Thermal expansion and high temperature structure evolution of zoisite by single-crystal X-ray and neutron diffraction

The thermo-elastic behaviour and the temperature-induced structure evolution of a natural Fe-free zoisite have been investigated by in situ single-crystal X-ray and neutron diffraction. Neither discontinuities in volume expansion nor changes in symmetry have been observed up to 1,023 K. Zoisite shows a negative thermal expansion along [100] at T>700 K, while a continuous positive expansion occurs on the (100) plane. Two different regimes in the anisotropic thermal behaviour of zoisite can be distinguished (i.e. at T700 K), corresponding to an increase in the volumetric thermal expansion at T>700 K. The structure evolution with temperature has been described by a series of X-ray and neutron refinements at different temperatures. In particular, the M(3) polyhedra show a significant octahedral flattening and expansion in the equatorial plane with T. All [SiO4] tetrahedra show a regularization with increasing T. The neutron refinements show no change in the configuration of the hydrogen bonding at least up to 873 K. The effects of the T-induced main deformation mechanisms on the anisotropic elastic behaviour of zoisite are discussed. A comparison with the thermal behaviour of epidote has been carried out