Particle Collision Electrochemistry (PCE) has gained considerable attention in heterogeneous catalysis, petroleum chemistry and pharmaceutical fields. The PCE refers to a phenomenon in which a particle strikes on an inert electrode surface as a consequence of its Brownian motion and produces a spike of current for the direct oxidation/reduction of the individual particle. This method allows us characterization of individual particles and in-situ study of electrochemical reactions coupled to the particle. Herein, emulsion droplets were studied by PCE where toluene droplets contained hydrophobic tetrachloro-1,4-benzoquinone (Q). This was investigated as a model system to study the molecular effects that arise due to hydrogen bonding reagents (oleic acid, acetic acid) inside and outside of the droplets. The emulsions were prepared by sonicating toluene-quinone solution with the water phase containing an ionic liquid to provide conductivity to the droplet. Each droplet produced a current spike while colliding with the electrode surface that was held at a potential to reduce tetrachoro-1,4-benzoquinone. In bulk acetonitrile and toluene, tetrachoro-1,4-benzoquinone undergoes a two electron reduction process to form the tetrachloro phenolate di-anion (Q2-). It was shown that the hydrogen bonding affinity of Q2- for acetic acid (pKa = 4.8) was higher than for oleic acid (pKa = 9.9) for both bulk systems (as acetic acid is stronger hydrogen bonding donor than oleic acid). However, the reversed trend was observed in emulsified toluene droplets when studied by PCE. This was attributed to the preferential partition of the carboxylic acids between the two phases in the emulsion. Oleic acid stays inside the droplets due its hydrophobic nature and hydrogen bonding with Q2- takes place inside the droplet. In contrast, solvation of acetic acid by the surrounding water, causes the hydrogen bonding with Q2- to occur significantly less inside the droplet. Another redox system studied by PCE was hydrophobic ferrocene (Fc) trapped in the toluene droplet to determine the effect of surfactant on the particle size. The diameter determined electrochemically was compared with Dynamic Light Scattering (DSL) measurements. The presence of nonionic surfactant (triton X-100) was observed to affect the droplet’s size easily monitored by PCE. The mediated oxidation of cysteine by the oxidized Fc inside the droplet was investigated at different concentrations of cysteine.

