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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Probing the Surface Chemistry of Lithium Nitridation

Chemical synthesis of Li 3 N through lithium nitridation has potential to advance rechargeable battery and nitrogen fixation technology. However, studies of the conditions for forming Li 3 N on the lithium surface via nitrogen gas exposure report contradictory findings, such as the spontaneous reaction of Li with pure N 2 , the impossibility of forming Li 3 N through pure Li and N 2 interaction, the requirement of trace H 2 O to catalyze the reaction, and evidence to the contrary. In this study, ambient pressure X-ray photoelectron spectroscopy (APXPS) was applied to evaluate the in situ chemical evolution of the lithium metal surface under nitrogen gas up to 800 mTorr. At pressures ≤10 mTorr, no Li 3 N was detected. At higher pressures, surface Li 3 N rapidly reacts with trace CO 2 . Additionally, because metallic lithium is readily oxidized by trace gases, the atomic nitrogen concentration of the lithium surface remains below 2%. When nitridation follows oxidation by O 2 gas, CO 2 gas, or H 2 O vapor, surface Li 3 N formation is inhibited. These results suggest that nitrogen gas can diffuse through the oxidized lithium metal surface to react with subsurface metallic lithium.

Binding energy↗
DOE OSTI2023

Experimental and computational investigation into the hydrodynamics and chemical dynamics of laser ablation aluminum plasmas

Laser ablation plasma chemistry is governed by a complex interplay between hydrodynamic plasma-gas mixing processes, thermodynamics, and rapid high-temperature chemical reactions. Here, in this work, we investigate the gas-phase oxidation chemistry of ns-laser ablation aluminum plasmas in air using optical spectroscopy combined with advanced multi-physics modeling. Experimental measurements demonstrate the formation of AlO in the plasma plume as early as 1 μs while computational results reveal that several Al x O y species are distributed in the periphery of the plume at even earlier times (<20 ns) in the presence of large temperature gradients and strong shockwaves. Interactions with the ablation crater during rapid plume expansion are shown to initiate vortex formation, followed by mixing dynamics that work to pull AlO into the vortices to react with gas-phase Al to form Al 2 O. Oxygen and several aluminum oxides are simultaneously pulled up through the stem of the fireball, encouraging further intermixing between reacting species and enhanced molecular formation. This work concludes that chemical dynamics in laser ablation plasmas is driven by diffusion processes, concentration gradients, and plume hydrodynamics while strong shockwaves generated during laser ablation do not impede chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A covalent inhibitor targeting the papain-like protease from SARS-CoV-2 inhibits viral replication

Covalent inhibitors of the papain-like protease (PLpro) from SARS-CoV-2 have great potential as antivirals, but their non-specific reactivity with thiols has limited their development. In this report, we performed an 8000 molecule electrophile screen against PLpro and identified an α-chloro amide fragment, termed compound 1, which inhibited SARS-CoV-2 replication in cells, and also had low non-specific reactivity with thiols. Compound 1 covalently reacts with the active site cysteine of PLpro, and had an IC50 of 18 μM for PLpro inhibition. Compound 1 also had low non-specific reactivity with thiols and reacted with glutathione 1–2 orders of magnitude slower than other commonly used electrophilic warheads. Finally, compound 1 had low toxicity in cells and mice and has a molecular weight of only 247 daltons and consequently has great potential for further optimization. Collectively, these results demonstrate that compound 1 is a promising lead fragment for future PLpro drug discovery campaigns.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Kinetics of Radiation-induced Cr( II ) and Cr( III ) Redox Chemistry in Molten LiCl-KCl Eutectic

