Dissertations / Theses on the topic 'Co-surfactant'

Supercritical C02 (SCC02) has attracted increasing attention as a promising alternative for volatile organic solvent s, due to its abundance, non-toxic, non-flammable, and non-hazardous properties which make C02 a strong candidate for use as a green solvent. However, SCC02 is generally a very poor solvent, especially for polar and high molecular weight solutes, which has largely limited the applications of this supercritical liquid as a processing medium. On the other hand, emulsions and microemulsions have been widely accepted as effective media to stabilize immiscible components, such as water and oil. Studies have been carried out extensively for water-in-scC02 (w/c) microemulsions over the last two decades, in particular, Small-Angle Neutron Scattering (SANS) has been recognised as a powerful technique characterise the self-assembly structures, and frequently applied to investigate such systems. In this thesis, the validity of contrast variation SANS (CV-SANS) has been examined in w/c microemulsions by employing mixtures of D20 and H20 as contrast agents. With this method, the core-shell structure of w/c microemulsions has been highlighted, which allows behaviour of the microemulsions and in particular, the properties of surfactant films to be studied in detail. In addition, a systematic study has also been conducted on the effects of amphiphilic additives known as 'hydrotropes' on surfactant films in both water-in-oil and water-in -C02 microemulsions. Based on these observations, a novel surfactant has been synthesised and applied to w/c microemulsions as an additive, which effectively triggers elongation of microemulsion droplets. This work takes significant step in both exploring the fundamental aspect of the self-assembly structures in C02, and also for the optimization of the physicochemical properties of such systems for potential applications.

Orientador: Watson Loh
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica
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Resumo: Polieletrólitos associam-se fortemente com surfatantes de carga oposta em meio aquoso, levando a uma separação de fases que resulta em uma fase concentrada, rica em polieletrólito e surfatante, em equilíbrio com uma fase diluída constituída pelos contra-íons. A fase concentrada pode ser constituída de interessantes estruturas supramoleculares advindas das propriedades de auto-organização destes sistemas, que aliadas à possibilidade de modificaremse a geometria da mesofase e as distâncias entre os agregados, tornam estes sistemas ferramentas importantes em processos de fabricação de estruturas micro e mesoporosas e em sistemas de liberação controlada de drogas. O estudo do equilíbrio de fases de sistemas constituídos por polieletrólitos e surfatantes de cargas opostas em água não é tão simples devido ao grande número de componentes presentes no sistema, porém é possível reduzir a quantidade de componentes através da síntese do sal complexo ¿puro¿ (polieletrólito-surfatante), facilitando dessa forma a análise dos diagramas de fases gerados. Neste trabalho o comportamento de fases de sais complexos formados pelo íon surfatante hexadeciltrimetilaônio (CTA) e pelo polieletrólito (PA) em água e na presença de diferentes solventes orgânicos foi investigado. Três efeitos principais foram analisados: efeito da natureza do solvente orgânico; efeito da adição de uma série homóloga de álcoois e efeito da hidrofobicidade do contra-íon polimérico. Os resultados obtidos indicam que a polaridade do solvente orgânico utilizado influencia intensamente nas estruturas formadas pelo sal complexo. Em geral, observou-se a predominância de estruturas lamelares em sistemas contendo co-surfatantes (n-álcoois) e a predominância de estruturas hexagonais em sistemas contendo p-xileno e ciclohexano. A hidrofobicidade do contra-íon polimérico não gerou mudanças significativas nos diagramas de fases obtidos.
Abstrat: Association between charged polymers and oppositely charged surfactants in aqueous solutions may lead to phase separation forming a concentrated phase rich in polyions and surfactant ions, and a more dilute phase, which mostly contains simple ions. The concentrated phases may display a variety of supramolecular structures with diverse and interesting features due to self-assembling properties of these systems, which have found applications in the field of controlled drug delivery and in templating the synthesis of materials with tailored geometries. A complete description of the phase equilibrium in these systems is quite demanding, because addition of polyelectrolyte and oppositely charged surfactant to water leads to the formation of several components, however it is possible to reduce the number of the components by the preparation of the pure complex-salt, which allows to analyze the phase equilibrium in a controlled manner. In this work the phase behavior of complex salts formed by the surfactant ion hexadecyltrimethylammonium (CTA) and the polyacrylate (PA) in water and with different organic solvents were investigated. Three principal effects were analyzed: the effect of the organic solvent nature; the effect of n-alcohol carbon chain length and the effect of the polyelectrolyte hidrophibicity. The obtained results revealed that the organic solvent nature has a strong influence in the structure assumed by the complex salt. From the general analysis, systems containing co-surfactants (n-alcohols) a predominance of lamellar structures was observed, and in systems containing p-xylene and ciclohexane a predominance of hexagonal structures was detected. The polyelectrolyte hidrophobicity did not display significant changes in the obtained phase diagrams.
