The theoretical part describes the principles of the free-radical induced grafting and the influence of various parameters on the reactions course. The literature research summarizes the latest knowledge in the field of the reactive modification of polypropylene (PP), it is mainly focused on the PP modification using an unsaturated acid anhydrides. Theoretical part describes the various procedures and modification of technology in order to increase the grafting yield of maleation. The experimental part is determined by the influence of the stabilizers concentration, the peroxide structure, and the binary mixture of monomers on the grafting yield and the reaction course. In the first part, the critical stabilizers concentration was determined based on the experimentally obtained relationship between the grafting yield and the stabilizers concentration. A kinetic schema of grafting of MAH onto PP in the presence of stabilizers has been proposed and compared with the experimental results. The effect of the stabilizers on the extent of the undesirable b-scission was evaluated based on the melt flow rate (MFR) and the rheological curves of PP-g-MAH. In the second part, the effect of the peroxide structure and the concentration of reactants on the grafting yield of PP modification with MAH and itaconic anhydride (IAH) was observed. The initial grafting yield Rg has been experimentally determined and compared with a defined area of theoretical values of Rg. The extent of b-scission was significantly influenced by the structure and the concentration of peroxide, as shown by the results of MFR and the rheological curves of PP-g-MAH. The last part of the doctoral thesis is focused on the assessment of the combination of MAH and IAH as comonomers on the grafting yield. At first, the reference polymers were prepared using the solution polymerization of MAH, and IAH, and copolymerization of MAH with IAH. The reference polymers were analyzed by FTIR, DSC, WAXS to confirm the probable copolymerization of MAH and IAH. The dependence of the reaction enthalpy on the reaction time was observed using simulations of bulk polymerization of MAH, IAH and mixtures MAH and IAH "in situ" in isothermal calorimeter. PP was subsequently modified with a combination of MAH and IAH as comonomers in order to assess its effect on the grafting yield

Polymeric coatings are being used in a growing number of applications, contributing to protection against weather conditions and localized corrosion, reducing the friction and erosion wear on the substrate. In this study, various polypropylene (PP) coatings were applied onto steel substrates by compression molding. Chemical modification of PP has been performed to increase its adhesion to metallic surfaces by grafting of maleic anhydride (MAH) onto PP in the presence of dicumyl peroxide (DCP). Influence of different concentrations of MAH and DCP on the properties of resulting materials have been examined. The coated steel samples are characterized by scanning electron microscopy (SEM), shear adhesion testing, FTIR and tribometry. The coatings with 3 wt. % MAH have shown the maximum adhesion strength due to maximum amount of grafting. The wear rates increased with increasing the amount of MAH due to simultaneous increase in un-reacted MAH.

As a preliminary starting point for the present study, physical and mechanical properties of polypropylene nanocomposites (PPNCs) for samples received from Queen's University Belfast have been evaluated. Subsequently, polymer/clay nanocomposite material has been produced at Bradford. Mixing and processing routes have been explored, and mechanical properties for the different compounded samples have been studied. Clay intercalation structure has received particular attention to support the ultimate objective of optimising tensile and fracture behaviour of isotropic and die-drawn PPNCs. Solid-state molecular orientation has been introduced to PPNCs by the die-drawing process. Tensile stress-strain measurements with video-extensometry and tensile fracture of double edge-notched tensile specimens have been used to evaluate the Young¿s modulus at three different strain rates and the total work of fracture toughness at three different notch lengths. The polymer composite was analyzed by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, wide angle x-ray diffraction, and transmission electron microscopy. 