No description available.

This thesis is concerned with aspects of the surface and colloid chemistry of various microemulsion systems stabilised by pure nonionic surfactants and alcohol as well as mixtures of nonionic and anionic surfactants. Phase equilibria and interfacial characteristics of the systems are studied with a view to their potential usefulness for enhanced oil recovery, in which salinity and temperature are important parameters. The equilibrium microemulsion phases are scanned at different temperatures and salinities and thus interfacial boundaries can be determined and optimum salinity scans can be performed accurately using a modified spectrophotometer. Several analytical techniques (e.g., high performance liquid chromatography, gas chromatography, ion-exchange chromatography, mass spectrometry, viscometry, electrical conductivity, photon correlation spectroscopy, UV-spectrophotometry, thermogravimetric analysis, transmission electron microscopy, surface and interfacial tension techniques) have been used to characterise and understand the microchemistry of the microemulsion systems. Ultra-low interfacial tensions (>0.1 µN/m) can be achieved in the microemulsion systems. Surfactant transfer between phases, and phase inversion of micro emulsions are shown to occur around the condition which produces minimum interfacial tension. Adsorption of the surfactants from aqueous and nonaqueous solutions has been investigated and the results show that the extent of adsorption can be reduced significantly in the presence of alcohols (co-solvent). The extent of adsorption increases with increasing temperature and salinity; however, it decreases with an increase in the hydrophilic head group of the surfactant. Adsorption of nonionic surfactants on quartz from the nonaqueous solution (decane) is much greater than from aqueous solution. In microemulsion applications, droplet combustion of w/o microemulsions is also studied for different surfaces (i.e. silica, oxidised Fecralloy and catalyst coated Fecralloy) in the temperature range of 313-573K. Formaldehyde and acetaldehyde are formed as intermediate combustion products. Thus the microemulsion combustion can lead to new oxygenate products. The w/o microemulsion route is used to synthesize colloidal silica of controlled particle size and morphology. The particle size can be varied by changing the molar ratio of water to TEOS using a water pH of 10.5.

The aim of this thesis work was to investigate theadsorption of surfactants to different nonpolar interfaces.Particularly, the effects of the polar group and the nature ofthe hydrophobic interface were elucidated. The interfacialbehavior of the liquid-vapor interface was investigated bymeans of surface tension measurements. Here the effect of thepolar group and the hydrocarbon chain length was investigatedin a systematic manner. It was found that the shorter of thetwo chains examined, decyl, generated a larger surface pressurecontribution than the longer, dodecyl. Furthermore, the sugarbased surfactants behaved differently as compared to theethylene oxide based ones. The former could be modelled byassuming a hard disc behavior of the head group while thelatter displayed polymeric behavior. The influence of saltconcentration on the surface tension behavior of an ionicsurfactant, sodium dodecyl sulphate, was investigated. Theresult could be rationalized by employing the Gouy- Chapmanmodel to the polar region. Furthermore, mixtures of two sugarbased surfactants were investigated by surface tensionmeasurements and the adsorbed amount of the two components atthe interface atdifferent concentrations and fractions in thebulk were obtained by applying the Gibbs surface tensionequation. It was found that the molecule with the smaller headgroup adsorbed preferentially, and more so as the totalsurfactant concentration was increased. These findings could beexplained by considering the interactions generated by thedifferent head groups. The adsorption of sugar surfactants toan isolated hydrophobic surface was studied by means of wettingmeasurements and the behavior was similar to that at theliquid-vapor interface. Wetting isotherms were measured on twodifferent hydrophobic surfaces where the covalently attachedhydrophobic layers were in a crystalline and fluid state,respectively. The wetting results revealed that the sugarsurfactants anchored in the fluid hydrophobic layer. This had asignificant influence on the force profile. For example, at thecrystalline surface the surfactant monolayers were easilyremoved as the surface came into contact at relatively lowapplied loads. This was not the case when the hydrophobic layerwas in a fluid state. Here a significant fraction of thesurfactants remained between the surfaces. Disjoining pressureisotherms were measured using a sugar based surfactant thatwere thoroughly purified and compared to the as receivedsample. Even the purified sample showed a double-layer forcealthough lower as compared to the as received, one. Asignificant difference in foam stability was also observed. / <p>NR 20140805</p>

