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The work contained in this thesis is concerned with the flow behaviour of polymer solutions and melts. It is a theoretical study, though it refers extensively to experimental work by others. Calculations are analytic where possible, though some numerical work is required. The principal source is the theoretical model of linear polymer melts developed by Doi and Edwards. The presentation is as follows: Chapter 1 reviews the experimental properties of polymeric liquids and some of the phenonenological schemes used to describe them. Review material extends into chapter 2 which covers molecular theory, the Doi-Edwards model, and developments in the last few years. Chapter 3 applies the model to the 'spurt effect', a well known unstable flow of linear polymer melts. We show that this may be explained quantitatively by the multivalued constitutive behaviour of the model. Chapter 4 examines the stability of the flow field associated with the spurt effect and shows how certain pulsing periodicities in the flow may be related to the 'normal stress' behaviour of the fluid. Chapter 5 is a case study of a more complex branched polymer: the 'H-polymer'. It is shown that both the linear and non-linear viscoelastic response may be calculated in a straightforward extension of the Doi-Edwards model, comparing favourably with experiments to date.

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Les expériences ont été menées pour déterminer les propriétés électriques des verres et liquides silicatés du Vésuve et du Kilauea par spectroscopie d’impédance. Une étude méthodologique des mesures à deux et quatre électrodes a amélioré la qualité des mesures électriques. Les mesures ont été faites entre 400 et 1400°C, 0.1 et 400MPa et pour des fugacités en oxygène de 10-8 à 0.2 bar. La conductivité électrique croît avec la température, les teneurs en eau et sodium et lorsque pression et fO2 diminuent. Des lois d’Arrhénius ont été déterminées dans les verres et liquides pour étudier les propriétés de transport. Des énergies d’activation de 60 à 150kJ/mol et un volume d’activation de 20cm3/mol ont été calculés. Une méthode semiempirique a été déduite pour estimer la conductivité d’une large gamme de melts. Une application géophysique de nos résultats a consisté en un modèle direct de la conductivité du Vésuve. Les fonctions de transfert s’expliquent par la seule présence d’une saumure. Sa forte conductivité rend la détection d’un corps magmatique profond difficile. Cependant, nos simulations ont démontré que les données géophysiques actuelles sont en accord avec un réservoir de magma cristallisé ou du magma plus chaud interconnecté dans l’encaissant carbonaté. Une application géochimique a consisté au suivi en temps réel des cinétiques redox dans des basaltes, en utilisant la dépendance au temps de la conductivité suite à un changement de fO2. L’évolution de la conductivité au cours du temps, liée à la mobilité du sodium, est identique à celle du ratio fer ferrique/fer ferreux du melt. La réduction sous CO-CO2 et l’oxydation à l’air sont limitées par la diffusion, mais pas l’oxydation sous CO2, probablement à cause de réactions à l’interface gaz/melt. Les valeurs calculées élevées de diffusivité et d’énergie d’activation ont été expliquées par des mécanismes redox impliquant une coopération entre flux d’alcalins, de cations divalents et d’oxygène. / Experiments were conducted to determine the electrical properties of silicate glasses and liquids from Mt Vesuvius and Kilauea volcanoes using impedance spectroscopy. A methodological study of the two and four electrode measurements improved the quality of the electrical measurements. Measurements were performed between 400 and 1400°C, from 0.1 to 400MPa and for oxygen fugacities ranging from 10-8 to 0.2 bar. The electrical conductivity increases with increasing temperature, water content, sodium content and with decreasing pressure and fO2. Arrhenius laws were determined for glasses and liquids to investigate the transport properties. Activation energies from 60 to 150kJ/mol and an activation volume of 20cm3/mol were calculated. A semi-empirical method was deduced to estimate the conductivity of a wide range of melts. A geophysical application of our results consisted in the forward modelling of the conductivity of Mt Vesuvius. Transfer functions are explained by the only presence of a brine. Its high conductivity makes difficult the detection of a deeper magmatic body. Still, our simulations demonstrated that present geophysical data are compatible with a crystallized magma reservoir or a hotter magma interconnected in the surrounding carbonates. A geochemical application consisted in the monitoring in real-time of redox kinetics in basaltic liquids, using the time-dependence of electrical conductivity following fO2 step changes. The evolution of the conductivity with time, related to sodium mobility, is identical to that of the ferric/ferrous ratio of the melt. Reduction under CO-CO2 and oxidation in air are diffusion-limited, while oxidations under CO2 are not, probably due to gas/melt interface reactions. High calculated diffusivities and activation energies have been explained by redox mechanisms involving cooperative alkali, divalent cation and oxygen fluxes.