Doutorado
Físico-Química
Doutor em Ciências

Thesis (Ph. D.)--Ohio State University, 2005.
Title from first page of PDF file. Document formatted into pages; contains xxxiv, 429 p.; also includes graphics (some col.). Includes bibliographical references (p. 402-429). Available online via OhioLINK's ETD Center

Polymeric microspheres have been used in a broad range of applications from chromatographic separation techniques to analysis of air flow over aerodynamic surfaces. The preparation of microspheres from many polymer families has consequently been extensively studied using a variety of synthetic approaches. Although there are a myriad of polymeric microsphere synthesis methods, free-radical initiated emulsion polymerization is one of the most common techniques. In this work, poly(styrene-co-methyl methacrylate) microspheres were synthesized via surfactant-free emulsion polymerization. The effects of the co-monomer composition and addition time on particle size distribution, particle formation, and particle morphology were investigated. Particles were characterized using dynamic light scattering and scanning electron microscopy to gain further insight into particle size and size distributions. Reaction kinetics were analyzed through consideration of characterization results. A particle formation mechanism for poly(styrene-co-methyl methacrylate) microspheres was proposed based on characterization results and known reaction kinetics.

Cette thèse vise à concevoir, synthétiser et étudier des systèmes photo-stimulables modèles en solution aqueuse formés à partir de polyélectrolytes (PEs) et de tensioactifs. La photosensibilité est liée à la présence de chromophores azobenzène (Azo) qui subissent une isomérisation trans → cis sous irradiation UV. Nous avons considéré dans un premier temps un PE hydrophile sur lequel nous avons greffé des groupements Azo. Ce système forme de agrégats globulaires en solution en raison du collapse des chaînes et des associations intermoléculaires. La taille des agrégats varie sous irradiation UV. Elle dépend également de la masse molaire des PEs et du taux de greffage des groupements Azo. Nous avons considéré dans un second temps des tensioactifs dans lesquels des groupements Azo ont été introduits (Azo-tensioactifs). Nous avons étudié leur complexation avec des PEs de charge opposée. Ces systèmes s’organisent en colliers de perles. Les polyions décorent les micelles et pénètrent à l’intérieur de celles-ci (co-micellisation). Sous irradiation UV, la taille des perles diminue sans vraiment modifier l’organisation des complexes. Nous nous sommes enfin intéressés à l’auto-assemblage d’Azo-tensioactifs et de co-tensioactifs. Ce mélange conduit à la formation des micelles allongées et à la création d’un gel. Sous irradiation UV, on observe une transition gel - fluide. L’origine ce phénomène est lié à un changement morphologique des agrégats micellaires (micelles allongées - micelles globulaires)
This thesis aims at designing, synthesizing and characterizing model photo-responsive systems in aqueous solution. These systems are based on polyelectrolytes (PEs) and surfactants. The photo-sensitivity arises from the presence of azobenzene (Azo) groups that undergo a transition from a trans to a cis isomer. We first considered a hydrophilic PE on which we grafted Azo groups. This system forms globular aggregates in solution due to chains collapse and intermolecular associations. The size of the aggregates varies under UV irradiation. It also depends on the molar mass of the PEs and the Azo content. We then considered surfactants in which Azo groups have been introduced (Azo-surfactants). We studied their complexation with oppositely charged PEs. These systems show a pearl necklace organization. The PEs decorate the micelles and penetrate inside (co-micellisation). Under UV irradiation, the size of the pearls decreases without really modifying the general organization of the complexes. Finally, we were interested in the self-assembly of Azo-surfactants and co-surfactants. This mixture leads to the formation of wormlike micelles and the creation of a gel. Under UV irradiation, a gel - fluid transition is observed. The origin of this phenomenon is linked to a morphological transition of the micellar aggregates (wormlike micelles - globular micelles)

Esse trabalho teve como objetivo verificar o efeito da adição do ácido oléico na moagem de alta velocidade/energia na obtenção de pós magnéticos em escala nanométricas da liga Pr12Fe65,9Co16B6Nb0,1. A primeira etapa deste trabalho, envolveu a obtenção de pós magnéticos por meio do processo de hidrogenação, desproporção, dessorção e recombinação (HDDR), utilizando a pressão de H2 de 930 mbar (hidrogenação e desproporção) e temperatura de dessorção e recombinação de 840 ºC. Inicialmente, os pós HDDR foram submetidos à moagem de alta velocidade/energia a 900 rpm, com variação do volume do meio de moagem (ciclohexano) sem adição de ácido oleico. Em seguida, os pós HDDR foram submetidos à moagem com adição de ácido oleico, variando o tempo de moagem. Após a moagem, foi realizado tratamento térmico dos pós a 700 ºC ou 800 ºC durante 30 min., com a finalidade de cristalização do pó. Foi verificado que, a utilização de 6,6 ml de ciclohexano como meio de moagem e com adição de ácido oleico há uma melhora na eficiência da moagem dos pós. Para adições de surfactante, de 0,02 a 0,05 ml e tempos de moagem até 360 minutos, não ocorre a aglomeração dos pós magnéticos no pote de moagem, obtendo acima de 90% de eficiência na moagem. A segunda etapa deste trabalho envolveu a caracterização dos pós magnéticos: utilizando magnetômetro de amostra vibrante, microscopia eletrônica de Varredura, microscopia eletrônica de transmissão e difração de raios-X. Os resultados obtidos mostraram que a adição de ácido oléico na moagem de alta velocidade/energia proporciona uma melhora nas propriedades magnéticas. Com a variação do tempo de moagem a fase Fe-α presente no pó HDDR apresenta diminuição no tamanho do cristalito (de 35 para ~ 10 nm) enquanto que, na fase Pr2Fe14B verifica-se menor grau de cristalinidade.
