It is a generally agreed internationally that high level nuclear wastes containing long-lived radioactive wastes should be disposed in deep and stable geological formations that are 500-1000 m below ground level. Deep geological disposal is based on the concept of multiple barriers to prevent deep ground-waters, present in almost all rock formations, from rapidly leaching the wastes and transporting radioactivity away from the repository. The multiple barrier system comprises of ‘engineered barriers’ that are constructed in the repository and ‘natural barriers’ in the surrounding geological environment. The engineered barrier components comprise of the vitrified solid waste, canister (to contain the vitrified waste), and a buffer or backfill material (clay or cement) that fills the annular space between the canister and the walls of the hole drilled in the floor of host-rock. The natural barrier is provided by the rocks and soils between the repository and earth’s surface. The canisters containing the hig level waste (HLW) upon placement in DGR need protection against tectonic activities and chemical attack by dissolved elements and from microbes. Densely compacted bentonite is identified suitable for this purpose owing to its large swell potential, low permeability, sufficient bearing capacity and high cation adsorption capacity. In the deep geological repository (DGR) for disposal of high level nuclear wastes, iodine-129 is one of the significant nuclides, owing to its long half-life (half life = 16 million years) and tendency to easily migrate out of the geological repository into the biosphere caused by its high solubility and poor sorption onto most geologic media. Bentonite buffer by virtue of negatively charged basal surface has negligible affinity for retention of iodide anions. Attempts have been made to improve the iodide retention capacity of bentonite by treating the clay with cationic polymers, this however occurs at the cost of reduced swelling ability of bentonite clay. The compacted bentonite employed in deep geological repositories must possess large swell potential to enable it to close fissures and cracks that form on drying of the expansive clay by the heat arising from the high level nuclear waste and thereby close pathways for migration of radionuclides (from breached canister) to the geo-environment. Therefore, it becomes important to identify an additive that enhances the iodide retention ability of the mix without significantly impairing its swelling ability. Based on the strong affinity of silver for iodide ions, the feasibility of mixing silver-kaolinite (termed AgK) clay with bentonite to improve the latter’s iodide sorption capacity and the impact of mixing AgK clay with bentonite on swelling ability of the mix forms one of the the focus of this thesis. Silver-kaolinite clay was prepared by heating 80% kaolinite + 20% silver nitrate mix at 400°C for 30 min, followed by washing (to remove unreacted silver nitrate) and oven-drying the resultant AgK clay. Physical mixing of AgK and bentonite was considered a viable proposition as small additions (10% to 20% on dry mass basis) besides imparting iodide sorption ability was expected to have minor influence on the swelling ability of the mix. As organo-bentonites are known to retain iodide ions, it was considered relevant to compare the iodide removal behaviour of AgK and organo¬bentonite clay. Hexadecylpyridinium-bentonite (termed as HDPy+B) is the organo¬bentonite examined in this thesis and is prepared by treating bentonite with hexadecylpyridinium chloride mono hydrate salt (C21H38ClN.H2O; molecular weight = 358.01). The hexadecylpyridinium chloride mono hydrate salt is a cationic quaternary ammonium compound and has been used by earlier researchers to prepare organo-bentonite for removal of iodide ions from aqueous solutions. The impact of mixing AgK and HDPy+B clays on the iodide retention and swelling behaviour of bentonite is also considered in the thesis. The mass-balance calculations, XRD analysis, X-ray photon emission survey spectrum and EPMA tests performed on kaolinite-silver nitrate mix/AgK/kaolinite specimen indicated