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At least 1,297 records · Page 72

Slow manifold reduction for plasma science

The classical Chapman–Enskog procedure admits a substantial geometrical generalization known as slow manifold reduction. This generalization provides a paradigm for deriving and understanding most reduced models in plasma physics that are based on controlled approximations applied to problems with multiple timescales. In this Review we develop the theory of slow manifold reduction with a plasma physics audience in mind. In particular we illustrate (a) how the slow manifold concept may be used to understand breakdown of a reduced model over sufficiently-long time intervals, and (b) how a discrete-time analogue of slow manifold theory provides a useful framework for developing implicit integrators for temporally-stiff plasma models. For readers with more advanced mathematical training we also use slow manifold reduction to explain the phenomenon of inheritance of Hamiltonian structure in dissipation-free reduced plasma models. Various facets of the theory are illustrated in the context of the Abraham–Lorentz model of a single charged particle experiencing its own radiation drag. As a culminating example we derive the slow manifold underlying kinetic quasineutral plasma dynamics up to first-order in perturbation theory. This first-order result incorporates several physical effects associated with small deviations from exact charge neutrality that lead to slow drift away from predictions based on the leading-order approximation n e = Z i n i .

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Platinum group metal-free Fe-based (Fe-N-C) oxygen reduction electrocatalysts for direct alcohol fuel cells

In direct alcohol fuel cells (DAFCs), the oxidation of alcohols happens at the expenses of the oxygen reduction reaction at the cathode. DAFCs' cathodes use a significant amount of platinum that is an expensive critical raw material. Moreover, platinum oxidizes alcohols, a fact that combined with alcohol crossover, decreases significantly the performance of the cells. The use of Fe-based (Fe-N-C) platinum group metal–free (PGM-free) cathodes is a convenient strategy to overcome these limitations. This review analyzes the application of PGM-free cathodes to DAFCs. The discussion focuses on acidic systems and covers the following subjects: (i) the breakdown of DAFC potential in its components, (ii) the analysis of the advantages from the use of the PGM-free cathode, and (iii) a review of the performance and durability of DAFCs. Finally, the review closes with a view of the authors of the future perspective for the research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measuring the flatband potential in 2D semiconductors: Pitfalls and a possible SECCM solution

The flatband potential (V fb ) is a critical parameter in semiconductor electrochemistry, defining the potential at which no excess charge exists at the semiconductor/electrolyte interface. It serves as a key reference for interpreting charge transfer kinetics and current–voltage behavior. However, conventional methods like Mott–Schottky analysis fail for atomically thin 2D materials due to the breakdown of the depletion approximation. This perspective examines the limitations of traditional V fb measurements for 2D semiconductors and the experimental challenges that arise. To address these issues, we propose using scanning electrochemical cell microscopy (SECCM) to spatially resolve the potential of zero charge (V pzc ), equivalent to V fb . This approach mitigates sample heterogeneity issues, such as pinholes or multilayer defects, and offers a pathway to more accurate electrochemical characterization. Ultimately, this method will enhance understanding of current–potential behavior in 2D materials, supporting the design of advanced systems for photoelectrocatalysis, energy conversion, and sensing.

2D semiconductors↗

Challenges and physiological implications of wood feeding in termites

Termites are fascinating insects for a number of reasons, one of which being their specialization on diets of wood lignocellulose. The goal of this review is to consider stress-inducing characteristics of wood and apparent molecular-physiological adaptations in termite guts to overcome these stressors. Defensive factors present in wood include extractive secondary plant metabolites, lignin and related phenolics, crystalline cellulose, and low nitrogen content. Molecular-physiological adaptations of the termite gut to deal with these factors include robust detoxification and antioxidant machinery, the production of a peritrophic matrix and a wide range of cellulases from host and symbiotic sources, and creation of niches available to nitrogen-fixing bacterial symbionts. Considering termite gut physiology and symbioses in the context of stress-response has applied implications. Overall, these outcomes can include development of efficient biomass breakdown strategies, protection of microbes during industrial processing applications, and safeguarding wooden structures from termite damage.

