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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

[Results of Simulation Studies]

Lattice Monte Carlo and off-lattice molecular dynamics simulations of h(sub 1)t(sub 4) and h(sub 4)t(sub l) (head/tail) amphiphile solutions have been performed as a function of surfactant concentration and temperature. The lattice and off-lattice systems exhibit quite different self-assembly behavior at equivalent thermodynamic conditions. We found that in the weakly aggregating regime (no preferred-size micelles), all models yield similar micelle size distributions at the same average aggregation number, albeit at different thermodynamic conditions (temperatures). In the strongly aggregating regime, this mapping between models (through temperature adjustment) fails, and the models exhibit qualitatively different micellization behavior. Incipient micellization in a model self-associating telechelic polymer solution results in a network with a transient elastic response that decays by a two-step relaxation: the first is due to a heterogeneous jump-diffusion process involving entrapment of end-groups within well-defined clusters and this is followed by rapid diffusion to neighboring clusters and a decay (terminal relaxation) due to cluster disintegration. The viscoelastic response of the solution manifests characteristics of a glass transition and entangled polymer network.

Source record↗
NASA NTRS1973

A quantum model for bending vibrations and thermodynamic properties of C3.

The investigation reported was conducted to clarify the thermodynamic properties of C3 by further developing the limit to the partition function suggested by Strauss and Thiele (1967). A quantum solution for the energy levels of a quadratically perturbed square well potential is presented and the consistency of this limit with observed energy levels is established. In the process a more complete physical picture of the bending C3 molecules emerges. The values of entropy deduced from various measurements of graphite pressure are compared with this limit, and the thermodynamic properties predicted for the limiting case are evaluated.

Hansen, C. F.↗
DOE OSTI2025

How Thermodynamic, Electronic, and Steric Factors Influence Mesitylcopper Oligomers

Mesitylcopper (CuMes) is a highly versatile organocopper reagent used in both organic and inorganic syntheses. It has previously been shown that CuMes exists as a tetrameric or pentameric cyclic oligomer [CuMes] n (n = 4, 5), both in solution and in the solid state. The bonding arrangement between the [CuMes] units has qualitatively been described as localized three-center twoelectron (3c-2e) bonds. However, the electronic, structural, and thermodynamic forces driving this aggregation are still not well understood. For this reason, we employed density functional theory (DFT) calculations to study mesitylcopper as a monomeric [CuMes] unit and [CuMes]n oligomers with n = 2 to n = 7. We found that there is a strong electronic driving force for aggregation caused by strong mixing between the Cu’s d orbitals and Mes’s π orbitals in oligomers larger than the dimer. This mixing is only optimized in oligomers with n ≥ 3, where the mesityl group is no longer bonded to a single copper center but instead becomes a bridging ligand. Beyond the trimer, steric and entropic factors become relevant for determining the relative stabilities of the different aggregates, with midsized oligomers (n = 4−5) having the optimal balance between the electronic Cu−C bonding character, Cu···Cu attractive forces, entropy, reduced internal ring strain, and reduced steric interactions between the mesityl groups.

Copper↗
NASA NTRS2006

Compositional Pathways and Capillary Effects during Early-stage Isothermal Precipitation in a Nondilute Ni-Al-Cr Alloy

For a Ni-5.2 Al-14.2 Cr at.% alloy with moderate solute supersaturations, the compositional pathways, as measured with atom-probe tomography, during early to later stage y'(LI2)-precipitation (R = 0.45-10 nm), aged at 873 K, are discussed in light of a multi-component coarsening model. Employing nondilute thermodynamics, detailed model analyses during quasistationary coarsening of the experimental data establish that the y/y' interfacial free-energy is 22- 23+/-7 mJ/sq m. Additionally, solute diffusivities are significantly slower than model estimates. Strong quantitative evidence indicates that an observed y'-supersaturation of Al results from the Gibbs-Thomson effect, providing the first experimental verification of this phenomenon. The Gibbs-Thomson relationship, for a ternary system, as well as differences in measured phase equilibria with CALPHAD assessments, are considered in great detail.

