Formation and evolution of magnetic nanoparticles in borate glass simultaneously doped with Fe and Mn oxides

Abstract

Evolution of the phase state of paramagnetic additions at various stages of synthesis and subsequent thermal treatment of glasses of the system Al2O3–K2O–B2O3 simultaneously doped with Fe2O3 and MnO is studied by means of a combination of experimental techniques: Faraday rotation (FR), electron magnetic resonance (EMR), transmission electron microscopy (TEM), Mössbauer spectroscopy, and magnetic measurements. Both FR and EMR show that magnetically ordered clusters occur already at the first stage of the glass preparation. In particular, for the ratio of the Fe and Mn oxides in the charge close to 3:2, fine magnetic nanoparticles are formed with characteristics similar to those of manganese ferrite. By computer simulating the EMR spectra at variable temperatures, a superparamagnetic nature of these nanoparticles is confirmed and their mean diameter is estimated as approximately 3.2 nm. In the thermally treated glasses larger magnetic nanoparticles are formed, giving rise to FR spectra, characteristic of magnetically ordered systems, and the EMR spectra different from those in as-prepared glasses but also showing superparamagnetic narrowing. The Mössbauer spectroscopy corroborates the manganese ferrite structure of the nanoparticles and indicates their coexistence in the ferrimagnetic and superparamagnetic states. The TEM shows the presence of polydisperse nanoparticles on the background of the glass matrix, and electron diffraction of a selected region containing larger particles indicates a crystal structure close to that of MnFe2O4. Energy-dispersive atomic x-ray spectra confirm that the major part of Fe and Mn introduced to the glass composition is gathered in the particles, with the concentration ratio close to 2:1, characteristic of bulk MnFe2O4. Magnetic hysteresis loops of samples subjected to an additional thermal treatment demonstrate a strong increase in the coercive force, remnant magnetization, and high-field magnetic susceptibility with temperature decrease. The consistent results obtained using various techniques demonstrate that the formation of nanoparticles with characteristics close to those of MnFe2O4 confers to these glasses magnetic and magneto-optical properties typical of substances possessing magnetic order.