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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 1,369 records · Page 76
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

X-ray Diffraction, Lattice Structure, and Equation of State of PdH x and PdD x to Megabar Pressures

High-pressure X-ray diffraction of PdH x and PdD x demonstrates that these materials remain in a face-centered cubic (fcc, $Fm\bar{3m}$) structure to megabar pressures at room temperature. The volumes indicate stoichiometric compositions under pressure with x = 1 for both materials. No indication of any phase transition was observed up to the highest pressures reached in the experiments. A third-order Birch–Murnaghan equation of state used to fit the pressure–volume data gives V 0 = 10.73 (±0.03) cm 3 /mol, K 0 = 147 (±11) GPa, and K 0 ' = 4.7 (±0.5), whereas a Vinet fit gives V 0 = 10.74 (±0.03) cm 3 /mol, K 0 = 143 (±11) GPa, and K 0 ' = 5.1 (±0.5), for the combined data for both PdH x and PdD x . Here, the results are used to obtain the pressure dependence of the effective volume of H and D atoms in PdH x and PdD x to megabar pressures for comparison with other simple hydrides with implications for superconductivity in this class of materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Reaction of Methane with MO x /CeO 2 (M = Fe, Ni, and Cu) Catalysts: In Situ Studies with Time-Resolved X-ray Diffraction

Changes in chemical state and structural transformations occurring in a series of MO x /CeO 2 (M = Cu, Ni and Fe) powder catalysts upon reaction with methane were investigated here using in situ time-resolved X-ray diffraction (TR-XRD), ex situ X-ray absorption near edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS shows the presence of adsorbed CH x and CO x species after exposing the powder catalysts to methane at room temperature. Temperature-programmed reduction (TPR) measurements point to reaction of the samples with methane and formation of CO, CO 2 , and H 2 O gas at temperatures as low as 100 °C. The TR-XRD results show that all of the transition-metal oxides in the as-prepared catalysts can be reduced to their metallic phase during the CH 4 -TPR process with the ceria support undergoing significant reduction from surface to bulk, yet the reduction temperature varies for different MO x /CeO 2 samples. Among these samples, CuO x /CeO 2 shows the lowest reduction temperature (below 260 °C) for both the oxide overlayer and the ceria support. The NiO x /CeO 2 and CoO x /CeO 2 powder catalysts also activate CH 4 at relatively low temperatures (below 350 °C), and the oxide overlayers undergo NiO → Ni and Co 3 O 4 → CoO → Co transformations. In the case of FeO x /CeO 2 , a series of complex changes in chemical state is observed for the oxide overlayer, Fe 2 O 3 → Fe 3 O 4 → FeO → Fe → Fe 3 C. The ceria support of the three MO x /CeO 2 (M = Cu, Ni, and Fe) samples undergoes severe reduction and forms Ce 2 O 3 at high temperature (>650 °C) during the CH 4 -TPR reaction. The in situ TR-XRD results highlight a rich and complex chemistry for methane on these MO x /CeO 2 mixed oxide systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Quantification of Metabolic Products from Microbial Hosts in Complex Media Using Optically Diffracting Hydrogels

In this work, we herein describe a highly versatile platform approach for the in situ and real-time screening of microbial biocatalysts for enhanced production of bioproducts using photonic crystal hydrogels. This approach was demonstrated by preparing optically diffracting films based on polymerized N-isopropylacrylamide that contracted in the presence of alcohols and organic acids. The hydrogel films were prepared in a microwell plate format, which allows for high-throughput screening, and characterized optically using a microwell plate reader. While demonstrating the ability to detect a broad range of relevant alcohols and organic acids, we showed that the response of the films correlated strongly with the octanol-water partition coefficient (log P) of the analyte. Differences in the secretion of ethanol and succinic acid from strains of Zymomonas mobilis and Actinobacillus succinogenes, respectively, were further detected via optical characterization of the films. These differences, which in some cases were as low as ~3 g/L, were confirmed by high-performance liquid chromatography, thereby demonstrating the sensitivity of this approach. Our findings highlight the potential utility of this multiplexed approach for the detection of small organic analytes in complex biological media, which overcomes a major challenge in conventional optical sensing methods.

