Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: The study of water-in-oil emulsion stability and separation was carried out for this thesis. The main objectives were as follows: to rank crude oil samples in terms of creating stable emulsions; to assess the effect of the brine pH on emulsion stability; to investigate the influence of different organic acids on emulsion stability; and to determine the efficiency of an electric separator in removing water droplets from a flowing organic liquid. Seven crude oil samples from different sources such as A, C, H, M, P, U, and V were used to investigate the water-in-crude-oil emulsion. Two crude oil blends were also used. Brine solution comprising 4 wt% NaCl and 1 wt% CaCl2 was used. In this study the gravity settling, critical electric field (CEF) and centrifuge test methods were used to estimate the emulsion stability created by the crude oil and crude oil blend samples. The experiments were carried out at 60°C. In the gravity test method, the brine pH, stirring speed, stirring time and water-cut (the fraction of water in the emulsion) were changed in 2IV-1 factorial design. The parameters for the centrifuge and CEF test methods were selected on the basis of the gravity test method. The crude oil samples were ranked in terms of creating stable emulsion in the following order V, U, P, H, A, M and C. The crude oil blends created more stable emulsions than their respective constituents. The ranking order of the crude oil samples did not correlate to asphaltenes, resins, wax or total acid number (TAN). There was a good correlation between the test methods used. There was an increase and decrease in the brine pH when different crude oil samples were in contact with the brine. It is believed that the structure of the surfactants present in crude oil may explain the emulsion-forming characteristics of different crude oil deposits around the world. To account for the effect of organic acids on emulsion stability, different organic acids were used. In this case, a mixture of equal volumes of heptane and toluene (here referred to as heptol) was used as the model for crude oil. The brine solution composition was the same as the one used in the crude oil experiments. Equal volumes of heptol and brine were mixed for a period of time and then separated. The brine pH was changed from acidic to basic. In this regard, gas chromatography and liquid chromatography were used to analyse the concentration of the acids in the brine and heptol samples. It was found that the partitioning coefficient for acids containing a straight-chain hydrocarbon moiety decreased with an increase in molecular weight. However, the partitioning coefficient depended on the structure of the acid. The presence of a benzene ring in the organic acid increased the partitioning coefficient. Organic acids with rings created an interface layer when the heptol sample was mixed with basic brine solution. This confirmed that the emulsion of water and crude oil starts with the formation of a film, and it also provides insight into the formation of naphthenate soap. It is believed that the naphthenic acids that cause stable emulsions have rings. More organic acids should be tested. It is recommended that the interaction of asphaltenes, resins and naphthenic acids should be investigated at different pH levels, temperatures and pressures. The separation of water droplets from a flowing organic liquid was carried out using a direct current (d.c.) electric separator. The separator used centrifugal forces and a d.c. electric field to enhance the removal of water drops from a flowing organic liquid. For this, vegetable oil, crude oil blend and heptane were used as the continuous phase. The experiments were carried out at room temperature (for heptane and vegetable oil) and at 70°C (for vegetable oil and crude oil blend). The flow rate to the separator was kept constant. The separator removed water droplets from flowing organic liquids. A maximum of 97% (at 100 V)of water droplets was removed from the heptane liquid; a maximum of 28% (at 100 V) of water droplets was removed from the vegetable oil at 70°C and 5% (at 100 V) of water droplets was removed from the crude oil blend. The d.c. electric field enhanced the efficiency of the separator in removing water droplets. The break-up of the droplets is suspected to decrease the efficiency of the separator. This separator can easily be installed into existing process lines and does not require much space. However, further improvements are needed in the design of this separator. Emulsions created in the petroleum industries are quite complex to deal with. The identification of the structure of the components in crude oil is a matter that still has to be investigated. An improvement in the techniques may lead to a better understanding of the cause of the ultra-stable emulsion encountered in the petroleum and related industries. / AFRIKAANSE OPSOMMING: Die studie van die stabiliteit en skeiding van water-in-olie-emulsies is vir hierdie tesis uitgevoer. Die hoofdoelstellings was as volg: om ruolie-monsters in terme van die skepping van stabiele emulsies te klassifiseer; om die effek van die pekel-pH op emulsie-stabiliteit te assesseer; om die invloed van verskillende organiese sure op emulsie-stabiliteit te ondersoek; en om die doeltreffendheid van ’n elektriese skeier in die verwydering van waterdruppels uit ’n vloeiende organiese vloeistof te bepaal. Sewe ruolie-monsters uit verskillende bronne soos was A, C, H, M, P, U en V gebruik om die water-in-ruolie-emulsie te ondersoek. Twee ruolie-mengels is ook gebruik. ’n Pekeloplossing wat 4 wt% NaCl en 1 wt% CaCl2 bevat, is gebruik. In hierdie studie is die gravitasie-afsakkings-, kritieke elektriese veld- (KEV-) en sentrifuge-toetsmetodes gebruik om die emulsie-stabiliteit te beraam wat deur die ruolie- en ruolie-mengsel-monsters geskep is. Die eksperimente is teen 60°C uitgevoer. In die gravitasietoetsmetode is die pekel-pH, roertempo en watersnyding (die fraksie van water in die emulsie) is in ‘n 2IV-1-faktoriaalontwerp ondersoek. Die parameters vir die sentrifuge- en KEV-toetsmetodes is op grond van die gravitasietoetsmetode resultate gekies. Die ruolie-monsters is in terme van die skepping van ’n emulsie stabiliteit geklassifiseer in die volyende orde V, U, P, H, A, M, en C. Die rudie-menysels het meer stabiele emulsies gerorm as die respektiewe samestellende dele. Die rangorde van emulsie stabiliteit van die ruolie-monsters het nie met asfaltene, hars, waks of totale suurgetal gekorreleer nie. Daar was ’n goeie korrelasie tussen die toetsmetodes wat gebruik is. Daar was ’n toename of afname in die pekel-pH wanneer verskillende ruolie-monsters in kontak met die pekel was. Die aanname is dat die struktuur van die surfaktante wat in die ruolie teenwoordig is, die emulsievormende karaktereienskappe van verskillende ruolie-neerslae regoor die wêreld kan verklaar. Om die effek van organiese sure op emulsie-stabiliteit te verklaar, is verskillende organiese sure gebruik. In hierdie geval is ’n mengsel van gelyke hoeveelhede heptaan en tolueen (voortaan verwys na as heptol) as die model vir ruolie gebruik. Die pekeloplossing-samestelling was dieselfde as die een wat in die ruolie-eksperimente gebruik is. Gelyke hoeveelhede heptol en pekel is vir ’n tydperk gemeng en toe geskei. Die pekel-pH is van suurvormend tot basies verander. Gaschromatografie en vloeistofchromatografie is gebruik om die konsentrasie van die sure in die pekel- en heptoloplossings te analiseer. Daar is gevind dat die verdelingskoëffisiënt vir sure wat ’n reguitketting-koolwaterstofhelfte bevat met ’n toename in molekulêre gewig afneem. Die verdelingskoëffisiënt het egter van die struktuur van die suur afgehang. Die teenwoordigheid van ’n benseenring in die organiese suur het die verdelingskoëffisiënt verhoog. Organiese sure met ringe het ’n tussenvlaklaag geskep toe die heptolmonster met die basiese pekeloplossing gemeng is. Dit het bevestig dat die emulsie van water en ruolie met die vorming van ’n vlies begin, en gee ook insig in die vorming van naftenaatseep. Dit blyk dat die naftenaatsure wat stabiele emulsies veroorsaak, ringe het. Meer organiese sure moet getoets word. Daar word aanbeveel dat die interaksie van asfaltene, hars en naftenaatsure teen verskillende pH-vlakke, temperature en drukke getoets word. Die skeiding van waterdruppels uit ’n vloeiende organiese vloeistof is uitgevoer met behulp van ’n gelykstroom- elektriese skeier. Die skeier het sentrifugiese kragte en ’n wisselstroomelektriese veld gebruik om die verwydering van waterdruppels uit ’n vloeiende organiese vloeistof te verhoog. Hiervoor is plantolie, ’n ruoliemengsel en heptaan gebruik as die deurlopende fase. Die eksperimente is teen kamertemperatuur (vir heptaan en plantolie) en teen 70°C (vir plantolie en ruolie-mengsel) uitgevoer. Die vloeitempo na die skeier is konstant gehou. Die skeier het waterdruppels uit die vloeiende organiese vloeistowwe verwyder. N’ maksimum van 97% (by 100 V) van die water drupples is verweider van die heptaan vloeistof; a maksimum van 28% (by 100 V) van die water druppels was verweider van die plantolie by 70°C en 5% (by 100 V) van die water druppels was verweider van die rudie mengsel. Die gelykstroom- elektriese veld het die doeltreffendheid van die skeier om waterdruppels te verwyder, verhoog. Daar word vermoed dat die afbreek van die waterdruppels die doeltreffendheid van die skeier verlaag. Die skeier kan met gemak in bestaande proseslyne geïnstalleer word en benodig nie veel spasie nie. Verdere verbeterings is egter nodig ten opsigte van die ontwerp van hierdie skeier. Emulsies wat in die petroleumbedrywe geskep word, is kompleks om te hanteer. Die identifikasie van die struktuur van die komponente in ruolie verg verdere ondersoek. ’n Verbetering in hierdie tegnieke kan tot beter begrip lei van die oorsaak van die ultrastabiele emulsie wat in die petroleum- en verwante bedrywe aangetref word.

