We study the influence of high NaCl concentrations on the equilibrium and dynamic surface tensions of ionic (CTAB) and nonionic (Tween 80) surfactant solutions. Equilibrium surface tension measurements show that NaCl significantly reduces the critical micellar concentration (CMC) of CTAB but has no effect on the CMC of Tween 80. Dynamic surface tension measurements allow comparing the surface tension as a function of time for pure surfactant solutions and in the presence of NaCl. For the ionic surfactant, the dynamics agree with the usual diffusion-limited interfacial adsorption kinetics; however, the kinetics become orders of magnitude slower when NaCl is present. Sum-frequency generation spectroscopy experiments and the equilibrium adsorption measurements show that the presence of NaCl in CTAB solution leads to the formation of ion pairs at the surface, thereby neutralizing the charge of the head group of CTAB. This change, however, is not able to account for the slowing down of adsorption dynamics; we find that it is rather the decreases in the monomer concentration (CMC) in the presence of salt which has the major influence. For the nonionic surfactant, the kinetics of interfacial tension is seen to be already very slow, and the addition of salt does not influence it further. This also correlates very well to the very low CMC of Tween 80.

The surface tension of water is an important parameter for many biological or industrial processes, and roughly a factor of 3 higher than that of nonpolar liquids such as oils, which is usually attributed to hydrogen bonding and dipolar interactions. Here we show by studying the formation of water drops that the surface tension of a freshly created water surface is even higher (∼90 mN m^–1) than under equilibrium conditions (∼72 mN m^–1) with a relaxation process occurring on a long time scale (∼1 ms). Dynamic adsorption effects of protons or hydroxides may be at the origin of this dynamic surface tension. However, changing the pH does not significantly change the dynamic surface tension. It also seems unlikely that hydrogen bonding or dipole orientation effects play any role at the relatively long time scale probed in the experiments.

We study the evaporation rate from single drops as well as collections of drops on a solid substrate, both experimentally and theoretically. For a single isolated drop of water, in general the evaporative flux is limited by diffusion of water through the air, leading to an evaporation rate that is proportional to the linear dimension of the drop. Here, we test the limitations of this scaling law for several small drops and for very large drops. We find that both for simple arrangements of drops, as well as for complex drop size distributions found in sprays, cooperative effects between drops are significant. For large drops, we find that the onset of convection introduces a length scale of approximately 20 mm in radius, below which linear scaling is found. Above this length scale, the evaporation rate is proportional to the surface area.

Amontons’ law defines the friction coefficient as the ratio between friction force and normal force, and assumes that both these forces depend linearly on the real contact area between the two sliding surfaces. However, experimental testing of frictional contact models has proven difficult, because few in situ experiments are able to resolve this real contact area. Here, we present a contact detection method with molecular-level sensitivity. We find that while the friction force is proportional to the real contact area, the real contact area does not increase linearly with normal force. Contact simulations show that this is due to both elastic interactions between asperities on the surface and contact plasticity of the asperities. We reproduce the contact area and fine details of the measured contact geometry by including plastic hardening into the simulations. These new insights will pave the way for a quantitative microscopic understanding of contact mechanics and tribology.

There is an ongoing discussion in the literature about the flow behavior of the widely used model yield-stress fluid Carbopol. Some papers show that it is indeed the simple model yield-stress fluid that many people believe it to be. However, other authors report rheological hysteresis in the flow curve, transient shear banding that persists for a very long time, and the breaking of fore-aft symmetry in a falling ball experiment. Such behaviors have in the past been associated with thixotropic yield stress fluids, which are very different from simple ones. We present experiments that suggest that both types of behavior may be found in the same type of Carbopol, depending on the preparation: After strong stirring for a long time, the system becomes slightly thixotropic. Flow visualization experiments with fluorescently labeled Carbopol elucidate the difference between the simple and thixotropic behavior of the systems: The stirring breaks the polymers into smaller fragments, some of which are so small that ...