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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

The acidity of atmospheric particles and clouds

Acidity, defined as pH, is a central component of aqueous chemistry. In the atmosphere, the acidity of condensed phases (aerosol particles, cloud water, and fog droplets) governs the phase partitioning of semivolatile gases such as HNO 3 , NH 3 , HCl, and organic acids and bases as well as chemical reaction rates. It has implications for the atmospheric lifetime of pollutants, deposition, and human health. Despite its fundamental role in atmospheric processes, only recently has this field seen a growth in the number of studies on particle acidity. Even with this growth, many fine-particle pH estimates must be based on thermodynamic model calculations since no operational techniques exist for direct measurements. Current information indicates acidic fine particles are ubiquitous, but observationally constrained pH estimates are limited in spatial and temporal coverage. Clouds and fogs are also generally acidic, but to a lesser degree than particles, and have a range of pH that is quite sensitive to anthropogenic emissions of sulfur and nitrogen oxides, as well as ambient ammonia. Historical measurements indicate that cloud and fog droplet pH has changed in recent decades in response to controls on anthropogenic emissions, while the limited trend data for aerosol particles indicate acidity may be relatively constant due to the semivolatile nature of the key acids and bases and buffering in particles. This paper reviews and synthesizes the current state of knowledge on the acidity of atmospheric condensed phases, specifically particles and cloud droplets. It includes recommendations for estimating acidity and pH, standard nomenclature, a synthesis of current pH estimates based on observations, and new model calculations on the local and global scale.

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

Simulating combustion of a seven-component surrogate for a gasoline/ethanol blend including soot formation and comparison with experiments

Combustion of a seven-component surrogate for a research grade 87 octane gasoline mixed with 10% ethanol is investigated experimentally and numerically from the perspective of an isolated droplet burning under conditions that promote one-dimensional gas transport. The numerical analysis included a kinetic mechanism comprised of 398 species and 24,814 reactions and a soot model that accounted for nucleation, surface growth, coalescence/aggregation of soot particles, and luminous flame radiation. Measurements of droplet and flame diameters were made for an initial droplet diameter (D o ) of approximately 0.63 mm. The simulations agreed well with the measurements including the location of the soot shell. Preferential vaporization was revealed by simulations of the liquid concentrations in the droplet. Predicted peak soot volume fractions coincided with temperatures between 1300 K and 1400 K as a soot inception temperature. Simulations were also carried out for D o between 0.25 mm and 5 mm to explore the effect of radiation and D o on burning. Below 0.25 mm radiation was negligible and burning rates and flame temperatures converged to a single value. Increasing D o up to 1.8 mm lowered the burning rate with luminous radiation having a strong effect. When radiation was entirely removed from the model the burning rate was nearly constant. Above D o = 2 mm droplets extinguished almost immediately after ignition. The flame temperature decreased with increasing D o while it increased when radiation was omitted. As a result, the simulations show that soot precursors including polyaromatic hydrocarbons were concentrated around the soot shell.

42 ENGINEERING↗
DOE OSTI2020

Crystal Structure and C–H Bond-Cleaving Reactivity of a Mononuclear Co IV –Dinitrate Complex

High-valent Fe IV =O intermediates with a terminal metal–oxo moiety are key oxidants in many enzymatic and synthetic C–H bond oxidation reactions. While generating stable metal–oxo species for late transition metals remains synthetically challenging, notably, a number of high-valent non-oxo–metal species of late transition metals have been recently described as strong oxidants that activate C–H bonds. In this work, we obtained an unprecedented mononuclear Co IV –dinitrate complex (2) upon one-electron oxidation of its Co(III) precursor supported by a tridentate dianionic N3 ligand. 2 was structurally characterized by X-ray crystallography, showing a square pyramidal geometry with two coordinated nitrate anions. Furthermore, characterization of 2 using combined spectroscopic and computational methods revealed that 2 is a low-spin (S = 1/2) Co(IV) species with the unpaired electron located on the cobalt d z2 orbital, which is well positioned for substrate oxidations. Indeed, while having a high thermal stability, 2 is able to cleave sp 3 C–H bonds up to 87 kcal/mol to afford rate constants and kinetic isotope effects (KIEs) of 2–6 that are comparable to other high-valent metal oxidants. The ability to oxidize strong C–H bonds has yet to be observed for Co IV –O and Co III =O species previously reported. Therefore, 2 represents the first high-valent Co(IV) species that is both structurally characterized by X-ray crystallography and capable of activating strong C–H bonds.

