Tourmaline is an aluminoborocyclosilicate mineral with a complex arrangement of atoms. With highly variable chemistry and multiple cation sites, tourmaline is one of the last complex minerals whose structure was unraveled, and its response to changes in Pressure-Temperature-Time (P-T-X) are not well understood. Due to its stability at high temperature and pressure, tourmaline has the potential to be an informative mineral in terms of petrogenetic indicators and could be used in assessing provenance, thermobarometry and geochronology. Three reactions were proposed to understand the cation exchange and disordering between the Y- and Z-sites in the tourmaline structure. These reactions include: 1. YFe2+ + ZAl + OH ; ZFe3+ + YAl + O + H ; in two samples with varying Fe2+ content. 2. YMg + ZAl ; ZMg + YAl. 3. YFe3+ + ZAl ; ZFe3+ + YAl. Using single crystal X-ray diffraction and stepwise heating, the extent and effect of the exchange between the Y- and Z-sites in response to changes in temperature was described. In response to increased temperature, equivalent amounts of Fe2+, Fe3+, Mg2+ of the Y-sites exchange with Al of the Z-sites. This leads to decreases in Y-site average bond length, increases in Z-site average bond length, shortening of a lattice parameters, lengthening of c lattice parameters and decreases in quadratic elongation. Additionally, the T-site experienced an increased in tetrahedral rotation and ditrigonality and changes to the crimping of the tetrahedral ring upon heating. The cation exchange and disordering in these samples relates to the stability of tourmaline at elevated temperatures in that tourmaline will undergo cation exchange and disordering to maintain the stability of the mineral. This has implications on the conditions in which tourmaline is formed as well as stability of tourmaline and other minerals and materials in different P-T-X conditions.

Inconel alloys are commonly used as structural materials in nuclear reactors. One of these alloys, the Inconel X-750, is a γ’ Ni3(Al, Ti) strengthened superalloy extensively used in the cores of reactors, such as spacers in CANada Deuterium Uranium (CANDU) fuel channels. Prior to their application in commercial reactors, accelerated irradiation tests had been conducted in liquid metal fast reactors. Results did not indicate any problem stemming from significant fast neutron irradiation. However, recently it has been found that the ex-service CANDU Inconel X-750 spacers became severely brittle after a lengthy exposure to reactor environment. The underlying mechanism remains unclear and thus forms the focus of this current investigation, predominantly through transmission electron microscopy (TEM). This dissertation unfolds with the literature review in Chapter 2, followed by presentation of novel techniques in Chapter 3 on the preparation of TEM samples from small reactor components, namely the spacers. Chapter 4 presents TEM characterizations of ex-service spacers removed from the reactors. To simulate neutron irradiation over wide temperature range in an effort to understand the damage mechanisms, heavy ion irradiations were conducted and reported in Chapter 5 and 6. Irradiations are found to significantly alter the stability of the primary strengthening phase γ’, a systematic experimental study of which is presented in Chapter 7. To fully understand the effects of transmutation produced helium on irradiation induced cavity and dislocation microstructures, TEM in-situ heavy ion irradiations with hot/cold pre-injected helium were conducted and reported in Chapter 8 and 9. Helium was found to play an important role in the irradiation-induced instability of γ’ in nickel-based superalloys, the discussion of which is presented in Chapter 10. As one of the most important defect structures induced from irradiation, the stacking-fault-tetrahedra, were dynamically observed and are described in a journal manuscript in Appendix A. In addition to broadening current understanding of material degradation mechanism for in-service CANDU spacer, this study also provides comprehensive information on irradiation damage in nickel based superalloys, irradiation induced lattice defects and phase instability in face centered cubic alloys, as well as helium’s effects on cavity formation, dislocation evolution, and phase transformation. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2013-09-06 15:21:02.334