This work verified the effect caused by adding the surfactant in the high speed/energy milling in order to obtain Pr12Fe65.9Co16B6Nb0.1 magnetic nanopowders. The first part of this work involved the magnetic powder obtainment through the process of hydrogenation, disproportionation, desorption and recombination (HDDR). The pressure of H2 during the hydrogenation and disproportion steps was 930 mbar and the temperature of desorption and recombination was 840 ºC. Initially, the HDDR powders were subjected a highspeed milling process at 900 rpm, with quantity variations of the milling medium (cyclohexane) and without the addition of oleic acid. Then, the HDDR powders were subjected to the milling process with the addition of oleic acid and with milling time variations. After the milling process, heat treatments of the powder were carried out at 700 °C or 800 °C for 30 minutes in order to obtain the crystallization of the powder. By performing the procedures, it was verified that the milling efficiency improved with the addition of 6.6 ml of cyclohexane as the milling medium and with the addition of oleic acid. It was determined that for the surfactant additions of 0.02 ml to 0.05 ml, with a milling time of up to 360 minutes, powder agglomeration does not occur in the milling pot and the milling efficiency is higher than 90%. The second stage of this work involved the magnetic powders characterization obtained by using vibrating sample magnetometer, scanning electron microscopy, transmission electron microscopy and X-ray diffraction. Through the characterizations it was found that the powders magnetic properties improved when the addition of oleic acid in a high-speed /energy milling occurred. It was also verified that the α-Fe phase, present in the powder, shows a crystallite size decrease (from 35 nm to ~ 10 nm) when the time milling variation occurred; meanwhile, the crystallinity degree was lower in the Pr2Fe14B phase when the time milling variations was carried out.

This research aimed to develop technology and processes to further beneficiate two southern African bentonites for applications in polymer/clay nanotechnology. The bentonites were from the Koppies mine in South Africa, and the Boane mine in Mozambique. The work was divided into two parts: (i) preparation of organomodified nanoparticulate smectite clays, and (ii) preparation of their poly(ethylene-co-vinylacetate) nanocomposites. Nanoparticulate organobentonites were prepared using purified bentonites. The conventional organomodification process uses a very low concentration of bentonites at 80 oC. In this study, a novel method was developed: concentrated slurries of naturally occurring Ca-bentonite partially activated with soda ash in the presence of a proprietary dispersant were contacted at ambient temperature with quaternary ammonium surfactants. A known amount of bentonite dispersion was placed in a planetary mixer before the mixture. Likewise, a known amount of surfactant, up to 50% excess, based on the estimated cation exchange capacity (CEC) of the bentonites, was added while mixing the dispersion. The surfactants added were either in solution or in powdered form. The intercalated bentonite was recovered by centrifugation and washed repeatedly with water until halide ions could not be detected using a 1M silver nitrate solution. The solids were dried at ambient temperature and humidity, and then crushed and milled into a fine powder using a mortar and pestle. Several instrumental techniques were used to characterise and examine the properties of the bentonite samples before and after organic treatment.The X-ray diffraction (XRD) results were consistent with: (i) paraffin-type extended chain intercalation; and (ii) interdigitated monolayer intercalation of the C12 and C14 single-chain alkyl surfactants and bilayer intercalation of the single-chain C16 surfactant and the surfactants with double alkyl chains. Fourier transform infrared (FTIR) spectroscopy analysis of the organobentonite powders confirmed disordered chain conformations. XRD also detected significant amounts of cristobalite in the samples of Boane bentonite (from Mozambique). This impurity could not be removed cost-effectively. The onset decomposition temperature ofthe present organobentonites was around 200 ºC, which is within the typical range of polymer/organoclay processing temperatures. The thermal stability of the organobentonites was independent of both the number of alkyl chain substituents and their length, and also independent of the degree of clay intercalation. SURFACTANT INTERCALATED KOPPIES AND BOANE BENTONITES FOR POLYMER NANOTECHNOLOGY ii Poly(ethylene-co-vinylacetate) nanocomposites were prepared with South African Koppies bentonite, organomodified with single-chain C12 (and polar 2-hydroxyethyl side chain) and double-chains C18 alkyl ammonium cationic surfactants. The later surfactant was intercalated both below and above the clay CEC. Nanocomposites were prepared by twin-screw melt compounding. Transmission electron microscopy (TEM) indicated