No description available.

In this study, instability and failure in complex fluids (Elastoviscoplastic fluids) is explored using the classic Considère (F˙ < 0) and stress curvature (σ¨ < 0) criteria. Employing the Saramito model, numerical simulation of the extensional protocol on non-Newtonian fluids is carried out. Validation is firstly performed (with a purely viscoelastic model) and in general found to be in agreement with previous works. Parameter variation of the Bingham number (Bi), capillary number (Ca) and extension rate (ε˙) is then undertaken. It is found out that for Oldroyd-B based fluids, the stress curvature condition almost always occurs from inception of the flow for all cases. Additionally, increasing surface tension has a stabilizing effect on the extending fluid when it is below a critical value, above which it aids breakup. Increasing the yield stress, though, delays the onset of instability, but reduces the final length of the extending filament. At mild to high extension rates, the Considère criterion and the extension at the maximum stress are suit-able indicators of the final extension at strain-to-break(εST B). Furthermore, the rate of the of necking instability till final breakup varies with the εST B at moderate to high ε˙. / I denna studie undersöks instabilitet och misslyckande i komplexa vätskor (Elastoviskoplas-tiska vätskor) med den klassiska Considère (F˙ < 0) och stresskurvatur (σ¨ < 0) kriterier. Genom att använda Saramito-modellen utförs numerisk simulering av det utökade protokol-let på icke-newtonska vätskor. Valideringen utförs först (med en rent viskoelastisk modell) och i allmänhet visar sig överensstämma med tidigare verk.Parametervariation av Bingham-numret (Bi), kapillärnummer (Ca) och förlängningshastighet (ε˙) genomförs sedan. Det har visat sig att för Oldroyd-B-baserade vätskor, uppträder stresskrökningstillståndet nästan alltid från början av flödet i alla fall. Dessutom har ökande ytspänningen stabiliserande effekt på den utsträckande vätskan när den är under ett kritiskt värde, över vilket den underlättar uppbrytning. En ökning av sträckgränsen fördröjer dock instabiliteten men minskar den slutliga längden på det utsträckta filamentet. Vid milda till höga utvidgningshastigheter är Considère-kriteriet och förlängningen vid maximal spänning lämpliga indikatorer för den slutliga förlängningen vid spänning till brott (εST B). Vidare varierar frekvensen av instabilitet i halsen till slutlig upplösning med εST B vid måttlig till hög ε˙.

