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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

High-pressure study of Ti{sub 50}Ni{sub 25}Fe{sub 25} powder produced by mechanical alloying

A nanostructured Ti{sub 50}Ni{sub 25}Fe{sub 25} phase (B2) was formed by mechanical alloying and its structural stability was studied as a function of pressure. The changes were followed by X-ray diffraction. The B2 phase was observed up to 7 GPa; for larger pressures, the B2 phase transformed into a trigonal/hexagonal phase (B19) that was observed up to the highest pressure used (18 GPa). Besides B2 and B19, elemental Ni or a SS-(Fe,Ni) and FeNi{sub 3} were observed. With decompression, the B2 phase was recovered. Using in situ angle-dispersive X-ray diffraction patterns, the single line method was applied to obtain the apparent crystallite size and the microstrain for both the B2 and the B19 phases as a function of the applied pressure. Values of the bulk modulus for the B2, B19, elemental Ni or SS-(Fe,Ni) and FeNi{sub 3} phases were obtained by fitting the pressure dependence of the volume to a Birch–Murnaghan equation of state (BMEOS)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Dynamics of Glyceline and Interactions of Constituents: A Multitechnique NMR Study

In this work, the dynamics of the organic components of the deep eutectic solvent (DES) glyceline are analyzed using an array of complementary nuclear magnetic resonance (NMR) methods. Fast-Field Cycling 1 H relaxometry, Pulsed Field Gradient diffusion, Nuclear Overhauser Effect Spectroscopy (NOESY), 13 C NMR relaxation and pressure dependent NMR experiments are deployed to sample a range of frequencies and modes of motion of the glycerol and choline components of the DES. Generally, translational and rotational diffusion of glycerol are more rapid than those of choline while short range rotational motions observed from 13 C relaxation indicate slow local motion of glycerol at low choline chloride (ChCl) content. The rates of glycerol and choline local motions become more similar at higher ChCl. This result taken together with pressure dependent NMR studies show that the addition of ChCl makes it easier to disrupt glycerol packing. Finally, a relatively slow hydroxyl H-exchange process between glycerol and choline protons is deduced from the data. Consistent with this, NOESY results indicate relatively little direct H-bonding between glycerol and choline. These results suggest that the glycerol H-bonding network is disrupted as choline is added, but primarily in regions where there is intimate mixing of the two components. Thus, the local dynamics of most of the glycerol, resembles that of pure glycerol until substantial choline chloride is present.

13C NMR relaxation↗
DOE OSTI2011

High-pressure phase transformations in MgO-Y2O3 nanocomposites

Temperature and pressure dependence of phase evolution in 0.5 MgO-0.5 Y{sub 2}O{sub 3} is studied using the diamond anvil method. At 300 K and 5.5 GPa, transformations in Y{sub 2}O{sub 3} are observed, resulting in co-existence of cubic, hexagonal, and monoclinic phases. Heating to 1293 K results in increased crystallinity and increase in hexagonal and monoclinic phase content. Isothermal and isobaric hold at 1273 K and 5.5 GPa for 120 min results in yttrium dissolution in cubic MgO, causing 0.83% volumetric strain. Cooling to 300 K and 0 GPa yields a four phase co-existence among cubic MgO and cubic, hexagonal, and monoclinic Y{sub 2}O{sub 3}. The residual MgO unit cell volume expansion is 0.67% at 300 K, indicating solid solution formation. Aging of the nanocomposites for 240 h does not change the observed 4 phase co-existence.

42 ENGINEERING↗
DOE OSTI2014

Shockless compression and release behavior of beryllium to 110 GPa

A magnetohydrodynamic loading technique was used to shocklessly compress beryllium to peak longitudinal stresses of 19–110 GPa and, subsequently, unload in order to determine both the compressive response and also the shear stress supported upon release. Loading strain rates were on the order of 10{sup 6 }s{sup −1}, while the unloading rates were nearly constant at 3 × 10{sup 5 }s{sup −1}. Velocimetry was used to monitor the ramp and release behavior of a beryllium/lithium fluoride window interface. After applying window corrections to infer in situ beryllium velocities, a Lagrangian analysis was employed to determine the material response. The Lagrangian wavespeed-particle velocity response is integrated to generate the stress-strain path, average change in shear stress over the elastic unloading, and estimates of the shear modulus at peak compression. These data are used to infer the pressure dependence of the flow strength at the unloading rate. Comparisons to several strength models reveal good agreement to 45 GPa, but the data indicate 20%–30% higher strength near 100 GPa.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Thermodynamic calculations of Fe–Mg interdiffusion in (Mg,Fe){sub 2}SiO{sub 4} polymorphs and perovskite

