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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
21

HYDROGEN GENERATION FROM HYDROUS HYDRAZINE DECOMPOSITION OVER SOLUTION COMBUSTION SYNTHESIZED NICKEL-BASED CATALYSTS

Wooram Kang (6997700) 14 August 2019 (has links)
<div>Hydrous hydrazine (N<sub>2</sub>H<sub>4</sub>·H<sub>2</sub>O) is a promising hydrogen carrier for convenient storage and transportation owing to its high hydrogen content (8.0 wt%), low material cost and stable liquid state at ambient temperature. Particularly, generation of only nitrogen as byproduct, in addition to hydrogen, thus obviating the need for on-board collection system for recycling, ability to generate hydrogen at moderate temperatures (20-80 °C) which correspond to the operating temperature of a proton exchange membrane fuel cell (PEMFC), and easy recharging using current infrastructure of liquid fuels make hydrous hydrazine a promising hydrogen source for fuel cell electric vehicles (FCEVs). Since hydrogen can be generated from catalytic hydrazine decomposition, the development of active, selective and cost-effective catalysts, which enhance the complete decomposition (N<sub>2</sub>H<sub>4</sub> → N<sub>2</sub>+2H<sub>2</sub>) and simultaneously suppress the incomplete decomposition (3N<sub>2</sub>H<sub>4</sub> → 4NH<sub>3</sub>+N<sub>2</sub>), remains a significant challenge.</div><div>In this dissertation, CeO<sub>2</sub> powders and various Ni-based catalysts for hydrous hydrazine decomposition were prepared using solution combustion synthesis (SCS) technique and investigated. SCS is a widely employed technique to synthesize nanoscale materials such as oxides, metals, alloys and sulfides, owing to its simplicity, low cost of precursors, energy- and time-efficiency. In addition, product properties can be effectively tailored by adjusting various synthesis parameters which affect the combustion process.</div><div>The first and second parts of this work (Chapters 2 and 3) are devoted to investigating the correlation between the synthesis parameters, combustion characteristics and properties of the resulting powder. A series of CeO<sub>2</sub>, which is a widely used material for various catalytic applications and a promising catalyst support for hydrous hydrazine decomposition, and Ni/CeO<sub>2</sub> nanopowders as model catalysts for the target reaction were synthesized using conventional SCS technique. This demonstrated that crystallite size, surface property and concentration of defects in CeO<sub>2</sub> structure which strongly influence the catalytic performance, can be effectively controlled by varying the synthesis parameters such as metal precursor (oxidizer) type, reducing agent (fuel), fuel-to-oxidizer ratio and amount of gas generating agent. The tailored CeO<sub>2</sub> powder exhibited small CeO<sub>2</sub> crystallite size (7.9 nm) and high surface area (88 m<sup>2</sup>/g), which is the highest value among all prior reported SCS-derived CeO<sub>2</sub> powders. The Ni/CeO<sub>2</sub> catalysts synthesized with 6 wt% Ni loading, hydrous hydrazine fuel and fuel-to-oxidizer ratio of 2 showed 100% selectivity for hydrogen generation and the highest activity (34.0 h<sup>-1</sup> at 50 ºC) among all prior reported catalysts containing Ni alone for hydrous hydrazine decomposition. This superior performance of the Ni/CeO<sub>2</sub> catalyst is attributed to small Ni particle size, large pore size and moderate defect concentration.</div><div>As the next step, SCS technique was used to develop more efficient and cost-effective catalysts for hydrous hydrazine decomposition. In the third part (Chapter 4), noble-metal-free NiCu/CeO<sub>2</sub> catalysts were synthesized and investigated. The characterization results indicated that the addition of Cu to Ni/CeO<sub>2</sub> exhibits a synergistic effect to generate significant amounts of defects in the CeO<sub>2</sub> structure which promotes catalytic activity. The 13 wt% Ni<sub>0.5</sub>Cu<sub>0.5</sub>/CeO<sub>2</sub> catalysts showed 100% H<sub>2</sub> selectivity and 5.4-fold higher activity (112 h<sup>-1</sup> at 50 ºC) as compared to the 13 wt% Ni/CeO<sub>2</sub> (20.7 h<sup>-1</sup>). This performance is also superior to that of most reported non-noble metal catalysts and is even comparable to several noble metal-based catalysts. In the fourth part (Chapter 5), low Pt loading NiPt/CeO<sub>2</sub> catalysts were studied. The modified SCS technique was developed and applied to prepare NiPt/CeO<sub>2</sub> catalysts, that overcomes the typical problem of conventional SCS which leads to deficiency of Pt at catalyst surface due to the diffusion of Pt into bulk CeO<sub>2</sub>. The Ni<sub>0.6</sub>Pt<sub>0.4</sub>/CeO<sub>2</sub> catalysts with 1 wt% Pt loading exhibited high activity (1017 h<sup>-1</sup> at 50 ºC) along with 100% H<sub>2</sub> selectivity owing to the optimum composition of NiPt alloy, high metal dispersion and a large amount of CeO<sub>2</sub> defects. Its activity is higher than most of the reported NiPt-based catalysts which typically contain high Pt loading (3.6-42 wt%).</div><div>Next, the intrinsic kinetics of hydrous hydrazine decomposition over the NiPt/CeO<sub>2</sub> catalysts, which are necessary for efficient design and optimization of the hydrous hydrazine-based hydrogen generator system, were investigated (Chapter 6). From the experimental data obtained at different reaction temperatures, the intrinsic kinetic model based on the Langmuir-Hinshelwood mechanism was established. The developed model</div><div>provides good predictions with the experimental data, especially over a wide range of initial reactant concentration, describing well the variation of reaction order from low to</div><div>high reactant concentration.</div><div>Finally, the conclusions of the dissertation and recommendations for future work are summarized in Chapter 7.</div>
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22

