Caracterização físico-química de sistemas micelares

The process of adsorption and micellization of the surfactants sodium dodecyl sulfate, dodecylammonium chloride and hexaethylene glycol mono-n-dodecyl ether in water-air interface has been studied using measurements of surface tension in aqueous media and NaCl 0.1 mol/L in temperatures of 25, 33 and 40 °C. From these data, critical micelle concentrations and thermodynamic parameters of micellization and adsorption were determined in order to elucidate the behaviors of micellization and adsorption for these surfactants in the proposed medium. For the determination of the thermodynamic parameters of adsorption we utilized the equations of isotherms of Langmuir and Gibbs. Γmáx values determined by the different equations were correlated to the explanation of results. Temperature and salinity were analyzed in terms of their influence on the micellization and adsorption process, and the results were explained based on intermolecular interactions. The values of Gmic have confirmed that the micelle formation for the surfactants studied occurs spontaneously

Estudo do comportamento da sinterização de compactos de cavacos de um aço SAE 1050 obtidos sob alta pressão

From an economic standpoint, the powder metallurgy (P/M) is a technique widely used for the production of small parts. It is possible, through the P/M and prior comminution of solid waste such as ferrous chips, produce highly dense sintered parts and of interest to the automotive, electronics and aerospace industries. However, without prior comminution the chip, the production of bodies with a density equal to theoretical density by conventional sintering techniques require the use of additives or significantly higher temperatures than 1250ºC. An alternative route to the production of sintered bodies with high density compaction from ferrous chips (≤ 850 microns) and solid phase sintering is a compression technique under high pressure (HP). In this work, different compaction pressures to produce a sintered chip of SAE 1050 carbon steel were used. Specifically, the objective was to investigate them, the effect of high pressure compression in the behavior of densification of the sintered samples. Therefore, samples of the chips from the SAE 1050 carbon steel were uniaxially cold compacted at 500 and 2000 MPa, respectively. The green compacts obtained were sintered under carbon atmosphere at 1100 and 1200°C for 90 minutes. The heating rate used was 20°C/min. The starting materials and the sintered bodies were characterized by optical microscopy, SEM, XRD, density measurements (geometric: mass/volume, and pycnometry) and microhardness measurements Vickers and Rockwell hardness. The results showed that the compact produced under 2000 MPa presented relative density values between 93% and 100% of theoretical density and microhardness between 150 HV and 180 HV, respectively. In contrast, compressed under 500 MPa showed a very heterogeneous microstructure, density value below 80% of theoretical density and structural conditions of inadequate specimens for carrying out the hardness and microhardness measurements. The results indicate that use of the high pressure of ferrous chips compression is a promising route to improve the sinterability conditions of this type of material, because in addition to promoting greater compression of the starting material, the external tension acts together with surface tension, functioning as the motive power for sintering process. Additionally, extremely high pressures allow plastic deformation of the material, providing an intimate and extended contact of the particles and eliminating cracks and pores. This tends to reduce the time and / or temperature required for good sintering, avoiding excessive grain growth without the use of additives. Moreover, higher pressures lead to fracture the grains in fragile or ductile materials highly hardened, which provides a starting powder for sintering, thinner, without the risk of contamination present when previous methods are used comminution of the powder.

Tensoativo derivado do ácido cítrico: síntese e aplicação em fluidos de perfuração de emulsão inversa

This work describes the synthesis and study of the application of a new surfactant (Triester Lipophilic – TEL) obtained by citric acid with octanol. It is reaction was followed by thin layer chromatography (TLC) and after purification the product was characterized by proton and 13 – carbon nuclear magnetic resonance spectroscopy ( H and 13C NMR), thermogravimetric analysis (TGA) and surface tension analysis of oil-in-water emulsions. The TEL performance as surfactant in ester, n-paraffin and biodiesel based drilling fluids on the 70/30 and 60/40 water- oil rations (WOR) was evaluated by comparative tests of two commercial products used in the fields. These drilling fluids were aged in roller oven at 200 0 F during 16 h. The rheological and electric stability measurements were carried out at 135 ºF, the phase separation was evaluated after seven days at rest and the filtrate volume of drilling fluids was determined at high temperature and high pressure. The rheological behavior of the drilling fluids was evaluated by the flow curves. The results showed that the drilling fluids studied here presented Binghamian behavior as well as the used in the oil fields. The laboratory tests showed that the TEL reduced the filtrate volume and promoted the enhance of the thermal and mechanical stabilities.

