Neste trabalho foi realizado o estudo térmico, cinético e dielétrico durante a cura de um compósito constituído de uma matriz de resina epóxi-anidrido e de talco como carga modificadora das características dielétricas e mecânicas da matriz polimérica. Foram analisadas também as propriedades dinâmicas mecânicas e morfológicas dos compósitos completamente curados. O interesse na investigação das características térmicas, cinéticas e dielétricas visou encontrar correlação entre essas características e as propriedades dinâmicas mecânicas finais dos compósitos. Foram estudados os compósitos com diferentes concentrações de carga, variando de 0 a 10% m/m, utilizando as técnicas de calorimetria exploratória diferencial (DSC), de análise dielétrica (DEA), análise termomecânica dinâmica (DMTA) e análise por microscopia eletrônica de varredura (MEV). Os resultados da análise DSC foram analisados por método isotérmico (modelo de Sourour-Kamal modificado) e por método dinâmico (modelo isoconversional). Os resultados da análise da cura dos compósitos mostraram que a concentração da carga retarda o processo de cura, conforme observado pela análise dielétrica; a temperatura de transição vítrea do compósito curado apresentou valores mínimos nas concentrações de 7 e 10%, enquanto que a análise térmica dinâmica previu que a energia de ativação aumenta com o grau de conversão. Os resultados da análise termomecânica dinâmica mostraram o aumento no módulo de armazenamento a 25ºC de 2,1 GPa (0% talco) a 3,3 GPa (10% talco), indicando haver o efeito reforçador do talco sobre a matriz polimérica. As micrografias dos compósitos foram um excelente recurso para estudar suas morfologias e se correlacionam com os resultados cinéticos e mecânicos. / In this work we performed the thermal, kinetics, dielectrical and morphological studies on the curing of a hybrid composite material composed of epoxy-anhydride matrix and talc as modifier agent of the dielectrical and mechanical properties of the polymer matrix. It also was studied the dynamic mechanical properties of the full-cured composite materials. This investigation aimed to correlate the thermal, kinetics, and dielectrical characteristics of the curing material with their final mechanical properties. Composite materials with different talc concentrations were studied in the range from 0% up to 10% w/w, employing the Differential Scanning Calorimetry (DSC), the Dielectric Analysis (DEA), Dynamic Mechanical Thermal Analysis (DMTA) and Microscopy Electron Scanning (SEM) techniques. The DSC experimental results were analyzed through the isothermal method (Modified Sourour-Kamal model) and the dynamic method (Isoconversional model). The cure analysis results of the composite specimens showed the talc acting as a cure retardant as observed from DEA results; the glass transition temperature of the full-cured composite materials showed minimum values at talc concentrations of 7 and 10%, while the dynamic thermal analysis predicted the activation energy is increasing with the conversion degree. The DMTA results exhibited the storage modulus at 25ºC increases from 2.1 GPa for the matrix without talc up to 3.3 GPa at 10% talc concentration composite, thus indicating the reinforcement role of the talc on the polymer matrix. The composites micrographs were an excellent resource for study their morphologies and for correlation of kinetics and mechanical results.

