The first part of this thesis is concerned with the synthesis, characterisation and applications of surface functionalised carbon nanoparticles. Synthetic techniques are used to modify the existing surface architecture of carbon nanoparticles towards high surface area modified electrodes and pH sensing applications. Electrochemical and synthetic techniques have been used to study triple phase boundaries and enhance their properties towards a bulk synthetic technique, in which an electrolyte phase and redox probe phase are held separate. A salt matrix, ultrasound, high shear force and a carbon fibre membrane have all been used to form unique triple phase boundary environments in which electron and ion transfer processes can be studied and enhanced towards analytical and electrosynthetic applications. A number of electro-reduction reactions have been shown to be feasible using the triple phase boundary methodology. Alkenes, aldehydes and imines have all been successfully electro-reduced, analysed and optimised to elucidate the synthetic triple phase boundary mechanism.

In this thesis, the adsorption of single-wall carbon nanotubes (SWCNTs) at the liquid/liquid interface, and the subsequent electrochemical investigation of the electrical properties of the adsorbed nanotubes have been studied. Prior to the adsorption of the nanotube, the stability of dispersion of SWCNTs in non-aqueous solvents was assessed by determining the onset of aggregation of the SWCNTs when organic electrolyte was introduced. It was found that electrostatic repulsion between the SWCNTs contributes significantly to the stability of the SWCNTs in non-aqueous solvents. Similar result was also found when the aggregation kinetics of molybdenum disulphide (MoS2) dispersion in non-aqueous media was studied using the same organic electrolyte. The formation of nanomaterial-polymer composites by deliberate electrochemical oxidation of pyrrole and the sonochemical polymerisation of the organic solvent was also studied. Electrolyte addition was shown to be a promising way to separate the 2D material from the sonopolymer.

Materials on the nanoscale have very interesting properties. Hence, they are commonly used for a variety of applications such as drug delivery, bio-imaging and sensing devices. Moreover, coating these particles with other materials forming core@shell or Janus particles can further enhance their properties. However, for the particles to be used in medical and electronic devices, their properties such as size, shape and composition need to be precisely controlled. In this PhD., an emulsification technique was chosen to investigate the synthesis of nanoparticles; it is a simple process, does not require any harsh chemicals or temperature and is fast. Emulsification occurs when two or more immiscible liquids and surfactants are mixed. Here, emulsion droplets were produced using a microfluidic device which allowed for the creation of uniform droplets. These were employed as templates to synthesise and assemble nanomaterials. The main aim of the Ph.D. was to develop a droplet based synthesis process to generate nanoparticles and then assemble them into core@shell particles. This Ph.D., starts by synthesising Fe3O4 nanoparticles (~ 12 nm) and assembling them into microparticles (~ 1µm 2µm) using emulsion droplets as microreactors. By tuning the surfactant, droplet size and evaporation rate of the dispersed phase, microparticles of varying shapes and sizes, such as spherical or crumbled shapes, were produced. When these particles are compared with the commercially available particles, the magnetic content of the in-house particles, or sometimes referred to as Loughborough University Enterprises Ltd. (LUEL), are much higher and more uniform, hence resulting in faster separation when used for extraction of analytes. LUEL particles were supplied as part of commercial collaboration. The use of Pickering emulsions were then explored to create core@shell particles using gold nanoparticles instead of a surfactant to produce gold shells and the addition of pre-synthesised Fe3O4 nanoparticles results in Fe3O4@Au core@shell particles. This is the first time Pickering emulsions were used to produce Fe3O4@Au core@shell particles (~ 1.5 µm) within a microfluidic device. However, the shells were not uniform in thickness. In order to improve the coverage, nanoparticles were synthesised in situ at the droplet interface. By placing the gold chloride (AuCl4-) in the continuous phase and by varying the concentration of the electron donor in hexane droplet, single crystal gold nanoparticles and platelets were formed. The reaction is spontaneous at room temperature, creating gold nanoparticles at the interface of the emulsion droplet. The size and shape of the gold nanoparticles were controlled by varying the concentration of the reactants and the size of the droplets. By adding pre-synthesised particles (Fe3O4 nanoparticles) to the droplet, Au@Fe3O4 core@shell particles were formed with an approximate size of 250 nm. The same concept of forming core@shell particles using gold nanoparticles was further expanded by using other metal ions; palladium and silver. Unlike gold, palladium and silver only formed spherical nanoparticles, no platelets were observed. The addition of preformed iron oxide nanoparticles to the palladium results in core@shell particles. However, in the case of silver, no core@shell particles were formed. The study of the rate of reaction was conducted to understand the details of the mechanism. Overall, the process developed in this Ph.D. study allows for the facile synthesis of core@shell particles in a rapid, high throughput reaction. In the future, it is believed it could be scaled up for commercial purposes.

The overuse of antibiotics in agriculture is an emerging concern, due to their potential detrimental impact to the environment. This study focuses on exploring antimicrobial properties of lignin derived compounds. Lignin is of interest as a feedstock to replacing some petroleum-based chemicals and products because it is the most abundant source of renewable aromatic compounds on the planet. Two lignin rich streams, residues from the enzymatic hydrolysis of dilute acid and alkaline pretreated corn stover, were decomposed via pyrolysis and hydrogenolysis, respectively. The resulting liquid oils were subjected to sequential extractions using a series of solvents with different polarities. Chemical compositions of the extracted fractions were characterized through HPLC and GC/MS. These extracted compounds were screened against Saccharomyces cerevisiae (S. cerevisiae), Escherichia coli, and Lactobacillus amylovorus for antimicrobial properties. Six lignin model monomers: guaiacol, vanillin, vanillic acid, syringaldehyde, 2,6-dimethoxyphenol, and syringic acid were compared to the oils and extracted fractions for antimicrobial properties. Development of lignin-derived chemicals with antimicrobial properties could provide a novel use for this underutilized natural resource.

