Abstract
A natural rutle sample was measured by in situ high-temperature X-ray diffraction (XRD) patterns, as well as Raman and Fourier transform infrared (FTIR). Crystal structure is refined on the sample with 1.4 mol.% Fe and 510±120 ppmw. H2O. The unit-cell and TiO6 octahedral volumes are expanded by 0.7%–0.8% for Fe3+ incorporation, as compared with the reported Ti-pure samples. The volumetric thermal expansion coefficient (α, K−1) could be approximated as a linear function of T (K): 4.95(3)×10−9×T+21.54(5)×10−6, with the averaged value α0=30.48(5)×10−6 K−1, in the temperature range of 300–1500 K. The internal Ti-O stretching (A1g and B2g) and O-Ti-O bending (Eg) modes show ‘red shift’, whereas the multi-phonon process exhibits ‘blue shift’ at elevated temperature. The rotational mode (B1g) for TiO6 octahedra is nearly insensitive to temperature variations. The OH-stretching bands at 3 279 and 3 297 cm−1 are measured by high-temperature spectroscopy experiments. Both the IR-active and Raman-active OH-stretching modes shift to lower frequencies at higher temperature, with the signal intensities decreasing. And after quenching, we expect about 43% dehydration around 873 K, and 85% dehydration at 1 273 K for this hydrous sample.
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Acknowledgments
This work was supported by the National Key Research and Development Program of China (No. 2016YFC0600204), and the National Natural Science Foundation of China (Nos. 41590621 and 41672041). The in situ high-temperature XRD, Raman and FTIR, as well as EPMA were conducted at China University of Geosciences (Wuhan). The single-crystal XRD at ambient condition was measured at Huazhong University of Science and Technology, and many thanks go to Yan Qin for his experimental assistance. The final publication is available at Springer via https://doi.org/10.1007/s12583-020-1351-5.
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Wang, S., Zhang, J., Smyth, J.R. et al. Crystal Structure, Thermal Expansivity and High-Temperature Vibrational Spectra on Natural Hydrous Rutile. J. Earth Sci. 31, 1190–1199 (2020). https://doi.org/10.1007/s12583-020-1351-5
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DOI: https://doi.org/10.1007/s12583-020-1351-5