Dissolution of the UO2 matrix is one of the potential routes for radionuclide release in a future deep geological repository for spent nuclear fuel. This doctoral thesis focuses on interfacial reactions of relevance in radiation-induced dissolution of UO2 and is divided in two parts: In the first part, we sought to explore the effects of solid phase composition: The impact of surface stoichiometry on the reactivity of UO2 towards aqueous radiolytic oxidants was studied. H2O2 reacts substantially faster with stoichiometric UO2 than with hyperstoichiometric UO2. In addition, the release of uranium from stoichiometric UO2 is lower than from hyperstoichiometric UO2. The behavior of stoichiometric powder changes with exposure to H2O2, approaching the behavior of hyperstoichiometric UO2 with the number of consecutive H2O2 additions. The impact of Gd-doping on the oxidative dissolution of UO2 in an aqueous system was investigated. A significant decrease in uranium dissolution and higher stability towards H2O2 for (U,Gd)O2 pellets compared to standard UO2 was found. In the second part, we sought to look at the effect of external factors: The surface reactivity of H2 and O2 was studied to understand the overall oxide surface reactivity of aqueous molecular radiolysis products. The results showed that hydrogen-abstracting radicals and H2O2 are formed in these systems. Identical experiments performed in aqueous systems containing UO2 powder showed that the simultaneous presence of H2 and O2 enhances the oxidative dissolution of UO2 compared to a system not containing H2. The effect of groundwater components such as bentonite and sulfide on the oxidative dissolution of UO2 was also explored. The presence of bentonite and sulfide in water could either delay or prevent in part the release of uranium to the environment. The Pd catalyzed H2 effect is more powerful than the sulfide effect. The poisoning of Pd catalyst is not observed under the conditions studied. / <p>QC 20170421</p>

Este trabalho apresenta um estudo sobre a influência do acréscimo de 4% de bentonita sódica, da anisotropia inerente, produzida pela compactação, e do estado de tensões no comportamento hidráulico de um solo areno-argiloso encontrado na região Costeira Sul do estado do Rio Grande do Sul. Neste estudo, busca-se não somente viabilizar o emprego do referido solo como barreira mineral em obras de proteção ambiental, mas também verificar seu desempenho, quando misturado ao aditivo, perante as condições de fluxo de água experimentalmente impostas, antes e depois da fase de consolidação, nas direções normal e paralela aos planos de orientação preferencial das partículas e poros a elas associados. Com o escopo de atingir tais objetivos, executaram-se dois métodos de compactação (ensaios Mini e Proctor Normal) para a moldagem de corpos de prova com planos de orientação preferencial das partículas ou de compactação normais (&#952; = 90º) e paralelos (&#952; = 0º) à vertical. As amostras de solo e mistura foram compactadas na energia Proctor Normal e submetidas aos ensaios triaxiais de condutividade hidráulica, em permeâmetro de parede flexível à carga constante, e de consolidação. A técnica permitiu determinar a condutividade hidráulica dos materiais para vazões desenvolvidas preferencialmente nas direções normal e paralela aos planos de compactação dos corpos de prova. Os resultados demonstram que o acréscimo de 4% de bentonita sódica provoca uma redução da condutividade hidráulica do solo, que supera o valor mínimo exigido de 10-9 m/s em ambas as direções de fluxo, habilitando o emprego deste material para a aplicação prevista. Além disso, verifica-se que a compactação confere um comportamento hidráulico anisotrópico ao solo, no entanto, quando misturado ao aditivo no teor indicado, seu comportamento se modifica, tornando-se mais isotrópico. Os resultados ainda revelam que o efeito da tensão de confinamento sobre a diminuição da condutividade hidráulica do solo e da mistura se mostra significativo para ambas as modalidades experimentais. / This work proposes to evaluate the influence of the inherent anisotropy, promoted by compaction, and the confining pressure on the hydraulic behavior of a clayey sand from the south coastal region of Rio Grande do Sul state (Brazil), in pure condition and mixed with 4% sodium bentonite content. This study aims to make possible the use of this soil as mineral barrier in environmental protection works, as well as evaluating the hydraulic behavior of both materials (soil and mixture), before and after the consolidation stage, when developed water flow conditions in the perpendicular and parallel directions in relation to the compaction planes of the compacted samples. In order to achieve these objectives, was performed a Standard Proctor Test and an alternative compaction test (Mini-test), intending to get specimens with compaction planes in the perpendicular (&#952;= 90º) and parallel (&#952; = 0º) directions in relation to the vertical. The soil and mixture samples were compacted at Normal Proctor energy and subjected to the triaxial consolidation and hydraulic conductivity tests. The technique allowed to evaluate the hydraulic conductivity of the specimens for flow perpendicular and parallel to the directions of the compaction planes. The results indicate that the increase of 4% sodium bentonite content reduces the hydraulic conductivity of the soil in both flow directions, making it suitable for employment as protection system in sanitary landfills or in other similar applications. Furthermore, it is observed that compaction provides anisotropic hydraulic behavior to the soil, however, when it is mixed with 4% sodium bentonite content, its behavior changes, becoming more isotropic. The results also reveal that the effect of the confining pressure on the decrease in hydraulic conductivity of the soil and mixture is significant in both adopted experimental conditions.

