Deciphering the structure and potassium-ion transport mechanism of potassium borate glass.

Potassium borate glass has great potential as an ion transport material. The ion transport rate is closely related to the microstructure of the glass. However, the disorder and variations in boron and oxygen atom types in the glass structure pose challenges in the analysis of this complex glass structure.

Structural analysis of potassium borate solutions.

In this work, H/D isotopic substitution neutron diffraction was combined with empirical potential structure refinement (EPSR) and DFT-based quantum calculations to study the interactions between B(OH) boric acid molecules, B(OH) metaborate ions, water molecules, and potassium cations in borate solutions. The results show that the solute ions and molecules have a marked effect on the second coordination shell of the water molecules, causing a greater deviation from a tetrahedral structure than is observed for pure water. Potassium ions and -B(OH) tend to form a monodentate contact ion pair (MCIP) with a K-B distance ∼3.

Unveiling the structure of aqueous magnesium nitrate solutions by combining X-ray diffraction and theoretical calculations.

The structure of aqueous magnesium nitrate solution is gaining significant interest among researchers, especially whether contact ion pairs exist in concentrated solutions. Here, combining X-ray diffraction experiments, quantum chemical calculations and molecular dynamics simulations, we report that the [Mg(NO)] molecular structure in solution from the coexistence of a free [Mg(HO)] octahedral supramolecular structure with a free [NO(HO)] ( = 11-13) supramolecular structure to an [Mg(HO)(NO)] ( = 3, 4, 5; = 3, 2, 1) associated structure with increasing concentration. Interestingly, two hydration modes of NO-the nearest neighbor hydration with a hydration distance less than 3.

Deciphering Fast Ion Transport in Glasses: A Case Study of Sodium and Silver Vitreous Sulfides.

High-capacity solid-state batteries are promising future products for large-scale energy storage and conversion. Sodium fast ion conductors including glasses and glass ceramics are unparalleled materials for these applications. Rational design and tuning of advanced sodium sulfide electrolytes need a deep insight into the atomic structure and dynamics in relation with ion-transport properties.

Preparation and Structure of the Ion-Conducting Mixed Molecular Glass GaI.

Modern functional glasses have been prepared from a wide range of precursors, combining the benefits of their isotropic disordered structures with the innate functional behavior of their atomic or molecular building blocks. The enhanced ionic conductivity of glasses compared to their crystalline counterparts has attracted considerable interest for their use in solid-state batteries. In this study, we have prepared the mixed molecular glass GaI and investigated the correlations between the local structure, thermal properties, and ionic conductivity.

Chemical and Structural Variety in Sodium Thioarsenate Glasses Studied by Neutron Diffraction and Supported by First-Principles Simulations.

Sodium-conducting sulfide glasses are promising materials for the next generation of solid-state batteries. Deep insight into the glass structure is required to ensure a functional design and tailoring of vitreous alloys for energy applications. Using pulsed neutron diffraction supported by first-principles molecular dynamics, we show a structural diversity of NaS-AsS sodium thioarsenate glasses, consisting of long corner-sharing (CS) pyramidal chains CS-(AsSS), small AsS rings ( + ≤ 11), mixed corner- and edge-sharing oligomers, edge-sharing (ES) dimers ES-AsS, and isolated (ISO) pyramids ISO-AsS, entirely or partially connected by sodium species.

Neutron Diffraction and Raman Studies of the Incorporation of Sulfate in Silicate Glasses.

The oxidation state, coordination, and local environment of sulfur in alkali silicate (RO-SiO; R = Na, Li) and alkali/alkaline-earth silicate (NaO-MO-SiO; M = Ca, Ba) glasses have been investigated using neutron diffraction and Raman spectroscopy. With analyses of both the individual total neutron correlation functions and suitable doped-undoped differences, the S-O bonds and (O-O) correlations were clearly isolated from the other overlapping correlations due to Si-O and (O-O) distances in the SiO tetrahedra and the modifier-oxygen (R-O and M-O) distances. Clear evidence was obtained that the sulfur is present as SO groups, confirmed by the observation in the Raman spectra of the symmetric S-O stretch mode of SO groups.

