Generation and migration of helium and other point defects under irradiation causes ferritic steels based on the Fe-Cr system to age and fail. This is motivation to study point defect migration and the He equation of state using atomistic simulations due to the steels' use in future reactors. A new potential for the Fe-Cr-He system developed by collaborators at the Lawrence Livermore National Laboratory was validated using published experimental data. The results for the He equation of state agree well with experimental data. The activation energies for the migration of He- and Fe-interstitials in varying compositions of Fe-Cr lattices agree well with prior work. This research did not find a strong correlation between lattice ordering and interstitial migration energy

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abstract: A mineral’s helium content reflects a balance between two competing processes: accumulation by radioactive decay and temperature-dependent diffusive loss. (U-Th)/He dating of zircon and other uranium and thorium-bearing minerals provides insight into the temperature histories of rocks at or near Earth’s surface that informs geoscientists’ understanding of tectonic and climate-driven exhumation, magmatic activity, and other thermal events. The crystal structure and chemistry of minerals affect helium diffusion kinetics, recorded closure temperatures, and interpretations of (U-Th)/He datasets. I used empirical and experimental methods to investigate helium systematics in two minerals chronometers: zircon and xenotime. The same radioactivity that makes zircon a valuable chronometer damages its crystal structure over time and changes zircon helium kinetics. I used a zircon, titanite, and apatite (U-Th)/He dataset combined with previously published data and a new thermal model to place empirical constraints on the closure temperature for helium in a suite of variably damaged zircon crystals from the McClure Mountain syenite of Colorado. Results of this study suggest that the widely-used zircon damage accumulation and annealing model (ZRDAAM) does not accurately predict helium closure temperatures for a majority of the dated zircons. Detailed Raman maps of Proterozoic zircon crystals from the Lyon Mountain Granite of New York document complex radiation damage zoning. Models based on these results suggest that most ancient zircons are likely to exhibit intracrystalline variations in helium diffusivity due to radiation damage zoning, which may, in part, explain discrepancies between my empirical findings and ZRDAAM. Zircon crystallography suggests that helium diffusion should be fastest along the crystallographic c-axis. I used laser depth profiling to show that diffusion is more strongly anisotropic than previously recognized. These findings imply that crystal morphology affects the closure temperature for helium in crystalline zircon. Diffusivity and the magnitude of diffusive anisotropy decrease with low doses of radiation damage. Xenotime would make a promising (U-Th)/He thermochronometer if its helium kinetics were better known. I performed classic step-wise degassing experiments to characterize helium diffusion in xenotime FPX-1. Results suggest that this xenotime sample is sensitive to exceptionally low temperatures (∼50 °C) and produces consistent (U-Th)/He dates. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2019

<p>  </p> <p>Materials performance under extreme conditions is pivotal to the design of advanced nuclear reactor materials. Nanocrystalline metals possess improved radiation resistance and superior mechanical properties. However, it remains a major challenge to stabilize the fine grains in nanocrystalline materials at elevated temperatures. The response of abundant interfaces and triple junctions to thermal annealing, plastic straining and radiation damage profoundly influence the overall performance of nanocrystalline metals. The objective of this thesis is to illustrate a new alloy design strategy via engineering the interfaces and triple junctions of triphase nanocomposites to enhance the thermal stability, mechanical strength and radiation tolerance of nanocrystalline metallic materials simultaneously. </p> <p>In triphase nanocomposites where each phase is nearly immiscible to the others, the triple junctions and phase boundaries form a 3D interlocking network that could significantly increase the thermal and radiation stability. In this thesis, two distinct triphase architectures were explored: nanolaminate and nanocrystalline Cu-Ag-Fe composites fabricated by magnetron sputtering. The effectiveness of Cu-Ag-Fe triphase triple junctions in mitigating thermal grooving was evaluated by considering grooving kinetics. Additionally, micropillar compression tests on Cu-Ag-Fe nanolaminate composites demonstrated substantial enhancement of strength and strain hardening capability comparing to Cu/Fe multilayers. The nanocrystalline Cu-Ag-Fe composites exhibited a distinct texture evolution and greatly enhanced resistance to grain coarsening. In situ sequential dual beam (He + Kr) irradiation studies show nanocrystalline Cu-Ag-Fe composites have a remarkable bubble swelling resistance, suggesting the strong He storage and defect annihilation capability of the triphase nanocomposites. The results obtained from this thesis provide innovative perspectives on the design of high strength nanostructured metals with enhanced thermal stability and radiation tolerance.</p>