In this study, we show that the temperature and pressure dependence of Fe–Mg interdiffusion in (Fe,Mg){sub 2}SiO{sub 4} polymorphs (olivine, wadsleyite, and ringwoodite) and perovskite can be successfully reproduced in terms of bulk elastic and expansivity data through a thermodynamic model (so-called cBΩ model) that interconnects point defect parameters with bulk properties. Under dry and wet conditions, our calculated Fe–Mg interdiffusion coefficients D{sub calc}{sup Fe-Mg} (particularly for anisotropic diffusivity in olivine), activation enthalpy h{sup act}, and activation volume υ{sup act} over a wide range of geologically relevant temperatures (1000–2400 K) and pressures (0–100 GPa) are consistent with the experimental ones when the uncertainties are considered.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Spiers Memorial Lecture: Theory of unimolecular reactions

One hundred years ago, at an earlier Faraday Discussion meeting, Lindemann presented a mechanism that provides the foundation for contemplating the pressure dependence of unimolecular reactions. Since that time, our ability to model and predict the kinetics of such reactions has grown in leaps and bounds through the synergy of ever more sophisticated experimental studies with increasingly high level theoretical analyses. Herein, this review begins with a brief historical overview of the progress from the Lindemann mechanism to the master equation, which now provides the cornerstone for most theoretical analyses. The current status of ab initio transition state theory based implementations of the master equation is then reviewed, beginning with a discussion of the energy resolved chemical conversion rates, followed by a review of the pressure dependence of the thermal kinetics. The latter discussion focusses on the collisional energy and angular momentum transfer rates as well as the complexities of non-thermal effects and of multiple-well multiple-channel reactions. The synergy with recent state-of-the-art experiments is used to motivate these discussions. Attempts to automate the calculations are also briefly reviewed. Throughout the discussion, we provide our perspective on current understanding and continuing challenges and opportunities. One key challenge relates to the coupling of sequences of reactions, which frequently leads to deviations from the classic presumption of thermal reactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Boron phosphide under pressure: In situ study by Raman scattering and X-ray diffraction

Cubic boron phosphide, BP, has been studied in situ by X-ray diffraction and Raman scattering up to 55 GPa at 300 K in a diamond anvil cell. The bulk modulus of B{sub 0} = 174(2) GPa has been established, which is in excellent agreement with our ab initio calculations. The data on Raman shift as a function of pressure, combined with equation-of-state (EOS) data, allowed us to estimate the Grüneisen parameters of the TO and LO modes of zinc-blende structure, γ{sub G}{sup TO }= 1.26 and γ{sub G}{sup LO }= 1.13, just like in the case of other A{sup III}B{sup V} diamond-like phases, for which γ{sub G}{sup TO }> γ{sub G}{sup LO }≅ 1. We also established that the pressure dependence of the effective electro-optical constant α is responsible for a strong change in relative intensities of the TO and LO modes from I{sub TO}/I{sub LO} ∼ 0.25 at 0.1 MPa to I{sub TO}/I{sub LO} ∼ 2.5 at 45 GPa, for which we also find excellent agreement between experiment and theory.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2010

Tetragonal To Collapsed Tetragonal Phase Transition In BaFe{sub 2}As{sub 2} and CaFe{sub 2}As{sub 2}

Superconductivity in MFe{sub 2}As{sub 2} (M = Ba, Ca) compounds appears either at a critical doping level at ambient pressure or in the parent compound itself by application of pressure above a critical value. We report high pressure powder x-ray diffractions studies for these compounds at 300 K up to about 56 GPa using membrane diamond anvil cells. The measurements for BaFe{sub 2}As{sub 2} show a new tetragonal to collapsed tetragonal phase transition at about 22 GPa that remains stable upto 56 GPa. CaFe{sub 2}As{sub 2} is already known to transform to collapsed phase at 1.7 GPa at 300 K. Our measurements on CaFe{sub 2}As{sub 2} do not show any post collapsed phase transition on increase of pressure 50 GPa at 300 K. It is important to note that the transition in both compounds occurs when they are compressed to almost the same value of the unit cell volume and attain similar c{sub t}/a{sub t} ratios. We present a detailed analysis of the pressure dependence and structure phase transitions as well as equation of state in these important FeAs compounds that should be useful in the context of possible superconductivity in the collapsed phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Thermoelectric Properties of a Ferromagnetic Semiconductor Based on a Dirac Semimetal (Cd{sub 3}As{sub 2}) under High Pressure