Chromium (Cr) is a frequent constituent of the metal alloys proposed for molten salt nuclear reactor (MSR) applications, and is typically the least noble metal ion present. Consequently, chromium is preferentially corroded into molten salt solutions. Here, the redox poise and redox cycling of chromium ions in the salt can greatly influence its corrosivity towards structural alloys, ultimately impacting the longevity of MSR systems. Radiation-induced chemistry is expected to play a significant role in determining the chromium oxidation state distribution during MSR operations. In the present research, electron pulse radiolysis techniques were employed to characterize the reactivity of Cr(II) and Cr(III) ions with primary radiolysis products in molten lithium chloride–potassium chloride (LiCl–KCl) eutectic over a temperature range of 400–600 °C. Both chromium oxidation states were found to rapidly react with the primary products of molten chloride salt radiolysis, i.e., the solvated electron (e S - ) and the dichlorine radical anion (Cl 2 ˙ - ). For reactions with the e S - , second-order rate coefficients (k) of k = (4.1 ± 0.2) and (6.1 ± 0.3) × 10 10 M -1 s -1 at 400 °C for Cr(II) and Cr(III), respectively, were determined. Temperature-dependent measurements allowed for the derivation of activation parameters for electron capture by Cr(II) and Cr(III). Both chromium ions also react with Cl 2 ˙ - , k = (7.2 ± 0.3) and (1.4 ± 0.1) × 10 9 M -1 s -1 at 400 °C for Cr(II) and Cr(III), respectively.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2025

Reactive CO 2 capture and mineralization of magnesium hydroxide to produce hydromagnesite with inherent solvent regeneration

Valorization of multiple low value streams including CO 2 emissions and magnesium-hydroxide bearing mine tailings to produce magnesium carbonate through reactive CO 2 capture and mineralization provides a less explored opportunity to manage several gigatons of CO 2 emissions. To resolve the feasibility of converting magnesium hydroxide to magnesium carbonate through reactive CO 2 capture and mineralization, CO 2 capture solvents such as sodium glycinate are harnessed to capture CO 2 and react directly with Mg(OH) 2 to produce hydromagnesite (Mg 5 [(CO 3 )4(OH) 2 ]·4H 2 O). This approach eliminates the energy-intensive step of producing high purity CO 2 associated with regenerating the solvent, and redissolving CO 2 to produce magnesium carbonate. Interestingly, while temperatures below 50 °C facilitate CO 2 capture, the mineralization kinetics are slow. However, at higher temperatures, accelerated carbon mineralization is favored by the faster kinetics of Mg(OH) 2 dissolution and precipitation of magnesium carbonate. Reacting Mg(OH) 2 at 90 °C with 15 wt% solids in the presence of 2.5 M sodium glycinate after 3 hours under well-stirred conditions results in an extent of carbon mineralization of 75.5%. The theoretical maximum extent of carbon mineralization when hydromagnesite is formed is 80%. Pre-loading CO 2 on the solvent is also an effective approach to ensure that sufficient CO2 is available for reactive CO 2 capture and mineralization, particularly when dilute CO 2 and N 2 mixtures are used. Higher extents of carbon mineralization are associated with an increase in the particle size and a reduction in the cumulative pore volume. These insights unlock the feasibility of harnessing reactive CO 2 capture and mineralization as a pathway to convert magnesium-hydroxide bearing resources into industrially relevant magnesium carbonate products.

Reactive CO2↗
DOE OSTI2025

Understanding CO 2 adsorption on the surfaces of SrO and its hydroxylated variants Sr(OH) 2 · n H 2 O ( n = 0, 1, 8)

Strontium oxide (SrO) is a promising material for CO 2 capture through a reversible cycle of carbonation and calcination, where SrO reacts with CO 2 to form SrCO 3 and can be regenerated by calcination. In the presence of moisture, SrO forms strontium hydroxide and its hydrates (Sr(OH) 2 ·nH 2 O). Here, this study, which employs density functional theory, investigates the CO 2 adsorption mechanism of these processes on various crystal surfaces, including SrO, Sr(OH) 2 , Sr(OH) 2 ·1H 2 O, and Sr(OH) 2 ·8H 2 O. A significant finding is that the interaction of CO 2 with these surfaces leads to carbonate/bicarbonate formation via electron transfer, with notable differences in CO 2 orientation and bond characteristics between SrO surfaces and its hydroxylated surfaces. To explore the effects of moisture on CO 2 adsorption, H 2 O adsorption on these stable surfaces was investigated. The results showed that H 2 O reacts with the SrO (100) surface to form hydroxyl (OH) groups while it bonds with the surfaces of Sr(OH) 2 ·nH 2 O (n = 0, 1, 8) with hydrogen bonding. A small amount of H 2 O can enhance CO2 adsorption while a large amount of H 2 O could decrease the capability of CO 2 adsorption.

