Focused Ion Beam-scanning Electron Research Articles

Editors' Choice—Visualizing the Impact of the Composite Cathode Microstructure and Porosity on Solid-State Battery Performance

Abstract The kinetics of composite cathodes for solid-state batteries (SSBs) relies heavily on their micro-structure. Spatial distribution of the different phases, porosity, interface areas, and tortuosity factors are important descriptors that need accurate quantification for models to predict the elec-trochemistry and mechanics of SSBs. In this study, high-resolution focused ion beam-scanning electron microscopy tomography was used to investigate the microstructure of cathodes com-posed of a nickel-rich cathode active material (NCM) and a thiophosphate-based inorganic solid electrolyte (ISE). The influence of the ISE particle size on the microstructure of the cathode was visualized by 3D reconstruction and charge transport simulation. By comparison of experimen-tally determined and simulated conductivities of composite cathodes with different ISE particle sizes, the electrode charge transport kinetics is evaluated. Porosity is shown to have a major influence on the cell kinetics and the evaluation of the active mass of electrochemically active particles reveals a higher fraction of connected NCM particles in electrode composites utilizing smaller ISE particles. The results highlight the importance of homogeneous and optimized mi-crostructures for high performance SSBs, securing fast ion and electron transport.

Volume microscopic analysis of membrane contact sites in mouse kidney renal proximal tubule epithelial cells

Subcellular organelles communicate with one another and with the plasma membrane (PM). A wide variety of membrane contact sites (MCS) tether subcellular structures to one another and mediate inter-organelle communication and exchange. The nature, distribution and function of membrane contact sites within the segment-specific architecture of renal epithelial cells has only just begun to be elucidated. We have used advanced imaging techniques, including Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) and machine learning-based segmentation, to create a comprehensive, high resolution, 3D and quantifiable volume microscopic atlas of the ultrastructure of proximal tubule epithelial cells of the mouse kidney. We applied this data set to identify and quantify MCS between the endoplasmic reticulum and mitochondria and the PM in these cells. FIB-SEM was performed on a 50 μm by 50 μm by 44 μm block of tissue prepared from the renal cortex of a perfusion fixed 12-week-old male mouse. OsO4-stained tissue was embedded in Durcupan and a 3D X-ray tomogram of the block was used to select a volume of interest that included extended lengths of multiple proximal tubule (PT). The volume was imaged by a customized enhanced FIB-SEM system. The X-Y scanning resolution was set to 4-nm, and 4-nm FIB milling was used to expose surfaces for successive imaging. Generation of the complete image stack required ~11,000 cycles of scanning/FIB ablation over ~4 weeks of uninterrupted imaging. Segmentation of the resultant image set was performed with Zeiss Arivis Pro technology. The boundary box for reconstruction had the dimensions of 29.2 μm x 24.8 μm x 8 μm with a volume of 5793.280 μm3 comprising of 2000 consecutive images at an isotropic voxel size of 4 nm. Deep learning segmentation teased apart 10 cells with distinct boundaries in the PT structure. The volume of the cells in our clipped volume ranged from 8.79 μm3 to 1438.53 μm3 with a median of 45.20 μm3. In one representative proximal tubule cell the volume of mitochondria makes up 84.91 μm3 (31.62%) of the cell volume and the volume of Endoplasmic Reticulum (ER) makes up 23.92 μm3 (8.91%) of the cell volume. The 3D reconstruction and quantitative analysis revealed that there is one dominant ER object accounting for most of the ER volume in the whole cell: i.e., the largest ER object takes up 22.37 μm3 or 93.5% of the ER volume in the cell. A post deep-learning processing algorithm used 3D object modifications to identify 11,109 3D MCS between mitochondria and ER in the 10 cells. The Mito-ER MCS ranged from 512 nm3 to 354,304 nm3 with a median volume of 1792 nm3. Visually we can see Mito-ER and Mito-PM MCS extending across a region of up to ~45 nm between the two organelles. Taken together, these data show that the basal lateral surfaces of PT cell PMs are generously invested with fenestrated smooth ER, as are mitochondria and peroxisomes. Extensive regions of direct contact between mitochondria and PM are also observed. The biochemical identities of these contacts and their physiological functions are being actively pursued. NIDDK DK072612 NIDDK DK120534. This is the full abstract presented at the American Physiology Summit 2024 meeting and is only available in HTML format. There are no additional versions or additional content available for this abstract. Physiology was not involved in the peer review process.

