Yes / Waxy crude oils are pumped hot but upon power cut, pumping stops, the oil cools leading below the wax appearance temperature to precipitation of the wax and the formation of a gel throughout the pipe. In such a situation, what is the minimum pressure required to restart flow, not to merely deform the gel or break it? This paper provides a solution to this problem using microscopic observations under controlled cooling conditions and rheological data conducted in constant stress mode under controlled temperature and cooling conditions and restart experiments in laboratory pipelines replicating the rheometric conditions and deviations from them to inform large diameter operation in the field. Three important findings derive from the experimental data collected: (i) A fragmentation stress , rather than the static stress that precedes it, is found to be the more accurate predictor of flow re-start pressures; (ii) Waxy crude oils gels exhibit true yield stress and yielding process but also show flow on application of the slightest stress below yielding; (iii) This flow, in the elastic region, is jagged rather than continuous suggesting a consolidation process of the crystals and their agglomerates forming the gel. In the broader context of the existence of a yield stress, the data presented here show that there is such a thing as a yield stress and the concepts of a yield stress and that everything flows are not mutually exclusive.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2008. / This study involved (a) the development and testing of a solution turbidity fractionation analyser (TFA) and (b) the investigation of possible molecular weight effects on solution crystallisation. To investigate the latter highly isotactic polypropylene was polymerised with a C2 symmetric metallocene catalyst. Blends were made of these homopolymers. The homopolymers as well as the blends were fractionated by means of temperature rising elution fractionation (TREF). The fractionated and unfractionated homopolymers as well as the fractionated blends were characterised by 13C NMR, differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). The TFA was successfully developed and helped in explaining the shifting of solution crystallisation temperature that was seen when blending of the homopolymers occurred. This was done performing analyses on the machine of blends of the homopolymers. Fractions, of the homopolymers and blends, obtained from TREF were also done. Subsequent runs of blends made from the fractions obtained from TREF were also done. In the end it was shown that the shift of the solution crystallisation temperature is either due to the tacticity or the molecular weight depending on the sample.

Ultra High Molecular Weight Polyethylene (UHMw-PE) is an engineering polymer that is widely used in demanding applications because of its un-paralleled properties such as high abrasion resistance, high-modulus and high-strength tapes and fibres, biaxial films etc. In common practice, to achieve the uniaxial and the biaxial products, the solution processing route is adopted to reduce the number of entanglements per chain, such as found in Dyneema(R) from DSM(R). Another elegant route to reduce the number of entanglements to ease solid-state processing is through controlled polymerisation using a single-site catalytic system. In this theses, how different polymerisation condition, such as temperature and time control molecular weight and the resultant entangled state in synthesised disentangled UHMw-PE is addressed. Linear dynamic melt rheology is used to follow entanglement formation in an initially disentangled melt. With the help of rheological studies, heterogeneity in the distribution of entanglements along the chain length and the crystal morphology produced during polymerisation is considered. For the understanding of influence of large shear flow on melt dynamics large amplitude oscillatory shear (LAOS) is used and the non-linear viscoelastic regime is explored. A remarkable feature of overshoot in loss (viscous) modulus with increasing deformation (strain) in UHMw-PE melt in the LAOS is observed. This observation is characteristic of colloidal systems. The role of entanglement density in the amorphous region of the synthesised disentangled UHMw-PE (semi-crystalline polymers) on the melting and crystallisation is presented. To understand the effect of topological differences on melting behaviour, nascent entangled, nascent disentangled and melt-crystallised samples have been used. The role of superheating on the melting process is also addressed. Preliminary results on characteristic melting time of a crystal using TM-DSC are also presented.

This thesis provides a background on the effects of applied and magnetic fields on crystallisation, and summarises the analytical techniques employed for characterisation and analysis. The study of applied fields was carried out on the crystallisation of one main system-solid nonadecane. This was then studied further to establish the effects of a solvent and a mixed solid system on the crystallisation of nonadecane. The systems studied were the crystallisations of: static and dynamic nonadecane, static and dynamic nonadecane in heptane, static and dynamic nonadecane and heneicosane, static and dynamic nonadecane and heneicosane in heptane and static and dynamic nonadecane and crude oil. The results of these studies showed that the magnetic and applied fields can affect electrostatic forces in molecular solids. It also showed that even the weakest of these forces, Van der Waals forces are affected by applied and magnetic fields.