The viscous oil-water hydrodynamics in a microchannel and phase equilibria of heavy oil and carbon dioxide gas have been investigated in connection with the enhanced recovery of heavy oil from petroleum reservoirs. The oil-water flow was studied in a circular microchannel made of fused silica with an I.D. of 250 µm. The viscosity of the silicone oil (863 mPa.sec) was close to that of the gas-saturated heavy oil in reservoirs. The channel was always initially filled with the oil. Two different sets of experiments were conducted: continuous oil-water flow and immiscible displacement of oil by water. For the case of continuous water and oil injection, different types of liquid-liquid flow patterns were identified and a flow pattern map was developed based on Reynolds, Capillary and Weber numbers. Also, a simple correlation for pressure drop of the two phase system was developed. In the immiscible displacement experiments, the water initially formed a core-annular flow pattern, i.e. a water core surrounded by a viscous oil film. The initially symmetric flow became asymmetric with time as the water core shifted off centre and also the waves at the oil-water interface became asymmetric. A linear stability analysis for core-annular flow was also performed. A characteristic equation which predicts the growth rate of perturbations as a function of the core radius, Reynolds number, and viscosity and density ratios of the two phases was developed. Also, two micro cells for gas solubility measurements in oils were designed and constructed. The blind cell had an internal volume of less than 2 ml and the micro glass cell had a volume less than 100 µl. By minimizing the cell volume, measurements could be made more quickly. The CO2 solubility was determined in bitumen and ashphaltene-free bitumen samples to show that ashphaltene has a negligible effect on CO2 solubility.

The viscous oil-water hydrodynamics in a microchannel and phase equilibria of heavy oil and carbon dioxide gas have been investigated in connection with the enhanced recovery of heavy oil from petroleum reservoirs. The oil-water flow was studied in a circular microchannel made of fused silica with an I.D. of 250 µm. The viscosity of the silicone oil (863 mPa.sec) was close to that of the gas-saturated heavy oil in reservoirs. The channel was always initially filled with the oil. Two different sets of experiments were conducted: continuous oil-water flow and immiscible displacement of oil by water. For the case of continuous water and oil injection, different types of liquid-liquid flow patterns were identified and a flow pattern map was developed based on Reynolds, Capillary and Weber numbers. Also, a simple correlation for pressure drop of the two phase system was developed. In the immiscible displacement experiments, the water initially formed a core-annular flow pattern, i.e. a water core surrounded by a viscous oil film. The initially symmetric flow became asymmetric with time as the water core shifted off centre and also the waves at the oil-water interface became asymmetric. A linear stability analysis for core-annular flow was also performed. A characteristic equation which predicts the growth rate of perturbations as a function of the core radius, Reynolds number, and viscosity and density ratios of the two phases was developed. Also, two micro cells for gas solubility measurements in oils were designed and constructed. The blind cell had an internal volume of less than 2 ml and the micro glass cell had a volume less than 100 µl. By minimizing the cell volume, measurements could be made more quickly. The CO2 solubility was determined in bitumen and ashphaltene-free bitumen samples to show that ashphaltene has a negligible effect on CO2 solubility.

Thesis (Ph. D.)--University of Oregon, 2002. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 187-198). Also available for download via the World Wide Web; free to University of Oregon users.

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Thesis (MAppSc)--University of South Australia, 1996

In this thesis we employ computer simulations and statistical physics to understand the origin of liquid-liquid phase transitions and their relationship with anomalies typical of liquid water. Compared with other liquids, water has many anomalies. For example the density anomaly: when water is cooled below 4 C the density decreases rather than increases. This and other anomalies have also been found to occur in a few other one-component liquids, sometimes in conjunction with the existence of a liquid-liquid phase transition (LLPT) between a low-density liquid (LDL) and a high-density liquid (HDL). Using simple models we explain how these anomalies arise from the presence of two competing length scales. As a specific example we investigate the cut ramp potential, where we show the importance of "competition" in this context, and how one length scale can sometimes be zero. When there is a clear energetic preference for either LDL or HDL for all pressures and temperatures, then there is insufficient competition between the two liquid structures and no anomalies occur. From the simple models it also follows that anomalies can occur without the presence of a LLPT and vice versa. It remains therefore unclear if water has a LLPT that ends in a liquid-liquid critical point (LLCP), a hypothesis that was first proposed based on simulations of the ST2 water model. We confirm the existence of a LLCP in this model using finite size scaling and the Challa-Landau-Binder parameter, and show that the LLPT is not a liquid-crystal transition, as has recently been suggested. Previous research has indicated the possible existence of a LLCP in liquid silica. We perform a detailed analysis of two different silica models (WAC and BKS) at temperatures much lower than was previously simulated. Within the accessible temperature range we find no LLCP in either model, although in the case of WAC potential it is closely approached. We compare our results with those obtained for other tetrahedral liquids and conclude that insufficient "stiffness" in the Si-O-Si bond angle might be responsible for the absence of a LLCP.