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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 289 records · Page 16

Electrolyte Vapor Induced Passivation and Transition Metal Redox on Electrode Active Materials

The gaseous environment that battery electrodes are exposed to is critical to their electrochemical performance, and yet, the impact of vapor-phase components in the glovebox is relatively unexplored. In this study, we examine how the surface of Li 4 Ti 5 O 12 and LiFePO 4 composite electrodes evolve upon exposure to 1 M LiPF 6 in ethylene carbonate:dimethyl carbonate electrolyte vapors in an argon-filled glovebox. Spatially resolved X-ray photoemission electron microscopy and X-ray photoelectron spectroscopy reveal that even brief (15 minutes) contact with electrolyte vapor initiates the formation of a LiF film and changes the oxidation state of transition metals at the particle surface. Notably, these modifications occur selectively on active material particles and not on binder or conductive carbon, underscoring the specificity of vapor-induced reactions. Prolonged exposure to electrolyte vapor over the course of 1 week yields thicker, more chemically complex interphases containing both LiF and lithium oxyfluorophosphate species (Li x PO y F z ). Subsequent electrochemical testing shows that vapor-induced passivation layers influence first cycle capacities, lithium (de)insertion overpotentials, and charge-transfer resistance values. In conclusion, these results indicate that vapor–electrode interactions may be a source of variability in electrochemical behavior over time and suggest that other, more reactive electrode materials may also be susceptible to interactions with electrolyte vapor.

36 MATERIALS SCIENCE↗

Chemical modification of semiconductor surfaces

Results of research on the chemical modification of TiO2 powders in the gas phase and the examination of the modified powders by infrared absorption spectroscopy are comprehensively summarized. The range of information obtainable by IR spectroscopy of chemically modified semiconductors, and a definition of the optimum reaction conditions for synthesizing a monolayer of methylsilanes using vapor phase reaction conditions were considered.

Finklea, H. O.↗

Volatiles on satellites of the outer solar system

Molecules of cosmochemically abundant elements can act as volatiles and hence play a dominant role in the climatic and surficial evolution of solid bodies. Examples on terrestrial planets are H2O on Earth and H2O and CO2 on Mars. Analogous processes in the outer solar system focussing on CH4, its associated hydrocarbons, and N2 on Titan and Triton, the large moons of Saturn and Neptune were explored. A kilometer-deep C2H6-CH4 ocean was proposed for the surface of Titan to reconcile data on the lower atmosphere with understanding of the photochemical conversion of methane to heavier hydrocarbons. If such ocean exists, then it has dissolved in it an amount of N2 equal to the present atmospheric abundance. Since N2 contributes with CH4 a substantial greenhouse effect, the atmospheric physical and chemical characteristics are strongly coupled to those of the ocean, which change with time as methane is photolyzed in the stratosphere. Some relationship exists to the runaway greenhouse model for primordial Venus and the possible climatic implications of the buffering of Earth's atmospheric CO2 by the oceans. Two important diagnostics, measurable in Titan's atmosphere, of the conditions under which icy satellites formed are the abundances of noble gases and the CHd/CH4 radio. Both of these indicators have been altered during the evolution of Titan's surface-atmosphere system, the former by interaction with the ocean and the latter by progressive photolysis of methane into heavier hydrocarbons. The physical state and composition of volatiles on the surface of Triton is controversial, but plausibly could include CH4 N2 and perhaps CO. If condensed CH4 and N2 are widespread, their transformation to and from the vapor phase dominates the surface energy balance with sunlight. The extreme seasonal modulation of subsolar latitude on Triton is thus primarily expressed by volatile transport rather than large teperature changes, with possibly drastic observational consequences. The presence of two volatile species differing greatly in their vapor pressures make Triton a crude analog of Mars. Triton might be more appropriately regarded as a deep-freeze version of Titan.