Sudbrack, Chantal K.↗
DOE OSTI2023

Thermodynamic re-modeling of the Yb-Sb system aided by first-principles calculations

Here, the thermodynamic description of the Yb-Sb binary system is developed by means of the CALculations of PHAse Diagrams (CALPHAD) method by combining experimental data in the literature and predictions from first-principles calculations based on density functional theory (DFT) in the literature and the present work. Two pseudopotentials of Yb are compared in the present DFT-based calculations with 14 and 13 f-electrons frozen in the core, i.e., 5p 6 6s 2 and 5p 6 6s 2 5 d 1 electrons as valence electrons, termed Yb_2 and Yb_3, respectively. It is shown that the phonon spectrum of the YbSb phase calculated using the Yb_3 pseudopotential does not have imaginary phonon modes and is subsequently used to predict its temperature dependent thermodynamic properties by the DFT-based quasiharmonic phonon calculations. The present thermodynamic database includes the Yb 16 Sb 11 phase in addition to five intermetallic phases that were considered in previous modeling studies, i.e., YbSb 2 , YbSb, Yb 11 Sb 10 , Yb 4 Sb 3 , and Yb 5 Sb 3 . The high temperature orthorhombic structure of the Yb 5 Sb 3 phase is not considered in the present work as it was stabilized by hydrogen. The associate solution model is used to describe the short-range ordering behavior in the liquid phase. The calculations from the present thermodynamic model show good agreement with thermochemical and phase equilibrium data from both the present work and the literature.

36 MATERIALS SCIENCE↗
NASA NTRS2011

Base Heating Sensitivity Study for a 4-Cluster Rocket Motor Configuration in Supersonic Freestream

In support of launch vehicle base heating and pressure prediction efforts using the Loci-CHEM Navier-Stokes computational fluid dynamics solver, 35 numerical simulations of the NASA TND-1093 wind tunnel test have been modeled and analyzed. This test article is composed of four JP-4/LOX 500 lbf rocket motors exhausting into a Mach 2 - 3.5 wind tunnel at various ambient pressure conditions. These water-cooled motors are attached to a base plate of a standard missile forebody. We explore the base heating profiles for fully coupled finite-rate chemistry simulations, one-way coupled RAMP (Reacting And Multiphase Program using Method of Characteristics)-BLIMPJ (Boundary Layer Integral Matrix Program - Jet Version) derived solutions and variable and constant specific heat ratio frozen flow simulations. Variations in turbulence models, temperature boundary conditions and thermodynamic properties of the plume have been investigated at two ambient pressure conditions: 255 lb/sq ft (simulated low altitude) and 35 lb/sq ft (simulated high altitude). It is observed that the convective base heat flux and base temperature are most sensitive to the nozzle inner wall thermal boundary layer profile which is dependent on the wall temperature, boundary layer s specific energy and chemical reactions. Recovery shock dynamics and afterburning significantly influences convective base heating. Turbulence models and external nozzle wall thermal boundary layer profiles show less sensitivity to base heating characteristics. Base heating rates are validated for the highest fidelity solutions which show an agreement within +/-10% with respect to test data.

Mehta, Manish↗
DOE OSTI2021

Role of thermo-mechanical gyrations on the α/β interface stability in a Ti6Al4V AM alloy

Fluctuating energy distributions experienced during Additive Manufacturing yield an evolution of spatial and temporal transients within a part. In general, the in-situ monitoring of these transients is near to impossible during manufacturing. In order to then gain perspective into the impact on these localized thermo-mechanical transients on the interface stability, rapid thermo-mechanical reversals with known boundary conditions are imposed on an AM Ti6Al4V alloy which resulted in a phase transformation leading to an increased β phase stability. Our goal with this study is to comprehend the kinetics of this phase transformation with concepts of stored energy due to plastic strain accumulation and diffusion kinetics. Atom Probe Tomography is employed to study the partitioning of the solute elements across the interface. As expected, the thermo-mechanically cycled samples showed a reduced Vanadium concentration across the β phase. Finally, this concentration profile across the interface, alongside a full-width-half-max analysis, provided insight on the potential phase transformation kinetics involved in the α → β transformation subject to thermo- mechanical gyrations.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Kinetic Pathways Templated by Low-Temperature Intermediates during Solid-State Synthesis of Layered Oxides

Layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-nickel (Ni) systems are attractive because of their high capacity. For practical use, synthetic control of stoichiometry and structural ordering is crucial but has been nontrivial due to the complexity inherent to synthesis reactions, which often proceed via nonequilibrium pathways. In this paper, we report here a combined in situ synchrotron X-ray diffraction and ab initio study of solid-state synthesis of layered oxides starting from acetate precursors for LiCoO 2 and LiNiO 2 and their solid solution LiNi 0.8 Co 0.2 O 2 . While all three systems ultimately evolve into the same thermodynamically stable layered phase ($R\overline{3}m$), each chemistry involves distinct metastable intermediates. We explain the phase progressions using a structural template model, demonstrating that during the synthesis of LiCoO 2 , the formed metastable spinel polymorph (Li 2 Co 2 O 4 ; $Fd\overline{3}m$) is a kinetically facile lithiation product of spinel Co 3 O 4 —the low-temperature (LT) intermediate from the decomposed Co-acetate. Similarly, in the Ni-based systems, the acetate decomposition products, rocksalts (Ni,Co)O, topotactically template the kinetic pathways of forming disordered rocksalts (Li x (Ni,Co) 2–x O 2 ; $Fm\overline{3}m$), consequently leading to off-stoichiometric Li x (Ni,Co)O 2 with undesired high Li/Ni mixing. These findings highlight new opportunities for engineering precursors to form LT intermediates that template the synthesis of target phases and structural properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations

Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here in this paper, electrospray ionization was used to generate gas-phase complexes [ML 3 ] 3+ , where M = La, Lu, or Am and L is EtBTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine. Collision-induced dissociation (CID) of [ML 3 ] 3+ in the presence of H 2 O yielded a protonated ligand [L(H)] + and hydroxide [ML 2 (OH)] 2+ or hydrate [ML(L–H)(H 2 O)] 2+ , where (L–H) - is a deprotonated ligand. Although solution affinities indicate stronger binding of BTPs toward Am 3+ versus Ln 3+ , the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accordance with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL 3 ] 3+ versus [LaL 3 ] 3+ and for both product isomers, [ML 2 (OH)] 2+ and [ML(L–H)(H 2 O)] 2+ . More facile removal of a ligand from [AmL 3 ] 3+ by CID does not necessarily contradict stronger Am 3+ –L binding, as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predicting the seemingly anomalous CID behavior, the computational results indicate greater participation of Am 5f versus La 4f orbitals in metal–ligand bonding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1966

Computer program determines chemical composition of physical system at equilibrium

FORTRAN 4 digital computer program calculates equilibrium composition of complex, multiphase chemical systems. This is a free energy minimization method with solution of the problem reduced to mathematical operations, without concern for the chemistry involved. Also certain thermodynamic properties are determined as byproducts of the main calculations.

Kwong, S. S.↗
NASA NTRS1986

Smoothing and the second law

The technique of obtaining second order, oscillation free, total variation diminishing (TVD), scalar difference schemes by adding a limited diffusion flux (smoothing) to a second order centered scheme is explored. It is shown that such schemes do not always converge to the correct physical answer. The approach presented here is to construct schemes that numerically satisfy the second law of thermodynamics on a cell by cell basis. Such schemes can only converge to the correct physical solution and in some cases can be shown to be TVD. An explicit scheme with this property and second order spatial accuracy was found to have an extremely restrictive time step limitation (Delta t less than Delta x squared). Switching to an implicit scheme removed the time step limitation.

