Assembly of plate-like nanoparticles in immiscible polymer blends – effect of the presence of a preferred liquid–liquid interface

The assembly of lamellar (clay) nanoparticles in a blend of polystyrene (PS) and poly(methyl methacrylate) (PMMA) with drop-matrix morphology is studied combining viscoelastic measurements and morphological analyses. A reference system based on pure PS is used to highlight the effect on the assembly process of the presence of liquid interfaces where the particles are inclined to gather. The filler content is varied in a wide range to cover all the possible structures, from isolated flocs up to space-spanning networks. The goal is to elucidate whether the particles govern the blend morphology or the structural evolutions of the fluids dictate the space arrangement of the filler. The PMMA drops anchor the lamellae frustrating their peculiar mobility in the polymer melt. On the other hand, the clay radically affects the blend morphology, inducing irregularly-shaped drops and drop clustering phenomena even in case of partial coverage of the drop surface. Above the critical filler content for the saturation of the polymer-polymer interface, a space-spanning particle network eventually builds up. Despite the embedding of the PMMA drops, such a superstructure exhibits the same features of those forming in homogeneous mediums, enabling the use of approaches conceived for systems with single-phase matrix. Compared to the latter, the percolation and fractal models reveal subtle and yet meaningful differences in terms of stress-bearing mechanisms and structure of the building blocks which constitute the network.