Effect of surface texture on freezing in nanopores: surface-induced versus homogeneous crystallization

Freezing of argon in ordered and disordered carbon pores of a similar diameter D ∼ 2.4 nm is investigated using extensive molecular simulations with large system sizes up to 10(4) atoms. While crystallization in the atomistically smooth pore consists in a surface-induced phase transition occurring at a temperature larger than the bulk, crystallization in the disordered pores, which is only partial as it is spatially restricted to the pore center, occurs through homogeneous crystallization. These results shed light on solidification in pores by showing that there is a crossover between surface-induced and homogeneous crystallization upon increasing the surface disorder of the host material. In the latter case, the Gibbs-Thomson equation, in which crystallization is assumed to occur when the crystal size equals the pore size corrected for the thickness of the unfreezable layer at the pore surface, is in reasonable agreement with the observed freezing temperature.