Thesis (Ph. D.)--Lehigh University, 2005. / Includes vita. Includes bibliographical references.

Thesis (Ph. D.)--Lehigh University, 2004. / Includes bibliographical references and vita.

Thesis (MIng)--University of Stellenbosch, 2007. / Bibliography. Also available via the Internet.

Thesis (Ph. D.)--Lehigh University, 2006. / Includes bibliographical references and vita.

Thesis (Ph. D.)--Lehigh University, 2000. / Includes vita. Includes bibliographical references (leaves 36-43, 88-90, 139-140, 187, 238-241, 282-285, 323).

Separating oil/water emulsions is significant for the ecosystem and the petroleum and processing industry. To this end, we prepared an underwater superoleophobic membrane inspired by unique wettability of the fish scales. This membrane was fabricated by a facile vacuum filtration process of sepiolite nanofibers and chitosan, and after the cross-linking via glutaraldehyde, a self-standing membrane was obtained. The as-prepared membrane exhibited excellent capability of separating both the surfactant-free and surfactant-stabilized oil-in-water emulsions with high efficiency. This sepiolite fibrous membrane offers a convenient, reliable and efficient way for the large-scale de-emulsification process.

Droplet-based microfluidic devices have become a preferred versatile platform for various fields in physics, chemistry and biology to manipulate small amounts of liquid samples. In addition to microdroplets, microbubbles are also needed for various pro- cesses in the food, healthcare and cosmetic industries. Polydimethylsiloxane (PDMS) soft lithography, the mainstay for fabricating microfluidic devices, usually requires the usage of expensive apparatus and a complex manufacturing procedure. In ad- dition, current methods have the limited capabilities for fabrication of microfluidic devices within three dimensional (3D) structures. Novel methods for fabrication of droplet-based microfluidic devices for the generation microdroplets and microbubbles are therefore of great interest in current research. In this thesis, we have developed several simple, rapid and low-cost methods for fabrication of microfluidic devices, especially for generation of microdroplets and mi- crobubbles. We first report an inexpensive full-glass microfluidic devices with as- sembly of glass capillaries, for generating monodisperse multiple emulsions. Different types of devices have been designed and tested and the experimental results demon- strated the robust capability of preparing monodisperse single, double, triple and multi-component emulsions. Second, we propose a similar full-glass device for generation of microbubbles, but with assembly of a much smaller nozzle of a glass capillary. Highly monodisperse microbubbles with diameter range from 3.5 to 60 microns have been successfully produced, at rates up to 40 kHz. A simple scaling law based on the capillary number and liquid-to-gas flow rate ratio, successfully predicts the bubble size. Recently, the emergent 3D printing technology provides an attractive fabrication technique, due to its simplicity and low cost. A handful of studies have already demonstrated droplet production through 3D-printed microfluidic devices. However, two-dimensional (2D) flow structures are still used and the advantage of 3D-printing technique has not been fully exploited. Therefore, we apply 3D printing technology to fabricate 3D-miniaturized fluidic device for droplet generation (single emulsion) and droplet-in-droplet (double emulsion) without the need for surface wettability treat- ment of the channel walls, by utilizing 3D geometry design and fabrication. A scaling law is formulated to predict the drop size generated in the device. Furthermore, magnetically responsive microspheres are also produced with our emulsion templates, demonstrating the potential applications of this 3D emulsion generator in chemical and material engineering. Finally, we design and 3D-print a hybrid ?plug-and-play? microfluidic droplet generator, which involves a 3D-printed channel chamber and commercial tubings and fittings. By combination of 3D-printed part and market-available parts, this device can be easily assembled and disassembled, which provides a great flexibility for different demands. A scaling law has been proposed for prediction of drop size generated in the device. Furthermore, a 3D-printed concentration gradient generator and a droplet merging device based on the droplet generator have been developed to demonstrate the great scalability of 3D-printing technology.

In this work, we report a facile and robust surface membrane modification method via a simple coating of PVDF membrane using tannic acid (TA) followed by oxidation with sodium periodate (NaIO4). The modified membranes were investigated by SEM, AFM, XPS, FTIR, and a water contact angle measurement. The Contact angle measurement shows that the TA modified membrane exhibits superhydrophilicity and underwater oleophobicity. Results from FTIR and XPS indicate that the carboxylic groups were formed on the surface of the TA modified membrane due to the oxidation of quinone by NaIO4, which is the key to superhydrophilicity of the TA modified membrane surface. In addition, the modified membrane was tested for oil-in-water emulsion separation. A high TOC rejection of 99% was achieved for different kinds of surfactant-stabilized oil-in-water emulsions as well as the surfactant-free oil/water mixture. The modified membrane not only showed a good water flux and oil/water separation performance but also exhibited excellent recyclability and chemical stability. Also, the developed method is versatile and can be applied to the different types of substrate material. This robust, simple, and green approach gives great potential to fabricate large-scale material surfaces for the industrial oily wastewater treatment.

