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At least 1,135 records · Page 63

Pseudoelasticity at Large Strains in Au Nanocrystals

Pseudoelasticity in metals is normally associated with phase transformations (e.g., shape memory alloys) but has recently been observed in sub-10 nm Ag nanocrystals that rapidly recovered their original shape after deformation to large strains. The discovery of pseudoelasticity in nanoscale metals dramatically changes the current understanding of the properties of solids at the smallest length scales, and the motion of atoms at surfaces. However, it remains unclear whether pseudoelasticity exists in different metals and nanocrystal sizes. The challenge of observing deformation at atomistic to nanometer length scales has prevented a clear mechanistic understanding of nanoscale pseudoelasticity, although surface diffusion and dislocation-mediated processes have been proposed. We further the understanding of pseudoelasticity in nanoscale metals by using a diamond anvil cell to compress colloidal Au nanocrystals under quasihydrostatic and nonhydrostatic pressure conditions. Nanocrystal structural changes are measured using optical spectroscopy and transmission electron microscopy and modeled using electrodynamic theory. Here, we reveal that 3.9 nm Au nanocrystals exhibit pseudoelastic shape recovery after deformation to large uniaxial strains of up to 20%, which is equivalent to an ellipsoid with an aspect ratio of 2. Nanocrystal absorbance efficiency does not recover after deformation, which suggests that crystalline defects may be trapped in the nanocrystals after deformation.

36 MATERIALS SCIENCE↗

A Study of the Effect of Radiation on Recombination Loss in Heterojunction Solar Cells Based on Single-Crystal Silicon

A method has been developed for numerically estimating the recombination loss in silicon heterojunction solar cells under irradiation. The calculations are based on an analysis of the experimental short-circuit currents. The suggested model makes it possible to evaluate the degree of degradation of semiconductor structures by calculating the decrease in the bulk lifetime and in the diffusion length of carriers. The results obtained are of practical importance for examining the possibility of using this type of solar cells in space conditions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Experimental measurements of the ground cloud growth during the 11 February 1974, Titan-Centaur launch at Kennedy Space Center

The Titan-Centaur was launched from Kennedy Space Center on February 11, 1974 at 0948 eastern daylight time. Ground level effluent measurements were obtained from the solid rocket motors for comparison with NASA diffusion models for predicting effluent ground level concentrations and cloud behavior. The results obtained provide a basis for an evaluation of such key model inputs such as cloud rise rate, stabilization altitude, crosswind growth, volume expansion, and cloud trajectory. Ground level effluent measurements were limited because of changing meteorological conditions, incorrect instrument location, and operational problems. Based on the measurement results, operational changes are defined. Photographs of the ground exhaust clouds are shown. The chemical composition of the exhaust gases was analyzed and is given.

Stewart, R. B.↗

Kinetics of pack aluminization of nickel

The kinetics of pack aluminization of unalloyed nickel in packs of varying aluminum activity with various halide activators were studied. Surface compositions of the coatings as functions of time, temperature, and pack composition were obtained in order to establish the boundary conditions for diffusion in the system. The structure of the packs was also examined in order to clarify the mechanism of aluminum transport. The results indicate that the kinetics of pack aluminization are controlled jointly by gas diffusion in the pack and solid diffusion in the coating. Levine and Caves' model for gas diffusion was combined with calculations of rates of diffusion in the solid to formulate a more complete theory for the kinetics of pack aluminization.

Seigle, L. L.↗

A numerical solution of the supersonic flow over a rearward facing step with transverse non-reacting hydrogen injection

The present investigation represents an application of computational fluid dynamics to a problem associated with the flow in the combustor region of a supersonic combustion ramjet engine (scramjet). The governing equations are considered, taking into account the Navier-Stokes equations, a molecular viscosity calculation, the molecular thermal conductivity, molecular diffusion, and a turbulence model. The employed numerical solution is patterned after the explicit, time-dependent, unsplit, predictor-corrector, finite-difference method given by MacCormack (1969). The calculation is concerned with the supersonic flow over a rearward-facing step with transverse H2 injection at conditions germane to the combustor region of a scramjet engine. The H2 jet acts as an effective body which essentially shields the primary flow from the rearward-facing step, thus substantially changing the wave pattern in the primary flow.

