Contribuição ao estudo do envelhecimento de ligantes asfálticos : influência da adição de polímeros e comportamento frente a radiação uv

A malha rodoviária brasileira apresenta-se, em sua maior extensão, em má condições de serventia. Uma das alternativas para se evitar deformações permanentes e trincamentos no pavimento é a adição, a quente e em reatores especiais, de polímeros ao asfalto. Esta prática já é realizada no Brasil há alguns anos, porém ainda não se tem um domínio do assunto, principalmente no caso da modificação de ligantes asfálticos brasileiros. O objetivo deste trabalho é avaliar a influência de algumas propriedades do polímero modificador no envelhecimento do ligante asfáltico modificado. Para tanto se realizou inicialmente um estudo sobre o mecanismo de envelhecimento de ligantes puros, inclusive frente a radiação ultravioleta do sol, e em seguida utilizou-se a mesma metodologia para avaliar o papel do polímero neste processo. Além disso, relacionou-se através de um projeto de experimentos a massa molar e teor de estireno do polímero SBS linear com suas propriedades clássicas, estabilidade, temperatura de transição vítrea e morfologia. Observou-se que a simulação de envelhecimento UV em laboratório, desenvolvida neste estudo, foi extremamente satisfatória. Os processos de foto-oxidação e termooxidação resultam em mecanismos diferentes de envelhecimento. A origem e composição química dos ligantes é de suma importância no mecanismo de envelhecimento UV destes. A massa molar e o teor de estireno do polímero modificador representam propriedades importantes para a estabilidade e durabilidade do ligante asfáltico modificado.

Caracterização físico-química e avaliação dos perfis de liberação in vitro de micropartículas revestidas com nanocápsulas poliméricas

Micropartículas nanorrevestidas foram preparadas através da secagem por aspersão empregando-se suspensões de nanocápsulas poliméricas como material de revestimento. Uma matriz 2³ foi empregada, e os fatores analisados foram o método de preparação de nanocápsulas (nanoprecipitação e emulsificação-difusão), o polímero [poli(ε-caprolactona) e Eudragit® RS100] e a forma de inclusão da indometacina nas micropartículas (nanocápsulas ou núcleo). Duas formulações adicionais foram preparadas associando a indometacina ao dióxido de silício em etapa única, empregando nanocápsulas obtidas através do método de nanoprecipitação com a poli(ε-caprolactona) e com o Eudragit® RS100. As suspensões de nanocápsulas foram caracterizadas através da medida do pH, do tamanho médio de partícula, do potencial zeta e da eficiência de encapsulação. As micropartículas nanorrevestidas foram caracterizadas quanto ao tamanho de partícula, a taxa de associação, ao rendimento, a área superficial e ao volume de poros. A análise morfológica foi realizada através da microscopia eletrônica de varredura e da microscopia óptica. Também foram determinados o tamanho médio de partícula e o potencial zeta dos pós ressuspendidos. Os perfis de dissolução foram avaliados em tampão fosfato pH 6,8 através da eficiência de dissolução, dos fatores de similaridade e de diferença, da modelagem matemática e do modelo da Lei da Potência. O conjunto dos resultados permitiu selecionar as formulações preparadas com Eudragit® RS100 como sendo as mais promissoras, porque apresentaram maior controle da liberação do fármaco. Em relação à técnica de preparação das nanocápsulas foi selecionada a nanoprecipitação, pois possibilitou a redução de tensoativos, o que torna o processo de secagem mais eficiente. Além disso, a estratégia de associação do fármaco em uma etapa demonstrou perfis de liberação mais controlados para as micropartículas nanorrevestidas. A modelagem matemática empregando a Lei da Potência permitiu a proposição de um modelo de dissolução, a desaglomeração do sistema nanorrevestido microparticulado.

