The role of B and Si in the formation of (FeCoCrNi)100-x-yBxSiy high-entropy metallic glasses is studied. It is found that a content of B between 10 and 20 at% and of Si between 5 and 15 at% is able to produce a completely amorphous structure. The microstructural evolution of two of this high-entropy metallic glass compositions, (FeCoCrNi)80B20 and (FeCoCrNi)80B10Si10, have been studied by X-ray diffraction and Transmission Mössbauer Spectroscopy. In both compositions, the first crystallization process corresponds to the formation of metastable, M3B, and stable, M2(B,Si), borides where M stands for metallic atoms. In the Si containing sample a BCC phase also appears. At the second crystallization stage the metastable and the BCC phases disappear and stable M2B or M2(B,Si) phases begin to grow simultaneously with an FCC structure that presents a distribution of possible environs. The fully crystallized structure consists of boride and silicide phases and a paramagnetic FCC phase. The presence of Si promotes the crystallization of a BCC phase and the refinement of the microstructure leading to smaller and more uniform grains.
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