L'objectif de ma thèse est d'étudier des oligonucléotides et mononucléotides par de nouvelles techniques de fragmentation comme l'EDD (Electron-Detachment-Dissociation) et l'EID (Electron-Induced-Dissociation) qui font intervenir un bombardement d'électrons. Les échantillons sont d'abord ionisés par une source electrospray (ESI) qui permet une ionisation douce. Au cours de mon travail de thèse, je me suis intéressé à l'étude de petits oligonucléotides (ADN et ARN simples brins) et de mononucléotides par EDD et EID. Tout d'abord nous optimisons les différents paramètres qui ont permis d'obtenir en ESI les espèces multichargées pour étudier les processus EDD, EID d'oligonucléotides à des états de charge différents, afin d'obtenir le maximum d'ions fragments. Ces spectres seront comparés avec les spectres SORI-CID (Collision-Induced-Dissociation) et IRMPD (Infrared-Multiphoton-Dissociation) pour mettre en évidence les spécificités de l'EDD et EID par rapport au SORI-CID. Les spectres EDD et EID montrent quelques ions fragments qui ne sont pas observés dans les spectres SORI-CID et IRMPD parce que ces derniers ne conduisent pas aux ions radicalaires. Grâce aux ions fragments radicalaires obtenus en EDD et en EID, nous avons pu accéder au séquençage d'oligonucléotides riches en thymine pour lesquels il est difficile d'obtenir des informations par les méthodes conventionnelles. Enfin nous avons utilisé des techniques particulières de la technologie ICR et qui seront présentées dans ce manuscrit

Le développement durable et l'éducation qui lui est affiliée, sont aujourd'hui des questions socialement vives. Ces questions sont au cœur de nombreuses initiatives qu'elles soient politiques ou non. Les nombreux acteurs mobilisés sur le sujet sont d'origine diverse. L'Etat bien sur, et ses services déconcentrés se sont engagés mais également des collectivités territoriales, des institutions publiques ou parapubliques, l'Ecole et les associations d'éducation non formelle ou de protection de l'environnement. La diversité et la multiplicité des actions menées interrogent leur cohérence. Cette recherche doctorale propose un tableau des pratiques actuelles en éducation relative à l'environnement et/ou au développement durable. Elle analyse la place des parties prenantes, les enjeux sous-jacents et leurs stratégies territoriales. C'est aussi un regard critique sur les savoirs qui structurent aujourd'hui le champ.

Apresenta-se um framework que permite a caracterização, conformação e escalonamento de todas as categorias de serviços A TM, dentro do ambiente de usuário (CEP). Propõem-se um modelo de tráfego otimizado para este ambiente que oferece condições de garantias de QoS individuais para fluxos VBR, tempo real ou não, CBR, ABR e UBR. O modelo proposto, denominado de PCSTS (priority class services traffic shaping), inclui um módulo que permite a obtenção do descritor de tráfego de fluxos desconhecidos. Os fluxos são conformados de forma individual, e em tempo real, segundo um conformador baseado num algoritmo de escalonamento virtual duplo baseado no GCRA do ITU/ ATM Forum. Para a multiplexação dinâmica dos diferentes fluxos do ambiente de usuário, no enlace de acesso, é proposto um algoritmo de escalonamento EDD, modificado através de um sinal de realimentação entre conformador e escalonador, e desta forma tem-se condições de oferecer garantias de limite de atraso e jitter para fluxos individuais de serviços rt-VBR ou nrt-VBR. São apresentadas simulações, tanto da caracterização dos fluxos desconhecidos como da arquitetura do escalonador, que comprovam o comportamento esperado do modelo de tráfego PCSTS. / We present a framework that enhances the characterization, shaping and scheduling of ATM traffic flows for ali ATM service categories in the customer prernise equipment (CPE) environment. We propose an optirnized traffic model, capable to guarantee QoS parameters at per connection levei for VBR services, real time or not, CBR, ABR and UBR services. The model proposed, narned PCSTS (priority classes services traffic shaping), includes a module that performs the characterization of services with unknown traffic descriptor. The flows are shaped individually, in real time, through a shaper based on the double discrete time scheduling algorithm of the GCRA from ITU/ ATM Forum. For the dynarnic multiplexing of the different service flows , at the link levei, a modified EDD scheduling algorithm is proposed with a feedback signal between the scheduling and shaping modules. As a result, it is demonstrated that it is possible to grant jitter and delay bounds for the rt-VBR and nrt-VBR services. We present simulations of the traffic characterization module and of the scheduling architecture, for different services, which confirms the expected behavior of the PCSTS model.