CO2 capture↗
DOE OSTI2025

Unusual products arising from the tandem dehydrogenation of Mg(BH 4 ) 2 and pyrrolidine

The dehydrogenation of Mg(BH 4 ) 2 in the presence of O-Lewis base donors has been widely explored but there have been very few studies of dehydrogenation of the borohydride in the presence of N-Lewis bases. Mg(BH 4 ) 2 has been found to react with pyrrolidine at room temperature to form BH 3 -pyrrolidine adduct. Upon heating, further dehydrogenation reactions occur to form bis(pyrrolidino)borane, tris(pyrrolidino)borane and other B–N intermediates. Reacting Mg(BH 4 ) 2 and pyrrolidine in a 1 : 6 molar ratio exclusively yields tris(pyrrolidino)borane which is in accordance with predicted stoichiometric factors. The formation of these products contrasts with the routine production of higher boranes and/or intractable polymers from the dehydrogenation of Mg(BH 4 ) 2 in the presence O-Lewis bases. The amount of H 2 released in these reactions was determined both by the Parr autoclave pressure readings and the eudiometer measurements. Both measurements align with the values predicted by the stoichiometric factors associated by the proposed pathway.

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

Formation of tungsten ethylidene complexes from diethyl complexes through a proton-catalyzed rearrangement of ethylene

Here, W(NAr) 2 Et 2 (Ar = 2,6-diisopropylphenyl) reacts with two equivalents of R F9 OH (OR F9 = OC(CF 3 ) 3 ) to yield W(NAr)(ArNH 2 )(OR F9 )2(C 2 H 4 ) complexes and ethane. In solution W(NAr)(ArNH 2 )(OR F9 ) 2 (C 2 H 4 ) decomposes to give R F9 OH, ethane, W(NAr)(OR F9 ) 2 (C 2 H 4 ), and W(NAr)(NHAr′)(ArNH 2 )(OR F9 ), in which Ar′ contains a dehydrogenated isopropyl group (Ar′ = (2-i-Pr)(6-CMe=CH 2 )C 6 H 3 ) coordinated to the metal. On a similar time scale W(NAr)(OR F9 ) 2 (CHCH 3 ) complexes are formed from W(NAr)(OR F9 ) 2 (C 2 H 4 ) through an ArNH 2 -catalyzed rearrangement of the ethylene ligand. W(NAr)(NHAr′)(ArNH 2 )(OR F9 ) reacts with cyclohexene to form methylenecyclohexene and complexes that contain an NHAr″ ligand where Ar″ is a disubstituted (methyl/aryl) alkylidene, (2-i-Pr)(6-CMe)C 6 H 3 ) that is tethered to the metal through the amido nitrogen. In contrast to W(NAr)(ArNH 2 )(OR F9 ) 2 (C 2 H 4 ), analogous OR F6 (OCMe(CF 3 ) 2 ) and OR F3 (OCMe 2 (CF 3 )) complexes are relatively stable at 22 °C.

Maji, Milan [University of California, Riverside, ↗
DOE OSTI2025

Oxygenates production in a microfluidic dielectric barrier discharge device sustained in Ar/CH 4 /O 2

