Pressure dependent structure of amorphous magnesium aluminosilicates: The effect of replacing magnesia by alumina at the enstatite composition.

The effect of replacing magnesia by alumina on the pressure-dependent structure of amorphous enstatite was investigated by applying in situ high-pressure neutron diffraction with magnesium isotope substitution to glassy (MgO)0.375(Al2O3)0.125(SiO2)0.5. The replacement leads to a factor of 2.4 increase in the rate-of-change of the Mg-O coordination number with pressure, which increases from 4.76(4) at ambient pressure to 6.51(4) at 8.2 GPa, and accompanies a larger probability of magnesium finding bridging oxygen atoms as nearest-neighbors. The Al-O coordination number increases from 4.17(7) to 5.24(8) over the same pressure interval at a rate that increases when the pressure is above ∼3.5 GPa. On recovering the glass to ambient conditions, the Mg-O and Al-O coordination numbers reduce to 5.32(4) and 4.42(6), respectively. The Al-O value is in accordance with the results from solid-state 27Al nuclear magnetic resonance spectroscopy, which show the presence of six-coordinated aluminum species that are absent in the uncompressed material. These findings explain the appearance of distinct pressure-dependent structural transformation regimes in the preparation of permanently densified magnesium aluminosilicate glasses. They also indicate an anomalous minimum in the pressure dependence of the bulk modulus with an onset that suggests a pressure-dependent threshold for transitioning between scratch-resistant and crack-resistant material properties.

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)'.

Structure of amorphous materials in the NASICON system Na1+xTi2SixP3-xO12.

The structure of glasses in the sodium (Na) super-ionic conductor (NASICON) system Na1+xTi2SixP3-xO12withx= 0.8 andx= 1.0 was explored by combining neutron and high-energy x-ray diffraction with29Si,31P and23Na solid-state nuclear magnetic resonance (NMR) spectroscopy. The29Si magic angle spinning (MAS) NMR spectra reveal that the silica component remains fully polymerized in the form of Si4units, i.e. the silicon atoms are bound to four bridging oxygen atoms. The31P{23Na} rotational echo adiabatic passage double resonance (REAPDOR) NMR data suggest that the31P MAS NMR line shape originates from four-coordinated Pnunits, wheren= 1, 2 or 3 is the number of bridging oxygen atoms per phosphorus atom. These sites differ in their31P-23Na dipolar coupling strengths. The results support an intermediate range order scenario of a phosphosilicate mixed network-former glass in which the phosphate groups selectively attract the Na+modifier ions. Titanium takes a sub-octahedral coordination environment with a mean Ti-O coordination number of 5.17(4) forx= 0.8 and 4.86(4) forx= 1.0. A mismatch between the P-O and Si-O bond lengths of 8% is likely to inhibit the incorporation of silicon into the phosphorus sites of the NASICON crystal structure.

Effect of antifluorite layer on the magnetic order in Eu-based 1111 compounds, EuTAsF (T = Zn, Mn, and Fe).

The 1111 compounds with an alternating sequence of fluorite and antifluorite layers serve as structural hosts for the vast family of Fe-based superconductors. Here, we use neutron powder diffraction and density-functional-theory (DFT) band-structure calculations to study magnetic order of Eu2+ in the [EuF]+ fluorite layers depending on the nature of the [TAs]- antifluorite layer that can be non-magnetic semiconducting (T = Zn), magnetic semiconducting (T = Mn), or magnetic metallic (T = Fe). Antiferromagnetic transitions at TN ∼ 2.4-3 K due to an ordering of the Eu2+ magnetic moments were confirmed in all three EuTAsF compounds. Whereas in EuTAsF (T = Zn and Mn), the commensurate k1 = (½ ½ 0) stripe order pattern with magnetic moments within the a-b plane is observed, the order in EuFeAsF is incommensurate with k = (0 0.961(1) ½) and represents a cycloid of Eu2+ magnetic moments confined within the bc-plane. Additionally, the Mn2+ sublattice in EuMnAsF features a robust G-type antiferromagnetic order that persists at least up to room temperature, with magnetic moments along the c-direction. Although DFT calculations suggest stripe antiferromagnetic order in the Fe-sublattice of EuFeAsF as the ground state, neutron diffraction reveals no evidence of long-range magnetic order associated with Fe. We show that the frustrating interplane interaction J3 between the adjacent [EuF]+ layers is comparable with in-plane J1-J2 interactions already in the case of semiconducting fluorite layers [TAs]- (T = Zn and Mn) and becomes dominant in the case of the metallic [FeAs]- ones. The latter, along with a slight orthorhombic distortion, is proposed to be the origin of the incommensurate magnetic structure observed in EuFeAsF.

