Processing method determines the long-term stability of particle dispersions in concentrated nanoparticle/polymer...

Since the degree of particle dispersion can determine the physical properties of polymer nanocomposites (PNCs), plenty of studies have focused on the intrinsic parameters of PNCs such as the concentration/size/chemistry of nanoparticles/polymers relevant to the particle microstructure. While the consideration of these parameters is based on PNCs being in their equilibrium states, PNCs can be kinetically trapped in a nonequilibrium state during the multiple steps of processing. In other words, processing conditions can contribute more significantly to particle dispersion and the properties of PNCs beyond the effects of the intrinsic parameters. Hence, a systematic understanding of the nonequilibrium behaviour of PNCs is required to achieve the desired properties. In this work, we prepared concentrated suspensions with two different preparation pathways. The two different pathways yield different polymer conformations particularly near the particle surface despite the same composition of particles/polymers as the systems are trapped in a nonequilibrium state. Accordingly, the particle microstructures are also greatly changed by the preparation pathway. We found that even in the presence of solvents, these preparation pathway-dependent nonequilibrium effects on particle microstructures persist after several months of aging and ultimately determine the long-term stability of the particle dispersion.