In this thesis we studied theoretically and numerically dynamics, order and fluctuations in two dimensional active matter with specific reference to the nematic phase in collections of self-driven particles.The aim is to study the ways in which a nonequilibrium steady state with nematic order differs from a thermal equilibrium system of the same spatial symmetry. The models we study are closely related to “flocking”[1], as well as to equations written down to describe the interaction of molecular motors and filaments in a living cell[2,3] and granular nematics [4]. We look at (i) orientational and density fluctuations in the ordered phase, (ii) the way in which density fluctuations evolve in a nematic background, and finally (iii) the coarsening of nematic order and the density field starting from a statistically homogeneous and isotropic initial state. Our work establishes several striking differences between active nematics and their thermal equilibrium counterparts. We studied two-dimensional nonequilibrium active nematics. Two-dimensional nonequilibrium nematic steady states, as found in agitated granular-rod monolayers or films of orientable amoeboid cells, were predicted [5] to have giant number fluctuations, with the standard deviation proportional to the mean. We studied this problem more closely, asking in particular whether the active nematic steady state is intrinsically phase-separated. Our work has close analogy to the work of Das and Barma[6] on particles sliding downhill on fluctuating surfaces, so we looked at a model in which particles were advected passively by the broken-symmetry modes of a nematic, via a rule proposed in [5]. We found that an initially homogeneous distribution of particles on a well-ordered nematic background clumped spontaneously, with domains growing as t1/2, and an apparently finite phase-separation order parameter in the limit of large system size. The density correlation function shows a cusp, indicating that Porod’s Law does not hold here and that the phase-separation is fluctuation-dominated[7]. Dynamics of active particles can be implemented either through microscopic rules as in[8,9]or in a long-wavelength phenomenological approach as in[5]It is important to understand how the two methods are related. The purely phenomenological approach introduces the simplest possible (and generally additive)noise consistent with conservation laws and symmetries. Deriving the long-wavelength equation by explicit coarse-graining of the microscopic rule will in general give additive and multiplicative noise terms, as seen in e.g., in [10]. We carry out such a derivation and obtain coupled fluctuating hydrodynamic equations for the orientational order parameter (polar as well as apolar) and density fields. The nonequilibrium “curvature-induced” current term postulated on symmetry grounds in[5]emerges naturally from this approach. In addition, we find a multiplicative contribution to the noise whose presence should be of importance during coarsening[11]. We studied nonequilibrium phenomena in detail by solving stochastic partial differential equations for apolar objects as obtained from microscopic rules in[8]. As a result of “curvature-induced” currents, the growth of nematic order from an initially isotropic, homogeneous state is shown to be accompanied by a remarkable clumping of the number density around topological defects. The consequent coarsening of both density and nematic order are characterised by cusps in the short-distance behaviour of the correlation functions, a breakdown of Porod’s Law. We identify the origins of this breakdown; in particular, the nature of the noise terms in the equations of motion is shown to play a key role[12]. Lastly we studied an active nematic steady-state, in two space dimensions, keeping track of only the orientational order parameter, and not the density. We apply the Dynamic Renormalization Group to the equations of motion of the order parameter. Our aim is to check whether certain characteristic nonlinearities entering these equations lead to singular renormalizations of the director stiffness coefficients, which would stabilize true long-range order in a two-dimensional active nematic, unlike in its thermal equilibrium counterpart. The nonlinearities are related to those in[13]but free of a constraint that applies at thermal equilibrium. We explore, in particular, the intriguing but ultimately deceptive similarity between a limiting case of our model and the fluctuating Burgers/KPZequation. By contrast with that case, we find that the nonlinearities are marginally irrelevant. This implies in particular that 2-dactive nematics too have only quasi-long-range order[14].