Doctor of Philosophy (PhD), Engineerig / Free radical emulsion polymerization (FRP) is widely adopted in industry due to its applicability to a wide range of monomers. Despite its many benefits and wide spread use, the fast chain growth and the presence of rapid irreversible termination impose limitations with respect to the degree of control in FRP. Furthermore, producing block copolymers and polymers with complex structures via FRP is not feasible. Closer control of macromolecular chain structure and molar mass, using novel polymerization techniques, is required to synthesize and optimize many new polymer products. Reversible addition fragmentation chain transfer (RAFT)-mediated polymerization is a novel controlled living free radical technique used to impart living characters in free radical polymerization. In combination with emulsion polymerization, the process is industrially promising and attractive for the production of tailored polymeric products. It allows for the production of particles with specially-tailored properties, including size, composition, morphology, and molecular weights. The mechanism of RAFT process and the effect of participating groups were discussed with reviews on the previous work on rate retardation. A mathematical model accounting for the effect of concentrations of propagating, intermediate, dormant and dead chains was developed based on their reaction pathways. The model was combined with a chain-length dependent termination model in order to account for the decreased termination rate. The model was validated against experimental data for solution and bulk polymerizations of styrene. The role of the intermediate radical and the effect of RAFT agent on the chain length dependent termination rate were addressed theoretically. The developed kinetic model was used with validated kinetic parameters to assess the observed retardation in solution polymerization of styrene with high active RAFT agent (cumyl dithiobenzoate). The fragmentation rate coefficient was used as a model parameter, and a value equal to 6×104 s-1 was found to provide a good agreement with the experimental data. The model predictions indicated that the observed retardation could be attributed to the cross termination of the intermediate radical and, to some extent, to the RAFT effect on increasing the average termination rate coefficient. The model predictions showed that to preserve the living nature of RAFT polymerization, a low initiator concentration is recommended. In line with the experimental data, model simulations revealed that the intermediate radical prefers fragmentation in the direction of the reactant. The application of RAFT process has also been extended to emulsion polymerization of styrene. A comprehensive dynamic model for batch and semi-batch emulsion polymerizations with a reversible addition-fragmentation chain transfer process was developed. To account for the integration of the RAFT process, new modifications were added to the kinetics of zero-one emulsion polymerization. The developed model was designed to predict key polymer properties such as: average particle size, conversion, particle size distribution (PSD), and molecular weight distribution (MWD) and its averages. The model was checked for emulsion polymerization processes of styrene with O-ethylxanthyl ethyl propionate as a RAFT based transfer agent. By using the model to investigate the effect of RAFT agent on the polymerization attributes, it was found that the rate of polymerization and the average size of the latex particles decreased with increasing amount of RAFT agent. It was also found that the molecular weight distribution could be controlled, as it is strongly influenced by the presence of the RAFT based transfer agent. The effects of RAFT agent, surfactant (SDS), initiator (KPS) and temperature were further investigated under semi-batch conditions. Monomer conversion, MWD and PSD were found to be strongly affected by monomer feed rate. With semi-batch mode, Mn and <r> increased with increasing monomer flow rate. Initiator concentration had a significant effect on PSD. The results suggest that living polymerization can be approached by operating under semi-batch conditions where a linear growth of polymer molecular weight with conversion was obtained. The lack of online instrumentation was the main reason for developing our calorimetry-based soft-sensor. The rate of polymerization, which is proportional to the heat of reaction, was estimated and integrated to obtain the overall monomer conversion. The calorimetric model developed was found to be capable of estimating polymer molecular weight via simultaneous estimation of monomer and RAFT agent concentrations. The model was validated with batch and semi-batch emulsion polymerization of styrene with and without RAFT agent. The results show good agreement between measured conversion profiles by calorimetry with those measured by the gravimetric technique. Additionally, the number average molecular weight results measured by SEC (GPC) with double detections compare well with those calculated by the calorimetric model. Application of the offline dynamic optimisation to the emulsion polymerization process of styrene was investigated for the PSD, MWD and monomer conversion. The optimal profiles obtained were then validated experimentally and a good agreement was obtained. The gained knowledge has been further applied to produce polymeric particles containing block copolymers. First, methyl acrylate, butyl acrylate and styrene were polymerized separately to produce the first block. Subsequently, the produced homopolymer attached with xanthate was chain-extended with another monomer to produce block copolymer under batch conditions. Due to the formation of new particles during the second stage batch polymerization, homopolymer was formed and the block copolymer produced was not of high purity. The process was further optimized by operating under semi-batch conditions. The choice of block sequence was found to be important in reducing the influence of terminated chains on the distributions of polymer obtained. It has been found that polymerizing styrene first followed by the high active acrylate monomers resulted in purer block copolymer with low polydispersity confirmed by GPC and H-NMR analysis.

Since oil-in-water emulsions combine good cooling and lubricating capabilities, they have been commonly used in cold rolling nowadays. In order to understand the tribology characteristics of the emulsion during the cold rolling process, the effects of load, sliding speed, material of specimen, surface roughness and type of emulsion on the tribology characteristics of cold rolling are investigated by using the multi-purpose friction and wear tester.The P (load) ¡VV (sliding speed) curve was investigated under the conditions of load (below 2.4GPa), sliding speed (below 2.2m/s) at lower specimen roughness. Results show that QK-N36 emulsion can differentiate between boundary lubrication regime and initial seizure according to their friction coefficient, but RL-61 emulsion cannot differentiate them. Therefore, the load carrying capacity of RL-61 emulsion is better than that of QK-N36 emulsion, and its friction coefficient is also lower than that of QK-N36 emulsion. However, this tendency of experimental results is different from the cold-rolling practice.Under the lower load and higher surface roughness conditions with different hardness of specimen, the friction coefficient of RL-61 emulsion is higher than that of QK-N36 emulsion. This tendency of experimental results is the same as the rolling practice. Under the lower load condition with SDK-11 specimen, the friction coefficient of RL-61 emulsion varies gradually in the range of 0.07 ~ 0.09 located in the boundary lubrication regime, but the friction coefficient of QK-N36 emulsion reduces to 0.02~0.04 located in the mixed lubrication regime.

