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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 73 records · Page 4

High Energy Density Matter for Rocket Propulsion

The objective of the High Energy Density Matter (HEDM) program is to identify, develop, and exploit high energy atomic and molecular systems as energetic sources for rocket propulsion applications. It is a high risk, high payoff program that incorporates both basic and applied research, experimental and theoretical efforts, and science and engineering efforts. The HEDM program is co-sponsored by the Air Force Office of Scientific Research (AFOSR) and the Phillips Laboratory (PURKS). It includes both in-house and contracted University/Industry efforts. Technology developed by the HEDM program offers the opportunity for significant breakthroughs in propulsion system capabilities over the current state-of-the-art. One area of great interest is the use of cryogenic solids to increase the density of the propellant and to act as a stable matrix for storage of energetic materials. No cryogenic solid propellant has ever been used in a rocket, and there remain engineering challenges to such a propellant. However, these solids would enable a wide class of highly energetic materials by providing an environment that is at very low temperatures and is a physical barrier to recombination or energy loss reactions. Previous to our experiments only hydrogen atoms had been isolated in solid hydrogen. To date we have succeeded in trapping B, Al, Li, N, and Mg atoms in solid H2. Small molecules, such as B2 and LiB, are also of interest. Current efforts involve the search for new energetic small molecules, increasing free radical concentrations up to 5 mole percent, and scale-up for propulsion testing.

Carrick, Patrick G.↗

Turbulent Diffusion and Concentration of "Chondrules" in the Protoplanetary Nebula

Turbulence is known to possess structure on many scales. The largest or integral scale L is usually taken to be the largest relevant dimension of the system; for the nebula as a whole, it would be on the order of a vertical gas scale height H approximately 0.1R where R is the distance from the sun. Turbulent kinetic energy cascades towards smaller scales; for fully developed, homogeneous turbulence, the turbulent kinetic energy peaks at the integral scale and is distributed within its "inertial range" according to the Kolmogorov energy spectrum dE(k) = E(sub 0)(kL)(sup -5/3)dk where k is the wavenumber or inverse wavelength. The smallest scale in a turbulent regime is the Kolmogorov scale (n)(sometimes referred to as the inner scale). On this scale, molecular viscosity can dissipate turbulent kinetic energy . Turbulent flows are characterized by their Reynolds number Re = UL/v, where U is a characteristic velocity scale and v is molecular viscosity. More energetic (higher Re) flows drive turbulence to smaller Kolmogorov scales: n = LRe(sup -3/4). Two different turbulent regimes are likely to be of importance; early stage convective turbulence in a hot nebula probably extends over the entire nebula scale height, and probably has typical eddy frequency comparable to the orbit frequency. At a later stage, midplane shear layer turbulence can be driven by the presence of a differentially rotating, densely settled particle layer, with different length and time scales.

Cuzzi, Jeffrey N.↗

A Spaceflight Experiment to Determine the Effect of Chamfered Sample Holders on Atomic Oxygen Erosion

The exteriors of low Earth orbit (LEO) spacecraft are subjected to many environmental threats that can cause the surface materials to degrade. One of these threats is atomic oxygen (AO), which is formed by photo dissociation of molecular oxygen by energetic UV radiation. Atomic oxygen exposure can result in oxidative erosion of polymers leading to structural or thermal failure of spacecraft components. The amount of AO erosion expected during a mission can be calculated by knowing the AO erosion yield (Ey, volume loss per incident atom) of the material and the AO fluence expected for the mission. The Ey can be determined through dehydrated mass loss measurements of test samples if one knows the AO fluence, density, and exposure area. Such measurements have been made as part of flight experiments, including the Materials International Space Station Experiment 2 (MISSE 2) Polymers Experiment. The MISSE 2 Polymers Experiment sample holders had chamfered circular apertures that controlled the exposure area, but also allowed some additional AO to scatter from the chamfered edges onto the samples thus causing some samples to erode thru and peel at their perimeter due to this scattering effect. By modeling the scattered AO flux one can predict the actual total AO fluence, and hence more accurate sample Ey. Sample holders with different chamfered-perimeter to exposed-area ratios have been designed for future spaceflight experiments that allow a more accurate determination of the Ey for large area polymers, representative of their use on spacecraft surfaces.

