Crystallisation of epoxy resins based on bisphenol A and bisphenol F is the natural property of these oligomers. However, manufacturers of paints and other systems based on these epoxy resins, strive to slow down the crystallisation process as much as possible, thereby prolonging the shelf life and improving the competitiveness of their products. The main aim of the thesis is generalisation of the factors influencing the crystallisation process of epoxy resins based on bisphenol A and bisphenol F, verifying new approaches to the possibility of influencing the crystallisation process and determining the possibility of using a certain degree of epoxy resins crystallinity based on bisphenol A and bisphenol F in the preparation and production of epoxy resinbased coating systems.

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.

Lastabtragende Klebverbindungen stellen im Konstruktiven Glasbau einen wesentlichen Forschungsgegenstand der vergangenen Jahre dar. Getrieben von gestalterischen Gesichtspunkten sind dabei die transparenten Klebstoffe von besonderem wissenschaftlichem und wirtschaftlichem Interesse. Die vorliegende Arbeit widmet sich ausschließlich der Klebstoffgruppe der zweikomponentigen Epoxidharze, da diese im Konstruktiven Glasbau bisher kaum Beachtung finden. Detaillierte Informationen zu den Eigenschaften und zum Verhalten fehlen fast vollständig und werden innerhalb der vorliegenden Arbeit geschaffen. Die durchgeführten Untersuchungen gliedern sich in die Untersuchungen zur Wahl eines geeigneten Epoxidharzes, in die Untersuchungen der Verarbeitungsbedingungen und in die Charakterisierung der optimierten Klebverbindung. Ferner wurden auch konstruktive Maßnahmen zum Schutz der Klebschicht in die Untersuchungen eingebunden. Innerhalb des Untersuchungsprogramms wurde großer Wert auf eine ausgewogene Gewichtung unterschiedlicher Kriterien gelegt. In die engere Auswahl kamen acht Epoxidharzklebstoffe, die grundlegend untersucht und analysiert wurden. Im Ergebnis konnte ein vielversprechender Klebstoff ausgewählt werden. Die weiterführenden Untersuchungen zu den Verarbeitungsbedingungen hatten die Optimierung des Eigenschaftsprofils zum Ziel. Sowohl die thermische Stabilität des Klebstoffs als auch das Anfangs- und das Restbruchverhalten der Glas-Metall-Verbindungen konnten nennenswert verbessert werden. Ebenso wurde die Wirksamkeit der konstruktiven Schutzmaßnahmen erfolgreich nachgewiesen. Aus den Ergebnissen und deren Wertung konnten abschließend Handlungsempfehlungen für den Einsatz transparenter Epoxidharze in Glastragwerken abgeleitet werden. Die sich nach den eigenen Untersuchungen ergebenden, weiteren offenen wissenschaftlichen Fragestellungen und deren zugehöriger Forschungsbedarf werden am Ende ebenfalls erörtert.

No description available.