Non-viral delivery of plasmid DNA has traditionally relied upon physical forces applied directly to target tissues. These physical methods typically involve contact between an applicator and the target tissue and often cause transient patient discomfort. To overcome the contact-dependent limitations of such delivery methodologies, an atmospheric direct current plasma source was developed to deposit ionized gas molecules onto localized treatment sites. The deposition of charged species onto a treatment site can lead to the establishment of an electric field with strengths similar to those used for traditional electroporation. In vitro experiments proved that this technology could transiently permeabilize cell membranes and that membrane restabilization followed first order kinetics. Optimum delivery of tracer molecules to cell suspensions occurred after 10 minutes of plasma exposure and was attained without adversely effecting cell viability. In vivo testing of the plasma discharge demonstrated the capability of this system to deliver plasmid DNA to murine skin. Initial experiments involved the injection of plasmid DNA encoding luciferase into the dermis of C57BL/6J mice and then exposing the tissue to plasma discharge for 10 mintues. Delivery by this method resulted in increased luminescence that was as much as 19-fold greater than DNA injection alone. Follow-up optimization experiments demonstrated it was possible to obtain luminescence results that were similar in magnitude to those obtained using electroporation, which under optimum conditions resulted in about a 40-fold increase in peak luminescence. Finally, optimum conditions were used to deliver a plasmid DNA encoding for the 120 kilodalton glycoprotein present on the surface of a macrophage tropic HIV. Results from this vaccination experiment indicated this method was capable of producing antigen specific humoral immune responses at similar levels as when electroporation was utilized as the delivery method.

No description available.

Nonequilibrium work methods for determining potentials of mean force (PMF) w(z) have recently gained popularity as an alternative to standard equilibrium based methods. Introduced by Kosztin et al., the forward-reverse (FR) method is a bidirectional work method in that it requires the work to be sampled in both forward and reverse directions along the reaction coordinate z. This bidirectional sampling leads to much faster convergence than other nonequilibrium methods such as the Jarzynski equality, and the calculation itself is extremely simple, making the FR method an attractive way of determining the PMF. Presented here is an extension to the FR method that deals with sampling problems along essentially irreversible reaction coordinates. By oscillating a particle as it is steered along a reaction coordinate, both forward and reverse work samples are obtained as the particle progresses. Dubbed the oscillating forward-reverse (OFR) method, this new method overcomes the issue of irreversibility that is present in numerous soft-matter and biological systems, particularly in the stretching or unfolding of proteins. The data analysis of the OFR method is non-trivial however, and to this end a software package named the ‘OFR Analysis Tool’ has been created. This software performs all of the complicated analysis necessary, as well as a complete error analysis that considers correlations in the data, thus streamlining the use of the OFR method for potential end users. Another attractive feature of the FR method is that the dissipative work is collected at the same time as the free energy changes, making it possible to also calculate local diffusion coefficients, D(z), from the same simulation as the PMF through the Stokes-Nernst-Einstein relation Fdrag = −γv, with γ = kB T /D. While working with the OFR method, however, the D(z) results never matched known values or those obtained through other methods, including the mean square displacement (or Einstein) method. After a reformulation of the procedure to obtain D(z), i.e. by including the correct path length and particle speeds, results were obtained that were much closer to the correct values. The results however showed very little variation over the length of the reaction coordinate, even when D(z) was known to vary drastically. It seemed that the highly variable and noncontinuous velocity function of the particle being steered through the “stiff-spring” method was incompatible with the macroscopic definition of the drag coefficient, γ. The drag coefficient requires at most a slowly varying velocity so that the assumption of a linearly related dissipative work remains valid at all times. To address this, a new dynamic constraint steering protocol (DCP) was developed to replace the previously used “stiff-spring” method, now referred to as a dynamic restraint protocol (DRP). We present here the results for diffusion in bulk water, and both the PMF and diffusion results from the permeation of a water molecule through a DPPC membrane. We also consider the issue of ergodicity and sampling, and propose that to obtain an accurate w(z) (and D(z)) from even a moderately complex system, the final result should be a weighted average obtained from numerous pulls. An additional utility of the FR and OFR methods is that the permeability across lipid bilayers can be calculated from w(z) and D(z) using the inhomogeneous solubility-diffusion (ISD) model. As tests, the permeability was first calculated for H2O and O2 through DPPC. From the simulations, the permeability coefficients for H2O were found to be 0.129 ± 0.075 cm/s and 0.141 ± 0.043 cm/s, at 323 K and 350 K respectively, while the permeability coefficients for O2 were 114 ± 40 cm/s and 101 ± 27 cm/s, again at 323 K and 350 K respectively. As a final, more challenging system, the permeability of tyramine – a positively charged trace amine at physiological pH – was calculated. The final value of P = 0.89 ± 0.24 Ang/ns is over two orders of magnitude lower than that obtained from experiment (22 ± 4 Ang/ns), although it is clear that the permeability as calculated through the ISD is extremely sensitive to the PMF, as scaling the PMF by ∼ 20% allowed the simulation and experimental values to agree within uncertainty. With accurate predictions for free energies and permeabilities, the OFR method could potentially be used for many valuable endeavors such as rational drug design.

