The objective of this work was to evaluate chemical interactions in phase behavior experiments that make surfactant-polymer formulations with alkali complex to design. This experimental study of sodium carbonate shows improvement of microemulsion phase behavior with many crude oils in addition to its classical use to produce soap in-situ and raise pH to reduce potential for surfactant adsorption. Soap is generally not sufficient by itself for chemical flooding because it has low tolerance to calcium ions and low optimal salinity. The blending of synthetic surfactant with sodium carbonate is needed to increase the optimum salinity, increase the tolerance to calcium, and reduce the sensitivity to changes in salinity by broadening the active salinity window. Sodium carbonate can also be added to the surfactant formulation to adjust electrolyte concentration for optimal salinity. Evidence suggests that additional consideration should be given to sodium carbonate in enhanced oil recovery applications because of benefits that extend beyond the traditional application. The research presented in this work discusses experiments that were conducted for the purpose of studying the benefits of sodium carbonate on surfactant phase behavior. After phase behavior screening, the formulations were tested to demonstrate their performance in porous media. Core floods were conducted to test the potential use of chemical flooding for a field application with several low acid crude oils. Two of the core flood experiments with Berea sandstone reduced the residual oil below 1% with chemical injection. An acceptable pressure gradient was maintained and good sweep was obtained using an AMPS polymer at high temperature. Polymer was needed to make the slug and drive sufficiently viscous to recover the mobilized oil and reduce surfactant retention through good sweep efficiency. The experiments reported in this research have contributed to an ongoing effort to design a suitable alkali-surfactant-polymer chemical formulation for the application in a high permeability, high temperature (85 ºC) sandstone reservoir located in Indonesia. / text

Amidine-based switchable surfactants can be used as stabilizers during emulsion polymerization and the resulting latexes can then be destabilized by the removal of CO2. High Tg polymers have been successfully redispersed, as shown by recovery of primary particle size (measured by light scattering methods), but an input of energy was required. Sonication was the first method used, but lower-energy methods such as rotor-stators and a blender have also been successful in redispersing aggregated latexes. Colloidal stability was found to be reversible for at least three aggregation/redispersion cycles, and redispersibility was retained after the removal of water and addition of fresh water. Stimuli-responsive polymer colloids with reversible colloidal stability may have many uses. The shipping of latexes, for example, would be easier and less energy intensive if the latex particles could be aggregated and the bulk of the water removed. The latexes would then have to be redispersed prior to use. Switchable surfactants have also been used for the semi-continuous copolymerization of butyl acrylate and methyl methacrylate to form a high solids content (42 wt%), low-Tg latex. The latex can be destabilized with air and heat but cannot undergo redispersion because the low Tg polymer particles fuse upon aggregation. The copolymer, when dried at room temperature, formed a continuous film. Latexes with high solids content and low Tg’s are representative of latex paint formulations. Because the switchable surfactants have been shown to be successful in preparing these latexes, it is possible that they may be useful in the latex paint industry, for example as fast setting paints. / Thesis (Master, Chemistry) -- Queen's University, 2011-09-26 13:18:33.905

Surface active agents have been successfully employed in numerous industrial, agricultural and biomedical applications for decades. Trisiloxane surfactants in particular have proved to be exceptionally effective as wetting enhancers; hence the name ‘superspreaders’. Since the early ‘90s these extraordinary surfactants have become an irreplaceable component in various products and processes. However, the true nature of their specific wetting behaviour has not been fully revealed and their underlying wetting mechanisms are still poorly understood despite substantial scientific interest during the last decades. In this thesis is an attempt to shed light on specific wetting and spreading behaviour of trisiloxane solutions. Commercial superspreader products were tested in various environments in order to get further insight into their performance in specific practical applications. Experimental investigation of wetting of superspreader solutions on surfaces of different hydrophobicity and comparison to that of a conventional surfactant revealed superiority of trisiloxanes. Exceptional interfacial activity was explained in terms of the specific chemical structure and ‘T’-shape of the molecule. However, sensitivity of the trisiloxane head to low pH and long-time ageing in aqueous environment was revealed. Performance of binary mixtures of commercial superspreaders and conventional surfactant was also assessed. Behaviour of trisiloxanes in the capillary action was studied. Finally, a comprehensive mathematical model for trisiloxane wetting, which incorporates diffusion as the governing factor of the wetting process, was developed.

No description available.

No description available.