that silver occurs as uniform coatings of AgO/Ag2O on kaolinite surface of the AgK specimen. The AgK clay has strong affinity for iodide ions reflected by the large distribution coefficients (Kd) values of 1367 and 293 mL/g at initial iodide concentrations of 750 mg/L and 1000 mg/L. Further, the sorption process was rapid, unaffected by the presence of co-ions, elevated temperature of sorption and was practically irreversible at range of pH conditions. The iodide retention by AgK is attributed to occurrence of hydrolysis and exchange reactions. On contacting the AgK with water, the AgO species hydrolyze to form AgOH; iodide ions are retained by replacing the hydroxyl group of AgOH leading to formation of AgI phase. The adsorption of HDPy+Cl- ions by bentonite occurs by replacement of the native exchangeable cations by HDPy+ ions and adsorption by van der Waals interactions between the organic cations and the clay surface. The adsorbed cationic polymer neutralize the negative charge of the clay surface. Zeta potential measurements of HDPy+B specimen indicated that adsorption of cationic polymer transforms the negatively charged clay particles into positively charged particles that favour anion adsorption. Sorption of iodide ions by HDPy+B specimen exhibits two distinct segments: 1) the iodide sorption increased rapidly at lower iodide concentration (91 mg/L to 475 mg/L) and are retained by Coulombic adsorption to the cationic groups contained in the loops and tails of the adsorbed polymer (primary adsorption sites) and 2) the relatively slower adsorption at higher iodide concentrations (larger than 475 mg/L) is attributed to exchange with chloride ions attached to HDPy+Cl-ion pair (secondary adsorption sites). The Kd values for iodide adsorption vary from 15 mL/g to 184 mL/g at initial iodide concentrations of 91 mg/L to 996 mg/L respectively. Comparing the iodide removal efficiencies of AgK and HDPy+B specimens revealed that the AgK clay exhibited larger iodide removal; further while the iodide removal by AgK specimen was almost instantaneous (complete in < 5 min), iodide removal by HDPy+B specimen was a slow process (18-24 h is needed to attain equilibrium). Likewise, the iodide retention capacity of the 50%B-50%HDPy+B mix (B = bentonite) is substantially smaller than of the 90%B-10%AgK and 80%B¬20%AgK mixes. Cation exchange capacity (CEC) measurements brought out that mixing AgK with bentonite besides imparting an iodide retention capacity essentially retains the large cation exchange capacity of the expansive clay. On the other hand mixing HDPy+B with bentonite imparts a smaller iodide retention capacity to the mix and leads to a notable reduction in the CEC of the expansive clay. Results of oedometer swell tests brought out that dilution of bentonite with 10% and 20% AgK specimen does not impact its swell potential and leads to some (10%) reduction in swell pressure, while dilution with 50% HDPy+B clay leads to notable (58%) reduction in swell potential and swell pressure (21%) underlining the superiority of AgK specimen as additive to bentonite in deep geological repositories. The swell pressure of the compacted 50%B-50%HDPy+B mix is 21% lower than that of the compacted bentonite specimen. Comparatively, dilution of bentonite with 10% and 20% AgK specimen induces 8-10% lower swell pressure in comparison to the undiluted counterpart. Swell pressure results of compacted 80%B-20%HDPy+B mix is not considered as this mix was unable to retain iodide ions. Superposing the field 129I concentration levels on I removal efficiency indicate that use of 90%B-10%AgK mix would suffice to provide 100% iodide removal efficiency and ensure that the swelling characteristics of bentonite is least affected by dilution.

