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Philosophiae Doctor - PhD / In this thesis, I present the electrochemical studies of three dendrimeric polypropylene imine (PPI) nanomaterials and their applications as a platform in the development of a novel label free DNA nanobiosensor based on electrochemical impedance spectroscopy. Cyclic voltammetry (CV), differentia pulse voltammetry (DPV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivities of the nanomaterials on glassy carbon electrode (GCE) as the working electrode. / South Africa

113 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-05T17:38:46Z No. of bitstreams: 1 Dissertação_Raildo Alves Fiuza Junior.pdf: 4123130 bytes, checksum: 5d64b18d9c873984e7609ecb4496b552 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-06-06T15:04:38Z (GMT) No. of bitstreams: 1 Dissertação_Raildo Alves Fiuza Junior.pdf: 4123130 bytes, checksum: 5d64b18d9c873984e7609ecb4496b552 (MD5) / Made available in DSpace on 2013-06-06T15:04:38Z (GMT). No. of bitstreams: 1 Dissertação_Raildo Alves Fiuza Junior.pdf: 4123130 bytes, checksum: 5d64b18d9c873984e7609ecb4496b552 (MD5) Previous issue date: 2012 / CAPES / A conversão catalítica do glicerol em insumos químicos de maior valor agregado é desejável para valorizar a cadeia de produção do biodiesel. O glicerol é obtido principalmente como co-produto do biodiesel, com rendimento de 10% em massa. Uma das vias mais promissoras na valorização do glicerol está na hidrogenólise do glicerol a propilenoglicol (1,2-PD), que é empregado como agente anti-congelante, na produção de polímeros, na indústria de alimentos e cosméticos. Muitos estudos têm relatado a hidrogenólise em fase líquida, que requer altas pressões de hidrogênio e demanda altos custos operacionais. Recentes estudos têm relatado a hidrogenólise do glicerol a 1,2-PDO em fase vapor, utilizando principalmente catalisadores a base de cobre. O principal catalisador empregado na hidrogenólise do glicerol tanto na fase liquida como vapor é a cromita de cobre, CuCr2O4. Neste trabalho, a atividade catalítica da cromita de cobre foi avaliada em fase vapor, estudando três fatores: a estruturação da cromita de cobre por diferentes temperaturas de calcinação (500-800°C); mudanças es truturais provocadas por diferentes métodos de síntese (Combustão e Pechini); e a modificação da estrutura da cromita pela introdução do alumínio em substituição do cromo. Todos os catalisadores foram caracterizados por DRX, FTIR, EDX, BET, TPR-H2 e área metálica do cobre. A hidrogenólise do glicerol em fase vapor se mostrou promissora e os resultados obtidos indicaram que a fase cromita de cobre propicia uma maior estabilidade para a fase ativa o cobre metálico. O aumento da área metálica do cobre é influenciado diretamente pelo método de síntese, maximizando a hidrogenólise. A introdução do alumínio provocou o aumento da seletividade ao propanodiol pela melhora nas propriedades texturais. / Salvador

abstract: Membrane-based gas separation is promising for efficient propylene/propane (C3H6/C3H8) separation with low energy consumption and minimum environment impact. Two microporous inorganic membrane candidates, MFI-type zeolite membrane and carbon molecular sieve membrane (CMS) have demonstrated excellent thermal and chemical stability. Application of these membranes into C3H6/C3H8 separation has not been well investigated. This dissertation presents fundamental studies on membrane synthesis, characterization and C3H6/C3H8 separation properties of MFI zeolite membrane and CMS membrane. MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H6/C3H8 mixture separation. CMS membranes were synthesized by coating/pyrolysis method on mesoporous γ-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N2 and C3H6 and C3H6/C3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores. CMS membranes demonstrate excellent C3H6/C3H8 separation performance over a wide range of feed pressure, composition and operation temperature. No plasticization was observed at a feed pressure up to 100 psi. The permeation and separation is mainly controlled by diffusion instead of adsorption. CMS membrane experienced a decline in permeance, and an increase in selectivity over time under on-stream C3H6/C3H8 separation. This aging behavior is due to the reduction in effective pore size and porosity caused by oxygen chemisorption and physical aging of the membrane structure. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2015

