Preparação e caracterização de coacervatos e vidros a base de fosfato, dopados com európio

Pós-graduação em Química - IQ

Avaliação de processos de degradação de corantes dispersos por técnicas eletroquímica e fotoeletroquímica usando eletrodos de Pt, filmes finos e nanotubos de 'TI'/'TIO IND. 2' e bicomponentes 'W'/'WO IND. 3'/'TIO IND. 2'

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Avaliação do comportamento de mistura de argamassas através de reometria rotacional

A principal etapa de preparação das argamassas consiste na mistura dos materiais sólidos com água. A introdução do líquido conduz a uma série de eventos de aglomeração e desaglomeração no sistema, que, por sua vez, irão resultar em esforços durante essa etapa. Estudos previamente realizados demonstraram a capacidade de mensuração desses esforços através de curvas que relacionam o torque com o tempo em equipamentos como os reômetros. Nessa perspectiva, o objetivo deste trabalho é avaliar como o tempo influencia a energia de mistura e as propriedades reológicas de argamassas de revestimento com e sem a utilização de aditivo dispersante. O material foi misturado no reômetro rotacional do tipo planetário por tempos distintos (17, 47, 87 e 297 s) e em seguida foi submetido a três ciclos de cisalhamento consecutivos. Em tempos curtos verificou-se que a energia de mistura é baixa, não sendo capaz de romper os aglomerados e homogeneizar o sistema, resultando em materiais reologicamente instáveis e menos fluidos. Por sua vez, a mistura de 297 s demonstrou ser mais eficiente, produzindo uma argamassa estável e fluida. Nas argamassas com o dispersante, os níveis de energia de mistura envolvidos foram mais baixos, e o sistema tendeu a homogeneizar-se mais rapidamente, além de ter resultado em argamassas mais fluidas.

Influência do tempo de adição do policarboxilato em pastas de cimento Portland para cimentação de poços petrolíferos

Cement pastes used in cementing oil wells operations are prepared according to the specific characteristics of each well. The physical properties requested for each folder formulation depend on the temperature and pressure of the well to be cemented. The rheological properties of the pulp are important control parameter for efficiency in transportation and positioning the folder during the cementing operation. One of the main types of additive used for the adjustment of rheological properties of cement pastes is the dispersant additive. This work aims to study the influence of variation of the time of addition of the polycarboxylate (0, 5, 10 and 15 minutes) in cement pastes, considering the initial periods of hydration of cement particles as fundamental point for better performance dispersant additive. Pastes were prepared with a density set at 15.6 lb/gal (1.87 g/cm3) and polycarboxylate concentrations ranging from 0.01 gpc to 0.05 gpc circulation temperature (BHCT) of 51°C and static temperature (BHST) of 76 C. The pastes were characterized from a rheological measurements, volume filtered, thickening time and resistance to compression formulations. Also were carried out tests Diffraction X-ray (XRD) and Scanning Electron Microscopy (MEV). The results showed that the addition of policaboxilato after 15 minutes decreased by 70% the values of rheological parameters. According to results of DRX and MEV, the addition of dispersant after 15 minutes did not affect the chemical reactions and subsequent formation of cement hydration products. A study of the economic feasibility to realize the financial benefits of the technique, which can be seen only with the use of the technique in this work to reduce the cost of production of cement paste was carried out, can get up to $ 1015.00 for each folder 100 barrels produced with said formulations.

