Influência da vermiculita expandida na resistência à compressão e reologia de pastas cimentantes de poços de petróleo

Several problems related to the loss of hydraulic seal in oilwells, causing gas migration and/or contamination of the production zone by water, have been reported. The loss of the hydraulic seal is a consequence of cracks which can be occasioned either by the invasion of gas during the wait on cement or by the expansion of the casing causing the fracture of the cement sheath. In case of the pressure of the formation is higher than the pressure in the annulus, gas can migrate into the slurry and form microannulus, which are channels where gas migrates after the cement is set. Cracks can be also occasioned by the fracture of the cement sheath when it does not withstand the thermal and dynamic loads. In reservoirs where the oil is heavy, steam water injection operation is required in order to get the oil flowing. This operation increases the temperature of the casing, and then it expands and causes the fracture of the cement sheath in the annulus. When the failures on the cement are detected, remedial cementing is required, which raise costs caused by the interventions. Once the use of cement in the construction civil sector is older than its use in the petroleum sector, it is common to bring technologies and solutions from the civil construction and apply them on the petroleum area. In this context, vermiculite, a mineral-clay widely encountered in Brazil, has been used, on its exfoliated form, in the civil construction, especially on the manufacture of lights and fireproof concretes with excellent thermal and acoustical properties. It has already been reported in scientific journals, studies of the addition of exfoliated vermiculite in Portland cements revealing good properties related to oilwell cementing operations. Thus, this study aimed to study the rheological behavior, thickening time, stability and compressive strength of the slurries made of Portland cement and exfoliated vermiculite in 5 different compositions, at room temperature and heated. The results showed that the compressive strength decreased with the addition of exfoliated vermiculite, however the values are still allowed for oiwell cementing operations. The thickening time of the slurry with no exfoliated vermiculite was 120 min and the thickening time of the slurry with 12 % of exfoliated vermiculite was 98 min. The stability and the rheological behavior of the slurries revealed that the exfoliated vermiculite absorbed water and therefore increased the viscosity of the slurries, even though increasing the factor cement-water. The stability experiment carried out at 133 ºF showed that, there was neither sedimentation nor reduction of the volume of the cement for the slurry with 12 % of exfoliated vermiculite. Thus, the addition of exfoliated vermiculite accelerates the set time of the cement and gives it a small shrinkage during the wait on cement, which are important to prevent gas migration

Obtenção de nanopartículas de hexaferrita de bário pelo método pechini

In this study barium hexaferrite was (general formulae BaFe12O19) was synthesized by the Pechini method under different conditions of heat treatment. Precursors like barium carbonate and iron nitrate were used. These magnetic ceramic, with magnetoplumbite type structure, are widely used as permanent magnet because of its excellent magnetic properties, such as: high Curie temperature, good magnetic anisotropy, high coercivity and corrosion resistance. The samples were characterized by thermal analysis (DTA and TG), X- ray Diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM) end Vibrating sample Magnetometer (VSM). The results confirm the expected phase, which was reinforced according to our analysis. A single phase powder at relatively high temperatures with particle sizes around 100 nm was obtained. The characteristic magnetic behavior one of the phases has been noted (probably superparamagnetic material), while another phase was identified as a ferrimagnetic material. The ferrimagnetic phase showed vortex configuration with two central and slightly inclined plateaus. In general, increase of heat treatment temperature and time, directly influenced the technological properties of the samples

Sinterização de aço inoxidável reforçado com partículas nanométricas dispersas de carbeto de nióbio - NbC

Metal powder sintering appears to be promising option to achieve new physical and mechanical properties combining raw material with new processing improvements. It interest over many years and continue to gain wide industrial application. Stainless steel is a widely accepted material because high corrosion resistance. However stainless steels have poor sinterability and poor wear resistance due to their low hardness. Metal matrix composite (MMC) combining soft metallic matrix reinforced with carbides or oxides has attracted considerable attention for researchers to improve density and hardness in the bulk material. This thesis focuses on processing 316L stainless steel by addition of 3% wt niobium carbide to control grain growth and improve densification and hardness. The starting powder were water atomized stainless steel manufactured for Höganäs (D 50 = 95.0 μm) and NbC produced in the UFRN and supplied by Aesar Alpha Johnson Matthey Company with medium crystallite size 16.39 nm and 80.35 nm respectively. Samples with addition up to 3% of each NbC were mixed and mechanically milled by 3 routes. The route1 (R1) milled in planetary by 2 hours. The routes 2 (R2) and 3 (R3) milled in a conventional mill by 24 and 48 hours. Each milled samples and pure sample were cold compacted uniaxially in a cylindrical steel die (Ø 5 .0 mm) at 700 MPa, carried out in a vacuum furnace, heated at 1290°C, heating rate 20°C stand by 30 and 60 minutes. The samples containing NbC present higher densities and hardness than those without reinforcement. The results show that nanosized NbC particles precipitate on grain boundary. Thus, promote densification eliminating pores, control grain growth and increase the hardness values

