Orientador: Rubens Maciel Filho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-17T01:43:12Z (GMT). No. of bitstreams: 1 ParadaHernandez_NataliaLorena_M.pdf: 3447077 bytes, checksum: 71ef0ac11523fdfcfd56b1e719487b5f (MD5) Previous issue date: 2010 / Resumo: O estudo das resinas epóxicas é de grande interesse científico e tecnológico devido à versatilidade apresentada por estes materiais. Esta versatilidade é o resultado das diferentes reações químicas envolvidas e das características físico-químicas dos diferentes endurecedores, catalisadores e reagentes que possibilitam diferentes processos e combinação de propriedades objetivando aplicações específicas. A resina epóxi obtida a partir de epicloridrina e bisfenol A, o diglicidil éter de bisfenol A, continua sendo um intermediário importante na tecnologia da resina epóxi. Os microreatores tem provado melhorar a distribuição da massa molar dos polímeros sintetizados dentro destes microaparelhos, isto como consequência das altas taxas de transferência de calor e massa e da mais rápida e melhor mistura apresentada nos microcanais graças à diminuição do tamanho. Levando isto em conta, foi estudada a síntese da resina epóxi em microreatores usando o laser na polimerização rápida da resina dentro destes pequenos reatores. Para o desenvolvimento do projeto foi estudada a síntese da resina em escala laboratorial e calculados os parâmetros cinéticos da reação de obtenção da resina epóxi líquida. O projeto de microreatores requer o conhecimento do comportamento da mistura dentro dos microcanais destes aparelhos, razão pela qual se fez uso da fluido dinâmica computacional, CFD, o qual permitiu a avaliação da mistura dos reagentes dentro das configurações testadas neste trabalho, uma configuração tipo T e tipo Y. / Abstract: Epoxy resin study is of a great scientific and technologic interest due to the versatility showed for these materials. This versatility is the result of different chemical reactions involved and the physical-chemical characteristics of the several hardeners, catalysts, and reagents that make possible uncountable process and properties combination objectify specific applications. Epoxy resin from epicholorohydrin and bisphenol-A continues being an important intermediary in the epoxy resin technology. Microreactors have shown to improve molecular weight distribution of the synthetized polymer within these microdevices; this can be explained by the high heat and mass transfer fluxes, and the faster and better mixture shown in the microchannel due to the size reduction. In this context, the epoxy resin synthesis was studied using a laser in the rapid polymerization of the resin within these small reactors. It was studied the resin synthesis in laboratorial scale and calculated the kinetic parameters of the liquid epoxy resin obtaining reaction. Since microreactor design requires knowing the mixture behavior in the microchannels, computational fluid dynamics (CFD) was used in order to evaluate the mixture grade of the reagents for the tested configuration in this work, the "T" and "Y" configuration types. / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