La présente étude concerne le comportement hydromécanique des matériaux compactés à base de bentonite pour le stockage des déchets radioactifs en grande profondeur. Trois matériaux candidats ont été étudiés : la bentonite (MX80) pure, le mélange bentonite/argilite broyée et le mélange bentonite/sable. Une étude expérimentale sur la pression de gonflement du mélange bentonite/argilite a été premièrement réalisée. Cette étude a mis en évidence l'effet de la salinité de l'eau, de la procédure et la durée d'hydratation, du pré-existant vide technologique et des méthodes expérimentales. Une importante relation entre la pression de gonflement et la densité sèche finale de la bentonite a été élaborée. Ensuite, des essais de rétention d'eau, des essais d'hydratation et des essais oedométriques à succion contrôlée ont été réalisés sur des échantillons à différentes porosités tout en considérant la présence du vide technologique. En introduisant les paramètres comme indice des vides de la bentonite et le ratio volume d'eau, une analyse globale des effets des vides sur la réponse hydromécanique de la barrière ouvragée a été effectuée. Pour obtenir un meilleur aperçu de l'évolution de l'étanchéité dans le cas de vide technologique, l'effet de densité sèche finale (densité après fermeture de vide technologique) et du temps d'hydratation sur la microstructure a été, de même, étudié. La perméabilité de ce matériau à l'état non saturé a été ensuite étudiée en réalisant des essais de rétention d'eau et d'infiltration ainsi que par des observations de la microstructure. Les résultats obtenus ont permis de relier la variation de la conductivité hydraulique non saturée aux changements de la microstructure. Une expérimentation en modèle réduit reproduisant à une échelle 1/10ème les essais in-situ (SEALEX) a été effectuée, et cela pour étudier la reprise des vides à long terme d'un mélange compacté bentonite/sable, tout en considérant la présence d'un vide technologique. Les résultats ont été utilisés pour interpréter les observations de l'essai in situ. A une échelle de temps réduite, cette étude fournit des informations utiles pour estimer la durée et l'efficacité de la conception en place. Finalement, les données expérimentales obtenues dans le laboratoire sur le mélange bentonite/sable ont été interprétées dans le cadre du modèle de Barcelone (BExM). Après comparaison des résultats expérimentaux avec le modèle, les performances et les limitations du modèle ont été analysées / 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

A utilização do solo natural compactado com bentonita empregado em camadas impermeáveis para retenção de contaminantes é bastante usual para aterros sanitários. Neste trabalho são apresentados resultados de ensaios condutividade hidráulica e de resistência ao cisalhamento, realizados em equipamentos triaxiais. Além do solo natural, foram utilizadas misturas solo-bentonita nos teores de 2%, 4% e 6%. O solo arenoso ensaiado é encontrado na Planície Costeira Sul do Estado do Rio Grande do Sul. Os valores de condutividade hidráulica diminuiram tanto com o acréscimo do teor de bentonita, quanto com o aumento da tensão de confinamento. A condutividade hidráulica do solo apresentou uma redução de três ordens de grandeza quando este foi compactado com 6% de bentonita (de \'10 POT.-7\' para \'10 POT.-10\' m/s). Em relação a resistência ao cisalhamento do material, constatou-se que com o acréscimo do teor bentonita de 0 para 6%, a coesão efetiva aumentou (de 2,3 para 12,8 kPa) e o ângulo de atrito efetivo diminuiu (de 22,7º pra 14,0º). / Compacted soil-bentonite mixtures used as impermeable layers for retention of contaminants is quite usual in landfills. This paper presents the results of hydraulic conductivity and shear strength tests conducted in a triaxial apparatus. Natural soil, and soil-bentonite mixtures at 2%, 4% and 6% concentrations were tested. The sandy soil tested is found in the Southern Coastal Plain of Rio Grande do Sul. The hydraulic conductivity decreased with both the increase of bentonite content and increase of confining stress. Compared to natural soil, the hydraulic conductivity of compacted soil-bentonite mixtures at 6% content decreased by three orders of magnitude (from \'10 POT.-7\' to \'10 POT.-10\' m/s). Regarding the material shear strength, it was found that when the natural soil is compared to compacted soil-bentonite mixtures at 6% content, the effective cohesion increased (from 2.3 to 12.8 kPa) and the effective friction angle decreased (from 22. 7º to 14.0º).

