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Results for “irreversible 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.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

The stability of amino acids at submarine hydrothermal vent temperatures

It has been postulated that amino acid stability at hydrothermal vent temperatures is controlled by a metastable thermodynamic equilibrium rather than by kinetics. Experiments reported here demonstrate that the amino acids are irreversibly destroyed by heating at 240 C and that quasi-equilibrium calculations give misleading descriptions of the experimental observations. Equilibrium thermodynamic calculations are not applicable to organic compounds under high-temperature submarine vent conditions.

Bada, Jeffrey L.↗
NASA NTRS1999

Dynamical and Chemical Behavior of the Lower Stratosphere and Interactions with the Troposphere

Equivalent-barotropic calculations, in tandem with Lagrangian analyses, reveal how changes of total ozone follow from vertical and horizontal transport by planetary waves. Those calculations also throw light on how diabatic motions comprising the Brewer-Dobson circulation develop from quasi-horizontal advection by planetary waves. Potential temperature along a material surface indicates organized subsidence inside the polar-night vortex, resembling tracer observations from UARS. Lagrangian histories illustrate that this sinking motion follows in large part from parcels being driven out of thermodynamic equilibrium by planetary waves, especially at high latitudes. Irreversible heat transfer then produces a net drift of air across isentropic surfaces as parcels orbit about the displaced vortex. By driving mean-meridional overturning in the stratosphere, this downward drift is ultimately responsible for transferring ozone from the tropics to the extratropical lower stratosphere. It also introduces horizontal structure into the distribution of total ozone, which surfaces clearly in ozone trends. High-resolution global cloud imagery constructed from 6 satellites simultaneously observing the Earth was used to investigate the spectrum of equatorial waves generated by tropical convection and propagating vertically into the stratosphere. The results indicate that temperature variability is dominated by planetary-scale equatorial waves like the Kelvin mode, which agrees with satellite observations of the tropical stratosphere. However, the Kelvin mode accounts for only about 30 - 50% of the eastward momentum flux radiating into the stratosphere, the remainder coming from gravity waves. An algorithm was developed to determine 3-dimensional atmospheric motion from satellite tracer measurements. Based on Lagrangian constraints, the algorithm circumvents limitations of the traditional scheme for inferring motion from temperature measurements and determines the circulation in the tropics as reliably as elsewhere. A study of deep convection revealed that the highest towers (those penetrating into stratospheric air and controlling tropopause height and composition through convective mixing) occur in close association with the diurnal cycle of convection. Clouds colder than 220 K develop almost entirely in association with the diurnal cycle of convection over tropical landmasses and substantially in association with it even over maritime regions.

Salby, Murry L.↗
NASA NTRS1994

Terminal Model Of Newtonian Dynamics

Paper presents study of theory of Newtonian dynamics of terminal attractors and repellers, focusing on issues of reversibility vs. irreversibility and deterministic evolution vs. probabilistic or chaotic evolution of dynamic systems. Theory developed called "terminal dynamics" emphasizes difference between it and classical Newtonian dynamics. Also holds promise for explaining irreversibility, unpredictability, probabilistic behavior, and chaos in turbulent flows, in thermodynamic phenomena, and in other dynamic phenomena and systems.

Zak, Michail↗
NASA NTRS1990

Some aeroacoustic and aerodynamic applications of the theory of nonequilibrium thermodynamics

An exact equation is derived for the dissipation function of a homogeneous, isotropic, Newtonian fluid, with terms associated with irreversible compression or expansion, wave radiation, and the square of the vorticity. This and other forms of the dissipation function are used to identify simple flows, such as incompressible channel flow, the potential vortex with rotational core, and incompressible, irrotational flow as minimally dissipative distributions. A comparison of the hydrodynamic and thermodynamic stability characteristics of a parallel shear flow suggests that an association exists between flow stability and the variation of net dissipation with disturbance amplitude, and that nonlinear effects, such as bounded disturbance amplitude, may be examined from a thermodynamic basis.

