Aujourd’hui, la durée d’exploitation de certaines structures en béton est amenée à être prolongée, en parallèle, des structures présentent prématurément des signes d’endommagements dû parfois à une mauvaise prise en compte des conditions environnementales. Assurer la durabilité des structures, c’est également assurer leur exploitation de façon sécuritaire, économique et écologique. Notre objectif est dans un premier temps de comprendre les phénomènes et mécanismes en jeu, ainsi que leur potentiels couplages ; puis, dans un deuxième temps, de créer des modèles prédictifs fiables de ces comportements.Le travail présenté s’intéresse en particulier aux structures nucléaires, qui en plus d’avoir un enjeu majeur, présentent des risques vis-à-vis de la dessiccation et de pathologies thermo-activées comme la réaction sulfatique interne (RSI). Plus précisément, l’objectif de cette thèse est de comprendre la participation des granulats dans les mécanismes de dégradation du matériau sous ces deux sollicitations respectives, puis leur couplage.A cet effet, une approche expérimentale multi-échelle est menée. Elle s’intéresse à l’évolution des déformations différées ainsi que des propriétés mécaniques et de transfert de matériaux cimentaires soumis soit à la dessiccation, soit à la RSI. Dans les deux cas, les paramètres influents des granulats dans les mécanismes ont été mis en évidence et une étude paramétrique a été mis en place afin de dégager clairement l’influence de ces paramètres.Dans un premier temps, l’étude de la dessiccation est basée sur le suivi et la caractérisation de sept formulations modèles ; i.e. dont les squelettes granulaires ont été contrôlés et sélectionnés selon la taille et la fraction volumique des granulats dans le matériau ; sur 200 jours. Les essais ont mis en évidence l’influence de ces paramètres dans le phénomène d’incompatibilités de déformations entre pâte de ciment et granulats. En parallèle, l’étude expérimentale de la réaction sulfatique interne s’intéresse à caractériser l’influence de la nature minéralogique des granulats sur la formation et la progression de la pathologie. Nous nous intéressons à l’influence de ce paramètre sur la cinétique et le taux de la réaction, mais également sur l’évolution des propriétés du matériau, afin d’identifier tous les mécanismes physico-chimiques présents. Enfin, une dernière étude s’intéresse au couplage entre RSI et dessiccation. Ici, les paramètres granulats ont été fixés, et des échantillons réactifs vis-à-vis de la RSI ont été soumis à des cycles de séchage-imbibition. / Today, the operating life of some concrete structures is likely to be extended, in parallel, structures show early signs of damage due sometimes to poor consideration of environmental conditions. Ensuring the sustainability of structures also means ensuring their safe, economical and ecological operation. Our objective is first to understand the phenomena and mechanisms at play, as well as their potential couplings; then, in a second step, to create reliable predictive models of these behaviours.The work presented is particularly interested in nuclear structures, which, in addition to having a major stake in our societies, present risks with regard to desiccation and thermo-activated pathologies such as the delayed ettringite formation (DEF). More precisely, the objective of this thesis is to understand the participation of aggregates in the degradation mechanisms of the material under these two respective stresses, and then their coupling.To this end, a multi-scale experimental approach is being conducted. It takes interest in the evolution of delayed deformations as well as the mechanical and transfer properties of cementitious materials subjected to either desiccation or DEF. In both cases, the influential parameters of the aggregates in the mechanisms were identified and a parametric study was carried out to clearly identify the influence of these parameters.First, the desiccation study is based on the monitoring and characterization of seven model formulations; i.e. granular skeletons were controlled and selected according to the size and volume fraction of the aggregates in the material; over 200 days. The tests revealed the influence of these parameters in the phenomenon of aggregate restraint.In parallel, the experimental study of DEF aims at characterizing the influence of the mineralogical nature of aggregates on the formation and progression of the pathology. We are interested in the influence of this parameter on the reaction kinetics and rate, but also on the evolution of the material properties, in order to identify all the physico-chemical mechanisms at stake. Finally, a final study is interested in the coupling between RSI and desiccation. Here, the aggregate parameters were set, and samples reactive to DEF were subjected to drying and soaking cycles.

