Phenol formaldehyde (PF) resol resins have long been used widely as wood adhesives due to their excellent bonding performance, water resistance and durability. With the growing concern for fossil fuel depletion and climate change, there is a strong interest in exploring renewable biomass materials as substitutes for petroleum-based feedstock. Bark, rich in phenolic compounds, has demonstrated potential to partially substitute phenol in synthesizing bio-based PF resins. In this study, acid-catalyzed phenol liquefaction and alkaline extraction were used to convert mountain pine beetle (MPB; Dendroctonus ponderosae) infested lodgepole pine (Pinus contorta) barks to phenol substitutes, liquefied bark and bark extractives. Two types of bio-based phenol formaldehyde (PF) resol resins, namely liquefied bark-PF resin and bark extractive-PF resins, were then synthesized and characterized. It was found that acid-catalyzed phenol liquefaction and alkaline extraction were effective conversion methods to obtain phenol substitute with the maximum yield of 85% and 68%, respectively. The bio-based PF resol resins had higher molecular weights, higher polydispersity indices, shorter gel times, and faster curing rates than the lab synthesized control PF resin without the bark components. Based on the lap-shear tests, the bio-based PF resol resins exhibited comparable wet and dry bonding strength to lab PF resin and commercial PF resin. The post-curing thermal stability of the bio-based PF resins was similar to the lab control PF resin. The liquid-state 13C nuclear magnetic resonance (NMR) study revealed significant influences on the resin structures by the inclusion of the bark components. Methylene ether bridges, which were absent in the lab PF resin, were found in the bio-based PF resins. The bark components favored the formation of para-ortho methylene linkages in the bio-based bark extractive-PF resins. The liquefied bark-PF resin showed a higher ratio of para-para/ortho-para methylene link (-CH2-), a higher unsubstituted/substituted hydrogen (-H/-CH2OH) ratio and a higher methylol/methylene (-CH2OH/-CH2-) ratio than the bark extractive-PF resin. Both tannin components of bark alkaline extractives and phenolated barks contributed to the acceleration of the curing rate of the bio-based resins. This research demonstrated the promise of the bio-based PF resins containing either bark alkaline extractives or liquefied barks as environmentally friendly alternatives to PF adhesives derived solely from fossil fuel based phenol and proposed a novel higher value-added application of the largely available barks from the mountain pine beetle-infested lodgepole pine trees.

Phenol formaldehyde (PF) resol resins have long been used widely as wood adhesives due to their excellent bonding performance, water resistance and durability. With the growing concern for fossil fuel depletion and climate change, there is a strong interest in exploring renewable biomass materials as substitutes for petroleum-based feedstock. Bark, rich in phenolic compounds, has demonstrated potential to partially substitute phenol in synthesizing bio-based PF resins. In this study, acid-catalyzed phenol liquefaction and alkaline extraction were used to convert mountain pine beetle (MPB; Dendroctonus ponderosae) infested lodgepole pine (Pinus contorta) barks to phenol substitutes, liquefied bark and bark extractives. Two types of bio-based phenol formaldehyde (PF) resol resins, namely liquefied bark-PF resin and bark extractive-PF resins, were then synthesized and characterized. It was found that acid-catalyzed phenol liquefaction and alkaline extraction were effective conversion methods to obtain phenol substitute with the maximum yield of 85% and 68%, respectively. The bio-based PF resol resins had higher molecular weights, higher polydispersity indices, shorter gel times, and faster curing rates than the lab synthesized control PF resin without the bark components. Based on the lap-shear tests, the bio-based PF resol resins exhibited comparable wet and dry bonding strength to lab PF resin and commercial PF resin. The post-curing thermal stability of the bio-based PF resins was similar to the lab control PF resin. The liquid-state 13C nuclear magnetic resonance (NMR) study revealed significant influences on the resin structures by the inclusion of the bark components. Methylene ether bridges, which were absent in the lab PF resin, were found in the bio-based PF resins. The bark components favored the formation of para-ortho methylene linkages in the bio-based bark extractive-PF resins. The liquefied bark-PF resin showed a higher ratio of para-para/ortho-para methylene link (-CH2-), a higher unsubstituted/substituted hydrogen (-H/-CH2OH) ratio and a higher methylol/methylene (-CH2OH/-CH2-) ratio than the bark extractive-PF resin. Both tannin components of bark alkaline extractives and phenolated barks contributed to the acceleration of the curing rate of the bio-based resins. This research demonstrated the promise of the bio-based PF resins containing either bark alkaline extractives or liquefied barks as environmentally friendly alternatives to PF adhesives derived solely from fossil fuel based phenol and proposed a novel higher value-added application of the largely available barks from the mountain pine beetle-infested lodgepole pine trees.

