This dissertation investigates the self assembly and automatic oscillation of intelligent poly (N-isopropylacrylamide) [PNIPAM] microgel particles. The equilibrium phase diagram as a function of temperature and concentration was constructed for the charged PNIPAM spheres. The PNIPAM microgel particles display rhythmic size oscillations when covalently coupled to a nonlinear chemical reaction, the Belousov-Zhabotinsky (BZ) reaction. The nonequilibrium dynamics of PNIPAM microgels in the presence of BZ reaction was studied by the systematic variation of substrate concentrations and temperature. In addition, the BZ chemical reaction was modeled to reveal the existence of upper temperature limits for nonlinear chemical systems. The experiments employ environment sensitive PNIPAM particles that are sensitive to temperature, pH, and ionic strength. The PNIPAM particles have been demonstrated here to behave as hard spheres at low pH values and soft spheres at high pH. This is done by measuring the freezing and melting boundary of fluid-crystal coexistence region with a new technique which is simpler and quicker compared to the traditional sedimentation method. A novel method was developed to achieve size uniformity of PNIPAM gel particles with covalently-bound tris(bipyridyl)ruthenium(II) via the coordination chemistry between a ruthenium complex and the monodispersed PNIPAM gel particles bearing bipyridine ligands. The correlation between the dynamic behavior of BZ reaction induced mechanical oscillations of PNIPAM particles and substrate concentrations was presented in a ternary phase diagram. In particular, the dependence of oscillation frequency and induction time on the substrate concentrations was studied. The temperature dependency of the induction time and oscillatory frequency of the BZ reaction in this polymerimmobilized catalyst system were compared to the bulk BZ reaction with the catalyst in the solution phase. Prolonged induction times were observed for the immobilized catalyst, compared with free catalyst, while little difference was observed on the oscillation frequency. A theoretical improvement has been achieved by incorporating the temperature dependence in the BZ Oregonator model. Bifurcation has been calculated in the phase space spanned by initial reagents concentration ratio, stoichiometric factor and temperature. The existence of upper temperature limits has been demonstrated.

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A utilização de combustíveis fósseis é percebida, cada vez mais, de forma negativa, visto seus elevados níveis de emissão de gases de efeito estufa. Por conta disso, busca-se a ampliação do uso de combustíveis de origem renovável de forma a diminuir o impacto ambiental. Dentre esses, o etanol se destaca pelas excelentes características físico-químicas. Ao se reduzir o nível de pureza (diluição em agua) durante o processo de destilação desse combustível, obtém-se um sensível decréscimo da energia dispendida na sua produção. Isso se deve ao crescimento exponencial do consumo energético para obtenção de misturas com teor de etanol superiores à 80% v/v. Assim, a possível utilização de misturas superhidratadas, mesmo que apresentem menor poder calorífico, resultam em uma economia direta de energia no processo de obtenção. Dessa forma, esse trabalho avalia o impacto da utilização de misturas de etanol com elevadas concentrações de água em um motor monocilíndrico de testes, com volume deslocado de 0,668 L, injeção de combustível no coletor de admissão, e ignição por centelha. Inicialmente, avaliou-se via testes de bancada o efeito da substituição direta do etanol comercial por misturas com maior hidratação nos parâmetros de desempenho e emissões. Em seguida, buscou-se explorar as características anti-detonantes da água através do aumento da razão de compressão visando ao aumento de eficiência indicada do motor. Por fim, estudos numéricos foram conduzidos de forma a verificar o efeito da concentração de água sobre os valores de velocidade de chama e temperatura adiabática em uma chama livre unidimensional. Foram também determinados os valores de tempo de indução para condições de temperatura e pressão experimentais. Com isso, observou-se a possibilidade de operação com elevadas razões de compressão para maiores percentuais de água com sensível aumento da eficiência indicada e nível de emissões semelhantes ao etanol comercial. O aumento de água causou uma diminuição na velocidade de queima e na temperatura adiabática de chama, enquanto que o tempo de indução possuiu efeitos opostos dependentes da condição de operação. / The use of fossil