Made available in DSpace on 2014-12-17T15:01:13Z (GMT). No. of bitstreams: 1 PaulaKLS.pdf: 655947 bytes, checksum: 42dfa97fce97ed099a5660c9d396a0eb (MD5) Previous issue date: 2008-02-29 / In the petroleum industry, water is always present in the reservoir formation together with petroleum and natural gas and this fact provokes the production of water with petroleum, resulting in a great environmental impact. Several methods can be applied for treatment of oily waters, such as: gravitational vases, granulated media filtration systems, flotation process, centrifugation process and the use of hydrocyclones, which can also be used in a combined way. However, the flotation process has showed a great efficiency as compared with other methods, because these methods do not remove great part of the emulsified oil. In this work was investigated the use of surfactants derived from vegetable oils, OSS and OGS, as collectors, using the flotation process in a glass column with a porous plate filter in its base for the input of the gaseous steam. For this purpose, oil/water emulsions were prepared using mechanical stirring, with concentrations around 300 ppm. The air flow rate was set at 700 cm3/min and the porous plate filter used for the generation of the air bubbles has pore size varying from 16 to 40 Pm. The column operated at constant volume (1500mL). A new methodology has been developed to collect the samples, where, instead of collecting the water phase, it was collected the oil phase removed by the process in the top of the flotation column. It has been observed that it is necessary to find an optimum surfactant concentration to achieve enhanced removal efficiency. Being for OSS 1.275 mmol/L and for OGS 0.840 mmol/L, with removal efficiencies of 93% and 99%, respectively, using synthetic solutions. For the produced water, the removal in these concentrations was 75% for OSS and 65% for OGS. It is possible to remove oil from water in a flotation process using surfactants of high HLB, fact that is against the own definition of HLB (Hydrophile-Lipophile Balance). The interfacial tension is an important factor in the oil removal process using a flotation process, because it has direct interference in the coalescence of the oil drops. The spreading of the oil of the air bubble should be considered in the process, and for the optimum surfactant concentrations it reached a maximum value. The removal kinetics for the flotation process using surfactants in the optimum concentration has been adjusted according to a first order model, for synthetic water as for the produced water. / Na ind?stria petrol?fera, a ?gua est? associada ao petr?leo e ao g?s natural, formando a ?gua de produ??o e gerando um grande impacto ambiental. Existem diversos m?todos de tratamento para as ?guas oleosas, tais como: vasos gravitacionais, sistemas de filtra??o em meio granular, flota??o, centrifuga??o e utiliza??o de hidrociclones, podendo ser utilizados de forma combinada. Entretanto, a flota??o tem mostrado maior efici?ncia com rela??o aos outros m?todos, pois eles n?o conseguem remover grande parte do ?leo emulsionado. O presente trabalho estuda a utiliza??o de tensoativos de origem vegetal, OSS (?leo de Soja Saponificado) e OGS (?leo de Girassol Saponificado), como coletores, atrav?s da flota??o em uma coluna com aera??o da suspens?o atrav?s de uma placa porosa. Para este fim, foram preparadas emuls?es ?leo/?gua por agita??o mec?nica, com concentra??es m?dias de 300 ppm. A vaz?o de ar utilizada foi de 700 cm3/min e o filtro de placa porosa utilizado para a gera??o das bolhas de ar foi de porosidade de (16-40) Pm. A coluna trabalhou a um volume constante de 1500mL. Desenvolveu-se uma nova metodologia para coletar as amostras, onde, ao inv?s de coletar a ?gua, coletou-se o ?leo removido na parte superior da c?lula de flota??o. Observou-se que ? necess?rio encontrar uma concentra??o ?tima de tensoativo para que haja uma maior efici?ncia de remo??o. S?o elas 1,275 mmol/L para o OSS e 0,840 mmol/L para o OGS, com efici?ncias de remo??o de 93 % e 99 %, respectivamente, em ?guas sint?ticas. Para a ?gua de produ??o, a remo??o nestas concentra??es foi de 75% para o OSS e 65% para o OGS. ? poss?vel remover ?leo de ?gua em um processo de flota??o utilizando tensoativos de BHL alto, fato que contraria a pr?pria defini??o de BHL (Balan?o Hidrof?lico-Lipof?lico). A tens?o interfacial ? um fator importante no processo de remo??o do ?leo na flota??o, pois interfere diretamente na coalesc?ncia das gotas de ?leo. O espalhamento do ?leo da bolha de ar deve ser considerado no processo, e para as concentra??es ?timas de tensoativo atingiu um valor m?ximo. A cin?tica da remo??o se ajustou para o modelo de primeira ordem na flota??o utilizando tensoativos na concentra??o ?tima, tanto para ?gua sint?tica como para a ?gua de produ??o.

