Nanoparticles can modulate network topological defects during multimodal elastomer formation

We experimentally show that nanoparticles (NPs) can significantly regulate the network topological defects during a molecularly controlled elastomeric synthesis. Using positron annihilation lifetime spectroscopy, we demonstrate this on well-defined model systems of poly(dimethyl siloxane) elastomers and layered silicate nanoparticles (NPs). The evolutions of topological defects in elastomeric networks prepared from unimodal, bimodal, and NP dispersed bimodal elastomers are sequentially investigated. The extent of NP induced defect regulation is identified by varying the particle concentration from moderately low to an approximate upper limit. The fraction of free volume hole defects present between packed chains in the network generated by molecular control is significantly reduced. The fraction of smaller interstitial cavities near the cross-link sites shows a moderate increase at the lowest NP concentration. However, this fraction decreases at a high NP concentration and is nearly the same as that of bimodal networks that are devoid of NP infusion. Despite the variations in their fractions with NP infusion, the sizes of both these types of defects that remain in the network are minimally affected. The collective topological defects arising from chain induced heterogeneity also show a qualitative reduction upon NP infusion.