Rapid solidification with high cooling rates of metal alloys determines both the improvement of mechanical properties, due to the finishing of the structure, as well as obtaining metastable structures in the form of supersaturated or amorphous/nano solid solutions, which could potentially confer the material outstanding properties. It is of particular interest to use the energies released during the heating stage for these materials, due to the potentially lower input energy required to melt/fuse these materials. This phenomenon could add to the development and diversification of additive manufacturing technologies. The paper presents results concerning the structural development and phase transformation of metastable structures from Al–Si–Ni-based alloys, obtained by melt spinning and atomization techniques. It was observed that the structural transformations occurring during the heating process, starting from metastable structures, generate significant amounts of energy. This is of practical importance in the use of metallic powders in additive manufacturing technology, due to potentially reduced energy input.