Les composites élastomères sont actuellement utilisés dans de nombreuses applications commerciales et ont montré de grandes promesses pour l'utilisation dans les nouvelles technologies. Cela soulève la pratique, ainsi que théorique nécessaire pour comprendre le lien entre la microstructure sous-jacente de composites en élastomère et de leurs propriétés mécaniques et physiques, et comment celui-ci peut être améliorée avec des changements dans l'ancienne. Dans ce contexte, l'objectif principal de cette thèse est le développement d'une analyse, le cadre homogénéisation non linéaire pour déterminer la réponse globale des composites élastomères soumis à des déformations finies. Les comptes-cadre pour l'évolution de la microstructure sous-jacente, ce qui entraîne des changements dans la géométrie finie induite par la charge appliquée. Ce point est essentiel que l'évolution de la microstructure peut avoir un assouplissement significatif géométrique (ou raidissage) effet sur la réponse globale du matériau, qui, à son tour, peut conduire à l'élaboration éventuelle d'instabilités macroscopiques. Le concept principal derrière la méthode d'homogénéisation non linéaire proposé est la construction de principes variationnels appropriés en utilisant l'idée d'un "portail composite linéaire», qui a finalement permettre la conversion des estimations disponibles homogénéisation linéaire dans les estimations analytiques pour la grande déformation de réponse global de l' non linéaire des composites en élastomère. Cette thèse comprend des applications de la théorie proposée pour les différentes classes des élastomères renforcés et poreux aléatoire et des microstructures périodiques. Une analyse complète du comportement efficace, l'évolution de la microstructure et le développement d'instabilités macroscopiques est prévu pour toutes ces applications.

Amphiphilic polymers are a class of polymers that self-assemble into different types of microstructure, depending on the solvent environment and external stimuli. Self assembly structures can exist in many different forms, such as spherical micelles, rod-like micelles, bi-layers, vesicles, bi-continuous structure etc. Most biological systems are basically comprised of many of these organised structures arranged in an intelligent manner, which impart functions and life to the system. We have adopted the atom transfer radical polymerization (ATRP) technique to synthesize various types of block copolymer systems that self-assemble into different microstructure when subject to an external stimuli, such as pH or temperature. The systems that we have studied are: (1) pH responsive fullerene (C60) containing poly(methacrylic acid) (PMAA-b-C60); (2) pH and temperature responsive fullerene containing poly[2-(dimethylamino)ethyl methacrylate] (C₆₀-b-PDMAEMA); (3) other responsive water-soluble fullerene systems. By varying temperature, pH and salt concentration, different types microstructure can be produced. In the presence of inorganic salts, fractal patterns at nano- to microscopic dimension were observed for negatively charged PMAA-b-C60, while such structure was not observed for positively charged PDMAEMA-b-C60. We demonstrated that negatively charged fullerene containing polymeric systems can serve as excellent nano-templates for the controlled growth of inorganic crystals at the nano- to micrometer length scale and the possible mechanism was proposed. The physical properties and the characteristics of their self-assembly properties will be discussed, and their implications to chemical and biomedical applications will be highlighted. / Singapore-MIT Alliance (SMA)

Tailoring the radiative properties of periodic micro/nanostructures can be used as an efficient way to create devices which have applications in energy harvesting, bioengineering and optical sensing. These structures are analyzed by a rigorous solution of the electromagnetic wave phenomena at the interfaces. The thesis explores the application of rigorous coupled-wave analysis (RCWA) method to study the optical responses of microstructure arrays. First section of the thesis elucidates the various mechanisms which are responsible for causing enhanced light absorption in inclined parallel plate grating arrays. Illustrative evidences of surface plasmon and magnetic resonances are provided by one and two-dimensional plots prepared by RCWA. Analytical agreement with visual data is obtained through use of LC circuit models. Finally, the effects of different geometric parameters on the resonance conditions are investigated. The second part of the thesis deals with application of RCWA to study the effect of light scattering on inclined silver nanorod (AgNR) arrays grown on compact disc (CD) gratings. Depending on the manner in which AgNRs are oriented with respect to CD gratings, they exhibit different optical behavior to incoming light. Effects of both incident light polarization and AgNR orientation with respect to the grating have been studied through the use of RCWA and effective medium theory. Calculated results are compared with experimental values and good agreements are observed for total reflection as well as trends of individual diffraction orders.

