Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (leaves 99-114).

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The effects of Ca and Ce on the precipitation behaviour and microstructural characteristics of Mg-Zn based alloys are investigated by comprehensive multi-scale characterization and analysis. The elements Ca and Ce are chosen for their potential to enhance (a) precipitation hardening and (b) alloy texture and ductility, and are examined at both alloying and microalloying (< 0.5 wt%) levels. When added individually to Mg-Zn, Ca is found to enhance precipitation, but Ce produces a generally adverse effect on the hardening response. A pre-ageing strategy is proposed to alleviate this negative effect of Ce. The highlight of this work is the double microalloying addition of Ce-Ca to Mg-Zn, as this combination and quantity proves to be the most effective at increasing the age-hardening response, and enhancing microstructural characteristics for improved ductility. Transmission electron microscopy analysis reveals the hardening increase to originate from a refined precipitate microstructure, and the formation of fine-scale basal plate precipitates. These fine precipitates form during early ageing as monolayer GP zones consisting of Ca and Zn. The formation of these GP zones is facilitated by the atomic size difference between those two solutes, and their observed tendency to co-cluster. The monolayer GP zones evolve to multi-layered forms in the peak-aged condition. These precipitates are observed to be uniformly distributed, even where apparent precipitate-free zones are observed for the Mg-Zn type phases in the grain boundary regions. Notably, the size of these precipitate-free zones for the Mg-Zn phases is also reduced in the Ce-Ca microalloyed samples, compared to the binary alloy. The Ce-Ca microalloying additions also promote grain refinement and a weakening of the basal textures, typical of conventional Mg-based alloys, compared to both Mg-Zn and Mg-Zn-Ce. As a result, the tensile behaviour of the alloys with Ce-Ca is similarly enhanced. Considering both the precipitation hardening capability and microstructural characteristics, it is concluded that the double microalloying additions of Ce-Ca can be considered as a new alloy design strategy to successfully achieve improvement in both the strength and ductility of Mg-Zn alloys.

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Neutral diorganotin compounds of the 1,3-dithiole-2-thione-4,5-dithiolate ligand have been prepared. The syntheses of Me₂Sndmit, Et₂Sndmit, Bu₂Sndmit, (C₈H₁₇)₂Sndmit, (C₁₀H₂₁)₂Sndmit and (C₁₄H₂₉)₂Sndmit are described. For the purposes of indicating the formation of different structural phases, D.S.C. powder patterns are reported for initial and recrystallised samples of Me₂Sndmit, Et₂Sndmit and Bu₂Sndmit. Since Et₂Sndmitshowed different tin environments by solid phase state N.M.R. and clearly different powder patterns after recrystallisation, the compound was recrystallised from various solvents in an attempt to determine how many crystalline forms exist. To date, two forms have been identified: orthorhombic and monoclinic. The single crystal X-ray structure analyses of these are described. It has also been shown that upon heating a transition from the orthorhombic to the monoclinic form occurs at 140°C. The crystal strict of Me₂Sndmit has also been determined and is reported, along with Mossbauer parameters for Me₂Sndmit and Me₂Sndmio (dmio = 1,3-dithiole-2-one-4,5-dithiolate). Anionic organotin bis-dmit complexes of the form [RSn(dmit)₂][Q]⁺ have also been prepared, with a view to investigating their electrochemical properties. The syntheses of complexes with R chain length ranging from 4 to 18 carbons are described. The problem of formation of [Sn(dmit)₃][Q]₂ is also discussed. D.S.C. curves and cyclic voltammograms for [C₁₄H₂₉Sn(dmit)₂][C₁₄H₂₉NMe₃] and [NEt₄][(dmit)₂SnC₁₀H₂₀Sn(dmit)₂][NEt₄] are also described. Chiral macrocycles have potential uses as catalysts for asymmetric bond-forming reactions and as selective to metal ions. A chiral macrocyclic derivative of dmit was synthesised from methyl-4,6-<I>O</I>-benzylidene-2,3-bis-<I>O</I>-[(2-iodoethoxyethyl)-ethyl]-α-D-glucopyranoside. Since reaction of this with dmit proved to be unexpectedly problematic, attempted reactions of the sugar derivative with Na₂dmit<I> in situ</I>, isolated Na₂dmit, [Zn(dmit)₂][NEt₄]₂, [Ph₂Sn(dmit)I][NEt₄] and Cs₂dmit are described.

