<p>This work describes how a fatty acid methyl ester (FAME) derived from a vegetable oil can be introduced as reactive diluent in a solvent-borne thermally cured coil-coating system. The evaluated reactive diluent, rape seed methyl ester (RME), has been evaluated both in a fully formulated clear coat system and via model studies.</p><p>A reactive diluent is a compound that acts as a solvent in the liquid paint, lowering the viscosity, and chemically reacts into the final film during cure. Introduction of a reactive diluent derived from vegetable oil give a more environmental compliant coating since a renewable material is incorporated in the coating and the amount of traditional solvent can be decreased. These positive environmental factors have increased the industrial interest.</p><p>The fully formulated clear coat studies describes how addition of reactive diluent affects rheological properties of the wet paint, film formation, incorporation, and final film properties in a hydroxyl-functional polyester/melamine coil-coating system. The coating were cured under industrial coil-coating cure conditions and analyzed with Raman, carbon-14 dating, extraction, dynamic mechanical analysis, and visually observed. Viscosity measurement of the wet paint show that RME works as a diluent. RME increase the mobility in the system enhancing the film formation process and occurrence of defect-free films. The incorporation of RME could not be confirmed by Raman analysis. However, carbon-14 dating did indicate the presence of RME that could not be extracted from the films. The appearance and mechanical properties of the films were also significantly affected by addition of RME. Dynamic mechanical analysis of the free standing films showed that the final film properties were affected by oven temperature, choice of co-solvent, and flash-off period.</p><p>Model studies were performed to further clarify how RME chemically can react through transesterification with the hydroxyl-groups of the polyester. RME and its two main components methyl oleate and methyl linoleate were reacted with primary alcohols with and without tertiary hydrogen both under low temperature (110, 130, 150, 170°C) and industrial cure conditions. The transesterification reaction was monitored with 1H-NMR and real time IR. Evaporation and side reactions, e.g. oxidation, are competing factors with the transesterification reaction. The fatty acid structure affects the conversion as a higher amount of unsaturations triggers higher degree of oxidation. The study also showed that reaction time and temperature affects the transesterification conversion, degree of side reactions, and catalyst choice.</p>

abstract: The alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts have been extensively studied due to the advantages they offer in terms enhanced material properties, while increasing sustainability by the reuse of industrial waste and byproducts and reducing the adverse impacts of OPC production. Fly ash and ground granulated blast furnace slag are commonly used for their content of soluble silica and aluminate species that can undergo dissolution, polymerization with the alkali, condensation on particle surfaces and solidification. The following topics are the focus of this thesis: (i) the use of microwave assisted thermal processing, in addition to heat-curing as a means of alkali activation and (ii) the relative effects of alkali cations (K or Na) in the activator (powder activators) on the mechanical properties and chemical structure of these systems. Unsuitable curing conditions instigate carbonation, which in turn lowers the pH of the system causing significant reductions in the rate of fly ash activation and mechanical strength development. This study explores the effects of sealing the samples during the curing process, which effectively traps the free water in the system, and allows for increased aluminosilicate activation. The use of microwave-curing in lieu of thermal-curing is also studied in order to reduce energy consumption and for its ability to provide fast volumetric heating. Potassium-based powder activators dry blended into the slag binder system is shown to be effective in obtaining very high compressive strengths under moist curing conditions (greater than 70 MPa), whereas sodium-based powder activation is much weaker (around 25 MPa). Compressive strength decreases when fly ash is introduced into the system. Isothermal calorimetry is used to evaluate the early hydration process, and to understand the reaction kinetics of the alkali powder activated systems. A qualitative evidence of the alkali-hydroxide concentration of the paste pore solution through the use of electrical conductivity measurements is also presented, with the results indicating the ion concentration of alkali is more prevalent in the pore solution of potassium-based systems. The use of advanced spectroscopic and thermal analysis techniques to distinguish the influence of studied parameters is also discussed. / Dissertation/Thesis / M.S. Engineering 2013

