Cette étude porte sur le mode d’action de tensio-actifs macromoléculaires à base d’alcools polyvinyliques (PVA) sur la stabilisation d’émulsions chlorure de vinyle (VCM)/eau utilisées pour la polymérisation en suspension du VCM. Cinq PVA dits primaires (PVA I) de différents degrés d'hydrolyse ( de 73 à 88 %mol) et différents degrés de polymérisation ( de 700 à 2500), ainsi qu’un PVA dit secondaire (PVA II) de 45%mol ont été étudiés sur un large domaine de concentration [0-1000 ppm/eau]. Les tensions interfaciales, ainsi que les tailles et distributions de taille des émulsions ClBu/eau, choisies comme modèle des émulsions VCM/eau, ont été déterminées en fonction du temps. Une technique originale de granulométrie en ligne : la spectroscopie par atténuation d’ultrasons a été mise en place. Les stabilisants les plus efficaces sont les PVA I de faible et . Pour chaque PVA I, une corrélation directe entre diamètre moyen des gouttelettes et tension interfaciale a pu être établie et l’importance de la viscoélasticité de l’interface a été démontrée. Le PVA II, du fait de son plus faible est insoluble dans l’eau. Des particules colloïdales bien définies de PVA II seul ou de combinaisons PVA I/ PVA II ont été préparées par coacervation. Pour une même concentration totale en PVA, ces nanoparticules de diamètre 150-200 nm abaissent davantage la tension interfaciale et les diamètres moyens des gouttelettes d’émulsion, que les PVA I seuls. Une stabilisation particulaire de type Pickering peut donc être envisagée en complément de la stabilisation stérique apportée par les PVA I. / This study focuses on the action mechanisms of poly vinyl alcohol-based macromolecular surfactants on the stabilization of vinyl chloride (VCM)/water emulsions used for the suspension polymerization of VCM. Five “primary” PVA (PVA I) with high hydrolysis degrees ( between 73 à 88 %mol) and different polymerization degrees ( between 700 à 2500), as well as one “secondary” PVA (PVA II) with 45%mol, have been studied on a large concentration range [0-1000 ppm/water]. The interfacial tensions and the size distributions of ClBu/water emulsions have been determined as a function of time. An original technique of on-line granulometry: the ultrasound attenuation spectroscopy has been used. The PVA I with low and are the most efficient stabilizers. For each PVA I, a direct correlation between mean diameter of droplets and interfacial tension has been established. Moreover, the importance of the interface viscoelasticity has been demonstrated. Because of their low , PVA II are insoluble in water. Well-defined colloidal particles of PVA II and combinations PVA I/ PVA II have been prepared by coacervation. For a given total PVA concentration, these nanoparticles of diameter 150-200 nm lower more the interfacial tension, and the mean droplet diameters, than PVA I alone. A Pickering stabilization by nanoparticles can be considered, in addition to the steric stabilization provided by PVA I.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第22081号 / 農博第2373号 / 新制||農||1073(附属図書館) / 学位論文||R1||N5235(農学部図書室) / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 矢野 浩之, 教授 和田 昌久, 教授 辻井 敬亘 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

This thesis contains both Parts A and B. / <p> Xenon induced flux oscillations are possible in large thermal reactors operating at high powers because of the inter-play between the xenon concentration, reactivity, and thermal flux, and the fact that xenon is produced mainly by radioactive decay of I-135, which has a half-life of 6.7 hours. Due to these nuclear characteristics along with size and operating conditions of the Pickering and Bruce cores, these oscillations in flux are inherently unstable with respect to xenon. That is, a local perturbation in reactivity will result in a divergent and cyclic time and space variation in the thermal flux distribution in the core.</p> <p> One group diffusion theory and a simple perturbation analysis yield for a bare thermal reactor, a threshold in the average flux level ∅ which satisfies (1) M^2λij^2 / αxe - αT/αxe ∅ = 1/1+λxe/σxe∅ - μxe / 1+(λxe + λ1)/σxe∅ for oscillations in ijth mode of the flux distribution (see Figure 1) M^2 is the migration area in cm^2, αxe is the reactivity load of Xe-135 at high flux levels; αT is the fuel temperature coefficient expressed in terms of reactivity change per unit flux. The function f(∅) depends only upon the decay constants λxe of Xe-135 and λ1 of I-135; μxe is the fraction of Xe-135 produced directly from the fission of the fuel rather than through iodine decay (which fraction is denoted by μ1). The dimensionless parameter λij^2 depends only upon the shape of the flux distribution and is equal to the difference between the bulking of the ijth mode and the fundamental model.</p> <p> The Bruce and Pickering reactors are used as models in this study to determine the threshold power level at which xenon instability is possible and in which mode this instability occurs.</p> <p> Bruce is found to be unstable in the fundamental and first azimuthal mode for fresh and equilibrium fuel conditions, and stable for the radial, axial and higher azimuthal modes.