No description available.

<div>Fluid interfaces containing surface-active species (e.g., surfactants, polymers, and particles) have rheological properties that are vital to the kinetic stability of emulsions. Many practical applications of emulsions necessitate superb stability during storage, such as in emulsion-based therapeutic delivery systems. While in other cases, stabilized systems are entirely unwanted (e.g., separating oil and aqueous phases in enhanced oil recovery and bilge water applications).</div><div><br></div><div>Techniques for modulating emulsion stability are highly desired and are largely determined by the mechanics of the interfacially-trapped species. However, the utility of these techniques is often limited by difficulties in measuring and interpreting the rheological characteristics of complex fluid interfaces. Lack of control over interface formation during emulsification magnifies this problem, further obscuring relationships between interfacial rheology and bulk emulsion stability. Thus, the objectives of this research were to (1) elucidate these fundamental relationships through emulsion stability and interfacial rheological measurements, and (2) present innovative methodologies for modulating the kinetic stability of model oil-in-water emulsions using physical chemistry principles.</div><div><br></div><div>Objective 1 was addressed by studying correlations between the dilatational rheology of single- and multi-component oil-water interfaces and the susceptibility to coalescence of the bulk systems they comprised. Oscillating pendant drop tensiometry was used to probe interfacial viscoelastic behavior, while dynamic light scattering and optical microscopy were used to characterize coalescence susceptibility in bulk oil-in-water emulsions. The magnitude of the low-frequency dilatational elastic modulus was shown to positively correlate with oil droplet coalescence resistance over time. Objective 2 was addressed by analyzing how physical chemistry principles can be applied to control various emulsion droplet destabilization phenomena and produce desirable bulk behavior. To this aim, two emulsion destabilization studies were performed; one related to the nanoparticle-induced flocculation of oil droplets in a dilute, electrostatically-stabilized emulsion and one related to the convective flows generated by the asymmetric dilatational rheology of coalescing droplets. <br></div><div><br></div><div>The knowledge garnered from this body of work is highly relevant to academic and industrial emulsion formulators who seek inexpensive, yet robust methods for predicting, characterizing and tailoring the kinetic stability of oil-in-water emulsions.</div>

No description available.

Complex interfaces stabilized with materials including surfactants, polymers, and particles have dilatational properties that are important in processing emulsions and foams. Dilatational rheology is difficult to measure on interfaces due to the coupling of dilatation and shear inherent in common measurement apparatuses. Compounding the problem is the lack of control over complex interface formation in emulsification, which can obscure relationships between interfacial rheology and bulk emulsion properties. This thesis provides tools to measure dilatational properties of interfaces and generate interfaces with controlled surface coverage. A small amplitude analysis of dilatational rheology on capillary pressure tensiometers is used to develop a method for separating intrinsic rheology from surface tension effects. This analysis is applied in dilatational measurements of insoluble interfaces at the microscale, and good agreement is observed between the microscale measurements and Langmuir trough measurements. The second half of the thesis focuses on the controlled generation of particle-stabilized interfaces. A two-lobed shape transition is observed for confined bubbles traveling in a surface active particle suspension, and a model is developed to predict the particle surface coverage on the bubble interface. This model is then applied to generate monodisperse bubbles with uniform nonspherical bubbles due to particle jamming at the interface. The tools developed in this thesis are crucial to future development of relationships between the dilatational rheology of interfaces and the bulk properties of emulsions and foams.

