No description available.

Les riboswitches sont des modules structurés dans les régions 5’ (voire 3’) UTR des ARNm. Chaque riboswitch reconnaît spécifiquement un petit métabolite, ce qui provoque un changement de conformation et permet de moduler au niveau transcriptionnel ou traductionnel (voire par épissage alternatif) l’expression d’un gène impliqué dans la synthèse du métabolite.Ce travail portait sur la cinétique de repliement des domaines aptamères de deux riboswitches homologues liant la thiamine pyrophosphate (TPP), un régulant la transcription du gène thiC (E. coli) et l’autre régulant l’épissage alternatif du gène THIC (A. thaliana).La première approche utilisée (méthode cinétique classique par quenched-flow) consistait à sonder la structure des aptamères par des radicaux hydroxyles au cours du repliement initié par l’addition de TPP. Nous avons également développé (coll. avec A.Griffiths), une approche microfluidique visant à remplacer l’appareillage classique et, à terme, de le dépasser en permettant d’augmenter le nombre d’entrées pour l’étude de systèmes complexes. Nous avons aussi utilisé une méthode (kinITC) récemment développée au laboratoire qui permet d’obtenir des informations thermodynamiques et cinétiques inédites par microcalorimétrie isotherme.Nos résultats ont montré que l’aptamère bactérien se replie beaucoup plus vite que celui d’A. thaliana. Cependant, l’aptamère d’A. thaliana étudié dérivait de la forme sauvage (raccourcissement de l’hélice P3). Par comparaison avec d’autres travaux récents, nos résultats soulignent le rôle fondamental de P3 dans la cinétique de repliement. La méthode kinITC a aussi mis en évidence que le régime cinétique du fonctionnement global du riboswitch de E. coli n’est pas contradictoire avec une première étape de fixation du TPP sous régime thermodynamique.Les résultats obtenus avec la nouvelle méthode de microfluidique sont mitigés. Si nous avons pu reproduire le schéma de coupure de l’ARN lié au TPP obtenu par sondage chimique classique (valide ainsi la première étape de ce développement), la cinétique de repliement observée est plus rapide sans que nous en ayons pour le moment une explication satisfaisante. / Riboswitches are RNA modules found in the 5’-UTR of bacterial mRNA where they control gene expression at the transcriptional or translational level. They are occasionally found in the 3’-UTR where they control alternative splicing. Each riboswitch-controlled gene is involved in the biosynthetic pathway of a metabolite and a feedback loop is ensured by the specific binding of the metabolite.To study the folding kinetics of TPP-binding riboswitch aptamer domains from E.coli (regulating transcription of thiC) and from A. thaliana, (regulating alternative splicing of THIC) two different approaches were used. First, each aptamer structure was probed by hydroxyl radical footprinting during RNA folding triggered by TPP . We also developed (coll. with A. Griffiths) a microfluidic approach aimed at replacing the classical quenched-flow apparatus and, eventually, superseding it by giving access to more entries. We also used a method recently developed in our lab (kinITC), which gives access to rich kinetic and thermodynamic information from isothermal titration calorimetry.Our results showed that the E. coli aptamer folds much faster than its A. thaliana counterpart. However, the form that we used for the latter had a helix P3 shorter than that of the wt and, when compared with recent results, our results highlight the fundamental role of this helix in the kinetics of folding. It was also clear that, globally, the E. coli riboswitch is kinetically controlled but the kinITC method allowed us to show that this is not in contradiction with a thermodynamic control of the first TPP binding step.The results obtained with the microfluidic device are mitigated. We were indeed able to make the proof of concept of hydroxyl RNA probing on a microfluidic chip, but the kinetics of RNA folding appeared to be faster than that observed with the quenched flow. We are not yet able to propose an explanation for this strange fact.