No description available.

Compte tenu de l'utilisation envisagée du graphite comme matériau de creuset à la place de la silice frittée pour la cristallisation dirigée des lingots de silicium multcristallin de qualité photovoltaïque, un objectif majeur de la thèse était de développer un revêtement spécifique au matériau de moule sélectionné. Une première tâche de ce travail a consisté à définir très précisément les conditions de fonctionnement du couple revêtement anti-adhérent / matériau de creuset et les modifications à apporter au procédé afin d'utiliser le revêtement standard à base de poudre de Si3N4 sur graphite, La deuxième tâche de la thèse a consisté à mettre en place le procédé de moulage à partir d'une étude préliminaire basée sur une configuration simplifiée de moulage par écrasement où un morceau de silicium s'étale à l'intérieur du moule au cours de sa fusion. Le but recherché est de mettre en évidence les conséquences de la configuration « moulage » (caractérisée par un rapport élevé surface de contact / volume de Si a priori très défavorable) et des conditions thermiques (gradient et vitesse de solidification) sur l'adhérence (collage), la pollution par le revêtement et la structure cristalline du silicium. / Considering the use of graphite as a crucible material instead of sintered silica for the directional crystallisation process of multicrystalline solar grade silicon, one of the main goals of this PhD program was to develop a dedicated releasing coating to be used with the identified mould material. A first task of this work consisted in a precise definition of the operating conditions for the releasing coating / crucible material couple and consequently modifying the process in order to be able to use the standard silicon nitride powder-based releasing coating on graphite. The second task was to design the moulding process based on a preliminary study of a simplified configuration of squeezing moulding experiments where the silicon piece spreads into the inner space of the mould when melting. The aim of these experiments was to enlighten the consequences of the “moulding” configuration (characterised by a high contact surface / Si volume ratio, a priori very detrimental) and of the thermal conditions (gradient and solidification speed) on adhesion (sticking), pollution coming from the coating, and on the crystalline structure of moulded silicon.

Innovations and process understanding is the current focus in pharmaceutical industry. The objective of this research was to explore application of high power ultrasound in the slurry crystallisation and application of low power ultrasound (3.5 MHz) as process analytical technology (PAT) tool to understand pharmaceutical processing such as hot melt extrusion. The effect of high power ultrasound (20 kHz) on slurry co-crystallisation of caffeine / maleic acid and carbamazepine / saccharin was investigated. To validate low power ultrasound monitoring technique, it was compared with the other techniques (PAT tools) such as in-line rheology and in-line NIR spectroscopy. In-line rheological measurements were used to understand melt flow behaviour of theophylline / Kollidon VA 64 system in the slit die attached to the hot melt extruder. In-line NIR spectroscopic measurements were carried out for monitoring any molecular interactions occurring during extrusion. Physical mixtures and the processed samples obtained from all experiments were characterised using powder X-ray diffraction, thermogravimetry analysis, differential scanning calorimetry, scanning Electron Microscopy, dielectric spectroscopy and high performance liquid chromatography, rotational rheology, fourier transform infrared spectroscopy and near infrared spectroscopy. The application of high power ultrasound in slurry co-crystallisation of caffeine / maleic acid helped in reducing equilibrium time required for co-crystal formation. During carbamazepine / saccharin co-crystallisation high power ultrasound induced degradation of carbamazepine was negligible. Low power ultrasound can be used as a PAT tool as it was found to be highly sensitive to the changes in processing temperatures and drug concentration.

No description available.

