Cette thèse présente une étude expérimentale de l'impact de gouttes de fluides à seuil. Au-delà des applications (impression à jet d'encre solide, modélisation d'impact solide à grandes vitesses), cette étude permet de sonder le rôle de l'élasticité sur le comportement à temps court de ces fluides complexes. D'abord, nous nous sommes intéressés aux impacts sur une surface rigide. L'utilisation de fluides à seuil modèles (solutions concentrées d'argiles, micro-gel de Carbopol) et de surfaces d'impact variées (partiellement mouillante ou super-hydrophobe), révèle une grande variété de comportements, allant de l'étalement viscoplastique irréversible jusqu'à des déformations élastiques géantes. Un modèle minimal d'étalement inertiel, incluant une rhéologie élasto/viscoplastique, permet de décrire dans un cadre unique les principaux régimes observés. Au cours de cette étude, nous avons mis en évidence un phénomène spécifique avec le Carbopol : pour des grandes vitesses d'impact, on observe un étalement beaucoup plus grand sur des surfaces rugueuses hydrophobes que sur des surfaces lisses. Cette réduction apparente du frottement basal est discutée en termes de longueur de glissement et d'instabilité de " splash ". Enfin, nous avons étudié l'impact d'une goutte de fluide sur un sol constitué du même fluide, en utilisant un fluide à seuil transparent (Carbopol). La combinaison de lois d'échelle, d'expériences en " micro-gravité " et de mesures locales du champ de déformation montre que la dynamique du cratère transitoire est dominée par l'élasticité, même au-delà du seuil d'écoulement. Ces résultats pourraient avoir des implications dans le contexte des impacts de météorites en astrophysique.

Ce travail propose une étude expérimentale visant à caractériser les processus dynamiques se produisant au sein de matériaux vitreux mous. La première partie présente des mesures de diffusion de traceurs nanométriques dans la Laponite (une suspension colloïdale) obtenues par une méthode de recouvrement de fluorescence (FRAP). Cette étude montre que la diffusion varie avec la concentration de Laponite et la taille du traceur. Un modèle hydrodynamique de diffusion confinée permet de décrire quantitativement les données expérimentales. Une deuxième partie concerne l'étude expérimentale du vieillissement de matériaux vitreux. Nous testons en pratique le concept théorique de température effective. Celle-ci est obtenue grâce à la technique de FRAP par la mesure simultanée de la diffusion et la convection de sondes fluorescentes dans la Laponite en cours de prise. Contrairement à certaines mesures de la littérature, le système est bien gouverné par la température ambiante. Nous présentons ensuite une étude visant à caractériser le comportement de la Laponite cisaillée. Nous avons pour cela mis au point un dispositif permettant d'appliquer un champ électrique au système, et ainsi créer des déformations locales. L'effet obtenu s'est révélé trop faible, avec d'assez grandes incertitudes (probablement liées à la complexité du système), pour être considéré comme significatif. Enfin, nous avons étudié les propriétés du Carbopol, un fluide à seuil, en mesurant sa dynamique d'ascension par capillarité. La rugosité de surface des capillaires influe énormément sur la montée du fluide. Nous montrons aussi que l'ascension est pilotée par la rhéologie du système, notamment par le seuil d'écoulement.

Des panaches sont connus pour migrer à travers le manteau ductile et quasi-Newtonien ; alors que les dikes se fracturent et se propagent dans la lithosphère solide. Cependant, la lithosphère est en fait visco-élastique. Afin de déterminer ce qui se passe dans ce cas complexe, nous avons réalisé une étude expérimentale et numérique sur le développement de panaches thermiques dans des solutions aqueuses de Carbopol, un gel de polymères formant un réseau continu d'éponges microscopiques. Ce fluide est rhéofluidifiant et présente un seuil de contrainte σ₀, de sorte que l'écoulement ne se produit que si la contrainte locale dépasse cette valeur critique σ₀. En dessous de cette valeur, le fluide agit comme un solide élastique. Les propriétés rhéologiques des solutions peuvent être systématiquement ajustées en variant la concentration de Carbopol. Le dispositif consiste en une source locale de chaleur de puissance constante placée au centre d'une cuve cubique. Selon la valeur du rapport entre la contrainte d'origine thermique et la contrainte seuil, Y₀, on peut observer trois régimes différents. A faible Y₀.

