In earlier experiments, plasma-sprayed Al 2 O 3 coatings were deposited on preheated Al 2 O 3 substrates to study the effect of substrate temperature on splat formation and phase transformations. The aim of the present work is to develop a model to better understand the factors that affect phase selection during the solidification of Al 2 O 3 splats. A model based on one-dimensional heat transfer and classic nucleation theory is presented and used to simulate the rapid solidification process and the influence of process parameters on phase selection. The model accounts for under-cooling phenomena, heterogeneous nucleation, and nucleation kinetics. The findings indicate that the relationship between initial substrate temperature and phase selection is primarily based on the catalytic effect of the alumina substrate on the nucleation of Al 2 O 3 phases as a function of contact angle.