Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “THERMODYNAMICS”

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 1,225 records · Page 68
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Quasiharmonic calculations of thermodynamic properties for La 3-x Te 4 system

We report an extensive first-principles quasiharmonic phonon calculation was carried out for the thermoelectric material La 3-x Te 4 at the compositions of x = 0.0, 0.25 and 0.33, focusing at the La site vacancy effects on the thermodynamic properties. The calculated quantities include the 0 K static total energy curves and electronic band structures as well as density-of-states, the phonon density-of-states, together with the linear thermal expansion coefficients, the entropies, the enthalpies, the heat capacities, the bulk moduli, and the Debye temperature as functions of temperature up to 1200 K. Both the standard Perdew-Burke-Ernzerhof (PBE) and the Perdew-Burke-Ernzerhof revised for solids (PBEsol) exchange-correlational functionals were examined and it was found that the PBEsol functional was generally better than the PBE functional in describing both the crystal and electronic properties for the La 3-x Te 4 .

36 MATERIALS SCIENCE↗
DOE OSTI2022

Q-POP-Thermo: A general-purpose thermodynamics solver for ferroelectric materials

We report that Q-POP-Thermo is a program designed to compute thermodynamic monodomain equilibrium states and their properties for ferroelectric single crystals and thin films based on the Landau-Ginzburg-Devonshire (LGD) Theory. Utilizing symbolic manipulation with the SymPy Library, the governing equations along with appropriate boundary conditions are solved for speedy minimization of the free energy of a crystal. Utilizing the popular Differential Evolution algorithm, with appropriate hybridization, multiple phase diagrams, such as the pressure-temperature phase diagram for bulk single crystals and the common strain-temperature phase diagram for monodomain thin-film systems can be readily generated. Furthermore, a variety of material properties of stable ferroelectric phases, including dielectric, piezoelectric, and electrocaloric properties, can simultaneously be calculated. Validation studies are presented for both thin-film and single crystal systems to test the effectiveness and capability of the open-source program.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Detailed thermodynamic investigation of an ICE-driven, natural gas-fueled, 1 kWe micro-CHP generator

Here, the purpose of this work is to record the baseline performance of a state-of-the-art micro-combined heat and power (mCHP) system. A second goal of this work is to provide detailed thermodynamic first and second law performance measurements of the internal combustion engine and generator subsystems. A global technology survey was conducted to identify the leading mCHP systems in the 1 kW electric range. The Honda ECOWILL was identified as the state-of-the-art system in the United States, and an unused unit was procured. The ECOWILL underwent round-robin performance testing at three independent laboratories. First law (energy) and second law (exergy) analyses were conducted on the steady state data. Analysis revealed the ECOWILL operated at a first law electrical efficiency of 23.5 ± 0.4% and a utilization factor of 74.5 ± 3.2%. The primary energy loss was heat transfer from the device, followed by chemical and thermal energy in the exhaust stack. The second law analysis showed the ECOWILL operated at a second law electrical efficiency of 23.1 ± 0.4% and total (including exergy in both the electrical and recovered waste heat streams) second law efficiency of 30.2 ± 2.3%. Key areas of exergy destruction were, in decreasing magnitude, heat transfer, combustion irreversibility, and generator and friction losses.

42 ENGINEERING↗
DOE OSTI2018

Thermodynamic performance and cost optimization of a novel hybrid thermal-compressed air energy storage system design

Compressed Air Energy Storage (CAES) can potentially allow renewable energy sources to meet electricity demands as reliably as coal-fired power plants. However, conventional CAES systems rely on the combustion of natural gas, require large storage volumes, and operate at high pressures, which possess inherent problems such as high costs, strict geological locations, and the production of greenhouse gas emissions. A novel and patented hybrid thermal-compressed air energy storage (HT-CAES) design is presented which allows a portion of the available energy, from the grid or renewable sources, to operate a compressor and the remainder to be converted and stored in the form of heat, through joule heating in a sensible thermal storage medium. The HT-CAES design incudes a turbocharger unit that provides supplementary mass flow rate alongside the air storage. The hybrid design and the addition of a turbocharger have the beneficial effect of mitigating the shortcomings of conventional CAES systems and its derivatives by eliminating combustion emissions and reducing storage volumes, operating pressures, and costs. Storage efficiency and cost are the two key factors, which upon integration with renewable energies would allow the sources to operate as independent forms of sustainable energy. The potential of the HT-CAES design is illustrated through a thermodynamic optimization study, which outlines key variables that have a major impact on the performance and economics of the storage system. The optimization analysis quantifies the required distribution of energy between thermal and compressed air energy storage, for maximum efficiency, and for minimum cost. This study provides a roundtrip energy and exergy efficiency map of the storage system and illustrates a trade off that exists between its capital cost and performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Thermodynamic modeling of MDEA(aq)-NH 3 (aq)-K 2 CO 3 (aq)-CO 2 (aq) using the Extended UNIQUAC model