Reforming of methane (CH 4 ) is a process to produce syngas (CO/H 2 ) and other value-added chemicals including oxygenates such as methanol (CH 3 OH). Atmospheric pressure plasmas have the potential to be more energy efficient than traditional reforming methods as value-added chemicals can be synthesized directly in the plasma without requiring an additional step. In this paper, we discuss the results from a computational investigation of the formation of oxygenates by CH 4 oxidation in the presence of Ar, including CH 3 OH and CH 2 O, in a nanosecond pulsed dielectric barrier discharge. The plasma is formed in a microfluidic channel whose small dimensions are ideal for plasma formation at atmospheric pressure. The production and consumption mechanisms of dominant radicals and long-lived species are discussed in detail for the base case conditions of Ar/CH 4 /O 2 = 50/25/25. CH 3 OH is produced primarily by CH 3 O reacting with CH 3 O and CH 3 O 2 reacting with OH, while CH 2 O formation relies on reactions involving CH 3 O and CH 3 . The most abundant oxygenate formed is CO (produced by H abstraction from CHO). However, the greenhouse gas CO 2 is also formed as a by-product. The effects of gas mixture are examined to maximize the CH 3 OH and CH 2 O densities while decreasing the CO 2 density. Increasing the Ar percentage from 0% to 95% decreased the CH 3 OH and CH 2 O densities. At low Ar percentages, this is due to an increase in consumption of CH 3 OH and CH 2 O, while at high Ar percentages (>40% Ar), the production of CH 3 OH and CH 2 O is decreased. However, both CO and CO 2 reached peak densities at 70%–90% Ar. Changing the CH 4 /O 2 ratio while keeping 50% Ar in the discharge led to increased CH 3 OH and CH 2 O production, reaching peak densities at 35%–40% CH 4 . The CO and CO 2 densities decreased beyond 20% CH 4 , indicating that a CH 4 rich discharge is ideal for forming the desired oxygenates.

03 NATURAL GAS↗
DOE OSTI2025

Investigation of High-Temperature Compatibility of Select Oxides with Yttrium Hydride for Micro and Space Reactor Applications

Yttrium hydride is a promising material for a high-temperature neutron moderator in advanced micro and space reactors due to its high hydrogen density and relative thermal stability compared to other metal hydrides. However, yttrium hydride desorbs hydrogen rapidly at temperatures above 800°C, which is below the operational temperature range of some reactor designs. A hydrogen barrier coating of oxide on the hydride surface may inhibit hydrogen loss at 800°C and beyond, but the high-temperature compatibility between yttrium hydride and many oxides is currently unknown. The high-temperature compatibility of Al 2 O 3 , MgO, and Y 2 O 3 with YH 1.92 was examined by subjecting mixed oxide–hydride pellets to a 1200°C heat treatment then using a combination of diffractometry, microscopy, and spectroscopy to determine changes in the pellet composition as a result. Yttrium scavenged oxygen from both Al 2 O 3 and MgO to form Y 2 O 3 , resulting in significant loss of YH 1.92 . Yttrium reacted with reduced aluminum to form YAl 2 and several other compounds. Reduced magnesium volatilized above 1091°C and vacated the pellet. Only Y 2 O 3 did not appreciably react with YH 1.92 . Of the three oxides tested, only Y 2 O 3 was compatible with YH 1.92 at 1200°C based on the experimental criteria.

compatibility↗
DOE OSTI2025

Investigation of N 2 /O 2 plasma interaction with Pt-catalyst: effect of metastable adsorbates on product hysteresis

