Valence electron concentration as key parameter to control the fracture resistance of refractory high-entropy carbides | Science Advances

Although high-entropy carbides (HECs) have hardness often superior to that of parent compounds, their brittleness—a problem shared with most ceramics—has severely limited their reliability. Refractory HECs in particular are attracting considerable interest due to their unique combination of mechanical and physical properties, tunable over a vast compositional space. Here, combining statistics of crack formation in bulk specimens subject to mild, moderate, and severe nanoindentation loading with ab initio molecular dynamics simulations of alloys under tension, we show that the resistance to fracture of cubic-B1 HECs correlates with their valence electron concentration (VEC). Electronic structure analyses show that VEC ≳ 9.4 electrons per formula unit enhances alloy fracture resistance due to a facile rehybridization of electronic metallic states, which activates transformation plasticity at the yield point. Our work demonstrates a reliable strategy for computationally guided and rule-based (i.e., VEC) engineering of deformation mechanisms in high entropy, solid solution, and doped ceramics.