Packing as a probe of structure in alkaline earth glass systems

Packing is an intrinsic property of glass, defined as the ratio of ionic volume to molar volume, and is a useful parameter for analyzing structural changes with composition. Alkali based glasses show two trends in packing, one dominated by the oxygen covalent network for the small ions, Li and Na, and one ionically dominated by the metal cations for the large, K, Rb and Cs cases [S. Giri, C. Gaebler, J. Helmus, M. Affatigato, S.A. Feller, J. Non-Cryst. Solids 347 (2004) 87]. We have found that alkaline earth glasses do not display these behaviors, and in this paper we determined the packing fractions of these glasses and compared them with the alkali case. Further, we considered the structural implications of the packing trends.     

Structure study of multi-component borosilicate glasses from high-Q neutron diffraction measurement and RMC modeling

A neutron diffraction structure study has been performed on multi-component borosilicate glasses with compositions (65 − x)SiO₂ · xB₂O₃ · 25Na₂O · 5BaO · 5ZrO₂, x = 5-15 mol%. The structure factor has been measured up to a rather high momentum transfer value of 30 Å⁻¹, which made high r-space resolution available for real space analyses. Reverse Monte Carlo simulation was applied to calculate the partial atomic pair correlation functions, nearest neighbor atomic distances and coordination number distributions. The Si-O network consists of tetrahedral SiO₄ units with characteristic first neighbor distances at r_Si-O = 1.60 Å and r_Si-Si = 3.0 Å. The boron environment contains two well-resolved B-O distances at 1.40 and 1.60 Å and both 3- and 4-fold coordinated B atoms are present. A chemically mixed network structure is proposed including ^[4]B-O-^[4]Si and ^[3]B-O-^[4]Si chain segments. The O-O and Na-O distributions suggest partial segregation of silicon and boron rich regions. The highly effective ability of Zr to stabilize glassy and hydrolytic properties of sodium-borosilicate materials is interpreted by the network-forming role of Zr ions.     

Structure of fluorochlorozirconate glasses using molecular dynamics

The structure of fluorochlorozirconate glass with composition Zr_0.55Ba_0.20La_0.05Na_0.20F_2.95−xCl_x with 0 ? x ? 0.9, i.e., up to ∼30% chlorine anions, has been simulated using molecular dynamics methods applied to a unit cell comprising 790 ions. The structure comprises a network of (mainly) corner and edge-linked ZrF_8−pCl_p, ZrF_7−qCl_q and LaF_7−rCl_r polyhedra with sodium, barium and additional chlorine ions occupying irregular positions in space between the polyhedra. For chlorine concentrations above about 15%, the number of chlorine ions occupying corner bridging positions increases markedly which is expected to reduce the glass temperature. For chlorine concentrations greater than about 20%, the spatial distribution of ions is not uniform and clustering into zirconium rich and sodium, barium and chlorine rich regions occurs. The possibility that this phenomenon may be a precursor to the observed precipitation of barium chloride crystals just above the glass temperature is discussed.     

Evolution of the local environment of lanthanum during simplified SON68 glass leaching

The evolution of the short- and medium-range local environment of lanthanum was determined by L_III-edge X-ray absorption spectroscopy (XAS) during leaching of simplified SON68-type glasses. In glass without phosphorus, lanthanum is found in a silicate environment, and its first coordination sphere comprises eight oxygen atoms at a mean distance of 2.51 Å. When this glass was leached at a high renewal rate, the lanthanum local environment was significantly modified: it was present at hydroxycarbonate and silicate sites with a mean La-O distance of 2.56 Å, and the second neighbors consisted of La atoms instead of Si for the glass. Conversely, in the gel formed at low renewal rates, lanthanum was found in a silicate environment similar to that of the glass. In phosphorus-doped glass, lanthanum is found in a phosphate environment, although the Si/P atomic ratio is 20:1. Lanthanum is surrounded by seven oxygen atoms at a mean distance of 2.37 Å. When phosphorus-doped glass is leached, regardless of the leaching solution flow rate, the short- and medium-range lanthanum local environment remains almost constant; the most significant change is a 0.05 Å increase in the La-O distance.     

