Made available in DSpace on 2014-12-17T14:08:39Z (GMT). No. of bitstreams: 1 Julio Cezar de oliveira Freitas_nao permite publicacao_pdf.pdf: 2629498 bytes, checksum: 933e76a7de6f0be7c8d579af7a68bb18 (MD5) Previous issue date: 2010-06-18 / The primary cementing is an important step in the oilwell drilling process, ensuring the mechanical stability of the well and the hydraulic isolation between casing and formation. For slurries to meet the requirements for application in a certain well, some care in the project should be taken into account to obtain a cement paste with the proper composition. In most cases, it is necessary to add chemicals to the cement to modify its properties, according to the operation conditions and thus obtain slurries that can move inside the jacket providing a good displacement to the interest area. New technologies of preparation and use of chemicals and modernization of technological standards in the construction industry have resulted in the development of new chemical additives for optimizing the properties of building materials. Products such as polycarboxylate superplasticizers provide improved fluidity and cohesion of the cement grains, in addition to improving the dispersion with respect to slurries without additives. This study aimed at adapting chemical additives used in civil construction to be used use in oilwell cement slurries systems, using Portland cement CPP-Special Class as the hydraulic binder. The chemical additives classified as defoamer, dispersant, fluid loss controller and retarder were characterized by infrared absorption spectroscopy, thermogravimetric analyses and technological tests set by the API (American Petroleum Institute). These additives showed satisfactory results for its application in cement slurries systems for oil wells. The silicone-based defoamer promoted the reduction of air bubbles incorporated during the stirring of the slurries. The dispersant significantly reduced the rheological parameters of the systems studied. The tests performed with the fluid loss controller and the retarder also resulted in suitable properties for application as chemical additives in cement slurries / A cimenta??o prim?ria ? uma etapa importante durante o processo de perfura??o de po?os petrol?feros, garantindo a estabilidade mec?nica do po?o e o isolamento hidr?ulico entre o tubo de revestimento e a forma??o. Para que a pasta de cimento atenda aos requisitos estabelecidos para sua aplica??o em um determinado po?o, alguns cuidados no seu projeto de execu??o devem ser levados em considera??o para a obten??o de uma pasta de cimento com composi??o adequada. Na grande maioria dos casos, ? necess?ria a adi??o de produtos qu?micos ao cimento para modificar suas propriedades, conforme as condi??es do po?o ou opera??o e, assim, obter pastas que possam se deslocar no interior do revestimento promovendo um bom deslocamento at? a zona de interesse. Novas tecnologias de prepara??o e uso de produtos qu?micos e a moderniza??o dos padr?es tecnol?gicos no setor da constru??o civil t?m resultado no desenvolvimento de novos aditivos qu?micos para a otimiza??o das propriedades dos materiais construtivos. Produtos como superplastificantes a base de policarboxilato proporcionam maior fluidez e coes?o dos gr?os de cimento, al?m de melhorar a dispers?o em rela??o ?s pastas sem aditivos. Este trabalho tem como objetivo adequar aditivos qu?micos utilizados na constru??o civil para aplica??o em sistemas de pastas de cimento de po?os petrol?feros, utilizando como aglomerante hidr?ulico o cimento Portland CPP-Classe Especial. Os aditivos qu?micos classificados como antiespumantes, dispersantes, controladores de filtrado e retardadores de pega foram caracterizados por espectroscopia de absor??o na regi?o do infravermelho, an?lise termogravim?trica e ensaios tecnol?gicos estabelecidos pelo API (American Petroleum Institute). Estes aditivos apresentaram resultados satisfat?rios para sua aplica??o em sistemas de pasta de cimento para po?os de petr?leo. O antiespumante, a base de silicone, promoveu redu??o do aprisionamento de ar durante o processo de agita??o das pastas. O aditivo dispersante reduziu consideravelmente os par?metros reol?gicos dos sistemas estudados. Os testes realizados com o controlador de filtrado e o retardador de pega tamb?m apresentaram propriedades adequadas para aplica??o como aditivos qu?micos em pastas para cimenta??o

Made available in DSpace on 2014-12-17T14:08:40Z (GMT). No. of bitstreams: 1 MariaRPF_DISSERT_partes_autorizadas.pdf: 435614 bytes, checksum: 36615dc20f70f58a222f546b112da5b2 (MD5) Previous issue date: 2009-12-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The production of heavy oil fields, typical in the Northeastern region, is commonly stimulated by steam injection. High bottom hole temperatures are responsible not only for the development of deleterious stresses of the cement sheath but also for cement strength retrogression. To overcome this unfavorable scenario, polymeric admixtures can be added to cement slurries to improve its fracture energy and silica flour to prevent strength retrogression. Therefore, the objective of the present study was to investigate the effect of the addition of different concentrations of polyurethane (5-25%) to cement slurries containing 40% BWOC silica flour. The