Detection of surface-immobilized components and their role in viscoelastic reinforcement of rubber-silica nanocomposites

Immobilized polymer fractions have been claimed to be of pivotal importance for the large mechanical reinforcement observed in nanoparticle-filled elastomers but remained elusive in actual application-relevant materials. We here isolate the additive filler network contribution to the storage modulus of industrial styrene-butadiene rubber (SBR) nanocomposites filled with silica at different frequencies and temperatures and demonstrate that it is viscoelastic in nature. We further quantify the amount of immobilized polymer using solid-state NMR and establish a correlation with the mechanical reinforcement, identifying a direct, strongly nonlinear dependence on the immobilized polymer fraction. The observation of a temperature-independent filler percolation threshold suggests that immobilized polymer fractions may not necessarily form contiguous layers around the filler particles but could only reside in highly confined regions between closely packed filler particles, where they dominate the bending modulus of aggregated particles.