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Physical aging measurements were performed on various polymeric glasses with the overriding goal of developing a better molecular picture of the nonequilibrium glassy state. To this end, aging-induced changes in mechanical properties and in the thermodynamic state (volume and enthalpy) were assessed for two different miscible polymer blends as a function of both composition and aging temperature. This investigation considered the physical aging behavior of blends containing atactic polystyrene (a-PS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) as well as mixtures of poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN). Substantial attractive chemical interactions are characteristic of a-PS/PPO blends but are absent in PMMA/SAN blends. The distinct nature of interactions for these two blends resulted in differences in the compositional dependence of secondary relaxation intensity, segmental cooperativity which dictates glass formation kinetics, and density (prior to aging). The variation of volume relaxation rate with aging temperature and composition was interpreted based upon these characteristics for the two systems. In addition, a general relationship was uncovered which linked structural relaxation rates for amorphous polymers to their respective segmental relaxation characteristics (glass transition cooperativity or fragility), which in turn are well understood from a molecular standpoint. This work, therefore, established a basis for comprehending glassy state volume and enthalpy relaxation rates based upon molecular characteristics. Developing an understanding of the connection between the evolving thermodynamic state and mechanical property changes fared less well. The fact that the thermodynamic and mechanical properties can have very different relaxation time responses governing their changes in the nonequilibrium glassy state was clearly evident in an extensive study of the physical aging characteristics of an amorphous polyimide material. For some materials, interpretation of mechanical aging behavior was obscured by thermorheological complexity arising due to overlap of a secondary relaxation with the main chain softening dispersion. / Ph. D.

Made available in DSpace on 2014-06-11T19:33:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-09-21Bitstream added on 2014-06-13T18:45:24Z : No. of bitstreams: 1 gomesfilho_js_dr_jabo.pdf: 765540 bytes, checksum: 15848770f797f69a1af286f79d7dc8d4 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Quatro experimentos foram conduzidos para avaliar o efeito do sombreamento artificial e da pintura dos telhados na melhoria do conforto térmico de modelos reduzidos simulando galpões avícolas. Em todos os experimentos foram utilizadas coberturas com telha de fibrocimento, novas, sem cimento amianto, com 4,0mm de espessura. O Experimento 1 foi realizado na Universidade Estadual do Maranhão (UEMA), câmpus de São Luís, onde foram testados cinco tipos de coberturas: 1- sem tela, sem pintura (STSP – controle); 2- com tela a 0,05m de altura da telha, sem pintura (CT5SP); 3- com tela a 0,05m de altura da telha, com pintura (CT5CP); 4- com tela a 0,08m de altura da telha, sem pintura (CT8SP) e 5- com tela a 0,08m de altura da telha, com pintura (CT8CP). Foram determinados o Índice de Temperatura de Globo Negro e Umidade (ITGU), a Carga Térmica de Radiação (CTR) e a Entalpia Específica (H). As colheitas das variáveis meteorológicas (temperaturas de globo negro, de bulbo seco, de bulbo úmido e velocidade do vento) foram realizadas durante 12 dias experimentais (04 a 15 de nov. de 2009) às 10:00, 12:00, 14:00 e 16:00 horas. O tipo de cobertura CT5SP foi o que apresentou os melhores valores para ITGUcorr (79,81) e H (78,84 KJ.Kg-1 de ar seco). O melhor resultado para CTRcorr foi apresentado pelo tratamento CT5CP (480,12 W.m-2). O Experimento 2 foi realizado na Universidade Estadual Paulista (UNESP), câmpus de Jaboticabal, onde foram testados os mesmos tipos de coberturas do Experimento 1. As colheitas e registro das variáveis meteorológicas foram realizadas por 40 dias (13 de fev. a 24 de mar. de 2010), nos mesmos horários do Experimento 1. O tipo cobertura que proporcionou menor resultado para o ITGU (83,86) e H (86,41 KJ.Kg-1 de ar seco) foi o CT8CP. A menor CTR (549,52 W.m-2) foi verificada na cobertura