ARTICLEorientational angles that are almost perpendicular to the surface normal vector in Figure 6. A possible consequence is that the mechanical coupling between silica nanoparticles and the surrounding polystyrene is less strong than expected. This is indeed found in experimental investigations. 70 ' ASSOCIATED CONTENT b S Supporting Information. Additional graphs presenting supporting analysis data. This material is available free of charge via the Internet at http://pubs.acs.org.

Silica nanoparticles (NPs) embedded in atactic polystyrene (PS) are simulated using coarse-grained (CG) potentials obtained via iterative Boltzmann inversion (IBI). The potentials are parametrized and validated on polystyrene of 2 kDa (i.e., chains containing 20 monomers). It is shown that the CG potentials are transferable between different systems. The structure of the polymer chains is strongly influenced by the NP. Layering, chain expansion, and preferential orientation of segments as well as of entire chains are found. The extent of the structural perturbation depends on the details of the system: bare NPs vs NPs grafted with PS chains, grafting density (0, 0.5, and 1 chains/nm 2 ), length of the grafted chains (2 and 8 kDa), and the matrix chains (2−20 kDa). For example, there is a change in the swelling state for the grafted corona (8 kDa, 1 chains/nm 2 ), when the matrix polymer is changed from 2 to > 8 kDa. This phenomenon, sometimes called "wet brush to dry brush transition", is in good agreement with neutron scattering investigations. Another example is the behavior of the radius of gyration of free polymer chains close to the NP. Short chains expand compared to the bulk, whereas chains whose unperturbed radius of gyration is larger than that of the NP contract.

The mechanical behavior of polystyrene and a silica-polystyrene nanocomposite under uniaxial elongation has been studied using a coarse-grained molecular dynamics technique. The Young's modulus, the Poisson ratio and the stress-strain curve of polystyrene have been computed for a range of temperatures, below and above the glass transition temperature. The predicted temperature dependence of the Young's modulus of polystyrene is compared to experimental data and predictions from atomistic simulations. The observed mechanical behavior of the nanocomposite is related to the local structure of the polymer matrix around the nanoparticles. Local segmental orientational and structural parameters of the deforming matrix have been calculated as a function of distance from nanoparticle's surface. A thorough analysis of these parameters reveals that the segments close to the silica nanoparticle's surface are stiffer than those in the bulk. The thickness of the nanoparticle-matrix interphase layer is estimated. The Young's modulus of the nanocomposite has been obtained for several nanoparticle volume fractions. The addition of nanoparticles results in an enhanced Young's modulus. A linear relation describes adequately the dependence of Young's modulus on the nanoparticle volume fraction.

Performing coarse-grained molecular dynamics simulations, the local dynamics of free and grafted polystyrene chains surrounding a spherical silica nanoparticle has been investigated, where the silica nanoparticle was either bare or grafted with 80-monomer polystyrene chains. The effect of the free (matrix) chain molecular weight and grafting density on the relaxation time of both the free and grafted polystyrene chains has been investigated. Furthermore, we have analyzed the local mobility of the grafted chains at different separations from the nanoparticle surface, as well as on the mean square displacement of the nanoparticles. Proximity to the surface, confinement by the surface, increased grafting density and increased matrix chain length were found to slow down the dynamics of the chain monomers and hence to increase the corresponding relaxation times. "Drying" of the grafted network of the nanoparticle via increasing the free chain lengths, which is known to shrink the brush-height, was found to slow down the relaxation of the brushes, too. The thickness of the interphase, beyond which the polymers showed bulklike behavior, was ∼2 nm for a bare nanoparticle, corresponding to four monomer layers, for all matrix chain lengths investigated. It increased to ∼3 nm for grafted nanoparticles depending on the grafting density and the matrix chain molecular weight.

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