Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Thermodynamic limit”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
NASA NTRS2019

Development of a Space-Flight ADR Providing Continuous Cooling at 50 mK with Heat Rejection at 10 K

Future astronomical instruments will require sub-Kelvin detector temperatures to obtain high sensitivity. In many cases large arrays of detectors will be used, and the associated cooling systems will need performance surpassing the limits of present technologies. NASA is developing a compact cooling system that will lift heat continuously at temperatures below 50 mK and reject it at over 10 K. Based on Adiabatic Demagnetization Refrigerators (ADRs), it will have high thermodynamic efficiency and vibration-free operation with no moving parts. It will provide more than 10 times the current flight ADR cooling power at 50 mK and will also continuously cool a 4 K stage for instruments and optics. In addition, it will include an advanced magnetic shield resulting in external field variations below 5 µT. We describe the cooling system here and report on the progress in its development.

Tuttle, Jim↗
DOE OSTI2021

Searching for a route to synthesize in situ epitaxial Pr 2 Ir 2 O 7 thin films with thermodynamic methods

In situ growth of pyrochlore iridate thin films has been a long-standing challenge due to the low reactivity of Ir at low temperatures and the vaporization of volatile gas species such as IrO 3 (g) and IrO 2 (g) at high temperatures and high P O2 . To address this challenge, we combine thermodynamic analysis of the Pr-Ir-O 2 system with experimental results from the conventional physical vapor deposition (PVD) technique of co-sputtering. Our results indicate that only high growth temperatures yield films with crystallinity sufficient for utilizing and tailoring the desired topological electronic properties and the in situ synthesis of Pr 2 Ir 2 O 7 thin films is fettered by the inability to grow with P O2 on the order of 10 Torr at high temperatures, a limitation inherent to the PVD process. Thus, we suggest techniques capable of supplying high partial pressure of key species during deposition, in particular chemical vapor deposition (CVD), as a route to synthesis of Pr 2 Ir 2 O 7 .

Chemistry↗
DOE OSTI2022

Investigating the limits of superconductivity in UTe 2

Abstract Spin-triplet bulk superconductors are a promising route to topological superconductivity, and UTe 2 is a recently discovered contender. The superconducting properties of UTe 2 , however, vary substantially as a function of the synthetic route, and even nonsuperconducting single crystals have been reported. To understand the driving mechanism suppressing superconductivity, we investigate UTe 2 single crystals grown close to the nonsuperconducting boundary (growth temperature ∼710 ∘ C) through a combination of thermodynamic and x-ray diffraction measurements. Specific heat measurements reveal a sharp decrease in the superconducting volume and a concomitant increase in the residual specific heat coefficient close to the nonsuperconducting boundary. Notably, these crystals are inhomogeneous and show an apparent double transition in specific heat measurements, similar to samples grown at much higher temperatures (∼1000 ∘ C). Our single crystal x-ray diffraction measurements reveal that there are two important tuning parameters: uranium vacancies and the atomic displacement along the c axis, which shows a twofold increase in samples with a reduced superconducting volume. Our results highlight the key role of local disorder along the uranium-uranium dimers and suggest that the apparent double superconducting transition is more likely to emerge close to the superconducting limits of UTe 2 .

Weiland, A. (ORCID:0000000171983559)↗
NASA NTRS2011

Demonstrating the Operational Value of Thermodynamic Hyperspectral Profiles in the Pre-Convective Environment

The Short-term Prediction Research and Transition Center (SPoRT) is a collaborative partnership between NASA and operational forecasting partners, including a number of National Weather Service (NWS) Weather Forecasting Offices (WFO). As a part of the transition to operations process, SPoRT attempts to identify possible limitations in satellite observations and provide operational forecasters a product that will result in the most impact on their forecasts. One operational forecast challenge that some NWS offices face, is forecasting convection in data-void regions such as large bodies of water. The Atmospheric Infrared Sounder (AIRS) is a sounding instrument aboard NASA's Aqua satellite that provides temperature and moisture profiles of the atmosphere. This paper will demonstrate an approach to assimilate AIRS profile data into a regional configuration of the WRF model using its three-dimensional variational (3DVAR) assimilation component to be used as a proxy for the individual profiles.