Micropartículas contendo pantoprazol sódico : preparação, caracterização físico-química e avaliação anti-ulcerativa in vivo e da absorção intestinal ex vivo

O pantoprazol (PAN) é um inibidor da bomba de prótons clinicamente empregado para o tratamento de úlcera gástrica e refluxo gastro-esofágico. Estudos relacionados à estabilidade físico-química mostraram que a degradação do PAN está diretamente relacionada com a acidez do meio, determinando a necessidade de administrá-lo em uma forma gastrorresistente. Desse modo, este trabalho propôs-se a desenvolver micropartículas à base de polímero gastrorresistente (Eudragit S100®), polímero de baixa permeabilidade (Eudragit RS30D®) ou de blenda polimérica (Eudragit S100®/ Eudragit RS30D®), contendo PAN pela técnica de spraydrying . O estudo de dissolução in vitro utilizando célula de fluxo demonstrou que o PAN foi liberado das micropartículas em 120 minutos, seguindo cinética de primeira ordem, de acordo com o modelo monoexponencial. A avaliação da gastrorresistência in vitro em célula de fluxo e em dissolutor evidenciou que as formulações de micropartículas à base de Eudragit S100® e da blenda (Eudragit S100®/ Eudragit RS30D®), garantiram adequada proteção ao fármaco em ambiente ácido. Estudos in vivo confirmaram esses resultados, pois possibilitaram a constatação da proteção do fármaco pelas micropartículas durante a passagem pelo estômago, o que possibilitou absorção entérica do PAN em quantidade adequada para exercer atividade farmacológica. Por fim, a investigação ex vivo da permeação do PAN carreado por micropartículas no epitélio intestinal mostrou que estes sistemas foram capazes de garantir a absorção da totalidade do fármaco carreado, constatando-se ainda que este processo ocorreu segundo o modelo monoexponencial.

Polimerização de propeno com catalisadores metalocênicos via suportação in-situ utilizando SMAO como suporte

Os catalisadores metalocênicos Me2Si(Ind)2ZrCl2 e Me2Si(2-Me-Ind)2ZrCl2 foram suportados in-situ sobre SMAO e empregados na polimerização de propeno na presença de alquilalumínios tais como TEA, IPRA ou TIBA. Os resultados obtidos demonstraram que o tipo e a concentração de alquilalumínio presente no meio reacional influenciaram tanto a atividade catalítica quanto as propriedades dos polímeros gerados. Os polímeros obtidos com o catalisador suportado in-situ apresentaram propriedades distintas das obtidas no polímero gerado através da polimerização homogênea, além de morfologia controlada, confirmando que de fato a polimerização ocorreu sobre a superfície do SMAO. Através da deconvolução das curvas de GPC foi constatado o aumento do número de tipos de sítios ativos no sistema catalítico suportado in-situ, resultado que também confirmou a heterogeneização do catalisador sobre o suporte. Com o auxílio de cálculos teóricos e da deconvolução das curvas de GPC foi possível propor estruturas para os sítios ativos dos sistemas homogêneo metaloceno/MAO e heterogêneo (suportado in-situ) metaloceno/SMAO/alquilalumínio. Quando eteno foi utilizado como monômero, o comportamento do sistema catalítico metaloceno/SMAO/alquilalumínio suportado in-situ foi distinto do obtido com propeno. O catalisador Me2Si(Ind)2ZrCl2 suportado ex-situ sobre SMAO através de técnicas convencionais de suportação foi avaliado por EXAFS e foi constatado que a vizinhança eletrônica do zircônio é influenciada pela razão Zr/SMAO. Os resultados obtidos por EXAFS foram correlacionados com a variação na atividade catalítica na polimerização de eteno em função da alteração na razão Zr/SMAO.

