Size-Dependent Phase Transformation Kinetics in Nanocrystalline ZnS

Abstract

Nanocrystalline ZnS was coarsened under hydrothermal conditions to investigate the effect of particle size on phase transformation kinetics. Although bulk wurtzite is metastable relative to sphalerite below 1020 °C at low pressure, sphalerite transforms to wurtzite at 225 °C in the hydrothermal experiments. This indicates that nanocrystalline wurtzite is stable at low temperature. High-resolution transmission electron microscope data indicate there are no pure wurtzite particles in the coarsened samples and that wurtzite only grows on the surface of coarsened sphalerite particles. Crystal growth of wurtzite stops when the diameter of the sphalerite−wurtzite interface reaches ∼22 nm. We infer that crystal growth of wurtzite is kinetically controlled by the radius of the sphalerite−wurtzite interface. A new phase transformation kinetic model based on collective movement of atoms across the interface is developed to explain the experimental results.