The synthesis of mesoporous silica thin films using surfactant templating typically leads to an inaccessible pore orientation, making these films not suitable for membrane applications. Recent advances in thin film synthesis provide for the alignment of hexagonal pores in a direction orthogonal to the surface when templated on chemically neutral surfaces. In this work, orthogonal thin film silica membranes are synthesized on alumina supports using block copolymer poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123) as the template. The orthogonal pore structure is achieved by sandwiching membranes between two chemically neutral surfaces, resulting in 90 nm thick films. Solvent flux of ethanol through the membrane demonstrates pore accessibility and suggests a silica pore size of approximately 10 nm. The permeability of ions and fluorescently tagged solutes (ranging from 4,000 to 70,000 Da) is used to demonstrate the membrane’s size selectivity characteristics. A size cut off occurs at 69,000 Da for the model protein BSA. By functionalizing the silica surface with a long chained alkyl group using n-decyltriethoxysilane (D-TEOS), the transport properties of the membranes can be altered. Contact angle measurements and FTIR results show the surface to be very hydrophobic after functionalization. Solvent flux of ethanol through the silica thin film membrane is similar before and after functionalization, but water flux decreases. Thin film silica membranes show much promise for applications in catalysis, bio-sensing, and affinity separations.

Le transport réactif des NPs en milieu poreux regroupe trois principaux processus : l'agrégation, le dépôt et le transport des NPs. Le système réel est caractérisé par la complexité et l'interdépendance de ces trois processus. En plus, ces derniers ne possèdent pas forcément la même échelle propre d'étude ou de modélisation. Cela explique la difficulté majeure pour décrire simultanément tous ces processus couplés et interdépendants dans un seul modèle aisément utilisable. Au départ, nous avons simplifié ce système en séparant les différents processus. Ensuite, nous résolvons le problème d'échelle, par l'approche d'homogénéisation ou par l'approche multi-échelles. La séparation du problème, en plusieurs processus et sur plusieurs échelles d'espace, facilite la résolution numérique et la compréhension des processus élémentaires. Dans cette étude, une approche multi-échelles a été développée pour modéliser ces trois processus (l'agrégation, le dépôt et le transport des NPs), chacun dans sa propre échelle. Nous avons considéré deux échelles de taille, l'échelle microscopique ou d'interface (nanométrique), et l'échelle mésoscopique correspondant à la taille des pores (micrométrique). A l'échelle microscopique, les processus d'agrégation et de dépôt ont été modélisés, de manière similaire, avec la théorie DLVO. Les propriétés électrostatiques de surface des NPs ou de la roche sont décrites par un modèle de complexation de surface développé sous PhreeqC. Ce modèle d'interface est testé pour deux types de matériaux, le titane pour les NPs et la silice pour la roche. A l'échelle mésoscopique, le dépôt est quantifié par la théorie classique de la filtration (CFT : Classical Filtration Theory) dans la phase initiale où le filtre est propre. Le processus de transport a été simulé par un modèle de réseau de pores (PNM : Pore Network Model) à l'échelle mésoscopique. Ce modèle de transport est couplé avec le modèle d'agrégation-dépôt et indirectement avec le modèle de complexation de surface en un seul modèle appelé PhreeqC Pore Network Transport(PPNT1.0).

In this work a model for the wetting and swelling of pores with water within a Nafion membrane is developed. This model is based on minimizing all contributions to the total free energy of the proposed system. We find that equilibrium state depends on entropic mixing forces and energetic surface forces. The wetting of the pore relies on the entropic forces exceeding the energetic forces. Specifically this indicates a critical pore size in which liquid is the favorable state. If the pore fills with liquid it will swell until balanced by the energy of the deforming membrane. Several factors including pressure relative to saturation and the phase which hounds the membrane are shown to dramatically affect the final equilibrium state of the system.

