Submitted by Biblioteca da Faculdade de Farmácia (bff@ndc.uff.br) on 2018-03-07T14:49:14Z No. of bitstreams: 1 MARIANA SOUZA ROCHA.pdf: 3905042 bytes, checksum: 6be4214c8a5cfbb4954b745d9aa9973f (MD5) / Made available in DSpace on 2018-03-07T14:49:15Z (GMT). No. of bitstreams: 1 MARIANA SOUZA ROCHA.pdf: 3905042 bytes, checksum: 6be4214c8a5cfbb4954b745d9aa9973f (MD5) / Na busca de melhorias das propriedades farmacocinética e farmacodinâmica, com propósito de minimizar efeitos adversos e melhorar a eficácia do tratamento, a tecnologia farmacêutica avança na procura por aperfeiçoamento no desenvolvimento de sistemas de liberação modificada de medicamentos. O objetivo deste trabalho foi desenvolver sistemas matriciais utilizando os polímeros hidrofílicos naturais extraídos da semente de Linum usitatissimum L. (Linhaça) com a finalidade de avaliar o potencial destes no controle de liberação do fármaco. Foi também avaliado o processo de extração da mucilagem. A análise por meio da Metodologia de Superfície e Resposta forneceu os pontos ótimos de extração para se obter o máximo de mucilagem extraída e o máximo de rendimento de extração de todas as substâncias solúveis da linhaça. Para estudar as melhores condições para se obter um equilíbrio entre esses objetivos conflitantes e explorar as opções disponíveis foi utilizado o método de interseção normal à fronteira também chamado de Normal Boundary Intersection (NBI). Com este foram encontradas as soluções Pareto ótimas uniformemente distribuídas e contínuas para o problema multiobjetivo não-linear. Através da caracterização por análise termogravimétrica (TGA) e espectroscopia na região do infravermelho com transformada de Fourier (IV- TF) foi verificado que a extração dos polímeros da linhaça no meio básico (pH 9,6) apresentou melhores características em relação a estabilidade térmica e grau de pureza quando comparado com a mucilagem adquirida no ponto ótimo (pH de 3,81) obtido pela MSR. A diferença em percentual de peso entre as duas extrações difere em apenas 5 %. A avaliação do potencial dos polímeros naturais no controle de liberação do fármaco foi realizada através do ensaio de dissolução. Este foi realizado com o objetivo de comparar os perfis de liberação do Ibuprofeno a partir de comprimidos contendo a mucilagem da linhaça (C-M), polímeros naturais, HPMC (C-HPMC), polímeros semi- sintéticos e comprimidos sem matriz polimérica (C-SP). As três formulações apresentaram um peso médio dentro do limite de variação permitido de 350 mg ± 5 % com baixo valor de DPR, friabilidade igual a zero e dureza com valores de aproximadamente 85 N que garante a resistência das unidades. O teor de Ibuprofeno nas três formulações de comprimido apresentou-se dentro da especificação farmacopéica (90- 110 %). Os resultados de comparação por ED e valores de f1 e f2 indicarem perfis de liberação semelhantes entre os comprimidos contendo mucilagem e HPMC. Entretanto a análise dos modelos matemáticos sugere que os mecanismos de liberação do ibuprofeno das formulações são diferentes. O comprimido contendo mucilagem apresentou uma liberação não- Fickiana com cinética de ordem zero. Já o contendo HPMC apresentou um modelo de pseudo- ordem zero, com uma liberação não- Fickiana e o de liberação imediata apresentou uma liberação Fickiana com um modelo matemático de Hixson- Crowell. Estudos sobre poder de intumescimento do polímero e resistência do gel são perspectivas para continuidade do estudo para compreensão dos mecanismos de liberação / In pursuit of improvements in pharmacokinetic and pharmacodynamic properties, in order to minimize adverse effects and improve treatment efficacy, the pharmaceutical technology is advancing in the search for improvement in the development of modified drug delivery systems. The objective of this work was to develop matrix systems using the natural hydrophilic polymers extracted from the Linum usitatissimum L. (Linseed) seed in order to evaluate their potential in the control of drug release. The process of extracting the mucilage was also evaluated. The analysis by means of the Surface and Response Methodology provided the optimum extraction points to obtain the maximum extracted mucilage and maximum extraction yield of all the soluble substances of the flaxseed. To study the best conditions to achieve a balance between these conflicting objectives and to explore the available options, the normal boundary intersection method (NBI) was also used. With this, the Pareto solutions were uniformly distributed and continuous for the non-linear multiobjective problem. Through the characterization by thermogravimetric analysis (TGA) and spectroscopy in the infrared region with Fourier transform (IV-TF), it was verified that the extraction of flax polymers in the basic medium (pH 9,6) presented better characteristics in relation to the thermal stability And degree of purity when compared to the obtained mucilage at the optimum point (pH 3.81) obtained by MSR. The difference in weight percentage between the two extractions differs by only 5 %. The evaluation of the potential of the natural polymers in the control of drug release was performed through the dissolution test. The aim of this study was to compare the release profiles of Ibuprofen from tablets containing flax mucilage (CM), natural polymers, HPMC (C-HPMC), semi- synthetic polymers and tablets without polymer matrix (C-SP ). The three formulations had a mean weight within the allowed range of 350 mg ± 5 % with low DPR value, friability equal to zero and hardness with values of approximately 85N that guarantees the strength of the units. The Ibuprofen content in the three tablet formulations was within the pharmacopoeial specification (90- 110 %). The comparison results by ED and values of f1 and f2 indicate similar release profiles between the mucilage containing tablets and HPMC. However, the analysis of the mathematical models suggests that the mechanisms of release of the ibuprofen of the formulations are different. The mucilage-containing tablet showed a non- Fickian release with zero order kinetics. The HPMC-containing model presented a zero-order pseudo-order model with a non- Fickian release and the immediate release model presented a Fickian release with a Hixson- Crowell mathematical model. Studies on polymer swelling power and gel strength are prospects for continuity of the study for understanding the release mechanisms