Aplicação de nanoemulsão ácida em acidificação de poços de petróleo

A constante busca da indústria de petróleo pelo aumento de produção à um baixo custo operacional faz necessário o desenvolvimento de tecnologias que una as duas necessidades. A Acidificação de matriz é um método de estimulação frequentemente empregado para aumentar produção de um poço de petróleo com um custo menor se comparado a um fraturamento. O objetivo deste trabalho é estudar a obtenção de nanoemulsões ácidas para aplicação em acidificação de matriz. As nanoemulsões são capazes de retardar reações, por diminuir a difusão do ácido no meio, possibilitando a acidificação em reservatórios com baixa permeabilidade. Os reagentes utilizados para formar os sistemas nanoemulsionados foram UNT L90/OMS e RNX 110 como tensoativos, Sec-butanol como cotensoativo, Xileno e Querosene como fase óleo e Solução de HCl como fase aquosa. As nanoemulsões foram obtidas a partir da diluição de microemulsões com água ou solução de HCl. Foi realizado estudo das tensões superficiais, estudo das cinéticas de reação, avaliação da injeção em rocha carbonática e remoção de borra asfáltica. As nanoemulsões apresentaram tensão superficial menor que suas microemulsões de origem. As nanoemulsões tiveram êxito em retardar a reação entre CaCO3 e HCl, onde o sistema mais eficiente é composto por UNT L90/OMS, Secbutanol, Querosene e solução de HCl. As nanoemulsões foram eficientes em formar wormholes em plugs de carbonato calcitico com baixa permeabilidade natural. As wormholes proporcionaram incremento de permeabilidade alcançando valores de até 390 mD. O sistema ácido apresentou bom resultado de remoção de borra asfáltica, mostrando o potencial das nanoemulsões em remover esse tipo de dano. Conclui-se que os sistemas nanoemulsionados têm grande potencial de aplicação em acidificação de matriz.

Estudo da influência de sistemas microemulsionados na molhabilidade de arenitos e na recuperação avançada de petróleo

Sandstone-type reservoir rocks are commonly responsible for oil accumulation. The wettability is an important parameter for the physical properties of the container, since it interferes in characteristics such as relative permeability to the aqueous phase, residual oil distribution in the reservoir, operating characteristics with waterflood and recovery of crude oil. This study applied different types of microemulsion systems - MES - in sandstone reservoirs and evaluated their influences on wettability and residual oil recovery. For this purpose, four microemulsion were prepared by changing the nature of ionic surfactants (ionic and nonionic). Microemulsions could then be characterized by surface tension analysis, density, particle diameter and viscosity in the temperature range 30° C to 70° C. The studied oil was described as light and the sandstone rock was derived from the Botucatu formation. The study of the influence of microemulsion systems on sandstone wettability was performed by contact angle measurements using as parameters the rock treatment time with the MES and the time after the brine surface contact by checking the angle variation behavior. In the study results, the rock was initially wettable to oil and had its wettability changed to mixed wettability after treatment with MES, obtaining preference for water. Regarding rock-MES contact time, it was observed that the rock wettability changed more when the contact time between the surface and the microemulsion systems was longer. It was also noted only a significant reduction for the first 5 minutes of interaction between the treated surface and brine. The synthesized anionic surfactant, commercial cationic, commercial anionic and commercial nonionic microemulsion systems presented the best results, respectively. With regard to enhanced oil recovery performance, all systems showed a significant percentage of recovered oil, with the anionic systems presenting the best results. A percentage of 80% recovery was reached, confirming the wettability study results, which pointed the influence of this property on the interaction of fluids and reservoir rock, and the ability of microemulsion systems to perform enhanced oil recovery in sandstone reservoirs.

