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

Modelagem Matemática e Computacional de fenômenos eletrocinéticos em meios porosos carregados eletricamente

In this work we present a mathematical and computational modeling of electrokinetic phenomena in electrically charged porous medium. We consider the porous medium composed of three different scales (nanoscopic, microscopic and macroscopic). On the microscopic scale the domain is composed by a porous matrix and a solid phase. The pores are filled with an aqueous phase consisting of ionic solutes fully diluted, and the solid matrix consists of electrically charged particles. Initially we present the mathematical model that governs the electrical double layer in order to quantify the electric potential, electric charge density, ion adsorption and chemical adsorption in nanoscopic scale. Then, we derive the microscopic model, where the adsorption of ions due to the electric double layer and the reactions of protonation/ deprotanaç~ao and zeta potential obtained in modeling nanoscopic arise in microscopic scale through interface conditions in the problem of Stokes and Nerst-Planck equations respectively governing the movement of the aqueous solution and transport of ions. We developed the process of upscaling the problem nano/microscopic using the homogenization technique of periodic structures by deducing the macroscopic model with their respectives cell problems for effective parameters of the macroscopic equations. Considering a clayey porous medium consisting of kaolinite clay plates distributed parallel, we rewrite the macroscopic model in a one-dimensional version. Finally, using a sequential algorithm, we discretize the macroscopic model via the finite element method, along with the interactive method of Picard for the nonlinear terms. Numerical simulations on transient regime with variable pH in one-dimensional case are obtained, aiming computational modeling of the electroremediation process of clay soils contaminated

Estudo por simulação computacional da interação entre polianfóteros fracos e macroíons cilíndricos

Pós-graduação em Biofísica Molecular - IBILCE

Qualidade de cavacos produzidos em sistemas florestais de curta rotação de eucalipto para fins energéticos

Pós-graduação em Agronomia (Energia na Agricultura) - FCA

Modelagem computacional de óxidos da família das perovskitas

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Amphiphilic planar membranes in ionic equilibrium: a study of pH position-dependent values

The pH values near a planar dissociating membrane are studied under a mean field approximation using the Poisson-Boltzmann equation and its linear form. The equations are solved in planar symmetry with the consideration that the charge density on the dissociating membrane surface results from an equilibrium process with the neighboring electrolyte. Results for the membrane dissociation degree are presented as a function of the electrolyte ionic strength and membrane surface charge density. Our calculations indicate that pH values have an appreciable variation within 2 nm from the membrane. It is shown that the dissociation process is enhanced due to the presence of bivalent ions and that pH values acquire better stability than in an electrolyte containing univalent ions.

Síntese de microesferas de quitosana para aplicação em liberação controlada de drogas pelo método de atomização e coagulação

Chitosan is a natural biodegradable polymer with great potential for pharmaceutical applications due to its biocompatibility, high charge density , nontoxicity and mucoadhesion. Gel formation can be obtained by the interactions of chitosans with low molecular counterions such as polyphosphates, sulphates and crosslinking with glutaraldehyde. This gelling property of chitosan allows a wide range of applications such as coating of pharmaceuticals and food products, gel entrapment of biochemicals, whole cells, microorganisms and algae. One of its main applications is the synthesis of microspheres for coating of pharmaceuticals , magnetic particles an other substances. In such a way, we can build targeted drug delivery systems. In the present work, we applied the method of spraying and coagulation. The resulting microspheres, then, were characterized by optical microscopy

Efeito da salinidade da água do mar no rendimento, composição e atividades biológicas de frações polissacarídicas da Chlorophyta Caulerpa cupressoides var. flabellata

