SEARCH · Engineering Papers
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Explore the source record for details and available documents.
In a high-beta plasma the so-called modified-two-stream instability, which results from strongly magnetized electrons drifting relative to unmagnetized ions across a homogeneous magnetic field, is misnamed because the mode is highly kinetic, particularly when the relative streaming velocity exceeds the Alfven speed of the plasma. This kinetic cross-field streaming instability is investigated in detail, examining the effect of the electromagnetic terms and the stability boundaries in both low- and high-beta plasmas. An approximate dispersion relation showing the relation of this mode to the whistler is derived and solutions of it are compared with those obtained from the exact dispersion relation. The kinetic mode, unlike the usual modified-two-stream instability, is not stabilized by electromagnetic effects when the relative electron-ion drift speed exceeds the Alfven speed.
In situ high-resolution interferometry on horizontal facets of the protein lysozyme reveal that the local growth rate R, vicinal slope p, and tangential (step) velocity v fluctuate by up to 80% of their average values. The time scale of these fluctuations, which occur under steady bulk transport conditions through the formation and decay of step bunches (macrosteps), is of the order of 10 min. The fluctuation amplitude of R increases with growth rate (supersaturation) and crystal size, while the amplitude of the v and p fluctuations changes relatively little. Based on a stability analysis for equidistant step trains in the mixed transport-interface-kinetics regime, we argue that the fluctuations originate from the coupling of bulk transport with nonlinear interface kinetics. Furthermore, step bunches moving across the interface in the direction of or opposite to the buoyancy-driven convective flow increase or decrease in height, respectively. This is in agreement with analytical treatments of the interaction of moving steps with solution flow. Major excursions in growth rate are associated with the formation of lattice defects (striations). We show that, in general, the system-dependent kinetic Peclet number, Pe(sub k) , i.e., the relative weight of bulk transport and interface kinetics in the control of the growth process, governs the step bunching dynamics. Since Pe(sub k) can be modified by either forced solution flow or suppression of buoyancy-driven convection under reduced gravity, this model provides a rationale for the choice of specific transport conditions to minimize the formation of compositional inhomogeneities under steady bulk nutrient crystallization conditions.
High-capacity metal oxide conversion anodes for lithium-ion batteries (LIBs) are primarily limited by their poor reversibility and cycling stability. In this study, a promising approach has been developed to improve the electrochemical performance of a MoO 2 anode by direct fluorination of the prelithiated MoO 2 . The fluorinated anode contains a mixture of crystalline MoO 2 and amorphous molybdenum oxyfluoride phases, as determined from a suite of characterization methods including X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy, and scanning transmission electron microscopy. Electrochemical measurements indicate that fluorination facilitates the conversion reaction kinetics, which leads to increased capacity, higher coulombic efficiency, and better cycling stability as compared to the nonfluorinated samples. Overall, these results suggest that fluorination after prelithiation not only favors formation of the oxyfluoride phase but also improves the lithium-ion diffusivity and reversibility of the conversion reaction, making it an attractive approach to address the problems of conversion electrodes. These findings provide a new route to design high-capacity negative electrodes for LIBs.
The stability of a solid-liquid interface in a hypercooled melt is studied, taking into account attachment kinetics, surface energy, and surface energy in the heat balance. There is a basic-state solution with the planar interface moving at constant speed. Linear-stability theory gives a long-wave absolute-stability limit. Near this point a string model is introduced in which a thermal-boundary-layer approximation is used and an evolution equation for the interface is obtained. In a limiting case this interface equation reduces to a Kuromoto-Sivashinsky equation. Comparison with experimental and numerical results are discussed, and a conceptual picture of unconstrained growth for all undercoolings is addressed.