Comparative Investigation on the Tribocorrosion Resistance of Ti6Al4V and 60NiTi Alloys in Simulated Seawater Environment

The Ti6Al4V alloy is extensively utilized in critical marine equipment components due to its low density, high specific strength, and exceptional corrosion resistance in marine environments. However, its low hardness and inadequate wear resistance pose challenges in meeting the urgent demand for prolonged service life of relative motion friction pairs under complex wear and corrosion conditions. As a newly developed lightweight friction pair material, hardened 60NiTi is considered highly desirable owing to its combination of high hardness, high compressive strength, and excellent corrosion resistance. Nevertheless, the tribocorrosion properties of 60NiTi compared to those of Ti6Al4V are not yet fully comprehended. The present study conducted a series of sliding wear tests using a ball-on-plate configuration in artificial seawater environment to compare the response of 60NiTi with Ti6Al4V. In order to gain a comprehensive understanding of the factors contributing to the divergence in tribocorrosion response between both materials, further analysis was performed on the wear track subsurface and transfer film using focused ion beam-scanning electron microscopy, Raman spectroscopy, and x-ray photoelectron spectroscopy respectively. The 60NiTi demonstrates significantly enhanced wear resistance in artificial seawater compared to Ti6Al4V, attributed to its combination of high hardness and excellent corrosion resistance. However, Ti6Al4V exhibits a lower friction coefficient (∼0.30) than 60NiTi (∼0.45) due to the formation of a stable transfer film primarily composed of SiO2, Al(OH)3, and Al2O3.

Synchrotron micro-computed tomography analysis of neutron-irradiated U-Mo fuel

The three-dimensional (3D) microstructure of neutron-irradiated uranium-10 wt.% molybdenum (U-10Mo) fuel with a burn-up of 9.8 × 1021 fissions/cm3 was characterized using a novel, multi-modal synchrotron micro-computed tomography approach combining propagation-based phase-contrast enhanced and absorption contrast techniques. The porosity development, porosity interconnectedness, swelling, composition, local thickness of the zirconium (Zr) diffusion barrier, and the influence of the fuel–cladding interaction on the local composition and pore morphology, were uniquely determined in 3D. Two cuboids were produced using a focused ion beam-scanning electron microscope at the Zr diffusion barrier–fuel interface and in the bulk fuel. The bulk fuel sample swelled by 53.3 [+9.7/−3.1]%, while the fuel near the Zr–fuel interface swelled by 63.3 [+14.7/−7.2]%. The average local thickness of the Zr diffusion barrier decreased by 53 %, compared to the expected pre-irradiated thickness. Four pore morphology regions were identified initiating parallel to the fuel–Zr interaction region: (1) an interaction layer of suppressed porosity, (2) a layer of elongated and interconnected porosity, (3) a transition zone of low porosity, and (4) a layer of unoriented porosity representative of the bulk fuel behavior. The increase in porosity near the diffusion barrier corresponded to a higher U concentration compared to that in the bulk fuel. The interconnected porosity in the fuel near the diffusion barrier was extensive and oriented parallel to the diffusion barrier, while the bulk fuel had more compact and isolated pore networks. The interaction layer, despite having suppressed porosity, was nearly 100 wt.% U. Porosity suppression at the diffusion barrier corresponds to the expected reduction in radiation-driven diffusion of Xe at the interface despite the anticipated increase in fission product nucleation originating from a higher U concentration. The novel 3D insights of the porosity, swelling, and compositional variations characterized herein can improve the fidelity of fuel performance codes for proliferation-resistant fuels for research and test reactors.