Précarité hydrique et développement local dans la commune urbaine de Téra, Niger / Hydrous precariousness and local development in the urban district of Tera, Niger

Moussa, Yayé 16 January 2018 (has links)
Au Niger, la maîtrise des ressources en eau demeure toujours un défi majeur après plus de 50 ans de politique hydraulique. Les investissements réalisés durant la Décennie Internationale de l’Eau Potable et de l’Assainissement (1981-1990) et les Objectifs du Millénaire pour le Développement (2000-2015) n’ont pas pu couvrir les besoins énormes en eau. Le déficit en infrastructures se pose au niveau de toutes les composantes du secteur de l’hydraulique. Les besoins en eau de plus en plus croissants et l’insuffisance des investissements publics pour y faire face expliquent ce sous-équipement en infrastructures hydrauliques. Au niveau de la commune urbaine de Téra, au-delà de la forte croissance démographique et de l’insuffisance des investissements dans le secteur de l’eau, il faut ajouter les contraintes climatiques et hydrogéologiques dans l’analyse de la situation hydraulique. Dans la ville de Téra, la précarité hydrique est due à un déficit considérable de production d’eau et à un réseau de distribution d’eau inadapté au site de la ville. Ainsi, de décembre à août, les trois quarts de la ville, principalement les quartiers Carré, Résidence, Douane, TP et Guenobon restent sans être desservis en eau. En milieu rural, l’insuffisance des points d’eau, leur localisation par rapport aux villages et le temps de rétention assez court (3 à 4 mois) des plans d’eau entraînent une situation d’extrême précarité hydrique qui bouleverse la vie socio-économique. En ville comme en campagne, en dépit des différences territoriales et des modalités d’accès à l’eau, les populations vivent le même niveau de précarité hydrique et y apportent les mêmes types de solutions. Elles recourent ainsi aux points d’eau traditionnels et développent une solidarité hydraulique à travers la mutualisation des points d’eau entre quartiers, entre villages et entre ville-villages. Mais, avec cette situation hydraulique particulièrement précaire réduisant systématiquement la pratique des activités économiques et la satisfaction des besoins humains fondamentaux, les défis de développement local deviennent de plus en plus lourds pour la commune urbaine de Téra. / In Niger, water resource management remains a major challenge after more than 50 years of water policy. Thus, the investments carried out during the International Decade of Driking Water and Sanitation (1981-1990) and the Millennium Development Goals (2000-2015) could not meet the enormous needs of water. The infrastructure deficit is being faced by all components of the hydraulic sector. The growing demand for water and insufficient public investment to meet it explain this under-equipment in water infrastructure. At the level of the urban district of Tera, in addition to the strong demographic growth and insufficient investments in the water sector, climatic and hydrogeological constraints must be added to the analysis of the hydraulic situation. In the city of Tera, the hydrous precariousness is due to a considerable lack of water production and an inadequate water distribution network at the city site. Thus, from december to august, three-quarters of the city, mainly the Carré, Résidence, Douane, TP and Guenobon neighbourhoods remain underserved. In rural areas, the insufficiency of water supply points, their location in relation to villages to the villages and the rather short time of retention (3 à 4 months) of lakes defines a situation of extreme hydrous precariousness which affects the socio-economic life. In town as in the countryside, despite the territorial differences and water access methods, the populations face the same level of hydrous precariousness and adopt the same types of solutions. Thus, they resort to the traditional water supply points and develop a hydraulic solidarity through the mutualisation of water supply points between districts, villages, villages and city. However, with this particularly precarious hydraulic situation systematically reducing the practice of economic activities and the satisfaction of the fundamental human needs, the challenges of local development become increasingly heavy for the urban district of Tera.
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23

