Dynamics of Architecturally Engineered All-Polymer Nanocomposites.

We present nanocomposite materials formed by using glassy star-shaped polymers as nanofillers and dispersing them in soft matrices. The resulting "architecturally engineered" polymer nanocomposites structurally reside between the linear homopolymer blends and the conventional polymer nanocomposites with inorganic fillers, inducing reinforcement, which can be as strong as that of solid nanoparticles, or softening depending on the compactness and concentration of the nanoparticles. Such behavior can be traced back to the dynamical features at the local segmental and the chain level, which we investigated using neutron scattering over a wide range of time and length scales in the glassy and melt states of the nanocomposites. The local and segmental dynamics as well as the degree of chain-chain entanglements are all modified by the star-shaped fillers. The presented approach to tuning the physical properties of all-polymer-based nanocomposites is readily adaptable to other polymer architectures with immediate applications in numerous areas including gas separation membranes, tissue engineering, drug delivery, and functional coatings.