The class of water-ice compound known as gas hydrate has been of interest to science for sometime where, for instance, gas hydrates make excellent candidates for studying the interactions of water and gas molecules. They are also of relevance to industry, where they present an interesting material for the separation, transport, and storage of different gases, and also due to the vast quantities of methane gas that are trapped in natural gas hydrate formations. While much is known about the behaviour of many gas hydrate systems at high-pressure, the CO2 hydrate system is less well studied, with apparent hydrate dissociation at just 10 kbar, and (prior to this work) an unsolved crystalline phase in the pressure range 6-10 kbar. In this work the CO2-H2O system has been studied at high-pressure and, by heating samples to the liquid state and observing their behaviour on refreezing, it has been confirmed that there are indeed no hydrate phases in the system above 10 kbar (up to at least 40 kbar). While performing this investigation, an interesting effect of CO2 on the behaviour of water crystallisation was also observed, and additionally, a simple yet effective technique for making solubility measurements in the system at high-pressure has been discovered. Using a combination of neutron and x-ray diffraction techniques, the crystal structure of the previously unsolved ‘HP’ CO2 hydrate phase has been determined by ab-initio methods. It has been found to be a new gas hydrate structure, but is shared by a small number of Zintl compounds, and may also be common to the unsolved C0 phase of H2 hydrate. The structure has a characteristic spiral of guest molecule sites, leading to its suggested label as the spiral hydrate structure (s-Sp). Its composition has been measured as a tri-hydrate, and the compressibility of s-Sp and the low-pressure s-I CO2 hydrate phases have also been measured. On cooling to 77 K it has been discovered that a third CO2 hydrate phase is formed with a significantly larger unit cell, which is thought to possess a structure similar to that of s-Sp, but with an ordered arrangement of CO2 molecules. Finally, a pilot study of the high-pressure behaviour of the binary H2-CO2 hydrate system has been performed. Using Raman spectroscopy it has been found that a new mixed hydrate phase exists in the pressure range 5-15 kbar, and it is speculated that this could exhibit a freely tunable H2/CO2 content, based on suspicion that it forms the s-Sp structure. Additionally, it has been found that H2 and CO2 chemically react at room temperature, when compressed to ~5 kbar in a rhenium gasket. From the Raman spectrum this reaction product has been identified to be aqueous-methanol.

abstract: Earthquake faulting and the dynamics of subducting lithosphere are among the frontiers of geophysics. Exploring the nature, cause, and implications of geophysical phenomena requires multidisciplinary investigations focused at a range of spatial scales. Within this dissertation, I present studies of micro-scale processes using observational seismology and experimental mineral physics to provide important constraints on models for a range of large-scale geophysical phenomena within the crust and mantle. The Great Basin (GB) in the western U.S. is part of the diffuse North American-Pacific plate boundary. The interior of the GB occasionally produces large earthquakes, yet the current distribution of regional seismic networks poorly samples it. The EarthScope USArray Transportable Array provides unprecedented station density and data quality for the central GB. I use this dataset to develop an earthquake catalog for the region that is complete to M 1.5. The catalog contains small-magnitude seismicity throughout the interior of the GB. The spatial distribution of earthquakes is consistent with recent regional geodetic studies, confirming that the interior of the GB is actively deforming everywhere and all the time. Additionally, improved event detection thresholds reveal that swarms of temporally-clustered repeating earthquakes occur throughout the GB. The swarms are not associated with active volcanism or other swarm triggering mechanisms, and therefore, may represent a common fault behavior. Enstatite (Mg,Fe)SiO3 is the second most abundant mineral within subducting lithosphere. Previous studies suggest that metastable enstatite within subducting slabs may persist to the base of the mantle transition zone (MTZ) before transforming to high-pressure polymorphs. The metastable persistence of enstatite has been proposed as a potential cause for both deep-focus earthquakes and the stagnation of slabs at the base of the MTZ. I show that natural Al- and Fe-bearing enstatite reacts more readily than previous studies and by multiple transformation mechanisms at conditions as low as 1200°C and 18 GPa. Metastable enstatite is thus unlikely to survive to the base of the MTZ. Additionally, coherent growth of akimotoite and other high-pressure phases along polysynthetic twin boundaries provides a mechanism for the inheritance of crystallographic preferred orientation from previously deformed enstatite-bearing rocks within subducting slabs. / Dissertation/Thesis / Great Basin Seismicity from 2004 to 2013 (event data) / Great Basin Seismicity from 2004 to 2013 (Google Earth) / Doctoral Dissertation Geological Sciences 2015