Kozlowski, Danielle↗
DOE OSTI2021

Thermodynamically Stable, Plasmonic Transition Metal Oxide Nanoparticle Solar Selective Absorbers towards 95% Optical-to-Thermal Conversion Efficiency at 750 °C

Generation 3 (Gen) concentrating solar power (CSP) systems requires a high operation temperature ≥750°C to increase the power-cycle efficiency towards ≥50%. However, such a high operation temperature poses a notable challenge to high temperature materials. On the receiver side, a critical challenge is the lack of solar selective absorbers that demonstrate both high optical-to-thermal energy conversion efficiency η therm approaching 95% and long-term thermal stability at >750°C in air. Existing solar absorbers either have limited η therm ≤89% or deteriorate significantly within 500 h at 750°C; some of these also require costly vacuum deposition for stringent thickness control. Therefore, it is highly desirable to simultaneously achieve η therm ~95% AND high thermal stability at 750°C for future generations of CSP receivers. This project has investigated and developed low-cost, highly scalable spray-coated transition metal oxide nanoparticle (NP) pigmented solar selective coatings on various types of Inconel alloy tube sections that are thermodynamically stable at 750-800°C in air, maintaining η therm >94.3%(93.2%) under a solar concentration ratio of C=1000 after 60 simulated day-night cycles at 750ºC (800ºC) (1 cycle=12 h at 750 or 800°C and 12h ramping down to 25°C). We have also coated up to 48 inches long receiver tubes for preliminary solar testing under Norwich Technology’s parabolic trough systems, demonstrating notably improved performance in solar heating compared to benchmark Pyromark 2500 coatings. Two key innovations have been developed in this project: (1) We achieved an unprecedented high thermal efficiency >94% by optimizing the d-band optical absorption spectra of transition metal ions, engineering their valences and stoichiometry; (2) We were able to maintain or even slightly increase the efficiency when operating at 750°C in air by engineering the interdiffusion of transition metal ions between the coating and the Inconel substrate to our advantage. Featuring high-temperature solar spectral selectivity and thermodynamic stability in air, as well as low-cost, highly scalable solution-chemical synthesis and spray coating techniques, this innovation in solar selective absorber technology alone accounts for nearly 40% of the targeted reduction in the levelized cost of electricity (LCOE) from the receiver, thermal energy storage, and operation & maintenance combined by 2030, as proposed by the U.S. Department of Energy. For a 110 MWe CSP power plant, this LCOE reduction from the solar selective coating alone transfers to ~$\$ $1.9 M increase in annual profit based on a sales price of 10¢/kWh (or an annual sale of $50 M/year). The high solar absorptance (~98%) NP pigment materials developed in this project are equally applicable to volumetric receivers either as a coating or as bigger ceramic microspheres after sintering, potentially benefiting Gen3 falling particle CSP technologies. All these contributions facilitate the larger scale deployment of CSP systems with energy storage capability to address the intermittency issue of solar energy towards dispatchable solar electricity, bridging the temporal gap between peak solar electricity production and peak electricity consumption. The collaboration with Norwich Technologies and Brayton Energy in this project will also facilitate the future commercialization of this new solar selective coating technology developed in this SIPS project.

14 SOLAR ENERGY↗
DOE OSTI2023

Thermal scattering law for ice based on neutron time-of-flight experiments carried out at the SEQUOIA spectrometer at the Oak Ridge National Laboratory

Precise estimation of neutron thermalization in moderators relies on high-fidelity thermal scattering cross-section data governed by the thermal scattering law (TSL). The Institut de Radioprotection et de Sûreté Nucléaire (IRSN) has been working on the development of improved TSL for light water ice. Many polymorphic phases of light water ice exist depending on the thermodynamic conditions. The most common type of ice at standard pressure and temperature below water freezing point (273.15 K) is ice-Ih. It is essential to have high-resolution experimental double differential data for developing and/or validating TSL for moderator materials.Existing experimental double-differential scattering data for ice-Ih are extremely sparse and of limited quality. New high-quality double-differential measurements for ice-Ih over multiple temperatures and incident neutron energies would directly support the validation and improvement of ice-Ih TSL models for criticality safety applications.Series of time-of-flight (TOF) inelastic neutron scattering experiments on ice-Ih at temperatures starting at 271 K and down to 6 K, have been carried out at the SEQUOIA spectrometer at the Spallation Neutron Source (SNS) at the Oak Ridge National Laboratory (ORNL), United States. The experiments have been performed for incident neutron energies, Ei= 11, 55, 160, 250, and 600 meV, to explore different excitation energies in the vibrational phonon spectrum. This paper presents the thermodynamic conditions and the details of the TOF measurements on ice-Ih and the derived phonon spectrum from the experimentally measured double differential data. A study of the variation of the phonon spectrum of ice-Ih as a function of temperature is highlighted, and a preliminary TSL evaluation is developed based on the experimental phonon spectrum.

