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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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NASA NTRS2023

Chemical Thermodynamics and the Mathematical Integration of Reaction Kinetics

Key advances in the development of numerical methods for non-reacting compressible flows have been enabled by translating physical requirements into concrete numerical guidelines, such as the satisfaction of entropy inequalities for shock-capturing techniques [Lax, Contributions to Nonlinear Functional Analysis (1971) 603-634]. In the present work, we present nonlinear numerical analysis tools that draw from Chemical Thermodynamics , the branch of Nonequilibrium Thermodynamics that deals with chemical reactions. Through Gibbs formalism, chemical thermodynamics provides a well-known theoretical expression for the chemical equilibrium constant of a reaction in terms of reduced chemical potentials. A less-known, yet extremely valuable result, due to [Krambeck, Arch. Ration. Mech. Anal. , 38 (1970) 317], states that when this expression is implemented, mass-action kinetic models are consistent with the dynamical prescriptions of the 2nd law of thermodynamics. For fixed-temperature ordinary differential equations modeling constant-volume reacting gas mixtures, this leads to a decreasing Helmholtz free energy. If the temperature is allowed to vary in accordance with conservation of energy (1st law), this leads to the statement of increasing entropy. These nonlinear prescriptions can, and should be, used to further develop temporal integration techniques for reaction kinetics. We demonstrate that Krambeck's result holds even when the equilibrium constants are approximated from data. We prove this result by constructing the implicit free energy and the implicit entropy inherent to a given approximation. This is first done for a 5-species, 17-reaction model problem for air. With this structure established, elements of discrete entropy-stability theory [Tadmor, Acta Numer. , 12 (2003) 451] are leveraged to examine the consistency of time-integration schemes with these prescriptions. Using chemical potentials, one can compute the respective contributions of the kinetics model and of the temporal scheme to free energy/entropy variations. We introduce a nonlinear-stable version of the Discontinuous-Galerkin (DG) scheme in time which shows robustness improvements over the standard linearly-stable version. Most notably, the maximum timestep that can be resolved with the nonlinearly-stable variant tends to grow with polynomial order, in contrast to the linearly-stable variant. We generalize our constructions to arbitrary systems of reversible chemical reactions, ultimately showing that the compressible reacting Euler system admits the opposite of the implicitly constructed thermodynamic entropy as a mathematical entropy . This lays important theoretical foundations towards robust scheme development [Harten, J. Comput. Phys. 49 (1983) 151-164].

STMD↗
NASA NTRS1985

Coated oxidizers for combustion stability in solid-propellant rockets

Experiments are conducted in a laboratory-scale (6.25-cm diameter) end-burning rocket motor with state-of-the-art, ammonium perchlorate hydroxy-terminated polybutadiene (HTPB), nonmetallized propellants. The concept of tailoring the stability characteristics with a small amount (less than 1 percent by weight) of COATING on the oxidizer is explored. The thermal degradation characteristics of the coat chemical are deduced through theoretical arguments on thermal diffusivity of the composite material (propellant). Several candidate coats are selected and propellants are cast. These propellants (with coated oxidizers) are fired in a laboratory-scale end-burning rocket motor, and real-time pressure histories are recorded. The control propellant (with no coating) is also tested for comparison. The uniformity of the coating, confirmed by SEM pictures and BET adsorption measurements, is thought to be an advance in technology. The frequency of bulk mode instability (BMI), the pressure fluctuation amplitudes, and stability boundaries are correlated with parameters related to the characteristic length (L-asterisk) of the rocket motor. The coated oxidizer propellants, in general, display greater combustion stability than the control (state-of-the-art). The correlations of the various parameters are thought to be new to a field filled with much uncertainty.