3% and 5% clay systems at various compatibilizer (PPMA) loadings were prepared by three different mixing routes for the isotropic sheets, produced by compression moulding, and tensile bars, produced by injection moulding process. Die-drawn oriented tensile bars were drawn to draw ratio of 2, 3 and 4. The results from the Queen's University Belfast samples showed a decrement in tensile strength at yield. This might be explained by poor bonding, which refers to poor dispersion. Voids that can be supported by intercalated PP/clay phases might be responsible for improvement of elongation at break. The use of PPMA and an intensive mixing regime with a two-step master batch process overcame the compatibility issue and achieved around 40% and 50% increase in modulus for 3% and 5% clay systems respectively. This improvement of the two systems was reduced after drawing to around 15% and 25% compared with drawn PP. The work of fracture is increased either by adding nanoclay or by drawing to low draw ratio, or both. At moderate and high draw ratios, PPNCs may undergo either an increase in the size of microvoids at low clay loading or coalescence of microvoids at high clay loading, eventually leading to an earlier failure than with neat PP. The adoption of PPMA loading using an appropriate mixing route and clay loading can create a balance between the PPMA stiffness effect and the degree of bonding between clay particles and isotropic or oriented polymer molecules. Spherulites size, d-spacing of silicate layers, and nanoparticles distribution of intercalated microtactoids with possible semi-exfoliated particles have been suggested to optimize the final PPNCs property. / SABIC

<p>Maleation is a common means of modification for many commodity polymers and is used to several ends. In this study, various waxes were functionalized with maleic anhydride through several maleation processes, with the end goal of obtaining a cost effective processes to make emulsifiers to be used in emulsions that impart water-resistance to building products, such as gypsum wallboards. Research was done in collaboration with an industrial partner, in order to replace commercially available emulsifiers currently being used in their processes with a less costly product that could easily be made on-site based on their consumption requirements, through a solvent-free approach. Reactions involving both the free-radical initiated maleation of paraffin waxes and thermal addition of maleic anhydride to alpha-olefins were examined extensively. It was found that emulsions with properties matching or exceeding those of control emulsion formulations were obtainable using experimental emulsifiers made through both maleation methods. When used in gypsum wallboards, emulsifiers made through thermal maleation showed levels of water-repellency that matched or exceeded those of control formulations at lower loading levels, while emulsifiers made through free-radical maleation were subject to performance issues.</p> / Master of Applied Science (MASc)

High molecular weight star-shaped polystyrenes were prepared via the coupling of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) terminated polystyrene oligomers with divinylbenzene (DVB) in m-xylene at 138 °C. Linear polystyrene oligomers (Mn = 19,300 g/mol, Mw/Mn = 1.10) were synthesized in bulk styrene using benzoyl peroxide in the presence of TEMPO at approximately 130 °C. In situ mid-infrared spectroscopy was successfully utilized to follow initiation, monomer conversion, and polymer formation. Real-time data allowed for the determination of apparent rate constants of 2.1E-5 s⁻¹ at 132 °C and 1.2E-5 s⁻¹ at 126 °C from the profile of the decaying styrene vinyl carbon-hydrogen (=CH₂) absorbance at 907 cm⁻¹. Coupling of the TEMPO terminated oligomers under optimum conditions resulted in a compact and dense product with a number average molecular weight exceeding 300,000 g/mol (Mw/Mn = 3.03) after 24 h, suggesting the formation of relatively well-defined star-shaped polymers. Synthetic factors that affected the molecular weight, yield, and composition of maleic anhydride (MAH), norbornene (Nb), and tert-butyl 5-norbornene-2-carboxylate (NbTBE) terpolymers were investigated. Pseudo first order kinetic analysis using in situ FTIR indicated that the observed rate of reaction was a strong function of the Nb/NbTBE ratio with a maximum of 6.7E-5 s⁻¹ for a 50/0/50 Nb/NbTBE/MAH monomer ratio and a minimum of 1.1E-5 s⁻¹ for a 0/50/50 Nb/NbTBE/MAH ratio. Polymer yields were also observed to be a function of the Nb/NbTBE ratio and also decreased with increasing NbTBE. Calculated work of adhesion values (Wadh) values were observed to increase as the content of NbTBE was increased. 193 nm photoresist formulations incorporating polymers with high NbTBE content showed increased imaging performance using 193 nm light and successfully produced sharp and defined features as small as 110 nm, which was demonstrated via scanning electron microscopy (SEM). Additional functionality was introduced via the copolymerization of MAH with several norbornene (Nb) derivatives that were synthesized from facile Diels-Alder cycloaddition reactions of cyclopentadiene with a-olefins containing electron withdrawing groups. Subsequent hydrolysis of the anhydride offered further versatility and provided an avenue to introduce aqueous base solubility into Nb/MAH copolymers. / Ph. D.

