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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

X-ray Spectroscopy Fingerprints of Pristine and Functionalized Graphene

In this work, we demonstrate how to identify and characterize the atomic structure of pristine and functionalized graphene materials from a combination of computational simulation of X-ray spectra, on the one hand, and computer-aided interpretation of experimental spectra, on the other. Despite the enormous scientific and industrial interest, the precise structure of these 2D materials remains under debate. As we show in this study, a wide range of model structures from pristine to heavily oxidized graphene can be studied and understood with the same approach. We move systematically from pristine to highly oxidized and defective computational models, and we compare the simulation results with experimental data. Comparison with experiments is valuable also the other way around; this method allows us to verify that the simulated models are close to the real samples, which in turn makes simulated structures amenable to several computational experiments. Our results provide ab initio semiquantitative information and a new platform for extended insight into the structure and chemical composition of graphene-based materials.

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

Revisiting Competitive Adsorption of Small Molecules in the Metal–Organic Framework Ni-MOF-74

To precisely evaluate the potential of metal-organic frameworks (MOFs) for gas separation and purification applications, it is crucial to understand how various molecules competitively adsorb inside MOFs. In this paper, we combine in situ infrared spectroscopy with ab initio calculations to investigate the mechanisms associated with co-adsorption of a number of small molecules including CO, NO, and CO 2 inside the prototypical framework Ni-MOF-74. Surprisingly, we find that the displacement of CO bound inside Ni-MOF-74 (binding energy of 53 kJ/mol) is readily driven by CO 2 exposure, even though CO 2 has a noticeably weaker binding energy of only 41 kJ/mol; meanwhile, the significantly more strongly binding NO molecule (90 kJ/mol) is not able to easily displace bound CO inside Ni-MOF74. These results show that single-phase binding energies of a molecule inside the MOF cannot completely describe their interaction with the MOF in the presence of other guest molecules. Here, we unveil a number of crucial factors such as the kinetic barrier, partial pressure, secondary binding sites, and guest-host/lateral interactions that control the co-adsorption process and combined with the binding energy are better descriptors of the behavior and adsorption of gas mixtures inside MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Characterization of latent image of electron beam resist via critical-dimension resonant soft X-ray scattering

Metrology plays a crucial role in semiconductor manufacturing by providing accurate and precise measurement and characterization of critical parameters. With the development of high-resolution extreme ultraviolet lithography (EUVL) processes, critical dimensions are shrinking to sub-10 nm. Resist materials encounter the challenge of providing heightened sensitivity and a handle on exacerbating stochastic variations. A comprehensive understanding of the chemical profile of the latent image is pivotal for mitigating stochastic effects and optimizing pattern quality. However, the subtle differences in chemistry between the exposed and unexposed regions of the resists make it extremely challenging to characterize the latent images with sub-nanometer precision. Here, we develop the metrology with critical-dimension resonant soft X-ray scattering (CD-RSoXS) to probe the chemical profiles of latent images stored in resist after exposure. The combination of absorption spectroscopy and enhanced scattering contrast makes it possible to characterize the subtle structural and chemical variations in the latent image. Moreover, the results of the measurements are compared with the simulations with a finite element method–based Maxwell solver to extract a detailed profile of the latent and developed images. We demonstrate that the CD-RSoXS technique can provide valuable insights into the high spatial resolution and local chemical sensitivity simultaneously, which is crucial to understanding the resolution limits and stochastic effects in EUVL processes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A Quasar Shedding Its Dust Cocoon at Redshift 2

We present the first near-IR spectroscopy and joint analyses of multiwavelength observations for SDSS J082747.14+425241.1, a dust-reddened, weak broad emission-line quasar (WLQ) undergoing a remarkable broad-absorption line (BAL) transformation. The systemic redshift is more precisely measured to be z = 2.070 ± 0.001 using Hβ compared to z = 2.040 ± 0.003 using Mg ιι from the literature, signifying an extreme Mg ιι blueshift of 2140 ± 530 km s –1 relative to Hβ. Using the Hβ-based single-epoch scaling relation with a systematic uncertainty of 0.3 dex, its black hole (BH) mass and Eddington ratio are estimated to be M BH ~ 6.1 × 10 8 M ⊙ and λ Edd ~ 0.71, indicative of being in a rapidly accreting phase. Our investigations confirm the WLQ nature and the LoBAL → HiBAL transformation, along with a factor of 2 increase in the Mg ιι+Fe ιι emission strength and a decrease of 0.1 in E(B – V) over two decades. The kinetic power of this LoBAL wind at R ~ 15 pc from its BH is estimated to be ~43% of the Eddington luminosity, sufficient for quasar feedback upon its host galaxy albeit with an order-of-magnitude uncertainty. This quasar provides a clear example of the long-sought scenario where LoBAL quasars are surrounded by dust cocoons, and wide-angle nuclear winds play a key role in the transition of red quasars evolving into the commonly seen blue quasars.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1984

