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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Method of tuning physical properties of thermosets

Polymerization-induced phase separation enables fine control over thermoset network morphologies, yielding heterogeneous structures with domain sizes tunable over 1-100 nm. However, the controlled chain-growth polymerization techniques exclusively employed to regulate morphology at these length scales are unsuitable for most thermoset materials typically formed through step-growth mechanisms. By employing binary mixtures in place of the classic constituents of phase-separating thermosets—resin, curing agent, and secondary polymer—facile tunability over morphology can be achieved through a single compositional parameter. Indeed, this method yields morphologies spanning nano-scale to macro-scale, controlled by the relative reactivities and thermodynamic compatibility of the network components. Due to the connection between chain dynamics and microstructure in these materials, the tunable morphology enables exquisite control over glass transition and other physical and mechanical properties.

Jones, Brad Howard↗
DOE OSTI2022

Deep learning-based quasi-continuum theory for structure of confined fluids

Predicting the structural properties of water and simple fluids confined in nanometer scale pores and channels is essential in, for example, energy storage and biomolecular systems. Classical continuum theories fail to accurately capture the interfacial structure of fluids. In this work, we develop a deep learning-based quasi-continuum theory (DL-QT) to predict the concentration and potential profiles of a Lennard-Jones (LJ) fluid and water confined in a nanochannel. The deep learning model is built based on a convolutional encoder–decoder network (CED) and is applied for high-dimensional surrogate modeling to relate the fluid properties to the fluid–fluid potential. The CED model is then combined with the interatomic potential-based continuum theory to determine the concentration profiles of a confined LJ fluid and confined water. Further, we show that the DL-QT model exhibits robust predictive performance for a confined LJ fluid under various thermodynamic states and for water confined in a nanochannel of different widths. The DL-QT model seamlessly connects molecular physics at the nanoscale with continuum theory by using a deep learning model.

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

Generalized Brunauer–Emmett–Teller Isotherm for Mixed-Gas Multilayer Adsorption Equilibria

Here, this work presents a rigorous thermodynamic framework to calculate mixed-gas multilayer adsorption equilibria from single-component isotherms and vapor–liquid equilibria. Named the generalized Brunauer–Emmett–Teller (gBET) isotherm, the newly formulated isotherm considers adsorbent surface heterogeneity, competitive adsorption on the monolayer, condensation–evaporation on the subsequent layers, and adsorbed phase nonideality for the monolayer and the subsequent layers. The monolayer adsorbed phase nonideality is tracked by using an area-based adsorption nonrandom two-liquid activity coefficient model. The adsorbed phase composition and corresponding nonideality in the subsequent layers are calculated at the dew point condition of the mixed gas with either an equation of state or an activity coefficient model for the vapor–liquid equilibria. The proposed model is validated with six single and three binary multilayer adsorption equilibrium systems, and the model results are compared against those from the classical BET isotherm for single-component adsorption and ideal adsorbed solution theory for mixed-gas adsorption equilibria.

09 BIOMASS FUELS↗
DOE OSTI2021

Theory of the effect of external stress on the activated dynamics and transport of dilute penetrants in supercooled liquids and glasses

We generalize the self-consistent cooperative hopping theory for a dilute spherical penetrant or tracer activated dynamics in dense metastable hard sphere fluids and glasses to address the effect of external stress, the consequences of which are systematically established as a function of matrix packing fraction and penetrant-to-matrix size ratio. All relaxation processes speed up under stress, but the difference between the penetrant and matrix hopping (alpha relaxation) times decreases significantly with stress corresponding to less time scale decoupling. A dynamic crossover occurs at a critical “slaving onset” stress beyond which the matrix activated hopping relaxation time controls the penetrant hopping time. This characteristic stress increases (decreases) exponentially with packing fraction (size ratio) and can be well below the absolute yield stress of the matrix. Below the slaving onset, the penetrant hopping time is predicted to vary exponentially with stress, differing from the power law dependence of the pure matrix alpha time due to system-specificity of the stress-induced changes in the penetrant local cage and elastic barriers. An exponential growth of the penetrant alpha relaxation time with size ratio under stress is predicted, and at a fixed matrix packing fraction, the exponential relation between penetrant hopping time and stress for different size ratios can be collapsed onto a master curve. Direct connections between the short- and long-time activated penetrant dynamics and between the penetrant (or matrix) alpha relaxation time and matrix thermodynamic dimensionless compressibility are also predicted. The presented results should be testable in future experiments and simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Extending model-based diagnosis for analog thermodynamical devices