Temperature-dependent anisotropy in the bond lengths of UO2as a result of phonon-induced atomic correlations.

Previous experiments on cubic UO2have suggested that the temperature dependences of the nearest-neighbour U-O and U-U distances aredifferent. We have acquired total-scattering neutron diffraction patterns out toQ = 23.5 Å-1for50

Structure of diopside, enstatite, and magnesium aluminosilicate glasses: A joint approach using neutron and x-ray diffraction and solid-state NMR.

Neutron diffraction with magnesium isotope substitution, high energy x-ray diffraction, and 29Si, 27Al, and 25Mg solid-state nuclear magnetic resonance (NMR) spectroscopy were used to measure the structure of glassy diopside (CaMgSi2O6), enstatite (MgSiO3), and four (MgO)x(Al2O3)y(SiO2)1-x-y glasses, with x = 0.375 or 0.25 along the 50 mol. % silica tie-line (1 - x - y = 0.5) or with x = 0.3 or 0.2 along the 60 mol. % silica tie-line (1 - x - y = 0.6). The bound coherent neutron scattering length of the isotope 25Mg was remeasured, and the value of 3.720(12) fm was obtained from a Rietveld refinement of the powder diffraction patterns measured for crystalline 25MgO. The diffraction results for the glasses show a broad asymmetric distribution of Mg-O nearest-neighbors with a coordination number of 4.40(4) and 4.46(4) for the diopside and enstatite glasses, respectively. As magnesia is replaced by alumina along a tie-line with 50 or 60 mol. % silica, the Mg-O coordination number increases with the weighted bond distance as less Mg2+ ions adopt a network-modifying role and more of these ions adopt a predominantly charge-compensating role. 25Mg magic angle spinning (MAS) NMR results could not resolve the different coordination environments of Mg2+ under the employed field strength (14.1 T) and spinning rate (20 kHz). The results emphasize the power of neutron diffraction with isotope substitution to provide unambiguous site-specific information on the coordination environment of magnesium in disordered materials.

Structure of molten NaCl and the decay of the pair-correlations.

The structure of molten NaCl is investigated by combining neutron and x-ray diffraction with molecular dynamics simulations that employed interaction potentials with either rigid or polarizable ions. Special attention is paid to the asymptotic decay of the pair-correlation functions, which is related to the small-k behavior of the partial structure factors, where k denotes the magnitude of the scattering vector. The rigid-ion approach gives access to an effective restricted primitive model in which the anion and cation have equal but opposite charges and are otherwise identical. For this model, the decay of the pair-correlation functions is in qualitative agreement with simple theory. The polarizable ion approach gives a good account of the diffraction results and yields thermodynamic parameters (density, isothermal compressibility, Debye screening length, and heat capacity) in accord with experiment. The longest decay length for the partial pair-distribution functions is a factor of ≃2.5 times greater than the nearest-neighbor distance. The results are commensurate with the decay lengths found for the effective restricted primitive model, which are much shorter than those found in experiments on concentrated electrolytes or ionic liquids using surface force apparatus.

From SmOF to SmH0.78OF0.22: H/F Substitution in Oxide Fluorides as a Synthesis Route to Heteroanionic Compounds.

Mixed anionic hydrides of the rare earths are a fascinating class of compounds as potential functional materials, especially in luminescence, as photochromic thin films and for ion conduction. For exploratory studies, the effectiveness of various synthesis methods must be investigated, which is done here for metathesis reactions. The reaction of Sm2O3 with PTFE yields SmOF (P21/c, a = 5.60133(19) Å, b = 5.65567(19) Å, c = 5.6282(2) Å, ß = 90.169(5)°, V = 178.295(11) Å3, and Z = 4) in a new, probably metastable, polymorph of the baddeleyite-type structure. Metathesis reactions of SmOF with LiH, NaH, or CaH2 led to a samarium hydride oxide fluoride, SmHxOF1-x; i.e., incomplete H/F exchange occurs. X-ray diffraction and neutron diffraction on a compound with x = 0.78 obtained via NaH reveal hydride, oxide, and fluoride ions to be partially ordered. SmH0.78OF0.22 (Ia3̅, a = 10.947(2) Å, V = 1311.7(4) Å3, Z = 32) crystallizes in an anti-Li3AlN2-type structure with distorted cubic anion coordination for samarium atoms (site symmetry 3̅ and 2) and distorted tetrahedral arrangement of samarium atoms around the anions (site symmetry 1 and 3). It is a fully structurally characterized hydride oxide fluoride and shows a rare crystal chemical feature─the occupation of a crystallographic site by three different anions (0.188 H + 0.667 O + 0.145 F). Interatomic distances between samarium and hydrogen and samarium and the mixed hydrogen/oxygen/fluorine site range from 2.45 to 2.48 Å and 2.29 to 2.42 Å, respectively, and are similar to those in samarium hydride, samarium oxide, and samarium fluoride. Fluoride extraction by reaction with alkali and alkaline earth hydrides has thus proven to be a useful synthesis route to hydride oxides and also hydride oxide halogenides, which might be further exploited in exploratory research on heteroanionic metal hydrides.