Made available in DSpace on 2017-07-24T19:37:53Z (GMT). No. of bitstreams: 1 Caetano, Elenice Hass.pdf: 4149328 bytes, checksum: b6eb52279243079ec9a5d88b5028ae4c (MD5) Previous issue date: 2015-03-02 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Clay minerals are hydrated silicates of Aluminum, Iron and Magnesium that has lamellar structure (phyllosilicates) composed by continuous SiO4 tetrahedral layers connected to bi and tri metals hydroxide octahedral layers. The layers are continuous and hexagonally ordered regarding to crystallographic axis a and b. The arrange of clays minerals determines the type of clay mineral as 1:1 or 2:1. The 2:1 clays minerals are divided in groups: Vermiculite, Mica, Chlorite, Saponite, Paligorskita and the Smectite group. Among the Smetectite group stands out the Bentonite, the most abundant clay mineral and that shows 2:1 phyllosilicates structure composed by two silicate tetrahedral layers and one alumina octahedral layers, both connected by oxygen atoms in common. The great technological interest in these clay results of the high cation exchange capacity, swelling by water and low size of crystals. Such properties favor the clays modification to discovery new applications. Thus, the clays minerals are an essential step for the discovery of technological applications as well as the fundamental properties of clays. In this work, were characterized four samples of clays through of X-Ray Diffraction, X-Ray Fluorescence Spectroscopy, Fourier Transform Infrared Spectroscopy, 27Al NMR-MAS and Field Emission Scanning Electron Microscopy. The obtained results indicate the predominance of Smectite phase in clays due to high swelling capacity and cation exchange observed. The predominance of Smectite phase was confirmed by XRD, XRF and FTIR, which also indicates the presence of quartz and other minerals. Were also evaluated the presence of organic compounds in the interlayer space of modified clays and was noted that have not changes in their crystalline structures, based on FTIR and 27Al NMR-MAS results. The SEM-FEG micrography confirms the irregularity of cluster size, according to expect to bentonite clays. The performed characterizations for these clays minerals determine its elementary composition and makes possible distinguish the four samples according to its place of origin by the amount of impurities, as well as the prevalence of smectite phase. The characterization analysis were used to quantification of fundamental properties and to evaluated the organic compounds presence in interlayer space through of delocalization of the most intense peak in 2θ angle. The obtained results are useful for the benefit of industrial areas such as pharmaceutical, food, environmental and others, once the mineral clays properties can be improved when properly identified and quantized. / Argilas são materiais naturais, terrosos, considerados finos grãos que contém partículas com diâmetro inferior a 2 μm e, quando umedecidos com água, apresentam plasticidade. São constituídas essencialmente por argilominerais (filossilicatos) e por matéria orgânica, sais solúveis, minerais como calcita, pirita, gibsita, quartzo entre outras impurezas. Bentonita, conhecida como o argilomineral mais abundante do grupo da esmectita, pertence ao grupo dos filossilicatos 2:1, sua estrutura cristalina é constituída por duas folhas tetraédricas de sílica com uma folha central octaédrica de alumina, ambas unidas por átomos de oxigênio em comum. O grande interesse tecnológico nessa argila está ligado à sua alta capacidade de troca catiônica, intumescimento pela água e às pequenas dimensões dos cristais, cujos fatores favorecem a modificação das argilas para a descoberta de novas aplicações. Para tanto, a caracterização da argila é uma etapa primordial para aplicações tecnológicas bem como suas propriedades fundamentais como alta adsortividade, alta capacidade de troca catiônica, capacidade de inchamento e alta propriedade de barreira. No presente trabalho, foram caracterizadas quatro amostras de argilas Bentonítas de diferentes procedências, sendo duas na sua forma pura e duas organofílicas pelas respectivas técnicas: difração de raios X, fluorescência de raios X, Espectroscopia Vibracional de Absorção na Região do Infravermelho, Ressonância Magnética Nuclear do estado sólido - 27Al RMN-MAS, Microscopia Eletrônica de Varredura com Efeito de Campo. Os resultados obtidos indicaram a predominância da fase esmectita evidenciada pela alta capacidade de inchamento e alta capacidade de troca catiônica. Além disso, os resultados de DRX, FRX e FTIR também evidenciaram a predominância da fase esmectita, bem como a presença de quartzo e outros minerais. Também foi possível avaliar a presença de compostos orgânicos no espaço interlamelar das