54 ENVIRONMENTAL SCIENCES↗

Molecularly engineered ZnO–carbon nanosheets from fumaric acid precursors for efficient photocatalytic water purification

The photocatalytic breakdown of organic contaminants is crucial for the development of water purification technology. Zinc oxide (ZnO) is an extensively researched photocatalyst; however, its efficacy is hindered by rapid charge recombination and limited utilization of UV irradiation. Resolving these issues necessitates integrating ZnO with conductive carbon phases via scalable, low-temperature synthesis. We provide a molecularly designed sol–gel method that converts zinc–fumarate coordination networks into two-dimensional ZnO–carbon nanosheets utilizing solely aqueous precursors and mild annealing temperatures (400–600 °C). This method utilizes fumaric acid as a dicarboxylate linker and polyvinylpyrrolidone (PVP) as a structural carbon source to produce ultrathin wurtzite ZnO nanosheets embedded inside an amorphous carbon matrix. The resultant ZnO-C hybrid achieves nearly complete methylene blue degradation within 10 min under UV-A illumination, demonstrating first-order kinetics and outstanding recyclability. Compared with commercial ZnO, the ZnO–C nanosheets exhibit comparable rapid photocatalytic degradation, enhanced adsorption behavior, a porous nanosheet morphology, and an integrated ZnO–carbon interfacial structure. These findings provide a viable molecular-templating approach to fabricating various metal oxide–carbon photocatalysts and underscore substantial enhancements in semiconductor efficacy in eco-friendly water treatment systems.

Ozcan, Muca [ORNL] (ORCID:0000000320020474)↗

Data-driven analysis of relight variability of jet fuels induced by turbulence

For safety purposes, reliable reignition of aircraft engines in the event of flame blow-out is a critical requirement. Typically, an external ignition source in the form of a spark is used to achieve a stable flame in the combustor. However, such forced turbulent ignition may not always successfully relight the combustor, mainly because the state of the combustor cannot be precisely determined. Uncertainty in the turbulent flow inside the combustor, inflow conditions, and spark discharge characteristics can lead to variability in sparking outcomes even for nominally identical operating conditions. Prior studies have shown that of all the uncertain parameters, turbulence is often dominant and can drastically alter ignition behavior. For instance, even when different fuels have similar ignition delay times, their ignition behavior in practical systems can be completely different. In practical operating conditions, it is challenging to understand why ignition fails and how much variation in outcomes can be expected. The focus of this work is to understand relight variability induced by turbulence for two different aircraft fuels, namely Jet-A and a variant named C1. A detailed, previously developed simulation approach is used to generate a large number of successful and failed ignition events. Using this data, the cause of misfire is evaluated based on a discriminant analysis that delineates the difference between turbulent initial conditions that lead to ignition or failure. From the discriminant analysis, a compressed sensing algorithm is then applied to help pinpoint the locations of relevant turbulent features. Findings from the discriminant analysis are confirmed with the time history of near kernel properties. Next, a clustering strategy is used to identify ignition and misfire modes. With this approach, it was determined that the cause of ignition failure is different for the two fuels. While it was found that Jet-A is influenced by fuel entrainment, C1 was found to be more sensitive to small scale turbulence features. Finally, a larger variability is found in the ignition modes of C1, which can be subject to extreme events induced by kernel breakdown.

42 ENGINEERING↗

An experimental and detailed kinetic modeling study of the pyrolysis and oxidation of allene and propyne over a wide range of conditions

