Synthetic membranes have a high separation efficiency, small footprint, low energy consumption and ease of operation, making them an attractive alternative to traditional separation operations. For this reason, membranes have been extensively studied for the treatment and recycling of bitumen-containing wastewaters. Such wastewaters include petroleum produced water, residual pipeline cleaning solutions and contaminated water from oil spills. Ceramic membranes are preferred in these applications over polymeric membranes because they are highly resistant to solvents and can be operated at high temperatures over a wide range of pH. Fine clays and silicates, coated with bitumen, are significant foulants for membrane filtration systems. These foulants possess acidic, basic and amphoteric groups, leading to the presence of both positive and negative surface charges. Ceramic membranes in aqueous media have a pH dependent surface charge. It was hypothesized that these surface charges are responsible for the high fouling of ceramic membranes that is observed when treating wastewaters containing bituminous fines. The overall objective of this research was to reduce fouling and increase the lifetime of ceramic membranes in treating oil sands produced water; an example of a wastewater containing bituminous fines. This goal was achieved through the surface modification of the ceramic membrane’s selective layer, as well as by the implementation of a novel in-place steam regeneration technique. All membrane filtration tests were performed with field samples of oil sands produced water that were supplied to CanmetMINING (NRCan) by three Canadian oil sands companies. Organosilanes are silicon-based monomers that can possess a wide array of chemical functionality due to their organic moieties. They are capable of reacting with oxide surfaces, and have seen extensive use as surface modification agents for ceramic membranes in various applications. To maintain desirable hydrophilic properties without surface charges, highly hydrophilic and non-ionic polyethylene oxide (PEO) based organosilanes were identified. These PEO-silanes were then used to modify ceramic membranes of several different selective layer materials, and the thermal stability of the silane layer was studied using FTIR, SEM, zeta potential and contact angle measurements. The modification procedure with PEO-silanes was first applied to lab-scale membrane disks, and subsequently to commercial scale multilumen membrane tubes that were tested in a pilot-scale system at CanmetMINING. Results obtained from both sets of experiments were promising and demonstrate that ceramic membranes can be surface modified in a way that successfully renders them fouling resistant to the bituminous fines present in these wastewaters. Upon surface modification, foulants were more readily released from the membrane surface, resulting in an enhanced flux and separation performance. A novel steam regeneration technique was also applied as a means of bituminous fouling alleviation. This technique was tested in the CanmetMINING pilot-scale system and consisted of periodically injecting steam into the membrane lumen feed channels during operation. Direct steam injection rapidly heated foulant cake layers, and water droplets in the saturated steam caused surface abrasions that ultimately resulted in the scouring of bitumen away from the membrane surface. Membrane fluxes when steam regeneration was active were up to 4 times higher when compared to tests where only traditional permeate backflushing was used. The fouling remediation techniques developed in this work have broad potential applicability in ceramic membrane filtration systems aimed at treating all wastewaters containing bituminous compounds, such as process waters in general and contaminated water from oil spills.

Produced water is formed in underground formations and brought up to the surface along with crude oil during production. It is by far the largest volume byproduct or waste stream. The most popular preference to deal with produced water is to re-inject it back into the formation. Produced water re-injection (PWRI) needs a treatment before injection to prevent formation blockage. Due to the increase of produced water during oil production in the west of Kuwait, an effluent treatment and water injection plants were established and commissioned in 2004 so that produced water could be used for re-injection purposes. It is estimated that oil wells in the west of Kuwait produce 15 to 40 % of produced water. The main aim of this treatment train is to reduce not only the oil-in-water amount to less than 10 ppm, but also total suspended solids to 5 ppm which is the maximum allowable concentration for re-injection and disposal. Furthermore, with respect to the upper limit for injection, the maximum number of particles between 5 and 8 microns is 200 in 0.1 ml. In practice the number is found to exceed this limit by 10 times...