ANÁLISE DE VIABILIDADE DA IRRIGAÇÃO DE PRECISÃO NA CULTURA DO MILHO (Zea mays L.) / ANALYSIS VIABILITY OF THE IRRIGATION OF PRECISION IN THE CULTURE OF THE MAIZE (Zea mays L.)

Soares, Fátima Cibéle 18 January 2010 (has links)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The hydrous availability in the soil, within the same cultivated area, varies on space and time. However, the application of the irrigation lamina is accomplished likewise in the entire irrigate tilth, without taking into account the variance of the physical-hydro characteristics of the soil that influence in its capacity of retention. This present work had as objective the analysis of the variability of physical-hydro characteristics of the soil in the cultivation area, connecting them to the morphologic characteristics of two corn cultivation types (BM 1120 e BM 1115), in an irrigate area with no variation of the irrigation lamina, in order to build up a scenery that allows us to evaluate the viability of the irrigation precision for the cultivation. The experiment was conducted in the experimental area of Technologic Center from Jaguari Valley , in a town called Jaguari, in RS, in an area of 4,35ha, with a sectorial pivot irrigation system of 270º, divided in six sectors of 45º each. Within each sector were made collection points for the characterization of physical and chemical properties of soil. To evaluate the different components of the plant canopy, were collected five whole plants, within each sector, every twenty days. The irrigation was carried out equally across the area through the estimation of crop evapotranspiration by a class "A", also monitored daily to the water content of soil from the dielectric humidity sensors, installed in different sectors. At the end of the cycle were determined components of crop production for estimation of grain production in different sectors. The results were subordinate to an analysis of variation, and the averages were compared to the Tukey test to 5%. Through the generated maps the spatial variability of productivity and the physical-hydro chemical characteristics of the soil were observed. Due to the variability of the area of study, the cultivation of corn presented a variation in the 40 % productivity to the BM 1120 variety and from 56 % in the BM 1115 variety. The S6 sector was the one that presented the greatest hydrous availability to the cultivations, ergo, it showed up in more grain productivity. The cultivated area must be considered, no matter how small it is, in a heterogeneous way, accomplishing the division in sub-areas for the precise application of the irrigation lamina, in order to optimize the use of natural resources and minimize the expenditures. / A disponibilidade hídrica no solo, dentro de uma mesma área cultivada, varia no espaço e no tempo. Entretanto, a aplicação da lâmina de irrigação é realizada igualitariamente em toda a lavoura irrigada, sem levar em conta as variações das características físico-hídricas do solo, que influem em sua capacidade de retenção. O presente trabalho teve por objetivo, analisar a variabilidade das características físico-hídricas do solo, na área de cultivo, relacionando-as com as características morfológicas de duas cultivares de milho (BM 1120 e BM 1115), em área irrigada sem variação de lâmina de irrigação, a fim de construir um cenário que permita avaliar a viabilidade da irrigação de precisão para a cultura. O experimento foi conduzido na área experimental do Centro Tecnológico do Vale do Jaguari, município de Jaguari/RS, em uma área de 4,35ha, com sistema de irrigação do tipo pivô setorial, de 270º, sendo esta dividida em seis setores de 45º cada. Dentro de cada setor foram realizados pontos de coletas, para a caracterização das propriedades físicas e químicas do solo. Para avaliar os diferentes componentes da parte aérea da planta, eram coletadas cinco plantas inteiras, dentro de cada setor, a cada vinte dias. O manejo da irrigação foi realizado igualitariamente em toda a área, através da estimativa da evapotranspiração da cultura pelo tanque classe A , também monitorou-se diariamente o conteúdo de água no solo, através de sensores dielétricos de umidade, instalados nos diferentes setores. No final do ciclo da cultura foram determinados os componentes de produção da cultura, para estimativa da produção de grãos nos diferentes setores. Os resultados foram submetidos a análise da variância, e as médias foram comparadas pelo teste de Tukey a 5%. Através dos resultados observou-se variabilidade espacial da produtividade e das características físico-hídricas e químicas do solo. Devido à variabilidade da área em estudo, a cultura do milho apresentou uma variação na produtividade de 40%, para a variedade BM 1120 e de 56% na variedade BM 1115. O setor S6 foi o que apresentou a maior disponibilidade hídrica às culturas, logo, destacou-se em maior produtividade de grãos. Deve-se considerar a área cultivada, por menor que seja, de forma heterogênea, realizando a divisão em subáreas para a aplicação precisa da lâmina de irrigação, a fim de otimizar o aproveitamento dos recursos naturais e minimizar custos.
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24