Desenvolvimento de tubulação em compósito polimérico revestida externamente com poliuretano de alta densidade

Pipelines for the transport of crude oil from the production wells to the collecting stations are named production lines . These pipes are subjected to chemical and electrochemical corrosion according to the environment and the type of petroleum transported. Some of these lines, depending upon the composition of the fluid produced, may leak within less than one year of operation due to internal corrosion. This work aims at the development of composite pipes with an external protecting layer of high density polyurethane for use in production lines of onshore oil wells, meeting operational requirements. The pipes were manufactured using glass fibers, epoxy resin, polyester resin, quartz sand and high density polyurethane. The pipes were produced by filament winding with the deposition of high density polyurethane on the external surface and threaded ends (API 15 HR/PM-VII). Three types of pipes were manufactured: glass/epoxy, glass/epoxy with an external polyurethane layer and glass/epoxy with an intermediate layer of glass fiber, polyester, sand and with an external polyurethane layer. The three samples were characterized by Scanning Electronic Microscopy (SEM) and for the determination of constituent content. In addition, the following tests were conducted: hydrostatic test, instant rupture, shorttime failure pressure, Gardner impact, transverse stiffness and axial tension. Field tests were conducted in Mossoró RN (BRAZIL), where 1,677 meters of piping were used. The tests results of the three types of pipes were compared in two events: after two months from manufacturing of the samples and after nine months of field application. The results indicate that the glass/epoxy pipes with an intermediate layer of fiber glass composite, polyester e sand and with an external layer of high density polyurethane showed superior properties as compared to the other two and met the requirements of pressure class, axial tensile strength, transverse stiffness, impact and environmental conditions, for onshore applications as production lines

Estudos de Durabilidade Frente ao Ataque Ácido de Compósitos Portland-Polímero para Cimentação de Poços de Petróleo

Portland-polymers composites are promising candidates to be used as cementing material in Northeastern oil wells of Brazil containing heavy oils submitted to steam injection. In this way, it is necessary to evaluate its degradation in the commonly acidizind agents. In addition, to identify how aggressive are the different hostile environments it is an important contribution on the decision of the acidic systems to be used in. It was investigated the performance of the Portland-polymer composites using powdered polyurethane, aqueous polyurethane, rubber tire residues and a biopolymer, those were reinforced with polished carbon steel SAE 1045 to make the electrochemical measurements. HCl 15,0 %, HCl 6,0 % + HF 1,5 % (soft mud acid), HCl 12,0 % + HF 3,0 % (regular mud acid) and HAc 10 % + HF 1,5 % were used as degrading environment and electrolytes. The more aggressive acid solution to the plain Portland hardened cement paste was the regular mud acid, that showed loss of weight around 23.0 %, followed by the soft mud acid, the showed 11.0 %, 15.0 % HCl with 7,0 % and, at last the 10.0 % HAc plus HF 1.5 % with just 1.0 %. The powdered polyurethane-composite and the aqueous polyurethane one showed larger durability, with reduction around 87.0 % on the loss of weight in regular mud acid. The acid attack is superficial and it occurs as an action layer, where the degraded layer is responsible for the decrease on the kinetic of the degrading process. This behavior can be seen mainly on the Portland- aqueous polyurethane composite, because the degraded layer is impregnated with chemically modified polymer. The fact of the acid attack does not have influence on the compressive strength or fratography of the samples, in a general way, confirms that theory. The mechanism of the efficiency of the Portland-polymers composites subjected to acid attack is due to decreased porosity and permeability related with the plain Portland paste, minor quantity of Ca+2, element preferentially leached to the acidic solution, wave effect and to substitute part of the degrading bulk for the polymeric one. The electrolyte HAc 10 % + HF 1,5 % was the least aggressive one to the external corrosion of the casing, showing open circuit potentials around +250 mV compared to -130 mV to the simulated pore solution to the first 24 hours immersion. This behavior has been performed for two months at least. Similar corrosion rates were showed between both of the electrolytes, around 0.01 μA.cm-2. Total impedance values, insipient arcs and big polarization resistance capacitive arcs on the Nyquist plots, indicating passivity process, confirm its efficiency. In this way, Portlandpolymers composites are possible solutions to be succeed applied to oilwell cementing concomitant submitted to steam injection and acidizing operation and the HAc 10,0 % + HF 1,5 % is the less aggressive solution to the external corrosion of the casing

