Melt ponds greatly increase the transmission of solar radiation through sea ice relative to snow covered or bare ice. This rise in transmittance has the potential to enhance water column heating and primary production. I examine how spatially variable sea ice surfaces control the under-ice salinity, temperature and photosynthetically active radiation (PAR) and provide estimates of solar heating and primary production during melt. Conductivity, temperature and PAR profiles were measured in the Canadian Arctic under snow covered ice, leads, bare ice and melt ponds. The under-ice light field to a depth of 10 to 13 m was highly variable, controlled by increased transmission under melt ponds and shading by bare ice. Below, the light field became relatively homogeneous showing the depth the surface heterogeneity had an effect on transmitted PAR. Furthermore, one water column profile is not representative of the PAR, salinity or temperature under a spatially heterogeneous surface.

The central segment of the Taupo Volcanic Zone (TVZ) is one of the world’s most productive areas of silicic volcanism and geothermal activity. Rhyolites largely predominate the eruptive output in the central TVZ, with only minor basalts, andesites and dacites. The rhyolites show diversity in composition, and form a compositional continuum between two end-member types (R1 and R2), as suggested in previous studies. In this thesis I present results from a quartz- (and rare plagioclase-) hosted melt inclusions study, focussing on the volatile concentration (i.e. H2O, Cl, F, CO2) and their relative distribution between R1 and R2 rhyolites. The main objective is to add further constraints on the magmatic systems with regard to their contribution to the hydrothermal systems in the central TVZ. A comparative study between R1 and R2 melt inclusions show distinct volatile, fluid-mobile, and highly incompatible element compositions. Differences in the bulk volatile concentration of the parental magmas (i.e. basalts intruding the lower crust) are suggested to be at the origin of these volatile disparities. Further analysis on the volatile exsolution of R1 and R2 melts lead to the observation that the two rhyolite types exsolve a volatile phase at different stages in their magmatic history. From Cl and H2O concentrations, it is suggested that R1 magmas exsolve a vapour phase first, whereas R2 rhyolites more likely exsolve a hydrosaline fluid phase. These results have considerable implications for the magmatic contribution into the hydrothermal systems in the central TVZ, as differences in the composition of the resulting volatile phase may be expected. The hydrothermal systems in the central TVZ are subdivided into two groups based on their gas and fluid chemistry; and the current model suggests that there are two distinct contributions: a typical ‘arc’ system, with geochemical affinity with andesitic fluids, located along the eastern margin of the TVZ, and a typical ‘rift’ system, with geochemical affinity with rhyolitic/basaltic fluids, located along the central and/or western region of the TVZ. The addition of the new data on the rhyolitic melt inclusions, leads to a re-evaluation of the magmatic contribution into the hydrothermal systems, with a particular focus on B and Cl. The results indicate a more diverse variety of contributions to the meteoric water in the hydrothermal systems, and also show that the east-west distribution of ‘arc’ and ‘rift’ fluids is not a viable model for the central TVZ. This work emphasises that melt inclusion data and their volatile degassing history cannot be underestimated when characterising and quantifying the magmatic component in hydrothermal fluids. The melt inclusion data also provide further insight into the pre-eruptive magmatic plumbing systems and are particularly important from a hazard perspective. Included in the thesis is a detailed petrological analysis of rhyolite melt inclusions across the central TVZ and an interpretation that large silicic magma systems (in the TVZ) are typically comprised of multiple batches of magma emplaced at some of the shallowest depths on Earth. Tectonic activity is suggested to play an important role in triggering large caldera-forming eruptions as the evacuation of one magma batch could cause a regional-scale readjustment that is sufficient enough to trigger and allow simultaneous eruption of an adjacent melt batch.

Melt ponds greatly increase the transmission of solar radiation through sea ice relative to snow covered or bare ice. This rise in transmittance has the potential to enhance water column heating and primary production. I examine how spatially variable sea ice surfaces control the under-ice salinity, temperature and photosynthetically active radiation (PAR) and provide estimates of solar heating and primary production during melt. Conductivity, temperature and PAR profiles were measured in the Canadian Arctic under snow covered ice, leads, bare ice and melt ponds. The under-ice light field to a depth of 10 to 13 m was highly variable, controlled by increased transmission under melt ponds and shading by bare ice. Below, the light field became relatively homogeneous showing the depth the surface heterogeneity had an effect on transmitted PAR. Furthermore, one water column profile is not representative of the PAR, salinity or temperature under a spatially heterogeneous surface.

