Supramolecular structures in nanocomposite multilayered films.

We investigate the multilayered structures of poly(ethylene)oxide/montmorillonite nanocomposite films made from solution. The shear orientation of a polymer-clay network in solution combined with simultaneous solvent evaporation leads to supramolecular multilayer formation in the film. The resulting films have highly ordered structures with sheet-like multilayers on the micrometer length scale. The polymer covered clay platelets were found to orient in interconnected blob-like chains and layers on the nanometer length scale. Inside the blobs, scattering experiments indicate the polymer covered and stacked clay platelets oriented in the plane of the film. The polymer is found to be partially crystalline although this is not visible by optical microscopy. Atomic force microscopy suggests that the excess polymer, which is not directly adsorbed to the clay, is wrapped around the stacked platelets building blobs and the polymer also interconnects the polymer-clay layers. Overall our results suggest the re-intercalation of clay platelets in films made from exfoliated polymer-clay solutions as well as the supramolecular order and hierarchical structuring on the nanometer, via micrometer to the centimeter length scale.

Growth of 'dizzy dendrites' in a random field of foreign particles.

Microstructure plays an essential role in determining the properties of crystalline materials. A widely used method to influence microstructure is the addition of nucleating agents. Observations on films formed from clay-polymer blends indicate that particulate additives, in addition to serving as nucleating agents, may also perturb crystal growth, leading to the formation of irregular dendritic morphologies. Here we describe the formation of these 'dizzy dendrites' using a phase-field theory, in which randomly distributed foreign particle inclusions perturb the crystallization by deflecting the tips of the growing dendrite arms. This mechanism of crystallization, which is verified experimentally, leads to a polycrystalline structure dependent on particle configuration and orientation. Using computer simulations we demonstrate that additives of controlled crystal orientation should allow for a substantial manipulation of the crystallization morphology.

Growth pulsations in symmetric dendritic crystallization in thin polymer blend films.

The crystallization of polymeric and metallic materials normally occurs under conditions far from equilibrium, leading to patterns that grow as propagating waves into the surrounding unstable fluid medium. The Mullins-Sekerka instability causes these wave fronts to break up into dendritic arms, and we anticipate that the normal modes of the dendrite tips have a significant influence on pattern growth. To check this possibility, we focus on the dendritic growth of polyethylene oxide in a thin-film geometry. This crystalline polymer is mixed with an amorphous polymer (polymethyl-methacrylate) to "tune" the morphology and clay was added to nucleate the crystallization. The tips of the main dendrite trunks pulsate during growth and the sidebranches, which grow orthogonally to the trunk, pulsate out of phase so that the tip dynamics is governed by a limit cycle. The pulsation period P increases sharply with decreasing film thickness L and then vanishes below a critical value L(c) approximately 80 nm. A change of dendrite morphology accompanies this transition.

Nonequilibrium pattern formation in the crystallization of polymer blend films.

We show that the morphology of polyethylene oxide crystallization in thin films can be tuned to obtain circular spherulites, seaweed and symmetric dendrites, and fractal aggregation forms through the addition of clay particles and the amorphous polymer, polymethyl methacrylate. The thin-film polymer crystallization patterns are compared to a two-dimensional phase field model of dendritic growth in Ni/Cu alloys with a variable surface tension anisotropy epsilon. Some aspects of polymer crystallization patterns can be understood from the phase field calculations, but a more general model is required to describe the full range of observed patterns.