Thesis (Ph.D.) - University of Queensland, 2003. / Includes bibliography.

Thesis (M.S.)--Brigham Young University. Dept. of Mechanical Engineering, 2005. / Includes bibliographical references (p. 59-61).

An investigation into the processes taking place at the surface interface of ferroelectric Pb(Zr1-x,Tix)O3 immersed in metal salt solution under ultraviolet illumination is presented. The semiconducting and switchable dipolar nature of this material allows the spatial separation and control of photo-induced reduction and oxidation across its surface interface. These properties can be of application in novel techniques such as the controlled growth of metallic nanoparticles across specific polar domains. 70nm thick Pb(Zr0.3,Ti0.7)O3 samples, PZT(30/70), are manufactured using the sol gel methodology, two crystallographic orientations being produced. The orientation being controlled by the substrate used; Si was used for [111] orientation and MgO for [100]. The initial work with wideband ultraviolet light shows that the reduction and growth of silver on the PZT surface is greatly influenced by the structure of the film. The crystallographic orientation of the film affects metal deposition such that on [111] films the metal deposits only on positive domains, where as the [100] films experience deposition on both positive and negative domains. This is shown to be due to the difference in width of the space charge region, Δw = 4.4nm, between the [111] and [100] samples so that the negative domain on [100] samples have 10 19 times higher chance of electron tunnelling compared to the [111]. It is also shown that grain boundaries have the greatest effect on the growth of metal, with a metal cluster growth rate 51 times faster than elsewhere on the surface. This increased rate of growth is due to the effect a grain boundary has on the surrounding area, the energy band bending at the boundary attracting charge carriers from the grains around it. The interface types ranked from greatest to lowest influence are grain boundaries, positive domains, domain boundaries and finally interphase boundaries.ii It is shown that the stern layer, strongly adsorbed charged ions of opposite sign to the surface charge, at the PZT/solution interface act as an insulating layer to metal reduction. The accumulation of photoexcited charge carriers at points along grain boundaries causes the surface potential gradient to alter and allows metal reduction and thus clusters to nucleate. The energy required to cause this variation is investigated by use of narrow band, 5nm bandwidth, ultraviolet. For energy from 4.4eV to 5 eV, it is found there is an increase in the average silver cluster cross sectional area by a ratio of ca 1.6 to 1 for both the [111] and [100] orientations of PZT. Finally it is shown that the type of metal salt used in the photochemical process affects the type of reaction that takes place at the sample surface. For a cation to reduce on positive domains its reduction potential needs to be below the bottom edge of the conduction band of PZT. Chloride salts, that sit above the conduction band, cause decomposition of the negative domains. Use is made of these effects to find the position of the bottom of the conduction band for PZT. It is found that across similar [111] PZT samples FeCl2 can both reduce on positive domains and decompose negative domains, this puts the bottom of the conduction band for PZT(30/70) between 4.06 and 4.36 eV from vacuum. It is also discovered that the type of anion affects the decomposition of the negative domains. Nitrate salts with cations above the conduction band cause no decomposition whereas chlorides do. The decomposition is shown to be the loss of Pb from the negative surface.

abstract: Because of their favorable ionic and/or electronic conductivity, non-stoichiometric oxides are utilized for energy storage, energy conversion, sensing, catalysis, gas separation, and information technologies, both potential and commercialized. Charge transport in these materials is influenced strongly by grain boundaries, which exhibit fluctuations in composition, chemistry and atomic structure within Ångstroms or nanometers. Here, studies are presented that elucidate the interplay between macroscopic electrical conductivity, microscopic character, and local composition and electronic structure of grain boundaries in polycrystalline ceria-based (CeO2) solid solutions. AC impedance spectroscopy is employed to measure macroscopic electrical conductivity of grain boundaries, and electron energy-loss spectroscopy (EELS) in the aberration-correction scanning transmission electron microscope (AC-STEM) is used to quantify local composition and electronic structure. Electron diffraction orientation imaging microscopy is employed to assess microscopic grain boundary character, and links these macro- and nanoscopic techniques across length scales. A model system, CaxCe1-xO2-x-δ, is used to systematically investigate relationships between nominal Ca2+ concentration, grain boundary ionic conductivity, microscale character, and local solute concentration. Grain boundary conductivity varied by several orders of magnitude over the composition range, and assessment of grain boundary character highlighted the critical influence of local composition on conductivity. Ceria containing Gd3+ and Pr3+/4+ was also investigated following previous theoretical work predicting superior ionic conductivity relative to state-of-the-art GdxCe1-xO2-x/2-δ. The grain boundary conductivity was nearly 100 times greater than expected and a factor four enrichment of Pr concentration was observed at the grain boundary, which suggested electronic conduction that was cited as the origin of the enhanced conductivity. This finding inspired the development of two EELS-based experimental approaches to elucidate the effect of Pr enrichment on grain boundary conductivity. One employed ultra-high energy resolution (~10 meV) monochromated EELS to characterize Pr inter-bandgap electronic states. Alternatively, STEM nanodiffraction orientation imaging coupled with AC-STEM EELS was employed to estimate the composition of the entire grain boundary population in a polycrystalline material. These compositional data were the input to a thermodynamic model used to predict electrical properties of the grain boundary population. These results suggest improved DC ionic conduction and enhanced electronic conduction under AC conditions. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