Nesse trabalho, são investigadas as propriedades dinâmicas de modelos da mecânica estatística na criticalidade. Inicialmente, trabalhando com modelos de spin e utilizando os conceitos de persistência global e de dimensão anômala da magnetização inicial, mostramos que o modelo de Baxter-Wu não está na mesma classe de universalidade dos modelos de Potts com quatro estados e de Ising com interação de três spins em uma direção, todos bidimensionais. Na segunda parte da tese, estudamos o fenômeno de crescimento da superfície gerada pela deposição segundo as regras que definem os autômatos celulares probabilísticos propostos por Grassberger (modelos A e B). Esses dois autômatos não pertencem à classe de universalidade de Domany-Kinzel e apresentam novos expoentes críticos, cuja origem se deve à conservação de paridade. Determinamos o expoente de crescimento beta w, válido em tempos curtos, assim como os outros expoentes críticos associados ao crescimento de superfície (alfa e z). Nossas estimativas se comparam bem com os resultados obtidos a partir de razões de inteiros propostas por Jensen para os expoentes beta, ni paralelo e ni perpendicular. Finalmente, investigamos a transição de fase entre o estado helicoidal e o estado desordenado (random coil) da polialanina e do fragmento peptídico PTH(1-34), que corresponde aos resíduos 1 a 34 da região aminoterminal do hormônio das paratireóides. Nosso cálculo, que leva em conta as interações entre todos os átomos da molécula, está baseado em uma abordagem de tempos curtos. Os resultados dessa análise indicam que a transição helix-coil das polialaninas e do PTH(1-34) é de segunda ordem e apontam para uma classe de universalidade para a transição helix-coil em homopolímeros e proteínas (partindo de um estado helicoidal). / In this work we investigated dynamic properties of statistical mechanical models at criticality. At first, using the concepts of global persistence and anomalous dimension of initial magnetization, we showed that the Baxter-Wu model does not belong to the same universality class as 4-state Potts model and Ising with multispin interaction in one direction. In the sequence, we studied the roughening behavior generated by deposition governed by rules defined by probabilistic cellular automata proposed by Grassberger (A and B models). Those models are known do not belong to the Domany-Kinzel universality class. They are characterized by different exponents which are related to the parity conserving (PC). We estimated the growth exponent beta w, in short-time regimen, such as, other critical exponents associated to the surface growth (alpha and z). Our results are in good agreement with those expected for parity conserving universality class. At last we studied the phase transition between the completely helical state and the random coil of the polyalanine, such as, for the 34-residue human parathyroid fragment PTH(1-34). Our short-time simulations of the helix-coil transition are based on a detailed all-atom representation of proteins. The results indicate that helix-coil transition in polyalanine and PTH(1-34) is a second-order phase transition and suggest a universality class to the helix-coil transition in homopolymer and (helical) proteins.

