[pt] Emulsões estáveis de óleo-em-água (O/A) e água-em-óleo (A/O) são criadas em diferentes processos de produção de óleo devido à presença de tensoativos naturais, tais como asfaltenos, resinas, ácidos orgânicos solúveis em óleo, sólidos e ceras. Um filme interfacial é formado causando interações químicas entre os surfactantes e outras espécies na fase aquosa. Este trabalho tem como objetivo estudar a formação e estabilidade de emulsões estabilizadas por um ácido graxo como um surfactante natural, sob condições ambientes e de alta pressão, bem como seu comportamento de fluxo através de testes de injetividade em arenitos. Para este fim, o estudo da estabilidade da emulsão e análise de reologia interfacial foram realizadas através da avaliação da distribuição do tamanho de gotas e do módulo viscoelástico da interface em função da concentração de surfactante, composição aquosa e condições de fluxo. Nos testes reológicos, os resultados mostraram que a presença do ácido graxo na fase oleosa promoveu redução na tensão interfacial óleo-água e módulo elástico maior que o módulo viscoso, evidenciando importante atividade superficial. Todas as emulsões formadas com uma solução alcalina sem sais foram estáveis sob condições ambientes. Durante a injeção de emulsão em fluxo monofásico, o controle da mobilidade da água foi observado através da redução da permeabilidade absoluta como uma função forte da distribuição do tamanho da gota da emulsão e do número de capilaridade. / [en] Stable oil-in-water (O/W) and water-in-oil (W/O) emulsions are created in different processes of oil production due to the presence of natural crude oil surfactants, such as asphaltenes, resins, oil-soluble organic acids, solids, and waxes. An interfacial film is formed causing chemical interactions between the surfactants and other species in the water phase. This work aims to study the formation and stability of emulsions stabilized by a fatty acid as natural surfactant, under ambient and high-pressure conditions, and their flow behavior through injectivity tests in sandstones. To this end, study of emulsion stability and interfacial rheology analysis were performed by evaluating the droplet size distribution and interfacial viscoelastic modulus as a function of the surfactant concentration, aqueous composition, and flow conditions. In the rheological tests, results showed that the presence of the fatty acid in the oil phase promoted a reduction in the oil-water interfacial tension and elastic modulus larger than the viscous modulus, evidencing important surface activity. All emulsions formed with an alkaline solution without salts were stable under ambient conditions. During emulsion injection in single-phase flow, water mobility control was observed through the reduction of the absolute permeability as a strong function of emulsion drop size distribution and capillary number.

京都大学 / 新制・課程博士 / 博士(農学) / 甲第23249号 / 農博第2456号 / 新制||農||1084(附属図書館) / 学位論文||R3||N5339(農学部図書室) / 京都大学大学院農学研究科農学専攻 / (主査)教授 松村 康生, 教授 田尾 龍太郎, 教授 丸山 伸之 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

<p>The development of both silica and silicones has led to enormous improvements in available products over the last 50 years: the compounds have now found practical applications in fields ranging from electronics to biomaterials. Both of these materials have several desirable intrinsic properties. The compounds can be combined as a blend, in a composite or at an interface with other compounds to tune the chemical and physical properties to those desired. On their own, silica and silicones also have many applications. Their utility would be enhanced if it was possible to improve morphological control of the materials independently or together.</p> <p>This thesis explores various parameters and factors that enable the structuring of elastomers, colloids/suspensions, films and foams with the use of unconventional or new organosilicon chemistries. Specifically, amine and boron based catalysts are utilized to catalyze silicone and silica formation at different interfaces to create the materials mentioned above. Potential applications for these materials include drug delivery, GC chromatography and paper-based diagnostics.</p> / Doctor of Philosophy (PhD)

Tesis por compendio / New tendencies in the development of innovative food packages could affect product microbial stability during storage. In this sense, antifungal systems such as emulsions, nanoemulsions and mesoporous silica supports, may be promising alternatives to preserve the product quality without having to apply further thermal treatments. The formulation of stable antifungal systems and the optimisation of the methodology to be employed to prepare these systems play an important role in: i) their antifungal effectiveness; ii) bioactive compounds losses during their preparation; and iii) their impact on the food product's sensory profile. Nanoemulsions prepared with essential oils generally presented higher antifungal effect than free essential oils applied at the same concentrations. Furthermore, the emulsifier played a key role in the resulting antifungal activity. Whey protein isolated-based nanoemulsions were more effective in inhibiting mycelial mould growth and spore germination than Tween 80-based ones. The great in vitro effectiveness of nanoemulsions to control mould development allowed to check their application to food products, and