The pressure dependences of thermal emf (a parameter that ranks among the most sensitive to phase transformations) are studied for the purpose of identifying baric phase transitions in the 10–50 GPa interval in the Cd{sub 3}As{sub 2} + MnAs (44.7% MnAs) structure formed by ferromagnetic MnAs granules in a semiconductor Cd{sub 3}As{sub 2} matrix.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2011

Is There a Connection Between Fragility of Glass Gorming Systems and Dynamic Heterogeneity/Cooperativity?

Although fragility of glass forming liquids is traditionally related to cooperativity in molecular motion, the connection between those parameters remains unclear. In this paper we present the estimates of cooperativity (heterogeneity) length scale obtained from the boson peak spectra. We demonstrate that agrees well with the dynamic heterogeneity length scale for the structural relaxation estimated by 4-dimensional NMR, justifying the use of . Presented analysis of large number of materials reveals no clear correlation between and fragility. However, there is a strong correlation between the cooperativity volume 3 and the activation volume measured at Tg. This observation suggests that only the volume (pressure) dependence of structural relaxation time correlates directly with the cooperativity size. However, the pure thermal (energetic) contribution to the structural relaxation, the so-called isochoric fragility, exhibits no correlation to the heterogeneity length scale , or the amount of structural units in 3. The presented results call for a revision of traditional view on the role of cooperativity/heterogeneity in structural relaxation of glass forming systems.

Hong, L↗
DOE OSTI2022

The role of collisional energy transfer in the thermal and prompt dissociation of 1-methyl allyl

Collisional energy transfer plays a pivotal role in a-priori calculations of the pressure-dependent rate constants obtained from a master equation. However, accurate determinations of collisional energy transfer parameters are rare and so most kinetic studies rely on best-fits of these parameters to experimental measurements (if available) or estimates guided from literature studies. In this work, we have quantified the effect of the uncertainty in energy transfer parameters on the thermal and prompt dissociation kinetics of a resonance stabilized radical, 1-methyl allyl (1MA), of relevance to the combustion of 1- and 2-butene isomers. Simulations using literature kinetics models were performed to assess the impact of these uncertainties on flame propagation and speciation data in laminar flames of 1- and 2-butene. Analyses of the uncertainty propagated by the energy transfer parameters for 1MA dissociation to the flame simulations, in particular the laminar flame speed, indicate an intricate coupling between the kinetics of 1MA dissociation (chain propagation) and its reaction with H-atoms (chain-termination). Ab-initio based theoretical calculations were also performed to obtain pressure-dependent kinetics for the reaction of 1MA with H-atoms. Lastly, theoretically calculated energy transfer parameters were used to best characterize the kinetics and branching between the chain propagating 1MA dissociation and the chain-terminating reaction 1MA + H.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Origin of the c-axis ultraincompressibility of Mo{sub 2}GaC above about 15 GPa from first principles

The mechanical properties and structural evolution of Mo{sub 2}GaC are calculated by first-principles under pressure. Our results unexpectedly found that the c axis is always stiffer than a axis within 0–100 GPa. An ultraincompressibility of c axis within 15–60 GPa is observed, with a contraction of about 0.2 Å, slightly larger than that of a axis (0.14 Å). The abnormal expansion of c axis and the fast decrease in a axis above about 15 GPa and 70 GPa failed to induce the structural instability, whereas such behavior caused the elastic softening in many mechanical quantities. The shrinkage anomaly of c axis is closely reflected by the internal coordinate (u) shift of Mo atom as it shows three different slopes within 0–15 GPa, 20–60 GPa, and 70–100 GPa, respectively. The longest Mo-Mo bond is responsible for the unusual shrinkage of c-axis under pressure as they experience nearly identical pressure dependences, whereas the a axis presents certain response with the variation of C-Mo bond particularly at 70 GPa. The electronic properties are investigated, including the energy band and density of states, and so on. At G point of K-M line, the energy decreases at 10 GPa first and increases at 30 GPa subsequently, the critical point is at about 15 GPa, with respective values of −0.17 of 0 GPa, −0.18 of 10 GPa, −0.16 of 15 GPa, and −0.13 of 30 GPa, respectively. This alternative energy change of G point, which is the symmetry center of the rhombic parallelogram of Ga atoms and the midpoint of the two bonded Mo atoms, convincingly reveal the origin of the anomalous ultraincompressibility of c axis as the Mo-Mo bond length shrinkage has to overcome the increasing energy barrier height. The Mo-Mo bond population and the electronegativity investigations of the Mo atom further reveal the most likely origin of the ultraincompressibility of c axis. This interesting result expects further experimental confirmation as this is the first nanolaminate ceramics compound presenting quite low-pressure axial ultraincompressibility.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2011