The resin transfer molding (RTM ) process, in which a thermosetting resin is injected into a mold cavity preloaded with a porous fiber preform, is a manufacturing method for producing advanced continuous fiber reinforced composite products with complex geometries. Numerical simulation of resin transfer molding process is an often needed tool in manufacturing design, in order to analyze the process before the mold is constructed. In this study, a numerical simulation of the resin impregnation process in RTM of composite materials is performed by using and modifying an existing simulation program. The parts that are molded in the simulations have their planar dimensions much larger than their thicknesses. Therefore, the mold filling process can be modeled as two dimensional by neglecting the variations along the thickness direction. The program is capable of simulating two-dimensional, isothermal impregnation processes through orthotropic fiber preforms of planar but complex geometries. The formulations of the physical problem, used in this study, were taken from the theory of macroscopic flow through anisotropic porous media. The formulated governing equation and boundary conditions are solved in a regular-geometry computational domain by transformation through boundary fitted coordinate system. The discretization for numerical solution is performed by the finite difference method. The current study extends the existing capabilities of the simulation program by enabling the simulation of impregnation through non-homogeneous fiber preforms. Furthermore, the capability to simulate injection from two gates (as opposed to a single gate injection that existed before) is developed and added to the program. Various one-dimensional impregnation simulations (as parametric studies) are performed to assess the influence of process parameters. Results are also compared with analytical solutions and found to be in agreement with them. Two-dimensional impregnation simulations are performed for a planar, complex geometry mold. The two-dimensional results are compared with experimental results from the literature and are found to be in acceptable agreement with them. In addition to the study of various parametric variations in two-dimensional impregnation, double-gate resin injection simulations are performed and discussed as well.

A aplicação de uma ou mais camadas de tinta sobre as superfícies metálicas é a maneira mais comum e eficaz de proteger os substratos metálicos contra o fenômeno da corrosão. No entanto, os sistemas de pintura podem vir a falhar precocemente por diferentes motivos, causando um ataque corrosivo inesperado no metal a ser protegido. Por esta razão, o processo de repintura em estruturas metálicas é realizado frequentemente para garantir a integridade da estrutura pintada e aumentar sua vida útil. Como o processo de repintura gera impactos econômicos e ambientais, sistemas de pintura capazes de sofrerem uma reparação sem a necessidade de uma intervenção humana, precisam ser desenvolvidos. O encapsulamento de agentes de reparação, com propriedades de formação de filme, em microcápsulas poliméricas é uma excelente alternativa para que os sistemas de pintura se autorreparem, aumentando os intervalos de repintura. Após o processo de encapsulamento, as microcápsulas contendo o agente de reparação são incorporadas na preparação da tinta, para que o sistema de pintura seja aplicado sobre a estrutura metálica. Este tipo de aditivação confere ao revestimento a propriedade de autorreparação, pois quando o sistema de pintura é danificado as microcápsulas são rompidas e liberam o agente de reparação no local danificado, protegendo novamente o substrato metálico. Neste trabalho foi desenvolvido um sistema autorreparador monocomponente, através do microencapsulamento de uma resina a base de éster de epóxi, pelo método de polimerização in-situ. Também foi desenvolvido um sistema autorreparador bicomponente, através do microencapsulamento de uma resina a base de epóxi, pelo método de emulsão e polimerização in-situ de ureia-formaldeído-melamina e do