resulting slurries were characterized using standard API (American Petroleum Institute) laboratory tests. In addition to them, the mechanical properties of the slurries, including elastic modulus and microhardness were also evaluated. The results revealed that density, free water and stability of the composite cement/silica/polyurethane slurries were within acceptable limits. The rheological behavior of the slurries, including plastic viscosity, yield strength and gel strength increased with the addition of 10% BWOC polyurethane. The presence of polyurethane reduced the fluid loss of the slurries as well as their elastic modulus. Composite slurries also depicted longer setting times due to the presence of the polymer. As expected, both the mechanical strength and microhardness of the slurries decreased with the addition of polyurethane. However, at high bottom hole temperatures, the strength of the slurries containing silica and polyurethane was far superior than that of plain cement slurries. In summary, the use of polyurethane combined with silica is an interesting solution to better adequate the mechanical behavior of cement slurries to heavy oil fields subjected to steam injection / Em campos que possuem ?leos pesados ? necess?rio um meio para estimular o ?leo a fluir pela forma??o, tais reservas s?o caracter?sticas da Regi?o Nordeste do Brasil e necessitam da inje??o de vapor para sua recupera??o. Temperatura elevada no fundo do po?o proporciona tens?es induzidas na bainha de cimento, al?m de favorecer a retrogress?o de resist?ncia do cimento, comprometendo a qualidade da cimenta??o. Sendo assim, adiciona-se em pastas cimentantes, o pol?mero, afim de se promover maior plasticidade e s?lica a para evitar o efeito da perda de resist?ncia mec?nica (retrogress?o). Diante disso, o presente trabalho teve como objetivo estudar o comportamento de pastas de cimento contendo poliuretana em diferentes concentra??es (5% a 25%) e 40% BWOC de s?lica flour. Foram realizados ensaios padronizados pelo API (American Petroleum Institute) e ensaios para obten??o do m?dulo de elasticidade e microdureza, al?m da caracteriza??o das pastas formuladas. Os resultados mostraram que as pastas comp?sitas cimento/s?lica/poliuretana apresentaram valores de peso espec?fico, ?gua livre e estabilidade dentro dos estabelecidos por norma. As propriedades reol?gicas foram modificadas, a viscosidade pl?stica, o limite de escoamento e os g?is aumentaram com a adi??o a partir de 10% BWOC de poliuretana. A poliuretana favoreceu melhor controle de filtrado e diminuiu o m?dulo de elasticidade das pastas. A mesma tamb?m promoveu retardamento da pega do cimento. As propriedades mec?nicas de resist?ncia e microdureza diminu?ram com a adi??o de s?lica e/ou s?lica/poliuretana, entretanto, em alta temperatura a resist?ncia mec?nica das pastas com s?lica e poliuretana tiveram um valor bem superior quando comparado com a pasta de cimento padr?o. A caracteriza??o das pastas mostrou que a adi??o de s?lica e pol?mero diminui o teor de c?lcio do cimento e que h? a forma??o do filme polim?rico. Pol?mero combinado com cimento e s?lica pode ser usado como aditivo para diminuir o m?dulo de elasticidade e, desta forma, fornecer maior plasticidade e resist?ncia ?s ciclagens t?rmicas ocasionadas pelo processo de inje??o de vapor

Made available in DSpace on 2014-12-17T15:01:28Z (GMT). No. of bitstreams: 1 RomeroGSAF_DISSERT.pdf: 5251211 bytes, checksum: 91e35eccdc843f543fbc2744a816fb64 (MD5) Previous issue date: 2012-03-16 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / All around the world, naturally occurring hydrocarbon deposits, consisting of oil and gas contained within rocks called reservoir rocks , generally sandstone or carbonate exists. These deposits are in varying conditions of pressure and depth from a few hundred to several thousand meters. In general, shallow reservoirs have greater tendency to fracture, since they have low fracture gradient, ie fractures are formed even with relatively low hydrostatic columns of fluid. These low fracture gradient areas are particularly common in onshore areas, like the Rio Grande do Norte basin. During a well drilling, one of the most favorable phases for the occurrence of fractures is during cementing, since the cement slurry used can have greater densities than the maximum allowed by the rock structure. Furthermore, in areas which are already naturally fractured, the use of regular cement slurries causes fluid loss into the formation, which may give rise to failures cementations and formation damages. Commercially, there are alternatives to the development of lightweight cement slurries, but these fail either because of their enormous cost, or because the cement properties were not good enough for most general applications, being restricted to each transaction for which the cement paste was made, or both reasons. In this work a statistical design was made to determine the influence of three variables, defined as the calcium chloride concentration, vermiculite concentration and nanosilica concentration in the various properties of the cement. The use of vermiculite, a low density ore present in large amounts in northeastern Brazil, as extensor for cementing slurries, enabled the production of stable cements, with high water/cement ratio, excellent rheological