Surface fluctuation spectroscopy - A novel technique for characterizing liquid interfaces

Surface fluctuation spectroscopy is a dynamic light scattering technique which involves the detection of thermal fluctuations (capillary waves) that cover every liquid interface. The advantages of this technique over conventional mechanical methods are discussed. The signal resolution and precision are improved by using a grating heterodyne technique coupled with a digital correlator. Detailed calculations showed that, for the measured power spectrum (the Fourier transform of the correlation function) to take the Lorentzian shape, it is necessary that certain optical conditions be met. These conditions are demonstrated with experimental data collected for ethanol at the ambient temperature as a function of the wave number. Once the optical parameters are adjusted correctly, the experimental results show excellent agreement with the literature values. It is also demonstrated that, using microcomputer technology, the entire system can be automated.

Shih, L. B.↗
NASA NTRS2002

Laboratory Studies of the Photochemistry of Peroxynitric Acid

Observations of odd hydrogen radicals at high SZA in the lower stratosphere have demonstrated that our understanding of the HO(x) chemistry is incomplete [Wennberg et al., 1994a; Salawitch et al., 1994; Wennberg et al., 1999]. In particular, the concentrations of the HO(x) radicals are significantly larger than expected under weak photolytic conditions. Donaldson et al. [1997] have speculated that excitation of overtones of the OH stretching frequency in molecules such as HNO3 and HO2NO2 may be significant sources of HO(x) under these conditions. Although weak, vibrationally mediated photolysis may be important because it occurs in the near IR and visible and can provide energy in excess of the dissociation energy (D(o)): HONO2 + hv yields OH + NO (D(o) approx. 600 nm) and HOONO2 + hv yields OH + NO3 (D(o) approx. 735 nm) HOONO2 + hv yields HO2 + NO2 (D(o) approx. 1250 nm). In this project we developed instrumentation to characterize the photodissociation yields of hydroxyl containing compounds in the visible and near IR. This effort has involved coupling a tunable photolysis optical parametric oscillator (OPO) laser system with precise determination of the hydroxyl radical. The OPO system [Wu et al., 1997] was developed with support from the NSF Major Research Instrumentation Fund in a proposal entitled "Development of Novel, Compact Light Sources for Advanced Spectroscopy in Atmospheric Science and Materials Research" (Geoffrey A. Blake, P.I. California Institute of Technology).

Wennberg, Paul O.↗
NASA NTRS2000

Difference-frequency-based tunable absorption spectrometer for detection of atmospheric formaldehyde

High-sensitivity detection of formaldehyde (CH2O) at 3.5315 micrometers (2831.64 cm-1) is reported with a diode-laser-pumped, fiber-coupled, periodically poled LiNbO3 spectroscopic source. This source replaced the Pb-salt diode laser Dewar assembly of an existing tunable diode-laser absorption spectrometer designed for ultrasensitive detection of CH2O. Spectra are recorded with 2f-modulation spectroscopy and zero-air rapid background subtraction. Initial measurements reported here, determined from multiple measurements of a flowing 7.7 parts per billion by volume (ppbv, parts in 10(9)) CH2O in air mixture, indicate replicate precisions as low as 0.24 ppbv.