Neste estudo foi caracterizado o processo de solubilização de solutos neutros em sistemas micelares compostos de surfactantes não iônicos da família de alcoóis secundários etoxilados com o mesmo grupo hidrofóbico e graus diferentes de etoxilação, variando de 5 a 30 subunidades de oxido de etileno. Para isso, foram utilizadas as Relações Lineares de Energias Livres de Solvatação (LSER) como modelo preditivo para a eficiência de incorporação de solutos. As análises de regressão múltipla e as validações apresentadas tiveram por base a constante de incorporação micelar KS como variável dependente e os descritores de soluto de Abraham como as variáveis independentes. A metodologia utilizada para a determinação de KS baseou-se em técnicas fotofísicas (supressão de fluorescência), medidas de solubilização (solubilização em saturação via espectrofotometria de UV-VIS) e técnicas de cromatografia líquida (Cromatografia Micelar) e gasosa (Cromatografia por Análise de Fase Vapor ou Headspace). A determinação realizada forneceu as seguintes LSERs: 15-S-5: Log KS = 0,054 - 0,227A - 1,197B - 0,600S + 0,938E + 1,854V 15-S-7: Log KS = + 0,267 + 0,435A - 1,475B - 0,831S + 1,045E + 1,805V 15-S-15: Log KS = -0,047 + 0,314A - 1,265B - 0,487S + 0,823E + 2,107V 15-S-30: Log KS = - 0,345 + 0,366A - 1,114B - 0,430S + 0,858E + 2,310V Como é típico para sistemas micelares, constatou-se que a partição dos solutos entre os agregados micelares e a fase aquosa é dominada pelas propriedades de volume molar (V) e capacidade receptora de pontes de hidrogênio ou basicidade (B) do soluto, com contribuições secundárias de dipolaridade (S) e refração molar em excesso (E) do soluto. O aumento do tamanho da cabeça hidrofílica de oligômeros de oxietileno (OE) torna a micela menos coesa, facilitando a acomodação de solutos e favorecendo também a penetração de moléculas de água de hidratação que formam pontes de hidrogênio com as unidades de OE. Isto é indicado pelas variações observadas nos coeficientes de B e V. As variações dos coeficientes de S respondem também ao tamanho da cadeia e ao grau de hidratação, o que foi verificado pelos espectros de bandas vibrônicas de fluorescência de pireno e por alterações de deslocamentos químicos de RMN-1H. Anomalias observadas para surfactante 15-S-5 provavelmente deveram-se à presença de isopropanol utilizado como aditivo para solubilizá-lo em meio aquoso. O conjunto de dados obtidos demonstra que o tamanho da cadeia de OE e da micela responde melhor ao modo do que à extensão de solubilização dos solutos analisados, uma vez que a variável KS não responde de maneira linear ao grau de etoxilação para o conjunto de detergentes estudados. / This study has characterized the solubilization of neutral solutes in micellar systems composed of nonionic surfactants belonging to the family of ethoxylated secondary alcohols with the same hydrophobic group and different degrees of ethoxylation ranging from 5 to 30 ethylene oxide units. Linear Solvation Energy Relationships (LSER) was used as a predictive model for the efficiency of incorporation of solutes. The multiple regression analysis and the validations presented were based on the micellar incorporation constant KS as the dependent variable and Abraham solute descriptors as the independent variables. The methodologies utilized to determine the KS values included photophysical techniques (fluorescence quenching), measurements of solubility at saturation (via UV-VIs spectrophotometry), micellar liquid chromatography and gas chromatography (Headspace analysis of the vapor phase above micellar solutions). This study provided the following LSERs: 15-S-5: Log KS = - 0,054 - 0,227A - 1,197B - 0,600S + 0,938E + 1,854V 15-S-7: Log KS = + 0,267 + 0,435A - 1,475B - 0,831S + 1,045E + 1,805V 15-S-15: Log KS = - 0,047 + 0,314A - 1,265B - 0,487S + 0,823E + 2,107V 15-S-30: Log KS = - 0,345 + 0,366A - 1,114B - 0,430S + 0,858E + 2,310V As typically observed for micellar systems, the partitioning of solutes between micellar aggregates and the aqueous phase is dominated by the properties of molar volume (V) and hydrogen bond basicity (B) of the solute, with secondary contributions from the dipolarity (S) and excess molar refraction (E) of the solute. The increase in the size of the hydrophilic oxyethylene (OE) headgroup decreases the cohesion of the micelle, facilitating the accommodation of solutes and also favoring the penetration of waters of hydration that hydrogen bond with the OE units. This is indicated by the changes observed in the coefficients of B and V. The changes observed for S also respond to the size of the OE chain, as reflected in the vibronic bands of the fluorescence spectra of pyrene and changes of proton chemical shifts in 1H-NMR spectra. Anomalies for the surfactant 15-S-5 were probably due to the necessity to include isopropanol as an additive to solubilize it in water. The data show that the OE chain and micelle sizes respond better to the mode than to the extent of solubilization for the solutes analyzed, since the predictor variable KS does not respond consistently to the degree of ethoxylation for the micellar systems studied.