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ymmetric tilt boundary [2 1 10] (01 12) in HCP titanium has been investigated by computer simulation methods using the embedded atom potential. The structure and energies of the considered boundary and the energies of formation of vacancies in it have been calculated by the method of molecular-static simulation. The stability of the boundary at elevated temperatures has been investigated by the molecular dynamics method, and the coefficients of grain-boundary diffusion have been calculated.

Atomistic computer simulations were performed using embedded atom method interatomic potentials in α-Fe with impurities and defects. The effects of intergranular carbon on fracture toughness and the mechanisms of fracture were investigated. It was found that as the average grain size changes the dominant energy release mechanism also changes. Because of this the role of the intergranular carbon changes and these mechanisms compete affecting the fracture toughness differently with changing grain size. Grain boundary accommodation mechanisms are seen to be dominant in the fracture of nanocrystalline α-Fe. To supplement this work we investigate grain boundary sliding using the Σ = 5,(310)[001] symmetrical tilt grain boundary. We observe that in this special boundary sliding is governed by grain boundary dislocation activity with Burgers vectors belonging to the DSC lattice. The sliding process was found to occur through the nucleation and glide of partial grain boundary dislocations, with a secondary grain boundary structure playing an important role in the sliding process. Interstitial impurities and vacancies were introduced in the grain boundary to study their role as nucleation sites for the grain boundary dislocations. While vacancies and H interstitials act as preferred nucleation sites, C interstitials do not. / Ph. D.

Microstructural data on the orientation and distribution of minerals can be utilized to better understand the processes controlling mineral crystallization during metamorphism and the extent to which equilibrium versus kinetic factors control the evolution of metamorphic rocks. Four studies in this dissertation address this, finding that: i) garnet crystals crystallize via epitaxial nucleation in which garnet crystallizes by templating on the crystal structure of muscovite; ii) the distribution of grain boundary void space at quartz-quartz and garnet-quartz grain boundaries is a function of the orientation of quartz crystals on either side of the grain boundary. There are more voids, and in some cases larger voids, at grain boundaries in which the a-axis of a neighboring quartz grain is perpendicular to the grain boundary than any other orientation; iii) the chemical potentials of garnet-forming components evolve differently in samples in which garnet growth either significantly or minimally overstepped equilibrium garnet-forming reactions; iv) the southwestern Meguma Terrane, Nova Scotia, experienced peak metamorphic conditions of ~630ºC and 4.0 kbar, likely resulting from regional metamorphism during the Neoacadian orogeny. A case study on the mechanisms controlling garnet crystallization in one Nova Scotian sample reveals that the rate limiting step of garnet crystallization was probably the diffusional transport of Al through the intergranular matrix. Taken together, this work has implications for understanding: i) the properties of grain boundaries in metamorphic rocks and ii) the extent to which equilibrium versus kinetic factors impact metamorphic petrogenesis. / Doctor of Philosophy / A fundamental question in the development of metamorphic rocks, or rocks that form due to changes in pressure and temperature conditions deep in the Earth's mountain belts, is: what controls the crystallization of new minerals? While pressure, temperature, and bulk composition likely play a major role in this, it is also possible that the distribution of reactant minerals and the transport of elements through the rock may also play a role in mineral crystallization. This dissertation explores several projects related to this broad topic. In one example, garnet, an important metamorphic mineral, was found to crystallize by utilizing the atomic structure of another mineral in the rock. This creates a favorable pathway for the crystallization of garnet, which preferentially grows on this 'parent' mineral. Further, the distribution of porosity, or void space, at the interfaces between mineral grains in metamorphic rocks is found to be controlled by the orientation of those minerals. This porosity likely formed when the rocks were exhumed from deep in the Earth towards its surface. Metamorphic rocks can also tell the story of continental plates colliding millions of years ago. In an example from the formation of the Appalachian Mountains ~400 million years ago, a combination of collisional tectonic forces and the heat from magmas in the shallow crust resulted in metamorphic rock, which make up much of southern Nova Scotia today. This work has important implications for understanding: i) porosity in metamorphic rocks and ii) how minerals crystallize during metamorphism.