Made available in DSpace on 2014-10-09T12:30:13Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:11Z (GMT). No. of bitstreams: 1 00476.pdf: 1052034 bytes, checksum: cb83f758dcd888e771ec379a99ddb0cd (MD5) / Dissertacao (Mestrado) / IEA/D / Instituto de Energia Atomica - IEA

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Nesta tese, estudamos as propriedades estruturais e dinÃmicas, bem como, a fusÃo de sistemas coloidais. Inicialmente, abordamos o problema de determinar as estruturas de mÃnima energia e o espectro de fÃnons de um sistema de dipolos magnÃticos carregados, organizados em uma estrutura de bicamadas e orientados perpendicularmente ao plano das camadas. Este sistema pode ser sintonizado atravÃs de seis diferentes fases cristalinas, atravÃs da variaÃÃo de parÃmetros tais como a separaÃÃo entre as camadas e/ou a carga e/ou o momento de dipolo das partÃculas. A presenÃa de carga elÃtrica nas partÃculas dipolares à responsÃvel pela nucleaÃÃo de cinco fases onde as camadas nÃo estÃo alinhadas verticalmente e uma fase desordenada, que nÃo sÃo encontradas no sistema em bicamadas de dipolos magnÃticos previamente apresentado na literatura. Estas fases extras sÃo uma consequÃncia da competiÃÃo entre a repulsÃo coulombiana e a interaÃÃo atrativa entre os dipolos em diferentes camadas. As estruturas de mÃnima energia sÃo sumarizadas em um diagrama de fases associado à separaÃÃo entre camadas e a importÃncia relativa entre as interaÃÃes elÃtrica e magnÃtica. Determinamos, ainda, a ordem das transiÃÃes estruturais entre as vÃrias configuraÃÃes de mÃnima energia. O espectro de fÃnons do sistema foi calculado usando a aproximaÃÃo harmÃnica. Um comportamento nÃo-monotÃnico do espectro de fÃnons à encontrado como funÃÃo da interaÃÃo efetiva entre as partÃculas. A estabilidade termodinÃmica das diferentes fases à determinada. Em seguida, estudamos o sistema de bicamadas de dipolos magnÃticos carregados para temperaturas diferentes de zero, investigando a fusÃo do sistema atravÃs do critÃrio de Lindemann modificado, em funÃÃo dos parÃmetros: (i) a distÃncia entre as camadas η e (ii) a intensidade relativa da interaÃÃo magnÃtica com respeito à interaÃÃo elÃtrica λ. Para λ suficientemente grande, uma das fases (a fase hexagonal com alinhamento vertical) exibe um comportamento reentrante na temperatura de fusÃo em funÃÃo de η. Uma vez que a carga e o momento de dipolo magnÃtico das partÃculas coloidais pode ser alterado, por exemplo, pela variaÃÃo do pH da soluÃÃo na qual estÃo imersos e por um campo magnÃtico externo, respectivamente, este sistema pode ser em princÃpio verificado experimentalmente. Por Ãltimo, um sistema bidimensional (2D) coloidal binÃrio consistindo de dipolos interagentes à investigado. Dentro da aproximaÃÃo harmÃnica, calculamos o espectro de fÃnons do sistema em funÃÃo da composiÃÃo, da razÃo entre os momentos de dipolo e da razÃo entre as massas das partÃculas pequenas e grandes. AtravÃs de uma anÃlise sistemÃtica dos espectros de fÃnons, determinamos a regiÃo de estabilidade das diferentes estruturas das ligas coloidais. As lacunas no espectro de frequÃncia dos fÃnons, as frequÃncias Ãticas no limite de longos comprimentos de onda e a velocidade do som sÃo tambÃm discutidos. Usando o critÃrio de Lindemann modificado e dentro da aproximaÃÃo harmÃnica, estimamos a temperatura de fusÃo da sub -rede gerada pelas partÃculas grandes. / This thesis presents the study of the structural and dynamical properties, as well as, melting of colloidal systems. Initially, we study the structure and phonon spectrum of a system of charged magnetic dipoles, organized in a bilayer structure and oriented perpendicular to the plane of the layers. This system can be tuned through six different crystalline phases by changing parameters such as the interlayer separation and/or the charge and/or dipole moment of the particles. The presence of the electric charge on the dipole particles is responsible for the nucleation of five staggered phases and a disordered phase which are not found in the magnetic dipole bilayer system previously presented in the literature. These extra phases are a consequence of the competition between the repulsive Coulomb and the attractive dipole interlayer interaction. The minimum energy structures are summarized in a phase diagram associated to the separation between the layers and to the relative importance between the magnetic and electric interactions. We determine the order of the structural phase transitions. The phonon spectrum of the system was calculated within the harmonic approximation. A non-monotonic behavior of the phonon spectrum is found as a function of the effective strength of the inter-particle interaction. The thermodynamic stability of the different phases is determined. Then, we study the bilayer system of charged magnetic dipoles for nonzero temperatures, investigating the melting behavior of the system through the modified Lindemann criterion, as a function of the parameters: (i) the distance between the layers η and (ii) the relative intensity of the magnetic interaction with respect to the electric interaction λ. For large enough λ, one of the phases (the matching hexagonal phase) exhibits a re-entrant melting behavior as a function of η. Since the charges and the magnetic dipole moment of the colloidal particles can be altered, for example, by changing the pH of the solution in which they are immersed or an external magnetic field, respectively, this system can be in principle verified experimentally. Last, a two-dimensional (2D) binary colloidal system consisting of interacting dipoles is investigated. Within the harmonic approximation, we obtained the phonon spectrum of the system as a function of the composition, dipole moment ratio and mass ratio between the small and big particles. Through a systematic analysis of the phonon spectra, we are able to determine the stability region of the different lattice structures of colloidal alloys. The gaps in the phonon frequency spectrum, the optical frequencies in the long-wavelength limit and the sound velocity are discussed as well. Using the modified Lindemann criterion and within the harmonic approximation, we estimated the melting temperature of the sub-lattice generated by the big particles.

