Crystal structure and the effect of annealing atmosphere on the dielectric properties of the spinels MgAl2O4, NiFe2O4, and NiAlFeO4

The non-transition metal spinel MgAl₂O₄ and the transition metal spinels (NiFe₂O₄, NiAlFeO₄) have been prepared by standard ceramic processing method in the air. The effect of annealing atmosphere on the dielectric properties after sintering has been studied. The annealing atmospheres were N₂, O₂, and N₂–H₂ mixture. Dielectric constant ? _r and tangent loss tanδ have been characterized by varying the measuring temperature and frequency (5 Hz–5 MHz) using the impedance analyzer. The ? _r and tanδ of the non-transition metal spinel MgAl₂O₄ remained unchanged even with varying the annealing atmosphere. While the dielectric properties of the transition metal spinels, NiFe₂O₄ and NiAlFeO₄ were critically dependent on the annealing atmosphere. Crystal structural models for the samples manufactured in air have been tested by the Rietveld refinement method for both the centrosymmetric Fd-3m and the noncentrosymmetric F-43m. The electron density distributions were determined by the whole pattern fitting based on the maximum entropy method (MEM). The dielectric properties of the samples have been also discussed in terms of the structure and electron distribution analysis results.