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.

Master of Science / Department of Food Science Institute / Fadi M. Aramouni / To find an optimal formulation of oil-in-water (O/W) emulsion pourable dressings containing 60% and 70% soybean oil, nine stabilizers common to the dressing industry were tested, each at three concentrations. The stabilizers tested were xanthan gum, propylene glycol alginate (PGA), a xanthan gum/guar gum/sodium alginate blend, a viscosifying modified corn starch, an emulsifying modified corn starch, microcrystalline cellulose (MCC), liquid salted egg yolks, liquid salted whole eggs, and dried egg whites (DEW). The emulsions were made with a laboratory high shear disperser and evaluated over 8 weeks by measurement of creaming in 100- mL graduated cylinders and by change in viscosity as measured by a Brookfield viscometer. The stabilizers and concentrations most effective at preventing separation and maintaining viscosity were MCC at 1%, 2%, and 3% in the 60% oil emulsion and 0.25% xanthan gum in the 70% oil emulsion. Average viscosities ranged from 3300 - 23,400 centipoise (cP). The emulsifying starch and dried egg whites were also effective at preventing creaming, but failed to maintain viscosity. The other ingredients showed some initial emulsion stability followed by either a gradual or sudden decrease in stabilization, as seen by decreasing viscosity and eventual separation.

Phospholipids, such as phosphatidylserine (PS) have been shown to work synergistically with tocopherols to extend the shelf life of oil-in-water emulsions. However, the high cost of PS prevents it from being used as a food additive. This work investigated the potential use of a high PS enzyme-modified lecithin to be used along with α-tocopherol to extend the lag phase of oil-in-water emulsions stabilized using Tween 20. Phospholipase D from Streptomyces sp. and L-serine were used to modify lecithin to increase PS concentration. Enzyme activity was optimized as a function of pH and temperature using a high PC soybean lecithin. The high PS modified lecithin was examined for its ability to enhance the activity of α-tocopherol in Tween 20-stabilized oil-in-water emulsions. The modification was also performed in high PC sunflower lecithin and egg lecithin which were later analyzed for their efficiency in controlling lipid oxidation. α-Tocopherol (3.0 µmol/kg emulsion) alone increased the lag phase of hydroperoxide and hexanal lag phases by 3 and 4 days compared to the control. Authentic PS (15.0 µmol/kg emulsion) increased hydroperoxide and hexanal lag phases by 1 and 3 days, respectively, whereas high PS soy lecithin increased hydroperoxide and hexanal lag phases by 3 and 4 days, respectively. The addition of high PS sunflower and egg lecithin did not have any considerable effects on lag phases compared to the control. Authentic PS (15.0 µmol/kg emulsion) and a-tocopherol (3.0 µmol/kg emulsion) decreased lipid oxidation by increasing the hydroperoxide and hexanal lag phase to 6 and 9 days. The combination of phospholipase D modified high PS lecithins (15.0 µmol/kg emulsion) and a-tocopherol (3.0 µmol/kg emulsion) were able to synergistically increase the antioxidant activity of a-tocopherol increasing the hydroperoxide and hexanal lag phase by 6 and 9 days for soy, 5 days, and 7 days for sunflower and 4 and 6 days for egg lecithin, respectively. This resulted in synergistic antioxidant activity (interaction index > 1.0) except for a-tocopherol and high PS Egg lecithin which showed an additive effect. This research shows that the combination of enzyme-modified high PS lecithin and α-tocopherol could be an effective and commercially viable clean label antioxidant strategy to control lipid oxidation in emulsions.

