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In this thesis, the discharge products formed at the cathode and the performance and cell chemistry of sodium-oxygen batteries have been studied. This was carried out using different NaOTf salt concentrations. The influence of different salt concentrations on sodium-oxygen batteries was investigated since it has been shown that increasing the salt concentration beyond conventional concentrations could result in advantages such as increased stability of the electrolytes towards decomposition, higher thermal stability and lower volatility. An increase in salt concentration has also been shown to influence the electrochemical potential window. The solubility of NaOTf was investigated in two different solvents, DME and diglyme. NaOTf was found to be more soluble in DME compared to diglyme but due to the volatile nature of DME, three different concentrations of NaOTf were prepared with diglyme as solvent. Experimentation involved discharging the batteries to either maximum or limited capacity. The discharge products were examined and characterized using XRD and SEM. The main discharge product was identified as sodium superoxide although sodium peroxide dihydrate was also identified in one battery. A trend of higher capacity and voltage plateaus with higher salt concentration was also found. The influence of trace amounts of water was suggested as one explanation as it works as a catalyst, promoting sodium superoxide cube growth due to improved transportation of superoxide. Another or contributing explanation could be a possible change in donor number with increased salt concentration, resulting in higher solubility and longer lifetime of superoxide, promoting the growth of sodium superoxide cubes.

Ce travail de recherche est dédié à la compréhension des mécanismes physiques de l’érosion de cavitation dans un fluide compressible à l’échelle fondamentale de l’implosion d’une bulle de cavitation. Suite à l’implosion d’une bulle de vapeur à proximité d’une surface solide, des très hautes pressions sont générées. Ces pressions sont considérées responsables de l’endommagement (érosion) des surfaces solides observé dans la plupart des applications. Notre approche numérique démarre avec le développement d’un solveur compressible capable de résoudre les bulles de cavitation au sein du code volumes finis YALES2 en utilisant un simple modèle de mélange homogène des phases fluides. Le solveur est étendu à une approche ALE (Arbitraire Lagrangien Eulérien) dans le but de mener des simulations d’interaction fluide-structure sur un maillage mobile. La réponse du matériau solide est calculée avec le code de calcul éléments finis Cast3M, et nous a permis de mener des simulation avec un couplage d’abord monodirectionnel, ensuite bidirectionnel, entre le fluide et le solide. On compare des résultats obtenus à deux dimensions, puis à trois, avec des observations expérimentales. On discute les chargements de pression estimés, et les réponses de différents matériaux pour des implosions de bulle à des différentes distances de la surface. Enfin, à travers l’utilisation de simulations avec couplage bidirectionnel entre fluide et solide, on identifie l’amortissement des chargements de pression pour les différents matériaux. / This research is devoted to understanding the physical mechanism of cavitation erosion in compressible liquid flows on the fundamental scale of cavitation bubble collapse. As a consequence of collapsing bubbles near solid wall, high pressure impact loads are generated. These pressure loads are believed to be responsible for the erosive damages on solid surface observed in most applications. Our numerical approach begins with the development of a compressible solver capable of resolving the cavitation bubbles in the finite-volume solver YALES2 employing a simplified homogenous mixture model. The solver is extended to Arbitrary Lagrangian-Eulerian formulation to perform fluid structure interaction simulation with moving mesh capabilities. The material response is resolved with the finite element solver Cast3M, which allowed us to perform one-way and two-way coupled simulations between the fluid and solid domains. In the end, we draw comparisons between 2D and 3D vapor bubble collapse dynamics and compare them with experimental observations. The estimated pressure loads on the solid wall and different responses of materials for attached and detached bubble collapses are discussed. Finally, the damping of pressure loads by different materials is identified with two-way coupled fluid-structure interaction.

