L'objectif du travail de thèse est d'étudier les effets de température et du dopage sur les caractéristiques de gravure du Si et des polymères : produits de réaction, cinétiques, énergie d'activation, anisotropie, et sélectivité. La gravure anisotrope des polymères est ensuite étudiée en fonction de la température en utilisant des mélanges de gaz permettant d'utiliser un procédé par passivation latérale. Les résultats expérimentaux obtenus sont discutés en tenant compte de l'étude thermodynamique des systèmes chimiques concernés. Le travail s'achève par l'étude de faisabilité de filtres pour microfiltration par perçage de pores à travers des films polymère.

The main objective of this research was to exploit the interrelations between the rheological behavior and nano-microstructure of complex fluids in solving two state-of-the-art problems, one in the field of biomedical engineering: controlling the amount and characteristics of bioaerosol droplets generated during coughing, and the other in the bitumen-heavy oil industry: characterizing the nano-microstructure of asphaltene particles in bitumen and heavy oil from their rheological behavior. For the first problem, effect of viscoelastic and surface properties of artificial mucus simulant gels on the size distribution and amount of airborne bioaerosol droplets generated during simulated coughing were investigated. The results revealed that suppressing the generation of bioaerosol droplets and/or reducing the number of emitted droplets to a minimum during coughing are practically achievable through modulation of mucus viscoelastic properties. While variation of surface tension did not show any change in the droplet size distribution, an increase in particle size was observed as the samples changed from elastic solid type to viscoelastic type to viscous fluid type samples. This knowledge will help in the development of a new class of drugs being developed at the University of Alberta, aimed at controlling the transmission of airborne epidemic diseases by modifying the viscoelastic properties of mucus. For the second problem, studies of viscoelastic behavior of Athabasca bitumen (Alberta) and Maya crude (Mexico) oil samples, along with their Nano-filtered and chemically separated-plus-reconstituted samples were performed. The results revealed that the rheological behaviors of the bitumen-heavy oil samples are governed by their multiphase nature. The rheological behavior of all feeds, permeates and retentate samples followed a single master curve over the entire temperature interval, consistent with that of a slurry comprising a Newtonian liquid plus a dispersed solid comprising non-interacting hard spheres. The behavior of asphaltenes in the reconstituted samples, however, was found to be significantly different from that in nanofiltered samples. The information about the characteristics and behaviors of asphaltenes obtained in this study will help better understand the asphaltene structures, and support the effort to determine solutions for numerous asphaltene-related industrial problems. In the long run, this knowledge will help to create more efficient extraction and upgrading processes for bitumen and heavy oils. / Thermo Fluids

Le but de cette thèse est d'étudier l'influence des propriétés d'une suspension colloïdale sur l'efficacité du procédé d'ultrafiltration appliqué au traitement de l'eau. Pour cela, les expériences, détaillées dans une première partie, sont menées avec une suspension colloïdale d'argile contenant des électrolytes. Les propriétés physico-chimiques d'un tel mélange font l'objet du deuxième chapitre où la stabilité de la suspension est définie à travers la théorie DLVO, c'est à dire en considérant les interactions électrostatiques. Le troisième chapitre analyse l'influence de la stabilité de la suspension sur le colmatage de la membrane. Des modélisations permettent d'expliciter physiquement ces résultats en prenant en compte l'influence des interactions électrostatiques sur les mécanismes de transfert qui régissent l'ultrafiltration: la cinétique de dépôt et la résistance hydraulique du dépôt. L'étape de décolmatage de la membrane après les filtrations est exposée dans un quatrième chapitre. Une cinquième partie présente le rejet de sel engendré par le dépôt de colloïdes. Ce phénomène est décrit par les répulsions électrostatiques entre les ions et les surfaces chargées du colloïde. En conclusion, cette thèse présente donc plus généralement l'influence de la stabilité d'une suspension ou des interactions électrostatiques sur l'ensemble des mécanismes de transfert intervenant lors du colmatage d'une membrane d'ultrafiltration par un colloïde.

