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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Observation of site-selective chemical bond changes via ultrafast chemical shifts

The concomitant motion of electrons and nuclei on the femtosecond time scale marks the fate of chemical and biological processes. Here we demonstrate the ability to initiate and track the ultrafast electron rearrangement and chemical bond breaking site-specifically in real time for the carbon monoxide diatomic molecule. We employ a local resonant x-ray pump at the oxygen atom and probe the chemical shifts of the carbon core-electron binding energy. We observe charge redistribution accompanying core-excitation followed by Auger decay, eventually leading to dissociation and hole trapping at one site of the molecule. The presented technique is general in nature with sensitivity to chemical environment changes including transient electronic excited state dynamics. This work provides a route to investigate energy and charge transport processes in more complex systems by tracking selective chemical bond changes on their natural timescale.

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

More chemical detection through less sampling: amplifying chemical signals in hyperspectral data cubes through compressive sensing

Compressive sensing (CS) is a method of sampling which permits some classes of signals to be reconstructed with high accuracy even when they were sampled at sub-Nyquist rates. In this paper we explore a phenomenon in which bandwise CS sampling of a hyperspectral data cube followed by reconstruction can actually result in amplification of chemical signals contained in the cube. Perhaps most surprisingly, chemical signal amplification generally seems to increase as the level of sampling decreases. In some examples, the chemical signal is significantly stronger in a data cube reconstructed from 10% CS sampling than it is in the raw, 100% sampled data cube. We explore this phenomenon in two real-world datasets including the Physical Sciences Inc. Fabry-Perot interferometer sensor multispectral dataset and the Johns Hopkins Applied Physics Lab FTIR-based longwave infrared sensor hyperspectral dataset. Each of these datasets contains the release of a chemical simulant, such as glacial acetic acid, triethyl phospate, and sulfur hexafluoride, and in all cases we use the adaptive coherence estimator (ACE) to detect a target signal in the hyperspectral data cube. We end the paper by suggesting some theoretical justifications for why chemical signals would be amplified in CS sampled and reconstructed hyperspectral data cubes and discuss some practical implications.

Hyperspectral imagery, Compressive Sensing, single↗
DOE OSTI2021

Specialty chemicals production case study: Economic analysis of modular chemical process intensification versus conventional stick‐built approaches

Abstract The beneficial synergies of chemical process intensification and plant modularization present a unique step‐wise advancement opportunity for many chemical manufacturers, but economic case studies are needed to raise awareness of such opportunities. The primary objective of this case study is to better understand the business case economics of a specialty chemical plant using modular chemical process intensification (MCPI), by comparing it with that of a conventional stick‐built (CSB) plant that produces the same product at the same production capacity. When comparing MCPI against CSB approaches for a plant project strategy decision, analysts should thoroughly understand and model the differences and similarities in scope bases. The MCPI approach for this case study benefitted from dramatic reductions in capital expenditures (CAPEX). A sizeable reduction in plant spatial volume likely explains some of these reductions. Sizeable operational expenditure (OPEX) reductions with the MCPI plant appear to be associated with the reduced operator staffing required from converting a labor‐intensive batch process into an automated, continuous flow process. Traditional project investment economic measures strongly favored the MCPI case for the design, construction, and operation of the specialty chemical plant. The net present value for the MCPI case was nearly twice that for the CSB case over a ten‐year period, and the payback period for the CSB case was nearly five times longer than that of the MCPI case. The opinion‐based perspective of the study participant identified significant contributors to superior MCPI economic performance for this case study. With the two conditions of low MCPI CAPEX and high product profit margin, economic analysis indicates that incorporation of a backup MCPI train, for operational redundancy when downtime occurs, is a very beneficial strategy.

O'Connor, James T.↗
DOE OSTI2022

Transmission electron microscopy characterization of the fuel-cladding chemical interactions in HT9 cladded U-10Zr fuel

