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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Analysis of Flow From Arc-Jet Spectra

Materials testing is carried out at the JSC Atmospheric Reentry Materials and Structures Facility. A flow diagnostics program is under development to characterize the energy distribution in arc-jet flows used to simulate atmospheric entry. Heat transfer to materials depends on flow properties which includes the composition of and energy distribution among the atoms, ions, molecules, and molecular ions which make up the flow. This project involves analysis of shock layer characteristics from the radiation emitted and experimentally collected from near the front of the shock to near the surface of the material. The analysis has yielded information on relative populations of neutral molecules and molecular ions within the layer. In determining non-equilibrium temperatures within the layer, some insight into the spectral constants used to compute radiative emission has been gained.

Blackwell, H. E.↗
NASA NTRS2015

Giant-Planet Chemistry: Ammonium Hydrosulfide (NH4SH), Its IR Spectra and Thermal and Radiolytic Stabilities

Here we present our recent studies of proton-irradiated and unirradiated ammonium hydrosulfide, NH4SH, a compound predicted to be an important tropospheric cloud component of Jupiter and other giant planets. We irradiated both crystalline and amorphous NH4SH at 10-160 K and used IR spectroscopy to observe and identify reaction products in the ice, specifically NH3 and long-chained sulfur-containing ions. Crystalline NH4SH was amorphized during irradiation at all temperatures studied with the rate being the fastest at the lowest temperatures. Irradiation of amorphous NH4SH at approximately 10-75 K showed that 60-80% of the NH4 + remained when equilibrium was reached, and that NH4SH destruction rates were relatively constant within this temperature range. Irradiations at higher temperatures produced different dose dependence and were accompanied by pressure outbursts that, in some cases, fractured the ice. The thermal stability of irradiated NH4SH was found to be greater than that of unirradiated NH4SH, suggesting that an irradiated giant-planet cloud precipitate can exist at temperatures and altitudes not previously considered.

Jupiter↗
NASA NTRS1988

A generalized chemistry version of SPARK

An extension of the reacting H2-air computer code SPARK is presented, which enables the code to be used on any reacting flow problem. Routines are developed calculating in a general fashion, the reaction rates, and chemical Jacobians of any reacting system. In addition, an equilibrium routine is added so that the code will have frozen, finite rate, and equilibrium capabilities. The reaction rate for the species is determined from the law of mass action using Arrhenius expressions for the rate constants. The Jacobian routines are determined by numerically or analytically differentiating the law of mass action for each species. The equilibrium routine is based on a Gibbs free energy minimization routine. The routines are written in FORTRAN 77, with special consideration given to vectorization. Run times for the generalized routines are generally 20 percent slower than reaction specific routines. The numerical efficiency of the generalized analytical Jacobian, however, is nearly 300 percent better than the reaction specific numerical Jacobian used in SPARK.

Carpenter, Mark H.↗
DOE OSTI2020

Molecular structure determination: Equilibrium structure of pyrimidine (m-C 4 H 4 N 2 ) from rotational spectroscopy (reSE) and high-level ab initio calculation (re) agree within the uncertainty of experimental measurement

The pure rotational spectrum of pyrimidine (m-C 4 H 4 N 2 ), the meta-substituted dinitrogen analog of benzene, has been studied in the millimeter-wave region from 235 GHz to 360 GHz. The rotational spectrum of the ground vibrational state has been assigned and fit to yield accurate rotational and distortion constants. Over 1700 distinct transitions were identified for the normal isotopologue in its ground vibrational state and least-squares fit to a partial sextic S-reduced Hamiltonian. Transitions for all four singly substituted 13 C and 15 N isotopologues were observed at natural abundance and were likewise fit. Deuterium-enriched samples of pyrimidine were synthesized, giving access to all eleven possible deuterium-substituted isotopologues, ten of which were previously unreported. Experimental values of rotational constants and computed values of vibration–rotation interaction constants and electron-mass corrections were used to determine semi-experimental equilibrium structures (r e SE ) of pyrimidine. The r e SE structure obtained using coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] corrections shows exceptional agreement with the re structure computed at the CCSD(T)/cc-pCV5Z level (≤0.0002 Å in bond distance and ≤0.03° in bond angle). Of the various computational methods examined, CCSD(T)/cc-pCV5Z is the only method for which the computed value of each geometric parameter lies within the statistical experimental uncertainty (2σ) of the corresponding semi-experimental coordinate. The exceptionally high accuracy and precision of the structure determination is a consequence of the large number of isotopologues measured, the precision and extent of the experimental frequency measurements, and the sophisticated theoretical treatment of the effects of vibration–rotation coupling and electron mass. Taken together, these demanding experimental and computational studies establish the capabilities of modern structural analysis for a prototypical monocyclic aromatic compound.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

