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O crescimento de células em arcabouços tridimensionais porosos tem se tornado progressivamente ativo na engenharia de tecidos. Os arcabouços guiam o crescimento celular, sintetizam uma matriz extracelular e outras moléculas biológicas, e facilitam a formação de tecidos e órgãos funcionais. Um cimento deste tipo pode ser preparado misturando um sal de fosfato de cálcio com uma solução aquosa para que se forme uma pasta que possa reagir à temperatura corporal dando lugar a um precipitado que contenha hidroxiapatita (Ca10(PO4)6(OH)2). A similaridade química e morfológica entre este biomaterial e a parte mineral dos tecidos ósseos permite a osteocondução, sendo o cimento substituído por tecido ósseo novo com o tempo e com a vantagem de não desencadear processos inflamatórios e de corpo estranho, com eventual expulsão do material implantado. O objetivo do presente trabalho foi a obtenção e caracterização de suportes tridimensionais para a engenharia de tecido, com o uso de matérias-primas nacionais, por meio da utilização de microesferas de parafina como corpos geradores de poros. As microesferas foram produzidas por suspensão em solução aquosa de poli (álcool vinílico) (PVA) e sulfato de sódio (Na2SO4). Foram analisadas as fases presentes no cimento sintetizado e após a reação de cura do mesmo, a variação do tamanho de partícula e da resistência mecânica com o tempo de moagem. Foi analisada a porosidade dos suportes e a forma de extração da parafina daqueles que a utilizaram na sua formação. O tamanho de poro dos suportes gerados com a variação da quantidade de fase líquida ficou aquém do tamanho considerado ideal para o crescimento de tecido ósseo. A porosidade dos arcabouços fabricados com esferas de parafina foi observada por microscopia eletrônica de varredura (MEV), e seu comportamento foi analisado a partir de ensaios in vitro em solução SBF (simulated body fluid) e em cultura de células. A utilização de esferas de parafina permitiu a formação de poros com tamanho tal que possibilitam potencialmente o crescimento tecidual e celular. / The growth of cells in three-dimensional porous scaffolds has been extensively studied for use in tissue engineering. They guide grow of cells, synthesize extra cellular matrix and other biological molecules, and facilitate the formation of functional tissues and organs. Bone cements has been developed for biomedical applications for a decade approximately. This kind of cement can be prepared mixing a calcium phosphate salt with aqueous solution forming a paste that can react at body temperature generating a hydroxyapatite precipitated (Ca10(PO4)6(OH)2). The chemical and morphological similarity between the cement composition and the mineral part of the bones allows osteoconduction in the tissue with replacement of cement by new bone formed with the advantage to not unchain inflammatory processes and of strange body. The objective of this work was the use of the α-TCP cement for making these scaffolds, through the variation of the amount of liquid phase in the cement and of the use of paraffin spheres as pore source. These spheres were produced by suspension in water solution of poly (vinyl alcohol) and sodium sulphate (Na2SO4). The phases had been analyzed in the synthesized cement and after the reaction of cure of cement, beyond variation of the particle size and the resistance mechanics with the milling time. It was analyzed the porosity of the scaffolds and the extraction of the paraffin in that supports. The pore size of the supports generated with the variation of the amount of liquid phase was on this side of the size considered ideal for the bone tissue growth. The porosity of scaffolds manufactured with paraffin spheres was observed by Scanning Electron Microscopy (SEM), and its behavior was analyzed from test in vitro in SBF solution (simulated body fluid). The use of paraffin spheres allowed the formation of pores size able to permit tissue growth.

