Multilayered materials and structures are of special interest to both academic researchers and industrial engineers as they have been used in an increasing number of applications, such as micro- electromechanical system (MEMS) on polymer substrate, protective coating on metal structure for anti-corrosion, ceramic coating on metal substrate for abrasion resistance, thermal barrier coatings, metal or metal oxide coating on metal-coated polymer for reflectance tuning and protection, as well as laminated composites and structures, etc. However, the surface layer and joint interface are commonly prone to premature failures because of cracking and delamination due to their different thermal and mechanical properties. In return, the premature failures will affect the performance and structural integrity of the device and eventually cause the failure of the multilayered structures to perform their functions. Therefore, it is essential to understand the mechanical behavior and corresponding failure mechanisms of the multilayered systems. This Ph.D. dissertation focuses on the study of opening-mode fracture (OMF) behavior and interfacial delamination in different types of multilayered structures, such as the aluminum plate or wire with alumina protective coating, multilayered advanced polymeric reflectors, and asphalt pavements. In addition, another failure mechanism, i.e. the material degradation and aging, is also studied. Firstly, a two-dimensional (2D) elasoplastic fracture model in Cartesian coordinates is developed to study the OMF in the thin alumina film fully bonded to an aluminum plate undergoing large- scale yielding. The stress field in the coating layer is described by one section between two adjacent cracks. The 2D plane strain formulations are employed to analyze the elastic field in the thin film, while a one-dimensional (1D) linear hardening plastic model is applied to account for the large plastic deformations in the substrate under substantial yielding. An elastoplastic shear lag model is established to transfer the tensile stress in the substrate to the thin film. General formulations and explicit expressions of the elastic/elastoplastic solutions of the thin film/substrate system under different loading stages have been presented. The elastic field in the thin film is then verified with the finite element (FE) results. The fracture energy release rate (ERR) is calculated and corresponding elastoplastic fracture analysis is conducted. Experimental characterization is further conducted to validate the present model; the results show that this fracture modle can capture the fracture initiation, infilling, and saturation in the thin film successfully. This model has been extended to cylindrical coordinates, where the alumina coating is fully bonded to an aluminum wire/rod. Due to the axial symmetry, the proposed 2D elasoplastic fracture model has been reproduced in polar coordinates and be used to study the OMF behavior of alumina coating fully bonded to an aluminum wire. For the case where thermal loading is applied on coating/substrate structures, neither the plane strain nor plane stress assumption can be applied because the thermal loading would introduce multi axial normal stress, therefore, a three-dimensional (3D) elastic fracture model is then developed to study the OMF in the coating fully bonded to the elastic substrate. When the temperature change reaches a certain level, block cracking will initiate in the surface layer to release the accumulated thermal stress. For simplicity, we assume the top surface of the coating would keep flat and in a rectangular shape after deformation. Then the elastic field in both coating and substrate is analyzed and verified with the FE results. The fracture ERR is then obtained based on the solved elastic field and used to analyze the fracture initiation, infilling, and saturation. In order to verify the fracture analysis, the theoretical fracture analysis results are compared with FE simulation results based on the cohesive zone model (CZM) and experimental data from the literature. The good agreement demonstrates the accuracy of the proposed 3D fracture model. In addition, this model for coating/substrate system is extended to study multilayered structures with arbitrary number of layers. In order to verify this extended model, the predicted elastic field in an advanced polymeric solar reflector is compared with FE simulation results and parametric studies are conducted to investigate the effect of geometry on the accuracy of this model. Furthermore, the fracture behavior of the surface layer in the advanced polymeric solar reflector is studied using the calculated fracture ERR. Additionally, the delamination behavior, as another common failure mode of the coating/substrate structures, is then studied. The delamination fracture energy of a multilayered glass solar reflec- tor is tested by employing the width-tapered beam method. The testing results indicate that the weakest interface of the multilayered solar reflector would be the glass-copper interface with a de- lamination fracture energy 4.4 J/m2. Using the tested fracture energy as an input, an FE model is built based on the CZM and the returned peeling force from simulation is then compared with the test results to verify the accuracy of the test method. The good agreement between the simulation and test results demonstrates that the width-tapered beam method is accurate enough to measure the delamination fracture energy of this multilayered solar reflector. Additionally, the effect of aging on the delamination fracture energy is investigated by measuring the delamination fracture energy after 50 hrs’ accelerated aging test. The results show that the aging has minor effect of delamination fracture energy for samples with alumina (Al2O3) protective coating, while it reduces the delamination fracture energy for samples with titania (TiO2) protective coating. As another failure mechanism, the material degradation or aging behavior is studied in this dissertation. The weight percentage of oxygen (WPO) in three types of asphalt binders extracted from reclaimed asphalt pavements (RAPs) and one extracted from fresh Hot Mix Asphalt (HMA), that have been aged under continuous ultraviolet (UV) or UV/moisture/condensation exposure for different period, is measured using a energy-dispersive X-ray spectroscopy (EDX). Then the tested data are fitted based on two classic aging models, namely the fast-rate constant-rate (FRCR) and nonlinear differential dynamic (NDD) models. The good fitted results show that both FRCR and NDD models can capture the aging behavior of asphalt binders extracted from both RAPs and fresh HMA under continuous UV or UV/moisture/condensation exposure. Meanwhile, although exposed under UV for the same time, the WPO in samples after UV/moisture/condensation aging are lower than those in samples after continuous UV aging, which indicates that condensation and moisture reduce the UV-induced photo-oxidative aging rate.

