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. In this work, the structure of potassium borate glass was unveiled through the neutron diffraction method and ab initio molecular dynamics (AIMD) simulations. The B-O, K-O, and O-O atomic interactions, bond lengths, coordination numbers, cavity distribution, ring structure distributions and other detailed information in the microstructure of potassium borate glass were obtained. By comparing the structure and properties of potassium borate glass with those of crystals of similar components, it is found that the bond lengths of 3B-BO (BO, bridging oxygen), 4B-BO and 3B-NBO (NBO, non-bridging oxygen) are longer than those of corresponding crystals, so the structure of the boron-oxygen network is looser and the density is smaller than that of similar crystals. Moreover, we found a rule that in both borate glass and crystal, the increase of NBO shortened the length of the B-O bond, and the increase of 4B increased the length of the B-O bond. The key structures affecting the transport rate of K+ were NBO, chain structure units and cavities. This work will provide reference data for designing and developing electrically conductive amorphous materials with faster potassium-ion transport rates.

Mapping the structural trends in zinc aluminosilicate glasses.

The structure of zinc aluminosilicate glasses with the composition (ZnO)x(Al2O3)y(SiO2)1-x-y, where 0 ≤ x < 1, 0 ≤ y < 1, and x + y < 1, was investigated over a wide composition range by combining neutron and high-energy x-ray diffraction with 27Al magic angle spinning nuclear magnetic resonance spectroscopy. The results were interpreted using an analytical model for the composition-dependent structure in which the zinc ions do not act as network formers. Four-coordinated aluminum atoms were found to be in the majority for all the investigated glasses, with five-coordinated aluminum atoms as the main minority species. Mean Al-O bond distances of 1.764(5) and 1.855(5) Å were obtained for the four- and five-coordinated aluminum atoms, respectively. The coordination environment of zinc was not observed to be invariant. Instead, it is dependent on whether zinc plays a predominantly network-modifying or charge-compensating role and, therefore, varies systematically with the glass composition. The Zn-O coordination number and bond distance were found to be 4.36(9) and 2.00(1) Å, respectively, for the network-modifying role vs 5.96(10) and 2.08(1) Å, respectively, for the charge-compensating role. The more open coordination environment of the charge-compensator is related to an enhanced probability of zinc finding bridging oxygen atoms as nearest-neighbors, reflecting a change in the connectivity of the glass network comprising four-coordinated silicon and aluminum atoms as the alumina content is increased.

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)3 boric acid molecules, B(OH)4- 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 trans-B(OH)3 tend to form a monodentate contact ion pair (MCIP) with a K-B distance ∼3.8 Å, which remains constant upon changing the solution concentration. Potassium ions and cis-B(OH)3 form both a MCIP at K-B ∼3.8 Å and a bidentate contact ion pair (BCIP) at K-B ∼3.4 Å. As the solution concentration increases, there is a BCIP to MCIP transformation. Boric acid molecules can undergo hydration in one of three ways: direct hydration, interstitial hydration, and axial hydration. The energetic hydration preference is direct hydration → interstitial hydration → axial hydration. Nine water molecules are required when all water molecules directly interact with the -OH groups of B(OH)4-, and a tenth water molecule is located at an interstitial position. The hydrogen bonding between boric acid molecule/metaborate ion and water molecules is stronger than that between water molecules in the hydration layer.

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 ab initio molecular dynamics simulations, we report that the [Mg(NO3)2] molecular structure in solution from the coexistence of a free [Mg(H2O)6]2+ octahedral supramolecular structure with a free [NO3(H2O)n]- (n = 11-13) supramolecular structure to an [Mg2+(H2O)n(NO3-)m] (n = 3, 4, 5; m = 3, 2, 1) associated structure with increasing concentration. Interestingly, two hydration modes of NO3--the nearest neighbor hydration with a hydration distance less than 3.9 Å and the next nearest neighbor hydration with hydration distance ranging from 3.9 to 4.3 Å-were distinguished. With an increase in the solution concentration, the hydrated NO3- ions lost outer layer water molecules, and the hexagonal octahedral hydration structure of [Mg(H2O)62+] was destroyed, resulting in direct contact between Mg2+ and NO3- ions in a monodentate way. As the concentration of the solution further increased, NO3- ions replaced water molecules in the hydration layer of Mg2+ to form three-ion clusters and even more complex chains or linear ion clusters.