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Trace elements are highly fractionated during large-scale melting associated with planetary differentiation events. The resulting partition coefficients are used to constrain a range of geological processes and are known to be influenced by pressure, temperature, and compositional changes in crystalline structures. Although recent studies have shown that melt compositional changes affect the partitioning of trace elements, the degree to which these ratios are influenced by alterations in the melt structure, especially with increasing pressure, is poorly constrained due to the difficulty of collecting structural information on bonding environments in situ. A basic understanding of how these elements are incorporated in silicate melts is critical to interpreting early planetary differentiation and crust forming events. This thesis presents results from both x-ray diffraction and absorption techniques on trace element (Y, Zr, Lu and Nd) incorporation in silicate melt structures. The structure of two rare Earth element doped model end member silicate liquids, a highly polymerised haplogranite (Si- Al-Na-K-O) and a less polymerised anorthite-diopside (Si-Al-Mg-Ca-O), have been studied. The results are the first to identify trace rare Earth element (REE) incorporation in silicate melts at high pressure using x-ray diffraction techniques. The local melt structure around Y and Zr in a highly polymerised haplogranite has been studied using x-ray absorption spectroscopy up to 8GPa and 1650 K. Both elements appear to adopt 8-fold coordination within the melt structure with no variation over the pressure range studied. This was also found for the Lu bonding environment in the same composition where the coordination number of Lu-O was found to be 8, with a bond distance rLu-O = 2:36A in the haplogranite melt. At low pressures, < 5GPa, the bonding environment of Lu-O was found to be dependent on composition with coordination decreasing to CNLu-O = 6 and rLu-O = 2:29A in the anorthite-diopside melt. This compositional variance in coordination number at low pressure is consistent with observations made for Y-O in glasses at ambient conditions and is coincident with a dramatic increase in the partition coefficients previously observed for rare Earth elements (REE) with increasing melt polymerisation. However, an abrupt change in both Lu-O coordination and bond distance is observed at 5GPa in the anorthite-diopside melt, with CNLu-O increasing from 6 to 8-fold and rLu-O from 2.29 to 2.39A. This occurs over a similar pressure range where a reduction in the reported heavy REE partition coefficients is observed. X-ray diffraction experiments up to 60GPa and 2000K have also been performed on the incorporation of the larger light REE, Nd, in basaltic-like melts. The results presented show that incorporation within the anorthite-diopside composition is dependent on the size of the REE. Nd-O initially shows the same 6-fold coordination as Lu-O at ambient conditions, although the change to 8-fold coordination appears to occur at considerably lower pressure between 1-2GPa. Coordination change in both cases can be attributed to collapse of the silicate network and an increase in the average number of available 'crystal like' sites in the liquid, with ionic radius of the REE controlling at which pressure the preference for these sites in the melt occurs. Published mineral-melt partition coefficients for Nd, with major mineral phases such as garnet, show very little variation with pressure, in contrast to Lu. The difference in structural incorporation of Lu and Nd in the melts presented in this thesis could explain this partitioning behaviour. Overall this thesis highlights that important structural changes of the trace element bonding environment in silicate melts occur with both compositional variation and pressure. Melt structural changes with pressure cannot be neglected in predictive models of trace element behaviour, and using a single melt term to normalise the effects of melt on trace element partitioning will not accurately predict partitioning behaviour at depth during magma formation or differentiation.

Quantitative chemical and scanning electron microscopical techniques have been employed to investigate the deoxidation kinetics and changes in oxidation product morphology in low carbon steel melts. The techniques have been used to study the deoxidation processes associated with aluminium, titanium, silicon, zirconium and a calcium-aluminium alloy. After the addition of the deoxidant, the total oxygen concentrations of all melts rapidly decreased corresponding with a decrease in the size and number of inclusions observed. This continued to a plateau level of total oxygen concentration and mean inclusion diameter. Samples removed from the melts prior to deoxidation were found to contain globular MnO-FeO inclusions. It was discovered that the morphological sequence for single element deoxidants involved a progressive evolution from liquid globular to solid spherical inclusions followed by polyhedral, dendritic and coralline morphologies. Finally, sintered agglomerates were formed when inclusion clusters collapsed. The extent to which the oxidation products went down the sequence depended on: the dissolution characteristics of the deoxidant; the thermodynamic affinity of the deoxidant for oxygen in the melt; the inclusion/melt interfacial energy characteristics; the refractoriness of the oxidation products and intermediate compounds; and the degree of turbulence experienced by the melt. Explanations have been postulated which elucidate the behaviour of the different deoxidants, as not all displayed the whole morphological sequence. Silicon deoxidation produced spherical silicates, whereas the zirconia inclusions were either spherical or dendritic and the titanium oxidation products had spherical or polyhedral morphologies. Aluminium exhibited all morphologies in the sequence. Deoxidation with the calcium-aluminium alloy was found to have preceded by a two stage process. The initial stage was dominated by the formation of aluminium rich solid oxides followed by the progressive reduction by calcium, resulting in an adhesive liquid calcium-aluminate surface coating. The role of refractory crucible as a collecting surface for the capture and removal of deoxidation products from the melt was investigated, which confirmed that the inclusions were generally incorporated into the low melting point matrix phases. Turbulence also increased the probability that emergence would take place at these capture sites.

No / Spectroscopic techniques have the potential to provide powerful, molecular-specific, non-invasive measurements on polymers during melt processing operations. An exploration is reported of the application and assessment of sensitivity of in-process vibrational spectroscopy¿on-line mid-infrared (MIR), on-line near-infrared (NIR), in-line NIR and in-line Raman¿for monitoring of single screw extrusion of high-density polyethylene and polypropylene blends. These vibrational spectroscopic techniques are compared with novel in-line ultrasound velocity measurements, which were acquired simultaneously, to assess the sensitivity of each method to changes in blend composition and to explore the suitability for their use in real time process monitoring and control.