Wettability Alteration of a Thiolene-Based Polymer (NOA81): Surface Characterization and Fabrication Techniques.

Wettability plays a significant role in controlling multiphase flow in porous media for many industrial applications, including geologic carbon dioxide sequestration, enhanced oil recovery, and fuel cells. Microfluidics is a powerful tool to study the complexities of interfacial phenomena involved in multiphase flow in well-controlled geometries. Recently, the thiolene-based polymer called NOA81 emerged as an ideal material in the fabrication of microfluidic devices, since it combines the versatility of conventional soft photolithography with a wide range of achievable wettability conditions. Specifically, the wettability of NOA81 can be continuously tuned through exposure to UV-ozone. Despite its growing popularity, the exact physical and chemical mechanisms behind the wettability alteration have not been fully characterized. Here, we apply different characterization techniques, including contact angle measurements, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) to investigate the impact of UV-ozone on the chemical and physical properties of NOA81 surfaces. We find that UV-ozone exposure increases the oxygen-containing polar functional groups, which enhances the surface energy and hydrophilicity of NOA81. Additionally, our AFM measurements show that spin-coated NOA81 surfaces have a roughness less than a nanometer, which is further reduced after UV-ozone exposure. Lastly, we extend NOA81 use cases by creating (i) 2D surface with controlled wettability gradient and (ii) a 3D column packed with monodisperse NOA81 beads of controlled size and wettability.

Bubble Formation in the Electrolyte Triggers Voltage Instability in CO2 Electrolyzers.

The electrochemical reduction of CO2 is promising for mitigating anthropogenic greenhouse gas emissions; however, voltage instabilities currently inhibit reaching high current densities that are prerequisite for commercialization. Here, for the first time, we elucidate that product gaseous bubble accumulation on the electrode/electrolyte interface is the direct cause of the voltage instability in CO2 electrolyzers. Although bubble formation in water electrolyzers has been extensively studied, we identified that voltage instability caused by bubble formation is unique to CO2 electrolyzers. The appearance of syngas bubbles within the electrolyte at the gas diffusion electrode (GDE)-electrolyte chamber interface (i.e. ∼10% bubble coverage of the GDE surface) was accompanied by voltage oscillations of 60 mV. The presence of syngas in the electrolyte chamber physically inhibited two-phase reaction interfaces, thereby resulting in unstable cell performance. The strategic incorporation of our insights on bubble growth behavior and voltage instability is vital for designing commercially relevant CO2 electrolyzers.

Comprehensive comparison of pore-scale models for multiphase flow in porous media.

Multiphase flows in porous media are important in many natural and industrial processes. Pore-scale models for multiphase flows have seen rapid development in recent years and are becoming increasingly useful as predictive tools in both academic and industrial applications. However, quantitative comparisons between different pore-scale models, and between these models and experimental data, are lacking. Here, we perform an objective comparison of a variety of state-of-the-art pore-scale models, including lattice Boltzmann, stochastic rotation dynamics, volume-of-fluid, level-set, phase-field, and pore-network models. As the basis for this comparison, we use a dataset from recent microfluidic experiments with precisely controlled pore geometry and wettability conditions, which offers an unprecedented benchmarking opportunity. We compare the results of the 14 participating teams both qualitatively and quantitatively using several standard metrics, such as fractal dimension, finger width, and displacement efficiency. We find that no single method excels across all conditions and that thin films and corner flow present substantial modeling and computational challenges.

Pore geometry control of apparent wetting in porous media.

Wettability, or preferential affinity of a fluid to a solid substrate in the presence of another fluid, plays a critical role in the statics and dynamics of fluid-fluid displacement in porous media. The complex confined geometry of porous media, however, makes upscaling of microscopic wettability to the macroscale a nontrivial task. Here, we elucidate the contribution of pore geometry in controlling the apparent wettability characteristics of a porous medium. Using direct numerical simulations of fluid-fluid displacement, we study the reversal of interface curvature in a single converging-diverging capillary, and demonstrate the co-existence of concave and convex interfaces in a porous medium-a phenomenon that we also observe in laboratory micromodel experiments. We show that under intermediate contact angles the sign of interface curvature is strongly influenced by the pore geometry. We capture the interplay between surface chemical properties and pore geometry in the form of a dimensionless quantity, the apparent wettability number, which predicts the conditions under which concave and convex interfaces co-exist. Our findings advance the fundamental understanding of wettability in confined geometries, with implications to macroscopic multiphase-flow processes in porous media, from fuel cells to enhanced oil recovery.

Forced Wetting Transition and Bubble Pinch-Off in a Capillary Tube.

Immiscible fluid-fluid displacement in partial wetting continues to challenge our microscopic and macroscopic descriptions. Here, we study the displacement of a viscous fluid by a less viscous fluid in a circular capillary tube in the partial wetting regime. In contrast with the classic results for complete wetting, we show that the presence of a moving contact line induces a wetting transition at a critical capillary number that is contact angle dependent. At small displacement rates, the fluid-fluid interface deforms slightly from its equilibrium state and moves downstream at a constant velocity, without changing its shape. As the displacement rate increases, however, a wetting transition occurs: the interface becomes unstable and forms a finger that advances along the axis of the tube, leaving the contact line behind, separated from the meniscus by a macroscopic film of the viscous fluid on the tube wall. We describe the dewetting of the entrained film, and show that it universally leads to bubble pinch-off, therefore demonstrating that the hydrodynamics of contact line motion generate bubbles in microfluidic devices, even in the absence of geometric constraints.

Wettability control on multiphase flow in patterned microfluidics.

Multiphase flow in porous media is important in many natural and industrial processes, including geologic CO2 sequestration, enhanced oil recovery, and water infiltration into soil. Although it is well known that the wetting properties of porous media can vary drastically depending on the type of media and pore fluids, the effect of wettability on multiphase flow continues to challenge our microscopic and macroscopic descriptions. Here, we study the impact of wettability on viscously unfavorable fluid-fluid displacement in disordered media by means of high-resolution imaging in microfluidic flow cells patterned with vertical posts. By systematically varying the wettability of the flow cell over a wide range of contact angles, we find that increasing the substrate's affinity to the invading fluid results in more efficient displacement of the defending fluid up to a critical wetting transition, beyond which the trend is reversed. We identify the pore-scale mechanisms-cooperative pore filling (increasing displacement efficiency) and corner flow (decreasing displacement efficiency)-responsible for this macroscale behavior, and show that they rely on the inherent 3D nature of interfacial flows, even in quasi-2D media. Our results demonstrate the powerful control of wettability on multiphase flow in porous media, and show that the markedly different invasion protocols that emerge-from pore filling to postbridging-are determined by physical mechanisms that are missing from current pore-scale and continuum-scale descriptions.

Interface pinning of immiscible gravity-exchange flows in porous media.

We study the gravity-exchange flow of two immiscible fluids in a porous medium and show that, in contrast with the miscible case, a portion of the initial interface remains pinned at all times. We elucidate, by means of micromodel experiments, the pore-level mechanism responsible for capillary pinning at the macroscale. We propose a sharp-interface gravity-current model that incorporates capillarity and quantitatively explains the experimental observations, including the x~t(1/2) spreading behavior at intermediate times and the fact that capillarity stops a finite-release current. Our theory and experiments suggest that capillary pinning is potentially an important, yet unexplored, trapping mechanism during CO(2) sequestration in deep saline aquifers.