Dissertations / Theses on the topic 'Sulfate de manganèse'

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
The dusty from the siderurgical industry (PD) it is an industrial solid residue originating from the processes of the metallurgy of the ore of manganese (Mn). This material contains significant concentration of Mn. The responsible industrial unit for the production of approximately 2000 ton/month of PD's is Rio Doce Manganês (RDM), company of the group of the Company is Worth of Rio Doce (CVRD), nowadays, Company is Worth. PD's were characterized chemically (stage 1) and soon afterwards, appraised as source of Mn for soy plants (Glicine max L.), of the variety it Conquers and eucalyptus plants (Eucalyptus globulus), of the hybrid Urograndis, vegetation home (stage 2). Para the stage 1 of the research, they were chosen ten materials of PD's collected in the industrial units of Barbacena/MG, Ouro Preto/MG, Salvador/Ba and Corumbá/MS, respectively. The samples of PD's were analyzed according to the lixiviação procedures and solubilization of solid residues (ABNT NBR 10005 and 10006, 2004). The tenors of metals of PD ́s were quantified through espectrofotometry in optic emission with plasma coupled induced (ICP-OES) and espectrofotometry for atomic absorption (AAS). Soon afterwards, the experiment was accomplished vegetation home (stage 2), being used samples of two Latossolos (LVa), a loamy one (TG) and other sandy (TM), of the cities Viçosa/MG and Three Marias/MG, respectively. As sources of Mn, were appraised samples of PD's in natura originating from five industrial units of RDM/CVRD and two prepared fertilizers starting from PD's: the sulfate of manganese (SM-PD) and the oxide of manganese (OM-PD). it was included as treatment controls another fertilizer sulfate of commercial manganese (SM- with). The materials were applied in equivalent amount to the doses 0,0; 2,5; 5,0; 7,5 and 30,0 mg kg-1 of Mn, except for applied OM-PD just in the doses 2,5 and 30,0 mg kg-1 of Mn. The plants were collected and droughts in greenhouses with ventilation forced of hot air. Soon afterwards, they were determined the tenors of P, Mn, Zn, Ass, Faith, Cr, Ni, You and If, with xiextraction of nítric acid and percloric (3:1), for espectrofotometry of optical emission with plasma coupled induced (ICP-OES). The data were submitted to the analysis of multiple lineal regression, being evaluated the production of the mass of dry matter, concentration and accumulation of the chemical elements in the aerial part and roots of the soy plants and eucalyptus. The results obtained with the extracts solubilizados (stage 1), they presented tenors of The, Pb, If, Hg, Mn, Faith and Al in values above the maximum limits established by ABNT (I Enclose G, ABNT NBR 10004, 2004). on the other hand, the tenors of metals found in the leached extracts didn't result in high values, second referred her norm. There was not significant answer with the sources of applied Mn in the treatments, in what he/she concerns the production of the mass of dry matter of the soy plants and eucalyptus (stage 2). there also was not, accumulation of heavy metals in the fabrics of the same ones in levels that represented any risk to his/her development. PD's in natura made available Mn to the cultivated plants, in amounts comparable to liberated them to SM-PD, OM-PD and the SM-COM. It is ended that, so much PD's in natura, as for the materials produced starting from PD's (SM-PD and OM-PD) they were efficient as sources of Mn to the soy plants and eucalyptus cultivated vegetation home. The obtained results indicate that the use of PD can be viable, as source of Mn for the industry of fertilizers.
O Pó de Despoeiramento (PD) é um resíduo sólido industrial proveniente dos processos da metalurgia do minério de manganês (Mn). Este material contém concentração significativa de Mn. A unidade industrial responsável pela produção de aproximadamente 2000 toneladas/mês de PD s é a Rio Doce Manganês (RDM), empresa do grupo da Companhia Vale do Rio Doce (CVRD), atualmente, Companhia VALE. Os PD s foram caracterizados quimicamente (etapa 1) e em seguida, avaliados como fonte de Mn para plantas de soja (Glicine max L.), da variedade Conquista e plantas de eucalipto (Eucalyptus globulus), do híbrido Urograndis, em casa de vegetação (etapa 2). Para a etapa 1 da pesquisa, foram escolhidos dez materiais de PD s coletados nas unidades industriais de Barbacena/MG, Ouro Preto/MG, Salvador/Ba e Corumbá/MS, respectivamente. As amostras de PD s foram analisadas segundo os procedimentos de lixiviação e solubilização de resíduos sólidos (ABNT NBR 10005 e 10006, 2004). Os teores de metais dos PD ́s foram quantificados por meio de espectrometria em emissão ótica com plasma acoplado induzido (ICP-OES) e espectrometria por absorção atômica (AAS). Em seguida, foi realizado o experimento em casa de vegetação (etapa 2), utilizando-se amostras de dois Latossolos (LVa), um argiloso (TG) e outro arenoso (TM), das cidades Viçosa/MG e Três Marias/MG, respectivamente. Como fontes de Mn, foram avaliadas amostras dos PD s in natura proveniente de cinco unidades industriais da RDM/CVRD e dois fertilizantes preparados a partir dos PD s: o sulfato de manganês (SM-PD) e o óxido de manganês (OM- PD). Foi incluído como tratamento controle um outro fertilizante sulfato de manganês comercial (SM-Com). Os materiais foram aplicados em quantidade equivalente às doses 0,0; 2,5; 5,0; 7,5 e 30,0 mg kg -1 de Mn, com exceção do OM-PD aplicado apenas nas doses 2,5 e 30,0 mg kg -1 de Mn. As plantas foram coletadas e secas em estufas com ventilação forçada de ar quente. Em seguida, determinaram-se os teores de P, Mn, Zn, Cu, Fe, Cr, Ni, Ti e Se, com ixextração de ácido nítrico e perclórico (3:1), por espectrometria de emissão óptica com plasma acoplado induzido (ICP-OES). Os dados foram submetidos à análise de regressão linear múltipla, avaliando-se a produção da massa de matéria seca, concentração e acúmulo dos elementos químicos na parte aérea e raízes das plantas de soja e eucalipto. Os resultados obtidos com os extratos solubilizados (etapa 1), apresentaram teores de As, Pb, Se, Hg, Mn, Fe e Al em valores acima dos limites máximos estabelecidos pela ABNT (Anexo G, ABNT NBR 10004, 2004). Por outro lado, os teores de metais encontrados nos extratos lixiviados não resultaram em valores elevados, segundo a referida norma. Não houve resposta significativa com as fontes de Mn aplicadas nos tratamentos, no que diz respeito à produção da massa de matéria seca das plantas de soja e eucalipto (etapa 2). Não houve também, acúmulo de metais pesados nos tecidos das mesmas em níveis que representassem qualquer risco ao seu desenvolvimento. Os PD s in natura disponibilizaram Mn às plantas cultivadas, em quantidades comparáveis às liberadas ao SM-PD, OM- PD e o SM-Com. Conclui-se que, tanto os PD s in natura, quanto aos materiais produzidos a partir dos PD s (SM-PD e OM-PD) foram eficientes como fontes de Mn às plantas de soja e eucalipto cultivadas em casa de vegetação. Os resultados obtidos indicam que o uso do PD pode ser viável, como fonte de Mn para a indústria de fertilizantes.