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

Calculation Of The First Moment Of Energy Using D-T Reactivity Formalisms Under The Maxwell-Boltzmann Distribution--Part II

Nuclear fusion science is an example of a scientific field with a rich history of expert involvement and scientific publications, which together, form an expert-knowledge base. One example of a nuclear fusion formalism is the utilization of published reaction rates from a variety of authors. Investigators for Deuterium- Tritium (D-T) ion fusion can choose from using frequently cited methods: the Bosch and Hal reactivity, thermonuclear reaction rates from Caughlan and Fowler, and the reactivity evaluation from Miley, Towner & Ivich which forms the basis of the Naval Research Lab (NRL) formulary. There are other choices available. Each of the reactivity formulations considered here, are based upon the Maxwell-Boltzmann velocity distribution for D-T fusion ion reactants. Numerical methods for computer codes simulating hot, energetic plasmas, include tabulations of the reactivity, and the first moment of energy. This report continues the step toward building understanding of nuclear fusion reactivity formalisms. It is part of a series of reports with the same goal, [5-10] and is the continuation of the Part I paper for defining the mathematical relationship of the first moment of D-T fusion ion kinetic energy, <$E$>, with the fusion cross-section, fusion reactivity and its derivative with ion-temperature. In Part I, three variants of the first moment <$E$> were analytically developed and explored: 1) constant cross-section, 2) a normalized first moment, and 3) a particular function of the first moment from Brysk. In Part II, attention is given to the definition of <$K$>, originally described as a ratio of moments from Brysk, and its relationship to the first moment definitions from Part I. One measure of the progress made in these documents is the identification that Brysk’s ratio of the second moment to the first moment ratio, <$K$>, does not correspond to his provided solution of the first moment of energy. Another measure of (our) progress from this work is the comparison of first moment variants. That comparison includes confirming the importance of cross sections defined in terms of energy. The analytical relationships we have developed among important physics quantities are useful tools in validation and verification (V&V). For example, we can calculate the kinetic energy as a mean or as a first moment, or as a function of the first moment. These analytically-determined values can be compared directly with numerically-determined values, supplied to the authors, representing <$E$>.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Influence of alkali-silica reaction on the shear capacity of reinforced concrete beams with minimum transverse reinforcement

A growing number of critical concrete infrastructure are affected by alkali-silica reaction (ASR) damage such as the Seabrook Nuclear Power Plant in New Hampshire, Parker arch-gravity dam in Arizona, and several highway bridges in California and Texas. ASR causes expansion and cracking and degrades the concrete mechanical properties. Despite a wealth of material level studies there is still limited large-scale experimental data regarding the effects of ASR on reinforced concrete (RC) members. Due to the brittle nature of the shear failure in RC structures, this study focuses on the shear response of full-scale ASR damaged RC beams with minimum shear reinforcement. Six RC beams were built with different levels of ASR susceptibility and conditioned in different environments during which continuous expansion monitoring was performed. The beams all contained reactive fine aggregate (sand) and two of them had additional alkali, 1.25% by weight of cement, to accelerate ASR. The highest expansion rate of the beams happened during the first 150 days and the expansions stayed constant after 240 days and 330 days for beams conditioned in outdoor and laboratory conditions, respectively, until the last measurement at 575 days. The highest expansion, 0.4%, was seen in the beams with additional alkali and conditioned outside with regular water spray. Out of the six beams, three were selected at different levels of ASR damage and two shear tests were performed on the minimally reinforced spans close to the ends of each beam. Results indicated that beams gain shear strength from ongoing cement hydration in the presence of moisture for ASR expansions less than 0.2%. Compared to one of the beams with 0.2% ASR expansion, one of the other samples with 0.4% expansion lost 6% of its shear strength, 25% of its shear stiffness, and showed about two times larger shear cracks and shear deformations at peak load. Finally, the shear reinforcement yielded at 20% less load in the beam with 0.4% expansion compared to the beam with 0.2% expansion.