Les catalyseurs Ziegler Natta pour la polymérisation des oléfines sont généralement obtenus par réaction entre un complexe de métal de transition avec un alkylaluminium ou un autre co-catalyseur. Généralement, pour le catalyseur Ziegler-Natta moléculaire, l'espèce active est un complexe cationique. Cependant, la coordination de l'oléfine sur l'espèce active peut concurrencer avec le métal alkyl, le solvant, ou le contre-ion qui se trouvent dans le milieu réactionnel. Par conséquent la détermination de la fraction des sites actifs est un des principaux défis dans le domaine des polyoléfines. Plusieurs méthodes ont été étudiées pour mesurer les sites actifs. La méthode la plus fiable est celle basée sur la mesure du nombre des macromolécules dans les premiers instants de la polymérisation. Cette méthode nécessite de travailler dans un régime contrôlé où les réactions de transfert de chaîne sont négligeables. Pour certains catalyseurs Ziegler-Natta qui polymérisent dans conditions « extrêmes » (très basses températures), ce régime contrôlé dure plusieurs minutes. Pour la plupart des catalyseurs le régime contrôlé dure quelque secondes ou fractions de secondes. Dans ces cases il faut appliquer une technique cinétique très rapide : le Quenched Flow. Cette technique a toujours été mise en œuvre pour travailler dans des faibles conditions expérimentales. Le réacteur Quenched Flow utilisé dans cet étude a été conçu pour mesurer la constante de propagation de chaîne et surtout la fraction des sites actifs [M*]/[M]. La première partie de cette thèse est dédiée à l'étude des catalyseurs métallocène. Le comportement de ces catalyseurs dans les premiers instants de polymérisation avec différents activateurs a été observé. Une description cinétique a été possible pour certains systèmes catalytiques. La partie finale de la thèse a été dédiée à l'étude des catalyseurs post métallocène. La fraction des sites actifs, [M*]/[M], est la constante de propagation de chaînes, kp, ainsi les principaux paramètres d'activation S‡ et H‡ pour le complexe Bis(cumyl)[ONNO]ZrBz2 activé en utilisant MAO/tBu2-PhOH ont été déterminés sur un large plage de températures. Pour le complexe [N-(3-tert-butylsalicylidene)-2,3,4,5,6 pentafluoroanilinato] titanium activé par le MAO un changement de régime cinétique a été observé à hautes températures / Ziegler-Natta catalysts are generally obtained by the combination of a transition metal complex with an alkylaluminium compound and possibly another co-catalyst. For molecular Ziegler-Natta catalyst, generally, the active species is a cationic compound. However, in regards to the actives species, the olefin may compete in the polymerization medium with other metal alkyl, the solvent or the counteranion. Thus, it is not an easy task to determine the total active metal site fraction which remains an important challenge in the field of polyolefins. Several methods have been developed to perform this measurement. Among these the most reliable one is rely on the determination of number of macromolecules formed initially, and it requires working in initial controlled regime where the chain transfer reactions are very limited. It should be possible to achieve the controlled regime for molecular catalyst for time going from several milliseconds to fraction of second. This means that technically demanding fast kinetic techniques such as quenched flow technique are necessary for the investigation of kinetic parameters of olefin polymerization catalysts. Up to now this technique has been only implemented in very mild conditions. Recently a stopped flow reactor operating at high temperature and high pressure has been developed in Lyon. In the present study, the usefulness of this reactor for measuring the chain propagation rate constant kp and the fraction of metal active site [M*]/[M] is assessed. In the first part of this work we have focused on the investigation of some metallocene-based catalysts. In particular, we have observed how these catalysts behave at initial stage of polymerization, when they are activated with different co-catalyst and in some case a kinetic description was also possible. The last part of this work was dedicated to kinetic study of some post-metallocene catalysts such as amine bisphenolate and (bis phenoxy-imine) -Zr and -Ti based complexes activated with MAO in a large range of polymerization temperatures. A successful kinetic investigation of Bis(cumyl)[ONNO]ZrBz2 complex activated with MAO/tBu2-PhOH has been performed which allowed the determination of [M*]/[M], kp and activation parameters such as H‡ and S‡. In the case of [N-(3-tert-butylsalicylidene)-2,3,4,5,6 pentafluoroanilinato] titanium dichloride activated with MAO an original changing in kinetic regime is reported by increasing the polymerization temperature

