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DOE OSTI2015

Ab initio atomistic thermodynamics study on the oxidation mechanism of binary and ternary alloy surfaces

Utilizing a combination of ab initio density-functional theory and thermodynamics formalism, we have established the microscopic mechanisms for oxidation of the binary and ternary alloy surfaces and provided a clear explanation for the experimental results of the oxidation. We construct three-dimensional surface phase diagrams (SPDs) for oxygen adsorption on three different Nb-X(110) (X = Ti, Al or Si) binary alloy surfaces. On the basis of the obtained SPDs, we conclude a general microscopic mechanism for the thermodynamic oxidation, that is, under O-rich conditions, a uniform single-phase SPD (type I) and a nonuniform double-phase SPD (type II) correspond to the sustained complete selective oxidation and the non-sustained partial selective oxidation by adding the X element, respectively. Furthermore, by revealing the framework of thermodynamics for the oxidation mechanism of ternary alloys through the comparison of the surface energies of two separated binary alloys, we provide an understanding for the selective oxidation behavior of the Nb ternary alloy surfaces. Using these general microscopic mechanisms, one could predict the oxidation behavior of any binary and multi-component alloy surfaces based on thermodynamics considerations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

On the thermodynamic efficiency of a nickel-based multiferroic thermomagnetic generator: From bulk to atomic scale

A model is developed to correlate the effects of size on the thermodynamic efficiency for a nickel-based multiferroic thermomagnetic generator device. Three existing models are combined in order to estimate this correlation, they are (1) thermodynamic efficiency relations, (2) a model of ferromagnetic transition behavior, and (3) the bond-order length strength correlation. At the smallest size considered, a monolayer of nickel atoms shows a reduction in Curie temperature from its bulk value of T{sub c,Bulk}=630 K to T{sub c,ML}=240 K. This difference is analytically shown to affect the thermodynamic efficiency values when compared to bulk. Various nickel nanofilms are considered as a working body, such that the combined model predicts relative efficiency values that are comparable to the bulk scale, but operating closer to room-temperature when compared to bulk form. This result is unexpected since the absolute efficiency is shown to increase as a function of decreasing size, this discrepancy is explained as a consequence of Curie point suppression. The combined model is also applied to a hypothetical composite made of separated layers of nickel with distinct thicknesses. This composite material is predicted to spread the ferromagnetic transition across a much larger temperature range as compared to bulk nickel, such that this material may be better suited for different applications; for example, as a sensor or thermal switch. Moreover, this combined model is also shown to give a lower-bound estimate for thermodynamic efficiency, since the actual performance depends on material characterizations that have yet to be determined.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2015

Fluids confined in wedges and by edges: From cluster integrals to thermodynamic properties referred to different regions

Recently, new insights into the relation between the geometry of the vessel that confines a fluid and its thermodynamic properties were traced through the study of cluster integrals for inhomogeneous fluids. In this work, I analyze the thermodynamic properties of fluids confined in wedges or by edges, emphasizing on the question of the region to which these properties refer. In this context, the relations between the line-thermodynamic properties referred to different regions are derived as analytic functions of the dihedral angle α, for 0 < α < 2π, which enables a unified approach to both edges and wedges. As a simple application of these results, I analyze the properties of the confined gas in the low-density regime. Finally, using recent analytic results for the second cluster integral of the confined hard sphere fluid, the low density behavior of the line thermodynamic properties is analytically studied up to order two in the density for 0 < α < 2π and by adopting different reference regions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2013

Thermodynamic behavior of particular f(R,T)-gravity models

We investigate the thermodynamics at the apparent horizon of the FRW universe in f(R, T) theory in the nonequilibrium description. The laws of thermodynamics are discussed for two particular models of the f(R, T) theory. The first law of thermodynamics is expressed in the form of the Clausius relation <##> } T h d } S }^ h = δ Q $ T{sub h} d/hat S{sub h} = /delta Q $ T{sub h}d S-hat {sub h}=δQ </##>, where δQ is the energy flux across the horizon and <##> } d } S }^ $ d/hat S $ d S-hat </##> is the entropy production term. Furthermore, the conditions for the generalized second law of thermodynamics to be preserved are established with the constraints of positive temperature and attractive gravity. We illustrate our results for some concrete models in this theory.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2024

