871 resultados para IN-OIL MICROEMULSIONS
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Due to the great challenges encountered in drilling wells, there is a need to develop fluids with appropriated properties and able to meet all the requirements of drilling operations. The physicochemical and rheological properties must be carefully controlled so that a fluid can exercise all its functions. In perforations sensitive to contact with water and "offshore", it becomes necessary the use of oil based drilling fluids, but the bentonite clay cannot be used without a previous surface modification so that their surfaces become hydrophobic. Lately, the oil companies in Brazil use imported organoclays in the preparation of oil-based drilling fluids. The study aimed to modify a calcium clay to increase the affinity of the same organic phase of oil-based drilling fluids, applying three surfactants (OCS, CTAB and UTM 150) at different concentrations. The results indicated that the surfactants UTM 150 and CTAB showed better results compared to OCS. Considering the type of surfactant and concentration as variables used in the statistical analysis, the results indicated that only the surface tension and concentration of calcium oxide in response to organophilization process showed statistically significant effects. The organophilizated clay has potential for application in oil-based drilling fluids.
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This study aims to evaluate the relationship between the export profile and the African GDP growth rate. Chapter 1 presents the literature on the subject and studies that analyze the specific case of Africa. There seems to be a consensus that exports contribute to economic growth. However, there is no consensus on the benefits that are incorporated from exported products. The divergence lies between the approach of the Natural Resources Curse, where concentration of exports in commodities does not contribute to economic growth. Another work line supports the idea there is no such relation. Chapter 2 presents, through descriptive analysis, macroeconomic and international trade data for African economies data. Based on data from 52 countries for the period 1990-2014, it can be observed that the African continent has improved in macroeconomic terms, with increased exports and economic growth rates, suggesting a positive relationship between the variables. Trade indicators show Africa's integration into the global economy, with European Union, USA, China and some emerging countries as main partners. In addition, the analysis showed that the export is concentrated in oil and agricultural commodities. Most African countries face a negative trade balance, depending of primary products exports with low added value and imports of manufactured goods. Finally, Chapter 3 presents an empirical research using panel data analysis. The results suggest, in general, evidences that exports are important for explaining the African economic growth rate of African economies can be stimulated by the expansion of the share of exports in GDP. The estimated coefficients are positive and statistically significant in both the fixed effect estimation, as the estimation by GMM System. The estimation of growth models for fixed or random effects indicates a direct and statistically significant relationship between export oil / minerals and the growth rate of African countries. Thus, the export profile turns out to be important to determine the growth rate. The results obtained from the estimates do not corroborate the literature arguments called Curse of Natural Resources for the period analyzed, since export natural resources, especially oil and minerals, were relevant to explain the performance of the growth rate of economies.
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Human activities represent a significant burden on the global water cycle, with large and increasing demands placed on limited water resources by manufacturing, energy production and domestic water use. In addition to changing the quantity of available water resources, human activities lead to changes in water quality by introducing a large and often poorly-characterized array of chemical pollutants, which may negatively impact biodiversity in aquatic ecosystems, leading to impairment of valuable ecosystem functions and services. Domestic and industrial wastewaters represent a significant source of pollution to the aquatic environment due to inadequate or incomplete removal of chemicals introduced into waters by human activities. Currently, incomplete chemical characterization of treated wastewaters limits comprehensive risk assessment of this ubiquitous impact to water. In particular, a significant fraction of the organic chemical composition of treated industrial and domestic wastewaters remains uncharacterized at the molecular level. Efforts aimed at reducing the impacts of water pollution on aquatic ecosystems critically require knowledge of the composition of wastewaters to develop interventions capable of protecting our precious natural water resources.
The goal of this dissertation was to develop a robust, extensible and high-throughput framework for the comprehensive characterization of organic micropollutants in wastewaters by high-resolution accurate-mass mass spectrometry. High-resolution mass spectrometry provides the most powerful analytical technique available for assessing the occurrence and fate of organic pollutants in the water cycle. However, significant limitations in data processing, analysis and interpretation have limited this technique in achieving comprehensive characterization of organic pollutants occurring in natural and built environments. My work aimed to address these challenges by development of automated workflows for the structural characterization of organic pollutants in wastewater and wastewater impacted environments by high-resolution mass spectrometry, and to apply these methods in combination with novel data handling routines to conduct detailed fate studies of wastewater-derived organic micropollutants in the aquatic environment.
