紫外光电子能谱和X射线光电子能谱表征在金属材料腐蚀中的应用

doi:10.11902/1005.4537.2016.096

中国腐蚀与防护学报

2016, Vol. 36

Issue (4): 287-294 DOI: 10.11902/1005.4537.2016.096

本期目录 | 过刊浏览

紫外光电子能谱和X射线光电子能谱表征在金属材料腐蚀中的应用

王胜刚(

),孙淼,龙康

中国科学院金属研究所沈阳材料科学国家 (联合) 实验室沈阳 110016

Progress in Characterization of Metallic Materials Corrosion by Ultraviolet Photoelectron Spectroscopy and X-ray Photoelectron Spectroscopy

Shenggang WANG(

),Miao SUN,Kang LONG

Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

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摘要:

利用紫外光电子能谱 (UPS) 对比表征了纳米和普通晶粒的304不锈钢、工业纯铝以及工业纯铁室温时的价电子结构。利用X射线光电子能谱 (XPS) 表征了上述材料在不同浓度盐酸溶液中浸泡不同时间后,表面氧化膜的电子结构;以及纳米和普通晶粒的304不锈钢在空气中高温氧化 (室温至900 ℃升温阶段,900 ℃下恒温24 h) 后,氧化膜的电子结构。根据这些实验结果建立了金属材料腐蚀性能与材料的价电子结构和氧化膜电子结构之间的关系,提出了金属材料腐蚀性能本征参量概念。

关键词 ：腐蚀, 价电子结构, 氧化膜电子结构, X射线光电子能谱, 紫外光电子能谱

Abstract：

In fact, the metallic material corrosion process may intrinsically involve subprocesses such as the exchange of valence electron between metallic atoms and ions in corrosive medium, the formation of oxide scale, the migration of corrosive species through the formed oxide scale, and the interaction between oxidation scale and corrosive medium. Therefore, the energy state of the valence electron of components of metallic material may play an important role in the corrosion process, thus for reveal which, ultraviolet photoelectron spectroscope (UPS) and X-ray photoelectron spectroscope (XPS) may become useful tool. Herewith new progress in this respect is subsequently introduced. The valence electron energy state of components for bulk nanocrystalline materials 304 stainless steel (BN-SS304), industrial pure aluminum (BN-Al) and ingot iron (BNII), as well as their counterparts of conventional microcrystalline ones (CP-SS304), (CP-Al) and (CPII) was characterized by UPS at room temperature. The valence electron energy state of components of the oxide scale formed on these metallic materials due to corrosion in hydrochloric acid solutions, and the oxide scales formed on BN-SS304 and CP-SS304 due to air oxidation at 900 ℃ were comparatively studied by XPS. The above aquired results may enable one to establish the relationship between the corrosion performance with the valence electron energy state of components of these metallic materials, and to figure the electron structure of components of the corresponding formed oxide scales, as well. Furthermore, a new concept of intrinsic parameter related with metallic material corrosion was proposed.

Key words： corrosion valence electron structure oxide scale XPS UPS

基金资助:国家自然科学基金项目 (51171199) 和国家重点基础研究发展计划项目 (2010CB934603) 资助

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引用本文:

王胜刚, 孙淼, 龙康. 紫外光电子能谱和X射线光电子能谱表征在金属材料腐蚀中的应用[J]. 中国腐蚀与防护学报, 2016, 36(4): 287-294.
Shenggang WANG, Miao SUN, Kang LONG. Progress in Characterization of Metallic Materials Corrosion by Ultraviolet Photoelectron Spectroscopy and X-ray Photoelectron Spectroscopy. Journal of Chinese Society for Corrosion and protection, 2016, 36(4): 287-294.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2016.096 或 https://www.jcscp.org/CN/Y2016/V36/I4/287

图1 纳米晶和普通工业纯铁的紫外光电子能谱[14]

图2 纳米晶和普通304不锈钢的紫外光电子能谱[15]

图3 纳米晶和普通工业纯铝的紫外光电子能谱[16]

图4 纳米和普通晶粒的304不锈钢在0.5 mol/L HCl溶液中室温浸泡30 d后的腐蚀形貌[15]

图5 纳米和普通晶粒的工业纯铝在0.25 mol/L HCl溶液中室温浸泡9 d后的腐蚀形貌[16]

图6 纳米和普通晶粒的304不锈钢在0.5 mol/L HCl 溶液中室温浸泡30 d后,氧化膜中Cl-的结合能和原子分数沿氧化膜的截面分布规律[15]

图7 纳米和普通晶粒的工业纯铝在0.25 mol/L HCl溶液中室温浸泡9 d后,氧化膜中Cl-的结合能和原子分数沿氧化膜的截面分布规律[16]

图8 纳米和普通晶粒的304不锈钢在空气中室温至900 ℃阶段以及900 ℃恒温24 h的氧化动力学曲线[17]

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