Fe-modified Mn2CuO4 spinel oxides: coatings based on abundant elements for solid oxide cell interconnects

The current state of the art steel interconnect coating materials are based on critical raw material - Co-oxide spinels. Replacing Co-oxide spinels with alternative, abundant materials can reduce the dependence on the critical raw materials. Cobalt-free coatings with the general formula Mn2-xCuFexO4, where x = 0, 0.1, 0.3, were electrophoretically deposited on a ferritic stainless-steel support and evaluated. Prior to deposition, the powders were prepared by a soft chemistry process and studied in terms of crystallographic phase analysis, electrical conductivity, thermal expansion, and sinterability behaviour. Coated steel samples were oxidised in an air atmosphere at 750 \ub0C for 3000 h. In parallel, a state-of-the-art MnCo2O4 spinel oxide was tested as a reference. The coatings and oxide scale microstructures of the surfaces and cross-sections were examined by XRD, and SEM-EDX. TEM-EDX, XRF, and micro-XRD were also performed on the cross-section lamellae. The electrical properties of the steel-coating system were evaluated by Area Specific Resistance measurement. The results confirm that Mn–Cu–Fe oxides exhibit higher conductivity and lower TEC than Mn–Co oxide. Based on the obtained results, it might be concluded that the proposed coatings are a promising alternative to coatings that contain cobalt

Chemical gradients in automotive Cu-SSZ-13 catalysts for NOx_{x} removal revealed by operando X-ray spectrotomography

NOx emissions are a major source of pollution, demanding ever improving performance from catalytic aftertreatment systems. However, catalyst development is often hindered by limited understanding of the catalyst at work, exacerbated by widespread use of model rather than technical catalysts, and global rather than spatially-resolved characterisation tools. Here we combine operando X-ray absorption spectroscopy with microtomography to perform 3D chemical imaging of the chemical state of copper species in a Cu-SSZ-13 washcoated monolith catalyst during NO$_{x}$ reduction. Gradients in copper oxidation state and coordination environment, resulting from an interplay of NOx reduction with adsorption-desorption of NH$_{3}$ and mass transport phenomena, were revealed with micrometre spatial resolution while simultaneously determining catalytic performance. Crucially, direct 3D visualisation of complex reactions on nonmodel catalysts is only feasible using operando X-ray spectrotomography, which can improve our understanding of structure-activity relationships including the observation of mass and heat transport effects

Non‐Destructive X‐Ray Imaging of Patterned Delta‐Layer Devices in Silicon

The progress of miniaturization in integrated electronics has led to atomic and nanometer-sized dopant devices in silicon. Such structures can be fabricated routinely by hydrogen resist lithography, using various dopants such as P and As. However, the ability to non-destructively obtain atomic-species-specific images of the final structure, which would be an indispensable tool for building more complex nano-scale devices, such as quantum co-processors, remains an unresolved challenge. Here, X-ray fluorescence is exploited to create an element-specific image of As dopants in Si, with dopant densities in absolute units and a resolution limited by the beam focal size (here ≈1 µm), without affecting the device's low temperature electronic properties. The As densities provided by the X-ray data are compared to those derived from Hall effect measurements as well as the standard non-repeatable, scanning tunneling microscopy and secondary ion mass spectroscopy, techniques. Before and after the X-ray experiments, we also measured the magneto-conductance, which is dominated by weak localization, a quantum interference effect extremely sensitive to sample dimensions and disorder. Notwithstanding the 1.5 × 10^{10} Sv (1.5 × 10^{16} Rad cm^{−2}) exposure of the device to X-rays, all transport data are unchanged to within experimental errors, corresponding to upper bounds of 0.2 Angstroms for the radiation-induced motion of the typical As atom and 3% for the loss of activated, carrier-contributing dopants. With next generation synchrotron radiation sources and more advanced optics, the authors foresee that it will be possible to obtain X-ray images of single dopant atoms within resolved radii of 5 nm

