Molecular hydrodynamics from memory kernels

The memory kernel for a tagged particle in a fluid, computed from molecular dynamics simulations, decays algebraically as $t^{-3/2}$. We show how the hydrodynamic Basset-Boussinesq force naturally emerges from this long-time tail and generalize the concept of hydrodynamic added mass. This mass term is negative in the present case of a molecular solute, at odds with incompressible hydrodynamics predictions. We finally discuss the various contributions to the friction, the associated time scales and the cross-over between the molecular and hydrodynamic regimes upon increasing the solute radius.Comment: 5 pages, 4 figure

Molecular hydrodynamics from memory kernels

The memory kernel for a tagged particle in a fluid, computed from molecular dynamics simulations, decays algebraically as t−3/2. We show how the hydrodynamic Basset-Boussinesq force naturally emerges from this long-time tail and generalize the concept of hydrodynamic added mass. This mass term is negative in the present case of a molecular solute, which is at odds with incompressible hydrodynamics predictions. Lastly, we discuss the various contributions to the friction, the associated time scales, and the crossover between the molecular and hydrodynamic regimes upon increasing the solute radius

Flots microscopiques et mécanisme de la diffusion en phase liquide

This work proposes to reconcile the points of view developed by microscopic theories and hydrodynamics on diffusion. We test the hydrodynamics hypothesis and try reformulate them from microscopic arguments. In particular, for a laminar viscous liquid, the exerced force on a spherical particle or the velocity field around the spherical particle with a prescribed velocity, respectively described by the Basset-Boussinesq force and the Stokes flow, will be the object of our investigation. Is their form relevant at microscopic scale ? If so, how can we express them at the molecular scale ? To do so, we realized molecular simulations and based our developement thanks to the Mori-Zwanzig theory which gives us exact microscopic relations. Initally, we study the evolution of fluctuations of the particle in order to interpret the behaviour at long times and link it with inertia, diffusion and hydrodynamics. Then we propose a novel approch to extract the microscopic flow of Lennard-Jones or granular fluids in order to compare it directly with the hydrodynamic solutions, which allows us to study boundary conditions. We were able to develop an analytical expression for boundary conditions of the flow where fluctuations play a key role. Thanks to our developed analysis tools, we also investigate the coupling between the translational and rotational movement. Finally, we extend our investigation to more realistic fluids such as aqueous solutions and water.Le manuscrit de thèse se propose de concilier les points de vue développés par les théories microscopiques et la théorie hydrodynamique sur la diffusion. Nous testons les hypothèses hydrodynamiques et tentons d'obtenir une reformulation de celles-ci à partir d'arguments microscopiques. En particulier, pour un fluide laminaire visqueux, la force exercée sur une particule sphérique ou encore le champ de vitesse autour d'une particule sphérique en mouvement, respectivement décrits par la force de Basset-Boussinesq et la solution de Stokes, seront l'objet de notre investigation. Leurs formes sont-elles pertinentes à l'échelle microscopique ? Si oui, comment peut-on les exprimer à l'échelle moléculaire ? Pour ce faire, nous avons réalisé des simulations moléculaires et basé notre développement à l'aide de la théorie de Mori-Zwanzig. Dans un premier temps, nous étudions l'évolution des fluctuations de la particule afin d'interpréter le comportement aux temps longs et réalisons le lien avec l'inertie, la diffusion et l'hydrodynamique. Puis nous proposons une nouvelle approche pour extraire le flot microscopique de fluides Lennard-Jones ou granulaires afin de le comparer directement aux solutions hydrodynamiques, ce qui nous permet d'étudier les conditions aux bords. Nous avons pu développer une expression analytique pour les conditions aux bords du flot où les fluctuations jouent un rôle clef. A l'aide des outils d'analyse développés, nous pouvons aussi investiguer le couplage entre le mouvement translationnel et rotationnel. Enfin nous étendons notre analyse à des systèmes tels que les ions aqueux et l'eau surfondue

Field-dependent ionic conductivities from generalized fluctuation-dissipation relations

We derive a relationship for the electric field dependent ionic conductivity in terms of fluctuations of time integrated microscopic variables. We demonstrate this formalism with molecular dynamics simulations of solutions of differing ionic strength with implicit solvent conditions and molten salts. These calculations are aided by a novel nonequilibrium statistical reweighting scheme that allows for the conductivity to be computed as a continuous function of the applied field. In strong electrolytes, we find the fluctuations of the ionic current are Gaussian and subsequently the conductivity is constant with applied field. In weaker electrolytes and molten salts, we find the fluctuations of the ionic current are strongly non-Gaussian and the conductivity increases with applied field. This nonlinear behavior, known phenomenologically for dilute electrolytes as the Onsager-Wien effect, is general and results from the suppression of ionic correlations at large applied fields, as we elucidate through both dynamic and static correlations within nonequilibrium steady-states.Comment: 6 pages, 3 figure