O propósito desta Tese é realizar o estudo da implementação do controle avançado do tipo controle preditivo baseado em modelo (MPC) e otimização em tempo real (RTO) em uma unidade de processo industrial usando como ferramentas softwares comerciais de simulação e otimização de processos. As soluções propostas podem ser consideradas como estratégias de integração entre RTO e MPC de uma e duas camadas. Na estratégia de duas camadas, a camada superior que considera um modelo rigoroso não linear do processo computa e envia targets otimizantes à camada dinâmica do MPC, que computa as ações de controle necessárias para alcançar esses targets e estabilizar o processo. Na estratégia de uma camada, mais conhecida como MPC econômico, temos a inclusão do gradiente da função econômica na função custo do controlador preditivo. Ambas as estratégias foram estudadas e suas implementações na coluna de destilação de propeno/propano com integração energética da unidade de produção de propeno da refinaria de Capuava da Petrobras foram simuladas. Este estudo foi realizado em varias etapas. Primeiro, uma simulação dinâmica do processo foi realizada usando o simulador dinâmico SimSci Dynsim® para ser usada como uma planta virtual que também foi usada para a identificação dos modelos usados nos controladores preditivos. Segundo, os algoritmos de controle avançado foram desenvolvidos em Matlab® baseados no controlador preditivo de horizonte infinito (IHMPC), no controlador preditivo robusto (RIHMPC) e no MPC econômico. Terceiro, o algoritmo de RTO foi desenvolvido no pacote de otimização em tempo real Simsci ROMeo®, onde o modelo rigoroso não linear do processo foi implantado incluindo as etapas de simulação, reconciliação de dados e otimização. Quarto, modificações e adaptações dos algoritmos e rotinas desenvolvidas foram feitas para permitir a comunicação de dados em tempo real usando o protocolo de transferência de dados OPC entre Matlab®, Simsci Dynsim® e Simsci ROMeo ®. Finalmente, foram desenvolvidos o sequenciamento e automação dos algoritmos tanto para leitura e escritura de dados, assim como, para a rotina do RTO. Para todas as estratégias propostas nesta Tese, foram incluídos exemplos de simulação representativos onde se pode evidenciar a estabilidade e convergência das estratégias propostas, chegando-se à conclusão que as estruturas propostas de RTO/MPC podem ser implementadas no sistema real. / The aim of this Thesis is to study the implementation of advanced control, specifically, Model Predictive Control (MPC) and real time optimization (RTO) in an industrial process system using tools such as commercial software for process simulation and optimization. The proposed solutions can be considered as integration strategies of RTO and MPC with one and two layers. In the two layer approach, the upper layer that considers a rigorous non-linear steady-state model of the process computes optimizing targets that are sent to the dynamic layer that are based on the MPC, which computes the necessary control actions to reach those targets and stabilize the process system. In the one layer strategy, also called as Economic MPC, the gradient of the economic function is included in the cost function of the predictive controller. Both strategies were studied and their implementation in the energy-recovery propylene/propane splitter system of the propylene production unit at the Capuava Refinery of Petrobras was simulated. In order to accomplish this objective, the work was developed in several steps. Firstly, a dynamic simulation of the process was built in the dynamic simulator Simsci Dynsim® so that it could be used as a virtual plant in which the model identification could also be performed. Secondly, the advanced control algorithms were developed in Matlab® based on the Infinite Horizon Model Predictive Control (IHMPC), the robust predictive controller (RIHMPC) and the Economic MPC. Thirdly, the RTO algorithm was developed in the real-time optimization package Simsci ROMeo®, where the non-linear rigorous model of the process was built including the stages of simulation, data reconciliation and optimization. Fourthly, modifications and adaptation of the developed algorithms and routines were included to allow the real-time data communication considering the OPC data transfer protocol between Matlab®, Dynsim® and ROMeo ®. Finally, a sequence of algorithms was developed and automated for data reading and writing, as well as, for the RTO sequence. For all the strategies developed in this Thesis, representative simulation examples were presented in order to show the closed-loop stability and convergence of the proposed approaches, leading to the conclusion that the proposed RTO/MPC structures can be implemented in the real system.

