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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1978

Equilibrium and kinetic aspects of brittle fracture

The lattice statics method for simulating a brittle crack will be employed to determine: (1) the energy-based criterion for crack stability, (2) at a given stress intensity in the stable region, the kinetic barrier for crack motion, and (3) the assumptions that break down in the Griffith theory when generalized to the lattice model. A simple model is used in the analysis, but this model is general enough to provide a conceptual framework for more realistic models.

Esterling, D. M.↗
NASA NTRS1988

Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

Gokoglu, Suleyman A.↗
NASA NTRS1992

Hydrothermal organic synthesis experiments

Ways in which heat is useful in organic synthesis experiments are described, and experiments on the hydrothermal destruction and synthesis of organic compounds are discussed. It is pointed out that, if heat can overcome kinetic barriers to the formation of metastable states from reduced or oxidized starting materials, abiotic synthesis under hydrothermal conditions is a distinct possibility. However, carefully controlled experiments which replicate the descriptive variables of natural hydrothermal systems have not yet been conducted with the aim of testing the hypothesis of hydrothermal organic systems.

Shock, Everett L.↗
NASA NTRS1992

Study of the oxygen transport through Ag (110), Ag (poly), and Ag 2.0 Zr

The transport of oxygen through high-purity membranes of Ag (110), Ag (poly), Ag (nano), and Ag 2.0 Zr has been studied by an ultrahigh vacuum permeation method over the temperature range of 400-800 C. The data show that there are substantial deviations from ordinary diffusion-controlled transport. A surface limitation has been confirmed by glow-discharge studies where the upstream O2 supply has been partially converted to atoms, which, for the same temperature and pressure, gave rise to over an order of magnitude increase in transport flux. Further, the addition of 2.0 wt percent Zr to the Ag has provided increased dissociative adsorption rates, which, in turn, increased the transport flux by a factor of 2. It was also observed that below a temperature of 630 C, the diffusivity exhibits an increase in activation energy of over 4 kcal/mol, which has been attributed to trapping of the atomic oxygen and/or kinetic barriers at the surface and subsurface of the vacuum interface. Above 630 C, the activation barrier decreases to the accepted value of about 11 kcal/mol for Ag (poly), consistent with zero concentration at the vacuum interface.

Outlaw, R. A.↗
NASA NTRS1996

Endogenous Synthesis of Prebiotic Organic Molecules

The necessary condition for the synthesis of organic compounds on the primitive earth is the presence of reducing conditions. This means an atmosphere of CH4, CO, or CO2 + H2. The atmospheric nitrogen can be N2 with a trace of NH3, but NH4(+) is needed in the ocean at least for amino acid synthesis. Many attempts have been made to use CO2 + H2O atmospheres for prebiotic synthesis, but these give at best extremely low yields of organic compounds, except in the presence of H2. Even strong reducing agents such as FeS + H2S or the mineral assemblages of the submarine vents fail to give significant yields of organic compounds with CO2. There appears to be a high kinetic barrier to the non-biological reduction of CO2 at low temperatures using geological reducing agents. The most abundant source of energy for prebiotic synthesis is ultraviolet light followed by electric discharges, with electric discharges being more efficient, although it is not clear which was the important energy source. Photochemical process would also make significant contributions. In an atmosphere Of CO2, N2, and H2O with no H2, the production rates of HCN and H2CO would be very low, 0.001 or less than that of a relatively reducing atmosphere. The concentration of organic compounds under these non-reducing conditions would be so low that there is doubt whether the concentration mechanism would be adequate for further steps toward the origin of life. A number of workers have calculated the influx of comets and meteorites on the primitive earth as a source of organic compounds. We conclude that while some organic material was added to the earth from comets and meteorites the amount available from these sources at a given time was at best only a few percent of that from earth bases syntheses under reducing conditions.

Miller, Stanley L.↗
NASA NTRS1998

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Shock, Everett L.↗
NASA NTRS1998

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

The results of the investigation were presented at a Astrobiology Institute General Meeting. Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions.