CT5CP. O Experimento 3 objetivou verificar o efeito de dois tipos de telas... / Four experiments were conducted to assess the effect of shading and painting of roofs improving thermal comfort in reduced models of poultry houses. In all the experiments were used with roofing cement tile, new, no asbestos cement, with 4.0 mm thick. The first experiment was conducted at the Universidade Estadual do Maranhão (UEMA), campus of São Luís, where were tested five types of coverage: 1 - no shading, no paint (STSP - control), 2 - with shading 0.05 m in height tile, unpainted (CT5SP) 3 - with shading 0.05 m in height tile with painting (CT5CP) 4 - with shading 0.08 m in height tile, unpainted (CT8SP) and 5 – with shading 0.08 m height of the tile with painting (CT8CP). Were evaluated the index of black globe temperature and humidity (BGTHI), the Heat Load (HL) and the specific enthalpy (H). The readings of meteorological variables (black globe temperature, dry bulb, wet bulb temperatures and wind speed) were measured during 12 experimental days (from nov. 4th to 15th, 2009) at 10:00, 12:00, 14: 00 and 16:00 hours. The type of coverage CT5SP had the lowest values for BGTHI (79,81) and H (78,84 KJ.Kg-1 dry air). The best result for CTRcorr (480,12 W.m-2) was presented by treatment CT5CP. The second experiment was conducted at Universidade Estadual Paulista (UNESP), campus of Jaboticabal, where were tested the same types of coverages of Experiment 1. The collection and recording of meteorological variables were performed for 40 days (from feb. 13th to 24th, 2010), at the same times of Experiment 1. The type coverage that provided smaller results for the BGTHI (83,86) and H (86,41 KJ.Kg-1 dry air) was CT8CP. The lower HL (549,52 W.m-2) was verified with the coverage CT5CP. The third experiment aimed at assessing the effect of two types of shading screens (50 and 80%) on the thermal comfort... (Complete abstract click electronic access below)

This diploma thesis is focused on problems of heat exchangers. There are two main objectives. The first objective is based on long-term measuring of enthalpy heat exchanger, processing of measured data and comparison of result with manufacturer's results. The second objective is design of variant solutions for two types of heat exchanger of air conditioning unit of selected shop. For variant without moisture transportation was selected cross flow exchangers. Thanks to knowledge from long-term measurement, was selected enthalpy heat exchanger for variant with moisture transportation. Chosen variants were compared with emphasis on heat and moisture exchange efficiency with requirements on Ecodesign.

Two numerical models have been developed to describe the volumetric changes during solidification in pure metals and alloys and to predict shrinkage defects in the castings of general three-dimensional configuration. The first model is based on the full system of the Continuity, Navier-Stokes and Enthalpy Equations. Volumetric changes are described by introducing a source term in the Continuity Equation which is a function of the rate of local phase transformation. The model is capable of simulating both volumetric shrinkage and expansion. The second simplified shrinkage model involves the solution of only the Enthalpy Equation. Simplifying assumptions that the feeding flow is governed only by gravity and solidification rate and that phase transformation proceeds only from liquid to solid allowed the fluid flow equations to be excluded from consideration. The numerical implementation of both models is based on an existing proprietary general purpose CFD code, FLOW-3D, which already contains a numerical algorithm for incompressible fluid flow with heat transfer and phase transformation. An important part of the code is. the Volume Of Fluid (VOF) algorithm for tracking multiple free surfaces. The VOF function is employed in both shrinkage models to describe shrinkage cavity formation. Several modifications to FLOW-3D have been made to improve the accuracy and efficiency of the metal/mould heat transfer and solidification algorithms. As part of the development of the upwind differencing advection algorithm used in the simulations, the Leith's method is incorporated into the public domain twodimensional SOLA code. It is shown that the resulting scheme is unconditionally stable despite being explicit.