Investigation of the chemical solubility of mixed-alkali fluorcanasite forming glasses

There is currently significant interest in all-ceramic dental restorations due to the demand to replace metals as the primary load-bearing tooth restorative material. A promising non-metallic material for such restorations is fluorcanasite, a chain-silicate glass-ceramic that is castable using conventional dental metal-casting techniques and which exhibits enhanced fracture toughness and flexural strength compared with currently available resin-bonded ceramics. Unfortunately, because of its relatively low silica content, it exhibits poor chemical durability. The aim of this study was to assess the influence of compositional changes on the formation and chemical solubility of the fluorcanasite forming glass, crystalline phase and residual glass. To this end, mixed-alkali compositions have been investigated and it has been shown that the solubility of the glass is a function of the alkali species present in the glass. By changing the alkali ratio of the fluorcanasite forming glass from 0.33 ([K]/[K + Na]) of the base composition derived from stoichiometry to 0.47, it was possible to reduce the chemical solubility of the fluorcanasite material significantly. The addition of extra CaF₂ to refine the grain structure resulted in a decrease in the durability of the material, making it currently unacceptable for dental applications. The glass-ceramic exhibits a minimum chemical solubility at the composition K⁷/Na⁸. The residual glass may have a slightly elevated K content compared to the original glass. The addition of extra CaF₂ to refine the grain structure resulted in an unacceptable decrease in the durability of the material.     

Reverse Monte Carlo simulations of an amorphous Cr25Nb75 alloy produced by mechanical alloying

The local atomic structure of an amorphous Cr₂₅Nb₇₅ alloy produced by mechanical alloying was determined using only one X-ray total structure factor S(K) as input data for reverse Monte Carlo simulations. The results showed that the amorphous alloy has a local atomic structure similar to that predicted by the additive hard sphere model for a Cr and Nb mixture with same composition of the alloy, and quite different of those found in the cubic and hexagonal Cr₂Nb crystals.     

High resolution O MAS and triple-quantum MAS NMR studies of gallosilicate glasses

Gallosilicate (or ‘galliosilicate’) glasses have been widely studied as analogs of aluminosilicates, and the variations with composition in properties are known to be similar in both systems. We have applied ¹⁷O MAS and triple-quantum MAS (3QMAS) NMR spectroscopy to investigate the oxygen local environments in Na-, Li-, Ca- and Y-gallosilicate glasses. Signals due to several different oxygen species can be resolved and their concentrations quantified and NMR parameters determined. The NMR spectra generally resemble those of aluminosilicate glasses, indicating that the current model of gallium ions occupying the same types of sites as aluminum ions is a good first approximation. Quadrupolar coupling constants for the various oxygen sites tend to be larger than those for aluminosilicates, however, and vary less among different types of sites. Broader ¹⁷O spectra at low to medium external magnetic fields result. In detail, several types of differences between the observed oxygen species populations for gallosilicate and aluminosilicate are consistent with the larger radius of Ga³⁺ in comparison to Al³⁺, and possibly with a somewhat greater tendency for the former to form groups with oxygen coordination numbers greater than four. These include more Si-Ga disorder than Si-Al disorder in corresponding sodium gallo- vs. aluminosilicates, and more ‘non-stoichiometric’ non-bridging oxygen in a calcium gallosilicate than in a calcium aluminosilicate glass.     

Simulation and scaling of ac conductivities in ion-conducting glasses

Simulation is made about ac conductivity, σ(ω), in ion-conducting glass by recurring to one of the Maxwell’s equations. It is concluded that (1) σ(ω) is made of conduction and conduction-related polarization of the mobile ions, both governed by the same relaxation time, τ, and that (2) high frequency dispersion in σ(ω), high frequency dispersion in the electric modulus peak, and distortion of a semicircle in the complex impedance plane, all arise from a distribution in τ, caused by the disordered structure of glass. Finally, a procedure of scaling ac data measured at various temperatures into a single master curve is given.     

Inhomogeneous structure and glass-forming ability in Zr-based bulk metallic glasses

Recently, a series of quaternary Zr-based bulk metallic glasses (BMGs), i.e., Zr₅₃Cu_18.7Ni₁₂Al_16.3, Zr_51.9Cu_23.3Ni_10.5Al_14.3 and Zr_50.7Cu₂₈Ni₉Al_12.3, have been developed and their glass-forming ability (GFA) increases with Cu concentration. In this work, atomic structures of the three BMGs were rebuilt by reverse Monte Carlo simulations based on the reduced pair distribution functions measured by high energy X-ray diffraction. The results show that a certain amount of substitution of short Zr-Cu, Cu-Cu pairs with long Zr-Zr and Zr-Al pairs enhances the local denser packing of Kasper polyhedral centered by Zr and Al atoms. A cell sub-divided method is proposed to describe the fluctuation of local number density which is found to follow the normal distribution function. The largest possible free volume in the three alloys is found to approaches to 3.8 Å. For the three alloys, the enhancement of GFA with increasing Cu content is due to the increase in the fluctuation degree of local density instead of the dense packing.     

