High-strength alloys are in urgent demand for engineering applications. Inducing multiple strengthening phases in a ductile matrix by microalloying is an effective alloy-strengthening strategy, especially the simultaneous formation of geometrically close-packed (GCP) phases and topologically close-packed (TCP) precipitation in high entropy alloys (HEAs). In this study, the microstructural evolution and mechanical properties of a series of (FeNi)67Cr15Mn10-xAl4Ti4Mox HEAs with x values of 1, 2, 3, 4, and 5 were analyzed in detail, with the substitution of Mn by Mo. This substitution does not change the L12 phase forming elements (Ni, Al and Ti) in the alloy, and enhance the σ phase precipitation, which meantime does not modify the oxidation resistance in thermal mechanical treatment. After aging at a temperature of 1023 K for 5 h, the matrix of the HEAs still maintains a face-cubic-centered structure. However, as Mn is replaced by Mo, hard σ precipitates are introduced into the matrix and the grains are significantly refined when x < 5. Therefore, the yield strength monotonically increases with increasing x. However, the formation of the hard σ precipitates also hinders the sustainability of the work hardening process, and thereby decreases the plasticity of the HEAs. Hence, the elongation at break monotonically decreases with increasing x. However, the high density of σ phase precipitates obtained at x = 5 prematurely terminates the work hardening process. Therefore, the highest ultimate tensile stress is obtained at x = 4, rather than x = 5. This also changes the fracture morphology from a coarse grain morphology for x < 5 to a typical brittle fracture at x = 5. Accordingly, (FeNi)67Cr15Mn6Al4Ti4Mo4 obtains the optimal mechanical properties overall.
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