the presence of mixed nanoand micron-sized clay morphologies. XRD studies revealed that the crystallinity of the particles improved and that the d-spacing values increased on incorporation of the modified bentonites in the polymer matrix. It is postulated that, rather than indicating polymer co-intercalation, this was caused by further intercalation of either excess surfactants or surfactant residues that were released by shear delamination of the clays during compounding. Improved mechanical properties were realised, especially when using the bentonite containing the longer double-chains surfactant intercalated at levels in excess of the CEC of the clay. The nanocomposites showed improved tensile modulus and elongation at break values at the expense of a reduction in impact strength, while tensile strength was about the same as for the neat polymer.
Thesis (PhD)--University of Pretoria, 2013.
gm2014
Chemistry
unrestricted

The nasal mucosa provides a rapid, noninvasive route for drug administration to the systemic circulation and even potentially to the CNS. Nanoparticles made from the biodegradable polymer, PLGA, are of great interest for use in drug delivery systems due to PLGA’s relative safety and ease of surface modification. Nanoparticles may provide improved targeting and transport through the nasal mucosa. However, the optimal nanoparticle sizes and surface properties for intranasal delivery are unknown. In this study, we prepared PLGA nanoparticles within a size range of 50-70 nm containing the lipophilic fluorescent dye, Nile Red, using a surfactant-free nanoprecipitation method. The resulting nanoparticles were evaluated using dynamic light scattering and scanning electron microscopy. Nanoparticle uptake into the nasal mucosa was determined by exposing the tissues to nanoparticle dispersions for 30 or 60 minutes. The in vitro uptake of the nanoparticles by the nasal mucosal tissues revealed that the Nile Red-loaded PLGA nanoparticles were transported across the epithelial layer and accumulated in the sub-mucosal connective tissues. Nanoparticle uptake in the full thickness tissues was time dependent where 2% of the total loads of nanoparticles exposed to the tissues were measured in the mucosal tissue after 30 minutes and 4% were present in the tissues after 60 minutes. The rapid and measurable transfer of PLGA nanoparticles into the nasal mucosal tissues indicate that they may be an efficient delivery vehicle for drugs with either local or systemic activities.

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Universidade Federal de Sao Carlos
Biosurfactants are a surface-active chemical compounds synthesized by microorganisms. These compounds have many advantages when compared to their chemically synthesized counterparts as specific action, low toxicity, higher biodegradability, effectiveness at extreme temperatures, pH and strength ionic. They appear as promising candidates to replace chemical surfactants produced from petrochemicals. The use of renewable and low cost substrates such as agro based industrial wastes is one of the attractive strategies for economical large scale biosurfactants production. In this work, it was evaluated glycerol, a co-product of biodiesel production, as carbon source for biosurfactant production. Two microorganisms, Pseudomonas aeruginosa MSCIC02 and Bacillus subtilis LAMI009, both isolated from environmental sources, were used thorough this work. In the first part of the work experiments were carried out in shake flasks using P. aeruginosa. The results showed that the increase in nitrogen source (sodium nitrate) and the decrease in the carbon source (glycerin) favored rhamnolipids production. In the range studied, the maximum biosurfactant concentration obtained was 2.3 g⋅L-1 (C/N ratio 12). The effect of nitrogen concentration on the biosynthesis of rhamnolipids and pH behavior as a function of the nitrate concentration in the cultures indicated that this strain probably carried a denitrification route favoring the production of rhamnolipids. Experimental runs carried out in bioreactor indicated that the integrated process of production and separation/concentration by fractionation in bubble column equipment caused many operation problems, such as the drag cell, and reducing the concentration of rhamnolipids to 0.4 g⋅L-1in the reaction medium. The kinetics of product formation was evaluated by two models. The Luedeking-Piret model was not able to represent the process. The model proposed by MERCIER et. al. (1992) could adequately describe the rhamnolipids production from P. aeruginosa strain. Emulsifying capacity of the cell-free culture medium was assessed by the emulsification index (EI24). The biosurfactant produced was able to emulsify vegetable oils as well as mineral oils. EI24 greater than 55% was reached. In the second part of the work experimental data from Bacillus subtilis LAMI009 cultivated in shake flasks showed that the growth of this strain was dependent on iv the medium supplementation with yeast extract. A change