Made available in DSpace on 2015-05-14T13:21:47Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2304381 bytes, checksum: 383faaa5d2a0cb26ce8f49ef357849d1 (MD5) Previous issue date: 2009-03-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The selective leaching of clay minerals is an important method in the preparation of porous silicates presenting as a simple, effective and low cost route. In this study, vermiculite was submitted to acid treatment at concentrations 1, 2, 3, and 4 mol dm-3, resulting the precursor solids named as VacX (x=1 a 4), respectively. The lixiviated matrices and vermiculite reacted covalently with the organosilanes aminepropyl-, propyletilenediamine-, propyldietilenetriamine- and glycidoxypropyltrimethoxisilane (GPTS). The hybrid Vac3G, derived from silanization reaction between Vac3 and GPTS, was submitted to subsequent reactions with ethyl, propyl, butyldiamines and 2- aminepiridine resulting in the entrance of new basic centres. The products were characterized by chemical analysis, infrared spectroscopy, X-ray diffraction, 29Si and 27Al NMR in solid state, SEM, and pore volume and surface area determination. The lixiviation of sodic vermiculite originated the restructured porous solids with high superficial area showing the values133, 334, 673 e 575 m2 g-1 for VacX where X = 1,2,3,4, respectively. These solids and sodic vermiculite reacted covalently with each organosilane through methoxyl groups of silane and the hydroxyl surface of matrices. Independently of solid, it was observed that the lixiviation favored the reactivity of activated matrices compared with sodic vermiculite, showing the Vac3 as more reactive comparing with others solids. All modified solids presented high nitrogen content showing the values of 6,31 %. The set of modified vermiculites containing aminepropyl group was applied as adsorbent for divalent cations as copper and nickel in aqueous solution. These solid showed highest affinity for Ni2+ than Cu2+ ions as illustrated by Nf values of 2,97 and 1,23 mmol g-1, respectively. Clay porous solids obtained of leaching treatment of vermiculite are potential substrates for grafting of silanes showing important applications as adsorbents for contaminant species as heavy metals. / A lixiviação seletiva de argilominerais é um método importante na preparação de silicatos porosos constituindo-se em uma rota simples, efetiva e de baixo custo. Neste estudo a vermiculita foi submetida a tratamento ácido com acido nítrico nas concentrações 1, 2, 3 e 4 mol dm- 3, originando os sólidos precursores denominados VacX (x=1 a 4), respectivamente. As matrizes ativadas e a vermiculita reagiram covalentemente com os organosilanos aminopropil-, propiletilenodiamino-, propildietilenotriamino- e glicidóxipropiltrimetoxissilano (GPTS) através dos grupos metoxilas do silano e as hidroxilas da superfície das matrizes. O híbrido Vac3G, derivado da silanização do Vac3 com GPTS, sofreu reações subseqüentes com as diaminas etil, propil, butildiamina e 2- aminopiridina, possibilitando a entrada de novos centros básicos. Os diversos sólidos foram caracterizados por análise química, espectroscopia na região do IV, DRX, RMN 29Si e 27Al, MEV, volume de poro e área superficial. A lixiviação da vermiculita sódica originou sólidos porosos reestruturados com elevadas áreas superficiais cujos valores foram 133, 334, 673 e 575 m2 g-1 para os sólidos Vac1, Vac2, Vac3 e Vac4, respectivamente. Independentemente do sólido, observou-se que à medida que a lixiviação se torna mais acentuada, houve um aumento na reatividade das matrizes ativadas em relação à vermiculita original, sendo a matriz Vac3 a mais reativa diante das reações aqui propostas. Todos os sólidos modificados apresentaram altos teores de grupos orgânicos incorporados. A série de vermiculitas modificadas com o grupo aminopropil foi utilizada para a adsorção de cátions divalentes de cobre e níquel em solução aquosa, mostrando maior afinidade para os íons de Ni2+ (aq) do que para Cu2+ (aq) como ilustrado pelos valores Nf de 2,97 e 1,23 mmol g-1, respectivamente. Os sólidos porosos argilosos derivados de tratamento ácido da vermiculita são substratos potenciais para imobilização de silanos apresentando importantes aplicações como adosrventes para espécies poluentes como metais pesados.