The chemical industry is an essential part of modern society and therefore has a responsibility to develop solutions for the problems facing it. A major problem is continuing to match the material demands of a growing global population whilst simultaneously decreasing the consumption of finite natural resources and limiting the emissions of greenhouse gasses. An optimised catalytic system that shortens, or intensifies, the process chain for the production of chemicals can be an effective solution to this challenge. Auto-tandem catalysis is where a single metal-ligand complex facilitates two or more sequential transformations. For example: alkenes are hydroformylated into aldehydes which are then hydrogenated into alcohols. The alcohols have use as plasticisers or surfactants for metal extraction. A previously reported auto-tandem catalysis system was shown to be capable of sequential hydroformylation-hydrogenation of 1-octene to nonanol. It consisted of the neutral rhodium precursor [Rh(acac)(CO)2] and the bidentate ligand xantphos in 10% iPrOH/H2O co-solvent at temperatures of 160°C. Investigations, reported in this thesis, revealed that xantphos type ligands, with their large bite-angle, and high temperatures are required to generate the hydrogenation activity. However, in contrast to the previous system, water is not necessary; with the same results produced in toluene:iPrOH solutions and water:iPrOH solutions. It is proposed that the iPrOH or H2O has a direct influence in the catalytic cycle, either as a hydrogen-shuttle or generates a cationic rhodium species, known to be active in hydrogenation. High temperature NMR studies show the standard resting state of the hydroformylation catalyst is still predominant at high temperatures therefore the proposed catalytic cycle starts from this step. A recurring problem in the industrial process chain is the separation of the catalyst from the final products. Combing a TiO2 ceramic membrane with a POSS (polyhedral oligomeric silsesquioxane) modified tin catalyst and phosphonium iodide co-catalyst, for the coupling of epoxides and CO2 to make cyclic carbonates, was investigated. The catalyst system showed good substrate compatibility for a range of epoxides. In a prototype membrane set-up the system demonstrated a long catalyst life time, however significant leaching was also observed.

Algal bloom can significantly impact reverse osmosis desalination process and reduce the drinking water production. In 2008, a major bloom event forced several UAE reverse osmosis plants to stop their production, and in this context, a better understanding of UF membrane fouling caused by algal organic matter (AOM) is needed, in order to adjust the filtration conditions during algal bloom events. Polymeric MF/UF membranes are already widely used for RO pretreatment, but ceramic UF membranes can also be an alternative for the filtration of marine algal solutions. The fouling potential of the Red Sea and the Arabian Sea, sampled at different seasons, along with four algal monocultures grown in laboratory, and one mesocosm experiment in the Red Sea was investigated. Algal solutions induce a stronger and more irreversible fouling than terrestrial humic solution, toward ceramic membrane. During algal bloom events, this fouling is enhanced and becomes even more problematic at the decline phase of the bloom, for a similar initial DOC. Three main mechanisms are involved: the formation of a cake layer at the membrane surface; the penetration of the algal organic matter (AOM) in the pore network of the membrane; the strong adhesion of AOM with the membrane surface. The last mechanism is species-specific and metal-oxide specific. In order to understand the stronger ceramic UF fouling at the decline phase, AOM quality was analyzed every two days. During growth, AOM is getting enriched in High Molecular Weight (HMW) structures (> 200 kDa), which are mainly composed by proteins and polysaccharides, and these compounds seem to be responsible for the stronger fouling at decline phase. In order to prevent the fouling of ceramic membrane, coagulation-flocculation (CF) using ferric chloride was implemented prior to filtration. It permits a high removal of HMW compounds and greatly reduces the fouling potential of the algal solution. During brief algal bloom events, CF should be implemented prior to UF to protect the membranes. A comparison between polymeric and ceramic UF membranes showed that ceramic membrane suffers from a stronger fouling but permits a better removal of DOC and particularly HMW compounds.

