Elucidation of segmental relaxations of silica‐filled cis‐polybutadiene rubber composites

There has been a lot of interest in characterizing polymer chain dynamics of rubber compounds because it is thought to underpin the exceptional mechanical properties of composites. We studied the effect of precipitated silica on segmental mobility of cis‐polybutadiene rubber by using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). It was found that the calorimetric glass and melting transitions of silica‐filled master batch materials were essentially identical to those of the gum rubber, showing no dependence of silica loading and silane treatment. And, we observed in calorimetric measurement a change in the melting transition step for the vulcanizates. The results were correlated to the change of chemical crosslinks caused by various factors filler agglomeration and adsorption effect that tended to decrease chemical crosslink density and silane modification increased it. The DMA results demonstrated that the second peak in loss modulus versus temperature curve for the quenched vulcanizates was assigned to melting peak, and this peak disappeared at a slow cooling rate, which coincided well with DSC results. Moreover, crystalline parts constrained amorphous regions such that the glass transition temperature was raised for the cooled vulcanizates with high chemical crosslinks.