Langmuir-monolayer formation at the air/water interface (A/W) can be achieved by spreading amphiphilic molecules on a liquid subphase and compressing them into an ordered arrangement. The use of the Langmuir-Blodgett technique (LB) to prepare ultra thin films on solid surfaces from monolayers at A/W has considerable utility for studying surface interactions. In particular, the phase behavior of polyhedral oligomeric silsesquioxanes (POSS) was examined using a combination of LB and Brewster angle microscopy (BAM).Polymer fillers have been shown to reduce the cost and often improve the properties of high performance polymer composites. The utility of POSS as a potential nanofiller in blends with polymers such as poly(dimethylsiloxane) (PDMS) and poly(vinylacetate) (PVAc) was explored using surface pressure-area per monomer isotherms (P-A) and BAM. Substantial morphological differences are seen between polymer blends with heptasubstituted trisilanol-POSS and fully condensed octasubstituted-POSS due to differences in subphase affinity.Several poly(1-alkene-alt-maleic anhydride) (PXcMA) polymers were studied at both the gas/liquid interface as Langmuir films and at the gas/solid interface as Langmuir-Blodgett thin films on silicon substrates. A 0.01 M HCl solution (pH~2) was used during film deposition to ensure the carboxylic acids were fully protonated. The PXcMA polymers included X=1-hexene, 1-octene, 1-decene, and 1-octadecene (represented as PHcMA, POcMA, PDcMA, and PODcMA respectively). The P-A isotherms of these polymers were consistent with those obtained previously.1Tensiometry was used to determine the critical micelle concentrations (c.m.c.) of variable molar mass poly(dimethylsiloxane-b-(3-cyanopropyl)methylsiloxane-b-dimethylsiloxane) (PDMS-PCPMS-PDMS) triblock copolymers and a poly(dimethylsiloxane-b-2-ethyl-2-oxazoline) diblock copolymer. Dynamic light scattering (DLS) corroborated interfacial tension results. The polymers exhibited well-defined temperature-independent c.m.c.'s. These measurements ensured that the synthesis of cobalt nanoparticles for biocompatible magnetic fluids occurred above the c.m.c. / Master of Science

A microscopia de fluorescência é uma das técnicas mais poderosas disponíveis atualmente, uma vez que proporciona uma combinação excepcional de alta sensibilidade na detecção, alta especificidade, além de ser consideravelmente não invasiva. Avanços recentes permitiram a detecção em resolução de subdifração, o que eleva sua potencialidade de investigação de um maior número de sistemas e, consequentemente, de avanço científico. O estudo de novas sondas fluorescentes é de fundamental importância para a aplicação em métodos avançados de microscopia óptica. Na primeira vertente da pesquisa, Capítulo 2, foi realizado o estudo fotofísico de uma série de compostos bisarilados derivados do anidrido maleico e de maleimidas sintetizados pela reação de Heck-Matsuda. Visando o aprimoramento do design dessas moléculas, foi realizada a ciclização fotoquímica de tais compostos, resultando em moléculas com anéis condensados, nomeados como derivados de fenantreno, as quais proporcionaram maior estabilidade fotoquímica. A dinâmica do estado excitado remete ao efeito push-pull, em que há um deslocamento de carga notável, mas não completo. Para os compostos com a substituição 4-hidroxifenil foi observado um processo de deslocamento de carga combinado com uma transferência de próton no estado excitado assistida por solvente. Ademais, o estudo dos compostos derivados de fenantreno em microscopia confocal demonstrou que as propriedades locais do solvente afetam a dinâmica de relaxação de fluorescência em diferentes meios condensados e que os mesmos são passíveis de serem aplicados a técnicas avançadas de microscopia de fluorescência. A segunda vertente desta tese, Capítulo 3, explora um sistema biológico em nível de uma única molécula. Especificamente, este capítulo concerne à investigação de uma metodologia ótima para a marcação fluorescente de DNA em sequência específica, através de microscopia de fluorescência com super-resolução. As reações foram conduzidas utilizando uma metodologia de marcação de duas etapas, de acordo com o princípio mTAG. Na primeira etapa, grupamentos contendo alquino terminal, azida ou amina primária são transferidos do cofator análogo ao S-adenosil-L-metionina para o DNA através de uma enzima metiltransferase. Foi utilizada a enzima M.TaqI, a qual tem como alvo a sequência 5\'- TGCA -3\' para modificação. Na