</p> <p> Pickering, on the other hand, is unstable for the equilibrium fuel condition in the fundamental and first azimuthal modes only and is stable in every mode except the fundamental in the fresh fuel condition.</p> (Part A of Thesis)-------------------------------------------------------------------------------------------------------(Part B of Thesis) </p> Trimming of thin-film resistor components by an electrical arc is investigated in this report as an inexpensive and simple alternative to the laser trim and mechanical scribe methods. A multitude of tests were effected on Garrett Manufacturing Limited production circuits containing nichrome thin film resistors. These tests included Temperature Coefficient of Resistivity, resistance stability, substrate damage, noise performance, dynamic trim with active devices operating, width of cut as compared to mechanical scribe and laser trim techniques, and optimum parameters for trimming. In all cases the trimmed circuits were within the design specifications of the resistor properties under test. It is the conclusion of the author that the obvious attributes of the arc-trim method as well as its outstanding performance in the above tests, warrants its serious consideration as a viable alternative to the laser trim and mechanical scribe methods of altering resistance levels.</p> / Thesis / Master of Engineering (MEngr)

Nanocellulose is a sustainable material and has shown interesting properties in various applications. One such application is Pickering emulsion, where the nanocellulose stabilizes the oil and water interface. Thus, this project aimed to evaluate a new type of nanocellulose, cellulose oxalate (COX), derived from different sources, dissolving pulp and bark, as a potential emulsifier. The properties of the nanocellulose, such as the chemical composition, morphology, aspect ratio, viscosity, and surface tension, are analyzed to determine how it affects the Pickering emulsion. Pectin has reported having emulsifying properties. Therefore, pectin derived from the bark was also studied as a potential emulsifier.  The emulsion capacity and emulsion stability of the Pickering emulsion were estimated. Additionally, the emulsions were observed and visualized in an optical microscope, and it showed that all Pickering emulsions were successful. The COX and pectin particles were successfully adsorbed at the interface to form individual droplets which were stable enough not to coalescence. With the images from AFM, the aspect ratio and morphology of the particles were measured. COX pulp had an average width of 5.5 nm and an average length of 372 nm. COX bark had an average width of 3.9 nm and an average length of 257 nm. Notably, COX pulp does have a slightly higher aspect ratio than COX bark. DLS was another way the particle size was measured. However, it was not a suitable technique because both COX did indicate a relatively polydisperse system and are therefore not suitable to be measured by DLS. Furthermore, the viscosity of the COX pulp and COX bark suspensions were measured with an Ubbelohde capillary viscometer which was not an ideal method because the COX suspensions were too thick and gel-like for the instrument and got clogged constantly. As expected, the surface tension decreased steadily, more so for COX pulp than COX bark with increasing concentration. Then again, this means that COX has a hydrophobic property that does reduce the surface tension of water. Lastly, the carbohydrate analysis did indicate that both COX do have a high amount of glucose. Moreover, both COX did also show a significant amount of other components.  Overall, this study does conclude that COX pulp, COX bark, and pectin did stabilize the Pickering emulsion to some degree, despite being inconsistent and can therefore be considered effective emulsifiers. / Nanocellulosa är ett hållbart material som har visat intressanta egenskaper i olika applikationer. En specifik applikation är Pickering emulsion, där nanocellulosan stabiliserar gränsytan mellan olje-och vatten fasen. Därav var syftet med detta projekt att utvärdera en ny typ av nanocellulosa, cellulosaoxalat (COX) producerad från olika källor såsom förhandlad pappersmassa och bark som ett potentiellt emulgeringsmedel. De olika egenskaperna hos nanocellulosan dvs. den kemiska sammansättningen, morfologin, partikelstorlek, viskositet och ytspänning undersöktes för att bestämma hur de påverkar Pickering emulsionen. Pektin har också rapporterats att ha emulgerande egenskaper. Därför studerades även pektin producerad från bark som ett potentiellt emulgeringsmedel.  