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. Using pulsed neutron diffraction and Raman spectroscopy supported by first-principles simulations, we show that preferential diffusion pathways in vitreous sodium and silver sulfides are related to isolated sulfur Siso, that is, the sulfur species surrounded exclusively by mobile cations with a typical stoichiometry of M/Siso ≈ 2. The Siso/Stot fraction appears to be a reliable descriptor of fast ion transport in glassy sulfide systems over a wide range of ionic conductivities and cation diffusivities. The Siso fraction increases with mobile cation content x, tetrahedral coordination of the network former and, in case of thiogermanate systems, with germanium disulfide metastability and partial disproportionation, GeS2 → GeS + S, leading to the formation of additional sulfur, transforming into Siso. A research strategy enabling to achieve extended and interconnected pathways based on isolated sulfur would lead to glassy electrolytes with superior ionic diffusion.

Preparation and Structure of the Ion-Conducting Mixed Molecular Glass Ga2I3.17.

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 Ga2I3.17 and investigated the correlations between the local structure, thermal properties, and ionic conductivity. The novel glass displays a glass transition at 60 °C, and its molecular make-up consists of GaI4- tetrahedra, Ga2I62- heteroethane ions, and Ga+ cations. Neutron diffraction was employed to characterize the local structure and coordination geometries within the glass. Raman spectroscopy revealed a strongly localized nonmolecular mode in glassy Ga2I3.17, coinciding with the observation of two relaxation mechanisms below Tg in the AC admittance spectra.

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 Na2S-As2S3 sodium thioarsenate glasses, consisting of long corner-sharing (CS) pyramidal chains CS-(AsSS2/2)k, small AspSq rings (p + q ≤ 11), mixed corner- and edge-sharing oligomers, edge-sharing (ES) dimers ES-As2S4, and isolated (ISO) pyramids ISO-AsS3, entirely or partially connected by sodium species. Polysulfide S-S bridges and structural units with homopolar As-As bonds complete the glass structure, which is basically different from structural motifs predicted by the equilibrium phase diagram. In contrast to superionic silver and sodium sulfide glasses, characterized by a significant population of isolated sulfur species Siso (0.20 < Siso/Stot < 0.28), that is, sulfur connected to only mobile cations M+ with a usual M/Siso stoichiometry of 2, poorly conducting Na2S-As2S3 alloys exhibit a modest Siso fraction of 6.2%.

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 (R2O-SiO2; R = Na, Li) and alkali/alkaline-earth silicate (Na2O-MO-SiO2; 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)S correlations were clearly isolated from the other overlapping correlations due to Si-O and (O-O)Si distances in the SiO4 tetrahedra and the modifier-oxygen (R-O and M-O) distances. Clear evidence was obtained that the sulfur is present as SO4 2- groups, confirmed by the observation in the Raman spectra of the symmetric S-O stretch mode of SO4 2- groups. The modifier-oxygen bond length distributions were deconvoluted from the neutron correlation functions by fitting. The Na-O and Li-O bond length distributions were clearly asymmetric, whereas no evidence was obtained for asymmetry of the Ca-O and Ba-O distributions. A consideration of the bonding shows that the oxygen atoms in the SO4 2- groups do not participate in the silicate network and as such constitute a third type of oxygen, "non-network oxygen", in addition to the bridging and non-bridging oxygens that are bonded to silicon atoms. Thus, each individual sulfate group is surrounded by a shell of modifier and is not connected directly to the silicate network. The addition of SO3 to the glass leads to a conversion of oxygen atoms within the silicate network from non-bridging to bridging so that there is repolymerization of the silicate network. There is evidence that SO3 doping leads to changes in the form of the distribution of Na-O bond lengths with a reduction in the fitted short-bond coordination number and an increase in the fitted long-bond coordination number, and this is consistent with repolymerization of the silicate network. In contrast, there is no evidence that SO3 doping leads to a change in the distribution of Li-O bond lengths with a total Li-O coordination number consistently in excess of 4.

