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.

Mechanical properties and cross-link density of model composites being solution styrene–butadiene rubbers filled with different amounts of nanosized silica particles or mixtures of nanosized silica particles and micrometer-sized borosilicate glass particles are studied. The cross-link density of the rubber matrix is measured based on a double-quantum NMR spectroscopy method. Shear data show that reinforcement and dissipation G″ in the rubber plateau range depend systematically on the total surface area of the filler per unit composite. Different contributions to reinforcement due to hydrodynamic effects, “filler network”, glassy polymer layer, and “occluded rubber” are quantified based on a comparison of linear response measurements with strain sweeps performed at different temperatures. The results show a percolation threshold at silica volume fractions of about 0.15. The load-carrying capacity of the “filler network” decreases significantly with temperature. This may indicate the existence of a glassy polymer layer on the surface of the filler particles which softens several ten degrees above the bulk T g of the rubber matrix. Two regimes are found in the dissipation above T g which both depend systematically on the surface area of the filler system: A strongly frequency-dependent dissipation regime with power-law behavior is observed in G″(ω) at temperatures up to 70 K above the bulk T g, and a nearly frequency-independent G″ regime dominates at higher temperatures. The molecular nature and importance of this finding for tire applications are discussed.

In the present work, the wetting concept was further developed for explanation of the kinetics of silica localization in binary and ternary rubber blends in the first mixing period. In the second mixing period when the wetting process is finished, a re‐localization process of silica within the blend phases takes place until an equilibrium state is reached. Material effects and mixing conditions on the silica localization were systematically characterized. A comparison between the kinetics of filler localization experimentally determined by the wetting concept, and the filler localization at an equilibrium theoretically predicted by our Z‐model, provides a deeper insight into the filler transfer process taking place during the mixing process.

The effect of curing additives on the dispersion kinetics of carbon black (CB) in styrene butadiene rubber (SBR) compounds was investigated by means of the method of the online measured electrical conductance. Addition of curing additives such as stearic acid and diphenylguanidine (DPG) accelerates the CB dispersion process significantly. The viscosity of the rubber matrix was not changed after their addition. The addition of stearic acid and DPG may alter the filler–filler interaction that consequently leads to faster dispersion processes. The obtained difference in morphologies of SBR mixtures containing stearic acid and DPG, respectively, are caused by their different infiltration behavior, which may lead to different dispersion mechanisms. Addition of ZnO could not improve the dispersion process of CB because of its limited interaction with CB. Sulfur and N-cyclohexylbenzothiazole-2-sulfenamide decelerate the CB dispersion process. The strong effect of the rubber microstructure such as styrene content and molecular weight on the CB dispersion in SBR mixtures without additives was found and discussed by taking into consideration the known dispersion mechanisms. The influence of addition of curing additives on the CB dispersion in low styrene-content SBR mixtures is much more pronounced than that in high styrene-content SBR mixtures.