Seaweeds sulfated polysaccharides have been described as having various pharmacological activities. However, nothing is known about the influence of salinity on the structure of sulfated polysaccharides from green seaweed and pharmacological activities they perform. Therefore, the main aim of this study was to evaluate the effect of salinity of seawater on yield and composition of polysaccharides-rich fractions from green seaweed Caulerpa cupressoides var. flabellata, collected in two different salinities beaches of the coast of Rio Grande do Norte, and to verify the influence of salinity on their biological activities. We extracted four sulfated polysaccharides-rich fractions from C. cupressoides collected in Camapum beach (denominated CCM F0.3; F0.5; F1.0; F2.0), which the seawater has higher salinity, and Buzios beach (denominated CCB F0.3; F0.5; F1.0; F2.0). Different from that observed for other seaweeds, the proximate composition of C. cupressoides did not change with increased salinity. Moreover, interestingly, the C. cupresoides have high amounts of protein, greater even than other edible seaweeds. There was no significant difference (p>0.05) between the yield of polysaccharide fractions of CCM and its CCB counterparts, which indicates that salinity does not interfere with the yield of polysaccharide fractions. However, there was a significant difference in the sulfate/sugar ratio of F0.3 (p<0.05) and F0.5 (p<0.01) (CCM F0.3 and CCB F0.5 was higher than those determined for their counterparts), while the sulfate/sugar ratio the F1.0 and F2.0 did not change significantly (p>0.05) with salinity. This result suggested that the observed difference in the sulfate/sugar ratio between the fractions from CCM and CCB, is not merely a function of salinity, but probably also is related to the biological function of these biopolymers in seaweed. In addition, the salinity variation between collection sites did not influence algal monosaccharide composition, eletrophoretic mobility or the infrared spectrum of polysaccharides, demonstrating that the salinity does not change the composition of sulfated polysaccharides of C. cupressoides. There were differences in antioxidant and anticoagulant fractions between CCM and CCB. CCB F0.3 (more sulfated) had higher total antioxidant capacity that CCM F0.3, since the chelating ability the CCM F0.5 was more potent than CCB F0.5 (more sulfated). These data indicate that the activities of sulfated polysaccharides from CCM and CCB depend on the spatial patterns of sulfate groups and that it is unlikely to be merely a charge density effect. C. cupressoides polysaccharides also exhibited anticoagulant activity in the intrinsic (aPTT test) and extrinsic pathway (PT test). CCB F1.0 and CCM F1.0 showed different (p<0,001) aPTT activity, although F0.3 and F0.5 showed no difference (p>0,05) between CCM and CCB, corroborating the fact that the sulfate/sugar ratio is not a determining factor for biological activity, but rather for sulfate distribution along the sugar chain. Moreover, F0.3 and F0.5 activity in aPTT test was similar to that of clexane®, anticoagulant drug. In addition, F0.5 showed PT activity. These results suggest that salinity may have created subtle differences in the structure of sulfated polysaccharides, such as the distribution of sulfate groups, which would cause differences in biological activities between the fractions of the CCM and the CCB

Efeitos do tratamento superficial da sílica ativa com soluções de ácidos nítrico e fosfórico em propriedades do concreto

The addition of active silica potentially improves the quality of concrete due to its high reactivity and pore refinement effect. The reactivity of silica is likely related to its charge density. Variations in surface charge alter the reactivity of the material consequently affecting the properties of concrete. The present study aimed at investigating variations in the charge density of silica as a function of acid treatments using nitric or phosphoric acid and different pH values (2.0, 4.0 and 6.0). Effects on concrete properties including slump, mechanical strength, permeability and chloride corrosion were evaluated. To that end, a statistical analysis was carried out and empirical models that correlate studied parameters (pH, acid and cement) with concrete properties were established. The quality of the models was tested by variance analysis. The results revealed that the addition of silica was efficiency in improving the properties of concrete, especially the electrochemical parameters. The addition of silica treated using nitric acid at pH = 4.0 displayed the best cement performance including highest strength, reduced permeability and lowest corrosion current

Ondas e instabilidades em plasmas com inomogeneidades suaves na densidade e no campo magnético de equilíbrio

