Focused Ion Beam Scanning Electron Microscopy Research Articles

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).

Pore development characteristics and controlling factors of Lower Cambrian Qiongzhusi shale gas reservoir in Sichuan Basin, China

Recently, the shale gas exploration of Lower Cambrian Qiongzhusi Formation in Sichuan Basin has made a great breakthrough. However, the pore characteristics and controlling factors of the shale-gas reservoir in the Qiongzhusi Formation are not clear, which hinders further exploration and development of shale gas. This paper focuses on the Qiongzhusi Formation in the Lower Cambrian of the Sichuan Basin. On the basis of mineral composition and the lithofacies types of shale-gas reservoirs in Qiongzhusi Formation were classified by microscopic observation. Additionally, focused ion beam-scanning electron microscope (FIB-SEM), advanced mineral identification and characterization system (AMICS) analysis, large-field stitching scanning electron microscope technology (MAPS) and nitrogen adsorption experiment were employed to comprehensively determine the differential characteristics and controlling factors of pore development. The results indicate that the pore types in Qiongzhusi Formation are mainly composed of interparticle pores and intercrystalline pores. The pore structure of Qiongzhusi Formation is complex. Significant differences in pore structure parameters are observed among different lithofacies. Quartz and feldspar contribute to the preservation of primary pores due to their strong compressive resistance. Clay minerals and carbonate minerals impede pore development by occluding pores. The influence of organic matter on the pore development is relatively small. According to the mineral composition and pore parameters, laminated shale is a relatively favorable reservoir facies among different lithofacies types.

The impact of macrophage phenotype and heterogeneity on the total internalized gold nanoparticle counts.

Macrophages play a pivotal role in the internalization and processing of administered nanoparticles (NPs). Furthermore, the phagocytic capacity and immunological properties of macrophages can vary depending on their microenvironment, exhibiting a spectrum of polarization states ranging from pro-inflammatory M1 to anti-inflammatory M2. However, previous research investigating this phenotype-dependent interaction with NPs has predominantly relied on semi-quantitative techniques or conventional metrics to assess intracellular NPs. Here, we focus on the interaction of human monocyte-derived macrophage phenotypes (M1-like and M2-like) with gold NPs (AuNPs) by combining population-based metrics and single-cell analysis by focused ion beam-scanning electron microscopy (FIB-SEM). The multimodal analysis revealed phenotype-dependent response and uptake behavior differences, becoming more pronounced after 48 hours. The study also highlighted phenotype-dependent cell-to-cell heterogeneity in AuNPs uptake and variability in particle number at the single-cell level, which was particularly evident in M2-like macrophages, which increases with time, indicating enhanced heteroscedasticity. Future efforts to design NPs targeting macrophages should consider the phenotypic variations and the distribution of NPs concentrations within a population, including the influence of cell-to-cell heterogeneity. This comprehensive understanding will be critical in developing safe and effective NPs to target different macrophage phenotypes.

UV-assisted nanoimprint lithography: the impact of the loading effect in silicon on nanoscale patterns of metalens.

This work studies the impact of the silicon (Si) loading effect induced by deep reactive ion etching (DRIE) of silicon master molds on the UV-nanoimprint lithography (NIL) patterning of nanofeatures. The silicon molds were patterned with metasurface features with widths varying from 270 to 60 nm. This effect was studied by focus ion beam scanning electron microscopy (FIB-SEM) and atomic force microscopy (AFM). The Si loading etching effect is characterized by the variation of pattern feature depth concerning feature sizes because smaller features tend to etch more slowly than larger ones due to etchants being more difficult to pass through the smaller hole and byproducts being harder to diffuse out too. Thus, the NIL results obtained from the Si master mold contain different pattern geometries concerning pattern quality and residual photoresist layer thickness. The obtained results are pivotal for NIL for fabricating devices with various geometrical nanostructures as the research field moves towards commercial applications.

Sample preparation and data collection for serial block face scanning electron microscopy of mammalian cell monolayers.