In Chapter 2, chemoinformatic tools were implemented along with novel non-targeted mass spectrometric analytical methods to characterize, map, and explore an environmentally-relevant “chemical space” in municipal wastewater. This was accomplished by characterizing the molecular composition of known wastewater-derived organic pollutants and substances that are prioritized as potential wastewater contaminants, using these databases to evaluate the pollutant-likeness of structures postulated for unknown organic compounds that I detected in wastewater extracts using high-resolution mass spectrometry approaches. Results showed that application of multiple computational mass spectrometric tools to structural elucidation of unknown organic pollutants arising in wastewaters improved the efficiency and veracity of screening approaches based on high-resolution mass spectrometry. Furthermore, structural similarity searching was essential for prioritizing substances sharing structural features with known organic pollutants or industrial and consumer chemicals that could enter the environment through use or disposal.
I then applied this comprehensive methodological and computational non-targeted analysis workflow to micropollutant fate analysis in domestic wastewaters (Chapter 3), surface waters impacted by water reuse activities (Chapter 4) and effluents of wastewater treatment facilities receiving wastewater from oil and gas extraction activities (Chapter 5). In Chapter 3, I showed that application of chemometric tools aided in the prioritization of non-targeted compounds arising at various stages of conventional wastewater treatment by partitioning high dimensional data into rational chemical categories based on knowledge of organic chemical fate processes, resulting in the classification of organic micropollutants based on their occurrence and/or removal during treatment. Similarly, in Chapter 4, high-resolution sampling and broad-spectrum targeted and non-targeted chemical analysis were applied to assess the occurrence and fate of organic micropollutants in a water reuse application, wherein reclaimed wastewater was applied for irrigation of turf grass. Results showed that organic micropollutant composition of surface waters receiving runoff from wastewater irrigated areas appeared to be minimally impacted by wastewater-derived organic micropollutants. Finally, Chapter 5 presents results of the comprehensive organic chemical composition of oil and gas wastewaters treated for surface water discharge. Concurrent analysis of effluent samples by complementary, broad-spectrum analytical techniques, revealed that low-levels of hydrophobic organic contaminants, but elevated concentrations of polymeric surfactants, which may effect the fate and analysis of contaminants of concern in oil and gas wastewaters.
Taken together, my work represents significant progress in the characterization of polar organic chemical pollutants associated with wastewater-impacted environments by high-resolution mass spectrometry. Application of these comprehensive methods to examine micropollutant fate processes in wastewater treatment systems, water reuse environments, and water applications in oil/gas exploration yielded new insights into the factors that influence transport, transformation, and persistence of organic micropollutants in these systems across an unprecedented breadth of chemical space.
