Exploring Cr and molten salt interfacial interactions for molten salt applications.

Molten salts play an important role in various energy-related applications such as high-temperature heat transfer fluids and reaction media. However, the extreme molten salt environment causes the degradation of materials, raising safety and sustainability challenges. A fundamental understanding of material-molten salt interfacial evolution is needed. This work studies the transformation of metallic Cr in molten 50/50 mol% KCl-MgCl2via multi-modal in situ synchrotron X-ray nano-tomography, diffraction and spectroscopy combined with density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Notably, in addition to the dissolution of Cr in the molten salt to form porous structures, a δ-A15 Cr phase was found to gradually form as a result of the metal-salt interaction. This phase change of Cr is associated with a change in the coordination environment of Cr at the interface. DFT and AIMD simulations provide a basis for understanding the enhanced stability of δ-A15 Cr vs. bcc Cr, by revealing their competitive phase thermodynamics at elevated temperatures and probing the interfacial behavior of the molten salt at relevant facets. This study provides critical insights into the morphological and chemical evolution of metal-molten salt interfaces. The combination of multimodal synchrotron analysis and atomic simulation also offers an opportunity to explore a broader range of systems critical to energy applications.

TXM-Sandbox: an open-source software for transmission X-ray microscopy data analysis.

A transmission X-ray microscope (TXM) can investigate morphological and chemical information of a tens to hundred micrometre-thick specimen on a length scale of tens to hundreds of nanometres. It has broad applications in material sciences and battery research. TXM data processing is composed of multiple steps. A workflow software has been developed that integrates all the tools required for general TXM data processing and visualization. The software is written in Python and has a graphic user interface in Jupyter Notebook. Users have access to the intermediate analysis results within Jupyter Notebook and have options to insert extra data processing steps in addition to those that are integrated in the software. The software seamlessly integrates ImageJ as its primary image viewer, providing rich image visualization and processing routines. As a guide for users, several TXM specific data analysis issues and examples are also presented.

Transmission x-ray microscopy and its applications in battery material research-a short review.

Transmission x-ray microscopy (TXM), which can provide morphological and chemical structural information inside of battery component materials at tens of nanometer scale, has become a powerful tool in battery research. This article presents a short review of the TXM, including its instrumentation, battery research applications, and the practical sample preparation and data analysis in the TXM applications. A brief discussion on the challenges and opportunities in the TXM applications is presented at the end.

Kinetic Limitations in Single-Crystal High-Nickel Cathodes.

High-nickel cathodes attract immense interest for use in lithium-ion batteries to boost Li-storage capacity while reducing cost. For overcoming the intergranular-cracking issue in polycrystals, single-crystals are considered an appealing alternative, but aggravating concerns on compromising the ionic transport and kinetic properties. We report here a quantitative assessment of redox reaction in single-crystal LiNi0.8 Mn0.1 Co0.1 O2 using operando hard X-ray microscopy/spectroscopy, revealing a strong dependence of redox kinetics on the state of charge (SOC). Specifically, the redox is sluggish at low SOC but increases rapidly as SOC increases, both in bulk electrodes and individual particles. The observation is corroborated by transport measurements and finite-element simulation, indicating that the sluggish kinetics in single-crystals is governed by ionic transport at low SOC and may be alleviated through synergistic interaction with polycrystals integrated into a same electrode.

PyXAS - an open-source package for 2D X-ray near-edge spectroscopy analysis.

In the synchrotron X-ray community, X-ray absorption near-edge spectroscopy (XANES) is a widely used technique to probe the local coordination environment and the oxidation states of specific elements within a sample. Although this technique is usually applied to bulk samples, the advent of new synchrotron sources has enabled spatially resolved versions of this technique (2D XANES). This development has been extremely powerful for the study of heterogeneous systems, which is the case for nearly all real applications. However, associated with the development of 2D XANES comes the challenge of analyzing very large volumes of data. As an example, a single 2D XANES measurement at a synchrotron can easily produce ∼106 spatially resolved XANES spectra. Conventional manual analysis of an individual XANES spectrum is no longer feasible. Here, a software package is described that has been developed for high-throughput 2D XANES analysis. A detailed description of the software as well as example applications are provided.

Versatile compact heater design for in situ nano-tomography by transmission X-ray microscopy.

