The present paper proposes a reliable alternative for the increasing stability of polypropylene (PP) by modified polyhedral oligomeric silsesquioxanes (POSS). The chemiluminescence measurements and FTIR records point complementarily out the determinant influence of substituents on the progress of oxidation during the accelerated degradation caused by γ-irradiation. The main kinetic approach of oxidation acting in radiation-induced aging recommends some of the studied structures of modified POSS as appropriate compounds for improving stability of polypropylene at low additive concentration. The analysis of the present results is based on the implication of substituted POSS, whose contribution to the limitation of oxidation is conditioned by the influence of substituents. The delay of the oxidative degradation in studied γ-irradiated polypropylene is the consequence of the interaction between molecular PP fragments and the silanol moieties generated during radiolysis, which are the most vulnerable points of POSS structure.

The stability of polymer materials is essentially determined by the molecular structure and the presence of additives and impurities. When a polymer substrate is subjected to vigorous damage by an energetic treatment, the molecular scission generates fragments, which may be oxidized by the diffused oxygen. The traces of oxide catalysts that may be accidentally incorporated into the polymer materials initiate a faster oxidation that influences the material durability. This study presents the behavior of poly (ε-caprolactone) (PCL) loaded with 2 wt% PbZrO₃ previously doped with foreign atoms (Cr, Nd, Mg, Mn, Ti) at the concentration of 0.1 mol%. The investigation procedure, chemiluminescence, reveals the acceleration of the degradation of PCL. The contribution of the metallic traces existing in the structure of PbTiO₃ powder is characterized by the activation energies (Ea) involved in the propagation of oxidation. The free radicals are involved in a faster oxidation, when the polymer substrate is heated at superior rates. The comparison of the oxidation levels at the extended period of heating and irradiation indicates the sustained activities of metallic traces acting in oxide powder fillers, especially at temperatures exceeding 150 °C. The essential considerations on material strength against oxidation are presented.