Les techniques d’analyse thermique et de calorimétrie sont des méthodes d’essai largement utilisées dans les laboratoires d’analyse physico-chimique, pour des finalités de recherche ou de contrôle qualité. Comme tout appareil de mesure, un analyseur thermique ou un calorimètre doit être étalonné en température et en énergie avec des matériaux de référence certifiés. Les matériaux de référence recommandés correspondent généralement aux points fixes de l'échelle internationale de température (EIT-90), à savoir gallium, indium, étain, zinc et aluminium. Il existe peu de matériaux de référence certifiés au-dessus de 420 °C, alors que certains analyseurs thermiques peuvent être utilisés jusqu'à 1000 °C, voire au-delà.L’élaboration et la certification de matériaux de référence doivent employer des méthodes de mesure très précises avec un raccordement métrologique des mesures au système international d’unités (SI). Le Laboratoire Commun de Métrologie (LCM) s'est engagé dans le développement d'un moyen de référence métrologique en calorimétrie permettant des mesures précises en enthalpie de fusion et en capacité thermique massique sur la plage de température [23 °C, 1000 °C]. La solution métrologique retenue a été de modifier un calorimètre de type Calvet, et de mettre au point des procédures d’étalonnage et de mesure afin d’atteindre des incertitudes de mesures suffisamment faibles pour la certification des matériaux de référence.Dans ce travail, un système d'étalonnage fonctionnant à haute température a été spécifiquement conçu et intégré dans le calorimètre pour permettre l'étalonnage par substitution électrique. Ce système permet de réaliser successivement des étalonnages par effet Joule et des mesures d’enthalpie de fusion, sans modification des conditions expérimentales.Ce travail comprend également le développement des systèmes d’acquisition et traitement des résultats des mesures. La détermination de l'enthalpie de fusion de plusieurs métaux (indium, étain et argent notamment) avec une recherche des facteurs d’influence sur cette grandeur, et une estimation des incertitudes de mesure. La mesure de l’enthalpie de fusion d’un alliage eutectique argent-cuivre, candidat comme matériau de référence en énergie à 779 °C, est également présentée. / Differential scanning calorimeters are widely used in many academic and industrial laboratories to study the thermal behavior of materials for research or quality control. Like any measuring device, a thermal analyzer or calorimeter must be calibrated in temperature and energy with certified reference materials. Recommended reference materials generally correspond to fixed points of the International Temperature Scale (ITS- 90), namely: gallium, indium, tin, zinc and aluminum. However, there are few certified reference materials above 420 °C, while the operating range of some thermal analyzers and calorimeters exceeds 1000 °C.The certification of reference materials insures the metrological traceability of measurements to the International System of Units (SI). The LCM-LNE has been working in the development of a metrological standard facility for accurate measurements of the enthalpy of fusion and heat capacity in the temperature range [23 °C, 1000 °C]. The metrological approach is based on the modification of a commercial Calvet calorimeter and of the procedures implemented for calibration and measurement, so as to get measurement uncertainties sufficiently low to fulfill the objectives of the certification of reference materials.A new in-situ high temperature calibration system (constituted by a resistance wire wound around the crucible containing the material sample) was integrated into the calorimeter to perform the calibration by electrical substitution. The system allows both calibration and measurement without modification of the apparatus, so that the experimental conditions during both steps remain unchanged.This work also includes the development of data acquisition system and processing of measurement results. The determination of the enthalpy of fusion of several metals (indium, tin and silver in particular) with an estimation of the measurement uncertainty has been made. The measurement of the enthalpy of fusion of a silver-copper eutectic alloy, as candidate reference material at 779 °C, is also presented.

