Iron coordination in liquid FeAl2O4.

The structure of aerodynamically levitated liquid [Formula: see text] was measured by neutron diffraction with isotope substitution (NDIS). Classical and ab initio molecular dynamics simulations were performed and their results were found to be in close agreement with each other and the NDIS data. The results reveal that molten [Formula: see text] may be considered as an ionic liquid without any preference for particular short-range structural motifs. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

Liquid structure under extreme conditions: high-pressure x-ray diffraction studies.

Under extreme conditions of high pressure and temperature, liquids can undergo substantial structural transformations as their atoms rearrange to minimise energy within a more confined volume. Understanding the structural response of liquids under extreme conditions is important across a variety of disciplines, from fundamental physics and exotic chemistry to materials and planetary science.In situexperiments and atomistic simulations can provide crucial insight into the nature of liquid-liquid phase transitions and the complex phase diagrams and melting relations of high-pressure materials. Structural changes in natural magmas at the high-pressures experienced in deep planetary interiors can have a profound impact on their physical properties, knowledge of which is important to inform geochemical models of magmatic processes. Generating the extreme conditions required to melt samples at high-pressure, whilst simultaneously measuring their liquid structure, is a considerable challenge. The measurement, analysis, and interpretation of structural data is further complicated by the inherent disordered nature of liquids at the atomic-scale. However, recent advances in high-pressure technology mean that liquid diffraction measurements are becoming more routinely feasible at synchrotron facilities around the world. This topical review examines methods for high pressure synchrotron x-ray diffraction of liquids and the wide variety of systems which have been studied by them, from simple liquid metals and their remarkable complex behaviour at high-pressure, to molecular-polymeric liquid-liquid transitions in pnicogen and chalcogen liquids, and density-driven structural transformations in water and silicate melts.

Internal resistive heating of non-metallic samples to 3000 K and >60 GPa in the diamond anvil cell.

High pressure-temperature experiments provide information on the phase diagrams and physical characteristics of matter at extreme conditions and offer a synthesis pathway for novel materials with useful properties. Experiments recreating the conditions of planetary interiors provide important constraints on the physical properties of constituent phases and are key to developing models of planetary processes and interpreting geophysical observations. The laser-heated diamond anvil cell (DAC) is currently the only technique capable of routinely accessing the Earth's lower-mantle geotherm for experiments on non-metallic samples, but large temperature uncertainties and poor temperature stability limit the accuracy of measured data and prohibits analyses requiring long acquisition times. We have developed a novel internal resistive heating (IRH) technique for the DAC and demonstrate stable heating of non-metallic samples up to 3000 K and 64 GPa, as confirmed by in situ synchrotron x-ray diffraction and simultaneous spectroradiometric temperature measurement. The temperature generated in our IRH-DAC can be precisely controlled and is extremely stable, with less than 20 K variation over several hours without any user intervention, resulting in temperature uncertainties an order of magnitude smaller than those in typical laser-heating experiments. Our IRH-DAC design, with its simple geometry, provides a new and highly accessible tool for investigating materials at extreme conditions. It is well suited for the rapid collection of high-resolution P-V-T data, precise demarcation of phase boundaries, and experiments requiring long acquisition times at high temperature. Our IRH technique is ideally placed to exploit the move toward coherent nano-focused x-ray beams at next-generation synchrotron sources.

Structure of levitated Si-Ge melts studied by high-energy x-ray diffraction in combination with reverse Monte Carlo simulations.

The short-range order in liquid Si, Ge and binary Six-Ge1-xalloys (x= 0.25, 0.50, 0.75) was studied by x-ray diffraction and reverse Monte Carlo simulations. Experiments were performed in the normal and supercooled liquid states by using the containerless technique of aerodynamic levitation with CO2laser heating, enabling deeper supercooling of liquid Si and Si-Ge alloys than previously reported. The local atomic structure of liquid Si and Ge resembles theß-tin structure. The first coordination numbers of about 6 for all compositions are found to be independent of temperature indicating the supercooled liquids studied retain this high-density liquid (HDL) structure. However, there is evidence of developing local tetrahedral ordering, as manifested by a shoulder on the right side of the first peak inS(Q) which becomes more prominent with increasing supercooling. This result is potentially indicative of a continuous transition from the stable HDLß-tin (high pressure) phase, towards a metastable low-density liquid phase, reminiscent of the diamond (ambient pressure) structure.

In situ observation of nanolite growth in volcanic melt: A driving force for explosive eruptions.

Although gas exsolution is a major driving force behind explosive volcanic eruptions, viscosity is critical in controlling the escape of bubbles and switching between explosive and effusive behavior. Temperature and composition control melt viscosity, but crystallization above a critical volume (>30 volume %) can lock up the magma, triggering an explosion. Here, we present an alternative to this well-established paradigm by showing how an unexpectedly small volume of nano-sized crystals can cause a disproportionate increase in magma viscosity. Our in situ observations on a basaltic melt, rheological measurements in an analog system, and modeling demonstrate how just a few volume % of nanolites results in a marked increase in viscosity above the critical value needed for explosive fragmentation, even for a low-viscosity melt. Images of nanolites from low-viscosity explosive eruptions and an experimentally produced basaltic pumice show syn-eruptive growth, possibly nucleating a high bubble number density.

