C Christian Diddens

Evaporation-triggered microdroplet nucleation and the four life phases of an evaporating Ouzo drop

Significance The evaporation of an Ouzo droplet is a daily life phenomenon, but the outcome is amazingly rich and unexpected: Here we reveal the four different phases of its life with phase transitions in-between and the physics that govern this phenomenon. The Ouzo droplet may be seen as a model system for any ternary mixture of liquids with different volatilities and mutual solubilities. Our work may open up numerous applications in (medical) diagnostics and in technology, such as coating or for the controlled deposition of tiny amounts of liquids, printing of light-emitting diode (LED) or organic LED devices, or phase separation on a submicron scale. Evaporating liquid droplets are omnipresent in nature and technology, such as in inkjet printing, coating, deposition of materials, medical diagnostics, agriculture, the food industry, cosmetics, or spills of liquids. Whereas the evaporation of pure liquids, liquids with dispersed particles, or even liquid mixtures has intensively been studied over the past two decades, the evaporation of ternary mixtures of liquids with different volatilities and mutual solubilities has not yet been explored. Here we show that the evaporation of such ternary mixtures can trigger a phase transition and the nucleation of microdroplets of one of the components of the mixture. As a model system, we pick a sessile Ouzo droplet (as known from daily life—a transparent mixture of water, ethanol, and anise oil) and reveal and theoretically explain its four life phases: In phase I, the spherical cap-shaped droplet remains transparent while the more volatile ethanol is evaporating, preferentially at the rim of the drop because of the singularity there. This leads to a local ethanol concentration reduction and correspondingly to oil droplet nucleation there. This is the beginning of phase II, in which oil microdroplets quickly nucleate in the whole drop, leading to its milky color that typifies the so-called “Ouzo effect.” Once all ethanol has evaporated, the drop, which now has a characteristic nonspherical cap shape, has become clear again, with a water drop sitting on an oil ring (phase III), finalizing the phase inversion. Finally, in phase IV, all water has evaporated, leaving behind a tiny spherical cap-shaped oil drop.

Evaporating pure, binary and ternary droplets: Thermal effects and axial symmetry breaking

The Greek aperitif Ouzo is not only famous for its specific anise-flavoured taste, but also for its ability to turn from a transparent miscible liquid to a milky-white coloured emulsion when water is added. Recently, it has been shown that this so-called Ouzo effect, i.e. the spontaneous emulsification of oil microdroplets, can also be triggered by the preferential evaporation of ethanol in an evaporating sessile Ouzo drop, leading to an amazingly rich drying process with multiple phase transitions (Tan et al., Proc. Natl Acad. Sci. USA, vol. 113 (31), 2016, pp. 8642-8647). Due to the enhanced evaporation near the contact line, the nucleation of oil droplets starts at the rim which results in an oil ring encircling the drop. Furthermore, the oil droplets are advected through the Ouzo drop by a fast solutal Marangoni flow. In this article, we investigate the evaporation of mixture droplets in more detail, by successively increasing the mixture complexity from pure water over a binary water-ethanol mixture to the ternary Ouzo mixture (water, ethanol and anise oil). In particular, axisymmetric and full three-dimensional finite element method simulations have been performed on these droplets to discuss thermal effects and the complicated flow in the droplet driven by an interplay of preferential evaporation, evaporative cooling and solutal and thermal Marangoni flow. By using image analysis techniques and micro-particle-image-velocimetry measurements, we are able to compare the numerically predicted volume evolutions and velocity fields with experimental data. The Ouzo droplet is furthermore investigated by confocal microscopy. It is shown that the oil ring predominantly emerges due to coalescence.

Modeling the evaporation of sessile multi-component droplets

We extended a mathematical model for the drying of sessile droplets, based on the lubrication approximation, to binary mixture droplets. This extension is relevant for e.g. inkjet printing applications, where ink consisting of several components are used. The extension involves the generalization of an established vapor diffusion-limited evaporation model to multi-component mixtures. The different volatilities of the liquid components generate a composition gradient at the liquid-air interface. The model takes the composition-dependence of the mass density, viscosity, surface tension, mutual diffusion coefficient and thermodynamic activities into account. This leads to a variety of effects ranging from solutal Marangoni flow over deviations from the typical spherical cap shape to an entrapped residual amount of the more volatile component at later stages of the drying. These aspects are discussed in detail on the basis of the numerical results for water-glycerol and water-ethanol droplets. The results show good agreement with experimental findings. Finally, the accuracy of the lubrication approximation is assessed by comparison with a finite element method.

Redeposition during ion-beam erosion can stabilize well-ordered nanostructures

Using a continuum formulation valid for arbitrary laterally two-dimensional surface profiles, we investigate the significance of redeposition of ion-beam eroded particles on spatio-temporally evolving surface morphologies of the target. Combining the effect of redeposition with standard roughening and smoothing effects of ion-beam erosion processes to a generalized nonlocal Kuramoto-Sivashinsky equation, we substantiate the decisive role of redeposition for the emergence of well-ordered ion-beam eroded hexagonally arranged dot structures as, e.g., experimentally observed on various semiconductor targets.

Detailed finite element method modeling of evaporating multi-component droplets

The evaporation of sessile multi-component droplets is modeled with an axisymmetic finite element method. The model comprises the coupled processes of mixture evaporation, multi-component flow with composition-dependent fluid properties and thermal effects. Based on representative examples of waterglycerol and waterethanol droplets, regular and chaotic examples of solutal Marangoni flows are discussed. Furthermore, the relevance of the substrate thickness for the evaporative cooling of volatile binary mixture droplets is pointed out. It is shown how the evaporation of the more volatile component can drastically decrease the interface temperature, so that ambient vapor of the less volatile component condenses on the droplet. Finally, results of this model are compared with corresponding results of a lubrication theory model, showing that the application of lubrication theory can cause considerable errors even for moderate contact angles of 40.

Evaporation-triggered segregation of sessile binary droplets

Droplet evaporation of multicomponent droplets is essential for various physiochemical applications, e.g., in inkjet printing, spray cooling, and microfabrication. In this work, we observe and study the phase segregation of an evaporating sessile binary droplet, consisting of a miscible mixture of water and a surfactantlike liquid (1,2-hexanediol). The phase segregation (i.e., demixing) leads to a reduced water evaporation rate of the droplet, and eventually the evaporation process ceases due to shielding of the water by the nonvolatile 1,2-hexanediol. Visualizations of the flow field by particle image velocimetry and numerical simulations reveal that the timescale of water evaporation at the droplet rim is faster than that of the Marangoni flow, which originates from the surface tension difference between water and 1,2-hexanediol, eventually leading to segregation.