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A Study of Microfluidic Reconfiguration Mechanisms Enabled by Functionalized Dispersions of Colloidal Material for Radio Frequency ApplicationsGoldberger, Sean A. 2009 May 1900 (has links)
Communication and reconnaissance systems are requiring increasing flexibility concerning functionality and efficiency for multiband and broadband frequency applications. Circuit-based reconfiguration mechanisms continue to promote radio frequency (RF) application flexibility; however, increasing limitations have resulted in hindering performance. Therefore, the implementation of a "wireless" reconfiguration mechanism provides the required agility and amicability for microwave circuits and antennas without local overhead. The wireless reconfiguration mechanism in this thesis integrates dynamic, fluidic-based material systems to achieve electromagnetic agility and reduce the need for "wired" reconfiguration technologies. The dynamic material system component has become known as electromagnetically functionalized colloidal dispersions (EFCDs). In a microfluidic reconfiguration system, they provide electromagnetic agility by altering the colloidal volume fraction of EFCDs - their name highlights the special considerations we give to material systems in applied electromagnetics towards lowering loss and reducing system complexity. Utilizing EFCDs at the RF device-level produced the first circuit-type integration of this reconfiguration system; this is identified as the coaxial stub microfluidic impedance transformer (COSMIX). The COSMIX is a small hollowed segment of transmission line with results showing a full reactive loop (capacitive to inductive tuning) around the Smith chart over a 1.2 GHz bandwidth. A second microfluidic application demonstrates a novel antenna reconfiguration mechanism for a 3 GHz microstrip patch antenna. Results showed a 300 MHz downward frequency shift by dielectric colloidal dispersions. Magnetic material produced a 40 MHz frequency shift. The final application demonstrates the dynamically altering microfluidic system for a 3 GHz 1x2 array of linearly polarized microstrip patch antennas. The parallel microfluidic capillaries were imbedded in polydimethylsiloxane (PDMS). Both E- and H-plane designs showed a 250 MHz frequency shift by dielectric colloidal dispersions. Results showed a strong correlation between decreasing electrical length of the elements and an increase of the volume fraction, causing frequency to decrease and mutual coupling to increase. Measured, modeled, and analytical results for impedance, voltage standing wave ratio (VSWR), and radiation behavior (where applicable) are provided.
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Soft Matter Under Electric Field And ShearNegi, Ajay Singh 04 1900 (has links)
‘Soft condensed matter’ is a newly-emerged sub-discipline of physics concerned with the study of systems that are mechanically soft such as colloids, emulsions, surfactants, polymers, liquid crystals, granular media and various biomaterials including DNA and proteins. These materials display a broad range of interesting microstructures and phase behaviours and have a myriad of applications in the materials, food, paint and cosmetic industries as well as medical technologies. Soft condensed matter physics presents new opportunities and challenges for the development of new ideas and concepts in experimental and theoretical physics alike. Because the field overlaps with many different disciplines, the study of soft matter also offers promising developments to other fields of science including chemistry, chemical engineering, materials science, biology, and environmental science. The behaviour of these systems is dominated by one simple fact: they contain mesoscopic structures in the size range 10 nm to 1 µm that are held together by weak entropic forces. The elastic constants of these materials are 109 times smaller than the conventional atomic materials and hence are easily deformable by external stresses, electric or magnetic fields, or even by thermal fluctuations. We have studied two important classes of soft matter systems in this thesis -colloidal suspensions and surfactant systems. The thesis is divided into two main themes: (a) Effects of electric field on the colloidal suspensions, and (b) Effects of shear on surfactant solutions. Motions of colloidal particles under the influence of applied electric field were observed under a microscope and were studied using image analysis and particle tracking. We have also used tracking of thermal fluctuations of colloidal particles embedded in surfactant gels to study microrheology of surfactant solutions. Linear and non-linear rheology of aqueous solutions of cationic cetyltrimethyl ammonium bromide (CTAB) and anionic sodium-3-hydroxynapthalene-2-carboxylate (SHNC) were studied using bulk rheology in a commercial rheometer. Rheological studies of an anionic surfactant sodium dodecyl sulphate (SDS) in the presence of strongly binding counterion p-toluidine hydrochloride (PTHC) has also been done.
