Melt rheology of nanocomposites based on acrylic copolymer and cellulose whiskers

Nanocomposites based on poly(styrene-co-hexylacrylate) copolymer and cellulose whiskers as the nanosize filler were prepared by in situ miniemulsion polymerization and their melt rheological behaviours were investigated under dynamic shear conditions. The effects of γ-methacryloxypropyl triethoxysilane (MPS) content along with the whisker loading were explored. In the absence of whiskers, a transition from a liquid- to a solid-like behaviour was observed when the polymer was synthesized in the presence of MPS. When cellulose nanofiller was added, the storage modulus G′ and the dynamic viscosities η of the nanocomposites increased monotonically with whisker content and the resulting materials displayed a solid-like behaviour. Above 2 wt.%. loading, a percolated interconnected whisker–whisker network is built up, producing a jump in the storage modulus and strong shear-thinning behaviour of the viscosity. However, as the nanocomposites were prepared in the presence of 3% of MPS, no enhancement nor in the storage modulus nor in the viscosity was observed up to 5 wt.%. of whisker loading. Such a phenomenon was ascribed to inhibition of build-up of the whisker network. The non-linear viscoelastic behaviour of the nanocomposites was also investigated and analysed in terms of the breakdown of different networks, namely the filler–filler and the polymer–filler networks.