Phonon anharmonicity and negative thermal expansion in SnSe

The anharmonic phonon properties of SnSe in the Pnma phase were investigated with a combination of experiments and first-principles simulations. Using inelastic neutron scattering (INS) and nuclear resonant inelastic X-ray scattering (NRIXS), we have measured the phonon dispersions and density of states (DOS) and their temperature dependence, which revealed a strong, inhomogeneous shift and broadening of the spectrum on warming. First-principles simulations were performed to rationalize these measurements, and to explain the previously reported anisotropic thermal expansion, in particular the negative thermal expansion within the Sn-Se bilayers. Including the anisotropic strain dependence of the phonon free energy, in addition to the electronic ground state energy, is essential to reproduce the negative thermal expansion. From the phonon DOS obtained with INS and additional calorimetry measurements, we quantify the harmonic, dilational, and anharmonic components of the phonon entropy, heat capacity, and free energy. The origin of the anharmonic phonon thermodynamics is linked to the electronic structure.

Chemical composition of ocean manganese nodules from the Pacific Ocean using different techniques

Mineralogical and chemical analyses performed on 67 ferromanganese nodules from widely varying locations and depths within the marine environment of the Pacific Ocean indicate that the minor element composition is controlled by the mineralogy and that the formation of the mineral phases is depth dependent. The pressure effect upon the thermodynamics or kinetics of mineral formation is suggested as the governing agent in the depth dependence of the mineralogy. The minor elements, Pb and Co, appear concentrated in the dMnO2 phase, whereas Cu and Ni are more or less excluded from this phase. In the manganites, Pb and Co are relatively low in concentration, whereas Cu and Ni are spread over a wide range of values. The oxidation of Pb and Co from divalent forms in sea water to higher states can explain their concentration in the dMnO2 phase.

Bubble Growth From First Principals

We consider the simplest relevant problem in the foaming of molten plastics, the growth of a single bubble in a sea of highly viscous Newtonian fluid, and without interference from other bubbles. This simplest problem has defied accurate solution from first principles. Despite plenty of research on foaming, classical approaches from first principles have neglected the temperature rise in the surrounding fluid, and we find that this oversimplification greatly accelerates bubble growth prediction. We use a transport phenomena approach to analyze the growth of a solitary bubble, expanding under its own pressure. We consider a bubble of ideal gas growing without the accelerating contribution from mass transfer into the bubble. We explore the roles of viscous forces, fluid inertia, and viscous dissipation. We find that bubble growth depends upon the nucleus radius and nucleus pressure. We begin with a detailed examination of the classical approaches (thermodynamics without viscous heating). Our failure to fit experimental data with these classical approaches, sets up the second part of our paper, a novel exploration of the essential decelerating role of viscous heating. We explore both isothermal and adiabatic bubble expansion, and also the decelerating role of surface tension. The adiabatic analysis accounts for the slight deceleration due to the cooling of the expanding gas, which depends on gas polyatomicity. We also explore the pressure profile, and the components of the extra stress tensor, in the fluid surrounding the growing bubble. These stresses can eventually be frozen into foamed plastics. We find that our new theory compares well with measured bubble behavior.

Heat Transfer in an Airfoil Shaped Strut

The heat transfer from a hot primary flow stream passing over the outside of an airfoil shaped strut to a cool secondary flow stream passing through the inside of that strut was studied experimentally and numerically. The results showed that the heat transfer on the inside of the strut could be reliably modeled as a developing flow and described using a power law model. The heat transfer on the outside of the strut was complicated by flow separation and stall on the suction side of the strut at high angles of attack. This separation was quite sensitive to the condition of the turbulence in the flow passing over the strut, with the size of the separated wake changing significantly as the mean magnitude and levels of anisotropy were varied. The point of first stall moved by as much as 15% of the chord, while average heat transfer levels changed by 2-5% as the inlet condition was varied. This dependence on inlet conditions meant that comparisons between experiment and steady RANS based CFD were quite poor. Differences between the CFD and experiment were attributed to anisotropic and unsteady effects. The coupling between the two flows was shown to be quite low - that is to say, heat transfer coefficients on both the inner and outer surfaces of the strut were relatively unaffected by the temperature of the strut, and it was possible to predict the temperature on the strut surface quite reliably using heat transfer data from decoupled tests, especially for CFD simulations.

