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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Enhancement in Mechanical Properties of Bulk Nanocrystalline Aluminum by Grain Boundary Strengthening Mechanism

In the present work, commercially pure aluminum (Al) powders were milled at cryogenic temperatures (a) without magnesium (Mg) and (b) with 5 wt.% Mg powders for different durations. The cryomilled powders were analyzed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-ray diffraction (XRD) to determine the changes in particle morphology, elemental composition, and crystallite size. The results showed a reduction in crystallite size with the increase in cryomilling duration. Thereafter, the spark plasma sintering (SPS) process was carried out to manufacture bulk samples. The mechanical properties of the bulk SPS samples were assessed by conducting microhardness, tensile, and fatigue tests. The Vickers microhardness tests showed improved hardness for the Al-Mg bulk samples as compared to pure Al. The Al-Mg samples also showed an increase in tensile strength with increasing cryomilling time. Fatigue test results showed an improvement in Al-Mg components' high-cycle fatigue response. Furthermore, the mechanism for the enhancement in mechanical properties as a result of crystallite size reduction and grain boundary strengthening by the addition of Mg dopant is also discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Assessment of two benzylation strategies for the analysis of nerve-agent derived ethyl- and pinacolyl methyl phosphonic acids in sandy loam soil by GC–MS

Despite their prohibition by the Chemical Weapons Convention, nerve agents (NAs) remain in use against military and civilian targets. Due to their high reactivity, NAs readily degrade to phosphonic acids, making them important markers in the inspection of areas of presumed NA use. In this work, we assess the use of benzylation to modify ethyl- and pinacolyl methylphosphonic acids, degradation products of VX and Soman respectively, for their efficient detection in a soil matrix at ~10 and ~1 μg/g using GC–MS. The soil matrix, Sandy Loam (SL), was chosen for its ubiquitous nature, complex composition with silica particles embedded in clay, and low organic content. In this study, we demonstrate that benzylation via benzyl bromide yields a LOD = 25.6 ng/mL for benzylated-EMPA and LOD = 30.1 ng/mL for benzylated-PMPA. This is superior to the use of p-methoxybenzyl trichloroacetimidate in providing stable phosphonic acid ester derivatives for analysis. A base-modified procedure for p-methoxybenzylation was explored in this study yielding a LOD = 29.1 ng/mL for p-methoxybenzylated-EMPA and LOD = 39.8 ng/mL for p-methoxybenzylated-PMPA. Both benzylation pathways (benzyl bromide and p-methoxybenzyl trichloroacetimidate) can be used to yield phosphonic acid derivatives that provide further confirmation of these Soman and VX degradation products in soil samples in investigative scenarios. The work herein represents the first application of benzylation methods for the analysis of these NA markers in the acidic, silicon-based SL soil.

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

Identification of uranium oxidation states using oxygen K-edge scanning transmission X-ray microscopy

The field of nuclear forensics is growing in importance, and the increasing capabilities at synchrotron radiation light sources enable non-destructive characterization of oxide particles with better spatial, compositional, and oxidation state speciation resolution than ever before. Here, uranium oxide particles derived from multiple wet chemical processing methods were examined using a scanning transmission X-ray microscope (STXM), and a weakly-supervised method was developed to automatically analyze the collected data. Multiple uranium oxidation states were observed and quantified within and between samples, yielding information about differences between particles produced via the various processing routes.

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

Influence of aluminum source and Ni/Al ratio in a batch stirred tank reactor on the structure, morphology, and electrochemical performance of Ni-rich NMA cathodes

