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At least 379 records · Page 21

Geometrical frustration and competing orders in the dipolar trimerized triangular lattice

Here, we introduce and explore low-energy configurations in two-dimensional arrays consisting of Ising-type dipolar coupled nanomagnets lithographically defined onto three-nanomagnet vertices arranged in a triangular coordination. Thus, the system is dubbed the trimerized triangular lattice. Employing synchrotron-based photoemission electron microscopy, we perform temperature-dependent magnetic imaging of moment configurations. These states are then characterized in terms of spin correlations and magnetic structure factors. The results reveal a competition between ferromagnetic and vortex dominated orders, which can be controlled by varying the relevant lattice parameter and the corresponding competing interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Studies of the Si/SiO2 interface using synchrotron radiation

Synchrotron radiation photoemission spectroscopy (SRPS) in the 1-4 KeV photon energy range is a useful tool for interface characterization. Results are presented of a series of studies of the near-interface region of Si/SiO2 which confirm that a bond strain gradient exists in the oxide as a result of lattice mismatch. These experiments include measurement of photoemission lineshape changes as a function of photon energy, corresponding changes in the electron escape depth near the interface, and surface extended X-ray absorption fine structure (SEXAFS) measurements directly indicating the shortening of the Si-Si second nearest neighbor distance in the near-interface region of the oxide.

Hecht, M. H.↗

Correlative nano-imaging of metals and proteins in primary neurons by synchrotron X-ray fluorescence and STED super resolution microscopy: Experimental validation

It is becoming increasingly clear that biological metals such as iron, copper or zinc are involved in synaptic functions, and in particular in the mechanisms of synaptogenesis and subsequent plasticity. Understanding the role of metals on synaptic functions is a difficult challenge due to the very low concentration of these elements in neurons and to the submicrometer size of synaptic compartments. To address this challenge we have developed a correlative nano-imaging approach combining metal and protein detection. First, stimulated emission depletion (STED) microscopy, a super resolution optical microscopy technique, is applied to locate fluorescently labeled proteins. Then, synchrotron radiation induced X-ray fluorescence (SXRF) is performed on the same regions of interest, e.g. synaptic compartments. Here, we present here the principle scheme that allows this correlative nano-imaging and its experimental validation. We applied this correlative nano-imaging to the study of the physiological distribution of metals in synaptic compartments of primary rat hippocampal neurons. We thus compared the nanometric distribution of metals with that of synaptic proteins, such as PSD95 or cytoskeleton proteins. Compared to correlative imaging approaches currently used to characterize synaptic structures, such as electron microscopy correlated with optical fluorescence, our approach allows for ultra-sensitive detection of trace metals using highly focused synchrotron radiation beams. We provide proof-of-principle for correlative imaging of metals and proteins at the synaptic scale and discuss the present limitations and future developments in this area.

59 BASIC BIOLOGICAL SCIENCES↗

Disentangling x-ray dichroism and birefringence via high-purity polarimetry

High-brilliance synchrotron radiation sources have opened new avenues for x-ray polarization analysis that go far beyond conventional polarimetry in the optical domain. With linear x-ray polarizers in a crossed setting, polarization extinction ratios down to 10 -10 can be achieved. This renders the method sensitive to probe the tiniest optical anisotropies that would occur, for example, in strong-field quantum electrodynamics due to vacuum birefringence and dichroism. Here we show that high-purity polarimetry can be employed to reveal electronic anisotropies in condensed matter systems with utmost sensitivity and spectral resolution. Taking CuO and La 2 CuO 4 as benchmark systems, we present a full characterization of the polarization changes across the Cu K-absorption edge and their separation into dichroic and birefringent contributions. At diffraction-limited synchrotron radiation sources and x-ray lasers, where polarization extinction ratios of 10 -12 can be achieved, our method has the potential to assess birefringence and dichroism of the quantum vacuum in extreme electromagnetic fields.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Operando Infrared Nanospectroscopy of the Silicon/Electrolyte Interface during Initial Stages of Solid-Electrolyte-Interphase Layer Formation

The solid electrolyte interphase (SEI) is a critical component in Li-ion batteries; however, its nanoscale structure and composition and unstable nature make it difficult to characterize and ascertain primary functional mechanisms. We use operando nanoscale Fourier transform infrared spectroscopy (nano-FTIR) with a broadband synchrotron IR source to study the SEI formation on a thin-film Si electrode at nanometer-scale spatial resolution as a function of time and voltage. By probing the Si/carbonate electrolyte interface through a 25 nm-thick amorphous Si window/electrode, we detect molecular vibrational modes within a 10s of nanometers region adjacent to the Si surface and observe that PF6 – anions react to form LiF at 0.5 V. Spatially resolved nano-FTIR spectra showcase subtle nanoscale heterogeneities in the initial solid/liquid interface and the resulting deposited LiF. With its nanoscale resolution and high chemical specificity, operando nano-FTIR provides unique insights into the dynamics and heterogeneous formation of SEIs and opens opportunities for connecting nanoscale interfacial properties to bulk performance metrics.

