Pages 154 and 155 were not included in the thesis. / <p> The post-irradiation annealing of highly converted styrene-polystyrene systems was explored. Experimental conditions necessary for the entrapment of high concentrations of free radicals in such systems were investigated. They were found to bear a relation to the glass transition temperature of the system.</p> <p> The concentration of free radicals formed by subjecting the polymer-monomer systems to Gamma rays, at room temperature, was measured, and the subsequent GM and GP values were calculated. The structure of the formed radical was found to be in agreement with that suggested by previous investigators. The free radicals decay was examined at varied temperatures above and below Tgs, and was found to follow a second order mechanism. The activation energy of decay was found to increase by raising the temperature above Tgs.</p> <p> When irradiation was executed at temperatures below Tgs, post-irradiation annealing led to high rates of polymerization when carried out at temperatures above Tgs. </p> <p> The number average molecular weight was practically unchanged during the polymerization of the last few percent monomer.</p> / Thesis / Master of Engineering (MEngr)

<p>Thorium dioxide (ThO₂) and metallic uranium (alpha-U) represent important alternative nuclear fuels. Investigating the behavior of defects introduced into these materials in an irradiation environment is critical for understanding microstructure evolution and property changes. The objective of this dissertation is to investigate the clustering of point defects in ThO₂ and alpha-U under irradiation, into voids and prismatic dislocation loops as a function of irradiation dose rate and temperature. To achieve this, we have developed a mean-field cluster dynamics (CD) model based on reaction rate theory to predict the evolution of self-interstitial atom (SIA) and vacancy loops in neutron-irradiated alpha-U. Detailed atomistic simulations have been carried out using molecular dynamics (MD) to study the configuration of such loops and compute their energetics, which are essential parameters of the CD model. Bond-boost hyper-MD simulations have been performed to compute the diffusivity of uranium SIA and vacancies, which govern the kinetics of the clustering phenomenon. Another CD model has been demonstrated for proton-irradiated ThO₂, considering the clustering of Th and O SIA and vacancies into SIA loops and voids, respectively, with varying sizes and stoichiometry. The compositions of all SIA loops and voids dictated by crystallography of ThO₂ in its fluorite structure have been presented in their respective cluster composition space (CCS). The CD model solves the density evolution of off-stoichiometric loops and voids, with irradiation, in their respective CCS. MD simulations have been performed to compute the energetics of different clusters in their CCS, as parameters of the CD model. Temperature-accelerated MD simulations have been performed to compute the diffusivity of Th and O point defects, that dictates the kinetics of defect clustering on irradiation. In alpha-U, the CD predictions show an accumulation of small sized vacancy loops and the growth of SIA loops with irradiation dose, which closely fits the reported size distribution of loops in neutron-irradiated alpha-U by Hudson and coworkers. The CD predicted density of defect clusters in proton-irradiated ThO₂, shows the evolution of near-stoichiometric SIA loops in their CCS. The size distribution of SIA loops at high irradiation doses closely corresponds to the transmission electron microscopy (TEM) observations reported in the literature. Also, the CD model did not predict the growth of voids and vacancy clusters, which is consistent with findings in literature. The model was further used to predict the density of sub-nanometric defect clusters and point defects, on low-dose irradiation, that significantly impairs the thermal conductivity of ThO₂. An extensive TEM and CD investigation has also been carried out to study the growth and coarsening of SIA loop and voids during post-irradiation isochronal annealing of ThO₂ at high temperatures.</p>