L'amphotéricine B (AmB) est une molécule utilisée en thérapeutique pour ses propriétés antifongiques remarquables. Cependant, ses caractéristiques physico-chimiques très particulières, rendent difficile la conception et la fabrication de systèmes thérapeutiques chargés en AmB qui soient simultanément efficaces et peu toxiques. La littérature montre qu'il existe une relation intime entre la façon dont l’AmB est associée au système transporteur et les effets pharmacologiques et toxicologiques qui sont observés. Malgré de très nombreuses études, l’état d’association des molécules d’AmB dans les différentes formulations commercialisées contenant de l'AmB n’est toujours pas connus avec suffisamment de précision. Pour cette raison, le but de ce travail expérimental est de caractériser différents systèmes contenant de l'AmB, dans l’objectif de prédire les effets biologiques induits par l’état d’association de cette molécule à ces systèmes supramoléculaires. Dans ce travail, nous avons caractérisé un système micellaire original ainsi que deux autres produits similaires tout en les comparant. De plus, nous avons étudié les mécanismes par lesquels se forment des super-agrégats d’AmB par l'augmentation de la stabilité des systèmes chauffés. Dans un second temps et pour la première fois, la capacité de l’AmBisome®, à former des super-aggrégats a également été caractérisée et testée. Enfin, l'incorporation de l'AmB dans des systèmes de type nano- et micro-émulsion a été étudiée, avant d’être appliquée au traitement des maladies oculaires fongiques et de la leishmaniose viscérale. Les principales techniques utilisées pour la caractérisation physico-chimiques de l’état d’agrégation ont été : la spectroscopie électronique (UV-Vis), le dichroïsme circulaire (DC) et la diffusion dynamique de la lumière (DLS). La calorimétrie à titrage isotherme (ITC) a été utilisée afin de tenter de mesurer l’énergie de formation des super-agrégats. De plus, un dérivé soluble de l’AmB a été développé et caractérisé par spectroscopie de masse atomique, infrarouge, UV-Vis et DC. Afin de disposer d’un système d’administration adéquat, ce dérivé soluble a été ensuite incorporé dans une micro-émulsion. Au total, l’ensemble des travaux expérimentaux conduits, montrent que l’état d'agrégation moléculaire de l’AmB dépend très largement du système d’administration utilisé, ainsi que des procédés par lesquels l’AmB est associées à ces systèmes. Ces résultats ont une réelle importance pratique puisque la littérature montre sans ambiguïté que l'efficacité du médicament ainsi qu’à sa toxicité dépendent étroitement de l'état d'agrégation de l’AmB. Ainsi, dans la nanoémulsion, l’AmB se trouve dans des états agrégés et multi-agrégés. Au contraire, dans la micro-émulsion, l’AmB se présente plutôt sous forme « monomère ». Une fois chauffés, les systèmes micellaires forment des super-agrégats d'AmB, tandis que les liposomes étudiés sont incapables de donner naissance à cette structure supramoléculaire. Enfin, le dérivé soluble d'AmB que nous avons préparé présente des caractéristiques distinctes par rapport à la molécule d'origine. Cependant, une fois associé à une microémulsion, son état d'agrégation est modifié et redevient similaire à celui de l'AmB originale, comme l’indique les études en UV-Vis et en DC. On peut donc conclure de ce travail que l'état d'agrégation d'AmB varie considérablement en fonction du type de système d’administration utilisé, de la concentration de l’AmB ainsi que du mode d'incorporation de la molécule, y compris pour un même système. Enfin, ce travail a permis la mise au point d’un dérivé soluble original de l’AmB qui offre la possibilité d’utiliser des formulations aqueuses adaptées à différentes voies d’administration et pourrait renouveler l’intérêt de cette molécule ancienne dans le traitement de différentes pathologies fongiques pour lesquelles il n’existe pas de formulations réellement adapatées. / The amphotericin B (AmB) is a drug of peculiar physicochemical features: being amphiphilic and amphoteric. These characteristics turn difficult the drug load into therapeutic systems. AmB is currently available in the market as micelles, liposomes and lipid complex for injection. The literature show that there is an intimate correlation between the AmB bound to the carrier and its biological response. However, there is a deficiency concerning the physicochemical characterization of the available AmB-containing products. Therefore, the aim of this work was to characterize AmB-containing carriers seeking a prediction to its biological response. The AmB-containing micellar system was the first product available for clinical use. The patent of this product has already expired some years ago. In this work we have characterized the original system and two other similar micellar products. In addition, we studied the stability increase of heated systems, by the formation of AmB “super-aggregates”. AmBisome®, an AmB-containing liposomal system, was also characterized and, for the first time, tested for the possibility of super-aggregates formation. The AmB incorporation into nano and microemulsion systems was presented and the physicochemical characteristics evaluated, focusing mainly on applications for the treatment of fungal ocular diseases and also for visceral leishmaniasis. The main techniques used for characterization were electronic spectroscopy, circular dichroism and dynamic