Dopilka, Andrew↗

First-principles-integrated Study of Blazar Synchrotron Radiation and Polarization Signatures from Magnetic Turbulence

Blazar emission is dominated by nonthermal radiation processes that are highly variable across the entire electromagnetic spectrum. Turbulence, which can be a major source of nonthermal particle acceleration, can widely exist in the blazar emission region. The Turbulent Extreme Multi-Zone (TEMZ) model has been used to describe turbulent radiation signatures. Recent particle-in-cell (PIC) simulations have also revealed the stochastic nature of the turbulent emission region and particle acceleration therein. However, radiation signatures have not been systematically studied via first-principles-integrated simulations. In this paper, we perform combined PIC and polarized radiative transfer simulations to study synchrotron emission from magnetic turbulence in the blazar emission region. We find that the multiwavelength flux and polarization are generally characterized by stochastic patterns. Specifically, the variability timescale and average polarization degree (PD) are governed by the correlation length of the turbulence. Interestingly, magnetic turbulence can result in polarization angle swings with arbitrary amplitudes and duration, in either direction, that are not associated with changes in flux or PD. Surprisingly, these swings, which are stochastic in nature, can appear either bumpy or smooth, although large-amplitude swings (>180°) are very rare, as expected. Our radiation and polarization signatures from first-principles-integrated simulations are consistent with the TEMZ model, except that in the latter, there is a weak correlation, with zero lag, between flux and degree of polarization.

79 ASTRONOMY AND ASTROPHYSICS↗

Grazing incidence optics; Proceedings of the Meeting, Orlando, FL, Apr. 3, 4, 1986

Papers are presented on the diffraction-limited performance of grazing incidence optical systems; transverse ray aberrations of Wolter type 1 telescopes; hybrid X-ray telescope systems; surface characterization of grazing incidence optics in the extreme UV and X-ray regions; and the surface roughness properties of synchrotron radiation optics. Topics discussed include the simulation of free-abrasive grinding of grazing incidence mirrors with vertical-honing and flexible blades; mirrors for the Extreme Ultraviolet Explorer; the design and development of conical X-ray imaging mirrors; thermal loading considerations for synchrotron radiation mirrors; and grazing incidence optics for synchrotron radiation insertion-device beams. Consideration is given to the interpretation of glancing incidence scattering measurements; damage processes in short wavelength coated FEL optics; the replication of grain incidence optics; and the assembly and alignment of the Technology Mirror Assembly.

Osantowski, John F.↗

Crystallization and Preliminary X-ray Analysis of Der f 2, a Potent Allergen Derived from the House Dust Mite

Although a number of allergens have been identified and isolated, the underlying molecular basis for the potent immune response is poorly understood. House dust mites (Dermatophugoides sp.) are particularly ubiquitous contributors to atopy in developed countries. The rhinitis, dermatitis, and asthma associated with allergic reactions to these arthropods are often caused by relatively small (125-129 amino acids) mite proteins of unclear biological function. Der f 2, a major allergen from the mite Dermatophagoides farinae, has been recombinantly expressed and characterized. The Der f 2 protein has been crystallized in our laboratory and a native data set collected at a synchrotron source. The crystals belong to the orthorhombic space group I422 with unit cell parameters of a = 95.2 Angstroms, b = 95.2 Angstroms, and c = 103.3 Angstroms. An essentially complete (97.2%) data set has been collected to 2.4 Angstroms. Attempts to solve the crystal structure of Der f 2 by molecular replacement using the available NMR coordinates for either Der f 2 or Der p 2 (the homologous protein from D. pterovssinus) failed to reveal a creditable solution.