Made available in DSpace on 2014-12-17T15:01:17Z (GMT). No. of bitstreams: 1 BentoPCN.pdf: 1568863 bytes, checksum: bd484a66a36dd1be9ccc75015b40e5e8 (MD5) Previous issue date: 2009-03-05 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Currently, studies in the area of polymeric microcapsules and nanocapsules and controlled release are considerably advanced. This work aims the study and development of microcapsules and nanocapsules from Chitosan/MDI, using a new technique of interfacial polycondensation combined to spontaneous emulsification, for encapsulation of BZ-3. It was firstly elaborated an experimental design of 23 of the particle in white without the presence of BZ-3 and Miglyol, where the variables were the concentrations of MDI, chitosan and solvent. Starting from the data supplied by the experimental design was chosen the experiment with smaller particle diameter and only added like this BZ-3 and Miglyol. The suspension containing concentrations of 6.25 mg/mL, 12.5 mg/mL, 18.75 mg/mL, 25 mg/mL of BZ-3 were prepared, nevertheless, during the storage time, these formulations presented drug precipitates in the suspensions of 18.75 mg/mL and 25 mg/mL of BZ-3. This apparition of precipitate was attributed to the diffusion of BZ-3 for the aqueous phase without any encapsulation, suggesting so the use of the smaller concentrations of the BZ-3. The suspension containing 6.25mg/mL of BZ3 presented average size of 1.47μm, zeta potential of 61 mV, pH 5.64 and this sample showed an amount of BZ-3 and drug entrapment of 100 %. The suspension containing 12.5mg/mL of BZ-3 presented average size of 1.76μm, zeta potential of 47.4 mV, pH 5.71 and this sample showed an amount of BZ-3 and drug entrapment of 100 %. Then, showing such important characteristics, these two formulations were chosen for futher continuity to the study. These formulations were also characterized by the morphology, FTIR, stability for Turbiscan, DSC and a study of controlled release of the BZ-3 was elaborated in different receiving means / O presente trabalho visou o estudo e desenvolvimento de um sistema micro e nanoestruturado de quitosana reticulada por diisocianato, pela t?cnica de policondensa??o interfacial combinada com emulsifica??o espont?nea, para encapsula??o de benzofenona-3 (BZ-3), um filtro solar qu?mico. Foi elaborado primeiramente um planejamento experimental de 23 para desenvolvimento da formula??o de part?culas de quitosana e MDI (4,4 -difenil metano diisocianato), onde as vari?veis foram ?s concentra??es de MDI, de quitosana e do solvente. A partir dos dados fornecidos pelo planejamento experimental, optou-se pelas condi??es de processo e formula??o capazes de gerar o menor di?metro de part?cula. O estudo prosseguiu com a incorpora??o de BZ-3 e Miglyol (n?cleo das c?psulas formadas). Suspens?es de nanoc?psulas com concentra??es de 6,25 mg/mL, 12,5 mg/mL, 18,75 mg/mL e 25 mg/mL de BZ-3 foram preparadas, por?m durante o per?odo de armazenamento ocorreu o aparecimento de precipitados cristalinos, nas suspens?es de 18,75 mg/mL e 25 mg/mL de BZ-3. Este aparecimento de precipitados cristalinos foi atribu?do ? difus?o da BZ-3 para a fase aquosa n?o ocorrendo sua encapsula??o. A suspens?o contendo 6,25 mg/mL de BZ-3 apresentou di?metro m?dio de 1,47μm, potencial zeta de 61 mV, pH de 5,64 e teor de encapsula??o pr?ximos a 100 %. A suspens?o contendo 12,5mg/mL de BZ-3 apresentou di?metro m?dio de 1,76μm, potencial zeta de 47,4mV, pH 5,71 e teor de encapsula??o pr?ximos a 100 % e foi selecionada juntamente com a de 6,25 mg/mL para a continuidade do estudo. Estas formula??es foram caracterizadas tamb?m pela morfologia, turbidimetria, espectroscopia de absor??o na regi?o do infravermelho, DSC e foi elaborado um estudo de libera??o controlada do f?rmaco em diferentes meios receptores. Em conclus?o, o conjunto dos resultados obtidos demonstra que estas formula??es s?o sistemas promissores para a aplica??o cut?nea de filtros solares

Uma nova metodologia para a medida não intrusiva da fração volumétrica e da área interfacial é proposta neste trabalho, com base em redes neurais para processar respostas obtidas de sinais acústicos. A distribuição geométrica das fases dentro do escoamento é mapeada pela velocidade local de propagação acústica, considerada na equação diferencial que governa o problema. Esta equação é resolvida numericamente pelo método de diferenças finitas com as condições de contorno reproduzindo a estratégia de pulso/eco. Um número significativo de distribuições das velocidades de propagação foi considerado na solução da equação diferencial para construir uma base de dados, da qual os parâmetros da rede podem ser ajustados. Especificamente, o modelo neural é construído para mapear características extraídas dos sinais obtidos de quatro sensores acústicos, localizados no contorno externo do domínio de