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At least 1,225 records · Page 68

Terrestrial growth of lead-tin-telluride by techniques related to low G growth

A modified Bridgman-Stockbarger furnace was constructed for a study of the solidification of silver, germanium and lead-tin-telluride. The melt-solid interface position with respect to the furnace and its temperature profile was determined by measuring the discontinuity in the slope of temperature as a function of position in the melt and in the solid. The results show that the interface position of the semiconductors germanium and lead-tin-telluride was essentially constant with respect to the furnace and hence the growth rate was constant and equal to the sample translation rate of 0.046 cm/min and 0.178 cm/min in each case. The metal, silver, on the other hand showed a continuous interface migration toward the hot zone of the furnace and always exhibited a growth rate which was higher than the ampoule translation rate. The K sub L/K sub S ratio of lead-tin-telluride was determined to be 2.33 + or - 0.06 where K sub L,S denotes the thermal conductivity of the liquid, solid respectively. The value of K sub L was calculated to be about 0.054 Watt 0.1 cm 0.1 K. The diffusion boundary layer thickness was calculated for lead-tin-telluride to be about 0.05 cm using a liquid diffusivity of .00007 sq cm/sec.

Jesser, W. A.↗

Fluid Flow in Crystal Growth: Analysis of the Verticle Bridgman and Floating Zone Process

Research is aimed at the fundamental understanding of the interactions of heat and mass transport and fluid mechanics in crystal growth from the melt, especially in how it pertains to experiments supported by the Microgravity Science and Applications program. Emphasis has been on studies of the vertical Bridgman system, on small-scale floating zone systems proposed for space flight, and on quantitative prediction of nonlinear transitions in melt/solid interface morphologies leading to the formation of dendrites in directional solidification. The analysis of vertical Bridgman growth has lead to the complete numerical analysis of transport phenomena in directional solidification and to a detailed comparison of calculations to the GaGe growth experiments of Wang and Witt. Calculations show the central role of the ampoule material in determining the radial temperature gradients in the melt and thus, the intensity of convection. Results indicate that diffusion-controlled growth can not be achieved on Earth with conventional growth systems, but are feasible in microgravity

Brown, R. A.↗

How Silica Surface Chemistry Modulates Interfacial Water: Insights from Machine Learning Molecular Dynamics

Controlling water structure and dynamics at silica interfaces are central to a wide range of technologies, including protective oxide layers for solar water splitting and nanoporous membranes. In this work, we develop a machine learning interatomic potential, trained via active learning, to achieve ab initio accuracy for water confined between hydroxylated silica surfaces over a range of silanol coverages and slit widths. We find that partially hydroxylated surfaces (50 and 75% OH) support stronger water−surface hydrogen bonding and more extended interfacial density profiles than fully hydroxylated (100% OH) surfaces, indicating that increasing OH coverage does not necessarily strengthen interfacial hydrogenbond networks. Translational diffusion decreases approximately linearly with slit width and OH coverage, whereas rotational dynamics respond nonlinearly. In particular, at the smallest slit width of 5 Å, 75% OH coverage produces an enhanced local tetrahedral ordered interfacial network that strongly suppresses reorientation, while 100% coverage yields a crowded, disordered interfacial layer that also hinders rotation. In contrast, the 50% OH coverage is sufficiently sparse that it does not markedly alter water structure or dynamics under confinement. These results show that coupled control of pore size and surface chemistry enables nonlinear tuning of interfacial water structure and transport, providing a design strategy for optimizing porous silica for either enhanced interfacial stability and controlled reactivity or rapid and selective transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Characterization of Bromine Reduction to Tribromide in Individual Nitrobenzene-in-Water Emulsion Droplets

