This thesis presents an investigation into the factors affecting the morphology of hybrid inorganic/organic photoactive layers used in photovoltaic cells. Although optimisation of the organic (polymer) phase has received substantial attention, research into the morphology of the inorganic phase (semiconducting nanocrystals) remains limited. It is believed that there is a strong link between the morphology of the final photoactive film and the quality of the initial nanocrystal dispersion. To this end, two nanocrystal systems were investigated; zinc oxide (ZnO) and lead sulphide (PbS). ZnO nanocrystals were synthesised and found to possess reproducible characteristics. It was determined that colloid stability was initially dependent upon the presence of acetate groups bound to the surface, which in turn required a small quantity of methanol to be present in the organic dispersant. It was also discovered that while methanol evaporated readily from the surface of the nanocrystals, another molecule, 1-propylamine (1-PA), did not. Further investigations showed that while methanol only weakly physisorbed to the surface of ZnO nanocrystals, 1-PA formed strong, dative covalent bonds with Zn2+, preventing evaporation despite a low boiling point. Subsequent investigations into the effects of different ligands upon colloid stability found that amine-based groups typically possessed superior stabilising capabilities compared to alcohol-based analogues. The characteristics of nanocrystal / polymer blends were also investigated. It was determined that the nanocrystal dispersion became unstable at higher concentrations of polymer due to depletion aggregation. Films of nanocrystal / polymer blends were cast from dispersions containing either alcohol or amine-based ligands, and it was observed that dispersions stabilised with 1-PA possessed smooth morphologies on the micrometer scale. Investigations at the nanometer scale, however, revealed aggregates large enough to favour recombination.The latter half of this thesis regards the characterisation of PbS nanocrystals and investigations into triggered aggregation. It was determined that while PbS nanocrystals possessed reproducible characteristics, the stabilising molecule, oleic acid (OA) was insulating. The effects of exchanging the OA groups for a shorter ligand, butylamine (BA) were investigated.Finally, PbS nanocrystals were treated with a bidentate ligand, 1,2-ethanedithiol (EDT) to induce triggered aggregation. It was observed that the system was highly sensitive to the concentration of EDT in dispersion, forming small, relatively dispersed aggregates at low [EDT], and micrometer-sized crystalline structures at high [EDT]. The characterisation and entrapment of these nanocrystal structures within semi-conducting polymer films is also discussed.

No description available.

Nous avons étudiés des fils quantiques dopés de semi-conducteurs gravés par spectroscopie de diffusion Raman. Nous avons observés les excitations du gaz d'électrons. Celles-ci présentent des règles de sélection différentes de celles établies pour les systèmes bi-dimensionnels. Nous avons montré théoriquement qu'elles proviennent de la modification de la structure du champ électromagnétique local provoquée par la géométrie particulière des fils gravés. Pour cela nous avons dû calculer le champ local et l'introduire dans la section efficace de diffusion Raman pour en déduire les règles de sélection de toutes les excitations. Cela a permis de déterminer sans équivoque la nature des excitations qui sont des plasmons. Aucune excitations à une particule ni fluctuations de densité de spin n'a été observées. Nous avons étudié l'évolution continue des dispersions de ces plasmons lorsque la largeur du fil est réduite de 1 micromètre à 30 nm. Jusqu'à 60 nm, celles-ci sont en très bon accord avec les résultats d'un modèle hydrodynamique. Au dessous de 60 nm, la comparaison avec un modèle RPA s'impose. Le plasmon intra-bande dispersif est observé jusqu'à 45 nm, largeur en dessous de laquelle les spectres Raman sont dominés par des excitations localisées qui nécessitent une analyse ultérieure pour en déterminer clairement leur nature. Nous montrons à l'aide du modèle RPA que nous avons atteint la limite quantique pour un fil de largeur 55 nm. Une gamme étroite de fils dont les largeurs sont comprises entre 55 nm à 45 nm permet donc l'étude de gaz strictement unidimensionnel.<br />Nous avons cherché à déterminer la contribution de la forte illumination dans les conclusions précédentes. Nous avons utilisé pour cela la spectroscopie de magnéto-transmission infra-rouge qui ne modifie pas les conditions d'équilibre du gaz d'électrons. Une largeur critique de 130 nm a été extraite, en dessous de laquelle nous n'avons plus aucun signe de la présence d'électrons libres. La comparaison des mesures Raman et infra-rouge a permis l'établissement et la validation d'un modèle microscopique du potentiel de confinement présent dans les fils. Enfin nous avons fabriqués des échantillons de géométries plus complexes. L'observation et l'analyse par diffusion Raman des plasmons dans ces fils a montré que nous pouvions contrôler la géométrie du potentiel confinant les électrons et a mis en évidence des effets nouveaux tels que le repliement et le confinement de plasmons unidimensionnels.

