Composite materials generally consist of different components which individually exhibit an entirely different material behaviour than within the composite. Here, two immiscible liquids are stabilised with solid particles forming liquid-liquid emulsions. Solid stabilised emulsions, also known as Pickering emulsions, have been thoroughly studied and find application in many industrial sectors. In these emulsions one liquid is generally suspended within the other in the form of droplets. Inspired by computer simulations, it should be possible to create a bicontinuous network of two immiscible liquids also stabilised with jammed particles. This will result in an attractive new material which could find possible industrial applications, for example as microreactors. This potential bicontinuous, interfacially jammed emulsion gel was dubbed bijel. Drawing together knowledge from different disciplines this thesis presents an experimental route to bijel formation. Accessing a certain type of phase separation called spinodal decomposition can be used to create a convoluted arrangement of bicontinuous interfaces. Liquid-liquid interfaces can be stabilised by exploiting the fact that solid particles can be irreversibly trapped at liquidliquid interfaces. Once trapped, the presence of the particles demands a minimum interfacial area between the two liquids. If the particles are jammed against each other this will result in the stabilisation of the liquid-liquid interfaces. To stabilise convoluted, bicontinuous interfaces in this way one type of particles must be able to concurrently stabilise two types of curvatures. Over the last three years it has been shown by several different research groups that this is possible. This thesis examines different types of temperature and pressure quenches on binary liquid systems to reach spinodal decomposition in the presence of particles. At the same time the ability of the particles to collect on the interfaces created during such phase separations is tested. It is found that temperature quenches through the critical point can lead to reproducible bijel formation resulting in the first experimental presentation of bijels. Using confocal microscopy the bijel formation process is studied in detail and properties of this new material are examined. To obtain insight into the behaviour of slowly ageing soft materials xray photon correlation spectroscopy is separately carried out on droplet emulsions.

In this thesis, the adsorption of single-wall carbon nanotubes (SWCNTs) at the liquid/liquid interface, and the subsequent electrochemical investigation of the electrical properties of the adsorbed nanotubes have been studied. Prior to the adsorption of the nanotube, the stability of dispersion of SWCNTs in non-aqueous solvents was assessed by determining the onset of aggregation of the SWCNTs when organic electrolyte was introduced. It was found that electrostatic repulsion between the SWCNTs contributes significantly to the stability of the SWCNTs in non-aqueous solvents. Similar result was also found when the aggregation kinetics of molybdenum disulphide (MoS2) dispersion in non-aqueous media was studied using the same organic electrolyte. The formation of nanomaterial-polymer composites by deliberate electrochemical oxidation of pyrrole and the sonochemical polymerisation of the organic solvent was also studied. Electrolyte addition was shown to be a promising way to separate the 2D material from the sonopolymer.

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.

Ce travail est consacré à l'étude expérimentale des écoulements diphasiques et triphasiques d'inclusions (bulles, gouttes, sphères) en milieux tant newtoniens que non newtoniens à l'échelle microscopique et mésoscopique, en utilisant la visualisation par une caméra rapide, la vélocimétrie par images des particules (PIV) ainsi que la micro-vélocimétrie par images des particules. Des bulles et des gouttes ont été étudiées expérimentalement depuis leur formation, en passant par leur déformation jusqu'à leur coalescence. La formation de bulles dans des micro-mélangeurs a été étudiée et caractérisée par l'obtention de champs de vitesses. Différents paramètres, tels que le cisaillement, la géométrie de la zone de formation, les débits ou encore les propriétés physiques ont été testés afin de développer des lois d'échelles. La traversée d'une interface liquide-liquide par une inclusion a été abordée par des expériences originales, permettant de décrire la dynamique du phénomène, de définir des nombres adimensionnels et de mettre en évidence des instabilités interfaciales. L'effet Weissenberg a également été étudié aux différentes échelles afin de comprendre les phénomènes conduisant à son amplification. Enfin, en milieu viscoélastique et rhéofluidifiant, nous avons caractérisé l'écoulement autour d'une inclusion isolée solide par l'obtention de champs de vitesses. Ces résultats ont permis de confirmer l'origine viscoélastique du sillage négatif et de prédire ses caractéristiques / The present work was devoted to the experimental study of the multiphase flow around inclusions in both Newtonian and non-Newtonian media at respectively microscopic and mesoscopic scales, by means of the Particle Image Velocimetry (both PIV and µ-PIV) and fast camera visualization. Bubbles and drops were experimentally studied starting from their formation, the rising and up to their coalescence and fragmentation. Bubble formation in micro-mixers was also investigated and characterized by measuring the liquid velocity fields. Different parameters, such as the shear rate, the geometry of the micro-mixer, the flow rates or the physical properties were tested to develop correlations of power-law kind. The deformation of a liquid-liquid interface due to the passage of an inclusion was investigated by original experiments in order to observe and describe the dynamics of the phenomenon, to define the reliable dimensionless numbers and also to highlight several interfacial instabilities. The Weissenberg effect was also studied at different scales in various non-Newtonian fluids in comparison with Newtonian fluids to understand the amplification phenomena under the combining effects of instability and normal forces. Finally, the flow around an isolated solid inclusion was characterized by performing the measurements of velocity fields in viscoelastic and shear-thinning fluids. These results were used to confirm the viscoelastic origin of the negative wake behind the solid sphere and to model its characteristics

