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At least 307 records · Page 17

Measurements and kinetic modeling of O 2 vibrational kinetics in O 2 –Ar mixtures partially dissociated by a Ns pulse discharge

Vibrational kinetics of O 2 is studied during the O atom recombination in an O 2 –Ar mixture, partially dissociated by a burst of ns discharge pulses in a heated plasma flow reactor. The time-resolved temperature in the discharge afterglow is determined by Rayleigh scattering. Time-resolved O atom number density is measured by ps Two-Photon absorption Laser Induced Fluorescence, calibrated in xenon. Time-resolved vibrational level populations of molecular oxygen, O 2 (v= 8–20), are measured by ps Laser Induced Fluorescence (LIF), with the absolute calibration by NO LIF. Time-resolved ozone number density is monitored by broadband UV absorption. The results are compared with the predictions of a state-specific kinetic model. The experimental data indicate a rapid initial decay of O 2 (v) populations generated by electron impact in the discharge, due to the vibration-translation (V–T) relaxation by O atoms. This is followed by a slower population reduction, on the time scale much longer compared to that for V–T relaxation or vibration-vibration (V–V) exchange. Both O atoms and the O 2 (v) populations decay on the same time scale, indicating that chemical reactions initiated by the O atom recombination result in the generation of vibrationally excited O 2 molecules. These trends are reproduced by the kinetic model, which shows that the reaction of O atoms with ozone is the dominant pathway of O 2 (v) generation at the present conditions. The predicted relative O 2 (v) populations are close to the experimental results, but absolute number densities differ from the experimental data. This is likely due to uncertainties in the absolute calibration of LIF measurements and in the spectroscopic model used in the data reduction. The present work demonstrates the capability for the absolute, time-resolved measurements of vibrationally excited O 2 in recombining gas flows, to quantify the energy partition in the recombination reactions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Water effects on NH 3 -SCR over Cu-based small-pore zeolite catalysts: A review

The selective catalytic reduction (SCR) of NO x with NH 3 as the reductant over small-pore Cu-zeolite catalysts is a leading strategy for controlling emissions from diesel engines and mobile sources. While the hydrothermal stability of Cu-zeolites such as Cu-SSZ-13, Cu-SAPO-34, and Cu-SSZ-39 has been extensively studied, the multifaceted role of water vapor under operating conditions has only recently received systematic attention. Water impacts multiple aspects of SCR catalysis, including NO x conversion, N 2 O formation, Cu ion speciation, redox kinetics, and surface reactions. This review comprehensively summarizes recent advances in understanding the effect of water on NH 3 -SCR over Cu-based catalysts. For Cu-SSZ-13, water vapor induces both inhibitory and promotive effects depending on temperature, Cu loading, and Si/Al ratio by altering NH 3 adsorption, Cu mobility, and redox half-cycle kinetics. Studies have revealed that water can suppress ammonium nitrate formation at low temperatures and enhance nitrate pathways at higher temperatures. Over Cu-SAPO-34, water promotes NO conversion by improving Cu(II) reducibility and strengthening Brønsted acidity. First-principles calculations confirm that water-coordinated Cu species lower O 2 activation barriers. In Cu-SSZ-39, water was found to facilitate Cu reduction, migration, and O 2 activation, resulting in superior water tolerance and unexpected catalytic promotion. Both experimental and computational studies highlight that water vapor exerts complex, catalyst-dependent effects on NH 3 -SCR performance, underscoring the need for tailored catalyst designs that leverage beneficial water interactions while minimizing inhibitory impacts.

Ammonia selective catalytic reduction↗

Flame dynamics and kinetic coupling of ammonia and dimethyl-ether in non-premixed cool and warm flames at elevated pressure