fuels have faced several restrictions due its higher greenhouse gas emissions during the combustion process in internal combustion engines. Thus, there is an urge aiming to diversify the number of renewable fuels in order to decrease the environmental impact. Among them, ethanol is notorious, presenting excellent physico-chemical properties. Decreasing the ethanol level on ethanol-in-water mixtures after the distillation process, a lower energy expense can be achieved. This is related to the exponential growing in the energy consumption to obtain mixtures containing ethanol in water concentrations higher than 80% v/v. Therefore, the use of highly hydrated mixtures, despite the decrease in heat values, results in energy savings during its production process. This work evaluates the impact of using mixtures containing high water concentrations in a single cylinder engine, 0.668L, with port fuel injection, and spark ignition combustion. The direct replace of commercial ethanol by highly hydrated mixtures was evaluated through dynamometer tests, so performance and emissions parameters were obtained. After this, it was explored the knock resistance increase due to water addition by increasing the compression ratio, aiming at reaching higher indicated efficiency values. Finally, numerical studies were conducted in order to verify the effect of water concentration increase on laminar flame speed and adiabatic flame temperatures in a one dimensional free flame simulation software. In addition, the induction time for temperature and pressure conditions obtained from experimental results was assessed. As conclusions, the increase in water concentration enabled the use of high compression ratios resulting in higher indicated efficiency values than for commercial ethanol with the same exhaust emission concentrations. Higher water volumes resulted in lower laminar flame speeds and adiabatic flame temperatures. In addition, the induction time values presented two different behavior according to the operating conditions.

Admixtures like reactants and byproducts are solublenon-crystallizing compounds that can be present in industrialsolutions and affect crystallization of the main substance.This thesis provides experimental and molecular modellingresults on the influence of admixtures on crystal nucleation ofvanillin (VAN). Seven admixtures: acetovanillone (AVA),ethylvanillin (EVA), guaiacol (GUA), guaethol (GUE), 4-hydroxy-acetophenone (HAP), 4-hydroxy-benzaldehyde (HBA), andvanillic acid (VAC) have been used in this study. Classicalnucleation theory is used as the basis to establish arelationship between experimental induction time andsupersaturation, nucleation temperature, and interfacialenergy. A novel multicell device is designed, constructed, andused to increase the experimental efficiency in thedetermination of induction times by using 15 nucleation cellsof small volumes simultaneously. In spite of the largevariation observed in the experiments, the solid-liquidinterfacial energy for each VAN-admixture system can beestimated with an acceptable statistical confidence. At 1 mole% admixture concentration, the interfacial energy is increasedin the presence of GUA, GUE, and HBA, while it becomes lower inthe presence of the other admixtures. As the admixtureconcentration increases from 1 to 10 mole %, the interfacialenergy also increases. The interfacial energies obtained are inthe range 7-10 mJ m-2. Influence of admixtures on metastable zone widthand crystal aspect ratio of VAN is also presented. Theexperimental results show that the admixtures studied arepotential modifiers of the nucleation of VAN. Molecularmodelling by the program Cerius2 is used to identify the likelycrystal growth faces. Two approaches, the surface adsorptionand the lattice integration method, are applied to estimatequantitatively the admixture-crystal interaction energy on thedominating crystal faces of VAN,i.e., {0 0 1} and {1 0 0}. However, a simple and clearcorrelation between the experimental values of interfacialenergy and the calculated interaction energies cannot beidentified. A qualitative structural analysis reveals a certainrelationship between the molecular structure of admixtures andtheir effect on nucleation. The determination of the influenceof admixtures on nucleation is still a challenge. However, themolecular and crystal structural approach used in this thesiscan lead to an improved fundamental understanding ofcrystallization processes. Keywords: Crystallization,nucleation, vanillin, admixtures, additives, impurities,induction time, interfacial energy, molecular modelling,interaction energy.