Increased Si NMR sensitivity in glasses with a Carr-Purcell-Meiboom-Gill echotrain

The use of a Carr-Purcell-Meiboom-Gill (CPMG) echotrain to increase the ²⁹Si NMR sensitivity in glasses was investigated. The echo intensity decay follows a stretched exponential behavior M(t) = M₀ exp[−(t/t2)^β] with values for the exponent β in the range of 0.41-0.65. The signal to noise in the spectra can be increased by a factor of up to 4 by taking the weighted sum of the spectra obtained from the individual echoes. However, differential T2 relaxation for the different Qⁿ species is observed, with a shorter relaxation time for Q⁴ than Q³. Thus, summing of the echoes leads to distorted spectral intensities and quantitative information can no longer be obtained from the spectra. To circumvent the problem with differential T2 relaxation, an alternative approach is developed in which the spectral intensity for each chemical shift value is determined from the stretched exponential fit to its echo decay. With this approach, the sensitivity can be increased by a factor of up to 2.4, while quantitative information can still be obtained from the spectra. The increased sensitivity permitted the detection of five-coordinated silicon in a potassium silicate glass with natural ²⁹Si abundance at ambient pressure.     

Deep-UV Raman spectroscopic analysis of structure and dissolution rates of silica-rich sodium borosilicate glasses

As part of ongoing studies to evaluate relationships between structure and rates of dissolution of silicate glasses in aqueous media, sodium borosilicate glasses of composition Na₂O·xB₂O₃·(3 − x)SiO₂, with x ≤ 1 (Na₂O/B₂O₃ ratio ≥ 1), were analyzed using deep-UV Raman spectroscopy. Results were quantified in terms of the fraction of SiO₄ tetrahedra with one non-bridging oxygen (Q³) and then correlated with Na₂O and B₂O₃ content. The Q³ fraction was found to increase with increasing Na₂O content, in agreement with studies on related glasses, and, as long as the value of x was not too high, this contributed to higher rates of dissolution in single pass flow-through testing. In contrast, dissolution rates were less strongly determined by the Q³ fraction when the value of x was near unity, and appeared to grow larger upon further reduction of the Q³ fraction. Results were interpreted to indicate the increasingly important role of network hydrolysis in the glass dissolution mechanism as the BO₄ tetrahedron replaces the Q³ unit as the charge-compensating structure for Na⁺ ions. Finally, the use of deep-UV Raman spectroscopy was found to be advantageous in studying finely powdered glasses in cases where visible Raman spectroscopy suffered from weak Raman scattering and fluorescence interference.     

The structure and optical properties of GeO2-GeS2 glasses

Oxy-chalcogenide glasses with compositions of xGeO₂-(100 − x)GeS₂, where 0 ? x ? 100 mol%, have been prepared and studied in terms of their structures and optical properties. X-ray fluorescence spectroscopy shows that Ge:S ratio can deviate from GeS₂ by ∼10 at.%, depending critically upon the preparation conditions. Raman scattering spectroscopy suggests that stoichiometric GeO₂-GeS₂ glasses have a heterogeneous structure in the scale of 1-100 nm. The optical gaps are nearly constant at 3.0-3.5 eV for glasses with 0 ? x ? 80 mol% and abruptly increase to ∼6 eV in GeO₂. This dependence suggests that the optical gap is governed by GeS₂ clusters, which are isolated and/or percolated. Composition-deviated glasses appear as orange and brown, and these glasses seem to have more inhomogeneous structures.     

Structural characterization of ionomer glasses by multinuclear solid state MAS-NMR spectroscopy

In the present study we report the results of ²⁹Si, ²⁷Al, ³¹P and ¹⁹F magic angle spinning nuclear magnetic resonance spectroscopy (MAS-NMR) of 4.5SiO₂-3Al₂O₃-1.5P₂O₅-(5−z)CaO-zCaF₂ glasses with z = 0-3 to elucidate the effect of fluoride content on the glass structure. The ²⁹Si MAS-NMR spectra gave a chemical shift of about −90 ppm corresponding to Q³(3Al) and Q⁴(3Al). The ²⁷Al MAS-NMR showed a large broad central peak around 50 ppm, which is assigned to four-coordinated Al linked via oxygen to P. A shoulder around 30 ppm and a small peak at about 0 to −10 ppm appeared in the ²⁷Al MAS-NMR spectra of the glasses on increasing the fluoride content assigned to five-coordinated and six-coordinated Al species, respectively. The ³¹P MAS-NMR spectra indicated the presence of Al-O-P bonds. The ³¹P chemical shift decreased with increasing fluoride content as a result of calcium being complexed with fluoride. This resulted in a reduction of the number of available cations to charge balance non bridging oxygens in phosphorus and an increase in the number of Al-O-P bonds being formed, instead. The ¹⁹F spectra indicated the presence of Al-F-Ca(n) and F-Ca(n) species in all the glasses containing fluoride as well as an additional Si-F-Ca(n) species in the glasses with higher fluoride content.     