Este trabalho estuda a influência do carbonato de cálcio (CaCO3) nas propriedades mecânicas e na formação da fase cristalina beta do polipropileno (PP). Com o intuito de produzir amostras para o estudo, foi feita uma análise preliminar sobre o enxerto do anidrido maléico no polipropileno, porque este material graftizado (PP-g-MA) contribui significativamente em blendas e compósitos ao melhorar a adesão superficial entre o PP e o CaCO3. Foram estudados dois métodos de obtenção deste produto (PP-g-MA) utilizando-se peróxido orgânico e os produtos obtidos foram caracterizados e comparados. Apesar dos resultados das análises feitas por calorimetria diferencial exploratória (DSC), análise termogravimétrica (TGA), microscopia eletrônica de varredura (MEV) e espectroscopia de energia dispersiva (EDS) indicarem importantes diferenças entre os dois métodos, a análise por espectroscopia no infravermelho (FTIR) trouxe conclusões sobre a eficácia dos métodos de graftização. Duas séries de compósitos a base de PP contendo CaCO3 foram produzidos por mistura intensiva em fusão (misturador Drais), uma contendo PP-g-MA e a outra sem. Quatro tipos de CaCO3 foram utilizados, diâmetros de 0,9 µm, 2,5 µm e 3 µm, sendo que o CaCO3 0,9 µm apresentou-se com superfície tratada e não-tratada. A concentração de CaCO3 foi mantida em 5% e a de PP-g-MA em 5% quando presente. Os compósitos foram submetidos a testes de resistência à tração, módulo na flexão e resistência ao impacto em duas temperaturas. As amostras contendo menores tamanhos de partículas de CaCO3 e PP-g-MA apresentaram melhora sinérgica na resistência mecânica, em que aumentos da resistência a impacto e da resistência a flexão foram observados. A análise da fase cristalina beta nestas amostras foi feita utilizando-se DSC e difratometria de raios-x. Também foi analisada a influência da adesão superficial entre a carga e a matriz de PP, quanto maior a adesão superficial e menor o tamanho de partícula do CaCO3, maior a formação da fase cristalina beta, o que contribuiu para a sinergia entre todas as propriedades mecânicas avaliadas neste trabalho. / This study aimed at improving the comprehension of the influence of calcium carbonate (CaCO3) in the formation of the beta crystalline phase of polypropylene (PP), as well as the changes in the mechanical properties of this polymer. A preliminary analysis of the grafting of the maleic anhydride in the polypropylene was carried out in order to produce specimens for the study, owing to the fact that this grafted polypropylene (PP-g-MA) contributes substantially to change the polarity of the polymer and therefore, enhance the superficial adhesion between PP and CaCO3. Two grafting methods using organic peroxide were studied. The grafted copolymers were analyzed by DSC, TGA, SEM, EDS, and FTIR. Two series of PP composites containing CaCO3 were produced by intensive melt mixing (Drais mixer), one of them having MA-g-PP. Four types of CaCO3 were used, which diameters were 0.9 µm, 2.5 µm and 3 µm, though the CaCO3 0.9 µm was surface-treated and non-treated. The concentration of CaCO3 was maintained at 5% and PP-g-MA at 5 % also, when present. The composites were tested for tensile strength, flexural modulus and impact strength (at two temperatures). Samples containing smaller particle sized CaCO3 and PP-g-MA showed synergistic improvement in the mechanical strength, and increases in the impact resistance and flexural strength were observed. Analysis of the beta crystal phase in these samples was performed using DSC and x-ray diffractometry. The influence of superficial adhesion between CaCO3 and PP was also analyzed, higher concentration of the beta crystalline phase was observed for better surface adhesion and smaller CaCO3 particle size, which contributed to the synergy between all the mechanical properties evaluated in this work.

