目的 探究氮气流量比对(Al0.5CoCrFeNiTi)Nx薄膜化学成分、微观结构及性能的影响规律,提升GCr15轴承钢表面的力学性能和耐腐蚀性能。方法 采用高功率脉冲磁控溅射和直流磁控溅射复合方法,在GCr15轴承钢表面双靶共溅射(Al0.5CoCrFeNiTi)Nx高熵氮化物薄膜,通过X射线衍射仪、扫描电子显微镜、能谱仪、原子力显微镜对薄膜物相结构、微观形貌、化学成分、表面粗糙度进行表征,通过纳米压痕仪器、电化学工作站分别测试硬度（H）、弹性模量（E）和耐腐蚀性能。结果 随着氮气引入与增加,薄膜从非晶态转变为包含TiN、CrN等多种氮化物相的纳米晶结构;随N2/(N2+Ar)比值RN2增大,“Al原子比”占“高熵元素原子比和”的百分含量由7.91%提升至9.89%（逐渐接近高熵靶材设计配比）,Ti元素在金属元素中的占比由47.62%降低至36.14%;随RN2增大,薄膜的H、H/E、H3/E2呈增大趋势,当RN2为40%时达到最大,分别为22.694 GPa、0.069、0.110 GPa。当RN2为20%时,耐腐蚀性能最为优异,腐蚀电位较GCr15基体提升37.895%,较不通氮气薄膜提升18.146%,腐蚀电流密度较GCr15基体下降68.091%,较不通氮气薄膜下降58.514%。结论 (Al0.5CoCrFeNiTi)N0.2薄膜能够有效提升GCr15轴承钢的耐腐蚀性能,N元素的引入能够显著提高(Al0.5CoCrFeNiTi)高熵合金薄膜的硬度和耐腐蚀性能。
Abstract
As a more advanced surface modification technique, HiPIMS/DCMS hybrid magnetron sputtering fully leverages the synergistic advantages of the highly ionized plasma of HiPIMS (which enhances densification and interfacial adhesion of films) and the high deposition rate of DCMS (which ensures process efficiency) compared with individual HiPIMS or DCMS processes. In this study, an innovative method is employed with a high-power impulse power supply to sputter the Al0.5CoCrFeNi high-entropy alloy target, while a DC power supply is concurrently used to sputter the high-purity Ti target, so as to achieve precise control and efficient co-deposition of multiple metallic elements. By systematically adjusting the nitrogen flow ratio (RN2), the influence of reactive gas concentration on film composition evolution, crystalline structure transformation, and performance is thoroughly investigated. A SP-0606ASI magnetron sputtering vacuum coating system is employed for the hybrid deposition experiments. (Al0.5CoCrFeNiTi)Nx high-entropy nitride films are deposited on polished and cleaned GCr15 bearing steel and silicon wafer substrates at different nitrogen flow ratios (0, 10%, 20%, 30%, and 40% by volume). During deposition, a Ti interlayer is first deposited at a constant current of 5 A for 10 minutes, followed by co-deposition of the functional (Al0.5CoCrFeNiTi)Nx high-entropy nitride layer via HiPIMS (constant power: 1.5 kW, pulse width: 40 μs, pulse frequency: 25 000 Hz, deposition time: 80 min) combined with DCMS (constant current: 7 A, deposition time: 80 min). Film microstructure and thickness are characterized by scanning electron microscopy (SEM), elemental composition at selected points is analyzed by energy-dispersive spectroscopy (EDS), and phase composition of the films is characterized by X-ray diffraction (XRD). Film hardness and elastic modulus are measured via nanoindentation (TI980). The electrochemical corrosion behavior of the films in a 3.5% NaCl solution is evaluated with a three-electrode system on a Princeton electrochemical workstation, and the electrochemical impedance spectra are fitted using Zview software. Nanocrystalline (Al0.5CoCrFeNiTi)Nx high-entropy nitride films are successfully fabricated on GCr15 bearing steel and silicon wafer substrates via HiPIMS/DCMS hybrid magnetron sputtering. With the introduction and increase of nitrogen, the films transition from an amorphous state to a nanocrystalline structure consisting of multiple nitride phases such as TiN and CrN. As the N2/(N2+Ar) ratio (RN2) increases, the atomic percentage of Al relative to the total high-entropy elements increases from 7.91% to 9.89% (gradually approaching the designed target composition), while the Ti proportion among metallic elements decreases from 47.62% to 36.14%. With the increasing RN2, film hardness (H) increases from 10.317 GPa to 22.7 GPa, while H/E and H3/E2 values increase simultaneously to 0.069 and 0.110 GPa, respectively. At RN2=40%, the hardness of the (Al0.5CoCrFeNiTi)N0.4 high-entropy nitride film is 119.967% higher than that of the Al0.5CoCrFeNiTi metallic film. At RN2=20%, the film exhibited optimal corrosion resistance: the corrosion potential increasing by 37.895% relative to the GCr15 substrate and by 18.146% compared with the nitrogen-free film, while the corrosion current density decreases by 68.091% and 58.514%, respectively. Simultaneously, its hardness (16.579 GPa) remains 60.696% higher than that of the nitrogen-free film. The introduction of nitrogen significantly improves both the hardness and corrosion resistance of (Al0.5CoCrFeNiTi) high-entropy alloy films. At the optimal nitrogen flow ratio (RN2=20%), the films exhibit the best corrosion performance along with excellent mechanical properties. Appropriate nitrogen incorporation not only enhances interfacial integrity but also effectively inhibits the penetration corrosive media. This study confirms that precise control of nitrogen flow can optimize the structure and performance of high-entropy nitride films, providing essential theoretical and technical guidance for the development of novel protective coatings suitable for harsh service environments.
