Tin valence and local environments in silicate glasses as determined from X-ray absorption spectroscopy

X-ray absorption spectroscopy (XAS) was used to characterize the tin (Sn) environments in four borosilicate glass nuclear waste formulations, two silicate float glasses, and three potassium aluminosilicate glasses. Sn K-edge XAS data of most glasses investigated indicate Sn⁴⁺O₆ units with average Sn-O distances near 2.03 Å. XAS data for a float glass fabricated under reducing conditions show a mixture of Sn⁴⁺O₆ and Sn²⁺O₄ sites. XAS data for three glasses indicate Sn-Sn distances ranging from 3.43 to 3.53 Å, that suggest Sn⁴⁺O₆ units linking with each other, while the 4.96 Å Sn-Sn distance for one waste glass suggests clustering of unlinked Sn⁴⁺O₆ units.     

Spectroscopic and structural properties of Cr in silicate glasses: Cr does not probe the average glass structure

Cr³⁺-containing alkali, alkaline earth and mixed alkali-alkaline earth silicate glasses have been investigated using Cr K-edge extended x-ray absorption fine structure (EXAFS) and optical absorption spectroscopy. The local environment of Cr³⁺ appears similar in all glasses regarding EXAFS analysis, in particular for Cr-O distance (1.99 Å). By contrast, optical absorption spectra show variations of crystal field values and disorder effects with the nature of the modifier cation, revealing that some differences exist in the local surrounding of Cr³⁺ in glasses. In addition, in mixed alkali-alkaline earth glasses optical absorption parameters remain close to the values found in binary silicate glasses with the same alkali, which reveals a preference for alkalis in the surrounding of Cr³⁺. As a whole, these data show that Cr³⁺ is not probing the average glass structure and demonstrate its heterogeneous distribution at a local scale.     

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.     

Silicate nanoparticles by bioleaching of glass and modification of the glass surface

Bioleaching is examined as a low temperature (50 °C) soft chemical approach to nanosynthesis and surface processing. We demonstrate that fungus based bioleaching of borosilicate glass enables synthesis of nearly monodispersed ultrafine (∼5 ± 0.5 nm) silicate nanoparticles. Using various techniques such as X-ray diffraction, X-ray photoelectron spectroscopy and FTIR we compare the constitution and composition of the nanoparticles with that of the parent glass, and establish the basic similarities between the two. The bioleaching process is shown to enhance the non-bridging oxygen component and correspondingly influence the Si-O-Si network. The root mean square roughness of glass surface is seen to increase from 1.27 nm for bare glass to 2.52 nm for 15 h fungal processed case, this increase being equivalent to that for glass annealed at 500 °C.     

Structure of praseodymium and neodymium gallate glasses

The rare-earth gallate glasses R₄Ga₆O₁₅, where R denotes Pr or Nd, were prepared using an aerodynamic levitator and laser heating system. The structure was studied by applying the method of isomorphic substitution in neutron diffraction which allows for an identification of the gallium and rare-earth coordination environments. The results give a mean Ga-O coordination number of 4.2(1) at a distance of 1.85(2) Å and a mean R-O coordination number of 7.4(2) at a mean distance of 2.38(2) Å. The experimental results are consistent with a glass network built from GaO₄ tetrahedra and with the presence of GaO₆ octahedra at the 10(5)% level.     

Sol-gel deposition of silica films on silicate glasses: Influence of the presence of lead in the glass or in precursor solutions

Many lead silicate historical glasses suffer degradation phenomena often observed as color changes and iridescence caused by lead ions leaching from the outer layers of the glass. In order to repair and to prevent these phenomena, glasses with large amounts of lead (6.7 and 14.3 at.% of lead) have been coated with silica films at neutral pH by dipping them in a precursor solution of TEOS (tetraethyl orthosilicate), ethyl alcohol and deionized water without any other acid or basic catalyst. Experiments with long dipping times (24 h) and temperatures around 20 °C have been performed to evaluate the role of lead ions of the glass as a catalyst. Silica films of very good quality and optical transparency have been also obtained on lead-free, soda-lime glasses by adding catalytic amounts of Pb(NO₃)₂ instead of HCl to the precursor solution. The films have been characterized by optical microscopy, AFM (Atomic Force Microscopy), XPS (X-ray Photoelectron Spectroscopy) and SIMS (Secondary Ion Mass Spectrometry).     