Approaching Technological Limit for Wet‐Pulling Technique

Carbon nanotube fibers (CNTFs) are a promising economical replacement material for contemporary metallic wired conductors due to their lightweight and advanced electromechanical properties. The wet‐pulling technique for CNTF manufacturing is highly versatile, adaptable for both laboratory as well as industrial‐scale production, and can be optimized for the maximum enhancement of electrophysical properties. Herein, a mechanosolvent‐based postfabrication approach for maximizing densification and improving electrical properties of wet‐pulled CNTFs is examined. The experimental process results in fibers achieving 60% of the theoretically maximum density and conductivity of maximally densified metallic single‐walled carbon nanotube bundles. The technique allows a corresponding increase of ≈700% in fiber density (from 100 to 704 kg m−3), a simultaneous ≈530% increase in electrical conductivity (from 748 to 3990 S cm−1), and reduced volume defects from 18% to 2%. The approach was combined with a step‐wise microstructure monitoring using focused ion beam–scanning electron microscopy to determine the mechanisms behind the optimized structures. This work is the first to provide an experimental and theoretical base for the postfabrication optimization of wet‐pulled CNTFs and lays the foundation for further enhancement with techniques such as chemical doping, fiber compounding, and combined infiltration/densification mechanisms.

High-Precision 3D reconstruction and quantitative structure description: Linking microstructure to macroscopic heat transfer of aerogels

The intricate interplay between microstructure and macroscopic transfer processes in porous materials has long been recognized, yet achieving a definitive link between them remains a formidable challenge. Herein, we propose an effective approach to address this challenge by introducing a high-precision 3D reconstruction and structure descriptor database analysis method of nanoporous aerogels, which enables deeper understanding and accurate predictions of structure-directed properties. By employing focused ion beam-scanning electron microscope (FIB-SEM) technique supplemented with image preprocessing and image segmentation, we successfully built a 3D reconstruction model that exhibits high consistency with experimental results. Then, a structure descriptor database from the view of original porous structure, structure connectivity, and topological information is established, and 10 descriptors are preliminarily filtered relevance with thermal conductivity. Consequently, the quantitative relationship between descriptor and thermal conductivity is evaluated via a back propagation (BP) neural network, and three categories structure descriptors which have the most significant impact are determined as (i) the description of gaseous heat transfer pathways, (ii) the description of three-dimensional connectivity, and (iii) the description of interface complexity. With the profound understanding of structure descriptor, the present work offers a novel, structure-focused strategy that closely link the microstructure to macroscopic properties of porous materials.

Integrated Physical and Digital Chalk Relative Permeability Evaluation: A Case Study

The Valhall chalk field has produced more than 1 billion barrels of oil equivalents over the last 40 years, primarily from the homogeneous Tor Formation. The underlying Hod Formation is more heterogeneous and is less maturely developed. The extent of heterogeneity poses a challenge in the evaluation of multiphase fluid flow properties. The objective of the work was to use digital core analysis to generate early relative permeability data to leverage and compare with conventional physical steady-state relative permeability data. Accurate digital and physical description of capillary pressure and relative permeability in the high-porosity chalk is complicated by both low permeabilities and heterogeneity. The main challenge with chalk is that flow occurs in a nano-environment. Physically, the nano-environment translates to low permeability, difficult rock preparation, and extensive experimental time, especiallyfor steady-state flow experiments. Representative three-dimensional (3D) digital rocks were generated using a combination of X-ray computed tomography (CT) and focused ion beam-scanning electron microscopy (FIB-SEM) methods. The digital rocks were used to simulate two-phase flow and generate relative permeabilities and sensitivity to wettability. Physical steady-state and digital relative permeabilities on several core plugs and subsets are compared in this study, which discusses the advantages of performing both as part of the formation evaluation process. The physical and digital results compare reasonably well. The physical results provide a relative permeability anchor, and the digital results provide the leverage of early results, parametric sensitivities, and quality assurance. Hence, integration between digital and physical core analysis yields a robust understanding and input for uncertainty modeling.

