Made available in DSpace on 2014-12-17T14:17:54Z (GMT). No. of bitstreams: 1 AureaPMS_DISSERT.pdf: 2426110 bytes, checksum: 8679cb89ec2b1a9d200750245aa86d51 (MD5) Previous issue date: 2014-03-31 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The present study aimed to characterize the thermal profile of wood fired oven used by the red ceramic industry in Parelhas, in the Serid? region/RN, aiming to propose structural interventions that can contribute to increasing productivity and product quality, optimize wood consumption and mitigate existing losses during the burning process. The study was conducted at Cer?mica Esperan?a in the city of Parelhas -RN, Brazil, during the period from August 2012 to September 2013. Four treatments were performed with three replicates, ie, with, a total of 12 experimental units (burnings). In the first stage 4 treatments were performed with three replicates, totaling 12 experimental units (firings). In the second stage 2 treatments were performed with three replications, totaling 6 experimental units (firings). The physical characteristics of the wood were analyzed using standard NBR 11941 and NBR 7190 for basic density and moisture, respectively. The clay was used as a reference parameter for distinguishing treatments. For both the analysis and characterization was carried out using techniques of fluorescence X (XRF) rays, X-ray diffraction (XRD) analysis, particle size analysis (FA). In the first and second stages were monitored: the time during the firing process, the amount of wood used at each firing, the number of parts enfornadas for subsequent determination of the percentages of losses, but also product quality. To characterize the thermal profile of the oven, we measured the temperature at 15 points scored in the surface charge put into the oven. Measurements were taken every 30 minutes from preheat until the end of burning, using a pyrometer laser sight sighting from preheating until the end of burning. In the second step 12 metal cylinders distributed on the oven walls, and the cylinder end walls 8 of the furnace 2 and rollers on each side walls are installed equidistant to 17 cm from the soil and the surface 30 of the wall are installed. The cylinders distributed on the front were placed 50 cm above the furnace, and the base of the oven 20 cm distant from the ground. 10 also thermocouples were installed, and five thermocouples distributed 1.77 cm above the combustion chambers, and one thermocouple on each side, and three thermocouples in front of the oven. We carried out the measurements of the temperatures every 1 hour during the burning two hours in cooling the cylinders with a pyrometer and thermocouples for dattaloger. These were fixed with depth of 30 cm from the wall. After statistical analysis it was found that: the thermal profile of the furnace surface and at different heights was heterogeneous; and the ranges of density and moisture content of wood are within recommended for use as an energy source standards. We conclude that even at low temperatures reached during firing there was a significant production of good quality products, this is due to high concentrations of iron oxide and potassium oxide found in clay, which lowers the melting point of the piece. The average burn time for each step varied 650-2100 minutes wood consumption was on average 20 m3, product quality was on average 16% of first quality, 70% second, third and 5% to 10% loss . The distance between the wire and the surface of the oven was a significant parameter for all treatments, but with different variations, meaning that the wire should not be so generic and unique form, used as a criterion for completion of the burn process. The central part of the furnace was the area that reached higher temperature, and in a unified manner, with the highest concentration of top quality products. The ideal temperature curve, which provided the highest quality of ceramic products was achieved in the central part of the furnace / O presente trabalho teve como objetivo geral caracterizar o perfil t?rmico de fornos tipo caipira utilizados pelo setor de cer?mica vermelha em Parelhas, na regi?o do Serid?/RN, visando propor interven??es que possam colaborar para aumentar a produtividade, a qualidade dos produtos, otimizar o consumo de madeira e mitigar as perdas existentes durante o processo de queima. O trabalho foi desenvolvido em duas etapas, entre agosto de 2012 e setembro de 2013, na Cer?mica Esperan?a localizada na cidade de Parelhas-RN, Brasil. Na primeira etapa foram realizados 4 tratamentos, com tr?s repeti??es, totalizando 12 unidades experimentais (queimas). Na segunda etapa foram realizados 2 tratamentos, com tr?s repeti??es, totalizando 6 unidades experimentais (queimas). Foram analisadas as caracter?sticas f?sicas da madeira utilizando-se norma NBR 11941 E NBR 7190 para densidade b?sica e umidade, respectivamente. O lote de argila foi o par?metro utilizado como refer?ncia para distinguir os tratamentos nas duas etapas. Para tanto a an?lise e caracteriza??o foi realizada a partir de t?cnicas de fluoresc?ncia por raios X (FRX), difra??o por raios X (DRX), an?lise granulom?trica (AG). Na primeira e segunda etapas foram monitorados: o tempo de queima durante todo o processo, a quantidade de madeira utilizada em cada queima, o n?mero de pe?as enfornadas para posterior determina??o das porcentagens de perdas, como tamb?m qualidade dos produtos. Para caracteriza??o do perfil t?rmico dos fornos na primeira etapa foram aferidas temperaturas em 15 pontos marcados na superf?cie da carga enfornada. Para avaliar a correla??o existente entre a dist?ncia da superf?cie da carga enfornada e o fio utilizado como par?metro de controle do processo, foram realizadas medi??es utilizando-se trena e, paralelamente, realizou-se as aferi??es das temperaturas a cada 30 minutos com pir?metro de mira laser a partir do pr?