42 ENGINEERING↗
DOE OSTI2023

Mathematical Framework Underlying the In Situ Electrochemical Diagnosis of Adsorbed Intermediates Formed during Redox Reactions at Electrode Surfaces

Previously, we have presented an electrochemical technique wherein an electroactive tracer species is employed to probe the rate-limiting factors governing redox reactions at an electrode surface. In this technique, the electrode is first held potentiostatically to facilitate a redox process (step 1), and then the potential is released to open circuit conditions (step 2) so as to monitor the time-dependent re-equilibration of the electrode potential in the presence of the tracer. The time-dependent potential response in step 2 has been shown to contain information about diffusion—limited or desorption—limited steps, enabling in situ probing of the electrochemistry at the electrode surface during step 1. In the present contribution, a theoretical model governing the transient response in step 2 is developed for two limiting cases: diffusion—limited and desorption—limited recovery of the electrode potential. Mathematical modeling shows that, during re-equilibration, the step 2 potential transient corresponding to a case where step 1 involves surface adsorbed species which undergo desorption in step 2 exhibits a much longer time constant than that when re-equilibration occurs under diffusion limitations. The mathematical framework presented herein provides a sound fundamental basis for applying the aforementioned technique to studying adsorption-desorption processes during electrochemistry. Also, technique limitations are presented in light of the modeling findings.

25 ENERGY STORAGE↗
DOE OSTI2023

Time dependent chlorination of CeO 2 , La 2 O 3 and Nd 2 O 3 by ZrCl 4 dissolved in eutectic LiCl–KCl

Partial chlorination of CeO 2 , La 2 O 3 , and Nd 2 O 3 was achieved using ZrCl 4 dissolved in molten LiCl-KCl at 450°C over a period of 4-5 hr. ZrCl 4 was pre-volatilized into an argon stream to maintain a constant vapor pressure for equilibration with the salt. This approach was effective at maintaining the ZrCl 4 concentration at the solubility limit of 1.3 mol% in the molten salt throughout the duration of two of the chlorination experiments and within about 60% of the solubility limit in the third experiment. Based on the analysis of salt samples, fractional conversion after four hours of reaction for CeO 2 , and five hours for La 2 O 3 , and Nd 2 O 3 were calculated to be 0.97, 0.28, and 0.65 respectively. Assuming a shrinking core diffusion-limited model, the diffusivity of ZrCl 4 through the hypothesized ZrO 2 layer was calculated for the chlorination of CeO 2 , La 2 O 3 , and Nd 2 O 3 were 1.76 x 10 -10 cm 2 /sec, 7.85 x 10 -12 cm 2 /sec, and 7.42 x 10 -12 cm 2 /sec, respectively. Given the extremely low values calculated for diffusivity, it was concluded that the process is chemical reaction rate limited and that a complete reaction of each rare earth oxide could be achieved. Furthermore, a chemically controlled shrinking core model was shown to also fit the experimental data closely.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Single-Well Push–Pull Tracer Test Analyses to Determine Aquifer Reactive Transport Parameters at a Former Uranium Mill Site (Grand Junction, Colorado)

At a former uranium mill site where tailings have been removed, prior work has determined several potential ongoing secondary uranium sources. These include locations with uranium sorbed to organic carbon, uranium in the unsaturated zone, and uranium associated with the presence of gypsum. To better understand uranium mobility controls at the site, four single-well push–pull tests (with a drift phase) were completed with the goal of deriving aquifer flow and contaminant transport parameters for inclusion in a future sitewide reactive transport model. This goes beyond the traditional use of a constant sorption distribution coefficient (K d ) and allows for the evaluation of alternative remedial injection fluids, which can produce variable K d values. Dispersion was first removed from the resulting data to determine possible reactions before conducting reactive transport simulations. These initial analyses indicated the potential need to include cation exchange, uranium sorption, and gypsum dissolution. A reactive transport model using multiple layers to account for partially penetrating wells was completed using the PHT-USG reactive transport modeling code and calibrated using PEST. The model results quantify the hydraulic conductivity and dispersion parameters using the injected tracer concentrations. Uranium sorption, cation exchange, and gypsum dissolution parameters were quantified by comparing the simulated versus observed geochemistry. All simulations required some cation exchange and calcite equilibrium, and one simulation required gypsum dissolution to improve the model fit for calcium and sulfate. Uranium sorption parameters were not strongly influenced by the other parameter values but were highly influenced by uranium concentrations during the drift phase, with possible kinetic rate limitations. Thus, a future recommendation for such push–pull tests is to collect more geochemical data during the drift phase. The final uranium sorption parameters were within the range of values determined from prior column testing. The flow and transport parameters derived from these single-well push–pull tests will provide initial parameters for any future sitewide reactive transport model.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Calculation of the First Moment of Energy Using D-T Reactivity Formalisms Under the Maxwell-Boltzmann Distribution (Pt. 1)