Estrutura e dinâmica da interação de éteres de celulose com surfactantes

As técnicas de fluorimetria, condutometria, viscosimetria, turbidimetria, espalhamento de luz e espalhamento de raios-X a baixo ângulo (SAXS) foram empregadas no estudo da agregação de diferentes surfactantes aniônicos em presença de soluções aquosas diluídas de (hidroxipropil)celulose (HPC) 0,25% m/m, (hidroxipropilmetil)celulose (HPMC) 0,20% m/m e HPMC 0,10% m/m / NaCl 0,10 mol L-1. Também foram investigadas através de SAXS soluções concentradas de HPC (30, 40 e 50% m/m). Admitindo-se uma faixa geral de concentração, entre 10-4 e 10-1 mol L-1, foram utilizados neste estudo os surfactantes colato de sódio (CS), deoxicolato de sódio (DC), derivados dos sais biliares, e o alquilsintético dodecilsulafato de sódio (SDS). Observou-se que os polímeros contribuem diferentemente no processo de agregação de cada surfactante, evidenciado pela mudança dos valores da concentração de agregação crítica (CAC) em relação à concentração micelar crítica (CMC). Os resultados condutométricos confirmaram a interação éteres de celulose/sais biliares, embora a mesma tenha se mostrado mais fraca em relação a éteres de celulose/SDS. Os dados termodinâmicos demonstraram que a formação de agregados polímero/surfactante apresenta maior estabilidade do que as próprias micelas livres. Os resultados de viscosimetria e turbidimetria evidenciaram as diferenças estruturais entre HPC e HPMC, assim como entre os surfactantes. Através do espalhamento de luz dinâmico, verificou-se a existência de dois modos de correlação, rápido e lento. O primeiro é atribuído à cadeia polimérica isolada, agregados polímero/surfactante intramoleculares ou mesmo a micelas livres. Por sua vez, o modo lento relaciona-se a clusters poliméricos ou agregados polímero/surfactante intermoleculares. Adicionalmente, as curvas de distribuição dos tempos de relaxação demonstraram a influência de cada surfactante sobre a dinâmica dos polímeros. Tal influência é percebida antes mesmo da CAC, contrariando o modelo da interação polímero/surfactante proposto por Cabane. Os resultados de SAXS acusaram a formação de domínios líquido-cristalinos em xx soluções concentradas de HPC, assim como confirmaram a presença de micelas livres a altas concentrações de surfactantes nos sistemas diluídos. Em linhas gerais, os resultados indicaram a interação dos polímeros com SDS mais efetiva do que os mesmos polímeros e os sais biliares. No que tange à natureza do polímero, a HPC mostrou uma maior estabilidade na sua interação com os surfactantes do que a HPMC.

Análise toxicológica in vitro e in vivo de uma fucana antitrombótica da alga marrom Spatoglossum schdöederi

Fucan is a term used to denominate a family of sulfated polysaccharides rich in L-fucose. They are extracted mainly from the extracellular matrix of brown algae and echinoderms. The brown alga Spatoglossum schröederi (Dictyotaceae) has three heterofucans named A, B and C. Our research group have been extracted non anticoagulant heterofucan from S. schröederi which possess antithrombotic activity in vivo. However, their toxicity in vitro and in vivo has not yet been determined. For the results in toxicity in vitro, we observed that the fucan A at 20, 500 and 1000 μg/plate showed no mutagenic activity in Kado test (Microsuspension), when the bacterial strains TA97a, TA98, TA100 and TA102, with and without S9 were used. The comet assay showed that fucan A (from 20 to 1000 μg/mL) did not cause any genotoxic effect on CHO cells. There was no damage to the DNA of these cells, as evidenced by the tail length and tail moment, which were similar to that found for the negative control. The fucan A from S. schröederi was administered at 20 μg/g of rat (dose which it showed high antithrombotic activity) during two months. After that, the animals were killed and examined. The data showed that fucan A did not cause any change in biochemistry and hematological parameters, as well as, in the morphology and size of the rat s organs analyzed. In conclusion, this study indicates that fucan is a compound with potential pharmacological that has no toxicity

Análises Estruturais e atividades biológicas de exopolissacarídeo extraído do fungo comestível pleurotus Sajor-Caju e de seu derivado sulfatado quimicamente.