In order to study suspensions of deformable particles, a hybrid numerical technique was developed that combined a lattice-Boltzmann (LB) fluid solver with a finite element (FE) solid-phase solver. The LB method accurately recovered Navier-Stokes hydrodynamics, while the linear FE method accurately modeled deformation of fluid-filled elastic capsules for moderate levels of deformation. The LB/FE technique was extended using the Message Passing Interface (MPI) to allow scalable simulations on leading-class distributed memory supercomputers. An extensive series of validations were conducted using model problems, and the LB/FE method was found to accurately capture proper capsule dynamics and fluid hydrodynamics. The dilute-limit rheology was studied, and the individual normal stresses were accurately measured. An extension to the analytical theory for viscoelastic spheres [R. Roscoe. J. Fluid Mech., 28(02):273-93, 1967] was proposed that included the isotropic pressure disturbance. Single-body deformation was found to have a small negative (tensile) effect on the particle pressure. Next, the rheology and microstructure of dense suspensions of elastic capsules were probed in detail. As elastic deformation was introduced to the capsules, the rheology exhibited rapid changes. Moderate amounts of shear thinning were observed, and the first normal stress difference showed a rapid increase from a negative value for the rigid case, to a positive value for moderate levels of deformation. The particle pressure also demonstrated a decrease in compressive stresses as deformation increased. The corresponding changes in microstructure were quantified. Changes in particle self-diffusivity were also noted.

