Hydrophobic nanoporous carbon scaffolds reveal the origin of polarity-dependent electrocapillary imbibition.

An engineered nanoporous carbon scaffold (NCS) consisting of a 3-D interconnected 85 nm nanopore network was used here as a model material to investigate the nanoscale transport of liquids as a function of the polarity and magnitude of an applied potential ('electro-imbibition'), all in 1 M KCl solution. A camera was used to track both meniscus formation and meniscus jump, front motion dynamics, and droplet expulsion, while also quantifying the electrocapillary imbibition height (H) as a function of the applied potential of the NCS material. Although no imbibition was seen over a wide range of potentials, at positive potentials (+1.2 V vs. the potential of zero charge (pzc)), imbibition was correlated with carbon surface electro-oxidation, as confirmed by both electrochemistry and post-imbibition surface analysis, with gas evolution (O2, CO2) seen visually only after imbibition was well underway. At negative potentials, vigorous hydrogen evolution reaction was observed at the NCS/KCl solution interface, well before imbibition began at -0.5 Vpzc, proposed to be nucleated by an electrical double layer charging-driven meniscus jump, followed by processes such as Marangoni flow, adsorption induced deformation, and hydrogen pressure driven flow. This study improves the understanding of electrocapillary imbibition at the nanoscale, being highly relevant in a wide range of multidisciplinary practical applications, including in energy storage and conversion devices, energy-efficient desalination, and electrical-integrated nanofluidics design.

Experimental and computational evaluation of cyclic solvent injection in fractured tight hydrocarbon reservoirs.

Multi-fractured horizontal wells have enabled commercial production from low-permeability ('tight') hydrocarbon reservoirs but recoveries remain exceedingly small (< 5-10%). As a result, operators have investigated the use of solvent (gas) injection schemes, such as huff-n-puff (HNP), to improve oil recovery. Previous HNP laboratory approaches, classified primary as 'flow-through-matrix' and 'flow-around-matrix' typically (1) are not fully representative of field conditions at near-fracture regions and (2) require long test times, even when performed on fractured cores. The objectives of this proof-of-concept study are to (1) design and implement a new experimental procedure that better reproduces HNP schemes in near-fracture regions and (2) use the results, simulated with a compositional lab-calibrated model, to explore the controls on enhanced hydrocarbon recovery in depleted tight oil plays. Performing multiple CO2 and (simplified) lean gas HNP cycles, the integrated experimental and simulation approach proposed herein achieves the ultimate recovery factors in a significantly shorter time frame (25-50%) compared to previous studies. The integrated experimental and computational approach proposed herein is valuable for core-based evaluation of cyclic solvent (CO2, CH4) injection in tight hydrocarbon reservoirs for (1) hydrocarbon recovery and (2) subsurface greenhouse (CO2, CH4) gas disposal/storage applications.

Wetting dynamics of nanoliter water droplets in nanoporous media.

HYPOTHESIS: The Lucas-Washburn (L-W) equation is the classical theory to describe the dynamics of spontaneous imbibition in single micro-channels and micro-scale porous media. However, for nanoliter droplets imbibition in nanoporous media, the L-W equation may not be suitable, due to the nanoscale liquid-solid interactions, e.g., contact line pinning and capillary condensation. In addition, for an intrinsically hydrophobic nanoporous substrate, spontaneous imbibition of a nanoliter droplet is hypothesized to occur if capillary condensation had occurred internally already. EXPERIMENTS: A nanoporous carbon scaffold was synthesized and used as a model nanoporous medium. A recently-developed micro-injection technique was used to generate a series of nanoliter water droplets (2.8-34 nL); the entire wetting dynamics (i.e., apparent contact angle and droplet volume as a function of time) were observed inside an environmental scanning electron microscope. FINDINGS: The L-W equation does not describe the wetting dynamics of nanoliter water droplets in nanoporous media. A new theoretical model is developed to characterize the corresponding dynamics. It is demonstrated that, even for an intrinsically hydrophobic nanoporous substrate, spontaneous imbibition of a nanoliter droplet can occur if capillary condensation had occurred internally already.

An alternative solvent for electrospinning of fibrinogen nanofibers.

Fibrinogen plays a necessary role in blood clotting and wound healing. In this study, a new solvent mixture of formic acid/acetic acid with low toxicity was investigated as an alternative solvent for fibrinogen electrospinning. The nanofibers were analyzed by scanning electron microscope (SEM), simultaneous thermal analysis (STA) and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). The results showed that when the ratio of formic acid to acetic acid was 75/25 (v/v) the finest defect-free fibres with diameters ranging from 184 ± 37 to 241 ± 70 nm were obtained. In addition, the average fibre diameters increase with increasing concentration of fibrinogen from 10wt% to 12wt%. It is concluded that solvent mixture consisting of formic acid/acetic acid can be a great solvent for electrospinning of fibrinogen and is able to produce nanofiber structures.

Live Imaging of Micro-Wettability Experiments Performed for Low-Permeability Oil Reservoirs.

Low-permeability (unconventional) hydrocarbon reservoirs exhibit a complex nanopore structure and micro (µm) -scale variability in composition which control fluid distribution, displacement and transport processes. Conventional methods for characterizing fluid-rock interaction are however typically performed at a macro (mm) -scale on rock sample surfaces. In this work, innovative methods for the quantification of micro-scale variations in wettability and fluid distribution in a low-permeability oil reservoir was enabled by using an environmental scanning electron microscope. Live imaging of controlled water condensation/evaporation experiments allowed micro-droplet contact angles to be evaluated, while imaging combined with x-ray mapping of cryogenically frozen samples facilitated the evaluation of oil and water micro-droplet contact angles after successive fluid injection. For the first time, live imaging of fluids injected through a micro-injection system has enabled quantification of sessile and dynamic micro-droplet contact angles. Application of these combined methods has revealed dramatic spatial changes in fluid contact angles at the micro-scale, calling into question the applicability of macro-scale observations of fluid-rock interaction.

"Multi-temperature" method for high-pressure sorption measurements on moist shales.

A simple and effective experimental approach has been developed and tested to study the temperature dependence of high-pressure methane sorption in moist organic-rich shales. This method, denoted as "multi-temperature" (short "multi-T") method, enables measuring multiple isotherms at varying temperatures in a single run. The measurement of individual sorption isotherms at different temperatures takes place in a closed system ensuring that the moisture content remains constant. The multi-T method was successfully tested for methane sorption on an organic-rich shale sample. Excess sorption isotherms for methane were measured at pressures of up to 25 MPa and at temperatures of 318.1 K, 338.1 K, and 348.1 K on dry and moisture-equilibrated samples. The measured isotherms were parameterized with a 3-parameter Langmuir-based excess sorption function, from which thermodynamic sorption parameters (enthalpy and entropy of adsorption) were obtained. Using these, we show that by taking explicitly into account water vapor as molecular species in the gas phase with temperature-dependent water vapor pressure during the experiment, more meaningful results are obtained with respect to thermodynamical considerations. The proposed method can be applied to any adsorbent system (coals, shales, industrial adsorbents) and any supercritical gas (e.g., CH4, CO2) and is particularly suitable for sorption measurements using the manometric (volumetric) method.