4D microvelocimetry reveals multiphase flow field perturbations in porous media.

Many environmental and industrial processes depend on how fluids displace each other in porous materials. However, the flow dynamics that govern this process are still poorly understood, hampered by the lack of methods to measure flows in optically opaque, microscopic geometries. We introduce a 4D microvelocimetry method based on high-resolution X-ray computed tomography with fast imaging rates (up to 4 Hz). We use this to measure flow fields during unsteady-state drainage, injecting a viscous fluid into rock and filter samples. This provides experimental insight into the nonequilibrium energy dynamics of this process. We show that fluid displacements convert surface energy into kinetic energy. The latter corresponds to velocity perturbations in the pore-scale flow field behind the invading fluid front, reaching local velocities more than 40 times faster than the constant pump rate. The characteristic length scale of these perturbations exceeds the characteristic pore size by more than an order of magnitude. These flow field observations suggest that nonlocal dynamic effects may be long-ranged even at low capillary numbers, impacting the local viscous-capillary force balance and the representative elementary volume. Furthermore, the velocity perturbations can enhance unsaturated dispersive mixing and colloid transport and yet, are not accounted for in current models. Overall, this work shows that 4D X-ray velocimetry opens the way to solve long-standing fundamental questions regarding flow and transport in porous materials, underlying models of, e.g., groundwater pollution remediation and subsurface storage of CO2 and hydrogen.

An Automated Wireless System for Monitoring Concrete Structures Based on Embedded Electrical Resistivity Sensors: Data Transmission and Effects on Concrete Properties.

Modern infrastructure heavily relies on robust concrete structures, underscoring the critical need for effective monitoring to ensure their safety and durability. This paper addresses this imperative issue by introducing an innovative automated and wireless system for continuous structural monitoring. By employing embedded electrical resistivity sensors coupled with a wireless-based data transmission mechanism, real-time data collection becomes feasible. We provide a general description of the system's architecture and its application in a pilot study covering the effects of the devices on concrete properties and data transmission. The dielectric properties of concrete specimens were investigated under natural and accelerated curing/degradation and the results were used in the final design of the antenna device. Furthermore, a pilot test comprising four reinforced concrete columns was used to investigate the range of data transmission from inside to outside of the concrete, the effects of the hardware device on the compressive strength and concrete distribution in the columns, and the data transmission quality in real time under realistic exposure conditions.

Dynamic Effects during the Capillary Rise of Fluids in Cylindrical Tubes.

The mathematical models for the capillary-driven flow of fluids in tubes typically assume a static contact angle at the fluid-air contact line on the tube walls. However, the dynamic evolution of the fluid-air interface is an important feature during capillary rise. Furthermore, inertial effects are relevant at early times and may lead to oscillations. To incorporate and quantify the different effects, a fundamental description of the physical processes within the tube is used to derive an upscaled model of capillary-driven flow in circular cylindrical tubes. The upscaled model extends the classical Lucas-Washburn model by incorporating a dynamic contact angle and slip. It is then further extended to account for inertial effects. Finally, the solutions of the different models are compared to experimental data. In contrast to the Lucas-Washburn model, the models with dynamic contact angle match well the experimental data, both the rise height and the contact angle, even at early times. The models have a free parameter through the dynamic contact angle description, which is fitted using the experimental data. The findings here suggest that this parameter depends only on the properties of the fluid but is independent of geometrical features, such as the tube radius. Therefore, the presented models can predict the capillary-driven flow in tubular systems upon knowledge of the underlying dynamic contact-angle relation.

Monte Carlo Simulation Aided Quantitative Laboratory X-ray Fluorescence Analysis and Its Application in Provenancing Studies for Geo-Archeological Samples.

A laboratory-based X-ray fluorescence (XRF) methodology is presented for standardless quantified analysis based on a monochromatic X-ray spectrometer coupled to Monte Carlo aided quantification. This procedure will be valuable for many scientific fields (e.g. archaeology, geology, etc.) where the unique nature of the investigated samples calls for the application of non-destructive techniques. To illustrate the value of the methodology, a case study is presented where flint artefacts from the Scheldt basin are analyzed in an attempt to provenance them. So far, little geochemical research has been done in this area. Our results contribute to the creation of a database that will help assign lithic artefacts to specific geological outcrops and will aid further research in this field.

Methane Bubble Growth and Migration in Aquatic Sediments Observed by X-ray µCT.