Gas Solubility and Vapor Pressure of Electrolytes Based on Alkylcarbonates Containing Litfsi, Lifap, and LiPF6 Lithium Salt: Measurement and Prediction

Most liquid electrolytes used in commercial lithium-ion batteries are composed by alkylcarbonate mixture containing lithium salt. The decomposition of these solvents by oxidation or reduction during cycling of the cell, induce generation of gases (CO2, CH4, C2H4, CO …) increasing of pressure in the sealed cell, which causes a safety problem [1]. The prior understanding of parameters, such as structure and nature of salt, temperature pressure, concentration, salting effects and solvation parameters, which influence gas solubility and vapor pressure of electrolytes is required to formulate safer and suitable electrolytes especially at high temperature.

We present in this work the CO2, CH4, C2H4, CO solubility in different pure alkyl-carbonate solvents (PC, DMC, EMC, DEC) and their binary or ternary mixtures as well as the effect of temperature and lithium salt LiX (X = LiPF6, LiTFSI or LiFAP) structure and concentration on these properties. Furthermore, in order to understand parameters that influence the choice of the structure of the solvents and their ability to dissolve gas through the addition of a salt, we firstly analyzed experimentally the transport properties (Self diffusion coefficient (D), fluidity (h-1), and conductivity (s) and lithium transport number (tLi) using the Stock-Einstein, and extended Jones-Dole equations [2]. Furthermore, measured data for the of CO2, C2H4, CH4 and CO solubility in pure alkylcarbonates and their mixtures containing LiPF6; LiFAP; LiTFSI salt, are reported as a function of temperature and concentration in salt. Based on experimental solubility data, the Henry’s law constant of gases in these solvents and electrolytes was then deduced and compared with values predicted by using COSMO-RS methodology within COSMOthermX software. From these results, the molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvents and electrolytes with the gases in its hypothetical liquid state were calculated and discussed [3]. Finally, the analysis of the CO2 solubility variations with the salt addition was then evaluated by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the gas solubility is entropy driven and can been influenced by the shape, charge density, and size of the anions in lithium salt.

References

[1] S.A. Freunberger, Y. Chen, Z. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novák, P.G. Bruce, Journal of the American Chemical Society 133 (2011) 8040-8047.

[2] P. Porion, Y.R. Dougassa, C. Tessier, L. El Ouatani, J. Jacquemin, M. Anouti, Electrochimica Acta 114 (2013) 95-104.

[3] Y.R. Dougassa, C. Tessier, L. El Ouatani, M. Anouti, J. Jacquemin, The Journal of Chemical Thermodynamics 61 (2013) 32-44.

Work Extraction and Energy Storage in the Dicke Model

We study work extraction from the Dicke model achieved using simple unitary cyclic transformations keeping into account both a non optimal unitary protocol, and the energetic cost of creating the initial state. By analyzing the role of entanglement, we find that highly entangled states can be inefficient for energy storage when considering the energetic cost of creating the state. Such surprising result holds notwithstanding the fact that the criticality of the model at hand can sensibly improve the extraction of work. While showing the advantages of using a many-body system for work extraction, our results demonstrate that entanglement is not necessarily advantageous for energy storage purposes, when non optimal processes are considered. Our work shows the importance of better understanding the complex interconnections between non-equilibrium thermodynamics of quantum systems and correlations among their subparts.

