Multiscale simulations of PS-SiO2 nanocomposites: from melt to glassy state.

The interaction energetics, molecular packing, entanglement network properties, segmental dynamics, and elastic constants of atactic polystyrene-amorphous silica nanocomposites in the molten and the glassy state are studied via molecular simulations using two interconnected levels of representation: (a) a coarse-grained one, wherein each polystyrene repeat unit is mapped onto a single "superatom" and the silica nanoparticle is viewed as a solid sphere. Equilibration at all length scales at this level is achieved via connectivity-altering Monte Carlo simulations. (b) A united-atom (UA) level, wherein the polymer chains are represented in terms of a united-atom forcefield and the silica nanoparticle is represented in terms of a simplified, fully atomistic model. Initial configurations for UA molecular dynamics (MD) simulations are obtained by reverse mapping well-equilibrated coarse-grained configurations. By analysing microcanonical UA MD trajectories, the polymer density profile is studied and the polymer is found to exhibit layering in the vicinity of the nanoparticle surface. An estimate of the enthalpy of mixing between polymer and nanoparticles, derived from the UA simulations, compares favourably against available experimental values. The dynamical behaviour of polystyrene (in neat and filled melt systems) is characterized in terms of bond orientation and dihedral angle time autocorrelation functions. At low concentration in the molten polymer matrix, silica nanoparticles are found to cause a slight deceleration of the segmental dynamics close to their surface compared to the bulk polymer. Well-equilibrated coarse-grained long-chain configurations are reduced to entanglement networks via topological analysis with the CReTA algorithm, yielding a slightly lower density of entanglements in the filled than in the neat systems. UA melt configurations are glassified by MD cooling. The elastic moduli of the resulting glassy nanocomposites are computed through an analysis of strain fluctuations in the undeformed state and through explicit mechanical deformation by MD, showing a stiffening of the polymer in the presence of nanoparticles. UA simulation results for the elastic constants are compared to continuum micromechanical calculations invoked in homogenization models of the overall mechanical behaviour of heterogeneous materials. They can be interpreted in terms of the presence of an "interphase" of approximate thickness 2 nm around the nanoparticles, with elastic constants intermediate between those of the filler and the matrix.

Effect of Surface Nanopatterning on Slip: The Case of Couette Flow of Long-Chain Polyethylene Melt Flowing Past Gold Surfaces.

The manifestation of slip during flow of a polymer melt past a solid surface depends on several parameters, such as film thickness, the strength of polymer-solid interactions compared to the cohesive energy of the polymer, and the roughness of the surface. Understanding the role of these molecular aspects for slip is crucial in microfluidics, friction-tuning, polymer extrusion, and nanocomposites applications. The present article investigates the effect of surface nanopatterning on slip, via Couette-flow simulations of long chain polyethylene melts past nanopatterned gold surfaces. Slip is quantified in terms of the true and effective slip velocity, and the slip length. When polymer chains are adsorbed to surfaces with periodic features (e.g., crystal planes), they develop preferential ordering in a way that enables them to minimize their free energy. The orientation of a chain is affected by that of its neighbors; thus, when several chains come together, they are prone to form regions with crystal-like orientation. We show that, in some cases, the introduction of nanopatterns on the surface can perturb and induce reorganization of these regions, and in turn affect slip. The nanopatterns are realized as periodic defect stripes of variable width, depth, areal density, and orientation angle. In situations in which the width of the defects becomes comparable to the diameter of individual chain backbones, slip is minimized (stick conditions). Cutting the nanopatterns in low symmetry directions can affect the quality of their edges and lead to enhanced friction. To characterize these edges we have devised a scheme for the quantification of the mean square roughness and mean position of the surface, which is general and applicable in 2 and 3 dimensions for any kind of material, either crystalline of amorphous. Applying the patterns on the opposing solid surfaces in a symmetric or antisymmetric manner has a profound effect on flow. We show that the application of nanopatterns in symmetric configurations generates zero net flow and induces additional shear along directions normal to the direction of the flow. The application of symmetry-breaking configurations can guide flow toward preferential directions, a result with possible applications in microfluidic devices.

Monte Carlo simulations of equilibrium solubilities and structure of water in n-alkanes and polyethylene.

Gibbs ensemble Monte Carlo methods based on a force field that combines the simple point charge [Berendsen et al., in Intermolecular Forces, edited by Pullman (Reidel, Dordrecht, 1981), p. 331] and transferable potentials for phase equilibria [Martin and Siepmann, J. Phys. Chem. B 102, 2659 (1998)] models were used to study the equilibrium properties of binary systems consisting of water and n-alkanes with chain lengths from hexane to hexadecane. In addition, systems where extended linear alkane chains (up to 300 carbon units long) were used to represent amorphous polyethylene were simulated in the presence of water using a connectivity altering osmotic Gibbs ensemble. In these simulations the equilibrium between a liquid water phase and a polymer phase into which water was inserted was studied. The predicted solubilities, which were determined between 350 and 550 K, are in good agreement with experiment, where experimental results are available, and the density of water molecules in the hydrocarbons is approximately 63% as high as in saturated water vapor under the same conditions. At the lower temperatures most of the water exists as monomers; increasing the temperature leads to an increase in the density of water in the alkane phase and hence in the fraction of molecules that participate in clusters. Dimers are the most prevalent clusters in all hydrocarbons and at all temperatures studied, and the fraction of clusters of given size decrease with increasing cluster size. A large fraction of trimers, tetramers, and pentamers, which are the cluster sizes for which topologies have been studied, are cyclic at low temperatures, but at higher temperatures linear structures predominate. The same properties are observed for pure water vapor clusters in equilibrium with the liquid phase, showing that the cluster topologies are not significantly affected by the surrounding hydrocarbon.

Formation of rodlike structures of water between oppositely charged ions in decane and polyethylene.

The Gibbs ensemble Monte Carlo method has been combined with the connectivity altering osmotic Gibbs ensemble to study water solubility and clustering in decane and polyethylene. We show that the presence of oppositely charged ion pairs that have fixed positions in the hydrocarbon matrices leads to an order of magnitude increase in the water solubility. This is important to a wide range of technical applications, since the uptake of the water leads to an increase in volume--or expansion--of the hydrocarbon phase which, in the case of polyethylene, may change the polymer properties and lead to water treeing. The increase in solubility is largest when the ions are sufficiently close so that rod-shaped clusters of water molecules form between the ions.