Orientadores: Vivaldo Silveira Junior, Flavio Vasconcelos da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-12T23:32:55Z (GMT). No. of bitstreams: 1 Fiori_JulianoJose_M.pdf: 6880493 bytes, checksum: d6458b990115262a0934b2886b8c7fb0 (MD5) Previous issue date: 2009 / Resumo: A utilização racional da energia é, atualmente, uma preocupação mundial. As questões ambientais referentes à degradação da camada de ozônio e ao aquecimento global caminham concomitante ao bom uso energético. A refrigeração destaca-se como sendo grande consumidora de energia elétrica, devido principalmente aos compressores. Focar um estudo no funcionamento desses componentes mostra-se coerente e vantajoso economicamente. Durante o horário de ponta, que corresponde a três horas do dia (das 18:00 as 21:00), há a possibilidade dos sistemas de refrigeração serem desligados, utilizando a energia a baixa temperatura que foi termoacumulada durante o período fora de ponta, com a diferença entre capacidade nominal e a necessária nas outras 21 horas do dia, podendo resultar em investimento fixo e custo variável menores, justificando o objetivo principal deste estudo. Apesar do coeficiente de performance (COP) de um sistema com fluido primário ser maior, a economia que ocorre em um sistema termoacumulado está no deslocamento da carga para horários em que a tarifa elétrica é menor. Estudando-se uma curva típica de carga térmica para uma câmara de estocagem pode-se verificar a aplicabilidade e economia de energia vinculada à utilização de um sistema com fluido secundário e termoacumulação. Para isso, foi realizado um estudo na carga térmica de uma câmara de estocagem de produtos resfriados com unidade frigorífica monobloco e localização interna a um prédio, avaliando-se diversas perturbações na mesma. Também foi construída uma instalação de fluido secundário (solução de propileno glicol) de um sistema de refrigeração (chiller) à câmara, adequandose trocadores de calor, tanques, isolamento térmico e instrumentação necessária. A estratégia de termoacumulação privilegiou o calor sensível, isto é, sem mudança de fase. Os ensaios realizados com o sistema construído e a estratégia de calor sensível mostraram que são eficientes para manter a temperatura da câmara abaixo de 5 ºC durante três horas no horário de ponta, racionalizando as curvas de demanda elétrica e térmica / Abstract: El uso racional de la energía es, en la actualidad, una preocupación mundial. Las cuestiones ambientales relativas a la degradación de la capa de ozono y el calentamiento global van conjuntamente al buen uso energético. La refrigeración se destaca como grande consumidora de energía eléctrica, debido principalmente al uso de los compresores. Hacer un estudio sobre el funcionamiento de estos componentes es coherente y económicamente ventajoso. Durante las horas punta, lo que corresponde a tres horas al día (de las 18:00 hasta las 21:00), existe la posibilidad de que no sea necesario el uso de los sistemas de refrigeración, utilizando la energía que se termoacumuló durante las horas fuera de punta, pudiendo resultar en la inversión fija y el costo variable inferiores, justificando el objetivo principal de este estudio. A pesar de que el coeficiente de performance (COP) de un sistema refrigerante primario sea superior, la economía que se produce en un sistema termoacumulado está en el desplazamiento de la carga durante horas en que la tarifa eléctrica es más baja. Estudiándose una típica curva de carga de calor para una cámara fría, se puede verificar la aplicabilidad y el ahorro de energía vinculado a la utilización de un sistema de fluido secundario y termoacumulación. Para ello, se realizó un estudio en la carga de calor de una cámara de almacenamiento en frío de productos alimenticios localizada interiormente a un edificio. También se construyó una instalación secundaria a la cámara del líquido utilizado (solución de propilenglicol) por el sistema de refrigeración (chiller), adecuándose intercambiadores de calor, tanques, aislamiento e instrumentación necesaria. La estrategia se concentró en la termoacumulación sensible, es decir, sin cambio de fase. Los ensayos realizados con el prototipo construido junto con la estrategia de calor sensible demostraron que son eficaces para mantener la temperatura de la cámara por debajo de 5 grados centígrados durante tres horas en el horario de punta, racionalizando las curvas de demanda eléctrica y térmica / Mestrado / Mestre em Engenharia de Alimentos

