Anomalous nanoparticle diffusion in polymer solutions and melts: A mode-coupling theory study

Mode-coupling theory is employed to study diffusion of nanoparticles in polymer melts and solutions. Theoretical results are directly compared with molecular dynamics simulation data for a similar model. The theory correctly reproduces the effects of the nanoparticle size, mass, particle-polymer interaction strength, and polymer chain length on the nanoparticle diffusion coefficient. In accord with earlier experimental, simulation, and theoretical work, it is found that when the polymer radius of gyration exceeds the nanoparticle radius, the Stokes-Einstein relation underestimates the particle diffusion coefficient by as much as an order of magnitude. Within the mode-coupling theory framework, a microscopic interpretation of this phenomenon is given, whereby the total diffusion coefficient is decomposed into microscopic and hydrodynamic contributions, with the former dominant in the small particle limit, and the latter dominant in the large particle limit. This interpretation is in agreement with previous mode-coupling theory studies of anomalous diffusion of solutes in simple dense fluids. (C) 2011 American Institute of Physics. [doi:10.1063/1.3556749]