Emulsionskapaciteten och emulsionsstabiliteten hos Pickering emulsionen uppskattades. Dessutom observerades och visualiserades emulsionerna i ett optiskt mikroskop som visade att alla Pickering emulsioner var successiva. Det innebär att COX- och pektinpartiklarna adsorberades successivt vid gränsytan för att bilda individuella droppar som var stabila nog att inte koalescensera. Med hjälp av bilderna från AFM mättes storleken på partiklarna och dess morfologi bestämdes. COX-massa hade en genomsnittlig bredd på 5,5 nm en medellängd på 372 nm. COX-bark hade en genomsnittlig bredd på 3,9 nm och en medellängd på 257 nm. Från resultatet, kan det noteras att COX-massa har något större partikelstorlek är COX-bark. DLS var ett annat sätt att mäta partikelstorleken. Dock, var det inte en lämplig teknik eftersom både COX-massa och COX-bark visade ett relativt polydisperst system och är därav inte lämplig att mättas i DLS. Vidare så mättes viskositeten för COX-massa och COX-bark med en Ubbelohde kapillärviskometer, vilket inte heller var en idealisk metod att mäta med eftersom COX lösningen var för tjock och gel-liknande och täppte till instrumentet. Däremot, som förväntad minskades ytspänningen stadigt med ökande koncentration. Detta var mer tydligt hos COX- massa än COX-bark. Oavsett så betyder det att COX har en hydrofob egenskap som minskar ytspänningen hos vatten. Sist men inte minst så indikerade kemiska sammansättningsanalysen att båda COX har en stor mängd glukos. De har även en betydande mängd av andra komponenter.  Sammantaget drar denna studie slutsatsen att COX-massa, COX-bark och pektin stabiliserade Pickering emulsionen till en viss del relativt väl, trots att det var inkonsekvent så anses de vara effektiva emulsionsmedel.

Abstract During the 1960s both the federal and provincial governments continued to take on new and larger responsibilities. During this same time period citizens began to mobilize and challenge the state on a number of social issues including race, gender, labour, urban sprawl and the environment. Citizens believed that not only did they have the right to challenge the authority of government in planning public policy, but they also had a right to participate in the decision-making process as much as any bureaucrat, expert, or elected official. In planning airports in Pickering, Ste. Scholastique and Sea Island, the federal government was opposed by citizen groups in each of these three cases. Citizens believed their voices were not being heard and that government officials did not respect them. As a result, they disrupted the meticulously laid out plans of elected officials and policy planners by drawing on evidence and expert advice. The conflict over federal airport development is an example of the evolution of the consultation process with citizens, as citizens challenged the way public policy was planned. Governments now had to justify policies like expropriation for the public good since citizen groups would form over any intrusion into their private lives. The debates over airport planning highlights the role of citizens, bureaucrats, provincial and federal politicians as they all tried to navigate the complex shifting landscape of the Canadian state. By 1976 the Pickering Airport had been canceled, Mirabel was opened, and the Sea Island runway expansion would be delayed for 15 years. Although the citizen groups never had complete victories, citizen participation became more paramount to state planning after these events. Public policy planning in Canada had become far more inclusive than ever before. Whether the politicians, bureaucrats or citizens were aware of the consequences remain to be seen. / Thesis / Doctor of Philosophy (PhD) / Abstract During the 1960s both the federal and provincial governments continued to take on new and larger responsibilities. During this same time period citizens began to mobilize and challenge the state on a number of social issues including race, gender, labour, urban sprawl and the environment. Citizens believed that not only did they have the right to challenge the authority of government in planning public policy, but they also had a right to participate in the decision-making process as much as any bureaucrat, expert, or elected official. In planning airports in Pickering, Ste. Scholastique and Sea Island, the federal government was opposed by citizen groups in each of these three cases. Citizens believed their voices were not being heard and that government officials did not respect them. As a result, they disrupted the meticulously laid out plans of elected officials and policy planners by drawing on evidence and expert advice. The conflict over federal airport development is an example of the evolution of the consultation process with citizens, as citizens challenged the way public policy was planned. Governments now had to justify policies like expropriation for the public good since citizen groups would form over any intrusion into their private lives. The debates over airport planning highlights the role of citizens, bureaucrats, provincial and federal politicians as they all tried to navigate the complex shifting landscape of the Canadian state. By 1976 the Pickering Airport had been canceled, Mirabel was opened, and the Sea Island runway expansion would be delayed for 15 years. Although the citizen groups never had complete victories, citizen participation became more paramount to state planning after these events. Public policy planning in Canada had become far more inclusive than ever before. Whether the politicians, bureaucrats or citizens were aware of the consequences remain to be seen.