The market for polyamide desalination membranes is expected to continue to grow during the coming decades. Purification of alternative water sources will also be necessary to meet growing water demands. Purification of produced water, a byproduct of oil and gas production, is of interest due to its dual potential to provide water for beneficial use as well as to reduce wastewater disposal costs. However, current polyamide membranes are prone to fouling, which decreases water flux and shortens membrane lifetime. This research explored surface modification using poly(ethylene glycol) diglycidyl ether (PEGDE) to improve the fouling resistance of commercial polyamide membranes. Characterization of commercial polyamide membrane performance was a necessary first step before undertaking surface modification studies. Membrane performance was found to be sensitive to crossflow testing conditions. Concentration polarization and feed pH strongly influenced NaCl rejection, and the use of continuous feed filtration led to higher water flux and lower NaCl rejection than was observed for similar tests performed using unfiltered feed. Two commercial polyamide membranes, including one reverse osmosis and one nanofiltration membrane, were modified by grafting PEGDE to their surfaces. Two different PEG molecular weights (200 and 1000) and treatment concentrations (1% (w/w) and 15% (w/w)) were studied. Water flux decreased and NaCl rejection increased with PEGDE graft density ([microgram]/cm2), although the largest changes were observed for low PEGDE graft densities. Surface properties including hydrophilicity, roughness and charge were minimally affected by surface modification. The fouling resistance of modified and unmodified membranes was compared in crossflow filtration studies using model foulant solutions consisting of either a charged surfactant or an oil in water emulsion containing n-decane and a charged surfactant. Several PEGDE-modified membranes demonstrated improved fouling resistance compared to unmodified membranes of similar initial water flux, possibly due to steric hindrance imparted by the PEG chains. Fouling resistance was higher for membranes modified with higher molecular weight PEG. Fouling was more extensive for feeds containing the cationic surfactant, potentially due to electrostatic attraction with the negatively charged membranes. However, fouling was also observed in the presence of the anionic surfactant, indicating hydrodynamic forces are also responsible for fouling. / text

No description available.

La problématique de l'élimination de l'excès d'ions fluorure présents dans les eaux de forage destinées à la consommation humaine peut être résolue en utilisant plusieurs méthodes. Dans cette thèse, les procédés testés sont : l'adsorption sur des particules d'os de seiche, l'adsorption sur des particules de calcite en présence d'acide acétique, la nanofiltration et l'échange d'ions. L'objectif est d'optimiser les différents procédés pour des solutions modèles en ions fluorure, puis de réaliser pour ces conditions optimales le traitement d'une eau de forage tunisienne. La concentration limite en ions fluorure imposée par la WHO est de 1.5 mg.L-1. Les essais d'adsorption en utilisant l'os de seiche, disponible en Tunisie, sont simples à mettre en œuvre et permettent des traitements à petite échelle avec des coûts très compétitifs en utilisant un matériau non toxique. La défluoration de l'eau souterraine avec l'os de seiche présente une concentration résiduaire en fluorure de 1,3 mg.L-1 (TR = 61,5%). Dans le cas de la précipitation des ions fluorures sous forme de fluorite suivi de microfiltration, l'addition d'acide acétique aux particules de calcite (CaCO3) favorise l'élimination des ions fluorure. La défluoration de l'eau souterraine montre que l'eau traitée présente une concentration résiduaire en fluorure de 1,24 mg.L-1 (TR = 53,7%). En utilisant une résine échangeuse d'ions Purolite A520E, la défluoration de l'eau souterraine montre que l'eau traitée présente une concentration résiduaire en fluorure de 1,2 mg.L-1 (TR = 54%). La nanofiltration permet de traiter des volumes importants d'eau et les taux de rétention des ions fluorure sont satisfaisants (88% et 57%)