Lunine, J. I.↗

Onset conditions for gas phase reaction and nucleation in the CVD of transition metal oxides

A combined experimental/theoretical study is presented of the onset conditions for gas phase reaction and particle nucleation in hot substrate/cold gas CVD of transition metal oxides. Homogeneous reaction onset conditions are predicted using a simple high activation energy reacting gas film theory. Experimental tests of the basic theory are underway using an axisymmetric impinging jet CVD reactor. No vapor phase ignition has yet been observed in the TiCl4/O2 system under accessible operating conditions (below substrate temperature Tw = 1700 K). The goal of this research is to provide CVD reactor design and operation guidelines for achieving acceptable deposit microstructures at the maximum deposition rate while simultaneously avoiding homogeneous reaction/nucleation and diffusional limitations.

Collins, J.↗

A Study of Nucleate Boiling with Forced Convection in Microgravity

Boiling is a rather imprecise term applied to the process of evaporation in which the rate of liquid-vapor phase change is large. In seeking to determine the role and significance of body forces on the process, of which buoyancy or gravity is just one agent, it becomes necessary to define the term more precisely. It is generally characterized by the formation and growth of individual vapor bubbles arising from heat transfer to the liquid, either at a solid/liquid or liquid/liquid interface, or volumetrically. The terms 'bubble' boiling and 'nucleate' boiling are frequently used, in recognition of the interactions of surface tension and other forces in producing discrete bubbles at distinctive locations (although not always). Primary considerations are that evaporation can occur only at existing liquid-vapor interfaces, so that attention must be given to the formation of an interface (the nucleation process), and that the latent heat for this evaporation can come only from the superheated liquid, so that attention must also be given to the temperature distributions in the liquid.

Merte, Herman, Jr.↗

Gas core reactor concepts and technology - Issues and baseline strategy

Results of a research program including phenomenological studies, conceptual design, and systems analysis of a series of gaseous/vapor fissile fuel driven engines for space power platforms and for thermal and electric propulsion are reviewed. It is noted that gas and vapor phase reactors provide the path for minimum mass in orbit and trip times, with a specific impulse from 1020 sec at the lowest technololgical risk to 5200 sec at the highest technological risk. The discussion covers various configurations of gas core reactors and critical technologies and the nuclear vapor thermal rocket engine.

Diaz, Nils J.↗

Numerical Modeling of Crystal of ZnSe by Physical Vapor Transport - Towards a more Comprehensive Formulations

Crystal growth from the vapor phase has various advantages over melt growth. The main advantage is from a lower processing temperature which makes the process more amenable in instances where the melting temperature of the crystal is high. Other benefits stem from the inherent purification mechanism in the process due to differences in the vapor pressures of the native elements and impurities, and the enhanced interfacial morphological stability during the growth process. Further, the implementation of PVT growth in closed ampoules affords experimental simplicity with minimal needs for complex process control which makes it an ideal candidate for space investigations in systems where gravity tends to have undesirable effects on the growth process. Bulk growth of wide band gap II-VI semiconductors by physical vapor transport has been developed and refined over the past several years at NASA MSFC. Results from a modeling study of PVT crystal growth of ZnSe are reported in this paper. The PVT process is numerically investigated using both two-dimensional and fully three-dimensional formulation of the governing equations and associated boundary conditions. Both the incompressible Boussinesq approximation and the compressible model are tested to determine the influence of gravity on the process and to discern the differences between the two approaches. The influence of a residual gas is included in the models. The results show that both the incompressible and compressible approximations provide comparable results and the presence of a residual gas tends to measurably reduce the mass flux in the system. Detailed flow, thermal and concentration profiles will be provided in the final manuscript along with computed heat and mass transfer rates. Comparisons with the 1-D model will also be provided. The effect of gravity on the process from numerical computations shows subtle effects although experimental evidence from vertically and horizontally grown samples show dramatic evidence of gravitational effects. The shortcomings of the problem formulation will be discussed and a framework will be provided leading up towards a more comprehensive model of PVT systems.

