Thesis(M.S.)--Auburn University, 2005. / Abstract. Vita. Includes bibliographic references (p.200-203).

Thesis (MTech (Mechanical Engineering))--Cape Peninsula University of Technology, 2010 / Development of safe storage for reactive combustible materials to prevent possible human and environmental hazards as well as ensure and enhance industrial safety can significantly benefit from mathematical modelling of systems. In the recent past, models with varying degrees of sophistication have been developed and applied to the problem of predicting thermal criticality conditions, temperature and concentration profiles of such system. In this thesis, a model showing the temperature history of an nth order exothermic oxidation reaction in a slab of combustible material with variable pre-exponential factor, taking the consumption of the reactant into account in the presence of a convective heating and oxygen exchange at the slab surface with the ambient is presented Both transient and steady state problems are tackled The critical regime separating the regions of explosive and non-explosive paths of a one step exothermic chemical reaction is determined The governing nonlinear partial differential equations are solved numerically by method of lines (MOL), with finite difference schemes used for the discretisation of the spatial derivatives. Moreover, both fourth order Runge-Kutta numerical integration coupled with shooting methods and perturbation techniques together with a special type of Hermite-Pade series summation and improvement method were employed to tackle the steady state problem. The crucial roles played by the boundary conditions in determining the location ofthe maximum heating were demonstrated. In chapter one, the relevant applications together with previous published work on the problem were highlighted The basic mathematical theory and equations needed to tackle the problem were derived in Chapter two. In chapter three, the transient model problem was formulated, analysed and discussed. The steady state problem was formulated and solved in Chapter four. Furtherwork and concluding remarks were highlighted in Chapter five.

<p> A half-order kinetic model (8-48 mg NO3+NO2-N/l), coupled with a temperature dependency described by the Arrhenius relationship (4°-27° C), adequately described biological denitrification of municipal wastewater in a pilot scale fluidized bed reactor. Biofilm support media (activated carbon or sand) and hydraulic flux (0.25-1.7 m^3/m^2·min) were not found to be significant factors in controlling denitrification rate within the reactor. Control of biofilm thickness on the support media was essential for satisfactory operation of the process; excess thickness contributed to elutriation of media and attached biofilm. Under similar influent wastewater conditions, the fluidized bed process was capable of equivalent NO3+NO2-N removal in about one-tenth of the time necessary in a suspended growth or a rotating biological contactor (RBC) process. Temperature dependency of the NO3+NO2-N removal rate appeared to be less than the dependency in a suspended growth or a RBC process, but similar to the dependency observed in a packed column.</p> / Thesis / Master of Engineering (MEngr)

Orientador: Francisco Maugeri Filho / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-19T12:18:04Z (GMT). No. of bitstreams: 1 Aguiar-Oliveira_Elizama_D.pdf: 4155399 bytes, checksum: 664192a1e372b0f5556340a23b235a02 (MD5) Previous issue date: 2012 / Resumo: A obtenção de fruto-oligossacarídeos (FOS), um açúcar prebiótico de vasta aplicação industrial, por enzimas imobilizadas abrange dois conceitos em grande expansão: aplicação industrial de enzimas imobilizadas e alimentos funcionais. A partir de flores da Mata Atlântica Brasileira uma cepa foi isolada e identificada como Rhodotorula sp. LEB-V10 e apresentou grande potencial para produção da enzima extracelular frutosiltransferase (FTase) - capaz de produzir FOS a partir da sacarose - sendo obtida apenas por precipitação com etanol (purificação parcial) direto do meio de cultivo livre de células, de acordo com estudos realizados previamente, a cinética entre a enzima imobilizada pura e a parcialmente purificada não apresentou diferenças significativas que justificassem etapas adicionais de purificação. Estudos anteriores selecionaram a adsorção em partículas do composto sólidoácido (Nb), uma liga formada por nióbio (~95%) e grafite (~5%) como metodologia sugerida para imobilização da FTase para produção de FOS. Dessa forma, este trabalho apresenta uma série de estudos