Polymorphic transformations between olivine, wadsleyite and ringwoodite; mechanisms of intracrystalline nucleation and the role of elastic strain

Kinetic models and rate equations for polymorphic reconstructive phase transformations in polycrystalline aggregates are usually based on the assumptions that (a) the product phase nucleates on grain boundaries in the reactant phase and (b) growth rates of the product phase remain constant with time at fixed P-T. Recent observations of experimentally induced transformations between (Mg,Fe) (sub 2) SiO (sub 4) olivine (alpha ) and its high pressure polymorphs, wadsleyite (beta ) and ringwoodite (gamma ), demonstrate that both these assumptions can be invalid, thus complicating the extrapolation of experimental kinetic data. Incoherent grain boundary nucleation appears to have dominated in most previous experimental studies of the alpha -beta -gamma transformations because of the use of starting materials with small (<10-20 mu m) grain sizes. In contrast, when large (0.6 mm) olivine single crystals are reacted, intracrystalline nucleation of both beta and gamma becomes the dominant mechanism, particularly when the P-T conditions significantly overstep the equilibrium boundary. At pressures of 18-20 GPa intracrystalline nucleation involves (i) the formation of stacking faults in the olivine, (ii) coherent nucleation of gamma -lamellae on these faults and (iii) nucleation of beta on gamma . In other experiments, intracrystalline nucleation is also observed during the beta -gamma transformation. In this case coherent nucleation of gamma appears to occur at the intersections of dislocations with (010) stacking faults in beta , which suggests that the nucleation rate is stress dependent. Reaction rims of beta /gamma form at the margins of the olivine single crystals by grain boundary nucleation. Measurements of growth distance as a function of time indicate that the growth rate of these rims decrease towards zero as transformation progresses. The growth rate slows because of the decrease in the magnitude of the Gibbs free energy (stored elastic strain energy) that develops as a consequence of the large volume change of transformation. On a longer time scale, growth kinetics may be controlled by viscoelastic relaxation.