A complexidade de desenvolver novas tecnologias para aplicações em reconstituição óssea se deve à necessidade de combinar várias propriedades químicas e físicas para que o material proporcione o desempenho almejado. Particularmente, em aplicações que visam osteogênese, os enxertos sintéticos devem ser bioativos, possuir porosidade com volume, geometria e interconectividade de poros controlados, além de ter boas propriedades mecânicas, dentro de limites relativamente rígidos. Por essa razão, o recobrimento de materiais bioinertes com cerâmicas bioativas se tornou o foco da presente pesquisa. O objetivo desse estudo foi desenvolver um novo método de produção de enxertos cerâmicos com macroporosidade funcionalizada, onde a formação e o revestimento dos poros são realizados em uma única etapa. Foi realizado o estudo de recobrimento com vidro bioativo e fosfato de cálcio. Para isso, agentes porogênicos na forma de grânulos (de 600 &#956m a 2 mm de diâmetro) foram sintetizados pelo método da gelificação de uma solução aquosa de alginato de sódio gotejada em solução de nitrato de cálcio (0,5 M), com incorporação de outros elementos para a formação de biovidro ou fosfato de cálcio. Esses grânulos foram conglomerados a um vidro ou alumina em pó, formando um compósito, que foi tratado termicamente para sinterização e formação de poros. No caso da matriz vítrea, a sinterização ocorreu com cristalização simultânea e concorrente. As cerâmicas resultantes foram caracterizadas por microscopia óptica e eletrônica de varredura, sendo possível observar a formação de macroporos aproximadamente esféricos (de 600 &#956m a 2 mm de diâmetro) revestidos internamente por uma camada de material com possível composição bioativa. / A tough requirement in the manufacture of implants for medicine is to conciliate appropriate mechanical properties and the porosity necessary for bone ingrowth. It is further important to control the fraction, morphology, size, surface to volume ratio and interconnectivity of pores. The difficulty in matching these characteristics is a deterrent for practical applications. High strength materials coated with a bioactive layer can overcome this problem. Therefore, the aim of the present study was to develop a new method for production of implants with functionalized macro porosity on ceramic. The production of a porous glass-ceramic and the internal coating of the pores with a bioactive material were performed in situ. The bioactive glass coating and calcium phosphate coating were studied. In order to achieve this goal, a porogenic agent in the form of beads (from 600 &#956m to 2 mm diameter) were prepared by the gelation of a water solution of sodium alginate into calcium nitrate solution (0.5 M), and incorporation of other components to yield the Bioglass composition or a calcium phosphate. The beads were further mixed with glass or ceramic powder and the assembly was heat treated for sintering. In the case of glass, the sintering occurred with concurrent crystallization. The obtained ceramics were characterized by optical and scanning electronic microscopy, which indicated that the porogenic beads acted successfully as a sacrificial template to produce functionalized macro pores.

Neste trabalho estudou-se a encapsulação de proteínas com diferentes pesos moleculares na sílica mesoporosa ordenada SBA-15 para avaliar sua aplicação como adjuvante imunológico. Para tanto, as proteínas IgG (150 kDa) e BSA (66,5 kDa) foram incorporadas à sílica mesoporosa com poros expandidos. Primeiramente estudou-se a dilatação dos poros utilizando-se um agente dilatador de estrutura no processo de síntese, através da preparação de amostras com diferentes quantidades de triisopropilbenzeno (TIPB). Resultados de isoterma de adsorção de nitrogênio (NAI) e espalhamento de raios X a baixo ângulo (SAXS) revelaram um aumento no diâmetro médio de poros da ordem de 23% e uma rede de poros mais desordenada. Para se ter uma estimativa das dimensões das proteínas, medidas de SAXS foram feitas e indicaram que ambas têm dimensões que permitiriam sua incorporação nos poros da SBA-15. As amostras com poros dilatados foram então utilizadas para a incorporação das proteínas IgG e BSA em solução tampão fosfato salina (PBS). Os resultados indicaram o preenchimento dos microporos pela solução de PBS com valor superior a 95%. Quanto ao preenchimento de mesoporos, observou-se maior variação no volume de poros e área superficial, para o material com maior diâmetro médio de poros, atingindo valores em torno de 80 % e 90%, respectivamente. Não houve diferença significativa nestas porcentagens entre a incorporação das duas proteínas, indicando que as proteínas devem estar encapsuladas na macroporosidade da sílica, obstruindo a entrada dos mesoporos. Um modelo teórico foi utilizado para analisar as medidas de SAXS e ele confirmou o preenchimento dos microporos e a presença da proteína nos mesoporos da sílica. Utilizando a técnica analítica de Particle Induced X-ray Emission (PIXE), o conteúdo de silício em fezes de camundongos isogênicos foi avaliado em função do tempo, com o intuito de analisar a liberação de sílica pelo organismo dos camundongos. Observou-se que após a primeira administração de sílica os camundongos inoculados por via oral liberaram uma quantidade de silício similar à liberada pelos camundongos controle, que receberam apenas a solução de PBS. Após a segunda administração os camundongos inoculados com sílica por via oral liberaram uma quantidade de silício superior à dos camundongos controle, devido à morte dos macrófagos e outras células que atuam na resposta imunológica, evidenciando a eliminação de silício pelo organismo. Um estudo paralelo de controle de qualidade foi realizado em amostras de SBA-15 preparadas pela Cristália Produtos Químicos Farmacêuticos Ltda. a fim de garantir a reprodutibilidade deste material, que será comercialmente utilizado para a formulação de vacina oral contra Hepatite B, produzida pelo Instituto Butantan. Os resultados mostraram propriedades texturais reprodutíveis das amostras produzidas pela Cristália indústria farmacêutica. / In this work we studied the encapsulation of proteins with different molecular weights into SBA-15 ordered mesoporous silica to evaluate its application as immunological adjuvant. Hence, the IgG protein (150 kDa) and BSA (66.5 kDa) were incorporated into the mesoporous silica with expanded pores. First we studied the expansion of the pores using a structure swelling agent in the synthesis process, by preparing samples with different amounts of triisopropylbenzene (TiPB). Results of Nitrogen Adsorption Isotherm (NAI) and Small Angle X-Ray Scattering (SAXS) showed an increase in average pore diameter of the order of 23% and a more disordered pore network. To provide an estimate of the size of proteins, SAXS measurements were performed and indicated that both have dimensions that allow its incorporation in the pores of SBA-15. These samples were used for the incorporation of IgG and BSA proteins in phosphate buffered saline (PBS) solution. The results indicated a filling of the micropores by PBS solution larger than 95%. Concerning the filling of mesopores, we observed a larger variation in pore volume and surface area for the material with highest average pore diameter, reaching values around 80% and 90%, respectively. There was no significant difference in these percentages between the incorporation of the two proteins, indicating that the proteins could be encapsulated in the silica macroporosity, blocking the entry of mesopores. A theoretical model was used to analyze the SAXS measurements and it confirmed the filling of micropores and the presence of protein in the silica mesopores. Using the analytical technique \"Particle-Induced X-ray Emission\"(PIXE), the silicon content in mice feces was evaluated as a function of time, in order to analyze the release of silica from the organism of the mice. We observed that after the first silica administration the isogenic mice inoculated by oral administration released a similar amount of silicon compared with the amount released by the isogenic control mice, which received only PBS solution. After the second oral administration, the mice inoculated with silica released a higher amount of silicon than the control mice, due to the death of macrophages and other cells that act on the immune response, indicating the elimination of silicon by the organism. A parallel study about quality control was performed on SBA-15 samples prepared by Cristália Produtos Químicos Farmacêuticos Ltda., to ensure the reproducibility of this material which will be used commercially for the formulation of an oral vaccine against hepatitis B, produced by the Butantan Institute. The results showed reproducible textural properties of the samples produced by the Cristália pharmaceutical industry.