On présente l'étude des mécanismes de formation des couches de transfert sélectif (CTS) de sulfures de manganèse sur un outil de coupe a partir des seules inclusions contenues de façon contrôlée dans l'acier usiné. On montre que la stabilité de la CTS sur l'outil correspond à un équilibre dynamique entre sa vitesse d'alimentation et sa vitesse d'érosion avec l'adhérence inclusion/outil comme mécanisme clé gouvernant cette stabilité. Cette adhérence est liée à l'affinité chimique entre l'élément métallique actif présent à la surface de l'outil (Zr, ti) et le soufre des inclusions de l'acier exprimée en termes d'enthalpie de formation du sulfure correspondant. Par spectroscopie des électrons Auger en mode balayage, nous avons réussi à comprendre le mécanisme le plus probable d'accrochage des sulfures de manganèse sur des outils mixtes composes de carbures WC et tic. A l'endroit des carbures simples de type wc, on assiste a une usure diffusionnelle classique qui se traduit par leur dissociation et évacuation continuelles. En revanche, l'élément de transition (ti) dans les carbures actifs également dissociés forme, avec les inclusions de l'acier usine, une fine couche d'oxysulfure stable, et certainement adhérente, qui interrompt cette dissociation et constitue une base d'accrochage pour d'autres sulfures. Dans la même logique, on constate que la continuité chimique du compose actif à la surface de l'outil (outils revêtus) favorise encore la stabilité des CTS. Bien que d'importance cruciale, la maitrise compositionnelle de la surface de l'outil ne peut avoir qu'un rôle de révélateur du flux d'alimentation en inclusions provenant du copeau. On montre le rôle capital qui revient au contrôle inclusionnaire en matière de composition des inclusions principalement mais aussi en termes de morphologie et de déformabilité relative inclusion/matrice