Shock tube and theoretical studies on the thermal decomposition of propane : evidence for a roaming radical channel.

The thermal decomposition of propane has been studied using both shock tube experiments and ab initio transition state theory-based master equation calculations. Dissociation rate constants for propane have been measured at high temperatures behind reflected shock waves using high-sensitivity H-ARAS detection and CH{sub 3} optical absorption. The two major dissociation channels at high temperature are C{sub 3}H{sub 8} {yields} CH{sub 3} + C{sub 2}H{sub 5} (eq 1a) and C{sub 3}H{sub 8} {yields} CH{sub 4} + C{sub 2}H{sub 4} (eq 1b). Ultra high-sensitivity ARAS detection of H-atoms produced from the decomposition of the product, C{sub 2}H{sub 5}, in (1a), allowed measurements of both the total decomposition rate constants, k{sub total}, and the branching to radical products, k{sub 1a}/k{sub total}. Theoretical analyses indicate that the molecular products are formed exclusively through the roaming radical mechanism and that radical products are formed exclusively through channel 1a. The experiments were performed over the temperature range 1417-1819 K and gave a minor contribution of (10 {+-} 8%) due to roaming. A multipass CH{sub 3} absorption diagnostic using a Zn resonance lamp was also developed and characterized in this work using the thermal decomposition of CH{sub 3}I as a reference reaction. The measured rate constants for CH{sub 3}I decomposition agreed with earlier determinations from this laboratory that were based on I-atom ARAS measurements. This CH{sub 3} diagnostic was then used to detect radicals from channel 1a allowing lower temperature (1202-1543 K) measurements of k1a to be determined. Variable reaction coordinate-transition state theory was used to predict the high pressure limits for channel (1a) and other bond fission reactions in C{sub 3}H{sub 8}. Conventional transition state theory calculations were also used to estimate rate constants for other tight transition state processes. These calculations predict a negligible contribution (<1%) from all other bond fission and tight transition state processes, indicating that the bond fission channel (1a) and the roaming channel (1b) are indeed the only active channels at the temperature and pressure ranges of the present experiments. The predicted reaction exo- and endothermicities are in excellent agreement with the current version of the Active Thermochemical Tables. Master equation calculations incorporating these transition state theory results yield predictions for the temperature and pressure dependence of the dissociation rate constants for channel 1a. The final theoretical results reliably reproduce the measured dissociation rate constants that are reported here and in the literature. The experimental data are well reproduced over the 500-2500 K and 1 x 10{sup -4} to 100 bar range (errors of {approx}15% or less) by the following Troe parameters for Ar as the bath gas: k{sub {infinity}} = 1.55 x 10{sup 24}T{sup -2.034} exp(-45490/T) s{sup -1}, k{sub 0} = 7.92 x 10{sup 53}T{sup -16.67} exp(-50380/T) cm{sup 3} s{sup -1}, and F{sub c} = 0.190 exp(-T/3091) + 0.810 exp(-T/128) + exp(-8829/T).

