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DOE OSTI2021

Observation of an Intermediate to H 2 Binding in a Metal–Organic Framework

Coordinatively unsaturated metal sites within certain zeolites and metal–organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through physical interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that nondissociative chemisorption of H 2 at the trigonal pyramidal Cu + sites in the metal–organic framework Cu I -MFU- 4 l occurs via the intermediacy of a metastable physisorbed precursor species. In situ powder neutron diffraction experiments enable crystallographic characterization of this intermediate, the first time that this has been accomplished for any material. Evidence for a precursor intermediate is also afforded from temperature-programmed desorption and density functional theory calculations. Here, the activation barrier separating the precursor species from the chemisorbed state is shown to correlate with a change in the Cu + coordination environment that enhances p-backbonding with H 2 . Ultimately, these findings demonstrate that adsorption at framework metal sites does not always follow a concerted pathway and underscore the importance of probing kinetics in the design of next-generation adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Description of reaction and vibrational energetics of CO 2 –NH 3 interaction using quantum computing algorithms

CO 2 capture is critical to solving global warming. Amine-based solvents are extensively used to chemically absorb CO 2 . Thus, it is crucial to study the chemical absorption of CO 2 by amine-based solvents to better understand and optimize CO 2 capture processes. Here, we use quantum computing algorithms to quantify molecular vibrational energies and reaction pathways between CO 2 and a simplified amine-based solvent model—NH 3 . Molecular vibrational properties are important to understanding kinetics of reactions. However, the molecule size correlates with the strength of anharmonicity effect on vibrational properties, which can be challenging to address using classical computing. Quantum computing can help enhance molecular vibrational calculations by including anharmonicity. We implement a variational quantum eigensolver (VQE) algorithm in a quantum simulator to calculate ground state vibrational energies of reactants and products of the CO 2 and NH 3 reaction. The VQE calculations yield ground vibrational energies of CO 2 and NH 3 with similar accuracy to classical computing. In the presence of hardware noise, Compact Heuristic for Chemistry (CHC) ansatz with shallower circuit depth performs better than Unitary Vibrational Coupled Cluster. The “Zero Noise Extrapolation” error-mitigation approach in combination with CHC ansatz improves the vibrational calculation accuracy. Excited vibrational states are accessed with quantum equation of motion method for CO 2 and NH 3 . Using quantum Hartree–Fock (HF) embedding algorithm to calculate electronic energies, the corresponding reaction profile compares favorably with Coupled Cluster Singles and Doubles while being more accurate than HF. Our research showcases quantum computing applications in the study of CO 2 capture reactions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2021

Data from: Niche differentiation of bacterial versus archaeal soil nitrifiers induced by ammonium inhibition along a management gradient

Soil nitrification, mediated mainly by ammonia oxidizing archaea (AOA) and bacteria (AOB), converts ammonium (NH4+) to nitrite (NO2−) and thence nitrate (NO3−). To better understand ecological differences between AOA and AOB, we investigated the nitrification kinetics of AOA and AOB under eight replicated cropped and unmanaged ecosystems (including two fertilized natural systems) along a long-term management intensity gradient in the upper U.S. Midwest. For five of eight ecosystems, AOB but not AOA exhibited Haldane kinetics (inhibited by high NH4+ additions), especially in perennial and successional systems. In contrast, AOA predominantly exhibited Michaelis-Menten kinetics, suggesting greater resistance to high nitrogen inputs than AOB. These responses suggest the potential for NH4+-induced niche differentiation between AOA and AOB. Additionally, long-term fertilization significantly enhanced maximum nitrification rates (Vmax) in the early successional systems for both AOA and AOB, but not in the deciduous forest systems. This was likely due to pH suppression of nitrification in the acidic forest soils, corroborated by a positive correlation of Vmax with soil pH but not with amoA gene abundance. Results also demonstrated that soil nitrification potentials were relatively stable, as there were no seasonal differences. Overall, results suggest that (1) NH4+ inhibition of AOB but not AOA could be another factor contributing to niche differentiation between AOA and AOB in soil, and (2) nitrification by both AOA and AOB can be significantly promoted by long-term nitrogen inputs.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1992