Solids-stabilized water-in-oil emulsions have been suggested as a drive fluid to recover viscous oil through a piston-like displacement pattern. While crude heavy oil was initially suggested as the base oil, an alternative oil ? used engine oil was proposed for emulsion generation because of several key advantages: more favorable viscosity that results in better emulsion injectivity, soot particles within the oil that readily promote stable emulsions, almost no cost of the oil itself and relatively large supply, and potential solution of used engine oil disposal. In this research, different types of used engine oil (mineral based, synthetic) were tested to make W/O emulsions simply by blending in brine. A series of stable emulsions was prepared with varied water contents from 40~70%. Viscosities of these emulsions were measured, ranging from 102~104 cp at low shear rates and ambient temperature. Then an emulsion made of 40% used engine oil and 60% brine was chosen for a series of coreflood experiments, to test the stability of this emulsion while flowing through porous media. Limited breakdown of the effluent was observed at ambient injection rates, indicating a stability of the emulsion in porous media. Pressure drops leveled off and remained constant at constant rate of injection, indicating steady-state flows under the experimental conditions. No plug off effect was observed after a large volume of emulsion passed through the cores. Reservoir scale simulations were conducted for the emulsion flooding process based on the emulsion properties tested from the experiments. Results showed significant improvement in both displacement pattern and oil recovery especially compared to water flooding. Economics calculations of emulsion flooding were also performed, suggesting this process to be highly profitable.

No description available.

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In this study, a model suitable for the plasto-hydrodynamic lubrication of cold rolling with the oil-in-water emulsions has been developed. The coupled modified Reynolds and von Karman equations are solved by the Newton-Raphson method. In the numerical simulation, the main factors of influencing the numerical convergence are the initial guess for the inlet film thickness and the inlet speed of strip. The inlet film thickness can be estimated by the Wilson and Walowit formula [5]. The effects of oil volume fraction, surface speed of roller, reduction ratio, forward tension, backward tension, pressure viscosity coefficient, and surface tension group on the lubricating properties of cold rolling are investigated. Results show that the film thickness increases with increasing surface speed of roller, but its effects on the film pressure, the roll force and the roll torque are not conspicuous. In addition, the film thickness increases as the pressure viscosity coefficient increases. In the condition of the very low pressure viscosity coefficient, hydrodynamic lubrication of cold rolling works by enhancing the forward tension. Ahead of the roll bite, the metal surface has a higher affinity to the oil phase so that water is excluded and the oil pooling is formed because of the difference in the viscosity of the two components of the emulsion. Hence, in the condition of the lower initial oil volume fraction, the thicker film thickness is formed by the higher oil volume fraction in the work zone due to the oil pooling. The oil pooling is mainly influenced by the surface tension group. The surface speed of roller and the reduction ratio could enhance the oil volume fraction ahead of the roll bite.

Thesis (Ph. D.)--University of Texas at Austin, 1999. / Vita. Includes bibliographical references (leaves 84-87). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph. D.)--Lehigh University, 2000. / Includes bibliographical references and vita.

Thesis (Ph. D.)--University of Texas at Austin, 2000. / Vita. Includes bibliographical references (leaves 105-108). Available also in a digital version from Dissertation Abstracts.