Mécanisme de salissage et de nettoyage en surface de matériaux polymères

Résumé: Le développement de l’industrie des polymères fourni de plus en plus de choix pour la formulation de matériaux pour les couvre-planchers. Les caoutchoucs, le PVC et le linoleum sont les polymères habituellement utilisés dans l’industrie des couvre-planchers. Ce projet répond à un problème de facilité de nettoyage des couvre-planchers de caoutchouc qui sont reconnus pour être mous, collants et ayant une surface rugueuse. L’INTRODUCTION couvrira l’état actuel de la recherche sur les couvre-planchers, surtout en regard au problème de la «nettoyabilité». La théorie pertinente et les informations générales sur les polymères, les composites polymériques et la science des surfaces seront introduites au CHAPITRE 1. Ensuite, le CHAPITRE 2 couvrira la méthode utilisée pour déterminer la nettoyabilité, l’évaluation des résultats ainsi que l’équipement utilise. Le CHAPITRE 3, discutera des premières expériences sur l’effet de la mouillabilité, la rugosité et la dureté sur la facilité de nettoyage des polymères purs. Plusieurs polymères ayant des surfaces plus ou moins hydrophobes seront investigués afin d’observer leur effet sur la nettoyabilité. L’effet de la rugosité sur la nettoyabilité sera investigué en imprimant une rugosité définie lors du moulage des échantillons; l’influence de la dureté sera également étudiée. Ensuite, un modèle de salissage/nettoyage sera établi à partir de nos résultats et observations afin de rationaliser les facteurs, ou « règles », qui détrminent la facilité de nettoyage des surfaces. Finalement, la réticulation au peroxyde sera étudiée comme une méthode de modification des polymères dans le but d’améliorer leur nettoyabilité; un mécanisme découlant des résultats de ces études sera présenté. Le CHAPITRE 4 étendra cette recherche aux mélanges de polymères; ces derniers servent habituellement à optimiser la performance des polymères purs. Dans ce chapitre, les mêmes tests discutés dans le CHAPITRE 3 seront utilisés pour vérifier le modèle de nettoyabilité établi ci-haut. De plus, l’influence de la non-miscibilité des mélanges de polymères sera discutée du point de vue de la thermodynamique (DSC) et de la morphologie (MEB). L’utilisation de la réticulation par peroxyde sera étudié dans les mélanges EPDM/ (E-ran-MAA(Zn)-ran-BuMA) afin d’améliorer la compatibilité de ces polymères. Les effets du dosage en agent de réticulation et du temps de cuisson seront également examinés. Finalement, un compatibilisant pré-réticulé a été développé pour les mélanges ternaires EPDM/ (E-ran-MAA(Zn)-ran-BuMA)/ HSR; son effet sur la nettoyabilité et sur la morphologie du mélange sera exposé.

Coupled diusion and mechanics in battery electrodes

Thesis (Ph.D.)--University of Washington, 2016-08

Ordering induced by chemical, thermal and mechanical constraints at solid interfaces

We know that classical thermodynamics even out of equilibrium always leads to stable situation which means degradation and consequently d sorder. Many experimental evidences in different fields show that gradation and order (symmetry breaking) during time and space evolution may appear when maintaining the system far from equilibrium. Order through fluctuations, stochastic processes which occur around critical points and dissipative structures are the fundamental background of the Prigogine-Glansdorff and Nicolis theory. The thermodynamics of macroscopic fluctuations to stochastic approach as well as the kinetic deterministic laws allow a better understanding of the peculiar fascinating behavior of organized matter. The reason for the occurence of this situation is directly related to intrinsic non linearities of the different mechanisms responsible for the evolution of the system. Moreover, when dealing with interfaces separating two immiscible phases (liquid - gas, liquid -liquid, liquid - solid, solid - solid), the situation is rather more complicated. Indeed coupling terms playing the major role in the conditions of instability arise from the peculiar singular static and dynamic properties of the surface and of its vicinity. In other words, the non linearities are not only intrinsic to classical steps involving feedbacks, but they may be imbedded with the non-autonomous character of the surface properties. In order to illustrate our goal we discuss three examples of ordering in far from equilibrium conditions: i) formation of chemical structures during the oxidation of metals and alloys; ii) formation of mechanical structures during the oxidation of metals iii) formation of patterns at a solid-liquid moving interface due to supercooling condition in a melt of alloy. © 1984, Walter de Gruyter. All rights reserved.

