Tesis sobre el tema "Thermo-Kinetics"

In recent decade growing concerns of CO2 emissions from power plants have increased, which led to development of technologies like oxy-fuel combustion process. P91 steel is profoundly used in power plants, but oxy fuel combustion exacerbates corrosion due to recycling of flue gas. This paper studied the kinetics of the corrosion rate on the boiler tubes and furnace and help achieve a corrosion resistant coating over it. Refractory metal diffusion coating is created and tested at high temperature in corrosive atmosphere. This was done by forming Ti and Zr diffusion coating on P91 steel using pack cementation. Coating thickness of 12 and 20 µm were obtained for Ti and Zr respectively. These samples were tested in thermo-gravimetric system by heating at 950˚C for 24 hours in 5% oxygen in Helium gas. Heating in an oxidizing environment lead to exfoliation corrosion on uncoated P91 steel. TGA procedure confirmed less mass change of Ti and Zr coated samples, than that of uncoated P91 steel sample. SEM and depth profiling confirms oxygen penetration is 2.7mm in uncoated P91 steel sample, whereas the Ti and Zr Coated samples oxygen penetration is just 16 and 56 µm respectively.

The reaction kinetics of Iroko and Mahogany were studied using TGA. The pyrolysis process was achieved using six different heating rates of 2,5,8,12,15 and 20˚C. A 15˚C/min heating rate was used for gasification in steam at different temperatures while varying the concentrations of nitrogen and steam in the process. The kinetic parameters, activation energy and pre exponential factor, were obtained by implementing two chosen kinetic models. These models are: Friedman’s Iso-conversional Method, Flynn-Wall-Ozawa Method (FWO). There were substantial differences in the values of the kinetic triplets found from the experiments. Due to the substantial differences in the values, it was not the best way to perform this kind of analysis (which is the traditional way) but instead to use pure regression analysis; but using it for the whole data set (that means for all heating rates) and minimize the difference with experimental data.

Phenylethynyl terminated imides (PETI) are high temperature, high performance matrix resins that can be processed into composites by various methods including resin transfer molding (RTM) arid vacuum assisted resin transfer molding (VARTM). PETI resins have experienced extremely rapid development in recent years, with major emphasis placed on engineering applications that take advantage of their high cured TgS,high thermooxidative stability, high strength to weight ratio, outstanding mechanical properties, and compatibility with RTM and VARTM processing. In recent years the addition of nanoparticles to resin systems has been shown to further enhance the mechanical properties and thermooxidative stability. In this study, we incorporated nanoporous aluminosilicate materials, otherwise known as zeolites, into PETI resin GRC-A, and investigated the effect the zeolites have on the viscosity, cure kinetics, thermooxidative stability and other thermomechanical properties of GRC-A. Rheological and differential scanning calorimetry studies conducted on the GRC-Alzeolite mixtures showed that zeolite L acts like a filler and retards the curing of the phenylethynyl end-groups, while zeolite Y catalyzes the curing process. Additionally, cure kinetic studies via melt rheology and DSC confirmed that the activation energies for GRC-A/zeolite Y mixtures as lower than for neat GRC-A and GRC-A/zeolite L mixtures, further supporting zeolite L acts as a filler while zeolite Y serves as a catalyst during the cure process. While the cured Tgs, from the DMA and TMA studies showed that in spite of the catalytic properties of zeolite Y; it did not afford additional properties over GRC-A and zeolite L mixtures. However, the catalytic properties of zeolite Y allows PETI resins to be cured at a lower temperatures, which could lead to lower energy costs in the production of composite parts from PETI resins.

The main reasons behind the success of the petrochemicals industry are not only the vast array of products that it provides - considered vital to our daily functions - but also the added value that it brings to the crude oil barrel price, making it a reliable venture for any concerned party. However, the industry is now faced with a fluctuating market and an unstable economy, which makes it imperative to find a more abundant and sustainable feedstock. Of all petrochemical derivatives, polymers (and their related industries) occupy the major share, and this makes the plastics industry a growing sector in terms of processing and conversion. Both virgin and waste plastics represent an attractive source of energy and product recovery. The main objective of this work was to investigate the thermo-chemical treatment (TCT) of polymers at different scales, and the reactors studied ranged from micro laboratory scale to industrial units suitable for covering large market demands. Within this framework, the degressive behaviour of polyolefin polymers (three virgin grades and two recyclate ones) was investigated alongside the products yielded (gases (C1-C4), liquids (non-aromatic C5-C10), aromatics (single ring structures) and waxes (> C11). This was achieved in a micro scale isothermal pyrolysis process, using 15 mg in a laboratory thermogravimetric analyser covering the temperature range of 500-600°C. The analysis led to the development of an nth order novel model on the basis of lumped products yielded by pyrolysis. The degradation mechanism was used to develop the mathematical breakdown of the primary, secondary and tertiary reactions. The model developed predicts the yield of the four different products and the polymer residual fraction at any operating condition proving to be a useful tool for reactor design and simulation, where the production of a specific chemical at a certain operating condition is paramount. In addition, laboratory scale isothermal pyrolysis experiments on end of life tyres (ELTs) were also conducted. This was achieved as a means to demonstrate the application of the concept previously applied to the polyolefins. A thermal cracking (degradation) scheme was proposed based on the global yielded products, which were lumped into four categories, namely gases (C1-C4), liquids (non-aromatic C5-C10), single ring aromatics (C5-C10), and char. The depolymerization kinetics (from primary, secondary and tertiary reactions) evaluation showed a high match with the experimental results obtained in this work. Finally, a life cycle assessment (LCA) was conducted for three integrated scenarios that reflect the current (2012) treatment of waste plastics in the Greater London area. The scenarios studied utilised a fraction of the polymers treated as a feedstock for two industrial scale TCT technologies; namely a low-temperature pyrolysis reactor that works using BP® technology and a hydrocracking unit that utilises the Veba-Combi Cracking (VCC®) concept. The scenarios studied also include transfer stations, a dry materials recovery facility (MRF) and a combined heat and power (CHP) incineration unit. The energy recovered via the different processes studied, as well as the chemicals and petrochemicals recovered, were all considered as credits in the LCA conducted. Chemicals obtained by the TCT units are very valuable and can replace refinery cuts and petrochemicals (e.g. syncrude (crude oil), naphtha, heavy (waxes) fraction (comparable to atmospheric residue), gases (C3 and C4) refinery cuts, etc.). This led to a technoeconomic analysis of the three integrated scenarios in order to assess the overall profitability. The analysis included capital, operating and maintenance costs, gate fees, transportation costs and corporation tax. The eligibility for governmental incentives (i.e. renewable obligation certificates (ROCs), levy exemption certificates (LECs) and packaging recovery notes (PRNs)) was also considered. The results obtained from the work carried out and reported in this thesis point towards ideal strategies for the treatment of polymers within the urban environment. It also provides a detailed understanding of potential products from polymers introduced to TCT units. This also aids the optimum recovery of petrochemicals, chemicals and energy from different TCT processes, and could help the UK Government in meeting its energy policy targets. It can also contribute to the energy security through diversification of supply. Finally, it provides a perspective on the integration between the crude oil upstream industry and different petrochemical complexes and oil refineries, through the use of different TCT units to increase the production of petrochemicals in existing plants.