Methane bubble formation and transport is an important component of biogeochemical carbon cycling in aquatic sediments. To improve understanding of how sediment mechanical properties influence bubble growth and transport in freshwater sediments, a 20-day laboratory incubation experiment using homogenized natural clay and sand was performed. Methane bubble development at high resolution was characterized by µCT. Initially, capillary invasion by microbubbles (<0.1 mm) dominated bubble formation, with continued gas production (4 days for clay; 8 days for sand), large bubbles formed by deforming the surrounding sediment, leading to enhanced of macropore connectivity in both sediments. Growth of large bubbles (>1 mm) was possible in low shear yield strength sediments (<100 Pa), where excess gas pressure was sufficient to displace the sediment. Lower within the sand, higher shear yield strength (>360 Pa) resulted in a predominance of microbubbles where the required capillary entry pressure was low. Enhanced bubble migration, triggered by a controlled reduction in hydrostatic head, was observed throughout the clay column, while in sand mobile bubbles were restricted to the upper 6 cm. The observed macropore network was the dominant path for bubble movement and release in both sediments.

In Situ Triaxial Testing To Determine Fracture Permeability and Aperture Distribution for CO2 Sequestration in Svalbard, Norway.

On Svalbard, Arctic Norway, an unconventional siliciclastic reservoir, relying on (micro)fractures for enhanced fluid flow in a low-permeable system, is investigated as a potential CO2 sequestration site. The fractures' properties at depth are, however, poorly understood. High resolution X-ray computed tomography (micro-CT) imaging allows one to visualize such geomaterials at reservoir conditions. We investigated reservoir samples from the De Geerdalen Formation on Svalbard to understand the influence of fracture closure on the reservoir fluid flow behavior. Small rock plugs were brought to reservoir conditions, while permeability was measured through them during micro-CT imaging. Local fracture apertures were quantified down to a few micrometers wide. The permeability measurements were complemented with fracture permeability simulations based on the obtained micro-CT images. The relationship between fracture permeability and the imposed confining pressure was determined and linked to the fracture apertures. The investigated fractures closed due to the increased confining pressure, with apertures reducing to approximately 40% of their original size as the confining pressure increased from 1 to 10 MPa. This coincides with a permeability drop of more than 90%. Despite their closure, fluid flow is still controlled by the fractures at pressure conditions similar to those at the proposed storage depth of 800-1000 m.

Integrated Three-Dimensional Microanalysis Combining X-Ray Microtomography and X-Ray Fluorescence Methodologies.

A novel 3D elemental and morphological analysis approach is presented combining X-ray computed tomography (µCT), X-ray fluorescence (XRF) tomography, and confocal XRF analysis in a single laboratory instrument (Herakles). Each end station of Herakles (µCT, XRF-CT, and confocal XRF) represents the state-of-the-art of currently available laboratory techniques. The integration of these techniques enables linking the (quantitative) spatial distribution of chemical elements within the investigated materials to their three-dimensional (3D) internal morphology/structure down to 1-10 µm resolution level, which has not been achieved so-far using laboratory X-ray techniques. The concept of Herakles relies strongly on its high precision (around 100 nm) air-bearing motor system that connects the different end-stations, allowing combined measurements based on the above X-ray techniques while retaining the coordinate system. In-house developed control and analysis software further ensures a smooth integration of the techniques. Case studies on a Cu test pattern, a Daphnia magna model organism and a perlite biocatalyst support material demonstrate the attainable resolution, elemental sensitivity of the instrument, and the strength of combining these three complementary methodologies.

A pore-scale study of fracture dynamics in rock using X-ray micro-CT under ambient freeze-thaw cycling.

Freeze-thaw cycling stresses many environments which include porous media such as soil, rock and concrete. Climate change can expose new regions and subject others to a changing freeze-thaw frequency. Therefore, understanding and predicting the effect of freeze-thaw cycles is important in environmental science, the built environment and cultural heritage preservation. In this paper, we explore the possibilities of state-of-the-art micro-CT in studying the pore scale dynamics related to freezing and thawing. The experiments show the development of a fracture network in a porous limestone when cooling to -9.7 °C, at which an exothermal temperature peak is a proxy for ice crystallization. The dynamics of the fracture network are visualized with a time frame of 80 s. Theoretical assumptions predict that crystallization in these experiments occurs in pores of 6-20.1 nm under transient conditions. Here, the crystallization-induced stress exceeds rock strength when the local crystal fraction in the pores is 4.3%. The location of fractures is strongly related to preferential water uptake paths and rock texture, which are visually identified. Laboratory, continuous X-ray micro-CT scanning opens new perspectives for the pore-scale study of ice crystallization in porous media as well as for environmental processes related to freeze-thaw fracturing.

