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Local Fine Structural Insight into Diffusivity of Anion Vacancies in Titanium Passive Film

机译：钛被无源膜中阴离子空位扩散性的局部细结构洞察

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The outstanding corrosion resistance of titanium results from the presence of a thin oxide film formed on metal surface, especially 1-5 nm thick. The local fine structure and interface interaction of such film requires a combination of sophisticated experimental techniques. Electrochemically formed passive film on titanium in 1.0 M H_2SO_4 solution and its local fine structure and semiconductor properties are examined by synchrotron radiation X-ray absorption fine structure (XAFS), electrochemical impedance spectroscopy (EIS) and Mott-Schottky analysis in conjunction with the point defect model (PDM). Quantitative X-ray absorption near edge structure (XANES) analysis of the local electronic structure exhibits the coexistence of various valences cations in the surface and further confirms the surface sensitivity (～5.0 nm) of XAFS measurements. Theoretical calculation and analysis of extended X-ray absorption fine structure spectra at Ti-K edge reveal the accurate value of Ti-Ti interatomic distance with different coordination numbers and structural disorder, which is the key parameter of diffusivity of anion vacancies. EIS and Mott-Schottky analysis indicate that the interfacial equilibrium within titanium passive film is governed by oxygen vacancies transmission and the donor density decreases exponentially with increasing applied potential, which is well consistent with the PDM prediction. The diffusivity of anion vacancies in titanium passive film is calculated to be approximately in the range of 10~(-18) cm~2 s~(-1) and this development opens the way for further applying the local fine structure to the electrochemical mechanism of passive film.
机译：钛的出色耐腐蚀性是由在金属表面上形成的薄氧化膜的存在，尤其是1-5nm厚。这种薄膜的局部精细结构和界面相互作用需要复杂的实验技术的组合。通过同步辐射X射线吸收细结构（XAF），电化学阻抗光谱（EIS）和Mott-Schottky分析，通过同步辐射X射线吸收细结构（EIS）和Mott-Schottky分析与该点相结合的电化学形成的钛溶液及其局部精细结构和半导体性能。缺陷模型（PDM）。局部电子结构附近的定量X射线吸收（XANES）分析局部电子结构的分析表现出各种价值阳离子在表面中的共存，并进一步证实XAFS测量的表面敏感性（〜5.0nm）。 Ti-k边缘延长X射线吸收细结构光谱的理论计算与分析揭示了与不同协调数和结构障碍的Ti-Ti外部距离的精确值，是阴离子空位扩散性的关键参数。 EIS和MOTT-SCOTTKY分析表明，钛被动膜内的界面平衡由氧空位传输控制，并且随着施加电位的增加，供体密度随着PDM预测的良好一致。计算钛被动膜中的阴离子空位的扩散性为大约10〜（-18）cm〜2 s〜（-1）的范围，并且该发射开辟了进一步将局部细结构进一步施加到电化学机理的方式被动胶片。

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