In the present work, the flow behavior of an oil-in-water emulsion around and inside the measurement chamber of an in-line optical sensor probe is studied. The emulsion consists of a metalworking fluid, with oil droplets diameter ranging from 100 nanometers to 100 micrometers. The design of the UV-Vis light spectrometer probe is in accordance with the concept proposed in the research project named EPM (Emulsion Process Monitor in Metalworking Processes), carried out within the scope of the BRAGECRIM program between the University of São Paulo and the University of Bremen. This study is based on the numerical simulation of the interactions between the emulsion and the measurement system using computational fluid dynamic techniques, and is aimed at evaluating the effects of the probe geometry, its position relative to the flow field, and fluid properties on the expected spectrometer readings. Such effects are correlated with changes in droplet concentration and or droplet size segregation inside the measurement chamber of the optical probe, which can cause changes in the scattered light intensity readings. Segregation effects due to flow disturbances around the probe can be neglected under normal measurement conditions, with the probe facing the slit area inlet against the flow stream. Based on the simulation results, even if the probe is misplaced, the effect on the measurements is still insignificant. In-situ measurements carried out in a laboratory set up installed in the injection tube of a drilling machine support the simulation results, since no segregation effect related to the measurement system was observed. In addition to the study, the possibility of bacteria attachment on the internal glass walls of the probe was evaluated and it was found that when the flow velocity is large enough to produce a wall shear stress of about 3-5 Pa the bacterial contamination may be avoided. Changes in the probe geometry are proposed in order to attain an isokinetic condition for the flow around and inside the probe, resulting in a higher wall shear stress for lower inlet flow velocities. An additional study was performed using a tracking particle model to understand the relevance of the individual particles behavior under different flow conditions. The results do not indicate any significant effect on the measurements inside the probe, although additional studies should be carried out in this topic by considering a population balance model for the oil droplets. / O presente trabalho tem como objetivo o estudo do comportamento do escoamento de uma emulsão do tipo óleo - em água que flui no interior de câmara/duto de medição e que tem como obstáculo em seu caminho uma sonda de um sensor óptico, sensor óptico este que deve avaliar em tempo real a estabilidade da emulsão onde está inserido. A emulsão é constituída por um fluido de corte para usinagem, com gotículas de óleo de diâmetro variando de 100 nanômetros para 100 micrometros. A sonda utilizada junto ao espectrômetro de luz UV- Vis está de acordo com o conceito proposto no projeto de pesquisa chamado EPM (Emulsion Process Monitor in Metalworking Fluid), realizado no âmbito do programa BRAGECRIM entre a Universidade de São Paulo e a Universidade de Bremen. Este estudo baseia-se na simulação numérica das interações entre a emulsão e o sistema de medição proposto, utilizando técnicas de Fluido Dinâmica Computacional (CFD), e tem por objetivo avaliar os efeitos da geometria da sonda, a sua posição em relação ao campo do escoamento, e propriedades do fluido, em especial as propriedades a serem medidas pelo espectrômetro. Tais efeitos estão correlacionadas com alterações na concentração de gotas e a segregação ou o tamanho das gotas dentro da câmara de medição da sonda óptica, o que pode causar mudanças nas leituras de intensidade de luz difusa. Efeitos de segregação devido a perturbações do escoamento em torno da sonda podem ser negligenciados, em condições normais de medição, com a sonda voltada para frente e sua área de entrada contra a corrente do escoamento. Com base nos resultados de simulação, mesmo que a sonda seja deslocada, o efeito sobre as medições ainda é insignificante. Medições foram efetuadas em laboratório e também foram realizadas medições in-situ utilizando um adaptador de medição acoplado diretamente no tubo de injeção de fluido de corte da máquina de perfuração, estes testes foram feitos para de validar os resultados obtidos por simulação, uma vez que não se observou qualquer efeito de segregação relacionada com o sistema de medição. Além disso, foi acrescentada ao estudo, a possibilidade de fixação de bactérias nas paredes de vidro internas da sonda e verificou-se que quando a velocidade de escoamento é suficientemente grande para produzir uma tensão de cisalhamento de cerca de 3-5 Pa a fixação de bacteriana pode ser evitado. Aproveitando os resultados do estudo para prevenção de contaminação por bactéria, mudanças na geometria da sonda foram propostas a fim de atingir uma condição isocinética para o escoamento ao redor e dentro da sonda, resultando em uma maior tensão de cisalhamento para baixas velocidades de fluxo de entrada. Por fim um estudo adicional foi realizado utilizando um modelo de rastreamento de partículas para compreender a relevância do comportamento individual de cada partícula no escoamento da emulsão. Os resultados não indicam qualquer efeito significativo sobre as medições no interior da sonda, embora estudos adicionais devem ser realizados neste tópico, considerando um modelo de balanço populacional para as gotículas de óleo.