strawberry jam was selected as the food matrix. To this end, clove and cinnamon leaf emulsions were incorporated into strawberry jams to control fungal decay. Although these emulsions were able to reduce jam spoilage, their incorporation negatively affected the aroma, taste and the overall acceptance of the jam. Regarding the methodology employed to prepare oil-in-water emulsions, the magnetic stirring and high pressure homogenisation combination was the most effective to reduce essential oil losses. Moreover, stable cinnamon bark-xanthan gum emulsions with good in vitro antifungal properties against the target fungi were obtained. Despite the promising use of cinnamon bark emulsions to control fungi decay in strawberry jam, their incorporation negatively affected the product's aroma, taste and overall acceptance. Given the strong impact of essential oils on the food product's sensory profile, two new approaches were investigated: i) combinations of different antifungal compounds in emulsions; and ii) immobilisation of bioactive compounds on mesoporous silica surfaces. The cinnamon bark essential oil, zinc gluconate and trans-ferulic acid combination allowed the obtention of a product considered microbiologically acceptable and with good organoleptic characteristics. However, total mould inhibition was not achieved. Consequently, the antifungal and sensory properties of the bioactive agents (eugenol and thymol) immobilised on mesoporous silica surfaces were studied. The preparation of jams with eugenol immobilised on MCM-41 microparticles induced better control of the fungal inhibition compared with the samples functionalised with thymol. The sensory analysis of the jams after incorporating the solids revealed that eugenol and thymol immobilisation cushioned the impact of these compounds on the jam flavour profile. / Las nuevas tendencias en el desarrollo de envases alimentarios innovadores podrían afectar a la estabilidad microbiana del producto durante el almacenamiento. En este sentido, sistemas antifúngicos tales como emulsiones, nanoemulsiones y soportes mesoporosos de sílice pueden ser alternativas prometedoras para preservar la calidad del producto sin tener que aplicar otros tratamientos térmicos. La formulación de sistemas antifúngicos estables y la optimización de la metodología a emplear para preparar estos sistemas, tienen un papel importante en: i) su eficacia antifúngica; ii) pérdidas de los compuestos bioactivos producidas durante su preparación; y iii) su impacto en el perfil sensorial del producto alimenticio. Las nanoemulsiones preparadas con aceites esenciales presentaron por norma general un mayor efecto antifúngico que los aceites libres aplicados a las mismas concentraciones. Asimismo, el tipo de emulsionante utilizado desempeñó un papel clave en la actividad antifúngica de las nanoemulsiones. Las nanoemulsiones preparadas con proteína de suero de leche fueron más eficaces en la inhibición del crecimiento micelial y en la germinación de las esporas que las formuladas con Tween 80. La gran eficacia in vitro de las nanoemulsiones en el control del desarrollo de moho permitió evaluar su aplicación en productos alimenticios, siendo seleccionada la confitura de fresa como matriz alimenticia. Con este fin, las emulsiones de los aceites esenciales de clavo y de hoja de canela fueron incorporadas a las confituras de fresa con el fin de controlar el deterioro fúngico. A pesar de que estas emulsiones fueron capaces de reducir el deterioro fúngico de las confituras de fresa, su incorporación afectó negativamente al aroma, el sabor y la aceptación global de la confitura. En cuanto a la metodología empleada para preparar emulsiones aceite-agua, la combinación de agitación magnética y homogeneización por altas presiones fue la más eficaz para reducir las pérdidas de aceite esencial. Asimismo, se obtuvieron emulsiones estables con una alta capacidad antifúngica, determinada in vitro, frente a los hongos objeto de estudio. A pesar del prometedor uso de las emulsiones de aceite esencial de la corteza de canela en el control del deterioro fúngico de las confituras de fresa, su incorporación al alimento afectó negativamente al aroma, sabor y aceptación global del producto. Debido al gran impacto de los aceites esenciales en el perfil sensorial del producto alimenticio, se investigaron dos nuevos enfoques: i) combinaciones de diferentes compuestos antifúngicos en emulsiones; y ii) inmovilización de compuestos bioactivos sobre superficies de sílice mesoporosas. La combinación de aceite esencial de corteza de canela, el gluconato de zinc y el ácido trans-ferúlico permitió la obtención de un producto considerado microbiológicamente aceptable con buenas características organolépticas pero no se consiguió la inhibición total del crecimiento de moho. Por ello, se estudiaron las propiedades antifúngicas y sensoriales de agentes bioactivos (eugenol y timol) inmovilizados sobre superficies de sílice mesoporosas. La preparación de las confituras con eugenol inmovilizado en las micropartículas de MCM-41, mostró un mejor control de la inhibición fúngica en comparación con las muestras preparadas con timol funcionalizado. El análisis sensorial de las muestras tras la incorporación de los sólidos a la confitura de fresa, reveló que la inmovilización de eugenol y timol reduce el impacto sensorial de estos compuestos en confituras de fresa. / Les noves tendències