A study of the subsolidus region of the BaO-La2O3-V 2O5 phase diagram has been carried out. Four ternary phases can be prepared, one of which has not been previously identified. The four ternary phases are a palmierite solid solution Ba3-3xLa2x V2O8, Ba2LaV3O11, BaLa10V4O26 (new phase) and Ba3La 40V12O93. Addition of BaLa10V 4O26 and the previously omitted phase La1.42V 0.58)3.58 to the ternary system has resulted n a re-determination of the complete phase diagram. A comprehensive study of the Ba3-3xLa 2xV2O8 solid solution has been carried out, employing a number of techniques including x-ray diffraction, infra-red spectroscopy, thermogravemetric analysis, impedance spectroscopy, electron paramagenetic resonance spectroscopy, inductively coupled plasma mass spectroscopy and x-ray absorption near edge structure spectroscopy. Conductivity measurements show the end-member Ba3V2O8 to be an oxide ion conductor, with the conduction mechanism being facilitated by the ease of transformation of the BaO3 layers to BaO2 and vice versa. The La-doped members show an increase in conductivity, with electrons becoming the dominant conducting species. The crystal structure of Ba2LaV 3O11 was confirmed to be isostructural with Ba2BiV 3O11. A full refinement of the structural parameters has been performed. The unit cell is primitive monoclinic, a = 12.44510(3)A, b = 7.78854(12)A, c = 11.26245(21)A and beta = 103.134(4)°, space group P21/c. Preliminary structural studies have begun on the new phase BaLa10V4O26. The x-ray powder pattern has been fully indexed and a possible monoclinic unit cell of a = 20.2939A, b = 5.886A, c = 12.6234A and beta = 118.05° is proposed. The serendipitous synthesis of a barium-deficient celsian phase, Ba0.8A11.6 Si2.4O8, is reported; the structure was solved using Patterson methods. The phase has a monoclinic unit cell with, a = 8.6090(8)A, b = 13.0858(12)A, c = 7.2047(7)A and beta = 115.418(2)°, space group C2/m.

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Global phase diagrams of binary systems in pressure-temperature (PT) space are very useful. In this project the techniques to automatically develop global phase diagrams in PT space were created. The codes to compute different components of a global phase diagram in PT space were developed. These codes were then successfully incorporated into a single functional program. <p>To generate the binary PT phase diagram, the overall composition was varied from pure component 2, the least volatile component (LVC) to pure component 1, the most volatile component (MVC). The step size for changing mole fraction was varied in the calculation of different parts of a global phase diagram. When the points near the joining points between different parts were computed, the step size was set to a rather small value. The step size was then increased to twice of the last value for each subsequent point computed. When the MVC mole fraction was approaching one, the step size was set to a small value to obtain enough points needed to minimize the chances of missing important phenomena. <p>The techniques to set initial guesses for evaluation of different components of a global phase diagram were discussed. The code performance, including the number of iterations for different convergence criteria and the sensitivity of the algorithm were presented. Using the code developed, phase diagrams of type I, type II, type III and type V were generated using representative binary systems from the petroleum processing field. <p>The boundary states between different types of phase behaviour were also explored. It was observed that with the increase of the binary interaction parameters, the phase behaviour of the ethane + ethanol binary system changes from type I to type II to type III while the methane + n-hexane binary system changes from type V to type III. These conclusions matched the results of van Konynenburg and Scott (1980). It was also concluded that with the increase of the binary interaction parameter for a binary system, the system showed a trend to exhibit more liquid-liquid immiscibility.

Global phase diagrams of binary systems in pressure-temperature (PT) space are very useful. In this project the techniques to automatically develop global phase diagrams in PT space were created. The codes to compute different components of a global phase diagram in PT space were developed. These codes were then successfully incorporated into a single functional program. <p>To generate the binary PT phase diagram, the overall composition was varied from pure component 2, the least volatile component (LVC) to pure component 1, the most volatile component (MVC). The step size for changing mole fraction was varied in the calculation of different parts of a global phase diagram. When the points near the joining points between different parts were computed, the step size was set to a rather small value. The step size was then increased to twice of the last value for each subsequent point computed. When the MVC mole fraction was approaching one, the step size was set to a small value to obtain enough points needed to minimize the chances of missing important phenomena. <p>The techniques to set initial guesses for evaluation of different components of a global phase diagram were discussed. The code performance, including the number of iterations for different convergence criteria and the sensitivity of the algorithm were presented. Using the code developed, phase diagrams of type I, type II, type III and type V were generated using representative binary systems from the petroleum processing field. <p>The boundary states between different types of phase behaviour were also explored. It was observed that with the increase of the binary interaction parameters, the phase behaviour of the ethane + ethanol binary system changes from type I to type II to type III while the methane + n-hexane binary system changes from type V to type III. These conclusions matched the results of van Konynenburg and Scott (1980). It was also concluded that with the increase of the binary interaction parameter for a binary system, the system showed a trend to exhibit more liquid-liquid immiscibility.

