Crystal Structure, Thermal Expansivity and High-Temperature Vibrational Spectra on Natural Hydrous Rutile

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 α ₀=30.48(5)×10⁻⁶ K⁻¹, in the temperature range of 300–1500 K. The internal Ti-O stretching (A _1g and B _2g) and O-Ti-O bending (E _g) modes show ‘red shift’, whereas the multi-phonon process exhibits ‘blue shift’ at elevated temperature. The rotational mode (B _1g) 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.

Keywords

rutile / crystal structure / thermal expansivity / high-temperature Raman / high-temperature FTIR / OH-stretching mode

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