Allene and propyne are important intermediates in the pyrolysis and oxidation of higher hydrocarbon fuels, and they are also a major source of propargyl radical formation, which can recombine into different C 6 H 6 isomers and finally produce soot. In a prior work (Panigrahy et al., “A comprehensive experimental and improved kinetic modeling study on the pyrolysis and oxidation of propyne”, Proc. Combust. Inst 38 (2021)), the pyrolysis, ignition , and laminar flame speed of propyne were investigated. To understand the kinetic features of initial fuel breakdown and oxidation of the two C 3 H 4 isomers, new measurements for allene pyrolysis and oxidation are conducted in the present paper at the same operating conditions as those studied previously for propyne. Ignition delay times of allene are measured using a high-pressure shock tube and a heated twin-opposed piston rapid compression machine in the temperature range 690– 1450 K at equivalence ratios of 0.5, 1.0 and 2.0 in ‘air’, and at pressures of 10 and 30 bar. Pyrolysis species measurements of allene and propyne are also performed using a gas chromatography integrated singlepulse shock tube in the temperature range 1000–1700 K at pressure of 2 and 5 bar. Furthermore, laminar flame speeds of allene are measured at elevated gas temperatures of 373 K at pressures of 1 and 2 bar for a wide range of equivalence ratios from 0.6 to 1.5. A newly updated kinetic mechanism developed for this study is the first model that can well reproduce all of the experimental results for both allene and propyne. It is observed that in the pyrolysis process, allene dissociates faster than propyne. Both isomers exhibit similar ignition delay times at high temperatures (>1000 K), while, at intermediate temperatures (770–1000 K) propyne is the faster to ignite, and at lower temperatures (< 770 K) allene becomes more reactive. Furthermore, laminar flame speeds for propyne are found to be slightly faster than those for allene under the conditions studied in this work

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Corrosion of rebar in concrete. Part III: Artificial Neural Network analysis of chloride threshold data

Active corrosion of carbon steel in reinforced concrete occurs when the chloride ion concentration exceeds the chloride threshold (CT). CT is affected by many physical and chemical parameters including primary variables (pH, corrosion potential, breakdown potential, and temperature) and secondary variables (cemenet composition, concreete porosity, and water/cement ratio). A Kohonen-self organized map (KSOM) and regression artificial neural network (ANN) coupled methodology was developed to find the missing values of independent variables in the sparse database and for quantitatively evaluating the effects of these variables on CT values that are expressed in %TotalCl/cem (or %FreeCl/cem), and [Cl - ]/[OH - ].

36 MATERIALS SCIENCE↗

Corrosion of rebar in concrete. Part II: Literature survey and statistical analysis of existing data on chloride threshold

The literature is reviewed with respect to defining, measuring, and interpreting the chloride threshold (CT). CT was defined with a strong fundamental basis in the Point Defect Model. which also dictates the nature of the statistical analysis of surveyed CT values. A database of CT for various primary and secondary independent variables has been established. Statistical analyses reveal that CT is lognormally distributed, in accordance with the PDM, with most probable values being 0.85, 0.69, and 1.19 for %total Cl/cem, %free Cl/cem, and [Cl - ]/[OH - ], respectively. The breakdown and corrosion potentials follow normal distributions with means of 0.056 and -0.322 V SCE , respectively.

36 MATERIALS SCIENCE↗

Corrosion of rebar in concrete. Part IV. On the theoretical basis of the chloride threshold

A theory is developed for calculating the chloride threshold (CT) from the Point Defect Model (PDM). CT is defined as the ratio [Cl - ]/[OH - ] at which the passivity breakdown voltage (E b ) equals the corrosion potential, ECP. CT is sensitive to the T, ECP, pH, and E b , because all four appear in the exponent X in CT = 10 X . Small uncertainties in these parameters translate into a large uncertainty in CT, emphasizing the need for accurate T, ECP, pH, and E b data. We demonstrate the theory by successfully calculating CT using data for selected systems.

36 MATERIALS SCIENCE↗

Influence of artificial aging on corrosion of abraded Al-Zn-Mg-Cu alloys

Surface abrasion has been shown to create altered surface layers (ASLs) that are hundreds of nm thick on all types of Al alloys. Such ASLs have lower corrosion resistance than the underlying substrate of Al-Zn-Mg-Cu alloys. Here, we demonstrate how heat treatments affect the ASL microstructure on abraded Al-Zn-Mg-Cu alloys using transmission electron microscopy and atom probe tomography, and also how the corrosion properties change using electrochemical polarization. Additionally, high temperature treatments on the abraded bulk samples enhance η phase precipitation in the ASL, leading to a decreased Zn content in the ASL solid solution, which ennobles the ASL breakdown potential.