O gênero Aegla Leach, 1820 representa o único táxon dentro de Decapoda Anomura com representantes adaptados exclusivamente a ambientes de água doce. As eglas são endêmicas da América do Sul e vivem em ambientes lóticos com alto nível de oxigenação. Estudos comparativos da morfologia de jovens recém-eclodidos podem contribuir para estabelecer relações de afinidade entre as cerca de 70 espécies já descritas que compõem a família Aeglidae. Porém, o número de trabalhos que descrevem a morfologia em detalhe nesta fase de vida é ainda escasso. O objetivo do presente estudo foi descrever detalhadamente a morfologia externa dos jovens recém-eclodidos das espécies Aegla paulensis e Aegla perobae, com base em Microscopia Óptica e em Microscopia Eletrônica de Varredura (MEV). Fêmeas ovígeras foram coletadas e transferidas para o laboratório a fim de se obter os jovens recém-eclodidos dos ovos. A descrição detalhada da morfologia do jovem recém-eclodido incluiu a carapaça, o abdome, os apêndices cefalotorácicos (antênula, antena, mandíbula, maxílula, maxila, maxilípedes, pereópodes) e a região do télson juntamente com os urópodes. As cerdas foram analisadas em detalhe quanto ao número, localização e tipo morfológico com o auxílio da MEV. Os resultados obtidos foram analisados e comparados com os das espécies que já tiveram seus jovens recém-eclodidos descritos e também com os adultos. As principais descobertas do estudo foram: as lineae aeglicae, os pleópodes rudimentares, a riqueza de tipos de cerdas e os poros sensoriais / Genus Aegla Leach, 1820 represents the one taxon within Decapoda Anomura with representatives exclusively adapted to freshwater environments. Aeglids are endemic to South America and they live in lotic environments with high levels of dissolved oxygen. Comparative studies of the newly-hatched juvenile morphology may contribute to establish affinity relations among the 70 species of the Aeglidae family already described. However, the number of studies which describe the morphology at this life phase in detail is still scarce. The objective of this study was to describe the external morphology of the newly-hatched juvenile of Aegla paulensis and Aegla perobae in detail, using Light Microscopy and Scanning Electron Microscopy (SEM). Newly-hatched juveniles were obtained from ovigerous females kept under laboratory conditions. Detailed description of the newly-hatched juveniles included the carapace, the abdomen, the cephalothoracic appendages (antennule, antenna, mandible, maxillule, maxilla, maxillipeds, pereiopods), and the telson-uropods region. SEM was used to analyze setae number, location and type. The results were analyzed and compared with those from newly-hatched juveniles already described and with adults. The main findings in this study were: lineae aeglicae, rudimentary pleopods, setae morphology diversity, and pores sensilla.