Des émulsions particulièrement stables peuvent être formulées à l’aide de particules colloïdales (émulsions dites de Pickering). L’objectif de cette étude est d’accéder à la compréhension des mécanismes de stabilisation des interfaces, ainsi que du lien entre propriétés interfaciales et propriétés macroscopiques des émulsions. Dans ce cadre, la stratégie adoptée repose sur l’utilisation de particules colloïdales dont les caractéristiques peuvent être variées continûment à la fois en amont par la chimie de synthèse (variation de la mouillabilité, de la déformabilité) et in situ par un stimulus (pH, sel, température...). De plus,les émulsions stabilisées par de telles particules deviennent, elles aussi, sensibles aux stimuli et la déstabilisation des émulsions peut être déclenchée à la demande. Les mécanismes d’adsorption, les interactions entre particules aux interfaces et les propriétés résultantes des émulsions sont étudiés. L’établissement de concepts généraux régissant la stabilisation/déstabilisation des émulsions permet d’en contrôler, via la formulation ou le procédé (température, cisaillement), les propriétés d’usage. Enfin les émulsions stabilisées par des particules colloïdales peuvent être utilisées en tant que précurseurs dans la formulation de matériaux plus complexes : ceci est illustré par l’élaboration de capsules à libération thermostimulée / Highly stable emulsions can be formulated using colloidal particles as stabilizers (so-calledPickering emulsions). This study aims at understanding the interfacial stabilizationmechanisms as well as the links between the interfacial properties and the macroscopicproperties of emulsions. In this context, our strategy consists in using colloidal particles forwhich characteristics can be continuously tuned either during the synthesis (variation of theparticles’ wettability or deformability) or in situ by using a stimulus (pH, salt, temperature…).Emulsions stabilized by such particles are stimuli responsive and their destabilization can betriggered on demand. We study and report the mechanisms of particle adsorption, theinteractions between particles anchored at interfaces and the resulting properties of emulsions.Such study allows us to draw general concepts governing the emulsionsstabilization/destabilization and to control their end-use properties via formulation oremulsification process (temperature, shear). Colloidal particle stabilized-emulsions can beused as templates to synthesize more complex materials as illustrated by the elaboration ofcapsules allowing a thermally controlled delivery of their content.

Ce travail de thèse est une contribution à l’étude des émulsions de Pickering qui ont vu unregain d’intérêt ces dernières années. Bien que l’effet Pickering ait été décrit depuis plus d’un siècle,des études plus systématiques pour comprendre l’activité des particules solides aux interfacesliquide/liquide n’est que partiellement entrepris, surtout en cours de déformation. Plusieurs questionsrestent d’actualité et, en premier, la localisation même des particules à l’interface et le mécanismed’adsorption associé.L’approche proposée dans ce travail de thèse s’inscrit dans cette optique avec en particulier laconsidération d’un événement élémentaire d’une émulsion : une goutte isolée dans une matrice etexaminée suite à un saut de déformation en cisaillement dans un dispositif de cisaillement contrarotatifdéveloppé à PCI. De manière générique, le but est de comprendre la relation entre le comportement dela goutte et la rhéologie complexe (en volume ou en surface) apportée par la dynamique de particulessolides aux interfaces liquide/liquide mobiles. Plusieurs paramètres ont été étudiés en commençant parl’affinité chimique des particules solides avec les phases liquides, la rhéologie des phases liquides, laconcentration et la taille des particules solides ; et pour finir, une attention particulière a été portée àl'effet de la déformation macroscopique et l’âge de la goutte.Plus particulièrement, la mise en évidence de la synergie entre la déformation macroscopiqueet l’âge de la goutte, sur la dynamique d’adsorption des particules à l’interface liquide/liquide et lastructuration de l’interface composée, a permis de proposer une méthodologie pour la modulation de« l’effet mémoire induite par la déformation » lors de la relaxation de la goutte en modifiant lasurface des particules par adsorption de tensioactifs choisis. Ainsi, il a été possible de figer les gouttesliquides dans des formes anisotropes contrôlées. Ce phénomène a été corrélé à une transition liquidesolidede l’interface composée mise en évidence par des mesures des modules rhéologiquesinterfaciaux. Ces derniers ont été, par ailleurs, reliés quantitativement à l’anisotropie des gouttesfigées. / This thesis is a contribution to the study of Pickering emulsions that have seen