La conception en vue de la fiabilité (DFR, Design for Reliability) consiste à simuler le vieillissement électrique des composants élémentaires pour évaluer la dégradation d'un circuit complet. C'est dans ce contexte de fiabilité et de simulation de cette dernière, qu'une stratégie de conception en vue de la fiabilité a été développée au cours de ses travaux. Cette stratégie, intégrant une approche « système » de la simulation, s'appuie sur l'ajout de deux étapes intermédiaires dans la phase de conception. La première étape est une étape de construction de modèles comportementaux compacts à l'aide d'une méthodologie basée sur une approche de modélisation multi niveaux (du niveau transistor au niveau circuit) des dégradations d'un circuit. La seconde étape consiste alors l'analyse descendante de la fiabilité de ce circuit, à l'aide de simulations électriques utilisant ses modèles comportementaux dits « dégradables », afin de déterminer les blocs fonctionnels et/ou les composants élémentaires critiques de l'architecture de ce dernier, vis-à-vis d'un mécanisme de défaillance et un profil de mission donnés. Cette analyse descendante permet aussi d'évaluer l'instant de défaillance de ce circuit. Les dispersions statiques, lies au procédé de fabrication utilisé, sur les performances d'un lot de CIs ont aussi été prises en compte afin d'évaluer leur impact sur la dispersion des instants de défaillance des circuits intégrés. Ces méthodes ont été appliquées à deux mécanismes de dégradation : les porteurs chauds et les radiations. / Design for reliability (DFR) consists in assessing the impact of electrical ageing of each elementary component, using electrical simulations, on performance degradations of a full device. According to DFR concept and reliability simulation, theses works present a new DFR strategy. This strategy based on the integration of two intermediate phases in the ICs and SoC design flow. The first phase is a bottom-up ageing behavioural modelling phase of a circuit (from transistor level to circuit level). The second phase is a « top-down reliability analyses » phase of this circuit, performing electrical simulations using its ageing behavioural models, in order to determine critical functional blocks and / or elementary components of its architecture according to a failure mechanism and a given mission profile. Theses analyses also allow determining the failure time of this circuit. Statistical dispersions on ICs performances, due to the used manufacturing process, have been taking into account in order to assess their impact on failure time dispersions of a ICs lot. The method has been applied on two degradation mechanisms: hot carriers and radiations.

O escoamento líquido-líquido, em especial o escoamento óleo-água, vem atraindo a atenção de pesquisadores devido à alta demanda pelo combustível fóssil no atual cenário petrolífero mundial e nacional. Os desafios tecnológicos colocados pelas descobertas de reservas de óleos pesados e altamente viscosos consideram, em especial, a preocupação por minimizar as perdas energéticas nas linhas. Emulsões inversas ou dispersões óleo-em-água, na qual o óleo se encontra disperso de maneira uniforme em água, caracteriza-se pela baixa viscosidade aparente, tornando-se um tipo de emulsão desejável em algumas etapas do transporte de petróleo. Esses fatos tornam essencial o estudo deste tipo de padrão para o dimensionamento e operação ótima de dutos de produção de petróleo. Contudo, não existe ainda um número abrangente de trabalhos sobre padrão disperso líquido-líquido, ao comparar com escoamento em fases separadas. Trabalhos sobre dispersões têm reportado redução de atrito sem a adição de substâncias químicas em regime turbulento. No entanto, não há ainda um entendimento satisfatório do fenômeno. Na maioria dos trabalhos, sendo quase todos realizados com óleos leves e pouco viscosos, a redução é reportada em dispersões água-em-óleo, com escassos trabalhos reportando o fenômeno em dispersões óleo-em-água. A pesquisa realizada tratou do estudo experimental e teórico de dispersões óleo-em-água em tubulações. O escoamento foi caracterizado a partir da obtenção de dados de holdup, gradiente de pressão por fricção, distribuição das fases e padrão de escoamento. Uma teoria foi proposta para explicar a redução de atrito detectada neste trabalho, baseada na existência de um filme fino de água que escoa em contato com a parede do tubo, a baixos números de Reynolds, evitando o contato direto do núcleo turbulento (mistura bifásica) com a parede do tubo. O referido filme líquido foi detectado e quantificado utilizando-se técnica visual. Além disso, um modelo dinâmico baseado na teoria de lubrificação hidrodinâmica foi desenvolvido como tentativa de explicar a formação do filme líquido parietal no escoamento turbulento de dispersões óleo-água. / Liquid-liquid flow, especially oil-water flow, has attracted the attention of researchers due to the high demand for petroleum in the current global scenario. The discovery of reserves of heavy and highly viscous oils creates new challenges which are mainly concerned with reducing the significant pressure drop in pipes. Inverse emulsion or oil-in-water dispersions in which the oil is dispersed in water is characterized by its low effective viscosity, making it a desirable type of emulsion in some steps of oil production. These facts make the study of dispersed liquid-liquid flow essential for the design and optimal operation of oil pipelines. However, the studies on such flow pattern are scanty in comparison to those on separate flows, as stratified and annular flow patterns. Drag reduction in oil-water turbulent flow without the addition of any chemical substance has been reported in some studies. This phenomenon has received increasing attention in recent years, because there is not a satisfactory understanding of its dynamics yet. Most studies, almost all using light oils, report drag reduction in dispersion of water-in-oil, with few studies reporting the phenomenon in oil-in-water dispersions. This research comprises an experimental and theoretical study on oil-in-water dispersions in pipes. Pressure gradient, holdup, phase distribution and flow patterns data were obtained to characterize the two-phase flow. A theory was proposed to explain the drag reduction detected in this work, based on the existence of a thin water film flowing in contact with the pipe wall at low Reynolds numbers, avoiding contact between the turbulent core (mixture) and the pipe wall. The liquid film was detected and quantified using visual technique. In addition, a dynamic model based on the hydrodynamic lubrication theory was developed as an attempt to explain the formation of the liquid film.

