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Results for “nonequilibrium 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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Light element ($$Z=1,2$$) production from spontaneous ternary fission of $$^{252}$$Cf

Abstract The yields of light elements ( $$Z=1,2$$ Z = 1 , 2 ) obtained from spontaneous ternary fission of $$^{252}$$ 252 Cf are treated within a nonequilibrium approach, and the contribution of unstable nuclei and excited bound states is taken into account. These light cluster yields may be used to probe dense matter, and to infer in-medium corrections such as Pauli blocking which is determined by the nucleon density. Continuum correlations are calculated from scattering phase shifts using the Beth-Uhlenbeck formula, and the effect of medium modification is estimated. The relevant distribution is reconstructed from the measured yields of isotopes. This describes the state of the nucleon system at scission and cluster formation, using only three Lagrange parameters which are the nonequilibrium counterparts of the temperature and chemical potentials, as defined in thermodynamic equilibrium. We concluded that a simple nuclear statistical equilibrium model neglecting continuum correlations and medium effects is not able to describe the measured distribution of H and He isotopes. Moreover, the freeze-out concept may serve as an important ingredient to the nonequilibrium approach using the relevant statistical operator concept.

Röpke, G.↗
DOE OSTI2021

Elastic forces drive nonequilibrium pattern formation in a model of nanocrystal ion exchange

The widely used process of nanocrystal ion exchange operates out of thermodynamic equilibrium and can require mixing components of varying sizes. Here we use theory and computer simulation to study a simple model which captures these two basic features of ion exchange reactions. We show that a strong driving force for exchange among different-sized species creates nonequilibrium patterns within model nanocrystals. We further demonstrate that such patterns can be thermodynamically stable within core/shell nanocrystals. These results help us understand the heterostructures formed in ion-exchanged nanocrystals and suggest strategies for leveraging elasticity to design patterns in nanoscale materials. Chemical transformations, such as ion exchange, are commonly employed to modify nanocrystal compositions. Yet the mechanisms of these transformations, which often operate far from equilibrium and entail mixing diverse chemical species, remain poorly understood. Here we explore an idealized model for ion exchange in which a chemical potential drives compositional defects to accumulate at a crystal’s surface. These impurities subsequently diffuse inward. We find that the nature of interactions between sites in a compositionally impure crystal strongly impacts exchange trajectories. In particular, elastic deformations which accompany lattice-mismatched species promote spatially modulated patterns in the composition. These same patterns can be produced at equilibrium in core/shell nanocrystals, whose structure mimics transient motifs observed in nonequilibrium trajectories. Moreover, the core of such nanocrystals undergoes a phase transition—from modulated to unstructured—as the thickness or stiffness of the shell is decreased. Our results help explain the varied patterns observed in heterostructured nanocrystals produced by ion exchange and suggest principles for the rational design of compositionally patterned nanomaterials.

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

Simulating dielectric spectra: A demonstration of the direct electric field method and a new model for the nonlinear dielectric response

Here we demonstrate a method to compute the dielectric spectra of fluids in molecular dynamics (MD) by directly applying electric fields to the simulation. We obtain spectra from MD simulations with low magnitude electric fields (≈0.01 V/Å) in agreement with spectra from the fluctuation–dissipation method for water and acetonitrile. We examine this method’s trade-off between noise at low field magnitudes and the nonlinearity of the response at higher field magnitudes. We then apply the Booth equation to describe the nonlinear response of both fluids at low frequency (0.1 GHz) and high field magnitude (up to 0.5 V/Å). We develop a model of the frequency-dependent nonlinear response by combining the Booth description of the static nonlinear dielectric response of fluids with the frequency-dependent linear dielectric response of the Debye model. We find good agreement between our model and the MD simulations of the nonlinear dielectric response for both acetonitrile and water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Achieving designed texture and flows in bulk active nematics using optimal control theory

Being intrinsically nonequilibrium, active materials can potentially perform functions that would be thermodynamically forbidden in passive materials. However, active systems have diverse local attractors that correspond to distinct dynamical states, many of which exhibit chaotic turbulent-like dynamics and thus cannot perform work or useful functions. Designing such a system to choose a specific dynamical state is a formidable challenge. Motivated by recent advances enabling optogenetic control of experimental active materials, we describe an optimal control theory framework that identifies a spatiotemporal sequence of light-generated activity that drives an active nematic system toward a prescribed dynamical steady state. Active nematics are unstable to spontaneous defect proliferation and chaotic streaming dynamics in the absence of control. We demonstrate that optimal control theory can compute activity fields that redirect the dynamics into a variety of alternative dynamical programs and functions. This includes dynamically reconfiguring between states, selecting and stabilizing emergent behaviors that do not correspond to attractors, and are hence unstable in the uncontrolled system. Furthermore, our results provide a roadmap to leverage optical control methods to rationally design structure, dynamics, and function in a wide variety of active materials.

