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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 163 records · Page 9

Regulating the surface Pt coordination environment in the PtN overlayers on PtCuN hollow nanospheres for efficient oxygen reduction reaction

Engineering the surface Pt coordination environment is a promising strategy for promoting the kinetically sluggish oxygen reduction reaction (ORR) on Pt-based catalysts. Here, in this study, we achieve the compressive strain effect and electronic effect by Cu and N co-doping to synthesize the PtCuN hollow nanospheres with PtN overlayers (PtCuN@PtN HNSs) using a facile solvothermal synthesis. Electrochemical investigations show that the constructed disordered Pt–N coordination structures effectively facilitate the ORR and stabilize Pt atoms in the compressed lattice, whereas an excessive N-doping can lead to the formation of a structurally unstable Pt nitride phase. Theoretical analyses confirm that the oxygen reduction kinetics on the compressed PtN overlayers are regulated by a synergistic effect resulting from N-doping and lattice compression, circumventing the traditional linear scaling relationships (LSR). The optimized PtCuN@PtN HNSs, with the composition of PtCu 0.29 N 1.1 , demonstrate an area-specific activity of 1.98 mA cm –2 and a mass-specific activity of 1.81 A mg Pt –1 .

36 MATERIALS SCIENCE↗

On the Application of Deformation Kinetics to Nonlinear Constitutive Relations at Higher Temperatures

A single phenomenological constitutive equation is derived theoretically from first principles and applied to aluminum, tin and lead. The theory is based on deformation kinetics of steady creep in which the fundamental mechanism is atomic transport over potential barriers whose conformation is distorted by the application of a stress field. The form of the functional dependence of barrier distortion and stress over the entire temperature range is found to be a sigmoidal curve which tends to straight lines of a unit slope in the small and high stress regions. With this form of barrier distortion, the constitutive equation prediction the steady creep behavior of aluminum, tin and lead over a wide range of temperature and stress.

Valanis, K. C.↗

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

30 DIRECT ENERGY CONVERSION↗

A theoretical analysis of the extinction limits of a methane-air opposed-jet diffusion flame

A theoretical analysis is described for a methane-air diffusion flame stabilized in the forward stagnation region of a porous metal cylinder in a forced convective flow. The analysis includes effects of radiative heat loss from the porous metal surface and finite rate kinetics but neglects the effects of gravity. The theoretically predicted extinction limits compare well with experimentally observed extinction limits from the literature. After the predicted limits compared well with the experimental limits, a parametric study of the effect of fuel surface emissivity and Lewis number was conducted with the numerical model. It was found that the computed blowoff limit is independent of radiative heat loss for high fuel blowing velocities but is a strong function of Lewis number. At low fuel blowing velocities, the extinction limit varies with both radiative heat loss and Lewis number. It is discovered, however, that even if thermal losses from the fuel surface are absent, the flame can extinguish at the fuel surface independently of Lewis number due to excessive reaction zone thinning.

Olson, S. L.↗

Automated identification and calculation of prompt effects in kinetic mechanisms using statistical models

The kinetics of prompt dissociation involves rovibrationally excited species (generally formed by exothermic reactions) which may dissociate or isomerize prior to thermalization via collisions with the bath gas. Treating such rovibrationally excited species (so-called "hot" species) with standard kinetic phenomenology may result in incorrect macroscopic representation of their reactivity. Here this work presents the first fully automated methodology for the calculation of prompt effects of a chosen species in a kinetic mechanism, including (i) reaction selection; (ii) theoretical calculation of rate constants and prompt branching fractions; and (iii) final rate constant fitting. The energy partition between hot fragments is estimated using a variety of statistical models, including a new physically sound microcanonical statistical model based on the rovibrational density of states of the fragments. The methodology is validated against literature data for the prompt dissociations of HCO and C 3 H 7 radicals. The microcanonical statistical model is in better agreement with trajectory simulations for larger species and is thus applicable for practical systems that typically involve large molecules, for which direct dynamics calculations are impractical. The automated workflow is applied to the evaluation of the effects of prompt dissociation for two isomeric radicals C 4 H 7 1-3 (1-methylallyl) and C 4 H 7 1-4 (3-buten-1-yl). Twelve H-atom abstraction reactions are selected and the corresponding rate constants are computed with first principles theory. The microcanonical statistical model predicts that prompt dissociations of C 4 H 7 1-3 and C 4 H 7 1-4 are already significant at 1000K, resulting in differences of up to an order of magnitude at 2000K with respect to the phenomenological thermal rate constants. To illustrate the effects of prompt dissociation on simulations of experimental data, the calculated prompt rate constants are implemented in both CRECK and C3MechV3.3 kinetic mechanisms. Simulations of experimental flame data illustrate the noticeable impact of prompt dissociation kinetics on the high-temperature combustion reactivity of C 4 H 8 -1 and C 4 H 8 -2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uranium hydride corrosion. II Modeling spatially random growth using reaction and nucleation kinetics