The past few years have seen an upsurge in the use of renewable biomass as a source of energy due to growing concerns over greenhouse gas emissions caused by the combustion of fossil fuels and the need for energy independence due to depleting fossil fuel resources. Although coal will continue to be a major source of energy for many years, there is still great interest in replacing part of the coal used in energy generation with renewable biomass. Combustion converts inherent chemical energy of carbonaceous feedstock to only thermal energy. On the other hand, partial oxidation processes like gasification convert chemical energy into thermal energy as well as synthesis gas which can be easily stored or transported using existing infrastructure for downstream chemical conversion to higher value specialty chemicals as well as production of heat, hydrogen, and power. Devolatilization or pyrolysis plays an important role during gasification and is considered to be the starting point for all heterogeneous gasification reactions. Pyrolysis kinetic modeling is, therefore, an important step in analyzing interactions between blended feedstocks. The thermal evolution profiles of different coal-biomass blends were investigated at various heating rates using thermogravimetric analysis. Using MATLAB, complex models for devolatilization of the blends were solved for obtaining and predicting the global kinetic parameters. Parallel first order reactions model, distributed activation energy model and matrix inversion algorithm were utilized and compared for this purpose. Using these global kinetic parameters, devolatilization rates of unknown fuel blends gasified at unknown heating rates can be accurately predicted using the matrix inversion method. A unique laboratory scale auto-thermal moving bed gasifier was also designed and constructed for studying the thermochemical conversion of coal-biomass blends. The effect of varying operating parameters was analyzed for optimizing syngas production. In addition, stable carbon isotope analysis using Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometry (GC-C-IRMS) was used for qualitatively and quantitatively measuring individual contributions of coal and biomass feedstocks for generation of carbonaceous gases during gasification. The predictive models utilized and experimental data obtained via these methods can provide valuable information for analyzing synergistic interactions between feedstocks and also for process modeling and optimization.