Materiais nanoestruturados têm recebido destaque na comunidade científica, destacando-se, dentre eles, os nanocompósitos à base de polímeros e argila. Quando esses materiais são obtidos no estado líquido, ressalta-se também o uso de água em substituição a solventes orgânicos, devido a questões ambientais. Neste trabalho foram sintetizadas dispersões aquosas à base de poliuretanos (WPUs) e argila hidrofílica do tipo montimorilonita (MMT) de natureza sódica, com o objetivo de avaliar as propriedades de barreira a gases conferidas pela presença de argila e pela variação nas proporções entre os segmentos flexíveis poli(glicol propilênico) (PPG) e o copolímero em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG). Os monômeros empregados na síntese foram: poli(glicol propilênico) (PPG); copolímero em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG), com teor de 7% de EG; ácido dimetilolpropiônico (DMPA), diisocianato de isoforona (IPDI) e etilenodiamina (EDA), como extensor de cadeia. Foram sintetizadas dispersões aquosas com e sem a presença de argila, fixando-se a razão entre o número de equivalentes-grama de grupos diisocianato e hidroxila (razão NCO/OH) em 1,5. Nas formulações foi variado também o teor de argila em relação à massa de prepolímero em 0,5% e 1%. Foi adicionada uma etapa de agitação adicional com dispersor Turrax em algumas formulações. A argila foi previamente deslaminada em água deionizada e incorporada à formulação na etapa da dispersão do prepolímero. As dispersões foram avaliadas, quanto ao teor de sólidos totais, tamanho médio de partícula e viscosidade aparente. Os filmes vazados a partir das dispersões foram caracterizados por espectrometria na região do infravermelho (FTIR) e permeabilidade ao CO2. A resistência térmica dos filmes foi determinada por termogravimetria (TG). Foram observadas modificações nas propriedades dos filmes obtidos com a inserção da argila e com a variação no teor de segmentos à base de poli(glicol etilênico). A inserção da argila promoveu uma melhoria na resistência térmica das membranas bem como uma redução na permeabilidade das mesmas. Foi observado um aumento na permeabilidade das membranas obtidas a partir das formulações com maior percentual de copolímero (EG-b-PG), com e sem argila. / Nanostructured materials have been receiving increasing attention of scientific community, especially systems of nanocomposites based on polymer and clay. These materials can be obtained in aqueous state and the use of water, replacing organic solvents, is an important line of research due to environmental issues. In this work, dispersions based on waterbone polyurethanes and sodic hydrophilic clay montmorillonite (MMT) were synthesized, in order to evaluate the possible formation of nanocomposites (NWPUs). The monomers employed in the synthesis were: poly (propylene glycol) (PPG), block copolymer based on poly (ethylene glycol) and poly (propylene glycol) (EG-b-PG), containing 7% ethylene glycol; dimethylolpropionic acid (DMPA); isophorone diisocyanate (IPDI); and ethylenediamine (EDA) as chain extender. Aqueous dispersions with and without clay were synthesized by fixing the ratio between the equivalent-grams of diisocyanate and hydroxyl groups (NCO/OH ratio) in 1.5. The clay content also varied from 0.5% to 1% related to prepolymer initial mass. An additional stirring step with Turrax disperser was made in some formulations. The clay was previously delaminated in deionized water and incorporated at prepolymer dispersion in water-addition step. The dispersions were then evaluated in terms of solids content, particle size and apparent viscosity. The films cast from dispersions were characterized by infrared spectrometry (FTIR), thermogravimetry (TG) and permeability to CO2. Cast films were obtained and the gas barrier properties imparted by the clay were analyzed as well as the influence of poly (ethylene glycol) segments content. The insertion of clay imparted an improvement in thermal resistance properties and a decrease in membrane permeability. It was also observed an increase in permeability to CO2 of membranes obtained from formulations containing the higher amount of copolymer (EG-b-PG), independent of clay content.

