The influence of additives on polymer matrix mobility and the glass transition

In the region near an interface, the microscopic properties of a glass forming liquid may be perturbed from their equilibrium bulk values. In this work, we probe how the interfacial effects of additive particles dispersed in a matrix can influence the local mobility of the material and its glass transition temperature, Tg. Experimental measurements and simulation results indicate that additives, such as nanoparticles, gas molecules, and oligomers, can shift the mobility and Tg of a surrounding polymer matrix (even for relatively small concentrations of additive; e.g., 5-10% by volume) relative to the pure bulk matrix, thus leading to Tg enhancement or suppression. Additives thus provide a potential route for modifying the properties of a polymer material without significantly changing its chemical composition. Here we apply the Limited Mobility (LM) model to simulate a matrix containing additive species. We show that both additive concentration, as well as the strength of its very local influence on the surrounding matrix material, will determine whether the Tg of the system is raised or lowered, relative to the pure matrix. We demonstrate that incorporation of additives into the simple LM simulation method, which has successfully described the behavior of bulk and thin film glassy solids, leads to direct connections with available experimental and simulation results for a broad range of polymer/additive systems.