研究论文

冷却速率对锆合金氢化物析出的影响

  • 公维佳 ,
  • 梁森茂 ,
  • 张敬翊 ,
  • 李时磊 ,
  • 孙勇 ,
  • 李中奎 ,
  • 李金山
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  • 1.西北工业大学 材料学院 西安 710072
    2.西北工业大学 太仓长三角研究院清洁能源研究中心 太仓 215400
    3.西北工业大学 伦敦玛丽女王大学工程学院 西安 710072
    4.北京科技大学 新金属材料国家重点实验室 北京 100083
    5.中国工程物理研究院 核物理与化学研究所 绵阳 621900
公维佳,男,1986年生,副教授
李中奎,lizhangyi@nwpu.edu.cn,主要从事难熔合金的研究

收稿日期: 2023-04-13

  修回日期: 2023-07-27

  网络出版日期: 2023-09-04

基金资助

国家自然科学基金项目(U2230124,12005170,U2067217);国防科技工业局乏燃料后处理科研专项项目

Effect of Cooling Rate on Hydride Precipitation in Zirconium Alloys

  • GONG Weijia ,
  • LIANG Senmao ,
  • ZHANG Jingyi ,
  • LI Shilei ,
  • SUN Yong ,
  • LI Zhongkui ,
  • LI Jinshan
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  • 1.School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, China
    2.Clean Energy Research Center, Yangtze River Delta Research Institute of Northwestern Polytechnical University, Taicang 215400, China
    3.Queen Mary University of London Engineering School, Northwestern Polytechnical University, Xi'an 710072, China
    4.State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China
    5.Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, China
LI Zhongkui, professor, Tel: 13991818960, E-mail: lizhangyi@nwpu.edu.cn

Received date: 2023-04-13

  Revised date: 2023-07-27

  Online published: 2023-09-04

Supported by

National Natural Science Foundation of China(U2230124,12005170,U2067217);State Administration of Science, Technology and Industry for National Defense

摘要

氢化物是影响核燃料固有性能与核结构材料服役安全的关键问题,而冷却速率显著影响氢化物的宏观形貌和微观特性。本工作借助OM、BSE-SEM以及EBSD等表征手段,对不同冷却条件下析出的锆氢化物进行了系统研究。实验结果发现,fcc结构δ相是锆合金中形成的主要氢化物结构,其在锆合金板材轧向与横向平面内呈条状分布,随冷却速率提高,亚稳态面心四方(fct)结构γ氢化物数量明显增多。2种结构的氢化物在α-Zr母体晶粒内取向一致,与基体保持{0001}//{111}、<112¯0>//<110>取向关系。证实氢化物尖端的强应变能够诱导新的纳米氢化物优先在已有氢化物尖端位置形核、生长,然后通过氢化物堆垛、排列构成条状氢化物。此外,锆合金中Zr(Fe, Cr)2第二相粒子作为微区氢陷阱与形核位点,对氢化物条状形貌的形成具有促进作用。

本文引用格式

公维佳 , 梁森茂 , 张敬翊 , 李时磊 , 孙勇 , 李中奎 , 李金山 . 冷却速率对锆合金氢化物析出的影响[J]. 金属学报, 2024 , 60(9) : 1155 -1164 . DOI: 10.11900/0412.1961.2023.00166

Abstract

Zirconium alloys have been used as nuclear fuel claddings for decades, owing to their low thermal neutron absorption cross-section, good thermal conductivity, suitable mechanical properties, and excellent corrosion resistance. During in-reactor service, zirconium alloy cladding undergoes a corrosion reaction with the coolant and absorbs part of the hydrogen produced due to corrosion, resulting in the formation of brittle zirconium hydrides. Hydrides impose great risk to the mechanical integrity of the fuel claddings during reactor operation and even during storage and transportation of spent fuel rods. Hydride morphological features such as size, distribution, and growth direction are closely related to the cooling rate, which also affects the microstructural characteristics of hydrides, including nucleation sites, crystal structure, and precipitation strain. These factors further influence the mechanical properties and corrosion resistance of zirconium alloy cladding. Therefore, investigation of the influence of cooling rate on hydride precipitation is crucial to develop a theoretical study that can aid in the prevention of hydride embrittlement in nuclear fuel claddings. Herein, multiscale characterization techniques including OM, BSE-SEM, and EBSD were used to systematically investigate the morphology and microstructure of hydride precipitation under various cooling conditions in a Zr-4 plate material. The fcc-structured δ phase, well aligned in the plane of rolling and transverse directions, is the predominant hydride formed in zirconium alloys was found. With rapid cooling rates, the thickness and spacing of the hydrides decreased, forming finely dispersed plate-like distribution morphology. Intragranular hydrides and metastable fcc-structured γ-hydrides increased in number density with rapid cooling rate. The two types of hydrides exhibited the same crystallographic orientation while sharing one α-parent grain, both holding an orientation relationship of {0001}//{111} and <112¯0>//<110> with the α-Zr matrix, independent of the cooling rate. Prior to complete transformation into the δ phase, the γ-hydride is proposed as a transitional phase during the initial stage of hydride precipitation, given that the γ-phase requires a lower hydrogen concentration for the phase transformation and exhibits lower precipitation strain than the δ phase. {111}<112¯> twinning structures were identified within the hydrides, which are expected to favor alleviating hydride precipitation strains. High angular resolution EBSD revealed that strong tensile strains induced by the volume expansion of hydride precipitation are present in the vicinity of the hydride tip, which might act as the preferential nucleation site for new hydride precipitation, promoting the formation of hydride plate morphology. Furthermore, nanohydrides were identified precipitating at the boundary of Zr(Fe, Cr)2 second-phase particles, which is expected to play a role in the morphologic development of plate hydrides.

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