Capillary penetration of a series of entangled poly(ethylene oxide) melts within nanopores of self-ordered alumina follows an approximate t behavior according to the Lucas-Washburn equation; t is the time. However, the dependence on the capillary diameter deviates from the predicted proportionality to d; d is the pore diameter. We observed a reversal in the dynamics of capillary rise with polymer molecular weight. Chains with 50 entanglements (M ≤ 100 kg/mol) or less show a slower capillary rise than theoretically predicted as opposed to chains with more entanglements (M ≥ 500 kg/mol) that display a faster capillary rise. Although a faster capillary rise has been predicted by theory and observed experimentally, it is the first time to our knowledge that a slower capillary rise is observed for an entangled polymer melt under conditions of strong confinement (with 2R/d = 1). These results are discussed in the light of theoretical predictions for the existence of a critical length scale that depends on the molecular weight and separates the microscopic (d < d) from the macroscopic (d > d) regime.
In this work we show that the forced dynamic dewetting of surfactant solutions depends sensitively on the surfactant concentration. To measure this effect, a hydrophobic rotating cylinder was horizontally half immersed in aqueous surfactant solutions. Dynamic contact angles were measured optically by extrapolating the contour of the meniscus to the contact line. Anionic (sodium 1-decanesulfonate, S-1DeS), cationic (cetyl trimethylammonium bromide, CTAB) and nonionic surfactants (CE, CE and CE) with critical micelle concentrations (CMCs) spanning four orders of magnitude were used. The receding contact angle in water decreased with increasing velocity. This decrease was strongly enhanced when adding surfactant, even at surfactant concentrations of 10% of the critical micelle concentration. Plots of the receding contact angle-versus-velocity almost superimpose when being plotted at the same relative concentration (concentration/CMC). Thus the rescaled concentration is the dominating property for dynamic dewetting. The charge of the surfactants did not play a role, thus excluding electrostatic effects. The change in contact angle can be interpreted by local surface tension gradients, i.e. Marangoni stresses, close to the three-phase contact line. The decrease of dynamic contact angles with velocity follows two regimes. Despite the existence of Marangoni stresses close to the contact line, for a dewetting velocity above 1-10 mm s the hydrodynamic theory is able to describe the experimental results for all surfactant concentrations. At slower velocities an additional steep decrease of the contact angle with velocity was observed. Particle tracking velocimetry showed that the flow profiles do not differ with and without surfactant on a scales >100 μm.
In this article the microfluidic synthesis and characterization of micrometer sized actuating Janus particles containing a liquid crystalline elastomer (LCE) is presented. On one side these Janus particles consist of a hydrophobic liquid crystalline part, featuring strong shape changes during the thermotropic phase transition, whereas the other side contains a hydrophilic polyacrylamide network. The synthesis is based upon the dispersion of two immiscible monomer mixtures in a continuously flowing silicone oil, using two glass capillaries side by side to form Janus microdroplets of different morphologies. Furthermore, the systematic adjustment of the morphology of the Janus particles as well as the optimization of the actuation properties is conducted by precise control and variation of the microfluidic parameters. The actuation properties of the particles are studied by polarized optical microscopy (POM), in which relative length changes up to 52% are investigated for the elongation of LCEs during the phase transition in rodlike Janus particles. Further wide-angle X-ray scattering (WAXS) measurements verify the mesogen's orientation in a bipolar director field, which corresponds to the observed geometry of the Janus particle's shape changes.
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