Experiments have shown that the mechanical properties of plasma-sprayed coatings depend to a large extent on the details of the spraying process, in particular, they are strongly dependent on the details of the solidification and deformation history of the individual droplets which are in turn highly affected by the substrate conditions such as its temperature, material, and surface thermal contact resistance. In this study, droplet-substrate interactions are investigated through a complete numerical solution of droplet impact and solidification for a typical thermal spray process. The energy equation is numerically solved for both droplet and substrate regions; the solution is based on the Enthalpy Method for the liquid and solidified parts of the droplet, and the conduction heat transfer in the substrate. The numerical solution for the complete Navier-Stokes equations is based on the modified SOLA-VOF method using rectangular mesh in axisymmetric geometry. The developed model is suited for investigating droplet impact and simultaneous solidification permitting any desired condition at the substrate. The splat shape, the solidification front, and the temperature profile in the entire droplet and substrate regions are obtained at any desired time elapsed after the impact. Through these results, the nucleation and growth of solidification and droplet-substrate interactions are extensively studied.