Over 18 billion barrels of waste fluids are generated annually from oil and gas production in the United States. As a large amount of water is used for oilfield operations, treating and reusing produced water can cut the consumption of fresh water in well sites. This research has helped to develop a membrane process train for a mobile produced water treatment unit for treating oilfield produced brine for reuse. To design the process train, over 30 sets of combination tests at pilot laboratory scale were performed using pretreatment, microfiltration and nanofiltration processes. Membrane performance was selected based on high flux separation efficiency, high tolerance for solids and fluid treatments. Over 95 % solids rejection and greater than 80 % oil removal efficiency were obtained in all these tests. Process train (pre-treatment and membrane) performance was monitored by chemical analysis of permeate and models fitting experimental data for the process. From the results, hydrocarbon rejection was analyzed; total organic carbon rejection was 47.9 %, total carbon content averaged 37.3 % rejection and total inorganic carbon rejection was at 3.66 %. BTEX removal efficiency ranged from 0.98 % to 52.7 % with the progressive pretreatment methods of using cartridge filters. The nanofiltration membrane showed significant reduction in total dissolved solids and in both anionic and cationic species. The process train is seen to follow a sequence of treatment from cartridge and oil removal filter treatment to microfiltration treatment to ultrafiltration, followed by nanofiltration for the purpose of this research. Further research still needs to be done on to determine the kind of analytical test which will give real time feedback on effectiveness of filters. In summary, the process train developed by TAMU-GPRI possesses distinct advantages in treating oilfield produced brine using membrane technology. These advantages include high quality of permeate, reduced sludge and the possibility of total recycle water systems. The small space requirement, moderate capital costs and ease of operation associated with the use of the mobile unit membrane technology also makes it a very competitive alternative to conventional technologies.

Per- and polyfluoroalkyl substances (PFASs) is a group of man-made, highly persistent chemicals. Due to the specific surface-active attributes of these molecules, applications are numerous and feed an economically important industry. During the last decade, PFASs have been detected globally in the environment, living organisms and tap water. The combination of toxic properties and high bioaccumulative potential, together with the discovery that conventional water treatment methods do not remove PFAS, renders further research on purification methods highly needed.  Three techniques of purifying water from PFASs were examined. Nanofiltration technology (NF) is a membrane filtration technique, which produces a purified product (the permeate) by generating an effluent of high contaminant concentration (the reject water). To decontaminate the reject water, adsorption by granular activated carbon (GAC) or anion exchange (AE) have been proposed. The efficiency of these three technologies was studied at Bäcklösa drinking water treatment plant (DWTP) in Uppsala. A nanofiltration pilot with two 270NF membranes (Dow Filmtech™), connected in series, was used. A high removal efficiency (>90%) was found for all PFASs. Furthermore, it was confirmed that the concentration in the permeate water was a function of the concentration in the incoming raw water; increased PFAS raw water concentration resulted in increased PFAS permeate concentration. Size-exclusion and electrostatic repulsion were deemed important mechanisms. For the comparison of GAC (Filtrasorb 400®) and AE (Purolite® A-600), a column experiment was set up. The perfluoroalkane (-alkyl) sulfonic acids (PFSAs) and perfluorooctanesulfonamide (FOSA) had similar removal efficiencies using both GAC and AE, and the efficiency increased with increasing chain length. AE was found to have a higher average removal efficiency of perfluoroalkyl carboxylic acid (PFCAs) (62-95%) than GAC (49-81%). In conclusion, longer chain length PFASs were removed more effectively than shorter-chained, and the PFSAs and FOSA showed higher removal efficiency compared to the PFCAs. Furthermore, linear isomers were removed more effectively than branched for GAC and AE. In contrast, the opposite was found for the NF membrane, where branched isomers were better retained. / Per- och polyfluorerade alkylsubstanser (PFAS) är en grupp syntetiska, ytterst persistenta kemikalier. På grund av deras ytaktiva egenskaper är de lämpliga för användning i många produkter och tillverkningsprocesser, och är således viktiga för en ekonomiskt betydande industri. Under det senaste årtiondet har PFAS påträffats i miljön, levande organismer och kranvatten världen över.  Kombinationen av toxiska egenskaper, en hög bioackumuleringspotential och upptäckten att konventionella reningsmetoder inte avlägsnar substanserna från vatten, gör att vidare forskning av reningsmetoder för PFAS är mycket angelägen. Tre reningsteknikers förmåga att rena vatten från PFAS undersöktes. Nanofiltrering (NF) är en membranfiltreringsteknik som utöver den renade produkten, permeatet, även framställer en biprodukt av hög föroreningsgrad, rententatet. För att rena rententatet har adsorption till granulärt aktivt kol (GAC) eller jonbytarmassa (AE) föreslagits. Teknikerna utvärderades på Bäcklösa Vattenverk i Uppsala.  Nanofiltreringen undersöktes i en pilotanläggning där två 270NF (Dow Filmtech™) membran var seriekopplade. En hög reningsgrad (>90%) konstaterades för alla typer av PFAS. Vidare visades PFAS-koncentrationen i permeatet vara en funktion av PFAS-koncentrationen i råvattnet; en ökad råvattenkoncentration gav en ökad permeatkoncentration. Storleksseparation och elektrostatisk repulsion befanns vara viktiga mekanismer som påverkade reningsgraden. För att undersöka de mekanismer som påverkar PFAS-adsorption jämfördes GAC (Filtrasorb 400®) och AE (Purolite® A-600) i ett kolonnexperiment. Reningsgraden för GAC och AE av perfluorerade sulfonsyror (PFSA) och perfluorooktan sulfonamider (FOSA) var lika hög och reningseffektiviteten ökade med ökande kolkedjelängd. AE återfanns ha en högre genomsnittlig reningsgrad av perfluorkarboxylsyror (PFCA) (62-95%) än GAC (49-81%). Sammanfattningsvis avlägsnades PFAS av längre kolkedjelängd mer effektivt än kortare kolkedjor, och PFAS med sulfonsyror och sulfonamider som funktionella grupper uppvisade en högre reningsgrad än karboxylsyrorna. Vidare renades linjära isomerer mer effektivt än grenade både genom GAC och AE. Däremot konstaterades det motsatta för NF-membranen, där grenade isomerer renades mer effektivt. / SafeDrink

