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1000 – 1100 °C下多弧离子镀Cr涂层Zr-4合金的高温蒸气氧化行为
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南华大学 机械工程学院

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TL352.1

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湖南省自然科学基金资助(项目号2020JJ5467,2022JJ40348),衡阳市科技计划项目资助(项目号202150063435)


High temperature steam oxidation behavior of Cr-coated Zr-4 alloy prepared by multi-arc ion plating at 1000 – 1100 °C
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School of Mechanical Engineering, University of South China

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    摘要:

    Cr涂层锆合金包壳是提高轻水反应堆燃料组件抗高温氧化性能的重要方法。本文旨在研究Cr涂层Zr-4合金在水蒸气环境中的高温氧化行为,采用多弧离子镀工艺制备Cr涂层Zr-4合金样品,在1000 °C和1100 °C水蒸气环境中开展高温氧化实验,采用高精度天平获得样品氧化增重,采用扫描电子显微镜(SEM)、能量色散谱仪(EDS)和X射线衍射仪(XRD)测试分析样品的表面与截面微观形貌、元素分布、物相及Cr-Zr扩散层厚度。结果显示,多弧离子镀制备的Cr涂层Zr-4合金样品表面存在大量尺寸不等的大颗粒,Cr涂层沿着(1 1 0)晶面择优生长。高温蒸气单位面积氧化增重与时间近似遵循抛物线规律,1100 °C的蒸气氧化速率明显高于1000 °C,相同温度下Cr涂层Zr-4合金的氧化速率低于无涂层Zr-4合金。高温蒸气氧化后,样品表面生成针须状氧化物,且氧化物间存在大量微孔。在1100 °C高温蒸气氧化3h和4h后,样品表面被氧化生成蠕虫状的团状物。样品截面呈层状结构,由外向内分别为Cr2O3层,Cr涂层,Cr-Zr扩散层,Zr-4合金层。但表面Cr2O3层的厚度并不是随着氧化时间的增加而同步增加的,而Cr-Zr扩散层的厚度随氧化温度和氧化时间的增加而增大,且与氧化时间基本呈线性关系。因此,采用多弧离子镀制备的Cr涂层Zr-4合金在1000 °C和1100 °C下表现出良好的抗高温蒸气氧化性能。

    Abstract:

    Cr-coated zirconium alloy cladding is an important method to improve the high temperature oxidation resistance of light water reactor fuel assembly. The purpose of this paper is to study the high-temperature oxidation behavior of Cr-coated Zr-4 alloys in steam environment. The Cr-coated Zr-4 alloy samples were prepared by multi-arc ion plating process. High temperature oxidation experiments were carried out in 1000 °C and 1100 °C steam environment. The oxidation weight gain of the sample was obtained by a high-precision balance, and the surface and cross-section micro-morphology, element distribution, phase and thickness of the Cr-Zr diffusion layer were analyzed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffractometer (XRD). The results show that there are a large number of droplets of different sizes on the surface of the Cr-coated Zr-4 alloy samples prepared by multi-arc ion plating, and the Cr coating grows preferentially along the (1 1 0) crystal plane. The oxidation weight gain per unit area and time approximately follows a parabolic law. The steam oxidation rate at 1100 °C is significantly higher than that at 1000 °C. At the same temperature, the steam oxidation rate of the Cr-coated Zr-4 alloy is lower than that of the uncoated Zr-4 alloy. After high-temperature steam oxidation, whisker-like oxides were formed on the surface of the samples, and there were a large number of micro-pores between the oxides. After 3 h and 4 h of high temperature steam oxidation at 1100 °C, the surface of the sample was oxidized to form worm-like agglomerates. The cross section of the sample has a layered structure, from the outside to the inside, there are Cr2O3 layer, Cr coating, Cr-Zr diffusion layer, and Zr-4 alloy layer. However, the thickness of the surface Cr2O3 layer does not increase synchronously with the increase of the oxidation time, while the thickness of the Cr-Zr diffusion layer increases with the increase of the oxidation temperature and oxidation time, and has a linear relationship with the oxidation time. Therefore, the Cr-coated Zr-4 alloy prepared by multi-arc ion plating showed good resistance to high temperature steam oxidation at 1000 °C and 1100 °C.

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刘世宏,肖魏魏,罗彪,黄景昊,邹树梁,刘义龙,任峥豪.1000 – 1100 °C下多弧离子镀Cr涂层Zr-4合金的高温蒸气氧化行为[J].稀有金属材料与工程,2024,53(7):1962~1969.[Liu Shihong, Xiao Weiwei, Luo Biao, Huang Jinghao, Zou Shuliang, Liu Yilong, Ren Zhenghao. High temperature steam oxidation behavior of Cr-coated Zr-4 alloy prepared by multi-arc ion plating at 1000 – 1100 °C[J]. Rare Metal Materials and Engineering,2024,53(7):1962~1969.]
DOI:10.12442/j. issn.1002-185X.20230332

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  • 收稿日期:2023-05-30
  • 最后修改日期:2023-08-22
  • 录用日期:2023-08-24
  • 在线发布日期: 2024-07-22
  • 出版日期: 2024-07-12