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At least 361 records · Page 20

Measuring the Thermodynamics of the Alloy/Scale Interface

A method is proposed for the direct measurement of the thermodynamic properties of the alloy and oxide compound at the alloy/scale interface observed during steady-state oxidation. The thermodynamic properties of the alloy/scale interface define the driving force for solid-state transport in the alloy and oxide compound. Accurate knowledge of thermodynamic properties of the interface will advance our understanding of oxidation behavior. The method is based on the concept of local equilibrium and assumes that an alloy+scale equilibrium very closely approximates the alloy/scale interface observed during steady-state oxidation. The thermodynamics activities of this alloy+scale equilibrium are measured directly by Knudsen effusion-cell mass spectrometer (KEMS) using the vapor pressure technique. The theory and some practical considerations of this method are discussed in terms of beta-NiAl oxidation.

Copland, Evan↗

ThermoBuild: Online Method Made Available for Accessing NASA Glenn Thermodynamic Data

The new Web site program "ThermoBuild" allows users to easily access and use the NASA Glenn Thermodynamic Database of over 2000 solid, liquid, and gaseous species. A convenient periodic table allows users to "build" the molecules of interest and designate the temperature range over which thermodynamic functions are to be displayed. ThermoBuild also allows users to build custom databases for use with NASA's Chemical Equilibrium with Applications (CEA) program or other programs that require the NASA format for thermodynamic properties. The NASA Glenn Research Center has long been a leader in the compilation and dissemination of up-to-date thermodynamic data, primarily for use with the NASA CEA program, but increasingly for use with other computer programs.

McBride, Bonnie↗

Comparison of Ablation Predictions for Carbonaceous Materials Using CEA and JANAF-Based Species Thermodynamics

In most previous work at NASA Ames Research Center, ablation predictions for carbonaceous materials were obtained using a species thermodynamics database developed by Aerotherm Corporation. This database is derived mostly from the JANAF thermochemical tables. However, the CEA thermodynamics database, also used by NASA, is considered more up to date. In this work, the FIAT code was modified to use CEA-based curve fits for species thermodynamics, then analyses using both the JANAF and CEA thermodynamics were performed for carbon and carbon phenolic materials over a range of test conditions. The ablation predictions are comparable at lower heat fluxes where the dominant mechanism is carbon oxidation. However, the predictions begin to diverge in the sublimation regime, with the CEA model predicting lower recession. The disagreement is more significant for carbon phenolic than for carbon, and this difference is attributed to hydrocarbon species that may contribute to the ablation rate.

Milos, Frank S.↗

Characteristics of Subcooled Liquid Methane During Passage Through a Spray-Bar Joule-Thompson Thermodynamic Vent System

NASA s Marshall Space Flight Center (MSFC) conducted liquid methane (LCH4) testing in November 2006 using the multipurpose hydrogen test bed (MHTB) outfitted with a spray-bar thermodynamic vent system (TVS). The basic objective was to identify any unusual or unique thermodynamic characteristics associated with subcooled LCH4 that should be considered in the design of space-based TVSs. Thirteen days of testing were performed with total tank heat loads ranging from 720 W to 420 W at a fill level of approximately 90%. During an updated evaluation of the data, it was noted that as the fluid passed through the Joule Thompson expansion, thermodynamic conditions consistent with the pervasive presence of metastability were indicated. This paper describes the observed thermodynamic conditions that correspond with metastability and effects on TVS performance.

Hastings, L. J.↗

Liquid Methane Testing With a Large-Scale Spray Bar Thermodynamic Vent System

NASA's Marshall Space Flight Center conducted liquid methane testing in November 2006 using the multipurpose hydrogen test bed outfitted with a spray bar thermodynamic vent system (TVS). The basic objective was to identify any unusual or unique thermodynamic characteristics associated with densified methane that should be considered in the design of space-based TVSs. Thirteen days of testing were performed with total tank heat loads ranging from 720 to 420 W at a fill level of approximately 90%. It was noted that as the fluid passed through the Joule-Thompson expansion, thermodynamic conditions consistent with the pervasive presence of metastability were indicated. This Technical Publication describes conditions that correspond with metastability and its detrimental effects on TVS performance. The observed conditions were primarily functions of methane densification and helium pressurization; therefore, assurance must be provided that metastable conditions have been circumvented in future applications of thermodynamic venting to in-space methane storage.

