Nanocrystalline (NC) metals with averaged grain size smaller than 100 nm have shown promising mechanical properties such as higher hardness and toughness than conventional coarse-grained metals. Unlike conventional metals in which the deformation is controlled by dislocation activities, the microstructural evolution in NC metals is mainly dominated by grain rotation and stress-driven grain boundary motion (SDGBM) due to the high density of grain boundaries (GBs). SDGBM is thus among the most studied modes of microstructural evolution in NC materials with particular interests on their fundamental atomistic mechanisms. In the first part of this thesis, molecular dynamics simulations were used to investigate the influences of Triple Junctions (TJs) on SDGBM of symmetric tilt GBs in copper by considering a honeycomb NC model. TJs exhibited asymmetric pinning effects to the GB migration and the constraints by the TJs and neighboring grains led to remarkable non-linear GB motion in directions both parallel and normal to the applied shear. Based on these findings, a generalized model for SDGBM in NC Cu was proposed. In the second part, the interaction of SDGBM with crack, voids and precipitates was investigated. It was found that depending on the GB structure, material type and temperature, there is a competition between different atomistic mechanisms such as crack healing, recrystallization and GB decohesion. It is hoped that the findings of this work could clarify the micro-mechanisms of various experimental phenomena such as grain refinement in metals during severe plastic deformation, which can be used to design optimized route of making stabilized bulk NC metals. / February 2016

Three sheet materials, including high purity aluminum, commercial purity aluminum, and an aluminum-magnesium alloy with 3 wt% magnesium, were produced into single-crystals in the solid-state. The method, developed in 1939 by T. Fujiwara at Hiroshima University, involves straining a fully recrystallized material then passing it into a furnace with a high temperature gradient at a specific rate. This method preserves composition and particulate distributions that melt-solidification methods do not. Large single crystals were measured for their orientation preferences and growth rates. The single-crystals were found to preferably orient their growth direction to the <120> to <110> directions, and <100> to <111> directions normal to the specimen surface. The grain boundary mobility of each material was found to be a function of impurity content. The mobility constants observed were similar to those reported in the literature, indicating that this method of crystal growth provides an estimate of grain boundary mobility. This is the first study the effect of impurities and alloying to this single-crystal production process, and to show this method’s applicability in determining grain boundary mobility information. / text

This research work presents the first comprehensive study on nanocrystalline materials produced in bulk quantities using a novel continuous electrodeposition process. A series of nanocrystalline Ni and Ni-Fe alloy continuous foils were produced and an intensive investigation into their structure and various properties was carried out. High-resolution transmission electron microscopy (HR-TEM) revealed the presence of local strain at high and low angle, and twin boundaries. The cause for these local strains was explained based on the interpretation of non-equilibrium grain boundary structures that result when conditions of compatibility are not satisfied. HR-TEM also revealed the presence of twin faults of the growth type, or &ldquo;growth faults&rdquo;, which increased in density with the addition of Fe. This observation was found to be consistent with a corresponding increase in the growth fault probabilities determined quantitatively using X-ray diffraction (XRD) pattern analysis. Hardness and Young&rsquo;s modulus were measured by nanoindentation. Hardness followed the regular Hall-Petch behaviour down to a grain size of 20 nm after which an inverse trend was observed. Young&rsquo;s modulus was slightly reduced at grain sizes less than 20 nm and found to be affected by texture. Microstrain based on XRD line broadening was measured for these materials and found to increase primarily with a decrease in grain size or an increase in intercrystal defect density (i.e., grain boundaries and triple junctions). This microstrain is associated with the local strains observed at grain boundaries in the HR-TEM image analysis. A contribution to microstrain from the presence of growth faults in the nanocrystalline Ni-Fe alloys was also noted. The macrostresses for these materials were determined from strain measurements using a two-dimensional XRD technique. At grain sizes less than 20 nm, there was a sharp increase in compressive macrostresses which was also owed to the corresponding increase in intercrystal defects or interfaces in the solid.