Volume electron microscopy encompasses a set of electron microscopy techniques that can be used to examine the ultrastructure of biological tissues and cells in three dimensions. Two block face techniques, focused ion beam scanning electron microscopy (FIB-SEM) and serial block face scanning electron microscopy (SBF-SEM) have often been used to study biological tissue samples. More recently, these techniques have been adapted to in vitro tissue culture samples. Here we describe step-by-step protocols for two sample embedding methods for in vitro tissue culture cells intended to be studied using SBF-SEM. The first focuses on cell pellet embedding and the second on en face embedding. En face embedding can be combined with light microscopy, and this CLEM workflow can be used to identify specific biological events by light microscopy, which can then be imaged using SBF-SEM. We systematically outline the steps necessary to fix, stain, embed and image adherent tissue culture cell monolayers by SBF-SEM. In addition to sample preparation, we discuss optimization of parameters for data collection. We highlight the challenges and key steps of sample preparation, and the consideration of imaging variables.

A Study on Electrochemical Properties of Fuel-Electrode-Supported Reversible Solid Oxide Cells

Introduction Reversible solid oxide cells (r-SOCs) enable both power generation and steam electrolysis, and have attracted attention as a solid state electrochemical energy device for a decarbonized society (1). R-SOCs have the advantage of high efficiency due to high temperature operation, but there exist various technical issues remained in materials selection, start-up and shutdown, and long-term durability. Therefore, reducing operating temperature is desirable for practical applications (2,3). Electrode-supported cells, in which the electrode acts as a structural support, enable lower temperature operation by reducing the thickness of the electrolyte, which has certain electrical resistivity. Here in this study, the current-voltage characteristics and reversible cycle durability under r-SOC operating conditions are evaluated using fuel-electrode-supported cells, with the aim of developing r-SOCs capable of highly efficient fuel cell power generation and steam electrolysis. Experimental For the experiments, fuel-electrode-supported cells were fabricated using fuel electrode-supported half-cells (Japan Fine Ceramics, Japan), schematically shown in Fig. 1. The half-cell consists of scandia-stabilized zirconia (ScSZ: 10 mol%Sc2O3-1mol%CeO2-89 mol%ZrO2) or yttria-stabilized zirconia (YSZ: 8 mol%Y2O3-92 mol%ZrO2) electrolyte and a Ni-cermet fuel electrode, such as Ni-ScSZ or Ni-YSZ. (La0.6Sr0.4)(Co0.2Fe0.8)O3 (LSCF) was applied for the air electrode, and Gd0.1Ce0.9O2 (GDC) was inserted between the electrolyte and the air electrode to suppress interdiffusion and chemical reactions. Four types of cells were used with different combinations of the electrolyte component (YSZ or ScSZ) in the electrolyte layer or the supporting fuel electrode.In electrochemical tests, 50%-humidified hydrogen (100 ml min-1) was supplied to the fuel electrode, and air (150 ml min-1) was supplied to the air electrode. R-SOC initial performance tests were conducted using an electrochemical analyzer (1255B, Solartron). Cell voltage and impedance were measured at 700-800°C at current densities ranging from -0.5 A cm-2 to +0.5 A cm-2. Positive current density means the value in SOFC mode, while negative current density means the value in SOEC mode. In r-SOC 1,000 cycle durability tests, cycles of switching between SOFC and SOEC operation were repeated 1,000 times by varying current density. The range of current density in the cycle tests was between -0.2 A cm-2 and +0.2 A cm-2. The cell impedance was measured before the cycling test and every 100 cycles. After each test, the cells were analyzed by using a focused-ion beam scanning electron microscopy (FIB-SEM) to observe and evaluate the electrode microstructure. Results and discussion Figure 2 (a) shows the r-SOC initial performance of each fuel-electrode-supported cell. The cell with the Ni-YSZ fuel electrode and the YSZ electrolyte showed better current voltage characteristics than other cells. Figure 2 (b) shows the r-SOC 1000-cycle durability of the cell with the Ni-YSZ fuel electrode and the YSZ electrolyte. The results showed a decrease in power generation and electrolysis performance with increasing the number of cycles in both SOFC and SOEC modes. Possible degradation mechanisms will be discussed. Acknowledgments This paper is based on results obtained from a project (Research and Development Program for Promoting Innovative Clean Energy Technologies Through International Collaboration), JPNP20005, commissioned by the New Energy and Industrial Technology Development Organization (NEDO). Collaborative support by Prof. H. L. Tuller and Prof. B. Yildiz at Massachusetts Institute of Technology (MIT) is gratefully acknowledged. References (1) Venkataraman, M. Pérez-Fortes, L. Wang, Y. S. Hajimolana, C. Boigues-Muñoz, A. Agostini, S. J. Mcphail, F. Mar échal, J. V. Herle, and P. V. Aravind, J. Energy Storage, 24, 100782 (2019).(2) Subotić, S. Pofahl, V. Lawlor, N. H. Menzler, T. Thaller, and C. Hochenauer, Energy Proc., 158, 2329 (2019).(3) B. Mogensen, Current Opinion Electrochem., 21, 265 (2020). Figure 1