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This thesis reports the synthesis and/or applications of three types of block copolymers that each bear a low-surface-energy block. First, poly(dimethylsiloxane)-block-poly(2-cinnamoyloxyethyl acrylate) (PDMS-b-PCEA) was synthesized and characterized. Cotton coating using a micellar solution of this block copolymer yielded superhydrophobic cotton fabrics. X-ray photoelectron spectroscopy (XPS) and surface property analyses indicated that the PDMS block topped the polymer coating. Photocuring the cotton swatches crosslinked the underlying PCEA layer and yielded permanent coatings. More interestingly, hydrophilically patterned superhydrophobic cotton fabrics were produced using photolithography that allowed the crosslinking of the coating around irradiated fibers but the removal, by solvent extraction, of the coating on fibers that were not irradiated. Since water-based ink only permeated the uncoated regions, such patterned fabric was further used to print ink patterns onto substrates such as fabrics, cardboard, paper, wood, and aluminum foil. Then, another PDMS-based diblock copolymer poly(dimethylsiloxane)-block-poly(glycidyl methacrylate) (PDMS-b-PGMA) was prepared. Different from PCEA that photocrosslinked around cotton fibers, PGMA reacted with hydroxyl groups on cotton fiber surfaces to get covalently attached. Further, different PGMA chains crosslinked with each other. PDMS-b-PGMA-coated cotton fabrics have been used for oil-water separations. In addition, polymeric nanoparticles were grafted onto cotton fiber surface before PDMS-b-PGMA was used to cover the surfaces of the grafted spheres and the residual surfaces of the cotton fibers. These two types of fabrics, coated by the block copolymer alone or by the polymer nanospheres and then the copolymer, were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and water repellency analyses. A comprehensive comparative study was made of their performances in oil-water separation. Finally, a fluorinated ABC triblock copolymer poly(acrylic acid)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(2-perfluorooctylethyl methacrylate) (PAA-b-PCEMA-b-PFOEMA) was used to iii encapsulate air nanobubbles. The produced air nanobubbles were thermodynamically stable in water and were some 100 times more stable than commercially available perfluorocarbon-filled microbubbles under ultrasound. These nanobubbles, due to their small sizes and thus ability to permeate the capillary networks of organs and to reach tumors, may expand the applications of microbubbles in diagnostic ultrasonography and find new applications in ultrasound-regulated drug delivery.
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Ernest Mercier est l’un des patrons les plus influents de l'entre-deux-guerres en France. Ses différentes activités industrielles l'ont conduit à siéger sur de vastes pans de l’économie française, notamment du secteur énergétique. La thèse retrace la carrière pétrolière d'un homme qui a joué un rôle central pour le développement d'une industrie devenue stratégique, mais qui est embryonnaire lorsqu'il rejoint ce secteur après la Première Guerre mondiale. Mercier assiste et assure la création d'une industrie pétrolière nationale. Les obstacles se font légion contre les ambitions pétrolières de la France. Elle se présente bien tard sur un marché étroitement contrôlé par de puissants trusts. La recherche et l'exploitation pétrolière demandent d'importantes ressources, et aucune société française n'a les moyens d'une politique indépendante. Certaines banques se lancent alors dans les affaires de pétrole en s'alliant aux grands trusts internationaux. C'est le cas de Paribas; la gestion de ses avoirs roumains représente la première expérience de Mercier dans ce secteur. L'État s'intéresse aussi au pétrole, il devient un acteur incontournable. Le gouvernement français n'a pourtant pas les moyens de ses ambitions dans le domaine pétrolier. La politique nationale mise en place durant l'entre-deux-guerres doit faire appel à l'épargne privée française. La création d'une compagnie nationale, la Compagnie française des pétroles, en 1924 regroupe ainsi les différentes banques et sociétés intéressées au pétrole. Mercier est personnellement choisi par le président Raymond Poincaré pour mener à bien cette mission. Cette carrière s'articule donc autour d'un fragile équilibre entre milieux privés et gouvernement. Mercier devient rapidement l'intermédiaire incontournable qui régit ces relations. La thèse s'appuie sur les archives bancaires et industrielles, mais aussi sur celles du gouvernement français et de ses différents ministères. Cette analyse de la carrière d'Ernest Mercier permet de retracer les origines du secteur pétrolier français et l'action déterminante d'un homme. Elle expose les mécanismes d'influence d'une puissante banque d'affaires et les conflits d'intérêts qu'engendre l'exploitation pétrolière.