Made available in DSpace on 2014-06-11T19:23:39Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-12-04Bitstream added on 2014-06-13T20:50:44Z : No. of bitstreams: 1 minussi_rb_me_ilha.pdf: 1918415 bytes, checksum: 5176f1d27a7b361288abf94e48919e04 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Denominam-se problemas tipo rompimento de barreira os fenômenos nos quais um fluido é liberado de maneira abrupta. Quando o fluido apresenta natureza hiperconcentrada, a relação entre a tensão de cisalhamento e a taxa de deformação pode se tornar não-linear, passando a apresentar reologia não-Newtoniana. Problemas deste tipo podem ser encontrados em muitos fenômenos tanto na natureza quanto em processos industriais. O estudo de tal problema é, geralmente, conduzido usando simplificações, como a aproximação de águas rasas e a separação do escoamento em regimes dominantemente inerciais ou viscosos. O presente trabalho é composto de duas partes, uma experimental e outra, numérica. No campo experimental, duas soluções controladas são usadas: soluções aquosas de açúcar e de Carbopol 940, esta última com várias concentrações volumétricas. O aparato experimental consiste em um canal retangular de acrílico, contendo uma comporta, a montante da qual, o fluido é retido e, pela ruptura (levantamento da comporta), começa a escoar. O escoamento é estudado através de técnicas avançadas de filmagem. No campo numérico, são realizadas simulações usando o programa CFX, no qual é usado um método de rastreamento de interface, o VOF e sem o emprego das simplificações citadas. Os resultados experimentais são comparados com os numéricos e com resultados da literatura que usam tais simplificações. Na comparação a aproximação de águas rasas, apesar de descrever bem a forma da interface, se distancia dos valores reais da posição da frente de onda. / The dam break problem describes a phenomenon in which there is an abrupt release of fluid. When the fluid is hiperconcentrated, the relation between the shear stress and the strain rate can become non-linear, and so present a non-Newtonian rheology. The non-Newtonian dam break problem may be found in many phenomena in nature and industrial process. The study of such a problem is, generally, conducted using simplified hypothesis such as the shallow water approximation and the separation of the flow in inertial and viscous dominated regimes. The present work is composed of two parts, one experimental and other, numerical. In the experimental field, two controlled solutions were used: water solutions of sugar and of Carbopol 940, the last one with a wide range of volume concentrations. These fluids have, respectively, Newtonian and non-Newtonian rheologies. The experimental setup consists of an acrylic rectangular channel, which has a dam and upstream of that the fluid is retained and, by the rupture, it begins to flow. The flow is studied by using advanced filming techniques. In the numerical field, simulations are conducted using the CFX software, which uses an interface tracking method, the VOF, and without the shallow water approximation and the division of the flow. So the experimental, numerical and literature results, that uses such simplifications, are compared and it is showed that the shallow water approximation, however describes very well the shape of the surface, is not accurate in calculate the wave front position.

Orientador: Geraldo de Freitas Maciel / Banca: Cassio Roberto Macedo Maia / Banca: Mônica Feijó Naccache / Resumo: Rompimentos de Barreira são fenômenos caracterizados por um campo de escoamento inicialmente represado e submetido nos instantes subseqüentes a uma liberação abrupta. Diversos modelos matemáticos e leis de comportamento reológico podem ser associados a este problema e cada um deles deve ser estudado e compreendido de maneira a predizer, a partir de testes físicos e numéricos, sua adequação à descrição da evolução espaço-temporal de frentes resultantes deste fenômeno, tipo ruptura de barragem, retendo água , rejeitos ou materiais de reologia complexa. O desenvolvimento de técnicas analíticas possibilitou entender de maneira impar o desenvolvimento desses fenômenos, porém, a difícil obtenção de dados que alcançassem consonância com aqueles obtidos experimentalmente, demonstrava a fragilidade desse tipo de análise perante a descrição de sistemas dinâmicos complexos. Sendo assim, optou-se pela tentativa de recriar estes fenômenos a partir de técnicas que utilizassem a manipulação de equações governantes completas. Sistemas contínuos podem ser analisados através de aproximações discretas, resultando em valores realísticos, muito próximos aos obtidos experimentalmente, e a capacidade computacional atual, permite diminuir sensivelmente os erros envolvidos, aumentando cada vez mais a consistência física destes métodos. Neste trabalho utilizou-se o software comercial ANSYS-CFX para simular os fenômenos de ruptura de barreira, configurando a reologia de dois materiais, o Carbopol 940 representando um material de reologia complexa (Herschel-Bulkley) e o Glicerol (Newtoniano), esses dados foram então confrontados com os obtidos experimentalmente através de um modelo em escala reduzida. Campos de velocidade, pressão e evolução temporal das frentes foram analisadas, verificando-se valores com grande consonância entre numérico e experimental, mostrando uma grande consistência física dos métodos utilizados / Abstract: The Dam Break problem is a phenomenon characterized by a flow field initially dammed and submitted in the subsequent moments of an abrupt release. Various mathematical models and laws of rheological behavior may be associated with this type of problem and each must be studied and understood in order to predict from physical and numerical tests the temporal evolution of their fronts resulting from this phenomenon, type Dan Break problems, retaining water or rheology complex materials. The development of analytical techniques enabled the understanding the development of these phenomena, however, the difficulty to obtain a reach agreement data with those obtained experimentally, showed the fragility of this type of analysis to the description of complex dynamic systems. But, it was decided by attempt of recreate these phenomena from techniques that use the manipulation of complete government equations. Continuous systems can be analyzed by discrete approximations, leading to realistic values, very close to those obtained experimentally, and current computational capacity, enables to reduce the errors involved significantly, increasing the consistency of these physical methods. This work used the commercial software ANSYSCFX to simulate the phenomena of breaking the barrier, setting the rheology of two materials, the Carbopol 940 representing a material of complex rheology (Herschel-Bulkley) and glycerol (Newtonian), these data were then compared with those obtained experimentally using a model in scale. Fields of velocity, pressure and temporal evolution of the fronts were analyzed. Found very similar values between numerical and experimental simulations, showing the physical consistency of the methods used / Mestre