La formation des microstructures est cruciale pour la sidérurgie. Pour les aciers Dual Phase (DP), utilisés dans l'automobile, celle-ci a lieu lors du recuit intercritique après le laminage à froid. Après la chauffe, la microstructure est composée de ferrite et d'austénite recristallisées. Lors du refroidissement, l'austénite se transforme partiellement en ferrite puis en martensite pour atteindre la microstructure ferrite/martensite finale. L'austénitisation est cruciale pour contrôler les fractions et tailles de phase finales et donc leurs propriétés mécaniques. De nombreuses études montrent que la vitesse de chauffe contrôle la cinétique de transformation et la morphologie de l'austénite ("collier" ou "bande"). Ces effets sont souvent attribués au chevauchement entre la recristallisation de la ferrite et la formation de l'austénite, mais les mécanismes sous-jacents restent controversés. En utilisant les progrès récents dans les expériences in situ sur les lignes de faisceaux synchrotron, ce travail de doctorat vise à proposer une nouvelle compréhension des interactions entre la recristallisation de la ferrite et la formation de l'austénite et à développer un modèle prédictif pour la cinétique de formation de l'austénite. Le développement expérimental principal de cette thèse est une nouvelle technique d'analyse basée sur la diffraction des rayons X de haute énergie pour suivre in situ la recristallisation et les transformations de phase pendant la phase de recuit, y compris à des vitesses de chauffe élevées. Notre nouvelle méthode, appelée Isolated Diffraction Spot Tracking (IDST), est d'abord validée pour étudier la recristallisation sur des aciers ferritiques modèles. Ces mesures in situ sont complétées par des observations des microstructures après traitements interrompus en microscopie (optique, microscopie électronique à balayage et à transmission), et par des mesures de chimie locale (spectroscopie de rayons X à dispersion d'énergie et de dispersion en longueur d'onde). Nous reproduisons d'abord des expériences pour étudier l'influence de la vitesse de chauffe sur l'acier étudié pendant le recuit intercritique. Dans celles-ci, le chevauchement entre la recristallisation de la ferrite et la formation de l'austénite est régi par la vitesse de chauffe. Ensuite, nous avons conçu des expériences pour décorréler l'effet de la vitesse de chauffe et ce chevauchement. La vitesse de chauffe est fixée pour maintenir les mêmes conditions pour les mécanismes thermo-activés, mais le micro-alliage au niobium et le taux de laminage à froid plus faible retardent la recristallisation de la ferrite. Ces expériences montrent que la cinétique de transformation de l'austénite n'est pas contrôlée par la recristallisation, mais par la seule condition thermodynamique de l'interface de transformation et peut-être par la distance de diffusion dans les microstructures. Enfin, une analyse thermocinétique détaillée des mécanismes de formation de l'austénite au cours du recuit intercritique est proposée sur la base de simulations DICTRA/Thermo-Calc et de notre travail expérimental. L'effet des éléments d'alliage mineurs sur la cinétique de croissance de l'austénite est étudié et un modèle prédictif pour la formation de l'austénite pendant le recuit intercritique est développé. Finalement, ce travail montre l'absence d'effet significatif de la concomitance des mécanismes étudiés sur la cinétique de formation de l'austénite au cours de la chauffe. Nous montrons que la cinétique de formation de l'austénite est contrôlée par la diffusion. La différence de cinétique de formation de l'austénite au cours de la phase de maintien est expliquée par des considérations microstructurales, affectant les distances de diffusion
The formation of microstructures is a crucial step for steelmakers. In the case of DP steels, used for automotive construction, this formation takes place during intercritical annealing after cold-rolling. During this thermal treatment, after the heating step, the microstructure is made of recrystallized ferrite and austenite. During cooling, the austenite partially transforms into ferrite and then into martensite to reach the expected final ferrite/martensite microstructure. The austenitization step is therefore crucial for the manufacturers of these steels, to control the final phase fractions and sizes and, consequently, their mechanical properties. Numerous studies show that the heating rate controls the transformation kinetics and the morphology of the austenite ("necklace" or "banded"), but the underlying mechanisms remains a bone of contention. The overlap between ferrite recrystallization and austenite formation is often made responsible for these effects, through different mechanisms. Using recent advances in in situ experiments on synchrotron beamlines, this PhD proposes a new insight in the understanding of the interactions between ferrite recrystallization and austenite formation and develops a predictive model for the austenite formation kinetics. The main experimental development of this thesis is a new coupled time-resolved analysis technique, based on in situ High-Energy X-Ray Diffraction to track recrystallization and phase transformations during the annealing phase, including at high heating speeds. Our new method, called Isolated Diffraction Spot Tracking (IDST), is first validated to study recrystallization on model ferritic steels. These in situ measurements are supplemented by observations of microstructures after interrupted treatments in microscopy (optical, Scanning Electron Microscopy and Transmission Electron Microscopy), and from local chemistry measurements (Energy-Dispersive X-ray Spectroscopy and Wavelength Dispersion Spectroscopy)We first reproduce experiments to study the influence of the heating rate on the studied steel during the intercritical annealing. In such experiments, the overlap between ferrite recrystallization and austenite formation is governed by the heating rate. To go further, we designed experiments to decorrelate the effect of the heating rate and this overlap. During these, the heating rate is fixed to maintain the same conditions for thermo-activated mechanisms, but the niobium micro-alloying and lower cold-rolling ratio are used to delay ferrite recrystallization. These experiments show unambiguously that austenite transformation kinetics is not controlled by the recrystallization, but by the sole thermodynamic condition of interfaces and maybe by the diffusion distance in the microstructures. Finally, we propose a detailed thermo-kinetics analysis of the mechanisms of austenite formation during the intercritical annealing based on DICTRA/Thermo-Calc simulations and on our experimental work. The effect of minor alloying elements on the austenite growth kinetics is investigated. This work finally proposes new predictive models for austenite formation during the intercritical annealing. This PhD work finally shows no significant effect of the concomitance of the two studied mechanisms on the austenite formation kinetics along the heating stage. We demonstrate that the austenite formation kinetics is diffusion-controlled. The difference in austenite formation kinetics along the holding stage is explained by microstructural considerations, affecting the diffusion distances

