Theory of microstructure-dependent glassy shear elasticity and dynamic localization in melt polymer nanocomposites.

We present an integrated theoretical study of the structure, thermodynamic properties, dynamic localization, and glassy shear modulus of melt polymer nanocomposites (PNCs) that spans the three microstructural regimes of entropic depletion induced nanoparticle (NP) clustering, discrete adsorbed layer driven NP dispersion, and polymer-mediated bridging network. The evolution of equilibrium and dynamic properties with NP loading, total packing fraction, and strength of interfacial attraction is systematically studied based on a minimalist model. Structural predictions of polymer reference interaction site model integral equation theory are employed to establish the rich behavior of the interfacial cohesive force density, surface excess, and a measure of free volume as a function of PNC variables. The glassy dynamic shear modulus is predicted to be softened, reinforced, or hardly changed relative to the pure polymer melt depending on system parameters, as a result of the competing and qualitatively different influences of interfacial cohesion (physical bonding), free volume, and entropic depletion on dynamic localization and shear elasticity. The localization of polymer segments is the dominant factor in determining bulk PNC softening and reinforcement effects for moderate to strong interfacial attractions, respectively. While in the athermal entropy-dominated regime, the primary origin of mechanical reinforcement is the stress stored in the aggregated NP subsystem. The PNC shear modulus is often qualitatively correlated with the segment localization length but with notable exceptions. The present work provides the foundation for developing a theory of segmental relaxation, T changes, and collective NP dynamics in PNCs based on a self-consistent treatment of the cooperative activated motions of segments and NPs.