Sodium diffusion in boroaluminosilicate glasses

Understanding the fundamentals of alkali diffusion in boroaluminosilicate (BAS) glasses is of critical importance for advanced glass applications, e.g., the production of chemically strengthened glass covers for personal electronic devices. Here, we investigate the composition dependence of isothermal sodium diffusion in BAS glasses by ion exchange, inward diffusion, and tracer diffusion experiments. By varying the [SiO₂]/[Al₂O₃] ratio of the glasses, different structural regimes of sodium behavior are accessed. We show that the mobility of the sodium ions decreases with increasing [SiO₂]/[Al₂O₃] ratio, revealing that sodium is more mobile when it acts as a charge compensator to stabilize network formers than when it acts as a creator of non-bridging oxygens on tetrahedrally-coordinated silicon and trigonal boron. The impacts of both the addition of iron and its redox state on the sodium diffusivity are explored in terms of the structural role of ferric and ferrous ions. By comparing the results obtained by the three approaches, we observe that both the tracer Na diffusion and the Na–K interdiffusion are significantly faster than the Na inward diffusion. The origin of this discrepancy could be attributed to the fact that for sodium inward diffusion, the charge compensation for electron holes is a rather slow process that limits the rate of diffusion.     

Sodium tracer diffusion in sodium boroaluminosilicate glasses

Sodium tracer diffusion coefficients, D*_Na, have been measured using the radioactive isotope Na-22 in sodium boroaluminosilicate (NBAS) glasses containing either a small amount of As₂O₃ or Fe₂O₃. The chemical compositions of the first type of glasses are given by the formula [(Na₂O)_0.71(Fe₂O₃)_0.05(B₂O₃)_0.24]_0.2[(SiO₂)_x(Al₂O₃)_1 ? x]_0.8 and those of the second type of glasses correspond to the formula [(Na₂O)_0.73(B₂O₃)_0.24(As₂O₃)_0.03]_0.18[(SiO₂)_x(Al₂O₃)_1 ? x]_0.82. Tracer diffusion measurements were performed at different temperatures between 198 and 350 °C. Pre-annealing of the glass samples at their glass transition temperatures in common air was found to lead to changes in the values of sodium tracer diffusion coefficients. For the NBAS glasses containing Fe₂O₃, after pre-annealing for 5 h, the activation enthalpy derived for the sodium tracer diffusion increases almost linearly from 57.5 to 71.3 kJ/mol with a decrease in the alumina content while the pre-exponential factor of the sodium tracer diffusion coefficient increases from 2.1 · 10^? 4 to 5.3 · 10^? 4 cm²/s. For the iron-free NBAS glasses pre-annealed for 5 h, the activation enthalpy varies between 63.9 and 71.4 kJ/mol while the pre-exponential factor varies between 1.5 · 10^? 4 and 1.2 · 10^? 3 cm²/s. In addition, it was observed that the considered glasses take up water when annealed at 300 °C in wet air with P_H2O = 474 mbar.     

Structural studies on AsSe–AgI glasses

The atomic structure of the binary AsSe, ternary (AsSe)₈₀Ag₂₀, (AsSe)₈₅I₁₅ and quaternary (AsSe)₆₅(AgI)₃₅ glasses has been studied with the X-ray and neutron diffraction. The local order was also probed with the extended X-ray absorption fine structure spectroscopy at Ag, As and Se K-edges. All experimental data were modeled simultaneously by the reverse Monte Carlo technique. Analysis of the partial pair distribution functions and their characteristics enabled to retrace the structural changes from binary AsSe to pseudo-binary (AsSe)_100−x(AgI)_x system and to study the influence of Ag and I incorporation on the local structure.     

Structural studies of lead aluminate glasses

Lead aluminate melts were quenched rapidly with a roller quencher and bulk glasses were formed over a composition range from 72.5 to 80.0 mol% PbO. Pulsed neutron diffraction, ²⁷Al MAS NMR and Raman spectroscopy were used to study the structure of a series of these glasses. The results show that in the glasses the aluminium is four coordinated by oxygen across the compositional range, with a bond length of about 1.76 Å. The Pb–O peak in the neutron correlation function is asymmetric, and it can be modelled in terms of two bond lengths of ∼2.25 Å and ∼2.47 Å, with the majority of the coordination at the shorter distance. There is evidence that most or all of the lead ions are on asymmetric sites, coordinated by three oxygens in a trigonal pyramid arrangement. Both the neutron diffraction and Raman results indicate that the Pb–O bond lengths become shorter with increasing lead content.     

Structural studies of phosphate glasses with high ionic conductivity

Lithium phosphate glasses with different chemical composition have been studied using infrared absorption spectroscopy (FTIR) and photoelectron spectroscopy (XPS). FTIR and XPS spectra were analyzed to determine the main structural units present in the glass. Absorption bands were identified and assigned to appropriate bond vibrations. It has been shown that analyzed glasses are built up mainly of short chains and rings consisting of metaphosphate structural units - Q². Some pyro- and orthophosphate units Q¹ and Q⁰, respectively are also present. Photoelectron spectroscopy studies have revealed that titanium exists in two valence states: as Ti³⁺ and Ti⁴⁺. Increasing TiO₂ content results in shortening of P-O bonds but leads to elongation of PO bonds in PO₄ tetrahedra.     