Shock, Everett L.↗
NASA NTRS2001

CO2 Snow on Mars and Early Earth: Experimental Constraints

Greenhouse warming due to carbon dioxide atmospheres may be responsible for maintaining the early Earth's surface temperature above freezing and may even have allowed for liquid water on early Mars. However, the high levels of CO2 required for such warming should have also resulted in the formation of CO2 clouds. These clouds, depending on their particle size, could lead to either warming or cooling. The particle size in turn is determined by the nucleation and growth conditions. Here we present laboratory studies of the nucleation and growth of carbon dioxide on water ice under Martian atmospheric conditions. We find that a critical saturation, S = 1.34, is required for nucleation, corresponding to a contact parameter between solid water and solid carbon dioxide of m = 0.95. We also find that after nucleation occurs, growth of CO2 is very rapid and proceeds without a surface kinetic barrier. Because growth would be expected to continue until the CO2 pressure is lowered to its vapor pressure, we expect particles larger than those being currently suggested for the present and past Martian atmospheres. Using this information in a microphysical model described in a companion paper, we find that CO2 clouds are best described as "snow", having a relatively small number of large particles.

Glandorf, David L.↗
NASA NTRS2013

Transient Climate Effects of Large Impacts on Titan

Titan's thick atmosphere and volatile-rich surface cause it to respond to big impacts in a somewhat Earth-like manner. Here we construct a simple globally-averaged model that tracks the flow of energy through the environment in the weeks, years, and millenia after a big comet strikes Titan. The model Titan is endowed with 1.4 bars of N2 and 0.07 bars of CH4, methane lakes, a water ice crust, and enough methane underground to saturate the regolith to the surface. We find that a nominal Menrva impact is big enough to raise the surface temperature by approx. 80 K and to double the amount of methane in the atmosphere. The extra methane drizzles out of the atmosphere over hundreds of years. An upper-limit Menrva is just big enough to raise the surface to water's melting point. The putative Hotei impact (a possible 800-1200 km diameter basin, Soderblom et al., 2009) is big enough to raise the surface temperature to 350-400 K. Water rain must fall and global meltwaters might range between 50 m to more than a kilometer deep, depending on the details. Global meltwater oceans do not last more than a few decades or centuries at most, but are interesting to consider given Titan's organic wealth. Significant near-surface clathrate formation is possible as Titan cools but faces major kinetic barriers.

Titan↗
NASA NTRS2015

Thermodynamics and Kinetics of Silicate Vaporization

Silicates are a common class of materials that are often exposed to high temperatures. The behavior of these materials needs to be understood for applications as high temperature coatings in material science as well as the constituents of lava for geological considerations. The vaporization behavior of these materials is an important aspect of their high temperature behavior and it also provides fundamental thermodynamic data. The application of Knudsen effusion mass spectrometry (KEMS) to silicates is discussed. There are several special considerations for silicates. The first is selection of an appropriate cell material, which is either nearly inert or has well-understood interactions with the silicate. The second consideration is proper measurement of the low vapor pressures. This can be circumvented by using a reducing agent to boost the vapor pressure without changing the solid composition or by working at very high temperatures. The third consideration deals with kinetic barriers to vaporization. The measurement of these barriers, as encompassed in a vaporization coefficient, is discussed. Current measured data of rare earth silicates for high temperature coating applications are discussed. In addition, data on magnesium-iron-silicates (olivine) are presented and discussed.

thermodynamics↗
NASA NTRSDate not supplied

Interfacial thermodynamics of cryogenic fluids: The effect on non-condensable gas on fluid storage

Propellant tanks that contain cryogenic fluids (CFs) in low gravity conditions are usually pressurized with non-condensable (NC) gases for fast extraction. Unfortunately, the presence of NC gases causes CFs to exhibit higher boil-offs compared to pure CF systems. For optimal utilization of the cryogenic fuels, these higher boil-off rates must be minimized. Our goal is to quantify the effects NC gases have on the evaporation and condensation dynamics of CFs to develop strategies that mitigate the higher boil-offs. The hypothesis is that the NC gas accumulates around the CF’s liquid vapor interface in the Knudsen layer, creating a kinetic barrier for both evaporation and condensation. Testing this hypothesis with experimental methods is difficult due to the transient nature of the Knudsen layer, which is only a few nanometers thick. Furthermore, experimental capabilities are limited in low gravity conditions and extremely expensive. Accordingly, we approach this problem from a theoretical perspective. In this study, we employ molecular dynamics (MD) simulations to probe the interfacial mechanisms that affect CF’s evaporation and condensation at varying concentrations of NC gases. Specifically, we use nitrogen (N2) and oxygen (O2) as our CFs and neon (Ne) as our NC gas. Using MD simulations, we show that Ne accumulates at N2 liquid vapor interface across a wide range of Ne concentrations, thereby impeding mass transport of N2. Our simulations allow for direct computation of the molar flux as well as the mass accommodation coefficient (MAC) which can then be used as input parameters to continuum fluid dynamics (CFD) models for optimal storage tank design.