Nuclear fusion science is an example of a scientific field with a rich history of expert involvement and scientific publications, which together, form an expert-knowledge base. One example of this history is the utilization of published reaction rates from a variety of authors. Investigators for Deuterium-Tritium (D-T) ion fusion can choose from using frequently cited methods: the Bosch and Hale reactivity, thermonuclear reaction rates from Caughlan and Fowler, and the reactivity evaluation from Miley, Towner & Ivich which forms the basis of the Naval Research Lab (NRL) formulary. There are other choices available. Each of the reactivity formulations considered here, are based upon the Maxwell- Boltzmann velocity distribution for D-T fusion ion reactants. Numerical methods for computer codes simulating hot, energetic plasmas, include tabulations of the reactivity, and the first moment of energy. The purpose of this study is to answer the question: what is the first moment of energy, and how has it been formulated? This report is part of a series of reports by the authors on D-T fusion-reaction formalism. The present focus is on defining the mathematical relationship of the first moment of D-T fusion ion kinetic energy, $\langle$E$\rangle$, with the fusion crosssection, fusion reactivity and its derivative with respect to ion-temperature. Three variants of the first moment $\langle$E$\rangle$ are analytically developed and explored: 1) constant cross-section, 2) a normalized first moment, and 3) a particular function of the first moment. Much of the mathematical development is relegated to the Appendices, for a concise presentation of topics and results. A research component of this discussion is our comparison of some of the reactivity and its derivative results between evaluations (1) versus (2) and (3), which the authors have not found in any other publication to date. This investigation is useful for validation, verification (V&V) and uncertainty quantification (UQ) as it compares the work of several authors.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Structure–property relations of binary ferrite melts

Molten ferrite systems are used in the smelting and refining processes in steelmaking, to reduce the loss of metals in slags and to accelerate reaction rates. Here, high-energy x-ray diffraction experiments have been performed on aerodynamically levitated molten spheres of 43BaO–57FeO X and 43SrO–57FeO X at 1873 K using laser beam heating. The composition was varied within the range of x = 1–1.5 by changing the oxygen partial pressure of the levitation gas. The corresponding x-ray pair distribution functions have been interpreted using empirical potential structure refinement (EPSR) modeling. In oxygen-rich melts (x = 1.5), our EPSR models indicate very similar structures for the different alkaline-earth liquids, with both the Ba–O and Sr–O coordination numbers to be ∼8.4 and the total Fe–O coordination numbers ∼5.7. However, our models show that in reducing environments, the Fe 3+ and Fe 2+ ions exhibit very different behaviors in the Ba- and Sr-ferrite liquids. In the Ba-ferrite melt, the Fe 3+ –O coordination number decreases from 5.7 (at x = 1.5) to 5.2 (at x = 1.07), whereas Fe 2+ –O remains constant at ∼5.0 across the same compositional range. In the Sr melts, both the Fe 2+ –O and Fe 3+ –O coordination numbers rise from ∼5.7 (at x = 1.5) to 6.3 (at x = 1.07). All models show the structures to be heterogeneous with intertwined nanometer sized clusters or channels of Ba/Sr–O and Fe–O polyhedra that grow as oxygen content is reduced. Changes in the viscosity and electrical properties are interpreted in terms of the number of bridging and non-bridging oxygens associated with FeO 4 tetrahedra and concentration of charge carriers, respectively.

