A number of leaks of radioactive liquors to ground are known to have occurred from several plant buildings, vaults and disposal trenches within and around the Separation area at the Sellafield nuclear site over the past 50 years1. The most significant of these leaks have occurred from the Magnox Silo, the Caesium Extraction Plant, the Magnox Reprocessing Pump House, the Sludge Storage Tanks, the Burial Pits and the Medium Active Evaporation and Thermal Denitration Plant. The radioactive contamination will be accompanied by other components of spent fuel reprocessing, including inorganic salts from neutralised acids, solvents and other organic compounds along with the typical contaminants commonly associated with large industrial activity such as heavy metals, fuel, oils, degreasing agents etc. The research in this thesis describes the effects of common industrial contaminants on the behaviour of Cs and Sr sorption to bentonite and montmorillonite clay minerals. Batch sorption experiments of Cs and Sr uptake onto bentonite and montmorillonite in a number of complex systems were investigated as follows: 1. Initial batch sorption experiments investigating the normal behaviour of the clay minerals. 2. Introduction of anthropogenic organic ligands EDTA, NTA and picolinic acid into the system and their influence on Sr and Cs uptake. 3. Time dependent studies investigating the effect that residence time of the anthropogenic organic ligands has on the sorption properties of montmorillonite and bentonite. 4. Quaternary systems where simulant Magnox sludge equilibrated water, at a number of concentrations, was introduced to ternary systems containing anthropogenic organic ligands. 5. Time dependent studies investigating the effect of hydrocarbons TCE, toluene and naphthalene on the uptake of Cs and Sr to bentonite and montmorillonite. The batch sorption experiments show that the presence of anthropogenic organic ligands reduces the uptake of Cs and Sr by both montmorillonite and bentonite. It is also shown that the presence of simulant Magnox sludge in quaternary systems can also reduce the uptake of Cs and Sr, with significant reductions in sorption observed for Sr sorption in EDTA quaternary systems. Further, the uptake of Cs and Sr to bentonite and montmorillonite appears to decrease with increasing anthropogenic organic ligand residence time. This suggests that the ligands are altering the surface of the clay minerals reducing the number of available binding sites. The influence of hydrocarbons shows a significant decrease in sorption after 3 months for Cs and Sr sorption to montmorillonite. There were no further significant changes for all other hydrocarbon systems investigated.

Géosynthétiques bentonitiques (GCLs) sont matériaux synthétiques composées par un noyau de bentonite sodique ou calcique, en poudre ou en granulats, liés à un ou plus couches de géosynthétiques (geotextiles ou geomembranes en générale). Les GCLs peuvent être aiguillettes, cousus, liés par adhésive, entre autres. Lorsque le GCL est confinée et hydratée, il présente de bonnes propriétés d'étanchéité pour accomplir la fonction de barrière. Sa performance dépend, généralement de la conductivité hydraulique de la bentonite. Grâce à leur faible perméabilité, les GCLs sont souvent installés au fond ou couverture des Installations de Stockage de déchets (ISD) associés avec l'argile compactée (CCL) ou avec la geomembrane (GM). Des études précédentes ont investigué les facteurs qui affectent la fuite de gaz/liquide au travers les GCLs ou les étanchéités composites. Malgré la nature de la bentonite soit si importante pour la perméabilité des GCLs, il n'y a pas dans la littérature concernant l'influence de la nature de la bentonite dans la fuite de gaz au travers les GCL ou la fuite de liquide au travers les étanchéités composites. C'est pour quoi cette étude s'intéresse. On propose d'étudier également l'effet du procès de manufacture du GCL dans l'écoulement de liquide et transmissivité de l'interface GM-GCL. Deux études sont été menés : (i) investigation de la perméabilité aux gaz des GCL ; (ii) investigation du transfert de liquide au travers des étanchéités composites GM-GCL-CCL du a un endommagement dans la GM. Pour la première étude un équipement proposé récemment, basée sur la méthode de chute de pression a été utilisé pour mesurer la perméabilité aux gaz des GCLs. Trois GCLs cousus à base de bentonites de différentes natures (sodique naturelle, calcique naturelle et calcique activée) ont été testés. Les résultats indiquent que la teneur en eau gravimétrique nécessaire pour atteindre une certaine valeur de perméabilité dépend de la