Developing advanced low-temperature combustion engines with ammonia-biofuel blends requires a comprehensive understanding of low-temperature flame dynamics and kinetic interactions between ammonia and oxygenated fuels at elevated pressures. This work aims to study the dynamics and kinetics of non-premixed Dimethyl Ether (DME)/Ammonia (NH 3 ) cool and warm flames, and their reignition to hot flames. A counterflow burner is employed to establish DME/NH 3 cool/warm flames at pressures up to 5 atm. The extinction limits of cool flame and the reignition limits of warm flame to hot flame are measured by varying NH 3 concentrations and compared to simulations to quantitatively examine the effects on DME/NH 3 flames. It is found that NH 3 inhibits low-temperature DME oxidation and results in lower cool flame extinction limits. Warm flames in the presence of NH 3 are observed for the first time, revealing a non-monotonic effect of NH 3 addition: a small amount of NH 3 presence enhances warm flame chemistry and promotes reignition to hot flames, while a high NH 3 concentration weakens the warm flame. This trend is further explained by 0-D PSR kinetic simulations and 1-D S-curve flame dynamic calculations. Three flame transition regimes between cool flames (CF), warm flames (WF), and hot flames (HF) by different levels of NH 3 additions at a specific strain rate are identified, namely WFHF reignition, WF-CF transition, and WF extinction. Reaction sensitivity analyses of OH at low temperatures show that NH3 inhibits DME oxidation through OH consumption via H-abstraction and the kinetic couplings of RO 2 /NH 2 , RO 2 /NO x , R/NO x , and O 2 QOOH/NO x further suppress the low-temperature branching. At intermediate-temperatures, NH 2 /NO x /HO 2 coupling promotes warm flames via the pathway NH 2 → H 2 NO → HNO → NO by converting O 2 → HO 2 → OH. At even higher NH₃ concentrations, radical termination reactions of NH 2 + NO/NO 2 and excessive OH consumption via H-abstraction inhibit the flame. The insights into the kinetic coupling between NH 3 and low-temperature chemistry at elevated pressure and its impact on the dynamics of cool-warm-hot flame transitions will contribute to advancing combustion technologies with reduced emissions and improved energy-efficiency.

42 ENGINEERING↗

Modeling Analysis of Ball-Milling Process for Battery-Electrode Synthesis

The mechanical alloying process is a promising method for synthesizing electrode materials for batteries owing to its benefits such as the ability to produce nanostructured, high-performing electrode alloys, no adverse effects on the solid electrolyte for solid-state batteries, stable production of thick electrodes, simple processing steps, and low processing costs. It is gaining intensive attention in the battery industry as one of the best methods to replace the conventional wet-slurry-solvent method, and its application is rapidly increasing these days. However, the operation is currently conducted purely based on trial-and-error methods without fully utilizing the features of its functions. Here, this may be attributed to a lack of understanding of the effect of operating parameters on the alloying process and final products. Surprisingly, there is a scarcity of the literature conducting fundamental research to comprehend the underlying physics of the entire mechanical alloying process, resulting in a significant knowledge gap. To address this knowledge gap, extensive research was conducted. The existing literature on mechanical alloying was reviewed to comprehend the current state of understanding and to discuss the direction for future research. Mathematical expressions were developed to create physics-based models capable of capturing the entire mechanical alloying process, including milling kinetics and defect-enhanced phase evolution. These methods were then applied to investigate the impact of operating parameters such as milling frequency, initial mole ratio of the alloyed materials, density of grinding balls, and energy required for the powders to become amorphous (i.e., the amorphization energy threshold). This research aimed not only to comprehend the direct effects of these operating parameters but also to unveil the physics underlying the ball-milling process. The results of our study can serve as crucial information for the battery industry in designing or operating the ball-milling process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental study of the edge radial electric field in different drift configurations and its role in the access to H-mode at ASDEX Upgrade