Ceramic membranes (CM) are robust membranes attributed with high production, long life span and stability against critical conditions. While capital costs are high, these are partially offset by lower operation and maintenance costs compared to polymeric membranes. Like any other low-pressure membrane (LPM), CM faces problems of fouling, low removal of organic matter and poor removal of trace organic compounds (TOrCs). Current pretreatment approaches that are mainly based on coagulation and adsorption can remove some organic matter but with a low removal of the biopolymers component which is responsible for fouling. Powdered activated carbon (PAC) accompanied with a LPM maintains good removal of TOrCs. However, enhanced removal of TOrCs to higher level is required. Submicron powdered activated carbon (SPAC), obtained after crushing commercial activated carbon into very fine particle, and novel activated carbon (KCU 6) which is characterized with larger pores and high surface area were employed. A pre-coating approach, which provides intimated contact between PAC and contaminants, was adopted for wastewater and (high DOC) surface water treatment. For seawater, in-line coagulation with iron III chloride was adopted. Both SPAC and KCU 6 showed good removal of biopolymers at a dose of 30 mg/L with > 85 % and 90 %, respectively. A dose of 40 mg/L of SPAC and 30 mg/L KCU 6 pre-coats were successful used in controlling membrane fouling. SPAC is suggested to remove biopolymers by physical means and adsorption while KCU 6 removed biopolymers through adsorption. Both KCU 6 and SPAC attained high removal of TOrCs whereas KCU 6 showed outstanding performance. Out of 29 TOrCs investigated, KCU 6 showed > 87 % TOrCs rejection for 28 compounds. In seawater pretreatment, transparent exopolymer particles (TEP) were found to be an important foulant. TEP promoted both reversible and irreversible fouling. TEP are highly electronegative while alumina CM is positively charged which support strong TEP–alumina binding. The influence of TEP fouling was minimized with a low dose of 0.5 – 1 mg/l Fe coagulant. Bacteria were almost completely removed; Silt Density Index (SDI) value was maintained to 2 % per minute and a constant permeate turbidity of 0.05 NTU was achieved.

O presente trabalho teve como objetivo estudar o processo de microfiltração tangencial com membranas tubulares cerâmicas, aplicado à clarificação da vinhaça originária do processamento de cana de açúcar, analisando as características fluidodinâmicas do processo e os tipos de bloqueios de poro por modelos matemáticos. Neste estudo foram utilizadas membranas cerâmicas de \'alfa\'-alumina (\'alfa\'-\'AL IND.2\'O IND.3\') com tamanho nominal de poros de 1,2 \'mü\'m e 0,8 \'mü\'m, respectivamente denominadas no texto como M12 e M08. Amostras do permeado (fluxo transmembrana) e retentado foram analisadas com medidas de propriedades tais como: densidade, pH, condutividade elétrica, viscosidade, tensão superficial, cor e turbidez. As características da permeação das membranas cerâmicas foram primeiramente analisadas com água potável em diferentes condições fluidodinâmicas e o fluxo transmembrana foi medido em função do tempo para quantificar as propriedades da membrana antes que houvesse impregnações diversas em sua superfície. Vinhaça diluída na proporção volumétrica de 50% vol. foi microfiltrada em condições fluidodinâmicas variadas utilizando pressões transmembrana de 200 kPa, 300 kPa, 400 kPa e 500 kPa em escoamento turbulento com número de Reynolds de 11.500, 22.500 e 33.500. Os resultados experimentais foram analisados através de gráficos do fluxo transmembrana em função do tempo e das resistências (resistência total, resistência da membrana, resistência de polarização e resistência de fouling) em função da pressão, e da análise do pH, condutividade elétrica, viscosidade, densidade, tensão superficial, quantidade de sólido solúveis totais (ºBrix), cor e turbidez. A influência da interação da vinhaça na superfície da membrana microporosa foi investigada a partir dos valores das resistências e aplicação de modelos matemáticos para bloqueio de poros. Os melhores resultados de fluxo transmembrana foi de 31,48 L/h.\'M POT.2\' para a M12 em condição fluidodinâmica de 500 kPa para a pressão transmembrana e 11.500 para o número de Reynolds e de 39,47 L/h.\'M POT.2\' para a membrana M08 com 500 kPa de pressão e 33.500 para o número de Reynolds. O estudo do modelo de bloqueio dos poros revelou que o fluxo de permeado diminui principalmente por fenômenos relacionados à formação da camada de polarização e do bloqueio parcial dos poros. As análises físico-químicas revelaram que o pH e a viscosidade do permeado foi afetado pelo número de Reynolds e que o processo tem potencial para remover partículas em suspensão, reduzir a turbidez e a cor do permeado. / This present work studied the process of cross flow microfiltration using tubular ceramic applied in the vinasse clarification from sugar cane, analyzing fluid dynamic features of process and the types of pore blocking applied to math models. In this research was used \'alfa\'-alumina (\'alfa\'-\'AL IND.2\'O IND. 3) ceramic membrane with pore size of 1.2 \'mü\'m and 0.8 \'mü\'m, respectively called M12 and M08. Permeate samples (transmembrane flux) and retentate were analyzed measuring their specific mass, pH, electrical conductivity, viscosity, surface tension, total soluble solid (ºBrix), color and turbidity. The virgin membranes were analyzed first with tap water in different fluid dynamics conditions and transmembrane flux was measured in function of the time to quantify its proprieties before to have impregnation in its surface. Vinasse was deluded in water in the proportion of 50% vol and it was microfiltered in varied fluid dynamics using transmembrane pressure of 200 kPa, 300 kPa, 400 kPa and 500 kPa in turbulent flow with Reynolds number 11,500; 22,500 and 33,500. The experimental data obtained were analyzed through to graphics of transmembrane flux versus time and resistances (membrane resistance, total resistance, polarization resistance and fouling resistance) versus pressure, and produced tables with physical-chemical proprieties values. The influence of interaction between vinasse and membrane surface was investigated using math models to pore blockage. The high performance was obtained with M12 membrane with permeate of 31.48 L/h.\'M POT.2\' in transmembrane pressure of 500 kPa (Re = 13,500). For M08 membrane permeate flux (39.47 L/h.\'M POT.2\') was higher for the situation of greater tangential velocity (Re = 33,500) and higher pressure (\'delta\'P = 500 kPa). The analysis for the pore blockage showed that the permeate flux decreases primarily by phenomena related to the cake formation of polarization and partial blockage of pores. Analyses of pH and viscosity of permeate flux showed that Reynolds number influences on values. The study showed that the clarification of vinasse by ceramic membranes of microfiltration has the potential to remove suspension particles and to reduce turbidity and color.

O presente trabalho teve como objetivo estudar o processo de microfiltração tangencial com membranas tubulares cerâmicas, aplicado à clarificação da vinhaça originária do processamento de cana de açúcar, analisando as características fluidodinâmicas do processo e os tipos de bloqueios de poro por modelos matemáticos. Neste estudo foram utilizadas membranas cerâmicas de \'alfa\'-alumina (\'alfa\'-\'AL IND.2\'O IND.3\') com tamanho nominal de poros de 1,2 \'mü\'m e 0,8 \'mü\'m, respectivamente denominadas no texto como M12 e M08. Amostras do permeado (fluxo transmembrana) e retentado foram analisadas com medidas de propriedades tais como: densidade, pH, condutividade elétrica, viscosidade, tensão superficial, cor e turbidez. As características da permeação das membranas cerâmicas foram primeiramente analisadas com água potável em diferentes condições fluidodinâmicas e o fluxo transmembrana foi medido em função do tempo para quantificar as propriedades da membrana antes que houvesse impregnações diversas em sua superfície. Vinhaça diluída na proporção volumétrica de 50% vol. foi microfiltrada em condições fluidodinâmicas variadas utilizando pressões transmembrana de 200 kPa, 300 kPa, 400 kPa e 500 kPa em escoamento turbulento com número de Reynolds de 11.500, 22.500 e 33.500. Os resultados experimentais foram analisados através de gráficos do fluxo transmembrana em função do tempo e das resistências (resistência total, resistência da membrana, resistência de polarização e resistência de fouling) em função da pressão, e da análise do pH, condutividade elétrica, viscosidade, densidade, tensão superficial, quantidade de sólido solúveis totais (ºBrix), cor e turbidez. A influência da interação da vinhaça na superfície da membrana microporosa foi investigada a partir dos valores das resistências e aplicação de modelos matemáticos para bloqueio de poros. Os melhores resultados de fluxo transmembrana foi de 31,48 L/h.\'M POT.2\' para a M12 em condição fluidodinâmica de 500 kPa para a pressão transmembrana e 11.500 para o número de Reynolds e de 39,47 L/h.\'M POT.2\' para a membrana M08 com 500 kPa de pressão e 33.500 para o número de Reynolds. O estudo do modelo de bloqueio dos poros revelou que o fluxo de permeado diminui principalmente por fenômenos relacionados à formação da camada de polarização e do bloqueio parcial dos poros. As análises físico-químicas revelaram que o pH e a viscosidade do permeado foi afetado pelo número de Reynolds e que o processo tem potencial para remover partículas em suspensão, reduzir a turbidez e a cor do permeado. / This present work studied the process of cross flow microfiltration using tubular ceramic applied in the vinasse clarification from sugar cane, analyzing fluid dynamic features of process and the types of pore blocking applied to math models. In this research was used \'alfa\'-alumina (\'alfa\'-\'AL IND.2\'O IND. 3) ceramic membrane with pore size of 1.2 \'mü\'m and 0.8 \'mü\'m, respectively called M12 and M08. Permeate samples (transmembrane flux) and retentate were analyzed measuring their specific mass, pH, electrical conductivity, viscosity, surface