Estudo sobre o efeito dos parâmetros de processamento dos pós e sinterização do aço inox 316l reforçado com NbC

This masther dissertation presents a contribution to the study of 316L stainless steel sintering aiming to study their behavior in the milling process and the effect of isotherm temperature on the microstructure and mechanical properties. The 316L stainless steel is a widely used alloy for their high corrosion resistance property. However its application is limited by the low wear resistance consequence of its low hardness. In previous work we analyzed the effect of sintering additives as NbC and TaC. This study aims at deepening the understanding of sintering, analyzing the effect of grinding on particle size and microstructure and the effect of heating rate and soaking time on the sintered microstructure and on their microhardness. Were milled 316L powders with NbC at 1, 5 and 24 hours respectively. Particulates were characterized by SEM and . Cylindrical samples height and diameter of 5.0 mm were compacted at 700 MPa. The sintering conditions were: heating rate 5, 10 and 15◦C/min, temperature 1000, 1100, 1200, 1290 and 1300◦C, and soaking times of 30 and 60min. The cooling rate was maintained at 25◦C/min. All samples were sintered in a vacuum furnace. The sintered microstructure were characterized by optical and electron microscopy as well as density and microhardness. It was observed that the milling process has an influence on sintering, as well as temperature. The major effect was caused by firing temperature, followed by the grinding and heating rate. In this case, the highest rates correspond to higher sintering.

Estudo da sinterabilidade de ligas de níquel obtidas por meio dos portadores de liga sic, si3n4 ou si metálico com grafita

Nickel alloys are frequently used in applications that require resistance at high temperatures associated with resistance to corrosion. Alloys of Ni-Si-C can be obtained by means of powder metallurgy in which powder mixtures are made of metallic nickel powders with additions of various alloying carriers for such were used in this study SiC, Si3N4 or Si metal with graphite. Carbonyl Ni powder with mean particle size of 11 mM were mixed with 3 wt% of SiC powders with an average particle size of 15, 30 and 50 μm and further samples were obtained containing 4 to 5% by mass of SiC with average particle size of 15 μm. Samples were also obtained by varying the carrier alloy, these being Si3N4 powder with graphite, with average particle size of 1.5 and 5 μm, respectively. As a metallic Si graphite with average particle size of 12.5 and 5 μm, respectively. The reference material used was nickel carbonyl sintered without adding carriers. Microstructural characterization of the alloys was made by optical microscopy and scanning electron microscopy with semi-quantitative chemical analysis. We determined the densities of the samples and measurement of microhardness. We studied the dissociation of carriers alloy after sintering at 1200 ° C for 60 minutes. Was evaluated also in the same sintering conditions, the influence of the variation of average particle size of the SiC carrier to the proportion of 3% by mass. Finally, we studied the influence of variation of the temperatures of sintering at 950, 1080 and 1200 ° C without landing and also with heights of 30, 60, 120 and 240 minutes for sintering where the temperature was 950 °C. Dilatometry curves showed that the SiC sintered Ni favors more effectively than other carriers alloy analyzed. SiC with average particle size of 15 μm active sintering the alloy more effectively than other SiC used. However, with the chemical and morphological analyzes for all leagues, it was observed that there was dissociation of SiC and Si3N4, as well as diffusion of Si in Ni matrix and carbon cluster and dispersed in the matrix, which also occurred for the alloys with Si carriers and metallic graphite. So the league that was presented better results containing Si Ni with graphite metallic alloy as carriers, since this had dispersed graphite best in the league, reaching the microstructural model proposed, which is necessary for material characteristic of solid lubricant, so how we got the best results when the density and hardness of the alloy