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Mestrado em Contabilidade e Análise Financeira
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Simultaneous Localization and Mapping (SLAM) is a procedure used to determine the location of a mobile vehicle in an unknown environment, while constructing a map of the unknown environment at the same time. Mobile platforms, which make use of SLAM algorithms, have industrial applications in autonomous maintenance, such as the inspection of flaws and defects in oil pipelines and storage tanks. A typical SLAM consists of four main components, namely, experimental setup (data gathering), vehicle pose estimation, feature extraction, and filtering. Feature extraction is the process of realizing significant features from the unknown environment such as corners, edges, walls, and interior features. In this work, an original feature extraction algorithm specific to distance measurements obtained through SONAR sensor data is presented. This algorithm has been constructed by combining the SONAR Salient Feature Extraction Algorithm and the Triangulation Hough Based Fusion with point-in-polygon detection. The reconstructed maps obtained through simulations and experimental data with the fusion algorithm are compared to the maps obtained with existing feature extraction algorithms. Based on the results obtained, it is suggested that the proposed algorithm can be employed as an option for data obtained from SONAR sensors in environment, where other forms of sensing are not viable. The algorithm fusion for feature extraction requires the vehicle pose estimation as an input, which is obtained from a vehicle pose estimation model. For the vehicle pose estimation, the author uses sensor integration to estimate the pose of the mobile vehicle. Different combinations of these sensors are studied (e.g., encoder, gyroscope, or encoder and gyroscope). The different sensor fusion techniques for the pose estimation are experimentally studied and compared. The vehicle pose estimation model, which produces the least amount of error, is used to generate inputs for the feature extraction algorithm fusion. In the experimental studies, two different environmental configurations are used, one without interior features and another one with two interior features. Numerical and experimental findings are discussed. Finally, the SLAM algorithm is implemented along with the algorithms for feature extraction and vehicle pose estimation. Three different cases are experimentally studied, with the floor of the environment intentionally altered to induce slipping. Results obtained for implementations with and without SLAM are compared and discussed. The present work represents a step towards the realization of autonomous inspection platforms for performing concurrent localization and mapping in harsh environments.
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International audience
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International audience
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Re-creating and understanding the origin of life represents one of the major challenges facing the scientific community. We will never know exactly how life started on planet Earth, however, we can reconstruct the most likely chemical pathways that could have contributed to the formation of the first living systems. Traditionally, prebiotic chemistry has investigated the formation of modern life’s precursors and their self-organisation under very specific conditions thought to be ‘plausible’. So far, this approach has failed to produce a living system from the bottom-up. In the work presented herein, two different approaches are employed to explore the transition from inanimate to living matter. The development of microfluidic technology during the last decades has changed the way traditional chemical and biological experiments are performed. Microfluidics allows the handling of low volumes of reagents with very precise control. The use of micro-droplets generated within microfluidic devices is of particular interest to the field of Origins of Life and Artificial Life. Whilst many efforts have been made aiming to construct cell-like compartments from modern biological constituents, these are usually very difficult to handle. However, microdroplets can be easily generated and manipulated at kHz rates, making it suitable for high-throughput experimentation and analysis of compartmentalised chemical reactions. Therefore, we decided to develop a microfluidic device capable of manipulating microdroplets in such a way that they could be efficiently mixed, split and sorted within iterative cycles. Since no microfluidic technology had been developed before in the Cronin Group, the first chapter of this thesis describes the soft lithographic methods and techniques developed to fabricate microfluidic devices. Also, special attention is placed on the generation of water-in-oil microdroplets, and the subsequent modules required for the manipulation of the droplets such as: droplet fusers, splitters, sorters and single/multi-layer micromechanical valves. Whilst the first part of this thesis describes the development of a microfluidic platform to assist chemical evolution, finding a compatible set of chemical building blocks capable of reacting to form complex molecules with endowed replicating or catalytic activity was challenging. Abstract 10 Hence, the second part of this thesis focuses on potential chemistry that will ultimately possess the properties mentioned above. A special focus is placed on the formation of peptide bonds from unactivated amino acids, despite being one of the greatest challenges in prebiotic chemistry. As opposed to classic prebiotic experiments, in which a specific set of conditions is studied to fit a particular hypothesis, we took a different approach: we explored the effects of several parameters at once on a model polymerisation reaction, without constraints on hypotheses on the nature of optimum conditions or plausibility. This was facilitated by development of a new high-throughput automated platform, allowing the exploration of a much larger number of parameters. This led us to discover that peptide bond formation is less challenging than previously imagined. Having established the right set of conditions under which peptide bond formation was enhanced, we then explored the co-oligomerisation between different amino acids, aiming for the formation of heteropeptides with different structure or function. Finally, we studied the effect of various environmental conditions (rate of evaporation, presence of salts or minerals) in the final product distribution of our oligomeric products.
