Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry

Interações entre a carboximetilcelulose, carbonato de cálcio e bentonita: repercussões sobre as propriedades dos fluidos de perfuração aquosos

The role of carboxymethylcellulose (CMC) in association to calcium carbonate particles (CaCO3) in most water-based drilling fluids is to reduce the fluid loss to the surrounding formation. Another essential function is to provide rheological properties capable of maintaining in suspension the cuttings during drilling operation. Therefore, it is absolutely essential to correlate the polymer chemical structure (degree of substitution, molecular weight and distribution of substituent) with the physical-chemical properties of CaCO3, in order to obtain the better result at lower cost. Another important aspect refers to the clay hydration inhibitive properties of carboxymethylcellulose (CMC) in drilling fluids systems. The clay swelling promotes an undesirable damage that reduces the formation permeability and causes serious problems during the drilling operation. In this context, this thesis consists of two main parts. The first part refers to understanding of interactions CMC-CaCO3, as well as the corresponding effects on the fluid properties. The second part is related to understanding of mechanisms by which CMC adsorption occurs onto the clay surface, where, certainly, polymer chemical structure, ionic strength, molecular weight and its solvency in the medium are responsible to affect intrinsically the clay layers stabilization. Three samples of carboximetilcellulose with different molecular weight and degree of substitution (CMC A (9 x 104 gmol DS 0.7), CMC B (2.5 x 105 gmol DS 0.7) e CMC C (2.5 x 105 gmol DS 1.2)) and three samples of calcite with different average particle diameter and particle size distribution were used. The increase of CMC degree of substitution contributed to increase of polymer charge density and therefore, reduced its stability in brine, promoting the aggregation with the increase of filtrate volume. On the other hand, the increase of molecular weight promoted an increase of rheological properties with reduction of filtrate volume. Both effects are directly associated to hydrodynamic volume of polymer molecule in the medium. The granulometry of CaCO3 particles influenced not only the rheological properties, due to adsorption of polymers, but also the filtration properties. It was observed that the lower filtrate volume was obtained by using a CaCO3 sample of a low average size particle with wide dispersion in size. With regards to inhibition of clay swelling, the CMC performance was compared to other products often used (sodium chloride (NaCl), potassium chloride (KCl) and quaternary amine-based commercial inhibitor). The low molecular weight CMC (9 x 104 g/mol) showed slightly lower swelling degree compared to the high molecular weight (2.5 x 105 g/mol) along to 180 minutes. In parallel, it can be visualized by Scanning Electron Microscopy (SEM) that the high molecular weight CMC (2.5 x 105 g/mol e DS 0.7) promoted a reduction in pores formation and size of clay compared to low molecular weight CMC (9.0 x 104 g/mol e DS 0.7), after 1000 minutes in aqueous medium. This behavior was attributed to dynamic of interactions between clay and the hydrodynamic volume of CMC along the time, which is result of strong contribution of electrostatic interactions and hydrogen bounds between carboxylate groups and hydroxyls located along the polymer backbone and ionic and polar groups of clay surface. CMC adsorbs on clay surface promoting the skin formation , which is responsible to minimize the migration of water to porous medium. With the increase of degree of substitution, it was observed an increase of pores onto clay, suggesting that the higher charge density on polymer is responsible to decrease its flexibility and adsorption onto clay surface. The joint evaluation of these results indicate that high molecular weight is responsible to better results on control of rheological, filtration and clay swelling properties, however, the contrary effect is observed with the increase of degree of substitution. On its turn, the calcite presents better results of rheological and filtration properties with the decrease of average viii particle diameter and increase of particle size distribution. According to all properties evaluated, it has been obvious the interaction of CMC with the minerals (CaCO3 and clay) in the aqueous medium

Obtenção de dispersões de complexos polieletrolíticos à base de quitosana e poli(ácido metacrílico) e análise de adsorção de albumina bovina sérica

Dispersions composed of polyelectrolyte complexes based on chitosan and poly(methacrylic acid), PMAA, were obtained by the dropping method and template polymerization. The effect of molecular weight of PMAA and ionic strength on the formation of chitosan/poly(methacrylic acid), CS/PMAA, complexes was evaluated using the dropping method. The increase in molecular weight of PMAA inhibited the formation of insoluble complexes, while the increase in ionic strength first favored the formation of the complex followed by inhibiting it at higher concentrations. The polyelectrolyte complexation was strongly dependent on macromolecular dimensions, both in terms of molecular weight and of coil expansion/contraction driven by polyelectrolyte effect. The resultant particles from dropping method and template polymerization were characterized as having regions with different charge densities: chitosan predominating in the core and poly(methacrylic acid) at the surface, the particles being negatively charged, as a consequence. Albumin was adsorbed on templatepolymerized CS/PMAA complexes (after crosslinking with glutardialdehyde) and pH was controlled in order to obtain two conditions: (i) adsorption of positively charged albumin, and (ii) adsorption of albumin at its isoelectric point. Adsorption isotherms and zeta potential measurements showed that albumin adsorption was controlled by hydrogen bonding/van der Waals interactions and that brushlike structures may enhance adsorption of albumin on these particles