Earth Orbital Environments↗

Dynamics of Nanoscale Grain-Boundary Decohesion in Aluminum by Molecular-Dynamics Simulation

The dynamics and energetics of intergranular crack growth along a flat grain boundary in aluminum is studied by a molecular-dynamics simulation model for crack propagation under steady-state conditions. Using the ability of the molecular-dynamics simulation to identify atoms involved in different atomistic mechanisms, it was possible to identify the energy contribution of different processes taking place during crack growth. The energy contributions were divided as: elastic energy, defined as the potential energy of the atoms in fcc crystallographic state; and plastically stored energy, the energy of stacking faults and twin boundaries; grain-boundary and surface energy. In addition, monitoring the amount of heat exchange with the molecular-dynamics thermostat gives the energy dissipated as heat in the system. The energetic analysis indicates that the majority of energy in a fast growing crack is dissipated as heat. This dissipation increases linearly at low speed, and faster than linear at speeds approaching 1/3 the Rayleigh wave speed when the crack tip becomes dynamically unstable producing periodic dislocation bursts until the crack is blunted.

Yamakov, V.↗

Infrared Line Emission from Molecular Gas Heated by X-Rays and Energetic Electrons

"I propose to carry out a detailed study using infrared observations (and in some cases, optical and ultraviolet observations) of dense interstellar gas exposed to intense fluxes of X-rays and/or energetic electrons. This is undoubtedly the dominant source of line emission for clouds exposed to X-rays from active galactic nuclei, supernova shocks, or embedded X-ray sources (e.g., X-ray binaries), or to high-temperature or relativistic electrons in galaxy clusters, near powerful radio sources, or supernova remnants. Detailed physical and chemical models of such clouds will be used to analyze infrared observations of the Great Annihilator X-ray source in the Galactic Center, cD galaxies in massive cooling flows, and the nuclei of Seyfert galaxies which will be obtained with the Infrared Space Observatory (ISO), UV and optical observations of the Crab Nebula obtained with the Hubble Space Telescope, and ground-based near-infrared observations of Seyfert nuclei. Results from this work will also be of great relevance to observations obtained with the Submillimeter Wave Astronomical Satellite (SWAS). In the first year of funding of this proposal, my chief collaborators (D.J. Hollenbach and A.G.G.M. Tielens, both of NASA Ames Research Center) and I concentrated on completing our models of the physical conditions in, and the resulting line emission from, dense gas irradiated by X-rays. As noted in the original proposal, some important physical processes were not yet thoroughly incorporated into our models at the time of submission. We completed our modeling of the physical conditions and line emission for essentially the entire range of parameter space (five orders of magnitude in X-ray flux to gas density ratio) occupied by typical dense interstellar clouds in which the gas is mostly neutral and X-rays are important for the ionization, chemistry, and thermal balance.

Maloney, Philip R.↗

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

This project is part of an ongoing and long-term collaboration among Alexandra Navrotsky (who moved recently from UC Davis to Arizona State University), Nancy Ross at Virginia Tech, and Brian Woodfield at Brigham Young University (BYU) on the thermodynamics and lattice dynamics of nanophase and porous materials. Navrotsky emphasizes energetics of formation and guest molecule sorption by ambient and high temperature calorimetry, Woodfield contributes cryogenic heat capacity measurements, and Ross uses inelastic neutron scattering, X-ray and neutron diffraction, and high pressure studies to probe lattice dynamics and phase transitions. Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size.

36 MATERIALS SCIENCE↗

Synthesis and investigation into explosive sensitivity for a series of new picramide explosives

Tailoring the molecular properties that govern energetic material sensitivity is essential to improve safety and help develop new energetic materials. Despite this need, understanding the complex chemistry and physics of explosive initiation and propagation is still a challenge. Recent work by our group has reinforced the view that explosive sensitivity under sub-shock conditions is connected to the strength of the weakest covalent bond in the molecule, that is, its “trigger linkage.” These correlations have been observed with different classes of energetic molecules and indicate that “trigger linkage” bond breaking, and heat of explosion are good indicators for the sensitivity trends. Herein we report the synthesis of aliphatic energetic materials with ethane, propane and neopentane backbones. Experimental and computational studies show that the trigger linkage model, based on results from quantum molecular dynamics simulations, correctly predicts trends observed in the impact sensitivity of the molecules. However, while the model predicts the impact sensitivities of the ethane series, the neopentane series has higher impact sensitivities than predicted, which is presumably influenced by crystal packing effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. The report below summarizes the work done at UC Davis, which is complemented by work done at BYU (Woodfield) and Virginia Tech (Ross).

