京都大学 / 0048 / 新制・論文博士 / 博士(農学) / 乙第12820号 / 論農博第2793号 / 新制||農||1025(附属図書館) / 学位論文||H26||N4815(農学部図書室) / 31307 / 京都大学農学研究科農学専攻 / (主査)教授 松村 康生, 教授 裏出 令子, 教授 安達 修二 / 学位規則第4条第2項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

The diploma thesis deals with the stability determination of model O/W (30/70) emulsions at 25°C. In fact, the time and emulsifier concentration (Tego Care PS) dependences of physical properties (aging) were monitored. In the second part of the work, the influence of conservant on emulsion stabilities were studied. In order to study physical properties of emusions rheometry, differential scanning calorimetry (DSC) and optical microscopy were employed. The rheological measurement provided information on viscosity and viscoelastic modulus. DSC experiments used the repeated freezing/thawing cycles which allowed monitoring of changes in crystallization temperature of water present in emulsions and melting enthalpy of ice formed during the cooling. The optical microscopy was used to examine the change in oil droplet size in the course of emulsion destabilization and phase separation. In this case the image analysis was carried out using program HarFA. The results showed that due to the emulsion creaming, the oil droplets diffuse and aggregate which causes phase separation. Those processes were quickest for the emulsion with lowest emulsifier concentration 0.1 % (destabilization during 51 days) The emulsions with emulsifier concentration about 1.5 and 1.3 % were stable at least for 4 months. The presence of the coemulsifiers increased the elastic modulus and descreased the phase difference due to the network formation. It was shown that for the stability determination is necessary to use conservant due to risk of microbial contamination. DSC experiments allowed to distingush samples prepared under different conditions. Lower rotational speed during emulsion preparation caused the appearance of two melting and crystalization peaks while for higher speed only one peak was observed.

[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.