Nesta tese utilizamos o modelo do replicador aleatório, proposto por Diederich e Opper, para analisar as propriedades de equilíbrio de ecossistemas complexos (formados por um grande número de espécies) em três situações distintas. Na primeira parte desta tese, investigamos os efeitos de interações variáveis sobre a estrutura do ecossistema, utilizando o método de réplicas generalizado, introduzido por Penney et al. Este formalismo propõe uma nova interpretação para o índice de réplicas n, a saber, como sendo a razão entre duas temperaturas características: a temperatura relacionada aos acoplamento e a temperatura associada às variáveis de spin. Empregando t\\\'ecnicas de campo m\\\'edio de Mec\\^anica Estat\\\'stica e tamb\\\'em simula\\c\\~oes num\\\'ericas tratamos, em particular, do estado fundamental ($\\beta ightarrow + \\infty$). Encontramos dois regimes distintos, um onde prevalece a coopera\\c\\~ao entre as diferentes esp\\\'ecies ($\\beta^{\\prime} > 0$) e outro no qual a competi\\c\\~ao \\\'e predominante ($\\beta^ < 0$). No primeiro caso temos uma transi\\c\\~ao descont\\\'{\\i}nua para um regime de diversidade nula e no outro temos uma m\\\'axima diversidade das esp\\\'ecies. Na segunda parte desta tese \\cite, estudamos as implica\\c\\~oes de uma temperatura finita sobre a estrutura do ecossistema. Utilizamos a regra de Hebb para descrever as intera\\c\\~oes entre as diferentes esp\\\'ecies. A temperatura surge, no modelo, atrav\\\'es de um ru\\\'do gaussiano introduzido na equa\\c\\~ao estoc\\\'astica que rege a din\\^amica do processo. Tratamos analiticamente o caso recozido ({\\em annealed}), no qual as caracter\\\'sticas das esp\\\'ecies evoluem t\\~ao rapidamente quanto suas concentra\\c\\~oes, e o caso temperado ({\\em quenched}), onde tais caracter\\\'sticas est\\~ao fixas. Conclu\\\'{\\i}mos que h\\\'a uma transi\\c\\~ao de fase descont\\\'{\\i}nua entre um estado onde a competi\\c\\~ao prevalece, determinando baixa diversidade, para outro estado onde predomina a coopera\\c\\~ao. Por fim \\cite, analisamos as poss\\\'veis consequ\\^encias de uma interven\\c\\~ao humana sobre as propriedades de equil\\\'{\\i}brio do ecossistema. Admitimos o princ\\\'pio da exclus\\~ao competitiva para modelar os acoplamentos entre as diferentes esp\\\'ecies, a regra de Hebb. Interferimos na comunidade impondo que um conjunto de caracteres, selecionados previamente, esteja presente em uma fra\\c\\~ao bem definida dos seus membros. O principal resultado deste estudo revela, desde que o par\\^ametro de competi\\c\\~ao entre indiv\\\'duos semelhantes n\\~ao seja muito pequeno, que o efeito de uma tal manipula\\c\\~ao conduz a perda da diversidade e, portanto, ao empobrecimento do ecossistema. / In this thesis we use the random replicator model, proposed by Diederich and Opper \\cite, to analyse the equilibrium properties of complex ecosystems (formed by a large number of species) in three distinct situations. In the first part of this thesis \\cite, we investigate the effects of variable interactions upon ecosystem structure, using the generalized replica method, introduced by Penney et al \\cite. In this formalism we find a new interpretation for the replica number $n$ as the ratio between two characteristic temperatures: the temperature related to the couplings ($\\beta^$) and the temperature associated to the spin variables ($\\beta$). We approach the problem using mean field methods of statistical mechanics and intensive numerical simulations; in particular we are concerned with the ground state ($\\beta ightarrow + \\infty$). We find two distinct regimes, one where cooperation between different species prevails ($\\beta^ > 0$) and the other in which competition is predominant ($\\beta^ < 0$). In the first case we have a discontinuous transition to the zero diversity regime and in the other we have the maximum species diversity. In the second part of this thesis \\cite, we examine the finite temperature implications upon ecosystem structure. Through the Hebb rule we can describe the interactions between different species. With the aid of a Gaussian noise in the stochastic