Experimental determination of Fe–Mg interdiffusion in orthopyroxene as a function of Fe content

We have measured the dependence of the Fe–Mg interdiffusion coefficient, DFe-Mg, on the ferrosilite component in orthopyroxene, which so far has not been experimentally calibrated. Diffusion couples, consisting of approximately 1 µm thin-films were deposited by pulsed laser ablation on orthopyroxene crystals of En91Fs9 composition. Diffusion experiments were carried out at atmospheric pressure in vertical gas mixing furnaces (CO-CO2) at temperatures between 950 and 1100 °C at constant fO2 = 10–7 Pa. Using a focused ion beam-scanning electron microscope (FIB-SEM), FIB-foils were cut from diffusion couples before and after annealing. Diffusion profiles were extracted by using combined backscattered electron (BSE) imaging and energy dispersive X-ray (EDXS) mapping on FIB-foils which allowed to resolve concentration gradients within 20 nm. The microstructure of the diffusion experiments was investigated using transmission electron microscopy (TEM). Using this method, we obtained the first experimentally determined data on the dependence of DFe-Mg on the ferrosilite content in orthopyroxene at different temperatures, appearing to increase with increasing a temperature. For the temperature range (950 – 1100 °C), log fO2 = -7 Pa, along [001] in the composition Fs9, the log DFe-Mg yields the following Arrhenius equation:DFe-Mg[m2/s]=3.8·10-9exp[-261.07±24[kJ/mol]/(R/T[K])]\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$D_{Fe - Mg} [m^2 /s] = 3.8 \\cdot 10^{ - 9} \\exp [ - 261.07 \\pm 24[kJ/mol]/(R/T[K])]$$\\end{document}The effect of XFe on DFe-Mg, given by D(XFe)=D(XFe=0.09)·10m(XFe-0.09),\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$D(X_{Fe} ) = D(X_{Fe} = 0.09) \\cdot {10}^{m (X_{Fe} - 0.09)},$$\\end{document} can be calculated by the following parameterization where m follows a linear regression of m on temperature: m=-2.711·104/T(K)+23.5408\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$m = - 2.711 \\cdot 10^4 /T(K) + 23.5408$$\\end{document}By considering the DFe-Mg dependence on XFe, the timescales of natural processes obtained from modelling the compositional zoning of natural crystal may considerably differ from previously estimated timescales.

Microscopic seepage simulation of gas and water in shale pores and slits based on VOF

Abstract The microscopic pore-fracture structure and wettability have a significant influence on the two-phase seepage of shale gas and water. Due to the limitation of experimental conditions, the seepage patterns of gas and water in shale pores and slits under different wetting conditions have not been clarified yet. In this study, the three-dimensional digital rock models of shale inorganic pores, organic pores, and microfractures are established by focused ion beam-scanning electron microscopy scanning, and gas-driven water seepage simulation in shale microscopic pore-fracture structure under different wetting conditions is carried out based on volume of fluid method. The simulation results show that the gas–water relative permeability curves of microfractures are up-concave, and the gas–water relative permeability curves of inorganic and organic pores are up-convex; the gas–water two-phase percolation in microfractures is least affected by the change of wettability, the gas–water two-phase percolation in inorganic pores is most affected by the change of wettability, and the organic pores are in between; the gas–water two-phase percolation zone of microfractures is the largest, and the isotonic saturation is the highest; under the water-wet conditions, the critical gas saturation of microfractures, inorganic pores, and organic pores are 0.13, 0.315, and 0.34, respectively, and the critical gas saturation of organic pores under non-water-wet conditions is 0.525, indicating that under water-bearing conditions, the shale gas flow capacity in water-wet microfractures is the strongest, followed by water-wet inorganic pores, water-wet organic pores, and hydrophobic organic pores, respectively.

Direct Visualization of Chemical Transport in Solid-State Chemical Reactions by Time-of-Flight Secondary Ion Mass Spectrometry.

