Journal of Polymer Science Part B: Polymer Physics, Vol.43, No.17, 2399-2412, 2005
Polymer-filler interactions in sol-gel derived polymer/silica hybrid nanocomposites
The effect of polymer-filler interaction on solvent swelling and dynamic mechanical properties of the sol-gel derived acrylic rubber (ACM)/silica, epoxidized natural rubber (ENR)/silica, and poly (vinyl alcohol) (PVA)/silica hybrid nanocomposites has been described for the first time. Tetraethoxysilane (TEOS) at three different concentrations (10, 30, and 50 wt %) was used as the precursor for in situ silica generation. Equilibrium swelling of the hybrid nanocomposites in respective solvents at ambient condition showed highest volume fraction of the polymer in the swollen gel in PVA/silica system and least in ACM/silica, with ENR/silica recording an intermediate value. The Kraus constant (C) also followed a similar trend. In dynamic mechanical analysis, the storage modulus dropped at higher strain (> 1%), which indicated disengagement of polymer segments from the filler surfaces. This drop was maximum in ACM/silica, intermediate in ENR/silica, and minimum in PVA/silica, both at 50 and 70 degrees C. The drop in modulus with theoretical volume fraction of silica (phi) was interpreted with the help of a Power law model Delta E' = alpha(1)phi(b1), where a, was a constant and b(1), was primarily a filler attachment parameter. Strain dependence of loss modulus was observed in ACM/silica hybrid nanocomposites, while ENR/silica and PVA/silica nanocomposites showed almost strain-independent behavior. The storage modulus showed sharp increase with increasing frequency in ACM/silica system, while that was lower in both ENR/silica (at higher frequency) and PVA/silica systems (in the entire frequency spectrum). The increase in modulus with phi also followed similar model Delta E' = alpha(2)phi(-b2) proposed in the strain sweep mode. (c) 2005 Wiley Periodicals, Inc.