Structural Ordering in Liquid Gallium under Extreme Conditions.

The atomic-scale structure, melting curve, and equation of state of liquid gallium has been measured to high pressure (p) and high temperature (T) up to 26 GPa and 900 K by in situ synchrotron x-ray diffraction. Ab initio molecular dynamics simulations up to 33.4 GPa and 1000 K are in excellent agreement with the experimental measurements, providing detailed insight at the level of pair distribution functions. The results reveal an absence of dimeric bonding in the liquid state and a continuous increase in average coordination number n[over ¯]_{Ga}^{Ga} from 10.4(2) at 0.1 GPa approaching ∼12 by 25 GPa. Topological cluster analysis of the simulation trajectories finds increasing fractions of fivefold symmetric and crystalline motifs at high p-T. Although the liquid progressively resembles a hard-sphere structure towards the melting curve, the deviation from this simple description remains large (≥40%) across all p-T space, with specific motifs of different geometries strongly correlating with low local two-body excess entropy at high p-T.

The HXD95: a modified Bassett-type hydrothermal diamond-anvil cell for in situ XRD experiments up to 5 GPa and 1300 K.

A new diamond-anvil cell apparatus for in situ synchrotron X-ray diffraction measurements of liquids and glasses, at pressures from ambient to 5 GPa and temperatures from ambient to 1300 K, is reported. This portable setup enables in situ monitoring of the melting of complex compounds and the determination of the structure and properties of melts under moderately high pressure and high temperature conditions relevant to industrial processes and magmatic processes in the Earth's crust and shallow mantle. The device was constructed according to a modified Bassett-type hydrothermal diamond-anvil cell design with a large angular opening (θ = 95°). This paper reports the successful application of this device to record in situ synchrotron X-ray diffraction of liquid Ga and synthetic PbSiO3 glass to 1100 K and 3 GPa.

From Molten Calcium Aluminates through Phase Transitions to Cement Phases.

Crystalline calcium aluminates are a critical setting agent in cement. To date, few have explored the microscopic and dynamic mechanism of the transitions from molten aluminate liquids, through the supercooled state to glassy and crystalline phases, during cement clinker production. Herein, the first in situ measurements of viscosity and density are reported across all the principal molten phases, relevant to their eventual crystalline structures. Bulk atomistic computer simulations confirm that thermophysical properties scale with the evolution of network substructures interpenetrating melts on the nanoscale. It is demonstrated that the glass transition temperature (T g) follows the eutectic profile of the liquidus temperature (T m), coinciding with the melting zone in cement production. The viscosity has been uniquely charted over 14 decades for each calcium-aluminate phase, projecting and justifying the different temperature zones used in cement manufacture. The fragile-strong phase transitions are revealed across all supercooled phases coinciding with heterogeneous nucleation close to 1.2T g, where sintering and quenching occur in industrial-scale cement processing.

CO3+1 network formation in ultra-high pressure carbonate liquids.

Carbonate liquids are an important class of molten salts, not just for industrial applications, but also in geological processes. Carbonates are generally expected to be simple liquids, in terms of ionic interactions between the molecular carbonate anions and metal cations, and therefore relatively structureless compared to more "polymerized" silicate melts. But there is increasing evidence from phase relations, metal solubility, glass spectroscopy and simulations to suggest the emergence of carbonate "networks" at length scales longer than the component molecular anions. The stability of these emergent structures are known to be sensitive to temperature, but are also predicted to be favoured by pressure. This is important as a recent study suggests that subducted surface carbonate may melt near the Earth's transition zone (~44 km), representing a barrier to the deep carbon cycle depending on the buoyancy and viscosity of these liquids. In this study we demonstrate a major advance in our understanding of carbonate liquids by combining simulations and high pressure measurements on a carbonate glass, (K2CO3-MgCO3) to pressures in excess of 40 GPa, far higher than any previous in situ study. We show the clear formation of extended low-dimensional carbonate networks of close CO32- pairs and the emergence of a "three plus one" local coordination environment, producing an unexpected increase in viscosity with pressure. Although carbonate melts may still be buoyant in the lower mantle, an increased viscosity by at least three orders of magnitude will restrict the upward mobility, possibly resulting in entrainment by the down-going slab.

Structure and dynamics of high-temperature strontium aluminosilicate melts.

