Please wait a minute...
Acta Metall Sin  2025, Vol. 61 Issue (9): 1413-1424    DOI: 10.11900/0412.1961.2023.00473
Research paper Current Issue | Archive | Adv Search |
Effect of Mo Content on the Microstructure, Mechanical and Tribological Properties of CrAlMoN Coatings
BI Jianhaonan1, ZHANG Yan2, WANG Zhenyu2(), ZHOU Shenghao2, LIU Yongyue3, ZHANG Xiaoyan4, WANG Aiying2
1 College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China
2 State Key Laboratory of Advanced Marine Materials, Zhejiang Key Laboratory of Extreme-environmental Material Surfaces and Interfaces, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
3 Ningbo Heli Mould Technology Co. Ltd., Ningbo 315799, China
4 Ningbo Tianzheng Mould Co. Ltd., Ningbo 315812, China
Cite this article: 

BI Jianhaonan, ZHANG Yan, WANG Zhenyu, ZHOU Shenghao, LIU Yongyue, ZHANG Xiaoyan, WANG Aiying. Effect of Mo Content on the Microstructure, Mechanical and Tribological Properties of CrAlMoN Coatings. Acta Metall Sin, 2025, 61(9): 1413-1424.

Download:  HTML  PDF(4477KB) 
Export:  BibTeX | EndNote (RIS)      
Abstract  

CrAlN coatings have garnered significant attention in the fields of cutting tools and plastic injection molds because of their high hardness, excellent thermal stability, and superior oxidation resistance. However, their applicability under the harsh conditions of aluminum alloy die casting and hot stamping dies is curtailed by the coatings' high coefficient of friction and limited impact toughness. By adopting a multiple alloying and high-throughput approach, this study focuses on the fabrication of CrAlMoN solid solution coatings with varying Mo contents on H13 steel substrates using arc ion plating technology. The effects of Mo content on the microstructure, mechanical and tribological properties of the coatings were thoroughly examined. Characterization techniques such as XRD, SEM, and EDS were employed to analyze the phase structures, surface cross-sectional morphology, and elemental distribution of the coatings. Mechanical properties, including hardness, film-base adhesion, and toughness, were assessed using a CMS scratch tester and a nanoindentation tester. The friction properties were evaluated using a tribometer in an atmospheric environment. The findings indicate that increasing the Mo content (atomic fraction) from 0.72% to 19.47% resulted in the incorporation of Mo atoms into the (Cr, Al)N lattice, forming a typical solid solution coating with a minor presence of Mo2N crystal phases. Notably, at a Mo content of approximately 2.55%, the coatings achieved peak hardness (38.7 ± 1.3) GPa and elastic modulus (580.9 ± 11.1) GPa, along with enhanced toughness due to improved crack resistance. Tribological experiments demonstrated remarkable wear resistance at 25 oC, with a coefficient of friction (COF) ranging from 0.32 to 0.51 and wear rates of (5.90-10.88) × 10-7 mm3/(N·m). The low COF and wear rates are attributed to the formation of Magnéli-phase oxide MoO3, which facilitates low shear during friction. A further increase in the Mo content to 19.47% led to even better tribological properties, as indicated by the lowest observed COF of 0.31 and a wear rate of 5.90 × 10-7 mm3/(N·m). The microstructural analysis revealed that the accumulation of MoO3 phases during friction contributed to the coatings' tribological performance, with wear primarily resulting from the combined effects of abrasive wear and severe oxidation, accompanied by minor pitting delamination from the substrates.

Key words:  CrAlMoN soild solution coating      high-throughput preparation      hard yet tough      Magnéli lubrication phase      wear resistance     
Received:  11 December 2023     
ZTFLH:  TG174.4  
Fund: National Natural Science Foundation of China(52171090);National Funds For Distinguished Young Scholars(52025014);Science and Technology Project of Ningbo(2022Z011);Science and Technology Project of Ningbo(2023QL049);Science and Technology Project of Ningbo(2023Z022)
Corresponding Authors:  WANG Zhenyu, professor, Tel: (0574)86697187, E-mail: wangzy@nimte.ac.cn

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2023.00473     OR     https://www.ams.org.cn/EN/Y2025/V61/I9/1413

Fig.1  Schematic of the deposition system (MFC—mass flow controller)
SampleDC pulsed bias / VN2 flow rate mL·min-1Target current / A

