In situ characterization of heterogeneous surface wetting in porous materials.

The performance of nano- and micro-porous materials in capturing and releasing fluids, such as during CO2 geo-storage and water/gas removal in fuel cells and electrolyzers, is determined by their wettability in contact with the solid. However, accurately characterizing wettability is challenging due to spatial variations in dynamic forces, chemical heterogeneity, and surface roughness. In situ measurements can potentially measure wettability locally as a contact angle - the angle a denser phase (e.g water) contacts solid in the presence of a second phase (e.g. hydrogen, air, CO2) - but suffer from difficulties in accurately capturing curvatures, contact areas, and contact loops of multiphase fluids. We introduce a novel extended topological method for in situ contact angle measurement and provide a comparative review of current geometric and topological methods, assessing their accuracy on ideal surfaces, porous rocks containing CO2, and water in gas diffusion layers. The new method demonstrates higher accuracy and reliability of in situ measurements for uniformly wetting systems compared to previous topological approaches, while geometric measurements perform best for mixed-wetting domains. This study further provides a comprehensive open-source platform for in situ characterization of wettability in porous materials with implications for gas geo-storage, fuel cells and electrolyzers, filtration, and catalysis.

Positron emission tomography dataset of [11C]carbon dioxide storage in coal for geo-sequestration application.

Positron Emission Tomography (PET) imaging has demonstrated its capability in providing time-lapse fluid flow visualisation for improving the understanding of flow properties of geologic media. To investigate the process of CO2 geo-sequestration using PET imaging technology, [11C]CO2 is the most optimal and direct radiotracer. However, it has not been extensively used due to the short half-life of Carbon-11 (20.4 minutes). In this work, a novel laboratory protocol is developed to use [11C]CO2 as radiolabelled tracer to visualise and quantify in-situ CO2 adsorption, spreading, diffusion, and advection flow in coal. This protocol consists of generation and delivering of [11C]CO2, lab-based PET scanning, subsequent micro-CT scanning, and data processing. The lab-based PET scanning setup integrates in-situ core flooding tests with PET scanning. The real-time PET images are acquired under different storage conditions, including early gas production stage, depleted stage, and late storage stage. These datasets can be used to study across-scale theoretical and experimental study of CO2 flow behaviour in coal with the application to CO2 geo-sequestration.

Large-scale physically accurate modelling of real proton exchange membrane fuel cell with deep learning.

Proton exchange membrane fuel cells, consuming hydrogen and oxygen to generate clean electricity and water, suffer acute liquid water challenges. Accurate liquid water modelling is inherently challenging due to the multi-phase, multi-component, reactive dynamics within multi-scale, multi-layered porous media. In addition, currently inadequate imaging and modelling capabilities are limiting simulations to small areas (<1 mm2) or simplified architectures. Herein, an advancement in water modelling is achieved using X-ray micro-computed tomography, deep learned super-resolution, multi-label segmentation, and direct multi-phase simulation. The resulting image is the most resolved domain (16 mm2 with 700 nm voxel resolution) and the largest direct multi-phase flow simulation of a fuel cell. This generalisable approach unveils multi-scale water clustering and transport mechanisms over large dry and flooded areas in the gas diffusion layer and flow fields, paving the way for next generation proton exchange membrane fuel cells with optimised structures and wettabilities.

Liquid metal synthesis solvents for metallic crystals.

In nature, snowflake ice crystals arrange themselves into diverse symmetrical six-sided structures. We show an analogy of this when zinc (Zn) dissolves and crystallizes in liquid gallium (Ga). The low-melting-temperature Ga is used as a "metallic solvent" to synthesize a range of flake-like Zn crystals. We extract these metallic crystals from the liquid metal solvent by reducing its surface tension using a combination of electrocapillary modulation and vacuum filtration. The liquid metal-grown crystals feature high morphological diversity and persistent symmetry. The concept is expanded to other single and binary metal solutes and Ga-based solvents, with the growth mechanisms elucidated through ab initio simulation of interfacial stability. This strategy offers general routes for creating highly crystalline, shape-controlled metallic or multimetallic fine structures from liquid metal solvents.

