Materials on the nanoscale have very interesting properties. Hence, they are commonly used for a variety of applications such as drug delivery, bio-imaging and sensing devices. Moreover, coating these particles with other materials forming core@shell or Janus particles can further enhance their properties. However, for the particles to be used in medical and electronic devices, their properties such as size, shape and composition need to be precisely controlled. In this PhD., an emulsification technique was chosen to investigate the synthesis of nanoparticles; it is a simple process, does not require any harsh chemicals or temperature and is fast. Emulsification occurs when two or more immiscible liquids and surfactants are mixed. Here, emulsion droplets were produced using a microfluidic device which allowed for the creation of uniform droplets. These were employed as templates to synthesise and assemble nanomaterials. The main aim of the Ph.D. was to develop a droplet based synthesis process to generate nanoparticles and then assemble them into core@shell particles. This Ph.D., starts by synthesising Fe3O4 nanoparticles (~ 12 nm) and assembling them into microparticles (~ 1µm 2µm) using emulsion droplets as microreactors. By tuning the surfactant, droplet size and evaporation rate of the dispersed phase, microparticles of varying shapes and sizes, such as spherical or crumbled shapes, were produced. When these particles are compared with the commercially available particles, the magnetic content of the in-house particles, or sometimes referred to as Loughborough University Enterprises Ltd. (LUEL), are much higher and more uniform, hence resulting in faster separation when used for extraction of analytes. LUEL particles were supplied as part of commercial collaboration. The use of Pickering emulsions were then explored to create core@shell particles using gold nanoparticles instead of a surfactant to produce gold shells and the addition of pre-synthesised Fe3O4 nanoparticles results in Fe3O4@Au core@shell particles. This is the first time Pickering emulsions were used to produce Fe3O4@Au core@shell particles (~ 1.5 µm) within a microfluidic device. However, the shells were not uniform in thickness. In order to improve the coverage, nanoparticles were synthesised in situ at the droplet interface. By placing the gold chloride (AuCl4-) in the continuous phase and by varying the concentration of the electron donor in hexane droplet, single crystal gold nanoparticles and platelets were formed. The reaction is spontaneous at room temperature, creating gold nanoparticles at the interface of the emulsion droplet. The size and shape of the gold nanoparticles were controlled by varying the concentration of the reactants and the size of the droplets. By adding pre-synthesised particles (Fe3O4 nanoparticles) to the droplet, Au@Fe3O4 core@shell particles were formed with an approximate size of 250 nm. The same concept of forming core@shell particles using gold nanoparticles was further expanded by using other metal ions; palladium and silver. Unlike gold, palladium and silver only formed spherical nanoparticles, no platelets were observed. The addition of preformed iron oxide nanoparticles to the palladium results in core@shell particles. However, in the case of silver, no core@shell particles were formed. The study of the rate of reaction was conducted to understand the details of the mechanism. Overall, the process developed in this Ph.D. study allows for the facile synthesis of core@shell particles in a rapid, high throughput reaction. In the future, it is believed it could be scaled up for commercial purposes.

