Miniemulsion technology is attracting increasing interest for the preparation of nano-size particles. However, the barrier to industrialising miniemulsion-based products is the lack of an energy efficient and scalable homogenisation device. Current laboratory techniques consist of batch units, however trends are leaning towards developing continuous processes. The objective of the work presented here is to investigate the use of the rotor-stator (RS) and static mixers (SM) as homogenisation devices and ultimately develop a continuous emulsification/polymerisation process for the preparation of miniemulsions. Initially we investigated the RS as a homogenisation device and found that we were able to generate droplets ranging from 300 nm to 2 μm, at industrially pertinent solids content. Subsequently, we investigated the use of SM and compared their performance in terms of mean droplet size evolutions with the rotor-stator. We were able to generate droplets < 200 nm in size and polymerise them in a stable fashion. All the available emulsification devices were then compared in terms of power/energy consumption, droplet size distributions and shear rates. It was observed that with energy costs being of similar orders of magnitude, SM imposed less shear, produced relatively narrow distributions and were better adapted to scale-up, making them the optimal choice for miniemulsification. Energy savings were increased by reducing coalescence during the emulsification step by using in situ generated surfactants, ultimately reducing emulsification time. Neutralising a water-soluble base with an oil-soluble acid almost instantaneously generates in situ surfactants at the oil-water interface. The reduction in emulsification time was partially attributed to the elimination of the relatively slow adsorption step typical of preformed surfactants. These results were used to show that emulsifying in situ formulations at moderate flow rates in line with SMX mixers can substantially reduce emulsification time from 30 minutes, with preformed surfactants, to ~30 seconds. With such a rapid emulsification step, it was possible to test the feasibility of the continuous emulsification process followed by polymerisation in a tubular reactor. Comparing this process with a batch operation, similar results for the ratio of NP/ND and conversion were obtained, but the continuous process was accomplished in a single step. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2010-04-19 03:32:08.766

Cette étude porte sur l'émulsification en continu du bitume à l'aide de mélangeurs statiques de type SMX, dans le domaine des émulsions concentrées, voire très concentrées. Ce travail suit une approche intégrant trois types de paramètres : procédé, formulation physico-chimique et composition, avec pour objectif ultime la maîtrise de la taille de gouttes. Il a été montré qu'une combinaison de fortes teneurs en bitume et de hautes températures d'émulsification favorisent l'obtention de très petites tailles de gouttes (diamètre médian inférieur ou égal à 1 µm). Cette observation contraste avec l'émulsification à forte teneur en phase dispersée en procédé discontinu. Ces résultats mettent en évidence une compétition entre les aspects énergétiques de l'émulsification et la formulation physico-chimique. Il a été mis en évidence, que lors de l'émulsification en continu à des fractions massiques en bitume supérieures à 90 %, la taille des gouttes n'est pas une fonction de l'énergie fournie mais que ce sont les paramètres de formulation qui contrôlent l'émulsification. Le suivi de la cinétique de l'émulsification et de la morphologie de l'émulsion au cours du processus d'émulsification a montré que le mécanisme d'émulsification à très fortes concentrations en bitume (90 % massique) passe par une étape d'inversion de phases catastrophique, suivie d'un affinage de l'émulsion dû aux effets de cisaillement et d'élongation lors de la phase finale de mélange. Une méthodologie basée sur une analogie de Poiseulle pour la mesure en ligne de la viscosité de procédé a été développée, permettant l'évaluation in-line du comportement rhéologique d'un fluide à travers des mesures de débit et de perte de charge / This work focuses on the continuous emulsification process (using SMX static mixers) of bitumen for concentrated and highly concentrated emulsions. This work uses an approach that integrates the process, the physic-chemical formulation and composition parameters, with the main objective of controlling the drop size of the emulsions. It was shown that the emulsification carried out at high bitumen concentrations and high temperatures favours the production of emulsions with very small droplets sizes (mean diameter ? 1 mm). This is in contrast with emulsification process in batch mode, in the same concentration and temperature conditions. These results demonstrate the competition between energy and physic-chemical formulation aspects. It was also revealed that when continuous emulsification is carried out at 90 % wt. of bitumen, droplet sizes are not a function of the energy provided and, hence, the emulsification process is controlled by the formulation parameters. Morphological analyzes, coupled with kinetics of emulsification obtained by in-situ monitoring of the viscosity, allowed the description of the mechanisms occurring during the emulsification at high internal phase ratio. It was possible to identify two principal steps in the mechanism: a catastrophic phase inversion followed by a droplet reduction by agitation, the largest size reduction being achieved thanks to the effects of shear and elongation in the static mixer. An inline process viscosity measurement methodology was developed. This methodology, based on a Poiseuille analogy, allows the evaluation of the rheological behavior of a fluid through flow rate and pressure drop measurements

No description available.