Thermal properties of complex suspension flows are investigated using numerical computations. The objective is to develop an efficient and accurate computational method to investigate heat transport in suspension flows. The method presented here is based on solving the lattice Boltzmann equation for the fluid phase, as it is coupled to the Newtonian dynamics equations to model the movement of particles and the energy equation to find the thermal properties. This is a direct numerical simulation that models the free movement of the solid particles suspended in the flow and its effect on the temperature distribution. Parallel implementations are done using MPI (message passing interface) method. Convective heat transfer in internal suspension flow (low solid volume fraction, φ<10%), heat transfer in hot pressing of fiber suspensions and thermal performance of particle filled thermal interface materials (high solid volume fraction, φ>40%) are investigated. The effects of flow disturbance due to movement of suspended particles, thermo-physical properties of suspensions and the particle micro structures are discussed.

The dynamics of fiber orientation is of great interest for efforts to predict the microstructure and material properties of a suspension flow system. In this research a fiber-level, hybrid simulation method, LBM‒EBF (coupled lattice‒Boltzmann method with the external boundary force method) is undertaken to advance the current understanding of the hydrodynamic interaction induced rotational diffusion mechanism for rigid fibers in semidilute suspension of low Reynolds number flow. The LBM‒EBF simulations correctly predict the orbit constant distribution of fibers in a sheared semidilute suspension flow. It is demonstrated that an anisotropic, weak rotary diffusion model can fit the orbit constant distribution very well, but it can not describe the asymmetry in Stokes flow observed in semidilute suspension. The rotational diffusion process is then characterized with a three dimensional spatial tensor representation of the rotational diffusivity. A scalar measure of the rotational diffusion‒'scalar Folgar‒Tucker constant', C[subscript I], is extracted from this tensor. The study provides substantial numerical evidence that the range of C[subscript I] (0.0038 to 0.0165) obtained by Folgar&Tucker (J. reinf. plast. and comp, v.3, 1984) in a semidilute regime is overly diffusive, and that the correct magnitude is of O(10⁻⁴). The study reveals that the interactions among fibers become more frequent with either the decrease of fiber aspect-ratio, r[subscript p] (keeping nL³ constant, where n is the fiber number density, and L is the fiber length) or with the increase of nL³ (keeping r[subscript p] constant) in the semidilute regime, which in consequence causes an increase in C[subscript I]. The rheological properties of sheared semidilute suspension are also computed with direct LBM‒EBF simulations. The LBM‒EBF investigation is extended to characterize the fiber orientation in a linearly contracting channel similar to a paper machine 'headbox'. It is found that the rotational diffusion is the predominant term over the strain rate in the semidilute regime for a low Reynolds number flow, and it results in a decreasing trend of rotational Peclet number, Pe, along the contraction centerline. Lastly, in order to improve the numerical consistency of the existing LBM‒EBF approach, a modification to the body force term in the LB equation is suggested, which can recover the exact macroscopic hydrodynamics from the mesoscale.