-aquecimento, at? o final da queima. Na segunda etapa foram instalados 12 cilindros met?licos distribu?dos nas paredes do forno, sendo 8 cilindros nas paredes frontais do forno e 2 cilindros em cada paredes laterais, foram instalados equidistantes, com 17 cm de dist?ncia do solo e 30 da parede da superf?cie. Os cilindros distribu?dos na parte frontal foram colocados a 50 cm da superf?cie do forno, e na base do forno distantes 20 cm do solo. Foram instalados tamb?m 10 termopares, sendo 5 termopares distribu?dos 1,77cm acima das c?maras de combust?o, e 1 termopar em cada lateral, e 3 termopares na parte frontal do forno. Realizou-se as aferi??es das temperaturas a cada 1 hora no per?odo de queima 2 horas no resfriamento com um pir?metro nos cilindros e um dattaloger para os termopares. Esses foram fixados com profundidade de 30 cm da parede. Ap?s an?lise estat?stica verificou-se que: o perfil t?rmico dos fornos na superf?cie e nas diferentes alturas foi heterog?neo; e as faixas de densidade e umidade da madeira est?o dentro dos padr?es recomendados para utiliza??o como fonte de energia. Conclui-se que mesmo com baixas temperaturas alcan?adas durante a queima houve uma produ??o significativa de produtos de boa qualidade, isso se deve a grande concentra??o de oxido de ferro e oxido de pot?ssio encontradas na argila, que baixa o ponto de fus?o das pe?as. O tempo m?dio de queima em cada etapa variou de 650 a 2100 minutos, consumo de madeira foi em m?dia 20 m3, qualidade dos produtos foi em m?dia 16 % de primeira qualidade,70% de segunda, 5 % de terceira e 10 % de perdas. A dist?ncia entre o fio e a superf?cie do forno foi um par?metro significativo para todos os tratamentos, mas com oscila??es diferenciadas, significando que o fio n?o deve ser o modo de forma gen?rico e exclusivo, utilizado como crit?rio para finaliza??o do processo de queimas. A parte central do forno foi ? ?rea que atingiu maior temperatura, e de maneira mais homog?nea, com maior concentra??o de produtos de primeira qualidade. A curva de temperatura ideal, que proporcionou a melhor qualidade dos produtos cer?micos foi atingida na parte central do forno

Made available in DSpace on 2014-12-17T14:36:38Z (GMT). No. of bitstreams: 1 RosaneFF_DISSERT.pdf: 1403621 bytes, checksum: ce1988ce4c25abf8d8913a589232da88 (MD5) Previous issue date: 2012-03-28 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / El concepto de paisaje, caracterizado por la colaboraci?n de distintos dominios cognitivos, atraviesa campos disciplinarios y formas de estructurar la producci?n de conocimiento a trav?s del Arte. Para Cauquelin (2007), la representaci?n occidental de la mirada paisaj?stica es siempre una mirada est?tica que indica una conexi?n inseparable de la forma percibida con la forma sentida. Esa mirada est?tica recuerda al hombre su condici?n bioantropol?gica. En ese sentido, entiendo que un paisaje se presenta como un medio donde el humano puede ejercer su singularidad po?tica, transitando, as?, por campos o capas de conocimientos diversos capaces de ampliar su visi?n rearticuladora del mundo. Motivada por esa percepci?n, eleg? como campo emp?rico el Museo Taller de Cer?mica Francisco Brennand, en Recife, Pernambuco. Reconstruido por el artista, el lugar, injertado de recuerdos de la infancia, pasa a abrigar, a partir de 1971, el conjunto de su obra de cer?mica y pint?rica. La frecuentaci?n del artista transform? la estrategia metodol?gica de la entrevista en sabias y agradables conversaciones, que me proporcionaron la experiencia de otras posibilidades de enfoque durante la realizaci?n de la investigaci?n. El objetivo de la investigaci?n es ampliar las relaciones conceptuales entre paisaje y representaci?n, en el sentido de privilegiar a la imaginaci?n creativa. Tom? al paisaje como una met?fora y como un operador cognitivo, imprescindibles para el aprendizaje de la condici?n humana. Compartir estrategias a la vez complementares y rec?procas es lo que proponen Almeida (2009) y Morin con vistas a volver a enlazar la cultura cient?fica y la cultura human?stica, en un metodo mestizo y bricoleur que es necesaria para una reforma del pensamiento que lleva en cuenta el ensue?o de la materia propuesto por Bachelard (2008). El arte se convierte, as?, en un operador cognitivo capaz de promover cambios en el contexto de la educaci?n, en direcci?n a una pedagog?a con base compleja, como propone Pereira (1999) / O conceito de paisagem, caracterizado pela colabora??o de diferentes dom?nios cognitivos, perpassa campos disciplinares e formas de estruturar a produ??o de conhecimento por meio da Arte. Para Cauquelin (2007), a representa??o ocidental do olhar paisag?stico ? sempre um olhar est?tico que indica uma conex?o insepar?vel da forma percebida com a forma sentida. Esse olhar est?tico recorda ao homem sua condi??o bioantropol?gica. Nesse sentido, compreendo que uma paisagem se apresenta como um meio em que o humano pode exercer sua singularidade po?tica, transitando, assim, por campos ou camadas de conhecimentos