Zirconium base alloys have very good metallic glass forming ability. In this study,the Zr-Cu-Ni ternary isotherm at 800¢J were determined by using metallography,electron-probe microanalysis and X-ray diffraction.The main objective is to provide the necessary information for alloy design to form new Zr-base with better glass forming ability.

Solid-liquid equilibrium in isomorphous amino acid systems has been investigated as a model for systems that form solid solutions. Solid- and liquid-phase compositions in L-valine + L-leucine, L-valine + L-isoleucine, and L-isoleucine + L-valine in water were measured over the entire range of solid composition, and it was shown (from mass balance and phase rule considerations) that these systems form solid solutions. The solid- phases resulting from isothermal and cooling crystallization experiments were also investigated using powder x-ray diffractometry which showed that homogeneous solid solutions could only be obtained in cooling crystallization experiments, whereas isothermal experiments generally produced inhomogeneous solids. This suggests that data reported in the literature from isothermal experiments may not represent true equilibrium values. Solid-phase activity coefficients were estimated using binary and ternary equilibrium data and the UNIFAC-Kuramochi model for liquid-phase nonidealities. The solid phases in the three systems investigated exhibited significant nonidealities that were correlated using the Margules model. The model parameters exhibited a linear relationship with the ratio of binary solubilities of the two solutes. Such simple relationship may be advantageous when solid-liquid equilibrium of thermally unstable solutes or components with unknown physical properties are crystallized.

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Solid hydrogen forms at extreme conditions, under high pressures. Although the hydrogen atom is easy to understand theoretically, when interacting in the solid state it becomes complicated. Up to now, five different solid phases have been confirmed experimentally and theory has predicted numerous competing crystal candidates. The goal is to obtain solid metallic hydrogen which has been predicted theoretically eighty years ago and has since been considered the holy grail of high pressure science. In nature, this form of matter is believed to exist at the core of large planets like Jupiter and Saturn, being responsible for the planets' large magnetic fields. Understanding the different phases of hydrogen is a test for our most advanced theories of quantum mechanics in condensed matter and it is fundamentally important for both planetary and material science. Recently discovered solid phase IV is stabilized by entropy and therefore only exists at relatively high temperatures. Using molecular dynamics (MD) I studied the room temperature behavior of phase IV starting with the ground state candidate structures reported in the literature. Additionally, I devised a velocity projection method for extracting Raman spectra from MD in light of direct comparison to experiment. My results helped establish the true nature of phase IV and validated the structure against experimental data. Applying the same method to the previously proposed C2=c crystal structure, I obtained results that confirm this structure is the best candidate for phase III. Within the last year, a new phase V of solid hydrogen was discovered in Raman experiments. While attempting to identify the crystal structure associated with this new phase, I discovered a manifestation of solid hydrogen in the form of long polymeric chains that could be stabilized by a charge density wave. Here I discuss the possibility of such a state of matter as an intermediate on the path to molecular dissociation of hydrogen. Chains could, however, be a spurious structure - the effect of a subtle non-convergence problem in the MD, which could indicate serious issues with many previous studies reported in the literature. A far more likely candidate for phase V is a structure similar to that of phase IV with a subtle dynamical modification. I will present Raman and phonon results from both static and dynamic calculations to support this claim. I conclude my work on pure solid hydrogen with an instructive model that could explain the entire phase diagram based on simple thermodynamic considerations. All of the assumptions were extracted from our previous ab initio studies through analysis and observations. This model encodes a comprehensive summary of the current understanding of solid hydrogen at high pressures. Raman and infrared spectroscopy have been the methods of choice in most hydrogen studies. Another way to look at the problem is to analyze the behavior of isotopic mixtures: hydrogen-deuterium binary alloys. Using isotopic substitutions, I revealed a textbook effect in hydrogen: phonon localization by mass disorder. The effect might be unique to this element, owing to the large mass ratio between hydrogen and deuterium. Phonon localization explains the complicated Raman spectra obtained experimentally in hydrogen-deuterium mixtures at various concentrations. More recent experimental results claim an unexpected phase transition in mixtures at low temperatures based on splittings in the infrared spectra. Here I will show that the infrared splitting seen experimentally could be induced by mass disorder in phase III and does not necessarily indicate a structural transformation.

The modern theory of phase transitions cannot explain the results of many experiments of interphase mass transfer. One reason for this is the assumption that during crystallization the solution is in the metastable state. The decomposition of the solution occurs by binodal scenario in this case. Crystallization nuclei form and grow in solution. The purpose of this study to show that in many cases the solution during crystallization is in an unstable state. The unstable condition leads to decomposition the solution by spinodal scenario.