Ultrasonic signal modality: A novel approach for concrete damage evaluation

[EN] In this paper, a new approach for characterizing material damage, using ultrasonic waves, is proposed. Two concrete series with two types of cement with different C3A content and similar mechanical properties were subjected to external sulphate attack (ESA) and evaluated using a novel Recurrence Plot Quantification Analysis (RQA) method. This brand new technique was compared with several methods, such as mechanical tests (compressive and flexural strength determination), dynamic test (dynamic modulus) measurements, and traditional ultrasonic measurements (propagation velocity and ultrasonic wave attenuation). In these experiments, RQA showed a high sensitivity to damage in spoiled series, improving the reliability of damage detection with ultrasonics in non-homogeneous materials compared to other non-destructive techniques. Interesting advantages of this new non-destructive technique are: a) the RQA parameter is normalized (range of 0 to 1); b) a calibration process is not required; c) the values of its standard deviation show the dispersion of the damage. It can contribute greatly to the diagnosis of the degree of damage to a material, when combined with other traditional measures such as the attenuation of the material.This work was supported by the Spanish Government under grants TEC2011-23403, BIA2014-55311-C2-1-P and BIA2014-55311-C2-2-P. This work is protected by the Spanish Patent and Trademark Office (SPTO) under reference P201630212.Carrión García, A.; Genovés, V.; Gosálbez Castillo, J.; Miralles Ricós, R.; Paya Bernabeu, JJ. (2017). Ultrasonic signal modality: A novel approach for concrete damage evaluation. Cement and Concrete Research. 101:25-32. https://doi.org/10.1016/j.cemconres.2017.08.011S253210

Nonlinear resonance methods for assessing ASR susceptibility during concrete prism testing (CPT)

This research focuses on the characterization of damage accumulation in concrete specimens. Specifically, a nonlinear vibration technique is used to characterize the damage introduced by ongoing alkali-silica reactions (ASR). The nonlinear resonance testing consists of an analysis of the frequency response of concrete specimens subjected to impact loading. ASR introduces a third gel like phase, which can be expansive in the presence of moisture. The result of ASR is the formation of microcracks and debonding between aggregate and cement phases. Collectively, these changes act to increase the specimens' nonlinearity. As a result, it is found that the concrete samples exhibit nonlinear behavior; mainly a decrease in resonance frequency with an increasing level of excitation strain. The relationship between the amplitude of the response and the amount of frequency shift is used as a parameter to describe the nonlinearity of the specimen. The specimens used in this research are of varying reactivity with respect to ASR, which is induced in accordance with ASTM C 1293. The level of nonlinearity is used as a measure of damage caused by the progress of ASR throughout the one year test duration. These nonlinear resonance results are compared to the traditional measures of expansion described in the standard. The robustness and repeatability of the proposed technique is also investigated by repeated testing of samples assumed to be at a specific damage state. Finally, a petrographic staining technique is used to complement nonlinearity measurements and to further gain understanding of ASR. The results of this study show that the proposed nonlinear resonance methods are very sensitive to microstructural changes and have great potential for quantitative damage assessment in concrete.M.S.Committee Chair: Jacobs, Laurence J.; Committee Co-Chair: Kurtis, Kimberly E.; Committee Member: Kim, Jin-Yeon; Committee Member: Pierron, Olivie

Microscopic flows and mechanism of diffusion in liquid phase

Le manuscrit de thèse se propose de concilier les points de vue développés par les théories microscopiques et la théorie hydrodynamique sur la diffusion. Nous testons les hypothèses hydrodynamiques et tentons d'obtenir une reformulation de celles-ci à partir d'arguments microscopiques. En particulier, pour un fluide laminaire visqueux, la force exercée sur une particule sphérique ou encore le champ de vitesse autour d'une particule sphérique en mouvement, respectivement décrits par la force de Basset-Boussinesq et la solution de Stokes, seront l'objet de notre investigation. Leurs formes sont-elles pertinentes à l'échelle microscopique ? Si oui, comment peut-on les exprimer à l'échelle moléculaire ? Pour ce faire, nous avons réalisé des simulations moléculaires et basé notre développement à l'aide de la théorie de Mori-Zwanzig. Dans un premier temps, nous étudions l'évolution des fluctuations de la particule afin d'interpréter le comportement aux temps longs et réalisons le lien avec l'inertie, la diffusion et l'hydrodynamique. Puis nous proposons une nouvelle approche pour extraire le flot microscopique de fluides Lennard-Jones ou granulaires afin de le comparer directement aux solutions hydrodynamiques, ce qui nous permet d'étudier les conditions aux bords. Nous avons pu développer une expression analytique pour les conditions aux bords du flot où les fluctuations jouent un rôle clef. A l'aide des outils d'analyse développés, nous pouvons aussi investiguer le couplage entre le mouvement translationnel et rotationnel. Enfin nous étendons notre analyse à des systèmes tels que les ions aqueux et l'eau surfondue.This work proposes to reconcile the points of view developed by microscopic theories and hydrodynamics on diffusion. We test the hydrodynamics hypothesis and try reformulate them from microscopic arguments. In particular, for a laminar viscous liquid, the exerced force on a spherical particle or the velocity field around the spherical particle with a prescribed velocity, respectively described by the Basset-Boussinesq force and the Stokes flow, will be the object of our investigation. Is their form relevant at microscopic scale ? If so, how can we express them at the molecular scale ? To do so, we realized molecular simulations and based our developement thanks to the Mori-Zwanzig theory which gives us exact microscopic relations. Initally, we study the evolution of fluctuations of the particle in order to interpret the behaviour at long times and link it with inertia, diffusion and hydrodynamics. Then we propose a novel approch to extract the microscopic flow of Lennard-Jones or granular fluids in order to compare it directly with the hydrodynamic solutions, which allows us to study boundary conditions. We were able to develop an analytical expression for boundary conditions of the flow where fluctuations play a key role. Thanks to our developed analysis tools, we also investigate the coupling between the translational and rotational movement. Finally, we extend our investigation to more realistic fluids such as aqueous solutions and water