The coupling of catalysts and atmospheric-pressure plasma has the potential to improve the efficiency of certain catalytic reactions. Understanding the changes that the catalyst surface undergoes during exposure to plasma is key to improving plasma–catalytic performance. In this work, long term exposure of Pt–Al 2 O 3 powder catalyst to an Ar/N 2 /O 2 non-equilibrium atmospheric-pressure plasma-jet was investigated. Products produced by the interaction were analyzed downstream with Fourier-transform infrared spectroscopy while surface species were analyzed operandi with diffuse reflectance infrared Fourier transform spectroscopy. During exposure, the catalyst temperature was ramped cyclically between 100 °C and 350 °C to understand how substrate temperature affects the plasma–catalyst interaction. Long-lasting changes were revealed to take place on the catalyst surface during plasma exposure. At low temperatures, Pt–O and Pt–NO accumulate on the surface which react at elevated temperatures to form NO 2 . NO 2 initially appears to spill on to the Al 2 O 3 support as nitrites and nitrates instead of desorbing. Stable surface conditions are only achieved after prolonged plasma exposure, when nitrate sites on the Al 2 O 3 support are filled. By changing the catalyst temperature at various rates, the impact of total plasma species flux to the surface was analyzed. It was found that decreasing the heating rate increased the hysteresis in the pattern of NO 2 formation during thermal cycling. The variation with temperature demonstrates that plasma exposure results in a buildup of surface NO x and oxygen species which react or desorb at high temperatures. The observed changes are discussed from the generic viewpoint that a non-equilibrium plasma interacting with a catalyst at low temperature introduces metastable steady-state surface conditions. Upon heating above a threshold temperature, the introduced surface modifications can change either due to thermal effects, or, for a plasma environment, by additional interaction with the incident plasma species flux. The surface/material changes take place in a highly predictable fashion and after sufficient time above the threshold temperature reach a steady-state condition that is different from the transient behavior that is observed during initial heating. During cooling the plasma-surface interaction exhibits a different behavior than during heating, and this results in hysteresis of diverse observables. The metastability/hysteresis description appears quite generic and analogous to hysteresis behavior seen for different systems. Furthermore, it is expected to be useful for understanding the consequences of plasma–catalyst surface interactions for various systems.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Measurement of Charged-Pion Production in Deep-Inelastic Scattering off Nuclei with the CLAS Detector

Background: Energetic quarks in nuclear deep-inelastic scattering propagate through the nuclear medium. Processes that are believed to occur inside nuclei include quark energy loss through medium-stimulated gluon bremsstrahlung and intranuclear interactions of forming hadrons. More data are required to gain a more complete understanding of these effects. Purpose: To test the theoretical models of parton transport and hadron formation, we compared their predictions for the nuclear and kinematic dependence of pion production in nuclei. Methods: We have measured charged-pion production in semi-inclusive deep-inelastic scattering off D, C, Fe, and Pb using the CLAS detector and the CEBAF 5.014-GeV electron beam. We report results on the nuclear-to-deuterium multiplicity ratio for π + and π - as a function of energy transfer, four-momentum transfer, and pion energy fraction or transverse momentum—the first three-dimensional study of its kind. Results: The π + multiplicity ratio is found to depend strongly on the pion fractional energy z and reaches minimum values of 0.67 ± 0.03, 0.43 ± 0.02, and 0.27 ± 0.01 for the C, Fe, and Pb targets, respectively. The z dependencies of the multiplicity ratios for π + and π - are equal within uncertainties for C and Fe targets but show differences at the level of 10% for the Pb-target data. The results are qualitatively described by the GIBUU transport model, as well as with a model based on hadron absorption, but are in tension with calculations based on nuclear fragmentation functions. Conclusions: These precise results will strongly constrain the kinematic and flavor dependence of nuclear effects in hadron production, probing an unexplored kinematic region. They will help to reveal how the nucleus reacts to a fast quark, thereby shedding light on its color structure and transport properties and on the mechanisms of the hadronization process.

Moran, S.↗
DOE OSTI2020

Analysis of the multicomponent relativistic Boltzmann equation for electron scattering in big bang nucleosynthesis

Big-bang nucleosynthesis (BBN) is valuable as a means to constrain the physics of the early universe and it is the only probe of the radiation-dominated epoch. A fundamental assumption in BBN is that the nuclear velocity distributions obey Maxwell-Boltzmann (MB) statistics as they do in stars. Specifically, the BBN epoch is characterized by a dilute baryon plasma for which the velocity distribution of nuclei is mainly determined by the dominant Coulomb elastic scattering with mildly relativistic electrons. One must therefore deduce the momentum distribution for reacting nuclei from the multicomponent relativistic Boltzmann equation. However, the full multicomponent relativistic Boltzmann equation has only recently been analyzed and its solution has only been worked out in special cases. Moreover, a variety of schemes have been proposed that introduce nonthermal components into the BBN environment which can alter the thermal distribution of reacting nuclei. Here, we construct the relativistic Boltzmann equation in the context of BBN. We also derive a Langevin model and perform relativistic Monte-Carlo simulations which clarify the baryon distribution during BBN and can be used to analyze any relaxation from a nonthermal injection. Further, we show by these analyses that the thermalization process leads to a nuclear distribution function that remains very close to MB statistics even during the most relativistic environment relevant to BBN. Hence, the predictions of standard BBN remain unchanged.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Structural uncertainty assessment for fire-engulfed objects in crosswind: Establishing credibility for a multiphysics wall-modeled large-eddy simulation paradigm