Various properties of the components and adhesives were modelled. The compatibility of the components were successfully incorporated into an extended Fox equation to predict the glass transition temperature. The peel strength of the adhesive was modelled in terms of the rheological properties of elastic moduli and loss tangent values at different temperatures. A second model based upon the value of the loss tangent at room temperature was also broadly successful but deviations from predicted behaviour were observed which were attributable to failure of the adhesive joints by a mode not included in the model. The modulus of the adhesive was modelled on the basis of an extended mixture rule in which the extent of compatibility was identified by a parameter n. The value of n varied as a function of adhesive composition and temperature, indicating that the behaviour of the adhesives changed subtly as the compatibility of the phases changed. The value of the parameter could not be directly related to the morphology of the adhesive phases. Fourteen commercially available poly(ethylene-co-vinyl acetate) (EVA) copolymer samples were selected in which there was a systematic change in the melt index, amount of vinyl acetate, and degree of crystallinity. Various hot melt adhesives were made using these copolymers and a standard amount of wax and resin. The materials were examined using differential scanning calorimetry (DSC), oscillatory rheometry (both controlled strain and controlled stress), and transient (creep) rheometry. The adhesives were also investigated using a variety of industrial tests which included peel adhesion and tensile testing at four different rates, open and setting time, shear and peel stress resistance at elevated temperatures, and viscosity determination over a wide range of temperatures. Detailed thermal analysis and characterisation have provided a range of accurate and systematic data on all of the materials and in particular showed that the components of the adhesive did not merely act as a mechanical mixture but had a distinct compatibility. The controlled stress technique was found to more discriminatory than the controlled strain, due to the more precisely controlled heating and cooling of the sample during loading and evaluation. Other key differences between the techniques are attributable to the different thermal histories imposed upon the semi-crystalline adhesive components. Detailed analysis of the complex rheological curves showed several key factors. One of the most important was the modulus crossover temperature Tx which was shown to correlate well with the softening point of the adhesive, its open time, and the heat resistance under shear as determined by the shear adhesion failure temperature (SAFT). It was possible to construct a linear relationship between Tx and SAFT which allowed prediction of this key adhesive parameter. There was no significant relationship established between the softening point of an adhesive and its heat resistance, open time, or critical thermal characteristics, and the use of the softening point as a useful indicator of adhesive performance is contested. The open time was shown to be clearly influenced by the properties of the copolymer. The relationship between open time and melt index is complex and two competing mechanisms are thought responsible. These are the inability to fully wet the substrate for high molecular weights and resistance to complete substrate penetration by capillary effects for adhesives formulated with low molecular weight polymers. Both of these effects cause a reduction in open time. The cloud points of the adhesives were independent of the molecular weight but strongly affected by composition. Degree of crystallinity was also an influence at higher molecular weights. Cloud point correlated slightly with the onset of crystallisation as determined by DSC however differences are extremely small and the method was not deemed robust enough for widespread industrial application. Various properties of the components and adhesives were modelled. The compatibility of the components were successfully incorporated into an extended Fox equation to predict the glass transition temperature. The peel strength of the adhesive was modelled in terms of the rheological properties of elastic moduli and loss tangent values at different temperatures. A second model based upon the value of the loss tangent at room temperature was also broadly successful but deviations from predicted behaviour were observed which were attributable to failure of the adhesive joints by a mode not included in the model. The modulus of the adhesive was modelled on the basis of an extended mixture rule in which the extent of compatibility was identified by a parameter n. The value of n varied as a function of adhesive composition and temperature, indicating that the behaviour of the adhesives changed subtly as the compatibility of the phases changed. The value of the parameter could not be directly related to the morphology of the adhesive phases.

A cartonboard package is often sealed and closed with an adhesive – either a hot-melt adhesive (adhesives that are applied in a molten state on the cartonboard) or a dispersion adhesive (adhesives that are applied as water-based dispersions). This thesis focuses on the process of hot-melt gluing, and how material properties and process conditions affect the performance of the adhesive joint. Requirements vary depending on how the package is to be used. A package that is only supposed to protect the product during transport differs from one that is supposed to attract consumers and facilitate their use of the product. If a package has been opened, due to external or internal forces that cause a fracture in the adhesive joint, the consumer may choose another package instead. A fracture of the adhesive joint may occur in several different ways; for example, a cohesive fracture in the adhesive, an interfacial fracture between the adhesive and one of the cartonboard surfaces, and a cohesive fracture in the cartonboard. The traditional way of testing the adhesive joint is to subjectively evaluate the fibre tear after manually tearing the joint apart. The primary interest of this study has been to find an objective method that can characterise the adhesive joint – that is, its strength and joint characteristics. The work has principally concentrated on physical experiments where the Y-peel method has been evaluated and further developed, including the construction of a laboratory adhesive applicator. Adhesive joint failure is analysed and correlated to the force-elongation curve during Y-peel testing in order to explore various mechanisms of the failure. The force versus elongation curves are transformed into a force versus inelastic deformation curve for the adhesive joint. The inelastic deformation of the adhesive joint is defined as the inelastic opening of the adhesive joint perpendicular to the cartonboard surface. The dissipative descending energy has been used to characterise the adhesive joint. High descending dissipative energy showed high resistance against final failure of the joint. This correlates very well with the manual fibre-tear test. Characteristic force-elongation curves in Y-peel testing – that is, the shape of the curve – have been analysed, and four main failure modes have been identified. The finite element method has been used to predict mechanical behaviour in the ascending part of the force-elongation curve. When it comes to local behaviour, a high stiffness adhesive results in bending behaviour while a low results in shearing, but on a global scale, no big difference was detected on the ascending part of the force-elongation curve. The new laboratory adhesive applicator and finite element method can be used to objectively design the interaction between the adhesive and the cartonboard for a specific application. This can be achieved by modifying the cartonboard, the adhesive or the process parameters.

