The evolution of materials at an atomistic level may have vital consequences for the properties of materials. Therefore, modelling long time scale behaviour of defects in a material is very important, particularly for those used in nuclear power plants. The materials used in nuclear power plants should have good mechanical properties to overcome the corrosive environment and high temperature. Examples of these materials are the austenitic stainless steel and the Ni-based alloys due to their high temperature properties. Molecular Dynamics (MD) and on the fly Kinetic Monte Carlo (otf-KMC) techniques have been used to model the radiation damage in austenitic stainless steel and the Ni-based alloys. This thesis represents the main findings obtained. Three potentials were implemented and used to study radiation damage in austenitic stainless steel. Structural properties such as the elastic constants for the point defects in the pure metals were first calculated. This was followed by calculating the formation energies and migration energies of vacancy and self interstitial defects in the pure metals. Different calculations were performed using each potential on the ternary alloy (Fe with 10 at.% Ni and 20 at.% Cr) and the binary alloy (Ni with 20 at.% Cr) . For example, the segregation in these alloys was investigated using Monte Carlo simulations and results obtained for both alloys at high temperature MD. Furthermore, the vacancy formation energies were calculated for both alloys using all the potentials. Radiation damage at Grain Boundaries (GBs) in fcc Ni and a Ni-Cr binary alloy has been studied using MD and otf-KMC techniques. From the results obtained, the mobility of interstitials were found to be higher than that of vacancies and tend to move quickly to the GB. Vacancies are found to migrate to the GB if they are near otherwise they tend to form clusters in the bulk. During the simulations, interesting mechanisms were observed for the point defects migration and recombinations. Large roughening at the GB was observed, especially in the alloy system and overall the total number of defects accumulated on the GB after multiple collision cascades were relatively small. The radiation in fcc Ni resulting from low energy collision cascades was also modelled using MD and otf-KMC techniques. This part of work aimed replicating the observations seen in experiment and trying to understand them. Recombinations between vacancies and interstitials were found to happen from large distances with low barriers. Most defects produced from low energy collision cascades were found to recombine or interstitials were found to form clusters. Modelling the evolution of the vacancies shows the possibility of producing Stacking Fault Tetrahedra (SFT) which were found to dissociate at 200°C.

In this project, we have assessed the structural tolerance of advanced refractory alloys to simulated nuclear fusion reactor environments, by using intense proton beams to mimic fusion neutron damage and analysing the proton damaged structures using in-situ/ex-situ transmission electron microscopy and nano-hardness measurements. Refractory metals such as tungsten or tantalum, and their binary alloy combinations, are considered as promising structural materials to withstand the unprecedented high heat loads and fast neutron/helium fluxes expected in future magnetically-confined fusion reactors. Tungsten is currently the frontrunner for the production of plasma-facing components for fusion reactors. The attractiveness of tungsten as structural material lies in its high resistance to plasma-induced sputtering, erosion and radiation-induced void swelling, together with its thermal conductivity and high-temperature strength. Unfortunately, the brittle nature of tungsten hampers the manufacture of reactor components and can also lead to catastrophic failure during reactor operations. We have focused on two potential routes to enhance the ductility of tungsten-containing materials, namely alloying tungsten with controlled amounts of tantalum, and using alternatively tantalum-based alloys containing specific tungsten additions, either as a full-thickness structural facing material or as a coating of first wall reactor components. The aim was to investigate the formation and evolution of radiation-induced damaged structures in these material solutions and the impact of those structures on the hardness of the material. The main results of this work are: (1) the addition of 5wt%Ta to W leads to saturation in the number density and average dimensions of the radiation-induced a/2 dislocation loops formed at 350C, whereas in W the loop length increases progressively and evolves into dislocation strings, and later into hydrogen bubbles and surface blisters, (2) the recovery behaviour of proton irradiated W5wt.%Ta alloy is characterized by dislocation loop growth at 600-900C, whereas voids form at 1000C by either vacancy absorption or loop collapse, (3) the presence of radiation-induced a loops at 590C in Ta hinders the formation and ordering of voids observed with increasing damage levels at 345C, (4) the addition of 5-10wt.%W to Ta delays the evolution of a/2 dislocation loops with increasing damage levels, and therefore the appearance of random voids. These results expand the composition palette available for the safe selection of refractory alloys for plasma facing components with enhanced, or at least predictable, tolerance to the heat-radiation flux combinations expected in future nuclear fusion plants.