Jaiswal, V↗
DOE OSTI2023

Near-extremal charged black holes: greybody factors and evolution

As a charged black hole reaches its extremal state via Hawking radiation, quantum effects become important for its thermodynamic properties when its temperature is below a mass gap scale. Using AdS 2 /CFT 1 correspondence and solutions for the corresponding Schwarzian action, we calculate the black hole greybody factors including the quantum effects. In the low temperature limit, the greybody factors scale as T 2s+3/2 with s the radiated field spin. Hence, the Hawking radiation of a near-extremal charged black hole (NEBH) is dominated by emitting scalar particles including the Higgs boson. Time evolution of an NEBH is also calculated and shows a stochastic feature. For an NEBH lighter than around 10 8 times the Planck mass, its temperature at the current universe is below the mass gap scale and is universally tens of GeV, which is important if one searches for primordial (hidden) charged black holes.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Computational analysis of the tryptophan cation radical energetics in peroxidase Compound $\mathrm{I}$

Three well-characterized heme peroxidases (cytochrome c peroxidase = CCP, ascorbate peroxidase = APX, and Leishmania major peroxidase = LMP) all have a Trp residue tucked under the heme stacked against the proximal His heme ligand. The reaction of peroxidases with H 2 O 2 to give Compound I results in the oxidation of this Trp to a cationic radical in CCP and LMP but not in APX. Considerable experimental data indicate that the local electrostatic environment controls whether this Trp or the porphyrin is oxidized in Compound I. Attempts have been made to place the differences between these peroxidases on a quantitative basis using computational methods. These efforts have been somewhat limited by the approximations required owing to the computational cost of using fully solvated atomistic models with well-developed forcefields. This now has changed with available GPU computing power and the associated development of software. Here we employ thermodynamic integration and multistate Bennett acceptance ratio methods to help fine-tune our understanding on the energetic differences in Trp radical stabilization in all three peroxidases. These results indicate that the local solvent structure near the redox active Trp plays a significant role in stabilization of the cationic Trp radical.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Synchrotron X-ray diffraction analysis of constituent phases in transition joint between nickel alloy 738LC and a MnFeCoNiCu alloy

Synchrotron x-ray diffraction (XRD) analysis was performed on transition joints between a single-phase MnFeCoNiCu alloy and Ni-base Alloy 738LC to efficiently identify the constituent phases across the interface, with different levels of material intermixing generated by laser-welding with variable power. Here, the intermixing extent was quantified by postmortem energy dispersive x-ray spectroscopy mapping. Diffraction-based analyses on complex composition spaces with limited prior data present significant challenges because elemental substitution in both disordered and ordered phases is more extensive than in conventional alloy spaces, which may effectuate relatively large shifts in the observed lattice parameters that convolute the analysis. Therefore, thermodynamic simulations and crystallographic literature data were employed to construct a system-specific diffraction library of twelve prospective phases for the composition space investigated. Subsequently, for predicted disordered cubic phases, statistical hard-sphere models were established to estimate the lattice parameters and predict diffraction peak positions for inclusion in the library. The library was then employed to analyze diffraction profiles measured from the variably intermixed transition joints, with focus on accounting for both high and low-intensity peaks. 99.0 % of diffraction peaks with relative intensity greater than 0.001 were assigned to phases from the system-specific library, exemplifying rigorous peak accounting and indicating that no unexpected phases were present. Up to six of the twelve library phases were experimentally found in the transition joints. The lattice parameters predicted by the statistical hard-sphere model based upon thermodynamic simulations agree reasonably well with the measured values for the disordered FCC matrix phase.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Navigating thermal stability intricacies of high-nickel cathodes for high-energy lithium batteries

High-nickel oxide cathodes, LiNi x M 1−x O 2 (x ≥ 0.8), are preferred in automotive lithium batteries, but they face thermal instability challenges. Inconsistent literature reports and unstandardized testing protocols further complicate quantitative assessments of the thermal stability of these cathodes. Here, we present here a statistical thermal analysis based on the differential scanning calorimetry measurements of 15 representative cathode materials with different compositions, morphologies and states of charge. The findings reveal that each cathode has a critical state of charge that defines its safe operating limit, which is affected by the metal–oxygen bond strength and surface reactivity. The thermal runaway temperature is dictated by the layered Li 1−x NiO 2 to LiNi 2 O 4 spinel-like phase transition, which is thermodynamically determined by the metal–oxygen bond covalency and kinetically influenced by the cation mixing and particle size. Raman spectroscopy is used to predict the thermal runaway temperature on the basis of the linear relationship between them. Finally, we propose a thermal stability index to quantify cathode thermal stability as a guide for developing safer high-nickel cathodes.