tension, total soluble solid (ºBrix), color and turbidity. The virgin membranes were analyzed first with tap water in different fluid dynamics conditions and transmembrane flux was measured in function of the time to quantify its proprieties before to have impregnation in its surface. Vinasse was deluded in water in the proportion of 50% vol and it was microfiltered in varied fluid dynamics using transmembrane pressure of 200 kPa, 300 kPa, 400 kPa and 500 kPa in turbulent flow with Reynolds number 11,500; 22,500 and 33,500. The experimental data obtained were analyzed through to graphics of transmembrane flux versus time and resistances (membrane resistance, total resistance, polarization resistance and fouling resistance) versus pressure, and produced tables with physical-chemical proprieties values. The influence of interaction between vinasse and membrane surface was investigated using math models to pore blockage. The high performance was obtained with M12 membrane with permeate of 31.48 L/h.\'M POT.2\' in transmembrane pressure of 500 kPa (Re = 13,500). For M08 membrane permeate flux (39.47 L/h.\'M POT.2\') was higher for the situation of greater tangential velocity (Re = 33,500) and higher pressure (\'delta\'P = 500 kPa). The analysis for the pore blockage showed that the permeate flux decreases primarily by phenomena related to the cake formation of polarization and partial blockage of pores. Analyses of pH and viscosity of permeate flux showed that Reynolds number influences on values. The study showed that the clarification of vinasse by ceramic membranes of microfiltration has the potential to remove suspension particles and to reduce turbidity and color.

Les membranes à transport d’oxygène (OTM) sont des membranes céramiques denses qui sont capables de transporter l’oxygène de manière totalement sélective à travers un gradient de pression partielle d’oxygène. Elles peuvent être utilisées pour diminuer les émissions de gaz à effet de serre dans le cadre de la capture et du stockage du CO2 ou pour augmenter l’efficacité de l’oxydation partielle du méthane. La semi-perméabilité de l’oxygène est proportionnelle à la conductivité ambipolaire du matériau. Cependant, les OTM avec des conductivités ambipolaires élevées sont plus susceptibles de se dégrader rapidement dans les conditions d’utilisation. Pour être compétitives, les OTMs doivent donc remplir plusieurs critères, notamment avoir un flux élevé mais être aussi stables chimiquement, thermiquement, mécaniquement et être peu chères. CaTi0.9Fe0.1O3−δ (CTF) a été récemment présenté comme étant un matériau prometteur pouvant remplir ces critères et mérite d’être étudié plus en détail.Cette thèse se focalise sur les performances (mesurées par le flux d’oxygène) et la stabilité chimique et thermique du CTF. Pour améliorer les performances d’une membrane, il est nécessaire de savoir si la semi-perméation est limitée par les réactions en surface ou par la diffusion en volume. Les premiers résultats de ces travaux détaillent les étapes limitantes du transport de l’oxygène dans le CTF. En particulier, grâce à un montage expérimental spécifique et des expériences complémentaires, il a été montré que le CTF est limité à la fois par la diffusion en volume et les réactions de surfaces pour T < 750°C mais est majoritairement limité par la diffusion en volume à plus haute température. Les chapitres suivant détaillent la diffusion dans le volume et la conductivité électrique en fonction de la pression partielle d’oxygène et de la température, au vu de la chimie des défauts du CTF. Dans les conditions de fonctionnement, le CTF doit être considéré comme étant un conducteur mixte, avec une conductivité ionique qui devient prédominante pour des températures supérieures à 800°C.La seconde partie est consacrée à l’étude de la stabilité du CTF sous des atmosphères réactives, spécifiques aux OTM, qui sont connues comme provoquant des dégradations pour certains matériaux. Des tests de vieillissement sous atmosphères de CO2, CO, H2 n’ont montré aucune dégradation du flux de semi-perméation sur plusieurs centaines d’heures. Seulement une légère diminution du flux (- 25%) a été observée en présence de CO2 et de vapeur d’eau mais après cent heures sous hélium, le flux initial a été retrouvé. Des analyses DRX, MEB et Raman post-mortem n’ont révélé aucun signe notable de dégradation en surface et dans le volume. Un test sous CH4 a également été effectué, et la formation de CO, CO2, H2 et H2O a été suivie pendant des centaines d’heures. Malgré la présence de ces gaz réactifs, la même valeur du flux de semi-perméation a été retrouvée après 1000 heures de test sous méthane, témoignant d’une très bonne stabilité du CTF dans ces conditions réductrices. En conséquence, malgré des valeurs de flux relativement faibles (5×10-3 mL.min-1.cm-1 à 900°C), ce matériau est plein de promesse et son excellente stabilité sous méthane notamment peut être très intéressante pour certaines applications. / Oxygen transport membranes (OTM) are dense ceramic membranes that allow oxygen diffusion along a chemical potential gradient. OTMs can