Influência do tempo de adição do policarboxilato em pastas de cimento Portland para cimentação de poços petrolíferos

Cement pastes used in cementing oil wells operations are prepared according to the specific characteristics of each well. The physical properties requested for each folder formulation depend on the temperature and pressure of the well to be cemented. The rheological properties of the pulp are important control parameter for efficiency in transportation and positioning the folder during the cementing operation. One of the main types of additive used for the adjustment of rheological properties of cement pastes is the dispersant additive. This work aims to study the influence of variation of the time of addition of the polycarboxylate (0, 5, 10 and 15 minutes) in cement pastes, considering the initial periods of hydration of cement particles as fundamental point for better performance dispersant additive. Pastes were prepared with a density set at 15.6 lb/gal (1.87 g/cm3) and polycarboxylate concentrations ranging from 0.01 gpc to 0.05 gpc circulation temperature (BHCT) of 51°C and static temperature (BHST) of 76 C. The pastes were characterized from a rheological measurements, volume filtered, thickening time and resistance to compression formulations. Also were carried out tests Diffraction X-ray (XRD) and Scanning Electron Microscopy (MEV). The results showed that the addition of policaboxilato after 15 minutes decreased by 70% the values of rheological parameters. According to results of DRX and MEV, the addition of dispersant after 15 minutes did not affect the chemical reactions and subsequent formation of cement hydration products. A study of the economic feasibility to realize the financial benefits of the technique, which can be seen only with the use of the technique in this work to reduce the cost of production of cement paste was carried out, can get up to $ 1015.00 for each folder 100 barrels produced with said formulations.

Uma nova proposta de fluidos de perfuração aquosos à base de polímeros vinílicos e bentonita para poços de alta temperatura e pressão

The advance of drilling in deeper wells has required more thermostable materials. The use of synthetic fluids, which usually have a good chemical stability, faces the environmental constraints, besides it usually generate more discharge and require a costly disposal treatment of drilled cuttings, which are often not efficient and require mechanical components that hinder the operation. The adoption of aqueous fluids generally involves the use of chrome lignosulfonate, used as dispersant, which provides stability on rheological properties and fluid loss under high temperatures and pressures (HTHP). However, due to the environmental impact associated with the use of chrome compounds, the drilling industry needs alternatives that maintain the integrity of the property and ensure success of the operation in view of the strong influence of temperature on the viscosity of aqueous fluids and polymers used in these type fluids, often polysaccharides, passives of hydrolysis and biological degradation. Therefore, vinyl polymers were selected for this study because they have predominantly carbon chain and, in particular, polyvinylpyrrolidone (PVP) for resisting higher temperatures and partially hydrolyzed polyacrylamide (PHPA) and clay by increasing the system's viscosity. Moreover, the absence of acetal bonds reduces the sensitivity to attacks by bacteria. In order to develop an aqueous drilling fluid system for HTHP applications using PVP, HPAM and clay, as main constituents, fluid formulations were prepared and determined its rheological properties using rotary viscometer of the Fann, and volume filtrate obtained by filtration HTHP following the standard API 13B-2. The new fluid system using polyvinylpyrrolidone (PVP) with high molar weight had higher viscosities, gels and yield strength, due to the effect of flocculating clay. On the other hand, the low molecular weight PVP contributed to the formation of disperse systems with lower values in the rheological properties and fluid loss. Both systems are characterized by thermal stability gain up to around 120 ° C, keeping stable rheological parameters. The results were further corroborated through linear clay swelling tests.

Uma nova proposta de fluidos de perfuração aquosos à base de polímeros vinílicos e bentonita para poços de alta temperatura e pressão

