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

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.H2 O.The unit-cell and Ti O6 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 valueα0=30.48(5)×10-6 K-1,in the temperature range of 300–1500 K.The internal Ti-O stretching(A1 g and B2 g)and O-Ti-O bending(Eg)modes show‘red shift',whereas the multi-phonon process exhibits‘blue shift'at elevated temperature.The rotational mode(B1 g)for Ti O6 octahedra is nearly insensitive to temperature variations.The OH-stretching bands at 3279 and 3297 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 1273 K for this hydrous sample.