diversos capazes de ampliar sua vis?o rearticuladora do mundo. Motivada por essa percep??o, escolhi como campo emp?rico o Museu Oficina Cer?mica Francisco Brennand, em Recife/ PE. Reconstru?do pelo artista, o lugar, enxertado de lembran?as da inf?ncia, passa a abrigar, a partir de 1971, o conjunto de sua obra cer?mica e pict?rica. A proximidade com o pr?prio artista transformou a estrat?gia metodol?gica da entrevista em s?bias e deliciosas conversas, que me proporcionaram experimentar outras vias de abordagem durante a realiza??o da pesquisa. O objetivo da pesquisa ? ampliar as rela??es conceituais entre paisagem e representa??o, no sentido de privilegiar a imagina??o criativa. Tomei a paisagem como uma met?fora e como um operador cognitivo, imprescind?veis ? aprendizagem da condi??o humana. Compartilhar estrat?gias ao mesmo tempo complementares e rec?procas ? o que prop?em Almeida (2009) e Morin com vistas a religar cultura cientifica e cultura human?stica, num m?todo mesti?o e bricoleur que ? necess?ria a uma reforma do pensamento que leva em conta o devaneio da mat?ria proposta por Bachelard (2008). A arte torna-se, assim, um operador cognitivo capaz de promover mudan?as no contexto da educa??o, em dire??o a uma pedagogia de base complexa, como prop?e Pereira (1999)

Made available in DSpace on 2015-03-13T17:10:44Z (GMT). No. of bitstreams: 1 LidianeSN_DISSERT.pdf: 4629879 bytes, checksum: d28e312771a5a0b81c006b055f5b7eb1 (MD5) Previous issue date: 2011-02-24 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The coastal zone has been studied worldwide with a focus on the coastal erosion. In the present days, much of the world's coastlines are being affected by erosion, which causes great damage to the economy. This work had as study case the beaches of Areia Preta, Artistas, Meio and Forte located in Natal in Rio Grande do Norte. It shows as result the monitoring of the beach strip that makes possible to obtain quantitative and qualitative data, allows the study of the coastal dynamics of the beaches and the Recovery Project of the Areia Preta beach interference on adjacent beaches. This research was guided by the integrated analysis method on the systemic perspective. The pratical procedures adopted were: bibliographic research; fieldwork during eleven months (environmental characterization, collection of hydrodynamic data, topographic leveling, collection of sediments) and; sedimentological analysis of samples collected. By monitoring of the points A, B, C, D and E we were able to find the occurrence of the coastal erosion on their biggest part except by the C and D profiles. It was noted the need for the government to complete the hydraulic fill, as it made only 60% of the landfill planed. It was found that the spikes built on the beach of Areia Preta are preventing the natural transport of sediments that the longshore performs towards South-North. This interference is causing the lack of sediment on the beaches of Forte and Meio and their coastal erosion in consequence / A zona costeira tem sido estudada em escala mundial com o enfoque na eros?o costeira. Atualmente, grande parte das linhas de costa mundial est? sendo afetada pela eros?o, o que gera grande preju?zo para a economia. O trabalho teve como ?rea de estudo as praias de Areia Preta, dos Artistas, do Meio e do Forte, localizadas em Natal/RN. Apresenta como resultado o monitoramento da faixa de praia, que possibilita a obten??o de dados quantitativos e qualitativos, permite o estudo da din?mica costeira das praias e da interfer?ncia do projeto de recupera??o da praia de Areia Preta nas praias adjacentes. Esta pesquisa foi norteada pelo m?todo da an?lise integrada, na perspectiva sist?mica. Os procedimentos pr?ticos adotados foram: pesquisa bibliogr?fica; trabalho de campo durante onze meses (caracteriza??o ambiental, coleta de dados hidrodin?micos, nivelamento topogr?fico e coleta de sedimentos) e; an?lise sedimentol?gica das amostras coletadas. Atrav?s do monitoramento dos pontos A, B, C, D e E, foi poss?vel constatar a ocorr?ncia de eros?o costeira em todos os perfis. Notou-se a necessidade do poder p?blico completar o aterro hidr?ulico, j? que este efetuou apenas 60% do aterro previsto. Constatou-se que os espig?es constru?dos na praia de Areia Preta est?o impedindo o transporte natural de sedimentos, que a deriva litor?nea realiza no sentido Sul-Norte. Essa interfer?ncia est? acarretando na falta de sedimentos nas praias do Meio e do Forte e, conseq?entemente, na eros?o costeira das referidas praias

Made available in DSpace on 2014-12-17T14:57:46Z (GMT). No. of bitstreams: 1 JoseCCSJ.pdf: 1343903 bytes, checksum: aa2a5fbffd13b95d16ec1f429e355eb5 (MD5) Previous issue date: 2008-08-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The industries of structural ceramics are among the most important production chains in the state of Rio Grande do Norte. The industry and other interest groups to target the replacement of firewood by natural gas. Studies accordingly concluded that simple change does not guarantee products of superior quality, and that the increase in spending on fuel can economically cripple the use of gas for burning the majority of products manufactured by that action. However some proposals of innovations in terms of process and product are being studied in an attempt to justify the use of natural gas in industry, structural ceramics. One of the aspects investigated is the development of ceramic