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Orientador: Prof. Dr. Anderson Orzari Ribeiro / Tese (doutorado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2016. / Este trabalho descreve a sintese de butadienos push-pull. Utilizou-se as reacoes de Vilsmeier-Haack para a obtencao de clorovinilaldeidos e posteriormente a reacao de Knoevenagel, obtendo-se assim os butadienos push-pull, que sao compostos de elevada conjugacao eletronica. Alem dos butadienos push-pull, obteve-se atraves de uma reacao de condensacao aldolica, catalisada por acido, uma nova pentadienona, a 2,6-bis-(4-hidroxi-3-metoxi-benziliden)-cicloexanona e uma tetraen-5-ona, a 9-dicloro-1,9-bis-(3,4-dimetoxi-fenil)-nona-1,3,6,8-tetraen-5-ona. Realizou-se a caracterizacao estrutural de todos esses compostos, confirmando-se assim a estrutura dos mesmos. Testou-se estes compostos a respeito de suas propriedades antioxidantes, bactericidas e fungicidas. O composto 2,6-bis-(4-hidroxi-3-metoxi-benziliden)-cicloexanona demonstrou elevada atividade antioxidante na concentracao de 260 ¿Êg/mL quando comparado com a quercetina, que e um fenol utilizado como padrao no teste de DPPH. Realizou-se dois testes de atividade bactericida e fungicida e os compostos apresentaram halo de inibicao a diversos micro-organismos sendo que o composto 2,6-bis-(4-hidroxi-3-metoxi-benziliden)-cicloexanona demonstrou ser o mais promissor, inibindo o crescimento de 7 das 9 especies de micro-organismos testados. / This work describes the synthesis of push-pull butadienes. The Vilsmeier-Haack reactions were used to obtain chloro-vinyl-aldehydes and later the Knoevenagel reaction to obtain the push-pull butadienes, which are compounds of high electronic conjugation. In addition to push-pull butadiene, applying acid catalyzed aldol condensation, new pentadienones were obtained, like 2,6-bis-(4-hydroxy-3-methoxy-benzylidene)¿cyclohexanone and a 9-dichloro-1,9-bis-(3,4-dimethoxy-phenyl)-1,3,6,8-tetraen-5-one. The structural characterization was carried out, confirming the structure the synthesized compounds. The compounds were tested for their antioxidant, bactericidal and fungicidal properties. The 2,6-bis-(4-hydroxy-3-methoxy-benzylidene) -cyclohexanone showed a high antioxidant activity at 260 ìg/mL when compared to quercetin, which is a phenol used as a standard in the DPPH test. They showed inhibition to several microorganisms and the compound, 2,6-bis- (4-hydroxy-3-methoxy-benzylidene) -cyclohexanone was the most promising, inhibiting the growth of 7 of the 9 species of microorganisms tested.

