RESUMO O isolamento zonal inadequado em poços de petróleo pode provocar problemas de segurança e ambientais. Novas pastas de cimento podem evitar esses problemas. Neste trabalho, novas pastas de cimento foram preparadas na presença de água do mar com resina epóxi- etilenodiamina formada in situ. As novas pastas foram testadas em relação às suas propriedades mecânicas e caracterizadas por FTIR, DRX, TG / DTG, porosimetria por adsorção-dessorção de N2 e RMN 29Si e 27Al no estado sólido. Algumas características cinéticas do contato de longo prazo das pastas com fluido ácido gerado in situ foram realizadas para avaliar o desempenho das novas pastas em procedimentos rotineiros de acidificação na indústria de poços de petróleo. Os dados cinéticos experimentais foram bem ajustados ao modelo cinético exponencial de ordem-variável e a um planejamento fatorial de quatro variáveis (24). Nesses estudos, foi possível avaliar detalhadamente como alguns fatores experimentais importantes atuam sobre as quantidades de ácido que interagem com as pastas, bem como verificar como esses fatores afetam a velocidade com a qual o fluido ácido interage com as pastas. Os resultados sugerem fortemente que as interações ocorridas nas interfaces de pasta de cimento epoxi/ etilenodiamina-fluido ácido são devidas às reações na superfície das pastas de cimento com preservação das suas estruturas químicas, mesmo após contato prolongado com o fluido. As novas pasta de cimento apresentam boas características para ser usada em procedimentos ecológicos no campo de poços de petróleo.

ABSTRACT Inadequate zonal isolation in oil wells can provoke safety and environmental problems. New cement slurries can avoid such problems. In this work, novel cement slurries were prepared in the presence of seawater with in situ-formed epoxy resin–ethylenediamine. The new slurries were tested in relation to their mechanical properties and characterized by FTIR, XRD, TG/DTG, porosimetry by N2 adsorption-desorption and solid-state 29Si and 27Al NMR. Some kinetic features of long-term contact of the slurries with in situ-generated mud-acid were performed to evaluate the performances of the new slurries in routine acidizing procedures in oil well industry. The experimental kinetic data were well fitted to order-variable exponential kinetic model and a factorial design of four variables (24). In these studies, it was possible to evaluate in detail how some important experimental factors act on the quantities of acid that interact with the pastes, as well as to verify how these factors affect the speed with which the mud-acid interacts with the slurries. The results strongly suggest that the interactions occurred at epoxy/ethylenediamine cement slurry/mud-acid interfaces are due to surface reactions with preservation of the chemical structures of the cement slurries, even after long-term contact with mud-acid. The new cement slurry present good features to be used in environmental-friendly procedures in oil well field.

ABSTRACT Oil is an important source of energy, mainly in developing countries. Important research has been conducted to find cementing procedures that guarantee safe and cost-effective oil exploration below pre-salt layers. This work aimed to make a new cement paste with cement, seawater, silica, biopolymers (chitosan and sodium alginate) and hydroxyapatite (HA), found in nature. For comparison purposes, slurry without additives was prepared and characterized. The HA used was extracted from fish scales (Cynoscion acoupa) in optimized condition NaOH concentration, temperature and reaction time. Both slurry were prepared with ratios water/cement (w/c) and silica/cement (s/c) equal to 0.50 and 0.35, respectively. The new cement slurry was obtained with proportions of 5% of each biopolymer and HA with respect to the total weight of the cement. In the immersion tests, specimens were immersed in samples of hyper production of saline water by 35°C for 15 days. Thereafter, they were washed, dried and its surface layers were scraped. Before, the resulting materials were characterized. The values of the ratios Ca/Si of new cement slurry (3.38 ± 0.06) were superior compared to standard (2.58 ± 0.05). The new slurry had high thermal stability and low amounts of small crystallite-type portlandite (35.70 nm). Conversely, a slurry standard formed larger crystals of about 50.3 nm. Significantly, after continuous long-term contact of both slurries with hyper-saline produced water from oil well fields operations, in comparison with standard slurry structural characteristics, the new slurry has practically maintained its pristine chemical structure, as well as has shown crystallite-type particles of NaCl and Friedel's/Kuzel's salts with lower proportion. The presence of the biopolymers and HA has driven the improved the self-healing properties observed in the new cement slurry. In this first study, the new slurry has shown adequate characteristics to contribute to cost effective and environmental-friendly oil well operations.

The objective of this study was to evaluate how silver can be inserted into hydroxyapatite (HA) via two distinct processes: co-doping with CO32- via precipitation in an aqueous medium and immersion of preformed HA crystals into Ag+ solutions. It was concluded that although Ag+ and Ca2+ have different radii, the accommodation of Ag+ ions in the Ca2+ sites of the hydroxyapatite lattice can be explained by the models proposed for inserting monovalent ions such as Na+. In this case, because Ag+ ions are larger than Ca2+ ions and have a different charge, the Ag+ ions are stabilized in the HA structure by co-substitution with CO32- ions in both the A- and B-type sites. This simultaneous insertion of Ag+ and CO32- appears to thermally stabilize the HA phase because no phase transformation is observed after calcination. In addition, the doping of HA with Ag+ ions can clearly occur via two routes: co-precipitation in the presence of these ions or diffusion in preformed hydroxyapatite crystals. This result appears to indicate the possibility of doping HA with Ag+ using less complex routes at ambient temperature and with prefabricated implants or biomaterials, which reduces the costs of producing devices with antibacterial effects.