Roeber, Dana↗

Hydrogen and Ferric Iron in Mars Materials

Knowledge of oxygen and hydrogen fugacity is of paramount importance in constraining phase equilibria and crystallization processes of melts, as well as understanding the partitioning of elements between the cope and silicate portions of terrestrial planets. H and Fe(3+) must both be analyzed in order to reconstruct hydrogen and oxygen fugacities on Mars. To date, SIMS data have elucidated D/H and H contents of hydrous phases in SNC meteorites, but until now anhydrous martian minerals have not been systematically examined for trace hydrogen. Ferric iron has been quantified using XANES in many martian phases, but integrated studies of both Fe(3+) and H on the same spots are really needed to address the H budget. Finally, the effects of shock on both Fe(3+) and H in hydrous and anhydrous phases must be quantified. Thus, the overall goal of this research was to understand the oxygen and hydrogen fugacities under which martian samples crystallized. In this research one-year project, we approached this problem by 1) characterizing Fe(3+) and H contents of SNC meteorites using both bulk (Mossbauer spectroscopy and uranium extraction, respectively) and microscale (synchrotron micro-XANES and SIMS) methods; 2) relating Fe(3+) and H contents of martian minerals to their oxygen and hydrogen fugacities through analysis of experimentally equilibrated phases (for pyroxene) and through study of volcanic rocks in which the oxygen and hydrogen fugacities can be independently constrained (for feldspar); and 3) studying the effects of shock processes on Fe(3+) and H contents of the phases of interest. Results have been used to assess quantitatively the distribution of H and Fe(3+) among phases in the martian interior, which will better constrain the geodynamic processes of the interior, as well as the overall hydrogen and water budgets on Mars. There were no inventions funded by this research.

Dyar, Melinda D.↗

A Deep X-Ray View of the Synchrotron-Dominated Supernova Remnant G330.2+1.0

We present moderately deep (125 ks) XMM-Newton observations of supernova remnant G330.2+1.0. This remnant is one of only a few known that fall into the "synchrotron-dominated" category, with the emission almost entirely dominated by a nonthermal continuum. Previous X-ray observations could only characterize the spectra of a few regions. Here, we examine the spectra from 14 regions surrounding the entire rim, finding that the spectral properties of the nonthermal emission do not vary significantly in any systematic way from one part of the forward shock to another, unlike several other remnants of this class. We confirm earlier findings that the power-law index, Γ, ranges from about 2.1-2.5, while the absorbing column density is generally between (2.0-2.6) × 10(exp 22) cm(exp -2). Fits with the srcut model find values of the roll-off frequency in the range of 10(exp 17.1)-10(exp 17.5) Hz, implying energies of accelerated electrons of approximately 100 TeV. These values imply a high shock velocity of approximately 4600 km s(exp -1), favoring a young age of the remnant. Diffuse emission from the interior is nonthermal in origin as well, and fits to these regions yield similar values to those along the rim, also implying a young age. Thermal emission is present in the east, and the spectrum is consistent with approximately 650 km s(exp -1) shock wave encountering interstellar or circumstellar material with a density of approximately 1 cm(exp -3).

Williams, Brian J.↗

Stresses within rare-earth doped yttria-stabilized zirconia thermal barrier coatings from in-situ synchrotron X-ray diffraction at high temperatures

There is a growing interest for smart coatings that can be integrated into turbine engines for in-situ temperature measurements or health monitoring. The addition of rare-earth dopants into standard thermal barrier ceramic top coat materials is used to obtain luminescent coatings that enable spectral measurements, for real-time temperature or health monitoring. The thermomechanical performance and durability of such novel coating compositions in extreme environments still remains to be evaluated. Consequently, the ability to manufacture sensor coatings which present suitable thermal properties needs to be demonstrated. For this study, highly luminescent erbium and europium doped yttria-stabilized zirconia and state-of-the-art yttria-stabilized zirconia coatings manufactured by air plasma spray were characterized to determine the effects of the embedded rareearth dopants on coating internal strain and stress and to quantify and compare their high temperature response using synchrotron X-ray diffraction. In-situ depth-resolved strain measurements were performed at 15 μm intervals along the depth of the coatings to evaluate materials response at key locations, specifically at layer interfaces. In-plane stress was calculated for the coatings and a finite element model was implemented to supplement the results and enable further predictions. The results show that the sensor coatings that were manufactured in this work revealed only minor variations in the strain response of sensor coatings under a typical thermal cycle and especially at temperatures closer to that of gas turbine operating conditions, compared to state-of-the-art coatings. This work demonstrates the viability of manufacturing rare-earth doped yttria-stabilized zirconia coatings that provide beneficial spectroscopic monitoring capabilities while having minimal impact on the thermomechanical response of the thermal barrier coatings.