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No. of bitstreams: 1 DissAMRS.pdf: 6125625 bytes, checksum: 9805401aaa2ce2f249b4e2c4bb9032a0 (MD5) Previous issue date: 2016-05-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Ethanol has been largely studied in the past few decades as a substitute to fossil fuels in the synthesis of a large variety of chemicals. 1,3-Butadiene, one of these compounds, is an important chemical intermediate and also a monomer for some polymers such as synthetic rubbers. It is mainly produced as a by-product from naphtha steam cracking, which has ethylene as the major product. As crude oil prices have been fluctuating in the latest years and with the discovery of shale gas in the US, a promising source for ethylene, there is an urgency for developing alternative routes to produce 1,3-Butadiene. Several studies have been carried since the 1940s trying to create viable processes and using many different catalysts, indicating MgO/SiO2 - with or without the addition of transition metals - as being the most promising one. However, there is still a lot of missing information on how does the interaction between silica and magnesia affect the yields and selectivity. In the present work it was studied how the morphology of the MgO affects the interaction with the SiO2 to generate active sites. The MgO with different morfologies were synthesized and then wet-kneaded with SiO2 to provide catalysts with different MgO/SiO2 ratio. The samples were calcined and catalytic tests were carried out. X-Ray Diffraction, Temperature Programmed Desorption of CO2 and Scanning Electron Microscopy were also performed on the catalysts. The obtained micrographs for the oxides confirmed the successful preparation of different morphologies, and the results for catalytic tests showed that there is some influence from the morphology over conversion and selectivity of SiO2/MgO. For the MgO morphologies at the temperature of 425 oC, ethanol conversions between 11.7% and 21.9% were obtained for different samples, with selectivities for butadiene between 5.6% and 30.4%. For SiO2/MgO catalysts, in the same temperature, different yields were obtained for distinct morphologies and Mg:Si ratios. For 3:1 catalysts, yields between 21.5% and 34.3% were observed, while for 7:1 catalysts the yields vary from 18.5% to 35.4%. Catalytic properties could not be clearly correlated to the TPD-CO2 and specific surface area, indicating that they are dependant on a complex set of factors, among them the accessibility of the surface for the SiO 2 contact. Variation of the silica content for all morphologies showed that the SiO2/MgO ratio is extremely important for the preparation of active and selective catalysts for the production of 1,3-butadiene. / O etanol vem sendo largamente estudado, recentemente, como um substituto aos combustíveis fósseis na síntese de diversos produtos industriais. O 1,3-Butadieno (BD), um destes compostos, é um importante intermediário químico e monômero para alguns polímeros e borrachas sintéticas. BD atualmente é produzido principalmente como um subproduto do craqueamento a vapor do nafta, que tem o etileno como principal produto. Flutuações no preço do petróleo e a descoberta de grandes reservas de shale gas nos Estados Unidos fazem com que haja uma necessidade de busca de rotas alternativas para a produção do BD. Muitos estudos vêm sendo realizados desde os anos 1940, utilizando diferentes catalisadores, indicando o MgO/SiO2 - com ou sem a adição de metais de transição - como o mais promissor. No entanto, ainda falta informação sobre a forma como a interação entre a sílica e a magnésia afeta os resultados da reação. No presente trabalho foi verificada a influência que a morfologia do MgO tem sobre a interação com SiO2 para formação de sítios ativos. As amostras de MgO com diferentes morfologias foram sintetizadas e, então, adicionadas de sílica para gerar os catalisadores com diferentes razões MgO/SiO2. Após calcinação, testes reacionais foram realizados. As amostras de MgO e SiO2 /MgO foram caracterizadas por Difração de Raios-X, Dessorção a Temperatura Programada de CO 2 (TPD-CO2) e Microscopia Eletrônica de Varredura (MEV). As imagens de MEV dos óxidos permitiram confirmar a síntese das diferentes morfologias de MgO, e resultados para testes de atividade catalítica mostram uma influência da morfologia na atividade e seletividade do SiO2/MgO. Para os MgO, em uma temperatura de 425 oC, foram obtidas conversões entre 11.7% e 21.9% para diferentes morfologias, com seletividades para BD entre 5.6% e 30.4%. Para os catalisadores SiO2/MgO, na mesma temperatura, foram obtidos rendimentos variáveis com a morfologia e com o teor Mg:Si. Para os catalisadores 3:1, foram observados rendimentos entre 21.5% e 34.3%, enquanto que para os catalisadores 7:1 puderam ser observados rendimentos variando entre 18.5% e 35.4%. As propriedades catalíticas não puderam ser claramente correlacionadas com os dados de TPD-CO2 e área superficial específica, evidenciando que estas são dependentes de um complexo conjunto de fatores, dentre eles a acessibilidade da superfície para o contato com o SiO2 . A variação do teor de sílica mostra que a razão SiO 2/MgO é extremamente importante para obtenção de catalisadores ativos e seletivos para formação do 1,3-butadieno.

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Indiana University-Purdue University Indianapolis (IUPUI) / Acrylonitrile Butadiene Styrene (ABS) is the most widely used thermoplastics in 3D printing for making models, prototypes, patterns, tools and end-use parts. However, there is a lack of systematic understanding of the mechanical properties of 3D printed ABS components, including orientation-dependent tensile strength, creep, and fatigue properties. These mechanical properties are critically needed for design and application of 3D printed components. The main objective of this research is to systematically characterize key mechanical properties of 3D printed ABS components, including tensile, creep, and fatigue properties. Additionally, the eff ects of printing orientation on the mechanical prop- erties are investigated. There are two research approaches employed in the thesis: rst, experimental investigation of the tensile, creep, and fatigue properties of the 3D printed ABS components; second, laminate based finite-element modeling of tensile test to understand the stress distributions in different printing layers. The major conclusions of the thesis work are summarized as follows. The tensile test experiments show that the 0 printing orientation has the highest Young's modulus, 1.81 GPa, and ultimate strength, 224 MPa. The tensile test simulation shows a similar Young's modulus as the experiment in elastic region, indicating the robustness of laminate based finite element model. In the creep test, the 90 printing orientation has the lowest k value of 0.2 in the plastics creep model, suggesting the 90 is the most creep resistant among 0 , 45 , and 90 printing orientations. In the fatigue test, the average cycle number under load of 30 N is 3796 revolutions. The average cycle number decreases to 128 revolutions when the load is below 60N. Using the Paris Law, with the crack size of 0.75 mm long and stress intensity factor is varied from 352 to 700 MN -m^3/2 , the predicted fatigue crack growth rate is 0.0341 mm/cycle.