in culture medium was implemented in order to reduce the length of the lag phase. The use of inorganic nitrogen sources showed that both ammonium nitrate and ammonium sulphate reached similar values of surfactin concentration and volumetric productivity. It was obtained 35 mg⋅L-1 and 6.1 mg⋅L-1⋅h-1, respectively. Surface tension of the cell-free culture medium was similar for both nitrogen sources. The minimal value obtained was 29.7 mN⋅m-1. Sodium nitrate was found to be an adequate nitrogen source for cell growth. However, in these assays low productivity and low surface tension reduction were obtained when compared to the other nitrogen sources evaluated. The supplementation of the culture medium with yeast extract improves the surfactin concentration (60.0 mg⋅L-1) and volumetric productivity (5.2 mg⋅L-1⋅h-1). In this assay the surface tension reached 28.1 mN⋅m-1. The inoculum size had a great influence on cell growth and production of surfactin. When 2% (v/v) of inoculum was used the surfactin concentration and volumetric productivity obtained were 148.2 mg⋅L-1 e 14.22 mg⋅L-1⋅h-1, respectively. The search for genes responsible for production of lipopeptides surfactin and iturine indicated the presence of the genes lpa14 and ituD in B. subtilis LAMI009 genome. Analysis of the chromatography profile of methanol extracts of the lipopeptides from culture medium with ammonium nitrate and sodium nitrate as nitrogen source showed characteristic peaks of the surfactin and iturine. Thereby, it is believed that this strain is a co-producer of both surfactin and iturine. Emulsifying capacity of the cell-free culture medium showed higher stability with the media that employed ammonium nitrate and sodium nitrate as nitrogen source. It was obtained EI24 of 65% with n-hexadecane and 45% with kerosene. The acid precipitation of biosurfactant from the cell-free culture medium showed that this prepurification step promoted an increase in the emulsifying capacity of the mixture of lipopeptides synthesized by B. subtilis LAMI009. The aqueous solution of crude biosurfactant was able to emulsify naphthenic oils, vegetable oils, and an aromatic hydrocarbon. Values of EI24 greater than 65% were obtained. Emulsions formed with naphthenic oils were more stable according to droplet-size distribution. The smaller the size of droplets, the more stable was the emulsion.
Biossurfactantes são compostos químicos tensoativos sintetizados por microrganismos. Estes compostos possuem muitas vantagens quando comparados com seus equivalentes sintetizados quimicamente como ação específica, baixa toxicidade, alta biodegradabilidade, efetividade em condições extremas de temperatura, pH e força iônica. Apresentam-se como substitutos promissores aos surfactantes químicos derivados da indústria do petróleo. A utilização de substratos renováveis e de baixo custo, como os resíduos agroindustriais, consiste em um dos fatores mais importantes para a viabilização econômica da produção destes compostos em escala industrial. Neste trabalho avaliou-se o uso da glicerina, um coproduto da produção de biodiesel, como fonte de carbono para produção de biossurfactante. Dois microrganismos, Pseudomonas aeruginosa MSIC02 e Bacillus subtilis LAMI009, ambos isolados a partir de amostras ambientais, foram empregados neste trabalho. Na primeira parte do trabalho experimentos realizados em frascos agitados com a P. aeruginosa mostraram que o aumento da produtividade de ramnolipídeos foi favorecido pelo aumento da concentração da fonte de nitrogênio (nitrato de sódio) e pela redução da concentração da fonte de carbono (glicerina). Na faixa estudada a concentração máxima de biossurfactante obtida foi de 2,3 g⋅L-1 (razão C/N de 12). O efeito da concentração de nitrogênio sobre a biossíntese de ramnolipídeos e o comportamento do pH em função da concentração de nitrato durante os cultivos indicou que esta cepa possivelmente realizou uma rota denitrificante favorecendo a produção de ramnolipídeos. Os cultivos realizados em biorreator indicaram que o processo de produção integrado a extração/concentração por fracionamento em coluna de bolhas acarretou diversos problemas operacionais, como o arraste de células, e a redução da concentração de ramnolipídeos no meio reacional para 0,4 g⋅L-1. Foram avaliados dois modelos cinéticos de formação de produto para os ensaios realizados. O modelo de Luedeking-Piret não apresentou boa representatividade do processo. O modelo proposto por MERCIER et al. (1992) mostrou-se mais adequado para representar a produção de ramnolipídeos pela cepa estudada. A avaliação da capacidade emulsificante do meio de cultivo livre de células mostrou que o biossurfactante produzido pela P. aeruginosa teve um desempenho eficiente, sendo capaz de emulsificar óleos de origem vegetal e mineral e atingir índice de emulsificação (IE24) maior que 55 %. Na segunda parte do trabalho, cultivos realizados em frascos agitados para avaliação da produção de biossurfactantes lipopeptídeos por B. subtilis LAMI009 indicaram que o crescimento desta cepa