Predicting the Effect of Mo Addition on Metastable Phase Equilibria and Diffusion Path of Fe in NiAl Laser-Clad Coatings Using First-Principle Calculations and CALPHAD Simulations

This study used first-principle calculations and CALPHAD simulations to investigate the effects of adding Mo to NiAl laser-clad coatings in terms of metastable phase equilibria and Fe diffusion path with a focus on thermodynamic phase stability and element diffusion behavior. First-principle calculations were performed using 3 × 3 × 3 supercells to determine the formation energies of NiAl and Mo-rich phases within a Mo-doped NiAl cladding layer. The findings of this analysis are consistent with the d-orbital energy and bond order results obtained using DV-Xa molecular orbital calculations and phase diagrams obtained using Thermo-Calc simulations. The results also revealed that the substitution of Ni and Al atoms for Fe and Mo in the NiAl matrix decreased the stability of the B2 structure, thereby reducing phase formation energy. DICTRA simulations were also performed to characterize the diffusion behavior of Fe from the substrate to the surface of the coating. This analysis revealed that the rate of Fe diffusion was slower in the Mo phase than in the NiAl phase. Furthermore, the rate of Fe diffusion in molten material was inversely proportional to the Mo content. These results are consistent with the substitution mechanism used to describe diffusion, wherein diffusivity is inversely proportional to Mo content, due to its high melting point and the fact that un-paired electrons in the outer shell of Mo atoms increase the bonding strength, thereby hindering the diffusion of Fe. Due to the high cooling rates involved in the laser-cladding process, DICTRA simulations tend to overestimate the Fe diffusion distance. Nonetheless, the theoretical results obtained in this study were in good agreement with experiment observations (EPMA line scans). These results confirm the feasibility of using quantum modeling techniques and first-principle calculations to predict the effects of Mo addition on phase formation and element diffusion behavior in the NiAl laser-cladding process.