Made available in DSpace on 2014-12-17T14:08:39Z (GMT). No. of bitstreams: 1 Julio Cezar de oliveira Freitas_nao permite publicacao_pdf.pdf: 2629498 bytes, checksum: 933e76a7de6f0be7c8d579af7a68bb18 (MD5) Previous issue date: 2010-06-18 / 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 / A cimenta??o prim?ria ? uma etapa importante durante o processo de perfura??o de po?os petrol?feros, garantindo a estabilidade mec?nica do po?o e o isolamento hidr?ulico entre o tubo de revestimento e a forma??o. Para que a pasta de cimento atenda aos requisitos estabelecidos para sua aplica??o em um determinado po?o, alguns cuidados no seu projeto de execu??o devem ser levados em considera??o para a obten??o de uma pasta de cimento com composi??o adequada. Na grande maioria dos casos, ? necess?ria a adi??o de produtos qu?micos ao cimento para modificar suas propriedades, conforme as condi??es do po?o ou opera??o e, assim, obter pastas que possam se deslocar no interior do revestimento promovendo um bom deslocamento at? a zona de interesse. Novas tecnologias de prepara??o e uso de produtos qu?micos e a moderniza??o dos padr?es tecnol?gicos no setor da constru??o civil t?m resultado no desenvolvimento de novos aditivos qu?micos para a otimiza??o das propriedades dos materiais construtivos. Produtos como superplastificantes a base de policarboxilato proporcionam maior fluidez e coes?o dos gr?os de cimento, al?m de melhorar a dispers?o em rela??o ?s pastas sem aditivos. Este trabalho tem como objetivo adequar aditivos qu?micos utilizados na constru??o civil para aplica??o em sistemas de pastas de cimento de po?os petrol?feros, utilizando como aglomerante hidr?ulico o cimento Portland CPP-Classe Especial. Os aditivos qu?micos classificados como antiespumantes, dispersantes, controladores de filtrado e retardadores de pega foram caracterizados por espectroscopia de absor??o na regi?o do infravermelho, an?lise termogravim?trica e ensaios tecnol?gicos estabelecidos pelo API (American Petroleum Institute). Estes aditivos apresentaram resultados satisfat?rios para sua aplica??o em sistemas de pasta de cimento para po?os de petr?leo. O antiespumante, a base de silicone, promoveu redu??o do aprisionamento de ar durante o processo de agita??o das pastas. O aditivo dispersante reduziu consideravelmente os par?metros reol?gicos dos sistemas estudados. Os testes realizados com o controlador de filtrado e o retardador de pega tamb?m apresentaram propriedades adequadas para aplica??o como aditivos qu?micos em pastas para cimenta??o

Made available in DSpace on 2016-06-02T19:28:57Z (GMT). No. of bitstreams: 1 TeseMVR.pdf: 1800586 bytes, checksum: c44cb463d61ffeb5394f543684f66e59 (MD5) Previous issue date: 2003-06-24 / Concern with the effect of oil spills in coastal regions resulting from the production, refining and transport of this product has been one of the priorities of the institutions working with this sector. Consequently, there is a large demand for research on the impacts of by accidents on the environment and, particularly, on natural communities. In the present study, a mesocosm experiment was used to evaluate the effects of a mixture of light Arabian and Russian oil with the chemical dispersant Corexit® 9500, over a coastal plankton community. The experiment was carried out in Rio de Janeiro and lasted 25 consecutive days. Three replicates were used as control, with only seawater, three were treated with 800 mL of petroleum and the other three were treated with the mixture 800 mL of petroleum and 80 mL of dispersant. The chemical alterations in the water were striking, especially the rise in the concentration of organic compounds. The results demonstrated a severe reduction of phytoplankton density, as a result of the addition of oil. There was also a change in the composition of the organism groups, with alteration of dominance of diatoms to phytoflagelates. Similar effect was found for the zooplankton. Both the oil and its mixture with dispersant resulted in a reduction of population densities and changes, or disappearance, of some components. Meroplanktonic organisms had a higher sensitivity to the acute effects of the oil and oil-dispersant mixture than holoplanktonic organisms. Copepods were resistant to the effects of oil and oil-dispersant mixture. Among the herbivores, Acartia lilljeborgi had greater resistance to the acute toxic effect of oil, whereas Pseudodiaptomus acutus was more resistant to the chronic effects of both oil and the mixture. Among carnivores, Oithona hebes appeared as a resistant species to both acute and chronical effects. Mesocosms were shown to be useful for investigating the effects of oil spills on marine environments since standardized laboratory tests with algae and invertebrate test-organisms corroborated the field findings. / A avaliação dos efeitos de derrames de petróleo nas regiões costeiras decorrentes das atividades de produção, refinamento ou transporte deste produto tem sido uma das prioridades das instituições ligadas a este setor e há uma demanda muito grande de pesquisas sobre os impactos ocasionados por estes sobre o ambiente e as comunidades naturais, em particular. No presente estudo a experimentação em mesocosmos foi utilizada para avaliar os efeitos do derrame do petróleo ARLE/URAL e deste tratado com o dispersante químico Corexit® 9500, sobre uma comunidade planctônica costeira. O experimento foi realizado no Rio de Janeiro, Brasil e teve a duração de 25 dias consecutivos (19/06 a 13/07/2002). Os tratamentos foram feitos em triplicata com um volume aproximado de 1,7m3 de água do mar em cada unidade. Foram utilizadas três réplicas como controle, contendo apenas água do mar, três réplicas foram tratadas com 800 mL de petróleo e três outras réplicas foram tratadas com a mistura de 800 mL de petróleo e 80 mL de dispersante. As alterações químicas na água foram marcantes, principalmente em relação ao aumento na concentração dos compostos orgânicos. Os resultados evidenciaram uma redução severa na densidade do fitoplâncton, em decorrência da adição do óleo ou da mistura de óleo e dispersante. Houve também uma mudança na composição dos grupos, com alteração da dominância de diatomáceas para fitoflagelados. Em relação aos grupos zooplanctônicos também foi observado um efeito mais acentuado no tratamento com petróleo e dispersante. Os organismos meroplanctônicos foram mais sensíveis ao petróleo do que os holoplanctônicos. Os copépodes foram dominantes, em todos os tratamentos. A espécie herbívora Acartia lilljeborgi foi mais resistente ao efeito agudo do petróleo, enquanto Pseudodiaptomus acutus foi mais resistente ao efeito crônico Entre os Copepoda carnívoros Oithona hebes foi a espécie mais resistente, tanto ao impacto agudo quanto ao impacto crônico. Os mesocosmos são adequados para a avaliação dos efeitos do derrame de petróleo ou da mistura de petróleo e dispersante, como corroborado pelos estudos de toxicidade com algas e organismos-teste invertebrados, que corroboraram os efeitos observados em campo. A utilização de dispersante químico na etapa de remediação após os derrames necessita ser reavaliada tendo em vista os resultados deste trabalho que indicam que a mistura petróleodispersante é ainda mais tóxica do que o petróleo sozinho.

