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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 163 records · Page 9

Goethite and Hematite Nucleation and Growth from Ferrihydrite: Effects of Oxyanion Surface Complexes

The presence of oxyanions, such as nitrate (NO 3 – ) and phosphate (PO 4 3– ), regulates the nucleation and growth of goethite (Gt) and hematite (Hm) during the transformation of ferrihydrite (Fh). Our previous studies showed that oxyanion surface complexes control the rate and pathway of Fh transformation to Gt and Hm. However, how oxyanion surface complexes control the mechanism of Gt and Hm nucleation and growth during the Fh transformation is still unclear. Here, we used synchrotron scattering methods and cryogenic transmission electron microscopy to investigate the effects of NO 3 – outer-sphere complexes and PO 4 3– inner-sphere complexes on the mechanism of Gt and Hm formation from Fh. Our TEM results indicated that Gt particles form through a two-step model in which Fh particles first transform to Gt nanoparticles and then crystallographically align and grow to larger particles by oriented attachment (OA). In contrast, for the formation of Hm, imaging shows that Fh particles first aggregate and then transform to Hm through interface nucleation. This is consistent with our X-ray scattering results, which demonstrate that NO 3 – outer-sphere and PO 4 3– inner-sphere complexes promote the formation of Gt and Hm, respectively. These results have implications for understanding the coupled interactions of oxyanions and iron oxy-hydroxides in Earth-surface environments.

54 ENVIRONMENTAL SCIENCES↗

A Quantum Interpretation of Light Scattering near the Boundary between Transparent Media with Kerr Nonlinearity

The transformation of light by a nonlinear beamsplitter is considered. The beamsplitter is formed by a plane interface between two transparent dielectrics, at least one of which has a Kerr nonlinearity; i.e., its refractive index depends on the intensity of the penetrating radiation. It is shown that the interpretation of the result of calculation of quantum fields at the outputs from such a beamsplitter indicates a violation of the principle of causality in the sense that a subsequent event affects the previous one.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Observation of solid-state bidirectional thermal conductivity switching in antiferroelectric lead zirconate (PbZrO 3 )

Materials with tunable thermal properties enable on-demand control of temperature and heat flow, which is an integral component in the development of solid-state refrigeration, energy scavenging, and thermal circuits. Although gap-based and liquid-based thermal switches that work on the basis of mechanical movements have been an effective approach to control the flow of heat in the devices, their complex mechanisms impose considerable costs in latency, expense, and power consumption. As a consequence, materials that have multiple solid-state phases with distinct thermal properties are appealing for thermal management due to their simplicity, fast switching, and compactness. Thus, an ideal thermal switch should operate near or above room temperature, have a simple trigger mechanism, and offer a quick and large on/off switching ratio. In this study, we experimentally demonstrate that manipulating phonon scattering rates can switch the thermal conductivity of antiferroelectric PbZrO 3 bidirectionally by –10% and +25% upon applying electrical and thermal excitation, respectively. Our approach takes advantage of two separate phase transformations in PbZrO 3 that alter the phonon scattering rate in different manners. In this study, we demonstrate that PbZrO 3 can serve as a fast (<1 second), repeatable, simple trigger, and reliable thermal switch with a net switching ratio of nearly 38% from ~1.20 to ~1.65 W m –1 K –1 .

25 ENERGY STORAGE↗

Imaging Wavepackets in Real-Space & Disentangling Ultrafast Solvation Dynamics with High-Energy Ultrafast X-ray Scattering

