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

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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Beyond Volume Variation: Anisotropic and Protrusive Lithiation in Bismuth Nanowire

Materials storing energy via an alloying reaction are promising anode candidates in rechargeable lithium-ion batteries (LIBs) due to their much higher energy density than the current graphite anode. Until now, the volumetric expansion of such electrode particles during lithiation has been considered as solely responsible for cycling-induced structural failure. Here, we report different structural failure mechanisms using single-crystalline bismuth nanowires as the alloying-based anode. The Li–Bi alloying process exhibits a two-step transition, that is, Bi–Li 1 Bi and Li 1 Bi–Li 3 Bi. Interestingly, the Bi–Li 1 Bi phase transition occurs not only in the bulk Bi nanowire but also on the particle surface showing its characteristic behavior. The bulk alloying kinetics favors a Bi-(012)-facilitated anisotropic lithiation, whose mechanism and energetics are further studied using the density functional theory calculations. More importantly, the protrusion of Li 1 Bi nanograins as a result of anisotropic Li–Bi alloying is found to dominate the surface morphology of Bi particles. The growth kinetics of Li 1 Bi protrusions is understood atomically with the identification of two different controlling mechanisms, that is, the dislocation-assisted strain relaxation at the Bi/Li 1 Bi interface and the short-range migration of Bi supporting the off-Bi growth of Li 1 Bi. As loosely rooted to the bulk substrate and easily peeled off and detached into the electrolyte, these nanoscale protrusions developed during battery cycling are believed to be an important factor responsible for the capacity decay of such alloying-based anodes at the electrode level.

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

Machine learning to accelerate screening for Marcus reorganization energies

Understanding and predicting the charge transport properties of π-conjugated materials is an important challenge for designing new organic electronic devices, such as solar cells, plastic transistors, light-emitting devices, and chemical sensors. A key component of the hopping mechanism of charge transfer in these materials is the Marcus reorganization energy which serves as an activation barrier to hole or electron transfer. While modern density functional methods have proven to accurately predict trends in intramolecular reorganization energy, such calculations are computationally expensive. In this work, we outline active machine learning methods to predict computed intramolecular reorganization energies of a wide range of polythiophenes and their use toward screening new compounds with low internal reorganization energies. Our models have an overall root mean square error (RMSE) of ±0.113 eV, but a much smaller RMSE of only ±0.036 eV on the new screening set. Since the larger error derives from high-reorganization energy compounds, the new method is highly effective to screen for compounds with potentially efficient charge transport parameters.

14 SOLAR ENERGY↗
DOE OSTI2022

Simultaneous quantification of uranium( VI ), samarium, nitric acid, and temperature with combined ensemble learning, laser fluorescence, and Raman scattering for real-time monitoring

In this work, laser-induced fluorescence spectroscopy (LIFS), Raman spectroscopy, and a stacked regression ensemble was developed for near real-time quantification of uranium(VI) (1–100 μg mL –1 ), samarium (0–200 μg mL –1 ) and nitric acid (0.1–4 M) with varying temperature (20 °C–45 °C). LIFS applications range from fundamental lab-scale studies to real-time process monitoring at industrial levels, such as nuclear reprocessing applications, provided the phenomena affecting the fluorescence spectrum are accounted for (e.g., absorption, quenching, complexation). Multiple chemometric models were examined and compared to a more traditional multivariate regression approach called partial least squares (PLS). Results obtained on synthetic samples selected using D-optimal experimental design indicated that a stacked regression method, which included ridge regression, random forest, PLS, and an eXtreme gradient boost algorithm, successfully measured uranium(VI) concentrations directly in nitric acid without measuring luminescence lifetimes or standard addition. The top model resulted in percent root-mean-square error of prediction values of 5.2, 1.9, 3.0, and 2.3% for U(VI), Sm 3+ , HNO 3 , and temperature, respectively. The approach may be useful for quantifying fluorescent fission products (e.g., Sm 3+ ) to provide information on burnup of irradiated nuclear fuel. This novel framework reinforces the applicability of LIFS for real-time applications in nuclear fuel cycle applications.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Deeply Rooted: Evaluating Plant Rooting Depth as a Means for Enhanced Soil Carbon Sequestration (Abbreviated Final Report)