Interaction of Metal Oxides with Carbon Monoxide and Nitric Oxide for Gas Sensing Applications

Adeyemo, Adedunni D. 20 June 2012 (has links)
No description available.
25

Preparação e caracterização de compósitos com matriz de poliuretano e híbridos fibrosos modificados com óxido de magnésio hidratado / Preparation and characterization of polyurethane based composites with hybrid fibrous modified by hydrous magnesium oxide

Carvalho, Thaís 02 December 2016 (has links)
A versatilidade das espumas poliuretanas permite sua aplicação em inúmeros setores industriais, devido à possibilidade de se obter diferentes conjuntos de propriedades apenas alterando sua formulação básica. Um tipo recorrente de alteração é a incorporação de diferentes tipos de fibras em matrizes de poliuretano, vastamente estudada com o objetivo de gerar materiais compósitos com melhores propriedades mecânicas do que a matriz original. Inúmeros autores reportaram a utilização de celulose cristalina como uma alternativa renovável aos agentes de reforço e revelaram que a celulose utilizada como aditivo em matrizes poliméricas afetou as propriedades mecânicas da matriz original e, em menor escala, exerceu influência sobre a estabilidade térmica do compósito. O presente trabalho dedicou-se a isolar a celulose cristalina contida nas fibras de bananeira mediante tratamento com ácido acético concentrado. Os tratamentos químicos são necessários para modificar a superfície do material e melhorar a adesão do agente de reforço à matriz. Tendo em vista os resultados associados à estabilidade térmica dos compósitos de poliuretano reforçados com celulose, buscou-se sintetizar materiais híbridos de celulose e MgO.nH2O. Foi observado que, mesmo em pequenas quantidades, a presença do óxido hidratado de magnésio afetou significativamente a estabilidade térmica do HB 98:2. Estudos térmicos indicam que os materiais compósitos estudados apresentaram comportamento semelhante ao da matriz PU. Estudos das propriedades compressivas dos materiais poliméricos gerados mostraram que a incorporação do HB 98:2 ao PU afetou positivamente as propriedades mecânicas do material, sendo que o compósito PU + 1 HB 98:2 apresentou desempenho mecânico superior ao da matriz pura. / The versatility of polyurethanes foams allows its application in numerous industries because of the possibility of obtaining different sets of properties just by changing its basic formulation. A recurrent type of modification is the incorporation of different types of fibers in polyurethane matrices widely studied with the objective of generating composite materials with better mechanical properties than the original matrix. Numerous authors have reported the use of crystalline cellulose as a renewable alternative to fillers and showed that the cellulose used as additive in polymer matrices affect the mechanical properties of the original matrix and, to a lesser extent, influence upon thermal stability of the composite. This work was dedicated to isolate the crystalline cellulose contained in banana fibers by treatment with concentrated acetic acid. The chemical treatments are needed to modify the surface of the material and improve adhesion of the filler to the matrix. In view of the results associated with the thermal stability of the composite polyurethane reinforced with cellulose, sought to synthesize hybrid materials cellulose and MgO.nH2O. It has been observed that even in small quantities, the presence of hydrated magnesium oxide significantly affect the thermal stability of HB 98: 2. thermal studies indicate that the studied composites showed similar behavior to the PU matrix. Studies of the compressive properties of polymeric materials generated showed that the incorporation of HB 98: 2 to PU positively affect the mechanical properties of the material, and the composite PU + HB 98 1: 2 had mechanical performance superior to that of pure matrix.
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26