Pyrophosphate-free glycolysis in Clostridium thermocellum increases both thermodynamic driving force and ethanol titers

Background: Clostridium thermocellum is a promising candidate for production of cellulosic biofuels, however, its final product titer is too low for commercial application, and this may be due to thermodynamic limitations in glycolysis. Previous studies in this organism have revealed a metabolic bottleneck at the phosphofructokinase (PFK) reaction in glycolysis. In the wild-type organism, this reaction uses pyrophosphate (PP i ) as an energy cofactor, which is thermodynamically less favorable compared to reactions that use ATP as a cofactor. Previously we showed that replacing the PP i -linked PFK reaction with an ATP-linked reaction increased the thermodynamic driving force of glycolysis, but only had a local effect on intracellular metabolite concentrations, and did not affect final ethanol titer. Results: In this study, we substituted PP i -pfk with ATP-pfk, deleted the other PPi-requiring glycolytic gene pyruvate:phosphate dikinase (ppdk), and expressed a soluble pyrophosphatase (PPase) and pyruvate kinase (pyk) genes to engineer PP i -free glycolysis in C. thermocellum. We demonstrated a decrease in the reversibility of the PFK reaction, higher levels of lower glycolysis metabolites, and an increase in ethanol titer by an average of 38% (from 15.1 to 21.0 g/L) by using PP i -free glycolysis. Conclusions: By engineering PP i -free glycolysis in C. thermocellum, we achieved an increase in ethanol production. These results demonstrate that optimizing the thermodynamic landscape through metabolic engineering can enhance product titers. While further increases in ethanol titers are necessary for commercial application, this work represents a significant step toward engineering glycolysis in C. thermocellum to increase ethanol titers.

09 BIOMASS FUELS↗

DOE OSTI2014

Perform Thermodynamics Measurements on Fuel Cycle Case Study Systems

This document was prepared to meet FCR&D level 3 milestone M3FT-14IN0304022, “Perform Thermodynamics Measurements on Fuel Cycle Case Study Systems.” This work was carried out under the auspices of the Thermodynamics and Kinetics FCR&D work package. This document reports preliminary work in support of determining the thermodynamic parameters for the ALSEP process. The ALSEP process is a mixed extractant system comprised of a cation exchanger 2-ethylhexyl-phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and a neutral solvating extractant N,N,N’,N’-tetraoctyldiglycolamide (TODGA). The extractant combination produces complex organic phase chemistry that is challenging for traditional measurement techniques. To neutralize the complexity, temperature dependent solvent extraction experiments were conducted with neat TODGA and scaled down concentrations of the ALSEP formulation to determine the enthalpies of extraction for the two conditions. A full set of thermodynamic data for Eu, Am, and Cm extraction by TODGA from 3.0 M HNO3 is reported. These data are compared to previous extraction results from a 1.0 M HNO3 aqueous medium, and a short discussion of the mixed HEH[EHP]/TODGA system results is offered.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Thermodynamic Cloud Phase Classifications Using Machine Learning at NSA and ANX