As atividades humanas em bacias hidrográficas introduzem nos cursos de água nutrientes que aceleram o processo natural de eutrofização, favorecendo a ocorrência de florações de algas e cianobactérias. Estas florações se caracterizam por um crescimento explosivo destes microrganismos. Entre os diversos impactos negativos trazidos pelas florações está a emissão potencial dos compostos 2-metilisoborneol (MIB) e geosmina (GEO), os quais conferem gosto e odor de mofo e terra a água. Estes compostos não são totalmente removidos pelos processos convencionais de tratamento de água – clarificação química, filtração em meio granular e desinfecção com cloro, e permanecem na água até seu consumo, ocasionando alto índice de rejeição do produto por parte da população consumidora. Desta forma, a pesquisa foi planejada para avaliar alternativas de processos de tratamento visando à remoção de compostos odoríferos na água. Além de MIB e geosmina, foram feitas investigações relativas a remoção de ferro (Fe+2), manganês (Mn+2) e enxofre (H2S), nos processos estudados. Estas formas são normalmente encontradas em ambientes redutores, como águas subterrâneas e no hipolímnio de lagos e reservatórios, podendo contribuir para a deterioração das características organolépticas da água, ocasionando gosto e odores desagradáveis na água potável. Os processos estudados na pesquisa foram aeração em cascata, dessorção gasosa e nanofiltração. Os mecanismos do primeiro e segundo processos são: a oxidação de formas reduzidas e a dessorção de compostos voláteis e gases da água para o ar. O sistema de nanofiltração remove contaminantes da água através de retenção física imposta pelo tamanho dos poros da membrana. / Human activities in watersheds introduce nutrients to water bodies, accelerating the natural process of eutrophication and favoring the occurrence of algae and cyanobacterial blooms. The blooms are characterized by explosives growths of those microorganisms. Among the several negative impacts brought by the blooms is the potential emission of the compounds 2-methylisoborneol (MIB) and geosmin (GEO), which confer earthy and moldy taste and odor to drinking water. MIB and GEO are not completely removed by the conventional water treatment processes – chemical clarification, granular filtration and chorine disinfection, causing consumer’s rejection of the distributed drinking water This research was planned to evaluate the capability of alternative treatment processes to remove odorous compounds from water. Besides MIB and geosmin, the research encompassed tests with iron (Fe+²), manganese (Mn+²) and hydrogen sulfide (H2S). These species are usually found in reduced environments such as lake and reservoir hypolimnion and groundwater. They can cause problems associated with color, taste and odor in drinking water. Processes studied in the research were cascade aeration, air stripping and nanofiltration. Prevailing mechanisms in the first two processes are oxidation of the reduced forms by air oxygen and stripping of volatile compounds and gases dissolved in water to air. Nanofiltration systems remove contaminants dissolved in water by physical retention imposed by the membrane pore size.