Chapter 1 starts with a general introduction to soft condensed matter systems and then we proceed to describe two specific class of soft condensed materials which we have studied in this thesis -colloidal suspensions and surfactant/water systems. After describing different types of colloids, we discuss why colloids are suitable as model systems in condensed matter physics. This is followed by a discussion on the chemical structure, phase behaviour and self assembling properties of surfactant molecules in water. We then discuss the inter-macromolecular forces such as van der Waals interaction, the screened Coulomb repulsion, hydrogen bond, hydrophobic and hydration forces and steric repulsion which are the major players in the interaction in soft condensed matter systems. The systems that have been the subject of our experimental studies, viz. polystyrene colloidal suspensions, CTAB+SHNC, SDS+PTHC and CTAT have also been discussed in detail. Then we have given an overview of effects of electric field on the colloidal suspensions. Two types of geometries have been discussed: one in which the field is parallel to the plates and another when the field is perpendicular to the electrodes. Application of colloidal particles in diagnostic tests (Latex Agglutination Tests) has been discussed after this. Some methods used to enhance the sensitivity of LATs have also been reviewed. This is followed by a theoretical background of linear and non-linear rheology. We have also given an introduction to digital video microscopy, its advantages and discussed few quantities like pair correlation function, structure factor which can be extracted using digital video microscopy and particle tracking. The concluding part of this chapter describes the organization of this thesis.
Chapter 2 discusses the experimental apparatus and techniques used in our studies. We describe our setup for applying the electric field to the colloidal particles and imaging and tracking their motion. We also discuss the image processing and analyzing methods for extracting the useful quantities from the digitized images. We have described the various components of the MCR-300 stress-controlled rheometer (Paar Physica, Germany) and the AR-1000N stress-controlled rheometer (T. A. Instruments, U. K.) followed by different experimental geometries that we have used for our experiments. Next we have described the various experiments that can be done using a commercial rheometer. Calculation of surface charge of colloidal particles using a conductivity meter has been demonstrated for our colloidal particle suspensions. We also describe the sample preparation methods employed in different experiments.
In Chapter 3, we have discussed our study of clustering of colloidal particles under the influence of an ac electric field as a function of frequency. The field was applied in a direction perpendicular to the confining walls. Two regimes are observed, a low frequency regime where the clusters are isotropic with a local triangular order and a new high-frequency regime where the clusters are highly elongated (anisotropic) with no local order. The crossover from one regime to the other occurs at a critical frequency, fc. The formation of elongated clusters seen at high frequencies is explained in terms of rotation of particles due to a phase lag between the polarization of the electric double layer around a particle and the applied electric field that arises because of inhomogeneities of the conducting surface. We have also observed that the threshold field for the cluster formation, Eth, increases with frequency in both the regimes. We did these studies on two different sizes of particles and found that both Eth and fc were lower for the larger particles. Our model based on particle rotation was able to estimate the value of fc correctly for both the sizes of the particles.
Chapter 4 describes a method employing an ac electric field applied perpendicular to the confining walls to increase the sensitivity of recognition of ligands by their corresponding receptors grafted on Brownian latex particles. Application of electric field assists the colloidal micro-particles grafted with receptors to come nearer due to electro-hydrodynamic drag. This increase in the local concentration of the latex particles results in improving the chances of ligand-receptor interaction leading to the aggregation of the latex particles. With this technique we have been able to increase the sensitivity of the ligand-receptor recognition by a factor as large as 50. We have demonstrated the utility of our method using streptavidin as the model receptor and biotinylated RNase A as the model ligand. We have also applied our technique to a commercially available kit for rheumatoid factor (RF) with successful results. The same method was also successfully applied for the detection of typhoid whose antibodies were purified and attached to polystyrene particles by our collaborators from DRDE Gwalior.