The formation of the equilibrium radial electric field (Er) has been studied experimentally at ASDEX Upgrade (AUG) in L-modes of “favorable” (ion ∇ B-drift toward primary X-point) and “unfavorable” (ion ∇ B-drift away from primary X-point) drift configurations, in view of its impact on H-mode access, which changes with drift configurations. Edge electron and ion kinetic profiles and impurity velocity and mean-field Er profiles across the separatrix are investigated, employing new and improved measurement techniques. The experimental results are compared to local neoclassical theory as well as to a simple 1D scrape-off layer (SOL) model. It is found that in L-modes of matched heating power and plasma density, the upstream SOL Er and the main ion pressure gradient in the plasma edge are the same for either drift configurations, whereas the Er well in the confined plasma is shallower in unfavorable compared to the favorable drift configuration. The contributions of toroidal and poloidal main ion flows to Er, which are inferred from local neoclassical theory and the experiment, cannot account for these observed differences. Furthermore, it is found that in the L-mode, the intrinsic toroidal edge rotation decreases with increasing collisionality and it is co-current in the banana-plateau regime for all different drift configurations at AUG. This gives rise to a possible interaction of parallel Pfirsch–Schlüter flows in the SOL with the confined plasma. Thus, the different H-mode power threshold for the two drift configurations cannot be explained in the same way at AUG as suggested by LaBombard et al. [Phys. Plasmas 12, 056111 (2005)] for Alcator C-Mod. Finally, comparisons of Er profiles in favorable and unfavorable drift configurations at the respective confinement transitions show that also the Er gradients are all different, which indirectly indicates a different type or strength of the characteristic edge turbulence in the two drift configurations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The Transition From Rebound to Bonding in High-Velocity Metallic Microparticle Impacts: Jetting-Associated Power-Law Divergence

A metallic microparticle impacting a metallic substrate with sufficiently high velocity will adhere, assisted by the emergence of jetting—the splash-like extrusion of solid matter at the periphery of the impact. In this work, we compare real-time observations of high-velocity single-microparticle impacts to an elastic–plastic model to develop a more thorough understanding of the transition between the regimes of rebound and bonding. We first extract an effective dynamic yield strength for copper from prior experiments impacting alumina spheres onto copper substrates. We then use this dynamic yield strength to analyze impacts of copper particles on copper substrates. We find that up to moderate impact velocities, impacts and rebound velocities follow a power-law behavior well-predicted on the basis of elastic-perfectly plastic analysis and can be captured well with a single value for the dynamic strength that subsumes many details not explicitly modeled (rate and hardening effects and adiabatic heating). However, the rebound behavior diverges from the power-law at higher impact velocities approaching bonding, where jetting sets on. This divergence is associated with additional lost kinetic energy, which goes into the ejection of the material associated with jetting and into breaking incipient bonds between the particle and substrate. These results further support and develop the idea that jetting facilitates bonding where a critical amount of bond formation is required to effect permanent particle deposition and prevent the particle from rebounding.

36 MATERIALS SCIENCE↗

Influence of metal ion complexation on the radiolytic longevity of butyramide extractants under direct dissolution conditions

The direct dissolution of volox-treated used nuclear fuel (UNF) into an organic solution—comprised of diluent and specialized extractants—poses a promising alternative to the traditional liquid-liquid solvent extraction approach to reprocessing UNF. However, moving to direct dissolution removes the presence of a concentrated nitric acid aqueous phase, which has been shown to significantly influence the radiolytic longevity of extractants in liquid-liquid solvent extraction flowsheets. With this in mind, and given the limited knowledge of radiation effects under direct dissolution conditions, we present a time-resolved and dose accumulation study on the impact of direct dissolution conditions on the radiolytic longevity of two candidate butyramide extractants—N,N-di-(2-ethylhexyl) butyramide (DEHBA) and N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA)—in pre-equilibrated n-dodecane solvent in the presence and absence of process relevant metal ions, uranium and rhenium. Rhenium, and by extension technetium, extraction had little impact (=10%) on the overall radiolytic stability of these ligands, despite observed increases in chemical kinetic reactivity (>2×) of the corresponding complexes with the n-dodecane radical cation. Uranium-loading on the other hand, significantly improved the lifetime of both ligands (>30%) under gamma irradiation, with a greater stabilization observed for DEHBA over DEHiBA. This draft manuscript has been prepared in fulfillment of NTRD-MRWFD-2024 M3FT-24IN030101115.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Hanford Tank Waste Matrix Impact on Ion Exchange Performance Using Crystalline Silicotitanate