Apresenta-se um framework que permite a caracterização, conformação e escalonamento de todas as categorias de serviços A TM, dentro do ambiente de usuário (CEP). Propõem-se um modelo de tráfego otimizado para este ambiente que oferece condições de garantias de QoS individuais para fluxos VBR, tempo real ou não, CBR, ABR e UBR. O modelo proposto, denominado de PCSTS (priority class services traffic shaping), inclui um módulo que permite a obtenção do descritor de tráfego de fluxos desconhecidos. Os fluxos são conformados de forma individual, e em tempo real, segundo um conformador baseado num algoritmo de escalonamento virtual duplo baseado no GCRA do ITU/ ATM Forum. Para a multiplexação dinâmica dos diferentes fluxos do ambiente de usuário, no enlace de acesso, é proposto um algoritmo de escalonamento EDD, modificado através de um sinal de realimentação entre conformador e escalonador, e desta forma tem-se condições de oferecer garantias de limite de atraso e jitter para fluxos individuais de serviços rt-VBR ou nrt-VBR. São apresentadas simulações, tanto da caracterização dos fluxos desconhecidos como da arquitetura do escalonador, que comprovam o comportamento esperado do modelo de tráfego PCSTS. / We present a framework that enhances the characterization, shaping and scheduling of ATM traffic flows for ali ATM service categories in the customer prernise equipment (CPE) environment. We propose an optirnized traffic model, capable to guarantee QoS parameters at per connection levei for VBR services, real time or not, CBR, ABR and UBR services. The model proposed, narned PCSTS (priority classes services traffic shaping), includes a module that performs the characterization of services with unknown traffic descriptor. The flows are shaped individually, in real time, through a shaper based on the double discrete time scheduling algorithm of the GCRA from ITU/ ATM Forum. For the dynarnic multiplexing of the different service flows , at the link levei, a modified EDD scheduling algorithm is proposed with a feedback signal between the scheduling and shaping modules. As a result, it is demonstrated that it is possible to grant jitter and delay bounds for the rt-VBR and nrt-VBR services. We present simulations of the traffic characterization module and of the scheduling architecture, for different services, which confirms the expected behavior of the PCSTS model.

Apresenta-se um framework que permite a caracterização, conformação e escalonamento de todas as categorias de serviços A TM, dentro do ambiente de usuário (CEP). Propõem-se um modelo de tráfego otimizado para este ambiente que oferece condições de garantias de QoS individuais para fluxos VBR, tempo real ou não, CBR, ABR e UBR. O modelo proposto, denominado de PCSTS (priority class services traffic shaping), inclui um módulo que permite a obtenção do descritor de tráfego de fluxos desconhecidos. Os fluxos são conformados de forma individual, e em tempo real, segundo um conformador baseado num algoritmo de escalonamento virtual duplo baseado no GCRA do ITU/ ATM Forum. Para a multiplexação dinâmica dos diferentes fluxos do ambiente de usuário, no enlace de acesso, é proposto um algoritmo de escalonamento EDD, modificado através de um sinal de realimentação entre conformador e escalonador, e desta forma tem-se condições de oferecer garantias de limite de atraso e jitter para fluxos individuais de serviços rt-VBR ou nrt-VBR. São apresentadas simulações, tanto da caracterização dos fluxos desconhecidos como da arquitetura do escalonador, que comprovam o comportamento esperado do modelo de tráfego PCSTS. / We present a framework that enhances the characterization, shaping and scheduling of ATM traffic flows for ali ATM service categories in the customer prernise equipment (CPE) environment. We propose an optirnized traffic model, capable to guarantee QoS parameters at per connection levei for VBR services, real time or not, CBR, ABR and UBR services. The model proposed, narned PCSTS (priority classes services traffic shaping), includes a module that performs the characterization of services with unknown traffic descriptor. The flows are shaped individually, in real time, through a shaper based on the double discrete time scheduling algorithm of the GCRA from ITU/ ATM Forum. For the dynarnic multiplexing of the different service flows , at the link levei, a modified EDD scheduling algorithm is proposed with a feedback signal between the scheduling and shaping modules. As a result, it is demonstrated that it is possible to grant jitter and delay bounds for the rt-VBR and nrt-VBR services. We present simulations of the traffic characterization module and of the scheduling architecture, for different services, which confirms the expected behavior of the PCSTS model.