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-07-12T15:24:09Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO Crisleide Maria da Siolva Nascimento Acioly.pdf: 1856527 bytes, checksum: 9769ca344829feac7bd75efa5065a57c (MD5) / Made available in DSpace on 2016-07-12T15:24:09Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO Crisleide Maria da Siolva Nascimento Acioly.pdf: 1856527 bytes, checksum: 9769ca344829feac7bd75efa5065a57c (MD5) Previous issue date: 2015-04-24 / FACEPE / A indústria de refino de óleo vegetal encontra-se em expansão na demanda produtiva nos últimos anos, consequentemente tem aumentado os resíduos gerados no processo produtivo. A argila impregnada com óleo, resultante da etapa de clarificação deste, passa a ser um resíduo considerado altamente contaminante. A proposta deste trabalho consiste na reutilização da argila contaminada, pós tratamento térmico, como adsorvente dos corantes NB 180 - Nylosan Azul Brilhante (ácido) e RR 133 - Remazol Red (reativo), estes utilizados na indústria têxtil e fortemente presentes no efluente gerado por esta. Inicialmente foi realizado um planejamento fatorial completo 23 , tendo como variáveis de entrada a massa de argila, bem como a temperatura e o tempo de calcinação, a fim de verificar a melhor condição para a remoção do óleo da argila pela redução da massa (variável resposta). Foi realizada a caracterização do material por análises de Difração de Raio X (DRX), área superficial (BET) e Microscopia Eletrônica de Varredura (MEV). Em seguida todas as amostras de argila do planejamento fatorial foram submetidas a um processo adsortivo, no qual foi utilizando 0,5 g de adsorvente, submetido a uma agitação de 300 rpm na temperatura de 30 ºC. Os experimentos foram conduzidos em batelada e em duplicata para a minimização de erros. Os resultados mostraram que a argila beneficiada, pós tratamento térmico apresentou uma capacidade de remoção de 96,7 % para o corante ácido NB 180 e 58,7 % para o corante Reativo RR 133, resultado este que indica a viabilidade de utilização da argila recuperada no tratamento de efluentes advindos da indústria têxtil. / The vegetable oil refining industry is booming in the production demand in recent years, as a result has increased the waste generated in the production process. The clay impregnated with oil, resulting from the clarification stage of this, it becomes a residue considered highly polluting. The purpose of this work is the reuse of contaminated clay, after heat treatment, as adsorbent of dyes NB 180 - Nylosan Brilliant Blue (acid) and RR 133 - Remazol Red (reactive), these used in the textile and strongly present in the effluent generated it is. Initially we performed a full factorial design 23, having as input variables the mass of clay, as well as the temperature and time of calcination, in order to establish the best condition for the clay oil removal by reducing the mass (dependent variable ). The characterization of the material by diffraction of X-ray analysis (XRD), surface area (BET) and Scanning Electron Microscopy (SEM) was performed. Then all samples clay factorial design were subjected to an adsorptive process, which was using 0.5 g of adsorbent, undergoes a 300 rpm agitation at a temperature of 30 ° C. The experiments were conducted in batch and in duplicate to minimize errors. The results showed that the clay favored, after heat treatment had a 96.7% removal capacity for acid dye NB 180 and 58.7% for the dye Reactive RR 133, a result that indicates the feasibility of the use of recovered clay in the treatment of effluent coming from the textile industry.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-06-09T18:33:58Z No. of bitstreams: 0 / Made available in DSpace on 2015-06-09T18:33:58Z (GMT). No. of bitstreams: 0 / Este trabalho apresenta a preparação e caracterização de compósitos baseados em poli (tereftalato de butileno) PBT e argila brasileira modificada preparados por intercalação por fusão. Os nanocompósitos de PBT com 3 e 5 %, em peso, de argila organicamente modificada, pela adição de um sal quaternário amônio, foram preparadas pelo processo de extrusão utilizando-se uma máquina extrusora dupla rosca. Após o processo de extrusão, os materiais foram injetados para obtenção de corpos-de-prova para os ensaios de caracterização. Parte dos corpos-de-prova foram submetidos ao processo de irradiação utilizando-se um acelerador de feixes de elétrons de 1,5 MeV, à temperatura ambiente e na presença de ar. As amostras de PBT puro e nanocompósitos irradiadas e não irradiadas foram caracterizadas por meio de ensaios mecânicos de tração, flexão e impacto, ensaios de temperatura de distorção térmica (HDT), difração de raios - X (DRX), microscopia eletrônica de varredura (MEV), índice de fluidez, termogravimetria (TG) e calorimetria exploratória diferencial (DSC) e a correlação entre as propriedades foi discutida. Os resultados mostraram que a adição da argila, em ambas as porcentagens, promoveu aumento superior a 50 % na resistência a tração na ruptura e um ganho de cerca de 35 % na temperatura de distorção térmica quando comparado ao polímero puro. O tratamento por radiação ionizante de feixe de elétrons nas doses utilizadas neste estudo não apresentaram mudanças significativas nas propriedades dos materiais. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2016-08-19T12:56:32Z (GMT). No. of bitstreams: 1 GILVAN PEREIRA DE FIGUEREDO.pdf: 11579757 bytes, checksum: dda638ee3ac748c09fb726ca60cc9e98 (MD5) Previous issue date: 2010-03-12 / The State of the Maranhão, Northeast of Brazil, has large occurrences of clays and zeolites. Nevertheless, these materials are not commercially exploited, due to lack of studies on its mineralogical and chemical composition. In this context, the objective this paper has as to study the physico-chemical features, particularly textural and structural properties and surface acidity of some natural clays and zeolites from the State of Maranhão. Thirteen samples of clays and four of zeolites were collected in Governador Edson Lobão, Montes Altos, Barra do Corda, Presidente Dutra, Grajaú, Codó and Carolina. All materials were characterized by X ray diffraction (XRD), X ray fluorescence (XRF), thermal analysis (TGA/DTA/DSC), N2 and n-butylamine adsorption/desorption. The obtained results revealed that the clays are, under a mineralogy view point, constituted by, basically, smectites and kaolinites, being some of these solid composites for 100% of sand and another one for a mixture of minerals of iron and clay, showing diversified chemical compositions and specific areas which varying from 2 m2/g until 85 m2/g. The zeolites showed to be structurally similar with a mixed mineralogical composition, presenting stilbite phases as well as smectite, with quite low specific areas (5 m2/g until 13 m2/g). Zeolites revealed to be more acidic than the clays. However, it should be emphasized that the surface acidity of all clays is also significant, being characterized by strong acid sites. In the particular case of the smectites, mainly of A5 sample, it was verified that the chemical activation, through acid treatment, modified its crystalline structure and increased its specific area for 136,53 m2/g. The adsorption capacity of the acid-activated clays had been more of natural clays and in some cases, these values had been similar to those gotten when using commercial clays. In a general way, this study indicates that the evaluated solids can be applied as adsorbents, as catalysts and as raw materials for refractory and ceramics production. / O Estado do Maranhão, Nordeste do Brasil, possui diversas ocorrências de argilas e de zeólitas. Apesar disso, esses materiais não são explorados comercialmente, devido à falta de estudos sobre sua composição mineralógica e química. Diante disso, este trabalho tem como objetivo estudar as características físico-químicas, especialmente as propriedades texturais e estruturais e acidez superficial de algumas argilas e zeólitas naturais do Estado do Maranhão. Foram coletadas treze amostras de argilas e quatro de zeólitas, nos municípios de Governador Edson Lobão, Montes Altos, Barra do Corda, Presidente Dutra, Grajaú, Codó e Carolina. Os materiais foram caracterizados por DRX, FRX, TGA/DTA/DSC, adsorção/dessorção de N2 e de n-butilamina. Os resultados obtidos revelaram que as argilas são mineralogicamente constituídas por, basicamente, esmectitas e caulinitas, sendo alguns desses sólidos compostos por quase 100% de areia e outro por uma mistura de minerais de ferro e argila, apresentando composições químicas variadas e áreas específicas que vão de 2 a 84 m2/g. As zeólitas são estruturalmente semelhantes, de composição mineralógica mista, apresentado estruturas de estilbita cálcica e esmectita, com áreas específicas bastante baixas (5 m2/g a 13 m2/g). As zeólitas mostraram-se muito mais ácidas do que as argilas. Porém, deve-se ressaltar que a acidez superficial das argilas é também apreciável, possuindo sítios ácidos mais fortes. No caso particular das esmectitas, principalmente da amostra A5, verificou-se que a ativação química, através de tratamento ácido, modificou sua estrutura cristalina e aumentou sua área específica para 136,53 m2/g. A capacidade de adsorção das argilas ativadas foram superiores a das argilas naturais e em alguns casos, esses valores foram semelhantes àqueles obtidos ao empregar argilas comerciais. De um modo geral, este estudo indica que os sólidos avaliados podem ser aplicados tanto como adsorventes e catalisadores quanto como matérias-primas para a produção de material cerâmico e refratário.

