Please wait a minute...
金属学报  2026, Vol. 62 Issue (4): 649-668    DOI: 10.11900/0412.1961.2024.00185
  研究论文 本期目录 | 过刊浏览 |
耐腐蚀磨损CrN/NbN涂层的沉积机制及缺陷控制
刘永康, 陆媛媛, 杨英(), 刘兴光, 郑军, 张世宏()
安徽工业大学 先进金属材料绿色制备与表面技术教育部重点实验室 马鞍山 243002
Deposition Mechanism and Defect Control of CrN/NbN Coatings with Excellent Tribocorrosion Performance
LIU Yongkang, LU Yuanyuan, YANG Ying(), LIU Xingguang, ZHENG Jun, ZHANG Shihong()
Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials, Ministry of Education, Anhui University of Technology, Ma'anshan 243002, China
引用本文:

刘永康, 陆媛媛, 杨英, 刘兴光, 郑军, 张世宏. 耐腐蚀磨损CrN/NbN涂层的沉积机制及缺陷控制[J]. 金属学报, 2026, 62(4): 649-668.
Yongkang LIU, Yuanyuan LU, Ying YANG, Xingguang LIU, Jun ZHENG, Shihong ZHANG. Deposition Mechanism and Defect Control of CrN/NbN Coatings with Excellent Tribocorrosion Performance[J]. Acta Metall Sin, 2026, 62(4): 649-668.

全文: PDF(8398 KB)   HTML
摘要: 

CrN/NbN涂层因其优异的抗腐蚀和耐磨损性能,在海洋服役环境中具有良好的应用前景。本工作采用电弧离子镀技术在45#钢基体上沉积了6种CrN/NbN涂层(S1~S6),通过多层/纳米多层结构设计和引入离子刻蚀工艺降低了涂层缺陷密度,提升了涂层综合性能,并针对涂层的腐蚀磨损失效行为进行了初步探讨。结果表明,S2~S6涂层均具有细小的柱状晶结构,主要物相为CrN和NbN,且S2和S3多层涂层层间界面清晰、结合良好。S6涂层为纳米多层结构,调制周期为8.9 nm,子层界面共格且存在一定程度的Nb、Cr元素互扩散。涂层中的层错提升了涂层的力学性能。离子刻蚀工艺在不改变涂层物相结构和恶化涂层力学性能的同时,打断了大颗粒的连续生长,平滑了涂层表面/界面,从而显著降低了涂层的表面缺陷占比,其中S3和S5涂层的表面缺陷占比分别为(2.70 ± 0.19)%和(2.43 ± 0.49)%。随着子层厚度的降低,涂层的耐电化学腐蚀性能和耐腐蚀磨损性能逐渐提升,其中S6涂层具有最低的腐蚀磨损率,为2.42 × 10-6 mm3/(N·m)。

关键词 CrN/NbN多层/纳米多层涂层离子刻蚀腐蚀磨损    
Abstract

The rapid exploitation of marine resources in China has heightened the need for advanced marine engineering equipment and imposed more stringent requirements on the surface performance of its key components. CrN/NbN coatings, with their excellent corrosion and wear resistances, demonstrate potential for applications in marine service environments. In this study, CrN/NbN coatings were deposited on 45# steel substrates using arc ion plating technology. A multilayer/nanolayer design and ion etching process were implemented to reduce coating defect densities, thereby enhancing overall coating performance. SEM analysis revealed that S2-S6 coatings exhibited fine columnar structures, with well-defined and cohesive sublayer interfaces in S2 and S3 multilayer coatings. XRD and TEM analyses confirmed that the primary phases of the coatings were CrN and NbN. HRTEM analyses demonstrated that S6 coating present nanolayer structure with a modulation period of 8.9 nm, where CrN and NbN sublayer thicknesses were approximately 2.7 and 6.2 nm, respectively. A coherent interface was observed in the S6 coating, accompanied by the interdiffusion of Nb and Cr elements between the CrN and NbN sublayers. The fast Fourier transform (FFT) image displayed streak-like features characteristic of stacking faults, as well as two sets of diffraction patterns indicative of coherent sublayer interfaces. Nanoindentation tests revealed that among the fabricated coatings, the S1 monolayer coating exhibited the lowest hardness of (21.8 ± 0.7) GPa, while the S4 coating demonstrated the highest hardness of (30.1 ± 1.4) GPa, attributed to its coherent interfaces and stacking faults. Ion etching had minimal impact on coating phases and mechanical properties. However, ion bombardment effectively interrupted the continuous growth of large particles, resulting in smoother surfaces and interfaces and thereby reducing surface defect proportions. The defect percentages for S3 and S5 coatings were (2.7 ± 0.19)% and (2.43 ± 0.49)%, respectively. These lower defect densities contributed to higher pore resistance (Rpo) and charge transfer resistance (Rct). As sublayer thickness decreased, the electrochemical and tribocorrosion performance of CrN/NbN coatings improved progressively, with the S6 sample achieving the lowest corrosive wear rate of 2.42 × 10-6 mm3/(N·m). The tribocorrosion failure mechanism was preliminarily explored, identifying layer-by-layer peeling as the dominant failure mode. Compared to NbN monolayer coatings, CrN/NbN multilayer/nanolayer coatings exhibited superior mechanical properties and corrosion resistance due to interface blocking and reinforcing effects. Furthermore, the application of ion etching to CrN/NbN multilayer/nanolayer coatings enhanced their electrochemical corrosion and tribocorrosion properties by disrupting the growth of large defects.

