Electrical conductivity of diopside: evidence for oxygen vacancies

Impedance spectra for two natural single crystals of diopside were obtained at 800 to 1300??C and 1-bar pressure over the frequency range 0.001 Hz to 100 kHz in a system closed to all components but oxygen. At both higher and lower fO2 values, no fO2 dependence of conductivity was observed, indicating the presence of different conduction mechanisms. At temperatures less than 1000??C, the activation energy is 1.3 eV, also suggesting a different conduction mechanism. Thus, at least four regimes are necessary to describe the conductivity of this diopside in T-fO2 space. The approximately -1/(7 ?? 1) value of d(log ??)/d(log fO2) in a high-temperature geologic region suggests a reaction by which oxygen vacancies control the conductivity. This relatively pure diopside is much less conducting than olivine or orthopyroxene. A second diopside with greater Fe content but otherwise similar in composition to the near-end-member diopside, is more conducting, has a smaller activation energy (1.0 eV) over the range 1050 to 1225??C, and shows only a weak negative fO2 dependence; suggesting that oxygen vacancies are present but are not the dominant defect in controlling the conductivity. -from Authors