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.

Microphysiological model of PIK3CA-driven vascular malformations reveals a role of dysregulated Rac1 and mTORC1/2 in lesion formation.

Somatic activating mutations of PIK3CA are associated with development of vascular malformations (VMs). Here, we describe a microfluidic model of PIK3CA-driven VMs consisting of human umbilical vein endothelial cells expressing PIK3CA activating mutations embedded in three-dimensional hydrogels. We observed enlarged, irregular vessel phenotypes and the formation of cyst-like structures consistent with clinical signatures and not previously observed in cell culture models. Pathologic morphologies occurred concomitant with up-regulation of Rac1/p21-activated kinase (PAK), mitogen-activated protein kinase cascades (MEK/ERK), and mammalian target of rapamycin (mTORC1/2) signaling networks. We observed differential effects between alpelisib, a PIK3CA inhibitor, and rapamycin, an mTORC1 inhibitor, in mitigating matrix degradation and network topology. While both were effective in preventing vessel enlargement, rapamycin failed to reduce MEK/ERK and mTORC2 activity and resulted in hyperbranching, while inhibiting PAK, MEK1/2, and mTORC1/2 mitigates abnormal growth and vascular dilation. Collectively, these findings demonstrate an in vitro platform for VMs and establish a role of dysregulated Rac1/PAK and mTORC1/2 signaling in PIK3CA-driven VMs.

Refining the in vitro release test method for a dapivirine-releasing vaginal ring to match in vivo performance.

Previously reported in vitro release test methods for drug-releasing vaginal rings containing poorly water-soluble drugs have described use of water-alcohol systems or surfactant solutions in efforts to maintain sink conditions. Here, as part of efforts to more closely match in vitro and in vivo release for the 25 mg dapivirine matrix-type silicone elastomer vaginal ring for HIV prevention, we have investigated alternatives to the 1:1 v/v water/isopropanol medium described previously. Specifically, we evaluated dapivirine release from rings into (i) monophasic water/isopropanol mixtures of varying compositions and (ii) biphasic buffer/octanol systems using pH 4.2 and pH 7.0 buffers. The rate and mechanism of dapivirine release were dependent upon the isopropanol concentration in the release medium, in accordance with the observed trend in drug solubility. At 0 and 10% v/v isopropanol concentrations, dapivirine release followed a partition-controlled mechansim. For media containing ≥ 20% v/v isopropanol, in vitro release of dapivirine was significantly increased and obeyed permeation-controlled kinetics. Cumulative release of ~3.5 mg dapivirine over 28 days was obtained using a water isopropanol mixture containing 20% v/v isopropanol, similar to the ~4 mg dapivirine released in vivo. Dapivirine release into the biphasic buffer/octanol system (intended to mimic the fluid/tissue environment in vivo) was constrained by the limited solubility of dapivirine in the buffer component in which the ring resided, such that cumulative dapivirine release was consistently lower than that observed with the 20% v/v isopropanol in water medium. Release into the biphasic system was also pH dependent, in line with dapivirine's pKa and with potential implications for in vivo release and absorption in women with elevated vaginal pH.

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.

Thermodynamics of fluctuations based on time-and-space averages.

We develop nonequilibrium theory by using averages in time and space as a generalized way to upscale thermodynamics in nonergodic systems. The approach offers a classical perspective on the energy dynamics in fluctuating systems. The rate of entropy production is shown to be explicitly scale dependent when considered in this context. We show that while any stationary process can be represented as having zero entropy production, second law constraints due to the Clausius theorem are preserved due to the fact that heat and work are related based on conservation of energy. As a demonstration, we consider the energy dynamics for the Carnot cycle and for Maxwell's demon. We then consider nonstationary processes, applying time-and-space averages to characterize nonergodic effects in heterogeneous systems where energy barriers such as compositional gradients are present. We show that the derived theory can be used to understand the origins of anomalous diffusion phenomena in systems where Fick's law applies at small length scales, but not at large length scales. We further characterize fluctuations in capillary-dominated systems, which are nonstationary due to the irreversibility of cooperative events.

Direct Measure of Electrode Spatial Heterogeneity: Influence of Processing Conditions on Anode Architecture and Performance.

In this work, the spatial (in)homogeneity of aqueous processed silicon electrodes using standard poly(acrylic acid)-based binders and slurry preparation conditions is demonstrated. X-ray nanotomography shows segregation of materials into submicron-thick layers depending on the mixing method and starting binder molecular weights. Using a dispersant, or in situ production of dispersant from the cleavage of the binder into smaller molecular weight species, increases the resulting lateral homogeneity while drastically decreasing the vertical homogeneity as a result of sedimentation and separation due to gravitational forces. This data explains some of the variability in the literature with respect to silicon electrode performance and demonstrates two potential ways to improve slurry-based electrode fabrications.

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.

Beyond Darcy's law: The role of phase topology and ganglion dynamics for two-fluid flow.

In multiphase flow in porous media the consistent pore to Darcy scale description of two-fluid flow processes has been a long-standing challenge. Immiscible displacement processes occur at the scale of individual pores. However, the larger scale behavior is described by phenomenological relationships such as relative permeability, which typically uses only fluid saturation as a state variable. As a consequence pore scale properties such as contact angle cannot be directly related to Darcy scale flow parameters. Advanced imaging and computational technologies are closing the gap between the pore and Darcy scale, supporting the development of new theory. We utilize fast x-ray microtomography to observe pore-scale two-fluid configurations during immiscible flow and initialize lattice Boltzmann simulations that demonstrate that the mobilization of disconnected nonwetting phase clusters can account for a significant fraction of the total flux. We show that fluid topology can undergo substantial changes during flow at constant saturation, which is one of the underlying causes of hysteretic behavior. Traditional assumptions about fluid configurations are therefore an oversimplification. Our results suggest that the role of fluid connectivity cannot be ignored for multiphase flow. On the Darcy scale, fluid topology and phase connectivity are accounted for by interfacial area and Euler characteristic as parameters that are missing from our current models.

