Fundamental processes of cement hydration were studied at elevated temperatures, between 100 and 200oC at saturated steam pressure, using hydrothermal curing. Initial investigations centred on treatments on Ca3SiO5 and -Ca_2SiO_4, synthesised in the laboratory, having compositions similar to those which occur in cement clinker. Their reaction products, either separately or with blending agents such as quartz or silicic acid, were identified by x-ray diffraction. Further characterisation data were obtained for tobermorite, xonotlite, hillebrandite, gyrolite, truscottite, kilchoanite, calciochondrodite, -dicalcium silicate hydrate and tricalcium silicate hydrate using scanning electron microscopy, infrared spectroscopy and nuclear magnetic resonance spectroscopy. The current postulated structures of hillebrandite and tricalcium silicate hydrate were reassessed. The factors affecting compressive strength development of cement pastes were reviewed. Theoretical volume changes were calculated for the formation of hydrothermal calciumsilicate hydrates. These may be a useful aid in assessing the suitability of a particular phase and estimating the likely consequences of phase changes on strength. The nature of the silica source affects the type of products obtained. A more detailed study of the reaction between Ca3SiO5 and various blending agents was undertaken in order to correlate between formulation, mineralogy after hydrothermal treatment, compressive strength and porosity. Actual cement blends were studied using a typical class G oilwell cement and various blending agents. In short term tests the mineralogy and compressive strength were determined with varying compositions and temperatures. It is hoped that this information will be an aid in predicting optimum compositions by correlating properties with the nature of the materials and their chemistry. Class J cement hydration and class G cement blends were also studied by infrared and nuclear magnetic resonance spectroscopy.

Made available in DSpace on 2014-12-17T14:06:55Z (GMT). No. of bitstreams: 1 CarinaGMM_DISSERT.pdf: 2881294 bytes, checksum: 3b5fb2cb077e76e3477ec04b95724ee5 (MD5) Previous issue date: 2009-12-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / One of the major current challenges for oilwell companies is the extraction of oil from evaporitic zones, also known as pre-salt basins. Deep reservoirs are found under thick salt layers formed from the evaporation of sea water. Salt layers seal the flow of oil from underneath rock formations, which store hydrocarbons and increase the probability of success in oil and gas exploration. Oilwells are cemented using Portland-based slurries to promote mechanical stability and zonal isolation. For pre-salt oilwells, NaCl must be added to saturate the cement slurries, however, the presence of salt in the composition of slurries affects their overall behavior. Therefore, the objective of the present study was to evaluate the effect of the addition of 5 to 25% NaCl on selected properties of Portland-based slurries. A series of tests were carried out to assess the rheological behavior, thickening time, free water and ultrassonic compressive strength. In addition, the slurries were also characterized by thermal analysis, X ray diffraction and scanning electron microscopy. The results showed that the addition of NaCl affected the thickening time of the slurries. NaCl contents up to 10% shortened the thickening time of the slurries. On the other hand, concentrations in excess of 20% not only extended the thickening time, but also reduced the strength of hardened slurries. The addition of NaCl resulted in the formation of a different crystalline phase called Friedel?s salt, where free chlorine is bonded to tricalcium aluminate / Atualmente, um dos grandes desafios para as empresas petrol?feras ? a explora??o de petr?leo em bacias dominadas por estruturas salinas, mais conhecidas por zonas evapor?ticas. A camada de sal ? formada pela evapora??o da ?gua do mar, cuja composi??o qu?mica inclui altas concentra??es de cloreto de s?dio (NaCl). Reservat?rios profundos s?o encontrados abaixo de espessas camadas de sal que vedam o fluxo de ?leo para fora da rocha, aprisionando hidrocarbonetos e aumentando, assim, a probabilidade de sucesso na prospec??o de ?leo e g?s. Atendendo ?s condi??es de po?o, s?o utilizadas pastas de cimento do tipo Portland para isolar, promover resist?ncia mec?nica ao po?o e impedir a intercomunica??o zonal das forma??es rochosas produtoras. Deste modo, as pastas de cimento devem atender ?s necessidades do sal, pois este se encontra na natureza com distintas caracter?sticas. Assim, este trabalho teve como objetivo avaliar o comportamento de sistemas de pastas saturadas com NaCl, em concentra??es de 5% a 25%, frente as propriedades f?sicas e qu?micas das mesmas. Tais propriedades foram analisadas atrav?s de ensaios laboratoriais de reologia, tempo de espessamento, ?gua livre e resist?ncia ? compress?o (UCA), bem como com o uso de t?cnicas de caracteriza??o t?rmica, difra??o de raios X e microscopia eletr?nica de varredura. Os resultados mostraram que a presen?a do NaCl, quando em pequenas concentra??es (at? 10%) atua como acelerador de pega. J? quando em altas concentra??es (a partir de 20%), n?o s? apresenta efeito oposto em rela??o ? pega, retardando-a, bem como atua deleteriamente na resist?ncia ? compress?o. Foi observada, tamb?m, a forma??o de uma nova fase denominada sal de Friedel, resultado da liga??o dos cloretos livres ao aluminato tric?lcico, incorporado ?s fases s?lidas do cimento hidratado

Made available in DSpace on 2014-12-17T14:06:44Z (GMT). No. of bitstreams: 1 TulioWBJ.pdf: 572575 bytes, checksum: 5effde52c942d11015aa333c7bd07b5f (MD5) Previous issue date: 2008-02-29 / 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 / A pasta de cimento Portland ? uma mistura de part?culas s?lidas de cimento dispersas em ?gua. Tal sistema deve possuir fluidez suficiente para penetrar de forma eficiente em meio poroso, al?m de proporcionar controle na ?gua perdida por filtrado na forma??o, garantindo o sucesso da opera??o de bombeio. Em determinados campos as condi??es geol?gicas das forma??es, bem como a profundidade das faces explorat?rias do po?o podem favorecer ao acr?scimo de temperatura. Na constru??o civil os superplastificantes reduzem o fator ?gua cimento das argamassas proporcionando aumento de propriedades como resist?ncia mec?nica e fluidez, j? o anti-segregante proporciona uma melhor trabalhabilidade das argamassas. Sistemas com a adi??o de dispersantes e anti?segregante utilizados convencionalmente em cimento Portland CPII-Z-32 RS foram analisados em pastas de cimento Portland Especial, utilizadas para opera??es de squeeze e cimenta??o em po?os petrol?feros, com ?nfase em tr?s aspectos: fluidez, perda do volume de filtrado e efeito sinerg?tico. Os par?metros analisados foram estudados por meio de ensaios de desempenho nas temperaturas de 2rC e 56?C, seguindo as recomenda??es pr?ticas da norma API RP 108. Para o estudo foram selecionados materiais com car?ter dispersante como superplastificantes. e preparadas pastas com concentra??es variando de 2,60 Kgf/m3 (0,02 gal/p?3) a 5,82 Kgf/m3 (0,045 gal/p?3) em peso de cimento, com densidade constante de 1,89 g/cm3 (15,8 Ib/gal). Para o controle da ?gua perdida por filtra??o foi utilizado um agente anti-segregante a base de CMC com concentra??es variando de 0,30 % a 0,60 % em peso de cimento. Os resultados mostraram que a adi??o do anti-segregante em concentra??es acima de 0,55 % em peso de cimento resultou no aumento da viscosidade das pastas nas temperaturas avaliadas. Foi verificado que o aumento da temperatura dos testes provocou uma redu??o no desempenho do anti-segregante. Nas concentra??es de 5,20 kgf/m3 (0,040 gal/p?3) e 5,82 Kgf/m3 (0,045 gal/p?3) observou-se um melhor desempenho das propriedades avaliadas no sistema proposto. Na temperatura ambiente foi verificado instabilidade nas leituras de reologia para todas as concentra??es do anti-segregante. Foi verificado que o aumento da concentra??o de anti-segregante ? limitada as concentra??es superior a 0,55 % em peso de cimento nas temperaturas analisadas. O uso do sistema contendo superplastificante, aliado ao anti-segregante promoveu um bom desempenho face ?s propriedades reol?gicas e de controle de filtrado das pastas. A fun??o principal do anti-segregante foi otimizada com o aumento da concentra??o do superplastificante, a temperaturas acima da ambiente. Por?m o aumento da concentra??o do agente dispersante nas pastas de cimento pode provocar o retardamento das pastas em temperaturas pr?ximas da ambiente. O estudo do comportamento sist?mico dos aditivos resultou na obten??o de pastas de cimento, que podem ser otimizadas face estudos de outras propriedades intr?nsecas a sua utiliza??o nas opera??es em campos petrol?feros