Various configurations of unidirectional carbon/epoxy composite rods were impacted radially, inspected using micro-CT scanning equipment, and tested in axial compression to measure the residual strength after impact. This data was used to correlate the relationship between impact energy, residual strength, and the peak crack area and total crack volume along the length of the specimens. These specimens represent local members of open three-dimensional composite lattice structures (e.g., based on isogrid or IsoTruss® geometries) that are continuously fabricated using advanced three-dimensional braiding techniques. The specimens were radially impacted with 2.5 J (1.9 ft-lbs), 5.0 J (3.7 ft-lbs), 7.5 J (5.6 ft-lbs), 10 J (7.4 ft-lb), 15 J (11 ft-lbs), and 20 J (15 ft-lbs) of energy, and compared to undamaged control specimens. The unidirectional core specimens were 8 mm (5/16") in diameter and were consolidated with various sleeve configurations and materials. Sleeves differed in types (bi-directional braided sleeves or unidirectional spiral wraps), nominal sleeve coverage of the core fibers (full or half), and sleeve material (Nomex Thread or Dunstone Hi-Shrink Tape). The unsupported length of the specimens used in this research was 50.8 mm (2") to ensure a strength-controlled compression failure rather than a failure due to buckling. After impact, the specimens were scanned using a micro-CT scanner at resolutions of 50 and 35 microns and subsequently tested in axial compression. The micro-CT scan images were analyzed to measure the crack areas along the specimen. From this analysis, the peak crack area and total crack volume along the length of the specimen was calculated. Similar to past research, as the impact energy increases, the residual compression-strength-after-impact decreases. As the impact energy increases, specimens with shrink tape sleeves had the largest increase in peak crack area and overall crack volume while specimens with full spiral sleeves had the lowest increase in peak crack area and overall crack volume. A bimodal increase is evident in the peak crack area and total crack volume over the length of the specimen where specimens impacted at 15 J (11 ft-lbs) showed the highest peak crack area across all sleeve types. There is a slight correlation between the increase in peak crack area and overall crack volume and the decrease in residual compression strength after impact. Shrink Tape, while yielding a higher quality specimen with greater compression strength prior to impact, did not protect the specimens against damage due to impact as well as other sleeve types. This was shown by the large decrease in residual compression strength after impact and increase in peak crack area and overall crack volume as the impact energy increased.

Compósitos desenvolvidos a partir da incorporação de rejeitos industriais além de serem mais uma opção disponível às mais diversas aplicações, podem promover a redução de passivos ambientais gerados durante anos. Visando atender à essas questões, foram desenvolvidos compósitos com matriz de resina epóxi carregados com rejeito de scheelita nas proporções de 1%, 5%, 10%, 20 % e 30%. Para tanto, o rejeito de scheelita foi, inicialmente, caracterizado por meio de FRX, DRX e MEV. Já a resina epóxi foi analisada por meio de FTIR antes e após a cura. Duas condições de cura foram adotadas para a confecção dos corpos de prova, uma realizada somente a temperatura ambiente e outra executada à temperatura ambiente com uma etapa de pós cura térmica realizada a 80°C por 5 horas. Os corpos de prova foram moldados por casting em molde de silicone e as proporções foram calculadas em volume. A massa específica dos compósitos foi determinada. Para caracterizar o desempenho mecânico das composições foram realizados ensaios de tração e ensaios de dureza os quais evidenciaram que as frações de carga mineral influenciam positivamente o módulo de elasticidade e a dureza e afetam negativamente a resistência à tração. Os parâmetros Ra, Rq e Rz foram medidos e considerados na caracterização do acabamento superficial. Ensaios de deslizamento com a configuração pino contra disco foram realizados para caracterizar o desempenho tribológico dos compósitos que geraram respostas de coeficiente de atrito e profundidade da trilha do desgaste. Os corpos de prova em forma de disco foram confeccionados com os diferentes compósitos e como pinos foram utilizadas esferas de aço AISI 52100. O compósito com 10% de carga apresentou o melhor desempenho tribológico com coeficiente de atrito variando entre 0,1 e 0,4 e profundidade da trilha do desgaste entre 25 e 50 µm. As imagens de MEV realizadas nas superfícies de ruptura dos corpos de prova de tração e nas superfícies desgastas dos discos utilizados nos ensaios pino contra disco revelaram desprendimento de material e partículas soltas sugerindo baixa adesão interfacial carga/matriz. De modo geral, as respostas obtidas estão de acordo com o que expressa a literatura. / Composites that incorporate industrial waste are an option for a wide range of applications and can also reduce the environmental passive generated over years. To address these issues, composites of epoxy resin loaded Scheelite Tailings in proportions of 1%, 5%, 10%, 20% and 30% were developed. For this, the Scheelite Tailings was characterized by XRF, XRD and SEM. The epoxy resin was analyzed by FTIR before and after curing. Two curing conditions were used for the preparation of the test specimens, at ambient temperature and the other at room temperature with a post-curing step at 80 ° C for 5 hours. The specimens were molded by casting in silicone mold and the proportions were calculated by volume. The specific mass was determined. The mechanical performance of the compositions was characterized by tensile and hardness tests which, the results showed that the mineral filler fractions generate positive effect on the Young\'s modulus and hardness and negative effect on the tensile strength. The parameters Ra, Rq and Rz were measured and considered as characterization of the surface finishing. Sliding tests with the pin on disk configuration were performed to characterize the tribological performance of the composites that generated friction coefficient responses and depth of the wear track. The disk specimens were made with the different compositions and the pins were AISI 52100 steel balls. The composite with 10% of scheelite tailings presented the best tribological performance with coefficient of friction varying between 0.1 and 0.4 and depth of the wear track between 25 and 50 50 µm. The SEM images performed on the tensile test specimen rupture surfaces and on the wear surfaces of the disks used in the pin to disk tests indicate release of material and loose particles suggesting low interfacial adhesion of mineral filler/matrix. In general, the answers obtained are in agreement with what is expressed in the literature.