properties and low densities, which were set at 12.5 lb / gal, despite the fact that lower densities could be achieved. It is also seen that the calcium chloride is very useful as gelling and thickening agent, and their use in combination with nanosilica has a great effect on gel strength of the cement. Hydrothermal Stability studies showed that the pastes were stable in these conditions, and mechanical resistance tests showed values of the order of up to 10 MPa / Em todo o mundo, ocorrem naturalmente dep?sitos de hidrocarbonetos, constitu?dos de petr?leo e g?s natural, contidos dentro de rochas denominadas "rochas reservat?rio", em geral arenitos ou carbonatos. Esses dep?sitos existem em variadas condi??es de press?o e profundidade, desde poucas centenas at? milhares de metros. Em geral, reservat?rios mais "rasos" t?m a tend?ncia a fraturar mais facilmente, pois possuem baixo gradiente de fratura, ou seja, as fraturas s?o formadas mesmo com colunas hidrost?ticas de fluido relativamente baixas. Essas zonas de baixo gradiente de fratura s?o particularmente mais comuns em zonas onshore, como aqui no Rio Grande do Norte. Um dos momentos mais prop?cios para a ocorr?ncia de fraturas ? durante a cimenta??o do po?o, ao se utilizar uma pasta cimentante de densidade superior ao m?ximo permitido pela estrutura rochosa. Al?m disso, em zonas j? naturalmente fraturadas, o uso de cimentos comuns causa perda de fluido para a forma??o, o que pode dar causa a cimenta??es falhas. Comercialmente, existem alternativas para o desenvolvimento de sistemas de pastas de cimento leves, mas esses falham ou em raz?o de seu elevad?ssimo custo, ou em fun??o das propriedades da pasta obtida n?o serem suficientemente boas para aplica??es mais gen?ricas, ficando restritas a cada opera??o para qual a pasta de cimento foi feita. Nesse trabalho foi realizado um planejamento estat?stico para determinar a influ?ncia de tr?s vari?veis, definidas como a concentra??o de cloreto de c?lcio, concentra??o de vermiculita e concentra??o de nano s?lica, nas v?rias propriedades do cimento. O uso da vermiculita, um min?rio de baixa densidade presente em grandes quantidades no nordeste brasileiro, como extensor para pastas cimentantes, permitiu a produ??o de pastas est?veis, com alta raz?o ?gua/cimento, propriedades reol?gicas excelentes e baixas densidades, que foram fixadas em 12,5 lb/Gal. Viu-se tamb?m que o cloreto de c?lcio ? um poderoso viscosificante e gelificante, e seu uso combinado com a nano s?lica possui grande efeito nas for?as g?is do cimento. Estudos de estabilidade hidrot?rmica mostraram que as pastas foram est?veis nessas condi??es, e os ensaios de resist?ncia mec?nica mostraram valores da ordem de at? 10 MPa

Made available in DSpace on 2014-12-17T14:07:09Z (GMT). No. of bitstreams: 1 Marcus VCB_DISSERT_PARCIAL.pdf: 2643130 bytes, checksum: 5d46e76949be4c4eb0ad9dfdafb24bcb (MD5) Previous issue date: 2013-02-18 / The materials engineering includes processes and products involving several areas of engineering, allowing them to prepare materials that fulfill the needs of various new products. In this case, this work aims to study a system composed of cement paste and geopolymers, which can contribute to solving an engineering problem that directly involves the exploitation of oil wells subject to loss of circulation. To correct it, has been already proposed the use of granular materials, fibers, reducing the drilling fluid or cement paste density and even surface and downhole mixed systems. In this work, we proposed the development of a slurry mixed system, the first was a cement-based slurry and the second a geopolymer-based slurry. The cement-based slurry was formulated with low density and extenders, 12.0 ppg (1.438 g/cm ?), showing great thixotropic characteristics. It was added nano silica at concentrations of 0.5, 1.0 and 1.5 gps (66.88, 133.76 and 200.64 L/m3) and CaCl2 at concentrations of 0.5, 1, 0 and 1.5%. The second system is a geopolymer-based paste formulated from molar ratios of 3.5 (nSiO2/nAl2O3), 0.27 (nK2O/nSiO2), 1.07 (nK2O/nAl2O3) and 13.99 (nH2O/nK2O). Finally, we performed a mixture of these two systems, for their application for correction of circulation lost. To characterize the raw materials, XRD, XRF, FTIR analysis and titration were performed. The both systems were characterized in tests based on API RP10B. Compressive strength tests were conducted after curing for 24 hours, 7 and 28 days at 58 ?C on the cement-based system and the geopolymer-based system. From the mixtures have been performed mixability tests and micro structural characterizations (XRD, SEM and TG). The results showed that the nano silica, when combined with CaCl2 modified the rheological properties of the cement slurry and from the concentration of 1.5 gpc (200.64 L / m?) it was possible to obtain stable systems. The system mixture caused a change in the microstructure of the material by favoring the rate of geopolymer formation to hinder the C3S phase hydration, thus, the production of CSH phases and Portlandite were harmed. Through the mixability tests it can be concluded that the system, due to reduced setting time of the mixture, can be applied to plug lost circulation zones when mixed downhole / A engenharia de materiais abrange processos e produtos envolvendo v?rias ?reas da engenharia, permitindo