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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A trapping tolerant drain current based temperature measurement of β -Ga 2 O 3 MOSFETs

The drain current temperature dependence is an efficient way to determine the channel temperature in semiconductor devices; however, it has been challenging to use due to the potential interference of trapping effects. A trapping tolerant method is proposed, illustrated here for Ga 2 O 3 MOSFETs, making in situ temperature measurements possible, allowing a thermal resistance of 59 K∙mm/W to be measured in Ga 2 O 3 MOSFETs. However, neglecting the effect of trapping causes an error of ~15% in the channel temperature measured using the drain current. 3D simulations show that the measured channel temperature is the average temperature value between source and drain contact.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Kinetic study of reaction C 2 H 5 + HO 2 in a photolysis reactor with time-resolved Faraday rotation spectroscopy

The rate constant and branching ratios of ethyl reaction with hydroperoxyl radical, C 2 H 5 + HO 2 (1), a key radical-radical reaction for intermediate temperature combustion chemistry, were measured in situ for the first time in a photolysis Herriott cell by using mid-IR Faraday rotation spectroscopy (FRS) and UV-IR direct absorption spectroscopy (DAS). The microsecond time-resolved diagnostic technique in this work enabled the direct rate measurements of the target reaction at 40 and 80 mbar and reduced the experimental uncertainty considerably. C 2 H 5 and HO 2 radicals were generated by the photolysis of (COCl) 2 /C 2 H 5 I/CH 3 OH/O 2 /He mixture at 266 nm. By direct measurements of the transient profiles of C 2 H 5 , HO 2 and OH concentrations, the overall rate constant for this reaction at 297 K was determined as k 1 (40 mbar) = (3.8 ± 0.8) × 10 –11 cm 3 molecule –1 s –1 and k 1 (80 mbar) = (4.1 ± 1.0) × 10 –11 cm 3 molecule –1 s –1 . As a result, the direct observation of hydroxyl radical (OH) indicated that OH formation channel was the major channel with a branching ratio of 0.8 ± 0.1.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Reaction Pathways over ZnZrO 2 -Based Catalysts and Catalytic Sorbents

Reactive capture and conversion (RCC) is a process intensification approach that integrates CO 2 capture and hydrogenation within a single unit, removing the CO 2 purification and storage steps of traditional process flow schemes. This alters the catalytic step from a traditional steady-state (SS) flow process to a transient capture and conversion cycle, which could lead to product distributions distinct from those observed in conventional SS experiments. Such differences are investigated in the combined capture and hydrogenation of carbon dioxide to methanol over a ZnZrO 2 catalyst and a ZnZrO 2 + NaNO 3 /Mg 3 AlO x catalytic sorbent (CS) using fixed-bed kinetic measurements, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and steady-state isotopic transient kinetic analysis-DRIFTS (SSITKA-DRIFTS). Under SS conditions, ZnZrO 2 produced methanol through sequential hydrogenation of HCOO* and CH 3 O* intermediates. On the contrary, CO was attributed primarily to CO 2 dissociation at oxygen vacancies, as supported by isotopic shifts and measured reaction orders. For the CS, isotopic switching experiments suggested that monodentate carbonate species (CO 3 2− , abbreviated as m-CO 3 2− ) act as active intermediates that can be hydrogenated to HCOO* and subsequently to CH 3 O. Under RCC conditions, in situ DRIFTS and isotopic experiments reveal that m-CO 3 2− species formed during the CO 2 capture step follow two competing routes upon H 2 exposure: (i) direct hydrogenation to methane on the sorbent domain or (ii) migration of m-CO 3 2− to the ZnZrO 2 domain, where they are hydrogenated to methanol through the HCOO pathway. Overall, RCC enables carbonate hydrogenation routes not observed under SS cofeed conditions. Thus, the reaction pathways and rates during RCC can be different from operation under conventional SS conditions, and the product distribution is determined here by competition between carbonate hydrogenation on sorbent sites and migration to ZnZrO 2 for methanol synthesis.