All proposed methods are demonstrated by several 2D and 3D examples which have been extensively studied in the recent literature of topology optimization. / The fourth-order nonlinear parabolic C-H equations with elasticity are solved by a powerful nonlinear implicit mutigrid algorithm. To validate its correctness and efficiency, I first use it for the quadternary C-H equations without elasticity and get good results. To my best knowledge, it is the first simulation for such C-H models composed of more than three phases both in 2D and 3D. / The Optimization of Structural Topology (OST) is a breakthrough in product design because it can optimize size, shape and topology synchronously under different physical constraints. It has promising applications in industry ranging from automobile and aerospace engineering to micro electromechanical system. / Then this dissertation introduces a gradient flow in the norm of H-1 for the problem of multi-material structural topology optimization in 2/3D with a generalized Cahn-Hilliard (C-H) model with elasticity. Unlike the traditional C-H model applied to spinodal separation which only has bulk energy and interface energy, the generalized model couples the macroscopic elastic energy (mean compliance) into the total free energy. As a result, the grain morphology is not random islands or zigzag web-like objects but regular truss or bar structure. Although disturbed by elastic energy, the C-H system still keeps its two most important properties: mass conservation and energy dissipation. Therefore, it is unnecessary to compute the Lagrange multipliers for the volume constraints and make extra effort to minimize the mean compliance (elastic energy) for the optimization of structural topology. On the other hand, when pure phases separate from disordered original state, their boundaries will merge and split resulting in natural and flexible topology variation. Such aforementioned properties make the C-H model especially suitable for the problem of optimization of multi-material structural topology. / This dissertation also extends the famous Solid Isotropic Material with Penalization (SIMP) model from 2D to 3D for topology optimization of the structure with single material. A short 177-line Matlab code including 3D Finite Element Method (FEM), filter technique, Optimality Criteria (OC) algorithm and bisection method is listed in appendix A for clear understanding of this model in 3D. / This dissertation first substitutes the nonlinear diffusion method for filter process in the optimization of structural topology. Filtering has been a major technique used in a homogenization-based method for topology optimization of structures. It plays a key role in regularizing the basic problem into a well-behaved setting. But it has a drawback of smoothing effect around the boundary of material domain. A diffusion technique is presented here as a variational approach to the regularization of the topology optimization problem. A nonlinear or anisotropic diffusion process not only leads to a suitable problem regularization but also exhibits strong "edge"-preserving characteristics. Thus, it shows that the use of the nonlinear diffusions brings desirable effects of boundary preservation and even enhancement of lower-dimensional features such as flow-like structures. The proposed diffusion techniques have a close relationship with the diffusion methods and the phase-field methods of the fields of materials and digital image processing. / Zhou Shiwei. / "December 2005." / Source: Dissertation Abstracts International, Volume: 67-11, Section: B, page: 6713. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (p. 140-151). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Nos últimos anos, a aplicação de tecnologias de manufatura aditiva tem crescido, estendendo seus benefícios para áreas diversas, como saúde, e encurtando o tempo de desenvolvimento de produto. Contudo, são encontrados apenas fabricantes nacionais de versões \"open-source\" de baixo custo de tecnologias de modelagem por fusão deposição (FDM), não existindo desenvolvedor de uma tecnologia nacional. Em função disto, o objetivo principal deste trabalho é apresentar e validar uma nova concepção de processo de fabricação aditiva. Esta proposta consiste na geração seletiva de compósito de celulose e acrílico através de fonte coerente de luz UV. Para isto, foram realizados estudos referentes a duas áreas principais, desenvolvimento de material e validação da concepção de processo proposto. Para o desenvolvimento de material, foram estudados materiais fotopoliméricos a base de acrilatos de forma a ser obtida uma formulação de material adequada para ser validado o processo. Da mesma forma, a seleção do material celulósico empregado foi realizado a partir da caracterização