The removal of radiocesium from Hanford tank waste supernate is a critical step in preparing feed for low-activity waste immobilization. This study evaluated cesium ion exchange performance using crystalline silicotitanate (CST) media in a series of tests designed to evaluate the influence of waste matrix variability on capacity and kinetics. Tank waste supernate subsampled from five Hanford double-shell tanks encompassed a range of sodium, hydroxide, nitrate, and nitrite concentrations in order to assess the impact of feed variability on the performance of the ion exchange system. Both equilibrium and dynamic ion exchange tests were conducted to quantify cesium distribution coefficients and breakthrough behavior under prototypic operating conditions. Results indicated that effective cesium capacity varied by up to a factor of five across the matrices tested, with higher sodium concentrations significantly reducing uptake. Kinetic behavior was similarly matrix-dependent, with solution viscosity contributing to a twofold variation in mass-transfer rates. These results demonstrate the strong dependence of CST ion exchange performance on waste composition and must be incorporated into predictive models for future treatment system design and optimization.

Westesen, Amy M.↗

Atmospheric ice nucleation

Atmospheric ice nucleation is crucial for global precipitation and affects the structure, lifetime and reflectivity of clouds, thereby impacting climate. Ice nucleates in various ways from aerosol particles, termed ice-nucleating particles, over an extensive temperature and humidity range. Quantifying the kinetic and thermodynamic regimes of nucleation is necessary to relate fundamental physics to theoretically based predictions of ice formation for implementation in cloud and climate models. We review how the molecular picture of ice nucleation has advanced in recent years and consequential impacts on the interpretation and parameterization of ice nucleation. Advances include the role of interfacial free energy and pressure on ice nucleation rates, mobility regions of water that generate the critical ice nucleus, classical and non-classical pathways of nucleation, the type of ice polymorph that forms, the impact of solutes on freezing and the role of nanopores as surface features promoting ice nucleation. We also introduce currently debated and evaluated freezing parameterizations for application in model environments. Finally, we outline what we believe are the current needs for improving predictive understanding of ice nucleation.

54 ENVIRONMENTAL SCIENCES↗

Intermittent oxidation kinetics and metal/oxide interfacial undulation

The phenomenon of oxygen-adsorption-induced surface restructuring is widespread across various metal-oxygen systems, yet its impact on initiating bulk oxide formation remains largely unexplored. In this study, through in-situ atomic-resolution electron microscopy observations of surface oxidation of Cu(110) and Cu 85 Au 15 (110), we unveil intermittent oxide-film growth modulated by oxygen-induced surface restructuring. This modulation is evidenced by repeated pinning of Cu 2 O growth front at isolated Cu columns of the c(6×2)-O reconstruction, owing to required long-range diffusion of Cu and O atoms to the Cu 2 O growth front. We reveal that Cu vacancies, generated at the Cu 2 O growth front, are injected into the Cu 2 O/Cu interface, inducing hill-and-valley undulation of the Cu 2 O film. In contrast, atomic vacancies produced during the Cu 85 Au 15 (110) oxidation preferentially migrate into interfaces between Au-rich and Au-poor regions in the bulk, resulting in a flat and adherent Cu 2 O film. These findings demonstrate the critical role of oxygen-induced surface restructuring in modulating oxide-film-growth kinetics and manipulability of the fate of injected vacancies by alloying, thereby offering insights applicable to a broader range of metal-oxygen systems for fine-tuning oxidation kinetics and enhancing oxide/metal interfacial adhesion.

25 ENERGY STORAGE↗

Scaling Laws of Exciton Recombination Kinetics in Low Dimensional Halide Perovskite Nanostructures

Carrier recombination is a crucial process governing the optical properties of a semiconductor. Although various theoretical approaches have been utilized to describe carrier behaviors, a quantitative understanding of the impact of defects and interfaces in low dimensional semiconductor systems is still elusive. Here, we develop a model system consisting of chemically tunable, highly luminescent halide perovskite nanocrystals to illustrate the role of carrier diffusion and material dimensionality on the carrier recombination kinetics and luminescence efficiency. Our advanced synthetic methods provide a well-controlled colloidal system consisting of nanocrystals with different aspect ratios, halide compositions, and surface conditions. Using this system, we reveal the scaling laws of photoluminescence quantum yield and radiative lifetime with respect to the aspect ratio of nanocrystals. The scaling laws derived herein are not only a phenomenological observation but proved a powerful tool disentangling the carrier dynamics of microscopic systems in a quantitative and interpretable manner. The investigation of our model system and theoretical formulation bring to light the dimensionality, as a hidden constraint on carrier dynamics, and identify the diffusion length as an important parameter that distinguishes nanoscale and macroscale carrier behaviors. Furthermore, the conceptual distinction in carrier dynamics in different dimensionality regimes informs new design rules for optical devices where complex microstructures are involved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cations Enhance Hydride Transfer to Noncatalytic Metals in Concentrated Alkaline Electrolytes