The increasing complexity of process control applications have posed difficult problems in fault detection, isolation, and recovery. Deep knowledge-based approaches, such as model-based diagnosis, have offered some promise in addressing these problems. However, the difficulties of adapting these techniques to situations involving numerical reasoning and noise have limited the applicability of these techniques. This paper describes an extension of classical model-based diagnosis techniques to deal with sparse data, noise, and complex noninvertible numerical models. These diagnosis techniques are being applied to the External Active Thermal Control System for Space Station Freedom.

Rouquette, Nicolas↗
DOE OSTI2020

Large-Scale Molecular Dynamics Simulation of the Dehydration of a Suspension of Smectite Clay Nanoparticles

Fine-grained sediments and sedimentary rocks play important roles in a variety of modern energy technologies from petroleum geology to geological carbon sequestration and radioactive waste management. However, despite their utility and ubiquity, many of their properties remain poorly understood. In particular, the ability to predict the permeability and mechanics of these media remains a persistent fundamental challenge in the geosciences. In the present work, we show how large-scale classical molecular dynamics (MD) simulations can help interpret the properties of fine-grained sedimentary material. All-atom simulations containing 30 discrete clay particles are utilized to understand the evolution of a clay nanoparticle suspension during its progressive dehydration. Microstructural (pore size distribution, tortuosity, anisotropy), thermodynamic (enthalpy and free energy of hydration, anion exclusion), mechanical (total suction), and transport properties (diffusion coefficient tensors of water and sodium) are calculated and compared to the experiment. Overall, our results provide new insight into the coupled chemistry, mechanics, and transport properties of disordered nanoparticle assemblages and shed light upon the important role of water films in controlling these properties.

02 PETROLEUM↗
DOE OSTI2024

Development and application of hybrid AIMD/cDFT simulations for atomic-to-mesoscale chemistry

Many important chemical processes involve reactivity and dynamics in complex solutions. Gaining a fundamental understanding of these reaction mechanisms is a challenging goal that requires advanced computational and experimental approaches. However, important techniques such as molecular simulation have limitations in terms of scales of time, length, and system complexity. Furthermore, among the currently available solvation models, there are very few designed to describe the interaction between the molecular scale and the mesoscale. To help address this challenge, here, we establish a novel hybrid approach that couples first-principles plane-wave density functional theory with classical density functional theory (cDFT). In this approach, a region of interest described by ab initio molecular dynamics (AIMD) interacts with the surrounding medium described using cDFT to arrive at a self-consistent ground state. cDFT is a robust but efficient mesoscopic approach to accurate thermodynamics of bulk electrolyte solutions over a wide concentration range (up to 2M concentrations). Benchmarking against commonly used continuum models of solvation, such as SMD, as well as experiments, demonstrates that our hybrid AIMD–cDFT method is able to produce reasonable solvation energies for a variety of molecules and ions. With this model, we also examined the solvent effects on a prototype S N 2 reaction of the nucleophilic attack of a chloride ion on methyl chloride in the solution. The resulting reaction pathway profile and the solution phase barrier agree well with experiment, showing that our AIMD/cDFT hybrid approach can provide insight into the specific role of the solvent on the reaction coordinate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Thermal decoupling of deuterium and tritium during the ICF shock-convergence phase