CCUS↗
DOE OSTI2021

Monitoring Radiochemical Processing Streams for the 238 Pu Supply Program with Process Pulse II

Oak Ridge National Laboratory (ORNL) is developing advanced spectroscopic and real-time monitoring capabilities to improve the timeliness of analytical measurements and process decisions for the 238Pu Supply Program. Reducing the time, resources, and costs associated with each production campaign is critical because overlapping campaigns will be required to meet the production goals of the National Aeronautics and Space Administration. Real-time, in situ analytical measurements in the heavily shielded hot cells at the Radiochemical Engineering Development Center (REDC) will allow for rapid process information feedback and operational benefits that help the 238Pu supply program scale-up production efforts. Noteworthy steps were taken during Campaign 5 to establish the ability to monitor processing streams in real time with spectrophotometry and a commercially available online monitoring software called The Unscrambler X Process Pulse II (PP) multivariate statistical process monitoring system by Camo Analytics (version 5.60). PP automates univariate-type calculations within the software itself and executes multivariate models built using The Unscrambler X (version 10.4 or newer). The Unscrambler is a commercially available data analysis software made by the same company. PP is composed of easy-to-use-tools for all personnel, including data scientists and technicians. The software can be used to plot analyte concentration profiles, spectral data, and other process variables in real time. All process data are represented in a single view with interactive charts useful for viewing how a process evolves over time.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2023

Parasitic Effects in Impedance Spectrum of PEM Water Electrolysis Cells: Case Study of High-Frequency Inductive Effects

Electrochemical impedance spectroscopy (EIS) is a powerful tool to characterize and distinguish electrochemical, electrical, and diffusive processes in an electrolysis cell. The EIS response with small impedance (mΩ) depends on components and materials of the cell, but often also on the electrical setup, cables, and connectors, leading to incorrect conclusions about the performance of the electrolysis cells. These parasitic effects are assessed via a short-circuit measurement and confirmed to be external from the membrane electrode assembly (MEA). In the setup, the inductive characteristic is described by a modified inductive reactance and must be included in the equivalent circuit model (ECM) which is fitting the cell EIS spectra in operation (in situ). If points of the spectra showing inductive characteristic (below x-axis in Nyquist plot) are excluded from the ECM evaluation, an artificially increased ohmic resistance at high frequencies is obtained. In addition, considerations on other components of the ECM can be misleading and significantly incorrect. The only way to avoid that inductive behavior caused by the external setup is incorrectly assigned to the ECM describing properties of the MEA is to include the inductive effects in the ECM analysis of in situ EIS measurements.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Identifying the Gate-Opening Mechanism in the Flexible Metal–Organic Framework UTSA-300

Atomic-level understanding of the gate-opening phenomenon in flexible porous materials is an important step toward learning how to control, design, and engineer them for applications such as the separation of gases from complex mixtures. Here, we report such mechanistic insight through an in-depth study of the pressure-induced gate-opening phenomenon in our earlier reported metal–organic framework (MOF) Zn(dps) 2 (SiF 6 ) (dps = 4,4'-dipyridylsulfide), also called UTSA-300, using isotherm and calorimetry measurements, in situ infrared spectroscopy, and ab initio simulations. UTSA-300 is shown to selectively adsorb acetylene (C 2 H 2 ) over ethylene (C 2 H 4 ) and ethane (C 2 H 6 ) and undergoes an abrupt gate-opening phenomenon, making this framework a highly selective gas separator of this complex mixture. The selective adsorption is confirmed by pressure-dependent in situ infrared spectroscopy, which, for the first time, shows the presence of multiple C 2 H 2 species with varying strengths of bonding. A rare energetic feature at the gate-opening condition of the flexible MOF is observed in our differential heat energies, directly measured by calorimetry, showcasing the importance of this tool in adsorption property exploration of flexible frameworks and offering an energetic benchmark for further energy-based fundamental studies. Based on the agreement of this feature with ab initio-based adsorption energies of C 2 H 2 in the closed-pore structure UTSA-300a (“a” refers to the activated form), this feature is assigned to the weakening of the H-bond C–H···F formed between C 2 H 2 and fluorine of the MOF. Furthermore, our analysis identifies the weakening of this H-bond, the expansion of the closed-pore MOF upon successive C 2 H 2 coadsorption until its volume is close to that of the open-pore MOF, and the spontaneous gate opening to energetically favor C 2 H 2 adsorption in the open-pore structure as crucial steps in the gate-opening mechanism in this system.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Kinetic and X-ray Absorption Spectroscopic Analysis of Catalytic Redox Cycles over Highly Uniform Polymetal Oxo Clusters