In the present work, the flow behavior of an oil-in-water emulsion around and inside the measurement chamber of an in-line optical sensor probe is studied. The emulsion consists of a metalworking fluid, with oil droplets diameter ranging from 100 nanometers to 100 micrometers. The design of the UV-Vis light spectrometer probe is in accordance with the concept proposed in the research project named EPM (Emulsion Process Monitor in Metalworking Processes), carried out within the scope of the BRAGECRIM program between the University of São Paulo and the University of Bremen. This study is based on the numerical simulation of the interactions between the emulsion and the measurement system using computational fluid dynamic techniques, and is aimed at evaluating the effects of the probe geometry, its position relative to the flow field, and fluid properties on the expected spectrometer readings. Such effects are correlated with changes in droplet concentration and or droplet size segregation inside the measurement chamber of the optical probe, which can cause changes in the scattered light intensity readings. Segregation effects due to flow disturbances around the probe can be neglected under normal measurement conditions, with the probe facing the slit area inlet against the flow stream. Based on the simulation results, even if the probe is misplaced, the effect on the measurements is still insignificant. In-situ measurements carried out in a laboratory set up installed in the injection tube of a drilling machine support the simulation results, since no segregation effect related to the measurement system was observed. In addition to the study, the possibility of bacteria attachment on the internal glass walls of the probe was evaluated and it was found that when the flow velocity is large enough to produce a wall shear stress of about 3-5 Pa the bacterial contamination may be avoided. Changes in the probe geometry are proposed in order to attain an isokinetic condition for the flow around and inside the probe, resulting in a higher wall shear stress for lower inlet flow velocities. An additional study was performed using a tracking particle model to understand the relevance of the individual particles behavior under different flow conditions. The results do not indicate any significant effect on the measurements inside the probe, although additional studies should be carried out in this topic by considering a population balance model for the oil droplets. / O presente trabalho tem como objetivo o estudo do comportamento do escoamento de uma emulsão do tipo óleo - em água que flui no interior de câmara/duto de medição e que tem como obstáculo em seu caminho uma sonda de um sensor óptico, sensor óptico este que deve avaliar em tempo real a estabilidade da emulsão onde está inserido. A emulsão é constituída por um fluido de corte para usinagem, com gotículas de óleo de diâmetro variando de 100 nanômetros para 100 micrometros. A sonda utilizada junto ao espectrômetro de luz UV- Vis está de acordo com o conceito proposto no projeto de pesquisa chamado EPM (Emulsion Process Monitor in Metalworking Fluid), realizado no âmbito do programa BRAGECRIM entre a Universidade de São Paulo e a Universidade de Bremen. Este estudo baseia-se na simulação numérica das interações entre a emulsão e o sistema de medição proposto, utilizando técnicas de Fluido Dinâmica Computacional (CFD), e tem por objetivo avaliar os efeitos da geometria da sonda, a sua posição em relação ao campo do escoamento, e propriedades do fluido, em especial as propriedades a serem medidas pelo espectrômetro. Tais efeitos estão correlacionadas com alterações na concentração de gotas e a segregação ou o tamanho das gotas dentro da câmara de medição da sonda óptica, o que pode causar mudanças nas leituras de intensidade de luz difusa. Efeitos de segregação devido a perturbações do escoamento em torno da sonda podem ser negligenciados, em condições normais de medição, com a sonda voltada para frente e sua área de entrada contra a corrente do escoamento. Com base nos resultados de simulação, mesmo que a sonda seja deslocada, o efeito sobre as medições ainda é insignificante. Medições foram efetuadas em laboratório e também foram realizadas medições in-situ utilizando um adaptador de medição acoplado diretamente no tubo de injeção de fluido de corte da máquina de perfuração, estes testes foram feitos para de validar os resultados obtidos por simulação, uma vez que não se observou qualquer efeito de segregação relacionada com o sistema de medição. Além disso, foi acrescentada ao estudo, a possibilidade de fixação de bactérias nas paredes de vidro internas da sonda e verificou-se que quando a velocidade de escoamento é suficientemente grande para produzir uma tensão de cisalhamento de cerca de 3-5 Pa a fixação de bacteriana pode ser evitado. Aproveitando os resultados do estudo para prevenção de contaminação por bactéria, mudanças na geometria da sonda foram propostas a fim de atingir uma condição isocinética para o escoamento ao redor e dentro da sonda, resultando em uma maior tensão de cisalhamento para baixas velocidades de fluxo de entrada. Por fim um estudo adicional foi realizado utilizando um modelo de rastreamento de partículas para compreender a relevância do comportamento individual de cada partícula no escoamento da emulsão. Os resultados não indicam qualquer efeito significativo sobre as medições no interior da sonda, embora estudos adicionais devem ser realizados neste tópico, considerando um modelo de balanço populacional para as gotículas de óleo.