In Chapter 5, we have studied the statics and dynamics of colloidal particles at different applied electric fields from zero to beyond the threshold field. We have taken a series of time-lapsed images and calculated out the pair-correlation function, mean squared displacement, structure factor, non-Gaussian parameter etc. We have studied both mono-dispersed colloidal system and binary colloidal system (mixture of two different sizes of particles). The aggregates formed in the two cases were analysed with the help of Voronoi polygons to quantify the microscopic structure. In mono-dispersed system, the aggregates formed were two-dimensional hexagonal crystals and we have used this system to study the freezing transition in 2-dimension. The properties of the system in the liquid and the crystalline state satisfy various criteria for the 2-d freezing transition. The first maximum of the structure factor at the voltage at which freezing occurs, is 5.5 as has been suggested for the 2-d freezing. This is reflected in the dynamics of the system also, where the ratio D/D0 falls below 10%, in accordance with the LPS (L¨owen, Palberg, Simon) criterion for freezing in 2-d colloidal systems [Phys. Rev. Lett. 70, 1557 (1993)]. However, in the binary colloidal system the clusters formed were not crystalline but more like 2-d dense liquids. A closer inspection of these clusters reveals that the motion of a smaller subset of particles is cooperative and follows string-like paths. The mean square displacement of such a system shows a plateau in the intermediate times which indicates the “caging” of particles by its neighbours. A peak in non-gaussian parameter indicates the presence of dynamical heterogeneities in the system.
In Chapter 6, we have described the use of multiple particle tracking to study the microrheology of semidilute solutions of wormlike micelles and compared the results with those from macrorheology experiments done on the same samples. Two concentrations of CTAT (1.3% and 2%) were used. We observed that, in spite of the mesh size being much smaller than the size of the probe particles, the viscoelastic response function calculated using the one-point microrheology does not match with that measured from macrorheology. This can be attributed to the fact that there is another important length scale in the system, the mean micellar length, and it is comparable to the probe particle size. Two-point microrheology was successful in verifying the macrorheology results for CTAT 1.3% but it fails to do so for CTAT 2%. We attribute this to the fact that in a higher viscosity sample (2%), the hydrodynamic force propagate to a lesser distance, thereby limiting the measurable correlation between the particles and precluding the success of two-point microrheology.
Chapter 7 describes a rheological study of aqueous solutions of varying concentration of cationic cetyltrimethyl ammonium bromide (CTAB) and anionic sodium-3-hydroxynapthalene-2-carboxylate (SHNC) kept at a fixed molar concentration ratio [CTAB]/[SHNC] = 2. At this molar ratio, the surfactants self-assemble into wormlike micelles which get entangled above the overlap concentration to form viscoelastic gel. The range of the total surfactant concentration φ varies from 1.17% to 5.16% by weight. We found that, plateau modulus, G0, shows a power law dependence on the surfactant concentration, φ, with an exponent 3, which is higher than the expected value of 2.25 observed for the one-component wormlike micelles. Zero shear viscosity, η0, and relaxation time, τR show a maximum at the surfactant concentration, φmax = 1.9% in contrast to a monotonic increase with φ. We propose that this non-monotonic behaviour is due to the unusual dependence of the average micellar length L ¯on φ, showing a maximum in average micellar length L at φmax. This argument provides a strong support to the model of micellar growth in the presence of electrostatic interactions developed by Mackintosh et. al [Europhys. Lett. 12, 697 (1990)]. The presence of electrostatic interactions also appears in the behaviour of the plateau modulus G0 that exhibits a larger φ dependence than in highly screened micelles. In the non-linear flow experiments, a minimum observed in critical shear rate (the shear rate at which shear thinning starts), ˙γc, at φmax strengthens our arguments.
In Chapter 8, we describe the phase behaviour and rheology of SDS+PTHC (sodium dodecyl sulphate + p-toluidine hydrochloride) micellar solutions at different molar ratios α=[PTHC]/[SDS]) of the two components. At low values of α, polarizing microscopy observations reveal a transition from an isotropic to a nematic phase of disk-like micelles, whereas a transition to a lamellar phase occurs at higher α values > 0.5, on increasing the surfactant content. Linear rheology of the isotropic micellar solution reveal a viscous behaviour over a large range of surfactant concentrations. Surprisingly, this also extends to the nematic phase of disk-like micelles observed at α =0.2 and φ =0.35. These systems also exhibit a viscoelastic behaviour over a narrow range of surfactant concentration as reported in earlier studies. The extent of the viscoelastic region of the isotropic micellar solution also decreases with increase in α. Frequency sweep curves in this region, scaled on to a master curve is reminiscent of dilute suspensions of hard spheres or rigid Brownian rods. Consistent with the results from oscillatory shear measurements, the f;ow behaviour examined under steady shear is Newtonian over a large range of surfactant content in the isotropic micellar solution. An interesting result in these studies is the non-monotonic behaviour of the viscosity with increase in surfactant concentration. It is likely that the sharp rise in viscosity arises from a jamming effect of the rigid rods. Dynamic light scattering studies suggest that the drop in viscosity is due to the decrease in the length of the micellar aggregates. This is followed by a change in the morphology of the micelles from rods to disks as indicated by the transition to a nematic phase of disk-like micelles or a lamellar phase. A change in the morphology of micellar aggregates with increase in α is expected in mixed surfactant systems with strongly binding counterions. However, the surprising result is the change in morphology of the micellar aggregates with surfactant content. Such a behaviour is seen in mixed surfactant systems for the first time.