sensoriamento, estimando a fração volumétrica e a área interfacial correspondentes. Estas características correspondem às amplitudes e aos tempos de chegada dos três maiores picos da onda acústica. Os resultados numéricos mostram que o modelo neural pode ser treinado em um tempo computacional razoável e é capaz de estimar os valores da fração volumétrica e da área interfacial dos exemplos do conjunto de teste. / A new methodology for measuring the volumetric fraction and interfacial area in two-phase flows is proposed in this work, based on neural network for processing the responses obtained from an acoustic interrogation signal. The geometrical distribution of the phases within the flow is mapped by the local acoustic propagation velocity which is considered in the governing differential equation. This equation is solved numerically by the finite difference method with boundary conditions reproducing the pulse/echo strategy. A significant number of propagation velocities distributions were considered in the solution of the differential equation in order to construct a database from which the neural model parameters could be adjusted. Specifically, the neural model is constructed to map the features extracted from the signals delivered by four acoustic sensors, placed on the external boundary of the sensing domain, into the corresponding volumetric fraction and interfacial area. These features correspond to the amplitudes and the times of arrival on the three first peaks of the acoustic wave. Numerical results showed that the neural model can be trained in a reasonable computational time and it is capable of estimating the values of the volumetric fraction and the interfacial area of examples of the set of test.

O escoamento estratificado óleo-água é bastante comum na indústria do petróleo, especialmente em poços direcionas offshore, oleodutos e gasodutos. Entretanto, existem poucos trabalhos na literatura sobre a natureza da estrutura ondulatória observada no escoamento em dutos ascendentes ou descendentes a partir da horizontal. O objetivo deste trabalho foi estudar as propriedades geométricas e cinemáticas da onda interfacial, i.e, forma média, comprimento, amplitude e celeridade, e assim contribuir para a compreensão do papel da onda interfacial na dinâmica do escoamento estratificado. Um software baseado em plataforma Labview® possibilitou a automação para obtenção dos dados das ondas interfaciais extraídas de imagens de vídeos de alta resolução. Além das propriedades das ondas, também se coletaram valores de fração volumétrica in situ e de gradiente de pressão bifásico para cinco ângulos de inclinação (-20°, -10°, 0°, 10° e 20°) em diferentes pares de vazões de óleo e água. Desenvolveu-se um modelo fenomenológico considerando os termos ondulatórios do escoamento para o cálculo da fração volumétrica in situ e do gradiente de pressão bifásico, sendo comparado com modelos disponíveis na literatura e dados experimentais. A concordância do modelo proposto com os dados coletados neste trabalho se mostrou muito boa, o que sugere um avanço em comparação ao existente na literatura. O estudo da equação da onda de perturbação interfacial para o escoamento estratificado óleo-água indicou que a natureza da onda observada é cinemática e não dinâmica; e baseado na equação da celeridade da onda cinemática pode-se confrontar a celeridade experimental com a teórica, revelando boa concordância. / The oil-water stratified flow is quite common in the oil industry, especially in offshore directional wells and pipelines. However, there are few studies on the physics of the wavy structure observed in upward and downward stratified flow. The goal of this work was to study the geometric and kinematic properties of interfacial waves, i.e., the average shape, wavelength, amplitude and celerity. A homemade Labview®-based software enabled the automatic acquisition of data extracted from frames obtained via high resolution video recording. In situ volume fraction and two-phase pressure gradient data for five inclination angles (-20°, -10°, 0°, 10° and 20°) at several pairs of oil and water flow rates were also collected. A phenomenological model that takes into account the wavy structure is proposed to calculate volume fractions and two-phase pressure gradient and it was compared with available models from the literature and experimental data. The good agreement of the proposed model with the data collected in this study is promising and suggests that it may provide better predictions in comparison with models from the literature. The study of the interfacial perturbation wave equation for stratified flow indicates that the observed waves nature is kinematic and not dynamic; and based on the kinematic wave velocity equation we could compare the experimental celerity with the theoretical one, with good agreement.

