A reflectometria no domínio do tempo permite estimar o teor de umidade de um meio através da sua correlação com a constante dielétrica. Uma sonda helicoidal TDR, que pode ser cravada em conjunto outros ensaios de penetração in situ para a estimativa do teor de umidade em diversas profundidades, tem aplicação interessante para a investigação geotécnica do subsolo. No presente trabalho, uma sonda TDR foi adaptada e utilizada em conjunto ao ensaio CPT para caracterização de um perfil de solo arenoso não saturado que ocorre na região de Bauru (SP). A calibração dessa sonda foi feita em laboratório especificamente para esse solo. As equações de calibração que mostraram os melhores resultados foram definidas correlacionando a constante dielétrica, condutividade elétrica aparente e a massa específica seca com o teor de umidade. Com o intuito de melhorar a acurácia na determinação do teor de umidade em campo e eliminar possíveis interferências no registro da onda eletromagnética, foram efetuadas modificações em algumas características do projeto original dessa sonda. Tais modificações consistiram em separar os eletrodos condutores e as partes metálicas da sonda, e eliminar o cabo coaxial de extensão, conectando a sonda diretamente a um cabo coaxial de 12 m de comprimento. Tais mudanças levaram a uma melhoria significativa na determinação do perfil de teor de umidade do local estudado. Os valores de teor de umidade de campo determinados usando o TDR ao longo de 8 m de profundidade foram comparados com os valores de referência obtidos de amostras deformadas retiradas com trado mecânico. O erro médio na estimativa do perfil de teor de umidade gravimétrico utilizando a sonda TDR helicoidal foi de 1.61%, na última campanha de ensaios realizados. Os resultados dessa pesquisa indicam que esta ferramenta é adequada para estimar do perfil de teor de umidade para uso em conjunto com o ensaio CPT. / The time domain reflectometry allows estimating the moisture content of a medium by means of its correlation with the dielectric constant. A coil TDR probe, which can be driven into the ground together with others in situ penetration tests, can be used to estimate the moisture content at different depths. It is an interesting approach for geotechnical site characterization. In this work, a coil TDR probe was adapted and used in combination with the CPT test for the site characterization of an unsaturated sandy soil profile which occurs in the region of Bauru (SP). The probe calibration was performed in laboratory specifically for that soil. The calibration equation, which presented the best results, were defined correlating the dielectric constant, electrical conductivity and dry density with the moisture content. In order to improve the accuracy for determining the water content in the field and to eliminate possible interference on the electromagnetic wave registration, modifications were made in some characteristics of the original design of this probe. Such modifications consisted in separating the conductive electrodes from the metal parts of the probe, and eliminating the coaxial extension cable, connecting the probe directly to a coaxial cable 12 m long. Such changes have led to a significant improvement in the determination of the moisture content profile of the studied site. The moisture content values determined in situ by using the TDR along 8 m depth were compared with reference values obtained from disturbed soil samples collected using mechanical augers. The root mean square error of the gravimetric water content profile using the TDR coil probe was 1.61% in the last test campaign. The results of this research indicate that this tool is suitable to estimate the gravimetric moisture content together with the CPT test.