Helmy, A. M.↗
NASA NTRS1990

The electrochemical generation of useful chemical species from lunar materials

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Tsai, Kan J.↗
NASA NTRS1989

The electrochemical generation of useful chemical species from lunar materials

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density (i sub o) values being greater than 60mA sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent (compared to H2) for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed tha basis for the lithium oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Tsai, Kan J.↗
NASA NTRS1975

Flame stability in combusting turbulent jets

A simplified theoretical model for turbulent methane/air flames from a subscale power plant burner is developed and applied to predict the stability of flames as a function of (1) ambient atmosphere temperature and composition, (2) initial preheat temperature, and (3) percentage of external product gas recirculation. The flame model equates the rate at which mass is supplied per unit volume to the rate it is chemically reacted per unit volume using a one-step reaction and a perfectly stirred reactor (PSR). The model contains a free parameter which is evaluated by comparing the theoretical results to experimental results available in the literature. The stability results show that premixed, turbulent flames are stable over a wide equivalence ratio range if the ambient gas is air; however, if combustion products are entrained, the stability is sharply reduced.

Nelson, H. F.↗
NASA NTRS1984

Research on aviation fuel instability

Current aircraft turbine fuels do not present a significant problem with fuel thermal stability. However, turbine fuels with broadened properties or nonpetroleum derived fuels may have reduced thermal stability because of their higher content of olefins, heteroatoms, and trace metals. Moreover, advanced turbine engines will increase the thermal stress on fuels because of their higher pressure ratios and combustion temperature. In recognition of the importance of this problem, NASA Lewis is currently engaged in a broadly based research effort to better understand the underlying causes of fuel thermal degradation. The progress and status of our various activities in this area are discussed. Topics covered include: nature of fuel instability and its temperature dependence, methods of measuring the instability, chemical mechanisms involved in deposit formation, and instrumental methods for characterizing fuel deposits. Finally, some preliminary thoughts on design approaches for minimizing the effects of lowered thermal stability are briefly discussed.

Baker, C. E.↗
NASA NTRS1989

The development of an explicit thermochemical nonequilibrium algorithm and its application to compute three dimensional AFE flowfields

This study presents a three-dimensional explicit, finite-difference, shock-capturing numerical algorithm applied to viscous hypersonic flows in thermochemical nonequilibrium. The algorithm employs a two-temperature physical model. Equations governing the finite-rate chemical reactions are fully-coupled to the gas dynamic equations using a novel coupling technique. The new coupling method maintains stability in the explicit, finite-rate formulation while allowing relatively large global time steps. The code uses flux-vector accuracy. Comparisons with experimental data and other numerical computations verify the accuracy of the present method. The code is used to compute the three-dimensional flowfield over the Aeroassist Flight Experiment (AFE) vehicle at one of its trajectory points.

Palmer, Grant↗
NASA NTRS1991

Total Organic Carbon Analyzer

The development and testing of a breadboard version of a highly sensitive total-organic-carbon (TOC) analyzer are reported. Attention is given to the system components including the CO2 sensor, oxidation reactor, acidification module, and the sample-inlet system. Research is reported for an experimental reagentless oxidation reactor, and good results are reported for linearity, sensitivity, and selectivity in the CO2 sensor. The TOC analyzer is developed with gravity-independent components and is designed for minimal additions of chemical reagents. The reagentless oxidation reactor is based on electrolysis and UV photolysis and is shown to be potentially useful. The stability of the breadboard instrument is shown to be good on a day-to-day basis, and the analyzer is capable of 5 sample analyses per day for a period of about 80 days. The instrument can provide accurate TOC and TIC measurements over a concentration range of 20 ppb to 50 ppm C.