Velocity measurement in rocket exhaust and general aerodynamic flows by photolysis of H2O and laser induced fluorescence of OH

A 'tagging' approach in which the photolysis of H2O by an excimer laser creates a zone of enhanced OH concentration, while a second, pulsed-UV laser detects tagged-zone convection via time-delayed excitation of OH fluorescence, depends on the photodissociation process and the kinetics of OH decay (relative to velocity). For application to the fuel-rich, high supersonic Mach number exhaust flow of the SSME, the detection of OH is being accomplished with either a pulsed narrowband UV dye laser or a tunable XeCl excimer laser for excitation of an OH 0-0 band transition, while the two-photon photolysis of H2O is conducted by focusing an injection-locked KrF excimer laser into the flow.

Boedeker, Laurence R.↗

NASA NTRS2000

Remobilizing the Interfaces of Thermocapillary Driven Bubbles Retarded by the Adsorption of a Surfactant Impurity on the Bubble Surface

Thermocapillary migration is a method for moving bubbles in space in the absence of buoyancy. A temperature gradient is applied to the continuous phase in which a bubble is situated, and the applied gradient impressed on the bubble surface causes one pole of the drop to be cooler than the opposite pole. As the surface tension is a decreasing function of temperature, the cooler pole pulls at the warmer pole, creating a flow which propels the bubble in the direction of the warmer fluid. A major impediment to the practical use of thermocapillarity to direct the movement of bubbles in space is the fact that surfactant impurities which are unavoidably present in the continuous phase can significantly reduce the migration velocity. A surfactant impurity adsorbed onto the bubble interface is swept to the trailing end of the bubble. When bulk concentrations are low (which is the case with an impurity), diffusion of surfactant to the front end is slow relative to convection, and surfactant collects at the back end of the bubble. Collection at the back lowers the surface tension relative to the front end setting up a reverse tension gradient. For buoyancy driven bubble motions in the absence of a thermocapillarity, the tension gradient opposes the surface flow, and reduces the surface and terminal velocities (the interface becomes more solid-like). When thermocapillary forces are present, the reverse tension gradient set up by the surfactant accumulation reduces the temperature tension gradient, and decreases to near zero the thermocapillary velocity. The objective of our research is to develop a method for enhancing the thermocapillary migration of bubbles which have been retarded by the adsorption onto the bubble surface of a surfactant impurity, Our remobilization theory proposes to use surfactant molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher concentrations than the impurity, it adsorbs to the bubble much faster than the impurity when the bubble is formed, and thereby prevents the impurity from adsorbing onto the surface. In addition the rapid kinetic exchange and high bulk concentration maintain a saturated surface with a uniform surface concentrations. This prevents retarding surface tension gradients and keeps the velocity high. In our first report last year, we detailed experimental results which verified the theory of remobilization in ground based experiments in which the steady velocity of rising bubbles was measured in a continuous phase consisting of a glycerol/water mixture containing a polyethylene glycol surfactant C12E6 (CH3(CH2)11(OCH2CH2)6OH). In our report this year, we detail our efforts to describe theoretically the remobilization observed. We construct a model in which a bubble rises steadily by buoyancy in a continuous (Newtonian) viscous fluid containing surfactant with a uniform far field bulk concentration. We account for the effects of inertia as well as viscosity in the flow in the continuous phase caused by the bubble motion (order one Reynolds number), and we assume that the bubble shape remains spherical (viscous and inertial forces are smaller than capillary forces, i e. small Weber and capillary numbers). The surfactant distribution is calculated by solving the mass transfer equations including convection and diffusion in the bulk, and finite kinetic exchange the bulk and the surface. Convective effects dominate diffusive mass transfer in the bulk of the liquid (high Peclet numbers) except in a thin boundary layer near the surface. A finite volume method is used to numerically solve the hydrodynamic and mass transfer equations on a staggered grid which accounts specifically for the thin boundary layer. We present the results of the nondimensional drag as a function of the bulk concentration of surfactant for different rates of kinetic exchange, from which we develop criteria for the concentration necessary to develop a prescribed degree of remobilization. The criteria compare favorably with the experimental results.

