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Solvent Exchange in a Hele-Shaw Cell Universality of Surface Nanodroplet Nucleation

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 Added by Binglin Zeng
 Publication date 2020
  fields Physics
and research's language is English




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Solvent exchange (also called solvent shifting or Ouzo effect) is a generally used bottom-up process to mass-produce nanoscale droplets. In this process, a good solvent for some oil is displaced by a poor one, leading to oil nanodroplet nucleation and subsequent growth. Here we perform this process on a hydrophobic substrate so that sessile droplets so-called surface nanodroplets-develop, following the work of Zhang et al. [Zhang, X.; Lu, Z.; Tan, H.; Bao, L.; He, Y.; Sun, C.; Lohse, D. Proc. Natl. Acad. Sci. U.S.A. 2015, 122, 9253-9257]. In contrast to what was done in that paper, we chose a very well-controlled Hele-Shaw geometry with negligible gravitational effects, injecting the poor solvent in the center of the Hele-Shaw cell, and characterize the emerging nanodroplets as a function of radial distance and flow rates. We find that the mean droplet volume per area <Vol>_area strongly depends on the local Peclet number Pe and follows a universal scaling law <Vol>_area~Pe^(3/4). Moreover, the probability distribution function of the droplet volume strongly depends on the local Pe as well, regardless of the flow rates and radial distance, giving strong support to the theoretical model of the solvent exchange process developed in Zhang et al.s work.



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Micro and nanodroplets have many important applications such as in drug delivery, liquid-liquid extraction, nanomaterial synthesis and cosmetics. A commonly used method to generate a large number of micro or nanodroplets in one simple step is solvent exchange (also called nanoprecipitation), in which a good solvent of the droplet phase is displaced by a poor one, generating an oversaturation pulse that leads to droplet nucleation. Despite its crucial importance, the droplet growth resulting from the oversaturation pulse in this ternary system is still poorly understood. We experimentally and theoretically study this growth in Hele-Shaw like channels by measuring the total volume of the oil droplets that nucleates out of it. In order to prevent the oversaturated oil from exiting the channel, we decorated some of the channels with a porous region in the middle. Solvent exchange is performed with various solution compositions, flow rates and channel geometries, and the measured droplets volume is found to increase with the Peclet number $Pe$ with an approximate effective power law $Vpropto Pe^{0.50}$. A theoretical model is developed to account for this finding. With this model we can indeed explain the $Vpropto Pe^{1/2}$ scaling, including the prefactor, which can collapse all data of the porous channels onto one universal curve, irrespective of channel geometry and composition of the mixtures. Our work provides a macroscopic approach to this bottom-up method of droplet generation and may guide further studies on oversaturation and nucleation in ternary systems.
We study microfluidic self digitization in Hele-Shaw cells using pancake droplets anchored to surface tension traps. We show that above a critical flow rate, large anchored droplets break up to form two daughter droplets, one of which remains in the anchor. Below the critical flow velocity for breakup the shape of the anchored drop is given by an elastica equation that depends on the capillary number of the outer fluid. As the velocity crosses the critical value, the equation stops admitting a solution that satisfies the boundary conditions; the drop breaks up in spite of the neck still having finite width. A similar breaking event also takes place between the holes of an array of anchors, which we use to produce a 2D array of stationary drops in situ.
The flow in a Hele-Shaw cell with a time-increasing gap poses a unique shrinking interface problem. When the upper plate of the cell is lifted perpendicularly at a prescribed speed, the exterior less viscous fluid penetrates the interior more viscous fluid, which generates complex, time-dependent interfacial patterns through the Saffman-Taylor instability. The pattern formation process sensitively depends on the lifting speed and is still not fully understood. For some lifting speeds, such as linear or exponential speed, the instability is transient and the interface eventually shrinks as a circle. However, linear stability analysis suggests there exist shape invariant shrinking patterns if the gap $b(t)$ is increased more rapidly: $displaystyle b(t)=left(1-frac{7}{2}tau mathcal{C} tright)^{-{2}/{7}}$, where $tau$ is the surface tension and $mathcal{C}$ is a function of the interface perturbation mode $k$. Here, we use a spectrally accurate boundary integral method together with an efficient time adaptive rescaling scheme, which for the first time makes it possible to explore the nonlinear limiting dynamical behavior of a vanishing interface. When the gap is increased at a constant rate, our numerical results quantitatively agree with experimental observations (Nase et al., Phys. Fluids, vol. 23, 2011, pp. 123101). When we use the shape invariant gap $b(t)$, our nonlinear results reveal the existence of $k$-fold dominant, one-dimensional, web-like networks, where the fractal dimension is reduced to almost one at late times. We conclude by constructing a morphology diagram for pattern selection that relates the dominant mode $k$ of the vanishing interface and the control parameter $mathcal{C}$.
We report experimental results for the Kelvin-Helmholtz instability between two immiscible fluids in parallel flow in a Hele-Shaw cell. We focus our interest on the influence of the gap size between the walls on the instability characteristics. Experimental results show that the instability threshold, the critical wavelength, the phase velocity and the spatial growth rate depend on this gap size. These results are compared to both the previous two-dimensional analysis of Gondret and Rabaud (1997) and the three-dimensional analysis recently derived by Plourabou=E9 and Hinch (2001), showing that the agreement is still not complete especially when gap size increases.
We adopt a boundary integral method to study the dynamics of a translating droplet confined in a Hele-Shaw cell in the Stokes regime. The droplet is driven by the motion of the ambient fluid with the same viscosity. We characterize the three-dimensional (3D) nature of the droplet interface and of the flow field. The interface develops an arc-shaped ridge near the rear-half rim with a protrusion in the rear and a laterally symmetric pair of higher peaks; this pair of protrusions has been identified by recent experiments (Huerre et al., Phys. Rev. Lett., vol. 115 (6), 2015, 064501) and predicted asymptotically (Burgess and Foster, Phys. Fluids A, vol. 2 (7), 1990, pp. 1105-1117). The mean film thickness is well predicted by the extended Bretherton model (Klaseboer et al., Phys. Fluids, vol. 26 (3), 2014, 032107) with fitting parameters. The flow in the streamwise wall-normal middle plane is featured with recirculating zones, which are partitioned by stagnation points closely resembling those of a two-dimensional droplet in a channel. Recirculation is absent in the wall-parallel, unconfined planes, in sharp contrast to the interior flow inside a moving droplet in free space. The preferred orientation of the recirculation results from the anisotropic confinement of the Hele-Shaw cell. On these planes, we identify a dipolar disturbance flow field induced by the travelling droplet and its $1/r^2$ spatial decay is confirmed numerically. We pinpoint counter-rotating streamwise vortex structures near the lateral interface of the droplet, further highlighting the complex 3D flow pattern.
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