First-Principles Investigation on Adsorption Poisoning and Heterogeneous Nucleation Mechanisms in Ca Modified Primary Mg2Si Phase

We employed first-principles calculations to investigate the adsorption poisoning and heteroepitaxial nucleation mechanisms in the Ca modification of the primary Mg2Si phase. The extensive computations considering various factors such as lattice mismatch, interface energy, adsorption energy, charge density, work of adhesion, and interface mechanical properties, as well as comparisons of interface stacking modes reveal that Ca modification of the primary Mg2Si phase can occur through both adsorption poisoning and heteroepitaxial nucleation mechanisms simultaneously. The adsorption poisoning mechanism implies that Ca preferentially adsorbs on the Mg-terminated surfaces of Mg2Si(100) and Mg2Si(111). Meanwhile, the heteroepitaxial nucleation mechanism indicates the nucleation interface of Mg2Si(100)//CaSi2(001), where the Mg2Si(100) surface is terminated by Si, and the CaSi2(001) surface is terminated by Ca, with stacking modes of Si-Top and Si-Center. In addition, the inclusion of Ca in the primary Mg2Si phase through heteroepitaxial nucleation not only leads to refinement of the primary Mg2Si phase but also displays excellent interface mechanical properties, which suggests that Ca can be considered as an optimal modifier for the primary Mg2Si phase. This study provides a fundamental insight into the role of Ca in modifying the primary Mg2Si phase and has potential implications for the development of Si-containing magnesium alloys.