Attractive particle interactions which lead to the hetero-aggregation or 'sliming' of silicate clay gangue and valuable sulphide mineral particles are encountered in a number of hydrometallurgical and flotation processes. Sliming leads to poor recovery of the valuable minerals and high recovery of the clay gangue minerals in flotation concentrates. In the present work, the hetero-aggregation mechanism of hydrophilic mica clay mineral sericite (or muscovite) and hydrophobic chalcocite was investigated by probing the particle interactions and the prevailing interfacial chemistry under dispersion conditions where the individual chalcocite and sericite particles displayed negative zeta potentials. The mitigation/suppression of the hetero-aggregation was examined via the prudent control of dispersion conditions and pulp chemistry (i.e., pH modification and solution speciation control) and the use of two, anionic, polymeric dispersants with different molecular weight and functionality (carboxylate-substituted polyacrylamide, Cyquest 3223 and sulphonate-substituted polymaleic acid, P80 co-polymers) as dispersants. The adsorption behaviour of both polymers onto both minerals under industrially relevant suspension conditions have been quantified in terms of the polymer adsorption density and the adsorbed layer characteristics. These interfacial layer properties which impact on the mineral particles' zeta potentials and interactions, and also underpin the dispersion efficacy of polymers were characterized, using interfacial and solution analytical methods and TM-AFM imaging analysis.

The development of analytical methods for emerging contaminants creates many unique challenges for analytical chemists. By their nature, emerging contaminants have inherent data gaps related to their environmental occurrence, fate, and impact. This dissertation is a compilation of three studies related to method development for the structural identification of emerging contaminants, the detection and quantification of chemicals used in unprecedented quantities and applications, and the extraction of compounds from complex matrices where the solvent-solute-matrix interactions are not completely understood. The three studies present analytical methods developed for emerging contaminants in complex matrices, including: fluorochemical surfactants in aqueous film-forming foams, oil dispersant surfactants in seawater, and fullerene nanomaterials in carbonaceous solids. Aqueous film-forming foams, used in military and commercial firefighting, represent environmentally-relevant commercial mixtures that contain a variety of fluorochemical surfactants. Combining the surfactant-selective ionization of fast atom bombardment mass spectrometry with high resolution mass spectrometry, chemical formulas for 11 different fluorochemical classes were identified. Then AFFF-related patents were used to determine the structures. Of the eleven classes of fluorochemicals, ten have little, if any, data on their environmental occurrence, fate, and potential impacts in the peer-reviewed literature. In addition, nine of the identified classes had either cationic or zwitterionic functionalities and are likely to have different transport properties compared to the well-studied anionic fluorochemicals, such as perfluorooctanoate. After the Deepwater Horizon oil spill in the summer of 2010, one of the emergency response methods for the mitigation of the oil's environmental impact was the use of unprecedented amounts of oil dispersant to break down the oil slick and encourage biodegradation. This event illustrated the need for rapid analytical method development in order to respond to the potential environmental disaster in a timely manner. Using large volume injection liquid chromatography with tandem mass spectrometry, an analytical method was developed for the trace analysis of the multiple dispersant surfactant classes and the potential degradation products of the primary surfactant. Limits of detection ranged from 49 ��� 3,000 ng/L. The method provided excellent recovery (86 ��� 119%) and precision (10 ��� 23% RSD), while also accommodating for the high salinity of seawater samples and analyte contamination. Despite the fact that fullerene nanomaterials have been studied for almost three decades, research is still being conducted to fully understand the environmental properties of these materials. Previous studies to extract fullerenes from environmental matrices have resulted in low efficiency, high variability, or the extraction efficiencies have gone unreported. Extraction by ultrasonication with toluene and 1-methylnaphthalene increased the recovery 5-fold of a spiked, isotopically-labeled C������ surrogate from carbon lampblack as compared to that of the conventional approach of extracting with 100% toluene. The study revealed the importance of evaluating experimental variables such as extraction solvent composition and volume, and sample mass, as they have a significant impact on the quantitative extraction of fullerenes from environmental matrices. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Aug. 15, 2012 - Aug. 15, 2013