Structure and dynamics of aqueous NaCl solutions at high temperatures and pressures.

The structure of a concentrated solution of NaCl in D2O was investigated by in situ high-pressure neutron diffraction with chlorine isotope substitution to give site-specific information on the coordination environment of the chloride ion. A broad range of densities was explored by first increasing the temperature from 323 to 423 K at 0.1 kbar and then increasing the pressure from 0.1 to 33.8 kbar at 423 K, thus mapping a cyclic variation in the static dielectric constant of the pure solvent. The experimental work was complemented by molecular dynamics simulations using the TIP4P/2005 model for water, which were validated against the measured equation of state and diffraction results. Pressure-induced anion ordering is observed, which is accompanied by a dramatic increase in the Cl-O and O-O coordination numbers. With the aid of bond-distance resolved bond-angle maps, it is found that the increased coordination numbers do not originate from a sizable alteration to the number of either Cl⋯D-O or O⋯D-O hydrogen bonds but from the appearance of non-hydrogen-bonded configurations. Increased pressure leads to a marked decrease in the self-diffusion coefficients but has only a moderate effect on the ion-water residence times. Contact ion pairs are observed under all conditions, mostly in the form of charge-neutral NaCl0 units, and coexist with solvent-separated Na+-Na+ and Cl--Cl- ion pairs. The exchange of water molecules with Na+ adopts a concerted mechanism under ambient conditions but becomes non-concerted as the state conditions are changed. Our findings are important for understanding the role of extreme conditions in geochemical processes.

Molecular Dynamics and Neutron Scattering Studies of Potassium Chloride in Aqueous Solution.

Neutron diffraction with isotopic substitution (NDIS) experiments were done on both natural abundance potassium and isotopically labeled 41KCl heavy water solutions to characterize the solvent structuring around the potassium ion in water. Preliminary measurements suggested that the literature value for the coherent neutron scattering length (2.69 fm) for 41K was significantly in error. This value was remeasured using a neutron powder diffractometer and found to be 2.40 fm. This revision increases significantly the contrast between the natural abundance K and 41K by about 30% (from 1.0 to 1.3 fm). The experimentally determined structure factor of the potassium ion was then compared to that calculated from molecular dynamics (MD) simulations. Previous neutron scattering measurements of potassium gave a solvation number of 5.5 (see below). In this study, the NDIS and MD results are in good agreement and allowed us to derive a coordination number of 6.1 for water molecules and 0.8 for chloride ions around each K+ ion in 4 molal aqueous KCl solution.

Femtosecond x-ray diffraction reveals a liquid-liquid phase transition in phase-change materials.

In phase-change memory devices, a material is cycled between glassy and crystalline states. The highly temperature-dependent kinetics of its crystallization process enables application in memory technology, but the transition has not been resolved on an atomic scale. Using femtosecond x-ray diffraction and ab initio computer simulations, we determined the time-dependent pair-correlation function of phase-change materials throughout the melt-quenching and crystallization process. We found a liquid-liquid phase transition in the phase-change materials Ag4In3Sb67Te26 and Ge15Sb85 at 660 and 610 kelvin, respectively. The transition is predominantly caused by the onset of Peierls distortions, the amplitude of which correlates with an increase of the apparent activation energy of diffusivity. This reveals a relationship between atomic structure and kinetics, enabling a systematic optimization of the memory-switching kinetics.

Adjustable Magnetic Phase Transition Inducing Unusual Zero Thermal Expansion in Cubic RCo2-Based Intermetallic Compounds (R = Rare Earth).