We report that a series of thin glass-shell shock-driven DT gas-filled capsule implosions was conducted at the OMEGA laser facility. These experiments generate conditions relevant to the central plasma during the shock-convergence phase of ablatively driven inertial confinement fusion (ICF) implosions. The spectral temperatures inferred from the DTn and DDn spectra are most consistent with a two-ion-temperature plasma, where the initial apparent temperature ratio, $\frac{T_T}{T_P}$, is 1.5. This is an experimental confirmation of the long-standing conjecture that plasma shocks couple energy directly proportional to the species mass in multi-ion plasmas. The apparent temperature ratio trend with equilibration time matches expected thermal equilibration described by hydrodynamic theory. This indicates that deuterium and tritium ions have different energy distributions for the time period surrounding shock convergence in ignition-relevant ICF implosions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Model-Free Measurement of Local Entropy Production and Extractable Work in Active Matter

Time-reversal symmetry breaking and entropy production are universal features of nonequilibrium phenomena. Despite its importance in the physics of active and living systems, the entropy production of systems with many degrees of freedom has remained of little practical significance because the high dimensionality of their state space makes it difficult to measure. Here, in this work, we introduce a local measure of entropy production and a numerical protocol to estimate it. We establish a connection between the entropy production and extractability of work in a given region of the system and show how this quantity depends crucially on the degrees of freedom being tracked. We validate our approach in theory, simulation, and experiments by considering systems of active Brownian particles undergoing motility-induced phase separation, as well as active Brownian particles and E.coli in a rectifying device in which the time-reversal asymmetry of the particle dynamics couples to spatial asymmetry to reveal its effects on a macroscopic scale.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2021

On the origin & thermal stability of Arrokoth's and Pluto's ice

In this paper we discuss in a thermodynamic, geologically empirical way the long-term nature of the stable majority ices that could be present in Kuiper Belt object (KBO) 2014 MU69 (also called Arrokoth; hereafter “MU(69)”) after its 4.6 Gyr residence in the Edgeworth-Kuiper belt (EKB) as a cold classical object. We compare the upper bounds for the gas production rate (~10^(24) molecules/s) measured by the New Horizons (NH) spacecraft flyby on 01 Jan 2019 to estimates for the outgassing flux rates from a suite of common cometary and KBO ices at the average ~ 40 K sunlit surface temperature of MU69, but do not find the upper limit very constraining except for the most volatile of species (e.g. CO, N2, CH4). More constraining is the stability versus sublimation into vacuum requirement over Myr to Gyr, and from this we find only 3 common ices that are truly refractory: HCN, CH3OH, and H2O (in order of increasing stability), while NH3 and H2CO ices are marginally stable and may be removed by any positive temperature excursions in the EKB, as produced every 10^(8)–10^(9) years by nearby supernovae and passing O/B stars. To date the NH team has reported the presence of abundant CH3OH and H2O on MU69's surface (Stern et al., 2019; Grundy et al., 2020). NH3 has been searched for, but not found. We predict that future absorption feature detections, if any are ever derived from higher signal-to-noise ratio spectra, will be due to an HCN or poly-H2CO based species. Consideration of the conditions present in the EKB region during the formation era of MU69 lead us to state that it is highly likely that it “formed in the dark”, in an optically thick mid-plane, unable to see the nascent, variable, highly luminous Young Stellar Object (YSO)/TTauri Sun, and that KBOs contain HCN and CH3OH ice phases in addition to the H2O ice phases found in their short period (SP) comet descendants. Finally, when we apply our ice thermal stability analysis to bodies/populations related to MU69, we find that methanol ice is likely ubiquitous in the outer solar system; that if Pluto isn't a fully differentiated body, then it must have gained its hypervolatile ices from proto-planetary disk (PPD) sources in the first few Myr of the solar system's existence; and that hypervolatile rich, highly primordial comet C/2016 R2 was placed onto an Oort Cloud orbit on a similar few Myr timescale.