de caracterização deste biocatalisador imobilizado. Após a imobilização, foi possível observar que além do pH de máxima atividade apresentado pela enzima livre (pH 4,5) um segundo ponto distinto de máxima atividade (25% menor que em pH 4,5) também foi observado, o pH 6,0 que demonstrou também ser uma condição de maior estabilidade térmica e também melhor condição de síntese com a enzima imobilizada. O estudo da termo-estabilidade revelou também que a imobilização induziu a formação de duas zonas de energias de ativação da desnaturação (Ead) diferenciadas: entre 47 e 51°C a enzima imobilizada é mais estável que a enzima livre e entre 52 e 70°C ela é menos estável. A incubação da FTase, imobilizada e livre, em 52°C por 15 min resultou numa ativação dos biocatalisadores, sendo mais pronunciada com a enzima imobilizada e em pH 4,5 apresentando um aumento de 1,8 vezes na atividade enzimática; no entanto, observou-se que esta ativação é momentânea e não acumulativa com outras metodologias como a liofilização; isto sugere que esta temperatura representa algum tipo de limite energético para a FTase que é um hetero-dímero e pode apresentar diversas interações com o nióbio. A otimização da síntese de FOS realizada pela aplicação da metodologia de planejamento experimental com a enzima imobilizada permitiu um aumento do rendimento (YFOS = 0,58) em 5%, uma redução no tempo de síntese (24 h) em 4 vezes e um aumento da produtividade (12,05 g/L.h) em 6 vezes. A adsorção da FTase ao nióbio demonstrou não utilizar os sítios ativos uma vez que, a adição da sacarose ao meio de dispersão para adsorção, não alterou o desempenho do biocatalisador, porém a adição de CuSO4 que é um forte estabilizador térmico para esta enzima, resultou num biocatalisador incapaz de produzir FOS. Tendo em vista a aplicação industrial da FTase, avaliou-se também os efeitos da liofilização sobre a enzima livre e imobilizada. Com a enzima livre a liofilização causou perda de atividade enzimática em função da densidade da solução de partida, mas, resultou num pó com até 6 vezes mais atividade por grama do que em relação à enzima livre não liofilizada; a adição individual de compostos crio-protetores apresentou maior efeito estabilizador do que em formulações. Com a enzima imobilizada, a liofilização não apresentou grandes diferenciações, observou-se de forma geral uma manutenção das características originais do imobilizado de partida. Todavia, uma importante diferenciação proveniente da liofilização foi observada tanto para a enzima livre quanto imobilizada: a cinética de produção de FOS, o rendimento foi aumentado em diferentes proporções mas, especialmente, foi observada uma elevada composição de GF4. Estudos mais específicos sobre a estrutura tridimensional forneceriam informações mais precisas sobre o efeito da liofilização. Adicionalemente, duas enzimas comerciais (inulinase e invertase) foram igualmente imobilizadas em nióbio, mas, não foram observadas alterações tão expressivas quanto às observadas com a FTase. Dessa forma, a imobilização da FTase em nióbio revela ser uma metodologia com grande potencial de aplicação em reatores. Como resultado deste trabalho, encontram-se publicados até o momento os Capítulos 2 e 4 e aceito para publicação o Capítulo 5 / Abstract: The production of fructooligosaccharides (FOS) - a prebiotic sugar with wide industrial application - from immobilized enzymes includes two modern concepts: industrial application of immobilized enzymes and functional food. A strain isolated from flowers from the Brazilian Atlantic Forest identified as Rhodotorula sp. LEB-V10 showed great potential for production of the extracellular fructosyltransferase (FTase), which is capable of producing FOS from sucrose. It can be recovered only by precipitation with ethanol (partial purification), directly from the cell-free culture medium. According to previous studies, the kinetics between purified and partially purified immobilized enzymes showed no significant differences that could justify additional purification steps. Other previous studies have selected the adsorption on particles of a solid-acid support (Nb) an alloy consisting of niobium (~95%) and graphite (~5%) as suggested methodology for the immobilization of FTase for FOS production. Thus, this work presents a series of characterization studies of this immobilized biocatalyst. After the immobilization, it was observed that besides the pH of maximum activity presented by the free enzyme (pH 4.5), a second distinct point of maximum activity (25% lower than at pH 4.5) was also observed, pH 6.0, wich