de materiais celulósicos laminados (papéis) comumente encontrados no mercado. Adicionalmente, foi identificado potencial de viabilidade preliminar da proposta ao longo da caracterização do compósito, visto que foi avaliada a aderência entre camadas, resistência mecânica à tração, resistência à água e microestrutura do compósito. Após o desenvolvimento do material, foi desenvolvido o projeto preliminar do equipamento de validação da proposta, assim como a fabricação de um protótipo e sua calibração. Foram realizados estudos de otimização para implementação do projeto do sistema de posicionamento, assim como dimensionamento de \"error Budget\" e custo relativo de equipamento. Foi também desenvolvido sistema de deposição de material polimérico, sistema de polimerização e alimentação de material, sendo realizados estudos de caracterização e validação do processo proposto. Foram identificados os efeitos principais dos principais parâmetros de processo para a largura da linha de polimerização, interferência da formação de compósito para camadas anteriores e, por fim a construção de corpo de prova. Através destes estudos, foi possível identificar a viabilidade funcional da proposta, sendo observadas as vantagens e desvantagens desta nova concepção em relação aos principais processos de fabricação aditiva no mercado. / In recent years, the application of additive manufacturing technologies has grown, extending its benefits to diverse areas such as health, and shortening the time product development. However, national manufacturers are only found to provide versions of open-source and low cost FDM technologies, highlighting the absence of a national technology developer. Due to that, the main goal of this work is to present and evaluate a novel concept of additive manufacturing process. This proposal consists in selectively generate composite of cellulose and acrylic through a coherent UV light source. For this, studies have been conducted concerning two main areas, material development and validation of proposed process. For the development of material, we have studied photopolymeric materials based on acrylates so as to obtain a composition of material suitable for validating the process. Likewise, the selection of cellulosic substrate was made from the characterization of laminated cellulosic materials (sheet of paper) which are commonly found at market. Additionally, we identified the potential feasibility of the proposal along the preliminary characterization the composite, whereas it was evaluated the adhesion between layers, tensile strength, water resistance and microstructure of the composite. After development the material, it was developed a preliminary design of equipment for validation of proposal, in addition to fabricating and calibrating a prototype. Studies were performed to optimize and implement the mechanical design of the positioning system as well as sizing error Budget and relative cost of equipment. It was also developed the systems of poylmerization, photopolymeric material deposition, and feed of substrate, being conducted studies for the characterization and validation of proposed process. We identified the main effects of the main process parameters on the polymerization line width, interference of the formation of composite layers for and previous layers, and the construction of the test ix body. Through these studies, it was possible to identify the functional feasibility of the proposal, being observed the advantages and disadvantages of this novel design in comparison with the main additive manufacturing process in the market.

Orientador: Maria Odila Hilário Cioffi / Coorientador: Tessie Gouvea da Cruz / Banca: Andressa Cecília Milanese / Banca: Mirabel Cerqueira Rezende / Banca: Carlos Yujiro Shigue / Banca: José Daniel Diniz Melo / Resumo: Devido às suas elevadas propriedades mecânicas específicas, os materiais compósitos estão enfrentando demandas novas, onde a capacidade de produção em massa a um custo mais acessível se tornou indispensável. O processo de Moldagem por Transferência de Resina ou RTM (Resin Transfer Molding) constitui um promissor processo de fabricação de materiais compósitos. Na produção de compósitos estruturais de alto desempenho, considerando os critérios aeronáuticos, a reprodutibilidade e o baixo custo, a indústria tem mostrado grande interesse no processo RTM. Neste trabalho de tese, foi realizado um estudo experimental para a fabricação de compósitos com propriedades adequadas às aplicações tecnológicas, tendo como principal objetivo a otimização dos parâmetros de processamento: tempo de degasagem da resina, temperatura de injeção e temperatura de cura, além de avaliar a influência desses parâmetros no volume de vazios gerados em compósitos carbono/epóxi. O mérito da pesquisa está no uso