Here, the structural, morphological, and electrochemical performance of Ni-rich LiNi 0.9 Mn 0.05 Al 0.05 O 2 (955NMA) and LiNi 0.85 Mn 0.05 Al 0.1 O 2 (85,510) cathodes strongly depends on the properties of their hydroxide precursors. Ni-Mn-Al hydroxide precursors were synthesized through controlled co-precipitation in a batch stirred tank reactor, where pH, reaction time, metal-ion feed rate, aluminum source, and aluminum concentration were systematically varied to tailor particle morphology, phase composition, and dopant distribution. Two aluminum sources, aluminum nitrate and sodium aluminate produced two distinct hydroxide precursors NMA(OH) 2 -1 and NMA(OH) 2 -2, which were lithiated to form LiNMA1 (Li 0.992 [Ni 0.905 Mn 0.049 Al 0.046 ]O 2 ) and LiNMA2 (Li 0.990 [Ni 0.850 Mn 0.047 Al 0.103 ]O 2 ). Structural and compositional analyses revealed that aluminum incorporation and phase formation in Ni–Mn–Al hydroxides are governed by local supersaturation and interfacial growth kinetics. Rapid dilute aluminum addition produced aluminum-free β-phase hydroxides, intermediate conditions generated mixed α/β phases, whereas slow concentrated dosing enabled uniform aluminum incorporation and stabilization of the β-phase structure. LiNMA1 delivers a high initial discharge capacity of 223 mAhg −1 but significant capacity fading with 67% retention after 100 cycles, associated with structural instability. In contrast, LiNMA2 delivers a lower initial capacity 172 mAhg −1 yet excellent cycling stability 91% retention, attributed to improved TM–O framework stability and reduced cation disorder.

Capacity↗
DOE OSTI2022

Chemical compatibility of hollow ceramic cenospheres as thermal insulation for high-temperature thermal energy storage applications with molten nitrate salt

An effective insulation material that is both thermally and chemically stable in molten salts could transform the design of molten-salt-based thermal energy storage (TES) tanks. Most current molten salt TES tanks hold the metallic tank structure in direct contact with hot salt inventory, a design which leads to thermal expansion of the tank and triggers stresses that can lead to thermomechanical failures. With an internal insulation to lower the temperature at the tank structure, the extent of thermal expansion can be reduced, thereby reducing expansion-induced stresses and allowing for consideration of lower-cost tank structure materials. Conventional insulation materials are either 1) too porous and allow molten salts to permeate into the matrix, which significantly increases the thermal conductivity or 2) too dense and have a thermal conductivity that cannot provide sufficient thermal insulation. This paper presents an alternative thermal insulation concept using cenospheres which have an alumino-silicate structure. The cost analysis suggests that the low-density cenospheres can be one of the cheapest materials to provide cost-effective thermal insulation. The chemical compatibility of cenospheres is investigated in molten 60 wt% NaNO3/40 wt% KNO3 salt which is close to industrial-grade Solar Salt. This paper shows that diffusion of the sodium and potassium cations from the salt into the cenospheres occurs based on weight analysis, energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. The cation diffusion breaks the bridging oxygen bonds and causes volume expansion of the microstructure which is responsible for the failure of the cenosphere particles. The chemical composition of the cenospheres is found to affect their compatibility with molten nitrate salt. A cenosphere product with low iron content showed the best compatibility with an average survival rate of 77.9% +/- 9.8% after 7 days of immersion in the molten nitrate salt. While even the low-iron cenospheres appear to require protection from direct molten salt contact, their slow degradation rate, closed-cell porosity, and low cost hold potential for effective use as internal tank insulation.

14 SOLAR ENERGY↗
DOE OSTI2023

Observationally Constrained Modeling of the Reactive Uptake of Isoprene-Derived Epoxydiols under Elevated Relative Humidity and Varying Acidity of Seed Aerosol Conditions