abstract: Shock metamorphism in meteorites constrains the impact histories of asteroids and planets. Shock-induced high-pressure (HP) minerals can provide more precise estimates of shock conditions than shock-induced deformation effects. In this research, I use shock features, particularly HP minerals, in ordinary-chondrite samples to constrain not only shock pressures but also the pressure-temperature-time (P-T-t) paths they experienced. Highly shocked L5/6 chondrites Acfer 040, Mbale, NWA 091 and Chico and LL6 chondrite NWA 757 were used to investigate a variety of shock pressures and post-shock annealing histories. NWA 757 is the only highly shocked LL chondrite that includes abundant HP minerals. The assemblage of ringwoodite and majoritic garnet indicates an equilibration shock pressure of ~20 GPa, similar to many strongly shocked L chondrites. Acfer 040 is one of the only two chondrite samples with bridgmanite (silicate perovskite), suggesting equilibration pressure >25 GPa. The bridgmanite, which is unstable at low-pressure, was mostly vitrified during post-shock cooling. Mbale demonstrates an example of elevated post-shock temperature resulting in back-transformation of ringwoodite to olivine. In contrast, majoritic garnet in Mbale survives as unambiguous evidence of strong shock. In these two samples, HP minerals are exclusively associated with shock melt, indicating that elevated shock temperatures are required for rapid mineral transformations during the transient shock pulse. However, elevated post-shock temperatures can destroy HP minerals: in temperature sequence from bridgmanite to ringwoodite then garnet. NWA 091 and Chico are impact melt breccias with pervasive melting, blackening of silicates, recrystallization of host rock but no HP minerals. These features indicate near whole-rock-melting conditions. However, the elevated post-shock temperatures of these samples has annealed out HP signatures. The observed shock features result from a complex P-T-t path and may not directly reflect the peak shock pressure. Although HP minerals provide robust evidence of high pressure, their occurrence also requires high shock temperatures and rapid cooling during the shock pulse. The most highly shocked samples lack HP signatures but have abundant high-temperature features formed after pressure release. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2016

Part 1 The viscosity of silicate melts is a fundamental physical property that determines the mobility and transport behaviour of magma on the surface and in planetary interiors. The viscosity of liquid fayalite (Fe2SiO4), the Fe-rich end-member of the abundant upper mantle mineral olivine, was determined up to 9.2 GPa and 1850 °C using in situ falling sphere viscometry and X-ray radiography imaging. The viscosity of liquid fayalite was found to decrease with pressure both along the melting curve and an isotherm, with temperature having very little influence on viscosity at high pressure. This work is the first to determine the viscosity of a highly depolymerized silicate melt at high pressure as only recent advances in experimental techniques have allowed the difficulties associated with studying depolymerized liquids at high pressure to be overcome. The results are in contrast with previous studies on moderately depolymerized silicate melts such as diopside and peridotite which found viscosity to initially increase with pressure. In accordance with recent in situ structural measurements on liquid fayalite, the viscosity decrease is likely a result of the increase in Fe-O coordination with pressure. The results show that the behaviour of silicate melts at depth is strongly dependent on the melt structure and composition. Part 2 The magnitude of the thermal anomaly at hotspot locations has a fundamental influence on the dynamics of mantle melting and therefore has an important role in shaping the surface of our planet. The North Atlantic Igneous Province (NAIP) is the surface expression of a major