Certain strains of hydrophobic bacteria are known to play critical roles in petroleum-related applications. The aim of this study was to investigate how hydrophobic bacteria in their stationary phase could adsorb onto the hexadecane-water interface and alter its mechanical properties. The two strains of bacteria used in forming the interfacial films were Acinetobacter venetianus RAG-1 (a Gram-negative bacterium) and Rhodococcus erythropolis 20S-E1-c (Gram-positive). Experiments at two different length scales (millimetre and micrometre) were conducted and the results were compared. In addition, a simple flow experiment was designed in a constricted channel and the results were related to the intrinsic mechanical properties of bacteria-adsorbed films. On the millimetre scale, using the pendant drop technique, the film interfacial tension was monitored as the surface area was made to undergo changes. Under static conditions, both types of bacteria showed no significant effect on the interfacial tension. When subjected to transient excitations, the two bacterial films exhibited qualitatively similar, yet quantitative distinct rheological properties (including film elasticities and relaxation times). Under continuous reduction of surface area, the RAG-1 system showed a “paper-like” interface, while the interface of the 20S-E1-c system was “soap film-like.” These macroscopic observations could be explained by the surface ultrastructures of the two cell strains. On the micrometre scale, using the micropipette technique, colloidal stability of the bacteria-coated oil droplets was examined through direct-contact experiments. Both types of bacteria were seen to function as effective stabilizers. In addition, the adsorbed bacteria also interacted with one another at the interface, giving rise to higher order 2-D rheological properties. A technique of directly probing the mechanical properties of the emulsion drop surfaces revealed that (a) the films behaved as purely elastic sheets, and (b) with a reduction in cell concentration in the aqueous phase, less oil was emulsified, but the elastic moduli of the adsorbed films remained unchanged. These results are in contrast to the above millimetre-scale study. Therefore the rheological properties of these bacteria-adsorbed films appear to be length scale-dependent. An oil displacement experiment was designed to investigate the flow behaviour of micron-scale emulsion drops in a constricted channel. The qualitative results can be correlated with the interfacial rheological properties and may have valuable relevance to the study of multiphase flow through constricted channels in porous rocks (e.g. in MEOR operations). / Chemical Engineering

La formation d’émulsions stables eau/huile lors des processus de récupération et de raffinage du pétrole peut impacter défavorablement l’efficacité de ces opérations. Bien que résines et asphaltènes soient généralement tenus pour responsables de la stabilité des émulsions, la composition exacte des molécules présentes à l’interface eau/huile est en réalité assez mal connue. L’identification de ces molécules et la connaissance de leur influence sur la propriété des interfaces est une étape nécessaire pour mieux prédire les problèmes de stabilité des émulsions dans l’industrie pétrolière. Cette thèse présente des résultats de caractérisation analytique par GPC-ICP-HRMS et FTMS du matériel interfacial (IM) extrait de quatre bruts différents et des espèces transférées dans la phase aqueuse lorsque ces bruts contactent l’eau, ainsi que des propriétés rhéologiques en cisaillement et en dilatation des interfaces eau/huile en présence de ces composés. Les bruts ont été choisis en raison de leur capacité à former des émulsions eau-dans-huile de stabilités différentes. Les mesures d’élasticité de cisaillement ont montré que la majorité des interfaces eau/huile étudiées formaient une structure élastique susceptible de fausser la mesure du module dilatationnel de Gibbs par la méthode d’analyse du profil de goutte. Néanmoins, nous montrons à l’aide de simulations numériques que le module apparent Eapp mesuré dans un tel cas est proche de la somme du module de Gibbs et du module de cisaillement (G) multiplié par 2 du réseau interfacial dès lors que G reste petit (G < 10 mN/m), ce qui est très souvent le cas puisque nous observons que le réseau interfacial formé se rompt lors des expériences de dilatation. Une équation phénoménologique a été développée permettant d’attribuer un temps de relaxation unique aux processus de relaxation qui ont lieu aux interfaces eau/huile, ce qui nous permet de classer les différents systèmes entre eux. Nous avons également étudié les IM extraits des bruts selon la technique chromatographique dite « wet silica method » récemment développée par Jarvis et al. (Energy Fuels, 2015). Les expériences de rhéologie interfaciale confirment que cette méthode permet d’extraire les composés les plus tensioactifs présents aux interfaces eau-brut. Les analyses chimiques montrent que les IM sont partiellement composés d’asphaltènes et suggèrent que les composés contenant du soufre jouent un rôle important dans la stabilité des émulsions. Enfin, nous avons trouvé que les composés hydrosolubles transférés du brut à l’eau ont un comportement bénéfique, dans le sens où leur présence rend les émulsions eau-dans-brut moins stables. L’analyse FTMS de ces composés montre qu’ils appartiennent aux classes d’hétéroatomes suivant : O2, O3, S1, OS et O2S2 et qu’une partie de ces composés appartient à la classe des asphaltènes. / Crude oil recovery and refining operations rely on high consumption water processes, which may induce the formation of stable water-in-oil emulsions. Although asphaltenes and resins are known to influence the stability of crude oil emulsions, much is still unknown about the real composition of the w/o interfacial layer. Therefore, identifying these molecules and understanding their impact on the w/o interfacial properties are key points for better predicting emulsion problems in the petroleum industry. This thesis presents results on water/oil (w/o) interface characterization using shear and dilatational interfacial rheology as well as results on molecular characterization (GPC-ICP-HRMS and FTMS) of the crude oil interfacial material (IM) and of the amphiphilic crude oil species, which are transferred to the aqueous phase during the emulsification process. Four crude oils forming w/o emulsions of different stability were used in this study. Shear interfacial rheology experiments showed that most of the studied w/o interfaces were capable of forming an elastic interfacial network exhibiting shear elasticity G. A non-null G value interferes on drop deformation and thus on drop shape analysis (DSA) results. Nevertheless, the dilatational elasticity modulus measured by DSA (Eapp) was found to be representative of the sum of the Gibbs modulus plus 2 times G, as long as G  10 mN/m. This condition is generally satisfied since the asphaltene network is broken during dilatational experiments. Consequently, Eapp gives a good approximation of the real Gibbs modulus of the interface. A new phenomenological equation was proposed to fit the dilatational Eapp experimental data, allowing the assignment of a unique characteristic time to describe the w/o interfacial relaxation process and thus sample comparison. The IM of the crude oils was extracted using the “wet silica method” recently developed by Jarvis et al. (Energy Fuels, 2015). Results showed that this method collects the most-surface active compounds that adsorb in the time frame of the extraction procedure. Successive extractions collected species that were larger and less concentrated in the crude oil, but with higher adsorption energies. Molecular characterization revealed that the IM was partially composed of asphaltene compounds, and suggested that sulfur-containing compounds may play a major role in emulsion stability. Lastly, the oil-to-water transferred species were proven to impact the w/o interfacial properties and emulsion stability. Interestingly, concentrating these water-soluble species led to more efficient crude oil dehydration. FTMS analysis of the transferred species revealed that part of the compounds belonged to O2, O3, S1, OS and O2S2 heteroatom classes, and some of them have an asphaltene-type of molecules classification.