Ces travaux de recherche portent sur le développement d’un procédé permettant de mélanger, directement en sortie de polycondensation, du polyamide fondu avec d’autres polymères immiscibles en tant qu’additifs. Ce procédé se distingue ainsi des méthodes d’élaboration conventionnelles pour lesquelles une fusion préalable des polymères est nécessaire. L’étude concerne le mélange de polymères de viscosités très différentes (polyamide 66 et polyéthylène glycol) et le mélange de polymères de viscosités similaires (polyamide 66 et copolymère d’éthylène propylène, en présence ou non d’un agent d’interface : polypropylène greffé par de l’anhydride maléique).Une première partie de ce travail a consisté à caractériser la dispersion de ces mélanges élaborés selon des procédés conventionnels. Ce travail a conduit à développer un modèle reliant la taille de la phase dispersée aux principaux paramètres opératoires de chaque procédé, pour le cas rarement recensé dans la littérature, des mélanges de polymères de viscosités très différentes.La seconde partie a été consacrée à la conception et à la réalisation d’une installation constituée d’un pilote de polycondensation équipé, en sortie de réacteurs, d’un dispositif de mélange reposant sur la technologie des mélangeurs statiques. Son fonctionnement a ensuite été éprouvé pour les deux mélanges considérés, grâce des expériences qui ont permis d’analyser l’influence de différentes conditions opératoires sur la morphologie des mélanges générés. La comparaison des résultats obtenus à ceux issus des procédés conventionnels, a alors permis de préciser les performances et les limites du procédé développé dans cette étude / The aim of this work is to develop a process, which enables to blend polyamide in molten state with others polymers, directly at the outlet of a polycondensation reactor. Contrary to currently industrial processes, no remelting stage is needed in this one. The study has been carried out with polyamide 66 / polyethylene glycol blends (products with very different viscosities) and with polyamide 66 / ethylene propylene blends (products with similar viscosities), with or without polypropylene-graft-maleic-anhydride as interfacial agent. The first part of this work deals with the characterization of the dispersions obtained for these blends when their elaborations are carried out using conventional processes. Only few studies are available on blends, which exhibit a large difference between components viscosity. This work led us to develop a model to correlate, in this case, the dispersed phase size to the main operating conditions of each processes.The second part is dedicated to the design and the realization of an experimental installation, which is composed of polycondensation plant equipped, at the outlet of reactors, with a blending device based on static mixers technology. Its operation has been tested and experiments have been carried out in order to study the influence of the different processing parameters on blends morphology. The comparison of the results with those previously obtained using conventional processes allowed then to precise the performances and the limits of the process developed in this study

No description available.

<p>In this research, liquid-liquid dispersion of viscous fluids was studied in an SMX static mixer in the laminar regime. Backlighting technique was used for flow visualization, and the Hough transform for circle detection was used in OpenCV to automatically detect and measure drop diameters for obtaining the size distribution. Silicone oil and an aqueous solution of high fructose corn syrup were used for dispersed and continuous phases respectively, and sodium dodecyl sulfate was used as the surfactant to modify the interfacial tension. Experiments were conducted at varying viscosity ratios and flow rates-each at zero, low (~200 ppm) and high (~1000 ppm) surfactant concentrations. The effect of holdup was explored only for a few cases, but it was found to have a minimal effect on the weighted average diameter D₄₃.</p> <p>It was found that the superficial velocity and the continuous phase viscosity had a dominant effect on D₄₃. The tail at the higher end of the droplet size distribution decreased with increasing superficial velocity and continuous phase viscosities. It was also found that D₄₃ decreased with lowering of the interfacial tension. Furthermore, the effect of the dispersed phase viscosity was significant only at non zero surfactant concentrations.</p> <p>An approximate model has been proposed that relates D₄₃ to the capillary number. It is based on an energy analysis of the work done by the viscous and surface forces on a drop of an initial diameter that is largely determined by the gap distance between the cross bars in the element</p> / Master of Applied Science (MASc)