segunda etapa é realizado o acoplamento do fluoróforo aos sítios funcionais do plasmídeo (pUC19) através de reações químicas bioortogonais, tais como reação click catalisada por cobre (CuAAC), reação click na ausência de cobre (SPAAC) e acoplamento do grupo amina primária com NHS-éster. Também foi desenvolvida uma metodologia direta de uma etapa, na qual o fluoróforo é diretamente transferido do cofator análogo para o DNA em uma única etapa reacional. Para acompanhar o desempenho das reações foi desenvolvido um ensaio single-molecule para a contagem do número de moléculas de corante ligadas a plasmídeos individuais. A topologia dos plasmídeos após a marcação foi investigada por imagens de AFM em alta resolução. A combinação de ambas as análises demonstrou que a reação SPAAC assim como a reação direta de uma etapa promoveram uma marcação fluorescente quase completa e a técnica de AFM confirmou que o acoplamento de fluoróforos não induziu danos à estrutura dos plasmídeos, os quais preservaram sua morfologia nativa, superenrolada. Além disso, os plasmídeos marcados foram aplicados com sucesso a procedimentos de transfecção em células de mamíferos, indicando que o DNA reteve sua capacidade de codificar informação genética, mesmo na presença de fluoróforos ligados. / Fluorescence microscopy is one of the most powerful techniques currently available, since it provides the unique combination of a high sensitivity in detection, a high specificity, and a considerable non-invasiveness. Recent developments have allowed the detection at a sub-diffraction resolution, which elevates its potentiality to investigate several systems and hence to go further in science. The study of new fluorescent probes is crucial for the application in advanced methods in optical microscopy. In the first extent of this research, Chapter 2, a photophysical study of maleic anhydride and maleimide derivatives, synthesized by the Heck-Matsuda reaction, was performed. Aiming at the improvement of the design of these molecules, a photochemical cyclization was carried out, resulting in molecules with condensed rings, termed as phenanthrene derivatives, which promoted more photochemical stability. The excited state dynamics rely on the push-pull effect, in which a notable, but not complete, charge shift takes place. For the compounds with a 4-hydroxyl substituent, a charge shift combined with an excited state solvent-assisted proton transfer was observed. Additionally, the confocal microscopy study of the phenanthrene derivatives showed that the local properties of the solvent modulate the fluorescence relaxation dynamics in condensed media and hence such dyes can be potential candidates for use in advanced fluorescence microscopy techniques. The second extent of this thesis, Chapter 3, explores a biological system at the single-molecule level. Specifically, this chapter concerns to an investigation of an optimal sequence-specific DNA fluorescent labelling, using super-resolution fluorescence microscopy. The reactions were performed using a two-step methodology, according to the mTAG approach. In the first step, moieties containing a terminal alkyne, azide, or primary amine group are transferred from an S-adenosyl-L-methionine analogue cofactor to the DNA by a methyltransferase enzyme. Herein, the enzyme M.TaqI was used, which targets the 5\'- TCGA -3\' sequence for modification. In the second step, a fluorophore is coupled to the functional sites of the plasmid (pUC19) using bio orthogonal reactions, such as the click reaction catalysed by copper (CuAAC), the copper-free click reaction (SPAAC), and the amino-to-NHS-ester coupling reaction. A direct one-step approach in which the fluorophore is directly transferred to the DNA from the analogue cofactor in a single reaction step, was also developed. A single-molecule assay was developed for counting the number of fluorophores associated with the individual plasmids. The topology of the plasmids after labelling was also investigated by high-resolution AFM imaging. Combining both analysis, the SPAAC as well as the direct one-step reactions were found to promote near-complete labelling and the AFM showed that the fluorophore coupling did not damage the structure of the plasmids and that their native, supercoiled, morphology was preserved. Moreover, labelled plasmids were successfully applied for transfection into mammalian cells, implying that the DNA retained its ability to encode genetic information, even while carrying bound fluorophores.