light scattering. The isothermal titration calorimetry (ITC) was used as an attempt to measuring the super-aggregates energy formation. Besides, an AmB soluble derivative was developed and characterized by atomic mass spectroscopy, infra-red, UV-Vis and circular dichroism. Then, this AmB-derivative was loaded into a microemulsion as a vehiculation strategy. The overall results show that the AmB-containing systems presented different molecular aggregation states that depends on the carrier, the way the drug is incorporated and also on the diluent. According to the literature, the aggregation state is associated with both, drug efficiency and toxicity. In nanoemulsion systems, the drug is found aggregated and multi-aggregated. In microemulsions, AmB is loaded as monomers. The heated micellar systems form AmB super-aggregates while the liposomal system is unable to form such molecular structure. Moreover, the AmB soluble derivative presented distinct features when compared to the original molecule. However, once incorporated into the microemulsion, the aggregation state is similar to that of the original AmB molecule, as supported by UV-Vis and circular dichroism results. It can be concluded that the AmB aggregation state varies according to the kind of carrier, the drug concentration and also the way of drug incorporation, even into one same carrier. Finally, the soluble derivative opens the possibility for drug carrying into aqueous vehicles for the treatment of many diseases by different administration routes.

La situation durable de volatilité des prix du pétrole est considérée à la fois comme une menace et un défi par l'industrie pétrolière. Au cours de cette crise, les compagnies pétrolières ont l’opportunité de se recentrer sur la recherche de solutions de production rentables, ce qui implique souvent l’apport des nouvelles technologies, en plus de l'amélioration des processus.Ce travail présente une avancée pour la synthèse d’une nouvelle génération de fluides de forage pétrolier sans surfactants/émulsifiants pour des applications dans le forage des puits profonds et ultra profonds. Cette nouvelle génération repose sur l’introduction des émulsions de Pickering dans la formulation des fluides de forage. Ces dernières sont des émulsions stabilisées uniquement par des particules solides (dans ce cas des particules de silice). Différents types de nano particules de silice de différentes hydrophobicités ont été utilisées pour stabiliser des fluides de forage de types huile-dans-eau et eau-dans-huile. Ces fluides ont été conçus pour être utilisés dans des conditions hostiles de température et de pression. Par conséquent, une caractérisation expérimentale de leur stabilité ainsi que de leurs propriétés rhéologiques sous ces conditions extrêmes étaient nécessaires. Au cours de ce travail, les profils rhéologiques de ces fluides reflétant leurs capacités de nettoyage du puits, leur coulabilité ainsi que leurs capacités à transporter les débris jusqu'à la surface, ont été établis. D’autre part, la stabilité électrique des émulsions ainsi que leur morphologie (distribution de taille des gouttelettes) ont été étudiées et une comparaison avec celles stabilisées par des agents tensioactifs a été établie. Les fluides ont été exposés à un processus de vieillissement qui permet d’étudier l'effet de l'environnement du réservoir hostile sur la stabilité et la rhéologie des nouveaux fluides préparés. Ces fluides de haute qualité se sont révélés très fiables, offrant une grande stabilité et une capacité à résister à des conditions extrêmes de réservoir. Ils représentent une nouvelle génération de fluides de forage ouvrant la voie à une exploitation optimisée de réservoirs profonds et ultra profonds. / This enduring situation of volatile oil prices has been seen as a decline and a challenge at the same time for the oil and gas industry. It is during this slump that the oil and gas companies own the opportunity to focus on cost-effective production solutions, which very often means bringing new technologies and further improving processes.This work presents a novel frontier of surfactant-free drilling and completion fluids for deep and ultra-deep wells. This new generation of drilling fluids is based on the principle of Pickering emulsions (emulsions stabilized solely by solid nano particles). Hydrophobic and hydrophilic silica nano particles were used to stabilize Oil-Based Mud and Water-Based Mud. These fluids were designed to be used under hostile conditions of temperature and pressure. Therefore, a concrete characterization of their stability as well as their rheological properties under HTHP conditions was mandatory. Rheological profiles reflecting the flowability, hole cleaning capacity as well as cutting transport ability of the fluids were established. On the other hand, the electrical stability as well as the morphology (Droplet Size Distribution) of the emulsions were studied and compared with surfactant-stabilized drilling fluids. The fluids were submitted to an aging process allowing one to study the effect of hostile reservoir environment on the stability and rheology of the new fluids prepared.These high quality fluids were seen very reliable offering high stability as well as high capacity to withstand extreme reservoir conditions giving rise to a new generation of drilling fluids allowing breaking the frontiers of deep and ultra-deep reservoirs.