<p> Part One deals with thin films of SnO₂ which were prepared by ion-beam sputtering, reactive sputtering and anodic oxidation. The films were found to be either amorphous or crystalline in their prepared state. </p> <p> The structure of the as-deposited amorphous films, as revealed by transmission electron microscopy, presented interesting features: there was a continuous structure in the case of high-temperature deposition, whereas an "island structure" was revealed in the case of low-temperature deposition. Furthermore, heat treatment of films having an "island structure" showed this structure to be maintained provided the heating was done with unsupported films, while the structure became continuous when heat treatment was performed on supported specimens. </p> <p> The crystalline form of the films has been worked out, and found to generally be cassiterite; nevertheless a phase different from cassiterite has been occasionally noticed during this work. In some cases it could be tentatively identified as SnO, while other cases it remains unidentified. Crystallization temperatures found here are somewhat different from those indicated in the literature, namely: 500, 300, 225ºC according to substrate temperature and nature and type of heat treatment. Anodic oxidation of tin has been performed(apparently for the first time) in a non-solvent electrolyte, the films being consistently crystalline. </p> <p> The results obtained in the case of films deposited on water-cooled substrates, have revealed a dependence of film structure on film thickness and this effect has been confirmed in supplementary experiments. Thus thick films appear to crystallize spontaneously at room temperature. </p> <p> Part Two deals with radiation damage studies. Our experiments on krypton-ion bombarded SnO₂ films show that amorphous specimens remain amorphous following ion bombardment. The electron-microscope evidence of whether crystalline SnO₂ is amorphized by ion bombardment was tentatively negative, while the gas-release evidence was strongly negative. </p> Part Three deals with diffusion in inert-gas implanted SnO₂. In the first section we give the theoretical background that enabled us to deduce from our experiments rough estimates of the melting temperature, self-diffusion temperature. and activation-energy for self-diffusion of the less mobile ion in SnO₂. In particular, we obtain the following results: </p> <p> T_melting = 2600 - 3000ºK </p> <p> T_self-diffusion = 1480 - 1870ºK for a 2 min. time scale and 134±44Å distance scale. </p> <p> ∆H_self-diffusion = 87,200 - 131,00 cal/mole </p> <p> Note that the melting point for tine oxide is variously reported in different handbooks to lie between 1400 and 2200ºK. From a comparison with other work we have concluded that our value for ∆H is very likely that for oxygen-ion diffusion. </p> / Thesis / Master of Science (MSc)