The exopolysaccharides are extracellular compounds produced by some species of fungi and bacteria. It is suggested that these molecules, even when in the form of complex polysaccharide-peptide, are the main bioactive molecules of many fungus. Some of the biological activities displayed by these compounds can be accentuated and others may arise when you add chemically polar or nonpolar groups to polysaccharides. The fruiting body of Pleurotus sajor-caju produces a heteropolysaccharide with antineoplastic and antimicrobial activity, but other biological activities of this polymer have not been evaluated. In this work the exopolysaccharide of Pleurotus sajor-caju was sulfated chemically and structurally characterized. We also evaluated the antiproliferative, antioxidant and anticoagulant activities from native exopolysaccharide (PN) and its sulfated derivated (PS). Polyacrylamide gel electrophoresis, infrared spectroscopy and nuclear magnetic resonance (¹³C) proved successful in sulfation of PN to obtain PS. Analysis by gas chromatography-mass spectroscopy showed that PN and PS are composed of mannose, galactose, 3-O-methyl-galactose and glucose in proportion percentage of 44,9:16,3:19,8:19 and 49, 7:14,4:17,7:18,2, respectively. The percentage of sulfate found in PS was 22.5%. Antioxidants assays revealed that the sulfation procedure affects differently the activities of exopolysaccharides, while the total antioxidant capacity, the scavenging activity of superoxide radical and ferric chelating were not affected by sulfation, on the other hand the chemical modification of PN enhanced the scavenging activity of hydroxyl radical and reducing power. PS also showed anticoagulant activity in a dose-dependent manner and clotting time was 3.0 times higher than the baseline value in APTT at 2 mg/mL. The exopolysaccharide not presented antiproliferative activity against HeLa tumor cells, but PS affects the cellular proliferation in a time-dependent manner. After 72 h, the inhibition rate of PS (2.0 mg/mL) on HeLa cells was about 60%. The results showed that PN sulfation increase some of their activities.

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

Aspectos estruturais, farmacológicos e biológicos de fucanas da alga marrom sargassum vulgare

The present study examines the chemical composition and their effects on free radicals, inflammation, angiogenesis, coagulation, VEGF effects and cellular proliferation of a polysaccharides from alga Sargassum vulgare. The sulfated polysaccharide was extracted from brown seaweed by proteolysis with enzymes maxataze. The presence of proteins and sugars were observed in crude polysaccharides. Fractionation of this crude extract was made with growing concentration of acetone (0.3-1.5 v) and produced four groups of polysaccharides. Anionic polysaccharides from brown seaweed Sargassum vulgare, SV1and PSV1 were fractionated (SV1) and purified (PSV1), and displayed with high total sugars and sulfate content and very low level of protein. This fucan SV1 contains low levels of protein and high carbohydrate and sulfate content. This polysaccharides prolonged activated partial thromboplastin time (aPTT) at 50 μg (>240 s). SV1 was found to have no effect on prothrombin time (PT), corresponding to the extrinsic pathway of coagulation. SV1 exhibits high antithrombotic action in vivo, with a concentration ten times higher than heparin. Polysaccharides from S. vulgare promoted direct inhibition enzymatic activity of thrombin and stimulated enzymatic activity of FXa. SV1 showed optimal inhibitory activity of thrombin (50.2±0.28%) at a concentration of 25 μg/mL. Its antioxidant action on scavenging radicals by DPPH was (22%), indicating the polymer has no cytotoxic action (hemolytic) on ABO and Rh blood types in different erythrocyte groups and displays strong anti-inflammatory action on all concentrations tested in the carrageenan-induced paw edema model, demonstrated by reduced edema and cellular infiltration. Angiogenesis is a dynamic process of proliferation and differentiation. It requires endothelial proliferation, migration, and tube formation. In this context, endothelial cells are a preferred target for several studies and therapies. The antiangiogenic efficacy of polysaccharides was examined in vivo in the chick chorioallantoic membrane (CAM) model by using fertilized eggs. Decreases in the density of the capillaries were assessed and scored. The results showed that SV1 and PSV1 have an inhibitory effect on angiogenesis. These results were also confirmed by inhibition tubulogenesis in rabbit aorta endothelial cell (RAEC) in matrigel. These compounds were assessed in Apoptosis assay (Annexin V - FITC / PI) and cell viability by MTT assay of RAEC. These polysaccharides do not affect the viability and do not have apoptotic or necrotic action. RAEC cell when incubated with SV1 and PSV1showed inhibition of VEGF secretion, observed when compounds were incubated at 25, 50 and 100 μg/μL. The VEGF secretion with the RAEC cell line for 24 h, was more effective for PSV1 at 50 μg/μL(71.4%) than SV1 100 μg/μL (75.9%). SV1 and PSV1 had an antiproliferative action (47%) against tumor cell line HeLa. Our results indicate that these sulfated polysaccharides have antiangiogenic and antitumoral actions