El concentrado de plomo-plata que es materia de investigación tiene un contenido de plata de 210.7 oz/tc, 16.20% de plomo y 18.7 % manganeso, el cual es difícil comercializar. El objetivo de esta investigación consiste en minimizar el contenido de manganeso del concentrado de plomo-plata, por ser este elemento que diluye los contenidos de plomo y plata, perjudicando la comercialización del concentrado mencionado. El proceso de disminución de manganeso de un concentrado plomo-plata se puede adaptar a minerales con el mismo problema, alto contenido de manganeso (18.7%). Como subproducto de la lixiviación de manganeso se obtiene, una solución un sulfato de manganeso la cual mediante procesos se obtendrá sulfato de manganeso monohidratado. En la etapa de flotación se corrieron 4 pruebas iniciales que constan de tres etapas, la primera etapa fue a una lixiviación a pH=4, le segunda etapa la flotación del residuo de lixiviación de la etapa anterior y la tercera etapa la lixiviación del concentrado de flotación de la etapa anterior a un pH=2. Se obtuvo como resultado un concentrado de plomo de 20% y un contenido de plata de 259.33 oz/tc. En vista que con este procedimiento no dio los resultados esperados se procedió a cambiar el diagrama de flujo. La primera etapa fue a una lixiviación a pH=4, la segunda etapa la lixiviación del residuo anterior a un pH=2 y la tercera etapa la flotación del residuo de lixiviación de la etapa anterior. Bajo estas condiciones es posible lixiviar el 95% de manganeso con una pérdida de peso total de 30% y un consumo de H2SO4 de 486 kg/t. Después de realizar varias pruebas con este nuevo diagrama de flujo se obtuvo un concentrado hasta de 27% Pb, el contenido de plata es de 326 oz/tc y un contenido de manganeso de 1.81 %. Realizadas las pruebas de lixiviación se prosigue a la neutralización de la solución de lixiviación, utilizando el concentrado de plomo-plata. En esta prueba se trabajó con porcentajes de sólidos de 10%, 20%, 30%, 40% y 50% para determinar cuál es la adecuada para lograr precipitar los elementos no deseables como el fierro, el plomo, el zinc entre otros y además la de enriquecer de manganeso a la solución. En un tiempo de neutralización de 3 horas con un porcentaje de solido del 20% se obtuvo la disminución de los valores hasta 49ppm de zinc, 1 ppm de fierro y 9 ppm de plomo, a su vez la concentración de manganeso aumento hasta 89900 ppm. En la etapa de purificación de solución neutralizada, se usó sulfuro de sodio en una cantidad de 0.064 gr, disminuyendo el contenido de plomo en 0.2 ppm y el zinc en 0.2 ppm. Luego de esta etapa de purificación de la solución lixiviante, se procedió a la cristalización de la solución mediante la evaporación, se toma una muestra de un litro y se empezó el proceso de evaporación a una temperatura de 70 °C. En esta etapa empiezan a aparecer los primeros cristales que son los de sulfato de calcio por lo cual se procede a filtrar la solución y retirar los cristales formados. Se toma una muestra de este residuo y da un contenido de calcio de 22.17%. Posteriormente la solución se dispone a calentar para proseguir con la etapa de evaporación de la solución a una temperatura de 50 °C y la formación de los cristales de sulfato de manganeso monohidratado. Al cabo de todo este proceso se obtiene 180 gr de sulfato de manganeso monohidratado, con una concentración de manganeso de 32.2%, el sulfato de manganeso monohidratado es un elemento adicional vendible y usado en la industria agrícola como fertilizante.
Tesis

L'évaluation des capacités non-destructives de la Microscopie Raman en Archéologie est la ligne directrice de ce travail de recherche. Trois domaines ont été choisis afin d'estimer les avantages et les limites d'une telle technique d'analyse ; il s'agit de l'étude 1) des pigments issus des peintures préhistoriques, 2) des produits de corrosion de métaux d'origine archéologique et 3) des vitraux (le verre, la coloration et l'altération). Les résultats plus ou moins « positifs » selon les domaines, mettent en
évidence, par exemple, les capacités de la MR à distinguer les oxydes de Mn du carbone dans les peintures noires préhistoriques ou encore, la facile identification de l'hématite ; ils permettent également de distinguer assez facilement les différentes phases
d'altérations existantes sur les métaux corrodés (sulfates, oxydes, chlorures...). Enfin, si l'étude du verre et des colorations en surface offrent des résultats assez positifs (complexes de type : PbCrO4.PbO), l'identification de la coloration dans la masse des vitraux par des colloï des métalliques reste plus complexe. La fluorescence constitue
également un des désavantages certain de cette méthode. Toutefois, la réussite de cette technique, dans le domaine de l'archéometrie, où elle est encore peu appliquée, permet d'entrevoir un avenir prospère et une utilité incontestable pour les archéologues,
restaurateurs et conservateurs.

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro Tecnológico, Programa de Pós-Graduação em Engenharia Química, Florianópolis, 2013.
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O manganês foi descoberto em 1774 pelo sueco Johan GottliebGahn, através da redução com dióxido de carbono. Sua principal aplicação é na fabricação de ligas metálicas, na qual é um agente removedor de enxofre e oxigênio e outros usos de seus principais compostos incluem o dióxido de manganês na confecção de pilhas secas e o permanganato de potássio em laboratório como agente oxidante em várias reações químicas. É o 12° elemento mais abundante da crosta terrestre e seus principais minérios são a pirolusita e a rodocrosita. As maiores jazidas estão localizadas na África do Sul, Brasil, Austrália, Índia, China e Gabão. No território brasileiro os estados do Pará, Minas Gerais e Mato Grosso do Sul são as principais regiões de mineração. O sulfato de manganês é o composto inorgânico com fórmula MnSO4. Este sólido incolor e deliquescente é um sal de manganês comercialmente significativo. Aproximadamente 260 milhões de kg/ano foram produzidos mundialmente em 2005. Ele é percursor para o metal manganês e muitos compostos químicos. Solos deficientes de Mn são remediados com este sal. Desta forma, esta pesquisa objetivou a obtenção do sulfato de manganês a partir do minério de manganês. O trabalho experimental constituiu primeiramente na caracterização do minério pelo método de difração de raios X (DRX). Na análise de caracterização foi verificado que o minério continha 32% de Óxido de Manganês (MnO). Para obtenção do sulfato de manganês foi desenvolvida uma rota utilizando ácido sulfúrico para a formação do sal a 90°C + 5°C. A variável de processo foi o tempo (60, 90 e 120 minutos). A solução obtida foi filtrada com uma bomba a vácuo. Após a filtragem foi adicionado álcool etílico à solução para que ocorresse uma maior precipitação dos cristais de sulfato de manganês. Uma segunda filtração foi realizada obtendo assim o sulfato de manganês purificado.