The compound (Pb 2 MnSe 3 ) 0.6 VSe 2 was predicted to be kinetically stable based on density functional theory (DFT) calculations on an island of Pb 2 MnSe 3 between layers of VSe 2 . This approach provides a high degree of freedom by not forcing interlayer lattice match, making it ideal to investigate the likelihood of formation of new incommensurate layer misfit structures. The free space around the island is critical, as it allows atoms to diffuse and hence exploring the local energy landscape around the initial configuration. (Pb 2 MnSe 3 ) 0.6 VSe 2 was synthesized via a near diffusionless reaction from precursors where a repeating sequence of elemental layers matches the local composition and layer sequence of the predicted compound. The VSe 2 layer consists of a Se–V–Se trilayer with octahedral coordination of the V atoms. The Pb 2 MnSe 3 layer consists of three rock-salt-like planes, with a MnSe layer between the planes of PbSe. The center MnSe plane stabilizes the puckering of the outer PbSe layers. Electrical properties indicate that (Pb 2 Mn 1 Se 3 ) 0.6 VSe 2 undergoes a charge density wave transition at ~100 K and orders ferromagnetically at 35 K. Overall, the combination of theory and experiment enables a faster convergence to new heterostructures than either approach in isolation.
A general study of the structure and stability of intermediate shocks (IS) in an isotropic plasma is presented using a hybrid as well as a resistive Hall MHD code. Special emphasis is put on the question of whether the rotational layers observed at the magnetopause can be intermediate shocks. The shocks are formed dynamically by the interaction between a flowing plasma and a stationary piston. Coplanar ISs (both strong and weak) are found to be stable in a collisionless plasma. The existence of slow shocks in a high beta plasma is also established for the first time. Noncoplanar ISs are found to be time-dependent, evolving toward a rotational discontinuity (RD) after some characteristic time tau which can be quite long (1000 Omega(exp -1), where Omega is the ion gyrofrequency). The value tau is larger the closer the rotation angle is to 180 deg. Rotations larger than 180 deg are found to be unstable, decaying into a state of minimum shear (i.e., rotation angle less than 180 deg). There are various length scales associated with an IS in the kinetic regime. The shortest scale is found to be the length scale over which rotation of the transverse component of the magnetic field takes place. This scale can have a half width as small as one ion inertial length (c/omega(sub p)) for electron sense rotations and 3c/omega(sub p) for ion sense rotations, for an upstream ion beta of unity. Both of these scales are consistent with the observed thickness at the magnetopause and identical to the corresponding RD scales. A detailed study of the mode conversion of the Alfven ion cyclotron waves (A/IC) waves across both slow and intermediate shocks and the resulting downstream wave spectrum are presented. The possibility that the large number of relfected ions observed at the magnetopause may be due to the presence of strong ISs is considered. The identification of strong ISs and their distinction from RDs should be possible in observations due to significant differences that exist between jump conditions and overall structure of the two discontinuities. The jumps in the plasma parameters across a weak IS are typically small. This together with the fact that the weak ISs and RDs have very similar thickness and other overall properties makes the distinction between weak ISs and RDs in the observations largely inconsequential. However, at large noncoplanarity angles the weak IS approaches the RD limit in a relatively short time (approximately less than 100 Omega (exp -1)). Thus, magnetopause rotations with large noncoplanarity angles are most likely either RDs or strong ISs. Finally, direct comparisons between fluid (resistive Hall MHD) and kinetic simulations show that fluid theory is not applicable to study of ISs in a collisionless plasma.
Transformative and reconstructive reactions impart significant structural changes at particle boundaries of hybrid perovskites, which influence environmental stability and optoelectronic properties of these materials. Here, we investigate the moisture-induced transformative reactions in formamidinium based perovskites FAPbX 3 (X=I, Br) and show that the ambient stability of these materials can be adjusted from a few hours to several months. For FAPbI 3 , roles of water vapor, particle size, and light illumination on the kinetic pathways of the cubic (a) transformation to the hexagonal (d) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence and solid-state NMR spectroscopy techniques. The grain and sub-grain boundaries exhibit different α→δ-FAPbI 3 phase transformation kinetics. Our study suggests that the dynamic transformation involves the local water-induced dissolution of the cubic phase occurring at the crystal surfaces followed by precipitation of the hexagonal phase. Insights into structures and dynamics of a kinetically trapped α-|δ-FAPbI 3 are obtained by 1 H, 2 H, and 207 Pb ssNMR spectroscopy.
