Insight into the kinetics of flocculation in silica reinforced compounds

Flocculation plays an important role in reinforcement of silica filled rubber compounds, even if coupling agents are applied. It is well known that silica tends to flocculate during the early stages of vulcanization, when no dense rubber network has been formed yet. In the present study, flocculation was monitored by following the change in storage modulus at low strain, the so-called Payne effect, using a RPA2000 dynamic mechanical tester. The kinetic parameters: the rate constant and the activation energy of the silica flocculation were calculated according to the well-known
Arrhenius equation. On basis of the value of the activation energy obtained for flocculation, it can be concluded that the silica flocculation is a purely physical phenomenon. Bound rubber measurements were also done in order to estimate the interfacial interaction layer between silica and polymer resulting from the coupling agent. The silica flocculation rate decreases with increasing interfacial
interaction layer on the silica surface. This indicates that the decrease of the flocculation rate is due to the shielding effect of coupling agent. In addition, according to Fickis law, it is also suggested that the attractive flux from forces related to polarity differences between the silica and the rubber is the determining factor for silica flocculation.