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Acta Metall Sin  2026, Vol. 62 Issue (4): 649-668    DOI: 10.11900/0412.1961.2024.00185
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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
Cite this article: 

LIU Yongkang, LU Yuanyuan, YANG Ying, LIU Xingguang, ZHENG Jun, ZHANG Shihong. Deposition Mechanism and Defect Control of CrN/NbN Coatings with Excellent Tribocorrosion Performance. Acta Metall Sin, 2026, 62(4): 649-668.

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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 words:  CrN/NbN      multilayer/nanomultilayer coating      ion etching      tribocorrosion     
Received:  03 June 2024     
ZTFLH:  TG174.4  
Fund: National Natural Science Foundation of China(52101063);Natural Science Foundation of Anhui Province(2108085QE187);Natural Science Foundation of the Higher Education Institutions of Anhui Province(KJ2021A0392)

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2024.00185     OR     https://www.ams.org.cn/EN/Y2026/V62/I4/649

Fig.1  Schematics of coating equipment and deposition process (Nos.1-4 are the metal targets, S1-S6 represents coatings with different preparation processes)

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
Table 1  Deposition parameters of CrN/NbN multilayer/nanolayer coatings
Fig.2  Cross-sectional SEM images of morphologies of different coatings
Fig.3  Cross-sectional low (a) and high (b, c) magnified TEM images of S6 coating (Dashed line areas in Fig.3b represent the columnar crystals); and selected area electron diffraction (SAED) pattern corresponding to the selected area in Fig.3c (d—interplanar spacing) (d)
Fig.4  High-angle annular dark field (HAADF) image and corresponding EDS elemental distribution mappings (Dark and light areas in HAADF image represent CrN and NbN, respectively, the same below) (a) and EDS line scanning result (b) of S6 coating
Fig.5  TEM analyses of middle region in S6 coating cross-section
(a) bright field TEM image
(b, d) high-resolution TEM (HRTEM) images of rectangle areas in Fig.5a
(c, e) fast Fourier transform (FFT) corresponding to the selected regions in Fig.5b (c) and Fig.5d (e)
Fig.6  TEM analyses of cross-section of S5 coating
(a, d) TEM images
(b) HAADF image
(c) EDS line scanning result along the line in Fig.6b
(e, g) HRTEM images of the selected region in Fig.6d (e) and coherent interface (g)
(f, h) FFT images corresponding to the selected region in Fig.6e (f) and Fig.6g (h)
Fig.7  Cross-sectional SEM images of micro-defects in coatings prepared by different processes (Areas 1 and 2 in Figs.7c and e represent the positions where the large particles were interrupted by ion etching)
(a) S1 (b) S2 (c) S3 (d) S4 (e) S5 (f) S6
Fig.8  Backscattered electrons (BSE) images of surface morphologies of coatings prepared by different processes (Insets are the defect area distributions)
(a) S2 (b) S3 (c) S4 (d) S5
Fig.9  Surface defect ratios and surface roughnesses of S2-S5 coating
Fig.10  XRD patterns of S1-S6 coating samples
(a) S1-S3 (b) S4-S6
Fig.11  Hardnesses of S1-S6 coatings
Fig.12  Low and high (insets) magnified OM images of Rockwell indentation morphologies of S1-S6 coating samples
(a) S1 (b) S2 (c) S3 (d) S4 (e) S5 (f) S6
Fig.13  Electrochemical impedance spectroscopies (EIS) (a-c) and equivalent circuit (d) of S1-S6 coating samples in 3.5%NaCl solution
(a) Nyquist plots (Inset is the partially enlarged view, Zim—imaginary part of impedance, Zre—real part of impedance)
(b) Bode impedance magnitude plots (Inset is the partially enlarged view, |Z|—modulus of impedance, f—frequency)
(c) Bode phase angle plots
(d) modeled equivalent circuit (Rs—solution resistance, Q1 and Q2—constant phase elements, Rpo—coating pore resistance, Rct—charge transfer resistance, RE—reference electrode, WE—working electrode)
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
Table 2  EIS fitting results of S1-S6 coating samples in 3.5%NaCl solution
Fig.14  Variations of open circuit potential (OCP) and friction coefficients of S1-S6 coating samples during tribocorrosion processes (COF—coefficient of friction)
(a) S1 (b) S2 (c) S3 (d) S4 (e) S5 (f) S6
Fig.15  SEM image and corresponding EDS mappings of unworn surface morphology of S5 coating sample after tribocorrosion test
Fig.16  Tribocorrosion rates of S1-S6 coating samples
Fig.17  Low (a, c, e, g, i, k) and high (b, d, f, h, j, l) magnified SEM images of wear track region morphologies (a, b) S1 (c, d) S2 (e, f) S3 (g, h) S4 (i, j) S5 (k, l) S6
Fig.18  Two dimensional profiles of S1-S6 coating wear tracks after tribocorrosion test (X—width, Y—depth; values in Fig.18 represent the width of wear tracks)
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-
Table 3  Chemical compositions of wear track regions in Fig.17
Fig.19  Low (a) and high (b, c) magnified SEM images of wear track cross-section in S2 coating sample
Fig.20  SEM image and EDS elemental distribution mappings of wear track cross-section in S2 coating sample
Fig.21  Schematics of tribocorrosion mechanism of different coatings
(a) single-layer coating
(b) multilayer/nanomultilayer coating
(c) multilayer/nanomultilayer coating + ion etching
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