In-situ polymerization is one of the most efficient methods for production of polymer clay nanocomposites. In-situ polymerization of olefins using coordination catalysts is a type of heterogeneous polymerization. In order to achieve acceptable clay nanolayer dispersion in the polyolefin matrix, the clay layer exfoliation and particle break up during the polymerization are essential requirements. A literature review on polyolefin/clay nanocomposite is given in Chapter 2. In Chapter 3, we present a new mathematical model, which is as an extension of the multigrain model (MGM), to describe the intercalative polymerization and expansion of clay interlayer spaces during polymerization using clay-supported metallocenes. The results from the model show that, under the studied conditions, mass transfer is not a strong factor controlling clay exfoliation and particle break up. If the polymerization active sites are supported uniformly on all clay surfaces, effective exfoliation will be achieved after a relative short polymerization time. In practice, obtaining good dispersion of clay nanolayers with uniform properties requires that the active sites be exclusively located on the clay nanolayer surfaces, and not extracted by the solvent to form a homogeneous solution. Factors favouring active site extraction would result in nanocomposites with poor properties. In addition, high polymerization activities, stable polymerization runs, and ease of supporting are other criteria for a successful in-situ polymerization. For this purpose we established a catalyst supporting method by which most of these requirements were met. In this method, the water content on the clay surface, which is considered as poison for the metallocene catalyst, was used to produce MAO upon reaction with trimethylaluminum (TMA). Using this method, polymerization was highly active in absence of MAO cocatalyst, knowing that MAO cocatalyst promotes active site extraction from the clay surface and results in poor powder morphology. Chapter 4 describes the development of this supporting methodology. Chapter 4 also investigates the effect of the organic modification type existing on the clay surface on the success of catalyst supporting and in-situ polymerization. We found that using the proposed supporting procedure, only tertiary ammonium type modification enhanced the in-situ polymerization, whereas the quaternary ammonium worsened the catalyst supporting efficiency and led to catalyst with poor or no polymerization activity. It is suggested that, in addition to enhancing clay surface-organic solvent compatibility (which facilitates catalyst supporting), the tertiary ammonium cation reacts with the in-situ produced MAO and increases the stability of the cocatalyst bonded to the clay surface. The effect of different polymerization conditions on the polymerization behavior and nanocomposite structural properties, such as catalyst loading during supporting, polymerization temperature and triisobutylaluminum (TIBA) concentration, were studied in Chapter 5. It was found that TIBA acts merely as scavenger. High polymerization activities were obtained with low Al/Zr ratios (Al from TIBA) and increased Al concentration decreased the polymerization activity and also the quality of powder morphology. Catalyst loading in the supporting step showed to have an important role in determining the final properties. The clay particles with higher catalyst loading resulted in better exfoliation and powder morphologies The effect of solvent type during catalyst supporting and polymerization was studied in Chapter 6. It was shown that catalyst supporting in n-hexane resulted in polymerizations with higher activities and polymers with higher molecular weight were produced. Polymerization with catalyst supported in hexane showed different ethylene uptake profiles, suggesting different mechanism of exfoliation. It is suggested that using this catalyst, the clay is mostly exfoliated before polymerization started. Similar to the original clay, the catalyst supporting efficiency on the organically modified clay was close to 100 percent. However, comparing the polymerization activities of these catalysts to those that were supported directly in the reactor just before the polymerization (in-reactor, or in-situ, supported catalysts) shows that a considerable fraction of the active sites are deactivated during the prolonged contact between catalyst and clay support surface. In Chapter 5, it was shown that the in-reactor supported catalyst had considerably higher polymerization activities, up to 40 percent of that of the homogeneous catalyst. Nanocomposites made with in-reactor supported catalysts had powder morphology and nanaolayer dispersion comparable to those made with clay-supported catalysts.