Neste trabalho, sondas solvatocrômicas foram empregadas no estudo da solvatação em solventes puros e misturas aquosas de solventes polares práticos e apráticos. A partir da polaridade de misturas aquosas de solventes orgânicos, determinou-se a concentração de água interfacial de micelas catiônicas. Finalmente, avaliou-se o efeito da polaridade e força iônica interfaciais de micelas catiônicas sobre a velocidade da reação entre p-nitrofenildifenilfosfato e o íon fluoreto. No estudo de misturas aquosas de solventes orgânicos, um novo modelo de solvatação preferencial foi elaborado, segundo o qual três espécies presentes em solução competem pela camada de solvatação da sonda: água, solvente orgânico e o \"complexo\" formado por uma molécula de água e outra de solvente orgânico (Solv-Água). Através deste modelo, analisou-se o efeito da temperatura e das propriedades das sondas e dos solventes orgânicos sobre o fenômeno da solvatação. Em soluções aquosas de micelas catiônicas, observou-se uma desidratação da interface em função do aumento do grupo hidrofílico do tensotativo e da mudança de geometria micelar de esférica para cilíndrica. Verificou-se que a velocidade da reação entre pnitrofenildifenilfosfato e fluoreto é pouco afetada pela interface micelar e pode ser reproduzida, na ausência de micelas, em soluções com mesma concentração de água e força iônica que as micelas. / Solvatochromic probes have been employed to study the polarity of pure solvents and binary mixtures of water with protic and aprotic polar solvents. From polarity data of aqueous organic mixtures, the concentration of interfacial water of cationic micelles has been determined. In aqueous solutions of cationic micelles, the dehydration of interfacial region has been observed as a result of increasing the volume of the surfactant head group and changing micellar geometry from spherical to cylindrical. Finally, the effect of interfacial polarity and ionic force on the rate of the reaction between 4-nitrophenyldiphenylphosphate and fluoride ion has been evaluated. In studying aqueous organic mixtures, a new preferential solvation model has been developed, that considers the competition between three species in solution for the probe micro-solvation shell: water, organic solvent and a 1:1 \"complex\" formed by water and organic solvent (Solv-Água). Based on this new model, the effect of temperature, as well as probe and organic solvent properties on solvation has been analyzed. It has been observed that the rate of the reaction between p-nitrophenyldiphenylphosphate and fluoride ion shows little dependence on the properties of interfacial region of cationic micelles and can be reproduced, in the absence of micelles, in solutions containing the same water concentration and ionic force as the micellar pseudo-phase.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23506号 / 工博第4918号 / 新制||工||1768(附属図書館) / 京都大学大学院工学研究科原子核工学専攻 / (主査)教授 中島 健, 教授 横峯 健彦, 准教授 山本 俊弘 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Les problématiques liées aux surfaces et interfaces prennent de plus en plus d’importance dans de nombreux secteurs, aussi bien académiques qu’industriels. Dans de nombreuses applications, il n’est parfois pas nécessaire de conférer la réactivité désirée à la totalité du volume du matériau : une surface aux propriétés bien contrôlées peut suffire.Lieu de discontinuité des propriétés d’un matériau, la surface possède un comportement qui lui est propre, généralement apporté par une étape de fonctionnalisation. Dans ce contexte, ce travail de thèse vise à élaborer des surfaces polymères aux propriétés thermoréversibles, de comprendre les mécanismes réactionnels mis en jeu aux interfaces et de proposer de nouvelles surfaces aux pouvoirs adhésifs réversibles.Il existe de nombreuses techniques permettant de modifier la surface des matériaux. La littérature est abondante et variée, on y trouve notamment des techniques visant à introduire des groupements fonctionnels à la surface d’un substrat. Parmi elles, la polymérisation plasma est une technique de dépôt chimique en phase vapeur, sans solvant, permettant le dépôt de films minces de polymères aux propriétés physico-chimiques contrôlées sur une grande variété de matériaux. Le plasma, état très excité de la matière, est généré grâce à un champ électromagnétique. C’est cette technique de fonctionnalisation qui a été choisie dans ce travail de thèse dans le but de déposer un film mince de polymère possédant des propriétés thermoréversibles sur divers substrats.Les propriétés de thermoréversibilité sont apportées grâce à la présence de groupements furanes, capables de réagir avec un diénophile par une réaction de Diels-Alder (DA). Cette réaction, dite « click », entre un diène et un diénophile a été décrite pour la première fois en 1928 par Otto Diels et Kurt Alder, et fut à l’origine de l’obtention de leur Prix Nobel en 1950. Dans la littérature, les études