The microscopic information of solute and solute-solvent motions can be measured using ultrafast diffuse x-ray scattering, and compared to molecular dynamics simulations, as demonstrated in studies of solvated molecular systems done in X-ray free-electron lasers. However, for the typical photon energies used in these experiments, the photon momentum transfer range was limited to lower Q values where the signals arising from different parts of the studied system overlap significantly. Recently, this limitation was greatly alleviated by extending the photon energy at the Linac Coherent Light-Source (LCLS), significantly increasing the accessible momentum transfer range. This improvement is transformative for ultrafast diffuse x-ray scattering measurements, enabling for the first time to disentangle the solute scattering difference signal, that persists to higher Q values, from the bulk solvent and solute-solvent cross-terms difference signals. In addition, it enhances the prediction ability of modeling and simulation methods such as the hybrid QM/MM approach. The extended Q range also opens the way to resolve in real-space details regarding coherent wavepackets motions beyond their center-of-mass positions. Here, we present the first results on high-energy (18keV) diffuse x-ray scattering in solution, demonstrating high fidelity time-resolved scattering and analysis of the photoexcited model photocatalysts PtPOP ([Pt2(POP)4]4-), and IrDimen ([Ir2(dimen)4]2+) in several solvents. These complexes provide ideal systems for demonstrating the ability of high-Q ultrafast scattering and QM/MM simulations to decompose ultrafast solvation dynamics into specific changes in the solute-solvent pair distribution function with a particular focus on how electronically excited states change the interaction between the solvent and photo-catalytically active metal sites. We introduce an approach to further utilize the high-energy capability and demonstrate a single-shot ultra-wide-angle X-ray Scattering modality using two perpendicular detectors, spanning a scattering angle range of more than 100 degrees, allowing to extend the accessible momentum transfer range up to Q~14 Å-1. We develop a model-free method to invert the x-ray scattering signals and enable the recovery of multiple pair-density motions that happen simultaneously, allowing us to directly measure in real-space nuclear wavepacket motions. . [1] Natan, Adi. "Real-Space Inversion and Super-Resolution of Ultrafast X-ray Scattering using Natural Scattering Kernels." arXiv preprint arXiv:2107.05576 (2021)

Natan, Adi↗

Scattering and Diffraction of Electromagnetic Radiation: An Effective Probe to Material Structure

Scattered electromagnetic waves from material bodies of different forms contain, in an intricate way, precise information on the intrinsic, geometrical and physical properties of the objects. Scattering theories, ever deepening, aim to provide dependable interpretation and prediction to the complicated interaction of electromagnetic radiation with matter. There are well-established multiple-scattering formulations based on classical electromagnetic theories. An example is the Generalized Multi-particle Mie-solution (GMM), which has recently been extended to a special version ̶ the GMM-PA approach, applicable to finite periodic arrays consisting of a huge number (e.g., >>106) of identical scattering centers [1]. The framework of the GMM-PA is nearly complete. When the size of the constituent unit scatterers becomes considerably small in comparison with incident wavelength, an appropriate array of such small element volumes may well be a satisfactory representation of a material entity having an arbitrary structure. X-ray diffraction is a powerful characterization tool used in a variety of scientific and technical fields, including material science. A diffraction pattern is nothing more than the spatial distribution of scattered intensity, determined by the distribution of scattering matter by way of its Fourier transform [1]. Since all linear dimensions entered into Maxwell's equations are normalized by wavelength, an analogy exists between optical and X-ray diffraction patterns. A large set of optical diffraction patterns experimentally obtained can be found in the literature [e.g., 2,3]. Theoretical results from the GMM-PA have been scrutinized using a large collection of publically accessible, experimentally obtained Fraunhofer diffraction patterns. As far as characteristic structures of the patterns are concerned, theoretical and experimental results are in uniform agreement; no exception has been found so far. Closely connected with the spatial distribution of scattered intensities are cross sections, such as for extinction, scattering, absorption, and radiation pressure, as a critical type of key quantity addressed in most theoretical and experimental studies of radiative scattering. Cross sections predicted from different scattering theories are supposed to be in general agreement. For objects of irregular shape, the GMM-PA solutions can be compared with the highly flexible Discrete Dipole Approximation (DDA) [4,5] when dividing a target to no more than ~106 unit cells. Also, there are different ways to calculate the cross sections in the GMM-PA, providing an additional means to examine the accuracy of the numerical solutions and to unveil potential issues concerning the theoretical formulations and numerical aspects. To solve multiple scattering by an assembly of material volumes through classical theories such as the GMM-PA, the radiative properties of the component scatterers, the complex refractive index in particular, must be provided as input parameters. When using a PA to characterize a material body, this involves the use of an adequate theoretical tool, an effective medium theory, to connect Maxwell's phenomenogical theory with the atomistic theory of matter. In the atomic theory, one regards matter as composed of interacting particles (atoms and molecules) embedded in the vacuum [6]. However, the radiative properties of atomic-scaled particles are known to be substantially different from bulk materials. Intensive research efforts in the fields of cluster science and nanoscience attempt to bridge the gap between bulk and atom and to understand the transition from classical to quantum physics. The GMM-PA calculations, which place virtually no restriction on the component-particle size, might help to gain certain insight into the transition.