Particle suspensions are common both in nature and in various technological applications. The complex nature of hydrodynamic interactions between particles and the solvent makes such analysis difficult that often requires numerical modeling to understand the behavior of particle suspensions. In this dissertation, we employ a hybrid computational model that integrates a lattice spring model for solid mechanics and a lattice Boltzmann model for fluid dynamics. We use this model to study several practical problems in which the dynamics of spherical and spheroidal particles and deformable capsules in dilute suspensions plays an important role. The results of our studies yield new information regarding the dynamics of solid particle in pressure-driven channel flows and disclose the nonlinear effects associated with fluid inertia leading to particle cross-stream migration. This information not only give us a fundamental insight into the dynamics of dilute suspensions, but also yield engineering guidelines for designing high throughput microfluidic devices for sorting and separation of synthetic particles and biological cells. We first demonstrate that spherical particles can be size-separated in ridged microchannels. Specifically, particles with different sizes follow distinct trajectories as a result of the nonlinear inertial effects and secondary flows created by diagonal ridges in the channel. Then, separation of biological cells by their differential stiffness is studied and compared with experimental results. Cells with different stiffness squeeze through narrow gaps between solid diagonal ridges and channel wall, and migrate across the microchannel with different rates depending on their stiffness. This deformability-based microfluidic platform may be valuable for separating diseased cells from healthy cells, as a variety of cell pathologies manifest through the change in mechanical cell stiffness. Finally, the dynamics of spheroid particles in simple shear and Poiseuille flows are studied. Stable rotational motion, cross-stream migration, and equilibrium trajectories of non-spherical particles in flow are investigated. Effects of particle and fluid inertia on dynamics of particles are disclosed. The dependence of equilibrium trajectory on particle shape reveals a potential application for shape based particle separation.

Thesis (Ph.D)--Mathematics, Georgia Institute of Technology, 2008. / Committee Chair: Goldsztein, Guillermo; Committee Member: Dieci, Luca; Committee Member: McCuan, John; Committee Member: Santamarina, Juan; Committee Member: Zhou, Haomin.

The purpose of this work is to find a method of determining the average particle size in samples of clays and ceramical materials, and to attempt to classify their physical properties according to the size of the particles. Such data should be useful to compare the properties of clays, to match different samples for uniformity, and to better control processes where clays are used, as for instance in manufacture of paper, rubber, and burned wear. / M.S.

This thesis concerns the production of thermoplastic/carbon fiber composites via aqueous suspension prepregging. Suspension prepregging requires the use of a binder dispersant: i) to disperse the polymer particles so as to get good fiber-matrix distribution in the prepreg, and ii) to improve the handling characteristics of the prepreg, by holding the matrix to the fibers and the fibers to themselves. The effects of the binder on the processability, properties, and performance of composites were assessed. It was found that the addition of the binder can affect both the matrix and the composite performance depending on the binder concentration and chemistry. For example an increase of 250 % on the complex dynamic viscosity of LaRC TPI matrix was measured upon the addition of 21.3 wt% of imidized LaRC TPI polyamic acid binder at a frequency of 1 Hz. The greatest fiber-matrix adhesion was observed for PEEK composites when BisP BTDA polyamic acid was used as a binder. A preliminary, qualitative study on the possibility of using suspension prepregging as means of manufacturing thermoplastic/carbon fabric composites was performed. Good penetration of PEEK polymer particles into the fabric was obtained when the fabric was previously desized by acid digestion. A preliminary study was made on the binding and dispersing capabilities of a novel copolymer poly(pyridine ether-eo-ether ether ketone). The addition of the copolymer to PEEK drastically increased the melt viscosity due to an ionomer effect. This resulted in poorly consolidated panels with high void volumes. / Master of Science

