Onset of heterogeneous crystal nucleation in colloidal suspensions

The addition of small 'seed' particles to a supersaturated solution can greatly increase the rate at which crystals nucleate. This process is understood, at least qualitatively, when the seed has the same structure as the crystal that it spawns(1,2). However, the microscopic mechanism of seeding by a 'foreign' substance is not well understood. Here we report numerical simulations of colloidal crystallization seeded by foreign objects. We perform Monte Carlo simulations to study how smooth spherical seeds of various sizes affect crystallization in a suspension of hard colloidal particles. We compute the free-energy barrier associated with crystal nucleation(3,4). A low barrier implies that nucleation is easy. We find that to be effective crystallization promoters, the seed particles need to exceed a well-defined minimum size. Just above this size, seed particles act as crystallization 'catalysts' as newly formed crystallites detach from the seed. In contrast, larger seed particles remain covered by the crystallites that they spawn. This phenomenon should be experimentally observable and can have important consequences for the control of the resulting crystal size distribution.