Theory of polymer diffusion in polymer-nanoparticle mixtures: effect of nanoparticle concentration and polymer length

The dynamics of polymer-nanoparticle (NP) mixtures, which involves multiple scales and system-specific variables, has posed a long-standing challenge on its theoretical description. In this paper, we construct a microscopic theory for polymer diffusion in mixtures based on a combination of the generalized Langevin equation, mode-coupling approach, and polymer physics ideas. The parameter-free theory has an explicit expression and remains tractable on a pair correlation level with system-specific equilibrium structures as input. Taking a minimal polymer-NP mixture as an example, our theory correctly captures the dependence of polymer diffusion on NP concentration and average interparticle distance. Importantly, the polymer diffusion exhibits a power law decay as the polymer length increases at dense NPs and/or a long chain, which marks the emergence of entanglement-like motion. The work provides a first-principles theoretical foundation to investigate dynamic problems in diverse polymer nanocomposites. Changes of polymer diffusion in polymer-nanoparticle mixtures influenced by nanoparticle concentration and polymer length are captured by a newly developed microscopic theoretical approach.