Dynamic grouting in rock mass has been studied since 1985 while desired penetration in rock masses with fine fractures is still a challenge because of uncertainty and complexity in the grouting process. This has attracted the attention of researchers in different countries and regions, especially in some Nordic countries such as Sweden. This study presents a comprehensive review of grouting relevant research, including factors that influence penetration, different evaluation systems (equipment, and methods), and a variety of grouting techniques. Filtration as the main obstacle is a tendency that particles of suspensions would gradually separate from the flow and block the flow path. Hence, the effects of various factors on filtration are discussed in detail based on previous research and experiments. Factors such as temperature, grain size, and w/c ratio were found to have a dominant influence on filtration stability and rheology. This means rheology and filtration are highly coupled and brings more difficulties in penetration investigation with dynamic grouting. Therefore, the influence of each factor on rheology and filtration was discussed to help with the understanding of the mechanism in different grouting techniques. Then a review of dynamic grouting methods from 1985 is made in chronological order to find the limitations on existing equipment and evaluation methods. Even it is difficult to conclude the most efficient grouting method in micro-fractures without the quantitative comparison of efficiency, this review paves the way to a more systematic exploration of novel grouting equipment and techniques. Meanwhile, a contradiction regarding the influence of high-frequency oscillatory pressure on viscosity was revealed. Rather than rapid dissipation of pressure in the slots, the thermal effect caused by high-frequency oscillatory grouting is introduced to explain its adverse impact on penetration in fractures (250 and 100μm). The potential reason is the faster hydration of grouts resulted from the increased temperature and the speed of molecular motion. In the end, by evaluating the benefits from different combinations of grouting methods. It was found that the ultrasound dispersing method along with low-frequency rectangular pressure impulse would contribute to the rheology and filtration stability in the mixing and grouting phase respectively. With the application of CDF simulation, this proposal and the assumption of the thermal effect of high-frequency oscillatory pressure can be better verified in future research. / Dynamisk injektering i bergmassa har studerats sedan 1985. Önskad tätning av bergmassor med fina sprickor är dock fortfarande en utmaning på grund av osäkerhet och komplexitet i injekteringsprocessen. Detta har uppmärksammats av forskare i olika länder och regioner, särskilt i nordiska länder såsom Sverige. Denna studie presenterar en omfattande granskning av relevant forskning, inklusive faktorer som påverkar penetration, olika utvärderingssystem (utrustning och metoder) och en mängd olika injekteringstekniker. Filtrering som ett huvudsakligt hinder är en tendens att partiklar av cementsuspensioner gradvis separerar och blockerar flödesbanan, främst i små sprickor. Därför diskuteras effekterna av olika faktorer på filtrering i detalj baserat på tidigare forskning och experiment. Faktorer som temperatur, kornstorlek och vattencementtal har en dominerande påverkan på filtreringsstabilitet och reologi. Detta innebär att reologi och filtrering är starkt kopplade och medför fler svårigheter vid injektering. Därför diskuteras varje faktors påverkan på reologi och filtrering för att hjälpa till att förstå mekanismen i olika injekteringstekniker. Därefter görs en översyn av dynamiska injekteringsmetoder från 1985 i kronologisk ordning för att hitta begränsningarna för befintlig utrustning och utvärderingsmetoder. Även om det är svårt att avgöra den mest effektiva injekteringsmetoden vid mikrofrakturer, utan den kvantitativa jämförelsen av effektivitet, banar denna översyn vägen för en mer systematisk studie av ny injekteringsutrustning och teknik. Samtidigt påvisades en motsättning angående påverkan av högfrekvent oscillerande tryck på viskositeten. I stället för en snabb tryckförlust i sprickor introduceras den termiska effekten som orsakas av högfrekvent oscillerande injektering för att förklara dess negativa inverkan på penetration i tunna sprickor (250 och 100μm). Den potentiella orsaken är den snabbare hydratiseringen av injekteringsmedel som beror på den ökade temperaturen och hastigheten på molekylär rörelse. Genom att i slutändan utvärdera fördelarna med olika kombinationer av injekteringsmetoder. Det har visat sig att metoden med ultraljud för att dispergera injekteringsbruket tillsammans med lågfrekvent rektangulär tryckimpuls påverkar reologin och filtreringsstabiliteten i blandnings- och injekteringsfasen. Med tillämpningen av CDF-simulering kan antagandet om den termiska effekten av högfrekvent oscillerande tryck verifieras bättre i framtida forskning.