A versatile, compact heater designed at National Synchrotron Light Source-II for in situ X-ray nano-imaging in a full-field transmission X-ray microscope is presented. Heater design for nano-imaging is challenging, combining tight spatial constraints with stringent design requirements for the temperature range and stability. Finite-element modeling and analytical calculations were used to determine the heater design parameters. Performance tests demonstrated reliable and stable performance, including maintaining the exterior casing close to room temperature while the heater is operating at above 1100°C, a homogenous heating zone and small temperature fluctuations. Two scientific experiments are presented to demonstrate the heater capabilities: (i) in situ 3D nano-tomography including a study of metal dealloying in a liquid molten salt extreme environment, and (ii) a study of pore formation in icosahedral quasicrystals. The progression of structural changes in both studies were clearly resolved in 3D, showing that the new heater enables powerful capabilities to directly visualize and quantify 3D morphological evolution of materials under real conditions by X-ray nano-imaging at elevated temperature during synthesis, fabrication and operation processes. This heater design concept can be applied to other applications where a precise, compact heater design is required.

Anisotropically Electrochemical-Mechanical Evolution in Solid-State Batteries and Interfacial Tailored Strategy.

All-solid-state batteries have attracted attention owing to the potential high energy density and safety; however, little success has been made on practical applications of solid-state batteries, which is largely attributed to the solid-solid interface issues. A fundamental elucidation of electrode-electrolyte interface behaviors is of crucial significance but has proven difficult. The interfacial resistance and capacity fading issues in a solid-state battery were probed, revealing a heterogeneous phase transition evolution at solid-solid interfaces. The strain-induced interfacial change and the contact loss, as well as a dense metallic surface phase, deteriorate the electrochemical reaction in solid-state batteries. Furthermore, the in situ growth of electrolytes on secondary particles is proposed to fabricate robust solid-solid interface. Our study enlightens new insights into the mechanism behind solid-solid interfacial reaction for optimizing advanced solid-state batteries.

Mouthpart conduit sizes of fluid-feeding insects determine the ability to feed from pores.

Fluid-feeding insects, such as butterflies, moths and flies (20% of all animal species), are faced with the common selection pressure of having to remove and feed on trace amounts of fluids from porous surfaces. Insects able to acquire fluids that are confined to pores during drought conditions would have an adaptive advantage and increased fitness over other individuals. Here, we performed feeding trials using solutions with magnetic nanoparticles to show that butterflies and flies have mouthparts adapted to pull liquids from porous surfaces using capillary action as the governing principle. In addition, the ability to feed on the liquids collected from pores depends on a relationship between the diameter of the mouthpart conduits and substrate pore size diameter; insects with mouthpart conduit diameters larger than the pores cannot successfully feed, thus there is a limiting substrate pore size from which each species can acquire liquids for fluid uptake. Given that natural selection independently favoured mouthpart architectures that support these methods of fluid uptake (Diptera and Lepidoptera share a common ancestor 280 Ma that had chewing mouthparts), we suggest that the convergence of this mechanism advocates this as an optimal strategy for pulling trace amounts of fluids from porous surfaces.

Multigenerational Effects of Rearing Atmospheric Oxygen Level on the Tracheal Dimensions and Diffusing Capacities of Pupal and Adult Drosophila melanogaster.

Insects are small relative to vertebrates, and were larger in the Paleozoic when atmospheric oxygen levels were higher. The safety margin for oxygen delivery does not increase in larger insects, due to an increased mass-specific investment in the tracheal system and a greater use of convection in larger insects. Prior studies have shown that the dimensions and number of tracheal system branches varies inversely with rearing oxygen in embryonic and larval insects. Here we tested whether rearing in 10, 21, or 40 kPa atmospheric oxygen atmospheres for 5-7 generations affected the tracheal dimensions and diffusing capacities of pupal and adult Drosophila. Abdominal tracheae and pupal snorkel tracheae showed weak responses to oxygen, while leg tracheae showed strong, but imperfect compensatory changes. The diffusing capacity of leg tracheae appears closely matched to predicted oxygen transport needs by diffusion, perhaps explaining the consistent and significant responses of these tracheae to rearing oxygen. The reduced investment in tracheal structure in insects reared in higher oxygen levels may be important for conserving tissue PO2 and may provide an important mechanism for insects to invest only the space and materials necessary into respiratory structure.

Meniscus formation in a capillary and the role of contact line friction.

We studied spontaneous formation of an internal meniscus by dipping glass capillaries of 25 µm to 350 µm radii into low volatile hexadecane and tributyl phosphate. X-ray phase contrast and high speed optical microscopy imaging were employed. We showed that the meniscus completes its formation when the liquid column is still shorter than the capillary radius. After that, the meniscus travels about ten capillary radii at a constant velocity. We demonstrated that the experimental observations can be explained by introducing a friction force linearly proportional to the meniscus velocity with a friction coefficient depending on the air/liquid/solid triplet. It was demonstrated that the friction coefficient does not depend on the capillary radius. Numerical solution of the force balance equation revealed four different uptake regimes that can be specified in a phase portrait. This phase portrait was found to be in good agreement with the experimental results and can be used as a guide for the design of thin porous absorbers.

Sharpening the surface of magnetic paranematic droplets.

