In this work, three as-cast L12-type HEIs with different content of Co element were carefully examined combined with TEM, SEM and XRD technologies. The main matrix of three alloys was L12 ordered phase, and Si,Ti-rich grain-boundary precipitate phase generated with the addition of Co. In Co1 alloy, distinct dual-phase core–shell structure was found within grain due to the precipitation of extra FCC disordered secondary phase, which leads to a better strength-plasticity combination (compressive strength of 3441 ± 50 MPa, and fracture strain of 46.0 ± 1.5%) than Co0 and Co0.5 alloy at room temperature. With the increase of temperature, particular anomalous yield effect was discovered in Co1 alloy. It is clear that SFs became main deformation substructure in Co1 alloy at elevated temperature, and the interaction between non-coplanar SFs motivated the generation of L-C Locks, which assists the K-W Locks to pin dislocations movement and enhance the yield strength from room temperature to about 650 ℃. In addition, the interaction between SFs resulted in the formation of nano-spaced SF network, which contributes to the dynamic Hall-Petch effect. Finally, excellent high-temperature yield strength was achieved in as-cast Co1 alloy, which is higher than room-temperature yield strength until 950 ℃.
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