A multistep oriented attachment kinetics: coarsening of ZnS nanoparticle in concentrated NaOH.

Crystal growth of ZnS nanoparticles during hydrothermal coarsened in 4 M NaOH occurs via a two-stage process. In the first stage, the primary particles grow into a size over hundred times of the original volume. The initial growth rate can be fitted by an asymptotic curve. High-resolution transmission electron microscope (HRTEM) data indicate that in this stage, crystal growth mainly occurs via a multistep crystallographically specific oriented attachment (OA). The higher the coarsening temperature, the earlier the first stage ends. In the second stage, an abrupt transition from asymptotic to square parabola growth kinetics occurs. The crystal growth data can be fitted by a standard Ostwald ripening (OR) model consistent with growth controlled by dissolution/precipitation of ions in solution. HRTEM data indicate that a minor amount of OA-based growth also occurs in the early period of the second stage. A new multistep OA kinetics model analogous to the reaction between molecules was proposed to illustrate the asymptotic growth in the first stage of coarsening. The effect of concentrated NaOH was discussed and proved to be the key that hindered the OR process, attributing to the almost exclusive pure OA-based growth of ZnS particles in the first stage.