The advance of drilling in deeper wells has required more thermostable materials. The use of synthetic fluids, which usually have a good chemical stability, faces the environmental constraints, besides it usually generate more discharge and require a costly disposal treatment of drilled cuttings, which are often not efficient and require mechanical components that hinder the operation. The adoption of aqueous fluids generally involves the use of chrome lignosulfonate, used as dispersant, which provides stability on rheological properties and fluid loss under high temperatures and pressures (HTHP). However, due to the environmental impact associated with the use of chrome compounds, the drilling industry needs alternatives that maintain the integrity of the property and ensure success of the operation in view of the strong influence of temperature on the viscosity of aqueous fluids and polymers used in these type fluids, often polysaccharides, passives of hydrolysis and biological degradation. Therefore, vinyl polymers were selected for this study because they have predominantly carbon chain and, in particular, polyvinylpyrrolidone (PVP) for resisting higher temperatures and partially hydrolyzed polyacrylamide (PHPA) and clay by increasing the system's viscosity. Moreover, the absence of acetal bonds reduces the sensitivity to attacks by bacteria. In order to develop an aqueous drilling fluid system for HTHP applications using PVP, HPAM and clay, as main constituents, fluid formulations were prepared and determined its rheological properties using rotary viscometer of the Fann, and volume filtrate obtained by filtration HTHP following the standard API 13B-2. The new fluid system using polyvinylpyrrolidone (PVP) with high molar weight had higher viscosities, gels and yield strength, due to the effect of flocculating clay. On the other hand, the low molecular weight PVP contributed to the formation of disperse systems with lower values in the rheological properties and fluid loss. Both systems are characterized by thermal stability gain up to around 120 ° C, keeping stable rheological parameters. The results were further corroborated through linear clay swelling tests.

Scaffolds porosos à base de fosfatos de cálcio para regeneração óssea

Graças ao aumento da esperança média de vida do ser humano, a engenharia de tecidos tem sido uma área alvo de enorme investigação. A utilização de estruturas tridimensionais porosas e biodegradáveis, denominadas de scaffolds, como matriz para a adesão e proliferação celular tem sido amplamente investigada. Existem atualmente diversas técnicas para a produção destas estruturas mas o grau de exigência tem vindo a aumentar, existindo ainda lacunas que necessitam ser preenchidas. A técnica de robocasting consiste numa deposição camada a camada de uma pasta coloidal, seguindo um modelo computorizado (CAD) e permite a produção de scaffolds com porosidade tamanho de poro e fração de porosidade controlados, boa reprodutibilidade, e com formas variadas, as quais podem ser idênticas às dos defeitos ósseos a preencher. O presente estudo teve como objetivo produzir scaffolds porosos à base de fosfatos de cálcio através de robocasting. Para tal, foram estudadas duas composições de pós à base de β-TCP, uma pura e outra co-dopada com estrôncio, zinco e manganês. Inicialmente os pós foram sintetizados pelo método de precipitação química por via húmida. Após a síntese, estes foram filtrados, secos, calcinados a 1000ºC e posteriormente moídos até possuírem um tamanho médio de partícula de cerca de 1,5 μm. Os pós foram depois peneirados com uma malha de 40μm e caracterizados. Posteriormente foram preparadas várias suspensões e avaliado o seu comportamento reológico, utilizando Targon 1128 como dispersante, Hidroxipropilmetilcelulose (HPMC) como ligante e polietilenimina (PEI) como agente floculante. Por fim, e escolhida a melhor composição para a formação da pasta, foram produzidos scaffolds com diferentes porosidades, num equipamento de deposição robótica (3D Inks, LLC). Os scaffolds obtidos foram secos à temperatura ambiente durante 48 horas, sinterizados a 1100ºC e posteriormente caracterizados por microscopia eletrónica de varrimento (SEM), avaliação dos tamanhos de poro, porosidade total e testes mecânicos. Ambas as composições estudadas puderam ser transformadas em pastas extrudíveis, mas a pasta da composição pura apresentou uma consistência mais próxima do ideal, tendo originado scaffolds de melhor qualidade em termos de microestrutura e de propriedades mecânicas.