Electro-Chemo-Mechanical Study of Cathode-Interface-Engineered All-Solid-State Lithium Batteries

All-solid-state lithium batteries (ASSLBs) have been regarded as one of the most promising next-generation batteries in terms of their superior safety and great potential to meet the requirements of high energy and power density.1 However, the performance of ASSLBs based on even state-of-the-art solid electrolytes (SEs) with a high room-temperature ion conductivity of 10−2 S·cm−1 is still inferior to that of commercially available LIBs, because fast solid electrode/electrolyte interfacial lithium-ion transport remains a vital challenge in ASSLBs.2 The sluggish lithium-ion transport across the solid electrode/electrolyte interface mainly results from the electro-chemo-mechanical degradation, such as the space charge layer (SCL), interface reaction generating ionically resistive products, and poor physical contact.3,4 On the cathode side, coating high-voltage cathodes with chemically compatible and stable buffering layers with high ionic conductivity but low electronic conductivity has been widely confirmed to be an effective approach to overcome these problems.However, a mechanistic understanding of the coating functionality remains unresolved, and there is still much room for improvement regarding the methodology and associated material properties.5 Here, from electro-chemo-mechanical perspectives, we have fully studied the improvement mechanism of cathode interface engineering for ASSLBs based on the complementary analyses including calculations (e.g., first-principles, finite element methods), in-situ (e.g., differential phase contrast scanning transmission electron microscopy (DPC-STEM), Raman, electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT)) and ex-situ (X-ray absorption spectra (XAS), X-ray photoelectron spectroscopy (XPS), focused-ion beam scanning electron microscopy (FIB-SEM)) characterizations. We find that discontinuous ferroelectric BaTiO3 coating can effectively suppress the SCL formation and lead to fast continuous interfacial lithium-ion conduction pathways, thus significantly improving the interfacial migration kinetics between cathode materials and the sulfide SEs.6 The bidirectionally compatible NASICON-type LixZr2(PO4)3 (LZPO) buffering layer enables the high-voltage cathode interface (4.5 V LiCoO2/Li6PS5Cl) with high chemical/electrochemical stability and fast Li-ion transport dynamics.7 Additionally, the high Young’s modulus of the coating layer (e.g., LZPO) can remarkably decrease stress inside cathodes and prevent cathode/SE interface separation, which is beneficial to mitigate microcracks in cathodes and cathode/SE interface contact loss, respectively.8 We believe these findings will help advance the fundamental scientific understanding of the coating functionality and the interfacial lithium-ion transport mechanism in ASSLBs, thus shed light on rational electrode/electrolyte interface design for high-rate performance ASSLBs.References Janek, J. & Zeier, W. G. A solid future for battery development. Nat. Energy 1, 16141 (2016).Janek, J. & Zeier, W. G. Challenges in speeding up solid-state battery development. Nat. Energy, doi:10.1038/s41560-023-01208-9 (2023).Banerjee, A., Wang, X., Fang, C., Wu, E. A. & Meng, Y. S. Interfaces and Interphases in All-Solid-State Batteries with Inorganic Solid Electrolytes. Chem. Rev. 120, 6878–6933 (2020).Chen, R., Li, Q., Yu, X., Chen, L. & Li, H. Approaching Practically Accessible Solid-State Batteries: Stability Issues Related to Solid Electrolytes and Interfaces. Chem. Rev. 120, 6820–6877 (2020).Culver, S. P., Koerver, R., Zeier, W. G. & Janek, J. On the functionality of coatings for cathode active materials in thiophosphate-based all-solid-state batteries. Adv. Energy Mater. 9, 1900626 (2019).Wang, L. et al. In-situ visualization of the space-charge-layer effect on interfacial lithium-ion transport in all-solid-state batteries. Nat. Commun. 11, 5889 (2020).Wang, L. et al. Bidirectionally compatible buffering layer enables highly stable and conductive interface for 4.5 V sulfide-based all-solid-state lithium batteries. Adv. Energy Mater. 11, 2100881 (2021).Sun, X. et al. A Bifunctional Chemomechanics Strategy To Suppress Electrochemo-Mechanical Failure of Ni-Rich Cathodes for All-Solid-State Lithium Batteries. ACS Appl. Mater. Interfaces 14, 17674–17681 (2022).

