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At least 181 records · Page 10

In situ monitoring of microstructure evolution during thermal processing of uranium-zirconium alloys using laser-generated ultrasound

In this study, laser-generated ultrasound was used to monitor microstructure evolution during thermal processing of as-cast, polycrystalline binary uranium-zirconium metallic fuel alloys with compositions of U-20wt.%Zr (U-20Zr), U-50wt.%Zr (U-50Zr) and U-80wt.%Zr (U-80Zr). Ultrasonic waveforms were recorded during heating and cooling the samples from room temperature to >973 K and back. A phase transition temperature for all three compositions was estimated from the temperature at which an abrupt and rapid reduction in ultrasonic velocities was observed. Microstructural features on the length scale of tens of micrometers were inferred from the observation of scattering of ultrasonic waves by elastic heterogeneities above ~823 K in U-20Zr, while a hysteresis in the ultrasonic velocities of U-80Zr upon cooling was attributed to a partial retention of the high temperature phase following thermal annealing. The U-50Zr alloy exhibited a reversible viscoelastic response above 933 K, as evidenced by the observation of high frequency attenuation of the shear component of the waveforms at high temperature. Ultrasonic measurements were supplemented by in situ transmission electron microscopy (TEM). The TEM images revealed that the δ-U-Zr matrix in the three compositions underwent a spinodal decomposition above ~823 K into nanoscale regions. The ultrasonic measurements revealed larger, micron-scale structure evolution in the U-20Zr alloy at the same temperature. This large-scale structure is associated with heterogeneous regions having different Zr content. Our findings show the potential heating rate dependence of microstructural evolution in U-Zr alloys and highlight differences in the thermomechanical response and associated length scales during thermal annealing between single- and dual-phase compositions. These results demonstrate the utility of laser ultrasonics to rapidly and efficiently scan phase boundaries and monitor micrometer-scale structure evolution in metallic fuel alloys.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Engineering anisotropic electrodynamics at the graphene/CrSBr interface

Abstract Graphene is a privileged 2D platform for hosting confined light-matter excitations known as surface plasmon polaritons (SPPs), as it possesses low intrinsic losses and a high degree of optical confinement. However, the isotropic nature of graphene limits its ability to guide and focus SPPs, making it less suitable than anisotropic elliptical and hyperbolic materials for polaritonic lensing and canalization. Here, we present graphene/CrSBr as an engineered 2D interface that hosts highly anisotropic SPP propagation across mid-infrared and terahertz energies. Using scanning tunneling microscopy, scattering-type scanning near-field optical microscopy, and first-principles calculations, we demonstrate mutual doping in excess of 10 13 cm –2 holes/electrons between the interfacial layers of graphene/CrSBr. SPPs in graphene activated by charge transfer interact with charge-induced electronic anisotropy in the interfacial doped CrSBr, leading to preferential SPP propagation along the quasi-1D chains that compose each CrSBr layer. This multifaceted proximity effect both creates SPPs and endows them with anisotropic propagation lengths that differ by an order-of-magnitude between the in-plane crystallographic axes of CrSBr.

Science & Technology - Other Topics↗

An electronic microemulsion phase emerging from a quantum crystal-to-liquid transition

Strongly interacting electronic systems often exhibit a complicated phase diagram that results from the competition between different quantum ground states. One feature of these phase diagrams is the emergence of microemulsion phases, where regions of different phases self-organize across multiple length scales. The experimental characterization of these microemulsions can pose considerable challenges, as the long-range Coulomb interaction microscopically mingles with the competing states. Here we observe the signatures of the microemulsion between an electronic Wigner crystal and an electron liquid in a MoSe 2 monolayer using cryogenic reflectance and magneto-optical spectroscopy. We find that the transition into this microemulsion state is marked by anomalies in exciton reflectance, spin susceptibility and umklapp scattering, establishing it as a distinct phase of electronic matter.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ionic Liquid-Mediated Interfacial Polymerization for Fabrication of Reverse Osmosis Membranes