Hydrogen embrittlement in ferrous and non-ferrous alloys is, and has been for over a century, a prominent issue within many sectors of industry. Despite this, the mechanisms by which hydrogen embrittlement occurs and the suitable means for its prevention are yet to be fully established. As hydrogen fuel becomes a prominent feature in modern concepts of a sustainable global energy infrastructure and nuclear power enters its renaissance, with commercially viable fusion plants on the horizon, hydrogen embrittlement is becoming an ever more pertinent issue. This has led to a considerable demand for novel alloys resistant to hydrogen embrittlement, notably within the bearings industry, where the commonly conflicting properties of high strength and hydrogen embrittlement resistance are required. This work investigates the mechanisms through which hydrogen embrittlement and irradiation damage occur in steels and nickel-based alloys respectively, with novel alloys designed for improved resistance. Through the engineering of secondary phases, optimised for helium and/or hydrogen trapping capacity, the novel alloys present the benefits of such trapping species with respect to embrittlement resistance. Such species have been studied in depth with respect to their interactions with hydrogen, establishing a novel mechanism of hydrogen embrittlement - the hydrogen enhanced dissolution and shearability of precipitates, leading to enhanced localised plasticity.

In medical and health physics, we are interested in the effects of ionizing radiation on biological systems, in particular, human biology. The main process by which ionizing radiations causes damage to biological systems, is through the creation of radicals close to DNA strands. The radicals are very reactive and those created within close proximity to DNA will react with the DNA causing damage, in particular single strand or double strand breaks. This damage to the DNA can cause mutations that can kill the cell, either mitotically or apoptotically, or possibly lead to a cancerous formation. Therefore it is important to study how these radicals interact with DNA strands for a correlation between the resultant products of radical reactions and DNA strand breaks. For this study, we look at the most important radical, the OH radical and it's addition to DNA bases. We will study, through quantum chemistry, the thermodynamics of OH radical addition to the four bases, Adenine, Guanine, Cytosine and Thymine. The Jaguar program developed by Schrodinger was used for DFT calculations of the Gibbs free energy of the addition. In addition, calculations for the partial charge, HOMO's and Fukui indices were calculated and compared to experiment.

Zircon (U-Th)/He (zircon He) dating has become a widely used thermochronologic method in the geosciences. Practitioners have traditionally interpreted (U-Th)/He dates from zircons across a broad spectrum of chemical compositions with a single set of ⁴He diffusion kinetics derived from only a handful of crystals (Reiners et al., 2004). However, it has become increasingly clear that a "one-size-fits-all" approach to these kinetics is inadequate, leading to erroneous conclusions and incongruent data. This dissertation develops a more grain-specific approach by showing the fundamental role that intracrystalline radiation damage plays in determining the He diffusivity in a given zircon. I present three appendices that seek to quantify the radiation damage effect on He diffusion in zircon, explain how this effect manifests in zircon He dates, and show how to exploit such manifestations to better constrain sample thermal histories. Of particular importance, this dissertation represents the first comprehensive study to concentrate on the entire damage spectrum found in natural zircon and also the first to show that two different mechanisms affect He diffusion in zircon in different ways across this spectrum. In the first appendix, I and my fellow co-authors describe results from a series of step-heating experiments that show how the alpha dose of a given zircon, which we interpret to be correlated with accumulated radiation damage, influences its He diffusivity. From 1.2 × 10¹⁶ α/g to 1.4 × 10¹⁸ α/g, He diffusivity at a given temperature decreases by three orders of magnitude, but as alpha dose increases from ~2 × 10¹⁸ α/g to 8.2 × 10¹⁸ α/g, He diffusivity then increases by about nine orders of magnitude. We parameterize both the initial decrease and eventual increase in diffusivity with alpha dose with a function that describes these changes in terms of increasing abundance and size of intracrystalline radiation damage zones and resulting effects on the tortuosity of He migration pathways and dual-domain behavior. This is combined with another equation that describes damage annealing in zircon. The end result is a new model that constrains the coevolution of damage, He diffusivity, and He date in zircon as a function of its actinide content and thermal history. The second and third appendices use this new model to decipher zircon He datasets comprising many single grain dates that are correlated with effective uranium (eU, a proxy for the relative degree of radiation damage among grains from the same sample). The model is critical for proper interpretation of results from igneous settings that show date-eU correlations and were once considered spurious (appendix B). When applied to partially reset sedimentary rocks, other sources of date variability, such as damage and He inheritance, have to be considered as well (appendix C).