seu endurecedor a base de poliamida, pelo método de extração de solvente em paredes de poliestireno. Foi realizado um planejamento estatístico para estudar a emulsão precursora das microcápsulas de poli(ureia-formaldeído-melamina) contendo o sistema monocomponente, onde foram estudados: o tipo e a velocidade de agitação, a presença de cloreto de sódio na formulação, o uso de uma sonda ultrassônica após a etapa de dispersão, a concentração de tensoativo na formulação e o tensoativo utilizado. Como variáveis de resposta foram determinadas: a estabilidade visual das emulsões e o diâmetro das gotículas formadas. A melhor condição de emulsificação determinada foi utilizada para a obtenção das microcápsulas de poli(ureia-formaldeídomelamina) contendo a resina éster de epóxi e das microcápsulas de poli(ureiaformaldeído-melamina) contento a resina epóxi. Entre as condições de emulsificação estudadas, apenas a condição utilizando o tensoativo goma arábica possibilitou a obtenção das microcápsulas de poli(ureia-formaldeído-melamina) na faixa de diâmetro desejada. O método escolhido para o encapsulamento do endurecedor possibilitou a obtenção de microcápsulas de poliestireno, porém com uma baixa capacidade de armazenamento. A liberação dos agentes de reparação encapsulados foi observada pela microscopia óptica e comprovada pela técnica de espectroscopia na região do infravermelho (FTIR) e pela técnica de espectroscopia Raman. Os aditivos autorreparadores desenvolvidos (mono e bicomponente) foram adicionados separadamente em uma tinta epóxi, nas proporções mássicas em base seca de 10 e 15 %. O sistema de pintura foi aplicado em um esquema de três camadas e o aditivo de autorreparação foi incorporado na primeira e/ou segunda camada aplicada. O sistema de pintura contendo o aditivo autorreparador monocomponente apresentou um aspecto visual melhor do que o sistema de pintura contendo o aditivo autorreparador bicomponente, porém o sistema bicomponente forneceu melhores propriedades de aderência, de impermeabilidade, anticorrosivas e de autorreparação à tinta aditivada. As medidas com as técnicas eletroquímicas de espectroscopia de impedância eletroquímica (EIE) e de varredura com eletrodo vibratório (SVET) comprovaram que os dois aditivos desenvolvidos proporcionaram o efeito autorreparador aos sistemas de pintura aditivados, quando estes foram danificados mecanicamente com uma microbroca ou com um estilete. Ensaios acelerados de corrosão em câmara de névoa salina e ensaios de exposição ao intemperismo natural mostraram que os aditivos desenvolvidos promoveram uma proteção adicional ao aço carbono, quando o sistema de pintura foi danificado mecanicamente. / The application of one or more coating layers on the metallic surfaces is the most common and effective way to protect metallic substrates against corrosion. Nevertheless, the coating layer may fail early for different reasons, leading to an unexpected corrosive attack on the protected metal. For this reason, the coating repair process is performed to ensure the integrity during the service life of the coated metallic structures. Due to the fact that coating repair process generates economic and environmental impacts; there is a great need for the development of systems capable to repair themselves, without human intervention. The encapsulation of repairing agents, with film forming properties, in polymeric microcapsules is an excellent alternative to the coating self-repair, decreasing the coating repair process frequency. After the encapsulation process, the microcapsules containing the repair agent are incorporated into the paint preparation and the coating system could be applied normally to the metallic surface. This kind of additivation confers to the coating the self-healing property, because when the coating system is damaged the microcapsules suffers a rupture and release the repair agent into the damaged site, protecting the metallic substrate from corrosion. In this work, a mono-component self-healing system was developed, through the microencapsulation of an epoxy ester resin, by the in-situ polymerization method. A bi-component self-healing system was also developed, by the microencapsulation of an epoxy resin, through the emulsion and in-situ polymerization method and by the microencapsulation of a polyamide hardener, by the double emulsion and solvent extraction method. A factorial design was developed to study the precursor emulsion of the poly (urea-formaldehyde-melamine) microcapsules containing the monocomponent system, where the studied factors were: the type and speed of the agitation, the presence of sodium chloride in the formulation, the use of an ultrasonic probe after the emulsification, the surfactant type and concentration. The analyzed response variables were: the visual stability of the emulsions and the mean diameter of the formed droplets. The best obtained emulsification conditions were employed to produce the poly(urea-formaldehyde-melamine) microcapsules containing the epoxy ester resin and poly(urea-formaldehyde-melamine) microcapsules containing the epoxy resin. Among the studied emulsification conditions, only using arabic gum surfactant the poly (urea-formaldehyde-melamine) microcapsules were obtained. The selected method for the hardener encapsulation was efficient to obtain polystyrene microcapsules, but with low loading capacity. The release of the encapsulated repair agents was observed by optical microscopy and confirmed by infrared spectroscopy (FTIR) technique and Raman spectroscopy technique. The developed self-healing additives (mono and bicomponent) were added separately in an epoxy commercial coating, using the dry mass ratios 10% and 15 %. The coating system was applied in a three layer coating system and the self-healing additive was incorporated into the first and/or second layer. The coated samples containing the mono-component additive had a better visual appearance than the bi-component additive system; nevertheless the bi-component system provided better adhesion, impermeability, anti-corrosion and self-healing properties to the doped coating. The electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET) measurements proved that the two developed additives provided self-healing properties to the doped coating systems, when they were mechanically damaged with a micro drill or a blade. Accelerated corrosion tests in the salt spray chamber and natural atmospheric corrosion tests showed that the developed additives provided an additional protection to the carbon steel, when the coating system has been mechanically damaged.

Muitas das lesões dentárias necessitam de restaurações indiretas que requerem cimentos adesivos para a sua fixação à estrutura dentária. Em algumas situações não é possível realizar o isolamento absoluto do campo operatório, o que pode levar à contaminação com saliva da dentina previamente aos procedimentos adesivos. Assim é necessário saber o nível de comprometimento da adesão em função deste fato. O presente estudo teve como objetivo analisar o tratamento da dentina contaminada com saliva na resistência adesiva dos cimentos resinosos convencional e autoadesivo através de testes de cisalhamento. Foram utilizados 50 incisivos bovinos que foram lixados até a exposição de dentina superficial e divididos em 6 grupos: Grupo ARC (controle): condicionamento ácido por 15s + sistema adesivo Scotchbond Multipurpose (3M/ESPE) + cimento RelyX ARC (3M/ESPE); Grupo ARClav: condicionamento ácido por 15s + contaminação com saliva + lavagem com água/ar 20 segundos + sistema adesivo + cimento RelyX ARC; Grupo ARCsec: condicionamento ácido por 15s + contaminação com saliva + secagem com papel absorvente + cimento autoadesivo RelyX ARC; Grupo ARCre: condicionamento ácido por 15s, contaminação + secagem jato de ar + recondicionamento por 15s + sistema adesivo Scotchbond Multipurpose + cimento RelyX ARC; Grupo U100 (controle): sem contaminação + cimento autoadesivo RelyX U100 (3M/ESPE); Grupo U100sec: contaminação + secagem jato de ar + cimento autoadesivo RelyX U100. Após a cimentação, os dentes foram armazenados em água destilada a 37ºC por 24 horas antes da realização do teste