Alkali metal cations are known to influence the kinetics of the hydrogen evolution reaction (HER), acting as either promoters or inhibitors to the rate-determining step depending on the metal surface, local pH, and cation concentration. Despite the importance of concentrated electrolytes for commercial electrochemical cells, the impact of cations on the HER in concentrated alkaline environments (>1 M) and in mixed cation systems remains poorly understood. Here, this study quantifies the HER kinetics at polycrystalline metal surfaces (Pt, Au, Cu, and Fe) and the equilibrium solvation environment in pure and mixed alkali metal hydroxide electrolytes at concentrations up to 3.0 M. Kinetic analyses of Au, Cu, and Fe revealed a positive cation-concentration-effect that was primarily driven by changes to the charge transfer coefficient. Multinuclear NMR spectroscopy examined the solvation of H 2 O/OH – species and the alkali cations as a function of (mixed) alkali cation concentration(s), and demonstrated rapid exchange between solvent, hydroxide, and solvated cations. Together, these findings support models where HER kinetics on noncatalytic metal surfaces in strongly alkaline conditions are primarily governed by the average polarization and polarizability of the metal/solution interface and that increasing cation activity continues to increase the transfer coefficient at metal-hydroxide concentrations up to 3.0 M. Electrolytes and additives which can outcompete weakly hydrated cations and disrupt the interfacial water structure are expected to suppress parasitic HER at electrodes for energy storage and electroplating.

Cations↗

Long-term impact of light- and elevated temperature-induced degradation on photovoltaic arrays

Low levelized cost of electricity (LCOE) has been identified as critical for widespread adoption of photovoltaics (PV) without subsidies. Maintaining decades-long high-energy production is often an under-recognized opportunity in meeting cost goals because component lifetimes are not fully quantified at the time of manufacture. Whereas certain standardized tests minimize risk of early failure, there is little guidance to quantitatively predict degradation (or lack thereof) over decades, based on accelerated tests. In this article, we move toward bridging the understanding between indoor accelerated tests and outdoor performance data, with the goal of predicting energy yield with enough accuracy to inform financial decisions. Light- and elevated temperature-induced degradation (LETID) in p-type Si modules is analyzed in terms of impact on long-term module performance and thus LCOE. A method to predict the progression of LETID, using fixed kinetic constants and a numerical solution to the basic reaction rate equations, is detailed. Predictions are compared against both published data and that new to this study. These data include both indoor accelerated tests and fielded modules. We use the results in financial models to derive LCOE of modules in different climates with varying amounts of LETID, including uncertainty. Cost models based on the predictions indicate that LETID has a significant and climate-dependent impact on LCOE. Finally, we show that - even given the uncertainties identified in the study - these financial calculations can provide useful guidance to quantify risk based on accelerated test results. The analysis serves as an example of developing a predictive approach to PV reliability using physics of failure.

14 SOLAR ENERGY↗

Aldehyde cool-flame chemistry explains a missing source of organic acids

Combustion emission is a significant source of organic acids, impacting atmospheric chemistry and climate. Their formation mechanisms, however, remain poorly understood, leading to underestimation in kinetic models. We investigate the cool-flame oxidation of key combustion intermediates—C 1 –C 4 aldehydes and benzaldehyde. Using in-situ synchrotron vacuum ultraviolet photoionization mass spectrometry, we observe the direct conversion of aldehydes to organic acids, a process enhanced by HO 2 radicals. Quantum chemistry calculations reveal that the reaction of RC(O)O 2 with HO 2 on the singlet potential energy surface contributes to organic acids. Incorporating this pathway into a kinetic model significantly improves organic acid prediction. Despite the high-temperature nature of engine combustion, significant spatial and temporal inhomogeneities (e.g., near-wall regions and crevice volumes) lead to localized cool-flame conditions, facilitating organic acid formation and emission. Elucidating the acid formation under cool-flame conditions provides a critical mechanism for accurately modelling anthropogenic organic acid emissions and developing mitigation strategies.