products differentiated, with new designs and greater value added. Inserted in that context, this paper aims to investigate the potential use of clay-firing clear fabrication of the "bricks of apparent joins drought", a new ceramic product with an innovative way. The development of the work was done in three stages. In the initial stage was held the characterization of raw materials, sought information on physical, chemical, mineralogical and mechanical samples. In the second stage five bodies were made using two of the nine ceramic clay characterized the first step. The masses were analyzed and compared with respect to the size distribution, plasticity and technological properties. In the last part of this work was carried out tests on massive bricks manufactured on an industrial scale. The results show that the nine clays can be used in the manufacture of new ceramic products, is the only constituent of mass ceramic or by mixing with other(s) clay(s / As ind?strias de cer?mica estrutural figuram entre as cadeias produtivas mais importantes do estado do Rio Grande do Norte. O setor e outros grupos de interesse almejam a substitui??o da lenha pelo g?s natural. Estudos realizados nesse sentido conclu?ram que a simples mudan?a n?o garante produtos de qualidade superior, e que o aumento no gasto com combust?vel pode inviabilizar economicamente o uso do g?s para queima da maioria dos produtos fabricados por esse seguimento. Entretanto algumas propostas de inova??es em termos de processo e produto v?m sendo estudadas na tentativa de justificar o uso do g?s natural na ind?stria de cer?mica estrutural. Uma das vertentes pesquisadas ? o desenvolvimento de produtos cer?micos diferenciados, com novos designs e maior valor agregado. Inserido nesse contexto, o presente trabalho tem como objetivo investigar a potencialidade do uso de argilas de queima clara para fabrica??o dos tijolos de junta seca , um novo produto cer?mico com forma inovadora. O desenvolvimento do trabalho foi efetuado em tr?s etapas. Na etapa inicial foi realizada a caracteriza??o das mat?rias-primas, buscando obter informa??es em rela??o ?s propriedades f?sicas, qu?micas, mineral?gicas e mec?nicas das amostras. Na segunda etapa foram formuladas cinco massas cer?micas utilizando duas das nove argilas caracterizadas na primeira etapa. As massas foram analisadas e comparadas em rela??o ? distribui??o granulometria, plasticidade e propriedades tecnol?gicas. Na ?ltima parte desse trabalho foi realizado testes em tijolos maci?os fabricados em escala industrial. Os resultados mostram que as nove argilas podem ser utilizadas na fabrica??o dos novos produtos cer?micos, seja como ?nica constituinte da massa cer?mica ou pela mistura com outra(s) argila(s)

Atualmente, a participação da energia elétrica na matriz energética mundial é um assunto em evidência. O estudo do compósito isolante da barra estatórica, um dos componentes principais da máquina hidrogeradora, permite a obtenção de informações físico-químicas relevantes ao aperfeiçoamento do sistema, e também de estudos de comportamento térmico quando este é exposto à alta temperatura, por diferentes intervalos de tempo submetidos a estresses mecânicos, elétricos e/ou químicos. O sistema em estudo é o MICALASTIC®, desenvolvido pela empresa Siemens em 1960. Neste trabalho, as propriedades térmicas do compósito isolante, formado por uma fita de mica, resina epóxi (DGEBA), endurecedor (MHHPA) e acelerador naftenato de zinco (N-Zn) foram estudadas. Utilizando-se as técnicas termoanalíticas Calorimetria Exploratória Diferencial (DSC) e Termogravimetria e Termogravimetria Derivada (TG/DTG), o comportamento térmico de cada um dos materiais foi avaliado. As curvas DSC e TG/DTG também evidenciaram as possíveis interações químicas entre os componentes. Os estudos referentes à cura do material e da degradação térmica do compósito curado foram realizados. Observou-se claramente a influência da quantidade de acelerador na polimerização do sistema. A partir das curvas DSC, observou-se dois mecanismos de cura diferentes coexistentes, um com menor quantidade de N-Zn e outro com concentração maior, resultando em eventos de cura com início em temperaturas diferentes. Esse fato ainda não havia sido estudado desde a origem do sistema. Além disso, a perda de massa referente à evaporação do endurecedor no início do processo de cura foi confirmada a partir da caracterização do compósito por espectroscopia de absorção na região do infravermelho, comparando-se os espectros antes e após o fenômeno. Na prática, dois perfis de impregnação, o Homogêneo e o Heterogêneo, de barras condutoras são utilizados, e uma diferença significativa entre eles foi observada. Os estudos desenvolvidos devem ser associados a testes elétricos específicos para o melhor entendimento da relação entre a aplicação do material e suas propriedades teóricas termoanalíticas. Além disso, foi realizado o estudo cinético da decomposição térmica do compósito curado por métodos termogravimétricos, isotérmico e dinâmico. / Currently, the electric energy participation in the world energy matrix is a significant issue. The insulating composite in stator bars, which are one of the most important components in hydrogenerator machines, allows the attainment of relevant physical and chemical information to system optimization, in addition to study thermal behavior when the material is exposed to high temperatures, for different time intervals and