Análise de uso e cobertura do solo no município de Parelhas/RN

The human interference in the semiarid region of Seridó Potiguar has promoted the increase of degraded areas. The economic dynamic that was established in the Seridó territory, especially after the fall of the trinomial cattle-cotton-mining in the 70s and 80s of the 20th century as pillars of the regional economy, resulted in an accelerated process of erosion of natural resources. The municipalities of the Seridó region have been spatially reordered by this new economic dynamic, marked by the growth of existing enterprises, and the development of new agricultural practices. One of the municipalities in the region that restructured its territorial space with the emergence of new agro-industrial activities was the town of Parelhas. With the demise of the trinomial cattle-cotton-mining in the 1980s, other productive activities were intensified from the 1990s, amongst them, pottery, responsible for the vegetal extraction for use as energy source. This recent economic and spatial restructuring in the region, reflected in the Parelhense municipal territory, required new productive ingredients responsible for the modification of past production relations that were based on cattle, cotton and mining. By that a process of exploring the environment was unleashed, especially the native vegetation, in an uncontrolled manner. In this context, the objective of this study was to survey and detect deforestation in the areas of Caatinga vegetation, used indiscriminately as energy supply for new agricultural practices, using remote sensing techniques based on the quantification of the Normalized Difference Vegetation Index / NDVI, Soil-Adjusted Vegetation Index / SAVI, surface temperature and rainfall data in the years 1990 and 2010. The results indicated that SAVI values above 0.2 in 1990 and 2010 represent the areas with the highest density of vegetation that occur exclusively along the major drainages in the town and areas of higher elevations. The areas between the ranges of values from 0.5 to 0.15 SAVI are areas with poor vegetation. On the other hand the highest values of temperature are distributed in the western and southeastern parts of the township, usually in places where the soil is exposed or there is sparse vegetation. The areas of bare soil decreased in extension in 2010 at 11, 6% when related to 1990, this was caused by a higher rainfall intensity in the first half of 2010, but no regeneration of vegetation occurred in some places in the western and southeastern areas of the municipality today, due to the extraction of firewood to fuel the furnaces of industries in town

Análises clínicas, radiográfica e microscópica de molares permanentes sem ou com lesão de cárie na superfície oclusal

O presente trabalho, objetivou avaliar comparativamente o diagnóstico clínico, radiógráfico e histológico de molares permanentes humanos sem ou com lesão de cárie na superfície oclusa!. Vinte e quatro dentes que estavam armazenados em formalina a 10% foram selecionados e em seguida submetidos a um exame clínico, através da inspeção visual, onde foram separados em 3 grupos: grupo 1 (G1), formado por dentes hígidos; grupo 2(G2), por dentes com pigmento na superfície oclusal e grupo 3(G3), aqueles com lesão de cárie na oclusal. Este exame foi realizado com auxílio de luz artificial proveniente de um refletor odontológico, sem qualquer manipulação da superfície. Para cada dente foram realizados duas tomadas radiográficas com e sem tela milimetrada, no sentido vestibulo lingual por um dos avaliadores, simulando uma radiografia interproximal, onde o feixe incidiu perpendicular ao longo eixo do dente. Em seguida os dentes foram preparados histomorfologicamente para coloração com hematoxilina e eosina e análise microscópica. Pela avaliação dos resultados a partir da amostra de 100%, foi possível concluir: 1) Os dentes clinicamente considerados hígidos (G1) apresentaram radiograficamente 74,99% de ausência de imagem radiolúcida e em 25% presença desta imagem na Junção Amelo¬dentinária e microscopicamente ausência de cárie em 100%; 2) os dentes que clinicamente apresentaram fissura pigmentada' (G2) notou-se em 33,33%, ausência da imagem radiolúcida e em 66,66% presente esta imagem na junção amelodentinária, 100% de ausência de cárie através da análise microscópica; 3) clinicamente, os dentes que apresentaram lesão de cárie (G3), radiograficamente foram comprovados 100% de imagem radiolúcida sugestiva de cárie e microscopicamente dos 100% destas, foram considerados cáries rasa (16,66%), média (61,10%) e profunda (22,22%) respectivamente