Complex systems theory↗
DOE OSTI2024

Medium-density amorphous ice unveils shear rate as a new dimension in water’s phase diagram

Recent experiments revealed a new amorphous ice phase, medium-density amorphous ice (MDA), formed by ball-milling ice I h at 77 K [Rosu-Finsen et al., Science 379, 474–478 (2023)]. MDA has density between that of low-density amorphous (LDA) and high-density amorphous (HDA) ices, adding to the complexity of water’s phase diagram, known for its glass polyamorphism and two-state thermodynamics. The nature of MDA and its relation to other amorphous ices and liquid water remain unsolved. Here, we use molecular simulations under controlled pressure and shear rate at 77 K to produce and investigate MDA. Here. we find that MDA formed at constant shear rate is a steady-state nonequilibrium shear-driven amorphous ice (SDA), that can be produced by shearing ice I h , LDA, or HDA. Our results suggest that MDA could be obtained by ball-milling water glasses without crystallization interference. Increasing the shear rate at ambient pressure produces SDAs with densities ranging from LDA to HDA, revealing shear rate as a new thermodynamic variable in the nonequilibrium phase diagram of water. Indeed, shearing provides access to amorphous states inaccessible by controlling pressure and temperature alone. SDAs produced with shearing rates as high as 10 6 s −1 sample the same region of the potential energy landscape than hyperquenched glasses with identical density, pressure, and temperature. Intriguingly, SDAs obtained by shearing at ~10 8 s −1 have density, enthalpy, and structure indistinguishable from those of water “instantaneously” quenched from room temperature to 77 K over 10 ps, making them good approximants for the “true glass” of ambient liquid water.

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

The coupling of radiative transfer to quasi 1-D flows with thermochemical nonequilibrium

Quasi-one-dimensional nonequilibrium nozzle flows with coupled radiative transfer are considered. The strongly coupled formulation of radiation and flowfield leads to a governing set of integro-differential equations. A fully implicit numerical method using the full matrix inversion or block iteration methods is presented to solve these equations. The nonequilibrium gas model consists of two chemical species, molecular and atomic nitrogen. The thermodynamic state of the gas is described by two temperatures, translational-rotational and vibrational, and the thermal radiation is assumed to be governed by the vibrational temperature. In radiative transfer, gases are assumed to be absorbing and emitting, and a detailed spectral dependency of the absorption coefficient is prescribed for a non-gray gas. The numerical solutions of strongly radiating nonequilibrium flows are presented for both gray and non-gray gases.

Gokcen, Tahir↗
NASA NTRS1980

Influence of nonequilibrium radiation on heating of an ablating Jovian entry probe

The influence of non-local thermodynamic equilibrium (NLTE) radiative transfer on the entire shock-layer flow phenomena around a Jovian entry body is investigated. The flow in the shock layer is assumed to be viscous, axisymmetric, laminar, and in chemical equilibrium. The entry body considered is a 35-deg hyperboloid and the results have been obtained for the peak heating entry conditions. The results indicate that the radiative heating of the entry body is significantly higher under NLTE conditions.

Tiwari, S. N.↗
DOE OSTI2022

Thermodynamic Control of Activity Patterns in Cytoskeletal Networks

Biological materials, such as the actin cytoskeleton, exhibit remarkable structural adaptability to various external stimuli by consuming different amounts of energy. In this Letter, we use methods from large deviation theory to identify a thermodynamic control principle for structural transitions in a model cytoskeletal network. Specifically, we demonstrate that biasing the dynamics with respect to the work done by nonequilibrium components effectively renormalizes the interaction strength between such components, which can eventually result in a morphological transition. Further, our work demonstrates how a thermodynamic quantity can be used to renormalize effective interactions, which in turn can tune structure in a predictable manner, suggesting a thermodynamic principle for the control of cytoskeletal structure and dynamics.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1983