que sejam preparados materiais que atendam a v?rias necessidades de novos produtos. Neste caso, este trabalho tem por objetivo estudar um sistema de pasta composto por cimento e geopol?meros, que possa contribuir para a resolu??o de um problema de engenharia que envolve diretamente a explora??o de po?os de petr?leo sujeitos ? perda de circula??o. Para corrigi-la, j? foi proposto na literatura o uso de materiais granulares, fibrosos, redu??o da densidade do fluido de perfura??o ou pasta de cimento e at? mesmo sistemas mistos de fluidos misturados na superf?cie ou no fundo do po?o. Neste trabalho, foi proposto o desenvolvimento de um sistema misto de pastas, sendo o primeiro ? base de cimento Portland e o segundo ? base de geopol?mero. A pasta ? base de cimento, foi formulada com baixa massa espec?fica e aditivos extendedores, 12,0 lb/gal (1,438 g/cm?), apresentando grande car?ter tixotr?pico. Essa pasta foi aditivada com nanoss?lica, em concentra??es de 0,5; 1,0 e 1,5 gpc (66,88; 133,76 e 200,64 L/m3) e CaCl2, em concentra??es de 0,5; 1,0 e 1,5 %. A segunda pasta se constitui ? base de geopol?mero, sendo formulada a partir das raz?es molares de 3,5 (nSiO2/nAl2O3); 0,27 (nK2O/nSiO2); 1,07 (nK2O/nAl2O3) e 13,99 (nH2O/nK2O). E por fim, foi realizada a mistura desses dois sistemas, visando sua aplica??o para corre??o de perda de circula??o. Para caracterizar os precursores foram utilizadas as t?cnicas de DRX, FRX, FTIR e titula??o. Foram realizados os ensaios de caracteriza??o baseados na API RP10B para ambas as pastas puras. Ensaios de resist?ncia ? compress?o foram realizados ap?s a cura por 24 horas, 7 e 28 dias ? 58 ?C, para os sistemas de pasta de cimento e geopol?mero, separadamente. A partir das misturas, foi realizado o ensaio de misturabilidade e caracteriza??es microestruturais (DRX, TG e MEV). Os resultados mostraram que a nanoss?lica, quando combinada ao CaCl2 modificou as propriedades reol?gicas da pasta de cimento e a partir da concentra??o de 1,5 gpc (200,64 L/m?) foi poss?vel se obter sistemas est?veis. A mistura dos sistemas ocasionou uma modifica??o da microestrutura do material, atrav?s do favorecimento da rea??o de geopolimeriza??o em detrimento da hidrata??o da fase C3S, com isso, a produ??o das fases Portlandita e C-S-H foram prejudicadas. Atrav?s dos ensaios de misturabilidade, devido ao reduzido tempo de pega das misturas, pode-se concluir que o sistema misturado, pode ser aplicado para tamponar zonas de perda de circula??o quando misturado no fundo do po?o

Made available in DSpace on 2014-12-17T14:08:56Z (GMT). No. of bitstreams: 1 LuannaCMP_DISSERT.pdf: 3195149 bytes, checksum: 9c2b834c5beeb3439f6a0d1955159637 (MD5) Previous issue date: 2013-09-02 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Although there are a wide variety of additives that act in fresh state, to adjust the properties of cement, there is also a search by additions that improve the tenacity of the cement in the hardened state. This, in turn, can often be increased by inserting fibers, which act on the deflection of microcracks. This study aimed to use a microfiber glass wool (silica-based) as an additive reinforcing the cement matrix, improving the rupture tenacity, in order to prevent the propagation of microcracks in the cement sheath commonly found in oil wells submitted to high temperatures. The fibers were added at different concentrations, 2 to 5% (BWOC) and varied average sizes, grinding for 90 s, 180 s, 300 s, 600 s. The cement slurries were made with a density of 1,90 g/ cm3 (15,6 lb/gal), using Portland cement CPP- Special Class as the hydraulic binder and 40% silica flour. The characterization of the fiber was made by scanning electron microscopy (SEM), particle size by sieving, X-ray fluorescence (XRF), X-ray diffraction (XRD) and thermogravimetry (TG / DTG). Were performed technological tests set by the API (American Petroleum Institute) by rheology, stability, free water, compressive strength, as well as testing rupture energy, elastic modulus and permeability. The characterization results showed good thermal stability of the microfiber glass wool for application in oil wells submitted to steam injection and, also, that from the particle size data, it was possible to suggest that microfibers milled up to 300 s, are ideal to act as reinforcement to the cement slurries. The rheological parameters, there was committal of plastic viscosity when larger lengths were inserted of microfiber (F90). The values obtained by free water and stability were presented according to API. The mechanical properties, the incorporation of microfiber to the cement slurries gave better rupture tenacity, as compared to reference cement slurries. The values of compressive strength, elastic modulus and permeability have been maintained with respect to the reference cement slurries. Thus, cement slurries reinforced with microfiber glass wool can ensure good application for cementing oil wells submitted to steam injection, which requires control of microcracks, due to the thermal gradients / Embora exista uma grande variedade de aditivos que atuam no estado fresco, para ajuste das propriedades do cimento, existe tamb?m uma busca por adi??es que melhorem a tenacidade do cimento no estado endurecido. Esta, por sua vez, pode comumente ser aumentada pela inser??o de fibras, as