No description available.

Thesis (doctoral)--Lund University, 1994. / Added t.p. with thesis statement inserted.

Thesis (Ph. D.)--University of Chicago, Dept. of Physics, June 2002. / Includes bibliographical references. Also available on the Internet.

No description available.

Much research has been carried out in recent years on Pickering emulsions, but understanding of the underlying physics requires considerable strengthening. This thesis seeks to address several fundamental aspects by presenting the results of recent experimental work. This work has focused on a model oil-in-water emulsion system stabilised by fluorescent colloidal silica particles and using a mixture of dodecane and isopropyl myristate as the oil phase. The phase behaviour of the particle dispersions has been altered using sodium chloride and sodium iodide, whilst sodium hydroxide and hydrochloric acid have been used to adjust the pH of samples. Comparisons are also made to emulsions stabilised by commercially available fumed silica. Conventionally, it was assumed that a weakly flocculating particle dispersion is required in order to generate a stable Pickering emulsion. It is shown in this work, however, that in some circumstances a weakly flocculating dispersion leads to the least stable emulsion. It is therefore argued that a more nuanced view of Pickering stabilisation is required, taking into account the factors affecting whether particles will adsorb to the interface during emulsification. Very recently it has begun to be suspected that Pickering emulsions sometimes aggregate due to the sharing of particles between two droplets, an effect known as bridging. In this thesis it is also shown that particle bridges can form in Pickering emulsions at high shear, and that they can subsequently be broken by low shear or by modifying the particle wettability. For the first time, electron microscopy has been used to provide direct evidence of droplets sharing particles. A simple theoretical model is developed, based on collisions between partially coated droplets, which captures the trends observed experimentally. It is argued that particle bridging may have been overlooked in the literature, and that the shear history of emulsions is a crucial determinant of subsequent behaviour. The deaggregation of bridged emulsions has been studied using a novel method where two different colours of particles are used. By starting with two emulsions which are bridged, each stabilised by a different colour of particle, and then using confocal microscopy to study them as they are mixed together and deaggregate, the processes involved in deaggregation can be elucidated. These experiments have also shown, for the first time, the dynamic nature of particles in Pickering emulsions; particles transfer readily between droplets when the samples are placed on a roller bank. It is found that a period of unbridging and rebridging takes place prior to deaggregation of the emulsions, and the timescale of deaggregation can be tuned by varying the particle wettability. The two-colour method has also been applied to the study of Pickering emulsions which are repeatedly sheared. It is found that limited coalescence is not reestablished simply by re-applying the shear rate which was used in the initial emulsification. This behaviour is attributed to the presence of an elastic shell of particles at the interface, which inhibits droplet breakup, and is in contrast to that of surfactant-stabilised emulsions, where increasing the stabiliser concentration makes droplets more liable to deform and breakup. Finally, a short study has been carried out attempting to increase the scale of the experiments presented in this thesis to sample volumes of approximately one litre. This study has demonstrated the relevance of particle bridging to industrial emulsification processes. Overall, experiments with carefully controlled model Pickering emulsions, including those using two colours of particles, have revealed the fundamental workings of these arrested systems.

An apparatus is described that can determine electrophoretic mobilities of polar and non-polar colloidal dispersions down to -12 2 10 msV -1 -1 with typical resolutions of 0.5 to 5%, depending on the nature of the dispersion being studied. The diffusion coefficient and settling/convection velocity of the sample may be determined simultaneously in real time with the electrophoretic mobility. The technique, phase analysis light scattering (PALSY, is based upon classical laser-Doppler electrophoresis, but employs signal processing of the time domain phase information within the scattered light signal, rather than analysis of its frequency spectrum. This allows much smaller electric field strengths to be employed, thereby alleviating the usual heating problems associated with electrophoretic studies of non-polar dispersions. PALS measurements of typical aqueous latex dispersions with large mobilities and non-polar dispersions with very small mobilities (down to 5x 10_12 m2 s-1 V-1) are presented to illustrate the versatility of the technique.

No description available.