09 BIOMASS FUELS↗
DOE OSTI2020

Lattice Strain Measurement of Core@Shell Electrocatalysts with 4D Scanning Transmission Electron Microscopy Nanobeam Electron Diffraction

Strain engineering enables the direct modification of atomic bonding and is currently an active area of research aimed at improving electrocatalytic activity. However, directly measuring the lattice strain of individual catalyst nanoparticles is challenging, especially at the scale of a single unit cell. In this study, we quantitatively map the strain present in rhodium@platinum (core@shell) nanocube electrocatalysts using conventional aberration-corrected scanning transmission electron microscopy (STEM) and the recently developed technique of 4D-STEM nanobeam electron diffraction. We demonstrate that 4D-STEM combined with data preconditioning allows for quantitative lattice strain mapping with subpicometer precision and without the influence of scan distortions. When combined with multivariate curve resolution, 4D-STEM allows us to distinguish the nanocube core from the shell and to quantify the unit cell size as a function of distance from the core–shell interface. Our results demonstrate that 4D-STEM has significant precision and accuracy advantages in strain metrology of catalyst materials compared to aberration-corrected STEM imaging and is beneficial for extracting information about the evolution of strain in catalyst nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Dynamic Hosts for High-Performance Li–S Batteries Studied by Cryogenic Transmission Electron Microscopy and in Situ X-ray Diffraction

Developing a high-performance sulfur host is central to the commercialization and general development of lithium–sulfur batteries. Here, for the first time, we propose the concept of dynamic hosts for lithium–sulfur batteries and elucidate the mechanism through which TiS 2 acts in such a fashion, using in situ X-ray diffraction and cryogenic scanning transmission electron microscopy (cryo-STEM). A TiS 2 –S composite electrode delivered a reversible capacity of 1120 mAh g –1 at 0.3 C after 200 cycles with a capacity retention of 97.0% and capacities of 886 and 613 mAh g –1 at 1.0 C up to 200 and 1000 cycles, respectively. Finally, our results indicate that it is Li x TiS 2 (0 < x ≤ 1), rather than TiS 2 , that effectively traps polysulfides and catalytically decomposes Li 2 S.

25 ENERGY STORAGE↗
DOE OSTI2020

Operando Bragg Coherent Diffraction Imaging of LiNi 0.8 Mn 0.1 Co 0.1 O 2 Primary Particles within Commercially Printed NMC811 Electrode Sheets

Due to complex degradation mechanisms, disparities between the theoretical and practical capacities of lithium-ion battery cathode materials persist. Specifically, Ni-rich chemistries such as LiNi 0.8 Mn 0.1 Co 0.1 O 2 (or NMC811) are one of the most promising choices for automotive applications; however, they continue to suffer severe degradation during operation that is poorly understood, thus challenging to mitigate. Here in this paper we use operando Bragg coherent diffraction imaging for 4D analysis of these mechanisms by inspecting the individual crystals within primary particles at various states of charge (SoC). Although some crystals were relatively homogeneous, we consistently observed non-uniform distributions of inter- and intracrystal strain at all measured SoC. Pristine structures may already possess heterogeneities capable of triggering crystal splitting and subsequently particle cracking. During low-voltage charging (2.7–3.5 V), crystal splitting may still occur even during minimal bulk deintercalation activity; and during discharging, rotational effects within parallel domains appear to be the precursor for the nucleation of screw dislocations at the crystal core. Ultimately, this discovery of the central role of crystal grain splitting in the charge/discharge dynamics may have ramifications across length scales that affect macroscopic performance loss during real-world battery operation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Imaging Strain-Localized Single-Photon Emitters in Layered GaSe below the Diffraction Limit

Nanoscale strain control of exciton funneling is an increasingly critical tool for the scalable production of single photon emitters (SPEs) in two-dimensional materials. However, conventional far-field optical microscopies remain constrained in spatial resolution by the diffraction limit and thus can provide only a limited description of nanoscale strain localization of SPEs. Here, we quantify the effects of nanoscale heterogeneous strain on the energy and brightness of GaSe SPEs on nanopillars with correlative cathodoluminescence, photoluminescence, and atomic force microscopy, supported by density functional theory simulations. We report the strain-localized SPEs have a broad range of emission wavelengths from 620 to 900 nm. We reveal substantial strain-controlled SPE wavelength tunability over a ~100 nm spectral range and 2 orders of magnitude enhancement in the SPE brightness at the pillar center due to Type-I exciton funneling. In addition, we show that radiative biexciton cascade processes contribute to observed CL photon superbunching. Also, the GaSe SPEs show excellent stability, where their properties remain unchanged after electron beam exposure. Importantly, we anticipate that this comprehensive study on the nanoscale strain control of two-dimensional SPEs will provide key insights to guide the development of truly deterministic quantum photonics.