Pluto↗
DOE OSTI2023

Real-space observation of ergodicity transitions in artificial spin ice

Abstract Ever since its introduction by Ludwig Boltzmann, the ergodic hypothesis became a cornerstone analytical concept of equilibrium thermodynamics and complex dynamic processes. Examples of its relevance range from modeling decision-making processes in brain science to economic predictions. In condensed matter physics, ergodicity remains a concept largely investigated via theoretical and computational models. Here, we demonstrate the direct real-space observation of ergodicity transitions in a vertex-frustrated artificial spin ice. Using synchrotron-based photoemission electron microscopy we record thermally-driven moment fluctuations as a function of temperature, allowing us to directly observe transitions between ergodicity-breaking dynamics to system freezing, standing in contrast to simple trends observed for the temperature-dependent vertex populations, all while the entropy features arise as a function of temperature. These results highlight how a geometrically frustrated system, with thermodynamics strictly adhering to local ice-rule constraints, runs back-and-forth through periods of ergodicity-breaking dynamics. Ergodicity breaking and the emergence of memory is important for emergent computation, particularly in physical reservoir computing. Our work serves as further evidence of how fundamental laws of thermodynamics can be experimentally explored via real-space imaging.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Counterdiabatic Driving with Performance Guarantees

Counterdiabatic (CD) driving has the potential to speed up adiabatic quantum state preparation by suppressing unwanted excitations. However, existing approaches either require intractable classical computations or are based on approximations that do not have performance guarantees. We propose and analyze a nonvariational, system-agnostic CD expansion method and analytically show that it converges exponentially quickly in the expansion order. In finite systems, the required resources scale inversely with the spectral gap, which we argue is asymptotically optimal. To extend our method to the thermodynamic limit and suppress errors stemming from high-frequency transitions, we leverage finite-time adiabatic protocols. In particular, we show that a time determined by the quantum speed limit is sufficient to prepare the desired ground state, without the need to optimize the adiabatic trajectory. Numerical tests of our method on the quantum Ising chain show that our method can outperform state-of-the-art variational CD approaches.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Fluctuation–dissipation relation for a quantum Brownian oscillator in a parametrically squeezed thermal field

In this paper we study the nonequilibrium evolution of a quantum Brownian oscillator, modeling the internal degree of freedom of a harmonic atom or an Unruh–DeWitt detector, coupled to a nonequilibrium and nonstationary quantum field bath and inquire whether a fluctuation–dissipation relation (FDR) can exist after/if it approaches equilibration. This is a nontrivial issue because a squeezed field bath cannot reach equilibration and yet, as this work shows, the system oscillator indeed can, which is a necessary condition for FDRs. We discuss three different settings: (A) The bath field essentially remains in a squeezed thermal state throughout, whose squeeze parameter is a mode- and time-independent constant. This situation is often encountered in quantum optics and quantum thermodynamics. (B) The bath field is initially in a thermal state, but is subjected to a parametric process leading to mode- and time-dependent squeezing. This scenario is encountered in cosmology and dynamical Casimir effects. The squeezing in the bath in both types of processes will affect the oscillator’s nonequilibrium evolution. We show that at late times it approaches equilibration and this stationarity condition warrants the existence of a FDR. The trait of squeezing is marked by the oscillator’s effective equilibrium temperature, and the proportionality factor in the FDR is only related to the stationary component of the noise kernel of the bath field. Setting (C) is more subtle: A finite system–bath coupling strength can set the oscillator in a squeezed state even though the bath field is stationary and does not engage in any parametric process. The squeezing of the system in this case is in general time-dependent but becomes constant when the internal dynamics is fully relaxed. We begin with comments on the broad range of physical processes involving squeezed thermal baths and end with some remarks on the significance of FDRs in capturing the essence of quantum backreaction in nonequilibrium and stochastic systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2015