This work describes how a fatty acid methyl ester (FAME) derived from a vegetable oil can be introduced as reactive diluent in a solvent-borne thermally cured coil-coating system. The evaluated reactive diluent, rape seed methyl ester (RME), has been evaluated both in a fully formulated clear coat system and via model studies. A reactive diluent is a compound that acts as a solvent in the liquid paint, lowering the viscosity, and chemically reacts into the final film during cure. Introduction of a reactive diluent derived from vegetable oil give a more environmental compliant coating since a renewable material is incorporated in the coating and the amount of traditional solvent can be decreased. These positive environmental factors have increased the industrial interest. The fully formulated clear coat studies describes how addition of reactive diluent affects rheological properties of the wet paint, film formation, incorporation, and final film properties in a hydroxyl-functional polyester/melamine coil-coating system. The coating were cured under industrial coil-coating cure conditions and analyzed with Raman, carbon-14 dating, extraction, dynamic mechanical analysis, and visually observed. Viscosity measurement of the wet paint show that RME works as a diluent. RME increase the mobility in the system enhancing the film formation process and occurrence of defect-free films. The incorporation of RME could not be confirmed by Raman analysis. However, carbon-14 dating did indicate the presence of RME that could not be extracted from the films. The appearance and mechanical properties of the films were also significantly affected by addition of RME. Dynamic mechanical analysis of the free standing films showed that the final film properties were affected by oven temperature, choice of co-solvent, and flash-off period. Model studies were performed to further clarify how RME chemically can react through transesterification with the hydroxyl-groups of the polyester. RME and its two main components methyl oleate and methyl linoleate were reacted with primary alcohols with and without tertiary hydrogen both under low temperature (110, 130, 150, 170°C) and industrial cure conditions. The transesterification reaction was monitored with 1H-NMR and real time IR. Evaporation and side reactions, e.g. oxidation, are competing factors with the transesterification reaction. The fatty acid structure affects the conversion as a higher amount of unsaturations triggers higher degree of oxidation. The study also showed that reaction time and temperature affects the transesterification conversion, degree of side reactions, and catalyst choice. / QC 20101117

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.

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.