Monitoring of stainless-steel slag carbonation using X-ray computed microtomography.

Steel production is one of the largest contributors to industrial CO2 emissions. This industry also generates large amounts of solid byproducts, such as slag and sludge. In this study, fine grained stainless-steel slag (SSS) is valorized to produce compacts with high compressive strength without the use of a hydraulic binder. This carbonation process is investigated on a pore-scale level to identify how the mineral phases in the SSS react with CO2, where carbonates are formed, and what the impact of these changes is on the pore network of the carbonated SSS compact. In addition to conventional research techniques, high-resolution X-ray computed tomography (HRXCT) is applied to visualize and quantify the changes in situ during the carbonation process. The results show that carbonates mainly precipitate at grain contacts and in capillary pores and this precipitation has little effect on the connectivity of the pore space. This paper also demonstrates the use of a custom-designed polymer reaction cell that allows in situ HRXCT analysis of the carbonation process. This shows the distribution and influence of water and CO2 in the pore network on the carbonate precipitation and, thus, the influence on the compressive strength development of the waste material.

Circular design, material properties, service life and cradle-to-cradle carbon footprint of lime-based building materials.

The massive extraction of virgin raw materials has substantially intensified the focus on circular economy of building materials. As a Cradle-to-Cradle service life and circular approach for lime-based construction materials (LBCM) is lacking, the present study evaluates the environmental impact and feasibility of creating a fully recycled second-life render (SL) by designing a closed-loop upcycling process for first-life renders (FL). To achieve this, a second-life binder was thermally activated (900, 1000, 1100, 1200 °C), while its microstructure, compressive strength, and thermal conductivity were investigated. SL had up to 33 % open porosity (FL 29 %), its compressive strength ranged from 2.5 to 3.4 MPa (FL 4.4 MPa) and the thermal conductivity from 1.002 to 1.107 W/mK (FL 1.231 W/mK). Resistance of SL and FL against sulfate attack was found to be equivalent, measured based on the recent RILEM TC 271-ASC recommendation. The environmental impact indicators integrating material properties and durability confirm that the second life-render can reduce CO2 emissions up to 55 %. The present research provides insights into unlocking essential sustainability gains through circular practices in the life-cycle of LBCM.

Micro computed tomography images of capillary actions in rough and irregular granular materials.

The present work investigates the effect of both surface roughness and particle morphology on the retention behaviour of granular materials via X-ray micro-computed tomography (µCT) observations. X-ray µCT images were taken on two types of spherical glass beads (i.e. smooth and rough) and two different sands (i.e. natural and roughened). Each sample was subjected to drainage and soaking paths consisting in a multiphase 'static' flow of potassium iodine (KI) brine (wetting phase) and dry air (non-wetting phase). Tomograms were obtained at different saturation states ranging from fully brine saturated to air dry conditions with 6.2 µm voxel size resolution. The data acquisition and pre-processing are here described while all data, a total of 48 tomograms, are made publicly available. The combined dataset offers new opportunities to study the influence of surface roughness and particle morphology on capillary actions as well as supporting validation of pore-scale models of multiphase flow in granular materials.

Modeled versus Experimental Salt Mixture Behavior under Variable Humidity.

This study investigates the kinetics of salt mixture crystallization under relative humidity (RH) conditions, varying between 15 and 95% (at 20 °C), to inform applications in built heritage preservation, geology, and environmental sciences. We focused on commonly found, sulfate-rich and calcium-rich salt mixtures containing five to six ions, Cl-, NO3-, Na+, and K+, including or excluding less common Mg2+, and including either an excess of SO42- or Ca2+, with respect to gypsum. Using time-lapse micrographs and dynamic vapor sorption, we explore how crystallization and dissolution behavior depend on RH and mixture composition under constant temperature. A range of RH change rates were studied to simulate realistic weather events. Microstructural analyses through environmental scanning electron microscopy (ESEM) confirmed the crystal habit corresponding with RH transitions. Phases predicted from thermodynamic modeling (ECOS/RUNSALT) were confirmed using micro-Raman spectroscopy, X-ray diffraction (XRD), and elemental mapping via energy-dispersive X-ray spectroscopy (EDX). We identify a strong correlation between phase transition kinetics and RH change rates, with crystallization deviating by -15% and dissolution by +7% from modeled values under rapid (several seconds) and slow (several days) RH changes. These insights are important for preservation strategies in built heritage, salt deposition, and dissolution mechanisms in diverse geological and realistic environmental contexts, laboratory experiments, future modeling efforts, and the understanding of stone decay in general.