A uranium hydride (UH 3 ) corrosion kinetics model has been developed, based on dimensionally restricted nucleation kinetics, which combines heretofore separate reaction and nucleation kinetics models into a single predictive construct. This theoretical framework accounts for the superficial and random pitting behaviour of UH 3 corrosion. The model can be used to generate the net corrosion surface area and volume fractions for a uranium specimen, generally accounting for its geometric form factor through the surface-to-volume ratio. Furthermore, the combined corrosion kinetics model enables the generation of quantities which may be directly compared to those obtained by non-destructive, non-contact evaluation methods.

36 MATERIALS SCIENCE↗

Tailoring Na⁺ Chelation Dynamics for Expedient Sulfur Redox Kinetics in Low‐Temperature Sodium–Sulfur Batteries

Sodium–sulfur (Na–S) batteries have attracted considerable attention due to their high theoretical energy density and the abundant natural availability of sodium and sulfur. However, sluggish kinetics of sulfur conversion, slow Na⁺ transport, and interfacial instability at low temperatures pose significant challenges for their operation and limit their practical application. Herein, three solvents with well-designed molecular configurations are examined. We systematically investigate the impact of chelation effect on the desolvation behavior, sulfur conversion process, ion dynamics, and Na⁺ plating/stripping behavior. Compared with conventional linear ether solvents, the incorporation of methyl groups not only weaken the chelation capability and tailors the inner solvation sheath, but also reduces the energy barrier for Na⁺ transport, thus promoting enhanced sulfur conversion kinetics under low temperature conditions. This work elucidates the relationship among solvent molecules, Na⁺ desolvation behavior, and sulfur reaction kinetics, and offers a strategy for rational design of electrolytes for low-temperature metal–sulfur batteries.

25 ENERGY STORAGE↗

Theory of terahertz pulse transmission through ferroelectric nanomembranes

An analytical model is developed to predict the temporal evolution of the lattice polarization in ferroelectric nanomembranes upon the excitation by a terahertz (THz) electromagnetic pulse of an arbitrary waveform and the concurrent transmission of the THz pulse in both linear and nonlinear regimes. It involves the use of the perturbation method to solve the equation of motion for the lattice polarization in both unclamped and strained ferroelectric nanomembranes within the framework of Landau-Ginzburg-Devonshire theory. The model is applicable to perovskite oxides such as BaTiO 3 and SrTiO 3 , wurtzite Al 1−𝑥 ⁢Sc 𝑥 ⁢N, and trigonal LiNbO 3 . Our analytical model provides a theoretical basis for determining the thermodynamic and kinetic parameters of ferroelectric materials through a THz transmission experiment. The calculation results also suggest an approach to reversing the chirality of a circularly polarized THz pulse by harnessing the resonant polarization-photon coupling in ferroelectrics. This capability of chirality reversal, along with the high tunability from a strain applied along any arbitrarily oriented in-plane axis, provides new opportunities for THz wave modulation without relying on complex metasurface designs.

36 MATERIALS SCIENCE↗

Is the Orbital-Selective Mott Phase Stable against Interorbital Hopping?

