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Passivity of titanium, part IV: reversible oxygen vacancy generation/annihilation

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Abstract

A simplified Point Defect Model incorporating reversible oxygen vacancy generation/annihilation at the metal/film interface has been used to investigate the impedance of anodized titanium in 0.5 M H2SO4, the oxygen vacancy profile in the anodic titanium oxide film, and the surface oxygen vacancy concentration. This simplified Point Defect Model (PDM), which considers the oxygen vacancy as the only point defect in the film, successfully accounts for the impedance of anodized titanium over the potential range explored. The results indicate that there is a thin region of the non-uniform oxygen vacancy concentration adjacent to the film/solution interface, which has an exponentially decreasing dopant (\( {V}_O^{\cdot \cdot } \)) concentration. The results of the investigation show that the surface oxygen vacancy concentration normalized to the bulk oxygen vacancy concentration is in the range of 0.05–0.15 and is essentially independent of potential.

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Acknowledgments

The authors gratefully acknowledge the support of this work at the Pennsylvania State University by the US Department of Energy through Grant No. DE-FG02-01ER15238 and by the Hyundai Motor Company. Additionally, Investigator No. 2 gratefully acknowledges the partial support of this work by FUTURE (Fundamental Understanding of Transport Under Reactor Extremes), an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) (neutron scattering studies).

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Authors and Affiliations

  1. Hyundai Motor Company, Mabuk-Ri, Gyeonggi-Do, Republic of Korea

    Bumwook Roh

  2. Departments of Nuclear Engineering, University of California at Berkeley, Berkeley, CA, 94720, USA

    Digby D. Macdonald

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  1. Bumwook Roh
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  2. Digby D. Macdonald
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Correspondence to Digby D. Macdonald.

Additional information

“Passivity of titanium, part 1: film growth model diagnostics” was published in (2014) J Solid State Electrochem 18(5):1485–1493

“Passivity of titanium: part II, the defect structure of the anodic oxide film” was published in (2019) J Solid state Electrochem 23(7):1967–1979

“The passivity of titanium—part III: characterization of the anodic oxide film” was published in (2019) J Solid State Electrochem 23(7):2001–2008

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"Passivity of titanium, part I: film growth model diagnostics" was published in (2014) J Solid State Electrochem 18(5):1485-1493

"Passivity of titanium: part II, the defect structure of the anodic oxide film" was published in (2019) J Solid state Electrochem 23(7):1967-1979

"The passivity of titanium-part III: characterization of the anodic oxide film" was published in (2019) J Solid State Electrochem 23(7):2001-2008

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Roh, B., Macdonald, D.D. Passivity of titanium, part IV: reversible oxygen vacancy generation/annihilation. J Solid State Electrochem 23, 2863–2879 (2019). https://doi.org/10.1007/s10008-019-04363-w

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  • DOI: https://doi.org/10.1007/s10008-019-04363-w

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