[pt] Um tipo de resina epoxídica (RE) foi modificada com polibutadieno líquido hidroxilado (PBLH) a partir da mistura física de ambos os componentes (EPH) ou a partir da obtenção de copolímeros em bloco da resina epoxídica com PBLH funcionalizado com grupos isocianato (EPI) e carboxila (EPA). Foi realizado um estudo do comportamento mecânico desses sistemas epoxídicos, após a cura com um endurecedor a base de aminas, antes e após envelhecimento. Também foram avaliadas as propriedades adesivas, antes e após envelhecimento, através de ensaios com juntas de topo e juntas sobrepostas simples fabricadas com esses adesivos e com substratos de aço. O estudo do envelhecimento abrangeu absorção de água a temperatura ambiente e envelhecimento térmico. Foi possível concluir que a condição de pós-cura estabelecida em um trabalho anterior não acarretou na densidade máxima de ligações cruzadas dos sistemas e isto afetou o comportamento dos mesmos após os envelhecimentos. Para as condições de cura e pós-cura aplicadas, a água, no período de tempo estudado, acarretou na plastificação dos sistemas, mas não afetou as propriedades adesivas das juntas fabricadas com os adesivos RE, EPA e EPI. Já o tratamento de envelhecimento térmico a 150oC por 7 dias acarretou na queda de algumas propriedades mecânicas, mas teve o efeito distinto de melhorar as propriedades adesivas das juntas fabricadas com EPI, EPH e EPA em relação à carga de ruptura, todavia resultando num aumento da rigidez efetiva dessas juntas. / [en] A kind of epoxy resin was modified with hydroxyl- terminated polybutadiene (HTPB), using a physical blend of both components (EPH) or using a block copolymer of HTPB-RE. The block copolymers were prepared by reacting RE with isocyanate-funcionalized HTPB (EPI) or carboxyl- funcionalized HTPB (EPA). The cure agent was a blend of amines. A study of the mechanical behavior of these systems was carried out, before and after aging. Also the adhesive properties were evaluated, before and after aging, testing bonded joints (both butt and single-lap) manufactured with these adhesives and employing a steel adherent. This ageing study enclosed water absorption, at ambient temperature, and thermal aging. It can be concluded that the condition of post-cure, established in a previous work, did not promote the maximum crosslink density of the systems and this affected the behavior of these systems after aging. Considering the conditions of cure and post-cure and the period of time applied in this work, the water caused the plasticization of the systems, but it did not affect the adhesive properties of the joints manufactured with the adhesives RE, EPA and EPI. Considering the thermal aging treatment at 150oC during 7 days, it caused the decrease of some mechanical properties, but it had the distinct effect to improve the adhesive properties of the joints manufactured with EPI, EPH and EPA regarding the rupture load, however resulting in an increase of the joints stiffness.

Master of Science / Department of Grain Science and Industry / Xiuzhi Susan Sun / Soybean oil-based resin for transparent flexible coating applications were formulated by dihydroxyl soybean oil (DSO) with commercial epoxy monomers (i.e., epoxidized soybean oil (ESO) and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ECHM)). The resin was formed to thermoset polymers using cationic ring-opening photopolymerization. The ether crosslinking and post-polymerization of the polymeric network were observed using Fourier transform infrared spectroscopy. Thermal properties of the bio-based coating materials and their copolymerization behaviors were examined using a differential scanning calorimetry and a thermogravimetric analyzer. Crosslink density and molecular weight between crosslink were obtained from dynamic mechanical analysis. ECHM/DSO (1: 1.43 weight ratio) films showed the highest elongation at break (49.2 %) with a tensile strength of 13.7 MPa. After 2 months storage, the elongation at break and tensile strength of films were 32 % and 15.1 MPa, respectively. ESO/DSO films (w/w ratios of 1:0.1, 1:0.15, and 1:0.2) exhibited stable flexibility around 11-13 % of elongations at break without significant reductions of tensile strengths (2.5 to 4.4 MPa) during 2-months shelf life. Optical transparencies of the films were comparable to commercial glass and polymers, and water uptake properties (0.72 and 2.83%) were significantly low.