a renewedinterest in recent years. Although the effect Pickering has been described for over a century, moresystematic studies to understand the activity of solid particles at liquid/liquid interfaces is onlypartially undertaken, especially during flow. Several issues are still relevant and, in particular, thelocation of particles at the interface and the involved adsorption mechanism.The approach proposed in this thesis is to consider an elementary event of an emulsion: asingle droplet in a matrix undergoing a strain jump in a shear flow. This experiment was performed ina counter-rotating shear device developed at PCI. Generically, the aim is to understand the relationshipbetween the behavior of the droplet and the bulk and interfacial rheology induced by the dynamics ofsolid particles at a liquid/liquid interfaces. Several parameters were studied starting with the chemicalaffinity of solid particles with the liquid phases, the rheology of the liquid phases, the concentrationand the size of solid particles, and finally, special attention was paid to the effect of macroscopicdeformation and the age of the interface.More specifically, the demonstration of synergy between the macroscopic strain and the age ofthe interface, the dynamic adsorption of particles at the liquid/liquid interface and the structure of theinterface, allowed to propose a methodology for the modulation of the "memory effect induced by thedeformation" during the relaxation of the droplet by changing the particle surface using the adsorptionof a selected surfactants. Thus, it was possible to freeze the liquid drops in a controlled anisotropicshapes. This phenomenon was correlated to a liquid-solid transition of the interface demonstrated byrheological measurements of the interfacial moduli. These were, moreover, quantitatively related tothe anisotropy of frozen droplets.

L’objectif de cette étude est de valoriser des coproduits végétaux tout en proposant une alternative biosourcée, économique et performante aux tensioactifs classiques. Des émulsions de type huile-dans-eau sont fabriquées à partir de poudres végétales finement broyées comme seul matériel tensioactif. Les systèmes dispersés qui en résultent, stabilisés par des particules solides, sont des émulsions dites de Pickering. La première partie de ce manuscrit décrit l’influence du procédé d’émulsification (rotorstator en régime turbulent, ultrasons et homogénéisation haute pression) et des paramètres de formulation sur les propriétés d’émulsions stabilisées par de la poudre de cacao. Le rôle des différentes fractions de la poudre est déterminé et le phénomène de coalescence limitée propre aux émulsions de Pickering est étudié. Nous mettons en évidence une évolution structurale des particules (« dépliement ») sous l’effet du cisaillement appliqué lors de l’émulsification, permettant d’augmenter leur performance en tant qu’agents stabilisants. L’influence de la nature végétale est explorée en élargissant l’étude à des poudres de compositions différentes issues de tourteaux de colza et de lupin. La stabilité de ces émulsions face à l’élimination de la phase continue est ensuite évaluée au regard de la technique de séchage, par lyophilisation et atomisation. Des émulsions sèches riches en huile et redispersables dans l’eau sont ainsi obtenues. Enfin, le pouvoir antioxydant des poudres végétales avant et après séchage des émulsions est caractérisé. / This study aimed at valorizing vegetal byproducts while offering a bio-sourced, cheap and efficient alternative to conventional surfactants. Oil-in-water emulsions were obtained from finely ground plant powders as the only surfactant material. The resulting dispersed systems, stabilized by solid particles, are so-called Pickering emulsions. The first part of this manuscript describes the influence of the emulsification process (rotor-stator in turbulent regime, sonication and high-pressure homogenization) and of the formulation parameters on the properties of emulsions stabilized by cocoa powder. The role of the different fractions of the powder was determined and a phenomenon characteristic of Pickering emulsions, namely limited coalescence, was identified. We evidenced a structural evolution of the particles ("unwrapping") under the effect of the shear applied during the emulsification process, allowing to increase their performance as stabilizing agents. The influence of the vegetal origin was explored by extending the study to powders deriving from rapeseed and lupin oilcakes. The stability of these emulsions with respect to the elimination of the continuous phase was evaluated using 2 drying techniques, freeze-drying and spray-drying. Dry emulsions rich in oil and redispersable in water were obtained. Finally, the antioxidant properties of vegetable powders before and after the drying process were characterized.