sur la réaction de DA sont majoritairement réalisées en solution voire sur des matériaux massifs. Cette chimie a été beaucoup moins étudiée sur/dans des films minces, où la notion de confinement prend toute son importance. C’est dans ce contexte que se posent ces travaux de thèse.Dans un premier temps, une étude expérimentale approfondie sur la réactivité de DA (étude cinétique et thermodynamique) a été réalisée. Des polymères plasma ayant des propriétés physico-chimiques variées ont été synthétisés et un couple diène/diénophile modèle, le furane présent dans le polymère plasma et l’anhydride maléique en solution, a été choisi. La compréhension de la réactivité interfaciale de DA sur des polymères plasma constitue la première grande partie de cette thèse. Diverses méthodes de caractérisation des propriétés du film mince fonctionnel (spectroscopie infrarouge, spectrométrie photo-électronique X, mesures d’angle de contact, mesures par microbalance à cristal de quartz avec dissipation, microscopie à force atomique et ellipsométrie) ont été utilisées pour confirmer dans un premier temps la faisabilité du procédé de fonctionnalisation basé sur la polymérisation plasma puis de quantifier la réactivité interfaciale de DA. Dans une seconde partie, la méthodologie développée a été élargie à la compréhension de la réactivité interfaciale de DA et rétro-DA mettant en jeu un autre couple diène/diénophile, à savoir le furane (toujours greffé sur le polymère plasma) et le maléimide (en solution). Enfin, le greffage du maléimide sur un substrat a permis de s’interroger sur la faisabilité d’une adhésion covalente réversible, à l’échelle moléculaire mais aussi macroscopique, entre deux substrats solides fonctionnalisés, l’un avec des groupements furanes, l’autre avec des groupements maléimides. [...] / Should we adapt to materials or can we modify materials to obtain what we want and what we need? Since the beginning of humanity, natural materials (stone, wood, etc.) have allowed civilizations to develop. Thanks to the increase of knowledge in the field of materials and to the development of more and more sophisticated fabrication processes, civilizations have also allowed the development of materials such as metal alloys, ceramics and, more recently, synthetic polymers. Since the second-half of the 20th century, researchers and engineers have found interest in responsive materials and particularly responsive polymers, able to adapt to their surrounding environment such as the mostly studied poly(N-isopropylacrylamine). The number of studies to design new smart materials keeps increasing because they play an important role in the development of advanced technologies. Today, we can find smart materials in all areas of activity.According to the targeted application, different stimuli are considered and can be classified amongchemical or physical stimuli.Recently, chemical stimuli have been studied for various applications, such as the elaboration of pH-stimuli responsive materials to control drug delivery and separation processes. The presence of specific molecules, for instance containing polar groups or able to form hydrogen bonds, can also modify the properties of materials and may be used to induce self-healing processes. Biomolecules may also provide chemical signals for the selective conjugation of proteins or sugars. Besides, physical stimuli have also gained interest because they can be remotely applied. Indeed, electro- or magneto-active polymers respond to an applied electric or magnetic field by changing their size or shape for instance. They are used to elaborate sensors, robotic muscles, to store data and in nanomagnetic materials for various biomedical applications. Photo-sensitive polymers can change their physicochemical properties in response to light irradiation at a given wavelength and intensity. The photoresponsive polymers are broadly used in nano- or bio-technology, such as for bio-patterning and photo-triggered drug delivery. Another highly-studied physical stimulus consists in the variation of the environmental temperature. This method is used for drug delivery, in liquid chromatography to vary the power of separation without changing the column and/or the solvent composition or to elaborate self-healing materials (composites) thanks to weak (H-bonds) or covalent interactions forinstance.In the former examples, the whole composition of the system is usually specifically formulated to react to environmental conditions, although many phenomena locally occur at the surface of the material. This strategy is thus economically non-viable because only few percents of the material volume are exploited for their smart properties. Consequently, industrial renewal can be stimulated by the fabrication of stimuli-responsive coatings that could cover any material, preserving the characteristics of the bulk material and limiting the cost of these additional smart properties. [...]