Non-NASA Center↗
DOE OSTI2022

Titrating Controlled Defects into Si-LTA Zeolite Crystals Using Multiple Organic Structure-Directing Agents

Controlling defects in zeolites is crucial for tuning their adsorption and catalytic properties. In this work, we have performed an integrated zeolite synthesis, spectroscopy, and density functional theory study to test the limit of F– as a charge-balancing agent that mitigates defects in siliceous zeolites. We focused on the synthesis of siliceous zeolite LTA at 150 °C with 1,2-dimethyl-3-(4-methylbenzyl) imidazolium as the primary organic structure-directing agent (OSDA) and tetramethyl ammonium (TMA) as the secondary OSDA. By varying the amount of TMA in the synthesis gel, positive charges were titrated into the resulting as-made Si-LTA. Surprisingly, we found that greater TMA concentration does not induce more F– to enter into the zeolite. 29Si solid-state MAS NMR, Raman spectroscopy, and density functional theory suggest that this system has surpassed its capacity for F– to balance OSDA charge, and additional positive charge is balanced by Si–O– framework defects. The number of defects in the as-made Si-LTA can be precisely titrated by the amount of TMA in the zeolite structures. For the Si-LTA synthesized without TMA, framework defects formed in the early stage of crystal growth were found to heal during later crystallization, leading to defect-free Si-LTA. However, for the Si-LTA synthesized with TMA, the defects formed in early stages do not heal. A DFT thermodynamic analysis explains that crowding of Si-LTA pores by TMA impedes defect healing; this prediction is corroborated by synthesis experiments at an elevated temperature (170 °C). These results indicate that F– can have a limited capacity to balance OSDA charge in zeolite synthesis, opening up a third route to zeolite synthesis intermediate between the fluoride and hydroxide routes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

Future Probes of the Neutron Star Equation of State Using X-ray Bursts

Observations with NASA s Rossi X-ray Timing Explorer (RXTE) have resulted in the discovery of fast (200 - 600 Hz), coherent X-ray intensity oscillations (hereafter, %urstoscillations ) during thermonuclear X-ray bursts from 12 low mass X-ray binaries (LMXBs). Although many of their detailed properties remain to be fully understood, it is now beyond doubt that these oscillations result from spin modulation of the thermonuclear burst flux from the neutron star surface. Among the new timing phenomena revealed by RXTE the burst oscillations are perhaps the best understood, in the sense that many of their properties can be explained in the framework of this relatively simple model. Because of this, detailed modelling of burst oscillations can be an extremely powerful probe of neutron star structure, and thus the equation of state (EOS) of supra-nuclear density matter. Both the compactness parameter beta = GM/c(sup 2)R, and the surface velocity, nu(sub rot) = Omega(sub spin)R, are encoded in the energy-dependent amplitude and shape of the modulation pulses. The new discoveries have spurred much new theoretical work on thermonuclear burning and propagation on neutron stars, so that in the near future it is not unreasonable to think that detailed physical models of the time dependent flux from burning neutron stars will be available for comparison with the observed pulse profiles from a future, large collecting area X-ray timing observatory. In addition, recent high resolution burst spectroscopy with XMM/Newton suggests the presence of redshifted absorption lines from the neutron star surface during bursts. This leads to the possibility of using large area, high spectral resolution measurements of X-ray bursts as a precise probe of neutron star structure. In this work I will explore the precision with which constraints on neutron star structure, and hence the dense matter EOS, can be made with the implementation of such programs.

Strohmayer, Tod E.↗
DOE OSTI2021

Sculpting the Plasmonic Responses of Nanoparticles by Directed Electron Beam Irradiation

Spatial confinement of matter in functional nanostructures has propelled these systems to the forefront of nanoscience, both as a playground for exotic physics and quantum phenomena and in multiple applications including plasmonics, optoelectronics, and sensing. In parallel, the emergence of monochromated electron energy loss spectroscopy (EELS) has enabled exploration of local nanoplasmonic functionalities within single nanoparticles and the collective response of nanoparticle assemblies, providing deep insight into associated mechanisms. However, modern synthesis processes for plasmonic nanostructures are often limited in the types of accessible geometry, and materials and are limited to spatial precisions on the order of tens of nm, precluding the direct exploration of critical aspects of the structure-property relationships. Here, the atomic-sized probe of the scanning transmission electron microscope is used to perform precise sculpting and design nanoparticle configurations. Using low-loss EELS, dynamic analyses of the evolution of the plasmonic response are provided. It is shown that within self-assembled systems of nanoparticles, individual nanoparticles can be selectively removed, reshaped, or patterned with nanometer-level resolution, effectively modifying the plasmonic response in both space and energy. This process significantly increases the scope for design possibilities and presents opportunities for unique structure development, which are ultimately the key for nanophotonic design.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Comparison of gamma-ray spectral analysis methods for thick-walled UF 6 cylinders

