Imaging the sublimation dynamics of colloidal crystallites.

We studied the kinetics of sublimating crystals with single-particle resolution by experiments with colloidal spheres and by computer simulations. A short-range attraction between spheres led to crystallites one to three layers thick. The spheres were tracked with optical microscopy while the attraction was reduced and the crystals sublimated. Large crystallites sublimated by escape of particles from the perimeter. The rate of shrinkage was greatly enhanced, however, when the size decreased to less than 20 to 50 particles, depending on the location in the phase diagram. At this size, the crystallites transformed into a dense amorphous structure, which rapidly vaporized. The enhancement of kinetics by metastable or unstable phases may play a major role in the melting, freezing, and annealing of crystals.