Xu, Yu-Lin↗

Influence of aerosol scattering on atmospheric blurring of surface features

The influence of the shape of atmospheric scattering phase functions on blurring of surface detail in images acquired from space is investigated. The effects are characterized by computing atmospheric transfer functions and by solving the multidimensional equation of radiative transfer using a Fourier transform method. It is predicted that increased forward scattering enhances the detectability of atmospheric blurring near reflectance boundaries. Results for off-nadir viewing are also presented.

Diner, D. J.↗

Multislice forward modeling of coherent surface scattering imaging on surface and interfacial structures

To study nanostructures on substrates, surface-sensitive reflection-geometry scattering techniques such as grazing incident small angle X-ray scattering are commonly used to yield an averaged statistical structural information of the surface sample. Grazing incidence geometry can probe the absolute three-dimensional structural morphology of the sample if a highly coherent beam is used. Coherent surface scattering imaging (CSSI) is a powerful yet non-invasive technique similar to coherent X-ray diffractive imaging (CDI) but performed at small angles and grazing-incidence reflection geometry. A challenge with CSSI is that conventional CDI reconstruction techniques cannot be directly applied to CSSI because the Fourier-transform-based forward models cannot reproduce the dynamical scattering phenomenon near the critical angle of total external reflection of the substrate-supported samples. To overcome this challenge, we have developed a multislice forward model which can successfully simulate the dynamical or multi-beam scattering generated from surface structures and the underlying substrate. The forward model is also demonstrated to be able to reconstruct an elongated 3D pattern from a single shot scattering image in the CSSI geometry through fast-performing CUDA-assisted PyTorch optimization with automatic differentiation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Water or Anion? Uncovering the Zn 2+ Solvation Environment in Mixed Zn(TFSI) 2 and LiTFSI Water-in-Salt Electrolytes

Applications of aqueous zinc batteries for grid-scale energy storage are limited by their poor reversibility and the competing water splitting reaction. The recent invention of a water-in-salt (WIS) electrolyte concept provides a new route enabling a stable and highly reversible aqueous zinc battery chemistry. In the present work, a mixed zinc bis(trifluoromethane sulfonyl)imide (Zn(TFSI) 2 ) and LiTFSI WIS electrolyte was studied using X-ray total scattering, X-ray absorption, and Fourier transform infrared spectroscopy in conjunction with classical molecular dynamics simulations. It was found that, in the highly concentrated WIS electrolyte consisting of 1 m Zn(TFSI) 2 and 20 m LiTFSI, Zn 2+ cations are mainly solvated by six waters in their first solvation shell, while the TFSI – anions are completely excluded. This ion solvation picture is fundamentally different from the previous understandings. The results suggest that additional studies are needed to fully understand the unusual stability and reversibility of zinc-WIS electrolyte-based batteries.

25 ENERGY STORAGE↗

Revealing and Engineering Assembly Pathways of 3D DNA Origami Crystals

Recent developments in nanomaterial self-assembly demonstrate the capability to create tailored nanostructures by engineering both the binding coordination and specificity of interactions between material subunits. DNA origami frames allow for the design and fabrication of a broad variety of ordered 3D nanoscale architectures through self-assembly, facilitated by frame-to-frame bonds with designable strength and specificity. While the bond design is critical to lattice formation, the assembly process itself is often dependent on a thermal pathway. Highly ordered nanoscale frameworks, assembled from DNA frames, are predominantly crystallized through thermal annealing pathways that typically follow a “slow” cooling approach, with experiments on the time scale of days yielding DNA origami crystals in the range of 1−10 μm. This extended assembly time scale hinders the study of crystal formation pathways, necessitating a deeper understanding of factors governing successful annealing. Lack of insight into time scale also presents a practical limitation for material fabrication. Here, we investigate key factors affecting lattice assembly pathways and demonstrate that precise engineering of assembly conditions greatly reduces assembly times by up to nearly 2 orders of magnitude. We evaluate the nucleation and growth of crystals via optical and electron microscopy, and small-angle X-ray scattering techniques, mapping the time−temperature-transformation of superlattices from the melt through single-crystal optical tracking. The results show that origami frame assembly can be described by classical nucleation and growth theory, which can, in turn, be used to prescribe the growth of the crystals. Lastly, these findings are applied to demonstrate thermal pathway-dependent assembly, forming distinct assemblies based on different thermal annealing profiles.