Deposition time

min

CrCrAlCrCrMo
Ar+ etching-2000000025
Cr adhesive layer-300070070010
CrN transition layer-7055070070020
CrAlMoN layer-706500800100120
Table 1  Deposition parameters in detail of the CrAlMoN coatings
SampleAtomic fraction / %

Thickness

μm

Roughness

μm

CrAlMoN
A122.28 ± 0.0136.76 ± 0.250.72 ± 0.0237.48 ± 0.249.320.150 ± 0.044
A222.74 ± 0.1236.18 ± 0.221.21 ± 0.0337.39 ± 0.227.150.219 ± 0.010
A323.42 ± 0.2534.15 ± 0.322.55 ± 0.0336.71 ± 0.306.350.137 ± 0.024
A426.89 ± 0.2827.53 ± 0.166.38 ± 0.2233.90 ± 0.176.010.080 ± 0.029
C138.40 ± 0.578.64 ± 0.0916.50 ± 0.3125.14 ± 0.416.160.200 ± 0.043
C244.73 ± 0.841.04 ± 0.0419.47 ± 0.3420.51 ± 0.348.860.082 ± 0.005
Table 2  Chemical compositions, thicknesses, and surface roughnesses of CrAlMoN coatings at different positions
Fig.2  Surfacial (a-d) and cross-sectional (e-h) SEM images of CrAlMoN coatings with different compositions
(a, e) A1 (b, f) A3 (c, g) C1 (d, h) C2
Fig.3  XRD spectra of CrAlMoN coatings with different compositions
(a) A1-A4 samples (b) the enlarged view of (111) peak in Fig.3a (c) C1 and C2 samples
Fig.4  STEM image of A3 coating illustrated with EDS results for light and dark layers (insets), and corresponding Mo element mapping
Fig.5  Phase structure and microstructure characterization of A3 coating (a-d) and C2 coating (e-h) (d—crystal spacing)
(a, e) low magnification morphologies (b, c) HRTEM images at different regions and inverse fast Fourier transform (IFFT) (insets) of A3 coating (f, g) HRTEM images at different region and IFFT (insets) of C2 coating (d, h) selected area electron diffraction (SEAD) patterns
Fig.6  Hardnesses (H) and elastic moduli (E) (a), and H / E and H3/ E2 (b) of CrAlMoN coatings with different compositions
Fig.7  Nanoindentation morphologies of CrAlMoN coatings with different compositions
(a) A1 (b) A3 (c) C1 (d) C2
Fig.8  Scratch morphologies of CrAlMoN coatings with different composition (a-d) and enlarged views of the corresponding crack propagation (e-h)
(a, e) A1 (b, f) A3 (c, g) C1 (d, h) C2
Fig.9  Friction curves (a) and average friction coefficients and wear rates (b) of CrAlMoN coatings sliding relative to Al2O3 ball in atmospheric environment
Fig.10  Morphologies of wear marks of CrAlMoN coatings with different composition (a-d) and the corresponding wear spot morphologies for the Al2O3 friction pair (e-h)
(a, e) A1 (b, f) A3 (c, g) C1 (d, h) C2
Fig.11  Raman spectra at the wear mark of CrAlMoN coatings (a) and SEM image of the wear mark and corresponding EDS element mappings for A3 sample (b)
[1] Yang B, Chen L, Chang K K, et al. Thermal and thermo-mechanical properties of Ti-Al-N and Cr-Al-N coatings [J]. Int. J. Refract. Met. Hard Mater., 2012, 35: 235
[2] Reiter A E, Mitterer C, de Figueiredo M R, et al. Abrasive and adhesive wear behavior of arc-evaporated Al1 - x Cr x N hard coatings [J]. Tribol. Lett., 2010, 37: 605
[3] Li W Z, Polcar T, Evaristo M, et al. High temperature properties of the Cr-Nb-Al-N coatings with increasing Al contents [J]. Surf. Coat. Technol., 2013, 228: 187
