The fabrication of dense coatings with appropriate properties using a high velocity oxygen fuel (HVOF) spray process requires an in-depth understanding of the complete gas flow field and particle behavior during the process. A computational fluid dynamics (CFD) model is implemented to investigate the gas flow behavior that occurs during the HVOF process and a simplified one-dimensional decoupled model of the in-flight thermal behavior of the amorphous Fe-based powder particles was developed and applied for three different spray conditions. The numerical results were used to rationalize the different coating microstructures described in the experimental results. Low porosity and amorphous coatings were produced using two different particle size distributions (16 to 25 μm and 25 to 53 μm). The amorphous characteristics of the powder were retained in the coating due to melting and rapid solidification in the case of very fine powder or ligaments (<16 μm) and to the fact that the crystallization temperature was not reached in the case of the large particles (16 to 53 μm).