bentonite. Concernant la teneur en eau volumique, pratiquement la même relation a été obtenue, indépendamment de la bentonite. D'autres facteurs ont affecté plus significativement la perméabilité au gaz des GCLs : la dessiccation du au flux de gaz peut causer l'augmentation de la perméabilité et compromettre la performance du GCL comme barrière étanche. La deuxième étude s'est concentré dans l'investigation de l'influence des caractéristiques du GCL sur l'écoulement de liquide au travers une étanchéité composite.GM-GCL-CCL. Quatre types de GCLs avec deux procès de manufacture (aiguilleté ou cousu) et deux natures de bentonite (sodique naturelle ou calcique naturelle) ont été testés. Les résultats indiquent que la nature de la bentonite n'affecte le flux que pendant le régime transitoire. Les valeurs de transmissivité de l'interface GM-GCL ont été calculées par une solution analytique qui a également possibilité des prédictions du débit de fuite au travers des étanchéités composites en configurations typiques du fond des ISD. Les résultats indiquent une faible influence de la nature de la bentonite dans l'écoulement de liquide au travers les étanchéités composites. Au même temps on a note une certaine influence des chemins préférentielles de flux, notamment pendant le régime transitoire.

Synthetic polymer fluids have been used as an alternative to conventional bentonite slurries for the excavation of foundation elements over the last two decades. Thus far their use has excited polarised views in the industry – some construction professionals avoid using them after hearing ‘horror stories’ about past failures whereas others believe that they are the future of support fluids because of the many benefits that they can offer. This situation has been found to be mainly due to a lack of understanding of what polymers really are and their properties. To address this issue, the various polymer products currently available in the market have been categorised based on their intended functions, and the fundamental properties of some of them have been characterised. The research showed that significant difference exists between polymers even of the same chemical family. Based on a series of rheological experiments, it was found that the properties of polymer fluids are highly dependent on the governing shear rate, time, and a range of site dependent factors. The research also showed that the current procedure for the interpretation of viscosity data is incorrect. After an analysis of the properties of currently available polymers, the latter part of the thesis describes a field trial carried out at a site in Stratford, East London. The aims of the trial were twofold: to compare the performance between piles constructed using bentonite and polymer fluids, and to assess the effect of extended pile bore open time for pile bores supported by polymers. From the results, it was found that the polymer piles showed much stiffer load–settlement response than the bentonite pile, and that a pile bore open time of up to 26 h had no adverse effect on the pile performance. The load test results have been carefully back-analysed using a range of methods. It was found that, compared to their bentonite counterparts, polymer fluids can improve the interface shearing resistance with Thanet Sand and the shear modulus of the Lambeth clay.

The influence of temperature and hydration on the long term stability of the buffer material was studied during two experimental studies - "Mock-Up-CZ" experiment and "Long-term stability of engineering barriers" project. The objectives of these studies is to identify mineralogical, chemical and geochemical changes and describe transformation processes in the bentonite materials due to heating and interaction with various saturation media (with different chemical composition) under controlled laboratory and in situ conditions. The Rokle bentonite suitability for its use in the Czech deep repository of high-level radioactive waste was investigated. Mineralogical changes in the bentonites were evaluated by X-ray diffraction. The material of the barrier of the Mock-Up-CZ experiment is a mixture of non­activated Rokle bentonite (85 vol.%), quartz sand (10 vol.%) and graphite (5 vol.%). The barrier has been subjected to thermal stress (up to 90 řC) and synthetic granitic water for 45 months. No sample from 70 analysed samples taken at different depth levels and distances from the source of the heat and/or water showed measurable transformation of original smectites. Newly formed gypsum bordered by illite aureole was detected in the upper part of the experimental set-up (backfill samples), i.e. in the...