increase the efficiency of oxycombustion processes or partial oxidation of methane, resulting in lower CO2 emissions overall. The oxygen transport is proportional to the ambipolar conductivity of the OTM material. However, OTM materials with the highest ambipolar conductivity are more prone to fast degradation under operation conditions. To be competitive, OTMs must associate high oxygen transport properties but also must be chemically, thermally, and mechanically stable, and preferably not expensive. CaTi0.9Fe0.1O3−δ (CTF) has recently been shown to match these demands, appearing as a promising OTM material that is worth studying in further detail.This PhD is therefore dedicated to study the performance and stability of CTF in typical operation conditions of an OTM. To improve the performance of a membrane, it is necessary to determine if the semi-permeation is limited by surface exchange reactions or by bulk diffusion. The first results of this work will detail the nature of the limiting reaction step for oxygen transport in CTF. Specifically, CTF is co-limited by bulk diffusion and surface exchange reactions at T < 750 °C, but is mainly limited by bulk diffusion at higher temperatures. The following chapter details the bulk diffusion process and electrical conductivity in light of the defect chemistry of CTF, as a function of oxygen partial pressure and temperature. Under typical operation conditions, CTF must be regarded as a mixed ionic and electronic conductor, with increasing predominance of ionic conductivity at T > 800°C. The second part is dedicated to the stability of the CTF under atmospheric compositions typically found in standard operating conditions, known to degrade the performance of usual membrane materials. The oxygen transport of CTF is shown to remain extremely stable under CO2, CO, and H2 atmospheres over several hundred hours. Some degradation (- 25% of oxygen semi permeation flux) was observed when exposed to humidified CO2, but returning to initial values when exposed to dry helium for a hundred hour. Post-mortem XRD, SEM and Raman analyses did not show any obvious signs of surface or bulk degradation. CTF was tested for CH4 oxidation for a thousand hours and the formation of CO, CO2 and H2O was followed. Despite this reactive environment, the oxygen transport CTF membrane fully regenerates upon returning to helium atmosphere. Therefore, despite relatively low performance (5×10-3 mL.min-1.cm-1 at 900°C), this material is full of promises and especially its outstanding stability under methane can be very interesting for some applications.

Membrane fouling, which is caused by deposition/adsorption of foulants on the surface or within membrane pores, still remains a bottleneck that hampers the widespread application of membrane bioreactor (MBR) technology for wastewater treatment. Recently membrane surface modification has proved to be a useful method in water/wastewater treatment to improve the surface hydrophilicity of membranes to obtain higher water fluxes and to reduce fouling. In this study, membrane modification was investigated by depositing a thin film of same thickness of TiO2 on the surface of an ultrafiltration alumina membrane. Various thin-film deposition (TFD) methods were employed, i.e. electron-beam evaporation, sputter and atomic layer deposition (ALD), and a comparative study of the methods was conducted to assess fouling inhibition performance in a lab-scale anaerobic MBR (AnMBR) fed with synthetic municipal wastewater. Thorough surface characterization of all modified membranes was carried out along with clean water permeability (CWP) tests and fouling behavior by bovine serum albumin (BSA) adsorption tests. The study showed better fouling inhibition performance of all modified membranes; however the effect varied due to different surface characteristics obtained by different deposition methods. As a result, ALD-modified membrane showed a superior status in terms of surface characteristics and fouling inhibition performance in AnMBR filtration tests. Hence ALD was determined to be the best TFD method for alumina membrane surface modification for this study. ALD-modified membranes were further characterized to determine an optimum thickness of TiO2-film by applying different ALD cycles. ALD treatment significantly improved the surface hydrophilicity of the unmodified membrane. Also ALD-TiO2 modification was observed to reduce the surface roughness of original alumina membrane, which in turn enhanced the anti-fouling properties of modified membranes. Finally, a same thickness of ALD-TiO2 and ALD-SnO2 modified membranes were tested for alginate fouling inhibition performance in a dead-end constant-pressure filtration system. This is the first report on the application of SnO2-modified ceramic membrane for testing its alginate fouling potential; which was determined to be nearly-same for both modified membranes with a negligible amount of difference. This revealed SnO2 as a potential future anti-foulant to be tested for membrane modification/fabrication for application in water/wastewater treatment systems.

