Interrelation between preparation conditions, structure and mechanical reinforcement in isoprene rubber filled with in situ generated silica

The sol–gel technique was used to reinforce isoprene rubber (IR) by generating silica in situ from tetraethoxysilane (TEOS). The aim of the research was to elucidate the effect of the preparation conditions on the structural and morphological characteristics of silica and the resulting mechanical reinforcement. The structure of the in situ generated silica was analyzed by 29Si high-resolution solid-state NMR spectroscopy, which evidenced a high condensation degree of TEOS that decreased with increasing the sol–gel reaction time. The silica dispersion became less homogeneous as the TEOS content and the reaction time were increased. The incorporation of a coupling agent (OTES, octyltriethoxysilane) in the reaction mixture promoted full conversion of TEOS. Lower particle size, better silica dispersion, and higher filler-matrix adhesion were noticed if the incorporation of OTES was delayed compared to TEOS. Uniaxial tensile tests evidenced that the tensile strength typically increased in the first 60 min of reaction and then leveled off. A similar behavior was observed for the high deformation stiffness, whereas at low deformations, the stiffness increased monotonically with the reaction time. In the vulcanizates with silica contents higher than 25 wt %, a drastic stiffness decrement was observed passing from low to high deformations. This reduction was ascribed to the disruption of the secondary filler network occurring in these materials when severely stretched.