[pt] No método de injeção de água, o óleo no reservatório é varrido até os poços produtores através de frentes de deslocamento não uniformes, deixando óleo estagnado em grandes regiões do reservatório. Frentes uniformes de deslocamento e uma melhor varredura do reservatório podem ser obtidas diminuindo a razão de mobilidade entre a água e o óleo. Normalmente, esta diminuição é feita através da modificação da razão de viscosidade entre ambas as fases. No método de injeção de emulsões, o controle da mobilidade é alcançado bloqueando os poros ou caminhos gerados pela água com gotas da fase dispersa com diâmetro da mesma ordem ou maior do que o tamanho de poro. A aplicação de emulsões no controle da mobilidade e o efeito do bloqueio de poro podem ser desenvolvidos mediante a análise de diferentes regimes de escoamento de emulsões em meios porosos. Neste trabalho, o estudo do escoamento de emulsões em meios porosos foi realizado mediante duas abordagens experimentais utilizando um micro-capilar com garganta para modelar uma garganta conectando dois poros adjacentes. Na primeira abordagem experimental, quantificou-se a queda de pressão para diferentes vazões com emulsões de três tamanhos de gota e duas concentrações de óleo em dois capilares diferentes. Os resultados confirmam que a razão entre o diâmetro da garganta do capilar e o tamanho de gota influencia fortemente a relação vazão-queda de pressão. Os resultados mostram que, para baixos números de capilaridade, o escoamento de emulsões é dominado por efeitos capilares e leva a uma diminuição da mobilidade local. Na segunda montagem experimental, o sistema de micro-velocimetria por imagem de partículas ou u-PIV foi utilizado para medir campos de velocidade do escoamento através de micro-capilares com garganta. Resoluções espaciais da ordem de 20um foram obtidas para o campo de velocidade calculado pela média amostral de vários campos instantâneos de velocidade. Os resultados experimentais da relação vazão-queda de pressão e os campos de velocidade obtidos mediante o u-PIV representam informação de grande valor para o desenvolvimento de modelos de redes de capilares no estudo do escoamento de emulsões em meios porosos. / [en] During water injection, oil is swept through the reservoir to production wells by non-uniform displacement fronts originating large areas of entrapped oil in the reservoir. Uniform displacement fronts and better reservoir sweep can be achieved by improving the mobility ratio between water and oil. Usually, mobility ratio is reduced by changing the viscosity ratio between both phases. When injecting emulsions, mobility control is achieved by blocking water paths with dispersed phase drops with diameter of the same order of magnitude of the pore throats size. The application of emulsions as mobility control agents and the pore blocking effect may be developed by analyzing different flow regimes of emulsions through porous media. In the analysis presented here, two experimental setups were used using a constricted quartz capillary to represent a pore throat that connects two adjacent pore bodies to study the flow of emulsions in the pore scale. In the first experiment, pressure drop was measured at different imposed volumetric flow rates for three oil drop size emulsions at two oil concentrations and two different quartz capillaries. The results show that the ratio between the capillary constriction diameter and the oil drop size has a strong influence on the flow rate-pressure drop relation. Experimental results also indicate that the emulsion flow dominated by capillary effects (low capillary number) leads to a decrease of local mobility. In the second experiment, a microscopic particle image velocimetry (u-PIV) system was used to measure velocity fields of the flow of emulsion through a constricted micro-capillary. Ensemble-average was used in order to obtain resolution in the order of 20 um. The flow rate-pressure drop relation results and the u-PIV velocity fields of the emulsion flow through a constricted micro-capillary represent invaluable information that can be used in the development of a capillary network model to study the flow of emulsions through porous media.

The objective of this research was to systematically study the effect of processing conditions on crystallization behavior and destabilization mechanisms of oil-in-water (o/w) emulsions. The effects of oil content (20 and 40 wt %); crystallization temperature (Tc = 10, 5, 0, -5, -10 °C); homogenization conditions, such as high shear (HS), very low pressure homogenization (VLPH), and high pressure homogenization (HPH); and cooling rate (0.2 and 30 °C/min) on both thermal behavior and destabilization mechanisms were analyzed. Docosahexaenoic acid (DHA) was added to VLPH emulsions and its effect on the physicochemical and oxidative stabilities and flavor was studied. Emulsions with 20% oil were less stable than those with 40% oil with a fast-cooling rate; however, stability increased when the emulsions were cooled slowly. Stability was also affected by oil and droplet size; the smaller the droplet the more stable the system. Smaller droplets (i.e., VLPH, HPH) had an effect on crystallization by delaying the onset of the crystal formation, which was promoted in emulsions with larger droplets (i.e., HS); 20% o/w emulsion crystallization was delayed more than 40%; and in emulsions crystallized using a slow-cooling rate, the crystal formation was less inhibited (i.e., crystals formed at a higher onset temperature [Ton], but at lower Tc) than when using a fast-cooling rate. The formation of lipid crystals either helped stabilize (small droplets) the emulsion and melted in a less fractionated manner or destabilized (big droplets) the emulsion. In addition, fast-cooling rates have greater fractionation than slow-cooling rates. Due to the greater stability of VLPH emulsions after thawing from being at -10 °C for 3 h, DHA was added to evaluate its effect on flavor (besides the effect on stability) of the emulsion. A descriptive panel was used to evaluate four attributes: oxidized, rancid, fishy, and buttery. The panelists were given samples after 72 h, because contrary to the TBA analysis which showed no significant differences between samples with and without DHA, the fishy smell was evident. The sensory evaluation results showed that there was a significant (p < 0.05) difference in fishiness between the VLPH emulsions with and without DHA, and that the odor was repulsive. No significance was seen for rancid and buttery flavors, and only a marginal significance was seen for oxidized.

