Cloud-to-ground lightning strikes produce natural glasses on the surface of the Earth, called fulgurites. These natural glasses are tubular in shape with a central void surrounded by an inner glass, and the inner glass is surrounded by an outer crust or toasted region. Previous studies report different kinds of melts existing in several different types of fulgurites; however, little to no chemical data has been collected that tracks chemical variations from the inner glass to the outer crust of a fulgurite. This study uses microprobe and laser ablation inductively coupled plasma mass spectrometer analytical techniques to collect transects of chemical composition from the inner glass to the outer crust of eleven fulgurites. Five of the eleven fulgurite samples show a well-mixed, volatile-depleted inner glass, enclosed in a poorly mixed volatile enriched outer melt, suggesting that these fulgurites formed from the vaporization and condensation of materials on the inner fulgurite wall. The remaining six fulgurites show poorly mixed melts in both the inner glass and outer crust regions, and most likely originated as lightning-produced melting phenomena. These data suggest that certain enigmatic natural glasses, such as Edeowie, Dakhleh and other unknown desert glasses, may be lightning-produced, in contrast to the meteorite burst or impact related origins that have commonly been propounded.

The number of newly developed chemical entities exhibiting poor water solubility has increased dramatically in recent years. In many cases this intrinsic property results in poor or erratic dissolution in biological fluids. Improving aqueous solubility of these compounds, even temporarily, can have a significant impact on in vivo performance. Single phase amorphous solid dispersions of a drug and polymer have emerged as a technique to not only increase the level of drug supersaturation but also maintain these levels for extended periods of time. Hot-melt extrusion (HME) has become the preferred processing technique to prepare systems such as these but has a number of limitations that prevent the successful formulation of many drug substances. Within this dissertation, the use of concentration enhancing polymers was investigated in parallel with a thorough evaluation of a novel fusion-based processing technique, KinetiSol® Dispersing (KSD), to prepare single phase amorphous solid dispersions that could not be successfully prepared by HME. Studies showed that the KSD technique is suitable for rendering thermally labile and high melting point drug substances amorphous through a combination of frictional and shearing energy. Compounds such as these were shown to degrade during HME processing due to relatively long residence times and low shear forces. Similarly, the KSD process was shown to successfully process solid dispersion compositions containing a high viscosity polymer with significantly lower levels of polymer degradation than obtained by HME processing. In the final study, KSD processing was used to prepare solid dispersions containing the hydrophilic polymer Soluplus[superscript TM] and methods were evaluated to formulate a tablet with rapid tablet disintegration characteristics, a requirement for sufficient dissolution enhancement. Combined, the studies demonstrated the effectiveness of combining proper polymer selection and formulation approaches with a suitable processing technique to form solid dispersion systems that provide rapid and extended durations of supersaturation. / text

Formulation intervention, through the application of processing technologies, is a requirement for enabling therapy for the vast majority of drugs. Without these enabling technologies, poorly soluble drugs may not achieve therapeutic concentrations in the blood or tissue of interest. Conversely, freely soluble and/or rapidly cleared drugs may require frequent dosing resulting in highly cyclic tissue concentrations. During the last several years, thermal processing techniques, such as melt mixing, spray congealing, sintering, and hot-melt extrusion (HME), have evolved rapidly. Several new technologies, specifically dry powder coating, injection molding, and KinetiSol® dispersing (KSD), have been adapted to the pharmaceutical arena. Co-rotating twin screw extrusion is routinely applied for the purposes of dissolving poorly soluble drugs into glassy polymers to prepare amorphous solid dispersions, which create supersaturated drug concentrations in the gastro-intestinal tract. A potentially more advantageous alternate geometry, counter-rotating twin screw extrusion was evaluated for preparation of model amorphous solid dispersion and was observed to be more efficient in forming a solid solution and reduced the thermal stress on the drug. HME and KSD processes were utilized to prepare two phase systems consisting of a lipid, glyceryl behenate, and a polymeric amorphous solid dispersion intended to provide both controlled release of drug and supersaturated drug concentrations in the release medium. Such systems are challenging due to the potential for crystallization of the drug within the dosage form during release, which was observed to be influenced by lipophilicity and porosity of the formulation, as well as the surface area to volume ratio of the system. High molecular weight cellulose based glassy dispersions were prepared using a weakly basic model drug by KSD, which when formulated into tablets were optimized to provide either immediate or approximately 2 hours of controlled release under the pH conditions simulating the environment of the stomach. Without formulation intervention in the external phase of the tablet, these compositions gel, muting drug release and missing the drug absorption window. Compositions optimized by an in vitro dissolution test were compared to a lower molecular weight HME prepared commercial product in a beagle dog model and observed to have statistically similar bioavailability, and in one case improved variability. A modified twin screw extrusion machine was utilized to develop a continuous granulation process capable of producing granules that do not require subsequent grinding or sizing. This novel process, which employs previously un-reported temperature profiles, produces lipid based granules that when compressed into tablets produce a controlled release of tramadol hydrochloride, which were not susceptible to alcohol induced dose dumping. / text