Fluorine and chlorine fractionation in the sub-arc mantle : an experimental investigation

Dalou, Célia 21 January 2011 (has links) (PDF)
Volatile elements released from the subducting slab play a fundamental role during the formation of arc magmas in the mantle wedge. Advances of melt inclusion studies enlarged the data on volatile abundance in arc magmas, and it is now possible to characterize some volatile contents in arc primary magmas, in particular F and Cl. A recent study of Mt Shasta melt inclusions (LeVoyer et al., 2010) shows that fractionation of F and Cl potentially contains information about arc magma genesis. In order to trace the source of arc magmas, fluorine and chlorine partitioning was investigated. Here, I present new experimental determinations of Cl and F partition coefficients between dry and hydrous silicate melts and mantle minerals: olivine, orthopyroxene, clinopyroxene, plagioclase, garnet and also pargasite and phlogopite. The values were compiled from more than 300 measurements in 24 melting experiments, conducted between 8 and 25 kbars and between 1180 and 1430˚C. The low abundance F, Cl measurements in minerals were done by Cameca IMF 1280 at WHOI using the negative secondary ion mode. The results show that DOpx/meltF ranges from 0.123 to 0.021 and DCpx/meltF ranges from 0.153 to 0.083, while Cl partition coefficient varies from DOpx/meltCl from 0.002 to 0.069 and DCpx/meltCfrom 0.008 to 0.015, as well. Furthermore, DOl/meltF ranges from 0.116 to 0.005 and DOl/meltCl from 0.001 to 0.004; DGrt/meltF ranges from 0.012 to 0.166 and DGrt/meltCl from 0.003 to 0.087 with the increasing water amount and decreasing temperature. I also show that F is compatible in phlogopite DPhl/meltF > 1.2) while DAmp/meltF is incompatible in pargasite DAmp/meltF from 0.36 to 0.63). On the contrary, Cl is more incompatible in phlogopite (DPhl/meltCl > 1.2 on average 0.09 ± 0.02), than in pargasite (DPhl/meltCl from 0.12 to 0.38). This study demonstrates that F and Cl are substituted in specific oxygen site in minerals that lead then to be more sensitive than trace elements to crystal chemistry and water amount variations thus melting conditions. Using those new partition coefficients, I modelled melting of potential sub-arc lithologies with variable quantity aqueous-fluid. This model is able to decipher 1) amount of aqueous-fluid involved in melting, 2) melting induced by fluid or melting of an hydrous mineral-bearing source and 3) melting of either pargasite-bearing lithology or phlogopite-bearing lithology and shows that sources of some primitive melts, for instance from Italy, bear pargasite and phlogopite, while some primitve melts seem to be the results of fluid-induced melts.
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27

Preparação e caracterização de compósitos com matriz de poliuretano e híbridos fibrosos modificados com óxido de magnésio hidratado / Preparation and characterization of polyurethane based composites with hybrid fibrous modified by hydrous magnesium oxide

