Influence of n-ZnO Morphology on Sulfur Crosslinking and Properties of Styrene-Butadiene Rubber Vulcanizates

This paper examines the influence of the morphology of zinc oxide nanoparticles (n-ZnO) on the activation energy, vulcanization parameters, crosslink density, crosslink structure, and mechanical properties in the extension of the sulfur vulcanizates of styrene-butadiene rubber (SBR). Scanning electron microscopy was used to determine the particle size distribution and morphology, whereas the specific surface area (SSA) and squalene wettability of the n-ZnO nanoparticles were adequately evaluated using the Brunauer–Emmet–Teller (BET) equation and tensiometry. The n-ZnO were then added to the SBR in conventional (CV) or efficient (EV) vulcanization systems. The vulcametric curves were plotted, from which the cure rate index (CRI) rate of the vulcanization and the activation energy were calculated. The influence on the mechanical properties of the SBR vulcanizates was stronger in the case of the EV curing system than when the CV curing system was used. Of the vulcanizates produced in the EV curing system, the best performance was detected for n-ZnO particles with a hybrid morphology (flat-ended rod-like particles on a “cauliflower” base) and high SSA. Vulcanizates produced using the CV curing system showed slightly better mechanical properties after the addition of nanoparticles with a “cauliflower” morphology than when the rod-like type were used, irrespective of their SSA. In general, nanoparticles with a rod-like structure reduced the activation energy and increased the speed of vulcanization, whereas the cauliflower type slowed the rate of the process and the vulcanizates required a higher activation energy, especially when using the EV system. The crosslink structures were also more clearly modified, as manifested by a reduction in the polysulfidic crosslink content, especially when n-ZnO activators with a rod-like morphology were applied.