The localization-delocalization transition is at the heart of strong correlation physics. Recently, there is great interest in multiorbital systems where this transition can be restricted to certain orbitals, leading to an orbital-selective Mott phase (OSMP). Theoretically, the OSMP is widely studied for kinetically decoupled orbitals, but the effect of interorbital hopping remains unclear. Here, we show how nonlocal interorbital hopping leads to local hybridization in single-site dynamical mean-field theory (DMFT). Under fairly general circumstances, this implies that, at zero temperature, the OSMP, involving the Mott-insulating state of one orbital, is unstable against interorbital hopping to a different, metallic orbital. We further show that the coherence scale below which all electrons are itinerant is very small and gets exponentially suppressed even if the interorbital hopping is not overly small. Within this framework, the OSMP with interorbital hopping may thus reach down to extremely low temperatures T, but not to T = 0. Accordingly, it is part of a coherence-incoherence crossover and not a quantum critical point. Finally, we present analytical arguments supported by numerical results using the numerical renormalization group as a DMFT impurity solver. We also compare our findings with previous slave-spin studies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A Limited-Ranged Two-Phase Iron Equation of State Model

This report describes the construction of a two-phase EOS for Fe that includes both (hcp) and liquid phases, and which is meant to be valid over the restricted range: V ϵ [4 : 7] °A 3 /atom, and T ϵ [1000 : 20000] K. It was recently used as the basis for a theoretical study of liquid → solid phase transformation kinetics in Fe which appeared in the Supplemental Material for a paper describing a series of NIF shock + ramp compression experiments aimed at constraining the high-P melt curve of Fe.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Theoretical study of the ionospheric G factor

A derivation from kinetic theory of the energy balance equation used in wave interaction work is reviewed. Then G is defined and two models for G are presented: one, a model based on Gerjuoy-Stein cross sections for both O2 and N2; the other based on a more recent model for O2 cross sections. The two models differ considerably in their temperature dependence. The limits of applicability of the useful energy balance equation (hence of the concept of G) are discussed and it is found that no difficulty arises unless the transmitter power is more than 1000 times that now employed at the present operating frequency.

Hagenbuch, K. M.↗

Interstellar C2 molecules in a Taurus dark cloud

Five relatively strong interstellar absorption lines of C2 in the (2-0) Phillips band near 8670 A have been detected toward the heavily reddened, late B star HD 29647, which lies behind a substantial part of one of the darkest regions of the nearest molecular cloud complex, the dark clouds of Taurus. Stringent upper limits on the C2 absorption toward two lightly reddened stars, Nu Cyg and Omicron And, are also reported. The observations yield a column density of about 9 x 10 to the 13th/sq cm, comparable to those of widely distributed molecules like CH and H2CO. Theoretical treatment of the data yields a kinetic temperature of 14 K and a mean density of less than about 1000/cu cm. A narrow, anomalously strong, stellar Mn II line yields a projected rotational velocity of less than about 7 km/s and is explained by previous identifications of the star as Hg-Mn peculiar.

Hobbs, L. M.↗

Hydrogen chemistry - Perspective on experiment and theory

A review is presented of the advantages and limitations of various experimental methods for the investigation of the kinetics of hydrogen chemistry, including classic thermal and photochemical methods and the crossed molecular beam method. Special attention is given to the flash photolysis-resonance fluorescence apparatus developed by Braun et al, in which repetitive vacuum UV flashes result in the photolytic generation of the desired species, and to the discharge-flow technique. The use of various theoretical methods for the selection or elimination of kinetic data is considered in a brief discussion of the rate theory of two-body encounters and recombination-dissociation processes in neutral reactions. Recent kinetic studies of a series of OH reactions and of a major loss process for odd H in the stratosphere are summarized.

Kaufman, F.↗

Macroscale particle simulation of kinetic Alfven waves

Two types of simulations of the kinetic Alfven wave are presented using a macroscale particle simulation code (Tanaka and Sato, 1986) which enables individual particle dynamics to be followed in the MHD scales. In this code, low frequency electromagnetic fields are solved by eliminating high frequency oscillations such as the light modes, and the scalar potential electric field is solved by eliminating Lagrangian oscillations. The dependences of the frequency and the Landau damping on the perpendicular wavenumber were studied, and good agreement was found between simulation and theoretical predictions. Some fundamental nonlinear interactions of the kinetic Alfven wave with the particles (parallel acceleration of the electrons) were also noted.

