锆合金高温氧化层多尺度微观结构演化机制研究

Study on Multiscale Microstructural Evolution Mechanism of High-temperature Oxide Layer on Zirconium Alloy

  • 摘要: 锆合金作为核燃料包壳材料,其高温氧化层的微观结构演化直接影响包壳失效行为与后续回收工艺。本文针对锆合金在不同氧-氮分压气氛、850~1 100 ℃多温度梯度下的氧化行为,结合动力学分析与SEM、TEM、EBSD等多尺度表征,揭示氧化规律与结构演变机制。结果表明:850~1 000 ℃氧化呈典型4阶段特征,依次为升温期薄氧化层快速生成、扩散控制的抛物型氧化、应力诱导氧化加速,最终达到完全氧化动力学平台;1 100 ℃氧化行为差异显著,快速形成致密连续的氧化层,内层柱状ZrO2晶粒呈〈001〉择优取向。高温塑性氧化层可缓释内部应力,避免开裂剥落与氧化加速,全程受扩散控制保持抛物型增长,氧分压对动力学的调控作用大幅削弱。本文研究为阐释锆包壳高温氧化机制、优化回收工艺提供理论支撑。

     

    Abstract: Zirconium alloys are widely used as nuclear fuel cladding materials owing to their favorable neutron economy and excellent corrosion resistance. However, under high-temperature mixed oxygen-nitrogen atmosphere oxidation conditions, such as those encountered during accident scenarios or spent fuel management, the rapid degradation of the oxide layer can severely compromise cladding integrity and complicate subsequent recycling and reprocessing operations. Although extensive efforts have been devoted to oxidation kinetics and macroscopic degradation behavior, a comprehensive understanding of the multiscale microstructural evolution of the oxide layer and its correlation with oxidation kinetics remains limited. In this study, the oxidation behavior of zirconium alloy was systematically investigated over a temperature range of 850-1 100 ℃ under controlled oxygen-nitrogen atmospheres. Thermogravimetric analysis was combined with multiscale characterization techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron backscatter diffraction (EBSD), to establish a correlation between oxidation kinetics and oxide-scale microstructure. The results show that oxidation at 850-1 000 ℃ exhibits a characteristic four-stage behavior, including rapid formation of a thin non-protective oxide layer during heating, diffusion-controlled parabolic growth, stress-induced acceleration associated with crack formation, and a final saturation stage. In this temperature range, the oxide scale becomes progressively unstable due to stress accumulation and crack propagation, leading to deviations from parabolic kinetics. In contrast, at 1 100 ℃, the oxidation behavior differs significantly, with a dense and continuous oxide layer forming rapidly, exhibiting a bilayer morphology with an outer fine-grained region and an inner columnar-grained region. EBSD analysis reveals that the columnar ZrO2 grains in the inner layer display a pronounced 〈001〉 preferred orientation along the growth direction, reflecting a strong crystallographic anisotropy during oxide growth. This oriented growth behavior suggests that competitive grain growth under diffusion control governs the development of the columnar structure. With increasing oxidation time, longitudinal microcracks gradually develop due to growth-induced stresses. Although these cracks locally modify oxygen transport paths, the overall oxidation kinetics remain parabolic, confirming that bulk diffusion through the dense oxide layer continues to dominate. Nanoscale TEM observations reveal severe intragranular lattice distortion and orientation fluctuations, indicating a highly strained oxide microstructure. Nb-rich second-phase particles (SPPs) at grain boundaries exhibit delayed oxidation behavior, leading to localized chemical and structural heterogeneities. These heterogeneities promote stress concentration and facilitate the nucleation of microvoids and microcracks, thereby progressively weakening the protective capability of the oxide layer. The combined effects of lattice distortion, second-phase particle behavior, and microcrack formation highlight the intrinsic microstructural complexity of the oxide scale. By integrating oxidation kinetics with multiscale microstructural analysis, this study establishes a mechanistic correlation between oxidation behavior and microstructural evolution. The results provide critical insights into the microstructural origins of oxide layer instability and high-temperature oxidation failure of zirconium alloy cladding. These findings offer valuable guidance for predicting cladding degradation behavior and for optimizing recycling and reprocessing strategies of zirconium alloy materials in nuclear fuel cycle applications.

     

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