La thèse est intitulée « Modifications chimiques de polysaccharides pour l'obtention de nouveaux systèmes polymère-principe actif ». Le thème de la recherche porte sur trois axes principaux, dont l’objectif majeur est la synthèse et la caractérisation de nouveaux systèmes pour la libération contrôlée de principes actifs. Le premier chapitre traite de l’optimisation de la méthode pour préparer des émulsions stables simples inverses (eau/huile) et multiples (eau/huile/eau) à base de polysaccharides (amidon et 2-hydroxyethyle cellulose). On a étudié le processus de relargage de la caféine, l’influence de la présence d’amidon dans la phase aqueuse sur la stabilité et cinétique de libérations. Le second chapitre a pour objet l’obtention de nouveaux principes actifs à partir d’aminoacides et leur immobilisation sur polysaccharides par couplage chimique covalent. Les conjugues polymère-médicament obtenus ont été caractérisés par spectroscopie, physico-chimie. Leur activité antimicrobienne, leur toxicité in vivo, l’efficacité de l’immobilisation et la cinétique de relargage in vitro de médicaments couplés ont été étudiées. Le dernier chapitre traite de la synthèse des dérivés de chitosane avec l’anhydride maléique et l’acide acrylique, ainsi que leur utilisation dans la préparation d’hydrogels sous forme de films et de nanoparticules par copolymérisation avec le méthacrylate de 2-hydroxyethyle et l’acrylamide de N- isopropyl. Les dérivés ont été évalués par leur degré de fonctionnalisation. Les nanosystèmes ont été caractérisés par leur potentiel zêta, leur capacité de gonflement, d’adhésion et de relargage in vitro. Tous les résultats expérimentaux ont été soutenus par importantes études bibliographiques / The thesis is entitled “Chemical modifications of polysaccharides for the obtaining of new drug-polymer systems“. The topic of research includes four main working axes, diverted from the major objective to synthesize and characterize new drug delivery systems. The first chapter treats the optimization of the preparation method of stable simple W/O emulsions and multiple W/O/W emulsions, based on polysaccharides (starch and 2-hydroxyethyle cellulose). We also studied the process of caffeine release outside the multiple emulsions particles and the influence of starch in the internal aqueous phase stage upon the stability and the drug release kinetics. The second chapter studies the obtaining of new active principles from aminoacid and their immobilization on polysaccharides by covalent coupling. The new drug-polymer conjugates were characterized by spectral, physicochemical properties, antimicrobial activity, in vivo toxicity, immobilization efficiency and I vitro drug release kinetics. The last chapter treats the synthesis of the chitosan derivatives with maleic anhydride or acrylic acid, and their use in the preparation of hydrogels as film and nanoparticles by copolymerization with 2-hydroxymethacrilate or N-isopropyl acrylamide. The derivatives were evaluated by determining the degree of functionalization and by spectral methods. The nanosystems were characterized by measurements of zeta potential, swelling and adhesion capacity and membership and in vitro drug release kinetics. All experimental results were supported by important bibliographic studies

Cellulose nanocrystals (CNCs) are bio-based nanoparticles with the ability to stabilize oil and water emulsions thanks to their intermediate wettability and nanometric size. These and other types of particle-stabilized emulsions, commonly referred to as Pickering emulsions, are of great academic and industrial interest due to their superior stability against drop coalescence compared to classical surfactant-stabilized emulsions. In addition, the presence of a densely packed layer of particles at the oil-water interface is expected to impact the encapsulation ability of the emulsion droplets opening up for the possibility to use these systems to modulate the release of active substances in the context of oral or topical delivery formulations used in pharmaceutical and cosmetic applications. In these types of applications, the use of emulsions with nano-sized drops is advantageous due to their longtermcolloidal stability, improved dermal and mucosal transport of actives, improved bioavailability and greater aesthetic appeal and skin feel. This study had two main objectives. The first one was to explore to possibility to produce o/w emulsions with submicron-size drops by means of microfluidization using a combination of CNCs and hydroxypropyl methylcellulose (HPMC), a