In alkalischen Lösungen führt die Reaktion von Hydroxylionen mit den Si-O-Si-Bindungen des Glasnetzwerks zur Bildung hydratisierter Oberflächen und gelöstem Silikat. Der Grad der Korrosion bzw. der Alterung der Glasfaser ist abhängig von der chemischen Zusammensetzung des Glases und Korrosionslösung sowie von Zeit und Temperatur. Die Untersuchung von Glasfasern verschiedener chemischer Zusammensetzung in NaOH- sowie Zementlösungen zeigte, dass die inhibierende Wirkung von Ca-Ionen zu einem veränderten Korrosionsmechanismus führt. Dies konnte anhand der mechanischen Eigenschaften der Glasfasern sowie rasterelektronenmikroskopischen Untersuchungen gezeigt werden. Während die Korrosion in NaOH-Lösung zu einer ausgeprägten Umwandlung der gesamten äußeren Glasfaserschicht in Reaktionsprodukte führte, zeigten Glasfasern in Zementlösung bei gleichem pH-Wert einen stark lokal begrenzten, punktförmigen Angriff. Daraus resultieren unterschiedliche mechanische Eigenschaften der Glasfasern in Abhängigkeit von der gewählten Korrosionslösung.

In-situ polymerization is one of the most efficient methods for production of polymer clay nanocomposites. In-situ polymerization of olefins using coordination catalysts is a type of heterogeneous polymerization. In order to achieve acceptable clay nanolayer dispersion in the polyolefin matrix, the clay layer exfoliation and particle break up during the polymerization are essential requirements. A literature review on polyolefin/clay nanocomposite is given in Chapter 2. In Chapter 3, we present a new mathematical model, which is as an extension of the multigrain model (MGM), to describe the intercalative polymerization and expansion of clay interlayer spaces during polymerization using clay-supported metallocenes. The results from the model show that, under the studied conditions, mass transfer is not a strong factor controlling clay exfoliation and particle break up. If the polymerization active sites are supported uniformly on all clay surfaces, effective exfoliation will be achieved after a relative short polymerization time. In practice, obtaining good dispersion of clay nanolayers with uniform properties requires that the active sites be exclusively located on the clay nanolayer surfaces, and not extracted by the solvent to form a homogeneous solution. Factors favouring active site extraction would result in nanocomposites with poor properties. In addition, high polymerization activities, stable polymerization runs, and ease of supporting are other criteria for a successful in-situ polymerization. For this purpose we established a catalyst supporting method by which most of these requirements were met. In this method, the water content on the clay surface, which is considered as poison for the metallocene catalyst, was used to produce MAO upon reaction with trimethylaluminum (TMA). Using this method, polymerization was highly active in absence of MAO cocatalyst, knowing that MAO cocatalyst promotes active site extraction from the clay surface and results in poor powder morphology. Chapter 4 describes the development of this supporting methodology. Chapter 4 also investigates the effect of the organic modification type existing on the clay surface on the success of catalyst supporting and in-situ polymerization. We found that using the proposed supporting procedure, only tertiary ammonium type modification enhanced the in-situ polymerization, whereas the quaternary ammonium worsened the catalyst supporting efficiency and led to catalyst with poor or no polymerization activity. It is suggested that, in addition to enhancing clay surface-organic solvent compatibility (which facilitates catalyst supporting), the tertiary ammonium cation reacts with the in-situ produced MAO and increases the stability of the cocatalyst bonded to the clay surface. The effect of different polymerization conditions on the polymerization behavior and nanocomposite structural properties, such as catalyst loading during supporting, polymerization temperature and triisobutylaluminum (TIBA) concentration, were studied in Chapter 5. It was found that TIBA acts merely as scavenger. High polymerization activities were obtained with low Al/Zr ratios (Al from TIBA) and increased Al concentration decreased the polymerization activity and also the quality of powder morphology. Catalyst loading in the supporting step showed to have an important role in determining the final properties. The clay particles with higher catalyst loading resulted in better exfoliation and powder morphologies The effect of solvent type during catalyst supporting and polymerization was studied in Chapter 6. It was shown that catalyst supporting in n-hexane resulted in polymerizations with higher activities and polymers with higher molecular weight were produced. Polymerization with catalyst supported in hexane showed different ethylene uptake profiles, suggesting different mechanism of exfoliation. It is suggested that using this catalyst, the clay is mostly exfoliated before polymerization started. Similar to the original clay, the catalyst supporting efficiency on the organically modified clay was close to 100 percent. However, comparing the polymerization activities of these catalysts to those that were supported directly in the reactor just before the polymerization (in-reactor, or in-situ, supported catalysts) shows that a considerable fraction of the active sites are deactivated during the prolonged contact between catalyst and clay support surface. In Chapter 5, it was shown that the in-reactor supported catalyst had considerably higher polymerization activities, up to 40 percent of that of the homogeneous catalyst. Nanocomposites made with in-reactor supported catalysts had powder morphology and nanaolayer dispersion comparable to those made with clay-supported catalysts.

