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

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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
NASA NTRS1983

On photochemical heating of cometary comae - The cases of H2O and CO-rich comets

It is found that the effect of energy addition due to photochemical processes in the cometary coma on the heating and accelerating of the expanding neutral gas is limited by the kinematic property of the energy transfer from the energetic fragments to the bulk flow. The effective scale length of the photochemical zone for an H2O comet is estimated to be only 10% of the dimension of the collision region due to the large mass ratio of H atom and H2O molecule. When this physical property is taken into consideration, the H2O gas is found to be expanding at a highly supersonic speed. In addition, it is shown that the addition of a mixture of CO and/or CO2 molecules in a medium-bright comet with total production rate of 10 to the 29th molecules/s would not change this conclusion since the photodissiation length scales of these molecules are a factor of 10-30 larger than that of the H2O molecules. Thus, most of the CO and CO2 molecules will be dissociated outside of the collision zone without depositing the excess kinetic energy to the neutral atmosphere. However, if the gas production rate is controlled by CO or CO2, the dimension of the collision zone of a CO comet at 1 AU will be increased by a factor of seven. The photochemical heating due to CO dissociation would thus be more effective, causing the atmospheric flow to be weakly supersonic. It is concluded that the neutral gas outflows from H2O comets and CO comets could be substantially different.

Ip, W.-H.↗
NASA NTRS1976

Physical processes in comets

The paper discusses physical processes in comets which involve solar and nuclear radial forces that affect the motions of gases and icy grains, gas-phase chemistry very close to the nuclei of large comets near the sun, sublimation of icy grains, dissociation of parent molecules into radicals and of radicals into atoms, and ionization by sunlight and collisions. The composition and dimensions of nuclei are examined along with variations in intrinsic brightness, the nature of volatiles, gas production rates in the coma, characteristics of icy grains in the coma, and the structure of streamers, ion tails, and dust tails. The structure of the coma is described in detail on the basis of spectroscopic observations of several comets. The origin of comets is briefly reviewed together with the relation of comets to earth, the interplanetary complex, and the interstellar medium. Desirable future observations are noted, especially by space missions to comets.

Whipple, F. L.↗
NASA NTRS1991

Observations of forbidden Si II (35 microns) and Si I (25 microns) in Orion - Evidence of a wind shock near IRc2

Forbidden Si II and Si I line emission from Orion's BN-KL was measured using a cryogenic grating spectrometer aboard NASA's Kuiper Airborne Observatory. It is believed that the bulk of the forbidden Si II emission in Orion originates in photodissociated gas at the interface between the H II region and its parent molecular cloud. There is, however, a twofold enhancement in forbidden Si II emission near IRc2, which is attributed to fast dissociative J-shock where the wind from IRc2 impact slower moving material. Model fits suggest a silicon gas-phase depletion near ITc2 of 0.3-1.0 relative to solar. The spatial distribution of the forbidden Si II emission has a centralized peak.

Haas, Michael R.↗
DOE OSTI2024

Deuterium Permeation Through a Self-Supported Palladium-Silver Membrane in Helium Gas Mixtures

Palladium membranes and membrane reactors can separate and purify tritium from impurities in the plasma exhaust processing system for the fusion energy fuel cycle. Membranes can also act as a continuous separation method to remove tritium from helium streams in the breeder blanket tritium extraction system, such as from the purge gas of solid breeders. To investigate the potential of these membranes for these applications, we performed a deuterium permeation campaign with a self-supported palladium-silver (Pd-25Ag wt%) tube of 0.15 m length, 76 µ m wall thickness, and 3.0 mm inner diameter. A gas mixture of 3.95% D 2 and a balance of He was delivered to the inside of the tube and D permeated radially outwards through the membrane into a vacuum chamber. Permeation experiments were conducted at 300 ° C, 350 ° C, 400° C, and 450°C, from 100 to 1000 sccm total flow rate, and with total pressures of 90, 150, 190, and 250 kPa. Further, deuterium permeation was consistently lower than predicted from diffusion-limited permeation models, thus we developed a transport model that included gas-phase mass transfer and surface reactions to model experimental results. The dissociation constant was optimized to fit the developed model to experimental data.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

In-Situ Laser Diagnostics to Understand Plasma-Surface Interactions in Titanium Thin Film Deposition