Estudo da influência de sistemas microemulsionados na molhabilidade de arenitos e na recuperação avançada de petróleo

Sandstone-type reservoir rocks are commonly responsible for oil accumulation. The wettability is an important parameter for the physical properties of the container, since it interferes in characteristics such as relative permeability to the aqueous phase, residual oil distribution in the reservoir, operating characteristics with waterflood and recovery of crude oil. This study applied different types of microemulsion systems - MES - in sandstone reservoirs and evaluated their influences on wettability and residual oil recovery. For this purpose, four microemulsion were prepared by changing the nature of ionic surfactants (ionic and nonionic). Microemulsions could then be characterized by surface tension analysis, density, particle diameter and viscosity in the temperature range 30° C to 70° C. The studied oil was described as light and the sandstone rock was derived from the Botucatu formation. The study of the influence of microemulsion systems on sandstone wettability was performed by contact angle measurements using as parameters the rock treatment time with the MES and the time after the brine surface contact by checking the angle variation behavior. In the study results, the rock was initially wettable to oil and had its wettability changed to mixed wettability after treatment with MES, obtaining preference for water. Regarding rock-MES contact time, it was observed that the rock wettability changed more when the contact time between the surface and the microemulsion systems was longer. It was also noted only a significant reduction for the first 5 minutes of interaction between the treated surface and brine. The synthesized anionic surfactant, commercial cationic, commercial anionic and commercial nonionic microemulsion systems presented the best results, respectively. With regard to enhanced oil recovery performance, all systems showed a significant percentage of recovered oil, with the anionic systems presenting the best results. A percentage of 80% recovery was reached, confirming the wettability study results, which pointed the influence of this property on the interaction of fluids and reservoir rock, and the ability of microemulsion systems to perform enhanced oil recovery in sandstone reservoirs.

Estudo de tensoativos na organofilização de argila bentonítica para uso em fluido de perfuração à base de óleo

Due to the great challenges encountered in drilling wells, there is a need to develop fluids with appropriated properties and able to meet all the requirements of drilling operations. The physicochemical and rheological properties must be carefully controlled so that a fluid can exercise all its functions. In perforations sensitive to contact with water and "offshore", it becomes necessary the use of oil based drilling fluids, but the bentonite clay cannot be used without a previous surface modification so that their surfaces become hydrophobic. Lately, the oil companies in Brazil use imported organoclays in the preparation of oil-based drilling fluids. The study aimed to modify a calcium clay to increase the affinity of the same organic phase of oil-based drilling fluids, applying three surfactants (OCS, CTAB and UTM 150) at different concentrations. The results indicated that the surfactants UTM 150 and CTAB showed better results compared to OCS. Considering the type of surfactant and concentration as variables used in the statistical analysis, the results indicated that only the surface tension and concentration of calcium oxide in response to organophilization process showed statistically significant effects. The organophilizated clay has potential for application in oil-based drilling fluids.

Otimização da produção biotecnológica de lipases e correlação com a produção de biossurfactantes