Este trabalho apresenta duas técnicas de ensaios não-destrutivos por ultra-som realizados em um tanque com água para determinar as constantes elásticas de materiais compostos de fibra de vidro/epóxi. A primeira técnica é a transmissão direta utilizando um par de transdutores. A segunda é a técnica de pulso-eco, utilizando um único transdutor. A água do tanque atua como um acoplante para transferir a energia mecânica do transdutor para a amostra. Como o transdutor não fica em contato direto com a amostra, pode-se garantir um acoplamento constante. O sistema de medição dota de um dispositivo que permite medir a velocidade da onda elástica sob diferentes ângulos de incidência, através da rotação manual da amostra. Devido ao fenômeno de conversão de modos com incidência oblíqua na interface amostra-água, ensaios por ultra-som em tanques com água fornecem as informações necessárias para o cálculo das constantes elásticas em amostras de materiais anisotrópicos, numa dada direção, a partir das medições das velocidades longitudinal e de cisalhamento. Numa dada direção de propagação em um meio anisotrópico, existem três ondas elásticas distintas: uma longitudinal e duas de cisalhamento. Se as constantes elásticas do material são conhecidas, é possível obter as três velocidades em uma dada direção bastando resolver a equação de Christoffel. Invertendo a equação de Christoffel, obtém-se as constantes elásticas a partir das velocidades medidas em uma dada direção. Os experimentos são realizados com amostras de fibra de vidro/epóxi unidirecionais e bidirecionais, utilizando transdutores com freqüências de 0,5 MHz, 1 MHz e 2,25 MHz. Os resultados experimentais obtidos utilizando ambas as técnicas são comparados com um modelo denominado “Regra das Misturas" e com resultados da literatura. / In this work, two ultrasonic non destructive techniques were implemented in a water tank and used to determine the elastic constants of glass-epoxy composites samples. The first is the through-transmission technique implemented with a pair of ultrasonic transducers. The second is the back-reflection technique that uses a single transducer in pulse-eco mode. The water acts as a couplant and transfers the mechanical energy from the transducer to the sample. As the transducer is not in direct contact with the sample, we can guarantee a good coupling with the immersion technique. With the system device, it is possible to measure the velocities of the elastic waves in different angles by manually rotating the sample. Due to wave mode conversion phenomenon at the sample-water interface with oblique incidence, ultrasonic immersion testing provides information to calculate the elastic constants of the specimen by measuring longitudinal and shear wave speeds. There are three different modes of waves, one longitudinal and two shear waves, for any given direction of propagation in an anisotropic medium. If the elastic constants of a medium are known, it is possible to obtain the three wave speeds in particular propagations directions by solving the Christoffel equation. Inverting the Christoffel equation, it is possible to obtain the elastic constants from the measured wave speed in several specific directions of the anisotropic material. Measurements were carried out on unidirectional and bidirectional glass-epoxy composite samples, using transducers with central frequency of 0.5 MHz, 1 MHz, and 2.25 MHz. The experimental results obtained with both techniques are compared with a model denominated “Rule of Mixture" estimation and with the literature.

abstract: Being a remarkably versatile and inexpensive building material, concrete has found tremendous use in development of modern infrastructure and is the most widely used material in the world. Extensive research in the field of concrete has led to the development of a wide array of concretes with applications ranging from building of skyscrapers to paving of highways. These varied applications require special cementitious composites which can satisfy the demand for enhanced functionalities such as high strength, high durability and improved thermal characteristics among others. The current study focuses on the fundamental understanding of such functional composites, from their microstructural design to macro-scale application. More specifically, this study investigates three different categories of functional cementitious composites. First, it discusses the differences between cementitious systems containing interground and blended limestone with and without alumina. The interground systems are found to outperform the blended systems due to differential grinding of limestone. A novel approach to deduce the particle size distribution of limestone and cement in the interground systems is proposed. Secondly, the study delves into the realm of ultra-high performance concrete, a novel material which possesses extremely high compressive-, tensile- and flexural-strength and service life as compared to regular concrete. The study presents a novel first principles-based paradigm to design economical ultra-high performance concretes using locally available materials. In the final part, the study addresses the thermal benefits of a novel type of concrete containing phase change materials. A software package was designed to perform numerical simulations to analyze temperature profiles and thermal stresses in concrete structures containing PCMs. The design of these materials is accompanied by material characterization of cementitious binders. This has been accomplished using techniques that involve measurement of heat evolution (isothermal calorimetry), determination and quantification of reaction products (thermo-gravimetric analysis, x-ray diffraction, micro-indentation, scanning electron microscopy, energy-dispersive x-ray spectroscopy) and evaluation of pore-size distribution (mercury intrusion porosimetry). In addition, macro-scale testing has been carried out to determine compression, flexure and durability response. Numerical simulations have been carried out to understand hydration of cementitious composites, determine optimum particle packing and determine the thermal performance of these composites. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2018