Isoprene is the non-methane volatile organic compound (VOC) emitted in largest amounts to the atmosphere, and it is a significant source of secondary organic aerosol (SOA) mass. The uptake of isoprene oxidation products followed by multiphase chemistry in fine particles is the key pathway to form isoprene epoxydiol-derived SOA (IEPOX-SOA). However, many parameters that relate to diffusion and reaction of IEPOX in the particle phase remain uncertain, since reaction kinetics previously measured in bulk aqueous phase solutions might be different from atmospheric aerosols. Here, we use simultaneous environmental chamber measurements of multiple parameters governing IEPOX-SOA formation at timescales of ~hours: particle size distribution, composition, and volatility of IEPOX-SOA to constrain the key parameters governing IE-POX-SOA formation under humid (i.e., 50% relative humidity, RH) and varying seed aerosol acidity conditions. Reducing the 2-methyltetrol (tetrol) reaction rate constants by a factor of 4 brings the model predictions in agreement with the IEPOX-SOA measurements with acidified ammonium bisulfate seed aerosols. For less acidic ammonium sulfate aerosols both the organo-sulfate (OS) and tetrol reaction rate constants need to be reduced to bring model predictions closer to chamber observations. Using the measured non-volatile content of IEPOX-SOA we constrain the oligomerization timescale of 2-methyltetrols. We find that the oligomerization timescale is 4 hours with acidified seed aerosols, but a much longer time scale of 24 hours is needed for non-acidified seed aerosols, indicating that the aerosol acidity greatly affects the oligomerization rate of tetrols. Here we show that the actual kinetics of IEPOX-SOA formation rate on aerosol seeds consisting of both ammonium bisulfate and ammonium sulfate are a factor of 4~5 slower under 50-60% RH conditions compared to their application in previous models, which were based on bulk aqueous solution measurements.

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

Symmetry-Breaking and Self-Sorting in Block Copolymer-Based Multicomponent Nanocomposites

Co-assembly of inorganic nanoparticles (NPs) and nanostructured polymer matrix represents an intricate interplay of enthalpic or entropic forces. Particle size largely affects the phase behavior of the nanocomposite. Theoretical studies indicate that new morphologies would emerge when the particles become comparable to the soft matrix's size, but this has rarely been supported experimentally. By designing a multicomponent blend composed of NPs, block copolymer-based supramolecules, and small molecules, a 3-D ordered lattice beyond the native BCP's morphology was recently reported when the particle is larger than the microdomain of BCP. The blend can accommodate various formulation variables. In this work, when the particle size equals the microdomain size, a symmetry-broken phase appears in a narrow range of particle sizes and compositions, which we named the "train track" structure. In this phase, the NPs aligned into a 3-D hexagonal lattice and packed asymmetrically along the c axis, making the projection of the ac and the bc plane resemble train tracks. Computational studies show that the broken symmetry reduces the polymer chain deformation and stabilizes the metastable hexagonally perforated lamellar morphology. Given the mobility of the multicomponent blend, the system shows a self-sorting behavior: segregating into two macroscopic phases with different nanostructures based on only a few nanometers NP size differences. Smaller NPs form "train track" morphology, while larger NPs form a "simple hexagon" structure, where the NPs take a symmetric hexagonal arrangement. Detailed structural evolution and simulation studies confirm the systematic-wide cooperativity across different components, indicating the strong self-regulation of the multicomponent system.

"train track" morphology↗
DOE OSTI2024

Structural, Electrochemical, and (De)lithiation Mechanism Investigation of Cation-Disordered Rocksalt and Spinel Hybrid Nanomaterials in Lithium-Ion Batteries

Significant demand for lithium-ion batteries necessitates alternatives to Co- and Ni-based cathode materials. Cation-disordered materials using earth-abundant elements are being explored as promising candidates. Here, in this paper, we demonstrate a coprecipitation synthetic approach that allows direct preparation of disordered rocksalt Li 2.4 Fe 1.0 Ti 1.0 O 4.7 (r-LFTO·C) and spinel structured hybrid Li 0.5 Fe 1.0 Ti 0.9 O 3.2 ·C (s-LFTO·C) nanoparticles with a conformal conductive carbon coating. High-angle annular dark-field imaging coupled with electron energy loss spectroscopy mapping shows uniform Fe/Ti distribution with minor compositional variation among particles. Cation disorder was confirmed for both of the materials at an atomic level, with a short-range order more pronounced in r-LFTO·C. Operando X-ray absorption spectroscopy, ex situ hard X-ray photoelectron spectroscopy, ex situ soft X-ray absorption spectroscopy, and ex situ synchrotron X-ray diffraction were used to investigate (de)lithiation in the bulk and at the surface. Structurally, the r-LFTO·C demonstrated reversible partial Fe center migration between octahedral and tetrahedral sites during (de)lithiation. The r-LFTO·C evidenced that the redox of O was coincident with iron redox during initial electrochemical cycling, while iron redox dominated later cycling. In contrast, s-LFTO·C electrochemistry involved iron redox throughout the cycling process. The findings rationalize the differences in the electrochemistry where r-LFTO·C shows higher initial capacity yet poorer capacity retention over a voltage window where O redox can be accessed, while the s-LFTO·C shows lower initial capacity yet improved capacity retention.

