Friedrich Gunther Mugele

Droplets Formation and Merging in Two-Phase Flow Microfluidics

Two-phase flow microfluidics is emerging as a popular technology for a wide range of applications involving high throughput such as encapsulation, chemical synthesis and biochemical assays. Within this platform, the formation and merging of droplets inside an immiscible carrier fluid are two key procedures: (i) the emulsification step should lead to a very well controlled drop size (distribution); and (ii) the use of droplet as micro-reactors requires a reliable merging. A novel trend within this field is the use of additional active means of control besides the commonly used hydrodynamic manipulation. Electric fields are especially suitable for this, due to quantitative control over the amplitude and time dependence of the signals, and the flexibility in designing micro-electrode geometries. With this, the formation and merging of droplets can be achieved on-demand and with high precision. In this review on two-phase flow microfluidics, particular emphasis is given on these aspects. Also recent innovations in microfabrication technologies used for this purpose will be discussed.

How to make sticky surfaces slippery: Contact angle hysteresis in electrowetting with alternating voltage

Contact angle hysteresis caused by random pinning forces is a major obstacle in moving small quantities of liquid on solid surfaces. Here, we demonstrate that the contact angle hysteresis for sessile drops in electrowetting almost disappears with increasing alternating voltage, whereas for direct voltage it remains constant. This observation is explained in terms of a balance of surface tension, pinning, and (time-dependent) electrostatic forces at the contact line.

Microfluidic mixing through electrowetting-induced droplet oscillations

We used electrowetting to trigger self-excited oscillations of millimeter-sized sessile droplets of water-glycerol mixtures in a viscosity range from 1 to 65 mPa s. During the oscillations the contact angle of the droplets varied periodically between [approximate]130° and 80° with a frequency between 10 and 125 s–1, depending on the viscosity and the drop size. By initially staining drops partially with fluorescent dye, we found that the liquid within the drop is completely mixed within 100–2000 oscillation cycles for low and high viscosities, respectively. Compared to pure diffusion, droplet oscillations accelerated mixing by approximately two orders of magnitude for millimeter-sized droplets

Fundamental challenges in electrowetting: from equilibrium shapes to contact angle saturation and drop dynamics

Electrowetting is a versatile tool for manipulating typically submillimetre-sized drops in various microfluidic applications. In recent years the microscopic understanding of the electrowetting effect has substantially improved leading to a detailed description of the drop shape and the (singular) distribution of the electric field in the vicinity of the contact line. Based on these findings, novel quantitative models of contact angle saturation, the most important and longstanding fundamental problem in the field, have recently been developed. Future challenges arise in the context of dynamic electrowetting: neither the translational motion of drops nor the generation of internal flow patterns are currently well understood.

Equilibrium drop surface profiles in electric fields

Electrowetting is becoming a more and more frequently used tool to manipulate liquids in various microfluidic applications. On the scale of the entire drop, the effect of electrowetting is to reduce the apparent contact angle of partially wetting conductive liquids upon application of an external voltage. Microscopically, however, strong electric fields in the vicinity of the three phase contact line give rise to local deformations of the drop surface. We determined the equilibrium surface profile using a combined numerical, analytical, and experimental approach. We find that the local contact angle in electrowetting is equal to Youngs angle independent of the applied voltage. Only on the scale of the thickness of the insulator and beyond does the surface slope assume a value consistent with the voltage-dependent apparent contact angle. This behaviour is verified experimentally by determining equilibrium surface profiles for insulators of various thicknesses between 10 and 250 µm. Numerically and analytically, we find that the local surface curvature diverges algebraically upon approaching the contact line with an exponent −1