This work is concerned with an alternative method for metal ion removal from aqueous solutions - surfactant enhanced ultrafiltration. Surfactant monomers aggregate above a certain concentration, specific to the surfactant, to form micelles. Anionic surfactant micelles will attract and bind metal cations. Free metal ions and surfactant monomers pass freely through an ultrafiltration membrane, but if the micelle-metal ion complex is sufficiently large it is rejected. Research reported in this thesis has been carried out on well defined aqueous solutions containing only one type of metal ion together with the natural surfactant lecithin. Lecithin is a food grade by-product of the soybean processing industry and it was chosen because it is non-toxic, biodegradable, abundant and inexpensive. It has a high molecular weight of about 750 Daltons and forms large size micelles. The main aim was to identify the basic mechanisms which influence the permeate flux and rejection levels of the process. The project was carried out in three stages. Stage one was the characterisation of the feed solution which included the determination of the critical micelle concentration using surface tension measurements, measurement of micelle size and zeta potential using a Malvern zeta sizer and visualisation of the micelle shape using scanning electron microscopy of freeze fractured lecithin solution droplet. In the second stage filtration experiments were carried out at a wide range of lecithin concentrations, metal ion concentrations and operating conditions. The experiments were run for 5 hours, by which stage a steady state condition was reached in all cases. Permeate samples were taken after I, 3 and 5 hours. Permeate flux was monitored throughout the experiment. The following properties were monitored for the feed solution at the beginning and the end of each experiment and for all permeate samples: lecithin concentration, copper concentration, pH, conductivity. In the 3 stage Electron Dispersive Analysis by X-ray (EDAX), Scanning Electron Microscopy (SEM) and a X-ray Photoelectron Spectrum Technique (XPS) were employed to investigate any membrane feed solution interactions. The results of the 3 stages were used to identify the basic mechanisms which control the permeate flux levels and the extent of component rejection in lecithin enhanced ultrafiltration.

Thesis (Ph. D.)--University of Texas at Dallas, 2007. / Includes vita. Includes bibliographical references (leaves 101-105).

Th.--Sc. pétrolières--Paris VI, 1986. / Bibliogr., 3 p.

Philosophiae Doctor - PhD / Carbon dioxide emissions have become a major concern as they are one of the contributing factors to the “green-house” effect. Recently, much effort has been put into separating carbon dioxide (CO2) from flue gases linked to the combustion processes at fixed point sources. The development of solid sorbents for adsorption based on CO2 capture has attracted much attention. Ordered Mesoporous Silica (OMS) materials have recently attracted much attention as solid adsorbents for capturing CO2. OMS have been investigated for this purpose owing to their high pore volume, large surface area and ease of functionalizationIn this work we report on the synthesis of OMS viz. MCM-41 and SBA-15 along with amorphous silica as adsorbents for CO2 capture. MCM-41 was prepared with surfactants having different alkyl chain lengths (C14TABr, C16TABr and C18TABr) where TABr is trimethylammonium bromide. SBA-15 was prepared using a Triblock copolymer as a structure directing agent for the organization of polymerizing silica species. Commercial amorphous silica gel was used for comparative purposes. Initial characterization OMS with powder X-Ray diffraction (XRD) and small angle diffraction (SAXS) yielded diffraction patterns which may be associated with well-ordered structures of hexagonal mesoporous material. Ease of preparation for MCM-41 materials allowed for convenient scale- up, obtaining highly ordered mesoporous silica MCM-41 at room temperature. SBA-15 was also found to be scaled up with considerable ease through increasing the volume of the autoclave during hydrothermal treatment. Structural, morphological and textural properties of the adsorbents were characterized by N2 physisorption measurements, Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM) and Thermogravimetric Analysis (TGA). TEM confirmed the hexagonal structure; SEM showed that C14MCM-41 had spheroidal particle morphology whereas SBA-15 displayed rod-like structures. High surface areas of up to 1302, 1186, 1211 and 1024 m2/g for C14MCM-41, C16MCM-41, C18MCM-41 and SBA-15, respectively were obtained. The pore size of MCM-41 materials was increased from 2.6 nm for C14MCM-41 to 4.4 nm in diameter for C18MCM-41 using surfactants with different alkyl chain lengths. CO2 adsorption characteristics of OMS were studied using CO2-temperature programmed desorption (TPD). The results showed that C14MCM-41, C16MCM- 41, C18MCM-41 and SBA-15 desorbed 0.19, 0.16, 0.11 and 0.26 mmol/g respectively. The synthesized OMS were then further modified by grafting various amine moieties on their surfaces in order to increase their CO2 adsorptive capabilities. 3-(Aminopropyl)triethoxysilane (APS), N-[3-(trimethoxysilyl)propyl]ethylene- diamine (TPED), 3-chloropropyl)-trimethoxysilane (CPS), ethyl 2-bromopropanoate, tris(2-aminoethyl)amine (TREN) and guanidine. Several characterization techniques such as XRD, SAXS, HRTEM, HRSEM, TGA, Fourier Transform Infra-Red (FT-IR) spectroscopy, CO2 isotherms and CO2-TPD were used to analyze amine grafted solid sorbents for CO2 capture. The results revealed that the structural integrity of the amine modified sorbents was not compromised during the grafting process. The structural properties of the supports, such as surface area and pore size, nature of amine and the number of amine groups, affected the loading and CO2 adsorption capacity of chemically grafted sorbents. APS grafted amorphous silica gel adsorbed 0.67 mmol/g CO2, which proved to be the highest compared to C18MCM-41 and SBA-15 grafted with APS and TPED. C18MCM-41, SBA-15 and amorphous silica gel were also grafted with TREN and adsorbed 0.42, 0.51 and 0.27 mmol/g of CO2, respectively. A systematic study of guanidine grafted on C14MCM-41, C16MCM-41 and C18MCM-41 was investigated, for the first time, to the best of our knowledge. Structural properties like variation in pore size, proved to enhance the adsorption capacity of the adsorbent, coupled with the guanidine molecules grafted on MCM-41 materials. C18MCM-41-guanidine showed the highest CO2 uptake of the guanidine grafted MCM-41 materials, adsorbing 0.30 mmol/g. A novel synthetic route to TPED-TREN grafted C18MCM-41 and SBA-15, using ethyl 2-bromopropanoate as a linker, was investigated as a potential adsorbent for CO2 capture, for the first time. C18MCM-41-TPED-TREN and SBA-15-TPED-TREN CO2 adsorption capacity were found to be 0.14 and 0.14 mmol/g, respectively.