Highly reversible Mg plating/stripping is key for rechargeable Mg batteries and has typically been successfully demonstrated using transient electrochemical techniques such as cyclic voltammetry measurements. Furthermore, little effort has been invested in studying the stability of the electrode/electrolyte interface over an extended time. We report here the development of an in situ generated surface film for Mg anodes based on electrodeposited bismuth (E_Bi). This film improves the interfacial stability of Mg in contact with the electrolyte, particularly over an extended time, and possesses fast charge-transfer kinetics (<30 Ω∙cm 2 ) and low non-time-sensitive interfacial film resistance (ca. 5 Ω∙cm 2 ) for active Mg species.
Abstract In view of the sluggish kinetics suppressing the oxygen evolution reaction (OER), developing efficient and robust OER catalysts is urgent and essential for developing efficient energy conversion technologies. Herein, hybrid amorphous/crystalline FeCoNi layered double hydroxide (LDH)‐supported single Ru atoms (Ru SAs/AC‐FeCoNi) are developed for enabling a highly efficient electrocatalytic OER. The amorphous outer layer in Ru SAs/AC‐FeCoNi is composed of abundant defect sites and unsaturated coordination sites, which can serve as anchoring sites to stabilize single Ru atoms. The crystalline inner has a highly symmetric rigid structure, thereby strengthening the stability of support for a long‐lasting OER. The synergistic effects endow this hybrid catalyst with extremely low overpotential (205 mV at 10 mA cm −2 ). Density functional theory calculation indicates that single Ru atoms stabilized by hybrid amorphous/crystalline FeCoNi LDH facilitate the formation of Ru–O* (rate‐determining step), thus accelerating the OER process.
Here, we analyze the heat transfer between the melt pool and the layer of reacting materials called cold cap, which is the determining factor for the glass production rate in Joule-heated air-bubbled nuclear waste glass melters. We consider the effects of bubbling rate, melt viscosity, melt thermal conductivity, conversion kinetics, and shear rate at the cold-cap bottom, and develop simple relationships for the cold-cap bottom temperature and glass production rate. We show that the melt convection enhances the heat transfer to the cold cap by suppressing the thermal boundary layer and primary foam, while the conversion kinetics opposes these effects. Additionally, we mention how dissolving silica particles affects the primary foam stability and discuss the limitations of the presented approach for vigorously foaming feeds.
Abstract Manganese‐rich layered oxide materials hold great potential as low‐cost and high‐capacity cathodes for Na‐ion batteries. However, they usually form a P2 phase and suffer from fast capacity fade. In this work, an O3 phase sodium cathode has been developed out of a Li and Mn‐rich layered material by leveraging the creation of transition metal (TM) and oxygen vacancies and the electrochemical exchange of Na and Li. The Mn‐rich layered cathode material remains primarily O3 phase during sodiation/desodiation and can have a full sodiation capacity of ca. 220 mAh g −1 . It delivers ca. 160 mAh g −1 specific capacity between 2–3.8 V with >86 % retention over 250 cycles. The TM and oxygen vacancies pre‐formed in the sodiated material enables a reversible migration of TMs from the TM layer to the tetrahedral sites in the Na layer upon de‐sodiation and sodiation. The migration creates metastable states, leading to increased kinetic barrier that prohibits a complete O3‐P3 phase transition.
Protic and non-protic solvents influence the rate of benzaldehyde hydrogenation on Pd by one order of magnitude in the following sequence of increasing reactivity, dioxane < tetrahydrofuran < water < methanol. Despite these differences, the reaction pathway does not change; the majority of turnovers occurs via a Langmuir-Hinshelwood mechanism by stepwise addition of sorbed H to sorbed benzaldehyde, first to the carbonyl O and then to the C atom of the formyl group, forming benzyl alcohol. An analysis of the solvation energies shows that both ground and transition states are destabilized by the solvents compared to the same reaction at the gas-solid interface. The destabilization extent of the reacting organic substrates in both states are similar and, therefore, compensate each other, making the net kinetic effects inconsequential. In consequence, the marked reactivity differences arise solely from the differences in the surface stabilization of adsorbed hydrogen adatoms moderated by the four solvents-more weakly bound hydrogen adatoms, because of their solvation by solvent, exhibit higher rates of their hydrogenation reaction in kinetically relevant attack on the C atom.