This study revealed the effects of incorporating ionic liquid (IL) molecules: 1-ethyl, 1-butyl, and 1-octyl-3-methyl-imidazolium chlorides with different alkyl chain lengths, in interfacial polymerization (IP) on the structure and property (i.e., permeate-flux and salt rejection ratio) relationships of resulting RO membranes. The IL additive was added in the aqueous meta-phenylene diamine (MPD; 0.1% w/v) phase, which was subsequently reacted with trimesoyl chloride (TMC; 0.004% w/v) in the hexane phase to produce polyamide (PA) barrier layer. The structure of resulting free-standing PA thin films was characterized by grazing incidence wide-angle X-rays scattering (GIWAXS), which results were correlated with the performance of thin-film composite RO membranes having PA barrier layers prepared under the same IP conditions. Additionally, the membrane surface properties were characterized by zeta potential and water contact angle measurements. It was found that the membrane prepared by the longer chain IL molecule generally showed lower salt rejection ratio and higher permeation flux, possibly due to the inclusion of IL molecules in the PA scaffold. This hypothesis was supported by the GIWAXS results, where a self-assembled surfactant-like structure formed by IL with the longest aliphatic chain length was detected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Derivation of Physical and Optical Properties of Midlatitude Cirrus Ice Crystals for a Size-Resolved Cloud Microphysics Model

Single-crystal images collected in mid-latitude cirrus are analyzed to provide internally consistent ice physical and optical properties for a size-resolved cloud microphysics model, including single-particle mass, projected area, fall speed, capacitance, single-scattering albedo, and asymmetry parameter. Using measurements gathered during two flights through a widespread synoptic cirrus shield, bullet rosettes are found to be the dominant identifiable habit among ice crystals with maximum dimension (Dmax) greater than 100μm. Properties are therefore first derived for bullet rosettes based on measurements of arm lengths and widths, then for aggregates of bullet rosettes and for unclassified (irregular) crystals. Derived bullet rosette masses are substantially greater than reported in existing literature, whereas measured projected areas are similar or lesser, resulting in factors of 1.5-2 greater fall speeds, and, in the limit of large Dmax, near-infrared single-scattering albedo and asymmetry parameter (g) greater by approx. 0.2 and 0.05, respectively. A model that includes commonly imaged side plane growth on bullet rosettes exhibits relatively little difference in microphysical and optical properties aside from approx. 0:05 increase in mid-visible g primarily attributable to plate aspect ratio. In parcel simulations, ice size distribution, and g are sensitive to assumed ice properties.

asymmetry↗

Correlating structural changes in thermoresponsive hydrogels to the optical response of embedded plasmonic nanoparticles

Stimuli-responsive microgels, composed of small beads with soft, deformable polymer networks swollen through a combination of synthetic control over the polymer and its interaction with water, form a versatile platform for development of multifunctional and biocompatible sensors. The interfacial structural variation of such materials at a nanometer length scale is essential to their function, but not yet fully comprehended. Here, we take advantage of the plasmonic response of a gold nanorod embedded in a thermoresponsive microgel (AuNR@PNIPMAm) to monitor structural changes in the hydrogel directly near the nanorod surface. By direct comparison of the plasmon response against measurements of the hydrogel structure from dynamic light scattering and nuclear magnetic resonance, we find that the microgel shell of batch-polymerized AuNR@PNIPMAm exhibits a heterogeneous volume phase transition reflected by different onset temperatures for changes in the hydrodyanmic radius (R H ) and plasmon resonance, respectively. The new approach of contrasting plasmonic response (a measure of local surface hydrogel structure) with R H and relaxation times paves a new path to gain valuable insight for the design of plasmonic sensors based on stimuli-responsive hydrogels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Y-shaped tricatenar azobenzenes – functional liquid crystals with synclinic–anticlinic transitions and spontaneous helix formation

A series of achiral tricatenar rod-like molecules with a 3,5-disubstitution pattern at one end and a single alkyl chain at the other end of a rod-like azobenzene derived core is reported. Depending on temperature and alkyl chain length, these Y-shaped compounds self-assemble into different types of liquid crystalline (LC) phases, ranging from non-tilted and synclinic tilted hexatic, via non-tilted and anticlinic tilted smectic and bicontinuous cubic LC phases, to a spontaneous mirror symmetry broken isotropic liquid (Iso 1 [*]) or a related achiral liquid network phase (Iso 1 ). An additional tilted, but uniaxial smectic phase was observed at the transition between anticlinic and synclinic tilt correlation and was investigated by soft resonant X-ray scattering with respect to possible helix formation. This work provides a new concept for the design of technological interesting azobenzene based LC materials with anticlinic tilted smectic C phases (SmC a ) and with azobenzene units organized in the long range or short range helical network structures of bicontinuous cubic and chiral isotropic liquid phases, respectively. Core fluorination removes all lamellar phases, leaving only the cubic phase over wide temperature ranges, even at ambient temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of the Edge Crack Torsion (ECT) Test for Mode III Fracture Toughness Measurement of Laminated Composites

