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NASA NTRS1985

Bulk Formation of Metallic Glasses and Amorphous Silicon from the Melt

By using metallic glass compositions with a high relative glass transition temperature, such as Pd40Ni40P20, homogeneous nucleation also becomes negligible. Large (5g) masses of this alloys were obtained using a molten B2O3 flux. Presently, bulk glass formation in iron based glasses is being investigated. It is expected that if an undercooling of about 250K can be achieved in a Ge or Si melt, formation of the amorphous semiconductor phase (rather than the crystal) may be kinetically favored. The volumetric behavior of undercooled liquid Ga droplet dispersion is investigated by dilatometry. A theoretical model (both analytical and numerical) was developed for transient nucleation in glass forming melts. The model, originally designed for isothermal conditions, was extended to continuous quenching. It is being applied to glass formation in various metallic and oxide systems. A further refinement will be the inclusion of diffusion controlled interfacial rearrangements governing the growth of the crystal embryos.

Spaepen, F.↗

NASA NTRS1992

Rocket plume flowfield characterization using laser Rayleigh scattering

A Doppler-resolved laser Rayleigh scattering diagnostic was applied to a 111 N thrust, regenerative and fuel-film cooled, gaseous hydrogen/gaseous oxygen rocket engine. The axial and radial mean gas velocities were measured from the net Doppler shifts observed for two different scattering angles. Translational temperatures and number densities were estimated from the Doppler widths and scattered intensities, respectively, by assuming that water was the dominant scattering species in the exhaust. The experimental results are compared with theoretical predictions from a full Navier-Stokes code (RD/RPLUS) and the JANNAF Two-Dimensional Kinetics (TDK) and Standardized Plume Flowfield (SPF-II) codes. Discrepancies between the measured and predicted axial velocities, temperatures, and number densities are evident. Radial velocity measurements, however, show excellent agreement with predictions. The discrepancies are attributed primarily to inefficient mixing and combustion caused by the injection of excessive oxidizer along one side of the thrust chamber. Thrust and mass flow rate estimates obtained from the Rayleigh measurements show excellent agreement with the globally measured values.

Zupanc, Frank J.↗

NASA NTRS1992

Rocket plume flowfield characterization using laser Rayleigh scattering

Zupanc, Frank J.↗

NASA NTRS1958

Survey of Hydrogen Combustion Properties

This literature digest of hydrogen-air combustion fundamentals presents data on flame temperature, burning velocity, quenching distance, flammability limits, ignition energy, flame stability, detonation, spontaneous ignition, and explosion limits. The data are assessed, recommended values are given, and relations among various combustion properties are discussed. New material presented includes: theoretical treatment of variation in spontaneous ignition lag with temperature, pressure, and composition, based on reaction kinetics of hydrogen-air composition range for 0.01 to 100 atmospheres and initial temperatures of 0 degrees to 1400 degrees k.

Drell, Isadore L↗

DOE OSTI2021

Ring Opening in Cycloheptane and Dissociation of 1-Heptene at High Temperatures

Cycloalkanes and alkenes are important components of real fuels but there is little kinetic and mechanistic data on the dissociation of most large cyclic and olefinic molecules at elevated temperatures. We present here the first experimental and theoretical investigation of dissociation of cycloheptane and the initial product from ring opening, 1-heptene. Experiments were performed in a diaphragmless shock tube using laser schlieren densitometry. Pyrolysis of cycloheptane (0.5-4% in Kr) was studied over 1450-2000 K and 30-120 Torr. Experiments with 1-heptene (1-4% in Kr) covered 1200-1650 K and 30-120 Torr. A newly developed chemical kinetic mechanism for pyrolysis of cycloheptane and 1-heptene is presented herein. Simulations are in very good agreement with the experimental measurements. Rate coefficients for the initial ring-opening process in cycloheptane, k 1 , and dissociation of 1-heptene, k 2 , were determined from the experiments. Both k 1 and k 2 are in falloff, and the pressure and temperature dependencies were well reproduced by theoretical calculations allowing extrapolation to conditions beyond the scope of this work. These calculations yielded the following expressions for k 1 and k 2 with the uncertainties estimated as +/- 40% and +/- 50% respectively: k 1 , infinity = 5 . 94 & times; 10 17 exp ( & minus;44 T, 521 ) s & minus;1 and k 2 , infinity = 8 . 86 & times; 10 16 exp ( & minus;35 , 887 T ) s & minus;1 . The results of this study indicate that cycloheptane dissociates similarly to cyclopentane and cyclohexane, i.e. ring-opening via C -C scission to a diradical that rapidly isomerizes to a conjugate 1-alkene. The secondary chemistry is dominated by the dissociation products of the 1-alkenes i.e. allyl and n-alkyl radicals. Furthermore, rates of dissociation of the cycloalkanes are size dependent and k cyclopentane << k cyclohexane < k cycloheptane . (c) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Chemical kinetics↗

