Orientador: Massao Ionashiro / Banca: Mario Cilense / Banca: Mercedes de Moraes / Banca: Lázaro Moscardini D'Assunção / Banca: Jeosadaque José de Sene / Resumo: Foram sintetizados os 4-metoxibenzoatos de lantanídeos e ítrio trivalentes e no estado sólido. Esses compostos foram caracterizados e estudados utilizando-se as técnicas de análise elementar, complexometria, difratometria de raios x pelo método do pó, espectroscopia de absorção na região do infravermelho, termogravimetria-análise térmica diferencial simultânea (TG-DTA) e calorimetria exploratória diferencial (DSC). Os resultados permitiram obter informações sobre a estequiometria, desidratação, transformação polimórfica (transição de fase), modo de coordenação, comportamento térmico e decomposição térmica. / Abstract: Solid 4-methoxybenzoates of trivalent lanthanides and yttrium have been synthesized. Elemental analysis, complexometry, X-ray powder diffractometry, infrared spectroscopy, simultaneous thermogravimetry and differential thermal analysis (TG-DTA), and differential scanning calorimetry (DSC) were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, polymorphic transformation (phase transition), coordination mode, thermal behaviour and thermal decomposition of the isolated compounds. / Doutor

Philosophiae Doctor - PhD / Metal matrix composites harness the superior attributes of their individual constituents to form high performance materials that would rather be impossible from monolithic substances. Owing to many possible combinations, a myriad of metal matrix composite systems can be fabricated with a metal (or a metal alloy) as a matrix (continuous) phase and a ceramic as a reinforcement (discontinuous) phase. The current study focuses on two matrices, namely Nickel Aluminide and Austenitic Steel as well as two reinforcements namely, Titanium Carbide and Oxynitrides. NiAl alloys are candidates for high temperature structural materials due to their high melting temperature, low density, good thermal conductivity, and excellent oxidation resistance.

The syntheses and characterization of the palladium complexes [Pd(accp)2] (7), [Pd(acch)2] (8), [Pd(η3-CH2CMeCH2)(accp)] (11), [Pd(η3-CH2CMeCH2)(acch)] (12), [Pd(η3-CH2CtBuCH2)(accp)] (13) and [Pd(η3-CH2CtBuCH2)(acch)] (14) (accp = 2-acetylcyclopentanoate; acch = 2-acetylcyclohexanoate) are reported. These complexes are available by the reaction of Haccp (2-acetylcyclopentanone) and Hacch (2-acetylcyclohexanone) with Na2[Pd2Cl6] forming 7 and 8 or with [(Pd(η3-CH2CRCH2)(μ-Cl))2] (9, R = Me; 10, R = tBu) forming 11–14. The molecular structures of 7, 8 and 14 are discussed. Complexes 7 and 8 consist of a square-planar coordinated Pd atom with two trans-positioned bidentate β-diketonate ligands. The asymmetric unit of 14 exhibits one molecule of the palladium complex and a half molecule of water. The thermal behavior of 7, 8 and 11–14 and their vapor pressure data were investigated to show, if the appropriate complexes are suited as CVD precursors for palladium layer formation. Thermogravimetric studies showed the evaporation of the complexes at atmospheric pressure upon heating. The vapor pressure of 7, 8 and 11–14 was measured by using thermogravimetric analysis, giving vapor pressure values ranging from 0.62 to 2.22 mbar at 80 °C. Chemical vapor deposition studies were carried out applying a vertical cold wall CVD reactor. Either oxygen or forming gas (N2/H2, ratio 90/10, v/v) was used as reactive gas. Substrate temperatures of 350 and 380 °C were utilized. With 11–14 dense and conformal as well as particulate palladium films were obtained, as directed by SEM studies, whereas 7 and 8 failed to give thin films, which is probably attributed to their high thermal stability in the gas phase. For all deposited layers, XPS measurements confirmed the partial oxidation of palladium to palladium(II) oxide at 380 °C, when oxygen was used as reactive gas. In contrast, thin layers of solely metallic palladium were obtained utilizing forming gas during the deposition experiments. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Os meios confinados restringirem o grau de liberdade dos reagentes e podem afetar significativamente seus estados energéticos e perfis de coordenada de reação. Macrociclos são muito utilizados nessa perspectiva graças a capacidade de hospedar moléculas em suas cavidades e modificar o momento de dipolo das mesmas. Isso permite que estes cavitandos sejam usados como catalisadores, sensores ou simples carreadores, por exemplo. A bambus[6]urila (BU[6]), sintetizada recentemente, ganhou atenção graças à sua capacidade de formar caviplexos estáveis com ânions. Os reagentes de partida são glioxal e ureia, compostos relativamente baratos e comuns, mas a rota síntetica descrita na literatura, no entanto, não contém uma série de informações importantes, o que dificulta a síntese da BU[6]. Muitos estudos computacionais foram realizados para prever e entender as interações deste macrociclo com outras moléculas. No entanto, informações relevantes sobre a BU[6] como a estabilidade térmica, capacidade de complexar cátions ou solubilidade em soluções salinas e solventes comuns, ainda não foram publicados. Nesse trabalho foram determinadas as propriedades fundamentais (densidade, condutividade elétrica e pH de solução saturada, ponto de fusão) da BU[6] vazia e de seu caviplexo BU[6]HCl, bem como a estabilidade térmica das mesmas por meio de análises termogravimétricas. Além disso, tentamos reduzir o tempo de síntese BU[6]HCl utilizando ultrassom e os produtos obtidos foram analisados por técnicas espectrométricas e espectroscópicas. A solubilidade da BU[6]HCl foi estudada utilizando diversos solventes, soluções salinas de metais alcalinos e alcalino-terrosos e meios com diferente acidez. Titulações condutimétricas de soluções de BU[6]HCl com soluções salinas de metais alcalinos e alcalino-terrosos foram realizadas para avaliar a interação entre a BU[6] e os cátions. Por fim, foram realizados experimentos para avaliar a interação dos gases bromo e iodo com as BU[6] vazia e BU[6]HCl, em estado sólido, e os produtos obtidos submetidos à analises espectroscópicas e espectrométricas. / Confined media restrain degrees of freedom and can affect considerably their energetic states and reaction coordinate profiles. Macrocycles are widely used for such purpose thanks to their capacity to include molecules in their cavities, changing their eletric dipole moments. This is why they can be used as calalyst, sensors or simple carriers for example. Bambus[6]uril (BU[6]), recently synthesized, has drawn attention due to its ability to form stable caviplexs with anions. The starting reagents are glyoxal and urea, two afordable and common compounds, but the synthetic route described in the literature however, lacks many important information make it difficult to prepare BU[6]. Many computer calculations were done to preview and understand the interactions between this macrocycle and other molecules. However, relevantly informations about BU[6], such as thermal stability, its ability to complex cations or its solubility in salt solutions and common solvents were not published yet. In this work the fundamental properties (density, pH and conduvity of saturated solution, melting point) of empty BU[6] and BU[6]HCl has been determined, as well the thermal behaviour of the compounds by thermogravimetric analysis. Beyond that, we have attempted to reduce BU[6]HCl synthesis time using ultrasound and the obtained products were analyzed by spectrometric and spectroscopic techniques. The solubility of BU[6]HCl has been studied with diversal solvents, alkaline and alkaline earth metals saline solutions and different acidity media. Condutimetric titrations of BU[6]HCl with alkaline and alkaline earth metals saline solutions were realized to evaluate the interaction of BU[6] and cations. Lastly, experiments to evaluate the interaction between the gases bromine and iodine with empty BU[6] and BU[6]HCl, in solid state, were realized and the obtained products submitted to spectroscopic and spectrometric analysis.