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Ernest Mercier est l’un des patrons les plus influents de l'entre-deux-guerres en France. Ses différentes activités industrielles l'ont conduit à siéger sur de vastes pans de l’économie française, notamment du secteur énergétique. La thèse retrace la carrière pétrolière d'un homme qui a joué un rôle central pour le développement d'une industrie devenue stratégique, mais qui est embryonnaire lorsqu'il rejoint ce secteur après la Première Guerre mondiale. Mercier assiste et assure la création d'une industrie pétrolière nationale. Les obstacles se font légion contre les ambitions pétrolières de la France. Elle se présente bien tard sur un marché étroitement contrôlé par de puissants trusts. La recherche et l'exploitation pétrolière demandent d'importantes ressources, et aucune société française n'a les moyens d'une politique indépendante. Certaines banques se lancent alors dans les affaires de pétrole en s'alliant aux grands trusts internationaux. C'est le cas de Paribas; la gestion de ses avoirs roumains représente la première expérience de Mercier dans ce secteur. L'État s'intéresse aussi au pétrole, il devient un acteur incontournable. Le gouvernement français n'a pourtant pas les moyens de ses ambitions dans le domaine pétrolier. La politique nationale mise en place durant l'entre-deux-guerres doit faire appel à l'épargne privée française. La création d'une compagnie nationale, la Compagnie française des pétroles, en 1924 regroupe ainsi les différentes banques et sociétés intéressées au pétrole. Mercier est personnellement choisi par le président Raymond Poincaré pour mener à bien cette mission. Cette carrière s'articule donc autour d'un fragile équilibre entre milieux privés et gouvernement. Mercier devient rapidement l'intermédiaire incontournable qui régit ces relations. La thèse s'appuie sur les archives bancaires et industrielles, mais aussi sur celles du gouvernement français et de ses différents ministères. Cette analyse de la carrière d'Ernest Mercier permet de retracer les origines du secteur pétrolier français et l'action déterminante d'un homme. Elle expose les mécanismes d'influence d'une puissante banque d'affaires et les conflits d'intérêts qu'engendre l'exploitation pétrolière.
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Oil well cementing materials consist of slurries of Special class Portland cement dispersed in water. Admixtures can be used to provide the necessary fluidity, so the material can be efficiently pumped down as well as penetrate porous rocks with controlled filter loss. Construction admixtures can be used to modify the properties of oil well cements provided they can withstand and hold their properties at the higher than ambient temperatures usually encountered in oil fields. In civil construction, superplasticizer play the role of dispersants that reduce the facto r of water cement improve mechanical properties and fluidity of the cement, whereas anti-segregation agents improve the workability of the slurry. In the present study, oil well cement slurries were produced adding both a dispersant and an anti-segregation agent conventionally used in Portland CPII-Z-32 RS cement aiming at materials for primary cementing and squeeze operations. Three basic aspects were evaluated: fluidity, filter loss and the synergetic effect of the admixtures at two temperatures, i.e., 27°C and 56°C, following API RP 10B practical recommendations. The slurries were prepared using admixture concentrations varying from 2.60 Kgf/m3 (0.02 gallft3) to 5.82 Kgf/m3 (0.045 galJft3) BWOC. The density of the slurries was set to 1.89 g/cm3 (15.8 Ib/gal). 0.30 to 0.60% BWOC of a CMC-based anti-segregation agent was added to the cement to control the filter loss. The results showed that the addition of anti-segregation at concentrations above 0.55% by weight of cement resulted in the increased viscosity of the folders in temperatures evaluated. The increasing the temperature of the tests led to a reduction in the performance of anti-segregation. At concentrations of 5.20 kgf/m3 (0,040 gallft3) and 5.82 Kgf/m3 (0,045 gal/ft 3) observed a better performance of the properties evaluated in the proposed system. At low temperature was observed instability in the readings of rheology for all concentrations of anti-segregation. Contents that increasing the concentration of anti¬-segregation is limited concentrations greater than 0.55 % BWOC of the CMC in temperature analyzed. The use of the system with CMC promoted a good performance against the properties evaluated. The principal function of anti¬-segregation was optimized with increasing concentration of superplasticizer, at temperatures above the 2rC. The study of the behaviour of systemic additives, resulting in slurries of cement, which can be optimized face studies of other intrinsic properties in oil fields