en el desenvolupament d'envasos alimentaris innovadors podrien afectar l'estabilitat microbiana del producte durant l'emmagatzematge. En aquest sentit, sistemes antifúngics com les emulsions, nanoemulsions i suports mesoporosos de sílice poden ser alternatives prometedores per preservar la qualitat del producte sense haver d'aplicar altres tractaments tèrmics. La formulació de sistemes antifúngics estables, així com l'optimització de la metodologia a emprar per preparar aquests sistemes, tenen un paper important en: i) la seva eficàcia antifúngica; ii) pèrdues dels compostos bioactius produïdes durant la seva preparació; i iii) el seu impacte en el perfil sensorial del producte alimentari. Les nanoemulsions preparades amb olis essencials van presentar per norma general, un major efecte antifúngic que els olis lliures aplicats a les mateixes concentracions. Així mateix, el tipus d'emulsionant utilitzat va tenir un paper clau en l'activitat antifúngica de les nanoemulsions. Les nanoemulsions preparades amb proteïna de sèrum de llet van ser més efectives en la inhibició del creixement micelial i en la germinació de les espores que les formulades amb Tween 80. La gran eficàcia in vitro de les nanoemulsions en el control del desenvolupament de fongs va permetre avaluar la seva aplicació a productes alimentaris, sent seleccionada la confitura de maduixa com a matriu alimentària. Amb aquesta finalitat, les emulsions dels olis essencials de clau i de fulla de canyella van ser incorporades a les confitures de maduixa per tal de controlar el deteriorament fúngic. Tot i que aquestes emulsions reduïren el deteriorament fungic de les confitures de maduixa, la seva incorporació va afectar negativament a l'aroma, el sabor i l'acceptació global de la confitura. Pel que fa a la metodologia emprada per preparar emulsions oli-aigua, la combinació d'agitació magnètica i homogeneïtzació per altes pressions va ser la més eficaç per reduir les pèrdues d'oli essencial. A més, es van obtenir emulsions estables amb una alta capacitat antifúngica, determinada in vitro, davant dels fongs objecte d'estudi. Malgrat el prometedor ús de les emulsions d'oli essencial de l'escorça de canyella en el control del deteriori fúngic de les confitures de maduixa, la seva incorporació a l'aliment va afectar negativament a l'aroma, sabor i acceptació global del producte. A causa del gran impacte dels olis essencials en el perfil sensorial del producte alimentari, es van investigar dos nous enfocaments: i) combinacions de diferents compostos antifúngics en les emulsions; i ii) immobilització de compostos bioactius sobre superfícies de sílice mesoporoses. La combinació d'oli essencial d'escorça de canyella, el gluconat de zinc i l'àcid trans-ferúlic va permetre l'obtenció d'un producte considerat microbiològicament acceptable amb bones característiques organolèptiques però no es va aconseguir la inhibició total del creixement del fong. Per això, es van estudiar les propietats antifúngiques i sensorials d'agents bioactius (eugenol i timol) immobilitzats sobre superfícies de sílice mesoporoses. La preparació de les confitures amb eugenol immobilitzat en les micropartícules de MCM-41, va mostrar un millor control de la inhibició fúngica en comparació amb les mostres preparades amb timol funcionalitzat. L'anàlisi sensorial de les mostres després de la incorporació dels sòlids a la confitura de maduixa, va revelar que la immobilització de eugenol i timol redueix l'impacte sensorial d'aquests compostos en confitures de maduixa. / Ribes Llop, S. (2017). Study of different antifungal systems to preserve strawberry jams against fungi spoilage [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/82306 / Premios Extraordinarios de tesis doctorales / Compendio

No / The influence of surfactants on the stability of cyclodextrin (CD) Pickering emulsions is not well understood. In this study, we report two-way effects of Tween 80 and soybean lecithin (PL) on the long term stability of Pickering emulsions stabilized by the self-assembled microcrystals of alpha-CD and medium chain triglycerides (MCT). The CD emulsions in the absence and presence of Tween 80 or PL at different concentrations were prepared and characterized by the droplet size, viscosity, contact angle, interfacial tension and residual emulsion values. After adding Tween 80 and PL, similar effects on the size distribution and contact angle were observed. However, changes of viscosity and interfacial tension were significantly different and two-way effects on the stability were found: (i) synergistic enhancement by Tween 80; (ii) inhibition at low and enhancement at high concentrations by PL. The stability enhancement of Tween 80 was due to the interfacial tension decrease caused by the interaction of Tween 80 with CD at the o/w interface at lower concentrations, and significant viscosity increase caused by the Tween 80-CD assembly in the continuous phase. For PL at low concentrations, the replacement of alpha-CD/MCT by alpha-CD/PL particles at the o/w interface was observed, leading to inhibitory effects. High concentrations of PL resulted in an extremely low interfacial tension and stable emulsion. In conclusion, the extensive inclusion of surfactants by CD leads to their unique effects on the stability of CD emulsions, for which the changes of viscosity and interfacial tension caused by host-guest interactions play important roles.

