目的 研究氮气流量比（RN2）对(TiSiAlCrV)N薄膜化学成分、相组成、沉积速率、微观结构及性能的影响,提高65Mn钢的耐磨和耐蚀性能。方法 使用相位可控三靶高功率脉冲磁控共溅射,在不加热条件下制备(TiSiAlCrV)N高熵合金氮化物薄膜,通过掠入射X射线衍射仪、纳米压痕仪、摩擦磨损试验机和电化学工作站分别测试薄膜物相、硬度（H）和弹性模量（E）、耐磨性能、耐蚀性能,并通过扫描电子显微镜、能谱仪和白光干涉仪表征薄膜的化学成分、表面形貌、截面形貌及磨痕形貌。结果 (TiSiAlCrV)N薄膜均具有NaCl（B1）型FCC结构,氮气流量比不影响薄膜物相。随着RN2的增大,薄膜氮元素含量略有增加,沉积速率逐渐减小,晶格常数逐渐增大,晶粒尺寸逐渐减小;在RN2为25%时,薄膜的择优取向为(220),其他RN2薄膜的择优取向为(111);薄膜的H、H/E、H3/E2随着RN2的增大而增大,当RN2为66.7%时达到最大值,分别约为14.77 GPa、0.071、0.075 GPa;在RN2为66.7%时,薄膜的磨损率最低,约为6.84× 10-6 mm3/(N·m),其磨损机制为磨粒磨损和氧化磨损,其他RN2薄膜磨损机制均为磨粒磨损、疲劳磨损和氧化磨损;RN2为66.7%时薄膜的结构致密,具有最优的耐蚀性能。结论 (TiSiAlCrV)N高熵合金氮化物薄膜可有效提高65Mn钢的耐磨和耐蚀性能,RN2为66.7%时薄膜具有最优的耐磨和耐蚀性能。
Abstract
High-entropy alloy films exhibit high hardness, excellent wear resistance, and corrosion resistance. Magnetron sputtering is usually used to fabricate high-entropy alloy films, especially for the preparation of high-entropy alloy nitride films by reactive sputtering. Magnetron sputtering can be divided into direct-current magnetron sputtering (DCMS), radio-frequency magnetron sputtering (RFMS), and high-power impulse magnetron sputtering (HiPIMS), etc. According to the number of targets, magnetron sputtering can be divided into single-target magnetron sputtering and multi-target magnetron co-sputtering. Compared with single-target sputtering, multi-target co-sputtering can improve the deposition rate, and effectively control the corresponding target element content in the film by adjusting the process parameters. HiPIMS has the characteristics of low duty cycle and high peak power on the target surface, which can highly ionize the sputtered material with a low average power. By bombarding the substrate with a high-energy ion beam, the phase composition and microstructure of the films can be effectively controlled, and the low-temperature preparation of dense high-entropy alloy films can even be achieved. Furthermore, the interval between the discharge voltage pulses for each sputtering target in high-power impulse magnetron co-sputtering must be determined to broaden the process window, enhance the glow discharge stability, and ensure uniformity of the film composition and microstructure as well as experimental repeatability. Thus, the three-target high-power impulse magnetron co-sputtering with controllable time interval between pulses is employed to deposit high-entropy alloy nitride films.
65Mn steel and single-crystalline Si (100) were used as substrates. Prior to the (TiSiAlCrV)N films, a TiSiAlCrV buffer layer with the thickness of 200-250 nm was prepared on the substrates to increase the adhesion. (TiSiAlCrV)N high-entropy alloy nitride films were prepared via three-target high-power impulse magnetron co-sputtering without substrate heating. TiSi alloy target, AlCr alloy target, and V target were used and the interval between voltage pulses of these targets was controlled. The nitrogen content was controlled by varying the flow ratio of N2/(Ar+N2) from 25% to 66.7%, donated as RN2. The effect of RN2 on the chemical composition, phase composition, deposition rate, microstructure, and properties of the (TiSiAlCrV)N films was investigated. The phase composition, hardness (H) and elastic modulus (E), wear and corrosion resistance of the films were analyzed respectively through glancing incidence X-ray diffraction (GIXRD), nano-indenter, tribometer, and electrochemical workstation. The scanning electron microscope (SEM) equipped with energy-dispersive spectrometry (EDS) and a white-light interferometer were used to test the chemical composition, surface and cross-sectional morphologies, and wear tracks.
The results indicated that the nitrogen flow ratio did not alter the phase composition of the film and all the (TiSiAlCrV)N films had NaCl (B1) type FCC structure. As RN2 increased, the nitrogen content of the film increased slightly, the deposition rate decreased, the lattice constant increased, and the grain size decreased, reaching the minimum value of 6.7 nm at 66.7%. The preferential orientation was the (220) plane when the film was fabricated at RN2 of 25%, and it was altered to the (111) plane with RN2 increasing to 40%, 50%, 57.1% and 66.7%. The H, H/E, and H3/E2 increased with RN2 increasing, and reached their maximum values of about 14.77 GPa, 0.071 and 0.075 GPa, respectively, at RN2 of 66.7%. The film deposited at RN2 of 66.7% has the lowest wear rate of around 6.84×10-6 mm3/(N·m), indicating the highest wear resistance. This film shows abrasive and oxidation wear mechanisms, whereas films fabricated at RN2 of 25%, 40%, 50% and 57.1% experience abrasive, fatigue, and oxidation wear. All films can provide effective corrosion protection for 65Mn steel in simulated soil solution. The film prepared at RN2 of 66.7% has the best corrosion resistance due to the dense structure.
关键词
高功率脉冲磁控共溅射 /
氮气流量比 /
高熵合金氮化物薄膜 /
摩擦磨损 /
腐蚀
Key words
high-power impulse magnetron co-sputtering /
nitrogen flow ratio /
high-entropy alloy nitride films /
friction and wear /
corrosion
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基金
山西省基础研究计划（202203021212467,202403021221075）; 山西省回国留学人员科研资助项目（2022-092）; 山西农业大学大学生创新训练计划（S202510113057）
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