DOE OSTI2025

Investigating Kinetic Mechanisms of Soot Formation in Plasma Pyrolysis of Methane via Active Learning (Final Technical Report)

Plasma pyrolysis of methane is an effective route for zero-carbon hydrogen production. Yet, soot generated from pyrolysis of hydrocarbons is detrimental to the climate and human health. There is ample experimental and theoretical evidence that suggests polycyclic aromatic hydrocarbons (PAHs) are the molecular precursors to soot particles. The reaction pathways of PAH formation are intricately dependent on a multitude of process parameters, whose kinetic mechanisms are not well-understood in plasma pyrolysis. This project aims to leverage advances in the kinetic modeling of soot formation in combustion, as well as in surrogate modeling and active learning, to systematically investigate the effects of process parameter on the kinetics of PAH formation in plasma pyrolysis of methane. To this end, we propose to use the PAH formation kinetics model developed by the PPPL/PU group based on the well-established ABF and HACA mechanisms, coupled with low-temperature plasma models. We will develop an active learning (AL) framework based on Bayesian optimization to systematically and data-efficiently explore the complex and multivariable parameter space of plasma pyrolysis in order to quantify the effects of plasma and feed parameters on the ABF and HACA kinetic pathways. AL is the branch of machine learning concerned with systematically querying samples from a system (experimental or computational) to train a data-driven model that maps design parameters to a performance criterion. We will use the data generated via AL to perform global sensitivity analysis, combined with uncertainty quantification, to elucidate the impact of different reaction pathways on minimizing formation of soot precursors. This study will result in an improved understanding of kinetics of PAH formation in plasma pyrolysis and can pave the way for more advanced mechanistic studies (e.g., soot nucleation mechanisms). Additionally, the findings will be useful for establishing practical strategies for increasing the pyrolysis efficiency and producing high-grade carbon for synthesis of nanomaterials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2022

