Made available in DSpace on 2014-10-09T12:23:49Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:52Z (GMT). No. of bitstreams: 1 01106.pdf: 7271038 bytes, checksum: 0782814eac2bd5593952b215dd48d0e7 (MD5) / Tese (Doutoramento) / IEA/T / Instituto de Fisica, Universidade de Sao Paulo - IF/USP

High resolution fluorescence spectra are presented of the sideband of the 5D0+ 7F0 transition of Sm++ in KBr and KCl. Several Van Hove singularities of the phonon spectrum of the host material are directly observed. They occur at slightly different frequenciesfromthose predicted by density of states calculations based on neutron diffraction measurements. Numerical calculations of both sidebands are given and compared with experiment, with quite good agreement. Sidebands observed for Eu++ in KBr and KCl are also presented and discussed. / Thesis / Doctor of Philosophy (PhD)

no abstract provided. / Thesis / Master of Science (MSc)

Laser Engineered Net Shaping (LENS™) is a rapid-manufacturing procedure that involves complex thermal, mechanical, and metallurgical interactions. The finite element method (FEM) may be used to accurately model this process, allowing for optimized selection of input parameters, and, hence, the fabrication of components with improved thermo-mechanical properties. In this study the commercial FEM code SYSWELD® is used to predict the thermal histories and residual stresses generated in LENS™-produced thin plates of AISI 410 stainless steel built by varying the process parameters laser power and stage translation speed. The computational results are compared with experimental measurements for validation, and a parametric study is performed to determine how the thermo-mechanical properties vary with these parameters. Thermal calculations are also performed with the code ABAQUS® to evaluate its potential use as a modeling tool for the LENS™ process.

No description available.

In this work the method of isotopic substitution in neutron diffraction is used to measure the partial structure factors of several binary systems. Molten sodium chloride at 820(5) °C is investigated and an improvement is made on the previously available data. The applicability of a simple model pair potential for the asymptotic decay of the pair correlation functions is discussed. The glass forming system zinc chloride is also investigated in both the molten phase at 332(5) °C and the glassy phase at 25(1) °C. The measured partial pair distribution functions show that the zinc atoms are fourfold coordinated in both the glass and the liquid and that the first sharp diffraction peak in the total structure factor is mainly due to the zinc-zinc correlations. A simple ionic model can account for several factors associated with the ultimate decay of the partial pair correlation functions.

Hybrid lead halide perovskites, AMX 3 compounds in which A = CH 3 NH 3 (MA), CH(NH 2 ) 2(FA), Cs; M = Pb,Sn; X = I, Br, Cl, display remarkable performance in solution-processed optoelectronic devices, including > 22% efficient thin film photovoltaic cells. These compounds represent the first class of materials discovered to exhibit properties associated with high performance compound semiconductors, while being formed at or near room temperature using simple solution chemistry techniques. This thesis is focused on the synthesis, structural characterisation and phase behaviour of MAPbI 3 , FAPbI 3 , A-site solid solutions and novel organic metal halide framework materials. The complete atomic structure and phase behaviour of methylammonium lead iodide is elucidated for the first time, including hydrogen positions, using high flux, constant wave-length neutron powder diffraction. At 100 K an orthorhombic phase, space group Pnma, is observed, with the methylammonium cations ordered as the C–N bond direction alternates in adjacent inorganic cages. Above 165 K a first order phase transition to tetragonal, I4/mcm, occurs with the unlocking of cation rotation, which is disordered primarily in the ab plane. Above 327 K a cubic phase, space group Pm3m, is formed, with the cations isotropically disordered on the timescale of the crystallographic experiment. The high temperature phase of formamidinium lead iodide, α-FAPbI 3 is shown for the first time to be cubic, (Pm3m), at room temperature using time-of-flight, high resolution neutron powder diffraction. Polymorphism and the low temperature phase behaviour of FAPbI 3 have been further investigated using reactor and spallation neutron sources with high resolution in temperature. A tetragonal phase, P4/mbm, is confirmed in the temperature range 140-285 K.The composition, structural and optical parameters of ’A’ site solid solutions (MA/FA)PbI 3 have been investigated by single crystal X-ray diffraction, UV-vis spectroscopy and 1 H solution NMR. A composition-dependent transition in the crystal class from tetragonal to cubic(or pseudo-cubic) at room temperature is identified and correlated to trends in the optical absorption. Novel hybrid materials with inorganic frameworks of varying dimensionality from 0D to 2D, including imidazolium lead iodide and piperazinium lead iodide, have been synthesised using various templating organic cations and their atomic structures solved by single crystal X-ray diffraction.