Godec, Richard G.↗
NASA NTRS1998

EOS Interdisciplinary Investigation: Observational and Modeling Studies of Radiative, Chemical, and Dynamical Interactions in the Earth's Atmosphere

A 3-dimensional model of atmospheric dynamics and photochemistry has been developed from the primitive equations in isentropic coordinates. The model extends from the upper troposphere through the middle atmosphere and is driven by observed dynamical and chemical structure in the troposphere. The model's formulation is entirely spectral: Horizontal structure is represented in terms of vector Hough functions, which explicitly partition the motion into its rotational and divergent components. This formulation enables the model's computational performance to be increased dramatically by filtering high-frequency gravity waves, which do not affect PV conservation. Vertical structure is represented in terms of eigenfunctions that follow from the primitive equations in isentropic coordinates. The model's fully spectral formulation enables scale-selective dissipation, necessary for numerical stability, to be applied at 6th order-in all 3 coordinate directions. This feature leaves all but the shortest vertical scales undamped and, consequently, allows potential vorticity and chemical tracers to be conserved quite accurately, distinctly better than in the model's layered counterpart. These dynamical features are complemented by a basic but fairly complete treatment of gas phase photochemistry, which accounts for some 48 chemical species, diurnally-varying SW absorption by O2 and O3, and LW cooling calculated via a detailed band calculation of radiative transfer. Driven by observed tropospheric structure, the 3D model reproduces observed structure in the middle atmosphere, inclusive of transport by the Brewer-Dobson circulation and accompanying chemical variations. Calculated residual motion is consistent with diabatic cooling rates, poleward transport, and descent in the polar night derived from satellite measurements of chemical tracers made from LIMS, SAGE, and UARS. The model also reproduces the observed structure of chemical species like O3, HNO3, and ClO. At the same time, it provides a respectable 3D simulation of the wintertime increase of midlatitude total ozone, as well as its geographical structure observed by Nimbus-7 TOMS. The 3D model has been used to explore the origin of diabatic upwelling in the tropical lower stratosphere, which has been related to planetary wave absorption in the winter- time stratosphere, as well as to influences from tropospheric convection at the tropical tropopause.

Salby, Murry L.↗
NASA NTRS1981

Solar Mesosphere Explorer

Five experiments and the instruments packages designed for use in studying reactions between sunlight, ozone, and other chemicals in the atmosphere as well as for determining how ozone concentrations are transported in the mesosphere are described. The spin-stabilized satellite carrying the experiments consists of an observatory module and a spacecraft bus. Powered by a solar array which charges the nickel-cadmium batteries, the satellite is to be inserted into a sun synchronous orbit by a two stage Delta 2310 launch vehicle. The mission objectives, spacecraft configurations, and various subsystems are described as well as the ground support and prelaunch operations.

Source record↗
NASA NTRS1993

Studies of Premixed Laminar and Turbulent Flames at Microgravity

The work of the Principal Investigator (PI) has encompassed four topics related to the experimental and theoretical study of combustion limits in premixed flames at microgravity, as discussed in the following sections. These topics include: (1) radiation effects on premixed gas flames; (2) flame structure and stability at low Lewis number; (3) flame propagation and extinction is cylindrical tubes; and (4) experimental simulation of combustion processes using autocatalytic chemical reactions.

Ronney, Paul D.↗
NASA NTRS1997

Plasma-Sprayed Refractory Oxide Coatings on Silicon-Base Ceramics

Silicon-base ceramics are promising candidate materials for high temperature structural applications such as heat exchangers, gas turbines and advanced internal combustion engines. Composites based on these materials are leading candidates for combustor materials for HSCT gas turbine engines. These materials possess a combination of excellent physical and mechanical properties at high temperatures, for example, high strength, high toughness, high thermal shock resistance, high thermal conductivity, light weight and excellent oxidation resistance. However, environmental durability can be significantly reduced in certain conditions such as when molten salts, H2 or water vapor are present. The oxidation resistance of silicon-base materials is provided by SiO2 protective layer. Molten salt reacts with SiO2 and forms a mixture of SiO2 and liquid silicate at temperatures above 800C. Oxygen diffuses more easily through the chemically altered layer, resulting in a catastrophic degradation of the substrate. SiC and Si3N4 are not stable in pure H2 and decompose to silicon and gaseous species such as CH4, SiH, SiH4, N2, and NH3. Water vapor is known to slightly increase the oxidation rate of SiC and Si3N4. Refractory oxides such as alumina, yttria-stabilized zirconia, yttria and mullite (3Al2O3.2SiO2) possess excellent environmental durability in harsh conditions mentioned above. Therefore, refractory oxide coatings on silicon-base ceramics can substantially improve the environmental durability of these materials by acting as a chemical reaction barrier. These oxide coatings can also serve as a thermal barrier. The purpose of this research program has been to develop refractory oxide chemical/thermal barrier coatings on silicon-base ceramics to provide extended temperature range and lifetime to these materials in harsh environments.