Cette recherche vise à analyser et à identifier, par des essais, le comportement au fluage d'une argile de type kaolinite sous un état de contraintes triaxial. Une investigation fine de l’état microstructural, avant et après fluage, a par ailleurs été réalisée. Les résultats macroscopiques ont permis de constater que des phénomènes de dilatance et de contractante s’amplifient pendant le fluage. Les résultats montrent également que la position, sur le plan des contraintes (p'-q), du niveau de contrainte vis-à-vis des différents domaines volumétriques, contrôle le développement de la déformation au fluage et du taux de déformation. Les résultats de MEB ont montré que l'évolution microstructurale de l'argile, après le chargement mécanique, dépend fortement de l'histoire du chargement. / The objective of this research is to analyze the creep behavior of a typical clay along triaxial tests, moreover, to analyze the microstructural mechanisms of creep. Analysis on the macroscopic results ascertained that both dilatancy and contractancy phenomena could occur during creep. The magnitude of the dilatancy/contractancy during creep was guided by the test conditions: stress level and the over consolidation ratio, which specifically governed the direction of the volumetric strain variations. The results of SEM indicated that the microstructural evolution of the clay after the mechanical loading depend on the stress history. Afterwards, the structural evolution in creep phase depends on the structural pattern developed in monotonic loading

[pt] Este trabalho teve por objetivo avaliar a morfologia de biofilmes, formados em superfície de aço API 5L X80 submetida a um fluido com baixo BSW (Basic Sediment Water), ou seja, baixo teor de água em óleo, através de análise por Microscopia Eletrônica de Varredura (MEV), determinar a cinética e quantificar os grupos bacterianos de formação destes biofilmes, e avaliar a biocorrosão causada por estes microrganismos. Foram realizadas alterações no protocolo original de preparo de amostras, com a finalidade de obter melhor definição das morfologias avaliadas. Realizaram-se estudos dinâmicos (looping) e em condições estáticas, com e sem a adição de agente biocida. Utilizando-se como fluido de processo o óleo coletado no terminal da Petrobras em Barra do Furado que tem como característica um BSW de aproximadamente 1 por cento de água. Para alcançar os objetivos descritos foram quantificadas bactérias sésseis (bactérias facultativas heterotróficas, bactérias precipitantes do ferro, bactérias anaeróbias heterotróficas e bactérias redutoras de sulfato) através da técnica do número mais provável (NMP). A intensidade do processo corrosivo foi avaliada através da análise dos pites formados nos cupons por microscopia óptica. A seqüência de fixação com alteração do protocolo inicial, permitiu uma melhor preservação estrutural do biofilme obtendo-se assim imagens com melhor resolução, tendo em vista que a fixação primária com glutaraldeído fixa principalmente proteínas pelo estabelecimento de ligações divalentes com grupamento amino, e a pós-fixação em tetróxido de ósmio reage com os lipídios. Quanto a cinética, observou-se também que na presença de fluido oleoso, a formação do biofilme só é detectada após 15 dias de exposição. A adição do agente biocida inibiu o crescimento do biofilme, não sendo detectada a presença de células cultiváveis após 7 dias em contato com o fluido contendo o agente químico. / [en] This study aims to evaluate the morphology of biofilms formed on the surface of API 5L X80 steel exposed