超临界水环境中三种<strong>Ni-Cr</strong>涂层氧化特性研究

doi:10.11902/1005.4537.2023.042

中国腐蚀与防护学报

2024, Vol. 44

Issue (1): 119-129 CSTR: 32134.14.1005.4537.2023.042 DOI: 10.11902/1005.4537.2023.042

研究报告

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超临界水环境中三种Ni-Cr涂层氧化特性研究

袁小虎¹^,², 李定骏², 王天剑², 郭显平², 张乃强³, 朱忠亮³(

)

^1.重庆大学材料科学与工程学院重庆 400044
^2.东方电气集团东方汽轮机有限公司长寿命高温材料国家重点实验室德阳 618000
^3.华北电力大学电站能量传递转化与系统教育部重点实验室北京 102206

Oxidation Behavior of Three Different Ni-Cr Coatings in 630^oC/25 MPa Supercritical Water

YUAN Xiaohu¹^,², LI Dingjun², WANG Tianjian², GUO Xianping², ZHANG Naiqiang³, ZHU Zhongliang³(

)

^1.School of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
^2.State Key Laboratory of Long-Life High Temperature Materials, Dongfang Electric Corporation Dongfang Turbing Co., Ltd., Deyang 618000, China
^3.Key Laboratory of Power Station Energy Transfer, Conversion and System, Ministry of Education, North China Electric Power University, Beijing 102206, China

引用本文:

袁小虎, 李定骏, 王天剑, 郭显平, 张乃强, 朱忠亮. 超临界水环境中三种Ni-Cr涂层氧化特性研究[J]. 中国腐蚀与防护学报, 2024, 44(1): 119-129.
Xiaohu YUAN, Dingjun LI, Tianjian WANG, Xianping GUO, Naiqiang ZHANG, Zhongliang ZHU. Oxidation Behavior of Three Different Ni-Cr Coatings in 630^oC/25 MPa Supercritical Water[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(1): 119-129.

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摘要:

开展了汽轮机用FB2钢及3种工艺制备的热喷涂Ni-Cr涂层在630℃/25 MPa超临界水环境氧化实验研究。利用电子天平、SEM、XRD以及XPS对材料的氧化动力学、氧化膜微观形貌、物相成分进行了分析。结果表明：由于实验过程氧化膜发生剥落，FB2钢氧化动力学偏离抛物线规律，而不同工艺制备涂层的氧化动力学严重偏离抛物线规律。FB2材料氧化膜为典型的双层结构，外层富铁由Fe₃O₄或Fe₂O₃组成，内层由富铬尖晶石组成；涂层的表面氧化物主要是富铬氧化物。FB2钢和涂层的氧化膜物相成分都随着氧化时间增加而发生变化。同时讨论了FB2材料及3种表面涂层在超临界水中的氧化机理。

关键词 ：涂层, 氧化, 超临界水, 氧化机理, 氧化膜

Abstract：

Oxidation behavior of FB2 steel for steam turbine and FB2 steel coated with three different coatings was comparatively investigated in 630^oC/25 MPa supercritical water (SCW). The three coatings are supersonic flame spraying Ni-Cr coating (SFS-NiCr), glass shot peened SFS-NiCr and emery belt grinded SFS-NiCr. Their oxidation mass change was intermittently measured by electron balance, while their microstructure and phase composition were characterized by means of SEM, XRD and XPS before and after oxidation test. Results show that the oxidation kinetics curve of FB2 material deviated from the parabola due to the spallation of the formed oxide scale during the oxidation process. The oxidation kinetics curves of coatings prepared by different processes seriously deviated also from the parabola. A double-layered oxide scale formed on FB2 steel, consisting of an Fe-rich outer Fe₃O₄, Fe₂O₃ and a Cr-rich inner oxide layer. The oxide scale formed on the three coatings are mainly composed of chromium-rich oxide. The phase composition of the oxide scales formed on FB2 steel and the three coatings changed with the increase of oxidation time. Finally, the oxidation mechanism of FB2 steel and three coatings in supercritical water was discussed.

Key words： coating oxidation supercritical water oxidation mechanism oxide film

收稿日期: 2023-02-21 32134.14.1005.4537.2023.042

ZTFLH:

TK245

基金资助:国家重点研发计划项目(2022YFB4100403)

通讯作者: 朱忠亮，E-mail: zhzl@ncepu.edu.cn，研究方向为超临界水环境下金属材料腐蚀性能

Corresponding author: ZHU Zhongliang, E-mail: zhzl@ncepu.edu.cn

作者简介: 袁小虎，男，1984年生，硕士，高级工程师

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图1 630℃超临界水环境下FB2基材及涂层氧化增重与时间关系

图2 原始态喷丸和磨削处理试样表面状态

图3 630℃/25 MPa超临界水中FB2基材、喷涂态、喷丸态以及磨削态NiCr涂层不同氧化时间后的表面形貌

图4 630℃/25 MPa超临界水中FB2钢以及喷涂态、喷丸态和磨削态Ni-Cr涂层氧化100 h后的表面形貌

表1 FB2基材表面及Ni-Cr涂层不同处理工艺下氧化100 h后氧化膜表面元素含量 (atomic fraction / %)

图5 FB2基材以及喷涂态、喷丸态和磨削态Ni-Cr涂层在630℃/25 MPa超临界水中氧化1000 h后的表面形貌

图6 FB2基材在630℃/25 MPa超临界水中氧化3000 h后的表面形貌

图7 喷涂态、喷丸态以及磨削态Ni-Cr涂层在630℃/25 MPa超临界水中氧化3000 h后的表面形貌

表2 图7中不同位置处原子分数 (atomic fraction / %)

图8 FB2钢及不同Ni-Cr涂层在630℃超临界水环境中氧化不同时间后的XRD谱

图9 FB2合金在630℃超临界水环境中氧化3000 h后表面XPS谱

图10 不同表面处理Ni-Cr涂层在630℃超临界水环境中氧化3000 h后表面XPS谱

图11 FB2合金及不同Ni-Cr涂层在630℃超临界水环境中氧化3000 h后的横截面形貌及元素分布图

图12 Fe和Cr氧化物在不同温度下的平衡氧分压

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