The structural role of Zr within alkali borosilicate glasses for nuclear waste immobilisation

Zirconium is a key constituent element of High Level nuclear Waste (HLW) glasses, occurring both as a fission product and a fuel cladding component. As part of a wider research program aimed at optimising the solubility of zirconium in HLW glasses, we have investigated the structural chemistry of zirconium in such materials using X-ray Absorption Spectroscopy (XAS). Zirconium K-edge XAS data were acquired from several inactive simulant and simplified waste glass compositions, including a specimen of blended Magnox/UO₂ fuel waste glass. These data demonstrate that zirconium is immobilised as (octahedral) six-fold coordinate ZrO₆ species in these glasses, with a Zr-O contact distance of 2.09 Å. The next nearest neighbours of the Zr species are Si at 3.42 Å and possibly Na at 3.44 Å, no next nearest neighbour Zr could be resolved.     

Effect of electron irradiation on Na-K silicate glass investigated using X-ray photoelectron spectroscopy and pattern recognition method

Alkali silicate glasses and melts play an important role in material science. Electron interaction with glasses is important for radioactive waste deposition, where electrons of various energies lead to irreversible changes. These changes are caused mainly by ionization and ballistic interaction of electrons with atoms, introducing structural disorder, changes in atomic composition and chemical state, accompanied by alkali ions diffusion. The Na-K silicate glass (5Na₂O · 10K₂O · 85SiO₂), pristine and electron irradiated (doses from 25 C m⁻² to 20 236 C m⁻²) are investigated using X-ray photoelectron spectroscopy (XPS) and the pattern recognition (PR) and fitting procedures. Changes of composition and chemical state of atoms dependent on electron dose are analyzed. At low doses (100-300 C m⁻²), decrease followed by increase of O and Si concentrations was observed. Surface segregation, probable desorption, and in-bulk diffusion of K and Na ions (doses of about 50 C m⁻² and 2000 C m⁻², respectively) were observed. This was accompanied by changes in the chemical state of K atom, where with an electron dose increasing content of elemental K form accompanied by decreasing potassium peroxide form were observed. No difference in chemical state of Si and O atoms was visible under electron irradiation dose to 20 236 C m⁻², within the sensitivity of the applied method.     

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.     

Leaching studies on naturally weathered potash-lime-silica glasses

Within the international, EU-supported research project MULTI-ASSESS more than 150 glass samples with a chemical composition similar to medieval stained glasses were exposed in six European cities (Athens, Krakow, London, Prague, Rome and Riga) to the local environmental and climatic conditions. After exposure periods of 6 or 12 months the samples were investigated in the scanning electron microscope with energy dispersive X-ray microanalysis (SEM/EDX). Surface analyses indicate that the main weathering products were sulphates such as syngenite (CaSO₄ · K₂SO₄ · H₂O) and gypsum (CaSO₄ · 2H₂O). Chlorides, organic compounds and/or carbonates or nitrates of the elements K, Ca and Na were predominantly detected on the 6-months samples, whereas Si-containing compounds appeared particularly on the 12-months samples. Linescan measurements performed on the cross-sectioned glass samples allowed for the determination of leaching depths of the network modifier ions according to an evaluation procedure recently presented. The average leaching depths after 6 months of exposure were d(K) = 0.88 ± 0.43 μm, d(Ca) = 0.62 ± 0.37 μm, d(Na) = 0.34 ± 0.32 μm and d(Mg) = 0.16 ± 0.18 μm. After 12 months an average increase of the leaching depths between 38% (K) and 63% (Mg) is observed. No leaching could be determined for the network former elements Al and P. A clear influence of the environmental conditions at the atmospheric test sites on the degree of weathering was observed. In a first approximation, the leaching depths exhibit a linear dependence on a general pollution factor comprising the concentrations of the acidifying gases SO₂, NO₂ and O₃.     

