On the key role of SiO 2 @POSS hybrid filler in tailoring networking and interfaces in rubber nanocomposites

The present study provides a comprehensive investigation at the micro and nanoscale of the interface between hybrid SiO2@POSS nanofiller, where silica nanoparticles (NPs) and POSS nanocages are intimately inter- connected, and Styrene Butadiene Rubber (SBR). SEM and AFM inspection and, more in depth, solid state 1H NMR revealed a remarkable fraction of rigid rubber close to the SiO2@POSS surfaces, which increases with the curing temperature. Instead, a reduced amount of immobilized rubber was detected for SBR/SiO2+POSS na- nocomposites, obtained by simply mixing SBR, SiO2 and POSS. The results allowed us to propose a model for the network formation in C-SBR/SiO2@POSS. This is based on the progressive activation by dicumylperoxide (DCP) of the methacryl functionalities of POSS nanounits which, being closely connected to SiO2 NPs in SiO2@POSS, promote crosslinking in proximity of the filler surfaces, and lead to the generation of a tight network strongly bonded to the rubber chains.