Abstract : Manganese was discovered in 1774 by Swedish Johan Gottlieb Gahn , by reducing its oxide carbonate . Its main application is in the manufacture of alloys , which is an agent remover sulfur and oxygen and other uses of their main compounds include manganese dioxide in the manufacture of dry cell batteries and potassium permanganate in the laboratory as an oxidizing agent in various chemical reactions . It is the 12th most abundant element in the earth's crust and its main ores are pyrolusite and rhodochrosite . The largest deposits are located in South Africa , Brazil , Australia, India , China and Gabon in the territory Brazilian states of Pará , Minas Gerais and MatoGrosso do Sul are the main mining regions . The manganese sulfate is the inorganic compound with the formula MnSO4 . This colorless, deliquescent solid manganese salt is a commercially significant. Approximately 260 million kg / year were produced worldwide in 2005 . It is a precursor to manganese metal and many chemical compounds. Mn deficient soils are remediated with this salt. Thus , this study aimed to obtain the manganese sulfate from manganese ore . The experimental work consisted primarily in the characterization of the residue by the method of X-ray diffraction ( XRD ) . In characterization analysis it was found that the residue contained 32% of manganese oxide ( MnO ) . To obtain manganese sulphate route was developed using sulfuric acid to form the salt at 90 ° C ± 5 ° C. The process variable was the time (60, 90, and 120 minutes). The obtained solution was filtered with a vacuum pump. After filtering ethyl alcohol was added to the solution for precipitation to occur more of manganese sulfate crystals . A second filtration was performed thus obtaining purified manganese sulfate .

$\rm Mn\sb2SiS\sb4$ is a synthetic Olivine in which we have discovered an exceptional temperature dependent magnetic behavior that may lead to interesting applications. A state of spontaneous magnetization was found to exist in this material, but only between 83 and 86.5 K. In order to explain this unusual magnetic phenomena, polycrystalline samples of $\rm Mn\sb2SiS\sb4$ were first prepared from the elements and studied by SQUID magnetometry in low fields, by X-ray and neutron diffraction, by electron spin resonance (ESR) and by specific heat calorimetry. This research, in which the author was a member of a team, is described. His specific contributions include among others; the debugging and extension of some of the computer programs used to analyze the neutron diffraction results, the interfacing of the Bruker ESR spectrometer to a IBM compatible computer and the development of the computer progams to acquire the resonance curves and analyze the line spectra, the analysis of the ESR results, the assembly of parts of an apparatus and the development of a procedure to measure the specific heat of small samples in the 77 to 150 K range as well as some preliminary measurements on a sample of $\rm Mn\sb2SiS\sb4.$ These contributions are emphasized in this thesis. (Abstract shortened by UMI.)

The treatment of Mn and SO42- contaminated mine drainage via a sulfate reducing bioreactor is expected to result in near-permanent immobilization of significant amounts of Mn and a portion of the sulfates within the matrix. This study tested several different combinations of organic amendments and inorganic substrates in an attempt to optimize sulfate reducing conditions and Mn removal capacity. Five different organic carbon sources, including corn mash, wood mulch, biosolids, soybean oil, and sorghum syrup in combination with five different inorganic substrates, including creek sediment, marble and limestone chips, polished gravel, and sand were tested in batch experiments. Results indicate a widely Mn variant removal potential among the treatments, ranging from 35% for soybean oil to 97% for the mulch mixture, with respective Eh ranges of +60 mV and -320 mV. Sulfate removal ranged from less than 10% to 85%. The most favorable combinations were tested in small scale bioreactors under dynamic conditions. Greater than 90% of Mn and 70% of sulfate was removed over a 65 day test period. Results indicate Mn removal mechanisms include sulfide, oxide, and carbonate formation and simple sorption and SO42- removal mechanisms of sulfide gas evolution, gypsum and MnS precipitation, and anion sorption/cation bridging.

