Corrosion behavior of thermoelectric clathrates α- and β-Eu8Ga16−xGe30+x in air

The corrosion of thermoelectric clathrates α- and β-Eu8Ga16−xGe30+x is studied under static air (DSC/TG) up to 650 °C. Oxidation product layers with thicknesses of 10.5 μm (α-Eu8Ga16−xGe30+x) and 4.5 μm (β-Eu8Ga16−xGe30+x) are formed. The oxidation begins at 360 and 380 °C, respectively. XRD pattern of the β-Eu8Ga16−xGe30+x oxidized layer shows Ge and four Eu2O3 reflections; while α-Eu8Ga16−xGe30+x data (sample crushed and grinded) shows α-Eu8Ga16−xGe30+x reflections (majority phase), two EuGa2±xGe4∓x strongest reflections and Ge (minority phases). These results indicate the amount of oxides is very small or they are amorphous. High temperature powder XRD measurements on α-Eu8Ga16−xGe30+x under air confirm the oxidation onset temperature determined in DSC studies.

► Thermoelectric materials convert directly heat from different sources into electricity.
► It is crucial to study their corrosion for potential applications at high temperature.
► The oxidation of europium clathrates in air begins at 360 °C (α-) and 380 °C (β-).
► The oxidized layer is twice thicker in the (α-) (10.5 μm) than in the β-phase (4.5 μm).