Zr-1Nb-xFe合金在模拟LOCA下的高温蒸汽氧化行为

doi:10.11900/0412.1961.2022.00632

金属学报

2024, Vol. 60

Issue (5): 670-680 DOI: 10.11900/0412.1961.2022.00632

研究论文

本期目录 | 过刊浏览

Zr-1Nb-xFe合金在模拟LOCA下的高温蒸汽氧化行为

王金鑫¹, 姚美意¹(

), 林雨晨¹, 陈刘涛², 高长源², 徐诗彤¹, 胡丽娟¹, 谢耀平¹, 周邦新¹

1 上海大学材料研究所上海 200072
2 中广核研究院有限公司深圳 518031

High Temperature Steam Oxidation Behavior of Zr-1Nb- xFe Alloy Under Simulated LOCA Condition

WANG Jinxin¹, YAO Meiyi¹(

), LIN Yuchen¹, CHEN Liutao², GAO Changyuan², XU Shitong¹, HU Lijuan¹, XIE Yaoping¹, ZHOU Bangxin¹

1 Institute of Materials, Shanghai University, Shanghai 200072, China
2 China Nuclear Power Technology Research Institute Co. Ltd., Shenzhen 518031, China

引用本文:

王金鑫, 姚美意, 林雨晨, 陈刘涛, 高长源, 徐诗彤, 胡丽娟, 谢耀平, 周邦新. Zr-1Nb-xFe合金在模拟LOCA下的高温蒸汽氧化行为[J]. 金属学报, 2024, 60(5): 670-680.
Jinxin WANG, Meiyi YAO, Yuchen LIN, Liutao CHEN, Changyuan GAO, Shitong XU, Lijuan HU, Yaoping XIE, Bangxin ZHOU. High Temperature Steam Oxidation Behavior of Zr-1Nb- xFe Alloy Under Simulated LOCA Condition[J]. Acta Metall Sin, 2024, 60(5): 670-680.

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摘要:

为探究Fe对核燃料包壳锆合金抗高温蒸汽氧化性能的影响，利用配置蒸汽发生器的同步热分析仪模拟失水事故(LOCA)下的高温蒸汽氧化环境，对Zr-1Nb-xFe (x = 0、0.05、0.2、0.4，质量分数，%)合金进行了800~1200℃下恒温3600 s的高温蒸汽氧化行为研究。采用金相显微镜、Vickers硬度仪观察分析了氧化前后样品横截面的显微组织和硬度。结果表明，在800~1100℃蒸汽中氧化时，添加Fe使Zr-1Nb合金的抗高温蒸汽氧化性能变差，且影响复杂，不随Fe含量的增加呈单一变化规律；在1200℃蒸汽中氧化时，添加Fe对Zr-1Nb合金的抗高温蒸汽氧化性能影响甚微；随氧化温度升高，4种合金的氧化动力学规律发生变化，总体由抛物线→直线规律转变，还会发生多次转折，这与锆合金基体的α↔β和氧化膜的单斜(m)↔四方(t)相变过程密切相关。

关键词 ：锆合金, 失水事故, 高温蒸汽氧化, 显微组织, 相变

Abstract：

Zirconium alloys are widely used as fuel cladding materials in water-cooled nuclear reactors due to their properties such as small thermal neutron absorption cross section, good corrosion resistance to high-temperature steam and high-pressure water, excellent mechanical properties and good compatibility with UO₂. However, under loss of coolant accident (LOCA) conditions, zirconium alloy undergoes high-temperature steam oxidation and loses its structural integrity, threatening nuclear reactor safety. With the development of the nuclear power industry, increasing demands are put forward for zirconium alloys to withstand higher burnup; hence, studying their behavior under high-temperature steam oxidation during simulated LOCA is crucial. Fe is a significant alloying element in zirconium alloys, and its addition can improve their properties. Zr-1Nb alloy is a commercial alloy with excellent corrosion resistance, and adding an appropriate amount of Fe (0.1%-0.4%; mass fraction) can further enhance the corrosion resistance of the Zr-1Nb alloy under normal operating conditions. However, the effect of adding Fe on the high-temperature steam oxidation behavior of the Zr-1Nb alloy is unclear. Therefore, the oxidation behavior of Zr-1Nb-xFe (x = 0, 0.05, 0.2, and 0.4; mass fraction, %) alloys were investigated in steam at 800, 900, 1000, 1100, and 1200^oC for 3600 s using a simultaneous thermal analyzer with a steam generator. The microstructure and microhardness of the samples before and after oxidation were analyzed using a metallographic microscope and Vickers hardness tester. The results revealed that adding Fe generally reduced the high-temperature steam oxidation resistance of Zr-1Nb-xFe alloys from 800^oC to 1100^oC for 3600 s. The effect of Fe contents on the oxidation behavior of the Zr-1Nb alloy was complex and did not show a consistent change with increasing Fe content. When oxidized at 1200^oC for 3600 s, the difference in Fe content had hardly any effect on the high-temperature steam oxidation resistance of Zr-1Nb-xFe alloys. As the oxidation temperature increased, the oxidation kinetics of the four alloys generally changed from a parabolic to a linear pattern, even occurring to multiple transitions, which was closely related to the change process of the α↔β phase for the zirconium matrix and the monoclinic (m) ↔ tetragonal (t) phase for ZrO₂.

Key words： zirconium alloy loss of coolant accident (LOCA) high-temperature steam oxidation microstructure phase transition

收稿日期: 2022-12-18

ZTFLH:

TL341

基金资助:国家自然科学基金项目(51871141)

通讯作者: 姚美意，yaomeiyi@shu.edu.cn，主要从事核燃料包壳材料锆合金和容错燃料(ATF)包壳材料的研究

Corresponding author: YAO Meiyi, professor, Tel: 13818897458, E-mail: yaomeiyi@shu.edu.cn

作者简介: 王金鑫，男，2000年生，硕士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2022.00632 或 https://www.ams.org.cn/CN/Y2024/V60/I5/670

表1 Zr-1Nb-xFe合金成分 (mass fraction / %)

图1 4种合金在800~1200℃的高温蒸汽条件下恒温3600 s的氧化动力学曲线

表2 4种合金在800~1200℃的高温蒸汽中恒温3600 s的氧化动力学参数

表3 与0Fe合金相比，0.05Fe、0.2Fe和0.4Fe合金在800~1200℃蒸汽中恒温3600 s的增重变化百分比 (%)

图2 0Fe、0.05Fe、0.2Fe和0.4Fe合金在800℃高温蒸汽中恒温3600 s后横截面的OM像

图3 0Fe、0.05Fe、0.2Fe和0.4Fe合金在900℃高温蒸汽中恒温3600 s后横截面的OM像

图4 0Fe、0.05Fe、0.2Fe和0.4Fe合金在1000、1100和1200℃高温蒸汽中恒温3600 s后横截面的OM像

图5 4种合金在800~1200℃蒸汽中恒温3600 s后横截面各部分厚度占比

表4 4种合金在800~1200℃蒸汽中恒温3600 s后横截面不同组织层的Vickers硬度 (HV)

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