Palaparthi, Ravi↗

DOE OSTI2020

Dynamic load balancing with enhanced shared-memory parallelism for particle-in-cell codes

Furthering our understanding of many of today’s interesting problems in plasma physics – including plasma based acceleration and magnetic reconnection with pair production due to quantum electrodynamic effects – requires large-scale kinetic simulations using particle-in-cell (PIC) codes. However, these simulations are extremely demanding, requiring that contemporary PIC codes be designed to efficiently use a new fleet of exascale computing architectures. To this end, the key issue of parallel load balance across computational nodes must be addressed. We discuss the implementation of dynamic load balancing by dividing the simulation space into many small, self-contained regions or ‘‘tiles,’’ along with shared-memory (e.g., OpenMP) parallelism both over many tiles and within single tiles. The load balancing algorithm can be used with three different topologies, including two space-filling curves. Here, we tested this implementation in the code Osiris and show low overhead and improved scalability with OpenMP thread number on simulations with both uniform load and severe load imbalance. Compared to other load-balancing techniques, our algorithm gives order-of-magnitude improvement in parallel scalability for simulations with severe load imbalance issues.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1991

Computer-based video digitizer analysis of surface extension in maize roots: kinetics of growth rate changes during gravitropism

We used a video digitizer system to measure surface extension and curvature in gravistimulated primary roots of maize (Zea mays L.). Downward curvature began about 25 +/- 7 min after gravistimulation and resulted from a combination of enhanced growth along the upper surface and reduced growth along the lower surface relative to growth in vertically oriented controls. The roots curved at a rate of 1.4 +/- 0.5 degrees min-1 but the pattern of curvature varied somewhat. In about 35% of the samples the roots curved steadily downward and the rate of curvature slowed as the root neared 90 degrees. A final angle of about 90 degrees was reached 110 +/- 35 min after the start of gravistimulation. In about 65% of the samples there was a period of backward curvature (partial reversal of curvature) during the response. In some cases (about 15% of those showing a period of reverse bending) this period of backward curvature occurred before the root reached 90 degrees. Following transient backward curvature, downward curvature resumed and the root approached a final angle of about 90 degrees. In about 65% of the roots showing a period of reverse curvature, the roots curved steadily past the vertical, reaching maximum curvature about 205 +/- 65 min after gravistimulation. The direction of curvature then reversed back toward the vertical. After one or two oscillations about the vertical the roots obtained a vertical orientation and the distribution of growth within the root tip became the same as that prior to gravistimulation. The period of transient backward curvature coincided with and was evidently caused by enhancement of growth along the concave and inhibition of growth along the convex side of the curve, a pattern opposite to that prevailing in the earlier stages of downward curvature. There were periods during the gravitropic response when the normally unimodal growth-rate distribution within the elongation zone became bimodal with two peaks of rapid elongation separated by a region of reduced elongation rate. This occurred at different times on the convex and concave sides of the graviresponding root. During the period of steady downward curvature the elongation zone along the convex side extended farther toward the tip than in the vertical control. During the period of reduced rate of curvature, the zone of elongation extended farther toward the tip along the concave side of the root. The data show that the gravitropic response pattern varies with time and involves changes in localized elongation rates as well as changes in the length and position of the elongation zone. Models of root gravitropic curvature based on simple unimodal inhibition of growth along the lower side cannot account for these complex growth patterns.

NASA Discipline Plant Biology↗

DOE OSTI2026

Adsorption of hydroxamic acid ligands for improved extraction of rare earth elements from monazite ores