Les floculants à base de polyacrylamide (PAM) sont produits à partir du monomère toxique : l’acrylamide (AMD) et peuvent en contenir des quantités résiduelles (jusqu’à 0,1% en Europe). Après utilisation pour faciliter la séparation solide/liquide des eaux de procédés dans les industries de granulat, ces floculants sont stockés avec les boues de décantation dans des lagunes à partir desquelles une dissémination de l’AMD et du PAM vers les eaux de surface ou les eaux souterraines peut avoir lieu. Dans ces travaux de thèse, les interactions du PAM et de l’AMD avec des particules de boue et des phases argileuses (kaolinite et illite, utilisées pour étanchéifier les lagunes de décantation) ont été étudiées. Pour pouvoir quantifier correctement l’AMD, une méthode d’analyse basée sur la HPLC/MS/MS en injection directe a été développée. Cette méthode a été validée avec les normes Afnor NF T 90-210 et NF T 90-220 avec une limite de quantification égale à 1 µg/L. L’étude de l’interaction de l’AMD avec des particules de boue d’un site de granulat et deux argiles (kaolinite et illite) a mis en évidence une faible adsorption de l’AMD sur ces phases solides (<10%), indépendante du temps, de la concentration en AMD et du pH. Inversement, le PAM s’adsorbe fortement et irréversiblement sur la boue, la kaolinite et l’illite avec une cinétique rapide de 1er ordre. Les isothermes d’adsorption sont bien corrélées avec les modèles de Langmuir et de Freundlich. Les quantités d’adsorption du PAM sont indépendantes du pH des suspensions mais fortement impactées par la force ionique qui influence les interactions électrostatiques entre le PAM et les surfaces solides. / Polyacrylamide (PAM) based floculants are produced from the highly toxic acrylamide (AMD) monomer and can contain residual amounts (up to 0.1% in Europe) of AMD. After they are used to facilitate liquid/solid separation of process water in aggregate quarries, PAM floculants are stored, with the sewage sludge, in decantation lagoons. Dissemination of AMD and PAM to groundwater and surface water from these lagoons can occur. In this work, we aimed to study the interactions of AMD and PAM with sludge particles and clays (kaolinite and illite used for decantation lagoon sealing) from aggregate quarry. To correctly quantify the AMD, analytical method based on HPLC/MS/MS with direct injection was developed. This method was validated according to the Afnor guidelines (NF T 90-210 and NF T 90-220) with a limit of quantification of 1 µg/L. Results of AMD adsorption experiments showed a low adsorption of AMD to sludge and clay (kaolinite and illite) particles, which is independent of time, AMD concentration and pH. Inversely, PAM was found to adsorb strongly and irreversibly to sludge, kaolinite and illite with a rapid kinetic of adsorption which consists of first order kinetic. Adsorption isotherms are well correlated with Langmuir and Freundlich models. PAM adsorption quantities are independent on the pH of suspensions, but are strongly impacted by the ionic strength which affects electrostatic interactions between PAM and solid surfaces.