京都大学 / 新制・課程博士 / 博士(農学) / 甲第23520号 / 農博第2467号 / 新制||農||1086(附属図書館) / 学位論文||R3||N5351(農学部図書室) / 京都大学大学院農学研究科食品生物科学専攻 / (主査)教授 谷 史人, 教授 保川 清, 准教授 中川 究也 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

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Covalent SP3-hybridization defects in single-walled carbon nanotubes (CNTs) have been prevalent in recent experimental and theoretical studies for their interesting photophysical properties. These systems are able to act as excellent sources of single, infrared photons, even at room temperature, making them marketable for applications to sensing, telecommunications, and quantum information. This work was motivated by recent experimental studies on controllable defect placement and concentration as well as investigating carrier multiplication (CM) using DFT-based many-body perturbation theory (MBPT) methods to describe excitonic relaxation processes. We find that pristine CNTs do not yield appreciable MEG at the minimum threshold of twice the optical gap 2Eg, but covalent functionalization allows for improved MEG at the threshold. Finally, we see that defect-defect interactions within CNT systems can be modeled simply as HJ-aggregates in an effective Hamiltonian model, which is shown to be valid for certain, highly-redshifted defect configurations at low defect-defect separation lengths.

Pressure is mounting in the concrete industry to adopt eco-efficient methods to reduce CO₂ emissions. Portland cement (PC), an essential concrete ingredient, is responsible for over two-thirds of the embodied energy of the concrete, generating about 8% of global greenhouse gas emissions. Extraction and transportation of aggregates and raw materials that comprise concrete mixes are also directly linked to their embodied energy; thus, recycled concrete aggregates (RCA) have been proposed as a promising alternative to increase sustainability in new construction. In this context, many studies have been conducted over the past decades on the properties of RCA concrete. Recent studies have shown that suitable fresh (i.e., flowability) and short-term hardened (i.e., compressive strength) properties might be achieved when the unique microstructural features of RCA are accounted for in the mix-design process of the recycled concrete. However, manufacturing RCA from construction demolition waste (CDW) or returned concrete (RC) presents its unique challenges. Amongst others, the variation in the source of RCA and the presence of damage due to several deterioration mechanisms causes major concern. Due to the presence of reactive aggregates in many quarries in Canada, alkali-silica reaction (ASR) is one of the most common deterioration mechanisms. The durability and long-term performance of RCA concrete are not fully understood and should be further investigated, especially in regards to a) the potential of further (secondary) deterioration of recycled concrete bearing coarse and fine alkali-silica reactive aggregates b) the impact of the severity of the initial reaction on mechanical properties and kinetics of expansion in recycled concrete and c) the impact of using sound and alkali-silica reaction (ASR) affected RCA on the chloride diffusivity (and thus corrosion initiation) of concrete. This work aims to appraise the durability performance of RCA concrete made of 100% coarse RCA, particularly two families of RCA selected (i.e., returned concrete RCA, demolished concrete RCA) to represent waste currently being generated. Furthermore, two types of reactive aggregates are selected to investigate the impact of the source of the reaction (i.e. reactive coarse aggregate as original virgin aggregate - OVA and reactive sand within the residual mortar - RM) within the RCA. ASR is the distress mechanism used to introduce damage to the manufactured RCA. A new mix design technique was used to produce recycled concrete mixtures to increase eco-efficiency, improve fresh-state properties, and reduce cement use in RCA concrete. In conclusion, the initial reaction's location and severity significantly impact the compressive strength, SDT parameters, chloride diffusion rate, and shear strength of concrete specimens. Specifically, the location of the initial reaction can influence the distribution and extension of damage within the various parts of recycled concrete, while the severity of the initial reaction can affect the overall integrity of the aggregates as well as the availability of silica and alkalis for secondary reaction. These results demonstrate the importance of assessing the severity of the initial reaction and its source in order to ensure the durability and long-term performance of recycled concrete made with reactive RCA.

Yes / Recycled aggregate concrete filled stainless steel tube (RAC-FSST) is a new type of composite member combining the advantage of stainless steel and RAC. In this paper, a total of twenty-four RAC-FSST stub columns were tested under axial load, considering the influences of coarse recycled aggregate (CRA) content, steel ratios and compressive strengths of RAC. The obtained results, including the failure patterns, responses of axial load vs. deformation, stress states of external stainless steel tube and inner RAC and confinement effects, were systematically analyzed. Results indicated that all specimens presented good ductility and high residual strengths after reaching the maximum axial load. The elastic stiffness of RAC-FSSTs obviously declined with the increasing CRA content, while the strain at the ultimate load was larger. The inclusion of CRA could advance the occurrence of the confinement and lead to lower confining stress. Based on the experimental results, an analytical model with consideration of confinement action was developed to predict the axial response of RAC-FSST stub columns. Besides, the current design provisions for the normal CFST and RAC-FST members were employed to evaluate their applicability to RAC-FSSTs. In general, the design rules EN 1994-1-1:2004, GB 50936-2014 and T/CECS 625-2019 gave a conservative and relatively accurate prediction on ultimate strength of RAC-FSST stub columns. / This work was supported by the National Natural Science Foundation.

