Evidence for the molecular-scale origin of the suppression of physical ageing in confined polymer: Fluorescence and dielectric spectroscopy studies of polymer-silica nanocomposites

Fluorescence spectroscopy was used to characterize the rate of physical ageing at room temperature in nanocomposites of silica (10-15 nm diameter) nanoparticles in poly(methyl methacrylate) (PMMA). The physical ageing rate was reduced by more than a factor of 20 in 0.4 vol% silica-PMMA nanocomposites relative to neat PMMA. The molecular-scale origin of this nearly complete arresting of physical ageing was investigated with dielectric spectroscopy. The strength of the β relaxation process was reduced by nearly 50% in the nanocomposite relative to neat PMMA. This reduced strength of the β process results from dipoles (ester groups) having hindered motions or being virtually immobile on the timescale being probed at a frequency of 100 Hz. This hindered mobility results from hydrogen bonding between PMMA ester side groups and hydroxyl units on the surface of the silica nanoparticles. In contrast, no reduction in physical ageing rate was observed upon addition of silica to polystyrene, which cannot form hydrogen bonds with the silica surfaces. Thus, the molecular origin of the suppressed physical ageing in silica-PMMA nanocomposites is the interfacial hydrogen bonding, which leads to a major reduction in the strength of the β process, i.e., the β process is largely responsible for the observed physical ageing.