There is a constant need of new synthetic emulsifiers in the food industry. Sugar esters are widely used as food grade synthetic emulsifiers, amongst which sucrose esters are the most common. Although sucrose esters are used very frequently, little is known about the use of lactose esters in food. There is a need for characterization of lactose esters before they can be used in foods. The objective of this study was to characterize a lactose ester, lactose monolaurate (LML) as an antimicrobial agent on food pathogens, evaluate its effect on 20 % oil-in-water emulsions as an emulsifier, and to explore its effect on crystallization behavior of anhydrous milk fat. In the first study (Chapter 3), the effect of LML was evaluated on survival of some Gram-positive and Gram-negative bacteria. For Listeria monocytogenes, a concentration of 1 mg/ml showed some inhibition in growth media whereas the cells were completely killed at 5 mg/ml. For Mycobacteria, an LML concentration between 0.1-1mg/ml was lethal. Scanning electron microscopy was also conducted to examine any changes in the morphology of cells. Listeria exhibited a change in morphology and a wrinkling effect was shown in Mycobacteria. In the second study (Chapter 4), the effect of LML as an emulsifier was evaluated in 20 % oil-in-water emulsions. The use level of LML was comparable to commercially available emulsifier polysorbate 20, and produced comparable stabilization in the emulsions upon use. In this study, an attempt was also made to optimize the synthesis of LML with respect to the immobilized enzyme and solvent combination. It was concluded that for 20 % oil-in-water emulsions, LML is a promising emulsifier at 0.5%. In the third study (Chapter 5), the effect of LML was evaluated at two concentrations on the crystallization behavior of anhydrous milk fat at two temperatures with high and low supercooling. On application of high intensity ultrasound (HIU) to anhydrous milk fat (AMF) at 31°C and 0.05 % LML the effect on viscosity of sample and crystallization behavior was evaluated. It was concluded that the viscosity of AMF decreased with the addition of 0.05% LML. The lower viscosity of anhydrous milk fat on addition of LML could be restored with the application of HIU.

No description available.

There is a constant need of new synthetic emulsifiers in the food industry. Sugar esters are widely used as food grade synthetic emulsifiers, amongst which sucrose esters are the most common. Although sucrose esters are used very frequently, little is known about the use of lactose esters in food. There is a need for characterization of lactose esters before they can be used in foods. The objective of this study was to characterize a lactose ester, lactose monolaurate (LML) as an antimicrobial agent on food pathogens, evaluate its effect on 20 % oil-in-water emulsions as an emulsifier, and to explore its effect on crystallization behavior of anhydrous milk fat. In the first study (Chapter 3), the effect of LML was evaluated on survival of some Gram-positive and Gram-negative bacteria. For Listeria monocytogenes, a concentration of 1 mg/ml showed some inhibition in growth media whereas the cells were completely killed at 5 mg/ml. For Mycobacteria, an LML concentration between 0.1-1mg/ml was lethal. Scanning electron microscopy was also conducted to examine any changes in the morphology of cells. Listeria exhibited a change in morphology and a wrinkling effect was shown in Mycobacteria. In the second study (Chapter 4), the effect of LML as an emulsifier was evaluated in 20 % oil-in-water emulsions. The use level of LML was comparable to commercially available emulsifier polysorbate 20, and produced comparable stabilization in the emulsions upon use. In this study, an attempt was also made to optimize the synthesis of LML with respect to the immobilized enzyme and solvent combination. It was concluded that for 20 % oil-in-water emulsions, LML is a promising emulsifier at 0.5%. In the third study (Chapter 5), the effect of LML was evaluated at two concentrations on the crystallization behavior of anhydrous milk fat at two temperatures with high and low supercooling. On application of high intensity ultrasound (HIU) to anhydrous milk fat (AMF) at 31°C and 0.05 % LML the effect on viscosity of sample and crystallization behavior was evaluated. It was concluded that the viscosity of AMF decreased with the addition of 0.05% LML. The lower viscosity of anhydrous milk fat on addition of LML could be restored with the application of HIU.