Air plasma spray↗

Ca Metal Batteries and Sn Anode Alloying: Resolving Misconceptions in Ca–Sn Alloy Formation

Ca metal anode suffers from surface passivation and struggles to effectively plate and strip in conventional Ca electrolytes, making the development of alloy anode for calcium metal battery essential. This work systematically and carefully evaluates the electrochemical formation and feasibility of the Sn anode and its possibility of alloying with Ca using a combination of cyclic voltammetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDS), X-ray diffraction (XRD), and synchrotron transmission X-ray microscopy (TXM). Electrochemical measurements and SEM/EDS analyses indicate apparent Ca alloy formation. However, detailed XRD and TXM characterization reveal substantial lithium-ion involvement when lithium metal is employed as the reference electrode, even in electrolytes with high Ca salt concentrations. These findings highlight a significant risk of misinterpretation: Although limited Ca–Sn alloying may occur, the faster kinetics of Li + can dominate the alloying process, leading to a Li-driven reactions at the Sn anode. In contrast, cells constructed with Ca metal as both reference and counter electrodes exhibit distinct redox features only during the initial cycles, followed by rapid cell failure. The high oxidation currents induce severe Ca passivation, occurring nearly concurrently with Sn dealloying. Overall, this study provides critical insight into the practical limitations and common experimental artifacts associated with Ca metal battery systems and underscores the necessity for rigorous cell design and cautious interpretation when evaluating alloy chemistry in multivalent Ca-based batteries.

36 MATERIALS SCIENCE↗

Structure and Stability of the Iodide Elpasolite, Cs 2 AgBiI 6

Iodide elpasolites (or double perovskites, A 2 B'B"I 6 , B' = M + , B" = M 3+ ) are predicted to be promising alternatives to lead-based perovskite semiconductors for photovoltaic and optoelectronic applications, but no iodide elpasolite has ever been definitively prepared or structurally characterized. Iodide elpasolites are widely predicted to be unstable due to favorable decomposition to the competing A 3 B 2 I 9 (B = M 3+ ) phase. Here, we report the results of synchrotron XRD and X-ray total scattering measurements on putative Cs 2 AgBiI 6 nanocrystals made via anion exchange from parent Cs 2 AgBiBr 6 nanocrystals. Rietveld refinement of XRD and PDF data shows that these nanocrystals indeed exhibit a tetragonal ($I$$\overline{4}$$m$) elpasolite structure, making them the first example of a structurally characterized iodide elpasolite. In conclusion, a series of experiments probing structural relaxation and the effects of surface ligation or grain size all point to the critical role of surface free energy in stabilizing the iodide elpasolite phase in these nanocrystals.

36 MATERIALS SCIENCE↗

A method for mapping submicron-scale crystallographic order/disorder applied to human tooth enamel

Tooth enamel, the outermost layer of human teeth, is a complex, hierarchically structured biocomposite. The details of this structure are important in multiple human health contexts, from understanding the progression of dental caries (tooth decay) to understanding the process of amelogenesis and related developmental defects. Enamel is composed primarily of long, nanoscale crystallites of hydroxyapatite that are bundled by the thousands to form micron-scale rods. Studies with transmission electron microscopy show the relationships between small groups of crystallites and X-ray diffraction characterize averages over many rods, but the direct measurement of variations in local crystallographic structure across and between enamel rods has been missing. Here, we describe a synchrotron X-ray-based experimental approach and a novel analysis method developed to address this gap in knowledge. A ~500-nm-wide beam of monochromatic X-rays in conjunction with a sample section only 1 μm in thickness enables 2D diffraction patterns to be collected from small well-separated volumes within the enamel microstructure but still probes enough crystallites (~300 per pattern) to extract population-level statistics on crystallographic features like lattice parameter, crystallite size, and orientation distributions. Furthermore, the development of a quantitative metric to characterize relative order and disorder based on the azimuthal autocorrelation of diffracted intensity enables these crystallographic measurements to be correlated with their location within the enamel microstructure (e.g., between rod and interrod regions). These methods represent a step forward in the characterization of human enamel and will elucidate the variation of the crystallographic structure across and between enamel rods for the first time.

crystallographic order/disorder↗

Effect of oxidation on the release of multiple metals from industrially polluted sediments and synchrotron-based evidence of Cu–S dynamic association