Resumo: Este trabalho teve como objetivo o desenvolvimento das técnicas fundição de semicubos do trem de pouso principal do cargueiro C-115 Buffalo da Força Área Brasileira, pelo processo de fundição de liga de magnésio em moldes de areia a verde para atender as necessidades emergenciais nas atividades de apoio logístico, tático e transporte. Por ser um item estrutural cujas exigências em relação às propriedades de engenharia e segurança são rigorosas, foi necessário o desenvolvimento de técnicas de fundição diferenciadas para a obtenção do modelo com suas respectivas superespessuras de contração e usinagem; ângulos de saída; sistemas especiais de canais de alimentação; molde preparado com areia sintética, bentonita, enxofre, ácido bórico e água; magnésio, alumínio, zinco e alumínio-manganês de grau metalúrgico para a obtenção da liga; tratamento e refino do banho metálico, técnica de vazamento com frentes de alimentação simétricas; controle de qualidade por meio de inspeção visual, análise da composição química e metalográfica das fases e constituintes da liga, ensaios mecânicos e radiográficos para qualificação do fundido, conforme padrões aeronáuticos. Os ensaios apresentaram resultados cujos valores obtidos foram comparados com os padrões aeronáuticos internacionais, permitindo viabilizar a transferência desse desenvolvimento para o processo produtivo de forma a atender necessidades emergenciais e estimular a evolução do setor aeronáutico do País. / Abstract: This work had as objective the development of the techniques of semicubes casting of the main landing gear of the C-115 Buffalo freighterm from Brazilian Air Force, by the process of magnesium alloy casting in green sand molds to attend to the emergent necessities in the activities of logistic, tactical support and air service. The creation of the Project of Nationalization of Aeronautical Components was necessary for the maintenance of the operationalization of the aircraft and to prevent the collapse of the fleet. Aeronautical wells are a structural item whose requirements in relation to the security and engineering properties are rigorous, it was necessary the development of differentiated techniques of casting for the attainment of the model with its respective superthicknesses contraction adn machining; pattern draft; special gate systems; mold prepared in synthetic sand, bentonite sand, sulphur, acid boric and water; magnesium, aluminium, zinc and aluminum-manganese of metallurgical degree for obtention of the alloy; treatment and refining of the metallic bath, pouring technique with symmetrical fronts of feeding; quality control by means of visual inspection, analysis of the chemical and metallographic composition of the phase and mechanical and radiografic constuent of the alloy, assays for qualification of the casting, as aeronautical standards. The assays had presented resulted whose gotten values had been compared with international aeronautical standards, allowing to make possible the transference of this devolopment for the productive process to pay attention to emergency necessities and to stimulate the evolution of the aeronautical sector of the Country. / Orientador: Valdir Alves Guimarães / Coorientador: Francisco Cristovão Lourenço de Melo / Banca: Carlos Kiyan / Banca: Mirian de Lourdes Noronha Motta Melo / Mestre

A conformação em torno elétrico é um dos métodos utilizados na fabricação de peças cerâmicas, principalmente utilitários e decorações. Porém nem todas as massas cerâmicas possuem plasticidade adequada para serem torneadas. A porcelana fosfática é um desses exemplos devido à composição de 50 % de cinza de ossos bovinos, 25 % de caulim e 25 % de feldspato. Uma massa de porcelana comercial de alta temperatura, branca e com boa plasticidade foi a referência de massa propícia para se trabalhar no torno elétrico e foi feito a caracterização desse material como distribuição granulométrica, picnometria a gás, composição química por fluorescência de raio X (FRX) e difração de raio X (DRX). Os mesmos métodos de caracterização foram feitos na porcelana fosfática. O limite de Atterberg foi utilizado como técnica para medir os teores de água das massas e a reometria por squeeze flow foi o método de análise para diferenciar massas cerâmicas plásticas e não-plásticas. Testes no torno elétrico foram feitos para concluir sobre melhoria na plasticidade da porcelana fosfática através da adição de aditivo como