Horne, W. Clifton↗
DOE OSTI2023

Lattice Oxygen Redox Reversibility Modulation in Enhancing the Cycling Stability of Li-Rich Cathode Materials

The practical application of lithium-rich layered oxides is prohibited by the drawbacks such as severe capacity and voltage degradation resulting from unstable oxygen redox environment and the accompanied irreversible oxygen release. In this report a facile and effective strategy is proposed to regulate the oxygen redox chemistry via foreign Fe doping and its induced intrinsic transition metal (TM) doping as well as the in situ constructed spinel surface layer. The Fe doping, together with the induced intrinsic TM dual doping, can stabilize the lattice oxygen in the bulk due to the formed stronger Fe—O bond, and restrain the irreversible TM migration and then the undesirable phase transformation. More importantly, thermodynamical energy barrier of oxygen activation is dramatically decreased by the O 2p–Fe 3d charge-transfer, allowing stable oxygen redox activity. And the pre-constructed spinel layer can effectively stabilize the surface lattice oxygen and suppress harmful interfacial side-reactions. Such a simple optimizing method make the modified cathode exhibit a high specific capacity of 298 mAh g -1 at 0.2 C, outstanding cycling stability with a superior capacity and voltage retentions of 92.5% and 90.8%, respectively, after 400 cycles at 1 C. This study provides a new direction for developing advanced Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Molecular Origins of the Barriers to Proton Transport in Acidic Aqueous Solutions

The self-consistent iterative multistate empirical valence bond (SCI-MS-EVB) method is used to analyze the structure, thermodynamics, and dynamics of hydrochloric acid solutions. The reorientation timescales of irreversible proton transport are elucidated by simulating 0.43 M, 0.85 M, 1.68 M, and 3.26 M HCl solutions at 270 K, 285 K, 300 K, 315 K, and 330 K. The results indicate increased counter-ion pairing with increasing concentration, which manifests itself via a reduced hydronium oxygen–chloride (O*-Cl) structuring in the radial distribution functions. Increasing ionic concentration also reduces the diffusion of the hydrated excess protons, principally by reducing the contribution of the Grotthuss proton hopping (shuttling) mechanism to the overall diffusion process. In agreement with prior experimental findings, a decrease in the activation energy of reorientation timescales was also observed, which is explicitly explained using activated rate theory and an energy-entropy decomposition of the state-averaged radial distribution functions. Furthermore, these results provide atomistic verification of suggestions from recent two-dimensional infrared spectroscopy experiments that chloride anions (as opposed to hydrated excess protons) create entropic barriers to proton transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Equilibrium gas flow computations. I - Accurate and efficient calculation of equilibrium gas properties

This paper treats the accurate and efficient calculation of thermodynamic properties of arbitrary gas mixtures for equilibrium flow computations. New improvements in the Stupochenko-Jaffe model for the calculation of thermodynamic properties of diatomic molecules are presented. A unified formulation of equilibrium calculations for gas mixtures in terms of irreversible entropy is given. Using a highly accurate thermo-chemical data base, a new, efficient and vectorizable search algorithm is used to construct piecewise interpolation procedures with generate accurate thermodynamic variable and their derivatives required by modern computational algorithms. Results are presented for equilibrium air, and compared with those given by the Srinivasan program.

Liu, Yen↗
DOE OSTI2026

Time irreversibility as an indicator of approaching tipping points in Earth subsystems

With shifting environmental trends, many Earth system elements may be poised to undergo critical transitions or ‘tipping’. Reliable anticipation of these tipping elements is vital to inform policy decisions. Many of the current methods for tipping point detection are based on loss of resilience or ‘critical slowdown’ of the system as it approaches a tipping point. However, these methods are prone to false alarms; the detected slowdown may be an artifact of nonstationary noise unrelated to tipping behavior. Here, we explore the efficacy of early warning signs based on a nonequilibrium thermodynamics framework. The model-free detection method relies on the increased intrinsic time-irreversibility due to detailed balance breaking, preceding the onset of tipping or instabilities. We demonstrate that these EWSs are effective for tipping point detection and robust against false alarms due to nonstationary noise, using idealized models for two key elements of the Earth system that are prone to tipping: the Atlantic Meridional Overturning Circulation and Arctic sea-ice loss.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Thermodynamics shapes the in vivo enzyme burden of glycolytic pathways