to a low BSW (Basic Sediment Water) fluid comprising oil of a low water content. The analisys was performed using scanning electron microscopy (SEM) in order to determine the formation kinetics, to quantify and identify the bacterial groups present as the film formed, and to evaluate the biocorrosion caused by these organisms. Modifications were made to the original sample preparation protocol, in order to better define the film morphologies. Studies were undertaken applying either static or dynamic (looping) conditions, bith with and without the addition of biocides. The process fluid used was oil collected from the Petrobras Barra do Furado Terminal, characterized by its 1 percent BSW. The evaluation was performed quantifying the sessile bacteria present in the film (heterotrophic bacteria, iron bacteria, anaerobic bacteria e sulphate reducing bacteria) via the Most Probable Number (MPN) technique. The intensity of the corrosion process was determined by the analysis of pits forme in the testpieces, by optical microscopy. The application of a sample fixation sequence, in addition to modifications of the inicial sample preparation protocol, permitted the improved preservation of the biofilm structures, thereby permitting higher resolution images. The primary fixing agent, containing gluteraldehyde, principally fixes proteins, by establishing divalent bonds with amino groups, while the post-fixation stage with osmium tetroxide invloves reactions with lipid groups.With regard to the film deposition kinetics, it was observed that biofilm formation could only be detected after 15 day s exposure to the oily fluid. The addition of a biocide, inhibited the growth of the film, no cultivatable cells being present after 7 days contact with the treated fluid.

Formaldehyde-based adhesives have been reported to be detrimental to health. Petrochemical-based adhesives are non-renewable, limited and costly. Therefore, the improvement of environmental-friendly adhesive from natural agricultural products has awakened noteworthy attention. A novel adhesive for wood application was successfully prepared with enhanced shear strength and water resistance. The Fourier transmform infrared spectra showed the surface functionalities of the functionalized carbon nanotubes (FCNTs) and soy protein isolate nanocomposite adhesive. The attachment of carboxylic functional group on the surface of the carbon nanotubes (CNTs) after purification contributed to the effective dispersion of the CNTs in the nanocomposite adhesive. Hence, enhanced properties of FCNTs were successfully transferred into the SPI/CNTs nanocomposite adhesive. These unique functionalities on FCNTs however, improved the mechanical properties of the adhesive. The shear strength and water resistance of SPI/FCNTs was higher than that of the SPI/CNTs. SEM images showed the homogenous dispersion of CNTs in the SPI/CNTs nanocomposite adhesive. The carbon nanotubes were distributed uniformly in the soy protein adhesive with no noticeable clusters at relatively reduced fractions of CNTs as shown in the SEM images, which resulted into better adhesion on wood surface. Mechanical (shear) mixing and ultrasonication with 30 minutes of shear mixing both showed an improved dispersion of CNTs in the soy protein matrix. However, ultrasonication method of dispersion showed higher tensile shear strength and water resistance than in mechanical (shear) mixing method. Thermogravimetric analysis of the samples also showed that the CNTs incorporated increases the thermal stability of the nanocomposite adhesive