quais agem na deflex?o de microtrincas. Este trabalho tem como objetivo utilizar microfibras de l? de vidro (? base de s?lica) como aditivo de refor?o ? matriz ciment?cia, melhorando a tenacidade ? ruptura, a fim de evitar a propaga??o de microfissuras na bainha cimentante comumente encontradas em po?os de petr?leo submetidos a altas temperaturas. As fibras foram adicionadas em diferentes teores, de 2 a 5% (BWOC), e variados tamanhos m?dios, obtidos variando o tempo de moagem de 90 s, 180 s, 300 s e 600 s. As pastas foram formuladas com densidade de 1,90 g/ cm3 (15,6 lb/gal), utilizando o cimento Portland CPP-Classe Especial como aglomerante hidr?ulico e 40% de s?lica flour. A caracteriza??o da fibra foi feita por microscopia eletr?nica de varredura (MEV), granulometria por peneiramento, fluoresc?ncia de raios X (FRX), difra??o de raios X (DRX) e termogravimetria (TG/DTG). Foram realizados ensaios tecnol?gicos padronizados pela API (American Petroleum Institute) de reologia, estabilidade, ?gua livre, resist?ncia ? compress?o, bem como testes de energia de ruptura, m?dulo de elasticidade e permeabilidade. Os resultados da caracteriza??o mostraram boa estabilidade t?rmica da microfibra de l? de vidro para aplica??o em po?os submetidos ? inje??o de vapor. A partir dos dados de granulometria, foi poss?vel verificar que microfibras mo?das at? 300 s s?o ideais para agirem como refor?o ? pasta de cimento. Dos par?metros reol?gicos, houve o comprometimento da viscosidade pl?stica quando foram inseridos comprimentos maiores de microfibra (F90). Os valores obtidos de ?gua livre e estabilidade se apresentaram conformes ? norma API. Das propriedades mec?nicas, a incorpora??o de microfibra ? pasta de cimento conferiu melhor tenacidade ? ruptura, comparada a pasta de refer?ncia. Os valores obtidos de resist?ncia ? compress?o, m?dulo de elasticidade e permeabilidade foram mantidos com rela??o ? pasta padr?o. Desse modo, pastas ciment?cias refor?adas com microfibra de l? de vidro podem garantir boas aplica??es em cimenta??o de po?os de petr?leo sujeitas ? inje??o de vapor, que exija o controle de microfissuras em virtude do gradiente de temperatura

Cement slurries are used in oil wells to isolate the production area from the rock formation. An important property of these materials is their durability. Due to the interactions of the cement slurries with aggressive media in the oil wells, the durability can be threatened or lost. Cement slurries modified with polymers are promising materials candidates for cementing oil wells. Thus, it is necessary to evaluate new materials in hostile environments. In this work, new cement slurries were prepared with the Epoxy resin and the ethylenediamine hardener in two different media: distilled water and sea water. The new slurries were tested for their mechanical properties and characterized before and after interaction with the following media: production water, hydrochloric acid solution and mud acid solution. After 365 days of contact with the production water, the modified slurries showed greater chemical and mechanical resistance compared to the slurries without the polymer network (Standard slurries). Moreover, for the modified slurries after contact with the production water, a decrease of 9% in the compressive strength occurred, whereas for the slurries without the polymer network, the reduction reached 40%. Kinetic studies, chemical and thermodynamic equilibrium were carried out in the investigation of the interaction of the cement slurries with the solutions of HCl and mud acid. The results have suggested that the interactions between the modified slurries and the acid media are due to surface reactions with preservation of the hydrated compounds of the cement, causing a mass loss around 25%. For the standard slurries, the mechanism is predominantly diffusion, with structural deterioration of these slurries and mass loss of approximately 46%. Thus, the modified slurries with the polymer network Epoxy-EDA presented good characteristics to be used in the oil well procedures. / Pastas de cimento são utilizadas em poços de petróleo para isolar a zona de produção da formação rochosa. Uma propriedade importante desses materiais é sua durabilidade. Devido suas interações com meios agressivos, essa propriedade pode ser ameaçada ou perdida. Pastas de cimento modificadas com polímeros são materiais promissores candidatos à cimentação de poços de petróleo. Assim, é necessário avaliar novos materiais em meios hostis. Neste trabalho, novas pastas de cimento foram preparadas com a resina Epoxy e o endurecedor Etilenodiamina em dois meios distintos: água destilada e água do mar. As novas pastas foram testadas em relação às suas propriedades mecânicas e caracterizadas antes e após a interação com os seguintes meios: água de produção, solução de ácido clorídrico e solução de mud acid. Após 365 dias de contato com a água de produção, as pastas modificadas apresentaram maior resistência química em comparação com as pastas sem a rede polimérica (pastas padrão). Além disso, para as pastas modificadas após o contato com a água de produção, ocorreu uma diminuição de 9% na resistência à compressão, já para as pastas sem a rede polimérica, a redução atingiu 40%. Estudos cinéticos, equilíbrio químico e termodinâmico foram realizados na investigação da interação das pastas de cimento com as soluções de HCl e mud acid. Os resultaram sugerem que as interações entre as pastas modificadas e os meios ácidos são devido a reações superficiais com preservação dos compostos hidratados do cimento, ocasionando uma perda de massa em torno de 25%. Para as pastas padrão, o mecanismo é predominantemente por difusão, com deterioração estrutural dessas pastas e perda de massa de aproximadamente de 46%. Desta forma, as pastas modificadas com a rede polimérica Epoxy-EDA apresentaram boas características para serem utilizadas em ambientes subterrâneos dos poços de petróleo. / São Cristóvão, SE