This research investigation examines the thermal behaviour of single and arrays of fluid jets impinging at heated surfaces, and formulates enhancement schemes for the jet impingement heat transfer processes for high-intensity cooling applications. The proposed techniques are numerically modelled and analysed over a wide parametric range to identify flow characteristics leading to thermal enhancement and optimum performance. The first scheme applies to a single fluid jet and incorporates a protruding object at the impingement surface to improve heat transfer. In this, a conical protrusion of high thermal conductivity is attached to the heated surface directly beneath the jet. Three different aspect ratios of 0.5, 1 and 2 are investigated for the protrusion while the inclusion of a fillet at the base of the cone is also studied. Jet Reynolds numbers between 100 and 30,000 are modelled. The observed thermal performance is compared with a reference case having no surface attachment. With this arrangement, the heat transfer rate typically varies between 10 and 40 percent above the reference case although depending on certain parametric combinations, the heat transfer may increase above or decrease below the reference performance. The highest indicated increase in heat transfer is about 90 percent while 15 percent below is the lowest. Careful selection of cone surface profile creates potential for further thermal enhancement. / The second scheme applies to a single fluid jet and incorporates a recess in the impingement surface to improve heat transfer. In this, a cylindrical cavity is introduced to the surface beneath the jet into which the fluid jet impinges. The effects of the cavity on heat transfer are examined for a number of different cavity diameters, cavity depths and jet discharge heights wherein a surface without a cavity is taken as the reference surface. Cavity diameters of 2, 3 and 4 times the jet diameter are investigated at cavity depths between zero and 4 times the jet diameter. Jet discharge heights range between 2 jet diameters above the reference surface to 2 jet diameters below the reference surface. The jet Reynolds number is varied between 100 and 30,000. With this enhancement technique, increases in heat transfer rates of up to 45 percent are observed when compared to the reference performance. The thermal performance of fluid jet arrays is examined by altering square or hexagonal array configurations to identify flow characteristics leading to optimal heat transfer rates. For this, the jet to jet spacing is varied between 1.5 and 7 times the jet diameter while the jet to surface height is varied between 2 and 6 times the jet diameter. Jet Reynolds numbers between 100 and 30,000 are investigated. For each configuration, a critical jet-to-jet spacing is identified below which the heat transfer is observed to reduce significantly. Correlations for the expected heat transfer for a square or hexagonal array are presented in terms of the jet to jet spacing, jet height and jet Reynolds number.

Made available in DSpace on 2014-06-11T19:29:05Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-01-18Bitstream added on 2014-06-13T19:17:16Z : No. of bitstreams: 1 caires_fj_me_araiq.pdf: 493700 bytes, checksum: 3407a17ff8fb345606e061ffb146a15f (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Esse trabalho descreve a síntese e caracterização dos succinatos de metais de transição bivalentes, MC2H4C2O4·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), no estado sólido. Inicialmente prepararam-se os carbonatos dos respectivos íons metálicos adicionando-se lentamente e sob agitação solução saturada de hidrogeno carbonato de sódio à solução de cloreto (Mn, Co, Ni, Zn) ou sulfato (Fe, Cu), até precipitação completa dos íons metálicos. Os succinatos foram obtidos fazendo-se reagir os carbonatos dos íons metálicos com solução de ácido succínico. Os compostos sintetizados foram estudados empregando termogravimetria e análise térmica diferencial simultânea (TG-DTA), termogravimetria derivada (DTG), calorimetria exploratória diferencial (DSC), difratometria de raios X pelo método do pó, espectroscopia no infravermelho, termogravimetria acoplada à espectroscopia de absorção na região do infravermelho com transformada de Fourier (TG-FTIR) e complexometria. Os resultados forneceram informações sobre o comportamento térmico, cristalinidade, modos de coordenação etc. Também foi possível identificar os produtos liberados durante o aquecimento. Os resíduos finais foram Mn3O4, Fe2O3, Co3O4, NiO, CuO e ZnO / In this work, the synthesis and characterization of bivalent transition metal ion succinates in the solid state, MC2H4C2O4·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), are described. Firstly, the respective metal ion carbonates were prepared by slow addition of sodium hydrogen carbonate saturate solution