de cisalhamento. Os resultados obtidos foram submetidos à análise de variância a dois critérios e teste de Tukey com nível de significância de 5%. As médias gerais, dos grupos,expressas em MPa, foram G ARC: 9,02 ± 1,36 - G U100: 4,38 ± 0,74 - GARClav: 6,43 ± 0,98 GARCsec: 7,71 ± 1,14 GARCre: 5,68 ± 1,10 G U100sec: 3,87 ± 0,51. A análise dos resultados permitiu concluir que a adesão do cimento RelyX à dentina contaminada com saliva, lavada ou recondicionada com ácido fosfórico diminui significantemente quando comparada à adesão à dentina não contaminada ou àquela contaminada e apenas seca com papel absorvente. Já a contaminação com saliva não afetou significantemente a adesão do cimento RelyX U100 à dentina. / Many dental injuries require indirect restorations fixed by adhesive cements. In some situations is not possible to isolate the operative field, which can lead to contamination by saliva of the dentin. The aim of this study was to analyze the treatment of dentin contaminated with saliva on shear bond strength of conventional and self-adhesive resin cements. Fifty bovine incisors were ground until exposure of dentin surface and divided into six groups: Group ARC (control) no contamination + acid etch for 15s + Scotchbond Multipurpose system (3M/ESPE) + cement Rely X ARC (3M/ESPE); Group U100 (control): no contamination + self-adhesive cement RelyX U100 (3M/ESPE), Group ARClav: acid etch for 15s + saliva contamination + rising with water / air + adhesive system RelyX ARC, Group ARCsec: acid etch + contamination with saliva + drying with absorbent paper cement RelyX ARC, Group ARCre: acid etched, contamination with saliva + drying with absorbent paper + reetched for 15s + adhesive system Scotchbond Multipurpose + cement RelyX ARC, Group U100sec: contamination + drying with absorbent paper + self-adhesive cement RelyX U100. After cementation, the teeth were stored in distilled water at 37° C for 24 hours prior to shear testing. The results were analyzed by One-way ANOVA and Tukey\'sTests with a significance level of 5% were: G ARC: 9.02 ± 1.36 G U100: 4.38 ± 0.74 G ARClav: 6.43 ± 0.98 G ARCsec: 7.71 ± 1.14 G ARCre: 5, 68 ± 1.10 G U100sec: 3.87 ± 0.51.The results showed that there was a significant difference in bond strength of RelyX ARC to dentin contaminated by saliva when it was rinsed or re-etched, but there was no difference when the contaminated dentin was just dried with absorbent paper. No statistical difference was found between the adhesion resistance of the RelyX U100 to dentin with or without saliva contamination.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Nos Ãltimos anos, houve um acelerado desenvolvimento na Ãrea de compÃsitos reforÃados por fibras naturais, como (juta, sisal, coco, linho etc.) Fibras naturais sÃo uma importante alternativa, pois apresentam as seguintes vantagens: abundÃncia, biodegrabilidade, baixo peso, regenerabilidade, nÃo sÃo tÃxicas, apresentam baixo custo de aplicaÃÃo comparado com as fibras sintÃticas e podem ser modificadas por tratamento quÃmico. O presente trabalho teve por objetivo a preparaÃÃo e caracterizaÃÃo de compÃsitos suportados, em matriz fenÃlica derivadas do LCC, reforÃados por fibras naturais de coco e juta. Foram conduzidas modificaÃÃes superficiais nas fibras atravÃs de tratamento alcalino (mercerizaÃÃo) NaOH nas concentraÃÃes 5% e 10% (75 0C) e branqueamento com hipoclorito de sÃdio (NaClO/H20 1:1) (60 0C). Os compÃsitos foram preparados por moldagem aberta com fibras de coco e juta para todos os tratamentos. As propriedades mecÃnicas, tÃrmicas, dielÃtricas bem como as investigaÃÃes superficiais das fibras antes e apÃs o tratamento quÃmico e interface dos compÃsitos foram investigados pelas tÃcnicas de ensaios de traÃÃo (elongaÃÃo à ruptura, mÃdulo elÃstico, resistÃncia à ruptura); TG/DTG (Termogravimetria/Derivada); DSC (Calorimetria ExploratÃria Diferencial); DRX (Difratograma de Raios X); propriedades dielÃtricas, (Perda DielÃtrica, Condutividade DielÃtrica) e MEV (Microscopia de Varredura EletrÃnica). Fibras de coco, juta e compÃsitos apresentaram um aumento global das