Spontaneous Imbibition and Evaporation in Rocks at the Nanometer Scale.

Understanding multiphase fluid displacement dynamics in porous media is of great importance in efficiently designing hydrogen storage projects in porous reservoirs. During gas injection and extraction, cyclic evaporation and spontaneous imbibition processes have an impact on storage efficiency. In both imbibition and evaporation, capillary films on the surface of grains play a role in the transport of water through the pore space. In this study, we use atomic force microscopy to study the formation of these films in carbonate rock during imbibition and their dynamic behavior during evaporation. The imbibition dynamics are related to pore-scale processes determined by micro-CT experiments. We find that imbibition through the mesoporous structure of the grains is slower compared to imbibition in macropores. The formation of the water film on the outer grains is also slower, indicating that a film is evolving due to water flow through intragranular mesopores rather than film flow around the grains. Evaporation experiments reveal that the film shows both local swelling and shrinkage behavior, which we relate to pore-scale processes causing disconnection of the water film. Our results show the close relationship between pore-scale processes and water film dynamics during both spontaneous imbibition and evaporation. This work forms a basis for a more quantitative study of the impact of pore structure on wetting and drying dynamics and can be extended to reactive flow processes.

Characterization of Pharmaceutical Tablets by X-ray Tomography.

Solid dosage forms such as tablets are extensively used in drug administration for their simplicity and large-scale manufacturing capabilities. High-resolution X-ray tomography is one of the most valuable non-destructive techniques to investigate the internal structure of the tablets for drug product development as well as for a cost effective production process. In this work, we review the recent developments in high-resolution X-ray microtomography and its application towards different tablet characterizations. The increased availability of powerful laboratory instrumentation, as well as the advent of high brilliance and coherent 3rd generation synchrotron light sources, combined with advanced data processing techniques, are driving the application of X-ray microtomography forward as an indispensable tool in the pharmaceutical industry.

Salt mixtures in stone weathering.

Salt related weathering of stones has been attributed to pressures exerted by repeated cycles of crystallization within pores. Relative Humidity (RH) is a key driver for dissolution and crystallization processes. Despite the prevalence of salt mixtures in natural environments, most experimental work has focused on single salts. Thus, the identification of salt mixture composition and their behavior is necessary to understand weathering. Thermodynamic calculations are used to analyze several thousand realistic salt mixtures found in weathered stone. We identify two common mixture types and their behavior. From at least 85 salt species theoretically present, 14 common salts are identified that occur most frequently and their critical RH points are discussed. These findings have wide-reaching implications for understanding salt weathering processes and informing the design of experimental stone weathering research.

Charge balance calculations for mixed salt systems applied to a large dataset from the built environment.

Understanding salt mixtures in the built environment is crucial to evaluate damage phenomena. This contribution presents charge balance calculations applied to a dataset of 11412 samples taken from 338 sites, building materials showing signs of salt deterioration. Each sample includes ion concentrations of Na+, K+, Mg2+, Ca2+, Cl-, NO3-, and SO42- adjusted to reach charge balance for data evaluation. The calculation procedure follows two distinct pathways: i) an equal adjustment of all ions, ii) adjustments to the cations in sequence related to the solubility of the theoretical solids. The procedure applied to the dataset illustrates the quantification of salt mixture compositions and highlights the extent of adjustments applied in relation to the sample mass to aid interpretation. The data analysis allows the identification of theoretical carbonates that could influence the mixture behavior. Applying the charge balance calculations to the dataset validated common ions found in the built environment and the identification of three typical mixture compositions. Additionally, the data can be used as direct input for thermodynamic modeling.

Exploration of the X-ray Dark-Field Signal in Mineral Building Materials.

