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Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-03-14T14:39:42Z No. of bitstreams: 1 Tese versão para homologação (30.07.15).pdf: 2226080 bytes, checksum: c8b1fccaa6da441fc65b1fccc4411d92 (MD5) Approved for entry into archive by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-05-10T13:21:21Z (GMT) No. of bitstreams: 1 Tese versão para homologação (30.07.15).pdf: 2226080 bytes, checksum: c8b1fccaa6da441fc65b1fccc4411d92 (MD5) Made available in DSpace on 2016-05-10T13:21:22Z (GMT). No. of bitstreams: 1 Tese versão para homologação (30.07.15).pdf: 2226080 bytes, checksum: c8b1fccaa6da441fc65b1fccc4411d92 (MD5) CNPq Esta tese descreve o planejamento, construção, otimização e aplicação de um sistema experimental dedicado ao estudo do processo de dispersão de parafinas em microfluxos de petróleo. O sistema consiste na combinação das técnicas de Análise por Injeção em Fluxo (FIA), Fluorescência Induzida por Laser (LIF), Despolarização da Fluorescência Induzida por Laser (PLF) e Lente Térmica (LT), com alta resolução espacial. Um dispositivo de injeção em fluxo, baseado em micro válvulas solenóides controladas remotamente, foi construído para gerenciar o fluxo de amostra. Esta consiste de petróleo parafínico, proveniente da Bacia do Recôncavo da Bahia, dissolvido em óleo mineral. A amostra é analisada numa cela de fluxo com seção reta de 1mm2 disposta em um posicionador automático, de construção própria, capaz de varrer a zona de amostragem com resolução de 400 pontos/mm2. Um laser de Argônio é responsável por gerar, simultaneamente, os sinais LT e LIF/PLF, que são detectados em duas linhas de luz distintas. A rotina de aquisição de dados consistiu em sucessivas injeções de amostra num percurso analítico de 30cm. Após as injeções os perfis de dispersão são individualmente detectados em diferentes posições da cela de fluxo e interpolados numa matriz de dados, gerando um mapa bidimensional de dispersão. Foram adicionados padrões de 3 tipos diferentes de parafina à amostra com o objetivo de determinar a sensibilidade do sistema à concentração e ao tamanho da cadeia parafínica. Os resultados mostram que os sinais fototérmico e fluorescente revelam informações distintas acerca da amostra, mas que ao mesmo tempo são complementares. Nas condições descritas nesta tese, tanto a LT quanto o LIF variaram linearmente com a concentração de petróleo, apresentaram boa resolução temporal e alta resolução espacial. Os mapas LIF mostraram um perfil de distribuição de massa compatível com um fluxo laminar. Foi verificado uma clara modificação no comportamento do fluxo de petróleo, a nível molecular, em função do tamanho da cadeia das parafinas adicionadas e da concentração em que estas se encontravam na solução. Durante o desenvolvimento do sistema foi possível implementar uma metodologia para a determinação do grau de polarização/anisotropia da amostra de petróleo em fluxo por absorção, à partir dos dados LT. Enfim, não apenas foi demonstrada a viabilidade de se utilizar detecção fototérmica em amostras de petróleo, como também se mostrou possível a adaptação de um sistema FIA com detecção simultânea de fluorescência em tempo real. Além disto, o sistema se mostrou eficiente na observação da dinâmica molecular do fluxo permitindo verificar a influência de moléculas parafínicas no processo de dispersão molecular de amostras de petróleo injetadas em óleo mineral, bem como a influência do tamanho da cadeia parafínica na estrutura e nas propriedades fotofísicas do fluido em processo de escoamento This thesis describes the planning, construction, optimization and application of an experimental system dedicated to the study of paraffin dispersion process in oil micro flows. The system consists of the combination of Flow Injection Analysis (FIA), Laser Induced Fluorescence (LIF), Polarized Laser Induced Fluorescence (PLF) and Thermal Lens (TL) techniques, with high spatial resolution. An flow injection device based on solenoid valves, controlled remotely, was built to manage the flow of