Efficient separation of rare earth element (REE) ores via froth flotation requires the development of novel ligands with enhanced adsorption capacity and selectivity. To realize these advances, understanding the mechanisms underlying interactions between the ligand and mineral surfaces is essential. This study systematically evaluates the adsorption behavior of alkyl- and aromatic alkyl-substituted hydroxamic acid ligands on monazite surfaces using complementary spectroscopic techniques, including UV–visible (UV–vis) spectroscopy, Raman spectroscopy, infrared spectroscopy, and vibrational sum frequency generation (SFG) spectroscopy, together with the ab initio molecular dynamics (AIMD) simulations. Among the studied ligands, octanohydroxamic acid (OHA) and 4-ethoxy-N,2-dihydroxybenzamide (EDHBA) exhibit high adsorption capacity under basic pH (8–10) by forming multilayers on the surface. OHA has a higher equilibrium adsorption capacity compared to EDHBA, but it forms a less stable multilayer susceptible to disruption in the presence of interfering ions. AIMD results show that OHA adopts a single stable chelating geometry, while EDHBA exhibits multiple binding modes involving distinct interactions with La surface atoms and phosphate-bound oxygens, resulting in more complex adsorption kinetics. The variations in surface binding and intermolecular interactions observed between alkyl and aromatic molecules influence the differences in adsorption kinetics, equilibrium adsorption capacities on the mineral surface, and their flotation performance. This work provides valuable insight into the adsorption mechanism of ligands at mineral interfaces, which is crucial for guiding the design of new ligands with enhanced separation performance.

Zhou, Muchu [ORNL] (ORCID:0000000182650215)↗

DOE OSTI2022

Environmental effects on aerosol–cloud interaction in non-precipitating marine boundary layer (MBL) clouds over the eastern North Atlantic

Abstract. Over the eastern North Atlantic (ENA) ocean, a total of 20 non-precipitating single-layer marine boundary layer (MBL) stratus and stratocumulus cloud cases are selected to investigate the impacts of the environmental variables on the aerosol–cloud interaction (ACIr) using the ground-based measurements from the Department of Energy Atmospheric Radiation Measurement (ARM) facility at the ENA site during 2016–2018. The ACIr represents the relative change in cloud droplet effective radius re with respect to the relative change in cloud condensation nuclei (CCN) number concentration at 0.2 % supersaturation (NCCN,0.2 %) in the stratified water vapor environment. The ACIr values vary from −0.01 to 0.22 with increasing sub-cloud boundary layer precipitable water vapor (PWVBL) conditions, indicating that re is more sensitive to the CCN loading under sufficient water vapor supply, owing to the combined effect of enhanced condensational growth and coalescence processes associated with higher Nc and PWVBL. The principal component analysis shows that the most pronounced pattern during the selected cases is the co-variations in the MBL conditions characterized by the vertical component of turbulence kinetic energy (TKEw), the decoupling index (Di), and PWVBL. The environmental effects on ACIr emerge after the data are stratified into different TKEw regimes. The ACIr values, under both lower and higher PWVBL conditions, more than double from the low-TKEw to high-TKEw regime. This can be explained by the fact that stronger boundary layer turbulence maintains a well-mixed MBL, strengthening the connection between cloud microphysical properties and the below-cloud CCN and moisture sources. With sufficient water vapor and low CCN loading, the active coalescence process broadens the cloud droplet size spectra and consequently results in an enlargement of re. The enhanced activation of CCN and the cloud droplet condensational growth induced by the higher below-cloud CCN loading can effectively decrease re, which jointly presents as the increased ACIr. This study examines the importance of environmental effects on the ACIr assessments and provides observational constraints to future model evaluations of aerosol–cloud interactions.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Optimized In Situ Doping Strategy Stabling Single-Crystal Ultrahigh-Nickel Layered Cathode Materials