The primary objective of this thesis is to analyse the relationship between money and the macro-economy in Sri Lanka between 1977 and 1985, in order to identify the paths through which monetary policy impulses are transmitted over this period. In doing so, - we also hope to highlight the use of macro-simulation as a tool for the analysis of the monetary transmission mechanism and to emphasise the importance of formulating monetary policy within an explicit monetary control framework. This is especially important in Sri Lanka since monetary policy has been a key instrument of demand management since 1977 and historically there has been a noticeable absence of an explicit monetary control framework. Empirical research on the monetary transmission mechanism has been very limited as far as developing countries are concerned. An exception here is the SEACEN (1981) study which simulates the effects of monetary shocks on a number of South East Asian countries, including Sri Lanka, using a flexible monetarist approach. Our research is based upon a revision of the specification of this model for Sri Lanka and a more comprehensive disaggregation of the monetary transmission channels. Our empirical model produces statistical results which are generally acceptable and conform to a Priori expectations. This model is then simulated dynamically, both, to validate the equations in the context of a complete model and to quantify the impact of alternative policy scenarios relating to the monetary transmission mechanism in Sri Lanka. We believe that our results will help to shed light on the nature of the monetary transmission mechanism in developing countries as well as provide the basis for an on-going analysis of monetary management in Sri Lanka. / Central Bank of Sri Lanka

<p dir="ltr">Long-range exciton transport, when coupled with reduced exciton-exciton annihilation (EEA), is pivotal for the enhanced performance of organic photovoltaics and the efficiency of natural light-harvesting systems. This thesis explores strategies to optimize exciton transport and EEA rates in molecular materials by manipulating the quantum nature of excitons, particularly exciton delocalization. In addition, we also aim to understand factors limiting the transport of delocalized excitons within molecular materials. To this end, self-assembled perylene diimide (PDI) molecular aggregates are ideal candidates for this study due to their conducive properties for engineering exciton delocalization. <b>Chapter 1 </b>establishes a fundamental understanding of exciton delocalization, outlining strategies to tune this phenomenon within PDI aggregates and presenting the open questions this thesis addresses. <b>Chapter 2 </b>details the synthesis of PDI aggregates and delineates the spectroscopic techniques used for characterization, including steady-state absorption and emission, transient photoluminescence (PL), and transient absorption spectroscopy. It also describes the microscopy methods implemented to visualize exciton transport, such as transient PL microscopy and transient absorption microscopy (TAM). <b>Chapter 3 </b>introduces the thesis's primary theme: the suppression of exciton-exciton annihilation (EEA) in molecular aggregates through quantum interference. This chapter demonstrates that the spatial phase relationship of delocalized excitons is crucial in EEA, with band bottom excitons in H aggregates exhibiting an oscillating spatial phase relationship displaying a coherent suppression of EEA. <b>Chapter 4 </b>discusses how coupling to static and dynamic disorder affects coherent exciton propagation. High spatial and temporal resolution TAM experiments, along with temperature-dependent studies, help disentangle the contributions of static and dynamic disorder to exciton transport. <b>Chapter 5 </b>delves into the concept of band shape engineering, whereby the microscopic electronic couplings within PDI aggregates are fine-tuned by altering the packing motifs to regulate exciton transport. Through low-temperature TAM experiments, this chapter illustrates how the interplay between long-range Coulombic and short-range charge transfer electronic couplings can determine exciton bandwidth and influence the coherent propagation of excitons. <b>Chapter 6 </b>provides a summary of the work and discusses future directions, paving the way for continued exploration in the field of exciton transport and interaction in molecular aggregates.</p>

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24964号 / 理博第4989号 / 新制||理||1712(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 倉重 佑輝, 教授 渡邊 一也, 教授 林 重彦 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

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