氮气流量对不锈钢多弧离子镀 TiN 薄膜性能的影响

Effect of nitrogen flow rate on properties of TiN film deposited on stainless steel by multi-arc ion plating

摘要

[目的]研究氮气流量对多弧离子镀 TiN 薄膜微观结构、力学性能及光学特性的影响，为 TiN 薄膜在装饰领域的应用提供理论支撑与工艺指导。[方法]采用多弧离子镀技术，在 316L 不锈钢基体上通过改变氮气流量沉积一系列 TiN 薄膜，通过扫描电子显微镜、X 射线衍射仪、纳米压痕仪、球盘摩擦磨损试验机和台式分光测色仪分别对薄膜的表面形貌、相组成、纳米硬度、耐磨性和颜色进行了表征分析。[结果]所制备的 TiN 薄膜均为具有(111)晶面择优取向的面心立方结构。随着氮气流量增加，薄膜晶粒尺寸逐渐增大，Ti/N 原子比逐渐降低，表面颗粒数量先减后增，在 150 cm 3/min 时表面品质最优。当氮气流量为 50 cm 3/min 时，薄膜呈现富钛状态，纳米硬度达到 43.6 GPa，平均摩擦因数最低，耐磨性最佳。随着流量增大，硬度和耐磨性均呈下降趋势。在光学性能方面，150 cm 3/min 条件下制备的薄膜亮度 L 值最高，与纯金的色差 ΔE 最小，呈现出最接近黄金的色泽。[结论]通过调节氮气流量可有效调控多弧离子镀 TiN 薄膜的微观结构、力学性能及光学特性，其中 50 cm 3/min 适于制备高硬耐磨涂层，150 cm 3/min 则更适用于仿金装饰性涂层的制备。

Abstract

[Objective] The effect of nitrogen flow rate on the microstructure, mechanical properties, and optical characteristics of TiN films deposited by multi-arc ion plating needs to be studied to provide theoretical support and process guidance for the application of TiN films in the decorative field. [Method]A series of TiN films were deposited on 316L stainless steel substrates by multi-arc ion plating at various nitrogen flow rates. The surface morphology, phase composition, hardness, wear resistance, and color of the films were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), nanoindentation, ball-on-disc tribological testing, and a desktop spectrophotometer, respectively. [Result]All the deposited TiN films exhibited a face-centered cubic structure with a preferred (111) crystal orientation. As the nitrogen flow rate increased, the grain size of TiN film gradually increased, while the Ti-to-N atomic ratio decreased. The number of microparticles on film surface first decreased and then increased, with optimal surface quality achieved at a flow rate of 150 cm ³/min. The TiN film deposited at a nitrogen flow rate of 50 cm ³/min exhibited a Ti-rich state and optimal wear resistance as shown by the highest hardness of 43.6 GPa and the lowest average friction coefficient. With a further increase in nitrogen flow rate, both hardness and wear resistance showed a decreasing trend. Regarding optical properties, the film deposited at 150 cm ³/min exhibited the highest luminance value ( L*) and the lowest color difference (Δ E) compared to pure gold, displaying a color closest to that of gold. [Conclusion]The microstructure, mechanical properties, and optical characteristics of TiN films deposited by multi-arc ion plating can be effectively controlled by adjusting the nitrogen flow rate. The TiN film deposited at a nitrogen flow rate of 50 cm ³/min exhibits high hardness and excellent wear resistance, while the film deposited at 150 cm ³/min is more suitable for gold-like decorative coatings.

关键词

多弧离子镀 / 氮化钛薄膜 / 氮气流量 / 微观结构 / 力学性能 / 颜色

Key words

multi-arc ion plating / titanium nitride film / nitrogen flow rate / microstructure / mechanical property / color

参考文献

[1] CHATTERJEE D. Behind the development of advanced high strength steel (AHSS) including stainless steel for automotive and structural applications- an overview[J]. Materials Science and Metallurgy Engineering, 2017, 4 (1): 1-15.

[2] FAN C F, WANG X, WANG W, et al. Fabrication and properties of superhydrophobic colored stainless steel surface for decoration and anti-corrosion[J]. Coatings, 2024, 14(9): 1117.

[3] WOOD R J K, LU P. Coatings and surface modification of alloys for tribo-corrosion applications[J]. Coatings, 2024, 14(1): 99.

[4] YU Q H, PEI J X, HUANG J K, et al. Influence of alloy substrate treatment on microstructure and surface performances of arc-ion plated gold-like film[J]. Materials, 2019, 12(1): 180.

[5] MILSCHI L, BELAHSEN I, LAIN C G, et al. Optical and tribological properties of decorative titanium carbonitride coatings[J]. Surface Engineering, 2018, 34(7): 562-568.

[6] LAIN C G, CEMIN F, MENEZES M C, et al. Bias influence on titanium interlayer for titanium nitride films[J]. Surface Engineering, 2016, 32(4): 279-283.

[7] MAHAJAN U, DHONDE M, SAHU K, et al. Titanium nitride (TiN) as a promising alternative to plasmonic metals: a comprehensive review of synthesis and applications[J]. Materials Advances, 2024, 5(3): 846-895.