25 ENERGY STORAGE↗
DOE OSTI2024

Redox dynamics and surface structures of an active palladium catalyst during methane oxidation

Catalysts based on palladium are among the most effective in the complete oxidation of methane. Despite extensive studies and notable advances, the nature of their catalytically active species and conceivable structural dynamics remains only partially understood. Here, we combine operando transmission electron microscopy (TEM) with near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT) calculations to investigate the active state and catalytic function of Pd nanoparticles (NPs) under methane oxidation conditions. We show that the particle size, phase composition and dynamics respond appreciably to changes in the gas-phase chemical potential. In combination with mass spectrometry (MS) conducted simultaneously with in situ observations, we uncover that the catalytically active state exhibits phase coexistence and oscillatory phase transitions between Pd and PdO. Aided by DFT calculations, we provide a rationale for the observed redox dynamics and demonstrate that the emergence of catalytic activity is related to the dynamic interplay between coexisting phases, with the resulting strained PdO having more favorable energetics for methane oxidation.

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

Hybrid quantum-classical simulations of magic angle spinning dynamic nuclear polarization in very large spin systems

Solid-state nuclear magnetic resonance can be enhanced using unpaired electron spins with a method known as dynamic nuclear polarization (DNP). Fundamentally, DNP involves ensembles of thousands of spins, a scale that is difficult to match computationally. This scale prevents us from gaining a complete understanding of the spin dynamics and applying simulations to design sample formulations. We recently developed an ab initio model capable of calculating DNP enhancements in systems of up to ~1000 nuclei; however, this scale is insufficient to accurately simulate the dependence of DNP enhancements on radical concentration or magic angle spinning (MAS) frequency. We build on this work by using ab initio simulations to train a hybrid model that makes use of a rate matrix to treat nuclear spin diffusion. We show that this model can reproduce the MAS rate and concentration dependence of DNP enhancements and build-up time constants. Finally, we then apply it to predict the DNP enhancements in core–shell metal-organic-framework nanoparticles and reveal new insights into the composition of the particles’ shells.

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

Development and validation of a humidified CAPS-PMSSA with an improved methodology to calculate the truncation correction factor

Absorbing aerosols play an important role in the Earth’s radiation budget, and current uncertainties associated with their radiative impacts remain substantial. An element of this uncertainty derives from insufficient understanding of the extent to which water, as a coating on absorbing particles, enhances the absorption. Here, we describe and characterize the performance of a cavity-attenuated phase shift single scatter albedo spectrometer (CAPS-PMSSA) system that has been modified to enable concurrent aerosol extinction and scattering measurements, from which aerosol absorption is derived, at relative humidities up to ~90%. The modified instrument is referred to as the humidified CAPS (HCAPS). Additionally, we develop and validate an update to a method to calculate the truncation correction factor, used to correct the scattering measurements, that can account for the effects of particle growth and compositional changes resulting from water uptake. The method can be applied to experiments that use either size-selected or polydisperse aerosol samples of either known or unknown composition. Overall, we show that measurements made with the HCAPS, when processed using the updated truncation correction method, enable accurate measurement of the influence of water uptake on light absorption.