Hastings, L. J.↗

Propulsion System Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic System T-MATS

A simulation toolbox has been developed for the creation of both steady-state and dynamic thermodynamic software models. This paper describes the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS), which combines generic thermodynamic and controls modeling libraries with a numerical iterative solver to create a framework for the development of thermodynamic system simulations, such as gas turbine engines. The objective of this paper is to present an overview of T-MATS, the theory used in the creation of the module sets, and a possible propulsion simulation architecture. A model comparison was conducted by matching steady-state performance results from a T-MATS developed gas turbine simulation to a well-documented steady-state simulation. Transient modeling capabilities are then demonstrated when the steady-state T-MATS model is updated to run dynamically.

gas path dynamics↗

Propulsion System Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic System (T-MATS)

A simulation toolbox has been developed for the creation of both steady-state and dynamic thermodynamic software models. This presentation describes the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS), which combines generic thermodynamic and controls modeling libraries with a numerical iterative solver to create a framework for the development of thermodynamic system simulations, such as gas turbine engines. The objective of this presentation is to present an overview of T-MATS, the theory used in the creation of the module sets, and a possible propulsion simulation architecture.

aerothermodynamics↗

Propulsion System Simulation Using the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS)

A simulation toolbox has been developed for the creation of both steady-state and dynamic thermodynamic software models. This paper describes the Toolbox for the Modeling and Analysis of Thermodynamic Systems (T-MATS), which combines generic thermodynamic and controls modeling libraries with a numerical iterative solver to create a framework for the development of thermodynamic system simulations, such as gas turbine engines. The objective of this paper is to present an overview of T-MATS, the theory used in the creation of the module sets, and a possible propulsion simulation architecture. A model comparison was conducted by matching steady-state performance results from a T-MATS developed gas turbine simulation to a well-documented steady-state simulation. Transient modeling capabilities are then demonstrated when the steady-state T-MATS model is updated to run dynamically.

aerothermodynamics↗

Thermodynamic Spectrum of Solar Flares Based on SDO/EVE Observations: Techniques and First Results

The Solar Dynamics Observatory (SDO)/EUV Variability Experiment (EVE) provides rich information on the thermodynamic processes of solar activities, particularly on solar flares. Here, we develop a method to construct thermodynamic spectrum (TDS) charts based on the EVE spectral lines. This tool could potentially be useful for extreme ultraviolet (EUV) astronomy to learn about the eruptive activities on distant astronomical objects. Through several cases, we illustrate what we can learn from the TDS charts. Furthermore, we apply the TDS method to 74 flares equal to or greater than the M5.0 class, and reach the following statistical results. First, EUV peaks are always behind the soft X-ray (SXR) peaks and stronger flares tend to have faster cooling rates. There is a power-law correlation between the peak delay times and the cooling rates, suggesting a coherent cooling process of flares from SXR to EUV emissions. Second, there are two distinct temperature drift patterns, called Type I and Type II. For Type I flares, the enhanced emission drifts from high to low temperature like a quadrilateral, whereas for Type II flares the drift pattern looks like a triangle. Statistical analysis suggests that Type II flares are more impulsive than Type I flares. Third, for late-phase flares, the peak intensity ratio of the late phase to the main phase is roughly correlated with the flare class, and the flares with a strong late phase are all confined. We believe that the re-deposition of the energy carried by a flux rope, which unsuccessfully erupts out, into thermal emissions is responsible for the strong late phase found in a confined flare. Furthermore, we show the signatures of the flare thermodynamic process in the chromosphere and transition region in the TDS charts. These results provide new clues to advance our understanding of the thermodynamic processes of solar flares and associated solar eruptions, e.g., coronal mass ejections.

Wang, Yuming↗

CFD and Thermodynamic Model Predictions of No-Vent Tank Filling in Microgravity

Cryogenic Fluid Management (CFM) of propellant fluids under low gravity conditions present an important challenge in the pursuit of NASA’s future long-duration space missions. Success of these missions relies to a large extent on the ability to store and transfer the cryogenic liquid fuels efficiently and safely. To this end, the Zero-Boil-Off Tank Filling and Transfer Experiment (ZBOT-FT) undertaken by University of Bremen in collaboration with Case Western Reserve University aims at studying two phase flow tank-to-tank transfer operations in microgravity using a simulant fluid, Perfluoro-n-pentane (PNP). As part of this effort, in this work, we present a system level homogeneous thermodynamic model and a two-phase Computational Fluid Dynamics (CFD) model of a no-vent cylindrical tank filling in microgravity. Both 2D axisymmetric and 3D parametric simulations case studies are performed to show the detailed physics of the filling process and the evolution of tank pressure for filling flow rates between 1.0 and 1.65 mL/s. A zero-dimensional homogeneous thermodynamic model is also developed to predict the final steady state tank pressure analytically. Comparison of the 2D and 3D CFD predictions of final pressures to the steady state thermodynamic results displays very good agreement. However, it is shown that the 2D axisymmetric model predicts a maxima in tank pressure before reaching steady state. It is indicted that this pressure maxima is caused by the constraints inherent in the axisymmetric model and is absent in the 3D and thermodynamic pressure predictions.

