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. / This work is based on an experimental analysis of the dynamical processes which occur within soft glassy materials. The first part provides measurement results of nanotracers diffusion in Laponite (a colloidal suspension) obtained by a method of fluorescence recovery (FRAP). This study shows that the diffusion is affected by the concentration of Laponite as well as the size of the tracer. A hydrodynamic model with confined diffusion allows a quantitative description of the experimental data. In a second part, an experimental study is carried out, dealing with the aging processes of glassy materials. The theoretical concept of effective temperature is probed experimentally. The effective temperature is determined using the technique of FRAP, by simultaneously measuring diffusion and convection of fluorescent probes within the aging Laponite. Contrary to some measurements found in literature, results show that the system is controlled by the bath temperature. The following study then aims at characterizing the behavior of the sheared Laponite : an experimental device is developed in this perspective, by applying an electric field to the system and thus creating local deformations. However, the observed effect appears to be too low, with relatively large uncertainties (probably linked to the complexity of the system), which impede on the significance of our results. Finally, the properties of Carbopol, a yield stress fluid, are analyzed by measuring the dynamics of capillary rise. It is shown that the surface roughness of capillary strongly affects the rise of the fluid and that the latter is controlled by the rheology of the system, and more specifically by the yield stress value.

Les fluides complexes tels que les gels, les pâtes ou les émulsions présentent une large gamme d'applications, tant dans la vie quotidienne que dans l'industrie. Parmi ces fluides, les fluides dits ”à seuil” se comportent soit comme des solides élastiques, soit comme des fluides nonnewtoniens selon la contrainte qu'on leur applique. Ces propriétés sont décrites par des lois phénoménologiques (telle que la loi d'Herschel Bulkley), bien que leurs origines soient encore mal comprises. Dans cette thèse, nous nous intéressons à la question des petites échelles, où la structure et les phénomènes interfaciaux jouent des rôles prépondérants dans les écoulements. Ce travail expérimental a été essentiellement mené sur du carbopol, un microgel de polymères et un fluide à seuil modèle. L'étude se concentre essentiellement sur trois points : – La caractérisation rhéologique et structurale des échantillons. L'accent est porté sur l'influence du protocole de préparation sur les propriétés des gels.– Le cas des écoulements confinés de fluides complexes. Ce travail met en évidence l'existence d'effets non-locaux aux échelles micrométriques, faisant intervenir une taille caractéristique interprétée dans le cadre du modèle de fluidité. – Les ascensions capillaires de fluides complexes, aux échelles millimétriques. En revisitant l'expérience classique des ascensions capillaires dans le cas des fluides complexes, cette étude propose une extension de la loi de Jurin au cas des fluides à seuil. Il est montré que cette expérience simple permet de mesurer la tension de surface et quelques paramètres rhéologiques de fluides complexes tels que le seuil et l'exposant d'Herschel-Bulkley / Complex fluids such as gels, pastes or emulsions have a wide range of applications, both in everyday life and in the industry. Among them, Yield Stress Fluids (YSF) behave either as solids or as non-Newtonian fluids depending on the shear stress applied. These features are modeled by phenomenological laws ( such as the Herschel-Bulkley one ) although their origins are still poorly understood. In this thesis, we focus on the issue of small lengthscales where the structure and interfacial phenomena play predominant roles in the flows. This experimental work was essentially carried out on carbopol, a polymer microgel and a model YSF. The study mainly focuses on three points : – The rheological and structural characterization of the samples. The emphasis is put on the influence of the preparation protocol on the microgel properties. – The case of confined flows of complex fluids. This work highlights the existence of nonlocal effects at the micrometer scales, involving a characteristic length, interpreted in the frame of the fluidity model. – Capillary ascents of complex fluids, involving millimeter scales. This work suggests an extension of Jurin’s law to the case of YSFs. It is shown that this simple experiment allows to measure the surface tension and some rheological parameters of complex fluids such as the yield stress and the Herschel-Bulkley exponent