The aim of the work reported here was to determine the influence of an amine curing agent, and postcure cycle on the mechanical and thermal properties of diglycidyl ether of bisphenol A (DGEBA) epoxy resin. The results of this initial study were then used as the basis for selecting material to obtain optimum toughness in epoxy/glass fibre systems. These basic materials were further used to make comparisons with the properties of modified resin systems which contained commercial elastomers. Differential Scanning Calorimetry (DSC), Dynamic Mechanical Thermal Analysis (DMTA), Fourier Transform Infrared Spectroscopy (FTIR), flexural and interlaminar shear tests, Instrumented Falling Weight Impact (IFWI), visual observation, Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM) were all used to investigate various properties and the structures which gave rise to them. The properties of cured products were found to be affected by the amounts of curing agent, curing times and temperatures, and the structure of the elastomers. Not surprisingly the maximum thermal and mechanical properties tended to be found in the stoichiometric (standard) mix systems. However, postcuring at higher than room temperature, which was used as the basic curing temperature, led to more conversion. This effect improved the thermal and mechanical properties of both the unmodified and modified resin systems. The maximum flexural strength of 104 MPa of the unreinforced resins was found in the stoichiometric mix ratio after postcure at 150°C for 4 hr. However, the maximum flexural modulus and glass transition temperature (Tg) were found after postcuring at the same temperature for 48 hr. This was believed to be due to increased crosslinking, but unfortunately the longer curing time led to degradation of the resins. In the systems modified with -20 phr of polyetheramine elastomers, the one modified with the lowest molecular weight (2000) was found to have the highest flexural strength (85.8 MPa) and modulus (2.5 GPa). The impact properties of all the composites with modified resin matrices were found to be higher than the unmodified resin matrix composites. The best impact properties were, however, obtained with the elastomer modifier with a molecular weight of 4000. The impact energy at maximum force increased from 11.9 to 16.4 J, and energy at failure increased from 18.7 to 21.6 J. This increase in impact properties was due to the increase in areas of phase separated elastomer particles over similar systems with lower molecular weight modifier.

Nanocompósitos híbridos a base de resinas epoxídicas e argilas organofílicas têm sido desenvolvidos resultando em materiais com características mecânicas e térmicas melhoradas em relação aos compósitos convencionais. Entretanto, a incorporação de argila modificada altera as características reocinéticas de cura do polímero epoxídico ao mesmo tempo em que influencia nas características microestruturais responsáveis pelas propriedades mecânicas finais do compósito. Na literatura poucos estudos foram feitos sobre o efeito da carga nanoestruturada sobre as características reocinéticas de cura e também a aplicação de técnicas analíticas dielétricas que permitam o monitoramento do processo de cura nas condições atuais de trabalho. O estudo das características reocinéticas, dinâmico-mecânicas e dielétricas de compósitos de matriz epoxídica reforçado com argila do tipo montmorilonita organofílica foi realizado neste trabalho. Foram usados três tipos de argilas montmoriloníticas organofílicas comerciais Cloisite, com diferentes agentes modificadores e capacidade de troca iônica. Foi determinado pela análise por calorimetria exploratória diferencial (DSC) que a cinética de cura do sistema epóxi-anidrido, constituído por resina éter diglicidílico de bisfenolA (DGEBA), agente endurecedor anidrido hexahidroftálico (HHPA) e acelerador benzildimetilamina (BDMA), curado em dois estágios de temperatura, a 85 e 150oC, obedece ao modelo cinético de Sourour-Kamal no estágio de 85oC e ao modelo cinético de ordem n no estágio de 150oC. A análise cinética mostrou o efeito de aceleração da cura pelos diferentes tipos e composições de argilas. A análise dinâmico-mecânica (DMA) revelou dois picos nas curvas da tangente de perda, tan d, relacionados com as etapas de reação autocatalítica e de ordem n no estágio de cura a 85oC. Entretanto, os resultados do DMA não evidenciaram o efeito de aceleração da argila sobre a cura dos compósitos. Por outro lado, a análise dielétrica (DEA) apresentou resultados equivalentes aos da análise por DSC, evidenciando o papel de acelerador da cinética de cura da argila organofílica. A difração de raios X mostrou que as argilas sofreram intercalação no processo de cura. Como conclusão, o trabalho mostrou que as técnicas de análise cinética por DSC e DEA podem determinar a influência dos diferentes tipos e composições de argilas organofílicas. Não se determinou a influência específica que um tipo de argila teve sobre as características cinéticas e mecânicas dos compósitos nas composições estudadas. / Hybrid nanocomposites based upon epoxy resin and organophylic clay mixes have been intensively studied because of their better mechanical and thermal properties as compared to conventional composites. Nevertheless when the organoclay is added to the epoxy reactive medium it does affect the thermoset polymer chemorheological behavior. Such interaction can define the composite ultimate mechanical properties. In the literature few works were done concerning the influence of nanostructured filler on the reactive medium chemorheology. Also the use of dielectric analysis as a tool for monitoring and evaluating the curing process of nanostructured composite will be of practical interest because this analytical technique can be used to study the curing process under actual processing condition. The aim of this work is the study of chemorheological, dynamic mechanical, and dielectric analysis of epoxyorganoclay composites. Composites prepared with epoxy-anhydride resin and three different modified organoclays were analysed through differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), dielectric analysis (DEA), and X-ray diffraction. The epoxy system is a diglycidyl ether of bisphenol A (DGEBA) resin, a hexahydrophtalic anhydride as curing agent, and benzyldimethylamine (BDMA) as accelerator mechanically mixed with commercial organoclay Cloisite and heat treated in two stages: one, at 85oC where the chemical reaction occurs; and a second higher temperature stage, at 150oC, where the full cure is attained. The kinetics analysis revealed that the lower temperature cure obeys the Sourour-Kamal model, whereas the higher temperature post cure stage follows the order n model kinetics. The kinetics analysis also revealed the effect of clay as accelerator. The DMA tan d presented two distinct peaks related to the autocatalytic and n-order kinetics steps. However, the DMA results did not showed any evidence of the accelerating effect of clay. On the other side the DEA analysis presented equivalent results of DSC. The X-ray difractograms showed clay intercalation on composites studied. As conclusion the DSC and DEA techniques can be used as analytical tool to determine the influence of incorporation of organoclay on reactive polymer medium.