关键词
高熵氮化物薄膜 /
高功率脉冲磁控溅射 /
复合磁控溅射 /
纳米晶 /
硬度 /
耐腐蚀性能
Key words
high-entropy nitride films /
high power impulse magnetron sputtering /
hybrid magnetron sputtering /
nanocrystalline /
hardness /
corrosion resistance
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
参考文献
[1] TSAI K Y, TSAI M H, YEH J W.Sluggish Diffusion in Co-Cr-Fe-Mn-Ni High-Entropy Alloys[J]. Acta Materialia, 2013, 61(13): 4887-4897.
[2] 蔡静雯, 冯璇璇, 王杭宁, 等. CoCrFeNi系高熵合金耐腐蚀性能研究进展[J]. 中国有色金属学报, 2024, 34(12): 3899-3922.
CAI J W, FENG X X, WANG H N, et al.Research Progress on Corrosion Resistance of CoCrFeNi-Based High Entropy Alloys[J]. The Chinese Journal of Nonferrous Metals, 2024, 34(12): 3899-3922.
[3] LEE C, SONG G, GAO M C, et al.Lattice Distortion in a Strong and Ductile Refractory High-Entropy Alloy[J]. Acta Materialia, 2018, 160: 158-172.
[4] 盛颖航, 王凯, 高鹏, 等. 高熵合金耐腐蚀性能研究现状与展望[J]. 材料保护, 2024, 57(12): 53-66.
SHENG Y H, WANG K, GAO P, et al.Research Status and Prospects of Corrosion Resistance of High Entropy Alloys[J]. Materials Protection, 2024, 57(12): 53-66.
[5] NAIZABEKOV A, SAMODUROVA M, BODROV E, et al.Use of Laser Cladding for the Synthesis of Coatings from High-Entropy Alloys Reinforced with Ceramic Particles[J]. Case Studies in Construction Materials, 2023, 19: e02541.
[6] WANG Y Q, WANG R J, LIN J, et al.Mechanical and High-Temperature Wear Resistance Properties of WC- Reinforced AlCoCrFeNiTi0.5 High Entropy Alloy Matrix Composite[J]. Ceramics International, 2024, 50(1): 2162-2176.
[7] GUO Y J, LI C G, ZENG M, et al.In-Situ TiC Reinforced CoCrCuFeNiSi0.2 High-Entropy Alloy Coatings Designed for Enhanced Wear Performance by Laser Cladding[J]. Materials Chemistry and Physics, 2020, 242: 122522.
[8] 汪震, 尚晓娟, 贾义旺, 等. 高熵合金涂层微观结构与服役性能的研究进展[J]. 材料保护, 2025, 58(7): 1-18.
WANG Z, SHANG X J, JIA Y W, et al.Research Progress on the Microstructure and Service Performance of High-Entropy Alloy Coatings[J]. Materials Protection, 2025, 58(7): 1-18.
[9] 黄灿, 杜翠薇, 代春朵, 等. 高熵合金涂层的研究进展[J]. 表面技术, 2019, 48(11): 15-22.
HUANG C, DU C W, DAI C D, et al.Research Progress of High-Entropy Alloy Coatings[J]. Surface Technology, 2019, 48(11): 15-22.
