Ce travail porte sur l’inversion de phase catastrophique induite par l’agitation continue d’un système anormal eau-huile-surfactif, sans addition de phase, afin de réaliser des émulsions eau-dans-huile concentrées et finement dispersées. Les suivis rhéologiques et conductimétriques des systèmes sous agitation indiquent que l’inversion passe, en général, par la formation d’une émulsion multiple e/H/E dans laquelle une partie de la phase continue est inclue comme gouttelettes dans les gouttes de phase dispersée. Ainsi, le volume apparent de phase dispersée augmente jusqu’à atteindre une valeur critique à laquelle l’inversion se produit. Afin de maîtriser ce processus, l’influence de variables de formulation, composition et agitation sur le mécanisme d’inversion et sur ses paramètres caractéristiques a été étudié. Les données recueillies permettent de choisir les conditions de formulation et de procédé pour préparer, en un temps minimal, des émulsions E/H avec des propriétés requises. / This study deals with the catastrophic phase inversion produce by continuous stirring of an abnormal water-oil-surfactant system, without internal phase addition, in order to prepare concentrated and fine water-in-oil emulsions. The simultaneous conductivity and viscosity measurements of the system under stirring show that generally, the inversion takes place through the formation of a multiple w/O/W emulsion in which a portion of the external phase is continuously included as droplets in the dispersed phase drops. Consequently, the dispersed phase apparent volume increases until a critical value is reached and the inversion is triggered. In order to control this process, the influence of formulation, composition and stirring variables on the inversion mechanism and on its characteristic parameters is studied. The data collected can be used to prepare, in a minimal time, emulsions with required properties, by controlling the formulation and process conditions.

Ce travail porte sur la description et la compréhension de l’inversion de phase catastrophique utilisée pour l’émulsification de produits visqueux, à travers l’analyse des effets de formulation et de procédé sur la fraction de phase dispersée à laquelle le processus se produit et sur les mécanismes mis en jeu. Les suivis rhéologique et conductimétrique simultanés in situ de l’émulsification ont permis, du point de vue procédé, de mettre en avant l’influence du débit d’addition de la phase aqueuse sur la formation d’émulsions multiples du type e/H/E lesquelles, en augmentant notablement la fraction de phase dispersée apparente, sont responsables de l’inversion dès de faibles fractions de phase dispersée ajoutée. Au niveau formulation, l’augmentation de la viscosité de l’huile induit de manière remarquable la tendance de cette phase à devenir le milieu dispersé, conduisant à une inversion pour de très faibles fractions de phase aqueuse et donc à des émulsions finales très concentrées (de 80 à 95% en volume). Le suivi au microscope du phénomène d’inversion de phase par l’intermédiaire d’un écoulement de type « squeezing flow », a permis d’établir les conditions et les mécanismes conduisant à une inversion complète ou seulement partielle. La viscosité relative des phases aqueuse et huileuse est responsable d’une inversion catastrophique suivant un mécanisme de type agglomération – coalescence plutôt que de type inclusion/fuite tel que généralement admis. L’établissement d’un modèle mathématique basé sur les bilans de population et le caractère fractal du phénomène a permis de décrire l’évolution de la taille des gouttes multiples ainsi que la fraction de phase dispersée ajoutée à laquelle l’inversion se produit / This study deals with the description and understanding of catastrophic phase inversion during high viscous oil emulsification, through the analysis of the effects of formulation and process variables on the dispersed phase fraction at which the inversion is triggered and on the involved mechanisms. The simultaneous follow – up in situ of viscosity and conductivity measurements allowed, from a process point of view, to emphasize on the effect that the aqueous phase addition rate has on the formation of multiple w/O/W emulsions. Due to the formation of w/o/W emulsions, the volume of the effective dispersed phase greatly increases while at the same time, if the aqueous phase is added by very small fractions inversion of the w/o/W system can occur. In relation with formulation, an increase in oil viscosity greatly increased the tendency of the oily phase to become the dispersed phase. At the same time, it promoted the formation of highly concentrated emulsions (about 80 to 95 % in volume) after the inversion had occurred. The microscopical follow-up of emulsion morphology by means of squeezing flow, allowed us to establish the conditions and mechanisms that lead to partial or complete inversion. Even though literature sources lead us believe that inversion will occur through the “inclusion/escape” mechanism, experimental results showed that the relative viscosity between the phases promoted inversion through the mechanism of “agglomeration – coalescence” rather than “inclusion/escape”. A mathematical model based on population balances and on the fractal nature of multiple emulsions allowed us to describe the multiples drop size and effective dispersed phase evolution until inversion phenomena