Structure and lattice dynamics of binary lead silicate glasses investigated by infrared spectroscopy

The polar lattices dynamics of seven binary lead silicate glasses have been studied by infrared spectroscopy. The analysis of the reflectivity spectra with a dielectric function model, based on a modified Gaussian profile, allows a quantitative evaluation of the presence of lead cations within different structural sites. From the role of the lead cations versus the degree of polymerization of the silicate network and the comparison with literature results, we may to give a scenario for explaining the observed structural evolution of the glass matrix and more particularly the drastic change occurring around 45% of lead content. Below this threshold, lead cations act only as modifiers of the silicate network. Above, the glass structure is deeply modified; a lead network involving around 10% of the lead content appears in glasses whose composition is just above the threshold and progressively grows at the expense of the silicate network with the increase of lead content. For high lead content, lead cations can act as modifiers of the silicate network or as network formers. Results also show that the analysis of far infrared measurements combined with the knowledge of the UV edge optical response is very promising to characterize the local disorder around cations in glasses.     

Irradiation-induced changes in the local environment of Si and Al in LnSiAlON glasses as probed by Al and Si NMR

Two compounds have been studied: an oxide glass from the Y-Si-Al-O system and an oxynitride glass from the Y-Si-Al-O-N system, both bombarded with Sn-ions (975 MeV, fluences ranging from 10¹² to 2.7 × 10¹³ Sn/cm²). The changes in the environment of the silicon and the aluminium were investigated using NMR spectroscopy. Irradiation by Sn ions leads to a loss of nitrogen in the silicon and probably the aluminium environments. Part of the aluminium changes from a network former coordination to a network modifier coordination while the oxide silicate network exhibits a higher cross-linking due to an increase of the population of bridging oxygen. Part of the aluminium in five-fold coordination is formed at the expense of aluminium in six-fold coordination in the case of the oxynitride glass and the changes in the silicon environment occur at lower fluences than for the oxide glass.     

Atomic structure of beryllium boroaluminate glasses: A multi-nuclear NMR spectroscopic study

The short-range structure and network speciation have been studied in a series of beryllium boroaluminate glasses using ¹¹B, ²⁷Al and ⁹Be NMR spectroscopy. All glasses are characterized by a coexistence of BeO₄, BO₃, BO₄, AlO₄, AlO₅ and AlO₆ species. The concentrations of BO₃, AlO₅ and AlO₆ species in these glasses are significantly higher and the geometry of the B-O and Al-O coordination polyhedra are unusually disordered compared to those in other alkali and alkaline-earth boroaluminate glasses reported previously in the literature. These results indicate that Be atoms may not play the typical role of a network-modifying cation in these glasses. This structural scenario is consistent with the highest field strength and electronegativity of Be among all alkali and alkaline-earth metals.     

Three-dimensional structure of fast ion conducting 0.5Li2S + 0.5[(1 − x)GeS2 + xGeO2] glasses from high-energy X-ray diffraction and reverse Monte Carlo simulations

A high-energy X-ray diffraction study has been carried out on a series of 0.5Li₂S + 0.5[(1 − x)GeS₂ + xGeO₂] glasses with x = 0.0, 0.1, 0.2, 0.4, 0.6 and 0.8. Structure factors were measured to wave vectors as high as 30 Å⁻¹ resulting in atomic pair distribution functions with high real space resolution. The three dimensional atomic-scale structure of the glasses was modeled by reverse Monte Carlo simulations based on the diffraction data. Results from the simulations show that at the atomic-scale 0.5Li₂S + 0.5[(1 − x)GeS₂ + xGeO₂] glasses may be viewed as an assembly of independent chains of (Li^+-S)₂GeS_2/2 and (Li^+-O)₂GeO_2/2 tetrahedra as repeat units, where the Li ions occupy the open space between the chains. The new structure data may help understand the reasons for the sharp maximum in the Li⁺ ion conductivity at x ∼ 0.2.     

The ionic transition and the glass transition in ion-conducting glasses

In an ion-conducting glass, there may be the ionic transition which characterizes ‘melting’ of the modifying ions in a similar way as the glass transition characterizes ‘melting’ of the glass network former. The ionic transition can be observed, electrically, by the thermally stimulated depolarization current technique. It is demonstrated that the relaxation time for the ionic transition is the same (near 100 s) with that for the glass transition in so far as the heating/cooling rate lies within, say, 10⁻¹-10⁻⁵ K/s as adopted in our routine works.