surface-active cellulose derivative that has been shown to have the ability to modify the wettability of CNCs (thereby enhancing their ability to adsorb at the oil/water interface). An important aspect of this first part of the study also involved gaining better understanding on the separate contributions of CNCs and HPMC to the properties of the resulting emulsions. The second objective of the work was to assess the performance of selected o/w CNC/HPMC compared to that of surfactant-stabilised emulsions in terms of their ability to deliver lutein, a hydrophobic prototype active of interest for topical delivery applications. / Cellulosa-nanokristaller (CNC) är biobaserade nanopartiklar med förmågan att stabilisera emulsioner av olja i vatten (o/w) tack vare deras medelhöga vätbarhet och storlek i nanometerskalan. Dessa och andra typer av partikelstabiliserade emulsioner, så kallade Pickering-emulsioner, är av stort akademiskt och industriellt intresse på grund av deras överlägsna stabilitet mot droppkoalescens jämfört med klassiska tensidstabiliserade emulsioner. Det tätt packade skiktet av partiklar vid gränsytan mellan olja och vatten påverkar också inkapslingsförmågan hos emulsionsdropparna vilket kan utnyttjas för att reglera frisättning av aktiva substanser i läkemedel eller kosmetiska produkter. I dessa typer av applikationer är användningen av emulsioner med droppar i nano-storlek fördelaktig på grund av deras långsiktiga kolloidala stabilitet, förbättrad hud- och slemhinnetransport, förbättrad biotillgänglighet och hudkänsla. Denna studie hade två huvudmål. Det första var att undersöka möjligheten att producera o/w emulsioner med droppar av submikron-storlek med hjälp av mikrofluidisering och genom att använda en kombination av CNC och hydroxypropylmetylcellulosa (HPMC), ett ytaktivt cellulosa-derivat som har visat sig ha förmågan att modifiera vätbarheten hos CNC och därigenom förbättra dess förmåga att adsorbera vid olja/vatten-gränsytan. En viktig aspekt av denna första del av studien var att få bättre förståelse för hur CNC och HPMC var för sig påverkar egenskaperna hos emulsionerna. Det andra målet med arbetet var att bedöma prestandan hos o/w CNC/HPMC-emulsioner för frisättning av lutein, ett hydrofob aktivt ämne, och jämföra med tensidstabiliserade emulsioner. / nanocellulosa, hydroxipropylmetylcellulosa, Pickering emulsioner, microfluidization, drogleverans

[pt] Emulsões podem ser formadas durante o processo de exploração dos reservatórios de petróleo. Essas emulsões podem trazer diversos prejuízos, como mudanças nas características dos óleos e problemas no bombeamento. Diante disso, aditivos químicos capazes de promover a desestabilização de emulsões de petróleo são importantes para otimizar o processo produtivo e mitigar os problemas causados. Há diversos estudos dedicados à avaliação de substâncias para atuar como desemulsificantes. Porém, a compreensão de como a estrutura química dos aditivos está correlacionada com as características físico-químicas dos óleos e emulsões ainda é escasso. Esse trabalho tem como objetivo entender como as características dos aditivos estão relacionadas com as particularidades de óleos parafínicos e asfaltênicos. Para isso, três óleos brasileiros foram usados para preparar e caracterizar emulsões água-óleo e avaliar sua estabilidade após o uso de diferentes aditivos. As emulsões preparadas com esses óleos apresentaram grandes diferenças nas propriedades reológicas. Entre elas, a viscosidade e gelificação em um dos óleos parafínicos, o que pode impactar diretamente na eficiência de desemulsificação devido à dificuldade de incorporação dos aditivos no bulk da emulsão. A estabilidade das emulsões foi estudada por testes de envelhecimento em diferentes condições de temperatura sem e com adição de diferentes aditivos: surfactantes, polímeros, ácidos orgânicos e inorgânicos e álcoois. De forma geral, aditivos anfifílicos com grupos aniônicos apresentaram melhor eficiência desemulsificante para todos os óleos. A aromaticidade, a acidez e o volume molecular dos aditivos também foram características importantes para a desemulsificação, porém, dependem da temperatura. Confirmou-se que a escolha de um desemulsificante para emulsões de petróleo depende da composição dos óleos e das características reológicas das emulsões formadas. Para emulsões de óleos parafínicos a temperatura foi determinante na eficiência de desemulsificação, enquanto para o óleo asfaltênico, a acidez influenciou mais. / [en] Emulsions can be formed during the exploration process of oil reservoirs. These