Les surfactifs catalytiques équilibrés (baptisés "Catasurfs") permettent d'élaborer des systèmes de microémulsions polyphasiques utilisés comme milieux réactionnels. Dans ce contexte, des alkylammonium et des alkylsulfonates amphiphiles bicaténaires ont été développés. Leurs comportements en système aqueux (solubilité, concentration micellaire critique, diagramme binaire, cristaux liquides) ainsi qu'en système biphasique eau/huile (diagramme en poisson, formation de systèmes de microémulsions) ont été étudiés en fonction de la nature des contre-ions. Les phases cristallines lyotropes ont été identifiées par microscopie optique à polarisation et par diffusion des rayons X aux petits angles (SAXS). Une classification des surfactifs selon leur amphiphilicité a été établie à partir des diagrammes de Fish construits selon un balayage en huiles. Le comportement de phases de ces surfactifs dans l'eau (micelles) et en système biphasique eau/huile (microémulsion) dépend non seulement de la longueur de la chaîne mais aussi du degré d'hydratation des contre-ions, en accord avec la série d’Hofmeister. L’intérêt des microémulsions polyphasiques à base de Catasurfs a été démontré d'une part en microémulsion Winsor III à base de [DiC10]2WO4 appliquée à l'époxydation des oléfines et à l’oxydation de sulfures en présence de H2O2 et d'autre part, via l'élaboration de microémulsions Winsor IV thermosensible utilisant la synergie entre les C8E4 et [DiC8]2MoO4 pour la "Dark Singlet Oxygenation". Par ailleurs, une nouvelle voie de synthèse « one-pot» de la (+)-nootkatone, fragrance à haute valeur ajoutée, à partir du(+)-valencène a été mise au point dans conditions sans solvant. / Balanced Catalytic Surfactants (abbreviated as “Catasurfs”) allow the design of multiphase microemulsion systems used as reaction media. In this context, the double tailed alkylammonium and alkylsulfonate amphiphiles have been developed. Their behavior in aqueous system (solubility, critical micellar concentration, binary diagram, lyotropic liquid crystal) as well as biphasic oil/water system (Fish diagram, forming microemulsions systems Winsor Type I, II, III and IV) were studied based on the nature of counter ions (Br, Cl, WO42−, MoO42−, SO42− for anionic and H+, Li+, Na+, K+, Cu2+, Zn2+, Ca2+, Sc3+ for cationic). Lyotropic crystal phases were identified by polarization optical microscopy and small angle X-ray scattering diffusion (SAXS). A classification of surfactants according to their amphiphilicity was established from the Fish diagrams constructed by scanning oil polarities. The phase behavior of these surfactants in water (micelles) and biphasic oil / water system (microemulsion) does not only depend on the alkyl chain length but also the counter ions hydration degree, in agreement with the Hofmeister series. The advantages of multiphase microemulsions based on “Catasurfs” were on one hand demonstrated by the epoxidation of olefins and oxidation of sulfides in a Winsor III microemulsion based on [DiC10]2WO4 in the presence of H2O2 and, on the other hand, by the development of a thermosensitive Winsor IV microemulsions using synergy between C8E4 and [DiC8]2MoO4 for “Dark Singlet Oxygenation”. In addition, a new “one-pot” synthetic route of the (+)- nootkatone, a high value-added fragrance, from the (+)-valencene was developed under solvent-free conditions.