Metallic materials that exhibit negligible thermal expansion or zero thermal expansion (ZTE) have great merit for practical applications, but these materials are rare and their thermal expansions are difficult to control. Here, we successfully tailored the thermal expansion behaviors from strongly but abruptly negative to zero over wide temperature ranges in a series of (Gd,R)(Co,Fe)2 (R = Dy, Ho, Er) intermetallic compounds by tuning the composition to bring the first-order magnetic phase transition to second-order. Interestingly, an unusual isotropic ZTE property with a coefficient of thermal expansion of α l = 0.16(0) × 10-6 K-1 was achieved in cubic Gd0.25Dy0.75Co1.93Fe0.07 (GDCF) in the temperature range of 10-275 K. The short-wavelength neutron powder diffraction, synchrotron X-ray diffraction, and magnetic measurement studies evidence that this ZTE behavior was ascribed to the rare-earth-moment-dominated spontaneous volume magnetostriction, which can be controlled by an adjustable magnetic phase transition. The present work extends the scope of the ZTE family and provides an effective approach to exploring ZTE materials, such as by adjusting the magnetism or ferroelectricity-related phase transition in the family of functional materials.

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 Strontium Aluminosilicate Glasses from Molecular Dynamics Simulation, Neutron Diffraction, and Nuclear Magnetic Resonance Studies.

The structure of strontium glasses with the composition (SiO2)1-2 x(Al2O3) x(SrO) x ( R = [SrO]/[Al2O3] = 1) and (SiO2)1-4 x(Al2O3) x(SrO)3 x ( R = 3) has been explored experimentally over both short- and intermediate-length scales using neutron diffraction, 27Al and 29Si nuclear magnetic resonance, and classical molecular dynamics simulations in model systems containing around 10 000 atoms. We aim at understanding the structural role of aluminum and strontium as a function of the chemical composition of these glasses. The short- and medium-range structure such as aluminum coordination, bond angle distribution, Q( n) distribution, and oxygen speciation have been systematically studied. Two potential forms of the repulsive short-range interactions have been investigated, namely, the Buckingham and Morse forms. The comparison of these forms allows us to derive general trends independent of the particular choice of the potential form. In both cases, it is found that aluminum ions are mainly fourfold coordinated and mix with the silicon network favoring the Al/Si mixing in terms of Al-O-Si linkages. For the R = 1 glass series, despite the full charge compensation ([SrO] = [Al2O3]), a small fraction of fivefold aluminum is observed both experimentally and in MD simulations, whereas the concentration of sixfold aluminum is negligible. MD shows that the fivefold aluminum units AlO5 preferentially adopt a small ring configuration and link to tricoordinated oxygen atoms whose population increases with the aluminum content and are mainly found in OAl3 and OAl2Si configurations. The modeled Sr speciation mainly involves SrO7 and SrO8 polyhedra, giving a range of average Sr2+ coordination numbers between 7 and 8 slightly dependent on the short-range repulsive potential form. A detailed statistical analysis of T-O-T' (T, T' = Al,Si), accounting for the population of the various oxygen speciations, reveals that both potentials predict a nearly identical Al/Si mixing.

Calcium ions in aqueous solutions: Accurate force field description aided by ab initio molecular dynamics and neutron scattering.

We present a combination of force field and ab initio molecular dynamics simulations together with neutron scattering experiments with isotopic substitution that aim at characterizing ion hydration and pairing in aqueous calcium chloride and formate/acetate solutions. Benchmarking against neutron scattering data on concentrated solutions together with ion pairing free energy profiles from ab initio molecular dynamics allows us to develop an accurate calcium force field which accounts in a mean-field way for electronic polarization effects via charge rescaling. This refined calcium parameterization is directly usable for standard molecular dynamics simulations of processes involving this key biological signaling ion.

Characterization of Oxygen Defect Clusters in UO2+ x Using Neutron Scattering and PDF Analysis.

In hyper-stoichiometric uranium oxide, both neutron diffraction work and, more recently, theoretical analyses report the existence of clusters such as the 2:2:2 cluster, comprising two anion vacancies and two types of anion interstitials. However, little is known about whether there exists a region of low deviation-from-stoichiometry in which defects remain isolated, or indeed whether at high deviation-from-stoichiometry defect clusters prevail that contain more excess oxygen atoms than the di-interstitial cluster. In this study, we report pair distribution function (PDF) analyses of UO2 and UO2+ x ( x ≈ 0.007 and x ≈ 0.16) samples obtained from high-temperature in situ neutron scattering experiments. PDF refinement for the lower deviation from stoichiometry sample suggests the system is too dilute to differentiate between isolated defects and di-interstitial clusters. For the UO2.16 sample, several defect structures are tested, and it is found that the data are best represented assuming the presence of center-occupied cuboctahedra.