[pt] As atuais técnicas propostas para a destinação final dos pneus não são 100 por cento eficientes, existindo um grande déficit do material em questão. Um outro material que necessita de uma destinação final é o PET (polietileno tereftalato), que hoje em dia, apesar da grande quantidade reciclada, necessita de mais opções de destinação. O estudo apresentado propõe a utilização da borracha triturada (em forma de fibras e em pó - granulometria inferior a 2mm) em diferentes teores (de 5 por cento e 10 por cento, em relação ao peso seco da bentonita) e do PET triturado (na forma de fibras e em pó), como reforço de uma bentonita, para aumento dos parâmetros de resistência desta. O objetivo da pesquisa consiste em avaliar a possibilidade da utilização da borracha e do PET como melhoramento de bentonita em obras geotécnicas, como por exemplo em camadas impermeabilizantes para aterros sanitários, visto que com a utilização da borracha e do PET em obras geotécnicas seria possível a destinação de um grande volume desses materiais. Para o desenvolvimento do estudo experimental foram realizados ensaios de caracterização física e de caracterização mecânica, como ensaios de cisalhamento direto e adensamento. Com resultados obtidos a partir dos ensaios de cisalhamento direto e ensaio de adensamento, pode se perceber que as misturas B90BF10 e B90PETT10 se mostraram mais favoráveis a utilização como barreira impermeabilizando para aterros sanitários, tendo em vista o aumento nas resistências de Pico, pós pico e residual, além do aumento do coeficiente de adensamento (cv) e redução da permeabilidade (k). / [en] The current techniques proposed for the final destination of the tires are not 100 percent efficient, and there is a great deficit of the material in question. Another material that needs an end destination is the PET (polyethylene terephthalate), which nowadays, despite the large amount recycled, needs more disposal options. the present study proposes the use of crushed rubber (in the form of fibers and powder - granulometry of less than 2 mm) in different contents (5 percent and 10 percent, in relation to the dry weight of bentonite) and crushed PET (in the form of fibers and powder), as reinforcement of a bentonite, to increase the resistance parameters of this one. The objective of the research is to evaluate the possibility of using rubber and PET as an improvement of bentonite in geotechnical works, such as waterproofing layers for sanitary landfills, since with the use of rubber and PET in geotechnical works it would be possible to allocate a large volume of these materials. For the development of the experimental study, physical characterization and mechanical characterization tests were performed, such as direct shear tests and densification. With results obtained from the direct shear tests and the densification test, it can be seen that the mixtures B90BF10 and B90PETT10 were more favorable to use as a waterproofing barrier for sanitary landfills, in view of the increase in peak and residual, besides the increase of the coefficient of densification (cv) and reduction of the permeability (k).

La presente tesi di dottorato ha riguardato la valutazione di differenti campioni di bentoniti sodiche. Le attività pianificate sono state indirizzate a comprendere l’interazione dei suddetti materiali con proteine a diverso peso molecolare naturalmente contenute nei vini bianchi. Ulteriori indagini hanno riguardato l’eventuale impatto delle argille testate sui composti aromatici di origine varietale e fermentativa dei mosti e/o dei vini. I risultati sottolineano il ruolo chiave esercitato dal “fattore matrice”: oltre al tipo di vino, prima di pianificare un trattamento di fining, devono essere considerate anche la tipologia e la dose di bentonite da utilizzare. / This PhD thesis dealt with the evaluation of different sodium bentonite samples. The planned activities were aimed to understand the interactions between bentonites and different molecular weight proteins naturally contained in white wines. Further investigations were related to the impact of the clays on varietal and fermentative aroma compounds of musts and/or wines. Results underscore the key role exerted by the “matrix factors”: bentonite dose and typology and wine style have to be carefully considered before planning a fining treatment.

Pipe jacking, has seen a rise in popularity, particularly in urban areas where infrastructure does not permit cut-and-cover methods. As pipe jacking has becomes more commonplace, engineers are pushing the limits of the technology more and more by designing longer drives in more difficult ground conditions. Lubrication is essential to reduce the frictional resistance generated at the pipe-soil interface. Even though lubrication is widely utilized, there is not a clear understanding of the conditions required to obtain the full benefit of lubrication. This dissertation focuses on bentonite slurry characteristics and interface behavior under different lubricating conditions with the goal to further the understanding of the mechanisms responsible for the large friction reductions observed in the field. An interface shear device capable of measuring interface behavior on pipe surfaces was