Metal–organic framework materials (MOFs) offer an opportunity for investigating catalytic properties of polymetal oxo clusters that are highly well defined and uniform in nature, in contrast to other classes of catalysts that may exhibit a propensity toward active site heterogeneity. We report herein a kinetic and X-ray absorption spectroscopy (XAS) analysis of the two-electron oxidation of CO over divalent metal sites in MIL-100(M = Fe, Cr) (MIL = Materials of Institut Lavoisier) materials carrying μ 3 -oxo bridged trimers, and connect observations about the kinetic relevance of redox steps to density functional theory (DFT) predictions published previously. The high degree of uniformity evident from in situ titration measurements leads to a congruence in mechanistic inferences made from steady-state catalytic, transient stoichiometric, isotopic exchange, and isotopic tracer data that all point to a sequential mechanism comprised of separate oxidation and reduction half-cycle steps conjoined by an active oxygen intermediate. In situ XAS data reinforce mechanistic conclusions derived from kinetic analysis, and suggest that the active oxygen intermediate may be more appropriately characterized as an iron-oxyl (Fe 3+ –O – ) rather than an iron-oxo (Fe 4+ =O 2– ) species. The Cr analogue of MIL-100 exhibits contrasting rate features that can be rationalized using an identical sequence of steps as MIL-100(Fe), but with a highly dissimilar set of kinetic parameters that can also be validated using transient stoichiometric experiments. The larger coverages of active oxygen intermediates on MIL-100(Cr) are consistent with predictions from prior DFT studies that suggest more stable and less reactive active oxygen species for metals with lower d-electron counts, and point to metal identity as a lever for precisely controlling the kinetic relevance of oxidation and reduction half-cycles in catalytic redox sequences over polymetal oxo clusters. Importantly, the results presented point to the utility of developing broadly applicable structure–catalytic property relationships over MOF nodes specifically, and highly uniform catalysts more generally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrochemical Characterization of Dissolved Oxides in Molten FLiNaK

Molten fluoride salts have long been the subject of investigation given their application in a variety of industrial processes. Oxides are a common exogeneous impurity within these systems, and can lead to many operational and regulatory concerns. In recent studies, the electro-oxidation of dissolved metallic oxides has been attributed to a single step oxygen evolution reaction despite voltametric evidence suggesting otherwise. Here, we first use square wave voltammetry to confirm that the oxidation of dissolved oxides in fluorides proceeds via a two-electron transfer reaction and then demonstrate that the presence of a peroxide-mediated redox reaction better explains the electrochemical data. Numerical simulations were then used to support the determination of improved diffusion coefficients to enable electroanalytical measurements of the oxide concentration across at a variety of temperatures. A linear Arrhenius relationship was observed when the experimental data was corrected for ohmic resistance effects. Concentration measurements using the corrected square wave voltammetry data demonstrated high accuracy across a large range of concentrations, while the uncorrected data showed plateauing and high errors. In total, this work serves to rectify previously misconstrued electrochemical data of oxides in molten salts and demonstrate how accurate, in situ concentration measurements can be achieved in real-world systems.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Impact of exposure to brine/CO 2 on the mechanical and transport properties of the Mt. Simon Sandstone