Merriam, Marshal L.↗
NASA NTRSDate not supplied

In Pursuit of CFD-based Wind Tunnel Calibrations

Computational fluid dynamic simulations of models tested in wind tunnels require a high level of fidelity and accuracy, particularly for the purposes of CFD validation efforts. Considerable effort is required to ensure a sufficient characterization of both the physical geometry of the wind tunnel, the thermodynamics of the tunnel, and flow conditions in the test section. The condition setting process among subsonic wind tunnels, closed or open throat, is generally the same, though they can differ in specific details of the thermodynamics. The derivation, application, and error estimation of condition setting and calibration is discussed. Computational flow solutions of the high-speed leg of the NASA Langley Research Center 14- by 22-Foot Subsonic Tunnel are used to evaluate the calibration process and discuss calibration curve sensitivities. Duplicating the characteristics of a particular wind tunnel is difficult at best. A calibration curve derived from the computational method is the most consistent method to use for tunnel condition setting.

wind tunnel↗
NASA NTRS1972

An implicit finite-difference solution to the viscous shock layer, including the effects of radiation and strong blowing

An implicit finite-difference scheme is developed for the fully coupled solution of the viscous, radiating stagnation-streamline equations, including strong blowing. Solutions are presented for both air injection and injection of carbon-phenolic ablation products into air at conditions near the peak radiative heating point in an earth entry trajectory from interplanetary return missions. A detailed radiative-transport code that accounts for the important radiative exchange processes for gaseous mixtures in local thermodynamic and chemical equilibrium is utilized in the study. With minimum number of assumptions for the initially unknown parameters and profile distributions, convergent solutions to the full stagnation-line equations are rapidly obtained by a method of successive approximations. Damping of selected profiles is required to aid convergence of the solutions for massive blowing. It is shown that certain finite-difference approximations to the governing differential equations stabilize and improve the solutions. Detailed comparisons are made with the numerical results of previous investigations. Results of the present study indicate lower radiative heat fluxes at the wall for carbonphenolic ablation than previously predicted.

Garrett, L. B.↗
DOE OSTI2025

Development of a kinetic-thermodynamic model for lime-stabilization of Na-bentonite

This study presents the first kinetic model to predict the solid and pore solution composition of Na-bentonite clay reacting with slaked lime over a period of 720 days. The model successfully accounts for most experimental data using a single kinetic rate constant. The following sequence of reactions was predicted by the model: initial rapid dissolution of portlandite within the first 7 days, leading to a decrease in pH and dissolved calcium, and concurrent formation of calcium silicate hydrates (C-S-H: jennite), calcium aluminate hydrate (C-A-H: C₄AH₁₃), calcium aluminosilicate hydrates (stratlingite) and hydrotalcite. After 7 days, jennite and stratlingite are predicted to transform into tobermorite-II, contributing to strength development up to 28 days. From 28 to 90 days, continued montmorillonite dissolution is predicted, along with minor formation of ettringite, partial tobermorite-II dissolution, and precipitation of secondary phases such as albite and talc. Experimentally, portlandite dissolution was confirmed by TGA and XRD and found to be complete within 7 days, in agreement with model predictions. However, other predicted solid-phase transformations (e.g., tobermorite-II formation and dissolution, ettringite, albite, and talc formation) could not be conclusively verified through experimental techniques. Aqueous phase measurements confirmed that the pH and Ca trends in solution, and that equilibrium was reached by 90 days.