sample. This consists of paraffinic oil, from the Recôncavo da Bahia Basin, dissolved in mineral oil. The sample is analyzed in a flow cell with 1mm2 cross section disposed in a homemade automatic positioner, able to scan the sample zone with a resolution of 400 dots/mm2. An Argon-ion laser is responsible for generating both TL and LIF/PLF signals, which are detected in two different lines of light. The data acquisition routine consisted of successive injections of sample in a 30cm analytical path. After injections the dispersion profiles are individually detected at different positions of the flow cell and interpolated in a data matrix, generating a two-dimensional dispersion map. 3 different types of paraffin standards were added in to the sample in order to determine the sensitivity of the system to the concentration and size of the paraffinic chain. The results show that the photothermal and fluorescent signals show different information about the sample, but at the same time are complementary. Under the conditions described in this thesis, both the TL and the LIF varied linearly with oil concentration, showed good temporal resolution and high spatial resolution. The LIF maps showed a mass distribution profile compatible with a laminar flow. A clear change in the oil flow behavior was observed at the molecular level, depending on the size of the chain of added paraffins and concentration as they were in solution. During development of the system it was possible to implement a methodology for determining the degree of polarization/anisotropy of the oil sample in flow by absorption, starting by TL data. Finally, not only been demonstrated the feasibility of using photothermal detection on oil samples, such as adaptation of a FIA system with simultaneous detection of real-time fluorescence was also possible. In addition, the system was efficient in the observation of molecular dynamics flow allowing verifying the influence of paraffinic molecules in the molecular dispersion process of oil samples injected in mineral oil, as well as the influence of the size of the paraffin chain on the structure and photophysical properties of the fluid.

Texto completo: acesso restrito. p.620–624 Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-08-28T15:34:56Z No. of bitstreams: 1 ef050267p.pdf: 167516 bytes, checksum: 79320d484955c126069761ce99be4190 (MD5) Made available in DSpace on 2013-08-28T15:34:56Z (GMT). No. of bitstreams: 1 ef050267p.pdf: 167516 bytes, checksum: 79320d484955c126069761ce99be4190 (MD5) Previous issue date: 2006 Pipelines for heavy crude oils have recurrent clogging situations due to paraffin deposition that may lower production rates and be responsible for leakages. This work evaluates the effect of three polymers on crude oil wettability and on paraffin deposition inhibition: polypropylene (PP), high-density polyethylene (HDPE), and a vinyl acetate copolymer with 28% oxygen content (EVA28). Under static conditions, the interfacial tension between the crude oil and the linings was determined by the contact angle being 12% and 17% higher for EVA28 and HDPE, respectively, than for that of PP. As the crude oil inside the pipelines is flowing at high rates, the dynamic interfacial tension was also observed for high flow rates when molecular effects overtake hydrodynamic ones. For this, the perturbation of intermolecular orientation within the flow, caused by the beginning of deposit formation and by the wettability, was determined using depolarization of the fluorescence induced by laser. Under flow, EVA28 and HDPE caused an increase of interaction with the crude oil of 79% and 43%, respectively, compared to that of PP. HDPE yielded globular wax deposits. The higher tendency of HDPE than PP to form deposits was attributed to the absence of methyl branches in the first. The EVA28 tendency to form deposits was attributed to the oxygen atoms on the surface as well as to its high polycyclic aromatic hydrocarbon sorption. Thus, under a high flow rate, PP is better suited to inhibit wax deposition than HDPE and EVA28.