During the current project period the following tasks were completed: (1) We demonstrated the feasibility of a new way of measuring CH3 radicals in a plasma environment using a single, femtosecond (fs) pulsed laser for the first time, in a CH4 + Ar flow. A single fs pulsed Ti:Sa laser was split into two beams and with beam conversion using crystals we generatedtwo beams of 275 nm and 205 nm. The 275 nm was used to predissociate the CH3 radicals to CH2+H, followed by 205 nm Two Photon Laser Induced Fluorescence (TALIF) detection of H atoms, with a 11 ns delay from 275 nm predissociation pulse. (2) We demonstrated preliminary CH3 concentration measurements with spatial (< 100 µm) and time resolution (< 10 ns) by image processing of H and Kr TALIF signal images. (3) The methodology to quantify CH3 concentrations was developed. (4) Preliminary measurements of laser dissociation cross sections for CH4 and CH3 to (CH3+H), and (CH2+H), respectively, were conducted. (5) 275 nm laser dissociation of CH4 is a multiphoton process, and the CH4 dissociation cross section is a more sensitive function of the laser pulse energy than CH4 concentration. In the coming months, we will make more precise measurements of the dissociation cross sections, 𝑘275, 𝐶𝐻4 and 𝑘275, 𝐶𝐻3, by varying the laser energy while keeping the flow composition and conditions constant. This will enable more precise quantification of CH3 radical concentrations. More detailed measurements of CH3 radicals will be conducted in the following months of 2025 (Sept-Dec) in a Titanium Isopropoxide (TIP) + H2 + Ar flow meant for pure phase Ti thin film deposition by Chemical Vapor Deposition (CVD). More precise measurements of 275 nm laser dissociation cross sections for CH4 (to CH3 + H) and CH3 (to CH2 + H) will be conducted in the future. Detailed 275 nm laser predissociation cross sections for CH4 and CH3 dissociation to (CH3+H), and (CH2+H), respectively, as a function of gas heating, plasma power, and laser pulse energy will be evaluated. This will enable quantification of CH3 concentrations in the precursor flow over a substrate with time and spatial resolution. Comparison of the concentrations with 2D numerical simulations can lead to understanding of plasma surface interactions during pure metallic Ti thin film deposition using environmentally safer non-halogen TIP precursor. Flow conditions for pure Ti thin film deposition using non-halogen precursor (TIP) will be identified in the following months.

Uddi, Mruthunjaya [Advanced Cooling Technologies, ↗
NASA NTRS1971

A thin-shock-layer solution for nonequilibrium, inviscid hypersonic flows in earth, Martian, and Venusian atmospheres

An approximate inverse solution is presented for the nonequilibrium flow in the inviscid shock layer about a vehicle in hypersonic flight. The method is based upon a thin-shock-layer approximation and has the advantage of being applicable to both subsonic and supersonic regions of the shock layer. The relative simplicity of the method makes it ideally suited for programming on a digital computer with a significant reduction in storage capacity and computing time required by other more exact methods. Comparison of nonequilibrium solutions for an air mixture obtained by the present method is made with solutions obtained by two other methods. Additional cases are presented for entry of spherical nose cones into representative Venusian and Martian atmospheres. A digital computer program written in FORTRAN language is presented that permits an arbitrary gas mixture to be employed in the solution. The effects of vibration, dissociation, recombination, electronic excitation, and ionization are included in the program.

Grose, W. L.↗
NASA NTRS2003

Theoretical Studies of Chemical Reactions following Electronic Excitation

The use of multi-configurational wave functions is demonstrated for several processes: tautomerization reactions in the ground and excited states of the DNA base adenine, dissociation of glycine molecule after electronic excitation, and decomposition/deformation of novel rare gas molecules HRgF. These processes involve bond brealung/formation and require multi-configurational approaches that include dynamic correlation.

Chaban, Galina M.↗
NASA NTRS2003

Real Gas Effects on the Performance of Hydrocarbon-fueled Pulse Detonation Engines

This paper presents results for a single-pulse detonation tube wherein the effects of high temperature dissociation and the subsequent recombination influence the sensible heat release available for providing propulsive thrust. The study involved the use of ethylene and air at equivalence ratios of 0.7 and 1.0. The real gas effects on the sensible heat release were found to be significantly large so as to have an impact on the thrust, impulse and fuel consumption of a PDE.