Single-crystal Ni-rich cathodes offer promising prospects in mitigating intergranular microcracks and side reaction issues commonly encountered in conventional polycrystalline cathodes. However, the utilization of micrometer-sized single-crystal particles has raised concerns about sluggish Li + diffusion kinetics and unfavorable structural degradation, particularly in high Ni content cathodes. Herein, we present an innovative in situ doping strategy to regulate the dominant growth of characteristic planes in the singlecrystal precursor, leading to enhanced mechanical properties and effectively tackling the challenges posed by ultrahigh-nickel layered cathodes. Compared with the traditional dry-doping method, our in situ doping approach possesses a more homogeneous and consistent modifying effect from the inside out, ensuring the uniform distribution of doping ions with large radius (Nb, Zr, W, etc). Further, this mitigates the generally unsatisfactory substitution effect, thereby minimizing undesirable coating layers induced by different solubilities during the calcination process. Additionally, the uniformly dispersed ions from this in situ doping are beneficial for alleviating the two-phase coexistence of H2/H3 and optimizing the Li + concentration gradient during cycling, thus inhibiting the formation of intragranular cracks and interfacial deterioration. Consequently, the in situ doped cathodes demonstrate exceptional cycle retention and rate performance under various harsh testing conditions. Our optimized in situ doping strategy not only expands the application prospects of elemental doping but also offers a promising research direction for developing high-energy-density single-crystal cathodes with extended lifetime.

25 ENERGY STORAGE↗

DOE OSTI2021

Diastereomers and Low-Temperature Oxidation

Diastereomers have historically been ignored when building kinetic mechanisms for combustion. Low-temperature oxidation kinetics, which continues to gain interest in both combustion and atmospheric communities, may be affected by the inclusion of diastereomers in radical chain-branching pathways. In this work, key intermediates and transition states lacking stereochemical specification in an existing diethyl ether low-temperature oxidation mechanism were replaced with their diastereomeric counterparts. Rate coefficients for reactions involving diastereomers were computed with ab initio transition state theory master equation calculations. The presence of diastereomers increased rate coefficients by factors of 1.2-1.6 across various temperatures and pressures. Ignition delay simulations incorporating these revised rate coefficients indicate that the diastereomers enhanced the overall reactivity of the mechanism by almost 15% and increased the peak ketohydroperoxide concentration by 30% in the negative temperature coefficient region at combustion-relevant pressures. Furthermore, these results provide an illustrative indication of the important role of stereomeric effects in oxidation kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Crystallographic Insight of Reduced Lattice Volume Expansion in Mesoporous Cu 2+ -Doped TiNb 2 O 7 Microspheres during Li + Insertion

TiNb 2 O 7 represents a promising anode material for lithium-ion batteries (LIBs), but its practical applications are currently hampered by the non-negligible volumetric expansion and contraction during the charge/discharge process and the sluggish ion/electron kinetics. Here a combination technique is reported by systematically optimizing the porous and spherical morphology, crystal structure, and surface decoration of mesoporous Cu 2+ -doped TiNb 2 O 7 microspheres to enhance the electrochemical Li + storage performance and stability simultaneously. The Cu 2+ dopants preferentially replace Ti 4+ in crystal lattices, which decreases the Li + diffusion barrier and increases the electronic conductivity, as confirmed by density functional theory (DFT) calculation and demonstrated by diverse electrochemical characterizations. The successful Cu 2+ doping significantly reduces the lattice expansion coefficient from 7.26% to 4.61% after Li + insertion along the b-axis of TiNb 2 O 7 , as visualized from in situ and ex situ XRD analysis. The optimal 5% Cu 2+ -doped TiNb 2 O 7 with surface coating of N-doped carbon exhibits significantly enhanced specific capacity and rate and cyclic performances in both half- and full-cell configurations, demonstrating an excellent electrochemical behavior for fast-charging LIB applications.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Pore Aperture Control Toward Size‐Exclusion‐Based Hydrocarbon Separations

Abstract Metal–organic frameworks (MOFs) have been proposed as a promising material for non‐thermal chemical separations owing to their high structural diversity and tunability. Here, we report the synthesis of a zinc‐based MOF containing a three‐dimensional (3D) linker, bicyclo[2.2.2]octane‐1,4‐dicarboxylic acid, with high thermal stability towards the separation of hexane isomers. The incorporation of the 3D linker enhances the structural stability and provides well‐defined pore apertures/channels with sub‐Ångstrom precision. This precision allowed for the separation of similarly sized hexane isomers based on subtle differences in their kinetic diameters. Multi‐component liquid phase batch experiments confirmed the separation of hexanes mixture into linear, monobranched, and dibranched isomers. This work represents a significant milestone in the construction of stable Zn‐based MOFs and the incorporation of 3D linkers as a potential solution to challenging separations.