This work presents the development of a test program and the results from the final round of testing to better understand the effect a submerged anchor installation has on the pullout strength of epoxy anchors. Two different epoxies were tested at embedment depths of two, four, and six bar diameters. These tests utilized three distinct installation procedures under dry and submerged conditions. The testing program occurred over five phases, with the final round used in analysis consisting of 24 anchor pullout tests. These tests showed that the presence of water did not have an effect on the epoxy bond when anchor holes were cleaned dry and installed underwater, but it did have a significant impact on the ability to consistently clean each anchor when it was submerged.

Malgré leur grande activité antioxydante, l'utilisation de phénols naturels en tant qu'additifs antioxydants phénoliques pour les polyoléfines est limitée en raison de leur faible stabilité thermique et de leur caractère hydrophile. Nous présentons ici une synthèse chimio-enzymatique durable d’antioxydants lipophiles renouvelables spécifiquement conçus pour surmonter ces restrictions en utilisant de l’acide férulique naturel (présent dans la lignocellulose) et des huiles végétales (c.-à-d. acides lauriques, palmitiques, stéariques et glycérol). L'activité antiradicalaire (DPPH) ainsi que l'activité anti-oxydante (OIT) de ces nouveaux additifs entièrement biosourcés ont été rapportées à des antioxydants à base de carbone fossile disponibles dans le commerce tels que l'Irganox 1010® et l'Irganox 1076®. En outre, les tests d'activité œstrogénique n'ont révélé aucune perturbation du système endocrinien pour ces bisphénols nouvellement créés. La glycidylation de tous les composés a donné des précurseurs époxy biosourcés inoffensifs. Les analyses DSC, ATG et DMA démontrent que les propriétés thermomécaniques des résines époxy-amine obtenues peuvent être adaptées avec précision par le choix la longueur de la chaîne d’acides gras. / Despite their great antioxidant activities, the use of natural phenols as antioxidant additives for polyolefins is limited owing to their weak thermal stability and hydrophilic character. Herein, we report a sustainable chemo-enzymatic synthesis of renewable lipophilic phenolic antioxidants specifically designed to overcome these restrictions using naturally occurring ferulic acid (found in lignocellulose) and vegetal oils (i.e., lauric, palmitic, stearic acids, and glycerol) as starting materials. Antiradical activity (DPPH) as well as antioxidant activity (OIT) of these new fully biobased additives were reported to commercially available fossil-based antioxidants such as Irganox 1010® and Irganox 1076®. In addition, estrogenic activity tests revealed no endocrine disruption for newly created bisphenols. Glycidylation of all compounds afforded innocuous bio-based epoxy precursors. DSC, TGA and DMA analysis demonstrated that the thermo-mechanical properties of the obtained epoxy-amine resins can be finely tailored by judiciously selecting the fatty acid chain length.