<div>Thermal barrier coatings (TBCs) made of low thermal conductivity ceramic topcoats have been extensively used in hot sections of gas turbine engines, in aircraft propulsion and power generation applications. TBC damage may occur during gas turbine operations, due to either time- and cycle-dependent degradation phenomena, external foreign object damage, and/or erosion. The damaged TBCs, therefore, need to be removed and repaired during engine maintenance cycles. Although several coating removal practices have been established which are based on the trial-and-error approach, a fundamental understanding of coating fracture mechanisms during the removal process is still limited, which hinders further development of the process.</div><div>The objective of the thesis is to develop a particle-based coating removal modeling framework, using both the smoothed particle hydrodynamics (SPH) and discrete element modeling (DEM) methods. The thesis systematically investigates the processing-property relationships in the TBC removal processes using a modeling approach, thus providing a scientific tool for process design and optimization.</div><div>To achieve the above-mentioned objective, the following research tasks are identified. First a comprehensive literature review of major coating removal techniques is presented in Chapter 2. Chapter 3 discusses an improved SPH model to simulate the high-velocity particle impact behaviors on TBCs. In Chapter 4, the abrasive water jet (AWJ) removal process is modeled using the SPH method. In Chapter 5, an SPH model of the cutting process with regular electron beam physical vapor deposition (EB-PVD) columnar grains is presented. In Chapter 6, a 3D DEM cutting model with regular EB-PVD column grains is discussed. In Chapter 7, a 2D DEM cutting model based on the realistic coating microstructure is developed. Finally, in Chapter 8, based on the particle-based coating removal modeling framework results and analytical solutions, a new fracture mechanism map is proposed, which correlates the processing parameters and coating fracture modes.</div><div>The particle-based modeling results show that: (1) for the SPH impact model, the impact hole penetration depth is mainly controlled by the vertical velocity component. (2) The SPH AWJ simulation results demonstrate that the ceramic removal rate increases with incident angle, which is consistent with the fracture mechanics-based analytic solution. (3) The SPH model with regular EB-PVD columnar grains shows that it is capable to examine the stress evolutions in the coating with columnar grain structures, which is not available if a uniform bulk coating model was used. Additional analysis reveals that the fracture of the columnar grains during the cutting process is achieved through deflection and fracture of the grains, followed by pushing against neighboring grains. (4) The 3D DEM model with regular coating columnar grains shows that, during the coating removal process, a ductile-to-brittle transition is identified which depends on the cutting depth. The transition occurs at the critical cutting depth, which is based on the Griffith fracture criterion. At small cutting depths, the ductile failure mode dominates the cutting process, leading to fine cut particles. As the cutting depth exceeds the critical cutting depth, a brittle failure mode is observed with the formation of chunk-like chips. (5) The 2D DEM model with the realistic coating microstructure shows that there are densification and fracture during the foreign object compaction process, which qualitatively agrees with the experimental observations. (6) The newly proposed coating fracture mechanism map provides guidance to predict three fracture modes, i.e., ductile brittle, and mixed ductile-brittle, as a function of processing parameters, including the cutting depth and cutting speed. The map can be used to determine the processing conditions based on required TBC removal operations: rough cut (brittle mode), semi-finish (mixed ductile-brittle mode), and finish (ductile mode).</div><div><br></div>