<p>Admixtures like reactants and byproducts are solublenon-crystallizing compounds that can be present in industrialsolutions and affect crystallization of the main substance.This thesis provides experimental and molecular modellingresults on the influence of admixtures on crystal nucleation ofvanillin (VAN). Seven admixtures: acetovanillone (AVA),ethylvanillin (EVA), guaiacol (GUA), guaethol (GUE), 4-hydroxy-acetophenone (HAP), 4-hydroxy-benzaldehyde (HBA), andvanillic acid (VAC) have been used in this study. Classicalnucleation theory is used as the basis to establish arelationship between experimental induction time andsupersaturation, nucleation temperature, and interfacialenergy. A novel multicell device is designed, constructed, andused to increase the experimental efficiency in thedetermination of induction times by using 15 nucleation cellsof small volumes simultaneously. In spite of the largevariation observed in the experiments, the solid-liquidinterfacial energy for each VAN-admixture system can beestimated with an acceptable statistical confidence. At 1 mole% admixture concentration, the interfacial energy is increasedin the presence of GUA, GUE, and HBA, while it becomes lower inthe presence of the other admixtures. As the admixtureconcentration increases from 1 to 10 mole %, the interfacialenergy also increases. The interfacial energies obtained are inthe range 7-10 mJ m^-2. Influence of admixtures on metastable zone widthand crystal aspect ratio of VAN is also presented. Theexperimental results show that the admixtures studied arepotential modifiers of the nucleation of VAN. Molecularmodelling by the program Cerius2 is used to identify the likelycrystal growth faces. Two approaches, the surface adsorptionand the lattice integration method, are applied to estimatequantitatively the admixture-crystal interaction energy on thedominating crystal faces of VAN,<i>i.e</i>., {0 0 1} and {1 0 0}. However, a simple and clearcorrelation between the experimental values of interfacialenergy and the calculated interaction energies cannot beidentified. A qualitative structural analysis reveals a certainrelationship between the molecular structure of admixtures andtheir effect on nucleation. The determination of the influenceof admixtures on nucleation is still a challenge. However, themolecular and crystal structural approach used in this thesiscan lead to an improved fundamental understanding ofcrystallization processes. Keywords: Crystallization,nucleation, vanillin, admixtures, additives, impurities,induction time, interfacial energy, molecular modelling,interaction energy.</p>

In this study, Tetrahydrofuran (THF) hydrates were formed in-situ in the Zetasizer Nano ZS90. With various concentrations of SDS, we attempted to characterize the SDS adsorption on the surface of the hydrate particles. In doing so, we tried to correlate the adsorption of SDS to THF hydrate induction times with respect to SDS concentration (0 – 3.47 mM), to determine whether the fast nucleation of THF hydrates is due to the adsorption of SDS. The measured ζ-potential for pure THF hydrates was -100 ± 10 mV, indicating anion adsorption. An adsorption curve was observed where there is saturation leveling. Correlating this data to the hydrate induction times, we see that when the saturation level is reached, a significant reduction in induction time can be seen.

In this study, Tetrahydrofuran (THF) hydrates were formed in-situ in the Zetasizer Nano ZS90. With various concentrations of SDS, we attempted to characterize the SDS adsorption on the surface of the hydrate particles. In doing so, we tried to correlate the adsorption of SDS to THF hydrate induction times with respect to SDS concentration (0 – 3.47 mM), to determine whether the fast nucleation of THF hydrates is due to the adsorption of SDS. The measured ζ-potential for pure THF hydrates was -100 ± 10 mV, indicating anion adsorption. An adsorption curve was observed where there is saturation leveling. Correlating this data to the hydrate induction times, we see that when the saturation level is reached, a significant reduction in induction time can be seen.