argilas organofílicas e notou-se que não houve alterações em suas estruturas cristalinas, informações estas corroboradas pelas técnicas de FTIR e 27Al RMN-MAS. As micrografias obtidas por MEV-FEG puderam confirmar a irregularidade de tamanho dos aglomerados de partículas típico de bentonitas. As Caracterizações obtidas para as argilas determinaram sua composição elementar, sendo possível distinguir argilas de diferentes procedências pela quantidade de impurezas, bem como a predominância da fase esmectita. Além disso, por meio da caracterização também foi possível determinar a quantificação de suas propriedades fundamentais, e também confirmar a presença de composto orgânico no espaço interlamelar por meio do deslocamento do pico de maior intensidade do ângulo 2θ. Essas caracterizações podem ser utilizadas em benefício das áreas industriais, como farmacêutica, alimentícia, ambientais entre outras, podendo ser aprimoradas as propriedades quando bem identificadas e quantizadas.

Dans le but de vérifier l'efficacité des dispositifs de scellement ou des barrières ouvragées dans le stockage géologique des déchets radioactifs, l'Institut de Radioprotection et de Sûreté Nucléaire (IRSN) a mis en œuvre le projet expérimental SEALEX (SEALing performance EXperiments) auquel ce travail est étroitement lié. Dans le cadre de ce projet, des essais in-situ sont effectués à l'échelle représentative et dans des conditions naturelles sur un mélange compacté de bentonite et de sable. Ce matériau de mélange a été choisi pour sa faible perméabilité et surtout pour sa capacité de gonflement qui permet de colmater les vides existant dans le système, notamment le vide technologique correspondant au vide radial entre le noyau de scellement et la roche hôte et qui est inévitable au cours de l'installation du noyau dans le forage. Une fois les vides scellés, le gonflement à volume constant engendre une pression de gonflement aussi bien sur la roche hôte (radiale) que sur les structures de confinement en béton (axiale). Le comportement de ce matériau dans ces conditions de couplages hydromécaniques est alors étudié dans ce travail. La microstructure du matériau à son état initial a été premièrement examinée par micro-tomographie rayons-X. Ceci a permis de voir la distribution des grains de bentonite et de sable ainsi que le réseau de pores dans l'échantillon. Des macro-pores se sont retrouvés concentrés à la périphérie de l'échantillon ainsi qu'entre les grains de sable, ce qui pourra affecter à court terme la perméabilité. L'hydratation du même matériau en condition de gonflement limité a été ensuite observée par une photographie 2D et par la micro-tomographie aux rayons-X. Le mécanisme de gonflement par production de gel de bentonite, la cinétique de gonflement, la diminution de densité et l'homogénéisation du matériau final on été analysés. L'hydratation en conditions de gonflement empêché a été aussi étudiée par des essais où la pression de gonflement a été mesurée dans deux directions : radialement et axialement. La différence retrouvée entre les pressions de gonflement axiales et radiales a évoqué la présence d'une anisotropie de microstructure qui a été analysée en fonction de la masse volumique sèche de bentonite dans le mélange. Des essais en modèle réduit reproduisant à une échelle 1/10ème les essais in situ (SEALEX) ont été également effectués afin d'étudier le comportement du noyau compacté après la reprise des vides au cas d'un accident détruisant les éléments de confinement. Des mesures locales de pression de gonflement le long des échantillons ont permis de mettre en évidence l'évolution du gradient de densité durant le gonflement axial. Finalement une comparaison entre les résultats obtenus dans ce travail et ceux d'un essai in situ (SEALEX) a été faite. Une bonne correspondance entre les valeurs d'humidités relatives a été retrouvée pour les mêmes longueurs d'hydratation tout en prenant en compte la saturation par le vide technologique radial. Par contre, la comparaison des évolutions et des valeurs de pressions de gonflement était plus compliquée vu les différences de configurations des essais / In order to verify the effectiveness of the geological high-level radioactive waste disposal, the French Institution of Radiation protection and Nuclear Safety (IRSN) has implemented the SEALEX project to control the long-term performance of swelling clay-based sealing systems, and to which this work is closely related. Within this project, In-situ tests are carried out on compacted bentonite-sand mixture in natural conditions and in a representative scale. This material is one of the most appropriate sealing materials because of its low permeability and good swelling capacity. Once installed, this material will be hydrated by water from the