to the chloride (Mn, Co, Ni, Zn) or sulphate (Fe, Cu) solution under continuous magnetic stirring until complete precipitation of the metal ions. The succinates were obtained by reacting carbonate of the metal ions with succinic acid solution. The synthesized compounds were characterized by simultaneous thermogravimetry and differential thermal analysis (TGDTA), Thermogravimetry derivative (DTG), differential scanning calorimetry (DSC), Xray powder diffractometry, infrared spectroscopy, thermogravimetry coupled to absorption spectroscopy in the region of infrared with Fourier transform (TG-FTIR) and complexometry. The results provided information about the thermal behavior, crystallinity, modes of coordination etc. It was also possible to identify the products evolved during heating. The final residues were Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO

Os meios confinados restringirem o grau de liberdade dos reagentes e podem afetar significativamente seus estados energéticos e perfis de coordenada de reação. Macrociclos são muito utilizados nessa perspectiva graças a capacidade de hospedar moléculas em suas cavidades e modificar o momento de dipolo das mesmas. Isso permite que estes cavitandos sejam usados como catalisadores, sensores ou simples carreadores, por exemplo. A bambus[6]urila (BU[6]), sintetizada recentemente, ganhou atenção graças à sua capacidade de formar caviplexos estáveis com ânions. Os reagentes de partida são glioxal e ureia, compostos relativamente baratos e comuns, mas a rota síntetica descrita na literatura, no entanto, não contém uma série de informações importantes, o que dificulta a síntese da BU[6]. Muitos estudos computacionais foram realizados para prever e entender as interações deste macrociclo com outras moléculas. No entanto, informações relevantes sobre a BU[6] como a estabilidade térmica, capacidade de complexar cátions ou solubilidade em soluções salinas e solventes comuns, ainda não foram publicados. Nesse trabalho foram determinadas as propriedades fundamentais (densidade, condutividade elétrica e pH de solução saturada, ponto de fusão) da BU[6] vazia e de seu caviplexo BU[6]HCl, bem como a estabilidade térmica das mesmas por meio de análises termogravimétricas. Além disso, tentamos reduzir o tempo de síntese BU[6]HCl utilizando ultrassom e os produtos obtidos foram analisados por técnicas espectrométricas e espectroscópicas. A solubilidade da BU[6]HCl foi estudada utilizando diversos solventes, soluções salinas de metais alcalinos e alcalino-terrosos e meios com diferente acidez. Titulações condutimétricas de soluções de BU[6]HCl com soluções salinas de metais alcalinos e alcalino-terrosos foram realizadas para avaliar a interação entre a BU[6] e os cátions. Por fim, foram realizados experimentos para avaliar a interação dos gases bromo e iodo com as BU[6] vazia e BU[6]HCl, em estado sólido, e os produtos obtidos submetidos à analises espectroscópicas e espectrométricas. / Confined media restrain degrees of freedom and can affect considerably their energetic states and reaction coordinate profiles. Macrocycles are widely used for such purpose thanks to their capacity to include molecules in their cavities, changing their eletric dipole moments. This is why they can be used as calalyst, sensors or simple carriers for example. Bambus[6]uril (BU[6]), recently synthesized, has drawn attention due to its ability to form stable caviplexs with anions. The starting reagents are glyoxal and urea, two afordable and common compounds, but the synthetic route described in the literature however, lacks many important information make it difficult to prepare BU[6]. Many computer calculations were done to preview and understand the interactions between this macrocycle and other molecules. However, relevantly informations about BU[6], such as thermal stability, its ability to complex cations or its solubility in salt solutions and common solvents were not published yet. In this work the fundamental properties (density, pH and conduvity of saturated solution, melting point) of empty BU[6] and BU[6]HCl has been determined, as well the thermal behaviour of the compounds by thermogravimetric analysis. Beyond that, we have attempted to reduce BU[6]HCl synthesis time using ultrasound and the obtained products were analyzed by spectrometric and spectroscopic techniques. The solubility of BU[6]HCl has been studied with diversal solvents, alkaline and alkaline earth metals saline solutions and different acidity media. Condutimetric titrations of BU[6]HCl with alkaline and alkaline earth metals saline solutions were realized to evaluate the interaction of BU[6] and cations. Lastly, experiments to evaluate the interaction between the gases bromine and iodine with empty BU[6] and BU[6]HCl, in solid state, were realized and the obtained products submitted to spectroscopic and spectrometric analysis.