Michael Robert DeLyser↗
DOE OSTI2021

Evaluating steam oxidation kinetics of environmental barrier coatings

Environmental barrier coatings (EBCs) are a commercially proven means of protecting SiC-based materials in gas turbine environments. However, there are little specific data in the literature on the impact of coatings like Yb 2 Si 2 O 7 on preventing accelerated SiO 2 growth in the presence of H 2 O. Quantification of reduced rates are necessary for evaluating and comparing EBC effectiveness and incorporation of silica growth rates into future EBC lifetime models. In this study, baseline kinetics of silica formation on bare Si and chemically vapor deposited (CVD) SiC in the 1250–1425 °C range were obtained via 100 h isothermal exposures in dry air and steam environments utilizing a SiC reaction tube to mitigate specimen volatility. An Arrhenius plot of the resulting rates was constructed, representing baseline minimum and maximum rates for Si and SiC oxidation at ambient pressure. Various EBC systems on CVD SiC substrates including air plasma sprayed (APS) EBCs with and without a Si bond coating and with surface roughening to enhance Yb 2 Si 2 O 7 adhesion were subjected to 1-h furnace cycle testing in air with 90vol%H 2 O at 1250–1350°C for up to 500 cycles. After exposure, silica formation rates were measured and compared to the baseline rates to assess EBC effectiveness, where EBC effectiveness is gauged as the propensity to reduce underlying rates of silica formation. With a Si bond coating, a ~180 µm Yb 2 Si 2 O 7 (YbDS) top coating reduced rates over the entire 1250°-1350°C range. Without a Si bond coating, ~60 µm (YbDS) coatings deposited directly onto CVD SiC exhibited poor adhesion, and had to be deposited onto substrates with enhanced roughness at 1350°C. Finally, while exhibiting good adhesion at 1350°C, overall the single layer YbDS coating exhibited a decreasing effectiveness from 1250° to 1350°C.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Safer Roadside Crash Walls Would Limit Deceleration

The figure depicts the aspects of a proposed deceleration-limiting design for crash walls at the sides of racetracks and highways. The proposal is intended to overcome the disadvantages of both rigid barriers and kinetic-energy-absorbing barriers of prior design. Rigid barriers can keep high-speed crashing motor vehicles from leaving roadways and thereby prevent injury to nearby persons and objects, but they can also subject the occupants of the vehicles to deceleration levels high enough to cause injury or death. Kinetic-energy-absorbing barriers of prior design reduce deceleration levels somewhat, but are not designed to soften impacts optimally; moreover, some of them allow debris to bounce back onto roadways or onto roadside areas, and, in cases of glancingly incident vehicles, some of them can trap the vehicles in such a manner as to cause more injury than would occur if the vehicles were allowed to skid along the rigid barriers. The proposed crash walls would (1) allow tangentially impacting vehicles to continue sliding along the racetrack without catching them, (2) catch directly impacting vehicles to prevent them from injuring nearby persons and objects, and (3) absorb kinetic energy in a more nearly optimum way to limit decelerations to levels that human occupants could survive.

Schneider, William C.↗
DOE OSTI2024

The Role of Nonequilibrium Solvent Effects in Enhancing Direct CO 2 Capture at the Air–Aqueous Amino Acid Interface