emulsions, when unwanted, can bring several losses, such as loss of oil and changes in its characteristics and problems in pumping. Therefore, the development of chemical additives capable of promoting the destabilization of oil emulsions is important to optimize the production process and mitigate the problems caused. In the literature, there are several studies dedicated to the evaluation of substances to act as demulsifiers. However, the understanding of how the chemical structure of additives is correlated with the physicochemical characteristics of oils and emulsions is still scarce. This work aims to understand how the characteristics of the substances are related to the particularities of oils and their emulsions to better understand how demulsification occurs and also to propose additives with greater efficiency for the systems studied. To this end, three Brazilian oils were used to prepare water-oil emulsions and to evaluate the demulsifying capacity of different chemical additives. The stability of the emulsions was studied by aging tests under different temperature conditions without and with the addition of the different additives: surfactants, polymers, organic and inorganic acids and alcohols. The tests were carried out under different conditions to evaluate the effect of temperature mainly due to the high paraffin content in some oils. The characterization of the emulsions (without additives) showed large differences in rheological properties between the systems prepared with oils. These include viscosity, thixotropy and gelation in one of the paraffinic oils, which can directly impact the demulsification efficiency due to the difficulty of incorporating the additives into the emulsion bulk. From the aging tests, it was generally observed that amphiphilic substances with high interfacial activity and with anionic groups showed better demulsifying efficiency for all oils. The aromaticity, acidity and molecular volume of the additives were also important characteristics for demulsification, but they are temperature dependent. Finally, it was concluded that in general, the choice of a demulsifier for petroleum emulsions depends on the composition of the oils and the rheological characteristics of the emulsions formed. For paraffinic oil emulsions, the temperature was decisive for the demulsification efficiency, whereas, for the others, the acidity proved to be more decisive.

[pt] A motivação deste trabalho consiste no uso do four-roll mill para aumentar a separação de fases de emulsões água em óleo (A/O) presente no processamento primário da indústria de petróleo. A partir da conservação de massa e momento, a fase contínua foi modelada como escoamento incompressível, bi-dimensional e isotérmico. Simulações numéricas utilizando o método de elementos finitos foram implementadas para revelar a influência das diversas configurações de escoamento no comportamento mecânico do material. A partir dos resultados obtidos, a habitual forma de classificar o escoamento no four-roll mill de acordo com a literatura se demonstrou ineficiente. Este trabalho sugere classificações locais de escoamento a cada posição dependendo se a mesma está ocupada pela fase contínua ou dispersa da emulsão. O efeito da fase dispersa é descrito via pós-processamento. Microelementos no formato de vetores foram inseridos no domínio e investigou-se suas deformações e trajetórias. Consequentemente, analisou-se a deformação de gotas e a sua respectiva influência na instabilidade da emulsão. / [en] The motivation of this work consists in the use of four-roll mill in order to increase the phase separation of water-in-oil emulsions (W/O) present in the primary process of oil industry. With mass and momentum conservation, the continuous phase is modeled by an incompressible, bi-dimensional and isothermal flow. Numerical simulations employing the finite element method were implemented to reveal the influence of the several flow configurations in the material mechanical behavior. From the obtained results, the standard way of classifying the flow in the four-roll mill according to the literature was proved inefficient. This work suggests local flow classifications for each position depending if it is occupied by the continuous or dispersed phase. The effect of the dispersed phase was described by a post-processing scheme. Microelements in shape of vectors were inserted in the domain and their deformations and pathlines were investigated. Thus, the deformation of droplets and their respective influences in the emulsion instability were analyzed.