Aluminium alloys, including both foundry and wrought alloys, have been extensively used for light-weight structural and functional applications. A grain refined as-cast microstructure is generally highly desirable for either subsequent processing ability or mechanical properties of the finished components. In this thesis, the grain refined microstructures in Al alloys have been achieved by intensive melt shearing using the melt conditioning by advanced shearing technology (MCAST) without deliberate grain refiner additions. Such grain refinement has been attributed to the enhanced heterogeneous nucleation on the dispersed oxide particles. It has been established that the naturally occurring oxides in molten Al alloys normally have a good crystallographic match with the a-Al phase, indicating the high potency of oxide particles as the nucleation sites of the a-Al phase. The governing factors for these oxide particles to be effective grain refiners in Al alloys have been proposed, including the achievement of good wetting between oxide particles and liquid aluminium, a sufficient number density and uniform spatial distribution of the dispersed oxide particles, and near equilibrium kinetic conditions in liquid alloys. In the present study, near equilibrium kinetic conditions can be achieved by intensive melt shearing using a twin screw mechanism, which has been confirmed by the observed equilibrium a-AlFeSi phase in a cast Al alloy and the transformation from g- to a-Al2O3 at 740±20oC under intensive shearing. For different alloy systems, depending on the alloy system, and melting conditions, due to the particular types of oxide formed and its crystallographic and chemical characteristics, the nucleation site of the nucleated phase is different. Specifically, MgAl2O4 relative to MgO, and a-Al2O3 relative to g-Al2O3, have higher potency as heterogeneous nucleation sites of a-Al phase in Al alloys. In future, the modification of the crystallographic match, and of the other surface characteristics related to the interfacial energy between the specific oxides and nucleated phase by trace alloying addition through segregation to the interface between oxides and nucleated phases combined with physical melt processing (such as intensive shearing in the present study) should be investigated in more detail.

Over the last fifty years, our knowledge of the Solar System has increased exponentially. Many planetary surfaces were seen for the first time through spacecraft observations. Yet the interiors of most planetary bodies remain poorly studied. This dissertation focuses on two main topics: the formation of central pit craters and what this reveals about the subsurface volatile content of the target material, and the mantle dynamics of Io and how they relate to the extensive volcanism on its surface. Central pit craters are seen on icy satellites, Mars, the Moon, and Mercury. They have terraced rims, flat floors, and a pit at or near their center. Several formation mechanisms have been suggested. This dissertation assesses the feasibility of central pit crater formation via drainage of impact melt through impact-generated fractures. For impacts on Ganymede, the expected volume of melt and volume of fracture space generated during the impact and the volume of melt able to drain before fractures freeze shut all exceed the observed central pit volumes on Ganymede. This suggests that drainage of impact melt could contribute to central pit crater formation on Ganymede. Molten rock draining through solid rock fractures will freeze shut more rapidly, so this work suggests that impact melt drainage is unlikely to be a significant factor in the formation of central pit craters on rocky bodies unless a significant amount of volatiles are present in the target. Io is the most volcanically active body in the Solar System. While volcanoes are most often associated with plate tectonics on Earth, Io shows no signs of plate tectonics. Previous work has suggested that Io could lose a significant fraction of its internal heat through volcanic eruptions. In this dissertation, I investigate the relationship between mantle convection and magma generation, migration by porous flow, and eruptions on Io. I couple convective scaling laws to a model solving the two-phase flow equations applied to a rising column of mantle. I show that Io has a partially molten upper mantle and loses the majority of its internal heat through volcanic eruption. Next, I present two-dimensional numerical simulations that self-consistently solve the two-phase flow equations including mantle convection and magma generation, migration by porous flow, and eruption. These simulations produce a high heat flux due to volcanic eruption, a thick lithosphere, a partially molten upper mantle, and a high eruption rate—all consistent with observations of Io. This model also reveals the eruption rate oscillates around the statistical steady state average eruption rate suggesting that the eruption rate and total heat flux measurements from the past 35 years may not be representative of Io's long term behavior.