L’écomobilité en milieu scolaire, étudiée à travers le Pédibus ou walking school bus, système de ramassage pédestre organisant bénévolement le trajet domicile-école à l’initiative des parents, peut questionner l’éducation relative à l’environnement (ERE) et l’éducation au développement durable (EDD). S’inscrivant à la suite des travaux de Lucie Sauvé, Sandrine Depeau, Alain Legardez, Angela Barthes, Marie-Louise Martinez et Jean-Marc Lange, les analyses ont cherché à montrer comment la pratique du Pédibus peut devenir un enjeu éducatif qui touche aux finalités de l’éducation : « construire des savoirs », « construire une identité de sujet et de citoyen », « devenir une personne responsable évoluant au sein d’une communauté ». Le point de départ a été d’interroger la façon dont le discours véhiculé par les textes officiels, dont les grandes déclarations onusiennes fondatrices du développement durable (DD), voient en l’école le lieu fondamental de la formation des esprits conscients et responsables. A ces discours prônant une réforme par le haut, la thèse a mis en regard les discours des acteurs du Pédibus en Métropole Rouen Normandie, recueillis entre 2016 et 2018, afin de montrer comment s’articule un discours écocitoyen, inscrit dans un processus de réforme par la base et par l’action quotidienne. S’inspirant des études sur l’écocitoyenneté, en particulier des travaux de Marie-Louise Martinez, l’analyse interlocutive des discours a mis en évidence la constitution d’une conscience écocitoyenne et l’émergence d’une personne écoresponsable, inscrite dans son milieu urbain et naturel, ainsi que dans son milieu social (rue, quartier, ville). Par ailleurs, cette thèse constitue la première monographie universitaire consacrée au Pédibus, incluant un état de la recherche inspiré de divers pays et de domaines différents (sciences de l’éducation, médecine, sociologie, géographie) concernés par le « car-à-pattes », à l’origine des principaux types de discours portant sur un objet complexe (discours sécuritaire, hygiéniste, sociétal, environnemental). Conformément à la nature même d’un processus d’apprentissage dénué de curriculum et dont la compréhension peut s’inspirer des travaux de l’éco-ontogénèse dans l’esprit de Tom Berryman, les relations entre apprentissage non formel et apprentissage formel ont été interrogées, d’autant que les élèves concernés relèvent du « cycle des observations » et du « cycle de consolidation » de l’école primaire. Sur ces bases, la thèse a formulé des pistes de remédiation, susceptibles de renforcer la synergie entre éducation non formelle et éducation formelle d’une part, et de contribuer à la multiplication et à la pérennisation des lignes de Pédibus d’autre part, très engagée depuis des décennies dans les « déplacements doux », pourrait servir de modèle dans le domaine de l’écomobilité. / Eco-mobility in connection with schools, studied through the Walking School Bus, a pedestrian collecting system that voluntarily organizes the home-school journey for young pupils at the initiative of some parents, can raise questions about environmental education (EE) and education for sustainable development (ESD). Following the work of Lucie Sauvé, Sandrine Depeau, Alain Legardez, Angela Barthes, Marie-Louise Martinez and Jean-Marc Lange, the analyses sought to show how the practice of the Walking School Bus can become an educational issue that touches on the aims of education: "building knowledge", "building an identity as a subject and a citizen", "becoming a responsible person evolving within a community". The starting point was to question how the discourse conveyed by official texts, including the major UN declarations founding sustainable development (SD), see schools as the fundamental place for the training of conscious and responsible minds. To these discourses advocating a reform from above, the thesis compared the discourses of the actors of the Walking School Bus in Rouen Normandy Metropolis, collected between 2016 and 2018, in order to show how an eco-citizen discourse is articulated, as part of a reform process from the bottom up, and through daily action. Inspired by studies on eco-citizenship, in particular the work of Marie-Louise Martinez, the interlocutory analysis of the discourses highlighted the creation of an eco-citizen awareness and the emergence of an eco-responsible person, inscribed in its urban and natural environment, as well as in its social environment (street, neighborhood, city). Moreover, this thesis is the first university monograph devoted to the Walking School Bus, including a state of research inspired by various countries and different fields of science (educational sciences, medicine, sociology, geography) concerned by the WSB, at the origin of the main types of discourse on a complex subject (safety, hygienist, societal, environmental discourse). In accordance with the very nature of a curriculum-free learning process whose understanding can be inspired by the work of eco-ontogenesis in Tom Berryman's mind, the relationship between non-formal and formal learning was questioned, especially because the pupils concerned fall within the "observation cycle" and the "consolidation cycle" of primary school. On this basis, the thesis formulated remedial approaches that could strengthen the synergy between non-formal and formal education on the one hand, and contribute to the multiplication and sustainability of the Walking School Bus lines on the other hand. Rouen Normandy Metropolis, which has been very much involved for decades in "soft mobility", could serve as a model in the field of eco-mobility.

