Surface Degradation of MgX-Based Composites at Room Temperature: Assessing Grain Boundary and Bulk Diffusion Using Atomic Force Microscopy and Scanning Electron Microscopy.

Practical application of thermoelectric generators necessitates materials that combine high heat-to-electricity conversion efficiency with long-term functional stability under operation conditions. While Mg(Si,Sn)-based materials exhibit promising thermoelectric properties and module prototypes have been demonstrated, their stability remains a challenge, demanding thorough investigation. Utilizing atomic force microscopy (AFM) and scanning electron microscopy (SEM), we investigate the surface degradation of a composite material comprising Si-rich and Sn-rich Mg(Si,Sn) solid solutions. The investigation reveals a pronounced dependence of stability on Sn content, with the Sn-rich phase MgSiSn displaying the formation of a nonprotective oxide layer. Subsequent AFM measurements provide evidence of dominating grain boundary diffusion of loosely bound Mg, compared to bulk diffusion, observed within a few days, ultimately resulting in a complete surface oxidation of the Sn-rich phase within several weeks. On the other hand, MgSi and Si-rich MgSiSn remain stable against Mg diffusion to the surface even after prolonged exposure. Comparison with previous investigations confirms that the degradation rate is found to be highly dependent on the Sn content, with markedly higher rates observed for = 0.87 compared to = 0.70 in MgSiSn. These findings contribute to a better understanding of the stability challenges associated with Mg(Si,Sn)-based materials, essential for the development of robust thermoelectric materials for practical applications.