张君松, 吴军, 廖京京, 韦天国, 龙冲生. 锆合金氧化膜及基体中氧的扩散[J]. 原子能科学技术, 2024, 58(1): 175-180. DOI: 10.7538/yzk.2023.youxian.0116
引用本文: 张君松, 吴军, 廖京京, 韦天国, 龙冲生. 锆合金氧化膜及基体中氧的扩散[J]. 原子能科学技术, 2024, 58(1): 175-180. DOI: 10.7538/yzk.2023.youxian.0116
ZHANG Junsong, WU Jun, LIAO Jingjing, WEI Tianguo, LONG Chongsheng. Oxygen Diffusion in Oxide Film and Matrix of Zirconium Alloys[J]. Atomic Energy Science and Technology, 2024, 58(1): 175-180. DOI: 10.7538/yzk.2023.youxian.0116
Citation: ZHANG Junsong, WU Jun, LIAO Jingjing, WEI Tianguo, LONG Chongsheng. Oxygen Diffusion in Oxide Film and Matrix of Zirconium Alloys[J]. Atomic Energy Science and Technology, 2024, 58(1): 175-180. DOI: 10.7538/yzk.2023.youxian.0116

锆合金氧化膜及基体中氧的扩散

Oxygen Diffusion in Oxide Film and Matrix of Zirconium Alloys

  • 摘要: 锆合金氧化膜及基体中氧的扩散系数是锆合金腐蚀动力学中的重要参数,目前文献报道的氧在锆及氧化膜中的扩散系数数值差异较大。本文通过真空退火试验,得到不同温度下氧化膜中氧浓度分布,计算了氧在锆合金基体中的扩散系数;通过氧化膜的等效扩散模型,由腐蚀转折前的腐蚀增重曲线,估算锆合金氧化膜中氧的扩散系数,得到Zr-Sn-Nb合金基体中氧的扩散系数随温度的变化规律为DZr(cm2/s)=0.18exp(-180 000/RT);通过转折前的腐蚀增重曲线,估算得到氧化膜中氧的扩散系数随温度的变化规律为Dox(cm2/s)=3×10-7exp(-101 550/RT)。

     

    Abstract: The diffusion coefficient of oxygen in zirconium alloy oxide film and matrix is an important parameter in corrosion kinetics of zirconium alloys. At present, there are some reports on the diffusion coefficient of oxygen in zirconium and oxide film, but the numerical values in the literature are quite different. In this paper, zirconium alloy was corroded in pure water to obtain a sample with an oxide film thickness of 1 μm. Through vacuum annealing test, the oxygen concentration distribution of the oxide film at four different temperatures was obtained, the diffusion coefficient of oxygen in zirconium alloy matrix was calculated, and the Arrhenius relation of the diffusion coefficient in this temperature range was obtained by fitting. Compared with the literature data, the trend is similar, but the values are different. The main reasons may be the following two aspects:One is the measurement deviation of oxygen concentration distribution curve, including spatial position deviation and concentration error, and the other is the different grain size of samples. The diffusion coefficient of oxygen in zirconium metal without irradiation obtained in this work can be mutually verified with the literature data, which has high reliability. Based on the corrosion weight gain curves of two zirconium alloys at four different temperatures, the diffusion coefficient of oxygen in the zirconium alloy oxide film was estimated by the equivalent diffusion model of the oxide film and the corrosion weight gain curve before the corrosion transition. It is found that the diffusion coefficient of oxygen in the zirconium alloy oxide film increases obviously with the increase of temperature, and the diffusion speed of atoms is significantly affected by the microstructure of the diffusion medium except temperature. Based on the research of two parts, it is found that the diffusion coefficient of oxygen in the oxide film is greater than that in zirconium metal when the temperature is below 440℃, and the diffusion coefficient of oxygen in the oxide film is more than twice that in zirconium metal when the temperature is below 400℃, which shows that the diffusion of oxygen in the oxide film of zirconium alloy is main at the interface at lower temperature (440℃ in this paper), and further shows that grain boundaries, pores and microcracks in the oxide film play a very important role in the corrosion behavior of the alloy. The above research provides important calculation parameters and basic research theory for the corrosion kinetic model of zirconium alloy. The results show that the diffusion coefficient of oxygen in Zr-Sn-Nb matrix follows a relationship as DZr(cm2/s)=0.18·exp(-180 000/RT). The diffusion coefficient of oxygen in oxide film, which follows a relationship as Dox(cm2/s)=3×10-7exp(-101 550/RT), is also evaluated by the weight gain profile in pre-transition stage.

     

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