propriedades mecÃnicas apÃs o tratamento quÃmico com NaOH 5% e 10% .Os melhores resultados foram aqueles observados para os compÃsitos de juta apÃs tratamento com NaOH 5% onde se observou um aumento de 28% na resistÃncia à ruptura, jà para os compÃsitos de coco os melhores resultados foram os apÃs tratamento com NaOH 10% com aumento de 48%. Os resultados de anÃlise termogravimÃtrica em atmosfera inerte mostraram processos de estabilidade tÃrmica para as fibras e compÃsitos apÃs o II tratamento quÃmico com NaOH 5% e 10 % respectivamente. Para as fibras de juta observou-se um aumento de (218-228 0C) para as de coco o aumento foi de (259- 276 0C). Os compÃsitos de juta e coco tambÃm apresentaram um aumento na estabilidade tÃrmica apÃs o tratamento quÃmico, onde os melhores resultados obtidos foram: compÃsitos de juta (302-3060C) apÃs tratamento com NaOH 5%, e os de coco (288-310 0C) apÃs tratamento com NaOH 10%. Esses resultados comprovaram que o tratamento alcalino de fato proporcionou uma melhora da estabilidade tÃrmica dos compÃsitos. As anÃlises de investigaÃÃo superficial das fibras de juta e coco apresentaram claramente modificaÃÃes estruturais como conseqÃÃncia da remoÃÃo parcial de constituintes apÃs o tratamento quÃmico. Para os compÃsitos dessas fibras, foi observado que apÃs o tratamento quÃmico, com a remoÃÃo de componentes nÃo celulÃsicos, ocorreu de fato uma melhor adesÃo, ou seja, interface agente de reforÃo/matriz fenÃlica. / In recent years there was a rapid development in the field of composites reinforced by natural fibers like (jute, sisal, coir, hemp etc). Natural fibers are an important alternative, offering several advantages such their abundant, biodegrability, light weight, renewability, are not toxic, presents low cost application compared with synthetic fibers and may be easily modified by chemical treatment. The present work aimed the study, preparation and characterization of composites of phenolic resin (matriz) based on CNSL, reinforced by natural fibers of coir and jute. Superficial modification on the fibers were carried out through alkali treatment (mercerization) NaOH 5% and NaOH 10% (75 0C) and bleaching with sodium hipoclorite (NaClO/H20 1:1) (60 0C). All the fibers composites were prepared by open mold. The composites and fibers were characterized by analysis techniques such mechanical tensile strength (elongation at break, youngâs modulus, resistant at break); TG/DTG (Thermogravimetry); DSC (Differential Scanning Calorimetric); DRX (Difractrogram X - Ray); dielectric properties (Dielectric Conductivity, Dielectric Loss) and SEM (Scanning Electron Microscopy) investigation on the surface modification in fibers and composites after chemical treatment. The results to coir and jute fibers composites showed an increase of mechanical properties. The best mechanical performance was generally obtained for composites of jute and coir after NaOH 5% and NaOH 10% showing an enhancement of mechanical properties resistant at break (28%) and (48%) respectively. IV The thermal degradation behavior of composites and coir - jute fibers under a nitrogen atmosphere showed an increase of thermal stability after alkaline treatment NaOH 5% e 10 % compared with untreated fibers. To jute fibers it was observed an improvement of (218-228 0C) to coir fibers this increased it was (259- 276 0C). The same thermal stability was evaluated to composites of theses fibers after alkaline treatment NaOH 5% and NaOH 10%. To jute fibers composites the best results were (302-3060C) while coir composites were (288-310 0C). From the results obtained, it is possible to conclude that alkaline treatment contribute to significant improvement of thermal behaviour of the composites The SEM investigation showed significant improvement on surfaces of jute and coir fibers after chemical treatment. The alkali treatment, removed non-celluloic components from fibers surface, expoding their internal fibrillar structure. As a consequence the treatment promoted an increase on interfacial adhesion between coir and jute fibers reinforced phenolic resin composite.