Berman, H. A.↗

The growth of metastable peritectic compounds

The influence of gravitationally driven convection on the directional solidification of peritectic alloys was evaluated. The Pb-Bi peritectic was studied as a model solidification system. Analyses of directionally solidified Pb-Bi peritectic samples indicate that appreciable macrosegregation occurs due to thermosolutal convection and/or Soret diffusion. The macrosegregation results in sequantial change of phase and morphology as solidification progresses down the length of the sample. Banding was eliminated when furnace conditions were selected which resulted in a planar solidification interface. The directional solidification that occurs in the vicinity of the Pb-Bi peritectic isothermal was found to be isocompositional and to consist solely of the equilibrium terminal solid solution and peritectic phases on an extremely fine scale. Evidence was found to support the peritectic supercooling mechanism, but not the proposed peritectic superheat mechanism.

Larson, D. J., Jr.↗

Thermal fluctuations and the diffuse electrostatic emissions

The suggestion that the weak-banded electrostatic emissions observed in the magnetosphere at frequencies between the electron gyrofrequency and upper hybrid frequency are thermal fluctuations is quantitatively explored, by means of a hot-cold model for dayside electron distributions with density and temperature ratios much greater than unity. It is determined that, for typical dayside conditions, the observed waves are weakly damper Bernstein-Harris modes whose spectral density and polarization, perpendicular to the ambient magnetic field, can be accounted for by the theory. It is suggested that the formalism developed may be applicable to weak electron cyclotron emissions at Jupiter and Saturn, and can be extended to lower-frequency ion cyclotron fluctuations by modifying the theory to include ion contributions.

Sentman, D. D.↗

INTERPLANETARY PROPAGATION OF SOLAR ENERGETIC PARTICLE HEAVY IONS OBSERVED AT 1 AU AND THE ROLE OF ENERGY SCALING

We have studied {approx}0.3 to >100 MeV nucleon{sup -1} H, He, O, and Fe in 17 large western hemisphere solar energetic particle events (SEP) to examine whether the often observed decrease of Fe/O during the rise phase is due to mixing of separate SEP particle populations, or is an interplanetary transport effect. Our earlier study showed that the decrease in Fe/O nearly disappeared if Fe and O were compared at energies where the two species interplanetary diffusion coefficient were equal, and therefore their kinetic energy nucleon{sup -1} was different by typically a factor {approx}2 ({sup e}nergy scaling{sup )}. Using an interplanetary transport model that includes effects of focusing, convection, adiabatic deceleration, and pitch angle scattering we have fit the particle spectral forms and intensity profiles over a broad range of conditions where the 1 AU intensities were reasonably well connected to the source and not obviously dominated by local shock effects. The transport parameters we derive are similar to earlier studies. Our model follows individual particles with a Monte Carlo calculation, making it possible to determine many properties and effects of the transport. We find that the energy scaling feature is preserved, and that the model is reasonably successful at fitting the magnitude and duration of the Fe/O ratio decrease. This along with successfully fitting the observed decrease of the O/He ratio leads us to conclude that this feature is best understood as a transport effect. Although the effects of transport, in particular adiabatic deceleration, are very significant below a few MeV nucleon{sup -1}, the spectral break observed in these events at 1 AU is only somewhat modified by transport, and so the commonly observed spectral breaks must be present at injection. For scattering mean free paths of the order of 0.1 AU adiabatic deceleration is so large below {approx}200 keV nucleon{sup -1} that ions starting with such energies at injection are cooled sufficiently as to be unobservable at 1 AU. Because of the complicating factors of different spectral break energies for different elements, it appears that SEP abundances determined below the break are least susceptible to systematic distortions.