Soils store three times as much carbon (C) as the atmosphere, but are not at capacity, and enhanced soil C storage is considered an essential strategy to mitigate rising atmospheric CO 2 levels. Agricultural soils have experienced substantial C loss in the past century due to poor agricultural practices and erosion. A shift towards deep-rooting crops and low-impact soil management could potentially increase long-term sequestration of C fixed by plants and stored in their root tissues, particularly for crops that have naturally deep root systems (>1 meter). A substantial amount of the CO 2 taken up by plants is allocated to their root systems, and because C deposited in deep soil layers has a longer residence time (up to millennia, in contrast to C deposited in topsoils), C increases at depth may have better long-term C sequestration potential than topsoils. However, the accrual, turnover, and stabilization of C in subsoils is a critical knowledge gap.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Best practices in catalysis: A perspective

Catalysis, from its roots in petrochemical refining and conversion, has emerged as a transdisciplinary field that now encompasses synthesis of materials and molecules that enable applications in energy conversion and storage, environmental remediation, medicine, plastics, and fertilizer production, among numerous others. A handful of disciplines can claim relevance and success over such an extended period of time and continue to claim a preeminent role in defining the state-of-the-art in science and technology. Syncretic and rapid advancements in formulation and spectroscopic characterization of materials and molecules useful as catalysts, high-level density functional and molecular orbital theory calculations, and a strong foundation in concepts of physical chemistry, thermodynamics, and chemical kinetics offer new and abundant opportunities at the present day for addressing the grand challenge of controlling chemical transformations using catalysis. Here, we examine what we have learned of concepts that underpin heterogeneous catalysis but more importantly, how we learned to archive our knowledge in context of a set of best practices and standards that have emerged in the course of our learnings—ones we seek to highlight herein. Our perspective emphasizes concepts in synthesis, characterization, kinetics, and theory, because these four elements combined enable description of molecular acts that happen on surfaces and how fast they occur. In revisiting best practices in heterogeneous catalysis in these sub-fields and in authorship and peer review we aspire to augment clarity, reproducibility, and rigor in the science and practice of catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Carbon dioxide, water vapor and methane soil efflux (soil respiration) in a Pinus palustris root exclusion in Georgetown, SC

This dataset contains processed data from a combination of survey flux chambers and long-term automated flux chambers. Soil flux measurements were conducted from June 2023 through December 2025 in a mature longleaf pine forest in Georgetown, SC. Soil respiration measurements were conducted approximately biweekly for two and a half years, before and after a root exclusion that took place on May 5, 2024. Processed, QAQC’d data for the treatment (root exclusion) and control (roots intact) before and after the root exclusion can be found in the file: 1_DATA_ESS_DOE_HR_RS_HB2_QAQC_Survey_Data_20260223.csv. Two multiday deployments were also conducted prior to the root exclusion using long-term automated chambers to continuously monitor greenhouse gas soil efflux. Processed, QAQC’d data for both long-term deployments can be found in the file: 2_DATA_ESS_DOE_HR_RS_HB2_QAQC_Longterm_Data_20260209.csv. Raw and working data files (.json, .81x, & .82z format) from LI-COR equipment are included for reference and can be accessed using SoilFluxPro software. CSV metadata files describe the raw data and modifications made using SoilFluxPro v5 and Matlab R2024b, as well as formatting and units for processed CSVs. Matlab code is included for reading in the processed CSVs, with sample figures comparing treatment and control. This research was performed as part of the project: “Improving models of stand and watershed carbon and water fluxes with more accurate representations of soil-plant-water dynamics in southern pine ecosystems”, which examines in part the effects hydraulic redistribution on soil efflux of carbon dioxide, water vapor and methane, as well as soil moisture and temperature in a southern pine ecosystem with sandy soils and high water table.