Thermodynamically constrained reactions and pathways are hypothesized to impose greater protein demands on cells, requiring higher enzyme amounts to sustain a given flux compared to those with stronger thermodynamics. To test this, we quantified the absolute concentrations of glycolytic enzymes in three bacterial species— Zymomonas mobilis, Escherichia coli , and Clostridium thermocellum —which employ distinct glycolytic pathways with varying thermodynamic driving forces. By integrating enzyme concentration data with corresponding in vivo metabolic fluxes and ΔG measurements, we found that the highly favorable Entner-Doudoroff pathway in Z. mobilis requires only one-fourth the amount of enzymatic protein to sustain the same flux as the thermodynamically constrained pyrophosphate-dependent glycolytic pathway in C. thermocellum , with the Embden-Meyerhof-Parnas pathway in E. coli exhibiting intermediate thermodynamic favorability and enzyme demand. Across all three pathways, early reactions with stronger thermodynamic driving forces generally required lower enzyme investment than later, less favorable steps. Additionally, reflecting differences in glycolytic strategies, the highly reversible ethanol fermentation pathway in C. thermocellum requires 10-fold more protein to maintain the same flux as the irreversible, forward-driven ethanol fermentation pathway in Z. mobilis . Thus, protein investment across glycolytic pathways reflects differences in their thermodynamic favorability.

Clostridium thermocellum↗
DOE OSTI2024

Bromine Incorporation Affects Phase Transformations and Thermal Stability of Lead Halide Perovskites

Mixed-cation and mixed-halide lead halide perovskites show great potential for their application in photovoltaics. Many of the high-performance compositions are made of cesium, formamidinium, lead, iodine, and bromine. However, incorporating bromine in iodine-rich compositions and its effects on the thermal stability of the perovskite structure has not been thoroughly studied. In this work, we study how replacing iodine with bromine in the state-of-the-art Cs 0.17 FA 0.83 PbI 3 perovskite composition leads to different dynamics in the phase transformations as a function of temperature. Through a combination of structural characterization, cathodoluminescence mapping, X-ray photoelectron spectroscopy, and first-principles calculations, we reveal that the incorporation of bromine reduces the thermodynamic phase stability of the films and shifts the products of phase transformations. Our results suggest that bromine-driven vacancy formation during high temperature exposure leads to irreversible transformations into PbI 2 , whereas materials with only iodine go through transformations into hexagonal polytypes, such as the 4H-FAPbI 3 phase. This work sheds light on the structural impacts of adding bromine on thermodynamic phase stability and provides new insights into the importance of understanding the complexity of phase transformations and secondary phases in mixed-cation and mixed-halide systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

Thermomechanical coupling in fatigue fracture of viscoelastic materials

Subcritical crack growth in a linear viscoelastic material subjected to cyclic loading is investigated starting with the thermodynamic power balance. Physically, it is supposed that the subcritical slow crack growth is due to local weakening of the material in the neighborhood of the crack tip. Under fatigue loading it is assumed that all energy dissipation goes into heat and that this heat build-up is the dominant irreversible process governing crack growth. The cycle averaged temperature distribution around the crack tip is obtained from local application of the first law of thermodynamics (i.e., conservation of energy). The analysis leads to the solution of a nonlinear integro-differential equation for crack length as a function of time which is coupled with the local energy equation. A regular perturbation technique is used to obtain an analytical solution which compares very well with experimental results.

Hufferd, W. L.↗
DOE OSTI2021

Reversible disorder-order transitions in atomic crystal nucleation

Nucleation in atomic crystallization remains poorly understood, despite advances in classical nucleation theory. The nucleation process has been described to involve a nonclassical mechanism that includes a spontaneous transition from disordered to crystalline states, but a detailed understanding of dynamics requires further investigation. In situ electron microscopy of heterogeneous nucleation of individual gold nanocrystals with millisecond temporal resolution shows that the early stage of atomic crystallization proceeds through dynamic structural fluctuations between disordered and crystalline states, rather than through a single irreversible transition. Our experimental and theoretical analyses support the idea that structural fluctuations originate from size-dependent thermodynamic stability of the two states in atomic clusters. These findings, based on dynamics in a real atomic system, reshape and improve our understanding of nucleation mechanisms in atomic crystallization.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1976

Retrodictive determinism

With respect to irreversible, non-homeomorphic maps, contravariant and covariant tensor fields have distinctly natural covariance and transformational behavior. For thermodynamic processes which are non-adiabatic, the fact that the process cannot be represented by a homeomorphic map emphasizes the logical arrow of time, an idea which encompasses a principle of retrodictive determinism for covariant tensor fields.

Kiehn, R. M.↗
NASA NTRS1976

Oxygen electrocatalysts for life support systems

The irreversibility of the oxygen electrode increases by 30 to 60 percent the energy required for water electrolysis over the thermodynamic value in life support systems involving conventional water electrolysis cells. To minimize this voltage loss, high area electrocatalysts, such as platinum metal, are often used for the O2 anode, but even so, the losses are still very substantial. In an attempt to find more effective electrocatalysts for this application, a number of defect metal oxides have been examined.