Adição de superplastificante e anti-segregante à base de CMC em pastas de cimento para Poços de Petróleo

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

Modificación de las propiedades de matrices cementantes mediante la adición de nanopartículas de sílice

En la presente investigación, se evaluó el efecto de adicionar nanopartículas de sílice a dos matrices cementes buscando establecer su influencia en las propiedades finales de dichos materiales. Para llevar a cabo esta evaluación, se adicionaron las nanopartículas en dosificaciones desde 0.30% - 5.0% en peso, con la finalidad de determinar la dosificación a la cual se obtienen los mejores resultados. Una de las conclusiones obtenidas de la presente investigación señala que al utilizar este tipo de materiales, el mayor reto a superar, es la correcta dispersión de las nanopartículas en las matrices cementantes, ya que de no asegurar dicha dispersión y debido a la alta energía superficial que poseen las nanopartículas, se presenta una tendencia natural a aglomerarse conformando así materiales de tamaños muy superiores a los que presentan en su estado original, perdiendo así la ventaja de su uso. Para prevenir este efecto y como resultado de la primera etapa de esta investigación, se propuso un método de mezclado en el cual se utilizó como dispersante un aditivo superplastificante (en adelante llamado SP) de base policarboxilato de calcio en dosificaciones de 0.5% en peso que se adicionó a ambas matrices cementantes. Los resultados obtenidos sugieren que algunas propiedades tales como la resistencia mecánica a la compresión, la resistencia a la flexión y sobre todo, la resistencia al ataque químico por sulfatos, se ven mejoradas mediante la adición de nanopartículas de sílice. Dicha mejoría se observó tanto en la matriz de cemento Portland como en la matriz de cemento sulfoaluminoso. Los resultados finales de la investigación mostraron que la resistencia mecánica a la compresión para un cemento Portland ordinario se mejoró hasta en un 40% a edad de 24 h cuando se adicionaron las nanopartículas en porcentaje de 0.50% en peso, sin embargo, los resultados al resto de las edades no presentaron mejoría. Para la matriz de cemento sulfoaluminoso (en adelante CSA), los mejores resultados se obtuvieron también con la dosificación de 0.50% en peso con relación al cemento, sin embargo, la mejoría no fue de la misma magnitud a la obtenida con la matriz de cemento Portland. Por otro lado, la resistencia al ataque químico por sulfatos presentó una mejoría de hasta un 80% para la matriz de cemento sulfoaluminoso cuando se adicionaron las nanopartículas de sílice. Este resultado sugiere que la matriz con nanopartículas presenta una mayor densificación propiciando por ende, un menor grado de porosidad.

Comportamento reológico de materiais cimentícios para poços de petróleo contendo naftaleno condensado ou policarboxilato

Pastas a base de cimento Portland são utilizadas na cimentação de poços de petróleo. Elas consistem de uma mistura de partículas sólidas de cimento dispersas em água e aditivos. Atualmente, diversos materiais alternativos são utilizados como aditivos, objetivando a modificação e a melhoria das propriedades das pastas de cimento, especialmente no aumento da fluidez. Novos aditivos plastificantes são capazes de suportar as diversas condições de poços, promovendo propriedades no estado fluido compatíveis às condições exigidas para cimentação.Dispersantes são os componentes da pasta que garantem fluidez, além de proporcionar controle na água perdida por filtração na formação porosa, garantindo o sucesso da operação de bombeio. Em deter minados campos, além do efeito da profundidade, as condições geológicas das formações promovemvariações do gradiente de pressão e temperatura ao longo da profundidade vertical do poço. Recentemente, diversos aditivos químicos da indústria da construção civil tem sido estudados em condições de cimentação de poços de petróleo. Vários produtos testados tem apresentado desempenho superior aos produtos normalmente empregados pela indústria de petróleo com boa relação custo/benefício em função do volume de mercado da construção civil. Resultados promissores na seleção de aditivos com função dispersante da construção civil para operações de cimentação de poços de petróleo onshore foram obtidos para temperaturas até 80°C. O potencial de uso desses aditivos permite estabelecer novas soluções para problemas encontrados na cimentação de poços de petróleo HPHT, poços sujeitos à injeção de vapor, poços depletados e poços produtores de gás. Na construção civil, os superplastificantes permitem reduzir o fator água/cimento das argamassas proporcionando melhoria de propriedades como resistência mecânica e fluidez. Assim, o objetivo deste trabalho foi o estudo e a caracterização reológica de pastas constituídas de cimento Portland, água e aditivos do tipo plastificante, com função dispersante a base de naftaleno condensado e policarboxilato, na faixa de temperaturas de 58°C e 70ºC. As condições utilizadas para a avaliação dos aditivos alternativos foram baseadas em uma cimentação primária para um poço hipotético de 2200 m de profundidade e gradientes geotérmicos de 1,7°F/100 pés e 2,1°F/100 pés. Os resultados demonstraram a grande eficiência e o poder dispersivo do policarboxilato para as temperaturas estudadas. O aditivo promoveu alta fluidez, sem efeitos de sedimentação da pasta. O dispersante à base de naftaleno reduziutant o a viscosidade plástica como o limite de escoamento acimada concentração a partir de 0,13%. O modelo de Bingham descreveu bem o comportamento reológico das pastas com policarboxilato para todas as concentrações