We report an electrochemical study of bromine reduction to tribromide in a single nitrobenzene (NB) droplet during a single collision event. The feasibility of this study is based on the favorable distribution of Br 2 in NB rather than in water, which was demonstrated by voltammetry at the NB/water interface. The NB-in-water emulsions containing the ionic liquids trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide (ILPA) as the supporting electrolyte and sodium dodecyl sulfate (SDS) as the surfactant were prepared by a high-power ultrasonication. Its single droplet as an attoliter reactor, colliding on a 25 μm Pt UME, was monitored by chronoamperometry. The spike-type current transients of Br 2 reduction can elucidate the size and size distribution of NB, and measure the diffusion in the droplet as analyzed by a bulk electrolysis model. The frequency of collisions can provide diffusion coefficient of the droplets to the UME. Moreover, the i-t decay behavior can be simulated, which fits well with the experimental one.

25 ENERGY STORAGE↗

Tape-Drop Transient Model for In-Situ Automated Tape Placement of Thermoplastic Composites

Composite parts of nonuniform thickness can be fabricated by in-situ automated tape placement (ATP) if the tape can be started and stopped at interior points of the part instead of always at its edges. This technique is termed start/stop-on-the-part, or, alternatively, tape-add/tape-drop. The resulting thermal transients need to be managed in order to achieve net shape and maintain uniform interlaminar weld strength and crystallinity. Starting-on-the-part has been treated previously. This paper continues the study with a thermal analysis of stopping-on-the-part. The thermal source is switched off when the trailing end of the tape enters the nip region of the laydown/consolidation head. The thermal transient is determined by a Fourier-Laplace transform solution of the two-dimensional, time-dependent thermal transport equation. This solution requires that the Peclet number Pe (the dimensionless ratio of inertial to diffusive heat transport) be independent of time and much greater than 1. Plotted isotherms show that the trailing tape-end cools more rapidly than the downstream portions of tape. This cooling can weaken the bond near the tape end; however the length of the affected region is found to be less than 2 mm. To achieve net shape, the consolidation head must continue to move after cut-off until the temperature on the weld interface decreases to the glass transition temperature. The time and elapsed distance for this condition to occur are computed for the Langley ATP robot applying PEEK/carbon fiber composite tape and for two upgrades in robot performance. The elapsed distance after cut-off ranges from about 1 mm for the present robot to about 1 cm for the second upgrade.

Costen, Robert C.↗

Enhanced Electrocatalytic and Cathode‐Electrolyte Interfacial Properties With a Pr‐Based Simple Perovskite/Ruddlesden‐Popper Nanocomposite Cathode in Protonic Ceramic Fuel Cells

The sluggish kinetics and poor stability of the oxygen reduction reaction (ORR) remain the primary bottleneck for achieving high performance in protonic ceramic fuel cells (PCFCs) at intermediate temperatures (400–650°C). In this work, a Pr-based nanocomposite cathode comprised of simple perovskite phase (PrNi 0.7 Co 0.3 O 3-δ ) and Ruddlesden-Popper phase (Co-doped Pr 4 Ni 3 O 10+δ ) is developed. Although PrNi 0.7 Co 0.3 O 3-δ solely stands as a good cathode with facile proton transfer, combining the superior catalytic activity against oxygen on the Ruddlesden-Popper phase boosts the ORR performance further. The designed nanocomposite cathode outperforms the simple perovskite cathode, attributed to enhanced oxygen absorption and surface diffusion with the Ruddlesden-Popper phase. A precursor-based cathode deposition technique is also developed to achieve cathode grain sizes of ∼100 nm. A single cell with the nanocomposite cathode delivers a peak power density of 1.38 W cm −2 at 650°C, among the highest in reported PCFCs with Pr-based cathodes, with a small degradation rate of 0.145 mV h −1 during 250 h stability test. Further investigation of cathode-electrolyte interface revealed interfacial PrO 2 phase formation, promoted by abundant Pr 6 O 11 in the nanocomposite precursor powder, thereby improving both ohmic resistance and stability. These findings highlight the effectiveness of the nanocomposite cathode and underscore its advantages on interfacial properties.