Dal Porto, Rachael [University of California, Davi↗
DOE OSTI2025

Hetero-Orbital Two-Component Fractional Quantum Hall States in Bilayer Graphene

A two-dimensional electron system exposed to a strong magnetic field produces a plethora of strongly interacting fractional quantum Hall (FQH) states, the complex topological orders of which are revealed through exotic emergent particles, such as composite fermions, and fractionally charged Abelian and non-Abelian anyons. Much insight has been gained by the study of multicomponent FQH states, where spin and pseudospin indices of the electron contribute additional correlation. Traditional multicomponent FQH states develop in situations where the components share the same orbital states and the resulting interactions are pseudospin independent; this homo-orbital nature is also crucial to their theoretical understanding. Here, we study “hetero-orbital” two-component FQH states, in which the orbital index is part of the pseudospin, rendering the multicomponent interactions strongly SU(2) anisotropic in the pseudospin space. Such states, obtained in bilayer graphene at the isospin transition between 𝑁 = 0 and 𝑁 = 1 electron Landau levels, are markedly different from previous homo-orbital two-component FQH states. In particular, we observe strikingly different behaviors for the parallel-vortex and reverse-vortex attachment composite fermion states, and an anomalously strong two-component 2/5 state over a wide range of magnetic field before it abruptly disappears at a high field. Our findings, combined with detailed theoretical calculations, reveal the surprising robustness of the hetero-orbital FQH effects, significantly enriching our understanding of FQH physics in this novel regime.

Bilayer graphene↗
DOE OSTI2021

Formation of Aerosol Nanoparticles by Gas-Phase Hydrolysis Reaction of Uranium Hexafluoride

The aerosol physics of uranyl particle formation has been addressed in this research using advanced aerosol instrumentation and an aerosol dynamics model. Based on the research works, we conclude that the formation and growth of aerosol particles by gas-phase UF6 hydrolysis strongly depends on the availability of water molecules in our reactor conditions. The total number concentration of the UO 2 F 2 particulate material that could be produced in the hydrolysis reaction is also regulated primarily by the availability of water molecule concentration. The higher the water molecule concentration, the higher the number and the larger the size of UO 2 F 2 aerosol particles that could be produced in a reactor custom-built at ORNL. Although the aerosol reactor was enabling the study of particle formation kinetics, the instrumentation was still insufficient in characterizing the chemical composition of the produced particles as well as the time-dependent evolution of the particulate species. The temporal evolution could impact the eventual fate of the particles upon release to the environment (i.e., the physio-chemical transformation, transport, and removal). On uranyl particle formation kinetics, we found that the growth rates of aerosol particles appeared to approach a single number in the range of 0.05 ± 0.03 - 0.08 ± 0.04 nm/s, statistically, as the ω value becomes smaller than 1. The size of primary particles from the UF6 hydrolysis at water-deprived condition was estimated to be 3.6 ± 0.4 nm; the higher the availability of water molecules, the larger the primary particles. The ability to precisely control the availability of water molecules in the reaction could lead to the production of nearly monodispersed aerosol particles. In other words, the result suggests that one can precisely manipulate the size of UO 2 F 2 aerosol particles by controlling the water vapor availability and interaction of water molecules with U F6 in the reaction. This finding has significant implications in the engineering manufacturing of fuel powder materials and possibly to future development and deployment of an environmental sampling apparatus.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

ETF Grout Expansion: Effects of Different Slags and Struvite Precipitation Protocols (Stirring Time)

The ETF ammonia tolerant grout waste form was developed by the Vitreous State Laboratory (VSL) to stabilize ammonium and thereby prevent emission of ammonia vapor during solidification of an ammonium-rich, concentrated sodium sulfate aqueous waste stream generated at the Hanford Effluent Treatment Facility (ETF). VSL personnel did not observe expansion in samples prepared during the waste form development work. However, Savannah River National Laboratory (SRNL) personnel detected expansion, in a few ETF grout samples, up to ~ 20 percent vertical expansion, while preforming work scope to evaluate the effect of ETF brine compositional ranges on the precipitation and solidification processes. The initial work requests can be found in Washington River Protection Services (WRPS) Statement of Work (SOW, Requisitions #: 339922 Revisions 0 and 1, March 11, 2021, and November 2021, respectively. As a result of the waste form expansion observed by SRNL, additional evaluation was requested by WRPS SOW Requisitions #: 356730 Revision 0 and Revision 1, February 1, 2022, and July 11, 2022, respectively. The goal of these requests was to determine whether differences in the slags and / or in sample preparation protocols used by VSL and SRNL were the cause of the expansion observed in the SRNL samples. G. Chen, WRPS, arranged a materials exchange between VSL and SRNL and coordinated the VSL protocol(s) for grouting and curing 1L batches of Base Case ETF base case simulant. Materials were exchanged between VSL and SRNL. Both laboratories performed the VSL struvite precipitation-solidification protocol and cured samples for at least 28 days. Differences in VSL and SRNL slag compositions, mineralogy and particle size results in themselves or combined were determined to not be the cause of the expansion because all samples expanded regardless of whether the VSL or SRNL slags were used. The fundamental cause of the observed expansion could not be attributed to minor variations in the following: 1) chemistry of the slag and other reagents, 2) container wall thickness, 3) ambient bench top curing conditions at VSL and SRNL, 4) pH adjustments to 7 ± a few tenths of unit, nor 5) stirring time between the precipitation and solidification process steps. Additional observations include: grout samples prepared with VSL slag expanded less than those prepared with the SRNL slag and, based on a very limited sample set, some samples stirred for longer times expanded less than those stirred for 20 minutes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Adaptive Sampling for In Situ Cloud Probe (Final Report)