Distribution of Relaxation Times of Fuel Electrodes for Reversible Solid Oxide Cells Fabricated Under Various Conditions

Introduction Reversible solid oxide cells (r-SOCs) are electrochemical energy devices that can switch reversibly between power generation as a solid oxide fuel cell (SOFC) and hydrogen production as a solid oxide electrolysis cell (SOEC). It is important to systematically understand the electrode reaction processes and degradation factors in these two modes to tailor high-performance and durable r-SOC electrodes. The dependence of polarization resistance on cell fabrication conditions and operating conditions has been individually investigated for SOFC and SOEC by impedance measurement and distribution of relaxation times (DRT) analysis [1-4], but it is necessary to evaluate r-SOC as a whole [5]. Here in this study, we aim to systematically clarify the similarities and differences in the electrode reaction processes at the fuel electrodes of both SOFC and SOEC modes of r-SOCs, with respect to fuel electrode fabrication conditions. Experimental Several types of cells were fabricated with different fuel electrode constituent materials, thicknesses, and sintering temperatures. Three types of fuel electrode materials were used: Ni-GDC cermet, a composite of Ni and mixed ionic-electronic conductor Gd0.9Ce0.1O3 (GDC); Ni-YSZ cermet, a composite of Ni and pure ionic conductor YSZ (8 mol% Y2O3 - stabilized ZrO2); and Ni-GDC co-impregnated electrode with LST-GDC as a backbone support (LST: La0.1Sr0.9TiO3). Scandia-stabilized zirconia (ScSZ) was used as the electrolyte plate, and (La0.6Sr0.4)(Co0.2Fe0.8)O3 (LSCF) was used as the air electrode. GDC buffer layer was prepared between the electrolyte and the air electrode to suppress the formation of interfacial insulting layers.Electrochemical impedance measurements were performed for the fuel electrode of the fabricated cell under SOFC and SOEC modes by supplying H2-H2O mixture and varying operating temperature, fuel humidification, and current density. The DRT analysis was conducted to separate various polarization resistance components of the fuel electrode with different relaxation times. The area of each DRT peak corresponds to the resistance of each electrode reaction process. In this study, activation energy was derived based on the assumption that the electrical conductance is of an Arrhenius-type thermally activated character. Its dependence on the fuel electrode fabrication conditions was investigated. Furthermore, electrode microstructure was observed by using focused-ion beam scanning electron microscopy (FIB-SEM). Results and Discussion Figure 1 shows typical DRT peaks of the Ni-GDC cermet fuel electrode in (a) SOFC and (b) SOEC modes, measured at different temperatures. In the range of 10-1 to 106 Hz where the frequency response was measured, three DRT peaks appeared, P1: 10-1 to 100 Hz, P2: 100 to 102 Hz, and P3: 102 to 103 Hz, all with a DRT peak area decreasing with increasing operating temperature. This indicates that there are at least three electrode reaction processes with different relaxation times, which are thermally active processes. Activation energies of 0.1-0.3 eV (SOFC mode) and 0.2-0.5 eV (SOEC mode) were obtained for P1, and 0.9-1.0 eV (SOFC mode) and 1.1-1.3 eV (SOEC mode) for P2. The activation energies in SOEC mode were higher than those in SOFC mode for both P1 and P2. In the presentation, the dependence of activation energies on the fuel electrode constituent materials and related electrode reaction processes will be discussed.