08 - HYDROGEN↗

Preflight status of the External Tank portion of the Space Shuttle Main Propulsion System

The development progress of the External Tank (ET) of the Shuttle Main Propulsion System (MPS) is described. 87% of ET propulsion components have satisfactorily completed qualification tests in preparation for the first Shuttle flight and their performance has been verified in the Main Propulsion Test Article (MPTA) firings of up to 100 seconds duration. The design changes in the LH2 tank pressurant diffuser, the LO2 feed system, and the ground test LO2 tank are discussed. Propellant loading information from MPTA tests may be used to predict loading operations and performance at KSC and VAFB, while ullage pressure profiles and boil-off rates during loading, chilldown rates, and final bulk density data have been obtained with geyser suppression evaluated and loading procedures established and verified. The MPTA test experience provided data to evaluate pressurization system and ET to Orbiter interface propellant performance noting thus that the fluid interface requirements will be satisfied for the first Shuttle flight. The Intertank inerting system was found to be effective in minimizing hazardous gas mixtures and full scale separation tests of the ET to Ground Umbilical Carrier Plate system were successfully completed.

Norquist, L.↗

Characterization of Fuel and Cladding In and Near the Pellet-Pellet Gap of a High-Burnup Pressurized Water Reactor Fuel Rod

At TopFuel 2021, we reported on metallographic examinations of a high burnup ZIRLO-clad spent fuel rod operated at the North Anna Power Station having a 3-mm gap between pellets at an elevation of ~1,403 mm. The rod was sectioned axially at that elevation to reveal the pellet-pellet interfaces and the pellet-pellet gap. Sections were mounted and polished to reveal the distribution of cladding inner and outer oxide layer thicknesses above, below, and within the gap. Since then, total cladding hydrogen measurements have been performed to quantify the cladding hydrogen content through the gap and above and below the pellet-pellet gap region. This paper provides the cladding hydrogen concentrations and discusses the overall findings regarding cladding waterside oxidation and cladding hydrogen diffusion to a pellet-pellet gap.

Montgomery, Rose↗

Spatial coupling of gyrokinetic simulations, a generalized scheme based on first-principles

In this paper, we present a scheme that spatially couples two gyrokinetic codes using first-principles. Coupled equations are presented and a necessary and sufficient condition for ensuring accuracy is derived. This new scheme couples both the field and the particle distribution function. The coupling of the distribution function is only performed once every few time-steps, using a five-dimensional (5D) grid to communicate the distribution function between the two codes. This 5D grid interface enables the coupling of different types of codes and models, such as particle and continuum codes, or delta-f and total-f models. Transferring information from the 5D grid to the marker particle weights is achieved using a new resampling technique. Demonstration of the coupling scheme is shown using two XGC gyrokinetic simulations for both the core and edge. We also apply the coupling scheme to two continuum simulations for a one-dimensional advection–diffusion problem.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Oxidation of Al2O3 continuous fiber-reinforced/NiAl composites

The 1200 C and 1300 C isothermal and cyclic oxidation behavior of Al2O3 continuous fiber-reinforced/NiAl composites were studied. Oxidation resulted in formation of Al2O3 external scales in a similar manner as scales formed on monolithic NiAl. The isothermal oxidation of an Al2O3/NiAl composite resulted in oxidation of the matrix along the fiber/matrix interface near the fiber ends. This oxide acted as a wedge between the fiber and the matrix, and, under cyclic oxidation conditions, led to further oxidation along the fiber lengths and eventual cracking of the composite. The oxidation behavior of composites in which the Al2O3 fibers were sputter coated with nickel prior to processing was much more severe. This was attributed to open channels around the fibers which formed during processing, most likely as a result of the diffusion of the nickel coating into the matrix.