equation, that governs the temporal evolution, we have a way to introduce the finite temperature in the model. We treat analytically the annealed case, in which the species characteristics evolve so fast as its concentrations, as well as the quenched case, in which such characteristics are fixed. We conclude that there is a discontinuous phase transition between a state where competition prevails, implying low diversity, to another state in which cooperation is stronger. At last \\cite, we analyse the possible consequences of human intervention upon the equilibrium properties of the ecosystem. We assume the competitive exclusion principle to model the couplings between different species, the Hebb rule. We interfere in the community by imposing that a set of characters, previously selected, be present in a well defined fraction of its members. The main result of this study reveals, provided that the intraspecies competition parameter is not too weak, that the effect of such a manipulation leads to the impoverishment of the ecosystem.

[Truncated abstract] New, double-doped, Bi2O3-based materials in the Bi2O3 Ln2O3 PbO (Ln = La, Nd, Er and Yb) and Bi2O3 WO3 PbO systems were prepared using solid-state reactions. For the Bi2O3 Er2O3 PbO and Bi2O3 Yb2O3 PbO systems, the air-quenchable compositional domain of the fcc fluorite-type phase was partially established. Temperature dependent conductivity measurements were performed on these quenched-in fluorite-type materials using AC impedance spectroscopy. Conductivity at 750[degrees Celsius] generally increased with increasing Pb2+/Ln3+ and decreasing (Ln3++Pb2+)/Bi3+ ratios. The material (BiO1.5)0.70(ErO1.5)0.15(PbO)0.15 had a conductivity of 0.66 [plus-minus] 0.05 S cm-1 at 750[degrees Celsius], placing it among the most highly conductive Bi2O3-based materials, and was the best new fluorite-type material from a combined conductivity and structural stability viewpoint. Some of the new materials in the Bi2O3 La2O3 PbO and Bi2O3 Nd2O3 PbO systems appeared to have the quenched-in fluorite type structure based on powder X-ray diffraction data. These materials had very high conductivities at 750[degrees Celsius] of `~ 1 S cm-1, but underwent rapid symmetry lowering transformations during heating, thus making them unsuitable for use as solid electrolytes. The fluorite-type structure was not air-quenchable in the Bi2O3 WO3 PbO system, for the compositions synthesised. Room temperature neutron powder diffraction data were collected for quenched-in fluorite-type materials in the (BiO1.5)0.80(LnO1.5)0.20-x(PbO)x, Ln = Er and Yb, x = 0, 0.03, 0.06 and 0.09, and (BiO1.5)0.97-y(ErO1.5)y(PbO)0.03, y = 0.27, 0.17 and 0.12, series. ... This suggests that Pb2+ dopant cations occupy face-centre positions in the fcc unit cell, and the Pb2+ lone pair electrons are likely to be orientated towards an oxide ion vacancy in an adjacent tetrahedral site. Pb2+/oxide ion vacancy interactions affect the migration of oxide ions/oxide ion vacancies through the structure, and are responsible for the significantly larger activation energy for oxide ion migration in the Pb2+-doped materials relative to the Pb2+-free materials. For example, the activation energies of (BiO1.5)0.80(ErO1.5)0.20-x(PbO)x, x = 0.03 and 0.06, were 1.50 [plus-minus] 0.02 and 1.54 [plus-minus] 0.02 eV, respectively, while the activation energy for (BiO1.5)0.80(ErO1.5)0.20 was 1.25 [plus-minus] 0.04 eV. Long-term annealing of the quenched in fluorite-type materials in the Bi2O3 Er2O3 PbO and Bi2O3 Yb2O3 PbO systems at 500 and 600[degrees Celsius] resulted in conductivity lowering structural transformations, making these materials unsuitable for practical use as solid electrolytes at these temperatures. For example, the materials (BiO1.5)0.80(ErO1.5)0.20-x(PbO)x, x = 0.03, 0.06 and 0.09, underwent a fluorite-type to tetragonal transformation during annealing at 500[degrees Celsius] due to <100> oxide ion vacancy ordering, and the rate of conductivity decay at 500[degrees Celsius] increased with increasing Pb2+/Er3+ ratio. Long-term annealing experiments at 500[degrees Celsius] performed on air quenched (Bi2O3)0.705(Er2O3)0.245(WO3)0.050 showed that the disordered fluorite-type structure of this material was not fully stabilised, as evidenced by the presence of superlattice reflections in selected area electron diffraction patterns for the material annealed for 2000 hours, and a gradual conductivity decay after ~ 150 hours annealing.