Vertically resolved thermodynamic cloud phase classifications are essential for studies of atmospheric cloud and precipitation processes. The Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) THERMOCLDPHASE Value-Added Product (VAP) uses a multi-sensor approach to classify thermodynamic cloud phase by combining lidar backscatter and depolarization, radar reflectivity, Doppler velocity, spectral width, microwave radiometer-derived liquid water path, and radiosonde temperature measurements. The measured voxels are classified as ice, snow, mixed-phase, liquid (cloud water), drizzle, rain, and liq_driz (liquid+drizzle). We use this product as the ground truth to train three machine learning (ML) models to predict the thermodynamic cloud phase from multi-sensor remote sensing measurements taken at the ARM North Slope of Alaska (NSA) observatory: a random forest (RF), a multilayer perceptron (MLP), and a convolutional neural network (CNN) with a U-Net architecture. Evaluations against the outputs of the THERMOCLDPHASE VAP with one year of data show that the CNN outperforms the other two models, achieving the highest test accuracy, F1-score, and mean Intersection over Union (IOU). Analysis of ML confidence scores shows ice, rain, and snow have higher confidence scores, followed by liquid, while mixed, drizzle, and liq_driz have lower scores. Feature importance analysis reveals that the mean Doppler velocity and vertically resolved temperature are the most influential datastreams for ML thermodynamic cloud phase predictions. The ML models’ generalization capacity is further evaluated by applying them at another Arctic ARM site in Norway using data taken during the ARM Cold-Air Outbreaks in the Marine Boundary Layer Experiment (COMBLE) field campaign. Finally, we evaluate the ML models’ response to simulated instrument outages and signal degradation.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Synthesis, characterization, and thermodynamic study of selected K-based zeolites

Potassium-rich zeolites often occur in cementitious systems, as K{sup +} is widespread in various cementitious materials, such as Portland, blended and alkali-activated cements. The knowledge of their stability and of thermodynamic models for solid solutions with Na{sup +} and Ca{sup 2+} are critical to understand long-term development and durability in such cements. Completing previous studies on Na- and Ca-based zeolites, the current work aims to determine the thermodynamic data of 14 types of K-based zeolites, which could possibly form in cementitious systems. The zeolites were synthesized hydrothermally, exchanged with K{sup +}, and characterized thoroughly with respect to framework structures, elemental compositions, water contents, and bond variations. Their thermodynamic properties were derived from the experimental solubility data, which allowed establishing predominance diagrams in the K{sub 2}O-SiO{sub 2}-Al{sub 2}O{sub 3}-H{sub 2}O system. The K-based zeolites typically showed the lowest solubility between 0 and 100 °C, with the notable exception of Ca-gismondine and two Na-based zeolites: natrolite and Na-mordenite.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Determining all thermodynamic transport coefficients for an interacting large N quantum field theory

Thermodynamic transport coefficients can be calculated directly from quantum field theory without requiring analytic continuation to real time. We determine all second-order thermodynamic transport coefficients for the uncharged N-component massless (critical) scalar field theory with quartic interaction in the large N limit, for any value of the coupling. We find that in the large N limit, all thermodynamic transport coefficients for the interacting theory can be expressed analytically in terms of the in-medium mass and sums over modified Bessel functions. We expect our technique to allow a similar determination of all thermodynamic transport coefficients for all theories that are solvable in the large N limit, including certain gauge theories.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2016

Black hole thermodynamics from a variational principle: asymptotically conical backgrounds

The variational problem of gravity theories is directly related to black hole thermodynamics. For asymptotically locally AdS backgrounds it is known that holographic renormalization results in a variational principle in terms of equivalence classes of boundary data under the local asymptotic symmetries of the theory, which automatically leads to finite conserved charges satisfying the first law of thermodynamics. We show that this connection holds well beyond asymptotically AdS black holes. In particular, we formulate the variational problem for N = 2 STU supergravity in four dimensions with boundary conditions corresponding to those obeyed by the so called ‘subtracted geometries’. We show that such boundary conditions can be imposed covariantly in terms of a set of asymptotic second class constraints, and we derive the appropriate boundary terms that render the variational problem well posed in two different duality frames of the STU model. This allows us to define finite conserved charges associated with any asymptotic Killing vector and to demonstrate that these charges satisfy the Smarr formula and the first law of thermodynamics. Moreover, by uplifting the theory to five dimensions and then reducing on a 2-sphere, we provide a precise map between the thermodynamic observables of the subtracted geometries and those of the BTZ black hole. Finally, surface terms play a crucial role in this identification.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2013

