Doctor of Philosophy

dissertationTitanium dioxide (TiO2) is used as a whitening agent in numerous domestic and technological applications and is mainly produced by the high temperature chloride process. A new hydrometallurgical process for making commercially pure TiO2 pigment is described with the goal of reducing the necessary energy consumption and CO2 emissions. The process includes alkaline roasting of titania slag with subsequent washing, HCl leaching, solvent extraction, hydrolysis, and calcination stages. The thermodynamics of the roasting reaction were analyzed, and the experimental parameters for each step in the new process were optimized with respect to TiO2 recovery, final product purity, and total energy requirements. Contacting the leach solution with a tertiary amine extractant resulted in complete Fe extraction in a single stage and proved effective in reducing the concentration of discoloring impurities in the final pigment to commercially acceptable levels. Additionally, a new method of producing Ti powders from titania slag is proposed as a potentially more energy efficient and lower cost alternative to the traditional Kroll process. Thermodynamic analysis and initial experimental results validate the concept of reducing titanium slag with a metal hydride to produce titanium hydride (TiH2 ) powders, which are subsequently purified by leaching and dehydrided to form Ti powders. The effects of reducing agent type, heating time and temperature, ball milling, powder compaction, and eutectic chloride salts on the conversion of slag to TiH2 powders were determined. The purification of reduced powders through NH4Cl, NaOH, and HCl leaching stages was investigated, and reagent concentration, leaching temperature, and time were varied in order to determine the best conditions for maximum impurity removal and recovery of TiH2. A model plant producing 100,000 tons TiO2 per year was designed that would employ the new method of pigment manufacture. A comparison of the new process and the chloride process indicated a 25% decrease in energy consumption and CO2 emissions. For the Ti powder making process, a 10,000 tons per year model plant employing the metal hydride reduction was designed and a comparison with the Kroll process indicated potential for over 60% less energy consumption and 50% less CO2 emission

Temozolomide induces senescence but not apoptosis in human melanoma cells

Temozolomide (TMZ), a DNA alkylating agent used in the treatment of melanoma, is believed to mediate its effect by addition of a methyl group to the O6 position of guanine in DNA. Resistance to the agent may be in part due to the activity of O6-methylguanine-DNA methyl transferase (MGMT). In the present study, we show that sensitivity of melanoma cells to TMZ was dependent on their p53 status and levels of MGMT. Analysis of the mechanisms underlying reduced viability showed no evidence for induction of apoptosis even though marked levels of apoptosis was seen in TK6 lymphoma cells. Sensitivity of melanoma cells was associated with p53-dependent G2/M cell cycle arrest and induction of senescence. To verify the role of p53, the assays were repeated in presence of pifithrin-α, an inhibitor of p53. This resulted in increased viability of melanoma cells with wild-type p53 and reversed G2/M cell cycle arrest. Paradoxically, apoptosis was increased in melanoma but decreased as expected in TK6 lymphoma cells. These results are consistent with the view that TMZ is relatively ineffective against melanoma due to defective apoptotic signalling resulting from activation of p53. The nature of the defects in apoptotic signalling remains to be explored

Multimessenger Search for Sources of Gravitational Waves and High-Energy Neutrinos: Results for Initial LIGO-Virgo and IceCube

We report the results of a multimessenger search for coincident signals from the LIGO and Virgo gravitational-wave observatories and the partially completed IceCube high-energy neutrino detector, including periods of joint operation between 2007-2010. These include parts of the 2005-2007 run and the 2009-2010 run for LIGO-Virgo, and IceCube's observation periods with 22, 59 and 79 strings. We find no significant coincident events, and use the search results to derive upper limits on the rate of joint sources for a range of source emission parameters. For the optimistic assumption of gravitational-wave emission energy of $10^{-2}$\,M$_\odot$c$^2$ at $\sim 150$\,Hz with $\sim 60$\,ms duration, and high-energy neutrino emission of $10^{51}$\,erg comparable to the isotropic gamma-ray energy of gamma-ray bursts, we limit the source rate below $1.6 \times 10^{-2}$\,Mpc$^{-3}$yr$^{-1}$. We also examine how combining information from gravitational waves and neutrinos will aid discovery in the advanced gravitational-wave detector era