Biomimetic Metal-Free Hydride Donor Catalysts for CO 2 Reduction

The catalytic reduction of carbon dioxide to fuels and value-added chemicals is of significance for the development of carbon recycling technologies. One of the main challenges associated with catalytic CO 2 reduction is product selectivity: the formation of carbon monoxide, molecular hydrogen, formate, methanol, and other products occurs with similar thermodynamic driving forces, making it difficult to selectively reduce CO 2 to the target product. Significant scientific effort has been aimed at the development of catalysts that can suppress the undesired hydrogen evolution reaction and direct the reaction toward the selective formation of the desired products, which are easy to handle and store. Inspired by natural photosynthesis, where the CO 2 reduction is achieved using NADPH cofactors in the Calvin cycle, in this study we explore biomimetic metal-free hydride donors as catalysts for the selective reduction of CO 2 to formate. Here, we outline our recent findings on the thermodynamic and kinetic parameters that control the hydride transfer from metal-free hydrides to CO 2 . By experimentally measuring and theoretically calculating the thermodynamic hydricities of a range of metal-free hydride donors, we derive structural and electronic factors that affect their hydride-donating abilities. Two dominant factors that contribute to the stronger hydride donors are identified to be (i) the stabilization of the positive charge formed upon HT via aromatization or by the presence of electron-donating groups and (ii) the destabilization of hydride donors through the anomeric effect or in the presence of significant structural constrains in the hydride molecule. Hydride donors with appropriate thermodynamic hydricities were reacted with CO 2 , and the formation of the formate ion (the first reduction step in CO 2 reduction to methanol) was confirmed experimentally, providing an important proof of principle that organocatalytic CO 2 reduction is feasible. The kinetics of hydride transfer to CO 2 were found to be slow, and the sluggish kinetics were assigned in part to the large self-exchange reorganization energy associated with the organic hydrides in the DMSO solvent. Finally, we outline our approaches to the closure of the catalytic cycle via the electrochemical and photochemical regeneration of the hydride (R–H) from the conjugate hydride acceptors (R + ). We illustrate how proton-coupled electron transfer can be efficiently utilized not only to lower the electrochemical potential at which the hydride regeneration takes place but also to suppress the unwanted dimerization that neutral radical intermediates tend to undergo. Overall, this account provides a summary of important milestones achieved in organocatalytic CO 2 reduction and provides insights into the future research directions needed for the discovery of inexpensive catalysts for carbon recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Shock-driven kinetic and diffusive mix in high-Z pusher ICF designs

Revolver and Double Shell Inertial Confinement Fusion capsule designs hope to achieve a robust volumetric thermonuclear burn via the use of a high-Z pusher shell filled with a cryogenic D–T fuel. Unfortunately, mix of the pusher material into the fuel (gas) may adversely impact the burn performance. Hydrodynamic instability of the metal/gas interface as the mix source is an obvious concern, but 1D effects may also be detrimental. Such effects include plasma diffusion at material interfaces, which has been the subject of numerous theoretical, computational, and experimental investigations. However, other 1D mix mechanisms may exist, which have yet to be thoroughly explored. In particular, plasma kinetic effects may drive the mix when a shock breaks out of the metal/gas interface. Using the state-of-the-art, hybrid (kinetic-ion/fluid electron), multi-ion Vlasov–Fokker–Planck code, iFP, we show herein that shock-driven kinetic effects can reconfigure the interface and the interfacial width subsequently grows diffusively. Finally, we consider any implications for high-Z pusher designs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2023

Influence of External Conditions on the Black-to-Yellow Phase Transition of CsPbI 3 Based on First-Principles Calculations: Pressure and Moisture

All-inorganic CsPbI 3 perovskite has emerged as a promising candidate for next-generation solar cells. However, owing to the poor structural stability of black phase CsPbI 3 perovskite at room temperature, it spontaneously transforms to the yellow, photoinactive, nonperovskite phase at room temperature, limiting further development of CsPbI 3 perovskite solar cells. Here, to better understand the mechanism driving such undesirable phase transformation, we examine the thermodynamics and kinetics associated with γ-to-δ phase transformation using density functional theory calculation. A solid-state nudged elastic band method was employed to find minimum energy pathways assuming a concerted solid-state phase transformation between these two phases. The gas molecules representing atmospheric (H 2 O, O 2 , and N 2 ) and inert (Ar) ambient environments, as well as applied external pressure, were considered to examine the influence of external conditions on the black-to-yellow phase transition. Our calculation reveals that, with increasing pressure, the thermodynamic driving force for converting the γ-phase to the δ-phase increases, whereas a larger activation energy must be overcome for the phase transition to occur. We also investigate the moisture-induced phase transformation with an H 2 O molecule and its dissociated species (H + /OH – ) and demonstrate that the reaction energy barriers can be significantly lowered in the presence of H 2 O or OH – . On the other hand, other nonpolar species (O 2 , N 2 , and Ar) have a negligible effect on the phase transformation kinetics, while they might reduce the thermodynamic driving force for the phase transformation and suppress the undesirable phase transformation. Our theoretical prediction could support recent observations that the γ-to-δ phase transformation occurs rapidly and catalytically in the presence of moisture, whereas in dry argon and dry oxygen atmospheres, the γ-CsPbI 3 remains stable.