Zircaloy-2 and its sister alloy, Zircaloy-4, have extensive applications in the nuclear industry as core components in heavy water reactors and fuel cladding in both heavy and light water reactors. Intergranular stresses and texture can greatly affect the mechanical performance of these components. A complete understanding of the development of intergranular constraints and texture in Zircaloy-2 will allow an improved understanding of the plastic deformation of zirconium alloys, and the prediction of in-reactor deformation of tubes made by different manufacturing routes. Neutron diffraction was used to track the development of lattice strain and peak intensity in three dimensions for various crystallographic planes in samples cut from a rolled Zircaloy-2 slab. The samples were subject to room temperature compression or tension in-situ in the neutron spectrometer in each of the three principal directions of the slab. Textures in the deformed samples were measured using neutron diffraction. Strong evidence was found for tensile twinning in tensile tests in the plate normal direction and compression tests in the transverse and rolling directions. The lattice strain development inside the newly formed twins was recorded for the first time in a Zr alloy. An elasto-plastic self-consistent model and a visco-plastic self-consistent model were used to interpret the lattice strain and texture data, respectively. Various slip and twinning modes were considered in both models. Prism <a> slip, basal <a> slip, pyramidal <c+a> slip and tensile twinning were concluded to be indispensable, while pyramidal <a> slip was unnecessary in the modeling. The critical resolved shear stresses and hardening parameters were obtained by simultaneously achieving a ‘best-fit’ with the complete experimental data set. The effects of anisotropic latent hardening due to dislocation interactions were found to be critical, and the inclusion of Lankford coefficients as modeling constraints was necessary. This research provided a comprehensive experimental data set obtained by neutron diffraction, forming a sound basis to investigate active plastic deformation mechanisms and to rigorously test plasticity models and twinning models. The research also made a substantial improvement in understanding the plastic deformation of Zircaloy-2 through polycrystalline modeling by introducing extensive data sets to constrain the modeling parameters. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2007-12-21 11:56:23.743 / NSERC, COG, OPG and Nu-Tech Precision Metals

With the increasing requirements for higher strength materials with high electrical conductivity, a lot of interest has been paid to develop Cu-based composites in the last 25 years. These composites have superior tensile strength, combined with good electrical conductivity, to that exhibited by pure Cu and conventional Cu alloys. To date, much of the research carried out on this composite has focused on the mechanical and electrical properties of the as processed material. However, there is a basic lack of understanding of the way in which the properties may change or degrade during service. Without this knowledge, these composites cannot be fully and safely exploited. Thus the objective of this study was to investigate the thermo-mechanical behaviour of a Cu-Cr composite, and the nature and extent of any damage mechanisms occurring within the composite over a wide range of experimental conditions. Neutron diffraction was used to investigate the deformation behaviour of the individual phases in the composite and their interaction through elastic and plastic loading at room temperature. For the composite, a fairly good agreement was observed in the phase strains predicted by the Eshelby theory and measured by neutron diffraction. In-situ tensile tests in the SEM were also performed to study the damage mechanism of the composite. Tensile and creep tests were carried out in air and in vacuum over a wide range of temperatures. To provide data for comparison with the composite material, pure Cu specimens were tested whenever possible. Creep resistance increases significantly with the introduction of Cr fibres into Cu. The higher creep rate of the composite in air than in vacuum is due to the gradual decrease of the cross-sectional area of the matrix due to increasing thickness of the oxide layer. Damage characteristics and distributions were found to be similar during tensile and creep testing.

The class of water-ice compound known as gas hydrate has been of interest to science for sometime where, for instance, gas hydrates make excellent candidates for studying the interactions of water and gas molecules. They are also of relevance to industry, where they present an interesting material for the separation, transport, and storage of different gases, and also due to the vast quantities of methane gas that are trapped in natural gas hydrate formations. While much is known about the behaviour of many gas hydrate systems at high-pressure, the CO2 hydrate system is less well studied, with apparent hydrate dissociation at just 10 kbar, and (prior to this work) an unsolved crystalline phase in the pressure range 6-10 kbar. In this work the CO2-H2O system has been studied at high-pressure and, by heating samples to the liquid state and observing their behaviour on refreezing, it has been confirmed that there are indeed no hydrate phases in the system above 10 kbar (up to at least 40 kbar). While performing this investigation, an interesting effect of CO2 on the behaviour of water crystallisation was also observed, and additionally, a simple yet effective technique for making solubility measurements in the system at high-pressure has been discovered. Using a combination of neutron and x-ray diffraction techniques, the crystal structure of the previously unsolved ‘HP’ CO2 hydrate phase has been determined by ab-initio methods. It has been found to be a new gas hydrate structure, but is shared by a small number of Zintl compounds, and may also be common to the unsolved C0 phase of H2 hydrate. The structure has a characteristic spiral of guest molecule sites, leading to its suggested label as the spiral hydrate structure (s-Sp). Its composition has been measured as a tri-hydrate, and the compressibility of s-Sp and the low-pressure s-I CO2 hydrate phases have also been measured. On cooling to 77 K it has been discovered that a third CO2 hydrate phase is formed with a significantly larger unit cell, which is thought to possess a structure similar to that of s-Sp, but with an ordered arrangement of CO2 molecules. Finally, a pilot study of the high-pressure behaviour of the binary H2-CO2 hydrate system has been performed. Using Raman spectroscopy it has been found that a new mixed hydrate phase exists in the pressure range 5-15 kbar, and it is speculated that this could exhibit a freely tunable H2/CO2 content, based on suspicion that it forms the s-Sp structure. Additionally, it has been found that H2 and CO2 chemically react at room temperature, when compressed to ~5 kbar in a rhenium gasket. From the Raman spectrum this reaction product has been identified to be aqueous-methanol.