The lubricants that are applied during metal cutting acts on the interface between the tool and the nascent surfaces generated by the cutting process. Dispersions of oil in water made using suitable emulsifier(s) are used as metal cutting lubricants. The efficiency of the emulsion in rendering a low friction layer on the freshly cut surface will depend on the composition of the emulsion and on the speed, load and temperature characteristics in the tribological system. A unique tribometer which can perform friction testing on freshly cut surfaces has been designed and built for the experimental investigation. In this experimental facility experiments are conducted by performing cutting operation inside a pool of the lubricant and friction force is measured in-situ. Experiments at different loads and speeds were performed. The surfaces were subsequently subjected to spectroscopic analysis using X-ray Photoelectron spectroscopy and Fourier Transform Infrared Spectroscopy (FTIR). Lubricity of the base oils on nascent and preformed (oxidized) surfaces are compared by performing friction tests on surfaces which are cut and friction tested without exposing them to the environment, and on surfaces which were cut and exposed to the environment. While the freshly cut surfaces were seen to be sensitive to the structure of the base oil, the oxidized surfaces did not differentiate between the oil structures. Amongst the three base oils tested, aromatic oil was found to exhibit the least friction. This is attributed to tendency of the aromatic chains to react with the surface and form a film, due to the formation of radical anion-metal cation complexes. Results from spectroscopic investigations are presented to substantiate these arguments. The thesis then explores the differences in the tribological behavior promoted by an emulsion between, when it acts on a cut surface and is slid just once, and when it acts on a cut surface slid repeatedly. Due to repeated sliding, friction was found to decrease with sliding time (distance), and the transition from a freshly formed surface to a repeatedly slid one was found to follow a smooth transition. The improvement in lubricity is attributed to the formation of carboxylate type structures (C=O) which get generated due to the tribological action under repeated sliding conditions in the presence of water. Under repeated sliding conditions, the friction as a function of emulsifier concentration is found to exhibit a minimum at a value which is much below the critical micellar concentration of the emulsifier (CMC). However, the variation under continuous cutting followed a different pattern, with the friction undergoing a sharp decrease close to the CMC. The effect of speed on the tribological performance was investigated and friction was found to increase dramatically beyond a critical speed which is marked as the onset of starvation. The characteristic time required for a film to develop on a newly created surface, together with the contact pressure conditions dictated by the load and speed dictates starvation. The films formed at speeds corresponding to starvation conditions was found to have a significantly different chemical structure from that corresponding to a speed less than the starvation speed.. The effect of temperature was found to affect the lubricity adversely. At elevated temperature, the nature of the film was found to change to that to starved condition, even at a speed which does not register starvation when operating at a lower temperature. The effect of solubility of the emulsifier on the friction characteristics were explored by using emulsifiers of varying hydrophilic-lypophilic values (HLB). Lower HLB emulsifiers were found to exhibit lesser friction, than those corresponding to high HLB value. The variation in lubricity is examined in the light of the morphology of the micellar structures which evolve using these emulsifiers. The main conclusions of the thesis are: 1 Evaluation of lubricity of metal cutting fluids warrants a testing strategy which tests their lubricity on freshly cut surfaces. 2 The formation of carboxylate structures aids lubricity while using an emulsion; emulsions which can result in the formation of such structures exhibit better lubricity under cutting conditions. 3 Tribofilms which show characteristic peaks related to chemisorbed oxygen is found to exhibit good lubricity under the test conditions. 4 Emulsifiers which form lamellar micellar structures which aid easy shear give better lubricity in cutting than those which yield spherical micelles.