Universal description of wetting on multiscale surfaces using integral geometry.

HYPOTHESIS: Emerging energy-related technologies deal with multiscale hierarchical structures, intricate surface morphology, non-axisymmetric interfaces, and complex contact lines where wetting is difficult to quantify with classical methods. We hypothesise that a universal description of wetting on multiscale surfaces can be developed by using integral geometry coupled to thermodynamic laws. The proposed approach separates the different hierarchy levels of physical description from the thermodynamic description, allowing for a universal description of wetting on multiscale surfaces. THEORY AND SIMULATIONS: The theoretical framework is presented followed by application to limiting cases of wetting on multiscale surfaces. Limiting cases include those considered in the Wenzel, Cassie-Baxter, and wicking state models. Wetting characterisation of multiscale surfaces is explored by conducting simulations of a fluid droplet on a structurally rough surface and a chemically heterogeneous surface. FINDINGS: The underlying origin of the classical wetting models is shown to be rooted within the proposed theoretical framework. Integral geometry provides a topological-based wetting metric that is not contingent on any type of wetting state. The wetting metric is demonstrated to account for multiscale features along the common line in a scale consistent way; providing a universal description of wetting for multiscale surfaces.

Characterization of wetting using topological principles.

HYPOTHESIS: Understanding wetting behavior is of great importance for natural systems and technological applications. The traditional concept of contact angle, a purely geometrical measure related to curvature, is often used for characterizing the wetting state of a system. It can be determined from Young's equation by applying equilibrium thermodynamics. However, whether contact angle is a representative measure of wetting for systems with significant complexity is unclear. Herein, we hypothesize that topological principles based on the Gauss-Bonnet theorem could yield a robust measure to characterize wetting. THEORY AND EXPERIMENTS: We introduce a macroscopic contact angle based on the deficit curvature of the fluid interfaces that are imposed by contacts with other immiscible phases. We perform sessile droplet simulations followed by multiphase experiments for porous sintered glass and Bentheimer sandstone to assess the sensitivity and robustness of the topological approach and compare the results to other traditional approaches. FINDINGS: We show that the presented topological principle is consistent with thermodynamics under the simplest conditions through a variational analysis. Furthermore, we elucidate that at sufficiently high image resolution the proposed topological approach and local contact angle measurements are comparable. While at lower resolutions, the proposed approach provides more accurate results being robust to resolution-based effects. Overall, the presented concepts open new pathways to characterize the wetting state of complex systems and theoretical developments to study multiphase systems.

Linking continuum-scale state of wetting to pore-scale contact angles in porous media.

HYPOTHESIS: Wetting phenomena play a key role in flows through porous media. Relative permeability and capillary pressure-saturation functions show a high sensitivity to wettability, which has different definitions at the continuum- and pore-scale. We hypothesize that the wetting state of a porous medium can be described in terms of topological arguments that constrain the morphological state of immiscible fluids, which provides a direct link between the continuum-scale metrics of wettability and pore-scale contact angles. EXPERIMENTS: We perform primary drainage and imbibition experiments on Bentheimer sandstone using air and brine. Topological properties, such as Euler characteristic and interfacial curvature are measured utilizing X-ray micro-computed tomography at irreducible air saturation. We also present measurements for the United States Bureau of Mines (USBM) index, capillary pressure and pore-scale contact angles. Additional studies are performed using two-phase Lattice Boltzmann simulations to test a wider range of wetting conditions. FINDINGS: We demonstrate that contact angle distributions for a porous multiphase system can be predicted within a few percent difference of directly measured pore-scale contact angles using the presented method. This provides a general framework on how continuum-scale data can be used to describe the geometrical state of fluids within porous media.

Oil mobilization and solubilization in porous media by in situ emulsification.