Doctor of Philosophy / Department of Horticulture, Forestry, and Recreation Resources / Kimberly A. Williams / The use of calcined clays contributes properties of nutrient and water retention to soilless root media, which varies greatly depending on the parent clay and calcining treatment. This research characterized phosphate (PO[subscript]4) sorption of various calcined clay products, including low volatile and regular volatile material (LVM and RVM) 2:1 Attasorb clays (Engelhard Corp.), 2:1 Terra Green LVM clays (Oil-Dri Co.), and Turface (Profile Products LLC) at various particle sizes; 1:1 kaolin clays (Thiele Kaolin Co.) in powder form, and diatomaceous earth (Diatomite, Eagle Picher Minerals, Inc.). Three of the calcined materials, Terra Green montmorillonite and Attasorb attapulgite (which had high PO[subscript]4-sorption based on isotherms), and diatomaceous earth (which had negligible PO[subscript]4-sorption) were evaluated as components of soilless root media in two separate greenhouse experiments. The effect of the calcined materials, rate of incorporation (0%, 5%, 10% and 20% by volume in a mix with peat and perlite), and PO[subscript]4-P application rate (0, 5, 15, 45 mg.L[superscript]-1 PO[subscript]4-P) on plant growth, effluent P content and water use were determined during production and post-production of Impatiens wallerana Hook f. 'Tempo Rose'. The calcined materials varied in their ability to adsorb PO[subscript]4-P and generally yielded L-type isotherms. Laboratory results indicated potential for substantive P retention by several of the calcined materials when used in container production. For most materials, PO[subscript]4-P sorption did not show pronounced pH dependence. During production and post-production, the test materials not only improved PO[subscript]4-P retention but also water retention and water use efficiency while still maintaining optimal physical properties at incorporation rates of 5 to 10%. Diatomaceous earth resulted in PO[subscript]4-P retention not significantly different from the calcined clays.

>Magister Scientiae - MSc / Understanding fluid flow and solute transport within the vadose (unsaturated) zone is an essential prerequisite for protection of groundwater from contaminant sources occurring overland. Preferential flow paths in the vadose zone pose a significant problem because they are potential avenues for rapid transport of chemicals from contamination sources to the water table. The objectives of this study were: i) To review and understand flow and transport processes in unsaturated zones. In this study, particular emphasis is placed on understanding mechanisms that cause non-uniform (preferential) flow for two case studies, namely the Cape Flats sandy environment and the Mpumalanga Highveld fractured rock environment. ii) To evaluate the adequacy of models, in particular MACRO 5.0, in simulating flow and transport in the vadose zone, by making use of two case study sites (Cape Flats and Mpumalanga Highveld). Of particular importance is the evaluation of transfer coefficients to represent fluid and solute exchange between macropores and matrix. iii) To run a sensitivity analysis with MACRO 5.0 in order determine which input model parameters are the most relevant in describing the effects of preferential flow in water and solute transport. Two case studies were investigated, the first at a landfill site overlying sandy unconfined aquifer (Coastal Park, Cape Town), and the second at an industrial site overlying cracking clayey soil and fractured rocks (Mpumalanga Highveld - Secunda, Mpumalanga Province). For the Coastal Park site, simulations of soil water content and leaching of a generic mobile contaminant were compared to monitored soil water contents and chloride concentrations in groundwater. For the Mpumalanga Highveld site, simulations of soil water content and concentrations of boron and fluoride originating from effluent irrigation were compared to soil profile measurements. In both cases, the MACRO 5.0 model predictions agreed with measurements well, provided appropriate input calibration data were used. The sensitivity analysis indicated that soil water properties related to preferential flow (hydraulic conductivity at the boundary between macropores and matrix, soil water content and tension, and diffusion) have influence on simulation results. Similarly, the solute balance is mostly influenced by degradation rate coefficients (both in solid and liquid phases), sorption distribution coefficients and solute concentrations.