The high functionality epoxy resins tetraglycidyl-4,4’-diaminodiphenyl-methane(TGDDM) and triglycidyl-p-aminophenol (TGPAP) are the main components in most aerospace grade epoxy resin formulations. Owing to their high reactivity and high viscosity, TGDDM and TGPAP pose difficulties when used in wet layup composite manufacturing. As such, these resins are often modified to achieve the desired performance both in the liquid and cured states. The main objective of this thesis is to optimise a low viscosity multi-component epoxy resin formulation suitable for use as an aerospace grade composite matrix. The formulation will allow for the addition of high levels of thermoplastic to improve the fracture toughness of the resin whilst also maintaining resin processability. Through the use of thermal analytical techniques this thesis aims to study the effects of varying the TGDDM/TGPAP ratio, incorporation of a low viscosity bi-functional epoxy resin, the diglycidyl ether of bisphenol F (DGEBF) and changes to the stoichiometric ratio (r)between reactive groups of the epoxy resin and amine hardener (4,4’-diaminodiphenylsulphone, DDS) in multi-component epoxy resin formulations. Resin formulations were optimised using factorial experimental design (FED). Results from two FED’s showed curing multi-component resins at a low stoichiometric ratio significantly increased the processing window whilst also increasing the glass transition temperature (Tg) of the cured resin. No apparent benefit could be assigned to the inclusion of TGDDM owing to its poor processability and a Tg similar to TGPAP. Up to 60% DGEBF was incorporated in a multi-component resin formulation whilst still attaining a Tg greater than 220°C. Its inclusion at 60% had the additional benefit of increasing the processing window by 48 minutes over TGPAP, an increase of 62%. Two optimised resin formulations, 100% TGPAP (100T) and a binary mix of 60% DGEBF and 40% TGPAP (60D) were taken forward to study the effects of adding a thermoplastic toughener (polyethersulphone, PES) in incremental amounts up to 50wt%. SEM images showed all toughened 100T resins had a phase separated morphology whilst all 60D resins were homogenous. The phase separation seen in 100T did not improve the matrix fracture toughness when loaded at 10 wt% and 30 wt% PES. Only when 50 wt% PES was added did fracture toughness increase in comparison to the homogenous 60D resins. Through factorial experimental design two epoxy resin formulations which excluded TGDDM were optimised with a low stoichiometric ratio. The optimum aerospace formulation is dependent on the desired processability and fracture toughness of the resin. High DGEBF-containing formulations give the longest processing windows whilst the 100% TGPAP formulation toughened with 50% PES has the highest fracture toughness.