mantle plume and is unique in the fact that it has a complete magmatic history. The highest 3He/4He volcanic rocks on Earth are found in the early NAIP picrites of West Greenland and Bafin Island and high 3He/4He rocks are still erupted on Iceland today. However, the relationship between 3He/4He and mantle plumes has remained enigmatic. The main aim of this work is to use the ideal opportunity provided by the NAIP to investigate the relationship between temperature, mantle melting dynamics and helium isotopes within a mantle plume. The magmatic temperatures of a suite of picrites and primitive basalts spanning the spatial and temporal range of the NAIP was determined using traditional olivine-melt thermometry, a forward mantle melting model and the newly developed Al-in-olivine thermometer. This study is the first to provide a detailed petrologic approach to investigating the mantle temperature of the NAIP throughout its magmatic history and is the first to compare all three techniques in detail. The Al-in-olivine thermometer was found to be the most robust proxy for mantle temperature. The early stage of volcanic activity in the NAIP is associated with the arrival of the ancestral Iceland plume head and resulted in a uniform temperature anomaly with Al-in-olivine temperatures 250-300° above that of ambient MORB across an area 2000 km in diameter. In addition, the temperature of the plume is shown to have been subject to large temperature fluctuations on a timescale of 107 years and is currently increasing, which has had profound effects on the melting dynamics and bathymetry of the North Atlantic region. Using existing and new 3He/4He measurements, no clear relationship between 3He/4He and temperature is observable. However, it is noted that the maximum 3He/4He of primitive basalts from the NAIP has decreased through time. These relationships are explicable if the high 3He/4He reservoir is located in either the core or the core-mantle boundary (CMB), from which helium diffuses into the lower mantle. The high 3He=4He signature is incorporated into a plume when it breaks away from the base of the mantle and over the lifetime of the plume, the 3He/4He source is gradually depleted. The temperature of the plume can vary independently in responses to heat flow at the CMB, which is in turn related to changes in mantle convection. Global plate tectonics and mantle processes are therefore intricately linked with melting dynamics at hotspot locations.

The study of hydrogen and the understanding of its response to extended pressure and temperatures is of great importance due to its significant universal abundance. Hydrogen is currently not well understood in these extended regimes due to it being inherently difficult to work with experimentally as well as having a poor response to a wide range of diagnostics. Consequently, there have been long standing predicted phenomena which still remain experimentally elusive: (1) melting driven by large zero point oscillations [Brovman 72] and (2) adopting a purely atomic state at higher pressures [Wigner 35]. Coupling high-pressure, high-temperature techniques with in-situ optical diagnostics, the stability of the solid phases of hydrogen were evaluated over an extended pressure-temperature regime. The first ever H2 solid-solid transitions above 300 K are reported and the evolution of the I-IV phase line after the III-IV-I triple point is constrained. A transition which could be attributed to melting is observed at 480 K and 225 GPa, the lowest known melting temperature for any material under these conditions. A new triple point between phase I-IV-Liquid is identified, the third known triple point in the phase diagram and the first on the melting curve. The possible continuations of the melting line are discussed, ultimately revising the melting transition at 300 K and at 0 K to much higher pressures than previously thought [Bonev 04]. The contributing work also marks a new high pressure achievement, obtaining some of the highest ever recorded static pressures in the laboratory. Hydrogen and its heavier isotopes hydrogen deuteride and deuterium were compressed to pressures of 384 GPa, 388 GPa and 380 GPa respectively. These experimental data are indicative that above 325 GPa H2 and HD adopt a new solid phase, phase V. Analysis of the spectra over the IV-V transition is suggestive that under compression the molecular bonding in the G-layers of the Pc structure lengthen and symmetrise, evolving into the Ibam structure. It is speculated that this phase could be a precursor to the elusive, purely atomic I41/amd structure predicted to be stable at higher pressures (>400 GPa) [McMahon 11, Azadi 14].