La présente étude vise à comprendre le comportement chimico-hydro-mécanique des argiles raides à travers deux formations géologiques, l'argile de Boom et les argiles yprésiennes, qui sont censées être des formations hôtes potentielles pour le stockage de déchets radioactifs en Belgique. Le comportement volumique a été étudié tant à l'état intact qu'à l'état reconstitué, et sous différentes conditions : K0 et isotrope, sous des boucles de chargement - déchargement. Les résultats obtenus montrent que le comportement volumique de ces argiles est gouverné par la compétition entre l'effet physico-chimique et l'effet mécanique, caractérisée par une contrainte seuil qui correspond à la contrainte de gonflement en termes de changements de structure. Une loi de comportement volumique a été ainsi développée afin de décrire cet aspect. La perméabilité a été déterminée, comparée avec les résultats dans la littérature et corrélée avec les paramètres comme l'indice des vides. La variation de la perméabilité avec la profondeur ont mis en évidence le rôle déterminant des macro-pores dans le transfert des fluides. Le comportement volumique et la perméabilité des argiles de Boom et yprésiennes intactes sont aussi influencés par la variation de la composition chimique de l'eau de pore, qui modifie la double couche diffuse et favorise l'agrégation des particules argileuses. Les caractéristiques élastiques, la surface de charge et l'enveloppe de rupture ont été identifiées pour le comportement déviatorique des argiles de Boom et yprésiennes. Un modèle élasto-plastique conceptuel a été développé permettant de tenir compte des effets du gonflement et de la compétition entre l'effet mécanique et l'effet physico-chimique / The present research aims to understand the chemo-hydro-mechanical behavior of stiff clays through two geological formations, the Boom Clay and the ypresian clays which are considered as possible host formations for the radioactive wastes disposal in Belgium. The volume change behavior was studied in both intact and reconstituted states, and under different conditions: under K0 and isotropic loading, under loading/unloading loops. The results show that the volume change behavior is governed by the competition between the physico-chemical effect and the mechanical effect, characterized by a threshold stress which corresponds to the swelling stress in terms of structure changes. A constitutive law was developed to capture this aspect. The permeability was determined, compared with the results in literature and correlated with the parameters as void ratio. The permeability variation with depth shows the important role of macro-pores in fluids' transfer. The volume change behavior and permeability of intact Boom Clay and ypresian clays are also influenced by pore water chemical composition changes which modify the diffuse double layer and give rise to the aggregation of clay particles. The elastic parameters, yield curve and failure envelope of Boom Clay and ypresian clays were identified. A conceptual elasto-plastic model was developed, accounting for the swelling effects and the competition between the physico-chemical effect and the mechanical effect

L’étude de l’adsorption et de la mobilité des ions dans les argiles est importante pour mieux appréhender de nombreux processus géochimiques et environnementaux, de même que pour prédire le comportement des radionucléides dans les conditions du stockage géologique. A cause de leurs tailles très petites (< 2μm), il n’est pas toujours évident d’étudier les argiles à l’aide des méthodes et techniques expérimentales existantes. L’une des alternatives à ce problème consiste alors à utiliser la modélisation moléculaire pour les étudier. En plus de leurs tailles fines, les argiles présentent également des structures complexes, qui peuvent survenir en raison de la multiplicité de possibilités de distributions et d’arrangements des substitutions isomorphiques dans leurs couches. Il a été clairement démontré qu’il existe une corrélation entre la distribution des substitutions dans les couches des argiles et les propriétés de ces dernières. En revanche, ceci reste à démontrer en ce qui concerne l’arrangement de ces substitutions dans les couches de l’argile. Dans ce travail, la modélisation moléculaire est utilisée pour déterminer et comparer les propriétés d’hydratation, ainsi que la structure et la mobilité des ions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ni²⁺, UO₂²⁺) et de l’eau dans l’espace interfoliaire de trois modèles de montmorillonite, différents entre eux par l’arrangement des substitutions isomorphiques dans les couches de l’argile.L’adsorption et la diffusion des cations cités plus haut et de l’eau sont également étudiées à la surface de la montmorillonite et les résultats sont comparés à ceux obtenus dans