This work describes the production and characterization of colloidal solution of silver nanoparticles (AgNPs) and insertion of this colloidal solution in a polymeric ma-trix of epoxy resin. The first stage of this work was the preparation of AgNPs in colloi-dal solution, using AgNO3 as the precursor, ethylene glycol as a medium and dispersant sodium citrate as reducing agent and stabilizer. Were also measured the temporal sta-bility of the solution of AgNPs for possible use over time. The colloidal solution of Ag-NPs was characterized by UV-Vis, DLS (dynamic light scattering) and Zeta potential and through its measures. We found that the colloidal solution of AgNPs is composed of stable nanoparticles, and spherical with average diameter around 10 to 12 nm. In the second stage the preparation and characterization of polymeric matrix of epoxy resin with different solution concentrations (2 ml, 5 ml, 8 ml and 10 ml) of AgNPs inseted manually into the matrix. Structural characterization of components of the polymeric matrix was performed using the techniques of FTIR spectroscopy (Fouri-er transform infrared) and Raman. The indication of the presence of AgNPs and their state of dispersion in the epoxy matrix was studied by UV-Vis spectroscopy and TEM (transmission electron microscopy), and through the results showed the presence of nanoparticles in a dispersed and an average size around 50 nm. Thermogravimetric analysis (TGA) to check the maximum thermal stability of nanocomposite were per-formed. The TGA results indicated that the degradation temperature of the polymer underwent a slight decrease with increasing the volume of solution to resin AgNPs in-serted. In addition, analysis was performed microhardness of the epoxy resin produced with different concentrations of AgNPs solution and subjected to heat treatment. Ac-cording to the microhardness tests, the presence of ethylene glycol in the epoxy matrix significantly altered their microhardness values, acting as a plasticizer. / Neste trabalho descreve-se a produção e caracterização de solução coloidal de nanopartículas de prata (AgNPs) e a inserção dessa solução coloidal em uma matriz polimérica de resina epóxi. A primeira etapa desse trabalho consistiu na síntese de AgNPs em solução coloidal, utilizando AgNO3 como o precursor, o etilenoglicol como meio dispersante e o citrato de sódio como agente redutor e estabilizante. Também foram realizadas medidas de estabilidade temporal da solução de AgNPs, para possí-veis usos ao longo do tempo. A solução coloidal de AgNPs foi caracterizada pela espec-troscopia UV-Vis, DLS (espalhamento dinâmico da luz) e potencial Zeta, e através de suas medidas, constatou que a solução coloidal de AgNPs foi composta de nanopartí-culas estáveis, esféricas e com diâmetro médio em torno de 10 12 nm.Na segunda etapa foi realizada a preparação e caracterização de matriz polimé-rica de resina epóxi com diferentes concentrações (2 ml, 5 ml, 8 ml e 10 ml) de solução de AgNPs inseridas manualmente à matriz. A caracterização estrutural dos componen-tes da matriz polimérica foi realizada utilizando-se as técnicas de espectroscopia por FTIR (infravermelho por transformada de Fourier) e Raman. A indicação da presença das AgNPs e do seu estado de dispersão na matriz epóxi foi estudado empregado a espectroscopia UV-Vis e MET (microscopia eletrônica de transmissão), e por meio dos resultados, constatou-se a presença das nanopartículas de forma dispersa e com um tamanho médio em torno de 50 nm. Foram realizadas análises termogravimétricas (TGA) para verificar a estabilidade térmica da resina epóxi. Os resultados de TGA indi-caram que a máxima temperatura de degradação do polímero sofreu uma leve redu-ção com o aumento do volume de solução de AgNPs inserida à resina. Além disso, também foram realizadas análises de microdureza Vickers da resina epóxi produzida com diferentes concentrações de solução de AgNPs e submetidas a tratamento térmi-co. De acordo com os ensaios de microdureza, a presença do etilenoglicol na matriz epóxi alterou significativamente seus valores de microdureza, atuando como plastifi-cante.

FundaÃÃo de Amparo à Pesquisa do Estado do Cearà / Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Neste trabalho analisou-se a integridade mecÃnica do material compÃsito constituÃdo por uma matriz polimÃrica, resina epoxi DER 331, e por fibra de vidro tipo âEâ como agente de reforÃo. Esta anÃlise foi realizada utilizando-se o ensaio de emissÃo acÃstica, com o objetivo de correlacionar as formas de onda dos sinais com os mecanismos de falhas associados aos esforÃos de traÃÃo e flexÃo aplicados a espÃcimes fabricados com tal material. Na anÃlise dos sinais como funÃÃo do tempo foram utilizados os mÃtodos de contagem de caixas, que fornece a dimensÃo fractal, e o do intervalo re-escalado de Hurst, sendo tambÃm utilizado o mÃtodo espectral de Fourier para a anÃlise no domÃnio da freqÃÃncia. Mostrou-se que os expoentes calculados pelos mÃtodos espectral de Fourier e re-escalado de Hurst estÃo correlacionados com a dimensÃo fractal obtida pelo mÃtodo de contagem de caixa, e satisfazem as relaÃÃes previstas pelas leis de escala. Os resultados mostraram tambÃm a existÃncia de duas regiÃes de escala distintas, sendo uma caracterizada pela persistÃncia do sinal e outra por um comportamento aleatÃrio caracterÃstica do ruÃdo presente. As dimensÃes fractais obtidas apresentaram-se independentes da taxa de aquisiÃÃo da forma da onda emitida indicando a propriedade de auto-similaridade dos sinais estudados, o que confirma a sua caracterÃstica fractal. Finalmente, à conjecturado uma correlaÃÃo entre o coeficiente de Hurst/dimensÃo fractal e as falhas mecÃnicas observadas. / In this work it is analysed the mechanical integrity of the composite material constituted of a polymeric matrix, epoxy resin DER 331, reinforced by glass fiber type E. This analysis has been done by using the acoustic emission testing with the aim to correlating the wave-form of the pulse with the flaw mechanisms associated to the tensile and bending loads applied to the samples. The analysis of the pulses as a function of time has been made by using box counting method, which provides the fractal dimension, and the rescaled Hurst analysis. The analysis in the frequency domain has been made by using the spectral Fourier method It has been shown that the exponents obtained from the spectral Fourier method and the rescaled Hurst analysis are correlated to the box counting fractal dimension, and satisfy the known relations obtained from the scaling laws. The results have also shown the existence of two scaling regions, characterized by the persistence of the pulse and by a random behaviour, respectively. The fractal dimensions have also been shown to be independent of time acquisition of the emitted pulse, and this indication of self-similarity confirms its fractal characteristics. Finally, it is conjectured a correlation between the Hurst coefficient/fractal dimension and the mechanical flaws observed.