<p>Hydrogenated castor oil (HCO) crystals as a rheology modifier have been widely used in paints, cosmetics and household products. In this thesis, we are interested in the effect of crystal morphology on the suspension rheology of products. Three major types of micron-sized crystal morphologies have been observed: fiber, rosette and irregular crystal. Fibers show a high aspect ratio with the length ranging from 5 to 33 µm and width around 1~3 µm. The rosette (2~50 µm) is a three-dimensional spherulitic structure with nano-fibrous arms extruding from a heterogeneous central point. Irregular crystals with equivalent diameter ranging from 4 to 84 µm are hard solid and show irregular shapes. There is an additional fourth type of crystal morphology which is a nano-sized fibrous structure that is assumed to be broken down from arms of micron-sized rosettes and fibers. Due to the relatively small amount, the effects of nano-fibrous fragments on rheology were not considered separately in this work.</p> <p>The effect of temperature and shear history on the HCO crystal morphology has been studied. The energy barrier to nucleation for fibers is suggested to be higher than that of rosettes. Irregular crystals are thermodynamically less stable and tend to transform into stable polymorphs. A non-isothermal crystallization study showed that the formation of rosettes and fibers was favored by a slow cooling rate (1°C/min) while the formation of irregular crystals was favored by a fast cooling rate (5°C/min). Shear rates from zero to 100 s^-1 have been applied at cooling rates from 1°C/min to 5°C/min. Nucleation has been found to be promoted with the increase of shear rate. Morphological analysis indicated that the formation of fibers was favored by gentle shear (e.g., 1 s^-1), but fibers can be broken with the increase of shear time.</p> <p>Kinetics of isothermal crystallization of hydrogenated castor oil in water emulsions exhibiting multiple crystal morphologies has been studied in the temperature range of 55°C to 70°C. The induction time of nucleation increases with the increase of the isothermal temperature under which crystallization occurred. A linear increase in induction time with increased temperature was found for both fibers and rosettes. A modified Avrami model was developed by introducing the volume fraction of each type of morphology into three dimensional and one dimensional full Avrami models. It was found that the experimental trends for mixed crystal morphologies could be captured by the modified Avrami model.</p> <p>Due to the difficulty of obtaining samples with a single crystal morphology, rheological studies of suspensions containing mixtures of the three morphologies in a surfactant solution have been undertaken. The viscometry of dilute suspensions has shown that the magnitude of intrinsic viscosity is dominated by the fraction of a crystal morphology type, i.e. fiber > rosette > irregular crystal. A modified Farris model was fitted to the rheology data from mixtures of crystal morphology with interacting particles. A yield stress exists for concentrated suspensions followed by a shear thinning behavior with the increase of shear rate. A power-law relation has been found between yield stress and total particle volume fraction with a constant exponent of 1.5 regardless of crystal morphology.</p> / Doctor of Philosophy (PhD)

No description available.

No / A small-scale flow cell has been developed and used for small-angle neutron scattering (SANS) investigations of polymer melts in Poiseuille flow through a 4:1 contraction. The cell enables the investigation of polymer melt flow subject to a volumetric flow rate of up to 6 cm3 s-1, at pressures up to 10 MPa, temperatures up to 230°C, and a melt viscosity up to 65000 Pas. The cell has recirculating flow path and a relatively small capacity (circa 200 g of polymer) so that polymers with novel and well-defined molecular architectures may be investigated. The details of its construction and operation are described. When two walls of the cell are composed of zero order birefringent sapphire, both small-angle neutron scattering and birefringence studies can be undertaken in the same cell providing a link between macroscopic and molecular level descriptions of the influence of melt flow. Both birefringence and the first melt flow SANS data for a monodisperse, linear polystyrene are presented. These demonstrate the capability and potential of the apparatus to provide data which provide a crucial test for molecular theories of the rheology of entangled polymer melts. However, the use of sapphire windows limits the maximum flow rate that can be used and higher flows necessitated an all aluminum flow cell to cope with the higher pressures developed in flow. Clear evidence of a stretching of the molecule in the direction of the melt flow and a contraction perpendicular to the flow direction has been provided

A slit die has been constructed to use both flow birefringence and direct pressure measurements to study the extrapolated exit pressure (Px) and the exit pressure theory used to evaluate the magnitude of the primary normal stress difference (N1) from the value of the exit pressure. Flow birefringence is used to directly assess the principal assumptions in the exit pressure theory and to evaluate the magnitude of Px from an expression derived from the macroscopic momentum balance equation. The effect of stress field rearrangement upstream of the die exit plane on the value of the exit pressure was then evaluated using flow birefringence data. The effect of stress field rearrangement was also shown to affect the pressure drop ΔP/ΔL in the exit region of the die and the pressure distribution from the centerline of the slit to the die wall. To complement the experimental investigation, a mixed penalty method finite element simulation of the die swell problem was performed using the White-Metzner and upper-convected Maxwell constitutive equations. The flow birefringence experiments were performed for a polystyrene (Styron 678), LDPE (NPE 952), and HDPE (LY600-00) melts for the following shear rate (γ̇) and wall shear stress (σw) 0.05 ≤ γ̇w ≤ 3.2 s⁻¹ and 4.84 ≤ σw ≤ 16.4 KPa. It was found that the flow in the die exit region is not a unidirectional shear flow, which is direct violation of the assumptions in the exit pressure theory. Normal stresses generated by an elongational flow field were observed along the slit centerline and in the region adjacent to the die walls. Also, shear stress contributions due to stress field rearrangement evaluated using an expression obtained from a macroscopic momentum balance, comprise over 50% of the magnitude of the calculated exit pressure. The numerically calculated stress field was in good agreement with the results of the flow birefringence results. Convergence for the numerical technique was limited to Deborah numbers of 0.61 for the White-Metzner model and 0.75 for the upper-convected Maxwell constitutive equation. / Ph. D.