Tewari, Surendra↗
NASA NTRS1993

Component Selection, Accelerated Testing, and Improved Modeling of AMTEC Systems for Space Power

Alkali metal thermal to electric converter (AMTEC) designs for space power are numerous, but the selection of materials for construction of long-lived AMTEC devices has been limited to electrodes, current collectors, and the solid electrolyte. AMTEC devices with lifetimes greater than 5 years require careful selection and life testing of all hot-side components. The likely selection of a remote condensed design for initial flight test and probable use with a radioisotope heat source in AMTEC powered planet probes requires the device to be constructed to tolerate operating T greater than 1150K, as well as exposure to Na (g) , and Na (liq) on the high pressure side. The temperatures involved make the characterization of high strength and chemical resistance to Na containing Na 2 O critical. Selection among materials which can be worked should not be driven by ease of fabricablity, as high temperature stability is the critical issue. These concepts drive the selecton of Mo alloys for Na (liq) containment in AMTEC cells for T to 1150K operation, as they are significantly stronger than comparable Nb or Ta alloys, are less soluble in Na (liq) containing dissolved Na 2 O, are workable compared with W alloys (which might be used for certain components), and are ductile at the T greater than 500K of proposed AMTEC modules in space applications.

AMTEC↗
NASA NTRS1975

The isotopic composition of galactic cosmic ray Li, Be, and B

New measurements are reported of the isotopes of cosmic-ray Li, Be, and B and of the elements C, N, and O, with cosmic ray telescopes on board the IMP-7 and IMP-8 satellites during 1973-74 in the energy range 35-210 MeV/nucleon. High mass resolution and stability together with a set of data more extensive than in previous experiments lead to a clear isotopic separation. The measured isotopic and chemical abundances provide a stringent test for models of interstellar propagation and solar modulation. We find not only that for a steady state propagation and solar modulation model all light isotopes and medium element abundances are explained by 5 g/sq cm average pathlengths, as was earlier found from element analysis, but that also these results, taken along with our Be-10 measurements, indicate a longer lifetime for cosmic rays than predicted by the usual assumption of an average interstellar density of 1 to 3 atoms/cu cm.

Garcia-Munoz, M.↗
NASA NTRS2006

Long-term Evolution of Upper Stratospheric Ozone at Selected Stations of the Network for the Detection of Stratospheric Change (NDSC)