Systematic control and design of solid-state chemical reactions are required for modifying materials properties and in novel synthesis. Understanding chemical dynamics at the nanoscale is therefore essential to revealing the key reactive pathways. Herein, we combine focused ion beam-scanning electron microscopy (FIB-SEM) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) to track the migration of sodium from a borate coating to the oxide scale during in situ hot corrosion testing. We map the changing distribution of chemical elements and compounds from 50 to 850 °C to reveal how sodium diffusion induces corrosion. The results are validated by in situ X-ray diffraction and post-mortem TOF-SIMS. We additionally retrieve the through-solid sodium diffusion rate by fitting measurements to a Fickian diffusion model. This study presents a step change in analyzing microscopic diffusion mechanics with high chemical sensitivity and selectivity, a widespread analytical challenge that underpins the defining rates and mechanisms of solid-state reactions.

Synthesis of submicron-sized LiNi0.5Co0.2Mn0.3O2 cathode particles via reverse microemulsion method: Tailoring size, interfacial properties, and enhanced electrochemical performance for lithium-ion battery

This study explores the impact of submicron-sized cathode materials on lithium-ion battery performance, an area with limited prior research due to synthetic challenges. Employing the reverse microemulsion method, LiNi0.5Co0.2Mn0.3O2 (NCM) cathode particles with tunable sizes (180 nm to 340 nm) were synthesized. Notably, NCM6.67-4.5, which prepared under the volume ratio of the oil phase to the water phase (i.e. 6.67) and applying 4.5 mL NH4OH as the complexing agent, obtained the largest particle size (340 nm). Further investigation revealed that NCM6.67-4.5 exhibited superior discharge specific capacity (177.54 mAh·g−1) and a high coulomb efficiency (99.5 %). The larger particle size in the submicron range facilitated heightened lithium-ion diffusion rates and reduced polarization. Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) confirmed that increased particle size diminishes specific surface area, mitigating interfacial side reactions during battery cycling. This research underscores the importance of controlling cathode particle size for optimizing electrochemical performance in lithium-ion batteries.

A Multiscale Approach for Assessing Shale Oil Availability: Digital Core, Molecular Simulation, and Machine Learning Analysis

Summary This study presents a novel multiscale approach for assessing the accessibility of shale oil in cores by use of focused ion beam-scanning electron microscopy (FIB-SEM) equipment to build digital core, watershed, and maximum ball methods to extract pore size and shape factor. Then, molecular simulation is used to study the availability of shale oil in individual pores with different shapes and radii. Finally, combining the results of the above two scales, machine learning is used to predict shale oil availability across the entire core. On the core scale, the watershed and maximum ball methods are used to extract the core pore network model, and it is found that square pores occupy the highest proportion among the three pore types, and most of the radii are distributed in the range of 2–3 nm. The molecular-scale dynamic simulation results show that the adsorption forms of shale oil are different in different pores, and the adsorption of shale oil in circular pores is less than that in flat pores. The proportion of shale oil adsorption in square pores is the highest, followed by triangular pores, and the proportion of shale oil adsorption in circular pores is the lowest. The random forest machine learning algorithm is used to predict the availability of shale oil with different pore shapes and obtain the shale oil availability ratio of the whole core. The results show that the pores with a more obvious angular structure show a lower shale oil availability ratio. In general, the impact of pore shapes on shale oil availability is not significant, and the difference between different pore shapes is only 10%. The multiscale evaluation method for shale oil availability proposed in this study is helpful to better understand the availability of shale oil in reservoirs and to optimize recovery strategies.

Pt-Black-Modified (Hemi)spherical AFM Sensors: In Situ Imaging of Light-Driven Hydrogen Peroxide Evolution.

In this work, we present (hemi)spherical atomic force microscopy (AFM) sensors for the detection of hydrogen peroxide. Platinum-black (Pt-B) was electrodeposited onto conductive colloidal AFM probes or directly at recessed microelectrodes located at the end of a tipless cantilever, resulting in electrocatalytically active cantilever-based sensors that have a small geometric area but, due to the porosity of the films, exhibit a large electroactive surface area. Focused ion beam-scanning electron microscopy tomography revealed the porous 3D structure of the deposited Pt-B. Given the accurate positioning capability of AFM, these probes are suitable for local in situ sensing of hydrogen peroxide and at the same time can be used for (electrochemical) force spectroscopy measurements. Detection limits for hydrogen peroxide in the nanomolar range (LOD = 68 ± 7 nM) were obtained. Stability test and first in situ proof-of-principle experiments to achieve the electrochemical imaging of hydrogen peroxide generated at a microelectrode and at photocatalytically active structured poly(heptazine imide) films are demonstrated. Force spectroscopic data of the photocatalyst films were recorded in ambient conditions, in solution, and by applying a potential, which demonstrates the versatility of these novel Pt-B-modified spherical AFM probes.