A reflectometria no domínio do tempo permite estimar o teor de umidade de um meio através da sua correlação com a constante dielétrica. Uma sonda helicoidal TDR, que pode ser cravada em conjunto outros ensaios de penetração in situ para a estimativa do teor de umidade em diversas profundidades, tem aplicação interessante para a investigação geotécnica do subsolo. No presente trabalho, uma sonda TDR foi adaptada e utilizada em conjunto ao ensaio CPT para caracterização de um perfil de solo arenoso não saturado que ocorre na região de Bauru (SP). A calibração dessa sonda foi feita em laboratório especificamente para esse solo. As equações de calibração que mostraram os melhores resultados foram definidas correlacionando a constante dielétrica, condutividade elétrica aparente e a massa específica seca com o teor de umidade. Com o intuito de melhorar a acurácia na determinação do teor de umidade em campo e eliminar possíveis interferências no registro da onda eletromagnética, foram efetuadas modificações em algumas características do projeto original dessa sonda. Tais modificações consistiram em separar os eletrodos condutores e as partes metálicas da sonda, e eliminar o cabo coaxial de extensão, conectando a sonda diretamente a um cabo coaxial de 12 m de comprimento. Tais mudanças levaram a uma melhoria significativa na determinação do perfil de teor de umidade do local estudado. Os valores de teor de umidade de campo determinados usando o TDR ao longo de 8 m de profundidade foram comparados com os valores de referência obtidos de amostras deformadas retiradas com trado mecânico. O erro médio na estimativa do perfil de teor de umidade gravimétrico utilizando a sonda TDR helicoidal foi de 1.61%, na última campanha de ensaios realizados. Os resultados dessa pesquisa indicam que esta ferramenta é adequada para estimar do perfil de teor de umidade para uso em conjunto com o ensaio CPT. / The time domain reflectometry allows estimating the moisture content of a medium by means of its correlation with the dielectric constant. A coil TDR probe, which can be driven into the ground together with others in situ penetration tests, can be used to estimate the moisture content at different depths. It is an interesting approach for geotechnical site characterization. In this work, a coil TDR probe was adapted and used in combination with the CPT test for the site characterization of an unsaturated sandy soil profile which occurs in the region of Bauru (SP). The probe calibration was performed in laboratory specifically for that soil. The calibration equation, which presented the best results, were defined correlating the dielectric constant, electrical conductivity and dry density with the moisture content. In order to improve the accuracy for determining the water content in the field and to eliminate possible interference on the electromagnetic wave registration, modifications were made in some characteristics of the original design of this probe. Such modifications consisted in separating the conductive electrodes from the metal parts of the probe, and eliminating the coaxial extension cable, connecting the probe directly to a coaxial cable 12 m long. Such changes have led to a significant improvement in the determination of the moisture content profile of the studied site. The moisture content values determined in situ by using the TDR along 8 m depth were compared with reference values obtained from disturbed soil samples collected using mechanical augers. The root mean square error of the gravimetric water content profile using the TDR coil probe was 1.61% in the last test campaign. The results of this research indicate that this tool is suitable to estimate the gravimetric moisture content together with the CPT test.

O monitoramento em campo de fundações em estacas metálicas helicoidais é baseado em correlações empíricas entre a capacidade de carga à tração e o torque medido durante a instalação. Nesta pesquisa é proposto um modelo teórico da relação entre o torque de instalação e a capacidade de carga à tração deste tipo de estaca em areias para ser utilizado como procedimento de controle durante a execução deste tipo de fundação. Para validar esta relação teórica e para avaliar o desempenho desta fundação em solos arenosos, foi realizado um programa experimental dividido em dois grupos: ensaios de campo e ensaios de laboratório. Em campo foram realizadas provas de carga à tração na Escola de Engenharia de São Carlos (EESC) e em Contagem (Minas Gerais). Os ensaios de laboratório foram divididos em três grupos. O primeiro corresponde aos ensaios de modelagem física em centrífuga realizados no Laboratoire Central des Ponts et Chaussées (LCPC) em Nantes, França. O segundo engloba ensaios de cisalhamento direto de interface entre o aço da hélice da estaca e diferentes areias, parte executada no LCPC e parte na EESC. O terceiro grupo refere-se a ensaios de torção de tubos de estacas metálicas helicoidais efetuados na EESC. A partir dos resultados dos ensaios, o modelo teórico proposto nesta tese foi verificado e mostrou-se adequado para estacas metálicas helicoidais profundas com diferentes dimensões e número de hélices instaladas em solos arenosos. Os resultados das provas de carga realizadas em centrífuga e em campo foram examinados por meio dos métodos existentes na literatura para estimativa de capacidade de carga à tração desenvolvidos para este tipo de fundação. Por meio dos resultados obtidos nos ensaios em centrífuga, constatou-se que nas estacas multi-hélices a porcentagem de capacidade de carga relativa à hélice da ponta aumenta de acordo com o diâmetro da hélice e com a densidade da areia. Nos ensaios de torção de fustes de estacas helicoidais observou-se que, para tubos de mesmo diâmetro e espessura, a ruptura se inicia a partir do mesmo valor de momento torçor aplicado, independentemente de conter ou não emenda. / Empirical correlations between installation torque and uplift capacity of helical screw piles are routinely used as a procedure for quality control on site of this type of foundation. In this work, a theoretical model of the relationship between uplift capacity and installation torque of deep helical screw piles in sand was presented to be used as a quality control method for this type of foundation. An experimental program of laboratory and field investigations was carried out in order to validate this theoretical relationship. The field study included uplift tests of full-scale piles installed at the Escola de Engenharia de São Carlos (EESC) and in Contagem (Minas Gerais). The laboratory tests were performed in the Laboratoire Central des Ponts et Chaussées (LCPC/ Nantes) and at the EESC. In the LCPC a program of centrifuge and direct shear interface tests was completed. A set of torsion tests on pile shafts and of direct shear interface tests were carried out at the EESC. The results showed that the theoretical model presented is applicable to different pile dimensions, number of helices, and sand relative density. The methods existing in the literature for estimating uplift capacity of helical screw piles were used to verify the results of uplift capacities measured in field and in centrifuge studies. The results of centrifuge modelling tests demonstrated that the fraction of uplift capacity corresponding to the bottom helix increases with helix diameter and sand density. The torsion tests showed that the failure of the pile shaft begins at the same torque magnitude in experiments on shafts with and without connections.