Structure of semiconducting versus fast-ion conducting glasses in the Ag-Ge-Se system.

The transition from a semiconductor to a fast-ion conductor with increasing silver content along the Ag x (Ge0.25Se0.75)(100-x) tie line (0≤x≤25) was investigated on multiple length scales by employing a combination of electric force microscopy, X-ray diffraction, and neutron diffraction. The microscopy results show separation into silver-rich and silver-poor phases, where the Ag-rich phase percolates at the onset of fast-ion conductivity. The method of neutron diffraction with Ag isotope substitution was applied to the x=5 and x=25 compositions, and the results indicate an evolution in structure of the Ag-rich phase with change of composition. The Ag-Se nearest-neighbours are distributed about a distance of 2.64(1) Å, and the Ag-Se coordination number increases from 2.6(3) at x=5 to 3.3(2) at x=25. For x=25, the measured Ag-Ag partial pair-distribution function gives 1.9(2) Ag-Ag nearest-neighbours at a distance of 3.02(2) Å. The results show breakage of Se-Se homopolar bonds as silver is added to the Ge0.25Se0.75 base glass, and the limit of glass-formation at x≃28 coincides with an elimination of these bonds. A model is proposed for tracking the breakage of Se-Se homopolar bonds as silver is added to the base glass.

Understanding Local Structure versus Long-Range Structure: The Case of UO2.

A recent trend in the development of new optimized materials makes use of crystalline domains having nanometer sizes for which characterization methods at the atomic scale are mandatory. Amongst them is pair-distribution function analysis (PDF-analysis), a diffraction technique that has already shown that a short-range or "local" atomic structure of a given domain, having a lower symmetry than the average long-range structure, often exists in many compounds having valuable properties for industrial applications, such as pyrochlores, spinels, and doped ceria among others. However, the manner by which these domains are arranged to produce the average long-range structure is still an open question. Herein, the first structural model that accounts for both the local structure (inside a given domain) and the long-range structure (averaged over all domains) that is observed in the PDF of uranium dioxide is presented. The structural model describes domain walls in such a way as to preserve the uranium coordination polyhedron and to obey the needed symmetry rules. The proper description of domain walls is an important step in the understanding and the modelling of nanostructured materials.

Hydration and Ion Pairing in Aqueous Mg2+ and Zn2+ Solutions: Force-Field Description Aided by Neutron Scattering Experiments and Ab Initio Molecular Dynamics Simulations.

Magnesium and zinc dications possess the same charge and have an almost identical size, yet they behave very differently in aqueous solutions and play distinct biological roles. It is thus crucial to identify the origins of such different behaviors and to assess to what extent they can be captured by force-field molecular dynamics simulations. In this work, we combine neutron scattering experiments in a specific mixture of H2O and D2O (the so-called null water) with ab initio molecular dynamics simulations to probe the difference in the hydration structure and ion-pairing properties of chloride solutions of the two cations. The obtained data are used as a benchmark to develop a scaled-charge force field for Mg2+ that includes electronic polarization in a mean field way. We show that using this electronic continuum correction we can describe aqueous magnesium chloride solutions well. However, in aqueous zinc chloride specific interaction terms between the ions need to be introduced to capture ion pairing quantitatively.

From atomic structure to excess entropy: a neutron diffraction and density functional theory study of CaO-Al2O3-SiO2 melts.

Calcium aluminosilicate CaO-Al2O3-SiO2 (CAS) melts with compositions (CaO-SiO2)(x)(Al2O3)(1-x) for x < 0.5 and (Al2O3)(x)(SiO2)(1-x) for x ≥ 0.5 are studied using neutron diffraction with aerodynamic levitation and density functional theory molecular dynamics modelling. Simulated structure factors are found to be in good agreement with experimental structure factors. Local atomic structures from simulations reveal the role of calcium cations as a network modifier, and aluminium cations as a non-tetrahedral network former. Distributions of tetrahedral order show that an increasing concentration of the network former Al increases entropy, while an increasing concentration of the network modifier Ca decreases entropy. This trend is opposite to the conventional understanding that increasing amounts of network former should increase order in the network liquid, and so decrease entropy. The two-body correlation entropy S2 is found to not correlate with the excess entropy values obtained from thermochemical databases, while entropies including higher-order correlations such as tetrahedral order, O-M-O or M-O-M bond angles and Q(N) environments show a clear linear correlation between computed entropy and database excess entropy. The possible relationship between atomic structures and excess entropy is discussed.