This study evaluated alternative sulfide treatment processes for potable water systems that rely on groundwater supplies. Research for this study was conducted at the Imperial Lakes (IL) and Turner Road (TR) water treatment plants (WTPs) in Polk County, Florida. These WTPs are in the process of refurbishment and expansion, and will require the installation of a new groundwater well. The IL and TR WTPs both rely upon groundwater sources that contain total sulfide at concentrations ranging from 1.4 to 2.6 mg/L. Sulfide is a concern because if left untreated it can impact finished water quality, corrosivity, create undesirable taste and odor, and oxidize to form visible turbidity. For this reason, the raw water will require treatment per Florida Department of Environmental Protection (FDEP) "Sulfide Rule" 62-555.315(5)(a). This rule does not allow the use of conventional tray aeration (currently in use at the IL and TR WTPs) for wells that have significant total sulfide content (0.6 to 3.0 mg/L). This research was commissioned because the potential water treatment method identified in the Sulfide Rule (i.e. forced-draft aeration) would not adequately fit within the confines of the existing sites and would pose undue burden to neighboring residents. In addition, an effective sulfide treatment process was desired that offered a low profile, did not necessitate the need for additional complex chemical feed systems, minimized the extent of electrical infrastructure upgrades, and was inexpensive to construct and operate. To meet these goals, several alternative technologies were evaluated at the desktop and bench-scale; these included anion exchange, various oxidation methods, and alternative media filtration processes. From that effort, several processes were selected for evaluation at the pilot scale: bleach (NaOCl) oxidation preceding electromedia filtration; manganese (IV) oxide (MnO2) filtration continuously regenerated with bleach; and ferrate (Fe(VI)) oxidation. Electromedia and MnO2 filtration were shown to be effective for total sulfide treatment. Both processes reduced total sulfide content to below detection levels (< 0.1 mg/L) for groundwater supplies containing as much as 2.6 mg/L of total sulfide. The use of bleach oxidation ahead of media filtration also produced finished water with low turbidity (< 1.0 NTU) as compared to conventional tray aeration and chlorination processes (6-16 NTU, as observed in this study). It was determined that the media filtration approach (electromedia and MnO2) was effective for sulfide treatment and met the County's site objectives established at the outset of the project. Ferrate was also shown to reduce total sulfide content to below detection levels (< 0.1 mg/L) for groundwater supplies containing as much as 2.6 mg/L of total sulfide. An opinion of probable capital costs for installing a sulfide oxidation/filtration process at either the Imperial Lakes or Turner Road WTP was estimated to range from roughly $830,000 to $1,100,000. That equates to a $/kgal capital cost of $0.10 to $0.32 (at 8% for 20 years). An opinion of annual probable bleach chemical costs was estimated to range from $3,500 to $9,800 for the IL WTP and $3,500 to $5,800 for the TR WTP.
M.S.Env.E.
Department of Civil and Environmental Engineering
Engineering and Computer Science
Environmental Engr MSEnvE

Este trabalho tem por objetivo definir a sistemática da correta detecção de indicações de inclusões do tipo sulfeto no aço 15V45 durante a inspeção por ultrassom (US) em linha automática, de forma a garantir uma inspeção confiável, detectando as inclusões existentes com a mínima incidência de indicações falsas. Para atingir o objetivo, os sulfetos foram identificados através da realização do ensaio por ultrassom (US) manual e, por amostragem, foram analisadas as morfologias destas inclusões encontradas via técnica de microscopia eletrônica de varredura (MEV) para conhecer sua distribuição, visando a definição de testes no equipamento automático. As inclusões do tipo sulfeto são descontinuidades de difícil detecção devido a sua morfologia, semelhante a pequenas trincas ramificadas. Como metodologia para garantir o melhor ajuste do US automático, foi realizado um brainstorming de onde surgiram as variáveis com maior impacto na detecção das descontinuidades. Estas variáveis foram computadas e analisadas em um Diagrama de Ishikawa, a partir do qual foram identificados alguns parâmetros do equipamento influentes na falha de detecção das descontinuidades, tais como, rotação, taxa de repetição de pulso, curva de correção altura distância, bem como foram ajustadas as rotinas de limpeza e manutenção. Por fim, foi realizado um estudo de Planejamento de Experimentos para testar estas variáveis e foi elaborado o Plano de Ação. Com o direcionamento correto de todas as ações propostas, a meta do trabalho é garantir uma detecção mais assertiva, buscando (i) evitar a alta incidência de indicações falsas, conhecendo a possibilidade de que o problema não seja eliminado, mas minimizado, principalmente devido a ruídos e vibrações existentes no processo e (ii) reduzir ao máximo a falha na detecção dos defeitos, conhecendo as limitações do equipamento automático e dos defeitos existentes, respectivamente em relação à confiabilidade e à morfologia.
This work aims to define a methodology for the correct detection of the sulfide type inclusions in 15V45 steel during the inline ultrasound (US) inspection to ensure a reliable test, detecting the existing discontinuities with the minimum incidence of false indications. To achieve this purpose, the sulfides were first identified through portable ultrasound (US) inspection. Then, some samples were analyzed by scanning electron microscopy (SEM) technique to evaluate the morphology and the distribution of these discontinuities in order to define the tests parameters for the automated equipment. The difficulty of detection of sulfide inclusions by inline US is due to their morphology, that is similar to branch and discontinuous small cracks. As a methodology to ensure the best online US parameters, brainstorming was used to identify the variables with greater impact in the discontinuities detection. These variables were computed and analyzed in a Ishikawa diagram, in wich influential parameters of the equipment failure in the discontinuities detection were identified, such as rotation, pulse repetition rate, time distance curve correction, as well as some cleaning and maintenance routine adjustments. Finally, a design of experiments study was conducted to test these variables, resulting in an Action Plan. With the proper guidance of all proposed actions, the aim of this work is to guarantee a more assertive discontinuities detection, seeking to (i) avoid the high incidence of false indications, knowing the possibility that the problem will not be eliminated, but minimized, mainly due to the process noise and vibration (ii) reduce the discontinuities misdetection, knowing the limitations of the automated equipment and the discontinuities morphology, with the single goal of ensuring customer satisfaction.