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.

O objetivo deste trabalho foi estudar o comportamento mecânico de cilindros de compósito polimérico reforçado com fibras. Para isso, foram produzidos cilindros com extremidades abertas reforçados com fibra de basalto e fibra de vidro, utilizando a técnica de enrolamento filamentar (filament winding). Estes cilindros foram submetidos a ensaio hidrostático com carregamento circunferencial, ensaio de ruptura de anel (split disk test) e ensaio de resistência ao cisalhamento interlaminar (ILSS). Uma placa do compósito de fibra de basalto foi produzida por enrolamento filamentar, para caracterização por ensaio de resistência à tração. Todos cilindros submetidos ao ensaio hidrostático apresentaram fratura localizada em uma faixa de altura do cilindro, com extensas delaminações das camadas circunferenciais. Os compósitos epóxi/fibra de basalto superaram ou igualaram os de compósito epóxi/fibra de vidro nas comparações entre resultados dos valores das propriedades mecânicas avaliadas, nas porcentagens: resistência à tração aparente de ruptura de anel em 45% e 43% em resistência específica; ILSS, em 11%; resistência/tensão de membrana de ruptura no ensaio hidrostático, em 55%. / The aim of this work was to study the mechanical behavior of fiber reinforced polymer composite cylinders. For this purpose, cylinders reinforced with basalt and glass fibers were produced, with open-ended geometry, using filament winding technique. These cylinders were submitted to hydrostatic test under circunferential loading, split disk (ring segment) test and interlaminar shear strength (ILSS). A basalt fiber composite plate was produced by filament winding for characterization by tensile strength test. All cylinders submitted to hydrostatic test presented fracture located in the height range of the cylinder, with extensive delamination of the circumferential layers. The epoxy/basalt fiber composites overcame or equated the epoxy/glass fiber composites in comparisons between results of the mechanical properties, tensile strength in split disk, in 45% and 43% in specific strength; ILSS in 11%; membrane tensile strength in the hydrostatic test, in 55%.

