Reactive molecular dynamics study of Mo-based alloys under high-pressure, high-temperature conditions

Structural metal alloys are of vital importance for a clean energy economy, but the current trial-and-error alloy development methodology is expensive and time consuming. In this study, we demonstrate the capability of the ReaxFF force field model to predict mechanical properties and provide a fully dynamic description of oxidation and sulfidation of Mo-based alloys under high-pressure, high-temperature conditions using molecular dynamics (MD) method. The advantage of the ReaxFF approach is in its ability to model the formation and breaking of chemical bonds within the quantum framework but several orders of magnitude faster than the traditional density functional theory models. ReaxFF-MD predictions were compared to the literature Mo shock compression measurements at 300 K and 1673 K in the pressure range of 0-350 Pa, and densities and Young's modulus in the temperature range of 300-1500 K. Analysis of oxidation of Mo and Ni clusters and surface slabs showed that Mo oxidation proceeded at a significantly higher rate than the Ni oxidation and involved oxygen transport inside the metal cluster coupled to large heat release that caused extensive surface melting. The oxidation simulations of Mo₃Ni clusters showed high production of Mo oxides and a low concentration of Ni-oxides in the gas phase. This was attributed to the higher chemical stability of Mo-oxide gas phase species. Modeling of H₂S interactions with Mo slab demonstrated that sulfur atoms increasingly agglomerated in the surfaces layers of the slab as the simulation proceeded, diffusing deeper into the slab in their atomic forms. A combined ReaxFF Mo/Ni/C/O/N/S/H parameter set enabled us to obtain a detailed atomistic analysis of complex physical and chemical events during the combustion of a complex fuel molecule on a reactor surface.