36 MATERIALS SCIENCE↗

Protective role of silicon in the high-temperature oxidation of titanium

We investigated the oxidation of pure titanium and Ti-0.8 at.% Si at 800 ° C in Ar-O 2 and O 2 to clarify how dilute silicon additions enhance the oxidation resistance of titanium. The effect of silicon stemmed from differences in oxide growth rather than oxygen dissolution in the metal. Initially, silicon reduced outward oxide growth and completely eliminated inward growth, which we attributed to the continuous Ti 5 Si 3 layer formed at the oxide-metal interface. Furthermore, after breakdown of the Ti 5 Si 3 layer, the oxide — containing silicon — became lamellar but remained more compact and possibly slower growing than the oxide on pure titanium.

36 MATERIALS SCIENCE↗

Microstructure and corrosion of CrFeMnV multi-principal element alloy

In this study, a multi-principal element alloy consisting of equiatomic concentrations of Cr, Fe, Mn, and V was produced by arc melting. The combination of X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy indicated that the CrFeMnV MPEA was comprised of a BCC matrix with a dispersion of a secondary phase. Cyclic potentiodynamic polarization tests in 0.6M NaCl revealed high corrosion resistance – superior to that of stainless steel 304L, as evident from high breakdown and repassivation potentials. X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry provided insight into the formed multi-layer surface film after constant immersion and potentiostatic conditioning.

36 MATERIALS SCIENCE↗

Reverse martensitic transformation on the corrosion behavior of a 2304 lean duplex stainless steel

This study investigates the influence of the reverse martensitic transformation on the corrosion behavior of 2304 lean duplex stainless steel (LDSS) at low temperatures (400–600°C). The steel underwent cold rolling, followed by isochronal annealing for 0.5 h. Phase transformations and microstructures were analyzed using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Corrosion resistance was evaluated using a syringe cell with cyclic potentiodynamic polarization in 0.6 M NaCl solution and double-loop electrochemical potentiokinetic reactivation in 0.5 M H 2 SO 4 + 0.001 M KSCN solution. A bimodal breakdown potential behavior, associated with either pitting or transpassivity, was observed in the as-received (AR) and samples annealed at 400°C. Pitting in the AR sample was associated with Al–Mg–Si–Ca–O inclusions, while pitting on the samples annealed at 400°C was linked to local reduced passive film resistance. Severe cold rolling enhanced the pitting resistance of 2304 LDSS. Selective electrochemical etching revealed preferential corrosion at phase interfaces and within the austenite phase. Additionally, annealing at 500°C to 600°C led to a marked decrease in pitting resistance and increased sensitization. Electron backscatter diffraction analysis of the corroded pits in the annealed specimens indicated that pits tend to nucleate and grow in α'-martensite/austenite regions. Furthermore, the nanostructure formed during low-temperature reversion, characterized by dislocation-cell martensite with high dislocation density and stacking faults, may adversely affect corrosion resistance due to heterogeneities associated with alloying element redistribution.

36 MATERIALS SCIENCE↗

Benchmark of the KGMf with a coupled Boltzmann equation solver

The Kinetic Global Model framework (KGMf) is an open-source general-purpose global model (spatially averaged) simulation code developed to explore the reaction kinetics and pathways in plasma discharge systems. It contains species continuity and electron energy balance equations, with a time-dependent evaluated electron energy distribution function (EEDF) for electron impact reactions. The EEDF is utilized to determine the rate coefficients for electron impact reactions, which can have profound impact on the temporal evolutions of plasma parameters. Previously, the EEDF was commonly assumed as Maxwellian or an analytical function of the effective electron temperature. In this work, the KGMf is coupled with a Boltzmann equation (BE) solver to self-consistently compute the EEDF. The EEDF evolution frequency is determined based on relative changes of the reduced electric field. The KGMf is benchmarked with the ZDPlasKin code based on high-pressure low-temperature argon plasma discharge cases. Additionally, the temporal evolutions of reduced electric field, electron temperature, EEDF, reaction rates, and species densities, are obtained and compared under different discharge conditions, showing good agreement between the KGMf and the ZDPlasKin simulations. The application of the KGMf for predicting breakdown times in high power microwave discharges is also presented, which shows qualitative agreement with particle-in-cell simulations. The KGMf can be further applied for more complicated plasma discharge systems, where the reaction kinetics are more intricate (e.g., plasma-assisted combustion systems).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Stirring and peristaltic pumping alter flow electrode particle size and morphology