Trabalho completo: acesso restrito, p. 201–208 Submitted by Bruna Lessa (lessbruna@gmail.com) on 2012-08-31T19:01:36Z No. of bitstreams: 1 (183).pdf: 371831 bytes, checksum: 7eae9ece1dd4f13ec39e763a0689a7f9 (MD5) Made available in DSpace on 2012-08-31T19:01:36Z (GMT). No. of bitstreams: 1 (183).pdf: 371831 bytes, checksum: 7eae9ece1dd4f13ec39e763a0689a7f9 (MD5) Previous issue date: 2005-01-01 This work was concerned with the dependence of the interfacial tension (ΓSL) on surface degree of oxygen content and on polymer branching degree. The static ΓSL was evaluated by contact angle (θc) and the dynamic ΓSL by fluorescence depolarization of molecular probes seeded in induced flows of monoethylene glycol. The latter results were interpreted using statistical covariant analysis. Two different systems of flowing films were studied: free films flowing on the surfaces on which they impinge and films flowing inside 1-mm-thick microflow cells. The solid surfaces were polyethylene of low density, medium density, high density, and linear with low density, polypropylene, vinyl acetate co-polymer with oxygen content of 15% and 28%, borosilicate, and tin dioxide. Increase in oxygen content of the surface decreased both the static and the dynamic ΓSL, which demonstrated that the presence of oxygen atoms hindered wetting. Only the dynamical ΓSL was sensitive to polymer branching, and it increased as branching degree decreased. This was attributed to the higher hydrogen-atom density at the surface, which favored temporary intermolecular bonds between the surface and the flowing liquid.

Texto completo: acesso restrito. p. 293–300 Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-12-03T11:32:08Z No. of bitstreams: 1 Cristina M. Quintella.pdf: 263933 bytes, checksum: 641798a44a72a4095dc78fc3fdc95998 (MD5) Made available in DSpace on 2013-12-03T11:32:08Z (GMT). No. of bitstreams: 1 Cristina M. Quintella.pdf: 263933 bytes, checksum: 641798a44a72a4095dc78fc3fdc95998 (MD5) Previous issue date: 2004 A fully mechanized set-up was built for the experimental determination of bi-dimensional dispersion with high spatial resolution (2400 μm2). Gravitational and wall effects in a single stream were evaluated by using time-based sampling and a micro-flow cell. Vertical upward and downward flows as well as horizontal flows were investigated. Ethylene glycol (MEG) and Rhodamine B in MEG were used as carrier and sample solutions, respectively. Longitudinal profiles were obtained by laser induced total fluorescence (LIF) at up to 19 transversal sites and combined to generate high-resolution bi-dimensional profiles. A two frontal maxima pattern was observed for all flows. The volumetric fraction of RB shape was highly stretched for downward flow and there was high asymmetry for horizontal flow. The sensitivity of three dispersion parameters was evaluated: maximum peak value, peak half-width at half-height, and peak area. Data modeling showed that the tanks-in-series was more sensitive to wall effects, had good adjustment with only one tank for upward and horizontal flow and needed two tanks for downward flow which was attributed to the latter having higher dispersion. A black box empirical modeling described better the gravitational effect and allowed to identify a parameter sensitive to upward and downward flow as well as hinting to two inner streams within the horizontal flow. It also pointed to a wall dispersion contribution of twice that of the liquid–liquid dispersion.

p. 201–205 Submitted by Ana Valéria de Jesus Moura (anavaleria_131@hotmail.com) on 2012-01-24T12:18:33Z No. of bitstreams: 1 S0021979703009251-main.pdf: 299759 bytes, checksum: c66ed76d14a5df4bad3cbac2fa29a09b (MD5) Made available in DSpace on 2012-01-24T12:18:33Z (GMT). No. of bitstreams: 1 S0021979703009251-main.pdf: 299759 bytes, checksum: c66ed76d14a5df4bad3cbac2fa29a09b (MD5) Previous issue date: 2004 A recent trend is the production of workable microchannel flow cells (MF cells). The nondestructive methods used to assess their reliability are based mainly on output monitoring and do not evaluate internal chemical interactions. We investigate a nondestructive method for evaluating changes in the chemical composition of the inner walls based on evaluation of the extent of alignment of a fluorescent probe in a liquid flowing within MF cells. Two MF cells were built with a 10-μm inner spacing. Their inner walls had four parallel SnO2 strips, 2.00 mm wide, separated by 0.50-mm-wide glass strips. One cell had strips parallel to the flow and the other perpendicular. Flow-induced intermolecular alignment of rhodamine B in monoethylene glycol was scanned with 28-μm precision by fluorescence depolarization, using polarized-laser-induced fluorescence within induced flows (PLF-FI).No changes of polarization were seen when the flow was stopped. Under flowing conditions, polarization was always 4% lower in the glass region as compared to SnO2. Glass had a higher solid–liquid interfacial tension (determined by contact angle measurements), thus being more wettable and increasing the drag, which propagates into the liquid flow, decreasing polarization. PLF-FI can thus identify regions with different chemical constitutions.

