Ultra-High Mixing Entropy Alloys with Single bcc, hcp, or fcc Structure in Co–Cr–V–Fe–X (X = Al, Ru, or Ni) Systems Designed with Structure-Dependent Mixing Entropy and Mixing Enthalpy of Constituent Binary Equiatomic Alloys

Abstract

Non-equiatomic high-entropy alloys (HEAs) for which the mixing (S_mix), configuration (S_config), and equivalent ideal (S_ideal) entropies satisfy S_mix > S_config = S_ideal were reported for Co–Cr–V–Fe–(Al, Ru, or Ni) systems. Three Co₂₀Cr₂₀Fe₂₀V₁₀X₃₀ (X = Al, Ru, or Ni) alloys (referred to as Al₃₀, Ru₃₀, and Ni₃₀ alloys) were studied here using conventional arc melting and subsequent annealing. The X-ray diffraction profiles revealed that the Al₃₀, Ru₃₀, and Ni₃₀ alloys annealed at 1600 K for 1 h exhibited B2 ordered, hcp, and fcc structures, respectively. A single structure was verified by scanning electron microscopy observations combined with elemental mapping via energy-dispersive X-ray spectroscopy. Thermodynamic calculations of S_mix normalized by the gas constant (S_mix/R) revealed that Al₃₀, Ru₃₀, and Ni₃₀ alloys at 1600 K had S_mix/R = 0.833, 1.640, and 1.618, respectively, where the latter two alloys exceeded S_config/R = 1.557. A compositionally optimized Al-containing HEA for S_mix with a single bcc structure was computationally predicted and verified experimentally for the Al₆Co₂₇Cr₃₄Fe₁₉V₁₄ alloy (Al₆ alloy). The non-equiatomic Al₆ alloy with S_config/R = 1.480 exhibited S_mix/R of 1.703 at 1600 K, surpassing S_config/R = ln 5 = 1.609 for the exact equiatomic (EE) quinary alloy. The bcc Al₆, hcp Ru₃₀, and fcc Ni₃₀ alloys were regarded as ultra-high mixing entropy alloys (UMHEAs) according to S_mix > S_config. Structure-dependent S_mix and the mixing enthalpy of constituent binary EE alloys are useful for future UHMEAs as a subset of HEAs.