Key wordsCrN/NbN    multilayer/nanomultilayer coating    ion etching    tribocorrosion
收稿日期: 2024-06-03     
ZTFLH:  TG174.4  
基金资助:国家自然科学基金项目(52101063);安徽省自然科学基金项目(2108085QE187);安徽省高校自然科学研究项目(KJ2021A0392)
通讯作者: 杨 英,yangying@ahut.edu.cn,主要从事材料腐蚀与防护技术研究;
张世宏,shzhang@ahut.edu.cn,主要从事金属表面涂层技术研究
作者简介: 刘永康,男,1997年生,博士
图1  镀膜设备及沉积过程示意图

Coating

Temperature

oC

N2 Pressure PaBias voltage VCr target current ANb target current A

Working mode of Cr and Nb targets

Rotating speed

r·min-1

Ion etching

Note

S13003.5-80-140-3NoSingle layer
S23003.5-80120140Switch on alternatively3NoMultilayer
S33003.5-80120140Switch on alternatively3YesMultilayer
S43003.5-80120140Switch on simultaneously3NoNanolayer
S53003.5-80120140Switch on simultaneously3YesNanolayer
S63003.5-80120140Switch on simultaneously5NoNanolayer
表1  CrN/NbN多层/纳米多层涂层的沉积参数
图2  S1~S6涂层截面的SEM像(a) S1 (b) S2 (c) S3 (d) S4 (e) S5 (f) S6
图3  S6涂层截面的TEM像和选区电子衍射(SAED)花样
图4  S6涂层的高角环形暗场(HAADF)像及EDS分析
图5  S6涂层截面中部区域TEM分析
图6  S5涂层截面TEM分析
图7  S1~S6涂层截面微观缺陷的SEM像
图8  S2~S5涂层表面形貌的背散射电子(BSE)像及缺陷面积分布
图9  S2~S5涂层表面缺陷占比及表面粗糙度
图10  S1~S6涂层样品的XRD谱
图11  S1~S6涂层的硬度
图12  S1~S6涂层样品Rockwell压痕形貌的OM像
图13  S1~S6涂层样品在3.5%NaCl (质量分数)溶液中的电化学阻抗谱(EIS)和等效电路
CoatingRsQ1RpoQ2Rct
Ω·cm2Ω·cm2Ω·cm2