CARBON DIOXIDE FLUX↗
DOE OSTI2020

An approach for broad molecular imaging of the root-soil interface via indirect matrix-assisted laser desorption/ionization mass spectrometry

Understanding of rhizospheric processes is limited by the need for imaging complex molecular transformations at relevant spatial scales within the root soil continuum. In this work, we demonstrate a method to enable this analysis by first extracting organic compounds from the rhizosphere onto a PVDF membrane while maintaining their 2D distribution. We then image the distribution of chemical compounds using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). This approach permitted us to visualize and identify compounds on the root surface and presumed root exudates in the rhizosphere. Within a 1.8 cm x 0.6 cm sampling area of a switchgrass rhizosphere, we could observe at least four chemically distinct zones. Using high performance Fourier transform ion cyclotron MS, we were able to accurately annotate numerous molecules co-localized to each of these zones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A dual membrane-adsorption evaporator for solar-powered lithium extraction from complex brines

A reliable supply of lithium is required to meet the increased demand for batteries over the coming decades. In this work, we demonstrated the potential to effectively extract lithium from brines by coupling solar-powered evaporation, adsorption, and membrane technologies together. We first synthesized a three-dimensional adsorptive evaporator by coating a lithium manganese oxide material onto a cotton stick using an easily scalable, one-step method. An osmotic membrane was then installed at the root of the evaporator to enhance the lithium to magnesium selectivity, prevent scaling caused by divalent cations, and thus further increase the water evaporation flux. The operation of the dual membrane-adsorption evaporator is entirely driven by osmosis and capillary force, demanding no extra energy input. The integration of the osmotic membrane was found to increase the lithium to magnesium selectivity over 10-fold to higher than 40. The dual process also produced high lithium to calcium selectivity and proved to sustain long-term stability by self-managing its internal osmotic pressure. Last, a test was done in three simulated brine solutions with varied brine chemistry and the evaporation rate stayed high and consistent throughout the long-term test. This illustrates that this technology can be used in varied brine solutions throughout the world providing efficient lithium capture and separation from competing divalent cations.

Eskafi, Aydin F. [University of California, Berkel↗
DOE OSTI2026

Ensemble Effects on Hydroxide Bond Dissociation Free Energies in Polyoxovanadate Clusters

Understanding structure-property relationships is foundational to numerous modern chemistries, such as proton-coupled electron transfer (PCET). However, an experimentally measured property is the result of the behavior from an ensemble of molecules. Neglecting ensemble effects, especially under complex chemical environments, may obfuscate these relationships and lead to discrepancies between theory and experiment. In this work, we demonstrate the impact of configurational entropy and local chemical environments on hydroxide bond dissociation free energies [BDFE- (O−H)] for a set of polyoxovanadate nanoclusters, at ambient conditions. The O−H bond strengths are investigated via density functional theory (DFT) coupled with statistical thermodynamic analysis and bilinear modeling, and compared with previous experimental results on the same systems, namely electrochemical solutions of: [V 6 O 13−x (OH) x (TRIOL R ) 2 ] −2 (x = 2, 4, 6; R = NO 2 , Me) and [V 6 O 11−x (OMe) 2 (OH) x (TRIOL NO 2 ) 2 ] −2 (x = 2, 4). Interestingly, we find that ensemble effects, even at room temperature, can account for a significant portion of the BDFE(O−H) trend with the degree of reduction via H atom binding, which cannot be fully captured by single-structure, static DFT calculations. Moreover, we find that the ensemble effects may be replicated statistically, requiring only enumeration of energetically accessible H-binding sites. With the ensemble effects resolved, we present a simple bilinear model to reconcile remaining biases between experiment and ensemble-informed theory, which corelate with clusterspecific electronic environment differences. The bilinear model achieves outstanding accuracy vs experiments with a root-mean squared error of 0.4 kcal/mol. Finally, based on the physicochemical characteristics of hydrogen interaction with polyoxometalates, we present a simple methodology that captures the BDFE(O−H) trend while dramatically reducing required DFT calculations by 98% and achieving accuracy within 1 kcal/mol. Overall, this work elucidates the roles and structural origins of configurational entropy and chemical effects on polyoxometalate hydroxide bond energies, with potential applicability to various atomically precise metal oxide systems. Importantly, it introduces models for rapid and highly accurate property calculations in connection with experiments.