<div>In this thesis, the role of location-specific microstructural features in the fatigue performance of the safety-critical aerospace components made of Nickel (Ni)-base superalloys and linear friction welded (LFW) Titanium (Ti) alloys has been studied using crystal plasticity finite element (CPFE) simulations, energy dispersive X-ray diffraction (EDD), backscatter electron (BSE) images and digital image correlation (DIC).</div><div><br></div><div>In order to develop a microstructure-sensitive fatigue life prediction framework, first, it is essential to build trust in the quantitative prediction from CPFE analysis by quantifying uncertainties in the mechanical response from CPFE simulations. Second, it is necessary to construct a unified fatigue life prediction metric, applicable to multiple material systems; and a calibration strategy of the unified fatigue life model parameter accounting for uncertainties originating from CPFE simulations and inherent in the experimental calibration dataset. To achieve the first task, a genetic algorithm framework is used to obtain the statistical distributions of the crystal plasticity (CP) parameters. Subsequently, these distributions are used in a first-order, second-moment method to compute the mean and the standard deviation for the stress along the loading direction (σ_load), plastic strain accumulation (PSA), and stored plastic strain energy density (SPSED). The results suggest that an ~10% variability in σ_load and 20%-25% variability in the PSA and SPSED values may exist due to the uncertainty in the CP parameter estimation. Further, the contribution of a specific CP parameter to the overall uncertainty is path-dependent and varies based on the load step under consideration. To accomplish the second goal, in this thesis, it is postulated that a critical value of the SPSED is associated with fatigue failure in metals and independent of the applied load. Unlike the classical approach of estimating the (homogenized) SPSED as the cumulative area enclosed within the macroscopic stress-strain hysteresis loops, CPFE simulations are used to compute the (local) SPSED at each material point within polycrystalline aggregates of 718Plus, an additively manufactured Ni-base superalloy. A Bayesian inference method is utilized to calibrate the critical SPSED, which is subsequently used to predict fatigue lives at nine different strain ranges, including strain ratios of 0.05 and -1, using nine statistically equivalent microstructures. For each strain range, the predicted lives from all simulated microstructures follow a log-normal distribution; for a given strain ratio, the predicted scatter is seen to be increasing with decreasing strain amplitude and are indicative of the scatter observed in the fatigue experiments. Further, the log-normal mean lives at each strain range are in good agreement with the experimental evidence. Since the critical SPSED captures the experimental data with reasonable accuracy across various loading regimes, it is hypothesized to be a material property and sufficient to predict the fatigue life.</div><div><br></div><div>Inclusions are unavoidable in Ni-base superalloys, which lead to two competing failure modes, namely inclusion- and matrix-driven failures. Each factor related to the inclusion, which may contribute to crack initiation, is isolated and systematically investigated within RR1000, a powder metallurgy produced Ni-base superalloy, using CPFE simulations. Specifically, the role of the inclusion stiffness, loading regime, loading direction, a debonded region in the inclusion-matrix interface, microstructural variability around the inclusion, inclusion size, dissimilar coefficient of thermal expansion (CTE), temperature, residual stress, and distance of the inclusion from the free surface are studied in the emergence of two failure modes. The CPFE analysis indicates that the emergence of a failure mode is an outcome of the complex interaction between the aforementioned factors. However, the possibility of a higher probability of failure due to inclusions is observed with increasing temperature, if the CTE of the inclusion is higher than the matrix, and vice versa. Any overall correlation between the inclusion size and its propensity for damage is not found, based on inclusion that is of the order of the mean grain size. Further, the CPFE simulations indicate that the surface inclusions are more damaging than the interior inclusions for similar surrounding microstructures. These observations are utilized to instantiate twenty realistic statistically equivalent microstructures of RR1000 – ten containing inclusions and remaining ten without inclusions. Using CPFE simulations with these microstructures at four different temperatures and three strain ranges for each temperature, the critical SPSED is calibrated as a function of temperature for RR1000. The results suggest that critical SPSED decreases almost linearly with increasing temperature and is appropriate to predict the realistic emergence of the competing failure modes as a function of applied strain range and temperature.