Magnetic nanoparticles coated with polymers hold great promise as materials for applications in biotechnology. In this body of work, magnetic fluids for the treatment of retinal detachment are examined closely in three regimes; motion of ferrofluid droplets in aqueous media, size analysis of the polymer-iron oxide nanoparticles, and calculation of interparticle potentials as a means for predicting fluid stability. The macromolecular ferrofluids investigated herein are comprised of magnetite nanoparticles coated with tricarboxylate-functional polydimethylsiloxane (PDMS) oligomers. The nanoparticles were formed by reacting stoichiometric concentrations of iron chloride salts with base. After the magnetite particles were prepared, the functional PDMS oligomers were adsorbed onto the nanoparticle surfaces. The motion of ferrofluid droplets in aqueous media was studied using both theoretical modeling and experimental verification. Droplets (~1-2 mm in diameter) of ferrofluid were moved through a viscous aqueous medium by an external magnet of measured field and field gradient. Theoretical calculations were made to approximate the forces on the droplet. Using the force calculations, the times required for the droplet to travel across particular distances were estimated. These estimated times were within close approximation of experimental values. Characterization of the sizes of the nanoparticles was particularly important, since the size of the magnetite core affects the magnetic properties of the system, as well as the long-term stability of the nanoparticles against flocculation. Transmission electron microscopy (TEM) was used to measure the sizes and size distributions of the magnetite cores. Image analyses were conducted on the TEM micrographs to measure the sizes of approximately 6000 particles per sample. Distributions of the diameters of the magnetite cores were determined from this data. A method for calculating the total particle size, including the magnetite core and the adsorbed polymer, in organic dispersions was established. These estimated values were compared to measurements of the entire complex utilizing dynamic light scattering (DLS). Better agreement was found for narrow particle size distributions as opposed to broader distributions. The stability against flocculation of the complexes over time in organic media were examined via modified Derjaguin-Landau-Verwey-Overbeek (DLVO) calculations. DLVO theory allows for predicting the total particle-particle interaction potentials, which include steric and electrostatic repulsions as well as van der Waals and magnetic attractions. The interparticle potentials can be determined as a function of separation of the particle surfaces. At a constant molecular weight of the polymer dispersion stabilizer, these calculations indicated that dispersions of smaller PDMS-magnetite particles should be more stable than those containing larger particles. The rheological characteristics of neat magnetite-PDMS complexes (i.e, no solvent or carrier fluid were present) were measured over time in the absence of an applied magnetic field to probe the expected properties upon storage. The viscosity of a neat ferrofluid increased over the course of a month, indicating that some aggregation occurred. However, this effect could be removed by shearing the fluids at a high rate. This suggests that the particles do not irreversibly flocculate under these conditions. / Ph. D.