2D materials↗
DOE OSTI2025

Attosecond Transient Grating Spectroscopy with Near-Infrared Grating Pulses and an Extreme Ultraviolet Diffracted Probe

Transient grating spectroscopy has become a mainstay among metal and semiconductor characterization techniques. Here, we extend the technique toward the shortest achievable time scales by using tabletop high-harmonic generation of attosecond extreme ultraviolet (XUV) pulses that diffract from transient gratings generated with sub-5 fs near-infrared (NIR) pulses. We demonstrate the power of attosecond transient grating spectroscopy (ATGS) by investigating the ultrafast photoexcited dynamics in an Sb semimetal thin film. ATGS provides an element-specific, background-free signal unfettered by spectral congestion, in contrast to transient absorption spectroscopy. With ATGS measurements in Sb polycrystalline thin films, we observe the generation of coherent phonons and investigate the lattice and carrier dynamics. Among the latter processes, we extract carrier thermalization, hot carrier cooling, and electron-hole recombination, which are on the order of 20 fs, 50 fs, and 2 ps time scales, respectively. Furthermore, the simultaneous collection of transient absorption and transient grating data allows us to extract the total complex dielectric constant in the sample dynamics with a single measurement, including the real-valued refractive index, from which we are also able to investigate carrier-phonon interactions and longer-lived phonon dynamics. The outlined experimental technique expands the capabilities of transient grating spectroscopy and attosecond spectroscopies by providing a wealth of information concerning carrier and lattice dynamics with an element-selective technique at the shortest achievable time scales.

Quintero-Bermudez, Rafael↗
DOE OSTI2018

Polarization-Dependent Second Harmonic Diffraction from Resonant GaAs Metasurfaces

Resonant semiconductor metasurfaces are an emerging versatile platform for nonlinear photonics. Here, we investigate second-harmonic generation from metasurfaces consisting of two-dimensional square arrays of gallium arsenide nanocylinders as a function of the polarization of the fundamental wave. To this end, we perform nonlinear second harmonic microscopy, where the pump wavelength is tuned to the resonances of the metasurfaces. Furthermore, imaging the generated nonlinear signal in Fourier space allows us to analyze the spatial properties of the generated second harmonic. Our experiments reveal that the second harmonic is predominantly emitted into the first diffraction orders of the periodic arrangements, and that its intensity varies with the polarization angle of the fundamental wave. While this can be expected from the structure of the GaAs nonlinear tensor, the characteristics of this variation itself are found to depend on the pump wavelength. Interestingly, we show that the metasurface can reverse the polarization dependence of the second harmonic with respect to an unstructured GaAs wafer. These general observations are confirmed by numerical simulations using a simplified model for the metasurface. In conclusion, our results provide valuable input for the development of metasurface-based classical and quantum light sources based on parametric processes.

36 MATERIALS SCIENCE↗
DOE OSTI2024

UV-Induced Reaction Pathways in Bromoform Probed with Ultrafast Electron Diffraction

For many chemical reactions, it remains notoriously difficult to predict and experimentally determine the rates and branching ratios between different reaction channels. This is particularly the case for reactions involving short-lived intermediates, whose observation requires ultrafast methods. The UV photochemistry of bromoform (CHBr 3 ) is among the most intensely studied photoreactions. Yet, a detailed understanding of the chemical pathways leading to the production of atomic Br and molecular Br 2 fragments has proven challenging. In particular, the role of isomerization and/or roaming and their competition with direct C–Br bond scission has been a matter of continued debate. Here, in this work, gas-phase ultrafast megaelectronvolt electron diffraction (MeV-UED) is used to directly study structural dynamics in bromoform after single 267 nm photon excitation with femtosecond temporal resolution. The results show unambiguously that isomerization contributes significantly to the early stages of the UV photochemistry of bromoform. In addition to direct C–Br bond breaking within <200 fs, formation of iso-CHBr 3 (Br-CH-Br-Br) is observed on the same time scale and with an isomer lifetime of >1.1 ps. The branching ratio between direct dissociation and isomerization is determined to be 0.4 ± 0.2:0.6 ± 0.2, i.e., approximately 60% of molecules undergo isomerization within the first few hundred femtoseconds after UV excitation. The structure and time of formation of iso-CHBr 3 compare favorably with the results of an ab initio molecular dynamics simulation. The lifetime and interatomic distances of the isomer are consistent with the involvement of a roaming reaction mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Intrinsic Elastic Anisotropy of Westerly Granite Observed by Ultrasound Measurements, Microstructural Investigations, and Neutron Diffraction