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Este estudo tem como objetivo a modificação da superfície de revestimentos poliméricos utilizando plasma, com o intuito de se criar materiais com superfícies resistentes a corrosão química e com baixa energia de superfície. Além disso, durante o trabalho foram estudadas diferentes maneiras de se viabilizar a aplicação em compartimentos de armazenamento e dutos de transporte de petróleo de modo a evitar a corrosão e diminuir a criação de depósitos de parafina e outras substâncias nas paredes dessas estruturas metálicas. Durante o projeto foi constatada a possibilidade de utilização dos processos estudados também em outras aplicações eletroquímicas, como por exemplo, a modificação da superfície de membranas seletivas. Portanto, a idéia geral do trabalho é a criação e modificação de materiais com características específicas para aplicações eletroquímicas, tendo como foco principal a proteção contra a corrosão e geração de filmes poliméricos com funções especiais. Para isso, foram estudadas a fluoração das superfícies de camadas poliméricas utilizando-se de um ambiente reativo de plasma, a deposição de filmes nanoestruturados sobre filmes poliméricos, e a avaliação de aplicações para os filmes desenvolvidos para redução da adsorção química. A partir dos resultados obtidos foi possível criar um revestimento que combina alta aderência à superfície do aço e baixa tensão superficial, devido à criação de uma camada com alta concentração de flúor. Os resultados mostraram-se promissores na modificação de revestimentos comerciais, pois apenas a superfície do revestimento anticorrosivo é alterada, utilizando-se uma quantidade pequena de reagentes e criando uma superfície antiaderente, e consequentemente, diminuindo a taxa de deposição da parafina no revestimento tratado. / The objective of this study is to modify the surface of polymeric coatings using plasma, with the aim of creating materials able to form low energy surface and chemical corrosion resistance. Moreover, in this work, was studied the application of the materials in storage compartments and pipelines transporting oil to check corrosion prevention and the reduction of paraffin deposits and other substances in the walls of these structures. Over the project it was found the possibility to use the studied processes in other electrochemical applications, such as the surface modification of selective membranes. So the general idea of this work is to create and/or modify materials with specific properties for electrochemical applications, focusing mainly on the corrosion protection and in the deposition of polymeric films with special functions. Thus, the fluorination of the polymeric layer surface using a reactive plasma environment, the deposition of nanostructured films on polymer films, and the performance evaluation for the films developed to reduce the chemical adsorption were studied. The results have shown that it is possible to develop a coating that combines high adhesion to steel surfaces and low surface tension, due to the creation of a layer with high concentration of fluorine. The processes were promising for modification of commercially available coatings, as only the surface is changed, only small amounts of reagents are used and an anti-adherent surface is created, which decreases the rate of paraffin deposition on the treated surface.

To date there exists a great deal of energetic and economic inefficiency in the separation of olefins from paraffins because the principal means of achieving industrial purity requirements is accomplished with very energy intensive cryogenic distillation. Mitigation of the severe energy intensity of the propylene/propane separation has been identified as one of seven chemical separations which can change the landscape of global energy use, and membranes have been targeted as an emerging technology because they offer scalability and lower capital and operating costs. The focus of this work was to evaluate a new direction of material development for the very industrially relevant propylene/propane separation using membranes. The objective was to develop a rational design approach for generating highly selective membranes using a relatively new platform of materials known as polyimides of intrinsic microporosity (PIM-PIs), the prospects of which have never been examined for the propylene/propane separation. Structurally, PIMs comprise relatively inflexible macromolecular architectures integrating contortion sites that help disrupt packing and trap microporous free volume elements (< 20 Å). To date most of the work reported in the literature on this separation is based on conventional low free volume 6FDA-based polyimides which in the best case show moderate C3H6/C3H8 selectivities (<20) with C3H6 permeabilities too low to garner industrial interest. Due to propylene and propane’s relatively large molecular size, we hypothesized that the use of more open structures can provide greater accessibility to the pores necessary to enhance membrane sieving and flux. It has been shown for numerous key gas separations that introduction of microporosity into a polymer structure can defy the notorious permeability/selectivity tradeoff curve and induce simultaneous boosts in both permeability and selectivity. The cornerstone approach to designing state of the art high performance PIM-PI membranes for the light gas separations involving maximizing the intra-segmental rigidity of the polymer chain was applied to the C3H6/C3H8 separation. A study regarding a stepwise maximization of intra-molecular rigidity and its effects on C3H6/C3H8 permeation was evaluated by conducting systematic structural modifications to high performance PIM-PIs. State of the art increases in performance were observed in pure-gas measurements as there were significant increases in C3H6/C3H8 selectivity and C3H6 permeability upon doing so. However, mixed-gas measurements showed that there were 65% losses in selectivity due to competitive sorption and mainly plasticization. Based on the conclusions drawn, a fundamental departure from conventional PIM design principles was used, instead emphasizing enhancing inter-chain interactions by introduction of a flexible diamine and functionalization with hydroxyl groups to attempt to immobilize the polymer chains. In doing so, the polymer chains may be able to pack more efficiently and upon sub-Tg annealing cause a microstructural reorganization to form a coplanarized configuration due to the combination of inter-chain charge transfer complexes (CTC) and hydrogen bonding networks. This approach successfully mitigated plasticization, but more importantly resulted in a tightening of the microstructure, especially in the ultra-microporous range (<7 Å) thereby yielding significant boosts in C3H6/C3H8 selectivity. Based on the PIM platform and novel polymer design approach thereof, the C3H6/C3H8 upper bound was thrust to new limits and led to the generation of the most selective solution processable polymers reported for the C3H6/C3H8 separation. Although the PIM platform has redefined the polymer upper bound, the permeability/selectivity tradeoff still endures, as the C3H6 permeabilities were on the order of 1 to 3.5 Barrer for the most selective polymers. To bridge that gap in permeability, several different approaches were taken. For the first time attempted for C3H6/C3H8 separation, high temperature heating of a PIM-PI to form thermally-rearranged and carbon molecular sieve membranes was employed. The TR membrane showed increased C3H6 permeability and about 50% losses in C3H6/C3H8 selectivity, while the CMS membrane formed at 600 oC showed modest gains in C3H6/C3H8 selectivity with significant improvements in C3H6 permeability. Finally, hybrid nanocomposite membranes incorporating a metal-organic framework structure into a PIM-PI matrix was used. ZIF-8, which has demonstrated high diffusive selectivities for C3H6/C3H8, was dispersed within the polymer, since previous work by the Koros group indicated that its incorporation into polyimide matrices can facilitate major improvements in both C3H6/C3H8 selectivity and C3H6 permeability compared to the respective neat polymer. Focus was directed towards attempting to improve polymer/nanoparticle adhesion by enhancing the interactions between the polymer and filler particles to mitigate the interfacial defects notorious in mixed-matrix membranes (MMM). To do so, ZIF-8 was dispersed into one of the best performing hydroxyl functionalized PIM-PI for the C3H6/C3H8 separation. The highest loaded mixed-matrix membrane in a glassy polymer to date of 65% (w/w) was achieved. The membranes showed pure-gas selectivities ranging from 34 with 10 Barrer at 30% loading to 43 with 38 Barrer at 65% loading. Strong performance and plasticization resistance were sustained in mixed-gas experiments even to feed pressures approaching the vapor pressure of the C3H6/C3H8 mixture, as selectivities well over 20 were achieved with high permeabilities, thereby demonstrating the potential commercial viability. Based on the work reported in this dissertation, we hope to help lay a framework to be able to tailor membrane performance and future membrane design to meet the demands of the different applications of the propylene/propane separation and hence show that there can be a marketplace for membranes in the separation. These include the debottlenecking of cryogenic distillation towers for production of polymer-grade propylene (99.5%) to reduce the associated extensive energy load, production of chemical-grade propylene (92-95% propylene), or for the recovery and recycling of olefins from reactor purges of petrochemical processes.