Clouds play a leading role in the Earth's global energy and solar radiation balance and hydrological cycle. Improving cloud models requires detailed information on the cloud microphysical properties, such as droplet size distribution and number density, liquid water content and cloud composition (droplets, ice particles), which can only be provided by aerial in situ measurements. However, for many atmospheric measurement instruments, the lack of flexibility in selecting the operational mode during operation can lead to uncertainties in sampling and measurement characteristics under continuously varying atmospheric conditions. This SBIR project is developing an advanced, compact optical imaging technology for in situ characterization of cloud hydrometeors. The development involves a deep modification of the existing Mesa Photonics’ Cloud Droplet Measurement System (CDMS) in order to implement real-time automatic adaptive sampling based on the acquired in situ data and environmental parameters. The new system, CDMS-2, implements two measurement modes: side-scatter imaging for smaller hydrometeors and direct bright-field-illumination imaging for larger hydrometeors in a significantly larger sample volume. The system measures the droplet size distribution (DSD) and number density with an added capability of discriminating between liquid water and ice hydrometeors (based on polarization-resolved side-scatter imaging). The instrument will implement automatic switching or alternating between the regular side-scatter imaging mode and sparse/large hydrometeor mode (based on the acquired data). Other adaptive sampling capabilities include variable sample volume and dynamic range (based on the measured DSD). The preferred deployment platforms are uncrewed aircraft systems (UAS) and tethered balloon/kite systems (TBS). The Phase I project achieved (or exceeded) the goals listed in the Work Plan. A CDMS-2 laboratory prototype implementing the polarization-resolved side-scatter imaging mode and direct bright-field-illumination imaging mode was designed and built. Additional capabilities included the variable illumination pulse energy and sample volume. The smallest detectable droplet diameter was improved to 3–4 μm (from the nominal 10 μm value specified for the original CDMS). Discrimination between water droplets and ice particles was experimentally demonstrated. The Phase I prototype was extensively tested and calibrated in the laboratory and also tested in the Pi Cloud Chamber at Michigan Technological University (MTU). The two intensive experimental campaigns at MTU provided unique opportunities of testing the CDMS-2 laboratory prototype under realistic warm and mixed-phase cloud conditions (stable for long periods of time), testing different sampling modes and intercomparing the CDMS-2 prototype to other co-located cloud characterization instruments. The Phase I project successfully demonstrated the feasibility of the proposed technology and identified the engineering challenges of designing a field deployable prototype instrument in Phase II. The Phase I study provides a solid basis for development, characterization and field-testing of the proposed advanced cloud probe with adaptive sampling in Phase II followed by commercialization of the technology in Phase III.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Thermodynamics of Minerals Stable near Earth's Surface