Povinelli, Louis A.↗
NASA NTRS1993

Thermophysical properties of gas phase uranium tetrafluoride

Thermophysical data of gaseous uranium tetrafluoride (UF4) are theoretically obtained by taking into account dissociation of molecules at high temperatures (2000-6000 K). Determined quantities include specific heat, optical opacity, diffusion coefficient, viscosity, and thermal conductivity. A computer program is developed for the calculation.

Watanabe, Yoichi↗
NASA NTRS1995

Numerical Simulations of High Enthalpy Pulse Facilities

Axisymmetric flows within shock tubes and expansion tubes are simulated including the effects of finite rate chemistry and both laminar and turbulent boundary layers. The simulations demonstrate the usefulness of computational fluid dynamics for characterizing the flows in high enthalpy pulse facilities. The modeling and numerical requirements necessary to simulate these flows accurately are also discussed. Although there is a large body of analysis which explains and quantifies the boundary layer growth between the shock and the interface in a shock tube, there is a need for more detailed solutions. Phenomena such as thermochemical nonequilibrium. or turbulent transition behind the shock are excluded in the assumptions of Mirels' analysis. Additionally there is inadequate capability to predict the influence of the boundary layer on the expanded gas behind the interface. Quantifying the gas in this region is particularly important in expansion tubes because it is the location of the test gas. Unsteady simulations of the viscous flow in shock tubes are computationally expensive because they must follow features such as a shock wave over the length of the facility and simultaneously resolve the small length scales within the boundary layer. As a result, efficient numerical algorithms are required. The numerical approach of the present work is to solve the axisymmetric gas dynamic equations using an finite-volume formulation where the inviscid fluxes are computed with a upwind TVD scheme. Multiple species equations are included in the formulation so that finite-rate chemistry can be modeled. The simulations cluster grid points at the shock and interface and translate this clustered grid with these features to minimize numerical errors. The solutions are advanced at a CFL number of less than one based on the inviscid gas dynamics. To avoid limitations on the time step due to the viscous terms, these terms are treated implicitly. This requires a block tri-diagonal matrix inversion along each line of cells normal to the wall. The cost of this inversion is more than offset by the larger allowable time step. The source terms representing the finite-rate chemical kinetics are also treated implicitly. An algebraic turbulence model for compressible flow is used. The flow in a low pressure shock tube is computed and the results are compared with Mirels'analysis. The driven gas is nitrogen at 70 Pa, and the incident shock speed is approximately 2.9 km/sec so that there is little dissociation. The simulations include a laminar boundary layer and are run until the limiting flow regime is achieved. At this limit, the shock and interface travel at the same velocity because the amount of driven gas between these two features remains the same: the mass flow across the shock is equal to the mass of gas being entrained at the interface by the boundary layer. Simulations with several grids are presented to establish the grid independence of the solution, Good agreement is achieved between Mirels' correlations and the computations. This is expected since the flow conditions are chosen to be consistent with the assumptions used in Mirels' analysis. This comparison adds credibility to the numerical approach and highlights some of the differences between the theory and the detailed simulations. In addition, simulations of the HYPULSE expansion tube are presented for two operating conditions and the computations are compared to experimental data. The operating gas for both cases is nitrogen. One test condition is at a total enthalpy of 15.2 MJ/Kg and a relatively low pressure of 2 kPa. This case is characterized by a laminar boundary layer and significant chemical nonequilibrium. in the acceleration gas. The second test condition is at a total enthalpy of 10.2 MJ/Kg and a pressure of 38 kPa and is characterized by a turbulent boundary layer. The simulations compare well with experiment and reveal that the nonuniformity in pressure observed during the test time is related to variations in the boundary layer displacement thickness.