Nesta tese utilizamos o modelo do replicador aleatório, proposto por Diederich e Opper, para analisar as propriedades de equilíbrio de ecossistemas complexos (formados por um grande número de espécies) em três situações distintas. Na primeira parte desta tese, investigamos os efeitos de interações variáveis sobre a estrutura do ecossistema, utilizando o método de réplicas generalizado, introduzido por Penney et al. Este formalismo propõe uma nova interpretação para o índice de réplicas n, a saber, como sendo a razão entre duas temperaturas características: a temperatura relacionada aos acoplamento e a temperatura associada às variáveis de spin. Empregando t\\\'ecnicas de campo m\\\'edio de Mec\\^anica Estat\\\'stica e tamb\\\'em simula\\c\\~oes num\\\'ericas tratamos, em particular, do estado fundamental ($\\beta ightarrow + \\infty$). Encontramos dois regimes distintos, um onde prevalece a coopera\\c\\~ao entre as diferentes esp\\\'ecies ($\\beta^{\\prime} > 0$) e outro no qual a competi\\c\\~ao \\\'e predominante ($\\beta^ < 0$). No primeiro caso temos uma transi\\c\\~ao descont\\\'{\\i}nua para um regime de diversidade nula e no outro temos uma m\\\'axima diversidade das esp\\\'ecies. Na segunda parte desta tese \\cite, estudamos as implica\\c\\~oes de uma temperatura finita sobre a estrutura do ecossistema. Utilizamos a regra de Hebb para descrever as intera\\c\\~oes entre as diferentes esp\\\'ecies. A temperatura surge, no modelo, atrav\\\'es de um ru\\\'do gaussiano introduzido na equa\\c\\~ao estoc\\\'astica que rege a din\\^amica do processo. Tratamos analiticamente o caso recozido ({\\em annealed}), no qual as caracter\\\'sticas das esp\\\'ecies evoluem t\\~ao rapidamente quanto suas concentra\\c\\~oes, e o caso temperado ({\\em quenched}), onde tais caracter\\\'sticas est\\~ao fixas. Conclu\\\'{\\i}mos que h\\\'a uma transi\\c\\~ao de fase descont\\\'{\\i}nua entre um estado onde a competi\\c\\~ao prevalece, determinando baixa diversidade, para outro estado onde predomina a coopera\\c\\~ao. Por fim \\cite, analisamos as poss\\\'veis consequ\\^encias de uma interven\\c\\~ao humana sobre as propriedades de equil\\\'{\\i}brio do ecossistema. Admitimos o princ\\\'pio da exclus\\~ao competitiva para modelar os acoplamentos entre as diferentes esp\\\'ecies, a regra de Hebb. Interferimos na comunidade impondo que um conjunto de caracteres, selecionados previamente, esteja presente em uma fra\\c\\~ao bem definida dos seus membros. O principal resultado deste estudo revela, desde que o par\\^ametro de competi\\c\\~ao entre indiv\\\'duos semelhantes n\\~ao seja muito pequeno, que o efeito de uma tal manipula\\c\\~ao conduz a perda da diversidade e, portanto, ao empobrecimento do ecossistema. / In this thesis we use the random replicator model, proposed by Diederich and Opper \\cite, to analyse the equilibrium properties of complex ecosystems (formed by a large number of species) in three distinct situations. In the first part of this thesis \\cite, we investigate the effects of variable interactions upon ecosystem structure, using the generalized replica method, introduced by Penney et al \\cite. In this formalism we find a new interpretation for the replica number $n$ as the ratio between two characteristic temperatures: the temperature related to the couplings ($\\beta^$) and the temperature associated to the spin variables ($\\beta$). We approach the problem using mean field methods of statistical mechanics and intensive numerical simulations; in particular we are concerned with the ground state ($\\beta ightarrow + \\infty$). We find two distinct regimes, one where cooperation between different species prevails ($\\beta^ > 0$) and the other in which competition is predominant ($\\beta^ < 0$). In the first case we have a discontinuous transition to the zero diversity regime and in the other we have the maximum species diversity. In