</div><div><br></div><div>LFW process leads to the development of significant residual stress in the components, and the role of residual stress in the fatigue performance of materials cannot be overstated. Hence, to ensure fatigue performance of the LFW Ti alloys, residual strains in LFW of similar (Ti-6Al-4V welded to Ti-6Al-4V or Ti64-Ti64) and dissimilar (Ti-6Al-4V welded to Ti-5Al-5V-5Mo-3Cr or Ti64-Ti5553) Ti alloys have been characterized using EDD. For each type of LFW, one sample is chosen in the as-welded (AW) condition and another sample is selected after a post-weld heat treatment (HT). Residual strains have been separately studied in the alpha and beta phases of the material, and five components (three axial and two shear) have been reported in each case. In-plane axial components of the residual strains show a smooth and symmetric behavior about the weld center for the Ti64-Ti64 LFW samples in the AW condition, whereas these components in the Ti64-Ti5553 LFW sample show a symmetric trend with jump discontinuities. Such jump discontinuities, observed in both the AW and HT conditions of the Ti64-Ti5553 samples, suggest different strain-free lattice parameters in the weld region and the parent material. In contrast, the results from the Ti64-Ti64 LFW samples in both AW and HT conditions suggest nearly uniform strain-free lattice parameters throughout the weld region. The observed trends in the in-plane axial residual strain components have been rationalized by the corresponding microstructural changes and variations across the weld region via BSE images. </div><div><br></div><div>In the literature, fatigue crack initiation in the LFW Ti-6Al-4V specimens does not usually take place in the seemingly weakest location, i.e., the weld region. From the BSE images, Ti-6Al-4V microstructure, at a distance from the weld-center, which is typically associated with crack initiation in the literature, are identified in both AW and HT samples and found to be identical, specifically, equiaxed alpha grains with beta phases present at the alpha grain boundaries and triple points. Hence, subsequent fatigue performance in LFW Ti-6Al-4V is analyzed considering the equiaxed alpha microstructure.</div><div><br></div><div>The LFW components made of Ti-6Al-4V are often designed for high cycle fatigue performance under high mean stress or high R ratios. In engineering practice, mean stress corrections are employed to assess the fatigue performance of a material or structure; albeit this is problematic for Ti-6Al-4V, which experiences anomalous behavior at high R ratios. To address this problem, high cycle fatigue analyses are performed on two Ti-6Al-4V specimens with equiaxed alpha microstructures at a high R ratio. In one specimen, two micro-textured regions (MTRs) having their c-axes near-parallel and perpendicular to the loading direction are identified. High-resolution DIC is performed in the MTRs to study grain-level strain localization. In the other specimen, DIC is performed on a larger area, and crack initiation is observed in a random-textured region. To accompany the experiments, CPFE simulations are performed to investigate the mechanistic aspects of crack initiation, and the relative activity of different families of slip systems as a function of R ratio. A critical soft-hard-soft grain combination is associated with crack initiation indicating possible dwell effect at high R ratios, which could be attributed to the high-applied mean stress and high creep sensitivity of Ti-6Al-4V at room temperature. Further, simulations indicated more heterogeneous deformation, specifically the activation of multiple families of slip systems with fewer grains being plasticized, at higher R ratios. Such behavior is exacerbated within MTRs, especially the MTR composed of grains with their c-axes near parallel to the loading direction. These features of micro-plasticity make the high R ratio regime more vulnerable to fatigue damage accumulation and justify the anomalous mean stress behavior experienced by Ti-6Al-4V at high R ratios.</div><div><br></div>