Benmore, Chris J. [Argonne National Laboratory (AN↗
DOE OSTI2026

Exploring Excited State Proton Transfer Dynamics upon Ultraviolet Excitation

Excited state intramolecular proton transfer (ESIPT) has been investigated in two prototypical systems─salicylaldehyde azine (SAA) and 1,5-dihydroxyanthraquinone (DHAQ)─using transient absorption spectroscopy upon ultraviolet excitation into the less studied higher excited (S n ) manifold. Excitation with sub-30 fs pulses and broadband visible probing has allowed for direct measurement of the ESIPT rate. In conjunction with steady-state measurements and TD-DFT calculations, a complete delineation of the ultrafast photophysics has been carried out. In SAA, ESIPT remains ultrafast (∼30 fs), consistent with previous S 1 excitation studies. Coherent vibrational beats maps reveal significant wavelength dependence, however. Theoretical analysis suggests that the observed modes and their intensities in coherent vibrational spectra are modulated by the nature of the electronically excited state. In DHAQ, the first direct observation of ESIPT presents a time-constant of ∼85 fs, and a slower component of 9 ps, akin to previous reports on double-proton transfer systems. Collectively, the results suggest that while the ultrafast ESIPT rate remains largely invariant vis-à-vis the excitation energy, the product yield, as well as accompanying coherent oscillations, may be substantively altered, owing to the existence of alternative decay pathways.

excited states↗
DOE OSTI2022

Optimizing group structures using hierarchical division

Creating group structures with few groups that give low errors is a difficult problem in reactor analysis. In recent years, automated optimization techniques have been applied to this task. We continue this trend by applying the hierarchical division algorithm to generate optimized group structures that minimize a cost function. At each stage, the algorithm adds a single group boundary to an existing group structure, dividing one group into two to increase the resolution of the group structure. The location of the added boundary is the one that gives the lowest error over all possible new boundary locations. Our implementation requires a beginning group structure, a set of candidate new boundary locations, and a set of reference reaction rates. As a proof of concept, we used WIMS-69 as the initial group structure, XMAS-172 as the ending group structures, and a 344-group reference group structure. Testing on two simple, homogenized reactor problems, we found that hierarchical division was able to reduce the error by a factor of around 5 with an increase of only 15% in the number of groups. Because hierarchical division can get stuck in local minima, it often reaches a plateau in its error reduction capability as many groups are added. Nevertheless, we find hierarchical division has strong potential to make good group structures into great group structures at a modest increase in computational cost. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Photoactivation Transition State and Dynamical Response of the Orange Carotenoid Protein

The orange carotenoid protein (OCP) regulates light harvesting in cyanobacteria by acting as a photoreceptor in its resting form, OCP O , and by effecting the quenching of bilin excitons upon binding to the core of the phycobilisome in its photoactivated red form, OCP R . We show herein using fluorescence anisotropy measurements and the action spectra for the rate constants of the two light-driven steps in the mechanism that the photoactivation of the OCP from Synechocystis sp. PCC 6803 is triggered by excited-state motions of the canthaxanthin chromophore that yield a twisted and bent conformation. Well-tempered metadynamics simulations reveal that a bicycle-pedal configuration, due to twisting of the two adjacent C=C bonds at the C13−C14 and C15−C15′ positions in the center of canthaxanthin’s π-conjugated isoprenoid backbone, can be accommodated by the binding site in the OCP, with the energy of a captured photon required to cross the local activation energy barriers from the dark equilibrium structure. The bicycle-pedal configuration breaks the conserved hydrogen-bonding interactions between the carbonyl substituent of the β-ionone end ring of canthaxanthin and the adjacent W288 and Y201 residues in the C-terminal domain. The action spectra are modulated by the vibronic excitation prepared by absorption transitions to the S 2 state, indicating that the photoactivation reactions are triggered by the canthaxanthin chromophore well prior to vibrational equilibration. These findings show that an ultrafast structural response of the OCP protein to the excited-state motions of the canthaxanthin chromophore controls the photoactivation yield and the sensing of blue light.