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

Group 13 trihalides MY3 (M = Al, Ga, and In; Y = Cl, Br, and I) mostly having a dimeric M2Y6 molecular structure in the solid state and a mixture of M2Y6 dimers and MY3 monomers in the vapor phase are potential candidates for entropy-driven liquid-liquid transition M2Y6 ⇄ 2MY3 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 GaCl3 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 D2h symmetry, the ES Ga2Cl6 molecules in the melt have a puckered structure of the central four-membered ring with shorter Cl-Cl (2.90-3.09 Å) and longer Ga-Ga (3.20-3.26 Å) second-neighbor correlations. The elongation of Ga-Ga intramolecular distances with increasing temperature simultaneously with diminished Cl-Cl nearest neighbor contacts destabilizes the ES dimers, indicating the first step toward dimer dissociation.

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. This study shows the cytocompatibility and osteogenic potential of PBGs where CaO is gradually replaced by SrO in the near invert glass system 40P2 O5 ·(16-x)CaO·20Na2 O·24MgO·xSrO (x = 0, 4, 8, 12, and 16 mol%). Direct seeding of MG63 cells onto glass discs showed no significant difference in cell metabolic activity and DNA amount measurement across the different formulations studied. Cell attachment and spreading was confirmed via scanning electron microscopy (SEM) imaging at Days 3 and 14. Alkaline phosphatase (ALP) activity was similarly maintained across the glass compositions. Follow-on studies explored the effect of each glass composition in microsphere conformation (size: 63-125 µm) on human mesenchymal stem cells (hMSCs) in 3D cultures, and analysis of cell metabolic activity and ALP activity showed no significant differences at Day 14 over the compositional range investigated, in line with the observations from MG63 cell culture studies. Environmental SEM and live cell imaging at Day 14 of hMSCs seeded on the microspheres showed cell attachment and colonisation of the microsphere surfaces, confirming these formulations as promising candidates for regenerative medicine strategies addressing compromised musculoskeletal/orthopaedic diseases.

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.

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. The zinc and calcium bonding shows differences between composition: the distribution of Zn-Ca bond lengths becomes narrower with increasing Zn content, and the preference for Zn and Ca to avoid bonding to themselves or each other becomes less strong, and, for Zn-Ca, transforms into a positive preference to bond to each other. This transition occurs at about the same Zn content at which the behaviour on implantation changes, hinting at a possible structural connection. A very broad distribution of Voronoi polyhedra are also found, and this distribution broadens with increasing Zn content. The efficient cluster packing model, which is often used to describe the structure of bulk metallic glasses, was found not to describe these systems well.

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. Using a combination of diffraction methods (X-ray and neutron) and inelastic neutron scattering spectroscopy, we show that the CuH from the borohydride route has the same bulk structure as CuH produced by other routes. Our work shows that the product consists of a core of CuH with a shell of water and that this may be largely replaced by ethanol. This offers the possibility of modifying the properties of CuH produced by aqueous routes.

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. The results show that, while all methods for the synthesis of CuH result in the same bulk product, the synthetic path taken engenders differing surface properties. The different behaviors of CuH obtained by aqueous and nonaqueous routes can be ascribed to a combination of very different particle size and dissimilar surface termination, namely, bonded hydroxyls for the aqueous routes and a coordinated donor for the nonaqueous routes. This work provides a particularly clear example of how the nature of an adsorbed layer on a nanoparticle surface determines the properties.

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)(Fe1.06Mn0.17Bi0.77)O6.87 and (K0.24Bi1.51)(Fe1.07Mn0.15Bi0.78)O6.86 are described. With preparation at 200 °C for 6 h in solutions of sodium or potassium hydroxide, the alkali metals introduced from these mineralizers are essential to the synthesis of the phases. The average long-range order of the pyrochlore structure, with space group Fd3̅m, was investigated and refined against X-ray and neutron diffraction data, and it was shown that disorder is present in both the metal and coordinating oxygen positions, along with metal-mixing across both the A and B sites of the structure. XANES analysis confirms the presence of Mn(4+), mixed valence Bi(3+) and Bi(5+), and Fe(3+), the last also verified by (57)Fe Mössbauer spectroscopy. Magnetic measurements show a lack of long-range magnetic ordering that is typical of geometrically frustrated pyrochlores. The observed glasslike interactions occur at low temperatures, with the onset temperature depending upon the magnitude of the applied external field. Variable temperature X-ray diffraction shows that these pyrochlores are metastable and collapse on heating at ca. 395 °C, which suggests that their formation by conventional solid-state synthesis would be impossible.

