Fabrication of Porous High-Entropy Mn-Fe-Co-Ni-Cu-Zn Alloys by Vapor Phase Dealloying

Porous multicomponent 3d transition-metal (TM) alloys were fabricated by eliminating Zn from rapidly quenched ribbons with distinct compositions, TM7Zn93 and TM4Zn96 (TM - a mixture of Mn, Fe, Co, Ni, and Cu) using vapor phase dealloying (VPD). Phase composition and microstructure of the ribbons in an as-quenched state and resulting porous materials were investigated in detail by S/TEM-EDS, XRD, SEM, and EDXRF methods. In the as-quenched state, the majority of the alloy is composed of the CoZn13 type structure (C2/m space group). Atomically resolved EDS mapping clarified the chemical site occupancy of the TM elements in the structure. The resulting fabricated porous high-entropy alloys (HEA) have a spongy microstructure with a bimodal pore size and their surface area was estimated at 2-4 m2/g. Analysis of pore size distribution revealed their macro-mesoporous structure. The formation of the solid solution with the FCC (Fm3m space group) crystal structure during VPD was confirmed by XRD data. STEM-EDS analysis revealed the existence of several FCC solid solution phases within the porous HEA. A nanoscale elemental/phase separation into Co- and Cu-rich FCC solid solution regions with coherent interfaces across the individual crystalline grains has been found. A general route to prepare porous HEA using rapid solidification and vapor phase dealloying has been discussed.