Les émulsions de Pickering ont suscité un intérêt croissant dans de nombreux domaines de la recherche en raison de leur grande stabilité et versatilité. Une attention particulière a été accordée à la fabrication des systèmes complexes et originaux qui peuvent être obtenus avec différentes particules. Cette étude a consisté dans l'analyse des différents paramètres physico-chimiques des particules, des milieux liquides et des systèmes dispersées, et leur relation avec le comportement mécanique et la structure des émulsions afin de prédire et de moduler les caractéristiques de ces dernières. Nous avons étudié plus particulièrement pour la première fois, le diagramme de phase concernant les inversions de phase du type catastrophique et transitionnelle des émulsions de Pickering. Nous avons utilisé des particules de silice avec des structures et hydrophobicités différentes. En particulier, nous avons montré que le mélange de particules de différente hydrophobicités peut moduler finement l'inversion de phase aussi bien que les propriétés rhéologiques et structurales des émulsions. La fabrication de membranes à partir des émulsions de Pickering précédentes a été proposée comme un exemple de l'utilisation de ces systèmes modèles pour la conception de matériaux complexes. / Pickering emulsions have gained interest in many fields of research due their properties like higher stability and versatility. Special attention has been given to the processing of complex and original systems which can be obtained by using different particles. This study consists in the analysis of the different physicochemical parameters of particles, liquid media as well dispersion systems, and their relationship with emulsions structural and mechanical behavior in order to predict and modulate the emulsions characteristics. We studied extensively for the first time the phase diagram of catastrophic and transitional phase inversion of Pickering emulsions. We used silica particles with different structure and hydrophobicity. In particular we showed that mixing particles with different hydrophobicity can finely modulate the phase inversion as well the rheological and structural properties of the emulsions. The manufacturing of emulsified membranes based on previous Pickering emulsions was proposed as an example of the use of these systems as templates for the design of complex materials.

Solvent-free extrusion emulsification (SFEE) is a recently developed process for producing submicron particles with high viscosity polymers inside a twin-screw extruder without the use of hazardous solvents. Its dependency on a catastrophic phase inversion makes the process knowingly sensitive to a variety of formulation and operational variables, causing a narrow window of production. The purpose of this thesis was to investigate and improve process stability as well as widening operational window. Transient effects of the start-up procedure was investigated by considering the process stability and particle size distribution. The transient sensitivity corresponded to the residency of material in the dispersion zone. When a sub-optimal water/surfactant fraction was allowed to produce an undesired polymer-water (thick lamella) morphology, this morphology continued to persist until the critical first half of the dispersion zone was purged of existing mass. Lot to lot variability of polyester resin was used to investigate the sensitivities of the SFEE process more deeply to better understand the mechanism involved. In this case, acid number was shown to have a significant effect on the initial amount of water needed in the dispersion zone for phase inversion, resulting in an emulsification boundary dependent on the resin acid number. In fact, a significant correlation was found between the acidic end groups of the resin and the maximum amount of water content that could be used in the dispersion zone. The effect of feed rate, screw speed, dispersion length, and surfactant concentration were studied for their individual influence on widening the emulsification boundary. The most significant improvement was observed by applying a longer dispersion length or lower feed rate because both significantly increase the residence time. The effect of residence time on the emulsification boundary was attributed to the total strain imposed on the polymer/water mixture which was related to interfacial growth in the dispersion zone. / Dissertation / Doctor of Philosophy (PhD)