In a non-uniform magnetic field, the droplets of colloids of nickel nanorods and nanobeads aggregate to form a cusp at the droplet surface not deforming the entire droplet shape. When the field is removed, nanorods diffuse away and the cusp disappears. Spherical particles can form cusps in a similar way, but they stay aggregated after the release of the field; finally, the aggregates settle down to the bottom of the drop. The X-ray phase contrast imaging reveals that nanorods in the cusps stay parallel to each other without visible spatial order of their centers of mass. The formation of cusps can be explained with a model that includes magnetostatic and surface tension forces. The discovered possibility of controlled assembly and quenching of nanorod orientation under the cusped liquid surface offers vast opportunities for alignment of carbon nanotubes, nanowires and nanoscrolls, prior to spinning them into superstrong and multifunctional fibers. Magnetostatic and electrostatic analogies suggest that a similar ideal alignment can be achieved with the rod-like dipoles subject to a strong electric field.

Dynamics of tracheal compression in the horned passalus beetle.

Rhythmic patterns of compression and reinflation of the thin-walled hollow tubes of the insect tracheal system have been observed in a number of insects. These movements may be important for facilitating the transport and exchange of respiratory gases, but observing and characterizing the dynamics of internal physiological systems within live insects can be challenging due to their size and exoskeleton. Using synchrotron X-ray phase-contrast imaging, we observed dynamical behavior in the tracheal system of the beetle, Odontotaenius disjunctus. Similar to observations of tracheal compression in other insects, specific regions of tracheae in the thorax of O. disjunctus exhibit rhythmic collapse and reinflation. During tracheal compression, the opposing sides of a tracheal tube converge, causing the effective diameter of the tube to decrease. However, a unique characteristic of tracheal compression in this species is that certain tracheae collapse and reinflate with a wavelike motion. In the dorsal cephalic tracheae, compression begins anteriorly and continues until the tube is uniformly flattened; reinflation takes place in the reverse direction, starting with the posterior end of the tube and continuing until the tube is fully reinflated. We report the detailed kinematics of this pattern as well as additional observations that show tracheal compression coordinated with spiracle opening and closing. These findings suggest that tracheal compression may function to drive flow within the body, facilitating internal mixing of respiratory gases and ventilation of distal regions of the tracheal system.

Hypoxia-induced compression in the tracheal system of the tobacco hornworm caterpillar, Manduca sexta.

Abdominal pumping in caterpillars has only been documented during molting. Using synchrotron X-ray imaging in conjunction with high-speed flow-through respirometry, we show that Manduca sexta caterpillars cyclically contract their bodies in response to hypoxia, resulting in significant compressions of the tracheal system. Compression of tracheae induced by abdominal pumping drives external gas exchange, as evidenced by the high correlation between CO2 emission peaks and body movements. During abdominal pumping, both the compression frequency and fractional change in diameter of tracheae increased with body mass. However, abdominal pumping and tracheal compression were only observed in larger, older caterpillars (>0.2 g body mass), suggesting that this hypoxic response increases during ontogeny. The diameters of major tracheae in the thorax increased isometrically with body mass. However, tracheae in the head did not scale with mass, suggesting that there is a large safety margin for oxygen delivery in the head in the youngest animals. Together, these results highlight the need for more studies of tracheal system scaling and suggest that patterns of tracheal investment vary regionally in the body.

Temperature-Dependent Morphological Evolution during Corrosion of the Ni-20Cr Alloy in Molten Salt Revealed by Multiscale Imaging.

Understanding the mechanisms leading to the degradation of alloys in molten salts at elevated temperatures is significant for developing several key energy generation and storage technologies, including concentrated solar and next-generation nuclear power plants. Specifically, the fundamental mechanisms of different types of corrosion leading to various morphological evolution characteristics for changing reaction conditions between the molten salt and alloy remain unclear. In this work, the three-dimensional (3D) morphological evolution of Ni-20Cr in KCl-MgCl2 is studied at 600 °C by combining in situ synchrotron X-ray and electron microscopy techniques. By further comparing different morphology evolution characteristics in the temperature range of 500-800 °C, the relative rates between diffusion and reaction at the salt-metal interface lead to different morphological evolution pathways, including intergranular corrosion and percolation dealloying. In this work, the temperature-dependent mechanisms of the interactions between metals and molten salts are discussed, providing insights for predicting molten salt corrosion in real-world applications.

Evolution of micro-pores in Ni-Cr alloys via molten salt dealloying.