Το αντικείμενο της παρούσας Διδακτορικής Διατριβής είναι η αλληλεπίδραση της ηλεκτρομαγνητικής ακτινοβολίας με νανοδομημένους ημιαγωγούς. Για το σκοπό αυτό σχεδιάστηκε και κατασκευάστηκε μια διάταξη καταγραφής φασμάτων φωτοφωταύγειας, συναρτήσει της θερμοκρασίας. Τα δείγματα που εξετάστηκαν περιέχουν νανοκρυστάλλους του πυριτίου. Ερευνήθηκαν δυο διαφορετικές προσεγγίσεις για την παρασκευή τέτοιων δειγμάτων. Η πρώτη αφορά την θερμική αποσύνθεση του SiO σε θερμοκρασίες άνω των 850 ºC και οδηγεί στην παρασκευή δειγμάτων με νανοκρυστάλλους πυριτίου σε μια μήτρα από οξείδιο του πυριτίου. Η δεύτερη είναι ο σχηματισμός πορώδους πυριτίου μέσω ανοδικής ηλεκτροδιάβρωσης, τόσο σε συνθήκες ανοδικής πόλωσης, όσο και σε συνθήκες ανοιχτού κυκλώματος. Τα δείγματα που προήλθαν από θερμική αποσύνθεση του SiO επιδεικνύουν έντονη φωτοφωταύγεια, σε θερμοκρασία περιβάλλοντος, στο εγγύς υπέρυθρο και σε ενέργειες μεγαλύτερες του ενεργειακού χάσματος του πυριτίου (1.12 eV), ως αποτέλεσμα της εξιτονικής επανασύνδεσης υπό συνθήκες κβαντικού εντοπισμού. Τα φάσματα φωτοφωταύγειας και ο δομικός χαρακτηρισμός, έδωσαν χρήσιμες πληροφορίες σχετικά με την αλληλεπίδραση και προέλευση της εκπεμπόμενης ακτινοβολίας, της δομής και κινητικής του SiO που υπόκειται σε θερμική αποσύνθεση. Με την παρασκευή πορώδους πυριτίου, αναπτύχθηκε μια νέα μεθοδολογία για την ανάπτυξη μικροδομών πορώδους πυριτίου σε συνθήκες ανοιχτού κυκλώματος, με απολύτως ελεγχόμενη γεωμετρία και ιδιότητες φωτοφωταύγειας. Η μεθοδολογία αυτή είναι ενδιαφέρουσα για την ανάπτυξη μιας πληθώρας μικρο-ηλεκτρομηχανικών συστημάτων βασισμένα στο πορώδες πυρίτιο, όπως οπτοηλεκτρονικές διατάξεις και αισθητήρες. / The objective of this Thesis is the study of the interaction of electromagnetic radiation with nanostructured semiconductors. For this purpose we have designed and constructed a photoluminescence setup for the recording of spectra at various temperatures. The samples that have been investigated contain nanocrystals of silicon. We investigated two different approaches for the synthesis of such samples. The first one involves the thermal decomposition of SiO at temperatures above 850 ºC and results in silicon nanocrystals embedded in silicon oxide matrix. The second is the formation of porous silicon using the anodic dissolution of silicon under external anodic bias, as well as under open circuit potential conditions. Samples prepared by thermal decomposition of SiO exhibit strong photoluminescence, at room temperature, in the near infrared and at energies higher than the band gap of bulk silicon (1.12 eV), as a result of excitonic recombination under quantum confinement conditions. The recorded spectra and the structural characterization, gave us valuable information about the interaction, the origin of the emitted radiation, the structure and the kinetics of SiO undergoing thermal decomposition. The investigations concerning the formation of porous silicon, resulted in the development of a novel technique for the formation of porous silicon microstructures under open circuit potential conditions. The microstructure geometry and photoluminescence characteristics can be tuned. This technique is interesting for the fabrication of a variety of micro-electromechanical systems, based on porous silicon, such as optoelectronic devices and sensors.