Este trabalho trata das falhas que podem ocorrer em uniões e juntas de materiais compósitos unidas mecanicamente por parafusos. O compósito de fibra de carbono (tecido) embutido em resina epoxy foi estudado neste trabalho devido ao amplo uso em estruturas de vários segmentos da indústria. O trabalho apresenta vários critérios de falha, demonstrando as vantagens e desvantagens de cada um para materiais compósitos. A fabricação dos corpos de provas e os ensaios necessários para obtenção de parâmetros e validação de estruturas são descritos. A resistência da junta mostrou-se muito menor do que a da estrutura de compósito, demonstrando a importância de estudos assim. Criou-se um modelo numérico utilizando critérios de falhas como o critério de Hashin e o de máxima tensão. Os resultados da simulação de elementos finitos tiveram uma boa relação com os ensaios experimentais e o modelo foi então validado e considerado representativo. / This work shows failures that can occur in composite mechanically fastened joints. The composite carbon fiber embedded in epoxy resin, used in this study, was chosen due to it\'s wide use in structures of any segment of the industry. Many failure criteria, showing the advantages and disadvantages for each, regarding composite structures are presented in this work. Test specimens\' manufacturing is described along with required tests for parameter definition and structures validation. The countersunk fastened joint strength is much lower than the composite structure itself, demonstrating the necessity of studies like this. A numerical model using criteria like Hashin and maximum stress was created. The finite elements\' simulation results had a close response to the experimental results and the model was validated and considered representative.

Ce travail de thèse porte sur l’étude et la mise en évidence de relations microstructure-propriétés dans des revêtements modèles à base époxy représentatifs de peinture anticorrosion. Ces relations sont établies aussi bien à l’état initial que lors de vieillissements hygrothermiques. Cette étude a tout d’abord consisté à caractériser les propriétés physico-chimiques et mécaniques du système stœchiométrique DGEBA/DAMP totalement réticulé. Ces propriétés ont été comparées à celles du système DGEBA/TETA et ont permis de montrer la forte influence de la microstructure sur ces propriétés initiales. Des vieillissements hygrothermiques cycliques à différentes températures sur films libres ont été effectués pour mesurer l’impact de la microstructure sur la durabilité des systèmes époxy. Ces travaux ont pu montrer l’influence des interactions eau-polymère dans les phénomènes de diffusion. De plus, les évolutions de certaines propriétés physico-chimiques et mécaniques ont pu être caractérisées à l’aide de la DMA (mors submersibles), lors des différentes étapes de sorption-désorption. Un comportement pseudo-fickien a pu être mis en évidence lors de la première sorption, suivi d’un comportement fickien lors des autres étapes. Les causes inhérentes à cette évolution ont pu être avancées, en mettant en jeu des réorganisations microstructurales des systèmes époxy étudiés. D’autres vieillissements hygrothermiques ont été réalisés à l’aide de la SIE sur des revêtements pour étudier l’effet de l’interface revêtement/substrat acier sur les phénomènes de diffusion, notamment le rôle des contraintes résiduelles. L’influence de la contrainte visco-élastique sur les phénomènes de prise en eau des revêtements a finalement été étudiée. / This work highlights the microstructure-properties relations inside representative epoxy based model coatings for anticorrosion paints. These relations have been established for the initial state as well as the hygrothermal ageing. First, we characterised physico-chemical and mechanical properties of the totally crosslinked DGEBA/DAMP stoichiometric system. These properties have been compared to the DGEBA/TETA system and they showed the strong influence of the microstructure on these initial properties. Cyclic hygrothermal ageing have been completed at different temperatures on free films, in order to measure the impact of the microstructure on the durability of epoxy systems. This work has shown the influence of the water-polymer interactions on diffusion phenomena. Moreover, the evolutions of several physico-chemical and mechanical properties have been characterised using DMA (submersible clamps), during different sorption-desorption steps. A pseudo-fickian behaviour has been evidenced during the first sorption, and it was followed by a fickian behaviour for all other steps. The inherent causes of this evolution have been proposed, by considering microstructural reorganisations of the studied epoxy systems. Other hygrothermal ageing have been carried out using EIS on coatings, in order to study the effects of the coating/steel substrate interface on diffusion phenomena, especially the role of residual stresses. We finally studied the influence of the visco-elastic stress on the coating water intake phenomena.