was proved to be the best condition for thermal stability and also better for synthesis with the immobilized enzyme than pH 4.5. The study of thermal stability has also shown that immobilization induces the formation of two distinct phases with different denaturation activation energy (Ead): between 47 and 51°C, the immobilized enzyme is more stable than the free enzyme, and between 52 and 70°C it is less stable. Incubation of free and immobilized FTase at 52°C for 15 min resulted in enzymatic activation, being more pronounced with the immobilized enzyme at pH 4.5 with a 1.8-fold increase in enzyme activity. However, due to other studies carried out in this work, it has been shown that this activation is merely transient and not cumulative regarding other methodologies, indicating that this temperature is a kind of energetic threshold, and also because FTase is a hetero-dimer, which may lead to different interactions with the niobium support. The optimization of the synthesis of FOS carried out by applying the methodology of experimental design with the immobilized enzyme, allowing a yield increase (YFOS = 0.58) of 5%, a reduction in synthesis time (24 h) of 4 times and an increased productivity (12.05 g/L.h) of 6 times. The adsorption on niobium has shown not to involve the FTase active sites, since the addition of sucrose to the dispersion medium for adsorption did not affect the performance of the biocatalyst. On the other hand, the addition of CuSO4, which is a strong thermal stabilizing agent for this enzyme, resulted in a biocatalyst incapable of producing FOS. Considering the industrial application of FTase, it was also evaluated the effects of lyophilization over the free and immobilized enzyme. With the free enzyme, lyophilization caused loss of enzyme activity in dependence on the density of the starting solution, but in general, resulted in a powder with up to 6 times more activity per gram as compared to non-lyophilized free enzyme; the individual effects of cryo-protectants additives presented higher stabilizing effect than with the presence of other protectants. The lyophilization of the immobilized enzyme did not show drastic effects and it was observed, in general, the maintenance of the initial properties and characteristics before lyophilization. For both, free and immobilized enzyme was possible to observe significant changes in the kinetics of FOS production, the yield was increased in different proportions but, especially, there was a high composition of GF4, which was not observed before lyophilization. In addition, two commercial enzymes (inulinase and invertase) were immobilized on niobium but no significant changes were observed as those with FTase. Thus, the immobilization of FTase in niobium proves to have a big potential for application due to operational features. As a result of this work, two articles have been published (Chapters 2 and 4) and one has been accepted for publication (Chapter 5) / Doutorado / Engenharia de Alimentos / Doutor em Engenharia de Alimentos

There are many products, including hard drives, which require trace amounts, on the order of several mg, of lubricants for proper operation. The following study investigated the evaporation rates of pump oil and several alkanes, which have a wide range of applications, using a thermogravimetric machine. Both static and dynamic temperature tests were conducted. The rate of evaporation of the test specimen was determined as the percentage of mass loss per unit time. Using the Arrhenius Equation, the activation energy of the evaporation process, Ea, can be calculated as the slope of the best fit line for a plot of the ln(k) vs. 1/T (where k represents the rate of the evaporation). These values were shown to have good agreement with the enthalpy of vaporization calculated from the Clausius Clapeyron Equation and with the activation energy calculated using the Freeman and Carroll Method. The alkanes were compared using the rate of evaporation and the amount of activation energy required for evaporation as model systems. Further investigations were conducted to determine the relationship of surface area of the evaporating liquid and the rate of evaporation. It is suggested that the surface area is a function that depends on the activation, bonding, and interfacial energies of the liquid. However, the wetting angle, which aids in the description of the surface area, depends on the surface energy. Subsequent modeling was conducted in an attempt to predict the evaporation characteristics of other lubricants for the purpose of comparison.