The effect of large size ratios of solute to solvent on the critical properties and phase behaviour of binary mixtures of spherical particles is investigated using an "augmented van der Waals" equation of state. The equation used is essentially a van der Waals equation with an improved hard sphere repulsive term. Molecular dynamics and constant-pressure Monte Carlo simulations of binary mixtures of hard spheres with different diameter ratios and mole fractions are undertaken to check the adequacy of the hard sphere equation. Good agreement is found, even for systems with large differences in size. Furthermore, many of the hard sphere mixtures exhibited a transition from a fluid to a solid phase at high densities. Phase boundaries are calculated for model mixtures comprising spheres of different sizes between which there are long-ranged attractive forces. Particular attention is paid to the case in which the ratio of sizes is infinite. The systems show a wide variety of behaviour that includes liquid-liquid and gas-gas immiscibility, and the formation of negative azeotropes. Calculations investigating the effect of different attractive interactions between the small and large spheres show that as the magnitude of this interaction is increased, liquid-liquid immiscibility becomes the dominant feature of the phase diagram at moderate temperatures. The extent of liquid-liquid coexistence is greatest at large size differences. These model systems are shown to reproduce some of the behaviour of aqueous solutions of surfactants if it is assumed that the large spheres are models of the micelles and the small spheres models of the solvent molecules. The properties of binary lattice mixtures of bifunctional molecules whose ends are chosen to mimic surfactant and solvent molecules are also briefly investigated, to determine the effect of the asymmetric surfactant molecule on the phase separation. Closed-loops emerge in the phase diagrams as the surfactant character of one of the species is increased.

Ferromagnetic shape memory alloys FSMAs have diverse application, especially in the aerospace and bio-medical industries. They are a class of active and smart materials exhibiting strains under the influence of an applied magnetic field. These magnetic properties are mainly attributed to the martensitic structural phase trans- formation these material experience in response to temperature variation. Co-Ni-Al based alloys are one of the most promising ferromagnetic shape memory alloy FSMA that has been put recently under extensive study by researchers. They have shown extensive and promising features specifically those related to self-actuation. The effect of valence electron concentration and magnetic properties of Co-Ni-Al based ferromagnetic shape memory alloys on the martensitic transformations were analyzed utilizing Ab-initio first principle calculations. The variations of martensite start temperatures (Ms) and magnetic properties of a number of stoichiometric and mnon-stoichiometric Co-Ni-Al ferromagnetic shape memory alloys (FSMA’s) with B2 austenite structure were studied and analyzed as a function of composition and lattice site ordering and site preference. A major conclusion of this thesis suggests that the magnetic valence number (Zm) should be considered in conjunction to the e/a ratio if the composition profile of the Ms is to be determined. Both Monte-Carlo and Ab-initio simulations were implemented to obtain the magnetic Heisenberg’s exchange coupling parameters (J m) and model the magnetic transformations in stoichiometric Co2NiAl FSMAs. Two different cubic structures, ordered and disordered were compared to their tetragonal distortions martensitic phases and their Curie temperature (TC ) were obtained from the Monte-Carlo magnetic susceptibility temperature profile.

Solid-state amorphization of a crystalline solid to an amorphous phase is extensively studied as a first order phase transition at low temperature for almost thirty years. In this dissertation, we report the recent progress on phenomenological models employed for thermodynamic description of macroscopic systems and fluctuations and nucleation of mesoscopic inhomogeneous systems in binary solid solutions under polymorphic constraints with no long-range diffusion involved. Based on our understanding on atomic picture of solid-state amorphization in binary solid solutions, we propose a Landau free energy to describe amorphization as the first order phase transition. The order parameter is defined which represents the loss of long-range translational order. The elastic strain field induced by composition disorder plays the important role through the bilinear coupling with the order parameter. Elastic softening and amorphization happen simultaneously. From the similarity between the melting and amorphization, we use the temperature and composition as two external variables and treat solid-state amorphization as low temperature melting under polymorphic constraints. For homogeneous system, the phase diagrams for endothermic melting and exothermic melting are built separately and the corresponding thermodynamic quantities are presented. A microscopic homogeneous nucleation mechanism is proposed conceptually in binary solid solutions under polymorphic constraints. The formation of an amorphous embryo is initiated from the composition modulation in the crystal state and a subsequent polymorphous nucleation within the as-formed heterophase fluctuation. This homogeneous nucleation path is thought to be associated with the nonlinear energy localization mechanism connected with the localized large-amplitude excitations of atoms, which are induced by nonlinear and disorder. A Landau-Ginzburg free energy is constructed to describe the critical nucleus and the growth of the new phase in one-dimensional systems. Analytical and numerical methods contribute to the understanding the fluctuations and nucleation processes. Size-dependent melting and amorphization in nanosolids are investigated. Two models are proposed for nanocrystalline solid solutions to glass transformations. Based on the thin film model with finite thickness, we build one-dimensional Landau-Ginzburg approach, which includes surface contribution and size dependence, and numerical results do show similarity with experimentsâ results qualitatively.