Ces travaux s’articulent autour de la modélisation cinétique de l’hydratation des ciments alumino-calciques (CAC) pour en améliorer la compréhension et la maîtrise. L’aspect cinétique pour ces ciments est essentiel en raison des nombreux états métastables qu’ils traversent (e.g. conversion).Des modèles de cinétique intégrés dans l’espace existent déjà pour simuler des pâtes de mortier mais ils requièrent la connaissance des lois de cinétiques. Malheureusement, ces lois sont mal identifiées pour les CAC et c’est ce qui motive la création d’un modèle pour des suspensions minérales. L’étude de suspensions permet d’étudier ces lois sans l’influence de l’empilement granulaire et du réseau poreux. Le modèle créé est un modèle de thermochimie où les quantités de matières sont pilotées par des équations différentielles-algébriques. L’information sur la granulométrie est, elle, portée par des Population Balance Equations permettant de répercuter chaque phénomène physico-chimiques (e.g. Nucléation, Dissolution, Croissance, Agglomération...) de manière adaptable et indépendante sur les tailles de particules. L’étude de ce modèle a permis de mettre en évidence le rôle fondamental que joue la formation de l’hydroxyde d’aluminium dans l’hydratation des CAC. Cette formation permet l’apport en solution d’ions hydroxyde déficitaires à la formation de la plupart des hydrates en consommant des ions aluminates. Cette formation d’hydroxyde d’aluminium a été démontrée comme étant complexe à expliquer expérimentalement et à modéliser. Toutefois, l’utilisation de précurseurs pré-hydroxylés permet de la modéliser partiellement
This work focuses on the kinetic modeling of calcium aluminate cements (CAC) to improve the knowledge and the control of these chemical systems. The kinetic aspect of this modeling is essential since their hydration goes through several metastable states (e.g. CAC conversion). Kinetic models integrated over a volume of mortar paste already exist yet they require appropriate kinetic laws. Unfortunately, these laws are poorly identified for CACs and this is what motivates the creation of a model for mineral suspensions. The simulation of suspension allows the evaluation of these kinetic laws without the interference of granular stacking or porous network assumptions. The created model is a thermo-chemical model where the molar quantities are driven by differential-algebraic equations. The particle size information is borne by Population Balance Equations allowing to manage each physic-chemical phenomenon (e.g. Nucleation, Dissolution, Growth, Agglomeration...) independently and in a flexible way. The evaluation of this model highlighted the key role of aluminium hydroxide formation in CAC hydration. This reaction converts the excess of aluminate ions into the deficient hydroxide ion which are required by most of the hydrates. This work demonstrated that aluminium hydroxide formation is complex to explain experimentally and to model. Nevertheless, the use of prehydroxylated precursors allows a partial modeling of this reaction

Stainless steels are high-alloyed, usually with multiple components and often also dual matrix phases, as for duplex stainless steels. This make predictions and calculations of alloying effects on equilibria and transformations complicated. Computational thermodynamics has emerged as an indispensable tool for calculations within these complex systems with predictions of equilibria and precipitation of phases. This thesis offers examples illustrating how computational methods can be applied both to thermodynamics, kinetics and coarsening of stainless steels in order to predict microstructure and, to some extent, also properties. The performance of a current state-of-the-art commercial thermodynamic database was also explored and strengths and weaknesses highlighted.

QC 20130429

Cálculos usando métodos de estrutura eletrônica (Hartree-Fock, Mõller-Plesset de segunda ordem e DFT, B3LYP) foram efetuados pelo programa Gaussian98 em microcomputadores e estações de trabalho, com o objetivo de elucidar os canais de decomposição unimolecular de éter dietílico em fase gasosa e foram comparados com valores obtidos através de aproximações baseadas na mecânica estatística pela metodologia de Benson. O éter dietílico vem sendo usado como um aditivo para o óleo diesel e combustível alternativo e o conhecimento de suas vias vias de decomposição é fundamental nestas investigações. Dezesseis modos primários, do qual, quatro ocorrem através de cisão de ligações simples C-O, C-C,C(1)-H e C(2)-H e doze ocorrendo através de estados de transição cíclicos, os quais eliminam produtos como hidrogênio etano, acetaldeído, etano, álcool etílico, metil etil éter, metano, alguns carbenos e também di-radicais, foram considerados para a determinação das barreiras de ativação, entalpias de reação, entropias de reação e energia livre de Gibbs de reação. Vias primárias ocorrendo através de cisão de ligação, não reproduziram os valores experimentais para as barreiras de ativação, mas reproduziram de modo significante, valores da entalpia da reação. Eliminação de eteno e álcool etílico, ocorrendo através de um estado de transição de quatro centros, apresentou a barreira de ativação mais baixa. Acetaldeído e eliminação de etano, ocorrendo através de quatro centros, apresentou barreira significativamente alta, mas por outro lado, a menor entalpia, ligeiramente exotérmica por -0,8 kcal.mol-1. Eliminações 1,2 de metano e carbeno ocorrendo através de três centros, junto com a eliminação 1, 1 de hidrogênio e carbeno por três centros, eliminação 2,2 hidrogênio e carbeno por três centros e eliminação 1,4 de hidrogênio, acetaldeído e eteno por seis centros, apresentaram barreiras de ativação relativamente próximas mostrando que elas são competitivas entre si. Os valores computados dos canais que ocorrem por estados de transição cíclicos foram comparados com os resultados experimentais disponíveis e discutida a validade desta abordagem computacional para o estudo de reações unimoleculares de multi-canais. Determinação de parâmetros termoquímicos, como calor de formação para espécies radicalares dos canais de decomposição primário e alguns radicais alcóxidos, junto com a estimativa de afinidade eletrônica e protônica (com a abordagem ab initio Gaussian 2 a qual estima energias eletrônicas muito precisas) foram efetuados e seus resultados foram comparados com os valores experimentais disponíveis e valores obtidos através de energias de ligação e da regra de aditividade de Benson.
Calculations using methods of electronic structure(Hartree-Fock, second order Moller-Plesset and DFT: B3LYP) had been effected through the Gaussian98 program in microcomputers and workstations, with the objective to elucidate the unimolecular decomposition channels of diethyl ether in gaseous phase. These results also had been compared to those obtained by the methodology based in statistical mechanics through Benson\'s approach. Sixteen primary ways, which, four occur through the break of simple bonds C-O, C-C,C(1)-H, C(2)-H, and twelve occur through cyclical transistion states, which eliminate products as hydrogen, ethene, acetaldehyde, ethane, ethyl alcohol, methyl ethyl ether, methane, some carbenes and also diradicals. These products had been considered to the determination of the activation barriers, enthalpies of reaction, entropies of reaction and free energy of Gibbs of reaction. Primary ways occurring through the break of bonds, had not reproduced experimental values for the activation barriers, however they had reproduced in a significant way, values of the enthalpy of the reaction. Elimination of ethene and ethyl alcohol, occurring by a transition state of four centers, presented the lowest activation barrier. Acetaldehyde and ethane elimination occurring through four centers, presented a high significantly barrier, but on the other hand it presented the smallest enthalpy, lightly exothermic above -0,8 kcal.mol-1. Eliminations 1,2 of methane and carbene occurring through three centers, together with the elimination 1,1 of hydrogen and carbene through three centers, elimination 2,2 of hydrogen and carbene through three centers and elimination 1,4 of hydrogen, acetaldehyde and ethene through six centers, had presented relatively next activation barriers, showing that they are competitive among themselves. The computed values of the channels that occur through cyclical transition states had been compared with the available experimental results and the trustworthiness of this computational boarding for the study of unimolecular reactions in multi-channel had been dicussed. Determination of thermochemical parameters, as heat of formation for radicalar species of the primary channel of decomposition and some alcoxyde radicais, together with the estimative of the electronic and protonic affinities,( with the ab initio Gaussian 2 boarding which estimate very precise eletronic energies ) and their results had been compared with the available experimental values and with values gotten through energies of bond and Benson\'s additivity rule.