Chemical kinetics↗
DOE OSTI2025

Kerr effective black hole geometries in supergravity

We derive the explicit embedding of the effective Kerr spacetimes, which are pertinent to the vanishing of static Love numbers, soft hair descriptions of Kerr black holes, and low-frequency scalar-Kerr scattering amplitudes, as solutions within 𝑁 = 2 supergravity. These spacetimes exhibit a hidden 𝑆⁢𝐿⁡(2,𝑅) × 𝑈⁡(1) or 𝑆⁢𝑂⁡(4,2) symmetry resembling the so called subtracted geometries with 𝑆⁢𝐿⁡(2,𝑅) × 𝑆⁢𝐿⁡(2,𝑅) symmetry, which accurately represent the near-horizon geometry of Kerr black holes and, as we will argue most accurately represents the internal structure of the Kerr black hole. To quantify the differences among the effective Kerr spacetimes, we compare their physical quantities, internal structures, and geodesic equations. Although their thermodynamic properties, including entropy, match those of Kerr, our study uncovers significant differences in the interiors of these effective Kerr solutions. A careful examination of the internal structure of the spacetimes highlights the distinctions between various effective Kerr geometries and their quasinormal spectra.

quantum aspects of black holes↗
DOE OSTI2021

Phase Relationships in the Carbon–Titanium–Uranium System for Ultra-High Temperature Nuclear Fuels

Carbides of uranium have attracted interest as fuels for nuclear thermal propulsion (NTP) to drive deep-space exploration owing to their attractive thermal and neutronic properties. Optimization of NTP technology, however, requires ultra-high temperature reactor environments to maximize the ratio of thrust to propellant to achieve peak rocket engine efficiency. Incorporation of transition metals into uranium carbides offers a pathway to increase the melting point of carbide fuels to address the operational challenges posed by NTP. Here, a thermodynamic model has been developed to examine the phase relationships in the C–Ti–U system at NTP conditions. Calculated phase relationships at ultra-high temperatures predict a stable (U, Ti)C solid solution. Additionally, experimental work on C–Ti–U synthesis via arc melting has been carried out, providing data on phase constitution and compositions that can be used to further refine the thermodynamic model that has been developed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Ensemble Effects on Hydroxide Bond Dissociation Free Energies in Polyoxovanadate Clusters

Understanding structure-property relationships is foundational to numerous modern chemistries, such as proton-coupled electron transfer (PCET). However, an experimentally measured property is the result of the behavior from an ensemble of molecules. Neglecting ensemble effects, especially under complex chemical environments, may obfuscate these relationships and lead to discrepancies between theory and experiment. In this work, we demonstrate the impact of configurational entropy and local chemical environments on hydroxide bond dissociation free energies [BDFE- (O−H)] for a set of polyoxovanadate nanoclusters, at ambient conditions. The O−H bond strengths are investigated via density functional theory (DFT) coupled with statistical thermodynamic analysis and bilinear modeling, and compared with previous experimental results on the same systems, namely electrochemical solutions of: [V 6 O 13−x (OH) x (TRIOL R ) 2 ] −2 (x = 2, 4, 6; R = NO 2 , Me) and [V 6 O 11−x (OMe) 2 (OH) x (TRIOL NO 2 ) 2 ] −2 (x = 2, 4). Interestingly, we find that ensemble effects, even at room temperature, can account for a significant portion of the BDFE(O−H) trend with the degree of reduction via H atom binding, which cannot be fully captured by single-structure, static DFT calculations. Moreover, we find that the ensemble effects may be replicated statistically, requiring only enumeration of energetically accessible H-binding sites. With the ensemble effects resolved, we present a simple bilinear model to reconcile remaining biases between experiment and ensemble-informed theory, which corelate with clusterspecific electronic environment differences. The bilinear model achieves outstanding accuracy vs experiments with a root-mean squared error of 0.4 kcal/mol. Finally, based on the physicochemical characteristics of hydrogen interaction with polyoxometalates, we present a simple methodology that captures the BDFE(O−H) trend while dramatically reducing required DFT calculations by 98% and achieving accuracy within 1 kcal/mol. Overall, this work elucidates the roles and structural origins of configurational entropy and chemical effects on polyoxometalate hydroxide bond energies, with potential applicability to various atomically precise metal oxide systems. Importantly, it introduces models for rapid and highly accurate property calculations in connection with experiments.

Cluster chemistry↗