Orientador: Daniel Barrera Arellano / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-20T11:35:24Z (GMT). No. of bitstreams: 1 Rocha_JulioCesarBarbosa_M.pdf: 24598807 bytes, checksum: 90f87fe1c3e7c9e31d7d85e39bf82613 (MD5) Previous issue date: 2012 / Resumo: Os óleos e gorduras representam um papel nutricional chave na alimentação humana e apresentam importância como estrutura de muitos produtos alimentícios que consumimos, como margarinas, por exemplo. Gorduras sólidas, ricas em ácidos graxos saturados foram, durante muito tempo, utilizadas para obter produtos com as características tecnológicas desejáveis de textura e dureza, sendo substituídas por gorduras ricas em ácidos graxos trans. Com a descoberta dos efeitos negativos dos ácidos graxos trans para a saúde esses materiais foram substituídos por gorduras de alta tecnologia obtidas por processos químicos de interesterificação que novamente se utilizam da presença de ácidos graxos saturados. Alternativas tecnológicas visando à redução dos teores de ácidos graxos saturados se fazem necessárias. Sendo o óleo de soja de baixo custo, elevada disponibilidade e baixo teor de ácidos graxos saturados, ele se mostra adequado ao desenvolvimento de novas gorduras tecnológicas utilizando ceras vegetais como agentes estruturantes, para a obtenção de organogéis. Organogéis são misturas com capacidade de se auto-sustentarem, formadas por uma fase contínua líquida e um agente estruturante, neste caso a cera. A cera de cana- de-açúcar tem seu interesse elevado devido ao alto potencial produtivo brasileiro, aliado à suas características físicas. O objetivo deste trabalho foi avaliar o potencial de formação de organogéis com a cera de cana-de-açúcar e suas frações solúvel e insolúvel em etanol a quente e avaliar o comportamento físico desses organogéis. Os três estruturantes estudados apresentaram capacidade de formar organogéis na condição de cristalização estática a 5°C nas concentrações estudadas (1, 2, 3 e 4% m/m), e apenas a fração insolúvel em etanol a quente incapaz de formar organogéis estáveis sob a condição de cristalização estática a 25°C. As propriedades térmicas dos géis foram as esperadas para o material, sendo diferentes para cada um dos estruturantes as temperaturas de início de cristalização variaram entre 42 e 47°C e de fusão entre 49 e 59°C. Os géis apresentaram resistência mecânica, sendo que os géis mais resistentes foram os de 4% (m/m) da cera clarificada e purificada e da fração solúvel em etanol. O comportamento reológico foi típico para géis termorreversíveis com aumento de viscosidade nas temperaturas entre 40 e 44°C, coincidindo com a temperatura encontrada por DSC. A microestrutura observada para os organogéis foi característica de uma rede tridimensional organizada para as amostras contendo cera cristalizada e purificada e a fração solúvel em etanol e desorganizada para o organogel obtido pela fração insolúvel em etanol. Os organogéis apresentaram estabilidade por 7 dias em diferentes condições de temperatura (5, 25 e 35°C) com exceção do organogel obtido com a fração insolúvel em etanol cristalizada em 25°C. Os organogéis formados apresentaram baixa resistência mecânica e térmica, sendo de fácil fusão, porém podem ser adequados para aplicações industriais como substitutos de gorduras moles / Abstract: Fats and oils present a key role in our diet, as nutrients and as structure for many food products that we consume such as margarines. Solid fats rich in saturated fatty acids were used during a long time to obtain food products with desirable technological characteristics of hardness and texture, being replaced by rich in trans fatty acids fats. With the discovery of the negative health effects of trans fatty acids, these materials were replaced by high technology fats such as chemically modified interesterified fats that again used saturated fatty acids to get the desirable texture. Technological alternatives to reduce the intake of saturated fatty acids are needed. Soybean oil is a low cost, highly available and low in saturated fatty acids source of lipid, being adequate for the development of new technological fats using vegetable waxes as structuring agents, forming organogels. Organogels are mixtures that are capable of self-support, formed by a liquid continuous phase and a structuring agent, in this case wax. Sugarcane wax is interesting because of its high productive potential presented in Brazil and because of its physical characteristics. The goal of this study was to evaluate the potential of sugarcane wax and its hot ethanol soluble and insoluble fractions to form organogels and evaluate the physical behavior of these organogels. The three structurants presented the ability to form organogels at static crystallization at 5°C at the studied concentration (1, 2, 3 and 4%, w/w), but the hot ethanol insoluble fraction wasn¿t capable of forming stable organogels at static crystallization at 25°C. The thermal properties of the studied organogels were as expected for the kind of material, being different for each structurant in a range of 42 to 47°C for crystallization and 49 to 59°C for melting. The organogels presented mechanical hardness, being the most resistant the 4% (w/w) of clarified and purified wax and hot ethanol soluble fraction. The organogels also presented a typical rheological behavior presenting thermoreversibility and an increase of viscosity at the temperature range of 40 to 44°C, similar to measure on DSC. The observed microstructure was a tridimensional organized network for the samples clarified and purified sugarcane wax and hot ethanol soluble fraction and more disorga nized for the hot ethanol insoluble fraction. The organogels presented stability for 7 days at different temperature conditions (5, 25 and 35°C) with the exception being the hot ethanol insoluble fraction crystallized at 25°C. The developed organogels presented low mechanical and thermal resistance, being easily melted, however they can be adequate for technological application as replacement for soft fats / Mestrado / Tecnologia de Alimentos / Mestre em Tecnologia de Alimentos

