The thermal behavior of pure ZrO2 and four ZrO2-based organic-inorganic hybrids (OIHs) containing increasing amount (6, 12, 24 and 50 wt%) of poly(ε-caprolactone) (PCL) (named Z, ZP6, ZP12, ZP24 and ZP50 respectively) has been studied by simultaneous thermogravimetry (TG) and differential scanning calorimetry (DSC). The FTIR analysis of the gas mixture evolved at defined temperatures from the samples submitted to the TG experiments identified the mechanism of each thermally activated process. The obtained results suggest that the inorganic matrix of the OIHs prepared by this method exerts a stabilizing effect on the polymer, in particular for poor-PCL hybrid materials. In fact, the different thermal behavior of the ZP50 sample suggests that the polymer is not entirely bonded to the -OH groups of the zirconia matrix due to their saturation. For this reason a part of PCL is not affected by the stabilizing effect of the matrix and is subjected to thermal degradation. Finally, by observing their thermal behavior it was possible to select the most suitable temperatures for thermal pretreatment: 400, 600 and 1000 °C. The structural analysis by X-ray diffraction (XRD) revealed that at 400 °C the materials are amorphous, while at 600 °C they are mostly tetragonal, and the content of the tetragonal phase decreases with increasing the amount of PCL in the OIHs. All the materials treated at 1000 °C are monoclinic, but their crystallinity decreases with increasing the PCL content. © 2018

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