The material development cycle is becoming too slow if compared with other technologies sectors like IT and electronics. The materials scientists’ community needs to bring materials science back to the core of human development. ICME (Integrated Computational Materials Engineer) is a new discipline that uses advanced computational tools to simulate material microstructures, processes and their links with the final properties. There is the need for a new way to design tailor-made materials with a faster and cheaper development cycle while creating products that meet “real-world” functionalities rather than vague set of specifications. Using the ICME approach, cutting edge computational thermodynamics models were employed in order to assist the microstructure characterization and refinement during the TIG welding of a functionally graded composite material with outstanding wear and corrosion resistance. The DICTRA diffusion model accurately predicted the carbon diffusion during sintering, Thermo-Calc and TC-PRISMA models described the thermodynamic and kinetics of harmful carbide precipitation, while COMSOL Multhiphysic furnished the temperature distribution profile at every timestep during TIG welding of the material. Bainite transformation and the influence of chromium and molybdenum was studied and modelled with MAP_STEEL software. The simulations were then compared with experimental observations and a very good agreement between computational works and experiments was found for both thermodynamic and kinetics predictions. The use of this new system proved to be a robust assistance to the classic development method and the material microstructures and processes were carefully adjusted in order to increase corrosion resistance and weldability. This new approach to material development can radically change the way we think and we make materials. The results suggest that the use of computational tools is a reality that can dramatically increase the efficiency of the material development.

Os processos de soldagem por atrito apresentam diversas vantagens na união de materiais metálicos. O Friction Hydro Pillar Processing (FHPP) é um processo recente utilizado para fabricação e reparo de estruturas, que surge como uma alternativa à soldagem convencional. As interfaces das soldas FHPP são geralmente as partes mais suscetíveis à falha, devido à concentração de defeitos e microestrutura heterogênea. Por ser uma técnica recente e pouco difundida é importante avaliar as juntas soldadas por esse processo. Diante desse contexto, este trabalho teve como objetivo analisar os resultados macro e microestruturais de um aço C-Mn submetido ao processo FHPP, utilizando-se diferentes parâmetros, e relacioná-los com o perfil de microdureza. Além disso, avaliar a tenacidade ao impacto nas regiões de interface da solda e no material base. Para isso, foram realizados estudos metalográficos e perfis de microdureza Vickers em diferentes regiões das soldas. Complementarmente foram ensaiadas as interfaces das soldas que obtiveram os melhores resultados, através do ensaio Charpy, para avaliação de tenacidade ao impacto. Durante a soldagem foram utilizadas diferentes forças axiais e de recalque, obtendo como resultados variações, principalmente, nas interfaces soldadas. As alterações visualizadas nas interfaces, geraram uma tenacidade ao impacto menor do que a do material base. Esse fato pode ser atribuído, principalmente, porque o material base apresentou uma microestrutura predominantemente ferrítica, enquanto as interfaces soldadas apresentaram microestruturas heterogêneas, com presença de ferrita acicular, ferrita de Widmanstätten, martensita revenida e bainita. / Friction welding processes offer several advantages to join metallic materials. Friction Hydro Pillar Processing (FHPP) is a recent process used to manufacture and repair of underwater structure, emerging as an alternative for the conventional welding. FHPP welding interface are generally most susceptible to failure due to its heterogeneous microstructure and defects concentration. As FHPP is a quite recent little known technic, evaluate joints welded by this process is important. In this context, this study objective is to analyze macro and microstructural results of a C-Mn steel welded under different FHPP process parameters, and relate this results to a microhardness profile. Besides that, evaluate welding interface and base material impact toughness. To do that, metallographic analysis and microhardness profiles were done in different regions of the welded joint. In addition welded interfaces with the best results were Charpy tested for impact toughness evaluation. Different axial and forging forces were used, achieving macro and microstructural variations mainly in welded interface as a result. These variations caused interface to have lower impact toughness than base material. It can be explained by the base material mainly ferritic structure, whilst welded interface showed heterogeneous microstructures with acicular ferrite, Widmantätten ferrite, tempered martensite and bainite.