Vascular calcification is a prominent cardiovascular condition found worldwide. This condition is predominantly found in the elderly population, and patients who suffer from chronic kidney disease, due to an imbalance of serum phosphate and calcium levels. For many years, vascular calcification was believed to be a passive pathological process which develops with ageing and/or lifestyle. Little has been documented about the disease until the 20th century, when interest in cardiovascular research grew amongst scientists. Indeed, vascular calcification underpins severe clinical outcomes and cardiovascular diseases have been labelled the global leading cause of death. Calcific aortic valve diseases (CAVD) is a progressive degenerative condition characterised by the development of lipo-calcification around the aortic valve leaflets leading to severe aortic stenosis and aortic regurgitation, which may ultimately lead to heart failure. At present there are no pharmaceutical therapies that can stop its progression and its molecular mechanisms are not fully understood. Recent findings have suggested that vascular smooth muscle cell (VSMC) calcification shares many common features with physiological skeletogenesis via the release of matrix vesicles (MVs), which are specialised structures that initiate mineralisation during bone formation. The ability for MVs to nucleate calcium and phosphate highly depend on their protein composition, as this may vary depending on active cell signalling and the microenvironment. This mechanism involving MV-regulated calcification has yet to be examined in CAVD. In this study, examined whether calcium and/or phosphate regulate VIC-derived MVs to induce calcification in the aortic valve. I used a primary rat valve interstitial cell (VIC) model, coupled with stenotic human valve tissues to characterise and study the mechanisms underpinning CAVD. X-ray fluorescence and diffraction analysis showed the mineral found in calcified human aortic valves to be hydroxyapatite (HA), the main component in bone. Additional imaging studies employing transmission electron microscopy (TEM) revealed particles that were similar in size and morphology to skeletal MVs. To further characterise VIC-derived MVs in vitro, I harvested MVs from rat VICs, and subsequently studied their protein composition using Isobaric tag for relative and absolute quantitation (iTRAQ) mass spectrometry. The data obtained from the proteomics analysis was compared to previous published studies on MV proteins derived from osteoblasts and VSMCs. The results showed the upregulation of numerous calcification regulators in MVs isolated from all 3 cell types, in particular, the Annexin family, which are known calcium binding proteins. Further studies conducted with Annexin 6, an established calcium regulator in arterial calcification, revealed its colocalisation with MV-enriched areas in calcified human aortic valve tissue suggesting it may play an important role in calcium regulation during CAVD.

Thin film silicon on low temperature glass substrates is currently seen as the best path toreduce the $/W cost of photovoltaic (PV) modules. However, producing thin film polysilicon, on glass, is an ongoing research challenge. Laser crystallisation of a-Si is one of the possible methods. Typically excimer (XMR) lasers are used for laser crystallisation. This thesis introduces the copper vapour laser (CVL) as a viable alternative for thin film photovoltaic applications. The CVL, like the XMR, is a high powered, pulsed laser. However, the CVL has higher pulse rates (4-20kHz), better beam quality and a visible wavelength output (578 & 511nm). Preliminary experiments, using 600K-heated silicon-on-quartz samples, confirmed that CVL crystallisation can produce area weighted average grain size of 0.1-0.15??m, which is comparable to results reported for XMR??? s. Importantly, the CVL results used thicker films (1??m), which is more applicable to thin photovoltaic devices that need 1-10??m of silicon to be viable. The CVL??? s longer wavelength and therefore longer penetration depth (1/alpha) are proffered as the main reason for this result. Extensive laser-thermal modelling highlighted further opportunities specific to CVL crystallisation. Through-the-glass doublesided irradiation was shown in simulations to reduce thermal gradients, which would enhance crystal growth. The simulations also produced deeper melts at lower surface temperatures, reducing the thermal stress on the sample. Subsequent experiments, using silicon-on-glass, confirmed the benefit of through-the-glass doublesided irradiation by maintaining grain sizes without the usual need for substrate heating. Furthermore, Raman analysis showed that doublesided crystallisation achieved full depth crystallisation, unlike single side irradiation which produced partial crystallisation. A new mode of crystallisation, stepwise crystallisation, was also postulated whereby a series of CVL pulses could be used to incrementally increase the crystallisation depth into the silicon. Simulations confirmed the theoretical basis of the concept, with HeNe Raman spectroscopy and analysis of surface grain sizes providing indirect experimental support. The CVL??? s ability to crystallise thicker films more directly applicable to photovoltaic devices secures its viability as an alternative laser for photovoltaic applications. The through-the-glass doublesided irradiation and the stepwise crystallisation provide additional potential for increased process flexibility over XMR???s.