Made available in DSpace on 2014-10-09T12:30:13Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:11Z (GMT). No. of bitstreams: 1 00476.pdf: 1052034 bytes, checksum: cb83f758dcd888e771ec379a99ddb0cd (MD5) / Dissertacao (Mestrado) / IEA/D / Instituto de Energia Atomica - IEA

A novel colloidal model system is developed for the purpose of achieving simultaneous three-dimensional (3D) confocal imaging and optical tweezing of impurity probe particles embedded in a dense material of colloidal host particles. First, the colloidal host particles are developed from 3-trimethoxysilyl-propylmethacrylate (TPM), and the solvent mixture is tuned to match the refractive index and the density of the particles. A sedimentation-diffusion equilibrium profile of the TPM particles was imaged in 3D to establish suitability of the system for 3D confocal laser scanning microscopy, and to study its phase behaviour and particle dynamics. Then, core-shell particles, which consist of a high refractive index core and a TPM shell, are synthesised to be used as the impurities. The versatility of the two-step coating procedure with TPM has been demonstrated on several core materials, and the optical properties of the core-shell particle are established using digital holographic microscopy and their optical trapping strengths. Together with the TPM host particles, the core-shell particles are shown to be suitable impurity probes in dense colloidal materials, as they can be manipulated using optical tweezers in all three-dimensions, whilst the structure and dynamics of the surrounding host particles can be imaged simultaneously using fast confocal laser scanning microscopy. Subsequently, to demonstrate the capability of the TPM-based colloidal model system, the depletion potential of a pair of core-shell probe particles embedded in a sea of TPM host particles has been measured using optical tweezing. This is derived from comparing the direct pair potential between the core-shell particles in a TPM refractive index matching solvent, and the potential of mean force for the core-shell particles embedded in a dense fluid region of the TPM host particles. Direct visualisation of the liquid structures of the TPM host particles in the binary system around the probe particles has been linked to the form of the depletion potential, and its oscillatory nature as a function of the particle separation. Lastly, the formation of colloidal dumbbell particles is discussed. The dumbbell formation has been rationalised in terms of the total surface energy of droplet formation on spherical surfaces and the calculations are compared with experimental results from coating various seed particles with TPM. Using optically anisotropic dumbbell particles and tuning the refractive index of the dispersion medium, a preliminary two-trap experiment has been conducted which shows unusual trapping behaviour when a time-delayed feedback trapping trajectory has been applied.

