Apparent line tension induced by surface-active impurities

Abstract

Line tension in wetting processes is of high scientific and technological relevance, but its understanding remains vague, mainly because of its difficult determination. A widely used method to extract the line tension relies on the variation of a droplet's contact angle with the droplet's size. This approach yields the apparent line tension, which factors in numerous contributions to the finite-size dependence, thus masking the actual line tension in terms of the excess free energy of the three-phase contact line. Based on our recent computer simulation study, we investigate how small amounts of nonionic surfactants, such as surface-active impurities, contribute to the apparent line tension in aqueous droplets. When depositing polydisperse droplets, their different surface-area-to-volume ratios can result in different final bulk concentrations of surfactants, different excess adsorptions to interfaces, and, consequently, different contact angles. We show that already trace amounts of longer-chained surfactants are enough to cause a measurable effect on the apparent line tension. Our analysis quantifies to what extent "background" impurities, inevitably present in all experimental settings, limit the resolution of line-tension measurements, which is crucial for avoiding data misinterpretation.