In this thesis I will present an approach and apparatus for detecting and precisely characterizing any dose-dependent changes in the functional behaviour of a data converter in a neutron radiation environment. Depending on the data converter such changes could include shifts in the gain, offset, noise, or linearity of the device output. The approach leverages the neutron flux produced by an Americium-Beryllium radioisotope neutron source, and is meant to emulate the neutron environment near a Cm-244 source, as found in the sensor head of the APXS instrument. This method uses a relatively low dose rate (configurable by proximity to the source) which allows for long-term monitoring and characterization of parametric changes in device behaviour. It has the additional benefit of not requiring a reactor or accelerator, and can therefore run unattended when necessary. The prototype system, which is designed to allow the data converter to be operating during irradiation, uses LVDS signalling to drive and extract data from a minimal test board which is placed in proximity to the neutron source, and a Virtex-4 FPGA board to provide clock and power, and to perform signal processing. By separating the majority of the test equipment from the neutron environment, any radiation effects will be isolated to the DUT and a minimal set of supporting devices. The prototype design is presented here, along with initial characterization results and first test results on a commercial, off-the-shelf data converter. / Canadian Space Agency, Ontario Centres of Excellence, MacDonald, Dettwiler, and Associates

This thesis addresses various issues in U-Pb zircon geochronology, proposing new experimental protocols in conventional chemical abrasion-isotope dilution thermal ionization mass spectrometry or CA-(ID)-TIMS and developing a new method for Pb evaporation-condensation from zircon that allows high precision Pb-Pb age determination on Precambrian samples. Various experiments are also done on zircon to extract U-Pb information by in situ flux aided fusion methods and to optimize a better silica gel Pb-ionization activator. Radiation damage caused by U decay in zircon disrupts its ‘closed system’ behavior leading to the loss of daughter radiogenic Pb and resulting in inaccurate ages. A high temperature thermal annealing procedure has been proposed to prevent such Pb loss. Studies presented here have been carried out using Laser Raman Spectroscopy and Scanning Electron Microscopy to characterize radiation damage and effects of laboratory induced thermal annealing on such damage. Backscattered electron images reveal a variety of textures for ZrO2 overgrowths on zircon annealed at 1450oC. Highly damaged zircon produces finer polycrystalline aggregates (<5µm) than zircon with less damage. Raman spectroscopy indicates that crystals with different levels of radiation damage are only partially restored by annealing at 1000oC for 2–3 or 20 days. Annealing at 1450oC for 1 h results in partial breakdown of zircon but restores Raman peak widths and wave numbers. Raman spectra are much less sensitive to polarization angle for annealed highly damaged grains than for weakly damaged zircon showing that when highly damaged zircon is recrystallized, it becomes a polycrystalline aggregate that pseudomorphs the original single crystal. The whole grain Pb evaporation-condensation method is based on 206Pb-207Pb age analyses where zircon grains are pre-treated at 1450oC to drive out all disturbed Pb and then they are kept at 1600oC for an hour or two during which Pb atoms are evaporated out of the grain and deposited directly into a clean Savillex teflon vial or a wide Re filament. This technique allows the use of a 202Pb-205Pb double spike for precise isotopic fractionation correction. Examples are shown in which application of this technique to zircon from Precambrian samples has successfully yielded sub-million year age precisions.

Bulk nanocrystalline 304L and 316L austenitic stainless steels (SS) were produced by equal channel angular pressing(ECAP) at elevated temperature. The average grain size achieved in 316L and 304 L SS is ~ 100 nm, and grain refinement occurs more rapid in 316 L SS than that in 304L. Also the structures are shown to retain a predominant austenite phase. Hardness increases by a factor of about 2.5 in both steels due largely to grain refinement and an introduction of a high density of dislocations. Tensile strength of nanocrystalline steels exceeds 1 GPa with good ductility in both systems. Mechanical properties of ECAPed 316L are also shown to have less dependence on strain rate than ECAPed 304L. ECAPed steels were shown to exhibit thermal stability up to 600oC as indicated by retention of high hardness in annealed specimens. Furthermore, there is an increased tolerance to radiation-induced hardening in the nanocrystalline equiaxed materials subjected to 100 keV He ions at an average dose of 3-4 displacement-per-atom level at room temperature. The large volume fraction of high angle grain boundaries may be vital for enhanced radiation tolerance. These nanocrystalline SSs show promise for further research in radiation resistant structural materials for next-generation nuclear reactor systems.