Ypo

Ω-1·cm-2·S n

n1

Yct

Ω-1·cm-2·S n

n2
S129.265.53 × 10-50.88653.53 × 1021.11 × 10-40.72901.04 × 104
S231.472.88 × 10-50.91841.03 × 1033.95 × 10-50.50095.58 × 104
S331.512.07 × 10-50.94104.22 × 1034.22 × 10-50.55957.07 × 104
S427.081.57 × 10-50.87561.03 × 1033.30 × 10-50.44902.88 × 105
S525.551.28 × 10-50.88173.58 × 1035.01 × 10-50.52386.19 × 105
S628.182.58 × 10-50.88584.03 × 1032.26 × 10-50.53871.38 × 105
表2  S1~S6涂层样品在3.5%NaCl溶液中的EIS拟合结果
图14  S1~S6涂层样品腐蚀磨损过程中开路电位(OCP)及摩擦系数变化规律
图15  腐蚀磨损实验后S5涂层样品未磨损区域的表面形貌及EDS面扫图
图16  S1~S6涂层样品腐蚀磨损率
图17  S1~S6涂层样品磨痕表面形貌SEM像
图18  腐蚀磨损实验后S1~S6涂层磨痕的二维形貌图
SamplePointNbCrNAlOFeNa
S1123.62--2.4072.04-1.93
247.98-43.77-8.24--
S21-41.7134.768.5414.98--
246.63-48.91-4.47--
3-52.1245.27-2.61--
S3124.17-0.562.9869.88-2.41
245.20-48.45-6.35--
3-50.4547.100.172.28--
S4119.1516.0210.160.4154.26--
231.1316.8450.27-1.75--
S5121.0511.846.971.0859.05--
229.7421.1948.01-1.06--
329.2918.1832.16-18.152.21-
S6114.0918.982.541.5560.71-2.13
227.2321.5849.57-1.62--
326.0911.3631.21-21.0710.26-
表3  S1~S6样品磨痕区域的元素成分 (atomic fraction / %)
图19  S2涂层样品磨痕截面形貌的SEM像
图20  S2样品磨痕截面形貌的SEM像和EDS元素面分布图
图21  涂层腐蚀磨损机理示意图
[1] Ghorbani A, Elmkhah H, Imantalab O, et al. The impact of mechanical post-treatment on the tribological and corrosion behavior of CrN/CrAlN coatings applied using the CAE-PVD technique [J]. Appl. Surf. Sci. Adv., 2023, 18: 100477
[2] Vengesa Y, Fattah-Alhosseini A, Elmkhah H, et al. Investigation of corrosion and tribological characteristics of annealed CrN/CrAlN coatings deposited by CAE-PVD [J]. Ceram. Int., 2023, 49: 3016
[3] Zhou S G, Qin B D, Wang S C, et al. Multilayer interfaces to achieve excellent corrosion and tribological performances for CrAlCN nanocomposite coating in the seawater [J]. Mater. Chem. Phys., 2023, 301: 127689
[4] Kumar S, Maity S R, Patnaik L. Effect of tribological process parameters on the wear and frictional behaviour of Cr-(CrN/TiN) composite coating: An experimental and analytical study [J]. Ceram. Int., 2021, 47: 16018
[5] Yu H Y, Liang W P, Miao Q, et al. Effect of shot peening pretreatment on the high-temperature tribological behaviours of a TaN coating prepared via double-cathode glow plasma alloying [J]. Surf. Coat. Technol., 2021, 427: 127825
[6] Liu Z X, Li Y, Xie X H, et al. The tribo-corrosion behavior of monolayer VN and multilayer VN/C hard coatings under simulated seawater [J]. Ceram. Int., 2021, 47: 25655
[7] González-Carmona J M, Triviño J D, Gómez-Ovalle Á, et al. Wear mechanisms identification using Kelvin probe force microscopy in TiN, ZrN and TiN/ZrN hard ceramic multilayers coatings [J]. Ceram. Int., 2020, 46: 24592
[8] Er D, Azar G T P, Kazmanlı K, et al. The corrosion protection ability of TiAlN coatings produced with CA-PVD under superimposed pulse bias [J]. Surf. Coat. Technol., 2018, 346: 1
[9] Panjan P, Drnovšek A, Gselman P, et al. Review of growth defects in thin films prepared by PVD techniques [J]. Coatings, 2020, 10: 447
[10] Liu Y R, Li S Y, Zhou X H, et al. Enhanced anti-tribocorrosion property of a-C film under high hydrostatic pressure by high power pulsed magnetron sputter (HiPIMS) [J]. J. Mater. Res. Technol., 2024, 28: 3052