bentonita e polímero à base de éter celulose (MHEC). Adição de 4 % de bentonita na porcelana fosfática aumentou o índice de plasticidade de Atterberg em cerca de 100 % e as curvas de squeeze flow ficaram próximos das curvas do material de referência, apresentando assim plasticidade suficiente para fabricar peças no torno elétrico. / Throwing on electric wheel is one of techniques used to forming ceramic wares as tableware and decorative. However, ceramic body needs to have enough plasticity for hands working on throwing wheel. The phosphatic porcelain composition is 50 % of bone ash, 25 % of kaolin and 25 % of feldspar and generally has low plasticity. A commercial porcelain for throwing on the electric wheel was used as default and compared with the phosphatic porcelain. Raw material characterization as particle size distribution analysis, gas pycnometry, chemical composition by x-ray fluorescence (XRF), zeta potential and x-ray diffraction (XRD) was doing to compare both porcelains. Atterberg limits were used to measure moisture content of ceramic body and rheometry was evaluated by squeeze flow technique to determine the viscosity difference between porcelain and phosphatic porcelain. Test on the throwing wheel were made to verify plasticity improvement by addition of bentonite or a polymer based on ether cellulose (MHEC). The 4 % of bentonite addition increased about 100 % the Atterberg limit and the consequent change in the squeeze flow curves demonstrate to be similar with reference and with enough plasticity to throwing on the electric wheel. Keyword: Phosphatic porcelain. Plasticity. Throwing wheel. Bentonite. Squeeze flow.

Novos materiais obtidos a partir de polímeros biodegradáveis são uma alternativa para a redução do impacto ambiental causado pelo uso excessivo de polímeros derivados do petróleo. Atualmente, vários estudos têm sido realizados na busca de matéria-prima para o desenvolvimento de filmes biodegradáveis, com boa viabilidade técnica e econômica. Dentre estas matérias-primas, destacam-se as que são provenientes de fontes renováveis, de baixo custo e que tenham grande importância econômica e ambiental, como, por exemplo, o amido, as argilas, e a quitosana. Nos filmes que preparamos, adicionamos como plastificante a glicerina, um subproduto do biodiesel, e que contribui para maior estabilidade térmica dos filmes, em conjunto com o amido. O propósito deste trabalho foi o preparo de um biopolímero a base de quitosana e argila com propriedades de nanocompósitos, pois estes materiais costumam exibir propriedades físico-químicas diferenciadas em relação a outros materiais, devido à redução no seu tamanho. Sendo assim, através do estudo e comparação de duas argilas esmectíticas sódicas naturais, Bentogel e Corral, pôde-se observar o comportamento dos filmes formados em presença de amido e glicerina. Os filmes obtidos, através do método de dispersão em solução do polímero, foram caracterizados através das técnicas de DRX, MEV, IV, TG e DSC. Os resultados obtidos mostraram a formação de filmes nanocompósitos esfoliados de boa estabilidade térmica. / New materials made from biodegradable polymers are an alternative to reducing the environmental impact caused by excessive use of polymers derived from petroleum. Currently, several studies have been conducted in search of raw material for the development of biodegradable films, with good technical and economic feasibility. Among these materials, we highlight those that are from renewable resources, low cost and have great economic and environmental importance, such as, starch, clays, and chitosan. In preparing films, we added glycerol as a plasticizer, a byproduct of biodiesel, and contributes to better thermal stability of the films, together with starch. The purpose of this study was the preparation of a biopolymer based on chitosan and clay nanocomposites properties, because these materials tend to display different physico-chemical properties compared to other materials because of the reduction in size. Thus, through the study and comparison of two natural sodium smectite clays, Bentogel and Corral, it was observing the behavior of films formed in the presence of starch and glycerol. The films obtained by the method of dispersion in the polymer solution, were characterized by techniques of XRD, SEM, FTIR, TG and DSC. The results obtained showed the formation of exfoliated nanocomposites films and good thermal stability.