Os processos de soldagem por atrito apresentam diversas vantagens na união de materiais metálicos. O Friction Hydro Pillar Processing (FHPP) é um processo recente utilizado para fabricação e reparo de estruturas, que surge como uma alternativa à soldagem convencional. As interfaces das soldas FHPP são geralmente as partes mais suscetíveis à falha, devido à concentração de defeitos e microestrutura heterogênea. Por ser uma técnica recente e pouco difundida é importante avaliar as juntas soldadas por esse processo. Diante desse contexto, este trabalho teve como objetivo analisar os resultados macro e microestruturais de um aço C-Mn submetido ao processo FHPP, utilizando-se diferentes parâmetros, e relacioná-los com o perfil de microdureza. Além disso, avaliar a tenacidade ao impacto nas regiões de interface da solda e no material base. Para isso, foram realizados estudos metalográficos e perfis de microdureza Vickers em diferentes regiões das soldas. Complementarmente foram ensaiadas as interfaces das soldas que obtiveram os melhores resultados, através do ensaio Charpy, para avaliação de tenacidade ao impacto. Durante a soldagem foram utilizadas diferentes forças axiais e de recalque, obtendo como resultados variações, principalmente, nas interfaces soldadas. As alterações visualizadas nas interfaces, geraram uma tenacidade ao impacto menor do que a do material base. Esse fato pode ser atribuído, principalmente, porque o material base apresentou uma microestrutura predominantemente ferrítica, enquanto as interfaces soldadas apresentaram microestruturas heterogêneas, com presença de ferrita acicular, ferrita de Widmanstätten, martensita revenida e bainita. / Friction welding processes offer several advantages to join metallic materials. Friction Hydro Pillar Processing (FHPP) is a recent process used to manufacture and repair of underwater structure, emerging as an alternative for the conventional welding. FHPP welding interface are generally most susceptible to failure due to its heterogeneous microstructure and defects concentration. As FHPP is a quite recent little known technic, evaluate joints welded by this process is important. In this context, this study objective is to analyze macro and microstructural results of a C-Mn steel welded under different FHPP process parameters, and relate this results to a microhardness profile. Besides that, evaluate welding interface and base material impact toughness. To do that, metallographic analysis and microhardness profiles were done in different regions of the welded joint. In addition welded interfaces with the best results were Charpy tested for impact toughness evaluation. Different axial and forging forces were used, achieving macro and microstructural variations mainly in welded interface as a result. These variations caused interface to have lower impact toughness than base material. It can be explained by the base material mainly ferritic structure, whilst welded interface showed heterogeneous microstructures with acicular ferrite, Widmantätten ferrite, tempered martensite and bainite.

Microestruturas poliméricas dopadas despertam grande interesse nas áreas de óptica, fotônica e biologia, pois viabilizam a produção de dispositivos com propriedades específicas. Contudo, a dopagem de microestruturas com mais de um dopante é pouco explorada na literatura. Nesse contexto, o presente trabalho propõe o desenvolvimento de uma metodologia para fabricar microestruturas poliméricas com múltiplas dopagens, através de fotopolimerização por absorção de dois fótons. Esta técnica de microfabricação faz uso de um feixe laser pulsado (Ti:safira, 780 nm, 100 fs) que é focalizado, através de lentes de microscópio, no volume de uma resina polimérica contendo fotoiniciador composto orgânico responsável por iniciar o processo de polimerização. A intensidade dos pulsos de femtossegundos é alta o bastante para que processos não lineares absorcivos, nesse caso absorção de dois fótons, ocorram apenas no volume focal, induzindo a polimerização apenas ao seu redor. Como dopantes utilizamos os corantes fluorescentes Rodamina e Fluoresceína. Para averiguar a eficácia do sistema de fabricação desenvolvido, produzimos estruturas com apenas um dopante, e as caracterizamos utilizando microscopia óptica e eletrônica. Microestruturas contendo mais de um dopante, em regiões distintas, foram produzidas através da fabricação sequencial de estruturas dopadas. Essa metodologia permite a produção de estruturas com dupla dopagem, as quais apresentam boa integridade estrutural e preservam as propriedades ópticas dos dopantes. Por fim, visando aplicações em biologia, empregamos a metodologia desenvolvida para fabricar microambientes dopados, em sítios específicos, com o antibiótico cloridrato de ciprofloxacino. Estudos iniciais do desenvolvimento da bactéria Escherichia coli nestes microambientes