[11] Creus J, Mazille H, Idrissi H. Porosity evaluation of protective coatings onto steel, through electrochemical techniques [J]. Surf. Coat. Technol., 2000, 130: 224
[12] Kong J Z, Zhai Q W, Shen J J, et al. Role of atomic layer deposited TiO x N y interlayer in tribological and corrosion properties of CrN coating [J]. Surf. Coat. Technol., 2022, 429: 127981
[13] Staszuk M, Reimann Ł, Pakuła D, et al. Investigations of TiO2/nano TiO2 bimodal coatings obtained by a hybrid PVD/ALD method on Al-Si-Cu alloy substrate [J]. Coatings, 2022, 12: 338
[14] Liu Y R, Li S Y, Li H, et al. Controllable defect engineering to enhance the corrosion resistance of Cr/GLC multilayered coating for deep-sea applications [J]. Corros. Sci., 2022, 199: 110175
[15] Wang D S, Hu M, Jiang D, et al. The improved corrosion resistance of sputtered CrN thin films with Cr-ion bombardment layer by layer [J]. Vacuum, 2017, 143: 329
[16] Wan Z X, Zhang T F, Lee H B R, et al. Improved corrosion resistance and mechanical properties of CrN hard coatings with an atomic layer deposited Al2O3 interlayer [J]. ACS Appl. Mater. Interfaces, 2015, 7: 26716
[17] Lin K F, Chang Y C, Chang S H, et al. Improving the corrosion and wear resistance of CoCrNiSi0.3 medium-entropy alloy by magnetron sputtered (CrN/Cr) x multilayer films [J]. Surf. Coat. Technol., 2024, 478: 130407
[18] Shi X W, Zhao Y M, Gao X, et al. Anti-corrosive yet color-tunable AlN/Si multilayer hard coatings on 304 stainless steel by magnetron sputtering [J]. Ceram. Int., 2024, 50: 1166
[19] Noori M, Atapour M, Ashrafizadeh F, et al. Nanostructured multilayer CAE-PVD coatings based on transition metal nitrides on Ti6Al4V alloy for biomedical applications [J]. Ceram. Int., 2023, 49: 23367
[20] Guo H X, Sun Q S, Zhou D P, et al. Erosion behavior of CrN, CrAlN and CrAlN/CrN multilayer coatings deposited on Ti6Al4V [J]. Surf. Coat. Technol., 2022, 437: 128284
[21] Ma F L, Li J L, Zeng Z X, et al. Structural, mechanical and tribocorrosion behaviour in artificial seawater of CrN/AlN nano-multilayer coatings on F690 steel substrates [J]. Appl. Surf. Sci., 2018, 428: 404
[22] Wang T, Zhang G J, Jiang B L. Comparison in mechanical and tribological properties of CrTiAlMoN and CrTiAlN nano-multilayer coatings deposited by magnetron sputtering [J]. Appl. Surf. Sci., 2016, 363: 217
[23] Cai F, Zhou Q, Chen J K, et al. Effect of inserting the Zr layers on the tribo-corrosion behavior of Zr/ZrN multilayer coatings on titanium alloys [J]. Corros. Sci., 2023, 213: 111002
[24] Ortíz C H, Hernandez-Renjifo E, Caicedo J C. Study of corrosion protection through the implementation of TiC/TiSiCN multilayer coatings [J]. Mater. Chem. Phys., 2024, 315: 128821
[25] Chen Y M. Study on microstructure regulation and strengthening mechanism of nano-multilayer ceramic coatings [D]. Beijing: University of Science and Technology Beijing, 2023
[25] 陈彦梦. 纳米多层陶瓷涂层的微观结构调控及强化机制研究 [D]. 北京: 北京科技大学, 2023
[26] Wang D, Lin S S, Yang Z, et al. Failure mechanisms of CrN and CrAlN coatings for solid particle erosion resistance [J]. Vacuum, 2022, 204: 111313
[27] Ji C C, Guo Q Q, Li J P, et al. Microstructure and properties of CrN coating via multi-arc ion plating on the valve seat material surface [J]. J. Alloys Compd., 2022, 891: 161966
