Stefan Karpitschka

Due to capillarity, sessile droplets of identical liquids will instantaneously fuse when they come in contact at their three-phase lines. However, with drops of different, completely miscible liquids, instantaneous coalescence can be suppressed. Instead, the drops remain in a state of noncoalescence for some time, with the two drop bodies connected only by a thin neck. The reason for this noncoalescence is the surface tension difference, Δγ, between the liquids. If Δγ is sufficiently large, then it induces a sufficiently strong Marangoni flow, which keeps the main drop bodies temporarily separated. Studies with spreading drops have revealed that the boundary between instantaneous coalescence and noncoalescence is sharp (Karpitschka, S.; Riegler, H. J. Fluid. Mech. 2014, 743, R1). The boundary is a function of two parameters only: Δγ and Θ̅_a, the arithmetic mean of the contact angles in the moment of drop–drop contact. It appears plausible that surface forces (the disjoining pressure) could also influence the coalescence behavior. However, in experiments with spreading drops, surface forces always promote coalescence and their influence might be obscured. Therefore, we present here coalescence experiments with partially wetting liquids and compare the results to the spreading case. We adjust different equilibrium contact angles (i.e., different surface forces) with different substrate surface coatings. As for spreading drops, we observe a sharp boundary between regimes of coalescence and noncoalescence. The boundary follows the same power law relation for both partially and completely wetting cases. Therefore, we conclude that surface forces have no significant, explicit influence on the coalescence behavior of sessile drops from different miscible liquids.

We analyze the evolution of the vertical composition profile during hydrodynamic-evaporative film thinning as it typically occurs during spin casting mixtures of non-volatile solutes and volatile solvents. We assume that the solvent dominates the hydrodynamic-evaporative film thinning. The internal spatio-temporal evolution of the composition is analyzed with a diffusive-advective approach. The analysis provides transparent physical insights into the influence of the experimental conditions on the evolution of the internal composition. We present power laws that link the process control parameters to the composition evolution, process duration, and final solute coverage. The analysis reveals a characteristic Sherwood Number as fundamental process parameter. It identifies for which stages of the process our analysis is quantitatively relevant and discloses the dominance of either diffusion or evaporation. The analysis is valid for dilute solutions e.g., for the deposition of solute (sub)monolayers. But it is also relevant for the deposition of thicker (polymer) films.

Individual surface nanobubbles are visualized with nonintrusive optical interference-enhanced reflection microscopy, demonstrating that their formation is not a consequence of the hitherto used intrusive atomic force microscopy technique. We then use this new and fast technique to demonstrate that surface nanobubbles form in less than a few seconds after ethanol-water exchange, which is the standard procedure for their preparation, and examine how they react to temperature variations.

The existence of surface nanobubbles has been previously suggested using various experimental techniques, including attenuated total reflection spectroscopy, quartz crystal microbalance, neutron reflectometry, and x-ray reflectivity, but all of these techniques provide a sole number to quantify the existence of gas over (usually) hundreds of square microns. Thus `nanobubbles' are indistinguishable from a `uniform gassy layer' between surface and liquid. Atomic force microscopy, on the other hand, does show the existence of surface nanobubbles, but the highly intrusive nature of the technique means that a uniform gassy layer could break down into nanobubbles \textit{due to} the motion of the microscope's probe. Here we demonstrate \textit{optical} visualisation of surface nanobubbles, thus validating their individual existence non-intrusively.

Quantitative experimental data on the coalescence behavior of sessile droplets with different but completely miscible liquids are presented. The liquids consist of various aqueous mixtures of different nonvolatile diols and carbon acids with surface tensions ranging from 33 to 68 mN/m, contact angles between 9° and 20°, and viscosities from 1 to 12 cP. Two distinctly different coalescence behaviors, a delayed and a fast regime, are found. The transition between the two behaviors is remarkably sharp. It is found that the coalescence mode depends predominantly on the differences in the surface tensions of the two droplets. If the surface tension difference exceeds ∼3 mN/m, the coalescence is delayed. If it is less, droplet fusion occurs fast. Within the investigated parameter space, the transition seems independent from droplet size, absolute values of the surface tensions, and viscosity. Certain aspects of the experimental findings are explained with the simple hydrodynamic model presented in a recent publication.