Dosage forms have been developed over the years for various applications. The dosage form consists of the active drug in combination with pharmaceutical excipients. The pharmaceutical excipients solubilise, suspend, thicken, dilute, emulsify, stabilise, preserve, colour and flavour medicinal agents into efficacious and appealing dosage forms. The dosage form under investigation in this study is of the oral type. The Pheroid® is a unique drug delivery system which consists of an oil-in-water emulsion system. Emulsion based drug systems provide a suitable medium for the delivery of both hydrophobic and hydrophilic drugs which can be incorporated into its oil or water phase for delivery to the site of action. These advantages make them more efficient as dosage form. Emulgels are either emulsion of oil-in-water or water-in-oil type, which is gelled by mixing with gelling agents. Incorporation of emulsion into gel increases its stability and makes it a dual control release system. The presence of the gel phase makes it a non-greasy formulation which favours good patient compliance. A strategy followed to improve the stability of the emulgel system is the packaging of the formula into single dose sachets to protect the product against physical and chemical breakdown during patient usage. All factors such as selection of gelling agent, preservatives and formulation methods influencing the stability and efficacy of Pheroid® emulgel are discussed. In this study, three different emulsifiers were added to the formula and the analysis of visual appearance, pH measurements, rheological studies, light microscopy and confocol laser scanning microscopy (CLSM) will provide an insight to the potential usage of emulgel as drug delivery system. A range of para-hydroxybenzoate esters was tested in the Pheroid® emulgel and the most suitable candidate chosen for further accelerated stability testing. It was thus possible to prepare a single dose emulgel with Carbopol® 934P (0.2% w/v) as an emulsifier, with Nipastat® (0.175% w/v) and PG (10% v/v) as preservatives into a stable dosage form suitable for further product development. / PhD (Pharmaceutics), North-West University, Potchefstroom Campus, 2014

Dosage forms have been developed over the years for various applications. The dosage form consists of the active drug in combination with pharmaceutical excipients. The pharmaceutical excipients solubilise, suspend, thicken, dilute, emulsify, stabilise, preserve, colour and flavour medicinal agents into efficacious and appealing dosage forms. The dosage form under investigation in this study is of the oral type. The Pheroid® is a unique drug delivery system which consists of an oil-in-water emulsion system. Emulsion based drug systems provide a suitable medium for the delivery of both hydrophobic and hydrophilic drugs which can be incorporated into its oil or water phase for delivery to the site of action. These advantages make them more efficient as dosage form. Emulgels are either emulsion of oil-in-water or water-in-oil type, which is gelled by mixing with gelling agents. Incorporation of emulsion into gel increases its stability and makes it a dual control release system. The presence of the gel phase makes it a non-greasy formulation which favours good patient compliance. A strategy followed to improve the stability of the emulgel system is the packaging of the formula into single dose sachets to protect the product against physical and chemical breakdown during patient usage. All factors such as selection of gelling agent, preservatives and formulation methods influencing the stability and efficacy of Pheroid® emulgel are discussed. In this study, three different emulsifiers were added to the formula and the analysis of visual appearance, pH measurements, rheological studies, light microscopy and confocol laser scanning microscopy (CLSM) will provide an insight to the potential usage of emulgel as drug delivery system. A range of para-hydroxybenzoate esters was tested in the Pheroid® emulgel and the most suitable candidate chosen for further accelerated stability testing. It was thus possible to prepare a single dose emulgel with Carbopol® 934P (0.2% w/v) as an emulsifier, with Nipastat® (0.175% w/v) and PG (10% v/v) as preservatives into a stable dosage form suitable for further product development. / PhD (Pharmaceutics), North-West University, Potchefstroom Campus, 2014

