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Re-oxidation mechanism and kinetics of fine scale Ti-Magnéli phases in fibre form using thermo-gravimetric analysis

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Abstract

This paper describes the manufacture and properties of fine scale (Ø 260 μm) and dense (>96 % theoretical density) fibres consisting of Magnéli (TinO2n-1) phases for sensing and energy storage applications. In order to understand their operational limits, the re-oxidation of the Magnéli phases in air was examined using thermo-gravimetric analysis at temperatures up to 900 °C under a variety of heating rates. The material was characterised before and after re-oxidation via X-ray diffraction and scanning electron microscopy. The re-oxidation of the Magnéli phases was observed to begin at 650 °C, and the kinetics of the process was studied using the iso-conversional method. The calculated activation energy was consistent with Jander’s three-dimensional diffusion model, where oxidation is limited by diffusion of oxygen through a layer of the oxidised product. An activation energy of 0.71 eV was obtained from kinetic analysis of the thermogravimetry data, which is in agreement with previous work on electrical conduction of Magnéli phases using impedance spectroscopy.

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Acknowledgements

Adamaki acknowledges funding by the European Union Seventh Framework Programme (FP7/2007-2013) under the Grant Agreement no. CP-TP 229099-2 as part of the ‘MesMesh’ project. Bowen acknowledges funding from the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC Grant Agreement No. 320963 on Novel Energy Materials, Engineering, Science and Integrated Systems (NEMESIS).

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Authors and Affiliations

  1. Materials Research Centre, Department of Mechanical Engineering, University of Bath, Bath, UK

    Vaia Adamaki & Christopher R. Bowen

  2. High Performance Ceramics, EMPA Materials Science and Technology, Zurich, Switzerland

    Frank Clemens

  3. Department of Electronic and Electrical Engineering, University of Bath, Bath, UK

    John Taylor

  4. Department of Chemical Engineering, University of Bath, Bath, UK

    Tim J. Mays

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  1. Vaia Adamaki
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  2. Frank Clemens
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  3. John Taylor
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  4. Tim J. Mays
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  5. Christopher R. Bowen
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Correspondence to Christopher R. Bowen.

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Adamaki, V., Clemens, F., Taylor, J. et al. Re-oxidation mechanism and kinetics of fine scale Ti-Magnéli phases in fibre form using thermo-gravimetric analysis. J Mater Sci 49, 7597–7603 (2014). https://doi.org/10.1007/s10853-014-8468-9

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  • DOI: https://doi.org/10.1007/s10853-014-8468-9

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