Mineral building materials suffer from weathering processes such as salt efflorescence, freeze-thaw cycling, and microbial colonization. All of these processes are linked to water (liquid and vapor) in the pore space. The degree of damage following these processes is heavily influenced by pore space properties such as porosity, pore size distribution, and pore connectivity. X-ray computed micro-tomography (µCT) has proven to be a valuable tool to non-destructively investigate the pore space of stone samples in 3D. However, a trade-off between the resolution and field-of-view often impedes reliable conclusions on the material's properties. X-ray dark-field imaging (DFI) is based on the scattering of X-rays by sub-voxel-sized features, and as such, provides information on the sample complementary to that obtained using conventional µCT. In this manuscript, we apply X-ray dark-field tomography for the first time on four mineral building materials (quartzite, fired clay brick, fired clay roof tile, and carbonated mineral building material), and investigate which information the dark-field signal entails on the sub-resolution space of the sample. Dark-field tomography at multiple length scale sensitivities was performed at the TOMCAT beamline of the Swiss Light Source (Villigen, Switzerland) using a Talbot grating interferometer. The complementary information of the dark-field modality is most clear in the fired clay brick and roof tile; quartz grains that are almost indistinguishable in the conventional µCT scan are clearly visible in the dark-field owing to their low dark-field signal (homogenous sub-voxel structure), whereas the microporous bulk mass has a high dark-field signal. Large (resolved) pores on the other hand, which are clearly visible in the absorption dataset, are almost invisible in the dark-field modality because they are overprinted with dark-field signal originating from the bulk mass. The experiments also showed how the dark-field signal from a feature depends on the length scale sensitivity, which is set by moving the sample with respect to the grating interferometer.

Influence of pore structure on the effectiveness of a biogenic carbonate surface treatment for limestone conservation.

A ureolytic biodeposition treatment was applied to five types of limestone in order to investigate the effect of pore structure on the protective performance of a biogenic carbonate surface treatment. Protective performance was assessed by means of transport and degradation processes, and the penetration depth of the treatment was visualized by microtomography. Pore size governs bacterial adsorption and hence the location and amount of carbonate precipitated. This study indicated that in macroporous stone, biogenic carbonate formation occurred to a larger extent and at greater depths than in microporous stone. As a consequence, the biodeposition treatment exhibited the greatest protective performance on macroporous stone. While precipitation was limited to the outer surface of microporous stone, biogenic carbonate formation occurred at depths of greater than 2 mm for Savonnières and Euville. For Savonnières, the presence of biogenic carbonate resulted in a 20-fold decreased rate of water absorption, which resulted in increased resistance to sodium sulfate attack and to freezing and thawing. While untreated samples were completely degraded after 15 cycles of salt attack, no damage was observed in biodeposition-treated Savonnières. From this study, it is clear that biodeposition is very effective and more feasible for macroporous stones than for microporous stones.

Three-dimensional analysis of high-resolution X-ray computed tomography data with Morpho+.

Three-dimensional (3D) analysis is an essential tool to obtain quantitative results from 3D datasets. Considerable progress has been made in 3D imaging techniques, resulting in a growing need for more flexible, complete analysis packages containing advanced algorithms. At the Centre for X-ray Tomography of the Ghent University (UGCT), research is being done on the improvement of both hardware and software for high-resolution X-ray computed tomography (CT). UGCT collaborates with research groups from different disciplines, each having specific needs. To meet these requirements the analysis software package, Morpho+, was developed in-house. Morpho+ contains an extensive set of high-performance 3D operations to obtain object segmentation, separation, and parameterization (orientation, maximum opening, equivalent diameter, sphericity, connectivity, etc.), or to extract a 3D geometrical representation (surface mesh or skeleton) for further modeling. These algorithms have a relatively short processing time when analyzing large datasets. Additionally, Morpho+ is equipped with an interactive and intuitive user interface in which the results are visualized. The package allows scientists from various fields to obtain the necessary quantitative results when applying high-resolution X-ray CT as a research tool to the nondestructive investigation of the microstructure of materials.

Fast micro-computed tomography data of solute transport in porous media with different heterogeneity levels.

Solute transport processes are influenced by pore-scale heterogeneity. To study this, transient micron-scale solute concentration fields were imaged by fast laboratory-based X-ray micro-computed tomography. We performed tracer injection experiments in three types of porous material with increasing levels of heterogeneity (sintered glass, Bentheimer sandstone and Savonnières limestone). Different Peclet numbers were used during the experiments. For each sample and Peclet number, datasets of 40 to 74 3D images were acquired by continuous scanning with a voxel size of 13.4 to 14.6 µm and a temporal resolution of 15 to 12 seconds. To determine the measurement uncertainty on the obtained concentration fields, we performed calibration experiments under similar circumstances (temporal resolution of 12 seconds and voxel size of 13.0 µm). Here, we provide a systematic description of the data acquisition and processing and make all data, a total of 464 tomograms, publicly available. The combined dataset offers new opportunities to study the influence of pore-scale heterogeneity on solute transport, and to validate pore-scale simulations of this process in increasingly complex samples.