<p>Seme tikve (Cucurbita pepo) obiluje kako uljem tako i proteinima. Nakon izdvajanja ulja, proteini se koncentri&scaron;u u uljanoj pogači, sekundarnom proizvodu procesa proizvodnje ulja, gde njihov sadrţaj dostiţe do 65%. Proteini semena tikve su primamljiv sastojak za prehrambenu, farmaceutsku i kozmetičku industriju zbog svoje farmakolo&scaron;ke aktivnosti i visoke biolo&scaron;ke vrednosti. Pored toga, budući da su mnogi proizvodi ovih industrija po svojoj koloidnoj prirodi emulzije, proteini semena tikve bi se u njima mogli naći i kao prirodne povr&scaron;inski aktivne materije. Međutim, koloidna funkcionalnost proteina semena tikve se jo&scaron; uvek potcenjuje zbog globularne strukture za koju se vezuju slabija funkcionalna svojstva u odnosu na proteine sa fleksibilnijom strukturom. Prema tome, cilj ove disertacije je ispitivanje funkcionalnih osobina proteinskog izolata semena tikve, pre svega njegovih adsorpcionih i emulgujućih svojstava, kao i ispitivanje uticaja promene proteinske strukture putem enzimske hidrolize na ispitivana svojstva.<br />Pripremljeni su izolat proteina semena tikve (IPST) i dva enzimska hidrolizata, H1 i H2. IPST, H1 i H2 su okarakterisani određivanjem sadržaja vlage, proteina i pepela, zatim, određivanjem prinosa, molekulske mase i zeta potencijala. Ispitan je uticaj koncentracije proteina/peptida (0,0001&ndash;1 g/100 cm³), pH (3&ndash;8) i jonske jačine (0&ndash;1 mol/dm³ NaCl) na rastvorljivost i adsorpciona svojstva: dinamički međupovr&scaron;inski pritisak (ulje/voda), statički povr&scaron;inski (vazduh/voda) i međupovr&scaron;inski (ulje/voda) pritisak, kinetiku adsorpcije i dilatacionu reologiju proteinskih adsorpcionih filmova. Nakon toga, ispitan je i uticaj pomenutih parametara na emulziona svojstva IPST, H1 i H2. Emulgujuća svojstva IPST, H1 i H2 su okarakterisana na osnovu prosečnog prečnika kapljica emulzija, raspodele veličina kapljica i stabilnosti emulzija.<br />Utvrđeno je da je prinos IPST veći od prinosa oba hidrolizata za oko 65 %. IPST ima najniţu rastvorljivost na pH=5, &scaron;to ujedno predstavlja i njegovu izoelektričnu tačku. Enzimskom hidrolizom IPST značajno se povećava rastvorljivost, posebno na pI=5. Povećanje jonske jačine je izazvalo salting&ndash;in ili salting&ndash;out efekat rastvorljivosti kod svih uzoraka u zavisnosti od pH. IPST, H1 i H2 poseduju povr&scaron;insku aktivnost pri čemu je povr&scaron;inski/međupovr&scaron;inski pritisak H1 i H2 manje zavistan od promene pH i jonske jačine u poređenju sa povr&scaron;inskim/međupovr&scaron;inskim pritiskom IPST. Adsorpcijom na granicu faza IPST i oba hidrolizata obrazuju adsorpcione filmove sa dominantnom elastičnom komponentom. Emulgujuća svojstva IPST, H1 i H2 zavise od koncentracije uzorka, pH vrednosti i jonske jačine kontinualne faze. Pri koncentraciji od 1 g/100 cm³ i Ic=0 mol/dm³ pripremljene emulzije su stabilne na svim pH osim emulzije IPST na pH 5. Sve emulzije podležu gravitacionoj nestabilnosti.</p> / <p>Pumpkin (Cucurbita pepo) seed is rich source of both, oil and proteins. Once the oil has been extracted, proteins concentrate in oil cake, a by&ndash;product of the oil<br />extraction process, where their content can reach up to 65%. Pumpkin seed proteins are desirable ingredient in food, pharmaceutical and cosmetic industry due to their pharmacological activities and high biological value. Moreover, since many of products of these industries are, in colloidal terms, emulsions, pumpkin seed proteins could serve as surface active materies. However, colloidal functionality of pumpkin seed proteins is still underestimated for their globular structure which entails inferior functional properties to functional properties of proteins with more flexible structure. Based on that, the aim of this dissertation is to investigate functional properties of pumpkin seed protein isolate, adsorption and emulsifying properties, in the first place, and then to investigate the influence of modification of the protein structure, by means of enzymatic hydrolysis, on the aforementioned properties.