Wilson, Gregory J.↗
DOE OSTI2020

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science

The abundance of inexpensive, natural gas has transformed the energy landscape, whereby revealing new possibilities for sustainable chemical technologies or impacting those that have relied on traditional fossil fuels. The primary component, methane, is underutilized and wastefully exhausted, leading to anthropogenic global warming. Historically, the manipulation of methane remained “ clavis aurea ,” an insurmountable yet rewarding challenge and thus the focus of intense research. This is primarily due to an inability to dissociate C–H bonds in methane selectively, which requires a high energy penalty and is an essential prerequisite for the direct conversion of methane into a large set of value-added products. The discovery of such processes would promise an energy gainful use of natural gas benefiting several essential chemical processes associated with C1 chemistry. This first C–H bond dissociation step of the methane molecule appears in numerous catalytic mechanisms as the rate-determining step or most essential barrier sequence for all subsequent steps that follow in the production of C–C, C–O, or C x –H y –O z bonds found in value added products. A main goal is to catalytically reduce the energy barrier for the first C–H bond dissociation to be able to achieve the activation of methane at low or moderate temperatures. As such there is great value in understanding the fundamental nature of the active sites responsible for bond breaking or formation and thus be able to facilitate better control of this chemistry, leading to the development of new technologies for fuel production and chemical conversion. Surface science studies offer enhanced perspectives for a careful manipulation of bonds over the last layer atoms of catalyst surfaces, an essential factor for the design of atomically precise catalysts and unravelling of the reaction mechanism. With the advent of new surface imaging, spectroscopy, and in situ tools, it has been possible to decipher the surface chemistry of complex materials systems and further our understanding of atomic active sites on the surfaces of metals, oxides, and carbides or metal–oxide and metal–carbide interfaces. The once considered near impossible step of C–H bond activation is now observed at low temperatures with high propensity over a collection of oxide, metal–oxide, and metal–carbide systems in a conventional or inverse configuration (oxide or carbide on metal). The enabling of C–H activation at low temperature has opened interesting possibilities for the specific production of chemicals such as methanol directly from methane, a step toward facile synthesis of liquid fuels. We highlight the most recent of these results and present the key aspects of active site configurations engineered from surface science studies which enable such a simple reactive event through careful manipulation of the last surface layer of atoms found in the catalyst structure. New concepts which help in the activation and conversion of methane are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ultrafast infrared transient absorption spectroscopy of gas-phase Ni(CO) 4 photodissociation at 261 nm

Here, we employ ultrafast mid-infrared transient absorption spectroscopy to probe the rapid loss of carbonyl ligands from gas-phase nickel tetracarbonyl following ultraviolet photoexcitation at 261 nm. Here, nickel tetracarbonyl undergoes prompt dissociation to produce nickel tricarbonyl in a singlet excited state; this electronically excited tricarbonyl loses another CO group over tens of picoseconds. Our results also suggest the presence of a parallel, concerted dissociation mechanism to produce nickel dicarbonyl in a triplet excited state, which likely dissociates to nickel monocarbonyl. Mechanisms for the formation of these photoproducts in multiple electronic excited states are theoretically predicted with one-dimensional cuts through the potential energy surfaces and computation of spin–orbit coupling constants using equation of motion coupled cluster methods (EOM-CC) and coupled cluster theory with single and double excitations (CCSD). Bond dissociation energies are calculated with CCSD, and anharmonic frequencies of ground and excited state species are computed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Visualizing oxygen transport pathways during intergranular oxidation in Ni-Cr

The transport paths of O during intergranular oxidation in binary Ni-Cr were investigated. To isolate the selective oxidation of Cr, oxidation was performed with a CO/CO 2 gas mixture in which the oxygen partial pressure was kept under the NiO dissociation pressure. A combination of electron microscopy and atom probe tomography (APT) was used to study the nanometer-scale details of the passivation and penetrative intergranular oxidation processes at high-energy grain boundaries. Oxygen transport towards the terminating oxidation front is elucidated with dedicated usage of oxygen tracer exchange experiments. Secondary ion mass spectroscopy and APT support classical theories of internal oxidation, revealing preferred transport paths at the oxide/alloy interface with sub-nanometer resolution.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Triboplasma assisted chemical conversion in granular systems: a semi-analytic model

We present a semi-analytic model for a novel plasma-assisted chemical conversion pathway using triboplasmas generated in granular flows. Triboelectric charge relaxation is a well known phenomena where the potential generated from contact charging of particles exceeds the breakdown voltage of the background gas. In this work, we extend the triboelectric charge relaxation theory to include non equilibrium plasma energy and particle balance equations to predict the formation of dissociated and excited species that act as precursors to chemical conversion, for example in plasma-assisted ammonia synthesis. Our example case study with nitrogen background gas and teflon/aluminum tribomaterial system yielded high excited nitrogen species densities per collision that are comparable to current plasma-assisted conversion pathways. We also present a regime diagram for various gases where Paschen breakdown parameters are used to determine whether triboplasmas can be formed for a given effective work-function difference between two materials. Our sensitivity studies indicate particle velocity, particle radius, solids fraction and space charge effects play a critical role in overall plasma densities and excited species production.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2005