A pre-eminent emulsion-based micellar drug delivery system, "microemulsion", comprising drug in oil or water phase, stabilized by surfactants and co-surfactants, has been evidenced to have a phenomenal role in a number of applications. Oils play an important role in the formation of ME and increase the drug absorption at the site of action. Oils employed in microemulsion formulation solubilize lipophilic drug. As the concept of "natural" therapies is recently gaining importance amongst researchers all over the world, scientists are employing essential oil as an organic component in this system. The active components of essential oils include flavonoids, phenylpropanoids, monoterpenes and polyunsaturated mega-6-fatty acids. These oils are enriched with characteristic intrinsic properties such as anti-oxidant, anti-bacterial, anti-viral, etc., bestowing enhanced supremacy to the whole microemulsion system. This mini-review is the first to document various types of essential oils employed in microemulsion systems and highlight their therapeutic potential and applications as drug delivery vehicles. Key inferences from this study suggest: 1) Clove oil is the most explored oil for incorporation into a microemulsion based system, followed by peppermint and Tea Tree Oil (TTO). 2) Penetration enhancing effects of these oils are due to the presence of terpenic constituents. 3) Essential oil based microemulsions protect volatility of ethereal oils and protect them from degradation in the presence of light, air, temperature. 4) These systems may also be explored for their applications in different industries like aromatherapy, food, drink, fragrance, flavour, cosmeceutical, soap, petroleum and pharmaceutical industry.

<p>Ships, including those in the US Navy, collect oily wastewater in their bilge due to onboard cleaning and mechanical operations. Oil-in-water emulsions (O/W) are present in bilgewater, and their filtration is difficult due to surfactants provided by cleaning products. Despite cleaning efforts, over 457,000 tons of oil are discharged into the ocean every year. An often overlooked aspect of bilgewater emulsions is their evolution, as the ship's movement at sea provides extra energy that can further emulsify the collected oil. This work aims to understand the effects of motion on model bilgewater emulsions by tracking their evolution in dynamic (rocking motion) and static conditions. The model bilgewater emulsion comprises mineral oil, deionized water with 0.42 M NaCl to mimic the salinity of seawater and sodium lauryl ether sulfate and Triton X-100, as commonly found anionic and nonionic surfactants, respectively. A rocker is used to simulate a ship motion; 15 mL of emulsion were placed in 50 mL centrifuge tubes to mimic partially filled bilgewater tanks. Emulsions were characterized via laser diffraction and optical microscopy. Model bilgewater emulsions with either SLES or Triton X-100 at concentrations above 100 ppm and 500 ppm, respectively, show long-term stability in static (no-rocking) conditions up to 20 days of observation. These concentrations represent the minimum surfactant concentration needed to obtain stable emulsions under static conditions. Under dynamic conditions, the minimum surfactant concentration to obtain stable emulsions increases to 500 ppm and 1000 ppm for SLES and Triton X-100, respectively. These results mean that the ship motion can induce drop coalescence in unstable emulsions with lower surfactant concentrations. However, the drop size distributions for stable emulsions under dynamic conditions show further emulsification as the average drop size decreases. The ship motion can help further reduce the size of the emulsion drops to diameters < 2.8 µm, which are significantly harder to filter out using current methods. A bilgewater tank partially filled will likely show a higher amount of sloshing than a filled one. To understand the effects of bilgewater storage volume on emulsification, a series of dynamic experiments were carried out with samples that contained up to 100% of the centrifuge tube volume occupied by the model bilge water emulsion. Even when 100% of the centrifuge volume is occupied and sloshing is eliminated, the oil moves due to density differences, and the shear stress between fluids can induce the generation of drops < 2.8 µm. In summary, this work shows that the ship motion provides enough energy for emulsification once a minimum surfactant concentration is reached regardless of the volume of emulsion stored in the tanks. The data suggests that the best way to mitigate stable bilgewater emulsion formation is by reducing surfactant concentration.</p>

