title: Anomalous chain diffusion in polymer nanocomposites for varying polymer-filler interaction strengths.
abstract: Anomalous diffusion of polymer chains in a polymer nanocomposite melt is investigated for different polymer-nanoparticle interaction strengths using stochastic molecular dynamics simulations. For spherical nanoparticles dispersed in a polymer matrix the results indicate that the chain motion exhibits three distinct regions of diffusion, the Rouse-like motion, an intermediate subdiffusive regime followed by a normal Fickian diffusion. The motion of the chain end monomers shows a scaling that can be attributed to the formation of strong "networklike" structures, which have been seen in a variety of polymer nanocomposite systems. Irrespective of the polymer-particle interaction strengths, these three regimes seem to be present with small deviations. Further investigation on dynamic structure factor shows that the deviations simply exist due to the presence of strong enthalpic interactions between the monomers with the nanoparticles, albeit preserving the anomaly in the chain diffusion. The time-temperature superposition principle is also tested for this system and shows a striking resemblance with systems near glass transition and biological systems with molecular crowding. The universality class of the problem can be enormously important in understanding materials with strong affinity to form either a glass, a gel or networklike structures.
authors.affiliation: Computational Chemical Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA. goswamim@ornl.gov
authors.forename: Monojoy
authors.initials: M
authors.lastname: Goswami
authors.forename: Bobby G
authors.initials: BG
authors.lastname: Sumpter
mesh_terms: D004058:Diffusion; D056004:Molecular Dynamics Simulation; D009038:Motion; D053761:Nanocomposites / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D013997:Time Factors
chemical_list: D011108:Polymers