Effect of Oxidation Time on the Steam Oxidation Behavior of MAO/Cr-coated Zr-1Nb Alloy at 1 100 ℃

WANG Xingping; DONG Xiaoli; LIN Shujia; WANG Dongtang; LU Wenjuan; XUE Wenbin; LIAO Yizhao

doi:10.16490/j.cnki.issn.1001-3660.2025.15.013

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Surface Technology ›› 2025, Vol. 54 ›› Issue (15) : 145-155. DOI: 10.16490/j.cnki.issn.1001-3660.2025.15.013

Technology and Application

Effect of Oxidation Time on the Steam Oxidation Behavior of MAO/Cr-coated Zr-1Nb Alloy at 1 100 ℃

WANG Xingping^{1, 2}, DONG Xiaoli³, LIN Shujia⁴, WANG Dongtang¹, LU Wenjuan¹, XUE Wenbin^{2, *}, LIAO Yizhao^{1, 2, *}

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Abstract

The work aims to investigate the effect of oxidation time on the steam oxidation behavior of MAO/Cr-coated Zr-1Nb alloy in 1 100 ℃ steam environment. By micro-arc oxidation (MAO) and filtered cathodic vacuum arc deposition (FCVAD) techniques, a uniform and dense MAO/Cr composite coating was deposited on the surface of Zr-1Nb alloy. The oxidation resistance of bare and MAO/Cr-coated Zr-1Nb alloy in a 1 100 ℃ steam environment was evaluated by a thermogravimetric analyzer (TGA). The cross-sectional microstructures, metallographic microstructures, phase composition and composition depth distribution of the composite coating before and after oxidation were analyzed by scanning electron microscope (SEM), optical microscope (OM), X-ray diffractometer (XRD) and glow discharge optical emission spectrometer (GDOES). In the 1 100 ℃ steam environment, as the oxidation time increased from 600 s to 5 400 s, the outer Cr layer for the composite coating was completely oxidized. Afterwards, the Cr₂O₃ near the Cr/Zr interface was reduced by Zr, forming a reduced metal Cr layer. The Zr alloy substrate below the composite coating was oxidized to generate an inner ZrO₂layer of approximately 7.0 μm thick again after 5 400 s oxidation. Furthermore, a thin Cr₂O₃ layer with a thickness of about 0.8 μm was still attached to the coating surface after oxidation for 5 400 s, since the outer surface of Cr layer was directly exposed to the steam environment. Meanwhile, some Zr atoms from Zr alloy substrate diffused outwards into the reduced Cr layer and the top Cr₂O₃ layer of the composite coating, forming ZrO₂oxide. The trace amounts of ZrO₂ in the reduced Cr and Cr₂O₃ layers accelerated the diffusion of oxygen atoms into Zr alloy substrate. On the other hand, the intermediate MAO layer for the composite coating underwent serious dissolution in the 1 100 ℃ steam environment and the cross-sectional metallographic microstructure of the MAO layer changed from dark black to light gray after exposure from 600 s to 3 600 s. Some oxygen atoms in the MAO layer diffused into Zr alloy substrate and Cr coating, but the phosphorus element was still enriched in the original region of MAO coating after exposure of 600-5 400 s. The ZrO₂ in the MAO layer transformed into the Zr₃O phase, but it still slowed down the inward oxygen diffusion. Meanwhile, the dissolution phenomenon of the intermediate MAO layer also occurred after annealing in the 1 100 ℃ Ar environment and more oxygen atoms of MAO layer diffused into Zr alloy substrate and metallic Cr layer with the increase of annealing time. Compared to the 1 100 ℃ Ar environment, the high-temperature steam environment accelerated the dissolution of the intermediate MAO layer. Consequently, the ZrO₂ phase in the MAO layer disappeared after oxidation of 600-3 600 s and the phase component was only composed of Cr₂O₃, Cr and trace Zr₃O. However, the ZrO₂ phase appeared again after 5 400 s oxidation and the Zr alloy substrate was oxidized to form a newborn ZrO₂ layer. In addition, the MAO/Cr composite coating effectively prevented hydrogen permeation into Zr alloy substrate during the high-temperature steam oxidation process. As a result, the mass gain of MAO/Cr-coated Zr-1Nb alloy was 41.5% of that of bare Zr alloy after 5 400 s exposure at 1 100 ℃ and the MAO/Cr composite coating excellently improved the oxidation resistance of Zr-1Nb alloy substrate in the 1 100 ℃ steam environment.

Key words

MAO/Cr composite coating / oxidation time / high-temperature steam oxidation / high-temperature annealing / dissolution of MAO layer

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WANG Xingping, DONG Xiaoli, LIN Shujia, WANG Dongtang, LU Wenjuan, XUE Wenbin, LIAO Yizhao. Effect of Oxidation Time on the Steam Oxidation Behavior of MAO/Cr-coated Zr-1Nb Alloy at 1 100 ℃[J]. Surface Technology. 2025, 54(15): 145-155 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.15.013

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Funding

National Natural Science Foundation of China (12405329); Science and Technology Program of Gansu Province (23JRRA1699); Innovation Fund Project of Colleges and Universities in Gansu Province (2024A-041, 2025B-069); Young Scholars Science Foundation of Lanzhou Jiaotong University (2023002, 2024001); Open Fund of Key Laboratory of Beam Technology of Ministry of Education (BEAM2024G03); Beijing Normal University and Tianyou Youth Talent Lift Program of Lanzhou Jiaotong University