Here, the development of advanced processes for carbon dioxide capture requires reliable thermodynamic models to ensure accurate process design. This work presents an optimized parameter set of the Extended UNIQUAC model for advanced mixed solvent solutions containing CO 2 -MDEA-NH 3 -K 2 CO 3 in water. The model was parameterized using vapor–liquid equilibrium, pure component saturation pressure, excess enthalpy, heat of absorption, molar heat capacity, apparent molar heat capacity, and solid–liquid equilibrium. These thermal and equilibrium properties cover temperatures between 253.6 K to 600 K and pressures up to 75.6 bar. The current model represents an extension of previous versions that were suitable for modeling aqueous NH 3 and K 2 CO 3 solutions. This parametrization accounts for molecular interactions between MDEA and these two components, which allows for the design of advanced capture processes. This paper demonstrates that the new model parameters are valid within the range of operational conditions typically found in CO 2 capture processes.

42 ENGINEERING↗
DOE OSTI2019

Magnesian calcite solid solution thermodynamics inferred from authigenic deep-sea carbonate

Magnesian calcite is perhaps the most well studied solid solution in the geosciences due to the widespread use of marine carbonates to reconstruct paleoenvironment. Despite decades of research, the low temperature thermodynamic properties of magnesian calcite in seawater are poorly constrained, largely because very slow reaction kinetics prevent the direct measurement of equilibrium distribution coefficients ($K_d^{Mg}$) for anhydrous Mg-bearing minerals. In this study, we use the Mg content of authigenic calcite formed in deep-sea marine carbonate sediments to determine the dependence of $K_d^{Mg}$ on temperature and aqueous Mg/Ca between ~2 and 25 °C. We find that the solid activity coefficient of magnesite in Mg-calcite is strongly temperature dependent in this range, leading to predicted exsolution of Mg at low temperatures. At the temperatures typical of ocean bottom water, equilibrium Mg distribution coefficients are at least an order of magnitude lower than values inferred from inorganic calcite growth experiments. Moreover, the equilibrium temperature dependence of $K_d^{Mg}$ agrees well with field-based paleotemperature calibrations determined for low-Mg benthic and planktonic foraminifera at temperatures <20 °C. Partitioning of Mg in foraminiferal tests is expected to be highly dependent on the Mg/Ca ratio in the calcifying fluid, so ignoring secular variations in seawater Mg/Ca can lead to significant underestimation of paleotemperatures.

58 GEOSCIENCES↗
DOE OSTI2020

Using Thermodynamic Availability to Predict the Transitional Film Reynolds Number between the Droplet and Jet Modes in Falling Liquid between Horizontal Tubes

The objective of this paper is to propose and validate a model for predicting the transitional film Reynolds number between the droplet and jet modes of falling film flows. The proposed model relies on thermodynamic availability with no fitting to mode transition data. The model directly predicts the numerical values of the transitional film Reynolds numbers at different operating conditions. The results of the model are validated against 43 experimental data points from the literature, which cover 10 working fluids and a wide range of tube geometries. The accuracy of the proposed model in predicting the validation data is -on average- more than 20 % better than that of the widely used Re = a (Ga) b and Re = a (Ga) b (S/ξ) c models. The model also achieves low computation time (less than 30 seconds for the 43 validation data points). The model presented in this paper has the potential of integration with heat transfer, mass transfer, and pressure drop models for optimizing the design and operation of falling film heat and mass exchangers.

