Understanding the role of nanosilica particle surfaces in the thermal degradation of nanosilica–poly(methyl methacrylate) solution-blended nanocomposites: From low to high silica concentration

Nanocomposites of poly(methyl methacrylate) and 12 nm silica particles have been prepared by a casting procedure which allows the homogeneous dispersion of up to 35 wt% of silica. Twelve nanocomposites with compositions ranging from 1 to 35 wt% have been prepared and studied by Scanning Electron Microscopy, Fourier Transform Infrared Spectroscopy, Differential Scanning Calorimetry, Thermogravimetric Analysis and Isothermal Chemiluminescence. Thermal stability increases outstandingly as soon as 1 wt% of silica is added to PMMA. This effect is well-known but had not been explained up to now. Of the two main processes which initiate degradation in PMMA, radical formation at labile chain ends and random chain scission, it is the former which disappears in composites with 3 wt% of silica. The origin of the thermal stabilization in these polymer composites is thus the blocking of the PMMA chain end by the silica particle. At the same time, viscous flow decreases progressively, and composites with 20 wt% of silica or over are dimensionally stable even if heated at 300 °C for several hours. The concomitant decrease of viscous flow and increase of low temperature thermal stability shift the temperature range of application of these composites strongly, and the understanding of the silica surface role allows envisaging the control of the behaviour.