Controlling the thermomechanical behavior of nanoparticle/polymer films.

Abstract

We show that the mesoscale (∼200 nm) thermomechanical properties of polymer nanocomposites formed from silica nanoparticles (NPs) and poly(2-vinylpyridine) (P2VP) critically depend on their interfacial structure, which can be controlled by the casting solvent. The composite films are solvent cast from either pyridine (PYR) or methylethylketone (MEK), with uniform NP spatial distribution obtained in both cases. In the films cast from MEK, our previous work has shown that a bound layer of P2VP is formed at the NP surfaces, while no such bound layer is formed when PYR is used as the casting solvent. In PYR as-cast films, Brillouin light scattering reveals a single acoustic phonon with its longitudinal sound velocity increasing with NP loading. This implies a homogeneous mixture of the NP and the polymer on the mesoscopic scales for all compositions examined. However, in the MEK as-cast films, two longitudinal and two transverse acoustic phonons are observed at NP loadings above ∼20 wt % (or ∼11 vol %), reminiscent of two metastable microscopic phases. The dense microphase is attributed to the bridging of NPs by P2VP chains, whereas for the softer medium, we conjecture that there exists an interfacial lower density P2VP layer whose longitudinal sound velocity barely changes with NP loading. These solvent-induced differences in the (elastic) mechanical behavior disappear upon thermal annealing, suggesting that these nanocomposite interfacial structures in the as-cast state (far from equilibrium) locally approach equilibrium (i.e., near equilibrium after annealing). Consistent with these conclusions, the abrupt decrease of the longitudinal sound velocity with temperature occurs at a single glass transition temperature for the annealed nanocomposites irrespective of the casting solvent used, which assumes only a slightly higher (∼5 K at 45 wt % or ∼29 vol %) value than that in bulk P2VP. The results emphasize the important role of solvent in determining the interfacial structure of nanocomposites, which can be used to tailor their thermomechanical behavior.