Why Volume and Dynamics Decouple in Nanocomposite Matrices: Space that Cannot Be Accessed is Not Free

Polymer nanocomposites have important material applications and are an ongoing focus of many molecular level investigations, however, puzzling experimental results exist. For example, specific volumes for some polymer nanocomposite matrices are 2% to 4% higher than for the neat polymer; in a pure polymer melt this would correspond to a pressure change of 40 to 100 MPa, and a decrease in isothermal segmental relaxation times of 3 to 5 orders of magnitude. However, the nanocomposite segmental dynamics do not show any speed up. We can explain this apparent uncoupling of dynamics from specific volume, and the key is to consider the system expansivity, i.e., the temperature dependence of the volumetric data, together with the concept of limiting volume at close liquid packing. Using pressure, volume, temperature data as a path to both, we are able to predict the effect of nanoadditives on the accessible, i.e., free, space in the material, which is critical for facilitating molecular rearrangements in dense systems. Our analysis explains why an increase in specific volume in a material may not always lead to faster segmental dynamics.