Ramachandran, N.↗

Crystal Growth of ZnSe by Physical Vapor Transport: A Modeling Study

Crystal growth from the vapor phase has various advantages over melt growth. The main advantage is from a lower processing temperature which makes the process more amenable in instances where the melting temperature of the crystal is high. Other benefits stem from the inherent purification mechanism in the process due to differences in the vapor pressures of the native elements and impurities, and the enhanced interfacial morphological stability during the growth process. Further, the implementation of Physical Vapor Transport (PVT) growth in closed ampoules affords experimental simplicity with minimal needs for complex process control which makes it an ideal candidate for space investigations in systems where gravity tends to have undesirable effects on the growth process. Bulk growth of wide band gap II-VI semiconductors by physical vapor transport has been developed and refined over the past several years at NASA MSFC. Results from a modeling study of PVT crystal growth of ZnSe arc reported in this paper. The PVI process is numerically investigated using both two-dimensional and fully three-dimensional formulation of the governing equations and associated boundary conditions. Both the incompressible Boussinesq approximation and the compressible model are tested to determine the influence of gravity on the process and to discern the differences between the two approaches. The influence of a residual gas is included in the models. The preliminary results show that both the incompressible and compressible approximations provide comparable results and the presence of a residual gas tends to measurably reduce the mass flux in the system. Detailed flow, thermal and concentration profiles will be provided in the final manuscript along with computed heat and mass transfer rates. Comparisons with the 1-D model will also be provided.

Ramachandran, Narayanan↗

Crystal Growth by Physical Vapor Transport: Experiments and Simulation Dynamics

Crystal growth from the vapor phase has various advantages over melt growth. The main advantage is from a lower processing temperature, which makes the process more amenable in instances where the melting temperature of the crystal is high. Other benefits stem from the inherent purification mechanism in the process due to differences in the vapor pressures of the native elements and impurities, and the enhanced interfacial morphological stability during the growth process. Further, the implementation of PVT growth in closed ampoules affords experimental simplicity with minimal needs for complex process control, which makes it an ideal candidate for space investigations in systems where gravity tends to have undesirable effects on the growth process. Bulk growth of wide band gap II-VI semiconductors by PVT has been developed and refined over the past several years at NASA MSFC. A new modeling approach for PVT has also been recently formulated and its validation and testing is the main objective of this work.

Ramachandran, N.↗

Examining Metasomatism in Low fO2 Environments: Exploring Sulfidation Reactions in Various Planetary Bodies

Hydrothermal systems are common on Earth in a variety of tectonic environments and at different temperature and pressure conditions. These systems are commonly dominated by H2O, and they are responsible for element transport and the production of ore deposits. Unlike the Earth (fO2~FMQ), many other planetary bodies (e.g., Moon and asteroids) have fO2 environments that are more reduced (IW+/-2), and H2O is not the important solvent responsible for element transport. One example of a texture that could result from element transport and metasomatism, which appears to occur on numerous planetary bodies, is sulfide-silicate intergrowths. These subsolidus assemblages are interpreted to form as a result of sulfidation reactions from a S-rich fluid phase. The composition of fluids may vary within and among parent bodies and could be sourced from magmatic (e.g. Moon) or impact processes (e.g. HED meteorites and Moon). For example, it has been previously demonstrated on the Moon that the interaction of olivine with a hydrogen- and sulfur-bearing vapor phase altered primary mineral assemblages, producing sulfides (e.g. troilite) and orthopyroxene. Formation of these types of "sulfidation" assemblages can be illustrated with the following reaction: Fe2SiO4(ol) + 1/2 S(2 system) = FeS(troi)+ FeSiO3(opx) + 1/2 O2 system. The products of this reaction, as seen in lunar rocks, is a vermicular or "worm-like" texture of intergrown orthopyroxene and troilite. Regardless of the provenance of the S-bearing fluid, the minerals in these various planetary environments reacted in the same manner to produce orthopyroxene and troilite. Although similar textures have been identified in a variety of parent bodies, a comparative study on the compositions and the origins of these sulfide-silicate assemblages has yet to be undertaken. The intent of this study is to examine and compare sulfide-silicate intergrowths from various planetary bodies to explore their petrogenesis and examine the nature of low fO2 (IW+/-2) element migration and sulfidation reactions.