A conformação em torno elétrico é um dos métodos utilizados na fabricação de peças cerâmicas, principalmente utilitários e decorações. Porém nem todas as massas cerâmicas possuem plasticidade adequada para serem torneadas. A porcelana fosfática é um desses exemplos devido à composição de 50 % de cinza de ossos bovinos, 25 % de caulim e 25 % de feldspato. Uma massa de porcelana comercial de alta temperatura, branca e com boa plasticidade foi a referência de massa propícia para se trabalhar no torno elétrico e foi feito a caracterização desse material como distribuição granulométrica, picnometria a gás, composição química por fluorescência de raio X (FRX) e difração de raio X (DRX). Os mesmos métodos de caracterização foram feitos na porcelana fosfática. O limite de Atterberg foi utilizado como técnica para medir os teores de água das massas e a reometria por squeeze flow foi o método de análise para diferenciar massas cerâmicas plásticas e não-plásticas. Testes no torno elétrico foram feitos para concluir sobre melhoria na plasticidade da porcelana fosfática através da adição de aditivo como bentonita e polímero à base de éter celulose (MHEC). Adição de 4 % de bentonita na porcelana fosfática aumentou o índice de plasticidade de Atterberg em cerca de 100 % e as curvas de squeeze flow ficaram próximos das curvas do material de referência, apresentando assim plasticidade suficiente para fabricar peças no torno elétrico. / Throwing on electric wheel is one of techniques used to forming ceramic wares as tableware and decorative. However, ceramic body needs to have enough plasticity for hands working on throwing wheel. The phosphatic porcelain composition is 50 % of bone ash, 25 % of kaolin and 25 % of feldspar and generally has low plasticity. A commercial porcelain for throwing on the electric wheel was used as default and compared with the phosphatic porcelain. Raw material characterization as particle size distribution analysis, gas pycnometry, chemical composition by x-ray fluorescence (XRF), zeta potential and x-ray diffraction (XRD) was doing to compare both porcelains. Atterberg limits were used to measure moisture content of ceramic body and rheometry was evaluated by squeeze flow technique to determine the viscosity difference between porcelain and phosphatic porcelain. Test on the throwing wheel were made to verify plasticity improvement by addition of bentonite or a polymer based on ether cellulose (MHEC). The 4 % of bentonite addition increased about 100 % the Atterberg limit and the consequent change in the squeeze flow curves demonstrate to be similar with reference and with enough plasticity to throwing on the electric wheel. Keyword: Phosphatic porcelain. Plasticity. Throwing wheel. Bentonite. Squeeze flow.

O processo de adsorção vem sendo utilizado como uma técnica eficaz para a remoção de íons metálicos em efluentes. Neste trabalho são apresentados os estudos para avaliar da capacidade de adsorção de cobalto em caulinita, um adsorvente de baixo custo, visando à remoção deste íon de soluções aquosas. Foi analisada a área superficial específica (S) em 25 amostras de materiais preparadas de diferentes modos: caulinita, bentonita e carvão ativado e, misturas de caulinita-bentonita e caulinita-carvão ativado. Estas misturas foram preparadas pela adição de 10, 20, 30, 40 e 50% de carvão ativado ou bentonita à caulinita. As amostras de caulinita-carvão ativado e caulinita in natura foram calcinadas a 600 e 1000 °C por 4 horas. Foi escolhida para os testes de adsorção a mistura de caulinita com 10% de carvão ativado por apresentar a melhor relação custo benefício em relação à S. Os parâmetros de adsorção investigados nesta mistura foram: tempo de contato, pH, concentração inicial de soluto, competição iônica e força iônica. Verificou-se que o tempo de contato e o pH otimizados para o propósito do trabalho foram 30 min e pH 6. Nestas condições a eficiência de remoção do íon cobalto da solução foi superior a 80%. Verificou-se que a presença de íons Cr e Zn, bem como o aumento da força iônica diminuem a capacidade de adsorção do Co na mistura adsorvente. As isotermas de Langmuir e Freundlich apresentaram R2 iguais a 0,906 e 0,597, respectivamente. Os parâmetros determinados nestas isotermas indicaram um processo espontâneo, ou seja, energeticamente favorável, para a adsorção do Co nas condições e que foram realizadas este trabalho. / The adsorption process has been used as an efficient technique for the removal of metallic ions in industrial effluent. In this work, it is presented the studies to evaluate the adsorption capacity of cobalt in kaolinite, a low cost adsorbent, aiming at the removal of this ion from aqueous solutions. The specific surface area (S) was analyzed in 25 samples prepared in different ways: kaolinite, bentonite and activated carbon and, mixtures of kaolinite-bentonite and kaolinite-activated carbon. These mixtures were prepared by adding to kaolinite 10, 20, 30, 40 or 50% of activated charcoal or bentonite. Samples of kaolinite-activated charcoal mixture and raw kaolinite were also calcined at 600 and 1000 °C for 4 hours. The adsorption parameters investigated for these adsorbents were: contact time, pH, solute initial concentration, ionic competition and ionic strength. It was found that the optimized contact time and pH, for the purpose of this work, were 30 min and pH 6. Under these conditions the cobalt ion removal efficiency was greater than 80%. It was verified that the presence of Cr and Zn ions, as well as the increase in ionic strength caused a decrease in the adsorption capacity of Co in the adsorbent mixture. The Langmuir and Freundlich isotherms presented R2 equal to 0.906 and 0.597, respectively. The parameters determined by these isotherms indicated a spontaneous process, i.e., energetically favorable, for the adsorption of Co under the conditions that this work was carried out.