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.

Monitoring Copper Ion Leaching from a Metalloporphyrin-Based Cathode for Rechargeable Magnesium Batteries

Great efforts are being undertaken to characterize the fundamental processes of solid electrolyte interphase (SEI) formation, degradation, and initial conditioning steps of battery electrode materials, including organic electrode materials.[1] Imaging techniques, such as focused ion beam / scanning electron microscopy (FIB/SEM) tomography in combination with element mapping using energy- and wavelength-dispersive X-ray spectroscopy are employed to gain insight into distribution, interconnectivity, and porosity of active materials as well as electrolyte penetration and their influence on degradation processes after longer cycling times.[2] Additionally, electrochemical impedance spectroscopy[3] and anodic stripping voltammetry[4] are used to shed light on those processes. The metalloporphyrin-based material [5,15-bis(ethynyl)-10,20-diphenylporphinato]copper(II) (CuDEPP) has been used as an interesting material for cathodes and anodes of various battery chemistries. These materials undergo initial self-conditioning by electro-polymerization for monovalent ions. With respect to multivalent ions, like magnesium, this polymerization is far less pronounced and an exchange of the copper from the CuDEPP by magnesium ions appears to be occurring.[5] Gaining insight into this trans- or demetallation process induced by parameters like the electrochemical driving force during galvanostatic cycling is a complex analytical challenge.We report the use of Hg ultramicroelectrodes and anodic stripping voltammetry as a sensitive strategy to detect copper ion leaching from metalloporphyrin-based CuDEPP composite electrodes. We demonstrate in-situ/intermittent monitoring of copper ion release during the initial self-conditioning step of the active material while galvanostatic cycling of the battery electrode in dimethoxy ethane. This method could be used to assess the release of an ionic species from complex systems, like composite battery electrodes.

Insights into Performance and Degradation of Commercial Ni-Rich Cathodes: A Modeling Perspective