36 MATERIALS SCIENCE↗

Introducing metal–sulfur active sites in metal–organic frameworks via post-synthetic modification for hydrogenation catalysis

Metal–sulfur active sites play a central role in catalytic processes such as hydrogenation and dehydrogenation, yet the majority of active sites in these compounds reside on the surfaces and edges of catalyst particles, limiting overall efficiency. Here we present a strategy to embed metal–sulfur active sites into metal–organic frameworks (MOFs) by converting bridging or terminal chloride ligands into hydroxide and subsequently into sulfide groups through post-synthetic modification. We apply this method to two representative MOF families: one featuring one-dimensional metal–chloride chains and another containing discrete multinuclear metal clusters. Crystallographic and spectroscopic analyses confirm structural integrity and sulfide incorporation, and the transformation is monitored by in situ total scattering methods. The sulfided MOFs display enhanced catalytic activity in the selective hydrogenation of nitroarenes using molecular hydrogen. Density functional theory calculations indicate that sulfur incorporation promotes homolytic metal–ligand bond cleavage and facilitates H 2 activation. This work establishes an approach to construct MOFs featuring accessible metal–sulfide sites.

Catalyst synthesis↗

Silver Nanoparticles Functionalized Nanosilica Grown over Graphene Oxide for Enhancing Antibacterial Effect

The continuous growth of multidrug-resistant bacteria due to the overuse of antibiotics and antibacterial agents poses a threat to human health. Silver nanoparticles, silica-based materials, and graphene-based materials have become potential antibacterial candidates. In this study, we developed an effective method of enhancing the antibacterial property of graphene oxide (GO) by growing nanosilica (NS) of approximately 50 nm on the graphene oxide (GO) surface. The structures and compositions of the materials were characterized through powdered X-ray diffraction (P-XRD), transmission electron microscopy (TEM), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS), ultraviolet–visible spectroscopy (UV–VIS), dynamic light scattering (DLS), Raman spectroscopy (RM), Fourier-transform infrared spectroscopy (FTIR), Brunauer–Emmet–Teller (BET) surface area, and pore size determination. The silver nanoparticles (AgNPs) with an average diameter of 26 nm were functionalized on the nanosilica (NS) surface. The composite contained approximately 3% of silver nanoparticles. The silver nanoparticles on nanosilica supported over graphene oxide (GO/NS/AgNPs) exhibited a 7-log reduction of Escherichia coli and a 5.2-log reduction of Bacillus subtilis within one hour of exposure. Both GO/NS and GO/NS/AgNPs exhibited substantial antimicrobial effects against E. coli and B. subtilis.

36 MATERIALS SCIENCE↗

A laser tomographic investigation of liquid fuel sprays

A light scattering technique is combined with a tomographic transformation to convert line of sight integrated data, measured in sprays, to measurements of droplet size and concentration in volume elements within the spray. The technique is developed and assessed by systematic experiments in axisymmetric sprays generated by twin-fluid atomisers. The good agreement found shows that, provided certain conditions are satisfied by the local spray structure, the technique provides information on spray structure, similar in detail and extent to that derived by photography, but with reduced experimental time. The technique is applied to an investigation of a kerosene spray vaporizing in a hot gas stream.

Yule, A. J.↗

Harnessing quantum light for microscopic biomechanical imaging of cells and tissues

The biomechanical properties of cells and tissues play an important role in our fundamental understanding of the structures and functions of biological systems at both the cellular and subcellular levels. Recently, Brillouin microscopy, which offers a label-free spectroscopic means of assessing viscoelastic properties in vivo, has emerged as a powerful way to interrogate those properties on a microscopic level in living tissues. However, susceptibility to photodamage and photobleaching, particularly when high-intensity laser beams are used to induce Brillouin scattering, poses a significant challenge. This article introduces a transformative approach designed to mitigate photodamage in biological and biomedical studies, enabling nondestructive, label-free assessments of mechanical properties in live biological samples. By leveraging quantum-light-enhanced stimulated Brillouin scattering (SBS) imaging contrast, the signal-to-noise ratio is significantly elevated, thereby increasing sample viability and extending interrogation times without compromising the integrity of living samples. The tangible impact of this methodology is evidenced by a notable three-fold increase in sample viability observed after subjecting the samples to three hours of continuous squeezed-light illumination, surpassing the traditional coherent light-based approaches. The quantum-enhanced SBS imaging holds promise across diverse fields, such as cancer biology and neuroscience where preserving sample vitality is of paramount significance. By mitigating concerns regarding photodamage and photobleaching associated with high-intensity lasers, this technological breakthrough expands our horizons for exploring the mechanical properties of live biological systems, paving the way for an era of research and clinical applications.