Thaís Carvalho 02 December 2016 (has links)
A versatilidade das espumas poliuretanas permite sua aplicação em inúmeros setores industriais, devido à possibilidade de se obter diferentes conjuntos de propriedades apenas alterando sua formulação básica. Um tipo recorrente de alteração é a incorporação de diferentes tipos de fibras em matrizes de poliuretano, vastamente estudada com o objetivo de gerar materiais compósitos com melhores propriedades mecânicas do que a matriz original. Inúmeros autores reportaram a utilização de celulose cristalina como uma alternativa renovável aos agentes de reforço e revelaram que a celulose utilizada como aditivo em matrizes poliméricas afetou as propriedades mecânicas da matriz original e, em menor escala, exerceu influência sobre a estabilidade térmica do compósito. O presente trabalho dedicou-se a isolar a celulose cristalina contida nas fibras de bananeira mediante tratamento com ácido acético concentrado. Os tratamentos químicos são necessários para modificar a superfície do material e melhorar a adesão do agente de reforço à matriz. Tendo em vista os resultados associados à estabilidade térmica dos compósitos de poliuretano reforçados com celulose, buscou-se sintetizar materiais híbridos de celulose e MgO.nH2O. Foi observado que, mesmo em pequenas quantidades, a presença do óxido hidratado de magnésio afetou significativamente a estabilidade térmica do HB 98:2. Estudos térmicos indicam que os materiais compósitos estudados apresentaram comportamento semelhante ao da matriz PU. Estudos das propriedades compressivas dos materiais poliméricos gerados mostraram que a incorporação do HB 98:2 ao PU afetou positivamente as propriedades mecânicas do material, sendo que o compósito PU + 1 HB 98:2 apresentou desempenho mecânico superior ao da matriz pura. / The versatility of polyurethanes foams allows its application in numerous industries because of the possibility of obtaining different sets of properties just by changing its basic formulation. A recurrent type of modification is the incorporation of different types of fibers in polyurethane matrices widely studied with the objective of generating composite materials with better mechanical properties than the original matrix. Numerous authors have reported the use of crystalline cellulose as a renewable alternative to fillers and showed that the cellulose used as additive in polymer matrices affect the mechanical properties of the original matrix and, to a lesser extent, influence upon thermal stability of the composite. This work was dedicated to isolate the crystalline cellulose contained in banana fibers by treatment with concentrated acetic acid. The chemical treatments are needed to modify the surface of the material and improve adhesion of the filler to the matrix. In view of the results associated with the thermal stability of the composite polyurethane reinforced with cellulose, sought to synthesize hybrid materials cellulose and MgO.nH2O. It has been observed that even in small quantities, the presence of hydrated magnesium oxide significantly affect the thermal stability of HB 98: 2. thermal studies indicate that the studied composites showed similar behavior to the PU matrix. Studies of the compressive properties of polymeric materials generated showed that the incorporation of HB 98: 2 to PU positively affect the mechanical properties of the material, and the composite PU + HB 98 1: 2 had mechanical performance superior to that of pure matrix.
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28

Etude des propriétés physico-chimiques des magmas hydratés par dynamique moléculaire / Study of the physico-chemical properties of hydrous magmatic melts by molecular dynamics simulations

Dufils, Thomas 19 September 2017 (has links)
Dans ce manuscrit, nous nous sommes intéressés aux propriétés des magmas ainsi qu’aux effets de l’eau sur celles-ci en utilisant la dynamique moléculaire classique. Après avoir mis en avant l’importance de l’eau dans les phénomènes géologiques et présenté quelques bases de dynamique moléculaire, nous présentons un champ de force pour les liquides silicatés anhydres. Nous utilisons ce champ de force pour étudier l’équation d’état, la structure et les propriétés de transport (viscosité, conductivité électrique, coefficient de diffusion) de liquides silicatés de composition aussi bien terrestre qu’extra-terrestre. Ces résultats sont systématiquement comparés avec les données de la littérature. Nous développons ensuite un champ de force pour l’eau pure compatible avec celui proposé pour les silicates. La validité de ce champ de force est étudiée par comparaison avec des résultats expérimentaux, de simulations ab-initio et d’autre champs de force classiques. Nous ajoutons enfin une interaction eau-silicate aux deux champs de forces précédents pour obtenir un champ de force décrivant les silicates hydratés. Celui-ci est utilisé pour étudier les propriétés des mélanges eau-silicate (solubilité, tension de surface). La structure et les propriétés des silicates hydratés sont ensuite étudiées, notamment la spéciation de l’eau, la densité, la viscosité, la conductivité électrique et les coefficients de diffusion. La structure locale autour des espèces protonées (OH-,H2O et H3O+) et leurs coefficients de diffusion sont également déterminés. Ces différents résultats sont là encore comparés aux données existantes dans la littérature. / In this manuscript, we focused on the properties of magmas and the effects of water on these properties using classical molecular dynamics simulations. After having pointed out the importance of water in geological processes and presented some basic principles of molecular dynamics simulations, we present a force field for dry silicate melts. We use this force field to study the equation of state, the structure and the transport properties (viscosity, electrical conductivity, diffusion coefficient) of silicate melts of terrestrial and extra-terrestrial compositions. These results are systematically compared with data of the literature. We then develop a force field for pure water compatible to the one proposed for silicates. The validity of this force field is investigated by comparison with experimental studies, ab-initio simulations and other MD simulations using classical force fields. At last we add a water-silicate interaction to the two former force fields in order to describe hydrous silicate melts. This force field is used to study the properties of water-silicate mixtures (solubility, surface tension). The structure and properties of hydrous silicate melts are evaluated as well as the speciation of water, the density, the viscosity, the electrical conductivity and the diffusion coefficients. The local structure around protonated species (OH-,H2O and H3O+) and their diffusion coefficients are also determined. All these results are compared with available data of the literature.
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29

