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The passivity of titanium—part III: characterization of the anodic oxide film

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Abstract

The thickness of the anodic titanium oxide film formed on titanium in 0.5 M H2SO4 at 22 °C was measured by ellipsometry, and the Forouhi interband single-layer model was used to analyze the data. The anodizing constant was determined experimentally to be 2.75 nm/V, which is in good agreement with literature data, and indicates that the anodizing constants for barrier layers of anodic oxide films formed on a wide variety of metals and alloys lie within the range of 2.2–3.0 nm/V. Using a value for the polarizability of the barrier layer/solution interface obtained via electrochemical impedance spectroscopy (EIS) together with the anodizing constant, the electric field is estimated to be a voltage-independent 1.82 × 106 V/cm. For the anodic oxide film formed on titanium in 0.5 M H2SO4 solution by galvanostatic polarization, the thickness was maintained to be virtually constant even though the oxygen vacancy concentration (donor density) analyzed by the Mott-Schottky relation varied over a wide range, as a function of the film formation rate (current density), with higher donor densities being found for lower current densities. The increase in the donor density leads to a decrease in the modulus of the impedance.

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Acknowledgments

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).

Funding

The study was financially supported by the US Department of Energy through Grant No. DE-FG02-01ER15238 and by the Hyundai Motor Company.

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Authors and Affiliations

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

    Bumwook Roh

  2. Departments of Nuclear Engineering and Materials Science and 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.

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Passivity of titanium, part 1: film growth model diagnostics was published in (2014) J Solid State Electrochem 18:1485-1493; part 2: the defect structure of the anodic oxide film was published in (2019) J Solid State Electrochem https://doi.org/10.1007/s10008-019-04254-0.

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Roh, B., Macdonald, D.D. The passivity of titanium—part III: characterization of the anodic oxide film. J Solid State Electrochem 23, 2001–2008 (2019). https://doi.org/10.1007/s10008-019-04255-z

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  • DOI: https://doi.org/10.1007/s10008-019-04255-z

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