On the role of the three-phase contact line in surface deformation.

Viscoelastic braking theories developed by Shanahan and de Gennes and by others predict deformation of a solid surface at the solid-liquid-air contact line. This phenomenon has only been observed for soft smooth surfaces and results in a protrusion of the solid surface at the three-phase contact line, in agreement with the theoretical predictions. Despite the large (enough to break chemical bonds) forces associated with it, this deformation was not confirmed experimentally for hard surfaces, especially for hydrophobic ones. In this study we use superhydrophobic surfaces composed of an array of silicon nanostructures whose Young modulus is 4 orders of magnitude higher than that of surfaces in earlier recorded viscoelastic braking experiments. We distinguish between two cases: when a water drop forms an adhesive contact, albeit small, with the apparent contact angle θ < 180° and when the drop-surface adhesion is such that the conditions for placing a resting drop on the surface cannot be reached (i.e., θ = 180°). In the first case we show that there is a surface deformation at the three-phase contact line which is associated with a reduction in the hydrophobicity of the surface. For the second case, however, there cannot be a three-phase contact line associated with a drop in contact with the surface, and indeed, if we force-place a drop on the surface by holding it with a needle, no deformation is detected, nor is there a reduction in the hydrophobic properties of the surface. Yet, if we create a long horizontal three-phase contact line by partially immersing the superhydrophobic substrate in a water bath, we see a localized reduction in the hydrophobic properties of the surface in the region where the three-phase contact line used to be. The SEM scan of that region shows a narrow horizontal stripe where the nanorods are no longer there, and instead there is only a shallow structure that is lower than the nanorods height and resembles fused or removed nanorods. Away from that region, either on the part of the surface which was exposed to bulk water or the part which was exposed to air, no change in the hydrophobic properties of the surface is observed, and the SEM scan confirms that the nanorods seem intact in both regions.

Measurement of lateral adhesion forces at the interface between a liquid drop and a substrate.

A novel instrument allows for the first time measurements of the lateral adhesion forces at a solid-liquid interface, f(parallel), in a way that is decoupled from the normal forces, f(perpendicular). We use it to measure how f(parallel) between a drop and a surface is influenced by different f(perpendicular) and different histories of drop resting periods on the surface prior to sliding, t(rest). The variation of f(parallel) with t(rest) is similar for different f(perpendicular) and always plateaus as t(rest)-->infinity. We show that the f(parallel) plateau value is higher when f(perpendicular) is lower. This seemingly counterintuitive result is in agreement with recent theories.

Water tribology on graphene.

Classical experiments show that the force required to slide liquid drops on surfaces increases with the resting time of the drop, t(rest), and reaches a plateau typically after several minutes. Here we use the centrifugal adhesion balance to show that the lateral force required to slide a water drop on a graphene surface is practically invariant with t(rest). In addition, the drop's three-phase contact line adopts a peculiar micrometric serrated form. These observations agree well with current theories that relate the time effect to deformation and molecular re-orientation of the substrate surface. Such molecular re-orientation is non-existent on graphene, which is chemically homogenous. Hence, graphene appears to provide a unique tribological surface test bed for a variety of liquid drop-surface interactions.

Chasing drops: following escaper and pursuer drop couple system.

We study experimentally six different systems in which Marangoni flow is induced by two chemically different drops on a solid surface in air. In such systems one drop seems to chase away the other. We show that in all the systems studied, the Marangoni flow is induced at the solid-vapor interface as opposed to the air-liquid interface. This is true even for the case of water drop and alcohol drop on a glass surface (which corresponds to the "tears of wine" classical case). Thus we explain the drop motion as a result of an interfacial tension gradient which takes place primarily at the air-surface region and less, if at all, at the two other interfaces in the problem: the liquid-substrate or liquid-air interfaces. Then we follow the motion of drops on surfaces and find that it is discontinuous, i.e. characterized by stops and jumps as in a stick slip mechanism. We explain this behavior by an increase in the Laplace pressure that creates a higher anchoring pinning effect at the front edge of the moving drop. The understanding of this process has implications for passively separating mixed liquids.

Drop retention force as a function of drop size.

The force, f, required to slide a drop past a surface is often considered in the literature as linear with the drop width, w, so that f/w = const. Furthermore, according to the Dussan equation for the case that the advancing and receding contact angles are constant with drop size, one can further simplify the above proportionality to f/V(1/3) = const where V is the drop volume. We show, however, that experimentally f/V(1/3) is usually a decaying function of V (rather than constant). The retention force increases with the time the drop rested on the surface prior to sliding. We show that this rested-time effect is similar for different drop sizes, and thus the change of f/V(1/3) with V occurs irrespective of the rested-time effect which suggests that the two effects are induced by different physical phenomena. The time effect is induced by the unsatisfied normal component of the Young equation which slowly deforms the surface with time, while the size effect is induced by time independent properties. According to the Dussan equation, the change of f/V(1/3) with V is also expressed in contact angle variation. Our results, however, show that contact angle variation that is within the scatter suffices to explain the significant force variation. Thus, it is easier to predict contact angle variation based on force variation rather than predicting force variation based on contact angle variation. A decrease of f/V(1/3) with V appears more common in the system studied compared to an increase.

Drop retention force as a function of resting time.

The force, f, required to slide a drop on a surface is shown to be a growing function of the time, t, that the drop waited resting on the surface prior to the commencement of sliding. In this first report on the resting time effect, we demonstrate the existence of this phenomenon in different systems, which suggests that this phenomenon is general. We show that d f/d t is never negative. The shorter the resting times, the higher d f/d t is. As the resting time increases, d f/d t decreases toward zero (plateau) as t --> infinity. The increase in the force, Delta f, due to the resting time effect (i.e., f( t --> infinity) - f( t --> 0)) correlates well with the vertical component of the liquid-vapor surface tension, and we attribute this phenomenon to the corrugation of the surface by the drop due to this unsatisfied normal component of Young's equation.