Tanaka, Motohiko↗

Planar Strain-Rate-Free Diffusion Flames: Initiation, Properties, and Extinction

An effectively strain-rate-free diffusion flame constitutes the most vigorous laminar combustion of initially unmixed reactive gases. Such a diffusion flame is characterized by a relatively long residence time and by a relatively large characteristic length scale. If such a flame were also planar, providing high symmetry, it would be particularly suitable for experimental and theoretical investigations of key combustion phenomena, such as multicomponent diffusion, chemical kinetics, and soot inception, growth, and oxidation. Unfortunately, a planar strain-rate-free diffusion flame is highly disrupted in earth-gravity (e.g., in a counterflow-diffusion-flame apparatus) because of the very rapid onset (approx. 100 ms) of gravity-induced instability. Accordingly, a specially dedicated apparatus was designed, fabricated, and initially checked out for the examination of a planar strain-rate-free diffusion flame in microgravity. Such a diffusion flame may be formed within a hollowed-out squat container (initially configured as 25 cm x 25 cm x 9 cm), with isothermal, noncatalytic, impervious walls. At test initiation, a thin metallic sheet (approx. 1 mm in thickness) that separates the internal volume into two equal portions, each of dimensions 25 cm x 25 cm x 4.5 cm, is withdrawn, by uniform translation (approx. 50 cm/s) in its own plane, through a tightly fitting slit in one side wall. Thereupon, diluted fuel vapor (initially confined to one half-volume of the container) gains access to diluted oxygen (initially with the same pressure, density, and temperature as the fuel, but initially confined to the other half-volume). After a brief delay (approx. 10 ms), to permit limited but sufficient-for-flammability diffusional interpenetration of fuel vapor and oxidizer, burning is initiated by discharge of a line igniter, located along that side wall from which the trailing edge of the separator withdraws. The ignition spawns a triple-flame propagation across the 25 cm x 25 cm centerplane. When a diffusion flame is emplaced in the centerplane, any subsequent travel, and change in temperature, of that planar diffusion flame may be tracked, along with the effectively spatially uniform but temporally evolving pressure within the container. Eventually, nearly complete depletion of the stoichiometrically deficient reactant, along with heat loss to the container surfaces, effects extinction. These data afford an opportunity to check theoretical models of diffusion and chemical kinetics under conditions ranging from intense burning to flame out, or, alternatively, to evolve simple empirical representations of these phenomena. Thus, the project sought to utilize microgravity testing to elucidate commonly encountered phenomenology, arising in the commonly-encountered mode of combustion (whether related to heating, manufacturing, boiling, and propulsion, or to uncontrolled, free-burning fire in structures and wildland vegetation), of those commonly utilized fuels usually categorized as gaseous fuels (such as hydrogen, natural gas, and propane, which are gaseous under atmospheric conditions).

Fendell, Francis↗

First-Row Transition Metal Antimonates for the Oxygen Reduction Reaction

The development of inexpensive and abundant catalysts with high activity, selectivity, and stability for the oxygen reduction reaction (ORR) is imperative for the widespread implementation of fuel cell devices. Herein, we present a combined theoretical–experimental approach to discover and design first-row transition metal antimonates as excellent electrocatalytic materials for the ORR. Theoretically, we identify first-row transition metal antimonates–MSb 2 O 6 , where M = Mn, Fe, Co, and Ni–as nonprecious metal catalysts with good oxygen binding energetics, conductivity, thermodynamic phase stability, and aqueous stability. Among the considered antimonates, MnSb 2 O 6 shows the highest theoretical ORR activity based on the 4e – ORR kinetic volcano. Experimentally, nanoparticulate transition metal antimonate catalysts are found to have a minimum of a 2.5-fold enhancement in intrinsic mass activity (on transition metal mass basis) relative to the corresponding transition metal oxide at 0.7 V vs RHE in 0.1 M KOH. MnSb 2 O 6 is the most active catalyst under these conditions, with a 3.5-fold enhancement on a per Mn mass activity basis and 25-fold enhancement on a surface area basis over its antimony-free counterpart. Electrocatalytic and material stability are demonstrated over a 5 h chronopotentiometry experiment in the stability window identified by theoretical Pourbaix analysis. Furthermore, this study further highlights the stable and electrically conductive antimonate structure as a framework to tune the activity and selectivity of nonprecious metal oxide active sites for ORR catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