[8] ATTA S, NARENDRAKUMAR U, KUMAR K V A N P S, et al. Recent developments and applications of TiN-based films synthesized by magnetron sputtering[J]. Journal of Materials Engineering and Performance, 2023, 32(22): 9979-10015.

[9] NOVIKOV V, STEPANOV N, ZHEREBTSOV S, et al. Structure and properties of high-entropy nitride coatings[J]. Metals, 2022, 12(5): 847.

[10] SSENNYIMBA K W, NKELE A C, BYARUHANGA P, et al. Recent advances in titanium nitride (TiN) nanostructures and thin films for bio-sensing applications[J]. JOM, 2025, 77(6): 4286-4300.

[11] LI S S. Salt-assisted chemical vapor deposition of two-dimensional transition metal dichalcogenides[J]. iScience, 2021, 24(11): 103229.

[12] 梁愉, 李钰, 赵敏霞, 等. TiAlN 涂层对钛合金的热腐蚀防护作用研究[J]. 材料研究与应用, 2022, 16(6): 928-933.

[13] LIANG Y, LI Y, ZHAO M X, et al. Study on hot corrosion protection effect of TiAlN coating on titanium alloy[J]. Materials Research and Application, 2022, 16(6): 928-933.

[14] LIN X K, FAN D X, LI F Q, et al. Characterization of pulsed plasma nitriding and physical vapor deposition duplex-treated CrAlN coatings[J]. Thin Solid Films, 2025, 825: 140726.

[15] YAN D Y, XU W J, LI J F, et al. Effect of nitrogen/argon ratios on structures and properties of high-entropy (ZrTiNbV) N nitride films by multi-arc ion plating[J]. Vacuum, 2024, 225: 113173.

[16] 杨通晗, 朱晖朝, 李福球, 等. 周期数对Ti/TiN/Zr/ZrN 多层膜耐摩擦和耐腐蚀性能的影响[J]. 电镀与涂饰, 2025, 44(3): 103-111.

[17] YANG T H, ZHU H C, LI F Q, et al. Effect of cycle number on friction and corrosion resistance of Ti/TiN/Zr/ZrN multilayer film[J]. Electroplating & Finishing, 2025, 44(3): 103-111.

[18] 郑彩凤, 郭建云, 唐鹏, 等. 热力耦合对电弧离子镀 NiCoCrAlYHf 涂层/镍基单晶高温合金界面组织结构的影响[J]. 电镀与涂饰, 2023, 42 (18): 33-42.

[19] ZHENG C F, GUO J Y, TANG P, et al. Effect of thermodynamic coupling on microstructure of the interface between arc ion plated NiCoCrAlYHf coating and single-crystal nickel-based superalloy[J]. Electroplating & Finishing, 2023, 42 (18): 33-42.

[20] SAKTHINATHAN S, MEENAKSHI G A, VINOTHINI S, et al. A review of thin-film growth, properties, applications, and future prospects[J]. Processes, 2025, 13(2): 587.

[21] ICHOU H, ARROUSSE N, BERDIMURODOV E, et al. Exploring the advancements in physical vapor deposition coating: a review[J]. Journal of Bio- and Tribo-Corrosion, 2024, 10(1): 3.

[22] 向雄志, 马松峰, 白晓军. 铝黄铜仿金合金色度研究[J]. 特种铸造及有色合金, 2011, 31(9): 874-877.

[23] XIANG X Z, MA S F, BAI X J. Chromaticity of brass based stimulant gold alloy with al additions[J]. Special Casting & Nonferrous Alloys, 2011, 31(9): 874-877.

[24] CHEN Q S, YANG H Y, WU L, et al. Effect of the Ar/N₂ flow ratio on the microstructure, mechanical properties, and high-temperature steam oxidation behavior of Cr/Cr_xN coatings for accident-tolerant fuel coatings [J]. Corrosion Science, 2021, 192: 109833.

[25] GONG Z Y, CHEN R F, LI J, et al. Effect of N₂ flow rate on structure and corrosion resistance of AlCrN coatings prepared by multi-arc ion plating [J]. International Journal of Electrochemical Science, 2020, 15(2): 1117-1127.

[26] HUANG M D, LIN G Q, ZHAO Y H, et al. Macro-particle reduction mechanism in biased arc ion plating of TiN[J]. Surface and Coatings Technology, 2003, 176(1): 109-114.

[27] JIA H L, LIU X J, LI Z X, et al. The effect of grain size on the deformation mechanisms and mechanical properties of polycrystalline TiN: a molecular dynamics study[J]. Computational Materials Science, 2018, 143: 189-194.

[28] ZOU G P, WANG Q Q, SHENG R X, et al. Wear-resistant HfC_x film with infrared-visible compatible stealth property [J]. Ceramics International, 2025, 51(19): 28382-28393.

基金资助

五粮液集团公司产学研合作项目(CXY2022ZR001)

四川轻化工大学留学归国项目(2022RC15)

四川轻化工大学大创项目(cx2026003)