Multiscale investigation of pore structure heterogeneity in carbonate rocks using digital imaging and SCAL measurements: A case study from Upper Jurassic limestones, Abu Dhabi, UAE.

This study presents a comprehensive analysis of rock properties for a selected group of six carbonate reservoir rock samples revealing complex structures at various length scales. Experimental laboratory methods as well as image analysis techniques were conducted in this study to characterize the macro- and micro-pores in mud- and grain-dominated limestones samples from the Upper Jurassic Arab Formation (Arab D member). Mercury Injection Capillary Pressure (MICP), porosimeter, and permeameter lab measurements were employed to assess the pore network heterogeneity and complexity. In addition, a multiscale rock imaging approach was implemented to detect grain and pore phases at several length scales using Thin Sections (TS), Scanning Electron Microscopy (SEM), Focused Ion Beam Scanning Electron Microscopy (FIB-SEM), as well as 3D X-ray Computed Tomography (CT), and micro-computed tomography images (MCT). Furthermore, the multifractal analysis method was applied on the MICP and FIB-SEM to characterize quantitatively the heterogeneity of the pores in the studied samples. Heterogeneous samples 3R, 4M, 5W, and 6M display the highest non-uniformity degree Δα values, falling within the range of [1.21, 1.39] based on FIB-SEM images. Samples 1G, 2R, 3R, and 5W exhibit more heterogeneous pore structure, with Δα values ranging from 0.73 to 1.49 based on the MICP experiments. The results and findings confirm the effectiveness of multifractal parameters Δα and the asymmetry degree in the vertical axis Δf(α) in quantifying and characterizing rock heterogeneity.

Three-dimensional correlative microscopy of the Drosophila female reproductive tract reveals modes of communication in seminal receptacle sperm storage

In many taxa, females store sperm in specialized storage organs. Most insect sperm storage organs have a tubular structure, typically consisting of a central lumen surrounded by epithelial cells. These specialized tubules perform the essential tasks of transporting sperm through the female reproductive tract and supporting long-term sperm survival and function. Little is known about the way in which female sperm storage organs provide an environment conducive to sperm survival. We address this using a combined light microscopy, micro computed tomography (microCT), and Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) approach for high-resolution correlative three-dimensional imaging to advance our understanding of sperm-female interactions in Drosophila melanogaster. Using this multimodal approach, we were able to scan the lower female reproductive tract and distal portion of the seminal receptacle at low magnification, and to subsequently zoom in for further analysis on an ultrastructural level. Our findings highlight aspects of the way in which the seminal receptacle keeps sperm viable in the lumen, and set the stage for further studies. The methods developed are suitable not only for Drosophila but also for other organisms with soft, delicate tissues.

Quantitative characterization of organic and inorganic pores in shale based on deep learning

Organic matter (OM) maturity is closely related to organic pores in shales. Quantitative characterization of organic and inorganic pores in shale is crucial for rock-physics modeling and reservoir porosity and permeability evaluation. Focused ion beam-scanning electron microscopy (FIB-SEM) can capture high-precision three-dimensional (3D) images and directly describe the types, shapes, and spatial distribution of pores in shale gas reservoirs. However, due to the high scanning cost, wide 3D view field, and complex microstructure of FIB-SEM, more efficient segmentation for the FIB-SEM images is required. For this purpose, a multiphase segmentation workflow in conjunction with a U-net is developed to segment pores from the matrix and distinguish organic pores from inorganic pores simultaneously in the entire 3D image stack. The workflow is repeated for FIB-SEM data sets of 17 organic-rich shales with various characteristics. The analysis focuses on improving the efficiency and relevance of the workflow, that is, quantifying the minimum number of training slices while ensuring accuracy and further combining the fractal dimension (FD) and lacunarity to study a simple and objective method of selection. Meanwhile, the computational efficiency, accuracy, and robustness to noise of the 2D U-net model are discussed. The intersection over the union of automatic segmentation can amount to 80%–95% in all data sets with manual labels as ground truth. In addition, calculated by the FIB-SEM multiphase segmentation, the organic porosity is used to quantitatively evaluate the OM decomposition level. Deep-learning-based segmentation shows great potential for characterizing shale pore structures and quantifying OM maturity.