Water pollution is a major concern in vast countries such as India and other developing nations. Several methods of water purification have been practiced since many decades, Semiconductor photocatalysis is a promising technique, for photodegradation of various hazardous chemicals that are encountered in waste waters. The great significance of this technique is that, it can degrade (detoxify) various complex organic chemicals, which has not been addressed by several other methods of purification. This unique advantage made this field of research to attract many investigators particularly in latter eighties and after. This thesis incorporates the studies on the various semiconductor photocatalysts that have been employed for the detoxification purposes. The fundamental principles involved in the photoelectrochemistry, reactions at the interface (solid - liquid or solid - gas) and photocatalytic reactions on fine particles are briefed. General nature and size quantization in semiconductor particles, photocatalytically active semiconductors, TiCh and ABO3 systems, chemical systems and modifications for solar energy conversions are brought out in the introduction chapter besides giving brief description about photocatalytic mineralization of water pollutants with mechanism involved, formation of reactive species and the factors influencing photomineralization reactions. Scope of the present work is given at the end of the first chapter. Second chapter deals with the materials used for the preparation of photocatalyst, preparative techniques, methods of analysis, instruments employed for the photodegradation experiments and a brief description of material characterization methods such as X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential thermal analysis, optical absorption spectro photometry, Electron paramagnetic resonance (EPR), and gas chromatograph - mass spectroscopy (GC - MS). Various preparative routes such as wet chemical and hydrothermal methods for obtaining TiO2 (both rutile and anatase forms), BaTiOs and SrTiO3 fine particles and the chemical analysis of their constituents have been described in brief. Third chapter presents the results of materials characterization. T1O2 (rutile and anatase), BaTiO3 and SrTiO3 have been characterized separately using various techniques. Different routes of obtaining the photocatalyst fine particles, heat treatment at various temperature ranges, experimental procedures and the results of characterization are brought out in this chapter. Fourth and fifth chapters present the details of degradation studies carried out on the photomineralization of chlorophenol, trichloroethylene and formaldehyde. Studies include photodegradation of the pollutants with different catalysts varying experimental conditions to check the effects of change in concentration of pollutants, oxidizer, pH, surface hydroxylation, etc. The most favorable conditions for the complete mineralization of the pollutants have been studied. In case of TiO2, anatase form has shown greater photoactivity when compared to rutile and complete mineralization of chlorophenols has been achieved at low pollutant concentrations, neutral pH, with H2O2 and UV illumination. Retarding effects of surface hydroxylation and the formation of peroxotitanium species during photodegradation have been presented. TCE and HCHO degradation with BaTiO3/SrTiO3 has been studied. Photocatalyst heat-treated at 1100°G-1300°C is found to be highly active in combination with H2O2 as electron scavenger. HCHO is not getting degraded to its completeness in aqueous conditions owing to the strong competition in surface adsorption posed by H2O molecules. Vapour-solid phase reaction however gave good results in the detoxification of HCHO via disproportionation. Summary and conclusions are given at the end of the thesis.

In this thesis the magnetic properties of novel amorphous magnetic materials grown on a flexible substrate of polyethylene naphthalate and a silicon wafer have been analyzed and characterized. The analyzed films are two films of amorphous Cobalt-Iron-Zirconium(Co36Fe53Zr11 & Co37Fe55Zr8) grown on the flexible substrate and two films of amorphous (Fe89Zr11) doped with boron (B). The B is implanted in a lattice of rings with inner diameter of 10 μm and outer diameter of 20 μm and with the distance between the center of the rings of either 50 μm or 25 μm. The composition in the doped region is Fe80Zr10B10. Various magneto-optical Kerr effect(MOKE) magnetometers are used to measure hysteresis loops of the samples and a superconducting quantum interference device (SQUID) is used to find the volume magnetization of the flexible samples. To measure the anisotropy in the flexible films a series of sample holders has been developed to measure various amount of stress using the same sample in magneto-optical magnetometers. The stress induced uniaxial anisotropy is found by measuring hysteresis loops of the flexible samples while bending them with different curvatures. The induced anisotropy is related to the magnetostriction and the magnetostriction constants is estimated for the two flexible samples by assuming values for Young’s modulus and Poisson’s ratio. The estimated values for the magnetostriction constant are found to vary with the amount of Zr and to be in the correct order of magnitude for magnetic films. The implanted B rings with the short distance of 25 μm between the center showed to have some interaction between the rings. This conclusion is drawn after analyzing first order reversal curves of the samples and looking at the domains under a MOKE-microscope. At very low temperatures the (unimplanted) FeZr matrix is ferromagnetic and seem to have an anti-ferromagnetic coupling with the B rings. At room temperature the rings are still ferromagnetic and they couple to each other.