Propriedades fisicas do monocristal fe/mgo(100) e estudo da expansao termica da superficie da ag(100)

In this work we have developed a way to grow Fe/MgO(100) monocrystals by magnetron sputtering DC. We investigated the growing in a temperature range among 100 oC and 300 oC. Structural and magneto-crystalline properties were studied by different experimental techniques. Thickness and surface roughness of the films were investigated by atomic force microscopy, while magneto-crystalline properties were investigated by magneto-optical Kerr effect and ferromagnetic resonance. Our results show that as we increase the deposition temperature, the magneto-crystalline anisotropy of the films also increases, following the equation of Avrami. The best temperature value to make a film is 300 oC. As the main result, we built a base of magnetoresistence devices and as an aplication, we present measurements of Fe/Cr/Fe trilayer coupling. In a second work we investigated the temperature dependence of the first three interlayer spacings of Ag(100) surface using low energy electron diffraction. A linear expansion model of crystal surface was used and the values of Debye temperatures of the first two layers and thermal expansion coefficient were determinated. A relaxation of 1% was found for Ag(100) surface and these results are matched with faces (110) and (111) of the silver. iv

Geoprocessamento de dados meteo-oceonográficos (cor do oceano e temperatura da superfície do mar) aplicado ao monitoramento ambiental na costa setentrional do Rio Grande do Norte

Orbital remote sensing has been used as a beneficial tool in improving the knowledge on oceanographic and hydrodynamic aspects in northern portion of the continental shelf of Rio Grande do Norte, offshore Potiguar Basin. Aspects such as geography, temporal and spatial resolution combined with a consistent methodology and provide a substantial economic advantage compared to traditional methods of in situ data collecting. Images of the Moderate Resolution Imaging Spectroradiometer (MODIS) sensor onboard NASA's AQUA satellite were obtained to support systematic data collections related to the campaign of environmental monitoring and characterization of Potiguar Basin, held in May 2004. Images of Total Suspension Matter (TSM) and values of radiance standard were generated for the calculation of concentrations of total suspension matter (TSM), chlorophyll-a and sea surface temperature (SST). These data sets were used for statistical comparisons between measures in situ and satellite estimates looking validate algorithms or develop a comprehensive regional approach empirically. AQUA-MODIS images allowed the simultaneous comparison of two-dimensional water quality (total suspension matter), phytoplankton biomass (chlorophyll-a) variability and physical (temperature). For images of total suspension matter, the generated models showed a good correlation with the field data, allowing quantitative and qualitative analysis. The images of chlorophyll-a showed a consistent correlation with the in situ values of concentration. The algorithms adjusted for these images obtained a correlation coefficient fairly well with the data field in order that the sensor can be having an effect throughout the water column and not just the surface. This has led to a fit between the data of chlorophyll-the integration of the average sampling interval of the entire water column up to the level of the first optical depth, with the data generated from the images. This method resulted in higher values of chlorophyll concentration to greater depths, due to the fact that we are integrating more values of chlorophyll in the water column. Thus we can represent the biomass available in the water column. Images SST and SST measures in situ showed a mean difference DT (SST insitu - SST sat) around -0.14 ° C, considered low, making the results very good. The integration of total suspension matter, chlorophyll-a, the temperature of the sea surface (SST) and auxiliary data enabled the recognition of some of the main ways to fund the continental shelf. The main features highlighted were submerged canyons of rivers Apodi and Açu, some of the lines and beachrocks reefs, structural highs and the continental shelf break which occurs at depths around -60 m. The results confirmed the high potential for use of the AQUA-MODIS images to environmental monitoring of sea areas due to ease of detection of the field two-dimensional material in suspension on the sea surface, temperature and the concentration of chlorophyll-a

Arquitetura deposicional e evolução tectono-estratigráfica das sequências pré-rifte e rifte, na porção central do Vale do Cariri, Bacia do Araripe, NE do Brasil

