目的 研究氧化时间对MAO/Cr复合涂层1 100 ℃蒸汽氧化行为的影响,揭示该涂层在高温环境中的组织结构变化和氧化机制。方法 采用微弧氧化（MAO）技术在Zr-1Nb合金表面制备MAO膜,并借助磁过滤阴极真空弧离子镀（FCVAD）技术沉积Cr层,组成均匀致密的MAO/Cr复合涂层。采用热重分析仪（TGA）评估二者在1 100 ℃蒸汽环境中的抗氧化性,考察复合涂层在氧化前后的截面结构、金相组织、物相组成、成分深度分布。结果 在1 100 ℃蒸汽环境中,当氧化时间从600 s延长至5 400 s时,MAO/Cr复合涂层外表面Cr层完全氧化后,Cr/Zr界面附近的Cr2O3通过Zr的还原作用,形成了还原金属Cr层。在还原Cr层中,微量的ZrO2加速了氧原子向锆合金基体内的扩散速度。MAO膜中间层在高温蒸汽环境中出现了溶解现象,ZrO2转变为Zr3O相,但依然减缓了氧原子向锆合金基体内的扩散。同样,在1 100 ℃氩气中高温退火处理后,MAO膜也出现了溶解现象,随着退火时间的延长,更多的氧原子溶解,并进入锆合金基体和金属Cr层。相对于1 100 ℃氩气环境,高温蒸汽环境加速了MAO膜中间层的溶解。结论 在1 100 ℃蒸汽环境中,MAO/Cr复合涂层提高了Zr-1Nb合金基体的抗氧化能力。
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 ZrO2 layer 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 ZrO2 oxide. 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.
关键词
MAO/Cr复合涂层 /
氧化时间 /
高温蒸汽氧化 /
高温退火 /
微弧氧化膜溶解
Key words
MAO/Cr composite coating /
oxidation time /
high-temperature steam oxidation /
high-temperature annealing /
dissolution of MAO layer
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基金
国家自然科学基金（12405329）; 甘肃省科技计划（23JRRA1699）; 甘肃省教育厅创新基金（2024A-041,2025B-069）; 兰州交通大学青年基金（2023002,2024001）; 射线束技术教育部重点实验室（北京师范大学）开放研究基金（BEAM2024G03）; 兰州交通大学“天佑青年托举人才计划”
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