Lal, Bhajan↗

DOE OSTI2024

Coupled Transport, Reactivity, and Mechanics in Fractured Shale Caprocks

Abstract Shales are low‐permeability caprocks that confine fluid, such as CO 2 , nuclear waste, and hydrogen, in storage formations. Stress‐induced fractures in shale caprocks provide pathways for fluid to leak and potentially contaminate fresh water aquifers. Fractured shales are also increasingly considered as resources for CO 2 sequestration, enhanced geothermal, and unconventional energy recovery. Injecting reactive fluids into shales introduces chemical disequilibrium, causing an onset of a series of dissolution, precipitation, and fines mobilization mechanisms. The reactions have rapid kinetics and significant impact on porosity and permeability; consequently, flow and storage properties of caprocks. While previous research has explored the separate effects of these reactions, this study aims to uncover their simultaneous occurrence and collective influence. This study unveils these highly coupled transport and reactivity mechanisms by tracking and visualizing the reaction‐induced alterations in the matrix, microcracks, and fractures of shales over time. We conducted brine injection experiments sequentially at pH 4 and 2 in a naturally fractured Wolfcamp shale sample while simultaneously imaging the dynamic processes using X‐ray computed tomography (CT). CT images are validated by finer resolution images obtained using micro‐CT and scanning electron microscopy. We also tracked the sample permeability and fluid chemistry using brine permeability and inductively coupled plasma mass spectrometry, respectively. Findings show that fluid primarily flowed through fractures, dissolving reactive minerals and mobilizing fines on fracture surfaces. Dissolution of fracture asperities under confining stress resulted in the closing of fractures. Clogging in narrow fracture pathways, caused by fines accumulation, diverted fluid flow into matrix pores.

58 GEOSCIENCES↗

DOE OSTI2022

Exploring extreme magnetization phenomena in directly driven imploding cylindrical targets

Abstract This paper uses extended-magnetohydrodynamics (MHD) simulations to explore an extreme magnetized plasma regime realizable by cylindrical implosions on the OMEGA laser facility. This regime is characterized by highly compressed magnetic fields (greater than 10 kT across the fuel), which contain a significant proportion of the implosion energy and induce large electrical currents in the plasma. Parameters governing the different magnetization processes such as Ohmic dissipation and suppression of instabilities by magnetic tension are presented, allowing for optimization of experiments to study specific phenomena. For instance, a dopant added to the target gas-fill can enhance magnetic flux compression while enabling spectroscopic diagnosis of the imploding core. In particular, the use of Ar K-shell spectroscopy is investigated by performing detailed non-LTE atomic kinetics and radiative transfer calculations on the MHD data. Direct measurement of the core electron density and temperature would be possible, allowing for both the impact of magnetization on the final temperature and thermal pressure to be obtained. By assuming the magnetic field is frozen into the plasma motion, which is shown to be a good approximation for highly magnetized implosions, spectroscopic diagnosis could be used to estimate which magnetization processes are ruling the implosion dynamics; for example, a relation is given for inferring whether thermally driven or current-driven transport is dominating.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2023

Development and evaluation of a skeletal mechanism for EHN additized gasoline mixtures in large Eddy simulations of HCCI combustion

