Thermodynamic Underpinnings Affecting Compressive and Tensile Plasticity in Refractory Compositionally Complex Alloys

Abstract

Refractory compositionally complex alloys (R-CCAs) show great promise as next generation structural materials for extreme conditions, but alloys with excellent high temperature mechanical properties most often exhibit virtually zero room temperature tensile ductility, hindering potential commercial application. Several semi-empirical metrics have been employed for predicting plasticity in R-CCAs, including valence electron concentration, Pugh ratio, Rice criteria, and the D-parameter. While many currently available ductility metrics correlate very well when compressive plasticity is considered, only the density functional theory (DFT) based D-parameter shows a strong correlation in tension. A new ductility metric is developed using CALculation of PHAse Diagrams (CALPHAD) thermodynamics, Gamma, with includes the free energy difference between the body-centered cubic (BCC) and hexagonal close-packed (HCP) phases, the interfacial free energy of a (110) BCC surface, and an electronegativity-corrected lattice distortion. The Gamma parameter exhibits better correlation with tensile ductility than D-parameter and performs equally well in compression. While this improvement is modest, a thermodynamically grounded ductility metric is clearly required to capture intrinsic ductility behavior. Extrinsic contributions to brittle behavior in R-CCAs, namely interstitial oxygen content, are also briefly discussed. Combining the Gamma ductility parameter with CALPHAD-calculated oxygen solubility is proposed as a first order attempt to capture both intrinsic and extrinsic contributions to ductile behavior in R-CCAs.