The oil and gas industry is often plagued by the formation of clathrate hydrates in oil pipelines. While the industry originally had a heuristic of avoidance of clathrate hydrates they are moving to a heuristic of risk management. To successfully implement a risk management heuristic, time dependent phenomena of clathrate hydrate formation and flowline plugging must be known. The study of time dependent phenomena of formation and agglomeration are investigated using a TA Instruments AR-G2 rheometer with a pressure cell capable of operating at up to 13.8 MPa. Pressurized rheological experiments examine clathrate hydrates formed in situ. Both shear and oscillatory experiments have been conducted on the samples, giving flow and viscoelastic parameters. Shear experiments show sharp increases in viscosity upon clathrate hydrate formation indicating rapid aggregation. Transient oscillation experiments show a sharp increase in the elastic and loss moduli followed by a decrease in the loss moduli. Thus, both in situ clathrate hydrate formation and annealing are quantified. In addition these oscillatory measurements provided a novel technique for non-destructive investigation of clathrate hydrate aggregation over time.

As the oil industry moves from a heuristic of avoidance of hydrates to a heuristic of risk management time dependent phenomena of hydrate formation and plugging must be known. One of the key parameters to this process is the aggregation of hydrate particles, the fractal networks they form, and the effect these two parameters have on flow. Unfortunately the aggregation and fractal structure information is extremely difficult to acquire experimentally, for this reason a three-dimension discrete element method (3D-DEM) model has been implemented. The 3D-DEM model calculates detailed solutions to Newton's equations of motion for individual particles. In addition these particles are coupled with the surrounding fluid through computational fluid dynamics (CFD). This coupled 3D-DEM can be used to investigate what the effects of shear, suspending viscosity, attractive forces, and other relevant variables have on the structure, stresses, and positions of the hydrate particles over time. In addition, the effect on viscosity has been calculated using CFD and compared back to basic hard sphere theory.

Gas hydrates are known to form plugs in pipelines. Hydrate plug dissociation times can be predicted using the CSMPlug program. At high methane mole fractions of a methane + ethane mixture the predictions agree with experiments for the relative dissociation times of structure I (sI) and structure II (sII) plugs. At intermediate methane mole fractions the predictions disagree with experiment. Enthalpies of dissociation were measured and predicted with the Clapeyron equation. The enthalpies of dissociation for the methane + ethane hydrates were found to vary significantly with pressure, the composition, and the structure of hydrate. The prediction and experimental would likely agree if this variation in the enthalpy of dissociation was taken in to account. In doing the plug dissociation studies at high methane mole fraction a discontinuity was observed in the gas evolution rate and X-ray diffraction indicated the possibility of the presence of both sI and sII hydrate structures. A detailed analysis by step-wise modelling utilising the hydrate prediction package CSMGem showed that preferential enclathration could occur. This conclusion was supported by experiment. Salts such as tetraisopentylammonium fluoride form semi-clathrate hydrates with melting points higher than 30 ℃ and vacant cavities that can store cages such as methane and hydrogen. The stability of this semi-clathrate hydrate with methane was studied and the dissociation phase boundary was found to be at temperatures of about (25 to 30) K higher than that of methane hydrate at the same pressure.

Inhibiting the formation of ice is an essential process commercially, industrially, and medically. Compounds that work to stop the formation of ice have historically possessed drawbacks such as toxicity or prohibitively high active concentrations. One class of molecules, ice recrystallization inhibitors, work to reduce the damage caused by the combination of small ice crystals into larger ones. Recent advances made by the Ben lab have identified small molecule carbohydrate analogues that are highly active in the field of ice recrystallization and have potential in the cryopreservation of living tissue. A similar class of molecules, kinetic hydrate inhibitors, work to prevent the formation of another type of ice – gas hydrate. Gas hydrates are formed by the encapsulation of a molecule of a hydrocarbon inside a growing ice crystal. These compounds become problematic in high pressure and low temperature areas where methane is present - such as an oil pipeline. A recent study has highlighted the effects of antifreeze glycoprotein, a biological ice recrystallization inhibitor, in the inhibition of methane clathrates. Connecting these two fields through the synthesis and testing of small molecule ice recrystallization inhibitors in the inhibition of methane hydrates is unprecedented and may lead to a novel class of compounds.

Bibliography: leaves 178-186 / 186 leaves, [9] leaves of plates : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1989

Offprints of two author's journal articles inserted at end of the v. / Bibliography: leaves 10-12 / 216 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1985

Includes errata attached to first leaf. / Includes bibliographical references. / vi, 158 leaves : ill. (some col.) ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / The complexation of a range of monovalent and divalent metal ions by the bibracchial lariat ethers has been investigated. Also investigates the complexation of metal ions and the anionic azo dye Brilliant Yellow by the diazacrown linked cyclodextrin dimers. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemistry, 2000

Bibliography: leaf 179 / 179 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--Dept. of Physical and Inorganic Chemistry, University of Adelaide, 1986

Includes bibliographies / x, 149 leaves : ill. (some col.) ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, 1986

Thesis (Ph.D.)--McMaster University (Canada), 1991. / Source: Dissertation Abstracts International, Volume: 54-02, Section: B, page: 0917.