Materials adsorbed onto the surface of a fluid -for instance, crude oil, biogenic slicks or industrial/medical surfactants -will move in response to surface waves. Owing to the difficulty of non-invasive measurement of the spatial distribution of a molecular monolayer, little is known about the dynamics that couple the surface waves and the evolving density field. Here, we report measurements of the spatiotemporal dynamics of the density field of an insoluble surfactant driven by gravity-capillary waves in a shallow cylindrical container. Standing Faraday waves and travelling waves generated by the meniscus are superimposed to create a non-trivial surfactant density field. We measure both the height field of the surface using moiré imaging, and the density field of the surfactant via the fluorescence of NBD-tagged phosphatidylcholine, a lipid. Through phase averaging stroboscopically acquired images of the density field, we determine that the surfactant accumulates on the leading edge of the travelling meniscus waves and in the troughs of the standing Faraday waves. We fit the spatiotemporal variations in the two fields using an ansatz consisting of a superposition of Bessel functions, and report measurements of the wavenumbers and energy damping factors associated with the meniscus and Faraday waves, as well as the spatial and temporal phase shifts between them. While these measurements are largely consistent for both types of waves and both fields, it is notable that the damping factors for height and surfactant in the meniscus waves do not agree. This raises the possibility that there is a contribution from longitudinal waves in addition to the gravity-capillary waves.

The spreading dynamics of surfactant molecules on a thin fluid layer is of both fundamental and practical interest. A mathematical model formulated by Gaver and Grotberg [10] describing the spreading of a single layer of insoluble surfactant has become widely accepted, and several experiments on axisymmetric spreading have confirmed its predictions for both the height profile of the free surface and the spreading exponent (the radius of the circular area covered by surfactant grows as t 1/4 ). However, these prior experiments have primarily utilized surfactant quantities exceeding (sometimes far exceeding) a monolayer. In this paper, we report that this regime is characterized by a mismatch between the timescales of the experiment and model, and additionally find that the spatial distribution of surfactant molecules differs substantially from the model prediction. For experiments performed in the monolayer regime for which the model was developed, the surfactant layer is observed to have a spreading exponent of less than 1/10, far below the predicted value, and the surfactant distribution is also in disagreement. These findings suggest that the model is inadequate for describing the spreading of insoluble surfactants on thin fluid layers.

We investigate the dynamics of an insoluble surfactant on the surface of a thin viscous fluid spreading inward to fill a surfactant-free region. During the initial stages of surfactant self-healing, Marangoni forces drive an axisymmetric ridge inward to coalesce into a growing central distension; this is unlike outward spreading, in which the ridge only decays. In later dynamics, the distension slowly decays and the surfactant concentration equilibrates. We present results from experiments in which we simultaneously measure the surfactant concentration (using fluorescently-tagged lipids) and the fluid height profile (via laser profilometry). We compare the results to simulations of a mathematical model using parameters from our experiments. For surfactant concentrations close to but below the critical monolayer concentration, we observe agreement between the height profiles in the numerical simulations and the experiment, but disagreement in the surfactant distribution. In experiments at lower concentrations, the surfactant spreading and formation of a Marangoni ridge are no longer present, and a persistent lipid-free region remains. This observation, which is not captured by the simulations, has undesirable implications for applications where uniform coverage is advantageous. Finally, we probe the generality of the effect, and find that distensions of similar size are produced independent of initial fluid thickness, size of initial clean region, and surfactant type.

No abstract