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)4­n(NC)n tetrahedral species, which do not follow a simple binomial distribution. The Zn(CN)4 and Zn(NC)4 species occur with much lower probabilities than are predicted by binomial theory, supporting the conclusion that they are of higher energy than the other local arrangements. The lowest energy arrangement is Zn(CN)2(NC)2. The use of total neutron diffraction at 11.4 K, with analysis of both the Bragg diffraction and the derived total correlation function, yields the first experimental determination of the individual Zn­N and Zn­C bond lengths as 1.969(2) and 2.030(2) Å, respectively. The very small difference in bond lengths, of ~0.06 Å, means that it is impossible to obtain these bond lengths using Bragg diffraction in isolation. Total neutron diffraction also provides information on both the average and the local atomic displacements responsible for NTE in Zn(CN)2. The principal motions giving rise to NTE are shown to be those in which the carbon and nitrogen atoms within individual Zn­C≡N­Zn linkages are displaced to the same side of the Zn···Zn axis. Displacements of the carbon and nitrogen atoms to opposite sides of the Zn···Zn axis, suggested previously in X-ray studies as being responsible for NTE behavior, in fact make negligible contributions at temperatures up to 295 K.

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(0.973(8))O(3.752(8)), has been determined from total neutron scattering to be a partially defective spinel with mixed-valent cobalt (approximately 25% Co(3+) and 75% Co(2+)) and with vacancies on approximately 6% of oxygen sites. Pair distribution function (PDF) analysis reveals significant local deviations from the average cubic structure, which are attributed to the conflicting coordination preferences of the Co(2+) (potential Jahn-Teller distortion) and Ga(3+) (Ga off-centring). Reverse Monte Carlo (RMC) modelling supports this conclusion since different metal-oxygen bond-distance distributions are found for the two cations in the refined configuration. An investigation of magnetic properties shows evidence of short-range magnetic order and spin-glass-like behaviour, consistent with the structural disorder of the material.

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. The proposed turbostratic inner core explains the occurrence of the additional (002) and (004) graphitic peaks in the diffraction pattern of the studied sample and provides information about the interior structure of the dahlia-type aggregates.

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 ß-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. The oxygen atoms are coordinated predominantly to four cations. Explicit introduction of lone-pair entities into some models leads to modification of the local Pb environment, whilst still allowing for reproduction of the measured diffraction patterns, thus demonstrating the non-uniqueness of the solutions. Nonetheless, the models share many features with crystalline Pb11Si3O17, including the O-Pb-O bond angle distribution, which is more highly structured than reported for lower Pb content glasses using reverse Monte Carlo techniques. The lone-pair separation of 2.85 Å in the model glasses compares favourably with that estimated in α-PbO as 2.88 Å, and these lone-pairs organise to create voids in the glass, just as they create channels in Pb11Si3O17 and interlayer spaces in the PbO polymorphs.

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. In further solvothermal oxidation reactions a novel gallium oxyhydroxide, Ga(5)O(7)(OH), is formed, the thermal decomposition of which reveals a new, transient gallium oxide polymorph, κ-Ga(2)O(3), before transformation into ß-Ga(2)O(3). In contrast, the thermal decomposition of Ga(NO(3))(3)·9H(2)O first forms ε-Ga(2)O(3) and then ß-Ga(2)O(3). Examination of in situ thermodiffraction data shows that ε-Ga(2)O(3) is always contaminated with ß-Ga(2)O(3) and with this knowledge a model for its structure was deduced and refined--space group P6(3)mc with a ratio of tetrahedral/octahedral gallium of 2.2:1 in close-packed oxide layers. Importantly, thermodiffraction provides no evidence for the existence of the speculated bixbyite structured δ-Ga(2)O(3); at the early stages of thermal decomposition of Ga(NO(3))(3)·9H(2)O the first distinct phase formed is merely small particles of ε-Ga(2)O(3).