James W. E. Drewitt

Structural change in molten basalt at deep mantle conditions

Silicate liquids play a key part at all stages of deep Earth evolution, ranging from core and crust formation billions of years ago to present-day volcanic activity. Quantitative models of these processes require knowledge of the structural changes and compression mechanisms that take place in liquid silicates at the high pressures and temperatures in the Earth’s interior. However, obtaining such knowledge has long been impeded by the challenging nature of the experiments. In recent years, structural and density information for silica glass was obtained at record pressures of up to 100 GPa (ref. 1), a major step towards obtaining data on the molten state. Here we report the structure of molten basalt up to 60 GPa by means of in situ X-ray diffraction. The coordination of silicon increases from four under ambient conditions to six at 35 GPa, similar to what has been reported in silica glass. The compressibility of the melt after the completion of the coordination change is lower than at lower pressure, implying that only a high-order equation of state can accurately describe the density evolution of silicate melts over the pressure range of the whole mantle. The transition pressure coincides with a marked change in the pressure-evolution of nickel partitioning between molten iron and molten silicates, indicating that melt compressibility controls siderophile-element partitioning.

Interplay between non-bridging oxygen, triclusters, and fivefold Al coordination in low silica content calcium aluminosilicate melts

In the present work the structural properties of low silica content calcium aluminosilicate melts with concentration ratio CaO/Al2O3 = 1 are investigated in the liquid and undercooled states by neutron diffraction experiments and ab initio molecular dynamics simulations. The results show the presence of AlO5 units and triclusters as well as non-bridging oxygen in the fully charge balanced compositions. Moreover, our findings allow us to identify a possible interplay between these structural units. Finally, we discuss the influence of these defective structural units on the properties of tetrahedral network and more particularly their implication on the evolution of the viscosity and the fragility.

Density-driven structural transformations in network forming glasses: a high-pressure neutron diffraction study of GeO2 glass up to 17.5 GPa

The structure of GeO(2) glass was investigated at pressures up to 17.5(5) GPa using in situ time-of-flight neutron diffraction with a Paris-Edinburgh press employing sintered diamond anvils. A new methodology and data correction procedure were developed, enabling a reliable measurement of structure factors that are largely free from diamond Bragg peaks. Calibration curves, which are important for neutron diffraction work on disordered materials, were constructed for pressure as a function of applied load for both single and double toroid anvil geometries. The diffraction data are compared to new molecular-dynamics simulations made using transferrable interaction potentials that include dipole-polarization effects. The results, when taken together with those from other experimental methods, are consistent with four densification mechanisms. The first, at pressures up to approximately equal 5 GPa, is associated with a reorganization of GeO(4) units. The second, extending over the range from approximately equal 5 to 10 GPa, corresponds to a regime where GeO(4) units are replaced predominantly by GeO(5) units. In the third, as the pressure increases beyond ~10 GPa, appreciable concentrations of GeO(6) units begin to form and there is a decrease in the rate of change of the intermediate-range order as measured by the pressure dependence of the position of the first sharp diffraction peak. In the fourth, at about 30 GPa, the transformation to a predominantly octahedral glass is achieved and further densification proceeds via compression of the Ge-O bonds. The observed changes in the measured diffraction patterns for GeO(2) occur at similar dimensionless number densities to those found for SiO(2), indicating similar densification mechanisms for both glasses. This implies a regime from about 15 to 24 GPa where SiO(4) units are replaced predominantly by SiO(5) units, and a regime beyond ~24 GPa where appreciable concentrations of SiO(6) units begin to form.

Mechanisms of network collapse in GeO2 glass: high-pressure neutron diffraction with isotope substitution as arbitrator of competing models

The structure of the network forming glass GeO(2) is investigated by making the first application of the method of in situ neutron diffraction with isotope substitution at pressures increasing from ambient to 8 GPa. Of the various models, the experimental results are in quantitative agreement only with molecular dynamics simulations made using interaction potentials that include dipole-polarization effects. When the reduced density ρ/ρ(0) > or approximately equal to 1.16, where ρ(0) is the value at ambient pressure, network collapse proceeds via an interplay between the predominance of distorted square pyramidal GeO(5) units versus octahedral GeO(6) units as they replace tetrahedral GeO(4) units. This replacement necessitates the formation of threefold coordinated oxygen atoms and leads to an increase with density in the number of small rings, where a preference is shown for sixfold rings when ρ/ρ(0) = 1 and fourfold rings when ρ/ρ(0) = 1.64.