Advanced Low Temperature Combustion modes, such as the Sandia proposed Additive-Mixing Fuel Injection (AMFI), can unlock significant potential to boost fuel conversion efficiency and ultimately improve the energy conversion of internal combustion engines. This is a novel improved combustion process that is enabled by supplying small (<5%) variable amounts of autoignition improver to the fuel to enhance the engine operation and control. Common, diesel-fuel ignition-quality enhancing additive, 2-ethylexyl nitrate (EHN), is doped into gasoline to enable Sandia LTGC + AMFI combustion. This manuscript focuses on the development of a reduced sub-mechanism for EHN chemical kinetics at engine relevant conditions that is implemented into a skeletal mechanism for chemical kinetic studies of gasoline surrogate fuels. The mechanism validation utilized zero-dimensional numerical simulations and comparison to shock tube ignition-delay data of pure and EHN-doped n-heptane. Additional validation is presented with Homogeneous Charge Compression-Ignition (HCCI) engine data of pure and EHN-doped research-grade E10 gasoline. Then, the mechanism was deployed in a 3-D computational fluid dynamics (CFD) using Large Eddy Simulations (LES) to model the HCCI engine experiments of 0.4% vol EHN additized E10 gasoline at several equivalence ratios. Simulations showed a very good performance of the mechanism, and the model accurately reproduced (a) the ignition point, (b) combustion phasing, (c) combustion duration, and (d) the peak of the heat release rates of the engine experiments. The results show that EHN promotes Low-Temperature Heat Release, ultimately driving the gasoline to autoignite at thermodynamic conditions where the fuel would not otherwise ignite. Overall, this work demonstrates a viable reduced chemical-kinetic mechanism for EHN and shows that it can be combined with a skeletal gasoline mechanism for CFD-LES analysis of well-mixed LTGC that matches well with experimental results. The CFD-LES analysis also shows the spatial distribution of EHN-fuel interactions that control the autoignition throughout the combustion chamber.

Guleria, Gaurav↗

DOE OSTI2025

Rapid Oxidation of Uranium Steel Alloys: Combustion Synthesis

This project explored the use of combustion synthesis as a rapid, high-temperature method for oxidizing uranium-bearing steel alloys. Traditional laboratory-scale synthesis methods often fail to replicate the thermal and kinetic conditions experienced by real-world particulates, particularly those formed under rapid quenching or high-temperature scenarios. Combustion synthesis offers a promising alternative by enabling fast, localized heating and flexible precursor selection. A series of targeted experiments were conducted using a U 2 NiCrFe 4 alloy as the precursor. The alloy was oxidized using combustion synthesis reactions fueled by uranyl nitrate and glycine, achieving peak temperatures exceeding 1,200 °C. Postreaction analysis using scanning electron microscopy (SEM), elemental mapping, and Raman spectroscopy revealed the formation of iron-based oxides, with limited but detectable evidence of uranium oxide phases such as UO 2 . The results indicate that under the rapid reaction and cooling conditions of combustion synthesis, iron oxides form preferentially, but uranium oxide formation is kinetically limited. These findings validate combustion synthesis as a viable method for simulating the oxidation behavior of uranium steels in extreme environments and lay the groundwork for future studies aimed at enhancing uranium oxide formation through higher temperatures or modified precursor compositions.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Niche Differentiation of Bacterial Versus Archaeal Soil Nitrifiers Induced by Ammonium Inhibition Along a Management Gradient

Soil nitrification, mediated mainly by ammonia oxidizing archaea (AOA) and bacteria (AOB), converts ammonium (NH 4 + ) to nitrite (NO 2 – ) and thence nitrate (NO 3 – ). To better understand ecological differences between AOA and AOB, we investigated the nitrification kinetics of AOA and AOB under eight replicated cropped and unmanaged ecosystems (including two fertilized natural systems) along a long-term management intensity gradient in the upper U.S. Midwest. For five of eight ecosystems, AOB but not AOA exhibited Haldane kinetics (inhibited by high NH 4 + additions), especially in perennial and successional systems. In contrast, AOA predominantly exhibited Michaelis-Menten kinetics, suggesting greater resistance to high nitrogen inputs than AOB. These responses suggest the potential for NH 4 + -induced niche differentiation between AOA and AOB. Additionally, long-term fertilization significantly enhanced maximum nitrification rates (V max ) in the early successional systems for both AOA and AOB, but not in the deciduous forest systems. This was likely due to pH suppression of nitrification in the acidic forest soils, corroborated by a positive correlation of V max with soil pH but not with amoA gene abundance. Results also demonstrated that soil nitrification potentials were relatively stable, as there were no seasonal differences. Overall, results suggest that (1) NH 4 + inhibition of AOB but not AOA could be another factor contributing to niche differentiation between AOA and AOB in soil, and (2) nitrification by both AOA and AOB can be significantly promoted by long-term nitrogen inputs.

59 BASIC BIOLOGICAL SCIENCES↗