Uma das dificuldades relacionadas com a exploração de petróleo é o transporte de óleo pesado, que devido a sua alta viscosidade, acarreta em uma elevada perda de carga no sistema. Para proporcionar economia de energia aplica-se o método do Core Annular Flow (CAF) onde é utilizado um escoamento anular bifásico em que a água escoa na periferia da tubulação para redução do gasto energético. O presente trabalho visou compreender e reproduzir este fenômeno, desenvolvendo simulações em CFD através do pacote comercial ANSYS FLUENT considerando o escoamento 3D, turbulento, isotérmico e incompressível para casos estacionários e transientes. A interface entre a água e o óleo foi adequadamente reproduzida em diferentes geometrias como tubo reto e com curva. O método LES para simulação de grandes escalas provou ser o melhor método de turbulência dentre os testados, como k-epsilon e modelo de tensores de Reynolds, de forma com que a interface fosse representada corretamente. O modelo para sistema multifásico adotado foi o Volume de Fluido (VOF), comparado com o comportamento experimental e com dados da literatura. Os fenômenos de swirl observados experimentalmente também foram reproduzidos de forma satisfatória. / One of the difficulties related to oil exploration is the transportation of heavy oil, which due to its high viscosity, causes a high pressure drop in the system. In order to provide energy savings, the Core Annular Flow (CAF) method applies where a two-phase annular flow occurs in which water flows at the periphery adjacent to the pipe to reduce energy expenditure. The present work aimed to understand and reproduce this phenomenon, developing CFD simulations through the commercial package ANSYS FLUENT considering flow as 3D, turbulent, isothermal and incompressible for stationary and transient cases. The interface between water and oil has been properly reproduced in different geometries such as straight pipe and pipe with a curve. The LES method for large scale simulation proved to be the best turbulence method among the tested, such as k-epsilon and Reynolds stress model, so that the interface was correctly represented. The model for the multiphase system adopted was the Volume of Fluid (VOF), compared to the experimental behavior and with data from the literature. The experimentally observed swirl phenomena were also reproduced satisfactorily.

Uma das dificuldades relacionadas com a exploração de petróleo é o transporte de óleo pesado, que devido a sua alta viscosidade, acarreta em uma elevada perda de carga no sistema. Para proporcionar economia de energia aplica-se o método do Core Annular Flow (CAF) onde é utilizado um escoamento anular bifásico em que a água escoa na periferia da tubulação para redução do gasto energético. O presente trabalho visou compreender e reproduzir este fenômeno, desenvolvendo simulações em CFD através do pacote comercial ANSYS FLUENT considerando o escoamento 3D, turbulento, isotérmico e incompressível para casos estacionários e transientes. A interface entre a água e o óleo foi adequadamente reproduzida em diferentes geometrias como tubo reto e com curva. O método LES para simulação de grandes escalas provou ser o melhor método de turbulência dentre os testados, como k-epsilon e modelo de tensores de Reynolds, de forma com que a interface fosse representada corretamente. O modelo para sistema multifásico adotado foi o Volume de Fluido (VOF), comparado com o comportamento experimental e com dados da literatura. Os fenômenos de swirl observados experimentalmente também foram reproduzidos de forma satisfatória. / One of the difficulties related to oil exploration is the transportation of heavy oil, which due to its high viscosity, causes a high pressure drop in the system. In order to provide energy savings, the Core Annular Flow (CAF) method applies where a two-phase annular flow occurs in which water flows at the periphery adjacent to the pipe to reduce energy expenditure. The present work aimed to understand and reproduce this phenomenon, developing CFD simulations through the commercial package ANSYS FLUENT considering flow as 3D, turbulent, isothermal and incompressible for stationary and transient cases. The interface between water and oil has been properly reproduced in different geometries such as straight pipe and pipe with a curve. The LES method for large scale simulation proved to be the best turbulence method among the tested, such as k-epsilon and Reynolds stress model, so that the interface was correctly represented. The model for the multiphase system adopted was the Volume of Fluid (VOF), compared to the experimental behavior and with data from the literature. The experimentally observed swirl phenomena were also reproduced satisfactorily.