A structural uncertainty validation study for a large-scale, fire-engulfed, elevated object subjected to crosswind is presented to establish the credibility of a high-fidelity, low-Mach, turbulent reacting flow wall-modeled large-eddy simulation (WMLES) approach that includes multiphysics coupling to participating media radiation and conjugate heat transfer. To establish that WMLES can accurately predict surface quantities including drag and pressure coefficient in the low-Mach crosswind regime, a foundational elevated isothermal cylinder validation case is presented at a similar gap-to-diameter ratio of 0.25, spanning the subcritical to supercritical drag regime (Re 𝐷 = 1.1 × 10 5 and 4.3 × 10 5 , respectively). Here, this study exercised both static and dynamic coefficient LES (Smagorinsky and 𝑘 sgs ) with both local and exchange-based velocity sampling. Results showcase that the drag crisis (or the sudden drop in drag coefficient at increased Re 𝐷 ) is well captured when using an exchange-based dynamic coefficient WMLES methodology, while noting lack of mesh convergence and overall drag and pressure coefficient predictively when using a static coefficient, local velocity sampling WMLES. For the 𝒪⁡(10) m JP-8 liquid pool fire crosswind validation study presented, two experimental crosswind configurations (2 m/s and 9.5 m/s) are showcased for a fire-engulfed mock fuselage roughly 4 m in diameter. Using the best model-form practices identified in the isothermal study, dynamic coefficient 𝑘 sgs exchange-based WMLES fire validation findings demonstrate accurate peak irradiation and skin temperature predictions as a function of crosswind magnitude. Excessive yaw in the low-crosswind fuselage configuration, consistent with experimental findings, captured a significant predicted asymmetry in flame attachment and heat flux toward the downwind cylindrical cap—indicative of axial vortex structures transporting the flame along the upper and lower fuselage leeward surface. All fire mesh resolution simulations captured the experimental finding that as crosswind increased, predicted flame shape and peak irradiation magnitude onto the fuselage transitioned from a windward to a leeward cylinder location due to the migration of the upper- to lower-shear fuel/air mixing layer thereby demonstrating the novelty, significance, and credibility of this high-fidelity WMLES reacting flow framework.

Domino, Stefan Paul [Sandia National Laboratories ↗
DOE OSTI2025

Domain Wall Reactions in Multiple-Order Parameter Ferroelectrics

The motion of domain walls is crucial for ferroelectric switching. Conventionally, the switching dynamics is believed to be determined by the motion of one or a few low-energy domain wall types of dominant population. Here, we challenge this conventional idea in multiple-order-parameter ferroelectrics. Using hafnia as example, we show that the multiple-order-parameter nature not only provides various mobile domain walls and defectlike immobile domain walls, but also enables the domain wall reactions. In analogy with chemical reactions where substances react to form new substances, domain walls could also react to form other domain walls during switching. We identify several elementary domain wall reaction types including synthesis, decomposition, and exchange reactions. Domain walls are continually changed by these reactions during switching so that the switching behavior reflects the statistical average of many domain wall types with distinct mobility and stability. These reactions also lead to phenomenon like remanent nuclei and defect-site nucleation that facilitate switching and lower coercive field. Finally, the concept of domain wall reaction is not limited to hafnia but can be generalized to any multiple-order-parameter ferroelectric. As a result, this Letter conceptualizes domain wall reaction, expands the theory of ferroelectric switching, and suggests a practical way for defect engineering to control switching behavior.

36 MATERIALS SCIENCE↗