l’espace interfoliaire à 298 K et à 363 K. Les résultats obtenus dans ce travail s’accordent bien avec les observations expérimentales, et font ressortir une corrélation plus ou moins importante entre le modèle d’argile utilisé et le type de propriété calculée. Cette corrélation dépend également de la nature du cation présent dans la structure de la montmorillonite et de sa teneur en eau. / The study of adsorption and ion mobility in clay minerals is important for a better understanding of many geochemical and environmental processes, as well as to predict the behavior of radionuclides in geological storage conditions. Because of their very small size (<2μm), it is not always easy to study clays by using the existing experimental methods and techniques. One alternative to this issue is to use computational molecular modeling to carry out clay studies. In addition to their tiny size, clays minerals also have complex structures, which can appear due to various possibilities in the distribution and arrangement of isomorphic substitutions in their layers. It has been clearly demonstrated that there is a strong correlation between the distribution of substitutions in the clay layers and their properties. However, this remains to be shown regarding the arrangement of the substitutions in the layers of the clay. In this work, computational molecular modeling techniques are used to determine and compare the hydration properties, as well as the structure and mobility of ions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ni²⁺,UO₂²⁺) and water in the interlayer space of the three models of montmorillonite, that differ from each other by the arrangement of isomorphic substitutions in the clay layers.The adsorption and diffusion of the previously listed cations and water are also studied on the surface of montmorillonite clay and the results are compared to those obtained in the interlayer space both at 298 K and at 363 K. The data generated in this work agree well with experimental observations, and show a more or less significant correlation between the clay model used and the type of property calculated.

La présence d’argile dans les granulats (sables et graviers), influencent considérablement les propriétés rhéologiques des bétons. Considérant les évolutions techniques apportées au béton ces dernières années, la compréhension des mécanismes de nocivité des argiles est donc d’un intérêt majeur sur le plan industriel. Au cours de cette étude, nous avons scindé la problématique en deux parties, la première s’attardant plus spécifiquement sur les mécanismes d’adsorption aux surfaces des argiles. Une analyse fines des interactions polymere-argile par IR, SAXS-WAXS et mesure d’adsorption a alors permis de valider l’adsorption des superplastifiants par les argiles et le rôle bénéfique de l’utilisation de molécule cationique (F25) pour empêcher leur fixation. La détermination d’un processus d’adsorption par échange cationique de ces molécules explique d’une part leur effet inertant et d’autre part la restructuration des particules d’argile à l’échélle du micron comme du nanométre. Dans un deuxième temps, une étude rhéologique des systèmes granulaires a permis de caractériser l’effet intrinséque de argiles sur les propriétés d’écoulement de ces systèmes. L’étude des suspensions d’argile a démontré le rôle de la rétention d’eau par les argiles. L’anisotropie des particules, caractérisée au moyen de différentes techniques (MET, SAXS-WAXS), permet d’expliquer cette rétention d’eau / Clay minerals which can be found in granular materials strongly influence the rheological properties of fresh concrete. Due to the recent technical evolution of concrete, the understanding of the effect of clays in such systems takes on a significant industrial interest. This study was divided into two part, the first one dealing with the adsorption mechanisms of two polymers onto clay surfaces: a superplasticizer (PCP) and a polycation (F25). IR and SAXS-WAXS analysis together with adsorption measurment revealed that superplasticizer are adsorbed by clays and that the used of polycation inhibites clays-PCP interactions. The adsorption process of F25 onto clays by cationic exchange explains the preferential adsorption of cationic compounds rather than PCP and the restructuration of clay particles at the nano and micronic scale during the adsorption. In a second part, the rheological study of granular suspensions revealed a strong effect of clay particles on the flow behaviors of such systems. The rheological study of pure clay suspensions allowed the modelisation of the effect of clays on granular suspensions using excluded volume. In this case, the anistropic features of clays particles characterized by various technics (TEM, SAXS-WAXS) explains water retention properties of such nanometric minerals