The edge crack torsion (ECT) test is designed to initiate mode III delamination growth in composite laminates. An ECT specimen is a rectangular laminate, containing an edge delamination at the laminate mid-plane. Torsion load is applied to the specimens, resulting in relative transverse shear sliding of the delaminated faces. The test data reduction schemes are intended to yield initiation values of critical mode III strain energy release rate, G(sub IIIc), that are constant with delamination length. The test has undergone several design changes during its development. The objective of this paper was to determine the suitability of the current ECT test design as a mode III fracture test. To this end, ECT tests were conducted on specimens manufactured from IM7/8552 and specimens made from S2/8552 tape laminates. Several specimens, each with different delamination lengths are tested. Detailed, three-dimensional finite element analyses of the specimens were performed. The analysis results were used to calculate the distribution of mode I, mode II, and mode III strain energy release rate along the delamination front. The results indicated that mode III-dominated delamination growth would be initiated from the specimen center. However, in specimens of both material types, the measured values of G(sub IIIc) exhibited significant dependence on delamination length. Furthermore, there was a large amount of scatter in the data. Load-displacement response of the specimens exhibited significant deviation from linearity before specimen failure. X-radiographs of a sample of specimens revealed that damage was initiated in the specimens prior to failure. Further inspection of the failure surfaces is required to identify the damage and determine that mode III delamination is initiated in the specimens.

Ratcliffe, James G.↗

Multimodal Nanoscale Mapping of Local Structure and CO 2 Adsorption in Metal–Organic Frameworks

Diamine functionalization of the metal−organic framework Mg 2 (dobpdc) (dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) significantly enhances its selectivity for CO 2 capture from flue gases and air. The structure and CO 2 capacity of such materials are typically assessed using bulk techniques that rely on averaging signal over large ensembles of unit cells, obscuring local heterogeneities, such as variations in CO 2 occupancy across individual nanocrystals. To resolve this limitation, we demonstrate a multimodal, nanoscale characterization of Mg 2 (dobpdc) appended with 1,3-diaminopropane. By employing recently developed characterization techniques at progressively smaller length scales, we uncover insights from correspondingly smaller populations of unit cells. First, we use parallel-beam 3D electron diffraction (3D ED) to identify a prominent expansion in lattice parameters upon desorption of CO 2 , as observed at the level of single nanocrystals. Second, we use convergent-probe 4D scanning transmission electron microscopy (4D-STEM) to quantify associated differences in lattice strain as a function of gas loading and diamine appending. These measurements sample small subvolumes within individual nanocrystals. Finally, we apply infrared scattering scanning near-field optical microscopy (IR s- SNOM) to confirm variable CO 2 chemisorption across adsorption sites at the surface of single nanocrystals. This multimodal, multiscale approach allows us to map heterogeneity within individual nanocrystals. Collectively, these findings emphasize the importance of local, nanoscale characterization of metal−organic frameworks in revealing previously unresolvable features that impact their performance.

Karstens, Sarah L. [University of California, Berk↗

Guided-wave approaches to spectrally selective energy absorption

Results of experiments designed to demonstrate spectrally selective absorption in dielectric waveguides on semiconductor substrates are reported. These experiments were conducted with three waveguides formed by sputtering films of PSK2 glass onto silicon-oxide layers grown on silicon substrates. The three waveguide samples were studied at 633 and 532 nm. The samples differed only in the thickness of the silicon-oxide layer, specifically 256 nm, 506 nm, and 740 nm. Agreement between theoretical predictions and measurements of propagation constants (mode angles) of the six or seven modes supported by these samples was excellent. However, the loss measurements were inconclusive because of high scattering losses in the structures fabricated (in excess of 10 dB/cm). Theoretical calculations indicated that the power distribution among all the modes supported by these structures will reach its steady state value after a propagation length of only 1 mm. Accordingly, the measured loss rates were found to be almost independent of which mode was initially excited. The excellent agreement between theory and experiment leads to the conclusion that low loss waveguides confirm the predicted loss rates.

