Swelling-Induced Delamination Causes Folding of Surface-Tethered Polymer Gels

When a polymer film that is weakly attached to a rigid substrate is exposed to solvent, swelling-induced compressive stress nucleates buckle delamination of the film from the substrate. Surprisingly, the buckles do not have a sinusoidal profile, instead, the film near the delamination buckles slides toward the buckles causing growth of sharp folds of high aspect ratio. These folds do not result from a wrinkle-to-fold transition; instead, the film goes directly from a flat state to a folded state. The folds persist even after the solvent evaporates. We propose that patterned delamination and folding may be exploited to realize high-aspect ratio topological features on surfaces through control of a set of boundary constraints arising from the interrelation of film-surface adhesion, film thickness and degree of swellabilty

Swelling-Induced Delamination Causes Folding of Surface-Tethered Polymer Gels

When a polymer film that is weakly attached to a rigid substrate is exposed to solvent, swelling-induced compressive stress nucleates buckle delamination of the film from the substrate. Surprisingly, the buckles do not have a sinusoidal profile, instead, the film near the delamination buckles slides toward the buckles causing growth of sharp folds of high aspect ratio. These folds do not result from a wrinkle-to-fold transition; instead, the film goes directly from a flat state to a folded state. The folds persist even after the solvent evaporates. We propose that patterned delamination and folding may be exploited to realize high-aspect ratio topological features on surfaces through control of a set of boundary constraints arising from the interrelation of film-surface adhesion, film thickness and degree of swellabilty

Swelling-Induced Delamination Causes Folding of Surface-Tethered Polymer Gels

When a polymer film that is weakly attached to a rigid substrate is exposed to solvent, swelling-induced compressive stress nucleates buckle delamination of the film from the substrate. Surprisingly, the buckles do not have a sinusoidal profile, instead, the film near the delamination buckles slides toward the buckles causing growth of sharp folds of high aspect ratio. These folds do not result from a wrinkle-to-fold transition; instead, the film goes directly from a flat state to a folded state. The folds persist even after the solvent evaporates. We propose that patterned delamination and folding may be exploited to realize high-aspect ratio topological features on surfaces through control of a set of boundary constraints arising from the interrelation of film-surface adhesion, film thickness and degree of swellabilty

Salt Effects on the Phase Behavior and Cocrystallization Kinetics of POCB–Water Mixtures

Mixtures of water with polyoxacyclobutane (POCB) have a unique phase diagram which combines liquid–liquid equilibrium (LLE) at high temperatures and cocrystallization of a POCB-hydrate at low temperatures. Such cocrystal hydrate formation is extremely rare among polymers. We report on the effects of adding NaCl salt on the phase behavior of POCB–water mixtures and the kinetics of hydrate crystallization from such mixtures. Salt loadings of less than 0.1 wt % were found to greatly expand the LLE region. Salt loadings of ∼10 wt % were found to significantly decrease the melting temperature of the hydrate below its ∼37 °C value under salt-free conditions. The hydrate was found to be remarkably tolerant of salt and persists at room temperature even when equilibrated with salt-saturated water. Salt was found to slow down hydrate crystallization, and the degree of slowing was greater than that expected from the salt-induced decrease in undercooling due to melting point depression

Aggregation and Separation in Ternary Particle/Oil/Water Systems with Fully Wettable Particles

We report that a variety of ternary particle/liquid/liquid mixtures heavily aggregate or separate completely if (1) the particles are fully or almost fully wetted by one fluid, and (2) if the wetting fluid volume fraction is comparable to the particle volume fraction. Aggregation and separation do not happen if the particles are partially wetted by both fluids, in which case Pickering emulsions appear at all compositions. Rheological and geometric criteria for aggregation are proposed and compared with a state diagram of a ternary system composed of oil, water, and hydrophilic glass particles. Analogies are drawn to wet granulation and spherical agglomeration, two particle processing operations in which wetting phenomena are important

Liquids That Freeze When Mixed: Cocrystallization and Liquid–Liquid Equilibrium in Polyoxacyclobutane–Water Mixtures

We show that liquid polyoxacyclobutane −[CH₂–CH₂–CH₂–O]_<i>n</i>– when mixed with water at room temperature precipitates solid cocrystals of the polymer and water. Cocrystals can also be formed by simply exposing the liquid polymer to saturated humidity. This appears to be the only known example of nonreacting liquids combining to form a solid cocrystal, also known as a clatherate, at room temperature. At high temperatures, the same polymer–water mixtures phase separate into two coexisting liquid phases. This combination of cocrystal formation and LCST-type liquid–liquid equilibrium gives rise to an unusual, possibly unique, type of phase diagram