host-rock and start swelling to close all gaps in the system, in particular the internal pores, rock fractures and technological voids. Afterwards, swelling pressure will develop. In the present work, laboratory experiments were performed to investigate the sealing properties under this complex hydro-mechanical conditions taking into consideration the effect of technological voids. The microstructure of the material in its initial state was first examined by microfocus X-ray computed tomography (µCT). This allowed identification of the distribution of grains of sand and bentonite as well as the pores in the sample. Macro-pores are found concentrated at the periphery of the sample and between the grains of sand, which could affect in the short term the permeability. The hydration of the same material in limited swelling conditions was then observed by 2D photography and 3D µCT. The swelling mechanism with bentonite gel production, the swelling kinetics, the density decrease and the homogenisation of the material were analyzed. The hydration in the conditions of prevented swelling was also studied by swelling pressure tests with radial and axial measurements of swelling pressure. The difference found between the axial and radial swelling pressures suggested the presence of an anisotropic microstructure. Mock-up tests at a 1/10 scale of the in situ SEALEX tests were carried out for the study of the recovery capacity of the mixture in case of an accident causing the failure of the confining structures. Local measurements of swelling pressures along the sample allowed analysis of the density gradient evolution during axial swelling. Finally, a comparison between the laboratory results and those from an in-situ test was done, showing a good fitting in the relative humidity curves for the same infiltration length while considering the saturation effect from the technological void. The swelling pressure comparison was more complex because of the different configurations of the tests (existence of technological void in-situ that could affect the kinetics)

The effects of crop load and berry exposure on the composition of Marlborough Sauvignon blanc grapes and wine from the Brancott vineyard, Blenheim, were explored. Commercially grown, 2-cane and 4-cane Sauvignon blanc vines were used with a row orientation of north-south. Two exposure treatments were imposed in the following manner: complete leaf removal was undertaken in the fruit zone and 50% shade cloth was erected to give a uniform shading treatment to half the trial vines. Weekly thirty-berry and whole bunch samples were taken from each of the 32 plots with the exception of the veraison period when two samples per week were taken. Vine vigour was assessed using pruning and leaf area per vine data. Harvest occurred on different dates for 2-cane and 4-cane pruned vines so that fruit attained from both treatments had similar °Brix. Fruit was processed at the Lincoln University winery. Must analysis and wine analysis were undertaken. As expected, 4-cane vines had almost double the yield of 2-cane vines. Higher crop load significantly reduced leaf area per shoot and shoot thickness. Lower leaf area to fruit ratio for 4-cane berries resulted in delayed onset of veraison and slowed the rate of sugar accumulation. Crop load, which limited leaf area to fruit ratio, appeared to be the dominant factor in determining timing of grape physiological ripeness as expressed by °Brix over other factors such as fruit exposure. Malic acid, tartaric acid, IPMP (iso-propylmethoxypyrazine) and IBMP (iso-butyl-methoxypyrazine) were lower at equivalent °Brix in 4-cane compared with 2-cane berries. Significantly higher concentrations of quercetin were found in exposed compared to shaded berries. Must analysis showed a significant influence of crop load on berry titratable acidity and pH, reflecting berry ripening results. Exposure significantly increased the concentrations of nitrogenous compounds in 4-cane must yet showed no influence on 2-cane must. After wine processing lower malic acid concentrations in wines made from 100% exposed fruit became evident in lower wine titratable acidity but showed no influence on wine pH. Bentonite addition to wines had a small but statistically significant influence on wine by reducing pH, titratable acidity and alcohol. Bound sulphur concentrations were significantly higher in 4-cane versus 2-cane wines. At harvest, methoxypyrazine levels in grapes and wines were very low; IBMP concentrations where significantly lower than those normally found in Sauvignon blanc wines from Marlborough. This was attributed to the absence of basal leaves from the shoots of ripening berries. The results suggest that leaf area to fruit ratio is a powerful determinant of grape and wine quality.