When sandstone rocks are exposed to CO 2 -saturated brine, their transport and mechanical properties can, potentially, change due to chemical reactions as a result of such exposure. This paper investigates changes in the flow-through characteristics, porosity, and the mechanical properties of Mt. Simon Sandstone samples caused by such exposure to brine/CO 2 . A core, extracted from the Mt. Simon formation, was first characterized for its porosity and relevant transport properties, and it was then aged for over 500 hr in CO 2 -saturated brine at formation-relevant pressure, temperature, and confining stress conditions. The deformation of the sample was measured in situ during aging via strain gauges attached to the core's surface. Following the aging experiment, the sample's porosity and transport properties were again analyzed. Our experiments show that both the porosity and permeability of the Mt. Simon sandstone sample increase due to exposure to brine/CO 2 , with the impact on permeability being more significant. The deformation measurements employing strain gauges indicate a weakening of the core material. Analysis of the composition of the brine at the conclusion of the testing reveals changes, specifically, an increase in the concentration of several of the cations. These changes are indicative of mineral/clay dissolution, consistent with the porosity, permeability, and strain gauge measurements.

58 GEOSCIENCES↗
DOE OSTI2023

Ion-Selective Scattering Studied Using the Variable-Energy Electron Irradiation in the Ba 0.2 K 0.8 Fe 2 As 2 Superconductor

Low-temperature variable-energy electron irradiation was used to induce non-magnetic disorder in a single crystal of a hole-doped iron-based superconductor, Ba $1-x$ K $x$ Fe 2 As 2 , $x$ = 0.80. To avoid systematic errors, the beam energy was adjusted non-consequently for five values between 1.0 and 2.5 MeV when sample resistance was measured in situ at 22 K. For all energies, the resistivity raises linearly with the irradiation fluence suggesting the creation of uncorrelated dilute point-like disorder (confirmed by simulations). The rate of the resistivity increase peaks at energies below 1.5 MeV. Comparison with calculated partial cross-sections points to the predominant creation of defects in the iron sublattice. Simultaneously, superconducting $T_c$, measured separately between the irradiation runs, is monotonically suppressed as expected, since it depends on the total scattering rate, hence on the total cross-section, which is a monotonically increasing function of the energy. Our work experimentally confirms an often-made assumption of the dominant role of the iron sub-lattice in iron-based superconductors.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Realism of Lagrangian Large Eddy Simulations Driven by Reanalysis Meteorology: Tracking a Pocket of Open Cells Under a Biomass Burning Aerosol Layer

An approach to drive Lagrangian large eddy simulation (LES) of boundary layer clouds with reanalysis data is presented and evaluated using satellite (Spinning Enhanced Visible and Infrared Imager, SEVIRI) and aircraft (Cloud-Aerosol-Radiation Interactions and Forcing, CLARIFY) measurements. The simulations follow trajectories of the boundary layer flow. They track the formation and evolution of a pocket of open cells (POC) underneath a biomass burning aerosol layer in the free troposphere. The simulations reproduce the evolution of observed stratocumulus cloud morphology, cloud optical depth, and cloud drop effective radius, and capture the timing of the cloud state transition from closed to open cells seen in the satellite imagery on the three considered trajectories. They reproduce a biomass burning aerosol layer identified by the in-situ aircraft measurements above the inversion of the POC. Entrainment of aerosol from the biomass burning layer into the POC is limited to the extent of having no impact on cloud- or boundary layer properties, in agreement with the CLARIFY observations. The two-moment bin microphysics scheme used in the simulations reproduces the in-situ cloud microphysical properties reasonably well. A two-moment bulk microphysics scheme reproduces the satellite observations in the non-precipitating closed-cell state, but overestimates liquid water path and cloud optical depth in the precipitating open-cell state due to insufficient surface precipitation. A boundary layer cold and dry bias occurring in LES can be counteracted by reducing the grid aspect ratio and by tightening the large scale wind speed nudging towards the surface.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Facile Measurement of the Rotation of a Single Optically Trapped Nanoparticle Using the Diagonal Ratio of a Quadrant Photodiode

