We investigated the influence of mixing enthalpy and cooling rate on phase formation and selected the melt-spun AlxCoCrCuFeNi (x = 0, 0.1, 0.5, 0.8 and 1.0 in molar ratios) high-entropy alloys (HEAs) as a model system. The mean mixing enthalpy (ΔHmix) of the alloy system is tuned from positive to negative by increasing Al molar ratios while the mixing entropy (ΔSmix) only has an insignificant variation. Microstructure analyses revealed that the dominant phase in the AlxCoCrCuFeNi HEAs changes from a face-centered cubic (FCC) to body-centered cubic (BCC) structure with the variation of the ΔHmix. Accompanying with phase changing, the lattice constant of the FCC phase increases linearly with Al molar ratio regardless of cooling rate, indicating that the lattice expansion caused by the substitutional alloying of Al plays an important role in the phase evolution, in addition to the effect of the ΔHmix. The increasingly negative enthalpy ΔHmix with Al addition also leads to more pronounced phase separation with the formation of ordered intermetallic phases in the BCC-dominant HEAs than the FCC-dominant ones. Interestingly, when the magnitude of the mean ΔHmix is small, both the coarsening of Cu-rich nanophase and decomposition of the solid-solution phase in the Al0.5CoCrCuFeNi HEA are suppressed. This observation is in line with thermodynamic predictions that a weak ΔHmix benefits the stabilization of the solid-solution phase.
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