The application of epitaxially grown, III-V semiconductor-based nanostructures to the development of electro-optical and all-optical switches is investigated through the fabrication and testing of integrated photonic devices designed using multimode interference (MMI) waveguides. The properties and limitations of the materials are explored with respect to the operation of those devices through electrical carrier injection and optical pumping. MMI waveguide geometry was employed as it offered advantages such as a very compact device footprint, low polarization sensitivity, large bandwidth and relaxed fabrication tolerances when compared with conventional single-mode waveguide formats. The first portion of this dissertation focuses on the characterization of the materials and material processing techniques for the monolithic integration of In0.15Ga0.85As/GaAs self-assembled quantum dots (SAQD) and InGaAsP/InGaAsP multiple quantum wells (MQW). Supplemental methods for post-growth bandgap tuning and waveguide formation were developed, including a plasma treatment process which is demonstrated to reliably inhibit thermally induced interdiffusion of Ga and In atoms in In0.15Ga0.85As/GaAs quantum dots. The process is comparable to the existing approach of capping the SAQD wafer with TiO2, while being simpler to implement along-side companion techniques such as impurity free vacancy disordering. Study of plasma-surface interactions in both wafer structures suggests that the effect may be dependent on the composition of the contact layer. The second portion of this work deals with the design, fabrication, and the testing of MMI switches which are used to investigate the limits of electrical current control when employing SAQD as the active core material. A variable power splitter based on a 3-dB MMI coupler is used to analyze the effects of sub-microsecond electrical current pulses in relation to carrier and thermal nonlinearities. Electrical current controlled switching of the variable power splitter and a tunable 2 x 2 MMI coupler is also demonstrated. The third part of this dissertation explores the response of In0.15Ga0.85As/GaAs SAQD waveguide structures to photogenerated carriers. Also presented is a simple, but effective, design modification to the 2 x 2 MMI cross-coupler switch that allows control over the carrier distribution within the MMI waveguide. This technique is combined with selective-area bandgap tuning to demonstrate a compact, working, all-optical MMI based switch.

In this thesis, we study the kinetic disordering of systems interacting with an agent or a walker. Our studies divide naturally into two classes: for the first, the dynamics of the walker conserves the total magnetization of the system, for the second, it does not. These distinct dynamics are investigated in part I and II respectively. In part I, we investigate the disordering of an initially phase-segregated binary alloy due to a highly mobile vacancy which exchanges with the alloy atoms. This dynamics clearly conserves the total magnetization. We distinguish three versions of dynamic rules for the vacancy motion, namely a pure random walk , an "active" and a biased walk. For the random walk case, we review and reproduce earlier work by Z. Toroczkai et. al., [9] which will serve as our base-line. To test the robustness of these findings and to make our model more accessible to experimental studies, we investigated the effects of finite temperatures ("active walks") as well as external fields (biased walks). To monitor the disordering process, we define a suitable disorder parameter, namely the number of broken bonds, which we study as a function of time, system size and vacancy number. Using Monte Carlo simulations and a coarse-grained field theory, we observe that the disordering process exhibits three well separated temporal regimes. We show that the later stages exhibit dynamic scaling, characterized by a set of exponents and scaling functions. For the random and the biased case, these exponents and scaling functions are computed analytically in excellent agreement with the simulation results. The exponents are remarkably universal. We conclude this part with some comments on the early stage, the interfacial roughness and other related features. In part II, we introduce a model of binary data corruption induced by a Brownian agent or random walker. Here, the magnetization is not conserved, being related to the density of corrupted bits ρ. Using both continuum theory and computer simulations, we study the average density of corrupted bits, and the associated density-density correlation function, as well as several other related quantities. In the second half, we extend our investigations in three main directions which allow us to make closer contact with real binary systems. These are i) a detailed analysis of two dimensions, ii) the case of competing agents, and iii) the cases of asymmetric and quenched random couplings. Our analytic results are in good agreement with simulation results. The remarkable finding of this study is the robustness of the phenomenological model which provides us with the tool, continuum theory, to understand the nature of such a simple model. / Ph. D.

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