Este trabalho objetivou a caracterização mecânica e a análise de falha de dois tipos de juntas compósitas através de ensaios mecânicos, em que uma das juntas era composta por dois laminados de fibras de carbono recoberto em ambas as faces por tecido de fibra de vidro reforçando uma matriz termoplástica (PPS-C) unidos via soldagem por resistência elétrica, e a outra confeccionada com dois laminados de fibras de carbono reforçando uma matriz de resina epóxi (EPX-C) unidos via colagem por filme de resina epoxídica. Os dois tipos de juntas foram submetidos a impacto único transversal de 10 J, condicionamento higrotérmico, além de carregamento em fadiga compressiva no plano nas mais diversas combinações destes processos degradativos de suas propriedades mecânicas. Observou-se, que a junta termorrígida colada de EPX-C apresentou a maior resistência mecânica em flexão em quatro pontos (F4P) na condição original (como-manufaturada), assim como os maiores valores de resistência residual para as várias condições de degradação mecânica e higrotérmica a que foi submetida. Por sua vez, a junta termoplástica soldada de PPS-C exibiu, em termos percentuais, menores reduções dos valores de resistência à flexão sob as condições avaliadas, relativamente às perdas apresentadas pela junta EPX-C em idênticas circunstâncias. A análise macroscópica da superfície de fratura de ambas as juntas indicou que o modo de falha predominante da junta termorrígida foi interfacial enquanto que, para a junta PPS-C, o modo de falha predominante foi o intralaminar. Análises fratográficas através da microscopia eletrônica de varredura (MEV) evidenciaram para a junta termorrígida EPX-C, uma alta adesão entre fibra/matriz, porém uma relativamente fraca interação entre os aderentes (laminado) e o filme adesivo de colagem, enquanto que, para a junta termoplástica PPS-C, reduzidas interações fibra/matriz forem inferidas na camada externa de PPS-V do aderente assim como entre a malha metálica resistiva e os filmes puros de PPS que a revestiam. Em ensaios de resistência ao cisalhamento interlaminar (ILSS), os espécimes retirados da junta EPX-C na condição virgem evidenciaram uma colagem uniforme/homogênea, enquanto que, para a junta PPS-C, os espécimes de ensaio usinados a partir da junta virgem indicaram a ocorrência de efeitos de degradação térmica altamente localizada nas bordas soldadas. / This study aimed to mechanical characterization and failure analysis of two kinds of composite single-lap joints by mechanical tests, in which a single-lap joint was made of two adherents of carbon fibers coated on both sides with glass fiber fabric reinforcing a thermoplastic matrix (PPS-C) welded via resistance welding, and the another type made of two adherents of carbon fibers reinforcing an epoxy matrix (EPX-C) bonded by epoxy adhesive film. The two types of single-lap joints were subjected to single transverse impact of 10 J, hygrothermal conditioning, and compressive fatigue loading in the plane in various combinations of these degradative processes of mechanical properties. It was observed that the thermosetting bonded joint EPX-C showed the highest strength in four point-flexure test in the original condition (as-manufactured), as well as greater residual strength values for the various conditions of mechanical and hygrothermal degradation which was subjected. In turn, the welded thermoplastic joint PPS-C exhibited, in percentage terms, smaller reductions in flexural strength values under the tested conditions, in respect of losses showed by EPX-C in similar circumstances. Macroscopic analysis of the fracture surfaces from both joints indicated that the predominant failure mode was interfacial to thermosetting while for PPS-C joint, the predominant failure mode was intralaminar. Analysis of fracture surfaces by scanning electron microscopy (SEM) showed, for thermosetting joints EPX-C, a high adhesion between fiber/matrix, but a relatively weak interaction between adherents and the bonding adhesive film, whereas for thermoplastic joint PPS-C, reduced interactions fiber/matrix are inferred in the outer layers of PPS-V and between metal mesh and the pure PPS films that coated it. In the interlaminar shear strength tests (ILSS), the specimens removed from the EPX-C joint in the pristine condition showed a uniform/homogeneous bonding along the joint area, while for PPS-C joint, coupons extracted from pristine condition joint indicated the occurrence of degradation caused by thermal effects localized in the welded edges.