batteries↗
DOE OSTI2023

Real-time latent heat emission during dynamic-compression freezing of water

Abstract Dynamic compression studies have been used to study the nucleation kinetics of water to ice VII for decades. Diagnostics such as photon Doppler velocimetry, transmission loss, and imaging have been used to measure pressure/density, and phase fraction, while temperature has remained the difficult thermodynamic property to quantify. In this work, we measured pressure/density and implemented a diagnostic to measure the temperature. In doing so the temperature shows quasi-isentropically compressed liquid water forms ice at pressures below the previously defined metastable limit, and the liquid phase is not hypercoooled as previously thought above that limit. Instead, the latent heat raises the temperature to the liquid-ice-VII melt line, where it remains with increasing pressure. We propose a hypothesis to corroborate these results with previous work on dynamic compression freezing. These results provide constraints for nucleation models, and suggest this technique be used to investigate phase transitions in other materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Low-temperature breakdown of many-body perturbation theory for thermodynamics

It is shown analytically and numerically that the finite-temperature many-body perturbation theory in the grand canonical ensemble has zero radius of convergence at zero temperature when the energy ordering or degree of degeneracy for the ground state changes with the perturbation strength. When the degeneracy of the reference state is partially or fully lifted at the first-order Hirschfelder-Certain degenerate perturbation theory, the grand potential and internal energy diverge as T → 0. Contrary to earlier suggestions of renormalizability by the chemical potential μ, this nonconvergence, first suspected by W. Kohn and J. M. Luttinger, is caused by the nonanalytic nature of the Boltzmann factor e –E/k e T at T = 0, also plaguing the canonical ensemble, which does not involve chemical potential. The finding reveals a fundamental flaw in perturbation theory, which is deeply rooted in the mathematical limitation of power-series expansions and is unlikely to be removed within its framework.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Interfacial water asymmetry at ideal electrochemical interfaces

Controlling electrochemical reactivity requires a detailed understanding of the charging behavior and thermodynamics of the electrochemical interface. Experiments can independently probe the overall charge response of the electrochemical double layer by capacitance measurements and the thermodynamics of the inner layer with potential of maximum entropy measurements. Relating these properties by computational modeling of the electrochemical interface has so far been challenging due to the low accuracy of classical molecular dynamics (MD) for capacitance and the limited time and length scales of ab initio MD. Here, we combine large ensembles of long-time-scale classical MD simulations with charge response from electronic density functional theory to predict the potential-dependent capacitance of a family of ideal aqueous electrochemical interfaces with different peak capacitances. We show that while the potential of maximum capacitance varies, this entire family exhibits an electrode charge of maximum capacitance (CMC) between -2.9 and -2.2 μC/cm 2 , regardless of the details in the electronic response. Simulated heating of the same interfaces reveals that the entropy peaks at a charge of maximum entropy (CME) of -5.1 ± 0.6 μC/cm 2 , in agreement with experimental findings for metallic electrodes. The CME and CMC both indicate asymmetric response of interfacial water that is stronger for negatively charged electrodes, while the difference between CME and CMC illustrates the richness in behavior of even the ideal electrochemical interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Study of Am electrodeposition from AmCl 3 -LiCl-KCl Molten Salt

In this work, the electrodeposition reaction of Am in AmCl 3 -LiCl-KCl molten salt was studied using voltammetry and chronoamperometry. Electrodeposition of Am was shown to proceed via a two – step reaction scheme, involving the one-electron transfer reduction of Am 3+ to Am 2+ , followed by the two-electron transfer reduction of intermediate Am 2+ to Am 0 . A low Coulombic efficiency of Am deposition was measured despite the Am deposition occurring within the thermodynamic stability window of the supporting LiCl-KCl electrolyte. We hypothesize that the low efficiency is due to out-diffusion of the intermediate Am 2+ species away from the electrode surface. Experimental observations provide evidence of a kinetically – limited electrodeposition reaction, which allows for the loss of intermediate Am 2+ via diffusion leading to Am deposition inefficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Early results from the MIT millimeter and sub-millimeter balloon-borne anisotropy measurement