foi dependente da suplementação do meio com extrato de levedura. Uma adaptação ao meio de fermentação foi necessária para eliminar a extensa fase lag durante o processo fermentativo. A utilização de fontes de nitrogênio inorgânicas mostrou que tanto o nitrato de amônio quanto o sulfato de amônio apresentaram valores de concentração de surfactina e produtividade volumétrica da ordem de 35 mg⋅L-1 e 6,1 mg⋅L-1⋅h-1, respectivamente. A tensão superficial do meio de cultivo livre de células também foi semelhante para ambas fontes de nitrogênio, cujo valor mínimo foi 29,7 mN⋅m-1. O nitrato de sódio foi fonte de nitrogênio adequada para o crescimento celular, entretanto apresentou baixa produtividade quando comparado com as demais fontes de nitrogênio avaliadas. Com a suplementação do meio de cultivo com extrato de levedura ii obteve-se maior concentração de surfactina (60,0 mg⋅L-1) e produtividade volumétrica (5,2 mg⋅L-1⋅h-1) e menor tensão superficial (28,1 mN⋅m-1) relativamente ao meio de cultivo contendo fonte de nitrogênio inorgânica. O tamanho do inóculo exerceu grande influência sobre a concentração de surfactina e a produtividade volumétrica. Quando se utilizou 2% (v/v) de inóculo a concentração de surfactina e a produtividade volumétrica alcançaram valores de 148,2 mg⋅L-1 e 14,22 mg⋅L-1⋅h-1, respectivamente. A pesquisa de genes responsáveis pela produção dos lipopeptídeos surfactina e iturina indicou a presença dos genes lpa14 e ituD no genoma da linhagem B. subtilis LAMI009. A avaliação do perfil cromatográfico dos extratos metanólicos de lipopeptídeos obtidos a partir dos cultivos com as fontes de nitrogênio nitrato de amônio e nitrato de sódio apresentou picos característicos de outro lipopeptídeo além da surfactina, a iturina,. Portanto, acredita-se que esta linhagem é uma co-produtora de surfactina e iturina. A capacidade emulsificante do meio de cultivo livre de células apresentou maior estabilidade com os cultivos com nitrato de amônio e nitrato de sódio, obtendo-se IE24 de 65 % com n-hexadecano e 45 % com querosene. A separação do biossurfactante por precipitação ácida a partir do meio de cultivo livre de células mostrou que esta etapa de pré-purificação promoveu um aumento da capacidade emulsificante da mistura de lipopeptídeos sintetizada por B. subtilis LAMI009. A solução aquosa do biossurfactante bruto foi capaz de emulsificar óleos naftênicos, óleos vegetais e um hidrocarboneto aromático, apresentando IE24 maiores que 65 % com os óleos avaliados. As emulsões formadas com óleos naftênicos, utilizados como base para lubrificantes, foram mais estáveis. Quanto menor o tamanho das gotas mais estável foi a emulsão formada.

Détermination des diagrammes de phase de systèmes à base de poly(oxyethylène) ether dodécyle et de faibre quantité de décane, à l'aide de la méthode isotherme et par balayage automatique en température. Étude structurale des zones cristallines par diffraction des rayons X

The interfacial properties of a surfactant in a CO₂-aqueous system at a temperature above 100 °C, and how they influence foams are essentially unknown. A cationic surfactant, C₁₂₋₁₄N(EO)₂ in the protonated state below pH 5.5, was demonstrated to be soluble in an aqueous phase with up to 22% total dissolved salt (TDS) at 120 °C. Moreover, the strong solvation in brine (high cloud point) and simultaneous affinity for CO₂ led to significant adsorption of the surfactant at the CO₂-water interface. Given that the surfactant favored the brine phase over the CO₂ phase, the preferred curvature was a CO₂-in-water (C/W) macroemulsion (foam). The surfactant stabilized foam in the presence of crushed calcium carbonate at ~ pH 4 upon suppressing the dissolution of calcium carbonate upon addition of Ca²⁺ and Mg²⁺ according to the common ion effect. Cationic alkyltrimethylammonium surfactants with an alkyl tail of average carbon number less than 15 were soluble in 22% TDS brine up to 120 oC. The head group was properly balanced with a C₁₂₋₁₄ hydrocarbon tail for a sufficiently dense surfactant layer at the CO₂-water interface to reduce the interfacial tension. For C₁₂₋₁₄N(CH₃)₃Cl the solubility in brine and the surfactant adsorption were sufficient to stabilize C/W foam at 120 °C in both a crushed calcium carbonate packed bed (76 Darcy) and a capillary tube at the downstream of the bed. The stability of the foam at high temperature may be attributed to the high surfactant adsorption at the interface. The use of nonionic surfactants as a foam stabilizer is usually limited by their poor aqueous solubility at elevated temperatures, particularly at high salinity. A nonionic surfactant C₁₂₋₁₄(EO)₂₂ with high degree of ethoxylation gave higher salt tolerance at elevated temperature. The surfactant stabilize C/W foam at 80 °C in the presence of 90 g/L NaCl brine in a 30 Darcy sand pack, which has not yet been reported by a nonionic surfactant. Both the formation of strong foam in the porous media and the low of oil-brine partition coefficient suggest C₁₂₋₁₄(EO)₂₂ is a potential candidate for a CO₂ EOR field trial.