foram feitos, com o objetivo de demonstrar a viabilidade para este tipo de aplicação. / Doped microstructures have attracted interest in optics, photonics and biology, because they allow the production of devices with specific proprieties. However, doping microstructures with more than one dopant is not much exploited in the literature. In this work we demonstrate the development of a method to fabricate multi-doped microstructures by two-photon absorption polymerization. For the microfabrication we used a femtosecond laser (Ti:sapphire laser, 780 nm, 100 fs) that is focused, by a microscope objective, in the volume of a polymeric resin containing a photoinitiator organic compound responsible to initiate the polymerization. The intensity of the femtosecond pulses is high enough to induced two-photon absorption, and consequently polymerization, only around the focal volume. As dopants we employed the fluorescent dyes Rhodamine and Fluorescein. In order to verify the microfabrication system, we have initially fabricated microstructures with only one dopant, which were characterized using optical and electron microscopies. Microstructures containing more than one dopant, in distinct regions, were produced by sequential fabrication of single doped structures. Such method allowed the fabrication of double doped structures, which presents good structural integrity and maintain the characteristic optical properties of the dyes. Finally, aiming at biological applications, we employed the developed method to fabricate micro-environments doped, in specific sites, with the antibiotics ciprofloxacin hydrochloride. Initial studies on the growth of the bacterium Escherichia coli, on such microstructures, were carried out to demonstrate the feasibility for such type of application.

Os processos de soldagem por atrito apresentam diversas vantagens na união de materiais metálicos. O Friction Hydro Pillar Processing (FHPP) é um processo recente utilizado para fabricação e reparo de estruturas, que surge como uma alternativa à soldagem convencional. As interfaces das soldas FHPP são geralmente as partes mais suscetíveis à falha, devido à concentração de defeitos e microestrutura heterogênea. Por ser uma técnica recente e pouco difundida é importante avaliar as juntas soldadas por esse processo. Diante desse contexto, este trabalho teve como objetivo analisar os resultados macro e microestruturais de um aço C-Mn submetido ao processo FHPP, utilizando-se diferentes parâmetros, e relacioná-los com o perfil de microdureza. Além disso, avaliar a tenacidade ao impacto nas regiões de interface da solda e no material base. Para isso, foram realizados estudos metalográficos e perfis de microdureza Vickers em diferentes regiões das soldas. Complementarmente foram ensaiadas as interfaces das soldas que obtiveram os melhores resultados, através do ensaio Charpy, para avaliação de tenacidade ao impacto. Durante a soldagem foram utilizadas diferentes forças axiais e de recalque, obtendo como resultados variações, principalmente, nas interfaces soldadas. As alterações visualizadas nas interfaces, geraram uma tenacidade ao impacto menor do que a do material base. Esse fato pode ser atribuído, principalmente, porque o material base apresentou uma microestrutura predominantemente ferrítica, enquanto as interfaces soldadas apresentaram microestruturas heterogêneas, com presença de ferrita acicular, ferrita de Widmanstätten, martensita revenida e bainita. / Friction welding processes offer several advantages to join metallic materials. Friction Hydro Pillar Processing (FHPP) is a recent process used to manufacture and repair of underwater structure, emerging as an alternative for the conventional welding. FHPP welding interface are generally most susceptible to failure due to its heterogeneous microstructure and defects concentration. As FHPP is a quite recent little known technic, evaluate joints welded by this process is important. In this context, this study objective is to analyze macro and microstructural results of a C-Mn steel welded under different FHPP process parameters, and relate this results to a microhardness profile. Besides that, evaluate welding interface and base material impact toughness. To do that, metallographic analysis and microhardness profiles were done in different regions of the welded joint. In addition welded interfaces with the best results were Charpy tested for impact toughness evaluation. Different axial and forging forces were used, achieving macro and microstructural variations mainly in welded interface as a result. These variations caused interface to have lower impact toughness than base material. It can be explained by the base material mainly ferritic structure, whilst welded interface showed heterogeneous microstructures with acicular ferrite, Widmantätten ferrite, tempered martensite and bainite.