Depuis plusieurs années de nouveaux procédés industriels destinés à la réfrigération et à la climatisation sont étudiés et mis sur le marché. Parmi ceux qui commencent à connaître des débouchés commerciaux on compte les systèmes utilisant des fluides frigoporteurs diphasiques solide/liquide. Ces dispositifs offrent en effet les avantages de réduire l’utilisation des fluides frigorigènes de plus en plus réglementée et de pouvoir lisser la production de froid sur 24 heures grâce à la possibilité de stocker ces fluides diphasiques. Le domaine de la réfrigération connaît au niveau européen, grâce à plusieurs industriels, un premier essor de l’utilisation de « coulis » ou « sorbet » de glace. La climatisation industrielle ou collective représente également un enjeu énergétique majeur tant du point de vue de la consommation énergétique instantanée qu’elle nécessite que du point de vue des “pics” qu’elle génère à certaine périodes de la journée.Dans ce domaine et sur le continent asiatique (particulièrement au Japon), l’utilisation de sorbets est également en phase d’expansion. Dans ce cas, les sorbets utilisés sont des « coulis d’hydrates » qui présentent l’intérêt de cristalliser à des températures positives plus adaptées à la climatisation que celles des « coulis de glace ».Ces travaux de thèse ont donc consisté à adapter une technologie de réfrigération disponible sur le marché européen au domaine de la climatisation. Le fluide utilisé est une solution de TBAB (Bromure de Tetra-ButylAmmonium) qui est une solution aqueuse dont la température de cristallisation à pression atmosphérique peut être ajustée entre environ 6 et 12°C. Le dispositif expérimental conçu et construit est donc un prototype industriel de taille réelle capable de climatiser 4 pièces. A la fois démonstrateur industriel et banc d’essais instrumenté, il est destiné à mener à bien des séances d’essais afin de démontrer la faisabilité du procédé, de diagnostiquer des améliorations et de prévoir de nouvelles évolutions. Parallèlement aux travaux de construction et aux séances d’essais, des mesures complémentaires concernant certaines caractéristiques thermo-physiques des sorbets d’hydrates de TBAB ont été menées en laboratoire. Enfin, un outil de modélisation a également été développé afin de rattacher les expériences à des phénomènes thermo-physiques théoriques. Cette modélisation a pour but d’être un outil prédicatif à la conception de nouvelles installations et au développement du prototype. / For some years, new industrial processes have been developed and marketed in the refrigeration and air conditioning fields. Among systems which begin to have good business opportunities some are using two-phase secondary refrigerants solid / liquid. This kind of technology offers the advantages of reducing the use of classical refrigerants which are regulated and can smooth the production of cold over 24 hours with its ability to store the slurry. At the European level, thanks to the efforts of several manufacturers, the refrigeration field is developing fast with respect to the use of ice slurries. Moreover the industrial or district air conditioning field is a major energetic issue in terms of the immediate energy it requires as well as in terms of "peaks" generated during certain periods of the day.In this field, especially in Japan, the use of “PCM” (Phase Change Material) is additionally developing. In this technological segment, the PCM used are hydrate slurries. This solution has the advantage of crystallizing at positive temperatures which is more suited for the air conditioning than ice slurries.This research work deals with the adaption of a refrigeration technology available on the European market to the field of air conditioning. The fluid used is an aqueous solution of TBAB (Tetra-Butylammonium Bromide) with a crystallization temperature at atmospheric pressure which can be adjusted to a temperature between 6 and 12°C. The experimental device designed and installed is a real size prototype able to cool 4 rooms. Both the industrial demonstrator as well as instrumented test bench allowed us to carry out practice sessions which demonstrated the feasibility of the process. It also allowed us to design improvements and new developments. In parallel to the construction and the experiments, additional measurements concerning some thermo-physical characteristics of TBAB hydrate slurries were conducted in specialised laboratory. Finally, a modelling tool was also developed in order to relate our experiments with theoretical thermo-physical phenomena. This numerical model is intended to be a predicative tool for the design of new installations and for the development of the prototype.