The development of lightweight concretes has made a contribution to advances in structural design. It would be useful to further improve the mechanical properties of lightweight concrete formulations whilst enhancing their resistance to fire degradation and reduced thermal conductivity. Improving the sustainability of any new proposed lightweight concrete formulation is desirable, for example by the inclusion of waste stream components into the formulation.This thesis describes an investigation of the mechanical, thermal and fire resistance properties of a new type of expanded clay lightweight concrete formulation in which varying quantities of sand are replaced by crushed glass aggregate, in conjunction with the addition of metakaolin (which may be available as a waste component from the manufacture of paper) as a partial replacement for the cement. The investigation involved short and long-term laboratory testing of a range of mechanical and thermal properties of individual concrete formulations and small scale structural elements consisting of masonry blocks made from these formulations (so called wallettes). An extensive programme of Finite Element Analysis using Abaqus was also performed.The results obtained show that it is possible to produce a structural expanded clay lightweight concrete that possesses good thermal properties by incorporating of ground glass and metakaolin. Compressive and splitting tensile strengths, as well as the modulus of elasticity, increased with an increase in the metakaolin content, while concrete density decreased. Reductions in thermal conductivity and improvements in fire resistance criteria were also observed in comparison with conventional lightweight concrete mixtures. For example, measured thermal conductivity values ranged from 0.092 W/m.K to 0.177 W/m.K, and the insulation criterion (an indicator of resistance to fire) reached up to 110 minutes for a concrete member with a thickness of 29 mm. The highest resistance to the effects of high temperatures was observed for concrete mixes containing either 15% or 30% recycled glass with 10% metakaolin.The maximum axial loads at failure were 474 kN and 558 kN for reference and modified wallettes respectively, implying corresponding bearing capacities of 7.1 MPa and 8.3 MPa. The critical path of the failure mode was similar for all of the wallettes tested and normally began underneath the load point, then passed through the concrete blocks and head joint to reach the toe of the wallette. The masonry wallettes formulated using reference lightweight concrete blocks exhibited failure due to explosive spalling at 400 oC with no applied mechanical load, whereas the second type of masonry wallettes (the modified wallettes) did not show such behaviour.The results of Finite Element Analysis showed that the coefficient of thermal convection had the most influence upon the insulation criterion. From a structural perspective, the key parameters were the value of penalty stiffness and imperfections in wallette construction. In general, a close agreement between the measured and simulated results was observed for both the thermal and structural finite element models at ambient and high temperatures.