Fuel cladding chemical interaction (FCCI) is a key phenomenon needs to be better understood to establish the design basis for U-10Zr metallic fuel performance. Characterizing the microstructure and chemical composition of FCCI at micron and sub-micron scale is critically important toward a more mechanistic understanding of FCCI phenomenon and its potential effects on cladding integrity and metallic fuel performance. This paper, by using transmission electron microscopy, investigated the FCCI region in HT9 cladded U-10Zr fuel irradiated to 5.7% FIMA burnup at a peak inner cladding temperature of 615 °C in Fast Flux Test Facility (FFTF). Four distinct layers are identified in the FCCI region. The migration of Fe into the fuel side leads to the formation of several U-Zr-Fe ternary phases, including ?-Fe0.5Zr0.32U0.18, e-Fe0.3Zr0.4U0.3, and ?-Fe0.06Zr0.23U0.71, mingled with UFe2, U6Fe, and U phase at various Fe penetration depth up to ~ 150 µm. On the cladding side, grain coarsening and significant lanthanides infiltration along grain boundaries are observed. Laves phase, (Fe,Cr)2(Mo,W), which typically does not exist in fresh HT9, is identified in a wide radial range in the cladding. The typical HT9 martensitic lath structure and pre-existing M23C6 precipitates disappear, partially or completely, depending on the radial distance from the fuel-cladding interface. Those microstructural and compositional changes could cause mechanical degradation in the HT9 cladding. The present characterization results will improve the understanding of FCCI phenomenon and facilitate the development of microstructure-informed FCCI modeling for metallic fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Molecular Polaritonics: Chemical Dynamics Under Strong Light–Matter Coupling

Chemical manifestations of strong light–matter coupling have recently been a subject of intense experimental and theoretical studies. Here we review the present status of this field. Section 1 is an introduction to molecular polaritonics and to collective response aspects of light–matter interactions. Section 2 provides an overview of the key experimental observations of these effects, while Section 3 describes our current theoretical understanding of the effect of strong light–matter coupling on chemical dynamics. A brief outline of applications to energy conversion processes is given in Section 4. Pending technical issues in the construction of theoretical approaches are briefly described in Section 5. Finally, the summary in Section 6 outlines the paths ahead in this exciting endeavor.

Chemistry↗
DOE OSTI2020

Chemical–Switching Strategy for Synthesis and Controlled Release of Norcantharimides from a Biomass–Derived Chemical

Catalytic strategies were developed to synthesize and release chemicals for applications in fine chemicals, such as drugs and polymers, from a biomass-derived chemical, 5-hydroxymethyl furfural (HMF). The combination of the diene and aldehyde functionalities in HMF enabled catalytic production of acetalized HMF derivatives with diol or epoxy reactants to allow reversible synthesis of norcantharimide derivatives upon Diels-Alder reaction with maleimides. Reverse-conversion of the acetal group to an aldehyde yielded mismatches of the molecular orbitals in norcantharimides to trigger retro Diels-Alder reaction at ambient temperatures and released reactants from the coupled molecules under acidic conditions. In conclusion, these strategies provide for the facile synthesis and controlled release of high-value chemicals.

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

Structural and chemical changes from CO2 exposure to self-healing polymer cement composites for geothermal wellbores

Wellbore cement is subjected to a number of mechanical, thermal and chemical stress regimes over its lifetime. Therefore, next generation wellbore cement formulations need to be evaluated in conditions relevant to these environments. In this work, we investigate the mechanism of the alteration of a novel self-healing polymer-cement composite recently reported by our group after exposure to a CO2-rich environment by using synchrotron based X-ray Fluorescence (XRF) and X-ray absorption near edge structure (XANES) and scanning electron microscopy coupled with energy dispersive spectroscopy. Results showed that chemical alteration of the polymer-cement follows the rim carbonation mechanism, similar to conventional cement although carbonation takes place to a lesser extent in polymer-cements despite the higher porosity. Along with detailed mechanistic insights on carbonation in polymer-cement composite, the performance of these in CO2-rich environment is further studied using standard compressive strength analysis.

Elbakhshwan, Mohamed↗
DOE OSTI2023

Tip-Enhanced Raman Chemical and Chemical Reaction Imaging in H 2 O with Sub-3-nm Spatial Resolution

Reproducible chemical and chemical reaction nano-imaging at solid-liquid interfaces remains challenging, particularly when resolutions on the order of a few nm are sought after. In this work, we demonstrate the latter through liquid tip-enhanced Raman (TER) measurements that target gold nanoplates functionalized with 4-mercaptobenzonitrile (MBN). In addition to chemical imaging and local optical field nano-visualization with high spatial resolution, we observe the signatures of 4-mercaptobenzoic acid, which forms as a result of plasmon-induced hydrolysis of MBN. Evidently, the solvent leads to distinct plasmon-induced/enhanced chemical reaction pathways that have not been documented. Here this work shows that such reactions that take place at solid-liquid interfaces can be tracked with a record sub-3 nm spatial resolution via TER spectral nano-imaging in liquids.