14 SOLAR ENERGY↗

NASA NTRS2000

Stellar Coronae: The First Twenty - Five Years

Hot X-ray emitting coronae were detected on stars other than the Sun about twenty-five years ago. Within only a few years of the first detections, the Einstein Observatory had mapped out coronal activity across the HR diagram. These observations provided the foundations for a coarse theoretical understanding of the physical mechanisms responsible for hot coronae on stars that has changed relatively little in the intervening years: plasma trapped in magnetic structures generated by dynamo processes somewhere beneath the photosphere is heated by as yet unidentified mechanisms that appear to transfer kinetic energy from underlying convective regions of the stellar envelope into the outer atmosphere. This review will describe the observational advances that have lead to some further theoretical understanding of stellar coronae, including the first results from high resolution X-ray spectroscopy obtained by Chandra and XMM-Newton, and will highlight the observational directions needed to make further progress.

Drake, Jeremy↗

DOE OSTI2020

Irradiation Tests of Superconducting Detectors and Comparison with Simulations

For the future satellite mission at the second sun–earth Lagrangian point (L2), we need to mitigate phonon propagation created by cosmic rays to superconducting detectors. We simulate phonon propagation in silicon substrate and show that putting a metal layer on the substrate or making hole in the substrate reduces the propagation. We also show a function which shows the response of a TES bolometer on a substrate. To validate these theoretical expectations, we make irradiation tests using two types of superconducting detectors: transition edge sensor bolometers and kinetic inductance detectors. From the tests, we show that putting metal can reduce correlations between detectors and number of hit events from charged particles.

47 OTHER INSTRUMENTATION↗

DOE OSTI2025

Integrative mapping reveals molecular features underlying the mechanism of nucleocytoplasmic transport

Nuclear pore complexes (NPCs) enable rapid, selective, and robust nucleocytoplasmic transport. To explain how transport emerges from the system components and their interactions, we used experimental data and theoretical information to construct an integrative Brownian dynamics model of transport through an NPC, coupled to a kinetic model of transport in the cell. The model recapitulates key aspects of transport for a wide range of molecular cargoes, including preribosomes and viral capsids. Our model quantifies how flexible phenylalanine-glycine (FG) repeat proteins create an entropic barrier to passive diffusion and how this barrier is selectively lowered in facilitated diffusion by the many transient interactions of nuclear transport receptors with the FG repeats. Selective transport is enhanced by “fuzzy” multivalent interactions, redundant FG repeat mass, coupling to the energy-dependent RanGTP concentration gradient, and exponential dependence of transport kinetics on the transport barrier. Our model will facilitate rational modulation of the NPC and its artificial mimics.

Raveh, Barak [School of Computer Science and Engin↗

DOE OSTI2022

Discovery of multimechanisms of screw dislocation interaction in bcc iron from open-ended saddle point searches

Dislocation motion and interactions determine mechanical properties in body-centered cubic (bcc) metallic materials. However, studying mechanisms for the screw dislocation interaction is fundamentally challenging since many underlying processes involve mesotimescales and atomistic resolution, currently inaccessible by either experimental techniques or continuum theoretical methods. Here, in this paper, we develop a computational capability based on self-evolving atomistic kinetic Monte Carlo (SEAKMC) to sample the critical events and saddle point energies related to screw dislocations and their junctions. The method is first validated by calculating the stress dependence of Peierls barriers and formation energies of kink pairs and cross-slip kink pairs on a single screw dislocation in bcc iron. Then the method is applied to a binary junction of a pair of intersecting screw dislocations, the structure of which is crucial for low-temperature plastic deformation. We identify three important mechanisms: coplanar cross-slipping, jog-pinning, and a previously unknown unzipping mechanism during the evolution of the binary junction. The mechanisms are then further validated using classical molecular dynamics simulations. The computational capability developed in this paper provides an effective tool to evaluate screw dislocation related thermally activated events in complex stress conditions. The mechanisms discovered in this paper provide critical insights into temperature dependence of the anomalous slip, a breakdown of the Schmidt law, during the plastic deformation in bcc iron and can be generalized to other bcc metals.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Modeling of flash sintering of ionic ceramics