The MIT balloon-borne bolometric search for Cosmic Microwave Background Radiation (CMBR) anisotropies places the most stringent constraints to date on fluctuations in the CMBR. Four maps of half of the Northern Hemisphere at 1.8, 1.1, 0.63 and 0.44 mm wavelength, have a beam size of 3.8 deg with a 1 sigma sensitivity of less than 0.1 mK (thermodynamic) per FOV in each of the first two channels. Analysis of the sky map at 1.8 mm wavelength using a likelihood ratio test for galactic latitudes of 15 deg and greater yields a 95 percent confidence level (CL) upper limit on fluctuations of the CMBR at DeltaT/T less than or equal to 1.6 x 10 exp -5 with a statistical power of 92 percent for Gaussian fluctuations at a correlation angle of 13 deg. Between 3 deg and 22 deg, the upper limit for fluctuations is DeltaT/T less than or equal to 4.0 x 10 exp -5 (95 percent CL).

Meyer, Stephan S.↗
NASA NTRS1994

Solar flare model atmospheres

Solar flare model atmospheres computed under the assumption of energetic equilibrium in the chromosphere are presented. The models use a static, one-dimensional plane-parallel geometry and are designed within a physically self-consistent coronal loop. Assumed flare heating mechanisms include collisions from a flux of nonthermal electrons and X-ray heating of the chromosphere by the corona. The heating by energetic electrons accounts explicitly for variations of the ionized fraction with depth in the atmosphere. X-ray heating of the chromosphere by the corona incorporates a flare loop geometry by approximating distant portions of the loop with a series of point sources, while treating the loop leg closest to the chromospheric footpoint in the plane-parallel approximation. Coronal flare heating leads to increased heat conduction, chromospheric evaporation and subsequent changes in coronal pressure; these effects are included self-consistently in the models. Cooling in the chromosphere is computed in detail for the important optically thick H I, Ca II and Mg II transitions using the non-local thermodynamic equilibrium (non-LTE) prescription in the program MULTI. Hydrogen ionization rates from X-ray photoionization and collisional ionization by nonthermal electrons are included explicitly in the rate equations. The models are computed in the 'impulsive' and 'equilibrium' limits, and in a set of intermediate 'evolving' states. The impulsive atmospheres have the density distribution frozen in the pre-flare configuration, while the equilibrium models assume the entire atmosphere is in hydrostatic and energetic equilibrium. The evolving atmospheres represent intermediate stages where hydrostatic equilibrium has been established in the chromosphere and corona, but the corona is not yet in energetic equilibrium with the flare heating source. Thus, for example, chromospheric evaporation is still in the process of occurring. We have computed the chromospheric radiation that results from a range of coronal heating rates, with particular emphasis on the widely observed diagnostic H(alpha). Our conclusion is that the H(alpha) fluxes and profiles actually observed in flares can only be produced under conditions of a low-pressure corona with strong beam heating. Therefore we suggest that H(alpha) in flares is produced primarily at the footprints of newly heated loops where significant evaporation has not yet occurred. As a single loop evolves in time, no matter how strong the heating rate may become, the H(alpha) flux will diminish as the corona becomes denser and hence more effective at stopping the beam. This prediction leads to several observable consequences regarding the spatial and temporal signatures of the X-ray and H(alpha) radiation during flares.

Hawley, Suzanne L.↗
NASA NTRS1995

Computing Equilibrium Chemical Compositions

Chemical Equilibrium With Transport Properties, 1993 (CET93) computer program provides data on chemical-equilibrium compositions. Aids calculation of thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93/PC is version of CET93 specifically designed to run within 640K memory limit of MS-DOS operating system. CET93/PC written in FORTRAN.

Mcbride, Bonnie J.↗
NASA NTRS2008

Growth Control and Disease Mechanisms in Computational Embryogeny

This paper presents novel approach to applying growth control and diseases mechanisms in computational embryogeny. Our method, which mimics fundamental processes from biology, enables individuals to reach maturity in a controlled process through a stochastic environment. Three different mechanisms were implemented; disease mechanisms, gene suppression, and thermodynamic balancing. This approach was integrated as part of a structural evolutionary model. The model evolved continuum 3-D structures which support an external load. By using these mechanisms we were able to evolve individuals that reached a fixed size limit through the growth process. The growth process was an integral part of the complete development process. The size of the individuals was determined purely by the evolutionary process where different individuals matured to different sizes. Individuals which evolved with these characteristics have been found to be very robust for supporting a wide range of external loads.

Genetic algorithm↗