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This work investigates the performance of CO₂ soluble surfactants used for CO₂ foam flooding in fractured carbonate reservoirs. Oil recovery associated with the reduction of CO₂ mobility in fractures is assessed by monitoring oil saturation and pressure drops during injection of CO₂ with aqueous surfactant solution in artificially fractured carbonate cores. Distinct novel CO₂ soluble surfactants are evaluated as well as a conventional surfactant. Water flooding and pure CO₂ injection are conducted as baseline. Characterization of fluids and rock are also reported which include Amott test, oil phase behavior and slim tube test. Transport and thermodynamic properties of surfactant and supercritical CO₂ are used to evaluate the process on a core scale using a commercial reservoir simulator.
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For the first time the interfacial properties of nonionic hydrocarbon surfactants at both the air-water and CO₂-water interfaces are investigated in terms of surfactant structure to determine the changes in surfactant efficiency (negative of the logarithm of the surfactant concentration to create a surface pressure of 20 mN/m). At the air-water interface, linear surfactant tails are more efficient due to the higher packing ability of the straight chains in the dense surfactant monolayer. However, at the CO₂-water interface, surfactant adsorption is small and tails can be solvated. Thus, branching which increases both tail solvation and tail hydrophobicity also enlarges the hard disk area of the surfactant to ultimately increase the efficiency of the surfactant at the CO₂-water interface. CO₂-in-water concentrated emulsions (foams) are studied over short and long times to evaluate the foam stability as a function of both surfactant structure and foam conditions using in-situ optical microscopy. The surface pressure measured at the CO₂- water interface is correlated with the short time stability of coalescing foams with very small cell sizes (under 0.4 [mu]m in diameter). Long time stability of bubbles to coalescence is shown under a variety of conditions. The rheology of these bulk CO₂-in-water foams under high-pressure conditions are also evaluated through measurements of the pressure drop over a capillary tube. Viscosities in excess of 200 cP are measured, an increase of over 1000 time that of pure CO₂ (0.09 cP at 24 °C and 2000 psia). The viscosity of the C/W foams are found to correlate with bubble size, continuous phase viscosity, shear rate, and interfacial tension. Hydrophobic silica particles adsorbed at the interface are also used to stabilize water-in-CO₂ emulsions as an alternative to surfactant stabilizers. The difficulties of tail solvation associated with many hydrocarbon surfactants in CO₂ can be removed by using particles instead of surfactant. A porous cross-linked shell is formed about the hydrophilic (colloidal and fumed) silica to render the particles CO₂-philic and the crosslinking removes ligand tails from the particle surface.
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Organochlorine pesticides (OCPs) were used in agriculture throughout the world for a long time because they are very effective for pest control, but OCPs such as DDT and its metabolites can threaten human health and ecological systems. Although DDT has been banned for use in Canada since 1972, it still persists in Canadian farmland at detectable levels due to its chemical stability. The soils contaminated with DDT require economical remediation strategies because of the low land value and rural location. Although soil washing has been proposed as a possible economical technique to remove DDT, it has very low water solubility and so it is necessary to consider using surfactants to improve the soil-washing process. Building on previous research, we hypothesize that combinations of surfactants can be used to improve the performance of this remediation method. The surfactants Tween 80, Brij 35, and sodium dodecylbenzene sulfonate (SDBS) were selected based on environmental and reported performance criteria. Combinations of surfactants were tested in both batch and leaching column experiments. Experiments indicated that removal efficiency and flowrate in leaching columns were optimized when a mixture of 2% Brij 35 and 0.1% SDBS was employed. The presence of Tween 80 was found to be less effective, possibly due to its higher biodegradability in the soil. Since the measurement of surfactant concentration in the wash solution is important, several methods were tested before finally selecting a simple COD analysis as a surrogate parameter. Using the COD analysis, partitioning experiments were performed to measure the adsorption of surfactant on the soil. For economic reasons, it would be desirable to reuse the surfactant in a washing process. For this purpose, we employed activated carbon to selectively remove the more hydrophobic DDT from the surfactant solutions. Preliminary results have shown that carbon adsorption can remove some DDT, but additional work is required to understand and optimize the process.