[pt] O petróleo raramente é produzido puro, na maioria das vezes ele é produzido junto com água, podendo assumir a forma de emulsão. A formação de emulsões durante a produção de petróleo é altamente problemática para o escoamento e processamento do óleo, causando problemas de garantia de escoamento e aumentando o custo de separação das fases. Esse processo de emulsificação começa no interior do reservatório, no escoamento de água e óleo pelo meio poroso e continua no escoamento bifásico no poço, no fluxo turbulento nas bombas, válvulas e nas instalações de superfície. Existe incerteza em relação às condições que favorecem a emulsificação dentro dos reservatórios. Este trabalho é focado na formação de emulsões no fluxo multifásico de óleo e água em meios porosos. Um estudo experimental foi desenvolvido para analisar o efeito das variáveis do processo e das características do meio poroso e dos fluidos, na morfologia das emulsões formadas. Água e óleo foram injetados como fases separadas num meio poroso formado por micro-esferas de vidro. Os fluidos produzidos foram coletados e analisados para determinar o tipo de emulsão produzida e suas características morfológicas. Os resultados dos experimentos mostraram que a morfologia das emulsões depende principalmente das condições operacionais nas quais os fluidos são produzidos. O tamanho das gotas da fase dispersa diminui com o aumento da vazão total e aumenta com o incremento da razão de vazão água-óleo. Constatou-se também que as características do meio poroso são determinantes nas características físicas das emulsões. Um meio poroso de maior permeabilidade levou à produção de emulsões com distribuições de tamanho de gota mais dispersas e maior diâmetro médio de massa. Nesse meio poroso observou-se também em algumas condições, produção simultânea de emulsões a/o e o/a, enquanto num meio poroso de menor permeabilidade ocorreu inversão total das fases. Depois da inversão foi comum a presença de emulsões múltiplas. / [en] Crude oil is rarely produced alone. Usually it is produced together with water in the form of emulsion. Emulsion formation during oil production is extremely problematic in terms of flow characteristics and further processing of the produced fluids. It can cause flow assurance problems and increase the cost of phase separation. The emulsification process starts inside the reservoir with the flow of oil and water through the porous media and continues in the multi phase flow inside the well, the turbulent flow through valves, pumps and in surface facilities. There are still uncertainties related to the conditions that promote emulsification inside the reservoirs. This dissertation is focused in the emulsion formation in multi phase flow of oil and water in porous media. An experimental study was carried out to analyze the effects of process variables and properties of the fluids and porous media in the morphology of the emulsions formed. Water and oil were injected as separate phases into a porous media formed of glass micro spheres. The produced fluids were collected and analyzed to determine the type of emulsion and its morphological characteristics. The results of the experiments indicate that the morphology of the emulsions depends strongly on the operational conditions in which the fluids are produced. Emulsion drop sizes decrease at higher total flow rates and increase as the water-oil ratio falls. It was also established that the characteristics of the porous media have a strong effect on the morphology of emulsions. The use of a porous media with higher permeability resulted in the production of emulsions with broader droplet size distributions and larger mass medium diameters. Simultaneous production of w/o and o/w emulsions was observed in that porous media, while only total phase inversion was observed in a less permeable porous media. Multiple emulsions were common after total phase inversion.