Une nouvelle famille de dérivés amphiphiles du dextrane a été obtenue par réaction du dextrane avec le 1,2-époxydodécane en milieu basique. Deux voies de synthèse ont été étudiées. La première en milieu aqueux dispersé n’a permis d’obtenir que des taux de modification faibles (< 10 %) car l’homopolymérisation de l’époxyde est prépondérante. Au contraire, la réaction en milieu organique homogène a permis la synthèse de dérivés dont le taux de modification atteint 164 %. Des émulsions huile dans eau ont été préparées par sonication en présence de plusieurs dérivés hydrosolubles (τ ≤ 25 %). La fraction volumique d’huile (hexadécane ou nujol) est comprise entre 10 % et 50 %. La taille des gouttelettes augmente avec la fraction volumique d’huile mais ne dépend pas du taux de modification du dextrane entre 10 et 25 %. Ces émulsions ont un comportement de gel d’autant plus marqué que la fraction volumique d’huile dispersée augmente. Des émulsions inverses eau : chloroforme, stables pendant au moins 2 mois, ont été obtenues par sonication en présence de dérivés organosolubles (τ = 164 %). Le processus dynamique d’émulsification sous cisaillement a été étudié pour des émulsions directes (hexadécane / eau) dont la fraction volumique d’huile était comprise entre 10 et 60 % et pour différents gradients de vitesse. Un suivi continu in situ de la viscosité des émulsions et du rayon des gouttes formées montre que le temps caractéristique d’émulsification dépend du gradient de vitesse et du rapport des viscosités mais pas de la fraction volumique d’huile dispersée. Dans le cas d’un système newtonien, la viscosité finale et la taille finale des gouttes dépendent du gradient de vitesse appliqué alors qu’elles sont invariantes dans le cas du système non newtonien sur tout l’intervalle exploré / A new family of amphiphilic dextran derivatives was obtained by reaction of 1,2-epoxydodecane on dextran in basic medium. Two reaction procedures were examined. The first one was carried out in biphasic medium but produced only low degrees of hydrophobic substitution. Epoxide homopolymerization was indeed predominant. On the contrary, the reaction in a homogeneous organic medium allowed the synthesis of dextran derivatives with substitution degrees as high as 164 %. Oil-in-water emulsions were prepared by sonication in the presence of different hydrosoluble derivatives (τ ≤ 25 %). Oil volume fraction (hexadecane or nujol) ranged from 10 % to 50 %. The size of the emulsion droplets increased with the oil volume fraction but did not depend on the substitution degree of modified dextran between 10 and 25 %. These emulsions behave like a gel which strengthened with the oil volume fraction. Water-in-oil emulsions (water in chloroform) were obtained by sonication in the presence of organosoluble derivatives (τ = 164 %). They were stable over at least two months.Furthermore, dynamic emulsification process under shear flow was investigated for oil-in-water emulsions (hexadecane in water). The volume fraction of oil ranged from 10 % to 60 % and various shear rates were applied. Simultaneous in situ measurements of viscosity of emulsions and droplet size were performed. The characteristic time of emulsification depended on shear rate and viscosity ratio but was independent of the oil volume. For the newtonian system, final shear stress and final droplet size depended on the applied shear rate while they were invariant in the non newtonian system

Le phénomène de dérive constitue un enjeu environnemental et sanitaire majeur lors de la pulvérisation de solutions phytosanitaires sur les surfaces agricoles. Sous l'action du vent, des gouttelettes peuvent dériver loin des champs ciblés et être source de pollution. Une stratégie pour limiter la dérive est de contrôler la distribution de taille des gouttes de spray, en réduisant la proportion de petites gouttes. Dans ce but, des additifs anti-dérives, tels que des émulsions diluées d'huile dans l'eau, ont été développés. Bien que largement étudiés, les effets de ces émulsions ne sont pas encore bien compris. L'objectif de cette thèse est d'élucider les mécanismes à l'origine de l'augmentation de la taille des gouttes de spray à base d'émulsions.La pulvérisation implique la fragmentation d'un flux de liquide par une buse hydraulique. A la sortie de la buse, une nappe libre de liquide est formée, puis déstabilisée en gouttes. Afin d'élucider les mécanismes à l'origine des effets anti-dérives des émulsions, nous étudions l'influence de ces émulsions sur les mécanismes de