Depercolation of aggregates upon polymer grafting in simplified industrial nanocomposites studied with dielectric spectroscopy

The dynamics of polymer and filler in simplified industrial silica-styrene-butadiene nanocomposites (silica Zeosil 1165 MP, volume fraction 0-21%v) have been studied with broadband dielectric spectroscopy (BDS) and nuclear magnetic resonance (NMR). The fraction of graftable matrix chains was varied from 0 to 100%D3. The introduction of silica nanoparticles is shown to leave the segmental relaxation unaffected, an observation confirmed by the measurement of only a thin (some Angstroms thick) immobilized layer by NMR. The low-frequency measurements are resolved in two distinct dielectric Maxwell-Wagner-Sillars (MWS) processes of different behavior with respect to changes of large-scale silica structures induced by variations of filler fraction and grafting. It is found that increasing grafting leaves the first MWS-process unaffected, while it decreases the strength of the (slower) second MWS by about a decade. At constant silica volume fraction, this indicates depercolation of the filler, thereby providing a microscopic explanation of the evolution of rheological reinforcement. The sensitivity to large-scale reorganizations together with a characterization of local polymer dynamics provides insight over many length- and time-scales into structure and dynamics of nanocomposites, and thus the physical origin of the reinforcement effect.We are thankful for a “Chercheur d'Avenir” grant by the Languedoc-Roussillon region (J.O.) and Ph.D. funding “CIFRE” by Michelin (G.P.B.). The authors acknowledge financial support from the European Commission under the Seventh Framework Program by means of the grant agreement for the Integrated Infrastructure Initiative N. 262348 European Soft Matter Infrastructure (ESMI).Peer Reviewe