mechanical, chemical and/or electrical stress. The studied system is MICALASTIC®, developed by Siemens Company in 1960. In this work, thermal properties of this insulating composite, composed by mica tape, epoxy resin (DGEBA), hardener (MHHPA) and zinc naphtenate (N-Zn) as accelerator, were studied. Using thermoananalytical techniques as Differential Scanning Calorimetry (DSC) and Thermogravimetry and Derivative Thermogravimetry (TG/DTG), thermal behavior of each material was evaluated. DSC and TG/DTG curves evidenced chemical interactions between components. The study relative to material curing and cured composite thermal degradation were described. It was clearly observed the N-Zn amount influence in the cure of system, and through DSC curves, it was possible to observe two distinct polymerization coexisting mechanisms, one with lower quantity of N-Zn and another one with bigger concentration, resulting in cure events starting in different temperatures. This fact has not been studied yet since the system has been originated. Besides that, the weight loss related to hardener evaporation starting with curing process was confirmed by composite characterization by FTIR spectra, before and after phenomenon. In practice, two impregnation patterns (Homogeneous and Heterogeneous) of conductive bars are used and a significant difference between them was observed. The developed studies have to be associated to electrical tests to a best understanding about material application and theoretical thermoanalytical properties. In addition, it was performed thermal decomposition of cured composite kinetic study by isothermic and dynamic thermogravimetric methods

Ce travail nous a permis de réaliser une étude de capteurs de gaz et d’humidité à base de graphène. Cette étude pourrait être utile non seulement pour améliorer les performances des capteurs à base de graphène mais aussi pour mieux comprendre l’interaction entre le graphène et les molécules de gaz. Ceci semble indispensable pour faire avancer les applications du graphène comme un matériau prometteur pour la détection des gaz. Des avancées significatives ont été présentées au niveau de la fabrication de ces capteurs, leurs différentes caractérisations électriques ainsi que d’autres techniques employées pour analyser le mécanisme contrôlant la détection des molécules de gaz/vapeur. Ces outils ont été mis en place pour concevoir et fabriquer plusieurs structures de capteur en utilisant différents substrats support du graphène d’une part et en modifiant les propriétés du graphène par utilisation des produits chimiques d’autres part. La caractérisation de ces capteurs sous différents environnements a permis de comparer les différentes réponses des capteurs et d’en tirer plusieurs conclusions sur le fonctionnement de ces dispositifs. En effet, le Mica, un substrat lisse et transparent, a été utilisé comme substrat pour le graphène. Le dopage induit par le mica a été étudié ainsi que son impact sur la sensibilité du graphène au gaz d’ammoniac. Ceci a permis de mettre en évidence le fait que le substrat joue un rôle important pour la détection de l’ammoniac. De plus, ces capteurs fabriques sur mica et SiO2 ont été testés sous différentes conditions de températures et d’oxygène. Dans une autre approche, un polymère a été utilisé pour doper le graphène. Une étude détaillée a été menée pour analyser le comportement de ce graphène fonctionnalisé par rapport aux molécules d’eau. Ces nouveaux résultats expérimentaux obtenus pendant cette thèse constituent un bon support à plusieurs résultats théoriques établis et permettent d’optimiser la conception des capteurs de gaz à base de graphène pour des meilleures performances. / In this research, we report on a study of graphene based gas and humidity sensors. This study could be useful not only to improve the performance of graphene based sensors but also to better understand the interaction between graphene and gas molecules. This seems necessary to promote the applications of graphene as a promising material for gas sensing. Significant advances have been made to design and fabricate these sensors: the different electrical characterizations as well as other techniques used to analyze the mechanism controlling the detection of gas/vapor molecules. These tools have been set up to design and manufacture various sensor structures using different underlying substrates for graphene on one hand and chemical modification of graphene properties on the other hand. The characterization of these sensors under different environments was used to compare the different responses of the sensors and draw several conclusions about gas sensing mechanism. Indeed, Mica, a smooth and transparent substrate, was used as a supporting substrate for graphene. Doping induced to graphene by mica and its impact on graphene sensitivity to ammonia gas were studied. This has made it possible to highlight the fact that the substrate plays an important role for the detection of ammonia. In addition, these sensors made on mica and SiO2 were tested under a variety of temperatures and oxygen. In another approach, a polymer was used to dope graphene. A detailed study was realized about the behavior of water molecules on functionalized graphene. The obtained experimental results, reported for the first time, represent a good support for several theoretical studies already made and could be used to optimize the design of graphene based gas sensors.

