合金元素Sn、Nb对锆合金腐蚀氧化膜相稳定性影响的第一性原理研究

陈暾; 崔节超; 李敏; 陈文; 孙志鹏; 付宝勤; 侯氢

doi:10.7498/aps.73.20240602

摘要
锆合金的水侧腐蚀是核燃料棒包壳材料设计的关键问题之一．包壳材料的耐腐蚀性能与锆合金氧化膜中 t-ZrO₂含量和 t-m 相变密切相关．目前，Zr-Sn-Nb 系合金是新型锆合金发展的主流方向．合金元素 Sn、Nb 在氧化膜中可呈现多种价态，显著影响 ZrO₂ 稳定性，然而 Sn、Nb 对 t-ZrO₂含量和 t-m 相变的影响机制尚不明晰．本文基于第一性原理计算了不同价态 Sn、Nb 掺杂 ZrO₂ 的晶体结构性质、形成焓和氧空位形成能，从原子尺度揭示了 Sn、Nb 对 ZrO₂ 稳定性的影响机理．研究表明 Sn²⁺、Nb³⁺引起显著晶格膨胀；Sn⁴⁺则造成轻微晶格膨胀，而 Nb⁵⁺引起晶格收缩，可见高氧化态下 Nb 比 Sn 更利于减小氧化膜的内应力．低价合金元素降低 ZrO₂ 稳定性，且会增大 t、m 相形成能差距；高价的 Nb⁵⁺、Sn⁴⁺均可提高 t-ZrO₂ 相对稳定性从而抑制 t-m 相变，其中 Nb⁵⁺效果显著，Sn⁴⁺则作用微弱．0-3.5GPa 范围内，t-ZrO₂ 相对稳定性随压力增大而增强．合金元素的低价态比高价态更利于在 t-ZrO₂ 中形成氧空位，因而在氧化膜/金属界面附近低氧化态区域，低价元素和压应力是稳定 t-ZrO₂ 的主要因素．通过电子结构分析，发现氧空位形成能与合金元素离子和氧空位间的电荷转移幅度（或电子局域化程度）呈正相关．这些结果有助于针对锆合金耐腐蚀性的成分优化和结构设计．

关键词:
第一性原理 /

Zr-Sn-Nb合金 /

氧化膜 /

相稳定性
Abstract
Water-side oxidative corrosion of zirconium alloys is a critical concern in the design of cladding materials for nuclear fuel rods in pressurised water reactors (PWRs), and their corrosion resistance is one of the main factors limiting service life. At present, Zr-Sn-Nb system alloys are still the main development direction of advanced zirconium alloys. Sn and Nb can exhibit a variety of valence states in the oxide film of the cladding and significantly affect the stability of ZrO₂. However, the influence mechanism of Sn and Nb on the fraction of t-ZrO₂ and the t-m phase transition is unclear. In this paper, the lattice properties, formation enthalpies, and oxygen vacancy formation energies of ZrO₂ under the doping conditions of Sn and Nb with different valence states are calculated based on the first-principles, and the influence mechanism of Sn and Nb on the stability of ZrO₂ is revealed from the atomic scale. The results show that there is a significant difference in the effects of Sn and Nb, as well as low-valent and high-valent elements. Sn²⁺ and Nb³⁺ cause significant lattice swelling distortion, Nb⁵⁺ causes lattice shrinkage which contributed to the reduction of stresses within the film, and Sn⁴⁺ causes slight lattice swelling. The low-valent elements all make ZrO₂ less stable and are unfavourable to the stability of t-ZrO₂ relative to m-ZrO₂. The high-valent Nb⁵⁺、Sn⁴⁺ promote the relative stability of t-ZrO₂ and thus inhibit the t-m phase transition, with Nb⁵⁺ having a significant effect and Sn⁴⁺ having a weak effect. The relative stability of t-ZrO₂ increases with pressure in the range of 0-3.5 GPa. Compared with high-valent elements, low-valent elements are more favourable to introduce oxygen vacancies in t-ZrO₂, thus stabilising the interfacial t-ZrO₂ and enhancing the corrosion resistance of the cladding. By investigating the electronic structure, it is found that the oxygen vacancy formation energy is positively correlated with the magnitude of charge transfer (or degree of electron localisation) between the alloying element ion and the oxygen vacancy. These results contribute to composition optimisation and structural design for corrosion resistance of zirconium alloys.

Keywords:
First-principles /

Zr-Sn-Nb alloys /

Oxide films /

Phase stability
施引文献

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合金元素Sn、Nb对锆合金腐蚀氧化膜相稳定性影响的第一性原理研究

A first-principles study on the effects of alloying elements Sn and Nb on the phase stability of corrosion oxide films of zirconium alloys

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合金元素Sn、Nb对锆合金腐蚀氧化膜相稳定性影响的第一性原理研究

A first-principles study on the effects of alloying elements Sn and Nb on the phase stability of corrosion oxide films of zirconium alloys

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