Dynamism or Disorder at High Pressures?

Phase transitions in minerals at elevated temperatures typically involve dynamics as a natural consequence of the increase in thermal energy available to the system. Classic examples include quartz, cristobalite, and carbonates in which the high-temperature, high symmetry phase is dynamically disordered. This disorder has important thermodynamic consequences, including displacement and curvature of phase boundaries (e.g. calcite-aragonite). In other minerals such as clinopyroxenes and anorthite feldspar, the dynamic behaviour is restricted to the neighbourhood of the phase transition. The fundamental question is whether increasing pressure generally suppresses such dynamic behaviour (as in anorthite; Angel, 1988), or not. In the latter case it must be included in thermodynamic models of high-pressure phase equilibria and seismological modelling of the mantle; the potential dynamics and softening in stishovite may provide the critical observational constraint on the presence or otherwise of free silica in the lower mantle. We have continued to use the lead phosphate as a prototype ferroelastic in which to understand dynamic behaviour, simply because its dynamics and transition behaviour is far better characterised than any mineral. Furthermore, the phase transition is at a pressure where experimental difficulties do not dominate the experimental results. Our previous neutron diffraction study (Angel et al., 2001) revealed that some disorder, either dynamic or static, is retained in the high-symmetry, high-pressure phase just above the phase transition. New neutron diffraction data on the pure material now suggests that this disorder slowly decreases with increasing pressure until at twice the transition pressure it is ordered. Further data for doped material provides insights into the nature of this disorder. Angel (1988) Amer. Mineral. 73:1114. Angel et al (2001) J PhysC 13: 5353.