Cluster chemistry↗
DOE OSTI2022

Soil oxidoreductase zymography: Visualizing spatial distributions of peroxidase and phenol oxidase activities at the root-soil interface

Decomposition of organic material in the rhizosphere – the most dynamic microbial habitat in soil – involves arrays of oxidoreductase and hydrolytic enzymes. Spatial distributions of various hydrolytic activities in soil have already been explored by zymographic techniques. However, the distribution of oxidative activity in the rhizosphere remains to be studied. Thus, we extended a Time-Lapse Zymography technique, using Amplex Red® reagent, to visualize and quantify distributions of phenol oxidase and peroxidase activities in the rhizosphere of Zea mays L. growing in a Haplic Phaeozem and the non-rhizospheric soil. The gross oxidative activity was greatest at the root surfaces, and fell to background soil levels 1.26 and 0.73 mm from seminal (>1 mm diameter) and lateral (<0.5 mm diameter) roots, respectively. The rhizosphere extent relative to the root radius was 59% broader around lateral than around seminal roots. The greatest activities, up to 30 nmol cm –2 min –1 , were peroxidase-dominated and closely associated with roots. Here, the results confirm the utility of the approach for studying spatio-temporal distributions of oxidative activities in soil. However, actual activity of oxidoreductases in the field will be strongly controlled by fluctuating environmental conditions such as soil aeration and the gradient of reactive oxygen species, which need to be considered especially in anoxic soils.

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

Vacuum-ultraviolet absorption cross-sections of functionalized four-carbon species

Absorption cross-sections were measured in the vacuum ultraviolet from 5.17 – 9.92 eV using differential absorption spectroscopy for 33 four-carbon species: n-butane, trans-2-butene, cis-2-butene, butanal, butyric acid, ethyloxirane, trans-2,3-dimethyloxirane, cis-2,3-dimethyloxirane, 2-methyloxetane, 2,2'-bioxirane, vinyl oxirane, 3,4-epoxybutan-2-one, diacetyl, diethyl ether, ethyl vinyl ether, vinyl acetate, acetic anhydride, 1-butanol, 3-buten-1-ol, 1–hydroxy-butan-2-one, 1–hydroxy-butan-3-one, 2,3-epoxybutan-1-ol, 3,4-epoxybutan-1-ol, 2-oxetanemethanol, butanone, methyl vinyl ketone, 4H-1,3-dioxine, allyl formate, 2-oxobutanal, 4-hydroxybutanal, 2-methyloxetan-3-one, cis–but-2-en-1-ol, and trans-2–but-enal. Uncertainties were quantified in all cases by accounting for errors in gas-phase concentration, experimental repeatability, and signal-to-noise ratio as a function of photon energy. With the exception of 2-oxobutanal, which is reported with an uncertainty of 10%, convolving the sources of error using the root-sum-square method led to an upper limit of 5% uncertainty above the detection limit, which is largely attributable to chemical purity. Here, the primary objective of the present work is to provide absolute cross-sections along with quantified uncertainty limits. The majority of the absorption spectra, which reflect electronic transitions such as σ → σ* and n → σ*, are reported for the first time and provide insight into fundamental chemical physics, such as vibrational band structure and Rydberg transitions. The quantitative spectra in the present work facilitates the discovery of chemical intermediates that support improvement in the accuracy of computational models for low-temperature combustion and atmospheric chemistry.