36 MATERIALS SCIENCE↗

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. This research was a collaboration between UC Davis (A. Navrotsky) BYU (B. Woodfield) and Virginia Tech (N. Ross).

36 MATERIALS SCIENCE↗

New Perspectives on Vibrational Energy Transfer in Energetic Materials: Insights from Pressure-Tuned Ultrafast Spectroscopy

Understanding the manner in which vibrational energy flows between molecular and lattice vibrations is of great interest in physical chemistry due to its central role in reactivity and energy dissipation in molecular materials. Here, in this feature article, we highlight our recent efforts employing ultrafast broadband infrared spectroscopy toward understanding the interplay between molecular and lattice vibrations in energetic materials, motivated by the open questions surrounding the role of vibrational energy transfer (VET) in reaction initiation in these materials. Our work addresses the ongoing debate on the participation of doorway modes in VET. We further present new results from high-pressure ultrafast experiments on RDX, a hydrogen-bonded material, and BNFF, a hydrogen-free material, to explore how intermolecular interaction strength governs VET pathways and time scales. Collectively, our findings reveal that vibrational dynamics in these systems occurs across three distinct time regimes, with VET being incomplete out to hundreds of picoseconds, suggesting the importance of considering nonstatistical reactions in the modeling of these materials. These time scales vary as intermolecular interaction strength is indirectly modified by application of static pressure, indicating dramatic changes to the vibrational structure of these materials under shock-relevant conditions. Our results thus shed light on how intermolecular interactions shape vibrational energy redistribution in molecular materials, and highlight the need for further theoretical and experimental investigation.

Carlson, Daniel Ryan [Sandia National Laboratories↗

TATB thermal decomposition: Expanding the molecular profile with cryo-focused pyrolysis GC-MS

Understanding the molecular composition of high explosives during thermal decomposition is vital for predicting the sensitivity, safety, and performance of explosive materials. The thermal decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) has been linked to the formation of furazans through a series of dehydration reactions of the NO2 and NH2 groups on the phenyl ring, along with breakdown into small molecules (≤120 amu). Molecular identification of compounds formed in this transformation of the furazans to light gases has been lacking. To address this, we have applied a pseudo-confined sampling system in a cryo-focused pyrolysis gas chromatography-mass spectrometry (pyGC-MS) system to molecularly identify these intermediates. By design, sublimation of TATB, which has complicated MS analyses of thermal degradation, was significantly reduced and additional compounds were identified with potential structural information. In addition to the known furazan compounds, one of these compounds forms from the loss of oxygen from benzo-trifurazan (F3) and produces an open ring structure that may be the first step in the formation of lower molecular weight furazan breakdown products. The loss of a nitro group from benzo-monofurazan (F1) was also discovered and implicates the formation of oxidizing NO2 gas in the thermal decomposition mechanism. So these findings are vital for understanding the proper heat flow from energetic materials on a molecular level, necessary when measuring enthalpy and developing decomposition models based on kinetic parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Planned investigation of infrared emissions associated with the induced spacecraft glow: A shuttle infrared glow experiment (SIRGE)

The characteristics of infrared molecular emissions induced by energetic collisions between ambient atmospheric species and surfaces in Earth orbit are investigated, using a low-nitrogen-cooled filter wheel photometer covering the wavelength range 0.9-.5 microns with a resolving power Lambda/Delta Lambda of approximately 100. This resolving power is sufficient for identification of the molecular or atomic fluorescent spaces causing the glow.

Mumma, M. J.↗

The 158 micrometer (CII) line: A measure of global star formation activity in galaxies

Some 158 micron (CII) fine structure line observations from a sample of fourteen gas rich galaxies are reported. These measurements confirm and generalize previous basic results that the (CII) line is bright amounting to approximately 0.1 to 1 percent of the Far Infra Red (FIR) luminosity of the nuclear regions of galaxies; the (CII) line is formed in the warm (temperature of the gas is greater than 200 K), dense (n sub H greater than 1000/cu cm) photodissociated gas at the interfaces between giant molecular clouds and ionized gas regions and is therefore associated with the molecular gas component in spiral galaxies; the (CII) line tracks the FIR continuum in a manner consistent with the PDR models; the integrated (CII) to isotope (12)CO (transition 1 to 0) line ratio is large (greater than or equal to 1000) in all galaxies studied, and is similarly large for galactic molecular clouds; the (CII) line is therefore energetically very important for the study of giant molecular clouds. Conclusions obtained from these results are given.

Stacey, G. J.↗

Structure, vibrational spectrum, and energetics of the CH5(+) ion - A theoretical investigation

Analytic derivative techniques are utilized to determine molecular geometries, vibration spectra, molecular force field, proton affinity, and energetics of clustering of protonated methane. It is observed that the geometries are gradient optimized, while the harmonic force fields and IR intensities are also determined analytically at the SCF level. It is determined that the frequency of the torsional model for rotation of the H2 about the pseudothreefold axis of the CH3(+) group is extremely low, and the proton affinity of CH4 is calculated as 129.0 kcal/mol.

Komornicki, Andrew↗

Fragmentation of interstellar clouds and star formation

The principal issues are addressed: the fragmentation of molecular clouds into units of stellar mass and the impact of star formation on molecular clouds. The observational evidence for fragmentation is summarized, and the gravitational instability described of a uniform spherical cloud collapsing from rest. The implications are considered of a finite pressure for the minimum fragment mass that is attainable in opacity-limited fragmentation. The role of magnetic fields is discussed in resolving the angular momentum problem and in making the collapse anisotropic, with notable consequences for fragmentation theory. Interactions between fragments are described, with emphasis on the effect of protostellar winds on the ambient cloud matter and on inhibiting further star formation. Such interactions are likely to have profound consequences for regulating the rate of star formation and on the energetics and dynamics of molecular clouds.

Silk, J.↗

High-pressure and temperature neural network reactive force field for energetic materials

Reactive force fields for molecular dynamics have enabled a wide range of studies in numerous material classes. These force fields are computationally inexpensive compared with electronic structure calculations and allow for simulations of millions of atoms. However, the accuracy of traditional force fields is limited by their functional forms, preventing continual refinement and improvement. Therefore, we develop a neural network-based reactive interatomic potential for the prediction of the mechanical, thermal, and chemical responses of energetic materials at extreme conditions. The training set is expanded in an automatic iterative approach and consists of various CHNO materials and their reactions under ambient and shock-loading conditions. Further, this new potential shows improved accuracy over the current state-of-the-art force fields for a wide range of properties such as detonation performance, decomposition product formation, and vibrational spectra under ambient and shock-loading conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Catalysis under 2D Silica: A CO Oxidation Study

Interfacially confined microenvironments have recently gained attention in catalysis, as they can be used to modulate reaction chemistry. The emergence of a 2D nanospace at the interface between a 2D material and its support can promote varying kinetic and energetic schemes based on molecular level confinement effects imposed in this reduced volume. We report on the use of a 2D oxide cover, bilayer silica, on catalytically active Pd(111) undergoing the CO oxidation reaction. We “uncover” mechanistic insights about the structure-activity relationship with and without a 2D silica overlayer using in situ IR and X-ray spectroscopy and mass spectrometry methods. We find that the CO oxidation reaction on Pd(111) benefits from confinement effects imposed on surface adsorbates under 2D silica. Finally, this interaction results in a lower and more dispersed coverage of CO adsorbates with restricted CO adsorption geometries, which promote oxygen adsorption and lay the foundation for the formation of a reactive surface oxide that produces higher CO 2 formation rates than Pd alone.

36 MATERIALS SCIENCE↗

Enhanced Catalysis under 2D Silica: A CO Oxidation Study

Abstract Interfacially confined microenvironments have recently gained attention in catalysis, as they can be used to modulate reaction chemistry. The emergence of a 2D nanospace at the interface between a 2D material and its support can promote varying kinetic and energetic schemes based on molecular level confinement effects imposed in this reduced volume. We report on the use of a 2D oxide cover, bilayer silica, on catalytically active Pd(111) undergoing the CO oxidation reaction. We “uncover” mechanistic insights about the structure–activity relationship with and without a 2D silica overlayer using in situ IR and X‐ray spectroscopy and mass spectrometry methods. We find that the CO oxidation reaction on Pd(111) benefits from confinement effects imposed on surface adsorbates under 2D silica. This interaction results in a lower and more dispersed coverage of CO adsorbates with restricted CO adsorption geometries, which promote oxygen adsorption and lay the foundation for the formation of a reactive surface oxide that produces higher CO 2 formation rates than Pd alone.

Eads, Calley N.↗