Corrosion Behavior of Smy(FexNi1-x)4Sb12 (0.40 <= x <= 0.80) in NaCl Solutions Studied by Electron Microscopy and ICP-AES

Filled skutterudites are currently studied as thermoelectric materials to be used in the automotive and nautical field; the study of their resistance to a saline environment is therefore mandatory. To this purpose, the corrosion behavior of several compositions belonging to the Smy(FexNi1-x)4Sb12 skutterudites system was investigated by immersing samples in differently concentrated (0.1 and 0.5 M) NaCl solutions. The effect of the treatment was analyzed both by SEM-EDS on the sample surface and at fixed times by ICP-AES on the solution. The formation of an oxide layer was observed on the surface of all the samples: the film results uniformly grown on specimens treated in NaCl at the lower concentration, while it is cracked and not spread over the whole surface in the other samples. Relying on the oxide layer thickness, the oxidation resistance results to increase with increasing the Fe content; correspondingly, the Sb concentration in the more diluted solution decreases at each time considered with increasing the Fe amount, pointing at a strict correlation between the cationic release and the oxide formation, and suggesting a possible mechanism for the growth of the protective film.