Three data analysis methods were compared for gamma ray spectra collected by planar and coaxial high-purity germanium detectors (HPGe) on thick-walled uranium hexafluoride cylinders. The cylinder contents range from natural to low-enriched uranium (4.95% 235 U). Each spectrum was analyzed with the traditional 185.7 keV enrichment meter method, a 185.7/1001 keV ratio method, and the Fixed Energy Response Function Analysis with Multiple Efficiency (FRAM) software that utilizes low- and high-energy gamma rays and X-rays. When results for all cylinders were compared, the enrichment meter method and the 185.7/1001 keV peak ratio method consistently provided the most accurate data for all detector types. The error on the enrichment calculations analyzed with FRAM did not meet the international target value whereas those calculated with the enrichment meter and ratio method did. Enrichments calculated by FRAM were found to skew to higher values on natural uranium and to lower values on low-enriched uranium. FRAM calculated the least-precise enrichments; replicate analyses of single cylinders resulted in 235 U values that varied by as much as 19%. FRAM does have the significant advantages in that it does not require the use of calibration cylinders, infinite thickness criteria are not necessary, and it can be applied to any HPGe detector. Finally, if calibration cylinders are available, the enrichment meter and 185.7/1001 peak ratio are the recommended methods as they are the most accurate and precise.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Real-time tracking of structural evolution in 2D MXenes using theory-enhanced machine learning

In situ Electron Energy Loss Spectroscopy (EELS) combined with Transmission Electron Microscopy (TEM) has traditionally been pivotal for understanding how material processing choices affect local structure and composition. However, the ability to monitor and respond to ultrafast transient changes, now achievable with EELS and TEM, necessitates innovative analytical frameworks. Here, we introduce a machine learning (ML) framework tailored for the real-time assessment and characterization of in operando EELS Spectrum Images (EELS-SI). We focus on 2D MXenes as the sample material system, specifically targeting the understanding and control of their atomic-scale structural transformations that critically influence their electronic and optical properties. This approach requires fewer labeled training data points than typical deep learning classification methods. By integrating computationally generated structures of MXenes and experimental datasets into a unified latent space using Variational Autoencoders (VAE) in a unique training method, our framework accurately predicts structural evolutions at latencies pertinent to closed-loop processing within the TEM. This study presents a critical advancement in enabling automated, on-the-fly synthesis and characterization, significantly enhancing capabilities for materials discovery and the precision engineering of functional materials at the atomic scale.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

A Scalable Method for Thickness and Lateral Engineering of 2D Materials

The physical properties of two-dimensional (2D) materials depend strongly on the number of layers. Hence, methods for controlling their thickness with atomic layer precision are highly desirable, yet still too rare, and demonstrated for only a limited number of 2D materials. Here we present a simple and scalable method for the continuous layer-by-layer thinning that works for a large class of 2D materials, notably layered germanium pnictides and chalcogenides. It is based on a simple oxidation/etching process, which selectively occurs on the topmost layers. Through a combination of atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and X-ray diffraction experiments we demonstrate the thinning method on germanium arsenide (GeAs), germanium sulfide (GeS) and germanium disulfide (GeS 2 ). We use first-principles simulation to provide insights into the oxidation mechanism. Our strategy, which could be applied to other classes of 2D materials upon proper choice of the oxidation/etching reagent, could pave the way for the realization of 2D material-based devices, such as electronic or optoelectronic ones, where a precise control over the number of layers (hence over the material’s physical properties) is needed. We also show that when used in combination with lithography, our method can be used to make precise patterns in the 2D materials.