Ce travail s'inscrit dans le cadre des études de l'interaction argile/polluant, concernant l'utilisation des argiles comme barrière d'un site de stockage de surface. Le travail présenté se propose de relier les variations de la perméabilité avec les modifications structurales et microtexturales pouvant être induites par la fixation d'un cation métallique sur une argile. Parmi 3 matériaux argileux albanais présélectionnés, celui de Prrenjas, formé par pédogenèse puis sédimentation continentale aux dépens d'une roche mère (ultrabasique), a été choisi en raison de ses caractéristiques proches d'une bentonite. Cette bentonite se caractérise par la présence majoritaire de smectite, par une CEC élevée, (90 meq/100 g), de Mg2+ majoritaire en position interfoliaire et la présence d'illite (11%) interstratifiée. Au MET la bentonite de Prrenjas a une morphologie particulière, avec une texture en microagrégats constitués de petites particules, qui la différencie des bentonites «modèles», du type Wyoming. Les études de l'interaction de l'argile en suspension avec des solutions de concentrations variées en Pb(NO3)2 couplées à l'étude de l'évolution structurale et microtexturale du matériau ont permis d'observer l'effet de Pb2+ sur l'argile de Prrenjas et sur l'argile de référence, Wyoming (SPV) échangée-Mg. Une diminution de l'hydratation de l'espace interfoliaire en fonction de la fraction molaire de Pb2+ a été observée par DRX. Les clichés de MET ont montré, pour l'argile de Prrenjas, une fragmentation des microagrégats qui la constituent en petites particules. Par contre, l'argile de référence paraît peu modifiée. La spectrométrie XPS indique une fixation de Pb2+, en surface des particules, plus importante pour l'argile de Prrenjas que pour l'argile de référence. Les essais de longue durée de fixation de Pb2+, par percolation d'une solution de Pb(NO3)2 à forte concentration (10-2 M) à travers l'argile compactée, ont montré une augmentation de la perméabilité d'un facteur 40, comportement, sans commune mesure, avec celui de la montmorillonite de référence (facteur 2). Les observations au cryo-MEB de l'argile compactée après la percolation de Pb(NO3)2 10-2M montrent des chemins d'écoulement connectés qui expliquent l'augmentation observée du débit. Finalement, ce travail montre que l'augmentation de la perméabilité, observée pour l'argile de Prrenjas, est une conséquence des modifications structurales aux différentes échelles d'organisation du matériau.