[4] Wang Y X, Tang Y J, Wan W, et al. Effect of Ni doping on the microstructure and toughness of CrAlN coatings deposited by magnetron sputtering [J]. Mater. Res. Express, 2020, 7: 026414
[5] Wang C C, Xu B B, Wang Z Y, et al. Tribological mechanism of (Cr, V)N coating in the temperature range of 500-900 oC [J]. Tribol. Int., 2021, 159: 106952
[6] Zhang Y P, Wang Z Y, Guo P, et al. Enhanced tribological behavior of VAlN hard ceramic coating with intermittent amorphous carbon layer [J]. Ceram. Int., 2023, 49: 15091
[7] Liu C B, Pei W, Huang F, et al. Improved mechanical and thermal properties of CrAlN coatings by Si solid solution [J]. Vacuum, 2016, 125: 180
[8] Hollerweger R, Zhou L, Holec D, et al. Controlling microstructure, preferred orientation, and mechanical properties of Cr-Al-N by bombardment and alloying with Ta [J]. J. Appl. Phys., 2016, 119: 065304
[9] Qi Z B, Wu Z T, Wang Z C. Improved hardness and oxidation resistance for CrAlN hard coatings with Y addition by magnetron co-sputtering [J]. Surf. Coat. Technol., 2014, 259: 146
[10] Tian J L, Hu C, Chen L, et al. Structure, mechanical and thermal properties of Y-doped CrAlN coatings [J]. Trans. Nonferrous Met. Soc. China, 2021, 31: 2740
[11] Bobzin K, Brögelmann T, Kalscheuer C. Arc PVD (Cr, Al, Mo)N and (Cr, Al, Cu)N coatings for mobility applications [J]. Surf. Coat. Technol., 2020, 384: 125046
[12] Chen L, Liu Z Q, Xu Y X, et al. Influence of Zr on structure, mechanical and thermal properties of Cr-Al-N coatings [J]. Surf. Coat. Technol., 2015, 275: 289
[13] Rajput S S, Gangopadhyay S, Yaqub T B, et al. Room and high temperature tribological performance of CrAlN(Ag) coatings: The influence of Ag additions [J]. Surf. Coat. Technol., 2022, 450: 129011
[14] Shi J, Chen Y, Liu H, et al. Effect of Mo and C contents on the crystal structure and properties of AlCrN films [J]. China Surf. Eng., 2022, 35(6): 286
施 杰, 陈 云, 刘 浩 等. Mo和C含量对AlCrN薄膜组织和性能的影响 [J]. 中国表面工程, 2022, 35(6): 286
[15] Wang Y X, Ji Y. Influence of Mo doping on the microstructure, friction, and wear properties of CrAlN films [J]. J. Mater. Eng. Perform., 2021, 30: 1938
[16] Sergevnin V S, Blinkov I V, Belov D S, et al. Phase formation in the Ti-Al-Mo-N system during the growth of adaptive wear-resistant coatings by arc PVD [J]. Inorg. Mater., 2016, 52: 735
[17] Fu Y Q, Zhou F, Zhang M D, et al. Structural, mechanical and tribocorrosion performances of CrMoSiN coatings with various Mo contents in artificial seawater [J]. Appl. Surf. Sci., 2020, 525: 146629
[18] Qi D L, Chen J J, Liu J, et al. Influence of molybdenum addition on oxidation resistance of CrN coatings [J]. Rare Met. Mater. Eng., 2021, 50: 1505
齐东丽, 陈建金, 刘 俊 等. 钼添加对CrN涂层抗氧化性能的影响(英文) [J]. 稀有金属材料与工程, 2021, 50: 1505
[19] Wang Y X, Lou B Y. Microstructure and high-temperature friction and wear properties of CrAlMoN film [J]. Oxid. Met., 2021, 95: 239
[20] Fu X J, Li R C, Li Y, et al. Tribological properties of CrN and CrAlN coatings in the presence of organic molybdenum additives [J]. China Surf. Eng., 2021, 34(6): 181
付小静, 李瑞川, 李 阳 等. 有机钼添加剂作用下CrN和CrAlN涂层的摩擦学性能 [J]. 中国表面工程, 2021, 34(6): 181
[21] Zhou D W, Wang Z Y, Zhang Y, et al. Stimulated corrosion damage of Ti-Al-N multilayer coatings under interval salt spray and hot condition [J]. Corros. Sci., 2023, 222: 111431