Unraveling structural and compositional information in 3D FinFET electronic devices

Non-planar Fin Field Effect Transistors (FinFET) are already present in modern devices. The evolution from the well-established 2D planar technology to the design of 3D nanostructures rose new fabrication processes, but a technique capable of full characterization, particularly their dopant distribution, in a representative (high statistics) way is still lacking. Here we propose a methodology based on Medium Energy Ion Scattering (MEIS) to address this query, allowing structural and compositional quantification of advanced 3D FinFET devices with nanometer spatial resolution. When ions are backscattered, their energy losses unfold the chemistry of the different 3D compounds present in the structure. The FinFET periodicity generates oscillatory features as a function of backscattered ion energy and, in fact, these features allow a complete description of the device dimensions. Additionally, each measurement is performed over more than thousand structures, being highly representative in a statistical meaning. Finally, independent measurements using electron microscopy corroborate the proposed methodolog

Vadose-Zone Alteration of Metaschoepite and Ceramic UO2 in Savannah River Site Field Lysimeters

Uranium dioxide (UO2) and metaschoepite (UO3•nH2O) particles have been identified as contaminants at nuclear sites. Understanding their behavior and impact is crucial for safe management of radioactively contaminated land and to fully understand U biogeochemistry. The Savannah River Site (SRS) (South Carolina, USA), is one such contaminated site, following historical releases of U-containing wastes to the vadose zone. Here, we present an insight into the behavior of these two particle types under dynamic conditions representative of the SRS, using field lysimeters (15 cm D x 72 cm L). Discrete horizons containing the different particle types were placed at two depths in each lysimeter (25 cm and 50 cm) and exposed to ambient rainfall for 1 year, with an aim of understanding the impact of dynamic, shallow subsurface conditions on U particle behavior and U migration. The dissolution and migration of U from the particle sources and the speciation of U throughout the lysimeters was assessed after 1 year using a combination of sediment digests, sequential extractions, and bulk and μ-focus X-ray spectroscopy. In the UO2 lysimeter, oxidative dissolution of UO2 and subsequent migration of U was observed over 1–2 cm in the direction of waterflow and against it. Sequential extractions of the UO2 sources suggest they were significantly altered over 1 year. The metaschoepite particles also showed significant dissolution with marginally enhanced U migration (several cm) from the sources. However, in both particle systems the released U was quantitively retained in sediment as a range of different U(IV) and U(VI) phases, and no detectable U was measured in the lysimeter effluent. The study provides a useful insight into U particle behavior in representative, real-world conditions relevant to the SRS, and highlights limited U migration from particle sources due to secondary reactions with vadose zone sediments over 1 year.Peer reviewe

Evidence for Metabolic Diversity in Meso-Neoproterozoic Stromatolites (Vazante Group, Brazil)

Deciphering the evolution of ecological interactions among the metabolic types during the early diversification of life on Earth is crucial for our understanding of the ancient biosphere. The stromatolites from the genus Conophyton cylindricus represent a datum for the Proterozoic (Meso to Neoproterozoic) on Earth. Their typical conical shape has been considered a result of a competition between microorganisms for space, light and nutrients. Well-preserved records of this genus from the Paleontological Site of Cabeludo , Vazante Group, São Francisco Craton (Southern Brazil) present in situ fossilized biofilms, containing preserved carbonaceous matter. Petrographic and geochemical analyses revealed an alternation between mineral laminae (light grey laminae) and fossilized biofilms (dark grey laminae). The dark grey laminae comprise three different biofilms recording a stratified microstructure of microbial communities. These three biofilms composing the dark grey laminae tend to be organized in a specific pattern that repeats through the stromatolite vertical section. Iron and manganese are distributed differently along the dark and light grey laminae; X-ray absorption and luminescence data showed possible different areas with authigenic iron and iron provided from diagenetic infiltration. Cryptocrystalline apatite in the lowermost biofilms in each dark grey laminae may suggest past metabolic activity of sulfide-oxidizing bacteria. These findings suggest that the microorganisms reached a complex metabolic diversification in order to maintain an equilibrium situation between the three different biofilms along the vertical section of the structures, thus benefiting the whole microbial community. This means that the stromatolites from the Conophyton genus may have formed as a result of a greater complexity of interactions between microorganisms, and not only from competition between photosynthesizers