This research work presents the first comprehensive study on nanocrystalline materials produced in bulk quantities using a novel continuous electrodeposition process. A series of nanocrystalline Ni and Ni-Fe alloy continuous foils were produced and an intensive investigation into their structure and various properties was carried out. High-resolution transmission electron microscopy (HR-TEM) revealed the presence of local strain at high and low angle, and twin boundaries. The cause for these local strains was explained based on the interpretation of non-equilibrium grain boundary structures that result when conditions of compatibility are not satisfied. HR-TEM also revealed the presence of twin faults of the growth type, or &ldquo;growth faults&rdquo;, which increased in density with the addition of Fe. This observation was found to be consistent with a corresponding increase in the growth fault probabilities determined quantitatively using X-ray diffraction (XRD) pattern analysis. Hardness and Young&rsquo;s modulus were measured by nanoindentation. Hardness followed the regular Hall-Petch behaviour down to a grain size of 20 nm after which an inverse trend was observed. Young&rsquo;s modulus was slightly reduced at grain sizes less than 20 nm and found to be affected by texture. Microstrain based on XRD line broadening was measured for these materials and found to increase primarily with a decrease in grain size or an increase in intercrystal defect density (i.e., grain boundaries and triple junctions). This microstrain is associated with the local strains observed at grain boundaries in the HR-TEM image analysis. A contribution to microstrain from the presence of growth faults in the nanocrystalline Ni-Fe alloys was also noted. The macrostresses for these materials were determined from strain measurements using a two-dimensional XRD technique. At grain sizes less than 20 nm, there was a sharp increase in compressive macrostresses which was also owed to the corresponding increase in intercrystal defects or interfaces in the solid.

Our study is focused on the behavior of grain boundaries in uranium dioxide system under irradiation conditions. The research can be seen as two parts: the study of interaction of the grain boundary and the damage cascade, and the calculation of Kapitza resistance of grain boundaries. The connection between these two parts lies in that damage cascades bring in changes in the structure and other properties of grain boundaries, and inevitably the Kapitza resistance of the grain boundary changes as well. For the first part, we studied interactions of grain boundaries and damage cascades in uranium dioxide system by simulating two types of bombardments: one direct bombardment into a grain boundary leading to ballistic-collision-mediated interface mixing; the other bombardment is in the close vicinity of a grain boundary causing interface biased defect migration. We found that more defects are trapped by the grain boundary followed by the first type of bombardment, resulting in enhanced grain boundary energy. By comparing with the second type of bombardment, we are able to reveal the mechanisms of the interaction between defects and grain boundaries. For the second part, we employed the non-equilibrium molecular dynamics method to calculate the Kapitza resistance of different coincident site lattice boundaries with or without defects loaded, and later we found that a universal positive correlation between the Kapitza resistance and the grain boundary energy can be well established, regardless of the cause of boundary energy changes. Our study provides a deeper understanding of the Kapitza resistance of the grain boundary and its evolutions under irradiation, which benefits multi-scale modeling of uranium dioxide thermal properties under extreme radiation conditions as well as experimental studies of fuel material thermal properties.

The aim of this thesis is to investigate the effects of additives, reactive elements and impurities, on the lifetime of thermal barrier coatings. The thesis consists of a number of studies on interface adhesion, impurity diffusion, grain boundary sliding and cleavage processes and their impact on the mechanical behaviour of grain boundaries. The effects of additives and impurity on interface adhesion were elaborated by using total energy calculations, electron localization and density of states, and by looking into the atomic separations. The results of these calculations allow the assessment of atomic level contributions to changes in the adhesive trend. Formation of new bonds across the interface is determined to improve the adhesion in reactive element(RE)-doped structures. Breaking of the cross interface bonds and sulfur(S)-oxygen(O) repulsion is found responsible for the decreased adhesion after S segregation. Interstitial and vacancy mediated S diffusion and the effects of Hf and Pt on the diffusion rate of S in bulk NiAl are studied. Hf is shown to reduce the diffusion rate, and the preferred diffusion mechanism of S and the influence of Pt are revealed to be temperature dependent. Finally, the effects of reactive elements on alumina grain boundary strength are studied. Reactive elements are shown to improve both the sliding and cleavage resistance, and the analysis of atomic separations suggest an increased ductility after the addition of quadrivalent Hf and Zr to the alumina grain boundaries.

Turbine components operate under severe loading conditions and at high and varying temperatures that result in thermal stresses in the presence of temperature gradients created by hot gases and cooling air. Moreover, static and cyclic loads as well as the motion of rotating components create mechanical stresses. The combined effect of complex thermo-mechanical stresses promote nucleation and propagation of cracks that give rise to fatigue and creep failure of the turbine components. Therefore, the relationship between thermo-mechanical stresses, chemical composition, heat treatment, resulting microstructure, operating temperature, material damage, and potential failure modes, i.e. fatigue and/or creep, needs to be well understood and studied. Artificial neural networks are promising candidate tools for such studies. They are fast, flexible, efficient, and accurate tools to model highly non-linear multi-dimensional relationships and reduce the need for experimental work and time-consuming regression analysis. Therefore, separate neural network models for γ’ precipitate strengthened Ni based superalloys have been developed for predicting the γ’ precipitate size, thermal expansion coefficient, fatigue life, and hysteresis energy. The accumulated fatigue damage is then estimated as the product of hysteresis energy and fatigue life. The models for γ’ precipitate size, thermal expansion coefficient, and hysteresis energy converge very well and match experimental data accurately. The fatigue life proved to be the most challenging aspect to predict, and fracture mechanics proved to potentially be a necessary supplement to neural networks. The model for fatigue life converges well, but relatively large errors are observed partly due to the generally large statistical variations inherent to fatigue life. The deformation mechanism map for 1.23Cr-1.2Mo-0.26V rotor steel has been constructed using dislocation glide, grain boundary sliding, and power law creep rate equations. The constructed map is verified with experimental data points and neural network results. Although the existing set of experimental data points for neural network modeling is limited, there is an excellent match with boundaries constructed using rate equations which validates the deformation mechanism map.

Nanocrystalline (NC) metals and alloys are known to possess superior mechanical properties, e.g., strength, hardness, and wear-resistance, as compared to conventional microcrystalline materials. NC metals are characterized by a mean grain size <100 nm; in this grain size regime, inelastic deformation can occur via a combination of interface-mediated mechanisms viz., grain boundary sliding/migration, and dislocation nucleation from grain boundary sources. Recent studies have suggested that these interface-mediated inelastic deformation mechanisms in fcc metals are influenced by non-glide stresses and interfacial free volume, unlike dislocation glide mechanisms that operate in microcrystalline fcc metals. Further, observations of tension-compression strength asymmetry in NC metals raise the possibility that yield and inelastic flow in these materials may not be adequately described by solely the deviatoric stress. Unfortunately, most literature concerning the mechanical testing of NC metals is limited to uniaxial deformation or nanoindentation techniques, and the multiaxial deformation behavior is often predicted assuming initially isotropic yield and subsequent flow normal to the yield surface. The primary objective of this thesis is to obtain a better understanding of the nature of inelasticity in NC metals by simulating multiaxial deformation at the atomistic resolution, and developing methods to interpret the results in ways that would be useful from a continuum constitutive modeling viewpoint. First, we have presented a novel, statistical mechanics-based approach to unambiguously resolve the elastic-plastic transition as an avalanche in the proliferation of mobile defects. This approach is applied to nanocrystalline Cu to explore the influence of pressure and multiaxial stress states on the inelastic deformation behavior. The results suggest that initial yield in nanocrystalline Cu under biaxial loading is only weakly anisotropic in the 5 nm grain size regime, and that plastic flow evolves in a direction normal to the von Mises yield surface. However, triaxial deformation simulations reveal a significant effect of the superimposed hydrostatic stress on yielding under shear. These results are analyzed in detail in order to assess the influence of pre-existing internal stresses and interfacial excess volume on the inelastic deformation behavior. Further, we have studied the effects of imposed hydrostatic pressure on the shear deformation behavior of Cu bicrystals containing symmetric tilt interfaces, as well as Cu nanocrystals of different grain sizes. Most interfaces exhibit an increase in shear strength with imposed compressive hydrostatic pressure. However, for some interfaces, this trend is reversed. Neither the sign nor the magnitude of the pressure-induced elevation in shear strength appears to correlate with interface structure or particular deformation mechanism(s). In Cu nanocrystals, we observe that imposed compressive pressure leads to strengthening under shear deformation, and the effect of imposed pressure on the shear strength becomes stronger with increase in grain size or temperature. Activation parameters for shear deformation have been computed for these nanocrystals, and computed values seem to agree with existing experimental and theoretical estimates. Finally, we have proposed some modifications to conventional isothermal molecular dynamics algorithms, in order to isolate dislocation nucleation events from interfacial sources, and thereby permit explicit computation of the activation parameters for such events.

Fuel cladding is one of the most critical components of nuclear reactors; so it is important to improve our understanding of various properties and behaviors of the cladding under different conditions approximating the nuclear reactor environment. Moreover, the efficiency of energy production, in addition to safety concerns, has resulted in progressive improvement of nuclear reactors design from Generation I to Generation IV. To complement this progressive trend, materials used for fuel cladding need to be improved or new materials should be developed. In this thesis, I address problems in the improvement of present fuel cladding and also investigate fuel cladding materials to be used in future Generation IV nuclear reactors. In the case of current Zircaloy-4 fuel claddings, a detailed evaluation of the surface roughness effects on their performance and properties of Zircaloy-4 fuel claddings was studied. A smoother surface on Zircaloy-4 cladding tubes is demanded by the customers; however no systematic study is available addressing the effect of surface roughness on the claddings’ performance. Thus the effects of surface roughness on texture, oxidation, hydriding behaviors and mechanical properties of Zircaloy-4 cladding tubes were investigated using various methods. It was found that surface roughness has some effects on the oxidation of Zircaloy-4. Increasing the surface roughness would increase the weight gain, however, this effect was more pronounced at the initial oxidation stages. Synchrotron techniques were used to characterize the electronic structure of zirconium alloys in their oxidized and hydrided states. With this approach, complex interactions between hydrogen and oxygen in the zirconium matrix could be investigated, which could not be resolved using conventional methods. As a candidate for future fuel cladding material, Incoloy 800H/HT, which is expected to be considered in super-critical water-cooled Gen IV reactors, was studied in order to optimize microstructure, texture and grain boundary characteristics. A specific Thermo-Mechanical Processing (TMP) was employed to manipulate the texture, microstructure and grain boundary character distribution. The deformation and annealing textures of thermo-mechanically processed samples were investigated by means of X-ray diffraction and orientation imaging microscopy. It was found that different rolling paths lead to different textures. The origin of different textures in differently (unidirectional and cross) rolled Incoloy 800H/HT at high deformation strains were investigated. In addition, the recrystallization kinetic of differently rolled samples was studied. It was found that the oriented nucleation plays an important role in determining the recrystallization texture. Unidirectional rolled samples exhibited a faster recrystallization kinetic compared with cross rolled ones, due to the presence of γ-fibre. The effect of the aforementioned microstructural parameters (grain size, texture and GBCD) on the oxidation resistance of Incoloy 800H/HT in super-critical water was investigated. It was found that the oxidation resistance of Incoloy 800H/HT can be improved by TMP. The optimum TMP process for enhancing the oxidation resistance was proposed. Microstructural parameters that can improve the oxidation resistance of Incoloy 800H/HT were identified. These findings will contribute to the effective selection of fuel cladding material for application in Gen IV SCW reactors.

Fabrication of nanoscale Josephson junctions and Superconducting Quantum Interference Devices (SQUID) is very promising but challenging topic in the superconducting electronics and device technology. In order to achieve best sensitivity of SQUIDs and to reproduce them easily with a straightforward method, new fabrication techniques for realization of nanoSQUIDs needs to be investigated. This study concentrates on investigation of new fabrication methodology for manufacturing nanoSQUIDs with High Temperature Bi-Crystal Grain Boundary Josephson Junctions fabricated onto SrTiO3 bi-crystal substrates using YBa2Cu3O7-δ (YBCO) thin-films. In this process nanoscale patterning of YBCO was realized by using electron beam patterning and physical dry etching of YBCO thin films on STO substrates. YBCO thin films were deposited using RF magnetron sputtering technique in the mixture of Ar and O2 gases and followed by annealing at high temperatures in O2 atmosphere. Structural characterization of YBCO thin films was done by Scanning Electron Microscope (SEM) and Energy Dispersive X-ray Spectroscopy (EDX). Superconducting properties of thin films was characterized by AC magnetic susceptibility measurements. Nanoscale structures on YBCO thin films were fabricated by one E-Beam Lithography (EBL) step followed by Reactive Ion Etching (RIE) and physical dry etching. First SiO2 thin film were deposited on YBCO by RF magnetron sputtering and it was patterned by EBL using Polystyrene (PS) as resist material and RIE. Then SiO2 was used as an etch mask for physical dry etching of YBCO and nanoscale structures on YBCO were formed.