En la presente Memoria se ha efectuado un estudio de las gráficas conductimétricas que se producen en continuo durante el proceso de elaboración de emulsiones de tipo O/A de parafina líquida en agua de baja conductividad, elaboradas por inversión de fase en caliente. Para ello se han diferenciado las dos etapas características de esta elaboración:- Adición de la fase acuosa al concentrado emulsionable constituido por la mezcla emulgente + aceite, a una temperatura elevada, previamente elegida por el operador (en la Memoria: etapa de vertido o de dilución del concentrado emulsionable, en caliente)- Enfriamiento del producto obtenido en la etapa anterior (etapa de enfriamiento)En el primer caso se obtienen las gráficas de conductancia/dilución del concentrado emulsionable, a temperatura constante, y en el segundo, las gráficas de conductancia/temperatura decreciente, del producto obtenido en la etapa anterior (para estos fines se ha utilizado un utillaje y estandarizado una metódica, que se describen detalladamente).En ambos casos se ha razonado la correlación entre los perfiles de las gráficas y las variaciones de estructura del producto estudiado, así como las características de las emulsiones O/A. obtenidas en las condiciones de la experiencia.a) Etapa de dilución del concentrado emulsionableEn esta etapa se pueden obtener emulsiones fluidas finamente divididas y de estabilidad aceptable. Estas dos características están íntimamente correlacionadas con la aptitud del emulgente para formar, a una temperatura previamente establecida, mesofases laminares agua/emulgente (E/A) equilibrados con la película monomolecular del emulgente adsorbida en la interfase agua/aceite (A/O). Los parámetros conductimétrícos t(i) y t(M) permiten establecer, en el diagrama ternario agua (A), aceite (O), emulgente (E) la región de emulsiones en la zona de equilibrio de estos sistemas, y su relación con la estabilidad del producto, de acuerdo con la estructura de la mesofase laminar de la mesofase condensada, en que se produce la inversión de fases, que da lugar a la emulsión naciente, hasta mesofase expandida, en la que se constituye la emulsión primaria de máxima estabilidad.En esta etapa, las emulsiones elaboradas en el IILB requerido para el emulgente en el sistema se caracterizan por los parámetros conductimétricos t(i) y t(M) mínimos a la temperatura de la experiencia y son las más estables frente a la coalescencia para el emulgente utilizado, en función de su concentración en la mesofase laminar que constituye la fase continua acuosa (E/A) en equilibrio con la fase oleosa (E/O) de la emulsión primaria.Esta emulsión, estabilizada frente a la coalescencia, puede diluirse con el resto del agua de la formulación, que da lugar a un isótropo acuoso que puede considerarse como "agua libre" de la fase continua acuosa en la emulsión fluida diluida.En este sistema se mantienen prácticamente las características de resistencia a la coalescencia debida a la acción protectora de la mesofase laminar expandida, altamente viscoelástica, pero el fenómeno de cremado (separación densitaria de la emulsión primaria del "agua libre") se produce con cierta rapidez.b) Etapa de enfriamientoLa gráfica conductancia/temperatura decreciente que se obtiene durante esta etapa de enfriamiento del producto obtenido en la etapa anterior, es útil cuando interesa averiguar la temperatura a que se produce la inversión de fases en emulsiones que no se forman en la etapa de dilución en caliente. En este caso, la gráfica conductancia/temperatura decreciente se caracteriza por los parámetros t(i) que corresponden al inicio de la transición lenta A/O -> O/A, y t(M), temperatura en que culmina dicha transición, dando lugar a un sistema emulsionado más o menos estable.Siguiendo en el supuesto anterior (emulsiones que no se forman durante la etapa de vertido en caliente) el estudio de las gráficas conductimétricas de enfriamiento tiene especial interés en emulsiones espesadas mediante la asociación de exceso de un anfifilo lipófilo no iónico (en nuestra Memoria, alcohol cetoestearílico, (ACE)) con el emulgente básico (formador) de la emulsión. La gráfica conductimétrica se caracteriza por los parámetros t(i) y t(M) que corresponden a una transición lenta A/O -> O/A. El valor t(M) suele coincidir con el inicio de la gelificación de la fase continua acuosa ("agua libre") que se produce en esta etapa de enfriamiento. La