As emulsões múltiplas mostram-se como veículos promissores em várias áreas das ciências cosmética e farmacêutica. O estudo do método de obtenção de emulsões múltiplas em etapa única é ferramenta útil para elucidação de seus aspectos físico-químicos e para viabilizar sua aplicação tecnológica. O objetivo da pesquisa foi desenvolver e caracterizar os aspectos físico-químicos do processo de emulsificação em etapa única, das emulsões múltiplas A/O/A obtidas e dos tensoativos empregados. Testes preliminares de estabilidade e avaliação do seu perfil de liberação (cafeína) foram realizados. Nanoemulsões foram inicialmente obtidas pela metodologia proposta, resultado de processo de emulsificação por inversão de fases. Suas características físico-químicas foram determinadas (valores de pH, potencial zeta e granulometria) e a influência de aditivos avaliada. Para o desenvolvimento da emulsão múltipla foram realizadas análises qualitativas e quantitativas das variáveis relevantes à composição (tipo de fase oleosa, de tensoativo hidrofílico, valor de EHL, emprego de diagrama ternário) e ao método de emulsificação (temperatura de aquecimento das fases e de emulsificação, ordem de adição e velocidade de agitação). Os estudos das propriedades físico-químicas dos tensoativos e do filme interfacial formado (cloud point, tensão superficial, CMC, reologia interfacial, reologia de fluxo e isotermas de Langmuir) foram primordiais para compreensão dos fenômenos envolvidos e relevantes ao processo de emulsificação proposto. As emulsões múltiplas foram caracterizadas quanto aos aspectos macro e microscópico, granulometria, valores de pH, potencial zeta, viscosidade relativa, perfil reológico e influência da adição de macromoléculas. A temperatura de manipulação e de emulsificação (78±2grausC) foram parâmetros fundamentais para obtenção destes sistemas em etapa única. Seus aspectos macro e microscópico foram extremamente dependentes da temperatura de emulsificação. Os resultados indicam glóbulos múltiplos consideravelmente menores do que os relatados pela literatura. Foi possível observar, no intervalo de temperatura considerado crítico para o processo, valores de tensão superficial/interfacial mínimos. Os resultados de elasticidade superficial sugerem que o comportamento das moléculas de tensoativos, em associação ou não, foi marcadamente influenciado pela temperatura e que o aumento do número de moléculas do tensoativo hidrofólico na superfície foi desfavorável as interações intramoleculares. A isoterma para os tensoativos em associação e em função da temperatura exibiu marcante inflexão para a faixa de temperatura crítica. Este comportamento indica uma dramática alteração na microestrutura do filme interfacial. O processo de encapsulação foi considerado eficiente. Os resultados obtidos indicam que, no atual estágio de desenvolvimento, não foi possível definir um perfil de liberação para a emulsão múltipla em análise. O método de emulsificação escolhido permitiu a obtenção de sistema múltiplo em etapa única, determinado pelas características físico-químicas dos tensoativos empregados, em especial do tensoativo hidrofílico derivado do óleo de rícino e do processo proposto. A formação de emulsões múltiplas anormais não ocasionais ou momentâneas sugere uma combinação dos processos de inversão de fases transicional, influência do emprego de tensoativos não-iônicos etoxilados, e catastrófica, influência da razão entre o volume da fase dispersa e dispersante. As emulsões múltiplas obtidas apresentaram difícil reprodutibilidade microestrutural; entretanto podem ser consideradas estáveis frente às metodologias de avaliação e análise empregadas. / Multiple emulsions are potential vehicles not only for the cosmetic science, but also for the pharmaceutical science. Study the manufacture process of multiple emulsions by one step is a useful tool for understanding their physical-chemistry aspects and making their technological application practicable as well. The goals of this research were to development and characterize the physical chemistry features of the emulsification process by one step, the W/O/W multiple emulsions produced and the surfactants employed. Preliminary stability tests and evaluation of the release profile (caffeine) were carried out. Initially, nano-emulsions were produced by the proposed methodology, resulting from phase inversion emulsification process. Their physical chemistry aspects (pH and zeta potential values and size distribution) and electrolytes addition influence were evaluated. In order to develop the multiple emulsions, noteworthy qualitative and quantitative variables related to the composition (oil phase and hydrophilic surfactant types, HLB values, phase diagram) and to emulsification process (heating and emulsification temperatures, addition order and agitation speed) were analyzed. Analyses of the physical chemistry aspects of the surfactants in solution and their interfacial film (cloud point, surface tension, CMC, interfacial and flux rheology, and Langmuir isotherms) were essential in order to understand the phenomena related to proposed emulsification process. Multiple emulsion analyses (macroscopic, microscopic, size