A time resolved high energy X-ray diffraction study of cooling liquid SiO2.

The evolution of the X-ray structure factor and corresponding pair distribution function of SiO2 has been measured upon cooling from the melt using high energy X-ray diffraction combined with aerodynamic levitation. Small changes in the position of the average Si-O bond distance and peak width are found to occur at ~1500(100) K in the region of the calorimetric glass transition temperature, T(g) and the observed density minima. At higher temperatures deviations from linear behavior are seen in the first sharp diffraction peak width, height and area at around 1750(50) K, which coincides with the reported density maximum around 1.2T(g).

Relationship between topological order and glass forming ability in densely packed enstatite and forsterite composition glasses.

The atomic structures of magnesium silicate melts are key to understanding processes related to the evolution of the Earth's mantle and represent precursors to the formation of most igneous rocks. Magnesium silicate compositions also represent a major component of many glass ceramics, and depending on their composition can span the entire fragility range of glass formation. The silica rich enstatite (MgSiO(3)) composition is a good glass former, whereas the forsterite (Mg(2)SiO(4)) composition is at the limit of glass formation. Here, the structure of MgSiO(3) and Mg(2)SiO(4) composition glasses obtained from levitated liquids have been modeled using Reverse Monte Carlo fits to diffraction data and by density functional theory. A ring statistics analysis suggests that the lower glass forming ability of the Mg(2)SiO(4) glass is associated with a topologically ordered and very narrow ring distribution. The MgO(x) polyhedra have a variety of irregular shapes in MgSiO(3) and Mg(2)SiO(4) glasses and a cavity analysis demonstrates that both glasses have almost no free volume due to a large contribution from edge sharing of MgO(x)-MgO(x) polyhedra. It is found that while the atomic volume of Mg cations in the glasses increases compared to that of the crystalline phases, the number of Mg-O contacts is reduced, although the effective chemical interaction of Mg(2+) remains similar. This unusual structure-property relation of Mg(2)SiO(4) glass demonstrates that by using containerless processing it may be possible to synthesize new families of dense glasses and glass ceramics with zero porosity.

High-energy X-ray diffraction from aluminosilicate liquids.

Containerless high energy X-ray diffraction measurements have been performed on molten Al(2)O(3)-SiO(2) as a function of composition. The data show a strong distortion of the SiO(4) tetrahedral units and a breakdown of intermediate range order as alumina is added. For silica-rich compositions, the X-ray pair distribution functions are consistent with the presence of 4-fold oxygen triclusters predicted by molecular dynamics simulations, where these liquids exhibit relatively high viscosities compared to other binary silicates. For higher alumina content liquids, the average cation-oxygen coordination number gradually increases with increasing Al(2)O(3) content, but the pair distribution functions change very little with composition, suggesting the increased presence of disordered AlO(n) (n = 4,5,6) polyhedra are associated with low viscosity melts. A comparison of the liquid and glassy X-ray pair distributions functions at the alumina-rich mullite composition indicate a significant distortion of the polyhedra in the melt, suggesting structural changes are temperature dependent.

Detection of first-order liquid/liquid phase transitions in yttrium oxide-aluminum oxide melts.

We combine small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS) with aerodynamic levitation techniques to study in situ phase transitions in the liquid state under contactless conditions. At very high temperatures, yttria-alumina melts show a first-order transition, previously inferred from phase separation in quenched glasses. We show how the transition coincides with a narrow and reversible maximum in SAXS indicative of liquid unmixing on the nanoscale, combined with an abrupt realignment in WAXS features related to reversible shifts in polyhedral packing on the atomic scale. We also observed a rotary action in the suspended supercooled drop driven by repetitive transitions (a polyamorphic rotor) from which the reversible changes in molar volume (1.2 +/- 0.2 cubic centimeters) and entropy (19 +/- 4 joules mole(-1) kelvin(-1)) can be estimated.

Structure of molten yttrium aluminates: a neutron diffraction study.

We used the aerodynamic levitation technique combined with CO2 laser heating to study the structure of liquid yttrium aluminates above their melting point with neutron diffraction. For various yttria contents, we determined the structure factors and corresponding pair correlation functions describing the short-range order in the liquids. In particular, we derived Al-O and Y-O bond distances and coordination numbers. Experimental data are compared with ab initio molecular dynamics, carried out using the VASP code where the interatomic forces are obtained from density functional theory. In particular, partial pair correlation functions have been calculated and are in relatively good agreement with the experimental observations.

X-ray and neutron diffraction studies and MD simulation of atomic configurations in polyamorphic Y2O3-Al2O3 systems.

Supercooled liquids in the Y(2)O(3)-Al(2)O(3) system undergo a liquid-liquid phase transition between a high-temperature, high-density amorphous (HDA) polymorph form and one with lower density (LDA form) that is stable at lower temperature. The two amorphous polymorphs have the same chemical composition, but they differ in their density (ca. 4% difference) and in their heat content (enthalpy) and entropy determined by calorimetry. Here we present new results of structural studies using neutron and high-energy X-ray diffraction to study the structural differences between HDA and LDA polyamorphs. The combined datasets show no large differences in the average nearest-neighbour Al-O or Y-O bond lengths or coordination numbers between the low- and high-density liquids. However, the data indicate that substantial changes occur among the packing geometries and clustering of the Al-O and Y-O coordination polyhedra, i.e. within the second-nearest-neighbour shell defined by the metal-metal (i.e. Y-Y, Y-Al, Al-Al) interactions. Polarizable ion model molecular dynamics simulations of Y(2)O(3)-Al(2)O(3) liquids are used to help interpret the pair-correlation functions obtained from X-ray and neutron scattering data. Unexpectedly large density fluctuations are observed to occur during the simulation of nominally equilibrated systems. These are interpreted as being due to dynamic sampling of high- and low-density configurations within the single-phase liquid at temperatures above the critical point or phase transition line. Calculated partial radial distribution functions indicate that the primary differences between HDA and LDA configurations occur among the Y-Y correlations.