Stegeman, G. I.↗

AVIRIS Inflight Calibration Experiments, Analysis, and Results in 2000

The NASA Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) measures spectra from 370 to 2500 nm with nominally 10-nm sampling and resolution. The spectra are acquired as images with an 11 km width and up to 800 km length from the ER-2 platform or 2.1 km width and 160 km length from the Twin Otter platform. AVIRIS measurements are used for a range of Earth science research and application objectives. The molecular absorption and particle scattering properties expressed in the calibrated AVIRIS measurements are used. For both science research and application objectives, calibration of the AVIRIS spectra is required to produce useful results. Each year prior to the flight season AVIRIS is calibrated in the laboratory. However, the temperature, pressure, vibration, and observational geometry, as well as mechanical, electrical, and operational interfaces of the laboratory are different than the environment on board the airborne platform. To validate the calibration of AVIRIS in the flight environment, an inflight calibration experiment is orchestrated at the beginning of each flight season. In most years additional inflight calibration experiments occur towards the middle and end of the flight season as well. For an inflight calibration experiment, AVIRIS acquires airborne data over a designated calibration target. In concert with the airborne data acquisition, surface and atmospheric properties at the calibration target are measured in situ. These in situ measurements are used to constrain a radiative transfer code and predict the radiance incident at the AVIRIS instrument from the calibration target. This prediction is compared with the AVIRIS-measured radiance to validate the calibration of AVIRIS in the flight environment. Additional properties (such as the AVIRIS inflight measurement precision) are determined as well. This paper presents measurements, analyses, and results from the inflight calibration experiment held on the dry lake bed surface of Rogers Dry Lake, California, on June 5, 2000.

Green, Robert O.↗

Comparison of short-range order in irradiated dysprosium titanates

Abstract The structural response of Dy 2 TiO 5 oxide under swift heavy ion irradiation (2.2 GeV Au ions) was studied over a range of structural length scales utilizing neutron total scattering experiments. Refinement of diffraction data confirms that the long-range orthorhombic structure is susceptible to ion beam-induced amorphization with limited crystalline fraction remaining after irradiation to 8 × 10 12 ions/cm 2 . In contrast, the local atomic arrangement, examined through pair distribution function analysis, shows only subtle changes after irradiation and is still described best by the original orthorhombic structural model. A comparison to Dy 2 Ti 2 O 7 pyrochlore oxide under the same irradiation conditions reveals a different behavior: while the dysprosium titanate pyrochlore is more radiation resistant over the long-range with smaller degree of amorphization as compared to Dy 2 TiO 5 , the former involves more local atomic rearrangements, best described by a pyrochlore-to-weberite-type transformation. These results highlight the importance of short-range and medium-range order analysis for a comprehensive description of radiation behavior.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Structural Insights into Low and High Recalcitrance Natural Poplar Variants Using Neutron and X-ray Scattering

Here, we used small-angle neutron scattering (SANS) and wide-angle X-ray scattering (WAXS) to study two Populus trichocarpa variants, GW-11012 and BESC-316, with lignin contents of 17.8 and 23.2%, respectively, to understand why the low lignin variant has increased sugar release during liquid hot water (LHW) pretreatment. SANS showed differences in cell wall polymer arrangement in the variants. In GW-11012, the cellulose microfibrils were similar in size to BESC-316 but were not equally spaced and lignin was aggregated rather than homogenously interspersed with other matrix co-polymers. However, after LHW pretreatments, the SANS profiles of the pretreated variants were almost indistinguishable, indicating that the nanoscale structural features could not adequately explain the increased sugar release observed in GW-11012. WAXS analysis revealed higher cellulose crystallinity and larger crystallite size in native and pretreated GW-11012. However, the most significant difference was that the crystallite orientation was approximately 2-fold higher in GW-11012. This suggests that higher crystallite orientation may be favorable for the action of processive cellulases leading to increased sugar release from GW-11012. Our study shows that there is a complex interplay between cell wall polymers during their deposition resulting in changes in lignin distribution and cellulose structure, highlighting the importance of investigating plant cell wall architecture across multiple length scales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering

Abstract The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip) 2 ] 2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered ( 3 MC) excited state surface. This 3 MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a 3 MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electromagnetic scattering by coated convex surfaces and wedges simulated by approximate boundary conditions

Asymptotic/high-frequency solutions are developed for analyzing the non-specular scattering mechanisms associated with coated convex surfaces and edges simulated by approximate boundary conditions. In particular, the standard impedance boundary conditions (SIBC's) and the second order generalized impedance boundary conditions (GIBC's) are employed for a characterization of the edge diffraction, creeping wave, and surface diffracted wave contributions. To study the creeping wave and surface diffracted wave mechanisms, rigorous UTD (uniform geometrical theory of diffraction) diffraction coefficients are developed for a convex coated cylinder simulated with SIBC's and GIBC's. The ray solutions obtained remain valid in the transition region and reduce uniformly to those in the deep lit and shadow regions. A uniform asymptotic solution is also presented for observations in the close vicinity of the cylinder. The diffraction coefficient for a convex cylinder are obtained via a generalization of the corresponding ones of the circular cylinder. To validate the asymptotic/high-frequency solution, integral equations are derived for both E and H-polarization and solved numerically using the method of moments. Results are presented for a single and three layered coated convex cylinder. Some insights are also provided on the accuracy of the employed GIBC's versus SIBC's for application to curved surfaces. To characterize the scattering by impedance wedges illuminated at skew incidence, diffraction coefficients are derived from an approximate solution of the governing functional difference equations. This solution exactly recovers the known ones for an impedance half plane or an arbitrary wedge at normal incidence, and to validate it for other wedge angles, a moment method code was used. Finally, to test the usefulness of the approximate skew incidence impedance wedge diffraction coefficient for three dimensional structures, equivalent currents are derived in the context of the physical theory of diffraction (PTD) for a finite length impedance wedge of arbitrary internal angles. These are incorporated in a standard general purpose PTD code and results are presented for a number of different impedance structures.