Relativistic distribution function for particles with spin at local thermodynamical equilibrium

We present an extension of relativistic single-particle distribution function for weakly interacting particles at local thermodynamical equilibrium including spin degrees of freedom, for massive spin 1/2 particles. We infer, on the basis of the global equilibrium case, that at local thermodynamical equilibrium particles acquire a net polarization proportional to the vorticity of the inverse temperature four-vector field. The obtained formula for polarization also implies that a steady gradient of temperature entails a polarization orthogonal to particle momentum. The single-particle distribution function in momentum space extends the so-called Cooper–Frye formula to particles with spin 1/2 and allows us to predict their polarization in relativistic heavy ion collisions at the freeze-out. -- Highlights: •Single-particle distribution function in local thermodynamical equilibrium with spin. •Polarization of spin 1/2 particles in a fluid at local thermodynamical equilibrium. •Prediction of a new effect: a steady gradient of temperature induces a polarization. •Application to the calculation of polarization in relativistic heavy ion collisions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2017

First-principles calculations and thermodynamic modeling of the Yb-Ni binary system

A complete thermodynamic description of the Yb-Ni binary system is developed by means of the CALculation of PHAse Diagram (CALPHAD) method in combination with first-principles calculations based on density functional theory (DFT) and available experimental data in the literature. Finite temperature thermodynamic properties of the Yb-Ni intermetallic compounds are predicted using the quasi-harmonic approach, where first-principles phonon calculations are performed to calculate the lattice vibrational entropy. Here, the associate solution model is used to describe the complex thermodynamic behavior of the liquid phase. The calculated phase diagram agrees well the experimental phase equilibrium data in the literature. By the coupling of CALPHAD modeling with first-principles calculations, the present work provides a more thermodynamically accurate model of the Yb-Ni system when compared to previous models.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Simulation of the properties of MgO-MgfCl{sub 2}-H{sub 2}O system by thermodynamic method

Magnesium oxychloride cement (MOC) has been investigated by many researchers who have studied its hydration products and properties. Previous works mainly concentrated on experimental studies. This study uses a thermodynamic approach to understand the formation conditions of two major hydration products of MOC, Mg{sub 3}(OH){sub 5}Cl · 4H{sub 2}O (phase 5) and Mg{sub 2}(OH){sub 3}Cl · 4H{sub 2}O (phase 3) at room temperature. The hydration reaction equilibrium of MOC phases has been predicted by using the geochemistry speciation code PHREEQC together with the extended ‘Pitzer.dat’ database. The results show that the formation of the hydration products are controlled by MgCl{sub 2} concentration, activity of H{sub 2}O and pH values of the system. The equilibrium of solid phase diagram, the solubility of different hydration phases are consistent with those results obtained from experimental studies, which validates the thermodynamic model. The phase diagram provides qualitative insights on the synthesis of pure phase 3 and phase 5. For MgO-MgCl{sub 2}-H{sub 2}O system, the minimum MgCl{sub 2} concentration for phase 5 and phase 3 to form are 1.47 mol · kg{sup −} {sup 1} and 2.25 mol · kg{sup −} {sup 1}, respectively. Increasing water volume can result in the transformation from phase 5 and phase 3 to brucite. Additionally, the stability analysis suggests that phase 5 prefers to formation at a higher condition of the a{sub Mg}2 +, pH and a{sub H2O} as compared to the phase 3. Phosphate can significantly influence the hydration products composition of MOC during hydration but no new phosphate appears. - Highlights: • A thermodynamic database was established for magnesium oxychloride cement system on the basis of Pitzer.dat. • Thermodynamic behaviors of magnesium oxychloride cement hydration was modeled. • Calculated phase diagram of magnesium oxychloride cement was plotted.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2016