the second part of this thesis \\cite, we examine the finite temperature implications upon ecosystem structure. Through the Hebb rule we can describe the interactions between different species. With the aid of a Gaussian noise in the stochastic equation, that governs the temporal evolution, we have a way to introduce the finite temperature in the model. We treat analytically the annealed case, in which the species characteristics evolve so fast as its concentrations, as well as the quenched case, in which such characteristics are fixed. We conclude that there is a discontinuous phase transition between a state where competition prevails, implying low diversity, to another state in which cooperation is stronger. At last \\cite, we analyse the possible consequences of human intervention upon the equilibrium properties of the ecosystem. We assume the competitive exclusion principle to model the couplings between different species, the Hebb rule. We interfere in the community by imposing that a set of characters, previously selected, be present in a well defined fraction of its members. The main result of this study reveals, provided that the intraspecies competition parameter is not too weak, that the effect of such a manipulation leads to the impoverishment of the ecosystem.

Specimens of steel 42CrMoS4 were quenched from the austenite (γ) and the ferrite (α) + austenite + cementite phase fields to produce fully martensitic matrices with 0 – 14 % ferrite dispersed in the matrix. After tempering at 300°C or 600°C mechanical and fatigue properties were determined. As expected yield strength, tensile strength and hardness decreased with increased tempering temperature and ferrite content. Quite unexpected, the fatigue properties were mildly affected. A small amount of ferrite, approximately 3% even appears to improve the fatigue strength. Then, at even higher ferrite amounts, slightly below 20% the fatigue strength appears to decrease again.

O presente trabalho propõe o estudo da cromodinâmica quântica (QCD) através de simulações numéricas da teoria na rede. Inicialmente será apresentada a formulação de integral de trajetória da mecânica quântica para em seguida generalizar os resultados para a teoria quântica de campos. A teoria na rede exigirá a discretização do espaço-tempo e mostraremos como colocar os graus de liberdade bosônicos e fermiônicos na rede. Usaremos a formulação de Wilson para a ação de glúons e férmions na rede. Simulações numéricas em QCD na rede envolvendo férmions são consideravelmente complicadas e têm um custo computacional altamente limitante. Mais precisamente, não é possível simular a estrutura do vácuo fermiônico sem algum tipo de aproximação. Neste trabalho usaremos a aproximação quenched da QCD, que consiste em negligenciar os efeitos de loops de quarks do vácuo. Também empregaremos apenas dois sabores de quarks degenerados, correspondendo às duas espécies de quarks leves presentes na teoria. Ao longo deste trabalho serão exploradas as dificuldades encontradas em colocar quarks na rede e também será determinado o espectro de hádrons como uma aplicação de interesse. Contudo, também estudaremos um problema simples envolvendo a teoria de gauge pura na rede, isto é, calcularemos o valor esperado para o operador plaqueta. Este estudo servirá como um pré aquecimento antes de lidar com o problema mais desafiador do espectro de hádrons e também permitirá aprender algumas técnicas de simulação que serão utilizadas na determinação do espectro de hádrons, a saber, o método de Monte Carlo e os algoritmos banho térmico e sobre-relaxação, que servem para construir configurações de gauge (glúons). A interpretação dos resultados obtidos deverá ser realizada a partir da análise estatística dos dados. Estimaremos o tempo de termalização do operador plaqueta a partir da visualização da equilibração do resultado e usaremos