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

TL;DR

This study introduces a valence electron concentration criterion to design high-entropy ceramics with enhanced plasticity, demonstrating that increasing VEC improves fracture resistance and ductility at high temperatures.

Contribution

It proposes a fundamental VEC-based design rule for high-entropy ceramics to achieve better plasticity and validates it through synthesis, testing, and simulations of specific compositions.

Findings

(MoNbTaVW)C exhibits higher fracture resistance than (HfTaTiWZr)C.

(MoNbTaVW)C can retain fracture resistance up to 1200K.

VEC > 9.5 e-/f.u. correlates with improved plasticity in ceramics.

Abstract

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-/f.u. 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 statistically show that (HfTaTiWZr)C (VEC=8.6 e-/f.u.) is hard but brittle, whilst (MoNbTaVW)C (VEC=9.4 e-/f.u.) is hard and considerably more resistant to fracture than (HfTaTiWZr)C. Ab initio molecular dynamics simulations and electronic-structure analysis reveal that the improved fracture-resistance of (MoNbTaVW)C subject to tensile and shear 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 ~900-1200K, whereas (HfTaTiWZr)C is predicted to remain brittle at all investigated temperatures.