Within a colloidal dispersion, the presence of negatively adsorbing material can produce a variety of effects on the dispersion properties and interactions. With increasing concentration, the negatively adsorbing material induces both depletion and structural forces on the dispersion, which can dramatically affect both colloidal stability and near-contact hydrodynamics. This project focused on expanding our understanding of the effects of such negatively adsorbing materials on both equilibrium and dynamic interactions between particles. The effects of charged, hard spheres (silica nanoparticle) on the hydrodynamic drag force a particle experiences as it approaches a flat plate were measured experimentally using colloid probe atomic force microscopy (CP-AFM). Deviation was found between the measured drag force and predictions for the drag force in a simple, Newtonian fluid. The measured drag force was always smaller than the predicted drag force as the particle approached contact with the plate. An effective viscosity, that approached the dispersing fluid viscosity at contact and the bulk viscosity at large separations, was determined for the system. This effective viscosity displayed similar characteristics to those predicted theoretically by Bhattacharya and Blawzdziewicz (J. Chem. Phys. 2008, 128, 214704.). The effects of both anionic and cationic micelles on the depletion and structural forces in a colloidal dispersion were studied both experimentally (with CP-AFM) and theoretically. The depletion and structural forces between a microparticle and a flat plate were measured and compared with the depletion force predicted by the force-balance model of Walz and Sharma (J. Colloid Interface Sci. 1994, 168, 485-496.). Consistent with previous work, the measured depletion force for both micelles was smaller in magnitude than that predicted by the Walz and Sharma model for hard, charged spheres. It is theorized that rearrangement of the micelle surfaces charges or physical deformation of the micelles may be responsible for the observed result. An effective surface potential for the micelles is proposed as a correction to the Walz and Sharma model. Finally, the stability of colloidal dispersions was studied macroscopically in solutions of ionic micelles. The colloidal dispersions displayed clear flocculation behavior in both cationic and anionic micelles. This flocculation behavior was compared with energy profiles determined from CP-AFM experiments between a single particle and a flat plate. A simple phase diagram was proposed for predicting the stability of colloidal dispersions based solely on the depth of the depletion energy well and the height of the repulsive energy barrier. / Ph. D.

An experimental investigation was conducted to evaluate the possible use of highly-charged spherical nanoparticles to stabilize an aqueous dispersion of weakly-charged microspheres. At low pH values, the surface of silica is weakly charged, which leads to flocculation of colloidal suspensions of silica microspheres. Binary solutions of weakly charged silica microspheres and highly charged polystyrene latex nanoparticles result in adsorption of the nanoparticles onto the surface of the silica microspheres. This effectively "recharges" the silica spheres, with effective zeta potentials increased to the range that is unfavorable for flocculation of microspheres in a silica-only solution. However, this does not guarantee stability, and comparisons between positively charged amidine latex nanoparticles and negatively charged sulfate latex nanoparticles indicate that the degree of coverage plays an important role in the restabilization. The sulfate latex nanoparticles do not cover the surface sufficiently, and though they seemingly provide sufficient charge, the weakly charged patches of the exposed silica substrate can lead to flocculation. The amidine latex nanoparticles, on the other hand, cover the surface more completely, and effectively prevent flocculation of the silica microspheres. The mechanisms responsible for this different adsorption and stabilizing behavior are not entirely understood, as both the amidine and sulfate latex nanoparticles are of similar size and the magnitude of the zeta potentials of the different particle types are comparable. / Master of Science

One of the most significant problems faced in the geothermal power industry is that of scaling due to amorphous silica. The silica can deposit out of super-saturated brine in monomeric form and as colloidal particles. Deposition can occur at problematic rates on pipe surfaces and in the rocks of the re-injection wells. Currently there are a number of methods for controlling deposition but the fundamental mechanisms that govern the transport and attachment of silica are not well understood. Many field experiments on silica scaling have been conducted but, due to differences in brine chemistry and operational conditions, the results are hard to compare. Many laboratory experiments have also been performed but these are difficult to correlate with the field experiments. Previous research has found that hydrodynamics are important for the deposition of colloidal particles and inertial impaction was proposed to be the dominant transport mechanism. These results were analysed and, in contradiction, the dominant transport mechanism of the particles was theoretically expected to be that of diffusion. A series of experiments were planned that could test the effect of hydrodynamics on colloidal silica deposition in cylindrical pipe flow. Three parameters were to be varied in the experiment: particle size (10nm and 100nm), Reynolds number (750 - 23,600) and viscous boundary layer thickness (0.06 - 0.38mm). To perform this experimentation, a Silica Scaling Test Rig was designed, built and commissioned. A method for producing synthetic brine was developed which can provide sols that are stable for at least one month and have a particle size of 10-20nm. Silica deposition has successfully been obtained in three preliminary experiments using the rig. Without the exclusion of air from the rig significant corrosion occurs in the mild steel test piece. Protrusions that were likely to be silica deposits were found to be co-located with the corrosion, suggesting that one process promotes the other. Neither deposition nor corrosion was found on the pipe’s weld seam and heat affected zone. Corrosion was prevented using an oxygen exclusion system and two amorphous silica deposition structures were observed: a flat plate-like structure and a globular structure that consisted of 1-5μm diameter globules that built up on each other. Other field and laboratory experiments have produced globular structures similar to those found in this research. To perform the planned experimentation, future work is required: the silica deposition rate must be increased, colloidal silica sol stability must be improved, and some modifications must be made to the rig.