Síntese e caracterização de TaC e óxido misto de tântalo e cobre nanoestruturados a partir do precursor oxálico de tântalo através de reações gás-sólido e sólido-sólido a baixa temperatura

The research and development of nanostructured materials have been growing significantly in the last years. These materials have properties that were significantly modified as compared to conventional materials due to the extremely small dimensions of the crystallites. The tantalum carbide (TaC) is an extremely hard material that has high hardness, high melting point, high chemical stability, good resistance to chemical attack and thermal shock and excellent resistance to oxidation and corrosion. The Compounds of Tantalum impregnated with copper also have excellent dielectric and magnetic properties. Therefore, this study aimed to obtain TaC and mixed tantalum oxide and nanostructured copper from the precursor of tris (oxalate) hydrate ammonium oxitantalato, through gas-solid reaction and solid-solid respectively at low temperature (1000 ° C) and short reaction time. The materials obtained were characterized by X-ray diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), Spectroscopy X-Ray Fluorescence (XRF), infrared spectroscopy (IR), thermogravimetric (TG), thermal analysis (DTA) and BET. Through the XRD analyses and the Reitiveld refinement of the TaC with S = 1.1584, we observed the formation of pure tantalum carbide and cubic structure with average crystallite size on the order of 12.5 nanometers. From the synthesis made of mixed oxide of tantalum and copper were formed two distinct phases: CuTa10O26 and Ta2O5, although the latter has been formed in lesser amounts

Comportamento magnético de compósitos de matriz polimérica com adição de ferritas

Polymer matrix composites offer advantages for many applications due their combination of properties, which includes low density, high specific strength and modulus of elasticity and corrosion resistance. However, the application of non-destructive techniques using magnetic sensors for the evaluation these materials is not possible since the materials are non-magnetizable. Ferrites are materials with excellent magnetic properties, chemical stability and corrosion resistance. Due to these properties, these materials are promising for the development of polymer composites with magnetic properties. In this work, glass fiber / epoxy circular plates were produced with 10 wt% of cobalt or barium ferrite particles. The cobalt ferrite was synthesized by the Pechini method. The commercial barium ferrite was subjected to a milling process to study the effect of particle size on the magnetic properties of the material. The characterization of the ferrites was carried out by x-ray diffraction (XRD), field emission gun scanning electron microscopy (FEG-SEM) and vibrating sample magnetometry (VSM). Circular notches of 1, 5 and 10 mm diameter were introduced in the composite plates using a drill bit for the non-destructive evaluation by the technique of magnetic flux leakage (MFL). The results indicated that the magnetic signals measured in plates with barium ferrite without milling and cobalt ferrite showed good correlation with the presence of notches. The milling process for 12 h and 20 h did not contribute to improve the identification of smaller size notches (1 mm). However, the smaller particle size produced smoother magnetic curves, with fewer discontinuities and improved signal-to-noise ratio. In summary, the results suggest that the proposed approach has great potential for the detection of damage in polymer composites structures

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

Estudo da influência da temperatura de brasagem nas uniões zircônia/aço inox 304 utilizando metalização mecânica

Metal-Ceramic (M/C) Zirconia-stainless steel interfaces have been processed through brazing techniques due to the excellent combination of properties such as high temperature stability, high corrosion resistance and good mechanical properties. However, some M/C interfaces show some defects, like porosity and cracks results in the degradation of the interfaces, leading even to its total rupture. Most of time, those defects are associated with an improper brazing parameters selection to the M/C system. In this work, ZrO2 Y-TZP and ZrO2 Mg - PSZ were joint with the stainless steel grade 304 by brazing using a eutectic silver-copper (Ag28Cu) interlayer alloy with different thermal cycles. Ceramic surfaces were previous mechanically metallized with titanium to improve adhesion of the system. The effect of temperature on the M/C interface was studied. SEM-EDS and 3 point flexural bend test were performed to evaluate morphology, chemical composition and mechanical resistance of the M/C interfaces. Lower thermal cycle temperatures produced better results of mechanical resistance, and more regular/ homogeneous reaction layers between braze alloy and metal-ceramic surfaces. Also was proved the AgCu braze alloy activation in situ by titanium