The thesis concludes with a summary of our main results and a brief discussion of the scope of future work in Chapter 9.
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Ionene and ionene alkyl sulfate stoichiometric complexes / Temperature and humidity sensitive materials / Ionene und Stöchiometrische Ionene-Alkylsulfat-KomplexeYu, Quanwei 03 October 2004 (has links) (PDF)
Stoichiometric polyelectrolyte-surfactant complexes represent a type of comb-shaped polymers, in which every polymer chain unit has an electrostatically bound "side chain". These complexes are water-insoluble. In the solid state they assemble spontaneously into mesogenic structures. The [X,Y]-ionenes ([(CH2)XN+(CH3)2(CH2)YN+(CH3)2]nBr-2n) investigated formed stoichiometric complexes with alkyl sulfates. The ionene alkyl sulfate complexes display mesogenicity, i.e. optically isotropic dry complexes underwent lyotropic and thermotropic phase transitions to the optically anisotropic phase (and vice versa) under controlled relative humidity. The optically anisotropic phases exhibited hexagonal textures as revealed by polarizing microscopy. A new feature is the lyotropic transition brought about by the uptake of water through the gas phase. The complexes were all sensitive to both humidity and temperature. In principle, the effects can be applied to measure humidity.
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Nichtionische polyethoxylierte Tenside in methansulfonsauren Zinn- und Zinn-Silber-Elektrolyten / Nonionic polyethoxylated surfactant in methanesulfonic Tin- and Tin-Silver-ElectrolytesWehner, Susanne 24 December 2005 (has links) (PDF)
The investigations are related to the influence of nonionic polyethoxylated surfactant on Tin- and Tin-Silver depositions. Cyclovoltammetry, electrochemical depositions in Hull cell, with quartz crystal microbalance, impedance spectroscopy, X-ray diffraction, REM and others were used as methods of characterization. / Die Untersuchungen befasssen sich mit dem Einfluss von nichtionischen polyethoxylierten Tenside auf die Zinn- und Zinn-Silber-Abscheidung, die durch Zyklovoltammetrie, Abscheidungen in der Hullzelle, mit der elektrochemischen Quarzmikrowaage, der Impedanzspektroskopie, Röntgendiffraktometrie, Rasterelektronenmikroskopie und Tensiometrie charakterisiert wurden.
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Adsorption of polyhydroxyl based surfactantsMatsson, Maria January 2005 (has links)
<p>Adsorption on solid surfaces from solution is a fundamental property of a surfactant. It might even be the most important aspect of surfactant behavior, since it influences many applications, such as cleaning, detergency, dispersion, separation, flotation, and lubrication. Consequently, fundamental investigations of surfactant adsorption are relevant to many areas.</p><p>The main aim of this thesis has been to elucidate the adsorption properties, primarily on the solid/water interface, of a particular class of polyhydroxyl based surfactants: the alkyl glucosides. By the use of ellipsometry, the equilibrium and kinetic aspects of adsorption on titanium dioxide with respect to structural effects has been studied. Furthermore, the effects of small amounts of cationic surfactant additives on the adsorption on silica have been investigated. The results have been compared with similar studies for other nonionic surfactants.</p><p>We have found that the surfactant structure has a strong effect on the adsorption properties. An increase in the surfactant chain length increases the cooperativity of the system. An increase in the head group polymerization decreases the cooperativity and the plateau adsorbed amount at equilibrium. The effect of surfactant structure on the adsorption kinetics depends on the concentration relative to the cmc, while the there is a decrease in the rate of desorption with increasing hydrophobic chain length independent of the concentration. The adsorption/desorption process is concluded to be diffusion driven, as suggested by the model used. When comparing these results with studies on ethylene oxide based surfactants, we conclude that the two types of surfactants exhibit similar trends on surfaces onto which they adsorb.</p><p>Adsorption from binary surfactant solutions is even more interesting than adsorption from single surfactant solutions, since it brings us one step closer to the systems used in applications. In addition, adsorption from a mixture can be very different from adsorption from any of the single surfactants in the mixture. Alkyl glucosides alone do not adsorb on silica, but addition of small amounts of a cationic surfactant to the alkyl glucoside solution allows for adsorption on silica. A comparison between the adsorption and bulk properties has shown that mixed micellization explains most, but not all, effects of the coadsorption properties. Changing the pH in the mixed systems reveals that a surfactant with a pH-dependent charge and the ability to adapt its charge to the environment, e.g. a surface, enhances the adsorbed amount over a wider range of pH values than a purely cationic surfactant.</p><p>It is well known that alkyl glucosides and ethylene oxides adsorb differently on different types of hydrophilic surfaces. As a consequence, replacing ethylene oxides with alkyl glucosides might not be all straight-forward; however, we have shown that the effect of the surface can be eliminated by the use of a cosurfactant.</p>
