Effects of long storage in La-Sr manganites with pared divalent and quadrivalent substituents for manganese

The results of investigation on the ageing of ceramic manganites La1-cSrcMn0.90Ni0.05Ge0.05O3+γ and La1-cSrcMn0.90Zn0.05Ti0.05O3+γ (c = 0.15, 0.17, 0.19) during long-term storage at normal conditions are presented. Unit cell volume of all manganites having rhombohedral structure decreased over time. The width of X-ray diffraction reflexes from (Ni,Ge)-compositions varied irregularly within the measurement error, and the width of reflexes from (Zn,Ti)-contained manganites decreased significantly. Magnetization of all samples increased in the end of storage period. Curie point of compositions with c > 0.17 exhibited some trend of increase. Ageing leaded to the lowering of “metal-semiconductor” transition temperature in (Ni,Ge)-substituted manganites. (Zn,Ti)-contained compositions showed only semiconductor behavior in investigated temperature range from 100 to 300 K, and the changes of their magnetic parameters were most considerable. The increase in magnetization and Curie point reached 7.5 % and 11 %, respectively. Possible mechanisms of ageing in considered materials are discussed in terms of oxidation processes, formation of microinhomogeneities and relaxation of internal stresses.