Thesis (Ph. D.)--University of Missouri-Columbia, 1996. / Typescript. Vita. Includes bibliographical references (leaves 201-208). Also available on the Internet.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 221-229).

The mechanisms and timescales associated with the triggering of caldera-forming eruptions remain ambiguous and poorly constrained. Do such eruptions start vigorously, then escalate, or can there be episodicity? Are they triggered through internal processes (e.g. recharge, buoyancy), or can external modulations play an important role? Key to answering these questions is the ability to reconstruct the state of the magma body immediately prior to eruption. My dissertation research seeks to answer these questions through detailed investigation of four voluminous caldera-forming eruptions: (1) 650 km3, 0.767 Ma Bishop Tuff, Long Valley, (2) 530 km3, 25.4 ka Oruanui eruption, Taupo, (3) 2,500 km3, 2.08 Ma Huckleberry Ridge Tuff, Yellowstone and (4) 250 km3, 26.91 Ma Cebolla Creek Tuff, Colorado. The main techniques I applied integrated glass geochemistry (major, trace and volatile), diffusion modeling, and detailed field sampling. In chapters two, three, and four these methods are applied to the initial fall deposits of three supereruptions (Bishop, Oruanui and Huckleberry Ridge) that preserve field-evidence for different opening behaviors. These behaviors range from continuous deposition of fall deposits and ignimbrite (Bishop), to repetitive start/stop behavior, with time breaks between eruptive episodes on the order of weeks to months (Oruanui, Huckleberry Ridge). To reconstruct the timescales of opening activity and relate this to conduit processes, I used two methods that exploit diffusion of volatiles through minerals and melt, providing estimates for the rate at which magmas ascended to the surface. This knowledge is then integrated with the pre-eruptive configuration of the magma body, based on melt inclusion chemistry, to interpret what triggered these systems into unrest. Finally, in chapter five I take a different approach by integrating geochemical data for melt inclusions and phenocryst minerals to test whether the mechanism of heat and volatile recharge often called upon to trigger crystal-rich dacitic magmas (the so-called monotonous intermediates), is applicable to the Cebolla Creek Tuff. This dissertation includes both previously published and unpublished co-authored material, and three online supplementary excel files.

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.

Aluminium applications can be found in the vast majority of industries – particularly the automotive, aerospace and building sectors. Light weight, good corrosion resistance, high strength with good machining and weldability has led 6xxx series alloy to be the most widely used for extrusion products. Semi-continuous direct-chill (DC) casting is a well established process and the most widely used in the production of wrought aluminium extrusion billets. The techniques have continuously evolved since its invention in the 1930s. To ensure high productivity and a quality billet by DC casting, grain refiners are added during casting prior to solidification. It is efficient, cost effective and considered optimized in modern production techniques. However, some problems still persist, for example, macrosegregation, centerline cracking, porosity, hot tearing, etc. For surface finish critical products, particles in added grain refiners may cause surface defects during downstream processing. Additions of grain refiners are also not desirable for recycling of the end use products. As a novel DC casting technology, the melt conditioned DC casting (MC-DC) technology is developed to achieve uniform fine equiaxed grains without deliberate additions of grain refiners. The MC-DC process is implemented by submerging a rotor-stator high shear device into the mould assembly of a conventional hot-top vertical DC caster. In this work, the fundamentals of MC-DC process has been investigated by studying the flow patterns in the sump using computer modelling in combination with thermal field measurement and delineation of the sump profile. Followed is the microstructural evolution of the MC-DC castings. Then the formation of Fe-bearing intermetallics which are critical to the arrangement of homogenisation treatment are presented. The grain refining mechanism by MC-DC is due to enhanced heterogeneous nucleation on dispersed oxides and grain fragments by intensive melt shearing, in combination with dendrite fragmentation and transportation in a uniform temperature and solute field. By optimising MC-DC parameters, alleviation of macrosegregation can be achieved even compared with DC-GR castings. Another finding is the correlation between grain structure and the distribution of the Fe-intermetallic particles. It has been demonstrated that equiaxed dendritic grains with fine secondary dendritic arm spacings achieved in MC-DC are preferred rather than finer granular grains in grain refined material. MC-DC also promotes the formation of α- Fe-bearing intermetallics. All these offer the potential for the reduction of homogenisation practices currently required as part of the DC process.