The focus of the following research was to provide an optimized particle stabilized foam of Laponite and Pluronic L62 in water by understanding (1) the Laponite-Pluronic interactions and properties for improved performance in a particle stabilized foam and (2) the interfacial properties between air and the Laponite-Pluronic complex. These studies were conducted using both bulk and interfacial rheology, XRD, sessile droplet, TGA and UV-vis. Two novel and simple techniques, lamella break point and capillary breakup extensional rheometry, were used to both understand the Laponite Pluronic L62 interaction and determine a different mechanism for foaming properties. Bulk rheological properties identified an optimal Laponite concentration of 2% with Pluronic L62 ranging from 2.5% and 6.5%, due to the ease of flow for the dispersion. The Pluronic L62 was observed to enhance the Laponite bulk rheological properties in solution. Additionally TGA showed a similar trend in thermal resistance to water with both addition of Laponite and Pluronic L62. XRD demonstrated that 0.25% Pluronic intercalated into Laponite from dried 2% Laponite films. XRD demonstrated that the Laponite matrix was saturated at 1% Pluronic L62. UV-vis demonstrated that a monolayer of Pluronic L62 is observed up to 0.65% Pluronic L62 onto Laponite. Interfacial rheology showed that Laponite enhances Pluronic L62 at the air-liquid interface by improving the storage modulus as low at 0.65% Pluronic L62 with 2% Laponite. The lamella breakpoint of Laponite with Pluronic films indicate strong film interaction due to higher increases in mass. Extensional rheology indicates that 2.5% to 6.5% Pluronic with 2% Laponite show the most filament resistance to stretching.