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Additively manufactured fuels are becoming more common in the area of hybrid rockets due to the enhanced possibilities provided by computer aided design and improved additive material technology. When integrated with a highly compliant yet energetic paraffin wax, the additive manufactured material can help support the paraffin wax during the burn, and improve overall performance. This study investigates thin-walled acrylonitrile butadiene styrene structures that separate paraffin wax into azimuthally partitioned cells. The fuel grains are tested using a vertical test stand, custom nitrous system, and data acquisition system. The computer program Chemical Equilibrium with Applications is used to compare common hybrid fuels such as sorbitol, polybutadiene acrylic acid acrylonitrile, and poly(methyl methacrylate) along with the manufactured fuel. The experimental results indicate the promise of higher performance using paraffin. The analyses, however, show that refinements in grain design are necessary to fully realize the advantages of paraffin.

The development of acrylonitrile-butadiene-styrene (ABS) resins for use in rotational molding would provide a medium performance material, thus opening doors to new markets for the rotational molding industry. Unfortunately, ABS resins have shown serious problems during the rotational molding process, namely discoloration, bridging, and poor impact strength. It is believed that these effects are due to degradation of the carbon-carbon double bond in the butadiene, through attack by either oxygen or heat. Previous efforts have shown some success in addressing these issues. However, additional improvements are necessary to make ABS resins commercially viable to rotational molders. This study, fourth in a series of similar projects conducted though Brigham Young University, was focused on remediation of the ABS difficulties via two different approaches. First, a survey of several additives was performed with the intent of investigating four different strategies: increased protection from oxygen, decreased butadiene concentration, increased butadiene concentration, and promotion of flow. The best formulation was achieved when 15 wt % of a benzoate ester (XP-2280 available though ChemPoint) was blended into MAGNUM 342 EZ, an ABS resin (The Dow Chemical Company). This formulation showed the best balance between increased impact strength and improvement of cosmetic properties. Second, optimization of several rotational molding processing parameters was executed. These included particle size distribution of the resin, drying of the resin, internal mold atmosphere, and oven temperature. It was found that using coarse particle sizes (ground at 20-mesh rather than the industry standard of 35-mesh) increased the impact strength by about 19%. None of the other parameters proved to have a significant effect upon the system, except for the use of a nitrogen atmosphere, which lowered the impact strength. Final properties testing of this best formulation at the optimal processing conditions showed increased impact strength from 2 ft-lbs (the previous best value) to 8 ft-lbs. There was also a marginal decrease in surface hardness (95 to 78 on the Rockwell R scale) and yield tensile strength (3,900 psi to 3,300 psi). Larger differences were observed in flexural modulus (200,000 psi to 110,000 psi) and heat distortion temperature (95°C to 61°C). Therefore, these formulation and processing changes show a trade-off where stiffness and thermal stability (i.e. flexural modulus and heat distortion temperature) can be sacrificed for an increase in toughness and aesthetics, made manifest by increased impact strength, elimination of bridging, and eradication of discoloration.

Made available in DSpace on 2016-03-15T19:36:55Z (GMT). No. of bitstreams: 1 Paula Aparecida Bergamini.pdf: 11467964 bytes, checksum: f444fac5ebd5632e2cdcc942570f6e37 (MD5) Previous issue date: 2015-08-10 / This study proposes the production and characterization of blends of ABS/PC through reuse of discarded PC in the automotive panel production process. The developed alloy ratios are (ABS/PC) 30/70, 50/50 and 70/30, in addition to the neat materials. For comparative purposes the mixtures were developed for both materials recycled PC (PCr) and neat PC (PCn). The blends were processed in a twin screw extruder under controled heating temperature. / Este estudo propõe a produção e caracterização de blendas de ABS/PC por meio do reuso do policarbonato (PC) descartado no processo de produção de painéis automotivos. As proporções de mistura desenvolvidas para estudo foram (ABS/PC) 30/70, 50/50 e 70/30, além dos materiais puros. Para efeitos comparativos, as misturas foram desenvolvidas tanto com o PC reciclado (PCr) como com o PC natural (PCn). As blendas foram processadas em extrusora de dupla rosca, sob temperatura controlada.