Raman spectra and X-ray diffraction of tuite at various temperatures

Abstract

High-temperature Raman spectra and thermal expansion of tuite, γ-Ca3(PO4)2, have been investigated. The effect of temperature on the Raman spectra of synthetic tuite was studied in the range from 80 to 973 K at atmospheric pressure. The Raman frequencies of all observed bands for tuite continuously decrease with increasing temperature. The quantitative analysis of temperature dependence of Raman bands indicates that the changes in Raman frequencies for stretching modes (ν3 and ν1) are faster than those for bending modes (ν4 and ν2) of PO4 in the present temperature range, which may be attributed to the structural evolution of PO4 tetrahedron in tuite at high temperature. The thermal expansion of tuite was examined by means of in situ X-ray diffraction measurements in the temperature range from 298 to 923 K. Unit cell parameters and volume were analyzed, and the thermal expansion coefficients were obtained as 3.67 (3), 1.18 (1), and 1.32 (3) × 10−5 K−1 for V, a, and c, respectively. Thermal expansion of tuite shows an axial anisotropy with a larger expansion coefficient along the c-axis. The isothermal and isobaric mode Gruneisen parameters and intrinsic anharmonicity of tuite have been calculated by using present high-temperature Raman spectra and thermal expansion coefficient combined with previous results of the isothermal bulk modulus and high-pressure Raman spectra.