A complex depositional history, related to Atlantic rifting, demonstrates the geological evolution during the late Jurassic and early Neocomian periods in the Araripe Basin NE Brazil. Based on outcrop, seismic and remote sensing data, a new model of the tectono-stratigraphic evolution of the section that covers the stages Dom João, Rio da Serra and Aratu (Brejo Santo, Missão Velha and Abaiara formations) is presented in this paper. In the stratigraphic section studied, ten sedimentary facies genetically linked to nine architectural elements were described, representing depositional systems associated with fluvial, aeolian and deltaic environments. Based on the relationship between the rates of creation of accommodation space and sediment influx (A / S) it was possible to associate these depositional systems with High and Low accommodation system tracks. These system tracks represent two tectono-sequences, separated by regional unconformities. The Tectono-sequence I, which includes lithotypes from the Brejo Santo Formation and is related to the pre-rift stage, is bounded at the base by the Paleozoic unconformity. This unit represents only a High Accommodation System Track, composed by a succession of pelitic levels interbedded with sandstones and limestones, from a large fluvial floodplain origin, developed under arid climatic conditions. The Tectono-sequence II, separated from the underlying unit by an erosional unconformity, is related to the rift stage, and is composed by the Missão Velha and Abaiara Formation lithotypes. Changes in depositional style that reflect variations in the A / S ratio, and the presence of hydroplastic deformation bands, make it possible to divide this tectonosequence into two internal sequences. Sequence IIA, which includes the lower portion of the Missão Velha Formation and sequence IIB, is composed by the upper section of the Missão Velha and Abaiara Formations The Sequence IIA below, composed only by the Low Accommodation System Track, includes crossbedding sandstones interbedded with massive mudstones, which are interpreted as deposits of sandy gravel beds wandering rivers. Sequence IIB, above, is more complex, showing a basal Low Accommodation System Track and a High Accommodation System Track at the top, separated by an expansion surface. The lower System Track, related to the upper portion of the Missão Velha Formation, is composed by a series of amalgamated channels, separated by erosion surfaces, interpreted as deposits of a belt of braided channels. The High Accommodation System Track, correlated with the Abaiara Unit, is marked by a significant increase in the A / S, resulting in the progradation of a system of braided river deltas with aeolic influence. Regarding tectonic evolution, the stratigraphic study indicates that the Tectonosequence Rift in the Araripe basin was developed in two phases: first characterized by a beginning of rifting, related to Sequence IIA, followed by a phase of syndepositional deformation, represented by sequence IIB. The first phase was not influenced by the development of large faults, but was influenced by a sharp and continuous decrease of accommodation space that permitted a change in depositional patterns, establishing a new depositional architecture. In turn, the stage of syndepositional deformation allowed for the generation of enough accommodation space for the preservation of fluvial-lacustrine deposits and conditioned the progradation of a braided river-dominated delta system.

Iinterpretação conjunta de dados de GPR e medidas de permeabilidade sobre um análogo de reservatório siliciclástico falhado na bacia de Tucano, no NE do Brasil

It is presented an integrated geophysical investigation of the spatial distribution of faults and deformation bands (DB´s) in a faulted siliciclastic reservoir analogue, located in Tucano Basin, Bahia State, northeastern Brazil. Ground Penetrating Radar (GPR) and permeability measurements allowed the analysis of the influence of DB´s in the rock permeability and porosity. GPR data were processed using a suitable flow parametrization in order to highlight discontinuities in sedimentary layers. The obtained images allowed the subsurface detection of DB´s presenting displacements greater that 10 cm. A good correlation was verified between DB´s detected by GPR and those observed in surface, the latter identified using conventional structural methods. After some adaptations in the minipermeameter in order to increase measurement precision, two approaches to measure permeabilities were tested: in situ and in collected cores. The former approach provided better results than the latter and consisted of scratching the outcrop surface, followed by direct measurements on outcrop rocks. The measured permeability profiles allowed to characterize the spatial transition from DB´s to undeformed rock; variation of up to three orders of magnitude were detected. The permeability profiles also presented quasi-periodic patterns, associated with textural and granulometric changes, possibly associated to depositional cycles. Integrated interpretation of the geological, geophysical and core data, provided the subsurface identification of an increase in the DB´s number associated with a sedimentary layer presenting granulometric decrease at depths greater than 8 m. An associated sharp decrease in permeability was also measured in cores from boreholes. The obtained results reveal that radagrams, besides providing high resolution images, allowing the detection of small structures (> 10 cm), also presented a correlation with the permeability data. In this way, GPR data may be used to build upscaling laws, bridging the gap between outcrop and seismic data sets, which may result in better models for faulted reservoirs