Neste estudo foi caracterizado o processo de solubilização de solutos neutros em sistemas micelares compostos de surfactantes não iônicos da família de alcoóis secundários etoxilados com o mesmo grupo hidrofóbico e graus diferentes de etoxilação, variando de 5 a 30 subunidades de oxido de etileno. Para isso, foram utilizadas as Relações Lineares de Energias Livres de Solvatação (LSER) como modelo preditivo para a eficiência de incorporação de solutos. As análises de regressão múltipla e as validações apresentadas tiveram por base a constante de incorporação micelar KS como variável dependente e os descritores de soluto de Abraham como as variáveis independentes. A metodologia utilizada para a determinação de KS baseou-se em técnicas fotofísicas (supressão de fluorescência), medidas de solubilização (solubilização em saturação via espectrofotometria de UV-VIS) e técnicas de cromatografia líquida (Cromatografia Micelar) e gasosa (Cromatografia por Análise de Fase Vapor ou Headspace). A determinação realizada forneceu as seguintes LSERs: 15-S-5: Log KS = 0,054 - 0,227A - 1,197B - 0,600S + 0,938E + 1,854V 15-S-7: Log KS = + 0,267 + 0,435A - 1,475B - 0,831S + 1,045E + 1,805V 15-S-15: Log KS = -0,047 + 0,314A - 1,265B - 0,487S + 0,823E + 2,107V 15-S-30: Log KS = - 0,345 + 0,366A - 1,114B - 0,430S + 0,858E + 2,310V Como é típico para sistemas micelares, constatou-se que a partição dos solutos entre os agregados micelares e a fase aquosa é dominada pelas propriedades de volume molar (V) e capacidade receptora de pontes de hidrogênio ou basicidade (B) do soluto, com contribuições secundárias de dipolaridade (S) e refração molar em excesso (E) do soluto. O aumento do tamanho da cabeça hidrofílica de oligômeros de oxietileno (OE) torna a micela menos coesa, facilitando a acomodação de solutos e favorecendo também a penetração de moléculas de água de hidratação que formam pontes de hidrogênio com as unidades de OE. Isto é indicado pelas variações observadas nos coeficientes de B e V. As variações dos coeficientes de S respondem também ao tamanho da cadeia e ao grau de hidratação, o que foi verificado pelos espectros de bandas vibrônicas de fluorescência de pireno e por alterações de deslocamentos químicos de RMN-1H. Anomalias observadas para surfactante 15-S-5 provavelmente deveram-se à presença de isopropanol utilizado como aditivo para solubilizá-lo em meio aquoso. O conjunto de dados obtidos demonstra que o tamanho da cadeia de OE e da micela responde melhor ao modo do que à extensão de solubilização dos solutos analisados, uma vez que a variável KS não responde de maneira linear ao grau de etoxilação para o conjunto de detergentes estudados. / This study has characterized the solubilization of neutral solutes in micellar systems composed of nonionic surfactants belonging to the family of ethoxylated secondary alcohols with the same hydrophobic group and different degrees of ethoxylation ranging from 5 to 30 ethylene oxide units. Linear Solvation Energy Relationships (LSER) was used as a predictive model for the efficiency of incorporation of solutes. The multiple regression analysis and the validations presented were based on the micellar incorporation constant KS as the dependent variable and Abraham solute descriptors as the independent variables. The methodologies utilized to determine the KS values included photophysical techniques (fluorescence quenching), measurements of solubility at saturation (via UV-VIs spectrophotometry), micellar liquid chromatography and gas chromatography (Headspace analysis of the vapor phase above micellar solutions). This study provided the following LSERs: 15-S-5: Log KS = - 0,054 - 0,227A - 1,197B - 0,600S + 0,938E + 1,854V 15-S-7: Log KS = + 0,267 + 0,435A - 1,475B - 0,831S + 1,045E + 1,805V 15-S-15: Log KS = - 0,047 + 0,314A - 1,265B - 0,487S + 0,823E + 2,107V 15-S-30: Log KS = - 0,345 + 0,366A - 1,114B - 0,430S + 0,858E + 2,310V As typically observed for micellar systems, the partitioning of solutes between micellar aggregates and the aqueous phase is dominated by the properties of molar volume (V) and hydrogen bond basicity (B) of the solute, with secondary contributions from the dipolarity (S) and excess molar refraction (E) of the solute. The increase in the size of the hydrophilic oxyethylene (OE) headgroup decreases the cohesion of the micelle, facilitating the accommodation of solutes and also favoring the penetration of waters of hydration that hydrogen bond with the OE units. This is indicated by the changes observed in the coefficients of B and V. The changes observed for S also respond to the size of the OE chain, as reflected in the vibronic bands of the fluorescence spectra of pyrene and changes of proton chemical shifts in 1H-NMR spectra. Anomalies for the surfactant 15-S-5 were probably due to the necessity to include isopropanol as an additive to solubilize it in water. The data show that the OE chain and micelle sizes respond better to the mode than to the extent of solubilization for the solutes analyzed, since the predictor variable KS does not respond consistently to the degree of ethoxylation for the micellar systems studied.