Le PVDF, réputé particulièrement stable chimiquement et thermiquement, est largement utilisé dans le domaine du forage pétrolier « off shore ». Dans ce type d'utilisation, la contrainte en température peut atteindre plus de 140°C. Or, jusqu'à présent, la plupart des études de dégradation menées ont été faites à des températures très supérieures. Nous avons étudié les différentes réactions de dégradation du PVDF sur une large gamme de température (400 à 140°C) dans des atmosphères neutres ou oxydantes. Il s'est avéré que la déhydrofluoration et la réticulation étaient les principaux phénomènes de dégradation, ainsi que l'oxydation en présence d'oxygène. La déhydrofluoration a tout particulièrement été étudiée et modélisée au début de la dégradation. Des différences de comportement entre l'état fondu et semi-cristallin ont permis de conclure que les zones cristallines étaient plus sensibles thermiquement que les zones amorphes ; chaque phase cristalline ayant sa propre cinétique. L'action dégradante du DMF et de différentes amines a également été étudiée. Il s'avère que la dégradation en solution se traduit majoritairement par une déhydrofluoration et des coupures de chaîne.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
The present work aimed at investigating the biodiesel issuing from the transesterification of used frying oil with ethanol, via alkaline catalysis. Such investigation covers its thermo-oxidative stability during heating (thermal analysis and rheological properties) as well the kinetic profiles of the samples in the best oxidative induction time by the technique of Pressurized Differential Scanning Calorimetry (PDSC). The behavior of such biodiesel, as part of binary blends with fossil diesel at the proportions of 3, 5, 10, 25, 50, 75 and 100%, was also studied. The biodiesel synthesis used the ethanol route and was carried out under the following conditions: oil/alcohol molar ratio of 1:6 (m/m), 1 % de KOH, temperature of 32 °C, washing with 0.1M HCl and hot water. The reaction yield, determined by means of a mass balance aided by the technique of gas chromatography coupled to mass spectrometry, was of 90.56% and the ester content was of 99.56%. According to the physicochemical analyses, all the specifications for the biodiesel and blends met the requirements from Technical Regulation # 7 from the Brazilian National Agency of Petroleum, Natural Gas and Biofuels, with the exceptions of the odixative induction time (1.72 h) and kinematic viscosity (6.10 mm2s-1), which displayed values outside the limits established by the standard. In the thermal study, the thermogravimetric curves showed that the biodiesel blends in diesel are more volatile than the biodiesel derived from used frying oil (B100), whereas at lower concentrations (3, 5, 10 and 25%) are similar to fossil diesel. At higher concentrations (50 and 75%) the blends presented lower volatility and higher thermal stability in relation to fossil diesel and thus, biodiesel and its more concentrated blends showed higher safety in relation to transport, storage, handling and utilization. The study of the fluid dynamic properties of biodiesel and its blends showed that all the samples behave as Newtonian fluids at the studied (10, 25 and 40 ºC) temperatures. Also the results of cloud point, pour point and cold filter plugging point showed that the behavior of the blends with 3, 5 and 10% are similar to fossil diesel, therefore at these concentrations biodiesel acts as a lubricity additive to fossil diesel. The study by Pressurized Differential Scanning Calorimetry (PDSC) in the dynamic mode and the Rancimat technique revealed that the best antioxidant for the storage of biodiesel is BHT at the concentration of 2500 ppm. The determination of the kinetic parameters by the isothermal PDSC technique allowed determining the theoretical value of the shelf life of used frying oil biodiesel with 2500 ppm of the antioxidant BHT. Therefore, used frying oil biodiesel and its blends B3, B5, B10, B25, B50 and B75 may be used as an alternative source of biofuels.
O presente trabalho buscou investigar o biodiesel proveniente da transesterificação do óleo de fritura usado com álcool etílico, via catálise básica, e elucidar a sua estabilidade termo-oxidativa durante o aquecimento (análise térmica e propriedade reologicas) e estudar o perfil cinético da amostra com o melhor tempo de indução oxidativa pela técnica de calorimetria exploratória diferencial pressurizada (PDSC). Também, foi observado o comportamento do referido biodiesel, inserido em misturas binárias com o diesel fóssil nas proporções de 3, 5, 10, 25, 50, 75 e 100% também foi estudada. A síntese do biodiesel na rota etanólica processou-se sob condições de: razão molar óleo-álcool de 1:6 (m/m), 1 % de KOH, temperatura de 32 °C, lavagem com HCl 0,1 M e água quente. O rendimento reacional determinado por balanço de massa com auxilio da técnica de cromatografia gasosa acoplada a espectrometria de massa, foi de 90,56 %, com teor de esteres de 99,56 %. Nas análises físicoquímicas, todos as especificações para ambos biodiesel e blendas satisfizeram as exigências dos limites permitidos pelo Regulamento Técnico nº 7 da Agência Nacional do Petróleo, Gás Natural e Biocombustíveis. Com exceção do tempo de indução oxidativa (1,72 h) e a viscosidade cinemática (6,10 mm2s-1) que apresentaram valores fora dos limites estabelecidos pela norma. No estudo térmico, as curvas termogravimétricas evidenciaram que as blendas de biodiesel em diesel são mais voláteis em relação ao biodiesel derivado de óleo de fritura usado (B100) e em baixas concentrações (3, 5, 10 e 25%) se assemelham ao diesel fóssil. Em concentrações mais elevadas (50 e 75%) as blendas apresentam menor volatilidade e maior estabilidade térmica em relação ao diesel fóssil, e, portanto, o biodiesel e suas blendas mais concentradas apresentam maior segurança em relação ao transporte, armazenagem, manuseio e utilização. O estudo das propriedades fluído-dinâmicas do biodiesel e suas blendas, demostraram que todas as amostras comportam como fluídos newtonianos a temperatura (10, 25 e 40 ºC) e que tanto os resultados de ponto de nevoa, fluidez e ponto de entupimento de filtro a frio, apresentaram comportamento para as blendas 3, 5 e 10% semelhantes ao observado para o diesel fossil, e, portanto nestas concentrações o biodiesel atua como um aditivo de lubricidade do óleo diesel fossil. O estudo por calorimetria exploratória diferencial pressurizada no modo dinâmico e a técnica de rancimat revelou que o melhor antioxidante para o armazenamento do biodiesel é o BHT com concentração de 2500 ppm. A determinação dos parâmetros cinéticos pela técnica de PDSC isotérmica foi possível determinar teoricamente o tempo de vida de prateleira do biodiesel derivado de óleo de fritura usado com 2500 ppm do antioxidante BHT. Então, o biodiesel de fritura usado e blendas B3, B5, B10, B25, B50 e B75 podem ser utilizados como uma fonte alternativa de biocombustíveis.