used to perform tests under two lubricating conditions. Pipes were sheared against a mixture of sand and slurry and the effect of the slurry was quantified. In another series of tests, slurry was injected at the pipe-soil interface. An axisymmetric interface shear device was developed to further investigate the lubrication mechanism associated with injection of slurry into sand. The device was designed to inject slurry through injection ports built into a shaft displaced within a sealed sand-filled chamber. A series of tests were performed on dry sand as well as sand where water or slurry was injected during shearing. The effect of sand type and viscosity are also investigated. Findings from the experimental studies are related back to full-scale behavior with the objective of assessing the lubrication methods and their effectiveness. A rational procedure for predicting non-lubricated and lubricated jacking forces is proposed to optimize design and serve as a framework for evaluating jacking forces in the field.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-04T19:50:45Z No. of bitstreams: 1 IVNA DANIELE SOUZA PEREIRA - DISSERTAÇÃO PPG-CEMat 2014..pdf: 2113912 bytes, checksum: e7cd84f19623986d5ca5b0df7875190e (MD5) / Made available in DSpace on 2018-04-04T19:50:45Z (GMT). No. of bitstreams: 1 IVNA DANIELE SOUZA PEREIRA - DISSERTAÇÃO PPG-CEMat 2014..pdf: 2113912 bytes, checksum: e7cd84f19623986d5ca5b0df7875190e (MD5) Previous issue date: 2014-08-29 / Capes / No Estado da Paraíba há grandes ocorrências de minerais não metálicos principalmente de argilas bentoniticas, ball clays, caulins, feldspatos, quartzo, calcários e micas. Recentemente foram descobertos novos depósitos de argilas no município de Sossego, propiciando assim, uma expectativa de ampliação de insumos minerais na região. Assim, este trabalho tem por objetivo caracterizar física, mineralógica e tecnologicamente argilas esmectíticas do Município de Sossego, PB, Brasil, para uso em fluidos de perfuração. Para tanto, as argilas foram beneficiadas e caracterizadas através das seguintes técnicas: granulometria a laser (AG), difração de raios-X (DRX), análise química (EDX), capacidade de troca de cátions (CTC), análise termogravimétrica(TG) e térmica diferencial (DTA). Em seguida as argilas foram transformadas em sódicas por meio de tratamento com carbonato de sódio (Na2CO3), hexametafosfato de sódio (NaPO3)6 nos teores: 75, 100, 125 e 150meq/100g de argila seca, além de serem ativadas com a combinações de (Na2CO3) e óxido de magnésio (MgO), em seguida realizou-se o estudo do comportamento reológico das dispersões no intuito de determinar viscosidade aparente (VA), viscosidade plástica (VP), volume de filtrado e pH. Os resultados mostraram que as argilas estudadas eram constituídas de esmectítica, caulinita e quartzo, apresentando teores de MgO e CaO, evidenciando que são bentonitas policatiônicas. Com relação ao uso das argilas como agente viscosificante para fluidos de perfuração, observou-se que as amostras de AM2 ativadas com Na2CO3 atenderam parcialmente as especificações necessária para uso em fluidos de perfuração base água. Já as amostra ativadas com (NaPO3)6 não desenvolveram melhoria nas suas característica reológicas, logo seu uso como fluido de perfuração não é viável. A combinação de Na2CO3 e de MgO produziu um melhoramento nas propriedades dos fluidos produzidos, demonstrando ser aplicável na perfuração de poços. / In Paraíba's large occurrences of non-metallic minerals mainly of bentonite clays, ball clays, kaolin, feldspar, quartz, limestone and mica. Recently discovered new deposits of clays in the city of Sossego, providing an expected expansion of mineral inputs in the region. This work aims to characterize physical, mineralogical and technologically smectite clays Municipality Sossego, PB, Brazil, for use in drilling fluids. For both, the clays were processed and characterized by the following techniques: laser granulometry (AG), X-ray diffraction (XRD), chemical analysis (EDX), cation exchange capacity (CEC), thermogravimetric analysis (TG) and differential thermal analysis (DTA). The clays were then transformed into sodic by treatment with sodium carbonate (Na2CO3), sodium hexametaphosphate (NaPO3) 6 in levels: 75, 100, 125 and 150meq / 100g of dry clay, and being activated with combinations (Na2CO3) and magnesium oxide (MgO), then held up the study of the rheological behavior of the dispersions in order to determine apparent viscosity (VA), plastic viscosity (PV), filtrate volume and pH. The results showed that the clays of smectite were formed, kaolinite and quartz, with MgO and CaO contents, showing that bentonites are polycationic. Regarding the use of clays as viscosity agent for drilling fluids, it was observed that the samples activated with Na2CO3 AM2 partially met the necessary for use in water based drilling fluids specifications. As for the sample activated to (NaPO3)6 did not develop improvement in rheological characteristic, then its use as drilling fluid is not feasible. The combination of Na2CO3 and MgO produced an improvement in the properties of the produced fluids, proving to be applicable in drilling wells Keywords: bentonite, rheology, characterization, drilling fluids.

