Design and Development of Stable Nanocrystalline High-Entropy Alloy: Coupling Self-Stabilization and Solute Grain Boundary Segregation Effects

Grain growth is prevalent in nanocrystalline (NC) materials at low homologous temperatures. Solute element addition is used to offset excess energy that drives coarsening at grain boundaries (GBs), albeit mostly for simple binary alloys. This thermodynamic approach is considered complicated in multi-component alloy systems due to complex pairwise interactions among alloying elements. Guided by empirical and GB-segregation enthalpy considerations for binary-alloy systems, a novel alloy design strategy, the "pseudo-binary thermodynamic" approach, for stabilizing NC-high entropy alloys (HEAs) and other multi-component-alloy variants is proposed. Using Al25Co25Cr25Fe25 as a model-HEA to validate this approach, Zr, Sc, and Hf, are identified as the preferred solutes that would segregate to HEA-GBs to stabilize it against growth. Using Zr, NC-Al25Co25Cr25Fe25 HEAs with minor additions of Zr are synthesized, followed by annealing up to 1123 K. Using advanced characterization techniques- in situ X-ray diffraction (XRD), scanning/transmission electron microscopy (S/TEM), and atom probe tomography, nanograin stability due to coupling self-stabilization and solute-GB segregation effects is reported in HEAs up to substantially high temperatures. The self-stabilization effect originates from the preferential GB-segregation of constituent HEA-elements that stabilizes NC-Al25Co25Cr25Fe25 up to 0.5T(m) (T-m-melting temperature). Meanwhile, solute-GB segregation originates from Zr segregation to NC-Al25Co25Cr25Fe25 GBs; this results in further stabilization of the phase and grain-size (approximate to 14 nm) up to approximate to 0.58 and approximate to 0.64T(m), respectively.