A series of new cobalt(II) beta-keto iminato complexes and cobalt(II) salens have been made and the effect of chirality in the northern, southern and peripheral quadrants of these catalysts, with respect to induced enantiomeric excess, during the ring-opening of 1,2-dioxines has been determined. Synthesis of a series of cobalt beta-keto iminato complexes was achieved after modification of literature procedures used for the synthesis of manganese beta-keto iminato complexes and this procedure was applied to generate ligands with ethyl, t-butyl, (-)-bornyl, (+)-menthyl and (-)-menthyl esters and a methyl side chain. Synthesis of the cobalt salens was also achieved using a modified literature procedure, in respect to the more complex aldehydes made. It was ascertained that chirality in the northern quadrant of these catalysts, obtained by the use of optically pure diamines, was of greatest importance in introducing enantiomeric excess into the products of ring-opening of 1,2-dioxines; namely gamma-hydroxy enones, and chirality in the southern and peripheral quadrants was of lesser, although still significant, importance. The reaction conditions were optimised and the conditions under which the highest enantiomeric excess was introduced were determined. The ideal solvent for the ring-opening was found to be THF with a catalyst concentration between 5 and 10 mol% at a temperature of -15oC. These conditions were found to be applicable to all catalysts and 1,2-dioxines tested. Enantiomeric excess as high as 76 % could be introduced when the optimised reaction conditions were used in large scale syntheses of cyclopropane (61). LC-MS studies indicate the presence of a solvent chelated species present in the reaction mixture when the solvent used is THF, however, the use of non-chelating solvents, such as dichloromethane, did not exhibit this same solvent chelated species. Catalyst dimers were also present in the mixture when analysed by LC-MS. The presence of oxygen in the reaction mixture was found to inhibit rearrangement of the dioxine with catalyst oxygen dimers (two molecules of catalyst bound to a single molecule of oxygen) present when analysed by LC-MS, however, the catalyst could be 're-activated' by de-aeration of the solution and was able to introduce the same enantiomeric excess, as prior to the addition of oxygen was unaffected. It was found that not only cobalt(II) tetradentate complexes were useful in the ring-opening of meso 1,2-dioxines. Achiral iron(II) salen and ruthenium(II) salen were also made and shown to be capable of ring-opening the dioxine. A purchased chiral manganese(III) salen was also shown to be capable of ring-opening the 1,2-dioxine, however, the time taken for the rearrangement to occur led to ring closure of the gamma-hydroxy enone and dehydration of the cyclic hemiacetal. The catalysts were also applied to the enantioselective ring-opening of epoxy-1,2-dioxines for the first time with a high level of success with enantiomeric excesses of between 60 and 90 % introduced with most of the catalysts. To show that these catalysts have the potential for use in the synthesis of potentially bioactive cyclopropyl amino acids, amines, acids and alcohols a small number were prepared, including both racemic and optically enriched or optically pure cyclopropanes. / Thesis (Ph.D.)--School of Chemistry and Physics, 2003.

Cette thèse a pour but d'apporter une contribution à la compréhension des mécanismes de dégradation d'une résine organique thermodure soumise à un vieillissement thermo-radiatif. Les conditions de vieillissement sont un rayonnement gamma d'intensité 2 kGy/h à une température de 120°C, sous air. la durée de vie requise est de 4 ans, ce qui implique une dose cumulée de 70 MGy.<br />La première étape de l'étude concerne le choix bibliographique d'une résine époxy intrinsèquement résistante aux rayonnements. Cette résine a été retenue sur des critères d'aromaticité et de température de transition vitreuse élevée. Une fois la résine formulée, la deuxième étape a été dédiée au suivi des propriétés thermiques et mécaniques sous l'influence de vieillissements thermiques et radiochimiques :<br />i) sous vieillissements thermiques, il est apparu que la température de transition vitreuse reste constante après 600 heures à 220°C. Par contre, une fragilisation mécanique a été observée amenant à une forte diminution des propriétés à rupture. Cette fragilisation a été attribuée à une épaisseur de couche oxydée critique de l'ordre de 30 µm.<br />ii) sous vieillissements radiochimiques, la même fragilisation a été constatée avec une épaisseur de couche oxydée critique similaire. Il est apparu, de plus, une diminution de la température de transition vitreuse avec la dose d'irradiation. Ceci indique que le mécanisme prépondérant de dégradation de la résine est la coupure de chaîne sous atmosphère anaérobie. Un schéma mécanistique associé à un schéma cinétique a été proposé pour décrire l'évolution de la température de transition vitreuse en fonction des conditions d'irradiation. Les paramètres du modèle cinétique ont été identifiés par RMN du solide et RPE. Le modèle a été validé pour deux débits de dose à 120°C. L'accord global entre les valeurs calculées et expérimentales est satisfaisant.