Thesis (MScEng)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Chip and spray surfacing seals has been widely used in South Africa as the preferred surface treatment for rural roads. The design of these seals has also experienced renewed interest and continuous development in several other countries over the past two decades. In South Africa seals are continually used as increasing attention is given to the periodic maintenance of existing surfaced roads. There is also a significant increase in the use of surfacing seals in North America as the need to develop more energy and resource efficient surfacing options becomes a priority. Despite this growing use of surface seals, the seal design and especially the selection of binder type and grade does not always follow scientific processes. Seals are often designed based on client preference, previous experience, material availability and industry trends. With an ageing road network and limited funding to ensure timeous maintenance, the focus in South Africa is moving towards more stringent and scientific design processes. The USA and Europe, forced by increasing traffic volumes and heightened performance demands, are moving towards performance- based specification to account for deficiencies in their current surface seal design methods. One of the major failure mechanisms of surface seals is ravelling which takes place when the binder and the aggregate bond becomes weak and are broken by the forces generated by traffic. This leads to loose aggregate on the road which in turns leads to bare surface patches and broken windscreens. To prevent and address this as part of the development of performance-based specifications, the need for a simple and inexpensive technique for evaluating bitumen and bitumen emulsion bond strength development over time, as well as binder-aggregate compatibility, was identified. Although various tests exist for investigating adhesion between bituminous emulsions and aggregate chips most of the tests does not deliver the level of information required by the performance-based specifications. The Bitumen Bond Strength (BBS) test method was therefore developed with the aim to address some of the limitations encountered in evaluating bond strength between binders and aggregates. The BBS test (AASHTO TP-91, 2011) was developed by the University of Wisconsin – Madison (UWM) in partnership with the University of Ancona – Italy (UAI) and the University of Stellenbosch – South Africa (US) specifically for evaluating bond strength between aggregates and hot applied binders and emulsions, respectively. US became involved in BBS test efforts in 2008 to assist in the development and practical evaluation of the BBS test method. UAI contributed significantly to the development of the test apparatus through their work in conjunction with UWM. Due to time and resources available, the involvement of the US was limited to various discussion sessions, a study tour, the evaluation of the BBS test, and conducting a series of control tests. By using the Bitumen Bond Strength test it was possible to evaluate the practicality and repeatability of the developed procedure and the results measured was successfully used to evaluate the bond strength development of modified and unmodified bitumen emulsions on tillite and granite aggregates. It was also possible to correlate the results achieved at the University of Stellenbosch with results from the University of Wisconsin-Madison due to the fact that testing took place at both institutions. The development of the test and the inter-laboratory test results in essence reinforced the hypothesis that the BBS test protocol can be used to effectively evaluate bond strength of different emulsion types and aggregate types. Except for the loading rate which is a known critical influence, the emulsion type and curing intervals are both identified as the most significant other factors contributing to bond strength development. Aggregate type is also identified as a significant factor that will influence the bond strength development. Interactions between emulsion type and curing interval are identified as the most significant interaction. A lot of further validation test on the BBS test method is still required for the test to be integrated into a performance-based specification system for surface seals. / AFRIKAANSE OPSOMMING: “Chip and Spray” oppervlak seëls is die verkose seël tipe vir gebruik op Suid Afrikaanse plattelandse paaie. Die ontwerp van hierdie tipe seëls is ook tans besig om hernude aandag te trek in heelwat lande. In Suid Afrika word die tipe seël al meer gebruik soos die behoefte na herseël projeke op die verouderde pad netwerk groei . Daar is ook heelwat groei in die gebruik van “Chip en Spray” seëls in Noord Amerika aangesien daar n behoefte is om n meer energie en materiaal effektiewe seëls te gebruik. Ten spyte van die groeiende gebruik van hierdie seëls het daar min wetenskaplike ontwikkeling plaasgevind in the ontwerp daarvan. Seëls word meestal ontwerp gebaseer op klient voorkeur , ondervinding, materiaal beskikbaarheid en ook industrie norms. ‘n Verouderde pad netwerk dwing die Suid Afrikaanse industrie om meer deeglike en wetenskaplike ontwerp prosedures te volg. Die VSA en Europa word deur vinnig groeiende verkeersvolumes en verhoogte kwaliteits behoeftes gedwing om prestasie gebaseerde spesifikasies te ontwikkel. Een van die hoof defekte op seëls is klipverlies wat plaasvind as die verbinding tussen die bitumen en aggregaat