at higher loading fraction. Incorporation of CNTs into soy protein isolate adhesive improved both the shear strength and water resistance of the adhesive prepared at a relatively reduced concentration of 0.3%.The result showed that tensile shear strength of SPI/FCNTs adhesive was 0.8 MPa and 7.25MPa at dry and wet state respectively, while SPI/CNTs adhesive had 6.91 MPa and 5.48MPa at dry and wet state respectively. There was over 100% increase in shear strength both at dry and wet state compared to the pure SPI adhesive. The 19% decrease in value of the new adhesive developed compared to the minimum value of ≥10MPa of European standard for interior wood application may be attributed to the presence of metallic particles remaining after purification of CNTs. The presence of metallic particles will prevent the proper penetration of the adhesive into the wood substrate. The type of wood used in this study as well as the processing parameters could also result into lower value compared to the value of European standard. Therefore, optimization of the processing parameter as well as the conversion of carboxylic acid group on the surface of the CNTs into acyl chloride group may be employed in future investigation. However, the preparation of new nanocomposite adhesive from soy protein isolate will replace the formaldehyde and petrochemical adhesive in the market and be of useful application in the wood industry. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

Gegenstand der Arbeit ist die Analyse der bei hohen Verformungsgraden in Werkstoffen durch kollektive Bewegung der Versetzungen entstandenen neuen Defektkonfigurationen, die auf der mesoskopischen Skala agieren. Diese so genannte Disklinationen rufen neben starken Gitterdehnungen auch erhebliche lokale Gitterrotationen hervor. Es wurde der Nachweis der Existenz der Disklinationen in plastisch verformten Kristallen geliefert sowie die qualitative und quantitative Analyse der Disklinationskonfigurationen und der Disklinationsstärke durchgeführt. Die Untersuchungen an stark verformten Ein- und Vielkristallen wurden mittels sowohl lokalen Methoden der Transmissions- (TEM, CBED) und Rasterelektronenmikroskopie (REM, EBSD) als auch der integralen Methoden der Röntgenstrukturanalyse (XRD) durchgeführt. Die Ergebnisse haben gezeigt, dass die Entwicklung der Zellblockstruktur mit erheblichem Anstieg der Desorientierungen und Versetzungsdichten in Versetzungswänden verbunden ist und durch die Bildung der Netzwerke von Disklinationen gefördert wird.

In alkalischen Lösungen führt die Reaktion von Hydroxylionen mit den Si-O-Si-Bindungen des Glasnetzwerks zur Bildung hydratisierter Oberflächen und gelöstem Silikat. Der Grad der Korrosion bzw. der Alterung der Glasfaser ist abhängig von der chemischen Zusammensetzung des Glases und Korrosionslösung sowie von Zeit und Temperatur. Die Untersuchung von Glasfasern verschiedener chemischer Zusammensetzung in NaOH- sowie Zementlösungen zeigte, dass die inhibierende Wirkung von Ca-Ionen zu einem veränderten Korrosionsmechanismus führt. Dies konnte anhand der mechanischen Eigenschaften der Glasfasern sowie rasterelektronenmikroskopischen Untersuchungen gezeigt werden. Während die Korrosion in NaOH-Lösung zu einer ausgeprägten Umwandlung der gesamten äußeren Glasfaserschicht in Reaktionsprodukte führte, zeigten Glasfasern in Zementlösung bei gleichem pH-Wert einen stark lokal begrenzten, punktförmigen Angriff. Daraus resultieren unterschiedliche mechanische Eigenschaften der Glasfasern in Abhängigkeit von der gewählten Korrosionslösung.