A safe storage of radioactive waste in repositories is an important task to protect humans and the environment from radio- and chemotoxicity. Long-term safety assessments predict the behavior of potential environmental contaminants like the actinides plutonium, uranium, or neptunium, in the near and far field of repositories. For such safety assessments, it is necessary to know the migration behavior of the contaminants in the environment, which is mainly dependent on the aquatic speciation, the solubility product of relevant solid phases, and the retardation due to sorption on surrounding minerals. Thus, an investigation of sorption processes of contaminants onto different minerals as well as the derivation of mineral specific surface complexation model (SCM) parameters is of great importance. Feldspar and mica are widely distributed in nature. They occur as components of granite, which is considered as a potential host rock for a repository in Germany, and in numerous other rocks, and thus also in the far field of nearly all repositories. However, their sorption behavior with actinides has only been scarcely investigated until now. In order to better characterize these systems and subsequently to integrate these minerals into the long-term safety assessments, this work focuses on the investigation of the sorption behavior of U(VI), Np(V), and Nd(III) as analogue for An(III) onto the minerals orthoclase and muscovite, representing feldspars and mica, respectively. All investigations were performed under conditions relevant to the far field of a repository. In addition to the extensive characterization of the minerals, batch sorption experiments, spectroscopic investigations, and surface complexation modeling were performed to elucidate the uptake and speciation of actinides on the mineral surfaces. In addition, the influence of microorganisms naturally occurring on the mineral surfaces and the effect of Ca2+ on U(VI) uptake on the minerals was studied. The obtained sorption curves exhibit a similar characteristic for orthoclase and muscovite. As expected Nd(III) shows the highest amount of sorption followed by U(VI) and finally Np(V). With spectroscopic investigations of the aquatic U(VI) solution in presence of Ca2+, the Ca2UO2(CO3)3 complex could be identified. Furthermore, with spectroscopic methods the U(VI) surface species onto orthoclase could be characterized, of which a novel uranium-carbonate surface species was observed. Based on the results of batch experiments and spectroscopic methods new SCM parameters for the sorption of U(VI), Np(V), and Nd(III) onto orthoclase and for Np(V) and Nd(III) onto muscovite could be derived. SCM parameters for U(VI) sorption onto muscovite confirmed earlier investigations. The obtained SCM parameters increase the amount of data available for sorption processes onto feldspar and mica. With this the relevance of feldspars for the sorption of actinides and lanthanides could be shown. Thus, this work contributes to a better understanding of interactions of actinides and lanthanides, in particular U(VI), Np(V), and Nd(III), with mineral phases ubiquitous in the environment. This in turn adds confidence to long-term safety assessments essential for the protection of humans and the environment from the hazards of radioactive waste.