Orientador: Massao Ionashiro / Banca: João Olímpio Tognolli / Banca: Eder Tadeu Gomes Cavalheiro / Resumo: Esse trabalho descreve a síntese e caracterização dos succinatos de metais de transição bivalentes, MC2H4C2O4·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), no estado sólido. Inicialmente prepararam-se os carbonatos dos respectivos íons metálicos adicionando-se lentamente e sob agitação solução saturada de hidrogeno carbonato de sódio à solução de cloreto (Mn, Co, Ni, Zn) ou sulfato (Fe, Cu), até precipitação completa dos íons metálicos. Os succinatos foram obtidos fazendo-se reagir os carbonatos dos íons metálicos com solução de ácido succínico. Os compostos sintetizados foram estudados empregando termogravimetria e análise térmica diferencial simultânea (TG-DTA), termogravimetria derivada (DTG), calorimetria exploratória diferencial (DSC), difratometria de raios X pelo método do pó, espectroscopia no infravermelho, termogravimetria acoplada à espectroscopia de absorção na região do infravermelho com transformada de Fourier (TG-FTIR) e complexometria. Os resultados forneceram informações sobre o comportamento térmico, cristalinidade, modos de coordenação etc. Também foi possível identificar os produtos liberados durante o aquecimento. Os resíduos finais foram Mn3O4, Fe2O3, Co3O4, NiO, CuO e ZnO / Abstract: In this work, the synthesis and characterization of bivalent transition metal ion succinates in the solid state, MC2H4C2O4·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), are described. Firstly, the respective metal ion carbonates were prepared by slow addition of sodium hydrogen carbonate saturate solution to the chloride (Mn, Co, Ni, Zn) or sulphate (Fe, Cu) solution under continuous magnetic stirring until complete precipitation of the metal ions. The succinates were obtained by reacting carbonate of the metal ions with succinic acid solution. The synthesized compounds were characterized by simultaneous thermogravimetry and differential thermal analysis (TGDTA), Thermogravimetry derivative (DTG), differential scanning calorimetry (DSC), Xray powder diffractometry, infrared spectroscopy, thermogravimetry coupled to absorption spectroscopy in the region of infrared with Fourier transform (TG-FTIR) and complexometry. The results provided information about the thermal behavior, crystallinity, modes of coordination etc. It was also possible to identify the products evolved during heating. The final residues were Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO / Mestre

Made available in DSpace on 2017-07-21T18:53:09Z (GMT). No. of bitstreams: 1 SIMONE CRISTINE WOSNIACKI BICUDO.pdf: 856559 bytes, checksum: d069ed257c254bc2a62e80ada3a1d5a0 (MD5) Previous issue date: 2008-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Starch is a very imp ortant polysaccharide for food processing. It is extracted from different sources and presents very important particular thermal characteristics. The most important temperature for food industry applications is the gelatinization, investigated in this work by techniques of thermal analysis, Differential Scanning Calorimetry (DSC), in various native starches. The thermal behaviour of starch granules was investigated by Thermogravimetry (TG), Differential Thermogravimetry (DTG) and Differential Thermal Analysis (DTA). Also the amylose content was measured for characterization of the native starches. The native starch that presented the lowest gelatinization temperature was the pinhão seed, with peak temperature of 50.8ºC, whereas the lowest amylose content, among non waxy starches, was of banana, with apparent amylose content of 8.1% and total amylose of 9.0%. / O amido é um carboidrato muito importante para o processamento dos alimentos. Está presente em diferentes fontes e apresenta características térmicas também variadas. O intervalo de temperatura de maior importância para a indústria é a de gelatinização, investigada neste trabalho através da técnica de análise térmica, Calorimetria Exploratória Diferencial (DSC), em diversos amidos nativos. Como muitos fatores influenciam o processamento dos alimentos, outras análises foram feitas para auxiliar na obtenção de informações para caracterizar diferentes amidos nativos, como Termogravimetria (TG) Termogravimetria Derivada (DTG) e Análise Térmica Diferencial (DTA), para investigar a degradação térmica dos grânulos de amido e os teores de amilose. O amido nativo que apresentou as menores temperaturas de gelatinização foi o de pinhão, com temperatura de pico de 50,8ºC enquanto que, os menores teores de amilose apresentados, dentre os amidos nativos não cerosos, foi o de banana, com amilose aparente de 8,1% e amilose total de 9,0%.