Mars Atmospheric Chemistry in Electrified Dust Devils and Storms

Laboratory studies, simulations and desert field tests all indicate that aeolian mixing dust can generate electricity via contact electrification or "triboelectricity". In convective structures like dust devils or storms, grain stratification (or charge separation) occurs giving rise to an overall electric dipole moment to the aeolian feature, similar in nature to the dipolar electric field generated in terrestrial thunderstorms. Previous simulation studies [1] indicate that this storm electric field on Mars can approach atmospheric breakdown field strength of 20 kV/m. In terrestrial dust devils, coherent dipolar electric fields exceeding 20 kV/m have been measured directly via electric field instrumentation. Given the expected electrostatic fields in Martian dust devils and storms, electrons in the low pressure CO2 gas can be energized via the electric field to values exceeding the electron dissociative attachment energy of both CO2 and H2O, resulting in the formation of new chemical products CO and O- and OH and H- within the storm. Using a collisional plasma physics model we present a calculation of the CO/O- and OH/H- reaction and production rates. We demonstrate that these rates vary geometrically with ambient electric field, with substantial production of dissociative products when fields approach breakdown levels of 20-30 kV/m.

Farrell, W. M.↗
NASA NTRS1991

Validation of chemistry models employed in a particle simulation method

The chemistry models employed in a statistical particle simulation method, as implemented in the Intel iPSC/860 multiprocessor computer, are validated and applied. Chemical relaxation of five-species air in these reservoirs involves 34 simultaneous dissociation, recombination, and atomic-exchange reactions. The reaction rates employed in the analytic solutions are obtained from Arrhenius experimental correlations as functions of temperature for adiabatic gas reservoirs in thermal equilibrium. Favorable agreement with the analytic solutions validates the simulation when applied to relaxation of O2 toward equilibrium in reservoirs dominated by dissociation and recombination, respectively, and when applied to relaxation of air in the temperature range 5000 to 30,000 K. A flow of O2 over a circular cylinder at high Mach number is simulated to demonstrate application of the method to multidimensional reactive flows.

Haas, Brian L.↗
NASA NTRS1992

Magnetic fields and radiative shocks in protogalaxies and the origin of globular clusters

The paper examines the hypothesis that globular clusters formed from gravitational instability in dense sheets of gas produced behind radiative shocks inside protogalaxies, such as those produced by the collision of subgalactic mass fragments partaking of the virial motions within the protogalaxy, in order to determine the differences which result if a magnetic field is present in the preshock medium. The MHD conservation equations are solved along with rate equations for nonequilibrium ionization, recombination, molecular formation and dissociation, and the equations of radiative transfer for steady-state shocks of velocity 300 km/s in a gas of preshock densities of 0.1-1 cu cm, and magnetic field strengths of 0.1-6 micro-G. The magnetic field is found to limit the degree of postshock compression and, thereby, to reduce the level of external radiation flux required to suppress H2 formation and cooling.

Shapiro, Paul R.↗
DOE OSTI2022

Challenges in Kinetic modeling of ammonia pyrolysis

Ammonia pyrolysis reactions have implications for its ignition and oxidation in engines and gas turbines. In the present work, the chemistry of ammonia pyrolysis is investigated by kinetic modeling and theory. Rate constants for key reactions are carefully evaluated based on available experimental and theoretical results. The high pressure limit k1,∞ for NH 2 + H (+M) &rlarr; NH 3 (+M) (R1) is calculated to be essentially the collision frequency, indicating that dissociation of ammonia in combustion processes will be at or close to the low pressure limit even at engine and gas turbine conditions. The chemical kinetic model is validated against reported shock tube measurements of NH 3 , NH 2 , and NH in ammonia pyrolysis. Predictions are in good agreement with observations for dilute conditions (≤ 0.5% NH 3 ), but the model appears to underpredict the NH 3 consumption rate at longer times in less dilute mixtures. At short reaction times, thermal dissociation of NH3, together with the NH 3 + H reaction, controls conversion. At longer times, secondary reactions involving NH 2 and NH become important due to their impact on the radical pool. Predictions become sensitive to formation and consumption of diazene (tHNNH and cHNNH). Several of the key steps in the ammonia pyrolysis mechanism are radical-radical reactions that are difficult to measure accurately and challenging to calculate theoretically, and a more comprehensive experimental characterization is desirable to support further model development.

10 SYNTHETIC FUELS↗