Ultrasonic chemical synthesis of zinc-manganese ferrites with improved magnetic properties

Zinc-Manganese spinel ferrites (Zn1-xMnxFe2O4) are nowadays very attractive magnetic materials for cancer diagnostic and therapy. With the help of intense ultrasonic waves, sonochemical synthesis method was used to prepare stoichiometric and chemically homogenous nanoparticles by varying the manganese content. The crystal structure along with the size and shape of the as-prepared nanoparticles were described using XRD, TEM and FT-IR techniques, while cations distribution was carefully investigated using XPS and Mössbauer spectroscopic techniques and supported with density functional theory calculations. The crystal structure study revealed the presence of a pure single cubic spinel phase, where the unit-cell and the size were observed to decrease as the manganese incorporation was increased with clear indication of cationic redistribution and degree of inversion variations. Due to the very small variation of the total energy between different configurations, the probability of formation of a mixed phase was found to be very high in such a way that the more mixed was the phase, the more stable it was. A relevant fact was the noticed quasi-systematic ionic exchange made possible by the very short reaction times and high energy offered by the ultrasonic waves. For manganese concentrations up to 60%, the systematic ionic process started by incorporating manganese ions into octahedral sites and pushing iron ions to migrate and replace those of zinc in tetrahedral sites. Such an ionic movement was of central importance for the improvement of the magnetic properties due to the establishment of super-exchange interactions. Such an ionic engineering should definitely open the way to promising applications in biomedical imaging.