This thesis describes the comparison of time-lapse field observations of suncups on alpine snow with numerical simulations. The simulations consist of solutions to a nonlinear partial differential equation which exhibits spontaneous pattern formation from a low amplitude, random initial surface. Both the field observations and the numerical solutions are found to saturate at a characteristic height and fluctuate chaotically with time. The timescale of these fluctuations is found to be instrumental in determining the full set of parameters for the numerical model such that it mimics the nonlinear dynamics of suncups. These parameters in turn are related to the change in albedo of the snow surface caused by the presence of suncups. This suggests the more general importance of dynamical behaviour in gaining an understanding of pattern formation phenomena.

Titanium carbonitride (Ti(C,N)) cermets have become more popular in recent research due to their mix of high hardness, high hot hardness, good ductility, chemical stability, and low densities. These mechanical properties make Ti(C,N)-cermets especially desirable as a replacement for current ‘hardmetals’, such as tungsten carbide cobalt (WCCo), as it is known that WC-Co exhibits poor mechanical behaviour at elevated temperatures. Additional interest and research has been conducted in reference to binders which enhance the cermet’s capability to retain strength at high temperatures while remaining ductile. One such binder, Ni3Al actually increases in yield strength up to a temperature of ~900°C. In this thesis, the production method utilizing melt infiltration for TiC, Ti(C0.7,N0.3), Ti(C0.5,N0.5), and Ti(C0.3,N0.7)-based cermets with Ni3Al binder contents of 20, 30 and 40 vol. % have successfully been developed and utilized. This process produced high density samples at each nitrogen content for all binder contents, excluding Ti(C0.3,N0.7). Ti(C0.3,N0.7)-Ni3Al samples at 20 and 30 vol. % suffered from poor infiltration and could not be tested. The reciprocating wear mechanisms were examined, using a ball-on-flat test, utilizing WC-Co spheres with a diameter of 6.35 mm as a counter-face, and test parameters of 20 Hz, 2 hrs., and applied loads of 20, 40, 60 and 80 N. The wear tracks were examined using optical profilometry, SEM, and EDS to determine the volumetric wear rate, and the dominant wear mechanisms. The wear volume, and wear mechanisms were compared with the effect of binder content, nitrogen content, and applied load.

The seasonal cycle of snow and sea ice is a fundamental feature of the Arctic climate system. In the Northern Hemisphere, about 55 million km2 of sea ice and snow undergo complete melt and freeze processes every year. Because snow and sea ice are much brighter (higher albedo) than the underlying surface, their presence reduces absorption of incoming solar energy at high latitudes. Therefore, changes of the sea-ice and snow cover have a large impact on the Arctic climate and possibly at lower latitudes. One of the most important determining factors of the seasonal snow and sea-ice cover is the timing of the seasonal melt-freeze transitions. Hence, in order to better understand Arctic climate variability, it is key to continuously monitor these transitions. This thesis presents an algorithm for obtaining melt-freeze transitions using scatterometers over both the land and sea-ice domains. These satellite-borne instruments emit radiation at microwave wavelengths and measure the returned signal. Several scatterometers are employed: QuikSCAT (1999–2009), ASCAT (2009–present), and OSCAT (2009–present). QuikSCAT and OSCAT operate at Ku-band (λ=2.2 cm) and ASCAT at C-band (λ=5.7 cm), resulting in slightly different surface interactions. This thesis discusses these dissimilarities over the Arctic sea-ice domain, and juxtaposes the time series of seasonal melt-freeze transitions from the three scatterometers and compares them with other, independent datasets. The interactions of snow and sea ice with other components of the Arctic climate system are complex. Models are commonly employed to disentangle these interactions. But this hinges upon robust and well-formulated models, reached by perpetual testing against observations. This thesis also presents an evaluation of how well eleven state-of-the-art global climate models reproduce the Arctic sea-ice cover and the summer length—given by the melt-freeze transitions—using surface observations of air temperature. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: In press. Paper 4: Submitted.</p>