42 ENGINEERING↗
DOE OSTI2023

Thermodynamic parametric analysis of refueling heavy-duty hydrogen fuel-cell electric vehicles

Reliable design and safe operation of heavy-duty hydrogen refueling stations are essential for the successful deployment of heavy-duty fuel cell electric vehicles (FCEVs). Fueling heavy-duty FCEVs is different from light-duty vehicles in terms of the dispensed hydrogen quantities and fueling rates, requiring tailored fueling station design for each vehicle class. In particular, the selection and design of the onboard hydrogen storage tank system and the fueling performance requirements influence the safe design of hydrogen fueling stations. A thermodynamic modeling and analysis are performed to evaluate the impact of various fueling parameters and boundary conditions on the fueling performance of heavy-duty FCEVs. Here, we studied the effect of dispenser pressure ramp rate and precooling temperature, initial tank temperature and pressure, ambient temperature, and onboard storage design parameters, such as onboard storage pipe diameter and length, on the fueling rate and final vehicle state-of-charge, while observing prescribed tank pressure and temperature safety limits. An important finding was the sensitivity of the temporal fueling rate profile and the final tank state of charge to the design factors impacting pressure drop between the dispenser and vehicle tank, including onboard storage pipe diameter selection, and flow coefficients of nozzle, valves, and fittings. The fueling rate profile impacts the design and cost of the hydrogen precooling unit upstream of the dispenser.

08 HYDROGEN↗
DOE OSTI2020

An analytical expression for temperature in a thermodynamically consistent model with a Mie-Gruneisen equation for pressure

The objective of this paper is to develop an analytical expression for temperature in a thermodynamically consistent model with a Mie-Gruneisen equation for pressure. This expression for the temperature is obtained for both constant and variable specific heat models and can be used in common models for the material yield strength that include thermal softening due to increase in temperature. Additionally, the material parameters in the model can easily be calibrated to match known experimental data and the model has been used to determine the value of the shock pressure at the onset of melting during shock loading.

42 ENGINEERING↗
DOE OSTI2024

Thermodynamic Analysis of Nano-Electrospray Induced Gas Jets

Nano-electrospray (nES) produces a plume of charged liquid droplets which have drag interactions with the surrounding gas after they are emitted from a source capillary. The resulting induced gas flow has often been considered unimportant, but we have demonstrated that a gas microjet of significant velocity up to 10s of m/s can be produced. In this work we present a thermodynamic framework that enables analysis of gas jet generation from electrosprays and introduce the important metrics for such analysis, effectiveness (a measure of momentum transfer from the electrosprayed aerosol to gas) and efficiency (a measure of energy conversion from electrical energy generating the electrospray to gas kinetic energy). This analytical framework is applicable to any two-phase flows consisting of discrete conservative-force-driven particles which exchange momentum with an inert, otherwise quiescent fluid medium to yield a co-flowing two-phase jet. Here, we apply this framework to sprays of water from nano-electrospray emitters to demonstrate that increasing the applied electrical potential difference, increasing liquid mass flowrate, and decreasing droplet size all can increase electrospray induced gas jet strength, but only the latter two do so while also increasing the momentum transfer effectiveness and energy conversion efficiency.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Reliable thermodynamic estimators for screening caloric materials

Reversible, diffusionless, first-order solid-solid phase transitions accompanied by caloric effects are critical for applications in the solid-state cooling and heat-pumping devices. Accelerated discovery of caloric materials requires reliable but faster estimators for predictions and high-throughput screening of system-specific dominant caloric contributions. We assess reliability of the computational methods that provide thermodynamic properties in relevant solid phases at or near a phase transition. Here, we test the methods using the well-studied B2 FeRh alloy as a “fruit fly” in such a materials genome discovery, as it exhibits a metamagnetic transition which generates multicaloric (magneto-, elasto-, and baro-caloric) responses. For lattice entropy contributions, we find that the commonly-used linear-response and small-displacement phonon methods are invalid near instabilities that arise from the anharmonicity of atomic potentials, and we offer a more reliable and precise method for calculating lattice entropy at a fixed temperature. Then, we apply a set of reliable methods and estimators to the metamagnetic transition in FeRh (predicted 346 ± 12 K, observed 353 ± 1 K) and calculate the associated caloric properties, such as isothermal entropy and isentropic temperature changes.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Coupling sample paths to the thermodynamic limit in Monte Carlo estimators with applications to gene expression

Many biochemical systems appearing in applications have a multiscale structure so that they converge to piecewise deterministic Markov processes in a thermodynamic limit. The statistics of the piecewise deterministic process can be obtained much more efficiently than those of the exact process. We explore the possibility of coupling sample paths of the exact model to the piecewise deterministic process in order to reduce the variance of their difference. We then apply this coupling to reduce the computational complexity of a Monte Carlo estimator. Motivated by the rigorous results in , we show how this method can be applied to realistic biological models with nontrivial scalings.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Thermodynamic evaluation and modeling of the CeF 3 -LaF 3 -LiF-NaF system