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

Obtenção de pós de tântalo metálico a partir da redução aluminotérmica com ignição a plasma

Metallic tantalum has a high commercial value due to intrinsic properties like excellent ductility, corrosion resistance, high melt and boiling points and good electrical and thermal conductivities. Nowadays, it is mostly used in the manufacture of capacitors, due to excellent dielectric properties of its oxides. In the nature, tantalum occurs in the form of oxide and it is extracted mainly from tantalite-columbite ores. The tantalum is usually produced by the reduction of its oxide, using reductants like carbon, silicon, calcium, magnesium and aluminum. Among these techniques, the aluminothermic reduction has been used as the industrial method to produce niobium, tantalum and their alloys, due to the easy removal of the Al and Al2O3 of the system, easing further refining. In conventional aluminothermic reduction an electrical resistance is used to trigger the reaction. This reaction self-propagates for all the volume of material. In this work, we have developed a novel technique of aluminothermic reduction that uses the hydrogen plasma to trigger the reaction. The results obtained by XRD, SEM and EDS show that is possible to obtain a compound rich in tantalum through this technique of aluminothermic reduction in the plasma reactor

Influência da substituição de areia natural por pó de pedra no comportamento mecânico, microestrutural e eletroquímico de concretos

The construction industry is one of the largest consumers of natural raw materials, and concrete is considered today the most used material wide. This accentuated consumption of natural resources has generated concern with the preservation of the environment, and has motivated various studies related to the use of resid ues, which can partially or entirely substitute, with satisfactory performance, some materials such as the aggregate, and in so doing, decrease the impact on the environment caused by the produced residues. Research has been done to better understand and improve the microstructure of concrete, as well as to understand the mechanism of corrosion in reinforced steel. In this context, this work was developed aiming at discovering the influence of the substitution of natural sand by artificial sand, with rega rd to mechanical resistance, microstructure, and durability. To obtain the electrochemical parameters, an adaptation was made to the galvanostatic electrochemical method to study the corrosion in reinforced steel. Concretes of categories 20 MPa and 40 MPa were produced, containing natural sand, and concretes of the same categories were produced with artificial sand substituting the natural sand, and with the addition of sodium nitrate and sodium chloride. Due to the use of rock dust reject (artificial sand), an evaluation was made of its environmental risk. The results indicate that the concretes of category 20 MPa present a better performance than the concrete made with natural sand, thus making it a viable substitute. For the category 40 MPa, the better performance is from the concrete containing natural sand. The adaptation of the galvanostatic electrochemical technique to the study of the corrosion of reinforced steel within concrete proved to be valid for obtaining electrochemical parameters with a high degree of reliability, considering the number of degrees of freedom

Incorporação de resíduo cerâmico para prevenção da retrogressão da resistência de cimentos de poços de petróleo submetidos à injeção de vapor

Steam injection is the most used thermal recovery method of oil nowadays because of the high degree of development of the technique that allows high recovery factors. However, injection of superheated steam into the reservoir affects the entire structure of the well, including the cemented layer that presents a retrogression of compressive strength and increases the permeability due to formation of more crystalline and denser phases at temperatures above 110 °C. These changes result in failures in the cement that favor the entrance of formation fluids into the annulus space resulting in unsafe operations and restrictions in the economic life of the well. But the strength retrogression can be prevented by partial replacement of cement by silica-based materials that reduce the CaO/SiO2 ratio of cement slurries changing the trajectory of the reactions, converting those deleterious phases in phases with satisfactory mechanical strength and permeability. The aim of this study was to evaluate the behavior of a ceramic waste material rich in silica in partial and total substitution of a mineral additive used to fight the strength retrogression of cement slurries subjected to high temperatures. The evaluation was made by compression, X-ray diffraction (XRD) and thermogravimetry (TG/DTG). The samples were submitted to a cycle of low temperature (38 °C) for 28 days and a cycle of low temperature followed by exposure to 280 ºC and 1000 psi by 3 days. The results showed that slurries with additions of up to 30% of the waste material are not enough to prevent the strength retrogression, while slurries with additions of the waste material combined with silica flour in various proportions produced hydrated products of low Ca/Si ratios that maintained the compressive strength at satisfactory levels