Fluctuations in and out of equilibrium: Thermalization, quantum measurements and Coulomb disorder

This purely theoretical thesis covers aspects of two contemporary research fields: the non-equilibrium dynamics in quantum systems and the electronic properties of three-dimensional topological insulators. In the first part we investigate the non-equilibrium dynamics in closed quantum systems. Thanks to recent technologies, especially from the field of ultracold quantum gases, it is possible to realize such systems in the laboratory. The focus is on the influence of hydrodynamic slow modes on the thermalization process. Generic systems in equilibrium, either classical or quantum, in equilibrium are described by thermodynamics. This is characterized by an ensemble of maximal entropy, but constrained by macroscopically conserved quantities. We will show that these conservation laws slow down thermalization and the final equilibrium state can be approached only algebraically in time. When the conservation laws are violated thermalization takes place exponential in time. In a different study we calculate probability distributions of projective quantum measurements. Newly developed quantum microscopes provide the opportunity to realize new measurement protocols which go far beyond the conventional measurements of correlation functions. The second part of this thesis is dedicated to a new class of materials known as three-dimensional topological insulators. Also here new experimental techniques have made it possible to fabricate these materials to a high enough quality that their topological nature is revealed. However, their transport properties are not fully understood yet. Motivated by unusual experimental results in the optical conductivity we have investigated the formation and thermal destruction of spatially localized electron- and hole-doped regions. These are caused by charged impurities which are introduced into the material in order to make the bulk insulating. Our theoretical results are in agreement with the experiment and can explain the results semi-quantitatively. Furthermore, we study emergent lengthscales in the bulk as well as close to the conducting surface.

Application of gas hydrate equilibria prediction in process engineering

Desde hace cerca de dos siglos, los hidratos de gas han ganado un rol importante en la ingeniería de procesos, debido a su impacto económico y ambiental en la industria -- Cada día, más compañías e ingenieros ganan interés en este tema, a medida que nuevos desafíos muestran a los hidratos de gas como un factor crucial, haciendo su estudio una solución para un futuro próximo -- Los gases de hidrato son estructuras similares al hielo, compuestos de moléculas huéspedes de agua conteniendo compuestos gaseosos -- Existen naturalmente en condiciones de presiones altas y bajas temperaturas, condiciones típicas de algunos procesos químicos y petroquímicos [1] -- Basado en el trabajo doctoral de Windmeier [2] y el trabajo doctoral the Rock [3], la descripción termodinámica de las fases de los hidratos de gas es implementada siguiendo el estado del arte de la ciencia y la tecnología -- Con ayuda del Dortmund Data Bank (DDB) y el paquete de software correspondiente (DDBSP) [26], el desempeño del método fue mejorado y comparado con una gran cantidad de datos publicados alrededor del mundo -- También, la aplicabilidad de la predicción de los hidratos de gas fue estudiada enfocada en la ingeniería de procesos, con un caso de estudio relacionado con la extracción, producción y transporte del gas natural -- Fue determinado que la predicción de los hidratos de gas es crucial en el diseño del proceso del gas natural -- Donde, en las etapas de tratamiento del gas y procesamiento de líquido no se presenta ninguna formación, en la etapa de deshidratación una temperatura mínima de 290.15 K es crítica y para la extracción y transporte el uso de inhibidores es esencial -- Una composición másica de 40% de etilenglicol fue encontrada apropiada para prevenir la formación de hidrato de gas en la extracción y una composición másica de 20% de metanol en el transporte