As atividades humanas em bacias hidrográficas introduzem nos cursos de água nutrientes que aceleram o processo natural de eutrofização, favorecendo a ocorrência de florações de algas e cianobactérias. Estas florações se caracterizam por um crescimento explosivo destes microrganismos. Entre os diversos impactos negativos trazidos pelas florações está a emissão potencial dos compostos 2-metilisoborneol (MIB) e geosmina (GEO), os quais conferem gosto e odor de mofo e terra a água. Estes compostos não são totalmente removidos pelos processos convencionais de tratamento de água – clarificação química, filtração em meio granular e desinfecção com cloro, e permanecem na água até seu consumo, ocasionando alto índice de rejeição do produto por parte da população consumidora. Desta forma, a pesquisa foi planejada para avaliar alternativas de processos de tratamento visando à remoção de compostos odoríferos na água. Além de MIB e geosmina, foram feitas investigações relativas a remoção de ferro (Fe+2), manganês (Mn+2) e enxofre (H2S), nos processos estudados. Estas formas são normalmente encontradas em ambientes redutores, como águas subterrâneas e no hipolímnio de lagos e reservatórios, podendo contribuir para a deterioração das características organolépticas da água, ocasionando gosto e odores desagradáveis na água potável. Os processos estudados na pesquisa foram aeração em cascata, dessorção gasosa e nanofiltração. Os mecanismos do primeiro e segundo processos são: a oxidação de formas reduzidas e a dessorção de compostos voláteis e gases da água para o ar. O sistema de nanofiltração remove contaminantes da água através de retenção física imposta pelo tamanho dos poros da membrana. / Human activities in watersheds introduce nutrients to water bodies, accelerating the natural process of eutrophication and favoring the occurrence of algae and cyanobacterial blooms. The blooms are characterized by explosives growths of those microorganisms. Among the several negative impacts brought by the blooms is the potential emission of the compounds 2-methylisoborneol (MIB) and geosmin (GEO), which confer earthy and moldy taste and odor to drinking water. MIB and GEO are not completely removed by the conventional water treatment processes – chemical clarification, granular filtration and chorine disinfection, causing consumer’s rejection of the distributed drinking water This research was planned to evaluate the capability of alternative treatment processes to remove odorous compounds from water. Besides MIB and geosmin, the research encompassed tests with iron (Fe+²), manganese (Mn+²) and hydrogen sulfide (H2S). These species are usually found in reduced environments such as lake and reservoir hypolimnion and groundwater. They can cause problems associated with color, taste and odor in drinking water. Processes studied in the research were cascade aeration, air stripping and nanofiltration. Prevailing mechanisms in the first two processes are oxidation of the reduced forms by air oxygen and stripping of volatile compounds and gases dissolved in water to air. Nanofiltration systems remove contaminants dissolved in water by physical retention imposed by the membrane pore size.