[28] Ding J C, Zhang T F, Wang Q M, et al. Microstructure and mechanical properties of the Cr-Mo-Si-N nanocomposite coatings prepared by a hybrid system of AIP and HiPIMS technologies [J]. J. Alloys Compd., 2018, 740: 774
[29] Guan X Y, Wang Y X, Zhang G G, et al. Microstructures and properties of Zr/CrN multilayer coatings fabricated by multi-arc ion plating [J]. Tribol. Int., 2017, 106: 78
[30] Panjan P, Čekada M, Panjan M, et al. Growth defects in PVD hard coatings [J]. Vacuum, 2009, 84: 209
[31] Jasempoor F, Elmkhah H, Imantalab O, et al. Improving the mechanical, tribological, and electrochemical behavior of AISI 304 stainless steel by applying CrN single layer and Cr/CrN multilayer coatings [J]. Wear, 2022, 504-505: 204425
[32] Guan X Y, Wang Y X, Xue Q J, et al. Toward high load bearing capacity and corrosion resistance Cr/Cr2N nano-multilayer coatings against seawater attack [J]. Surf. Coat. Technol., 2015, 282: 78
[33] Abusuilik S B, Inoue K. Effects of intermediate surface treatments on corrosion resistance of cathodic arc PVD hard coatings [J]. Surf. Coat. Technol., 2013, 237: 421
[34] Guan X Y, Wang Y X, Zhang G G, et al. Effects of intermediate Ar plasma treatments on CrN coating microstructures and property evolutions [J]. Surf. Interface. Anal., 2017, 49: 323
[35] Purandare Y P, Robinson G L, Ehiasarian A P, et al. Investigation of high power impulse magnetron sputtering deposited nanoscale CrN/NbN multilayer coating for tribocorrosion resistance [J]. Wear, 2020, 452-453: 203312
[36] Biswas B, Purandare Y, Khan I, et al. Effect of substrate bias voltage on defect generation and their influence on corrosion and tribological properties of HIPIMS deposited CrN/NbN coatings [J]. Surf. Coat. Technol., 2018, 344: 383
[37] Hovsepian P E, Ehiasarian A P, Purandare Y P, et al. Novel HIPIMS deposited nanostructured CrN/NbN coatings for environmental protection of steam turbine components [J]. J. Alloys Compd., 2018, 746: 583
[38] Ramadoss R, Kumar N, Dash S, et al. Wear mechanism of CrN/NbN superlattice coating sliding against various counterbodies [J]. Int. J. Refract. Met. Hard Mater., 2013, 41: 547
[39] Huang W, Zalnezhad E, Musharavati F, et al. Investigation of the tribological and biomechanical properties of CrAlTiN and CrN/NbN coatings on SST 304 [J]. Ceram. Int., 2017, 43: 7992
[40] Chen M H, Ding J C, Kwon S H, et al. Corrosion resistance and conductivity of NbN-coated 316L stainless steel bipolar plates for proton exchange membrane fuel cells [J]. Corros. Sci., 2022, 196: 110042
[41] Lao J J, Kong M, Zhang H J, et al. Growth structure and mechanical properties of TiN/SiC nano-multilayers [J]. Acta Phys. Sin., 2004, 53: 1961
[41] 劳技军, 孔 明, 张惠娟 等. TiN/SiC纳米多层膜的生长结构与力学性能 [J]. 物理学报, 2004, 53: 1961
[42] Chen Y M, Guo T, Pang X L, et al. Formation of high-density stacking faults in ceramic films induced by Ti transition layer [J]. Scr. Mater., 2022, 211: 114496
[43] Zhang H, He Y Z, Pan Y, et al. Thermally stable laser cladded CoCrCuFeNi high-entropy alloy coating with low stacking fault energy [J]. J. Alloys Compd., 2014, 600: 210
