Multi-principal element alloys (MPEAs) have attracted growing attention owing to the vast compositional field and the comprehensive properties. In this work, Fe7(CoNi)77B16 MPEA was undercooled by vacuum melting furnace with low (61 K, 95 K), medium (115 K, 148 K), and high undercoolings (200 K). The maximum growth velocity of the alloy was 0.21 m/s due to the sluggish kinetics effect. The regular eutectic transformed to anomalous eutectic and the primary dendrite refined from 9.1 μm to 3.5 μm with the increase of undercooling. Meanwhile, the phase selection behavior at high undercooling was observed between the stable (Fe, Co, Ni) phase and the metastable (Fe, Co, Ni)23B6 phase. The hardness of primary phase and compressive strength of the undercooled MPEAs were increased to 952.19 HV and 2061.72 MPa, which is much higher than the as-cast alloy. The enhancement of the mechanical properties was attributed to microstructure evolution. The decrease in plasticity resulted from the increasing volume fraction of brittle intermetallic phases. This study helps to theoretically understand the solidification mechanism of the Fe-Co-Ni-B MPEAs and provides a promising way to enhance the mechanical properties of the novel MPEAs.
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