Syed, H. H.↗

Structure of diopside, enstatite, and magnesium aluminosilicate glasses: A joint approach using neutron and x-ray diffraction and solid-state NMR

Neutron diffraction with magnesium isotope substitution, high energy x-ray diffraction, and 29 Si, 27 Al, and 25 Mg solid-state nuclear magnetic resonance (NMR) spectroscopy were used to measure the structure of glassy diopside (CaMgSi 2 O 6 ), enstatite (MgSiO 3 ), and four (MgO) x (Al 2 O 3 ) y (SiO 2 ) 1–x–y glasses, with x = 0.375 or 0.25 along the 50 mol. % silica tie-line (1 – x – y = 0.5) or with x = 0.3 or 0.2 along the 60 mol. % silica tie-line (1 – x – y = 0.6). The bound coherent neutron scattering length of the isotope 25 Mg was remeasured, and the value of 3.720(12) fm was obtained from a Rietveld refinement of the powder diffraction patterns measured for crystalline 25 MgO. The diffraction results for the glasses show a broad asymmetric distribution of Mg–O nearest-neighbors with a coordination number of 4.40(4) and 4.46(4) for the diopside and enstatite glasses, respectively. As magnesia is replaced by alumina along a tie-line with 50 or 60 mol. % silica, the Mg–O coordination number increases with the weighted bond distance as less Mg 2+ ions adopt a network-modifying role and more of these ions adopt a predominantly charge-compensating role. 25 Mg magic angle spinning (MAS) NMR results could not resolve the different coordination environments of Mg 2+ under the employed field strength (14.1 T) and spinning rate (20 kHz). The results emphasize the power of neutron diffraction with isotope substitution to provide unambiguous site-specific information on the coordination environment of magnesium in disordered materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relating ground truth collection to model sensitivity

The importance of collecting high quality ground truth before a SAR mission over a forested area is two fold. First, the ground truth is used in the analysis and interpretation of the measured backscattering properties; second, it helps to justify the use of a scattering model to fit the measurements. Unfortunately, ground truth is often collected based on visual assessment of what is perceived to be important without regard to the mission itself. Sites are selected based on brief surveys of large areas, and the ground truth is collected by a process of selecting and grouping different scatterers. After the fact, it may turn out that some of the relevant parameters are missing. A three-layer canopy model based on the radiative transfer equations is used to determine, before hand, the relevant parameters to be collected. Detailed analysis of the contribution to scattering and attenuation of various forest components is carried out. The goal is to identify the forest parameters which most influence the backscattering as a function of frequency (P-, L-, and C-bands) and incident angle. The influence on backscattering and attenuation of branch diameters, lengths, angular distribution, and permittivity; trunk diameters, lengths, and permittivity; and needle sizes, their angular distribution, and permittivity are studied in order to maximize the efficiency of the ground truth collection efforts. Preliminary results indicate that while a scatterer may not contribute to the total backscattering, its contribution to attenuation may be significant depending on the frequency.

Amar, Faouzi↗

Imaging Anisotropic Waveguide Exciton Polaritons in Tin Sulfide

In recent years, novel materials supporting in-plane anisotropic polaritons have attracted a great deal of research interest due to their capability of shaping nanoscale field distributions and controlling nanophotonic energy flows. Here we report a nano-optical imaging study of waveguide exciton polaritons (EPs) in tin sulfide (SnS) in the near-infrared (near-IR) region using scattering-type scanning near-field optical microscopy (s-SNOM). With s-SNOM, we mapped in real space the propagative EPs in SnS, which show sensitive dependence on the excitation energy and sample thickness. Moreover, we found that both the polariton wavelength and propagation length are anisotropic in the sample plane. In particular, in a narrow spectral range from 1.32 to 1.44 eV, the EPs demonstrate quasi-one-dimensional propagation, which is rarely seen in natural polaritonic materials. Here, a further analysis indicates that the observed polariton anisotropy originates from the different optical band gaps and exciton binding energies along the two principal crystal axes of SnS.

77 NANOSCIENCE AND NANOTECHNOLOGY↗