A primitive equation linear model is shown to be capable of quantitatively predicting the neutral curve for a baroclinic annulus. Flows unstable to small nonaxisymmetric perturbations are assumed to lie on the nonaxisymmetric side of a transition curve, while the stable flows are on the axisymmetric side. The stability in the presence of perturbations is tested with linearized hydrostatic primitive equations. Attention is given to the fastest growing eigenmodes, demonstrating that the linear and nonlinear wave have similar structures at a particular point in the nonaxisymmetric regime. All the waves are similar to the Eddy wave except at the extreme to the transition curve, where the waves maintain little structure with height. The eddy kinetic energy is baroclinic with a potential energy suppresed by the large static stability of the basic state. Eddy dissipation is noted to be significant near all boundaries.
Redox-active polymers (RAPs) are promising organic electrode materials for affordable and sustainable batteries due to their flexible chemical structures and negligible solubility in the electrolyte. Developing high-dimensional RAPs with porous structures and crosslinkers can further improve their stability and redox capability by reducing the solubility and enhancing reaction kinetics. Further, this work reports two three-dimensional (3D) RAPs as stable organic cathodes in Na-ion batteries (NIBs) and K-ion batteries (KIBs). Carbonyl functional groups are incorporated into the repeating units of the RAPs by the polycondensation of Tetrakis(4-aminophenyl)methane and two different dianhydrides. The RAPs with interconnected 3D extended conjugation structures undergo multi-electron redox reactions and exhibit high performance in both NIBs and KIBs in terms of long cycle life (up to 8000 cycles) and fast charging capability (up to 2 A g -1 ). The results demonstrate that developing 3D RAPs is an effective strategy to achieve high-performance, affordable, and sustainable NIBs and KIBs.
Most of the sedimentary carbonates deposited in the marine environments are composed of calcium carbonate minerals with varying amounts of incorporated Mg 2+ . However, understanding how interactions of impurities with carbonate and their incorporation affect sediments behavior remains a challenge. Here, a new insight is obtained by monitoring solution composition, morphology, and electrokinetic potential of carbonate particles formed in a spontaneous unseeded batch precipitation experiment using electrochemical and scanning electron microscopy methods. The solid composition and growth rate are extracted from changes in the bulk composition and fitted to chemical affinity rate law, revealing that the precipitation pathway consists of second-order dissolution and first-order precipitation. The molecular dynamics simulations show that the lattice strain induced by randomly substituting Ca 2+ by Mg 2+ stabilizes spherical nanoparticles and reduces their surface area and volume. Combining kinetics and thermodynamics insight, we conclude that variation in the carbonate bulk and interfacial energies, along with the solution supersaturation, lead to the dissolution-precipitation transformation pathway from Mg-rich to Mg-poor carbonate phase that preserves spherulitic morphology. Furthermore, our findings are relevant for long-standing questions of how impurities influence diagenesis of carbonate sediments and spherulitic carbonate particles' origin.
Abstract Ideas about resonant valence bond liquids and spin–charge separation have led to key concepts in physics such as quantum spin liquids, emergent gauge symmetries, topological order and fractionalization. Despite extensive efforts to demonstrate the existence of a resonant valence bond phase in the Hubbard model that originally motivated the concept, a definitive realization has yet to be achieved. Here we present a solution to this long-standing problem by uncovering a resonant valence bond phase exhibiting spin–charge separation in realistic Hamiltonians. We show analytically that this ground state emerges in the dilute-doping limit of a half-filled Mott insulator on corner-sharing tetrahedral lattices with frustrated hopping, in the absence of exchange interactions. We confirm numerically that the results extend to finite exchange interactions, finite-sized systems and finite dopant density. Although much attention has been devoted to the emergence of unconventional states from geometrically frustrated interactions, our work demonstrates that kinetic energy frustration in doped Mott insulators may be essential for stabilizing robust, topologically ordered states in real materials.
In this report, we demonstrate how a uniform angstrom-level oxide overcoat (0.7–1.5 Å) by atomic layer deposition is highly effective not only in enhancing the thermal stability of underlying infiltrated ceria nanoparticles but also in facilitating electrode kinetics.