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-02-26T11:28:38Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Taiana Huslia Gomes Daniel.pdf: 2854921 bytes, checksum: 558ae7bad090562fb907f55b5c80bd02 (MD5) / Made available in DSpace on 2019-02-26T11:28:38Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Taiana Huslia Gomes Daniel.pdf: 2854921 bytes, checksum: 558ae7bad090562fb907f55b5c80bd02 (MD5) Previous issue date: 2018-11-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Os nanocristais de amido são partículas de tamanho nanométrico que vêm recebendo atenção por parte dos pesquisadores pois são abundantes, biodegradáveis, não tóxicos e apresentam relativo baixo custo. Essas nanopartículas cristalinas podem ser utilizadas como estabilizantes de emulsões Pickering, sistemas onde o tamanho das partículas é fator primordial para a estabilidade. Entretanto, a forte tendência dessas partículas em formar agregados de tamanho micrométrico limita a aplicação tecnológica. Desta forma, a oxidação química com hipoclorito de sódio pode ser uma alternativa para minimizar esse comportamento indesejado. Os amidos de mandioca e de milho são abundantes e baratos, enquanto o amido de feijão, apesar de ter características tecnológicas interessantes e promissoras, ainda não é extraído comercialmente. O objetivo deste trabalho foi caracterizar nanocristais produzidos a partir de amidos de mandioca, de feijão e de milho, proceder a oxidação dos nanocristais e utilizá-los como estabilizadores de emulsões Pickering. Os nanocristais foram obtidos por hidrólise com ácido sulfúrico e oxidados com hipoclorito de sódio. As emulsões foram preparadas utilizando-se óleo de soja e água. O amido de feijão foi o mais resistente à hidrólise, seguido dos amidos de milho e de mandioca. Em ambas as fontes botânicas a hidrólise ácida diminuiu consideravelmente o conteúdo de amilose nas nanopartículas. A oxidação aumentou o potencial zeta de todos os nanocristais, além de diminuir a polidispersividade. Por meio da espectroscopia na região do infravermelho médio detectou-se um pico a 1735 cm-1 característico dos grupos carboxilas livres (forma ácida – COOH), típico de amidos oxidados. Os amidos de mandioca e de milho apresentaram padrão cristalino tipo A, assim como seus nanocristais. Contudo, foi observado no feijão padrão cristalino tipo C - A, que permaneceu no nanocristal; por meio da oxidação, entretanto, o padrão foi alterado para o tipo A. Após a hidrólise, a cristalinidade relativa aumentou para todas as amostras, porém com a oxidação a mesma diminuiu, exceto para o amido de feijão que resultou em efeito contrário. As amostras oxidadas apresentaram maior estabilidade coloidal, quando comparadas com as não oxidadas. Os nanocristais não apresentaram pico endotérmico detectável pela análise de DSC (Calorimetria Exploratória Diferencial). Na análise de microscopia os nanocristais exibiram formas redondas ou ovais, independentemente da origem do amido, mesmo após terem sido submetidos à oxidação. Em geral a oxidação dos nanocristais melhorou o índice de emulsão das amostras, independente da fonte botânica de origem, além disso o índice foi maior para as amostras com maior proporção de óleo em relação com as com maior fração de água. Contudo o aumento da fase oleosa aumentou o diâmetro médio das gotículas. O valor de PDI variou de 1,6, para emulsão com proporções de água e óleo 1:1 estabilizada com 5% nanocristal de mandioca oxidado, até 3,5, para emulsão com proporção de água e óleo 1:3 estabilizada com 1% de nanocristal de feijão oxidado. / The nanocrystals of starch are particles of nanometric size that have been studied, since they are abundant, biodegradable, non-toxic and with relative low cost. However, the tendency to form micrometricsize aggregates limits the technological application; therefore, chemical oxidation with sodium hypochlorite may be an alternative for limiting such unwanted behavior. These nanocrystals can be used as stabilizers for Pickering emulsions, systems where particle size is a prime factor for stability. Cassava and maize starches are abundant and cheap, while bean starch, although an interesting and promising technological product, is not yet commercially available. The present work had as objective the production and characterization of nanocrystals from cassava, bean and corn starches, following chemical oxidation of the nanocrystals and using them as emulsion stabilizers. The nanocrystals were obtained by hydrolysis with sulfuric acid and oxidized with sodium hypochlorite. The emulsions were prepared using soybean oil and water. Bean starch was less susceptible to hydrolysis, followed by maize and cassava starches. In both