Effects of N<sub>2</sub>/Ar Flow Ratio on the Microstructure and Properties of TiZrN/TiN Nano-multilayer Films

Effects of N₂/Ar Flow Ratio on the Microstructure and Properties of TiZrN/TiN Nano-multilayer Films

WEI Yongqiang, ZHANG Huasen, ZHANG Xiaoxiao, GU Yanyang, LIU Chang, LYU Yidong, WEI Chunbei, ZHONG Sujuan

Surface Technology ›› 2025, Vol. 54 ›› Issue (14) : 92-104.

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Surface Technology ›› 2025, Vol. 54 ›› Issue (14) : 92-104. DOI: 10.16490/j.cnki.issn.1001-3660.2025.14.009

Corrosion and Protection

Effects of N₂/Ar Flow Ratio on the Microstructure and Properties of TiZrN/TiN Nano-multilayer Films

WEI Yongqiang^1,*, ZHANG Huasen¹, ZHANG Xiaoxiao¹, GU Yanyang¹, LIU Chang¹, LYU Yidong¹, WEI Chunbei², ZHONG Sujuan³

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Abstract

The work aims to investigate the changes of the microstructure and properties of TiZrN/TiN nano-multilayer films by varying the N₂/Ar flow ratio. TiZrN/TiN nano-multilayer films were deposited on M2 high-speed steel and single-crystal Si(100) substrates by a hybrid deposition technique of arc ion plating (AIP) and high-power impulse magnetron sputtering (HiPIMS), with controlled modulation of the N₂/Ar flow ratio during growth. The effects of the N₂/Ar flow ratio on the morphology, elemental composition, phase structure, nanohardness, adhesion strength, tribological properties, and corrosion resistance of TiZrN/TiN nano-multilayer films were analyzed systematically. As the N₂/Ar flow ratio increased from 25/75 to 35/65, the surface roughness of TiZrN/TiN nano-multilayer films initially increased and then decreased, with the minimum value of 0.298 μm at a N₂/Ar flow ratio of 35/65. As the flow ratio further increased to 40/60, the surface roughness reached a maximum of 0.387 μm, while the surface roughness decreased to 0.318 μm as the N₂/Ar flow ratio increased to 45/55. The thickness of the film initially increased before subsequently decreasing. As the N₂/Ar flow ratio increased 40/60, the film reached to a maximum thickness of 574 nm. All the TiZrN/TiN nano-multilayer films exhibited a preferential orientation along the (111) crystal plane. The hardness of these films ranged from 22.95 GPa to 27.15 GPa, which was more than 2.5 times that of M2 high-speed steel (9 GPa). At the N₂/Ar flow ratio of 25/75, the ion bombardment effect on the TiZrN/TiN nano-multilayer films was the most significant, corresponding to a relatively high Zr/(Ti+Zr) ratio of 0.088, which induced the hardness and the elastic modulus to 27.15 GPa and 271.14 GPa, respectively. At the N₂/Ar flow ratio of 45/55, the ion bombardment effect was the weakest and the Zr/(Ti+Zr) ratio decreased to a minimum of 0.058, which weakened the solid solution strengthening. The hardness and elastic modulus reached to the lowest values 22.95 GPa and 250.74 GPa, respectively. The adhesion of the TiZrN/TiN nano-multilayer films was optimal at N₂/Ar flow ratios of 25/75 and 30/70, achieving the highest level of HF1. All the stable coefficients of friction of TiZrN/TiN nano-multilayer films reached an average value ~0.8, while the wear rate increased at the initial stage, followed by a decrease with the increasing N₂/Ar flow ratio. At the N₂/Ar flow ratio of 25/75, the self-corrosion potential and self-corrosion current density of the TiZrN/TiN nano-multilayer films were -0.546 V and 1.167 μA/cm², respectively. The protective efficiency of the TiZrN/TiN nano-multilayer films for the M2 high-speed steel substrate reached a maximum of 87.9%. At the N₂/Ar flow ratio of 45/55, the self-corrosion potential of the TiZrN/TiN nano-multilayer films decreased to a minimum of -0.56 V, the self-corrosion current density increased to a maximum 2.011 μA/cm², and the protective efficiency for the substrate declined to a minimum of 79.15%, which indicated that the corrosion resistance weakened. The hybrid deposition technique of arc ion plating and high-power pulsed magnetron sputtering can be used to significantly improve the surface quality of the TiZrN/TiN nano-multilayer films. The N₂/Ar flow ratio can affect the intensity of ion bombardment. With the increasing N₂/Ar flow ratio, the intensity of ion bombardment gradually decreases, which results in a corresponding decline in film hardness and corrosion resistance. At the N₂/Ar flow ratio of 25/75, the TiZrN/TiN nano-multilayer films demonstrate optimal comprehensive performance. These results provide experimental guidance and potential applications for the further optimization of hybrid deposition technique and enhancement of film performance.

Key words

high power pulsed magnetron sputtering / arc ion plating / TiZrN/TiN nano-multilayer films / N₂/Ar flow ratio / nanohardness / wear resistance

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WEI Yongqiang, ZHANG Huasen, ZHANG Xiaoxiao, GU Yanyang, LIU Chang, LYU Yidong, WEI Chunbei, ZHONG Sujuan. Effects of N₂/Ar Flow Ratio on the Microstructure and Properties of TiZrN/TiN Nano-multilayer Films[J]. Surface Technology. 2025, 54(14): 92-104 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.14.009

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Funding

National Natural Science Foundation of China (51401182); State Scholarship Fund of China (CSC202108410274); Natural Science Foundation of Henan Province (242300420053); International Cultivation program of High-level Talents of Henan Province; Program of Open Project of the State Key Laboratory of New Brazing Materials and Technology (SKLABFMT-2023-09); Transformation Special Program and Scientific Research Team of Zhengzhou University of Aeronautics (23ZHTD01010); The Youth Research Funds Plan (24ZHQN01010); The Key and Major Achievements Cultivation

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