Aluminium alloys have been seen a dramatic increase in transport manufacturing in past two decades. This is primarily driven by the achievement of effective weight-savings, increased vehicle fuel efficiency and reduced CO2 emissions in transport. One of the significant progresses in most recent years has been in the application of aluminium-intensive car body structure, in which the manufacturing of thin wall castings with improved ductility is one of the critical issues. High pressure die casting (HPDC) is a fast and economical near-net shape manufacturing method to produce thin wall components. Therefore the application of HPDC process to make thin wall structural components for aluminium-intensive car body structure is one of the most challenges in recent development. However, the currently available die cast aluminium alloys are unable to fulfil this requirement because of the insufficient ductility, which is essential for joining castings with sheets and extruded parts. This has become critical in further development and extensive acceptance in car manufacturing industry. Generally, the mechanical properties of die castings are determined by alloy composition, defect levels and microstructure in the castings. In the present study, the significant achievement is the development of Al-Mg-Si-Mn alloy for HPDC process to provide improved ductility in die castings in order to satisfy the requirement of mechanical properties, in particular ductility for the application in automotive body structure. Starting from the thermodynamic analysis and CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) modelling of Al-Mg-Si system for solidification and phase formation, the alloy composition was optimised using international standard tensile samples to review the effect of various alloying elements on the mechanical properties. Another achievement is the understanding of the solidification and microstructural evolution, the relationship between the microstructure and mechanical properties, and the strengthening mechanisms in the developed alloy. The solidification behaviour in the shot sleeve and in the die cavity was examined for the formation of the primary α-Al phase, eutectic Al-Mg2Si phases in the alloy. The morphology, size and size distribution of the primary α-Al phase were characterised under different solidification conditions. The growth morphology of the primary α-Al phase formed in the shot sleeve and in the die cavity was analysed using the Mullins-Sekerka instability theory and the growth rate of eutectic Al-Mg2Si phases during solidification was calculated using Jackson-Hunt theory. Still another achievement is the study of the effect of Mn and Fe on the morphology, size and distribution of various Fe-rich compounds in the Al-Mg-Si alloy produced by HPDC process. The assessment was associated with the mechanical properties of yield strength, ultimate tensile strength and elongation with different Fe and Mn contents. CALPHAD modelling of multi-component Al-Mg-Si-Mn-Fe and Al-Mg-Si-Fe systems was studied to find out the effect of Fe impurity in the Al-Mg-Si alloy. The precise accumulation of iron during HPDC using fully recycled materials was examined to predict the maximum cycles to produce castings with required mechanical properties. The strengthening mechanism and the relationship between the microstructure and mechanical properties are explored in the alloy made by secondary materials. Furthermore, the effect of nickel on the microstructure and mechanical properties of the die-cast Al-Mg-Si-Mn alloy was also studied in association with the formation of Ni-rich intermetallics during solidification in the die-cast Al-Mg-Si-Mn alloy containing different Ni contents. The final achievement is the understanding of the repeatability of die castings made by the new alloy with industrial scale components. The tensile properties of standard samples that were obtained directly from HPDC process and made by the machined die castings at different locations were further assessed for the reproducibility of casting components made by the Al-Mg-Si-Mn alloy. The distributions of yield strength, ultimate tensile strength and elongation of the tensile samples were analysed by the average values with standard deviations and by the Weibull statistical model with three parameters. The correlations between the mechanical properties and the microstructural features, porosity levels and fracture morphology were investigated for the different types of samples. It was found that three-parameter Weibull analysis was capable of analysing the reproducibility of die cast components and the scattering of tensile properties was mainly due to the presence of porosity and non-uniform microstructure in the die-castings.

