Hydroxyl stretching in phyllosilicates at high pressures and temperatures: an infrared spectroscopic study

Abstract

The hydroxyl stretching frequencies of four phyllosilicates have been measured at high pressures and temperatures using an externally heated diamond-anvil cell and synchrotron infrared spectroscopy. Spectra were measured up to 26, 31, 21 and 8 GPa at room temperature for samples of talc, pyrophyllite, muscovite and 10-A phase, respectively. Spectra were also measured in the range 273–500 K at ambient pressure for all samples and at 8–9 GPa for talc and pyrophyllite. The frequency of the Mg3OH band in talc increases with pressure due to the absence of hydrogen bonding. The different orientation of the hydroxyl group in pyrophyllite and muscovite leads to hydrogen bonding and a decrease in the frequency of the Al2OH band with pressure. 10-A phase is approximately equivalent to talc with the addition of interlayer H2O. In a spectrum of a sample synthesised for 143 h, two hydroxyl stretching bands are clearly resolved on compression. One is the same as the Mg3OH band in talc, indicating the presence of intra-layer hydroxyl in a talc-like environment with no hydrogen bonding. The other, which separates from the talc-like band at 1 GPa, is associated with intra-layer hydroxyl that is hydrogen bonded to interlayer H2O. There are equivalent bands in high-pressure spectra of a sample of deuterated 10-A phase, synthesised for 400 h. This sample shows a greater extent of hydrogen bonding at ambient pressure than the 143 h sample. For all of the phases studied, increasing temperature leads to a decrease in frequency for every hydroxyl stretching vibration, both at low and high pressures. The shifts in frequency with temperature are an order of magnitude greater than the shifts with pressure when normalised to previously measured structural parameters.