Desenvolvimento de sistemas de aditivos químicos para aplicação em cimentações de poços de petróleo

The primary cementing is an important step in the oilwell drilling process, ensuring the mechanical stability of the well and the hydraulic isolation between casing and formation. For slurries to meet the requirements for application in a certain well, some care in the project should be taken into account to obtain a cement paste with the proper composition. In most cases, it is necessary to add chemicals to the cement to modify its properties, according to the operation conditions and thus obtain slurries that can move inside the jacket providing a good displacement to the interest area. New technologies of preparation and use of chemicals and modernization of technological standards in the construction industry have resulted in the development of new chemical additives for optimizing the properties of building materials. Products such as polycarboxylate superplasticizers provide improved fluidity and cohesion of the cement grains, in addition to improving the dispersion with respect to slurries without additives. This study aimed at adapting chemical additives used in civil construction to be used use in oilwell cement slurries systems, using Portland cement CPP-Special Class as the hydraulic binder. The chemical additives classified as defoamer, dispersant, fluid loss controller and retarder were characterized by infrared absorption spectroscopy, thermogravimetric analyses and technological tests set by the API (American Petroleum Institute). These additives showed satisfactory results for its application in cement slurries systems for oil wells. The silicone-based defoamer promoted the reduction of air bubbles incorporated during the stirring of the slurries. The dispersant significantly reduced the rheological parameters of the systems studied. The tests performed with the fluid loss controller and the retarder also resulted in suitable properties for application as chemical additives in cement slurries

Efeito da adição de cargas minerais leves na resistência mecânica de grautes para cimentação de poços offshore

The preparation of cement slurries for offshore well cementing involves mixing all solid components to be added to the mixing water on the platform. The aim of this work was to study the formulation of pre-prepared dry mixtures, or grouts, for offshore oilwell cementing. The addition of mineral fillers in the strength of lightweight grouts applied for depths down to 400 m under water depths of 500 m was investigated. Lightweight materials and fine aggregates were selected. For the choice of starting materials, a study of the pozzolanic activity of low-cost fillers such as porcelain tile residue, microsilica and diatomaceous earth was carried out by X-ray diffraction and mechanical strength tests. Hardened grouts containing porcelain tile residue and microsilica depicted high strength at early ages. Based on such preliminary investigation, a study of the mechanical strength of grouts with density 1.74 g/cm3 (14.5 lb/gal) cured initially at 27 °C was performed using cement, microsilica, porcelain tile residue and an anti-foaming agent. The results showed that the mixture containing 7% of porcelain tile residue and 7% of microsilica was the one with the highest compressive strength after curing for 24 hours. This composition was chosen to be studied and adapted for offshore conditions based on testes performed at 4 °C. The grout containing cement, 7% of porcelain tile residue, 7% of active silica and admixtures (CaCl2), anti-foaming and dispersant resulted satisfactory rheology and mechanical strength after curing for 24 hours of curing