As lipases e os biossurfactantes são compostos produzidos por microrganismos através de fermentações em estado sólido (FES) ou sumberso (FSm), os quais são aplicáveis nas indústrias alimentícia e farmacêutica, na bioenergia e na biorremediação, entre outras. O objetivo geral deste trabalho foi otimizar a produção de lipases através de fermentação em estado sólido e fermentação submersa. Os fungos foram selecionados quanto à habilidade de produção de lipases através de FES e FSm e aqueles que apresentaram as maiores atividades lipolíticas foram utilizados na seleção de variáveis significativas e na otimização da produção de lipases nos dois modos de cultivo. Foram empregadas técnicas seqüenciais de planejamento experimental, incluindo planejamentos fracionários, completos e a metodologia de superfície de resposta para a otimização da produção de lipases. As variáveis estudadas na FES foram o pH, o tipo de farelo como fonte de carbono, a fonte de nitrogênio, o indutor, a concentração da fonte de nitrogênio, a concentração do indutor e a cepa do fungo. Na FSm, além das variáveis estudadas na FES, estudaram-se as variáveis concentração inicial de inóculo e agitação. As enzimas produzidas foram caracterizadas quanto à temperatura e pH ótimos e quanto à estabilidade a temperatura e pH. Nas condições otimizadas de produção de lipases, foi avaliada a correlação entre a produção de lipases e bioemulsificantes. Inicialmente foram isolados 28 fungos. Os fungos Aspergillus O- 4 e Aspergillus E-6 foram selecionados como bons produtores de lipases no processo de fermentação em estado sólido e os fungos Penicillium E-3, Trichoderma E-19 e Aspergillus O-8 como bons produtores de lipases através da fermentação submersa. As condições otimizadas para a produção de lipases através de fermentação em estado sólido foram obtidas utilizando-se o fungo Aspergillus O-4, farelo de soja, 2% de nitrato de sódio, 2% de azeite de oliva e pHs inferiores a 5, obtendo-se atividades lipolíticas máximas de 57 U. As condições otimizadas para a produção de lipases na fermentação submersa foram obtidas utilizando-se o fungo Aspergillus O-8, farelo de trigo, 4,5% de extrato de levedura, 2% de óleo de soja e pH 7,15. A máxima atividade obtida durante a etapa de otimização foi 6 U. As lipases obtidas por FES apresentaram atividades máximas a 35ºC e pH 6,0, enquanto que as obtidas por FSm apresentaram ótimos a 37ºC e pH 7,2. A estabilidade térmica das lipases produzidas via FSm foi superior a das lipases obtidas via FES, com atividades residuais de 72% e 26,8% após 1h de exposição a 90ºC e 60ºC, respectivamente. As lipases obtidas via FES foram mais estáveis em pH´s alcalinos, com atividades residuais superiores a 60% após 24 h de exposição, enquanto as lipases produzidas via FSm foram mais estáveis em pH´s ácidos, com 80% de atividade residual na faixa de pH entre 3,5 e 6,5. Na fermentação submersa a correlação entre a produção de lipases e a atividade emulsificante óleo em água (O/A) e água em óleo (A/O) dos extratos foi 95,4% e 86,8%, respectivamente, obtendo-se atividades emulsificantes máximas O/A e A/O de 2,95 UE e 42,7 UE. Embora a maior produção de lipases tenha sido obtida na fermentação em estado sólido, não houve produção concomitante de biossurfactantes. Os extratos da fermentação submersa apresentaram redução da tensão superficial de 50 mN m -1 para 28 mN m -1 e atividade antimicrobiana frente ao microrganismo S. aureus ATCC 25923, com potenciais antimicrobianos de 36 a 43% nos três primeiros dias de fermentação. A fermentação submersa foi a técnica que apresentou os melhores resultados de otimização da produção de lipases, bem como de produção simultânea de biossurfactantes.

Cultivo de microalgas para produção de biossurfactantes

Há uma crescente procura por alimentos mais saudáveis e seguros para atender uma população cada vez maior e mais exigente. Nos últimos anos o interesse por surfactantes de origem microbiana tem aumentado significativamente em decorrência de serem naturalmente biodegradáveis diminuindo assim o impacto ambiental. Uma grande variedade de microorganismos produz biossurfactantes, sendo que o tipo, a quantidade e a qualidade do biossurfactante são influenciados pelos constituintes do meio, tais como, fontes de carbono, nitrogênio e sais inorgânicos, além das condições de cultivo, como pH, temperatura, agitação e disponibilidade de oxigênio. Os biossurfactantes são metabólitos microbianos de superfície ativa que apresentam uma vasta aplicação no setor industrial. Os objetivos deste trabalho foram selecionar microalgas com potencial para produzir biossurfactantes e estudar a produção por microalgas em diferentes fotobiorreatores e condições nutricionais. O trabalho foi dividido em quatro etapas: 1) cultivo autotrófico e mixotrófico de microalgas para produção de biossurfactantes; 2) Seleção de microalgas para produção de biossurfactantes; 3) Produção de biossurfactantes por microalgas em diferentes fotobiorreatores e 4) Cultivo outdoor da microalga marinha Tetraselmis suecica OR para produção de biossurfactantes. Na primeira etapa Spirulina sp. LEB-18, Synechococcus nidulans LEB-25, Chlorella vulgaris LEB-106, Chlorella minutissima LEB-108 e Chlorella homosphaera foram cultivadas com glicose (cultivo mixotrófico). Spirulina sp. LEB-18 apresentou concentrações máximas de biomassa (2,55 g.L-1 ) quando foi utilizada 5 g.L-1 de glicose no meio de cultivo. A tensão superficial dos meios das microalgas foi reduzida de 70 para 43 mN.m-1 para as microalgas estudadas utilizando glicose como fonte de carbono. Resultados da segunda etapa mostraram que a microalga Scenedesmus sp. 3PAV3 apresentou valor de atividade emulsificante óleo em água (AE o/a) superior (339,8 UE.g-1 ) ao encontrado para as demais microalgas. Os menores valores de tensões superficiais variaram de 27,4 a 31,2 mN.m-1 . Na terceira etapa verificou-se que a microalga Chlorella sp. PROD1 apresentou valor de AE o/a semelhante (258,2 UE g -1 ) ao encontrado para o emulsificante comercial lecitina de soja (257,0 UE g -1 ) e ambas as microalgas estudadas alcançaram valores de tensões superficiais abaixo de 30 mN.m -1 . Na última etapa, Tetraselmis suecica OR cultivada em fotobiorreator do tipo Green Wall Panel apresentou menores valores de tensões superficiais para cultura com limitação de nitrogênio. Os resultados demonstraram a potencialidade das microalgas estudadas na produção de biossurfactantes, tanto pela redução da tensão superficial e interfacial, como pelo aumento da atividade emulsificante, confirmando uma possível aplicação como emulsificante, detergente, lubrificante, estabilizante, entre outras.

