Thermoanalytical, Optical, and Magnetic Investigations on Nanocrystalline Li0.5Fe2.5O4 and Resulting Ceramics Prepared by a Starch-Based Softchemistry Synthesis
Journal of Solid State Chemistry 287 (2020) 121380
23 Pages Posted: 29 Jun 2020
Date Written: February 7, 2020
Nanocrystalline Li0.5Fe2.5O4 was prepared by a starch-based soft-chemistry synthesis. Calcining of the (LiFe)-gel between 350 and 1000 °C results in Li0.5Fe2.5O4 powders with crystallite sizes from 13 to 141 nm and specific surface areas between 35 and 7.1 m2 g-1. XRD investigations reveal the formation of ordered Li0.5Fe2.5O4. Sintering between 1050 and 1250 °C leads to ceramics with relative densities of 67–95% consisting of grains between 0.3 and 54 μm. As the sintering temperature increases a rising weight loss of the ceramic samples was observed due to the loss of Li2O. Temperature-dependent magnetic measurements indicate a superparamagnetic behaviour for the nano-sized samples. Field-dependent measurements at 3 K of ceramics sintered between 1050 and 1200 °C show increasing saturation magnetization values (Ms) of 70.0–73.0 emu g-1 most likely due to the formation of lithium vacancies and a decrease of the inversion parameter. The magnetization drops down to 67.7 emu g-1 after sintering at 1250 °C caused by the formation of hematite. Diffuse reflectance spectra reveal an indirect allowed band gap decreasing from 1.93 to 1.60 eV depending on thermal treatment. DSC measurements of the order ⇆ disorder phase transition on nano-sized powders and bulk ceramics exhibit transition temperatures between 734 and 755 °C and enthalpy changes (ΔtrsH) ranging from 5.0 to 13.5 J g-1. The linear thermal expansion coefficient was found to be 11.4*10-6 K-1.
Keywords: spinel, ferrite, magnetism, superparamagnetism, band gap, enthalpy, entropy, nanoparticle, Li0.5Fe2.5O4, LiFe5O8, inversion parameter
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