déstabilisation des nappes liquides. Une expérience modèle basée sur la collision d'une goutte de solution sur une cible solide est utilisée pour produire et visualiser des nappes liquides. Lors de l'impact, la goutte s'aplatit en une nappe qui s'étend radialement dans l'air, bordée par un bourrelet plus épais. Différents mécanismes de déstabilisation sont observés en fonction des propriétés des fluides. Une nappe d'eau pure s'étale radialement puis se rétracte par effet de la tension de surface ; simultanément, le bourrelet est déstabilisé en gouttes. Pour une émulsion diluée d'huile dans l'eau, le mécanisme de déstabilisation dominant est considérablement modifié: les nappes sont déstabilisées par la nucléation de trous qui perforent le film liquide lors de son expansion; les trous grandissent jusqu'à la formation d'un réseau de ligaments, qui est ensuite déstabilisé en gouttes.Une étude systématique de l'influence des paramètres physico-chimiques de l'émulsion, tels que la concentration en huile et la distribution de taille de gouttelettes d'huile, sur le mécanisme de perforation est conduite. Nous établissons une corrélation entre le nombre d'évènements de perforations observés dans les nappes modèles et la distribution de taille de gouttes de sprays formés avec des buses de pulvérisation agricoles. Ce résultat démontre la pertinence expérimentale de notre expérience modèle pour comprendre les mécanismes d'actions des formulations anti-dérives. Nous montrons ainsi que le mécanisme à l'origine de l'augmentation de la taille des gouttes de spray à base d'émulsion est un mécanisme de perforation.Pour comprendre les mécanismes à l'origine de la perforation, nous développons une technique optique permettant de mesurer le champ d'épaisseur de nappes liquides. Nous constatons que la formation d'un trou dans la nappe est systématiquement précédée par un amincissement local du film liquide. Nous montrons que cet amincissement est le résultat de l'entrée puis de l'étalement par effet Marangoni de gouttelettes d'huile à l'interface air/eau. L'amincissement du film liquide conduit in fine à sa rupture.Nous proposons un mécanisme de perforation en deux étapes: les gouttelettes d'huile (i) entrent à l'interface air/eau, et (ii) s'étalent à l'interface. La formulation de l'émulsion est un paramètre critique pour contrôler le processus de perforation. L'addition de sels ou de copolymères amphiphiles à des émulsions stabilisées par des tensio-actifs ioniques peut soit déclencher, soit inhiber le mécanisme de perforation. Nous montrons que l'entrée de gouttes d'huile à l'interface air/eau est l'étape limitante de ce mécanisme. Les interactions répulsives de nature stérique et/ou électrostatique entre les gouttelettes d'huile et l'interface stabilisent le film liquide, empêchant les gouttelettes d'entrer à l'interface, et ainsi inhibent le processus de perforation. / One of the major environmental issues related to spraying of pesticides on cultivated crops is the drift phenomenon. Because of the wind, small droplets may drift away from the targeted crop and cause contamination. One way to reduce the drift is to control the spray drop size distribution and reduce the proportion of small drops. In this context, anti-drift additives have been developed, including dilute oil-in-water emulsions. Although being documented, the effects of oil-in-water emulsions on spray drop size distribution are not yet understood. The objective of this thesis is to determine the mechanisms at the origin of the changes of the spray drop size distribution for emulsion-based sprays.Agricultural spraying involves atomizing a liquid stream through a hydraulic nozzle. At the exit of the nozzle, a free liquid sheet is formed, which is subsequently destabilized into droplets. In order to elucidate the mechanisms causing the changes of the spray drop size distribution, we investigate the influence of emulsions on the destabilization mechanisms of liquid sheets. Model single-tear experiments based on the collision of one tear of liquid on a small solid target are used to produce and visualize liquid sheets with a fast camera. Upon impact, the tear flattens into a sheet radially expanding in the air bounded by a thicker rim. Different destabilization mechanisms of the sheet are observed depending on the fluid properties. A pure water sheet spreads out radially and then retracts due to the effect of surface tension. Simultaneously, the rim corrugates forming radial ligaments, which are subsequently destabilized into