Srinivasan, P.↗

Modeling Self-Pressurization and Spray Bar Pressure Control of A Cryogenic Storage Tank in Normal Gravity

This paper presents computational fluid dynamics (CFD) models for simulating self-pressurization and spray-bar pressure control processes in a large-scale liquid hydrogen storage tank under normal gravity conditions. For self-pressurization, the model employs the kinetics-based Schrage equation alongside the volume-of-fluid (VOF) method to account for interfacial mass transfer. The CFD predictions of pressure and temperature are compared with experimental data from the Multipurpose Hydrogen Test Bed (MHTB) experiment, and the predicted interfacial mass transfer rates are also presented. A CFD model simulating pressure control using a spray bar has also been developed. An Eulerian-Lagrangian approach models the interactions between discrete droplets and the continuous ullage (vapor) phase. The spray model is coupled with the VOF method by tracking droplets in the ullage and removing them when they reach the liquid interface. The T-sat model calculates droplet-ullage heat and mass transfer, where droplets warm up to the saturation temperature corresponding to the ullage vapor pressure before evaporating while remaining at the saturation temperature. The evolution of tank pressure, vapor temperature, and liquid temperature predicted by the CFD model is validated against data from the MHTB spray-bar mixing experiment. Overall, the CFD models agree with experimental data, demonstrating their capability to simulate self-pressurization and pressure control processes in large-scale cryogenic storage tanks. These models can be valuable tools for designing and optimizing cryogenic fluid management systems in future applications.

Computational Fluid Dynamics↗

Modeling Self-Pressurization and Spray Bar Pressure Control of A Cryogenic Storage Tank in Normal Gravity

This paper presents computational fluid dynamics (CFD) models for simulating self-pressurization and spray-bar pressure control processes in a large-scale liquid hydrogen storage tank under normal gravity conditions. For self-pressurization, the model employs the kinetics-based Schrage equation alongside the volume-of-fluid (VOF) method to account for interfacial mass transfer. The CFD predictions of pressure and temperature are compared with experimental data from the Multipurpose Hydrogen Test Bed (MHTB) experiment, and the predicted interfacial mass transfer rates are also presented. A CFD model simulating pressure control using a spray bar has also been developed. An Eulerian-Lagrangian approach models the interactions between discrete droplets and the continuous ullage (vapor) phase. The spray model is coupled with the VOF method by tracking droplets in the ullage and removing them when they reach the liquid interface. The T-sat model calculates droplet-ullage heat and mass transfer, wherein droplets warm up to the saturation temperature corresponding to the ullage vapor pressure before evaporating while remaining at the saturation temperature. The evolution of tank pressure, vapor temperature, and liquid temperature predicted by the CFD model is validated against data from the MHTB spray-bar mixing experiment. Overall, the CFD models agree with experimental data, demonstrating their capability to simulate self-pressurization and pressure control processes in large-scale cryogenic storage tanks. These models can be valuable tools for designing and optimizing cryogenic fluid management systems in future applications.

Self-Pressurization↗

Multi-dimensional analysis of combustion instabilities in liquid rocket motors

A three-dimensional analysis of combustion instabilities in liquid rocket engines is presented based on a mixed finite difference/spectral solution methodology for the gas phase and a discrete droplet tracking formulation for the liquid phase. Vaporization is treated by a simplified model based on an infinite thermal conductivitiy assumption for spherical liquid droplets of fuel in a convective environment undergoing transient heating. A simple two parameter phenomenological combustion response model is employed for validation of the results in the small amplitude regime. The computational procedure is demonstrated to capture the phenomena of wave propagation within the combustion chamber accurately. Results demonstrate excellent amplitude and phase agreement with analytical solutions for properly selected grid resolutions under both stable and unstable operating conditions. Computations utilizing the simplified droplet model demonstrate stable response to arbitrary pulsing. This is possibly due to the assumption of uniform droplet temperature which removes the thermal inertia time-lag response of the vaporization process. The mixed-character scheme is sufficiently efficient to allow solutions on workstations at a modest increase in computational time over that required for two-dimensional solutions.