Aims Novel low toxicity formulations using biomaterial (i.e. gelatin) for triggered release and controlled manner of formulated therapeutic agent for treatment of immuno-inflammatory disease on the skin were studied in the PhD project. It is a challenging concept because of difficulties in targeting and controlling for the releases that is tailored to disease severity or lesional inflammation extent. Background Psoriasis is a complicated disease with multi-factorial pathogenesis. Potent anti-psoriatic drugs are available but for managing the symptoms of the disease. Due to the toxicity of the therapeutic agents, different strategies have been suggested to avoid severe side effects from long term or high dose usage. Psoriasis is an optimal representative for this investigation in terms of the toxicities of recognized drugs, unpredictable or relapsed nature of the disease or even life threatening developments if generalised symptoms develop as they can in some types. Method Using the rheometry in temperature sweep mode, a series of concentrations of pure gelatin and gelatin mixture were developed. In addition, using tryptic enzyme, their action was studied rheologically. A Petri dish observational method was used to investigate the permeability of formulations chosen on the basis of the rheometric performance. Then, combining the Copley diffusion cell kit and UV/VIS spectrophotometer, the release of the model drug was investigated in porous artificial membranes and porcine skin for one or more of the formulations. The preliminary part using porous artificial membranes was to investigate the amount of the release of tartrazine from a candidate gel into the circulation system. In this part, alternatives were considered for dealing with gelatin or gelatin/carbomer swelling by using mechanical stress approach or changing to octanol solvent. For the latter a dye, rhodamine, which would partition into octanol had to be substituted for tartrazine (which has iv negligible organic solubility). In the final part, using skin membrane, the amount of the release tartrazine to the skin was measured because in this, skin staining, rather than partition was needed. Results Promising results were observed in each stage. The rheological investigation on the developed gelatin/water system and gelatin/carbomer intimate system in absence and presence of tryptic enzyme showed that a responsive but convenient formulation was possible and was independent of the presence of tartrazine. Analysis of these resulting rheological profiles suggested a prediction for the best gelatin/carbomer formulations to select for the permeability tests. The latter used Petri dishes to compare differential diffusion of these candidates showed the carbomer was able to stop three-dimensional spreading of the dye through the pure gelatin or its residue (after enzyme action). The drug release studies using artificial porous membranes for preliminary work showed significant differential release between enzyme free and enzyme treated versions of the 20% gelatin/0.9% carbomer formulation. The final success was the in vitro skin experiment in which the result was obtained for the pure gelatin and shown to deliver very substantially more to areas with applied enzyme s a simulated lesion.

Made available in DSpace on 2014-06-11T19:23:39Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-12-02Bitstream added on 2014-06-13T18:50:59Z : No. of bitstreams: 1 leite_lob_me_ilha.pdf: 7876959 bytes, checksum: 679218273f75952f4df0237622251b57 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / 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 / 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

No description available.

Siekiant pagaminti stabilias smulkiadispersines emulsines sistemas, naudojant mažas emulsiklių koncentracijas (0,1-0,4%), optimizuojant technologinį procesą, tiriamos naujų emulsiklių panaudojimo galimybės. Poliakrilo rūgšties polimerai (Pemulen™ TR-1 ir TR-2 )-universalūs a/v emulsijų emulsikliai, nepasižymintys toksiškumu aplinkai bei žmogui, kuriuos naudojant mažomis koncentracijomis – 0,1-0,4% - gali būti pagamintos įvairių formų stabilios emulsijos. Šio darbo tikslas ištirti ir įvertinti poliakrilo rūgšties polimerų Pemulen™ TR-1 ir Pemulen™ TR-2 bei pagalbinių medžiagų, nejonogeninio emulsiklio Span 80 ir Carbopol® Ultrez 20, įtaką emulsijų a/v stabilumui, tyrimo rezultatus panaudoti, kuriant pusiau kietų preparatų receptūras. / In order to prepare stable dispersive emulsion systems using low concentration of emulsifiers (0,1-0,4%) optimizing technological process, the use of new emulsifiers is investigated. Different kinds of stable emulsions can be prepared using polyacrylic acid polymers (Pemulen™ TR-1 and TR-2) while using low concentrations - 0,1-0,4% – environmentally non-toxic and human friendly universal o/w emulsion emulsifiers. Goal of this thesis - to analyse and evaluate the influence of polyacrylic acid polymer Pemulen™ TR-1 and Pemulen™ TR-2 and auxiliary substances nonionic surfactant Span 80 and Carbopol® Ultrez 20 for o/w emulsion stability and to use results of analysis in designing semi-solid formulas.

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. / This thesis presents an experimental study dedicated to characterise the hydraulic propertiesof free surface flows of complex fluids : viscoplastic fluids and mixtures made of viscoplasticfluids and grains. This study is motivated by the need to improve knowledge on properties ofthe flow of debris flows in a context of protection against natural hazards in the mountains.We have developed an original laboratory device - a channel with a mobile bottom - togenerate gravitary flows that are globally stationary in the laboratory frame. The flows have avery steep front followed upstream by a zone of uniform thickness. Viscoplastic fluids used(carbopol and kaolin) were selected so to model the matrix of natural mud flows, taking intoaccount the criteria of similarity adapted. These fluids follow a behavior law of Herschel-Bulkley, and their rheological properties were determined using a laboratory rheometer byproviding a particular care to the establishment of the associated uncertainties. We presentaccurate measurements of the evolution of the thickness of the flow in the uniform zone withthe the velocity speed of channel belt. These results are compared with theoretical predictionscorresponding to a steady uniform flow of a fluid of Herschel-Bulkley, and we show that theagreement is satisfactory through the uncertainties on the rheological measurements. We alsoanalyzed the shape of front, and here too, the agreement with hydraulic models (models likeSaint-Venant) is good. Both of the studies allowed to validate the hydraulic predictionsobtained from behavior laws measured with the rheometer. Finally, in a last section, wepresent a Preliminary study about the dynamics of isolated rigid particles placed in the flow,by paying attention to longitudinal velocities and falling velocities for different particle sizesand densities.