[22] Wang L, Fu Z Q, Yue W, et al. Effect of W content on tribological performance of CrWN coating under dry friction and oil lubrication conditions [J]. Rare Met. Mater. Eng., 2019, 48: 2371
王 莉, 付志强, 岳 文 等. W含量对CrWN涂层在干摩擦和油润滑下的摩擦学性能影响 [J]. 稀有金属材料与工程, 2019, 48: 2371
[23] Yu G Q, Tay B K, Lau S P, et al. Effects of N ion energy on titanium nitride films deposited by ion assisted filtered cathodic vacuum arc [J]. Chem. Phys. Lett., 2003, 374: 264
[24] Wang L, Wang Z Y, Chen R D, et al. Preparation and erosion performance of composite CrN coatings through zigzag structural design [J]. China Surf. Eng., 2023, 36(3): 65
王 丽, 王振玉, 陈仁德 等. 复合zigzag结构CrN涂层的设计制备及冲蚀性能 [J]. 中国表面工程, 2023, 36(3): 65
[25] Zhou S H, Kuang T C, Qiu Z G, et al. Microstructural origins of high hardness and toughness in cathodic arc evaporated Cr-Al-N coatings [J]. Appl. Surf. Sci., 2019, 493: 1067
[26] Zhou S H, Zhao W C, Qiu Z G, et al. Improved load-bearing capacity of Mo-doped Ti-N coatings: Effects of Mo alloying and GB plasticity [J]. Surf. Coat. Technol., 2021, 424: 127630
[27] Meindlhumer M, Ziegelwanger T, Zalesak J, et al. Precipitation-based grain boundary design alters inter- to trans-granular fracture in AlCrN thin films [J]. Acta Mater., 2022, 237: 118156
[28] Iram S, Wang J M, Cai F, et al. Effect of bilayer number on mechanical and wear behaviours of the AlCrN/AlCrMoN coatings by AIP method [J]. Surf. Eng., 2021, 37: 536
[29] Zhang Y, Zhou Y J, Lin J P, et al. Solid-solution phase formation rules for multi-component alloys [J]. Adv. Eng. Mater., 2008, 10: 534
[30] Chen Y, Xu Y X, Zhang H Q, et al. Improving high-temperature wear resistance of arc-evaporated AlCrN coatings by Mo alloying [J]. Surf. Coat. Technol., 2023, 456: 129253
[31] Fan Q X, Zhang J J, Wu Z H, et al. Influence of Al content on the microstructure and properties of the CrAlN coatings deposited by arc ion plating [J]. Acta Metall. Sin. (Engl. Lett.), 2017, 30: 1221
[32] Lu C, Jia J H, Fu Y Y, et al. Influence of Mo contents on the tribological properties of CrMoN/MoS2 coatings at 25-700  oC [J]. Surf. Coat. Technol., 2019, 378: 125072
[33] Zhang S, Sun D E, Fu Y Q, et al. Toughness measurement of thin films: A critical review [J]. Surf. Coat. Technol., 2005, 198: 74
[34] Perfilyev V, Moshkovich A, Lapsker I, et al. The effect of vanadium content and temperature on stick-slip phenomena under friction of CrV(x)N coatings [J]. Wear, 2013, 307: 44
[35] Sergevnin V S, Blinkov I V, Volkhonskii A O, et al. Structure formation of adaptive arc-PVD Ti-Al-Mo-N and Ti-Al-Mo-Ni-N coatings and their wear-resistance under various friction conditions [J]. Surf. Coat. Technol., 2019, 376: 38
[36] Camacho-López M A, Escobar-Alarcón L, Picquart M, et al. Micro-Raman study of the m-MoO2 to α-MoO3 transformation induced by cw-laser irradiation [J]. Opt. Mater., 2011, 33: 480
[37] Xu B B, Guo P, Wang Z Y, et al. Anti-wear Cr-V-N coating via V solid solution: Microstructure, mechanical and tribological properties [J]. Surf. Coat. Technol., 2020, 397: 126048