Des gammes de membranes en poly(étherimide) (PEI) fonctionnalisées avec des tailles de pores contrôlées ont été préparées en se basant sur deux étapes successives : élaboration des membranes UF de seuil de coupure (MWCO) de 120 ± 10 kDa par la technique inversion de phase induite par la coagulation dans l'eau suivie d'un traitement de surface par une solution aqueuse contenant des oligomères aminés. Une modification avec un dérivé monoaminé commercial, le Jeffamine M-2070, a donné des membrane recouvertes de brosses de courtes chaines de poly(éthylèneglycol) (PEG-PEI) qui ont rendu la membrane plus hydrophile et plus résistante au colmatage par le BSA avec un taux de récupération de flux de l'ordre de 80 à 93 % (traitement de 1 à 3 h). Le MWCO des membranes PEG-PEI traitées plus que 3 h augmente progressivement pour atteindre 500 kDa après 5 h de traitement. D'autre part, une réaction avec des oligomères de poly(éthylèneimine) a donné des membranes chargées positivement (Cat-PEI) en rétrécissant la taille des pores pour atteindre des gammes de membranes d'UF serrée et de NF. Des membranes Cat-PEI de NF de MWCO de l'ordre de 300-500 Da sont adaptées au dessalement avec par un ordre de rétention décroissant de sels simples de CaCl2 > NaCl > MgSO4 > Na2SO4. La forte rétention des ions Ca2+ (plus que 90 %) rend ces membranes très efficaces pour l'adoucissement d'eau (diminution de la dureté d'une eau du robinet de 37 à 7°F). Les membranes Cat-PEI ont montré aussi, une bonne rétention des acides aminés basiques (plus que 80 % pour l'Arginine et la Lysine) à un pH entre 3 et 6. Ainsi une sélectivité expérimentale de l'ordre de 20 a été obtenue pour des mélanges d'acide glutamique et d'arginine avec des membranes de MWCO entre 500 et 750 Da. / Functionalized poly(etherimide) (PEI) membranes with controlled pore size were prepared based on two steps : preparation of UF membranes with a molecular weight cut-Off (MWCO) of 120 ± 10 kDa by phase inversion induced by coagulation in water followed by a surface treatment with an aqueous solution containing amino oligomers. Modification with a commercial monoamine derivative, Jeffamine M-2070, gave membranes (PEG-PEI) coated with brushes of poly (ethylene glycol) short chains that made the membrane more hydrophilic and more resistant to fouling by BSA with a recovery flow rate of of 80 to 93 % (treatment of 1 to 3 h). The MWCO of PEG-PEI membranes treated more than 3 h became progressively larger and reached 500 kDa after 5 h of treatment. On the other hand, reaction with oligomers of poly (ethyleneimine) gave positively charged membranes (Cat-PEI) by narrowing the pore size yielding tight UF and NF membranes. Cat-PEI NF membranes with MWCO of about 300-500 Da are suitable for desalination with a retention order of decreasing simple salts CaCl2> NaCl> MgSO4> Na2SO4. The high retention of Ca2+ ions (more than 90%) make Cat-PEI effective membranes for softening water (reducing the hardness of tap water from 37 to 7 °F). In addition, Cat-PEI membranes showed a good retention of basic amino acids (more than 80% for arginine and lysine) at pH between 3 and 6. Thus, an experimental selectivity of about 20 was obtained for a glutamic acid and arginine mixture using Cat-PEI membranes with a MWCO between 500 and 750 Da.

This research presents the results on an experimental investigation to identify the effects of rebar temperature, fly ash and water to cement ratio on concrete porosity in continuously reinforced concrete pavements (CRCP). Samples were cast and analyzed using pullout tests. Water to cement ratio (w/c) and rebar temperature had a significant influence on the rebar-concrete bond strength. The 28-day shear strength measurements showed an increase in rebar-concrete bond strength as the water to cement ratio (w/c) was reduced from 0.50 to 0.40 for both fly ash containing and non fly ash control samples. There was a reduction in the peak pullout load as the rebar surface temperature increased from 77o F to 150o F for the cast samples. A heated rebar experiment was performed simulating a rebar exposed to hot summer days and the rebar cooling curves were plotted for the rebar temperatures of 180o F - 120o F. Fourier transform infrared spectroscopy was performed to show the moisture content of cement samples at the rebar-concrete interface. Mercury intrusion porosimetry test results on one batch of samples were used for pore size distribution analysis. An in-depth analysis of the morphological characteristics of the rebar-concrete interface and the observation of pores using the scanning electron microscope (SEM) was done.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

No description available.