botanical sources the acid hydrolysis greatly reduced the amylose content in the nanoparticles. Oxidation increased the zeta potential of all the nanocrystals, besides the value of polydispersity decreased. A peak at 1,735 cm-1 was detected by means of mid-infrared spectroscopy, which is characteristic of the free carboxyl group (acid form - COOH), expected on oxidized starches. Cassava and corn starches have Atype crystallinity pattern, as their nanocrystals. For bean starch, the original C-Atype crystallinity pattern remained for the non-oxidized nanocrystals but changed for A-type after oxidation. After hydrolysis, the relative crystallinity increased for nanocrystals, but decreased after oxidation. The exception was for bean starch that resulted in oxidized nanocrystals with higher relative crystallinity. Oxidized samples are considered as colloidal when compared to non-oxidized ones. Nanocrystals did not show detectable endothermic peak on DSC (differential scanning calorimetry) analysis. The microscopic analysis of the nanocrystals showed round or oval particles, independently of the botanical source and of oxidation treatment. In general, the oxidation of nanocrystals improved their emulsification index. The emulsification index was higher for the emulsions with larger amounts of oil, even though the average diameter of the droplets increased in this situation. The polydispersity index ranged from 1.6 for 1: 1 (water to oil ratio), stabilized with 5% oxidized cassava nanocrystal, up to 3.5 for 1: 3 (water to oil ratio), stabilized with 1% of oxidized bean nanocrystal.

Nous décrivons dans ce travail l’élaboration de latex nanocomposites à base d’oxyde de cérium en vue d’applications dans le domaine des revêtements. Deux procédés originaux ont été développés afin de contrôler la morphologie des particules. Dans un premier temps, nous avons tiré parti de la forte densité de charges des nanoparticules d’oxyde de cérium pour stabiliser des particules de latex obtenues par polymérisation en émulsion ou en miniémulsion « de Pickering ». Dans les deux cas, la réaction est conduite en présence des particules inorganiques et d’un agent complexant à caractère acide, l’acide méthacrylique, en l’absence de tout tensioactif. Des particules de latex, décorées en surface par les nanoparticules d’oxyde de cérium ont été ainsi synthétisées. Par la suite, une stratégie qui consiste à utiliser des chaînes de polymères hydrophiles, réactivables (macro-agent RAFT) et préalablement adsorbées à la surface des nanoparticules d’oxyde de cérium a été envisagée. Ces chaînes polymères comportant à la fois des fonctions carboxyliques et un groupe trithiocarbonate terminal sont capables de stabiliser la suspension colloïdale des nanoparticules et de réamorcer la polymérisation en mode semi-continu permettant ainsi l’encapsulation de l’oxyde de cérium. Une optimisation visant à utiliser un procédé batch a également été évaluée. Quelle que soit la stratégie employée, une attention toute particulière a été portée à la stabilité colloïdale du milieu ainsi qu’à la cinétique de la réaction. La morphologie des particules composites a été caractérisée par MET et cryo-MET et reliée aux conditions de modification de surface et de polymérisation / This work describes the elaboration of nanocomposite latexes containing cerium dioxide nanoparticles for coating applications. Two original approaches have been developed to control the particle morphology. First, we took advantage of the high charge density of cerium dioxide nanoparticles to stabilize latex particles obtained via emulsion or “Pickering” miniemulsion polymerization. In both cases the reaction was conducted in the presence of the inorganic particles and methacrylic acid as a complexing agent, in the absence of any added surfactant. Armored latex particles covered with cerium dioxide nanoparticules were obtained by this method. Subsequently, another approach based on the use of living hydrophilic polymer chains (macroRAFT agents) previously adsorbed on the surface of the cerium dioxide nanoparticles was considered. These copolymers both containing carboxylic acid groups and carrying a thiocarbonylthio end group led to stable aqueous dispersion of the nanoparticles and could chain extend to form an encapsulating polymer shell under starved feed emulsion polymerization conditions. An optimization using a batch process was also evaluated. For both approaches, particular attention was paid to the colloidal stability of the medium and to the kinetics of the reaction. The morphology of the nanocomposite latex particles was characterized by TEM and cryo-TEM and correlated with the surface modification and the experimental conditions