<p>Drug delivery to the nasal and ocular mucosa faces several obstacles. One of these is from the effective clearance mechanisms present in the nose and eye. Polymer gels with suitable rheological properties can facilitate the absorption of poorly absorbed drugs by increasing the contact time of the drug with the mucosa. This has been attributed to the rheological and mucoadhesive properties of the gel. The main objective of this thesis was to investigate the importance of these features for the anticipated in vivo contact time, here exemplified by the ocular and nasal routes of administration.</p><p>The in situ gelling polymer gellan gum was found to have a favourable rheological and in vivo performance. When administered in the nasal cavity of rats, a gel was formed that could remain at the site of administration for up to 4 hours. In addition, the epithelial uptake and transfer of a 3 kDa fluorescein dextran was higher than for a mannitol solution. Therefore, it was concluded that a gellan gum formulation should be a promising strategy for nasal drug delivery.</p><p>The potential mucoadhesive properties of a variety of polymer gels were investigated using a rheological method and by measuring the tensile force required to detach the gel from a mucosa. With both methods the rheological properties of the gel were a determining factor for the results obtained. The rheological method was found to have several limitations. One of these was that a positive response, interpreted as mucoadhesion, was only seen with weak gels. The tensile method could, in contrast, detect strengthening of the mucus only for strong gels. However, this method reflects the in vivo performance of the gel better than the rheological method.</p><p>Finally, dielectric spectroscopy was explored as a tool for investigating the likelihood of intimate surface contact between the gel and the mucus layer. This novel approach involved determining the ease with which a charged particle can pass the gel-mucus interface layer, and may enable the study of the events at the interface closer to the molecular level, than is possible with the rheological and tensile strength methods.</p>

<p>This thesis concerns the development and utilisation of techniques for characterisation and transdermal delivery of various systems for pharmaceutical applications.</p><p>The degree of dissociation of drug molecules and the mobilities of the different species formed are essential factors affecting the rate of drug delivery by iontophoresis. Hence, determination of drug mobility parameters and equilibrium constants are important for the development of iontophoretic systems. With capillary zone electrophoresis using a partial filling technique and methyl-β-cyclodextrin as chiral selector, the enantiomers of orciprenaline were separated. The association constants between the enantiomers of the drug and the selector were also evaluated. Precision conductometry studies were performed for the hydrochloride salts of lidocaine and 5-aminolevulinic acid in aqueous propylene glycol and water as media, respectively.</p><p>Iontophoresis is a technique for drug delivery where charged molecules are transported into and through skin by application of a weak direct electrical current. The drugs 5-aminolevulinic acid and its methyl ester were used as model compounds and incorporated in two different drug delivery vehicles, a sponge phase and carbopol gel. The bicontinuous structure of the sponge phase, constituted of monoolein and a mixture of propylene glycol and water, makes it interesting for use in iontophoretic delivery, since ions can move more or less freely in the aqueous as well as in the lipid domains. Furthermore, all three components are known for their penetration enhancing abilities. Hydrogels like carbopol gels are interesting media with respect to iontophoretic studies, since devices for iontophoresis often utilize hydrogels as contact interfaces between the skin and the electrodes. The results indicate that the transport achieved iontophoretically using the gel (1 % active substance) was comparable with the passive delivery of clinically used formulations (16 % - 20 % active substance).</p>