La chiralité inhérente, provenant d’une structure concave associée à une substitution dissymétrique, est la forme de chiralité la plus répandue et est une des bases fondamentales de la reconnaissance enzymatique : outre le fait que les briques constitutives des protéines présentent un carbone asymétrique, leur repliement définit la chiralité inhérente de la poche du site actif, et est responsable de l’étonnante sélectivité des réactions enzymatiques. De façon générale, les calixarènes ont été notamment utilisés afin de modéliser les processus enzymatiques complexes. Ils sont ainsi à la base de la construction de nombreux récepteurs moléculaires artificiels, capables de reconnaître des cations, des anions ou des molécules neutres par des interactions spécifiques. L’objectif de cette thèse est la synthèse de calix[6]arènes présentant une chiralité inhérente, en leur introduisant différentes fonctionnalités différentes en l’absence de carbone asymétrique, ainsi que l’étude de leurs propriétés de reconnaissance de molécules chirales. Cet objectif est indissociable du challenge classique de la chimie organique qu’est la monofonctionnalisation de molécules possédant plusieurs fonctions réactives équivalentes. Dans un premier temps, nous avons utilisé une stratégie biomimétique et supramoléculaire pour monofonctionnaliser très sélectivement un complexe zincique de calix[6]arène portant trois bras imidazole ou un chapeau Tris(2-aminoÉthyl)AmiNe. En tirant profit de la nature réceptrice de ces complexes, différents substrats ont pu être greffés à la structure sur un seul des trois sites équivalents du grand col. Les limites de cette réaction « monoclick » biomimétique ont été quantifiées. Les complexes monofonctionnalisés sont de nouveaux objets aux propriétés réceptrices considérablement différentes des « complexes entonnoirs » décrits par notre équipe. Le contrôle de l’accès de la cavité des complexes de Zn(II), Cu(I) et Cu(II) pour des ligands exogènes a été étudiés en présence de différents ligands compétiteurs. Par ailleurs, nous avons montré que dans le cas des complexes de cuivre, l’accès à la cavité pouvait être contrôlé par un switch électrochimique. Nous avons également développé deux stratégies de synthèse de calix[6]arènes chiraux de façon inhérente à partir de précurseurs monofonctionnalisés, et nous avons synthétisé le premier »complexe entonnoir » présentant cette propriété. Sa chiralité a été mise en évidence par l’inclusion de ligands achiraux et achiraux. Nous avons également prouvé que ces phénomènes complexes pouvaient être étudiés simplement grâce à la technique RMN 19F. / Inherent chiralty, which arises from a concave structure associated with asymetric substitution, is the most common form of chiralty and is fundamental in enzymatic recognition : although aminoacids have an asymetric center, the folding of proteins creates the inherently chiral active site of enzymes and is responsible for the extraordinary selectivity of enzymatic reactions. Calix[6]arenes have been used as a tool to study complex enzymatic processes. They have also been used to build artificial molecular receptors for cations, anions or neutral molecules through very specific interactions. The goal of this thesis is the synthesis of inherently chiral calix[6]arenes by introducing different functionalities devoid of asymetric centers, and the study of the recognition of chiral molecules. First, we developped a biomimetic and supramolecular strategy to monofunctionalize a zinc calix[6]arene complex bearin three imidazole arms or a tris(2-aminoethyl)amine cap, with high selectivity. By using the recognition abilities of theses substrates, several molecules were liked only one of the three equivalent sites of the big rim of the calixarene. The limits of the biomimetic « monoclick » reaction were also quantified. The monofunctionalized complexes are new objects whose abilities as molecular receptors greatly differ from the previous « funnel complexes » described by our team. The control of the access of the cavity of Zn(II), Cu(II) and Cu(I) complexes to exogenous ligands was thoroughly studied with different competitive ligands. Also, we proved that the access to the cavity could be controled with an electrochemical switch. We also developed strategies to synthesize inherently chiral calix[6]arenes from monofunctionalized complexes and we synthesized the first inherently chiral funnel complex. Its chirality was evidenced by the inclusion of chiral and achiral guests. We also provided the proof of concept that these particular phenomena could be simply studied with 19F NMR spectroscopy.