La dynamique de particules colloïdales à l'interface entre deux fluides joue un rôle central dans la micro-rhéologie, l'encapsulation, l'émulsification, la formation de biofilms, la décontamination de l'eau. En outre, ce sujet est également stimulant d'un point de vue théorique en raison de la complexité de l'hydrodynamique à l'interface et du rôle de la ligne de contact. Malgré ce grand intérêt, le comportement d'une particule à une interface fluide n'a jamais été caractérisé directement. Dans cette thèse, nous étudions le mouvement brownien de billes micrométriques de silice et de sphéroïdes de polystyrène à une interface eau-air. Nous contrôlons expérimentalement tous les paramètres d'intérêt. L'angle de contact des billes est finement ajusté dans la gamme 30°-140° par des traitements chimiques de surface et mesuré in situ par interférométrie. Le rapport d'aspect de particules sphéroïdales varie dans la gamme 1 -10 par étirage de billes sphériques commerciales. Les dynamiques de translation et de rotation sont suivies par particle tracking. Contre intuitivement et contre tous les modèles hydrodynamiques la diffusion est beaucoup plus lente que prévu. Pour expliquer cette dissipation supplémentaire nous concevons un modèle tenant compte de la contribution des fluctuations thermiques de l'interface à la ligne de contact. Les fluctuations donnent origine à des forces aléatoires qui s'ajoutent à celles dues aux chocs de molécules. Le théorème de fluctuation-dissipation permet d'obtenir la friction supplémentaire associée à ces forces flottantes. La friction totale est discutée en termes d'hétérogénéités de la surface des particules et d'ondes capillaires à l'interface. / The dynamics of colloidal particles at the interface between two fluids plays a central role in micro-rheology, encapsulation, emulsification, biofilms formation and water remediation. Moreover, this subject is also challenging from a theoretical point of view because of the complexity of hydrodynamics at the interface and of the role of the contact line. Despite this great interest, the behavior of a single particle at a fluid interface was never directly characterized.In this thesis, we study the Brownian motion of micrometric spherical silica beads and anisotropic polystyrene spheroids at a flat air-water interface. We fully characterize and control all the experimentally relevant parameters. The bead contact angle is finely tuned in the range 30-140° by surface treatments and measured in situ by a homemade Vertical Scanning Interferometer. The spheroid aspect ratio varies in the range 1 – 10 by stretching of commercial beads. The translational and the rotational dynamics are followed by particle tracking.Counter-intuitively, and against all hydrodynamic models, the diffusion is much slower than expected. To explain this extra dissipation we devised a model considering the contribution of thermally activated fluctuations of the interface at the triple line. Such fluctuations couple with the lateral movement of the particle via random forces that add to the ones due to the shocks of surroundings molecules. Fluctuation-dissipation theorem allows obtaining the extra friction associated to this additional mechanism. The fitting values of the total friction are discussed in term of the typical scales of particle surface heterogeneities and of surface capillary waves.

The growth of strontium sulfate precipitate by diffusion in various gels was studied by using optical transmission and confocal microscopies, scanning and transmission electron microscopies, and energy dispersive X ray fluorescence. Pure silica gel, pure agarose gel and the silica/agarose mixed gel at pH 7 - 10 were used throughout the present study. Precipitate morphology is sensitive to pH and to the nature of the growth medium. The morphology was observed as a function of time. The lack of change is presumably because of rapid depletion of the limiting reagent after the very beginning of precipitation. The problem of separating strontium sulfate precipitate from the gel medium is discussed.