Fluorescence↗
DOE OSTI2025

Numerical Investigation of Ammonia/n-Heptane Dual-Fuel Spray Flames Using Large Eddy Simulations

Diesel engines are extensively used in heavy-duty transportation, power generation, and marine vehicles due to their superior thermal efficiency and extended high-load operability compared to spark ignition (SI) engines. However, combustion in diesel engines is generally characterized by locally rich fuel–air mixtures and high combustion temperatures, causing significant amounts of soot and NO x emissions from these engines. Utilizing carbon-free alternative fuels and enhancing fuel efficiency represent promising strategies to mitigate greenhouse gas (GHG) and other emissions in the heavy-duty transportation sector. In this context, ammonia (NH 3 ), as a hydrogen carrier, has received significant attention as a viable substitute for hydrocarbon fuels due to its carbon-free composition, relatively high energy density, and well-established infrastructure. Many previous studies have considered combustion and emission characteristics of ammonia-hydrocarbon fuel blends in engines and simplified flames. But, detailed investigations on the effects of ammonia on the performance of hydrocarbon fuels under engine conditions are lacking. In the present study, we perform large eddy simulations (LES) of the ignition and flame processes in a constant-volume combustion reactor, where n-heptane is injected in an ammonia/air ambient mixture in a diesel-like environment. A detailed and validated reaction mechanism containing 302 species and 1981 reactions is employed. The Engine Combustion Network Spray H experimental data is used to validate the spray model under both non-reacting and reacting conditions. Dual-fuel combustion is simulated using the well-stirred reactor (WSR) approach. Results are presented for two spray cases: (1) single fuel (SF) with n-heptane injected into a mixture of air and combustion products and (2) dual-fuel (DF) with the injection of n-heptane in a mixture of air, ammonia, and combustion products. It is observed that the presence of ammonia has a significant effect on the ignition and flame development processes. With ammonia addition, both the first- and second-stage ignition delay times increase, but the effect of ammonia on the second-stage ignition is significantly more prominent. In addition, the ignition kernel size and growth rate decrease noticeably. For SF spray, the main ignition is characterized by multiple ignition kernels near the spray tip, whereas for DF spray, a single relatively small ignition kernel forms and grows slowly in the downstream direction. The flame development and the final quasi-steady flame structure are also modified due to ammonia. Here, the outcome of this research would enable a better understanding of ammonia–diesel dual-fuel spray flame behavior and guide the development of associated engine combustion strategies.

ammonia↗
DOE OSTI2020

ZND Verification Tests for Reactive Burn Models in FLAG

The ZND theory, named after Zeldovich, von Neumann, and Doering, provides a simple model for one-dimensional ideal steady-state detonation. It assumes that the detonation wave front starts with a shock that is a discontinuous jump and is followed by a finite-length reaction zone. Reactive burn (also called reactive flow) models are based on ZND theory, as they model the shock initiation and detonation process with a finite reaction rate. The ZND wave propagation test is essentially the only available test case where an analytic solution exists for verification of reactive burn models in numerical codes. However, there are extensions and variants of the ZND test that have been devised for verification of multidimensional flows. The objective of this work is to provide verification of the reactive burn models currently implemented in the Lagrangian hydrocode FLAG and investigate the influence of mesh resolution, artificial viscosity models, and the Arbitrary Lagrangian-Eulerian (ALE) Euler relaxer on the simulation results. The burn models of interest are the Wescott-Stewart-Davis (WSD) model, the Scaled Uniform Reactive Flow (SURF) model (specifically with the SURFplus model extension), and the Arrhenius shock temperature state dependent WSD (AWSD) model. Previously, Ralph Menikoff has used ZND tests for verification of the SURF and SURFplus models in the Eulerian hydrocode xRAGE. The ZND tests here are somewhat different than the approach by Menikoff. In particular, we use a piston-driven ZND detonation wave (via a prescribed constant velocity boundary condition) in a Lagrangian framework whereas Menikoff had a ZND wave followed by a invariant rarefaction wave. The xRAGE simulations were carried out on uniform grids and adaptive mesh refinement (AMR) grids. Although AMR was recently implemented in FLAG and now fully functional for 2D simulations, it will not be evaluated with ZND tests at this time. Some work has been done previously for validating the reactive burn models in FLAG. For example, the validation studies of SURF with shock-to-detonation (SDT) tests, cylinder tests, and gap-stick tests. Further validation of the AWSD, WSD, and SURF models is described in for SDT, multi-shock, cylinder, and corner-turning tests. Recently, a large parameter study with approximately twenty SDT tests was performed to validate the AWSD, WSD, SURF, and SURFplus models while also investigating mesh resolution and artificial viscosity settings. To the best of our knowledge, the current work represents the first documented verification of these burn models in FLAG. The reader should note that many of the tables and figures in this report use units of cm/g/µs, which are the default units for FLAG. However, some lengths and velocities are expressed in µm and mm/µs, respectively, which are typical units for detonation analyses.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2023