Ogrady, W. E.↗
NASA NTRS1991

On the thermodynamic framework of generalized coupled thermoelastic-viscoplastic-damage modeling

A complete potential based framework using internal state variables is put forth for the derivation of reversible and irreversible constitutive equations. In this framework, the existence of the total (integrated) form of either the (Helmholtz) free energy or the (Gibbs) complementary free energy are assumed a priori. Two options for describing the flow and evolutionary equations are described, wherein option one (the fully coupled form) is shown to be over restrictive while the second option (the decoupled form) provides significant flexibility. As a consequence of the decoupled form, a new operator, i.e., the Compliance operator, is defined which provides a link between the assumed Gibb's and complementary dissipation potential and ensures a number of desirable numerical features, for example the symmetry of the resulting consistent tangent stiffness matrix. An important conclusion reached, is that although many theories in the literature do not conform to the general potential framework outlined, it is still possible in some cases, by slight modifications of the used forms, to restore the complete potential structure.

Arnold, S. M.↗
DOE OSTI2022

Numerical fluid dynamics for FRG flow equations: Zero-dimensional QFTs as numerical test cases. II. Entropy production and irreversibility of RG flows

Herein we demonstrate that the reformulation of renormalization group (RG) flow equations as nonlinear heat equations has severe implications on the understanding of RG flows in general. We demonstrate by explicitly constructing an entropy function for a zero-dimensional Z 2 -symmetric model that the dissipative character of generic nonlinear diffusion equations is also hard-coded in the functional RG equation. This renders RG flows manifestly irreversible, revealing the semigroup property of RG transformations on the level of the flow equation itself. Additionally, we argue that the dissipative character of RG flows, its irreversibility and the entropy production during the RG flow may be linked to the existence of a so-called C– / A-function. In total, this introduces an asymmetry in the so-called RG time—in complete analogy to the thermodynamic arrow of time—and allows for an interpretation of infrared actions as equilibrium solutions of dissipative RG flows equations. The impossibility of resolving microphysics from macrophysics is evident in this framework. Furthermore, we directly link the irreversibility and the entropy production in RG flows to an explicit numerical entropy production, which is manifest in diffusive and non-linear partial differential equations (PDEs) and a standard mathematical tool for the analysis of PDEs. Using exactly solvable zero-dimensional Z 2 -symmetric models, we explicitly compute the (numerical) entropy production related to the total variation nonincreasing property of the PDE during RG flows toward the infrared limit. Finally, we discuss generalizations of our findings and relations to the C– / A-theorem as well as how our work may help to construct truncations of RG flow equations in the future, including numerically stable schemes for solving the corresponding PDEs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1975

Electrolytic hydrogen production: An analysis and review

The thermodynamics of water electrolysis cells is presented, followed by a review of current and future technology of commercial cells. The irreversibilities involved are analyzed and the resulting equations assembled into a computer simulation model of electrolysis cell efficiency. The model is tested by comparing predictions based on the model to actual commercial cell performance, and a parametric investigation of operating conditions is performed. Finally, the simulation model is applied to a study of electrolysis cell dynamics through consideration of an ideal pulsed electrolyzer.

Evangelista, J.↗
DOE OSTI2024

A non-isothermal breakage-damage model for plastic-bonded granular materials incorporating temperature, pressure, and rate dependencies

Plastic-bonded granular materials (PBM) are widely used in industrial sectors, including building construction, abrasive applications, and defense applications such as plastic-bonded explosives. The mechanical behavior of PBM is highly nonlinear, irreversible, rate dependent, and temperature sensitive governed by various micromechanical attributions such as grain crushing and binder damage. This paper presents a thermodynamically consistent, microstructure-informed constitutive model to capture these characteristic behaviors of PBM. Key features of the model include a breakage internal variable to upscale the grain-scale information to the continuum level and to predict grain size evolution under mechanical loading. In addition, a damage internal state variable is introduced to account for the damage, deterioration, and debonding of the binder matrix upon loading. Temperature is taken as a fundamental external state variable to handle non-isothermal loading paths. The proposed model is able to capture with good accuracy several important aspects of the mechanical properties of PBM, such as pressure-dependent elasticity, pressure-dependent yield strength, brittle-to-ductile transition, temperature dependency, and rate dependency in the post-yielding regime. Furthermore, the model is validated against multiple published datasets obtained from confined and unconfined compression tests, covering various PBM compositions, confining pressures, temperatures, and strain rates.

Breakage↗