do planejamento de experimentos em apoio à otimização do processamento de compósitos, com a utilização da metodologia de Taguchi e da Superfície de Respostas, para o controle e a minimização da formação de vazios, contribuindo dessa maneira, na concepção e caracterização de compósitos laminados poliméricos para aplicações aeronáuticas. As frações volumétricas de vazios foram determinadas por três diferentes métodos: método de Arquimedes (ASTM C830), digestão ácida da matriz (ASTM D3171) e porosimetria de mercúrio. Dentre os três métodos estudados para a determinação de vazios, o de digestão ácida mostrou-se mais adequado para quantificação de vazios em compósitos carbono/epóxi, uma vez que considera os poros abertos e em contato com a superfície do laminado, além dos poros fechados. A partir dos ...( Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Due to their high specific mechanical properties, composite materials are facing new demands, in which the capacity of mass production at a more affordable cost became important. The Resin Transfer Molding process or RTM is a promising process for manufacturing composite materials. In the production of high performance structural composites, taking into account the aeronautical criteria, the reproducibility and the low cost, industries have shown great interest in RTM process. In this thesis, an experimental study for the manufacturing of composites with properties suitable for technological applications was performed with the main objective of optimizing the processing parameters: time of resin degassing, injection temperature and curing temperature, as well as the evaluation of the influence of these parameters on the volume of voids generated in carbon/epoxy composites. The merit of the research is the use of the design of experiments to support the optimization of composites processing, using Taguchi's Methodology and Response Surface Methodology, in order to control and to minimize the formation of voids, thus contributing in the design and characterization of polymeric laminate composites for aircraft applications. The volumetric fractions of voids were determined by three different methods: the Archimedes' method (ASTM C830), acid digestion of the matrix (ASTM D3171) and mercury porosimetry method. Among the three methods considered for the determination of voids, the acid digestion one was the most suitable for the quantification of voids in carbon/epoxy composites, since it considers the open pores and the ones in contact with the surface of the laminate, in addition to the closed pores. From the results of the volumetric fractions of voids obtained by the acid digestion method, taking into account the optimization parameters levels for the RTM ... (Complete abstract click eletronic access below) / Doutor

Orientador: Michelle Leali Costa / Coorientador: Edson Cocchieri Botelho / Banca: Mirabel Cerqueira Rezende / Banca: Luis Rogério de Oliveira Hein / Banca: Antonio Carlos Ancelot Junior / Banca: José Maria Fernandes Malet / Resumo: Ao encontro das necessidades de um mercado cada vez mais exigente, uma série de novas resinas vem sendo desenvolvidas; dentre estas as resinas polibenzoxazinas, que constituem uma nova classe de resinas fenólicas termorrígidas, que vem superando as propriedades das tradicionais resinas epóxi e fenólica, quando aplicadas na indústria aeroespacial. Com isto, o presente trabalho tem como objetivo sintetizar a resina benzoxazina de alto desempenho denominadas oAI-a (benzoxazina orto-amida-imida), processar compósitos de benzoxazina/fibra de carbono via'Hand lay up', utilizando as resinas benzoxazina fenol-diamino difenil metano (P-DDM), a resina oAI-a e a resina benzoxazina comercialmente disponível (Epsilon 99100 RTM), via moldagem por compressão a quente, e caracterizar suas propriedades físico-químicas, tanto em condições secas como expostas a radiação ultravioleta, umidade e calor e querosene de aviação, dando subsídios para o domínio da produção e caracterização de novos materiais com aplicações aeroespaciais. Os resultados obtidos a partir deste trabalho foram comparados entre si e com as propriedades mecânicas e térmicas das tradicionais resinas epóxi e fenólica disponíveis na literatura. Os resultados mostram que os compósitos de resina benzoxazina Epsilon 99100 RTM e P-DDM apresentam boa consolidação, temperatura de transição vítrea em torno de 162°C, para a resina Epsilon 99100 RTM e 168°C para a resina P-DDM e boa estabilidade térmica. No caso dos compósitos obtidos com a resina Epsilon 99100 RTM, o condicionamento por imersão em água reduziu sua Tg em 12%, e até 4,5% para as amostras condicionadas em UV, quando comparadas com as amostras não condicionadas. Foi também observado que para as amostras expostas ao querosene de aviação houve um aumento