The focus of this study was the development of an improved correlation that more accurately quantifies the relationships between optimum salinity, optimum solubilization ratios, chemical formulation variables such as surfactant and co-solvent structures, and the EACN. Entrained in this study are improved correlations for co-solvent partition coefficients and correlations for the optimum salinity and solubilization ratio with EACN. Several trends in the oil-water partition coefficient were observed with the alcohol type (IBA and phenol), the number of ethylene oxide groups in the co-solvent, the EACN of the oil, temperature, and salinity. New EACN measurements were made using optimized formulations containing various combinations of primary surfactants, co-surfactants, co-solvents and alkali. The new EACN measurements ranged from 11.3 to 21.1. These new data significantly expand the total number of reliable EACN values available to understand and correlate chemical EOR formulation results. An improved correlation that more accurately quantifies the relationship between surfactant structure, co-solvents, oil, temperature, and optimum salinity was developed using a new and much larger high quality formulation dataset now available from studies done in recent years in the Center for Petroleum and Geosystems Engineering at the University of Texas at Austin. The correlation is useful for understanding the now very large number of microemulsion phase behavior experiments as well as the uncertainties associated with these data, and for suggesting new chemical structures to develop and test.
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Chemical EOR processes such as polymer flooding and surfactant polymer flooding must be designed and implemented in an economically attractive manner to be perceived as viable oil recovery options. The primary expenses associated with these processes are chemical costs which are predominantly controlled by the crude oil properties of a reservoir. Crude oil viscosity dictates polymer concentration requirements for mobility control and can also negatively affect the rheological properties of a microemulsion when surfactant polymer flooding. High microemulsion viscosity can be reduced with the introduction of an alcohol co-solvent into the surfactant formulation, but this increases the cost of the formulation. Experimental research done as part of this study combined the process of hot water injection with ASP flooding as a solution to reduce both crude oil viscosity and microemulsion viscosity. The results of this investigation revealed that when action was taken to reduce microemulsion viscosity, residual oil recoveries were greater than 90%. Hot water flooding lowered required polymer concentrations by reducing oil viscosity and lowered microemulsion viscosity without co-solvent. Laboratory testing of viscous microemulsions in core floods proved to compromise surfactant performance and oil recovery by causing high surfactant retention, high pressure gradients that would be unsustainable in the field, high required polymer concentrations to maintain favorable mobility during chemical flooding, reduced sweep efficiency and stagnation of microemulsions due to high viscosity from flowing at low shear rates. Rough scale-up chemical cost estimations were performed using core flood performance data. Without reducing microemulsion viscosity, field chemical costs were as high as 26.15 dollars per incremental barrel of oil. The introduction of co-solvent reduced chemical costs to as low as 22.01 dollars per incremental barrel of oil. This reduction in cost is the combined result of increasing residual oil recovery and the added cost of an alcohol co-solvent. Heating the reservoir by hot water flooding resulted in combined chemical and heating costs of 13.94 dollars per incremental barrel of oil. The significant drop in cost when using hot water is due to increased residual oil recovery, reduction in polymer concentrations from reduced oil viscosity and reduction of microemulsion viscosity at a fraction of the cost of co-solvent.
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Title: Self-assembly of polymers with amphiphilic compounds (surfactants) in aqueous solutions Abstract: This PhD Thesis is devoted to the co-assembly in systems containing electrically charged polymers (polyelectrolytes and block copolymers containing polyelectrolyte sequences). I studied the interactions between block copolymers and oppositely charged surfactants in aqueous solutions, and the structure and properties of co-assembled nanoparticles by a combination of several experimental methods. I found that the spontaneous formation, solubility and stability of complex nanoparticles depend not only on the electrostatic attractive forces but also on the hydrophobic effects. In a major part of my Thesis, I studied the interaction of polyelectrolytes with oppositely charged gemini surfactants (containing two charged head-groups interconnected by a short linker and two hydrophobic tails) which is a relatively new topic - much less studied than the co-assembly with conventional single tail surfactants. Better understanding of the formation and properties of complexes containing gemini surfactants and polymers provides knowledge that should lead to novel tailor-made nanoparticles with desired properties for applications in medicine and new technologies (including nano-technologies). We have shown that the...