No presente trabalho, estudamos a absorção e amplificação de ondas eletromagnéticas que se propagam em plasmas com densidade e temperatura fracamente inomogêneas, imersos em um campo magnético também inomogêneo, tendo como base a teoria cinética, dentro do contexto da aproximação local. Esse estudo se dá efetivamente a partir da obtenção do tensor dielétrico do plasma, que deve ser empregado na relação de dispersão. Iniciamos com uma revisão dos conceitos básicos sobre plasmas homogêneos e inomogêneos. Os fundamentos da teoria cinética também foram abordados. Apresentamos uma revisão de trabalhos anteriores que enfocam o mesmo tema, embora descrevendo separadamente os dois tipos de inomogeneidades. A partir desses trabalhos, obtivemos um tensor dielétrico geral, que descreve de forma simultânea as inomogeneidades do campo magnético de equilíbrio e da função distribuição de equilíbrio.Tal tensor foi obtido a partir de um sólido desenvolvimento teórico, que garante a correta descrição da troca de energia entre as ondas e as partículas do plasma. Abordamos os aspectos gerais das instabilidades de deriva, direcionando o estudo à faixa de frequência das ondas híbridas inferiores, e às instabilidades LHDI e MTSI (IWI). Utilizamos perfis lineares de inomogeneidades de campo magnêtico ambiente e densidade para modelar a região da magnetosfera conhecida como neutral sheet. Particularizamos o tensor dielétrico para o estudo específico das instabilidades LHDI e MTSI (IWI), para o tipo de perfil citado acima. Apresentamos uma nova rela»c~ao de dispers~ao para plasmas inomogêneos, que incorpora explicitamente as derivadas espaciais do tensor dielétrico do plasma. Usamos o tensor que unifica os tratamentos das inomogeneidades do campo e densidade nessa relação de dispersão, e obtivemos uma descrição unificada das instabilidades LHDI e MTSI (IWI).

Medição da densidade óssea através de ondas eletromagnéticas e classificação por MVS

This work holds the purpose of presenting an auxiliary way of bone density measurement through the attenuation of electromagnetic waves. In order to do so, an arrangement of two microstrip antennas with rectangular configuration has been used, operating in a frequency of 2,49 GHz, and fed by a microstrip line on a substrate of fiberglass with permissiveness of 4.4 and height of 0,9 cm. Simulations were done with silica, bone meal, silica and gypsum blocks samples to prove the variation on the attenuation level of different combinations. Because of their good reproduction of the human beings anomaly aspects, samples of bovine bone were used. They were subjected to weighing, measurement and microwave radiation. The samples had their masses altered after mischaracterization and the process was repeated. The obtained data were inserted in a neural network and its training was proceeded with the best results gathered by correct classification on 100% of the samples. It comes to the conclusion that through only one non-ionizing wave in the 2,49 GHz zone it is possible to evaluate the attenuation level in the bone tissue, and that with the appliance of neural network fed with obtained characteristics in the experiment it is possible to classify a sample as having low or high bone density

Determinação da densidade mineral e da elasticidade óssea após a aplicação de ondas de choque extracorpóreas no terceiro metacarpiano de equinos atletas

The porpoise of this study was to evaluate the effects of extracorporeal shock waves in third metacarpus bone from healthy horses by determination of bone elasticity. It were used 20 Thoroughbred horses, male and female, with two years old, on top of training and selected as the state healthy. At the beginning of the experiment (D0), all animals were submitted for evaluation of bone elasticity held in the third metacarpus bone. The animals were divided into two groups (Control Group - CG and Experimental Group - EG). The application of extracorporeal shock wave therapy (ESWT) was performed on the right forelimb of the animals in the experimental group in the same place evaluated for bone elasticity and was used apparatus for extracorporeal therapy of waves with 0.15 mJ/mm2 energy flux density and 2000 pulses with E6R20 probe, with focus feature of the shock wave of 20 mm. The ESWT were repeated every 21 days, a total of three sessions (D0, D21 and D42). The analysis of bone elasticity determination was realized at D21, D42 and D72. The average of speed ultrasound differed between groups at D21, D42 and D72, and the animals from EG had lower bone mineral density after applications of ESWT. There was also difference in the analysis of bone mass (Z-Score) between the groups at D21 and D42, which animals from EG showed a significant decrease in bone mass. The risk of fracture was higher in animals from experimental group at D21. It was concluded that ESWT is able to promote change in bone mineral density.