do valor da Tg de até 3,5%, quando comparado com os ... (Resumo completo, clicar acesso eletronico abaixo) / Abstract: A series of new resins have been developed meeting the needs of an increasingly demanding market, among these the polibenzoxazin resins which constitute a new class of thermoset phenolic resin, which is overcoming the properties of traditional epoxy and phenolic resins when applied in the aerospace industry. With this, the present work aims to synthesize high performance benzoxazine resin called oAI-a (ortho-amide-imide benzoxazin), process composite benzoxazin/carbon fiber via'Hand lay up'using the benzoxazin phenol resins diamino diphenyl methane (P-DDM), the resin oAI-a and the benzoxazine resin commercially available (Epsilon 99100 RTM) via compression hot molding and characterize their physical and chemical properties both under dry conditions and exposed to ultraviolet radiation, humidity and heat and jet fuel, helping it to control production and characterization of new materials with aerospace applications. The results obtained from this study were compared between themselves and with the mechanical and thermal properties of traditional epoxy and phenolic resins available in the literature. The results show that benzoxazine resin composites Epsilon 99100 RTM and P-DDM exhibit good consolidation glass transition temperature around 162°C to the resin Epsilon 99100 RTM and 168°C to the resin P-DDM and good thermal stability. In the case of the composites obtained with Epsilon 99100 RTM resin the conditioning by immersion in water its Tg was reduced 12%, and up to 4.5% for samples UV conditioned when compared to nonconditioned samples. It was also observed that for the samples exposed to aviation kerosene was an increase in the Tg value of up to 3.5% compared with the results obtained in nonconditioned samples. In addition, samples conditioned in water showed an increase of interlaminar shear strength(22%) compared to non-conditioned samples; while the samples immersed in jet fuel showed no significant variation in their performance / Doutor

Orientadora: Michelle Leali Costa / Coorientador: Edson Cocchieri Botelho / Banca: Mirabel Cerqueira Rezende / Banca: Koshun Iha / Resumo: As resinas fenólica e furfurílica possuem elevada densidade de ligações cruzadas e alto teor de carbono fixo, sendo, portanto, amplamente aplicadas na área aeroespacial, principalmente na obtenção de carbono vítreo. Apesar do domínio da produção de resinas fenol-furfurílica (FF) já se encontrar disponível em literatura, poucos dados a respeito de suas propriedades são publicados. Além disso, quase nenhuma informação pode ser encontrada a respeito da produção de compósitos nanoestruturados de resina fenol-furfurílica reforçada com nanotubos de carbono. Desta forma, o objetivo do presente trabalho é a obtenção de resina fenol-furfurílica e seus compósitos nanoestruturados com diferentes concentrações de nanotubos de carbono (0,1; 0,5 e 1,0 % m/m) e a caracterização térmica dos mesmos. Durante o desenvolvimento deste trabalho, as amostras foram avaliadas via calorimetria exploratória diferencial (DSC), visando obter informações a respeito do seu calor específico (cp); análise termomecânica (TMA) para obtenção do coeficiente de expansão térmica linear (α) e termogravimetria (TGA) para o conhecimento da temperatura de degradação térmica, tanto via análises reais como simuladas por software, conhecido como Highway Simulation. As análises de DSC mostram que os valores de cp tendem a aumentar com a temperatura até aproximadamente 150°C, a partir da qual tendem a decrescer. Além disso, a introdução dos CNT na resina FF aumenta o valor de cp até a concentração de 0,5%. O coeficiente de expansão térmica linear obtido pela técnica de TMA para a amostra de FF foi 33.10-6 °C-1. A introdução de CNT nas amostras de FF não afeta significativamente sua estabilidade térmica. Os valores encontrados de cp, α e temperatura inicial de degradação térmica para a resina FF são próximos aos valores da resina fenólica encontrados na literatura / Abstract: Phenolic and furfuryl alcohol resins have a high density of cross-links and high carbon yield, and thus widely applied in the aerospace area, mainly in the vitreous carbon processing. The production of phenol-furfuryl alcohol resin (FF) is already available in the literature, however, few works report its properties. Furthermore, almost no information can be found regarding the production of nanostructured composites of FF/carbon nanotubes (CNT). In this way, the aim of this work is to obtain nanostructured composites of FF/CNT with different concentrations of carbon nanotubes (0.1, 0.5 and 1.0% w/w) and thermal characterization. The specimens were evaluated by differential scanning calorimetry (DSC), in order to obtain