Pseudo-percolation: Critical volume fractions and mechanical percolation in polymer nanocomposites

Polymer nanocomposites offer a basis for the design and manufacture composite materials with greatly enhanced properties at relatively low volume fractions of the included phase. One underlying mechanism, thought to contribute to these properties is the presence of an interfacial region, ∼15 nm thick, between the polymer matrix and included particles. The size of the interface makes relatively little contribution to the effective properties of composites with micro-sized particles but, because its thickness is comparable to the size of the nanoscaled included phase, its potential impact within nanocomposites is much greater. In particular, percolated nano-microstructures may result at volume fractions below theoretical thresholds, due to connectivity achieved through rod-interface-rod, or ‘pseudo-percolation’, contact. In this work the influence of the interface layer is incorporated into estimates of critical volume fraction through an excluded volume model. Results show a significant reduction in the range of critical volume fractions. These values are incorporated into a mean-field micromechanics model to illustrate mechanical percolation through changes in predicted effective elastic composite properties.

► This work examines the effect of scale on the properties of polymer nanocomposites. ► One effect is an interface region; a significant third phase of a nanocomposite. ► A second effect is number density, which may facilitate mechanical percolation. ► This work includes both effects in an excluded volume model. ► The model predicts tighter bounds on percolation threshold volume fractions.