Focused ion beam-SEM 3D study of osteodentin in the teeth of the Atlantic wolfish Anarhichas lupus

The palette of mineralized tissues in fish is wide, and this is particularly apparent in fish dentin. While the teeth of all vertebrates except fish contain a single dentinal tissue type, called orthodentin, dentin in the teeth of fish can be one of several different tissue types. The most common dentin type in fish is orthodentin. Orthodentin is characterized by several key structural features that are fundamentally different from those of bone and from those of osteodentin. Osteodentin, the second-most common dentin type in fish (based on the tiny fraction of fish species out of ∼30,000 extant fish species in which tooth structure was so far studied), is found in most Selachians (sharks and rays) as well as in several teleost species, and is structurally different from orthodentin.Here we examine the hypothesis that osteodentin is similar to anosteocytic bone tissue in terms of its micro- and nano-structure. We use Focused Ion Beam-Scanning Electron Microscopy (FIB/SEM), as well as several other high-resolution imaging techniques, to characterize the 3D architecture of the three main components of osteodentin (denteons, inter-denteonal matrix, and the transition zone between them). We show that the matrix of osteodentin, although acellular, is extremely similar to mammalian osteonal bone matrix, both in general morphology and in the three-dimensional nano-arrangement of its mineralized collagen fibrils. We also document the presence of a complex network of nano-channels, similar to such networks recently described in bone. Finally, we document the presence of strings of hyper-mineralized small ‘pearls’ which surround the denteonal canals, and characterize their structure.

A Dynamic Permeability Model in Shale Matrix after Hydraulic Fracturing: Considering Mineral and Pore Size Distribution, Dynamic Gas Entrapment and Variation in Poromechanics

Traditional research on apparent permeability in shale reservoirs has mainly focussed on effects such as poromechanics and porosity-assisted adsorption layers. However, for a more realistic representation of field conditions, a comprehensive multi-scale and multi-flowing mechanism model, considering the fracturing process, has not been thoroughly explored. To address this research gap, this study introduces an innovative workflow for dynamic permeability assessment. Initially, an accurate description of the pore size distribution (PSD) within three major mineral types in shale is developed using focussed ion beam-scanning electron microscopy (FIB-SEM) and nuclear magnetic resonance (NMR) data. Subsequently, an apparent permeability model is established by combining the PSD data, leading to the derivation of dynamic permeability. Finally, the PSD-related dynamic permeability model is refined by incorporating the effects of imbibition resulting from the fracturing process preceding shale gas production. The developed dynamic permeability model varies with pore and fracture pressures in the shale reservoir. The fracturing process induces water blockage, water-film formation, and water-bridging phenomena in shale, requiring additional pressure inputs to counteract capillary effects in hydrophilic minerals in shale, But also increases the overall permeability from increasing permeability at larger scale pores. Unlike traditional reservoirs, the production process commences when the fracture is depleted to 1–2 MPa exceeds the pore pressure, facilitated by the high concentration of hydrophobic organic matter pores in shale, this phenomenon explains the gas production at the intial production stage. The reduction in adsorption-layer thickness resulting from fracturing impacts permeability on a nano-scale by diminishing surface diffusion and the corresponding slip flow of gas. this phenomenon increases viscous-flow permeability from enlarged flow spacing, but the increased viscous flow does not fully offset the reduction caused by adsorbed-gas diffusion and slip flow. In addition to the phenomena arising from various field conditions, PSD in shale emerges as a crucial factor in determining dynamic permeability. Furthermore, considering the same PSD in shale, under identical pore spacing, the shape factor of slit-like clay minerals significantly influences overall permeability characteristics, much more slit-shaped pores(higher shape factor) reduce the overall permeability. The dynamic permeability-assisted embedded discrete fracture model (EDFM) showed higher accuracy in predicting shale gas production compared to the original model.

