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X-ray photon correlation spectroscopy is employed to investigate the motion of dilute suspensions of gold nanoparticles in low-molecular-weight polystyrene melts. At high temperatures, the observed motion is diffusive, with a rate that follows a Vogel-Fulcher temperature dependence. Closer to the glass transition temperature Tg, diffusion is superseded by a hyperdiffusive process that first becomes observable near a crossover temperature Tc approximately 1.1Tg and is identified with heterogeneous strain in the melts. Following rapid cooling to temperatures sufficiently below Tc, but still above Tg, the hyperdiffusive dynamics displays a time dependence similar to aging in polymer glasses.

We describe x-ray photon correlation spectroscopy (XPCS) experiments tracking the motion of gold nanoparticles within solutions of high-molecular-weight polystyrene. Over displacements from nanometers to tens of nanometers, the particles undergo subdiffusive motion that is dictated by the temporal evolution of the entangled polymer mesh in the immediate vicinity of the particles. The results thus provide a novel microscopic dynamical characterization of this key structural property of polymers and more broadly demonstrate the capability of XPCS-based microrheology to interrogate heterogeneous mechanical environments in nanostructured soft materials.

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