estabilización de la emulsión se debe al espesamiento del isótropo acuoso, que se opone al cremado de la emulsión diluida. De esta manera se introduce en la formulación un factor importante de estabilidad pero que sólo actúa dentro de 1ímites de temperatura que conviene conocer.En emulsiones espesadas con ACE, que se forman durante el proceso de dilución del concentrado emulsionable, en caliente, el parámetro t(e) indica la temperatura de estructuración de la fase acuosa, caracterizada por un incremento acusado de la viscosidad del producto.El valor práctico de estos parámetros se ha comprobado en emulsiones de parafina líquidas elaboradas con emulgentes no iónicos (mezcla de anfifilos de este tipo) solos o asociados con tensiactivos iónicos, (laurilsulfato sódico) y adicionados de cantidades crecientes de alcohol ceto-esteárico. / In this work, the continuous conductimetric records produced during the elaboration of o/w 1iquid paraffin emulsions in low conductivity water, prepared by the phase inversion method, has been studied.The different emulsions has been formulated with non ionic surfactant mixtures, alone or jointly with ionics ones (sodium 1auryl sulphate), and with increasing proportions of cetostearyl alcohol.During the elaboration of emulsions by the phase inversion method, the two characteristic steps of this process has been differenciated:- Addition of heated water over the emulsiflable concentrated (oil and surfactant mixture) at the same temperature, previously chosen by the operator. In the Work this phase has been said "water addition phase" or "dilution of the emulsifiable concentrated phase".- Cooling of the product obtained in the previous phase ("cooling phase").In the first phase, the graphics of conductance vs. time of dilution of the emulsifiable concentrated (at constant temperature) are obtained. In the second phase, the graphics of conductance vs. decreasing temperature of the product are obtained. The standarized procedure and the equipment used is fully commented in the memory.The experimental results allowed us to get the objectives of the work: A correlation between the conductimetric graphics and structural variations of the emulsions fluid emulsions and creams) has been established.The usefulness of these graphics as a monitorizing method during the elaboration process has been demonstrated.These graphics allow us to establish the significance of some variables to know the process of elaboration and to predict the probable stability of the emulsions.

Immiscible dispersions of oil and water are encountered in many industries such as food, pharmaceuticals, and petroleum. Phase inversion is a key phenomenon that takes place in such systems whereby the dispersed phase and the continuous phase invert spontaneously. Stabilizers such as surfactants or solid nanoparticles have been used in the past to improve the stability of emulsions. However, the combined effects of surfactants and nanoparticles on phase inversion and stability of oil and water emulsions have not been studied. This study investigates the synergistic effects of silica nanoparticles (of varying hydrophobicities) and non-ionic surfactant on phase inversion of water-in-oil emulsion to oil-in-water emulsion. The effect of oil viscosity on phase inversion phenomenon is also studied. Stabilizers were initially dispersed in the oil phase with the help of a homogenizer. The water concentration of the system was gradually increased while maintaining the mixing. Online conductivity measurements were carried out to obtain the phase inversion point. Experimental results on the effects of pure stabilizers (either silica nanoparticles or surfactant) and mixed stabilizers (combined silica nanoparticles and surfactant) on phase inversion of emulsions are presented. The stability of these emulsions is also investigated. From the results obtained in this study it is clear that catastrophic phase inversion phenomenon and stability of water-in-oil emulsions can be controlled with the help of different stabilizers. In order to extend the critical dispersed phase volume fraction at which phase inversion occurs surfactant type stabilizer was found to be more effective than solid nanoparticles. On the other hand, emulsion stability was mainly dominated by solid nanoparticles. The hybrid of the two stabilizers and its effect on phase inversion and stability are discussed in the thesis.