Mathematical Modeling of Fines Migration and Clogging in Porous Media Guido Kampel 87 Pages Directed by Dr. Guillermo H. Goldsztein A porous medium is a material that contains regions filled with fluid embedded in a solid matrix. These fluid filled regions are called pores or voids. Suspensions are fluids with small particles called fines. As a suspension flows through a porous material, some fines are trapped within the material while others that were trapped may be released. Filters are an example of porous media. We model filters as networks of channels. As a suspension flows across the filter, particles clog channels. We assume that there is no flow through clogged channels. In the first part of this thesis, we compute a sharp upper bound on the number of channels that can clog before fluid can no longer flow through the filter. Soil mass is another example of porous media. Fluid in porous media flows through tortuous paths. This tortuosity and inertial effects cause fines to collide with pore walls. After each collision, a particle looses momentum and needs to be accelerated again by hydrodynamic forces. As a result, the average velocity of fines is smaller than that of the fluid. This retardation of the fines with respect to the fluid may lead to an increase of the concentration of fines in certain regions which may eventually result in the plugging of the porous medium. This effect is of importance in flows near wells where the flow has circular symmetry and thus, it is not macroscopically homogeneous. In the second part of this thesis we develop and analyze a mathematical model to study the physical effect described above. In the third and last part of this thesis we study particle migration and clogging as suspension flows through filters by means of numerical simulations and elementary analysis. We explore the effect that network geometry, probability distribution of the width of the channels and probability distribution of the diameter of the particles have on the performance of filters.

Determination of the relation between the bulk or rheological properties of a particle suspension and its microscopic structure is an old and important problem in physical science. In general, the rheology of particle suspension is quite complex, and the problem becomes even more complicated if the suspending particle is deformable. Despite these difficulties, a large number of theoretical and experimental investigations have been devoted to the analysis and prediction of the rheological behavior of particle suspensions. However, among these studies there are very few investigations that focus on the role of particle deformability. A novel method for full coupling of the fluid-solid phases with sub-grid accuracy for the solid phase is developed. In this method, the flow is computed on a fixed regular 'lattice' using the lattice Boltzmann method (LBM), where each solid particle, or fiber, is mapped onto a Lagrangian frame moving continuously through the domain. The motion and orientation of the particle are obtained from Newtonian dynamics equations. The deformable particle is modeled by the lattice-spring model (LSM).The fiber deformation is calculated by an efficient flexible fiber model. The no-slip boundary condition at the fluid-solid interface is based on the external boundary force (EBF) method. This method is validated by comparing with known experimental and theoretical results. The fiber simulation results show that the rheological properties of flexible fiber suspension are highly dependent on the microstructural characteristics of the suspension. It is shown that fiber stiffness (bending ratio BR) has strong impact on the suspension rheology in the range BR < 3. The relative viscosity of the fiber suspension under shear increases significantly as BR decreases. Direct numerical simulation of flexible fiber suspension allows computation of the primary normal stress difference as a function of BR. These results show that the primary normal stress difference has a minimum value at BR ∼ 1. The primary normal stress differences for slightly deformable fibers reaches a minimum and increases significantly as BR decreases below 1. The results are explained based on the Batchelor's relation for non-Brownian suspensions. The influence of fiber stiffness on the fiber orientation distribution and orbit constant is the major contributor to the variation in rheological properties. A least-squares curve-fitting relation for the relative viscosity is obtained for flexible fiber suspension. This relation can be used to predict the relative viscosity of flexible fiber suspension based on the result of rigid fiber suspension. The unique capability of the LBM-EBF method for sub-grid resolution and multiscale analysis of particle suspension is applied to the challenging problem of platelet motion in blood flow. By computing the stress distribution over the platelet, the "blood damage index" is computed and compared with experiments in channels with various geometries [43]. In platelet simulation, the effect of 3D channel geometry on the platelet activation and aggregation is modeled by using LBM-EBF method. Comparison of our simulations with Fallon's experiments [43] shows a similar pattern, and shows that Dumont's BDI model [40] is more appropriate for blood damage investigation. It has been shown that channels with sharp transition geometry will have larger recirculation areas with high BDI values. By investigating the effect of hinge area geometry on BDI value, we intend to use this multiscale computational method to optimize the design of Bileaflet mechanical heart valves. Both fiber simulations and platelet simulations have shown that the novel LBM-EBF method is more efficient and stable compare to the conventional numerical methods. The new EBF method is a two-Cway coupling method with sub-grid accuracy which makes the platelet simulations possible. The LBM-EBF is the only method to date, to the best of author's knowledge, that can simulate suspensions with large number of deformable particles under complex flow conditions. It is hoped that future researchers may benefit from this new method and the algorithms developed here.