Cette thèse porte sur le comportement hydromécanique d’un mélange de poudre et pellets de bentonite MX80 avec une proportion 80/20 en masse sèche. Il s’agit d’un matériau étudié par l’Institut de Radioprotection et de Sûreté Nucléaire (IRSN) dans le cadre du projet SEALEX qui a pour objectif principal la vérification de l’efficacité des dispositifs de scellement ou des barrières ouvragées dans le system du stockage géologique des déchets radioactifs. Le comportement hydromécanique du matériau à différentes échelles a été étudié par différents essais en laboratoire. Premièrement, les changements à l’échelle microstructurale d’un seul pellet de bentonite durant l’hydratation a été abordée à l’aide de deux techniques : la porosimétrie au mercure et la tomographie aux rayons-X. Les résultats ont montré que le gonflement d’un pellet peut être expliqué par deux mécanismes : la création des fissures surtout à des succions entre 38 et 9 MPa, et le gonflement des grains de bentonite, correspondant à l’hydratation des smectites à l’échelle nano. A des succions inférieures à 9 MPa, une diminution de l’épaisseur des feuillets d’argile et une augmentation du désordre des ceux-ci sont observées. Des essais de rétention d’eau, de pression de gonflement et de compression à l’odomètre à succion contrôlée ont été effectués sur le mélange de poudre et pellets. Les propriétés de rétention d’eau sous conditions de volume constant et pour un seul pellet sous conditions de gonflement libre apparaissent similaires pour des valeurs de succion supérieures à 4 MPa. Cela implique que la succion physico-chimique est prédominante devant la succion capillaire. Pour des valeurs de succions plus basses, une capacité de rétention plus faible a été observée sous conditions de volume constant, à relier à la disparition des macro-pores par le gonflement des grains de bentonite. Des valeurs de pression de préconsolidation plus petites que celles des mélanges de bentonite pure ont été obtenues pour des succions non-nulles, montrant l’effet granulaire des pellets dans le mélange. Deux colonnes d’infiltration ont été réalisés afin d’étudier deux cas extrêmes avec une densité sèche globale identique (1.49 Mg/m3). Avec la première colonne, un mélange de poudre et pellets relativement homogène, fabriqué en suivant un protocole spécial a été étudié. En revanche, un mélange fortement hétérogène a été fabriqué dans la deuxième colonne d’infiltration. Les résultats montrent que la pression de gonflement radiale dépend fortement de la distribution des pellets et de la poudre ainsi que de l’évolution du front d’hydratation. Une anisotropie de gonflement a été observée dans les deux cas, avec la pression de gonflement axiale inférieure à celle radiale. De plus, la valeur finale de pression de gonflement axiale est différente pour les deux colonnes, bien que les deux échantillons aient fabriquées avec la même densité sèche globale. En parallèle, plusieurs observations à la tomographie aux rayons-X ont été réalisées sur le mélange de pellets et poudre pendant l’hydratation. Un mélange complètement homogène a été observé après 100 jours d’hydratation à l’échelle étudiée (50 μm/voxel). Un nouveau modèle d’endommagement qui prend en compte des fissures observées au sein du pellet pendant hydratation a été développé en adaptant le Barcelona Expansive Model (BExM). L’essai d’infiltration sur l’échantillon relativement homogène a été simulé avec succès en utilisant le modèle développé. L’hétérogénéité initiale de la porosité a été aussi considérée dans la simulation afin de reproduire l’anisotropie de gonflement. Les résultats expérimentaux obtenus dans le cadre de cette étude permettent de mieux comprendre la réponse des ouvrages de scellement avec le mélange de pellets et poudre de bentonite dans le projet SEALEX. De plus, le modèle développé, qui prend en compte des fissures observées au sein du pellet et l’hétérogénéité initiale du matériau, permettra d’améliorer / The present investigation deals with the hydro-mechanical behavior of a mixture composed of pellets and powder of MX80 bentonite with a proportion of 80/20 in dry mass. This is one of the studied materials by the French Institute for Radiation protection and Nuclear Safety (IRSN) within the SEALEX project, which aims at investigating the long-term performance of swelling clay-based sealing systems in the context of geological high-level radioactive waste disposal. This study has been conducted by following an experimental program covering different