2D materials↗
DOE OSTI2020

Charging Reactions Promoted by Geometrically Necessary Dislocations in Battery Materials Revealed by In Situ Single-Particle Synchrotron Measurements

Crystallographic defects exist in many redox active energy materials, e.g., battery and catalyst materials, which significantly alter their chemical properties for energy storage and conversion. However, there is lack of quantitative understanding of the interrelationship between crystallographic defects and redox reactions. Herein, crystallographic defects, such as geometrically necessary dislocations, are reported to influence the redox reactions in battery particles through single-particle, multimodal, and in situ synchrotron measurements. Through Laue X-ray microdiffraction, many crystallographic defects are spatially identified and statistically quantified from a large quantity of diffraction patterns in many layered oxide particles, including geometrically necessary dislocations, tilt boundaries, and mixed defects. The in situ and ex situ measurements, combining microdiffraction and X-ray spectroscopy imaging, reveal that LiCoO 2 particles with a higher concentration of geometrically necessary dislocations provide deeper charging reactions, indicating that dislocations may facilitate redox reactions in layered oxides during initial charging. The present study illustrates that a precise control of crystallographic defects and their distribution can potentially promote and homogenize redox reactions in battery materials.

25 ENERGY STORAGE↗
DOE OSTI2025

Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters

Abstract Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4‐vinylpyridine) thin films result in the 3D‐nucleation of clusters consistent with a cubane‐type Cd 4 S 4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few‐atom Cd‐based clusters are consistent with electronic and vibrational spectroscopy and grazing‐incidence total X‐ray scattering measurements of 3D‐cluster‐arrays synthesized at 80 °C. The direct synthesis of few‐atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light‐absorbing materials including solar energy harvesting and conversion applications.

Jayaweera, Nuwanthaka P. [Material Science Divisio↗
DOE OSTI2025

Phase transition in two-dimensional monolayer (1L)-molybdenum disulfide induced by atomic S-basal plane gliding via synchrotron X-ray monochromatic beam radiation for superior electronic performance

Here, in this work, we report a novel approach to reduce the channel resistance by inducing a phase transition behavior from 2H to 1T in a monolayer MoS 2 (1L-MoS 2 ) by a synchrotron X-ray monochromatic beam (mono-beam) radiation. The effects of the biphase structure by the mono-beam on the 1L-MoS2 film were investigated using Raman spectra, photoluminescence (PL) spectra, scanning tunneling microscopy, and scanning tunneling spectroscopy, respectively. Through material characterization, we identified that the lateral sliding of S-vacancies along the S-plane in the 1L-MoS 2 is the key reason for the origin of unidirectional phase transition. The precise phase engineering triggered by the mono-beam radiation process allows the realization of field-effect transistors (FET) with 2X improvement in mobility toward a high on/off ratio (~10 8 ) and a near-ideal subthreshold swing of ~88 mV per decade. The validity of the phase engineering could be further extended for its application as a memory device, exhibiting a gate tunable conduction modulation behavior and a high resistance ratio of ~10 2 at a gate bias of 5 V with endurance of ~100 cycles. Furthermore, an artificial neural network using the synaptic weight update with accuracy of ~93 % was achieved.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effects of Cofeeding Hydrogen on Propane Dehydrogenation Catalyzed by Isolated Iron Sites Incorporated into Dealuminated BEA

Iron sites dispersed on nonacidic siliceous supports have been reported to be catalytically active for propane dehydrogenation (PDH), yet the precise relationship between site structure and catalytic activity remains elusive. Here, this study provides a comprehensive understanding of the catalytic performance of iron supported on dealuminated BEA (DeAlBEA) zeolites for PDH. Using XAS, UV-vis, and IR spectroscopy of adsorbed pyridine and deuterated acetonitrile, it was found that, at an Fe/Al 0 of 0.04, isolated Fe sites form. These isolated sites exhibit a forward rate of PDH of 213 mol propene/mol Fe·h at 823 K and a feed containing 15 kPa propane. When 15 kPa of H 2 is added to the feed, the forward rate of PDH rises to 391 mol of propene/mol of Fe·h. In both cases, the propene selectivity is over 99%. IR spectroscopy of d 3 -acetonitrile suggests that the open Lewis acid site ((-Si-O-) 2 Fe 3+ -OH) serves as the active site responsible for PDH, while Brønsted acid sites (≡Fe 3+ -O(H)-Si≡) contribute to propane cracking with increasing Fe/Al 0 ratios. Kinetic analysis of the effects of H 2 addition to the propane feed on PDH kinetics shows that H 2 enhances the activity of 0.04FeDeAlBEA primarily by enhancing the strength of the propane adsorption.

Alghannam, Afnan [University of California, Berkel↗