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Vibrational Sum Frequency Spectroscopy Studies at the Air-Liquid InterfaceTyrode, Eric January 2005 (has links)
<p>In this thesis the structure and hydration of small organic and amphipilic compounds adsorbed at the air-liquid interface, have been studied using the nonlinear optical technique Vibrational Sum Frequency Spectroscopy (VSFS). The second order nature of the sum frequency process makes this technique particularly surface sensitive and very suitable for interfacial studies, as molecules at the surface can be distinguished even in the presence of a vast excess of the same molecules in the bulk. Particular emphasis was given to the surface water structure and how it is affected by the presence of small model compounds such as acetic acid and formic acid, and also non-ionic surfactants with sugar based and ethylene oxide based polar headgroups. Understanding the structure of water at these interfaces is of considerable fundamental importance, and here VSFS provided unique information. Upon addition of tiny amounts of these surface active compounds, the ordered surface structure of water was found to be significantly perturbed, as revealed by the changes observed in the characteristic spectroscopic signature of the dangling OH bond of water molecules, which vibrate free in air and are present in the top monolayer. Dramatic differences between the different compounds were also observed in the bonded OH region, providing a valuable insight into the hydration of polar groups at interfaces. Additionally, by employing different polarization combinations of the laser beams involved in the sum frequency process, information about the different water species present at the surface and their average orientation were extracted. In particular an unusual state of water was found with a preferred orientation in a non-donor configuration in close proximity to the hydrophobic region formed by the hydrocarbon tails of the surfactant molecules.</p><p>The conformation and orientation of the different adsorbates were also characterized, targeting their specific vibrational frequencies. Noteworthy is the orientation of the fluorocarbon chain of ammonium perfluorononanoate (APFN), which in contrast to the hydrocarbon chains of the other surfactant molecules studied, remained constant over a wide range of surface densities. This behaviour was also observed for the anionic headgroup of sodium dodecyl sulphate (SDS). Other interesting findings were the formation of a cyclic dimer bilayer at the surface of concentrated aqueous solutions of acetic acid and the water structuring effect induced by poly(ethylene-oxide) headgroups, in spite of being themselves disordered at the air-liquid interface.</p>
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Untersuchungen zur Tensidverteilung in Reinigungsbädern in der Metall verarbeitenden IndustrieSteiner-Ander, Andrea 02 November 2001 (has links) (PDF)
In dieser Arbeit wird ein industriell genutzter Metallreiniger auf Basis nichtionischer Tenside untersucht. Dabei werden ausschließlich Messmethoden verwendet, die sich auch für eine industrielle Fertigung eignen.
Zu Anfang enthält die Arbeit kurze Abrisse zum gegenwärtigen Kenntnisstand bezüglich der Inhaltstoffe industriell genutzten Reiniger, der Analytik von Tensiden in Reinigern und der Adsorption der Tenside auf Feststoffoberflächen. Im Mittelpunkt der Arbeit steht neben der Charakterisierung und Analyse des Reinigers die quantitative Bestimmung der im Reiniger enthaltenen Tenside in industriellen Reinigungsbädern. Mit Hilfe der Hochleistungsflüssigkeitschromatografie mit einem Verdampfungs - Lichtstreudetektor wird die quantitative Verteilung der Tenside in Reinigungsbädern unter verschiedenen der industriellen Fertigung entsprechenden Bedingungen untersucht. Die Adsorption der im Reiniger enthaltenen Tenside auf der Metalloberfläche unter Fertigungsbedingungen wird mit Fluoreszenzspektroskopie und IR-Spektroskopie quantitativ bestimmt. Im letzten Kapitel wird auf die Umsetzung der gefundenen Ergebnisse in die industrielle Praxis eingegangen.