The mechanical property of polymeric materials changes over time, especially when they are subjected to long-term loading scenarios. To predict the time-dependent viscoelastic behaviors of epoxy-based adhesive materials, it is imperative that reliable accelerated tests be developed to determine their long-term performances under different exposed environments. A neat epoxy resin system and a commercial structural adhesive system for bonding aluminum substrates are investigated. A series of moisture diffusion tests have been performed for more than three months in order to understand the influence of the absorbed moisture on creep behavior. The material properties, such as elastic modulus and glass transition temperature, are also studied under different environmental conditions. The time-temperature superposition method produces a master curve allowing the long-term creep compliance to be estimated. The physics-based Coupling model is found to fit well the long-term creep master curve. The equivalence of the temperature and moisture effect on the creep compliance of the epoxy adhesives is also addressed. Finally, a methodology for predicting the long-term creep behavior of epoxy adhesives is proposed.

The structure-property relationships of epoxy nanocomposites with inorganic layer-structure nanofillers have been studied to obtain the fundamental understanding of the role of nanofillers and the physics of polymer nanocomposites in this dissertation. Several polymer nanocomposite systems with modified montmorillonite (MMT) or α-zirconium phosphate (ZrP) nanofillers were prepared with epoxy matrices of different ductility and properties. The successful nanofiller's exfoliations were confirmed with X-ray diffraction and transmision electronic microscopy (TEM). Dynamic mechanical analysis (DMA) on the prepared epoxy nanocomposites revealed the significant increase in rubbery plateau moduli of the epoxy nanocomposite systems above Tg, as high as 4.5 times, and tensile test results showed improved modulus by the nanofiller addition, while the fracture toughenss was not affected or slightly decreased by nanofillers. The brittle epoxy nanocomposite systems were toughened with core shell rubber (CSR) particles and showed remarkable increase in fracture toughness (KIC) value up to 270%. The CSR toughening is more effective at ductile matrices, and TEM observation indicates that major toughening mechanisms induced by the CSR addition involve a large scale CSR cavitation, followed by massive shear deformation of the matrix.

The flexible substrate was fabricated by BaTi4O9 mixed with O-Cresol Novolac Epoxy, polyether imide or surface active agents. The electrical and physical characteristic measured had been finished. The dielectric property influence of substrate was changed from percentage of BaTi4O9. The dielectric constant model was used by Jayasundere and Smith equation (J. S. eq.) and Lichtenecker equation (L. eq.) The study of crystalline grain, orientation and phase transfer temperature was used by SEM, XRD, and DSC, respectively. The dielectric constant and dielectric loss tangent of the composite was measured using an HP4294A impedance analyzer. The TM mode calculated by resonate frequency of the composite was measured using an HP4156C network analyzer. The dielectric constant was obtained to TM mode at high frequency. The result was showed that dielectric constant at low frequency of BaTi4O9, OCN Epoxy and PEI are 57, 5.8 and 3.65, respectively. OCN Epoxy is better than PEI of electrical characteristic. However, OCN Epoxy is not flexible. For this reason, the PEI was focused on electrical property at high frequency. The BaTi4O9 exhibited a dielectric constant of 39 at frequency during 3~10 GHz. The dielectric constant was measured of 10 at frequency during 2~16 GHz with 70 wt% PEI composite. The dielectric constant is higher than FR-4 substrate to 6.4 of the composite. The low dielectric constant is obtaining to reduce stuffing.