Este trabalho apresenta duas técnicas de ensaios não-destrutivos por ultra-som realizados em um tanque com água para determinar as constantes elásticas de materiais compostos de fibra de vidro/epóxi. A primeira técnica é a transmissão direta utilizando um par de transdutores. A segunda é a técnica de pulso-eco, utilizando um único transdutor. A água do tanque atua como um acoplante para transferir a energia mecânica do transdutor para a amostra. Como o transdutor não fica em contato direto com a amostra, pode-se garantir um acoplamento constante. O sistema de medição dota de um dispositivo que permite medir a velocidade da onda elástica sob diferentes ângulos de incidência, através da rotação manual da amostra. Devido ao fenômeno de conversão de modos com incidência oblíqua na interface amostra-água, ensaios por ultra-som em tanques com água fornecem as informações necessárias para o cálculo das constantes elásticas em amostras de materiais anisotrópicos, numa dada direção, a partir das medições das velocidades longitudinal e de cisalhamento. Numa dada direção de propagação em um meio anisotrópico, existem três ondas elásticas distintas: uma longitudinal e duas de cisalhamento. Se as constantes elásticas do material são conhecidas, é possível obter as três velocidades em uma dada direção bastando resolver a equação de Christoffel. Invertendo a equação de Christoffel, obtém-se as constantes elásticas a partir das velocidades medidas em uma dada direção. Os experimentos são realizados com amostras de fibra de vidro/epóxi unidirecionais e bidirecionais, utilizando transdutores com freqüências de 0,5 MHz, 1 MHz e 2,25 MHz. Os resultados experimentais obtidos utilizando ambas as técnicas são comparados com um modelo denominado “Regra das Misturas” e com resultados da literatura. / In this work, two ultrasonic non destructive techniques were implemented in a water tank and used to determine the elastic constants of glass-epoxy composites samples. The first is the through-transmission technique implemented with a pair of ultrasonic transducers. The second is the back-reflection technique that uses a single transducer in pulse-eco mode. The water acts as a couplant and transfers the mechanical energy from the transducer to the sample. As the transducer is not in direct contact with the sample, we can guarantee a good coupling with the immersion technique. With the system device, it is possible to measure the velocities of the elastic waves in different angles by manually rotating the sample. Due to wave mode conversion phenomenon at the sample-water interface with oblique incidence, ultrasonic immersion testing provides information to calculate the elastic constants of the specimen by measuring longitudinal and shear wave speeds. There are three different modes of waves, one longitudinal and two shear waves, for any given direction of propagation in an anisotropic medium. If the elastic constants of a medium are known, it is possible to obtain the three wave speeds in particular propagations directions by solving the Christoffel equation. Inverting the Christoffel equation, it is possible to obtain the elastic constants from the measured wave speed in several specific directions of the anisotropic material. Measurements were carried out on unidirectional and bidirectional glass-epoxy composite samples, using transducers with central frequency of 0.5 MHz, 1 MHz, and 2.25 MHz. The experimental results obtained with both techniques are compared with a model denominated “Rule of Mixture” estimation and with the literature.

Orientador: Marco Lucio Bittencourt / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-09T12:36:20Z (GMT). No. of bitstreams: 1 Martins_DanielLeonardo_M.pdf: 3435063 bytes, checksum: 5e1595f9983245a24712a596e4b1f0a1 (MD5) Previous issue date: 2007 / Resumo: Este trabalho apresenta uma metodologia de otimização de forma aplicada a estruturas submetidas a cargas de impacto, de modo a aumentar sua capacidade de absorção de energia de impacto. Para isso, é necessário conhecer as propriedades mecânicas dos materiais empregados em tais estruturas, as quais são obtidas através de uma metodologia de abordagem dupla experimental- otimização. São obtidos os parâmetros ótimos das leis constitutivas de Cowper-Symonds e Johnson-Cook para materiais sensíveis à taxa de deformação que melhor se ajustam aos respectivos dados experimentais. Finalmente, esses parâmetros são utilizados na análise de uma estrutura complexa, a qual tem sua capacidade de absorção de energia de impacto melhorada utilizando a Metodologia de Resposta da Superfície / Abstract: This work presents a shape optimization methodology applied to structures submitted to impact loads in order to improve their crashworthiness. To this end, it is necessary to know the structural material properties, which were obtained using a dual experimental-optimization methodology. Optimum parameters are obtained for the Cowper-Symonds and Johnson-Cook strain rate sensitive constitutive laws which best fit the material experimental data. These parameters were then used in the analysis of a complex structure, which is crashworthy optimized using a Response Surface Methodology / Mestrado / Mecanica dos Sólidos e Projeto Mecanico / Mestre em Engenharia Mecânica

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