En plus de la destruction des sites à proximités des volcans, l'accumulation de cendres volcaniques dans les zones distales peut causer de graves dommages. De plus l'évaluation de ces dangers n'est pas pleinement prise en compte dans les plans de mitigation actuels. L'étude de la dispersion des retombées pyroclastiques produites par les éruptions explosives des volcans Italiens lors du Quaternaire est le sujet de cette thèse. L'étude tephrostratigraphique de trois carottes lacustres des lacs de Shkodra et Ohrid (Albanie) et d'une carotte marine du Nord de la mer Ionienne a été réalisée. Dix-sept niveaux de tephra ont été corrélés aux éruptions explosives de A.D. 472, Avellino (3.9 cal. ka BP) du Vésuve, Monte Pilato (A.D.1200), Gabellotto-Fiumebianco (8.6 cal ka BP) et Monte Guardia (22 ka BP) de l'île de Lipari, FL (3.4 cal. ka BP) de l'Etna, Astroni (4.2 cal. ka BP), Agnano Monte Spina (4.5 cal. ka BP), Agnano Pomici Principali (12.3 cal. ka BP), SMP1-Y3 (31 ka) et l'Ignimbrite Campanienne-Y5 (39 ka) des Champs Phlégréens, X6 (107 ka) de la région Campanienne, et de P11 (131 ka) de l'île de Pantelleria. Cinq autres niveaux de tephra possèdent la composition que les dépôts de l'éruption vésuvienne de Mercato. Cela suggère une activité explosive entre les éruptions pliniennes de Mercato (8.9 cal ka BP) et Avellino (3.9 cal ka BP). Toutes ces données ont été intégrées, avec les données préexistantes de la littérature, dans la banque de données d'un SIG. Cette banque de données couplée à un SIG permet de grandement améliorer les dispersions des cendres et représente un outil qui améliore la mitigation des risques volcaniques dans la région centrale de la Méditerranée.

The potential applications of dispersed and self-assembled nanoparticles depend critically on accurate control and prediction of their phase behavior. The chemical potential is essential in describing the equilibrium distribution of all components present in every phase of a system and is useful as a building block for constructing phase diagrams. Furthermore, the chemical potential is a sensitive indicator of the local environment of a molecule or particle and is defined in a mathematically rigorous manner in both classical and statistical thermodynamics. The goal of this research is to use simulations and experiments to understand how particle size and composition affect the particle chemical potential of attractive nanoparticle-polymer mixtures. The expanded ensemble Monte Carlo (EEMC) simulation method for the calculation of the particle chemical potential for a nanocolloid in a freely adsorbing polymer solution is extended to concentrated polymer mixtures. The dependence of the particle chemical potential and polymer adsorption on the polymer concentration and particle diameter are presented. The perturbed Lennard-Jones chain (PLJC) equation of state (EOS) for polymer chains1 is adapted to calculate the particle chemical potential of nanocolloid-polymer mixtures. The adapted PLJC equation is able to predict the EEMC simulation results of the particle chemical potential by introducing an additional parameter that reduces the effects of polymer adsorption and the effective size of the colloidal particle. Osmotic pressure measurements are used to calculate the chemical potential of nanocolloidal silica in an aqueous poly(ethylene oxide) (PEO) solution at different silica and PEO concentrations. The experimental data was compared with results calculated from Expanded Ensemble Monte Carlo (EEMC) simulations. The results agree qualitatively with the experimentally observed chemical potential trends and illustrate the experimentally-observed dependence of the chemical potential on the composition. Furthermore, as is the case with the EEMC simulations, polymer adsorption was found to play the most significant role in determining the chemical potential trends. The simulation and experimental results illustrate the relative importance of the particles size and composition as well as the polymer concentration on the particle chemical potential. Furthermore, a method for using osmometry to measure chemical potential of nanoparticles in a nanocolloid-mixture is presented that could be combined with simulation and theoretical efforts to develop accurate equations of state and phase behavior predictions. Finally, an equation of state originally developed for polymer liquid-liquid equilibria (LLE) was demonstrated to be effective in predicting nanoparticle chemical potential behavior observed in the EEMC simulations of particle-polymer mixtures.