Produção de biossurfactantes e nanoemulsões a partir da microalga spirulina

As microalgas têm sido foco de muitos estudos tendo em vista sua grande aplicabilidade na indústria de alimentos e farmacêutica, como também nas áreas da biomedicina e ambiental. A Spirulina é uma microalga que possui alto valor nutricional, apresenta alto teor proteico e é rica em substâncias bioativas. Esta microalga apresenta em sua composição compostos como glicolípidios, fosfolipídios e lipídios neutros, que por sua vez possuem efeito biossurfactante. Assim, o objetivo deste estudo foi verificar a potencialidade de produção de biossurfactantes a partir de diferentes cepas de Spirulina. Para isso, foram realizados experimentos utilizando Delineamento Fatorial Completo 22 , visando avaliar a influência da concentração de fósforo e nitrogênio no cultivo das microalgas Spirulina platensis Paracas, Spirulina platensis LEB 52 e Spirulina sp. LEB 18, como também nos extratos oriundos das microalgas, através da medida da tensão superficial. Foi também avaliada a influência destes nutrientes em extratos de Spirulina platensis LEB 52 e Spirulina sp. LEB 18 a partir do índice de emulsificação e diâmetro médio das gotículas das emulsões preparadas a partir dos extratos. Para extrações de biossurfactantes foram testados os solventes metanol, etanol e hexano. Nas formulações das nanoemulsões utilizou-se homogeneizador de alta velocidade, como fase aquosa os extratos oriundos das microalgas e como fase oleosa, óleo de girassol. As formulações foram preparadas utilizando-se diferentes concentrações da fase aquosa e oleosa, bem como diferentes velocidades e tempos de agitação. De acordo com os cultivos de Spirulina platensis Paracas realizados foi verificado que o cultivo que atingiu maior valor de concentração máxima de biomassa e maior produtividade foi realizado com 114 mg.L-1 de fósforo e sem adição de nitrogênio. Porém em relação às microalgas Spirulina platensis LEB 52 e Spirulina sp. LEB 18, as variáveis fósforo e nitrogênio não apresentaram influência significativa na concentração máxima de biomassa e produtividade máxima. O extrato que apresentou a menor tensão superficial (26,75 mN.m-1 ) foi verificado quando foi utilizado etanol como solvente, sendo este obtido a partir de cultivo da microalga Spirulina sp. LEB 18 realizado sem adição de nitrogênio e de fósforo. Em relação ao índice de emulsificação foram atingidos valores superiores a 59%, porém as concentrações utilizadas de nitrogênio e fósforo não apresentaram influência significativa nesta resposta. Neste trabalho foi possível obter nanoemulsões estáveis por até 30 d e com diâmetro médio de gotículas de até 532 nm. Os resultados obtidos neste trabalho são favoráveis à pesquisa na aplicação tanto dos extratos microalgais como das nanoemulsões obtidas apresentando potencialidade de uso em diversos processos industriais, como nas áreas ambiental, farmacêutica, cosmética e alimentos.