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

Oxidation and pyrolysis of methyl propyl ether

The ignition, oxidation, and pyrolysis chemistry of methyl propyl ether (MPE) was probed experimentally at several different conditions, and a comprehensive chemical kinetic model was constructed to help understand the observations, with many of the key parameters computed using quantum chemistry and transition state theory. Experiments were carried out in a shock tube measuring time variation of CO concentrations, in a flow tube measuring product concentrations, and in a rapid compression machine (RCM) measuring ignition delay times. The detailed reaction mechanism was constructed using the Reaction Mechanism Generator software. Sensitivity and flux analyses were used to identify key rate and thermochemical parameters, which were then computed using quantum chemistry to improve the mechanism. Validation of the final model against the 1-20 bar 600-1500 K experimental data is presented with a discussion of the kinetics. The model is in excellent agreement with most of the shock tube and RCM data. Strong non-monotonic variation in conversion and product distribution is observed in the flow-tube experiments as the temperature is increased, and unusually strong pressure dependence and significant heat release during the compression stroke is observed in the RCM experiments. These observations are largely explained by a close competition between radical decomposition and addition to O2 at different sites in MPE; this causes small shifts in conditions to lead to big shifts in the dominant reaction pathways. The validated mechanism was used to study the chemistry occurring during ignition in a diesel engine, simulated using Ignition Quality Test (IQT) conditions. At the IQT conditions, where the MPE concentration is higher, bimolecular reactions of peroxy radicals are much more important than in the RCM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structural stability, vibrational, and bonding properties of potassium 1, 1′-dinitroamino-5, 5′-bistetrazolate: An emerging green primary explosive

Potassium 1,1′-dinitroamino-5,5′-bistetrazolate (K{sub 2}DNABT) is a nitrogen rich (50.3% by weight, K{sub 2}C{sub 2}N{sub 12}O{sub 4}) green primary explosive with high performance characteristics, namely, velocity of detonation (D = 8.33 km/s), detonation pressure (P = 31.7 GPa), and fast initiating power to replace existing toxic primaries. In the present work, we report density functional theory (DFT) calculations on structural, equation of state, vibrational spectra, electronic structure, and absorption spectra of K{sub 2}DNABT. We have discussed the influence of weak dispersive interactions on structural and vibrational properties through the DFT-D2 method. We find anisotropic compressibility behavior (b<a<c) from pressure dependent structural properties. The predicted equilibrium bulk modulus reveals that K{sub 2}DNABT is softer than toxic lead azide and harder than the most sensitive cyanuric triazide. A complete assignment of all the vibrational modes has been made and compared with the available experimental results. The calculated zone center IR and Raman frequencies show a blue-shift which leads to a hardening of the lattice upon compression. In addition, we have also calculated the electronic structure and absorption spectra using recently developed Tran Blaha-modified Becke Johnson potential. It is found that K{sub 2}DNABT is a direct band gap insulator with a band gap of 3.87 eV and the top of the valence band is mainly dominated by 2p-states of oxygen and nitrogen atoms. K{sub 2}DNABT exhibits mixed ionic (between potassium and tetrazolate ions) and covalent character within tetrazolate molecule. The presence of ionic bonding suggests that the investigated compound is relatively stable and insensitive than covalent primaries. From the calculated absorption spectra, the material is found to decompose under ultra-violet light irradiation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Probing the high-pressure densification of amorphous silica nanomaterials using SBA-15: An investigation into the paradoxical nature of the first sharp diffraction peak

The densification and X-ray scattering of mesoporous silica (SBA-15) were measured simultaneously under gigapascal (GPa) pressures. The results are compared to previous work on amorphous silica (aSiO 2 ) and demonstrate the feasibility of measuring the densification of aSiO 2 nanomaterials with small angle X-ray scattering (SAXS) in-situ in a diamond anvil cell. Compared to fused silica, the position of the SBA-15 first sharp diffraction peak (FSDP) is 7 times more sensitive to pressure and has a transition in its pressure dependance at a lower pressure (~2 GPa vs.~13 GPa). SBA-15 has two densification regimes, low-density amorphous and highdensity amorphous, which have equations of state comparable to low-density amorphous and high-density amorphous fused silica. Further, the transition between these two regimes occurs at a lower pressure than for fused silica (~1.5 GPa vs.~13 GPa). The results suggest that there is no direct relationship between the FSDP position and the aSiO 2 density during compression.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1976

Rate of the reaction of atomic hydrogen with propyne over an extended pressure and temperature range

The technique of flash photolysis coupled with time resolved detection of H via resonance fluorescence has been used to obtain rate constants for the reaction of atomic hydrogen with propyne at temperatures from 215 to 460 K and at pressures in the range 5-600 torr. The rate constants are strongly pressure dependent and the high pressure limiting values give rise to the Arrhenius expression K = approximately 6 x 10 to the minus 11th exp(-2450T) cu cm per molecule per sec. The results are discussed and compared with those of previous studies

Whytock, D. A.↗