Some of the challenges faced when developing novel functional materials, cannot be resolved without the correct understanding of their structure‐property relationships. Metal‐organic frameworks (MOFs) constitute a representative example where in-depth structural knowledge can greatly help improve and optimise their application into industrially relevant settings. Fortunately, the inherent crystalline nature of MOFs allows for analysis using the wide range of crystallographic experimental techniques that are currently available. This work covers the study of the structural properties of a particular family of MOFs, which have shown significant potential as molecular sieves and for gas storage. Sc-based MOFs first attracted attention for their particularly robust and inert nature, bypassing some of the physical challenges many MOFs have when undergoing industrial implementation. After an initial review of the state of the art in the field of MOFs and the techniques utilised to analyse their properties, this work then focuses on the mechanical properties of a series of functionalised and unfunctionalised Sc‐dicarboxylate MOFs. Using nano‐indentation techniques and high‐pressure crystallography, the hardness and elasticity of these materials are correlated to their different structural features, confirming their relative robustness when compared to other MOFs in the literature. An interesting property of Sc2BDC3 is its selective uptake of CO2 over other fuel-related gases such as CH4 and CO. In this context, the in situ adsorption crystallographic analysis of Sc2BDC3 and its amino‐functionalised derivative Sc2(BDC‐NH2)3 (BDC‐NH2 = 1,4‐amino‐2‐benzenedicarboxylate) is described, as performed using the gas cell set up of beamline I19 at the Diamond Light Source synchrotron. This study is the first example of a mixed gas atmosphere experiment using single‐crystal diffraction, which in conjunction with in silico, adsorption and breakthrough experiments, provides direct insight into the interactions that drive the selective behaviour of both frameworks. Following this, the MOF Sc2BDC3 (BDC = 1,4‐benzenedicarboxylate), is selected as a case study for branched and unbranched alkane separation. Here, high‐pressure crystallography shows how these relatively oversized guest molecules, can be forced at thousands of atmospheres of pressure inside the narrow triangular channels (< 4 Å diameter) of the framework. It is also possible to resolve the structural changes the framework undergoes upon uptake of the different guests, as well as locate the adsorption sites of the hydrocarbons in the pores of Sc2BDC3, which can be then correlated to the gas adsorption behaviour of the different guests. To conclude, the high‐pressure inclusion study of both CO2 and CH4 inside Sc2BDC3 shows how combining cryoloading techniques and molecular crystallography for the first time, can provide improved models of the adsorbed gaseous guests inside Sc2BDC3. This example not only provides a novel alternative in which to study more easily the adsorption sites in MOFs via diffraction techniques, but also reveals some of the interesting structural behaviour MOFs can have in these extreme conditions.

Steam is a commonplace utility in chemical processing plants across the globe. The many benefits of steam ensure its continued use, but concerns about the cost of energy and of the equipment associated with steam systems has led to the development of a number of techniques to reduce energy and capital costs. One such topic is the reduction of boiler purchase cost, brought about by a reduction in steam flowrate. Recent publications have shown that the flowrate of steam required for heating purposes can be minimised by employing hot liquid reuse, with systematic methods developed for targeting the minimum flowrate, and synthesising the heat exchanger network. In this work, a mathematical analysis has been performed to gain insight on how choosing different steam levels affects the minimum total steam flowrate. The analysis covered both the traditional practice of only utilising latent heat, as well as the new practice of hot liquid reuse. It was found that the lowest flowrate obtainable occurs in the case of hot liquid reuse, when only a single high pressure steam level is considered. Since the need to provide shaft work or generate electricity necessitates the presence of steam turbines on plants, the inclusion of additional steam levels is unavoidable. For this reason, a novel MINLP formulation was developed to provide a holistic coverage of the heat exchanger network and the power block. The purpose of the new formulation is to target the minimum total steam flowrate, whilst simultaneously selecting the optimum saturation temperatures for the additional steam levels, designing the turbines to meet shaft work requirements and synthesizing the heat exchanger network. Application of this new method to a case study yielded a 28.6% reduction in total steam flowrate, compared to common design practice. i I, Sheldon Grant Beangstrom, with student number 27069771, declare that:  I understand what plagiarism entails and am aware of the University of Pretoria‟s policy in this regard.  