The overall purpose of this dissertation is to develop a multi-scale framework that can simulate radiation defect accumulation across a broad range of time and length scales in metals. In order to accurately describe defect accumulation in heterogeneous microstructures and under complex irradiation conditions, simulation methods are needed that can explicitly account for the effect of non-homogeneous microstructures on damage accumulation. In this dissertation, an advanced simulation tool called spatially resolved stochastic cluster dynamics (SRSCD) is developed for this purpose. The proposed approach relies on solving spatially resolved coupled rate equations of standard cluster dynamics methods in a kinetic Monte Carlo scheme. Large-scale simulations of radiation damage in polycrystalline materials are enabled through several improvements made to this method, including a pseudo-adaptive meshing scheme for cascade implantation and implementation of this method in a synchronous parallel kinetic Monte Carlo framework. The performance of the SRSCD framework developed in this dissertation is assessed by comparison to other simulation methods such as cluster dynamics and object kinetic Monte Carlo and experimental results including helium desorption from thin films and defect accumulation in neutron-irradiated bulk iron. The computational scaling of the parallel framework is also investigated for several test cases of irradiation conditions. SRSCD is next used to investigate radiation damage in three main types of microstructures, using α-iron as a test material: iron thin films, coarse-grained bulk iron, and nanocrystalline iron. SRSCD is used to investigate the mechanisms involved with defect accumulation in irradiated materials, such as effective diffusivity of helium in thin films and the effect of grain boundary sink strength on defect accumulation in nano-grained metals, and to predict defect populations in irradiated materials for comparison with experiments. Particular emphasis is placed on the role of microstructural features such as free surfaces and grain boundaries in influencing damage accumulation. Finally, the methodology developed in this dissertation is applied in the context of multiscale modeling and experimental design. To complete the multi-scale transition between defect-level behavior and macroscopic material property changes caused by irradiation, the relationship between mechanical loading and radiation damage is investigated. The impact of radiation damage on hardening of irradiated materials is investigated by using the results of SRSCD as inputs into polycrystalline crystal plasticity simulations. This is carried out in bulk iron by fitting hardening models to experimental data from neutron irradiation of iron and then used to predict hardening under irradiation conditions beyond what has already been accomplished in experimental studies. In addition, SRSCD is used to demonstrate the temperature shift required to achieve equivalent damage accumulation in irradiation conditions with significantly differing dose rates, such as in the case of using ion irradiation to simulate damage from neutron irradiation. In this dissertation, the development of SRSCD and its application in a multi-scale framework to predict macroscopic material property changes in metals represents a significant improvement over the state of the art due to improved simulations of defect accumulation and direct upscaling of results into polycrystalline plasticity models. The tools and understanding of defect behavior developed here will allow predictive modeling of metal degradation in reactor-relevant damage environments, including the defected microstructure and macroscopic material property changes due to irradiation.

Alloys used in fission and in future fusion reactors are subjected to extreme conditions including high temperatures, corrosive and intense radiation environments. Understanding the processes occurring at the microscopic level during radiation events is essential for the further development of them. As a prospective candidate material for new reactors, oxide dispersion strengthened (ODS) steels have shown good radiation resistance and the ability to trap He into fine scale bubbles, thus preventing swelling and preserving high-temperature strength. This thesis represents the findings obtained by performing computational studies of radiation effects in pure iron, Y-Ti-O systems and a simplified model of ODS using Molecular Dynamics (MD) and on-the-fly Kinetic Monte Carlo (otf-KMC) techniques. MD studies of radiation damage were carried out in a perfect body-centred cubic (bcc) iron matrix (alpha-Fe) in which yttria nanoparticles are embedded as a simplified model of an ODS steel. The results have shown how the nanoparticles interact with nearby initiated collision cascades, through cascade blocking and energy absorption. Fe defects accumulate at the interface both directly from the ballistic collisions and also by attraction of defects generated close by. The nanoparticles generally remain intact during a radiation event and release absorbed energy over times longer than the ballistic phase of the collision cascade. Also the nanoparticles have shown ability to attract He atoms as a product of fission and fusion reactions. Moreover, studies showed that He clusters containing up to 4 He atoms are very mobile and clusters containing 5 He or more become stable by pushing an Fe atom out of its lattice position. The radiation damage study in the Y-Ti-O materials showed two types of residual damage behaviour: when the damage is localized in a region, usually close to the initial primary knock-on atom (PKA) position and when PKA is directed in the channelling direction and creates less defects compared to the localised damage case, but with a wider spread. The Y2TiO5 and Y2Ti2O7 systems showed increased recombination of defects with increased temperature, suggesting that the Y-Ti-O systems could have a higher radiation resistance at higher temperatures. The otf-KMC technique was used to estimate the influence of the prefactor in the Arrhenius equation for the long time scale motion of defects in alpha-Fe. It is shown that calculated prefactors vary widely between different defect types and it is thus important to determine these accurately when implementing KMC simulations. The technique was also used to study the recombination and clustering processes of post-cascade defects that occur on the longer time scales.

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.