Raman amplification in nanoparticles doped glasses

Resonant Raman effects are studied for CdS_xSe_1−x nanoparticles in a silicate glass matrix in order to explore new possibilities of Raman amplification for telecommunication fibers. Nanoparticles with diameters ranging from less than 2 nm up to 6 nm are excited with the 458 nm, 488 nm and 633 nm laser lines corresponding both to resonance and off-resonance conditions. Due to confinement effects the resonance conditions are achieved at a given frequency by varying the size of the nanoparticles. In resonance no enhancement is observed for the silicate glass matrix but the (1LO-CdS), (2LO-CdS), (1LO CdSe + 1 LO CdS) modes are strongly enhanced showing the possibility of resonant Raman amplification of the discrete frequencies of the LO modes and of their overtones.     

Structure of potassium germanophosphate glasses by X-ray and neutron diffraction: 2. Medium-range order

Characteristics of the medium-range order (MRO) of K₂O-GeO₂-P₂O₅ (KGP) glasses are obtained from X-ray and neutron scattering data. The behavior of the MRO is expressed in changes of pre-peaks and smooth contributions in the structure factors, S(Q), for Q < 12 nm^-1. Peaks at Q = (7.5 ± 0.5) nm^-1 (Q - magnitude of the scattering vector) are the outstanding features and reach maximum intensity for a glass of ∼25/50/25 mol% K₂O/GeO₂/P₂O₅. The pre-peaks are explained by a structural model in which K-rich and Ge-rich regions are separated by PO₄ units. The distance of repetition of similar regions (∼1 nm) is responsible for the pre-peak at ∼7.5 nm^-1. The intensity of this pre-peak is reduced and finally eliminated for glass compositions approaching the binary GeO₂-P₂O₅ system. The pre-peak is changed to a smooth scattering contribution and finally shifted to ∼9 nm^-1 for glass compositions approaching the binary K₂O-GeO₂ system. The strong tendency of the PO₄ units to coordinate K⁺ and Ge neighbors at their four corners is the source for the special MRO of the KGP glasses.     

Nucleation time-lag from nucleation and growth experiments in deeply undercooled glass-forming liquids

A new approach is proposed to explain the strong difference between the induction periods (nucleation time-lags) obtained from nucleation rate measurements and from crystal growth experiments for lithium silicate glasses; and their similar magnitude for a Na₂O · 2CaO · 3SiO₂ glass. For these two glass families, the time-lags for nucleation estimated from crystal growth kinetics were compared with those directly obtained from nucleation experiments. A theoretical analysis was performed employing analytical solutions of the Frenkel-Zeldovich equation. In such analysis, the frequently assumed condition of size-independence of the thermodynamic properties of the crystallites was used. Provided this assumption is correct, time-lag data obtained in the two above mentioned ways should coincide. Consequently the significant difference between the values of nucleation time-lag for lithium silicate glasses from nucleation and growth data gives a strong indirect evidence for the deviation of the properties of critical nuclei from the respective parameters characterizing the state of the newly evolving macrophase. For Na₂O · 2CaO · 3SiO₂ glass at intermediate stages of crystallization we show that the average composition of the growing crystals is close to that of the near-critical nuclei. The fact that the nucleation and growth rates of this soda-lime-silica glass refer to the same phase provides an explanation for the similarity of the induction periods estimated from nucleation and growth experiments.     

Short, intermediate and mesoscopic range order in sulfur-rich binary glasses

Pulsed neutron and high-energy X-ray diffraction, small-angle neutron scattering, Raman spectroscopy and DSC were used to study structural changes on the short, intermediate and mesoscopic range scale for sulfur-rich AsS_x (x ? 1.5) and GeS_x (x ? 2) glasses. Two structural regions were found in the both systems. (1) Between stoichiometric (As₂S₃ and GeS₂) and ‘saturated’ (AsS_2.3 and GeS_2.7) compositions, excessive sulfur atoms form sulfur dimers and/or short chains, replacing bridging sulfur in corner-sharing AsS_3/2 and GeS_4/2 units. (2) Above the ‘saturated’ compositions at [As] < 30.5 at.% and [Ge] < 27 at.%, sulfur rings and longer sulfur chains (especially in the AsS_x system) appear in the glass network. The glasses become phase separated with the domains of 20-50 Å, presumably enriched with sulfur rings. The longer chains S_n are not stable and crystallize to c-S₈ on ageing of a few days to several months, depending on composition.     