Ce travail de thèse porte sur l’étude d’une interface eau-huile où a lieu une complexation de deux polymères. La phase aqueuse est une solution de microgels de polyacide acrylique réticulé (carbomer) et la phase organique comprend un polyélectrolyte possédant des fonctions amines (amodiméthicone). Cette interface polymérique permet la stabilisation d’émulsions directes dont la taille des gouttes atteint le millimètre. Les gouttes sont ici fabriquées une à une via une technique millifluidique, ce qui permet d’obtenir une émulsion calibrée. Ce procédé a été mis au point par la société Capsum afin d’encapsuler des parfums ou bien des principes actifs pour la cosmétique. L’adsorption et la complexation des polyélectrolytes à l’interface eau-huile sont tout d’abord caractérisées à l’aide de méthodes de tensiométrie, en statique et en dynamique. Les propriétés mécaniques de la membrane polymérique ainsi que son potentiel stabilisateur d’émulsions sont ensuite étudiés à l’échelle d’une collection de gouttes, en compression par gravité ou bien par centrifugation, ainsi que pour des gouttes uniques en écoulement dans un tube. Ces diverses approches expérimentales permettent de mettre en lumière différents régimes de stabilisation des émulsions en fonction des conditions physico-chimiques. Une observation majeure est que la quantité d’amodiméthicone contrôle l’ancrage du carbomer à l’interface ainsi que l’état fluide ou bien solide de l’interface et donc la stabilité de l’émulsion correspondante. De plus, lorsque la membrane est solide, c’est-à-dire lorsqu’il y a réticulation des microgels via l’amodiméthicone, un phénomène remarquable de propagation de la rupture de la membrane au sein d’une émulsion sous compression est révélé. / This work focuses on the study of an oil-water interface where the complexation of two polymers takes place. The aqueous phase is a solution of cross-linked polyacrylic acid microgels (carbomer) and the oil phase contains a polyelectrolyte possessing amine groups (amodimethicone). The stabilization of an emulsion of millimeter-sized droplets is achieved with this polymeric interface. Designed by millifluidic, the droplets are made one by one and a calibrated emulsion of oil in water is obtained. The process was developed by the company Capsum, with the objective to encapsulate perfumes or active ingredients for cosmetics. First, we characterize the adsorption and complexation of the polyelectrolytes at the oil-water interface with both static and dynamic tensiometry methods. Then, we study the mechanical properties of the polymeric membrane along with its capacity to stabilize emulsions, at the level of a collection of droplets undergoing compression which is applied either by gravity or by centrifugation, and also at the level of single droplets flowing through a glass capillary. Thanks to those various experimental methods, and depending on the physico-chemical conditions, the different emulsion stabilization regimes are highlighted. A major observation is that the amount of amodimethicone controls the anchoring of the carbomer at the interface, setting the interface state from fluid to solid, and therefore the corresponding emulsion stability. Moreover, when the membrane is solid, that is to say when the microgels are electrostatically cross-linked with the amodimethicone, a remarkable propagation of membrane rupture within an emulsion undergoing compression is revealed.

Les peintures sont omniprésentes dans nos civilisations modernes et décorent presque tous les supports et ce dans des domaines très variés. L'utilisation massive des peintures pose cependant des problèmes environnementaux et de santé publique, de par la présence de solvants qui, lors du séchage, s'évaporent et émettent des composés organiques volatiles (COV) néfastes pour l'environnement et l'homme. Une démarche européenne et mondiale de réduction d'émission des COV est donc en cours depuis quelques années. De plus, l'engouement croissant pour le développement durable pousse à la transition de produits pétrosourcés vers des produits biosourcés, à coûts et performances similaires. Les résines alkydes en émulsions, développées au début du XXème siècle, constituent une alternative de choix car émettant une quantité limitée de COV et obtenues par polycondensation de matières premières renouvelables. Après un état de l'art sur le contexte des peintures actuelles et la composition d'une peinture alkyde en émulsion, leurs propriétés physiques et chimiques ont été étudiées. Après ce travail de formulation, deux additifs ont été synthétisés afin d'augmenter le taux de biosourcé des peintures alkydes en émulsion : un épaississant et un agent dispersant. De par la présence de surfactants, les formules de peintures alkydes en émulsion sont pour l'heure moins compétitives que les peintures alkydes en phase solvant. En conséquence, la première émulsion alkyde sans tensioactif a été développée et ses performances évaluées en peinture / Paints and coatings occupy a prominent place in the cultural history of mankind. People have always been fascinated by colors and used paints to decorate and beautify themselves and their environment. Nevertheless, these products bring a lot of problems. For instance, some paints still contain organic solvents, which have negative impacts on the environment and human health. Due to environmental legislations and the need to reduce VOCs emission (volatile organic compounds), water-based paints have attracted a lot of interest. Moreover, the raising sustainability awareness is a driving force for the transition from petrobased to biobased products with equivalent costs and performances. In this context, alkyd resin emulsion, introduced in the 1990s, still continue to be the most widely used binder, because they have low VOCs level and are synthesized by polycondensation reactions of renewable raw materials. After reviewing the current state of the art regarding the alkyd paint emulsion, their physical and chemical properties were studied. Two additives, respectively a rheology modifier and a dispersing agent, were also synthesized, in order to increase the biobased content of alkyd paint emulsion Due to the presence of wetting agent, alkyd emulsion paints are still less competitive than solvent-borne alkyd paints. The first surfactant free alkyd emulsion was consequently developed and its film properties characterized in paint formulation