Les technologies à membranes sont en plein développement ; toutefois, les problèmes de colmatage limitent cette expansion. Les acides humiques présents dans les eaux naturelles induisent des chutes de production des membranes et sont à l'origine de fortes diminutions des durées de vie des matériaux filtrants. L'objectif principal de ce travail a été de développer une approche originale du colmatage de membranes basses pression d'ultrafiltration (UF). L'originalité de ce travail est de proposer plusieurs outils d'autopsie de membranes à deux échelles, l'une macroscopique (par des mesures de perméabilité hydraulique, dont sont déduites les résistances de colmatage et l'indice de colmatage MFI-UF) et l'autre microscopique (par la détermination de la dimension fractale des particules d'acides humiques et leurs agrégats déposés à la surface de la membrane). En utilisant une combinaison de ces outils macroscopiques, microscopiques et in situ, nous avons développé une nouvelle méthodologie pour l'analyse d'un gâteau d'acides humiques sur une membrane et ainsi permis d'évaluer plus finement que jusqu'ici la nature, les mécanismes, et les conséquences du colmatage de membranes basses pression. Cette méthode a été appliquée aux fibres creuses (vierge et colmaté par l'eau de surface naturelle), combinées avec l'autopsie de membrane. De plus, un nouvel appareillage semi-automatique de la mesure du potentiel d'écoulement, mise au point par nos soins, a permis de réaliser des investigations à l'intérieur de la structure de la membrane afin d'y déceler le cas échéant la présence de matière organiques naturelles (MON). La dernière partie est consacrée à une étude du prétraitement d'une solution d'acides humiques en présence de.bentonite modifiée (dénommée mont-Al-CTAB) afin de tenter de limiter le colmatage par les MON. La méthode de prétraitement employant la bentonite s'est avérée efficace en réduisant la résistance totale du gâteau d'acides humiques, en particulier en provoquant la diminution de la dimension fractale du gâteau formé en présence de bentonite.

Acquisition and interpretation of 3-D seismic data led DeAngelo and Hardage (2001) to describe the channel system in the south central Cut Bank area in Glacier County, Montana. The presence of a low velocity layer called Bentonite was also discovered in the area with the help of well-logs. Bentonite is a volcanic ash, which lies on both sides of the channel system and is absent within the channel. DeAngelo and Hardage (2001) shot a vertical seismic profiling (VSP) survey at well # 54-8 to analyze the formation structure in depth, since seismic signals around the reservoir area were unclear in the 3-D survey. This research attempts to estimate the attenuation properties of the Bentonite layer in the Cut Bank oil field. VSP data is processed for velocity information and estimation of seismic Q using the spectral ratios method (SRM). The SRM theoretically assumes that the propagating signal is a plane seismic wave traveling vertically from one point to another in a homogeneous model. The amplitudes at the start and end points are known and relate to each other with the attenuation coefficient in a frequency range. The relation between the seismic amplitudes at z distance from each other can be expressed as a linear function of frequency after a few modifications. SRM uses the linearity of the logarithmic ratio of the seismic amplitudes over a frequency range. In theory, ratios plotted against a frequency range must produce a flat line. However, in practice, the logarithmic ratios are expected to draw an approximate line (curve), where some of the data points deviate from the origin of the line. Thus fitting a line to the ratios curve and calculating the slope of this curve are necessary. Slope of the curve relates to the seismic attenuation coefficient and further to the seismic Q. The SRM results suggest that Bentonite may have a Q value as low as 5. This highly attenuative and thin (20 to 40 feet throughout the south central Cut Bank Unit) layer alters seismic signals propagating through it. A thorough analysis of the amplitude spectra suggests that seismic signals dramatically lose their energy when they pass through Bentonite. Low energy content of the signals below the Bentonite layer highlights that the recovery of the seismic energy is less likely despite the presence of multiples, which are known to affect the seismic signals constructively. Therefore, separation of reflected events is a greater challenge for the thin reservoir sand units lying underneath the Bentonite layer. Thus the Bentonite layer in the Cut Bank oil field has to be taken seriously and data processing should be done accordingly for better accuracy.