Drug delivery to the nasal and ocular mucosa faces several obstacles. One of these is from the effective clearance mechanisms present in the nose and eye. Polymer gels with suitable rheological properties can facilitate the absorption of poorly absorbed drugs by increasing the contact time of the drug with the mucosa. This has been attributed to the rheological and mucoadhesive properties of the gel. The main objective of this thesis was to investigate the importance of these features for the anticipated in vivo contact time, here exemplified by the ocular and nasal routes of administration. The in situ gelling polymer gellan gum was found to have a favourable rheological and in vivo performance. When administered in the nasal cavity of rats, a gel was formed that could remain at the site of administration for up to 4 hours. In addition, the epithelial uptake and transfer of a 3 kDa fluorescein dextran was higher than for a mannitol solution. Therefore, it was concluded that a gellan gum formulation should be a promising strategy for nasal drug delivery. The potential mucoadhesive properties of a variety of polymer gels were investigated using a rheological method and by measuring the tensile force required to detach the gel from a mucosa. With both methods the rheological properties of the gel were a determining factor for the results obtained. The rheological method was found to have several limitations. One of these was that a positive response, interpreted as mucoadhesion, was only seen with weak gels. The tensile method could, in contrast, detect strengthening of the mucus only for strong gels. However, this method reflects the in vivo performance of the gel better than the rheological method. Finally, dielectric spectroscopy was explored as a tool for investigating the likelihood of intimate surface contact between the gel and the mucus layer. This novel approach involved determining the ease with which a charged particle can pass the gel-mucus interface layer, and may enable the study of the events at the interface closer to the molecular level, than is possible with the rheological and tensile strength methods.

This thesis concerns the development and utilisation of techniques for characterisation and transdermal delivery of various systems for pharmaceutical applications. The degree of dissociation of drug molecules and the mobilities of the different species formed are essential factors affecting the rate of drug delivery by iontophoresis. Hence, determination of drug mobility parameters and equilibrium constants are important for the development of iontophoretic systems. With capillary zone electrophoresis using a partial filling technique and methyl-β-cyclodextrin as chiral selector, the enantiomers of orciprenaline were separated. The association constants between the enantiomers of the drug and the selector were also evaluated. Precision conductometry studies were performed for the hydrochloride salts of lidocaine and 5-aminolevulinic acid in aqueous propylene glycol and water as media, respectively. Iontophoresis is a technique for drug delivery where charged molecules are transported into and through skin by application of a weak direct electrical current. The drugs 5-aminolevulinic acid and its methyl ester were used as model compounds and incorporated in two different drug delivery vehicles, a sponge phase and carbopol gel. The bicontinuous structure of the sponge phase, constituted of monoolein and a mixture of propylene glycol and water, makes it interesting for use in iontophoretic delivery, since ions can move more or less freely in the aqueous as well as in the lipid domains. Furthermore, all three components are known for their penetration enhancing abilities. Hydrogels like carbopol gels are interesting media with respect to iontophoretic studies, since devices for iontophoresis often utilize hydrogels as contact interfaces between the skin and the electrodes. The results indicate that the transport achieved iontophoretically using the gel (1 % active substance) was comparable with the passive delivery of clinically used formulations (16 % - 20 % active substance).

Cette thèse présente une étude expérimentale visant à caractériser les propriétés hydrauliquesd'écoulements à surface libre de fluides complexes: fluides viscoplastiques et mélangesfluides viscoplastiques-grains. Ce travail est motivé par la nécessité d'améliorer lesconnaissances sur les propriétés des écoulements de laves torrentielles, dans un contexte deprotection contre les risques naturels en montagne. Nous avons développé un dispositif delaboratoire original, un canal à fond mobile, permettant de générer des coulées gravitaires quisont globalement stationnaires dans le référentiel du laboratoire. Les coulées présentent unfront très raide, suivi à l'amont d'une zone d'épaisseur uniforme. Les fluides viscoplastiquesutilisés (carbopol et kaolin) ont été choisis de manière à modéliser la matrice des couléesboueuses naturelles en prenant en compte les critères de similitude adaptés. Ces fluidessuivent une loi de comportement de Herschel-Bulkley, et leurs propriétés rhéologiques ont étédéterminées au moyen d'un rhéomètre de laboratoire en accordant un soin particulier àl'établissement des incertitudes associées. Nous présentons des mesures précises de l'évolutionde l'épaisseur des coulées dans la zone uniforme en fonction de la vitesse du fond du canal etde la pente. Ces résultats sont comparés à des prédictions théoriques correspondant à unécoulement permanent et uniforme d'un fluide de Herschel-Bulkley, et nous montrons quel'accord est satisfaisant moyennant les incertitudes sur les mesures rhéologiques. Nous avonségalement analysé la forme du front des coulées et, là-aussi, l'accord avec des modèleshydrauliques (modèles de type Saint-Venant) est bon. Ces deux études permettent de validerles prédictions hydrauliques obtenues à partir de lois de comportement mesurées aurhéomètre. Enfin, dans une dernière partie, nous présentons une étude préliminaire de ladynamique de particules rigides isolées placées au sein de la coulée, en nous intéressant auxvitesses longitudinales et aux vitesses de chute pour différentes tailles et différentes densitésde particules.