Metaschoepite Dissolution in Sediment Column Systems-Implications for Uranium Speciation and Transport

Metaschoepite is commonly found in U-contaminated environments and metaschoepite-bearing wastes may be managed via shallow or deep disposal. Understanding metaschoepite dissolution and tracking the fate of any liberated U is thus important. Here, discrete horizons of metaschoepite (UO3 center dot nH(2)O) particles were emplaced in flowing sediment/groundwater columns representative of the UK Sellafield Ltd. site. The column systems either remained oxic or became anoxic due to electron donor additions, and the columns were sacrificed after 6- and 12-months for analysis. Solution chemistry, extractions, and bulk and micro/nano-focus X-ray spectroscopies were used to track changes in U distribution and behavior. In the oxic columns, U migration was extensive, with UO22+ identified in effluents after 6-months of reaction using fluorescence spectroscopy. Unusually, in the electron-donor amended columns, during microbially mediated sulfate reduction, significant amounts of UO2-like colloids (>60% of the added U) were found in the effluents using TEM. XAS analysis of the U remaining associated with the reduced sediments confirmed the presence of trace U(VI), noncrystalline U(IV), and biogenic UO2, with UO2 becoming more dominant with time. This study highlights the potential for U(IV) colloid production from U(VI) solids under reducing conditions and the complexity of U biogeochemistry in dynamic systems.Peer reviewe

Structural MRI predicts clinical progression in presymptomatic genetic frontotemporal dementia: findings from the GENetic Frontotemporal dementia Initiative (GENFI) cohort

Abstract Biomarkers that can predict disease progression in individuals with genetic frontotemporal dementia are urgently needed. We aimed to identify whether baseline MRI-based grey and white matter abnormalities are associated with different clinical progression profiles in presymptomatic mutation carriers in the GENetic Frontotemporal dementia Initiative. 387 mutation carriers were included (160 GRN, 160 C9orf72, 67 MAPT), together with 240 non-carrier cognitively normal controls. Cortical and subcortical grey matter volumes were generated using automated parcellation methods on volumetric 3 T T1-weighted MRI scans, while white matter characteristics were estimated using diffusion tensor imaging. Mutation carriers were divided into two disease stages based on their global CDR®+NACC-FTLD score: presymptomatic (0 or 0.5) and fully symptomatic (1 or greater). W-scores in each grey matter volumes and white matter diffusion measures were computed to quantify the degree of abnormality compared to controls for each presymptomatic carrier, adjusting for their age, sex, total intracranial volume, and scanner type. Presymptomatic carriers were classified as “normal” or “abnormal” based on whether their grey matter volume and white matter diffusion measure w-scores were above or below the cut point corresponding to the 10th percentile of the controls. We then compared the change in disease severity between baseline and one year later in both the “normal” and “abnormal” groups within each genetic subtype, as measured by the CDR®+NACC-FTLD sum-of-boxes score and revised Cambridge Behavioural Inventory total score. Overall, presymptomatic carriers with normal regional w-scores at baseline did not progress clinically as much as those with abnormal regional w-scores. Having abnormal grey or white matter measures at baseline was associated with a statistically significant increase in the CDR®+NACC-FTLD of up to 4 points in C9orf72 expansion carriers, and 5 points in the GRN group as well as a statistically significant increase in the revised Cambridge Behavioural Inventory of up to 11 points in MAPT, 10 points in GRN, and 8 points in C9orf72 mutation carriers. Baseline regional brain abnormalities on MRI in presymptomatic mutation carriers are associated with different profiles of clinical progression over time. These results may be helpful to inform stratification of participants in future trials