droplets. The destabilization mechanism is drastically modified when a dilute oil-in-water emulsion is used. Emulsion-based liquid sheets are destabilized through the nucleation of holes within the sheet that perforate the sheet during its expansion. The holes grow until they merge together and form a web of ligaments, which are then destabilized into drops.The physical-chemical parameters of the emulsion, such as emulsion concentration and emulsion droplet size distribution, are modified to rationalize their influence on the perforation mechanism. We correlate the size distribution of drops issued from conventional agricultural spray with the amount of perforation events in single-tear experiments, demonstrating that the single-tear experiment is an appropriate model experiment to investigate the physical mechanisms governing the spray drop size distribution of anti-drift formulations. We show that the relevant mechanism causing the increase of drops size in the emulsion-based spray is a perforation mechanism.To gain an understanding of the physical mechanisms at the origin of the perforation events, we develop an optical technique that allows the determination of the time and space-resolved thickness of the sheet. We find that the formation of a hole in the sheet is systematically preceded by a localized thinning of the liquid film. We show that the thinning results from the entering and Marangoni-driven spreading of emulsion oil droplet at the air/water interface. The localized thinning of the liquid film ultimately leads to the rupture of the film. We propose the perforation mechanism as a sequence of two necessary steps: the emulsion oil droplets (i) enter the air/water interface, and (ii) spread at the interface. We show that the formulation of the emulsion is a critical parameter to control the perforation. The addition of salt or amphiphilic copolymers can trigger or completely inhibit the perforation mechanism. We show that the entering of oil droplets at the air/water interface is the limiting step of the mechanism. Thin-film forces such as electrostatic or steric repulsion forces stabilize the thin film formed between the interface and the approaching oil droplets preventing the entering of oil droplets at the interface and so inhibit the perforation process.

In the present work, a new generation opaque polymer pigment with multihollow structure was synthesized by suspension polymerization of &ldquo / Water-in-Oil-in-Water&rdquo / (W/O/W) emulsion system. Oil phase was methyl methacrylate and ethylene glycol dimethacrylate monomer mixture at 1:1 weight ratio. The dimension and distribution of hollows inside polymer particles are dependent on the size of water droplets which are encapsulated in micelles. For Water-in-Oil (W/O) assembly, a hydrophobic surfactant and hydrophilic co-surfactant (Span 80-Tween 80) combination with a hydrophilic/lipophilic balance (HLB) value between 5-8 was used. The effects of surfactant and co-surfactant composition on the stability of the W/O emulsion and also on the size of water droplets were studied. In addition, the effect of the ultrasonication on the average size of water droplets was investigated. The hollow size distribution which may possibly give the maximum scattering efficiency was predicted by a mathematical model based on the Mie scattering. The optimum size distribution for W/O emulsion was obtained at the monomer/surfactant/water ratio of 75.5/9.4/15.1 after ultrasonication for 30 seconds at 80 W power. The W/O/W emulsion was prepared by dispersing the W/O emulsion in aqueous solution of hydrophilic Triton X-405. The influence of surfactant concentration and mechanical mixing on monomer droplets was investigated by size measurement and optical microscopy. After stabilizing with 1 %w/w polyvinylpyrrolidone (PVP) solution, the W/O/W emulsion was polymerized at 55 &deg / C for 20 h. The surface morphology of synthesized polymer pigments was analyzed by scanning electron microscopy (SEM) and the inner hollow structure was confirmed by transmission electron microscopy (TEM). The analysis indicated that multihollow opaque polymer pigments were successfully synthesized. The opacity, the L*a*b* color, and the gloss properties of polymer pigments were examined by spectrophotometer and glossmeter. The opacity values were assessed by contrast ratio measurements, and the synthesized polymer pigments provided up to 97.3 % opacity (50 %v/v solid content). In addition, the pigments exhibited low gloss values, and yielded matt films.

