Interfacially-Located Nanoparticles Anticipate the Onset of Co-Continuity in Immiscible Polymer Blends

The addition of nanoparticles has recently emerged as a clever tool to manipulate the microstructure and, through it, the macroscopic properties of immiscible polymer blends. Despite the huge number of studies in this field, the underlying mechanisms of most of the nanoparticle-induced effects on the blend microstructure remain poorly understood. Among others, the origin of effect of nanoparticles on the transition from distributed (drop-in-matrix) to co-continuous morphology is still controversial. Here we address this issue through a systematic study on a model blend of polystyrene (PS) and poly(methyl methacrylate) (PMMA) filled with small amounts of nanoparticles (organo-modified clay) selectively located at the polymer⁻polymer interface. Extraction experiments with selective solvents prove that the nanoparticles significantly anticipate the onset of co-continuity with respect to the unfilled blend. Morphological analyses reveal that such an effect is a consequence of the interconnection of nanoparticle-coated polymer domains. Such "ginger-like" clusters get into contact at low content due to their irregular shape, thus anticipating the onset of co-continuity.