Structure of liquid Al-Cu-Co alloys near the quasicrystal-forming range

A local short-to-intermediate range order in liquid Al_63.9Cu_19.4Co_16.7, Al₇₁Cu₆Co₂₃, and Al_6oCu₂₉Co₁₁ alloys was investigated by X-ray diffraction technique and the reverse Monte Carlo modeling. A prepeak at Q ~ 17 nm^− 1originating from the unique bonding between the TM-TM pair (TM = Co, Cu) is observed in the structure factors of all investigated melts. The Voronoi-Delaunay analysis of RMC models indicates that a medium-range ordering of TM atoms in dense non-crystalline polytetrahedral clusters is associated with a chemical short-range order. The icosahedral short-range order is also closely related to the dense packing polytetrahedral clusters. A decrease of temperature leads to an enhancement of both chemical short-range order and icosahedral short-range order.     

Structural changes between soda-lime silicate glass and melt

Neutron diffraction has been used to study the structure of a glass and melt of composition 75SiO₂-15Na₂O-10CaO. RMC modeling of the neutron and X-ray diffraction data for the glass allowed the determination of the Na and Ca environment. The structure has been investigated at 300K, just below the glass transition at 823 K and in the melt at 1273 K. The short range order does not present important modifications with temperature while significant reorganization appears at the medium range order. These latter changes can be associated with the Si and O pairs and indicate the relaxation of the silicate network. This indicates that the glass formation involved structural rearrangement during cooling.     

Leaching of some lithium silicate glasses and glass-ceramics by HCl

The leaching of some binary and ternary lithium silicate glasses and their respective glass-ceramics by HCl is reported.The leaching rate of lithium silicate glasses gradually decreases with the decrease of the percentage of Li₂O or by the introduction of small amounts of a third component, e.g. Al₂O₃, MgO, ZnO or B₂O₃. With a further increase in the proportions of B₂O₃ or ZnO the rate of leaching increases. The rate of leaching is also substantially modified by the conversion of glasses into glasses-ceramics.The results obtained are discussed in terms of the effects of the different ions on the rate of the interdifussion of the lithium and hydrogen ions in the glass and the leached layer, the phase separation developed in the glass, the type and concentration of crystalline phases developed in glass-ceramics and the composition of the residual glass phase.     

Molecular dynamics simulations of calcium aluminate glasses

Molecular dynamics simulations of a series of calcium aluminate glasses have been carried out using empirical potentials with a covalent term. The simulations closely reproduce the total neutron correlation function of glasses with 30 and 38 mol% Al₂O₃ and physical properties such as elastic constants. For compositions close to the eutectic 37 mol% Al₂O₃, aluminum is tetrahedrally coordinated by oxygen, but the proportion of five-fold and six-fold coordination and also edge-sharing tetrahedra gradually increases with increasing Al₂O₃ content. The coordination number for oxygen around calcium atoms is close to 6 and this involves a larger coordination at a shorter, well-defined distance, followed by a smaller coordination with a broader range of distances. When the Al₂O₃ content decreases, the calcium aluminate structure becomes depolymerised and the average ring size increases. Also reported is an X-ray photoelectron spectroscopy measurement on a glass sample with 38 mol% Al₂O₃, which shows that 38.6 ± 0.9% of the oxygens are non-bridging, in excellent agreement with the simulations.     

High-temperature XAFS study of solid and molten SrCl2

The local structure of solid and molten SrCl₂ was investigated by X-ray absorption fine structure technique. According to the curve fitting analysis with assessment of the anharmonic vibration effect, the nearest Sr²⁺-Cl⁻ distance and the coordination number are 2.99 ± 0.01 Å and 6.6 ± 0.2 in molten state. XAFS functions calculated from molecular dynamics simulation results were compared with the experimental XAFS data.     

Crystal growth of KInO2 from a hydroxide flux

Single crystals of KInO₂ were obtained from a reactive potassium hydroxide flux at 700 °C. KInO₂ crystallizes in the R-3m crystal system with a=3.2998(10) Å, c=18.322(10) Å and V=172.78(12) Å³. The crystal structure is isotypic with that of α-NaFeO₂ and consists of the (1 1 1) layers being occupied alternately by KO₆ and InO₆ octahedra. Three different AInO₂ structure types are discussed.