Ce travail de thèse vise à adapter un système polymère au procédé d’élaboration par infusion d’une structure en matériaux composite pour fuselage d’avion. Ce système doit répondre à certaines exigences de viscosité, de température d’infusion, de stockage mais également de prix. La méthodologie mise en place consiste à s’approprier le procédé de mise en oeuvre afin de valider le choix des résines, de les caractériser à l’état initial et enfin d’étudier leur durabilité vis-à-vis d’un vieillissement hygrothermique. La caractérisation des propriétés a mis en évidence des comportements différents à l’état initial en termes de transition vitreuse, résilience et viscosité. L’étude du vieillissement hygrothermique montre une chute des propriétés fortement liée à l’évolution chimique des réseaux polymères qui a pour origine majeure l’hydrolyse de plusieurs liaisons. Enfin, un test d’adhérence est mis en place afin d’évaluer l’interface fibre/résine. Ce test a permis d’estimer les différents traitements de surface effectués sur les fibres. / The work presented in this thesis was done to adapt a polymer to selected elaboration process by infusion of a composite material structure for an aircraft fuselage. The polymer system must meet certain requirements such as viscosity, infusion temperature, storage but also the price. Our methodology is to understand the process putting into practice in order to validate the resins choice, to characterize the initial state and the study their sustainability towards a hydrothermal ageing. Properties characterization showed different behaviours in initial state, in terms of glass transition, resilience and viscosity. The study of hydrothermal ageing reveals a drop properties closely related to the chemical evolution of polymer networks which has for major origin multiple links hydrolysis. At least an adherence test is carried out to assess the interface fiber/resin. This test was used to estimate the different surface treatments on the fiber.

Este trabalho trata das falhas que podem ocorrer em uniões e juntas de materiais compósitos unidas mecanicamente por parafusos. O compósito de fibra de carbono (tecido) embutido em resina epoxy foi estudado neste trabalho devido ao amplo uso em estruturas de vários segmentos da indústria. O trabalho apresenta vários critérios de falha, demonstrando as vantagens e desvantagens de cada um para materiais compósitos. A fabricação dos corpos de provas e os ensaios necessários para obtenção de parâmetros e validação de estruturas são descritos. A resistência da junta mostrou-se muito menor do que a da estrutura de compósito, demonstrando a importância de estudos assim. Criou-se um modelo numérico utilizando critérios de falhas como o critério de Hashin e o de máxima tensão. Os resultados da simulação de elementos finitos tiveram uma boa relação com os ensaios experimentais e o modelo foi então validado e considerado representativo. / This work shows failures that can occur in composite mechanically fastened joints. The composite carbon fiber embedded in epoxy resin, used in this study, was chosen due to it\'s wide use in structures of any segment of the industry. Many failure criteria, showing the advantages and disadvantages for each, regarding composite structures are presented in this work. Test specimens\' manufacturing is described along with required tests for parameter definition and structures validation. The countersunk fastened joint strength is much lower than the composite structure itself, demonstrating the necessity of studies like this. A numerical model using criteria like Hashin and maximum stress was created. The finite elements\' simulation results had a close response to the experimental results and the model was validated and considered representative.

The master thesis deals with the design and production of the mold for vacuum forming. Specifically, how the existing and new mold materials affect their design and, consequently, their production technology. The thesis contains a brief description of the principle of vacuum molding. Technological and design principles of designing molds. Furthermore, the realization of the solution variants and the simulation of their production. The solved variants are subsequently evaluated from a technical and economic point of view.

The present work deals with the electrical properties of nanocomposite materials. Samples for the experiment are made of epoxy resin as a matrix and oxides TiO2, Al2O3, WO3, SiO2 as nanofillers in 0.5 and 1 percent performance. The experimental samples are measured in temperature and frequency dependence of relative permittivity, dissipation factor, rezistivity and are broken down by the influence of filler on the electrical properties of the polymer. Attention is also paid to the mechanical properties of nanocomposites.

The present master´s thesis deals with the electrical properties of nanocomposite materials. Samples for the experiment are made epoxi resin and oxides TiO2 and Al2O3 as nanofillers in different percent performace. The samples nanocomposites are measured temperature dependence of the resistivity inside, dissipation factor and relative permittivity. It discusses the effect of the filler on the resulting electrical properties of the polymer.