Ce travail comporte trois parties. La première concerne l'étude magnétique de sites actifs de métallobiomolécules en utilisant un susceptomètre à SQUID. De par sa haute sensibilité, cet instrument permet de mesurer le signal paramagnétique de métalloprotéines en solution. Nous avons développé une méthodologie de ces mesures. Nous avons appliqué cette technique à des protéines fer-soufre comme la protéine Sulfite Réductase ou la protéine Ferrédoxine II et des protéines au fer à pont oxo comme la protéine Utéroferrine. Nous confrontons nos résultats à ceux obtenus par d'autres méthodes. Dans la deuxième partie de ce travail, nous exposons les propriétés magnétiques de complexes homo et hétérobinucléaires présentant le motif suivant [M(III)(μ - O)(μ -CH3CO2)2M'(III)]2+ avec M,M'=Fe,Fe; Fe,Mn ; Fe,Cr; Mn,Mn; V,V. Nous envisageons ensuite la relation entre les phénomènes d'échange et la liaison métal-métal en nous appuyant sur notre étude expérimentale d'un composé dinucléaire du Mn(IV) où les ions sont pontés par trois ligands μ-oxo. Enfin, dans la dernière partie, nous examinons la spectroscopie de systèmes polynucléaires à valence mixte au Mn(III) et Mn(IV) et élaborons différents modèles pour interpréter le spectre RPE multiligne observé pour l'état S2 du site de dégagement d'oxygène des plantes
This work is constituted of three parts. The first part involves magnetization studies of biomolecule metallic active sites using a SQUID susceptometer. Due to the high sensitivity of those new susceptometer, the paramagnetic signal of metallic centers of metalloproteins in solution can now be measured accurately. We developed new methods to achieve those measurements. We applied this technique to iron-sulfur proteins like Sulfite Reductase or Ferredoxine II and proteins containing two iron atoms bridged by an oxo group like Uteroferrin. We compare our results with those obtained by other methods. In the second part of this work, we present magnetic properties of homo and heterodinuclear compounds exhibiting the core [M(III)(μ - O)(μ -CH3CO2)2M'(III)]2+with M,M' = Fe,Fe; Fe,Mn; Fe,Cr; Mn,Mn; V,V. Then, we explore the relationship between exchange phenomena and metal­metal bonding using our experimental study of a Mn(IV) dinuclear compound where the two manganese atoms are bridged by three oxo groups. In the last part, we examine EPR spectroscopy of polynuclear Mn(III) and Mn(IV) compounds and build up various madel in order to interpret the multiline EPR spectra of the 82 state of the Oxygen Evolving Center of the Photosystem II of plants

Les travaux decrits dans ce memoire presentent les resultats obtenus lors de l'oxydation d'alcools tertiaires catalysee par un systeme biomimetique metalloporphyrine/donneur d'oxygene. Les metalloporphyrines, qui sont d'excellents modeles du cytochrome p-450, ont ete largement etudiees dans des reactions d'hydroxylation et d'epoxydation. En revanche, peu d'etudes ont ete menees sur l'oxydation d'alcools donnant lieu a des coupures de liaisons c-c. De telles reactions sont pourtant catalysees par le cytochrome p-450, par exemple lors de la degradation de la chaine laterale du cholesterol. Le premier chapitre est une revue bibliographique actualisee des differentes methodes decrites a ce jour pour oxyder les alcools tertiaires. Il s'agit majoritairement de transpositions, cyclisations ou fragmentations oxydantes. Dans tous les cas, la structure de l'alcool est particuliere et les reactifs les plus frequents sont les oxydes de cr(vi). L'acide 4-(1-hydroxy-1-phenylethyl)benzoique et quelques derives ont ete choisis comme substrats pour etudier les coupures de liaisons c-c sur les alcools tertiaires. L'etude de leur oxydation par la meso-tetrakis(4-n-methylpyridiniumyl)porphyrine de manganese (mn-tmpyp) en presence de khso#5 fait l'objet du deuxieme chapitre. Les produits formes, resultant de coupures de liaisons c-c, ont ete identifies et quantifies. Nous avons ainsi mis en evidence la formation inattendue d'un ester. L'analyse de l'influence de divers facteurs (solvant, atmosphere reactionnelle) ainsi que des experiences de marquages avec h#2#1#8o et #1#8o#2 ont permis de proposer un mecanisme reactionnel mettant en jeu -fragmentations et rearrangements neophyles. Le troisieme chapitre concerne l'utilisation du couple sulfite/o#2 a la place du khso#5 en tant que donneur d'atome d'oxygene. Les resultats obtenus pour l'epoxydation d'alcenes, l'hydroxylation d'alcanes et les coupures d'adn permettent de conclure que la reactivite du systeme mn-tmpyp/sulfite/o#2 est similaire a celle du systeme mn-tmpyp/khso#5 deja etudie au laboratoire avec les memes substrats. Le remplacement de khso#5 par le couple sulfite/o#2 rapproche encore davantage le fonctionnement du systeme catalytique utilise de celui du cytochrome p-450 qui est active en presence d'un reducteur et d'oxygene moleculaire.