Dimeric Molecular Structure of Molten Gallium Trichloride and a Hidden Evolution toward a Possible Liquid-Liquid Transition.

Group 13 trihalides MY (M = Al, Ga, and In; Y = Cl, Br, and I) mostly having a dimeric MY molecular structure in the solid state and a mixture of MY dimers and MY monomers in the vapor phase are potential candidates for entropy-driven liquid-liquid transition MY ⇄ 2MY at elevated temperatures. Using pulsed neutron diffraction and high-energy X-ray scattering supported by structural modeling, we show a dimer molecular structure of liquid GaCl above the melting point at 351 K and midway between the boiling point (474 K) and the critical temperature (694 K) with almost hidden characteristic evolution toward a possible liquid-liquid transition. In contrast to edge-sharing (ES) dimers in solid and vapor of symmetry, the ES GaCl molecules in the melt have a puckered structure of the central four-membered ring with shorter Cl-Cl (2.

In vitro cellular testing of strontium/calcium substituted phosphate glass discs and microspheres shows potential for bone regeneration.

Phosphate-based glasses (PBGs) are ideal materials for regenerative medicine strategies because their composition, degradation rates, and ion release profiles can easily be controlled. Strontium has previously been found to simultaneously affect bone resorption and deposition. Therefore, by combining the inherent properties of resorbable PBG and therapeutic activity of strontium, these glasses could be used as a delivery device of therapeutic factors for the treatment of orthopaedic diseases such as osteoporosis.

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](Ga X )(GeX ) 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 and GaX tetrahedra, and give R-S and R-Se coordination numbers of 8.

Atomic structure of Mg-based metallic glasses from molecular dynamics and neutron diffraction.

We use a combination of classical molecular dynamics simulation and neutron diffraction to identify the atomic structure of five different Mg-Zn-Ca bulk metallic glasses, covering a range of compositions with substantially different behaviour when implanted in vitro. There is very good agreement between the structures obtained from computer simulation and those found experimentally. Bond lengths and the total correlation function do not change significantly with composition.

Structure and spectroscopy of CuH prepared via borohydride reduction.

Copper(I) hydride (cuprous hydride, CuH) was the first binary metal hydride to be discovered (in 1844) and is singular in that it is synthesized in solution, at ambient temperature. There are several synthetic paths to CuH, one of which involves reduction of an aqueous solution of CuSO4·5H2O by borohydride ions. The product from this procedure has not been extensively characterized.

How the surface structure determines the properties of CuH.

CuH is a material that appears in a wide diversity of circumstances ranging from catalysis to electrochemistry to organic synthesis. There are both aqueous and nonaqueous synthetic routes to CuH, each of which apparently leads to a different product. We developed synthetic methodologies that enable multigram quantities of CuH to be produced by both routes and characterized each product by a combination of spectroscopic, diffraction and computational methods.

Metastable (Bi, M)2(Fe, Mn, Bi)2O(6+x) (M = Na or K) pyrochlores from hydrothermal synthesis.

The hydrothermal syntheses, structures, and magnetism of two new pyrochlore oxides of compositions (Na0.60Bi1.40)(Fe1.

Total neutron scattering investigation of the structure of a cobalt gallium oxide spinel prepared by solvothermal oxidation of gallium metal.

A new solvothermal synthesis route to mixed-metal gallium oxides with the spinel structure has been developed for ternary oxides of ideal composition Ga(3-x)M(x)O(4-y) (M=Co, Zn, Ni). The structure of the novel cobalt gallate produced in this manner, Ga(1.767(8))Co(0.

Local and average structure in zinc cyanide: toward an understanding of the atomistic origin of negative thermal expansion.

Neutron diffraction at 11.4 and 295 K and solid-state (67)Zn NMR are used to determine both the local and the average structures in the disordered, negative thermal expansion (NTE) material, Zn(CN)2. Solid-state NMR not only confirms that there is head-to-tail disorder of the C≡N groups present in the solid, but yields information about the relative abundances of the different Zn(CN)4–n(NC)n tetrahedral species, which do not follow a simple binomial distribution.