Grenda, Jeffrey M.↗

Modeling of mechanical properties of II-VI materials

This paper reviews some new developments in the theory of alloy correlations, order-disorder transitions, and solidus phase-transition curves. It is argued that semiconductor alloys are never truly random, and the various phenomena that drive deviations from random arrangements are introduced. Likely consequences of correlations on the ability to fine-tune the lattice match of epitaxial layers to substrates, on vacancy formation, on diffusion, and on vapor-phase crystal growth are discussed. Examples are chosen for the alloys Hg(1-x)Cd(x)Te, Hg(1-x)Zn(x)Te, Cd(1-y)Zn(y)Te, and CdSe(1-y)Te(y).

Sher, A.↗

Infrared spectra of crystalline phase ices condensed on silicate smokes at T less than 20 K

Infrared spectra of H2O, CH3OH, and NH3 condensed at T less than 20 K on amorphous silicate smokes reveal that predominantly crystalline phase ice forms directly on deposit. Spectra of these molecules condensed on aluminum substrates at T less than 20 K indicate that amorphous phase ice forms. On aluminum, crystalline phase H2O and CH3OH are formed by annealing amorphous deposits to 155 K and 130 K, respectively (or by direct deposit at these temperatures); crystalline NH3 is formed by direct deposit at 88 K. Silicate smokes are deposited onto aluminum substrates by evaporation of SiO solid or by combustion of SiH4 with O2 in flowing H2 followed by vapor phase nucleation and growth. Silicate smokes which are oxygen-deficient may contain active surface sites which facilitate the amorphous-to-crystalline phase transition during condensation. Detailed experiments to understand the mechanism are currently in progress. The assumption that amorphous phase ice forms routinely on grains at T less than 80 K is often used in models describing the volatile content of comets or in interpretations of interstellar cloud temperatures. This assumption needs to be reexamined in view of these results.

Moore, Marla H.↗

EPCAPE-PT-LANL Measurements: Humidified Cavity Attenuated Phase Shift Spectroscopy

Coastal cities offer a unique environment for studying aerosol-cloud interactions and the effects of urban emissions on cloud properties. As part of the Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE), the Partitioning Thrust by Los Alamos National Laboratory (EPCAPE-PT-LANL) was conducted. Our campaign focused on measuring the optical and chemical properties of aerosols and their interactions within marine stratocumulus clouds in La Jolla, California. EPCAPE-PT-LANL enhances the primary goals of EPCAPE through innovative observations of vapor-phase transitions between aerosols and cloud droplets, the impact of black carbon on aerosol-cloud dynamics, and the effects of cloud processing on aerosol optical properties. Instrument: Humidified Cavity Attenuated Phase Shift Particulate Matter Single Scattering Albedo (H-CAPS-PMSSA, Aerodyne Inc) Data Notes: The scattering truncation correction was not applied to Bsca. The Bext needs no correction. Files: data_10sec_CAPS.csv, data_10min_CAPS.csv Header: - Bext_wet_CAPS_450nm[1/Mm]: Wet aerosol extinction coefficient measured at 450 nm by the CAPS, in inverse megameters (Mm⁻¹). - Bsca_wet_CAPS_450nm[1/Mm]: Wet aerosol scattering coefficient measured at 450 nm by the CAPS, in inverse megameters (Mm⁻¹). - Temp_wet_CAPS[K]: Temperature inside the wet CAPS measurement chamber, in Kelvin. - Bext_dry_CAPS_450nm[1/Mm]: Dry aerosol extinction coefficient measured at 450 nm by the CAPS, in inverse megameters (Mm⁻¹). - Bsca_dry_CAPS_450nm[1/Mm]: Dry aerosol scattering coefficient measured at 450 nm by the CAPS, in inverse megameters (Mm⁻¹). - Temp_dry_CAPS[K]: Temperature inside the dry CAPS measurement chamber, in Kelvin. - Wet_RH_preCAPS[%]: Relative humidity before entering the wet CAPS, in percent. - Wet_RH_postCAPS[%]: Relative humidity after exiting the wet CAPS, in percent. - Humidifier_RH_CAPS[%]: Relative humidity inside the humidifier used with the CAPS, in percent. - dualCAPS_inlet_RH[%]: Relative humidity at the inlet of the dual (wet/dry) CAPS setup, in percent. - Wet_Temp_preCAPS[C]: Temperature before entering the wet CAPS, in degrees Celsius. - Wet_Temp_postCAPS[C]: Temperature after exiting the wet CAPS, in degrees Celsius. - Humidifier_Temp[C]: Temperature inside the humidifier used with the CAPS, in degrees Celsius. - dualCAPS_inlet_Temp[C]: Temperature at the inlet of the dual (wet/dry) CAPS setup, in degrees Celsius. - Zero_dry_CAPS: 1 is a calibration check for the dry CAPS to ensure zero reading under filter air conditions. - Zero_wet_CAPS: 1 is a calibration check for the wet CAPS to ensure zero reading under filter air conditions. - CVI_Flag[bool]: A boolean flag indicating whether the Counterflow Virtual Impactor (CVI) was active (true) or inactive (false) during the measurement.