information regarding your specific heat (cp); thermo-mechanical analysis (TMA) for obtaining the linear thermal expansion coefficient (α) and thermogravimetry (TGA) to knowledge of the temperature of thermal degradation, either by actual analyses as simulated by software known as Highway Simulation. The DSC analysis shows that the samples studied show that cp values tend to increase with the increase of temperature up to 150°C. Furthermore, the introduction of the CNT in FF resin increases the value of cp up to a concentration of 0.5%. The coefficient of linear thermal expansion obtained by the TMA technique for sample FF was 33.10-6 °C-1. The introduction of the CNT samples FF does not affect its thermal stability. The values found in the analyses are close to the values of the phenolic resin in the literature / Mestre

Orientador: Herman Jacobus Cornelis Voorwald / Coorientador: Maria Odila Hilário Cioffi / Banca: Mirabel Cerqueira Rezende / Banca: Maysa Furlan / Banca: Marcelo Ornaghi Orlandi / Banca: Heitor Luiz Ornaghi Júnior / Resumo: A produção de nanobiocompósitos tem crescido nos últimos anos considerando a necessidade no desenvolvimento de materiais que visam substituir aqueles produzidos com matéria-prima oriunda do petróleo e que demoram muito tempo para se degradarem, prejudicando o meio ambiente. Dentro deste contexto, foram confeccionados nanobiocompósitos de PHBV/nanocristais de celulose (NCC) por casting e eletrofiação. O desenvolvimento do trabalho consistiu inicialmente na determinação da melhor sequência de tratamentos químicos para a obtenção da celulose a partir do capim-sapê, e as condições determinadas foram: tratamento alcalino com solução de NaOH 5% (m/m), a 75°C, seguido por três etapas de branqueamento com H2O2/NaOH. Em seguida, foi realizado um planejamento de experimentos (PE) com o qual foi possível determinar as melhores condições de hidrólise ácida para a obtenção dos NCC, que foram: H2SO4 60% (m/m), a 60°C por 30 min (NCC4) e H2SO4 64% (m/m), a 35°C por 75 min (NCC9). Posteriormente, outro PE foi realizado para determinar os parâmetros mais adequados para a solubilidade e processamento do PHBV, e os resultados obtidos levaram à escolha dos seguintes parâmetros: solução de PHBV com 5% (m/m) de polímero em solventes dimetilformamida e clorofórmio (razão 22/78) solubilizados a 50°C por 30h, casting a 153°C e eletrofiação com agulha 20x10, rotação do tambor de 27 rpm, distância de trabalho de 10 cm, com condições ambientais próximas a 25°C e 50% de umidade. Por fim, foram confecionados os nanocompósitos PHBV/NCC4 e PHBV/NCC9, com a adição de 1% (m/m) de reforço, pelos processos de casting e eletrofiação, seguindo as condições de solubilidade e processamento estabelecidas no PE. A adição dos NCC nos nanocompósitos obtidos por casting não alterou a transparência dos filmes e proporcionou uma redução ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The production of nanobiocomposites has grown in recent years considering the need to develop materials to replace those produced using raw materials derived from petroleum and that take a long time to degrade, damaging the environment. However, nanobiocomposites of PHBV/cellulose nanocrystals (CNC), were obtained by solvent casting and electrospinning. First of all, was determined the best sequence of chemical treatments to obtain cellulose from brazilian satintail, and the conditions were: alkali treatment with NaOH solution (5% w/w) at 75°C , followed by three stages of bleaching with H2O2/NaOH. Then, following a design of experiments (DOE) it was possible to determine the best conditions of acid hydrolysis to obtain the CNC: H2SO4 60% (w/w) at 60°C for 30 min (CNC4) and H2SO4 64% (w/w) at 35°C for 75 min (CNC9). Afterwards, other DOE was conducted to determine the most appropriate PHBV solubility and processing parameters, and the results obtained led to the choice of the following parameters: PHBV solution containing 5% (w/w) of polymer in solvent dimethylformamide and chloroform (ratio 22/78), solubilized at 50°C for 30h; casting at 153°C, and electrospinning with needle (20x10), drum rotation of 27 rpm, working distance of 10 cm and environmental conditions close to 25°C and 50% of moisture. Finally, the nanocomposites PHBV/NCC4 and PHBV/NCC9 were obtained with the addition of 1% (w/w) of reinforcement by casting and electrospinning process, following the solubility and processing conditions determined at DOE. The addition of CNC in the nanocomposites obtained by solvent casting did not change the transparency of the films and provided a significant decrease in the polymer crystallization temperature, mainly with the addition of CNC4, whereas for electrospun nanocomposites, provided a considerable improvement in process efficiency, by ... (Complete abstract click electronic access below) / Doutor