Graphene Oxide Reduces the Hydrolytic Degradation in Polyamide-11

Graphene oxide (GO) was incorporated into polyamide-11 (PA11) via in-situ polymerization. The GO-PA11 nano-composite had elevated resistance to hydrolytic degradation. At a loading of 1 mg/g, GO to PA11, the accelerated aging equilibrium molecular weight of GO-PA11 was higher (33 and 34 kg/mol at 100 and 120 °C, respectively) compared to neat PA11 (23 and 24 kg/mol at 100 and 120 °C, respectively). Neat PA11 had hydrolysis rate constants (kH) of 2.8 and 12 ( × 10(exp -2) day(exp -1)) when aged at 100 and 120 °C, respectively, and re-polymerization rate constants (kP) of 5.0 and 23 ( × 10(exp -5) day(exp -1)), respectively. The higher equilibrium molecular weight for GO-PA11 loaded at 1 mg/g was the result of a decreased kH, 1.8 and 4.5 ( × 10(exp -2) day(exp -1)), and an increased kP, 10 and 17 ( × 10(exp -5) day(exp -1)) compared with neat PA11 at 100 and 120 °C, respectively. The decreased rate of degradation and resulting 40% increased equilibrium molecular weight of GO-PA11 was attributed to the highly asymmetric planar GO nano-sheets that inhibited the molecular mobility of water and the polymer chain. The crystallinity of the polymer matrix was similarly affected by a reduction in chain mobility during annealing due to the GO nanoparticles' chemistry and highly asymmetric nano-planar sheet structure.

Samuel J A Hocker↗
DOE OSTI2024

Catalytic Resonance Theory: The Catalytic Mechanics of Programmable Ratchets

Catalytic reaction networks of multiple elementary steps operating under dynamic conditions via a programmed input oscillation are difficult to interpret and optimize due to reaction system complexity. To understand these dynamic systems, individual elementary catalytic reactions oscillating between catalyst states were evaluated to identify their three fundamental characteristics that define their ability to promote reactions away from equilibrium. First, elementary catalytic reactions exhibit directionality to promote reactions forward or backward from equilibrium as determined by a ratchet directionality metric comprised of the input oscillation duty cycle and the reaction rate constants. Second, catalytic ratchets are defined by the catalyst state of strong or weak binding that permit reactants to proceed through the transition state. Third, elementary catalytic ratchets exhibit a cutoff frequency which defines the transition in applied frequency for which the catalytic ratchet functions to promote chemistry away from equilibrium. All three ratchet characteristics are calculated from chemical reaction parameters including rate constants derived from linear scaling parameters, reaction conditions, and catalyst state. The characteristics of the reaction network’s constituent elementary catalytic reactions provided an interpretation of complex reaction networks and a method of predicting the behavior of dynamic surface chemistry on oscillating catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Quantum Simulations of Vibrational Strong Coupling via Path Integrals

A quantum simulation of vibrational strong coupling (VSC) in the collective regime via thermostated ring-polymer molecular dynamics (TRPMD) is reported. For a collection of liquid-phase water molecules resonantly coupled to a single lossless cavity mode, the simulation shows that as compared with a fully classical calculation, the inclusion of nuclear and photonic quantum effects does not lead to a change in the Rabi splitting but does broaden polaritonic line widths roughly by a factor of 2. Moreover, under thermal equilibrium, both quantum and classical simulations predict that the static dielectric constant of liquid water is largely unchanged inside vs outside the cavity. Furthermore, this result disagrees with a recent experiment demonstrating that the static dielectric constant of liquid water can be resonantly enhanced under VSC, suggesting either limitations of our approach or perhaps other experimental factors that have not yet been explored.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Spontaneous Cyclogenesis without Radiative and Surface-Flux Feedbacks

Tropical cyclones (TCs) are among the most intense and feared storms in the world. What physical processes lead to cyclogenesis remains the most mysterious aspect of TC physics. Here, we study spontaneous TC genesis in rotating radiative–convective equilibrium using cloud-resolving simulations over an f plane with constant sea surface temperature. Previous studies proposed that spontaneous TC genesis requires either radiative or surface-flux feedbacks. To test this hypothesis, we perform mechanism-denial experiments, in which we switch off both feedback processes in numerical simulations. We find that TCs can self-emerge even without radiative and surface-flux feedbacks. Although these feedbacks accelerate the genesis and impact the size of the TCs, TCs in the experiments without them can reach similar intensities as those in the control experiment. We show that TC genesis is associated with an increase in the available potential energy (APE) and that convective heating dominates the APE production. Overall, our result suggests that spontaneous TC genesis may result from a cooperative interaction between convection and circulation and that radiative and surface-flux feedbacks accelerate the process. Furthermore, we find that increasing the planetary rotation favors spontaneous TC genesis.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1976

The broadening of the calcium resonance line in a high-temperature helium atmosphere

The paper describes experimental measurements of the shape of the Ca I resonance line at 4227 A in a high-temperature helium atmosphere. A ballistic piston compressor was used to produce hot helium in the temperature range from 3000 to 7000 K and the number-density range from 2 to 4 by 10 to the 20th power per cu cm, which conditions approximate those postulated for the atmospheres of certain cool white-dwarf stars. The Boltzmann temperature of the calcium atoms was measured by the brightness-emissivity method, the absorption line shape was measured with a twelve-channel polychromator, and the helium kinetic temperature was calculated from the equation of an ideal gas. The observed deviation from thermodynamic equilibrium is illustrated. The value of the ratio of the damping constant to the helium number density at 5000 K is found to be 45 (+ or - 4) by 10 to the -22nd power A cu cm, or 4.7 (+ or - 0.4) by 10 to the -9th power rad/s cu cm. It is noted that no existing line-broadening calculation for the calcium-helium system is consistent with the present results. Recent studies of the 4227-A line in spectra of the sun and the white dwarf van Maanen 2 are discussed.

Driver, R. D.↗
NASA NTRS1987

Interaction of transient radiation in nongray gaseous systems

A general formulation is presented to investigate the transient radiative interaction in nongray absorbing-emitting species between two parallel plates. Depending on the desired sophistication and accuracy, any nongray absorption model from line-by-line models to the wide band model correlations can be employed in the formulation to investigate the radiative interaction. Special attention is directed to investigate the radiative interaction in a system initially at a uniform reference temperature and suddenly the temperature of the bottom plate is reduced to a lower but constant temperature. The interaction is considered for the case of radiative equilibrium as well as for combined radiation and conduction. General as well as limiting forms of the governing equations are presented and solutions are obtained numerically by employing the method of variation of parameters. Specific results are obtained for CO, CO2, H2O, and OH. The information on species H2O and OH is of special interest for the proposed scramjet engine application. The results demonstrate the relative ability of different species for radiative interactions.

Tiwari, S. N.↗
NASA NTRS1987

Transient radiative energy transfer in nongray gases

A general formulation is presented to investigate the transient radiative interaction in nongray absorbing-emitting species between two parallel plates. Special attention is directed to investigate the radiative interaction in a system initially at a uniform reference temperature where suddenly the temperature of the bottom plate is reduced to a lower but constant temperature. The interaction is considered for the case of radiative equilibrium as well as for combined radiation and conduction. General as well as limiting forms of the govering equations are presented and solutions are obtained numerically by employing the method of variation of parameters. Specific results are obtained for CO, CO2, H2O, and OH. The information on species H2O and OH is of special interest for the proposed scramjet engine application. The results demonstrate the relative ability of different species for radiative interactions.

Tiwari, S. N.↗
NASA NTRS1993

Methods and apparatus for improving sensor performance

Methods and apparatus for improving performance of a sensor having a sensor proof mass elastically suspended at an initial equilibrium position by a suspension force, provide a tunable force opposing that suspension force and preset the proof mass with that tunable force to a second equilibrium position less stable than the initial equilibrium position. The sensor is then operated from that preset second equilibrium position of the proof mass short of instability. The spring constant of the elastic suspension may be continually monitored, and such continually monitored spring constant may be continually adjusted to maintain the sensor at a substantially constant sensitivity during its operation.

Kaiser, William J.↗
NASA NTRS1976

On the response of superpressure balloons to displacements from equilibrium density level

The response of a superpressure balloon to an initial displacement from its constant-density floating level is examined. An approximate solution is obtained to the governing vertical equation of motion for constant-density superpressure balloons. This solution is used to filter out neutrally buoyant oscillations in balloon records despite the nonlinear behavior of the balloon. The graph depicting the pressure data after deconvolution between the raw pressure data and the normalized balloon wavelet shows clearly the strong filtering-out of the neutral buoyancy oscillations.

Levanon, N.↗
NASA NTRS1976

Equations and approximations involved in computing vertical wind velocities from superpressure balloon data

Superpressure, or constant-level, balloons have long been used to obtain horizontal wind velocities in the atmosphere. This paper presents equations which can be used to evaluate omega, the vertical wind component in pressure coordinates, from on-board pressure and temperature sensors. These equations take into account the short-term displacements of a balloon from its equilibrium density level, and thus they do not assume that the balloon precisely maintains constant density. The longer-term and larger-amplitude diurnal oscillations in balloon level, and also an approximation used in deriving the vertical velocity equations, are both discussed in some detail. These equations can be used to obtain quantitative estimates of omega if reasonable estimates of the ambient lapse rate could be obtained.

Banta, R. M.↗
DOE OSTI2023

Direct Monte Carlo Simulations of Chemical Equilibrium Composition of Molecular Fluid Mixtures Under Shock Conditions

A new Monte Carlo simulation method is implemented which holds the number and kind of atoms constant rather than the number and kind of molecules for a molecular fluid mixture. Chemical reactions are allowed as a correlated move of atoms such as an interchange of atoms between molecules. Equilibrium chemical composition is determined as an average over the simulation along with equation of state quantities. Results are presented for N 2 + O 2 → 2NO at 30GPa and 3000K. The equilibrium composition is shown to be sensitive to the potentials between unlike species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

Isolating Curvature Effects in Computing Wall-Bounded Turbulent Flows

The flow over the zero-pressure-gradient So-Mellor convex curved wall is simulated using the Navier-Stokes equations. An inviscid effective outer wall shape, undocumented in the experiment, is obtained by using an adjoint optimization method with the desired pressure distribution on the inner wall as the cost function. Using this wall shape with a Navier-Stokes method, the abilities of various turbulence models to simulate the effects of curvature without the complicating factor of streamwise pressure gradient can be evaluated. The one-equation Spalart-Allmaras turbulence model overpredicts eddy viscosity, and its boundary layer profiles are too full. A curvature-corrected version of this model improves results, which are sensitive to the choice of a particular constant. An explicit algebraic stress model does a reasonable job predicting this flow field. However, results can be slightly improved by modifying the assumption on anisotropy equilibrium in the model's derivation. The resulting curvature-corrected explicit algebraic stress model possesses no heuristic functions or additional constants. It lowers slightly the computed skin friction coefficient and the turbulent stress levels for this case (in better agreement with experiment), but the effect on computed velocity profiles is very small.

Rumsey, Christopher L.↗
DOE OSTI2022

Dissociation-induced depletion of high-energy reactant molecules as a mechanism for pressure-dependent rate constants for bimolecular reactions

In 1922, Lindemann proposed the now-well-known mechanism for pressure-dependent rate constants for unimolecular reactions: reactant molecules with sufficiently high energies dissociate more quickly than collisions can reestablish the Boltzmann distribution of the internal energies of the molecule during its dissociation at low pressures – yielding pressure-dependent rate constants for unimolecular reactions due to the preferential depletion of the high energy states capable of dissociation. In the last century, incredible progress has been made in achieving a far greater understanding of and quantitative predictions for unimolecular and association reactions. In the modern era, pressure-dependent phenomenological rate constants are now nearly universally used to describe the rates of unimolecular and associative reactions in phenomenological kinetic modeling. However, there is a second, more indirect, implication of Lindemann’s mechanism that relates to how these dissociation-induced non-equilibrium distributions impact bimolecular reactions, including non-associative bimolecular reactions – which are generally not considered to have pressure-dependent rate constants. Yet, as we show herein, the same high energy states depleted due to dissociation would otherwise react most rapidly in high-activation-energy bimolecular reactions – yielding a mechanism for pressure-dependent rate constants for bimolecular reactions (including non-associative reactions). Here, we present results from a case study for CH 2 O dissociation, isomerization, and bimolecular reaction with O2 to explore this question. Results from our master equation calculations indicate that the effect of dissociation-induced non-equilibrium distributions on bimolecular reactions can be substantial – even when chemical timescales are well separated from internal energy relaxational timescales (i.e. when the traditional rate constant description would be thought to apply). This effect is found to be more pronounced – and more complex – for bimolecular reactions involving molecular entities whose chemical timescales are merged with the internal energy relaxational timescales. Lastly, we present some ideas for discussion regarding what should be considered as “chemical species” in phenomenological kinetic models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Desirable limits of accelerative forces in a space-based materials processing facility

There are three categories of accelerations to be encountered on orbiting spacecraft: (1) quasi-steady accelerations, caused by atmospheric drag or by gravity gradients, 10(exp -6) to 10(exp -7) g sub o; (2) transient accelerations, caused by movements of the astronauts, mass translocations, landing and departure of other spacecraft, etc.; and (3) oscillary accelerations, caused by running machinery (fans, pumps, generators). Steady accelerations cause continuing displacements; transients cause time-limited displacements. The important aspect is the area under the acceleration curve, measured over a certain time interval. Note that this quantity is not equivalent to a velocity because of friction effects. Transient motions are probably less important than steady accelerations because they only produce constant displacements. If the accelerative forces were not equal and opposite, the displacement would increase with time. A steady acceleration will produce an increasing velocity of a particle, but eventually an equilibrium value will be reached where drag and acceleration forces are equal. From then on, the velocity will remain constant, and the displacement will increase linearly with time.

Naumann, Robert J.↗