Expressão em superfície do sistema de falhas Poço Verde-caraúbas, Bacia Potiguar

The structural knowledge of the western portion of the Potiguar Basin is still in its infancy, especially these related to NW-trending fault systems. This paper analyzes the Poço Verde-Caraúbas Fault System, which was initially recognized in subsurface. The activities involved in this study correspond to remote-sensing analysis and, in particular, to the geometric and kinematic analysis of post-rift sequences of the basin. In addition, the study aimed to determine the stress fields operating in the area. The studies were carried out in an area of 1,000 km², located in the western portion of Potiguar Basin along the Poço Verde-Caraúbas Fault System, Rio Grande do Norte State. The remote sensing imagery indicates a predominance of NW-SE-trending lineaments, consistent with the fault system under study, followed by the NE-SW, N-S and E-W directions. The tectonic structures mapped were analyzed only in outcrops of the Jandaíra Formantion. They are joints (filled or not) in all directions, but with predominance of the NW-trending joints. Faults are usually N-S-trending normal faults and NW-SE and NE-SW-trending strike-slip faults. Geodynamic analysis identified two tectonic stress fields: the first field, "Field 1" is represented by an N-S-trending horizontal compression and E-W-trending horizontal extension. This field affected the Potiguar Basin at least until the Miocene. The second field, "Field 2", is represented by an E-W-trending horizontal compression and N-S-trending horizontal extension. This is the present-day stress field and has affected the Potiguar basin since the Pliocene

Dinâmica da paisagem no litoral oriental do Rio Grande do Norte: geocartografia e padrões espaciais dos campos de dunas móveis

This study shows the results of a research developed in the coastal regions of the Maxaranguape and Touros municipalities, more specific in the mobile dune fields of the Rio Grande do Norte's eastern coast. Although the coastal zones, represent a small percentage of the earth's surface it concentrates a great part of the world's population. The Rio Grande do Norte's state coastal landscape mosaic composed by the dune fields suggest a dynamic scene of changes in the spatial and temporal arranges, with significant changes in the geometry of the sedimentary cover. Following this perspective this research has the objective to map the emerged coastal zone of the Rio Grande do Norte's eastern coast under the perspective of the time-space evolution of the mobile dune fields using geoprocessing techniques, which includes remote sensing, digital images processing and geographic information system (GIS). The results imply the issue of thematic maps: Geologic map; multitemporal evolution map of the mobile dune fields; quantification of the mobile dune fields differences map; temporal evolution of the mobile dune fields surrounds map. The El Niño episodes have directly affected the atmospheric circulation, what have enhanced the sedimentary input in the sand dune, what can justify the relative area growth between the years of 1993 and 2001. The dynamic of the landscape transition were higher than the stability of the spatial pattern of the dune and it's surrounds, as a result the Rio Grande do Norte eastern coast dune fields, specially the mobile dunes from Touros, Zumbi and Maracajau have shown a decrease on the sedimentary cover without vegetation area from 1970 to 2007. Therefore, the data acquired and the techniques used, can be, eventually applied to the mobile dune fields monitoring in order to preserve the dune ecosystems in the Rio Grande do Norte coast

Dinâmica do uso e ocupação do solo no litoral de Macau-RN no período de 1978 a 2008

This study was developed in the northern coast of the city of Macau, a total area of 88,52 km², located in the State of Rio Grande do Norte. It presents relatively plain surface, with interlaced of streams and gamboas, characterized by contributions of oceanic water, flooding areas of swamps. Altogether, the climatic and topographical conditions provide an ideal environment for the development of saline activity. Inserted in the geologic context of the Potiguar Basin, the region presents favorable conditions for the production of hydro-carbons. It still presents natural conditions for shrimp breeding and artisanal fishing. This work analyzes the transformations occurred in the land use, using air photographs of 1978, Landsat 5 ETM Images of 1988, 1998 and 2008. A secular analyzes was carried through the dynamics of the use of the territory and the transformations occurred in the landscape due to the increment of the productive activities. In the survey of the data for study of the area, it was verified that little alteration occurred in the 30 years. The saline activity that was present since the year of 1978 having an increase of about 5% in thirty years; the shrimp breeding activity that had its presence in the decade of 1990, presented a high growth in the land use, therefore in 1998 it presented 0.45% and currently it presents 6.59%. In the field it was observed that great areas used previously for the saline activity, today it is prepared for shrimp breeding and that the areas of petroleum exploration occupy salt mines, beaches and trays. In 1988 it presented a percentage of 0, 07% and currently it occupies 0.46%, having grown 50% in the last 10 years. Although the variation of the occupation of the area has been little expressive, shrimp breeding showed a growth of 1,200% in only 10 years. In regards to petroleum activity, there wasn t any demonstration of an increasing impact in the land use in the area of study in 26 years of exploration