Direct air capture (DAC) technologies are limited by the poor understanding of the dynamic role of interfaces in modulating the chemisorption of CO 2 from air into solutions. While the reactivity of aqueous amine-based solvents in the bulk environment is strongly inhibited by nonequilibrium solvent effects, promoting DAC at interfaces posits a possibility to reduce the coupling with the solvent and significantly accelerate DAC. Building on an experimentally proven concept to bring an anionic glycine absorbent to the interface through ion-pairing interactions with a positively charged surfactant, we establish the fundamental time scales for key elementary steps involved in DAC with rate theory and enhanced-sampling ab initio molecular dynamics simulations. Here, we elucidate the mechanism by which water influences the free energy barriers and dynamical crossing-recrossing of those barriers, affecting the reaction rates. We find that water reorganizes to partially dehydrate [-NH 2 ], facilitating S N 2-based CO 2 conversion to a zwitterion, which then releases a proton via overhydration of [-NH 2 ]. The low-density interfacial water favors dehydration over overhydration, leading to a comparatively higher barrier (slower kinetics) for proton release. The barrier-recrossing events neutralize this effect, letting both steps occur at the same time scale (sub-microseconds) and making the overall DAC process faster at the interface than in the bulk water. Such an understanding of environment-sensitive solvent effects on the reaction kinetics will help design tailored interfaces for enhanced CO 2 capture kinetics via control of solvation and ion paring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2000

Thermal Conductivity Change Kinetics of Ceramic Thermal Barrier Coatings Determined by the Steady-State Laser Heat Flux Technique

A steady-state laser heat flux technique has been developed at the NASA Glenn Research Center at Lewis Field to obtain critical thermal conductivity data of ceramic thermal barrier coatings under the temperature and thermal gradients that are realistically expected to be encountered in advanced engine systems. In this study, thermal conductivity change kinetics of a plasma-sprayed, 254-mm-thick ZrO2-8 wt % Y2O3 ceramic coating were obtained at high temperatures. During the testing, the temperature gradients across the coating system were carefully measured by the surface and back pyrometers and an embedded miniature thermocouple in the substrate. The actual heat flux passing through the coating system was determined from the metal substrate temperature drop (measured by the embedded miniature thermocouple and the back pyrometer) combined with one-dimensional heat transfer models.

Zhu, Dongming↗
DOE OSTI2021

First-principles calculations for understanding microstructures and mechanical properties of co-sputtered Al alloys

Recent experimental studies show that co-sputtering solutes with Al, together, can refine columnar grain size around few tens of nanometers and promote the formation and enhance the stability of planar defects such as stacking faults (SFs) and grain boundaries (GBs) in Al alloys. These crystal defects and fine columnar grains result in high strength, enhanced strain hardening and thermal stability of Al alloys. Using first-principles density-functional theory (DFT) calculations, we studied the role of eleven solutes in tailoring kinetics and energetics of adatoms and clusters on Al {111} surface, stable and unstable stacking fault energies, and kinetic energy barriers for the migration of defects. The calculations show that most solutes can effectively refine columnar grain size by decreasing the diffusivity of adatoms and surface clusters. These solutes do not necessarily decrease the stacking fault energy of Al alloys, but reduce the formation energy of faulted surface clusters and increase the energy barriers for the recovery of faulted surface clusters. Correspondingly, the formation of SFs is kinetically promoted during sputtering. Furthermore, solutes are segregated into the core of Shockley partial dislocations and play a pinning effect on SFs, SF arrays and twin boundaries, enhancing the thermal stability of these crystal defects. These findings provide insights into the design of high-strength Al alloys for high-temperature applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Catalytic Resonance Theory: Experimental and Kinetic Interpretation of Programmable Catalysis

The complexity of programmable catalysts that change in the physical or electronic state on the time scale of a catalytic turnover results in uncertainty in the kinetic outcome of common measurements with dynamic catalyst experiments. To provide an interpretation of utility to experimentalists, a general programmable catalytic reaction exhibiting high turnover efficiency was simulated to understand the kinetic behavior of catalysts with varying frequency, binding energy, oscillation amplitude, and minimum oscillation binding energy at different temperatures and reactant gas pressures. The time-averaged catalytic rate for varying temperature in the form of an Arrhenius plot exhibited three distinct kinetic regimes, with the intermediate temperatures or applied frequencies exhibiting zero slope, indicative of barrier-free kinetic control. Transitions in experimentally measurable kinetic regimes with both temperature and applied catalyst oscillation frequency were associated with transitions in the sensitivity of reaction rate constants and degrees of rate control. Furthermore, these distinct kinetic macroscopic features specific to programmable catalysts were identified for observation in experimental dynamic kinetic measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