Tratamento termoquímico do titânio auxiliado por plasma de ar - N2 - O2

Discs were grade II cp Ti oxynitride by plasma of Ar - N2 - O2 using different proportions of individual gases. These ratios were established from analysis of optical emission spectroscopy (OES) of plasma species. The proportions that resulted in species whose spectra showed an abrupt change of light intensity were chosen for this study. Nanohardness tests revealed that there was a correlation between the intensity of N2 + species with the hardness, because the treatments where they had a higher intensity, obtained a higher value nanohardness, although the crystalline phases have remained unchanged. With respect to topography, it was observed that in general, the surface roughness is related to the intensities of plasma species, because they may have different values depending on the behavior of the species. Images obtained by optical microscopy revealed a surface with grains of different colors to optical reflectance showed a peak of reflection in the red area. Measures the contact angle and surface tension showed hydrophilic properties and hydrophilic with little variation of polar and dispersive components of surface tension

Influência das espécies do plasma de N2 + O2 nas propriedades físicoquímicas das superfícies do pet

This work reports the influence of the poly (ethylene terephthalate) textile and films surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The plasma surface polymeric modification has been used for many researchs, because it does not affect the environment with toxic agents, the alterations remains only at nanometric layers and this technique shows expressive results. Then, due to its good acceptance, the treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min, using oxygen plasma alternating the treatment time 10 to 60 min with an increase of 10 min to each subsequent treatment. Also, the samples were treated with a gas mixture (nitrogen + oxygen) which was varied only the gas composition from 0 to 100% leaving the treatment time remaining constant to all treatment (10 min). The plasma treatment was characterized in-situ with Optics Emission Spectroscopy (OES), and the samples was characterized by contact angle, surface tension, Through Capillary tests, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, scanning electronic Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that oxygen treated fabrics presented high wettability, due to the hydrophilic groups incorporation onto the surface formed through spputering of carbon atoms. For the nitrogen atmosphere, there is the a film deposition of amine groups. Treatment with small oxygen concentration in the mixture with nitrogen has a higher spputered species of the samples

Utilização de matérias primas vegetais para aplicabilidade como inibidores de corrosão

In the search for products that act as corrosion inhibitors and do not cause environmental, impact the use of plant extracts as corrosion inhibitors is becoming a promising alternative. In this work the efficiency of polar extracts (ethanol extracts) obtained from the plants Anacardium occidentale Linn (AO) and Phyllantus amarus Schum. & Thonn (PA) as corrosion inhibitors were evaluated in different concentrations. For that AO and PA extracts were solubilized in the microemulsion systems (SME) containing saponified coconut oil as surfactant (SME -OCS and SME-OCS-1) in saline (NaCl 3,5 %) solution, which was also used as electrolyte. Both SME-OCS and SME-OCS-1 were characterized by surface tension and viscosity methods showing a Newtonian fluid behavior. The SME-OCS and SME-OCS-1 systems satisfactorily solubilized the polar extracts AO and PA with measurements carried out by ultraviolet spectroscopy. The measurements of corrosion inhibition efficiencies were performed by the electrochemical linear polarization resistance (LPR) technique as well as weight loss, on the surface of AISI 1020 carbon steel. The maximum corrosion inhibition efficiencies were determined by extrapolation of Tafel plots, showing the following values: 95,6 % for the system SME-OCS-AO, 98,9 % for the system SME-OCS-AO-1 and 93,4 % for the system SME-OCS-PA

Síntese enzimática de ésteres de açúcar: surfactantes e polímeros como novos materiais ambientalmente seguros