Produção e caracterização de quitooligossacarídeos produzidos pelo fungo Metarhizium anisopliae e avaliação da citotoxicidade em células tumorais

Chitosan is a natural polymer, biodegradable, nontoxic, high molecular weight derived from marine animals, insects and microorganisms. Oligomers of glucosamine (GlcN) and N-acetylglucosamine (GlcNAc) have interesting biological activities, including antitumor effects, antimicrobial activity, antioxidant and others. The alternative proposed by this work was to study the viability of producing chitooligosaccharides using a crude enzymes extract produced by the fungus Metarhizium anisopliae. Hydrolysis of chitosan was carried out at different times, from 10 to 60 minutes to produce chitooligosaccharides with detection and quantification performed by High Performace Liquid Chromatography (HPLC). The evaluation of cytotoxicity of chitosan oligomers was carried out in tumor cells (HepG2 and HeLa) and non-tumor (3T3). The cells were treated for 72 hours with the oligomers and cell viability investigated using the method of MTT. The production of chitosan oligomers was higher for 10 minutes of hydrolysis, with pentamers concentration of 0.15 mg/mL, but the hexamers, the molecules showing greater interest in biological properties, were observed only with 30 minutes of hydrolysis with a concentration of 0.004 mg/mL. A study to evaluate the biological activities of COS including cytotoxicity in tumor and normal cells and various tests in vitro antioxidant activity of pure chitosan oligomers and the mixture of oligomers produced by the crude enzyme was performed. Moreover, the compound with the highest cytotoxicity among the oligomers was pure glucosamine, with IC50 values of 0.30; 0.49; 0.44 mg/mL for HepG2 cells, HeLa and 3T3, respectively. Superoxide anion scavenging was the mainly antioxidant activity showed by the COS and oligomers. This activity was also depending on the oligomer composition in the chitosan hydrolysates. The oligomers produced by hydrolysis for 20 minutes was analyzed for the ability to inhibit tumor cells showing inhibition of proliferation only in HeLa cells, did not show any effect in HepG2 cells and fibroblast cells (3T3)

Desenvolvimento de pastas de cimento flexíveis para poços de petróleo submetidos à injeção de vapor utilizando látex do tipo SBR

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.

Degradação do PMMA através da reação despolimerização uitlizando catalisadores de óxidos mistos