Li-ion batteries are widely used in consumer electronics due to their high energy density and currently gain further importance with regards to future mobility and their application in electric vehicles. While a high nickel content in stoichiometries like LiNi0.8Mn0.1Co0.1O2 (NMC811) increases the achievable capacity in a given voltage window, it also poses challenges to structural stability during cycling [1]. Therefore, application and further development of those materials requires a deep understanding of their performance limitations as well as their degradation. Since extensive testing is time-consuming and expensive, predictive simulation tools are needed that are able to describe the electrochemical behavior of the cell.In this contribution, we will present 3D microstructure-resolved electrochemical continuum simulations conducted in the simulation framework BEST. It is based on a thermodynamically consistent transport theory for mass and charge in the electrolyte and the active material [2]. Owing to the finite volume discretization of the governing equations, it is straightforward to use voxel-based image data obtained by focused ion beam - scanning electron microscopy (FIB-SEM) as the simulation domain. Previous studies have shown the importance of microstructural simulations with regards to battery operation [3] and contributed to a deeper insight into the cell aging [4]. This approach will be complemented by a pseudo-2D (p2D) model considering different aging modes, thus providing additional predictions on the cell aging.In our work we analyze commercial NMC811/graphite cells. We demonstrate a very good agreement at the beginning of life between our simulations and experimental data obtained in rate tests and electrochemical impedance spectroscopy (EIS). In the high-energy cathodes we found a very low content (3 vol-%) of carbon binder domain (CBD), which is insufficient to establish a conductive network. Hence, the electronic conductivity of the active material determines the effective conductivity of the electrode and limits the performance at high degrees of lithiation. Additionally, we evaluate the degradation of the NMC active material using our simulation approach.Combining the 3D microstructure-resolved simulations with an efficient p2D model provides a valuable toolchain to gain a comprehensive understanding of the performance limitations as well as the relevant aging modes in commercially available high-energy cathodes.Acknowledgement:This work has been funded by the ‘Bundesministerium für Bildung und Forschung’ within the project MiCha under the reference number 03XP0317D. The authors acknowledge support by the state of Baden-Württemberg through bwHPC (JUSTUS 2).

Ultrahigh-Resolution Reconstruction of Shale Digital Rocks from FIB-SEM Images Using Deep Learning

Summary Accurate characterization of shale pore structures is of paramount importance in elucidating the distribution and migration mechanisms of fluids within shale rocks. However, the acquisition of high-resolution (HR) images of shale rocks is limited by the precision of the scanning equipment. Even with higher-precision devices, compromising the image field of view becomes inevitable, making it challenging to faithfully represent the actual conditions of shale. We propose a stepwise 3D super-resolution (SR) reconstruction method for shale digital rocks based on the widely used focused-ion-beam scanning electron microscope (FIB-SEM) technique. This method effectively addresses the issues of inconsistent horizontal and vertical resolutions as well as low 3D image resolution in FIB-SEM images. By adopting this approach, we significantly enhance image details and clarity, enabling successful observations of pores smaller than 10 nm within shale and laying a foundation for further pore-scale flow simulations. Furthermore, we extract the pore network model (PNM) from the SR reconstructed digital rock to analyze the pore size distribution, coordination number, and pore-throat ratio of shale samples from the Jiyang Depression. The results demonstrate a pore radius distribution in the range of 0 nm to 40 nm, which aligns with the results from nitrogen adsorption experiments. Notably, pores with radii smaller than 10 nm account for 50% of the total connected pores. The proportion of isolated pores in the SR reconstructed shale PNM is significantly reduced, with the coordination number mainly distributed between 1 and 4. The pore-throat ratio of shale ranges from 1 to 3, indicating a relatively uniform development of pores and throats. This study introduces a novel method for accurately characterizing the shale pore structure, which aids researchers in evaluating the pore size distribution and connectivity of shales.

Segmentation of cellular ultrastructures on sparsely labeled 3D electron microscopy images using deep learning.

Focused ion beam-scanning electron microscopy (FIB-SEM) images can provide a detailed view of the cellular ultrastructure of tumor cells. A deeper understanding of their organization and interactions can shed light on cancer mechanisms and progression. However, the bottleneck in the analysis is the delineation of the cellular structures to enable quantitative measurements and analysis. We mitigated this limitation using deep learning to segment cells and subcellular ultrastructure in 3D FIB-SEM images of tumor biopsies obtained from patients with metastatic breast and pancreatic cancers. The ultrastructures, such as nuclei, nucleoli, mitochondria, endosomes, and lysosomes, are relatively better defined than their surroundings and can be segmented with high accuracy using a neural network trained with sparse manual labels. Cell segmentation, on the other hand, is much more challenging due to the lack of clear boundaries separating cells in the tissue. We adopted a multi-pronged approach combining detection, boundary propagation, and tracking for cell segmentation. Specifically, a neural network was employed to detect the intracellular space; optical flow was used to propagate cell boundaries across the z-stack from the nearest ground truth image in order to facilitate the separation of individual cells; finally, the filopodium-like protrusions were tracked to the main cells by calculating the intersection over union measure for all regions detected in consecutive images along z-stack and connecting regions with maximum overlap. The proposed cell segmentation methodology resulted in an average Dice score of 0.93. For nuclei, nucleoli, and mitochondria, the segmentation achieved Dice scores of 0.99, 0.98, and 0.86, respectively. The segmentation of FIB-SEM images will enable interpretative rendering and provide quantitative image features to be associated with relevant clinical variables.