La thèse porte sur la conception et la simulation d'un réservoir de stockage solide de l'hydrogène sous forme d'hydrure de magnésium (MgH2). La particularité du réservoir conçu réside dans sa capacité à stocker l'énergie d'absorption grâce à un matériau de changement de phase (MCP). Afin de pouvoir prouver la viabilité du système, une étude portant sur le comportement de l'hydrure de magnésium compacté lors du cyclage à été effectuée. Celle-ci montre qu'après 100 cycles, les cinétiques de réaction et les taux massiques de stockage d'hydrogène ne sont pas affectés. En revanche, un changement de morphologie important a été observé puisqu'une dilatation ainsi qu'une augmentation importante de la conductivité des matériaux composites ont été relevées. L'étude du MCP révéla l'importance de certains paramètres, en particulier la conductivité thermique et l'enthalpie de fusion. Le MCP sélectionné est un alliage métallique en composition eutectique. Celui ci est bon conducteur de chaleur, présente une enthalpie de fusion élevée et une stabilité de comportement thermique au cyclage. Le réservoir construit contient 10 kg d'hydrure de magnésium co-broyé + 5 % de Graphite Naturel Expansé. Il est capable de stocker 7000 NL d'hydrogène (625 g) en 3h. L'avantage principal du réservoir est son efficacité énergétique, puisque la chaleur stockée par le MCP à l'absorption est refournie lors de la désorption. Afin de pouvoir prédire les comportements thermiques et cinétiques des prochains réservoirs basés sur cette technologie, 2 modèles numériques utilisant Matlab et Fluent ont été développés et validés. / The thesis's subject is about creation and modeling of a solid state hydrogen tank using magnesium hydride (MgH2). The main characteristic of this tank is the ability to store the heat of absorption due to the use of a Phase Change Material (PCM). In order to prove the sustainability of this system, a study, on the magnesium hydride's behavior, has been carried out. On one hand, kinetic properties and the amount of the stored hydrogen do not decrease after 100 cycles. On the other hand, a significant change on material morphology has been noticed. Indeed, a swelling and an increasing of thermal conductivity have been measured. Investigations about the MCP showed the importance of the thermal conductivity and the heat of fusion. That's why a metallic eutectic alloy has been selected. His atomic composition is Mg69Zn28Al3, he is a good thermal conductor, having a high heat of fusion, and presenting a good chemical stability during cycling. The designed tank contains 10 kg of magnesium hydride ball-milled added with Expanded Natural Graphite. It can absorb 7000 NL (625 g) of hydrogen in 3 hours and a half. On one total cycle, the energetic efficiency can be estimated to more than 70 %. At the same time, two numerical modeling have been achieved with Fluent and Matlab softwares, in order to make the design of next generation of tanks easier.

Solid propellant gas generators that have high gas capacity are used for fast pressurization of inflatable devices or elastic shells. However, many applications such as control surface actuation, air bottle pressurization in rocket engines and safety systems of automobiles (airbags) require exit gases at near ambient temperature. A scheme suitable for short duration applications is passive cooling of gas generator gases by using a packed bed as compact heat exchanger. A study indicated that the mass flow rates of solid propellant gas generators for applications such as air bottle pressurization and control system actuators were of the order of 1 kg/s. Since pressure and enthalpy drop correlations for packed beds with mass flow rates (~1 kg/s) and packing sphere based Reynolds number (Red) ~ 9X104 were unavailable in open literature, an experimental investigation was deemed necessary. The objectives of the present study were (a) characterization of packed beds for pressure and enthalpy drop, (b) develop Euler and Nusselt number correlations at Red~105 and (c) evolve an engineering procedure for estimation of packed bed pressure and enthalpy drop. An experimental test facility with a hydrogen-air combustor was designed and fabricated for this purpose to characterize a variety of packed beds for pressure drop and heat transfer. Flow through separate packed beds consisting of 9.5mm and 5mm steel spheres and lengths ~200mm and ~300mm were studied in the sphere based Reynolds numbers (Red) range of 0.4X104 to 8.5X104. The average porosity (є) of the randomly packed beds was ~0.4. The ratios of packed bed diameter to packing diameter