HYPOTHESIS: For a wide range of subsurface engineering processes, such as geological carbon sequestration and enhanced oil recovery, it is critical to understand multiphase flow at a fundamental level. To this end, geomaterial microfluidic devices provide visual data that can be quantified to explain the physics of multiphase flow at the length scale of individual pores in realistic rock structures. For surfactant enhanced oil recovery, it is the underlying geometrical states of the capillary trapped oil that dictates the recovery process and the degree to which oil is recovered through either mobilization or solubilization during in situ emulsification. EXPERIMENTS: A novel geomaterial microfluidic device is fabricated and its integrity is checked using light microscopy and X-ray micro-computed tomography (µ-CT) imaging. Subsequently, alkaline surfactant (AS) flooding of an oil saturated device is studied for enhanced recovery. The recovery process is analyzed by collecting 2D radiographic projections of the device during water flooding and in situ emulsification. 3D µ-CT images are also collected to quantify the geometrical states of the fluids after each flooding sequence. FINDINGS: Our study reveals the processes of oil cluster mobilization and solubilization in porous media. After water flooding there are numerous oil clusters that are relatively large, extending over multiple pores, forming various loop-like structures. These clusters are mobile under AS flooding accounting for 75% of the recovered oil. The less mobile smaller clusters, isolated to single pores, forming no loop-like structures are immobile. These clusters are solubilized during AS flooding accounting for 25% of the recovered oil. The mobilized clusters coalesce forming an oil bank prior to total solubilization. The remaining oil clusters after AS flooding are highly non-wetting, as indicated by contact angle measurements and would only be recoverable after further solubilization.

On the challenges of greyscale-based quantifications using X-ray computed microtomography.

For X-ray computed microtomography (µ-CT) images of porous rocks where the grains and pores are not fully resolved, the greyscale values of each voxel can be used for quantitative calculations. This study addresses the challenges that arise with greyscale-based quantifications by conducting experiments designed to investigate the sources of error/uncertainty. We conduct greyscale-based calculations of porosity, concentration and diffusivity from various µ-CT experiments using a Bentheimer sandstone sample. The dry sandstone is imaged overtime to test the variation of greyscale values over sequential scans due to instrumentation stability. The sandstone is then imaged in a dry and contrast-agent saturated state at low resolution to determine a porosity map, which is compared to a porosity map derived from segmented high-resolution data. Then the linearity of the relationship between the concentration of a contrast agent and its corresponding attenuation coefficient is tested by imaging various solutions of known concentration. Lastly, a diffusion experiment is imaged at low resolution under dynamic conditions to determine local diffusivity values for the sandstone, which is compared to values derived from direct pore-scale simulations using high-resolution data. Overall, we identify the main errors associated with greyscale-based quantification and provide practical suggestions to alleviate these issues. LAY DESCRIPTION: X-ray computed microtomography (CT) imaging has become an important way to study the pore space of a porous medium. Using segmented images, we can build 3D pore space models for porous media and characterize the morphology and/or run simulations on the models. So, image segmentation is a critical image processing step. However, for low resolution images where image segmentation is not possible, grayscales are directly used for quantifications such as porosity and concentration calculations. Although these types of calculations have been widely accepted and used, the uncertainties and errors associated with grayscale-based quantifications are not fully discussed. Here we specifically design experiments with X-ray CT imaging to address the challenges that arise in grayscale-based quantifications. For instance, in order to validate porosity calculation results from low resolution images (with the help of high attenuating tracer), high resolution images are also acquired, which serve as a benchmark. The errors associated with concentration calculation using grayscale values are also discussed. In addition, numerical simulations using grayscale values are performed on a diffusion experiment images with X-ray CT. The problems that arise in dynamic imaging and the subsequent numerical simulations are discussed. The experiments, calculations and discussions provide a more comprehensive understanding on grayscale-based quantifications and aid in designing better X-ray CT experiments.

Functionalisation of Polydimethylsiloxane (PDMS)- Microfluidic Devices coated with Rock Minerals.