Clays are used for long for the control of soil and water pollution as they are inexpensive natural materials with a high adsorption capacity for a wide range of pollutants. However their use as components in engineered waste containment systems is often limited when it comes to the control of organic contaminants as the clays are organophobic in nature. Organic modification of the natural clays, by replacing the exchangeable inorganic cations of clay with organic cations, can facilitate to overcome this limitation. On modification the clays become organophilic which can enhance their sorption capacities for organic contaminants. There are several ways by which natural clays can be modified with organic cations. The type of clay, the type of modifier, and the extent of modification play an important role in enhancing the organic sorption capacity. Sorption of organics by the organo clays depends on a large extent on the specific interactions that occur between modified clay and the organic contaminants. The interaction between the clay and the contaminants depend on the physico-chemical properties of modified clay and nature of organic contaminants. Since the properties of natural clays are likely to be altered by the modification a detailed study has been taken up to understand the physico chemical characteristics of organo clays which essentially control their organic sorption efficiency. Apart from bentonite which is widely used as a component of barrier systems, the characteristics of other types of clays on organic modification also needs to be assessed as they can also form part of the containment system frequently. Further the modification of clays is bound to bring in significant changes on their geotechnical properties which may affect their performance when used as barrier material. Only limited research has been conducted in the past on the geotechnical characteristics of organo clay. Therefore extensive studies have been carried out on the evaluation of the geotechnical characteristics of organo clays and the effect of organic modification on important geotechnical properties. Since very often inorganic and organic contaminants can occur simultaneously, admixtures of bentonite and organically modified clays needs to be employed as a part of clay barrier system. Moreover clay alone is very rarely used as component of barrier systems and significant portion of barrier material usually include non clay fraction. Hence studies have been carried out on mixtures containing different proportions of organo clay and bentonite and sand – organo clay / bentonite to evaluate their geotechnical behavior. Important geotechnical properties considered for detailed studies are swelling, compressibility and permeability. Detailed studies on the organic sorption capacities of different organically modified and unmodified clays, mixtures of bentonite and organo clays have also been conducted. The results of studies conducted are presented in 9 chapters. The organization of the thesis is as follows: Chapter 1 gives detailed background information on the sources and hazards of organic contaminants, inadequacy of conventional barriers to contain organic contaminants, the need for modification of natural clays, and the methods for organic modification of clays. Extensive review of literature has highlighted the need to study the effect of organic modification on the physico chemical and geotechnical properties of clay in different pore fluids. Organo clays were prepared using a wide range of clays viz., two types of bentonites of different regions, black cotton clay and commercially available kaolinite with a long chain organic cation. The extent of organic modification was varied by varying the amount of organic cation exchanged as function of total cation exchange capacity of the clays. Detailed physico chemical characterization of these modified and unmodified clays has been carried out with the help of different state of art techniques. The Chapter 2 brings out the effect of modification, role of type of clay and type of modifiers on the characteristics of organo clays by comparing the physico chemical characteristics of different modified and unmodified clays. The organic modification of montmorillonitc clays with long chain organic cation is found to increase their lattice spacing with the amount of modification whereas no such increase was observed on modification of kaolinitic clays even when all the exchangeable inorganic cations were replaced with the organic cations. The XRD studies revealed that the intercalated organic cations of the modified montmorillonite clays assumed mono, bi, or pseudo tri layer depending on the extent of organic modification. Irrespective of the type of clay modified or the modifier used all the organo clays tend to become e hydrophobic, and the surface area of the clays was found to decrease. A comparison of the characteristics of clays modified in laboratory with organo clay obtained commercially revealed that the organic modification was more effective for the organo clay prepared in the laboratory. As the index properties of all clays are generally correlated with their geotechnical characteristics, the effect of organic modification on the index properties of clays was studied. Chapter 3 presents the effect of organic modification on the plasticity and free swell behavior of clays. The index properties of commercially available organo clay and the unmodified clay used for its preparation were evaluated with pore fluids of different dielectric constants. Fluids of varied dielectric constants were chosen as it is one of the important characteristics to understand the behavior of clays. It was observed that the organic modification of clays reduced the plasticity of the clays in water and increased the plasticity in less polar liquids like ethanol. As the organo clays are more hydrophobic, the water holding capacity and plasticity in water is decreased to a large extent. The free swell behavior of clays in different pore fluids were assessed in terms of the modified free swell index. It was found that trend of variation of free swell index with dielectric constant for modified and unmodified clays, as in the case of plasticity is quite opposite. The swell volume of the modified clays was observed to be controlled more by surface solvation than by the development of the inter particle repulsive forces and diffused double layer. The effect of incorporating unmodified bentonite with organically modified clay on the index properties of bentonite has also been studied. The results suggested that the effect of organo clay addition to bentonite was always to reduce its plasticity and free swell in water. However in pore fluids of lower dielectric an increase in the plasticity and free swell was observed with increasing organo clay content in the mixture. This owes to the fact that organo clays can interact strongly with organic fluids, changing its fabric arrangement. As reported from literature it is well established that the swell of clays has conflicting role on the stability and permeability of clay barriers. Swelling of clays is liable to cause a reduction in hydraulic conductivity, enhance the retention times of contaminants and attribute self healing capacity to the liners. Even though extensive studies have been carried out on the swell behaviour and mechanism of swell of unmodified clays, no systematic research is reported on the effect of organic modification on swell behavior of clays especially in the presence of different pore fluids. Chapter 4 describes the results of oedometer swell tests carried out on compacted samples of modified, unmodified clays and organo clay –bentonite mixture in the presence of different pore fluids such as water, ethanol, and their mixture and carbon tetra chloride. Swelling ability of the unmodified