Evaluation of magnetic inhomogeneities in non-stoichiometric Mg0.5Ca0.5Fe2O4 nanoferrite

Abstract

Present work reports a systematic study on the evaluation of magnetic inhomogeneities in non-stoichiometric Mg0·5Ca0·5Fe2O4 nanoferrite (MCNF) by conducting exhaustive dc-magnetization, ac-susceptibility and 57Fe Mössbauer spectroscopic measurements and exchange bias investigations using training protocol down to 6 K. Rietveld fitting to PXRD established the formation of anticipated spinel fcc phase of MCNF (non-stoichiometric) along with a minute impurity phase of calcite. Scherrer method and HRTEM micrographs illustrated broad size distribution of MCNF nanoparticles with an average nanocrystallite size of ∼15 nm. Combined 57Fe Mössbauer spectroscopic and dc-magnetization analysis establishes coexistence of ferrimagnetic (67 %) & superparamagnetic (33 %) states at 300 K with notable Ms = 22 emu/g, Mr = 4 emu/g & Hc = 130 Oe and blocking of most of the nanoparticles of MCNF below 300 K. The coercivity followed the size-modified Kneller law for ferrimagnetic nanoparticles and the saturation magnetization abides the Bloch law. Moreover the frequency-dependent ac-susceptibility investigations revealed two magnetic transitions: (i) A transition at ∼ 330 K in the low frequency data attributed to the relaxation of blocked particles of bigger sizes under the superparamagnetic (SPM) regime and (ii) an irregularity at low temperatures is assigned to surface spin glass freezing. Surface spin glass freezing was further affirmed by the ageing experiments and dynamic scaling law. Furthermore, even the best fit to the dynamic scaling couldn't assert the existence of conventional spin glass phase due to slower spin-flip time of surface spins. A soft ferrimagnetic core of MCNF is enveloped with disordered surface spins, which manifest spin glass state. Concurrently, the findings of exchange bias at 30 K and training effect at 6 K affirmed that MCNF nanoparticles are presenting themselves as FM core- SG shell system. Our experimental findings suggested magnetic inhomogeneities comprised of superparamagnetism, ferrimagnetism and disordered surface spin glass state in the non-stoichiometric MCNF.