Fluid flow in porous rocks is commonly capillary driven and thus, dependent on the surface characteristics of rock grains and in particular the connectivity of corners and crevices in which fluids reside. Traditional microfluidic fabrication techniques do not provide a connected pathway of crevices that are essential to mimic multiphase flow in rocks. Here, geo-material microfluidic devices with connected pathways of corners and crevices were created by functionalising Polydimethylsiloxane (PDMS) with rock minerals. A novel fabrication process that provides attachment of rock minerals onto PDMS was demonstrated. The geo-material microfluidic devices were compared to carbonate and sandstone rocks by using energy dispersive X-ray spectroscopy, scanning electron microscopy (SEM), contact angle measurements, and a surface profilometer. Based on SEM coupled with energy-dispersive X-ray spectrometry (SEM-EDS) analyses, roughness measurements, contact angle, wettability, and roughness were comparable to real rocks. In addition, semivariograms showed that mineral deposition across the different geo-material devices was nearly isotropic. Lastly, important multiphase flow phenomena, such as snap-off and corner flow mechanisms, equivalent to those occurring in reservoir rocks have been visualised. The presented approach can be used to visualise rock-fluid interactions that are relevant to subsurface engineering applications, such as hydrocarbon recovery and CO2 sequestration.

Insights into non-Fickian solute transport in carbonates.

[1] We study and explain the origin of early breakthrough and long tailing plume behavior by simulating solute transport through 3-D X-ray images of six different carbonate rock samples, representing geological media with a high degree of pore-scale complexity. A Stokes solver is employed to compute the flow field, and the particles are then transported along streamlines to represent advection, while the random walk method is used to model diffusion. We compute the propagators (concentration versus displacement) for a range of Peclet numbers (Pe) and relate it to the velocity distribution obtained directly on the images. There is a very wide distribution of velocity that quantifies the impact of pore structure on transport. In samples with a relatively narrow spread of velocities, transport is characterized by a small immobile concentration peak, representing essentially stagnant portions of the pore space, and a dominant secondary peak of mobile solute moving at approximately the average flow speed. On the other hand, in carbonates with a wider velocity distribution, there is a significant immobile peak concentration and an elongated tail of moving fluid. An increase in Pe, decreasing the relative impact of diffusion, leads to the faster formation of secondary mobile peak(s). This behavior indicates highly anomalous transport. The implications for modeling field-scale transport are discussed. Citation: Bijeljic, B., P. Mostaghimi, and M. J. Blunt (2013), Insights into non-Fickian solute transport in carbonates, Water Resour. Res., 49, 2714-2728, doi:10.1002/wrcr.20238.

Predictions of non-Fickian solute transport in different classes of porous media using direct simulation on pore-scale images.

We present predictions of transport through micro-CT images of porous media that include the analysis of correlation structure, velocity, and the dynamics of the evolving plume. We simulate solute transport through millimeter-sized three-dimensional images of a beadpack, a sandstone, and a carbonate, representing porous media with an increasing degree of pore-scale complexity. The Navier-Stokes equations are solved to compute the flow field and a streamline simulation approach is used to move particles by advection, while the random walk method is employed to represent diffusion. We show how the computed propagators (concentration as a function of displacement) for the beadpack, sandstone, and carbonate depend on the width of the velocity distribution. A narrow velocity distribution in the beadpack leads to the least anomalous behavior, where the propagators rapidly become Gaussian in shape; the wider velocity distribution in the sandstone gives rise to a small immobile concentration peak, and a large secondary mobile peak moving at approximately the average flow speed; in the carbonate with the widest velocity distribution, the stagnant concentration peak is persistent, with a slower emergence of a smaller secondary mobile peak, characteristic of highly anomalous behavior. This defines different types of transport in the three media and quantifies the effect of pore structure on transport. The propagators obtained by the model are in excellent agreement with those measured on similar cores in nuclear magnetic resonance experiments by Scheven, Verganelakis, Harris, Johns, and Gladden, Phys. Fluids 17, 117107 (2005).

Signature of non-Fickian solute transport in complex heterogeneous porous media.

We simulate transport of a solute through three-dimensional images of different rock samples, with resolutions of a few microns, representing geological media of increasing pore-scale complexity: a sandpack, a Berea sandstone, and a Portland limestone. We predict the propagators (concentration as a function of distance) measured on similar cores in nuclear magnetic resonance experiments and the dispersion coefficient as a function of Péclet number and time. The behavior is explained using continuous time random walks with a truncated power-law distribution of travel times: transport is qualitatively different for the complex limestone compared to the sandstone or sandpack, with long tailing, an almost immobile peak concentration, and a very slow approach to asymptotic dispersion.