Li, Tian↗

Evolution of the propagation vector of antiferroquadrupolar phases in Ce 3 Pd 20 Si 6 under magnetic field

Hidden-order phases that occur in a number of correlated $f$-electron systems are among the most elusive states of electronic matter. Their investigations are hindered by the insensitivity of standard physical probes, such as neutron diffraction, to the order parameter that is usually associated with higher-order multipoles of the $f$ orbitals. The heavy-fermion compound Ce 3 Pd 20 Si 6 exhibits magnetically hidden order at subkelvin temperatures, known as phase II. Additionally, for magnetic field applied along the [001] cubic axis, another phase II&prime; was detected, but the nature of the transition from phase II to phase II&prime; remained unclear. Here we use inelastic neutron scattering to argue that this transition is most likely associated with a change in the propagation vector of the antiferroquadrupolar order from (111) to (100). Despite the absence of magnetic Bragg scattering in phase II&prime; , its ordering vector is revealed by the location of an intense magnetic soft mode at the (100) wave vector, that is orthogonal to the applied field. At the II - II&prime; transition, this mode softens and transforms into quasielastic and nearly Q-independent incoherent scattering, which is likely related to the non-Fermi-liquid behavior recently observed at this transition. Our experiment also reveals sharp collective excitations in the field-polarized paramagnetic phase, after phase II&prime; is suppressed in fields above 4 T.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Photochromic Properties and Surface Enhanced Raman Scattering Spectra of Indoline Spiropyran in Silver-Based Nanocomposite Films

The structure and photochromic transformations of composite organometallic nanosystems composed of Ag nanoparticles covered with a layer of indoline-spiropyran (ISP) molecules from solutions were studied by spectrophotometry, surface Raman scattering spectroscopy (SERS) and quantum chemistry. Analysis of experimental data showed that studied nanostructured systems have photochromic properties, manifested in the reversible photo-induced changes both of the electronic-absorption spectra and of the relative intensity of the SERS bands. The open form of ISP, formed in the organometallic nanostructured film as a result of photochromic transformations, has an adsorption geometry, and, possibly, a conformation different from that formed as a result of chemisorption of ISP molecules on silver colloids.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Radar polarimetry for geoscience applications

The present volume on radar polarimetry for geoscience applications discusses wave properties and polarization, scattering matrix representation for simple targets, scattering models for point and distributed targets, polarimetric scatterometer systems and measurements, polarimetric radar system design, and polarimetric SAR applications. Attention is given to plane waves in a lossless homogeneous medium-wave polarization, polarization synthesis and response, and coordinate system transformations. Topics addressed include high- and low-frequency scattering, rough-surface scattering models, radiative transfer theory and deficiencies thereof, solutions for the radiative transfer equation, and a radiative transfer model for a forest canopy. Also discussed are network analyzer-based polarimetric scatterometers, calibration of polarimetric scatterometers, synthesized polarization response of distributed targets, and measurement of the propagation parameters of a forest canopy.

Ulaby, Fawwaz T.↗

Deep Learning Methods for Symbolic Calculations in HEP

This project develops machine learning methods to accelerate symbolic calculations in high-energy physics. Using sequence-to-sequence transformer models, we construct frameworks to predict squared amplitudes and related quantities for Standard Model processes, including quantum electrodynamics, quantum chromodynamics, and electroweak interactions. The results demonstrate that deep learning can successfully learn complex symbolic relationships and provide a scalable approach to symbolic computation with potential applications in precision calculations and collider phenomenology.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Insights into the Nanostructure, Solvation, and Dynamics of Liquid Electrolytes through Small-Angle X-Ray Scattering

The fundamental understanding of nanostructures of liquid electrolytes is expected to enable transformative gains in electrochemical energy storage capacities. However, the solvation structures and molecular dynamics in electrolytes are hard to probe, which limits further performance improvements in macroscopic properties such as ionic conductivity, viscosity, and stability. Small-angle X-ray scattering (SAXS), a non-destructive method for nanostructures characterization in liquids, offers a unique perspective on molecular clusters, anion-cation pairs, solvation sheath, percolating network, aggregates, and domain sizes of electrolytes. Notably, the SAXS method has excellent time-resolution, enabling the study of molecular dynamics by operando characterization. This review focuses on the microscopic understanding of liquid electrolytes by SAXS and operando SAXS. The unique capabilities of X-ray scattering for intra- and inter-molecular relationship and nanostructure characterization of electrolytes are highlighted.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