scales. Firstly, the microstructure changes while wetting of a single pellet was investigated by combining MIP results with μ-CT observations. Results revealed that swelling of a pellet is due to the development of cracks, with significant development between 38 and 9 MPa of suction, combined to swelling of bentonite grains, which is governed by the hydration mechanisms of smectite at nano-scale. The application of suctions below 9 MPa leads to a significant decrease of the platelet thickness and to an increase in the disorder of the platelet assembly. Water retention tests, swelling pressure tests and suction controlled oedometer tests on the pellet/powder mixture were performed. Similar water retention properties were observed for the mixture under constant-volume condition and pellet under free swelling condition under suctions higher than 4 MPa, suggesting that physico-chemical suction prevails on capillary suction. At lower suctions, constant-volume condition defined a lower water retention capacity because of the disappearance of macro-pores. Lower yield stress values than the common pure bentonite mixtures were found for the pellet/powder mixture for non-zero suctions, showing that the volume change behavior is governed by the rearrangement and crushing of pellets, and the loss of the granular structure in the case of zero suction. Two mock-up tests were performed, aiming at studying two extreme cases at a global dry density of 1.49 Mg/m3: a homogeneous pellet/powder mixture fabricated by following a special protocol, and a strong heterogeneous sample. Results revealed that the radial swelling pressure depends strongly on the local pellet/powder distribution combined with the evolution of the hydration front. An anisotropy swelling was found in both cases, being the axial swelling pressure lower than the radial one. Moreover, different values of axial pressure were found between the two tests, even though they have the same global dry density of samples. In parallel, μ-CT observations were carried out on the mixture while wetting, revealing a homogeneous sealed sample after 100 days of hydration. No density gradients were identified at the investigated resolution (50 μm/voxel) after this long time of hydration. A new damage model, which takes into account the development of fissures within a pellet while wetting, was proposed an included to the well-IVknown double porosity Barcelona Expansive Model (BExM) to carry out numerical simulations of one mock-up test. The initial heterogeneous porosity distribution was also considered to reproduce the anisotropy swelling. The experimental results obtained in this study will greatly help well understand the response of seals made up of pellets/powder bentonite mixture in the SEALEX in situ experiment. Moreover, the constitutive model developed taking into account the pellet cracking damage and the initial sample heterogeneity allows significantly improving the prediction of hydomechanical behavior of seals/plugs made up of this mixture, constituting thus an useful tool for the safety assessment of the nuclear waste disposal system

L’introduction des nano-charges dans le milieu des polymères donna naissance aux nanocomposites et révolutionna l’univers des matériaux. Les nanocomposites sont à l’instar des composites traditionnels, un mélange de polymère et d’une charge avec au moins une dimension nanoscopique. Dans le cadre de notre projet, nous avons travaillé avec des nanocomposites à base des polymères biodégradables : polyacidelactique et polycaprolactone, combinés avec différentes nano-argiles «kaolin et bentonite» et avec différentes nano-organo-argiles. Ces nanocomposites ont été préparés par différentes méthodes (intercalation en solution, polymérisation in situ et la méthode de la voie fondue). L’avantage de ces polymères est dans leur dégradabilité ainsi que leur biocompatibilité. Une étude des relations entre l’élaboration, la microsctructure et les propriétés physico-chimiques des nanocomposites, des argiles modifiées par 3-aminopropyltriéthoxysilane (APTES) et Bromure d’Hexadecyltriméthy ammonium (CTAB) et des argiles non traitées ont été réalisés. La polymérisation in situ et le mélange à l’état fondu sont les méthodes les plus appropriées pour obtenir une meilleure dispersion nommée exfoliation. L’étude de la capacité d’adsorption du Co (II), Cd (II), Cu (II) et Ni (II) par ces deux adsorbants bruts (kaolin et bentonite) croit considérablement avec l’augmentation du pH. Cette capacité est 2 fois et demie plus