biofuels↗
NASA NTRS1992

Monitoring small-crack growth by the replication method

The suitability of the acetate replication method for monitoring the growth of small cracks is discussed. Applications of this technique are shown for cracks growing at the notch root in semicircular-edge-notch specimens of a variety of aluminum alloys and one steel. The calculated crack growth rate versus Delta K relationship for small cracks was compared to that for large cracks obtained from middle-crack-tension specimens. The primary advantage of this techinque is that it provides an opportunity, at the completion of the test, to go backward in time towards the crack initiation event and 'zoom in' on areas of interest on the specimen surface with a resolution of about 0.1 micron. The primary disadvantage is the inability to automate the process. Also, for some materials, the replication process may alter the crack-tip chemistry or plastic zone, thereby affecting crack growth rates.

Swain, Mary H.↗
DOE OSTI2025

Molecular Origin of Nanoscale Anion Ordering of LiTFSI Electrolytes Revealed through SAXS/WAXS and Molecular Dynamics Simulations

Recent developments in “water-in-salt” electrolytes have precipitated a renewed effort to study imide-based electrolytes. While previous small-/wide-angle X-ray scattering (SAXS/WAXS) studies have attributed the emergence of a low-Q peak in the SAXS profile of aqueous LiTFSI electrolytes to nanometer-scale anion clustering, a molecular-level understanding of the root of these clusters remains unclear. Here, in this study, we combined molecular dynamics simulations and SAXS/WAXS to study the solvation structures of LiTFSI in acetonitrile, methanol, and water. We concluded that hydrogen bonding in water and MeOH stabilizes anion clusters, while nonpolar methyl groups on methanol and acetonitrile interrupt the nanoscale ordering of TFSI anions. This causes LiTFSI in water and MeOH electrolytes to exhibit two low-Q SAXS profile peaks while LiTFSI in acetonitrile exhibits only a single peak below Q = 1 Å –1 . These findings shed light on the underlying molecular origins of nanoscale anion clusters, which may help in the design of the next generation of electrolyte chemistries.

Trojanowski, Lucas [Univ. of Michigan, Ann Arbor, ↗
DOE OSTI2023

Experimental and Computational Studies of Stress Corrosion Cracking of Alloys 308/309 and 82/182 Weldments in Corrosive and Radiation Environment

The goal of the project was to determine factors that influence SCC and IASCC in weldments found in LWR nuclear power plants. We focused on a SA508-304L SS weldment fabricated by EPRI using gas tungsten arc welding and used an aggressive BWR normal water chemistry (NWC) immersion environment. This weldment used 309L butter and 308L groove filler material. The microstructure of the 309L butter was non-uniform, exhibiting a 20–30μm thick martensitic layer closest to the SA508 interface, a 1–4 mm thick single γ austenite phase dilution zone, and a γ–δ duplex region extending to the 308L groove filler. The 308L groove filler had an entirely γ–δ duplex microstructure. Two approximately 1-inch thick 304L and SA508 plates approximately 12 by 6 square inches were joined using standard nuclear grade welding techniques. This included a post weld heat treatment of the 309L butter after application, a 0.32 cm fit-up root opening, and 57 bead lines of 308L groove filler applied in 18 layers. A 60 degree weld bevel angle was used and the 309L butter was 1.5 cm thick. Displacement cascade damage was induced using proton irradiation at the Michigan Ion Beam Laboratory. The incident proton energy was 2 MeV, the sample temperature was 360 ºC, and the calculated dpa value at 10 μm (60% of the Bragg peak depth of ~18 μm) was 5 dpa using the quick Kinchin-Pease model. Proton irradiation to this damage level required approximately 125 hours of beam time. Two types of samples were irradiated, tensile specimens and TEM bars. Samples were selected from all regions of the weldment, including the SA508-309L butter interface, the 309L-308L interface, and 308L-304L interface. The stainless steel alloys (304L, 308L, and 309L) within the heat affected zone are characterized by a duplex skeletal morphology of δ-ferrite and γ-austenite resulting from the recrystallization associated with weld fabrication. Approximately 7 to 8 mm of length along the specimen was irradiated. The gauge volume surfaces were mechanically polished and then electro-polished to remove mechanical damage from the mechanical polishing step prior to irradiation. Immersion tests were performed in a recirculating autoclave under BWR NWC conditions (2000 ppb wt. dissolved oxygen, neutral pH, 288 ºC, 10 MPa, and inlet water conductivity <100 nS/cm) to accelerate corrosion. Constant strain rate tests were performed either to failure or to approximately 5% strain. Strain rates of 10 -7 to 10 -6 mm/mm/s were used and typical immersion testing required four to six weeks to achieve failure or strains near 5%. Analysis primarily used advanced electron microscopy techniques of FIB lift out specimens.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Effective Local Geometry Descriptor for 29Si NMR Q4 Anisotropy