A Ce:YAG-doped glass phosphor layer instead of conventional Ce:YAG-doped silicone phosphor layer as phosphor-converted white-light emitting diodes (PC-WLEDs) is demonstrated. The advantage of employing doped glass encapsulation in high power PC-WLEDs could be explained the material property of glass transition temperature of 750¢J was higher than silicone of 150¢J. The lumen degradation, chromaticity shift, color temperature change, transmittance, and fluorescence spectrum in glass and silicone based high-power PC-WLEDs under thermal aging at 150¢J, 200¢J, and 250¢J is compared and presented. Under highest temperature of 250¢J, the glass and silicone encapsulation base d PC-WLEDs exhibited 8.15% and 38.85% in lumen loss, 1.07 and 7.32 in chromaticity shift, 856 K and 3666 K in color temperature change, 4.21% and 28.1% in transmittance loss, respectively. However, the excitation spectrum altered as slight as emission spectrum before and after experiments. After aging test, the mean-time-to-failure (MTTF) evaluation of glass and silicone encapsulation materials for PC-WLEDs in accelerated thermal tests is also compared and presented by the using of Weibull distribution and Arrhenius equation. The MTTF of PC-WLEDs is defined the lumen decayed to 90%. The results showed that the glass as encapsulation material of PC-WLEDs exhibited higher MTTF than the silicone encapsulation by about 4.81, 5.92, and 7.53 times in lumen loss at 150¢J, 200¢J, and 250¢J, respectively. The results of the lumen loss, chromaticity shift, and MTTF investigations demonstrated that the thermal-stability performance of the glass based PC-WLEDs were better than silicone based PC-WLEDs at 150¢J, 200¢J, and 250¢J. A better thermal stability phosphor layer of glass as encapsulation material may be beneficial to the many applications where the LED modules with high power and high reliability are demanded.

We report an intriguing giant dielectric and magnetodielectric (MD) response on double perovskite Pr2CoMnO6(PCMO) system. The Arrhenius plot indicates that the origin of giant dielectric is internal barrier layer capacitance. Meanwhile, at the highest applied magnetic field 9T, the giant dielectric constant around Tm ~ 150 K is enhanced almost ~ 20% (at 10 kHz frequency) compared with that at zero field. The observed positive MD effect is considered to be associated with the direct consequence of negative magnetoresistance changes (~ -20% at 150 K) which was calculated by temperature dependent impedance spectras. Concomitantly, a pronounced ferromagnetic ordering is observed near Tc ~ 150 K coinciding with Tm of £`¡¬(T). These experimental results suggest that the magnetoresistive and MD effect response is very strongly by magnetic property of PCMO.

No description available.

The primary objective of this research was to examine the strength degradation of Glass Fiber Reinforced Polymer (GFRP) bars at high temperature and alkalinity and determine if an Arrhenius type relationship can be used as a means of projecting life. The work done includes a thorough literature review, experiments and development of strength prediction models. The experimental work involves exposure of GFRP bars incased in cement mortar to lime-water solution at 30, 45 and 57°C. Overall 100 specimens were included in the experimental program. The tensile strength and modulus of elasticity retention after 180 days of exposure at 57°C was 57% and 82% respectively. The secondary objective was to determine the moisture absorption properties of GFRP bars. The moisture absorption data available is till 80 days from the immersion of the specimens in the tank. The collected data was used in the development of strength retention models. Two strength prediction models, Time Shift Method and Fickian Model for moisture absorption are formulated. Using the Fickian Model, strength is predicted for GFRP bars, if used in bridge decks in Roanoke, Virginia. The strength loss predicted was 45% after 50 years of exposure in real life environment. A linear relationship was observed when the moisture content and strength retention were plotted. The study estimates a strength loss higher than the ACI-440H recommended environmental degradation factor of 0.7 to calculate the design ultimate tensile strength. / Master of Science