clays was not completely suppressed even in the presence of low polar miscible organic liquids as they were molded at water contents corresponding to the optimum moisture content (OMC). The order of the swelling for the unmodified bentonites was in the order of the polarity of the pore fluids used, while the order is reversed upon organic modification of clays. The mechanism of swell in the case of organo clays in organic liquids was related to the solvation of the organic liquid by the intercalated organic cations. And unlike in the case of unmodified clays, the organo clays showed “solvent induced swelling”. Both organic modification and addition of organo clay to bentonite resulted in the suppression of the swelling of clays in water irrespective of the type of modifier or the extent of organic modification. The Chapter 5 gives a detailed account of the compressibility behavior of organically modified clays and its mixtures with bentonite when the samples were molded with water at their respective OMC and later inundated with different fluids. Significant differences were observed on the compressibility of modified and unmodified clay in different fluids. Organic modification of clays reduced their affinity to water and resulted in lowering the compressibility. However there was an increased compressibility for the organo clays when the samples were inundated with non polar liquids and the compression of the organo clay in non polar fluid was not influenced by the nature of clay nor by the type of modifier. The compressibility of the mixtures of organo clay and bentonite in non polar liquids was generally controlled by the organo clay component of the mixture. Organo clays can be recommended as additives in bentonite slurries for construction of slurry walls in order to improve the containment of organics. But the amendment should not compromise the stability and integrity of the slurry walls. Moreover the influence of addition of sorptive material like organo clay on the compressibility behavior of bentonite slurry has received little attention and needs serious consideration as the studies in the previous chapter has brought out that the compressibility of compacted bentonite reduced significantly on organic modification as well as on addition of orgno clay. The Chapter 6 deals with the compressibility behavior of slurries of unmodified bentonite, organo clay, and their mixtures molded with respective liquid limits with water and later inundated with fluids of different dielectric constants as the slurries frequently get in contact with fluids other than water during their operational life. However it was observed that the effect of polarity of the inundating liquid is masked in all the cases by the presence of large amount of initial molding water as the possible specific chemical interactions between organo clay and non polar fluids were restricted in the presence of large amount of molding water. But the slurry samples molded and inundated with non polar carbon tetra chloride showed that the organo clay samples are more compressible when molded with carbon tetrachloride. The chapter also gives a brief discussion on the effect of initial molding water content on the compressibility of organo clays and its mixtures. The compression was found to increase with increase in initial water content irrespective of the type of inundating fluid in agreement with the behavior observed in the case of unmodified clays. However the effect was less pronounced at higher applied pressures. The Chapter 7 brings out the volume change behavior of organo clay amended sand bentonite mixtures (SOB) which form potential barrier to prevent and /or remove contaminants. The compaction behavior of mixtures showed that the degree of compaction achieved was controlled mainly by the sand content and proportion of organo clay in the total fine fraction. The volume change behavior of the SOB mixtures were assessed with the help of oedometer tests conducted on mixtures compacted at OMC conditions and inundated with different fluids same as those used for the swell tests. The samples with higher sand content showed no observable swell when inundated with liquids viz., water, ethanol and their mixture as all the swollen finer particles were accommodated in the voids created by sand particles. However a high swell percentage was measured when samples with high organo clay content were inundated with carbon tetrachloride. Moreover with increased amounts of organo clay in the mix the swelling of bentonite was suppressed and the same trend continued even when the pore fluids were changed to liquids of medium polarity. The organo clays are capable of interacting strongly with non polar liquids like carbon tetra chloride, and hence an appreciable swell was noted when inundated with them especially in the case of mixtures with high organo clay content. The swell behavior of SOB mixtures with lower sand contents were controlled mostly by the interaction of the pore fluid with bentonite and organo clay, interactions between organo clay and bentonite and the polarity of the pore fluid. As the pore fluid polarity was decreased the influence of organo clay component of the mixture was more pronounced. The Chapter 8 explains the hydraulic performance of modified and unmodified clays along with that of the mixtures of organo clay with bentonite and SOB. The coefficient of permeability was calculated from the consolidation data obtained on sample molded at OMC. The permeability variations observed on changing the pore fluids were studied at each applied pressure. The hydraulic conductivity showed a decreasing trend with the increase in applied pressure for all the clays. The specific interactions of the organo clay with the pore fluids and the clay content were found to play a role in controlling the permeability. Limited tests were carried out to simulate a condition where a SOB liner is proposed as a secondary liner below a punctured geo membrane and its hydraulic performance was evaluated with diesel and water as pore fluids. The permeability coefficients with diesel as permeant were observed to decrease with increase in organo clay content of the mixture irrespective of the applied pressure where as the reverse was true when permeated with water. Thus the use of SOB as secondary liner below storage tanks so as to control the transport of contaminants leaking containments systems is established. The organic sorption efficiency of the modified and unmodified clays and the mixture were evaluated in terms of removal of total organic carbon (TOC) and reduction in chemical oxygen demand (COD) of the different leachates including municipal solid waste (MSW) leachate when treated with different types of modified and unmodified clays. All the modified clays irrespective of the type of clay or the type of modifier used showed improved organic sorption capacity. The sorption of TOC was found to follow a linear sorption mechanism in the case of organo clays and the organic contaminants were partitioned on to the organic phase attached to the organo clays. The composition, age and type of leacahte played a major role in controlling the organic sorption efficiency of organo clays in the case of MSW leachates. The studies done with different mixtures of organo clay and bentonite and SOB mixtures clearly proved that the addition of organo clay always enhanced the organic sorption efficiency of the mixtures. The results are discussed in Chapter 9. The Chapter 10 highlights the major conclusions drawn from the study. The study, apart from satisfying the research zeal on understanding the behavior of organo clays, has generated important information useful for the geo environmental engineer to arrive at appropriate design of barrier systems incorporating organically modified clay, based on the characteristics of pore fluid.