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Neste trabalho, cristais de sulfato níquel dopados com íons de manganês (NSH: Mn) e cristais de sulfato níquel dopados com de íon de magnésio (NMgSH) foram crescidos e posteriormente caracterizados pelas técnicas de difração de raios X e de espectroscopia Raman. Os resultados obtidos mostraram que os cristais dopados possuem estrutura muito semelhante a do cristal de sulfato de níquel puro (NSH), com uma deformação anisotrópica nas dimensões da célula unitária em relação ao cristal puro. O objetivo do presente estudo foi crescer dois novos monocristais de boa qualidade óptica para serem usados como filtros ópticos de banda passante. Os cristais de sulfato de níquel hexa-hidratado (NHS) são conhecidos por possuírem espectros de transmissão óptica, que tem atraído muita atenção, pois apresentam duas regiões com alta eficiência de transmissão, aproximadamente 80%, sendo a primeira região entre 200 e 350 nm e a segunda entre 400 e 600 nm, e uma alta eficiência de absorção em outras regiões do espectro UV-VIS. Um espectro de transmissão de luz com estas características é semelhante a um filtro óptico. Analises Termogravimetric (TGA) foram realizadas para cristais puros e dopados. A temperatura de decomposição obtida para o NSH foi de 73 ° C, enquanto que os cristais de NSH:Mn e NMgSH apresentam valores de 82 ° C e 86 º C, respectivamente. Como pode ser facilmente percebido, a estabilidade térmica de cristais com o íons de Mn ou Mg em suas estruturas é significativamente maior. A banda de transmissão entre 200 e 350 nm no espectro óptico de NSH foi observada com redução significativa em sua largura nos espectros de transmissão dos cristais dopados restringindo assim a região do espectro conhecida como UVA.
In this work, manganese ions doped nickel sulphate crystals (NSH:Mn) and magnesium ion doped nickel sulphate crystals (NMgSH) were grown and later characterized by X-ray diffraction and Raman spectroscopy techniques. The results obtained showed that the doped crystals possess a structure very similar to that of the pure nickel sulphate crystal (NSH), with an anisotropic deformation in the unit cell dimensions compared to the pure crystal, undergoing expansion in unit. The aim of the present study was to grow two new single crystals of good optical quality to be used as optical bandpass filters. Nickel sulfate hexahydrate (NHS) crystals are known to possess an optical transmission spectrum which has attracted much attention because it presents two regions with high transmission efficiency of approximately 80%, the first region being between 200 and 350 nm and the second between 400 and 600 nm, and a high absorption efficiency in other regions of the UV-VIS spectrum. A light transmission spectrum with these characteristics is similar to an optical filter. Termogravimetric (TGA) analyses were carried out for pure and doped crystals. The obtained decomposition temperature of NSH was found to be 73 °C while that NSH: Mn and NMgSH crystals present values of 82 ° C and 86 C respectively. As can be easily perceived, the thermal stability of crystals with Mn or Mg ions in their structures is significantly higher. The transmission band between 200 and 350 nm in the optical spectrum of NSH was found to be narrower in the transmission spectrum of the doped crystal thus restricting the region of the spectrum known as UVA.

Trois nouvelles methodes de synthese de dicetones 1-4 sont proposees: la premiere par addition oxydante, a l'aide de sels de manganese et de cuivre, de cetones a des isopentenyl sulfones; la seconde par substitution allylique de sulfures ou de sulfones par des cetones enolisables; la troisieme par cycloaddition a une enone d'un nouveau reactif: la chloromethyl-2 allylphenylsulfone. Les produits de ces trois reactions sont des cetones comportant un groupe methylene en position 4 alors facilement transformees en dicetones par ozonolyse. L'utilite synthetique de ces trois methodes est illustree par la synthese de plusieurs composes naturels: pyrenophorine, acide chrysanthemique et jasmone

