Role of induced elastic deformations at the Mg/MgH2 transformation

The kinetics of magnesium hydride formation depends on many factors such as thermodynamic conditions, the presence/absence of additives and the mechanical treatments applied to the starting material. As a result, the impact on the reaction of the material is complex. Additionally, during repeated hydrogenation/dehydrogenation cycles, the microstructure of the material becomes significantly different from the original one. In such case, it is not so simple to order the relative importance of the different experimental contributions. In fact limited research efforts have been devoted to the impact of elastic deformation and its direct consequences on the hydride nucleation process. This motivates the present theoretical analysis of the mechanical energy balance between the Mg and MgH₂ entities. Here the formation and interaction of a hydride nucleus with structural defects as a pore or a free surface is carried out in the Mg-MgH₂ system.

The present work evidences that calculation makes it possible to underline and unequivocally analyze the importance of a single parameter among a set of multiple factors that potentially have an impact on the kinetic processes. It is demonstrated here that due solely to the change in volume during hydride nucleation, conditions develops in the magnesium matrix for predominant release of hydride onto free surfaces, including pores.

The calculation of the energy balance made it possible to classify the local impact on the nuclei for different typical configurations such as the vicinity of a free surface, a boundary and the vicinity of low rigidity defects (e.g. pores, vacancies, etc.). Hydride formation near a surface (external or internal, a twin plane or a grain boundary, etc.) results in a reduction in mechanical energy terms, which favors the easy nucleation step in magnesium. Nucleation occurs primarily on free surfaces rather than in bulk.