[pt] Este trabalho investiga o impacto de suspensões de grafeno funcionalizado sobre reologia de uma dispersão aquosa de Carbopol. Os derivados de grafeno usados foram óxido de grafeno (GO) e óxido de grafeno amino funcionalizado (AFGO). A variação da concentração e do grau de oxidação do grafeno funcionalizado foram avaliadas e relacionadas à reologia das suspensões. O GO foi produzido a partir da síntese de óxido de grafite pelo método de Hummers modificado, e caracterizado pelas técnicas de DRX, Raman, TGA, FTIR, XPS, TEM e AFM. O GO foi funcionalizado com trietilenotetramina por reação assistida por microondas para produzir AFGO, caracterizado por TGA e XPS. As suspensões foram caracterizadas por experimentos de potencial zeta e testes reológicos de escoamento em estado estacionário e oscilatório. A caracterização do GO mostra que grupos funcionais oxigenados foram incorporados em sua superfície grafítica. O GO oxidado por 96 horas (GO 96 h) apresentou maior distância interplanar e também apresentou menos camadas quando comparado com GO oxidado por 2 horas (GO 2 h). A caracterização do AFGO aponta que grupos aminados foram covalentemente ligados às nanofolhas GO e o GO com maior grau de oxidação produziu AFGO com maior nível de aminação. Todas as nanofolhas sintetizadas são coloidalmente estáveis quando suspensas em meio neutro. Todas as suspensões foram bem modeladas pela equação de Hershel-Bulkley. O aumento da concentração de nanofolhas nas suspensões prejudica a microestrutura do fluido e leva a uma diminuição da viscosidade, tensão de escoamento e elasticidade. O GO 96 h promoveu menor decréscimo na viscosidade, tensão de escoamento e elasticidade do que a suspensão GO 2 h. No caso do AFGO, o maior grau de aminação pode levar a uma queda mais pronunciada nas propriedades reológicas da suspensão. Para a suspensão com maior concentração de GO 96 h, observou-se o aparecimento de histerese em baixas taxas de cisalhamento. Esses resultados mostram que pequenas mudanças na superfície das nanofolhas de grafeno funcionalizado podem influenciar as respostas reológicas de um fluido não newtoniano. / [en] This work investigates the impact of functionalized graphene suspensions on the rheology of a Carbopol aqueous dispersion. The graphene derivatives used were graphene oxide (GO) and amino-functionalized graphene oxide (AFGO). The variation of the functionalized graphene concentration and oxidation was evaluated and related with the suspensions rheology. GO nanosheets were produced from synthesis of graphite oxide by modified Hummers method, and they were characterized by XRD, Raman,TGA, FTIR, XPS, TEM and AFM techniques. The GO was functionalized with triethylenetetramine by microwave assisted reaction to produce the AFGO, which was characterized by TGA and XPS techiniques. The suspensions were characterized by zeta potential experiments and rheological tests through steady-state and oscillatory flow. The GO characterization shows that oxygenated functional groups were incorporated in its graphitical surface. GO oxidized for 96 hours (GO 96 h) showed higher interplanar distance and also presented fewer layers when compared with GO oxidized for 2 hours (GO 2 h). The AFGO characterization points out that aminated groups were covalently attached to the GO nanosheets and the GO with a higher oxidation degree produced an AFGO with higher amination level. All synthesized nanosheets are colloidally stable when suspended at neutral media. All suspensions were well modeled by the Hershel-Bulkley equation. The increase of the nanosheets concentration in the suspensions impairs the level of fluid structure and leads to a decrease in viscosity, yield stress, and elasticity. The GO 96 h promoted a lower decrease in viscosity, yield stress and elasticity than the GO 2 h suspension. In the case of AFGO, the greater amination degree can lead to a more pronounced drop in the suspension rheological properties. For the suspension with a higher concentration of GO 96 h, it was observed the appearance of hysteresis at low shear rates. These results show that small changes in the graphene functionalized nanosheets surface can influence the rheological responses of a non-Newtonian fluid.