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The low tenacity presented by the Portland cement pastes used in the oil wells cementation has been motivating several researches with attention focused on alternative materials. Additives have been developed to generate flexible pastes with mechanical resistance capable to support the expansions and retractions of the metallic covering of the wells that submit to the steam injection, technique very used to increase the recovery factor in oil reservoirs with high viscosity. A fresh paste with inadequate rheological behavior may commit the cementation process seriously, involving flaws that affect the performance of the paste substantially in the hardened state. This work proposes the elaboration and the rheological analysis of Portland cement pastes with addition of residues of rubber tire in several proportions, with the aim of minimizing the damages provoked in the hem cementing of these wells. By thermogravimetric analysis, the particles of eraser that go by the sieve of 0,5mm (35 mesh) opening and treated superficially with NaOH solution of 1 mol/L presented appropriate thermal resistance for wells that submit to thermal cyclic. The evaluation of the study based on the results of the rheological analysis of the pastes, complemented by the mechanical analysis, thickening, stability, tenor of free water and filtrate loss, being used as parameter a paste reference, without rubber addition. The results showed satisfactory rheology, passive of few corrections; considerable loss of mechanical resistance (traction and compression), compensated by earnings of tenacity, however with established limits for its application in oil wells; satisfactory stability, free water and thickening time
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One of the major current challenges for oilwell companies is the extraction of oil from evaporitic zones, also known as pre-salt basins. Deep reservoirs are found under thick salt layers formed from the evaporation of sea water. Salt layers seal the flow of oil from underneath rock formations, which store hydrocarbons and increase the probability of success in oil and gas exploration. Oilwells are cemented using Portland-based slurries to promote mechanical stability and zonal isolation. For pre-salt oilwells, NaCl must be added to saturate the cement slurries, however, the presence of salt in the composition of slurries affects their overall behavior. Therefore, the objective of the present study was to evaluate the effect of the addition of 5 to 25% NaCl on selected properties of Portland-based slurries. A series of tests were carried out to assess the rheological behavior, thickening time, free water and ultrassonic compressive strength. In addition, the slurries were also characterized by thermal analysis, X ray diffraction and scanning electron microscopy. The results showed that the addition of NaCl affected the thickening time of the slurries. NaCl contents up to 10% shortened the thickening time of the slurries. On the other hand, concentrations in excess of 20% not only extended the thickening time, but also reduced the strength of hardened slurries. The addition of NaCl resulted in the formation of a different crystalline phase called Friedel´s salt, where free chlorine is bonded to tricalcium aluminate
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Novel cementing materials formulations containing flexible polymeric admixtures have been studied aiming at improving the mechanical behavior of oil well cement slurries submitted to steam injection. However, research activities in this sector are still under development. The steam injected directly into the well causes casing dilation, which after a reduction in temperature, tends to return to its original dimensions, resulting in crack formation and hydraulic isolation loss of the well, which will result in shortening of well life. In this scenario, the objective of the present study was to evaluate the mechanical behavior of Portland-based slurries containing SBR latex, applied in oil well cementing of wells submitted to steam injection. Were formulated slurries with densities of 1.797 g/cm3 (15.0 lb/Gal) and 1.869 g/cm3 (15.6 lb/Gal), containing admixtures with a latex concentration of 0; 66.88; 133.76; 200.64 and 267.52 L/m3 (0, 0.5, 1.0, 1.5 and 2.0 gpc). Tests including rheology, fluid loss control, thickening time, API compressive strength and splitting tensile strength, beyond steam injection simulation. Microstrutural characteristics of the slurries were also performed (XRD, TG, FTIR and SEM). The results showed that increasing the polymer concentration increased in the rheological properties and fluid loss, and a decrease in the elasticity modulus of the cement slurries. The results obtained showed that the slurries can be applied in cementing operations of oil wells submitted to steam injection.