O objetivo deste trabalho foi estudar o comportamento mecânico de cilindros de compósito polimérico reforçado com fibras. Para isso, foram produzidos cilindros com extremidades abertas reforçados com fibra de basalto e fibra de vidro, utilizando a técnica de enrolamento filamentar (filament winding). Estes cilindros foram submetidos a ensaio hidrostático com carregamento circunferencial, ensaio de ruptura de anel (split disk test) e ensaio de resistência ao cisalhamento interlaminar (ILSS). Uma placa do compósito de fibra de basalto foi produzida por enrolamento filamentar, para caracterização por ensaio de resistência à tração. Todos cilindros submetidos ao ensaio hidrostático apresentaram fratura localizada em uma faixa de altura do cilindro, com extensas delaminações das camadas circunferenciais. Os compósitos epóxi/fibra de basalto superaram ou igualaram os de compósito epóxi/fibra de vidro nas comparações entre resultados dos valores das propriedades mecânicas avaliadas, nas porcentagens: resistência à tração aparente de ruptura de anel em 45% e 43% em resistência específica; ILSS, em 11%; resistência/tensão de membrana de ruptura no ensaio hidrostático, em 55%. / The aim of this work was to study the mechanical behavior of fiber reinforced polymer composite cylinders. For this purpose, cylinders reinforced with basalt and glass fibers were produced, with open-ended geometry, using filament winding technique. These cylinders were submitted to hydrostatic test under circunferential loading, split disk (ring segment) test and interlaminar shear strength (ILSS). A basalt fiber composite plate was produced by filament winding for characterization by tensile strength test. All cylinders submitted to hydrostatic test presented fracture located in the height range of the cylinder, with extensive delamination of the circumferential layers. The epoxy/basalt fiber composites overcame or equated the epoxy/glass fiber composites in comparisons between results of the mechanical properties, tensile strength in split disk, in 45% and 43% in specific strength; ILSS in 11%; membrane tensile strength in the hydrostatic test, in 55%.

High performance polymer composites are materials with emphasis on specific chemical and mechanical properties due to their broad scope of applications. The main advantages are high strenght and toughness in comparison with their low weight and density. An increased adhesion at composite interfaces is important to ensure excellent composite properties. Bundles of glass fibers were coated by plasma-polymerised interlayers of tetravinylsilane (pp-TVS) of different thicknesses and at different effective powers. The prepared interlayers of pp-TVS were analyzed to evaluate chemical composition (RBS, FTIR, XPS) and mechanical properties (NI-AFM). Microindentation test and fiber-bundle pull-out test were used to determine the interfacial shear strenght.

We present results of an experimental and theoretical study of the magnetic properties of soft magnetic gels consisting of micron-sized magnetizable particles embedded in a polymer matrix. Experiments demonstrate hysteretic dependences of composite magnetization on an applied magnetic field and non-monotonic, with maximum, dependence of the sample susceptibilities on the field. We propose a theoretical approach which describes the main physical features of these experimental results.

Le composite à matrices polymériques renforcées de fibres de carbone (CFRP) est un matériau précieux en raison de ses excellentes propriétés mécaniques, légèreté et durabilité. Un gain important d’efficacité et une réduction des émissions de carbone peuvent être obtenus en remplaçant les pièces métalliques par les CFRPs dans l'industrie du transport. Toutefois, le recyclage de déchets CFRP est problématique, car le renfort de fibres de carbone est chimiquement lié à la matrice de résine réticulée. Néanmoins, la réutilisation de fibres de carbone couteuses rend le recyclage des CFRPs potentiellement viable en termes d’économie. Dans notre laboratoire, une étude multi-échelle d’un procédé de vapo-thermolyse a été réalisée, dont l'objectif est de séparer les fibres de carbone de matrices polymériques en utilisant la vapeur d’eau surchauffée. Afin d’obtenir une meilleure compréhension du comportement de dégradation thermique des matériaux CFRP, de nombreuses analyses thermiques ainsi que les caractérisations physico-chimiques ont été effectuées sur différentes fibres de carbone, résines polymériques (époxyde ou polyphénylène sulfide) et les composites correspondants. Une étude cinétique a été également abordée. Les plans d’expériences réalisées à l'échelle pilote dans un réacteur sophistiqué permettent de déterminer les conditions expérimentales optimales du procédé semi-industriel. Les fibres de carbone récupérées à partir de conditions optimisées apparaissent propres, sans résine et conservent plus de 90% de leur résistance à la traction d’origine. Les phases gazeuse et liquide émises ont également été quantitativement analysées. La modélisation de l’écoulement et des transferts thermiques du réacteur ainsi que la simulation de la dégradation de matrices polymériques montrent les résultats comparables avec les observations expérimentales. L’analyse du cycle de vie indique que le recyclage des CFRPs peut être favorable pour l’environnement par rapport au scénario de mise en décharge. / Carbon fiber reinforced polymer-matrix composite (CFRP) is a highly valued material because of its exceptional strength, rigidity, light weight and durability. Significant fuel efficiency gains and carbon emission reduction can be obtained by replacing metal parts in automotive components with CFRPs. However, the recycling of CFRP waste is problematic because the reinforcement (carbon fiber) is chemically bonded to the cross-linked matrix resin. Nevertheless, the reuse of expensive carbon fibers makes the recycling a potentially economically viable option. A thermal process to separate carbon fibers from polymer matrix by using superheated steam has been studied in our laboratory at both bench and pilot scale. In order to understand the thermal degradation behavior of the CFRP materials, the thermal analyses along with the physicochemical characterizations of various carbon fibers, polymer resins (epoxy or polyphenylene sulfide) as well as the corresponding composites have been carried out. A kinetic study has also been conducted. The experimental design performed in a sophisticated pilot reactor helps to determine the optimal experimental conditions of the process in a semi-industrial scale. Reclaimed carbon fibers from optimized steam-thermolysis appear resin free and exhibit over 90% of their original tensile strength. The gas and liquid phases emitted from the process have also been analyzed quantitatively. The flow modeling of the reactor and the simulation of the polymer thermal degradation are in close agreement with the experimental observations. The life cycle assessment shows that the CFRP recycling can be environmentally beneficial compared to the disposal scenario.