O presente estudo hipotetiza que cimentos resinosos com diferentes sistemas de ativação e mecanismo de condicionamento da estrutura dentária, têm a mesma resistência adesiva a uma cerâmica. Objetivos: avaliar a resistência de união de agentes de fixação resinosos, cimento resinoso autopolimerizável (C&B- Bisco), dual (Panavia F- Kuraray) e auto-adesivo (Relyx U-100-3M ESPE) frente a uma cerâmica a base de dissilicato de lítio (IPS Empress-Ivoclar Vivadent). Metodologia: nove blocos de cerâmica e 9 de compósito foram confeccionados com dimensões 6mmx6mmx6mm e fixados por meio de um agente de fixação resinoso (Panavia F, C&B, RelyX U-100). As superfícies da porcelana e do compósito foram tratadas, o sistema adesivo e o agente de fixação resinoso foram aplicados. O bloco de compósito foi posicionado e foi realizada a fotoativação, por quarenta segundos, em cada face dos blocos. Todas as amostras foram armazenadas em água deionizada a 37C por vinte e quatro horas. As amostras foram fixadas às placas de acrílico e seccionadas em uma cortadeira metalográfica. Foram obtidas fatias em forma de palito com 1mm de espessura, num total de 15 por grupo. Decorrido trinta dias foram submetidos ao ensaio de microtração em uma máquina de ensaio universal Kratos e os resultados analisados estatisticamente. O padrão de fratura foi analisado em lupa estereoscópica, classificados quanto ao tipo. Resultados: O cimento de dupla cura (Panavia F) apresentou maior resistência adesiva. O cimento auto-adesivo (Relyx U- 100- 3M ESPE) apresentou adesão inferior aos outros cimentos do estudo. A maioria das fraturas ocorreu dentro da zona adesiva, caracterizando a eficiência e confiabilidade deste teste, na avaliação dos cimentos. Conclusões: O agente de fixação auto-adesivo apresentou adesão inferior aos outros e o cimento dual se apresentou um pouco melhor que o quimicamente ativado. / This study hypothesized that resin cements with different activation modes and mechanisms have the same bond strength towards ceramic interface. Objectives: To evaluate the tensile bond strength of resin-fixing agent, self cured resin cement (C & B, Bisco), dual cement (Panavia, Kuraray) and self-adhesive (Relix U-100) towards the base of a ceramic of lithium disilicate (IPS-Empress Ivoclar Vivadent). Methodology: Nine blocks of ceramics and composite resins were prepared with dimensions 6mmx6mmx6mm. The surface of the porcelain and the composite was treated and the fixing agent (Panavia, C & B, ReLyX U-100), was applied. The composite block was photopolymerized for forty seconds on each side of the block. All samples were stored in deionized water at 37C for twenty-four hours. Afterwards, samples were cut to form matchstick slices 1mm -thick, with a total de 15 per group (n=15). The samples were submitted to microtensile testing at a Kratos universal testing machine (0.05mm/min) and the results were analyzed statistically. The pattern of fracture was observed in stereoscopic and classified. Result: The dual-cure cement (Panavia F) showed higher bond strengths whereas the self-adhesive cement (Relyx U-100) showed the lowest bond strength among groups. Most of the fracture occurred inside the adhesive interface, characterizing the efficiency and reliability of this test in the evaluation of cements. Conclusions: The self-adhesive cement exhibited lower bond strength compared to the other agents. The dual cured cement system presented a slightly better performance than the self-cured cement.

abstract: In this study, the stereolithography (SLA) 3D printing method is used to manufacture honeycomb-shaped flat sorbents that can capture CO2 from the air. The 3D-printed sorbents were synthesized using polyvinyl alcohol (PVA), propylene glycol, photopolymer resin, and an ion exchange resin (IER). The one-factor-at-a-time (OFAT) design-of-experiment approach was employed to determine the best combination ratio of materials to achieve high moisture swing and a good turnout of printed sorbents. The maximum load limit of the liquid photopolymer resin to enable printability of sorbents was found to be 44%. A series of moisture swing experiments was conducted to investigate the adsorption and desorption performance of the 3D-printed sorbents and compare them with the performance of IER samples prepared by a conventional approach. Results from these experiments conducted indicate that the printed sorbents showed less CO2 adsorptive characteristics compared to the conventional IER sample. It is proposed for future research that a liquid photopolymer resin made up of an IER be synthesized in order to improve the CO2-capturing ability of manufactured sorbents. / Dissertation/Thesis / Masters Thesis Mechanical Engineering 2020

Work was carried out in collaboration with SYNPO, Inc. Pardubice, which provided samples resins with various additives for measurement. The work is divided into three theoretical and one practical chapters. The first chapter focuses on dielectrics in general. It deals with their properties and storyline running in them. The second chapter discusses epoxy resins, their formulation, production and application in manufacturing. The third chapter offers a view of the measurement methods used for diagnosing electrical dielectrics. The practical part describes the preparation of samples and their composition, and consequently their measurement with the evaluation of measurement data.