It was found that there exist three major water environments when water is dissolved in nitrobenzene. 2H NMR has proved that these solvatomers exist irrespective of whether lithium salt is added to the system. 7Li NMR experiments suggested that the first solvatomer is majority nitrobenzene, the second a mixed solvation shell consisting of nitrobenzene and water and the third solvatomer is a large water aggregated at the glass surface. The mixed solvation state is short lived and is promoted by addition of water of by supersaturating the system upon cooling. This is a high energy state and decays either into the homogenous bulk NB state or to the surface of the glass wall, depending on if glass surface is present. In the 7Li NMR experiments, the hydrophobicity of the salt, determined by the anion, affects the relative intensity of the three 7Li resonances. Addition of lithium serves to promote hydrogen bonding in the majority nitrobenzene solvatomer, as confirmed by FTIR and neutron diffraction studies. There is no evidence that it has an effect on the size of the mixed solvatomer or the water aggregate immobilized on the glass surface. A reasonable hypothesis is that lithium exchanges between the water species which are formed independent of lithium involvement. The system is summarized as follows: Below critical water concentration (~200mM) nitrobenzene/water is a homogeneous distribution of water molecules in nitrobenzene. Addition of lithium salt to such a system has two main affects. First, the lithium promotes hydrogen bonding between the dissolved water molecules, as confirmed by FTIR and neutron scattering. Second, the hydrogen bonded water may precipitate causing microheterogeneity of the system, leading to a second resonance observed in both the 2H and 7Li NMR spectra (LiNB/W). In the presence of glass, a third solvation state can nucleate at the glass surface; this solvation state has character even closer to that of bulk water (LiW). These two supplementary solvation states can be artificially induced by either adding aliquots of water or cooling.

Die Effektivität der Reaktivextraktion als Verfahren zur Stoffabtrennung aus wässrigen Lösungen mit organischen Lösungsmitteln lässt sich durch den Zusatz weiterer Stoffe deutlich steigern. Das können Co-Ionen, Lösungsvermittler und Stoffe sein, die die Phasengrenzfläche beeinflussen. Wichtigste Vertreter der letzteren Gruppe sind Tenside, die die Grenzflächenspannung zwischen den Phasen verringern. Sie werden in der industriellen Technik bereits seit Jahrzehnten mit gleich bleibendem Erfolg angewandt. Dabei sind die Vorgänge an der Phasengrenze, die durch die Tenside beeinflusst werden, noch nicht vollständig geklärt. In diesem Umfeld ist auch die vorliegende Arbeit entstanden. Sie soll bereits am Lehrstuhl vorliegende Arbeiten ergänzen. Gegenstand der Untersuchungen ist der Einfluss von Tensiden auf die Extraktion von Schwermetallionen im elektrischen Feld, hier untersucht an dem kationischen Tensid Hexadecyltrimethylammoniumbromid (CTAB). Als Untersuchungsmethode wird die Polarographie verwendet. Der Ladungsdurchtritt durch die Grenzfläche Wasser/Quecksilber und deren Beeinflussung durch das Tensid werden für die Metallionen von Zink, Cadmium, Blei und Chrom bei unterschiedlichen pH-Werten untersucht. Es zeigt sich, dass die Modifizierung der Grenzfläche nur einen Teil der Beeinflussung ausmacht, weitere entstehen durch die chemische Modifizierung der vorhandenen Spezies. Weiterhin kann abgeleitet werden, dass trotz chemischer Verwandtschaft der eingesetzten Systeme eine klare Vorhersage der Beeinflussung nur begrenzt möglich ist. Der grundlegende Trend von Systemen mit chemisch ähnlicher Zusammensetzung ist zwar der gleiche, jedes System reagiert jedoch individuell in Abhängigkeit der genauen stofflichen Zusammensetzung und der Versuchsbedingungen, so dass stets konkrete Voruntersuchungen notwendig erscheinen.

