Some applications of thermally sprayed coatings need a metallurgical bonding of substrate and coating. This can be reached by laser remelting of a thermally sprayed coating, which causes, on the other hand, a certain dilution of the substrate elements into the coating. This article discusses the influence of reaction enthalpies on the microstructure formation in the alloying systems Ni-Al and Ti-Al. Experimental work and simulation were done to examine the time constants of solidification influenced by laser dwell time and reaction enthalpy. It was observed that, for short dwell times, the reaction heat dominates the solidification process and the microstructure formation.