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Topotaxial reactions during oxidation of ilmenite single crystal

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Abstract

The mechanism of ilmenite–rutile transformation during oxidation of natural ilmenite crystal was studied at elevated temperatures in air. The progress of oxidation with annealing time was studied in the temperature range between 600 and 900 °C. 2.5 mm cubes were cut from the single Mn-ilmenite crystal in two special orientations, [001]ILM and \( \left[ {1\bar{1}0} \right]_{\text{ILM}} \), that allowed determination of crystallographic relations among the reaction products. Using X-ray diffractometry, energy-dispersive spectroscopy, and electron microscopy (SEM, TEM) techniques, we determined that the ilmenite to rutile and hematite transformation is triggered by surface oxidation of divalent cations (Fe, Mn) from the starting ilmenite and their crystallization in the form of hematite and bixbyite on the surface of the single crystal. Surface oxidation and out-diffusion of Fe2+ and Mn2+ ions opens paths for exsolution of rutile within the pseudo-hexagonal oxygen sublattice of the parent ilmenite, following simple topotaxial orientation relationship \( {\langle{001}\rangle}_{\text{RUT}} \;\left\{ {010} \right\}_{\text{RUT}} \;||\;{\langle{210}\rangle}_{\text{ILM}} \;\left\{ {001} \right\}_{\text{ILM}} \). With this transformation, new channels for fast out-diffusion of divalent cations to the oxidation surface are opened along the c-axis of the rutile structure. The volume difference of the reaction products causes cracking of the single crystal, which opens additional free surfaces for accelerated oxidation. The results of this study contribute to better understanding of the recrystallization processes during pre-oxidation of ilmenite.

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Acknowledgements

This work was supported by the Slovenian Research Agency under the Project No. J1-6742 »Atomic-scale studies of initial stages of phase transformations in minerals« and PhD Grant No. 1000-11-310225. The research leading to these results has received funding from the European Union Seventh Framework Programme [FP7] under Grant agreement no. 312483 (ESTEEM2).

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  1. Department for Nanostructured Materials & Jožef Stefan International Postgraduate School, Jožef Stefan Institute, Jamova cesta 39, 1000, Ljubljana, Slovenia

    Nadežda Stanković, Aleksander Rečnik & Nina Daneu

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  1. Nadežda Stanković
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  2. Aleksander Rečnik
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  3. Nina Daneu
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Correspondence to Aleksander Rečnik.

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Stanković, N., Rečnik, A. & Daneu, N. Topotaxial reactions during oxidation of ilmenite single crystal. J Mater Sci 51, 958–968 (2016). https://doi.org/10.1007/s10853-015-9425-y

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