Bundling of collagen fibrils influences osteocyte network formation during bone modeling

Osteocytes form a cellular network by gap junctions between their cell processes. This network is important since intercellular communication via the network is essential for bone metabolism. However, the factors that influence the formation of this osteocyte network remain unknown. As the early stage of osteocyte network formation occurs on the bone surface, we observed a newly formed trabecular bone surface by orthogonal focused ion beam-scanning electron microscopy. The embedding late osteoblast processes tended to avoid bundled collagen fibrils and elongate into sparse collagen fibrils. Then, we examined whether the inhibition of bundling of collagen fibrils using a potent lysyl oxidase inhibitor, β-aminopropionitrile (BAPN) changed the cellular network of the chick calvaria. The osteocyte shape of the control group was spindle-shape, while that of the BAPN group was sphere-shaped. In addition, the osteocyte processes of the control group were elongated vertically to the long axis of the cell body, whereas the osteocyte processes of the BAPN group were elongated radially. Therefore, it was suggested that the bundling of collagen fibrils influences normal osteocyte network formation during bone modeling.

Characterization for 3D pore-fracture systems in Hot-Dry-Rock samples from Gonghe Basin, China

As a new type of renewable energy, Hot-Dry-Rock (HDR) is gaining increasing attention. The physical properties of rock influenced by the pore-fracture structure are vital for the hydraulic and chemical characteristics of HDR reservoirs. However, the natural pore-fracture structure in HDR has not been sufficiently studied. To fulfill this gap, we used focused ion beam-scanning electron microscopy (FIB-SEM) to construct three-dimensional (3D) digital models for four granite samples from the deep HDR reservoir in Gonghe Basin, Qinghai Province, China, and obtained the nanoscale structure of the pores and fractures in HDR reservoir for the first time. Our analysis based on the 3D models indicates that the heat transfer area in the HDR reservoir is mainly from fractures and crack-like pores, but a large amount of small but regular pores could be neglected when heat transfer in HDR is considered. The permeability of HDR reservoirs at nanoscale varies from 9.414 nD to 0.082 mD, and the high permeability in this study is accompanied by throughgoing fractures. The variation of porosity and permeability of deep HDR at nanoscale in this study is much more severe than that of shallow granites previously studied at microscale. The performance of geothermal field is significantly influenced by the size of throats and the average size and tortuosity of the interconnected pore-fracture network in HDR. The hydraulic aperture could be 32-58% lower than the mechanical aperture of the natural fractures in HDR reservoirs, which is a vital clue for the numerical simulation associated with enhanced geothermal systems.

CDK2 inhibition disorders centrosome stoichiometry and alters cellular outcomes in aneuploid cancer cells

