Enhancing plasticity in high-entropy refractory ceramics via tailoring valence electron concentration

[Display omitted] •Nanoindentation demonstrates that (MoNbTaVW)C is considerably more resistant to fracture.•AIMD shows that single-crystal (MoNbTaVW)C is inherently tougher than (HfTaTiWZr)C, up to 900 K.•(HfTaTiWZr)C exhibits brittle fracture whereas strain-induced plasticity occurs in (MoNbTaVW)C.•The VEC of (MoNbTaVW)C enables charge transfer with modifications in bonding network upon loading. Bottom-up design of high-entropy ceramics is a promising approach for realizing materials with unique combination of high hardness and fracture-resistance at elevated temperature. This work offers a simple yet fundamental design criterion – valence electron concentration (VEC)⪆9.5 e-/formula unit to populate bonding metallic states at the Fermi level – for selecting elemental compositions that may form rocksalt-structure (B1) high-entropy ceramics with enhanced plasticity (reduced brittleness). Single-phase B1 (HfTaTiWZr)C and (MoNbTaVW)C, chosen as representative systems due to their specific VEC values, are here synthesized and tested. Nanoindentation arrays at various loads and depths statisticallyshow that (HfTaTiWZr)C (VEC = 8.6 e-/f.u.) is hard but brittle, whilst (MoNbTaVW)C (VEC = 9.4 e-/f.u.) is hardandconsiderably more resistant to fracture than (HfTaTiWZr)C. Ab initiomolecular dynamics simulations and electronic-structure analysis reveal that the improved fracture-resistance of (MoNbTaVW)C subject to deformation may originate from the intrinsic material’s ability to undergo local lattice transformations beyond tensile yield points, as well as from relatively facile activation of lattice slip. Additional simulations, carried out to follow the evolution in mechanical properties as a function of temperature, suggest that (MoNbTaVW)C may retain good resistance to fracture up to ≈900-1200 K, whereas (HfTaTiWZr)C is predicted to remain brittle at all investigated temperatures.