碩士
國立臺北科技大學
化學工程系碩士班
91
Formulation of UV curable resins used in this study contains aliphatic polyester based urethane diacrylate oligomer, tripropylene glycol diacrylate as difunctional monomer diluter and photoinitiator. In this study, concentration of photoinitiator and monomer diluter and clay in the formulation was varied separately to investigate its effect on the curing behavior and the thermo- physical properties of cured film. FTIR was employed to monitor the UV curing reaction and find the radiating time for complete reaction. UV Curing kinetic study was carried out on Differential Photo Calorimeter. Thermal properties of UV cured film were determined by DSC, TGA and TMA . Surface hardness was measured by micro-scratch. Data from Photo-DSC study pointed out that increase the concentration of photoinitiator in the formulation accompanied with an increase in curing rate, and the cured films showed a lower decomposition temperature, glass transition temperature and surface hardness. When the concentration of diluter in the formulation was increased, curing rate also increased; the cured films showed a higher decomposition temperature and glass transition temperature. The following time (t) verse conversion ratio (α) equation is used for kinetic study where k is reaction constant, m is autoacceleration parameter, n is reaction order.

Organic conducting polymer, poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS), is widely recognized for its electro-actuation mechanism and is used in flexible electronics. Its high potential as actuator is based on a strong coupling between chemical, mechanical and electrical properties which directly depends on external stimuli. There is no model today to describe the interplay between moisture absorption, mechanical expansion and electrical stimulus. Elucidating the role of each component in the effective actuation properties is needed to further optimize and tailor such materials. The objective of this thesis is to develop a macroscopic model to describe water sorption kinetics of the PEDOT:PSS film. We used gravimetric analysis of pure PEDOT:PSS film of three different thicknesses to investigate absorption kinetics over a broad range of temperatures and relative humidity. Our results revealed that the moisture uptake of PEDOT:PSS film does not follow Fickian diffusion law due to the retained amount of water after desorption process. We used an existing diffusionreaction model to describe this behavior, and COMSOL Multiphysics and MATLAB software programs to implement it. We observed that the generic model we used in our work could predict polymer behavior with 95% accuracy. However, our model was not able to properly represent the data at very high relative humidity at low temperature, which was attributed to the excessive swelling of the film. Also, we examined a relation between the moisture content of PEDOT:PSS and its mechanical strain and electrical conductivity. The results presented here are the first step towards a general multiphysics electro-thermo-mechanical description of PEDOT:PSS based actuators.