54 ENVIRONMENTAL SCIENCES↗

Growth morphology with anisotropic surface kinetics

The morphological evolution of crystals growing from an incongruent vapor phase is studied using a Monte Carlo model, and the full range of growth morphologies is recovered. The diffusion in the bulk nutrient and the anisotropy in the interface kinetics are morphologically destabilizing and stabilizing, respectively. For a given set of simulation parameters and lattice symmetries there is a critical size, which scales linearly with the mean free path in the vapor, beyond which a crystal cannot retain its stable, macroscopically faceted growth shape. Surface diffusion stabilizes faceted growth on the shorter scale of the mean surface diffusion length. In simulations with a uniform drift superimposed on the random walk nutrient transport, crystal faces oriented toward the drift show enhanced morphological stability compared to the purely diffusive situation. Rotational drifts with periodic reversal of direction are morphologically stabilizing for all crystal facets.

Xiao, Rong-Fu↗

EPCAPE-PT-LANL Measurements: Gas Monitors

Coastal cities offer a unique environment for studying aerosol-cloud interactions and the effects of urban emissions on cloud properties. As part of the Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE), the Partitioning Thrust by Los Alamos National Laboratory (EPCAPE-PT-LANL) was conducted. Our campaign focused on measuring the optical and chemical properties of aerosols and their interactions within marine stratocumulus clouds in La Jolla, California. EPCAPE-PT-LANL enhances the primary goals of EPCAPE through innovative observations of vapor-phase transitions between aerosols and cloud droplets, the impact of black carbon on aerosol-cloud dynamics, and the effects of cloud processing on aerosol optical properties. Instrument: G2401 Gas Concentration Analyzer (Picarro) Data Notes: The Picarro G2401 gas concentration analyzer provides simultaneous, precise measurement of carbon monoxide (CO), carbon dioxide (CO2), methane (CH4) at parts-per-billion (ppb), and water (H2O) vapor at parts per-million (ppm) sensitivity with negligible drift for atmospheric science, air quality, and emissions quantification. Header: - CO[ppm]: Concentration of carbon monoxide (CO) measured at the time of sampling, expressed in parts per million (ppm). - CO2[ppm]: Concentration of carbon dioxide (CO2) measured at the time of sampling, expressed in parts per million (ppm). - CH4[ppm]: Concentration of methane (CH4) measured at the time of sampling, expressed in parts per million (ppm). - H2O[%]: Water vapor content in the air at the time of the measurement, expressed as a percentage

54 ENVIRONMENTAL SCIENCES↗