This dissertation is my own, original work. Where the work of another has been used (whether from a printed source, the internet or otherwise) due acknowledgement has been given and reference made in accordance with the departmental guidelines.  I have not made use of another student‟s previous work in an attempt to submit it as my own.  I have not allowed, nor will I allow another person to copy this work with the intention of presenting it as his or her own work.  The material presented in this dissertation has not been submitted to another institution in partial or whole fulfilment of another degree. / Dissertation (MEng)--University of Pretoria, 2013. / gm2014 / Chemical Engineering / unrestricted

Due to its exceptional mechanical and electrical properties, graphene (one layer sheet of carbon atoms) has attracted a lot of attention since its discovery in 2004. The purpose of this research is to compare the Raman spectra of graphene with plasma treated graphene sheets which have been treated by changing the different parameters affecting the plasma treatment like gas flow, power and pressure and treatment time. The graphene we used for our high pressure studies are 4-5 layer CVD deposited graphene samples prepared by our collaborators in Dr. W. B. Choi’s group. First we report a Raman spectroscopy study of graphene on copper substrate at high pressures. Diamond anvil cell (DAC) was used to generate pressure. In situ Raman spectra were collected at pressures up to 10 GPa. The results indicate that the G band of graphene shifts with pressure significantly (about 5 cm-1/GPa) whereas the 2D band changes very little. The plasma treated samples were loaded into DAC. Raman spectrum was captured. Parts of the spectrum which were not related to the grapheme peak position were eliminated. The background was reduced. Peaks were found and fitted using FITYK software and the shift of each peak compared to its last position was observed when the pressure was increased. Next we studied plasma treated graphene samples treated with different partial pressure treatments under high pressure and compared them to each other using zirconia anvil cell with the same method.

Commercial ebullated bed hydroprocessors, such as the LC-Finer, are used for the production of synthetic crude oil by upgrading bitumen extracted from the Alberta oil sands. The objective of this thesis was to investigate the impact of an increased vacuum distillation tower bottoms feed fraction on the reactor fluid dynamics (e.g., bed and freeboard phase holdups, bubble characteristics and local fluidization behaviour). Industrial conditions were simulated in a high pressure gas-liquid-solid fluidization system based on dimensional and geometric similitude. Considering important geometric characteristics and matching dimensionless groups, base-case conditions resulted in an ebullated bed of nitrogen, 0.5 wt.% aqueous ethanol, and aluminum cylinders (average lengths and diameters of 7.5 and 3.2 mm, respectively) operating at 6.5 MPa and a gas-to-liquid superficial velocity ratio of 0.78. The proposed scale-down method resulted in high gas holdup conditions similar to industrial measurements. The use of the Sauter mean diameter to account for particle size and shape at the simulation conditions was investigated by comparing glass spheres with diameters of 4 and 1.5 mm to aluminum cylinders with equivalent volume-to-surface area ratios. Local bubble characteristics, including gas holdups, bubble rise velocities, and chord lengths, were then investigated under various operating conditions using a monofibre optical probe. Overall fluid dynamics were studied when increasing the liquid viscosity and varying the gas and liquid superficial velocities due to their relevance for industrial ebullated bed hydroprocessors. Freeboard and bed region gas holdup relations were studied and correlations were developed for gas and solid holdups at the simulation conditions based on the dimensionless groups. Mesophase generation in hydroprocessors due to undesired secondary reactions was also considered for an increased vacuum residue feed fraction. Adding a dispersed immiscible liquid phase which preferentially wetted the particles was therefore experimentally studied at non-simulating conditions using nitrogen, biodiesel, glycerol and various particles, where fluidization behaviour and phase holdups were considerably affected due to particle clustering. A study on the impacts of particle size, shape and material demonstrated the influences of fluid and particle properties, specifically the relative surface energies and viscous forces, on agglomeration due to interparticle liquid bridging.