Improved fabrication techniques for infrared bolometers

Techniques are described for producing improved infrared bolometers from doped germanium. Ion implantation and sputter metalization have been used to make ohmic electrical contacts to Ge:Ga chips. This method results in a high yield of small monolithic bolometers with very little low-frequency noise. When one of these chips is used as the thermometric element of a composite bolometer, it must be bonded to a dielectric substrate. The thermal resistance of the conventional epoxy bond has been measured and found to be undesirably large. A procedure for soldering the chip to a metalized portion of the substrate is described which reduced this resistance. The contribution of the metal film absorber to the heat capacity of a composite bolometer has been measured. The heat capacity of a NiCr absorber at 1.3 K can dominate the bolometer performance. A Bi absorber has significantly lower heat capacity. A low temperature blackbody calibrator has been built to measure the optical responsivity of bolometers. A composite bolometer system with a throughput of approx. 0.1 sr sq cm was constructed using the new techniques. In negligible background it has an optical NEP of 3.6 10((exp -15) W/sq root of Hz at 1.0 K with a time constant of 20 ms. The noise in this bolometer is white above 2.5 Hz and is somewhat below the value predicted by thermodynamic equilibrium theory. It is in agreement with calculations based on a recent nonequilibrium theory.

Lange, A. E.↗
NASA NTRS1989

Hypervelocity atmospheric flight: Real gas flow fields

Flight in the atmosphere is examined from the viewpoint of including real gas phenomena in the flow field about a vehicle flying at hypervelocity. That is to say, the flow field is subject not only to compressible phenomena, but is dominated by energetic phenomena. There are several significant features of such a flow field. Spatially, its composition can vary by both chemical and elemental species. The equations which describe the flow field include equations of state and mass, species, elemental, and electric charge continuity; momentum; and energy equations. These are nonlinear, coupled, partial differential equations that have been reduced to a relatively compact set of equations in a self-consistent manner (which allows mass addition at the surface at a rate comparable to the free-stream mass flux). The equations and their inputs allow for transport of these quantities relative to the mass-average behavior of the flow field. Thus transport of mass by chemical, thermal, pressure, and forced diffusion; transport of momentum by viscosity; and transport of energy by conduction, chemical considerations, viscosity, and radiative transfer are included. The last of these complicate the set of equations by making the energy equations a partial integrodifferential equation. Each phenomenon is considered and represented mathematically by one or more developments. The coefficients which pertain are both thermodynamically and chemically dependent. Solutions of the equations are presented and discussed in considerable detail, with emphasis on severe energetic flow fields. Hypervelocity flight in low-density environments where gaseous reactions proceed at finite rates chemical nonequilibrium is considered, and some illustrations are presented. Finally, flight where the flow field may be out of equilibrium, both chemically and thermodynamically, is presented briefly.

Howe, John T.↗
DOE OSTI2020

Overcoming immiscibility toward bimetallic catalyst library

Bimetallics are emerging as important materials that often exhibit distinct chemical properties from monometallics. However, there is limited access to homogeneously alloyed bimetallics because of the thermodynamic immiscibility of the constituent elements. Overcoming the inherent immiscibility in bimetallic systems would create a bimetallic library with unique properties. Here, we present a nonequilibrium synthesis strategy to address the immiscibility challenge in bimetallics. As a proof of concept, we synthesize a broad range of homogeneously alloyed Cu-based bimetallic nanoparticles regardless of the thermodynamic immiscibility. The nonequilibrated bimetallic nanoparticles are further investigated as electrocatalysts for carbon monoxide reduction at commercially relevant current densities (>100 mA cm -2 ), in which Cu 0.9 Ni 0.1 shows the highest multicarbon product Faradaic efficiency of ~76% with a current density of ~93 mA cm -2 . The ability to overcome thermodynamic immiscibility in multimetallic synthesis offers freedom to design and synthesize new functional nanomaterials with desired chemical compositions and catalytic properties.