o método bloco de dados para estimar o tempo de correlação das configurações de gauge. Essas estimativas serão importantes para decidirmos os parâmetros de simulação adequados para o espectro de hádrons, pois neste caso não teremos acesso à quantidade suficiente de dados para determinar o valor desses parâmetros. Para a determinação de erros estatísticos será usado o método de jackknife. O cálculo do espectro de hádrons envolve a inversão de uma matriz esparsa não positiva definida, mais precisamente, o operador de Dirac. Esta será a parte que mais consumirá tempo nas simulações e usaremos o algoritmo gradiente biconjugado estabilizado (Bi-CGStab) para a inversão. A determinação da massa de hádrons somente será possível após a fixação da massa experimental de algum hádron (usaremos o píon), e após a extrapolação quiral dos resultados, que será realizada a partir do método dos mínimos quadrados não linear. Ao final deste trabalho obteremos uma estimava para a massa do próton e do méson rho. / This work proposes the study of quantum cromodynamics (QCD) through numerical simulations of the lattice theory. Initially we will present the path integral formulation of quantum mechanics and then generalize these results to quantum field theory. The lattice theory requires the discretization of space-time and we will show how to put the fermionic and gluonic degrees of freedom on the lattice. We will use Wilson&rsquo;s formulation for the action of fermions and gluons. Numerical simulations in lattice QCD with fermions are considerably complicated and their cost is highly limiting. More precisely, it is not possible to simulate the fermionic structure of the vacuum without any kind of approximation. We will use the quenched approximation in this work, which consists of neglecting the effects of vacuum quark loops. We also will employ only two flavors of degenerate quarks corresponding to the two species of light quarks present in the theory. Throughout the work we will discuss the difficulties related to putting quarks on the lattice and we will evaluate the hadron spectrum as an application of interest. However, we also must study a simple problem involving the lattice pure-gauge theory, i.e., we will compute the mean value of the plaquette operator. This will be a warm-up study before dealing with the more challenging problem of the hadron spectrum and will allow us to learn some simulation techniques that will be used in the hadron spectrum determination, namely the Monte Carlo method and the heat bath and overrelaxation algorithms, which are useful to build gauge configurations (i.e. gluon configurations). The interpretation of the results obtained should be performed using statistical analysis of the data. We will estimate the thermalization time of the plaquette operator from the visualization of the equilibration result and will estimate the correlation time of gauge configurations using the data blocking method. These estimates are important to decide the suitable simulation parameters for the hadron spectrum, because in that case we will not have access to a quantity of data large enough to determine the value of these parameters. For the statistical error determination we will use the jackknife method. The calculation of the hadron spectrum involves the inversion of a non positive definite sparse matrix, more precisely, the Dirac operator. This will be the most time-consuming step of the simulation and we will use the Bi-Conjugate Gradient Stabilized (Bi-CGRStab) algorithm to do the inversion. The determination of hadron masses will only be possible after fixing an experimental mass of some hadron (we will use the pion), and after the quiral extrapolation of the results, which will be performed using the non-linear least square method. At the end of this work we will obtain an estimate of the mass of the proton and of the rho meson.