Σκοπός της εργασίας είναι η μελέτη της συμπεριφοράς προσροφημένων πολυηλεκτρολυτών. Συγκεκριμένα έγιναν μετρήσεις των δυνάμεων αλληλεπίδρασης μεταξύ των πολυμερικών αλυσίδων. Από τις μετρήσεις αυτές είναι δυνατή η εξαγωγή συμπερασμάτων για το πάχος του προσροφημένου πολυμερικού στρώματος, όπως και για το ποσοστό προσρόφησης των πολυμερών. Τα πολυμερή που μετρήθηκαν είναι αμφίφυλα δυσυσταδικά συμπολυμερή, αποτελούνται από ένα υδρόφοβο τμήμα που προσροφάται σε επιφάνειες και από ένα υδρόφιλο τμήμα. Κατά μήκος της αλυσίδας τους τα πολυμερή μας φέρουν φορτία (είναι σουλφονομένα) και για αυτό τον λόγο αποκαλούνται πολυηλεκτρολύτες. Εξετάζουμε τέσσερα διαφορετικά Μ.Β. (90Κ. 120Κ, 150Κ, 400Κ).Τα δείγματα υπό εξέταση είναι αραιά υδατικά διαλύματα (1/10000) των πολυμερών με την παρουσία ηλεκτρολύτη (άλατος) σε διάφορες συγκεντρώσεις. Τα αιωρήματα αυτά διοχετεύονται εντός κελίου στο οποίο βρίσκονται εμβαπτισμένες οι επιφάνειες προσρόφησης (μίκα). Αυτές με την σειρά τους είναι προσαρμοσμένες σε ημικυλινδρικούς φακούς που βρίσκονται σε διάταξη σταυρού. Δια μέσου των φακών διέρχεται εστιασμένη δέσμη φωτός, που οδηγείται σε φασματοσκόπιο. Εκεί αναλύεται και παρατηρούνται κροσσοί συμβολής. Με την βοήθεια της συμβολομετρίας μπορούμε να παρατηρήσουμε την μετακίνηση που υφίστανται οι φακοί , αλλά και την παρεμπόδιση που εμφανίζεται όταν αναπτύσσονται οι δυνάμεις. Οι δυνάμεις γίνονται μετρήσιμες από την κάμψη ενός ελάσματος που φέρει πάνω του προσαρμοσμένο τον ένα φακό. Τα αποτελέσματα των μετρήσεων μας δίνουν πολύτιμες πληροφορίες για την συμπεριφορά των πολυμερών. Στα κυριότερα αποτελέσματα, που μπορεί κανείς να αναφερθεί είναι η παρατηρούμενη εξάρτηση του πάχους του πολυμερικού στρώματος από το Μ.Β. των πολυμερών.(αύξηση του πάχους με ελάττωση του Μ.Β.) Επίσης παρατηρείται μία εξάρτηση του πάχους του πολυμερικού στρώματος από την μεταβολή της συγκέντρωσης του ηλεκτρολύτη στα διαλύματά μας. Για μεγάλα μοριακά βάρη παρατηρούμε ελάττωση του πάχους με την ελάττωση της συγκέντρωσης του άλατος. Ένα αξιοσημείωτο συμπέρασμα είναι το γεγονός ότι από την επεξεργασία των μετρήσεών μας φαίνεται να σχηματίζεται ένα πυκνό στρώμα κοντά στην επιφάνεια προσρόφησης από το οποίο προεξέχουν με μορφή ακροτενών πολυμερών οι αλυσίδες με μορφολογία βούρτσας. Η έλλειψη υστέρησης από τις μετρήσεις μας, επιβεβαιώνει το συμπέρασμα ότι έχουμε ακροτενή πολυμερή (πολυμερικές βούρτσες). Τέλος παρατηρούμε μονότονα απωστικές δυνάμεις μεταξύ των πολυηλεκτρολυτικών αλυσίδων. / The forces between adsorbed charged diblock copolymers were measured, by the use of the Surface Force Apparatus. Diblock copolymers forming a polymer brush structure were investigated in order to measure the adsorbed layer thickness and their behavior in salt solutions with different concentrations. As we investigate there is an interesting conformation related with the adsorbed layer. It seems to consist by two sections, an anchoring layer and a solvated brush in solution. The anchoring layer is formed from the hydrophobic blocks of the diblock polyelectrolytes. The hydrophilic blocks form a brush in solution. Positive counter ions that are found in conjunction with the negative charges on the polyelectrolyte disassociate in solution. There are as many counter ions as charges on the chain. The presence of salt in the solution means more disassociated ions in the solution. Changes to the salt concentration leads to changes to the forces as well as to the adsorbed layer. We investigate four different molecular weights of the sulfonated polyelectrolyte PtBS-NaPSS (90K, 120K, 150K, 400K) by changing the salt concentration. We find out that the adsorbed layer thickness decreases while the molecular weight increases. We also detect reduce to the layer thickness with salt concentration reduction. The adsorbed amount seems to reduce by increasing the molecular weight and increases by salt concentration reduction. Although the most important conclusion is the anchoring layer which forms a stiff layer very close to the substrate. Finally these polymeric systems can be used in numerous industrial applications as colloid stabilization, biocompatibilization, adhesion, and water treatment e.t.c.