Hydrothermal transport, deposition, and fractionation of the REE: Experimental data and thermodynamic calculations

For many years, our understanding of the behavior of the REE in hydrothermal systems was based on semi-empirical estimates involving extrapolation of thermodynamic data obtained at 25 °C. Since then, a substantial body of experimental data has accumulated on the stability of aqueous complexes of the REE. These data have shown that some of the predictions of Haas et al. (1995) are accurate, but others may be in error by several orders of magnitude. However, application of the data in modeling hydrothermal transport and deposition of the REE has been severely hampered by the lack of data on the thermodynamic properties of even the most common REE minerals. The discrepancies between the predictions and experimental determinations of the thermodynamic properties of aqueous REE species, together with the paucity of data on the stability of REE minerals, raise serious questions about the reliability of some models that have been proposed for the hydrothermal mobility of these critical metals. In this contribution, we review a body of high-temperature experimental data collected over the past 15 years on the stability of REE aqueous species and minerals. Using this new thermodynamic dataset, we re-evaluate the mechanisms responsible for hydrothermal transport and deposition of the REE. We also discuss the mechanisms that can result in REE fractionation during their hydrothermal transport and deposition. Here, our calculations suggest that in hydrothermal solutions, the main REE transporting ligands are chloride and sulfate, whereas fluoride, carbonate, and phosphate likely play an important role as depositional ligands. In addition to crystallographic fractionation, which is based on the differing affinity of mineral structures for the REE, our models suggest that the REE can be fractionated hydrothermally due to the differences in the stability of the LREE and HREE as aqueous chloride complexes.

58 GEOSCIENCES↗

DOE OSTI2014

Film and membrane-model thermodynamics of free thin liquid films

In spite of over 7 decades of effort, the thermodynamics of thin free liquid films (as in emulsions and foams) lacks clarity. Following a brief review of the meaning and measurement of thin-film forces (i.e., conjoining/disjoining pressures), we offer a consistent analysis of thin-film thermodynamics. By carefully defining film reversible work, two distinct thermodynamic formalisms emerge: a film model with two zero-volume membranes each of film tension γ ƒ and a membrane model with a single zero-volume membrane of membrane tension 2γ m . In both models, detailed thermodynamic analysis gives rise to thin-film Gibbs adsorption equations that allow calculation of film and membrane tensions from measurements of disjoining-pressure isotherms. A modified Young–Laplace equation arises in the film model to calculate film-thickness profiles from the film center to the surrounding bulk meniscus. No corresponding relation exists in the membrane model. Illustrative calculations of disjoining-pressure isotherms for water are presented using square-gradient theory. In conclusion, we report considerable deviations from Hamaker theory for films less than about 3 nm in thickness. Such thin films are considerably more attractive than in classical Hamaker theory. Available molecular simulations reinforce this finding.

Conjoining/disjoining pressure↗

DOE OSTI2020

Thermodynamic theory of crystal plasticity: Formulation and application to polycrystal fcc copper

We present a thermodynamic description of crystal plasticity. Our formulation is based on the Langer-Bouchbinder-Lookman thermodynamic dislocation theory (TDT), which asserts the fundamental importance of an effective temperature that describes the state of configurational disorder and therefore the dislocation density of the crystalline material. We extend the TDT description from isotropic plasticity to crystal plasticity with many slip systems. Finite-element simulations show favourable comparison with experiments on polycrystal fcc copper under uniaxial compression, tension, and simple shear. Here, the thermodynamic theory of crystal plasticity thus provides a thermodynamically consistent and physically rigorous description of dislocation motion in crystals. We also discuss new insights about the interaction of dislocations belonging to different slip systems.