According to the 2019 Canadian infrastructure report card, a concerning amount of municipal infrastructure is in poor or very poor condition. The infrastructure in this condition requires immediate action for rehabilitation or replacement. For concrete infrastructure, an effective repair can extend its service life and ensure that the services it provides continue to meet the community expectations. However, unfavorable environmental factors such as repeated/cyclic loads and freezing and thawing cycles adversely affect the bond between substrate concrete and repair materials, which lowers the structural capacity of repaired structures. So far, researchers have found that bond strength of repair can be affected by surface roughness, surface moisture, chemical adhesion or cohesion, curing regime, properties of substrate and repair materials, use of bond agent, and curing regimes. These findings are mostly based on the studies that focused on cold-jointed cylinders or beams, but in real-life repair situations, repairs of beams or slabs are located at either tension or compression side of the structure. Currently, there is no comprehensive study that investigates the bond of concrete repair under a combination of freezing and thawing and repeated/cyclic loading conditions. In addition, it is challenging to provide a rapid and non-destructive evaluation of the bond deterioration of repair materials. To address these issues systematically, this dissertation breaks the task into four phases. Phase (I) focuses on the development of an engineered “crack-free” repair mix that contains polypropylene (PP) fiber. A novel method is used to surface treat the PP fibers with supplementary cementitious materials. The effectiveness of surface-treating fibers for improved bond strength and reduced cracking is investigated. The compressive, tensile, and flexural strength of this engineered repair mix are determined and compared with two commercially available repair materials. The results from Phase I show that by adding 0.2% (by weight) Metakaolin-treated fibers into concrete mix, the compressive strength improves by up to 15.7% compared to mixes with untreated fibers. This study achieved a strength increase of 13.5% as compared to the reported 3.3% in other studies that use 25 times the amount of metakaolin used in this study. The experimental results confirm that at 0.2% dosage level, the use of novel surface treating technique is a cost-effective way to improve the strength of repair materials. Phase (II) focuses on characterizing the bond strength of various repair systems after freezing-thawing (FT) damage using both non-destructive and destructive methods. Two innovative sounding methods, which overcome the subjectivity of the traditional chain drag method, are used to evaluate FT damage non-destructively. In the experimental study, beams with a U-shaped cut are made to simulate conditions experienced by a concrete structure during a typical repair project. Three types of repair materials are used including cementitious repair concrete, cementitious repair mortar, and polymer-modified cementitious mortar. After up to 300 cycles of freeze-thaw exposure, resonant frequency and bond flexural strength of the prismatic specimens are determined. The empirical equations relating Non-destructive test (NDT) measurements and flexural bond strength of the repaired structures after freeze-thaw (FT) exposure are proposed. The results from Phase II show that the change in dynamic modulus of elasticity determined from NDTs agrees well with the change in other measurements including flexural bond strength, interfacial crack width, and mass loss after freeze-thaw exposure. In this study, linear relationships are established between dynamic modulus of elasticity and flexural bond strength for both cementitious and polymer-modified cementitious repair mortar with a coefficient of determination ranging between 0.87 and 0.95. The proposed empirical models can be used to predict bond flexural strength of repaired structures based on NDT measurement. Also, it was found that the samples repaired with polymer-modified cementitious mortar (Mix P) have superior FT resistance compared to other repaired samples. Phase (III) focuses on investigating the structural capacity and bond performance of repaired beams after cyclic/repeated loading. To accelerate the test process, a novel modified loading regime consisting of cycle groups of increasing cyclic/repeated stress amplitude is proposed. The models proposed by literature and current codes and standards are used to validate the results. Phase (IV) focuses on the development of the damage models for both individual and combined FT and cyclic loading exposure on repaired concrete structures. The results in phase III show the feasibility of using the Palmgren-Miner rule and Goodman linear model to estimate the fatigue life of repaired structures. This was confirmed within the context of this study. This study established the usefulness of using groups of increasing cyclic stress amplitude to accelerate the fatigue test process. The two-million cycle fatigue endurance limit estimated using cycle groups of Mix S (70.8%) was very similar to what was reported in the literature (71%) using the traditional time-consuming cyclic loading method. This study found that the formulas proposed by CSA 23.3 can effectively predict the moment resistance of both intact (control) and repaired RC beams. The ratio of experimental moment resistance values to its predictions ranges from 0.91 to 1.04. Based on the experimental results of previous three phases, an empirical model that predicted the fatigue service life of FT-damaged concrete structures is proposed. Future research requires a more comprehensive study on the FT performance of various polymer-modified cementitious mortars of different mix designs in repairing concrete structures. By increasing the number of tested specimens, a better relationship could be established between destructive and NDT methods. Future research is also required to explore the combined effect of FT and cyclic loading on repaired RC structures experimentally. / Graduate / 2023-03-22

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