Thermodynamic properties and spin dynamics of some micro and nanostructured magnetoresistive lanthanum manganites

The spin dynamics and thermodynamic properties of micro- and nanostructured lanthanum manganites La0.67Ca0.33Mn1−xMexO3 (Me = Al; x = 0–0.05) have been studied in order to evidence new features related to the effect of different compositional variables on the thermodynamic and magnetic behaviour. By electron paramagnetic resonance (EPR) spectroscopy, the influence of the grain size and the Mn substitution effects on the spin dynamics were investigated. A solid state electrochemical method was used to obtain the relative partial molar free energies, enthalpies and entropies of oxygen dissolution in the perovskite phase, as well as the equilibrium partial pressures of oxygen. The influence of the oxygen stoichiometry change on the thermodynamic properties has been investigated. The results were correlated with the average Mn valence values as determined by redox titration. In this paper an alternative method is proposed to estimate the contribution made by oxygen vacancies in balancing the local charge in CMR manganites.