The long-term evolution of upper stratospheric ozone has been recorded by lidars and microwave radiometers within the ground-based Network for the Detection of Stratospheric Change (NDSC), and by the space-borne Solar Backscatter Ultra-Violet instruments (SBUV), Stratospheric Aerosol and Gas Experiment (SAGE), and Halogen Occultation Experiment (HALOE). Climatological mean differences between these instruments are typically smaller than 5% between 25 and 50 km. Ozone anomaly time series from all instruments, averaged from 35 to 45 km altitude, track each other very well and typically agree within 3 to 5%. SBUV seems to have a slight positive drift against the other instruments. The corresponding 1979 to 1999 period from a transient simulation by the fully coupled MAECHAM4-CHEM chemistry climate model reproduces many features of the observed anomalies. However, in the upper stratosphere the model shows too low ozone values and too negative ozone trends, probably due to an underestimation of methane and a consequent overestimation of ClO. The combination of all observational data sets provides a very consistent picture, with a long-term stability of 2% or better. Upper stratospheric ozone shows three main features: (1) a decline by 10 to 15% since 1980, due to chemical destruction by chlorine; (2) two to three year fluctuations by 5 to 10%, due to the Quasi-Biennial Oscillation (QBO); (3) an 11-year oscillation by about 5%, due to the 11-year solar cycle. The 1979 to 1997 ozone trends are larger at the southern mid-latitude station Lauder (45 S), reaching 8%/decade, compared to only about 6%/decade at Table Mountain (35 N), Haute Provence/Bordeaux (approximately equal to 45 N), and Hohenpeissenberg/Bern(approximately equal to 47 N). At Lauder, Hawaii (20 N), Table Mountain, and Haute Provence, ozone residuals after subtraction of QBO- and solar cycle effects have levelled off in recent years, or are even increasing. Assuming a turning point in January 1997, the change of trend is largest at southern mid-latitude Lauder, +11%/decade, compared to +7%/decade at northern mid-latitudes. This points to a beginning recovery of upper stratospheric ozone. However, chlorine levels are still very high and ozone will remain vulnerable. At this point the most northerly mid-latitude station, Hohenpeissenberg/Bern differs from the other stations, and shows much less clear evidence for a beginning recovery, with a change of trend in 1997 by only +3%/decade. In fact, record low upper stratospheric ozone values were observed at Hohenpeissenberg/Bern, and to a lesser degree at Table Mountain and Haute Provence, in the winters 2003/2004 and 2004/2005.

Steinbrecht, W.↗
NASA NTRS2000

Research Activities at Plasma Research Laboratory at NASA Ames Research Center

In order to meet NASA's requirements for the rapid development and validation of future generation electronic devices as well as associated materials and processes, enabling technologies are being developed at NASA-Ames Research Center using a multi-discipline approach. The first step is to understand the basic physics of the chemical reactions in the area of plasma reactors and processes. Low pressure glow discharges are indispensable in the fabrication of microelectronic circuits. These plasmas are used to deposit materials and also etch fine features in device fabrication. However, many plasma-based processes suffer from stability and reliability problems leading to a compromise in performance and a potentially increased cost for the semiconductor manufacturing industry. Although a great deal of laboratory-scale research has been performed on many of these processing plasmas, little is known about the gas-phase and surface chemical reactions that are critical in many etch and deposition processes, and how these reactions are influenced by the variation in operating conditions. Such a lack of understanding has hindered the development of process models that can aid in the scaling and improvement of plasma etch and deposition systems. Our present research involves the study of such plasmas. An inductively-coupled plasma (ICP) source in place of the standard upper electrode assembly of the Gaseous Electronics Conference (GEC) radio-frequency (RF) Reference Cell is used to investigate the discharge characteristics. This ICP source generates plasmas with higher electron densities and lower operating pressures than obtainable with the original parallel-plate version of the GEC Cell. This expanded operating regime is more relevant to new generations of industrial plasma systems being used by the microelectronics industry. The research goal is to develop an understanding of the physical phenomena involved in plasma processing and to measure much needed fundamental parameters, such as gas phase and surface reaction rates, species concentration, temperature, ion energy distribution, and electron number density.

Sharma, S. P.↗
NASA NTRS1989

The electrochemical generation of useful chemical species from lunar materials

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

Tsai, Kan J.↗
NASA NTRS1976

Fabrication and test of experimental automotive friction materials

Three classes of experimental ingredients having good high temperature stability were substituted, singly and in combination, for corresponding ingredients in a standard friction material. The effects of substitution were evaluated by physical and chemical analysis, and principally by determination of friction and wear properties as a function of temperature on a sample drag dynamometer. The major finding was the demonstration of the potential of potassium titanate fiber for the improvement of a friction material of the secondary lining type. For example, the maintenance of a mean friction coefficient of 0.35 between 232 and 343 C (450 and 650 F) was achieved in the presence of the titanate fiber, as opposed to a value of 0.30 in its absence. Wear improvement of the order of 30 to 40% also becomes possible by proper adjustment of resin content and potassium titanate fiber-to-asbestos ratio.

Halberstadt, M. L.↗