Orientador: Maria Odila Hilário Cioffi / Coorientador: Mauricio Vicente Donadon / Banca: Herman Jacobus Cornelis Voorwald / Banca: Antonio Carlos Ancelotti Júnior / Banca: Mirabel Cerqueira Rezende / Banca: Sérgio Roberto Montoro / Resumo: Os materiais compósitos em fibra de carbono são largamente empregados no setor de transporte aéreo e vem crescendo em outros setores. Esses materiais, porém ainda apresentam susceptibilidade à delaminação, devido à baixa resistência a carregamentos fora do plano, tornando-se força motriz para a redução da vida em fadiga de compósitos laminados. Devido à importância desse tipo de dano, esta pesquisa visa entender os mecanismos que geram delaminações em compósitos tramados (biaxiais), utilizando-se o conceito energético de Griffith da mecânica da fratura linear elástica, como parâmetro de controle da delaminação. Portanto, o objetivo deste trabalho é entender a interação dos modos de propagação I e II, bem como as frações de cada modo na delaminação em fadiga axial tração-tração (denominado modo misto), em corpos de prova planos. Para isso, foram estudados os modos puros I (DCB) e II (ENF) de propagação de trinca nos compósitos processados, além de se comparar a região que delimita a propagação estável com o modo misto, o qual exigiu estudos de uma geometria apropriada para a obtenção de delaminação bem definida. Para a decomposição dos modos que agem na fadiga axial, foram aplicados critérios de falha nos dados experimentais. O ensaio de fadiga, para todos os modos de propagação, foi conduzido à razão de carga de 0,1, frequência de 5 Hz e os dados de taxa de propagação versus energia de deformação foram ajustados por uma lei empírica, previamente estudada e comparada com os mecanismos de delaminação por análise fractográfica. Os resultados mostraram que a força motriz para delaminação possui maior influência da tenacidade à fratura (GIc) e do carregamento máximo (Gmax), os quais foram adaptados na lei de Paris para delaminação estável. Para o modo misto, constatou-se que a geometri ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Carbon fiber composite materials are currently widely employed in air transportation as structural components in Boeing 787 Dreamliner, which has around 80% (v/v) in composite. However these materials are susceptible to delamination due to low strength in through-the-thickness direction which is the driving force to reduce the fatigue life. Considering the importance of delamination, the aim of this research is to have a clear understanding of this type of damage in woven composites by using the Griffith energy approach of the linear elastic fracture mechanics as a delamination parameter. The aim of this work was to achieve insight into the interaction process of crack propagation modes I and II, and mainly to determine the mode fractions in the delamination process of tension-tension axial fatigue tests. For the mode decomposition process from axial fatigue tests, it was employed two failure criteria. In order to obtain it, the crack growth rate associated with pure modes I and II delamination were compared with the behavior of a specimen subjected to in-plane tension-tension cyclic loading that exhibits a mixed delamination mode for which needed an appropriate specimen geometry to generate a sharp delamination front. Fatigue test in all modes of propagation were conducted with a loading ratio of 0,1 and a frequency of 5 Hz. The crack growth rate versus energy release rate was described by an appropriate empirical power law which fits the experimental results and compared with delamination mechanisms observed by fractography. The results showed that the driving force for fatigue has major influence of GIc and Gmax based on the studied fractures, where both were considered in the Paris law. For the mixed mode, the geometry known as CLS had regions of crack propagation rate comparable to pure delamination modes in the stable propagation region which ... (Complete abstract click electronic access below) / Doutor

Ce travail de thèse consiste à caractériser l’endommagement subi par une mèche de carbone au cours des procédés de transformation textile, et plus particulièrement au cours du tissage des préformes pour les matériaux composites. Un protocole de caractérisation mécanique sur mèche sèche, ainsi qu’une méthode non-destructive d’analyse d’images, ont été mis au point pour quantifier cet endommagement. / This aim of this work is to characterize the damage suffered by a carbon tow in textile processing methods, and more particularly during preforms weaving for composites materials. A mechanical characterization protocol on dry tow tensile test and a non-destructive method of image analysis, have been developed to quantify this damage.