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Abstract In this study, the complexity of a steady-state flow through porous media is revealed using confocal laser scanning microscopy (CLSM). Micro-particle image velocimetry (micro-PIV) is applied to construct movies of colloidal particles. The calculated velocity vector fields from images are further utilized to obtain laminar flow streamlines. Fluid flow through a single straight channel is used to confirm that quantitative CLSM measurements can be conducted. Next, the coupling between the flow in a channel and the movement within an intersecting dead-end region is studied. Quantitative CLSM measurements confirm the numerically determined coupling parameter from earlier work of the authors. The fluid flow complexity is demonstrated using a porous medium consisting of a regular grid of pores in contact with a flowing fluid channel. The porous media structure was further used as the simulation domain for numerical modeling. Both the simulation, based on solving Stokes equations, and the experimental data show presence of non-trivial streamline trajectories across the pore structures. In view of the results, we argue that the hydrodynamic mixing is a combination of non-trivial streamline routing and Brownian motion by pore-scale diffusion. The results provide insight into challenges in upscaling hydrodynamic dispersion from pore scale to representative elementary volume (REV) scale. Furthermore, the successful quantitative validation of CLSM-based data from a microfluidic model fed by an electrical syringe pump provided a valuable benchmark for qualitative validation of computer simulation results. Graphic Abstract

In this study, the complexity of a steady-state flow through porous media is revealed using confocal laser scanning microscopy (CLSM). Micro-particle image velocimetry (micro-PIV) is applied to construct movies of colloidal particles. The calculated velocity vector fields from images are further utilized to obtain laminar flow streamlines. Fluid flow through a single straight channel is used to confirm that quantitative CLSM measurements can be conducted. Next, the coupling between the flow in a channel and the movement within an intersecting dead-end region is studied. Quantitative CLSM measurements confirm the numerically determined coupling parameter from earlier work of the authors. The fluid flow complexity is demonstrated using a porous medium consisting of a regular grid of pores in contact with a flowing fluid channel. The porous media structure was further used as the simulation domain for numerical modeling. Both the simulation, based on solving Stokes equations, and the experimental data show presence of non-trivial streamline trajectories across the pore structures. In view of the results, we argue that the hydrodynamic mixing is a combination of non-trivial streamline routing and Brownian motion by pore-scale diffusion. The results provide insight into challenges in upscaling hydrodynamic dispersion from pore scale to representative elementary volume (REV) scale. Furthermore, the successful quantitative validation of CLSM-based data from a microfluidic model fed by an electrical syringe pump provided a valuable benchmark for qualitative validation of computer simulation results. Graphic Abstract: [Figure not available: see fulltext.].

Modeling coupled systems of free flow adjacent to a porous medium by means of fully resolved Navier-Stokes equations is limited by the immense computational cost and is thus only feasible for relatively small domains. Coupled, hybrid-dimensional models can be much more efficient by simplifying the porous domain, e.g., in terms of a pore-network model. In this work, we present a coupled pore-network/free-flow model taking into account pore-scale slip at the local interfaces between free flow and the pores. We consider two-dimensional and three-dimensional setups and show that our proposed slip condition can significantly increase the coupled model’s accuracy: compared to fully resolved equidimensional numerical reference solutions, the normalized errors for velocity are reduced by a factor of more than five, depending on the flow configuration. A pore-scale slip parameter βpore required by the slip condition was determined numerically in a preprocessing step. We found a linear scaling behavior of βpore with the size of the interface pore body for three-dimensional and two-dimensional domains. The slip condition can thus be applied without incurring any run-time cost. In the last section of this work, we used the coupled model to recalculate a microfluidic experiment where we additionally exploited the flat structure of the micromodel which permits the use of a quasi-3D free-flow model. The extended coupled model is accurate and efficient., Projekt DEAL, Deutsche Forschungsgemeinschaft

Paper used in the printing industry generally contains a relatively thin porous coating covering a thicker fibrous base layer. The three-dimensional pore structure of coatings has a major effect on fluid flow patterns inside the paper medium. Understanding and quantifying the flow properties of thin coating layers is hence crucial. Pore spaces within the coating have an average size of about 180 nm. We used scanning electron microscopy combined with focused ion beam (FIB-SEM) to visualize the nano-scale pore structure of the paper coating layer. Post-processing of the FIB-SEM images allowed us to reconstruct the three-dimensional pore space of the coating. The 3D FIB-SEM images were analyzed in detail to obtain pore size distribution and porosity value. The permeability was estimated using the Geo-Dict software, based on solutions of the Stokes equation. By determining the porosity and the permeability for increasingly larger domain sizes, we estimated the size of a representative elementary volume (REV) for the coating layer to be 60 µm3, which is well within the volume analyzed by FIB-SEM. The estimated porosity and permeability of the REV domain were 0.34 and 0.09 mDarcy, respectively, relatively close to previous literature values for coatings ((Patrick A. Gane et al., 1996), (Alam et al., 2009)). Using the pore morphology method, the capillary pressure-saturation (Pc-S) and relative permeability curves of the REV domain could be constructed next. The Pc-S curves showed that the coating has a high air entry suction, which is very favorable for printing in that an ink will invade the coating as soon as it applied to the coating. Our results are essential for macroscale modelling of ink penetration into a coating layer during inkjet printing. Macroscopic models can be valuable tools for optimization of the penetration depth and the spreading of ink on and within paper substrates.

Emulsions stabilized by solid particles, called Pickering emulsions, offer promising applications in drug delivery, cosmetics, food science and the manufacturing of porous materials. This potential stems from their high stability against coalescence and ‘surfactant-free’ nature. Generally, Pickering emulsions require that the solid particles are wetted by both phases and as a result, the adsorption free energy is often large with respect to the thermal energy (kBT). Here we provide the first experimental proof for an alternative scenario: non-touching (effectively non-wetting), charged, particles that are completely immersed in the oil phase through a balance of charge induced attractions and repulsions caused by van der Waals forces. These particles nonetheless stabilize the emulsion. The main advantage of this novel adsorption mechanism is that these particles can easily be detached from the interface simply by adding salt. This not only makes the finding fundamentally of interest, but also enables a triggered de-emulsification and particle recovery, which is useful in fields like enhanced oil recovery, heterogeneous catalysis, and emulsion polymerization.

Break on through: Steaming-induced mesopores of individual ZSM-5 crystals were studied by a combination of focused ion beam (FIB) and scanning electron microscopy (SEM) tomography (see picture). In this manner, quantitative insight into the width, length, morphology, and distribution of mesopores generated within zeolite crystals has been obtained. Keywords:crystal intergrowth;scanning probe microscopy;mesoporosity;tomography;zeolites

The Focused Ion Beam – Scanning Electron Microscope (FIB-SEM) is a versatile instrument originating from the semiconductor industry. The FIB is used to produce cross sections of pre-defined locations of interest, which are imaged and analyzed with the SEM. Repeated FIB cross sectioning and subsequent SEM imaging –a process called FIB-SEM tomography– results in a full three-dimensional analysis of the structure of interest, allowing for the 3D reconstruction of cellular materials or porous media. In recent years, the capabilities of the FIB-SEM have attracted a considerable amount of attention from various scientific disciplines. This PhD Thesis presents a survey across samples from Life Sciences, Earth Sciences and Material Sciences, exploring and validating the application of the FIB-SEM instrument to scientific questions from the three disciplines. The common denominator of the various samples under investigation is their electrically insulating nature, requiring additional care in dealing with the samples in the microscope. Life Sciences Electron Microscopy (EM) in Life Sciences can be split in room temperature (cells are dehydrated, optionally embedded) and cryo applications. A contribution is made in both fields. Room temperature FIB-SEM tomography is demonstrated on cells embedded in a resin. The cellular membranes are stained with heavy metals, providing sufficient contrast in Back Scattered Electron (BSE) mode. It is shown that the distribution of endoplasmic reticulum and the mitochondria can be reconstructed in three dimensions. As for cryo-EM, a major quest in Life Sciences is the preparation of artifact-free thick cryo-sections or lamellas (>200 nm) for cryo-Transmission Electron Microscopy (TEM) tomography. A dedicated workflow has been developed to produce such thick cryo-sections with the FIB, while is SEM is used to check the quality of the sections in-situ. Earth Sciences The importance of 3D reconstructions over 2D imaging is demonstrated with an olivine sample. The permeability of olivine is linked to the wetting angle –the dihedral angle– of the melt and the rock. FIB-SEM tomography data of melt pockets indicates that measuring the dihedral angle based on 2D data may not be valid because of the presence of facets in the third dimension. Material Sciences Two different Material Sciences samples are investigated: 1) Large steamed zeolite ZSM-5 crystals and 2) Fluid Catalytic Cracking (FCC) particles. The steaming process of large ZSM-5 crystals creates mesoporosity, which is characterized by FIB-SEM tomography. To prevent charging artifacts, low-kV BSE imaging is used successfully. FIB-SEM tomography through the FCC particles revealed two major challenges considering the post-processing of the 3D data. The first challenge considers automated segmentation of the pore space from FIB-SEM tomography data. A combination of several techniques is found to be sufficiently accurate. The second challenge involves upscaling of transport properties from the dimensions analyzed by the FIB-SEM. A workflow is presented which employs experimentally based statistical means to extrapolate high resolution data to much larger length scales.

We report an experimental and microstructural study of the frictional properties of simulated fault gouges prepared from natural limestone (96 % CaCO3) and pure calcite. Our experiments consisted of direct shear tests performed, under dry and wet conditions, at an effective normal stress of 50 MPa, at 18–150 °C and sliding velocities of 0.1–10 μm/s. Wet experiments used a pore water pressure of 10 MPa. Wet gouges typically showed a lower steady-state frictional strength (μ = 0.6) than dry gouges (μ = 0.7–0.8), particularly in the case of the pure calcite samples. All runs showed a transition from stable velocity strengthening to (potentially) unstable velocity weakening slip above 80–100 °C. All recovered samples showed patchy, mirror-like surfaces marking boundary shear planes. Optical study of sections cut normal to the shear plane and parallel to the shear direction showed both boundary and inclined shear bands, characterized by extreme grain comminution and a crystallographic preferred orientation. Cross-sections of boundary shears, cut normal to the shear direction using focused ion beam—SEM, from pure calcite gouges sheared at 18 and 150 °C, revealed dense arrays of rounded, ~0.3 μm-sized particles in the shear band core. Transmission electron microscopy showed that these particles consist of 5–20 nm sized calcite nanocrystals. All samples showed evidence for cataclasis and crystal plasticity. Comparing our results with previous models for gouge friction, we suggest that frictional behaviour was controlled by competition between crystal plastic and granular flow processes active in the shear bands, with water facilitating pressure solution, subcritical cracking and intergranular lubrication. Our data have important implications for the depth of the seismogenic zone in tectonically active limestone terrains. Contrary to recent claims, our data also demonstrate that nanocrystalline mirror-like slip surfaces in calcite(-rich) faults are not necessarily indicative of seismic slip rates.

In this paper, lithographic methods are successfully employed to create growth templates for colloidal self-assembly, enabling the inclusion of crystallographic defects at predetermined positions. It is shown that through smart template design stacking faults can be grown predictably into face centered cubic structures. More interestingly, by precise guiding of the stacking faults hollow intergrowth channels can be grown at predetermined lateral and vertical positions. The mechanisms involved in defect growth are promising for extension of this technique to more complex crystal structures, such as the diamond structure, as well as to more complex faults, including corners and t-junctions.

A combination of atomic force microscopy (AFM), high-resolution scanning electron microscopy (HR-SEM), focused-ion-beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS), confocal fluorescence microscopy (CFM), and UV/Vis and synchrotronbased IR microspectroscopy was used to investigate the dealumination processes of zeolite ZSM-5 at the individual crystal level. It was shown that steaming has a significant impact on the porosity, acidity, and reactivity of the zeolite materials. The catalytic performance, tested by the styrene oligomerization and methanol-to-olefin reactions, led to the conclusion that mild steaming conditions resulted in greatly enhanced acidity and reactivity of dealuminated zeolite ZSM-5. Interestingly, only residual surface mesoporosity was generated in the mildly steamed ZSM- 5 zeolite, leading to rapid crystal coloration and coking upon catalytic testing and indicating an enhanced deactivation of the zeolites. In contrast, harsh steaming conditions generated 5–50 nm mesopores, extensively improving the accessibility of the zeolites. However, severe dealumination decreased the strength of the Brønsted acid sites, causing a depletion of the overall acidity, which resulted in a major drop in catalytic activity.

Starless molecular sieves: The starlike appearence of confocal fluorescence microscopy (CFM) images of large crystals of the AlPO-5 family of microporous materials is due to the presence of barriers to molecular diffusion in the internal crystal architecture (see picture) rather than a star-shaped subcrystal according to studies by CFM, focused ion beam milling, electron backscatter diffraction, and atomic force microscopy.

In this paper, we present a comprehensive study of the sol-gel transitions and liquid crystal phase transitions in aqueous suspensions of positively charged colloidal gibbsite platelets at pH 4-5 over a wide range of particle concentrations (50-600 g/L) and salt concentrations (10-4-10-1 M NaCl). A detailed sol-gel diagram was established by oscillatory rheological experiments. These demonstrate the presence of kinetically arrested states both at high and at low salt concentrations, enclosing a sol region. Birefringence and iridescence show that in the sol state nematic and hexagonal columnar liquid crystal phases are formed. The gel and liquid crystal structures are studied in further detail using small-angle X-ray scattering (SAXS) and cryo-focused ion beam/scanning electron microscopy (cryo-FIB-SEM). The gel formed at high salt concentration shows signatures of a sponge-like structure and does not display birefringence. In the sol region, by lowering the salt concentration and/or increasing the gibbsite concentration, the nematic phase gradually transforms from the discotic nematic (ND) into the columnar nematic (NC) with much stronger side-to-side interparticle correlations. Subsequently, this NC structure can be either transformed into the hexagonal columnar phase or arrested into a birefringent repulsive gel state with NC structure.