The nuclear shielding anisotropy, ζ, is a useful nuclear magnetic resonance (NMR) shielding tensor parameter in describing the extent of electron cloud distortion about an atom. Despite the advantages afforded by NMR in structural characterization, the relationship between ζ and local structure of an atom in high-symmetry environments, such as Si-Q 4 sites, is poorly understood. Here, we use a data-driven approach combining random forest feature ranking and the Sure Independence Screening and Sparsifying Operator (SISSO) approach to derive a simple and accurate geometric descriptor for ζ with a root-mean-squared prediction error of 6.77 ppm and an R 2 of 0.761. We then apply this descriptor to describe the local geometric distortion of zeolites Sigma-2 and silica-ZSM-5 whose chemical shift anisotropy tensor has been reported. We envision that this geometric descriptor will allow for structural description and refinement in previously difficult-to-describe materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

SimUAM: A Comprehensive Microsimulation Toolchain to Evaluate the Impact of Urban Air Mobility in Metropolitan Areas

Over the past several years, Urban Air Mobility (UAM) has galvanized enthusiasm from investors and researchers, marrying expertise in aircraft design, transportation, logistics, artificial intelligence, battery chemistry, and broader policymaking. However, two significant questions remain unexplored: (1) What is the value of UAM in a region’s transportation network?, and (2) How can UAM be effectively deployed to realize and maximize this value to all stakeholders, including riders and local economies? To adequately understand the value proposition of UAM for metropolitan areas, we develop a holistic multi-modal toolchain, SimUAM, to model and simulate UAM and its impacts on travel behavior. This toolchain has several components: (1) MANTA: A fast, high-fidelity regional-scale traffic microsimulator, (2) VertiSim: A granular, discrete-event vertiport and pedestrian, (3) 3: A high-fidelity, trajectory-based aerial microsimulation. SimUAM, rooted in granular, GPU-based microsimulation, models millions of trips and their exact movements in the street network and in the air, producing interpretable and actionable performance metrics for UAM designs and deployments. The modularity, extensibility, and speed of the platform will allow for rapid scenario planning and sensitivity analysis, effectively acting as a detailed performance assessment tool. As a result, stakeholders in UAM can understand the impacts of critical infrastructure, and subsequently define policies, requirements, and investments needed to support UAM as a viable transportation mode.

Urban air mobility↗
DOE OSTI2020

On the mechanism of soot nucleation

The mechanism of carbon particulate (soot) inception has been a subject of numerous studies and debates. The article begins with a critical review of prior proposals, proceeds to the analysis of factors enabling the development of a meaningful nucleation flux, and then introduces new ideas that lead to the fulfillment of these requirements. In the new proposal, a rotationally-activated dimer is formed in the collision of an aromatic molecule and an aromatic radical; the two react during the lifetime of the dimer to form a stable, doubly-bonded bridge between them, with the reaction rooted in a five-member ring present on the molecule edge. Several such reactions were examined theoretically and the most promising one generated a measurable nucleation flux. The consistency of the proposed model with known aspects of soot particle nanostructure is discussed. Here, the foundation of the new model is fundamentally the H-Abstraction-Carbon-Addition (HACA) mechanism with the reaction affinity enhanced by rotational excitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