[38] Iram S, Cai F, Wang J M, et al. Effect of addition of Mo or V on the structure and cutting performance of AlCrN-based coatings [J]. Coatings, 2020, 10: 298
[1] YOU Shiquan, CUI Gongjun, YANG Rongqian, LIU Yusong, FENG Xiaogang, KOU Ziming. High-Temperature Tribological Performance of Laser Clad MoNiCr Alloy Coatings Reinforced by Si[J]. 金属学报, 2025, 61(9): 1403-1412.
[2] ZHAO Guangdi, LI Yang, YAO Xiaoyu, WANG Liang, LI Weibin, PAN Yuhua, LI Weijuan, WANG Zhaoyu. Effect of Boron on Solidification Behavior, Strength-Toughness, and Wear Resistance of Fe-Cr-B-C Alloy[J]. 金属学报, 2025, 61(5): 699-716.
[3] WANG Hanming, DU Yin, PEI Xuhui, WANG Haifeng. Tribological Property and Wear Mechanism of NbMoZrVSi x Refractory High-Entropy Alloy Strengthened by Eutectic Structure[J]. 金属学报, 2024, 60(7): 937-946.
[4] WANG Haifeng, ZHANG Zhiming, NIU Yunsong, YANG Yange, DONG Zhihong, ZHU Shenglong, YU Liangmin, WANG Fuhui. Effect of Pre-Oxidation on Microstructure and Wear Resistance of Titanium Alloy by Low Temperature Plasma Oxynitriding[J]. 金属学报, 2023, 59(10): 1355-1364.
[5] ZHANG Baicheng, ZHANG Wenlong, QU Xuanhui. Composition Design of Additive Manufacturing Materials Based on High Throughput Preparation[J]. 金属学报, 2023, 59(1): 75-86.
[6] ZHANG Yu, LOU Liyan, XU Qinglong, LI Yan, LI Changjiu, LI Chengxin. Microstructure and Wear Resistance of Ni-Based WC Coating by Ultra-High Speed Laser Cladding[J]. 金属学报, 2020, 56(11): 1530-1540.
[7] Hulin DONG,Haiping BAO,Jianhong PENG. Effect of TiC Contents on Mechanical Properties and Wear Resistance of Iron-Based Composites[J]. 金属学报, 2019, 55(8): 1049-1057.
[8] Shilu ZHAO,Zhen ZHANG,Jun ZHANG,Jianming WANG,Zhenggui ZHANG. MICROSTRUCTURE AND WEAR RESISTANCE OF TiAlZrCr/(Ti, Al, Zr, Cr)N GRADIENT FILMS DEPOSITED BY MULTI-ARC ION PLATING[J]. 金属学报, 2016, 52(6): 747-754.
[9] Wenfang CUI,Dong CAO,Gaowu QIN. MICROSTRUCTURE AND WEAR RESISTANCE OF Ti/TiN MULTILAYER FILMS DEPOSITED BY MAGNETRON SPUTTERING[J]. 金属学报, 2015, 51(12): 1531-1537.
[10] LIU Xiaobo, ZHAO Yuguang. MICROSTRUCTURE EVOLUTION AND WEAR RESISTANCE OF IN SITU Mg2Si/Al COMPOSITES UNDER DIFFERENT PREPARATION CONDITIONS[J]. 金属学报, 2014, 50(6): 753-761.
[11] NIU Yunsong, WEI Jie, ZHAO Jian, HU Jiaxiu, YU Zhiming. PREPARATION AND PROPERTIES OF NANOSIZED MUL-TILAYERED Ni COATINGS BY ULTRASOUND-ASSISTED ELECTRODEPOSITION[J]. 金属学报, 2013, 49(12): 1617-1622.
[12] YU Yipeng HUANG Jinfeng CUI Hua CAI Yuanhua ZHANG Jishan. EFFECT OF Nb ON THE MICROSTRUCTURE AND PROPERTIES OF SPRAY FORMED M3 HIGH SPEED STEEL[J]. 金属学报, 2012, 48(8): 935-940.
[13] ZHANG Fenggang ZHU Xiaopeng WANG Mingyang LEI Mingkai. SURFACE MODIFICATION OF WC-Ni CEMENTED CARBIDE FOR SEALS BY HIGH-INTENSITY PULSED ION BEAM IRRADIATION[J]. 金属学报, 2011, 47(7): 958-964.
[14] WANG Yanqiu WANG Yue CHEN Paiming SHAO Yawei WANG Fuhui. MICROSTRUCTURE, CORROSION AND WEAR RESISTANCES OF MICROARC OXIDATION COATING ON Al ALLOY 7075[J]. 金属学报, 2011, 47(4): 455-461.
[15] LEI Mingkai WANG Kesheng OU Yi Xiang ZHANG Lei. PLASMA–BASED LOW–ENERGY NITROGEN ION IMPLANTATION OF 2Cr13 MARTENSITIC STAINLESS STEEL USED IN PUMPS AND VALVES[J]. 金属学报, 2011, 47(12): 1490-1494.
No Suggested Reading articles found!