importante dans le cas de la bentonite que dans celui du kaolin. L’étude comparative des cinétiques d’adsorption, nous a révélé une cinétique rapide de l’ordre de 6 min dans le cas du cobalt, 10 min dans le cas du nickel, 15 min dans le cas du cadmium et une cinétique moyenne de l’ordre de 120 minutes pour Cu (II) aussi bien pour la bentonite que pour le kaolin. L’étude de l’adsorption du Co (II), Cd (II), Cu(II) et Ni (II) par ces matériaux (argiles brutes, argiles organiquement modifiées et nanocomposites préparés par différentes méthodes) montre que la capacité d’adsorption de ces métaux lourds est importante dans le cas de l’argile modifiée par APTES / The introduction of nano-fillers into polymers field lead to the creation of the nanocomposites. This creation is starting up a new revolution into the world of materials. Nanocomposites are similar to traditional composite of a polymer blend and filler with at least one nano-scopic dimension. In our project, we worked with nanocomposites of biodegradable polymers: polyacidlactic and polycaprolactone, combined with different nanoclays "kaolin and bentonite" and with different nano-organo-clays. These nanocomposites have been prepared by different methods (solution intercalation, in situ polymerization and melt mixture methods). The advantage of these polymers is their degradability and biocompatibility. A study of the relationship between development, microsctructure and physico-chemical properties of nanocomposites, clays modified with 3-aminopropyltriethoxysilane (APTES) and Hexadecyltriméthy ammonium bromide (CTAB) and untreated clays were made. In situ polymerization and melt mixture methods are most suitable methods to get a better dispersion named exfoliation. The study of the adsorption capacity of Co (II), Cd (II), Cu (II) and Ni (II) by these two raw adsorbents (kaolin and bentonite) increases significantly with increasing pH. This capacity is two and half times higher in the case of bentonite than in kaolin. The comparative study of adsorption kinetics, we revealed rapid kinetics of the order of 6 minutes for the Co (II), 10 min for the Ni (II), 15 min for the Cd (II) and an average kinetic order of 120 minutes for Cu (II) both for the bentonite that for kaolin. The study of the adsorption of Co (II), Cd (II), Cu (II) and Ni (II) by these materials (raw clays, organically and nanocomposites prepared by different methods) shows that the adsorption capacity of these heavy metals is important in the case modified clay by APTES

A utilização do solo natural compactado com bentonita empregado em camadas impermeáveis para retenção de contaminantes é bastante usual para aterros sanitários. Neste trabalho são apresentados resultados de ensaios condutividade hidráulica e de resistência ao cisalhamento, realizados em equipamentos triaxiais. Além do solo natural, foram utilizadas misturas solo-bentonita nos teores de 2%, 4% e 6%. O solo arenoso ensaiado é encontrado na Planície Costeira Sul do Estado do Rio Grande do Sul. Os valores de condutividade hidráulica diminuiram tanto com o acréscimo do teor de bentonita, quanto com o aumento da tensão de confinamento. A condutividade hidráulica do solo apresentou uma redução de três ordens de grandeza quando este foi compactado com 6% de bentonita (de \'10 POT.-7\' para \'10 POT.-10\' m/s). Em relação a resistência ao cisalhamento do material, constatou-se que com o acréscimo do teor bentonita de 0 para 6%, a coesão efetiva aumentou (de 2,3 para 12,8 kPa) e o ângulo de atrito efetivo diminuiu (de 22,7º pra 14,0º). / Compacted soil-bentonite mixtures used as impermeable layers for retention of contaminants is quite usual in landfills. This paper presents the results of hydraulic conductivity and shear strength tests conducted in a triaxial apparatus. Natural soil, and soil-bentonite mixtures at 2%, 4% and 6% concentrations were tested. The sandy soil tested is found in the Southern Coastal Plain of Rio Grande do Sul. The hydraulic conductivity decreased with both the increase of bentonite content and increase of confining stress. Compared to natural soil, the hydraulic conductivity of compacted soil-bentonite mixtures at 6% content decreased by three orders of magnitude (from \'10 POT.-7\' to \'10 POT.-10\' m/s). Regarding the material shear strength, it was found that when the natural soil is compared to compacted soil-bentonite mixtures at 6% content, the effective cohesion increased (from 2.3 to 12.8 kPa) and the effective friction angle decreased (from 22. 7º to 14.0º).