With sufficient time, a high density polyethylene geomembrane will degrade and lose its engineering properties until ruptures signal the end of its service-life. This thesis examines the longevity of nine different geomembranes; five of them were of different thickness manufactured from the same resin. The degradation of properties and time to failure are investigated for geomembranes: in immersion tests; as a part of a landfill composite liner; and, exposed to the elements. The different thermal and stress histories associated with manufacturing geomembranes of different thickness are shown to affect their morphological structure; consequently, their stress crack resistance. When immersed in synthetic leachate, it was found that: (a) thicker geomembranes have a longer antioxidants depletion time but the effect of thickness decreases with temperature and is less than expected; (b) inferences of geomembrane’s longevity based on its initial properties may be misleading because a geomembrane may chemically degrade (as manifested by the change in melt index) despite the presence of a significant amount of stabilizers (as manifested by the measured high pressure oxidative induction time); and, (c) stress crack resistance may change before antioxidant depletion or chemical degradation takes place, likely, due to changes in geomembrane morphological structure with the maximum decrease being observed at 55oC. Reductions also were measured for geomembrane immersed in air and water at 55oC. The geomembrane aged in a simulated landfill liner at 85oC is shown to have service-life as little as three years with 30,000 to >2.0 million ruptures/hectare at failure. For exposed geomembranes in Alumbrera (Argentina), samples were exhumed from two mine facilities after ~16 years of exposure. The antioxidants in exposed samples depleted to residual and the stress crack resistance had dropped to as low as 70 hours. Samples were exhumed from a different exposed geomembrane in a test site in Godfrey (Canada) after six years of exposure. The antioxidants were partially depleted, with depletion to residual projected to take at least 20 years; however, despite no evidence of chemical ageing, the stress crack resistance had decreased from 330 to 190 hours, likely due to changes in the morphological structure of the geomembrane. / Thesis (Ph.D, Civil Engineering) -- Queen's University, 2014-02-28 04:59:20.834

A utilização de combustíveis fósseis é percebida, cada vez mais, de forma negativa, visto seus elevados níveis de emissão de gases de efeito estufa. Por conta disso, busca-se a ampliação do uso de combustíveis de origem renovável de forma a diminuir o impacto ambiental. Dentre esses, o etanol se destaca pelas excelentes características físico-químicas. Ao se reduzir o nível de pureza (diluição em agua) durante o processo de destilação desse combustível, obtém-se um sensível decréscimo da energia dispendida na sua produção. Isso se deve ao crescimento exponencial do consumo energético para obtenção de misturas com teor de etanol superiores à 80% v/v. Assim, a possível utilização de misturas superhidratadas, mesmo que apresentem menor poder calorífico, resultam em uma economia direta de energia no processo de obtenção. Dessa forma, esse trabalho avalia o impacto da utilização de misturas de etanol com elevadas concentrações de água em um motor monocilíndrico de testes, com volume deslocado de 0,668 L, injeção de combustível no coletor de admissão, e ignição por centelha. Inicialmente, avaliou-se via testes de bancada o efeito da substituição direta do etanol comercial por misturas com maior hidratação nos parâmetros de desempenho e emissões. Em seguida, buscou-se explorar as características anti-detonantes da água através do aumento da razão de compressão visando ao aumento de eficiência indicada do motor. Por fim, estudos numéricos foram conduzidos de forma a verificar o efeito da concentração de água sobre os valores de velocidade de chama e temperatura adiabática em uma chama livre unidimensional. Foram também determinados os valores de tempo de indução para condições de temperatura e pressão experimentais. Com isso, observou-se a possibilidade de operação com elevadas razões de compressão para maiores percentuais de água com sensível aumento da eficiência indicada e nível de emissões semelhantes ao etanol comercial. O aumento de água causou uma diminuição na velocidade de queima e na temperatura adiabática de chama, enquanto que o tempo de indução possuiu efeitos opostos dependentes da condição de operação. / The use of fossil fuels have faced several restrictions due its higher greenhouse gas emissions during the combustion process in internal combustion engines. Thus, there is an urge aiming to diversify the number of renewable fuels in order to decrease the environmental impact. Among them, ethanol is notorious, presenting excellent physico-chemical properties. Decreasing the ethanol level on ethanol-in-water mixtures after the distillation process, a lower energy expense can be achieved. This is related to the exponential growing in the energy consumption to obtain mixtures containing ethanol in water concentrations higher than 80% v/v. Therefore, the use of highly hydrated mixtures, despite the decrease in heat values, results in energy savings during its production process. This work evaluates the impact of using mixtures containing high water concentrations in a single cylinder engine, 0.668L, with port fuel injection, and spark ignition combustion. The direct replace of commercial ethanol by highly hydrated mixtures was evaluated through dynamometer tests, so performance and emissions parameters were obtained. After this, it was explored the knock resistance increase due to water addition by increasing the compression ratio, aiming at reaching higher indicated efficiency values. Finally, numerical studies were conducted in order to verify the effect of water concentration increase on laminar flame speed and adiabatic flame temperatures in a one dimensional free flame simulation software. In addition, the induction time for temperature and pressure conditions obtained from experimental results was assessed. As conclusions, the increase in water concentration enabled the use of high compression ratios resulting in higher indicated efficiency values than for commercial ethanol with the same exhaust emission concentrations. Higher water volumes resulted in lower laminar flame speeds and adiabatic flame temperatures. In addition, the induction time values presented two different behavior according to the operating conditions.