Dans cette thèse nous étudions les théorèmes limites dans l’analyse statistique dessystèmes dynamiques. Le premier chapitre est consacré aux notions des bases des systèmesdynamiques ainsi que la théorie ergodique. Dans le deuxième chapitre nous introduisonsun cadre fonctionnel abstrait pour lequel la version quenched du théorème de la limitecentrale (TLC) en dimension 1 pour les systèmes dynamiques uniformément dilatantsest satisfaite sous une condition de validité nécessaire et suffisante. Le troisième chapitreest consacré au principe d’invariance presque sûr (PIPS) pour les application aléatoiresdilatantes par morceaux. Nous présentons certaines hypothèses sous lesquelles le (PIPS)est vérifié en utilisant la méthode d’approximation des martingales de Cuny et Merlèvede.Nous étudions aussi le théorème de Sprindzuk et ses conséquences. Nous établissons dansle chapitre quatre la décroissance des corrélations pour les systèmes dynamiques aléatoiresuniformément dilatants par la méthode de couplage en dimension 1. Nous terminons cetravail par une présentation des concepts de base de la théorie des mesures et probabilitéset une présentation de l’espace des fonctions à variation bornée. / In this thesis we study the limit theorems in the statistical analysis of dynamicalsystems. The first chapter is devoted to the basic notions in dynamical systems as well asthe ergodic theory. In the second chapter we introduce an abstract functional frameworkunder which the quenched version of the central limit theorem (CLT) in dimension 1for uniformly expanding dynamic systems is satisfied under a necessary and sufficientcondition validity. The third chapter is devoted to the almost sure invariance principle(ASIP) for random piecewise expanding maps. We present some hypotheses under whichthe (ASIP) is verified using the method of approximation of the martingales of Cuny andMerlèvede. We also study the Sprindzuk theorem and its consequences. In chapter four,we define the decay of correlations for the random dynamical systems uniformly expandingby the coupling method in dimension 1. We finish this work with a presentation of thebasic concepts of the theory of measures and probabilities and a presentation of the spaceof functions with bounded variation.

La Fragilisation par l’hydrogène (FPH) est un phénomène complexe de dégradation des matériaux métalliques dont les mécanismes sont dépendants de nombreux paramètres tels que la nature du matériau (composition chimique, traitement thermique), l’environnement ou l’état de contrainte. L’objectif de ce travail est d’apporter des éléments de compréhension sur les mécanismes de transport et de ségrégation de l’hydrogène dans les aciers martensitiques trempés et revenus à haute limite d’élasticité utilisés pour les applications « Oil and Gas ». Notons que cette étude se situe en amont de la problématique endommagement. Dans ce contexte, il s’agit d’identifier les sites de piégeage de l’hydrogène en regard de la métallurgie des matériaux. La mise au point d’un montage de perméation électrochimique et d’un protocole de dépouillement des résultats a permis une nouvelle approche critique dans l’exploitation des résultats issus des essais électrochimiques. De cette procédure, plusieurs aspects ont été considérés : les rôles de l’épaisseur de la membrane, de l’état de surface de la face de détection, de la microstructure et enfin, d’un état mécanique. La mise en relation de l’évolution de la microstructure avec les paramètres physiques associés aux phénomènes de diffusion et de piégeage de l’hydrogène permettront de conduire une première réflexion « vers l’endommagement ». / Hydrogen Embrittlement (HE) is a complex phenomen on responsible of metal degradation. It mainly depends on the material (chemical composition, heat treatment), the environment or the mechanical state. The main goal of this study is to give new elements to understand hydrogen diffusion and trapping mechanisms in High Strength Low Alloy martensitic steels used in the field of “Oil and Gas” applications. In this way, the purpose is to identify hydrogen trapping sites related to microstructural features as a basis for a better knowledge concerning HE. Thus, accurate electrochemical permeation set-up (with or without a mechanical state) were developed as well as a procedure to thoroughly analyze experimental data. An original approach on how to interpret electrochemical permeation results has been there fore performed. Afterward, the effect of different critical parameters has been assessedi.e. the membrane thickness, the surface state of the detection side as well as the microstructure and the mechanical state. The relationship between physical parameters associated to diffusion and trapping with the microstructure evolution will give rise to a first thought “toward the embrittlement”.