Electrowetting: a convenient way to switchable wettability patterns

Electrowetting is a versatile tool to reduce the apparent contact angle of partially wetting conductive liquids by several tens of degrees via an externally applied voltage. We studied various fundamental and applied aspects of equilibrium liquid surface morphologies both theoretically and experimentally. Our theoretical analysis showed that surface profiles on homogeneous surfaces display a diverging curvature in the vicinity of the three phase contact line. The asymptotic contact angle at the contact line is equal to Youngs angle, independent of the applied voltage. With respect to the morphology of the liquid surface, contact angle variations achieved by electrowetting are equivalent to those achieved by varying the chemical nature of the substrates, except for electric field-induced distortions in a region close to the contact line. Experimentally, we studied the (global) morphology of liquid microstructure substrates with stripe-shaped electrodes. As the local contact angle is reduced by increasing the applied voltage, liquid droplets elongate along the stripe axis as expected. For droplets on a single surface with a stripe electrode, there is a discontinuous morphological transition where elongated droplets transform into translationally invariant cylinder segments with the contact line pinned along the stripe edge and vice versa. If the liquid is confined between two parallel surfaces with parallel stripe electrodes, the elongation of the droplet and its transformation into a translationally invariant morphology with pinned contact lines is continuous. Experimental results are compared to analytical and numerical models.

Hard and soft colloids at fluid interfaces: Adsorption, interactions, assembly and rheology

Soft microgel particles inherently possess qualities of both polymers as well as particles. We review the similarities and differences between soft microgel particles and stiff colloids at fluid-fluid interfaces. We compare two fundamental aspects of particle-laden interfaces namely the adsorption kinetics and the interactions between adsorbed particles. Although it is well established that the transport of both hard particles and microgels to the interface is driven by diffusion, the analysis of the adsorption kinetics needs reconsideration and a proper equation of state relating the surface pressure to the adsorbed mass should be used. We review the theoretical and experimental investigations into the interactions of particles at the interface. The rheology of the interfacial layers is intimately related to the interactions, and the differences between hard particles and microgels become pronounced. The assembly of particles into the layer is another distinguishing factor that separates hard particles from soft microgel particles. Microgels deform substantially upon adsorption and the stability of a microgel-stabilized emulsion depends on the conformational changes triggered by external stimuli.

Sorption‐Determined Deposition of Platinum on Well‐Defined Platelike WO3

The photodeposition of Pt nanoparticles from [PtCl6 ](2-) on platelike WO3 crystals occurs preferentially on the small, subordinate facets. Rather than the often-used explanation of preferred light-induced charge migration, we propose that this phenomenon is due to differences in the intrinsic surface charges of WO3 facets exposed to water; thus, the dark sorption of [PtCl6 ](2-) on positively charged facets/edges is preferred. This conclusion is based on 1) (dark) impregnation studies, which showed Pt deposition to also be facet-specific, and 2) aqueous-phase AFM studies, which suggest intrinsic surface charges to be in agreement with sorption-based Pt distributions.

Droplet Manipulations in Two Phase Flow Microfluidics

Even though droplet microfluidics has been developed since the early 1980s, the number of applications that have resulted in commercial products is still relatively small. This is partly due to an ongoing maturation and integration of existing methods, but possibly also because of the emergence of new techniques, whose potential has not been fully realized. This review summarizes the currently existing techniques for manipulating droplets in two-phase flow microfluidics. Specifically, very recent developments like the use of acoustic waves, magnetic fields, surface energy wells, and electrostatic traps and rails are discussed. The physical principles are explained, and (potential) advantages and drawbacks of different methods in the sense of versatility, flexibility, tunability and durability are discussed, where possible, per technique and per droplet operation: generation, transport, sorting, coalescence and splitting.

Salt dependent stability of stearic acid Langmuir-Blodgett films exposed to aqueous electrolytes

We use contact angle goniometry, imaging ellipsometry, and atomic force microscopy to study the stability and wettability of Langmuir-Blodgett (LB) monolayers of stearic acid on silica substrates, upon drying and exposure to aqueous solutions of varying salinity. The influences of Ca(2+) and Na(+) ions are compared by varying their concentrations, both in the subphase before the LB transfer, and in the droplets to which the dried LB layers are exposed. Ca(2+) ions in the subphase are found to enhance the stability, leading to contact angles up to 100°, as compared to less than 5° for Na(+). Consistent with the macroscopic wettability, AFM images show almost intact films with few holes exposing bare substrate when prepared in the presence of Ca(2+), while subphases containing Na(+) result in large areas of bare substrate after exposure to aqueous drops. The observations on varying the composition of the droplets corroborate the stabilizing effect of Ca(2+). We attribute these findings to the cation-bridging ability of Ca(2+) ions, which can bind the negatively charged stearate groups to the negatively charged substrates. We discuss the relevance of our findings in the context of enhanced oil recovery.