De modo geral, os ciclos de cura para resina epóxi demandam algumas horas e elevadas temperaturas. Em busca de novas soluções para a otimização de processos sem perda de qualidade, bem como a economia de energia, diversos processos de cura de resina epóxi não convencionais foram desenvolvidos ao longo dos anos. O uso de irradiação de micro-ondas teve início após a Segunda Guerra Mundial, com a invenção do RADAR. A radiação de micro-ondas é uma radiação não-ionizante, com bom poder de penetração e boa transferência de calor em materiais absorvedores, ou materiais com cargas absorvedoras. A frequência usualmente utilizada em trabalhos de pesquisa e desenvolvimento é de 2,45GHz, a mesma disponível nos equipamentos comerciais e industriais existentes. Para a cura de resinas epóxi não são necessárias alterações no sistema reativo, com iniciadores específicos sensíveis a micro-ondas. O \"efeito micro-ondas\" proporciona um aumento da velocidade de colisão entre os reagentes que, associada à energia absorvida pelo sistema reacional, acelera a reação de cura, possibilitando a cura de resinas de tempo de uso longo (superior a 24 horas, em temperatura ambiente) em questão de minutos. Neste estudo foi utilizado inicialmente um sistema epóxi do tipo DGEBA, com endurecedor à base de anidrido e acelerador à base de amina, nas mesmas condições comerciais indicadas pelo fabricante. Testes iniciais com os fornos de micro-ondas selecionados foram realizados previamente a operação com sistemas epóxi. A cura do sistema já catalisado foi realizada em dois diferentes fornos de micro-ondas adaptados para uso em laboratório. A temperatura de degradação, e a temperatura de transição vítrea, foram avaliadas por técnicas de análise térmica. Cargas, pigmentos e aditivos também foram avaliados, no sentido de determinar suas influências em misturas com o sistema epóxi escolhido. Após estudos preliminares com o sistema epóxi puro, foram realizados testes em compósitos reforçados com fibra de vidro. Os resultados indicam que o processo é promissor, correspondendo ao observado em diversos artigos na literatura. / Generally, the cure cycles epoxy resin demand for few hours, and elevated temperatures. In search of new solutions for process optimization without loss of quality as well as energy saving, various processes of curing epoxy resin unconventional were developed over the years. The use of microwave irradiation began after World War II, with the invention of RADAR. The microwave radiation is non-ionizing radiation, with good power of penetration and good heat transfer in absorbing materials, or materials with absorbing fillers. The frequency usually used in research and development is of 2.45 GHz, the same is available in commercial equipment. For curing epoxy resins are not necessary changes in the system reactive with specific initiators sensitive to microwaves. The \"microwave effect\" provides increased on collision velocity between the reactants, which combined with energy absorbed by the reaction system, its accelerates the reaction curing, allowing the resin to cure long pot-life (times greater than 24 hours) in minutes. In this study, a DGEBA epoxy resin with an anhydride based hardener, and an initiator based on amine was used under the same conditions indicated by the manufacturer. Preliminary tests with the microwave ovens selected were executed before the operation with epoxy systems. The curing of the catalyzed system was performed in two different adapted microwave ovens for use in laboratory. The degradation temperature and the glass transition temperature were evaluated by thermal analysis techniques. Fillers, pigments and additives also were evaluated to determinate the influences with and without the epoxy system. After previous tests with the epoxy system alone, it was realized tests in composites form with glass fiber. The initial results indicate that the curing process by microwave irradiation is promising, and corresponding with the literature.