Cellulose is the most abundant biopolymer on Earth as it is found in every plant cell wall; therefore, it represents one of the most promising natural resources for the fabrication of sustainable materials. In plants, cellulose is mainly used for structural integrity, however, some species organise cellulose in helicoidal nano-architectures generating strong iridescent colours. Recent research has shown that cellulose nanocrystals, CNCs, isolated from natural fibres, can spontaneously self-assemble into architectures that resemble the one producing colouration in plants. Therefore, CNCs are an ideal candidate for the development of new photonic materials that can find use to substitute conventional pigments, which are often harmful to humans and to the environment. However, various obstacles still prevent a widespread use of cellulose-based photonic structures. For instance, while the CNC films can display a wide range of colours, a precise control of the optical appearance is still difficult to achieve. The intrinsic low thermal stability and brittleness of cellulose-based films strongly limit their use as photonic pigments at the industrial scale. Moreover, it is challenging to integrate them into composites to obtain further functionality while preserving their optical response. In this thesis, I present a series of research contributions that make progress towards addressing these challenges. First, I use an external magnetic field to tune the CNC films scattering response. Then, I demonstrate how it is possible to tailor the optical appearance and the mechanical properties of the films as well as to enhance their functionality, by combining CNCs with other polymers. Finally, I study the thermal properties of CNC films to improve the retention of the helicoidal arrangement at high temperatures and to explore the potential use of this material in industrial fabrication processes, such as hot-melt extrusion.

<p> There is a current interest in exploring novel microstructural architectures that take advantage of the response of independent phases. Current guidelines in materials design are not just based on changing the properties of the different phases but also on modifying its base architecture. Hence, the mechanical behavior of composite materials can be adjusted by designing microstructures that alternate stiff and flexible constituents, combined with well-designed architectures. One source of inspiration to achieve these designs is Nature, where biologically mineralized composites can be taken as an example for the design of next-generation structural materials due to their low density, high-strength, and toughness currently unmatched by engineering technologies.</p><p><br></p> <p>The present work focuses on the modeling of biologically inspired composites, where the source of inspiration is the dactyl club of the Stomatopod. Particularly, we built computational models for different regions of the dactyl club, namely: periodic and impact regions. Thus, this research aimed to analyze the effect of microstructure present in the impact and periodic regions in the impact resistance associated with the materials present in the appendage of stomatopods. The main contributions of this work are twofold. First, we built a model that helped to study wave propagation in the periodic region. This helped to identify possible bandgaps and their influence on the wave propagation through the material. Later on, we extended what we learned from this material to study the bandgap tuning in bioinspired composites. Second, we helped to unveil new microstructural features in the impact region of the dactyl club. Specifically, the sinusoidally helicoidal composite and bicontinuous particulate layer. For these, structural features we developed finite element models to understand their mechanical behavior.</p><p><br></p> <p>The results in this work help to elucidate some new microstructures and present some guidelines in the design of architectured materials. By combining the current synthesis and advanced manufacturing methods with design elements from these biological structures we can realize potential blueprints for a new generation of advanced materials with a broad range of applications. Some of the possible applications include impact- and vibration-resistant coatings for buildings, body armors, aircraft, and automobiles, as well as in abrasion- and impact-resistant wind turbines.</p><br>