A utilização de combustíveis fósseis é percebida, cada vez mais, de forma negativa, visto seus elevados níveis de emissão de gases de efeito estufa. Por conta disso, busca-se a ampliação do uso de combustíveis de origem renovável de forma a diminuir o impacto ambiental. Dentre esses, o etanol se destaca pelas excelentes características físico-químicas. Ao se reduzir o nível de pureza (diluição em agua) durante o processo de destilação desse combustível, obtém-se um sensível decréscimo da energia dispendida na sua produção. Isso se deve ao crescimento exponencial do consumo energético para obtenção de misturas com teor de etanol superiores à 80% v/v. Assim, a possível utilização de misturas superhidratadas, mesmo que apresentem menor poder calorífico, resultam em uma economia direta de energia no processo de obtenção. Dessa forma, esse trabalho avalia o impacto da utilização de misturas de etanol com elevadas concentrações de água em um motor monocilíndrico de testes, com volume deslocado de 0,668 L, injeção de combustível no coletor de admissão, e ignição por centelha. Inicialmente, avaliou-se via testes de bancada o efeito da substituição direta do etanol comercial por misturas com maior hidratação nos parâmetros de desempenho e emissões. Em seguida, buscou-se explorar as características anti-detonantes da água através do aumento da razão de compressão visando ao aumento de eficiência indicada do motor. Por fim, estudos numéricos foram conduzidos de forma a verificar o efeito da concentração de água sobre os valores de velocidade de chama e temperatura adiabática em uma chama livre unidimensional. Foram também determinados os valores de tempo de indução para condições de temperatura e pressão experimentais. Com isso, observou-se a possibilidade de operação com elevadas razões de compressão para maiores percentuais de água com sensível aumento da eficiência indicada e nível de emissões semelhantes ao etanol comercial. O aumento de água causou uma diminuição na velocidade de queima e na temperatura adiabática de chama, enquanto que o tempo de indução possuiu efeitos opostos dependentes da condição de operação. / The use of fossil fuels have faced several restrictions due its higher greenhouse gas emissions during the combustion process in internal combustion engines. Thus, there is an urge aiming to diversify the number of renewable fuels in order to decrease the environmental impact. Among them, ethanol is notorious, presenting excellent physico-chemical properties. Decreasing the ethanol level on ethanol-in-water mixtures after the distillation process, a lower energy expense can be achieved. This is related to the exponential growing in the energy consumption to obtain mixtures containing ethanol in water concentrations higher than 80% v/v. Therefore, the use of highly hydrated mixtures, despite the decrease in heat values, results in energy savings during its production process. This work evaluates the impact of using mixtures containing high water concentrations in a single cylinder engine, 0.668L, with port fuel injection, and spark ignition combustion. The direct replace of commercial ethanol by highly hydrated mixtures was evaluated through dynamometer tests, so performance and emissions parameters were obtained. After this, it was explored the knock resistance increase due to water addition by increasing the compression ratio, aiming at reaching higher indicated efficiency values. Finally, numerical studies were conducted in order to verify the effect of water concentration increase on laminar flame speed and adiabatic flame temperatures in a one dimensional free flame simulation software. In addition, the induction time for temperature and pressure conditions obtained from experimental results was assessed. As conclusions, the increase in water concentration enabled the use of high compression ratios resulting in higher indicated efficiency values than for commercial ethanol with the same exhaust emission concentrations. Higher water volumes resulted in lower laminar flame speeds and adiabatic flame temperatures. In addition, the induction time values presented two different behavior according to the operating conditions.