Strategies for the synthesis of thermoplastic polymer nanocomposite materials with high inorganic filling fraction.

The governing parameters controlling the miscibility of particle additives within polymeric host media are analyzed for the particular case of silica particle fillers embedded within a poly(methyl methacrylate) (PMMA) matrix. For athermal polymer-graft modification of particles (corresponding to equal chemical composition of graft and matrix polymer), compatibility is found to be a sensitive function of the degree of polymerization of graft and host polymer chains as well as the particle radius. In agreement with theoretical predictions, uniform particle dispersion is observed if the degree of polymerization of grafted chains is comparable to (or exceeds) the corresponding value of the polymer matrix. The resulting restriction to high degree of polymerization limits the accessible inorganic fraction that is attainable in athermal particle/polymer blends. In contrast, favorable interaction between grafted polymer chains and the polymeric host (as realized in the case of poly(styrene-r-acrylonitrile)-grafted particles embedded within PMMA matrix) is shown to facilitate thermodynamically stable and uniform particle dispersion across the entire compositional range even in the limit of large particle size, short grafted chains, and high molecular matrix chains. The synthesis of thermoplastic composite materials with inorganic fraction exceeding 50 vol % combining quantitative optical limiting within the UV frequency range and polymer-like mechanical properties is demonstrated.