Cancer is the second leading cause of death in the United States and its onset is highly incident in the lungs, with very low long-term survival rates. Chemotherapy plays a significant role for lung cancer treatment, and pulmonary delivery may be a potential route for anticancer drug delivery to treat lung tumors. Coenzyme Q₁₀ (CoQ₁₀) is a poorly-water soluble compound that is being investigated for the treatment of carcinomas. In this work, we hypothesize that formulations of CoQ10 may be developed for pulmonary delivery with a satisfactory pharmacokinetic profile that will have the potential to improve a pharmacodynamic response when treating lung malignancies. The formulation design was to use a vibrating-mesh nebulizer to aerosolize aqueous dispersions of CoQ₁₀ stabilized by phospholipids physiologically found in the lungs. In the first study, a method was developed to measure the surface tension of liquids, a physicochemical property that has been shown to influence the aerosol output characteristics from vibrating-mesh nebulizers. Subsequently, this method was used, together with analysis of particle size distribution, zeta potential, and rheology, to further evaluate the factors influencing the capability of this nebulizer system to continuously and steadily aerosolize formulations of CoQ₁₀ prepared with high pressure homogenization. The aerosolization profile (nebulization performance and in vitro drug deposition of nebulized droplets) of formulations prepared with soybean lecithin, dimyristoylphosphatidylcholine (DMPC), dipalmitoylphosphatidylcholine (DPPC) and distearoylphosphatidylcholine (DSPC) were evaluated. The rheological behavior of these dispersions was found to be the factor that may be indicative of the aerosolization output profile. Finally, the pulmonary deposition and systemic distribution of CoQ₁₀ prepared as DMPC, DPPC, and DSPC dispersions were investigated in vivo in mice. It was found that high drug amounts were deposited and retained in the mouse lungs for at least 48 hours post nebulization. Systemic distribution was not observed and deposition in the nasal cavity occurred at a lower scale than in the lungs. This body of work provides evidence that CoQ₁₀ may be successfully formulated as dispersions to be aerosolized using vibrating-mesh nebulizers and achieve high drug deposition in the lungs during inhalation. / text

Cancer is the second leading cause of death in the United States and its onset is highly incident in the lungs, with very low long-term survival rates. Chemotherapy plays a significant role for lung cancer treatment, and pulmonary delivery may be a potential route for anticancer drug delivery to treat lung tumors. Coenzyme Q₁₀ (CoQ₁₀) is a poorly-water soluble compound that is being investigated for the treatment of carcinomas. In this work, we hypothesize that formulations of CoQ10 may be developed for pulmonary delivery with a satisfactory pharmacokinetic profile that will have the potential to improve a pharmacodynamic response when treating lung malignancies. The formulation design was to use a vibrating-mesh nebulizer to aerosolize aqueous dispersions of CoQ₁₀ stabilized by phospholipids physiologically found in the lungs. In the first study, a method was developed to measure the surface tension of liquids, a physicochemical property that has been shown to influence the aerosol output characteristics from vibrating-mesh nebulizers. Subsequently, this method was used, together with analysis of particle size distribution, zeta potential, and rheology, to further evaluate the factors influencing the capability of this nebulizer system to continuously and steadily aerosolize formulations of CoQ₁₀ prepared with high pressure homogenization. The aerosolization profile (nebulization performance and in vitro drug deposition of nebulized droplets) of formulations prepared with soybean lecithin, dimyristoylphosphatidylcholine (DMPC), dipalmitoylphosphatidylcholine (DPPC) and distearoylphosphatidylcholine (DSPC) were evaluated. The rheological behavior of these dispersions was found to be the factor that may be indicative of the aerosolization output profile. Finally, the pulmonary deposition and systemic distribution of CoQ₁₀ prepared as DMPC, DPPC, and DSPC dispersions were investigated in vivo in mice. It was found that high drug amounts were deposited and retained in the mouse lungs for at least 48 hours post nebulization. Systemic distribution was not observed and deposition in the nasal cavity occurred at a lower scale than in the lungs. This body of work provides evidence that CoQ₁₀ may be successfully formulated as dispersions to be aerosolized using vibrating-mesh nebulizers and achieve high drug deposition in the lungs during inhalation.