This study deals with the hydro-mechanical behaviour of compacted bentonite-based materials used as sealing materials in high-level radioactive waste repositories. The pure MX80 bentontie, mixtures of MX80/crushed claystone and MX80/sand were used in the investigation. An experimental study on the swelling pressure of the bentonite-based materials was first performed. The results evidenced the effects of water chemistry, hydration procedure and duration, pre-existing technological void and experimental methods. Emphasis was put on the relationship between the swelling pressure and the final dry density of bentonite. Afterwards, the water retention test, hydration test and suction controlled oedometer test were conducted on samples with different voids including the technological void and the void inside the soil. By introducing the parameters as bentonite void ratio and water volume ratio, an overall analysis of the effects of voids on the hydro-mechanical response of the compacted material was performed. To get better insight into the seal evolution in case of technological void, the effects of final dry density and hydration time on the microstructure features were also characterized. Then, the hydraulic properties under unsaturated state were investigated by carrying out water retention test and infiltration test as well as the microstructure observation. The results obtained allowed relating the variation of hydraulic conductivity to the microstructure changes. A small scale (1/10) mock up test of the SEALEX in situ experiment was also performed to study the recovery capacity of bentonite-based material with consideration of a technological void. The results were used for interpreting the in-situ observations. With a reduced time scale, it provides useful information for estimating the saturation duration and sealing effectiveness of the field design. Finally, the experimental data obtained in the laboratory on bentonite/sand mixture were interpreted in the framework of the Barcelona Expansive Model (BExM). By comparing the model with the experimental results, the performance and limitation of the model were analyzed

Submitted by Maike Costa (maiksebas@gmail.com) on 2017-06-21T13:34:41Z No. of bitstreams: 1 arquivototal.pdf: 8365560 bytes, checksum: 9864dee1c44924e2f7a2db5c50f4a7aa (MD5) / Made available in DSpace on 2017-06-21T13:34:41Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 8365560 bytes, checksum: 9864dee1c44924e2f7a2db5c50f4a7aa (MD5) Previous issue date: 2016-08-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The bentonite term designates gross clays containing at least 50% of smectite and particularly montmorillonite. The smectite have features like lamellar structures, ion exchange capacity, variability of the chemical composition and the electrical charge of the lamellae, which determine the properties in interactions with organic and inorganic substances. Changes in physical and chemical properties of these materials after intercalation of organic compounds has drawn attention due to wide applicability by these hybrids. polar organic molecules such as amines, may replace the water molecules that occupy the interlayer space, resulting in organofílicos materials. Within this perspective, we obtained hybrid bentonite intercalation / amines using bentonite exchanged with sodium and calcium cations. In this case we have used two cyclic diamines of pharmacological importance, an aliphatic, piperazine (PPZ) and an aromatic, pyrazine (PRZ) for hybrid formation by several synthesis routes. Then the drug amiloride hydrochloride, which has in its structure the pyrazine ring is loaded in calcium bentonite sample for subsequent emissions testing. The characterization techniques such as, XRD, IR, TEM, inter alia, the efficiency in all cases. Thus, the results indicate a possible application of such hybrids for obtaining the metal complexes and the use of these systems for controlled emission tests in view of the PPZ have pharmacological properties while PRZ is a base molecule for various drugs, such as amiloride, for example. / O termo bentonita designa as argilas brutas contendo pelo menos 50% de esmectitas e particularmente montmorillonita. As esmectitas possuem características como: estrutura lamelar, capacidade de troca iônica, variabilidade da composição química e da carga elétrica das lamelas, que determinam as propriedades nas interações com substâncias orgânicas e inorgânicas. As alterações nas propriedades físicas e químicas desses materiais após a intercalação de compostos orgânicos tem chamado atenção devido à vasta aplicabilidade apresentada por esses híbridos. Moléculas orgânicas polares, como aminas, podem substituir as moléculas de água, que ocupam o espaço interlamelar, resultando em materiais organofílicos. Dentro dessa perspectiva, foram obtidos híbridos de intercalação bentonitas/aminas utilizando bentonitas trocadas com cátions de sódio e cálcio. Neste caso foram utilizadas duas diaminas cíclicas de importância farmacológica, uma alifática, piperazina (PPZ) e uma aromática, pirazina (PRZ) para a formação de híbridos por diversas rotas de síntese. Em seguida o fármaco cloridrato de amilorida, que tem em sua estrutura o anel pirazínico, foi carregado na amostra cálcica da bentonita para consequentes ensaios de emissão. As técnicas de caracterização como, DRX, IV, MET, entre outros, comprovaram a eficiência em todos os casos. Sendo assim, os resultados indicam uma possível aplicação desses híbridos para obtenção de complexos metálicos, bem como o uso destes sistemas para ensaios de emissão controlada tendo em vista que a PPZ tem propriedades farmacológicas, enquanto a PRZ é uma molécula base para diversos fármacos, como a amilorida, por exemplo.