This thesis describes the reactions and emission spectra of propylene under radio frequency energy radiation.

Les interventions chirurgicales avec prothèses pour défauts de soutènement ont déjà nécessité l'implantation de plus d'un million de prothèses dans le monde. L'indication des prothèses de soutènement synthétiques non résorbables a permis de diminuer les récidives à court terme mais présente une incidence non négligeable de complications postopératoires. Le taux de réinterventions reste encore trop élevé. Cette thèse a pour objectif d'apporter de nouvelles propriétés à ces prothèses de polypropylène, pour à la fois améliorer leur résistance à l'infection et permettre leur visualisation en IRM clinique. Des treillis libérant des antibiotiques de façon contrôlée sont développés par enduction de polymère dégradable et biocompatible contenant des antibiotiques. Cette enduction présente une activité antibactérienne in vivo significative. Une autre enduction de polymères dégradables ou non dégradables, par une technique de pulvérisation par aérographie, permet une visualisation en IRM des treillis in vitro et après implantation. La stabilité du polymère greffé avec l'agent de contraste autorise une visualisation des treillis pendant au moins douze mois. / Surgical procedures with synthetic meshes have yet allowed more than one million operations. Non absorbable synthetic mesh used has permitted to decrease clinical recurrence at short term, but post operative complications still exist. Re operation rate is still too high. This study aims to develop new properties for those polypropylene meshes, such as infection resistance and MRI visualization. Meshes with controlled release of antibiotics were obtained after polymer coating and showed a significant in vivo antibacterial effect. Another mesh coating, with an aerograph procedure, has allowed MRI mesh visualization. To visualize by MRI, meshes after implantation, two new MRI visible polymer (degradable and non degradable) were coated onto meshes using an airbrush system. This coating allows the visualization of meshes in vitro and in vivo with experimental and clinical MR equipments. The stability of the MRI visible polymers permits to in vitro to visualize meshes during at least one year.

As far as the replacement of fossil fuels with more environmentally friendly options is concerned, hydrogen is considered as the most promising source of energy. Currently, hydrogen is mainly produced through the method of methane reforming. This method requires the utilisation of catalysts made of precious metals. This master's degree thesis therefore investigates perovskite materials SmCoO3, Sm0,8Ca0,2CoO2,9, SmCo0,8Al0,2O3 and Sm0,8Ca0,2Co0,8Al0,2O2,9, which could be utilised as catalysts in the production of hydrogen by methane reforming. Methane reformation occurs on the surface of a catalyst. Therefore, it is desirable to ensure that the specific surface area of a catalyst material is as large as possible. For that reason, the aforementioned perovskite materials were prepared by two sol-gel methods, which are expected to create perovskites with large specific surface areas. It was investigated in the course of the work how the method of synthesis affects the structure and catalytic properties of individual materials. The SmCo0,8Al0,2O3 material prepared by a sol-gel synthesis with propylene oxide as a gelation agent demonstrated the best results - the measurement of catalytic activity showed that the methane conversion had achieved the value of 99%.

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.