The IceCube Neutrino Observatory, the Pierre Auger Observatory and the Telescope Array: Joint Contribution to the 34th International Cosmic Ray Conference (ICRC 2015)

We have conducted three searches for correlations between ultra-high energy cosmic rays detected by the Telescope Array and the Pierre Auger Observatory, and high-energy neutrino candidate events from IceCube. Two cross-correlation analyses with UHECRs are done: one with 39 cascades from the IceCube `high-energy starting events' sample and the other with 16 high-energy `track events'. The angular separation between the arrival directions of neutrinos and UHECRs is scanned over. The same events are also used in a separate search using a maximum likelihood approach, after the neutrino arrival directions are stacked. To estimate the significance we assume UHECR magnetic deflections to be inversely proportional to their energy, with values $3^\circ$, $6^\circ$ and $9^\circ$ at 100 EeV to allow for the uncertainties on the magnetic field strength and UHECR charge. A similar analysis is performed on stacked UHECR arrival directions and the IceCube sample of through-going muon track events which were optimized for neutrino point-source searches.Comment: one proceeding, the 34th International Cosmic Ray Conference, 30 July - 6 August 2015, The Hague, The Netherlands; will appear in PoS(ICRC2015

The IceCube Neutrino Observatory, the Pierre Auger Observatory and the Telescope Array:Joint Contribution to the 34th International Cosmic Ray Conference (ICRC 2015)

We have conducted three searches for correlations between ultra-high energy cosmic rays detected by the Telescope Array and the Pierre Auger Observatory, and high-energy neutrino candidate events from IceCube. Two cross-correlation analyses with UHECRs are done: one with 39 cascades from the IceCube `high-energy starting events' sample and the other with 16 high-energy `track events'. The angular separation between the arrival directions of neutrinos and UHECRs is scanned over. The same events are also used in a separate search using a maximum likelihood approach, after the neutrino arrival directions are stacked. To estimate the significance we assume UHECR magnetic deflections to be inversely proportional to their energy, with values $3^\circ$, $6^\circ$ and $9^\circ$ at 100 EeV to allow for the uncertainties on the magnetic field strength and UHECR charge. A similar analysis is performed on stacked UHECR arrival directions and the IceCube sample of through-going muon track events which were optimized for neutrino point-source searches

Enhancing Thermal Conductivity of UO\u3csub\u3e2\u3c/sub\u3e with the Addition of UB\u3csub\u3e2\u3c/sub\u3e via Conventional Sintering Techniques

Uranium dioxide has been the primary fuel type used in light water reactors for more than 40 years and proven to be reliable and robust. However, the Fukushima-Daiichi nuclear accident has motivated new work evaluating fuels with characteristics promoting accident tolerance, including enhanced thermal conductivity. Recently, additives have been investigated to increase thermal conductivity, but research has been largely focused on non-fissile additions. This study investigated the use of fissile additives to not only increase the thermal conductivity but also increase the uranium loading. Uranium diboride was chosen as the additive for this study due to its promising corrosion behavior as well as its significantly higher thermal conductivity at 573 K (25 Wm−1K−1) when compared to UO2 (7 Wm−1K−1). Uranium diboride powder was fabricated via the arc melting technique and a ball milling process prior to mixing with UO2 in a 90/10 wt% UO2/UB2 ratio. Green bodies were made using a uniaxial die and subjected to a traditional pressureless sintering technique at 2073 K in argon. Sintered samples were analyzed via laser flash analysis for thermal diffusivity and differential scanning calorimetry for specific heat capacity in order to calculate thermal conductivity. The samples displayed an increase of 36–55% in thermal conductivity between 323 and 1273 K when compared to the benchmark samples (pure UO2) as reported in open literature