RESUMEN
Ultrathin (<100 nm) unstable polymer films exposed to a solvent vapor dewet by the growth of surface instability, the wavelength (λ) of which depends on the film thickness (h(f)). While the dewetting of a flat polymer thin film results in random structures, we show that the dewetting of a prepatterned film results in myriad ordered mesoscale morphologies under specific conditions. Such a film undergoes rupture over the thinnest parts when the initial local thickness of these zones (h(rm)) is lower than a limiting thickness h(lim) ≈ 10 nm. Additionally, the width of the pattern grooves (l(s)) must be wider than λ(s) corresponding to a flat film having a thickness of h(rm) for pattern-directed dewetting to take place over surface-tension-induced flattening. We first present an experimentally obtained morphology phase diagram that captures the conditions where a transition from surface-tension-induced flattening to pattern-directed-rupture takes place. Subsequently, we show the versatility of this technique in achieving a variety of aligned mesopatterns starting from a prepatterned film with simple grating geometry. The morphology of the evolving patterns depends on several parameters such as the initial film thickness (h(f)), prepattern amplitude (h(st)), duration of solvent vapor exposure (SVE), and wettability of the stamp used for patterning. Periodic rupture of the film at regular intervals imposes directionality on the evolving patterns, resulting in isolated long threads/cylindrical ridges of polymers, which subsequently disintegrate into an aligned array of droplets due to Rayleigh-Plateau instability under specific conditions. Other patterns such as a double periodic array of droplets and an array of holes are also possible to obtain. The evolution can be interrupted at any intermediate stage by terminating the solvent vapor annealing, allowing the creation of pattern morphology on demand. The created patterns are significantly miniaturized in size as compared to features obtained from dewetting a flat film with the same hf.
RESUMEN
The advent of a new method for measuring the zeta potential of planar surfaces, the rotating disk, allowed the investigation of the charging process of mica after immersion in water. The zeta potential of freshly cleaved muscovite mica was recorded within seconds of immersion of the sample and in fractions of a second thereafter. The zeta potential of mica in water at pH = 5.6 with no added potassium changed by 40-50 mV over approximately 1 min. A model of adsorption and desorption of potassium ions and protons captured this behavior and provided a framework for determination of surface adsorption rate constants. The charging of mica in alkaline KCl solutions of arbitrary concentration, however, was too fast for observation. The equilibrium zeta potential depended on the logarithm of salt concentration, in agreement with a model based on ion exchange reactions. The average values of the proton adsorption, proton desorption, potassium adsorption, and potassium desorption rate coefficients were 45 L/s +/- 15, 0.0014/s +/- 0.0006, 58 L/s +/- 5, and 0.14/s +/- 0.03, respectively. An equation giving the zeta potential as a function of the rate parameters and the concentrations of potassium ions and protons was derived. It is demonstrated that subtraction of zeta potentials, measured at different solution compositions within the same experiment, eliminates extrinsic factors and brings data from disparate measurements into agreement.