distribution, pH and zeta potential values, relative viscosity, rheological profile and macromolecule addition influence) were carried out. Production and emulsification temperatures (78±2grausC) were fundamental parameters in order to obtain multiple droplets by one step. Their macro and microscopic aspects were completely conditioned by the emulsification temperature. The sizes of the multiple droplets obtained were significantly smaller than those reported in the literature. For the critical temperature range, the minimum surface tension values were reached. Surface elasticity results suggest that the behavior of the surfactant molecules, in association or not, was fundamentally influenced by the temperature. Increasing surfactant molecule moieties on the surface, the intra molecular interactions were misplaced. The Langmuir isotherm as a function of the temperature demonstrated distinctive behavior for the critical temperature range, where the transition phase into solid state and soon afterwards some collapse could be observed. This phenomenon indicated some dramatic alteration of the surface film microstructure. The encapsulation process was regarded as efficient. The release profile studies demonstrated that the dispersed system in analysis was not ready yet for this research stage. The proposed emulsification process was able to produce multiple droplets by one step; moreover this result presented direct influence of the surfactant physical chemistry features, particularly the hydrophilic one, castor oil derivate, and of the methodology employed. The abnormal, non-occasional and non-transitory, multiple emulsion formation suggest a combination of transitional (ethoxylated non ionic surfactant influence), and catastrophic (dispersed/dispersant ratio influence) phase inversion processes. The obtained multiple emulsions presents microstructure aspects were not easily reproducible; however those were regarded stable for the analysis methodology employed.

As emulsões múltiplas mostram-se como veículos promissores em várias áreas das ciências cosmética e farmacêutica. O estudo do método de obtenção de emulsões múltiplas em etapa única é ferramenta útil para elucidação de seus aspectos físico-químicos e para viabilizar sua aplicação tecnológica. O objetivo da pesquisa foi desenvolver e caracterizar os aspectos físico-químicos do processo de emulsificação em etapa única, das emulsões múltiplas A/O/A obtidas e dos tensoativos empregados. Testes preliminares de estabilidade e avaliação do seu perfil de liberação (cafeína) foram realizados. Nanoemulsões foram inicialmente obtidas pela metodologia proposta, resultado de processo de emulsificação por inversão de fases. Suas características físico-químicas foram determinadas (valores de pH, potencial zeta e granulometria) e a influência de aditivos avaliada. Para o desenvolvimento da emulsão múltipla foram realizadas análises qualitativas e quantitativas das variáveis relevantes à composição (tipo de fase oleosa, de tensoativo hidrofílico, valor de EHL, emprego de diagrama ternário) e ao método de emulsificação (temperatura de aquecimento das fases e de emulsificação, ordem de adição e velocidade de agitação). Os estudos das propriedades físico-químicas dos tensoativos e do filme interfacial formado (cloud point, tensão superficial, CMC, reologia interfacial, reologia de fluxo e isotermas de Langmuir) foram primordiais para compreensão dos fenômenos envolvidos e relevantes ao processo de emulsificação proposto. As emulsões múltiplas foram caracterizadas quanto aos aspectos macro e microscópico, granulometria, valores de pH, potencial zeta, viscosidade relativa, perfil reológico e influência da adição de macromoléculas. A temperatura de manipulação e de emulsificação (78±2grausC) foram parâmetros fundamentais para obtenção destes sistemas em etapa única. Seus aspectos macro e microscópico foram extremamente dependentes da temperatura de emulsificação. Os resultados indicam glóbulos múltiplos consideravelmente menores do que os relatados pela literatura. Foi possível observar, no intervalo de temperatura considerado crítico para o processo, valores de tensão superficial/interfacial mínimos. Os resultados de elasticidade superficial sugerem que o comportamento das moléculas de tensoativos, em associação ou não, foi marcadamente influenciado pela temperatura e que o aumento do número de moléculas do tensoativo hidrofólico na superfície foi desfavorável as interações intramoleculares. A isoterma para os tensoativos em associação e em função da temperatura exibiu marcante inflexão para a faixa de temperatura crítica. Este comportamento indica uma dramática alteração na microestrutura do filme interfacial. O processo de encapsulação foi considerado eficiente. Os resultados obtidos indicam que, no atual estágio de desenvolvimento, não foi possível definir um perfil de liberação para a emulsão múltipla em análise. O método de emulsificação escolhido permitiu a obtenção de sistema múltiplo em etapa única, determinado pelas características físico-químicas dos tensoativos empregados, em especial do tensoativo hidrofílico derivado do óleo de rícino e do processo proposto. A formação