Made available in DSpace on 2017-07-21T20:42:32Z (GMT). No. of bitstreams: 1 dissertacao - arquivos para publicar.pdf: 1279347 bytes, checksum: a251737807cada580c8a5af0b1c88bff (MD5) Previous issue date: 2010-03-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work the ultra high molecular weight polyethylene grafting with maleic anhydride by ball milling process was studied. UHMWPE with molecular weight of 8x106 g.mol-1, maleic anhydride and benzoyl peroxide were used. The ball milling process was performed in Attritor and Spex mills. The milling time, peroxide concentration and, in case of Attritor mill, the rotation, were the variables studied. We used two distinct levels for each variable and all possible combinations were studied with the use of statistical analysis for better interpretation of the results. The residual maleic anhydride was extracted from the samples by soxhlet extractor with acetone as a solvent. FTIR, SEM, XRD and bulk density measurements were performed for characterization. FTIR results revealed that the UHMWPE graft with maleic anhydride occurred for the processing in both mills. In case of the Attritor mill, the milling time and the rotation were the most influent variables in UHMWPE grafting. The peroxide concentration also affected the process, but with less intensity. For the Spex mill processing, the milling time was the most influent variable in grafting process, with the peroxide concentration again affecting less the process. The ball milling modified the polymer particles morphology, transforming from sphere to flake like. This transformation occurred in different levels, being correlated with milling time and rotation in case of Attritor mill. According to the change in the shape of the polymer particles, the bulk density was also affected by the same variables. The polymer crystalline structure was studied by XRD, where the influence on the variables was determined for the formation of monoclinic and orthorhombic phases. It was found that for the Attritor mill, the milling process induces the formation of a monoclinic phase, but it proved independent of the variables involved in the ball milling process. To the Spex mill processing, no change was detected in the concentration of the monoclinic phase, probably due to the warming occurred in the process that promotes the monoclinic-orthorhombic inversion around 70 º C. The ball milling also affected the thermal properties of the polymer, such as temperature and enthalpy of melting and crystallization. In this case, any variable proved influential in differentiating these thermal properties of milled samples in different conditions. The only significant difference was observed between the thermal properties of the milled samples for the no milled sample. / No presente trabalho foi estudada a funcionalização do polietileno de ultra alta massa molar com anidrido maleico através do processo de moagem de alta energia. Utilizou-se o PEUAMM de massa molar de 8 milhões de gramas por mol, anidrido maleico e peróxido de benzoíla. As moagens foram realizadas nos moinhos Attritor e Spex e as variáveis envolvidas no processo foram o tempo de moagem, a concentração de peróxido e, no caso do moinho Attritor, a rotação. Foram utilizados dois níveis distintos para cada variável e todas as combinações possíveis foram estudadas, com a utilização de análise estatística para a melhor interpretação dos resultados. O anidrido maleico não reagido foi extraído das amostras moídas por meio de extrator soxhlet com o emprego de acetona. As caracterizações foram efetuadas através de FTIR, DSC, MEV, DRX e medidas de densidade aparente. Os resultados de FTIR das amostras revelaram que a funcionalização do PEUAMM com anidrido maleico ocorreu para o processamento em ambos os moinhos. No caso do moinho Attritor, o tempo de moagem e a rotação foram as variáveis mais influentes na funcionalização do PEUAMM. A concentração de peróxido também se mostrou influente no processo, mas de forma menos intensa. Para o processamento no moinho Spex, o tempo de moagem foi a variável mais influente no processo de funcionalização, com a concentração de peróxido novamente influenciando de maneira menos intensa. A moagem modificou a morfologia das partículas do polímero, transformando-as de aproximadamente esféricas para “flakes”. Esta transformação ocorreu em diferentes níveis, relacionados com o tempo de moagem e com a rotação do moinho no caso do Attritor. De acordo com a modificação no formato das partículas do polímero, a densidade aparente também foi afetada pelas mesmas variáveis. A estrutura cristalina do polímero foi estudada através dos dados de DRX, onde foi verificada a influência das variáveis na formação das fases monoclínica e ortorrômbica do polímero. Obteve-se que para o moinho Attritor o processo de moagem induziu a formação de fase monoclínica, mas sua quantidade se mostrou independente das variáveis envolvidas no processo de moagem. Para o processamento via Spex nenhuma mudança foi detectada na concentração da fase monoclínica, provavelmente devido ao aquecimento ocorrido no processo e que promove a reversão monoclínica-ortorrômbica por volta de 70ºC. A moagem também afetou propriedades térmicas do polímero, como temperaturas e entalpias de fusão e cristalização. Neste caso, nenhuma variável se mostrou influente para diferenciar tais propriedades térmicas das amostras moídas nas diferentes condições. A diferença significativa observada foi apenas entre propriedades térmicas de amostras moídas em relação à amostra não moída.

