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Boronizing has been considered as a promising strategy to enhance the surface hardness and corrosion resistance of the new emerged alloys, like CoCrNi medium-entropy alloy (MEA). However, recent studies showed that a brittle silicide layer was generated on the surface for Ni-containing alloys boronizied with the SiC-containing powder (SiC+KBF 4 +B 4 C). In this study, Si-free powder packing (900 °C 4 h) and electrochemical boronizing (900 °C 30 min) methods were explored to obtain the boronized layer for CoCrNi MEA. The morphology, element distributions and phases of the boronized layer were characterized by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectrometer (EDS) and X-ray diffraction (XRD). The results show that the powder-pack boronizing method with 90 wt% B 4 C + 10 wt% NaBF 4 (B 4 C) and electrochemical (EC) methods have the thickest boronized layer (~70 μm) with hardness of about 22 GPa. The boronized layer is dominated by columnar CrB and Co 2 B with obvious preferred orientation and strong texture. In addition, CoB, Ni 2 B and Ni 3 B also exists in the boronized layer, and these two optimal boronizing processes avoid the influence of Si. This study shows that the B 4 C and EC boronizing methods can be considered as the viable alternative strategy for the preparation of strengthened layers. • The optimal boronizing methods were selected to obtain the strengthened layers. • Si-free boride layers were observed on the CoCrNi MEA surface. • The surface hardness reached to 17–22 GPa. • Borides in the boronized layer have obvious preferred orientation and strong texture. [ABSTRACT FROM AUTHOR]

Boronizing has been considered as a promising strategy to enhance the surface hardness and corrosion resistance of the new emerged alloys, like CoCrNi medium-entropy alloy (MEA). However, recent studies showed that a brittle silicide layer was generated on the surface for Ni-containing alloys boronizied with the SiC-containing powder (SiC+KBF 4 +B 4 C). In this study, Si-free powder packing (900 °C 4 h) and electrochemical boronizing (900 °C 30 min) methods were explored to obtain the boronized layer for CoCrNi MEA. The morphology, element distributions and phases of the boronized layer were characterized by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectrometer (EDS) and X-ray diffraction (XRD). The results show that the powder-pack boronizing method with 90 wt% B 4 C + 10 wt% NaBF 4 (B 4 C) and electrochemical (EC) methods have the thickest boronized layer (~70 μm) with hardness of about 22 GPa. The boronized layer is dominated by columnar CrB and Co 2 B with obvious preferred orientation and strong texture. In addition, CoB, Ni 2 B and Ni 3 B also exists in the boronized layer, and these two optimal boronizing processes avoid the influence of Si. This study shows that the B 4 C and EC boronizing methods can be considered as the viable alternative strategy for the preparation of strengthened layers. • The optimal boronizing methods were selected to obtain the strengthened layers. • Si-free boride layers were observed on the CoCrNi MEA surface. • The surface hardness reached to 17–22 GPa. • Borides in the boronized layer have obvious preferred orientation and strong texture. [ABSTRACT FROM AUTHOR]