Flowable carbon-based electrodes are widely studied in electrochemical systems for energy storage and water treatment. Most laboratory- and pilot-scale studies employ active mixing for slurry preparation and handling and use peristaltic pumps for slurry circulation. Magnetic stirring is the most prevalent mixing method at the laboratory scale, and the combination of magnetic mixing and peristaltic pumping is favored for convenience and compatibility with particulate suspensions. However, these methods can strongly affect particle size and morphology (and therefore cell performance). In this study, we evaluate how mixing and pumping influence particle degradation in two commonly used carbon materials: spherical carbon black (CB) beads and powdered activated carbon (AC). We performed 24 h stirring-only experiments using magnetic, orbital, and overhead stirring. Separately, we conducted 32 h circulation experiments using a commercial peristaltic pump. Particle morphology and size were analyzed using optical microscopy and laser diffraction. The initially spherical CB beads (~580 μm, 1.5 wt%) exhibit rapid and extensive breakdown under both peristaltic pumping and magnetic stirring. By comparison, AC particles (initially ~31 μm) tested at 1.5 and 15 wt% showed measurable size reductions of up to ~25 % under either stirring or pumping. In conclusion, these findings highlight the need to account for and quantify morphological changes caused by both stirring and pumping in the design and associated evaluation of flowable electrode systems.

Chemistry↗

Bridging interfacial properties and cell performance: A multiscale model for proton-exchange-membrane fuel cells

Here, to elucidate the impact of local interfaces on mass-transport resistance and overall cell performance of low-loaded proton-exchange-membrane fuel cells (PEMFCs), we present a multiscale modeling framework incorporating a novel modified agglomerate model. The model considers three distinct Pt-electrolyte interfaces: Pt on the carbon surface covered by either ionomer or water film and Pt inside carbon nanopores. Detailed mass-transport voltage-loss breakdowns reveal that coupled agglomerate-interface-scale mass transport dominates the mass-transport loss. The ionomer poisons the exterior-Pt surface through suppressing O 2 adsorption and intrinsic ORR activity, leading to low current-density performance. Conversely, interior-Pt interface enhances the kinetic performance but limits high current-density performance due to its low interfacial permeability. The exterior-Pt/water interface demonstrates superior kinetic performance and mass transport, though its practical implementation requires ensuring proton transport. By coupling the multiscale CL properties with ink parameters, the model identifies an optimal I to C ratio of approximately 0.5, a moderate value where the ionomer content is sufficient to guarantee proton transport without fully covering the Pt surface and forming large agglomeration, thus allowing the utilization of the Pt-water interface and avoiding high mass-transport loss. Overall, the model helps unravel limiting phenomena across different operating regimes and provides routes for optimizing performance.

Cell diagnostic↗

Analysis of US Industrial Assessment Centers (IACs) implementation

Industrial energy assessments are a fundamental action toward developing a decarbonization strategy at any level. They provide an understanding of where energy efficiency opportunities exist and help to make informed business decisions about the costs and benefits of implementing sustainable policies and practices. This paper examines the effectiveness of the Department of Energy's Industrial Assessment Centers Program at providing useful energy-efficiency audits as well as the barriers faced by the program and plans for future growth and improvement. This paper presents an analysis of the program between 1981 and 2022, covering 20,290 industrial assessments and 151,198 recommendations, with $2.6 billion of recommended savings. The analysis includes a breakdown of the IAC recommendations and implemented projects based on both the industrial subsectors according to the Standard Industrial Classification code, energy type, and systems evaluated. The results include a 47 % implementation rate, a gap analysis to understand the missed opportunities, and a discussion about reasons for recommendation rejection. A comparison of the IAC Program with other country-level energy auditing or assessment programs was conducted, and suggestions for improving implementation rates were mentioned.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