for 9.5mm and 5mm sphere packing were ~ 9.5 and 18 respectively. The inlet flow temperature was unsteady and a suitable arrangement using mesh of spheres was used at either ends to eliminate flow entrance and exit effects. Stagnation pressures were measured at entry and exit of the packed beds. The pressure drop factor fpd, (ratio of Euler number (Eu) to packed bed dimensions) for packed bed with 9.5mm spheres exhibited an asymptotically decreasing trend with increasing Reynolds number, and a correlation for the pressure drop factor is proposed as, fpd=Eu/ [6(1-є) (L/dp)] =125.3 Red-0.4; 0.8X104 < Red < 8.5X104 (9.5mm sphere packing). However, for packed beds with 5mm spheres the pressure drop factor fpd, was observed to increase in the investigated Reynolds number range. The correlation based for pressure drop factor is proposed as, fpd= Eu/ [6(1-є) (L/dp)] =0.0479 Red0.37; 0.4X104 < Red < 3.9X104 (5mm sphere packing). The pressure drop factor was observed to be independent of the inlet flow temperature. Gas temperatures were measured at the entry, exit and at three axial locations along centerline in the packed beds. The solid packing temperature was measured at three axial locations in the packed bed. At Red~104, the influence of gas phase and solid phase thermal conductivity on heat transfer coefficient was found to be negligible based on order of magnitude analysis and solid packing temperature data obtained from the experiments. Evaluation of sphere based Nusselt number (Nud) at axial locations in the packed bed indicated a length effect on the heat transfer coefficient, which was a function of Reynolds number and size of spheres used in packing. The arithmetic average of Nusselt numbers at different axial locations in the packed bed were correlated as Nud=3.85 Red0.5; 0.5X104 < Red < 8.5X104. The Nusselt numbers obtained in the experiments were consistent with corresponding literature data available at lower Reynolds numbers. In this experimental study Euler number correlations for pressure drop and Nusselt number correlations for heat transfer were obtained for packed beds at Red~105. An engineering model for estimation of packed bed pressure and enthalpy drop was evolved, which is useful for sizing of packed bed heat exchanger in solid propellant gas generation systems.

It is of great interest to develop and utilize a high surface area material with optimized hydrogen sorption properties. The need for a renewable energy source to replace automobile gasoline has become more critical in the past decade. Hydrogen is a viable fuel source for automobile usage; however, the question of how hydrogen will be safely and efficiently stored still remains. Critical factors for optimum hydrogen storage include ambient conditions and low activation temperature for adsorption and desorption phenomena. In order for optimum hydrogen adsorption to be achieved, the properties of (1) high surface area, (2) optimum hydrogen adsorption energy, and (3) Kubas interactions between metals and hydrogen molecules need to be considered. Fullerenes have recently become more popular with the discovery and mass production of graphene sheets derived from graphite. Graphene is a modified form of graphite that takes the form of sheets with less agglomeration than its respective graphitic form. This form has the potential for high surface area and storage capabilities. Storage of hydrogen at room temperature must be optimized by increasing the surface area and having an adsorption enthalpy between 15 - 20 KJ/mol. Graphene (G) sheets and graphene oxide (GO) sheets have been utilized as a matrix for hydrogen storage. These materials can also be cross-linked with organic spacers in order to form a porous framework of higher surface area. Metal decorating by calcium and platinum of the G/GO matrix has been used to enhance Kubas interactions, adsorption enthalpies, and spillover phenomenon. The use of a polymer matrix has also been implemented. Polyaniline is a novel superconducting polymer with unique electronic properties. Complexes of Polyaniline with graphene and graphene oxide have been investigated for hydrogen storage properties. Graphene and graphene oxide surface modification via metal decoration have been investigated in order to determine the most efficient synthesis and particle size on the G/GO matrix. Characterization by XRD, BET, adsorption enthalpy, PCT, TGA, FT-IR, and TEM/SEM (when applicable) were employed to optimize and compare the materials in the effort to develop a suitable storage material.

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