Orientador : Maria Regina Wolf Maciel / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T15:22:51Z (GMT). No. of bitstreams: 1 Reis_MiriaHespanholMiranda_D.pdf: 3186781 bytes, checksum: ed9c594aabf9a348666496468982cf5b (MD5) Previous issue date: 2006 / Resumo: A destilação é, certamente, o processo mais aplicado na separação de misturas líquidas. Embora esta seja uma operação unitária conhecida de longa data, ainda, nos dias de hoje persistem algumas dificuldades na proposição de esquemas de destilação apropriados. Sendo assim, o objetivo deste trabalho de tese foi aplicar modelos mais realistas na caracterização de misturas e na simulação de processos de destilação, em regimes estacionários e dinâmicos. Para tanto, foram avaliados dois softawes, desenvolvidos no Laboratório de Desenvolvimentos de Processos de Separação, para simulações de colunas de destilação considerando os modelos de estágios de equilíbrio e de não equilíbrio. Os resultados obtidos mostraram que, geralmente, os perfis obtidos com as duas modelagens são diferentes, em ambos os regimes. A modelagem de estágios de não equilíbrio foi aplicada também para a caracterização de sistemas, utilizando mapas de curvas residuais. Avaliou-se, ainda, a influência das correlações de eficiência de Barros & Wolf em mapas de curvas residuais. Os perfis obtidos com as correlações de eficiência de Barros & Wolf mostram grande concordância com os calculados pelo modelo de estágios de não equilíbrio. Com os mapas de curvas residuais calculados concluiu-se que as trajetórias líquidas de composição não cruzam as fronteiras de destilação, sendo esta um questão de polêmica na atualidade, no entanto, nossos resultados mostram os perfis corretos. Além disso, desenvolveu-se, neste trabalho de tese, um programa computacional para a caracterização de sistemas reativos. A vantagem do novo algoritmo proposto está, principalmente, no fato do programa não depender de estimativas inicias e ser de fácil convergência. O programa é, também, capaz de predizer todos os azeótropos presentes na mistura, quando existam um ou mais de um, ou ainda de afirmar que a mistura é zeotrópica. Os resultados obtidos são concordantes com valores experimentais ou calculados por outros métodos. Na linha do processo de destilação reativa, sendo este um processo inovador, foi proposta a separação da mistura fenol + água. A separação desta mistura é de grande interesse, por questões econômicas e ambientais. Preliminarmente, fez-se um estudo na busca de uma reação apropriada para o consumo de fenol. O processo proposto atende completamente às questões ambientais, visto que gera somente correntes limpas e é, portanto, uma nova alternativa para o tratamento de correntes fenólicas. Por fim, desenvolveu-se neste trabalho um conjunto completo para caracterização de sistemas e simulação de processos, envolvendo desde o modelo de estágios de equilíbrio até o modelo de estágios de não equilíbrio. Propôs-se, ainda, um eficiente processo para o tratamento de águas fenólicas / Abstract: Distillation is, certainly, the most applied process in the separation of liquid mixtures. Although this is a very known unit operation, still nowadays some difficulties persist in the proposal of appropriate distillation schemes. Thus, the objective of this work was to apply more realistic models in the characterization of mixtures and in the simulation of distillation process in, both, steady state and dynamic regime. In this way, two softwares developed in the Laboratory of Separation Processes Development were evaluated. These softwares consider the equilibrium and the nonequilibrium stage models in steady state and dynamic regime. The results show that, generally, the profiles obtained with the two models are different, in both regimes. The nonequilibrium stage model was also applied for the systems characterization, in residue curve maps. It was evaluated, still, the influence of Barros & Wolf correlations for efficiencies on residue curve maps. The profiles obtained with the Barros & Wolf correlations show good agreement with the calculated with the nonequilibrium stage model. The calculated residue curve maps showed that residue curves do not cross distillation boundaries. Nowadays, this is a question of controversy, however our results show the correct behavior. Moreover, it was developed in this work a computational program for the characterization of reactive systems. The advantage of the new proposed algorithm is mainly because the program does not depend on initial estimates and it is of easy convergence. The program is, also, able to predict all the azeotropes present in the mixture, when one or more than one exist, or still to affirm that the mixture is zeotropic. The obtained results are in agreement with experimental values or values calculated by other methods. Regarding to reactive distillation, being an innovative process, it was proposed the separation of the mixture phenol + water. The separation of this mixture is of great interest, for economic and environmental issues. Preliminarily, it was carried out a study of an appropriate reaction for the phenol consumption. The considered process takes care of environmental questions, since it only generates current clean and it is, therefore, an alternative process for the phenolic wastewater treatment. Finally, in this work, it was developed a complete set for characterization of systems and simulation of processes, involving the equilibrium and the nonequilibrium stage modes, in steady state and dynamic regime. It was considered, still, an efficient process for the phenolic wastewater treatment / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Orientadores: Maria Regina Wolf Maciel, Antonio Andre Chivanga Barros / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-07-27T23:52:32Z (GMT). No. of bitstreams: 1 Soares_Cintia_M.pdf: 6610044 bytes, checksum: 4b52b82aa749a3987b506a6240f74361 (MD5) Previous issue date: 2000 / Resumo: Devido à sua abrangência com os fenômenos de transferência de massa, calor e quantidade de movimento, capacidade e características operacionais, relações termodinâmicas e o amplo envolvimento com outros equipamentos industriais, o estudo dos processos de separação por destilação toma-se muito complexo, apesar de sua extensiva utilização nas indústrias químicas e petroquímicas. Por isto, trabalhos de grande relevância científica são ainda desenvolvidos para melhor entender os fenômenos relacionados e que permitem melhorar a sua operacionalidade. Assim, este trabalho teve como objetivo a avaliação experimental de uma coluna de destilação com pratos perfurados, permitindo averiguar o comportamento das eficiências de Murphree, O'Connell e da correlação de Barros & Wolf, além da avaliação dos perfis dos coeficientes de transferência de massa e calor ao longo do equipamento. Os dados experimentais obtidos foram utilizados para a validação dos modelos de estágios de equilíbrio e de não equilíbrio e da correlação de eficiência desenvolvida por Barros & Wolf. Para a realização deste trabalho, uma coluna de destilação, em aço inoxidável, contendo 8 pratos perfurados com vertedor e um sistema para controle da potência foram projetados e construídos. A coluna contém 8 pontos para a coleta de amostras de líquido e termopares acoplados em cada prato para a leitura de temperatura. Para cada experimento foram variadas as composições do etanol na alimentação e a potência fomecida ao refervedor para avaliar a influência da carga térmica sobre o comportamento das frações molares e da temperatura em uma coluna operada a refluxo total. Nos ensaios, trabalhou-se com o sistema etanolágua por ser de fácil determinação analítica e por existirem dados de equilíbrio precisos e alguns valores de eficiência. Após o alcance do estado estacionário, determinado a partir de leituras periódicas de temperatura ao longo do equipamento, foram feitas coletas de amostras de líquido em cada estágio da coluna, as quais foram analisadas empregando a técnica de cromatografia à gás. Com os dados da temperatura, composição do etanol e da água em cada estágio e da potência fomecida ao refervedor, foram calculadas as eficiências de Murphree e de O'Connell. Com a utilização de programas computacionais envolvendo a modelagem de estágios de equilíbrio (com a correlação de Barros & Wolf) e de não equilíbrio, desenvolvidos no Laboratório de Desenvolvimento de Processos de Separação da UNICAMP, foram realizadas simulações nas condições de operação dos experimentos, cujos dados obtidos foram utilizados para comparação com dados experimentais de forma a corroborar tais modelos. Os resultados obtidos mostraram que as modelagens de estágios de equil íbrio e de não equilíbrio reproduzem, com grande fidelidade, as condições reais do processo e representam o comportamento real dos coeficientes de transferência de massa e calor ao longo da coluna de destilação. Os resultados obtidos mostraram-se compatíveis com os dados da literatura / Abstract: Due to the relation with the mass, heat and momentum transfer phenomena, capacity and operational characteristics, thermodynamic properties and the wide relationship with other industrial equipment, the study of the separation processes by distillation becomes very complex, in spite of its extensive use in the chemical and petrochemical industries. For this reason, researches of great scientific relevance are still being developed for better understanding the related phenomena and for allowing the improvement of the operation. Thus, this work presents as objective the experimental study of a distillation column with sieve plates to evaluate the behaviour of the Murphree efficiency, Q'Connell and Barros & Wolf correlations and the mass and heat transfer coefficients along the equipment. The experimental data were obtained used for the validation of the equilibrium and nonequilibrium stage