Use of a mixed triisobutylaluminum/1,1-diphenylhexyllithium intiator enabled the anionic polymerization of methyl methacrylate at room temperature, resulting in narrow molecular weight distributions and syndiorich structures. Polymerizations were controlled above Al:Li = 2, and control significantly decreased at elevated temperatures above 25 °C. A significant increase in Tg with increasing control of syndiotacticity demonstrated the ability to tailor polymer properties using this technique. Analysis with MALDI-TOF/TOF spectroscopy revealed the dominance of a back-biting side reaction at elevated temperatures. Hydroxy-functional random and block copolymers of n-butyl acrylate (nBA) and 2-hydroxyethyl acrylate were synthesized using nitroxide mediated polymerization. Controlled polymerization was demonstrated, resulting in narrow polydispersities and linear molecular weight vs. conversion plots. In situ FTIR spectroscopy monitored the polymerizations and revealed pseudo first order rate kinetics for random copolymerizations. Protection of the hydroxyl using trimethylsilyl chloride alleviated isolation issues of amphiphilic polymer products. For the first time zwitterion-containing copolymers were electrospun to form nanoscale fibers with diameters as low as 100 nm. Free radical copolymerization of nBA and sulfobetaine methacrylamide produced zwitterionic copolymers with 6-13 mol % betaine. Dynamic mechanical analysis revealed a rubbery plateau and biphasic morphology similar to ionomers. Electrospinning from chloroform/ethanol solutions (80/20 v/v) at 2-7 wt % afforded polymeric fibers at viscosities below 0.02 Pa™s, which is the lowest viscosity observed for fiber formation in our laboratories. We hypothesized that intermolecular interactions rather than chain entanglements dominated the electrospinning process. Solution rheology of zwitterionic copolymers containing 6 and 9 mol % sulfobetaine methacrylate functionality revealed two concentration regimes with a boundary at ~1.5 – 2.0 wt %, regardless of molecular weight. This transition occurred at an order of magnitude lower specific viscosity than the entanglement concentration (Ce) for poly(nBA), and correlated to the onset of fiber formation in electrospinning. Comparison to existing models for polymer solution dynamics showed closest agreement to Rubinstein's theory for associating polymers, in support of our hypothesis that zwitterionic interactions dominate solution dynamics. The effect of ionic liquid (IL) uptake on mechanical properties and morphology of zwitterionic copolymers was explored using 1-ethyl-3-methylimidazolium ethylsulfate (EMIm ES). Dynamic mechanical analysis and impedance spectroscopy revealed a significant change in properties above a critical uptake of ~10 wt % IL. X-ray scattering revealed a significant swelling of the ionic domains at 15 wt % IL, with a 0.3 nm-1 shift in the ionomer peak to lower scattering vector. Results indicated the water-miscible IL preferentially swelled ionic domains of zwitterionic copolymers. / Ph. D.

With this research, we work towards the overall objective of being able to accurately simulate fiber orientation in complex flow geometries of composite fluids of industrial significance. The focus of this work is to understand the rheological behavior of these materials and its connection to fiber orientation as determined in simple shear flow. The work includes the development of a novel approach to characterizing the transient rheology; an experimental study of the relationship between the stress growth functions in startup of flow and the fiber orientation; a critical assessment of the limitations of current fiber suspension theory; and an approach to determining unambiguous model parameters by fitting. A key difference between the rheological studies performed in this work and others is the use of a cone-and-plate device combined with "donut" shaped samples (CP-D) to prevent boundary effects on the measurement. The conventional method for obtaining transient rheological data is to use parallel disk (PP) geometry set at a gap where the measurements are independent of disk spacing. However, this work suggests that the inhomogeneous velocity gradient imposed by the PP geometry induces excessive fiber-fiber contact contributing to exaggerated measurements of the stress growth functions. An experimental study of the transient rheological behavior of a 30 wt% short glass fiber-filled polybutylene terephthalate was performed using the CP-D. Stress growth measurements during startup of flow were performed in combination with direct measurement of the fiber orientation to determine the relationship between the transient rheology and the fiber microstructure. The well defined fiber orientation and rheological experiments allowed for a quantitative assessment of current fiber suspension theory. Comparison between the experimental fiber orientation and predictions based on Jeffery's equation and the Folgar-Tucker model show that the fiber orientation evolves much slower than predicted. In addition, the addition of a "slip" term improved the agreement between the predictions and experimental results. Predictions using the Lipscomb model coupled with the Folgar-Tucker model, with slip, were fit to the transient stresses to determine the feasibility of fitting unambiguous model parameters for a specific composite fluid. Model parameters determined by fitting at a shear rate of 6 s-1 allowed for reasonable predictions of the transient stresses in flow reversal experiments at all the shear rates tested. / Ph. D.