Optical tweezers are a powerful tool for exploring physical properties of particles in various environments through analysis of their dynamics in a trapping potential. Analysis of the trapped particle's position is often done using interferometric back-focal-plane detection microscopy in which interference between the trapping laser and the light interacting with the trapped particle is projected on a quadrant photo-diode (QPD). The QPD measurements are almost universally the voltage ratios between the transverse components of the detector (left/right; up/down) that are calibrated to ascertain particle positions and orientations (i.e., rotation). In this paper, we demonstrate how measuring the diagonal ratio of the QPD allows tracking the spinning and orbital motion of optically trapped objects with enhanced sensitivity compared to the conventional transverse ratio and reveals additional information about particle dynamics. The diagonal ratio "balances" the signal from opposite sides of the QPD, allowing common mode noise reduction and increased measurement sensitivity of the rotating nanospheres at frequencies from below 200 Hz to above 15 kHz. We show that the variability in particle rotation rates is due to slight differences in the aspect ratio of the nanoparticles. We also measure in situ a gradual acceleration in the spinning frequency of trapped nanoparticles due to photothermal shedding of surface ligands and the resulting decrease of rotational friction in solution. The accelerating particles spin at rates exceeding 30 kHz and are eventually "optically printed" onto the glass coverslip on top of the liquid cell enclosure. The diagonal ratio is a simple, readily available, and powerful enabler for measuring rotational dynamics with a 5-fold sensitivity increase over conventional QPD measurements. This affords opportunities for controlling the orientational dynamics of trapped nanoparticles, which is crucial for various applications, including nanoscale mechanical motors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effects of Al:Si and (Al+Na):Si ratios on the static corrosion of sodium‐boroaluminosilicate glasses

Abstract Understanding alteration mechanisms of borosilicate glasses in aqueous media is essential to nuclear waste performance assessments to ensure radioisotopes are contained for extended durations. Aluminum is typically added to glass compositions to reduce the extent of alteration. However, previous work on 7‐day durability tests has suggested that Al has a nonlinear relationship with extent of alteration. The effects of Al:Si and (Al+Na):Si substitutions on glass durability were evaluated using series of glasses based on the International Simple Glass corroded in static conditions up to 13 months in deionized water at 90°C. The alteration behavior was determined by measurement of element release in solution. The ⁓7‐day alteration trends across the series were consistent with predicted trends. The 13‐month results indicated overall alteration decreased as Al:Si ratios increased and was unaffected by changes in (Al+Na):Si except for the glass with the highest (Al+Na):Si ratio (ISG‐A23N), which completely altered within 14 days. Frequent sampling and in situ Raman measurements of solutions revealed ISG‐A23N experienced several distinguishable alteration rate regimes within 7 days, forming a ⁓100 µm alteration layer and a NaSiAlO 4 zeolite.

Reiser, Joelle T.↗
DOE OSTI2021

Retrieved Number concentration of Cloud Condensation Nuclei (RNCCN) Value-Added Product (VAP)

The objective of Retrieved Number concentration of Cloud Condensation Nuclei (RNCCN) Value-Added Product (VAP) is to provide the vertical distribution of cloud condensation nuclei (CCN) number concentrations to better represent aerosol indirect effects in climate models. The RNCCN VAP allows to collect a large number of independent samples of vertical CCN measurements at various supersaturation values from the ground. This helps to avoid the high cost of aircraft and increases the temporal distribution of retrieved CCN in the planetary boundary layer. The VAP method is based on Ghan and Collins (2004) and Ghan et al. (2006) proposed parameterizations that retrieve the vertical profiles of CCN directly from the ground level CCN, humidification factor, and in-situ lidar measurements. Further, the VAP accuracy is improved by using the quality controlled data that ensures that the boundary layer is well mixed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Enhanced alcohol production over binary Mo/Co carbide catalysts in syngas conversion