36 MATERIALS SCIENCE↗

DOE OSTI2013

Structural, electronic and thermodynamic properties of R{sub 3}ZnH{sub 5} (R=K, Rb, Cs): A first-principle calculation

R{sub 3}ZnH{sub 5} (R=K, Rb, Cs) series have been investigated with respect to the crystal structure, electronic and thermodynamic properties using first-principle methods based on density functional theory with generalized gradient approximation. The optimized structures and atomic coordinates are in good agreement with the experimental data. The strong covalent interactions are obtained between Zn and H atoms in the 18-electron [ZnH{sub 4}]{sup 2-} complex, while an ionic interaction is found between [ZnH{sub 4}]{sup 2-} and R atom. The formation enthalpies show that the formations of R{sub 3}ZnH{sub 5} hydrides are all exothermic at 298 K. The vibration free energies of R{sub 3}ZnH{sub 5} show that the thermodynamic stabilities of R{sub 3}ZnH{sub 5} hydrides decrease with the increasing diameter of R atom. Two possible decomposition reactions of R{sub 3}ZnH{sub 5} series have been suggested in our work. One (reaction one) is that R{sub 3}ZnH{sub 5} hydrides decomposes to elements directly, and the other (reaction two) is that R{sub 3}ZnH{sub 5} hydrides decomposes to RH hydride. The results show that the first decomposition reaction is more favorable one. The spontaneous decomposition reaction of K{sub 3}ZnH{sub 5} hydrides occur upon 465 K via reaction one, and 564 K via reaction two, respectively. - Graphical abstract: Total charge density of K{sub 3}ZnH{sub 5}. Highlights: Black-Right-Pointing-Pointer Electronic and thermodynamic properties of R{sub 3}ZnH{sub 5} (R=K, Rb, Cs) were calculated. Black-Right-Pointing-Pointer The formations of R{sub 3}ZnH{sub 5} hydrides are all exothermic at 298 K. Black-Right-Pointing-Pointer The thermodynamic stabilities decrease with the increasing diameter of R atom. Black-Right-Pointing-Pointer Two possible decomposition pathways of R{sub 3}ZnH{sub 5} were investigated.

36 MATERIALS SCIENCE↗

DOE OSTI2013

Thermodynamic studies of CaLaFe₁₁O₁₉(s)

Thermodynamic studies on CaLaFe₁₁O₁₉(s) were carried out using Knudsen effusion mass spectrometry and calorimetry, viz. differential scanning calorimetry and high temperature oxide melt solution calorimetry. Standard molar Gibbs free energy of formation (Δ{sub f}G⁰{sub m}), enthalpy of formation and heat capacity (C⁰{sub ₚ,m}) of the compound were calculated as a function of temperature for the first time. C⁰{sub ₚ,m}(CaLaFe₁₁O₁₉) was determined and used for second law analysis, from which enthalpy and entropy of formation of the compound were calculated and the respective values are: Δ{sub f}H⁰{sub m}(298.15 K)/kJ mol⁻¹=-6057(±8) and S⁰{sub m}(298.15 K)/J K⁻¹ mol⁻¹=427(±5). Δ{sub f}H⁰{sub m}(298.15 K)/kJ mol⁻¹: -6055(±6) was also calculated using oxide melt solution calorimetry, which is in close agreement with the second law value. A heat capacity anomaly was also observed at T=684 K. A table of thermodynamic data from 298.15 K to 1000 K for CaLaFe₁₁O₁₉(s) was also constructed to represent an optimized set of data. - graphical abstract: Variation of standard molar heat capacities of CaLaF₁₁O₁₉(s) and MFe₁₂O₁₉(s) (M=Sr, Ba and Pb) as a function of temperature. Highlights: • Thermodynamic studies on CaLaFe₁₁O₁₉(s) were performed using KEQMS and solution calorimetry. • It was synthesized using gel combustion route and characterized by XRD technique. • The compound is magnetic in nature and shows a heat capacity anomaly at 684 K. • Thermodynamic table was constructed from 298 K to 1000 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