[pt] Geralmente, o ambiente marinho é o ambiente natural mais agressivo para tubulações metálicas, promovendo corrosão, levando a falhas catastróficas. O método de reparo tradicional metálico soldado é um método de reparo inconveniente e custoso para a indústria. Compósitos poliméricos (FRP) são um material com potencial para reparo devido a sua alta razão resistência/peso e alta resistência à corrosão e degradação ambiental. Porém, os compósitos poliméricos também são suscetíveis a degradação severa quando expostos a condições ambientais agressivas, incluindo absorção de água, temperatura, UV e pressão. Para um melhor entendimento do mecanismo de degradação, amostras de compósito de matriz polimérica reforçado por fibras de vidro e resina epóxi pura foram fabricados e analisados em função do tempo e temperatura de envelhecimento em uma atmosfera salina. Além disso, um grupo de compósitos tiveram suas bordas cobertas com resina epóxi para similar práticas reais comuns no campo, denominado coated FRP. Uma resina epóxi DGEBA bicomponente e um tecido bidirecional de fibras de vidro foram usados como matriz e reforço, respectivamente. O tecido de fibra de vidro detém de uma razão de fibras longitudinais por transversais de 2:1. Os materiais foram sujeitos a envelhecimento de névoa salina em três câmaras à 35, 55 e 70 Celsius por aproximadamente 15171 horas. A concentração de sal na solução usada foi 5.0 por cento por massa. As amostras foram periodicamente retiradas das câmaras de envelhecimento para terem seus ganhos de massa mensurados pelo método gravitacional. Suas mudanças dimensionais também foram capturadas para avaliação do comportamento de inchamento dos materiais. Análises térmicas com DSC e DMTA foram feitas para avaliar o grau de cura dos materiais poliméricos e os efeitos da temperatura na pós-cura do material. Análises químicas com testes FTIR foram feitas para investigar a ocorrência de processos de pós-cura, hidrólise e termo-oxidação durante o envelhecimento. Amostras de compósito para testes destrutivos de flexão e resistência ao cisalhamento (ILSS) foram testados periodicamente para terem suas degradações monitoradas com o tempo. Testes de Excitação por Impulso (IET) e Colorímetro foram realizados como testes não-destrutivos (NDT) complementares. A primeira parte deste trabalho foca na avaliação do comportamento de absorção de umidade nos compósitos e resina epóxi pura. A relação entre a capacidade de absorção de umidade dos materiais, considerando a fração volumétrica de fibras, foi investigada. Além disso, modelos de absorção não-Fickianos também foram aplicados aos dados experimentais do FRP e resina epóxi para considerar desvios do modelo Fickiano padrão. Com isso, relaxações poliméricas e interações polímero-água, assim como mudanças na rede polimérica induzidas por umidade e temperatura, foram investigados. Uma modificação ao modelo não-Fickiano de Berens-Hopfenberg (BH) foi proposta para incluir os efeitos de pós-cura na absorção de umidade; tal modificação aplicada a pós-cura não foi encontrada na literatura. Na segunda parte deste trabalho, o comportamento de inchamento da resina epóxi pura e compósitos revestidos e não-revestidos foi avaliado e correlacionado com a absorção de umidade. A ortotropia do compósito ficou evidente, visto que o material apresentou maior capacidade de inchamento na direção da espessura. Um modelo do tipo Fickiano foi implementado ao inchamento na espessura com o intuito de investigar deformação de inchamento de saturação e a frente de inchamento. A terceira parte deste trabalho foca nos testes destrutivos e na avaliação dos efeitos hidrotérmicos na degradação do material. A temperatura se mostrou um fator acelerador para degradação de propriedade. Além disso, uma metodologia para estimar a curva de serviço de sistemas de reparo e extrapolá-la para temperaturas mais baixas foi elaborada. Metodologias de extrapolação de propriedades para exposição hidrotérmica de longa duração não foram encontradas na literature. Parâmetros como platô de retenção de propriedade e taxa de degradação foram estimados para temperatura ambiente. Curvas de Arrhenius também foram plotadas para avaliar o tempo requerido para alcançar os níveis de retenção em cada temperatura testada. Por fim, duas técnicas não-destrutivas foram utilizadas no FRP e resina epóxi pura como testes complementares como forma de validar os resultados encontrados em outras técnicas. A Técnica de Excitação por Impulso (IET) foi realizada para obter o módulo de Young e boa correlação foi obtida entre o teste IET e o ensaio destrutivo de flexão. Através dos testes colorimétricos, os efeitos de umidade e temperatura foram visíveis, já que a mudança de cor da resina foi mais forte para tempos longos e temperaturas mais altas. / [en] Generally, the marine environment