The thermodynamic properties of the LiF-NaF-CeF 3 -LaF 3 pseudo-quaternary system have been evaluated, and models for the relevant phases have been revised or newly developed. The solid solubility of NaF in LaF 3 and CeF 3 was described in the model based on reported phase-equilibria observations and results from density functional theory calculations. The Gibbs energy functions for the NaCeF 4 and NaLaF 4 phases have been updated with recently reported thermochemical measurements. The Gibbs energy functions and model relations for the LiF-NaF-LaF 3 and LiF-NaF-CeF 3 pseudo-ternary systems were successfully optimized based on thermochemical properties and phase equilibria observations.

CALPHAD↗
DOE OSTI2020

Thermodynamic properties of Ca–Pb electrodes determined by electromotive force measurements

Thermodynamic properties of Ca–Pb alloys are investigated by electromotive force (emf) measurements to determine equilibrium cell potentials and phase properties for their application in energy storage systems such as liquid metal batteries. Using the electrochemical cell Ca(s) | CaF 2 (s) | Ca(in Pb) at 700–1060 K, cell emf is measured for thirteen Ca–Pb alloys at mole fractions, x Ca = 0.06–0.80. At 873 K, the equilibrium potentials of liquid Ca–Pb alloys are 0.57–0.62 V versus Ca and the activity values are as low as a Ca = 6.2 × 10 -8 at x Ca = 0.06. In addition, the emf values as a function of temperature provide partial molar quantities (entropy and enthalpy) as well as phase transitions which are corroborated by determining transition temperatures and phase constituents using differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD). This study establishes the fundamental data necessary for the design of Pb-containing liquid metal electrodes through the integration of electrochemical, thermal, and structural properties of Ca–Pb electrodes.

25 ENERGY STORAGE↗
DOE OSTI2013

First-principles study of structural, electronic and thermodynamic properties of EuMg{sub 2} and EuMg{sub 2}H{sub 6}

Within framework of the density functional theory, the structural and electronic properties of EuMg{sub 2} and its hydride EuMg{sub 2}H{sub 6} have been investigated. The calculated structural parameters are in good agreement with the experimental results, and the obtained formation enthalpies indicate that the stability of EuMg{sub 2} is lower than that of EuMg{sub 2}H{sub 6}. The calculated electronic structures show that both compounds exhibit a strong spin polarization feature near the Fermi level owing to the localized Eu-f electrons, and the EuMg{sub 2}H{sub 6} demonstrates mainly ionic characteristic. For thermodynamics of hydrogenation/dehydrogenation process of this system, the calculated reaction enthalpies along possible five reaction routes show that the most possible hydrogenation pathway is EuMg{sub 2}+3H{sub 2}{yields}EuMg{sub 2}H{sub 6}, while the favorable dehydrogenation pathway is EuMg{sub 2}H{sub 6}{yields}EuH{sub 2}+2Mg+2H{sub 2}. - The charge difference distribution (e/Bohr{sup 3}) (a) on (1010) plane of EuMg{sub 2}, (b) on (110) and (c) (020) planes of its hydride EuMg{sub 2}H{sub 6}. Highlights: Black-Right-Pointing-Pointer The Eu-f electron has important effects on stability and hydrogen storage behavior. Black-Right-Pointing-Pointer The hydride exhibits primary ionic characteristics. Black-Right-Pointing-Pointer Three types of Mg--H bonding display also obvious ionic feature with some covalence. Black-Right-Pointing-Pointer The dehydrogenation temperature of EuMg{sub 2}H{sub 6} is further determined.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Analysis of mechanical, thermodynamic, and thermoelectric properties of ferromagnetic SrFe{sub 4}As{sub 12} skutterudite

In the present work, the electronic, mechanical, thermal and thermoelectric properties of Sr-filled skutterudite have been investigated in the framework of density functional theory. SrFe{sub 4}As{sub 12} shows a ferromagnet character with a magnetic moment of 1.76 μ{sub B} at an optimized lattice parameter of 8.38 Å. The effect of high-pressures on thermodynamic properties viz. thermal expansion coefficient, specific heat capacity and Grüneisen parameter is also carried out by employing the quasi-harmonic Debye model. Temperature dependence of Seebeck coefficient, electrical conductivity, thermal conductivity, power factor, and figure of merit is observed up to 800 K. The lattice thermal conductivity decreases with temperature due to rattling behavior of the filler atom. SrFe{sub 4}As{sub 12} exhibits the high value of the figure of merit equal to 0.76 at 800 K. The present results clearly signify that SrFe{sub 4}As{sub 12} may be a good choice for thermoelectric applications due to its high-power factor and figure of merit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Thermodynamic, structural and magnetic studies of phase transformations in MnAl nanocomposite alloys