[10] FU Y, HUANG C, DU C W, et al.Evolution in Microstructure, Wear, Corrosion, and Tribocorrosion Behavior of Mo-Containing High-Entropy Alloy Coatings Fabricated by Laser Cladding[J]. Corrosion Science, 2021, 191: 109727.
[11] 李平, 陈金凯, 周晓东, 等. 高熵合金涂层的研究进展[J]. 材料保护, 2015, 48(4): 44-46.
LI P, CHEN J K, ZHOU X D, et al.Research Progress of High Entropy Alloy Coatings[J]. Materials Protection, 2015, 48(4): 44-46.
[12] 李伟华, 周文杰, 宋宝睿, 等. 防腐耐磨高熵合金涂层研究进展[J]. 材料导报, 2026, 40(2): 136-146.
LI W H, ZHOU W J, SONG B R, et al.Research Progress on the Tribo-and Corrosion-Resistant High-Entropy Alloy Coatings[J]. Materials Reports, 2026, 40(2): 136-146.
[13] 吴厚朴, 田修波, 张新宇, 等. 双脉冲HiPIMS放电特性及CrN薄膜高速率沉积[J]. 金属学报, 2019, 55(3): 299-307.
WU H P, TIAN X B, ZHANG X Y, et al.Discharge Characteristics of Novel Dual-Pulse HiPIMS and Deposition of CrN Films with High Deposition Rate[J]. Acta Metallurgica Sinica, 2019, 55(3): 299-307.
[14] WANG W R, WANG W L, YEH J W.Phases, Microstructure and Mechanical Properties of Al x CoCrFeNi High-Entropy Alloys at Elevated Temperatures[J]. Journal of Alloys and Compounds, 2014, 589: 143-152.
[15] 沙明红. CoCrFeNi-M高熵合金的制备、结构及性能研究[D]. 鞍山: 辽宁科技大学, 2021: 64-124.
SHA M H.Study on Preparation, Microstructure, and Properties of High Entropy Alloys CoCrFeNi-M[D]. Anshan: University of Science and Technology Liaoning, 2021: 64-124.
[16] LIU J H, LV Z J, WU Z F, et al.Research Progress on the Influence of Alloying Elements on the Corrosion Resistance of High-Entropy Alloys[J]. Journal of Alloys and Compounds, 2024, 1002: 175394.
[17] KUMAR T S, SOURAV A, MURTY B S, et al.Role of Al and Cr on Cyclic Oxidation Behavior of AlCoCrFeNi2 High Entropy Alloy[J]. Journal of Alloys and Compounds, 2022, 919: 165820.
[18] YUAN Z P, YANG Z K, LU Y F, et al.Microstructure Characterization and Corrosion Resistance of Eutectic and Near-Eutectic AlCoCrFeNi High-Entropy Alloys[J]. Journal of Materials Research and Technology, 2025, 36: 8367-8379.
[19] GAWEL R, ROGAL Ł, SMOŁA G, et al. High- Temperature Oxidation and Diffusion Studies on Selected Al-Cr-Fe-Ni High-Entropy Alloys for Potential Application in Thermal Barrier Coatings[J]. Intermetallics, 2024, 169: 108273.
[20] ODABAS O, OZGURLUK Y, KARAOGLANLI A C.Comparison of High Temperature Hot Corrosion Behavior of AlCoCrFeNiTi and AlCoCrFeNiZr High Entropy Alloy (HEAs) Coatings[J]. Surface and Coatings Technology, 2025, 511: 132285.
[21] OBEYDAVI A, SHAFYEI A, LEE J W.Investigating of the Microstructure, Mechanical Properties and Corrosion Behavior of CoCrFeMnNiSix High Entropy Alloy Thin Films Deposited by Co-Sputtering Method[J]. Journal of Alloys and Compounds, 2025, 1017: 178972.
[22] LU X L, ZHANG X, LU Y, et al.Characterization and Wear Role of (CrAlVTiNb)Nx High-Entropy Alloy Nitride Films Deposited by High Power Impulse Magnetron Sputtering[J]. Journal of Alloys and Compounds, 2025, 1020: 179395.
[23] LOU B S, LI C L, ANNALAKSHMI M, et al.Exploring the Effect of Ti and Al Contents on the Microstructural, Mechanical, and Corrosion Resistance Features of VNbMoTaWTiAlN Refractory High Entropy Alloy Coatings[J]. Materials Chemistry and Physics, 2025, 341: 130901.
[24] LIN Y X, CHANG W C, WANG Y C, et al.Effect of Substrate Temperature on the Formation of Nanotwin and Properties of NiCoFeCrAlTi High-Entropy Alloy Thin Films[J]. Journal of Alloys and Compounds, 2025, 1013: 178505.
