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Cr涂层锆合金包壳高温蒸汽氧化动力学及微观机理研究
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中广核研究院有限公司

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High-temperature steam oxidation kinetics and mechanisms of Cr-coated Zr alloy claddings
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    摘要:

    Cr涂层锆合金包壳具备抗高温蒸汽氧化性能优异、耐腐蚀和耐磨蚀性能良好、工程应用难度较小等特点,成为最具前景的近期型事故容错燃料候选材料之一。本文以Zr-1Nb合金管为基体材料,采用磁控溅射工艺制备均匀致密Cr涂层,涂层厚度范围12~15 μm。通过同步综合热分析仪开展双面高温蒸汽氧化试验,氧化温度为1000°C、1100°C和1200°C,氧化时间为300~5000 s不等,系统研究反应堆事故工况下Cr涂层锆合金包壳高温蒸汽氧化行为。采用扫描电子显微镜、能谱仪和X射线衍射仪表征高温氧化产物膜微观形貌特征、氧化层厚度、元素分布以及物相组成等,建立Cr涂层氧化动力学模型,探讨高温氧化机理。研究表明,高温蒸汽环境中,Cr涂层锆合金包壳外壁形成致密Cr2O3层,有效阻止O元素扩散至Zr合金基体,从而提升复合包壳的耐高温性能。其次,Cr涂层高温蒸汽氧化动力学曲线遵循抛物线规律,氧化速率常数比锆合金低大约2个数量级,显著提升锆合金包壳抗高温蒸汽氧化性能。

    Abstract:

    The Cr-coated Zr alloy materials appear to be one promising short-term accident tolerant fuel cladding concept, due to their outstanding high-temperature oxidation resistance and improved resistance to fretting wear. In addition, there are few barriers or challenges to be applied to nuclear reactors for coated Zr alloy claddings. In this paper, 12-15 μm-thickness coatings have been deposited by magnetron-sputtering process on the outer surface of Zr-1Nb alloy tubes. Two-sided isothermal oxidation tests were performed in flowing steam by synchronous thermogravimetric analyzer, at temperatures ranging from 1000°C to 1200°C and for oxidation times ranging from 300 s to 5000 s, with the object of systematically studying the behavior during accidents. Scanning electron microscopy equipped with energy dispersive X-ray spectroscopy and X-ray diffraction were utilized to characterize the microstructure, element distributions and phase of oxide scale to study the oxidation kinetics and mechanisms of Cr coating. Based on these analyses, dense chromia scale was developed on the outer surface of cladding during steam oxidation, preventing the oxygen atoms from diffusing into the substrate, to improve the high-temperature resistance of the composited claddings. In addition, the oxidation kinetics of the Cr coating was nearly parabolic and the rate constants was at least two orders of magnitude lower than the Zr alloy, enhancing high-temperature steam oxidation resistance of Zr alloy claddings.

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廖业宏,彭振驯,严俊,王占伟,李思功,任啟森. Cr涂层锆合金包壳高温蒸汽氧化动力学及微观机理研究[J].稀有金属材料与工程,2023,52(1):291~299.[Liao Yehong, Peng Zhenxun, Yan Jun, Wang Zhanwei, Li Sigong, Ren Qisen. High-temperature steam oxidation kinetics and mechanisms of Cr-coated Zr alloy claddings[J]. Rare Metal Materials and Engineering,2023,52(1):291~299.]
DOI:10.12442/j. issn.1002-185X.20220364

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  • 收稿日期:2022-04-27
  • 最后修改日期:2022-09-11
  • 录用日期:2022-09-22
  • 在线发布日期: 2023-02-13
  • 出版日期: 2023-02-08