79 ASTRONOMY AND ASTROPHYSICS↗

TWO-DIMENSIONAL CORE-COLLAPSE SUPERNOVA MODELS WITH MULTI-DIMENSIONAL TRANSPORT

We present new two-dimensional (2D) axisymmetric neutrino radiation/hydrodynamic models of core-collapse supernova (CCSN) cores. We use the CASTRO code, which incorporates truly multi-dimensional, multi-group, flux-limited diffusion (MGFLD) neutrino transport, including all relevant O(v/c) terms. Our main motivation for carrying out this study is to compare with recent 2D models produced by other groups who have obtained explosions for some progenitor stars and with recent 2D VULCAN results that did not incorporate O(v/c) terms. We follow the evolution of 12, 15, 20, and 25 solar-mass progenitors to approximately 600 ms after bounce and do not obtain an explosion in any of these models. Though the reason for the qualitative disagreement among the groups engaged in CCSN modeling remains unclear, we speculate that the simplifying ''ray-by-ray'' approach employed by all other groups may be compromising their results. We show that ''ray-by-ray'' calculations greatly exaggerate the angular and temporal variations of the neutrino fluxes, which we argue are better captured by our multi-dimensional MGFLD approach. On the other hand, our 2D models also make approximations, making it difficult to draw definitive conclusions concerning the root of the differences between groups. We discuss some of the diagnostics often employed in the analyses of CCSN simulations and highlight the intimate relationship between the various explosion conditions that have been proposed. Finally, we explore the ingredients that may be missing in current calculations that may be important in reproducing the properties of the average CCSNe, should the delayed neutrino-heating mechanism be the correct mechanism of explosion.

79 ASTRONOMY AND ASTROPHYSICS↗

Model of diffusion-assisted direct laser writing by means of nanopolymerization in the presence of radical quencher

Diffusion-assisted direct laser writing (DA-DLW) by multiphoton polymerization has been recently shown to be one of the most promising methods for the high-resolution 3D nanofabrication [I. Sakellari, et al., ACS Nano 6, 2302 (2012)]. The improvement of the writing spatial resolution has been observed under certain conditions when the mobile radical quencher (polymerization inhibitor) is added to the photosensitive composition. In this work, we present a theoretical study of this method, focusing on the resolution capabilities and optimal writing parameters. The laser beam absorption in the polymerizable composition causes the localized depletion of the quencher molecules. If the quencher depletion is balanced by its diffusion from the outside of the focal volume, the quasi-stationary non-equillibrium concentration spatial profile with zero minimum can be obtained. The polymer is then effectively formed only in the domain where the quencher is depleted. The spatially-distributed quencher, in this case, has the effect similar to that of the vortex beam in STimulated Emission Microscopy (STED)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

On the Impact of Mechanics on Electrochemistry of Lithium-Ion Battery Anodes

Abstract Models exploring electrochemistry-mechanics coupling in liquid electrolyte lithium-ion battery anodes have traditionally incorporated stress impact on thermodynamics, bulk diffusive transport, and fracture, while stress-kinetics coupling is more explored in the context of all solid-state batteries. Here, we showcase the existence of strong link between active particle surface pressure and reaction kinetics affecting performance even in liquid electrolyte systems. Traction-free and immobile particle surface mechanical boundary conditions are used to delineate the varying pressure magnitudes in graphite host during cycling. Both tensile and compressive stresses are generated in traction-free case, while a fixed surface subjects the entire particle to a compression state. Pressure magnitudes are nearly two to three orders of magnitude higher for the latter resulting in significant depression of open circuit potential and improvement of exchange current densities compared to stress-free state. The results demonstrate the need for incorporating stress-kinetics linkage in models and provide a rationale for putting battery electrodes under compression to improve kinetics.

