The line energy associated with the triple phase contact line is a function of local surface defects (chemical and topographical); however, it can still be calculated from the advancing and receding contact angles to which those defects give rise. In this study an expression for the line energy associated with the triple phase contact line is developed. The expression relates the line energy to the drop volume, the interfacial energies, and the actual contact angle (be it advancing, receding, or in between). From the expression we can back calculate the equilibrium Young contact angle, theta0, as a function of the maximal advancing, thetaA, and minimal receding, thetaR, contact angles. To keep a certain maximal hysteresis between advancing and receding angles, different line energies are required depending on the three interfacial energies and the drop's volume V. We learn from the obtained expressions that the hysteresis is determined by some dimensionless parameter, K, which is some normalized line energy. The value of K required to keep a constant hysteresis (thetaA-thetaR) rises to infinity as we get closer to theta0 = 90 degrees.
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.
Using high-resolution shear force measurements, we examine in detail the frictional drag between rubbing surfaces bearing end-tethered polymeric surfactants (brushes). The drag attains a maximum on initial motion, attributed to elastic stretching of the chains, which falls by a cascade of relaxations to a value characteristic of kinetic friction. This has a very weak velocity dependence, attributed to chain moieties dragging within a self-regulating, mutual interpenetration zone. When sliding stops, the shear stress across the polymer layers decays logarithmically with time, consistent with the relaxation of a network of dangling ends.
Oleic acid and stearic acid are similar surfactants which, however, lead respectively to stability and to precipitation of ferrofluid suspensions: to understand this, the forces between layers of oleic-like surfactants and between layers of stearic-like surfactants across a hexadecane (HD) medium were measured using a surface force balance (SFB). Separate measurements reveal that only the oleic layers are solvated by HD, while the SFB results reveal that for both surfactants a marked net attraction is present between the surfaces. Simple considerations based on these observations explain why, despite this attraction, ferrofluid dispersions are stabilized by oleic but not by stearic surfactants.
We establish a tool for direct measurements of the work needed to separate a liquid from a solid. This method mimics a pendant drop that is subjected to a gravitational force that is slowly increasing until the solid-liquid contact area starts to shrink spontaneously. The work of separation is then calculated in analogy to Tate's law. The values obtained for the work of separation are independent of drop size and are in agreement with Dupré's theory, showing that they are equal to the work of adhesion.
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