Orientador: Maria Helena Robert / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-13T05:19:05Z (GMT). No. of bitstreams: 1 Cristofolini_Renato_D.pdf: 5642775 bytes, checksum: 04967fdc1ef436f81dd6c3fb1fcb52d0 (MD5) Previous issue date: 2009 / Resumo: Este trabalho analisa a tixohabilidade, a viabilidade de produção de pastas tixotrópicas e as transformações de fase que ocorrem na tixofundição do ferro fundido nodular ASTM A536 60-40-18. A análise da tixohabilidade é feita através de análises térmicas utilizando técnicas de Análise Térmica Diferencial (ATD) e Calorimetria Exploratória Diferencial (CED) em diferentes condições operacionais (tipo de ciclo e taxas de aquecimento/resfriamento), e através de simulação termodinâmica utilizando software THERMOCALC®. São discutidas a influência das condições dos ensaios nas temperaturas de transformações e intervalos de solidificação, e os resultados comparados com os obtidos por simulação. São discutidas as transformações de fases que ocorrem e as respectivas temperaturas, sendo proposto diagrama de fases para a liga específica em estudo. São determinadas a sensibilidade da variação da fração líquida com a temperatura (dFL/dT) e sugeridas janelas de tixoconformação, para todas as condições analisadas. Os resultados obtidos indicam uma faixa de operação para a tixoconformação da ordem de 20oC, onde uma transformação eutética se faz presente e a variação da fração líquida com a temperatura pode ser controlada adequadamente. A janela de tixoconformação depende da taxa de transferência de calor empregada: quanto maior a taxa, maior o intervalo de transformação eutética e maior a janela de tixoconformação. Quanto à análise da viabilidade de produção de pastas tixotrópicas, foram produzidas pastas por fusão parcial controlada a distintas temperaturas dentro da faixa de operação para tixoconformação determinada previamente. As microestruturas resultantes foram analisadas por microscopia ótica (MO) e eletrônica de varredura (MEV), difratometria de raios-x e microanálise utilizando energia dispersiva (EDS). Os resultados mostram a viabilidade de produção de pastas com características tixotrópicas, nas condições analisadas, apesar da estreita faixa de temperaturas da janela de tixoconformação do material estudado. Mostram ainda que a temperatura de tratamento influencia a quantidade e dimensões dos nódulos de grafita presentes na matriz da pasta, sendo que temperaturas de tixofundição superiores à faixa de transformação eutética podem levar à rápida dissolução desses nódulos e como consequência, o aumento da dureza da liga e redução de sua ductilidade. O produto tixofundido apresenta, à temperatura ambiente, estrutura constituída essencialmente de martensita, resultado do resfriamento rápido da austenita, grafita nodular de pequenas dimensões e de fases complexas em contornos de grãos martensíticos. / Abstract: This work analyses the thixoability, the viability of actual production of thixotropic semi-solid of ferritic nodular cast iron ASTM A536 60-40-18, as well as the phase transformations taking place in the process. Thixoability evaluation is made through thermal analysis by Differential Thermal Analysis (DTA) and Differential Scanning Calorimetry (DSC) tests in different conditions (cycle type and heating/cooling rate), and also through thermodynamic simulations using THERMOCALC® software. Related to these analysis it is evaluated the influence of tests conditions on transformations temperatures and ranges; results are compared to those obtained by simulation. Phase transformations are discussed and a specific phase diagram for the alloy investigated is proposed. Liquid fraction sensitivities with temperature (dFL/dT) are determined, and thixoforming windows are suggested. Results indicate that a thixoforming window in the order of 20°C are available; in this range a eutectic transformation takes place and the liquid fraction can be controlled. Beyond the eutectic temperature liquid fraction increases significantly with temperature variation and processing control can not be assured. Thixoforming windows depend on heat transfer rates: higher the rate, higher the eutectic range and the thixoforming window. To analyse the viability of actually producing thixotropic slurries by partial melting, samples were heated to temperatures within the thixoforming windows previously suggested. Resulting microstructures were analysed by optical and electronic microscopy, X-R diffraction and EDS microanalysis. Results show the feasibility of producing thixotropic semi-solid of the studied nodular iron, in spite of its narrow thixoforming field; treatment temperature influences the size and amount of graphite nodules in the matrix. Higher temperatures can lead to fast dissolution of graphite, jeopardizing the ductility of the material. Thixocast product presents, at room temperature, small nodules of graphite in a martensitic matrix and a complex phase in grain boundaries. / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica