Simulating radiation effects in iron with embedded oxide nanoparticles

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

Helium bubbles in bcc Fe and their interactions with irradiation

The properties of helium bubbles in a body-centred cubic (bcc) Fe lattice have been examined. The atomic configurations and formation energies of different He-vacancy complexes were determined. The 0 K results show that the most energetically favourable He to Fe vacancy ratio increases from about 1:1 for approximately 5 vacancies up to about 4:1 for 36 vacancies. The formation mechanisms for small He clusters have also been considered. Isolated interstitials and small clusters can diffuse quickly through the lattice. MD simulations of randomly placed interstitial He atoms at 500 K showed clustering over the time scale of nanoseconds with He clusters containing up to 4 atoms being mobile over this time scale. He clusters containing 4 or 5 atoms were shown to eject an Fe dumbbell interstitial which could then detach from the He cluster and diffuse with the remaining He-vacancy complex being effectively immobile. Collision cascades initiated near larger bubbles showed that Fe vacancies produced by the cascades readily become part of the He-vacancy complexes. Energy barriers for He to join an existing bubble as a function of the He-vacancy ratio are also calculated. These can be larger than the diffusion barrier in the pristine lattice, but are lower when the bubbles contain excess vacancies, thus indicating that bubble growth may be kinetically constrained

Simulating radiation damage in a bcc Fe system with embedded yttria nanoparticles

We present a molecular dynamics study of radiation damage arising from nuclear collisions close to embedded yttria nanoparticles in a bcc Fe matrix. The model assumes a perfect body-centred cubic (bcc) iron matrix in which yttria nano-particles are embedded as a simplified model of an Oxide Dispersion Strengthened steel. It is shown how the nano-particles interact with nearby initiated collision cascades, through cascade blocking and absorbing energy. Fe defects accumulate at the interface both directly from the ballistic collisions and also by attraction of defects generated close by. The nano-particles generally remain intact during a radiation event and release absorbed energy over times longer than the ballistic phase of the collision cascade

Heterostructures of GaN with SiC and ZnO enhance carrier stability and separation in framework semiconductors

A computational approach, using the density functional theory, is employed to describe the enhanced electron-hole stability and separation in a novel class of semiconducting composite materials, with the so-called double bubble structural motif, which can be used for photocatalytic applications. We examine the double bubble containing SiC mixed with either GaN or ZnO, as well as related motifs that prove to have low formation energies. We find that a 24-atom SiC sodalite cage inside a 96-atom ZnO cage possesses electronic properties that make this material suitable for solar radiation absorption applications. Surprisingly stable, the inverse structure, with ZnO inside SiC, was found to show a large deformation of the double bubble and a strong localisation of the photo-excited electron charge carriers, with the lowest band gap of ca. 2.15 eV of the composite materials considered. The nanoporous nature of these materials could indicate their suitability for thermoelectric applications

Thermodynamically accessible titanium clusters TiN, N = 2–32

We have performed a genetic algorithm search on the tight-binding interatomic potential energy surface (PES) for small TiN (N = 2–32) clusters. The low energy candidate clusters were further refined using density functional theory (DFT) calculations with the PBEsol exchange–correlation functional and evaluated with the PBEsol0 hybrid functional. The resulting clusters were analysed in terms of their structural features, growth mechanism and surface area. The results suggest a growth mechanism that is based on forming coordination centres by interpenetrating icosahedra, icositetrahedra and Frank–Kasper polyhedra. We identify centres of coordination, which act as centres of bulk nucleation in medium sized clusters and determine the morphological features of the cluster

Simulating radiation damage in a bcc Fe system with embedded yttria nanoparticles

This paper was accepted for publication in the journal Journal of Nuclear Materials and the definitive published version is available at http://dx.doi.org/10.1016/j.jnucmat.2013.02.016We present a molecular dynamics study of radiation damage arising from nuclear collisions close to embedded yttria nanoparticles in a bcc Fe matrix. The model assumes a perfect body-centred cubic (bcc) iron matrix in which yttria nano-particles are embedded as a simplified model of an Oxide Dispersion Strengthened steel. It is shown how the nano-particles interact with nearby initiated collision cascades, through cascade blocking and absorbing energy. Fe defects accumulate at the interface both directly from the ballistic collisions and also by attraction of defects generated close by. The nano-particles generally remain intact during a radiation event and release absorbed energy over times longer than the ballistic phase of the collision cascade

Influence of the prefactor to defect motion in alpha-Iron during long time scale simulations

We present a study of the influence of the prefactor in the Arrhenius equation for the long time scale motion of defects in α-Fe. It is shown that calculated prefactors vary widely between different defect types and it is thus important to determine these accurately when implementing on-the-fly kinetic Monte Carlo (otf-KMC) simulations. The results were verified by reproducing many events using Molecular Dynamics (MD) and Temperature-Accelerated Dynamics (TAD). The calculated prefactor was shown to increase the relative interstitial-vacancy diffusion rates by an order of magnitude compared to the assumption of a constant prefactor value and the ordering of the rate table for the interstitial defect migration mechanisms was also changed. In addition, low prefactor values were observed for the 4 interstitial dumbbells configuration with low barrier transitions

Synthesis Target Structures for Alkaline Earth Oxide Clusters

Knowing the possible structures of individual clusters in nanostructured materials is an important first step in their design. With previous structure prediction data for BaO nanoclusters as a basis, data mining techniques were used to investigate candidate structures for magnesium oxide, calcium oxide and strontium oxide clusters. The lowest-energy structures and analysis of some of their structural properties are presented here. Clusters that are predicted to be ideal targets for synthesis, based on being both the only thermally accessible minimum for their size, and a size that is thermally accessible with respect to neighbouring sizes, include global minima for: sizes n = 9 , 15 , 16 , 18 and 24 for (MgO) n ; sizes n = 8 , 9 , 12 , 16 , 18 and 24 for (CaO) n ; the greatest number of sizes of (SrO) n clusters ( n = 8 , 9 , 10 , 12 , 13 , 15 , 16 , 18 and 24); and for (BaO) n sizes of n = 8 , 10 and 16