Influence of alloying elements on the mechanical and thermodynamic properties of ZrB12 ceramics from first-principles calculations

Although ZrB₁₂ is a promising advanced material because of the boron cuboctahedron cages, the hardness of ZrB₁₂ remains controversy. Here, we apply first-principles calculations to study the influence of transition metals (4d- and 5d-) on the hardness and thermodynamic properties of ZrB₁₂. The calculated hardness of ZrB₁₂ is 32.9 GPa, which is in good agreement with the previous theoretical result. Importantly, the calculated hardness of Re-doped ZrB₁₂ is up to 40.0 GPa, which is a potential superhard material. The essential reason is that the alloying element of Re enhances the localized hybridization of B B and Zr B atoms, and then forms the strong B B covalent bond and Zr B bond. The result is well demonstrated by the chemical bonding and lattice parameter. Here, our work shows that the alloying elements of Nb, Mo, and Re enhance the thermodynamic properties of ZrB₁₂. The Debye temperature of Re-doped ZrB₁₂ is 1225.2 K, which is larger than that of the parent ZrB₁₂ (1213.5 K).