sputtering[J]. Heat Treatment of Metals, 2019, 44(7): 186-189.
[13]Liu H X, Xu Q, Zhang X W, et al. Residual stress analysis of TiN film fabricated by plasma immersion ion implantation and deposition process[J]. Nuclear Instruments and Methods in Physics Research B, 2013, 297: 1-6.
[14]Chen Z, Prud'homme N, Wang B, et al. Residual stress gradient analysis with GIXRD on ZrO₂ thin films deposited by MOCVD[J]. Surface Coat Technology, 2011, 206(2/3): 405-410.
[15]李慕勤, 庄明辉, 尹柯, 等. 高速火焰喷涂钛-生物玻璃涂层残余应力分析[J]. 焊接学报, 2009, 30(2): 65-67.
Li Muqin, Zhuang Minghui, Ying Ke, et al. Residual stress analysis on the Ti-bioglass coatings produced by high velocity flame spraying[J]. Transactions of the China Welding Institution, 2009, 30(2): 65-67.
[16]李海涛, 李慕勤, 韩涛, 等. TIG焊对低合金钢焊缝金属元素分布状态的影响[J]. 焊接学报, 2012, 33(4): 89-90.
Li Haitao, Li Muqin, Han Tao, et al. Element distribution in weld metal of low alloy steel of TIG welding[J]. Transactions of the China Welding Institution, 2012, 33(4): 89-90.
[17]Sharma S K, Kim D Y. Abnormal residual stress in nanostructured Al thin films grown on Ti/glass substrates[J]. Current Applied Physics, 2013, 13(9): 1874-1879.
[18]曹慧, 郭玉利, 韩晓雷. 不同负偏压下磁控溅射纳米TiAlN薄膜的微观结构与耐蚀性能[J]. 材料保护, 2018, 51(12): 18-22.
Cao Hui, Guo Yuli, Han Xiaolei. Microstructure and corrosion resistance of nano TiAlN coatings prepared by magnetron sputtering under different negative bias[J]. Material Protection, 2018, 51(12): 18-22.