Dans le but de prédire l’évolution d’un hypothétique accident au sein d’un réacteur nucléaire, nous nous proposons au travers de cette étude de comprendre la dynamique de bulles de gaz évoluant dans un bain stratifié constitué de deux liquides superposés. Pour ce faire, un dispositif expérimental muni de caméras à haute cadence a été construit afin d’observer en détail la dynamique de bulles d’air isolées et de trains de bulles traversant une interface séparant deux liquides newtoniens immiscibles initialement au repos. En faisant varier la taille des bulles injectées ainsi que les contrastes de viscosité entre les liquides d’un et quatre ordres de grandeur respectivement, ce dispositif a permis d’observer une grande variété de régimes d’écoulement. Dans certaines situations, les bulles de taille millimétrique restent piégées à l’interface liquide-liquide, tandis que les bulles plus grosses parviennent à traverser l’interface, entraînant une importante colonne de liquide lourd derrière elles. Après que l’influence des paramètres physiques a été qualitativement établie à la lumière de modèles simples, des simulations numériques de plusieurs situations sélectionnées ont été réalisées. Celles-ci ont été menées à partir de deux approches basées sur les équations de Navier-Stokes incompressibles, l’une utilisant une technique de capture d’interface, l’autre une description de type « interface diffuse » de Cahn-Hilliard. Les comparaisons entre les résultats expérimentaux et numériques ont confirmé la fiabilité des prédictions numériques dans la plupart des cas, mais ont également souligné le besoin d’améliorer la capture de phénomènes physiques à petite échelle, en particulier ceux liés au drainage de film. / In order to predict the evolution of a hypothetical accident in pressurized water nuclear reactors, this study aims to understand the dynamics of gas bubbles ascending in a stratified mixture made of two superimposed liquids. To this aim, an experimental device equipped with two high-speed video cameras was designed, allowing us to observe isolated air bubbles and bubble trains crossing a horizontal interface separating two Newtonian immiscible liquids initially at rest. The size of the bubbles and the viscosity contrast between the two liquids were varied by more than one and four orders of magnitude respectively, making it possible to observe a wide variety of flow regimes. In some situations, small millimetric bubbles remain trapped at the liquid-liquid interface, whereas larger bubbles succeed in crossing the interface and tow a significant column of lower fluid behind them. After the influence of the physical parameters was qualitatively established thanks to simple models, direct numerical simulations of several selected experimental situations were performed with two different approaches. These are both based on the incompressible Navier-Stokes equations, one making use of an interfacecapturing technique, the other of a diffuse Cahn-Hilliard description. Comparisons between experimental and numerical results confirmed the reliability of the computational approaches in most situations but also highlighted the need for improvements to capture small-scale physical phenomena especially those related to film drainage.

Beim Stoffübergang einer grenzflächenaktiven Substanz in einem flüssigen Zweiphasensystem kann solutale Marangoni-Instabilität einsetzen. Die weitere nichtlineare Entwicklung der Marangoni-Instabilität geht mit einer enormen Vielfalt von Strömungsmustern einher. In der Literatur wird dieser Aspekt häufig unter dem unscharfen Ausdruck „Grenzflächenturbulenz“ zusammengefasst. Diese Arbeit stellt heraus, dass drei grundlegende Strukturformen existieren: Rollzellen, Relaxationsoszillationen und Relaxationsoszillationswellen. Ein großer Teil der Komplexität der Strömungsmuster ist dadurch begründet, dass die Grundstrukturen unterschiedliche Hierarchieebenen aufweisen. Es werden die zugrunde liegenden Bedingungen für das Auftreten der jeweiligen Strukturtypen, ihre transiente Natur und die Bildung der hierarchischen Strömungsmuster untersucht. Des Weiteren betrachtet diese Arbeit die Wechselwirkungen mit Dichteeffekten, die sowohl die Charakteristik der Strukturen als auch ihre zeitliche Entwicklung beeinflussen.