Westerly granite (WG) has been generally accepted as an isotropic homogeneous rock. Here, we return to WG and observe significant elastic anisotropy using multidirectional ultrasonic sounding on spherical samples at pressures up to 400 MPa. Thermal treatment of WG leads to formation of microcracks that reduce elastic wave velocities and increase its elastic anisotropy. The 3D distribution of P-wave velocities at low pressure is close to orthorhombic symmetry. Application of hydrostatic pressure closes most of thermally induced microcracks and decreases elastic anisotropy of WG, but at high pressure the anisotropy is practically reversed compared to low pressure: maximum P-wave velocity direction at low pressures is near minimum velocity direction at high pressure and vice versa. To understand this effect, microstructures of the rock were investigated by optical and scanning electron microscopy. Preferred orientations of four major rock-forming minerals—quartz, orthoclase, plagioclase, and biotite—were measured by time-of-flight neutron diffraction, which confirms significant crystal alignment. All these data were used to numerically model anisotropic elastic properties of WG. It is shown that WG possesses weak intrinsic elastic anisotropy related mainly to the preferred orientation of feldspars formed during igneous crystallization. Observed microcracks are mostly related to the cleavage planes of feldspars and biotite, and thus also demonstrate preferred orientation. Higher preheating temperatures produce larger quantity of longer microcracks. A numerical model shows that these microcracks act against the weak intrinsic elastic anisotropy of WG, and define the elastic anisotropy at low pressures.

58 GEOSCIENCES↗
DOE OSTI2017

Time-resolved diffraction of shock-released SiO 2 and diaplectic glass formation

Understanding how rock-forming minerals transform under shock loading is critical for modeling collisions between planetary bodies, interpreting the significance of shock features in minerals and for using them as diagnostic indicators of impact conditions, such as shock pressure. To date, our understanding of the formation processes experienced by shocked materials is based exclusively on ex situ analyses of recovered samples. Formation mechanisms and origins of commonly observed mesoscale material features, such as diaplectic (i.e., shocked) glass, remain therefore controversial and unresolvable. Here in this paper we show in situ pump-probe X-ray diffraction measurements on fused silica crystallizing to stishovite on shock compression and then converting to an amorphous phase on shock release in only 2.4 ns from 33.6 GPa. Recovered glass fragments suggest permanent densification. These observations of real-time diaplectic glass formation attest that it is a back-transformation product of stishovite with implications for revising traditional shock metamorphism stages.

36 MATERIALS SCIENCE↗
DOE OSTI2018

In situ coherent diffractive imaging

Coherent diffractive imaging (CDI) has been widely applied in the physical and biological sciences using synchrotron radiation, X-ray free-electron laser, high harmonic generation, electrons, and optical lasers. One of CDI’s important applications is to probe dynamic phenomena with high spatiotemporal resolution. Here, we report the development of a general in situ CDI method for real-time imaging of dynamic processes in solution. By introducing a time-invariant overlapping region as real-space constraint, we simultaneously reconstructed a time series of complex exit wave of dynamic processes with robust and fast convergence. We validated this method using optical laser experiments and numerical simulations with coherent X-rays. Our numerical simulations further indicated that in situ CDI can potentially reduce radiation dose by more than an order of magnitude relative to conventional CDI. With further development, we envision in situ CDI could be applied to probe a range of dynamic phenomena in the future.