O sucesso da conclusão de um poço por perfuração e o custo do projeto estão relacionados às propriedades dos fluidos de perfuração. O estudo experimental foi realizado a partir da determinação e análise das curvas de tensão de cisalhamento versus taxa de deformação de suspensões aquosas de bentonita e carboximetilcelulose com diferentes concentrações de NaCl. Investigou-se, inicialmente, o comportamento reológico de suspensões de carboximetilcelulose 0,5% (em massa) com concentrações de sal, NaCl de 0 a 4% (em massa), para temperaturas variando de 14 a 26ºC. Os resultados experimentais possibilitam a caracterização reológica destas soluções como fluidos pseudoplásticos e indicam que a adição de NaCl em soluções com CMC alteram significativamente o comportamento reológico desse tipo de solução. Numa segunda etapa, estudou-se o comportamento reológico de suspensões de bentonita e carboximetilcelulose em diferentes concentrações de sal, NaCl. Empregaram-se soluções contendo 4,8 % de bentonita, 0,5 % de carboximetilcelulose e concentrações de 0 a 4% de NaCl. Constata-se o comportamento tixotrópico destas suspensões e a forte dependência com a concentração de sal. O estudo foi complementado com uma análise comparativa dos resultados do comportamento reológico obtidos por reômetro de cilindros coaxiais modelo Brookfield e o viscosímetro FANN 35 A, usualmente empregado na análise de fluidos de perfuração. O equacionamento do escoamento do fluido nos aparelhos permitiu uma interpretação mais detalhada dos valores descritos na norma, obtendo-se uma equivalência dos valores medidos em campo com os obtidos no reômetro Brookfield apesar de as faixas de operação de taxas de deformação serem distintas. / The properties of drilling fluids have a very significant effect on the successful of a well completion and the project costs. The experimental study was conducted based on the determination and analysis of the curves of shear stress and shear rate of aqueous suspensions composed of bentonite and carboxymetil cellulose at different concentrations of NaCl. The rheological behaviour of carboxymetil cellulose suspensions 0.5% w/w at NaCl concentrations in the range of 0 to 4% w/w from 14 to 26°C was studied. The experimental results allow the rheological characterization of these solutions as pseudoplastic fluid. It was observed that the addition of NaCl to CMC solutions changes its rheological behaviour significantly. In addition, the rheological behaviour of 4,8% bentonite suspensions with 0,5% carboxymethyl cellulose at different concentrations of NaCl in the range of 0 to 4% was studied. The characterization of these solutions showed thixotropic behaviour and a strong dependence on the salt concentration. The study was complemented with a comparative analysis of the results obtained by using a coaxial cylinders rheometer model Brookfield and the FANN Model 35 A viscometer, usually employed in drilling fluids analysis. The analytical solutions allowed a more detailed interpretation of the values described in the standard resulting in an equivalence between the measured values obtained in the field and in the Brookfield rheometer despite the differents shear rate ranges.