Les colloïdes sont utilisés dans de nombreuses applications médicales tels les agents de contraste en IRM ou l'immuno-agglutination magnétique dans le diagnostic. Pour en améliorer leurs performances, l'interaction entre les particules et les milieux biologiques – en particulier les protéines – a été étudiée depuis plus de 150 ans, mais ce phénomène n'est toujours pas correctement décrit. La première partie de cette thèse est dédiée à une des applications des colloïdes : la détection de protéines cible. Basée sur l’orientation d’agrégats magnétiques anisotropes, une nouvelle méthode a été mise au point, permettant de mesurer un signal d'agrégation uniquement proportionnel à la quantité de protéines à doser, la limite de détection est donc abaissée. Cette technique a été validée sur un système réel : la protéine C-réactive. La seconde partie de cette thèse est consacrée à l’adsorption des protéines sur les colloïdes. Le premier objectif a été la mise au point d'un protocole de mesure capable de fournir des données fiables, l'adsorption a ainsi pu être caractérisée sur un système modèle, l'albumine de sérum bovin sur la silice. Les mesures obtenues ont ainsi permis de lever certains paradoxes et de proposer un nouveau modèle d’adsorption. Enfin, ces connaissances ont permis de comprendre comment des protéines, en s’adsorbant sur deux particules, agrègent les colloïdes. En quantité suffisante, elles peuvent également les protéger de l’agrégation, ouvrant la voie à une nouvelle méthode de stabilisation des particules. / Colloids are used in many applications such as contrast agents in MRI or magnetic immuno-agglutination in diagnosis. To improve their performance, the interaction between particles and biological media – in particular proteins – has been studied for more than 150 years, nevertheless this phenomenon is still not well described. The first part of this thesis is dedicated to an application of colloids: detection of target proteins. Based on orientation of anisotropic magnetic aggregates, a new method has been developed, which generates a signal of aggregation, directly proportional to the amount of protein in the sample: lowering the detection limit. This technique has been validated on a real system: C-reactive protein. The second part is dedicated to protein adsorption on colloids. The first objective was the development of a protocol to obtain reliable measurements, adsorption could then be characterized in a model system: bovine serum albumin and silica. Results obtained were thus able to dismiss certain paradoxes and to propose a new model. Ultimately the studies reveal how proteins, by adsorbing between two particles, aggregate colloids. In sufficient quantities, they can also protect against aggregation, enabling a new method of particle stabilization.

La formation de bouchon est un problème récurrent et presque inévitable lors de l'écoulement de solutions diluées dans des milieux poreux. Actuellement, on ne sait pas comment, à partir du processus initial de déposition de particules à la paroi, ces dernières s'accumulent dans le pore et finissent par le boucher. L'idée générale de ce travail est d'étudier la dynamique de formation de bouchon lors l'écoulement de particules colloïdales au sein de matériaux poreux modèles (canaux microfluidiques). Nous décrivons dans un premier temps, les différents phénomènes physiques impliqués dans la capture de particules et dans l'agrégation colloïdale. Nous faisons également une brève présentation des différentes techniques d'imagerie utilisées dans ce travail et des méthodes de préparation des solutions colloïdales ainsi que des dispositifs microfluidiques. Le troisième chapitre est consacré à l'étude du processus de colmatage en situation de fort confinement (2d). Nous avons identifié deux régimes de colmatage (régime de ''ligne'' et ''d'invasion''). Nous avons ensuite déterminé les processus de capture de particules à l'origine de ces deux régimes, à l'échelle de la particule. Nous avons montré que le processus de colmatage correspond à un phénomène d'auto-filtration. Alors que les premières particules sont capturées de manière « directe » par les parois du pore, la déposition de toutes les suivantes résulte systématiquement d'une interaction avec ces dernières. Finalement, nous avons abordé le colmatage de pore 3d, dont la hauteur est égale à la largeur du pore. Nous avons fourni une description détaillée de l'ensemble du processus de colmatage, à l'échelle du pore et de la particule. Nous avons déterminé les conditions d'adhésion des premières particules à la paroi du pore, les propriétés de croissance des agrégats, ainsi que la manière dont ils se connectent pour obstruer le pore. Nous avons montré que cette dynamique de formation conduit à une structure finale de bouchon très ténue. / Clog formation is a recurring and almost inevitable issue when dilute solution of particles flows in porous media. Currently, we do not know how, from the initial process of particle deposition on the pore wall, particles accumulate in the pore leading to its blocking. The main idea of this work is to study the dynamics of the clog formation, when colloidal particles flow through a single pore (microfluidics channels). In a first part, we describe the various physical phenomenon involved in the particle capture and the colloidal aggregation. We also describe briefly the imaging techniques used in this work as well as the colloidal solution and micro-fluidics chips preparation. The third chapter is devoted to the study of the clogging process in high confinement (2d). We identified two clogging regimes (“line” and “invasion”). We then studied the underlying capture mechanisms, at the particle scale, related to both clogging regimes. We showed that the blockage process corresponds to a self-filtration process. The first particles are captured “directly” by the pore walls, while the deposition of all the following ones systematically results from hydrodynamic interactions with those first still particles. Finally, we addressed the clogging of a 3d pore, in which the height of the pore is equal to its width. We gave a detailed description of the whole clogging process at the pore and at the particle scale. We provided the conditions for the adhesion of the first particles on the pore walls, the properties of subsequent aggregates growth, and how the aggregates eventually merge in order to block the pore. We showed that this dynamics of formation leads to a very loose clog structure.