<p>The aim of this thesis work was to investigate theadsorption of surfactants to different nonpolar interfaces.Particularly, the effects of the polar group and the nature ofthe hydrophobic interface were elucidated. The interfacialbehavior of the liquid-vapor interface was investigated bymeans of surface tension measurements. Here the effect of thepolar group and the hydrocarbon chain length was investigatedin a systematic manner. It was found that the shorter of thetwo chains examined, decyl, generated a larger surface pressurecontribution than the longer, dodecyl. Furthermore, the sugarbased surfactants behaved differently as compared to theethylene oxide based ones. The former could be modelled byassuming a hard disc behavior of the head group while thelatter displayed polymeric behavior. The influence of saltconcentration on the surface tension behavior of an ionicsurfactant, sodium dodecyl sulphate, was investigated. Theresult could be rationalized by employing the Gouy- Chapmanmodel to the polar region. Furthermore, mixtures of two sugarbased surfactants were investigated by surface tensionmeasurements and the adsorbed amount of the two components atthe interface atdifferent concentrations and fractions in thebulk were obtained by applying the Gibbs surface tensionequation. It was found that the molecule with the smaller headgroup adsorbed preferentially, and more so as the totalsurfactant concentration was increased. These findings could beexplained by considering the interactions generated by thedifferent head groups. The adsorption of sugar surfactants toan isolated hydrophobic surface was studied by means of wettingmeasurements and the behavior was similar to that at theliquid-vapor interface. Wetting isotherms were measured on twodifferent hydrophobic surfaces where the covalently attachedhydrophobic layers were in a crystalline and fluid state,respectively. The wetting results revealed that the sugarsurfactants anchored in the fluid hydrophobic layer. This had asignificant influence on the force profile. For example, at thecrystalline surface the surfactant monolayers were easilyremoved as the surface came into contact at relatively lowapplied loads. This was not the case when the hydrophobic layerwas in a fluid state. Here a significant fraction of thesurfactants remained between the surfaces. Disjoining pressureisotherms were measured using a sugar based surfactant thatwere thoroughly purified and compared to the as receivedsample. Even the purified sample showed a double-layer forcealthough lower as compared to the as received, one. Asignificant difference in foam stability was also observed.</p>

No description available.

Functionalized membranes provide an elegant platform for selective separations and sorptions. In this dissertation, application of functionalized membranes for surfactant and metal sorption studies are discussed. Sorption behavior of surfactants is also studied using quartz crystal microbalance (QCM) and other techniques. Adsorption of the ethoxylated surfactants on polymeric materials (cotton and polyester) and model gold surface was quantified from a non-aqueous siloxane based solvent (D5) and water. The role of ethylene oxide group and the effect of nature of polymeric materials on adsorption behavior was quantified and established. In the case of gold-water interface, the adsorption data was fitted to calculate adsorption/desorption rate constants. The study is important towards applications involving use of the surfactants in cleaning operations. PAA functionalized membranes were prepared and used for separation of the surfactants from the siloxane solvent. Finally the pH sensitivity of the PAA-surfactant complex was verified by successful regeneration of the membrane on permeation of slightly alkaline water. The preparation and application of thiol and sulfonic acid functionalized silica mixed matrix membranes for aqueous phase metal ion sorption is also studied. The functionalized particles were used as the dispersed phase in the polysulfone or cellulose acetate polymer matrix. The effects of the silica properties such as particle size, specific surface area, and porous/nonporous morphology on the metal ion sorption capacity were studied. Silver and ferrous ions were studied for metal sorption capacities. The ferrous ions were further reduced to prepare membrane immobilized iron nanoparticles which are attractive for catalytic applications. One dimensional unsteady state model with overall volumetric mass transfer coefficient was developed to model the metal ion sorption using mixed matrix membrane. The study demonstrates successful application of the functionalized mixed matrix membranes for aqueous phase metal capture with high capacity at low transmembrane pressures. The technique can be easily extended to other applications by altering the functionalized groups on the silica particles. The study is important towards water treatment applications and preparation of membrane immobilized metal nanoparticles for catalytic applications.

