High-entropy alloys(HEAs)have attracted extensive attention ascribed to their unique physical and chemical properties induced by the cocktail effect.However,their oxidation behaviors,in particular at nanoscale,are sti...High-entropy alloys(HEAs)have attracted extensive attention ascribed to their unique physical and chemical properties induced by the cocktail effect.However,their oxidation behaviors,in particular at nanoscale,are still lack because of multi-element complexity,which could also be completely differ-ent from the bulk counterparts.In this work,we synthesized FeCoNiTiCu five-element HEA nanopar-ticles(NPs)with uniform elemental distribution by arc-discharging approach,and further investigated their oxidation behaviors at 250 ℃,and 350 ℃.The morphology,structure and element distribution of NPs were analyzed by transmission electron microscopy(TEM),energy dispersive spectroscopy(EDS)and electron energy loss spectroscopy(EELS).The surface oxidation in FeCoNiTiCu NPs during the high-temperature process can induce nanoscale pores at core/shell interfaces by Kirkendall effect,and even the eventual coalescence into a single cavity.Additionally,the oxidation states of NPs with diameters(d)varying from 60 to 350 nm were analyzed in detail,revealing two typical configurations:hollow(d<150 nm)and yolk-shell structures(d>150 nm).The experimental results were complemented by first-principles calculations to investigate the diffusion behaviors of five elements,evidencing that the surface oxidation strongly alters the surface segregation preferences:(1)in the initial stage,Cu and Ni appear to prefer segregating on the surface,while Co,Ti and Fe tend to stay in the bulk;(2)in the oxidation process,Cu prefers to stay in the center,while Ti segregates to the surface ascribed to the reduced po-tential energies.The study gives new insights into oxidation of nanoscale HEA,and also provides a way for fabrication of high-entropy oxides with controllable architectures.展开更多
基金National Science Fund for Distinguished Young Scholars(No.52225312)Key Research and Development Program of Zhejiang Province(Nos.2021C01033,2023C01077)National Natural Science Foundation of China(No.U1908220).
文摘High-entropy alloys(HEAs)have attracted extensive attention ascribed to their unique physical and chemical properties induced by the cocktail effect.However,their oxidation behaviors,in particular at nanoscale,are still lack because of multi-element complexity,which could also be completely differ-ent from the bulk counterparts.In this work,we synthesized FeCoNiTiCu five-element HEA nanopar-ticles(NPs)with uniform elemental distribution by arc-discharging approach,and further investigated their oxidation behaviors at 250 ℃,and 350 ℃.The morphology,structure and element distribution of NPs were analyzed by transmission electron microscopy(TEM),energy dispersive spectroscopy(EDS)and electron energy loss spectroscopy(EELS).The surface oxidation in FeCoNiTiCu NPs during the high-temperature process can induce nanoscale pores at core/shell interfaces by Kirkendall effect,and even the eventual coalescence into a single cavity.Additionally,the oxidation states of NPs with diameters(d)varying from 60 to 350 nm were analyzed in detail,revealing two typical configurations:hollow(d<150 nm)and yolk-shell structures(d>150 nm).The experimental results were complemented by first-principles calculations to investigate the diffusion behaviors of five elements,evidencing that the surface oxidation strongly alters the surface segregation preferences:(1)in the initial stage,Cu and Ni appear to prefer segregating on the surface,while Co,Ti and Fe tend to stay in the bulk;(2)in the oxidation process,Cu prefers to stay in the center,while Ti segregates to the surface ascribed to the reduced po-tential energies.The study gives new insights into oxidation of nanoscale HEA,and also provides a way for fabrication of high-entropy oxides with controllable architectures.
