Help from a Hindrance: Using Astigmatism in Round Capillaries To Study Contact Angles and Wetting Layers.

Round glass capillaries are a basic tool in soft-matter science, but often are shunned due to the astigmatism they introduce in micrographs. Here, we show how refraction in a capillary can be a help instead of a hindrance to obtain precise and sensitive information on two important interfacial properties: the contact angle of two immiscible fluids and the presence of thin films on the capillary wall. Understanding optical cusps due to refraction allows direct mesurement of the inner diameter of a capillary at the meniscus, which, with the height of the meniscus cap, determines the contact angle. The meniscus can thus be measured without intrusive additives to enhance visibility, such as dyes or calibrated particles, in uniform, curved, or even tapered capillaries or under demanding conditions not accessible by conventional methods, such as small volumes (μL), high temperatures, or high pressures. We further elicit the conditions for strong internal reflection on the inner capillary wall, involving the wall and fluid refractive indices and the wall thickness, and show how to choose the capillary section to detect thin (submicron) layers on the wall, by the contribution of total internal reflection to the cusps. As examples, we report the following: (i) CO2-water or -brine contact angles at glass interfaces, measured at temperatures and pressures up to 200 °C and 600 bar, revealing an effect apparently so far unreported-the decrease in the water-wet character of glass, due to dissolved salts in brine, is strongly reduced at high temperatures, where contact angles converge toward the values in pure water; (ii) A tenuous gas hydrate layer growing from the water-guest contact line on glass, invisible in transmission microscopy but prominent in the cusps due to total internal reflection.