L’idée directrice de ce travail de thèse était d’introduire au sein de mésophases lipidiques des molécules de β-cyclodextrine (βCD) amphiphiles obtenue par bio-estérification afin d’obtenir des nano-assemblages plurimoléculaires et multi-compartimentés combinant trois fonctions essentielles pour le transport ou la vectorisation de molécules thérapeutiques : (i) la capacité d’incorporer une substance d’intérêt par formation de complexe d’inclusion avec la cyclodextrine ; (ii) être biocompatibles et aptes à passer facilement les barrières biologiques ; (iii) pouvoir co-incorporer une seconde substance d’intérêt, hydrophile ou hydrophobe, dont l’action biologique soit différente de celle assurée par la première substance. L’ensemble des travaux ont porté sur le dérivé βCD-C10 polysubstitué en face secondaire par des chaînes hydrocarbonées en C10 avec un degré moyen de substitution de 7,5. L’association de ce dérivé avec trois catégories de lipides a été envisagée : des tensioactifs micellaires non-ioniques (Brij 98, Polysorbate 80, n-dodécyl-β-D-maltoside), un lipide lyotrope non lamellaire formant des mésophases de type cubique bicontinue (monooléine), un phospholipide s’auto-organisant en bicouches propices à l’obtention de vésicules (dimyristoyl phosphatidylcholine). Selon une démarche principalement physico-chimique, différentes techniques ont été mises en œuvre pour caractériser les systèmes mixtes lipide/βCD-C10 aux échelles moléculaire et supramoléculaire : diffusion-diffraction des rayons X, calorimétrie différentielle, spectrophotométrie d’absorption UV-visible, spectroscopie de fluorescence, diffusion de la lumière statique (turbidimétrie) ou quasi-élastique, microscopie optique et microscopie électronique par cryo-transmission. L’ensemble des résultats démontrent que le dérivé βCD-C10 forme spontanément ou selon un protocole très simple, des assemblages plurimoléculaires mixtes avec les trois catégories de lipides, assemblages dont la topologie dépend de la structure chimique du lipide et du taux de cyclodextrine amphiphile incorporé (tubules, vésicules uni- ou oligolamellaires, cubosomes). Ces assemblages sont stables et capables d’incorporer une substance hôte hydrophobe, notamment les vésicules mixtes tensioactif non-ionique/ βCD-C10 et les cubosomes mixtes monooléine/P80/ βCD-C10. / The key idea of this Ph.D. thesis is to introduce amphiphilic β-cyclodextrin molecules (βCD), obtained by bio-transesterification, within lipid mesophases in order to obtain multi-compartment plurimolecular nano-assemblies, which combine three essential functions for transport or delivery of therapeutic molecules: (i) capacity to incorporate a substance of interest through formation of inclusion complexes with the modified cyclodextrin; (i) biocompatibility and ability to easily pass the biological barriers; and (iii) possibility for co-encapsulation of a second substance of interest, a hydrophilic or a hydrophobic one, whose biological action is different from that provided by the first substance. The performed Ph. D. work focused on the β-cyclodextrin derivative βCD-C10 with an average degree of substitution of 7.5 of the secondary face of the macrocycle by hydrocarbon chains C10. The association of this derivative with three classes of amphiphiles was studied: (i) nonionic micellar surfactants (Brij 98, Polysorbate 80, n-dodecyl β-D-maltoside), (ii) a lyotropic nonlamellar lipid forming bicontinuous cubic mesophases (monoolein), and (iii) a phospholipid (dimyristoyl phosphatidylcholine), which self-ssembles into bilayer membranes permitting the production of vesicles.The employed physical-chemical approach involved different techniques for characterization of the mixed βCD-C10/lipid systems at molecular and supramolecular levels: cryo-transmission electron microscopy, X-ray diffraction, differential scanning calorimetry, UV-visible absorption spectroscopy, fluorescence spectroscopy, turbidimetry, and quasi-elastic light scattering.The obtained results indicated that the βCD-C10 derivative forms spontaneously (or via a very simple preparation protocol) plurimolecular mixed nano-assemblies with the three types of lipids. The topologies of the resulting nano-assemblies essentially depend on the chemical structures of the lipids and the degree of incorporation of the amphiphilic cyclodextrin (tubules, unilamellar or oligolamellar vesicles, and cubosomes). These assemblies, namely the mixed vesicles of nonionic surfactant/βCD-C10 and the cubosomes of mixed monoolein/P80/βCD-C10 compositions, are stable and capable of incorporation of hydrophobic guest substances.