[en] DESIGN OF EXPERIMENTS FOR METROLOGICAL OPTIMIZATION AND RELIABILITY OF A NEW PH MEASUREMENT SYSTEM IN HYDRATED FUEL ETHANOL / [pt] PLANEJAMENTO DE EXPERIMENTOS PARA OTIMIZAÇÃO E CONFIABILIDADE METROLÓGICA DE UM NOVO SISTEMA DE MEDIÇÃO DE PH EM ETANOL HIDRATADO COMBUSTÍVEL

NATALIA CAMBIAGHI ATILIO 08 November 2022 (has links)
[pt] O pH constitui um dos parâmetros de controle de qualidade do etanol combustível, sendo estabelecido pela norma brasileira ABNT NBR 10891, cujo escopo é específico para etanol hidratado combustível, e pela norma americana ASTM D 6423, a qual o foco é o etanol anidro combustível. Neste contexto, o presente estudo apresenta uma análise crítica à composição dos eletrodos utilizados pelos diferentes sistemas de medições para pH de etanol, devido à presença de água na composição do eletrodo de vidro. Com isso, o objetivo do presente estudo consistiu em uma proposta de um novo sistema para medição de pH de etanol hidratado combustível, o qual foi o único solvente utilizado, empregando como referência indicadores ácido-base. Por meio do planejamento de experimentos Box-Behnken foi possível determinar a condição otimizada esperada para o novo sistema de medição, o qual foi comparado com os sistemas propostos pelos referenciais normativos e posteriormente com o intervalo de pH definido pelos indicadores. Os resultados revelaram que os valores de pH obtidos pelos diferentes sistemas utilizados, incluindo o proposto pelo presente estudo, são estatisticamente diferentes entre si, e que somente os valores obtidos pelo novo sistema de medição se adequa à faixa de pH encontrada pelos indicadores. O eletrodo otimizado apresentou uma sensibilidade de resposta adequada à equação de Nernst, tendo um comportamento operacional adequado ao novo sistema de medição proposto pelo presente estudo. / [en] The pH is one of the quality control parameters of fuel ethanol, established by the Brazilian standard ABNT NBR 10891, whose scope is specific for hydrated fuel ethanol, and by the American standard ASTM D 6423, which focuses on anhydrous ethanol fuel. In this context, the present study presents a critical analysis of the composition of the electrodes used by the different measurement systems for ethanol pH, due to the presence of water in the composition of the glass electrode. Thus, the objective of the present study was to propose a new system for measuring the pH of hydrated fuel ethanol, which was the only solvent used, using acid-base indicators as a reference. Box-Behnken Design made possible to determine the optimal condition expected for the new measurement system, which was compared with the systems proposed by the normative references and later with the pH range defined by the indicators. The results revealed that the pH values obtained by the different systems used, including the one proposed by the present study, are statistically different from each other, and that only the values obtained by the new measurement system are suitable for the pH range found by the indicators. The optimized electrode presented an adequate response sensitivity to the Nernst equation, having an operational behavior adequate to the new measurement system proposed by the present study.
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Hydrous Mineral Stability in Earth’s Mantle: Implications for Water Storage and Cycling

Rytel, Alexander L. 08 June 2016 (has links)
No description available.

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