Temperature-induced phase transition in phlogopite revealed by Raman spectroscopy

Raman study of a natural hydrous phlogopite was carried out at temperatures up to 500 °C for the first time. Evolution of four well-resolved Raman modes at wavenumbers 196, 278, 322, and 682 cm⁻¹ was followed in detail with temperature increase. The analysis of data reveals linear decrease of vibrational wavenumbers in the studied temperature range, with small but experimentally significant discontinuities occurring at a temperature of 365±15 °C. Although the overall appearance of Raman spectra remains intact on crossing this temperature, the presence of discontinuities, as well as a marked difference between Gruneisen parameters calculated for high- and low-temperature ranges, signifies the presence of a temperature-induced phase transformation. By combining and correlating the results of the present Raman study with the high-temperature X-ray work performed by Tutti et al. High-temperature study and thermal expansion of phlogopite, Phys. Chem. Miner. 27 (2000) 599-603] we arrive at the interpretation of a temperature-induced structural phase transformation in phlogopite without a significant symmetry change, with an underlying microscopic mechanism involving deformation of Mg octahedra and rotation of tetrahedral grid from ditrigonal toward hexagonal at the transition temperature.