verswak en gebreek word deur die kragte wat deur verkeer oorgedra word. Dit lei tot los klip op die pad wat weer tot skade aan voertuie lei. Om dit te voorkom en aan te spreek het die behoefte laat ontwikkel vir n maklike en goedkoop tegniek om te meet hoe sterk die verbinding is wat ontwikkel tussen verskillende bitumen, bitumen emulsies en aggregaat monsters. Alhoewel daar alreeds toetse bestaan wat kan toets hoe sterk die verbinding is , gee die meeste van die toetse nie die informasie wat benodig word deur die voorgestelde prestasie gedrewe spesfikasies nie. Die “Bitumen Bond Strength” (BBS) toets metode is daarom ontwikkel om die tekortkoming in die toets van die bitumen en aggregaat verdindinge aan te spreek. Die BBS toets (AASHTO TP-91, 2011) is ontwikkel by die Universiteit van Wisconsin – Madison (UWM) in vennootskap met die Universiteit van Ancona – Italy (UAI) en die Universiteit van Stellenbosch (US) , spesifiek om die die sterkte van die verbinding wat vorm tussen aggregaat en bitumen te meet. Die US het in 2008 betrokke geraak by die BBS toets studie om hulp te verleen met die ontwikkeling en praktiese evalueering van die BBS toets metode. As gevolg van tyd en personeel tekorte is die betrokkendheid by die US beperk tot verskeie besprekings sessies, n studie toer, die evalueering van die BBS toets sowel as die voltooing van n uitgebreide stel toetse. Deur die voltooing van eksperimente met die BBS toets was dit moontlik om die uitvoerbaarheid en herhaalbaarheid van die ontwikkelde prosedure te toets. Die resultate van die toetse is suksesvol gebruik om die ontwikkeling van die verbinding sterkte tussen gemodifiseerde en ongemodifiseerde bitumen emulsies en tilliet en graniet te definïeer en te evalueer. Dit was ook moontlik om die resultate van die Universiteit Stellenbosch en die Universiteit of Wisconsin-Madison suksesvol met mekaar te vergelyk aangesien toetse by beide die instansies voltooi is. Die ontwikkeling van die toets en die inter laboratorium toets resultate het dit moontlik gemaak om die hipotese te bevestig dat die BBS toets prosedure effektief gebruik kan word om die bitumen en aggregaat verdindinge te toets en te evalueer. Behalwe vir die tempo van die lading waarteen die aftrek sterkte getoets word , is die emulsie tipe en die nabehandeling tydperk beide geidentifiseer as die mees beduidende invloede wat bydrae tot die ontwikkeling van die verbinding sterkte. Die aggregaat tipe is ook geidentifiseer as n belangrike faktor wat die verbinding sterkte ontwikkeling sal beïnvloed. Die interaksie tussen die emulsie tipe en nabehandeling tydperk was geïdentifiseer as die mees beduidende interaksie. Daar sal wel nog heelwat eksperimente voltooi moet word met die BBS toets prosedure voordat dit volkome geïntegreer kan word as deel van n prestasie gebaseerde spesifikasie stelsel vir die ontwerp van seëls.

L’exploitation de pétrole s’accompagne de la modification des conditions thermodynamiques internes du puits et favorise, entre autres, la formation de dépôts minéraux pouvant obstruer les pores micrométriques de la formation rocheuse, rendant difficile l’extraction d’huile. L’efficacité du traitement anti-dépôts dépend de la concentration minimale d’inhibiteur et de la vitesse de relargage du produit. Dans ce contexte, nous avons étudié deux techniques d’encapsulation permettant d’obtenir un système préventif à libération prolongée contenant un polyélectrolyte anionique comme additif modèle. La première consiste en la formation de nanoparticules de polyélectrolytes complexés. La libération de l’actif encapsulé y a été stimulée par la modulation de la salinité du milieu. À pH basique, la libération de l’actif a lieu via le mécanisme de gonflement /dissociation des particules, à pH acide aucune libération ne parait avoir lieu car les objets précipitent. Le second système est une émulsion inverse (E/H) diluée contenant un actif modèle en phase dispersée. Ces systèmes sont stables et un faible pourcentage d’actif est libéré sous contrainte mécanique. / Many thermodynamic changes occur in reservoir rock when oil is produced. These changes enable scale formation on micrometric rock pores that can block them and impede/block oil extraction. Antiscale treatment efficiency depends on minimal inhibitor concentration and product release rate in fluids downhole. In this context, we have studied two encapsulation techniques allowing us to have a sustainable release system composed of an anionic polyelectrolyte as a model additive. The first formulation consists in formation of polyelectrolyte complexes nanoparticles. In this system, active ingredient release was stimulated through medium ionic strength modulation. Under basic conditions, release takes place in particles swelling/dissociation process; whereas, under acidic condition, particles precipitate and no release can be expected. The second system we have worked on is a diluted reverse (W/O) emulsion, in which dispersed aqueous droplets contain a model additive. These systems are stable and small additive percentage is released under mechanic strain.