Finite-size (d = 5.4–112 nm) and surface effects on the structural, optical, and magnetic properties of ferrimagnetic inverse-spinel MnCo2O4 are reported. For d ≥ 87 nm, partial tetragonal distortion of the inverse spinel-lattice was observed. The Curie temperature TC of MnCo2O4 nanostructures, as determined by dc-magnetic susceptibility (χ) measurements, follows a finite-size scaling relation TC(d) = TC(∞)[1−(ξ0/d)λ] with a shift exponent λ = 0.75 ± 0.15 and microscopic correlation length ξ0 = 1.4 ± 0.3 nm, which is consistent with the mean field theory. For T > TC, χ(T) fits Néel's expression for the two-sublattice model with antiferromagnetic molecular field (exchange) constants NBB ∼ 85.16 (JBB ∼ 2.94 × 10−22 J), NAB ∼ 110.96 (JAB ∼ 1.91 × 10−22 J), and NAA ∼ 43.8 (JAA ∼ 1.13 × 10−22 J) and asymptotic Curie temperature Ta ∼ 717.63 K. The optical energy bandgap Eg, evaluated from the Kubelka-Munk function ([F(R∞)ℏω]2 = C2(ℏω - Eg)) is blueshifted to 2.4 eV (d ∼ 5.4 nm) from 1.73 eV (d ∼ 112 nm) due to the quantum confinement and non-stoichiometry. The role of tetragonal distortion and grain-size-effects in the intensity of crystal field transitions and variation in the magnetic ordering are further discussed and compared with Co3O4 nanostructures.
Nanoparticles of Zn substituted lithium ferrite (Li0.31Zn0.38Fe2.31O4, LZFO) synthesized by the sol-gel route are successfully dispersed in layers of reduced graphene oxide (RGO) during the course of preparation. The analysis of X-ray diffractograms confirms the desired crystallographic phase of the nanocomposite sample of LZFO-RGO. The results of field emission scanning electron microscopy and high resolution transmission electron microscopy are consistent with the presence of dispersed nanoparticles in different layers of graphene oxide. Structural information obtained from selected area electron diffraction and nanocrystalline fringe patterns agree well with those obtained from X-ray diffractogram analysis. Mössbauer spectra recorded at 300 and 77 K suggest the presence of a fraction of superparamagnetic particles together with ferrimagnetic particles. Static magnetic measurements include observation of hysteresis loops at 300 and 5 K, magnetization vs. temperature curves under zero field cooling and field cooling conditions. Saturation magnetizations, coercive field, and saturation to remanence ratio are also evaluated. To explore the suitability of this nanocomposite for hyperthermia application, inductive heating of LZFO and LZFO-RGO is measured at different concentrations of nanoparticles. Interestingly, the inductive heating rate of LZFO nanoparticles is enhanced in the nanocomposite phase of LZFO-RGO, suggesting their high potential for hyperthermia therapy in cancer treatment.
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