Texto completo: acesso restrito. p. 221–226 Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-12-18T14:28:19Z No. of bitstreams: 1 Cristina M Quintella.pdf: 132092 bytes, checksum: 3fc41b07320f240670d19f3ef4fe83f3 (MD5) Made available in DSpace on 2013-12-18T14:28:19Z (GMT). No. of bitstreams: 1 Cristina M Quintella.pdf: 132092 bytes, checksum: 3fc41b07320f240670d19f3ef4fe83f3 (MD5) Previous issue date: 2003 Interfacial interactions control two processes empirically known to be critical for molecular anchoring in twisted nematic liquid crystal displays technology (TN-LCDs): surface treatment and filling procedure. Static and dynamical interfacial tensions (ΓSL) between liquids and several substrates with similar roughness were observed respectively by contact angle (θc) of sessile drops and by fluorescence depolarization of thin liquid films flowing at high velocity. ΓSL decreased when glass was coated with tin dioxide and increased with polyvinyl alcohol (PVA) deposition. Drops were circular for all substrates except rubbed PVA, where they flowed spontaneously along the rubbing direction, reaching an oblong form that had θc parallel and perpendicular to the rubbing direction respectively greater and smaller than θc for nonrubbed PVA. This is attributed to polar group alignment generating an asymmetric ΓSL distribution with nanometric preferential direction, inducing a capillary-like flow. Polarization and anisotropy maps for high-velocity flow parallel to the PVA rubbing direction showed an increase in the net alignment of molecular domains and a widening of the region where it occurred. This is attributed to preferential anchoring in the downstream direction, instead of in several directions, as for nonrubbed PVA. This explains why filling direction is crucial for TN-LCDs homogeneous behavior.

Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-04-23T14:35:12Z No. of bitstreams: 1 Yuji Watanabe.pdf: 3696013 bytes, checksum: 64d732d452c08c675e78db3f991bf851 (MD5) Made available in DSpace on 2013-04-23T14:35:12Z (GMT). No. of bitstreams: 1 Yuji Watanabe.pdf: 3696013 bytes, checksum: 64d732d452c08c675e78db3f991bf851 (MD5) Previous issue date: 2002 Este trabalho é constituído de três etapas, a saber: · planejamento e construção de um aparato experimental para medidas de fluorescência total (LIF) e depolarização fluorescente (PLF) em sistema de injeção em fluxo (FI); testes operacionais visando otimizar parâmetros experimentais; avaliação fotoquímica/fotofísica da cinética e dinâmica molecular duma reação química em FI. O aparato experimental automatizado é constituído de um sistema de detecção de fluorescência, um sistema FI e um sistema ótico. Permite a aquisição com alta resolução espacial (20mm) de perfis de distribuição de concentração (LIF) e de orientação molecular vertical e horizontal (PLF) em função do tempo de transporte do fluxo. Os perfis interpolados em mapas bidimensionais fornecem informações sobre a cinética e a dinâmica molecular dos processos de dispersão axial e radial de amostras em fluxo carregador. Foram medidas tensões interfaciais estáticas, pelo método do ângulo de contato, para escolher a constituição química do percurso analítico e minimizar a sua influência na cinética e na dinâmica molecular de dispersão. Foi determinada a influência da aceleração gravitacional e do número de injeções por período de amostragem, dentre outros parâmetros usuais, no processo de dispersão.Observou-se a existência de padrões de dispersão diferenciados para a Rodamina B (RB) a depender da sua orientação espacial. Isto foi atribuído ao grupo benzóico perpendicular ao grupo xantênico e comprovado pela utilização da Rodamina 6G (R6G) sob as mesmas condições. A contribuição da cinética e da dinâmica moleculares de dispersão no rendimento de uma reaçãoquímica em fluxo foi avaliado com adição de Ca(II), um agente supressor da fluorescência da RB. Salvador