Doychak, J.↗

Neural Network Enhanced RKPM for Electrochemical-Mechanical Coupled Damage Modeling of Energy Storage Materials

Energy storage materials undergo significant charge cycling, which makes understanding their reliability and durability fundamental in predicting performance and service life. Strong electrochemical-mechanical coupling and highly anisotropic material properties contribute to the formation and propagation of micro-cracking, largely along material interfaces and grain boundaries. For Li-ion batteries, for example, lithium moving between electrodes during charging and discharging process causes expansion and contraction of grains, and the strongly anisotropic and nonlinearly [Li]-dependent grain material properties can cause grains to expand into and contract away from each other, leading to chemo-mechanical cracking. In the first part of this work, a RKPM based computational framework for solving the coupled solid-phase lithium conservation with Fickian diffusion and the lithium concentration dependent anisotropic mechanical problem subjected to a highly nonlinear Butler-Volmer boundary condition is introduced. The choice of RKPM completeness conditions for lithium concentration and mechanical deformation fields, and the variational consistency condition for the domain integration of the coupled problem is first determined. In the second part of this work, a neural network-enhanced reproducing kernel particle method (NN-RKPM) [1] is leveraged to accurately capture damage and crack propagation throughout the material, by learning the location, orientation, and sharpness of discontinuity while allowing for a coarser nodal distribution than that is necessary for capturing sharp solution transitions using traditional mesh-based methods. NN-RKPM is used to inform how crack opening and closure in turn affect the coupled chemical equations and material microstructure.

damage modeling↗

Bridging the time scale in exascale computing of chemical systems (Final Technical Report)

This report summarizes the work carried out with support of the United States Department of Energy under Award DE-SC0019441. The theme of this project was to develop and apply methods that allowed for the acceleration of atomistic calculations, particularly in challenging areas such as multiphase systems, electrified interfaces, uncertainty estimation, and applications requiring chemical accuracy, which tend to be applications where simulation time is severely bottlenecked by the computational time requirements. Much of the focus was on the application of emerging machine-learning methodologies, although a wide range of methodologies were employed. This report has two major sections. The first focuses on the methodological advances themselves. Within this part, we report a number of major advances, a few examples of which are described here. We report the first machine-learning scheme for the acceleration of electronically grand-canonical calculations (that is, those applicable to electrochemistry). We report new methods of performing transfer learning, in which physics-based priors can be used to provide predictions, often with uncertainty estimates, of images well outside of training sets; we also offer ways to fine-tune these transfer-learning models. We provide a new systematic means to generate and apply minimal training data sets to very large (10,000’s of atoms) systems, with only small training sets appropriate for electronic structure. We developed new methodologies to integrate surface vibrations into surface adsorption calculations. We made advances to the applicability of diffusion Monte Carlo methods to allow (learned) force prediction, finite-size error correction, and force-free means of searching for transition states. We integrated machine-learned atomistic predictions into mechanism generation codes. Additionally, we released new software including AmpTorch, a modernized version of our original atomistic machine-learning code Amp. The second part of this report focuses on the scientific applications that accompanied, and were often enabled by, the methodological advances described earlier. A few examples follow, but full details are in the individual chapters of the report. For example, we developed a general theory of phonon-induced friction on molecular adsorbates. We showed fundamentally how solvent influences the adsorption and desorption process and how it differs from the processes typically involved at the solid–gas interface, making aqueous-phase and electrocatalysis different from traditional thermocatalysis. We examined how metal–insulator and magnetic transitions can be probed, and accelerated exciton dynamics via Frenkel Hamiltonian parameters. We showed that the nearsighted force-training approach, developed within this project, can predict both the stability and reactivity of large nanoparticles, and can also lead to insights on catalyst coverage on binding energies and entropies. These applied studies, which generally integrated with our method development, allowed us to push forward the theoretical understanding of several reaction classes.