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

27 AlNMR chemical shift of Al(OH)$^{-}_{4}$ calculated from first principles: Assessment of error cancellation in chemically distinct reference and target systems

Predicting accurate nuclear magnetic resonance chemical shieldings relies upon cancellation of different types of errors between the theoretically calculated shielding constant of the analyte of interest and the reference. Often, the intrinsic error in computed shieldings due to basis sets, approximations in the Hamiltonian, description of the wave function, and dynamic effects is nearly identical between the analyte and reference, yet if the electronic structure or sensitivity to local environment differs dramatically, this cannot be taken for granted. Detailed prior work has examined the octahedral trivalent cation Al(H 2 O)$^{3+}_{6}$, accounting for ab initio intrinsic errors. However, the use of this species as a reference for the chemically distinct tetrahedral anion Al(OH)$^{-}_{4}$ requires an understanding of how these errors cancel, in order to define the limits of accurately predicting 27 Al chemical shielding in Al(OH)$^{-}_{4}$. In this work, we estimate the absolute shielding of the 27 Al nucleus in Al(OH)$^{-}_{4}$ at the coupled cluster level (515.1± 5.3 ppm). Shielding sensitivity to the choice of method approximation and atomic basis sets used has been evaluated. Solvent and thermal effects are assessed through ensemble averaging techniques using ab-initio molecular dynamics. The contribution of each type of intrinsic error is assessed for the Al(H 2 O)$^{3+}_{6}$ and Al(OH)$^{-}_{4}$ ions, revealing significant differences that fundamentally hamper the ability to accurately calculate the 27 Al chemical shift of Al(OH)$^{-}_{4}$ from first principles.

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

¡Viva la mitochondria!: harnessing yeast mitochondria for chemical production

ABSTRACT The mitochondria, often referred to as the powerhouse of the cell, offer a unique physicochemical environment enriched with a distinct set of enzymes, metabolites and cofactors ready to be exploited for metabolic engineering. In this review, we discuss how the mitochondrion has been engineered in the traditional sense of metabolic engineering or completely bypassed for chemical production. We then describe the more recent approach of harnessing the mitochondria to compartmentalize engineered metabolic pathways, including for the production of alcohols, terpenoids, sterols, organic acids and other valuable products. We explain the different mechanisms by which mitochondrial compartmentalization benefits engineered metabolic pathways to boost chemical production. Finally, we discuss the key challenges that need to be overcome to expand the applicability of mitochondrial engineering and reach the full potential of this emerging field.

Biotechnology & Applied Microbiology↗
DOE OSTI2023

Biomass Gasification for Chemicals Production Using Chemical Looping Techniques (Final Report)

The Ohio State University (OSU) is investigating the Biomass to Syngas (BTS) chemical looping technology to produce syngas for chemical production applications from biomass under US Department of Energy (DOE) Award #DE-EE0007530. The BTS process aligns with the programmatic area of interest of “Conversion, via biological, thermal, catalytic or chemical means, of acceptable feedstocks into advanced biofuels and/or biobased products including intermediate and end-use products”. Compared to conventional biomass gasification processes, the BTS process eliminates the need for air separation units and tar reforming reactors, which leads to energy efficiency improvement and capital cost reduction. The overall objective is to ascertain the potential of biomass gasification based on the chemical looping technique through mitigation of the possible techno-economic challenges in the steps of scale up for commercialization. The scope of work consists of 1) designing, constructing and operating a 10 kWth commercially scalable sub-pilot BTS system and; 2) completing a comprehensive techno-economic analysis (TEA) of the BTS process using methanol production as an example. Over the course of the project, the project team completed the design, fabrication, and operation of a 10 kWth sub-pilot scale test unit for the BTS process. Corn cob and wood pellets were successfully tested in the unit for high purity syngas generation in extended test campaigns that totals over 200 hours. Syngas purity (H2 and CO) of >70% was achieved with a CH 4 concentration of <6%. The H 2 /CO ratio was greater than 1.8. A comprehensive techno-economic analysis was performed to compare the BTS process and a reference indirectly heated gasification process for methanol synthesis. The result, updated with experimental results for BTS process performance, shows a methanol required selling price (MSP) of $\$ $1.15/gal, compared to $1.28/gal for the reference case.