Two Phase Flow↗

Thermodynamics of Restricted Boltzmann Machines and Related Learning Dynamics

We investigate the thermodynamic properties of a restricted Boltzmann machine (RBM), a simple energy-based generative model used in the context of unsupervised learning. Assuming the information content of this model to be mainly reflected by the spectral properties of its weight matrix W, we try to make a realistic analysis by averaging over an appropriate statistical ensemble of RBMs. First, a phase diagram is derived. Otherwise similar to that of the Sherrington–Kirkpatrick (SK) model with ferromagnetic couplings, the RBM’s phase diagram presents a ferromagnetic phase which may or may not be of compositional type depending on the kurtosis of the distribution of the components of the singular vectors of W. Subsequently, the learning dynamics of the RBM is studied in the thermodynamic limit. A “typical” learning trajectory is shown to solve an effective dynamical equation, based on the aforementioned ensemble average and explicitly involving order parameters obtained from the thermodynamic analysis. In particular, this let us show how the evolution of the dominant singular values of W, and thus of the unstable modes, is driven by the input data. At the beginning of the training, in which the RBM is found to operate in the linear regime, the unstable modes reflect the dominant covariance modes of the data. In the non-linear regime, instead, the selected modes interact and eventually impose a matching of the order parameters to their empirical counterparts estimated from the data. Finally, we illustrate our considerations by performing experiments on both artificial and real data, showing in particular how the RBM operates in the ferromagnetic compositional phase.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Experimental Study on the Thermodynamics of the CaO-SiO{sub 2}-Ce{sub 2}O{sub 3} System at 1873 K

The phase relations in the CaO-SiO{sub 2}-Ce{sub 2}O{sub 3} system under the reducing atmosphere at 1873 K were determined by the conventional equilibrium and quenching method combined with scanning electron microscopy-electron probe microanalysis (SEM-EPMA) and X-ray diffraction (XRD) measurements on the quenched samples. Based on these analyses, a large part of the isothermal phase diagram was constructed. Furthermore, the thermodynamic activities of Ce{sub 2}O{sub 3} in the melts at 1873 K were measured by the chemical equilibrium method. Using the measured activity data, an empirical formula to estimate the activity coefficient of Ce{sub 2}O{sub 3} was proposed based on the regular solution model. It was found that, for the melts with the same Ce{sub 2}O{sub 3} contents, the thermodynamic activities of Ce{sub 2}O{sub 3} increase gradually with the rise of basicity (the ratio of CaO to SiO{sub 2}) of the melts. This implies that, from the thermodynamic point of view, the increase of basicity is favorable to the enrichment and precipitation of Ce-containing mineral phases.

36 MATERIALS SCIENCE↗

A modified thermodynamic sea ice model and its application

This paper presents a modified thermodynamic sea ice model based on the Winton’s three-layer model framework. Several improvements focused on the vertical thermodynamics have been made in the model. Results from a series of one-dimensional experiments show that equilibrium ice thickness in our modified model is increased by about 45 cm when compared with the original Winton’s model. Sensitivity tests indicate that all modifications mentioned above contribute to this change of ice thickness, among which the increase of ice layer has the most significant effect followed by the sea ice conductivity parameterization. The modified thermodynamic sea ice model is then coupled into the sea ice component SIS in GFDL MOM4 to exert long-term integration experiments forced by CORE2.0 data. Results indicate that the modified model shows significant improvement in simulating the Arctic sea ice, including an increase in both the sea ice thickness and volume over the whole Arctic region. This confirms the above founding from 1-D simulations.

54 ENVIRONMENTAL SCIENCES↗

Thermodynamic assessment of nonstoichiometric oxides for solar thermochemical fuel production