Doctor of Philosophy / Department of Physics / Amitabha Chakrabarti / This work is the result of a wide range of computer simulation research into the aggregation behavior of dispersed colloidal and aerosol particles in a number of different environments from the continuum to the free-molecular. The goal of this research has been to provide a bridge between experimental and theoretical researchers in this field by simulating the aggregation process within a known model. To this end, a variety of interparticle interactions has been studied in the course of this research, focusing on the effect of these interactions on the aggregation mechanism and resulting aggregate structures. Both Monte Carlo and Brownian Dynamics codes have been used to achieve this goal. The morphologies of clusters that result from aggregation events in these systems have been thoroughly analyzed with a range of diverse techniques, and excellent agreement has been found with other researchers in this field. Morphologies of these clusters include fractal, gel, and crystalline forms, sometimes within the same structure at different length scales. This research has contributed to the fundamental understanding of aggregation rates and size distributions in many physical system, having allowed for the development of improved models of the aggregation and gelation process. Systems studied include DLCA and BLCA in two and three dimension, free-molecular diffusional (Epstein) system, selective aggregation in binary colloids, ssDNA mediated aggregation in colloidal systems, and several others.

La prévision du transport et de la rétention des colloïdes représente un enjeu environnemental majeur car ces particules peuvent entraîner des polluants adsorbés ou bien être des polluants eux-mêmes. Les modèles utilisés actuellement pour prédire le devenir des colloïdes dans les sols sont basés sur des mécanismes déduits des courbes de percée (évolution de la concentration en fonction du volume de pore ou du temps) après injection de particules dans une colonne de milieu poreux. Le but de cette thèse est de compléter cette compréhension avec des mesures internes grâce à l’Imagerie par Résonance Magnétique (IRM).L’IRM permet de mesurer la distribution 1D et/ou 2D de particules super-paramagnétiques le long d’un échantillon pendant une expérience de transport dans un milieu poreux. Le couplage de cette technique avec l'étude des courbes de percée donne une approche globale. Nous avons effectué plusieurs expériences de transport dans des colonnes de milieux poreux de complexité de porosité croissante : billes de verre, sable, agrégats de sol, et sol non perturbé.A partir des expériences de transport dans les milieux poreux modèles saturés, nous avons montré que la dispersion est moins importante que la théorie le prévoit et qu’elle est fortement dépendante des effets d’entrée dans la colonne. Cette dépendance est aussi observée pour les mécanismes d’adsorption. Les expériences dans les agrégats de sol ont montré une forte adsorption et un relargage constant, dépendants de la vitesse d’injection. Finalement, des expériences de pluie dans des colonnes de sol non perturbé insaturé ont permis de suivre l’évolution des teneurs en eau et en particules dans le temps / The ability to predict transport and retention of colloidal particles is a major environmental concern as such particles can carry adsorbed pollutants towards the groundwater or be pollutants themselves. The models currently used to predict the fate of colloids in soils are based on mechanisms inferred from breakthrough curves (evolution of concentration as a function of pore volume or time) after injection of particles into a column of porous media. In this thesis we aim to complement this comprehension with internal measurements by Magnetic Resonance Imaging (MRI).MRI provides 1D and/or 2D distribution of contrast agent particles in time along the sample axis during transport experiment through a porous medium. This technique, together with the study of breakthrough curves gives a global approach. We performed several transport experiment in columns of porous media of increasing complexity: glass beads, sand, soil aggregates, and undisturbed soil.From transport experiments in model porous media we show that dispersion is less important than expected and strongly dependent on entrance effects in the column. This dependence is also observed for adsorption. Experiments in soil aggregates showed a strong adsorption but also a constant release, dependent on the flow rate. Finally, rain experiments in undisturbed sol columns allowed following water content and particles as a function of time