[pt] O presente trabalho visa a obtenção de um melhor conhecimento dos mecanismos de deposição de parafina em linhas de produção de petróleo, a fim de auxiliar nas atividades de manutenção preditiva, e de fornecer subsídios para o estudo da viabilidade econômica da exploração de campos petrolíferos. Os dados experimentais obtidos foram utilizados para calibrar o simulador numérico desenvolvido pela PUC-Rio. Experiências de deposição para várias condições e óleos foram realizados. O regime de escoamento foi sempre monofásico (líquido). Foi realizada uma comparação entre os dados experimentais e resultados numéricos correspondentes, tendo-se observado uma boa concordância entre ambos. / [en] This work aims at a better understanding of the paraffin deposition mechanism in oil production lines. This knowledge can be very helpful in maintenance activities and to perform economical feasibility studies of exploration of oil fields. Experimental results were used to adjust e numerical simulator developed at PUC-Rio to a number of different oils. Deposition experiments for several conditions and oils were performed. The flow regime imposed was a liquid single-phase. Comparisons between experimental results and numerical predictions showed reasonable agreement.

Environmental change in the Arctic proceeds at an unprecedented rate. The Pliocene epoch (5-2.65 million years ago) represents an analog for future climate conditions, with pCO2 and continental configurations similar to present. Yet conditions in the Pliocene Arctic are poorly characterized because of sparse sampling. The records that do exist indicate periods of extreme warmth, as well as the first expansion of large ice-sheets in the Northern Hemisphere, took place from the end of the Pliocene into the early Pleistocene. Understanding these deposits and their implications for our future requires developing a sense of climatic evolution across the Plio-Pleistocene transition and especially during the intensification of Northern Hemisphere Glaciation (iNHG) ~2.7 million years ago. Here we reconstruct environmental change in the Arctic using a suite of organic geochemical proxies in a sedimentary archive recovered from Lake El'gygytgyn, Arctic Northeast Russia. We use the distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) and the hydrogen isotopic composition (δD) of plant leaf-waxes (n-alkanes) to reconstruct relative temperature change across the interval spanning 2.8 to 2.4 million years ago. Our work demonstrates that, following the first major glaciation of the Northern Hemisphere, it took multiple glacial cycles for the Arctic to become synchronized with the climatic changes recorded in the deep ocean. This work has implications for understanding the role of sea-level, sea-ice, vegetation and carbon-cycle feedbacks in a changing Arctic.

This diploma thesis describes the process of production of the cast by the lost-wax casting method. It includes the manufacturing of prototype models by additive technology, creation of ceramic shell molds. The work also includes an experimental part focused on the production of the selected parts by the method of the lost-wax casting and the comparison of this method with other types of production.

abstract: This research is a comprehensive study of the sustainable modifiers for asphalt binder. It is a common practice to use modifiers to impart certain properties to asphalt binder; however, in order to facilitate the synthesis and design of highly effective sustainable modifiers, it is critical to thoroughly understand their underlying molecular level mechanisms in combination with micro and macro-level behavior. Therefore, this study incorporates a multi-scale approach using computational modeling and laboratory experiments to provide an in-depth understanding of the mechanisms of interaction between selected modifiers and the constituents of asphalt binder, at aged and unaged conditions. This study investigated the effect of paraffinic wax as a modifier for virgin binder in warm-mix asphalt that can reduce the environmental burden of asphalt pavements. The addition of wax was shown to reduce the viscosity of bitumen by reducing the self-interaction of asphaltene molecules and penetrating the existing nano agglomerates of asphaltenes. This study further examined how the interplay of various modifiers affects the modified binder’s thermomechanical properties. It was found that the presence of wax-based modifiers has a disrupting effect on the role of polyphosphoric acid that is another modifier of bitumen and its interactions with resin-type molecules. This study was further extended to using nanozeolite as a mineral carrier for wax to better disperse wax in bitumen and reduce the wax's adverse effects such as physical hardening at low service temperatures and rutting at high service temperatures. This novel technique showed that using a different method of adding a modifier can help reduce the modifier's unwanted effects. It further showed that nanozeolite could carry wax-based modifiers and release them in bitumen, then acting as a scavenger for acidic compounds in the binder. This, in turn, could promote the resistance of asphalt binder to moisture damage by reducing the quantity of acidic compounds at the interface between the binder and the stone aggregates. Furthermore, this study shows that iso-paraffin wax can reduce oxidized asphaltene molecules self-interaction and therefore, reduce the viscosity of aged bitumen while cause brittleness at low temperatures. Additionally, a cradle to gate life-cycle assessment was performed for a new bio-modifier obtained from swine manure. This study showed that by partially replacing the bitumen with bio-binder from swine manure, the carbon footprint of the binder can be reduced by 10% in conjunction with reducing the cost and environmental impact of storing the manure in lagoons. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2020

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