We report the study of high-temperature melts (1600-2300 °C) and related glasses in the SrO-Al2O3-SiO2 phase diagram considering three series: (i) depolymerized ([SrO]/[Al2O3] = 3); (ii) fully polymerized ([SrO]/[Al2O3] = 1); and (iii) per-aluminous ([SrO]/[Al2O3] < 1). By considering the results from high-temperature 27Al NMR and high-temperature neutron diffraction, we demonstrate that the structure of the polymerized melts is controlled by a close-to-random distribution of Al and Si in the tetrahedral sites, while the depolymerized melts show smaller rings with a possible loss of non-bridging oxygens on AlO4 units during cooling for high-silica compositions. A few five-fold coordinated VAl sites are present in all compositions, except per-aluminous ones where high amounts of high-coordinated aluminium are found in glasses and melts with complex temperature dependence. In high-temperature melts, strontium has a coordination number of 8 or less, i.e. less than in the corresponding glasses. The dynamics of high-temperature melts were studied from 27Al NMR relaxation and compared to macroscopic shear viscosity data. These methods provide correlation times in close agreement. At very high temperatures, the NMR correlation times can be related to the oxygen self-diffusion coefficient, and we show a decrease of the latter with increasing Si/(Al + Si) ratios for polymerized melts with no compositional dependence for depolymerized ones. The dominant parameter controlling the temperature dependence of the aluminum environment of all melts is the distribution of Al-(OSi)p(OAl)(4-p) units.

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.

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.

High-pressure transformation of SiO2 glass from a tetrahedral to an octahedral network: a joint approach using neutron diffraction and molecular dynamics.

A combination of in situ high-pressure neutron diffraction at pressures up to 17.5(5) GPa and molecular dynamics simulations employing a many-body interatomic potential model is used to investigate the structure of cold-compressed silica glass. The simulations give a good account of the neutron diffraction results and of existing x-ray diffraction results at pressures up to ~60 GPa. On the basis of the molecular dynamics results, an atomistic model for densification is proposed in which rings are "zipped" by a pairing of five- and/or sixfold coordinated Si sites. The model gives an accurate description for the dependence of the mean primitive ring size ⟨n⟩ on the mean Si-O coordination number, thereby linking a parameter that is sensitive to ordering on multiple length scales to a readily measurable parameter that describes the local coordination environment.

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.

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.

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.

Structural transformations on vitrification in the fragile glass-forming system CaAl2O4.

The structure of the fragile glass-forming material CaAl(2)O(4) was measured by applying the method of neutron diffraction with Ca isotope substitution to the laser-heated aerodynamically levitated liquid at 1973(30) K and to the glass at 300(1) K. The results, interpreted with the aid of molecular dynamics simulations, reveal key structural modifications on multiple length scales. Specifically, there is a reorganization on quenching that leads to an almost complete breakdown of the AlO(5) polyhedra and threefold coordinated oxygen atoms present in the liquid, and to their replacement by a predominantly corner-sharing network of AlO(4) tetrahedra in the glass. This process is accompanied by the formation of branched chains of edge and face-sharing Ca-centered polyhedra that give cationic ordering on an intermediate length scale, where the measured coordination number for O around Ca is 6.0(2) for the liquid and 6.4(2) for the glass.

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.

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.

Establishing the structure of GeS(2) at high pressures and temperatures: a combined approach using x-ray and neutron diffraction.

The change in structure of glassy GeS(2) with pressure increasing to [Formula: see text] at ambient temperature was explored by using in situ neutron and x-ray diffraction. Under ambient conditions, the glass structure is made from a mixture of corner- and edge-sharing Ge(S(1/2))(4) tetrahedra where 47(5)% of the Ge atoms are involved in edge-sharing configurations. The network formed by these tetrahedra orders on an intermediate range as manifested by the appearance of a pronounced first sharp diffraction peak in the measured total structure factors at a scattering vector k = 1.02(2) Å(-1) which has a large contribution from Ge-Ge correlations. The intermediate range order breaks down when the pressure on the glass increases above ≈2 GPa but there does not appear to be a significant alteration of the Ge-S coordination number or corresponding bond length with increasing density. The results for the glass are consistent with a densification mechanism in which there is a replacement of edge-sharing by corner-sharing Ge centred tetrahedral motifs and/or a reduction in the Ge-[Formula: see text]-Ge bond angle between corner-sharing tetrahedral motifs with increasing pressure. The change in structure with increasing temperature at a pressure of [Formula: see text] was also investigated by means of in situ x-ray diffraction as the glass crystallized and then liquefied. At 5.2(1) GPa and 828(50) K the system forms a tetragonal crystal, with space group [Formula: see text] and cell parameters a = b = 4.97704(12) and c = 9.5355(4) Å, wherein corner-sharing Ge(S(1/2))(4) tetrahedra pack to form a dense three-dimensional network. A method is described for correcting x-ray diffraction data taken in situ under high pressure, high temperature conditions for a cylindrical sample, container and gasket geometry with a parallel incident beam and with a scattered beam that is defined using an oscillating radial collimator. A method is also outlined for obtaining coordination numbers from direct integration of the peaks in measured x-ray total pair distribution functions.