During the case of a hypothetical severe accident in a light water reactor, core damage may occur and molten fuel may interact with water resulting in explosive interactions. A Fuel-Coolant Interactions (FCI) consists of many complex phenomena whose characteristics determine the energetics of the interactions. The fuel melt initially undergoes fragmentation after contact with the coolant which subsequently increases the melt surface area exposed to coolant and causes rapid heat transfer. A substantial amount of research has been done to understand the phenomenology of FCI, still there are gaps to be filled in terms of the uncertainties in describing the processes such as breakup/fragmentation of melt and droplets. The objective of the present work is to substantiate the understanding in the premixing phase of the FCI process by studying the deformation/pre-fragmentation of melt droplets and also the mechanism of melt jet breakup. The focus of the work is to study the effect of various influential parameters during the premixing phase that determine the intensity of the energetics in terms of steam explosion. The study is based on numerical analysis starting from smaller scale and going to the large scale FCI. Efforts are also taken to evaluate the uncertainties in estimating the steam explosion loads on the reactor scale. The fragmented core is expected to form a porous debris bed. A part of the present work also deals with experimental investigations on the coolability of prototypical debris bed. Initially, the phenomenology of FCI and debris bed coolability is introduced. A review of the state of the art based on previous experimental and theoretical developments is also presented. The study starts with numerical investigation of molten droplet hydrodynamics in a water pool, carried out using the Volume Of Fluid (VOF) method in the CFD code ANSYS FLUENT. This fundamental study is related to single droplets in a preconditioning phase, i.e. deformation/pre-fragmentation prior to steam explosion. The droplet deformation is studied extensively also including the effect of the pressure pulse on its deformation behavior. The effect of material physical properties such as density, surface tension and viscosity are investigated. The work is then extended to 3D analysis as a part of high fidelity simulations, in order to overcome the possible limitations of 2D simulations. The investigation on FCI processes is then continued to the analysis on melt jet fragmentation in a water pool, since this is the crucial phenomenon which creates the melt-coolant pre-mixture, an initial condition for steam explosion. The calculations are carried out assuming non-boiling conditions and the properties of Wood’s metal. The jet fragmentation and breakup pattern are carefully observed at various Weber numbers. Moreover, the effect of physical and material properties such as diameter, velocity, density, surface tension and viscosity on jet breakup length, are investigated. After the fundamental studies, the work was extended to reactor scale FCI energetics. It is mainly oriented on the evaluation of uncertainties in estimating the explosion impact loads on the surrounding structures. The uncertainties include the influential parameters in the FCI process and also the code uncertainties in calculations. The FCI code MC3D is used for the simulations and the PIE (propagation of input errors) method is used for the uncertainty analysis. The last part of the work is about experimental investigations of debris coolability carried out using the POMECO-HT facility at KTH. The focus is on the determination of the effect of the bed’s prototypical characteristics on its coolability, in terms of inhomogeneity with heap like (triangular shape) bed and the radial stratified bed, and also the effect of its multi-dimensionality. For this purpose, four particle beds were constructed: two homogeneous, one with radial stratification and one with triangular shape, respectively. The effectiveness of coolability-enhanced measures such as bottom injection of water and a downcomer (used for natural circulation driven coolability, NCDC) was also investigated. The final chapter includes the summary of the whole work. / Under ett svårt haveri i en kärnkraftsreaktor kan en härdsmälta bildas och smältan växelverka på ett explosivt sätt med kylvattnet. En sådan FCI (Fuel-Coolant-Interaction) inbegriper flera fysikaliska processer vilkas förlopp bestämmer hur stor den frigjorda energin blir. Vid kontakt med vattnet fragmenteras först härdsmältan vilket i sin tur leder till att en större yta exponeras för kylvattnet och att värmeöverföringen från smältan snabbt ökar. Mycket forskning har ägnats åt att förstå vad som sker under en FCI men det finns fortfarande luckor att fylla vad beträffar t ex osäkerheter i beskrivningen av fragmentering av såväl smälta som enskilda droppar av smält material. Syftet med detta arbete är främst att underbygga en bättre förståelse av den inledande delen av en FCI genom att studera dels hur enskilda droppar av smält material deformeras och splittras och dels hur en stråle av smält material fragmenteras. Vi studerar särskilt vilka parametrar som mest påverkar den energi som frigörs vid ångexplosionen. Problemet studeras med numerisk analys med början i liten skala och sedan i full skala. Vi söker också uppskatta de laster som explosionen utsätter reaktorns komponenter för. En annan viktig fråga gäller kylbarheten hos den slaggansamling som bildas under reaktorhärden efter en FCI. Slagghögen förväntas ha en porös struktur och en del av avhandlingen redogör för experimentella försök som genomförts för att utvärdera kylbarheten i olika prototypiska slaggformationer. I avhandlingens inledning beskrivs de fysikaliska processerna under en FCI och kylningen av en slaggansamling. Det aktuella kunskapsläget på dessa områden presenteras också utgående från tidigare experimentella och teoretiska studier. Studierna i avhandlingen inleds med numerisk analys av hydrodynamiken för en enskild droppe smälta i en vattentank där VOF-metoden i CFD-programmet ANSYS FLUENT används. Denna grundläggande studie rör en enskild droppe under förstadiet till fragmentering och ångexplosion då droppen deformeras alltmer. Deformationen studeras ingående också med hänsyn tagen till inverkan av en tryckpuls. Inverkan av olika egenskaper hos materialet, som densitet, ytspänning och viskositet studeras också. Arbetet utvidgas sedan till en beskrivning i 3D för att undvika de begränsningar som finns i en 2D-simulering. Studierna av FCI utvidgas sedan till en analys av fragmentering av en stråle smälta i vatten. Detta är en kritisk del av förloppet då smälta och vatten blandas för att ge utgångstillståndet för ångexplosionen. Beräkningarna genomförs under antagande att kokning inte sker och med materialegenskaper som för Wood´s metall. Mönstret för fragmentering och uppsplittring studeras ingående för olika Weber-tal. Dessutom studeras effekten på strålens uppsplittringslängd av parametrar som diameter och hastighet för strålen samt densitet, ytspänning och viskositet hos materialet. Efter dessa grundläggande studier utvidgas arbetet till FCI-energier i reaktorskala. Här ligger tonvikten på utvärdering av osäkerheter i bestämningen av den inverkan explosionen har på omgivande konstruktioner och komponenter. Osäkerheterna inkluderar eventuell bristande noggrannhet hos såväl de viktiga parametrarna i FCI-processen som i själva beräkningarna. Den sista delen av arbetet handlar om experimentella undersökningar av slaggformationens kylbarhet som genomförts i uppställningen POMECO-HT vid avdelningen för kärnkraftsäkerhet på KTH. Vi vill bestämma effekten av formationens prototypiska egenskaper på kylbarheten. För detta ändamål konstruerades fyra olika formationer: två homogena, en med radiell variation i partikelstorlek och en med triangulär variation. Vi undersökte också hur förbättrad kylning kan uppnås genom att tillföra kylvatten underifrån respektive via ett fallrör (kylning genom naturlig cirkulation). I det avslutande kapitlet ges en sammanfattning av hela arbetet. / <p>QC 20150507</p>