models and of the new efficiency correlation developed by Barros & Wolf. For these purposes, a stainless steel distillation column with eight sieve plates with down comer and a system for the power measuring were designed and built. The column contains eight spaced temperature/sample points. For each experiment, the ethanol feed composition and the heat duty were changed to evaluate the influence of the heat duty on the behaviour of the mole fractions and on the temperature profiles in the column operating at total reflux. After established the steady state, the liquid samples and the temperature were taken in each stage of the column, and the samples were analyzed using the gas chromatography technique. Using the temperature and ethanol and water compositions in each stage and the heat duty supplied to the reboiler, Murphree and Q'Connell efficiency were calculated. The programs involving the equilibrium stage model (with Barros & Wolf correlation) and the nonequilibrium stage model developed in the Laboratory of Separation Process Development (UNICAMP) were used in the simulations at the same conditions of the experiments. The data obtained with simulations were compared with experimental data to corroborate such models. The obtained results showed that the equilibrium stage model and the nonequilibrium stage model reproduce, with great fidelity, the real conditions of the process and they can be used to represent the real behaviour of the mass and heat transfer coefficients along the distillation column / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

L'objet de cette thèse est l'étude de phénomènes critiques hors-équilibre. Pour décrire ces systèmes, l'utilisation d'équations de Langevin est souvent incontournable car elles permettent une description heuristique relativement simple du phénomène, construite en ajoutant un terme de bruit à la dynamique macroscopique. J'ai montré qu'il est toutefois possible, dans le cas des processus de réaction-diffusion, d'aller au delà de cette approche et de dériver une équation de Langevin exacte qui décrit la dynamique au niveau microscopique. Une seconde partie de ma thèse est consacrée à l'étude de modèles spécifiques de phénomènes critiques hors-équilibre à l'aide du groupe de renormalisation non-perturbatif (NPRG), une version moderne des blocs de spins de Wilson et Kadanoff. À l'équilibre, cet outil tire son succès de sa capacité à contrôler les fluctuations au voisinage de la transition grâce à un régulateur. Hors équilibre, les fluctuations temporelles doivent être traitées de la même façon, et j'ai donc conçu un régulateur qui contrôle à la fois les fluctuations spatiales et temporelles. Enfin, j'ai appliqué le NPRG à un modèle d'érosion. En effet, l'apparition générique de lois d'échelles dans les paysages suggère l'existence d'un mécanisme sous-jacent qui conduit ces systèmes à leur point critique. L'équation de Kardar-Parisi-Zhang modélise l'érosion à grande échelle (>2 km), mais ne s'accorde pas aux observations à plus petite échelle. Un modèle différent, tenant compte de l'anisotropie (la pente d'une montagne), fut donc suggéré. À l'aide du NPRG, je montre que ce modèle possède une ligne de points fixes qui correspond à un domaine continu d'exposants d'échelle. / This manuscript is focused on the study of critical phenomena taking place out-of-equilibrium. In the description of such phenomena, Langevin equations are ubiquitous and are usually derived in a phenomenological way by adding a noise term to a deterministic mean-field equation. However, I show that for reaction-diffusion processes it is in fact possible to derive an exact Langevin equation from the microscopic process. A second part of my thesis work has been devoted to the study of specific nonequilibrium critical phenomena using the nonperturbative renormalization group (NPRG), which is a modern implementation of Wilson and Kadanoff's block-spin idea. This tool, very powerful in an equilibrium context, takes care of the growing spatial fluctuations that arise near criticality through the use of a regulator. In a nonequilibrium context, the temporal fluctuations also have to be controlled. I have therefore designed a regulator that tackles both spatial and temporal fluctuations. Finally, I have applied the NPRG techniques to a model of landscape erosion: indeed, the generic scaling behaviour that appear in erosional landscapes suggests the existence of an underlying mechanism naturally fine-tuned to be critical. The Kardar-Parisi-Zhang equation seems to give a correct model for landscape erosion at large length scale (>2 km), but fails to predict the scaling observed at smaller scale. A different model was thus suggested which takes into account the intrinsic anisotropy at smaller length scale (the slope of the mountain). Using NPRG techniques, I show that this model possesses a line of fixed points associated with a continuous range of scaling exponents.

