Spinodal clustering induced dewetting and non-monotonic stabilization of polymer blend films at high nanofiller concentrations

Abstract

We examine the effects of high fullerene nanoparticle (f-NP) concentrations, φf-NP ∼ (10-20) mass% on polystyrene (PS)/polybutadiene (PB) blend thin film stability. Dewetting of the polymer blend around spinodally clustered f-NPs in this high concentration limit leads to a spinodal like dewetting morphology. This is in contrast to our previously observed results on the stabilization effects of f-NPs on PS/PB blend thin films in the intermediate f-NP concentration range of 7-10 mass%, wherein, after saturating the polymer-blend interface, the NPs stabilize the film by segregating to the blend-substrate interface. We determine three regimes of polymer blend film stability as a function of filler concentration: a) φf-NP < 7 mass% where preferential segregation of the f-NPs to the polymer-polymer interface leads to macroscopic dewetting, b) φf-NP ∼ (7-10) mass% where PS/PB blend films exhibit complete film stability, and c) φf-NP ∼ (11-20) mass%, where spinodal clustering of the f-NPs gives rise to polymer-NP phase exclusion and subsequent dewetting. © 2013 Elsevier Ltd. All rights reserved.