Pore Scale Dynamics of Microemulsion Formation.

Experiments in various porous media have shown that multiple parameters come into play when an oleic phase is displaced by an aqueous solution of surfactant. In general, the displacement efficiency is improved when the fluids become quasi-miscible. Understanding the phase behavior oil/water/surfactant systems is important because microemulsion has the ability to generate ultralow interfacial tension (<10(-2) mN m(-1)) that is required for miscibility to occur. Many studies focus on microemulsion formation and the resulting properties under equilibrium conditions. However, the majority of applications where microemulsion is present also involve flow, which has received relatively less attention. It is commonly assumed that the characteristics of an oil/water/surfactant system under flowing conditions are identical to the one under equilibrium conditions. Here, we show that this is not necessarily the case. We studied the equilibrium phase behavior of a model system consisting of n-decane and an aqueous solution of olefin sulfonate surfactant, which has practical applications for enhanced oil recovery. The salt content of the aqueous solution was varied to provide a range of different microemulsion compositions and oil-water interfacial tensions. We then performed microfluidic flow experiments to study the dynamic in situ formation of microemulsion by coinjecting bulk fluids of n-decane and surfactant solution into a T-junction capillary geometry. A solvatochromatic fluorescent dye was used to obtain spatially resolved compositional information. In this way, we visualized the microemulsion formation and the flow of it along with the excess phases. A complex interaction between the flow patterns and the microemulsion properties was observed. The formation of microemulsion influenced the flow regimes, and the flow regimes affected the characteristics of the microemulsion formation. In particular, at low flow rates, slug flow was observed, which had profound consequences on the pore scale mixing behavior and resulting microemulsion properties.

An Examination of Metrics for a Simulated Ventriculostomy Part-Task.

As one of the most commonly performed neurosurgical procedures, ventriculostomy training simulators are becoming increasingly familiar features in research institutes and teaching facilities. Despite their widespread implementations and adoption, simulators to date have not fully explored the landscape of performance metrics that reflect surgical proficiency. They opt instead for measures that are qualitative or simple to compute and conceptualize. In this paper, we examine and compare the use of various metrics to characterize the performance of users on simulated part-task ventriculostomy scenarios derived from patient data. As an initial study, we examine how our metrics relate to expert classification of scenario difficulty as well as measures of anatomical variation.

Characterization and assessment of hyperelastic and elastic properties of decellularized human adipose tissues.

Decellularized adipose tissue (DAT) has shown potential as a regenerative scaffold for plastic and reconstructive surgery to augment or replace damaged or missing adipose tissue (e.g. following lumpectomy or mastectomy). The mechanical properties of soft tissue substitutes are of paramount importance in restoring the natural shape and appearance of the affected tissues, and mechanical mismatching can lead to unpredictable scar tissue formation and poor implant integration. The goal of this work was to assess the linear elastic and hyperelastic properties of decellularized human adipose tissue and compare them to those of normal breast adipose tissue. To assess the influence of the adipose depot source on the mechanical properties of the resultant decellularized scaffolds, we performed indentation tests on DAT samples sourced from adipose tissue isolated from the breast, subcutaneous abdominal region, omentum, pericardial depot and thymic remnant, and their corresponding force-displacement data were acquired. Elastic and hyperelastic parameters were estimated using inverse finite element algorithms. Subsequently, a simulation was conducted in which the estimated hyperelastic parameters were tested in a real human breast model under gravity loading in order to assess the suitability of the scaffolds for implantation. Results of these tests showed that in the human breast, the DAT would show similar deformability to that of native normal tissue. Using the measured hyperelastic parameters, we were able to assess whether DAT derived from different depots exhibited different intrinsic nonlinearities. Results showed that DAT sourced from varying regions of the body exhibited little intrinsic nonlinearity, with no statistically significant differences between the groups.

Patient-specific pipeline to create virtual endoscopic third ventriculostomy scenarios.

Graphically realistic, haptics-enabled, virtual reality surgical simulations are becoming increasingly popular training tools for neurosurgical procedures and surgical skills. Compared with traditional training models, virtual simulations are safe, versatile, consistent, and are relatively cost effective. Most simulations are deficient, however, in representing the diverse anatomical variations that occur clinically. In this work, we describe the design and implementation of a pipeline to create patient-specific surgical scenarios for simulator-based training of the endoscopic third ventriculostomy: the procedure of choice for treating obstructive hydrocephalus.

Evaluation of a mobile augmented reality application for image guidance of neurosurgical interventions.

Image guidance can provide surgeons with valuable contextual information during a medical intervention. Often, image guidance systems require considerable infrastructure, setup-time, and operator experience to be utilized. Certain procedures performed at bedside are susceptible to navigational errors that can lead to complications. We present an application for mobile devices that can provide image guidance using augmented reality to assist in performing neurosurgical tasks. A methodology is outlined that evaluates this mode of visualization from the standpoint of perceptual localization, depth estimation, and pointing performance, in scenarios derived from a neurosurgical targeting task. By measuring user variability and speed we can report objective metrics of performance for our augmented reality guidance system.