Water-in-oil (W/O) emulsions consist of water droplets dispersed in continuous oil phase. They are encountered at various stages of oil production. The oil produced from an oil-well usually carries a significant amount of water in the form of droplets. In enhanced oil recovery techniques involving the injection of polymer solution, the aqueous phase of the water-in-oil emulsions produced from the oil well consists of polymeric additive. A good understanding of the flow behavior of emulsions in pipelines is essential for the design and operation of oil production-gathering facilities and emulsion pipelines. A number of studies have been reported on simultaneous flow of oil and water in pipelines. However, the studies reported in the literature are mainly focused on either oil-water flow patterns and separated flows (annular and stratified flow of oil and water phases) or oil-in-water (O/W) emulsion flows. The pipeline flow of water-in-oil (W/O) emulsions has received less attention. Also, little work has been carried out on the effect of additives such as polymer. In this study, new experimental results are presented on the pipeline flow behavior of water-in-oil (W/O) emulsions, with and without the presence of polymeric additive in the aqueous phase. The emulsions were prepared from three different oils, namely EDM-244, EDM-Monarch, and Shell Pella of different viscosities (2.5 mPa.s for EDM-244, 6 mPa.s for EDM-Monarch, and 5.4 mPa.s for Shell Pella, at 25 0C). The water-in-oil emulsions prepared from EDM-244 and EDM-Monarch (without any polymeric additive in the dispersed aqueous phase) exhibited drag reduction behavior in turbulent flow. The turbulent friction factor data of the emulsions fell well below the standard Blasius equation for smooth pipes. The water-in-oil emulsions prepared from EDM-244 exhibited stronger drag reduction as compared with the EDM-Monarch emulsions. The Shell Pella emulsions (w/o type) did not exhibit any drag reduction in turbulent flow; the friction factor data followed the Blasius equation. The Shell Pella emulsions were more stable than the EDM-244 and EDM-Monarch emulsions. When left unstirred, the EDM-244 and EDM-Monarch emulsions quickly coalesced into separate oil and water phases whereas the Shell Pella emulsions took significantly longer time to separate into oil and water phases. The Shell Pella oil emulsions were also milkier than the EDM emulsions. The addition of polymer to the dispersed aqueous phase of water-in-oil emulsions had a significant effect on the turbulent drag reduction behavior. Emulsions were less drag reducing when polymer was present in the aqueous droplets. The effect of surfactant on the pipeline flow behavior of water/oil emulsions was also investigated. The surfactant-stabilized water-in-oil emulsions followed the single phase flow behavior. The presence of surfactant in the emulsions caused the dispersed droplets to become significantly smaller. It is believed that the droplets were smaller than the scale of turbulence when surfactant was present and consequently no drag reduction was observed.

Immiscible dispersions of oil and water are encountered in many industries such as food, pharmaceuticals, and petroleum. Phase inversion is a key phenomenon that takes place in such systems whereby the dispersed phase and the continuous phase invert spontaneously. Stabilizers such as surfactants or solid nanoparticles have been used in the past to improve the stability of emulsions. However, the combined effects of surfactants and nanoparticles on phase inversion and stability of oil and water emulsions have not been studied. This study investigates the synergistic effects of silica nanoparticles (of varying hydrophobicities) and non-ionic surfactant on phase inversion of water-in-oil emulsion to oil-in-water emulsion. The effect of oil viscosity on phase inversion phenomenon is also studied. Stabilizers were initially dispersed in the oil phase with the help of a homogenizer. The water concentration of the system was gradually increased while maintaining the mixing. Online conductivity measurements were carried out to obtain the phase inversion point. Experimental results on the effects of pure stabilizers (either silica nanoparticles or surfactant) and mixed stabilizers (combined silica nanoparticles and surfactant) on phase inversion of emulsions are presented. The stability of these emulsions is also investigated. From the results obtained in this study it is clear that catastrophic phase inversion phenomenon and stability of water-in-oil emulsions can be controlled with the help of different stabilizers. In order to extend the critical dispersed phase volume fraction at which phase inversion occurs surfactant type stabilizer was found to be more effective than solid nanoparticles. On the other hand, emulsion stability was mainly dominated by solid nanoparticles. The hybrid of the two stabilizers and its effect on phase inversion and stability are discussed in the thesis.