Lewis Acids and Electron-Withdrawing Ligands Accelerate CO Coordination to Dinuclear Cu I Compounds

A series of dinuclear molecular copper complexes were prepared and used to model the binding and Lewis acid stabilization of CO in heterogeneous copper CO 2 reduction electrocatalysts. Experimental studies (including measurement of rate and equilibrium constants) and electronic structure calculations suggest that the key kinetic barrier for CO binding may be a σ-interaction between CuI and the incoming CO ligand. The rate of CO coordination can be increased upon the addition of Lewis acids or electron-withdrawing substituents on the ligand backbone. Conversely, K eq for CO coordination can be increased by adding electron density to the metal centers of the compound, consistent with stronger π-backbonding. Lastly, the electrochemically measured kinetic results were mapped onto an electrochemical zone diagram to illustrate how these system changes enabled access to each zone.

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

Preservation of kinetics parameters generated by Monte Carlo calculations in two-step deterministic calculations

The generation of accurate kinetic parameters such as mean generation time Λ and effective delayed neutron fraction β eff via Monte Carlo codes is established. Employing these in downstream deterministic codes warrants another step to ensure no additional error is introduced by the low-order transport operator when computing forward and adjoint fluxes for bilinear weighting of these parameters. Another complexity stems from applying superhomogenization (SPH) equivalence in non-fundamental mode approximations, where reference and low-order calculations rely on a 3D full core model. In these cases, SPH factors can optionally be computed for only part of the geometry while preserving reaction rates and K-effective, but the impact of such approximations on kinetics parameters has not been thoroughly studied. This paper aims at studying the preservation of bilinearly-weighted quantities in the Serpent–Griffin calculation procedure. Diffusion and transport evaluations of IPEN/MB-01, Godiva, and Flattop were carried out with the Griffin reactor physics code, testing available modeling options using Serpent-generated multigroup cross sections and equivalence data. Verifying Griffin against Serpent indicates sensitivities to multigroup energy grid selection and regional application of SPH equivalence, introducing significant errors; these were demonstrated to be reduced through the use of a transport method together with a finer energy grid.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Performance and Durability of Heavy-Duty Fuel Cell Systems with an Advanced Ordered Intermetallic ORR Alloy Catalyst and Novel Support

Ordered PtCo intermetallic (OIM) catalyst (L1 0 -PtCo/C) is a promising candidate as the oxygen reduction reaction (ORR) catalyst in hybrid fuel cell systems (FCS) for class-8 heavy duty (HD) trucks. Compared to a baseline annealed Pt on high surface area carbon (a-Pt/HSC) catalyst, its mass activity (MA) is 71% higher initially and 144% higher after 90,000 potential cycles in an accelerated stress test (AST). Analysis of the AST data indicates that the ORR kinetic constants do not change with aging and the degradation in the OIM catalyst activity is linearly proportional to the loss in the electrochemically active surface area (ECSA). Several operational strategies are investigated to mitigate catalyst degradation and achieve 25,000-h electrode lifetime and 2.5 kW g −1 Pt utilization on a HD truck duty cycle including load sharing with the hybrid battery, regulating the radiator fan power to maintain the coolant temperature close to 60 °C, clipping the maximum cell voltage below 850 mV, limiting the ECSA loss to 55%, and oversizing the active area of the membrane electrode assemblies by 20%. Drive cycle simulations indicate that the lifetime average voltage degradation rate is about 1.8 μV h −1 and the integrated stack and FCS drive cycle efficiencies decrease by 3.5 to 3.9%.

25 ENERGY STORAGE↗