We
combine molecular dynamics simulations, imaging and data analysis,
and the Green–Kubo summation formula for the relaxation modulus G(t) to elicit the structure and rheology
of unentangled polymer–nanoparticle composites distinguished
by small NPs and strong NP–monomer attraction, εNPM ≫ k
B
T. A reptation-like plateau emerges in G(t) beyond a terminal relaxation time scale as the volume
fraction, c
NP, of NPs increases, coincident
with a structure transition. A condensed phase of NP-aggregates forms,
tightly interlaced with thin sheets of polymer chains, the remaining
phase consisting of free chains void of NPs. Rouse mode analyses are
applied to the two individual phases, revealing that long-wavelength
Rouse modes in the aggregate phase are the source of reptation-like
relaxation. Imaging reveals chain motion confined within the thin
sheets between NPs and exhibits a 2D analogue of classical reptation.
In the NP-free phase, Rouse modes relax indistinguishable from a neat
polymer melt. The Fourier transform of G(t) reveals a sol–gel transition across a broad frequency
spectrum, tuned by c
NP and εNPM above critical thresholds, below which all structure and
rheological transitions vanish.