Alterações da densidade mineral óssea em vértebras de ratos wistar submetidos à ausência de carga nos membros pélvicos

The suspension of rats by the tail model is used to investigate the behavior of bone in animals unable to move around. Bone is an adaptative tissue that develops in structure and function, among other factors, in response to mechanical forces applied to it and metabolic demands that it will suffer. The absence of mechanical forces and deformation of bone that occurs causes a decrease in calcium deposition in the absence of stimuli on osteoblasts and osteocytes, favoring the action of osteoclasts, making bones weak and brittle. Therefore, the mechanical action is necessary to stimulate local bone response and thus provide growth and remodeling. The aim of this study was to evaluable by radiographic densitometry, the tail suspension for 15 and 36 days alter the bone mineral density of cervical vertebrae (C3), thoracic (T6) and lumbar (L1 and L3) of Wistar rats. Thirty Rattus norvegicus albinus, adult, male, Wistar strain, average body mass ± 350g, were divided into 3 groups: control (n = 10) - not suspended; S15 (n = 10) - suspended for 15 days and S36 (n = 10) - suspended for 36 days. For densitometric analysis vertebrae were radiographed, scanned, digitized and analyzed by the computer program ImageJ®. There was a statistically significant increase in bone mineral density in group S15, probably by the restlessness of the animals to the suspension, with a decrease in group S36, and this hypothetically is linked to the accommodation of the rats, concluding that the tail suspension altered bone mineral density in first time with a decrease over time.

Nas ondas da informação: interfaces entre o pensamento geográfico e a geografia econômica para o estudo das telecomunicações no Brasil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Capacidade de suporte de carga e densidade do solo em áreas de plantio direto com e sem escarificação

No-till has been used in many different regions of Brazil. However, depending on the location and intensity of machinery traffic, this has caused the problem of soil compaction and many producers are scarification the land as a solution to break through the layer that is restricting plant growth. The objective of this study was to evaluate the influence of scarification (0.30 m) in the physical properties of a dystrophic Alfisol comparing the results with a non-scarified contiguous area; both were previously conducted using no-till. The density and pressure of pre-consolidation were sampled in two areas of non-tillage, one with chiseling (PDCE) and one without (PDSE) by using the UMAS -Mobile Soil Sampling Unit built by NEMPA – Agroforestry Machinery and Tire Testing Center/FCA / UNESP, Botucatu ,SP. The UMAS is equipped with GPS which allows the samples to be georeferenced. The samples were evaluated in the laboratory through the collection of standardized rings. Sampling was performed at a dimension of 15 x 50 m, with 160 rings being collected. The samples containing rings which were used in determining the density and also for testing the consolidometer, were collected from the layers of 0 to 0.10 m, 0.10 to 0.20 m, 0.20 to 0.30 0.30 to I 0.40 m. For the odometer test the undisturbed sample rings were used in obtaining the load bearing capacity of the soil. The soil management adopted provided a decrease in soil density using no-tillage with scarification depths from 0.0 to 0.10 0.10 to 0.20 m while the other depths did not show any decrease. The pre-consolidation pressure in combination with soil aggregate resistance identified that the management process PDCE within all layers was subjected to water content reliability regarding a greater load bearing capacity of the soil. For the PDSE that only was possible in the 0 to 0.10 m, showing greater consolidation of this layer.