Chemisorption and thermally induced transformations of polydimethylsiloxane on the surface of nanoscale silica and ceria/silica

Compositions of polydimethylsiloxane (PDMS) polymer with nanosized silica and ceria/silica were prepared. The influence of these nano-fillers on the thermal stability and degradation mechanism of silicone polymer was investigated using Thermogravimetric Analysis (TGA) and Temperature Programmed Desorption Mass Spectrometry (TPD MS). The results showed that thermal decomposition of pure and adsorbed PDMS differs significantly. The three main stages of the PDMS thermal transformations in the adsorbed state were determined to be: 1) chemisorption of PDMS chains involving the terminal trimethylsilyl groups of the polymer and silanol groups of the silica surface; 2) formation and desorption of cyclic oligomers; 3) high temperature radical degradation of the polymer accompanied by the formation of methane and ethylene. The kinetic parameters of the corresponding reactions were calculated from the TPD MS data. It was found that nanoparticles of cerium dioxide strongly influence the degradation pattern, lower the decomposition temperature and catalyze the formation of methane.