08 HYDROGEN↗

Highly-Cyclable Room-Temperature Phosphorene Polymer Electrolyte Composites for Li Metal Batteries

Despite significant interest toward solid-state electrolytes owing to their superior safety in comparison to liquid-based electrolytes, sluggish ion diffusion and high interfacial resistance limit their application in durable and high-power density batteries. Here, a novel quasi-solid Li + ion conductive nanocomposite polymer electrolyte containing black phosphorous (BP) nanosheets is reported. The developed electrolyte is successfully cycled against Li metal (over 550 h cycling) at 1 mA cm -2 at room temperature. The cycling overpotential is dropped by 75% in comparison to BP-free polymer composite electrolyte indicating lower interfacial resistance at the electrode/electrolyte interfaces. Molecular dynamics simulations reveal that the coordination number of Li + ions around (trifluoromethanesulfonyl)imide (TFSI - ) pairs and ethylene-oxide chains decreases at the Li metal/electrolyte interface, which facilitates the Li + transport through the polymer host. Here, density functional theory calculations confirm that the adsorption of the LiTFSI molecules at the BP surface leads to the weakening of N and Li atomic bonding and enhances the dissociation of Li + ions. This work offers a new potential mechanism to tune the bulk and interfacial ionic conductivity of solid-state electrolytes that may lead to a new generation of lithium polymer batteries with high ionic conduction kinetics and stable long-life cycling.

2D materials↗

Fabrication process development of SiC/superalloy composite sheet for exhaust system components

A chemical compatibility study was conducted between SiC filament and the following P/M matrix alloys: Waspaloy, Hastelloy-X, NiCrAlY, Ha-188, S-57, FeCrAlY, and Incoloy 800. None of the couples demonstrated sufficient chemical compatibility to withstand the minimum HIP consolidation temperatures (996 C) or intended application temperature of the composite (982 C). However, Waspaloy, Haynes 188, and Hastelloy-X were the least reactive with SiC of the candidate alloys. Chemical vapor deposited tungsten was shown to be an effective diffusion barrier between the superalloy matrix and SiC filament providing a defect-free coating of sufficient thickness. However, the coating breaks down when the tungsten is converted into intermetallic compounds by interdiffusion with matrix constituents. Waspaloy was demonstrated to be the most effective matrix alloy candidate in contact with the CVD tungsten barrier because of its relatively low growth rate constant of the intermediate compound and the lack of formation of Kirkendall voids at the matrix-barrier interface. Fabrication methods were developed for producing panels of uniaxial and angle ply composites utilizing CVD tungsten coated filament.

Cornie, J. A.↗

Oxidation Microstructure Studies of Reinforced Carbon/Carbon

Laboratory oxidation studies of reinforced carbon/carbon (RCC) are discussed with particular emphasis on the resulting microstructures. This study involves laboratory furnace (500-1500 C deg) and arc-jet exposures (1538 C deg) on various forms of RCC. RCC without oxidation protection oxidized at 800 and 1100 C deg exhibits pointed and reduced diameter fibers, due to preferential attack along the fiber edges. RCC with a SiC conversion coating exhibits limited attack of the carbon substrate at 500, 700 and 1500 C deg. However samples oxidized at 900, 1100, and 1300 C deg show small oxidation cavities at the SiC/carbon interface below through-thickness cracks in the SiC coating. These cavities have rough edges with denuded fibers and can be easily distinguished from cavities created in processing. Arc-jet tests at 1538 C deg show limited oxidation attack when the SiC coating and glass sealants are intact. When the SiC/sealant protection system is damaged, attack is extensive and proceeds through matrix cracks, creating denuded fibers on the edges of the cracks. Even at 1538 C deg, where diffusion control dominates, attack is non-uniform with fiber edges oxidizing in preference to the bulk fiber and matrix.