<br />Pumpkin seed protein isolate, IPST, and two enzymatic hydrolysates, H1 and H2, were prepared. IPST, H1 and H2 were characterized by determination of moisture, ash and protein content, then, by determination of protein recovery, molecular mass and zeta potential. Influence of the protein/peptide concentration (0.0001&ndash;1 g/100 cm³), pH (3&ndash;8) i ionic strength (0&ndash;1 mol/dm³ NaCl) on the solubility and adsorption properties: dynamic interfacial (oil/water) pressure, static surface (air/water) and interfacial (oil/water) pressure, adsorption kinetics and interfacial dilatational properties, was<br />investigated next. In the end, influence of the aforementioned pharameters on the emulsifying properties of IPST, H1 and H2 was investigated. Emulsifying properties of IPST, H1 and H2 were discussed in terms of mean droplet diameter, droplet size distribution and emulsion stability.<br />Protein recovery of IPST was determined to be 65 % higher than recovery of H1 and H2. Solubility of IPST was the lowest at pH 5, what presents the isoelectric point. The enzymatic hydrolysis of IPST significantly increased solubility, especialy at the isoelectric point. Increase in the ionic strenght led to salting&ndash;in or salting&ndash;out effect depending on pH of the sample. Three investigated samples, IPST, H1 and H2 exhibited surface activity, however, sufrace/interfacial pressure of H1 and H2 were found to be less influenced by change in pH or ionic strenght of the solution in comparison to the IPST. Once adsorbed to the interface IPST and both hydrolysates form interfacial film with dominant elastic component. Emulsifying properties of IPST, H1 and H2 depend on the concentration, pH and ionic strength of the continuous phase. Stabile emulsions were formed at concentration of 1 g/100 cm3 and Ic=0 mol/dm³ regardless of pH, with the exception of the IPST at pH 5. All emulsions were susceptibile to gravitational separation.</p>

[pt] As propriedades reológicas na interface ar/água de modelos de surfactantes pulmonares (DPPC, DPPC:DPPG, DPPC:DPPG:Colesterol, Survanta e Curosurf) foram investigadas utilizando técnicas de cisalhamento superficiais (reometria de cisalhamento interfacial) e dilatacionais (tensiometria da gota pendente). Assim, alguns parâmetros de interesse foram obtidos para o estudo da viscoelasticidade das amostras (como viscosidade e módulos de armazenamento e perda) e as limitações das técnicas também foram analisadas. Os experimentos foram realizados de forma dinâmica, em que a faixa de frequência de interesse abrange, inclusive, a frequência respiratória de um atleta. Os resultados obtidos mostram a maior viscosidade do Survanta, frente ao Curosurf, e mostram o caráter intermediário do DPPC, que pode ser alterado pela adição de DPPG (aumentando a elasticidade) e Colesterol (aumentando a viscosidade), sugerindo que a mistura DPPC:DPPG pode ser mais adequada do que com DPPC:DPPG:COL para simular o comportamento do surfactante pulmonar. A reometria dilatacional não se mostrou aplicável ao estudo dos surfactantes, o que pode ser causado pela alta viscoelasticidade e relativa instabilidade do Survanta. / [en] The interfacial rheological properties of lung surfactants models (DPPC, DPPC:DPPG, DPPC:DPPG:Cholesterol, Survanta and Curosurf) at the air/water interface were investigated using shear (interfacial shear rheometry) and dilatacional (pendent drop tensiometry) techniques. Thus, some parameters of interest were obtained to study the viscoelasticity of the samples (such as viscosity and storage and loss modules) and the limitations of the techniques were also analyzed. The experiments were carried out dynamically, in which the interest frequency range includes the respiratory rate of an athlete. The results obtained show the higher viscosity of Survanta, compared to Curosurf, and show the intermediate character of DPPC, which can be altered by addition of DPPG (increasing the elasticity) and Cholesterol (increasing the viscosity), suggesting the DPPC:DPPG mixture may be more suitable than with DPPC:DPPG:CHOL to simulate the lung surfactant behavior. The dilatacional rheometry does not shown to be applicable for surfactants studies, which can be caused by the high viscoelasticity and relative instability of Survanta.