Le grenaillage ultrason est un procédé mécanique de traitement de surfaces. Il consiste à projeter des billes à la surface de pièces métalliques, à l’aide d’un système acoustique vibrant ultrasonore. Lors du traitement, les billes sont contenues dans une enceinte spécialement conçue pour la pièce à traiter, et adoptent un comportement similaire à celui d’un gaz granulaire vibré. Le grenaillage ultrason sert à introduire des contraintes résiduelles de compression dans le matériau traité. Ces contraintes de compression sont bénéfiques pour la tenue en fatigue de la pièce et sa résistance à la corrosion sous contraintes.L’objectif des présents travaux de thèse consiste à modéliser la dynamique des billes pendant le traitement, et pour des pièces et géométries complexes. En effet, depuis son industrialisation, la mise au point du procédé se fait de manière empirique qui, avec la complexification des pièces mécaniques traitées pousse cette approche à ses limites. La mise au point peut donc s’avérer coûteuse en temps et aboutir à une solution partiellement optimisée. Ainsi, le modèle développé donne accès à une compréhension détaillée du grenaillage ultrason dans des conditions de traitement industrielles. Il constitue pour la première fois un outil d’aide à la conception des enceintes de traitement, offrant la possibilité d’une meilleure maitrise et optimisation du traitement, tout en réduisant les coûts de mise au point. La seconde contribution est de fournir aux modèles de prédiction des contraintes des données fiables et réalistes / Ultrasonic shot peening is a mechanical surface treatment process. It consists on projecting spherical shot onto a metallic surface, using an ultrasonic accoustic system. During the treatement, the shot are contained in a chamber, specially designed for the peened part, and behave similarely to a vibrated granular gas. Ultrasonic shot peening is used to introduce compressive residual stresses in the peened material. These compressive stresses help increasing the fatigue life span of the part and its resistance to stress corrosion cracking.The objectif of the present work consists on modeling the shot dynamics of the shot during the traitement, and for complex parts and geometries. Since its industrialization, the choice of the process parameters is done experimentally with trial and error. And with the ever increasing complexity of the peened parts, this approach is reaching its limits; thus becoming sometimes time consuming and providing partially optimized solutions.Therfore, the developped model gives access to a detailed understanding of ultrasonic shot peening in industrial treatment conditions. It represents for the first time a support tool for the design of peening chambers. This offers the possibility of a better control and optimization of the process, while reducing development costs. The second contribution lies in the model capacity to provide reliable and realistic input data to residual stresses prediction models

Cette thèse est consacrée à l'étude théorique des propriétés de transportd'un nanodispositif comme par exemple une boîte quantique. A faible dimensionnalité,les propriétés de transport sont fortement liées à la densité d'étatsélectroniques du système, il est donc important d'utiliser une approche capablede calculer cette dernière correctement notamment en tenant comptedu confinement électronique.En utilisant le modèle d'Anderson et l'approximation de non croisementafin de calculer la densité d'états, on a pu observer et caractériser les transfertsde poids spectral pour des orbitales simplement, doublement ou triplementdégénérées. Ces transferts de poids spectral sont typiques des systèmescorrélés, mais lorsqu'une différence de potentiel est appliquée, on a pu remarquerque ces transferts se faisaient en deux temps.Dans un second temps, on a analysé les signatures du couplage de Hundincluant le terme de saut de paires dans les diagrammes de stabilité. Ces deuxtermes, provenant de l'interaction Coulombienne, modifient sensiblement lastructure des diamants de Coulomb et doivent donc être considérés lorsqu'ondéduit les paramètres microscopiques à partir du diagramme de stabilitéexpérimental.Enfin, on s'est placé dans le régime de générateur thermoélectrique, et ona utilisé le pic de Kondo comme canal de transport. Cependant l'optimisationà la fois du rendement et de la puissance en utilisant les bandes de Hubbardcomme canaux de transport est impossible. Or les particularités et les grandeurscaractérisant le pic de Kondo permettent d'une part de s'affranchirpartiellement de ce compromis mais cela permet également de générer uneplus grande puissance. / This thesis is devoted to the theoretical study of a nanodevice transportproperties, such as a quantum dot. At low dimensionality, transport propertiesare strongly related to the local density of state, it is important to use anapproach able to compute the latter properly especially tanking into accountthe electronic containment.Using the Anderson model and the non-crossing approximation to computedensity of states, we observed and characterize spectral weight transfersfor simply, doubly and triply degenerated orbitals. These spectral weighttransfers are typical of correlated systems, but when potential bias is applied,we note that these transfers occur in two stages.In a second step, we analyze Hund coupling footprint including pair hoppingin stability diagrams. These two terms, from the Coulomb interaction,substantially alter the Coulomb diamonds structure and must be considerwhen microscopic parameters are derived from experimental stability diagrams.Finally, we placed in the thermoelectric generator regime, and we usedKondo peak as transport channel. However, optimization of both efficiencyand power output using Hubbard bands as transport channel is impossible.But the features and scales characterizing Kondo peak serve on the one handto overcome this compromise and on the other hand to generate a greaterpower output.