Disposal operations for industrially polluted sediments are usually accompanied by disturbance and resuspension, which can induce metal remobilization and secondary pollution. Evaluating the risk of metal release under various redox conditions is fundamental for predicting contaminant mobilization and guiding remediation measures. An abandoned oxidation pond, Yanjia Lake, China, was selected as a typical industrially polluted site. Re-suspension experiments were carried out by mixing polluted sediments with lake water under oxic or anoxic conditions, then investigating the effect of oxidation conditions on the release of multiple metals. Metal concentrations and aqueous chemistry in the overlying water were monitored. Synchrotron-based methods, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), were used to characterize oxidation states and coordination conditions of metals in sediments. The release of metals, including Cr, Co, Ni, Cu, Zn, Se, Mo, Sn, Cd, and Pb, was enhanced under oxic vs. anoxic conditions. The XANES analysis revealed that elevated Cr and Zn concentrations under oxic conditions likely resulted from the oxidation of Cr(III) and oxidizing dissolution of ZnS, respectively. K-edge Cu XANES, S XANES, and Cu EXAFS analyses reconstructed the Cu–S association, indicating that S-related oxidation promoted Cu release and Cu–O partly replaced Cu–S in the sediment after a 7-day oxic treatment. The release of most metals was promoted under oxic conditions, resulting from the oxidation of sulfides and metals as indicated by aqueous and synchrotron-based evidence. The risk of secondary pollution is greatly enhanced under oxic conditions, which suggests that measures should be taken to minimize the redox disturbance during sediment remediation. This information can guide the management of sediments in Yanjia Lake and other contaminated sites with similar properties.

54 ENVIRONMENTAL SCIENCES↗

Lipids status and copper in a single astrocyte of the rat model for amyotrophic lateral sclerosis: Correlative synchrotron-based X-ray and infrared imaging

Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disease, causing death of motor neurons controlling voluntary muscles. The pathological mechanisms of the disease are only partially understood. The hSOD1-G93A ALS rat model is characterized by an overexpression of human mutated SOD1, causing increased vulnerability by forming intracellular protein aggregates, inducing excitotoxicity, affecting oxidative balance and disturbing axonal transport. In this study we followed the bio-macromolecular organic composition and compartmentalization together with trace metal distribution in situ in single astrocytes from the ALS rat model and compared them to the control astrocytes from nontransgenic littermates by simultaneous use of two synchrotron radiation-based methods: Fourier transform infrared microspectroscopy (SRFTIR) and hard X-ray fluorescence microscopy (XRF). Here we show that ALS cells contained more Cu, which colocalized with total lipids, increased carbonyl groups and oxidized lipids, thus implying direct involvement of Cu in oxidative stress of lipidic components without direct connection to protein aggregation in situ.

59 BASIC BIOLOGICAL SCIENCES↗

Revealing the chemical environment of Cr, Fe, and Ni in high temperature-ultrafine precipitate strengthened steel subjected to low fluence neutron irradiation

High-temperature ultrafine-precipitate-strengthened (HT-UPS) steel has potential applications in advanced nuclear reactors as a structural material. However, little is currently known about its response to neutron irradiation. This research provides insight into the neutron irradiation-induced physicochemical changes of the major constituents in HT-UPS steels, including Fe, Cr, and Ni, using synchrotron X-ray absorption near edge structure (XANES) and diffraction. This study is the first known investigation using XANES to characterize HT-UPS steel to analyze the evolution of the atomic level chemistry. It was found that following irradiation, nucleation, ballistic dispersion, and/or coarsening of Cr 23 C 6 precipitates occurred at very low neutron irradiation fluences, from 0.003 displacements per atom (dpa) up to 0.3 dpa, at ~600°C, which were at least an order of magnitude lower than previous studies. Calculations of the angular momentum projections, partial density of states, and the XANES spectra confirmed the experimental findings of the Cr 23 C 6 precipitate evolution. In contrast, the local atomic structure around Fe and Ni atoms demonstrated irradiation resistance.

36 MATERIALS SCIENCE↗

Elucidating the Discharge Behavior of Aqueous Zinc Sulfur Batteries in the Presence of Molybdenum(IV) Chalcogenide Catalyst: The Criticality of Interfacial Electrochemistry

The aqueous zinc-sulfur battery holds promise for significant capacity and energy density with low cost and safe operation based on environmentally benign materials. However, it suffers from the sluggish kinetics of the conversion reaction. Here, we highlight the efficacy of molybdenum(IV) sulfide (MoS 2 ) to reduce the overpotential of S-ZnS conversion in aqueous electrolytes and study the discharge products formed at the solid-solid and solid-liquid interfaces using experimental and theoretical approaches. Specifically, the MoS 2 -catalyzed electrochemical conversion reaction is characterized via ex situ X-ray diffraction (XRD), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), Raman spectroscopy, synchrotron-based Mo K-edge X-ray absorption spectroscopy (XAS), and in situ synchrotron-based X-ray computed tomography (XCT). Additionally, operando synchrotron-based S K-edge XAS and X-ray fluorescence (XRF) maps are collected to determine the spatial evolution of sulfur-based species at the electrode-electrolyte interface. Further, coupling the operando S K-edge XAS data with the simulated spectra and fitting the data suggested a possible ZnS 2 intermediate phase.

25 ENERGY STORAGE↗