SVUV-PIMS↗

Improving Durability of Fuel Cells with Platinum-rich Alloy Cathode Catalysts

Pt 3 Co-alloy based nanoparticle catalysts are very active for oxygen reduction reaction (ORR) thereby enabling high performance of proton exchange membrane fuel cells (PEMFC) for automotive propulsion. However, these catalyst materials degrade due to a combination of electrochemical surface area (ECSA) loss and dissolution of cobalt-alloying element from the nanoparticles. Dissolution of cobalt has a two-fold impact on the durability of fuel cells—i) a loss in the low-current density kinetic region due to a decrease in specific activity and ii) a loss in the high-current density transport region due to Co 2+ contamination of the ionomer phase. Cobalt dissolution-contamination needs to be mitigated as it limits fuel cell performance and lifetime for heavy-duty automotive applications. In this article, we study the use of PtCo-alloy catalysts with Pt-rich compositions using catalyst-specific accelerated stress test measurement in membrane electrode assemblies to decrease the amount of dissolved Co and mitigate its subsequent contamination effects. We demonstrate Pt 5 Co and Pt 7 Co compositions to enable significant improvements in durability (∼50 mV and ∼100 mV with respect to Pt 3 Co after 30,000 voltage cycles) with a minor but acceptable compromise in the initial specific activity of the catalyst.

08 HYDROGEN↗

Characterizing cobalt sequestration in manganese-rich coal mine drainage treatment solids

This study investigates Co adsorption on synthesized birnessites over a wide pH range and in sulfate-rich solution to simulate CMD treatment conditions. Langmuir and Freundlich adsorption isotherms of Co at pH values of 3.5, 4.5, and 6.5 at 25°C onto Na-and H-birnessite were generated. Cobalt concentrations in supernatants were determined by ICP-MS and chelation ion chromatography. Mineralogy and morphology of pre- and post-adsorption experiment solids characterization by X-ray diffraction and scanning electron microscopy will be presented. These experiments suggest that cobalt sulfate complexes and pH of CMD, as well as the Mn-oxide mineral structures present in treatment beds, will impact cobalt adsorption in CMD solids, and can be used as calibration points for equilibrium and kinetic modeling approaches that are critical for developing effective and implementable remediation processes and to better inform future Co recovery efforts from CMD solids.

Schaffer, Camille↗

Gas Hydrate Film Growth in Microfluidic Channels for Carbon Dioxide Capture and Sequestration Applications

Gas or clathrate hydrates are a solid, crystalline compound composed of water and guest molecules that typically form at high pressure and low temperature conditions. Carbon dioxide (CO2) hydrates may be involved in several carbon dioxide capture and sequestration (CCS) applications, including CO2 pipeline transportation and CO2 offshore sequestration. Within these applications, the formation mechanism and kinetics must be well understood to manage the CCS processes, either by preventing or promoting hydrate formation. In this work, a high-pressure glass microfluidic reactor is used in tandem with visual microscopy and in-situ Raman spectroscopy to study both the morphological and kinetic behavior of gas hydrate crystals. Subcooling, pressure, and CO2 flow rate are investigated for their impact on the thickening behavior of pure CO2 hydrates, with flow rate being the only parameter to have a significant effect. Visual and Raman spectroscopy evidence show that both a dense hydrate layer and a porous hydrate layer form, and the latter may provide a path for mass transfer to continue hydrate crystallization. A first principles mass transfer model is developed to describe CO2 hydrate crystal thickening at the interface between gas and water. The impacts of gas impurities and channel wettability are also studied. This method is further applied to investigate the conversion of methane hydrate to CO2 hydrate for combined energy recovery and methane hydrate formation. The authors acknowledge the US Department of Energy Basic Energy Science award # DE-SC0022162.

Wadsworth, Lindsey [Colorado School of Mines, Gold↗