Electrical Conductivity of the Spinel CoFe$_2O_4$ Solid Solution

Spinel $CoFe_2O_4$ solid solutions containing up to 50 mol% CoO were synthesized with spectroscopically pure CoO and ${\alpha}-Fe_2O_3$ polycrystalline powders. The spinel structures of the $CoFe_2O_4$ solid solutions were analyzed from XRD patterns and the Mossbauer spectra showed that the quenched $CoFe_2O_4$ had a partially inversed spinel structure ($Co_{0.23}Fe_{0.77}$) < $Co_{0.77}Fe_{1.23}$ > $O_4$, while the slowly cooled $CoFe_2O_4$ was completely inversed spinel ($Co_{0.04}Fe_{0.96}$) <$Co_{0.96}Fe_{1.04}$ > $O_4$. The $CoFe_2O_4$ specimens containing 10, 20, 30 and 40 mol% CoO turned to be a mixture of corundum and spinel structures. Electrical conductivities were measured as a function of temperature from 300 to $900^{\circ}C$ under oxygen partial pressures from $10^{-3}$ to 1 atm. The temperature dependencies of the electrical conductivity show different behaviors in the low- and high-temperature regions. The average activation energies are 0.23 eV and 0.80 eV in the low- and high-temperature regions, respectively. It is suggested that $Co^{2+} {\to} CO^{3+} + e^-$ and $Fe^{2+} {\rightleftharpoons} Fe^{3+} + e^-$ are the main conduction mechanisms responsible for the electronic conduction in the low- and high-temperature regions, respectively.