Structural studies of ThO2 containing barium borosilicate glasses

Barium borosilicate glasses containing as much as 18.6 wt% ThO₂ have been prepared by a conventional melt–quench method and characterized by ²⁹Si and ¹¹B magic angle spinning nuclear magnetic resonance (MAS NMR), Infrared (IR) absorption and differential thermal analysis (DTA) techniques for their structural features. Based on ²⁹Si and ¹¹B MAS NMR and IR investigations, it has been established that the borosilicate network is not affected by such a large ThO₂ incorporation. Whereas Si exists as Q³ and Q² structural units in the ratio of ∼0.7, boron exists in both trigonal (BO₃) and tetrahedral (BO₄) configurations and their relative concentrations are not affected by ThO₂ incorporation in these glasses. The higher extent of ThO₂ incorporation in barium borosilicate glasses compared to borosilicate glasses has been attributed to the increased number of non-bridging oxygen atoms present in the barium borosilicate glasses. Based on DTA measurements it has been shown that there is neither any change in the glass transition temperature nor the occurrence of any crystallization up to 1000 °C, for ThO₂ incorporation up to 18.6 wt% in these glasses. For higher concentrations of ThO₂, there is phase separation during glass formation and fine crystallites of ThO₂ are formed as revealed by XRD. These findings are of significance for the nuclear waste management related to thorium fuel cycle.     

Structural studies of solution-made high alkali content borate glasses

The glass forming range of alkali borates has been extended to R = 5.0 (83 mol% alkali oxide) using a solution method. This method involves the reaction between solutions of boric acid (H₃BO₃) and alkali hydroxide (MOH). Physical properties and NMR studies were performed on the intermediate and final glass products of this method. We have obtained results for the entire alkali borate system including lithium, sodium, potassium, rubidium and cesium. The structure of these invert glasses remains enigmatic.     

Structural analysis of bioactive glasses

In this study four series of single and mixed alkali glass systems were made and investigated using MAS NMR. Additionally the densities of the glasses were measured experimentally, as well as calculated theoretically using Doweidar’s model. MAS NMR was used to obtain a quantitative structural understanding of glasses by calculating the concentrations of bridging and non-bridging oxygens per silicon oxygen tetrahedron as a function of the alkali oxide concentration expressed as Qⁿ. ²⁹Si MAS NMR spectra exhibited a single resonance corresponding closely with Si in a Q² state. The chemical shift of the ³¹P MAS NMR peak was attributed to phosphate in an orthophosphate environment. The ²⁹Si NMR spectra are in agreement with the density data. Using Doweidar’s model the proportions of Q² and Q³ were calculated, showing that all glasses studied are predominantly Q² in structure, i.e. silica chains which readily dissolve. The changes in the chemical shifts of the Q² and Q³ species with composition have been interpreted as resulting from the preferential association of Na⁺ with Q³ and Ca²⁺ with Q².     

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.     

Structural study of magnesium polyphosphate glasses

Magnesium polyphosphate glasses with molar ratios, y=n(MgO)/n(P₂O₅), ranging from 1.0 to 1.9 have been examined by X-ray and neutron scattering and ³¹P magic angle spinning nuclear magnetic resonance spectroscopy to extract information on their short-range, intermediate-range and submicroscopic structure. The depolymerization of the PO₄ chains with rising MgO content is quantitatively described by the increasing concentration of Q¹ and Q⁰ groups determined by NMR. In the pyrophosphate region the Q¹ sites disproportionate to Q⁰ and Q² groups, whereas there is no disproportionation of the Q² sites at metaphosphate composition. The shortening of the real-space distances, r_m, indicates that the structure of the glasses becomes more compact with progressive depolymerization which is due to the increasing connection of the MgO_n polyhedra by sharing the non-bridging oxygen atoms. The Mg–O co-ordination sphere was found to change not significantly in dependence on composition. Heterogeneities about 1 nm in diameter exist in the glasses with MgO content exceeding 46.6 mol% indicated by a weak small angle X-ray scattering.     

Structural studies on fullerenes

Amongst the other physical properties, the structure of fullerene solids, and the structural transformations with temperature, pressure and doping have all evoked considerable interest and during the last two years tremendous progress has been made in this area. This paper provides a brief review of the studies on the structural properties of pristine and doped fullerenes. The results of our own investigations are also presented.     

Elastic properties and structural studies on lead-boro-vanadate glasses

This paper describes elastic properties and spectroscopic studies on the xPbO-50B₂O₃-(50 - x)V₂O₅ (where x = 20, 25, 30, 35, 40, 45 and 49 mol%) glass system. Elastic moduli and spectroscopic parameters exhibit compositional dependent trends and the existence of characteristic borovanadate groups in these glasses. The bulk modulus and shear modulus increase with the concentration of [BO_4/2]⁻ and [B₂V₂O₉]²⁻ groups, which increases the dimensionality of the network. The scheme of modification of borate and vanadate groups has been explained by considering the Sanderson’s electronegativity principle. Analysis of infrared(IR) and magic angle spinning-nuclear magnetic resonance (MAS-NMR) spectra suggests the presence of characteristic diborovanadate groups also in these glasses. The results are examined in view of the structural groups formed due to the presence of PbO as a modifier.     