Project “Thermodynamics of Minerals Stable Near the Earth’s Surface” uses specialized calorimetric techniques to obtain new thermochemical data for solid phases of interest in the Earth’s “critical zone”, the near surface regions of the planet most directly affecting and affected by human activity. Major activity was in three areas: manganese oxide materials, aluminum clusters which are precursors to aluminum oxyhydroxide precipitates, and zeolites. All these classes of minerals are potential carriers of heavy metals and radionuclides in the environment, both within their crystal structures and as adsorbed layers or colloids. Their thermodynamic stability, as well as the sequence of stability of competing phases, governs the aqueous solubility of contaminants (and nutrients) in soil, groundwater, and sediments. The thermodynamics of these phases is strongly affected by particle size and crystallinity, since they often occur as very fine particles which do not coarsen in the near-surface environment. Many of these materials exhibit extensive polymorphism, multicomponent solid solution, and variable hydration states. Thus, one must define and systematize important thermodynamic variables, since one cannot make measurements on each and every possible phase, particle size, and composition. A major finding of the work on manganese oxides was labile water-induced oxidation-reduction reactions. These will be studied further by a combination of thermodynamic and synchrotron-based spectroscopic methods, the latter in collaboration with Peggy O’Day at UC Merced. The adsorption of other species, including simple organics, on such redox-active surfaces will also be investigated by a combination of thermochemical and spectroscopic studies. Studies of the energetics of water adsorption on mineral surfaces will be expanded to emphasize the adsorption of CO2 and small organic molecules, relevant to soil, groundwater, and the subsurface environment. Gas adsorption calorimetry, immersion calorimetry, and solution calorimetry will be combined with appropriate analytical and spectroscopic techniques to obtain a comprehensive picture of the interactions and their energetics. The evolution of aqueous aluminum clusters to form aluminum oxyhydroxide precipitates will be studied in detail by a combination of calorimetric and structural methods applied to aqueous samples aged at room temperature. The energetics of new classes of clusters will be explored. The project addresses several common themes relevant to the broad mission of the Department of Energy. Thermochemical data for minerals stable near the Earth’s surface, though still incomplete, are essential for understanding both natural and anthropogenic processes that affect our very existence on this planet. Such data contribute to the fundamental underpinning for mitigation and management strategies for the extraction and use of energy. Fundamental thermodynamic and mechanistic understanding is required to model processes ranging from heavy metal pollution to nuclear waste disposal to climate change.

58 GEOSCIENCES↗
DOE OSTI2025

Extinction of Laser Light Due to Arctic Haze Final Campaign Report

Recent changes in emission patterns may have altered the historical stability of light attenuation strengths within the Arctic and, more specifically, the polar dome. While there have been decades of past and ongoing research on how atmospheric constituents, such as aerosols, affect light absorption, the bulk of this work is focused on the visible region. In recent years, there has been renewed interest in understanding laser light propagation at wavelengths such as 1 and 2 µm in this area. There is a need to evaluate how specific environmental parameters affect the propagation of light in this wavelength region, in particular: the extinction, scattering, and absorption coefficients, and how they relate to particle concentration; cn 2 and refractive index variations. Seasonally dependent variations in particle concentrations and compositions introduce different absorption and scattering characteristics that, in conjunction with varying temperatures, index-of-refraction variations, and wind, can result in laser beam focus and irradiance degradation. Understanding the fundamental influence of these parameters with respect to the propagation of light across a wide spectral band could lead to new insights about the minimal required datastreams required to provide accurate light propagation forecasting.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Bismuth-Functionalized Silica Aerogels for Iodine Capture

The U.S. Department of Energy is looking into alternative sorbents for the removal of radioiodine from off-gas streams in a used nuclear fuel reprocessing plant. One class of sorbents considered are bismuth-functionalized silica aerogels which offer an efficient capture of iodine from off-gas streams and are environmentally friendly and lower cost when compared to silver-functionalized sorbents. Two types of bismuth-functionalized silica aerogels were successfully manufactured using a hierarchical synthesis approach:1) The Bi 3+ -aerogel with bismuth oxide nitrate hydroxide hydrate particles and 2) Bi-aerogel with bismuth metal and bismuth sulfide nanoparticles. Both sorbents exhibited high sorption capacity for iodine. However, presence of particles of different composition, size, and distribution on aerogel support resulted in different iodine loadings. The Bi 3+ -aerogel exhibited sorption capacity of 289 mg/g. In contrast, Bi-aerogel exhibited more that 20% higher sorption capacity. The heat-treatment of Bi 3+ -aerogel at 225? under hydrogen atmosphere increased iodine loading capacity to 351 mg/g.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