<div><div><div><p>Interfacial rheology describes the functional relationship between the deformation of an interface, the stresses exerted in and on it, and the resulting flows in the adjacent fluid phases. These interfacial properties are purported to influence emulsion stability. Protein emulsifiers tend to adsorb to the interface of immiscible phases, reduce interfacial tension as well as generate repulsive interactions. A magnetic interfacial shear rheometer was used to characterize the surface pressure-area isotherms as well as interfacial rheological properties of two proteins- sodium caseinate and b-lactoglobulin. Then, sodium caseinate was used as a carrier for b-carotene encapsulation.</p><p>b-carotene is a carotenoid that exhibits pro-vitamin A activity, antioxidant capacity and is widely used as a food colorant. It is however, highly hydrophobic and sensitive to heat, oxygen and light exposure. Thus b-carotene as food ingredient is mainly available as purified crystals or as oil-in-water emulsions. In this study, b-carotene stability, and solubility in water for application as a natural colorant was improved by preparation of a sodium caseinate/ b-carotene powder using high pressure homogenization, solvent evaporation and spray drying. The powders thus prepared showed good solubility in water and yielded an orange coloration from b-carotene. The effect of medium chain triglyceride concentration (1%, 10%) and incorporation of a natural antioxidant (Duralox, Kalsec) on powder stability was studied as a function of storage time and temperature.b-carotene stability was reduced at higher storage temperature (4oC> 21oC> 50oC) over 60 days and followed first order degradation kinetics at all temperatures. Incorporation of natural antioxidant improved b-carotene stability and resulted in a second first order degradation period at 50oC. As b-carotene content decreased, Hunter Lab color values denoting lightness increased, while those for redness and yellowness of the powder decreased. This sodium caseinate based b-carotene powder could be used as a food ingredient to deliver natural b-carotene to primarily aqueous food formulations.</p><div><div><div><p>In the last part of this work, an engagement workshop was developed as a means to educate young consumers about the function of emulsifiers in foods. Food additives are important for food product development, however to consumers, a discord between their objective purpose and subjective quality has led to confusion. Food emulsifiers, in particular, are associated with lower healthiness perception due to their unfamiliar names. In collaboration with the 4H Academy at Purdue, a workshop high school student was conducted to develop an increased understanding of emulsions and emulsifiers. A survey was conducted with the participants who self-evaluated their gain in knowledge and tendency to perform certain behaviors with regards to food ingredient labels. The participants reported a gain in knowledge in response to four key questions on emulsions and emulsifiers, as well as an increased likelihood to read ingredients on a food label and look up information on unfamiliar ingredients.</p></div></div></div></div></div></div>

Diese Doktorarbeit untersucht die verschiedenen dynamischen Prozesse, welche sich an der Tropfenoberfläche abspielen, und der Methoden, die für deren Untersuchung verwendet wurden. Das Ziel dieser Arbeit ist es, die entscheidenden Eigenschaften, die einen Einfluss auf das mechanische Verhalten der Grenzfläche haben, zu identifizieren. Wir verwenden die hydrodynamisch erzwungene Deformation eines Tropfens in einem Mikrokanal, um die mechanischen Eigenschaften der Oberfläche zu untersuchen. Diese Methode wird auf drei verschiedene Fälle angewendet. Als erstes verfolgen wir die zeitliche Entwicklung einer Grenzflächenverformung, um die Dynamik der Tensidadsorption an einer Oberfläche zu untersuchen. Dabei kalibrieren wir die Tropfenverformung als Funktion von Tropfengröße und Oberflächenspannung. Diese Technik wird auf den Fall eines perfluorierten Tensids, welches von industriellem und wissenschaftlichem Interesse ist, angewendet. Wir zeigen die Möglichkeit von Messungen der dynamischen Oberflächenspannung auf Zeitskalen von zehn Millisekunden und gewinnen daraus kinetische Eigenschaften der Moleküle. Wir vergleichen die Dynamik, welche mit der klassischen Pendant-Drop-Methode gemessen werden kann mit denen der Mikrofluidik. Es zeigt sich, dass die Adsorption für den Pendant Drop von der Di usion begrenzt wird, während in der Mikrofluidik die Anbindung an die Oberfläche der langsamere Prozess ist. Der Unterschied entsteht durch das Flussprofil in der Mikrofluidik, welches konvektiven Transport induziert. Danach untersuchen wir die Verformung unter verschiedenen räumlichen Beschränkungen im mikrofluidischen Kanal. Die Tropfenverformung wird mit einer zweidimensionalen numerischen Simulationen und mit einem dreidimensionalen Modell eines Rotationsellipsoids verglichen. In beiden Fällen wird eine qualitative Übereinstimmung festgestellt, jedoch existieren auch spürbare Abweichungen vom Experiment. Die Abweichungen vom zweidimensionalen Modell ist erklärbar mit dem sinkenden Einfluss der viskosen Spannungen mit der Kanalhöhe, hervorgerufen durch Beiträge von Deformationen außerhalb der Beobachtungsebene, welche von dem Modell nicht wiedergegeben werden. Die Abweichungen vom dreidimensionalen Modell kommen von den räumlichen Beschränkungen, welche die Tropfenform von einem Rotationsellipsoid abweichend verformt. Die Untersuchung zeigt die Schwierigkeiten bei der Beschreibung von viskosen Kräfte für Abmessungen, die zu groß sind um als zweidimensional betrachtet zu werden, aber wo die Wechselwirkungen mit den Kanalwänden nicht vernachlässigbar sind. Wir diskutieren ebenfalls den Fall der trägen Relaxation des Tropfens bei Reynoldszahlen von Re 10, für welchen Oszillationen der Tropfenoberfläche beobachtet werden. Wir zeigen, dass die Oszillationen als hydrodynamische Analogie zu einer hookeschen Feder beschrieben werden können, wobei die Oberflächenspannung als Federkonstante fungiert und die Dämpfung durch die Viskosität der Flüssigkeit bestimmt wird. Die Methode liefert korrekte Ergebnisse sowohl für reine Grenzflächen als auch für Grenzflächen mit Tensiden, was zu einer zusätzliche Möglichkeit führt, die Oberflächenspannung aus der Frequenz der Verformungen zu bestimmen. Die viskose Relaxation wurde auch hierbei von den Kanalwänden beeinflusst. Als letztes wenden wir die Methode der mikrofluidischen Tensiometrie auf die Kinetik einer Polymerisationsreaktion auf der Tropfenoberfläche an. Der Einfluss der Reagenzkonzentration auf die Reaktionszeit wird untersucht, ebenso wie der E ekt der Gegenwart von Tensidmolekülen. Erste Ergebnisse dieser Untersuchung zeigen, dass die Deformation einer komplexen Grenzfläche nicht mehr allein durch die Oberflächenspannung beschrieben werden kann. Vielmehr muss die Beschreibung der mechanischen Eigenschaften der Grenzfläche notwendigerweise die Entstehung der Viskoelastizität an der Oberfläche mit in Betracht ziehen. Diese Erkenntnis erö net neue Möglichkeiten, mit Hilfe von Mikrofluidik die mechanischen Eigenschaften von komplexen Grenzflächen, wie zum Beispiel kolloidbesetzte Grenzflächen oder Membranen, zu charakterisieren.