The structure of liquid calcium aluminates as investigated using neutron and high energy x-ray diffraction in combination with molecular dynamics simulation methods

The structure of laser heated aerodynamically levitated (CaO)(x)(Al₂O₃)(1-x) high temperature liquids, with x = 0.33, 0.5, 0.75, was measured by using neutron and high energy x-ray diffraction. The partial structure factors for the liquids at 2500 K were also determined using molecular dynamics computer simulations. The simulation results are in excellent agreement with the diffraction measurements. The results show a predominant tetrahedral Al coordination with approximately 20% of fivefold coordinated Al at x = 0.33 which reduces with increasing CaO concentration. The Ca atoms occupy a broad range of coordination environments but with a predominance of sixfold distorted octahedra. The simulations confirm the presence of 13, 7 and 0.6% OAl₃ triclusters connecting AlO₄ tetrahedra in the structure of CA2 (x = 0.33), CA (x = 0.5) and C3A (x = 0.75) liquids, respectively.

Development of chemical and topological structure in aluminosilicate liquids and glasses at high pressure.

The high pressure structure of liquid and glassy anorthite (CaAl(2)Si(2)O(8)) and calcium aluminate (CaAl(2)O(4)) glass was measured by using in situ synchrotron x-ray diffraction in a diamond anvil cell up to 32.4(2) GPa. The results, combined with ab initio molecular dynamics and classical molecular dynamics simulations using a polarizable ion model, reveal a continuous increase in Al coordination by oxygen, with 5-fold coordinated Al dominating at 15 GPa and a preponderance of 6-fold coordinated Al at higher pressures. The development of a peak in the measured total structure factors at 3.1 Å(-1) is interpreted as a signature of changes in topological order. During compression, cation-centred polyhedra develop edge- and face- sharing networks. Above 10 GPa, following the pressure-induced breakdown of the network structure, the anions adopt a structure similar to a random close packing of hard spheres.

The structure of molten CuCl, CuI and their mixtures as investigated by using neutron diffraction

The structure of molten CuCl, CuI and their mixtures (CuCl)(x)(CuI)(1-x) with x = 0.294, 0.576, 0.801 was studied by using neutron diffraction. The results are discussed by reference to the information that is available on the structure of CuCl and CuI from experiment, theory and computer simulation. The comparison points to a need for more realistic models for the CuCl-CuI system which should take into account the presence of chemical bonds that have been found in CuI by the application of ab initio molecular dynamics methods.

Neutron diffraction as a probe of liquid and glass structures under extreme conditions

Neutrons provide a unique tool for probing the structure of liquid and glassy materials, and deliver information that cannot be obtained from other experimental techniques. Advances in neutron diffraction instrumentation and measurement protocols now make it possible to measure the structure of these disordered materials under extremes of high temperatures or high pressures. Here, we consider the use of aerodynamic levitation with laser heating to explore the structure of glass-forming oxide melts at high temperatures, and the use of a Paris Edinburgh press to investigate the mechanisms of density-driven network collapse for glassy materials in the gigapascal (GPa) pressure regime.

Structure of rare-earth chalcogenide glasses by neutron and x-ray diffraction

The method of neutron diffraction with isomorphic substitution was used to measure the structure of the rare-earth chalcogenide glasses [Formula: see text](Ga2 X 3)0.33(GeX 2)0.60 with [Formula: see text] or Ce and [Formula: see text] or Se. X-ray diffraction was also used to measure the structure of the sulphide glass. The results are consistent with networks that are built from GeX 4 and GaX 4 tetrahedra, and give R-S and R-Se coordination numbers of 8.0(2) and 8.5(4), respectively. The minimum nearest-neighbour R-R distance associated with rare-earth clustering is discussed.