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We probe the viscous relaxation of structured liquid droplets in the partial wetting regime using a diblock copolymer system. The relaxation time of the droplets is measured after a step change in temperature as a function of three tunable parameters: droplet size, equilibrium contact angle, and the viscosity of the fluid. Contrary to what is typically observed, the late-stage relaxation time does not scale with the radius of the droplet-rather, relaxation scales with the radius squared. Thus, the energy dissipation depends on the contact area of the droplet, rather than the contact line.

We have examined the direct effect of manipulating the number of free surfaces on the measured glass transition temperature T(g) of thin polystyrene films. Thin films in the range 35 nm < h < 114 nm with molecular weights of 592 kg/mol and 1144 kg/mol were studied. Ellipsometry was used to determine the temperature dependence of the thickness and refractive index of freestanding films. By noting the change in slope in each of these quantities, a T(g) value can be assigned in quantitative agreement with previously reported results. For thin freestanding films this value is reduced from that of the bulk. The exact same films are then transferred to a Si substrate and the T(g) of the resulting supported film was determined. The T(g) values of the now supported films are the same as the bulk value and the same as previous reports of similar supported films. These experiments unambiguously show that free interfaces are the dominant cause of the T(g) reductions for the film thicknesses studied.

The surface of a thin liquid film with nonconstant curvature is unstable, as the Laplace pressure drives a flow mediated by viscosity. We present the results of experiments on one of the simplest variable curvature surfaces: a stepped polymer film. Height profiles are measured as a function of time for a variety of molecular weights. The evolution of the profiles is shown to be self-similar. This self-similarity offers a precise measurement of the capillary velocity by comparison with numerical solutions of the thin film equation. We also derive a master expression for the time dependence of the excess free energy as a function of the material properties and film geometry. The experiment and theory are in excellent agreement and indicate the effectiveness of stepped polymer films to elucidate nanoscale rheological properties., 5 pages, 4 figures, article accepted for publication in Physical Review Letters

Hydrodynamic boundary conditions play a crucial role in the flow dynamics of thin films and can be probed by the analysis of liquid front profiles. For long-chained polymer films it was reported that a deviation from a symmetric profile is a result of viscoelastic effects. In this Letter, however, evidence is given that merely a slip-boundary condition at the solid-liquid interface can lead to an asymmetric profile. Variation of molecular weight shows that slippage is directly linked to chain entanglements. We find a reduced entanglement density at the solid-liquid interface (factors 3 to 4), which stresses the importance of considering nonbulk polymer properties in the vicinity of an interface.