Tanha Design es una empresa dedicada a la elaboración y comercialización de productos a base de parafina. Actualmente, la empresa tiene 2 líneas de productos (velas y fanales) y una amplia variedad de modelos y diseños en ambas categorías. Esta empresa se encuentra en constante crecimiento y comercializa sus productos tanto en venta directa como en venta de sus productos para eventos sociales y corporativos. Actualmente, los eventos corporativos son los que representan mayor parte de sus ventas. Las entregas de productos para los eventos tienen una fecha limite; lo cual conlleva a una problemática para la capacidad de la línea de producción provocando que en ocasiones se rechacen ventas. En el presente proyecto se analiza la línea de producción de fanales de parafina debido a que estos productos representan mayor ingreso para la empresa. Asimismo, la capacidad de esta línea de producción no puede satisfacer la demanda actual y para ello requiere de personal adicional y horas extras. Dentro del análisis preliminar realizado se identificó que las causas de la disminución de la productividad son la falta de estandarización en el proceso, una deficiencia en el flujo productivo y desorden en las áreas de trabajo. Con la finalidad de solucionar esta problemática se implementó las 5”S” y el estudio de métodos, y con ello poder mejorar la productividad de la línea de elaboración de fanales con el objetivo de incrementar la capacidad productiva y disminuir las ventas perdidas. / Tanha Design is a company dedicated to the elaboration and commercialization of paraffin-based products. Currently, the company has 2 product lines (candles and lanterns) and a wide variety of models and designs in both categories. This company is constantly growing and markets its products both in direct sales and sale of its products for social and corporate events. Currently, corporate events are the ones that represent most of their sales. Product deliveries for events have a deadline; This leads to a problem for the capacity of the production line, causing that sales are sometimes rejected. This project analyzes the production line of paraffin lanterns because these products represent higher income for the company. In addition, the capacity of this production line cannot meet the current demand and requires additional staff and overtime. In the preliminary analysis, it was identified that the causes of the decrease in productivity are the lack of standardisation in the process, a deficiency in the productive flow and disorder in the areas of work. In order to solve this problem was implemented the 5 "S" and the study of methods, and thus be able to improve the productivity of the line of elaboration of lanterns with the aim of increasing the productive capacity and decrease the lost sales. / Tesis

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.

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