is the most aggressive natural environment for metallic pipelines, promoting corrosion, leading to catastrophic failures. The traditional welded metallic repairs are high-cost and inconvenient repair methods for the industry. Polymeric composites (FRP) are a potential repair material due to their high resistance/weight ratio and high resistance to corrosion and environmental degradation. However, polymeric composites are also susceptible to severe degradation when exposed to harsh environment conditions, including water absorption, temperature, UV and pressure. To better understand the degradation mechanism, glass-fiber reinforced polymer matrix composite (GFRP) and neat epoxy samples were fabricated and analyzed as a function of aging time and temperature in a saline atmosphere. In addition, a group of composites had their exposed edges coated with epoxy resin to simulate common real-life practices in the field, namely coated FRP. A two-component DGEBA epoxy resin and a bidirectional glass-fiber woven fabric were used as matrix and reinforcement, respectively. The fiberglass fabric had a longitudinal to transverse fiber ratio of 2:1. The materials were subjected to salt spray aging in three chambers at 35, 55 and 70 Celsius for approximately 15171 hours. The salt concentration in the solution used was 5.0 per cent by weight. Samples were periodically removed from the chambers to have their mass gain measured by the gravitational method. Their dimensional changes were also measured to evaluate the swelling behavior of the materials. Thermal analyses with DSC and DMTA were performed to evaluate the curing degree of the polymeric materials tested and the effects of temperature on the material’s post-curing. Chemical analyses with FTIR tests were performed to investigate the occurrence of post-curing, hydrolysis and thermo-oxidation processes during aging. Composite samples for bending and interlaminar shear strength (ILSS) destructive tests were periodically tested to have their degradation monitored over time. Impulse Excitation Technique and colorimetry tests were also performed as complementary non-destructive tests (NDT). The first part of this work focuses on the assessment of the moisture absorption behavior of both composite and neat epoxy resin. The relationship between the moisture gain capacity of the materials, considering the fiber volume fraction, was investigated. Besides, non-Fickian absorption models were also applied to the experimental data of FRP and neat epoxy resin to account for deviations from the standard Fickian model. Then, polymeric relaxations and polymer-water interactions, as well as network changes induced by moisture and temperature, were investigated. A modification to the Berens-Hopfenberg (BH) non-Fickian model was proposed to account for post-curing effects on the moisture absorption; such modification applied for post-curing was not found in literature. In the second part of this work, the swelling behavior of neat epoxy resin, uncoated and coated composites was evaluated and correlated with moisture absorption. The orthotropy of the composite was evident, since this material showed greater swelling capacity in the thickness direction. A Fickian-like model was implemented to the thickness swelling to investigate swelling strain saturation and swelling front. The third part of this work focuses on the destructive tests and evaluation of the hygrothermal effects on the material degradation. Temperature proved to be an accelerating factor for property degradation. In addition, a methodology to estimate the service-life curve of the repair systems and extrapolate it to lower temperatures was elaborated. The methodology of property extrapolation for long-term hygrothermal exposure in salt spray environments could not be found in literature. Parameters like property retention plateau and degradation rate were estimated for room temperature (25°C). Arrhenius curves were also plotted to evaluate the time required to reach the properties’ retention levels for each temperature. Finally, two non-destructive techniques were performed on the uncoated FRP and on neat epoxy resin as complementary tests in order to validate the results found in other techniques. The Impulse Excitation Technique (IET) was performed to evaluate the Young modulus and good correlation was found between IET and destructive bending tests. From the colorimetry tests, the effects of moisture and temperature were visible, as the resin s color change was stronger at longer aging time and higher temperatures.