Dans cette thèse on a étudié par diffraction des rayons X des polytypes à longue période de micas, qui sont des cristaux naturels formés en condition hors équilibre dans un système magmatique. Leur séquence d'empilement peut être considérée comme une combinaison plus ou moins complexe de trois polytypes à courte période 1M, 2M1 et 3T, appelés « structures de base ». L'objectif est d'obtenir les premiers affinements structuraux des ces polytypes avec attention particulière à la distribution des cations dans chaque feuillet, car, d'après la littérature, il existe vraisemblablement une relation entre cette distribution et le mécanisme de formation de ces polytypes. Plus de 120 cristaux ont été analysés, parmi lesquels deux polytypes, dont la période est formée respectivement par 4 et 5 feuillets (indiqués comme 4M3 et 5M3 respectivement en notation de Ramsdell), ont été sélectionnés. Grâce aux résultats de l'affinement, deux interprétations de formation sont possible pour le polytype 4M3, qui prennent en considération le fait que la séquence d'empilement peut-être formée par l'inter-croissance de deux sous-structures : une 3T avec une 1M ou deux sous-structures 2M1 ; dans le dernier cas il s'agit d'un exemple de « cell-twin ». Les résultats de l'affinement structural du polytype 5M3 ont permis de prouver pour la première fois la coexistence des feuillets de type M1 et M2, qui diffèrent pour la distribution cationique dans la couche octaédrique, dans le même polytype. La formation de ces polytype peut-être due à la combinaison de deux sous-structures de base et plusieurs interprétations sont possibles : 3T+1M, 3T+2M1, 1M+2M1, ou deux 1M. Une étude géologique a été effectuée pour reconstruire l'histoire de la rhyodacite contenant les polytypes à longue période. Cette roche s'est formée suite à un mélange de magma, comme indiqué par la présence de textures de déséquilibre de plusieurs minéraux, phénomène qui semble avoir un rôle important dans la formation des ces polytypes, en incrémentant l'activation et les interactions des spirales de croissance, mais aussi les interactions spirale-cristal et cristal-cristal. / We have studied by X-ray diffraction long period polytypes of micas, that are natural crystals formed far from the equilibrium condition in a magmatic system. Their stacking sequence can be considered as a more or less complex combination of three short polytypes 1M, 2M1 and 3T, called "basic structures". The aim was to obtain the first structural refinements of these polytypes, with special attention to the cationic distribution in the octahedral sheet, because, according to the literature, there seems to be a relation between this distribution and the formation of these polytypes. More than 120 crystals have been analysed, and two polytypes have been chosen, whose period is formed respectively by 4 and 5 layers (indicated as 4M3 and 5M3 respectively in Ramsdell notation). The refinement results suggest two interpretations for the formation of the 4M3 polytype, both indicating that the stacking sequence can be formed by the inter-growth of two sub-structures: a 3T with a 1M or two 2M1 sub-structures; the last case is an example of "cell twin". The results of the structural refinement of the 5M3 polytype show for the first time the coexistence of M1 and M2 types of layer, which differ for the cation distribution in the octahedral sheet, in the same polytype. The formation of this polytype can be due to the combination of two basic sub-structures and several interpretations are possible: 3T+1M, 3T+2M1, 1M+2M1, or two1M. A geological study has been done to reconstruct the history of the rhyodacite containing the long period polytypes. This rock is formed after a magma mixing, as showed by the presence of the disequilibrium textures of several minerals; this phenomenon seems to play a fundamental role for the formation of these polytypes, increasing the spiral?s activation and interactions, but also the spiral-crystal and crystal-crystal interactions.

Made available in DSpace on 2015-04-14T13:46:28Z (GMT). No. of bitstreams: 1 399151.pdf: 10146373 bytes, checksum: 195e7a855cb3087d79fbd5b86d2306ef (MD5) Previous issue date: 2008-01-14 / A presente disserta??o apresenta o estudo de uma cole??o de cer?mica pintada Tupiguarani, proveniente da regi?o de Itapiranga, SC. O objetivo do trabalho ? demonstrar, a partir da an?lise da decora??o cer?mica, que o modo normativo como os motivos decorativos s?o constru?dos, podem indicar a exist?ncia de uma tradi??o cultural, que demonstra uma tend?ncia ? prescritividade mas que essa tradi??o cultural n?o ? t?o r?gida, assinalando que ela tamb?m pode ser performativa em determinadas ocasi?es. Nesse sentido, a cultura material ? um bom indicador para se verificar tal possibilidade. Para tanto, os motivos decorativos analisados nessa cole??o, foram comparados com outras duas cole??es, Florian?polis, SC e Candel?ria, RS. A compara??o demonstrou que, al?m deles serem bastante similares, havia algumas varia??es, muito sutis, na constru??o dos motivos. Cogita-se a possibilidade de que tais varia??es representem parcialidades ?tnicas entre os grupos de uma mesma tradi??o cultural, afastadas regionalmente. Para expressar isso se usou, neste estudo, a express?o regionalismos culturais. No entanto, para que se possam apontar os regionalismos culturais, antes ? preciso compreender como as manifesta??es art?sticas, dentro das sociedades ind?genas funcionam, verificando a rela??o da comunidade ind?gena com a arte. Acredita-se que seja poss?vel relacionar a arte da confec??o e da decora??o cer?mica como uma esp?cie de comunica??o n?o-verbal, ou uma linguagem visual iconogr?fica, capaz de informar sobre como a sociedade pensa, age e compreende o mundo em sua volta.