In this work, mixed oxides were synthesized by two methods: polymeric precursor and gel-combustion. The oxides, Niquelate of Lanthanum, Cobaltate of Lanthanum and Cuprate of Lanthanum were synthesized by the polymeric precursor method, and treated at 300 º C for 2 hours, calcined at 800 º C for 6h in air atmosphere. In gel-combustion method were produced and oxides using urea and citric acid as fuel, forming for each fuel the following oxides Ferrate of Lanthanum, Cobaltato of Lanthanum and Ferrato of Cobalt and Lanthanum, which were submitted to the combustion process assisted by microwave power maximum of 10min. The samples were characterized by: thermogravimetric analysis, X-ray diffraction; fisisorção of N2 (BET method) and scanning electron microscopy. The reactions catalytic of depolymerization of poly (methyl methacrylate), were performed in a reactor of silica, with catalytic and heating system equipped with a data acquisition system and the gas chromatograph. For the catalysts synthesized using the polymeric precursor method, the cuprate of lanthanum was best for the depolymerization of the recycled polymer, obtaining 100% conversion in less time 554 (min), and the pure polymer, was the Niquelate of Lanthanum, with 100% conversion in less time 314 (min). By gel-combustion method using urea as fuel which was the best result obtained Ferrate of Lanthanum for the pure polymer with 100% conversion in less time 657 (min), and the recycled polymer was Cobaltate of Lanthanum with 100 % conversion in less time 779 (min). And using citric acid to obtain the best result for the pure polymer, was Ferrate of Lanthanum with 100% conversion in less time 821 (min and) for the recycled polymer, was Ferrate of Lanthanum with 98.28% conversion in less time 635 (min)

Adição do resíduo de biomassa da cana-de-açúcar em pastas para cimentação de poços petrolíferos produtores de óleos pesados

The Potiguar basin has large fields of viscous oil where the used method for recovering is based on vapor injection; this operation is carried out by injecting vapor in the oilwell directly, without the protection of a revetment through thermal insulation, what causes its dilation and, consequently, cracks in the cement placed on the annular, and lost of hydraulic insulation; this crack is occasioned by the phenomenon of retrogression of the compressive resistance due to the conversion of the hydrated calcium silicate in phases calcium-rich, caused by the high temperatures in the wells, subjected to thermal recuperation. This work has evaluated the application of composite pastes with addition of residue of biomass of ground sugar-cane bagasse as anti-retrogression mineral admixture for cementation of oil-wells subjected to thermal recuperation. The addition of the mineral residue was carried out considering a relative amount of 10, 20, 30, 40 and 59% in relation to cement mass, trying to improve the microstructure of the paste, still being developed a reference paste only with cement and a paste with addition of 40% of silica flour - renowned material in the oil industry as anti-retrogression additive. Pozzolanic activity of the ash was evaluated through XRD, TG/DTG, as the resistance to compression, and it was also determined the physical and mechanical behavior of the pastes when submitted to cure at low temperatures (22 and 38º C); besides it was evaluated the behavior of the pastes when submitted to two cycles of cure at high temperature (280ºC) and pressure (7 MPa). It was verified that the ash of the sugar-cane biomass presents pozzolanic reaction and has great efficiency in decrease the permeability of the paste by filler effect, as well as that addition of ash in a relative amount of 10, 20 e 30% increases cured compressive resistance at low temperatures. It was also showed that the ash in a relative amount of 40% and 59% has very significant efficiency as anti-retrogression additive, since it prevents the decrease of compressive resistance and forms hydrated calcium silicate type xenotlita and tobermorita which have more resistance and stability in high temperatures

Formulação de pastas cimentícias com adição de suspensões de quitosana para cimentação de poços de petróleo

Primary cementing is one of the main operations in well drilling responsible for the mechanical stability and zonal isolation during the production of oil. However, the cement sheath is constantly under mechanical stresses and temperature variations caused by the recovery of heavy oil. In order to minimize fracture and wear of the cement sheath, new admixtures are developed to improve the properties of Portland cement slurries and avoid environmental contamination caused by leaking gas and oil. Polymers with the ability to form polymeric films are candidates to improve the properties of hardened cement slurries, especially their fracture energy. The present study aimed at evaluating the effect of the addition of a chitosan suspension on cement slurries in order to improve the properties of the cement and increase its performance on heavy oil recovery. Chitosan was dissolved in acetic ac id (0.25 M and 2 M) and added to the formulation of the slurries in different concentrations. SEM analyses confirmed the formation of polymeric films in the cementitious matrix. Strength tests showed higher fracture energy compared to slurries without the addition of chitosan. The formation of the polymeric films also reduced the permeability of the slurry. Therefore, chitosan suspensions can be potentially used as cementing admixtures for heavy oil well applications