25 ENERGY STORAGE↗

Defect Thermodynamics and Transport Properties of Proton Conducting Oxide BaZr 1–x Y x O 3–δ (x ≤ 0.1) Guided by Density Functional Theory Modeling

Density functional theory-based thermodynamic modeling was performed to determine the effect of humidity and H 2 /O 2 gas pressure on the defect chemistry and transport properties of proton conducting oxide BaZr 1-x Y x O 3-δ (x ≤ 0.1) in the temperature range of 800–1200K, relevant for solid oxide fuel/electrolysis cell applications. The first-principles charge defect analysis was carried out to obtain the defect energetic ensembles as a function of Fermi level as well as the dependence of the hydration and oxidation reaction energies on complex defect-dopant configurations. It is shown that oxygen vacancies introduced to compensate for the extra Ba vacancies may cause a slight increase in the concentration of hydroxyl and proton species upon hydration of Ba deficient BaZr 1-x Y x O 3-δ , while the overall proton diffusivity is predicted to decrease with increased proton hopping barriers upon trapping near the Ba vacancies. The developed defect model is further demonstrated to be able to describe the bulk defect chemistry and transport properties of BaZr 0.9 Y 0.1 O 3-δ under the solid oxide cell operating conditions. Finally, the theoretical framework developed in this work further allows the inclusion of configurational, energetic and electronic characteristics of the defects that can be used as a complementary tool to experimental measurements for testing various mechanistic pathways or to provide essential mechanistic data.

36 MATERIALS SCIENCE↗

Melting and solidification dynamics during laser melting of reaction-based metal matrix composites uncovered by in-situ synchrotron X-ray diffraction

Laser additive manufacturing (AM) of reaction-based metal matrix composites (MMCs) involves highly complex and non-equilibrium material transformation behavior, including melting, dissolution, precipitation, and solidification. Yet, the dynamics and interplay of these phase transformation processes remain poorly understood, posing substantial challenges in identifying the microstructure formation mechanism, and predicting and controlling the microstructure in the printed parts. Here, in this study, we performed the in-situ X-ray diffraction experiment to characterize the phase evolution dynamics of the 316L + 10 vol.%TiC system during laser melting, which provides direct and quantitative insights of the complex phase reaction and evolution dynamics under rapid heating and cooling conditions relevant to additive manufacturing of reaction-based MMCs. Further in-depth thermodynamic and kinetic calculations revealed that most of the phase evolution behavior observed in the in-situ X-ray diffraction experiment cannot be solely explained by widely used equilibrium thermodynamic models, and diffusion-controlled nonequilibrium dissolution and precipitation kinetics must be considered to elucidate the complex phase evolution behavior, including incomplete TiC dissolution, and three-step TiC precipitation. The three distinct types of precipitates generate unique hierarchical TiC micro- and nanostructures, which enhances the yield strength from 513 MPa to 877 MPa by 71 %, tensile strength from 628 MPa to 1054 MPa by 68 %, and Young's modulus from 193 GPa to 221 GPa by 14 %. The findings of our research provide the knowledge foundation for the design of unique microstructures and advanced MMC materials through laser AM.

36 MATERIALS SCIENCE↗

Desolvation Processes in Channel Solvates of Niclosamide

The antiparasitic drug niclosamide (NCL) is notable for its ability to crystallize in multiple 1:1 channel solvate forms, none of which are isostructural. Here, using a combination of time-resolved synchrotron powder X-ray diffraction and thermogravimetry, the process-induced desolvation mechanisms of methanol and acetonitrile solvates are investigated. Structural changes in both solvates follow a complicated molecular-level trajectory characterized by a sudden shift in lattice parameters several degrees below the temperature where the desolvated phase first appears. Model fitting of kinetic data obtained under isothermal heating conditions suggests that the desolvation is rate-limited by the nucleation of the solvent-free product. The desolvation pathways identified in these systems stand in contrast to previous investigations of the NCL channel hydrate, where water loss by diffusion initially yields an anhydrous isomorph that converts to the thermodynamic polymorph at significantly higher temperatures. Taking the view that each solvate lattice is a unique “pre-organized” precursor, a comparison of the pathways from different starting topologies to the same final product provides the opportunity to reevaluate assumptions of how various factors (e.g., solvent binding strength, density) influence solid-state desolvation processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparing Constant and Transient Membrane Transport Parameters for Use in Wave Desalination Models

