Microstructure, oxidation behavior and tribological properties of AlCrN/Cu coatings deposited by a hybrid PVD technique

doi:10.1016/j.jmst.2021.06.007

Abstract

Abstract:

Achieving high hardness and low friction at elevated temperatures for nitride-based hard coatings has substantial scientific interest and application significance. In this study, AlCrN/Cu coatings were deposited by a hybrid PVD technique combining arc evaporation from an Al₆₀Cr₄₀ target and magnetron sputtering from a Cu target in a mixed Ar and N₂ atmosphere. The microstructure, oxidation behavior, and tribological properties of the coatings were investigated. AlCrN/Cu coatings show a dual-phase structure of (Al, Cr)N solid solution and Cu metallic phase. Excessive sputtering power of the Cu target induces the disintegration of interlayer interfaces of the nano-multilayered geometry, accompanied by a decline in hardness from above 30 GPa to 22.7 GPa. Moreover, the formation of fine CuO grains on the coating surface is conducive to reducing the friction coefficient of AlCrN/Cu when exposed to air at high temperatures. The AlCrN/Cu coating with a sputtering power of 0.5 kW obtains a friction coefficient of 0.39 ± 0.05 after pre-oxidation at 800 °C, distinctly lower than that of AlCrN, which exhibits a friction coefficient of ~0.65. The further transformation of CuO to cubic Cu(Al, Cr)₂O₄, which stems from the solid-state reaction of CuO, Al₂O₃, and Cr₂O₃, would cause a rise in friction coefficient and wear loss. The mechanism of oxidation and tribological behavior of the AlCrN/Cu coatings related to the temperature and Cu content was discussed.

Key words: AlCrN/Cu coatings, Microstructure, Oxidation, Friction

Dongsen Geng, Haiqing Li, Ziliang Chen, Yu X. Xu, Qimin Wang. Microstructure, oxidation behavior and tribological properties of AlCrN/Cu coatings deposited by a hybrid PVD technique[J]. J. Mater. Sci. Technol., 2022, 100: 150-160.

Figures/Tables 17

Fig. 1. Schematic diagram of the PVD deposition system used showing the cathode positions.

Table 1 Chemical compositions analyzed by EDS of AlCrN and AlCrN/Cu coatings deposited in different PCu.

Coating	P_Cu, kW	Elemental concentration, at.%				Al/(Al+Cr)
		Al	Cr	Cu	N
AlCrN	0	27.7	24.5	N/A	47.8	0.53
AlCrN/Cu	0.3	26.7	23.5	2.6	47.2	0.53
	0.5	25.4	22.0	7.9	44.7	0.53
	0.7	22.9	19.9	13.8	43.4	0.54

Fig. 2. SEM fracture cross sections of (a) AlCrN and (b-d) AlCrN/Cu coatings with PCu of (b) 0.3, (c) 0.5, and (d) 0.7 kW.

Fig. 3. (a) GIXRD patterns and (b) FWHM of (111) peak of (Al, Cr)N phase for AlCrN/Cu coatings with respect to PCu.

Fig. 4. XPS spectras of (a) Cu 2p3/2 and (b) N 1 s core level for as-deposited AlCrN/Cu coatings at various PCu.

Fig. 5. (a) Cross sectional TEM bright-field image and (b) SAED pattern of the AlCrN/Cu coating with PCu = 0.3 kW; (c) STEM-HADDF image indicating distinct nano-multilayer structure, consisting of AlCrN and Cu sublayers; (d) high-resolution TEM micrograph for two adjacent columnar grains in this coating.

Fig. 6. (a and b) TEM bright-field image of AlCrN/Cu with PCu = 0.7 kW showing fine-grain morphology; (c) SAED pattern of the polycrystalline coating; (d) STEM HADDF image and EDS compositional mapping around the film-substrate interface.

Fig. 7. (a) High-resolution TEM micrograph of AlCrN/Cu with PCu = 0.7 kW; (b) FFT pattern from the marked area in (a); (c) Enlarged HRTEM image focusing on a Cu grain.

Fig. 8. Indentation hardness (H), elastic modulus (E), and H/E ratio of AlCrN/Cu coatings.

Fig. 9. SEM surface micrographs of (a) AlCrN and (b to d) AlCrN/Cu coatings with PCu of (b) 0.3 kW, (c) 0.5 kW, and (d) 0.7 kW in the as-deposited state and after oxidation at various temperatures for 30 min.

Fig. 10. GIXRD patterns of AlCrN/Cu coatings deposited with PCu of (a) 0.3, (b) 0.5, and (c) 0.7 kW on cemented carbide after oxidation at 700, 800, and 900 °C.

Fig. 11. Friction coefficients of as-deposited and oxidized AlCrN coatings as a function of sliding distance recorded at RT.

Fig. 12. Friction coefficient curves of as-deposited and oxidized AlCrN/Cu coatings with the PCu of (a) 0.3, (b) 0.5, and (c) 0.7 kW recorded at RT.

Table 2 Surface roughness of as-deposited and oxidized AlCrN/Cu coatings with different PCu.

Coating	P_Cu, kW	Surface roughness, nm
		As-deposited	700 °C oxidized	800 °C oxidized	900 °C oxidized
AlCrN	0	121 ± 4	129 ± 5	127 ± 4	139 ± 8
AlCrN/Cu	0.3	121 ± 5	128 ± 3	116 ± 3	143 ± 2
	0.5	111 ± 2	118 ± 4	116 ± 6	151 ± 3
	0.7	146 ± 3	135 ± 2	232 ± 3	187 ± 5

Fig. 13. Specific wear rates of as-deposited and oxidized AlCrN/Cu coatings with different PCu after ball-on-disc tests.

Fig. 14. SEM surface morphologies of wear track with EDS analyses for 800 °C oxidized AlCrN/Cu with PCu of (a and c) 0.5 and (b and d) 0.7 kW.

Fig. 15. SEM cross sections of wear track for (a and b) 800 and (c and d) 900 °C oxidized AlCrN/Cu coatings with PCu of (a and c) 0.5 and (b and d) 0.7 kW.

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