Submitted by Erika Demachki (erikademachki@gmail.com) on 2014-10-23T17:14:40Z No. of bitstreams: 2 Dissertação - Mário Henrique Gomes Brito - 2013.pdf: 6257761 bytes, checksum: 3ff568c727b44a8a7e645c8475216a03 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Jaqueline Silva (jtas29@gmail.com) on 2014-10-23T18:50:27Z (GMT) No. of bitstreams: 2 Dissertação - Mário Henrique Gomes Brito - 2013.pdf: 6257761 bytes, checksum: 3ff568c727b44a8a7e645c8475216a03 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2014-10-23T18:50:27Z (GMT). No. of bitstreams: 2 Dissertação - Mário Henrique Gomes Brito - 2013.pdf: 6257761 bytes, checksum: 3ff568c727b44a8a7e645c8475216a03 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2013-04-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The overall objective of this research, which was essentially experimental, is to study the influence of the isothermal period and the maximum temperature of the thermal cure cycle steam under atmospheric pressure in the development of compressive strength of concrete blocks over time. The influences of two other types of curing are also being investigated; curing by enveloping with plastic sheet and open air curing, considered the last case scenario for reference. This study specifically aimed to further our understanding on how to; a) evaluate and quantify the importance of adopting procedures for curing the average resistance (Fbm) and characteristic (fbk) strength to compression of concrete blocks, comparing the processes of thermal curing and curing by enveloping plastic sheet to open air curing; b) evaluate statistically the aging effect of blocks over its compressive strength; c) evaluate the interaction effects of the variables "type of cure" and "age analysis" of the results of compressive strength of concrete blocks; and d) identify the main changes in the microstructure of the blocks subjected to a thermal curing process, especially observing eventual delayed ettringite formation in the internal structure of the material. To examine the influence of maximum curing temperature, two levels were adopted; 65°C and 85°C. As for analyzing the influence of isothermal period, three levels were adopted; 3 hours, 4 hours and 5 hours. The age analysis was evaluated in five levels; 1, 3, 7, 28 and 91 days. The results showed that the worst condition for curing, or curing type, was the open air curing (curing time approximately equal to 24 hours), which led to a lower overall average result of compressive strength of concrete blocks, proving the importance of adopting procedures of curing to optimize the mechanical performance of concrete blocks. Furthermore, it was also determined that the best curing conditions were the curing with enveloping plastic sheet (curing time approximately equal to 24 hours) and the thermal curing with steam under atmospheric pressure isotherm of 65°C and isothermal period of 3 hours (curing time approximately equals 8.5 hours), which were considered statistically equal. It was also observed that there was no significant influence of the curing in maximum temperature in relation to the compressive strength of the blocks. In the other hand, the isothermal period was very significant; the best condition was 3 hours, while 4 hours and 5 hours were considered statistically equal. Regarding the delayed ettringite formation, it was only verified for thermal curing conditions of isothermal of 85°C and isothermal period of 4 hours and 5 hours. / O objetivo geral desta pesquisa, de caráter essencialmente experimental, é estudar a influência do período isotérmico e da temperatura máxima do ciclo de cura térmica a vapor sob pressão atmosférica no desenvolvimento da resistência à compressão de blocos de concreto ao longo do tempo. Paralelamente, foram investigadas ainda as influências de dois outros tipos de cura, a saber: cura por envelopamento com lona plástica e cura ao ar livre, considerada esta última a situação de referência. De modo específico, o estudo visou ainda: a) avaliar e quantificar a importância da adoção de procedimentos de cura nas resistências média (fbm) e característica (fbk) à compressão de blocos de concreto, comparando os processos de cura térmica e cura por envelopamento com lona plástica com a cura ao ar livre; b) avaliar estatisticamente o efeito da idade dos blocos sobre a sua resistência à compressão; c) avaliar a interação dos efeitos das variáveis “tipo de cura” e “idade de análise” sobre os resultados de resistência à compressão dos blocos de concreto; e d) identificar as principais transformações ocorridas na microestrutura dos blocos submetidos aos processos de cura térmica, em especial observando eventual formação de etringita tardia na estrutura interna do material. Para analisar a influência da temperatura máxima de cura, foram adotados dois níveis: 65°C e 85°C. Já para analisar a influência do período isotérmico, foram adotados três níveis: 3 horas, 4 horas e 5 horas. Por sua vez, a idade de análise foi avaliada em cinco níveis: 1, 3, 7, 28 e 91 dias. Os resultados mostraram que a pior condição de cura, ou seja, o tipo de cura que conduziu ao menor resultado médio global de resistência à compressão dos blocos de concreto, foi a cura ao ar livre (tempo de cura aproximadamente igual a 24 horas), comprovando a importância da adoção de procedimentos de cura para a otimização do desempenho mecânico dos blocos de concreto. Além disso, foi verificado ainda que as melhores condições de cura foram a cura por envelopamento com lona plástica (tempo de cura aproximadamente igual a 24 horas) e a cura térmica a vapor sob pressão atmosférica com isoterma de 65°C e período isotérmico de 3 horas (tempo de cura aproximadamente igual a 8,5 horas), os quais foram considerados, estatisticamente, iguais. Também foi verificado que não houve influência significativa da temperatura máxima de cura em relação à resistência à compressão dos blocos. Já o período isotérmico foi significativo, de modo que a melhor condição foi 3 horas, enquanto 4 horas e 5 horas foram considerados, estatisticamente, iguais. Quanto à formação de etringita tardia, esta só foi verificada para as condições de cura térmica com isoterma de 85°C e períodos isotérmicos de 4 horas e 5 horas.