[44] Shin C S, Kim Y W, Hellgren N, et al. Epitaxial growth of metastable δ-TaN layers on MgO(001) using low-energy, high-flux ion irradiation during ultrahigh vacuum reactive magnetron sputtering [J]. J. Vac. Sci. Technol., 2002, 20A: 2007
[45] Huang Y, Chen Z, Wagner A, et al. High density of stacking faults strengthened TaN/TiN multilayer [J]. Acta Mater., 2023, 255: 119027
[46] Yu H, Bahadori M, Thompson G B, et al. Understanding dislocation slip in stoichiometric rocksalt transition metal carbides and nitrides [J]. J. Mater. Sci., 2017, 52: 6235
[47] Araujo J A, Giorjão R A R, Bettini J, et al. Modeling intrinsic residual stresses built-up during growth of nanostructured multilayer NbN/CrN coatings [J]. Surf. Coat. Technol., 2016, 308: 264
[48] Fang W, Chen J K, Cai F, et al. Surface stress release in AlCrN coatings determined by synchrotron radiation multi-reflection grazing-incidence X-ray diffraction [J]. Thin Solid Films, 2023, 787: 140142
[49] Cedeño-Vente M L, Manríquez J, Mondragón-Rodríguez G C, et al. Application of a transmission line model to evaluate the influence of structural defects on the corrosion behavior of arc-PVD CrN coatings [J]. Ceram. Int., 2021, 47: 20885
[50] Yang Y, Wang F, Wu Y D, et al. The corrosive wear behavior of Cr/NiCrN multilayer coatings with various cycle periods [J]. Surf. Technol., 2021, 50: 301
[50] 杨 英, 王 芳, 巫业栋 等. 不同循环周期Cr/NiCrN多层涂层腐蚀磨损行为 [J]. 表面技术, 2021, 50: 301
[51] Chu X, Wong M S, Sproul W D, et al. Deposition, structure, and hardness of polycrystalline transition-metal nitride superlattice films [J]. J. Mater. Res., 1999, 14: 2500
[52] Kao C M, Lee J W, Chen H W, et al. Microstructures and mechanical properties evaluation of TiAlN/CrSiN multilayered thin films with different bilayer periods [J]. Surf. Coat. Technol., 2010, 205: 1438
[53] Zhang S, Sun D E, Fu Y Q, et al. Toughening of hard nanostructural thin films: A critical review [J]. Surf. Coat. Technol., 2005, 198: 2
[54] Kong W C, Yu Z, Hu J. Electrochemical performance and corrosion mechanism of Cr-DLC coating on nitrided Ti6Al4V alloy by magnetron sputtering [J]. Diam. Relat. Mater., 2021, 116: 108398
[55] Park H S, Kappl H, Lee K H, et al. Structure modification of magnetron-sputtered CrN coatings by intermediate plasma etching steps [J]. Surf. Coat. Technol., 2000, 133-134: 176
[56] Liu Y K, Yang Y, Liu X G, et al. Tribocorrosion of CrN coatings on different steel substrates [J]. Surf. Coat. Technol., 2024, 484: 130829
[57] Liu L M, Zheng H, Dong M P, et al. Effect of bias voltage on the tribocorrosion performance of TiAlSiN coatings on FH790 steel by arc ion plating [J]. Surf. Coat. Technol., 2023, 454: 129177
[1] 王吉会;姜晓霞;李诗卓. 铜合金在3.5%NaCl+NH_3(NH_4~+)溶液中的腐蚀磨损行为[J]. 金属学报, 1997, 33(12): 1268-1274.
[2] 毕红运;姜晓霞;李诗卓;杨景祥. 铸造Cr-Mn-N系不锈钢腐蚀磨损行为的研究[J]. 金属学报, 1997, 33(10): 1069-1074.
[3] 方耀华;张明杰;孙玉珍;王文皓. 5454铝镁合金与工业纯铝管在碳化液中形成的表面膜研究[J]. 金属学报, 1996, 32(7): 763-768.
[4] 黄彦良;姜晓霞;李诗卓. 不锈钢在Cl~-+H_2SO_4溶液中轻载下的腐蚀磨损[J]. 金属学报, 1996, 32(1): 57-62.
[5] 路新春;李诗卓;张天成;姜晓霞. 固溶处理温度对双相不锈钢在硫酸介质中腐蚀磨损行为的影响[J]. 金属学报, 1994, 30(16): 159-164.
[6] 张天成;姜晓霞;李诗卓;师昌绪. 不锈钢在H_3PO_4+NaCl溶液中腐蚀磨损的交互作用[J]. 金属学报, 1993, 29(5): 74-79.
[7] 姜晓霞;孙理;李诗卓;肖耀天. CD-4MCu合金在磷酸介质中的腐蚀磨损行为[J]. 金属学报, 1992, 28(2): 59-63.
[8] 姜晓霞;李诗鋽;林晓娉;杨景祥. 不锈钢在稀硫酸介质中的腐蚀磨损行为[J]. 金属学报, 1991, 27(1): 98-101.