[pt] Inúmeros estudos têm sido realizados para melhor entender a formação e estabilidade de emulsões. Em algumas situações, é desejável ter emulsões estáveis; em outros, a separação de fases por coalescência de gotas é benéfica. Em ambos os casos, é importante entender os mecanismos associados ao processo de coalescência. O presente trabalho investiga a relação entre as propriedades reológicas das interfaces óleo-água e o tempo de drenagem de um filme fino de óleo entre duas gotas aquosas. A tensão interfacial e a reologia dilatacional interfacial foram medidas usando a análise axissimétrica da forma da gota. Foram avaliadas diferentes concentrações de um tensoativo não iônico (Span 80) dissolvido em óleo mineral (Primol 352). Os resultados indicam uma relação direta entre as propriedades da estrutura formada na interface óleo-água e a ausência de coalescência das gotas. Para concentrações de surfactante abaixo da concentração micelar crítica (CMC), a interface é fracamente elástica (fluid-like) e o processo de coalescência sempre ocorre; o tempo de drenagem não está relacionado ao tempo de envelhecimento da interface. Para concentrações de surfactante acima da CMC, os módulos elástico e viscoso mostraram mudanças significativas com o envelhecimento, levando à formação de um filme sólido na interface, impedindo a coalescência entre as gotas. Usamos experimentos de coalescência gota/gota para avaliar o efeito da reologia interfacial na dinâmica de coalescência. Para entender melhor o fenômeno da não coalescência, estudamos microscopicamente a estrutura do filme interfacial e observamos o aparecimento de pequenas gotas de água formadas na interface através de emulsificação espontânea. Descobrimos que a taxa de surgimento dessas microgotículas está diretamente relacionada à concentração de surfactante. À medida que a concentração de surfactante aumenta, mais rápido ocorre o processo de emulsificação espontânea, o que confirma os resultados obtidos com a reologia interfacial. Finalmente, um novo método para promover a desestabilização da emulsão impondo uma perturbação do filme interfacial pelo escoamento das gotas através de capilares constritos é proposto e testado. / [en] Several studies have been conducted to understand emulsions formation and stability. In some situations, it is desirable to have stable emulsions; in others, phase separation through drop coalescence is beneficial. In both cases, it is important to understand the mechanisms associated to the coalescence process. The present work investigates the relationship between rheological properties of oil-water interfaces and the drainage time of a thin oil film between two aqueous drops. Interfacial tension and dilatational rheology were measured using the axisymmetric drop shape analysis. We evaluated different concentrations of a nonionic surfactant (Span 80) dissolved in mineral oil (Primol 352) phase. The results indicate a direct relationship between the properties of the structure formed at the oil-water interface and the absence of droplet coalescence. For low surfactant concentrations, below the critical micelle concentration (CMC), the interface is weakly elastic (fluid-like) and the coalescence process always occurs; the draining time is not to related to the aging time of the interface. For surfactant concentrations above CMC, the elastic and viscous moduli showed significant changes with aging leading to the formation of a solid-like film at the interface preventing further coalescence. We used a drop/drop coalescence experiments to evaluate the effect of interfacial rheology on the coalescence dynamics. To better understand the phenomenon of non-coalescence, we study the structure of interfacial film microscopically and observe the appearance of small water droplets formed at the interface by spontaneous emulsification. We found that the emergence rate of these microdroplets is directly related to the surfactant concentration. As the surfactant concentration increases, faster the spontaneous emulsification process occurs, which confirms the results obtained with the interfacial rheology. Finally, a new method to promote emulsion destabilization by imposing a perturbation of the interfacial film by flowing the drops through constricted capillaries is proposed and tested.