Evaluation of ER;CR:YSGG Laser and Remineralization Agents on Mineral Density and Ion Levels of Primary and Permanent Enamel.

Objective: The aim of this study is to evaluate the efficacy of two different fluoride varnishes used alone or in combination with laser treatment on permanent and primary tooth enamel. Methods: Ninety-six primary and 96 permanent molar samples were divided into six groups. The levels of calcium, phosphorus, fluoride, and silver ions of each sample were analyzed using energy-dispersive X-ray spectroscopy (EDS). Six different treatments were applied to 12 different groups (n = 15) as control (g1/G1), fluoride varnish (g2/G2), casein phosphopeptide-amorphous calcium phosphate (CPP-ACP)-fluoride varnish (g3/G3), laser (g4/G4), laser+fluoride varnish (g5/G5), and laser+CPP-ACP-fluoride varnish (g6/G6). After the procedures, ion levels were reanalyzed with EDS. The teeth were subjected to the artificial caries-forming procedure and ion levels were again evaluated by EDS. One sample from each group was prepared separately for the focused ion beam-scanning electron microscope measurement; initial and final images were recorded. The obtained data were statistically analyzed with the SPSS 23.0 program. Results: Compared with the initial measurement, phosphorus percentages increased in most of the groups in the last measurement. Calcium percentages of primary teeth increased in the last measurement, except for the g1 group, but in permanent teeth, there was an increase only in the G6 group. There was a statistically significant difference between g1/G1 and g6/G6 groups in the last measurement of phosphorus and calcium percentages. Conclusions: The combined use of laser with CPP-ACP-fluoride varnish enhanced remineralization in the primary and permanent teeth. However, in permanent teeth, the use of laser alone was not as effective as in primary teeth. Therefore, combined usage with CPP-ACP-fluoride varnish can enhance its efficacy. This in vitro study was approved by the local ethics committee of Hacettepe University (Project No.: GO 20/441).

The Mg Electrode Cycling Mechanism in Simple Salt Glyme Electrolytes

The lithium-ion battery (LIB) has been at the forefront of innovations in energy storage since its commercialisation over 30 years ago. As we reach the practical specific capacity limit of current state-of-the-art materials, novel and innovative battery technologies are required to satiate the requirements of energy intensive applications such as electric vehicles. 1 The use of a lithium metal negative electrode has been proposed to increase the energy density, however the high reactivity causes poor cycling performance due to electrolyte degradation, dendrite formation and safety issues. 2 The magnesium electrode offers a solution that has double the theoretical volumetric capacity of the lithium electrode while simultaneously mitigating dendritic growth, reducing raw material costs and greatly increasing sustainability. 3,4 Previous work has shown that traditional LIB electrolytes are not compatible with magnesium metal, and the plating and stripping mechanism that underpins how magnesium electrodes cycle is poorly understood. 5 Here we explored the mechanism of magnesium plating and stripping in glyme-based electrolytes with a range of additional additives. We show that in the pure electrolyte solution, interphase formation is critical to stable cycling but that this is accompanied by significant degradation and accumulation of inactive Mg.6 We establish the three-dimensional chemical composition of Mg deposits in the different electrolyte formulations using a combination of focused ion beam-scanning electron microscopy (FIB-SEM), energy dispersive x-ray spectroscopy (EDX) and transmission electron microscopy (TEM). We use these findings to develop a mechanistic understanding that explains the electrochemical cycling performance of magnesium metal negative electrodes. In situ electrochemical quartz crystal microbalance (EQCM) measurements are used to evaluate the plating and stripping efficiency of the electrodes and to identify non-electrochemical degradation reactions between Mg and the electrolyte solutions.