Ce travail porte sur le greffage radicalaire de l'anhydride maléique sur un polyéthylène basse densité, en voie fondu, et en présence d'un abstracteur d'atome d'hydrogène. L'utilisation des radicaux nitroxyle, comme agent de terminaison, en présence d'un peroxyde a permis de bloquer la réaction de réticulation du polyéthylène, réaction secondaire fréquemment rencontré lors de l'utilisation de radicaux peroxyle, tout en permettant le greffage d'une faible quantité d'anhydride maléique. L'élimination d'une partie de l'anhydride maléique et des radicaux nitroxyle via des réactions secondaires à haute température semble toutefois inévitable. La substitution du peroxyde par une alcoxyamine dans le rôle d'abstracteur d'atome d'hydrogène a alors permis d'atteindre des taux de greffage en anhydride maléique supérieurs pour une modification des propriétés rhéologiques du polyéthylène équivalente. Néanmoins, des incertitudes demeurent encore sur le mécanisme de décomposition thermique de cette alcoxyamine permettant la réaction de greffage. / This work deals with melt grafting of maleic anhydride onto low density polyethylene using radical initiators which are able to abstract hydrogen from the polyolefin backbone. The use of a nitroxide radical as a termination reagent in presence of peroxide allowed to prevent the polyethylene crosslinking during the maleic anhydride grafting. Indeed, the polyethylene crosslinking is the main side reaction but the elimination of a small proportion of the reagents (monomer and nitroxide radical) through other side reactions seems to be unavoidable. The peroxide substitution by an alcoxyamine leaded to a higher grafted maleic anhydride rate for the same polyethylene rheological modification. Nevertheless, the thermal decomposition mechanism of the alcoxyamine which makes the grafting reaction possible is still uncertain.

Polypropylene (PP) and ethylene-co-octene copolymer (EOC) blends were prepared at various component ratios and reinforced with silica nanoparticles (SiO2). Strategies to improve filler dispersion involved the grafting of a silane coupling agent on the PP matrix, the addition of a maleated PP (PP-g-MA) as a compatibilizer and the use of hydrophobic silica nanoparticles. These approaches resulted in a fine dispersion of the nanoparticles within the PP phase and induced a reduction of the size of the EOC domains, due to a barrier effect. Tensile and flexural properties were significantly increased, whereas ductility and impact properties were not affected. These enhancements are attributed to the favourable microstructure of the blends, featuring a segregated microstructure, and to the improved interfacial adhesion between the functionalized polymer matrix and the surface of the nanoparticles. The microstructure and rheology of model melt compounded EOC-based nanocomposites were investigated. Functionalization of the polyolefin matrix was accomplished through silane grafting, or addition of a maleated EOC (EOC-g-MA) compatibilizer. Various grades of unmodified SiO2 having different specific surface areas (SSA), as well as a surface-modified grade were added to the EOC matrix at various loadings. The formation of covalent and hydrogen bonds between the silanol groups and the functionalized polymer generated strong polymer/filler (P/F) interactions, resulting in improved filler dispersion. Bound polymer characterization revealed that in the compatibilized materials, the amount of polymer physically attached to the nanoparticles was higher than in the non-compatibilized samples. In the absence of a compatibilizer, larger SiO2 aggregates formed upon increasing SSA because of increased probability of hydrogen bonding between the particles. The increased propensity for aggregation was revealed by time sweeps as well as by the increased strain sensitivity in stress sweeps. On the contrary, the compatibilized composites exhibited a stable response and a higher critical strain for the onset of non-linearity, indicative of stronger adhesion between the fillers and the matrix. Superposition of oscillatory and creep/recovery experiments revealed that the viscoelastic properties in the terminal region were influenced substantially by the state of dispersion of the nanoparticles. In the absence of a compatibilizer, substantial enhancements in the linear viscoelastic (LVE) functions were noted and an increasing SSA resulted in more significant deviations from terminal flow. On the contrary, the SSA of the particles had no effect on the viscoelastic and mechanical properties of the compatibilized composites. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2011-04-18 15:17:52.471