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Development and application of a 3D equation-of-state compositional fluid-flow simulator in cylindrical coordinates for near-wellbore phenomenaAbdollah Pour, Roohollah 06 February 2012 (has links)
Well logs and formation testers are routinely used for detection and quantification of hydrocarbon reserves. Overbalanced drilling causes invasion of mud filtrate into permeable rocks, hence radial displacement of in-situ saturating fluids away from the wellbore. The spatial distribution of fluids in the near-wellbore region remains affected by a multitude of petrophysical and fluid factors originating from the process of mud-filtrate invasion. Consequently, depending on the type of drilling mud (e.g. water- and oil-base muds) and the influence of mud filtrate, well logs and formation-tester measurements are sensitive to a combination of in-situ (original) fluids and mud filtrate in addition to petrophysical properties of the invaded formations. This behavior can often impair the reliable assessment of hydrocarbon saturation and formation storage/mobility. The effect of mud-filtrate invasion on well logs and formation-tester measurements acquired in vertical wells has been extensively documented in the past. Much work is still needed to understand and quantify the influence of mud-filtrate invasion on well logs acquired in horizontal and deviated wells, where the spatial distribution of fluids in the near-wellbore region is not axial-symmetric in general, and can be appreciably affected by gravity segregation, permeability anisotropy, capillary pressure, and flow barriers.
This dissertation develops a general algorithm to simulate the process of mud-filtrate invasion in vertical and deviated wells for drilling conditions that involve water- and oil-base mud. The algorithm is formulated in cylindrical coordinates to take advantage of the geometrical embedding imposed by the wellbore in the spatial distribution of fluids within invaded formations. In addition, the algorithm reproduces the formation of mudcake due to invasion in permeable formations and allows the simulation of pressure and fractional flow-rate measurements acquired with dual-packer and point-probe formation testers after the onset of invasion. An equation-of-state (EOS) formulation is invoked to simulate invasion with both water- and oil-base muds into rock formations saturated with water, oil, gas, or stable combinations of the three fluids. The algorithm also allows the simulation of physical dispersion, fluid miscibility, and wettability alteration.
Discretized fluid flow equations are solved with an implicit pressure and explicit concentration (IMPEC) scheme. Thermodynamic equilibrium and mass balance, together with volume constraint equations govern the time-space evolution of molar and fluid-phase concentrations. Calculations of pressure-volume-temperature (PVT) properties of the hydrocarbon phase are performed with Peng-Robinson's equation of state. A full-tensor permeability formulation is implemented with mass balance equations to accurately model fluid flow behavior in horizontal and deviated wells. The simulator is rigorously and successfully verified with both analytical solutions and commercial simulators.
Numerical simulations performed over a wide range of fluid and petrophysical conditions confirm the strong influence that well deviation angle can have on the spatial distribution of fluid saturation resulting from invasion, especially in the vicinity of flow barriers. Analysis on the effect of physical dispersion on the radial distribution of salt concentration shows that electrical resistivity logs could be greatly affected by salt dispersivity when the invading fluid has lower salinity than in-situ water. The effect of emulsifiers and oil-wetting agents present in oil-base mud was studied to quantify wettability alteration and changes in residual water saturation. It was found that wettability alteration releases a fraction of otherwise irreducible water during invasion and this causes electrical resistivity logs to exhibit an abnormal trend from shallow- to deep-sensing apparent resistivity. Simulation of formation-tester measurements acquired in deviated wells indicates that (i) invasion increases the pressure drop during both drawdown and buildup regimes, (ii) bed-boundary effects increase as the wellbore deviation angle increases, and (iii) a probe facing upward around the perimeter of the wellbore achieves the fastest fluid clean-up when the density of invading fluid is larger than that of in-situ fluid. / text
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Development of a four-phase flow simulator to model hybrid gas/chemical EOR processesLotfollahi Sohi, Mohammad 03 September 2015 (has links)
Hybrid gas/chemical Enhanced Oil Recovery (EOR) methods are such novel techniques to increase oil production and oil recovery efficiency. Gas flooding using carbon dioxide, nitrogen, flue gas, and enriched natural gas produce more oil from the reservoirs by channeling gas into previously by-passed areas. Surfactant flooding can recover trapped oil by reducing the interfacial tension between oil and water phases. Hybrid gas/chemical EOR methods benefit from using both chemical and gas flooding. In hybrid gas/chemical EOR processes, surfactant solution is injected with gas during low-tension-gas or foam flooding. Polymer solution can also be injected alternatively with gas to improve the gas volumetric sweep efficiency.