The UK Health & Safety Executive are responsible for advising on ways to ensure the safety of employees within the workplace. One of the main areas of concern is the potential problem of unwanted fire, and it has been identified that within the area of large-scale storage in warehouses, there is an uncertainty posed by large quantities of thermoplastic. Some forms of thermoplastic exhibit melt-flow behaviour when heated, and a large vertical array exposed to a fire may melt and ignite forming a pool fire in addition to a wall fire. This project is largely experimental, and aimed at quantifying the effect of a growing pool fire fuelled by a melting wall on overall fire growth rate. The pool fire has been found to increase melting and burning rates, producing a much faster growing fire. It has also been found that - 80% of flowing and burning material will enter a potential pool fire, with only 20 - 25% of total mass loss actually burning from the original array. During the project 400+ small-scale tests and several medium-scale experiments have been undertaken at both Edinburgh University and the HSE's Fire & Explosion Laboratory, Buxton. The experiments have confirmed the main parameters governing pool fire development are molecular weight degradation rate and mechanism, which control flow viscosity. There have also been investigations into other influences, the most significant of which was found to be flooring substrate. These parameters then form the basis of a simple 1-D model. A semi-infinite heat transfer approximation is used to determine temperature profile through a thermoplastic exposed to its own flame flux, with extrapolated temperature dependant material properties. The derived profile is then inserted into a gravity driven flow model, to produce estimates of flow rate and quantity for plastics undergoing either random or end chain scission thermal degradation processes. The model identifies property data which are required to permit its use as a hazard assessment tool.