Highlights: • Small changes in MnAl stoichiometry (5 at.%) produce different phase structure. • In Mn{sub 60}Al{sub 40} as-cast alloy only hcp ε phase can be found • In Mn{sub 55}Al{sub 45} as-cast alloy, there is a mixture of γ{sub 2} (Al{sub 8}Mn{sub 5}) and ε as well as ferromagnetic MnAl τ-phase. • Energies of phase transformation of about 165 kJ/mol for Mn{sub 60}Al{sub 40} and 290 kJ/mol for Mn{sub 55}Al{sub 45} alloys are found. • hcp ε phase decomposes through the migration of interphase interfaces. - Abstract: We have undertaken a temperature-dependent, investigation of the thermodynamics, structure, morphology and magnetism of two MnAl nanocomposite alloys (Mn{sub 60}Al{sub 40} and Mn{sub 55}Al{sub 45}). Differential scanning calorimetry (DSC) studies allowed the determination of the exo-effects occurring in the structural phase transformation of MnAl, while by using temperature-dependent X-ray diffraction of synchrotron radiation we were able to monitor the phase transformation effects and the evolution with temperature of various structural phases occurring in the samples. We have shown that slight changes in stoichiometry (5 at.%) give rise to different phase structure in the as-cast state. While in Mn{sub 60}Al{sub 40} only hcp ε phase can be found, in Mn{sub 55}Al{sub 45} as-cast alloy, there is a quite complex phase structure with a mixture of γ{sub 2} (Al{sub 8}Mn{sub 5}) and ε as well as ferromagnetic MnAl τ-phase. Activation energies of about 165 kJ/mol and 290 kJ/mol have been calculated from the Ozawa-Flynn-Wall analysis of DSC experimental data. These findings are in good agreement with the results obtained from XRD. For the Mn{sub 55}Al{sub 45} as-cast alloy, we have confirmed by temperature-dependent synchrotron XRD that the hcp ε phase decomposes through the migration of interphase interfaces with the transformation rate controlled by boundary diffusion processes. High-resolution transmission electron microscopy have confirmed the phase structure obtained by XRD, while magnetic properties, obtained for the as-cast alloys are consistent with the multiphase character of the samples and in good agreement with previously reported results. The magnetization does not saturate for the maximum applied field of about 4 × 10{sup 6} A/m and a marked coercivity of about 160 kA/m is obtained for the Mn{sub 55}Al{sub 45} as-cast alloy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Analysis of the structural, electronic, elastic and thermodynamic properties of CuAl2X4 (X = O, S) spinel structure

Highlights: • Fundamental properties of CuAl{sub 2}X{sub 4} (X = O, S) aluminate spinels have been investigated. • The pressure dependence of the elastic constants C{sub ij} can be successfully fit by a straight line. • CuAl{sub 2}X{sub 4} (X = O, S) compounds are mechanically stable at ambient conditions. • Temperature and pressure dependences of some macroscopic parameters are achieved. - Abstract: The structural, electronic, elastic and thermodynamic properties of oxo- and thio-spinels have been predicted based on the ultrasoft pseudo-potential scheme as implemented in the CASTEP code. The exchange-correlation potential was treated within the generalized gradient approximation (GGA-PBE). The calculated structural parameters such as lattice constants and internal parameters are in good agreement with the available experimental data. The ground state electronic band structure revealed that CuAl{sub 2}X{sub 4} (XO, S) spinels are direct band gap semiconductors with a transition along Γ-Γ symmetry points. The calculated values of elastic constants satisfy the Born criteria at ambient conditions and confirm that the spinel structures of CuAl{sub 2}O{sub 4} and CuAl{sub 2}S{sub 4} are mechanically stable. The thiospinel structure may have a phase transition under pressure, due to the negative value of C{sub 44}. The influence of temperature and pressure on macroscopic characteristics of CuAl{sub 2}O{sub 4} and CuAl{sub 2}S{sub 4} compounds was estimated using the quasi-harmonic Debye model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