08 HYDROGEN↗
DOE OSTI2021

Reply to “Comment on ‘Nomenclature, Chemical Abstracts Service numbers, isomer enumeration, ring strain, and stereochemistry: What does any of this have to do with an international chemical disarmament and nonproliferation treaty?’”

A letter to the Journal of Chemical Education provided comments and accurate enumerations of isomers for sets of organic compounds discussed in the paper “Nomenclature, Chemical Abstracts Service numbers, isomer enumeration, ring strain, and stereochemistry: What does any of this have to do with an international chemical disarmament and nonproliferation treaty?”. This is a reply to that letter to address the comments and propose updates to the original paper in order to incorporate the accurate enumeration values.

Alkanes/Cycloalkanes, Chemical Weapons Convention ↗
DOE OSTI2022

The Open Cluster Chemical Abundances and Mapping Survey. VI. Galactic Chemical Gradient Analysis from APOGEE DR17

The goal of the Open Cluster Chemical Abundances and Mapping (OCCAM) survey is to constrain key Galactic dynamic and chemical evolution parameters by the construction and analysis of a large, comprehensive, uniform data set of infrared spectra for stars in hundreds of open clusters. This sixth contribution from the OCCAM survey presents analysis of SDSS/APOGEE Data Release 17 (DR17) results for a sample of stars in 150 open clusters, 94 of which we designate to be "high-quality" based on the appearance of their color–magnitude diagram. We find the APOGEE DR17-derived [Fe/H] values to be in good agreement with those from previous high-resolution spectroscopic open cluster abundance studies. Using a subset of the high-quality sample, the Galactic abundance gradients were measured for 16 chemical elements, including [Fe/H], for both Galactocentric radius ($R$ GC ) and guiding center radius ($R$ guide ). We find an overall Galactic [Fe/H] versus RGC gradient of -0.073 ± 0.002 dex kpc -1 over the range of 6 > $R$ GC < 11.5 kpc, and a similar gradient is found for [Fe/H] versus $R$ guide . Significant Galactic abundance gradients are also noted for O, Mg, S, Ca, Mn, Na, Al, K, and Ce. Our large sample additionally allows us to explore the evolution of the gradients in four age bins for the remaining 15 elements.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Utility Energy Service Contract Boosts Chemical Weapons Destruction Mission at Army Pueblo Chemical Depot

For six decades, the U.S. Army has safely and securely stored chemical munitions at the Pueblo Chemical Depot in Colorado. To help fulfill international treaty obligations and to meet a congressional deadline of 2023 for the elimination of these aging weapons, initial destruction of the Pueblo chemical weapons stockpile began in 2015. A utility energy service contract (UESC) executed in 2016 between the U.S. Army Corps of Engineers and the Depot’s serving utility, Black Hills Energy (BHE), directly supported this mission with the installation of a new electrical substation that was essential to the Depot’s need for uninterrupted power.

Army Pueblo Chemical Depot↗
DOE OSTI2022

Effects of composition and canister centerline cooling on microstructure, phase distribution, and chemical durability of dehalogenated iron phosphate waste forms

This paper discusses the effects of composition and canister centerline cooling (CCC) on the microstructures, phase distribution, and chemical durability of dehalogenated iron phosphate waste forms starting from chloride-based salt simulants including KCl (Simple-1), NdCl3 (Simple-2), SrCl2 (Simple-3), LaCl3 (Simple-4), LiCl (Simple-5), CsCl (Simple-6), as well as a complex simulant containing LiCl, KCl, NaCl, CsI, SrCl2, CeCl3, and NdCl3 called ERV2. The simulants represent salt constituents present in salt wastes from electrorefiners used for electrochemical reprocessing. These salts are reacted with ammonium dihydrogen phosphate (ADP) resulting in a NH4Cl (dechlorination) byproduct that is captured and phosphate product containing oxides of the salt cations. This product is further stabilized using Fe2O3 through vitrification at higher temperatures. The results presented herein describe the properties of CCC-treated materials following dechlorination and vitrification including phase identification and quantification, elemental distributions, and chemical durabilities. The chemical durability in the CCC-cooled samples are lower durability than quenched materials for the ERV2 samples. The phases formed upon CCC cooling are very complex compositionally and microstructurally.

iron phosphate glass, iron phosphate waste forms, ↗