In the plasma spraying process, the mechanisms by which molten particles impact on and bond with the substrate are not fully understood. For this study a nickel-chromium powder was sprayed onto mirror polished aluminum 5052 and stainless steel 304 substrates to form single splats. The splats and their interface with the substrate were studied using detailed microstructural characterization with emphasis on the shape of the splats, the nature of the splat-substrate interface, including the degree of contact and the extent of melting of the substrate and mixing with the splat material, and the presence, either on or within the splats of phases such as oxides. It was shown that melting of the substrate, along with intermixing and diffusion between substrate and splat materials, occurred for the steel substrate, but not for the aluminum substrate. Oxides including nickel oxide, chromium oxide, and aluminum oxide were also observed, the type and distribution of these phases depended on the substrate type.