This work involved an investigation into the mechanisms governing the reduction of material in the solids bed of the Ifcon® process. Thermo gravimetric analyses were done to investigate the influence of various operational parameters on the rate of solid state reduction. The experiments were modeled, and model predictions were compared to experimental results. Kinetic data was analised and the reduction rate constants were calculated. The rate constants were used as inputs to a model, which describes the reduction behaviour and temperature profile in a composite solids bed (similar to that in the Ifcon® process). High temperature reduction- and melting tests were done in an 150 kW induction furnace, to simulate final reduction in a solids bed. The temperature profile through the solids bed was measured and results were compared to model predictions. Finally the extent to which solid state reduction occurs in the solids bed was estimated as a function of production rate.
Dissertation (MEng (Metallurgical Engineering))--University of Pretoria, 2008.
Materials Science and Metallurgical Engineering
unrestricted

The effect of Laves phase (Fe2Nb) formation on the Charpy impact toughness of the ferritic stainless steel type AISI 441 was investigated. The steel exhibits good toughness after solution treatment at 850°C, but above and below this treatment temperature the impact toughness decreases sharply. With heat treatment below 850°C the presence of the Laves phase on grain boundaries and dislocations plays a significant role in embrittlement of the steel whereas above that temperature, an increase in the grain size from grain growth plays a major role in the impact embrittlement of this alloy. The toughness results agree with the phase equilibrium calculations made using Thermo–Calc® whereby it was observed that a decrease in the Laves phase volume fraction with increasing temperature corresponds to an increase in the impact toughness of the steel. Annealing above 900°C where no Laves phase exists, grain growth is found which similarly has a very negative influence on the steel’s impact properties. Where both a large grain size as well as Laves phase is present, it appears that the grain size may be the dominant embrittlement mechanism. Both the Laves phase and grain growth, therefore, have a significant influence on the impact properties of the steel, while the Laves phase’s precipitation behaviour has also been investigated with reference to the plant’s manufacturing process, particularly the cooling rate after a solution treatment. The microstructural analysis of the grain size shows that there is a steady increase in grain size up to about 950°C, but between 950°C and 1000°C there is a sudden and rapid 60 % increase in the grain size. The TEM analysis of the sample that was annealed at 900°C shows that the Laves phase had already completely dissolved and cannot, therefore, be responsible for “unpinning of grain boundaries” at temperatures of 900°C and higher where this “sudden” increase in grain size was found. The most plausible explanation appears to be one of Nb solute drag that loses its effectiveness within this temperature range, but this probably requires some further study to fully prove this effect. During isothermal annealing within the temperature range of 600 to 850°C, the time – temperature – precipitation (TTP) diagram for the Laves phase as determined from the transformation kinetic curves, shows two classical C noses on the transformation curves. The first one occurring at the higher temperatures of about 750 to 825°C and the second one at much lower temperatures, estimated to possibly be in the range of about 650 to 675°C. The transmission electron microscopy (TEM) analyses show that there are two independent nucleation mechanisms that are occurring within these two temperature ranges. At lower temperatures of about 600°C, the pertaining nucleation mechanism is on dislocations and as the temperature is increased to above 750°C, grain boundary nucleation becomes more dominant. Also, the morphology of the particles and the mis-orientation with the matrix changes with temperature. At lower temperatures the particles are more needle-like in shape, but as the temperature is increased the shape becomes more spheroidal. The effect of the steel’s composition on the Laves phase transformation kinetics shows that by lowering the Nb content in these type 441 stainless steels, had no significance effect on the kinetics on precipitation of the Laves phase. However, a Mo addition and a larger grain size of the steel, retard the formation of the Laves phase, although the optimum values of both parameters still need further quantification. The calculation made for the transformation kinetics of the Laves phase, using the number density of nucleation sites No and the interfacial energy, as the fitting parameters in this work, demonstrated a reasonable agreement with experimental results.
Thesis (PhD)--University of Pretoria, 2010.
Materials Science and Metallurgical Engineering
unrestricted