O câncer é hoje a segunda maior causa de morte por doenças em vários países, inclusive no Brasil, sendo um dos problemas de saúde pública mais complexos. O câncer de próstata é o mais comum em homens no Brasil, desconsiderando o de pele do tipo não melanoma. A braquiterapia é uma modalidade da radioterapia na qual fontes radioativas seladas são colocadas dentro ou em contato com o órgão a ser tratado, uma das formas de tratamento para esse tipo de câncer. O radioisótopo mais utilizado é o iodo-125, que se apresenta fixado em um substrato de prata que é selado em uma cápsula de titânio. A técnica exige o implante de 80 a 120 sementes por paciente, sendo este tratamento considerado um procedimento de baixo impacto e não cirúrgico. A maioria dos pacientes pode retornar à atividade normal dentro de um a três dias, com pouca ou nenhuma dor. Este trabalho propõe a construção de um modelo de semente alternativo às sementes atualmente em uso, com a finalidade de reduzir o custo das mesmas. Para atingir esse objetivo, este trabalho buscou obter maior eficiência na fixação do iodo radioativo, utilizando um substrato polimérico. Foram desenvolvidos cinco métodos para a fixação do iodo-125 nesses substratos. Os parâmetros analisados nos experimentos foram: tipo de polímero, tempo de imersão, tipo de reação (estática ou dinâmica), concentração da solução de iodo radiativo, atividade específica da solução, necessidade do uso de carreador e a forma química do iodo radioativo. O estudo desses experimentos definiram o método mais eficaz da fixação do iodo no material polimérico (resina epóxi). Foram avaliados os rendimentos da reação de fixação, a atividade do iodo no substrato polimérico, a variação da distribuição da atividade num lote de núcleos poliméricos e a eficiência da resina epóxi em selar a semente. / Cancer is currently the second leading cause of death by disease in several countries, including Brazil. Prostate cancer is the most common among men. Brachytherapy is a modality of radiotherapy in which radioactive seeds are placed inside or in contact with the organ to be treated. The most widely used radioisotope in prostate brachytherapy is iodine- 125, which is presented fixated on a silver substrate that is subsequently placed inside a titanium capsule. A large dose of radiation is released only in the targeted tumor protecting healthy surrounding tissues. The technique requires the application of 80 - 120 seeds per patient. The implants of seeds have low impact and are non-surgical procedures. Most patients can return to normal life within three days with little or no pain. This work proposes an alternative to the seeds that have already been developed, in order to reduce the cost by obtaining a better efficiency on fixing the radioactive iodine onto the epoxy resin. Methods have been developed to perform the fixation of iodine-125 onto polymeric substrates. The parameters analyzed were the immersion time, type of static or dynamic reaction, concentration of the adsorption solution, the specific activity of the radioactive source, the need for carrier and chemical form of the radioactive iodine. These experiments defined the most effective method to fixate the iodine onto the polymeric material (epoxy resin), the iodine activity in the polymeric substrate, the variation of the distribution of activity in a plot of polymeric cores and the efficiency of the epoxy resin to seal the seed.