[25] 谷佳慧, 魏东博, 高泽宇, 等. 高熵陶瓷薄膜晶体结构、制备及其功能特性研究进展[J]. 表面技术, 2023, 52(12): 274-288.
GU J H, WEI D B, GAO Z Y, et al.Research Progress on Crystal Structure, Preparation and Functional Properties of High-Entropy Ceramic Thin Films[J]. Surface Technology, 2023, 52(12): 274-288.
[26] ZHANG F L, CHEN X M, LIU H, et al.Recent Developments in CoCrFeNi-Based High Entropy Alloy Coatings: Design, Synthesis, and Properties[J]. Journal of Alloys and Compounds, 2025, 1018: 179193.
[27] GUO J L, SU Y F, ZHANG C, et al.Influence of Nitrogen Flow Rate on the Structure and Properties of (AlTiVCrMoSi)Nx High-Entropy Alloy Nitride Coatings via Arc Ion Plating[J]. Surface and Coatings Technology, 2025, 496: 131732.
[28] 赵文济, 梅芳华, 董云杉, 等. 射频反应溅射(Al, Ti)N涂层的微结构与力学性能[J]. 材料工程, 2005, 33(9): 48-52.
ZHAO W J, MEI F H, DONG Y S, et al.Microstructure and Mechanical Properties of Reactively Sputtered(Al, Ti)N Coatings[J]. Journal of Materials Engineering, 2005, 33(9): 48-52.
[29] 连玉红, 张众, 黄秋实. 反应溅射气体对Ni、Ti薄膜成膜特性的作用机制[J]. 光学仪器, 2017, 39(1): 56.
LIAN Y H, ZHANG Z, HUANG Q S.The Effects of Sputtering Gas in the Characterization of Ni and Ti Monolayer Films[J]. Optical Instruments, 2017, 39(1): 56.
[30] HSUEH H T, SHEN W J, TSAI M H, et al.Effect of Nitrogen Content and Substrate Bias on Mechanical and Corrosion Properties of High-Entropy Films (AlCrSiTiZr)100-xNx[J]. Surface and Coatings Technology, 2012, 206(19/20): 4106-4112.
[31] HRUŠKA P, LUKÁČ F, CICHOŇ S, et al. Oxidation of Amorphous HfNbTaTiZr High Entropy Alloy Thin Films Prepared by DC Magnetron Sputtering[J]. Journal of Alloys and Compounds, 2021, 869: 157978.
[32] HUNG S B, WANG C J, CHEN Y, et al.Thermal and Corrosion Properties of V-Nb-Mo-Ta-W and V-Nb-Mo- Ta-W-Cr-B High Entropy Alloy Coatings[J]. Surface and Coatings Technology, 2019, 375: 802-809.
[33] 张玉芬, 于涵, 马凯丽, 等. 氮气流量比对三靶高功率脉冲磁控共溅射(TiSiAlCrV)N薄膜结构和性能的影响[J]. 表面技术, 2026, 55(1): 96-106.
ZHANG Y F, YU H, MA K L, et al.Effect of Nitrogen Flow Ratio on the Structure and Properties of (TiSiAlCrV)N Films via Three-Target High-Power Impulse Magnetron Co-Sputtering[J]. Surface Technology, 2026, 55(1): 96-106.
[34] 黄纯可, 李伟, 刘平, 等. 射频磁控溅射制备(AlCrTiZrNb)N高熵合金薄膜的微观组织和力学性能[J]. 真空科学与技术学报, 2018, 38(6): 487-493.
HUANG C K, LI W, LIU P, et al.Synthesis and Mechanical Properties of (AlCrTiZrNb)N High Entropy Alloy Films Grown by RF Magnetron Sputtering[J]. Chinese Journal of Vacuum Science and Technology, 2018, 38(6): 487-493.
[35] XU Y, LI G, XIA Y.Synthesis and Characterization of Super-Hard AlCrTiVZr High-Entropy Alloy Nitride Films Deposited by HiPIMS[J]. Applied Surface Science, 2020, 523: 146529.
[36] SUN S, WANG H, HUANG L, et al.Microstructure Evolution and Mechanical Properties of Refractory High-Entropy Alloy Nitride Film[J]. Surface and Coatings Technology, 2024, 483: 130775.
基金
石家庄市科技计划项目（246081487A）; 2025年度河北引智项目
PDF(9001 KB)
渝公网安备 50010702501715号 渝ICP备15012534号-3