ABSTRACT Cyclin-dependent Kinase 2 (CDK2) inhibition prevents supernumerary centrosome clustering. This causes multipolarity, anaphase catastrophe and apoptotic death of aneuploid cancers. This study elucidated how CDK2 antagonism affected centrosome stoichiometry. Focused ion beam scanning electron microscopy (FIB-SEM) and immunofluorescent imaging were used. Studies interrogated multipolar mitosis after pharmacologic or genetic repression of CDK2. CDK2/9 antagonism with CYC065 (Fadraciclib)-treatment disordered centrosome stoichiometry in aneuploid cancer cells, preventing centrosome clustering. This caused ring-like chromosomes or multipolar cancer cells to form before onset of cell death. Intriguingly, CDK2 inhibition caused a statistically significant increase in single centrioles rather than intact centrosomes with two centrioles in cancer cells having chromosome rings or multipolarity. Statistically significant alterations in centrosome stoichiometry were undetected in other mitotic cancer cells. To confirm this pharmacodynamic effect, CDK2 but not CDK9 siRNA-mediated knockdown augmented cancer cells with chromosome ring or multipolarity formation. Notably, engineered gain of CDK2, but not CDK9 expression, reversed emergence of cancer cells with chromosome rings or multipolarity, despite CYC065-treatment. In marked contrast, CDK2 inhibition of primary human alveolar epithelial cells did not confer statistically significant increases of cells with ring-like chromosomes or multipolarity. Hence, CDK2 antagonism caused differential effects in malignant versus normal alveolar epithelial cells. Translational relevance was confirmed by CYC065-treatment of syngeneic lung cancers in mice. Mitotic figures in tumors exhibited chromosome rings or multipolarity. Thus, CDK2 inhibition preferentially disorders centrosome stoichiometry in cancer cells. Engaging this disruption is a strategy to explore against aneuploid cancers in future clinical trials.

Visualizing the Structure, Composition and Activity of Single Catalyst Particles for Olefin Polymerization and Polyolefin Decomposition.

The structural and morphological characterization of individual catalyst particles for olefin polymerization, as well as for the reverse process of polyolefin decomposition, can provide an improved understanding for how these catalyst materials operate under relevant reaction conditions. In this review, we discuss an emerging analytical toolbox of 2D and 3D chemical imaging techniques that is suitable for investigating the chemistry and reactivity of related catalyst systems. While synchrotron-based X-ray microscopy still provides unparalleled spatial resolutions in 2D and 3D, a number of laboratory-based techniques, most notably focused ion beam-scanning electron microscopy, confocal fluorescence microscopy, infrared photoinduced force microscopy and laboratory-based X-ray nano-computed tomography, have helped to significantly expand the arsenal of analytical tools available to scientists in heterogeneous catalysis and polymer science. In terms of future research, the review outlines the role and impact of in situ and operando (spectro-)microscopy experiments, involving sophisticated reactors as well as online reactant and product analysis, to obtain real-time information on the formation, decomposition, and mobility of polymer phases within single catalyst particles. Furthermore, the potential of fluorescence microscopy, X-ray microscopy and optical microscopy is highlighted for the high-throughput characterization of olefin polymerization and polyolefin decomposition catalysts. By combining these chemical imaging techniques with, for example, chemical staining methodologies, selective probe molecules as well as particle sorting approaches, representative structure-activity relationships can be derived at the level of single catalyst particles.

Local Structural Modifications in Metallic Micropillars Induced by Plasma Focused Ion Beam Processing.

A focused ion beam scanning electron microscope (FIB-SEM) is a powerful tool that is routinely used for scale imaging from the micro- to nanometer scales, micromachining, prototyping, and metrology. In spite of the significant capabilities of a FIB-SEM, there are inherent artefacts (e.g., structural defects, chemical interactions and phase changes, ion implantation, and material redeposition) that are produced due to the interaction of Ga+ or other types of ions (e.g., Xe+, Ar+, O+, etc.) with the sample. In this study, we analyzed lattice distortion and ion implantation and subsequent material redeposition in metallic micropillars which were prepared using plasma focus ion beam (PFIB) milling. We utilized non-destructive synchrotron techniques such as X-ray fluorescence (XRF) and X-ray nanodiffraction to examine the micropillars prepared using Xe+ ion energies of 10 keV and 30 keV. Our results demonstrate that higher Xe ion energy leads to higher density of implanted ions within the redeposited and milled material. The mixing of ions in the redeposited material significantly influences the lattice structure, causing deformation in regions with higher ion concentrations. Through an X-ray nanodiffraction analysis, we obtained numerical measurements of the strain fields induced in the regions, which revealed up to 0.2% lattice distortion in the ion bombardment direction.