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Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Inúmeras regiões brasileiras apresentam problemas qualitativos em seus mananciais de abastecimento, originando dificuldades para a potabilização da água distribuída nas cidades. Geralmente, os consumidores julgam a segurança da água potável que bebem através de seus sentidos organolépticos. Os processos convencionais utilizados nas estações de tratamento de água não são efetivos na remoção de muitos compostos que causam cor, gosto e odor na água. Devido a isto, é comum que as companhias de saneamento recebam reclamações por parte dos consumidores sobre a qualidade da água distribuída. Dentre os compostos que causam gosto, odor e cor na água encontram-se o sulfeto de hidrogênio, o ferro e o manganês. O sulfeto gera um odor de “ovo podre”, perceptível a concentrações que variam entre 0,05 e 0,1 mg·L-1. Manganês e ferro estão associados principalmente a produção de cor e precipitados na água. Desta forma, o objetivo da pesquisa proposta foi estudar técnicas de tratamento alternativas as convencionais para controlar gosto, cor e odor na água potável pela presença de sulfeto de hidrogênio, ferro e manganês. Os processos investigados foram aeração em torre de dessorção, nanofiltração em membrana e oxidação com permanganato de potássio. Os testes foram realizados com água bruta oriunda do reservatório da Lomba do Sabão, em Porto Alegre. Os ensaios de oxidação anteriormente à clarificação físico-química constaram de 4 etapas. Na primeira, foram testados o cloreto férrico e o sulfato de alumínio, possibilitando a elaboração de diagramas de coagulação. Na segunda etapa, foi calculada a eficiência da coagulação na remoção de Fe(II), Mn(II) e H2S. Na terceira etapa, foi calculada a demanda do oxidante na água. Finalmente, na quarta etapa realizaram-se ensaios de oxidação do permanganato associado à clarificação físico-química. Os resultados mostraram que o processo de coagulação conseguiu remover o ferro satisfatoriamente, mas não o manganês. Nos ensaios usando permanganato os resultados mostraram que as remoções de ferro, manganês e sulfeto de hidrogênio foram de 92%; 59% e 94% (pH 7), e 93%; 74% e 100% (pH 8,0), respectivamente. No caso da relação estequiométrica, as reduções foram maiores quando foi usada a relação estequiométrica de 1,0 e pH 8,0 (89% para Mn e 95% para Fe). O protótipo de torre de dessorção, localizado na ETA Lomba do Sabão, foi operado com razões ar:água de 8 e 12 m3:m3. As remoções de ferro variaram entre 14% a 31%; para manganês, não houve redução aparente. As concentrações efluentes de sulfeto de hidrogênio foram inferiores ao limite de detecção do método analítico, mostrando que houve volatilização do gás neste processo. O protótipo do sistema de membranas de nanofiltração foi também instalado na ETA Lomba do Sabão. Foram realizados ensaios com vazões de 2 e 4 L∙min-1, correspondentes a taxas de aplicação de 14 e 28 L∙h-1∙m-2 a 25°C. As rejeições da membrana para a taxa de 14 L∙h-1∙m-2 foram de 91%, 96% e 100% (Many regions in Brazil have problems associated with the water quality of their supplies, which bring problems to the production of safe drinking water that is distributed in communities. Generally, consumers judge the drinking water safety through the use of their organoleptic senses. The conventional processes used in water treatment are not effective to remove many compounds that cause color, taste and odor in water. For this reason water utilities frequently receive complaints by angry consumers unsatisfied with the quality of drinking water. Among the compounds that cause taste, odor and color in drinking water are hydrogen sulfide, iron and manganese. Sulfide generates a "rotten egg" smell, perceptible at concentrations between 0.05 and 0.1 mg·L-1. Manganese and iron are mainly associated with the formation of color and precipitates in water. The objective of this research was to study alternative treatment technologies to remove hydrogen sulfide, iron and manganese from drinking water. The investigated processes were air-stripping, nanofiltration and oxidation with potassium permanganate. Air stripping and nanofiltration pilot plants were supplied with water from Lomba do Sabão reservoir, located in Porto Alegre. Potassium permanganate oxidation was studied in laboratory using Jar tests systems and water from Lomba do Sabão. Oxidation tests associated with chemical clarification were performed in four different phases. In the first, the coagulants ferric chloride and aluminum sulfate were tested, with preparation of coagulation diagrams. In the second phase, it was measured the removal of Fe(II), Mn(II) and H2S during chemical clarification. The water oxidation demand was tested in the third experimental phase. Finally, the fourth phase encompassed tests using potassium permanganate associated with chemical clarification for the removal of Fe(II), Mn(II) and H2S. The results demonstrated that coagulation removed iron efficiently, but not manganese. Using permanganate, reductions in iron, manganese and sulfide increased to 92%, 59% and 94% (pH 7,0), and 93%, 74% and 100% (pH 8,0), respectively. Higher removals were achieved at pH 8,0 and one time the compounds stoichiometric oxidation relation. The air-stripping tower prototype was located at the Lomba do Sabão Water Treatment Plant. It operated with air to water ratios between of 8 and 12 m3:m3. Iron removal rates varied from 14% to 31%, while there were no removal for manganese. Hydrogen sulfide concentrations in plant’s effluents were below the detection level, showing full volatilization of the gas during stripping. The nanofiltration system prototype was also installed at Lomba do Sabão Water Treatment Plant. Tests were performed using flowrates of 2 and 4 L·min-1, corresponding to hydraulic application rates of 14 e 28 L∙h-1∙m-2 a 25°C. The rejections for the 14 L∙h-1∙m-2 tests were 91%, 96% and 100% (