Effect of Vacuum Annealing on Microstructure and Properties of Zr-B-N/ZrO2 Multilayered Coatings

YE Jiani; MA Lisha; ZHANG Jifu; LIU Yanmei; CAO Fengting; FAN Qixiang; WANG Tiegang

doi:10.16490/j.cnki.issn.1001-3660.2025.13.010

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Surface Technology ›› 2025, Vol. 54 ›› Issue (13) : 107-120. DOI: 10.16490/j.cnki.issn.1001-3660.2025.13.010

Friction, Wear and Lubrication

Effect of Vacuum Annealing on Microstructure and Properties of Zr-B-N/ZrO₂ Multilayered Coatings

YE Jiani¹, MA Lisha^2*, ZHANG Jifu¹, LIU Yanmei¹, CAO Fengting¹, FAN Qixiang¹, WANG Tiegang^1*

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Abstract

The nano-composite structure of Zr-B-N coatings, consisting of amorphous nanocrystals, provides advantages such as high hardness, high toughness, and excellent wear resistance. However, during high-temperature operation, the amorphous BN phases within the coatings are prone to oxidation and volatilization, leading to poor high-temperature thermal stability and oxidation resistance. This significantly restricts its application in high-temperature environments like high-efficiency machining and dry cutting. To overcome these limitations, a nano-multilayer structure is designed to integrate the superior hardness-toughness balance of Zr-B-N layers with the excellent thermal resistance of ZrO₂ layers. Periodic deposition of ZrO₂ layers into the Zr-B-N coating is implemented to enhance thermal stability. Vacuum annealing further improves the properties of Zr-B-N/ZrO₂ multilayer composite coatings to systematically investigate the mechanisms of interfacial diffusion behavior, microstructure, mechanical properties, and tribological properties at high temperature.
Zr-B-N/ZrO₂ multilayer composite coatings are fabricated on YG 8 cemented carbide and single-crystal Si(100) substrates using composite magnetron sputtering technology. Vacuum annealing experiments are conducted at 500-800 ℃ (<10^‒3 Pa, 1 h) in a vacuum tube furnace. The phase composition, micro-morphology, microstructure, mechanical properties, and tribological properties of the coatings are analyzed using XRD, FESEM, HRTEM, nanoindentation, high-load scratch testing, high-temperature tribometry, ultra-depth-of-field 3D microscopy, and white light interferometry.
The Zr-B-N/ZrO₂ multilayer composite coating primarily consists of the t-ZrO₂ phase and fcc-ZrN phase. As the annealing temperature increases, the B content gradually decreases while the O content increases, accompanied by enhanced diffraction peak intensity of the t-ZrO₂ phase, which shifts toward larger angles. When annealing at 600 ℃, the coating surface remains dense with an intact nano-multilayer structure, exhibiting maximum hardness and elastic modulus values of 32.75 GPa and 391.70 GPa, respectively. The corresponding bonding strength reaches 47.95 N, with a friction coefficient of 0.658 and a wear rate of 1.11×10^‒5 mm³/(N·m). When the annealing temperature reaches 800 ℃, the O content decreases while the B content increases, with fcc-ZrO and hcp-ZrB₂ phases precipitating in the coating. The friction coefficient (0.507) and wear rate (4.54×10^‒6 mm³/(N·m)) reach their lowest values, representing reductions of 43.29% and 69.97%, respectively, compared with the values before vacuum annealing. However, due to grain size growth, numerous microcracks form at grain boundaries. The formation of extensive cross-sectional microcrack channels enhances mutual diffusion between elements, leading to significant interfacial solubility and nearly complete collapse of the nano-multilayer structure. Edge dislocations in the Zr-B-N layer penetrate the interface and propagate into the ZrO₂ layer. This interfacial degradation results in a notable reduction in adhesion between the coating and substrate, with hardness, elastic modulus, and bonding strength decreasing to their minimum values.
Appropriate vacuum annealing can significantly influence coating properties. When annealing at 600 ℃, the coating exhibits optimal comprehensive performance. Although wear resistance improves after annealing at 800 ℃, the overall performance deteriorates substantially due to structural damage.

Key words

hybrid magnetron sputtering / vacuum annealing / nano-multilayered coating / microstructure / mechanical property / tribological property

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YE Jiani, MA Lisha, ZHANG Jifu, LIU Yanmei, CAO Fengting, FAN Qixiang, WANG Tiegang. Effect of Vacuum Annealing on Microstructure and Properties of Zr-B-N/ZrO₂ Multilayered Coatings[J]. Surface Technology. 2025, 54(13): 107-120 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.13.010

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