金属钇高温吸氢动力学

Thermal Hydrogen Absorption Kinetics of Metallic Yttrium at High-temperature

  • 摘要: 金属钇及其氢化物(氢化钇,YHx)是高温、小型化、轻量化新型核反应堆的理想慢化剂候选材料。现有研究关于700~900 ℃高温区间的金属钇吸氢动力学数据较为匮乏,微观组织与吸氢速率的关联机制尚未明确。为此,本文以纯金属钇为对象,采用恒温定容吸氢法结合金相表征技术开展实验,探究高温下吸氢反应的动力学规律。结果表明:金属钇和YHx的吸氢反应更符合一级动力学模型;同一温度下,反应速率常数随氢化程度(H/Y比值)增加显著降低,而温度升高则会大幅提升速率常数,900 ℃时纯金属钇仅需10 s即可实现反应平衡;金属钇吸氢反应活化能为138.008 kJ/mol,吸氢相变遵循α-Y→α-Y+δ-YHx→δ-YHx的过程,晶界是δ-YH相的优先形核位点。本文研究填补了高温吸氢动力学数据的空白,阐明了速率控制机理,为三元基材料在高温储氢系统和核反应堆中的应用提供了关键数据支持。

     

    Abstract: Yttrium, as an important member of rare earth metals, its hydride, hydrogenated yttrium (YHx), due to its excellent high-temperature thermal stability, high hydrogen density, and small neutron absorption cross-section, has become an ideal candidate material for slow neutron moderators suitable for high-temperature, miniaturization, and lightweight new nuclear reactors. However, there is a gap in the hydrogen absorption kinetics data of yttrium in the 700-900 ℃ high-temperature range in existing research, and the correlation mechanism between the microstructure and hydrogen absorption rate has not been clarified. This paper takes pure metallic yttrium as the research object and conducts high-temperature hydrogen absorption kinetics experiments using the constant volume and pressure method. Data analysis was carried out using the first-order reaction model and Arrhenius equation, and the kinetic laws of hydrogen absorption reactions at high-temperatures were explored through the combination of metallographic characterization analysis systems. The main conclusions are as follows. Firstly, the hydrogen absorption reaction fraction (F) shows a rapid increase-slow stabilization parabolic characteristic over time in the initial stage, hydrogen atoms are rapidly adsorbed and react with the yttrium matrix, and F increases rapidly. In the later stage, due to the formation of the hydrogen compound layer and the increase in the resistance of hydrogen atom diffusion, the growth rate of F gradually slows down until equilibrium is reached. The temperature has a particularly significant effect on shortening the equilibrium time: pure yttrium (H/Y=0) has an equilibrium time of approximately 200 s at 700 ℃, 60 s at 800 ℃, and only 10 s at 900 ℃ for instant equilibrium; even for H/Y=1.3 with a higher hydrogenation degree, the equilibrium time at 900 ℃ is shortened from 1 700 s at 700 ℃ to 300 s, which is highly compatible with the core requirement of the nuclear reactor hydrogen purification system for rapid capture of hydrogen species. Secondly, the hydrogen absorption reaction of metal yttrium and its hydride more conforms to the first-order reaction kinetics model, and the fitting correlation coefficient R2 is generally ≥0.98. At the same temperature, the reaction rate constant (k) decreases significantly with the increase in the H/Y ratio; While increasing the temperature can significantly increase the k, at 900 ℃, indicating that high-temperature can effectively break through the diffusion barrier of hydrogen atoms in the yttrium matrix. Thirdly, based on the Arrhenius equation, the activation energy of the hydrogen absorption reaction of metal yttrium in the 700-900 ℃ range is 138.008 kJ/mol. Fourthly, the hydrogen absorption phase transition follows the process of α-Y→α-Y+δ-YHx→δ-YHx, with the grain boundaries being the preferred nucleation sites of the δ-YHx phase. This study fills the gap in high-temperature hydrogen absorption kinetics data, clarifies the rate control mechanism, and provides key data support for the application of yttrium-based materials in high-temperature hydrogen storage systems and nuclear reactors.

     

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