Carbon fibre reinforced composites are known for their high specific strength-to-weight ratio and are of great interest to the aerospace industry. Incorporating these materials into the fuselage, like in Boeing's 787 "Dreamliner", offers considerable weight reduction which increases flying efficiency, and reduces the cost of flying. In flight, aircraft are often subject to lightning strikes which, in the case of composites, can result in localized melting given the high resistive nature of the material. Aerospace carbon fibre composites often incorporate a metallic mesh or foil within the composite layers to dissipate the electrical charge through the large aircraft. The damage to the aircraft is minimized but not always eliminated. This research aims to elaborate a practical technique to deposit thin layers of conductive material on the surface of aerospace grade composites. Using Cold Gas Dynamic Spray (CGDS), such coatings could be used to repair damaged components. An experimental research approach was used to develop metallic coated composites. Using the CGDS equipment of Centerline (SST-P), specific parameters (such as gas temperature and stagnation pressure) were determined for each type of metallic coating (tin-based & copper-based). The use of bond coats was explored in order to attain the desired coatings. Once optimized, these coatings were evaluated with respect to their corrosive, adhesive, and electrical properties following industry standards.

Les polymères issus de la biomasse génèrent depuis quelques années un engouement certain puisqu’ils apparaissent comme de potentiels substituts aux polymères issus de l’industrie pétrolière. Parmi ces monomères récemment développés, l’acide succinique bio-sourcé a reçu une attention particulière notamment pour des applications dans le domaine des polyesters tels que le poly(butylène succinate). La présente thèse décrit la synthèse de ce polymère par estérification directe de l’acide succinique et du 1,4-butanediol dans un réacteur pilote de 7.5 L. Les principaux paramètres du procédé tels que l’excès de diol, la température de trans-estérification ainsi que la pureté de l’acide succinique ont été étudiés. Une attention particulière a été portée sur le choix du catalyseur (son type, la quantité utilisée …) afin d’observer son influence sur le procédé ainsi que sur la stabilité du polymère final. Puis différentes stratégies de modification du poly(butylene succinate) ont été testées pour améliorer à la fois sa mise en forme par extrusion gonflage et les propriétés des films obtenus. Dans ce but l’introduction d’agents de branchements, de silices nanométriques ainsi que des comonomères rigides a été étudiée. / Polymers issued from biomass present a growing interest, since they seem to be a suitable alternative to conventional petrochemical polymers. Among the newly developed monomers, bio-based succinic acid received a particular attention for its application in the synthesis of aliphatic polyesters such as poly(butylene succinate). The present thesis reports the synthesis of this polymer via the direct esterification of succinic acid and 1,4-butanediol in a 7.5 L pilote scale reactor. Main process parameters such as the diol exces, the trans-esterification temperature as well as the purity of succinic acid have been studied. In addition a special attention was taken to highlight the influence of the catalyst (its type, quantity ...) on the synthesis and on the stability of the resulting polymer. Then several strategies of modification of poly(butylene succinate) have been studied to improve the processability of the polymer via film extrusion blowing and to enhance the properties of polymer films. To that end the introduction of branching agents, silica nanofillers as well as rigid comonomers have been studied.