The safety case for a proposed geological disposal facility (GDF) for radioactive wastes relies upon a series of engineered and natural barrier systems to limit the migration of harmful radionuclides into the geosphere over geological timescales. Natural minerals, dominantly phyllosilicates, are expected to be the most reactive components of both the host rock and the clay-based backfill surrounding the highly radioactive waste canisters for as long as 100,000 years. Upon eventual canister degradation, alpha-emitting radionuclides will leach into the backfill material (and eventually beyond) and the constituent mineral systems will accumulate radiation damage upon radionuclide uptake and/or surface precipitation. The following study is an assessment of the structural and chemical effects caused by alpha-particle bombardment of silicate minerals, as proxies for the radiation stability of natural materials present in the near and far field of a GDF.Microscopy and spectroscopy studies from naturally occurring radiation damage accumulated in silicates over geological timescales (forming distinct 'radiohaloes') have shown that both alpha-particle and alpha-recoil bombardment results in altered unit cell dimensions caused by the accumulation of point (Frenkel) defects. In the example of highly damaged biotite, structural breakdown through the reorientation of discrete lattice crystallites was observed; the variability of the interlayer spacing within these regions reveal the potential for damaged mica to adopt the structure of phyllosilicate breakdown products over geological time. Controlled alpha-particle irradiation using the Dalton Cumbrian Facility's 5 MV tandem pelletron ion accelerator, combined with microfocus spectroscopy analysis has revealed the mechanisms of high fluence alpha-radiation damage across 2:1 phyllosilicate minerals (biotite and chlorite); reducing the layered structures into a series of loosely connected domains of alternating lattice expansion and collapse. Radiation induced Fe redox changes have been revealed, with Fe reduction apparent at relatively low alpha-particle doses, giving way to Fe oxidation at high doses. A 'redox gradient', based on alpha-particle energy deposition through a silicate structure has therefore been proposed. In addition, the increase in 'edge' sites generated by structural deformation has been shown to be favourable for the adsorption of the Se(IV) oxyanion to the mica surface. Comprising a body of additional work, a core sample has been extracted from a spent nuclear fuel pond wall at the decommissioned Hunterston A nuclear power station and the radioactive contamination on the painted core surface has been analysed by microfocus spectroscopy. The contaminant radiostrontium has been shown to be associated with the Ti rich pigment in the surface paint, resulting in a 'patchy' accumulation of radioactivity at the core surface. In addition, inert Cs reactivity experiments using the underlying concrete have shown that Cs is preferentially uptaken by phyllosilicates within the altered mafic clasts used in the concrete aggregate.

Serial Femtosecond X-ray crystallography (SFX) is a rapidly growing experimental technique by which the structure of a crystalline sample may be determined. The X- rays arrive at the sample in pulse trains of the order of femtoseconds. Each X-ray pulse train hits a unique crystal at a random orientation and produces a diffraction pattern on the detector and series of patterns is obtained, which is the reason for the denomination "serial". Here, the radiation damage done to a sample during an SFX experiment was studied by simulating diffraction patterns including damage. Throughout, a model reference structure in the form of a reflection list was used to simulate patterns. The aim was to minimise the effects of damage through a correction based on available damage data. Firstly, a simulation case with made-up damage data was performed. The made-up data was used to modify the structure factors such that they would appear damaged. After structural reconstruction, the same data was used to correct for the damage. This was done as a validation of the method pipeline. Secondly, a more realistic case, with actual simulated damage data and a distribution of incident intensities was carried out. The expectation value of the distribution was used to correct for damage. It is found for both cases that the damage correction improves the agreement between simulated data and the original model. This is a first step toward successfully correcting for radiation damage which would be a big step forward for SFX.