Recently metal carbide catalysts have attracted attention as alternatives to pure metals for the conversion of syngas to higher oxygenates, a process which could enable the sustainable production of fuels, polymers, and chemicals. Although Mo and Co carbides have both shown promise for higher oxygenate production, they have not achieved the requisite activity and selectivity for practical implementation. In this work we synthesize and characterize a binary Mo and Co carbide catalyst that exhibits improved activity and oxygenate selectivity relative to either pure metal carbide. In this work, we apply a combination of advanced electron microscopy and X-ray diffraction to show that the binary Mo/Co carbide catalyst forms uniformly mixed amorphous nanoparticles. Through in situ X-ray absorption spectroscopy studies, we determine that the structure of the mixed metal carbide catalyst under reaction conditions consists of both carbidic and bimetallic components. By testing the catalytic properties of a series of Mo/Co carbide catalysts prepared by different synthesis methods, we find that the Mo and Co sites must be in close contact to achieve improved syngas conversion to higher alcohols. Through in situ DRIFTS measurements, both Mo and Co atoms at the surface of the catalyst are identified as adsorption sites for reactive species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The International Soil Moisture Network: serving Earth system science for over a decade

In 2009, the International Soil Moisture Network (ISMN) was initiated as a community effort, funded by the European Space Agency, to serve as a centralised data hosting facility for globally available in situ soil moisture measurements (Dorigo et al., 2011b, a). The ISMN brings together in situ soil moisture measurements collected and freely shared by a multitude of organisations, harmonises them in terms of units and sampling rates, applies advanced quality control, and stores them in a database. Users can freely retrieve the data from this database through an online web portal (https://ismn.earth/en/, last access: 28 October 2021). Meanwhile, the ISMN has evolved into the primary in situ soil moisture reference database worldwide, as evidenced by more than 3000 active users and over 1000 scientific publications referencing the data sets provided by the network. As of July 2021, the ISMN now contains the data of 71 networks and 2842 stations located all over the globe, with a time period spanning from 1952 to the present. The number of networks and stations covered by the ISMN is still growing, and approximately 70% of the data sets contained in the database continue to be updated on a regular or irregular basis. The main scope of this paper is to inform readers about the evolution of the ISMN over the past decade, including a description of network and data set updates and quality control procedures. A comprehensive review of the existing literature making use of ISMN data is also provided in order to identify current limitations in functionality and data usage and to shape priorities for the next decade of operations of this unique community-based data repository.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

In Situ Non-Destructive Temporal Measurements of the Rhizosphere Microbiome ‘Hot-Spots’ Using Metaproteomics

Rhizosphere arguably embodies the most diverse microbial ecosystem on the planet, yet it is largely a functional ‘black box’ of belowground plant-microbiome interactions. The rhizosphere is the primary site of entry for subsurface injection of fixed carbon (C) into soil with impacts on local to global scale C biogeochemistry and ultimately Earth’s climate. While spatial organization of rhizosphere is central to its function, small scale and steep microbial and geochemical gradients within this dynamic region make it easily disrupted by sampling. The significant challenge presented by sampling blocks elucidation of discreet functions, drivers, and interactions within rhizosphere ecosystems. Here, we describe a non-destructive sampling method linked to metaproteomic analysis in order to measure temporal shifts in the microbial composition and function of rhizosphere. A robust, non-destructive method of sampling microbial hotspots within rhizosphere provides an unperturbed window into the elusive functional interactome of this system over time and space.

59 BASIC BIOLOGICAL SCIENCES↗