A fundamental understanding of the influence of defects in ionic ceramics at the atomic, microstructural, and macroscopic levels, before, during, and after the flash sintering event is key to the development of ceramic processing operations that lead to fast, low cost, and environmentally safe fabrication of materials. The observed phenomenology of the flash process encompasses multiple time and length scales and have resulted on a wide variety of what sometimes appears to be contradictory explanations. Here, this article summarizes the latest developments on the modeling and simulation of flash sintering, specifically those related to the understanding of the equilibrium and kinetic properties and the corresponding microstructural evolution of ionic ceramics. Challenges and opportunities in the development of theoretical analyses that include unidentified multiphysical effects are discussed, as they pertain to the processing of technologically relevant ceramic materials for advanced structures and devices.

36 MATERIALS SCIENCE↗

NASA NTRS1978

Calculated rate constants for the reaction ClO + O yields Cl + O2 between 220 and 1000 deg K

Classical trajectory calculations are presented for the reaction ClO + O yields Cl + O2, a reaction which is an important step in the chlorine-catalyzed destruction of ozone which is thought to occur in the 220 and 1000 K. The calculated rate constant is 4.36 x 10 to the minus 11th power exp (-191/T)cu cm molecule (-1)s(-1) and its value at 300 K is 2.3 plus or minus 10 to the 11th power cu cm molecule (-1)s(-1), about a factor of 2 lower than recent experimental data. The empirical potential energy surface used in the calculations was constructed to fit experimental data for ClO, O2 and ClOO molecules. Other important features of this potential surface, such as the barrier to reaction, were varied systematically and calculations were performed for a range of conditions to determine the best theoretical rate constants. Results demonstrate the utility of classical trajectory methods for determining activation energies and other kinetic data for important atmospheric reactions.

Jaffee, R. L.↗

NASA NTRS1978

Collisional excitation of interstellar molecules - Linear molecules CO, CS, OCS, and HC3N

Rates for excitation of CO, CS, OCS, and HC3N by collisions with He atoms and H2 molecules are presented. These have been obtained from extensive theoretical calculations using methods of known reliability. In general, rates necessary for modeling interstellar molecular clouds with kinetic temperatures to 100 K have been included. Methods for fitting these rates in more compact form are discussed.

Green, S.↗

NASA NTRS1980

Collisional excitation of interstellar molecules - Water

Rate constants for excitation of water molecules by collisions with He atoms have been obtained from extensive theoretical calculations. For ortho-H2O, rates are presented for all spectroscopic levels below 1000/cm and for kinetic temperatures to 500 K; for para-H2O, levels below 300/cm and kinetic temperatures to 250 K are included. It is suggested that rates of excitation by collisions with hydrogen molecules are similar to those for He atoms.

Green, S.↗

NASA NTRS1994

A Coulomb collision algorithm for weighted particle simulations

A binary Coulomb collision algorithm is developed for weighted particle simulations employing Monte Carlo techniques. Charged particles within a given spatial grid cell are pair-wise scattered, explicitly conserving momentum and implicitly conserving energy. A similar algorithm developed by Takizuka and Abe (1977) conserves momentum and energy provided the particles are unweighted (each particle representing equal fractions of the total particle density). If applied as is to simulations incorporating weighted particles, the plasma temperatures equilibrate to an incorrect temperature, as compared to theory. Using the appropriate pairing statistics, a Coulomb collision algorithm is developed for weighted particles. The algorithm conserves energy and momentum and produces the appropriate relaxation time scales as compared to theoretical predictions. Such an algorithm is necessary for future work studying self-consistent multi-species kinetic transport.

Miller, Ronald H.↗