Porous materials with high specific surface area, high porosity, and high electrical conductivity are promising materials for functional applications, including catalysis, sensing, and energy storage. Molten salt dealloying was recently demonstrated in microwires as an alternative method to fabricate porous structures. The method takes advantage of the selective dissolution process introduced by impurities often observed in molten salt corrosion. This work further investigates molten salt dealloying in bulk Ni-20Cr alloy in both KCl-MgCl2 and KCl-NaCl salts at 700 â„ƒ, using scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction (XRD), as well as synchrotron X-ray nano-tomography. Micro-sized pores with irregular shapes and sizes ranging from sub-micron to several microns and ligaments formed during the process, while the molten salt dealloying was found to progress several microns into the bulk materials within 1-16 h, a relatively short reaction time, enhancing the practicality of using the method for synthesis. The ligament size increased from ~ 0.7 µm to ~ 1.3 µm in KCl-MgCl2 from 1 to 16 h due to coarsening, while remaining ~ 0.4 µm in KCl-NaCl during 16 h of exposure. The XRD analysis shows that the corrosion occurred primarily near the surface of the bulk sample, and Cr2O3 was identified as a corrosion product when the reaction was conducted in an air environment (controlled amount sealed in capillaries); thus surface oxides are likely to slow the morphological coarsening rate by hindering the surface diffusion in the dealloyed structure. 3D-connected pores and grain boundary corrosion were visualized by synchrotron X-ray nano-tomography. This study provides insights into the morphological and chemical evolution of molten salt dealloying in bulk materials, with a connection to molten salt corrosion concerns in the design of next-generation nuclear and solar energy power plants.

Three-dimensional X-ray micro-velocimetry.

A direct measurement of three-dimensional X-ray velocimetry with micrometer spatial resolution is presented. The key to this development is the use of a Laue crystal as an X-ray beam splitter and mirror. Three-dimensional flow velocities in a 0.4 mm-diameter tubing were recorded, with <5 µm spatial resolution and speeds of 0.7 mm s(-1). This development paves the way for three-dimensional velocimetry in many cases where visible-light techniques are not effective, such as multiphase flow or flow of optically opaque liquids.

Full-field microimaging with 8 keV X-rays achieves a spatial resolutions better than 20 nm.

Fresnel zone plates (450 nm thick Au, 25 nm outermost zone width) used as objective lenses in a full field transmission reached a spatial resolution better than 20 nm and 1.5% efficiency with 8 keV photons. Zernike phase contrast was also realized without compromising the resolution. These are very significant achievements in the rapid progress of high-aspect-ratio zone plate fabrication by combined electron beam lithography and electrodeposition.

Hard x-ray Zernike microscopy reaches 30 nm resolution.

Since its invention in 1930, Zernike phase contrast has been a pillar in optical microscopy and more recently in x-ray microscopy, in particular for low-absorption-contrast biological specimens. We experimentally demonstrate that hard-x-ray Zernike microscopy now reaches a lateral resolution below 30 nm while strongly enhancing the contrast, thus opening many new research opportunities in biomedicine and materials science.

Adaptation to hard-object feeding in sea otters and hominins.

The large, bunodont postcanine teeth in living sea otters (Enhydra lutris) have been likened to those of certain fossil hominins, particularly the 'robust' australopiths (genus Paranthropus). We examine this evolutionary convergence by conducting fracture experiments on extracted molar teeth of sea otters and modern humans (Homo sapiens) to determine how load-bearing capacity relates to tooth morphology and enamel material properties. In situ optical microscopy and x-ray imaging during simulated occlusal loading reveal the nature of the fracture patterns. Explicit fracture relations are used to analyze the data and to extrapolate the results from humans to earlier hominins. It is shown that the molar teeth of sea otters have considerably thinner enamel than those of humans, making sea otter molars more susceptible to certain kinds of fractures. At the same time, the base diameter of sea otter first molars is larger, diminishing the fracture susceptibility in a compensatory manner. We also conduct nanoindentation tests to map out elastic modulus and hardness of sea otter and human molars through a section thickness, and microindentation tests to measure toughness. We find that while sea otter enamel is just as stiff elastically as human enamel, it is a little softer and tougher. The role of these material factors in the capacity of dentition to resist fracture and deformation is considered. From such comparisons, we argue that early hominin species like Paranthropus most likely consumed hard food objects with substantially higher biting forces than those exerted by modern humans.

Interpretation of dark-field contrast and particle-size selectivity in grating interferometers.

In grating-based x-ray phase sensitive imaging, dark-field contrast refers to the extinction of the interference fringes due to small-angle scattering. For configurations where the sample is placed before the beamsplitter grating, the dark-field contrast has been quantified with theoretical wave propagation models. Yet when the grating is placed before the sample, the dark-field contrast has only been modeled in the geometric optics regime. Here we attempt to quantify the dark-field effect in the grating-before-sample geometry with first-principle wave calculations and understand the associated particle-size selectivity. We obtain an expression for the dark-field effect in terms of the sample material's complex refractive index, which can be verified experimentally without fitting parameters. A dark-field computed tomography experiment shows that the particle-size selectivity can be used to differentiate materials of identical x-ray absorption.