Most fundamentally, wide applications of hybrid gas/chemical processes are limited due to uncertainties in reservoir characterization and heterogeneity, due to the lack of understanding of the process and consequently lack of a predictive reservoir simulator to mechanistically model the process. Without a reliable simulator, built on mechanisms determined in the laboratory, promising field candidates cannot be identified in advance nor can process performance be optimized.
In this research, UTCHEM was modified to model four-phase water, oil, microemulsion, and gas phases to simulate and interpret chemical EOR processes including free and/or solution gas. We coupled the black-oil model for water/oil/gas equilibrium with microemulsion phase behavior model through a new approach. Four-phase fluid properties, relative permeability, and capillary pressure were developed and implemented. The mass conservation equation was solved for total volumetric concentration of each component at standard conditions and pressure equation was derived for both saturated and undersaturated PVT conditions.
To model foam flow in porous media, comprehensive research was performed comparing capabilities and limitations of implicit texture (IT) and population-balance (PB) foam models. Dimensionless foam bubble density was defined in IT models to derive explicitly the foam-coalescence-rate function in these models. Results showed that each of the IT models examined was equivalent to the LE formulation of a population-balance model with a lamella-destruction function that increased abruptly in the vicinity of the limiting capillary pressure, as in current population-balance models. Foam models were incorporated in UTCHEM to model low-tension-gas and foam flow processes in laboratory and field scales.
The modified UTCEM reservoir simulator was used to history match published low-tension-gas and foam coreflood experiments. The simulations were also extended to model and evaluate hybrid gas/chemical EOR methods in field scales. Simulation results indicated a well-designed low-tension-gas flooding has the potential to recover the trapped oil where foam provides mobility control during surfactant and surfactant-alkaline flooding in reservoirs with very low permeability. / text
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Characterisation of Aqueous Solutions, Liquid Crystals and Solid State of Non-ionic Polymers in Association with Amphiphiles and DrugsRidell, Annika January 2003 (has links)
Cellulose ethers and polyethylene glycols are used in drug formulations as water swelling or water soluble matrices. Polar lipids, for example monoglycerides, and surfactants can be used to solubilise hydrophobic or amphiphilic drugs and to formulate potential drug delivery vehicles such as emulsions, liposomes and cubic phases. In this thesis mixtures of these excipients are characterised in various environments, from dilute aqueous solutions to solid dispersions. Special focus has been on the understanding of the associating processes involved. Detailed understanding of the association of cellulose ethers, of varying hydrophobicity, and amphiphilic substances is presented. The hydrophobicity of the polymer was found to have an impact on the interaction scheme. The amphiphiles were found to bind at lower amphiphile concentrations to a more hydrophobic polymer thus influencing both micro- and macroscopic structure of the aggregates. The choice of counterion to the amphiphile has a small but significant effect on the interaction and the structure of the aggregates. Also amphiphilic drug molecules can interact with nonionic polymers in a similar way as surfactants in aqueous solution. Due to the higher cmc of the drug ibuprofen the interaction is largely influenced by the ionic strength of the solution. The type of amphiphile also influences the cooperativity of the amphiphile-polymer binding. In more concentrated systems liquid crystals are formed into which the polymer interact with the amphiphiles. Both cubic and sponge phases were found with relatively large polymers interacting with polar lipids. These phases were found to swell and shrink mainly controlled by the amount of polymer inside them. Also membrane interacting substances added to the sponge phase could influence the size of the water channels in the phase. In water free systems polymers and polar lipids were found to interact as well as forming solid dispersions. The behaviour of the phase separation between polymer and lipid depended on the concentration of the dispersed phase. The polar lipid was found to be distributed in the lamellar part of the semicrystalline polymer influencing the polymer folding.
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