de emulsões múltiplas anormais não ocasionais ou momentâneas sugere uma combinação dos processos de inversão de fases transicional, influência do emprego de tensoativos não-iônicos etoxilados, e catastrófica, influência da razão entre o volume da fase dispersa e dispersante. As emulsões múltiplas obtidas apresentaram difícil reprodutibilidade microestrutural; entretanto podem ser consideradas estáveis frente às metodologias de avaliação e análise empregadas. / Multiple emulsions are potential vehicles not only for the cosmetic science, but also for the pharmaceutical science. Study the manufacture process of multiple emulsions by one step is a useful tool for understanding their physical-chemistry aspects and making their technological application practicable as well. The goals of this research were to development and characterize the physical chemistry features of the emulsification process by one step, the W/O/W multiple emulsions produced and the surfactants employed. Preliminary stability tests and evaluation of the release profile (caffeine) were carried out. Initially, nano-emulsions were produced by the proposed methodology, resulting from phase inversion emulsification process. Their physical chemistry aspects (pH and zeta potential values and size distribution) and electrolytes addition influence were evaluated. In order to develop the multiple emulsions, noteworthy qualitative and quantitative variables related to the composition (oil phase and hydrophilic surfactant types, HLB values, phase diagram) and to emulsification process (heating and emulsification temperatures, addition order and agitation speed) were analyzed. Analyses of the physical chemistry aspects of the surfactants in solution and their interfacial film (cloud point, surface tension, CMC, interfacial and flux rheology, and Langmuir isotherms) were essential in order to understand the phenomena related to proposed emulsification process. Multiple emulsion analyses (macroscopic, microscopic, size distribution, pH and zeta potential values, relative viscosity, rheological profile and macromolecule addition influence) were carried out. Production and emulsification temperatures (78±2grausC) were fundamental parameters in order to obtain multiple droplets by one step. Their macro and microscopic aspects were completely conditioned by the emulsification temperature. The sizes of the multiple droplets obtained were significantly smaller than those reported in the literature. For the critical temperature range, the minimum surface tension values were reached. Surface elasticity results suggest that the behavior of the surfactant molecules, in association or not, was fundamentally influenced by the temperature. Increasing surfactant molecule moieties on the surface, the intra molecular interactions were misplaced. The Langmuir isotherm as a function of the temperature demonstrated distinctive behavior for the critical temperature range, where the transition phase into solid state and soon afterwards some collapse could be observed. This phenomenon indicated some dramatic alteration of the surface film microstructure. The encapsulation process was regarded as efficient. The release profile studies demonstrated that the dispersed system in analysis was not ready yet for this research stage. The proposed emulsification process was able to produce multiple droplets by one step; moreover this result presented direct influence of the surfactant physical chemistry features, particularly the hydrophilic one, castor oil derivate, and of the methodology employed. The abnormal, non-occasional and non-transitory, multiple emulsion formation suggest a combination of transitional (ethoxylated non ionic surfactant influence), and catastrophic (dispersed/dispersant ratio influence) phase inversion processes. The obtained multiple emulsions presents microstructure aspects were not easily reproducible; however those were regarded stable for the analysis methodology employed.

Cette thèse concerne l’étude de l’influence de la formulation sur le comportement rhéologique des émulsions inverses très concentrées. Nous avons utilisé une démarche originale consistant à positionner le module élastique (G’) de ces émulions sur une carte bidimensionnelle formulation-composition, afin d’étudier, en particulier, l’effet de la formulation dite optimale. Deux effets nets sont liés à celle-ci: les émulsions préparées à HLB=10, c’est-à-dire à proximité de la valeur optimale (HLB=10,5), présentent des valeurs de G’ nettement plus faibles que les autres formulations, tandis qu’à une distance particulière (HLB=7,7), les valeurs de G’ sont toujours plus élevées comparativement aux autres formulations. Cette valeur particulière de HLB correspond aussi à une stabilité maximale de la dispersion et à une taille moyenne des gouttes minimale. Les émulsions très concentrées étant généralement opaques et fragiles, l’analyse du transport stationnaire incohérent de lumière polarisée, qui ne nécessite pas de dilution, a été utilisée comme méthode alternative aux techniques classiques pour déterminer l’épaisseur moyenne du film interfacial (h). La taille moyenne des gouttes (R) a pu ensuite être déterminée