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Measurements of thermal diffusivity κ (using laser flash analysis) for temperatures from 100 °C to 1200 °C and of the inversion parameter x (using X‐ray analysis) for the single crystal spinel MgGa2O4 have been performed. X‐ray analysis showed a small change in x for samples annealed at 800 °C (x = 0.838) and 1200 °C (x = 0.834). Thermal diffusivity revealed a significant rise of κ for temperatures higher than 950 °C, deviating from the typical 1/T drop of κ. An additional systematic rise of κ with time is observed for temperatures between 950 °C and 1100 °C. A connection between cation disordering processes typical for spinels at elevated temperatures and the observed deviation of κ is proposed: Data indicate that cations changing their occupancy site at equilibration processes contribute significantly to κ and therefore represent a new type of heat transport.

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