Directly pressurizing seawater for desalination with reverse osmosis membranes via wave motion is a promising and sustainable method for producing freshwater in coastal regions. However, such a system could result in significant pressure fluctuations and a departure from conventional steady-state desalination operations. This study sought to assess if membrane transport parameters (apparent water and salt permeability) should be modeled as transient or constant in solution–diffusion-based modeling efforts of dynamically operated desalination systems, such as those coupled to wave power. Two approaches were used to model membrane transport parameters: one considered each parameter to be a function of the net driving pressure of the system, and the other assumed they were constant across all conditions. A pilot-scale system was used to conduct steady-state and controlled ramping experiments. Data from steady-state experiments were used to calculate transient and constant transport parameters. Parameter combinations were used in a simulation model to predict water flux and effective permeate salinity, and simulation outcomes were compared against experimental ramping results. The transient relationships for both water and salt permeability produced the most accurate results for water flux and comparable results for effective permeate salinity. Development of such relationships would be unique to a specific system but could be valuable in modeling wave-driven desalination systems across the wide range of operating conditions they experience.

13 HYDRO ENERGY↗

The role of gravity wave induced drag and diffusion in the momentum budget of the mesosphere

A slight modification of the parameterization suggested by Lindzen (1981) for the zonal drag and eddy diffusion effects generated by breaking internal gravity waves in the mesosphere is tested using a severely truncated midlatitude beta-plane channel model. It is found that realistic mean zonal flow profiles with zonal wind reversals above the mesopause can be simulated for both winter and summer radiative heating conditions provided that a gravity-wave spectrum is assumed which includes both stationary waves and waves of relatively large phase speeds. These results contrast greatly with the unrealistic mean wind profiles produced when Rayleigh friction is used to parameterize the effects of small scale motions on the mean flow.

Holton, J. R.↗

Measurements of diffusion limited solidification at varying gravity

The environment of the NASA KC-135 low gravity aircraft was employed to examine the effects of g-jitter on the growth of a solidification diffusion layer for 28 wt pct NH4Cl-H2O, a metal alloy model material. The hypothesis that jitter (vibrational) effects account for previously observed low gravity growth anomalies was investigated by comparing optical data (central dark ground method) for 10-squared g(e) (earth's gravity) KC-135 growth conditions and 1 g(e) laboratory conditions. Accelerometer data obtained during the flight program showed the KC-135 low gravity environment to have extreme levels of jitters.

Mccay, T. D.↗

Analysis of vibrations of the National Transonic Facility model support system using a 3-D aeroelastic code

Vibrations of the National Transonic Facility model support system were analyzed using Computational Aeroelasticity Program-Transonic Small Disturbance, a three-dimensional transonic small disturbance code designed for aeroelastic analysis of complete aircraft. The model support system was represented as a tunnel-spanning flexible wing whose structural properties were obtained from measured responses. Aeroelastic transients were calculated and analyzed to obtain modal stability characteristics. The results show that there is tendency to exhibit a hump mode instability in one of the modes, and that there are other weakly damped or unstable modes. Most of the motion is in the aft section of the model support system. The close proximity of the solid wind-tunnel diffuser side walls to the model support system is shown to have adverse effects on its aeroelastic stability characteristics. When the effects of the wind-tunnel walls are modeled, the analyses indicate the presence of wind-tunnel resonance modes which are not present when free-air boundary conditions are used.

Whitlow, Woodrow, Jr.↗