Jacobson, Nathan S.↗

Ignition and Combustion of Bulk Metals in a Microgravity Environment

This annual report summarizes the latest results obtained in a NASA-supported project to investigate the effect of gravity on the ignition and combustion of bulk metals. The experimental arrangement used for this purpose consists of a 1000-W xenon lamp that irradiates the top surface of cylindrical titanium and magnesium specimens, 4 mm in diameter and 4 mm in height, in a quiescent, pure-oxygen environment at 1 atm. Reduced gravity is obtained from the NASA LeRC DC-9 aircraft flying parabolic trajectories. Values of critical and ignition temperatures are obtained from thermocouple records. Qualitative observations and propagation rates are extracted from high-speed cinematography. Emission spectra of gas-phase reactions are obtained with an imaging spectrograph/diode array system. It was found that high applied heating rates and large internal conduction losses generate critical and ignition temperatures that are several hundred degrees above the values obtained from isothermal experiments. Because of high conduction and radiation heat losses, no appreciable effect on ignition temperatures with reduced convection in low gravity is detected. Lower propagation rates of the molten interface on titanium and of ignition waves on magnesium are obtained at reduced gravity. These rates are compared to theoretical results from heat conduction analyses with a diffusion/convection controlled reaction. The close agreement found between experimental and theoretical values indicates the importance of the influence of natural convection-enhanced oxygen transport on combustion rates. Lower oxygen flux and lack of oxide product removal in the absence of convective currents appear to be responsible for longer burning times of magnesium diffusion flames at reduced gravity. The accumulation of condensed oxide particles in the flame front at low gravity produces a previously unreported unsteady explosion phenomenon in bulk magnesium flames. This spherically symmetric explosion phenomenon seems to be driven by increased radiation heat transfer from the flame front to an evaporating metal core covered by a porous, flexible oxide coating. These important results have revealed the significant role of gravity on the burning of metals, and are now being used as the database for future experiments to be conducted with different metals at various pressures, oxygen concentrations and gravity levels.

Branch, M. C.↗

Cobalt-free and high-rate stable 5V lithium nickel manganese oxide spinel cathodes enabled via surface oxygen vacancies

Spinel LiNi 0.5 Mn 1.5 O 4 offers both the high-rate, low-cost and safety advantages of LiFePO 4 and the high energy density of LiNiₓMnᵧCo₁₋ₓ₋ᵧO₂ and LiNiₓCoᵧAlzO₂ cathodes. However, the large operating voltage of these materials induces electrolyte oxidation, which degrades the interface and drives Mn dissolution. These reactions are further exacerbated at high rates due to temperature rise. In this study, we discover that ammoniacal treatment followed by annealing introduces a high density of oxygen vacancies in the “near-surface region” of LiNi 0.5 Mn 1.5 O 4 particles. These vacancies release electrons changing the oxidation state of Mn and suppressing its tendency to oxidize the electrolyte. Further, these vacancies enhance the electrode’s electronic conductivity (by ∼3-fold) and Li + diffusivity (by ∼2-fold) greatly improving charge transport, especially when operated at high rates. This results in an across-the-board improvement in self-discharge, specific capacity, energy density, rate capability, coulombic efficiency and cycling stability. When cycled at ∼200 mA g −1 , the capacity fade averaged over 3000 cycles for the surface vacancy-enriched material is ∼0.0167% per cycle compared to an order of magnitude higher fade rate for the baseline material. In conclusion, these findings reveal the potential of targeted surface oxygen vacancy doping to develop cobalt-free and high energy density cathodes that tolerate fast charging and deliver improved cycle life.

Cobalt-free cathodes↗

A Kinetic Model for Predicting Trace Gas Uptake and Reaction

A model is developed to describe trace gas uptake and reaction with applications to aerosols and microdroplets. Gas uptake by the liquid is formulated as a coupled equilibria that links gas, surface, and bulk regions of the droplet or solution. Previously, this framework was used in explicit stochastic reaction-diffusion simulations to predict the reactive uptake kinetics of ozone with droplets containing aqueous aconitic acid, maleic acid, and sodium nitrite. With the use of prior data and simulation results, a new equation for the uptake coefficient is derived, which accounts for both surface and bulk reactions. Lambert W functions are used to obtain closed form solutions to the integrated rate laws for the multiphase kinetics; similar to previous expressions that describe Michaelis-Menten enzyme kinetics. Together these equations couple interface and bulk processes over a wide range of conditions and do not require many of the limiting assumptions needed to apply resistor model formulations to explain trace gas uptake and reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