Electrochemical studies on ionic behavior in molten glasses

Some fundamental electrochemical studies on ionic behavior like the diffusion and redox equilibria of various foreign ions in molten glasses which were carried out by the authors are described.     

Structural features of hafnium iron phosphate glasses

Structural features and properties of a series of hafnium iron phosphate glasses have been investigated by Mössbauer spectroscopy and X-ray diffraction. Mössbauer spectra indicate that all of the glasses contain both Fe(II) and Fe(III) ions. The isomer shift values obtained from the Mössbauer fits show that both Fe(II) and Fe(III) ions are in octahedral or distorted octahedral coordination. The crystalline HfP₂O₇ phase was detected in all the samples by powder X-ray diffraction but this did not degrade the chemical durability of the glasses as the dissolution rates of the glasses are comparable to that of base iron phosphate glass.     

Diffraction studies of rare-earth phosphate glasses

A series of lanthanide oxides was incorporated in a vitreous phosphate host network. Molar constituents of the glasses were typically (La₂O₃)₁₀(R_xO_y)₁₀(Al₂O₃)₅(P₂O₅)₇₅. Each glass had a different lanthanide (R atom) from the series; La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er and the values of x and y depended on the valency of the rare-earth atom. Both X-ray and neutron diffraction were employed in examining their structures. The results indicate that the basic PO₄ tetrahedral unit remains unaltered with an average P–O distance of and predominant Q² linkages to its neighbouring units so as to form a continuous network while accommodating the included lanthanides. In accordance with this model, the average distance of rare-earth (comprising La and a second type of R atom) to oxygen decreased from 2.44 to 2.26 , a trend to be expected from the lanthanide contraction. The average oxygen coordination around the rare-earth was found to vary in the range of 6–8. With these average parameters, a small (74 atom) hand-built model was made to check the feasibility of constructing a continuous random network. Optical transmission measurements show all these glasses to absorb strongly in the UV region and to have marked absorption resonances in the visible region of 400–1000 nm except for the La, Ce, Eu, Tb containing glasses which have low or negligible absorption in the latter range.     

Kerr studies of several tellurite glasses

Estimates of Kerr electrooptical sensitivity of several tellurite glasses are presented. The highest value of Kerr coefficient B ～ 190 × 10^?16 m V^?2 is registered for 0.6TeO₂–0.3TlO_0.5–0.1ZnO glass. This evidences the prospects of thallium–tellurite glass system for electrooptical applications. A gradual decrease of B from 41 × 10^?16 to 26 × 10^?16 m V^?2 in (1 ? x) TeO₂ – xNbO_2.5 system is revealed for x increasing from 0.1 to 0.15. No crystalline phase was found in that system, thus allowing attributing its Kerr sensitivity to the intrinsic properties of the glass matrix. The Kerr coefficient variation from 66 to 81 × 10^?16 m V^?2 was observed for 0.85TeO₂–0.15WO₃ glasses co-doped with small amounts of silver and cerium. The analysis of optical absorption spectra of several silver-containing tellurium–tungsten oxide glasses makes it possible to think that introducing cerium provokes formation of new mid-range orderings.     

Electrical switching and thermal studies on bulk Ge-Te-Bi glasses

Bulk, melt quenched Ge₁₈Te_82-xBi_x glasses (1 ≤ x ≤ 4) have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of Ge-Te-Bi samples. A linear variation in switching voltages (V_th) has been found in these samples with increase in thickness which is consistent with the memory type electrical switching. Also, the switching voltages have been found to decrease with an increase in temperature which happens due to the decrease in the activation energy for crystallization at higher temperatures. Further, V_th of Ge₁₈Te_82-xBi_x glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of V_th, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content, which is consistent with the observed decrease in the switching voltages. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe, Bi₂Te₃ phases, suggesting that bismuth is not taking part in network formation to a greater extent, as reflected in the variation of switching voltages with the addition of Bi. SEM studies on switched and un-switched regions of Ge-Te-Bi samples indicate that there are morphological changes in the switched region, which can be attributed to the formation of the crystalline channel between two electrodes during switching.     

Calorimetric studies of AgI-doped tellurite glasses

The heat capacity changes during the glass transition of TeO₂---TlO_0.5 glasses containing AgI or (AgI)_0.75(TlI)_0.25 up to mole fractions of 0.4 or 0.55 have been measured by differential scanning calorimetry. The glass transition temperatures of the binary compositions decrease with increasing TlO_0.5/TeO₂ ratio. With rising Ag⁺ concentration, the cohesion of the glass network is weakened and the structural contributions to the relaxation phenomenon as well as its activation enthalpies diminish. There is no interaction between the iodide in probably crystalline form and the host glass network. Compared with binary and ternary silver tellurite glasses, the corresponding thallium tellurite compositions are less stable.