Le relargage contrôlé est un enjeu industriel auquel l'encapsulation peut répondre. Une méthode prometteuse pour fabriquer des micro-capsules consiste à déposer couche après couche des polymères à la surface de goutte d'huiles ou de bulles d'air. Cette thèse a pour objet ces assemblages en multicouches de polymères aux interfaces liquides. A partir d'expériences menées sur des interfaces modèles entre deux fluides non miscibles et leur modélisation, nous avons étudié l'effet des interactions à l'échelle des chaînes de polymère sur les propriétés rhéologiques de l'interface. Dans un premier temps nous avons utilisé la géométrie modèle qu'est la goutte pendante pour étudier indépendamment les différents phénomènes impliqués dans l'assemblage des multicouches et dans leur déformation. Nous avons revisité différents modèles classique pour décrire l'adsorption de nos polymères à l'interface, puis nous avons mesuré les modules interfaciaux de différents systèmes de polymères. Pour cela, à l'aide de mesures complémentaires, nous avons établi un cadre pour les mesures de modules élastiques en goutte pendante. Dans un second temps, nous avons utilisé la microfluidique pour fabriquer différents types de micro-capsules et pour mesurer leurs propriétés mécaniques. Celles-ci résultent des différents phénomènes étudiés dans la première partie de cette thèse. Nous avons établi un modèle et effectué des simulations numériques qui nous permettent d'extraire les principales propriétés interfaciales de nos capsules à partir de la mesure de leur déformation dans les canaux microfluidiques. / In order to improve control over the delivery of chemicals, industries seek a way to encapsulate them. A promising method to produce artificial micro-capsules consists in assembling several layers of polymer at the interface of an oil droplet or an air bubble. This thesis focuses on these multilayer assemblies of polymers at liquid interfaces. Through experimental observations on model interfaces and modeling, we studied the effect of the molecular interactions of polymer chains at an interface between two immiscible fluids on the rheological behaviour of this interface. In a first part, we used the model macroscopic geometry of the pendant drop to study independently the different phenomena taking place during the assembly and the deformation of the multilayers. We revisited classical models to describe the adsorption dynamics of our polymers, and we measured the interfacial dilational modulus of various systems. To this aim, by performing independent measurements, we delimited the range of validity of the pendant-drop apparatus. In the second part, we used microfluidics to create micro-capsules of different kinds and to probe their mechanical properties resulting from all the phenomena studied in the first part. We developed a model and we performed numerical simulations to extract the main interfacial properties of our capsules from the measurement of their deformation in the channels.