Structural modeling of dahlia-type single-walled carbon nanohorn aggregates by molecular dynamics.

The structure of dahlia-type single-walled carbon nanohorn aggregates has been modeled by classical molecular dynamics simulations, and the validity of the model has been verified by neutron diffraction. Computer-generated models consisted of an outer part formed from single-walled carbon nanohorns with diameters of 20-50 Å and a length of 400 Å and an inner turbostratic graphite-like core with a diameter of 130 Å. The diffracted intensity and the pair correlation function computed for such a constructed model are in good agreement with the neutron diffraction experimental data.

Lone-pair distribution and plumbite network formation in high lead silicate glass, 80PbO·20SiO2.

For the first time a detailed structural model has been determined which shows how the lone-pairs of electrons are arranged relative to each other in a glass network containing lone-pair cations. High energy X-ray and neutron diffraction patterns of a very high lead content silicate glass (80PbO·20SiO2) have been used to build three-dimensional models using empirical potential structure refinement. Coordination number and bond angle distributions reveal structural similarity to crystalline Pb11Si3O17 and α- and β-PbO, and therefore strong evidence for a plumbite glass network built from pyramidal [PbO(m)] polyhedra (m ~ 3-4), with stereochemically active lone-pairs, although with greater disorder in the first coordination shell of lead compared to the first coordination shell of silicon.

Structures of uncharacterised polymorphs of gallium oxide from total neutron diffraction.

A structural investigation is reported of polymorphs of Ga(2)O(3) that, despite much interest in their properties, have hitherto remained uncharacterised due to structural disorder. The most crystalline sample yet reported of γ-Ga(2)O(3) was prepared by solvothermal oxidation of gallium metal in ethanolamine. Structure refinement using the Rietveld method reveals γ-Ga(2)O(3) has a defect Fd3m spinel structure, while pair distribution function analysis shows that the short-range structure is better modelled with local F43m symmetry.

Mixed copper, silver, and gold cyanides, (M(x)M'(1-x))CN: tailoring chain structures to influence physical properties.

Binary mixed-metal variants of the one-dimensional MCN compounds (M = Cu, Ag, and Au) have been prepared and characterized using powder X-ray diffraction, vibrational spectroscopy, and total neutron diffraction. A solid solution with the AgCN structure exists in the (Cu(x)Ag(1-x))CN system over the range (0 ≤ x ≤ 1). Line phases with compositions (Cu(1/2)Au(1/2))CN, (Cu(7/12)Au(5/12))CN, (Cu(2/3)Au(1/3))CN, and (Ag(1/2)Au(1/2))CN, all of which have the AuCN structure, are found in the gold-containing systems.

Rearrangement of the structure during nucleation of a cordierite glass doped with TiO(2).

Ordering of disordered materials occurs during the activated process of nucleation that requires the formation of critical clusters that have to surmount a thermodynamic barrier. The characterization of these clusters is experimentally challenging but mandatory to improve nucleation theory. In this paper, the nucleation of a magnesium alumino-silicate glass containing the nucleating oxide TiO(2) is investigated using neutron scattering with Ti isotopic substitution and (27)Al NMR.

Structures of Pd(CN)2 and Pt(CN)2: intrinsically nanocrystalline materials?

Analysis and modeling of X-ray and neutron Bragg and total diffraction data show that the compounds referred to in the literature as "Pd(CN)(2)" and "Pt(CN)(2)" are nanocrystalline materials containing small sheets of vertex-sharing square-planar M(CN)(4) units, layered in a disordered manner with an intersheet separation of ~3.44 Å at 300 K. The small size of the crystallites means that the sheets' edges form a significant fraction of each material.

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.

Environment of titanium and aluminum in a magnesium alumino-silicate glass.

The structure of the glass 2MgO-2Al(2)O(3)-5SiO(2)-TiO(2) was investigated using neutron diffraction with isotopic substitution. Reverse Monte Carlo (RMC) modeling was used to reproduce experimental structure factors derived from diffraction experiments. The local environment of titanium atoms was determined and it corresponds to an average of 5.