25 ENERGY STORAGE↗
NASA NTRS1990

Hypervelocity atmospheric flight: Real gas flow fields

Flight in the atmosphere is examined from the viewpoint of including real gas phenomena in the flow field about a vehicle flying at hypervelocity. That is to say, the flow field is subject not only to compressible phenomena, but is dominated by energetic phenomena. There are several significant features of such a flow field. Spatially, its composition can vary by both chemical and elemental species. The equations which describe the flow field include equations of state and mass, species, elemental, and electric charge continuity; momentum; and energy equations. These are nonlinear, coupled, partial differential equations that were reduced to a relatively compact set of equations of a self-consistent manner (which allows mass addition at the surface at a rate comparable to the free-stream mass flux). The equations and their inputs allow for transport of these quantities relative to the mass-averaged behavior of the flow field. Thus transport of mass by chemical, thermal, pressure, and forced diffusion; transport of momentum by viscosity; and transport of energy by conduction, chemical considerations, viscosity, and radiative transfer are included. The last of these complicate the set of equations by making the energy equation a partial integrodifferential equation. Each phenomenon is considered and represented mathematically by one or more developments. The coefficients which pertain are both thermodynamically and chemically dependent. Solutions of the equations are presented and discussed in considerable detail, with emphasis on severe energetic flow fields. For hypervelocity flight in low-density environments where gaseous reactions proceed at finite rates, chemical nonequilibrium is considered and some illustrations are presented. Finally, flight where the flow field may be out of equilibrium, both chemically and thermodynamically, is presented briefly.

Howe, John T.↗
DOE OSTI2020

Thermal transport exceeding bulk heat conduction due to nonthermal micro/nanoscale phonon populations

While classical size effects usually lead to a reduced effective thermal conductivity, we report here that nonthermal phonon populations produced by a micro/nanoscale heat source can lead to enhanced heat conduction, exceeding the prediction from Fourier's law. We study nondiffusive thermal transport by phonons at small distances within the framework of the Boltzmann transport equation (BTE) and demonstrate that the transport is significantly affected by the distribution of phonons emitted by the source. We discuss analytical solutions of the steady-state BTE for a source with a sinusoidal spatial profile, as well as for a three-dimensional Gaussian “hot spot,” and provide numerical results for single crystal silicon at room temperature. If a micro/nanoscale heat source produces a thermal phonon distribution, it gets hotter than that predicted by the heat diffusion equation; however, if the source predominantly produces low-frequency acoustic phonons with long mean free paths, it may get significantly cooler than that predicted by the heat equation, yielding an enhanced heat transport beyond bulk heat conduction.

42 ENGINEERING↗
DOE OSTI2024

Rotational state-to-state transition rate coefficients for H 2 O + H 2 O collisions at nonequilibrium conditions

Aims.The goal is to develop a database of rate coefficients for rotational state-to-state transitions in H 2 O + H 2 O collisions that is suitable for the modeling of energy transfer in nonequilibrium conditions, in which the distribution of rotational states of H 2 O deviates from local thermodynamic equilibrium. Methods.A two-temperature model was employed that assumed that although there is no equilibrium between all possible degrees of freedom in the system, the translational and rotational degrees of freedom can be expected to achieve their own equilibria independently, and that they can be approximately characterized by Boltzmann distributions at two different temperatures,T kin andT rot . Results.Upon introducing our new parameterization of the collisional rates, taking into account their dependence on bothT kin andT rot , we find a change of up to 20% in the H 2 O rotational level populations for both ortho and para-H 2 O for the part of the cometary coma where the nonequilibrium regime occurs.

Astronomy & Astrophysics↗
DOE OSTI2020

Negative capacitance regime in ferroelectrics demystified from nonequilibrium molecular dynamics

Negative capacitance regime in ferroelectrics is associated with the negative slope in the dependence of the polarization on electric field and is prohibited by the laws of equilibrium thermodynamics. Very recently, it developed into a controversial but very productive area with a promise for next generation low-power transistors. At least, in part, the controversies arise from the lack of direct experimental insight into the mechanism for such phenomena. Although the experimental insight is, indeed, challenging at present, we probe the effect in ferroelectric PbTiO 3 bulk and a thin film with realistic first-principles-based nonequilibrium molecular dynamics simulations which model most closely experimental conditions. Here, the following insights emerge from the simulations: (i) the ferroelectric never enters the thermodynamically forbidden region even under extreme rates of electric-field application; (ii) the negative slope naturally arises when the compensating charge is either scarce or slowed down by the external circuitry; (iii) the negative slope is well controlled by the interplay between the applied step pulse field and the amount of the screening charge. The latter can be used to design the negative capacitance regime.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