Sugar esters are substances which possess surfactant, antifungical and bactericidal actions and can be obtained through two renewable sources of raw materials: sugars and vegetable oils. Their excellent biodegradability, allied to lhe fact that they are non toxic, insipid, inodorous, biocompatible, no-ionic, digestible and because they can resist to adverse conditions of temperature, pH and salinity, explain lhe crescent use of these substances in several sections of lhe industry. The objective of this thesis was to synthesize and characterize surfactants and polymers containing sugar branched in their structures, through enzymatic transesterification of vinyl esters and sugars, using alkaline protease from Bacillus subtilis as catalyst, in organic medium (DMF).Three types of sugars were used: L-arabinose, D-glucose and sucrose and two types of vinyl esters: vinyl laurate and vinyl adipate. Aiming to reach high conversions from substrates to products for a possible future large scale industrial production, a serie of variables was optimized, through Design of Experiments (DOE), using Response Surface Methodology (RSM).The investigated variables were: (1) enzyme concentration; (2) molar reason of substrates; (3) water/solvent rale; (4) temperature and (5) time. We obtained six distinct sugar esters: 5-0-lauroyl L-arabinose, 6-0-lauroyl D-glucose, 1'-O-lauroyl sucrose, 5-0-vinyladipoyl L-arabinose, 6-0-vinyladipoyl D-glucose and 1 '-O-vinyladipoyl sucrose, being lhe last three polymerizable. The progress of lhe reaction was monitored by HPLC analysis, through lhe decrease of sugar concentration in comparison to lhe blank. Qualitative analysis by TLC confirmed lhe formation of lhe products. In lhe purification step, two methodologies were adopted: (1) chromatographic column and (2) extraction with hot acetone. The acylation position and lhe chemical structure were determined by 13C-RMN. The polymerization of lhe three vinyl sugar esters was possible, through chemical catalysis, using H2O2 and K2S2O8 as initiators, at 60°C, for 24 hours. IR spectra of lhe monomers and respective polymers were compared revealing lhe disappearance of lhe vinyl group in lhe polymer spectra. The molar weights of lhe polymers were determined by GPC and presented lhe following results: poly (5-0-vinyladipoyl L-arabinose): Mw = 7.2 X 104; PD = 2.48; poly (6-0-vinyladipoyl D-glucose): Mw = 2.7 X 103; PD = 1.75 and poly (1'-O-vinyladipoyl sucrose): Mw = 4.2 X 104; PD = 6.57. The six sugar esters were submitted to superficial tension tests for determination of the critical micelle concentrations (CMC), which varied from 122 to 167 ppm. Finally, a study of applicability of these sugar esters, as lubricants for completion fluids of petroleum wells was' accomplished through comparative analysis of lhe efficiency of these sugar esters, in relation to three commercial lubricants. The products synthesized in this thesis presented equivalent or superior action to lhe tested commercial products

Avaliação da biodegradabilidade de petróleo utilizando microrganismos isolados do estuário do Rio Potengi (RN)

The oil activity in the Rio Grande do Norte State (RN) is a permanent threat to coastal ecosystems, particularly mangroves, with the possibility of oil spills. In this context, the objective of this study was to evaluate the potential resistance of the mangrove environment of a possible spill. Were selected and isolated microorganisms degrading oil by the technique of enrichment cultures and formation of a bacterial consortium. The kinetic study of the consortium was held in rotary incubator shaken at 150 rpm and 30° C. Samples were taken at intervals of 4 hours for analysis of cell concentration and surface tension. The biodegradation was monitored using two methods of respirometry: manometric (OxiTop-C ®) and conductivimetry, where the biodegradation of oil was estimated indirectly by oxygen consumption and CO2 production, respectively. Furthermore, it was used a full 2² factorial design with triplicate at central point to the runs that used the conductivimetric methodology.. The technique of enrichment cultures allowed to obtain thirteen bacterial strains. Kinetic study of the consortium, we can showed the absence of the lag phase, reaching a maximum cell concentration of 2.55 g / L at 16 h of cultivation and a reduction on surface tension. When we adopted the methodology of OxiTop-C was detected a band indicating biodegradability (1% oil v/v), however when we used the conductivimetry methodology did not observe any band that would indicate effective biodegradation. By monitoring a process of biodegradation is necessary to observe the methodology will be adopted to evaluate the biodegradation process, since for the same conditions adopted different methodologies can produce different results. The oil-degrading isolates from soils of the mangrove estuary Potengi / RN are largely to be used in bioremediation strategies of these places, in the case of a possible oil spill, or it can be used in the treatment of waste oil generated in saline environments, since they are optimized the conditions of the tests so that the efficiency of biodegradation reach the minimum level suggested by the standarts