Für eine effiziente und nachhaltige Nutzung von Georeservoiren sind bestmögliche Reservoirmanagementverfahren erforderlich. Oft setzen diese Verfahren auf Tracer-Tests. Dabei enthalten die aufgezeichneten Tracersignale integrale Informationen der Reservoireigenschaften. Tracer-Tests bieten somit eine leistungsfähige Technik zur Charakterisierung und Überwachung der bewirtschafteten Georeservoire. Im Gegensatz zu Tracer-Tests mit konservativen Tracern, welche bereits etablierte Testroutinen zur Verfügung stellen, ist die Verwendung von reaktiven Tracern ein neuer Ansatz. Aufgrund unpassender physikalisch-chemischer Modelle und/oder falschen Annahmen ist die Analyse und Interpretation von reaktiven Tracersignalen jedoch oft verzerrt, fehlinterpretiert oder sogar unmöglich. Reaktive Tracer sind dennoch unersetzbar, da sie durch die gezielte Ausnutzung selektiver und spezifischer Reaktionen mögliche Metriken von Reservoirtestverfahren auf einzigartige Weise erweitern. So liefern reaktive Tracer für ein integriertes Reservoirmanagement geforderten Aussagen über Reservoirmetriken wie z.B. Wärmeaustauschflächen oder in-situ Temperaturen. Um Unsicherheiten bei der Auswertung von Tracerexperimenten zu reduzieren, werden theoretische und experimentelle Untersuchungen zu hydrolysierenden Tracern vorgestellt. Diese Tracer sind durch ihre Reaktion mit Wasser charakterisiert. Einerseits können sie als thermo-sensitive Tracer Informationen über Temperaturen und abgekühlte Anteile eines beprobten Reservoirs liefern. Für die Interpretation von thermo-sensitiven Tracerexperimenten sind die Kenntnis der zugrunde liegenden Reaktionsmechanismen sowie bekannte Arrhenius-Parameter Voraussetzung, um die verwendete Reaktion pseudo erster Ordnung nutzen zu können. Darüber hinaus ermöglichen die verwendeten Verbindungen durch ihre Fluoreszenzeigenschaften eine Online-Messung. Um die Empfindlichkeit und praktischen Grenzen thermo-sensitiver Tracer zu untersuchen, wurden kontrollierte Laborexperimente in einem eigens dafür entwickelten Versuchsaufbau durchgeführt. Dieser besteht aus zwei seriell geschalteten Säulen, die beide mit Sand gefüllt sind und jeweils auf eine eigene Temperatur eingestellt werden können. Somit ist es möglich, verschiedene thermische Einstellungen zu betrachten. Die untersuchten experimentellen Szenarien imitieren größtenteils Feldanwendungen: Durchflussexperimente sowie auch Experimente mit einer Umkehr der Fließrichtung. Darüber hinaus wurde untersucht, ob thermo-sensitive Tracer auch sensitiv gegenüber der Position der Temperaturfront sind. Dabei wurden die Tracer kontinuierlich oder gepulst injiziert. Die Ergebnisse bestätigen die zugrunde liegende Theorie experimentell. Wenn die pH-Abhängigkeit der Hydrolyse bei der Analyse berücksichtigt wird, kann eine Temperaturschätzung mit einer Genauigkeit und Präzision von bis zu 1 K erreicht werden. Die Schätzungen sind von Verweilzeit und gemessenen Konzentrationen unabhängig. Weiterhin lässt sich eine Schätzung über den ausgekühlten Anteil des Systems erhalten. Durch die steuerbaren und definierten Laborbedingungen ist es erstmals möglich, die geforderte Anwendbarkeit von thermo-sensitiven Tracern belastbar nachzuweisen. Des Weiteren wird eine zweite Anwendung hydrolysierender Tracer vorgeschlagen. Beim Lösen von CO2 für „Carbon Capture and Storage“-Anwendungen hängt die Effizienz maßgeblich von der Grenzfläche zwischen CO2 und der Sole in tiefen Reservoiren ab. Somit ist diese Metrik wichtig, um die Effizienz der CO2 Auflösung in Wasser zu bewerten. Die gezielt entwickelten Kinetic-Interface-Senitive-Tracer (KIS-Tracer) nutzen, zusätzlich zur Hydrolyse an der Grenzfläche, die unterschiedlichen Lösungseigenschaften von Tracer und Reaktionsprodukt im entsprechenden Fluid. Somit lassen sich potentiell Aussagen über die Dynamik der Grenzfläche machen. Neben dem grundlegenden Konzept sowie den theoretischen Tracer-Anforderungen wird eine erste Anwendung im Laborexperiment vorgestellt. Diese zeigt das erfolgreiche, zielorientierte Moleküldesign und bietet eine experimentelle Basis für ein makroskopisches numerisches Modell, mit welchem numerische Simulationen verschiedener Testszenarien durchgeführt werden, um das Zusammenspiel von KIS-Tracer und dynamischer Grenzfläche zu untersuchen. Aufgrund der Temperaturabhängigkeit der Reaktionsgeschwindigkeit hydrolysierender Tracer werden in der Regel auch thermische Signale aufgezeichnet. Der letzte Teil prüft die Möglichkeit, Informationen aus den aufgezeichneten Temperaturen zu extrahieren. Für ein idealisiertes Einzelkluftsystem wird eine Reihe von analytischen Lösungen diskutiert. Aus thermischen Injektion-/Entzugsversuchen können damit räumliche und zeitliche Profile abgeleitet werden. Mit der Verwendung von mathematisch effizienten Inversionsverfahren wie der iterativen Laplace-Transformation lassen sich rechentechnisch effiziente Realraum-Lösungen ableiten. Durch die Einführung von drei dimensionslosen Kennzahlen können die berechneten Temperaturprofile auf Bruchbreite oder Wärmetransportrate, wechselnde Injektions-/ Pumpraten und/oder auf in der Nähe beobachtbare räumliche Informationen analysiert werden. Schließlich werden analytische Lösungen als Kernel-Funktionen für nichtlineare Optimierungsalgorithmen vorgestellt. Zusammenfassend bearbeitet die vorliegende Arbeit den Übergang zwischen Tracerauswahl und Traceranwendung. Die Ergebnisse helfen Planungs- und Analyseunsicherheiten zu reduzieren. Dies wird bezüglich der Empfindlichkeit gegenüber Temperaturen, Kühlungsanteilen, flüssig/flüssig-Grenzfläche, Kluftbreite und Wärmetransportrate gezeigt. Somit bieten die vorgestellten Tracerkonzepte neue Metriken zur Verbesserung von Reservoirmanagementverfahren. Die experimentellen Ergebnisse und die neuen analytischen Modelle ermöglichen einen tiefen Einblick in die kollektive Rolle der Parameter, welche die Hydrolyse und den Wärmetransport in Georeservoiren kontrollieren.