Abstract Nanocellulose is a renewable, biodegradable, and easily available material that is considered as an attractive resource for many different value-added applications in the emerging bio-based economy. Its outstanding properties, such as strength, lightness, transparency, and good thermal insulation, have inspired research and product development around nanocellulose. The potential of nanocellulose to replace synthetic chemicals made from non-renewable sources, for example, is considered to be very promising. Chemical functionalization, that is, the modification of the cellulosic surface properties, is seen to be beneficial in applications such as those in which higher hydrophobicity is needed. In this thesis, the ability of cellulose nanoparticles to stabilize oil droplets in oil-in-water emulsions was studied. The aim of the study was to explore the possibility of developing a new type of "green" oil spill chemical from cellulose. Therefore, the cellulose was chemically modified in an aquatic environment with a sequential periodate oxidation and chlorite oxidation followed by reductive amination reaction, which increased the hydrophobicity of the produced nanocellulose. In addition, the use of deep-eutectic solvents in the preparation of modified (succinylated and carboxylated) and non-modified cellulose nanoparticles was studied. Chemical (kraft) pulp, dissolving pulp, and semi-chemical fine fibers were used as raw materials in this research. The results demonstrated that chemically modified cellulose nanoparticles work well as stabilizers for oil-water emulsions resulting in small, stable oil droplets and impeding creaming, which is a typical phenomenon for particle stabilized emulsions. The modification of cellulose nanoparticles improved their ability to partition at the oil-water interface, which enabled efficient and irreversible adsorption. It was found that because of their small size, the cellulose nanocrystals can be compressed more tightly onto the surface of the oil droplet, while longer and more flexible cellulose nanofibrils formed a web structure between the oil droplets. All cellulose nanoparticle-stabilized emulsions were stable against droplet coalescence, and even at low temperatures, they retained their droplet size and stability. Salinity, on the other hand, improved stability when CNCs from chemical pulp were used, but it negatively affected stability when nanocrystals from semichemical pulp were used. / Tiivistelmä Uusiutuva, biohajoava ja helposti saatavilla oleva nanoselluloosa on merkittävä tulevaisuuden raaka-aine useissa erilaisissa käyttökohteissa. Sen ylivertaiset ominaisuudet, kuten lujuus, keveys, läpinäkyvyys ja lämmöneristävyys ovat olleet innoittamassa nanoselluloosan tutkimusta ja tuotekehitystä. Nanoselluloosan mahdollisuuksia ja käyttöä eri sovelluksissa korvaamaan esimerkiksi uusiutumattomista luonnonvaroista valmistettuja kemikaaleja, pidetään erittäin lupaavina. Kemiallisesta funktionalisoinnista eli selluloosan pintaominaisuuksien muokkauksesta nähdään olevan hyötyä, kun tavoitellaan nanoselluloosan toiminnallisuutta esimerkiksi hydrofobista luonnetta vaativissa sovelluksissa pinta-aktiivisen aineen tavoin. Tässä työssä tutkittiin erityisesti nanoselluloosapartikkeleiden kykyä stabiloida öljypisaroita dieselöljy-vesiemulsioissa. Tutkimuksen päämääränä oli selvittää mahdollisuutta kehittää uudentyyppistä, ”vihreää” öljyntorjuntakemikaalia selluloosasta. Tämän vuoksi selluloosaa muokattiin kemiallisesti vesiympäristössä yhdistetyllä hapetus- ja aminointikäsittelyllä, mikä lisäsi valmistetun nanoselluloosan hydrofobisuutta. Toisena käsittelyvaihtoehtona tutkittiin syväeutektisten liuottimien käyttöä sekä muokattujen (sukkinyloidut ja karboksyloidut) että muokkaamattomien nanoselluloosapartikkeleiden  valmistuksessa. Raaka-aineina työssä käytettiin kemiallista sellumassaa, liukosellua sekä puolikemiallista hienokuitua. Työn tuloksena voidaan todeta, että nanoselluloosasta valmistetut kemiallisesti muokatut (funktionalisoidut) nanopartikkelit toimivat hyvin öljy-vesiemulsiossa estäen emulsion öljypisaroiden yhteensulautumista. Nanopartikkelit stabiloivat emulsiossa olevan öljyn hyvin pieniksi pisaroiksi hidastaen kermottumista eli emulsion yleistä faasierottumista. Nanoselluloosan funktionalisointi paransi sen kykyä hakeutua öljy-vesi rajapintaan, mahdollistaen tehokkaan ja palautumattoman adsorption. Havaittiin, että pienen kokonsa vuoksi selluloosananokiteet pystyivät pakkautumaan tiiviimmin öljyn pinnalle, kun taas selluloosananokuidut, jotka ovat pidempiä, muodostivat verkkomaisen rakenteen myös öljypisaroiden väliin. Suolan lisäys vaikutti emulsion stabiilisuuteen vaihtelevasti eri näytteiden välillä, kun taas kylmät olosuhteet poikkeuksetta paransivat stabiilisuutta.