No abstract

We report the origin of the effect of nanoscale confinement on the local viscosity of entangled polystyrene (PS) films at temperatures far above the glass transition temperature. By using marker x-ray photon correlation spectroscopy with gold nanoparticles embedded in the PS films prepared on solid substrates, we have determined the local viscosity as a function of the distance from the polymer-substrate interface. The results show the impact of a very thin adsorbed layer (~7 nm in thickness) even without specific interactions of the polymer with the substrate, overcoming the effect of a surface mobile layer at the air-polymer interface and thereby resulting in a significant increase in the local viscosity as approaching the substrate interface.

The dynamics of supported polymer films were studied by probing the surface height fluctuations as a function of lateral length scale using x-ray photon correlation spectroscopy. Measurements were performed on polystyrene (PS) films of thicknesses varying from 84 to 333 nm at temperatures above the PS glass transition temperature. Within a range of wave vectors spanning 10(-3) to 10(-2) nm(-1), good agreement is found between the measured surface dynamics and the theory of overdamped thermal capillary waves on thin films. Quantitatively, the data can be accounted for using the viscosity of bulk PS.

a b s t r a c tWe discuss two methods by which high porosity silica aerogels can be engineered to exhibit global anisotropy. First, anisotropy can be introduced with axial strain (i.e. axial compression). In addition, intrinsic anisotropy can result during growth and drying stages and, suitably controlled, it can be correlated with preferential radial shrinkage in cylindrical samples. We have performed small angle X-ray scattering (SAXS) to characterize these two types of anisotropy. We show that global anisotropy originating from either strain or shrinkage leads to optical birefringence and that optical cross-polarization studies are a useful characterization of the uniformity of the imposed global anisotropy.

The surface dynamics of supported ultrathin polystyrene films with thickness comparable to the radius of gyration were investigated by surface sensitive x-ray photon correlation spectroscopy. We show for the first time that the conventional model of capillary waves on a viscous liquid has to be modified to include the effects of a shear modulus in order to explain both static and dynamic scattering data from ultrathin molten polymer films.

The technique of X-ray Photon Correlation Spectroscopy (XPCS) is reviewed as a method for studying the relatively slow dynamics of materials on time scales ranging from microseconds to thousands of seconds and length scales ranging from microns down to nanometers. We focus on the application of this technique to study dynamical fluctuations of surfaces, interfaces and thin films. We first discuss instrumental issues such as the effects of partial coherence (or alternatively finite instrumental resolution) and optimization of signal-to-noise ratios in the experiments. We then review what has been learned from recent XPCS studies of capillary wave fluctuations on liquid surfaces and polymer films, of nanoparticles used as probes to study the interior dynamics of polymer films, of liquid crystals and multilamellar surfactant films, and of metal surfaces, and magnetic domain wall fluctuations in antiferromagnets. We then discuss studies of non-equilibrium dynamics described by 2-time correlation functions. Finally, we briefly speculate on possible future XPCS experiments at new synchrotron sources currently under development including studies of dynamics on time scales down to femtoseconds.

Small angle x-ray scattering ͑SAXS͒ measurements were performed on nanoporous methyl silsesquioxane films that were generated by the incorporation of a sacrificial polymeric component into the matrix and subsequently removed by thermolysis. The average pore radii ranged from 1 to 5 nm over a porosity range of ϳ5-50%. The distribution in pore size was relatively broad and increases in breadth with porosity. The values and observations obtained by SAXS are in good agreement with field emission scanning electron microscopy.

By embedding "dilute" gold nanoparticles in single polystyrene thin films as "markers", we probe the local viscosity of the free surface at temperatures far above the glass transition temperature (T(g)). The technique used was x-ray photon correlation spectroscopy with resonance-enhanced x-ray scattering. The results clearly showed the surface viscosity is about 30% lower than the rest of the film. We found that this reduction is strongly associated with chain entanglements at the free surface rather than the reduction in T(g).