47 OTHER INSTRUMENTATION↗
DOE OSTI2018

Layer specific observation of slow thermal equilibration in ultrathin metallic nanostructures by femtosecond X-ray diffraction

Ultrafast heat transport in nanoscale metal multilayers is of great interest in the context of optically induced demagnetization, remagnetization and switching. If the penetration depth of light exceeds the bilayer thickness, layer-specific information is unavailable from optical probes. Femtosecond diffraction experiments provide unique experimental access to heat transport over single digit nanometer distances. Here, we investigate the structural response and the energy flow in the ultrathin double-layer system: gold on ferromagnetic nickel. Even though the excitation pulse is incident from the Au side, we observe a very rapid heating of the Ni lattice, whereas the Au lattice initially remains cold. The subsequent heat transfer from Ni to the Au lattice is found to be two orders of magnitude slower than predicted by the conventional heat equation and much slower than electron–phonon coupling times in Au. We present a simplified model calculation highlighting the relevant thermophysical quantities.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Three-dimensional X-ray diffraction imaging of dislocations in polycrystalline metals under tensile loading

Abstract The nucleation and propagation of dislocations is an ubiquitous process that accompanies the plastic deformation of materials. Consequently, following the first visualization of dislocations over 50 years ago with the advent of the first transmission electron microscopes, significant effort has been invested in tailoring material response through defect engineering and control. To accomplish this more effectively, the ability to identify and characterize defect structure and strain following external stimulus is vital. Here, using X-ray Bragg coherent diffraction imaging, we describe the first direct 3D X-ray imaging of the strain field surrounding a line defect within a grain of free-standing nanocrystalline material following tensile loading. By integrating the observed 3D structure into an atomistic model, we show that the measured strain field corresponds to a screw dislocation.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Anomalous X-ray diffraction studies of ion transport in K + channels

Potassium ion channels utilize a highly selective filter to rapidly transport K + ions across cellular membranes. This selectivity filter is composed of four binding sites which display almost equal electron density in crystal structures with high potassium ion concentrations. This electron density can be interpreted to reflect a superposition of alternating potassium ion and water occupied states or as adjacent potassium ions. Here, we use single wavelength anomalous dispersion (SAD) X-ray diffraction data collected near the potassium absorption edge to show experimentally that all ion binding sites within the selectivity filter are fully occupied by K + ions. These data support the hypothesis that potassium ion transport occurs by direct Coulomb knock-on, and provide an example of solving the phase problem by K-SAD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Imaging antiferromagnetic antiphase domain boundaries using magnetic Bragg diffraction phase contrast

Manipulating magnetic domains is essential for many technological applications. Recent breakthroughs in Antiferromagnetic Spintronics brought up novel concepts for electronic device development. Imaging antiferromagnetic domains is of key importance to this field. Unfortunately, some of the basic domain types, such as antiphase domains, cannot be imaged by conventional techniques. Herein, we present a new domain projection imaging technique based on the localization of domain boundaries by resonant magnetic diffraction of coherent X rays. Contrast arises from reduction of the scattered intensity at the domain boundaries due to destructive interference effects. We demonstrate this approach by imaging antiphase domains in a collinear antiferromagnet Fe 2 Mo 3 O 8 , and observe evidence of domain wall interaction with a structural defect. Here, this technique does not involve any numerical algorithms. It is fast, sensitive, produces large-scale images in a single-exposure measurement, and is applicable to a variety of magnetic domain types.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Coherent diffractive imaging of microtubules using an X-ray laser

X-ray free electron lasers (XFELs) create new possibilities for structural studies of biological objects that extend beyond what is possible with synchrotron radiation. Serial femtosecond crystallography has allowed high-resolution structures to be determined from micro-meter sized crystals, whereas single particle coherent X-ray imaging requires development to extend the resolution beyond a few tens of nanometers. Here we describe an intermediate approach: the XFEL imaging of biological assemblies with helical symmetry. We collected X-ray scattering images from samples of microtubules injected across an XFEL beam using a liquid microjet, sorted these images into class averages, merged these data into a diffraction pattern extending to 2 nm resolution, and reconstructed these data into a projection image of the microtubule. Details such as the 4 nm tubulin monomer became visible in this reconstruction. These results illustrate the potential of single-molecule X-ray imaging of biological assembles with helical symmetry at room temperature.

47 OTHER INSTRUMENTATION↗