Two-step solar thermochemical cycling (STC) based on nonstoichiometric oxides is an ideal means of solar fuel (e.g., H 2 , CO) production. Screening of nonstoichiometric oxides with excellent thermodynamic performance is key to achieving high solar-to-fuel efficiency. However, application-driven materials assessment intended for reactor-level solar fuel production performance requires mimicking realistic operating conditions of on-sun tests in a laboratory setting, which makes oxides assessment and screening an onerous task to accomplish experimentally. In this work, a rapid assessment and screening model of nonstoichiometric oxides for two-step solar thermochemical cycling assuming fixed-bed flow pattern and quasi-equilibration of the solid with the flowing gas phase is developed, with solar-to-fuel efficiency being the target function of optimization. The model accounts for the thermodynamic parameters of oxide materials and typical operating conditions of experimental thermochemical cycling. This study employed the model to explore and compare two groups of typical nonstoichiometric oxides (CeO 2 - and (LaSr)MnO 3 -based) for their maximum efficiency under their uniquely optimized cycling conditions. The results show that CeO 2 can reach a maximum efficiency of 12.9% at reduction temperature of 1500 °C, which is superior to other candidate materials, including 20 mol% Zr-doped CeO 2 (10.1%), La 0.6 Sr 0.4 MnO 3 (2.5%) and La 0.8 Sr 0.2 MnO 3 (3.3%). Even when the reduction temperature is lowered to 1350 °C, ceria yields the highest efficiency amongst the candidate STC materials considered. The optimal cycling strategy depends on the inherent thermodynamic properties of the oxides. This approach serves as a framework for assessing the maximum efficiency and optimal conditions of candidate thermochemical materials within a range of constraints rather than comparing materials under arbitrary cycling conditions, which may inherently favor one material over another. For oxidation temperatures below 800–1000 °C, the model could be further improved by considering reaction kinetics.

14 SOLAR ENERGY↗

Deuterated water as a substrate-agnostic isotope tracer for investigating reversibility and thermodynamics of reactions in central carbon metabolism

Stable isotope tracers are a powerful tool for the quantitative analysis of microbial metabolism, enabling pathway elucidation, metabolic flux quantification, and assessment of reaction and pathway thermodynamics. 13 C and 2 H metabolic flux analysis commonly relies on isotopically labeled carbon substrates, such as glucose. However, the use of 2 H-labeled nutrient substrates faces limitations due to their high cost and limited availability in comparison to 13 C-tracers. Furthermore, isotope tracer studies in industrially relevant bacteria that metabolize complex substrates such as cellulose, hemicellulose, or lignocellulosic biomass, are challenging given the difficulty in obtaining these as isotopically labeled substrates. In this study, we examine the potential of deuterated water ( 2 H 2 O) as an affordable, substrate-neutral isotope tracer for studying central carbon metabolism. We apply 2 H 2 O labeling to investigate the reversibility of glycolytic reactions across three industrially relevant bacterial species -C. thermocellum, Z. mobilis, and E. coli-harboring distinct glycolytic pathways with unique thermodynamics. We demonstrate that 2 H 2 O labeling recapitulates previous reversibility and thermodynamic findings obtained with established 13 C and 2 H labeled nutrient substrates. Furthermore, we exemplify the utility of this 2 H 2 O labeling approach by applying it to high-substrate C. thermocellum fermentations -a setting in which the use of conventional tracers is impractical-thereby identifying the glycolytic enzyme phosphofructokinase as a major bottleneck during high-substrate fermentations and unveiling critical insights that will steer future engineering efforts to enhance ethanol production in this cellulolytic organism. This study demonstrates the utility of deuterated water as a substrate-agnostic isotope tracer for examining flux and reversibility of central carbon metabolic reactions, which yields biological insights comparable to those obtained using costly 2 H-labeled nutrient substrates.

09 BIOMASS FUELS↗

A self-consistent thermodynamic model of metallic systems. Application for the description of gold

A self-consistent thermodynamic model of metallic system is presented. The expression for the Gibbs energy is derived, which incorporates elastic (static) energy, vibrational energy within the Debye model, and electronic part in Hartee-Fock approximation. The elastic energy is introduced by a volume-dependent anharmonic potential. From the Gibbs energy all thermodynamic quantities, as well as the equation of state, are self-consistently obtained. The model is applied for the description of bulk gold in temperature range 0 ≤ T ≲ 1300 K and external pressure up to 30 GPa. The calculated thermodynamic properties are illustrated in figures and show satisfactory agreement with experimental data. The advantages and opportunities for further development of the method are discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nonequilibrium thermodynamics of nucleation

We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fluids confined in wedges and by edges: Virial series for the line-thermodynamic properties of hard spheres

This work is devoted to analyze the relation between the thermodynamic properties of a confined fluid and the shape of its confining vessel. Recently, new insights in this topic were found through the study of cluster integrals for inhomogeneous fluids that revealed the dependence on the vessel shape of the low density behavior of the system. Here, the statistical mechanics and thermodynamics of fluids confined in wedges or by edges is revisited, focusing on their cluster integrals. In particular, the well known hard sphere fluid, which was not studied in this framework so far, is analyzed under confinement and its thermodynamic properties are analytically studied up to order two in the density. Furthermore, the analysis is extended to the confinement produced by a corrugated wall. These results rely on the obtained analytic expression for the second cluster integral of the confined hard sphere system as a function of the opening dihedral angle 0 < β < 2π. It enables a unified approach to both wedges and edges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