Zirconia-based plasma-sprayed coatings are extensively used in jet and land-based engines as thermal barrier coatings (TBCs) for protecting and insulating gas turbine metal components from the extreme temperature in the hot gas extending the engine life capabilities and service performances as well as reducing fuel consumption. Zirconia-based thermal barrier coatings stabilized with yttria and ceria were prepared by means of atmospheric plasma spray (APS) and thermal treated at different temperatures. The resulting fractured heated surfaces have been studied by means of X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM) combined with energy dispersive spectrometry (EDS) and secondary ion mass spectrometry (SIMS) in order to study the surface micro-chemical composition and morphology. The results disclose the variation of the stabilizing oxide amount, the occurrence of valence state modifications of cerium, impurity segregation phenomena and sintering. High temperature sintering influenced the porous microstructure leading to structural changes of the surface. This information confirmed that chemical and morphological aspects in plasma sprayed TBCs must be known in order to understand and predict relationships between the parameters of plasma spray process and TBC features, properties and performances for a better design of reliable TBCs. (C) 2013 Elsevier B. V. All rights reserved.