Made available in DSpace on 2014-12-17T14:07:20Z (GMT). No. of bitstreams: 1 EricaNMGP.pdf: 6433422 bytes, checksum: bf4255596957765009ee816c080d6b9a (MD5) Previous issue date: 2007-04-23 / The development of activities in the oil and gas sector has been promoting the search for materials more adequate to oilwell cementing operation. In the state of Rio Grande do Norte, the cement sheath integrity tend to fail during steam injection operation which is necessary to increase oil recovery in reservoir with heavy oil. Geopolymer is a material that can be used as alternative cement. It has been used in manufacturing of fireproof compounds, construction of structures and for controlling of toxic or radioactive waste. Latex is widely used in Portland cement slurries and its characteristic is the increase of compressive strength of cement slurries. Sodium Tetraborate is used in dental cement as a retarder. The addition of this additive aim to improve the geopolymeric slurries properties for oilwell cementing operation. The slurries studied are constituted of metakaolinite, potassium silicate, potassium hydroxide, non-ionic latex and sodium tetraborate. The properties evaluated were: viscosity, compressive strength, thickening time, density, fluid loss control, at ambient temperature (27 ?C) and at cement specification temperature. The tests were carried out in accordance to the practical recommendations of the norm API RP 10B. The slurries with sodium tetraborate did not change either their rheological properties or their mechanical properties or their density in relation the slurry with no additive. The increase of the concentration of sodium tetraborate increased the water loss at both temperatures studied. The best result obtained with the addition of sodium tetraborate was thickening time, which was tripled. The addition of latex in the slurries studied diminished their rheological properties and their density, however, at ambient temperature, it increased their compressive strength and it functioned as an accelerator. The increase of latex concentration increased the presence of water and then diminished the density of the slurries and increased the water loss. From the results obtained, it was concluded that sodium tetraborate and non-ionic latex are promising additives for geopolymer slurries to be used in oilwell cementing operation / O desenvolvimento das atividades do setor petr?leo e g?s tem promovido a busca de materiais mais adequados para cimenta??o de po?os de petr?leo. No estado do RN, a integridade da bainha cimentante tende a ser prejudicada durante a inje??o de vapor, procedimento necess?rio para aumentar a recupera??o do petr?leo em reservat?rios com ?leo de alta viscosidade. O geopol?mero ? um material que pode ser utilizado como cimento alternativo, uma vez que vem sendo empregado na produ??o de componentes resistentes ao fogo, na constru??o de estruturas, e para o controle de res?duos t?xicos ou radioativos. O l?tex ? extensamente usado em pastas de cimento Portland e tem como caracter?stica o aumento significativo da resist?ncia ? compress?o das pastas. O tetraborato de s?dio ? usado em cimentos odontol?gicos como retardador de pega em resinas. A adi??o deste aditivo tem a finalidade de melhorar a propriedades das pastas geopolim?ricas para cimenta??o de po?os de petr?leo. As pastas estudadas s?o constitu?das de metacaulim, silicato de pot?ssio, hidr?xido de pot?ssio, l?tex n?o i?nico e tetraborato de s?dio. As propriedades avaliadas foram: viscosidade, resist?ncia mec?nica, tempo de espessamento, densidade e controle de filtrado, na temperatura ambiente (27?C) e de especifica??o de cimento. Os testes foram realizados seguindo as recomenda??es pr?ticas da norma API RP 10B. As pastas aditivadas com tetraborato de s?dio n?o modificaram as propriedades reol?gicas em rela??o a pasta sem aditivo, assim como n?o modificaram as propriedades mec?nicas e a densidade das pastas. O aumento da concentra??o de tetraborato de s?dio aumentou o volume de filtrado das pastas nas duas temperaturas estudadas. A propriedade que o tetraborato de s?dio obteve o melhor desempenho foi em rela??o ao tempo de pega, onde a adi??o do aditivo conseguiu triplicar o tempo de espessamento das pastas. Com rela??o ?s pastas aditivadas com l?tex observou-se que a adi??o desse aditivo diminuiu as propriedades reol?gicas e a densidade do sistema. Na temperatura ambiente, o aditivo funcionou como acelerador de pega e aumentou a resist?ncia mec?nica das pastas. A presen?a de ?gua reduziu a densidade das pastas e aumentou o volume de filtrado a medida que aumentou a concentra??o do aditivo. A partir dos resultados obtidos concluiu-se que o tetraborato de s?dio e o l?tex n?o i?nico s?o aditivos promissores para pastas geopolim?ricas para cimenta??o de po?os de petr?leo