Tungsten will be a key material for the plasma-facing components in future fusion devices. Its mechanical performance under neutron irradiation will strongly influence the lifetime of these devices. Pure tungsten has been subjected to a variety of irradiating species - tungsten ions, helium ions and fission neutrons - between 500&deg;C and 900&deg;C and the change in mechanical properties measured by micro-mechanical testing methods. Pure tungsten has been ion-irradiated using self-ions and helium ions at 500&deg;C and 800&deg;C. Nanoindentation has been performed on all specimens, and the 800&deg;C specimens have been tested at temperatures up to 750&deg;C using high-temperature nanoindentation. The irradiation temperature has no effect on the hardening of tungsten. Hardening from self-ion irradiation has not saturated by 4.5 dpa with an increase in hardness of 3.3 GPa. The hardening from helium implantation is only 0.73 GPa, and a comparison with literature shows that this hardening only depends on the concentration of the injected helium. The difference is likely due to the much smaller defect size of helium-vacancy clusters when compared to dislocation loops. High-temperature nanoindentation shows that helium-implanted tungsten softens rapidly, with the hardening from the radiation damage becoming negligible above 450&deg;C. Self-ion implanted tungsten does not soften by 650&deg;C, again likely due to the size difference of the defects. Micro-mechanical tests - namely micro-cantilever bending - have been used to investigate the plastic and fracture characteristics of tungsten before and after irradiation. Plastic behaviour is dominated by size effects due to the 3 &mu;m depth of the implanted layers, which makes nanoindentation a better method for investigating radiation damaged layers. In fracture testing, fracture is rarely seen. Using the yield stress to calculate fracture toughness, the hardening from irradiation damage results in an increase in fracture toughness from 2.2 MPa&radic;m to 6.0 MPa&radic;m. The work of deformation at 1&percnt; is also increased after irradiation from 7.2 x 10^-11 Nm to 2.8 x 10^-10 Nm, implying that the implanted damage is not leading to an increase in embrittlement by reducing K^1c. Neutron irradiated tungsten also shows an increase in fracture toughness after irradiation from 6.5 MPa&radic;m to 14.5 MPa&radic;m. However, the BDTT increases by &Tilde; 100&deg;C in poly-crystal tungsten and &Tilde; 500&deg;C in single-crystal tungsten. The difference in BDTT does not exist in the unimplanted material. The change after irradiation is likely due to the fine (&tilde; 3 &mu;m) grain size and 900&deg;C irradiation temperature causing a significant amount of the displacement damage to be absorbed at the grain boundaries. The hardness of neutron irradiated and ion irradiated tungsten is very close: 10.4 GPa and 11.2 GPa respectively, demonstrating the ions are likely well-representing the neutron damage in pure tungsten.

Materials in nuclear reactors and satellites experience continually damaging radiation which leads to their degradation over time. Currently, a materials safe working lifetime within these environments is estimated with a large, costly, safety margin. The work of this thesis aims to improve the usefulness of an optical technique known as reflection anisotropy spectroscopy (RAS), which once fully characterised could allow materials to be actively monitored in such environments. The intrinsic optical anisotropy of the Cu(110) surface has been exploited to study nanoscale kinetics of ion bombarded surfaces. Within the Cu(110) RA spectrum the 2.1eV peak is particularly sensitive to surface defects and largely unaffected by the bulk of the substrate. Using the Poelsema-Comsa model (which assumes defects scatter surface electronic states within a patch centred on the defect) it can be demonstrated that at finite temperatures the decay of the 2.1eV peak contains information relating to the diffusion of surface defects. A kinetic Monte Carlo simulation has been created to model the destruction of this peak and allows further understanding of the diffusion processes involved. The decay of the 2.1eV peak with ion bombardment has been successfully modelled for a range of temperatures using experimental RAS data for comparison. Through a novel way of analysing RAS data, it has been shown that the total scattering cross section per ion impact decreases with bombardment time, which it is believed to be due to surface diffusion. This could give a novel way of measuring surface diffusion directly from RAS measurements. Clustering of ion induced surface defects has been analysed and the results found are consistent with STM images of the same surface obtained 30 minutes after bombardment. While molecular dynamics calculations have previously attempted to predict the surface topology and defect clustering nanoseconds after impact, using a kinetic Monte Carlo simulation improves on this, demonstrating that diffusion on long time scales (currently inaccessible using molecular dynamics calculations) play an important role in predicting nano-surface topology. 2.1eV peak recovery after surface damage by ion bombardment was also investigated. The peak was found to recover at finite temperatures, which is also seen in experimental data. It was concluded that the surface diffusivity values in the literature are too high and a new value for diffusivity has been calculated by comparing simulation and experimental data.