à partir d’un modèle géométrique qui relie R à l’épaisseur moyenne du film interfacial (h), à la fraction volumique de phase dispersée (f) et à un facteur géométrique moyen (f9) tenant compte du caractère polyédrique des gouttes. Ainsi, une expression modifiée du modèle proposé par Mougel et al. (2006) a été établie pour modéliser le module élastique (G’) en le reliant à la taille moyenne de gouttes (R), la tension interfaciale (s) et la fraction volumique de phase dispersée (f) / This thesis deals with the study of the influence of formulation on the rheological behavior of highly concentrated reverse emulsions. We used an original approach consisting in representing the elastic modulus (G’) of these emulsions on a formulation-composition bidimensional map to study, in particular, the effect of the so-called optimum formulation. Two major effects are observed in relation to this one: emulsions prepared at HLB=10, i.e. at the proximity of optimum value (HLB=10.5) present values of G’ remarkably lower than those at other formulations, while at a certain distance (HLB=7.7) the values of G’ are higher in comparison to others formulations. This last particular HLB matches with the occurrence of a maximum stability and a minimum drop size of dispersion. Highly concentrated emulsions being generally opaque and fragile, the analysis of incoherent polarized steady light transport, that does not imply any dilution, has been used as an alternative method to classical techniques to determine the average film thickness (h). The average drop size (R) has then to be determined from a geometrical model linking it to the average film thickness (h), to the dispersed phase volume fraction (f) and to a geometrical factor (f9) that takes into account the polyhedral shape of the drops. Hence, a modified expression of the model proposed by Mougel et al. (2006) has been established to model the elastic modulus (G’) by relating it to the average drop size (R), the interfacial tension (s) and the dispersed phase volume fraction (f)

Thesis (MScEng)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: Factors influencing surface run-off of bitumen emulsions were studied in order to understand binders for use in the construction of surfacing seals. Run-off of the binder from the road surface causes an inconsistent film thickness leading to ravelling (Johannes, Hanz & Bahia n.d.) and bleeding at the upstream and downstream regions, respectively. There is currently no accepted specification for surface run-off viscosity. Practice mainly relies on empirical tests and experience. As the establishment of such a specification encompasses performance of the binder in various environments or field conditions, this study was undertaken to determine performance of the selected binder. Viscosity was kept constant by spraying the emulsion at a constant temperature and also holding the pavement temperature constant. In order to study the run-off behaviour of the binder, run-off tests were conducted at various gradients, texture depths and spray rates. Surfacing seals of various texture depths were constructed in the laboratory. Using a spray bar, the emulsion was sprayed at various spray rates. The sample surfaces were tilted to various gradients. Results portrayed the effects of the three factors (spray rate, gradient and texture depth) on the amount of runoff. An increase in the magnitude of the factors resulted in a variation in the runoff (increase or decrease). One notable finding was that the runoff from the 9.5 mm seal was less than that from the 13.2 mm seal. The other significant finding was that spray rate had the largest effect on runoff, followed by texture depth, and gradient. / AFRIKAANSE OPSOMMING: Sekere eienskappe wat oppervlakdreinering van bitumen emulsies op paaie beinvloed, is bestudeer om sodoende binders wat gebruik word in die konstruksie van die seëls beter te verstaan. Afloop van die binder vanaf die padoppervlak kan lei tot die vorming van ‘n laag met ongelyke dikte wat moontlike rafeling (Johannes, Hanz & Bahia nd) en bloeing vanuit die onderkant van die pad tot gevolg kan hê. Daar is tans geen aanvaarde spesifikasies wat hierdie verskynsels inperk nie. Konstruksie praktyk berus hoofsaaklik op empiriese toetse en ondervinding. Hierdie studie is dus onderneem om prestasie van die geselekteerde binder vas te stel. Viskositeit was konstant gehou deur die aangewende emulsie en padtemperatuur konstant te hou. Ten einde die afloopgedrag van die binder te bestudeer, is toetse uitgevoer op verskeie hellings, tekstuurdieptes en aanwendingskoerse. Seëls van die verskillende tekstuurdieptes is gebou in die laboratorium, en emulsies op hierdie oppervlaktes aangewend. Die toetsoppervlakte is gekantel om die vereiste helling te kry. Resultate vir die drie faktore wys die invloed op afloop. ‘n Toename in die grootte van die faktore het gelei tot 'n variasie in die afloop (toename of afname). Een noemenswaardige bevinding was dat die afloop van die seël van 9,5 mm minder was as dié van die seël van 13,2 mm. Belangrike bevindinge sluit ook in dat die spuitkoers die grootste invloed het op afloop, gevolg deur die tekstuur diepte en die gradiënt.