Thermodynamic Derivation of the Activation Energy for Ice Nucleation

Cirrus clouds play a key role in the radiative and hydrological balance of the upper troposphere. Their correct representation in atmospheric models requires an understanding of the microscopic processes leading to ice nucleation. A key parameter in the theoretical description of ice nucleation is the activation energy, which controls the flux of water molecules from the bulk of the liquid to the solid during the early stages of ice formation. In most studies it is estimated by direct association with the bulk properties of water, typically viscosity and self-diffusivity. As the environment in the ice-liquid interface may differ from that of the bulk, this approach may introduce bias in calculated nucleation rates. In this work a theoretical model is proposed to describe the transfer of water molecules across the ice-liquid interface. Within this framework the activation energy naturally emerges from the combination of the energy required to break hydrogen bonds in the liquid, i.e., the bulk diffusion process, and the work dissipated from the molecular rearrangement of water molecules within the ice-liquid interface. The new expression is introduced into a generalized form of classical nucleation theory. Even though no nucleation rate measurements are used to fit any of the parameters of the theory the predicted nucleation rate is in good agreement with experimental results, even at temperature as low as 190 K, where it tends to be underestimated by most models. It is shown that the activation energy has a strong dependency on temperature and a weak dependency on water activity. Such dependencies are masked by thermodynamic effects at temperatures typical of homogeneous freezing of cloud droplets; however, they may affect the formation of ice in haze aerosol particles. The new model provides an independent estimation of the activation energy and the homogeneous ice nucleation rate, and it may help to improve the interpretation of experimental results and the development of parameterizations for cloud formation.

Cirrus clouds↗
DOE OSTI2021

Evaluation of two-particle properties within finite-temperature self-consistent one-particle Green’s function methods: Theory and application to GW and GF2

One-particle Green’s function methods can model molecular and solid spectra at zero or non-zero temperatures. One-particle Green’s functions directly provide electronic energies and one-particle properties, such as dipole moment. However, the evaluation of two-particle properties, such as $\langle$S 2 $\rangle$ and $\langle$N 2 $\rangle$, can be challenging because they require a solution of the computationally expensive Bethe–Salpeter equation to find two-particle Green’s functions. We demonstrate that the solution of the Bethe–Salpeter equation can be completely avoided. Applying the thermodynamic Hellmann–Feynman theorem to self-consistent one-particle Green’s function methods, we derive expressions for two-particle density matrices in a general case and provide explicit expressions for GF2 and GW methods. Such density matrices can be decomposed into an antisymmetrized product of correlated one-electron density matrices and the two-particle electronic cumulant of the density matrix. Cumulant expressions reveal a deviation from ensemble representability for GW, explaining its known deficiencies. We analyze the temperature dependence of $\langle$S 2 $\rangle$ and $\langle$N 2 $\rangle$ for a set of small closed-shell systems. Interestingly, both GF2 and GW show a non-zero spin contamination and a non-zero fluctuation of the number of particles for closed-shell systems at the zero-temperature limit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Dynamics of Subsiding Shells in Actively Growing Clouds with Vertical Updrafts

The dynamics of a subsiding shell at the edges of actively growing shallow cumulus clouds with updrafts is analyzed using direct numerical simulation. The actively growing clouds have a fixed in-cloud buoyancy and velocity. Turbulent mixing and evaporative cooling at the cloud edges generate a subsiding shell that grows with time. A self-similar regime is observed for first- and second-order moments when normalized with respective maximum values. Internal scales derived from integral properties of the flow problem are identified. A self-similarity analysis using these scales reveals that contrary to classical self-similar flows, the turbulent kinetic energy budget terms and velocity moments scale according to the buoyancy and not with the mean velocity. The shell thickness is observed to increase linearly with time. The buoyancy scale remains time invariant and is set by the initial cloud–environment thermodynamics. The shell accelerates ballistically with a magnitude set by the saturation value of the buoyancy of the cloud–environment mixture. In this regime, the shell is buoyancy driven and independent of the in-cloud velocity. Relations are obtained for predicting the shell thickness and minimum velocities by linking the internal scales with external flow parameters. The values thus calculated are consistent with the thickness and velocities observed in typical shallow cumulus clouds. The entrainment coefficient is a function of the initial state of the cloud and the environment, and is shown to be on the same order of magnitude as fractional entrainment rates calculated for large-scale models.

54 ENVIRONMENTAL SCIENCES↗